New color-forming compositions and recording material

FIELD: color-forming compositions and recording material.

SUBSTANCE: claimed composition includes developer containing urea-urethane compound and colorless or light colored leuco dye. Recording material based on this composition also is proposed.

EFFECT: color-forming compositions with improved image conservation ability and increased image intensity.

21 cl, 14 tbl, 153 ex

 

The present invention relates to a new urea-urethane compound. The present invention also relates to a new color-forming composition, which is obtained using urea-Urmanova connection, and the recording material, which is obtained using the color-forming composition.

Color-forming composition of the present invention is used as a color-forming composition for a recording material, which use recording energy, such as heat, pressure or the like, and, in particular, the present invention relates to a color-forming composition, which can improve the stability of the unpainted parts (the original surface of the recording material storage and developed color image to the recording material, in particular to a heat-sensitive recording material, which is obtained by use of color-forming composition.

Background of the invention

There are various color-forming chemical systems that use the recording energy, such as heat, pressure or the like. Among these systems have long been known color-forming system, usually consisting of two color-forming system containing a colorless or light-colored substance is precursor of dye and take the spruce, can cause color upon contact with the substance is a precursor of the dye, and, as a rule, used in recording materials. There are, for example, pressure-sensitive recording materials, which are recorded using pressure, heat-sensitive recording materials, which are recording, using the heat and light-sensitive recording materials, which are recording using light.

Pressure-sensitive recording materials are commonly used in planar form, such paper. Usually a pressure-sensitive recording material was obtained by dissolving substances, precursor of the dye in a suitable solvent, emulsifying the resulting solution to a few microns and forming emulsion microcapsules. The first layer of paper (also referred to here as the upper paper obtained by coating the substrate with the microcapsules and the second layer of paper (also referred to here as the lower paper obtained by coating other substrate showing the layer containing the developer, are placed on each other so that the surface coated with the microcapsules, and the surface covered by the developer, were facing each other. When the system is applied the pressure by writing, touch, or t the th like, microcapsules are destroyed, releasing content that includes substance is precursor of the dye. The substance is precursor of the dye moves in manifesting layer to interact with the developer, causing the degree of color development reaction, leading to the recording of the image.

In recent years, heat-sensitive recording method comprising recording using thermal energy, often used in various information devices such as facsimiles, printers, recorders and the like. Heat-sensitive recording material used in the heat-sensitive recording method has many excellent characteristics, such as high whiteness, clarity and sensitivity that is similar to the characteristics of the conventional planar paper, and perfect for recording, for example for high-quality color reproduction. Method thermosensitive recording suitable for such methods, which used the device features a small size, maintenance-free and produces no noise. Thus, the scope of application of the method thermosensitive recording in various fields, such as recording devices for measuring, facsimiles, printers, computer terminals, labels and the automatic machines for trade train tickets or the like, expands.

In the method thermosensitive recording mainly used recording material obtained by coating on the substrate color-forming layer containing a two-component color-forming composition, and heat-sensitive components of the composition come into contact with each other by processing the recording material with heat supplied in the form of a recording energy from the terminal of the recording head, a hot stamp, laser beams or the like, therefore, is the manifestation of color and the record. Many compositions that are used as color-forming composition obtained by using a colorless or light-colored electron-donating substances, precursor of the dye (in particular, leucogranites) and acidic developer such as a phenolic compound. An example of the recording material obtained through the use of substances, precursor of the dye is thermal paper is obtained by using as a heat-sensitive color-forming composition combination of crystal violet lactone and 4,4’-isopropylidenediphenol (bisphenol a) (see U.S. patent No. 3539375 and so on).

As a matter of the dye precursor and the developer used in each of the above recording the x methods mainly used electron-donating compound and the electron-acceptor compound, respectively. This is due to the fact that electron-donating compound and the electron-acceptor compound are, for example, the following excellent characteristics: substance is a dye precursor, such as an electron-donating compound and the developer, such as electron-acceptor compound, come into contact with each other with obtaining almost immediately high-intensity color image; and can be obtained almost white shade, and can be obtained in different colors such as red, orange, yellow, green, blue, black and so on. However, manifested a color image is so weak in terms of chemical stability, it quickly disappears upon contact with the plasticizer contained in the plastic sheet or the eraser, or chemicals contained in food or cosmetics. Also shown color image is so low retention period record that the record is dull or, worse, disappear under the action of direct sunlight in a relatively short period of time. Thus, the color-forming composition containing the substance, the precursor of the dye and the developer is largely limited in its p the changes, and their improvement is highly desirable.

In recent years, a phenolic compound represented by bisphenol a, are considered to be unsuitable for use, as they may cause damage to the endocrine system and therefore are preferred naftalene developers.

To implement this requirement, for example, in Japanese patent JP-A-59-115887 and U.S. patent No. 4521793 as recording materials with long shelf life describes a recording material containing a combination of color-forming compositions comprising an aromatic isocyanate compound and aminosidine. In these references describes the various recording materials, in which the two color-forming composition come into contact with each other to interact when using the recording energy, such as heat, pressure, light or the like. In the references described the fact that different colors such as red, orange, yellow, light brown, dark brown and so forth can be formed by appropriate selection of the color-forming compositions. However, in the inventions described in the links, not enough was evident black color, which is highly desirable in relation to typically the currently used recording materials.

In Japanese patent JP-A-8-2111 and Japanese patent JP-A-8-2112 as t is locustville recording materials, benefits of using nefrologia developer, describes heat-sensitive recording materials that have color-forming layer containing a colorless or slightly coloured substance is precursor of the dye and the compound of urea. However, these recording materials provide low intensity staining and have a poor shelf life.

In Japanese patent JP-A-5-116459 described heat-sensitive recording material containing heat-sensitive color-forming layer comprising a colorless or slightly coloured substance, the precursor and the connection sulfonylureas. However, this recording material has a low degree of whiteness and poor shelf life.

Description of the invention

The present invention relates to a new urea-urethane compound or a urea-urethane composition that/Aya shows excellent performance when used as a developer in the color-forming composition.

The present invention also relates to a new color-forming composition having excellent ability to save the image and intensity image, and the recording material, in particular to a heat-sensitive recording material, which is obtained by using cotobro the total composition, using any of the various urea-urethane compounds or urea-urethane compositions.

In addition, the present invention relates to a new color-forming composition having more improved performance by adding various additives to the urea-urethane compound, or urea-urethane composition and substance-the precursor of the dye, and the recording material obtained by using the color-forming composition.

The authors of this invention have thoroughly investigated the synthesis of various compounds for the color-forming composition and as a result discovered that certain compounds unexpectedly demonstrate superior performance on the basis of which was created by the present invention. In addition, the authors of this invention have found that certain compounds unexpectedly exhibit excellent performance characteristics in combination with a particular substance is a precursor of the dye on the basis of which was created by the present invention.

Thus, the present invention is as follows.

The first aspect of the invention relates to a urea-urethane compound, which is characterized by what is represented by the following formula (C) and has a molecular weight equal to the 5000 or less:

where R represents the residue of aliphatic compounds, A1and a2independently represent a residue of aromatic compounds, the nitrogen atom of the urea group directly linked to carbon atoms of aromatic rings A1and a2respectively, and R, A1and a2can have one or more substituents. The second aspect of the invention relates to a urea-urethane compound, which is characterized by what is represented by the following formula (d):

where R represents the residue of aliphatic compounds, atom(s) of each hydrogen of the benzene ring may be substituted(s) the remainder of aromatic compounds, a residue of aliphatic compounds, a residue of heterocyclic compounds, a hydroxyl group, a nitro-group, a nitrile group, carbamoyl group, sulfamoyl group, a carboxyl group, nitrosopropane, amino group, accelerograph, nitrolingual, hydratherapy, raidgroups, isocyanate group, mercaptopropyl, sulfopropyl or halogen atom, and R may have one or more deputies.

The third aspect of the invention relates to a urea-urethane compound, which is characterized by what is represented by the following formula (e) is whether (f), and includes at least one urethane group and at least one urea group with a total of not more than 10 and not less than 3, and has a molecular weight of 5000 or less:

where R represents the residue of aliphatic compounds, Y is a residue of aromatic compounds, a residue of a heterocyclic compound or a residue of aliphatic compounds, α1represents the residue of an aromatic, heterocyclic or aliphatic compounds, which is different from Y and has a valence equal to 2 or more, n represents an integer of 2 or more, and each of the residues may have one or more substituents; or

where Z1and Y independently represent a residue of an aromatic compound or a residue of heterocyclic compounds, β1represents a residue of aliphatic compounds having a valence of 2 or more, n represents an integer of 2 or more, and each of the residues may have one or more deputies.

A fourth aspect of the invention relates to a urea-urethane compound, which is characterized by the fact that is represented by the formula (g) or (h):

where the atom(s) of each hydrogen Benz is a high rings may be substituted(s) the remainder of aromatic compounds, the remainder of the aliphatic compounds, a residue of heterocyclic compounds, a hydroxyl group, a nitro-group, a nitrile group, carbamoyl group, sulfamoyl group, a carboxyl group, nitrosopropane, amino group, accelerograph, nitrolingual, hydratherapy, raidgroups, isocyanate group, mercaptopropyl, sulfopropyl or a halogen atom, β1represents a residue of aliphatic compounds, which has a valency of 2 or more, n is an integer equal to 2 or more, and each of the residues may have one or more substituents; or

where R independently represent a residue of aliphatic compounds, atom(s) of each hydrogen of the benzene ring may be substituted(s) the remainder of aromatic compounds, the aliphatic residue of a compound or a residue of heterocyclic compounds, each of the residues may have one or more substituents, γ1represents a group selected from the group comprising-SO2-, -O-, -(S)n-, -(CH2)n-, -CO-, -CONH-, -NH-, -CH(COOR1)-, -C(CF3)2-, -CR2R3and any of the groups represented by the formula (a):

or absent; each of R1, R2and R3pre is represents an alkyl group, and n is 1 or 2.

The fifth aspect of the invention relates to a urea-urethane composition which is characterized in that it includes a urea-urethane compound and the diluent.

The sixth aspect of the invention relates to a urea-urethane composition according to the fifth aspect of the invention, where the diluent is a compound of urea and/or urethane connection.

The seventh aspect of the invention relates to a urea-urethane composition according to the fifth aspect of the invention, where the diluent is a compound which is obtained by reacting polyisocyanate compounds with hydroxidealuminum or aminoguanidinium.

The eighth aspect of the invention relates to a urea-urethane composition, which is obtained by reacting polyisocyanate compounds with hydroxidealuminum and aminoguanidinium, which is characterized by the fact that includes 50 wt.% or more urea-urethane compounds containing at least one urea group and at least one urethane group with the total number of 2-10 in the molecular structure and having a molecular weight of 5000 or less.

The ninth aspect of the invention relates to a urea-urethane composition according to the eighth aspect of the invention, where hydroxidealuminum is phenolic joint is.

The tenth aspect of the invention relates to a urea-urethane composition according to the eighth aspect of the invention, where hydroxidealuminum is spirit connection.

The eleventh aspect of the invention relates to a urea-urethane composition according to any aspect of the invention, starting from the eighth to tenth, where aminoguanidinium is aromatic aminosilane.

The twelfth aspect of the invention relates to a urea-urethane composition according to any aspect of the invention, starting from the eighth and ending with the eleventh, where the polyisocyanate compound is an aromatic polyisocyanate compound.

The thirteenth aspect of the invention relates to a method for producing a urea-urethane composition, which is in the interaction between the polyisocyanate compound and hydroxycodone so that the ratio of the number of moles of the polyisocyanate compound to the number of hydroxyl equivalents hydroxycodone was 100/1-1/2, with the formation of one or more urethane groups from multiple isocyanate groups of the polyisocyanate compound, and then adding the amino compounds for its interaction with the rest(imisa) isocyanate(s) group(or groups) polyisocyanate compounds with getting one or a number of the x groups of the urea.

The fourteenth aspect of the invention relates to a method for producing a urea-urethane composition, which is in interaction polyisocyanate compounds and amino compounds so that the ratio of the number of moles of the polyisocyanate compound to the number of aminoquinolines of amino compounds was 100/1-1/2, with the formation of one or more groups of urea from multiple isocyanate groups of the polyisocyanate compound, and then adding hydroxycodone for its interaction with the rest(imisa) isocyanate(s) group(or groups) polyisocyanate compounds, obtaining one or more urethane groups.

The fifteenth aspect of the invention relates to a method for producing a urea-urethane composition in accordance with aspects of the invention, Dating from the thirteenth and ending with the fourteenth, which is that consistently spend interaction for the formation of one or more urethane groups and interaction for the formation of one or more urea groups.

The sixteenth aspect of the invention relates to a method for producing a urea-urethane composition, which consists in the interaction of amino compounds with polyisocyanate adduct obtained by reacting polyisocyanate compounds with hydroxidealuminum t is thus, so that the equivalent ratio of isocyanate group to the amino group became 2/1-1/100, with the formation of one or more urea groups, and the subsequent allocation of unreacted amino compounds.

The seventeenth aspect of the invention relates to a method for producing a urea-urethane composition, which consists in the interaction of hydroxycodone with polyisocyanate adduct obtained by reacting polyisocyanate compounds with aminoguanidinium so that the equivalent ratio of isocyanate group to hydroxyl group was 2/1-1/100, with the formation of one or more urethane groups, and the subsequent allocation of unreacted hydroxycodone.

The eighteenth aspect of the invention relates to a method for producing a urea-urethane composition according to any aspect of the invention, Dating from the thirteenth and ending on the seventeenth, which is the realization of interaction for the formation of one or more urethane groups, and/or interaction for the formation of one or more urea groups, without solvent or reactions for the formation of one or more urethane groups, and/or interaction for the formation of one or more urea groups, using the same solvent.

Nineteenth the eleventh aspect of the invention relates to a method for producing a urea-urethane composition according to any aspect of the invention, Dating from the thirteenth and ending with the eighteenth, where the interaction for the formation of one or more urethane groups, and/or interaction for the formation of one or more groups of urea is carried out at a temperature from 0 to 300° C.

The twentieth aspect of the invention relates to a method for producing a urea-urethane composition according to any aspect of the invention, Dating from the thirteenth and ending with the nineteenth, where the interaction for the formation of one or more urethane groups, and/or interaction for the formation of one or more groups of urea is carried out in the presence of a catalyst.

Twenty-first aspect of the invention relates to a color-forming composition comprising a developer containing a urea-urethane compound.

The twenty-second aspect of the invention relates to a color-forming composition comprising a developer containing a urea-urethane compound, colourless or slightly coloured substance is precursor of the dye.

The twenty-third aspect of the invention relates to a color-forming composition in accordance with the twenty-second aspect of the invention, where colourless or slightly coloured substance is a precursor of the dye is leucocrystal.

The twenty-fourth aspect of the invention relates to cotobro the overall composition in accordance with aspects of the invention, starting from twenty-first to twenty-third, where the specified developer is a urea-urethane compound according to any of the aspects of the invention, from the first to the fourth, urea-urethane composition according to any of the aspects of the invention, from the fifth to the twelfth, or a composition obtained by the method of obtaining, in accordance with any of the aspects of the invention, Dating from the thirteenth and ending on the twentieth."

Twenty-fifth aspect of the invention relates to a color-forming composition in accordance with either the twenty-third or twenty-fourth aspects of the invention, which is characterized by the fact that leucocrystal represents at least one leucocrystal selected from leucogranitee triarylmethane type, leucogranitee fluorolog type, leucogranitee fluorenone type and leucogranitee diphenylmethanone type.

The twenty-sixth aspect of the invention relates to a color-forming composition in accordance with either the twenty-third or twenty-fourth aspects of the invention, which is characterized by the fact that lenograstim is a compound represented by the following formula (i):

where both y2and Y3represent the FDS is th alkyl group or alkoxyalkyl group, Y4represents a hydrogen atom, alkyl group, or alkoxygroup, and each of Y5and Y6represents a hydrogen atom, halogen atom, alkyl group, or alkoxygroup.

The twenty-seventh aspect of the invention relates to a color-forming composition in accordance with either the twenty-third or twenty-fourth aspects of the invention, which is characterized by the fact that lenograstim is a compound represented by the following formula (j):

where each R5and R6is a group represented by the formula (k) or formula (l):

(where each R11-R15represents a hydrogen atom, halogen atom, alkyl group of 1-8 carbon atoms, alkoxygroup from 1-8 carbon atoms, or-NR16R17where each R16and R17represents an alkyl group of 1-8 carbon atoms), or

(where each R18and R19represents a hydrogen atom, an alkyl group of 1-8 carbon atoms, phenyl group), and each R7-R10represents a hydrogen atom, halogen atom, alkyl group of 1-8 carbon atoms, alkoxygroup from 1-8 carbon atoms, or-NR20R21where each R20and R21represents alkylen the th group of 1-8 carbon atoms.

The twenty-eighth aspect of the invention relates to a color-forming composition in accordance with any of the aspects of the invention, starting from twenty-first to twenty-seventh, which is characterized by the fact that the melting point of the urea-urethane compound developer is not higher than 500° and not less than 40° C.

Twenty-ninth aspect of the invention relates to a color-forming composition in accordance with any of the aspects of the invention, starting from twenty-first to twenty-seventh, which is characterized by the fact that the urea-urethane compound developer comprises a compound selected from compounds represented by the following General formula (V) or (VI):

where the atom(s) of each hydrogen of the benzene ring may be substituted(s) the remainder of aromatic compounds, a residue of aliphatic compounds, a residue of heterocyclic compounds, the nitro-group, a hydroxyl group, a carboxyl group, nitrosopropane, nitrile group, carbamoyl group, raidgroups, isocyanate group, mercaptopropyl, sulfopropyl, sulfamoyl group or a halogen atom, each of the residues may have one or more substituents, γ represents a group selected from the group comprising-SO2-, -O-, -(S)n-, -(CH2 )n-, -CO-, -CONH - and any group represented by the formula (a):

or absent, and n is 1 or 2; and

where the atom(s) of each hydrogen of the benzene ring may be substituted(s) remaining aromaticaccording, the residue of aliphatic compounds, a residue of heterocyclic compounds, a hydroxyl group, a nitro-group, a nitrile group, carbamoyl group, sulfamoyl group, a carboxyl group, nitrosopropane, amino group, accelerograph, nitrolingual, hydratherapy, raidgroups, isocyanate group, mercaptopropyl, sulfopropyl or a halogen atom, each of the residues may have one or more substituents, 5 represents a group selected from the group comprising-SO2-, -O-, -(S)n-, -(CH2)n-, -CO-, -CONH-, NH-, -CH(COOR1)-, -C(CF3)2- and-CR2R3or absent; each of R1, R2and R3represents an alkyl group, and n is 1 or 2.

The thirtieth aspect of the invention relates to a color-forming composition in accordance with any of the aspects of the invention, starting from twenty-first to twenty-seventh, which is characterized by the fact that the urea-urethane compound developer includes the connection, you the security of connections, represented by the following structural formula (XX) and (XXI):

Thirty-first aspect of the invention relates to a color-forming composition in accordance with any of the aspects of the invention, starting from twenty-first to thirtieth, which additionally includes Caloplaca substance.

Thirty-second aspect of the invention relates to a color-forming composition in accordance with the thirty-first aspect of the invention, which is characterized by the fact that Caloplaca the substance is at least one compound selected from β -aftermentioned ether, p-benzylbiphenyl, 1,2-di(m-methylphenoxy)ethane, di-p-methylanthranilate, 1,2-diphenoxyethane, m-terphenyl and stearamide.

Thirty-third aspect of the invention relates to a color-forming composition in accordance with the thirty-first aspect of the invention, where Caloplaca substance represented by the following structural formula (XVIII):

where Y represents any group of SO2-, -(S)n-, -O-, -CO-, -CH2-, -CH(C6H5)-, -C(CH3)2-, -COCO-, -CO3-, -COCH2CO-, -COOCH2-, -CONH-, -OCH2- and-NH-, n is 1 or 2, and the atom(s) of each hydrogen of the benzene ring may be for the of Eden(s) a halogen atom, a hydroxyl group, a nitrogroup, nitrosopropane, nitrile group, isocyanate group, isothiocyanato group, mercaptopropyl, sulfamoyl group, sulfonic acid group, an amino group, a residue of aromatic compounds, a residue of aliphatic compounds or heterocyclic residue of the connection.

Thirty-fourth aspect of the invention relates to a color-forming composition in accordance with the thirty-third aspect of the invention, where Caloplaca substance represented by the following structural formula (XIX):

where the atom(s) of each hydrogen of the benzene ring may be substituted(s) a halogen atom, a hydroxyl group, a nitrogroup, nitrosopropane, nitrile group, isocyanate group, isothiocyanato group, mercaptopropyl, sulfamoyl group, sulfonic acid group, an amino group, a residue of aromatic compounds, a residue of aliphatic compounds or heterocyclic residue of the connection.

Thirty-fifth aspect of the invention relates to a color-forming composition in accordance with any of the aspects of the invention, starting from twenty-first to thirty-fourth, which additionally includes an isocyanate compound.

Thirty-sixth aspect of the invention relates to t Loubressac composition in accordance with any of the aspects of the invention, starting from twenty-first to thirty-fourth, which additionally includes an isocyanate compound and aminosidine.

Thirty-seventh aspect of the invention relates to a color-forming composition in accordance with any of the aspects of the invention, starting from twenty-first to thirty-sixth, which additionally includes aminosidine.

Thirty-eighth aspect of the invention relates to a color-forming composition in accordance with any of the aspects of the invention, starting from twenty-first to thirty-seventh, where the developer additionally comprises an acid developer.

Thirty-ninth aspect of the invention relates to a color-forming composition in accordance with the thirty-eighth aspect of the invention, characterized in that the acid developer represents, at least one developer selected from 2,2-bis(4-hydroxyphenyl)propane, 4-isopropoxyphenyl-4’-hydroxyprednisolone, bis(3-alli-4-hydroxyphenyl)sulfone, 2,4’-dihydroxydiphenylsulfone and 4,4’-[oxybis(ethyleneoxy-p-phenylenesulfonyl)]diphenol.

The fortieth aspect of the invention relates to a color-forming composition in accordance with any of the aspects of the invention, starting from twenty-first to thirty-ninth, which additionally includes the t itself fluorescent paint.

Forty-first aspect of the invention relates to a color-forming composition in accordance with any of the aspects of the invention, starting from twenty-first to fortieth, which additionally includes the agent, giving stability during storage.

Forty-second aspect of the invention relates to a recording material comprising a substrate and a color-forming layer formed thereon, the specified color-forming layer includes a urea-urethane compound according to any of the aspects of the invention, from the first to the fourth, urea-urethane composition according to any of the aspects of the invention, from the fifth to the twelfth, or color-forming composition in accordance with any of the aspects of the invention, starting from twenty-first to the forty-first.

Forty-third aspect of the invention relates to a recording material in accordance with a forty-second aspect of the invention, which is characterized by the fact that color-forming layer to form a protective layer for the color-forming layer.

Forty-fourth aspect of the invention relates to a recording material in accordance with a forty-third aspect of the invention, which is characterized by the fact that the protective layer comprises a water-soluble polymer.

Forty-fifth aspect of the image is etenia relates to a recording material in accordance with either the forty-third, or the forty-fourth aspects of the invention, which is characterized by the fact that the protective layer includes an inorganic pigment and/or organic pigment.

Forty-sixth aspect of the invention relates to a recording material in accordance with any of the aspects of the invention, since the forty-third and to the forty-fifth, and is characterized by the fact that the protective layer comprises a lubricating agent.

Forty-seventh aspect of the invention relates to a recording material in accordance with a forty-second aspect of the invention, which is characterized by the fact that on the substrate to form the intermediate layer and the specified intermediate layer form a color-forming layer.

Forty-eighth aspect of the invention relates to a recording material in accordance with the forty-seventh aspect of the invention, which is characterized by the fact that the intermediate layer includes a water-soluble polymer.

Forty-ninth aspect of the invention relates to a recording material in accordance with either the forty-seventh or forty-eighth aspects of the invention, which is characterized by the fact that the intermediate layer includes an inorganic pigment and/or organic pigment.

Fiftieth aspect of the invention relates to a recording material in accordance with a forty-second aspect of the invention, which is characterized by the fact th, the layer covering the back side are formed on the substrate from the back side of the hand, having a color-forming layer formed on it.

Fifty-first aspect of the invention relates to a recording material according to the fiftieth aspect of the invention, which is characterized by the fact that the covering layer covering the reverse side includes a water-soluble polymer.

Fifty-second aspect of the invention relates to a recording material in accordance with either the fiftieth or fifty-first aspects of the invention, which is characterized by the fact that the coating layer of the reverse side includes an inorganic pigment and/or organic pigment.

Fifty-third aspect of the invention relates to a recording material in accordance with any of the aspects of the invention, since the forty-second and to the fifty-second, which is characterized by using at least one compound selected from water-soluble polymers and anionic surfactants, as dispersing agent for the urea-urethane compounds.

Fifty-fourth aspect of the invention relates to a recording material in accordance with any of the aspects of the invention, since the forty-second and to the fifty-second, which character is to be generated using, at least one compound selected from polyvinyl alcohol, modified polyvinyl alcohol, methyl cellulose, hydroxypropylmethylcellulose, condensed naphthalenesulfonate sodium, and ammonium salts of polycarboxylic acids, water-soluble low molecular weight copolymers and 2-ethylhexylacrylate sodium, as a dispersing agent, urea-urethane compounds.

Fifty-fifth aspect of the invention relates to a recording material in accordance with any of the aspects of the invention, since the forty-second and to the fifty-fourth, which is characterized by using at least one compound selected from water-soluble polymers, nonionic surfactants and anionic surfactants as dispersing agent for the substance, precursor of the dye.

Fifty-sixth aspect of the invention relates to a recording material in accordance with any of the aspects of the invention, since the forty-second and to the fifty-fourth, which is characterized by using at least one compound selected from methylcellulose,hydroxypropylmethylcellulose, polietilenglikolya esters of fatty acids, sulfates polyoxyethylenated esters and 2-ethylhexylacrylate, as a dispersing agent for the substance, precursor of the dye.

Fifty-seventh aspect of the invention relates to a recording material in accordance with any of the aspects of the invention, since the forty-second and to the fifty-sixth, which is a heat-sensitive recording material.

Fifty-eighth aspect of the invention relates to a thermosensitive recording material in accordance with a fifty-seventh aspect of the invention, which is characterized by the fact that the average particle size of the urea-urethane compound is not more than 5 μm and not less than 0.05 microns.

Fifty-ninth aspect of the invention relates to a thermosensitive recording material in accordance with the fifty-seventh and fifty-eighth aspect of the invention, which is characterized by the fact that the liquid temperature during grinding of the urea-urethane compound is 60° With or below.

The sixtieth aspect of the invention relates to a thermosensitive recording material in accordance with any of the aspects of the invention, since the fifty-seventh to fifty-ninth, which is characterized by the fact that the pH during grinding of the urea-urethane compound is from 5 to 10.

Sixty-first aspect of the invention relates to termodystylyatsiya material in accordance with any of the aspects of the invention, starting with the fifty-seventh and to the sixties, which is characterized by using at least one compound selected from water-soluble polymers and anionic surfactants as dispersing agent for Caloplaca substances.

Sixty-second aspect of the invention relates to a thermosensitive recording material in accordance with any of the aspects of the invention, since the fifty-seventh and to the sixties, which is characterized by using at least one compound selected from polyvinyl alcohol, modified polyvinyl alcohol, methyl cellulose, hydroxypropylmethylcellulose, condensed naphthalenesulfonate sodium, and ammonium salts of polycarboxylic acids, water-soluble low molecular weight copolymers and 2-ethylhexylacrylate sodium, as a dispersing agent for Caloplaca substances.

Sixty-third aspect of the invention relates to a thermosensitive recording material in accordance with any of the aspects of the invention, since the fifty-seventh to sixty-second, which is characterized by the fact that the urea-urethane compound and Caloplaca substance melkoizmelchennye together.

Sixty-fourth aspect of the invention, the relative is conducted to the heat-sensitive recording material in accordance with any of the aspects of the invention, starting with the fifty-seventh to sixty-third, which is characterized by the fact that the pH of the surface of the substrate, which covers the heat-sensitive recording layer of thermosensitive recording material is from 3 to 9.

Sixty-fifth aspect of the invention relates to a method for producing a thermosensitive recording material in accordance with any of the aspects of the invention, since the fifty-seventh to sixty-fourth, which is characterized by applying on a substrate a thermosensitive liquid for coating with pH from 5 to 12 for forming thermosensitive recording layer of thermosensitive recording material.

Sixty-sixth aspect of the invention relates to a recording material in accordance with a forty-second aspect of the invention, which is a heat-sensitive magnetic recording material.

The sixty-seventh aspect of the invention relates to a heat-sensitive magnetic recording material in accordance with a sixty-sixth aspect of the invention, which is characterized by the fact that the heat-sensitive recording layer comprising a urea-urethane compound developer, formed on one side of the substrate, and a magnetic recording layer on the other side.

Ø slideset eighth aspect of the invention relates to railway ticket which is a heat-sensitive magnetic recording material in accordance with the sixty-sixth or twenty-seventh aspect of the invention.

Sixty-ninth aspect of the invention relates to the ticket, which is a heat-sensitive magnetic recording material in accordance with the sixty-sixth or twenty-seventh aspect of the invention.

The seventieth aspect of the invention relates to a recording material in accordance with a forty-second aspect of the invention, which is a label for heat-sensitive recording.

Seventy-first aspect of the invention relates to a label for heat-sensitive recording according to the seventieth aspect of the invention, which is characterized by the fact that the heat-sensitive recording layer comprising a urea-urethane compound developer, formed on one side of the substrate, and an adhesive layer on the other side.

Seventy-second aspect of the invention relates to a label for heat-sensitive recording in accordance with a seventy-first aspect of the invention, which is characterized by the fact that the coating layer of the reverse side is formed between the adhesive layer and the substrate.

Seventy-third aspect of the invention relates to a label for heat-sensitive recording ACC is accordance or semidesert first or seventy-second aspects of the invention, which is characterized by the fact that the intermediate layer is formed between thermosensitive recording layer and the substrate.

Seventy-fourth aspect of the invention relates to a label for heat-sensitive recording in accordance with any of the aspects of the invention, since the seventy-first and to the seventy-third, which is characterized by the fact that the protective layer formed on thermosensitive recording layer.

Seventy-fifth aspect of the invention relates to a recording material in accordance with a forty-second aspect of the invention, which is a color thermosensitive recording material.

Seventy-sixth aspect of the invention relates to a color thermosensitive recording material in accordance with a seventy-fifth aspect of the invention, where at least two heat-sensitive recording layer formed on one side of the substrate, the specified recording material is characterized by the fact that at least one of the heat-sensitive recording layers includes a urea-urethane compound developer.

Seventy-seventh aspect of the invention relates to a color thermosensitive recording material in accordance with a seventy-sixth aspect of the Britania, which is characterized by the fact that the intermediate layer is formed MinuteMachine recording layers.

Seventy-eighth aspect of the invention relates to a color thermosensitive recording material, which is characterized by the fact that includes a substrate and two heat-sensitive recording layer, laminated on one side of the substrate, which have different temperatures, the degree of color development, respectively, and are the manifestation of the colors of different color tones, respectively, the upper heat-sensitive recording layer, includes any agent that is used both as a developer and as a tone reliever, or reversing the developer, and the lower thermosensitive recording layer comprising a urea-urethane compound developer.

Seventy-ninth aspect of the invention relates to a color thermosensitive recording material in accordance with a seventy-eighth aspect of the invention, which is characterized by the fact that their two heat-sensitive recording layers, the upper layer is a low-temperature color-forming layer capable of undergoing a color expression at low temperature and to be achromatization at high temperature, and the bottom layer is color-forming layer, sposobamiraboty color manifestation at a high temperature.

The eightieth aspect of the invention relates to an article for laser marking, which is characterized by having on the surface of thermosensitive recording layer comprising a urea-urethane compound developer.

Eighty-first aspect of the invention relates to an article for laser marking, which is characterized by having on the surface of thermosensitive recording layer comprising a colorless or slightly coloured substance is a dye precursor, urea-urethane compound developer and agent, which improves the recording sensitivity.

Eighty-second aspect of the invention relates to an article for laser marking in accordance with either of the eighties, or the eighty-first aspect of the invention, which is characterized by the fact that heat-sensitive recording layer a protective layer comprising a water binding agent having a glass transition point equal to 20-80° C.

Eighty-third aspect of the invention relates to an article for laser marking according to the eighty-first aspect of the invention, the agent that improves the recording sensitivity, represents at least one compound selected from aluminum hydroxide, white mica, wollastonite and kaolin.

Eighty-fourth aspect of the image is to be placed is the product for laser marking in accordance with any of the aspects of the invention, since the eighties and ending the eighty-third, which is any label, packaging material and containers.

Eighty-fifth aspect of the invention relates to a method of obtaining products for laser marking, which is characterized by coating the substrate color-forming composition for marking comprising a urea-urethane compound developer, and drying the thus obtained substrate.

Eighty-sixth aspect of the invention relates to a method of obtaining products for laser marking, which is characterized by coating the substrate color-forming composition for marking comprising a colorless or slightly coloured substance is a dye precursor, urea-urethane compound developer and agent, which improves the recording sensitivity, and drying the thus obtained substrate.

Eighty-seventh aspect of the invention relates to a method for labeling products, which is characterized by the irradiation heat-sensitive recording layer products for laser marking in accordance with any of the aspects of the invention, since the eighties and ending the eighty-fourth laser beams.

Eighty-eighth aspect of the invention relates to a color-forming composition for labeling, which h is the, that includes a urea-urethane compound developer.

Eighty-ninth aspect of the invention relates to a color-forming composition for marking, kotorayaraspolagaetsya that includes colorless or light-colored substance is a dye precursor, urea-urethane compound developer and agent, which improves the recording sensitivity.

The best method of carrying out the invention

The present invention is described hereinafter in more detail.

Each of the urea-urethane compounds of the aspects of the present invention, from the first to the fourth contains at least one group of the urea and urethane group.

In the urea-urethane compounds according to aspects of the invention first to fourth residue of aliphatic compounds attached to the terminal oxygen atom of the urethane group. Thus, urea-urethane compounds can be obtained as compounds with excellent physical and chemical stability, in particular stability to heat. Moreover, urea-urethane compounds can be obtained using relatively inexpensive products.

In addition, the original spirit connection for the remainder of aliphatic compounds attached to the terminal oxygen atom of the urethane group, can the be easily removed, even if it remains unreacted in the reaction of synthesis of urea-urethane compounds. Therefore, the urea-urethane compound can be obtained with a high degree of purity.

Preferred forms at the ends of the group of urea megalithomania depending on the molecular size of the urea-urethane compounds. In the urea-urethane compound of the formula (C), each end of the group of urea should be attached to the remainder of the aromatic compounds. The remainder of the aromatic compound is preferably an aromatic ring shown in the formula (d). In the urea-urethane compounds of the formulas (e) and (f)having a relatively large molecular size, the group at each end of the group of urea, for example, is the following: in the formula (e) group at each end can be any residue of aromatic compounds, a residue of heterocyclic compounds and a residue of aliphatic compounds, and in the formula (f) group at each end can be either a residue of an aromatic compound, or a residue of heterocyclic compounds. In both formulas, (e) and (f), the group at each end of the group of urea is preferably the residue of aromatic compounds. The group of urea and urethane group are adjacent with respect to each other, connected via at least dinostock compounds (such a structural fragment here and hereinafter referred to as urea-urethane structural fragment). Preferably, only one remaining connection was between the group of urea and urethane group. In addition, this residue is preferably an aromatic ring.

Although not known the specific mechanism by which urea-urethane compound according to aspects of the invention with a first through fourth, act as the developer, assume that the action takes place by the interaction between the urea group and urethane group, a urea-urethane structural fragment. In the formulas (e) and (f) the number of urea-urethane structural fragments is two or more. On the other hand, in the formula (C) or (d) the number of urea-urethane structural fragments in some cases equal to one. In this case, assume the following: in the urea-urethane compound of the formula (C) or (d) the remainder, which must be attached to each end of the group of urea, is limited to the most preferred balance, i.e. the balance of aromatic compounds, so that the connection could act as a developer to some extent; on the other hand, in the formulas (e) and (f) residue that is attached to each end of urethane groups, may not always be a residue of aromatic compounds.

It is sufficient that the number of urea-urethane structural fragments present in the molecules is, ranged from 1 to 10, preferably from 1 to 5, more preferably from 2 to 4.

In addition to the urea-urethane(s) structural(s) fragment(s) of the urea-urethane compound having in the molecule one or more other groups of urea and urethane groups.

The term “aliphatic”as used in the case of aspects of the invention from the first to the fourth includes the term “alicyclic”.

The term “residue of aliphatic compounds”, which is used in the case of aspects of the invention first to fourth means residue attached through the carbon atom of the aliphatic hydrocarbon moiety in the balance. The term “residue of aromatic compounds”, which is used here, means the residue, attached through a carbon atom of the aromatic ring such as benzene ring. The term “residue of heterocyclic compounds”, which is used here, means the residue, attached through a carbon atom, form a heterocyclic ring residue.

Preferred examples of the substituents of the aliphatic residue of the compound and the residue of heterocyclic compounds and residue aromatic compounds are alkyl groups, cycloalkyl group, phenyl group, amide group, CNS group, a nitrogroup, Kirilina the group, the atoms of halogen, formyl group, dialkylamino, toluensulfonyl group and methanesulfonyl group.

When the urea-urethane compound according to aspects of the invention from the first to the fourth used as a developer or in the heat-sensitive recording material, the total number of one or more aliphatic urethane groups and one or more urea groups present in the molecular structure of each urea-urethane compound aspect of the invention, from the first to the fourth, is not more than 11 and not less than 2, preferably not more than 11 and not less than 3, more preferably not more than 11 and not less than 4. The ratio of the urethane(s) group(s) to the group(s) of the urea is preferably from 1:3 to 3:1, more preferably from 1:2 to 2:1, most preferably 1:1. The molecular mass of the urea-urethane compounds is 5000 or less, preferably 2000 or less.

In thermosensitive recording substance is preferably used a compound having the melting point. The melting point of the urea-urethane compounds according to aspects of the invention from the first to the fourth is in the area of preferably from 40° 500° S, more preferably from 60° to 300° most prefer is Ino from the 60° With up to 250° C.

The method of synthesis of each urea-urethane compound according to aspects of the invention from the first to the fourth is not specifically limited. The way in which the urea-urethane compound is synthesized by reacting the isocyanate compound with an alcohol compound and aminoguanidinium, is preferred in view of its simplicity.

A method of obtaining a urea-urethane compound of the formula (C) according to the first aspect of the present invention is not limited. This compound can be obtained, for example, by reacting an alcohol compound of the following formula (m) with isocyanates compound of the following formula (n) and aminoguanidinium the following formula (o) in accordance with, for example, by the reaction equation (A’) or (’), is presented below:

where R represents the residue of aliphatic compounds, which may have one or more substituents;

where A1represents the balance of aromatic compounds, which may have one or more substituents; and

where a2represents the balance of aromatic compounds, which may have one or more deputies.

A method of obtaining a urea-urethane the new compounds of formula (d) no second aspect of the present invention is not specifically limited. This compound can be obtained, for example, by reacting an alcohol compound of formula (m) with an isocyanate compound of the following formula (p) and aminoguanidinium the following formula (q) in accordance with, for example, by the reaction equation (C’) or (D’)below:

where the atom(s) of the hydrogen of the benzene ring may be substituted(s) the remainder of aromatic compounds, a residue of aliphatic compounds, a residue of heterocyclic compounds, a hydroxyl group, a nitro-group, a nitrile group, carbamoyl group, sulfamoyl group, a carboxyl group, nitrosopropane, amino group, accelerograph, nitrolingual, hydratherapy, raidgroups, isocyanate group, mercaptopropyl, sulfopropyl or a halogen atom and where each residue can have one or more substituents; and

where the atom(s) of the hydrogen of the benzene ring may be substituted(s) the remainder of aromatic compounds, a residue of aliphatic compounds or balance geterotsiklicheskikh and each residue can have one or more deputies.

A method of obtaining a urea-urethane compound of the formula (e) according to a third aspect of the present invention the spiral is however not limited. This compound can be obtained, for example, by reacting an alcohol compound of General formula (m) with an isocyanate compound of the following General formula (r) and aminoguanidinium following General formula (s) in accordance with, for example, by the reaction formula (E’) or (F’)is presented below:

where Y represents the residue of aromatic compounds, a residue of a heterocyclic compound or a residue of aliphatic compounds and each residue can have one or more substituents; and

where α1represents the residue of an aromatic, aliphatic or heterocyclic compounds, which has a valency of 2 or more, n represents an integer of 2 or more and each residue can have one or more deputies.

A method of obtaining a urea-urethane compound of the formula (f) according to a third aspect of the present invention is not specifically limited. This compound can be obtained, for example, by reacting the amino compounds of the following General formula (t) with the isocyanate compound of the following General formula (r) and an alcohol compound of General formula (u) in accordance with, for example, by the reaction formula (G’) or (N’)is presented below:

where Z1represents the residue of an aromatic compound or a residue of heterocyclic compounds and each residue can have one or more substituents; and

where β1represents a residue of aliphatic compounds, which has a valency of 2 or more, and may have one or more substituents, and n is an integer of 2 or greater.

A method of obtaining a urea-urethane compound of the formula (g) according to the fourth aspect of the present invention is not specifically limited. This compound can be obtained, for example, by reacting an alcohol compound of the formula (I) with an isocyanate compound of the formula (R) and aminoguanidinium formula (q) in accordance with, for example, by the reaction formula (i’) or (J’), is presented below:

A method of obtaining a urea-urethane compound of the formula (h) according to the fourth aspect of the present invention is not specifically limited. This compound can be obtained, for example, by reacting the amino compounds of the following formula (XVII) with an isocyanate compound of the formula (R) and an alcohol compound of General formula (m) in accordance with, for example, by the reaction formula (K’) or (L’), is presented below:

where the atom(s) of each hydrogen of the benzene ring may be substituted(s) the remainder of aromatic compounds, a residue of aliphatic compounds, a residue of heterocyclic compounds, the nitro-group, a hydroxyl group, a carboxyl group, nitrosopropane, nitrile group, carbamoyl group, raidgroups, isocyanate group, mercaptopropyl, sulfopropyl, sulfamoyl group or a halogen atom, each residue can have one or more substituents, γ1represents a group selected from the group comprising-SO2-, -O-, -(S)n-, -(CH2)n-, -CO-, -CONH-, -NH-, -CH(COOR1)-, -C(CF3)2-, -CR2Rs - and any group represented by the formula (a):

or absent; each of R1, R2and R3represents an alkyl group and n is 1 or 2.

Compounds of formula (m)to(u), which can be used in the synthesis of urea-urethane compounds of the above formulae (C)-(h), hereinafter disclosed in more detail.

As the alcohol compound of General formula (m) can be used any alcohol compound, provided that it has one or more Oh groups attached to one or more carbon atoms, respectively alipac the mental connection. Examples of the alcohol compounds are alcohols, described in Solvent Handbook, Kodansha Scientific Co., Ltd., in the ninth reprint (1989), page 327-420 and p. 772-817. Alcohol compound includes, for example, aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, Isobutanol, sec-butanol, tert-butanol, pentanol, Cyclopentanol, tert-amyl alcohol, 2-pentanol, isoamyl alcohol, hexanol, 3-hexanol, cyclohexanol, cyclohexylmethanol, 4-methyl-2-pentanol, heptanol, isoheptane, octanol, 2-ethyl-1-hexanol, Caprylic alcohol, nonlevy alcohol, icononly alcohol, decanol, undecylenic alcohol, dodecyloxy alcohol, tridecylamine alcohol, tetradecanoyl alcohol, hexadecylamine alcohol, octadecylamine alcohol, isostearoyl alcohol and the like; unsaturated aliphatic alcohols such as allyl alcohol, 2-methyl-2-propen-1-ol, krotilova alcohol, propargilovyh alcohol and so forth; aliphatic alcohols having attached to it the rest of aromatic compounds such as benzyl alcohol, cinnamony alcohol and so forth; aliphatic alcohols having attached to it the rest of heterocyclic compounds such as 2-pyridinemethanol, 3-pyridinemethanol, 4-pyridinemethanol, furfuryl alcohol, and so on; halogenated aliphatic alcohols, such as 2-chloroethanol, 1-chloro-3-hydroxypropan and so on; glycol ethers, t is the cue as onomatology ether of ethylene glycol, monotropy ether of ethylene glycol, monopropylene ether of ethylene glycol, monoisopropylamine ether of ethylene glycol, ethylene glycol monobutyl ether, monoisobutyl ether of ethylene glycol, monohexadecyl ether of ethylene glycol, monopoloy ether of ethylene glycol, onomatology ether of diethylene glycol, monotropy ether of diethylene glycol, monopropylene ether of diethylene glycol, monoisopropylamine ether of diethylene glycol, monobutyl ether of diethylene glycol, monoisobutyl ether of diethylene glycol, monohexadecyl ether of diethylene glycol, monopoloy ether of diethylene glycol, onomatology ether of propylene glycol, monotropy ether of propylene glycol, monopropylene ether of propylene glycol, monoisopropylamine ether of propylene glycol, monobutyl ether of propylene glycol, monoisobutyl ether of propylene glycol, monopoloy ether of propylene glycol, onomatology broadcast dipropyleneglycol, monotropy broadcast dipropyleneglycol, monopropylene broadcast dipropyleneglycol, monoisopropylamine broadcast dipropyleneglycol, monobutyl broadcast dipropyleneglycol, monoisobutyrate broadcast dipropyleneglycol, monopoloy broadcast dipropyleneglycol and so on; diols, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propandiol, 1,2-propandiol, propylene glycol, dipropyleneglycol, tripropyleneglycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexa the diol, hexyleneglycol, 1,9-nonanediol, neopentylglycol, methylpentanediol and so forth; aliphatic polyols such as glycerol, castor oil, trimethylolpropane, trimethylacetyl, hexanetriol, pentaerythritol, α -methylglucoside, sorbitol, sucrose and the like; polyols, such as glycols, polypropylenglycol, polytetramethylene, adeptpro.info polyols, epoksipolyurethane polyols, polyether ester polyols, polycarbonate polyols, polycaprolactone diols, aminodiphenylamine polyols, polyester polyols obtained by adding one or a mixture of two or more alkilinity oxides (e.g. ethylene oxide and propylene oxide) to one or a mixture of two or more polyhydric alcohols (glycerin and propylene glycol), acrylic polyols, fluorinated polyols, polybutadiene polyols, polyhydroxy polyols, polyols derived from castor oil, polymer polyols, halogenated polyols, phosphorus-containing polyols, and so forth; and alkanolamines, such as N,N-dialkylacrylamide, N,N-dialkylhydroxylamines, N-alkyldiethanolamine, N-alkyldiethanolamine, triethanolamine, triisopropanolamine, N,N,N’,N’-tetrakis(2-hydroxyethyl)-Ethylenediamine, N,N,N’,N’-tetrakis(2-hydroxypropyl)Ethylenediamine, and so on.

From the above example alcohol preference for the equipment are monosperma, containing one Oh group, and more preferred are aliphatic alcohols and glycol ethers, which contain 10 or less carbon atoms.

Isocyanate compound of formula (n) is not specifically limited provided that represents aromatisation having two or more isocyanate groups attached to carbon atoms respectively. Isocyanate compound includes, for example, n-delete the entry, the m-delete the entry, delete the entry, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-colorvision, 2,6-colorvision, diphenylmethanediisocyanate, solidinvestment, diphenyl ether diisocyanate, 1,5-naphthylenediisocyanate, dianisidines, 3,3’-dimethyl-4,4’-difenilmetana diisocyanate, triphenylmethane triisocyanate, Tris(4-phenylisocyanate)thiophosphate, 4,4’,4’-triisocyanate-2,5-dimethoxyaniline and 4,4’,4’-triisocyanate. As the isocyanate compound of formula (n) can also be used diisocyanate dimers, such as N,N’-(4,4’-dimethyl-3,3’-diphenyldiisocyanate)uretidine (Desmodule TT, trade mark), colorvitality dimer; and diisocyanate trimers, such as 4,4’,4’-trimethyl-3,3’,3’-triisocyanate-2,4,6-triphenylene. You can also use water adducts of isocyanates, selected from colordistance, difenilmetana isocyanate and the like, such as 1,3-bis(3-isocyanato-4-were)urea; polyol as one admati, such as trimethylolpropane adducts selected from colordistance (Desmodule L, Coronate L, trade names); and eminiaddict. Can also be used compounds having two or more isocyanate groups, including isocyanate compounds and isocyanate adducts described in the detailed description of Japanese patent JP-A-10-76757 and detailed description of Japanese patent JP-A-10-95171 (the contents of these references are hereby incorporated by reference).

The above as examples of isocyanate compounds, aromatic diisocyanates having isocyanate groups attached to the benzene ring, are preferred. More preferred are n-delete the entry, the m-delete the entry, delete the entry, 2,4-colorvision, 2,6-colorvision, diphenylmethanediisocyanate, solidinvestment, diphenyl ether diisocyanate, 1,5-naphthylenediisocyanate, triphenyltetrazolium, N,N’-(4,4’-dimethyl-3,3’-diphenyldiisocyanate)uretdione (Desmodule TT, trade name), 4,4’,4’-trimethyl-3,3’,3’-triisocyanate-2,4,6-triphenylene, 1,3-bis (3-isocyanato-4-were)urea and trimethylolpropane adducts selected from colordistance (Desmodule L, Coronate L, trade name). Particularly preferred examples of isolan the spas compounds of formula (n) are colordistance. Of colordistance preferred is 2,4-colorvision. In addition, as well as isocyanate compounds of formula (n) can be used 2,4-colorvision, mixtures of 2,4-colordistance and 2,6-colordistance, which are widely spread on the market and available at a low price.

As the amine compound of General formula (o) can be specified, for example, aromatic amines such as aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-fenetidin, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xylidin, 2, 4-xylidin, 3,4-xylidene, 2,6-xylidene, 4-aminobenzonitrile, Anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α -naphtylamine, aminoanthracene, o-ethylaniline, o-Chloroaniline, m-Chloroaniline, p-Chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline, anilides acetoacetic acid, bromide of trimethylphenylammonium, 4,4’-diamino-3,3’-diethyldiphenylurea, 4,4’-diaminobenzanilide, 3,5-diaminophenol, diaminodiphenyl ether, 3,3’-dichloro-4,4’-diaminodiphenylmethane, 3,3’-dimethyl-4,4’-diaminodiphenylmethane, tolidine base, o-phenylenediamine, m-Fe is randilyn, p-phenylenediamine, 2-chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, p-(N-phenylcarbamoyl)aniline, n-[N-(4-chlorophenyl)-carbarnoyl]aniline, n-[N-(4-AMINOPHENYL)carbarnoyl]aniline, 2-methoxy-5-(N-phenylcarbamoyl)aniline, 2-methoxy-5-[N-(2’-methyl-3’-chlorophenyl)carbarnoyl]aniline, 2-methoxy-5-[N-(2’-chlorophenyl)carbarnoyl]aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminophenol, 4-(N-methyl-N-acetylamino)aniline, 2,5-diethoxy-4-(N-benzoylamine)aniline, 2,5-dimethoxy-4-(N-benzoylamine)aniline, 2-methoxy-4-(N-benzoylamine)-5-methylaniline, 4-sulfanilamide, 3-sulfanilamide, 2-(N-ethyl-N-phenylenesulfonyl)aniline, 4-dimethylaminoacetonitrile, 4-diethylaminoethylamine, sulfathiazole, 4-aminodiphenylamine, 2-chloro-5-N-phenylsulfonyl, 2-methoxy-5-N,N-diethylcarbamoyl, 2,5-dimethoxy-4-N-fensulfothion, 2-methoxy-5-benzisothiazolin, 2-phenoxycarbonylamino, 2-(2’-chlorophenoxy)sulfanilamide, 3-anilinomethyl-4-methylaniline, bis[4-(m-aminophenoxy)phenyl]sulfon, bis[4-(p-aminophenoxy)FeNi is]sulfon, bis[3-methyl-4-(p-aminophenoxy)phenyl]sulfon, 3,3’-dimethoxy-4,4’-diaminobiphenyl, 3,3’-dimethyl-4,4’-diaminobiphenyl, 2,2’-dichloro-4,4’-diamino-5,5’-dimethoxybiphenyl, 2,2’,5,5’-tetrachloro-4,4’-diaminobiphenyl, o-toluensulfonyl, 2,4’-diaminobiphenyl, 2,2’-diaminobiphenyl, 4,4’-diaminobiphenyl, 2,2’-dichloro-4,4’-diaminobiphenyl, 3,3’-dichloro-4,4’diaminobiphenyl, 2,2’-dimethyl-4,4’-diaminobiphenyl, 4,4’-thiodianiline, 2,2’-dicitionary, 4,4’-dicitionary, 4,4’-diaminodiphenyl ether, 3,3’-diaminodiphenyl ether, 3,4’-diaminodiphenyl ether, 4,4’-diaminodiphenylmethane, 3,4’-diaminodiphenylmethane, bis(3-amino-4-chlorophenyl)sulfon, bis(3,4-diaminophenyl)sulfon, 4,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylsulfone, 3,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylmethane, 4, 4-diaminodiphenylamine, 4,4’ -ethylendiamin, 4,4’-diamino-2,2’-dimethylbenzyl, 3,3’-diaminobenzophenone, 4,4’-diaminobenzophenone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-AMINOPHENYL)fluorene, 2,2-bis(4-aminophenoxy)propane, 4,4’-bis(4-aminophenoxy)diphenyl, 3,3’,4,4’-tetraaminodiphenyl ether, 3,3’,4,4’-tetraaminodiphenyl, 3,3’,4,4’-tetraaminobiphenyl, 3-aminobenzonitrile, 4-fenoxedilom, 3-fenoxedilom, 4,4’-Methylenebis-o-toluidine, 4,4’-(p-phenyleneisopropylidene)-bis-(2,6-xylidene), o-chloro-p-nitroaniline, o-nitro-p-Chloroaniline, 2,6-dichloro-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, metol, 2,4-diaminophenol, N-(β -hydroxyethyl)-o-aminophenolate, sulfanilic acid, Manilova acid, 4B acid, acid, 2B acid, p-ftoranila, ftoranila, 3-chloro-4-ftoranila, 2,4-diptiranjan, 2,3,4-triptorelin, m-aminobenzotrifluoride, m toluylenediamine, 2-aminothiophenol, 2-amino-3-bromo-5-nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, acceleratory diphenylamine, 2-methyl-4-methoxydiphenyl, N,N-diphenyl-p-phenylenediamine, dianisidine, 3,3’-dichlorobenzidine, 4,4’-diaminostilbene-2,2’-disulfonate acid, benzylideneaniline, 1,8-naphthaleneamine, national sodium, Tobias acid, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, 1,4-diamino-2,3-dichloronitrobenzene so on.

Aromatic isocyanate compound of the formula (p) include 2,4-colorvision, 2,6-colorvision, m-delete the entry, the n-delete the entry, delete the entry and so on. Of them, preferred are colordistance, the most preferred is 2,4-colorvision.

The aromatic amine compound of the formula (q) is not specifically limited provided that it has one or more amino groups directly related to one the or more carbon atoms, respectively, of the benzene ring. In addition, the atom(s) of the hydrogen of the benzene ring may be substituted(s) the remainder of aromatic compounds, a residue of aliphatic compounds, a residue of heterocyclic compounds, a hydroxyl group, a nitro-group, a nitrile group, carbamoyl group, sulfamoyl group, a carboxyl group, nitrosopropane, accelerograph, nitrolingual, hydratherapy, raidgroups, isocyanate group, mercaptopropyl, sulfopropyl or a halogen atom. The aromatic amine compound of the formula (q) includes, for example, aromatic monoamines such as aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-fenetidin, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, carboxyaldehyde anilines (for example, p-aminobenzoic acid), hydroxylamine anilines (e.g., o-aminophenol, m-aminophenol, p-aminophenol and 2-amino-4-chlorophenol), 2,3-xylidin, 2,4-xylidene, 3,4-xylidene, 2,6-xylidene, nitrosamine anilines (e.g., 4-aminobenzonitrile), Anthranilic acid, p-cresidine, halogen-substituted anilines (e.g., 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, o-Chloroaniline, m-Chloroaniline and p-Chloroaniline), α -naphtylamine, aminoanthracene, o-ethylaniline, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-PR the peel p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, carbamoylation (for example, p-(N-phenylcarbamoyl)aniline, n-[N-(4-chlorophenyl)carbarnoyl]aniline, n-[N-(4-AMINOPHENYL)carbarnoyl]aniline, 2-methoxy-5-(N-phenylcarbamoyl)aniline, 2-methoxy-5-[N-(2’-methyl-3’-chlorophenyl)carbarnoyl]aniline and 2-methoxy-5-[N-(2’-chlorophenyl)carbarnoyl]aniline), 5-acetylamino-2-methoxyaniline, 4-acetylaminophenol, 2-methoxy-4-(N-benzoylamine)-5-methylaniline, sulfamerazine (for example, 4-sulfanilamide, 3-sulfanilamide, 2-chloro-5-N-phenylsulfonyl, 2-methoxy-5-N, N-Diethylaminoethanol and 2, 5-dimethoxy-4-N-phenylsulfonyl), 2-(N-ethyl-N-phenylenesulfonyl)aniline, 4-dimethylaminoacetonitrile, 4-diethylaminoethylamine, sulfathiazole, 4-aminodiphenylamine, 2-methoxy-5-benzisothiazolin, 2-phenoxycarbonylamino, 2-(2’-chlorophenoxy)sulfanilamide, 3-anilinomethyl-4-methylaniline, nitrosamine anilines (e.g., o-chloro-p-nitroaniline, o-nitro-p-Chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine and 2-amino-5-nitro sonitrol), sulfanilic acid, Manilova acid, 4B acid, acid, 2B acid, p-ftoranila, ftoranila, 3-chloro-4-ftoranila, 2,4-diptiranjan, 2,3,4-triptorelin, m-aminobenzotrifluoride, 2-amino-3-bromo-5-nitrobenzonitrile and so forth; aromatic monoamines having one or more substituents, including carboxyl groups, nitrosolobus, accelerograph, nitrolingual, hydratherapy, raidgroup, isocyanate group, mercaptopropyl, alphagroup and so forth; and aromatic diamines such as 4,4’-diamino-3,3’-diethyldiphenylurea, 4,4’-diaminobenzanilide, 3,5-diaminophenol, diaminodiphenyl ether, 3,3’-dichloro-4,4’-diaminodiphenylmethane, 3,3’-dimethyl-4,4’-diaminodiphenylmethane, tolidine base, dianisidine, bis[4-(m-aminophenoxy)phenyl]sulfon, bis[4-(p-aminophenoxy)phenyl]-sulfon, bis[3-methyl-4-(p-aminophenoxy)phenyl]sulfon, 3,3’-dimethoxy-4,4’-diaminobiphenyl, 3,3’-dimethyl-4,4’-diaminobiphenyl, 2,2’-dichloro-4,4’-diamino-5,5’-dimethoxybiphenyl, 2,2’,5,5’-tetrachloro-4,4’-diaminobiphenyl, o-toluensulfonyl, 2,4’-diaminobiphenyl, 2,2’-diaminobiphenyl, 4,4’-diaminobiphenyl,2,2’-dichloro-4,4’-diaminobiphenyl, 3,3’-dichloro-4,4’-diaminobiphenyl, 2,2’-dimethyl-4,4’-diaminobiphenyl, 4,4’-thiodianiline, 2,2’-dicitionary, 4,4’-dicitionary, 4,4’-diaminodiphenyl ether, 3,3’-diaminodiphenyl ether, 3,4’-diaminodiphenyl ether, 4,4’-dia is nodefinition, 3,4’-diaminodiphenylmethane, bis(3-amino-4-chlorophenyl)sulfon, bis(3,4-diaminophenyl)sulfon, 4,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylsulfone, 3,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylmethane, 4,4’-diaminodiphenylamine, 4,4’-atelevision, 4,4’-diamino-2,2’-dimethylbenzyl, 3,3’-diaminobenzophenone, 4,4’-diaminobenzophenone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-AMINOPHENYL)fluorene, 2,2-bis(4-aminophenoxy)propane, 4,4’-bis(4-aminophenoxy)diphenyl, dianisidine, 3,3’-dichlorobenzidine and so on. Of these, preferably used are the monoamines, particularly preferred are aniline or aniline derivatives.

Isocyanate compound of the formula (r) is not specifically limited provided that it has two or more isocyanate groups attached to carbon atoms respectively. This compound includes, for example, n-delete the entry, the m-delete the entry, delete the entry, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-colorvision, 2,6-colorvision, diphenylmethanediisocyanate, solidinvestment, diphenyl ether diisocyanate, 1,5-naphthylenediisocyanate, dianisidines, 9-ethylcarbazole-3,6-diisocyanate, 3,3’-dimethyl-4,4’-diphenylmethanediisocyanate, hexamethylenediisocyanate, isophoronediisocyanate, triphenyltetrazolium, three is(4-phenylisocyanate)thiophosphate, 4,4’,4’-triisocyanate-2,5-dimethoxytrityl, 4,4’,4’-triisocyanate, m-xylylenediisocyanate, liaindizecign, dimeric acid diisocyanate, isopropylidene bis-4-cyclohexylaniline, dicyclohexylmethane and methylcyclohexanone.

As the isocyanate compound of the formula (r) may also be used diisocyanate dimers, such as N,N’-(4,4’-dimethyl-3,3’-diphenyldiisocyanate)uretdione (Desmodule

TT, trademark), colorvitality dimer; and diisocyanate trimers, such as 4,4’,4’-trimethyl-3,3’,3’-triisocyanate-2,4,6-triphenylene. You can also use a water adduct of isocyanate selected from colordistance, diphenylmethanediisocyanate and the like, such as 1,3-bis(3-isocyanato-4-were)urea; polyol as one adducts, such as trimethylolpropane adducts selected from colordistance (Desmodule L, Coronate L, trade name); and amine adducts. Can also be used compounds having two or more isocyanate groups, including isocyanate compounds and isocyanate adducts described in the detailed description of Japanese patent JP-A-10-76757 and detailed description of Japanese patent JP-A-10-95171 (the contents of these links are listed here as a reference).

Of the above as examples of isocyanate compounds, aroma is practical isocyanates, having isocyanate groups attached to the benzene ring, are preferred. More preferred are n-delete the entry, the m-delete the entry, delete the entry, 2,4-colorvision, 2,6-colorvision, diphenylmethanediisocyanate, solidinvestment, diphenyl ether diisocyanate, 1,5-naphthylenediisocyanate, triphenyltetrazolium, N,N’-(4,4’-dimethyl-3,3’-diphenyldiisocyanate)uretdione (Desmodule TT, trade name), 4,4’,4’-trimethyl-3,3’,3’-triisocyanate-2,4,6-triphenylene, 1,3-bis(3-isocyanato-4-were)urea and trimethylolpropane adducts selected from colordistance (Desmodule L, Coronate L, trade name). Particularly preferred examples of the isocyanate compounds of the formula (r) are colordistance. Of colordistance preferred is 2,4-colorvision. In addition, 2,4-colordistance as isocyanate compounds of the formula (r) may also be used mixtures of 2,4-colordistance and 2,6-colordistance, which are widespread on the market and available at a low price.

Amine compound of General formula (s) is not specifically limited provided that it has two or more aminopropanol compound includes, for example, aromatic amines such as 4,4’-diamino-3,3’-dietitian Lotan, 4,4’-diaminobenzanilide, 3,5-diaminophenol, diaminodiphenyl ether, 3,3’-dichloro-4,4’-diaminodiphenylmethane, 3,3’-dimethyl-4,4’-diaminodiphenylmethane, tolidine base, dianisidine, bis[4-(m-aminophenoxy) phenyl] sulfon, bis[4-(p-aminophenoxy) phenyl]sulfon, bis[3-methyl-4-(p-aminophenoxy) phenyl] sulfon, 3,3’-dimethoxy-4,4’-diaminobiphenyl, 3,3’-dimethyl-4,4’-diaminobiphenyl, 2,2’-dichloro-4,4’-diamino-5,5’-dimethoxybiphenyl, 2,2’,5,5’-tetrachloro-4,4’-diaminobiphenyl, o-toluensulfonyl, 2,4’-diaminobiphenyl, 2,2’-diaminobiphenyl, 4,4’-diaminobiphenyl, 2,2’-dichloro-4,4’-diaminobiphenyl, 3,3’-dichloro-4,4’-diaminobiphenyl, 2,2’-dimethyl-4,4’-diaminobiphenyl, 4,4’-thiodianiline, 2,2’-dicitionary, 4,4’-dicitionary, 4,4’-diaminodiphenyl ether, 3,3’-diaminodiphenyl ether, 3,4’-diaminodiphenyl ether, 4,4’-diaminodiphenylmethane, 3,4’-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl)sulfon, bis(3,4-diaminophenyl)sulfon, 4,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylsulfone, 3,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylmethane, 4,4’-diaminodiphenylamine, 4,4’-ethylendiamin, 4,4’-diamino-2,2’-dimethylbenzyl, 3,3’-diaminobenzophenone, 4,4’-diaminobenzophenone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-AMINOPHENYL)fluorene, 2,2-bis(4-aminophenoxy)propane, 4,4’-bis(4-aminophenoxy)diphenyl, dianisidine, 3,3’-dichlor Sedin, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine and the like; heterocyclic amines such as guanmin, acetogenin, 2,4-diamino-6-[2’-Mei-(1)]ethyl-s-triazine, 2,3-diaminopyridine, 2.5-diaminopyridine, 2,3,5-diaminopyridine, bis(aminopropyl)piperazine and the like; and aliphatic amines such as metandienon, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,3-diamino-2-hydroxypropane, Ethylenediamine, Diethylenetriamine, Triethylenetetramine, Tetraethylenepentamine, N-methyl-3,3’-iminobis(Propylamine), hexamethylenediamine were, bis(aminomethyl)cyclohexane, ISOPHORONEDIAMINE, isopropylidenebis(aminocyclohexane), 4,4’-diaminodicyclohexylmethane, xylylenediamine and so on. From the above example compounds of aromatic amines are preferred, and especially preferred are aniline derivatives having at least two amino groups, and which are represented by the following formula (VIII):

where R1, R2, R3and R4independently represent a hydrogen atom, halogen atom, alkyl group, alkoxygroup or amino group, X1and X2independently represent an amino group or a group represented by the formula (b):

and Y1is any one of-SO -, -O-, -(S)n-, -(CH2)n-, -CO-,-CONH-, -NH-, -CH(COOR1)-, -C(CF3)2-, -CR2R3- and a group represented by any of formulas (a)

or absent; each of R1, R2and R3represents an alkyl group, and n is 1 or 2.

Amine compound of General formula (t) include aromatic amines such as aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-fenetidin, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xylidin, 2,4-xylidin, 3,4-xylidene, 2,6-xylidene, 4-aminobenzonitrile, Anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α -naphtylamine, aminoanthracene, o-ethylaniline, o-Chloroaniline, m-Chloroaniline, p-Chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline, N,N-diglycidylether, N,N-diglycidyl-o-toluidine, acetoacetic anilide acid, bromide of trimethylphenylammonium, 4,4’-diamino-3,3’-diethyldiphenylurea, 4,4’-diaminobenzanilide, 3,5-diaminophenol, diaminodiphenyl ether, 3,3’-dichloro-4,4’-diaminodiphenylmethane, 3,3’-dimethyl-4,4’-diaminodiphenylmethane, tolidine the basis of Finlandia is in, m-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, p-(N-phenylcarbamoyl) aniline, n-[N-(4-chlorophenyl) carbarnoyl] aniline, n-[N-(4-AMINOPHENYL)carbarnoyl]aniline, 2-methoxy-5- (N-phenylcarbamoyl)aniline, 2-methoxy-5-[N-(2’-methyl-3’-chlorophenyl) carbarnoyl] aniline, 2-methoxy-5-[N-(2’-chlorophenyl)carbarnoyl]aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminophenol, 4-(N-methyl-N-acetylamino)aniline, 2,5-diethoxy-4-(N-benzoylamine)aniline, 2,5-dimethoxy-4-(N-benzoylamine)aniline, 2-methoxy-4-(N-benzoylamine)-5-methylaniline, 4-sulfanilamide, 3-sulfanilamide, 2-(N-ethyl-N-phenylenesulfonyl) aniline, 4-dimethylaminoacetonitrile, 4-diethylaminoethylamine, sulfathiazole, 4-aminodiphenylamine, 2-chloro-5-N-phenylsulfonyl, 2-methoxy-5-N,N-diethylcarbamoyl, 2,5-dimethoxy-4-N-phenylsulfonyl, 2-methoxy-5-benzisothiazolin, 2-phenoxycarbonylamino, 2-(2’-chlorophenoxy)sulfanilamide, 3-anilinomethyl-4-methylaniline, bis[4-(m-aminophenoxy)phenyl]sulfon, bis[4-(aminophenoxy)phenyl]sulfon, bis[3-methyl-4-(p-aminophenoxy)phenyl]sulfon, 3,3’-dimethoxy-4,4’-diaminobiphenyl, 3,3’-dimethyl-4,4’-diaminobiphenyl, 2,2’-dichloro-4,4’-diamino-5,5’-dimethoxybiphenyl, 2,2’,5,5’-tetrachloro-4,4’-diaminobiphenyl, o-toluensulfonyl, 2,4’-diaminobiphenyl, 2,2’-diaminobiphenyl, 4,4’-diaminobiphenyl, 2,2’-dichloro-4,4’-diaminobiphenyl, 3,3’-dichloro-4,4’diaminobiphenyl, 2,2’-dimethyl-4,4’-diaminobiphenyl, 4,4’-thiodianiline, 2,2’-dicitionary, 4,4’-dicitionary, 4,4’-diaminodiphenyl ether, 3,3’-diaminodiphenyl ether, 3,4’-diaminodiphenyl ether, 4,4’-diaminodiphenylmethane, 3,4’-diaminodiphenylmethane, bis(3-amino-4-chlorophenyl)sulfon, bis(3,4-diaminophenyl)sulfon, 4,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylsulfone, 3,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylmethane, 4,4-diaminodiphenylamine, 4,4’-ethylendiamin, 4,4’-diamino-2,2’-dimethylbenzyl, 3,3’-diaminobenzophenone, 4,4’-diaminobenzophenone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-AMINOPHENYL)fluorene, 2,2-bis(4-aminophenoxy)propane, 4,4’-bis(4-aminophenoxy)diphenyl, 3,3’,4,4’-tetraaminodiphenyl ether, 3,3’,4,4’tetraaminodiphenyl, 3,3’,4,4’-tetraaminobiphenyl, 3-aminobenzonitrile, 4-fenoxedilom, 3-fenoxedilom, 4,4’-Methylenebis-o-toluidine, 4,4’-(p-phenyleneisopropylidene)-bis-(2,6-xylidene), o-chloro-p-nitroaniline, o-nitro-p-Chloroaniline, 2,6-dichloro-4-nor is rosanilin, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, metol, 2,4-diaminophenol, N-(β -hydroxyethyl)-o-aminophenol sulfate, sulfanilic acid, Manilova acid, 4B acid, acid, 2B acid, p-ftoranila, ftoranila, 3-chloro-4-ftoranila, 2,4-diptiranjan, 2,3,4-triptorelin, m-aminobenzotrifluoride, m toluylenediamine, 2-aminothiophenol, 2-amino-3-bromo-5-nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, acceleratory diphenylamine, 2-methyl-4-methoxydiphenyl, N,N-diphenyl-p-phenylenediamine, dianisidine, 3,3’-dichlorobenzidine, 4,4’-diaminostilbene-2,2’-disulfonate acid, benzylideneaniline, 1,8-naphthaleneamine, national sodium, Tobias acid, H acid, J acid, phenyl J acid, 1,4-diaminoanthraquinone, 1,4-diamino-2,3-dichloroanthracene and so forth; and heterocyclic amines such as 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α -aminoε -caprolactam, acetogenin, 2,4-diamino-6-[2’-Mei-(1)]ethyl-s-triazine, 2, 3-diaminopyridine, 1, 2.5-diaminopyridine, 2,3,5-diaminopyridine, 1-amino-4-methylpiperazine, 1-(2-amino-ethyl)piperazine, bis(aminopropyl)piperazine, N-(3-aminopropyl)morpholine, and so forth. Most of them are preferably used aromatic monoamines.

Alcohol compound of General fo the mules (u) is not specifically limited, provided that it represents a polyol as one compound having two or more Oh groups.

Alcohol compound includes diols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propandiol, 1,2-propandiol, propylene glycol, dipropyleneglycol, tripropyleneglycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, hexyleneglycol, 1,9-nonanediol, neopentylglycol, methylpentanediol and so forth; aliphatic polyols such as glycerol, castor oil, trimethylolpropane, trimethylacetyl, hexanetriol, pentaerythritol, α -methylglucoside, sorbitol, sucrose and the like; polyols, such as glycols, polypropylenglycol, polytetramethylene, adeptpro.info polyols, epoxy-modified polyols, polyether ester polyols, polycarbonate polyols, polycaprolactone diols, aminodiphenylamine polyols, polyester polyols obtained by adding one or a mixture of two or more alkalisation (for example, ethylene oxide and propylene oxide) to one of or a mixture of two or more polyhydric alcohols (such as glycerin and propylene glycol), acrylic polyols, fluorinated polyols, polybutadiene polyols, polyhydroxyvalerate, polyols derived from castor oil, polymer polyols, halogenated polyols, phosphorus-containing polyols, and so forth; and alkanolamine, such as N-alkyldiethanolamine, N-alkyldiethanolamine, triethanolamine, triisopropanolamine, N,N,N’,N’-tetrakis(2-hydroxyethyl)Ethylenediamine, N,N,N’,N’-tetrakis(2-hydroxypropyl)Ethylenediamine, and so forth. Of these, preferably used are diols, aliphatic polyols, alkanolamine and polyols having a molecular weight of 2000 or less.

Amine compound of General formula (XVII) include, for example, aromatic diamines such as 4,4’-diamino-3,3’-diethyldiphenylurea, 4,4’-diaminobenzanilide, 3,5-diaminophenol, diaminodiphenyl ether, 3,3’-dichloro-4,4’-diaminodiphenylmethane, 3,3’-dimethyl-4,4’-diaminodiphenylmethane, tolidine base, dianisidine, bis[4-(m-aminophenoxy)phenyl]sulfon, bis[4-(p-aminophenoxy)phenyl]sulfon, bis[3-methyl-4-(p-aminophenoxy)phenyl]sulfon, 3,3’-dimethoxy-4,4’-diaminobiphenyl, 3,3’-dimethyl-4,4’-diaminobiphenyl, 2,2’-dichloro-4,4’-diamino-5,5’-dimethoxybiphenyl, 2,2’,5,5’-tetrachloro-4,4’-diaminobiphenyl, o-toluensulfonyl, 2,4’-diaminobiphenyl, 2,2’-diaminobiphenyl, 4,4’-diaminobiphenyl, 2,2’-dichloro-4,4’-diaminobiphenyl, 3,3’-dichloro-4,4’-diaminobiphenyl, 2,2’-dimethyl-4,4’-diaminobiphenyl, 4,4’-thiodianiline, 2,2’-dicitionary, 4,4’-dicitionary, 4,4’-diamino-diphenyl ether, 3,3’-diaminodiphenyl ether, 3,4’-diaminodiphenyl ether, 4,4’-diaminodiphenylmethane, 3,4’-diaminodiphenylmethane, b is(3-amino-4-chlorophenyl)sulfon, bis(3,4-diaminophenyl)sulfon, 4,4’ -diaminodiphenylsulfone, 3,3’-diaminodiphenylsulfone, 3,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylmethane, 4,4’-diaminodiphenylamine, 4,4’-ethylendiamin, 4,4’-diamino-2,2’-dimethylbenzyl, 3,3’-diaminobenzophenone, 4,4’-diaminobenzophenone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-AMINOPHENYL)fluorene, 2,2-bis(4-aminophenoxy)propane, 4,4’-bis(4-aminophenoxy)-diphenyl, dianisidine, 3,3’-dichlorobenzidine and so on. Amine compounds of General formula (XVII)in which γ1represents sulfonyloxy group or methylene group, are preferred.

For each urea-urethane compound according to aspects of the present invention with first through fourth isocyanate and the corresponding reagents are mixed for communicating in an organic solvent or without the solvent, and then to collect the crystals are filtered, crystallization, desolvation, thereby obtaining the desired compound. The interaction may be carried out using a method in which the substance having two or more groups in the molecule, is used in large excess and other substances that interact with groups, is added in small portions. When used this way it is possible to interact the only one of the two or more groups.

In addition, it is preferable to thoroughly mix system to obtain adequate dispersion of the added substance immediately after adding. The above applies to any of the urea-urethane compounds, shown here as examples. The way the interaction is not limited to the above method and can be used any way subject to obtaining the same result as the one above. As each of the reagents can be used one or more connections depending on the purpose. The solvent can be any solvent provided that it does not react with the isocyanate group and the functional groups of the reactants. The solvent includes, for example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons, and ketones. Especially preferred are methyl ethyl ketone, toluene and the like, which dissolve the isocyanate and the reaction products have low solubility. The reaction product obtained by the above reaction is not always a single connection, in some cases obtained in the form of a mixture of compounds different in position is of deputies.

Specific examples of the urea-urethane compounds of the aspects of the invention, from the first to the fourth, are the following compounds (S-1)-(S-70)).

Each urea-urethane composition in accordance with aspects of the present invention from the fifth to the twelfth and urea-urethane composition obtained by the method of receiving according to aspects of the invention from the thirteenth to the twentieth, preferably include 50 wt.% or more, more preferably 60 wt.% or more, more preferably 70 wt.% or more urea-urethane compounds having in the molecule at least one urethane group (-NHCOO - group) and at least one urea group (-NHCONH - group) with a total of from 2 to 10 and having a molecular weight of 5000 or less.

Such urea-urethane composition can be used in combination with a colorless or light-colored substance is a precursor of Kras is referred to to get a color-forming composition for heat-sensitive recording substance or pressure-sensitive recording material. This color-forming composition as effective, perfect for color formation and storage of print.

The urea-urethane compound as the main component of the urea-urethane composition has at least one urea group and at least one urethane group in the molecule. The group of urea and urethane group are adjacent with respect to each other, connected via at least one residue of a compound (such a structural fragment here and hereinafter referred to as urea-urethane structural fragment). The total number of urethane group(s) and group(s) of urea is not more than 10 and not less than 2, preferably no more than 10 and not less than 3, more preferably not more than 10 and not less than 4.

The ratio of the urethane(s) group(s) to the group(s) of the urea is preferably 1:3-3:1, more preferably 1:2-2:1, most preferably 1:1. The molecular mass of the urea-urethane compounds is 5000 or less, preferably 2000 or less.

The content of the urea-urethane compound in each urea-urethane composition in accordance with aspects n the present invention from the fifth to the twentieth equal to 50 wt.% or more. Such urea-urethane composition can be obtained by using a relatively simple method of obtaining. On the other hand, it can exhibit excellent performance characteristics due to the high content of urea-urethane compounds, which can exhibit excellent color-forming properties, and characteristics of storage that is required for the color-forming composition. In addition, as the urea-urethane compounds may be used either a single compound or a mixture of two or more compounds, including isomers.

In addition, a mixture of two or more compounds, including isomers, can be used as a urea-urethane compound in order to improve the color-forming ability, the storage characteristics and the like.

On the other hand, the urea-urethane compound according to the present invention can be appropriately diluted with a substance that does not affect the action of the present invention. Such diluents include, for example, Caloplaca substances, acid developers, amine compounds, isocyanate compounds, compounds of urea, urethane compounds, and the like, which are described here above. Of them, preferred are compounds of urea and urethane compounds that have the structure, under the service of the urea-urethane compound, as they improve sensitivity. Also preferred are compounds that are produced by the interaction of polyisocyanate compounds with hydroxidealuminum or aminoguanidinium. Such diluents are preferably contained in the resulting dilution in the proportion of 0.0001 to 50 wt.% relative to the total mass of the urea-urethane compound and diluent. For the manifestation of the properties of the storage content of the solvent is more preferably 40 wt.% or less, even more preferably 30 wt.% or less. To improve the sensitivity of the content of the solvent is more preferably 0.01 wt.% or more, even more preferably 1 wt.% or more. In some cases, this diluent is produced in the course of the synthesis reaction of the urea-urethane compounds. When to enhance the sensitivity, add the diluent, it is preferable to add it in the course of the synthesis reaction. For example, preferred is a urea-urethane composition comprising a diluent, and the urea-urethane compound having at least one urea group and at least one urethane group, with the total number in the molecular structure of 2 to 10 and having a molecular weight of 5000 or less, which(OE) is characterized by a diluent in a ratio of 0.0001 to 50 wt.%. Redactie was observed in the case of compositions in accordance with aspects of the present invention from the eighth through the twelfth, and compositions obtained by the method of obtaining, in accordance with aspects from the thirteenth to the twentieth.

Each urea-urethane composition in accordance with aspects of the present invention from the fifth to the twentieth is preferably colorless or light-colored solid with a melting point of from the point of view of use in heat-sensitive recording material. The melting point of the composition is preferably from 40° to 300° S, more preferably from 60° With up to 260° C.

As a method of obtaining any urea-urethane composition according to aspects of the present invention from the fifth to the twentieth preferred method of forming one or more urethane groups of the at least one isocyanate group of polyisocyanate compound and a hydroxyl group hydroxycodone and education then one or more urea groups remaining unreacted isocyanate group(s) of the same polyisocyanate compounds and amino group(s) of the amino compounds; or a method of forming one or more group(s) of urea from at least one isocyanate group of the polyisocyanate compound and the amino group(s) of amino compounds and education then one or more urethane(s) group(s) of the remaining who, for example by transferring them unreacted isocyanate(Oh) group(s) of the same polyisocyanate compound and a hydroxyl(s) group(s) hydroxycodone.

When polyisocyanate connection and hydroxycodone form one or more urethane groups, urea-urethane composition can be efficiently obtained using polyisocyanate connection in excess relative to the hydroxyl(s) group(s), by attaching a polyisocyanate compound to hydroxycoumarin in the amount of one molecule with a hydroxyl group hydroxycodone to interact with only one isocyanate group of the polyisocyanate compound, and leaving unreacted at least one isocyanate group, and then the remaining interaction neproreagirovavshikh isocyanate(Oh) group(s) with aminoguanidinium with the formation of one or more urea groups. In this case, it is preferable to obtain one or more urethane groups, through such interaction polyisocyanate compounds with hydroxidealuminum to the ratio of the number of moles of the polyisocyanate compound to the number of hydroxyl equivalents hydroxycodone was 100/1-1/2 and that the ratio of equivalents of isocyanate group of the polyisocyanate compound to the number of hydroxyl equivalents hydroxycodone became 1000/1-1/1.

Adding hydroxycodone to the polyisocyanate compound gidroksosoedinenii it is preferable to add a small and portions so to polyisocyanate compound is always in the reaction system in an excessive amount relative to the hydroxyl(Oh) groups(e). This method of addition is preferred in particular when the interaction is carried out at the ratio of the number of moles of the polyisocyanate compound to the number of hydroxyl equivalents hydroxycodone about 1/1, for example 5/1-1/2.

Similarly, when the polyisocyanate compounds and amino compounds have one or more groups of urea, urea-urethane composition can be efficiently obtained using the polyisocyanate compound in an excess amount relative to the amino group(s), by attaching a polyisocyanate compound to aminosidine in the amount of one molecule of the amino group of amino compounds to interact with only one isocyanate group of the polyisocyanate compound and leaving unreacted at least one isocyanate group, and then the remaining interaction neproreagirovavshikh isocyanate(Oh) group(s) with hydroxidealuminum with the formation of one or more urethane groups.

In this case, it is preferable to obtain one or more groups of urea by such interaction polyisocyanate compounds with aminoguanidinium to the ratio of the number of moles of the polyisocyanate with the unity among aminoquinolines of amino compounds was 100/1-1/2 and that the ratio of equivalents of isocyanate group of the polyisocyanate compound to the number of aminoquinolines of amino compounds was 1000/1-1/1.

Adding amino compounds to the polyisocyanate compound aminosidine it is preferable to add small portions so that the polyisocyanate compound is always in the reaction system in an excessive amount relative to the amino group(s). This method of addition is preferred in particular when the interaction is carried out at the ratio of the number of moles of the polyisocyanate compound to the number of aminoquinoline the amino compounds of about 1/1, for example 5/1-1/2.

In the method of obtaining any urea-urethane kompozitsiiu accordance with aspects of the present invention from the fifth to the twentieth, the interaction of polyisocyanate compounds and hydroxycodone with the formation of one or more urethane groups is preferably carried out without solvent, adding either dropwise or pouring out gidroksosoedinenii, either without solvent or diluting gidroksosoedinenii solvent or dispersive gidroksosoedinenii in the solvent, or continuously, or portions or diluted polyisocyanate compound with a solvent or dispersed in the polyisocyanate compound in the solvent. In this way the interaction of polyisocyanate compounds with aminoguanidinium with the formation of one or more urea groups can be carried out without solvents is I, adding either dropwise or pouring out aminosidine, either without solvent or diluting aminosilicone solvent or dispersive aminosidine in the solvent, or continuously, or portions or diluted polyisocyanate compound with a solvent or dispersed in the polyisocyanate compound in the solvent.

The above method of production, which includes adding hydroxycodone or amino compounds in the polyisocyanate compound in small portions, preferred, in particular, in the following case: in the reaction of obtaining a urea-urethane composition in a time when at least one isocyanate group in the polyisocyanate molecules connection goes, the other isocyanate(s) group(s) interact(s) with hydroxidealuminum or aminoguanidinium obtaining one or more urethane groups or urea groups, respectively. Moreover, the method of obtaining is preferred when gidroksosoedinenii having two or more hydroxyl groups, or aminosilane having two or more amino groups, interacts with a polyisocyanate compound having two or more isocyanate groups.

When carrying out the above reaction is preferably thoroughly mixed system so that add is in the polyisocyanate hydroxy or aminosidine dropwise or emptying immediately and adequately dispersibles. Preferably carefully stir the reaction system, for example, by adjusting the stirring speed in the reactor, selecting a mixing blade or partition.

Preferably the interaction with the formation of one or more urethane groups and interaction with the formation of one or more urea groups separately and sequentially. When performed at the same time, the content of the urea-urethane compound in the urea-urethane composition is undesirable decreases. Such a reaction is the formation of urethane groups and reaction formation, the group of urea, preferably sequentially. In the method according to the present invention, because in the process of obtaining a separation and purification stages are not mandatory, may be simplified to the two reaction stages in series.

Receipt of any urea-urethane composition in accordance with aspects of the present invention from the fifth to the twentieth, when used politcially adduct with hydroxidealuminum, which is an isocyanate, already having one or more urethane groups in the molecule, then the urea-urethane composition can be obtained by reacting this adduct with aminoguanidinium. In this case, preferably, formed of one or several flats which are groups of urea by conducting interaction equivalent relations isocyanate groups and amino groups is equal to 2/1-1/100, and removing napoleanville aminosidine.

Receipt of any urea-urethane composition in accordance with aspects of the present invention from the fifth to the twentieth, when used polyisocyanate adduct with aminoguanidinium that already contains one or more urea groups in the molecule, then the urea-urethane composition can be obtained by reacting this adduct with hydroxidealuminum. In this case, preferably, formed of one or more urethane groups by conducting interaction with the equivalent ratio of isocyanate groups and hydroxy-group is equal to 2/1-1/100, and removing napoleanville gidroksosoedinenii.

When conducting interaction(s) with obtaining any urea-urethane composition in accordance with aspects of the present invention from the fifth to the twentieth, used solvent, the solvent is not specifically organic, provided that it does not react with the isocyanate group and the like. The solvent includes, for example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons, ketones and phosphate esters. Especially preferred are what I acetone, methyl ethyl ketone, toluene and the like, which dissolve the isocyanate and the reaction product has a low solubility. When necessary soluble powder isocyanate are preferred phosphoric esters, in particular trimethylphosphate.

When using such a solvent, the formation of one or more urethane groups and the formation of one or more groups of the urea is preferably carried out in the same solvent, to facilitate reuse of the solvent, and continuously carry out the interaction for the formation of the group of urea and interaction for the formation of urethane groups.

The reaction temperature at which the polyisocyanate interacts with hydroxidealuminum and/or aminosilanes the formation of one or more urethane groups and/or one or more urea groups is from 0° to 300° S, preferably from 5° to 200° S, more preferably from 10° to 150° C. the Reaction temperature is properly determined depending on the selected polyisocyanate compounds, hydroxycodone and amino compounds. It is also possible to carry out the formation of urethane groups and the formation of urea at different temperatures suitable for such entities, respectively.

When EOI is modestie MDI with hydroxidealuminum, and/or aminoguanidinium with the formation of one or more urethane groups and/or one or more urea groups can be used catalyst. The catalyst includes, for example, tertiary amino compounds such as triethylamine, 1,4-diazabicyclo(2,2,2)octane and the like; and organic acid salts such as dilaurate dibutylamine and so on. Typically, the concentration of catalyst is from 1 to 10000 hours per million, preferably from 10 to 2000 hours/million, relative to the isocyanate compound. Among the above catalysts, preferred are tertiary amino compounds.

The urea-urethane composition comprising a urea-urethane compound having a lot urea-urethane structural fragments in the molecule may be a repetition of the stages of the method of receiving according to the present invention two or more times, using, for example, allinaday having two or more amino groups, and gidroksosoedinenii having two or more hydroxyl groups. As each stage during the interaction it is possible to achieve a sufficiently high yield, the method of receiving according to the present invention enables relatively simple to obtain a urea-urethane composition having a high performance.

The polyisocyanate compound used in each aspectratio invention from the fifth to the twentieth, not specifically restricted provided that it has two or more isocyanate groups attached to carbon atoms respectively. The polyisocyanate compound includes, for example, n-delete the entry, the m-delete the entry, delete the entry, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-colorvision, 2,6-colorvision, diphenylmethanediisocyanate, solidinvestment, diphenyl ether diisocyanate, 1,5-naphthylenediisocyanate, dianisidines, 9-ethylcarbazole-3,6-diisocyanate, 3,3’-dimethyl-4,4’-diphenylmethanediisocyanate, hexamethylenediisocyanate, isophoronediisocyanate, triphenyltetrazolium, Tris(4-phenylisocyanate)thiophosphate, 4,4’,4’-triisocyanate-2,5-dimethoxytrityl, 4,4’,4’triisocyanurate, m-xylylenediisocyanate, liaindizecign, diisocyanate dimer acid, isopropylidene bis-4-cyclohexylaniline, dicyclohexylmethane and methylcyclohexanone. As polyisocyanate compounds can also be used diisocyanate dimers, such as N,N’-(4,4’-dimethyl-3,3’-diphenyldiisocyanate)uretdione (Desmodule TT, trade name), colorvitality dimer; and diisocyanate trimers, such as 4,4’,4’-trimethyl-3,3’,3’-triisocyanate-2,4,6-triphenylene. Can also be used water adducts of isocyanates, selected from tolualdehyde Janata, diphenylmethanediisocyanate and the like, such as 1,3-bis(3-isocyanato-4-were)urea; polyol as one adducts, such as trimethylolpropane adducts selected from colordistance (Desmodule L, Coronate L, trade names); and amine adducts. Can also be used compounds having two or more isocyanate groups, including isocyanate compounds and isocyanate adducts described in the detailed description of Japanese patent JP-A-10-76757 and detailed description of Japanese patent JP-A-10-95171 (the contents of these links are given here as a reference). The above compounds can be used alone or in combination.

Among the above-mentioned as examples of compounds preferred examples of the polyisocyanate compounds are aromatic polyisocyanates having isocyanate groups attached to the benzene ring, such as n-delete the entry, the m-delete the entry, delete the entry, 2,4-colorvision, 2,6-colorvision, diphenylmethanediisocyanate, solidinvestment, diphenyl ether diisocyanate, 1,5-naphthylenediisocyanate, triphenyltetrazolium, N,N’-(4,4’-dimethyl-3,3’-diphenyldiisocyanate)uretdione (Desmodule TT, trade name), 4,4’,4’-trimethyl-3,3’,3’-triisocyanate-2,4,6-triphenylene, 1,3-bis(3-isocyanato-4-were)urea, trimethylol panowie adducts, selected from colordistance (Desmodule L, Coronate L, trade name) and so on. Particularly preferred examples of the polyisocyanate compounds are colordistance. Among colordistance preferred is 2,4-colorvision. In addition to 2,4-colordistance as polyisocyanate compounds may also be used mixtures of 2,4-colordistance and 2,6-colordistance, which are widely spread on the market and available at a low price.

As hydroxycodone, which interacts with the polyisocyanate connection with obtaining one or more urethane groups can be specified phenolic compounds and alcohol compounds.

Phenolic compounds include, for example, phenol, cresol, Xylenol, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-op, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-NITROPHENOL, o-chlorophenol, p-chlorophenol, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(hydroxyphenyl)butane, 2,2-bis(hydroxyphenyl)pentane, 2,2-bis(hydroxyphenyl)heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyragollole, hydroquinone, methylhydroquinone, 4-phenylphenol, p,p’-biphenol, 4-cumylphenol, butyl bis (4-hydroxyphenyl)acetate, benzyl bis(4-hydroxyphenyl)acetate, bis(4-hydroxyphenyl)sulfon, bis(3-methyl-4-hydroxyphenyl)sulfon, bis(3,5-di is ethyl-4-hydroxyphenyl)sulfon, 4-hydroxyphenyl-4’-methylphenylsulfonyl, 3-chloro-4-hydroxyphenyl-4’-methylphenylsulfonyl, 3,4-dihydroxyphenyl-4’-methylphenylsulfonyl, 4-isopropoxyphenyl-4’-hydroxyanisole, bis(2-allyl-4-hydroxyphenyl)sulfon, 4-hydroxyphenyl-4’-benzyloxyphenyl, 4-isopropylphenyl-4’-hydroxyanisole, 4-hydroxy-4’-isopropoxyphenyl, bis(2-methyl-3-tert-butyl-4-hydroxyphenyl)sulfide, 4,4’-dihydroxydiphenyl ether, 4,4’-thiodiphenol, 4,4’-dihydroxybenzophenone, 2,2-bis(4-hydroxyphenyl)hexaferrite, 4,4’-dihydroxydiphenylmethane, 3,3’-dihydroxydiphenyl, bis(4-hydroxy-3-were)sulfide, bis(4-(2-hydroxy)phenyl)sulfon, 2,4-dihydroxybenzophenone, 2,2’,4,4’-tetrahydroxybenzophenone, fenilsalitsilat, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, (4’-Chlorobenzyl) 4-hydroxybenzoate, ethyl 1,2-bis(4’hydroxybenzoate), pencil 1,5-bis(4’-hydroxybenzoate), hexyl 1,6-bis(4’-hydroxybenzoate), dimethyl 3-hydroxyphthalic, staringelf, laurelhurst, metalsalt, 4-methoxyphenol, 4-(benzyloxy)phenol, 4-hydroxybenzaldehyde, 4-n-octyloxybenzoic acid, 4-n-butiloxinazola acid, 4-n-petrogenetically acid, 3-n-dodecyloxybenzoic acid, 3-n-actinomycetoma acid, 4-p-octyloxybenzoate acid and 4-n-oceanoislascanariascom the acid.

Visayas is installed as examples of phenolic compounds, phenol, phenol derivatives represented by the following formula (w), and diprolene compounds represented by the following formula (XVI)are preferred.

where the atom(s) of each hydrogen of the benzene ring may be substituted(s) alkyl group, cycloalkyl group, phenyl group, amide group, alkogolnoy group, a nitro-group, a nitrile group, a formyl group, dialkylamino, methanesulfonyl group or IT group; and

where the atom(s) of each hydrogen of the benzene ring may be substituted(s) Deputy, which preferably represents the residue of aromatic compounds, the aliphatic residue of a compound or a residue of heterocyclic compounds, although the Deputy may be a hydroxyl group, a nitro-group, a nitrile group, carbamoyl group, sulfamoyl group, a carboxyl group, nitrosoureas, amino group, accelerograph, nitrolingual, hydratherapy, raidgroups, isocyanate group, mercaptopropyl, sulfopropyl or a halogen atom, each residue can have one or more substituents, δ represents a group selected from the group comprising -SO2-, -O-, -(S)n-, -(CH2)n-, -CO-, -CONH-, -NH-, -CH(COOR 1)-, -C(CF3)2- and- (CR2R3or absent, R1, R2and R3independently represent an alkyl group and n is 1 or 2.

The term “aliphatic”, as used in the case of aspects of the present invention from the fifth to the twentieth, includes the term “alicyclic”.

The term “residue of aliphatic compounds”, as used in the case of aspects of the present invention from the fifth to the twentieth, means the residue, attached through a carbon atom aliphatic hydrocarbon moiety in the balance. The term “residue of aromatic compounds”, as used here, means the residue, attached through a carbon atom of the aromatic ring such as benzene ring residue. The term “residue of heterocyclic compounds”, as used here, means the residue, attached through a carbon atom of the heterocyclic ring residue.

Preferred examples of the substituent residue of aliphatic compounds, residue of the heterocyclic compound or residue aromatic compounds are alkyl groups, cycloalkyl group, phenyl group, amide group, CNS group, the nitro-group, a nitrile group, a halogen atom, formyl group, dialkylamino, toluensulfonyl group and methansulfonate gr is the PAP.

As alcohol compounds indicated compounds having at least one Oh group attached to a carbon atom of aliphatic compounds. Examples of the alcohol compounds are alcohols, described in Solvent Handbook, Kodansha Scientific Co., Ltd., ninth edition (1989), str-420 and str-817. Alcohol compound includes, for example, aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, Isobutanol, s-butanol, tert-butanol, pentanol, Cyclopentanol, tert-amyl alcohol, 2-pentanol, isoamyl alcohol, hexanol, 3-hexanol, cyclohexanol, cyclohexylmethanol, 4-methyl-2-pentanol, heptanol, isoheptane, octanol, 2-ethyl-1-hexanol, Caprylic alcohol, nonlevy alcohol, icononly alcohol, decanol, undecylenic alcohol, dodecyloxy alcohol, tridecylamine alcohol, tetradecanoyl alcohol, hexadecylamine alcohol, octadecylamine alcohol, isostearoyl alcohol and the like; unsaturated aliphatic alcohols such as allyl alcohol, 2-methyl-2-propen-1-ol, krotilova alcohol, propargilovyh alcohol and so forth; aliphatic alcohols having attached to it the rest of aromatic compounds such as benzyl alcohol, cinnamony alcohol and so forth; aliphatic alcohols having attached to it the rest of heterocyclic compounds such as 2-pyridinemethanol, 3-pyridinemethanol, 4-pyridinato is l, furfuryl alcohol and the like; halogenated aliphatic alcohols, such as 2-chloroethanol, 1-chloro-3-hydroxypropan and so on; glycol ethers, such as onomatology ether of ethylene glycol, monotropy ether of ethylene glycol, monopropylene ether of ethylene glycol, monoisopropylamine ether of ethylene glycol, monobutyl ether of ethylene glycol, monoisobutyl ether of ethylene glycol, monohexadecyl ether of ethylene glycol, monopoloy ether of ethylene glycol, onomatology ether of diethylene glycol, monotropy ether of diethylene glycol, monopropylene ether of diethylene glycol, monoisopropylamine ether of diethylene glycol, monobutyl ether of diethylene glycol, monoisobutyl ether of diethylene glycol, monohexadecyl ether of diethylene glycol, monopoloy ether of diethylene glycol, onomatology ether of propylene glycol, monotropy ether of propylene glycol, monopropylene ether of propylene glycol, monoisopropylamine ether of propylene glycol, monobutyl ether of propylene glycol, monoisobutyl ether of propylene glycol, monopoloy ether of propylene glycol, onomatology broadcast dipropyleneglycol, monotropy broadcast dipropyleneglycol, monopropylene broadcast dipropyleneglycol, monoisopropylamine broadcast dipropyleneglycol, monobutyl broadcast dipropyleneglycol, monoisobutyrate broadcast dipropyleneglycol, monopoloy broadcast dipropyleneglycol and so gave the e; diols, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propandiol, 1,2-propandiol, propylene glycol, dipropyleneglycol, tripropyleneglycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, hexyleneglycol, 1,9-nonanediol, neopentylglycol, methylpentanediol and so forth; aliphatic polyols such as glycerol, castor oil, trimethylolpropane, trimethylacetyl, hexanetriol, pentaerythritol, α -methylglucoside, sorbitol, sucrose and the like; polyols, such as glycols, polypropylenglycol, polytetramethylene, adeptpro.info polyols, epoxy-modified polyols, polyester esters of polyols, polycarbonate polyols, polycaprolactone diols, amine-modified polyols, polyester polyols obtained by adding one or a mixture of two or more alkilinity oxides (e.g. ethylene oxide and propylene oxide) to one or a mixture of two or more polyhydric alcohols (glycerin and propylene glycol), acrylic polyols, fluorinated polyols, polybutadiene polyols, polyhydroxyvalerate, polyols derived from castor oil, polymer polyols, halogenated polyols, phosphorus-containing polyols, and so forth; and alkanolamines, such as N,N-dialkylacrylamide, N,N-dialkylhydroxylamines, N-alkyldiethanolamine N-alkyldiethanolamine, triethanolamine, industry is propanolamine, N,N,N’,N’-tetrakis(2-hydroxyethyl)-Ethylenediamine, N,N,N’,N’-tetrakis(2-hydroxypropyl)Ethylenediamine, and so on.

Above as examples of the alcohol compounds, aliphatic alcohols having 10 or less carbon atoms, glycol ethers, diols, aliphatic polyols, polyols having a molecular weight of 2000 or less and alkanolamine are preferred.

Above as examples of the alcohol compounds may be used alone or in combination and above as examples of phenolic compounds can also be used independently or in combination.

As amino compounds, which interacts with the polyisocyanate connection with obtaining one or more groups of urea, can be used in any connection, provided that it has one or more amino groups attached to carbon atoms respectively. Aminosidine includes, for example, aromatic amines such as aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-fenetidin, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xylidine, 2,4-xylidine, 3,4-xylidine, 2,6-xylidine, 4-aminobenzonitrile is, Anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α -naphtylamine, aminoanthracene, o-ethylaniline, o-Chloroaniline, m-Chloroaniline, p-Chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline, N,N-diglycidylether, N,N-diglycidyl-o-toluidine, anilide acetoacetic acid, bromide of trimethylphenylammonium, 4,4’-diamino-3,3’-diethyldiphenylurea, 4,4’-diaminobenzanilide, 3,5-diaminophenol, diaminodiphenyl ether, 3,3’-dichloro-4,4’-diaminodiphenylmethane, 3,3’-dimethyl-4,4’-diaminodiphenylmethane, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, p-(N-phenylcarbamoyl)aniline, n-[N-(4-chlorophenyl)-carbarnoyl]aniline, n-[N-(4-AMINOPHENYL)carbarnoyl]aniline, 2-methoxy-5-(N-phenylcarbamoyl)aniline, 2-methoxy-5-[N-(2’-methyl-3’-chlorophenyl)carbarnoyl]aniline, 2-methoxy-5-[N-(2’-chlorophenyl)carbarnoyl]aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminophenol, 4-(N-METI is-N-acetylamino) aniline, 2.5 diethoxy-4-(N-benzoylamine)aniline, 2,5-dimethoxy-4-N-benzoylamine)aniline, 2-methoxy-4-(N-benzoylamine)-5-methylaniline, 4-sulfanilamide, 3-sulfanilamide, 2-(N-ethyl-N-phenylenesulfonyl)aniline, 4-dimethylaminoacetonitrile, 4-diethylaminoethylamine, sulfathiazole, 4-aminodiphenylamine, 2-chloro-5-N-phenylsulfonyl, 2-methoxy-5-N,N-diethylcarbamoyl, 2,5-dimethoxy-4-N-phenylsulfonyl, 2-methoxy-5-benzisothiazolin, 2-phenoxycarbonylamino, 2-(2’-chlorophenoxy)sulfanilamide, 3-anilinomethyl-4-methylaniline, bis [4-(m-aminophenoxy) phenyl] sulfon, bis[4-(p-aminophenoxy)phenyl]sulfon, bis[3-methyl-4-(p-aminophenoxy)phenyl]sulfon, 3,3’-dimethoxy-4,4’-diaminobiphenyl, 3,3’-dimethyl-4,4’-diaminobiphenyl, 2,2’-dichloro-4,4’-diamino-5,5’-dimethoxybiphenyl, 2,2’,5,5’-tetrachloro-4,4’-diaminobiphenyl, o-toluensulfonyl, 2,4’-diaminobiphenyl, 2,2’-diaminobiphenyl, 4,4’-diaminobiphenyl, 2,2’-dichloro-4,4’-diaminobiphenyl, 3,3’-dichloro-4,4’-diaminobiphenyl, 2,2’-dimethyl-4,4’-diaminobiphenyl, 4,4’-thiodianiline, 2,2’-dicitionary, 4,4’-dicitionary, 4,4’-diaminodiphenyl ether, 3,3’-diaminodiphenyl ether, 3,4’-diaminodiphenyl ether, 4,4’-diaminodiphenylmethane, 3,4’-diaminodiphenylmethane, bis(3-amino-4-chlorophenyl)sulfon, bis(3,4-diaminophenyl)sulfon, 4,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylsulfone, 3,4’-diaminodiphenylsulfone, 3,3’-diamine is the difenilmetana, 4,4-diaminodiphenylamine, 4,4’-ethylendiamin, 4,4’-diamino-2,2’-dimethylbenzyl, 3,3’-diaminobenzophenone, 4,4’-diaminobenzophenone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-AMINOPHENYL)fluorene, 2,2-bis(4-aminophenoxy)propane, 4,4’-bis(4-aminophenoxy)diphenyl, 3,3’,4,4’-tetraaminodiphenyl ether, 3,3’,4,4’-tetraaminodiphenyl, 3,3’,4,4’-tetraaminobiphenyl, 3-aminobenzonitrile, 4-fenoxedilom, 3-fenoxedilom, 4,4’-Methylenebis-o-toluidine, 4,4’-(p-phenyleneisopropylidene)-bis-(2,6-xylidine, o-chloro-p-nitroaniline, o-nitro-p-Chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, metol, 2,4-diaminophenol, N-(β -hydroxyethyl)-o-aminophenolate, sulfanilic acid, Manilova acid, 4B acid, acid, 2B acid, p-ftoranila, ftoranila, 3-chloro-4-ftoranila, 2,4-diptiranjan, 2,3,4-triptorelin, m-aminobenzotrifluoride, m toluylenediamine, 2-aminothiophenol, 2-amino-3-bromo-5-nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, acceleratory diphenylamine, 2-methyl-4-methoxydiphenyl, N,N-diphenyl-p-phenylenediamine, dianisidine, 3,3’-dichlorobenzidine, 4,4’-diaminostilbene-2,2’-disulfonate acid, benzylideneaniline, 1,8-naphthaleneamine, national intothree is, the Tobias acid, H acid, J acid, phenyl J acid, 1,4-diaminoanthraquinone, 1,4-diamino-2,3-dichloroanthracene and so on; amines heterocyclic compounds such as 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α -aminoε -caprolactam, acetogenin, 2,4-diamino-6-[2’-methylimidazole-(1)]ethyl-S-triazine, 2,3-diaminopyridine, 2.5-diaminopyridine, 2,3,5-diaminopyridine, 1-amino-4-methylpiperazine, 1-(2-amino-ethyl)piperazine, bis(aminopropyl)piperazine, N-(3-aminopropyl)morpholine and the like; and aliphatic amines such as methylamine, ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, Isopropylamine, Diisopropylamine, 2-ethylhexylamine, ethanolamine, 3-(2-ethylhexyloxy)Propylamine, 3-ethoxypropylamine, diisobutylamine, 3-(diethylamino)Propylamine, di-2-ethylhexylamine, 3-(dibutylamino)Propylamine, tert-butylamine, Propylamine, 3-(methylamino)Propylamine, 3-(dimethylamino)Propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclohexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromethalin, 2-methoxyethylamine, 2-ethoxymethylene, 2-amino-1-propanol, 2-aminobutanol, 3-amino-1,2-propandiol, 1,3-diamino-2-hydroxypropane, 2-aminoethanol, Ethylenediamine, Diethylenetriamine, hexamethylenediamine were and so on.

In addition, of the above as examples and is of insidente preferred are aromatic amines and particularly preferred are derivatives of aniline, having at least one amino group and represented by the following formula (z) or (VIII):

where R1and R2independently represent a hydrogen atom, halogen atom, alkyl group, alkoxygroup or amino group;

or

where R1, R2, R3and R4independently represent a hydrogen atom, halogen atom, alkyl group, alkoxygroup or amino group, X1and X2independently represent an amino group or a group represented by the formula (b):

and Y1represents any group of SO2-, -O-, -(S)n-, -(CH2)n-, -CO-, -CONH-, -NH-, -CH(COOR1)-, -C(CF3)2-, -CR2R3and the group represented by any formula of the formula (a):

or absent; each R1, R2and R3represents an alkyl group and n is 1 or 2.

These amine compounds may be used alone or in combination.

The urea-urethane compound used as the developer in each of the aspects of the present invention or the twenty-first, or on adcat second, refers to the compound having at least one urea group (-NHCONH - group) and at least one urethane group (-NHCOO - group) in the molecule.

It was known that compounds having one or more urea groups, have svetoprelomlyayuschimi effect, but they are not used in practice, as they have low color intensity and are unsuitable stability during storage. However, unexpectedly, the urea-urethane compound having at least one urea group and at least one urethane group in the molecule is a wonderful developer colorless or light-colored substances, precursor of the dye, and the color-forming composition comprising a urea-urethane compound and the substance is precursor of the dye, and the recording material obtained by using the color-forming composition, gives a high color intensity and has an excellent storage stability.

Although the mechanism by which this urea-urethane compound exhibits excellent svetoprelomlyayuschimi effect is unknown, assume that the effect is caused by the interaction between group(s) of urea and urethane(s) group(s) in the molecule.

As the urea-urethane compound used as the developer in each of the aspects of this and the finding, or the twenty-first or twenty-second, any compound can be used provided that it has at least one urea group (-NHCONH-group)and at least one urethane group (-NHCOO-group) in the molecule. The urea-urethane compound is preferably an aromatic compound or heterocyclic compound. In addition, the urea-urethane compound is preferably a compound in which the remainder of the aromatic compounds or heterocyclic residue connect directly attached to each group(s) of the urea and urethane(nd) group(s). More preferably, in addition to the group(s) urea (-NHCONH - group(s)) and urethane(s) group(s) (-NHCOO-group(s)in the molecule was attended by one or more groups, sulfonic acid (-SO2groups), amide groups (-NHCO - group) or isopropylidene group (-C(CH3)2group), directly unattached to the group(s) of urea.

The molecular mass of the urea-urethane compound is preferably 5000 or less, more preferably 2000 or less. The total number of group(s) of urea and urethane(s) group(s) in the urea-urethane compound is preferably 20 or less, more preferably 10 or less. The ratio of groups is(groups) of urea to urethane(nd) group(s) in the molecular structure of the urea-urethane compound is preferably from 1:3 to 3:1, in particular from 1:2 to 2:1.

When the urea-urethane compound used in the heat-sensitive recording material preferably is a compound which has a melting point. The melting point is in the area of preferably from 40° 500° With, in particular from 60° to 300° C.

A method of obtaining a urea-urethane compound used as the developer, in each of the aspects of the present invention or the twenty-first or twenty-second, is not specifically limited provided that is formed of at least one urea group (-NHCONH-group) and at least one urethane group (-NHCOO - group). The way in which the urea-urethane compound formed by the interaction of the isocyanate compound with a compound containing an Oh group, and aminoven connection is preferred because it is lighter.

In more detail, in the case of the urea-urethane compound used as the developer of the present invention, the isocyanate having at least two isocyanate groups, is used as the source of the product, and one or more urethane groups are formed by the interaction of all isocyanate groups and at least one, with a compound containing an Oh group, then one or more urea groups can be images which are by the interaction of ostavshiesa(s) isocyanate(s) group(s) with aminoven connection. Also, the formation of first one or more urea groups by reacting all isocyanate groups and at least one, with aminoven connection and then the formation of one or more urethane groups by reacting the remaining(s) isocyanate(s) group(s) with a compound containing an Oh group.

The original isocyanate is not specifically limited provided that it has two or more isocyanate groups. The original isocyanate includes, for example, n-delete the entry, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-colorvision, 2,6-colorvision, diphenylmethanediisocyanate, solidinvestment, diphenyl ether diisocyanate, 1,5-naphthylenediisocyanate, dianisidines, 9-ethylcarbazole-3,6-diisocyanate, 3,3’-dimethyl-4,4’-diphenylmethanediisocyanate, hexamethylenediisocyanate, isophoronediisocyanate, triphenyltetrazolium, Tris(4-phenylisocyanate)thiophosphate, 4,4’,4’-triisocyanate-2,5-dimethoxytrityl, 4,4’,4’-triisocyanate, m-xylylenediisocyanate, liaindizecign, diisocyanate dimer acid, isopropylidene bis-4-cyclohexylaniline, dicyclohexylmethane and methylcyclohexanone. As a source of isocyanate can also be used diisocyanate dimers, such as N,N’-(4,4’-dimethyl-3,3’-diphenyldiisocyanate)in motion (Desmodule TT, commercial name), toluene diisocyanate dimer; and diisocyanate trimers, such as 4,4’,4’-trimethyl-3,3’,3’-triisocyanate-2,4,6-triphenylene. Can also be used water adducts of isocyanates, selected from colordistance, diphenylmethanediisocyanate and the like, such as 1,3-bis(3-isocyanato-4-were)urea; polyol as one adducts, such as trimethylolpropane adduct of toluene diisocyanate (Desmodule L, trade name); and amine adducts. Can also be used compounds having two or more isocyanate groups, including isocyanate compounds and isocyanate adducts described in the detailed description of Japanese patent A-8-225445 and detailed description of Japanese patent A-8-250623.

Particularly preferred examples of the original isocyanate are colordistance. Among colordistance preferred is 2,4-colorvision. In addition to 2,4-colordistance as a source of isocyanate may be used a mixture of 2,4-colordistance and 2,6-colordistance, which are widely spread on the market and available at a low price.

As the amine compound that interacts with the original isocyanate urea-urethane compounds as the developer with the formation of one or more groups of urea, can be used I the th connection provided it has one or more amino groups. Amine compound includes, for example, aromatic amines such as aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-fenetidin, N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xylidine, 2,4-xylidine, 3,4-xylidine, 2,6-xylidine, 4-aminobenzonitrile, Anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α -naphtylamine, aminoanthracene, o-ethylaniline, o-Chloroaniline, m-Chloroaniline, p-Chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline, N,N-diglycidylether, N,N-diglycidyl-o-toluidine, anilide acetoacetic acid, bromide of trimethylphenylammonium, 4,4’-diamino-3,3’-diethyldiphenylurea, 4,4’-diaminobenzanilide, 3,5-diaminophenol, diaminodiphenyl ether, 3,3’-dichloro-4,4’-diaminodiphenylmethane, 3,3’-dimethyl-4,4’-diaminodiphenylmethane, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-and who inabensa, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, p-(N-phenylcarbamoyl)aniline, n-[N-(4-chlorophenyl)-carbarnoyl]aniline, n-[N-(4-AMINOPHENYL)carbarnoyl]aniline, 2-methoxy-5-(N-phenylcarbamoyl)aniline, 2-methoxy-5-[N-(2’-methyl-3’-chlorophenyl)carbarnoyl]aniline, 2-methoxy-5-[N-(2’-chlorophenyl)carbarnoyl]aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminophenol, 4-(N-methyl-N-acetylamino)aniline, 2,5-diethoxy-4-(N-benzoylamine)aniline, 2,5-dimethoxy-4-(N-benzoylamine)aniline, 2-methoxy-4-(N-benzoylamine)-5-methylaniline, 4-sulfanilamide, 3-sulfanilamide, 2-(N-ethyl-N-phenylenesulfonyl)aniline, 4-dimethylaminoacetonitrile, 4-diethylaminoethylamine, sulfathiazole, 4-aminodiphenylamine, 2-chloro-5-N-phenylsulfonyl, 2-methoxy-5-N,N-diethylcarbamoyl, 2,5-dimethoxy-4-N-phenylsulfonyl, 2-methoxy-5-benzisothiazolin, 2-phenoxycarbonylamino, 2-(2’chlorphenoxy)sulfanilamide, 3-anilinomethyl-4-methylaniline, bis[4-(m-aminophenoxy)phenyl]sulfon, bis[4-(p-aminophenoxy)phenyl]sulfon, bis[3-methyl-4-(p-aminophenoxy)phenyl]sulfon, 3,3’-dimethoxy-4,4’-diaminobiphenyl, 3,3’-dimethyl-4,4’-diaminobiphenyl, 2,2’-dichloro-4,4’-diamino-5,5’-dimethoxybiphenyl, 2,2’,5,5’-tetrachloro-4,4’-diaminobiphenyl, telediscount is h, 2,4’-diaminobiphenyl, 2,2’-diaminobiphenyl, 4,4’-diaminobiphenyl, 2,2’ -dichloro-4,4’-diaminobiphenyl, 3,3’-dichloro-4,4’-diaminobiphenyl, 2,2’-dimethyl-4,4’-diaminobiphenyl, 4,4’-thiodianiline, 2,2’-dicitionary, 4,4’-dicitionary, 4,4’-diaminodiphenyl ether, 3,3’-diaminodiphenyl ether, 3,4’-diaminodiphenyl ether, 4,4’-diaminodiphenylmethane, 3,4’-diaminodiphenylmethane, bis(3-amino-4-chlorophenyl)sulfon, bis(3,4-diaminophenyl)sulfon, 4,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylsulfone, 3,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylmethane, 4,4-diaminodiphenylamine, 4,4’-ethylendiamin, 4,4’-diamino-2,2’-dimethylbenzyl, 3,3’-diaminobenzophenone, 4,4’-diaminobenzophenone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-AMINOPHENYL)fluorene, 2,2-bis(4-aminophenoxy)propane, 4,4’-bis(4-aminophenoxy)diphenyl, 3,3’,4,4’-tetraaminodiphenyl ether, 3,3’,4,4’-tetraaminodiphenyl, 3,3’,4,4’-tetraaminobiphenyl, 3-aminobenzonitrile, 4-fenoxedilom, 3-fenoxedilom, 4,4’-Methylenebis-o-toluidine, 4,4’-(p-phenyleneisopropylidene)-bis-(2,6-xylidine, o-chloro-p-nitroaniline, o-nitro-p-Chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, metol, 2,4-diaminophenol, N-(β -hydroxyethyl)-o-monopersulfate, sulfanilic acid, Manilova acid, 4B acid, acid, 2B acid, p-ftoranila, ftoranila, 3-chloro-4-ftoranila, 2,4-diptiranjan, 2, 3,4-triptorelin, m-aminobenzotrifluoride, m toluylenediamine, 2-aminothiophenol, 2-amino-3-bromo-5-nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, acceleratory diphenylamine, 2-methyl-4-methoxydiphenyl, N,N-diphenyl-p-phenylenediamine, dianisidine, 3,3’-dichlorobenzidine, 4,4’-diaminostilbene-2,2’-disulfonate acid, benzylideneaniline, 1,8-naphthaleneamine, national sodium, Tobias acid, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, 1,4-diamino-2,3-dichloroanthracene and so on; heterocyclic compounds amines, such as 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α -aminoε -caprolactam, acetogenin, 2, 4-diamino-6-[2’-methylimidazole-(1)]ethyl-S-triazine, 2,3-diaminopyridine, 2.5-diaminopyridine, 2,3,5-diaminopyridine, 1-amino-4-methylpiperazine, 1-(2-amino-ethyl)piperazine, bis(aminopropyl)piperazine, N-(3-aminopropyl)morpholine and the like; and aliphatic amines such as methylamine, ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, Isopropylamine, Diisopropylamine, 2-ethylhexylamine, ethanolamine, 3-(2-ethylhexyloxy)Propylamine 3-ethoxypropylamine, diisobutylamine, 3-(diethylamino)Propylamine, di-2-ethylhexylamine, 3-(dibutylamino)the PCC is Lamin, tert-butylamine, Propylamine, 3-(methylamino)Propylamine, 3-(dimethylamino)Propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclohexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromethalin, 2-methoxyethylamine, 2-ethoxymethylene, 2-amino-1-propanol, 2-aminobutanol, 3-amino-1,2-propandiol, 1,3-diamino-2-hydroxypropane, 2-aminoethanol, Ethylenediamine, Diethylenetriamine, hexamethylenediamine were and so on.

Among the above as examples of amine compounds particularly preferred are aniline derivatives having at least one amino group and represented by the following formula (VIII):

where r1, R2, R3and R4independently represent a hydrogen atom, halogen atom, alkyl group, alkoxygroup or amino group, X1and X2independently represent an amino group or a group represented by the formula (b):

and Y1represents any group of SO2-, -O-, -(S)n-, -(CH2)n-, -CO-, -CONH -, and a group represented by any formula of the formula (a):

what if absent and n is 1 or 2.

As compounds containing an Oh group, which interacts with the isocyanate with the formation of one or more urethane groups, can be used in any connection, provided that it contains one or more Oh groups. The compound containing an Oh group, includes, for example, phenols such as phenol, cresol, Xylenol, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-op, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-NITROPHENOL, o-chlorophenol, p-chlorophenol, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(hydroxyphenyl)butane, 2,2-bis(hydroxyphenyl)pentane, 2,2-bis(hydroxyphenyl)heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyragollole, hydroquinone, methylhydroquinone, 4-phenylphenol, p,p’-biphenol, 4-cumylphenol, butyl bis (4-hydroxyphenyl)acetate, benzyl bis(4-hydroxyphenyl)acetate, bis(4-hydroxyphenyl)sulfon, bis(3-methyl-4-hydroxyphenyl)sulfon, bis(3,5-dimethyl-4-hydroxyphenyl)sulfon, 4-hydroxyphenyl-4’-methylphenylsulfonyl, 3-chloro-4-hydroxyphenyl-4’-methylphenylsulfonyl, 3,4-dihydroxyphenyl-4’-methylphenylsulfonyl, 4-isopropoxyphenyl-4’-hydroxyanisole, bis(2-allyl-4-hydroxyphenyl)sulfon, 4-hydroxyphenyl-4’-benzyloxyphenyl, 4-isopropylphenyl-4’-hydroxyanisole, 4-hydroxy-4’-isopropoxyphenyl, bis(2-methyl-3-tert-butyl-4-hydroxyphenyl)sulfide, 4,4’-di is hydroxydiphenyl ether, 4,4’-thiodiphenol, 4,4’-dihydroxybenzophenone, 2,2-bis(4-hydroxyphenyl)hexaferrite, 4,4’-dihydroxydiphenylmethane, 3,3’-dihydroxydiphenyl, bis(4-hydroxy-3-were)sulfide, bis(4- (2-hydroxy)phenyl)sulfon, 2,4-dihydroxybenzophenone, 2,2’,4,4’-tetrahydroxybenzophenone, fenilsalitsilat, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, (4’-Chlorobenzyl) 4-hydroxybenzoate, ethyl 1,2-bis(4’-hydroxybenzoate), pencil 1,5-bis(4’-hydroxybenzoate), hexyl 1,6-bis(4’-hydroxybenzoate), dimethyl 3-hydroxyphthalic, staringelf, laurelhurst, metalsalt, 4-methoxyphenol, 4-(benzyloxy)phenol, 4-hydroxybenzaldehyde, 4-n-octyloxybenzoic acid, 4-n-butiloxinazola acid, 4-n-petrogenetically acid, 3-n-dodecyloxybenzoic acid, 3-n-actinomycetoma acid, 4-n-octyloxybenzophenone acid, 4-n-oceanoislascanariascom acid and so next. However, phenols, as such, have amino group, is not desirable. Because the amino group is more reaktsionnosposobnykh in relation to isocyanate groups than HE group, the amino group interacts with the isocyanate group before HE group, which thus makes it difficult to obtain the desired compounds in some cases.

The compound containing an Oh group, also includes alcohols such as methanol, ethanol, propanol, b is tonal, pentanol, hexanol, heptanol, octanol, isopropanol, Isobutanol, isopentanol, 2-ethyl-1-hexanol, 1-decanol, 2-pentanol, 3-hexanol, tert-butanol, tert-amyl alcohol, methylcellosolve, butylcellosolve, methylcarbamoyl, allyl alcohol, 2-methyl-2-propen-1-ol, benzyl alcohol, 4-pyridinemethanol, penicillosis, furfuryl alcohol, cyclohexanol, cyclohexylmethanol, Cyclopentanol, 2-chloroethanol, 1-chloro-3-hydroxypropan, glycerin, glycerol and so on; polyester polyols such as polypropyleneglycol, polytetramethylene glycol ether adeptpro.info polyols, epoxy-modified polyols, polyether ester polyols, polycarbonate polyols, polycaprolactone diols, phenolic polyols, aminodiphenylamine polyols and the like; and polyols, such as ethylene glycol, diethylene glycol, 1,3-propandiol, 1,2-propandiol, propylene glycol, dipropyleneglycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-hexandiol, 1,9-nonanediol, acrylic polyols, fluorocarbon polyols, polybutadiene polyols, polyhydroxyvalerate, trimethylolpropane, trimethylamin, hexanetriol, phosphoric acid neopentylglycol, pentaerythritol, polyols derived from castor oil, polymer polyols, methylpentanediol, halogenated polyols, phosphorus-containing polyols, Ethylenediamine, α -methylglucoside, sorbitol, sugar is for and so on.

The urea-urethane compound used as the developer in each of the aspects of the present invention or the twenty-first or twenty-second, is preferably urea-urethane compound having a molecular structure in which the number of groups of urea (a) and the number of urethane groups (C) satisfy the following numerical formula:

10≥ (a+b)≥ 3

where each a and b is an integer of 1 or greater.

The urea-urethane compound, in which the number of urea groups (a) and the number of urethane groups (C) satisfy the numerical formula 10≥ (a+b)≥ 3 (where each a and b is an integer of 1 or greater), is a compound having a molecular structure in which there is at least one urea group (-NHCONH - group) and at least one urethane group (-NHCOO - group) with a total of no more than 10 and not less than 3.

Such a connection has not been described and is completely new. This new compound is used in the case of recording materials, which use recording energy, such as heat, pressure or the like.

The method of obtaining the urea-urethane compounds, in which the number of urea groups (a) and the number of urethane groups (C) satisfy the numerical formula 10≥ (a+b)≥ 3 (where each a and b is an integer of 1 or greater), specifically the e limited, provided that at least one urea group (-NHCONH - group) and at least one urethane group (-NHCOO - group) are formed with a total of from 3 to 10. The way in which the urea-urethane compound obtained by reacting isocyanate compounds with a compound containing an Oh group, and aminoven connection is preferred because of its simplicity.

In more detail, as the urea-urethane compound used as the developer in each of the aspects of the present invention, either in the twenty-first or twenty-second, can be obtained urea-urethane compound having at least one urea group and at least one urethane group with the total number at least 3, for example, when using isocyanate having at least two isocyanate groups in the starting material, interacting with all the isocyanate groups with the exception of at least one with a compound containing an Oh group, with the formation of one or more urethane groups, and then interacting the remaining isocyanate groups of the two molecules formed urethane connections with each other while using the water attach them to each other.

In addition, can be obtained urea-urethane compound having, on the edge is her least one urea group and at least one urethane group with the total number at least 3, for example, when using isocyanate having at least two isocyanate groups in the starting material, interacting with all the isocyanate groups, except at least one, with a compound containing an Oh group, receiving one or more urethane groups, interacting remaining isocyanate(s) group(s) with aminoven compound having two or more amino groups, with the formation of one or more groups of urea and interacting remaining amino group(AMI) with the isocyanate compound.

In addition, the urea-urethane compound having at least one urea group and at least one urethane group with the total number at least 3, can also be obtained by the reaction of all isocyanate groups, except at least one, with aminoven connection, first with the formation of one or more urea groups, the interaction of the remaining isocyanate(s) group(s) with a compound containing two or more Oh groups, receiving one or more urethane groups, and then the interaction obtained connection with the isocyanate compound. In this case, the urea-urethane compound, have it at least one urea group and at least one urethane group, with the total number 3-10, can be obtained by using the isocyanate compound having two or more isocyanate groups, isocyanate, which in the end will react, and repeating the procedure of interaction of the remaining isocyanate(s) group(s) with a compound containing two or more Oh groups, or with aminosilane having two or more amino groups.

The original isocyanate is not specifically organic, provided that it has two or more isocyanate groups. The original isocyanate includes, for example, n-delete the entry, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-colorvision, 2,6-colorvision, diphenylmethanediisocyanate, solidinvestment, diphenyl ether diisocyanate, 1,5-naphthylenediisocyanate, dianisidines, 9-ethylcarbazole-3,6-diisocyanate, 3,3’-dimethyl-4,4’-diphenylmethanediisocyanate, hexamethylene diisocyanate, isophoronediisocyanate, triphenyltetrazolium, Tris(4-phenylisocyanate) thiophosphate, 4,4’,4’-triisocyanate-2,5-dimethoxytrityl, 4,4’,4’-triisocyanate, m-xylylenediisocyanate, liaindizecign, diisocyanate dimer acid, isopropylidene bis-4-cyclohexylaniline, dicyclohexylmethane and methylcyclohexanone.

As the source of the cyanate can also be used diisocyanate dimers, such as N,N’-(4,4’-dimethyl-3,3’-diphenyldiisocyanate)uretdione (Desmodule TT, trade name), colorvitality dimer; and diisocyanate trimers, such as 4,4’,4’-trimethyl-3,3’,3’-triisocyanate-2, 4, 6-triphenylene. Can also be used water adducts of isocyanates, selected from toluene diisocyanate, diphenylmethanediisocyanate and the like, such as 1,3-bis(3-isocyanato-4-were)urea; polyol as one adducts, such as trimethylolpropane adduct colordistance (Desmodule L, trade name); and amine adducts. Can also be used compounds having two or more isocyanate groups, including isocyanate compounds and isocyanate adducts described in the detailed description of Japanese patent JP-A-10-76757 and detailed description of Japanese patent JP-A-10-95171 (the contents of these links are given here as a reference).

Particularly preferred examples of the original isocyanate are colordistance. Among colordistance preferred are 2,4-colorvision. In addition to 2,4-colordistance as the original MDI can also be used a mixture of 2,4-colordistance and 2,6-colordistance, which are widely spread on the market and available at a low price.

Mixtures of these colorvitality isomers are liquid at normal temp is the temperature.

As the amine compound that interacts with the original isocyanate to form urea-urethane compounds with the formation of one or more groups of urea, can be used in any connection, provided that it has one or more amino groups. Amine compound includes, for example, aromatic amines such as aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-fenetidin, N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xylidine, 2,4-xylidine, 3,4-xylidine, 2,6-xylidine, 4-aminobenzonitrile, Anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α -naphtylamine, aminoanthracene, o-ethylaniline, o-Chloroaniline, m-Chloroaniline, p-Chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline, N,N-diglycidylether, N,N-diglycidyl-o-toluidine, anilide acetoacetic acid, bromide of trimethylphenylammonium, 4,4’-diamino-3,3’-diethyldiphenylurea, 4,4’-diaminobenzanilide, 3,5-diaminophenol, diaminodiphenyl ether, 3,3’-dichloro-4,4’-diaminodiphenylmethane, 3,3’-dimethyl-4,4’-diaminodiphenylmethane, tolidine base is, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, p-(N-phenylcarbamoyl)aniline, n-[N-(4-chlorophenyl)-carbarnoyl]aniline, n-[N-(4-AMINOPHENYL)carbarnoyl]aniline, 2-methoxy-5-(N-phenylcarbamoyl)aniline, 2-methoxy-5-[N-(2’-methyl-3’-chlorophenyl)carbarnoyl]aniline, 2-methoxy-5-[N-(2’-chlorophenyl)carbarnoyl]aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminophenol, 4-(N-methyl-N-acetylamino) aniline, 2,5-diethoxy-4-(N-benzoylamine)aniline, 2,5-dimethoxy-4-(N-benzoylamine)aniline, 2-methoxy-4-(N-benzoylamine)-5-methylaniline, 4-sulfanilamide, 3-sulfanilamide, 2-(n-ethyl-n-phenylenesulfonyl)aniline, 4-dimethylaminoacetonitrile, 4-diethylaminoethylamine, sulfathiazole, 4-aminodiphenylamine, 2-chloro-5-N-phenylsulfonyl, 2-methoxy-5-N,N-diethylcarbamoyl, 2,5-dimethoxy-4-phenylsulfonyl, 2-methoxy-5-benzisothiazolin, 2-phenoxycarbonylamino, 2-(2’-chlorophenoxy)sulfanilamide, 3-anilinomethyl-4-methylaniline, bis[4-(m-aminophenoxy)phenyl]Sul is he, bis[4-(p-aminophenoxy)phenyl]sulfon, bis[3-methyl-4-(p-aminophenoxy)phenyl]sulfon, 3,3’-dimethoxy-4,4’-diaminobiphenyl, 3,3’ -dimethyl-4,4’-diaminobiphenyl, 2,2’-dichloro-4,4’-diamino-5,5’-dimethoxybiphenyl, 2,2’,5,5’-tetrachloro-4,4’-diaminobiphenyl, o-toluensulfonyl, 2,4’-diaminobiphenyl, 2,2’-diaminobiphenyl, 4,4’-diaminobiphenyl, 2,2’-dichloro-4,4’-diaminobiphenyl, 3,3’-dichloro-4,4’-diaminobiphenyl, 2,2’-dimethyl-4,4’-diaminobiphenyl, 4,4’-thiodianiline, 2,2’-dicitionary, 4,4’-dicitionary, 4,4’-diaminodiphenyl ether, 3,3’-diaminodiphenyl ether, 3,4’-diaminodiphenyl ether, 4,4’-diaminodiphenylmethane, 3,4’-diaminodiphenylmethane, bis(3-amino-4-chlorophenyl)sulfon, bis(3,4-diaminophenyl)sulfon, 4,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylsulfone, 3,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylmethane, 4,4-diaminodiphenylamine, 4,4’-ethylendiamin, 4,4’-diamino-2,2’-dimethylbenzyl, 3,3’-diaminobenzophenone, 4,4’-diaminobenzophenone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-AMINOPHENYL)fluorene, 2,2-bis(4-aminophenoxy)propane, 4,4’-bis(4-aminophenoxy)diphenyl, 3,3’,4,4’-tetraaminodiphenyl ether, 3,3’,4,4’-tetraaminodiphenyl, 3,3’,4,4’-tetraaminobiphenyl, 3-aminobenzonitrile, 4-fenoxedilom, 3-fenoxedilom, 4,4’-Methylenebis-o-toluidine, 4,4’-(p-phenyleneisopropylidene)-bis-(2,6-xylidine, o-chloro-p-nitrone is in, o-nitro-p-Chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, metol, 2,4-diaminophenol, N-(β -hydroxyethyl)-o-aminophenolate, sulfanilic acid, Manilova acid, 4B acid, With acid, 2B acid, p-ftoranila, ftoranila, 3-chloro-4-ftoranila, 2,4-diptiranjan, 2,3,4-triptorelin, m-aminobenzotrifluoride, m toluylenediamine, 2-aminothiophenol, 2-amino-3-bromo-5-nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, acceleratory diphenylamine, 2-methyl-4-methoxydiphenyl, N,N-diphenyl-p-phenylenediamine, dianisidine, 3,3’-dichlorobenzidine, 4,4’-diaminostilbene-2,2’-disulfonate acid, benzylideneaniline, 1,8-naphthaleneamine, national sodium, Tobias acid, H acid, J acid, phenyl J acid, 1,4-diaminoanthraquinone, 1,4-diamino-2,3-dichloroanthracene and so on; heterocyclic compounds amines, such as 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α -aminoε -caprolactam, acetogenin, 2,4-diamino-6-(2’-methylimidazole-(1)]ethyl-S-triazine, 2,3-diaminopyridine, 2.5-diaminopyridine, 2,3,5-diaminopyridine, 1-amino-4-methylpiperazine, 1-(2-amino-ethyl)piperazine, bis(aminopropyl)piperazine, N-(3-aminopropyl)morpholine and the like; and aliphatic amines such as methylamine, atrami is, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, Isopropylamine, Diisopropylamine, 2-ethylhexylamine, ethanolamine, 3-(2-ethylhexyloxy)Propylamine, 3-ethoxypropylamine, diisobutylamine, 3-(diethylamino)Propylamine, di-2-ethylhexylamine, 3-(dibutylamino)Propylamine, tert-butylamine, Propylamine, 3-(methylamino)Propylamine, 3-(dimethylamino)Propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclohexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromethalin, 2-methoxyethylamine, 2-ethoxymethylene, 2-amino-1-propanol, 2-aminobutanol, 3-amino-1,2-propandiol, 1,3-diamino-2-hydroxypropane, 2-aminoethanol, Ethylenediamine, Diethylenetriamine, hexamethylenediamine were and so on.

Among the above as examples of amine compounds particularly preferred are aniline derivatives having at least one amino group and represented by the following formula (VIII):

where R1, R2, R3and R4independently represent a hydrogen atom, halogen atom, alkyl group, alkoxygroup or amino group, X1and X2independently represent an amino group or a group represented by the formula (b):

and Y1represents any group of SO2-, -O-, -(S) -, -(CH2)n-, -CO-, -CONH -, and a group represented by any of formula (a):

or is absent and n is 1 or 2.

As compounds containing an Oh group, which interacts with the isocyanate with the formation of one or more urethane groups, can be used in any connection, provided that it contains one or more Oh groups. The compound containing an Oh group, includes, for example, phenols such as phenol, cresol, Xylenol, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-op, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-NITROPHENOL, o-chlorophenol, p-chlorophenol, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(hydroxyphenyl)butane, 2,2-bis(hydroxyphenyl)pentane, 2,2-bis(hydroxyphenyl)heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyragollole, hydroquinone, methylhydroquinone, 4-phenylphenol, p,p’-biphenol, 4-cumylphenol, butyl bis(4-hydroxyphenyl)acetate, benzyl bis(4-hydroxyphenyl)acetate, bis(4-hydroxyphenyl)sulfon, bis(3-methyl-4-hydroxyphenyl)sulfon, bis(3,5-dimethyl-4-hydroxyphenyl)sulfon, 4-hydroxyphenyl-4’-methylphenylsulfonyl, 3-chloro-4-hydroxyphenyl-4’-methylphenylsulfonyl, 3,4-dihydroxyphenyl is -4’-methylphenylsulfonyl, 4-isopropoxyphenyl-4’-hydroxyanisole, bis(2-allyl-4-hydroxyphenyl)sulfon, 4-hydroxyphenyl-4’-benzyloxyphenyl, 4-isopropylphenyl-4’-hydroxyanisole, 4-hydroxy-4’-isopropoxyphenyl, bis(2-methyl-3-tert-butyl-4-hydroxyphenyl)sulfide, 4,4’-dihydroxydiphenyl ether, 4,4’-thiodiphenol, 4,4’-dihydroxybenzophenone, 2,2-bis(4-hydroxyphenyl)hexaferrite, 4,4’-dihydroxydiphenylmethane, 3,3’-dihydroxydiphenyl, bis(4-hydroxy-3-were) sulfide, bis(4-(2-hydroxy)phenyl)sulfon, 2,4-dihydroxybenzophenone, 2,2’,4,4’-tetrahydroxybenzophenone, fenilsalitsilat, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, (4’-Chlorobenzyl) 4-hydroxybenzoate, ethyl 1,2-bis(4’-hydroxybenzoate), pencil 1,5-bis(4’-hydroxybenzoate), hexyl 1,6-bis(4’-hydroxybenzoate), dimethyl 3-hydroxyphthalic staringelf, laurelhurst, metalsalt, 4-methoxyphenol, 4-(benzyloxy)phenol, 4-hydroxybenzaldehyde, 4-p-octyloxybenzoic acid, 4-n-butiloxinazola acid, 4-n-petrogenetically acid, 3-n-dodecyloxybenzoic acid, 3-n-actinomycetoma acid, 4-n-octyloxybenzophenone acid, 4-n-oceanoislascanariascom acid and so on. However, as such, phenols, which have the amino group, are undesirable. Because the amino group is more reactive is sposobnostey towards isocyanate group, than HE group, the amino group interacts with the isocyanate group before HE group, thus making it difficult to obtain the desired compounds in some cases. Compounds containing an Oh group, also includes alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, Isobutanol, isoheptyl, 2-ethyl-1-hexanol, 1-decanol, 2-pentanol, 3-hexanol, tert-butanol, tert-amyl alcohol, methylcellosolve, butylcellosolve, methylcarbamoyl, allyl alcohol, 2-methyl-2-propa-1-ol, benzyl alcohol, 4-pyridinemethanol, penicillosis, furfuryl alcohol, cyclohexanol, cyclohexylmethanol, Cyclopentanol, 2-chloroethanol, 1-chloro-3-hydroxypropan, glycerin, glycerol and the like; polyester polyols such as polypropyleneglycol, polytetramethylene afilliate, adipat-proizvodnye polyols, epoksipolyurethane polyols, polyether ester polyols, polycarbonate polyols, polycaprolactone diols, phenolic polyols, amine-modified polyols and the like; and polyols, such as ethylene glycol, diethylene glycol, 1,3-propandiol, 1,2-propandiol, propylene glycol, dipropyleneglycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-hexandiol, 1,9-nonanediol, acrylic polyols, percarbonate polyols, polybutadiene polyols, polyhydroxyvalerate, trimethylspiro the Academy of Sciences, trimethylated, hexanetriol, phosphoric acid, neopentylglycol, pentaerythritol, polyols, derived from the state reserve and karsts oil, polymer polyols, methylpentanediol, halogenated polyols, phosphorus-containing polyols, Ethylenediamine, α -methylglucoside, sorbitol, sucrose and so on

As the urea-urethane compound used as the developer in each of the aspects of the present invention or the twenty-first or twenty-second, the urea-urethane compound represented by any of the following General formulas (I)to(VII)are preferred:

where X and Z independently represent a residue of aromatic compounds, a residue of a heterocyclic compound or a residue of aliphatic compounds, each residue can have one or more substituents, and Y0represents a group selected from the group consisting of Torrenova group, xylylene group, Neftyanoy group, hexamethylene group, and -φ CH2-φ group,φ - represents fenelonov group;

where X and Y independently represent a residue of aromatic compounds, a residue of a heterocyclic compound or a residue of aliphatic compounds, and each residue can have one or more to cover up the oil;

where X and Y independently represent a residue of aromatic compounds, a residue of a heterocyclic compound or a residue of aliphatic compounds, α represents a residue having a valency of 2 or more, n is an integer of 2 or more, and each residue can have one or more substituents;

where Z and Y independently represent a residue of aromatic compounds, a residue of a heterocyclic compound or a residue of aliphatic compounds, β represents a residue having a valency of 2 or more, n is an integer of 2 or more, and each residue can have one or more substituents;

where the atom(s) of each hydrogen of the benzene ring may be substituted(s) Deputy, which preferably represents the residue of aromatic compounds, the aliphatic residue of a compound or a residue of heterocyclic compounds, although the Deputy may be a nitro-group, a hydroxyl group, a carboxyl group, nitrosopropane, nitrile group, carbamoyl group, raidgroups, isocyanate group, mercaptopropyl, sulfopropyl, sulfamoyl group or a halogen atom, each residue can have one or more substituents, #x003B3; represents a group selected from the group comprising-SO2-, -O-, -(S)n-, -(CH2)n-, -CO-, -CONH - and any group represented by the formula (a);

or is absent and n is 1 or 2;

where the atom(s) of each hydrogen of the benzene ring may be substituted(s) Deputy, which preferably represents the residue of aromatic compounds, the aliphatic residue of a compound or a residue of heterocyclic compounds, although the Deputy may be a hydroxyl group, a nitro-group, a nitrile group, carbamoyl group, sulfamoyl group, a carboxyl group, nitrosopropane, amino group, accelerograph, nitrolingual, hydratherapy, raidgroups, isocyanate group, mercaptopropyl, sulfopropyl or a halogen atom, each residue can have one or more substituents, δ represents a group selected from the group comprising -SO2-, -O-, -(S)n-, -(CH2)n-, -CO-, -CONH-, -NH-, -CH(COOR1)-, -C(CF3)2- and- (CR2R3or absent; each of R1, R2and R3represents an alkyl group which has, and n is 1 or 2; and

where X, Y and Z independently represent a residue of aromatic compounds, a residue of a heterocyclic compound or a residue of aliphatic compounds, each residue can have one or more substituents, and each of X, Y and Z preferably represents the residue of an aromatic compound or a heterocyclic residue of the connection.

The urea-urethane compounds of formulas (I)-(VII) also brand new. These new compounds are used in the case of recording materials, which use recording energy, such as heat, pressure or the like.

A method of obtaining a urea-urethane compound of the formula (I), which is used in each of the aspects of the present invention or the twenty-first or twenty-second, is not limited. This compound can be obtained, for example by reaction of compounds containing an Oh group, the following General formula (IX) with an isocyanate compound of the following General formula (X) and aminoven compound of the following General formula (XI) in accordance with, for example, the reaction formula (A)below:

where X and Z independently represent a residue of aromatic compounds, a residue of a heterocyclic compound or a residue of aliphatic compounds, which each residue can have one or more substituents, and Y0represents a group selected from the group comprising Torrenova group, xylylene group, Neftyanoy group, hexamethylene group, and -φ CH2-φ group,φ - represents fenelonov group.

The term “aliphatic”, as used here, includes the term “alicyclic”.

A method of obtaining a urea-urethane compound of the formula (II)used in each of the aspects of the present invention or the twenty-first or twenty-second, is not limited. This compound can be obtained, for example by reaction of compounds containing an Oh group, of General formula (IX) with an isocyanate compound of the following General formula (XII) and water in accordance with, for example, the reaction formula (C)shown below:

where Y represents the residue of aromatic compounds, a residue of a heterocyclic compound or a residue of aliphatic compounds, and each residue can have one or more deputies.

A method of obtaining a urea-urethane compound of the formula (III)used in each of the aspects of the present invention or the twenty-first or twenty-second, is not limited. This compound can be obtained, for example, provzaimodeystvuet connection containing an Oh group, of General formula (IX) with an isocyanate compound of General formula (XII) and aminoven compound of the following General formula (XIII) in accordance with, for example, the reaction formula (C) or (D) below:

where α represents a residue having a valency of 2 or more, and n represents an integer of 2 or greater.

A method of obtaining a urea-urethane compound of the formula (IV)used in each of the aspects of the present invention or the twenty-first or twenty-second, is not limited. This compound can be obtained, for example, in the interaction of amine compounds of General formula (XI) with an isocyanate compound of General formula (XII) and a compound containing an Oh group, the following General formula (XIV) in accordance with, for example, the reaction formula (E) or (F) below:

where β represents a residue having a valency of 2 or more, and n represents an integer of 2 or greater.

Compounds of General formula (IX)to(XIV), which are described in more detail below, can be used to obtain a urea-urethane compounds of formulas (I)to(IV) above.

The compound containing an Oh group, of General formula (IX) is not specifically limited provided that it has one or more Oh groups. This compound includes, for example, monophenol, such as phenol, cresol, Xylenol, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-op, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-NITROPHENOL, o-chlorophenol, p-chlorophenol, 4-phenylphenol, 4-hydroxyphenyl-4’-methylphenylsulfonyl, 3-chloro-4-hydroxyphenyl-4’-methylphenylsulfonyl, 4-isopropylphenyl-4’-hydroxyanisole, 4-isopropoxyphenyl-4’-hydroxyanisole, 4-hydroxyphenyl-4’-benzyloxyphenyl, 4-isopropylphenyl-4’-hydroxyanisole, 4-hydroxy-4’-isopropoxyphenyl, fenilsalitsilat, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, (4’-Chlorobenzyl) 4-hydroxybenzoate, ethyl 1,2-bis(4’-hydroxybenzoate), pencil 1,5-bis(4’-hydroxybenzoate), hexyl 1,6-bis(4’-hydroxybenzoate), dimethyl 3-hydroxyphthalic, 4-methoxyphenol, 4-(benzyloxy)phenol, 4-hydroxybenzaldehyde, 4-n-octyloxybenzoic acid, 4-n-butiloxinazola acid, 4-n-petrogenetically acid, 3-n-dodecyloxybenzoic acid, 3-n-actinomycetoma acid, 4-n-octyloxybenzophenone acid, 4-n-oceanoislascanariascom acid and so on. Connection total fo the formula (IX) also includes divinely, such as 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(hydroxyphenyl)butane, 2,2-bis(hydroxyphenyl)pentane, 2,2-bis(hydroxyphenyl)heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyragollole, hydroquinone, methylhydroquinone, 4-phenylphenol, 4,4’-biphenol, 4-cumylphenol, butyl bis(4-hydroxyphenyl)acetate, benzyl bis(4-hydroxyphenyl)acetate, bis(4-hydroxyphenyl)sulfon, bis(3-methyl-4-hydroxyphenyl)sulfon, bis(3,5-dimethyl-4-hydroxyphenyl)sulfon, 3,4-dihydroxyphenyl-4’-methylphenylsulfonyl, bis(2-allyl-4-hydroxyphenyl)sulfon, bis(2-methyl-3-tert-butyl-4-hydroxyphenyl)sulfide, 4,4’-dihydroxydiphenyl ether, 4,4’-thiodiphenol, 4,4’-dihydroxybenzophenone, 2,2-bis(4-hydroxyphenyl)hexaferrite, 4,4’-dihydroxydiphenylmethane, 3,3’-dihydroxydiphenyl, bis(4-hydroxy-3-were)sulfide and so on. However, essentially compounds containing an Oh group, which have the amino group, is undesirable. When the amino group is present together with Oh group(s), amino group has a higher reactivity towards isocyanate group than the HE group and therefore the amino group interacts with the isocyanate group before HE group, thus making it difficult to obtain the desired compounds in some cases. The compound of General formula (IX), in addition, includes a monohydroxy alcohols, such as methanol, ethanol, propanol, butanol, pentanol, Huck is anal, heptanol, octanol, isopropanol, Isobutanol, isopentanol, 2-ethyl-1-hexanol, 1-decanol, 2-pentanol, 3-hexanol, tert-butanol, tert-amyl alcohol, methylcellosolve, butylcellosolve, methylcarbamoyl, allyl alcohol, 2-methyl-2-propen-1-ol, benzyl alcohol, 4-pyridinemethanol, penicillosis, furfuryl alcohol, cyclohexanol, cyclohexylmethanol, Cyclopentanol, 2-chloroethanol, 1-chloro-3-hydroxypropan, glycerin, glycerol and so on. As compounds of General formula (IX) can also be used polyols polyester type, such as polypropyleneglycol, polytetramethylene afilliate, adipat-derived polyols, epoksipolyurethane polyols, polyether ester polyols, polycarbonate polyols, polycaprolactone diols, phenolic polyols, aminodiphenylamine polyols and the like; and polyols, such as ethylene glycol, diethylene glycol, 1,3-propandiol, 1,2-propandiol, propylene glycol, dipropyleneglycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-hexandiol, 1,9-nonanediol, acrylic polyols, fluorocarbon polyols, polybutadiene polyols, polyhydroxyamide, trimethylolpropane, trimethylacetyl, hexanetriol, phosphoric acid, neopentylglycol, pentaerythritol, polyols derived from castor oil, polymer polyols, methylpentanediol, halogenated polyols, phosphorus-containing polyols, ethyl is a diamine, α -methylglucoside, sorbitol, sucrose and so on. Of them it is preferable to use monophenol.

Isocyanate compound of General formula (X) include 2,4-colorvision, 2,6-colorvision, diphenylmethanediisocyanate, hexamethylenediisocyanate, 1,5-naphthylenediisocyanate, m-xylylenediisocyanate and so on. Of them, preferred are toluene diisocyanate.

Isocyanate compound of General formula (XII) is not specifically limited provided that it has two or more isocyanate groups. This compound includes, for example, n-delete the entry, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-colorvision, 2,6-colorvision, diphenylmethanediisocyanate, solidinvestment, 1,5-naftilan diisocyanate, dianisidines, 9-ethylcarbazole-3,6-diisocyanate, 3,3’-dimethyl-4,4’-diphenylmethanediisocyanate, hexamethylenediisocyanate, isophoronediisocyanate, triphenylmethane triisocyanate, Tris(4-phenylisocyanate)thiophosphate, 4,4’,4’-triisocyanate-2,5-dimethoxytrityl, 4,4’,4’-triisocyanate, m-xylylenediisocyanate, liaindizecign, diisocyanate dimer acid, isopropylidene bis-4-cyclohexylaniline, dicyclohexylmethane and methylcyclohexanone. As isocyanate compounds of General formula (XII) can also be used diisocyanate dimers, such as NN’-(4,4’-dimethyl-3,3’-diphenyldiisocyanate) uretdione (Desmodule TT, commercial name), toluene diisocyanate dimer; and diisocyanate trimers, such as 4,4’,4"-trimethyl-3,3’,3’-triisocyanate-2,4,6-triphenylene. Can also be used water adducts of isocyanates, selected from colordistance, diphenylmethanediisocyanate and the like, such as 1,3-bis(3-isocyanato-4-were)urea; polyol as one adducts, such as trimethylolpropane adduct of toluene diisocyanate (Desmodule L, trade name); and amine adducts.

Can also be used compounds having two or more isocyanate groups, including isocyanate compounds and isocyanate adducts described in the detailed description of Japanese patent JP-A-10-76757 and JP-A-10-95171. Especially preferred example of the isocyanate compounds of General formula (XII) is colorvision.

Amine compound of General formula (XI) is not specifically limited provided that it has one or more amino groups. This compound includes, for example, aromatic monoamines such as aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-fenetidin,2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3, 4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xylidine, 2,4-xylidine, 3,4-xylidine, 2,6-xylidine, 4-aminobenzonitrile, Anthranilic acid, p-krezi the in, 2.5 dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α -naphtylamine, aminoanthracene, o-ethylaniline, o-Chloroaniline, m-Chloroaniline, p-Chloroaniline, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, p-(N-phenylcarbamoyl)aniline, n-[N-(4-chlorophenyl)carbarnoyl]aniline, n-[N-(4-AMINOPHENYL)carbarnoyl]aniline, 2-methoxy-5-(N-phenylcarbamoyl)aniline, 2-methoxy-5-[N-(2’-methyl-3’-chlorophenyl)carbarnoyl]aniline, 2-methoxy-5-[N-(2’-chlorophenyl)carbarnoyl]aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminophenol, 2-methoxy-4-(N-benzoylamine)-5-methylaniline, 4-sulfanilamide, 3-sulfanilamide, 2-(N-ethyl-N-phenylenesulfonyl)aniline, 4-dimethylaminoacetonitrile, 4-diethylaminoethylamine, sulfathiazole, 4-aminodiphenylamine, 2-chloro-5-N-phenylsulfonyl, 2-methoxy-5-N,N-diethylcarbamoyl, 2,5-dimethoxy-4-N-phenylsulfonyl, 2-methoxy-5-benzisothiazolin, 2-phenoxycarbonylamino,2-(2’-chlorophenoxy)sulfanilamide, 3-anilinomethyl-4-methylaniline, o-chloro-p-nitroaniline, o-nitro-p-Chloroaniline, 2,6-di the ENT-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, sulfanilic acid, Manilova acid, 4B acid, acid, 2B acid, p-ftoranila, ftoranila, 3-chloro-4-ftoranila, 2,4-diptiranjan, 2,3,4-triptorelin, m-aminobenzotrifluoride, 2-amino-3-bromo-5-nitrobenzonitrile and so forth; and aromatic diamines such as 4,4’-diamino-3,3’-diethyldiphenylurea, 4,4’-diaminobenzanilide, 3,5-diaminophenol, diaminodiphenyl ether, 3,3’-dichloro-4,4’-diaminodiphenylmethane, 3,3’-dimethyl-4,4’-diaminodiphenylmethane, tolidine base, dianisidine, bis[4-(m-aminophenoxy)phenyl]sulfon, bis[4-(p-aminophenoxy)phenyl]sulfon, bis[3-methyl-4-(p-aminophenoxy)phenyl]sulfon, 3,3’-dimethoxy-4,4’-diaminobiphenyl, 3,3’-dimethyl-4,4’-diaminobiphenyl, 2,2’-dichloro-4,4’-diamino-5,5’-dimethoxybiphenyl, 2,2’,5,5’-tetrachloro-4,4’-diaminobiphenyl, o-toluensulfonyl, 2,4’-diaminobiphenyl, 2,2’-diaminobiphenyl, 4,4’-diaminobiphenyl, 2,2’-dichloro-4,4’-diaminobiphenyl, 3,3’-dichloro-4,4’-diaminobiphenyl, 2,2’-dimethyl-4,4’-diaminobiphenyl, 4,4’-thiodianiline, 2,2’-dicitionary, 4,4’-dicitionary, 4,4’-diaminodiphenyl ether, 3,3’-diaminodiphenyl ether, 3,4’-diaminodiphenyl ether, 4,4’-diaminodiphenylmethane, 3,4’-diaminodiphenylmethane, bis(3-amino-4-chlorophenyl)sulfon, bis(3,4-diaminophenyl is)sulfon,4,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylsulfone, 3,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylmethane, 4,4’-diaminodiphenylamine, 4,4’-ethylendiamin, 4,4’-diamino-2,2’-dimethylbenzyl, 3,3’-diaminobenzophenone, 4,4’-diaminobenzophenone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-AMINOPHENYL)fluorene, 2,2-bis(4-aminophenoxy)propane, 4,4’-bis(4-aminophenoxy)diphenyl, dianisidine, 3,3’-dichlorobenzidine and so on. Amine compound of General formula (XI) also includes, for example, heterocyclic compounds amines, such as 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α -aminoε -caprolactam, acetogenin, 2,4-diamino-6-[2’-methylimidazole-(1)]ethyl-S-triazine, 2,3-diaminopyridine, 2.5-diaminopyridine, 2,3,5-diaminopyridine, 1-amino-4-methylpiperazine, 1-(2-amino-ethyl)piperazine, bis(aminopropyl)piperazine, N-(3-aminopropyl)morpholine and the like; and aliphatic amines such as methylamine, ethylamine, stearylamine, allylamine, Isopropylamine, 2-ethylhexylamine, ethanolamine, 3- (2-ethylhexyloxy)Propylamine, 3-ethoxypropylamine, 3-(diethylamino)Propylamine, 3-(dibutylamino)Propylamine, tert-butylamine, Propylamine, 3-(methylamino)Propylamine, 3-(dimethylamino)Propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclohexanemethylamine, cyclohexylamine, 4-meth is cyclohexylamine, 2-bromethalin, 2-methoxyethylamine, 2-ethoxymethylene, 2-amino-1-propanol, 2-aminobutanol, 3-amino-1,2-propandiol, 1,3-diamino-2-hydroxypropane, 2-aminoethanol, Ethylenediamine, Diethylenetriamine, hexamethylenediamine were and so on. Of them it is preferable to use aromatic monoamines.

Amine compound of General formula (XIII) are not specifically ograniczenia provided that it has two or more amino groups. This compound includes, for example, aromatic amines such as 4,4’-diamino-3,3’-diethyldiphenylurea, 4,4’-diaminobenzanilide, 3,5-diaminophenol, diaminodiphenyl ether, 3,3’-dichloro-4,4’-diaminodiphenylmethane, 3,3’-dimethyl-4,4’-diaminodiphenylmethane, tolidine base, dianisidine, bis[4-(m-aminophenoxy)phenyl]sulfon, bis[4-(p-aminophenoxy)phenyl]sulfon, bis[3-methyl-4-(p-aminophenoxy)phenyl]sulfon, 3,3’-dimethoxy-4,4’-diaminobiphenyl, 3,3’-dimethyl-4,4’-diaminobiphenyl, 2,2’-dichloro-4,4’-diamino-5,5’-dimethoxybiphenyl, 2,2’,5,5’-tetrachloro-4,4’-diaminobiphenyl, o-toluensulfonyl, 2,4’-diaminobiphenyl, 2,2’-diaminobiphenyl, 4,4’-diaminobiphenyl, 2,2’-dichloro-4,4’-diaminobiphenyl, 3,3’-dichloro-4,4’-diaminobiphenyl, 2,2’-dimethyl-4,4’-diaminobiphenyl, 4,4’-thiodianiline, 2,2’-dicitionary, 4,4’-dicitionary, 4,4’-diaminodiphenyl ether, 3,3’-diaminodiphenyl ether, 3,4’-diaminodiphenyl ether, 4,4’-diaminodiphenylmethane, 3,4’-diminutive Ilmatar, bis(3-amino-4-chlorophenyl)sulfon, bis(3,4-diaminophenyl)sulfon, 4,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylsulfone, 3,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylmethane, 4,4’-diaminodiphenylamine,4,4’-ethylendiamin, 4,4’-diamino-2,2’-dimethylbenzyl, 3,3’-diaminobenzophenone, 4,4’-diaminobenzophenone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-AMINOPHENYL)fluorene, 2,2-bis(4-aminophenoxy)propane, 4,4’-bis(4-aminophenoxy)diphenyl, dianisidine, 3,3’-dichlorobenzidine, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, and so forth. From the above as examples of amine compounds particularly preferred are aniline derivatives having at least two amino groups and represented by the following formula (VIII):

where R1, R2, R3and R4independently represent a hydrogen atom, halogen atom, alkyl group, alkoxygroup or amino group, X1and X2independently represent an amino group or a group represented by the formula (b):

and Y1represents any group of SO2-, -O-, -(S)n-, -(CH2)n-, -CO-, -CONH -, and a group represented by any of formula (a):

or absent, and n is 1 or 2.

The compound containing an Oh group, of General formula (XIV) is not specifically limited provided that it has two or more HE gruppetto compound includes, for example, divinely, such as 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(hydroxyphenyl)butane, 2,2-bis(hydroxyphenyl)pentane, 2,2-bis(hydroxyphenyl)heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyragollole, hydroquinone, methylhydroquinone, p,p’-biphenol, butyl bis(4-hydroxyphenyl)acetate, benzyl bis (4-hydroxyphenyl)acetate, bis(4-hydroxyphenyl)sulfon, bis(3-methyl-4-hydroxyphenyl)sulfon, bis(3,5-dimethyl-4-hydroxyphenyl)sulfon, 3,4-dihydroxyphenyl-4’-methylphenylsulfonyl, bis(2-allyl-4-hydroxyphenyl)sulfon, bis(2-methyl-3-tert-butyl-4-hydroxyphenyl)sulfide, 4,4’-dihydroxydiphenyl ether, 4,4’-thiodiphenol, 4,4’-dihydroxybenzophenone, 2,2-bis(4-hydroxyphenyl)hexaferrite, 4,4’-dihydroxydiphenylmethane, 3,3’-dihydroxydiphenyl, bis(4-hydroxy-3-were) sulfide and so on. However, essentially divinely, which have the amino group, is undesirable. Because the amino group is more reaktsionnosposobnykh towards isocyanate group than the HE group, the amino group interacts with the isocyanate group before HE g is uppy, thus making it difficult to obtain the desired compounds in some cases. The compound containing an Oh group, of General formula (XIV) also includes the polyester polyols of the type, such as polypropyleneglycol, polytetramethylene glycol ethers, adipat-derived polyols, aproximatively, polyether ester polyols, polycarbonate polyols, polycaprolactone diols, phenolic polyols, aminodiphenylamine polyols and the like; and polyols, such as ethylene glycol, diethylene glycol, 1,3-propandiol, 1,2-propandiol, propylene glycol, dipropyleneglycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,6-hexandiol, 1,9-nonanediol, acrylic polyols, fluorocarbon polyols, polybutadiene polyols, polyhydroxyvalerate, trimethylolpropane, trimethylacetyl, hexanetriol, phosphoric acid, neopentylglycol, pentaerythritol, polyols derived from castor oil, polymer polyols, methylpentanediol, halogenated polyols, phosphorus-containing polyols, Ethylenediamine, α -methylglucoside, sorbitol, sucrose and so on.

A method of obtaining a urea-urethane compound of the formula (V), ispolzuemogo in each of the aspects of the present invention or the twenty-first or twenty-second, is not limited. This compound can be obtained, for example, when interacting monitoringo connection with Aro eticheskim diisocyanate connection and diamino compounds of the following General formula (XV) in accordance with, for example, the reaction formula (G) or (H)below:

where the atom(s) of each hydrogen of the benzene ring may be substituted(s) Deputy, which preferably represents the residue of aromatic compounds, the aliphatic residue of a compound or a residue of heterocyclic compounds, although the Deputy may be a nitro-group, a hydroxyl group, a carboxyl group, nitrosopropane, nitrile group, carbamoyl group, raidgroups, isocyanate group, mercaptopropyl, sulfopropyl, sulfamoyl group or a halogen atom, each residue can have one or more substituents, γ represents a group selected from the group comprising-SO2-, -O-, -(S)n-, -(CH2)n-, -CO-, -CONH - and any group represented by the formula (a);

or absent, and n is 1 or 2.

A method of obtaining a urea-urethane compound of the formula (VI), ispolzuemogo is in each of the aspects of the present invention, or the twenty-first or twenty-second, is not limited. This compound can be obtained, for example, in the interaction of aniline derivative with an aromatic diisocyanate connection and dihydroxytoluene following General formula (XVI) in accordance with, for example, the reaction formula (J) or (K) below:

where the atom(s) of each hydrogen of the benzene ring may be substituted(s) Deputy, which preferably represents the residue of aromatic compounds, the aliphatic residue of a compound or a residue of heterocyclic compounds, although the Deputy may be a hydroxyl group, a nitro-group, a nitrile group, carbamoyl group, sulfamoyl group, a carboxyl group, nitrosopropane, amino group, accelerograph, nitrolingual, hydratherapy, raidgroups, isocyanate group, mercaptopropyl, sulfopropyl or a halogen atom, each residue can have one or more substituents, and b is a group selected from the group comprising-SO2-, -O-, -(S)n-, -(CH2)n-, -CO-, -CONH-, -NH-, -CH(COOR1)-, -C(CF3)2- and- (CR2R3- or is absent, and n is 1 or 2.

Compounds used to obtain a urea-urethane compound of the formula (V) or (VI)used in each of the aspects of the present invention or the twenty-first or twenty-second, described in more detail below.

Phenolic compounds used for the synthesis of urea-urethane compound of the formula (V)is not specifically limited provided that it has one or more Oh groups on the benzene ring. In addition, the atom(s) of the hydrogen of the benzene ring may be substituted by the Deputy, other than the HE group, that is, the remainder of aromatic compounds, a residue of aliphatic compounds, a residue of heterocyclic compounds, the nitro-group, a carboxyl group, nitrosopropane, nitrile group, carbamoyl group, raidgroups, isocyanate group, mercaptopropyl, sulfopropyl, sulfamoyl group or halogen atom.

Preferred examples of the phenolic compounds are phenols, such as phenol, cresol, Xylenol, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-op, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, nitro-substituted phenols (for example, p-NITROPHENOL), halogen-substituted phenols (e.g., o-chlorophenol and p-chlorophenol), 4-phenylphenol-hydroxyphenyl-4’-methylphenylsulfonyl, 3-chloro-4-hydroxyphenyl-4’-methylphenylsulfonyl, 4-isopropylphenyl-4’-hydroxyanisole, 4-isopropoxyphenyl-4’-hydroxyanisole, 4-hydroxyphenyl-4/-benzyloxyphenyl, 4-isopropylphenyl-4’-hydroxyanisole, 4-hydroxy-4’-isopropoxyphenyl, fenilsalitsilat, salicylanilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, (4’-Chlorobenzyl) 4-hydroxybenzoate, dimethyl 3-hydroxyphthalic, 4-methoxyphenol, 4-(benzyloxy)phenol, 4-hydroxybenzaldehyde, 4-n-octyloxybenzoic acid, 4-n-butiloxinazola acid, 4-n-petrogenetically acid, 3-n-dodecyloxybenzoic acid, 3-n-actinomycetoma acid, 4-n-octyloxybenzophenone acid, 4-n-oceanoislascanariascom acid and so on. As phenolic compounds may also be used compounds having one or more substituents, including carboxyl group, nitrosolobus, nitrile group, carbamoyl group, raidgroup, isocyanate group, mercaptopropyl, alphagroup, sulfamoyl group and so on. However, essentially phenols, which have the amino group, is undesirable. Because the amino group is more reaktsionnosposobnykh towards isocyanate group than the HE group, the amino group interacts with the isocyanate group before HE group,thus making it difficult to obtain the desired compounds in some cases.

Aromatic diisocyanate connection used to obtain a urea-urethane compound of the formula (V) or (VI)is not specifically limited provided that it has two isocyanate groups attached to its benzene ring. Aromatic diisocyanate compound includes, for example, n-delete the entry, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-colorvision and 2,6-colorvision. Particularly preferred examples of the aromatic diisocyanates connections are colordistance. Of colordistance preferred is 2,4-colorvision. In addition to 2,4-colordistance as the aromatic diisocyanate may also be used mixtures of 2,4-colordistance and 2,6-colordistance, which are widely spread on the market and available at a low price. Mixtures of these colorvitality isomers are liquid at ordinary temperatures.

Diamino compound of General formula (XV), which is used to obtain a urea-urethane compound of the formula (V)includes, for example, aromatic diamines such as 4,4’-diamino-3,3’-diethyldiphenylurea, 4,4’-diaminobenzanilide, 3,5-diaminophenol, diaminodiphenyl ether, 3,3’-dichloro-4,4’-diaminodiphenylmethane, 3,3’-dimethyl-4,4’-diaminodiphenylmethane, tolidine base, dianisidine, bis[4-(m-am is noproxy)phenyl]sulfon, bis[4-(p-aminophenoxy)phenyl]sulfon, bis[3-methyl-4-(p-aminophenoxy)phenyl]sulfon, 3,3’-dimethoxy-4,4’-diaminobiphenyl, 3,3’-dimethyl-4,4’-diaminobiphenyl, 2,2’-dichloro-4,4’-diamino-5,5’-dimethoxybiphenyl, 2,2’,5,5’-tetrachloro-4,4’-diaminobiphenyl, o-toluensulfonyl, 2,4’-diaminobiphenyl, 2,2’-diaminobiphenyl, 4,4’-diaminobiphenyl, 2,2’-dichloro-4,4’-diaminobiphenyl, 3,3’-dichloro-4,4’-diaminobiphenyl, 2,2’-dimethyl-4,4’-diaminobiphenyl, 4,4’-thiodianiline, 2,2’-dicitionary, 4,4’-dicitionary, 4,4’-diaminodiphenyl ether, 3,3’-diaminodiphenyl ether, 3,4’-diaminodiphenyl ether, 4,4’-diaminodiphenylmethane, 3,4’-diaminodiphenylmethane, bis(3-amino-4-chlorophenyl)sulfon, bis(3,4-diaminophenyl)sulfon, 4,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylsulfone, 3,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylmethane, 4,4’-diaminodiphenylamine, 4,4’-ethylendiamin, 4,4’-diamino-2,2’-dimethylbenzyl, 3,3’-diaminobenzophenone, 4,4’-diaminobenzophenone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 9,9-bis(4-AMINOPHENYL)fluorene, 2,2-bis(4-aminophenoxy)propane, 4,4’-bis(4-aminophenoxy)diphenyl dianisidine, 3,3’-dichlorobenzidine and so on.

Aniline derivative used to obtain a urea-urethane compound of the formula (VI), is not specifically limited provided that the aniline compound has one or more aminogroup the p on the benzene ring. In addition, the atom(s) of each hydrogen of the benzene ring may be substituted(s) the remainder of aromatic compounds, the aliphatic residue of a compound or a residue of heterocyclic compounds, a hydroxyl group, a nitro-group, a nitrile group, carbamoyl group, sulfamoyl group, a carboxyl group, nitrosopropane, amino group, accelerograph, nitrolingual, hydratherapy, raidgroups, isocyanate group, mercaptopropyl, sulfopropyl or a halogen atom.

Preferred examples of such aniline compounds are aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-fenetidin, N,N-dimethyl-p-phenylenediamine, N,N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, carboxyaldehyde anilines (for example, p-aminobenzoic acid), hydroxylamine anilines (e.g., o-aminophenol, m-aminophenol, 2-amino-4-chlorophenol and p-aminophenol), 2,3-xylidine, 2,4-xylidine, 3,4-xylidine, 2,6-xylidine, nitrosamine anilines (e.g., 4-aminobenzonitrile), Anthranilic acid, p-cresidine, halogen-substituted anilines (e.g., 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, o-Chloroaniline, m-Chloroaniline and p-Chloroaniline), α -naphtylamine, aminoanthracene, o-ethylaniline, ethyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, carbamoylation (for example, p-(N-phenylcarbamoyl)aniline p-[N-(4-chlorophenyl)carbarnoyl]aniline, n-[N-(4-AMINOPHENYL)carbarnoyl]aniline, 2-methoxy-5-(N-phenylcarbamoyl)aniline, 2-methoxy-5-[N-(2’-methyl-3’-chlorophenyl)carbarnoyl]aniline and 2-methoxy-5-[N-(2’-chlorophenyl)carbarnoyl]aniline), 5-acetylamino-2-methoxyaniline, 4-acetylaminophenol, 4-(N-methyl-N-acetylamino)aniline, 2,5-diethoxy-4-(N-benzoylamine)aniline, 2,5-dimethoxy-4-(N-benzoylamine)aniline, 2-methoxy-4-(N-benzoylamine)-5-methylaniline, sulfamerazine (for example, 4-sulfanilamide, 3-sulfanilamide, 2-chloro-5-N-phenylsulfonyl, 2-methoxy-5-N,N-Diethylaminoethanol and 2, 5-dimethoxy-4-N-phenylsulfonyl), 2-(N-ethyl-N-phenylenesulfonyl)aniline, 4-dimethylaminoacetonitrile, 4-diethylaminoethylamine, sulfathiazole, 4-aminodiphenylamine, 2-methoxy-5-benzisothiazolin, 2-phenoxycarbonylamino, 2-(2’-chlorophenoxy)sulfanilamide, 3-anilinomethyl-4-methylaniline, nitro-substituted anilines (e.g., o-chloro-p-nitroaniline, o-nitro-p-chloron the Lin, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine and 2-amino-5-nitrobenzonitrile), p-ftoranila, ftoranila, 3-chloro-4-ftoranila, 2,4-diptiranjan, 2,3,4-triptorelin, m-aminobenzotrifluoride, 2-amino-3-bromo-5-nitrobenzonitrile and so on.

As aniline derivatives can also be used aniline derivative having one or more substituents, including carboxyl group, nitrosolobus, accelerograph, nitrolingual, hydratherapy, raidgroup, isocyanate group, mercaptopropyl, alphagroup and so on.

Dihydroxytoluene General formula (XVI), which is used to obtain a urea-urethane compound of the formula (VI), includes divinely, such as 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(hydroxyphenyl)butane, 2,2-bis(hydroxyphenyl)pentane, 2,2-bis(hydroxyphenyl)heptane, 4,4’-biphenol, butyl bis(4-hydroxyphenyl)acetate, benzyl bis (4-hydroxyphenyl)acetate, bis(4-hydroxyphenyl)sulfon, bis(3-methyl-4-hydroxyphenyl)sulfon, bis(3,5-dimethyl-4-hydroxyphenyl)sulfon, bis(2-allyl-4-hydroxyphenyl)sulfon, bis(2-methyl-3-tert-butyl-4-hydroxyphenyl)sulfide, 4,4’-dihydroxydiphenyl ether, 4,4’-thiodiphenol, 4,4’-dihydroxybenzophenone, 2,2-bis(4-hydroxyphenyl)hexaferrite, 4,4’-dihydroxydiphenylmethane, 3,3’-dig taxidermy, bis(4-hydroxy-3-were) sulfide and so on. However, as such, divinely, which have the amino group are undesirable. As the amino group has a higher reactivity towards isocyanate group than the HE group, the amino group interacts with the isocyanate group before HE group, thus making it difficult to obtain the desired compounds in some cases.

A method of obtaining a urea-urethane compound of the formula (VII)used in each of the aspects of the present invention or the twenty-first or twenty-second, is not specifically limited. This compound can be obtained, for example by reaction of compounds containing an Oh group, of General formula (IX) with an isocyanate compound of General formula (XII) and aminoven compound of General formula (XI) in accordance with, for example, the following reaction formula (L).

As the substituent X is attached to the urethane group, urea-urethane compounds of General formula (VII), preferred are alkyl groups, alkeline group, phenyl group, cycloalkyl group, amide group, CNS group, a nitrogroup, nitrosurea, nitrile group, toluensulfonyl group, methanesulfonyl group, acetyl group, halogen atoms, formyl group, is alkylamino and isocyanate group.

Such urea-urethane compounds of General formulas (I)to(VII) as a developer are the preferred compounds of General formulas (II)-(VI), and particularly preferred are compounds of General formulas (V) and (VI).

In addition, the compound of the following structural formula (XX) or (XXI) is particularly preferred.

In the case of the urea-urethane compound used as the developer in each of the aspects of the present invention or the twenty-first or twenty-second, and compounds of formulas (I)-(IV) and (VII) as a developer, if the remainder is attached to the group of urea or urethane group, a represents a residue of aliphatic compounds, color intensity and color stability when printing in some cases worse. Thus, the residue attached to the group of urea or urethane group, preferably represents the residue of an aromatic compound or a residue of heterocyclic compounds. However, the deterioration in the color intensity and color stability when printing, which is probably caused by introduction of the residue of aliphatic compounds decreases with the increase in the total number of group(s) of urea and urethane(s) group(s). In the case of the compounds of formula (III) and formula (I), even if the rest of aliphatic compounds is the number of residues attached to group(s) urea or urethane(nd) group(s), difficulties regarding operating characteristics practically does not occur.

The urea-urethane compound used in each of the aspects of the present invention or the twenty-first or twenty-second, can be obtained by mixing the isocyanate with the appropriate reagents in an organic solvent or without solvent, the interaction between them and then collect the resulting crystals by filtration. As each reagent can be used one or more connections depending on the purpose. The solvent can be any solvent provided that it does not react with the isocyanate group and the functional groups of the reactants. The solvent includes, for example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons, and ketones. Especially preferred are methyl ethyl ketone, toluene and the like, which dissolve the isocyanate and the reaction product has a low solubility. The reaction product, pelochelys by using the above reaction, not always is the only connection, and in some cases is formed in the form of a mixture of compounds different in the position of Deputy.

Specific examples of the urea-urethane compounds used in each of the aspects of the present invention or the twenty-first or twenty-second, are the following compounds (E-1)-(E-43)).

The urea-urethane compound used as the developer in the present invention, is usually a colorless or light-colored compound, which is solid at ordinary temperatures.

The molecular mass of the urea-urethane compound used as the developer in the present invention is preferably 5000 or less, more preferably 2000 or less.

The total number of groups(s) of urea and urethane(Oh) group(s) in the urea-urethane compound used as the developer in the present invention is preferably 20 or less, more preferably 10 or less. The ratio of the group(s) of urea to urethane(Oh) group(s) in the molecular is structrure urea-urethane compound is preferably from 1:3 to 3:1, in particular from 1:2 to 2:1.

To obtain a recording material with the use of urea-urethane compounds as the developer can use the urea-urethane compound of the same type or, if necessary, a combination of two or more types of urea-urethane compounds.

When used in heat-sensitive recording material is a urea-urethane compound is preferably a compound with melting point. The melting point of the urea-urethane compound used as the developer in the present invention is in the field from 40° 500° With, in particular from 60° to 300° C.

Colorless or light-colored substance is a precursor of the dye used in the twenty-second aspect of the present invention, is a compound well known as a coupler used in recording materials, pressure-sensitive and heat-sensitive recording materials and are not specifically limited. As a matter predecessor dye is particularly preferable are leucogranites and more preferred leucocrystal triarylmethane type, leucocrystal fluorolog type, leucocrystal fluorenone type, leucocrystal diphenylmethanone type and the like. Typical p is emery of leucogranitee below.

(1) Connection triarylmethane type of 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophenyl (crystal violet lactone), 3,3-bis(p-dimethylaminophenyl)ftale, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindole-3-yl)ftale, 3-(p-dimethylaminophenyl)-3-(2-methylindol-3-yl)ftale, 3-(p-dimethylaminophenyl)-3-(2-phenylindol-3-yl)ftale, 3,3-bis(1,2-dimethylindole-3-yl)-5-dimethylaminophenyl, 3,3-bis(1,2-dimethylindole-3-yl)-6-dimethylaminophenyl, 3,3-bis(9-ethylcarbazole-3-yl)-5-dimethylaminophenyl, 3,3-bis(2-phenylindol-3-yl)-5-dimethylaminophenyl, 3-p-dimethylaminophenyl-3-(1-methylpyrrole-2-yl)-6-dimethylaminophenyl and so on.

(2) Connection diphenylmethanone type

Benzyl ether of 4,4’-bis-dimethylaminobenzonitrile, N-halogenlampen, N-2,4,5-trichlorophenylacetic and so on

(3) xanthene Compounds such as

Rhodamine In onlinelast, Rhodamine B-p-Chloroaniline,3-dimethylamino-6-methyl-7-(m-triptoreline)fluoran,3 diethylamino-6-methylfluorene, 3 diethylamino-7-methylfluorene, 3 diethylamino - 7-chlorofluoro, 3 diethylamino - 7-dibenzylamino, 3 diethylamino-6-methyl-7-chlorofluoro, 3 diethylamino-7-octylaniline, 3 diethylamino-7-phenylfluorene, 3 diethylamino-6-methyl-7-anilinophenol, 3 diethylamino-6-methyl-7-p-methylanilinium, 3 diethylamino-6-chloro-7-methylfluorene, 3 diethylamino-7-(3,4-dichloraniline)fluoran, 3 diethylamino-7-(2-chloraniline)fluo the Academy of Sciences, 3 diethylamino-6-methyl-7-(o,p-dimethylaniline)fluoran, 3-(N-ethyl-N-tolyl)amino-6-methyl-7-penicillian, 3 diethylamino-7-(4-nitroaniline)fluoran, 3 diethylamino-6-methyl-7-(m-triptoreline)fluoran, 3 diethylamino-6-methyl-7-(o-chloroanilino)fluoran, 3 diethylamino-6-methyl-7-(p-chloraniline)fluoran, 3 diethylamino-6-methyl-7-(o-foronline)fluoran, 3 diethylamino-6-methyl-7-(p-n-butylaniline)fluoran, 3 diethylamino-6-methyl-7-n-octylaniline, 3 diethylamino-6-chloro-7-anilinophenol,3 diethylamino-6-ethoxyethyl-7-anilinophenol, 3 diethylamino-benzo[a]fluoran, 3 diethylamino-benzo[C]fluoran,3-diethylamino-6-methyl-7-benzylaminopurine, 3 diethylamino-6-methyl-7-dibenzylamino, 3 diethylamino-7-di(p-methylbenzyl)aminofluorene, 3 diethylamino-6-methyl-7-diphenylmethylsilane, 3 diethylamino-7-dinaftiletilena, 10-diethylamino-4-dimethylaminobenzoyl[and]fluoran, 3 diethylamino-7,8-benfluorex,3 diethylamino-6-methyl-7-(m-trichloroaniline)fluoran,3 diethylamino-7-(on-chloraniline)fluoran, 3 dibutylamino-7-(o-chloroanilino)fluoran, 3 diethylamino-6-methyl-7-(2’,4’-dimethylaniline)fluoran, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluoran, 3 morpholino-7-(N-propyltrichlorosilane)fluoran, 3-pyrrolidino-7-triftormetilfullerenov, 3 diethylamino-5-chloro-7-(N-benzyl-triptoreline)fluoran, 3-pyrrolidino-7-(di-p-chlorophenyl)methylaminopropane, 3 diethylamino-5-chloro-7-(α -phenylethylamine)fluoran, 3-(N-ethyl-N-p-toluidino)-7-(α -phenylethylamine)fluoran, 3 diethylamino-7-(o-ethoxycarbonylphenyl)fluoran, 3 diethylamino-5-methyl-7-(α -phenylethylamine)fluoran, 3 diethylamino-7-piperidinemethanol, 2-chloro-3-(N-methyltaurine)-7-(p-N-butylaniline) fluoran, 3-(N-ethyl-N-cyclohexylamino)-5,6-benzo-7-α -naphtylamine-4’-bromofluorene, 3 diethylamino-6-methyl-7-mesitylene-4’,5’-benzofuran, 3 dibutylamino-6-methylfluorene, 3 dibutylamino-6-methyl-7-chlorofluoro,3 dibutylamino-6-methyl-7-anilinophenol, 3 dibutylamino-6-methyl-7-p-methylanilinium, 3 dibutylamino-6-methyl-7-(o,p-dimethylaniline)fluoran, 3 dibutylamino-6-methyl-7-(m-triptoreline)fluoran, 3 dibutylamino-6-methyl-7-(o-chloroanilino)fluoran, 3 dibutylamino-6-methyl-7-(p-chloroanilino)fluoran, 3 dibutylamino-6-methyl-7-(o-foronline)fluoran, 3 dibutylamino-6-methyl-7-(p-n-butylaniline)fluoran, 3 dibutylamino-6-methyl-7-n-octylaniline, 3 dibutylamino-6-chloro-7-anilinophenol,3 dibutylamino-6-ethoxyethyl-7-anilinophenol, 3-di-n-pentylamine-6-methyl-7-anilinophenol, 3-di-n-pentylamine-6-methyl-7-(o,p-dimethylaniline)fluoran, 3-di-n-pentylamine-6-methyl-7-(m-triptoreline)fluoran, 3-di-n-pentylamine-6-methyl-7-(o-chloroanilino)fluoran, 3-di-n-pentylamine-6-methyl-7-(p-chloroanilino)fluoran, 3-di-n-pentylamine-6-methyl-7-(o-foronline)fluoran, 3-pyrrolidino-6-methyl-7-anilinium the Academy of Sciences, 3-piperidino-6-methyl-7-anilinophenol,3 cyclohexylamino-6-chlorofluoro, 3-dimethylamino-5,7-dimethylfuran, 3-(N-methyl-N-isoamylamine)-6-methyl-7-anilinophenol, 3-(N-methyl-N-n-propylamino)-6-methyl-7-anilinophenol, 3-(N-methyl-N-arylamino)-6-methyl-7-anilinophenol, 3-(N,N-di-n-arylamino)-6-methyl-7-anilinophenol, 3- (N-methyl-N-isopropylamino)-6-methyl-7-anilinophenol, 3-(N-ethyl-N-n-propylamino)-6-methyl-7-anilinophenol, 3-(N-ethyl-N-isopropylamino)-6-methyl-7-anilinophenol, 3-(N-ethyl-N-n-butylamino)-6-methyl-7-anilinophenol, 3-(N-ethyl-N-isobutylamino)-6-methyl-7-anilinophenol, 3-(N-ethyl-N-n-hexylamino) -6-methyl-7-p-methylaminopropane, 3-(N-ethyl-N-n-hexylamino)-6-methyl-7-(o,p-dimethylaniline) fluoran, 3-(N-ethyl-N-n-hexylamino)-6-methyl-7-(N-triptoreline) fluoran, 3-(N-ethyl-N-n-hexylamino)-6-methyl-7-(o-chloroanilino)fluoran, 3-(N-ethyl-N-isoamylamine)-6-methyl-7-anilinophenol, 3-(N-ethyl-N-isoamylamine)-6-chloro-7-anilinophenol, 3-(N-ethyl-N-3-methylbutylamine)-6-methyl-7-anilinophenol, 3-(N-ethyl-N-p-toluidino)-6-methyl-7-anilinophenol, 3-(N-ethyl-N-p-toluidino)-6-methyl-7-(p-methylaniline)fluoran, 3-(N-ethyl-N-p-toluidino)-6-methyl-7-(o,p-dimethylaniline)fluoran, 3-(N-ethyl-N-tetrahydrofurfurylamine)-6-methyl-7-anilinophenol, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinophenol, 3-(N-cyclohexyl-N-methylamino)-7-anilinophenol, 3-(N-ethyl-N-3-methoxypropylamine)-6-methyl-7-anilinophenol, 3-(N-ethyl-N-3-ethoxypropan the Mino)-6-methyl-7-anilinophenol, 2-(4-oxohexyl)-3-dimethylamino-6-methyl-7-anilinophenol, 2-(4-oxohexyl)-3-diethylamino-6-methyl-7-anilinophenol, 2-(4-oxohexyl)-3-dipropylamino-6-methyl-7-anilinophenol, 3,6-bis(diethylamino)fluoran-γ -(2’-nitro)anilinomethyl, 3,6-is(diethylamino)fluoran-γ -(3’-nitro)onlinelast, 3,6-is(diethylamino)fluoran-γ -(4’-nitro)anilinomethyl, 3,6-bis(diethylamino)fluoran-γ -anilinomethyl and so on.

(4) Connection casinomaha type

Benzoylacetone blue, p-nitrobenzylamine blue and so on.

(5) Spiraeoideae

3-methylmercaptopurine, 3-ateleportation, 3,3-dichlorophenolindophenol, 3-benzylpyridine, 3-methylnaphtho-(3-methoxybenzo)spiropyran, 3-profileparameter and so on.

Leucocrystal also includes, for example, the following compounds that can absorb wave long-wave infrared region: 3,6-bis(dimethylamino)fluorene-9-Spiro-3’-(6’-dimethylaminophenyl), 3-diethylamino-6-dimethylaminopropan-9-Spiro-3’-(6’-dimethylaminophenyl), 3,6-bis(diethylamino)fluoren-9-Spiro-3’-(6’-dimethylaminophenyl), 3-dibutylamino-6-dimethylaminopropan-9-Spiro-3’-(6’-dimethylaminophenyl), 3-dibutylamino-6-diethylaminocoumarin-9-Spiro-3’-(6’-dimethylaminophenyl), 3,6-bis(dimethylamino)fluorene-9-Spiro-3’-(6’-diethylaminophenyl), 3-diethylamino-6-dimethylaminopropan-9-Spiro-3’-(6 is-diethylaminophenyl), 3 dibutylamino-6-dimethylaminopropan-9-Spiro-3’-(6’-diethylaminophenyl), 3,6-bis(diethylamino)fluoren-9-Spiro-3’-(6’-diethylaminophenyl), 3,6-bis(dimethylamino)fluorene-9-Spiro-3’-(6’-dibutylaminoethanol), 3-dibutylamino-6-diethylaminocoumarin-9-Spiro-3’-(6’-diethylaminophenyl), 3-diethylamino-6-dimethylaminopropan-9-Spiro-3’-(6’-dibutylaminoethanol), 3,3-bis[2-(4-dimethylaminophenyl)-2-(4-methoxyphenyl)ethynyl]-4,5,6,7-tetrachlorophthalic and so on.

Above as examples of leucocrystal, leucocrystal triarylmethane type, leucocrystal fluorolog type, leucocrystal fluorenone type and leucocrystal diphenylmethanone type are preferred from the viewpoint of sensitivity and plasticizer resistance, and more preferred are compounds having a structure represented by the following chemical formula (i) or (j):

where both Y2and Y3represent alkyl groups or alkoxyalkyl group, Y4represents a hydrogen atom, alkyl group, or alkoxygroup, and each Y5and Y6represents a hydrogen atom, halogen atom, alkyl group, or alkoxygroup; or

every where. R5and R6represents a group represented by the formula (k) or formula (1):

(where each R11-R15represents a hydrogen atom, a halogen atom, a C1-C8alkyl group, a C1-C8alkoxygroup or-NR16R17where each R16and R17represents C1-C8alkyl group); or

(where each R18and R19represents a hydrogen atom, a C1-C8alkyl group or phenyl group), and each R7-R10represents a hydrogen atom, a halogen atom, a C1-C8alkyl group, a C1-C8alkoxy

the Rupp or-NR20R21where each R20and R21represents C1-C8alkyl group.

If necessary, such colorless or light-colored precursor chemicals, dye can be used in combination of two or more of them.

The urea-urethane compound as the developer is used in a proportion, preferably from 5 to 1000 parts by weight, more preferably from 20 to 500 parts by weight per 100 parts by weight of a colorless or light-colored substances, precursor of the dye. As the proportion of the urea-urethane compound as a developer, 5 parts by weight or more are sufficient to ensure that the substance is precursor of the dye showed color. If the same proportion the intensity of C is ETA high. When the proportion of the urea-urethane compound as the developer is equal to 1000 parts by mass or less, almost no excess urea-urethane compounds, and it is economically advantageous and therefore preferred.

As the urea-urethane compound or a urea-urethane composition that is used as a developer in the nineteenth aspect of the present invention, can be any urea-urethane compound of the aspects of the present invention, from the first to the fourth, or any urea-urethane composition aspects of the present invention, from the fifth to the twelfth. The process of obtaining these compounds and compositions already described in detail in the detailed description of aspects of the present invention, from the first to the twelfth.

The introduction of the isocyanate compound in the color-forming composition of the present invention improves the stability of the composition during storage. Isocyanate compound which is injected into the color-forming composition of the present invention, refers to a colorless or light-colored, aromatic or heterocyclic isocyanate compound, which is solid at ordinary temperatures. For example, you use one or more of the following isocyanate compounds

Input isocyanate compound include 2,6-dichlorophenylisocyanate, p-chloronicotinate, 1,3-delete the entry, 1,4-delete the entry, 1,3-xylene-4,6-diisocyanate, 1,4-xylene-2, 5-diisocyanate, 1-methoxybenzoyl-2,4-diisocyanate, 1-methoxybenzoyl-2,5-diisocyanate, 1-ethoxybenzoyl-2,4-diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,5-diethoxy-1-benzene-1,4-diisocyanate, 2,5-debutaniser-1,4-diisocyanate, azobenzene-4,4’-diisocyanate, diphenyl ether-4,4’-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate, 3,3’-dimethyl-biphenyl-4,4’-diisocyanate, 3,3’-dimethoxybiphenyl-4,4’-diisocyanate, difenilmetana-4,4’-diisocyanate, diphenylmethylene-4,4’-diisocyanate, benzophenone-3,3’-diisocyanate, fluoren-2,7-diisocyanate, anthraquinone-2,6-diisocyanate, 9-ethylcarbazole-3,6-diisocyanate, pyrene-3,8-diisocyanate, naphthalene-1,3,7-triisocyanate, biphenyl-2,4,4’-triisocyanate, 4,4’,4’-triisocyanate-2,5-dimethoxytrityl, 4,4’,4’-triisocyanate, p-dimethylaminobenzylidene, Tris(4-phenylisocyanate)thiophosphate and so on. If necessary, these isocyanates can be used in the form of a so-called block isocyanates, i.e. additional compounds with phenol, lactam, oxime or the like, they can be used in the form diisocyanate dimer, such as 1-m is TELESOL-2,4-diisocyanate dimer, or diisocyanate trimer as isocyanurate, and they can be used in the form of MDI, poluchaemogo as adduct with various polyols and the like. Can also be used water adducts of isocyanates, selected from 2,4-colordistance, diphenylmethanediisocyanate and the like, such as 1,3-bis(3-isocyanato-4-were)urea; polyol as one adducts, such as trimethylolpropane adduct selected from colordistance (Desmodule L, trade name); phenol adducts of isocyanates; amine adducts of isocyanates; and isocyanate compounds and isocyanate adducts described in the detailed description of Japanese patent JP-A-10-76757 and detailed description of Japanese patent JP-A-10-95171.

Isocyanate compound ispolzut in proportions preferably 5-500 parts by weight, more preferably 20-200 parts by weight, per 100 parts by weight of a colorless or light-colored substances, precursor of the dye. When the proportion of the isocyanate compound consists of 5 parts by mass or more, can be achieved sufficient improvement effect of stability during storage and the color intensity is higher. When the proportion of the isocyanate compound is 500 parts by weight or less, almost no excess isocyanate compounds and it is economically advantageous and traces the tion, preferred.

Introduction aminosidine in the color-forming composition of the present invention additionally improves the stability during storage.

Aminosidine, which can be entered in the color-forming composition of the present invention, is a colorless or light-colored compound, which has at least one aminogroup, and is solid at ordinary temperatures. Depending on the purpose in the combination can be entered in two or more aminosilane. As aminosidine can be mentioned compounds described in Japanese patent A-9-142032, and this link is provided here as a reference. From aminosidine described in the link, iminoisoindolin derivatives are preferable, and 1,3-diimino-4,5,6,7-tetrachloroaniline, 3-imino-4,5,6,7-tetrachloroaniline-1-he and 1,3-diimino-4,5,6,7-tetrabromophenol are more preferred.

Aminosidine used in proportions preferably 5-500 parts by weight, more preferably 20-200 parts by weight, per 100 parts by weight of a colorless or light-colored substances, precursor of the dye. When the proportion of aminosidine consists of 5 parts by mass or more, achieves the improvement of the effect of stability during storage and the color intensity is higher. When the proportion of Imin the connection is 500 parts by weight or less, almost no excess aminosidine and it is economically advantageous and therefore preferred.

In addition, the introduction of amino compounds in the color-forming composition of the present invention improves the stability during storage of the raw surface of the recording material and the printing. Aminosidine, which can be entered, is a colorless or light-colored substance having at least one primary, secondary or tertiary amino group. As such amino compounds may be mentioned a compound described in Japanese patent JP-A-9-142032. The amino compounds described in this reference, an aniline derivative having at least one amino group and represented by the following formula (VIII)are particularly preferred:

where R1, r2, r3and R4independently represent a hydrogen atom, halogen atom, alkyl group, alkoxygroup or amino group, X1and X2independently represent an amino group or a group represented by the formula (b):

and Y1represents any group of SO2-, -O-, -(S)n-, -(CH2)n-, -CO-, -CONH -, and a group represented by any of formula (a):

or is absent and n is 1 or 2.

These amino compounds may be used alone or as a mixture. To improve the safety of the imprint in the plasticizing additive for sustainability proportion of amino compounds is preferably 1-500 parts by weight per 100 parts by weight of a colorless or light-colored substances, precursor of the dye. When the contents of amino compounds is 1 part by weight or more on the part of the urea-urethane compounds, the safety of the imprint can be improved. When the content is 500 parts by weight or less, the operational characteristics of the resulting composition can be sufficiently improved, and this is advantageous from the point of view of the price.

The introduction also acidic developer in the color-forming composition of the present invention improves chuvstvitelnosti and enables color-forming composition to give a brilliant color.

As an acid developer, which is used when the color-forming composition of the present invention is used in heat-sensitive recording material using conventional electron-acceptor substance, in particular predpochtite lname are phenolic derivatives; derivatives of aromatic carboxylic acids or their metal compounds; salicylic acid derivatives or their metal salts; prosodie N,N-directively; derivatives of sulfonylurea; and so on. Especially preferred are prosodie phenol. Specific examples proizvodnyh phenol is 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(hydroxyphenyl)butane, 2,2-bis(hydroxyphenyl)pentane, 2,2-bis(hydroxyphenyl)heptane, 1,1-bis(4-hydroxyphenyl)cyclohexane, butyl bis (4-hydroxyphenyl)acetate, benzyl bis(4-hydroxyphenyl)acetate, bis(4-hydroxyphenyl)sulfon, bis(3-methyl-4-hydroxyphenyl)sulfon, 4-hydroxyphenyl-4’-methylphenylsulfonyl, 3-chloro-4-hydroxyphenyl-4’-methylphenylsulfonyl, 3,4-dihydroxyphenyl-4’-methylphenylsulfonyl, 4-isopropylphenyl-4’-hydroxyanisole, 4-isopropoxyphenyl-4’-hydroxyanisole, bis(2-allyl-4-hydroxyphenyl)sulfon, 4-hydroxyphenyl-4’-benzyloxyphenyl, 4-isopropylphenyl-4’-hydroxyanisole, bis(2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, (4’-Chlorobenzyl) 4-hydroxybenzoate, ethyl 1,2-bis(4’-hydroxybenzoate), pencil 1,5-bis(4’-hydroxybenzoate), hexyl 1,6-bis(4’-hydroxybenzoate), dimethyl 3-hydroxyphthalic, staringelf, laurelhurst and so on. Salicylic acid derivatives include 4-n-octyloxybiphenyl the Yu acid, 4-n-butyloxycarbonyl acid, 4-n-petrogenetically acid, 3-n-dodecyloxybenzoic acid, 3-n-Oceanological acid, 4-n-octyloxybenzophenone acid, 4-n-oceanoislascanariascom acid and so on. Derivatives, sulfonylureas include, for example, compounds containing one or more arylsulfonamides, such as 4,4-bis(p-colorselectionmodel)difenilmetana, 4,4-bis(o-colorselectionmodel)difenilmetana, 4,4-bis(p-colorselectionmodel)diphenylsulfide, 4,4-bis(p-colorselectionmodel)diphenyl ether, N-(p-toluensulfonyl)-N’-phenylacetone and so on. In addition, can also be used, for example, 4,4’-[oxybis(ethyleneoxy-p-phenylenesulfonyl)]diphenol and mixtures mainly containing this compound (for example, D-90 (trade name, made. Nippon Soda Co., Ltd.)).

From the above examples kislotih developers especially preferred are 2,2-bis(4-hydroxyphenyl)propane, 4-isopropoxyphenyl-4’-hydroxyanisole, bis(3-allyl-4-hydroxyphenyl)sulfon, 2,4’-dihydroxydiphenylsulfone and 4,4’-[oxybis(ethyleneoxy-p-phenylenesulfonyl)]diphenol, as they improve sensitivity and provide an opportunity to obtain a heat-sensitive recording material, with osoby to give brilliant color.

In order to improve the opacity, thermal response, and the like, can also be added phenolic compounds such as N-stearyl-N’-(2-hydroxyphenyl)urea, N-stearyl-N’-(3-hydroxyphenyl)urea, N-stearyl-N’-(4-hydroxyphenyl)urea, n-stearylamine, o-stearylamine, p-laurylamine, p-bucillamine, m-acetylaminophenol, o-acetylaminophenol, p-acetylaminophenol, o-butylaminoethyl, o-stelleninhaberin, p-stelleninhaberin, 1,1,3-Tris(3-tert-butyl-4-hydroxy-6-were)butane, 1,1,3-Tris(3-tert-butyl-4-hydroxy-6-ethylphenyl)butane, 1,1,3-Tris(3,5-di-tert-butyl-4-hydroxyphenyl)butane, 1,1,3-Tris(3-tert-butyl-4-hydroxy-6-were)propane, 1,2,3-Tris(3-tert-butyl-4-hydroxy-6-were)butane, 1,1,3-Tris(3-phenyl-4-hydroxyphenyl)butane, 1,1,3-Tris(3-cyclohexyl-4-hydroxy-5-were)butane, 1,1,3-Tris(3-cyclohexyl-4-hydroxy-6-were)butane, 1,1,3-Tetra(3-phenyl-4-hydroxyphenyl)propane, 1,1,3,3-Tetra(3-cyclohexyl-4-hydroxy-6-were)propane, 1,1-bis(3-tert-butyl-4-hydroxy-6-were)butane, 1,1-bis(3-cyclohexyl-4-hydroxy-6-were)butane, and so forth.

The above acid developers are used in proportions preferably 5-500 parts by weight, more preferably 20-200 parts by weight, per 100 parts by weight of a colorless or light-colored substances, precursor of the dye. When the proportion of acid developer is 5 parts by weight or more, the formation of the color substance is a precursor of the dye is satisfactory and the color intensity is high.

When the proportion of the acid of the developer is equal to 500 parts by weight or less, almost no excess acid developer, and it is economically advantageous and therefore preferred.

Also when the color-forming composition of the present invention is used in the recording material, a pressure-sensitive, the introduction of acid developer in the color-forming composition improves the intensity of staining and allows recording material, a pressure-sensitive, give brilliant color.

As acidic developer is used electron-acceptor substance. Acid developer includes, for example, inorganic compounds such as acid clay, activated clay, attapulgite, bentonite, zeolite, colloidal silica, magnesium silicate, talc, aluminum silicate and the like; phenol, cresol, butylphenol, op, phenylphenol, chlorophenol, salicylic acid and the like, or aldehyde Novolac condensed resin obtained from them, and their metal salts; and derivatives of salicylic acid such as 3-isopropylaniline acid, 3-phenylsalicylate acid, 3-cyclohexylurea acid, 3,5-di-tert-utililizes the Wai acid, 3,5-di(α -methylbenzyl)salicylic acid, 3,5-di-tert-octylsilane acid, 3-methyl-5-benzelconia acid, 3,5-di(α ,α -dimethylbenzyl)salicylic acid, 3-phenyl-5-(α ,α -dimethylbenzyl)salicylic acid and so forth, and their metal salts.

Introduction to color-forming composition of the present invention also fluorescent dye improves whiteness. As the insertion of a fluorescent dye in the color-forming composition of the present invention can be used in a variety of well-known dyes and the above-mentioned derivatives stilbene, derivatives of coumarin, derivatives of pyrazoline, derivatives bestiallity, derivatives of naphthalimide derived bisbenzimidazole and so on. Although fluorescent dyes are not specifically limited, especially preferred are derivatives diaminostilbene acid.

In relation to the number of fluorescent dye fluorescent dye is present in an amount of preferably from 0.01 to 3 wt.%, more preferably from 0.1 to 2 wt.%, based on the total mass (in units of solids) color-forming composition. When the number of used fluorescent dye is more than 3 wt.%, then, in some cases, the color-forming composition becomes is painted. When the amount is less than 0.01 wt.%, then the effect of the fluorescent dye on the white drops.

Then, the color-forming composition of the present invention may contain agents that improve the stability during storage. Agents that improve the stability during storage used in the present invention are additives, such as agents, stabilizing the image, light stabilizers, antioxidants and so on.

When using these agents improve the stability during storage, in combination with the urea-urethane compound developer (that is, the developer includes a urea-urethane compound) and colorless and light-colored substance is a dye precursor, siteprotect color-forming composition can be improved and can be obtained recording material excellent in terms of siteproject.

Agents, stabilizing the image, as preferred examples used in the present invention, agents that improve the stability during storage include, for example, 1,1,3-Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,1, 3-Tris(2-methyl-4-hydroxy-5-cyclohexylphenol)butane, retarded phenolic compounds [e.g., 4,4’-butylidene(2-tert-butyl-5-METHYLPHENOL), 4,4’-THIOBIS(2-tert-butyl-5-METHYLPHENOL), 2,2’-THIOBIS(6-tert-butyl-4-METHYLPHENOL)and 2,2’-Methylenebis(6-tert-butyl-4-METHYLPHENOL)], 4-benzyloxy-4’-(2-methylpyridine)diphenylsulfone, 4,4’-diglycidylether, 1,4-diglycidylether, sodium 2,2’-Methylenebis(4,6-di-tert-butylphenyl)phosphate, derivatives of 2-propanol and derivatives of salicylic acid. Usually these agents, stabilizing the image, are used in a ratio of preferably from 5 to 1000 parts by weight, more preferably from 10 to 500 parts by weight, per 100 parts by weight of a colorless or light-colored substances, precursor of the dye. When the proportion of agents, stabilizing the image is 5 parts by mass or more, siteprotect is appropriate and the intensity of staining is high. When the proportion of agents, stabilizing the image is more than 1000 parts by weight, the effect of siteprotect is not increased and, in addition, this proportion is economically disadvantageous.

The light stabilizers as preferred examples used in the present invention, agents that improve the stability during storage include, for example, 2-(2’-hydroxy-5’-were)benzotriazol, 2-(3’,5’-di-tert-butyl-2’-hydroxyphenyl)benzotriazol, 2-(5’-tert-butyl-2’-hydroxyphenyl)benzotriazole, 2-[2’-hydroxy-5’-(1,1,3,3-TETRAMETHYLBUTYL)phenyl]benzotriazole, 2-(3’,5’-di-tert-butyl-2’-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3’-tert-BU the Il-2’-hydroxy-5’-were)-5-chlorobenzotriazol, 2-(2’-hydroxy-4’-acetoxyphenyl)benzotriazol, 2-(3’,5’-di-tert-pentyl-2’-hydroxyphenyl)benzotriazol, 2-(3’-tert-butyl-2’-hydroxy-5’-octyloxybiphenyl)-5-chlorobenzotriazole and the like; 4-hydroxy-, 4-methoxy-, 4-actoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2’,4’-trihydroxy-, 2’-hydroxy-4,4’-dimethoxy - or 4-(2-ethylhexyloxy)-2-derivatives hydroxybenzophenone and the like; 4-tert-butylanisole, fenilsalitsilat, antifederalist, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate and the like; ethyl α -cyano-β thatβ -diphenylacetate, isooctyl α -cyano-β ,β -diphenylacetate, methyl α -carbomethoxyamino, methyl α -cyano-β -methyl-p-methoxycinnamate and the like; bis (2,2,6,6-tetramethyl-4-piperidyl)sebacina, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacina, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacina, bis(1,2,2,6,b-pentamethyl-4-piperidyl)adipate and the like; 4,4’-di-attractionsand, 2,2’-diethoxycarbonyl, 2,2’-di-octyloxy-5,5’-di-tert-butylanisole, 2,2’-di dodecyloxy-5,5’-di-tert-butylanisole, 2-ethoxy-2’-ethyloxazole, N,N’-bis(3-dimethylaminopropyl)oxanilide, 2-ethoxy-5-tert-butyl-2’-atoxigenic is d, and the like; and 2,4,6-Tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-proproxyphene-6-(2,4-dimetilfenil)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethyl-phenyl)-1,3,5-triazine and the like. Typically, these light stabilizers are used in a ratio of preferably from 5 to 1000 parts by weight, more preferably from 10 to 500 parts by weight, per 100 parts by weight of a colorless or light-colored substances, precursor of the dye. When the proportion of the light stabilizers is 5 parts by mass or more, siteprotect is appropriate and the intensity of staining is high. When the proportion of the light stabilizers is more than 1000 parts by weight, the effect of siteproject no longer increases and, in addition, this proportion is economically disadvantageous.

Antioxidants as preferred examples used in the present invention, agents that improve the stability during storage include, for example, 2,6-di-tert-butyl-4-METHYLPHENOL, 2-tert-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenyl, 2,6-dicyclopentyl-4-METHYLPHENOL, 2-(α -methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-METHYLPHENOL, 2,4,6-tricyclohexyltin, 2,6-dinonyl-4-METHYLPHENOL, 2,6-di-tert-butyl-4-methoxymethanol, 2,4-dimethyl-6-(1’-methyl-undeca-1’-yl)phenol, 2,4-dimethyl-6-(1’-methyl-heptadec-1’-yl)phenol, 2,4-dimethyl-6-(1’-methyl-Tribeca-1’-yl)phenol and a mixture thereof; 2,4-di-actitioner-6-tert-the butylphenol, 2,4-di-actitioner-6-METHYLPHENOL, 2,4-di-actitioner-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-Nonylphenol and their mixture; 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylketone, 2,6-diphenyl-4-octadecylphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylethyl, bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate and their mixture; 2,4-bis-artillerie-6-(3,5-di-tert-butyl-4-hydroxyanisole)-1,3,5-triazine, 2-artillerie-4,6-bis(3,5-di-tert-butyl-4-hydroxyanisole)-1,3,5-triazine, 2-artillerie-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxyphenylpropionic)hexahydro-1,3,5-triazine, 1,3,5-Tris(3,5-DICYCLOHEXYL-4-hydroxybenzyl)isocyanurate and the like; 2,2’-Methylenebis(6-tert-butyl-4-METHYLPHENOL), 2,2’-Methylenebis(6-tert-butyl-4-ethylphenol), 2,2’-ethylidene(4,6-di-tert-butylphenol) 2,2’-ethylidene(6-tert-butyl-4-isobutylphenyl), 4,4’-Methylenebis(2,6-di-tert-butylphenol), 4,4’-Methylenebis (6-tert-butyl-2-METHYLPHENOL), 1,1-bis(5-tert-butyl-4-hydroxy-2-were)butane, ethylene glycol bis[3,3’-bis(3’-tert-butyl-4’-hydroxyphenyl)butyrate], and the like; 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol and the like. Typically, these antioxidants are used in a ratio of preferably from 5 to 1000 parts by weight, more preferably from 10 to 500 parts by weight, per 100 parts by weight of a colorless or light-colored substances, precursor of the dye. When the proportion of agents, stabilizing the image is 5 parts by mass or more, siteprotect is appropriate and the intensity of staining is high. When the proportion of the antioxidant is more than 1000 parts by weight, the effect of siteprotect is not increased and, in addition, this proportion is economically disadvantageous.

Color-forming composition of the present invention may be incorporated in the recording material by formation of a color-forming layer of the composition on a substrate using a method such as coating. The structure of the recording material is changed depending on the grade of the recording in the society.

Color-forming composition of the present invention may be included in various recording materials such as heat-sensitive recording materials, recording materials, pressure-sensitive, and the like, and particularly suitable for heat-sensitive recording materials.

When the color-forming composition is used in heat-sensitive recording material, then heat-sensitive recording layer capable of giving color when heated, is formed on the substrate. In particular, the above urea-urethane compound of the above colorless or light-colored substance is a dye precursor, such as leucocrystal, Caloplaca substance, described hereinafter, and the like can be deposited on the substrate, each in the form of a dispersion, together with other necessary components with the formation of the heat-sensitive recording layer. The variance is obtained by fine grinding of one or more compounds as each component described above, a sand mill or the like, in an aqueous solution containing the compounds having the dispersion ability, such as water-soluble polymers, surfactants or the like. The particle size of each of the dispersion thus obtained, which is preferably set from 0.1 to 10 μm, in particular, up to approximately 1 μm. Specific examples of compounds with dispersive ability, which can be used in the present invention are water-soluble polymers, such as poly(vinyl alcohol), poly(vinyl alcohol), modified carboxylic acid, poly(vinyl alcohol), modified sulfonic acid, methylcellulose, hypromellose, hydroxypropylcellulose and the like; anionic surfactants, such as condensed naphthalenesulfonate, salt polyoxyethylenated esters of sulfuric acid (for example, sodium polyoxyethyleneglycol, sodium polyoxyethyleneglycol and sodium polyoxyethylenesorbitan), sodium salt diallylmalonate acid, alkylphosphate (for example, diethanolamine, alkylphosphate and kalyankrishna)special polymers based on carboxylic acids and the like; nonionic surfactants, such as polyoxyethylenesorbitan esters, polyoxyethylenesorbitan esters, esters of polyoxyethylenesorbitan and fatty acids, monoglycerides of fatty acids, esters of polyoxyethyleneglycol and fatty acids and the like; and cationic surfactants such as dicyanomethylene, salts of tertiary amines, the fourth is cnie ammonium salt and so on. Of them, particularly preferred are polyvinyl alcohols, polyvinyl alcohols, modified carboxylic acid, polyvinyl alcohols, modified sulfonic acid, and methyl cellulose. Given as examples of compounds can be used alone or as mixtures thereof.

When the urea-urethane compound developer in accordance with the present invention is used in heat-sensitive recording material, set the average particle size of the urea-urethane compound developer is not more than 5 μm and not less than 0.05 μm makes it possible to obtain a heat-sensitive recording material which has a sufficient color-forming sensitivity, gives a very stable color image printing and has a good plastificator stability. The average particle size is more preferably not more than 3 μm and not less than 0.1 μm. When the average particle size is less than 0.05 μm, the stability during storage of the raw surface of the recording material relative to the plasticizer is deteriorating. On the other hand, when the average particle size of more than 5 μm, the sensitivity of the heat-sensitive recording material decreases.

In particular, when the urea-urethane compound is exposed in the most important ground in the aquatic environment, the temperature of the aqueous medium preferably equal to 60° With or below. During grinding the urea-urethane compound developer interacts with water so that hydrolysis occurs its urethane(s) group(s) depending on conditions. Thus, the sensitivity of the heat-sensitive recording material obtained using urea-urethane compound developer tends to decrease. In particular, when the ambient temperature during grinding more than 60° C, the sensitivity is reduced significantly. The ambient temperature during grinding is preferably more than 40° With or below.

In addition, when the urea-urethane compound developer is mixed, it is preferable to grind in the neutral region of pH 5 to 10. When the pH when the grind is lower than 5, the inorganic pigment and the like dissolves when obtaining a heat-sensitive covering liquid, so that the sensitivity tends to decrease. On the other hand, when the pH is greater than 10, the urea-urethane compound developer hydrolyzed so that the sensitivity in some cases reduced. Specific examples of the dispersing agents used in the preparation of a dispersion of urea-urethane compound developer during grinding in this image is the situation, are water-soluble polymers, such as poly(vinyl alcohol), poly(vinyl alcohol), modified carboxylic acid, poly(vinyl alcohol), modified sulfonic acid, methylcellulose, hypromellose, hydroxypropylcellulose and the like; anionic surfactants, such as condensed naphthalenesulfonate, salt polyoxyethylenated esters of sulfuric acid (for example, sodium polyoxyethyleneglycol, sodium polyoxyethyleneglycol and sodium polyoxyethylenesorbitan), sodium salt diallylmalonate acid, alkylphosphate (for example, diethanolamine alkylphosphate and kalyankrishna), special polymers based on carboxylic acids and the like; nonionic surface-active substances such as polyoxyethylenesorbitan esters, polyoxyethyleneglycol ethers, esters polyoxyethylenesorbitan and fatty acids, monoglycerides of fatty acids, esters of polyoxyethyleneglycol and fatty acids and the like; and cationic surfactants such as dicyanomethylene, salts of tertiary amines, Quaternary ammonium salts and so on. Of these, particularly preferred are water-soluble polymers and anionic surfactants, as is any make it possible to obtain heat-sensitive recording material, which has high sensitivity, regardless of the conditions of the dispersion of the urea-urethane compound developer, and has improved stability during storage of the raw surface of the recording material relative to plasticizers, regardless of the average particle size of the urea-urethane compound developer. Polyvinyl alcohols, modified polyvinyl alcohols, methyl cellulose, hypromellose, condensed sodium naphthalenesulfonate, ammonium salts of polycarboxylic acids, water-soluble copolymers with low molecular weight and sodium 2-ethylhexylacrylate are more preferred. Of them, methylcellulose, hypromellose, condensed sodium naphthalenesulfonate and water-soluble low molecular weight copolymers are more preferred, and hypromellose is the most preferred. Above as examples of dispersing agents can be used alone or as mixtures.

As the dispersing agent used to obtain the dispersion of colorless or light-colored substances, precursor of the dye by grinding according to the present invention can be used some connections from those that were used in the image quality is as dispersing agent for dispersing the urea-urethane compound developer. Of these compounds, especially preferred are water-soluble polymers, anionic surfactants and mixtures of dispersing agents of these two types of compounds to improve the heat-sensitive recording material of sensitivity and stability during storage of the raw surface of the recording material. The mixture of dispersing agents containing methylcellulose or hypromellose as a water-soluble polymer and polyoxyethyleneglycol or sodium 2-ethylhexylacrylate as the anionic surfactant is more preferred. The mixture of dispersing agent hydroxypropylmethylcellulose and sodium 2-ethylhexylacrylate is the most preferred. the pH of the covering liquid containing urea-urethane compound and a colorless or light-colored substance is precursor of the dye is preferably from 5 to 12.

Heat-sensitive recording layer may contain, in addition to the above components, pigments such as diatomaceous earth, talc, kaolin, calcinated kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide, urea-formaldehyde resin and so on. In addition, the heat-sensitive recordings the surrounding layer may if necessary, contain metal salts of higher fatty acids such as zinc stearate, calcium stearate, and so forth; and waxes, such as paraffin, oxidized paraffin, polyethylene, oxidized polyethylene, stearamide, katory wax and so on, with the aim, for example, prevent wear of the head and sticky. If necessary, heat-sensitive recording layer may also contain dispersing agents, such as dioctylsulfosuccinate sodium and so forth; ultraviolet absorbers benzophenone type benzotryazolyl type, and the like; surfactants; fluorescent dyes; and the like.

As binding agents used to obtain heat-sensitive recording layer can be specified, for example, water-soluble binders such as starches, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, gelatin, casein, poly(vinyl alcohol)s, modified poly(vinyl alcohol)s, poly(acrylate)s sodium, copolymers of acrylamide-acrylic ester, trampoliner acrylamide-acrylic ester-methacrylic acid, alkali salts of copolymers of styrene-maleic anhydride, alkali metal salts of copolymers of ethylene-maleinovogo anhydride and the like; and water-insoluble binders latex type selected from copolymers of styrene-butadiene, SOP the materials acrylontrile-butadiene, copolymers of acrylate-butadiene and so on.

As a substrate for a heat-sensitive recording layer mainly used paper, although depending on the purpose in addition to paper can be used in a variety of woven material, nonwoven material, a synthetic polymer film, laminated paper, synthetic paper, metal foil and the composite sheets obtained by combining two or more of them. The basis weight of the substrate is preferably from 40 g/m2to 200 g/m2. The substrate should preferably be excellent in surface smoothness and flatness, as heat-sensitive recording material produced by using a substrate, preferably should be as flat as possible. Thus, the substrate is preferably subjected to surface treatment with the application of heat and pressure by means of any mechanical calender, soft calender, supercalender and the like.

The surface pH of the substrate is preferably 3 to 9, more preferably 5-9, preferably 6-8, when the surface pH of the substrate is lower than 3, you receive the Mat. When the surface pH of the substrate is higher than 12, the urea-urethane compound developer decomposes in such a way that intensivstation in some cases reduced.

Heat-sensitive recording layer may be composed of a single layer or two or more layers. Heat-sensitive recording layer can be, for example, a multilayer structure obtained by introducing each color-forming component in a single layer. A protective layer consisting of a single layer or two or more layers, can be obtained on the heat-sensitive recording layer and the intermediate layer consisting of a single or two or more layers can also be obtained between the substrate and the heat-sensitive recording layer. Heat-sensitive recording layer can be obtained by mixing aqueous dispersions obtained by fine grinding of each color-forming component or any other component with a binder agent, and the like, applying the resulting mixture on a substrate and drying the mixture. Covering the amount of this covering liquid is preferably from 1 to 15 g/m2when the covering liquid is in the dried state.

When the color-forming composition of the present invention is used in heat-sensitive recording material, teleplace material can be introduced into the color-forming composition to improve the sensitivity. Teleplace material preferably is what aka material, which has a melting point of 60° C-180° and such, in which the melting point of 80° to 140° C. Teleplace material includes, for example, benzyl p-benzyloxybenzoate, stearamide or emulsified product, palmitate, N-methyloctane, β -natively ether, N-storelocation, N,N’-DataRelation, phenyl β -aftout, phenyl 1-hydroxy-2-aftout, β -naphthol (p-methylbenzyl) ether, 1,4-dimethoxyethane, 1-methoxy-4-benzyloxyaniline, N-stearolecythine, p-benzylbiphenyl, 1,2-di(m-methylphenoxy)ethane, 1-phenoxy-2-(4-chlorophenoxy)ethane, 1,4-potentialenergy ether, terephthalate, m-terphenyl, dimensionsal and (p-Chlorobenzyl) oxalate.

In addition, as Caloplaca material preferred are 4,4’-dimethoxybenzophenone, 4,4’-dichlorobenzophenone, 4,4’-differentfrom, diphenylsulfone, 4,4’-dichlorodiphenylmethane, 4,4’-debtordefault, 4,4’-dichlorodiphenyl disulfide, diphenylamine, 2-methyl-4-methoxydiphenyl, N,N’-diphenyl-p-phenylenediamine, 1-(N-phenylamino)naphthalene, benzyl, 1,3-diphenyl-1,3-propandiol and so forth, as they very effectively improve the sensitivity.

As Caloplaca material can also be used benzyl 4-hydroxybenzoate, 4-(benzyloxy)phenol, 2,4-dihydroxybenzophenone, 2,2’,4,4’-tetrahydroxybenzophenone, 4,4’-dihydroxybenzophenone, 2, 2-b is(4-hydroxyphenyl)propane, 4,4’-dihydroxydiphenylsulfone, bis(3-methyl-4-hydroxyphenyl)sulfon, bis(3,5-dimethyl-4-hydroxyphenyl)sulfon, 3,4-dihydroxyphenyl-4’-methylphenylsulfonyl, bis(2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4’-dihydroxydiphenyl ether, 4,4’-thiodiphenol, 4,4’-dihydroxydiphenylmethane, 3,3’-dihydroxydiphenyl, bis(4-hydroxy-3-were) sulfide, 4-hydroxy-4’-isopropoxyphenyl, 4,4’-talibanzation, salicylanilide, 4,4’-diamino-3,3’-diethyldiphenylurea, 4,4’-diaminobenzanilide, 3,3’-dichloro-4,4’-diaminodiphenylmethane, 3,3’-dimethyl-4,4’-diaminodiphenylmethane, 4,4’-thiodianiline, 2,2’-dicitionary, 4,4’-dicitionary, 4,4’-diaminodiphenyl ether, 3,3’-diaminodiphenyl ether, 3,4’-diaminodiphenyl ether, 4,4’-diaminodiphenylmethane, 3,4’-diaminodiphenylmethane, bis(3-amino-4-chlorophenyl)sulfon, bis(3,4-diaminophenyl)sulfon, 4,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylsulfone, 3,4’-diaminodiphenylsulfone, 3,3’-diaminodiphenylmethane, 4,4’-diaminodiphenylamine, 3,3’-diaminobenzophenone, 4,4’-diaminobenzophenone, acetoacetic o-chloranilide, acetoacetic anilide, acetoacetic o-toluidin, acetoacetic p-toluidin, acetoacetic o-anisidin, acetoacetic m-xylidide and p-azotoluene and so on.

One of them is preferably used diphenylsulfone, di-p-methylbenzylamine, benzyl, β -natively ether, p-benzylbiphenyl, 1,2-d is(m-methylphenoxy)ethane, 1,2-diphenoxyethane, m-terphenyl and stearamide.

In addition, the use Caloplaca material of the following formula of the formula (XVIII), which is presented above as examples Caloplaca materials, heat-sensitive recording substance is significantly effective for improving the sensitivity of the recording material and improve plastificator stability of the printed part and thermal stability of the original surface of the recording material. Caloplaca materials represented by structural formula (XIX)below are particularly preferable.

where Y represents any group-SO2-, -(S)n-, -O-, -CO-, -CH2-, -CH(C6H5)-, -C(CH3)2-, -COCO-, -CO3-, -PINES2CO-, -SOON2-, -CONH-, -OCH2- and-NH-, n is 1 or 2, and the atom(s) of each hydrogen of the benzene ring may be substituted by a halogen atom, a hydroxyl group, a nitrogroup, nitrosopropane, nitrile group, isocyanate group, isothiocyanato group, mercaptopropyl, sulfamoyl group, sulfonic group, an amino group, a residue of aromatic compounds, a residue of aliphatic compounds or heterocyclic residue of the connection.

where the atom(s) vodorodnogo benzene ring may be substituted by halogen atom, a hydroxyl group, a nitrogroup, nitrosopropane, nitrile group, isocyanate group, isothiocyanato group, mercaptopropyl, sulfamoyl group, sulfonic group, an amino group, a residue of aromatic compounds, a residue of aliphatic compounds or heterocyclic residue of the connection.

Above as examples Caloplaca materials can be used alone or as mixtures thereof. To achieve sufficient thermal response teleplace material is used in a proportion preferably 10-300 parts by weight, more preferably 20 to 250 parts by weight, per 100 parts by weight of a colorless or light-colored substances, precursor of the dye.

As the dispersing agent, which can be used to obtain a dispersion Caloplaca material by grinding according to the present invention can be used in some compounds, like those that were used as a dispersing agent for dispersions of urea-urethane compound developer. Of these compounds to improve the heat-sensitive recording material stability during storage of the raw surface of the recording material relative to plasticizers particularly preferred are the water-soluble polymer and anionic surfactants. More preferred are poly(vinyl alcohol), modified poly(vinyl alcohol), methyl cellulose, hypromellose, condensed naphthalenesulfonate sodium, and ammonium salts of polycarboxylic acids, water-soluble copolymers of low molecular weight and sodium 2-ethylhexylacrylate. Of them, modified polyvinyl alcohols, methyl cellulose, hypromellose, condensed sodium naphthalenesulfonate, ammonium salts of polycarboxylic acids are more preferred, and hypromellose is the most preferred. Above as examples of dispersing agents can be used alone or as a mixture thereof.

When the urea-urethane compound developer crushed, fine grinding of the developer together with the above as an example Caloplaca material (joint grinding also improves the sensitivity and the stability during storage of heat-sensitive recording material compared to finely ground every connection with subsequent mixing of the powdered compounds. The reasons why these effects are not completely clear.

In addition, moisture resistance neotectonic part (original surface) of the heat-sensitive recording the covering material can be improved by using, at least one dispersing agent for the urea-urethane compound developer selected from methylcellulose, hydroxypropylmethylcellulose, condensed sodium naphthalenesulfonate and water-soluble copolymers of low molecular weight, and at least one dispersing agent for Caloplaca material selected from modified polyvinyl alcohols, methyl cellulose, hydroxypropylmethylcellulose, condensed sodium naphthalenesulfonate and ammonium salts of polycarboxylic acids.

Color-forming composition of the present invention can be used in various heat-sensitive recording materials and is particularly suitable for heat-sensitive magnetic recording materials, heat-sensitive labels for recording, color heat-sensitive recording material for laser marking.

When the color-forming composition of the present invention is used in heat-sensitive magnetic recording material, the recording material is preferably the following form: heat-sensitive recording layer containing a urea-urethane compound developer, formed on one side of a substrate and a magnetic layer formed on the other side.

The magnetic recording layer talacasto the part of the magnetic recording material is obtained by coating on the substrate covering material obtained using a homogeneous dispersion of the ferromagnetic powder such as barium ferrite, strontium ferrite, Co-γ -Fe2O2that γ -Fe2O2or the like, in an aqueous binder substance, such as water emulsified polymer, and drying the coating substrate. In this case, depending on their goals may be added various additives such as antistatic agents (for example, carbon graphite), lubricants (naprimer, wax), colored pigments for correcting tone with foil plasticizers [for example, poly(ethylene oxide)s], and so on.

Heat-sensitive magnetic recording material of the present invention is suitable as a heat-sensitive magnetic recording material to be used as train tickets, tickets, frankirovaniya cards and so on.

When the color-forming composition of the present invention is used as a label for heat-sensitive recording label preferably is in the form of a heat-sensitive recording layer containing a urea-urethane compound developer, is formed on one side of the substrate and the adhesive layer is formed on the other side.

The adhesive layer of this heat-sensitive recording material is mainly the zoom consists of adhesive, pressure-sensitive. Adhesive, pressure-sensitive, includes, for example, adhesives of the type emulsions based on synthetic rubber, adhesives type acrylic emulsion adhesives of the type of solvent based natural rubber adhesive type acrylic solvent and adhesive type solvent-based silicone. Of them, especially preferred are adhesive type acrylic emulsion.

When the layer back side coating (back side), if necessary, is formed between the adhesive layer and the substrate, the label for heat-sensitive recording obtained by using a method in accordance with the present invention, off the field, preventing electrostatic charge, and set the coefficient of friction in the label for heat-sensitive recording. As components of liquid to the coating layer for the back side, the method of coating for coating, and the like, can be used the same ingredients, method and the like while forming the heat-sensitive recording layer. Dry the distribution of the liquid coating is in the area of preferably from 0.2 to 10.0 g/m2.

The procedure nishes when it receives a label for heat-sensitive recording is not specifically limited. For example, you can use any of the following: telecoustic the capacity of the recording layer formed on one side of the substrate and then form a coating of the reverse side on the other side, after that, the coating of the reverse side form the adhesive layer; or coating the reverse side of the form on one side of a substrate and then heat-sensitive recording layer formed on the other side, and then coating the reverse side of the form the adhesive layer.

As a method of forming an adhesive layer on the surface of the reverse side, the liquid for formation of the adhesive layer may be directly deposited on the coating of the reverse side and dried, or a material obtained before applying liquid for forming an adhesive layer on the cushioning paper, followed by drying may be applied to cover the back side of the heat-sensitive recording material, having formed an adhesive layer.

In addition, thermal response can be improved when forming the intermediate layer consisting of a single layer or two or more layers, between the heat-sensitive recording layer and the substrate. The intermediate layer mainly consists of organic or inorganic pigment, hollow particles and aqueous binders such as water-soluble polymer or latex. As an organic or inorganic pigment and the aqueous binder can be used the same organic or inorganic pigment and water binder, used in heat-sensitive recording layer. The method for forming the intermediate layer is not specifically limited. This method can be used the same way as the method for forming heat-sensitive recording layer. Area distribution of dry matter of the intermediate layer is in the area of preferably from 2.0 to 15.0 g/m2.

When the color-forming composition of the present invention is used in a color heat-sensitive recording material, this recording material preferably is in the following form: at least two heat-sensitive recording layer formed on one side of a substrate and at least one of the heat-sensitive recording layers containing the urea-urethane compound developer.

As used substrate can be used synthetic paper obtained by mixing the polyolefin resin and a white inorganic pigment by heating, stamping mixed product through the mold, stretching mixed product in the longitudinal direction, by laminating one or two films made of polyolefin resin and a white inorganic pigment on each side of the extended product, and stretching the obtained system is in the transverse direction, to make it semi-transparent or opaque; film obtained by mixing one or a mixture of two or more thermoplastic resins, such as polyethylene, polypropylene, ethylenevinylacetate copolymer resin, poly(vinyl chloride)s, polystyrenes, polyesters, and so forth, with heating, pressing mixing capacity of the product through the mold and then dragging the mixed product in the longitudinal-transverse direction; an opaque film obtained by mixing a white inorganic pigment with any of the above as examples of the resins, with subsequent longitudinal-transverse stretching; and substrates derived from cellulose fibers, such as the paper containing wood pulp, paper with an average grade of wood pulp, paper, glazed on one side, recycled paper, coated paper and so on. Substrates made of cellulose fibers, preferably cover the heat-sensitive layer after the previous formation of the coating layer to improve the homogeneity of the image.

Heat-sensitive color-forming layer in accordance with the present invention includes, as main elements of the adhesive and color-forming composition capable of inducing the reaction of formation of color due to the contact of materials with each other when heat is assured. Specific examples of the color-forming composition is a combination of a colorless or light-colored substances, precursor of the dye and the above-mentioned urea-urethane developer capable of color formation specified substance is a dye precursor when heated, and a combination of diazocompounds and couples who are able to give a color by its interaction with diazoketones. If you want, in the color-forming composition can be activated crosslinking agent, pigments and Caloplaca materials. Normally, the amount of coating heat-sensitive color-forming layer is preferably from 3 to 15 g/m2from the point of view of the sensitivity of color formation and the intensity of the color.

As a color-forming dye, as described, is used colorless or light-colored substance is precursor of dye, which can exhibit a color when the interaction with the urea-urethane compound developer when heated.

On the other hand, in the heat-sensitive recording layer comprising as the main elements of vatsayayana and the coupling element capable of manifestation of color and its interaction with the above diazoketones, these compounds are well known switerzland diazoketones and the coupling element capable of Faure is the key pigment by its interaction with the above diazoketones. If necessary, can be added to the basic material and the like to speed up the interaction diazocompounds with the coupling element. The element of communication and basic material is preferably used as a mixture in the proportions of from 10 to 1000 parts by weight and from 10 to 2000 parts by weight, respectively, per 100 parts by weight of diazocompounds.

The term “svetorasseyanie vatsayana”used here means svetochuvstvitelnyye material diazotype capable of the formation of pigment in the interaction with the coupling element when heated, such as salt, page, diazomethane connection, diazoaminobenzene, financesee connection or the like. Sol, page relates to the compound represented by the General formula:

Ar-N

+
2
·X-

where AG represents an aromatic portion, N

+
2
represents a group of the page and X-is a counterion. Such compounds have different absorption maxima wavelengths depending on location and class of the Deputy AG part.

Specific examples of the compounds of the page used in the present invention, represent 4-dimethylaminobenzophenone, 4-diethylaminobenzaldehyde, 4-dipropylenetriamine, 4-methylbenzotriazole, 4-dibenzylideneacetone, 4-ethylhydroxylamine, 4-diethylamino-2-methoxybenzenediazonium, 4-dimethyl-3-methylbenzothiazole, 4-benzoylamino-2,5-diethoxybenzene, 4-morpholinobenzenediazonium, 4-morpholino-2,5-diethoxybenzene, 4-morpholino-2,5-dimetacrylate, 4-anilinomethylene, 4-TaylorMade-2,5-diethoxybenzene, 4-(N,N-dioctyltinbis)benzodiazepi, 2-octadecylsilane, 4-(4-tert-octylphenoxy)benzodiazepi, 4-(2,4-di-tert-AMYLPEROXY)benzodiazepi, 2-(4-tert-octylphenoxy)benzodiazepi, 5-chloro-2-(4-tert-octylphenoxy)benzodiazepi 2,5-bis-octadecylsilane, 2,4-bis-octadecylsilane, 4-(N-artillerymen)benzodiazepi and so on. Specific examples of the counterion diazonium salts used in the present invention, represent Cl· 1/2ZnCl

-
2
BF
-
4
PFtd align="left"> 6
-
, B(ph)
-
4
CnF2n+1COO-(n = 3-9), CmF2m+1SO
-
3
(m is 2-8), (CkF2k+1SO2)2SN-(k is 1-18) and so on.

Diazomethane compound used in the present invention, is a compound represented by the following General formula:

Ar-N2-SO3Na

where AG represents an aromatic portion. Specific examples diazomethane compounds used in the present invention, are benzodiazelines sodium with one or more substituents, including 2-methoxy, 2-phenoxy, 2-methoxy-4-phenoxy, 2,4-dimethoxy, 2-methyl-4-methoxy, 2,4-dimethyl, 2,4,6-trimethyl, 2,4,6-trimetoksi, 2,4-dimethoxy-5-chloro, 2-methoxy-5-nitro, 2-methoxy-5-acetamido, 2-methoxy-5-N,N-diethyltoluamide, 2-methoxy-5-N-phenylcarbamoyl, 3-methyl, 4-methyl, 4-methoxy, 4-ethoxy, 4-phenyl, 4-phenoxy, 4-acetamido, and so forth; and sodium benzodiazelines with one or more substituents, including 4-(N-ethyl-N-benzylamino), 4- (N,N-dimethylamino), 4-(N,N-diethylamino), 4-(N,N-diethylamino)-3-chloro, 4-(N-ethylamino)-3-methyl, 4-(N,N-diethyl-the Ino)-2-methyl, 4- (N-ethyl-N-β -hydroxyethylamino), 4-pyrrolidino-3-chloro, 4-pyrrolidino-3,5-dichloro, 4-morpholino, 4-morpholino-3-chloro, 4-morpholino-2-methoxy, 4-morpholino-2,5-diethoxy, 4-morpholino-2,5-dibutoxy, 4-(4’-tailormade)-2,5-dibutoxy, 4-(4’-tailormade)-2,5-diethoxy, 4-(4’-methoxybenzylamine)-2,5-dibutoxy, 4-diphenylamino and so on. When using any of these diazomethane compounds, diazomethane connection is preferably activated by light irradiation before printing.

Diazoaminobenzene that can be used in the present invention are a compound obtained by the interaction of diazogroup with dicyandiamide, sarcosine, methyltaurine, N-ethylanthranilate acid-5-sulfonic acid, monoethanolamine, diethanolamine, guanidine or the like.

Financialaid used in the present invention, are considered as the internal salt of diazonium salts from the point of view of structure and represents, for example, financialaid or on-nattokinaise. Financialaid includes salts, esters and amides of compounds selected from 1,2-financialaid-4-sulfonic acid, 1,2-nattokinase-5-sulfonic acid, 1,2-nattokinase-4-sulfonic acid and so on. Specific examples financialaid used in the present invention are 1,2-chikondi the Zid-4-sulfonate sodium 1,2-nattokinase-5-sulfonate sodium 1,2-nattokinase-4-sulfonate sodium p-cumylphenol 1,2-nattokinase-5-sulfonate, p-cumylphenol 1,2-nattokinase-4-sulfonate, methyl 1,2-nattokinase-5-sulfonate, ethyl 1,2-nattokinase-5-sulfonate, dimethylamide 1,2-nattokinase-5-sulfonic acid, esters of 1,2-nattokinase-5-sulfonic acid and Novolac resin and so on. In addition, these svetorasseyanie diazocompounds can be used independently or in combination.

The binder used in the present invention, is such an element, which interacts with diazoketones with the formation of pigment. For example, a typical actual pigment components, capable of forming a yellow pigment, are compounds which have a methylene group activated adjacent to it carbonyl group and represented by the General formula RCOCH2CO-R’, where R represents an alkyl group or allyl group, and R’ is an aromatic amine. Magenta - binding substance is, for example, 1) cyanoacetyl - derived cyclic compounds or (2) heterocyclic compounds with active methylene or any other connecting part on the heterocyclic ring. The actual pigment Magenta components including the indicate in themselves, for example, pyrazolone compounds and compounds indazole. Cyanide binders include, for example, phenols and Naphtali.

Specific examples of the binder of the present invention are 4-(p-toluensulfonyl)-ω -benzoylacetone, α -benzoyl-o-methoxyacetanilide, 2-cyanoacetamide, 1-(2,4,6-trichlorophenyl)-3-p-nitroamine-2-pyrazolone-5-he, resorcinol, phloroglucin, 2,3-dihydroxynaphthalene, 2,6-dibromo-1,5-dihydroxynaphthalene, N-(o-acetamidophenyl)-1-hydroxy-2-naftolin and so on. In addition, these color-forming components can be used independently or in combination.

For a more uniform passage of interaction diazocompounds and a binder in the main atmosphere of the basic material is preferably introduced into the heat-sensitive color-forming layer. As the primary material used is slightly soluble in water or insoluble in water main material or material capable of formation of alkali when heated. The main material includes, for example, nitrogen-containing compounds such as inorganic and organic ammonium salts, organic amines, amides, urea and thiourea and derivatives thereof, thiazole, pyrrole, pyrimidines, piperazines, guanidines, imidazoles, imidazolines, triazoles, morpholines, piperidine, amidine, formamidine, pyridine and so the alley.

Specific examples of these compounds are tricyclohexyltin, tribenzylamine, octadecylsilane, stearylamine, allylation, thiourea, methylthymidine, allithiamine, ethylendiamine, 2-benzylimidazole, 4-phenylimidazole, 2-phenyl-4-Mei, the 2-undetermination, 2,4,5-triphenyl-2-imidazoline, 1,2-diphenyl-4,4-dimethyl-2-imidazoline, 2-phenyl-2-imidazoline, 1,2,3-triphenylguanidine, 1,2-dicyclohexylbenzene, 1,2,3-tricyclohexyltin, the guanidine trichloroacetate, N,N’-dibenzylpiperazine, 4,4’-decimalpoint, trichloracetic morpholine 2-aminobenzothiazole, 2-benzoilhidrazonele and so on. These basic materials may be used alone or in combination.

In the present invention, the shelf life can be improved by adding a weak acid such as citric acid, tartaric acid, oxalic acid, boric acid, phosphoric acid, pyrophosphoryl acid or the like in the heat-sensitive color-forming layer formed by the combination of diazocompounds and binder.

Must say that the color-forming components used in the present invention can be used in the form of a solid dispersion, which is obtained by the dispersion of the components in the aqueous solution of the water-soluble polymer, followed by coating and drying, as in a normal IU the ode, used for heat-sensitive recording materials. It is also possible to improve the stability of the green seal color-forming substance with the formation of microcapsules and prevent contact of the color-forming substance with the developer at ordinary temperatures, using the insulating effect of the walls of the capsules, as described in Japanese patent JP-A-59-190886, JP-A-60-49991, JP-A-61-169281 and so on. Microcapsules are characterized by the fact that they pozvolilizobrazit substance and the developer to interact with each other when heated at a certain temperature or higher. The temperature at the beginning of the interaction of color-forming substance with the developer can be controlled by properly selecting the substance of the walls of the capsules, the basic substance capsules, supplements, and so forth.

As materials for the walls of the microcapsules in the present invention may be mentioned ordinary substances to the walls of the microcapsules, such as polyurethane, polyurea, polyesters, polycarbonates, urea-formaldehyde resins, melamine resins, polystyrene, styrene-methacrylate copolymers, gelatin, poly(vinyl pyrrolidone)s, poly(vinyl alcohol)s, and so on. These polymers can be used alone or in combination.

In the present invention as the adhesive contained in replaceselectioncommand layer, can be used any water-soluble resin or water dispersible resin. However, when any of these resins is mixed with dispersions of the above-mentioned color-forming dye and developer, respectively, the resulting mixture should be without pigment, conglomerates and not to be highly viscous. In addition, the film coating formed as a heat-sensitive recording layer, should be hard and should not have the effect of desensitization. The content of the adhesive in the heat-sensitive color-forming layer is preferably from 8 to 20% relative to the quantity (in units solids) heat-sensitive color-forming layer. The content is less than 8% is unfavorable because the strength of the film for coating is reduced. The content of more than 20% causes the problem of decreasing sensitivity. To improve the resistance heat-sensitive color-forming layer can be used cross-linking agent for curing the resin.

In the color heat sensitive recording material of the present invention the formation of an intermediate layer between the heat-sensitive recording layer is effective for improving thermal separation. The intermediate layer includes as a major component of the same resin as motorstore the traveler or water-dispersible resin, used as the adhesive in the heat-sensitive recording layers, and may also include pigments, Poperechnaya agents and so forth. Covering the amount of the intermediate layer is preferably from 1.0 to 5.0 g/m2. When covering a number less than 1.0 g/m2cannot be obtained sufficient preventive effect on the diffusion between the recording layers, which leads to deterioration of image quality. When the covering amount is more than 5.0 g/m2the sensitivity is adversely reduced.

As a particularly preferred form may be mentioned color heat-sensitive recording material, in which two heat-sensitive recording layer have different citaprolamin temperature and subjected to the color display in different colors, respectively, are laminated on one side of the substrate, and of these recording layers of the upper heat-sensitive recording layer contains either agent used as a developer and as a reductant tone, or a reversible developer, and poorly heat-sensitive recording layer containing a urea-urethane compound developer.

Of them, the agent is used as the developer, and tone as the reducing agent, in the upper telecoustic enom recording layer is an amphoteric compound, having the acid group with a function of the degree of color development, and the main group with the function of bleaching, which perform the function of svetoprestavlenie when heated at a low temperature and function discoloration when heated at high temperatures. Typical examples of the acid group is a phenolic hydroxyl group or carboxyl group. A typical example of a primary group is the amino group. Although amphoteric compound may have a core group as a functional group, it preferably has a core group in the form of connection parts of salt, and in complex with compound phenol carbonic acids and aminoven connection. Specific examples of such agents are used as the developer, and as the tone of the reducing agent, as described below. Compound phenol carbonic acid, which is the main part of the agent that is used both as a developer and as a reductant tone, includes 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, Gallic acid, bis(4-hydroxyphenyl)acetic acid, 3,3-the IP(4-hydroxyphenyl)propionic acid, and so forth.

Amine compound, which together with phenol carbonic acid forms salts or complex salts, includes octylamine, nonylamine, decylamine, laurylamine, tetradecyl, heptadecyl, stearylamine, beginelement, 3-methoxypropylamine, hexamethylenediamine were and so on.

Reversible solvent is, for example, phenolic connection or phosphonic acid, which has an aliphatic hydrocarbon group of 8 or more carbon atoms. Specific examples of such reversible developer are listed below. Reversible developer is not limited to those mentioned below and can be used any reversible developer, provided that it has the function of the degree of color development by heating at a low temperature and discoloration when heated at a high temperature.

Reversible developer includes 4-(octadecylamino)phenol, 4-(dodecylthio)phenol, 4-(octadecylamino)phenol, 4-(dodecyloxy)phenol, N-octadecyl-4-hydroxybenzamide, 4’-hydroxyacetanilide, N-(4-hydroxyphenyl)-N’-n-octadecylamino, domainfactory acid and so on. When recording is performed on a thermal printer or the like using a color heat-sensitive recording material of the present invention, the printing by heating at a low temperature causes the appearance of the only low is Imperatorskogo color-forming layer and the printing by heating at a high temperature causes discoloration in the low-temperature color-forming layer in the printed part and causes the appearance of only high-temperature color-forming layer.

The use of urea-urethane compounds makes it possible to obtain products for laser marking, which has sufficient intensity of staining and gives so stable color image when printing, the image is slightly discolored or fade even under the action of fats and oils, chemicals, fingerprints and so on. Consequently, the use is particularly preferred from the viewpoint of long term storage of records.

Heat-sensitive recording layer products for laser marking according to the present invention preferably contains an agent that improves the recording sensitivity.

As an agent that improves the recording sensitivity used here, the connection is used, which is able to absorb the laser beam used for irradiation. Specific examples of such agents are of various inorganic compounds such as aluminum hydroxide, wollastonite, bentonite, mica (e.g., Muscovite and phlogopite), calcium silicate, talc, kaolin, clay and silicate minerals (e.g., foyaite, amphibole and albite). Especially preferred are aluminum hydroxide, white mica, wollastonite and kaolin. These inorganic compounds may be used independently and is in the form of their mixtures.

Proportion colorless or light-colored substances, precursor of the dye and the agent for improving the recording sensitivity, used in heat-sensitive recording layer of the present invention, is not specifically limited and may be appropriately selected depending on the type of substance used, the predecessor of the dye and the agent for improving the recording sensitivity. Usually the agent that improves the recording sensitivity may be used in proportions of from 10 to 5,000 parts by weight, preferably from 100 to 2,000 parts by weight, per 100 parts by weight of color-forming substance.

The substance of the dye precursor, urea-urethane compound developer and agent, which improves the recording sensitivity in the heat-sensitive recording layer may be set as follows: based ontotal mass (in units of solids) of the specified layer, of a substance is the predecessor of the dye is in the range from 5 to 30 wt.%, preferably from 10 to 25 wt.%, the content of the urea-urethane compound developer is in the range from 10 to 60 wt.%, preferably from 20 to 50 wt.%, and the content of the agent, which improves the recording sensitivity is in the range from 5 to 40 wt.%, preferably from 10 to 30 wt.%.

Also introduced is their acidic developer in the heat-sensitive recording layer products for laser marking according to the present invention improves the sensitivity and allows the product for laser marking to give brilliant color. As acidic developer is used above as examples of conventional electron-acceptor substance.

To further improve the sensitivity of products for laser marking according to the present invention can be introduced Caloplaca substance. Caloplaca substance is preferably one which has a melting point of from 60° to 180° With, in particular 80° to 140° C.

Color-forming composition for marking according to the present invention can be obtained using as a critical component of the above colorless or light-colored substances, precursor of the dye, urea-urethane compound developer, agent, improving the recording sensitivity, and water binding agent and water, and mixing them with various auxiliary substances, if necessary.

Used water color-forming composition for marking has a pH in the range from 5 to 12, preferably from 6 to 9. When pH is lower than 5, then formed a haze. When pH is higher than 12, then you are likely experiencing unwanted effects, such as reduced color-forming ability of the urea-urethane compound developer. Water can be used in a mixture with water-soluble organic solvent, such as methanol, ethanol or the like./p>

In addition to the essential components described above, various excipients may, if necessary, be entered in the color-forming composition for marks used in the present invention, for example, to facilitate application of the composition on the substrate. Various excipients include, for example, dispersing agents (for example, dioctylsulfosuccinate sodium, dodecylbenzenesulfonate sodium, the sodium salt of the ester of lauric alcohol and sulfuric acid, and metal salts of fatty acids), shading agents (e.g. titanium oxide), antifoaming agents, viscosity modifiers, and fluorescent dyes, and coloring agents.

The substrate, on which (print) applied a color-forming composition for marking according to the present invention is not specifically limited provided that are necessary for marking. As a substrate, you can specify, for example, pre-split food containers, packaging materials, electronic components and the like, and articles (for example, substrates for labeling), they are done. As a substrate for shortcuts, depending on the purpose, essentially used paper (such as paper and synthetic paper, synthetic resin film, plastic, metalized paper and synthetic paper, metallizirovanaya film, m is of Tallaght, wood and so on.

Citabrias composition for marking obtained as follows. The binding agent is dissolved or dispersed in water or in a solvent consisting mainly of water. Among the components that can be dispersed in water or a solvent consisting mainly of water, are color-forming compounds, developer, agent, improving the recording sensitivity, and the like, which are processed together or independently with water or aqueous solvent which contains a dispersing agent, such as poly(vinyl alcohol), using the apparatus for dispersion, such as ball mill, cage mill, sand mill or the like, obtaining, thus, one or more of the dispersions. The average particle size of each component after dispersione is usually about 2 μ or less, preferably about 1 μ or less. Then mixed binding agent and the variance(and) to obtain the color-forming composition for marking according to the present invention. The solids content in the specified color-forming composition for marking ranges from 20 to 70 wt.%, preferably from about 30 to about 65 wt.%.

Color-forming composition for marking may Rositsa directly on the substrate or may be applied to the substrate, previously subjected to surface treatment, causing the substrate or the like. The application can be carried out using a suitable installation for coating, for example, can be carried out using a roller device for applying a coating device for coating corrugated roller, miroustroistva for coating corrugated roller, knife device for a coating device for coating by sputtering or the like. The thickness of the coating film (heat-sensitive recording layer obtained by applying and drying can usually be set from 1 to 4 μ . When the thickness is less than 1 μ then the manifestation of color laser irradiation is insufficient, in addition, the film coating is prone to peeling. On the other hand, when the thickness is more than 4 μ , drying characteristics and adhesiveness shortcut prone to deterioration. Drying varies depending on the conditions of the coating, such as conveyor speed, and can be conducted either at room temperature or when heated under conditions that do not cause color formation in the heat-sensitive recording layer.

The protective layer products for laser marking according to the present invention is obtained by applying a transparent liquid coating h is heat-sensitive recording layer. Transparent liquid coating is an aqueous composition comprising a water-binding agent, water and the like.

As a water binding agent used in the transparent liquid coatings for protective layer in the present invention, it is possible to mention the one that was obtained using as the basis of essentially known water-soluble or water-dispersible resin used in the substance of the coating or ink. This resin has a hydrophilic group (for example, carboxyl group or amino group), it is not necessarily made there to impart water solubility or FotoDepartament. As mentioned resins for water binding agent used for the resin having a glass transition temperature in the range from 20 to 80°C., preferably from 35 to 70° C. When the glass transition temperature is lower than 20°, abrasion resistance, chemical resistance, water resistance and the like of the protective layer deteriorates. On the other hand, when the glass transition temperature higher than 80°C., the protective layer becomes brittle, slightly elastic, and the like, and breaks easily. Therefore, both of such glass transition temperature are undesirable. If necessary, in addition to the components described above, in the above-mentioned transparent liquid coating can be entered leveling among the STV, agents, imparting sliding properties, defoamers and the like.

As a water binding agent used in the transparent liquid coating can be obtained acrylic resin using alkilany (the number of carbon atoms: 1 to 24) ester of acrylic acid or methacrylic acid as a main component in combination with any of, for example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and so on; hydroxycobalamin unsaturated monomers, such as hydroxyethylacrylate, hydroxypropylmethacrylate and so on; amino compounds unsaturated monomers, such as acrylamide, methacrylamide and so forth; and other unsaturated monomers such as styrene, Acrylonitrile, vinyl acetate, vinyl chloride, and so forth, and copolymerize akrilovye esters such co monomer. Polyester resin can be obtained ester reaction polonovski acid (including acid anhydrides)having two or more carboxyl groups in the molecule, with a polyhydric alcohol having two or more hydroxyl groups in the molecule. The glass transition point of such a water-binding agent can be set to any temperature essentially, when choosing the type, combination and proportions of the components that make up the specified binder.

Found pet is acou liquid obtained by dissolving or dispersing the above-mentioned water-binding agent in a suitable water, and if necessary, the introduction together with the leveling agents, agents, giving southwestairline, defoamers and the like. A solid component of the specified transparent liquid coating is in the range from 20 to 70 wt.%, in particular from 30 to 60 wt.%.

The specified transparent liquid coating can be printed(applied) on the surface of the dried film formed as a heat-sensitive recording layer. A printing method (application) is not specifically limited. The application can be carried out using a roller device for applying a coating device for coating corrugated roller, miroustroistva for coating corrugated roller, knife device for a coating device for coating by sputtering or the like.

The thickness of the coating film, thus obtained, can usually be set from 3 to 10 μ . When the thickness is less than 3 μ then protect heat-sensitive recording layer using the specified transparent coating is insufficient, and the chemical resistance, abrasion resistance and the like deteriorates. On the other hand, when the thickness is more than 10 μ , drying characteristics and physical characteristics of the covering film is prone to deterioration. Drying the specified transparent PVC is offered by the liquid coating varies depending on the conditions of the coating, such as the conveyor speed, and can be conducted either at room temperature or when heated under conditions that do not cause color formation in the heat-sensitive recording layer.

When the thus obtained heat-sensitive recording layer products for marking irrationals laser beams, radionovela part is heated, thus the urea-urethane compound developer and matter-of predshestvennika dye interact with each other with the formation of the color, which leads to labeling. Although the amount of energy of a laser beam used for irradiation is not specifically limited, it is preferably 1,4 J (Joule/cm2or less, if you take into account the possibility of cracking of the film. On the other hand, although the lower limit of the amount of energy required for the manifestation of color, is unknown, as there is no device that can give a low enough energy manifestation of color takes place even when the amount of energy of 0.4 J/cm2. Therefore, a suitable amount of energy of irradiation for the formation of color is found in the region from 0.4 to 1.4 J/cm2in particular from 0.45 to 1.2 J/cm2. As a laser used for irradiation, suitable is a pulsed laser or a scanning laser. As for the type of laser can be used I the th laser, for example, gas lasers, excimer lasers, and semiconductor lasers. Specific examples of the laser lasers are carbon dioxide mixed gas lasers, YAG lasers garnet, ruby lasers, and so forth.

As a way of erudirovana part of the desired shape laser beams can be mentioned a method of irradiation of the coating film laser beams through a metal mask for exposure of the coating film by the laser beams in accordance with the shape of the opening of the metal mask; and a method of introducing a desired shape in the computer and the irradiation of the coating film by the laser beams in accordance with the desired form by way of the so-called drawing with one stroke. When the heat-sensitive recording layer is irradiated with laser beams, exposed part of the core temperature increases to expose the color formation caused by melting and mixing the color-forming components in the heat-sensitive recording layer, which leads to the appearance of letters or numbers that have the exact desired shape. It changes color with exposure can be performed instantaneously, as the energy density of the laser beams is high.

Label as products for laser marking according to the present invention can be obtained by formation of a heat-sensitive recording layer and protect the private layer of the above methods on a substrate for the label, essentially selected depending on the purpose of the paper (such as paper and synthetic paper, synthetic polymer films, plastic, metalized paper and synthetic paper, metallisierung films, metals, wood and so on. Although the resulting shortcut can be used in all areas of conventional labels, it is preferably used in applications, in particular in the food, medicine, perfumery, book publishing, electronics and electronic parts and so on.

The packing material as products for laser marking according to the present invention is obtained by the formation of heat-sensitive recording layer and the protective layer of the above methods, any of various conventional packaging materials such as boxes, wrapping paper and bags, which are produced using the substrate essentially selected depending on the purpose of the paper (such as paper and synthetic paper, synthetic polymer films, plastic, metalized paper and synthetic paper, metallisierung films, metals, wood and so on. Although the resulting shortcut can be used in all areas of conventional labels, it is preferably used in applications, in particular in the food, medicine, perfumery, book publication, the electron is ke and electronic parts and so on.

The container as products for laser marking according to the present invention is obtained by the formation of heat-sensitive recording layer and a protective layer on the substrate, such as glass, plastic, metal or the like, the above-mentioned ways. This food container can be used as a conventional food containers, such as bottles for beverages and soft drinks, a rotary food containers, food containers for fast food, containers for cosmetics, medical containers, products, perfumes and so on.

When the color-forming composition of the present invention is used in the recording material, a pressure-sensitive recording material can have, for example, of the form described in U.S. patent No. 2505470, 2712507, 2730456, 2730457 and 3418250 and so on. There can be used various forms, such as the ones listed below: recording paper, pressure-sensitive, obtained by dissolving substances, precursor of the dye or mixture of substances, precursor of the dye in the solvent, containing one or a mixture of two or more alkyl naftalina, alkyl biphenyls, alkyl diphenylmethane, alkyl giarratano, synthetic oils (e.g., chlorinated paraffin), vegetable oils, is animal oils, mineral oils and so forth, by dispersing the resulting solution in a binder agent, or the introduction of a solution in microcapsules, causing the dispersion to the substrate or causing the microcapsules to the substrate together with a binder agent, placing the bottom of the paper thus obtained, and the top of the paper coated with the dispersion of the urea-urethane compounds (and aminoguanidinium and/or developer, and so on)each other so that their coated surfaces were facing each other; a recording paper, pressure-sensitive, obtained by the fixation between the aforementioned upper paper and bottom paper, intermediate paper coated with dispersion the urea-urethane compound on one side and the substance is a precursor of the dye on the other groans; a pressure-sensitive recording paper of mixed type, obtained by coating the above dispersion of the urea-urethane compounds and amino compounds and/or developer) and the above dispersion containing substance is precursor of dye on one surface of the substrate in the form of a mixture or multilayer form; and a pressure-sensitive recording paper of mixed type, obtained by the inclusion of each substance, precursor of the dye and urea-urethane compounds and amino compounds and/or developer) in microcapsules and grease the m mixture of two kinds of microcapsules on the same surface of the substrate.

As a method of producing microcapsules can be used, for example, the way koatservatsii described in U.S. patent No. 2800457 and 2800458, the method of interfacial polymerization described in patent JP-B-38-19574, JP-B-42-446 and JP-B-42-771 and so forth, the in situ method described in JP-B-36-9168, JP-B-51-9079 and so on, a method of cooling molten dispersion described in UK patent No. 952807 and 965074 and so forth, and a method of drying-spray, described in U.S. patent No. 311140, the United Kingdom patent No. 930422 and so on.

Color-forming composition of the present invention corresponds to a combination of substances, precursor of the dye developer described in each of the above link, and the like.

For formation of the recording layer, pressure-sensitive, each component, such as a urea-urethane compound can be used in the form of a solution or dispersion in a solvent. In the case of the color-forming system, optionally containing aminosilane and/or developer, each component can be used in the form of a solution or dispersion in a solvent, or a combination of the urea-urethane compounds, amino compounds and optional developer can be used in the form of a solution or dispersion in a solvent.

In the above methods, interfacial polymerization, is used to obtain microk the purs, the film is formed at the interface, using two types of monomers, i.e. oil monomer and a water-soluble monomer. Known, for example, the way in which the chloride polonovski acid is used as the oily phase and polyvalent amine as the aqueous phase and the polyamide film is obtained on the boundary; the way in which the chloride polonovski acid is used as the oil phase and polyhydric gidroksosoedinenii is used as the aqueous phase and the polyester film is formed on the boundary; the way in which the polyvalent isocyanate is used as the oil phase and the polyhydric alcohol or polyhydric phenol as the aqueous phase, and the polyurethane film is formed at the interface; and a technique in which the polyvalent isocyanate is used as oil phase and polyvalent amine as the aqueous phase, and polyurethane film is formed on the banks of the section. Thus, when the method of interfacial polymerization is used for the production of microcapsules, isocyanate compound used in some cases as a reactive monomer for formation of a film.

In this case, the specified isocyanate compound is consumed for the formation of a film of microcapsules and do not directly relate to occurrence of color depicted is I, and it is absolutely necessary to use a water-soluble monomer together with the isocyanate compound. In these cases, its use differs from the use of isocyanate compounds of the present invention.

Dispersion of compounds that are not filled microcapsules, get fine grinding of one or more compounds as a component in an aqueous solution containing a compound having a dispersive ability, such as water-soluble polymer, surfactant or the like. The urea-urethane compound may be dispersed together with aminoguanidinium and acidic developer.

As the substrate used in pressure-sensitive recording material, mainly used paper, although depending on the purpose, other than paper may be used in a variety of woven material, nonwoven material, a synthetic polymer film, laminated paper, synthetic paper, metal foil and the composite sheets obtained by combining two or more of them.

As a bonding agent may be used various binding agents. Binder includes, for example, water-soluble binders such as starches, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose gelatin, casein, poly(vinyl alcohol)s, modified poly(vinyl alcohol)s, poly(acrylate)s sodium, copolymers of acrylamide-acrylic ester, terpolymer acrylamide-acrylic ester-methacrylic acid copolymers, alkali salts of styrene-maleic anhydride copolymers, alkali salts of ethylene-maleinovogo anhydride and the like; and water-insoluble latex binders of the type selected from copolymers of styrene-butadiene, copolymers acrylontrile-butadiene, copolymers of acrylate-butadiene and so on.

In the recording material of the present invention, the recording layer may contain a connection difficulty phenol or an ultraviolet absorber. Hindered phenol or an ultraviolet absorber includes, for example, 1,1,3-Tris(3’-cyclohexyl-4’-hydroxyphenyl)butane, 1,1,3-Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 4,4’-THIOBIS(3-methyl-6-tert-butylphenol), 1,3,5-trimethyl-2,4,6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,2’-dihydroxy-4,4’-dimethoxybenzophenone, p-octylaniline, 2-(2’-hydroxy-5’-were)benzotriazole, ethyl-2-cyano-3,3’-diphenylacetate and Tetra(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylic.

A method of obtaining color-forming layer are not specifically limited. Color-forming layer receive, for example, applying a liquid coating to color-forming layer on the substrate p is chodashim coating method, such as curtain coating with the free fall, coated with an air knife, blade coating Bariber, pure blade coating, or the like, and drying the thus obtained substrate. Covering the amount of liquid coatings for color-forming layer are not specifically limited and is typically set in the range from 1 to 15 g/m2preferably about 3 to 10 g/m2in terms of dry weight.

Thermal response can be improved by formation of an intermediate layer between the heat-sensitive recording layer and the substrate. In the case of conventional heat-sensitive recording materials, for example, can be used sharing Caloplaca material in the color-forming layer. Improving the sensitivity of such a method is advantageous due to the fact that during heating or friction tends to cause fog. This facilitates the occurrence of fog especially in the heat-sensitive recording materials obtained with the use of the urea-urethane compound developer, excellent sensitivity the degree of color development. In the case of conventional heat-sensitive recording materials without saving printing, even if the mist is formed, it disappears like a thumbprint, so, in particular, the fog in the case of use of the recording material after storage rarely accept malsa into account. However, in the case of heat-sensitive recording materials obtained with the use of the urea-urethane compound developer, especially excellent for long-term storage of print, the following problem is typical of them, occur in some cases: appearing once the fog is saved and, therefore, accumulates each time the storage of the recording material and then use, thus the surface of the recording material becomes dirty when the recording material is used after long storage. In this case, the formation of the intermediate layer can be achieved practical sensitivity of the degree of color development without using Caloplaca material or using only a small amount Caloplaca material, and can be obtained heat-sensitive recording material, which is so excellent resistance to the formation of fog by heating or friction, the fog is hardly accumulated, even if the recording material is used after long-term storage.

The intermediate layer is composed mainly of an organic or inorganic pigment, hollow particles and a water-binding agent, such as water-soluble polymer or latex. As an organic or inorganic pigment and water tie the existing agent can be used the same organic or inorganic pigment and a water-binding agent, used in heat-sensitive recording layer.

The method of obtaining the intermediate layer is not specifically limited. As this method can be applied the method to obtain heat-sensitive recording layer. Dry distribution to obtain the intermediate layer is in the field, preferably from 2.0 to 15.0 g/m2. In this case, the pH on the surface of the intermediate layer obtained on the substrate, is preferably from 3 to 9, more preferably from 5 to 9, more preferably from 6 to 8.

In addition, in the present invention, the abrasion resistance of the obtained recording paper, if necessary, can be improved by formation of a protective layer composed mainly of a water-soluble polymer, heat-sensitive recording layer. When using urea-urethane compound developer of the present invention, which has excellent sensitivity to the manifestation of color and stability of the imprint during long-term storage, due to the high sensitivity can be left traces of friction. On the other hand, once left traces of friction persist for an indefinite time and, consequently, the friction traces are accumulated each time the storage of the recording material and then use. So Boo is the most important surface in some cases becomes dirty, when the recording paper is used after long-term storage. In this case, when forming the protective layer, the accumulation of traces of friction can be difficult, even if the recording paper is used after long-term storage. Specific examples of water-soluble polymer contained in the protective layer are water-soluble polymeric binding agents that are listed on the above-mentioned thermosensitive recording layer. Water-soluble polymer can be used in conjunction with conventional waterproofing agent capable of gidroizolirovat water-soluble polymer. Specific examples of the waterproofing agent include formaldehyde, glyoxal, chrome alum, melamine, melamine-formaldehyde resin, polyamide resin, polyamide-epichlorohydrine resin and so on.

In addition, pigments, metal soap, wax, Poperechnaya agents and so forth included in the protective layer in order, for example, improve compliance with thermal head during the printing process and improve the water resistance of the protective layer.

Pigments include zinc oxide, calcium carbonate, barium sulfate, titanium oxide, lithopone, talc, pagoda, kaolin, aluminum hydroxide, silica, amorphous silica, and so forth. The amount of added pigment is from 0.5 to 4 times, predpochtitelno of 0.8 to 3.5 times from the total mass of the polymers. When the number is below the lower limit mentioned above, the pigments are not effective to improve compliance with thermal head. When the number is above the upper limit, the sensitivity of the heat-sensitive recording material is remarkably reduced so that the commercial value of the recording material is reduced.

Metal Soaps include, for example, emulsions, metal salts of higher fatty acids such as zinc stearate, calcium stearate, aluminum stearate, and so forth. Metallic Soaps are added in proportions of from 0.5 to 20 wt.%, preferably from 1 to 10 wt.%, on the basis of the total mass of the protective layer. Waxes include, for example, emulsions of solid wax, microcrystalline wax, Carnauba wax, mediastreamer, polyethylene wax, and so forth. Wax was added in a proportion from 1 to 20 wt.%, preferably from 1 to 10 wt.%, on the basis of the total mass of the protective layer.

When the formation of a protective layer on the heat-sensitive recording layer to the liquid to cover, add a surfactant to form a protective layer, to obtain a uniform coating layer. Surfactants include alkali metal salts sulfonating acids, fluorine-containing surfactants, and so forth. To ncrete examples of surfactants include sodium or ammonium salts of di(2-ethylhexyl)sulfonterol acid, di-(n-hexyl)sulfonterol acid and so on. Effective in General is any surfactant, provided that it is anionic. In the protective layer may also contain the usual adjuvants such as fillers, Caloplaca materials (lubricants, surfactants, fluorescent dyes, and so forth. Specific examples of fillers, Caloplaca materials and fluorescent dyes are specified relative to the above-mentioned heat-sensitive recording layer. Dry distribution to obtain the protective layer is in the area of preferably from about 0.5 to about 10 g/m2in particular from about 1 to about 5 g/m2.

When using the retrieval method of the present invention on the rear side relative to the recording layer of the recording material to form a layer of the reverse side (back coating layer), if necessary, twist the obtained recording paper can be difficult. Especially in the case of the urea-urethane compound developer according to the present invention the formation of a layer on the reverse side is effective for the following reason: the specified developer outperforms other developer on the ability of the dispersion, which easily gives the dispersion of small particles, and has you will fetter sensitivity, but, when the liquid coating is obtained by mixing the specified developer with other necessary components, is applied to the substrate, adhesive force of a binding agent increases during drying due to the small particle size of the developer, therefore, the recording layer is easier compressed. In kachestvennostju liquid coating layer for the inside and method of coating the liquid coating can be used the same components and method as in the case of protective recording layer. Dry the distribution of the liquid coating is in the area of preferably from 2.0 to 10.0 g/m2.

The present invention is described in more detail in the following examples.

The analysis of substances and evaluation of physical properties were conducted by the following methods.

<IR spectrum>

Measured diffuse reflective spectroscopy using FTIK-8100M, production Shimadzu Corp.

<Mass spectrum>

Was measured using JMS-HX100, production JEOL LTD., nitrobenzyloxy alcohol as matrix and xenon as the primary gas.

<Sensitivity manifestations color thermal paper>

The intensity of this color when a voltage is 24 V and pulse duration of 1.5 MS was measured by an optical densitometer, using the printing device for testing, production Ohkura Denki K.K., and thermal g is lovko > KJT-256-8MG, production Kyocera Co., Ltd.

<a Resistance to plasticizer>

Heat-sensitive recording material was installed between vinyl chloride wrapping film or vinyl chloride file, and on top of it was applied load of 300 g/cm2. After 24 hours at 40° visually estimated the intensity of this color is printed parts and neotectonic part (the original surface of the recording material). When observed only a small decrease in the intensity of the printout, then the storage capacity of the print was evaluated as optimal.

<a thermal resistance of>

Heat-sensitive recording material was left at 60° C and relative humidity of 25% within 24 hours and visually assessed the degree of fading of the print. When the degree of discoloration was evaluated as low, then the storage capacity of the print was evaluated as optimal.

In addition, the heat-sensitive recording material was left at 80° C and relative humidity of 25% within 24 hours and visually assessed the degree of fading of the print. When the degree of discoloration was evaluated as low, then the storage capacity of the print was evaluated as optimal. Also visually estimated the intensity of this color is the original surface of the recording material. When observed only n is large, decrease the degree of color development, then the ability to preserve the original surface of the recording material was evaluated as optimal.

<the Intensity of staining of paper, pressure sensitive>

The top paper and the bottom paper placed one on another so that their coated surfaces in contact. The top was put on the pressure to get a color image on the bottom of the paper. The intensity of staining obtained color image was measured using Macbeth densitometer RD917.

<Resistance to solvents>

Hand cream (Atrix, trade name, made. Kao Corp.) put a thin layer on a portion of the color image obtained in the evaluation of staining intensity, and then left at ambient temperature for 7 days and were visually evaluated the intensity of staining. When observed only a small decrease in the intensity of the printout, then the storage capacity of the print was evaluated as optimal.

Example 1

To 27.8 g of 2,4-toluene diisocyanate was added 111 g of toluene as the solvent, and then was added dropwise a solution of 7.4 g of aniline in 37 g of toluene at room temperature for 1 hour and the interaction was carried out for another 1 hour. The white solid precipitate was obtained by filtration, washed with hexane and then dried overnight in vacuum to obtain 20 g of white crystal is impressive. Then 5 g of the thus obtained compounds were added in 50 ml of methanol and the interaction was carried out at 60° C for 30 minutes, after which the excess methanol was removed using an evaporator, and to effect crystallization to the precipitate was added toluene. The obtained white crystals were isolated by filtration, washed with hexane and then dried overnight in a vacuum with the receipt of 5.4 g of white crystals. The melting point of these white crystals were 196° C.

Analytical measurement of these white crystals showed the following.

The result of IR measurement:

The characteristic peaks were located at 1060 cm-1, 1250 cm-1, 1600 cm-1, 1650 cm-1, 1670 cm-1, 1700 cm-1and 3300 cm-1,

It was proved that the structural formula of the main component of this compound is structural formula of the above compound (S-1).

Then got a dispersion by dispersing 2 g of this compound, crushing it together with 8 g of 2.5 wt.% an aqueous solution of polyvinyl alcohol (Gohseran L-3266, trade name, made. The Nippon Synthetic Chemical Industry Co., Ltd.) in a paint shaker for 6 hours. The temperature of the dispersion immediately after the dispersion was 25° C. the Diameter of dispersed particles of the compound was approximately 0.6 microns.

Another dispersion was obtained by dispersing 70 g of 3-dibutylamino-6-ethyl-7-onlineflorida, crushing it with an aqueous solution of 130 g of a 8 wt.% polyvinyl alcohol in a sand mill (made. AIMEX CO., LTD.; tank volume 400 ml) with the number of revolutions of 2000 rpm for 3 hours.

Another dispersion was prepared by dispersing 70 g of diphenylsulfone, crushing it together with a water solution of 130 g of a 5.4 wt.% polyvinyl alcohol in a sand mill (made. AIMEX CO., LTD.; tank volume 400 ml) with the number of revolutions of 2000 rpm for 3 hours.

Another dispersion was prepared by mixing 10 g of calcium carbonate, 30 g of water and stirring the mixture using a mixer.

Covering liquid was obtained by stirring and mixing the above-mentioned dispersions and other components in the following proportions (the proportions of dry basis); the variance of the above compounds in terms of dry solid substance: 30 parts by weight, the dispersion of the 3-dibutylamino-6-methyl-7-onlineflorida in terms of dry solid substance: 15 parts by weight, dispersion of diphenylsulfone in terms of dry solid substance: 30 parts by weight, dispersion of calcium carbonate in terms of dry solid substance: 20 parts by weight, dispersion of zinc stearate (solid content: 16 wt.%) in terms of dry solid substance: 10 parts by mass and 15 wt.% poly(vinyl alcohol) in terms of dry solid substance: 7 parts by weight.

Covering the liquid was applied to the main paper with a weight basis of 50 g/m2using the installation for the coating to remove excess using a strap with a pin number 10. After drying were supercalendering obtaining thermosensitive recording material. Covering the covering number of the liquid was 4 g/m2in terms of dry mass.

The result of evaluating the sensitivity of the obtained heat-sensitive recording material was so optimal that the optical density was 1.2. The result of the assessment of the degree of thermal change the color of the original surface of the recording material (thermal resistance) was so good that the color change has been neglected. Thermal fading of the printed part was desirable weak. The results of these evaluations are summarized in table 1.

Example 2

To 17 g of 2,4-colordistance was added 40 g of methyl ethyl ketone as the solvent, and then thereto was added dropwise 3.8 g of methanol, and perform the interaction with stirring at 60° C for 5 hours. Then there was added to 9.9 g of 4,4’-diaminodiphenylsulfone and have interaction with stirring at 60° C for 4 hours. After the interaction the resulting solution was cooled to room tempera is URS and poured into 800 g of acetonitrile, and the crystalline precipitate obtained by filtration, washed with hexane and then dried overnight in vacuum to obtain 15 g of compound as white crystals.

The melting point of white crystals was 169° and their analytical measurement were as follows.

The result of IR measurement:

The characteristic peaks were located at 1220 cm-1, 1550 cm-1, 1590 cm-1, 1660 cm-1, 1740 cm1-and 3300 cm-1.

The results of the analysis of mass spectrum:

[M+H]+identified at m/z 661.

It was proved that the structural formula of the main component of this compound is structural formula of the above compound (S-13).

Then heat-sensitive recording material was obtained in the same manner as described in example 1, except that instead of the urea-urethane compound synthesized in example 1 was used the compound, obtained above, and evaluated it. The results obtained are summarized in table 1.

Example 3

In 100 ml of ethyl acetate was dissolved of 3.46 g of aniline and the resulting solution was stirred at room temperature. It was added dropwise a solution of 10 g trimethylolpropane adduct selected from toluene diisocyanate (Coronate L, trade name, made. Nippon Polyurethane Industry Co., Ltd.; 75% ethyl acetate solution) in 50 ml of ethyl acetate for 1 hour and were conducted entries batch is f for another 30 minutes. The resulting crystals were isolated by filtration and dried overnight in vacuum to obtain a 5.1 g of compound as white crystals. The melting point of white crystals was 161° and their analytical measurement was as follows. The result of IR measurement:

The characteristic peaks were located at 1070 cm-1, 1220 cm1-, 1550 cm-1, 1600 cm-1, 1700 cm-1and 3300 cm-1.

It was proved that the structural formula of the main component of this compound is structural formula of the above compound (S-33).

Then heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1 was used the compound, obtained above, and evaluated it. The results obtained are summarized in table 1.

Example 4

To 10.4 g of 2,4-colordistance was added 20 g of methyl ethyl ketone as the solvent, and then thereto was added dropwise a solution of 3.7 g of 4,4’-diaminodiphenylsulfone dissolved in 30 g of methyl ethyl ketone, and the interaction was carried out at ambient temperature for 20 hours. After completion of the interaction of methyl ethyl ketone was removed by concentration and then to the precipitate was added toluene, and the white solid precipitate was obtained by filtration, washed with hexane and then dried in a t is the significance of nights in vacuum to obtain 8.8 g of the compound in the form of white crystals. Then 4 g of the obtained compound were added 15 g of phenol, and then a small amount of dibutyltindilaurate, and the interaction was carried out at 50° C for 4 hours. After the interaction in the reaction solution was added toluene, and the crystalline precipitate obtained by filtration, washed with hexane and then dried overnight in vacuum to obtain 5.2 g of the urea-urethane compound as white crystals.

Then the solvent was added 30 g of toluene, 10 g of 2,4-colordistance, and then thereto was added 30 g of phenol, and the interaction was carried out at 100° C for 3 hours. After the interaction, the toluene was removed by concentration and to the precipitate was added hexane. A white crystalline precipitate obtained by filtration, washed with hexane and then dried overnight in vacuum to obtain 15 g of urethane compound as white crystals.

It was proved that the structural formula of the main component of this compound is structural formula of the compound (C-2), described further here.

Then 3 g of the above urea-urethane compound and 2 g of urethane compounds were mixed to obtain a urea-urethane composition. Thereafter, 2 g of urea-urethane compositions were crushed together with a water solution of 8 g of 2.5 wt.% methylcellulose in the cocktail shaker to the ASCI within 45 minutes for dispersion, thus was obtained a dispersion.

Then heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1 was used the compound, obtained above, and evaluated it. The results obtained are summarized in table 1.

Example 5

Heat-sensitive recording material was obtained in the same manner as in example 4, except that instead of a urea-urethane composition used in example 4 used a urea-urethane composition obtained by mixing 4.5 g of the urea-urethane compound and 0.5 g of urethane compounds, which were synthesized in example 4, and was evaluated. The results obtained are summarized in table 1.

Example 6

Heat-sensitive recording material was obtained in the same manner as in example 4, except that instead of a urea-urethane composition used in example 4 was used to 7.4 g urea-urethane composition obtained as white crystals by the same method as in example 4, except that was added 2.2 g of diphenylsulfone in the reaction system before precipitation by adding toluene after the synthesis reaction of the urea-urethane compound by stirring the resulting mixture, add the Yaya in a mixture of toluene, getting a crystalline precipitate by filtration, by washing the crystals with hexane and then by drying the crystals over night in a vacuum. Estimated heat-sensitive recording material. The results obtained are summarized in table 1.

Example 7

To 31,5 g of 2,4-colordistance was added dropwise a solution of 21.5 g of 4,4’-diaminodiphenylsulfone in 60 ml of MEK at 70° under stirring at 300-500 rpm for 4 hours, and the interaction was carried out for 4 hours to obtain a white viscous suspension of the reaction mixture. Then the reaction mixture was cooled to 50° and the reaction mixture was poured 17.1 g of phenol to dissolve it, and then as a catalyst to it was added 0.015 g of triethylamine, and the interaction was carried out for 4 hours to obtain a yellow, transparent and viscous reaction mixture. This reaction mixture was freed from solvent and concentrated under reduced pressure to harden, after which the solid product was ground and then dried overnight in vacuum to obtain approximately 70 g of a urea-urethane composition in the form of light yellow powder.

The melting point of light yellow powder was 160-180° C. In the IR measurement of powder broad peak formed by applying the characteristic peaks of the group of urea and urethane groups, respectively, n is located at 1700 cm -1.

The content of the urea-urethane core component in the urea-urethane composition was 68%, as shown by measurement using liquid chromatography.

Then heat-sensitive recording material was obtained in the same manner as in example 1, except for using the above composition instead of the urea-urethane compound synthesized in example 1 and evaluated.

The results obtained are summarized in table 1.

Example 8

To 158,5 g of 2,4-colordistance as a solvent was added 240 g of methyl ethyl ketone and there was added to 107.5 g of 4,4’-diaminodiphenylsulfone in the form of a powder at 30° under stirring at 400 rpm for 8 hours. After 1 hour there was added 26 g of methyl ethyl ketone and stirred for another 15 hours to obtain a white viscous suspension of the reaction mixture. Then the solution to 89.5 g of phenol 15.8 g of methyl ethyl ketone was poured into the reaction mixture to dissolve it, then as catalyst there was added 9.3 g of 1 wt.% a solution of triethylamine in ethyl ketone for 2 hours, and the interaction was continued for 1 hour. After the reaction mixture was cooled to 20°C and continuously stirred for 3 hours to obtain a suspension containing fallen slightly yellow crystals. Suspension was freed from solvent and concentrated under reduced Yes is the process for hardening, then the obtained solid product was ground and then dried overnight in a vacuum with getting 355 g urea-urethane composition in the form of a slightly yellow powder.

The melting point slightly yellow powder was 130-170° C. When the IR measurement of powder broad peak obtained by applying the characteristic peaks of the group of urea and urethane groups, respectively, are located at 1700 cm-1. The content of the urea-urethane core component in the urea-urethane composition was 65%, as shown by measurement using liquid chromatography.

Then heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1 was used the compound, obtained above, and evaluated it. The results obtained are summarized in table 1.

Example 9

To 27.8 g of 2,4-colordistance was added 100 g of toluene as a solvent, after which there was added dropwise a solution of 7.4 g of aniline in 37 g of toluene at room temperature for 1 hour, and the interaction was carried out for another 1 hour. The white solid precipitate obtained by filtration, washed with hexane and then dried overnight in vacuum to obtain 20 g of white crystals. Then 5 g of the thus obtained compounds were added to the 50 ml of methanol, and the interaction was carried out at 60° C for 30 minutes, after which the excess methanol was removed using an evaporator, and the residue was dried over night in vacuum with the receipt of 5.4 g of a urea-urethane composition in the form of white crystals. The melting point of white crystals was 196° C. When the IR dimension of the crystals of the characteristic peaks of the urea-urethane compounds are at 1670 cm-1and 1700 cm-1. The content of the urea-urethane core component in the urea-urethane composition was 92%, as showed measurement using liquid chromatography.

Then heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1 was used the compound, obtained above, and evaluated it. The results obtained are summarized in table 1.

Example 10

To 17 g of 2,4-colordistance as a solvent were added 40 g of methyl ethyl ketone, after which was added dropwise over there and 3.8 g of methanol, and the interaction was performed under stirring at 60° C for 5 hours. Then there was added to 9.9 g of 4,4’-diaminodiphenylsulfone, and the interaction was performed under stirring at 60° C for 4 hours. After the interaction of the solvent was removed methyl ethyl ketone, using ESPAR the tel, and the residue was dried overnight in vacuum to obtain 16 g of a urea-urethane composition in the form of white crystals. The melting point of white crystals was 169° C. When the IR dimension of the crystals of the characteristic peaks of the urea-urethane compounds are at 1660 cm-1and 1740 cm-1. The content of the urea-urethane core component in the urea-urethane composition was 52%, as shown by measurement using liquid chromatography.

Then heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1 was used the compound, obtained above, and evaluated it. The results obtained are summarized in table 1.

Example 11

253 ml of toluene was dissolved 27.5 g of 2,4-colordistance, then was dropwise added a solution of 14.7 g of aniline in 85 ml of toluene at 40° under stirring at 200 rpm for 30 minutes, and the interaction was carried out for another 30 minutes. To the thus obtained white suspension was added 18.0 g of 2,2-bis(4-hydroxyphenyl)propane, 262 ml of toluene and 0.42 mg of triethylamine as a catalyst, and the mixing speed was increased to 400 rpm To prevent aggregation of particles in suspension in the initial reaction by controlling the degree of interaction of interaction is otherwise carried out in a phased increase of the reaction temperature as follows: 60° C for 5 h, 65° C for 2 h, 70° C for 1 h and 75° C for 1 h and Then added 0,42 mg of triethylamine, and the interaction was carried out at 80° for a further 8 hours, the Reaction mixture was cooled to room temperature and the resulting white crystals were isolated by filtration. White crystals were dried overnight in vacuum to obtain 59 g of a urea-urethane composition in the form of white crystals. The melting point of these white crystals was 170° C. When the infrared analysis of the crystals broad characteristic peak of the urea-urethane compound was located at 1720 cm-1. The content of the urea-urethane core component in the urea-urethane composition was 81%, as shown by measurement using liquid chromatography.

Then heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1 was used the compound, obtained above, and evaluated it. The results obtained are summarized in table 1.

Examples 12-23

Heat-sensitive recording material was obtained in the same manner as in example 8, except for using 4,4’-dichlorodiphenylmethane (example 12), 4,4’-dihydroxydiphenylsulfone (example 13), 2,4’-dihydroxydiphenylsulfone (example 14), 4-(benzyloxy)pheno is a (example 15), salicylanilide (example 16), 4,4’-diaminodiphenylsulfone (example 17), 4,4’-dichlorobenzophenone (example 18), 4,4’-diaminodiphenylmethane (example 19), 4,4’-dimethoxybenzophenone (example 20), diphenylcarbonate (example 21), 4,4’-dimethoxyphenylacetone (example 22) or 4,4’-dialchilarilsulfonai (example 23) instead of diphenylsulfone, and assessed thermosensitive recording materials. The results obtained are summarized in table 1.

Comparative example 1

Heat-sensitive recording material was obtained in the same manner as in example 1, except for using 2,2-bis(4-hydroxyphenyl)propane instead of the urea-urethane compound synthesized in example 1 and evaluated. The results obtained are summarized in table 1.

Comparative example 2

To 17,4 g 2, 4-colordistance was added 5 ml of methyl ethyl ketone as the solvent, and then was added dropwise there a solution of 3.2 g of methanol in 5 ml of methyl ethyl ketone, and the interaction was conducted with stirring at room temperature for 2 hours. Then there was added dropwise a solution of 7.3 g of n-butylamine in 100 ml of methyl ethyl ketone by stirring at room temperature, and the resulting mixture was stirred for 1 hour. The crystalline precipitate was obtained by filtration, washed with hexane and then dried overnight in vacuum to obtain 27 g of soy is inane in the form of white crystals. The melting point of white crystals was 156° and analytical measurement was as follows.

The result of IR measurement:

The characteristic peaks were located at 1240 cm-1, 1550 cm-1, 1640 cm-1, 1720 cm-1and 3300 cm-1.

It was proved that the structural formula of the main component of this compound is formula (R-1), shown here next.

Then heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1 was used the compound, obtained above, and evaluated it. The results obtained are summarized in table 1.

Comparative example 3

To 10.0 g of 2,4-colordistance was added 100 g of toluene.

In the process of stirring the obtained mixture at 25° to it was added a solution of 15.5 g of stearylamine in 100 ml of toluene, and the interaction was carried out at 25° C for 22 hours. After the interaction of the white solid precipitate was obtained by filtration, washed with toluene and then dried overnight in vacuum to obtain 20.4 g of white crystals. After this was added 5 g of the thus obtained compound in 50 ml of methyl ethyl ketone. In the process of stirring the obtained mixture at 80° to it was added a solution of 8.6 g of p-hydroxybenzylidene acid in 20 ml of meth is latility and then 5 mg of dibutyltindilaurate as a catalyst, and the interaction was carried out at 80° C for 12 hours. After the interaction, the reaction mixture was cooled to room temperature, and the crystalline precipitate was obtained by filtration, washed with methyl ethyl ketone and then dried overnight in vacuum to obtain 5.6 g of white crystals.

Analytical measurement of these white crystals were as follows.

The result of IR measurement:

The characteristic peaks were 1220 cm-1, 1520 cm-1, 1630 cm-1, 1710 cm-1, 2900 cm-1and 3300 cm-1.

The result of mass spectroscopical measurement:

[M+H]+identified at m/z 596.

It was proved that the structural formula of the main component of this compound is formula (R-2), shown here and below.

Then heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1 was used the compound, obtained above, and evaluated it. The results obtained are summarized in table 1.

Comparative example 4

To 100 ml of dioxane was added 3.0 g of p-aminophenol. In the process of stirring the obtained mixture at 50° to it was added dropwise a solution of 5.4 g toluensulfonate in 30 ml of dioxane for 1 hour, and the interaction was carried out at 50° With those who tell 5 hours. After the interaction the reaction solution was concentrated and then poured into hexane to effect crystallization, and the solid precipitate was obtained by filtration, washed with hexane and then dried overnight in vacuum to obtain 4.9 g of brown crystals. Then 2 g of the thus obtained compounds were added in 50 ml of dioxane. In the process of stirring the obtained mixture at 80° to it was added a solution of 3.8 g octadecylsilane in 10 ml of dioxane and then 2 mg of dibutyltindilaurate as a catalyst, and the interaction was carried out at 80° C for 20 hours. After the interaction, the reaction mixture was cooled to room temperature, and the crystalline precipitate was obtained by filtration, washed with dioxane and then dried overnight in vacuum to obtain 2.7 g of a slightly pink crystals.

Analytical measurement of these slightly pink crystals was as follows.

The result of IR measurement:

The characteristic peaks were located at 1230 cm-1, 1470 cm-1, 1510 cm-1, 1570 cm-1, 1620 cm-1, 1700 cm-1, 2900 cm-1and 3300 cm-1.

It was proved that the structural formula of the main component of this compound is formula (R-3)shown below.

Then heat-sensitive recording material was obtained in the same manner as in example 1, except the rising, instead of the urea-urethane compound synthesized in example 1 was used the compound, obtained above, and evaluated it. The results obtained are summarized in table 1.

Comparative example 5

To 10 g of 2,4-colordistance was added 50 g of toluene as a solvent, after which there was added 30 g of aniline, and the interaction was carried out at 25° C for 3 hours. After the interaction of the white solid precipitate was obtained by filtration, washed with hexane and then dried overnight in vacuum to obtain 17 g of compound as white crystals.

The proposed structural formula of the main component of this compound is structural formula of the compound (C-1), shown here next.

Then 2 g of this compound were crushed together with 8 g of an aqueous solution of 2.5 wt.% polyvinyl alcohol in the paint shaker for 45 minutes for dispersion, whereby was obtained a dispersion.

Then heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1 was used the compound, obtained above, and evaluated it. The results obtained are summarized the table 1.

Comparative example 6

To 10 g of 2,4-colordistance was added 30 g of toluene as a solvent, after which there was added 30 g of phenol, and the interaction was carried out at 100° C for 3 hours. After the interaction, the toluene was removed by concentration and to the precipitate was added hexane and the white solid precipitate was obtained by filtration, washed with hexane and then dried overnight in vacuum to obtain 15 g of compound as white crystals.

The proposed structural formula of the main component of this compound is structural formula of the compound (C-2)shown below.

Then 2 g of the obtained compound were crushed together with 8 g of an aqueous solution of 2.5 wt.% polyvinyl alcohol in the paint shaker for 45 minutes for dispersion, whereby was obtained a dispersion.

Then heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1 was used the compound, obtained above, and evaluated it. The results obtained are summarized in table 1.

Comparative example 7

Heat-sensitive recording material was obtained in the same manner as in example 1, except for using the project 1,3-diphenylacetone instead of the urea-urethane compounds, synthesized in example 1 and evaluated. The results obtained are summarized in table 1.

Example 24

In the mixing process of 31.5 g of 2, 4-colordistance at 60° there was added dropwise a solution of 21.5 g of 4,4’-diaminodiphenylsulfone dissolved in 120 ml of methyl ethyl ketone, for 4 hours, and the interaction was carried out at 60° C for another 2 hours. After the interaction the reaction solution was cooled to room temperature and thereto was added toluene, and the white solid precipitate was obtained by filtration, washed with toluene and then dried overnight in vacuum to obtain 47 g of compound as white crystals. Then 30 g of the obtained compound was added 9.5 g of phenol and 95 ml of methyl ethyl ketone, after which there was added 30 mg of triethylamine, and the interaction was carried out at 25° C for 4 hours. After the interaction in the reaction solution was added toluene, and the crystalline precipitate was obtained by filtration, washed with toluene and then dried over night in vacuum with the receipt of 38.5 g of compound as white crystals. When performing infrared measurements of these white crystals were found characteristic peaks at 990 cm-1the 1110 cm-1, 1320 cm-1, 1590 cm-1, 1700 cm-1and 3350 cm-1.

Then got a dispersion by dispersing 2 g of the obtained compound by grinding the x together with 8 g of an aqueous solution of 2.5 wt.% polyvinyl alcohol in the paint shaker for 6 hours. The temperature of the dispersion immediately after the dispersion was 25° C. the Diameter of dispersed particles of the compound was 0.6 μm.

Another dispersion was obtained by dispersing 70 g of 3-dibutylamino-6-methyl-7-onlineflorida by grinding it together with 130 g of an aqueous solution of 5.4 wt.% hydroxypropylmethylcellulose (Metlose 60SH-03, p. Shin-Etsu Chemical Co., Ltd.) in a sand mill (made. AIMEX CO., LTD.; tank volume 400 ml) with the number of revolutions of 2000 rpm for 3 hours.

Another dispersion was obtained by dispersing 70 g of diphenylsulfone by grinding it together with 130 g of an aqueous solution of 8 wt.% polyvinyl alcohol in a sand mill (made. AIMEX CO., LTD.; tank volume 400 ml) with the number of revolutions of 2000 rpm for 3 hours.

One other dispersion was obtained by mixing 10 g of calcium carbonate, 30 g of water and stirring the mixture using a mixer.

Covering liquid was obtained by stirring and mixing the above-mentioned dispersions and other components in the following proportions (the proportions of dry basis); the variance of the above compounds in terms of dry solid substance: 20 parts by weight, the dispersion of the 3-dibutylamino-6-methyl-7-onlineflorida in terms of dry solid substance: 10 parts by weight, dispersion of diphenylsulfone in terms of dry solid substance: 25 parts by weight, the dispersion ka is Bonita calcium in terms of dry solid substance: 40 parts by weight, dispersion of zinc stearate (solid content: 16 wt.%) in terms of dry solid substance: 20 parts by mass and 15 wt.% poly(vinyl alcohol) in terms of dry solid substance: 15 parts by mass.

Covering the liquid was applied to the main paper with a weight basis of 50 g/m2using the installation for the coating to remove excess using a strap with a pin number 10. Covering the covering number of the liquid was 5 g/m2in terms of dry mass. After drying were supercalendering obtaining thermosensitive recording material.

The result of evaluating the sensitivity of the obtained heat-sensitive recording material was so optimal that the optical density was 1.3. The ability to save the fingerprint, which was evaluated with the use of vinyl chloride wrapping film, was the best. The degree of whiteness of the original surface of the recording material was almost 82. The results of these evaluations are summarized in table 2.

Examples 25 and 26

Heat-sensitive recording material was obtained in the same manner as in example 24, except using 3-diethylamino-6-methyl-7-onlineflorida (example 25) or 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminonaphthalene (example 26) instead of 3-dibutylamino-6-methyl-7-aniline is lurana, and evaluated. The results obtained are summarized in table 2.

Examples 27-29

Heat-sensitive recording material was obtained in the same manner as in example 24, except using methyl cellulose (Metlose M-15, production. Shine-Etsu Chemical Co., Ltd.) (example 27), sulfate polyoxyethyleneglycol ether (Rebenol WX, production. Kao Corp.) (example 28) or sodium 2-ethylhexylcarbonate (Neocol SWC, production. Dai-ichi, Kodwa Seiyaku Co., Ltd.) (example 29) instead of hydroxypropylmethylcellulose used in example 24, for dispersion 3-dibutylamino-6-methyl-7-onlineflorida, and heat-sensitive recording materials were evaluated. The results obtained are summarized in table 2.

Example 30

The dispersion of the urea-urethane compound developer, 3 dibutylamino-66-methyl-7-anilinophenol dispersion, diphenylsulfone dispersion and the dispersion of calcium carbonate was obtained in the same manner as in example 24.

On the other hand, the dispersion was prepared by dispersing 70 g of 2,2-bis(4-hydroxyphenyl)propane by grinding it together with 130 g of an aqueous solution of 5.4 wt.% polyvinyl alcohol in a sand mill (made. AIMEX Co., LTD.; tank volume 400 ml) with the number of revolutions of 2000 rpm for 3 hours.

Covering liquid was obtained by stirring and mixing the above-mentioned dispersions and other components in the following proportions (about what Orli dry basis); the dispersion of the urea-urethane compound in terms of dry solid substance: 10 parts by weight, the dispersion of the 3-dibutylamino-6-methyl-7-onlineflorida in terms of dry solid substance: 10 parts by weight, dispersion of diphenylsulfone in terms of dry solid substance: 20 parts by weight, dispersion of 2,2-bis-(4-hydroxyphenyl)propane in terms of dry solid substance: 10 parts by weight, dispersion of calcium carbonate in terms of dry solid substance: 20 parts by weight, dispersion of zinc stearate (solids content: 16 wt.%) in terms of dry solid substance: 10 parts by mass and 15 wt.% poly(vinyl alcohol) in terms of dry solid substance: 10 parts by mass.

Heat-sensitive recording material was obtained in the same manner as in example 24, except covering the liquid obtained above, and evaluated. The results obtained are summarized in table 2.

Examples 31-34

Heat-sensitive recording material was obtained in the same manner as in example 30 except for using 4-isopropoxyphenyl-4’-hydroxyprednisolone (D-8, trade name, made. Nippon Soda Co., Ltd.), (example 31), bis(3-allyl-4-hydroxyphenyl)sulfone (TG-SA, trade name, made. Nippon Kayaku Co., Ltd.) (example 32), 2,4’-dihydroxydiphenylsulfone (24BPS, trade name, made. Nicca Chemical Co., Ltd.) (p is the iMER 33) or mixtures composed mainly of 4,4’-[oxybis(ethyleneoxy-p-phenylenesulfonyl)]diphenol (D-90, trade name, made. Nippon Soda Co., Ltd.) (example 34) instead of 2,2-bis(4-hydroxyphenyl)propane and heat-sensitive recording materials were evaluated. The results obtained are summarized in table 2.

Examples 35-64

Heat-sensitive recording material was obtained in the same manner as in examples 30-34, except β -aftermentioned ether (BON, trade name, made. Ueno Fine Chemicals Industry Ltd.) (examples 35-39), p-benzylbiphenyl (RWR, trade name, made. Nippon Steel Chemical Co., Ltd.) (examples 40-44), 1,2-di(m-methylphenoxy)ethane (KS-235, trade name, made. SANKOSHA CO., LTD.) (examples 45-49), di-p-methylanthranilate (HS3520, trade name, made. Dainippon Ink and Chemicals, Inc.) (examples 50-54), 1,2-diphenoxyethane (RMV-2, trade name, made. Nicca Chemical Co., Ltd.) (examples 55-59) or m-terphenyl (mtp, trade name, made. Nippon Steel Chemical Co., Ltd.) (examples 60-64) instead of diphenylsulfone, and heat-sensitive recording materials were evaluated. The results obtained are summarized in table 2.

Examples 65-66

Heat-sensitive recording material was obtained in the same manner as in example 24, except using stearamide-emulsified product (Highmicron G-270, trade name, made. Chukyo Yushi Co., Ltd.) (example 65) or acetoxy the o-Chloroaniline (p. Mitsuboshi Chemical Co., Ltd.) (example 66) instead of diphenylsulfone, and evaluated. The results obtained are summarized in table 2.

Example 67

Heat-sensitive recording material was obtained in the same manner as in example 30, except for the addition of a fluorescent dye Stevenage type (Kayahol 3BS, trade name, made. Nippon Kayaku Co., Ltd.) in covering the liquid obtained in example 30, in a ratio of 1 part by weight per 100 parts by weight (in terms of dry solid) covering liquid and evaluated. The results obtained are summarized in table 2.

Example 68

The variance was obtained by dispersing 70 g of 1,1,3-Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane by grinding it together with 130 g of an aqueous solution of 5.4 wt.% polivinilovogo alcohol in a sand mill (made. AIMEX CO., LTD.; tank volume 400 ml) with the number of revolutions of 2000 rpm for 3 hours.

Then heat-sensitive recording material was obtained in the same manner as in example 30, except for the addition of the above 1,1,3-Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane dispersion in covering the liquid obtained in example 30, in the proportion of 10 parts by weight per 100 parts by weight (in terms of dry solid) covering liquid and evaluated. The results obtained are summarized in table 2.

Example 69

In 30 g of 2,4-tolualdehyde the ATA was added 30 g of toluene as a solvent, then there was added 3,24 g of phenol, and the interaction was carried out at 100° C for 1 hour and 30 minutes. After the interaction, the toluene was removed by concentration and to the precipitate was added hexane and the white solid precipitate was obtained by filtration, washed with hexane and then dried overnight in a vacuum with the receipt of 6.9 g of compound as white crystals. Then was added 100 g of toluene as a solvent to 5.0 g of the obtained compound, after which there was added 3.50 g of aniline, and the interaction was carried out at 25° C for 3 hours. The crystalline precipitate was obtained by filtration, washed with hexane and then dried overnight in vacuum to obtain 5.5 g of the compound in the form of white crystals. When performing infrared measurements of these white crystals was found that the characteristic peaks at 890 cm-1, 1000 cm-1, 1030 cm-1, 1440 cm-1, 1720 cm-1and 3350 cm-1.

Then heat-sensitive recording material was obtained in the same manner as in example 68, except for using the above connection instead of the urea-urethane compound used in example 68, and was evaluated. The results obtained are summarized in table 2.

Examples 70-75

Heat-sensitive recording material was obtained in the same manner as in example 68, except used is of 1,1,3-Tris(2-methyl-4-hydroxy-5-cyclohexylphenol)butane (Adecaarcles DH-43, production. Asahi Denka Kogyo K.K.) (example 70), 4-benzyloxy-4’-(2, 3-epoxy-2-methylprop-1 yloxy) diphenylsulfone (NTZ-95, production. Nippon Soda Co., Ltd.), (example 71), Methylenebis(2-hydroxy-3-(benzotriazol-2-yl)-5-tert-octylphenyl) (example 72), 2-(2’-hydroxy-5’-were)benzotriazole (Adecaarcles DN-13, production. Asahi Denka Kogyo K.K.) (example 73), 1,3,5-Tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocyanurate (Adecaarcles DH-48, p. Asahi Denka Kogyo K.K.) (example 74) or sodium 2,2-Methylenebis(4,6-di-tert-butylphenyl)phosphate (Adecaarcles F-85, p. Asahi Denka Kogyo K.K.) (example 75) instead of 1,1,3-Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, and heat-sensitive recording materials were evaluated. The results obtained are summarized in table 2.

Comparative example 8

Heat-sensitive recording material was obtained in the same manner as in example 24 except for using 2,2-bis(4-hydroxyphenyl)propane instead of the urea-urethane compound synthesized in example 24, and evaluated. The results obtained are summarized in table 2.

<abrasion Resistance>

The surface of the heat-sensitive recording material was strongly rubbed with a nail and visually evaluated whether the expression of color in the part where Ter. When the recording material showed no visible bands, the degree of abrasion resistance was good.

<Accumulation of friction strips>

Cylinder (weight: kg) have a slice with a diameter of 5 cm was moved 50 times on the same area length of 20 cm recording surface of each of the obtained thermosensitive recording material at a speed of 20 cm/sec, and then the recording material was left at room temperature for one week. After one week were visually evaluated the readability of the printed image. When the printed image can be adequately read, the recording material was evaluated as good.

Example 76

Thermosensitive liquid for coating was obtained in the same manner as in example 24. Then the liquid coating was applied to the main paper with a weight basis of 50 g/m2using the device for coating with a pin number 10. After drying were supercalendering obtaining thermosensitive color-forming layer on the substrate. Covering the amount of liquid to cover was 5 g/m2in terms of dry mass.

Then got a dispersion by dispersing 40 g of kaolin by grinding it together with 60 g of an aqueous solution of 0.7 % sodium hexametaphosphate in a sand mill (made. AIMEX CO., LTD.; tank volume 400 ml) with the number of revolutions of 2000 rpm for 3 hours.

Received covering liquid for protective layer formation by mixing and blending alinovi dispersion and other components in the following proportions (the proportions of dry basis); the dispersion of kaolin in terms of dry solid substance: 20 parts by weight, dispersion of zinc stearate (solid component: 16 wt.%) in terms of dry solid substance: 10 parts by weight, aqueous solution of carboxy-modified polyvinyl alcohol in terms of dry solid substance: 40 parts by weight, and an aqueous solution polyaryletheretherketone agent, forming cross-linkage, in terms of dry solid substance: 5 parts by mass.

Covering liquid for protective layer formation was applied to thermosensitive color-forming layer, using the device for coating with the rod 5. After drying were supercalendering obtaining thermosensitive recording material. Covering the amount of liquid to form a protective layer was 2 g/m2in terms of dry mass.

The result of evaluating the sensitivity of the obtained heat-sensitive recording material was so good that the optical density was 1.3. The ability to save the fingerprint, estimated using vinyl chloride wrapping film was good. The surface of the heat-sensitive recording material was strongly rubbed with a nail and visually evaluated the expression of color in the part where Ter, and found that no noticeable is the ice scrapes were not available, namely, that the abrasion resistance was good. The result of long-term trials to assess the resistance to abrasion was so good that the printed image could adequately be read. These evaluation results are summarized in table 3.

Examples 77 and 78

Heat-sensitive recording material was obtained in the same manner as in example 76, except for using polyvinyl alcohol (example 77) or acrylic copolymer (example 78) instead of carboxy-modified polyvinyl alcohol, and evaluated. The results obtained are summarized in table 3.

Examples 79-81

Heat-sensitive recording material was obtained in the same manner as in example 76, except for the use of aluminum hydroxide (example 79), cross-linking polimetilmetacrilato resin (example 80) or silicon dioxide (example 81) instead of kaolin, and evaluated. The results obtained are summarized in table 3.

Example 82

Liquid to cover for the intermediate layer was obtained by stirring and mixing the dispersion of 33 wt.% calcined kaolin and latex water dispersion based on 50 wt.% styrene/butadiene, in the proportions (proportion of dry basis) 100 parts by weight and 12 parts by weight, respectively.

Then received covering the liquid for the back side by mixing and shift the air traffic management 20 wt.% acrylic emulsion and 10 wt.% silicon dispersion in the form of fine powder (Fineseal SP-10) in proportions (proportion of dry basis) 100 parts by weight and 7 parts by weight, respectively.

The above liquid to cover for an intermediate layer was applied onto one side of the main paper (50 g/m2) in an amount of 10 g/m2in units of solids and dried, and heat-sensitive liquid for coating obtained in example 76, was applied on the same side in an amount of 5 g/m2in units of solids and dried, after which the liquid to cover for the protective layer obtained in example 76, was applied on the same side in the amount of 2 g/m2in units of solids and dried. Then the above-mentioned liquid for back-coating was applied to the side without coverage in the amount of 1 g/m2in units of solids and dried, and calendering was performed with obtaining a thermosensitive recording material was evaluated. The results obtained are summarized in table 3.

Comparative example 9

Heat-sensitive recording material was obtained in the same manner as in example 76, except that thermosensitive color-forming layer is not applied liquid for coating, forming a protective layer, and the recording material was evaluated. The results obtained are summarized in table 3.

Example 83

The variance was obtained by dispersing 2 g of the compound obtained in example 24, by grinding it together with 8 g of an aqueous solution of 2.5 wt.% polyvine the marketing of alcohol (Gohsenol KL-05, production. Nippon Syntic Chemical Industry Co., Ltd.) in the paint shaker for 6 hours. The temperature of the dispersion immediately after the dispersion was 25° and the pH of the dispersion was 8. The diameter of dispersed particles of the compound was 0.6 μm.

Another dispersion was obtained by dispersing 70 g of 3-dibutylamino-6-methyl-7-onlineflorida by grinding it together with 130 g of an aqueous solution of 5.4 wt.% polyvinyl alcohol in a sand mill (made. AIMEX CO., LTD.; tank volume 400 ml) with the number of revolutions of 2000 rpm for 3 hours.

Another dispersion was obtained by dispersing 70 g of diphenylsulfone by grinding it together with 130 g of an aqueous solution of 5.4 wt.% polyvinyl alcohol (Gohsenol KL-05, made. Nippon Syntic Chemical Industry Co., Ltd.) in a sand mill (made. AIMEX CO., LTD.; tank volume 400 ml) with the number of revolutions of 2000 rpm for 3 hours.

One other dispersion was obtained by mixing 10 g of calcium carbonate, 30 g of water and stirring the mixture using a mixer.

The liquid coating was obtained by stirring and mixing the above-mentioned dispersions and other components in the following proportions (the proportions of dry basis); the variance of the above compounds in terms of dry solid substance: 30 parts by weight, the dispersion of the 3-dibutylamino-6-methyl-7-onlineflorida in terms of dry solid substance: 15 parts by weight, the dispersion diphenylol the background in terms of dry solid substance: 30 parts by weight, dispersion of calcium carbonate in terms of dry solid substance: 20 parts by weight, dispersion of zinc stearate (solid component: 16 wt.%) in terms of dry solid substance: 10 parts by weight, and 15 wt.% polyvinyl alcohol in terms of dry solid substance: 7 parts by weight. the pH of the covering liquid was 8,2.

Then the liquid coating was applied to the surface of the paper not containing mechanical pulp, with a weight basis of 50 g/m2in an amount of 5 g/m2in terms of dry weight and dried using supercalendering obtaining thermosensitive recording material. The result of evaluating the sensitivity of the obtained heat-sensitive recording material was so good that the optical density was 1.3. The ability to save the fingerprint, estimated using vinyl chloride wrapping film, was so good that burnout was not. The obtained evaluation results are summarized in table 4.

Example 84

The variance was obtained by dispersing 2 g of the same urea-urethane compound, which was used in example 83, and 2 g of diphenylsulfone by grinding them together with 16 g of an aqueous solution of 2.5 wt.% modified polyvinyl alcohol (Gohsenol KL-05, made. Nippon Syntic Chemical Industry Co., Ltd.) in the paint shaker for 6 hours.

Then thermosensitive C is pitiayumi material was prepared in the same way, as in example 83, except for the addition of the above joint variance in the proportion of 60 parts by weight in terms of dry solid substance, instead of the dispersion of the urea-urethane compound used in example 83, and diphenylsulfone dispersion, and the recording material was evaluated. The results obtained are summarized in table 4.

Example 85

To 61 g of 2,4-colordistance was added 450 g of toluene as a solvent, after which there was added dropwise a solution of 26 g of aniline in 150 g of toluene for 6 hours and the interaction was carried out at 5° C for 7 hours. After the interaction of the white solid precipitate was obtained by filtration, washed with toluene and then dried overnight in vacuum to obtain 70 g of compound as white crystals. Then 365 g of toluene was added as a solvent to 30 g of the obtained compound, after which was added 12.2 g of 2,2-bis(4-hydroxyphenyl)propane and 0.3 mg of triethylamine, and the interaction was performed under stirring at 60° C for 4 hours, at 70° C for 3 hours and then at 80° C for 3 hours. After the interaction the reaction solution was cooled to room temperature and the crystalline precipitate was obtained by filtration, washed with toluene and then dried overnight in vacuum to obtain 42 g of compound as white Crist is low. Held infrared measurements of these white crystals were detected characteristic peaks at 750 cm-1, 840 cm-1, 1020 cm-1, 1500 cm-1, 1600 cm-1, 1720 cm-1and 3320 cm-1.

The variance was obtained by dispersing 2 g of this compound and 2 g

diphenylsulfone by grinding them together with 16 g of an aqueous solution of 2.5 wt.% modified polyvinyl alcohol (Gohseran L-3266, production. Nippon Syntic Chemical Industry Co., Ltd.) in the paint shaker for 6 hours.

Then heat-sensitive recording material was obtained in the same manner as in example 83, except for the addition of the joint variance of the above compounds and diphenylsulfone in proprecia 60 parts by weight in terms of dry solid material instead of the dispersion of the urea-urethane compound used in example 83, and dispersion of diphenylsulfone, and the recording material was evaluated. The results obtained are summarized in table 4.

Example 86

The variance was obtained by dispersing 2 g of the compound obtained in example 69, and 2 g of dimethylbenzylamine by grinding them together with 16 g of an aqueous solution of 2.5 wt.% modified polyvinyl alcohol (Gohseran L-3266, production. Nippon Syntic Chemical Industry Co., Ltd.) in the paint shaker for 6 hours.

Then heat-sensitive recording material was obtained in the same manner as in example 83, the claim is ucheniem add the above joint dispersion of the above compounds and dimethylphenylacetate in the proportion of 60 parts by weight in terms of dry solid material instead of the dispersion of the urea-urethane compounds, used in example 83, and diphenylsulfone dispersion, and the recording material was evaluated. The results obtained are summarized in table 4.

Example 87

The variance was obtained by dispersing 2 g of the compound obtained in example 2, by grinding it together with 8 g of an aqueous solution of 2.5 wt.% methylcellulose (Metlose SM-15, production. Shin-Etsu Chemical Co., Ltd.) in the paint shaker for 6 hours.

Then heat-sensitive recording material was obtained in the same manner as in example 83, except for using the dispersion of the above-mentioned connection instead of the dispersion of the urea-urethane compound used in example 83, and the recording material was evaluated. The results obtained are summarized in table 4,

Examples 88-92

Heat-sensitive recording material was obtained in the same manner as in example 83, except ammonium salt of polycarboxylic acid (Dispersant 5027, production. Sunnopco Co., Ltd.) (example 88), water-soluble low molecular weight copolymer (Discort N14, production. Dai-ichi, Kodwa Seiyaku Co., Ltd.) (example 89), sodium 2-ethylhexylcarbonate (Neocol SWC, production. Dai-ichi, Kodwa Seiyaku Co., Ltd.) (example 90), hydroxypropylmethylcellulose (Metlose 60SH-03, p. Shin-Etsu Chemical Co., Ltd.) (example 91), or condensed sodium naphthalenesulfonate (Roma D, production. Sunnopco Co., Ltd.) (example 92) instead of polyvinyl alcohol (Gohsenol KL-05, made. Nippon Syntic Cheical Industry Co., Ltd.), used as a dispersing agent for the urea-urethane compound in example 83, and the heat-sensitive recording materials were evaluated. The results obtained are summarized in table 4.

Examples 93-98

Heat-sensitive recording material was obtained in the same manner as in example 83, except for the use of methylcellulose (Metlose SM-15, production. Shin-Etsu Chemical Co., Ltd.) (example 93), water-soluble low molecular weight copolymers (Discord N14, production. Dai-ichi Kogyo Seiyaku Co., Ltd.) (example 94), 2-ethylhexylacrylate sodium (Neocol SWC, production. Dai-ichi, Kodwa Seiyaku Co., Ltd.) (example 95), hydroxypropylmethylcellulose (Metlose 60SH-03, p. Shin-Etsu Chemical Co., Ltd.) (example 96), condensed naphthalenesulfonate sodium (Roma D, production. Sunnopco Co., Ltd.) (example 97) or ammonium salts polycarboxylic acid (Dispersant 5027, production. Sunnopco Co., Ltd.) (example 98) instead of polyvinyl alcohol (Gosenol KL-05, made. Nippon Syntic Chemical Industry Co., Ltd.), used as a dispersing agent for diphenylsulfone in example 83, and the heat-sensitive recording materials were evaluated. The results obtained are summarized in table 4.

Examples 99-101

Heat-sensitive recording material was obtained in the same manner as in example 87, except using methyl cellulose (Metlose SM-15, production. Shin-Etsu Chemical Co., Ltd.) (example 99), gidroksipropilmetilzelluloza (Mtlose 60SH-03, production. Shin-Etsu Chemical Co., Ltd.) (example 100) or a modified polyvinyl alcohol (Gohseran L-3266, production. Nippon Syntic Chemical Industry Co., Ltd.) (example 101) instead of polyvinyl alcohol (Gohsenol KL-05, made. Nippon Syntic Chemical Industry Co., Ltd.), used as a dispersing agent for diphenylsulfone in example 87, and heat-sensitive recording materials were evaluated. The results obtained are summarized in table 4.

Example 102

Heat-sensitive recording material was obtained in the same manner as in example 99, except for the use of modified polyvinyl alcohol (Gohseran L-3266, production. Nippon Syntic Chemical Industry Co., Ltd.) instead of methylcellulose (Metlose SM-15, production. Shin-Etsu Chemical Co., Ltd.), used as a dispersing agent for the urea-urethane compound in example 99, and the recording material was evaluated. The results obtained are summarized in table 4.

Examples 103 and 104

Heat-sensitive recording material was obtained in the same manner as in example 89, except for the use of methylcellulose (Metlose SM-15, production. Shin-Etsu Chemical Co., Ltd.) (example 103) or hydroxypropylmethylcellulose (Metlose 60SH-03, p. Shin-Etsu Chemical Co., Ltd.) (example 104) instead of polyvinyl alcohol (Gohsenol KL-05, made. Nippon Syntic Chemical Industry Co., Ltd.), used as a dispersing agent for diphenylsulfone in example 89, and thermosensitive zapisyvaetal evaluated. The results obtained are summarized in table 4.

Examples 105-106

Heat-sensitive recording material was obtained in the same manner as in example 91, except for the use of methylcellulose (Metlose SM-15, production. Shin-Etsu Chemical Co., Ltd.) (example 105) or hydroxypropylmethylcellulose (Metlose 60SH-03, p. Shin-Etsu Chemical Co., Ltd.) (example 106) instead of polyvinyl alcohol (Gohsenol KL-05, made. Nippon Syntic Chemical Industry Co., Ltd.), used as a dispersing agent for diphenylsulfone in example 91, and heat-sensitive recording materials were evaluated. The results obtained are summarized in table 4.

Examples 107 and 108

Heat-sensitive recording material was obtained in the same manner as in example 104 except for using hydroxypropylmethylcellulose (Metlose 60SH-03, p. Shin-Etsu Chemical Co., Ltd.) (example 107) or mixed dispersing agent hydroxypropylmethylcellulose (Metlose 60SH-03, p. Shin-Etsu Chemical Co., Ltd.) and 2-ethylhexylacrylate sodium (Neocol SWC, production. Dai-ichi Kogyo Seiyaku Co., Ltd.) (mass ratio: 1/1) (example 108) instead of polyvinyl alcohol used as a dispersing agent for 3 dibutylamino-6-methyl-7-onlineflorida in example 104, and a heat-sensitive recording materials were evaluated. The results obtained are summarized in table 4.

Comparative example 10

Thermosensitive recording the th sheet was obtained in the same way, as in example 83, except for using 2,2-bis(4-hydroxyphenyl)propane instead of the urea-urethane compound used in example 83, and was evaluated. The results obtained are summarized in table 4.

Comparative examples 11 and 12

The same urea-urethane compound, which was ispolzolzovalsja in example 83 was dispersively in the same way as in example 83, except change the time dispersion and the average particle size of the obtained dispersions were measured and it was 0.04 μm (comparative example 11) and 6.5 μm (comparative example 12). Heat-sensitive recording sheet was obtained in the same manner as in example 83, except for using each of the above dispersion, and evaluated. The results obtained are summarized in table 4.

Comparative example 13

The same urea-urethane compound, which was ispolzolzovalsja in example 83 was dispersively the same way as in example 83, except for temperature maintenance dispersione at 65° during the process of dispersion. Except for using the thus obtained dispersion thermosensitive recording sheet was obtained in the same manner as in example 83, and was evaluated. The results obtained are summarized in table 4.

Comparative example 14

The same urea-urethane compound which is used is whether in example 83, was dispersively the same way as in example 83, except for establishing the pH of the dispersion medium used in the dispersion process, at 4. Except for using the thus obtained dispersion thermosensitive recording sheet was obtained in the same manner as in example 83, and was evaluated. The results obtained are summarized in table 4.

Comparative example 15

The same urea-urethane compound, which was ispolzolzovalsja in example 83 was dispersively the same way as in example 83, except for establishing the pH of the dispersion medium used in the dispersion process, at 11. Except for using the thus obtained dispersion thermosensitive recording sheet was obtained in the same manner as in example 83, and was evaluated. The results obtained are summarized in table 4.

Comparative example 16

the pH of the covering liquid obtained in example 83 was established to 4.0 using 1N sulfuric acid. Except for using the thus obtained covering the liquid heat-sensitive recording sheet was obtained in the same manner as in example 83, and was evaluated. The results obtained are summarized in table 4.

Comparative example 17

the pH of the covering liquid obtained in example 83 was set at 12,5 using 1N sodium hydroxide. For drop is by use of the thus obtained covering the liquid heat-sensitive recording sheet was obtained in the same way, as in example 83, and was evaluated. The results obtained are summarized in table 4.

Example 109

Covering the liquid obtained in example 83, was applied to the paper without wood pulp with a pH on the surface of 3.2 in an amount of 5 g/m2in units of dry weight and dried, and then spent supercalendering obtaining thermosensitive recording material. The result of evaluating the sensitivity of the obtained heat-sensitive recording material was so good that the optical density was 1.3. The ability to save the fingerprint, which was evaluated with the use of vinyl chloride wrapping film, was the best. The ability to preserve the original surface of the recording material was so good that the surface was barely painted. The results obtained are summarized in table 5.

Examples 110 and 111

Heat-sensitive recording material was obtained in the same manner as in example 109, except for the use of paper out of wood pulp with a pH of surface 5 (example 110) or paper out of wood pulp with a surface pH of 6.8 (example 111) instead of paper out of wood pulp with a surface pH of 3.2, and evaluated the results Obtained are summarized in table 5.

Comparative examples 18 and 19

Heat-sensitive recording material was obtained in the same manner as in example 109 except for the use of paper out of wood pulp with a surface pH of 2.8 (comparative example 18) or of paper out of wood pulp with a surface pH of 9.5 (comparative example 19) of paper out of wood pulp with a pH of surface the pH of 3,2, and evaluated the results Obtained are summarized in table 5.

Example 112

A) obtaining a covering liquid for the magnetic recording layer

Liquid for coating the magnetic recording layer was obtained, dispersive 100 parts by weight of barium ferrite (coercive force: 2700), 25 parts by weight of sodium polyacrylate (20 wt.% aqueous solution), 100 parts by weight of polyvinylidenechloride (49 wt.% dispersion), 15 parts by mass, black carbon (36 wt.% dispersion), 10 parts by weight of paraffin wax (20 wt.% the variance obtained using methylcellulose) and 100 parts by weight of water in a ball mill for 10 hours.

C) Obtaining covering liquid for thermosensitive recording layer

Liquid coatings for heat-sensitive recording layer was obtained in the same manner as in example 24.

Then cover the liquid for the magnetic recording layer obtained in (A), was applied onto one side of paper out of wood pulp by weight in the basics of 150 g/m2in the amount of 30 g/m2in units of dry weight and dried to obtain a magnetic recording layer. Then cover the liquid for heat-sensitive recording layer obtained in B)was applied on the other side of the substrate having the above-mentioned magnetic recording layer in an amount of 6 g/m2in units dry the mass, and dried, and then spent supercalendering with obtaining a heat-sensitive magnetic recording material.

The result of the evaluation of the sensitivity of the degree of color development of thermosensitive recording layer of the obtained heat-sensitive recording material was so optimal that the optical density was 1.3. The ability to save the fingerprint, which was evaluated with the use of vinyl chloride wrapping film, was so good that the optical density was 1.3. The results obtained are summarized in table 6.

Example 113

C) obtaining the covering liquid for the protective layer

Twenty parts by weight of zinc stearate, 20 parts by weight of aqueous solution of 5 wt.% methylcellulose and 60 parts by weight of water were mixed and then dispersively in a sand mill for 2 hours. Then 20 parts by weight of aqueous solution of 10 wt.% carboxy-modified polyvinyl alcohol, 1.5 parts by weight of silicon, 6.5 parts by weight of an aqueous solution of 12.5 wt.% polyamideimides and 15.0 parts by mass of water were mixed and then dispersively in a sand mill for 2 hours.

Then 0.7 parts by weight of a dispersion of zinc stearate, obtained above, 45.0 parts by weight of a dispersion of silicon, obtained above, and 11.3 parts by weight of water were mixed to prepare pokr is that the liquid for the protective layer. Heat-sensitive magnetic recording material was prepared in the same manner as in example 112, except for the application of the protective layer covering the above liquid for protective layer on thermosensitive recording layer of the heat-sensitive magnetic recording material of example 112 in the amount of 3 g/m2in units of dry mass, then dried, and heat-sensitive magnetic recording material was evaluated. The results obtained are summarized in table 6.

Example 114

D) obtaining the covering liquid for the intermediate layer

Received liquid to cover for the intermediate layer, which consisted of 80 parts by weight (in terms of dry solid) 48% dispersion of finely divided polystyrene and 20 parts by weight (in terms of dry solid) 40% styrene-acrylic ester copolymer emulsion.

Heat-sensitive magnetic recording material was prepared in the same manner as in example 113, except for the application of an intermediate layer covering the above fluid between the heat-sensitive recording layer and a substrate heat-sensitive magnetic recording material of example 113 in the amount of 8 g/m2in units of dry mass, then dried and heat-sensitive magnetic recording material was evaluated. Results the ATA are summarized in table 6.

Comparative example 20

Heat-sensitive recording sheet was obtained in the same manner as in example 112, except for using 2,2-bis(4-hydroxyphenyl)propane instead of the urea-urethane compound used in example 112, and evaluated. The results obtained are summarized in table 6.

Example 115

A) obtaining a covering liquid for thermosensitive recording layer

Covering liquid for heat-sensitive recording layer was obtained in the same manner as in example 24.

Covering liquid for heat-sensitive recording layer obtained in (A), was applied to the surface of paper out of wood pulp with a weight basis 150 g/m2in the amount of 7 g/m2in terms of dry weight and dried, followed by conducting superchildren with the receiving sheet, covered with a heat-sensitive recording layer.

B) Obtaining an anti-adhesive film

Extruded parting agent in the composition with oily dimethylsilicone inflicted on the main paper with a weight basis of 40 g/m2in the amount of 1 g/m2using the device for coating corrugated roller, to obtain the anti-adhesive layer. Then, component adhesive layer consisting of 100 parts by weight of chlorinated rubber, 20 parts by weight ester resin, 120 parts by weight dibutyltin is the put on the anti-adhesive layer in an amount of 10 g/m2.

C) Receiving label for heat-sensitive recording

Uncoated surface of the film covered heat-sensitive recording layer, which was obtained in paragraph a) above, and the surface of the anti-adhesive film coated with adhesive layer obtained in paragraph C) above, glued to each other so that they come into contact, thus received a label for heat-sensitive recording.

The result of the evaluation of the sensitivity of the degree of color development is obtained labels for thermosensitive recording was so good that the optical density was 1.3. The ability to save the fingerprint, which was evaluated with the use of vinyl chloride wrapping film, was so good that fading was not. The results obtained are summarized in table 7.

Example 116

D) obtaining the covering liquid to cover the reverse side

Liquid to cover for covering the layer of the reverse side was obtained by mixing 100 parts by weight of a styrene-maleic acid with 50 parts by weight of kaolin.

Label for heat-sensitive recording was obtained in the same manner as in example 115, except for the application of the covering layer to the back side of the above covering the fluid on the wrong side regarding the additional hand, covered with a heat-sensitive recording layer. Label for heat-sensitive recording example 115 was received in the amount of 1 g/m2in units of dry mass, then dried, and the label was evaluated. The results obtained are summarized in table 7.

Example 117

E) obtaining the covering liquid for the intermediate layer

Received liquid to cover for the intermediate layer consisting of 80 parts by weight (in terms of dry solid) 48% of the variance of the crushed particles of polystyrene and 20 parts by weight (in terms of dry solid matter) of a 40% emulsion of a copolymer of styrene-acrylic ester.

Label for heat-sensitive recording was obtained in the same manner as in example 116, except for the application of an intermediate layer covering the above fluid between thermosensitive layer and the substrate of the label for heat-sensitive recording example 116 in the amount of 8 g/m2in units of dry mass, then dried, and the label was evaluated. The results obtained are summarized in table 7.

Example 118

F) obtaining the covering liquid for the protective layer

Twenty parts by weight of zinc stearate, 20 parts by weight of aqueous solution of 5 wt.% methylcellulose and 60 parts by weight of water were mixed and then dispersively in a sand mill for 2 hours. Then mixed 20 parts of m is magnetic resonance aqueous solution of 10 wt.% carboxy-modified polyvinyl alcohol, 1.5 parts by weight of silica, 6.5 parts by weight of an aqueous solution of 12.5 wt.% polyamideimides and 15.0 parts by weight of water and then dispersively in a sand mill for 2 hours.

Then mixed 0.7 parts by weight of the above dispersion of zinc stearate, 45.0 parts by weight of the above dispersion and 11.3 parts by weight of water to obtain a covering of liquid for the protective layer. Label for heat-sensitive recording was obtained in the same manner as in example 117, except for the application of the protective layer obtained above covering the liquid of thermosensitive recording layer. Label for heat-sensitive recording example 117 was received in the amount of 3 g/m2in units of dry mass, then dried, and the label was evaluated. The results obtained are summarized in table 7.

Comparative example 21

Heat-sensitive recording sheet was obtained in the same manner as in example 115, except for using 2,2-bis(4-hydroxyphenyl)propane instead of the urea-urethane compound used in example 115, and evaluated. The results obtained are summarized in table 7.

Example 119

Covering materials for heat-sensitive color-forming layer and covering materials for the intermediate layer described below was applied on one side of commercial polyethylenterephthalat the Noah film thickness of 75 μm (Lumilar E, trade name, Toray Industries, Inc.) so that the substrate could be formed of a multilayer film in the following order: thermosensitive recording layer, which gives a blue color, an intermediate layer, a thermosensitive recording layer, giving a purple color, an intermediate layer, a thermosensitive recording layer, giving a yellow color, and the intermediate layer. The application was performed using the device for coating so that the amount of to cover each of thermosensitive recording layer and each intermediate layer after drying was 6.5 g/m2and 2.0 g/m2accordingly, the thus obtained color thermosensitive recording material.

- Receiving covering materials for heat-sensitive recording layer, giving a blue color

Liquid (dispersion thermosensitive tsvetopolymer dye)

Twenty parts by weight of 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophenyl, 20 parts by weight of a 10% aqueous solution of polyvinyl alcohol and 10 parts by weight of water were mixed and then dispersible and was ground in a sand mill (made. AIMEX CO., LTD.) obtaining a dispersion having an average particle size of 0.7 microns.

Liquid (the dispersion of the developer)

The urea-urethane compound synthesized in the same manner as in the use of the e 24, and the variance was obtained by dispersing 30 g of this compound, crushing it together with 120 g of an aqueous solution of 2.5 wt.% polyvinyl alcohol in a sand mill for 3 hours. The temperature of the dispersion immediately after the dispersion was 25° C. the Diameter of dispersed particles of the compound was 0.6 μm.

Coating material for heat-sensitive color-forming layer, giving a blue color was obtained by mixing 30 parts by weight of the liquid A, 120 parts by weight of the liquid In, 52 parts by weight of a 60% suspension of calcium carbonate, 40 parts by weight of a 10% aqueous solution of polyvinyl alcohol, 28 parts by weight of SBR latex (L-1537, trade name, ASAHI Chemical Industry, Co., Ltd.; a solid component 50%), 11 parts by weight of stearamide (Celozol A-877, trade name, made. Chukyo Yushi Co., Ltd.; a solid component 26.5%) and 82 parts by weight of water.

- Receiving covering materials for heat-sensitive recording layer, giving a purple color

Liquid (dispersion thermosensitive tsvetopolymer dye)

Twenty parts by weight of hexaflurophosphate 4-N-(2-(2,4-di-tert-AMYLPEROXY)butyryl)piperazinoazepine, 20 parts by weight of a 10% aqueous solution of polyvinyl alcohol and 10 parts by weight of water were mixed and then dispersible and was ground in a sand mill to obtain a dispersion having an average particle size of 0.7 is km

Liquid (the dispersion of the coupling agent)

Fifty parts by weight of 1-(2’-octylphenyl)-3-methyl-5-pyrazolone, 50 parts by weight of 1,2,3-triphenylguanidine, 50 parts by weight of a 10% aqueous solution of polyvinyl alcohol and 25 parts by weight of water were mixed and then dispersible and was ground in a sand mill to obtain a dispersion having an average particle size of 1.0 μm.

Coating material for heat-sensitive color-forming layer, giving a purple color was obtained by mixing 30 parts by weight of the liquid A, 90 parts by weight of the liquid In, 52 parts by weight of a 60% suspension of calcium carbonate, 40 parts by weight of a 10% aqueous solution of polyvinyl alcohol, 28 parts by weight of SBR latex (L-1537, trade name, ASAHI Chemical Industry, Co., Ltd.; a solid component 50%), 11 parts by weight of stearamide (Celozol A-877, trade name, made. Chukyo Yushi Co., Ltd.; a solid component 26.5%) and 82 parts by weight of water.

- Receiving covering materials for heat-sensitive recording layer, giving a yellow color

Liquid (dispersion thermosensitive tsvetopolymer dye)

Twenty parts by weight of hexaflurophosphate 2.5 dibutoxy-4-trillionodollarovoy, 20 parts by weight of a 10% aqueous solution of polyvinyl alcohol and 10 parts by weight of water were mixed and then dispersible and was ground in a sand mill with receipt is m dispersion, having the average particle size of 0.7 microns.

Liquid (the dispersion of the coupling agent)

Fifty parts by weight of 2-chloro-5-(3-(2,4-di-tert-pentyl)phenoxypropylamine)acetanilide, 50 parts by weight of 1,2,3-triphenylguanidine, 50 parts by weight of a 10% aqueous solution of polyvinyl alcohol and 25 parts by weight of water were mixed and then dispersible and was ground in a sand mill to obtain a dispersion having an average particle size of 1.0 μm.

Coating material for heat-sensitive color-forming layer, giving a yellow color was obtained by mixing 30 parts by weight of the liquid A, 90 parts by weight of the liquid In, 52 parts by weight of a 60% suspension of calcium carbonate, 40 parts by weight of a 10% aqueous solution of polyvinyl alcohol, 28 parts by weight of SBR latex (L-1537, trade name, ASAHI Chemical Industry, Co., Ltd.; a solid component 50%), 11 parts by weight of stearamide (Celozol A-877, trade name, made. Chukyo Yushi Co., Ltd.; a solid component 26.5%) and 82 parts by weight of water.

- Receiving covering substance (solid component: 15%) for the intermediate layer

Coating material for the intermediate layer was obtained by mixing 42 parts by weight of a dispersion of kaolin clay (average particle size: 0.6 μm), 200 parts by weight of an aqueous solution of carboxylic acid-modified polyvinyl alcohol (Gohsenol T-330, trade name, made. Nippon Syntic Chemicl Industry Co., Ltd.; a solid component 10%), 100 parts by weight of acrylic emulsion (SC-2250, trade name, made. Nippon Shokubai Co., Ltd.; the solid component is 40%), 33 parts by weight of a solution of dimethylamine (J-001, trade name, made. Showa Denko K.K.; solid component of 30%), 13 parts by weight of a 40% dispersion of zinc stearate (Highmicron F-930, trade name, made. Chukyo Yushi Co., Ltd.; the average particle size of 0.9 μm), 70 parts by weight of heavy calcium carbonate (NS-1000, trade name, made. Nitto Funka Kogyo Co., Ltd.), 25 parts by weight of the emulsion of urethaneacrylate (EM, trade name, made. Arakawa Chemical Industries Ltd.; the solid component is 40%), 5 parts by weight of polysiloxane (SM7025, trade name, made. Dow Corning Toray Silicone Co., Ltd.; a solid component 33%) and 40 parts by weight of water.

Example 120

An example of obtaining a two-color thermosensitive recording material are described below.

(A) Leucocrystal for high-temperature color-forming layer: 3-(4’-dibutylamino-2’-hydroxyphenyl)-3-(5’-aniline-4’-methyl-2’-methoxyphenyl)phtalic.

(B) Leucocrystal for low-temperature color-forming layer: 3-diethylamino-7-chlorofluoro.

(C) Developer: urea-urethane compound synthesized in example 119.

(D) a Sensitizer: diphenylsulfone.

Forty grams of each of the above organic compounds from (a) to (D) were mixed with 40 g of a 10% solution of polyvinyl Speer is a (degree of polymerization of 500 and a degree of saponification of 90%) and 20 g of water, and each thus obtained composition was dispersively in a vertical sand mill (sand mill produced by AIMEX CO., LTD.), thus, to obtain a particle size of 1 μm, thus obtained dispersion liquid (A)-(D) correspond to the compounds (A)to(D), respectively.

On the other hand, 40 g of a light calcium carbonate (Brilliant 15, p. Shiraishi Industrial Co., Ltd.; the average particle size of 0.15 μm) and 60 g of a 0.7% solution of sodium hexametaphosphate were mixed, and the resulting composition was dispersively in the dispersing device Cowles.

Separately, 21% dispersion of zinc stearate was obtained in the form of a dispersion of the lubricant, the fluid (F) and 10% polyvinyl alcohol (NM11, production. Nippon Syntic Chemical Industry Co., Ltd.) received as an adhesive liquid (G).

- Receiving covering liquid (I) for high-temperature heat-sensitive color-forming layer

Liquid coatings for high-temperature heat-sensitive color-forming layer was obtained by mixing the above liquids (A), (C), (D) and (G) so that the ratio of their mass after drying was as follows: (A): (): (E): (G) = 20: 40: 25: 15.

- Getting high-temperature heat-sensitive color-forming layer

High-temperature heat-sensitive color-forming layer was obtained by applying the above-mentioned covering liquid (I) DL the high-temperature heat-sensitive color-forming layer on the paper without wood pulp (neutral paper) with a weight basis 60 g/m 2in the amount of 8 g/m2in units of dry mass using the device for coating Mowag.

- Getting cover fluid (II) for low-temperature color-forming heat-sensitive layer

Liquid to cover for the low-temperature heat-sensitive color-forming layer was obtained by mixing the above liquids (In, (C), (D), (E), (F) and (G) so that the ratio of their mass after drying was as follows: (B): (C): (D): (E): (F): (G) = 10:20:20:20:10:10.

- Obtaining a two-color thermosensitive recording material

Covering the liquid (II) for low-temperature heat-sensitive color-forming layer was applied onto the above-mentioned high-temperature color-forming heat-sensitive layer in an amount of 5 g/m2in units of dry mass. Then the instrument to make the Bekk smoothness (JIS-P8119) thermosensitive recording surface was set at 150 seconds processing to impart smoothness using supercalendering, thus obtaining two-color thermosensitive recording material.

Comparative example 22

Color thermosensitive recording material was prepared in the same manner as in example 119, except for using 2,2-bis(4-hydroxyphenyl)propane instead of the urea-urethane compound synthesized in example 11, and evaluated. The results obtained are summarized in table 8.

Comparative example 23

Two-color thermosensitive recording material was prepared in the same manner as in example 120, except for using 2,2-bis(4-hydroxyphenyl)propane instead of the urea-urethane compound used in example 120, and evaluated. The results obtained are summarized in table 8.

- Evaluation of the color thermosensitive recording materials

On the color thermosensitive recording materials obtained in examples 119 and 120 and comparative examples 22 and 23, were printed using a commercial thermal printer (NC-1, trade name, made. Fuji Photo Film Co., Ltd.), and the image quality and the ability to save the image was evaluated by the following methods.

<image Quality>

5 sheets of each recording material was visually estimated the clarity, contrast, density non-uniformities in the image, and the like and they were assessed on the following 5 grades;: well,: almost good,: medium,almost bad: bad.

<the Ability to save the image>

Each recording material was placed between vinyl chloride wrapping and tapes or vinyl chloride files and applied a force of 300 g/cm 2on top of. After 24 hours at 40° visually estimated the intensity of this color is printed parts and neotectonic part (the original surface of the recording material). When the intensity of staining was only slightly reduced, the ability to save the image was evaluated as good.

The results obtained are summarized in table 8. Thus, the recording materials of examples 119 and 120 were good image quality and has demonstrated excellent ability to save images while recording materials of comparative examples 22 and 23 were worse than the recording materials of examples 119 and 120.

Example 121

The urea-urethane compound synthesized in the same manner as in example 24, and the variance was obtained by dispersing 2 g of this compound by grinding it together with 8 g of an aqueous solution of 2.5 wt.% polyvinyl alcohol in the paint shaker for 6 hours. The temperature of the dispersion immediately after the dispersion was 25°C. the Diameter of dispersed particles of the compound was 0.6 μm.

Another dispersion was obtained by dispersing 70 g of 3-dibutylamino-6-methyl-7-onlineflorida, grinding it together with 130 g of an aqueous solution of 5.4 wt.% polyvinyl alcohol in a sand mill (made. AIMEX CO., LTD.; tank volume 400 ml) with the number of revolutions of 2000 rpm for 3 hours.

Emekuku dispersion was obtained by dispersing 70 g of diphenylsulfone, by grinding it together with 130 g of an aqueous solution of 5.4 wt.% polyvinyl alcohol in a sand mill (made. AIMEX CO., LTD.; tank volume 400 ml) with the number of revolutions of 2000 rpm for 3 hours.

One other dispersion was obtained by mixing 10 g of calcium carbonate, 30 g of water and stirring the mixture using a mixer.

On the other hand, the dispersion of the aluminum hydroxide was obtained by processing a mixture of 60 parts by weight of aluminum hydroxide and 40 parts by weight of an aqueous solution of 12.5 wt.% polyvinyl alcohol for 2 hours using a sand mill for dispersion of aluminum hydroxide so that the average particle size was about 1 micron.

Covering liquid was obtained by stirring and mixing the above-mentioned dispersions and other components in the following proportions (the proportions of dry basis); the variance of the above compounds in terms of dry solid substance: 20 parts by weight, the dispersion of the 3-dibutylamino-6-methyl-7-onlineflorida in terms of dry solid substance: 10 parts by weight, dispersion of diphenylsulfone in terms of dry solid substance: 25 parts by weight, dispersion of calcium carbonate in terms of dry solid substance: 40 parts by weight, dispersion of aluminum hydroxide in terms of dry solid substance: 13 parts by weight, dispersion of zinc stearate (content is solids: 16 wt.%) in terms of dry solid substance: 20 parts by mass and 15 wt.% polyvinyl alcohol in terms of dry solid substance: 15 parts by mass.

Then this covering liquid for heat-sensitive recording layer was applied onto illyuminirovaniya paper speed of 50 m/min, using a device for coating corrugated roller (200 mesh; Cup depth 20 μ ). Thus treated illyuminirovaniya paper was dried at 80° C for 3 seconds with obtaining thermosensitive recording layer with a thickness of 2 μ . Then, a transparent covering liquid in the composition with the aqueous dispersion of the acrylic polymer (consisting mainly of units of methyl methacrylate units of 2-ethylhexyl acrylate and styrene units and having a glass transition point of approximately 40° (C) was applied to the coated surface aluminiumalloy paper to a thickness of 8 μ using the device for applying the coating roller, and dried at 80° within 10 seconds of receipt of metallized paper for laser marking in accordance with the present invention.

Metallized paper was irradiated with laser beams from laser carbon dioxide. Can be obtained the exact imprint color display was good. Test for resistance to plasticizer was performed by placing a metallized paper between wrapping films, and it was found that the resistance to plasticizer was good that the printed area was fog. The results obtained are summarized in table 9.

Example 122

The urea-urethane compound synthesized in the same manner as in example 85, and the variance was obtained by dispersing 2 g of this compound, by grinding it together with 8 g of an aqueous solution of 2.5 wt.% polyvinyl alcohol in the paint shaker for 6 hours.

Then metallized paper for laser marking was obtained in the same manner as in example 121, except for using dispersion of the above compounds instead of the dispersion of the compound obtained in example 121, and using diphenylsulfone instead of aluminum hydroxide, and evaluated. The results obtained are summarized in table 9.

Comparative example 24

Metallized paper for laser marking was obtained in the same manner as in example 121, except for using 2,2-bis(4-hydroxyphenyl)propane instead of the urea-urethane compound synthesized in example 121, and evaluated. The results obtained are summarized in table 9.

<Sensitivity manifestations color>

Products for laser marking was irradiated with laser beams with a dose of 0.6 J/cm2from laser carbon dioxide (Unimark, production. USHIO INC.) through the template, able to the appearance of numbers. When he had a clear track and the intensity of staining was high, the sensitivity of the degree of color development is estimated to be the Wali as good.

“Resistance to the action of the plasticizer>

Three vinyl chloride wrapping film was placed on each of the upper and lower surfaces marked product glaeserne marking and the resulting composition was left under the load of 300 kg/cm2at 40° C for 24 hours. Then visually evaluated the intensity of this color-printed part. When it was only a small decrease in density printing, the ability to save print was evaluated as good.

Example 123

(1) Receiving the upper paper

The solution obtained by dissolving 2.5 parts by weight of 3-diethylamino-7-chlorofluoride in 80 parts by weight of NISSEKI HISOL N-296 (oil, trade name, made. Nippon Sekiyu Depending K.K.)was emulsiable 100 parts by weight of an aqueous solution of 5 wt.%, pH 4.0, obtained by dissolving a styrene-maleic anhydride together with a small amount of sodium hydroxide. On the other hand, when a mixture of 10 parts by weight of melamine, 25 parts by weight of 37% aqueous formaldehyde solution and 65 parts by weight of water was set at pH of 9.0 with sodium hydroxide and heated at 60°C, the mixture became clear after 15 minutes and got precondensed melamine-formaldehyde. Precondensed added to the above emulsion and the resulting mixture was successively stirred for 4 hours, maintaining the mixture at 60°C, is then cooled at room temperature. A solid component obtained dispersion of microcapsules was 45%.

Thus obtained dispersion of microcapsules were applied to paper and dried to obtain the top of the paper.

(2) Receiving the lower paper

The variance was obtained by dispersing 15 g of the composition synthesized in the same manner as in example 7, by grinding it together with 45 g of an aqueous solution of 2 wt.% polyvinyl alcohol in the paint shaker at ambient temperature for 45 minutes.

Another dispersion was obtained by mixing 60 g of calcium carbonate with 90 g of water and stirring the mixture using a mixer.

The liquid coating was obtained by mixing and stirring 40 parts by weight of the above dispersion composition, 125 parts by weight of a dispersion of calcium carbonate and 120 parts by weight of an aqueous solution of 10 wt.% polyvinyl alcohol.

Covering the liquid was applied to the main paper with a weight basis of 40 g/m2using the device for coating with a pin number 10 with getting the bottom of the paper.

The result of evaluating the intensity of the color was so good that the optical density was 0,7.

The result of the evaluation of resistance to the action of the solvent using the hand cream was so good that it was possible to read the written part. The results obtained are summarized in table 10.

Comparative the example 25

A recording material sensitive to pressure, was obtained in the same manner as in example 123, except for use of activated alumina as a developer instead of the urea-urethane compound used in example 123, and evaluated. The results obtained are summarized in table 10.

INDUSTRIAL APPLICATION

The application of specific urea-urethane compounds makes it possible to provide at low cost color-forming composition and a recording material which is excellent in the ability to maintain image and the sensitivity of the degree of color development.

Examples 124-134

Similar to that described in example 9 to 27.8 g of 2,4-colordistance in the flask was added 100 g of toluene as a solvent, after which there was added dropwise a solution of 7.4 g of aniline in 37 g of toluene at room temperature for 1 hour. The interaction was carried out for another 1 hour. The white solid precipitate obtained by filtration, washed with hexane and then dried overnight in vacuum to obtain 20 g of white crystals (intermediate compound (I)). Then 5 g of the thus obtained intermediate compound (I) was added to ethanol (example 124), 1-propanol (example 125), 2-propanol (example 126), n-butyl alcohol (example 127), isobutyl alcohol (example 128), sec-butyl alcohol (example 12), the cyclohexanol (example 130), 1-hexanol (example 131), 1-decanol (example 132), stearyl alcohol (example 133) and benzyl alcohol (example 134), respectively, instead of methanol, is used as the aliphatic alcohol in example 9. The interaction was carried out at 60° C, after which the excess solvent was removed using an evaporator, and then added toluene. The obtained suspension was filtered to obtain white solids on the filter paper. White solid was washed with n-hexane and then dried overnight in vacuum to obtain a urea-urethane composition in the form of a white powder. The molar ratio of the starting materials, reaction conditions, HPLC purity (area ratio), the melting point and the intended structure of the main component of the obtained urea-urethane composition in each reaction are shown in table 11.

Then received a thermosensitive recording material in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1 was used above compound (S-1)-(S-11), and evaluated it. The results obtained are summarized in table 14.

Examples 135-138

As described in example 9, to 27.8 g of 2,4-colordistance in the flask was added 100 g of toluene as a solvent, after which there is added dropwise obavljale solution of 7.4 g of aniline in 37 g of toluene at room temperature for 1 hour. The interaction was carried out for another 1 hour. The white solid precipitate obtained by filtration, washed with hexane and then dried overnight in vacuum to obtain 20 g of white crystals (intermediate compound (I)). Then 5 g of the thus obtained intermediate compound (I) interacted with the supplied dropwise phenol (example 135), o-methoxyphenol (example 136), p-METHYLPHENOL (example 137) and p-chlorophenol (example 138) as an aromatic alcohol, dissolved in 30 ml of MEK, instead of methanol used in example 9.

The interaction was carried out at 60° C, after which the excess solvent was removed using an evaporator, and then there was added toluene. The obtained suspension was filtered to obtain white solids on the filter paper. White solid was washed with n-hexane and then dried overnight in vacuum to obtain a urea-urethane composition in the form of a white powder. The molar ratio of the starting materials, reaction conditions, HPLC purity (area ratio), the melting point and the intended structure of the main component of the obtained urea-urethane composition in each reaction are presented in table 11.

Then heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethanes is the first connection, synthesized in example 1 was used above compounds (E-1), (E-2), (E-4), (E-5) and evaluate it. The results obtained are summarized in table 14.

Examples 139-144

To 27.8 g of 2,4-colordistance in the flask was added 100 g of toluene as a solvent, after which there was added dropwise a solution of 7.5 g of phenol in 37 g of toluene at 40° C for 1 hour. Then the interaction was carried out at 40° C for another 1 hour. The white solid precipitate obtained by filtration, washed with hexane and then dried overnight in vacuum to obtain 20.5 g of white crystals (intermediate compound (II)). Then 5 g of the thus obtained intermediate compound (II) interacted with dropwise supplied aniline (example 139), 4-methyl-aniline production (example 140), 4-Chloroaniline (example 141), 2-methoxy-5-N,N-diethylaluminium (example 142), ethylamine (example 143) and 4-methoxybenzoate (example 144) as the amine compounds dissolved in 30 ml of MEK. The interaction was carried out at 30° C, after which the excess solvent was removed using an evaporator, and then there was added toluene. The obtained suspension was filtered to obtain white solids on the filter paper. White solid was washed with n-hexane and then dried overnight in vacuum to obtain a urea-urethane composition in the form of a white powder. M is regular the original products, the reaction conditions, the HPLC purity (area ratio), the melting point and the intended structure of the main component of the obtained urea-urethane composition in each interaction are presented in table 12.

Then heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1 was used above compound (S-8), (E-10), (11), (13), (E-44) and (E-9) and evaluated it. The results obtained are summarized in table 14.

Example 145

To 27.8 g of 2,4-colordistance in the flask was added 100 g of toluene as a solvent, after which there was added dropwise a solution of 9.8 g of p-anisidine in 37 g of toluene at room temperature for 1 hour. Then the interaction was carried out at 40° C for another 1 hour. The white solid precipitate obtained by filtration, washed with hexane and then dried overnight in vacuum to obtain 22 g of white crystals. Then 5.6 g thus obtained white crystals interacted with 10 g of phenol in 30 ml of MEK at 60° C, after which the excess solvent was removed using an evaporator, and then there was added toluene. The obtained suspension was filtered to obtain white solids on the filter paper. White solid was washed with n-hexane and the ATEM was dried overnight in vacuum to obtain 4.3 g of the urea-urethane composition in the form of a white powder. The HPLC purity (area ratio) was 95%, a melting point equal to 176° and the proposed structure of the main component of the obtained urea-urethane composition was (E-6).

Then heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1 was used above compound (S-6) and evaluated it. The results obtained are summarized in table 14.

Example 146

To 27.8 g of 2,4-colordistance in the flask was added 100 g of toluene as a solvent, after which there was added dropwise a solution of 10.7 g of p-aminoacetophenone in 37 g of toluene at room temperature for 1 hour. The interaction was carried out for another 1 hour. The white solid precipitate obtained by filtration, washed with hexane and then dried overnight in vacuum to obtain 23 g of white crystals. Then 5.8 g thus obtained white crystals interacted with 10 g of phenol in 30 ml of MEK at 60° C, after which the excess solvent was removed using an evaporator, and then there was added toluene. The obtained suspension was filtered to obtain white solids on the filter paper. White solid was washed with n-hexane and then dried overnight in vacuum to obtain 4.5 g urea-ur anovas composition in the form of a white powder.

The HPLC purity (area ratio) was equal to 95%, a melting point equal to 194%, and the anticipated structure of the main component of the obtained urea-urethane composition was (E-7).

Then heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1 was used above composition (E-7), and evaluated it. The results obtained are summarized in table 14.

Example 147

To and 39.9 g of 4,4’-difenilmetana diisocyanate (MDI) instead of 2,4-toluene diisocyanate, as in example 9, was added as a solvent of 100 g of toluene, and then was added dropwise a solution of 7.4 g of aniline in 37 g of toluene at room temperature for 1 hour. The interaction was carried out at room temperature for another 1 hour. Precipitated white solid was recovered by filtration, washed with hexane and then dried overnight in a vacuum with the receipt of 25.7 g of white crystals. Then 6.4 g thus obtained crystals interacted with 10 g of phenol in 30 ml of MEK at 60 S, after which the excess solvent was removed using an evaporator, and then added toluene. The obtained suspension was filtered to obtain a white solid product on the filter paper. The solid white product was washed with n-hexane and then dried over but is in vacuum to obtain 4.8 g of the urea-urethane composition in the form of a white powder. The HPLC purity (area ratio) was 95%, the melting point was 210° and the proposed structure of the main component of the obtained urea-urethane composition was (E-15).

Then heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1 was used above composition (E-15), and evaluated it. The results obtained are summarized in table 14.

Example 148

Repeating the same method described in example 4, except that instead of 3.7 g of 4,4’-diaminodiphenylsulfone used 3.7 g of 3,3’-diaminodiphenylsulfone, to obtain 5.0 g of the urea-urethane composition in the form of white crystals. The proposed structure of the main component of the obtained urea-urethane composition was (E-21).

Then heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1 was used above composition (E-21), and evaluated it. The results obtained are summarized in table 14.

Example 149

Repeating the same method described in example 4, except that instead of 3.7 g of 4,4’-diaminodiphenylsulfone used 2,95 g of 4,4’-diaminodiphenylmethane, Poluchenie 8.0 g urea-urethane composition in the form of white crystals. To 3.6 g of these crystals was added 15 g of phenol for conducting the similar reaction as described in example 4. Received 4.7 grams of a urea-urethane composition in the form of a white powder. The proposed structure of the main component of the obtained urea-urethane composition was (E-27).

Then heat-sensitive recording material was obtained in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1 was used above composition (E-27), and evaluated it. The results obtained are summarized in table 14.

Examples 150-153

Similar to that described in example 9 to 27.8 g of 2,4-colordistance in the flask was added 100 g of toluene as a solvent, after which there was added dropwise a solution of 7.4 g of aniline in 37 g of toluene at room temperature for 1 hour. The interaction was carried out for another 1 hour. The white solid precipitate obtained by filtration, washed with hexane and then dried overnight in vacuum to obtain 20 g of white crystals (intermediate compound (I)). Then, the thus obtained intermediate compound (I) interacted with dipropyleneglycol (example 150), glycerin (example 151), triethanolamine (example 152) and pentaerythritol (example 153) at 30° With 60 ml of trimethyl phosphate as a solvent added to the quality of the solid fuel catalyst 5 mg dibutyltin winner. The reaction mixture was added to distilled water and filtered to obtain a white solid product on the filter paper. White solid was dried overnight in vacuum to obtain a urea-urethane composition in the form of a white powder. The molar ratio of the starting materials, reaction conditions, HPLC purity (area ratio), the melting point and the intended structure of the main component of the obtained urea-urethane composition in each reaction are shown in table 13.

Then received a thermosensitive recording material in the same manner as in example 1, except that instead of the urea-urethane compound synthesized in example 1 was used above compound (S-31), (S-32), (S-33) and (S-35) and evaluated it. The results obtained are summarized in table 14.

fog.

1. Mocevinoobrazovania the compound represented by the following compounds (S-1)-(S-70):

2. Mocevinoobrazovania composition containing mocevinoobrazovania compound and a diluent, where motivirovochnuyu compound is any compound represented by the following formulas (I)to(VII):

where X and Z independently represent a residue of an aromatic compound or a residue alifaticheskih the connection, each residue can have one or more substituents;

Y0represents a group selected from the group consisting of Torrenova group, xylylene group, Neftyanoy group, hexamethylene group, and -φCH2-φ -, φ- represents fenelonov group;

where X and Y independently represent a residue of an aromatic compound or a residue of aliphatic compounds, each residue can have one or more substituents;

where X and Y independently represent a residue of an aromatic compound or a residue of aliphatic compounds;

α represents the balance with a valency of 2 or more; n is an integer of 2 or more,

and each residue can have one or more substituents;

where Z and Y independently represent a residue of an aromatic compound or a residue of aliphatic compounds;

β represents the balance with a valency of 2 or more;

n is an integer of 2 or more,

and each residue can have one or more substituents;

where the hydrogen atom of each benzene ring to which ICA can be substituted by the Deputy, which preferably is a residue of aromatic compounds, the aliphatic residue of a compound or a residue of heterocyclic compounds, the Deputy may be a nitro-group, a hydroxyl group, a carboxyl group, nitrosopropane, nitrile group, carbamoyl group, raidgroups, isocyanate group, mercaptopropyl, sulfopropyl, sulfamoyl group or a halogen atom, each residue can have one or more substituents;

γ represents a group selected from the group comprising-SO2-, -O-, -(S)n-, -(CH2)n-, -CO-, -CONH -, and any of groups represented by formulas (a);

or missing;

n is 1 or 2.

where the hydrogen atom of each benzene ring may be replaced by the Deputy, which preferably represents the residue of aromatic compounds, the aliphatic residue of a compound or a residue of heterocyclic compounds, the Deputy may be a hydroxyl group, a nitro-group, a nitrile group, carbamoyl group, sulfamoyl group, a carboxyl group, nitrosopropane, amino group, accelerograph, nitrolingual, gelasinospora,raidgroups, istianity group, mercaptopropyl, sulfopropyl or a halogen atom, each residue can have one or more substituents;

δ ξpredstavljaet a group selected from the group consisting of-SO2-, -O-, -(S)n-, -(CH2)n, -CO-, -CONH-, -NH-, -CH(COOR1)-, -C(CF3)2- and-CR2R3- or is absent;

each R1, R2and R3represents an alkyl group;

n is 1 or 2;

where X, Y and Z independently represent a residue of an aromatic compound or a residue of aliphatic compounds, each residue can have one or more substituents, and each X, Y and Z preferably represents the residue of aromatic compounds,

and where the diluent is a combination of urea and/or urethane compound obtained by the interaction of polyisocyanate compounds with hydroxidealuminum or aminoguanidinium.

3. The method of obtaining motivirovannogo compounds of formulas (I)-(VII)specified in clause 2, which lies in the interaction polyisocyanate compounds with hydroxidealuminum or aminoguanidinium so that the ratio of the number of moles of the polyisocyanate compound to the number of hydroxyl equivalents hydroxycodone or aminoacid allentow of amino compounds was 100/1-1/2 with the formation of one or more urethane or raidgroup from multiple isocyanate groups of the polyisocyanate compound.

4. The method according to claim 3, additionally comprising further adding amino or hydroxycodone, respectively, for its interaction with the rest of the isocyanate groups of the polyisocyanate compound with the receipt of one or more of ureido or urethane groups.

5. The method according to claim 3, characterized by the sequential reactions with the formation of one or more urethane groups and interaction with one or more raidgroup.

6. The method according to claim 3, characterized by reactions with the formation of one or more urethane groups, and/or interaction with the formation of one or more of ureido groups without solvent, or by reactions with the formation of one or more urethane groups and interaction with the formation of one or more raidgroup using the same solvent preferably at a temperature of 0-300°C and/or preferably in the presence of a catalyst.

7. The method of obtaining motivirovannogo compounds of formulas (I)-(VII)specified in clause 2, which lies in the interaction of the amino compounds or hydroxycodone with polyisocyanate adduct obtained by reacting polyisocyanate compounds with hydroxidealuminum or aminoguanidinium so that the equivalent respect of the isocyanate group to the amino or hydroxyl group became 2/1 - 1/100, with the formation of one or more raidgroup or urethane groups, and subsequent removal of unreacted amino compounds or hydroxycodone.

8. Color-forming composition comprising a developer containing mocevinoobrazovania connection defined in claim 2, which is obtained by the method according to any of PP-7, and, optionally, colourless or slightly coloured substance is precursor of the dye.

9. Color-forming composition of claim 8, where colourless or slightly coloured substance is a precursor of the dye is leucocrystal, which, for example, represents at least one leucocrystal selected from leucogranitee triarylmethane type, leucogranitee fluorolog type, leucogranitee fluorenone type and leucogranitee diphenylmethanone type; for example, leucocrystal is a compound selected from compounds represented by the following formula (i):

where both Y2and Y3represent an alkyl group or alkoxyalkyl group;

Y4represents a hydrogen atom, alkyl group, or alkoxygroup;

each of Y5and Y6represents a hydrogen atom, halogen atom, alkyl group, or alkoxygroup,

or connection, etc is stavlennie the following formula (j):

where each of R5and R6is a group represented by the formula (k) or formula (l)

where each of R11-R15represents a hydrogen atom, a halogen atom, a C1-C8is an alkyl group, a C1-C8-alkoxygroup or-NR16R17where each of R16and R17represents an alkyl group of 1-8 carbon atoms,

or

where each of R18and R19represents a hydrogen atom, an alkyl group of 1-8 carbon atoms or phenyl group;

each of R7-R10represents a hydrogen atom, halogen atom, alkyl group of 1-8 carbon atoms, alkoxygroup from 1-8 carbon atoms, or-NR20R21where each of R20and R21represents an alkyl group of 1-8 carbon atoms.

10. Color-forming composition of claim 8 or 9, characterized in that the melting point motivirovannogo connection of the developer is not higher than 500 and not less than 40°C.

11. Color-forming composition according to any one of p-10, characterized in that mocevinoobrazovania connection of the developer comprises a compound selected from the group comprising compounds represented by the General formula (V

where the hydrogen atom of each benzene ring may be replaced by a residue of aromatic compounds, a residue of aliphatic compounds, a residue of heterocyclic compounds, the nitro-group, a hydroxyl group, a carboxyl group, nitrosopropane, nitrile group, carbamoyl group, raidgroups, isocyanate group, mercaptopropyl, sulfopropyl, sulfamoyl group or a halogen atom, each of the residues may have one or more substituents;

γ represents a group selected from the group comprising-SO2-, -O-, -(S)n-, -(CH2)n-, -CO-, -CONH - and any group represented by the formula (a)

or missing;

n is 1 or 2,

and the connection represented by the General formula (VI)

where the hydrogen atom of each benzene ring may be replaced by a residue of aromatic compounds, a residue of aliphatic compounds, a residue of heterocyclic compounds, a hydroxyl group, a nitro-group, a nitrile group, carbamoyl group, sulfamoyl group, a carboxyl group, nitrosopropane, amino group, accelerograph, nitrolingual, Hijazi what agropol, raidgroups, isocyanate group, mercaptopropyl, sulfopropyl or a halogen atom, each of the residues may have one or more substituents;

δ represents a group selected from the group comprising-SO2-, -O-, -(S)n-, -(CH2)n-, -CO-, -CONH-, NH-, -CH(COOR1)-, -C(CF3)2- and-CR2R3-or is absent;

each of R1, R2and R3represents an alkyl group;

n is 1 or 2,

for example, the compound of formula (XX)

and the compound of formula (XXI)

12. Color-forming composition according to any one of paragraphs. 8-11, optionally containing Caloplaca substance, which is, for example, at least one compound selected from β-aftermentioned ether, p-benzylbiphenyl, 1,2-di(m-methylphenoxy)ethane, di-p-methylanthranilate, 1,2-diphenoxyethane, m-terphenyl and stearamide, or compounds represented by the following structural formula (XVIII):

where Y represents any group of SO2-, -(S)n-, -O-, -CO-, -CH2-, -CH(C6H5)-, -C(CH3)2-, -COCO-, -CO3-, -COCH2CO-, -COOCH2-, -CONH-, -OCH2 - and-NH-;

n is 1 or 2,

and the hydrogen atom of each benzene ring may be substituted by a halogen atom, a hydroxyl group, a nitrogroup, nitrosopropane, nitrile group, isocyanate group, isothiocyanato group, mercaptopropyl, sulfamoyl group, sulfonic acid group, an amino group, a residue of aromatic compounds, the aliphatic residue of a compound or a residue of heterocyclic compounds

or compounds represented by the following structural formula (XIX):

where the hydrogen atom of each benzene ring may be substituted by a halogen atom, a hydroxyl group, a nitrogroup, nitrosopropane, nitrile group, isocyanate group, isothiocyanato group, mercaptopropyl, sulfamoyl group, sulfonic acid group, an amino group, a residue of aromatic compounds, a residue of aliphatic compounds or heterocyclic residue of the connection.

13. Color-forming composition according to any one of p-12, which further comprises a component selected from the following group: isocyanate compound, an isocyanate compound and aminosidine; aminoguanidine; acid developer, where acidic developer represents, for example, at least one p is Avital, selected from 2,2-bis(4-hydroxyphenyl)propane, 4-isopropoxyphenyl-4’-hydroxyprednisolone, bis(3-allyl-4-hydroxyphenyl)sulfone, 2,4’-dihydroxydiphenylsulfone and 4,4’-[oxybis(ethyleneoxy-p-phenylenesulfonyl)]diphenol; fluorescent dye; and an agent that gives stability during storage.

14. Recording material containing a color-forming substrate and the layer formed thereon, where the specified color-forming layer includes mocevinoobrazovania connection defined in claim 2, or a color-forming composition as defined in any of paragraphs. 8-13.

15. The recording material 14, characterized in that on the color-forming layer deposited protective layer for the color-forming layer, which, for example, includes a water-soluble polymer, and/or the protective layer includes an inorganic pigment and/or organic pigment and/or the protective layer comprises a lubricating agent.

16. The recording material p. 14, characterized in that the substrate caused an intermediate layer, which caused color-forming layer and the intermediate layer includes a water-soluble polymer and, optionally, the intermediate layer includes an inorganic pigment and/or organic pigment.

17. The recording material 14, characterized in that the layer back-coating deposited on the substrate from the back side relative to the recreational side, having a color-forming layer formed thereon, and the coating layer of the reverse side includes a water-soluble polymer and, optionally, includes an inorganic pigment and/or organic pigment.

18. The recording material according to any one of p-17, characterized in that as a dispersing agent for motivirovannogo compounds it contains at least one compound selected from water-soluble polymers and anionic surfactants such as polyvinyl alcohols, modified polyvinyl alcohol, methylcellulose, hypromellose, condensed naphthalenesulfonate sodium, and ammonium salts of polycarboxylic acids, water-soluble low molecular weight copolymers and 2-ethylhexylacrylate sodium; as dispersing agent for the substance predecessor dye

contains at least one compound selected from water-soluble polymers, nonionic surfactants and anionic surfactants, for example, methylcellulose, hypromellose, polietilenglikolya esters of fatty acids, sulfates polyoxyethylenated esters and 2-ethylhexylacrylate sodium.

19. The recording material according to any one of p-18, which is a heat-sensitive recording material.

0. Heat-sensitive recording material according to claim 19, characterized in that preferably the average particle size motivirovannogo connection is not more than 5 μm and not less than 0.05 μm; liquid temperature during grinding motivirovannogo connection is 60°C or below; pH during grinding motivirovannogo connection is 5 to 10; as dispersing agent for Caloplaca substances it contains at least one compound selected from water-soluble polymers and anionic surfactants such as polyvinyl alcohols, modified polyvinyl alcohol, methylcellulose, hypromellose, condensed naphthalenesulfonate sodium, and ammonium salts of polycarboxylic acids water-soluble low molecular weight copolymers and 2-ethylhexylacrylate sodium; mocevinoobrazovania connection and Caloplaca matter thoroughly crushed together; the pH of the surface of the substrate, which covers the heat-sensitive recording layer of thermosensitive recording material is from 3 to 9.

21. The recording material p. 14, which represents a heat-sensitive magnetic recording material such as this, where thermosensitive recording layer comprising a urea-urethane compound have is Italia, defined above, is applied on one side of the substrate, and a magnetic recording layer on the other side.

22. Heat-sensitive magnetic recording material according to item 21, which represents a ticket, such as train ticket.

23. The recording material 14, which represents a label for heat-sensitive record such as this, where thermosensitive recording layer comprising mocevinoobrazovania connection of the developer deposited on one side of the substrate, and an adhesive layer on the other side, and where, optionally, the coating layer to the back side applied between the adhesive layer and the substrate and/or intermediate layer is applied between thermosensitive recording layer and the substrate, and/or a protective layer deposited on the heat-sensitive recording layer.

24. The recording material 14, which represents a color thermosensitive recording material, for example, where at least two heat-sensitive recording layer deposited on one side of the substrate and at least one of the above heat-sensitive recording layers includes mocevinoobrazovania connection of the developer, as defined above, with, optionally, between thermosensitive recording layer deposited intermediate layer.

25. Color thermocou the responsive record material according to paragraph 24, characterized in that includes a substrate and two heat-sensitive recording layer, laminated on one side of the substrate, which have different temperatures, the degree of color development, respectively, and are the manifestation of the colors of different color tones, respectively, the upper heat-sensitive recording layer, includes any agent that is used both as a developer and as a tone reliever, or reversing the developer, and the lower thermosensitive recording layer comprising mocevinoobrazovania connection of the developer, with preferably two heat-sensitive recording layers, the upper layer is a low-temperature color-forming layer capable of undergoing a color expression at low temperature and to be achromatization at high temperature, and the bottom layer is a high temperature color-forming layer capable of undergoing a color expression at high temperature.

26. The way to obtain heat-sensitive recording material as defined in 14, characterized in that for forming a thermosensitive recording layer on the substrate heat-sensitive liquid for coating with pH from 5 to 12 put the recording layer of thermosensitive recording material.

27. The product for the laser is nd marking, characterized in that it has on the surface of thermosensitive recording layer comprising mocevinoobrazovania connection of the developer, as defined in claim 2, and, optionally, colourless or slightly coloured substance is precursor of the dye and an agent that improves the recording sensitivity, representing, for example, at least one compound selected from aluminum hydroxide, white mica, wollastonite and kaolin, and, optionally, heat-sensitive recording layer a protective layer comprising a water binding agent having a glass transition point 20-80°C.

28. Products for laser marking according to item 27, which represents any label, packaging material and containers.

29. The method of obtaining products for laser marking, which consists in coating the substrate color-forming composition for marking, including mocevinoobrazovania connection of the developer, as defined in claim 2, and, optionally, colourless or slightly coloured substance is precursor of the dye and an agent that improves the recording sensitivity, and drying the thus obtained substrate.

30. The method of labeling articles, which consists in irradiation of thermosensitive recording layer products for laser marking according to item 27 or 28 laser beams.

31. Color-forming composition DL the marking, characterized in that it includes mocevinoobrazovania connection of the developer, as defined in claim 2, and, optionally, a colorless or light-colored substance is precursor of the dye and an agent that improves the recording sensitivity.



 

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using the diamine of General formula

where A=

R=2-furyl, 2-thienyl, 2-(1-methyl)pyrrolyl, 3-(1-methyl)indolyl, and aldehydes in the presence of acetate or copper sulfate, characterized in that the interaction takes place by boiling in 50% acetic acid, followed by decomposition of the copper salt, the effect on its suspension in 50% acetic acid sodium thiosulfate in 100With

The invention relates to derivatives of 6-sulfamoylbenzoic-4-carboxylic acid of formula (1), where R1, R2, R3and R4such as defined in the claims

The invention relates to 1-methyl-5-alkylsulfonyl-, 1-methyl-5-alkylsulfonyl - 1-methyl-5-alkylthiomethyl pyrazolylborate and herbicide tool based on them

The invention relates to tricyclic condensed heterocyclic compounds of the formula I, X is, for example, CH, CH2, СНR (where R means a lower alkyl group or a substituted lower alkyl group) or CRR' (where R and R' have the values specified above for R); Y means, for example, CH, CH2or C=O; z means, for example, S, S=O=; U denotes C; R1-R4independent means, for example, a hydrogen atom, SR (where R has the above values), phenyl group, substituted phenyl group, follow group, thienyl group, benzofuran or benzothiazyl at least one element of R5and R8means, for example, HE and the rest of the elements of R5and R8independent means, for example, a hydrogen atom; and their optical isomers, conjugates, and pharmaceutically acceptable salts

The invention relates to a new crystalline modification of 5-fluoro-1-(tetrahydro-2-furyl)uracil, as well as complex compounds of this form with 2,4-dioxo-6-methyl-1,2,3,4-tetrahydropyrimidine or licorice root extract (Radices Glycyrrhzae)

The invention relates to new non-steroidal compounds which are high-affinity modulators of steroid receptors

The invention relates to the production of active ingredients of the General formula I:

< / BR>
(1) where R is C1-C4is an alkyl group;

M is a hydrogen atom or an ion of sodium, potassium or calcium;

A - -S-, -,-SO - or-SO2group

The invention relates to benzosulfimide derivative of the formula I, where R1denotes hydrogen, R2denotes hydrogen, trifluoromethyl or (ness.)alkyl, R3denotes hydrogen or amino, or R1and R2or R3and R2together represent a group-CH= CH-CH= CH-, Z denotes pyrimidine-4-yl, pyridine-4-yl, pyridine-2-yl or phenyl, R4, R5each independently of one another denotes hydrogen, (ness.)alkyl, trifluoromethyl, halogen, (ness.)alkoxy, nitrile, amino, (ness.)alkylamino-, di(ness.)alkylamino, piperazinil, morpholinyl, pyrrolidinyl, vinyl, WITH3-C6cycloalkyl,3-C6cycloalkenyl, tert-butylamine, hydroxyalkylated, phenylethyl, naphthyl, thiophenyl or phenyl which may be substituted with halogen, (ness.)alkoxyl, (ness.)the alkyl, trifluoromethyl or nitro-group, or a group-NH(CH2)nNR6R7, -N(CH3)(CH2)nNR6R7, -NH(CH2)n-morpholine-4-yl or-NH(CH2)nOH, n denotes the number of 2-4, R6and R7each independently of one another denotes hydrogen or (ness.)alkyl, and their pharmaceutically acceptable salts

The invention relates to derivatives of 5-areolation formula I, where a represents-CH2-, -C(O)- or-S(O)2-; Z denotes a group of formula b or D:

< / BR>
where X is O or S; R6and R7independently from each other selected from the group including hydrogen, C1-C6alkyl, CF3WITH1-C6alkylthio,1-C6alkoxy, halogen, nitro, hydroxy, and-NR9R10where R9and R10independently of one another denote hydrogen or C1-C6alkyl; R1means hydrogen, C1-C6alkyl, C1-C6alkoxy, hydroxy2-C6alkyloxy, hydroxy, halogen, cyano, carboxy, co2SOP(CH3)2, -СОNR9R10, -ОСОNR9R10or ОSO2R11where R9and R10have the meanings indicated above, and R11means1-C6alkyl or CF3; R3means-SO2R12or-SO2NR13R14where R12means1-C6alkyl; R13means hydrogen or C1-C6alkyl, and R14means hydrogen, C1-C6alkyl, C3-C6cycloalkyl,2-C6alkenyl, hydroxy SS1-C6alkyl, benzyl, phenethyl, naphtalate, acyl, morpholino-C1-C6alkyl, pyrrolidino-C1-C6alkyl, pyridyl-C1-C6alkyl, furanyl-C1-C6alkyl, or R13and R14together with the nitrogen atom to which they are attached, optionally form heterocyclization selected from piperidino, morpholino, di-(C1-C6alkyl)morpholino, pyrrolidino, methylpiperazine, phenylpiperazine, forfilipino; and their pharmaceutically acceptable salts or their esters or carbamates, individual isomers and mixtures of isomers and method thereof
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