Amphoteric fluorescent whitening agent

FIELD: chemistry, textiles, paper.

SUBSTANCE: present invention relates to new amphoteric bis-triazinylaminostilbene fluorescent whitening agents for fluorescent whitening of organic materials, particularly paper. Description is given of use of compounds with formula (5) for fluorescent whitening of paper.

EFFECT: compounds have high bleaching power; fluorescence is not prevented by cation-active polymers or anion-active fluorescent whitening agents contained in the paper.

2 cl, 2 tbl, 48 ex

 

The present invention relates to amphoteric bis-creatinineclearance fluorescent optical brighteners (OSF), the method of their production and use for the fluorescent whitening of synthetic or natural organic materials, in particular paper.

Fluorescent optical brighteners for the fluorescent whitening of paper most commonly used types are the agents that belong to the class of derivatives of di-, Tetra - or hexachlorophane acid bis-triethynylbenzene, which by nature of anionactive. However, in modern methods of manufacturing paper as auxiliary substances commonly used cationic polymers, such as retention agents or facilitators to dehydration, particularly during the manufacture of recycled paper, which is most likely to contain residual amounts of anionic OSF. However, the presence of cationic polymers leads to quenching of fluorescence anionic OSF, which is obviously a disadvantage. There is therefore a need in the OLF of this type, which is not extinguished by such polymers and, in addition, able to be combined with anionic OSF.

It was found that some new amphoteric OSF does not have a negative impact not only prisutstviuyuschih polymers, but the presence of residual anionic OSF, and when applied to paper, these agents also exhibit excellent whitening properties.

Accordingly, a first object of the present invention offers new amphoteric fluorescent optical brighteners, which include a mixture of compounds of the formula

in which

A* denotes a group of the formula

in which

And means-X-Y-NR3R4,

With means-NR1R2a

* Denotes a group of the formula

,or,

in which

D represents-NR5R6and

E represents-X1-Y1-NR7R8resulting

X and X1each independently from each other represents-O - or-NH-,

Y and Y1each independently of one another denotes remotemachine2-C8alkylenes or branched C3-C8alkylenes chain which may be interrupted by one or two atoms of nitrogen, oxygen, or sulfur, or represents 5 - or 6-membered cycloaliphatic ring, preferably cyclohexyl,

R1, R2, R5and R6each independently one who represents a hydrogen atom, With1-C8alkyl, C2-C4hydroxyalkyl,1-C4alkoxyl1-C4alkyl, phenyl which is not substituted or substituted by a halogen atom, a C1-C4alkoxy, C1-C4the alkyl or sulfonamideubul, or

R1and R2and/or R5and R6together with the nitrogen atom to which they are attached, complete morpholino-, piperidino or pyrolidine ring,

R3, R4, R7and R8each independently of one another denotes a hydrogen atom, a C1-C4alkyl, C2-C4hydroxyalkyl or R3and R4and/or R7and R8together with the nitrogen atom to which they are attached, complete morpholino-, piperidino or pyrolidine ring, and

M denotes a hydrogen atom, an alkaline or alkaline-earth metal, ammonium or alkylammonium.

Amphoteric compounds of formulas (1A) to (1C) can exist in the form of either internal or common salt. For example, in the case in which M in the above formula denotes a hydrogen atom, compound (1A) to (1C) can exist as an equilibrium mixture of neutral molecules and amphoteric ion, in which M denotes a negative charge in the form of SO3-while the proton remains of amine residues in the form of ammonium salts-N+HR3R 4and-N+HR7R8. Therefore, in order for the connection formulas (1A) to (1C) had a really amphoteric properties, must equal the total number of acidic groups and basic amino groups contained in the molecule. Because the rest diaminodiphenylsulfone acid already contains two sulfonic acid groups, preferably, the molecules (1A) to (1C) no additional acid groups, and, moreover, that they are substituted with two amino groups, which are relatively high basicity, in order to have the ability to form amphoteric ions, i.e. in addition to the amino groups attached directly to the triazine ring.

In one preferred embodiment, the object of the invention is a fluorescent optical Brightener, which includes a mixture of compounds of the formula

,

in which

X, Y, R1, R2, R3, R4, R5, R6and M have the above meanings, and more preferably a mixture of compounds (1d), (1E) and (1f),

have

Y denotes remotemachine2-C6alkalinity or branched C3-C6alkalinity residue which may be interrupted by 1 or 2 oxygen atoms, R 1, R2, R5and R6each independently of one another denotes a hydrogen atom, a C1-C4alkyl, C2-C4hydroxyalkyl, phenyl which is not substituted or is substituted by methoxy, ethoxy or group-SO2NH2or

R1and R2and/or R5and R6together with the nitrogen atom to which they are attached, complete morpholino ring, R3and R4both indicate With1-C4alkyl, C2-C4hydroxyalkyl or together with the nitrogen atom to which they are attached, complete morpholino ring,

M denotes a hydrogen atom, lithium, potassium or sodium, and X has the previously specified values.

The most preferred mixtures of compounds (1d) - (1f) are a mixture of those compounds in which X represents-O - or-NH-,

Y denotes remotemachine2-C4alkalinity or branched C3-C4alkilinity the rest,

R1and R5both represent a hydrogen atom, a C1-C4alkyl, C2-C4hydroxyalkyl or phenyl,

R2and R6both denote a hydrogen atom or a C2-C4hydroxyalkyl,

R3and R4both indicate With1-C4alkyl, C2-C4hydroxyalkyl or together with the nitrogen atom to which they are attached, complete morpholino ring,

The m denotes the hydrogen atom or sodium.

In the second preferred embodiment, the object of the invention is a fluorescent optical Brightener, which includes a mixture of compounds of the formula

in which X, X1Y, Y1, R1, R2, R3, R4, R7, R8and M have the meanings mentioned above, and in more preferred embodiment, a mixture of compounds (1d), (1g) and (1h), whose

X and X1both represent-NH-,

Y and Y1each independently of one another denotes remotemachine2-C6alkalinity or branched C3-C6alkalinity residue which may be interrupted by 1 or 2 oxygen atoms,

R1and R2each independently of one another denotes a hydrogen atom, a C1-C4alkyl, C2-C4hydroxyalkyl, phenyl which is not substituted or is substituted by methoxy, ethoxy or group-SO2NH2or R1and R2together with the nitrogen atom to which they are attached, complete morpholino ring,

R3, R4, R7and R8each independently of one another denotes a hydrogen atom, a C1-C4alkyl, C2-C4hydroxyalkyl or

R3and R4and/or R7and R8together with the nitrogen atom to which they attach is I, complete morpholino ring, and M represents a hydrogen atom, lithium, potassium or sodium.

The most preferred mixtures of compounds (1d), (1g) and (1h) are a mixture of those compounds, in which

X and X1both represent-NH-,

Y and Y1each independently of one another denotes remotemachine2-C4alkalinity or branched C3-C4alkilinity the rest,

R1denotes a hydrogen atom, a C1-C4alkyl, C2-C4hydroxyalkyl or phenyl,

R2denotes a hydrogen atom or a C2-C4hydroxyalkyl or

R1and R2together with the nitrogen atom to which they are attached, complete morpholino ring,

R3, R4, R7and R8each independently of one another denotes a hydrogen atom, a C1-C4alkyl, C2-C4hydroxyalkyl or

R3and R4and/or R7and R8together with the nitrogen atom to which they are attached, complete morpholino ring, and M represents a hydrogen atom or sodium.

In the third embodiment, the object of the present invention are new amphoteric fluorescent optical brighteners of the formula

in which X1Y, Y1, R1, R2, R3, R4, R5, R6, R7, R8and M and EUT values, above, and preferred those compounds of formula (2), in which

X1denotes an oxygen atom

Y and Y1each independently of one another denotes remotemachine2-C6alkalinity or branched C3-C6alkalinity residue which may be interrupted by 1 or 2 oxygen atoms,

R1, R2, R5and R6each independently of one another denotes a hydrogen atom,

With1-C4alkyl, C2-C4hydroxyalkyl, phenyl which is not substituted or is substituted by methoxy, ethoxy or group-SO2NH2or

R1and R2and/or R5and R6together with the nitrogen atom to which they are attached, complete morpholino ring,

R3, R4, R7and R8each independently of one another denotes a hydrogen atom, a C1-C4alkyl, C2-C4hydroxyalkyl or

R3and R4and/or R7and R8together with the nitrogen atom to which they are attached, complete morpholino ring, and M represents a hydrogen atom, lithium, potassium or sodium.

The most preferred compounds of the formula (2) are those in which X1denotes an oxygen atom

Y and Y1both indicate remotemachine2-C4alkalinity or branched C3-C4Alki envy the rest,

R1and R5the same and each represents a hydrogen atom,

With1-C4alkyl, C2-C4hydroxyalkyl or phenyl,

R2and R6the same and each represents a hydrogen atom, a C1-C4alkyl, C2-C4hydroxyalkyl or

R1and R2and R5and R6together with the nitrogen atom to which they are attached, complete morpholino ring,

R3, R4, R7and R8all the same and represent a hydrogen atom or a C1-C4alkyl, and M denotes a hydrogen atom or sodium, mainly hydrogen atom.

In the fourth embodiment, the object of the invention is a fluorescent optical Brightener, which is a compound of the formula

,

in which

R9and R10each independently of one another denotes a hydrogen atom or a C2-C4hydroxyalkyl, a Y, Y1, R1, R2, R3, R4, R5, R6and M have the meanings stated above, provided that when Y and Y1both represent-CH2CH2CH2-, R1and R5both represent phenyl, a R2and R6both represent a hydrogen atom, R3, R4, R9and R10not all represent-CH2CH2HE, therefore the preferred link the mi formula (3) are those have

Y and Y1each independently of one another denotes remotemachine2-C6alkalinity or branched C3-C6alkalinity residue which may be interrupted by 1 or 2 oxygen atoms or one nitrogen atom, or denotes tsiklogeksilnogo the rest,

R1, R2, R5and R6each independently of one another denotes a hydrogen atom, a C1-C8alkyl, C2-C4hydroxyalkyl, phenyl which is not substituted or is substituted by methoxy, ethoxy or group-SO2NH2or

R1and R2and/or R5and R6together with the nitrogen atom to which they are attached, complete morpholino ring,

R3and R4 each independently of one another denotes a hydrogen atom, a C1-C4alkyl, C2-C4hydroxyalkyl or

R3and R4together with the nitrogen atom to which they are attached, complete morpholino ring, and

M denotes a hydrogen atom, lithium, potassium or sodium.

The most preferred compounds of the formula (3) are those in which

Y and Y1both indicate remotemachine2-C6alkylene, which may be interrupted by 1 or 2 oxygen atoms or one nitrogen atom, or denotes tsiklogeksilnogo the rest,

R1and R3the same and each represents in rodny atom, With1-C8alkyl, C2-C4hydroxyalkyl, ethoxyphenyl or phenyl,

R2and R6the same and each represents a hydrogen atom, a C1-C4alkyl, C2-C4hydroxyalkyl or each of R1and R2, R5and R6together with the nitrogen atom to which they are attached, complete morpholino ring,

R3and R9are the same and each represents a hydrogen atom or a hydroxyethyl,

R4and R10are the same and each represents a hydrogen atom or hydroxyethyl, and

M denotes a hydrogen atom or sodium, mainly hydrogen atom.

In the definition of substituents With1-C8alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, n-pentyl, ethylpropyl, dimethylpropyl, methylbutyl, n-hexyl, dimethylbutyl, methylpentyl, ethylbutyl, n-heptyl, etylhexyl, dimethylpentyl, ethylphenyl, trimethylpentyl, n-octyl, methylheptan, dimethyl, ethylhexyl or trimethylpentyl, whereas With1-C4alkoxygroup are, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-, sec-, ISO - or tert-butoxy.

With2-C8alkalinous chain in the definitions of the values of Y and Y1can be, for example, ethylene, n-propylene, metilidinovy, 1 - is 2-methylpropionate, n-butylene, ethylethylene, n-Panteleeva, ethylpropylamine, dimethylpropyleneurea, methylbutylamine, n-jaksilikova, dimethylbutylamine, methylpentanoate, ethylbutylamine, n-gatilova, methylhexanoate, dimethylpentylamine, utilitiesa, trimethylbutyramide, n-Actilingua, methylheptenone, Demetrio ethylhexanoate or trimethylpentene chain. When2-C8Allenova chain is interrupted by heteroatoms, they can serve sulfur atoms or predominantly oxygen atoms, whereas With2-C4hydroxyalkyl can be hydroxyethyl, hydroxy-n - or isopropyl or hydroxybutyl.

Moreover, within the definitions of the halogen atom is an atom of iodine, bromine, fluorine or mainly chlorine, while sulfonamideubul can be-SO2NHC1-C4alkyl, -SO2N(C1-C4alkyl)2or mostly-SO2NH2.

When M denotes an atom of an alkaline or alkaline-earth metal, they can be an atom of lithium, potassium, sodium, calcium or magnesium, while alkylammonium may be ammonium, mono-, di-, tri - or tetraparesis1-C4the alkyl or C2-C4hydroxyalkyl, or their mixture. In a preferred embodiment, M represents the hydrogen atom or sodium.

The mixture of compounds of formulas (1a), (1b) and (1C) on the image the structure can be obtained by reaction of cyanuric chloride in a known reaction conditions step by step in any desired sequence, with each of the following compounds: 4,4'-diaminostilbene-2,2'-disulfonate acid, amine compounds of the formulas R1R2NH and R5R6NH or their mixtures and compounds of the formulas R3R4NYXH and R7R8NY1X1H, or a mixture thereof, resulting in X, X1Y, Y1, R1, R2, R3, R4, R5, R6, R7and R8have the above values.

Depending on quantities and proportions of amines R1R2NH and R5R6NH, and compounds of the formulas R3R4NYXH and R7R8NY1X1H and add them sequentially or simultaneously in the form of a mixture, the proportion of the compounds (1A), (1b) and (1C) can greatly vary. Thus, an object of the present invention is a fluorescent optical Brightener, which includes a mixture of compounds (1A), (1b) and (1C), in which each of the components contained in a molar amount between 5 and 80%, and in the preferred embodiment, they are located in the following approximate molar quantities: 5 to 45% of the compounds of formula (1A), from 15 to 60% of the compound of formula (1b) and from 5 to 45% of the compound of formula (1C). In a more preferred embodiment, compounds (1a), (1b) and (1C) are located in the following approximate molar quantities of 20 to 50% of compounds of formula (1A), from 25 to 50% of compounds of formula (1b) and from 5 to 35% of the compound of formula (1C). Naturally, such a mixture can also be prepared fur the technical mixing separately the components.

Similarly, the compound of the formula (2) can be obtained by reaction of cyanuric chloride in a known reaction conditions step by step in any desired sequence, with each of the following compounds: 4,4'-diaminostilbene-2,2'-disulfonate acid, the amine compound of the formula R1R2NH, amine compound of the formula R5R6NH, gidroksosoedinenii formula R3R4NYOH and the compound of the formula R7R8NY1X1H, and X1Y, Y1, R1, R2, R3, R4, R5, R6, R7and R8have the same meanings as above.

Similarly, the compound of formula (3) can be obtained by reaction of cyanuric chloride in a known reaction conditions step by step in any desired sequence, with each of the following compounds: 4,4'-diaminostilbene-2,2'-disulfonate acid, the amine compound of the formula R1R2NH, amine compound of the formula R5R6NH, amine compound of the formula R3R4NYNH2and the compound of formula R9R10NY1NH2and Y, Y1, R1, R2, R3, R4, R5, R6, R9and R10have the same meanings as above.

In some cases it may be appropriate allocation of intermediate dichlorotriazinyl p is ossadnik 4,4'-diaminostilbene-2,2'-disulfonic acid or in the form of pure asymmetric connections, either in the form of their mixtures, which are involved in additional interactions with education or mixtures of compounds of formulas (1A), (1b) and (1C), or compounds of the formula (2)or compounds of formula (3). Since the number of these intermediate deklarirovannykh derivatives are new, another object of the invention is a compound of the formula

or mixture comprising compounds of the formula

in which

R11and R12each independently of one another denotes a hydrogen atom, a C1-C4alkyl, C2-C4hydroxyalkyl,1-C4alkoxyl1-C4alkyl or together with the nitrogen atom to which they are attached, they complete morpholino-, piperidino or pyrolidine ring,

R13denotes phenyl which is not substituted or substituted by a halogen atom, a C1-C4alkoxy, C1-C4the alkyl or sulfonamideubul, and

M denotes a hydrogen atom, an alkaline or alkaline-earth metal, ammonium or alkylammonium.

In the preferred embodiment, each of R11and R12independently of one another denotes a hydrogen atom, a C1-C4alkyl, C2-C4hydroxyalkyl, but mainly both oznachaet 1-C3hydroxyalkyl or together with the nitrogen atom to which they are attached, complete morpholino ring, whereas R13denotes phenyl which is not substituted or is substituted by methoxy, ethoxy or group-SO2NH2mainly unsubstituted, sulphonamido or ethoxysilanes phenyl, and M denotes a hydrogen atom, lithium, potassium or sodium, preferably hydrogen or sodium.

Similarly to the above methods, compounds of formula (4A) or a mixture of compounds of formulas (4A), (4b) and (4C) can be obtained by reaction of cyanuric chloride in a known reaction conditions step by step in any desired sequence, with each of the following compounds: 4,4'-diaminostilbene-2,2'-disulfonate acid, the amine compound of the formula R11R12NH and amine compound of the formula R13NH2or with a mixture of amine compounds R11R12NH and R13NH2and R11, R12and R13have the same meanings as above.

As mentioned above, the intermediate compounds of formula (4A) can be used to obtain those compounds of the formula (2), in which each of R1and R2independently of one another denotes a hydrogen atom, a C1-C4alkyl, C2-C4hydroxyalkyl,1-C4alkoxyl1-C4alkyl or together with the atom is the monk, to which they are attached, they complete morpholino-, piperidino or pyrolidine ring, R5denotes phenyl which is not substituted or substituted by a halogen atom, a C1-C4alkoxy, C1-C4the alkyl or sulfonamideubul, R6denotes a hydrogen atom, a X1Y, Y1, R3, R4, R7, R8and M have the meanings mentioned above, and can also be used to obtain those compounds of the formula (3), in which in the formula (3) each of R1and R2independently of one another denotes a hydrogen atom, a C1-C4alkyl, C2-C4hydroxyalkyl,1-C4alkoxyl1-C4alkyl or together with the nitrogen atom to which they are attached, they complete morpholino-, piperidino or pyrolidine ring, R5denotes phenyl which is not substituted or substituted by a halogen atom, a C1-C4alkoxy, C1-C4the alkyl or sulfonamideubul, R6denotes a hydrogen atom, and Y, Y1, R3, R4, R9, R10and M have the above values.

Moreover, mixtures of compounds of formulas (4A), (4b) and (4C) can be used to obtain mixtures of those compounds of formula (1a), (1b) and (1C), in which in the formula (1A), (1b) and (1C), each of R1and R2independently of one another denotes a hydrogen atom, a C1 -C4alkyl, C2-C4hydroxyalkyl,1-C4alkoxyl1-C4alkyl or together with the nitrogen atom to which they are attached, they complete morpholino-, piperidino or pyrolidine ring, R5denotes phenyl which is not substituted or substituted by a halogen atom, a C1-C4alkoxy, C1-C4the alkyl or sulfonamideubul, R6denotes a hydrogen atom, and X, X1Y, Y1, R3, R4, R7, R8and M have the meanings specified above.

It is also important to another aspect of some compounds and mixtures of compounds described above. In the case in which X or X1denotes the oxygen atom and at least one of the substituents R3, R4, R7and R8represents a hydrogen atom, in order to guarantee the reaction in the target direction may be necessary to introduce in the place of a nitrogen atom, a protective group, such as-Council, and this protective group is subsequently removed by conventional methods.

Another variant of the synthesis, which may have an advantage in obtaining asymmetric derivatives, is replacement of 4,4'-diaminostilbene-2,2'-disulfonic acid 4-amino-4'-nitrostilbene-2,2'-disulfonic acid and, after the target condensation reactions, in restoring the tion of nitro group to amino group, so in the future can be the next target the condensation reaction.

All starting materials are known compounds, which are easily available or can be obtained by known methods.

Another object of the invention is a composition for bleaching paper, which includes water, a fluorescent optical Brightener, which includes a mixture of compounds of formulas (1a), (1b) and (1C), fluorescent optical Brightener of the formula (2) or fluorescent optical Brightener of the formula

,

in which

R14and R15each independently of one another denotes a hydrogen atom, a C1-C4alkyl or C2-C4hydroxyalkyl, a Y, Y1, R1, R2, R3, R4, R5, R6and M have the meanings mentioned above, and optional excipients.

Such compositions may comprise a mixture of compounds of formulas (1A), (1b) and (1C), the compounds of formula (2) and the compounds of formula (5) itself, but also a mixture of a single component mixtures and components among themselves.

More specifically, such compositions, optical brighteners include water and (in each case calculated on the weight of the composition) from 3 to 25 wt.%, preferably from 5 to 15 wt.% the above mixture of fluorescent optical otmelivat the lei, and from 0 to 60%, preferably from 5 to 50 wt.% auxiliary substances.

Acceptable excipients include, for example, anionic or nonionic dispersing agents from the class of products of accession of ethylene oxide and fatty alcohols, higher fatty acids or the addition products of alkyl phenols or ethylendiaminetetraacetic-propylene oxide, copolymers of N-vinylpyrrolidone and 3-fenilpropionovoy acids, glycols, water retention additives such as glycol, glycerol and sorbitol, and biocides.

Since most of mixtures of compounds of formulas (1a), (1b) and (1C), compounds of the formula (2) and compounds of formula (5) are excellent fluorescent optical brighteners for such substrates as paper, an object of the present invention is, furthermore, the method of the fluorescent whitening of paper, comprising contacting the substrate with a fluorescent optical Brightener, which includes a mixture of compounds of formulas (1A), (1b) and (1C), the compound of the formula (2) and/or the compound of formula (5).

When they are used for the fluorescent whitening of paper, a mixture of compounds of formulas (1A), (1b) and (1C), the compound of the formula (2) and/or the compound of formula (5) in accordance with the present invention can be applied to the paper substrate in the fibrous mass in the form of compositions for coating h is paper or directly in the sizing press or plunger press.

In one preferred embodiment, the object of the present invention is a method for the fluorescent whitening of a paper surface, comprising contacting the paper surface with a composition for coating comprising a white pigment, a dispersion of a binder, an optional water-soluble shared binder and a fluorescent optical Brightener in accordance with the present invention in a quantity sufficient to ensure that the treated paper contains from 0.01 to 1 wt.% in terms of white pigment, a fluorescent Brightener according to the invention.

As a white pigment as a component of a composition for coating paper that is used in accordance with the method of the present invention, the preferred inorganic pigments, such as aluminum silicate and magnesium, such as kaolin, and, in addition, barium sulfate, satinet, titanium dioxide, calcium carbonate (chalk) or talc, and white organic pigments.

Compositions for coating paper, used in accordance with the method of the present invention, as the binder may include, among other things, dispersions of plastics on the basis of copolymers of butadiene/styrene, Acrylonitrile/butadiene/styrene, esters of acrylic acid, esters of acrylic is howling acid/styrene/Acrylonitrile, ethylene/vinyl chloride and ethylene/vinyl acetate; or homopolymers, such as polyvinyl chloride, grades, polyethylene, polyvinyl acetate and polyurethane. The preferred binder is composed of copolymers of styrene/butyl acrylate or styrene/butadiene/acrylic acid or styrene-butadiene rubbers. Other polymer latexes are described, for example, in US 3265654, 3657174, 3547899 and 3240740.

Optional water-soluble protective colloid can be, for example, soy protein, casein, carboxymethyl cellulose, natural or modified starch, chitosan or its derivative, or predominantly of polyvinyl alcohol. The preferred polyvinyl alcohol as a component of the protective colloid can be characterized by a wide range of the degree of saponification and molecular weight, for example, a degree of saponification in the range from 40 to 100 and an average molecular weight in the range of from 10000 to 100000.

Recipes compositions for coating paper described, for example, in J.P.Casey "Pulp and PapeR"; Chemistry and Chemical Technology, 2nd edition, volume III, s-1649, and in "Pulp and PapeR Manufacture", edition 2nd, 5th, volume II, s (McGRaw-Hill).

Preferred compositions for coating paper, used in accordance with the method of the present invention contain from 10 to 70 wt.% in terms of white pigment. In a preferred embodiment, a binder is emesto use in quantity, which is enough to bring the content of dry polymer compound to level from 1 to 30 wt.%, preferably from 5 to 25 wt.% in terms of white pigment. The number of fluorescent optical whitening agent used in accordance with the invention, calculated so that in the preferred embodiment, the fluorescent optical Brightener contained in an amount of from 0.01 to 1 wt.%, more preferably from 0.05 to 1 wt.%, but mainly from 0.05 to 0.6 wt.% in terms of white pigment.

Composition for coating paper that is used in the method in accordance with the invention, can be prepared by mixing the components in any desired sequence at temperatures of from 10 to 100C., preferably from 20 to 80C. the components also include conventional excipients that can be added to regulate the rheological properties such as viscosity or the ability of the compositions for the coating to retain water. Such auxiliary substances are, for example, natural binders, such as starch, casein, albumin and gelatin, ethers of cellulose, such as karboksimetilcelljuloza and hydroxyethylcellulose, alginic acid, alginates, polyethylene oxide and polietilenoksidnoy aliphatic ethers, with aimery of ethylene oxide and propylene oxide, polyvinyl alcohol, water-soluble products of condensation reactions of formaldehyde with urea or melamine polyphosphates or salts of polyacrylic acids.

In a preferred embodiment, the composition for coating used in accordance with the method of the present invention, used for the manufacture provided with a coating of printing or writing paper or special paper products, such as inkjet paper and photo paper and thick paper.

Composition for coating used in accordance with the method according to the invention may be applied to the substrate by any conventional method, for example using an air squeegee, squeegee coating, roller, conventional squeegee or rod or in the sizing press, after which the coating is dried at a temperature on the paper surface in the range from 70 to 200C., preferably from 90 to 130C., to a residual moisture content of 3 to 8%, for example, using radiation dryers and/or dryers for drying with hot air. Thus even at low temperatures drying achieve a relatively high degree of whiteness.

With the application of the method in accordance with the invention receive coverage, which differ in the optimal distribution of the dispersed fluorescent optical Brightener on the entire surface is ti and high degree of whiteness, high siteproject and resistance to elevated temperature (e.g., stable for 24 hours at a temperature of from 60 to 100C)and excellent resistance to soaking water liquids.

In the second preferred embodiment, the object of the present invention is a method for the fluorescent whitening of a paper surface, comprising contacting the paper in the size press with an aqueous solution containing glue, optional inorganic or organic pigment and from 0.1 to 20 g/l of fluorescent optical Brightener according to the invention. In a preferred embodiment, the adhesive is a starch-derived starch or synthetic sizing substance, mainly water-soluble copolymer.

In the third preferred embodiment, the object of the invention is a method for the fluorescent whitening of paper during formation of the paper, making the OLF add directly into the fibre mass. In this case, the OLF may be in the form of a solution, dispersion or in the form of powder, so that the OLF according to the invention is especially valuable because of their efficiency is not affected by the presence of the cationic polymer fixing substances, agents for imparting strength in the wet state or auxiliary substances in the laundering of printing ink, which also add to the ox is cristou mass before forming paper. Examples of such excipients may include the products of the reactions of condensation of dicyandiamide, polyvinylene, polyethylenimine, cationic starches, poly-DADMAC (diallyldimethylammoniumchloride), polyamidoamine and polyepoxide.

In conclusion, the object of the invention is paper, which is treated with a fluorescent optical Brightener comprising either a mixture of compounds of formulas (1a), (1b) and (1C), the compound of the formula (2)or the compound of formula (5).

A particular advantage of the compounds of the present invention lies in the fact that they are not only extremely high whitening capacity, including in the presence of cationic polymers or residues anionic OSF, but, in addition, in many cases exclusively required property water solubility and strength.

Illustrations of the invention are the following examples without intention to consider them inherently limiting; in all cases, unless otherwise stated, parts and percentages are mass. Percentage compositions of the reaction mixtures are calculated from the areas under the curves corresponding HPLC spectra taken at 350 nm.

Examples retrieve

Example 1

16,7 ginatrapani salt of 4,4'-bis-[(4-N-morpholino-6-chloro-1,3,5-triazine-2-yl)amino]still the n-2,2'-disulfonic acid for 30 min with stirring at 25C. is introduced into 50 ml of 3-N,N-dimethylamino-1-Propylamine, consequently during the addition the temperature rises to 60C. Next, the temperature increases to 100C and the mixture was kept at this temperature for a further 1 h and Then aging at elevated temperatures drop, the mixture allowed to stand overnight at room temperature, then diluted with 25 ml of water and evaporated under vacuum to approximately 30 g of the Obtained residue is dissolved in 50 ml of water and add 20 ml of concentrated hydrochloric acid the pH was adjusted to 1.0. Next, the pH increases to about 5, and the mixture is stirred over night at room temperature. Precipitated precipitated solids filtered off, washed with water and dried under vacuum at 60C. as a result, In the form of pale yellow crystals obtain 14.9 g of the compound of formula (101) with a basic substance content of 83%.

The source material, the disodium salt of 4,4'-bis-[(4-N-morpholino-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid of the formula (101A), is prepared as follows. A solution of 120 g cyanur chloride in 930 ml of methyl ethyl ketone for 10 minutes at a temperature of from 5 to 10C With stirring to 400 g of ice water. Then for 70 min at a pH of from 4.5 to 5.0 add 1042 g of a 12%aqueous solution of 4,4'-diaminostilbene-2,2'-disulfonic acid and sodium carbonate in such a way that no excess 4,4'-diaminostilbene-2,2 who-disulfonic acid. The mixture is stirred for additional 20 min at a temperature of from 5 to 10C. after this time, in the aggregate spend of 37.9 ml of 20%aqueous sodium carbonate solution. The mixture is heated up to 15-20C and the addition of 20%aqueous sodium carbonate solution pH was adjusted to 7.0. Then dropwise within 10 min type of 28.0 g of the research, within 60 min the mixture is heated to a temperature of from 70 to 75C and at this temperature, stirring is continued for 30 min, and the pH is maintained at the level of 7.0 to 7.5 by adding a total of 46,9 ml of 50%aqueous sodium hydroxide solution. Next, the temperature was raised to 90C. and methyl ethyl ketone is distilled off. Then the reaction mixture slowly over 60 min, cooled to 25C, precipitated precipitated solids filtered off, washed with 5%brine and dried under vacuum at 60C. the result is 232,2 g of compound formulas.

Example 2

8,9 g disodium salt of 4,4'-bis-[(4-bis-(2-hydroxyethyl)amino-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-

disulfonic acid obtained by the method similar to that described for compound (101A) in example 1 for 10 minutes with stirring at 25C is added to 25 ml of 3-N,N-dimethylamino-1-Propylamine, resulting while adding the temperature rises to 45C. Next, the temperature of the additive is about to increase to 100C and the mixture was kept at this temperature for up to 1.75 hours Then exposure at elevated temperatures drop, the mixture allowed to stand overnight at room temperature, then diluted with 25 ml of water and evaporated under vacuum to about 18, the resulting residue is diluted with 50 ml of water and adding water 17%hydrochloric acid the pH was adjusted to 1.0. Then add 90 ml of acetone, which leads to the formation of 2 phases. The aqueous phase is separated in a separating funnel and then added 4 N. aqueous sodium hydroxide solution of pH increase to 8.5. Precipitated precipitated solids filtered off, washed with water and dried under vacuum at 60C. as a result, In the form of yellow crystals obtain 5.0 g of the compound of the formula (102).

Example 3

Analogously to example 2, but with the replacement of the disodium salt of 4,4'-bis-[(4-bis-(2-hydroxyethyl)amino-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-

disulfonic acid equivalent amount of disodium salt of 4,4'-bis-[(4-bis-(2-hydroxy-n-propyl)amino-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-

disulfonic acid obtained by the method similar to that described for compound (101A) in example 1, in the form of pale yellow crystals obtain 6.4 g of the compound of formula (103).

Example 4

24,3 g disodium salt of 4,4'-bis-[(4-N-morpholino-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-dis is honowai acid (101A) for 15 min with stirring to 69,6 g 2-N,N-diethylamino-1-ethylamine. Next, the resulting suspension is heated to 115C. and the mixture was kept at this temperature for another 2 hours After dilution with 150 ml of water pale brown solution is evaporated under vacuum and this operation is repeated twice. Adding to the residue 100 ml of water leads to the formation of a beige suspension with a pH of 11.2. Then by adding 5 ml of 50%aqueous sodium hydroxide solution the pH was adjusted to 12.8, followed by addition of 35 ml of concentrated hydrochloric acid is reduced to 4, the yellow precipitate is stirred for 30 min, filtered and washed with 1000 ml of water. After drying under vacuum at 70C in the form of yellow crystals obtain 26.7 g of the compound of the formula (104).

Example 5

Analogously to example 4, but replacing 2-N,N-diethylamino-1-ethylamine equivalent amount of 3-N,N-diethylamino-1-Propylamine, in the form of a whitish-beige crystals get to 27.0 g of compound of formula (105).

Example 6

Analogously to example 4, but with the replacement of the disodium salt of 4,4'-bis-[(4-N-morpholino-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid equivalent amount of disodium salt of 4,4'-bis-[(4-aniline-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid obtained by the method similar to that described for compound (101A) in example 1, in the form of beige crystals floor is up to 19.9 g of compound of formula (106).

Example 7

Analogously to example 4, but with the replacement of the disodium salt of 4,4'-bis-[(4-N-morpholino-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid equivalent amount of disodium salt of 4,4'-bis-[(4-aniline-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid and 2-N,N-diethylamino-1-ethylamine equivalent amount of 3-N,N-diethylamino-1-Propylamine, in the form of beige crystals get to 26.6 g of compound of formula (107).

Example 8

9.5 g disodium salt of 4,4'-bis-{[4-(4-sulfonanilide)-6-chloro-1,3,5-triazine-2-yl]amino}stilbene-2,2'-disulfonic acid obtained by the method similar to that described for compound (101A) in example 1 for 20 min with stirring at 90C is added to 32,0 g 3-N,N-dimethylamino-1-Propylamine. Next, the temperature increases up to 115-120C and the mixture was kept at this temperature for a further 2 hours and Then aging at elevated temperatures drop, after which the mixture is diluted with 120 ml of water and evaporated under vacuum. After repeating this last operation the resulting residue is dissolved in 150 ml of water and the addition of an aqueous sodium hydroxide pH adjusted to 12-13. In further addition of concentrated hydrochloric acid the pH was adjusted to 6 and the precipitate is filtered off, washed with water and su is at under vacuum at 70C. As a result, in the form of pale yellow crystals gain of 8.4 g of compound of formula (108).

Example 9

10.0 g disodium salt of 4,4'-bis-[(4-aniline-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid for 15 min with stirring at 30C is added to 30 ml of 1,3-diaminopropane, so the temperature increases to 50C. Next, the yellow suspension is heated to 80C. and stirring is continued at this temperature for a further 90 minutes After cooling the mixture was poured into 300 ml of water and adding 65 ml of concentrated hydrochloric acid, the pH is brought to 2. Water liquid decanted, separating from the oily residue, which was pulverized with water in a mortar, then stirred for 2 h at pH 5. The solids filtered off, washed with 5%brine and dried under vacuum at 70C. as a result, In the form of yellow crystals get to 10.1 g of compound of the formula (109).

Example 10

Analogously to example 9, but with the replacement of the disodium salt of 4,4'-bis-[(4-aniline-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid equivalent amount of disodium salt of 4,4'-bis-{[4-(4-sulfonanilide)-6-chloro-1,3,5-triazine-2-yl]amino}stilbene-2,2'-disulfonic acid, in the form of pale brown crystals obtain 12.0 g of the compound of the formula (110).

Example 11

Analogously to example of 98.5 g of disodium salt of 4,4'-bis-[(4-N-morpholino-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid is introduced into reaction with 30 ml of 1,3-diaminopropane obtaining in the form of yellow crystals of 9.1 g of compound of formula (111).

Example 12

The mixture of compounds of the formula

16,46 g disodium salt of 4,4'-bis-[(4-aniline-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid for 30 min with stirring at 50C and add to the mixture 33,95 g 3-N,N-dimethylamino-1-Propylamine 12,25 g of 1,3-diaminopropane, whereupon the temperature rises to 85C. Next, yellowish-brown viscous solution is heated to 90C and at this temperature, stirring is continued for an additional 5 hours After cooling the mixture is then poured into 300 ml of water and the resulting yellow solution with a pH of 11.4 allowed to stand over night. Then add 85 ml of concentrated hydrochloric acid, the pH is brought to 3, the mixture is stirred for a further 2 hours and precipitated precipitated solids filtered off, washed with 5%brine and dried under vacuum at 70C. as a result, In the form of yellow crystals gain of 18.2 g of a mixture of compounds of the above formula, containing 40% (a), 44% (112b) and 13% (112c).

Example 13

The mixture of compounds of the formula

A solution of 120 g of cyanuric chloride in 930 ml of methyl ethyl ketone for 10 minutes at a temperature of from 5 to 10C With stirring to 400 g of ice water. Then for 70 min at a pH of from 4.5 to 5.0 add 1093 g of a 12%aqueous solution of 4,4'-diaminostilbene-2,2'-disulfonic acid and sodium carbonate in such a way that no excess 4,4'-diaminostilbene-2,2'-disulfonic acid. The mixture is stirred for another 10 min at a temperature of from 5 to 10C. after this time, the total spent of 21.2 ml of 20%aqueous sodium carbonate solution. The mixture is heated to 8-20C and addition of 50%aqueous sodium hydroxide solution the pH was adjusted to 7.5. Next dropwise within 10 min add a mixture of 29.9 g of aniline and 28.0 g of the research, the mixture is heated to a temperature of 70C for 60 min and at this temperature, stirring is continued for 90 min, and methyl ethyl ketone is distilled off. To maintain the pH during this period at the level of 7.5 in the aggregate are required to 54.2 ml of 50%aqueous sodium hydroxide solution. Then the reaction mixture is cooled to 30C for 60 min and allowed to stand overnight at room temperature. The upper liquid layer is decanted, the residue is suspended in 750 ml of a 5%brine, heated to 60C and then slowly cooled to 30C for 60 mi is. Precipitated precipitated solids filtered off, washed with 5%brine and dried under vacuum at 70C. the result is 259,1 g of yellow crystalline product containing 27% of the compounds of formula (a), 46% (113b) and 24% (101a).

Example 14

The mixture of compounds of the formula

Analogously to example 13, but with the replacement of 28.0 g of the research 33,7 g diethanolamine, get 287,3 g of yellow crystalline product containing 24% of compounds of formula (a), 38% (114b) and 30% (s).

Example 15

30.0 g disodium salt of 4,4'-bis-[(4-aniline-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid with stirring for 10 min at 80C is added to 100.0 g of 2-N,N-dimethylaminoethanol. Next beige suspension is heated to 120C and at this temperature, stirred for an additional 1.5 hours After cooling to 100C. the mixture is diluted with 100 ml of water and evaporated in a rotary evaporator. The remainder (56 g) was dissolved in 300 ml of water, adding hydrochloric acid pH yellowish-brown suspension was adjusted to 5 and the mixture is stirred for a further 1 h Precipitated precipitated solids filtered off, washed with water and dried under vacuum at 70C. as a result, In the form of a whitish-beige crystals get 30,2 g of compound of the formula (115).

the example 16

The mixture of compounds of the formula

A solution of 120 g of cyanuric chloride in 930 ml of methyl ethyl ketone for 10 minutes at a temperature of from 5 to 10C With stirring to 400 g of ice water. Then for 70 min at a pH of from 4.5 to 5.0 add 978 g of a 12%aqueous solution of 4,4'-diaminostilbene-2,2'-disulfonic acid and sodium carbonate in such a way that no excess 4,4'-diaminostilbene-2,2'-disulfonic acid. The mixture is stirred for additional 10 min at a temperature of from 5 to 10C. after this time spend in total and 24.2 ml of 20%aqueous sodium carbonate solution. The mixture is heated up to 10-20C and addition of 50%aqueous sodium hydroxide solution the pH was adjusted to 7.5. Next dropwise within 10 min type of 29.9 g of aniline, the mixture is heated to 30C and at this temperature, stirring is continued for 30 minutes Then added dropwise within 15 min add a solution of 17.2 g of ammoniaand in 50 ml of water and the resulting yellow suspension is heated to 70C. After stirring for an additional 60 min add 100 ml of 25%aqueous ammonia, the mixture is stirred for 30 min and ultimately distilled methyl ethyl ketone. The resulting mixture is cooled to 30C. the precipitated solids filtered off, washed the t a small amount of water, then 5%brine, and dried under vacuum at 70C. the result is 199,7 g of yellow crystalline product, comprising a mixture of compounds containing 26% (a), 26% (116b) and 36% (s).

Example 17

The mixture of compounds of the formula

30.0 g of a mixture of compounds of formulas (a), (113b) and (101A), obtained as described in example 13, with stirring for 20 min at 45C is added to 100 ml of 3-N,N-dimethylamino-1-Propylamine. The mixture is heated to 120C and at this temperature, stirred for another 1 h After cooling to 90C. add 100 ml of water and the reaction mixture is evaporated in a rotary evaporator. The residue is dissolved in 250 ml of water, the addition of concentrated hydrochloric acid pH adjusted to 5 and loose precipitated solids filtered off, washed with water and dried under vacuum at 70C. the result of 27.2 g of yellow crystalline product, which is a mixture of compounds containing 26% (a), 45% (117b) and 23% (101).

Example 18

Analogously to example 15, but replacing the disodium salt of 4,4'-bis-[(4-aniline-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid 30 g of disodium salt of 4,4'-bis-[(4-amino-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid obtained by the method similar to that described for compound (101A) in example 1, in the form of yellow crystals obtain 30.0 g of the compound of formula (118).

Example 19

Analogously to example 15, but replacing the disodium salt of 4,4'-bis-[(4-aniline-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid 30 g of disodium salt of 4,4'-bis-[(4-N-morpholino-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid (101A), in the form of yellow crystals obtain 30.0 g of the compound of formula (119).

Example 20

The mixture of compounds of the formula

30.0 g of a mixture of compounds of formulas (a), (113b) and (C), obtained as described in example 13, with stirring for 45 min at 80C is added to 100 ml of 2-N,N-dimethylamino-1-ethanol. The mixture is stirred for a further 2 h at 80C and then diluted with 100 ml water and the reaction mixture is evaporated in a rotary evaporator. The residue is dissolved in 100 ml of water, add 10 ml of concentrated hydrochloric acid the pH was adjusted to 5.5 and the upper liquid layer is decanted. The residue is pulverized in a mortar with 150 ml of a 5%brine, stirred overnight and the precipitated precipitated solids filtered off, washed with 5%aqueous brine, and dried under vacuum at 70C. the result is 28.6 g of a yellow crystalline product which p is ecstasy a mixture of compounds, containing 21% (115), 35% (120b) and 19% (119).

Example 21

The mixture of compounds of the formula

Analogously to example 20, but replacing 30.0 g of a mixture of compounds of formulas (a), (113b) and (C) 30.0 g of a mixture of compounds of formulas (a), (114b) and (C), obtained as described in example 14, in the form of yellow crystals gain of 27.3 g of a mixture of compounds containing 26% (115), 39% (121b) and 29% (s).

Example 22

The mixture of compounds of the formula

Analogously to example 13, but replacing the research equivalent number of diisopropanolamine, in the form of yellow crystals get 210,5 g of a mixture of compounds containing 31% of the compounds of formula (a), 45% (122b) and 20% (s).

Example 23

The mixture of compounds of the formula

Analogously to example 13, but replacing the research equivalent amount of monoethanolamine, in the form of yellow crystals get 244 g of a mixture of compounds containing 26% of compounds of formula (a), 40% (123b) and 33% (s).

Example 24

Analogously to example 15, but replacing the disodium salt of 4,4'-bis-[(4-aniline-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid 30 g DIN is treeway salt of 4,4'-bis-[(4-bis-(2-hydroxyethyl)amino-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid, in the form of yellow crystals get 27,3 g of compound of formula (124).

Example 25

Stir in a mixture of 150 ml water, 150 ml of dioxane and 40.7 g of ethylene diamine, at a temperature of from 70 to 75C. for 30 min add 40,0 g disodium salt of 4,4'-bis-[(4-amino-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid. Next brown solution is heated to 88C. and stirring is continued for another 2 hours After cooling to a temperature of 70With the addition of 115 ml of concentrated hydrochloric acid the pH was adjusted to 5.5 and loose precipitated solids filtered off at 60C and washed with a small amount of water. The filter cake is suspended in 350 ml of water, 50%aqueous solution of sodium hydroxide added to pH 11 and the resulting yellow solution is stirred for 1 h by the Addition of concentrated hydrochloric acid pH adjusted to 5, the yellow precipitate is filtered off, washed with water and dried under vacuum at 70C. as a result, In the form of yellow crystals get to 31.5 g of compound of formula (125).

Example 26

Analogously to example 25, but replacing 40,0 g disodium salt of 4,4'-bis-[(4-amino-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid 40,0 g disodium salt of 4,4'-bis-[(4-aniline-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid, in the de yellow crystals gain of 30.4 g of compound of formula (126).

Example 27

Analogously to example 25, but with the replacement of 40.7 g of Ethylenediamine to 91.6 g of N-(3-aminopropyl)diethanolamine, in the form of yellow crystals get of 50.4 g of compound of formula (127).

Example 28

The mixture of compounds of the formula

Reaction of 40.0 g of a mixture of compounds of formulas (a), (113b) and (C), obtained as described in example 13, with 100 ml of 3-N,N-dimethylamino-1-Propylamine essentially as described in example 20, the gain of 33.8 g of yellowish-brown crystals of a mixture of compounds containing 25% of the compounds of formula (a), 39% (128b) and 27% (102).

Example 29

Analogously to example 25, but replacing 40,0 g disodium salt of 4,4'-bis-[(4-amino-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid 40,0 g disodium salt of 4,4'-bis-[(4-aniline-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid and 40.7 g of Ethylenediamine to 68.1 g of 2-(3-aminopropylene)ethanol, in the form of yellow crystals get 35,8 g of compound of formula (129).

Example 30

Analogously to example 25, but replacing 40,0 g disodium salt of 4,4'-bis-[(4-amino-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid 35,0 g disodium salt of 4,4'-bis-[(4-ethanolamine-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2 disulfonic acid and 40.7 g of Ethylenediamine and 47.0 g of 3-N,N-dimethylamino-1-Propylamine, in the form of yellow crystals get to 39.3 g of compound of formula (130).

Example 31

Processing 30.0 g disodium salt of 4,4'-bis-[(4-aniline-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid 90 ml of N-(2-hydroxyethyl)Ethylenediamine essentially as described in example 9 results in the form of beige crystals of 28.0 g of compound of the formula (131).

Example 32

The mixture of compounds of the formula

Analogously to example 13, but replacing the research equivalent amount of 2-N-methylaminoethanol, in the form of yellow crystals get 213,3 g of a mixture of compounds containing 26% of compounds of formula (a), 34% (132b) and 32% (s).

Example 33

The mixture of compounds of the formula

Analogously to example 13, but replacing the research equivalent amount of 1-aminopropan-2-ol in the form of yellow crystals get 188,5 g of a mixture of compounds containing 33% of compounds of formula (a), 40% (133b) and 23% (s).

Example 34

A solution of 120 g of cyanuric chloride in 930 ml of methyl ethyl ketone for 10 minutes at a temperature of from 5 to 10C With stirring to 400 g of ice water. Then for 70 min at a pH of from 4.5 to 5.0 dobavlaut g of a 12%aqueous solution of 4,4'-diaminostilbene-2,2'-disulfonic acid and sodium carbonate thus, that no excess 4,4'-diaminostilbene-2,2'-disulfonic acid. The mixture is stirred for another 10 min at a temperature of from 5 to 10C. after this time spend in total 29,8 ml of 20%aqueous sodium carbonate solution. The mixture is heated up to 10-20C and addition of 50%aqueous sodium hydroxide solution the pH was adjusted to 7.0 and 7.5. Next dropwise within 10 min add 52,5 g 1-aminopropan-2-ol for 1 h the mixture is heated to 70C. and at this temperature, stirring is continued for another 90 min, and methyl ethyl ketone is distilled off, and then within 30 minutes, cooled to 50C., then for another 30 min to 25C, stirred for another 3 h at this temperature and, finally, allowed to stand overnight at room temperature. During this period the pH is maintained at the level of 7.0 to 7.5, so in total, spend 53,4 ml of 50%aqueous sodium hydroxide solution. Precipitated precipitated solids filtered off, washed with water, then with 2.5%brine, and dried under vacuum at 70C. as a result, In the form of yellow crystals get 230,6 g of compound of the formula

In a mixture of 150 ml water, 150 ml of dioxane and 43.1 g of 3-N,N-dimethylamino-1-Propylamine, pre-heated to a temperature of 70C., with stirring, to 35.0 g of compound of formula (134a). Yellowish to rickeby solution is heated to 86-88C and at this temperature, stirring is continued for 90 minutes After cooling to a temperature of 70C. add 100 ml of water and add 70 ml of concentrated hydrochloric acid the pH was adjusted to 5.0. After adjusting the pH to 1.5 and cooling to 10C. add 25 g of sodium chloride and the mixture is stirred over night. The mixture is then evaporated in a rotary evaporator and the resulting viscous residue portions added to 400 ml of acetone. The upper layers of the liquid thrown out and this operation is repeated until then, until you get a crystalline product. After filtration of solid particles is stirred overnight in 200 ml of water, the upper layers of the liquid discarded, the residue is evaporated in a rotary evaporator and finally dried under vacuum at 70C. as a result, In the form of pale yellow crystals gain of 13.0 g of compound of formula (134).

Example 35

Processing 30.0 g disodium salt of 4,4'-bis-[(4-aniline-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid 100 ml 2,2'-(Ethylenedioxy)diethylenediamine essentially as described in example 9 results in the form of pale brown crystals 34,0 g of compound of formula (135).

Example 36

Analogously to example 1 for obtaining compounds of formula (101A), but with the replacement of the research equivalent amount of p-phenetidine, in the form of a greenish-yellow crystals get 232,7 g of compound of the formula

Analogously to example 25, but replacing 40,0 g disodium salt of 4,4'-bis-[(4-amino-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid 35,0 g of compound of formula (a), in the form of yellow crystals get to 27.2 g of compound of the formula (136).

Example 37

Analogously to example 25, but replacing 40,0 g disodium salt of 4,4'-bis-[(4-amino-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid 40,0 g disodium salt of 4,4'-bis-[(4-aniline-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid and 40.7 g of Ethylenediamine 35.5 g of 1,2-Propylenediamine, in the form of yellow crystals get to 34.7 g of compound of the formula (137).

Example 38

Analogously to example 25, but replacing 40,0 g disodium salt

4,4'-bis-[(4-amino-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid 30.0 g disodium salt of 4,4'-bis-[(4-aniline-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid and 40.7 g of Ethylenediamine was 48.3 g of 1,2-diaminocyclohexane, in the form of yellow crystals get 27,1 g of compound of the formula (138).

Example 39

Analogously to example 13, but replacing the mixture of 29.9 g of aniline and 28.0 g of the research of 89.1 g of 2-anilinomethyl, in the form of yellow crystals get 281,5 g of compound of the formula

In 150 ml of water, preheated to those of the temperature from 70 to 75C, added to 35.0 g of compound of formula (139a). Next, the resulting yellow solution process of 12.6 g of diethylaminopropylamine and the mixture is stirred for 4 h at 95-97C, and the pH is maintained at the level of 10.0 to 10.5 by adding together 1.5 ml 4 N. aqueous sodium hydroxide solution. After cooling to a temperature of 70With the addition of 6.5 ml of concentrated hydrochloric acid the pH was adjusted to 4.0 and loose precipitated solids filtered off, washed with water and dried under vacuum at 80C. as a result, In the form of yellow crystals get with 37.4 g of compound of the formula (139).

Example 40

Processing of 25.0 g of disodium salt of 4,4'-bis-{[4-(4-sulfonanilide)-6-chloro-1,3,5-triazine-2-yl]amino}stilbene-2,2'-disulfonic acid (see example 8) 9.6 g of 3-diethylamino-1-Propylamine analogously to the method described for compound (139) in the previous example leads to the formation in the form of yellow crystals of 24.0 g of compound of formula (140).

Example 41

Analogously to example 30, but replacing 3-(N,N-dimethylamino-1-Propylamine 3-N,N-diethylamino-1-Propylamine as a yellow crystals get to 40.4 g of compound of formula (141).

Example 42

Processing of 65.2 g of disodium salt of 4,4'-bis-[(4-bis-(2-hydroxy-n-propyl)amino-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonate is islote (see example 3) of 13.9 g of 3-diethylamino-1-Propylamine according to the method similar to that described for compound (139) in example 39, leads to the formation in the form of yellow crystals of 28.8 g of compound of formula (142).

Example 43

Processing 25 g of disodium salt of 4,4'-bis-[(4-bis-(2-hydroxyethyl)amino-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid (see example 2) 11.6 g of 3-diethylamino-1-Propylamine analogously to the method described for compound (139) in example 39, leads to the formation in the form of yellow crystals and 24.1 g of compound of formula (143).

Example 44

Processing 25 g of compound of formula (134a) (see example 34) 9.95 g of 3-diethylamino-1-Propylamine according to the method similar to that described for compound (139) in example 39, leads to the formation in the form of yellow crystals of 24.6 g of compound of formula (144).

Example 45

Analogously to example 13, but replacing the mixture of 29.9 g of aniline and 28.0 g of the research of 84.0 g of 2-ethyl-1-hexylamine in the form of a yellowish-beige crystals get 270,7 g of compound of the formula

Processing of 25.0 g of compound of formula (a) 10,5 g 3-diethylamino-1-Propylamine according to the method similar to that described for compound (139) in example 39, leads to the formation in the form of pale yellow crystals 26.7 g connection Faure the uly (145).

Example 46

Analogously to example 13, but replacing the mixture of 29.9 g of aniline and 28.0 g of the research and 64.3 g of 2-amino-2-methyl-1-propanol in the form of yellow crystals get 162,4 g of compound of the formula

,

Processing 25 g of compound of formula (146a) 11.6 g of 3-diethylamino-1-Propylamine according to the method similar to that described for compound (139) in example 39, leads to the formation in the form of beige crystals 29,2 g of compound of formula (146).

Example 47

Analogously to example 25, but replacing 40,0 g disodium salt of 4,4'-bis-[(4-amino-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid 35,0 g disodium salt of 4,4'-bis-[(4-aniline-6-chloro-1,3,5-triazine-2-yl)amino]stilbene-2,2'-disulfonic acid and 40.7 g of Ethylenediamine 44,6 g Diethylenetriamine, in the form of yellow crystals get to 37.1 g of compound of formula (147).

Example 48

The mixture of compounds of the formula

The reaction of 25.0 g of a mixture of compounds of formulas (a), (123b) and (C), obtained as described in example 23, with 11.9 g of 3-N,N-diethylamino-1-Propylamine according to the method similar to that described for compound (139) in example 39, in the form of yellow crystals gain of 25.9 g of a mixture of compounds containing 29% of the compound of formula (107), 42% (148) and 28% (130).

Examples of the application

In 25 ml of a mixture of 9:1 DMSO/water dissolve various fluorescent optical brighteners (OSF), adding 4 N. aqueous sodium hydroxide solution the pH was adjusted to about 10 and the water volume of the solution is brought to 50 ml

In the dispersion of the fibres, containing 70 frequent. birch fibers and 30 frequent. pine Kraft pulp with a degree of grinding of 35 SR (instrument Shopper-Regler), as a filler to add a 10% calcium carbonate (HydRocaRb 60). Next, add the solutions of the OLF in a quantity sufficient to make the concentration of the OLF in terms of the weight of the fibrous component of the dispersion was 0.2%. Provide an opportunity for the depletion of the OLF for 15 min, as contributing to the retention means add 0,03% cationic polyacrylamide (PeRcol 292) and immediately using system Rapid-Koethen manually cast list.

Then on the device SCAN-P66-93 by using a spectrophotometer, determine the degree of whiteness of the sheets (W CIE).

The results of these determinations are summarized in the following table 1.

Table 1
Example No.Connection # W (CIE)
No 70,1
49(137)132
50(109)131
51A mixture of example 12131
52(125)130
53(115)128
54(111)125
55(135)124
56(101)115
57(102)113
58(136)112

The above results clearly demonstrate the excellent bleaching action of the fluorescent optical brighteners according to the invention.

Table 2
Product1Part of the FWA W-CIEFISQ
nono103,38,1
Tinopal ABP-Z0,4106,18,6
Tinopal ABP-Z0,7109,29,8
Tinopal ABP-Z1,0to 110.710,5
Tinopal ABP-Z1,5112,911,5
Tinopal ABP-Z3,0110,111,3
Tinopal RSP0,4106,98,8
Tinopal RSP0,7111,510,5
Tinopal RSP1,0111,310,8
Tinopal RSP1,5or 115.1 12,3
Tinopal RSP3,0116,413,3
Tinopal SHP0,4102,27,1
Tinopal SHP0,7105,88,3
Tinopal SHP1,0108,69,4
Tinopal SHP1,5111,810,5
Tinopal SHP3,0117,712,9
Tinopal SK0,4102,97,3
Tinopal SK0,7107,28,7
Tinopal SK1,0109,7the 9.7
Tinopal SK1,5112,010,6
Tinopl SK 3,0113,612,1
The compound (5A)0,4105,68,1
The compound (5A)0,7to 110.79,8
The compound (5A)1,0113,510,9
The compound (5A)1,5of 116.712,2
The compound (5A)3,0119,613,6
1Tinopal ABP-Z, RSP and SK are commercially available products supplied to the market by the firm Ciba Specialty of Chemicals as a fluorescent Brightener for drawing on paper

1. The use of the compounds of formula

in which Y and Y1each independently of one another denotes remotemachine2-C8alkylenes or branched C3-C8alkylenes chain which may be interrupted by one or two nitrogen atoms, oxygen is or sulfur, or represents 5 - or 6-membered cycloaliphatic ring,
R1, R2, R5and R6each independently of one another denotes a hydrogen atom,
With1-C8alkyl, C2-C4hydroxyalkyl,1-C4alkoxyl1-C4alkyl, phenyl which is not substituted or substituted by a halogen atom, a C1-C4alkoxy, C1-C4the alkyl or sulfonamideubul, or
R1and R2and/or R5and R6together with the nitrogen atom to which they are attached, form morpholino-, piperidino or pyrolidine ring,
R3and R4each independently of one another denotes a hydrogen atom, a C1-C4alkyl, C2-C4hydroxyalkyl or
R3and R4together with the nitrogen atom to which they are attached, form morpholino-, piperidino or pyrolidine ring, and
M denotes a hydrogen atom, alkali or alkaline earth metal, ammonium or alkylammonium;
R14and R15each independently of one another denotes a hydrogen atom, a C1-C4alkyl or C2-C4hydroxyalkyl, for the fluorescent whitening of paper.

2. Paper treated with a fluorescent optical Brightener comprising a compound of the formula (5) according to claim 1.



 

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FIELD: organic chemistry, paper industry.

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< / BR>
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