Introducible photoinitiating agent

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to photoinitiating agents of phenylglyoxylic acid order used in polymerizing compositions to be subjected for hardening. Invention describes a photoinitiating agent of the formula (I): wherein Y means (C3-C12)-alkylene, butenylene, butinylene or (C4-C12)-alkylene that are broken by groups -O- or -NR2- and not following in sequence; R1 means a reactive group of the following order: -OH, -SH, -HR3R4, -(CO)-OH, -(CO)-NH2, -SO3H, -C(R5)=CR6R7, oxiranyl, -O-(CO)-NH-R8-NCO and -O-(CO)-R-(CO)-X; R2 means hydrogen atom, (C1-C4)-alkyl, (C2-C4)-hydroxyalkyl; R3 and R4 mean hydrogen atom, (C1-C4)-alkyl, (C2-C4)-hydroxyalkyl; R, R and R mean hydrogen atom or methyl; R8 means linear or branched (C4-C12)-alkylene or phenylene; R9 means linear or branched (C1-C16)-alkylene, -CH=CH-, -CH=CH-CH2-, C6-cycloalkylene, phenylene or naphthylene; X, X1 and X2 mean -OH, Cl, -OCH3 or -OC2H5. Also, invention describes a method for synthesis of a photoinitiating agent, polymerizing composition and substrate covered by its. Proposed photoinitiating agent possesses the effective introducing capacity and absence of migration in thermal treatments.

EFFECT: improved and valuable properties of agent.

13 cl, 1 tbl, 16 ex

 

The invention relates to photoinitiator type phenylglyoxylic acid, which, thanks to the presence of special Deputy, able to enter into the composition polymerizable formulation.

Derivatives phenylglyoxylic acid known as photoinitiators and described, for example, in patents US 4038164, US 4475999 and US 4024297. Connection, in the molecule of which contains two functional groups of ether phenylglyoxylic acid, known for example from document US 6048660 and WO 00/56822. Derivatives phenylglyoxylic acids that contain acrylate groups, described in patents US 3930868, US 4308394 and US 4279718.

In the prior art there is a need to reactive photoinitiator with low volatility, which, in addition to the excellent properties of the initiator and a good dark stability during storage of the compositions with which they are mixed, also have a wide range of applications in the compositions of complex composition, such as a mixture of thermally and photochemically curable component; for such photoinitiators, or products of photolysis of possible binding in these compositions due to the rapid migration. In this invention, it was found that certain esters phenylglyoxylic acid are particularly suitable as photoinitiators with low volatility. These esters are connected to the tion, they acquire a rigid connection with the coating during the curing process, and the migration initiator is prevented.

Accordingly, the invention relates to introduce photoinitiator compounds of formula (I)

,

in which Y represents C3-C12alkylen, butylen, Butylin or4-C12alkylene, which is interrupted once or several times by groups-O -, or-NR2-not following each other, or Y represents a phenylene, cyclohexene,

R1represents a reactive group selected from HE, SH, NR3R4, -(CO)-OH, -(CO)-NH2, SO3H, -C(R5)=CR6R7, oxiranyl, -O-(CO)- NH-R8-NCO and-O-(CO)-R9-(CO)-X;

R2represents hydrogen, C1-C4alkyl or C2-C4hydroxyalkyl;

R3and R4represent, each independently, hydrogen, C1-C4alkyl or C2-C4hydroxyalkyl;

R5, R6and R7represent, each independently, hydrogen or methyl;

R8represents a linear or branched C4-C12alkylene, phenylene, methylphenylene, cyclohexanediyl, inforanger,,, ,,,,,,or;

R9represents a linear or branched C1-C16alkylene, -CH=CH-, -CH=CH-CH2-With6-cycloalkyl, phenylene, naftilan, the norbornene-5,6-diyl,

X, X1and X2represent, each independently of the others, HE, Cl, co3or OS2H5.

A characteristic feature of the compounds of formula (I) is that the radical R1in them is a reactive group. In this context, the term "reactive group" refers radicals, which are able to interact with the composition which will cure and thus be fixed in the composition. This reduces the migration of photoinitiator.

With1-C4Alkyl is linear or branched and is a methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl.

C2-C4Hydroxyalkyl represents a C2-C4alkyl, substituted one or multiple IT groups, and the above-defined alkyl contains the corresponding number of carbon atoms. Examples of which are hydroxyethyl, dihydroxypropyl, hydroxypropyl and dihydroxyethyl, especially hydroxyethyl.

With3-C12Alkylene means a linear or branched alkylene, for example, propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert-butylene, pentile, hexylen, reptile, octiles, Nonlin, deciles, modellen,,,or.

Group C4-C12alkylene, which is interrupted once or several times by groups-O -, or-NR2-not following each other, produces structural units such as-CH2CH2-O-CH2CH2-, -[CH2CH2O]y-, in which y=2-9, -(CH2CH2O)5CH2CH2-, -CH2-CH(CH3)-O-CH2-CH(CH3)-, -CH2CH2-(NR2)-CH2CH2-.

Oxiranyl is a group.

With6-Cycloalkyl meansor.

Preference is given to compounds of the formula (I)in which Y represents-CH2-CH(CH3)-, n-propylene, -CH2C(CH3)2CH2, hexylen, -CH2CH2-O-CH2CH2-, -(CH 2CH2-O)2CH2CH2-,or.

The compounds of formula (I)in which R1means the group HE present a special interest.

Especially interesting are the compounds in which R1HE is a and Y is-CH2CH2-O-CH2CH2-.

In addition, special interest are implemented photoinitiator formula (I), in which

Y represents a C4-C12alkylene, which is interrupted one or more times not following each other by groups-O-;

R1means reactive group selected from HE, oxiranyl and-O-(CO)-NH-R8-NCO; and R8represents,,,or

I. the compounds of formula (I) according to the invention can be obtained, for example, by reacting diols (by which are obtained the compounds of formula (I)in which R1=HE) or functionalized alcohols HO-Y-R1(A) monoamine phenylglyoxylic acid (In), for example, from the corresponding methyl ester, in the presence of a catalyst (when nahrawan and in vacuum):

where R1such as defined above.

As a catalyst can be used, for example, catalysts which are known to experts in this field of technology for the reactions of transesterification, for example, oxide dibutylamine or a pair of toluensulfonate. Some catalysts, although suitable for carrying out this reaction, cause discoloration of the products or are toxic or difficult to remove from the reaction mixture.

Suitable catalysts include sodium acetate, potassium acetate, magnesium acetate, barium acetate, zinc acetate, cadmium acetate, copper acetate(II), cobalt acetate(II), aluminum acetate, calcium oxide, lithium methylate, sodium methylate, Tetra-isopropyl titanium, triisopropyl aluminum; tert-butyl lithium, 4-(dimethylamino)pyridine and the diacetate dibutyrate (i.e. Fascat 4200) [catalytic activity of these acetates does not depend on the content of water of crystallization].

Especially suitable are, for example, various lithium salts, for example, isopropyl lithium, lithium acetate, lithium carbonate. Preferred are lithium acetate, and calcium oxide.

The lithium acetate is particularly suitable as a catalyst, especially in obtaining the compounds of formula I in which R1=IT.

The amount of catalyst is, for example, from 0.1 to 20 mo is.%, in the calculation of the component of the ester of Glyoxylic acid (V), but can be used and large quantities without harmful effects on the course of the reaction. Preferably use 4 mol.% catalytic Converter.

Appropriate, add an excess of the alcohol (a) and methanol formed during the reaction, Argonauts by applying a reduced pressure (approximately from 5 to 300 Torr). This reaction can be carried out at normal pressure or in vacuo, and the resulting specific alcohol in each case Argonauts. A suitable pressure is from 0.001 mbar to 1000 mbar, preferably from 5 to 10 mbar.

The amount of diethylene glycol may be, for example, from 1 equivalent to 100 equivalents, based on the methyl ester phenylglyoxylic acid (1 equivalent), preferably used 10 equivalents.

The reaction temperature may be from 20°to 180°C. Preferably the reaction is carried out at a temperature of from 40 to 120°With, especially when 50-60°C.

As a component of Glyoxylic acid (C)may use, for example, any of the lower ester (methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or sec-butyl ether, and others).

The reaction time is usually from 2 to 80 hours, preferably from 10 to 20 hours.

As Rast is orites for the reaction of transesterification can be used, for example, aromatic solvents such as benzene, toluene, cumene, o-, m - or p-xylene or their isomeric mixture, but it is also possible to use ethers, such as diethyl ether, diisopropyl ether, butyl methyl ether, methyl tert-butyl ether, 1,4-dioxane, tetrahydrofuran, etc. and hydrocarbons having a boiling point above 70°C. Preferably, the reaction is carried out without addition of solvent.

Processing of the reaction mixture is carried out, for example, by washing the mixture with water (removes catalyst and unreacted diethylene glycol); drying is carried out, for example, by adding a solvent which forms an azeotrope with water (e.g. toluene) and by azeotropic distillation. Any fluids diethylene glycol formed in the reaction is removed by extraction using a suitable organic solvent from a number of: benzene, toluene, cumene, o-, m - or p-xylene or their isomeric mixtures and/or diethyl ether, diisopropyl ether, butyl methyl ether, methyl tert-butyl ether, 1,4-dioxane and other

In addition, the treatment of the reaction mixture can also be carried out, for example, through column chromatography (removes unwanted by-products). The preferred solvent mixture for elution is a mixture of ethyl acetate with hexane or other hydrocarbon is m (heptane, petroleum ether and others). The ratio of ethyl acetate to the hydrocarbon may range from 90:10 to 30:70, and preferably 50:50.

II. In addition, a possible way of obtaining compounds of the invention involves the reaction of galodamadruga phenylglyoxylic acid (C), preferably the acid chloride phenylglyoxylic acid with alcohol (And)catalyzed by base:

The specialist in this field of technology are known, which are used in such reactions. Water base is not used. Examples of suitable bases include carbonates, tertiary-amine base, such as triethylamine and pyridine.

IIb. Another possible method of obtaining compounds of the invention includes a catalytic interaction phenylglyoxylic acid (S) with alcohol (A) and adding dicyclohexylcarbodiimide (DCC):

III. In addition, the compounds of the invention can be obtained, for example, by reacting alcohols (A) with the corresponding esters of phenylacetic acid (D) in the presence of a catalyst, followed by oxidation:

As catalysts may be used, for example, those described above in paragraph I. oxidation step may be performed, for example, as described in the publications J. Chem. Soc. Chem. Comm. 1993), 323 or Synthesis (1994), 915.

IV. As an additional method of obtaining compounds of formula I of this invention is subjected to discussion, for example, the interaction of the relevant replacement of phenylacetate (E) with alcohols (a) and subsequent oxidation:

This oxidation can be carried out, for example, in accordance with the method described in the journal J. Chem. Soc. Chem. Comm. (1994), 1807.

V. Additional possible way to obtain compounds of formula I of this invention involves the interaction of cyanide phenolcarboxylic acid (F) with alcohols (A), acid catalyzed:

VI. In addition, the compounds of formula I of this invention can be obtained, for example, by the reaction of the Friedel-benzene with dimeric anhydrides oxocarboxylic acids (H) in the presence of aluminium chloride:

Catalysts that may be used are well-known specialists in this field of technology conventional catalysts reaction Friedel-such as tin chloride, zinc chloride, aluminium chloride, titanium chloride or acid clay.

Usually the reaction I, IIb, III and IV can be carried out without using a solvent, with one of the reagents, which is a liquid, e.g. the alcohol, plays the role of the solvent. However, it is also possible to conduct the reaction in an inert solvent. Suitable solvents include, for example, aliphatic and aromatic hydrocarbons, for example alkanes and mixtures of alkanes, cyclohexane, benzene, toluene and xylene. Of course, it is advisable that the boiling temperature of these solvents was above the boiling point of the alcohol which is formed during the reaction.

The rest of the above expedient syntheses can be carried out in an inert solvent; suitable solvents are, for example, listed above.

In reaction I, III and IV is advisable to ensure removal from the reaction mixture of the alcohol which is formed during the reaction. This is done, for example, by distillation and, as described in paragraph I, using vacuum, if appropriate.

These reactions are carried out at different temperatures, in accordance with the applicable solvents and raw materials. Usually, the temperature and other conditions for the implementation of the discussed reactions well known to specialists in this field of technology.

The reaction products can be isolated and purified by using common methods, such as crystallization, distillation, extraction or chromatography.

Obtaining raw materials that are required for the synthetic is as compounds of formula I of the invention, usually well known to specialists in this field of technology. For example, some derivatives raw materials (B), (C), (D) and (F) may even be on sale.

For example, ethers () phenylglyoxylic acid obtained by the reaction of the Friedel-from benzene and appropriate methyl ester of the acid chloride oxocarboxylic acid or by esterification of the acid chlorides phenylglyoxylic acid (C) alcohols.

The acid chlorides (C) phenylglyoxylic acid can be obtained, for example, by chlorination of the corresponding acids, for example, using SOCl2.

Cyanides (F) phenolcarboxylic acid (F) can be obtained, for example, by reacting the appropriate acid chlorides of the acids with copper cyanide, CuCN.

You can obtain methyl ester of phenylacetic acid (D), for example, by interaction of benzylcyanide with methanol, catalyzed by acid. This reaction is described, for example, in the journal of Org. Syn. Coll. Vol.I, 270. Appropriate benzylcyanide can be obtained, for example, from the corresponding chlorides using NaCN, as described, for example, in the publications Org. Syn. Coll. Vol.I, 107 and Org. Syn. Coll. Vol.IV, 576.

Synthesis of ethyl ester of phenylacetic acid (D) are described, for example, in the journal J. Chem. Soc. Chem. Comm (1969), 515, and in the synthesis of the corresponding phenylboronic interacts with H2CH2SOOS2 H5in the presence of lithium in diethyl ether and CuBr. Another way interaction panelbased with ethyl acetate and NaH, described, for example, in the journal J. Am. Chem. Soc. (1959) 81, 1627. In the publication J. Org. Chem. (1968) 33, 1675 described the reaction of Grignard panibratov with BrCH2SOOS2H5with the formation of the ethyl ester of phenylacetic acid (D).

Getting alcohols (And) is well known to specialists in this field of technology and it is described in detail in the literature. Many such compounds are commercially available.

Of particular interest are compounds of the formula I, in which R1means hydroxyl. Such compounds can also be used as starting materials for obtaining the compounds of formula I, which are functionalized in the group R1in some other way.

Therefore, the invention also relates to a method for producing compounds of formula I as defined above in which R1is a HE, by the interaction of monoamino phenylglyoxylic acid of the formula II

,

where R represents a C1-C4alkyl, especially methyl or ethyl, with diola formula III

where the group

Y is the same as described above

where as the catalyst used, the lithium acetate, sodium acetate, potassium acetate, acetamide, the barium acetate, zinc acetate, cadmium acetate, copper acetate(II), cobalt acetate(II), aluminum acetate, calcium oxide, lithium methylate, sodium methylate, Tetra-isopropyl titanium, triisopropyl aluminum, tert-butyl lithium, 4-(dimethylamino)pyridine or the diacetate dibutylamine.

Further details relating to the conditions of this reaction, the above paragraph I.

Of interest is the way in which the catalyst is lithium acetate, and the way in which the reaction is carried out at a temperature of from 20°to 180°C.

Preferably, the amount of catalyst is from 0.1 to 20 mol.%, per component - ester of Glyoxylic acid of formula (II).

The compounds of formula I in which R1means the group HE represents photoinitiator implemented as such, but they can also be used for other implemented photoinitiators. Introducing photoinitiator according to the invention, produced from compounds of the formula I, in which R1means HE (in the following referred to as compounds of formula Ia)are, for example: urethanes obtained from isocyanates and compounds of the formula Ia; urethanes obtained from carbamoylation and compounds of the formula Ia; thiourethane obtained from diisocyanates and compounds of the formula Ia; esters of acids derived the C acid, acid chlorides of the acids, esters, acids, anhydrides, acids or anhydrides of phthalic acid and compounds of the formula Ia; carbonates derived from chloroformate and compounds of the formula Ia; glycidyloxy simple esters and diesters of glycerol, obtained from epichlorohydrin and compounds of the formula Ia.

Polyvalent participants reaction of compounds of formula Ia in the case of compounds of formula Ia in quantities less than the stoichiometric form products that are free of unreacted functional groups that can be embedded.

In this regard, of particular interest is the use of compounds With6H5-(CO)-(CO)-O-CH2-CH2-O-CH2-CH2HE as a starting material for obtaining the compounds of formula I, which are functionalized in the group R1that is different from the group, HE.

Below are examples of the use of the compounds of formula Ia, as intermediate compounds in the production of other implemented photoinitiators:

in which the values of R8, R9and Y is defined above.

Accordingly, the invention also relates to the use of compounds of formula I in which R1is a HE, as the source material upon receipt of the implemented photoinitiators, in which R1before the hat is SH, NR3R4, -(CO)-OH, -(CO)-NH2, SO3H, -C(R5)=CR6R7oxiranyl, -O-(CO)-NH-R8-NCO or-O-(CO)-R9-(CO)-X; and the radicals R3, R4, R5, R6, R7, R8, R9and X have the meanings specified above.

In addition, the invention relates to a method for introducing photoinitiators formula I, in which the compounds of formula I in which R1HE is a interacts with the isocyanate, carbamoylation, thioisocyanate, the acid chloride of the acid, ester, acid, acid anhydride, chloroformate or epichlorohydrin.

As components of the reaction mixture to obtain the implemented photoinitiators, proceeding from compounds of the formula I, in which R1is a HE, moreover, particularly suitable are the diisocyanates and oligopotent, which represents, for example, the technical mixture, which include hexamethylenediisocyanate, 1,6-diisocyanatohexane, tollen-2,4-diisocyanate, 4-methyl-m-delete the entry, 2,4-diisocyanato-1-methylcyclohexane, 1,3-biosocialities, m-xylylenediisocyanate, 1,3-visitorinformation, isophorondiisocyanate, 5-isocyanato-1-isocyanatomethyl-1,1,3-trimethylcyclohexane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexylisocyanate, difenilmetana-4,4'-diisocyanate, 4,4'-diphenylmethanediisocyanate, bis(4-and iinational)methane, 4,4-oxybis(phenylisocyanate), 4,4'-diisocyanato-3,3'-dimethyldiphenylamine, bis(4-isocyanato-3-were)methane, dicyclohexylmethane-4,4'-diisocyanate, 1,3,5-Tris(6-isocyanatophenyl)-[1,3,5]triazine-2,4,6-Trion, 1,3,5-Tris(6-isocyanatophenyl)biuret, diamid N,N',2-Tris(6-isocyanatophenyl)iminodicarboxylic acid, 1,3-bis(6-isocyanatophenyl)-[1,2]azetidin-2,4-dione, 2,5-2,6-Exo/endo-visitorinformation, 1,6-diisocyanato-2,2,4-trimethylhexane.

Appropriate industrial products come to market by Bayer AG under the name "Desmodur".

In the case of compounds of formula I, modified with isocyanate in fototerapia compositions, such as described below, is also suitable, for example, using the appropriate isocyanate resin as a curing component. Thus, increases compatibility photoinitiator with a composition which will cure.

According to the invention the compounds of formula I can be used as photoinitiators by photopolymerization ethylene-unsaturated compounds or mixtures containing such compounds. The use of these compounds is also possible in combination with another photoinitiator and/or other additives.

Therefore, the invention also relates to photopolymerizable compositions containing:

(a) at least one of these is enovo-unsaturated photopolymerization connection and

(b) at least one compound of formula I as photoinitiator, possibly, the composition, in addition to component (b)also contains other photoinitiator (in) and/or other additives (d).

The unsaturated compounds may contain one or more olefinic double bonds. They may have low molecular weight (monomer) or high molecular weight (oligomers). Examples of monomers having a double bond are alkyl and hydroxyethylacrylate and methacrylates, for example methyl, ethyl, butyl, 2-ethylhexyl and 2-hydroxyethylacrylate, isobutylacetate and methyl - and athletically. In addition, interest resin, modified silicon or fluorine, for example, siliconalley. Additional examples include Acrylonitrile, acrylamide, methacrylamide, N-substituted (meth)acrylamide, vinyl esters such as vinyl acetate, simple vinyl esters, such as isobutylphenyl ether, styrene, alkyl - and haloesters, N-vinyl pyrrolidone, vinyl chloride and vinylidenechloride.

Examples of monomers having several double bonds are etilenglikolevye, propilenglikolstearat, neopentylglycol, hexamethylenediamine and diacrylate bisphenol a, 4,4'-bis(2-acryloyloxyhexyloxy)diphenylpropane, triacrylate of trimethylolpropane, triacrylate pentaerythritol and tetraacrylate p is enteritica, vinylacetat, divinylbenzene, divinylbenzene, diallylphthalate, triethylphosphate, triallylisocyanurate and Tris(2-acrylonitril)isocyanurate.

Examples of polyunsaturated compounds with high molecular weight (oligomers) are epoxy acrylate resins, polyesters containing acrylate groups or simple vinyl esters or epoxy groups, polyurethanes and poly(simple) esters. Further examples of unsaturated oligomers are unsaturated polyester resins, which are usually obtained from maleic acid, phthalic acid and one or more diodes and have a molecular weight of approximately from 500 to 3000. Besides, it is also possible to use monomers and oligomers of vinyl ethers, as well as oligomers with maleate end groups with polyether, polyurethane, poly(simple)ether, polyvinyl(simple)ether and epoxy the main chain. Especially suitable are combinations of oligomers and polymers containing vinyl (simple) ether groups, which are described in the application WO 90/01512, however, can also be considered copolymers of monomers having functional groups of maleic acid and vinyl simple ether. Such unsaturated oligomers can also be called prepolymers.

Especially suitable are, for example, esters of ethylene is in the unsaturated carboxylic acids and polyols or polyepoxides, and polymers having ethylene unsaturated groups in the chain or in side groups, e.g. unsaturated polyesters, polyamides and polyurethanes and their copolymers, alkyd resins, polybutadiene and copolymers of butadiene, isoprene and copolymers of isoprene, polymers and copolymers having (meth)acrylic groups in side chains, and also mixtures of one or more of such polymers.

Examples of unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, taconova acid, cinnamic acid and unsaturated fatty acids such as linolenic acid or oleic acid. Preferred are acrylic and methacrylic acid.

Suitable polyols are aromatic and especially aliphatic and cycloaliphatic polyols. Examples of aromatic polyols are hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di(4-hydroxyphenyl)propane, and novolak, and resale. Examples of polyepoxides are those that are produced on the basis of these polyols, especially of aromatic polyols and epichlorohydrin. Also suitable as polyols are polymers and copolymers which contain hydroxyl groups in the polymer chain or in side groups, for example, polyvinyl alcohol and its copolymers or hydroxyalkyl esters of polymethacrylic acid or the copolymers. In addition, suitable polyols are oligoesters having hydroxyl end groups.

Examples of aliphatic and cycloaliphatic polyols include alkylenedioxy having preferably from 2 to 12 carbon atoms, such as ethylene glycol, 1,2 - or 1,3-propandiol, 1,2-, 1,3 - or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols having a molecular weight of preferably from 200 to 1500, 1,3-cyclopentanediol, 1,2-, 1,3 - or 1,4-cyclohexanediol, 1,4-dihydroxyphenylglycol, glycerol, Tris(β-hydroxyethyl)amine, trimethylacetyl, trimethylolpropane, pentaerythritol, and dipentaerythritol sorbitol.

These polyols may be partially or fully tarifitsirovana one (or various) unsaturated carboxylic acid (acid), and it is possible that the free hydroxyl groups in partial esters will be modified, for example, a group of simple ether, or tarifitsirovana other carboxylic acids.

Examples of esters are:

trimethylolpropane, Triethylenetetramine, trimethylolpropane, trimethylenetrinitramine, dimethacrylate of tetraethyleneglycol, triethylene glycol dimethacrylate, diacrylate tetraethyleneglycol, diacrylate pentaerythritol, triacrylate pentaerythritol, tetraacrylate pentameric the ITA, diacrylate of dipentaerythritol, triacrylate of dipentaerythritol, tetraacrylate of dipentaerythritol, pentacarinat of dipentaerythritol, hexagram of dipentaerythritol, actuariat of tripentaerythritol, pentaerythritol dimethacrylate, trimethacrylate pentaerythritol, dimethacrylate of dipentaerythritol, cerametallic of dipentaerythritol, octamethyl of tripentaerythritol, digitalnet pentaerythritol, traitement of dipentaerythritol, pentagonal of dipentaerythritol, exitement of dipentaerythritol, diacrylate of ethylene glycol, diacrylate 1,3-butanediol, dimethacrylate 1,3-butanediol, digitalnet 1,4-butanediol, triacrylate sorbitol, tetraacrylate sorbitol, modified triacrylate pentaerythritol, cerametallic sorbitol, pentakill sorbitol, hexagram sorbitol, oligoamine acrylates and methacrylates, di - and tri-acrylates glycerol, 1,4-cyclohexanediamine, bicarinate and mimetically of polyethylene glycol having a molecular weight of from 200 to 1500, and mixtures thereof.

Also suitable as component (a) are the amides of identical or different unsaturated carboxylic acids and aromatic, cycloaliphatic and aliphatic polyamines having preferably 2 to 6, especially from 2 to 4, amino groups. Examples of such polyamines are Ethylenediamine, 1,2 - or 1,3-Propylenediamine, 1,2-, 1,3 - or 1,4-butylenediamine, 1,5-pentanediamine, 1,6-hexylene is in, octylaniline, dodecylamine, 1,4-diaminocyclohexane, ISOPHORONEDIAMINE, phenylenediamine, biphenylamine, di-β-aminoacylase ether, Diethylenetriamine, Triethylenetetramine and di(β-aminoethoxy)ethane, di(β-aminopropoxy)ethane. In addition, suitable polyamines are polymers and copolymers, which may have additional amino group in the side chain, and oligoimide having terminal amino groups. Examples of such unsaturated amides are: methylenebisacrylamide, 1,6-hexamethylene-bisacrylamide, Diethylenetriamine-trimethacrylate, bis(methacryloyloxy)ethane, β-methacrylamido-methacrylate and N-[(β-hydroxyethoxy)ethyl]acrylamide.

Suitable unsaturated polyesters and polyamides are obtained, for example, from maleic acid and diols or diamines. Maleic acid may be partially replaced by other dicarboxylic acids. They can be used together with the ethylene-unsaturated comonomers, such as styrene. In addition, the polyesters and polyamides can be obtained from dicarboxylic acids and ethylene-unsaturated diols or diamines, especially from those who have more of a long chain, for example, from 6 to 20 carbon atoms. Examples of polyurethanes are those which consist of saturated diisocyanates and unsaturated diols or unsaturated diisocyanates and nasy the military diols.

Polybutadiene and polyisoprene, and their copolymers are known. Suitable comonomers include, for example, olefins such as ethylene, propylene, butene and hexene, (meth)acrylates, Acrylonitrile, styrene and vinyl chloride. Polymers having a (meth)acrylate groups in the side chain, are also known. Examples represents the interaction products of epoxy resins on the basis of novolak with (meth)acrylic acid; Homo - or copolymers of vinyl alcohol or hydroxyalkyl derivatives, which tarifitsirovana (meth)acrylic acid; and Homo - and copolymers of (meth)acrylates, which tarifitsirovana hydroxyalkyl(meth)acrylates.

Suitable components (a) include acrylates, which are modified by interaction with primary or secondary amines, for example, as described in patents US 3844916, EP 280222, US 5482649 or US 5734002. Such aminodiphenylamine acrylates are also called aminoacetate. Aminoacridine can be obtained, for example, by UCB Chemicals under the nameRTMEBECRYL 80,RTMEBECRYL 81,RTMEBECRYL 83,RTMEBECRYL 7100, from BASF under the nameRTMLaromer PO 83F,RTMLaromer PO 84F,RTMLaromer PO 94F, from Cognis under the name ofRTMPHOTOMER 4775F,RTMPHOTOMER 4967F or from Cray Valley under the name ofRTMCN501,RTMCN503,RTMCN550.

Photopolymerizing compounds may be used individually or in any desired mixture. Preferably used a mixture of polyol(meth)acrylates.

In addition, compositions according to the invention can be added as a binding agent, and this is especially advisable when photopolymerizing compounds are liquid or viscous substances. The amount of binder may be, for example, from 5 to 95 wt.%, preferably from 10 to 90 wt.% and especially from 40 to 90 wt.%, in the calculation of the amount of solids. The choice of the binder is performed in accordance with its scope of application and required properties, such as the ability to breed in water and organic solvents, adhesion to substrates and sensitivity to oxygen.

Suitable binders are, for example, polymers having a molecular weight of about 5000 to 2000000, preferably from 10000 to 1000000. Examples are: Homo - and copolymers of acrylates and methacrylates, e.g. copolymers of methyl methacrylate/acrylate/methacrylic acid, poly(alkalemia esters of methacrylic acid), poly(alkalemia esters of acrylic acid), cellulose ethers and ethers such as cellulose acetate, acetate butyrate cellulose, methylcellulose, ethylcellulose; butyral, polyvinylformal, recycled rubber, poly(ethers), such as polyethylene oxide, polypropyleneoxide, polytetrahydrofuran; poly the Tyrol, polycarbonate, polyurethane, chlorinated polyolefins, polyvinyl chloride, copolymers of vinyl chloride/vinylidenechloride, copolymers of vinylidenechloride with Acrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate, a copolymer of ethylene and vinyl acetate, polymers, such as polycaprolactam and poly(hexamethylene adipic acids), polyesters, such as poly(etilenglikolevye) and poly(hexamethylenediisocyanate).

In addition, the unsaturated compounds may be used in a mixture with non-photopolymerization film-forming components. They can represent, for example, physically drying polymers or their solutions in organic solvents, for example, nitrocellulose or acetobutyrate cellulose, but they can also be chemically or thermally curable resins, for example, polyisocyanate, polyepoxide or melamine resin. Concomitant use of thermally curable resin has a value for use in so-called hybrid systems, which photopolymerized in the first stage and fastened in the subsequent heat treatment in the second stage.

Photoinitiator according to the invention are also suitable initiators for curing, which undergo oxidative drying, such that the cat is who describes for example, in the book Lehrbuch der Lacke und Beschichtungen, volume III, 296-328, Verlag W.A.Colomb in der Heenemann GmbH, Berlin-Oberschwandorf (1976).

In addition, the compounds according to the invention, for example compounds of the formula I, in which R1is a HE, are particularly suitable as photoinitiators for hybrid binder systems. Typically, such systems include at least one thermally curable component and one photochemically curable component. Usually thermally curable component is a two-component or multi-component reactive resin, preferably a polyol/polyisocyanate type. As a photochemically curable components here can be seen all Monomeric, oligomeric or polymeric unsaturated compounds and their combinations used for this purpose, the polymerization or crosslinking which takes place under the action of radiation of high energy and using photoinitiators. Such compounds are described in detail below. In addition, suitable examples include isocyanates series "Desmodur"described above. Thermal/photochemical hybrid system can be obtained by co-mixing of all components, and it is advisable to add the isocyanate component only immediately prior to use, as is the normal practice for the PE klonopon resins, forming polyurethanes, in order to avoid a premature full curing thermally polymerizable component. For full curing of the coatings obtained with such hybrid systems, primarily covering exposed in a way that is normal for radiation curable systems, the process which is quick drying of the surface and the initial curing of the layer. State final curing is implemented when thermal reaction, which can also be accelerated by heat. However, it is also possible that the curing was carried out first thermally and then under the action of UV radiation. The advantage of such systems, compared with the slowly drying systems based only thermally reactive resins, lies in the substantial reduction of time and energy process; covered products can be laid directly or faster to carry out the subsequent processing.

The advantage of using photoinitiators according to the invention in a hybrid binder systems is that, unlike traditional photoinitiators, in definitive, fully cured polymeric material is almost no remnants of photoinitiator or products of photolysis of the initiator (data analysis). In line with this,the polymer products have a high final hardness; significantly reduced the likelihood of adverse impacts caused by the initiator, such as, for example, an unpleasant smell or yellowing. Due to the presence of Oh groups covalent introduction of photoinitiator according to the invention in the polymer material is due to the interaction with equivalent amounts of isocyanate component thermally-curable component in a hybrid binder system.

In accordance with this invention also relates to compositions, which are described above and which contain, in addition to the photochemically curable component and the component (b)and (C) and (d), if appropriate, also thermally curable component.

In addition, the compounds of formula I in which R1is a HE, can be covalently linked, as in a purely radiation-curable systems, and hybrid systems, as a result of esterification with components containing a carboxylic acid group. Examples of such components include, for example, terephthalic acid, pyromellitic acid and its anhydrides, and also oligomers or polymers derived from such compounds and still containing at least one functional group of a free carboxylic acid.

In addition, photopolymerized mixture may contain various additives (d), in addition to photon is Satoru. Examples of additives are thermal inhibitors, the purpose of which is to prevent premature polymerization, for example, hydroquinone, hydroquinone derivatives, n-methoxyphenol, β-naphthol or sterically difficult phenols, for example 2,6-di(tert-butyl)-n-cresol. To improve the dark stability during storage is possible using, for example, copper compounds, such as the naphthenate, stearate or octoate copper, phosphorus compounds, for example triphenylphosphine, tributylphosphine, triethylphosphine, triphenylphosphine or tribenzylphosphine, Quaternary ammonium compounds, for example, Tetramethylammonium chloride or trimethylphenylammonium, or derivatives of hydroxylamine, for example, N-diethylhydroxylamine. To exclude the presence of atmospheric oxygen during the polymerization can be added to a mixture of paraffin or similar wax-like substances, which due to insolubility in the polymer migrates to the surface at the beginning of the polymerization and form a transparent surface layer which prevents the flow of air. Another possibility is the application layer that is impermeable to oxygen. As light stabilizers can be added UV absorbers, for example, type hydroxyphenylacetate, hydroxyphenylpropionic, amide of oxalic acid or hydroxyphenyl-Symm.-Tria is in. Such compounds can be used individually or as mixtures, using sterically obstructed amines (HALS) or without them.

Examples of such UV absorbers and light stabilizers:

1). 2-(2'-Hydroxyphenyl)benzotriazole, for example, 2-(2'-hydroxy-5'-were)benzotriazol, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazol, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazol, 2-(2'-hydroxy-5'-(1,1,3,3-TETRAMETHYLBUTYL)phenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-were)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazol, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazol, 2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, a mixture of 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxyphenyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxyphenyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-were)benzotriazole and 2-(3-tert-butyl-2'-hydroxy-5'-(2-isooctylmercaptoacetate)phenyl)benzotriazole, 2,2'-methylene-bis[4-(1,1,3,3-TETRAMETHYLBUTYL)-6-benzotriazol-2-infenal]; the product of transesterification of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]benzotriazole with polyethylene glycol 300; [R-CH2CH2-COO(CH2)3]2-, where R is 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl.

2). 2-Hydroxybenzophenone, for example, 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy or 2'-hydroxy-4,4'-dimethoxy-derivative.

3). Esters of unsubstituted or substituted benzoic acids, for example, 4-tert-butylanisole, fenilsalitsilat, antifederalist, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylation, 2,4-di-tert-BUTYLPEROXY ester of 3,5-di-tert-butyl-4-hydroxybenzoic acid, hexadecylamine ester of 3,5-di-tert-butyl-4-hydroxybenzoic acid, octadecenoic ester of 3,5-di-tert-butyl-4-hydroxybenzoic acid and 2-methyl-4,6-di-tert-BUTYLPEROXY ester of 3,5-di-tert-butyl-4-hydroxybenzoic acid.

4). Acrylates, for example ethyl ester or isooctyl ester α-cyano-β,β-diphenylacetone acid, methyl ester α-methoxycarbonylamino acid, methyl ester or butyl ester α-cyano-βn-methyl-n-methoxycatechol acid, methyl ester α-methoxycarbonyl-n-methoxycatechol acid and N-(β-methoxycarbonyl-β -cyanovinyl)-2-methylindolin.

5). Steric employed amines, for example bis(2,2,6,6-tetramethylpiperidine)sebacina, bis(2,2,6,6-tetramethylpiperidine)succinate, bis(1,2,2,6,6-pentamethylpiperidin)sebacina, bis(1,2,2,6,6-pentamethylpiperidine) ether n-butyl-3,5-di-tert-butyl-4-hydroxybenzylidene acid, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product,

N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)diamine and 4-tert-octylamine-2,6-dichloro-1,3,5-s-triazine, Tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetriol, 1,1'-(1,2-ethandiyl)-bis(3,3,5,5-tetramethylpiperidine), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-sterilox-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidin)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,

3-n-octyl-7,7,9,9-tetramethyl-1,3,8-diazaspiro[4.5]decane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidine)sebacina, bis(1-octyloxy-2,2,6,6-tetramethylpiperidine)succinate, condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)diamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, condensation product of 2-chloro-4,6-di(4-n-butylamino-2,2,6,6-tetramethylpiperidine)-1,3,5-triazine and 1,2-bis(3-aminopropylene)ethane, condensation product of 2-chloro-4,6-di(4-n-butylamino-1,2,2,6,6-pentamethylpiperidin)-1,3,5-triazine and 12-bis(3-aminopropylene)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-diazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidin-2,5-dione, 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-N-butylamino]-6-(2-hydroxyethyl)amino-1,3,5-triazine, condensation product of 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-6-chloro-Siim-triazine and N,N'-bis(3-aminopropyl)Ethylenediamine.

6). The diamide of oxalic acid, for example, 4,4'-distractionware, 2,2'-diethoxyaniline, 2,2'-dioctyloxy-5,5'-di-tert-butylanisole, 2,2'-didodecyl-5,5'-di-tert-butylanisole, 2-ethoxy-2'-ethyloxazole, N,N'-bis(3-dimethylaminopropyl)oxalate, 2-ethoxy-5-tert-butyl-2'-ethyloxazole and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxyaniline and mixtures of o - and n-methoxy - and of o - and n-ethoxymethylene of oxanilide.

7). 2-(2-Hydroxyphenyl)-1,3,5-triazine, for example, 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-propyloxy-phenyl)-6-(2,4-dimetilfenil)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-were)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butylacetophenone)phenyl]-4,6-bis(2,4-dimetilfenil)-1,3,5-three the zine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxyphenyl)phenyl]-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine and 2-[4-dodecyloxy/tridecylamine-(2-hydroxypropyl)oxy-2-hydroxyphenyl]-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine.

8). The phosphites and phosphonites, for example, triphenylphosphite, diphenylacetate, phenyldichlorophosphine, Tris(nonylphenyl)FOSFA, trilaurylamine, trioctadecyl, the diphosphite of diseasespecific, Tris(2,4-di-tert-butylphenyl)FOSFA, the diphosphite of diisodecylphthalate, the diphosphite and bis(2,4-di-tert-butylphenyl)of pentaerythritol, the diphosphite and bis(2,6-di-tert-butyl-4-were)of pentaerythritol, the diphosphite bis(isodecyloxy)of pentaerythritol, the diphosphite and bis(2,4-di-tert-butyl-6-were)of pentaerythritol, the diphosphite bis(2,4,6-three-tert-butylphenyl)of pentaerythritol, triphosphate of tristearate, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediisocyanate, 6-isooctane-2,4,8,10-Tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphospholane, 6-fluoro-2,4,8,10-Tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphospholane, bis(2,4-di-tert-butyl-6-were)metaltastic and bis(2,4-di-tert-butyl-6-were)ethylphosphate.

Additional examples of UV absorbers and light stabilizers suitable as component (d)represent the "Krypto-UVA", which are described, for example, in document EP 180548. You can also use latent UV absorbers are described, for example, in the work of Hida and others, RadTech Aia 97, 1997, s.

In addition, can be used supplements, traditional art, such as, for example, antistatic additives, additives for improving the fluidity and adhesion promoters.

As additional additives (g) to accelerate the photopolymerization can be used numerous amines, for example triethanolamine, N-methyldiethanolamine, ethyl ester n-dimethylaminobenzoyl acid or michler ketone. The action of amines can be enhanced by the addition of aromatic ketones, such as benzophenone. Amines suitable for use as agents, exciting oxygen are, for example, substituted N,N-dialkylanilines, which are described in the document EP 339841. Additional accelerators, coinitiators and autocollapse are thiols, simple thioethers, disulfides and phosphines, which are described, for example, in documents EP 438123 and GB 2180358.

You can also add in the compositions according to the invention agents, chain transfer, the traditional prior art. Examples of agents include mercaptans, amines and benzotriazol. In addition, the photopolymerization can be accelerated by adding, as an additional additives (g), photosensitizers, which shift or broaden the spectral sensitivity. Specifically, they include aromatic Carbo is safe connection for example, derivatives of benzophenone, derivatives of thioxanthone, in addition, especially isopropylthioxanthone, derivatives of anthraquinone and derivatives 3-acicularis, terphenyls, strikeone and 3-(koimeterion)of thiazoline, camphor quinone, and eosinophile, rodnikovye and erythrosine dyes.

As photosensitizers can also be discussed, for example, the above-mentioned amines. Additional examples of such photosensitizers are listed below.

1). Thioxanthone

Thioxanthone, 2-isopropylthioxanthone, 3 isopropylthioxanthone, 2-chlorothioxanthone, 2-dodecylamine, 1-chloro-4-propoxyimino, 2,4-dietitican, 2,4-dimethyldioxanes, 1 methoxycarbonylamino, 2-ethoxycarbonylmethoxy, 3-(2-methoxyethoxymethyl)thioxanthone, 4-butoxycarbonylamino, 3-butoxycarbonyl-7-methylthionine, 1-cyano-3-chlorothioxanthone, 1-etoxycarbonyl-3-chlorothioxanthone, 1-etoxycarbonyl-3-etoxification, 1-etoxycarbonyl-3-aminothiazole, 1-etoxycarbonyl-3-phenylsulfonylacetate, 3,4-di[2-(2-methoxyethoxy)etoxycarbonyl]thioxanthone, 1-etoxycarbonyl-3-(1-methyl-1-morpholinoethyl)thioxanthone, 2-methyl-6-dimethoxymethylsilane, 2-methyl-6-(1,1-dimethoxybenzyl)thioxanthone, 2-morpholinoethoxy, 2-methyl-6-morpholinoethoxy, N-allithiamine-3,4-dicarboximide, N-artisticchardon-3,4-dicarboximide, N-(1,1,3,3-Tetra is ethylbutyl)thioxanthone-3,4-dicarboximide, 1 renoxification, 6-etoxycarbonyl-2-detoxification, 6-etoxycarbonyl-2-methylthionine, thioxanthen-2-polietilenglikolya ether, chloride, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanamine;

2). Benzophenone

Benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-dimethylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzoate, 4-methylbenzophenone, 3-methyl-4'-phenylbenzophenone, 2,4,6-trimethylbenzene, 2,4,6-trimethyl-4'-phenylbenzophenone, 4-(4-methylthiophenyl)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, methyl ester 2-benzoylbenzene acid, 4-(2-hydroxyethylthio)benzophenone, 4-(4-tolylthio)benzophenone, chloride, 4-benzoyl-N,N,N-trimethylindolenine, monohydrate chloride, 2-hydroxy-3-(4-benzoylperoxy)-N,N,N-trimethyl-1-propanamine, 4-(13-acryloyl-1,4,7,10,13-pentaacetate)benzophenone, chloride, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyl)oxy]ethylbenzylamine;

3). 3-Acicularis

3-Benzoyltartaric, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-5,7-di(propoxy)coumarin, 3-benzoyl-6,8-dichloroaniline, 3-benzoyl-6-chlorocoumarin, 3,3'-carbonyl-bis[5,7-di(propoxy)coumarin], 3,3'-carbonyl-bis(7-methoxycoumarin), 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-isobutylamino, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-5,7-diethoxyaniline, 3-benzoyl-5,7-dibutoxy is Rin, 3-benzoyl-5,7-di(methoxyethoxy)coumarin, 3-benzoyl-5,7-di(allyloxy)coumarin, 3-benzoyl-7-diethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3-isobutyryl-7-diethylaminocoumarin, 5,7-dimethoxy-3-(1-naphtol)coumarin, 5,7-dimethoxy-3-(1-naphtol)coumarin, 3-benzoylbenzene[f]coumarin, 7-diethylamino-3-tenormin, 3-(4-cyanobenzoyl)-5,7-dimethoxycoumarin;

4). 3-(Koimeterion)of thiazoline

3-Methyl-2-benzoylmethylene-β-negotiation, 3-methyl-2-benzoylmethylecgonine, 3-ethyl-2-propionitrile-β-negotiation;

5). Other carbonyl compounds

The acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, benzyl, 2-acetylation, 2-naphthaldehyde, 9,10-anthraquinone, 9-fluorenone, dibenzosuberone, xanthone, 2,5-bis(4-diethylaminobenzylidene)Cyclopentanone, α-(para-dimethylaminobenzylidene)ketones, such as 2-(4-dimethylaminobenzylidene)indan-1-one or 3-(4-dimethylaminophenyl)-1-indan-5-ispropanol, 3-phenylthiophene, N-methyl-3,5-di(ethylthio)phthalimide.

In addition, the curing process, especially in the case of pigmented compositions (e.g., compositions with pigment - titanium dioxide), can contribute to add, as a further additive (d)component, which generates free radicals under the conditions of heating, for example, azo compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), Triesen, dissolved, pentazocine is or peroxide compounds, for example, hydroperoxide or peroxocarbonate, for example, tert-butylhydroperoxide, as described, for example, in document EP 245639.

In addition, compositions according to the invention can contain, as further additives (d) photovoltaikanlagen dyes, for example, xanthene, benzoxanthene, benzodioxathiepin, casinowe, Pironkova, porphyrin or acridine dyes, and/or radiation split trihalomethyl connection. Such materials are described, for example, in EP 445624.

Furthermore, additional additives (g) are - depending on the intended use fluorescent whitening agents, fillers, pigments both white and colored pigments, dyes, antistatic agents, wetting agents or additives which improve the fluidity.

The addition of glass microspheres or pulverized glass, as described, for example, in US 5013768 is convenient for curing thick and pigmented coatings.

The composition can also contain dyes and/or white, or colored pigments. Depending on the intended use can be used as inorganic and organic pigments. Such additives can be well-known specialist in this field of technology; selected examples of pigments are titanium dioxide, such as rutile or anatase, carbon black, zinc oxide, such as zinc white, iron oxides, such as yellow iron oxide, red iron oxide, chrome yellow, green, black, yellow Nickel titanate, ultramarine blue, cobalt blue, bismuth Vanadate, cadmium yellow and cadmium red. Examples of organic pigments are mono - or bis-azo pigment, as well as their metal complexes, phthalocyanine pigments, polycyclic pigments, for example, Pereladova, antrahinonovye, thioindigo, chinaredorbit or triphenylmethane pigments, and diketopiperazine, isoindolines, for example, tetrachlorethylene, isoindoline, dioxazine, benzimidazolone and chieftancy pigments. Pigments can be used in the compositions in pure form or in a mixture.

Depending on the intended use of the pigments added to the composition in amounts that are adopted in the prior art, for example, in amounts of from 0.1 to 60 wt.%, from 0.1 to 30 wt.%, or from 10 to 30 wt.%, in the calculation of the total mass.

In addition, the composition may include, for example, organic dyes very wide variety of types. Examples are azo dyes, methine dyes, antrahinonovye dyes and metal complex dyes. Adopted by the concentrations are, for example, from 0.1 to 20%, especially from 1 to 5%, in races is to know the total mass.

Depending on the applied composition can also be used as stabilizers compounds that neutralize acids, especially amines. Suitable systems are described, for example, in document JP-A 11-199610, Examples are pyridine and its derivatives, N-alkyl - or N,N-dialkylanilines, derivatives pyrazine, derivatives of pyrrole and other

The choice of additives is determined by considering the scope and properties that are desirable in this area. The above-described additives (g) are traditional in this area, and respectively used in amounts conventional in this field. The share of additional additives in the compositions according to the invention is, for example, from 0.01 to 10 wt.%, for example from 0.05 to 5 wt.%, especially from 0.1 to 5 wt.%.

In addition, the invention relates to compositions comprising as component (a)at least one ethylene-unsaturated photopolymerization compound, dissolved or emulsified, or dispersed in water.

Water dispersion of the radiation-curable prepolymers obtained in industry in various forms and it should be understood that they constitute a dispersion comprising water as a continuous phase and at least one prepolymer dispersed in water. Radiation curing prepolymer and is a mixture of prepolymers dispersed in water at a concentration of from 20 to 95 wt.%, especially from 30 to 70 wt.%. In such compositions the amount of interest specified for water and prepolymer or a mixture of prepolymers, in each case equal to 100% in each case, and auxiliary substances and additives such as emulsifiers), which may be present in varying amounts in accordance with the intended use, are added in excess of 100%.

Water dispersion of the radiation-curable prepolymers are known polymer systems that contain mono - or poly-ethylene-unsaturated prepolymers which have an average molekulyarnuyu mass Mn(g/mol), at least 400, especially from 500 to 100000. However, the prepolymers having a higher molecular weight are also suitable, depending on the intended use.

For example, are polymerizable polyesters containing C=C double bond and having a maximum acid number of 10, polymerizable poly(simple)ethers containing C=C double bond containing hydroxyl groups, the reaction products of polyepoxide containing at least two epoxypropyl in the molecule, at least one α,β-ethylene-unsaturated carboxylic acid, polyurethane(meth)acrylates, and acrylic copolymers containing α,β-ethylene unsaturated acrylic radicals to the e described in the patent EP 12339. Additionally, there may be used mixtures of these prepolymers.

Also suitable are the polymerizable prepolymers are described in the document EP 33896, which are adducts of simple thioethers, which have an average molecular mass Mn(g/mol), at least 600, and which also contain polymerizable C=C double bonds.

Additional suitable aqueous dispersion of polymers, based on the products of polymerization of specific alilovic esters of (meth)acrylic acid, described in EP 41125.

Water dispersion of the radiation-curable prepolymers may also contain, as further additives, additional additives (g) described above, for example, dispersible excipients, emulsifiers, antioxidants, light stabilizers, creately, pigments, fillers, such as talc, gypsum, silicic acid, rutile, carbon black, zinc oxide, iron oxides, reaction accelerators, fluidity promoters, promoters slip, wetting agents, thickeners, matting agents, antifoaming agents and other AIDS, the traditional technology of surface coatings. Suitable auxiliary dispersant include water-soluble high-molecular organic compounds having polar groups, for example, polyvinyl alcohols, watering solerrain and ethers of cellulose. Emulsifiers which can be used are nonionic and ionic emulsifiers, if appropriate.

In addition, photoinitiator formula I according to the invention can be dispersed as such in aqueous solutions and in this dispergirovannom as added in the mixture to be cured. When mixed with suitable non-ionic or, if appropriate, also with ionic emulsifiers, compounds of formula I according to the invention can be introduced into the water by mixing, for example, grinding. Obtained a stable emulsion which can be used as such, as photoinitiators, especially for water fototerapia mixtures described above.

In some cases it may be desirable to use mixtures of two or more photoinitiators according to the invention. Of course, can also be used mixtures with known photoinitiators, examples of which are mixed with camporgiano, benzophenone, benzophenone derivatives, acetophenone derivatives of acetophenone, such as hydroxycarbonylmethyl or 2-hydroxy-2-methyl-1-phenylpropane, dialkoxybenzene, α-hydroxy - or α-aminoacetophenone, such as (4-methylthiophenyl)-1-methyl-1-morpholinoethyl, (4-morpholinomethyl)-1-benzyl-1-dimethylaminopropane, 4-aroyl-1,3-is oxolane, simple benzoylcholine esters and benzylacetone, such as benzyldimethylamine, other phenylglyoxylate and derivatives thereof, dimeric phenylglyoxylate, peroxides, esters, for example, periphery benzophenonetetracarboxylic acid, which are described, for example, in document EP 126541, monoolefins, such as (2,4,6-trimethylbenzoyl)phenylphosphine, besatisfied, such as bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpent-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine or bis(2,4,6-trimethylbenzoyl)(2,4-dipentylester)phosphine oxide, triarylphosphines, kaleidocycles, for example, 2-[2-(4-methoxyphenyl)vinyl]-4,6-bistriflate[1,3,5]triazine, 2-(4-methoxyphenyl)-4,6-bistriflate-[1,3,5]triazine, 2-(3,4-acid)-4,6-bistriflate[1,3,5]triazine, 2-methyl-4,6-bistriflate[1,3,5]triazine, system sexualvideo/coinitiator, for example, ortho-chlorhexidinegluconate in combination with 2-mercaptobenzothiazole; connection ferrocene or titanocene, such as dicyclopentadienyl-bis(2,6-debtor-3-pyrrolidinyl)titanium; or esters O-alloxylon, which are described, for example, in document GB 2339571. In addition, can be used borate compounds as coinitiators.

When photoinitiator of the invention are used in hybrid systems (in this context, it means mixed system, to the which can be solidified by free radicals and cations), they are used in addition to the reagents of free radical curing according to the invention, the cationic photoinitiators, such as benzoyl peroxide (other suitable peroxides are described in the patent US 4950581, column 19, lines IP-25), aromatic salts sulfone, phosphonium or iodone, which are described, for example, in patent US 4950581 (column 18, line 60 to column 19, line 10) or salts kompleksow cyclopentadienylmanganese(II), for example, hexaflurophosphate (η6-isopropylbenzene)(η5-cyclopentadienyl)iron(II) or focoltone acid-based Akimov, which are described, for example, in documents GB 2348644, US 4450598, US 4136055, WO 00/10972, WO 00/26219.

The invention relates also to compositions in which an additional photoinitiator (C) are compounds of formulas VIII, IX, X, XI or XII:

in which R25represents hydrogen, C1-C18alkyl, C1-C18alkoxy, -OCH2CH2-OR29morpholino, SCH3or groupor

n varies from 2 to 10;

of G1and G2each independently represent a terminal group is s polymer chain, especially hydrogen or CH3;

R26represents hydroxy, C1-C16Baldacci, morpholino, dimethylamino or-O(CH2CH2O)m-C1-C16alkyl;

R27and R28each independently represent hydrogen, C1-C6alkyl, phenyl, benzyl, allyl,1-C16alkoxy or-O(CH2CH2O)m-C1-C16alkyl, or R27and R28together with the carbon atom to which they are bound form a cyclohexane ring;

m denotes a number from 1 to 20;

in which all R26, R27and R28at the same time do not represent a1-C16alkoxy or-O(CH2CH2O)m-C1-C16alkyl, and

R29represents hydrogen,or;

R30and R32each independently mean hydrogen or methyl;

R31represents hydrogen, methyl, 2-hydroxyethylthio or phenylthio, and the benzene ring of phenylthiazole is unsubstituted or substituted With1-C4the alkyl 4-, 2-, 2,4 - or 2,4,6-positions;

R33and R34each independently denote With1-C20alkyl, cyclohexyl, cyclopentyl, phenyl, naphthyl or diphenyl, and these radicals are unsubstituted or are they replaced by ha is ogena, With1-C12the alkyl or/and group

With1-C12alkoxy, or R33is an S - or N-containing five - or six-membered heterocyclic ring, or;

R35represents cyclohexyl, cyclopentyl, phenyl, naphthyl or diphenyl, and these radicals are unsubstituted or substituted by one or more halogen atoms, With1-C4the alkyl or/and C1-C4alkoxy substituents, or R35is an S - or N-containing five - or six-membered heterocyclic ring;

R36and R37each independently represents a cyclopentadienyl which is unsubstituted or substituted one, two or three times

C1-C18the alkyl, C1-C18alkoxy, cyclopentyl, cyclohexyl or halogen; and

R38and R39each independently of the other represents phenyl, which is substituted by fluorine atoms or by a group of CF3at least in the two ortho-positions to the titanium-carbon connection and which may contain, as an additional substituent in the aromatic ring, pyrroline or polically, each of the

which is unsubstituted or substituted by one or two groups: With1-C12alkyl, di(C1-C12alkyl)aminomethyl, morpholinomethyl, sub> 2-C4alkenyl, methoxymethyl, ethoxymethyl, trimethylsilyl, formyl, methoxy or phenyl, or R38and R39representor;

R40, R41and R42each independently mean hydrogen, halogen, C2-C12alkenyl,1-C12alkoxy, C2-C12alkoxy which is interrupted by one to four oxygen atoms, cyclohexyloxy, cyclopentyloxy, phenoxy, benzyloxy, unsubstituted phenyl or diphenyl, or substituted groups With1-C4alkoxy-, halo-, phenylthio or1-C4alkylthio - phenyl or diphenyl, in which both R40and R42at the same time does not mean hydrogen, and the radicalat least one radical R40or R42represents a

With1-C12alkoxy, C2-C12the alkoxy group, which is interrupted by one to four oxygen atoms, cyclohexyloxy, cyclopentyloxy, phenoxy or benzyloxy;

E1represents O, S or NR43;

R43represents a C1-C8alkyl, phenyl or cyclohexyl; and

Y1represents a C3-C12alkylen, butylen, Butylin or4-C12alkylene, which is interrupted once or several times by groups-O -, or-NR44 -not following each other, or Y1represents a phenylene, cyclohexene,; and

R44represents hydrogen, C1-C4alkyl or C2-C4hydroxyalkyl.

Preferred are compositions in which, in the compounds of formulas VIII, IX, X, XI and XII

R25represents hydrogen, -OCH2CH2-OR29morpholino, SCH3or group;

R26represents hydroxy, C1-C16alkoxy, morpholino or dimethylamino;

R27and R28each independently of the other, means1-C4alkyl, allyl, phenyl, benzyl or C1-C16alkoxy, or R27and R28together with the carbon atom to which they are bound form a cyclohexane ring;

R29represents hydrogen or;

R30, R31and R32mean hydrogen atoms;

R33represents a C1-C12alkyl, unsubstituted phenyl or phenyl substituted With1-C12the alkyl or/and group C1-C12alkoxy;

R34represents; and

R35represents phenyl, which is substituted by one or more substituents With1-C4alkyl or C1-C4alkoxy

Preferred compounds of formulas VIII, IX, X, XI and XII are α-hydroxycyclohexanone and 2-hydroxy-2-methyl-1-phenylpropane, methyl ester phenylglyoxylic acid, phenyl-(CO)(CO)-co2CH2OCH2CH2O-(CO)(CO)-phenyl, (4-methylthiophenyl)-1-methyl-1-morpholinoethyl, (4-morpholinomethyl)-1-benzyl-1-dimethylaminopropane, (3,4-dimethoxybenzoyl)-1-benzyl-1-dimethylaminopropane, (4-morpholinomethyl)-1-(4-methylbenzyl)-1-dimethylaminopropane, benzyldimethylamine, (2,4,6-trimethylbenzoyl)phenylphosphine, bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpent-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine or bis(2,4,6-trimethylbenzoyl)-(2,4-dipentylester)phosphine oxide and dicyclopentadienyl-bis(2,6-debtor-3-pyrrole)titanium.

In addition, preference is given to compositions in which in formula VIII radicals R27and R28each independently represent a C1-C6alkali or, together with the carbon atom to which they are bound form a cyclohexane ring, and R26represents hydroxy.

The proportion of the compounds of formula I (corresponding to component (b) photoinitiator) in a mixture with compounds of formulas VIII, IX, X, XI and/or XII (corresponding to a component (C) photoinitiator) is from 5 to 99%, for example, from 20 to 80%, preferably from 25 to 75%.

Of particular interest com is osili, described above, which contain a mixture of photoinitiators formula I, VIII, IX, X, XI and/or XII and are liquid at room temperature.

The formation of compounds of formulas VIII, IX, X, XI and XII are usually known to specialists in this field of technology, and some of these compounds are produced in an industrial scale. Getting oligomeric compounds of the formula VIII is described, for example, in document EP 161463. Description obtain the compounds of formula IX can be found, for example, in EP 209831. Obtaining compounds of formula X are disclosed, for example, in documents EP 7508, EP 184095 and GB 2259704. Obtaining compounds of formula XI are described, for example, in EP 318894, EP 318893 and EP 565488. Obtaining compounds of formula XII are described, for example, in patent US 6048660.

Photopolymerizing compositions contain photoinitiator mainly in the amount of from 0.05 to 20 wt.%, for example, from 0.05 to 15 wt.%, preferably from 0.1 to 5 wt.%, in the calculation of the composition. The specified number of photoinitiator refers to the total number of all added photoinitiators when using mixtures thereof, in other words to photoinitiator (b), as well as to a mixture of photoinitiators (b)+(C).

Photopolymerizing compositions can be used in various fields, for example as printing inks, for example, inks screen printing inks flexographic printing or ink offset printing, quality is ve transparent coatings, as colored coatings, as white coatings, for example for wood or metal, as powder coatings, as inks for paper (among others), wood, metal or plastics, paints, curing light, for marking structures and roads, for photographic processes of reproduction, for holographic recording materials, processes for image recording or receiving printed circuit boards, which may occur with the use of organic solvents or using aqueous-alkaline medium, upon receipt of the inks for screen printing, as dental compositions of fillers, as glues, adhesives, pressure-sensitive, as resins for laminating, as photoresistors, such as galvanization, resistors etching or permanent resistors as liquid and dry films, as photostructurable dielectrics, and as a stencil for applying solder in electronic circuits, resistors in the production of color filters for flat screens of any type or in the formation of structures in the production of plasma displays and electroluminescent displays, in the manufacture of optical keys, optical grids (interference grids), the production of three-dimensional products by volume is about curing (UV curing in transparent moulds) or by the stereolithography method, as described, for example, in patent US 4575330, in the production of composite materials (for example, polyesters, styrene, which may include fiber and/or other fibres and other promoters) and other thick-film compositions, coating or sealing of electronic components or as coatings for optical fibres. In addition, these compositions are suitable for the production of optical lenses, e.g. contact lenses or manual lenses, and for medical equipment, assistive devices or implants.

These compositions are also suitable to obtain gels with thermotropic properties. Such gels are described, for example, in documents DE 19700064 and EP 678534.

In addition, the composition can be used in dry film inks, as described, for example, in the publications of Paint & Coatings Industry, April 1997, 72 or Plastics World, Volume 54, No. 7, p.48 (5).

Compounds according to the invention can also be used as initiators for emulsion polymerization, during polymerization in granules or suspension polymerization, or polymerization initiators for fixing the orientation States of liquid-crystalline monomers and oligomers, or as initiators for fixing on organic materials.

In the surface coatings are often used a mixture of prepolymers with inresidence monomers, which, in addition, contain monounsaturated monomer. In this case, prepolymer actually defines the properties of a film covering the surface, and due to its modification expert in this field of technology can vary properties utverzhdenii film. Polyunsaturated monomer plays the role of a cross-linking agent, which provides the insolubility of the film surface of the coating. Monounsaturated monomer plays the role of a reactive diluent, which decreases the viscosity of the mixture, without the use of solvent.

Usually unsaturated polyester resins are used in two-component systems, together with monounsaturated monomer, preferably styrene. For photoconductive often used specific one-component systems, for example, polymaleic, polyalkene or polyimides, which are described in the document DE 2308830.

In addition, the compounds according to the invention and their mixtures can be used as free radical photoinitiators or photoinitiator systems for radiation-curable powder coatings. Powder coating can be based on solid resins and monomers containing reactive double bonds, such as maleate, simple vinyl ethers, acrylates, acrylamide and mixtures thereof. The composition of the powder is covered with the I, svobodnoradikal UV curable by radiation, can be obtained by mixing unsaturated polyester resins with solid acrylamide (for example, methyl ether methylacrylamide acid) and free-radical photoinitiators according to the invention, as described, for example, in the report "Radiation curing of powder coating", see proceedings of the Conference Proceedings, Radtech Europe 1993, as amended .Wittig and Th.Gohmann. Similarly, the composition svobodnoradikal curing UV powder coating can be formulated by mixing unsaturated polyester resins with solid acrylates, methacrylates or simple vinyl esters and photoinitiator (or a mixture of photoinitiators) according to the invention. In addition, the powder coating may contain a binder such that, for example, described in documents DE 4228514 and EP 636669. Powder coatings, UV-curable, can also contain white or colored pigments. For example, specifically rutile/titanium dioxide can be used in a concentration of approximately 50 wt.%, in order to get utverjdenie powder coating, has good hiding power. Usually this method is electrostatic or tribostatic spray powder on the substrate, for example, metal or wood, melting of the powder when heated and, after forming smooth the th film, radiation curing the coating to UV radiation and/or visible light, for example, using mercury lamps, medium pressure, metallogenetic lamps or xenon lamps. A particular advantage of the radiation-curable powder coatings compared with the corresponding thermally-curable coatings is that, if desired, can extend the expiry time of the molten powder particles in order to obtain smooth coatings with high gloss. Unlike thermally curable systems, the composition of the radiation-curable powder coatings can have such a composition that they melt at a relatively low temperature without undesirable effect on the service life of materials. For this reason, these compositions are also suitable as coating for thermally sensitive substrates such as wood or plastic.

Composition of powder coatings, except photoinitiators according to the invention, can also contain UV absorbers. Relevant examples are listed above in items 1) to 8).

Fototerapia compositions of the invention are used, for example, as coating materials for substrates of any type, for example, wood, textiles, paper, ceramics, glass, plastics such as polyesters, polyethylene terephthalate, the polyol is ins or cellulose acetate, especially in the form of films, and also metals such as Al, Cu, Ni, Fe, Zn, Mr or Co and GaAs, Si or SiO2that can be applied to a protective layer or an image, for example, by exposing the image.

The substrates can be coated by applying a liquid composition, solution or suspension to the substrate. The choice of solvent and concentration is determined mainly by the nature of the composition and method of coating. The solvent should be inert, i.e. it should not enter into any chemical reaction with the components, and it should be easily removed again by drying after completion of the coating. Suitable solvents include, for example, ketones, ethers, and esters, such as methyl ethyl ketone, isobutylmethylxanthine, Cyclopentanone, cyclohexanone, N-organic, dioxane, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 1,2-dimethoxyethane, ethyl acetate, n-butyl acetate and ethyl ester of 3-ethoxypropionate acid.

The composition is evenly applied to the substrate using known methods, for example, coating by centrifuging, makanya, drawing knife, the coating applied by spray, brush application, spraying, especially by electrostatic spraying, and coating the reversing roller, and electrophoretic deposition. In addition, for the application of a photosensitive layer on the temporary flexible medium with subsequent coating target substrate, for example, on plakirovannyy copper circuit Board by moving a layer by lamination.

Applied amount (layer thickness) and the nature of the substrate (layer media) depend on the desired application. The specialist in this field of technology known layer thickness, suitable for the considered application areas, for example in the area of photoconductive, printing inks or pigments. Usually the interval thicknesses of the layers includes values approximately from 0.1 μm to more than 10 mm, depending on the application.

In addition, the radiation sensitive composition according to the invention are used, for example, as negative resistors, which have a very high value of photosensitivity and can be developed in aqueous-alkaline medium without swelling. These compositions find use as an electronic photoconductive such as galvanometry, resistors etching as a liquid and dry films, as solder in resistors as the resistors in the production of color filters for flat screens of any type or in the formation of structures in the production of plasma displays and electroluminescent displays, in the production of printing plates, such as offset printing plates, in the manufacture of blocks for printing, flat printing, metal is raffia, flexographic printing or blocks of screen printing in the production of relief copies, for example in the production of texts in Braille, in the manufacture of dyes for use in the etching of the molded products or for use as microresistors in the manufacture of integrated circuits. These compositions can also be used as photostructurable dielectrics, sealing materials or as insulating coatings in the manufacture of computer chips, circuit boards and other electrical or electronic components. Possible carriers with a layered structure, each with different treatment conditions covered substrates.

In addition, the compounds according to the invention are used in the manufacture of single or multi-layer materials for recording or copying images (reproduction, reprography), which can be monochrome or colored. In addition, such materials can also be used in systems determine the color. In this technology it is possible to use compositions comprising microcapsules, and to create the image after the stage of exposure may be followed by stage heat treatment. Such systems and technologies and their use are described, for example, in patent US 5376459.

For written and photographic information are used, for example, foils of polyester, cellulose acetate or paper covered with plastics; blocks for offset printing, for example, specially treated aluminum in the manufacture of printed circuits, for example clad copper laminates, and in the manufacture of integrated circuits on silicon wafers. Usually the thickness of the layer of photographic materials and units of offset printing is approximately from 0.5 μm to 10 μm, and for printed circuits from 1.0 μm to 100 μm.

After coating the substrate, the solvent is generally removed by drying with formation of a coating of the photoresistor on the media.

The term "display image" includes exposure using photomasks having a given configuration, for example, transparency, exposure using a laser beam, which moves on the surface of the coated substrate, for example, controlled by computers, and thus obtained image, and irradiation by an electron beam controlled by a computer. In addition, you can use the LCD mask with elementwise regulation, in order to obtain a digital image, as described, for example, articles A.Bertsch, J.Y.Jezequel, J.C.Andre, Journal of Photochemistry and Photobiology A: Chemistry 1997, 107, s-281 and K.-P.Nicolay, Offset Printing 1997, 6, p.34-37.

Conjugated polymers, such as polyaniline, can be transferred from poluprovodn the same state of the conductor by doping with protons. In addition, photoinitiator according to the invention can be used for display on the image polymerizable compositions containing such polymers, in order to form the conductive structures (in the irradiated areas)that are embedded in insulating material (non-irradiated region). Such materials can be used, for example, as components, wiring or connecting components in the manufacture of electrical or electronic products.

After exposure the image material before showing it may be appropriate to conduct a heat treatment for a relatively short time. During thermal processing of thermally otverzhdajutsja only the exposed region. Commonly used temperatures from 50 to 150°C, preferably from 80 to 130°; and the duration of heat treatment is usually from 0.25 to 10 minutes.

In addition, fototerapia compositions can be used in a method of producing printing blocks or photoconductive, as described, for example, in document DE 4013358. In this way, before, after or during the exposure radiation image composition briefly exposed to visible light with a wavelength of at least 400 nm without a mask. After exposure and optional heat treatment, quenching the TCI unexposed areas of the photosensitive coating is removed, basically, in a known manner, using a developer.

As already mentioned, the compositions according to the invention can be developed in aqueous-alkaline medium. Suitable aqueous-alkaline developing solutions specifically are aqueous solutions of tetraalkylammonium hydroxides, or silicates, phosphates, hydroxides or carbonates of alkali metals. Optionally, these solutions can also be added relatively small amounts of wetting agents and/or organic solvents. Typical organic solvents which can be added in a small amount in manifesting liquids are, for example, cyclohexanone, 2-ethoxyethanol, toluene, acetone and mixtures of such solvents.

Vodootvedenie is of great importance for printing inks, since the drying time of the binder is a factor determining the performance when retrieving graphical products, and this time should be about fractions of a second. Inks, UV curable by radiation, particularly important for screen printing, flexographic printing and offset printing.

As mentioned above, the mixtures according to the invention are also particularly suitable in the production of printing forms. In this area are used, for example, mixtures of soluble linear polyamides, Il is a styrene/butadiene or styrene/isoprene elastomer, polyacrylate or polymetylmetacrylate having carboxyl groups, polyvinyl alcohols or urethaneacrylate with photopolymerization monomers, for example inorganic salts of acrylic or methacrylic acid, or esters of acrylic or methacrylic acids, and photoinitiators. Films and plates made from these systems (wet or dried), exhibited by a negative (or positive) of the original and then the uncured areas are washed away with a suitable solvent.

Another area of application potootvedeniya materials are metallic coating, for example, when applying the finish on the sheets and tubes, cans or bottle caps, and vodootvedenie plastic coatings, for example, a finishing layer of floor coverings or walls based on PVC. Examples of fototerapia paper coatings include applying a clear finish on labels, envelopes for records or on the book cover.

Also of interest is the use of compounds of the invention when cured castings made of composite materials. The composite material consists of independent matrix material, such as woven fiberglass, or alternatively, for example, vegetable fibers [see the publication K.-Rmes, .Reussmann in the journal Kunststoffe 85 (1995), 366-370], which is impregnated fotoallergiyami composition. Ebb and, made of composite materials, which are obtained using the compounds according to the invention possess a very high mechanical stability and strength. In addition, the compounds according to the invention can be used as potootvedeniya agents in the casting materials, impregnation and coating, as described, for example, in document EP 7086. Such materials are, for example, a thin layer of resin, which has high demand in terms of activity during curing and resistance to yellowing, and reinforced fibre moulding materials, such as flat or longitudinally or perpendicularly corrugated light panels. Methods for such molding materials, such as molding products manually from the laminates, the dispersion of fibers, spinning, or winding, as described, for example, in the book ..Selden "Glasfaserverstärkte Kunststoffe", str, Springer Verlag Berlin-Heidelberg-New York 1967. Products that can be obtained, for example, in this way, represent boats, boards of pressed sawdust or panels of plywood, coated on both sides with plastic, reinforced with fiberglass, pipes, sporting equipment, roofing, containers and others for More examples of casting, impregnating and coating materials are thin layers of UP resins for lit is of evich materials, containing fiberglass (GRP), for example, corrugated panels and paper laminates. Paper laminates can be the basis of macewindow or melamine resin. A thin layer is obtained on the media (such as film) to obtain a laminate. In addition, fototerapia compositions according to the invention can be used for injection molding of resin or sealing products, such as electronic components, etc. in Addition, they can also be used for lining cavities and tubes. For curing used mercury lamps, medium pressure, traditionally used in UV curing, but also are of significant interest lamps less intensity, for example, type TL 40W/03 or TL 40W/05. The intensity of these lamps is approximately equivalent to the intensity of daylight. Curing may also be used in daylight. An additional advantage is that the composite material may be removed from the source of light emission in a partially cured, plastic condition and subjected to molding, and after this is the complete curing of the material.

In addition, photoinitiator according to the present invention can be used in such compositions as coatings for optical fibres. Typically, optical fibers are coated with a protective the layers immediately after receiving them. Glass fibers are extruded and then on the filament glass fibre is applied one or more coatings. Usually applied one, two or three coatings, for instance, the top floor is painted (the paint layer or coating of paint"). In addition, several optical fibers covered so can be taken in the form of a bundle and covered all together, i.e. a cable of fibers. Compositions according to the present invention in General are suitable for any of these coatings have good elasticity in a wide temperature range, tensile strength and toughness, and quickly cured by UV irradiation.

Each of the coatings mainly primary internal (usually soft cover), the primary external or secondary (usually a harder coating than the inner coating), tertiary or cable coating may include at least one radiation curable oligomer, at least one radiation-curable monomer diluent, at least one photoinitiator and additives.

Usually, all of the radiation-curable oligomers are suitable. Preferred are oligomers with a molecular weight of at least 500, for example 500-10000, 700-10000, 1000-8000 or of 1,000-7,000, especially urethane oligomers, operasie, at least one unsaturated group. Preferably radiation curable oligomer has two terminal functional groups. The coating may contain not only one specific oligomer, but also mixtures of different oligomers. Methods of obtaining suitable oligomers known to specialists in this field of technology and published, for example, in patent US 6136880 included in this invention as a reference. For example, the oligomers produced by the interaction of oligomeric diol, preferably a diol having 2 to 10 polyoxyalkylene groups with a diisocyanate or polyisocyanate and the ethylene unsaturated monomer with a hydroxyl functional group, for example, hydroxyalkyl(meth)acrylate. Specific examples of each of these components, as well as the appropriate ratio of these components is given in the patent US 6136880 included in this invention as a reference.

Radiation curable monomer may be used in such a way as to adjust the viscosity of the covering composition. Accordingly, the applied monomer with low viscosity, having at least one functional group capable of polymerization under the action of photoinitiator. The number of monomer chosen, for example, to control viscosity in the range from 1000 to 10000 MPa, which is usually used, for example from 10 is about 90, or 10-80 wt.% the monomer. Preferably, the functional group of the monomer diluent is the same as the functional groups of the oligomeric component, for example, acrylate or group of simple vinyl ether and fragments of higher alkyl or polyester (simple). Examples of Monomeric diluents suitable for coating compositions for optical fibers, published in the patent US 6136880 (column 12, line 11ff.), included in this invention as a reference.

In the primary coating preferably used monomers having functional groups of the acrylate or simple vinyl ether and a fragment of a polyester (simple)containing from 4 to 20 carbon atoms. Specific examples are given in the above cited U.S. patent, included in this invention as a reference.

In addition, the composition may contain a poly(siloxane), as described in patent US 5595820, in order to improve the adhesive properties of the composition on a glass substrate of the optical fibers.

In addition, the coating composition typically contains additional additives, for example antioxidants, light stabilizers, UV absorbers, such as those mentioned above in the list, in particularRTMIRGANOX 1035, 1010, 1076, 1222,RTMTINUVIN P, 234, 320, 326, 327, 328, 329, 213, 292, 144, 622LD (all are delivered by the company Ciba Specialty Chemicals),RTMANTIGENE P, 3C, FR, GA-80,RTMSUMISORB TM-061 (put the camping company Sumitomo Chemical Industries Co.), RTMSEESORB 102, 103, 501, 202, 712, 704 (are delivered by the company Sypro Chemical Co., Ltd.),RTMSANOL LS770 (supplied by company Sankyo Co. Ltd.), to prevent staining of the coating, in particular in the process, and to improve the stability of the cured coating. Especially interesting are the combinations of stabilizers - spatial obstructed the piperidine derivatives (HALS) and obstructed phenolic compounds, for example, the combination of IRGANOX 1035 and TINUVIN 292, for example, in a 1:1 ratio. Additional additives are, for example, wetting agents and other additives that affect the rheological properties of the coating. In addition, can be added amines, such as diethylamine.

Other examples of additives in the composition for coating optical fibers are combining silane agents, for example, γ-aminopropyltriethoxysilane, γ-mercaptopropionylglycine, γ-methacryloxypropyltrimethoxysilane, SH6062, SH6030 (supplied by the company Toray-Dow Corning Silcone Co., Ltd.), KBE 903, KBE 603, KBE 403 (supplied by the company Shin-Etsu Chemical Co., Ltd.). In addition, to prevent staining of the coating composition may include a fluorescent additive or optical Brightener, such asRTMUVITEX OB, (supplied by the company Ciba Specialty Chemicals).

Photoinitiator according to the present invention in the compositions covering the op is practical fiber, can be mixed with one or more other known photoinitiators, in particular mono - or bestinformation, as for example, diphenyl-2,4,6-trimethylbenzaldehyde, bis(2,4,6-trimethylbenzoyl)phenylphosphine (®IRGACURE 819), bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentanediol; α-hydroxyketone, as for example, 1-hydroxycyclohexane (®IRGACURE 184), 2-hydroxy-2-methyl-1-phenyl-1-propanone (®DAROCUR 1173), 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone (®IRGACURE 2959); α-aminoketone, as for example, 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone (®IRGACURE 907), 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone (®IRGACURE 369), 2-(4-methylbenzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-benzyl-2-(dimethylamino)-1-[3,4-acid]-1-butanone; a benzophenone such as benzophenone, 2,4,6-trimethylbenzene, 4-methylbenzophenone, 2-methylbenzophenone, 2-methoxycarbonylamino, 4,4'-bis(chloromethyl)benzophenone, 4-chlorobenzophenone, 4-phenylbenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, methyl ester 2-benzoylbenzene acid, 3,3'-dimethyl-4-methoxybenzophenone, 4-(4-methylphenylthio)benzophenone, 2,4,6-trimethyl-4'-phenylbenzophenone, 3-methyl-4'-phenylbenzophenone and Catalunya connection, for example, 2,2-dimethoxy-1,2-d is phenylethanol ( ®IRGACURE 651); Monomeric or dimeric esters phenylglyoxylic acid, such as ether methylphenylglycidate acid, 5,5'-oxadi(ethylenebisdithiocarbamate) or 1,2-(benzoylperoxy)ethane. Especially suitable are mixtures with mono - or bis-acylphosphatase and/or α-hydroxyketone.

Obviously, to improve the properties of photoinitiator composition can also contain a sensitizing compound, for example, amines.

The coating is applied under schemes or "wet on dry"or "wet on wet". In the first case, after applying the primary coating spend stage curing by UV irradiation, prior to application of the second coating layer. In the second case put both coverage and utverjdayut them together by UV-irradiation.

Curing by UV irradiation in this invention is usually carried out in a nitrogen atmosphere. In General, all sources of radiation that are used in the methods of fototerapia, can be used for curing coatings of optical fibers. For example, can be used radiation sources listed below. Generally used mercury lamps, medium-pressure or/and lamp Fusion D. in Addition, are suitable flash lamp. It is obvious that the emission of the lamps is consistent with the absorption of the used photoinitiator or mixture of photoinitiators. In addition,the composition of the coating of optical fibers can be solidified by irradiating the electron beam, in particular beams of low-energy electrons, as for example described in the application WO 98/41484. To distinguish between the various fibers in the layout of the fibre can be covered by third-stained floor ("floor paint"). The composition used for the coating, in addition to the polymerizable components and photoinitiator contain a pigment or dye. Examples of pigments suitable for coating optical fibers are inorganic pigments such as titanium dioxide, zinc oxide, zinc sulfide, barium sulfate, aluminum silicate, calcium silicate, carbon black, black iron oxide, black copper chromite, iron oxide green chromium oxide, Prussian blue, chrome green, purple pigment (for example, manganese violet, cobalt phosphate, CoLiPO4), the chromates of lead, molybdate of lead, cadmium titanate and pearlescent and metallic pigments, and organic pigments such as monoatomically, disability, diazolidinylurea pigments, chinaredorbit pigments, dioxazine violet, VAT pigments, Pereladova pigments, thioindigo pigments, phthalocyanine pigments and tetrachlorobenzoquinone. Examples of suitable pigments are carbon black coating, titanium dioxide for white coating, dialled yellow or pigments on osnovetehnologii for yellow coating, phthalocyanine blue and other phthalocyanine blue coatings, anthraquinone red, naphthol red, pigment-based monotonicity, chinaredorbit pigments, anthraquinones and perylenes for red coatings, phthalocyanine green and pigments based on nitrosoguanidine for green coatings, pigments mono - and deseasonalizing, chinaredorbit pigments, anthraquinones and perylenes for orange coatings, and chinagreen violet, basic dyes-pigments and pigments based on carbetocin for purple coating. Specialists in this field of technology are well aware of the formulation and combination of suitable additional pigments, if necessary in more than painted surfaces, such as sea-green, brown, grey, pink, etc. the Average particle size of the pigments is usually from about 1 μm or less. If necessary, the particle size of industrial pigments can be reduced by grinding. For example, pigments may be added to the composition in the form of a dispersion, in order to facilitate mixing with the other components of the composition. For example, the pigments are dispersed in a liquid with low viscosity, for example, a reactive diluent. Preferably used organic pigments. Appropriate amount of colored pigment in the second floor is for example, 1-20%, 1-15%, preferably 1-10 wt.%.

Typically, the coating of paint also includes a lubricating material to ensure superior properties breakthrough optical fibers with a single coating of the matrix. Examples of such lubricants are silicone, fluorocarbon oils or resins and the like, are preferably used silicone oil or functionalityand silicone compound, for example, silicondioxide.

In addition, compositions according to the present invention are suitable as matrix material for composition coated optical fibers. That is, in a matrix composed of several primary, secondary (and in some cases, tertiary) covered with fibers, for example, in the third floor they differ in color.

Preferably, the coating unit, in addition to the above additives, also contains a release agent to ensure easy access to individual fibers during installation of the cable optical fibers.

Examples of antiadhesive are Teflon, silicones, siliconalley, fluorocarbon oils or resins and the like. It is advisable, antiadhesive add in the amount of 0.5-20 wt.%. Examples of the colored coatings and matrix materials for coated optical fibers are given in the documents US 6197422, 6130980 and EP 614099, which are included in this invention ka is the link.

Compositions and compounds according to the invention can also be used in the manufacture of optical waveguides and optical keys, using the formation of the difference of refractive index between the exposed and unexposed areas.

Also important is the use of fototerapia compositions in the processes of reproduction and to obtain the optical information media. As already described above, in this application, supported on a carrier layer (wet or dry) is irradiated using photomasks UV radiation or visible light, and unexposed areas of the layer are removed by treatment with a solvent (i.e. a developer). In addition, phototherapy layer can be deposited on the metal deposition process. The exposed areas are crosslinked polymers, and therefore, they are insoluble and remain on the media. When the respective color layers are formed visible image. When the bearer is a metallized layer, after exposure and manifestation, there is the possibility of vitravene metal in the unexposed areas or hardening by means of electroplating. Thus, it is possible to obtain a printed electronic circuit and the photoconductive.

Usually the area of the photosensitivity of the compositions according to the invention forgive the correspondingly from about 200 nm to 600 nm (UV region). Suitable radiation include, for example, in sunlight or light from artificial light sources. Therefore, there may be used a large number of different types of light sources. Are suitable as point sources, and pastoobrazna emitters (group of lamps). Examples are: arc lamp with carbon electrodes, xenon arc lamps, mercury arc emitters medium pressure, high pressure and low pressure, doped, if appropriate, halides of metals (metallogenesis lamp), lamp microwave excitation with pairs of metals, the excimer lamp radiation, fluorescent tube with transuranium elements, fluorescent lamps, argon incandescent lamps, electronic flash lamps, photographic flood light bulb, light-emitting diodes (LED), electron beams and x-rays. The distance between the lamp and the substrate according to the invention, which will be on display may vary in accordance with the intended use and the type and power of lamp, and may be, for example, from 2 cm to 150, see Especially suitable are laser light sources, for example excimer lasers, such as lasers Krypton-F, for example, for exposure at 248 nm. In addition, can be used lasers in the visible range. Using the e is on the way you can get printed circuits in the electronics industry, lithographic offset printing plates or forms of letterpress printing, and photographic materials for recording images.

Therefore, the invention also relates to a method for the photopolymerization of nonvolatile Monomeric, oligomeric or polymeric compounds containing at least one ethylene unsaturated double bond, and this method is that irradiate the above-described composition of light with a wavelength from 200 to 600 nm. In addition, the invention relates to the use of compounds of the formula I as photoinitiators if photopolymerizable non-volatile Monomeric, oligomeric or polymeric compounds containing at least one ethylene unsaturated double bond by irradiation of light with a wavelength from 200 to 600 nm.

In addition, the invention relates to the use of the above compositions and to a method for producing pigmented and non-pigmented surface coatings, printing inks, such as inks screen printing inks offset printing inks flexographic printing, powder coatings, printing plates, adhesives, dental compositions, optical waveguides, optical keys, color detection, composite materials, coatings, fiber glass cables, forms the stencil is th printing, resistor materials, color filters, for use in sealing electrical and electronic components, in obtaining materials for magnetic recording, upon receipt of three-dimensional objects by stereolithography, photographic reproductions, and for use as materials for recording images, especially for holographic recordings, decolorizing materials, decolorizing materials for image capture, for materials for recording images using microcapsules.

The invention also relates to a coated substrate, the surface of which is covered at least on one side of the above described composition, and to a method of photographic obtain relief images, in which the coated substrate is exposed on the image and then the unexposed areas of the layer are removed using a solvent. The display image can be carried out using a mask or using a laser beam. Exposure using laser beam is of particular interest.

Compounds according to the invention not only possess the actual photoinitiation action, but they are also able (due to the presence in them of the special Deputy) to infiltrate and gain a foothold in the compositions that will dry out, then eat what they are able to interact with any desired components of these compositions, regardless of whether these components in future to take part in the reaction of the photopolymerization, and as a result, they are strongly linked with the resulting polymer structure.

Compounds according to the invention of the formula I, in which R1HE is a than those of the above-described properties have additional important property is that they represent a key intermediate compounds for preparing compounds of the formula I, which are optionally functionalized.

The following additional examples illustrate the invention. And throughout the description and in the claims, parts and percentages are given in terms of weight unless otherwise stated. References alkyl or alkoxy radicals containing more than three carbon atoms without specifying their isomeric forms, in each case, should be understood as referring to the corresponding normal isomer.

Example 1. Getting connection

As the initial load placed 137,9 g methyl ester phenylglyoxylic acid, 891,7 g of diethylene glycol and 2.2 g of dihydrate of lithium acetate, at room temperature, 1.5-liter mnogogolovy flask, equipped with a device for distillation. Under stirring the reaction flask slowly pumped to a pressure of 8-10 mbar. Then d is clonney the mixture is heated to a temperature of from 50 to 60° C. After approximately 72 hours, all the formed methanol is removed by distillation, and the reaction is finished. The reaction mixture is poured together with 500 ml of water in a separating funnel and extracted three times (100 ml) with toluene and then five times (500 ml) diethyl ether. The ether phases are combined, dried over sodium sulfate and filtered. The product obtained after distillation of the solvent using a rotary evaporator). The structure and composition of the product are confirmed by the data of NMR spectroscopy and Ehud (liquid chromatography high pressure).

Example 2. Obtaining the ethyl ester of 2-[2-(5-isocyanato-1,3 .3m-trimethylcyclohexylisocyanate)ethoxy]phenylglyoxylic acid

In an argon atmosphere was placed as a bootstrap to 4.28 g of ethyl ester of (2-hydroxyethoxy)phenylglyoxylic acid from example 1 and of 3.99 g of 5-isocyanato-1-isocyanatomethyl-1,1,3-trimethylcyclohexane (isophorondiisocyanate, from the company Fluka) in 15 g of toluene in mnogogolovy flask 50 ml) and refluxed at 110°C. After 18 hours the solution is cooled and the toluene is evaporated using a rotary evaporator. The residue is dried in high vacuum for two hours. Gain of 8.2 g of a viscous, yellowish oil. Chemical conversion and product composition are confirmed by spectral:1H-NMR and the (band NCO).

Elementary analysis: C24H32N2O7% [Calculated/found] 62,59/63,55; %H [calculated/found] 7,00/7,07; %N [calculated/found] between 6.08/6,07.

Example 3: obtaining the ethyl ester of 2-{2-[4-(4-isocyanatobenzyl)-phenylcarbamoyloxy]-ethoxy}phenylglyoxylic acid

In an argon atmosphere was placed as a bootstrap 2.14 g of ethyl ester of (2-hydroxyethoxy)phenylglyoxylic acid from example 1 and 2.24 g of 4,4'-diphenylmethanediisocyanate (Desmodur VL, Bayer) in 15 g of toluene in mnogogolovy flask 50 ml) and refluxed at 110°C. After 19 hours the solution is cooled and the toluene is evaporated using a rotary evaporator. The residue is dried in high vacuum for two hours. Obtain 4.6 g of a viscous, slightly brownish oil. Chemical transformation and composition of the mixture obtained are confirmed by spectral:1H-NMR and IR (band NCO).

Elementary analysis: C27H24N2O7% [Calculated/found] 66,39/67,54; %H [calculated/found] 4,95/5,19; %N [calculated/found] 5,73/5,52.

Example 4. Obtaining the ethyl ester of 2-(2-{6-[3-(6-isocyanatophenyl)-2,4,6-trioxo-5-(6-{2-[2-(2-oxo-2-phenylacetate)ethoxy]ethoxycarbonyl}hexyl)-[1,3,5]triazine-1-yl]hexylberberine}ethoxy)phenylglyoxylic acid

and ethyl ester of 2-(2{6-[3,5-bis(6-isocyanatophenyl)-2,4,6-trioxo-1,3,5]triazine-1-yl]hexylberberine}ethoxy)phenylglyoxylic acid

In an argon atmosphere was placed as a bootstrap 2.14 g of ethyl ester of (2-hydroxyethoxy)phenylglyoxylic acid from example 1 and to 3.02 g of 1,3,5-Tris(6-isocyanatophenyl)-[1,3,5]triazine-2,4,6-trione (Desmodur N3300, Bayer) in 15 g of toluene in mnogogolovy flask 50 ml) and refluxed at 110°C. After 16 hours the solution is cooled and the toluene is evaporated using a rotary evaporator. The residue is dried in high vacuum for 3 hours. Gain of 5.3 g of a viscous, colorless oil. Chemical transformation and composition of the mixture obtained are confirmed by spectral:1H-NMR and IR (band NCO). As photoinitiator, in equal shares present monoproduct and biproduct.

Elementary analysis: C48H64N6O16and C36H50N6About11

% [Calculated/found] 58,53/58,42%; N [calculated/found] 6,67/of 6.71;

%N [calculated/found] 9,75/9,18.

Example 5. Obtain 1,3-bis(6-{2-[2-(2-oxo-2-phenylacetate)ethoxy]-ethoxycarbonyl}hexyl)-5-(6-isocyanatophenyl)biureta

and 1-(6-{2-[2-(2-oxo-2-phenylacetate)ethoxy]ethoxycarbonyl}hexyl)for 3,5-bis(6-isocyanatophenyl)biureta

In an argon atmosphere was placed as a bootstrap 2.14 g of ethyl ester of (2-hydroxyethoxy)Fanelli kilowog acid from example 1 and 2.86 g of 1,3,5-Tris(6-isocyanatophenyl)biureta (Desmodur N3200, Bayer) in 15 g of toluene in mnogogolovy flask 50 YPD and refluxed at 110°C. After 19 hours the solution is cooled and the toluene is evaporated using a rotary evaporator. The residue is dried in high vacuum. Obtain 4.8 g of a viscous, colorless oil. Chemical transformation and composition of the mixture obtained are confirmed by spectral:1H-NMR and IR (band NCO). As photoinitiator, in equal shares present monoproduct and biproduct.

Elementary analysis: C47H66N6O15and C35H52N6O10

% [Calculated/found] 58,91/59,22%; N [calculated/found] 7,11/7,14;

%N [calculated/found] of 10.05/9,67.

Example 6. Obtaining the ethyl ester of 2-(2-{6-[3-(6-isocyanatophenyl)-2,4-dioxo-[1,3]azetidin-1-yl]hexylberberine}ethoxy)phenylglyoxylic acid

In an argon atmosphere was placed as a bootstrap 2.14 g of ethyl ester of (2-hydroxyethoxy)phenylglyoxylic acid from example 1 and to 3.02 g of 1,3-bis(6-isocyanatophenyl)-[1-3]azetidin-2,4-dione (Desmodur N3400, Bayer) in 15 g of toluene in mnogogolovy flask 50 ml) and refluxed at 110°C. After 19 hours the solution is cooled and the toluene is evaporated using a rotary evaporator. The residue is dried in high vacuum. Get 5,2 g highly viscous, colorless oil. Chemical is reversine and composition of the mixture obtained are confirmed by spectral: 1H-NMR and IR (band NCO).

Elementary analysis: C28H38N4About9

% [Calculated/found] 58,53/58,57; %

N [calculated/found] 6,67/6,95; %N [calculated/found] 9,75/9,63.

Example 7. Receive (2 oxiranylmethyl-ethoxy)phenylglyoxylic acid

7.1. Getting monoglycidyl ether of diethylene glycol

In an atmosphere of nitrogen was placed as a bootstrap 26,53 g of diethylene glycol, 0.25 g of uranyl perchlorate lanthanum and 50 ml of toluene in a sulphonation flask with a volume of 350 ml, equipped intensive reflux condenser and a propeller stirrer, and the mixture is heated to 105°C. After reaching the temperature of the mixture 105°C, keeping the temperature constant is added dropwise with 21.3 g of epichlorohydrin for 70 minutes. Followed by stirring the mixture for 14 hours at 105°and the reaction mixture was added 30 ml of toluene, to remove during subsequent azeotropic distillation residues of water present. When normal pressure is distilled off approximately 30 ml of azeotrope. After cooling to a temperature of from 48 to 50°With added dropwise approximately 19 g of databaseconnect within 30 minutes and the mixture is successively stirred for 2 hours. After cooling to room temperature the lower layer of the TLD is the phase of the reaction mixture is acidified to pH 5-8, using acetic acid, diluted with methylene chloride and extracted 3 times with saline solution (approximately 100 ml each time). After drying with magnesium sulfate thus obtained crude product is evaporated to dryness and receive 27,1 g (yield 73% of theory) of a slightly yellowish, viscous oil. The crude product (12 g) purified by the method of flash chromatography (800 g silica gel 60 F; a mixture of ethyl acetate/methanol = 95:5). The target product is obtained in the form of a slightly yellowish oil, with a purity of about 85% (determined by gas chromatography, GC). According to spectrum1H-NMR by-product (15%, determined by GC method) is the following connection:

Range1H-NMR monoglycidyl ether of diethylene glycol (CDCl3relative to trimethylsilane [TMS] as standard)

, ppm:

2,61-2,63 and 2,79-2,83 (2 m); 3,16-3,18 (m, Hb); 3,38-3,44 and 3,81-3,86 (2 DHD, Hc); 3,60 of 3.75 (m, Hd, He, Hf, Hg).

Range13C-NMR monoglycidyl ether of diethylene glycol (CDCl3relative to TMS as standard), ppm: 44,2; 50,8; 61,6; 70,4; 70,7; 72,0; 72,6.

7.2: Receive (2 oxiranylmethyl)phenylglyoxylic acid

Put as bootstrap 217 mg methyl ester phenylglyoxylic acid, 195 mg monoglycidyl ether of diethylene glycol, obtained in Example 7.1, and 0 mg of lithium acetate in pear-shaped flask. This flask is connected to a rotary evaporator with a bath temperature of 60°and reduce the pressure of 150 mbar. After two hours, the bath temperature was raised to 70°and reduce the pressure to 100 mbar. After another two hours the reaction solution is purified chromatographically on silica gel 60F using eluent - hexane/ethyl acetate 1:1. Specified in the title compound obtained as a slightly yellowish oil.

Range1H-NMR (2 oxiranylmethyl-ethoxy)phenylglyoxylic acid (CDCl3relative to TMS as standard),

ppm: 2,58-2,60 and was 2.76-2,79 (2 m); 3,14-and 3.16 (m, Hb); 3,38-3,44 and 3,78-3,79 (2 DHD, Hc); 3,69-3,71 and 3,82-3,86 (2 m, Hd, Hf); 4,55-4,58 (m, Hg); 7,49-of 7.55 and to 7.64-7,69 and 8,02-8,05 (5 aromatic H).

Range13C-NMR monoglycidyl ether of diethylene glycol (CDCl3relative to TMS as standard), ppm: 44,2, 50,8, 64.9, 68.7, 70,6, 70,7, 72,0, 128,9, 130,1, 132,5, 135,0. 163,8, 186,2.

Example 8

Fotoatelier composition was prepared by mixing the following components:

89,0 parts of epoxyacrylate (80% in hexaniacinate; Ebecryl®604)

10.0 parts of diacrylate of polyethylene glycol 400 (Sartomer®SR 344)

1.0 part of additive improving the fluidity (Ebecryl®350)

In the resulting composition is added 2% of the compound of example 1. This composition is applied to the sheet of aluminum with a knife (6 μm) and irradiated using two mercury is s average pressure lamp (80 W/cm). Get cured layer.

Examples 9-14

For examples 9-14 receive the following composition:

- Component a - 11,38 parts of polyacrylate containing hydroxyl group, 70% in butyl acetate (Desmophen And 870; Bayer AG); 21,23 parts poly(complex)ether polyol, 75% in butyl acetate (Desmophen VP LS 2089; Bayer AG); 0,55 part of the additive that increases 20 turnover (Byk 306; Byk Chemie); 32,03 parts of methanol

Component In (applicable amounts specified in table 1) - urethaneacrylate containing isocyanate groups (Roskydal UA VP LS 2337, Bayer AG).

Initiators to be tested is injected into the component And the concentration listed in table 1, with stirring. Then add component b and evenly distribute it. Thus obtained samples applied on a glass plate with a knife with a gap of 250 μm. The solvent is then evaporated at room temperature. After evaporation of the recorded UV-spectrum of the sample (spectrometer UV/VIS Perkin Elmer Lambda 900). Then the plate is placed for 10 minutes on a hot tile having a temperature of 120°so began the process of thermal crosslinking. Then write again UV spectrum of the sample. Then the samples utverjdayut UV radiation at belt speeds of 5 m/min, using two mercury lamp (120 W/cm medium pressure. The absorption of the samples after evaporation corresponds to 100%. The difference between the two spectra after evaporation and after thermal stivk which corresponds to the loss of photoinitiator due to volatility or due to the lack of implementation. These results are shown in table 1.

Table 1 (number of components are expressed in parts by weight)
Example91011121314
Component a65,1965,1965,1965,1965,1965,19
Component31,0731,0723,823,826,226,2
Initiator from example 11,67
Initiator from example 22,95
Initiator from example 32,95
Initiator from example 62,95
Initiator from example 42,59
The initiator of the example 5 2,59
Volatility in %00002,11,1

For all samples there is no loss (or very small losses) photoinitiator; this indicates that there is an optimal implementation of photoinitiator in the composition to be cured, and that photoinitiator is not removed from the composition during thermal process.

Additional examples 15-16

Receiving broadcast hexa-5-enyl-glyoxalic acid (GSID236-1, GB 2220)

Reaction:

A mixture of 10 g of methyl ether-glyoxalic acid, a 5.25 g of 4-penten-1-ol and 0.3 g dibutylated in 50 ml of toluene is heated for 4 hours to 120°With a small vacuum. The resulting methanol is distilled and the mixture concentrated. Chromatography (eluent: hexane/ethyl ester acetic acid 5:1) determines the ether hexa-5-enyl-glyoxalic acid (11.7 g, o. 88%) as a slightly yellow liquid color.

Range1H-NMR (CDCl3) δ (ppm): 8,00 (m, 2 H arene.), 7,66 (m, 1 H arene.), 7,52 (m, 2 H arene.), of 5.81 (m, 1 H,- N=CH2), of 5.05 (m, 2 H, -CH=CN2), to 4.41 (t, J=6,9, 2 H, CH2-O-C(O)-), 2,19 (m, 2 H, -CH2-), 1,89 (m, 2 H, -CH2-).

P is torching 3-oxiranyl-propyl ether oxo-phenyl-acetic acid (GSID237-1,GB2221)

Reaction:

The mixture 9,13 g ether hexa-5-enyl-glyoxalic acid (obtained above) and 8,66 g m-perchlorobenzene acid in 180 ml of dichloromethane for 8 hours was stirred at ambient temperature. The resulting methanol is distilled. After filtration, the mixture is extracted with saturated aqueous NaHCO3. The organic phase is washed with water and dried with MgSO4. After filtration, removal of the solvent exercise chromatography (eluent: hexane/ethyl ester acetic acid 2:1) determines the 3-oxiranyl-propyl ether oxo-phenyl-acetic acid (8.0 g, o. 69%) as a slightly yellow liquid color.

Range1H-NMR (CDCl3) δ (ppm): 8,04 (m, 2 H arene.), 7,66 (m, 1 H arene.), 7,52 (m, 2 H arene.), 4,43 (m, 2 H, CH2-O-C(O)-), 2,96 (m, 1 H, -CH-O (oxiranyl)), 2,77 (m, 1 H, -CH-O (oxiranyl)), 2,50 (m, 1 H, -CH-O (oxiranyl)), a 1.96 (m, 2 H, -CH2-), of 1.80 (m, 1 H, -CH2-), of 1.59 (m, 1H, -CH2-).

1. Photoinitiated compound of formula (I) implemented in photopolymerized composition

in which Y represents C3-C12alkylen,4-C12alkylene, which is interrupted once or several times by groups-O -, or-NR2-not following each other;

R1is the Wallpaper reactive group, selected from HE, SH, NR3R4, -(CO)-NH2, -C(R5)=CR6R7, oxiranyl and-O-(CO)-NH-R8-NCO;

R2represents hydrogen, C1-C4alkyl or C2-C4hydroxyalkyl;

R3and R4represent, each independently, hydrogen, C1-C4alkyl or C2-C4hydroxyalkyl;

R5, R6and R7represent, each independently, hydrogen or methyl;

R8represents a linear or branched C4-C12alkylene, phenylene, methylphenylene, cyclohexanediyl, inforanger,

or

R9represents a linear or branched C1-C16alkylene, -CH=CH-, -CH=CH-CH2-With6-cycloalkyl, phenylene, naftilan, the norbornene-5,6-diyl,,,,or; and

X1and X2predstavlyaet a, each independently of the others, HE, Cl, co3or OS2H5.

2. Photoinitiated compound of formula I according to claim 1, implemented in photopolymerized composition, in which

Y represents a C4-C12alkylen, interrupted once or several times by groups-O-, not following each other;

R1represents a reactive group selected from HE, oxiranyl and-O-(CO)-NH-R8-NCO; and

R8representsor

3. The method of obtaining the compounds of formula I in which R1is a HE, which is that monoether phenylglyoxylic acid II

in which R represents a C1-C4alkyl, especially methyl or ethyl,

interacts with diola III

where Y is as defined in claim 1,

where as the catalyst using the lithium acetate, sodium acetate, potassium acetate, magnesium acetate, barium acetate, zinc acetate, cadmium acetate, copper acetate(II), cobalt acetate(II), aluminum acetate, calcium oxide, the lithium methylate, the sodium methylate, tetraisopropyl titanium, triisopropyl aluminum, tert-butyl lithium, 4-(dimethylamino)pyridine or the diacetate dibutylamine.

4. The compound of the formula I, in which R1is a HE, as the source material upon receipt of the implemented photoinitiator, in which R1represents SH, NR3R4, -(CO)-OH, -(CO)-NH2, SO3H, -C(R5)=CR6R7oxiranyl, -O-(CO)-NH-R8-NCO or-O-(CO)-R9-(CO)-X and the radicals R3, R4, R5, R6, R7, R8, R9and X are such as defined in claim 1,

5. The method of obtaining the implemented photoinitiator formula I according to claim 1 in which the compound of formula I according to claim 1, in which R1HE is a interacts with the isocyanate, carbamoylation, thioisocyanate, the acid chloride of the acid, ester, acid, acid anhydride, chloroformate or epichlorohydrin.

6. Photopolymerizable composition, which includes:

(a) at least one ethylene unsaturated photopolymerization connection

(b) at least one compound of formula I according to claim 1 as photoinitiator.

7. The composition according to claim 6, containing, in addition to component (b), additional initiators (C) and/or additives (g).

8. The composition according to claim 7, in which more photo initiators (C) are connected to the I formula VIII, IX, X, XI and/or XII

in which R25represents hydrogen, C1-C18alkyl, C1-C18alkoxy, -och2CH2- OR29; morpholino, SCH3or the groupor

n denotes a number from 2 to 10;

of G1and G2each independently of the other, represent end groups of the polymer chain, especially hydrogen or CH3;

R26represents hydroxy, C1-C16alkoxy, morpholino, dimethylamino or-O(CH2CH2O)m-C1-C16alkyl;

R27and R28each independently represent hydrogen, C1-C6alkyl, phenyl, benzyl, allyl,1-C16alkoxy or-O(CH2CH2O)m-C1-C16alkyl, or R27and R28together with the carbon atom to which they are bound form a cyclohexane ring;

m denotes a number from 1 to 20;

in which all R26, R27and R28at the same time do not represent a1-C16alkoxy or-O(CH2CH2O)m-C1 -C16alkyl, and

R29represents hydrogen,or;

R30and R32each independently mean hydrogen or methyl;

R31represents hydrogen, methyl, 2-hydroxyethylthio or phenylthio, and the phenyl ring of phenylthiazole is unsubstituted or substituted With1-C4the alkyl in the 4-, 2-, 2,4 - or 2,4,6-positions;

R33and R34each independently of the other, means1-C20alkyl, cyclohexyl, cyclopentyl, phenyl, naphthyl or diphenyl, and these radicals are unsubstituted or they are substituted by halogen, C1-C12the alkyl or/and group

With1-C12alkoxy, or R33is an S - or N-containing five - or six-membered heterocyclic ring, or;

R35represents cyclohexyl, cyclopentyl, phenyl, naphthyl or diphenyl, and these radicals are unsubstituted or substituted by one or more halogen atoms, With1-C4the alkyl or/and C1-C4alkoxy substituents, or R35is an S - or N-containing five - or six-membered heterocyclic ring;

R36and R37each independently of the other, is with the battle cyclopentadienyl, which is unsubstituted or mono-, di - or tizamidine1-C18the alkyl, C1-C18alkoxy, cyclopentyl, cyclohexyl or halogen; and

R38and R39each independently of the other represents phenyl, which is substituted by fluorine atoms or by a group of CF3at least two ortobalagang to the titanium-carbon connection and which may contain as an additional substituent in the aromatic ring pyrrolidyl or polically, each of which is unsubstituted or substituted by one or two groups: With1-C12alkyl, di(C1-C12alkyl)aminomethyl, morpholinomethyl,2-C4alkenyl, methoxymethyl, ethoxymethyl, trimethylsilyl, formyl, methoxy or phenyl,

or R38and R39representor;

R40, R41and R42each independently mean hydrogen, halogen, C2-C12alkenyl,1-C12alkoxy, C2-C12alkoxy which is interrupted by one to four oxygen atoms, cyclohexyloxy, cyclopentyloxy, phenoxy, benzyloxy, unsubstituted phenyl or diphenyl, or substituted groups:1-C4alkoxy-, halo-, phenylthio or1-C4alkylthio - phenyl or diphenyl, in which the BA R 40and R42at the same time does not mean hydrogen, and the radicalat least one radical R40or R42represents a C1-C12alkoxy, C2-C12alkoxygroup, which is interrupted by one to four oxygen atoms, cyclohexyloxy, cyclopentyloxy, phenoxy or benzyloxy;

E1represents O, S or NR43;

R43represents a C1-C8alkyl, phenyl or cyclohexyl; and

Y1represents a C3-C12alkylen, butylen, Butylin or4-C12alkylene, which is interrupted once or several times by groups-O -, or-NR44-not following each other, or Y1represents a phenylene, cyclohexene,or; and

R44represents hydrogen, C1-C4alkyl or C2-C4hydroxyalkyl.

9. Composition according to one of p-8, containing from 0.05 to 20 wt.% component (b) photoinitiator or from 0.05 to 20 wt.% components (b)+(C) photoinitiator.

10. The composition according to claim 6, which in addition to the photochemically curable component also contains a thermally curable component.

11. The compound of formula I according to claim 1, used as photoinitiator when photopolymers is of nonvolatile Monomeric, oligomeric or polymeric compounds having at least one ethylene unsaturated double bond, by irradiation of light with a wavelength in the range from 200 to 600 nm.

12. The composition according to claim 6 to obtain pigmented and non-pigmented compositions of surface coatings, printing inks, inks screen printing inks offset printing inks flexographic printing, powder coatings, printing plates, adhesives, dental compositions, optical waveguides, optical keys, color detection, composite materials, coatings, fiber glass cables, forms for screen printing, resistor materials, color filters, gel coatings (thin layers), to seal electrical and electronic components, in obtaining materials for magnetic recording, upon receipt of three-dimensional objects by stereolithography, photographic reproductions, materials for recording images, especially for holographic recording, upon receipt decolorizing materials, especially decolorizing materials for image capture, or upon receipt of the materials for recording images using microcapsules.

13. Coated substrate, at least one side surface of which is coated with a composition according to claim 6.



 

Same patents:

The invention relates to photopolymerizable compositions based on unsaturated polyesters that can be used for the manufacture of parts by means of laser-induced polymerization (stereolithography) without air

FIELD: rocketry; production of the potting composition for armoring the charge made out of the ballistite propellant.

SUBSTANCE: the invention is pertaining to the field of rocketry and presents the potting composition for armoring the charge made out of the ballistite propellant. The potting composition includes polybutylmethacrylate, butylmethacrylate, methylmethacrylateand in the capacity of the initiator and activator of the hardening - benzoyl peroxide and dimethylaniline. At that polybutylmethacrylate is dissolved in the mixture of butylmethacrylate and methylmetacrylate. The invention ensures manufacture of the qualitative products with the required level of the physical-mechanical and adhesive properties, as well as to reduce smokiness of the gases, and to reduce temperature of the waste gases from 2200°С to 800°С.

EFFECT: the invention ensures manufacture of the qualitative products with the required level of the physical-mechanical and adhesive properties, as well as to reduce smokiness of the gases, and significantly to reduce temperature of the waste gases.

2 tbl

Composition makeup // 2277552

FIELD: polymer materials.

SUBSTANCE: invention relates to polymer composition based on binder, namely unsaturated polyether resin or oligoether acrylates, and may be used in medicine, in production of paint and lacquer materials, etc. Composition comprises, wt parts: unsaturated polyether resin or oligoether acrylates or mixtures thereof, 100; polymerization promoter, in particular complex compound prepared by reaction of vanadium derivatives (vanadium pentoxide, ammonium methavanadate, of methavanadic acid) with orthophosphoric acid/water/butanol mixture, 0.3-0.88; polymerization initiator: cumene hydroperoxide, 0.3-0.44; and modifying additives, 0-20.

EFFECT: optimized makeup involving inexpensive, easily available, and highly efficient promoter.

1 tbl, 6 ex

The invention relates to a method for producing polymer coatings with high protective physico-chemical properties, low toxicity, suitable for implantation in tissue of living organisms

FIELD: polymerization catalysts.

SUBSTANCE: invention relates to a method for preparing supported titanium -manganese catalyst for synthesis of super-high molecular weight polyethylene via suspension ethylene polymerization process in hydrocarbon solvent. Titanium-containing catalyst supported by magnesium-containing carrier is prepared by reaction of organomagnesium compound Mg(C6H5)2•nMgCl2•mR2O, where n=0.37-0.7, m=2, R20 represents ether wherein R is i-amyl or n-butyl, with a silicon compound, namely product obtained by reaction of compound R'kSiCl4-k (R' is methyl or phenyl and k=0-1) with silicon tetraethoxide Si(OEt)4 at molar ratio R'kSiCl4-k/Si(OEt)4 = 6 to 40. Ethylene polymerization process in presence of above-defined catalyst in combination with co-catalyst is also described, wherein obtained super-high molecular weight polyethylene has loose density ≥ 0.39 g/cc.

EFFECT: increased molecular weight and loose density of polyethylene.

4 cl, 1 tbl, 8 ex

FIELD: polymer production.

SUBSTANCE: invention relates to high-stereospecific 1-butene (co)polymer and a high-activity process for producing the same. Process comprises polymerization of reactive monomer 1-butene in presence of catalyst including solid component containing titanium compound and in presence of inert gas, the latter being introduced into reactor together with hydrogen in order inert gas to be present in reactor during polymerization. This step is performed at elevated pressure in polymerization reactor owing to use inert gas at higher pressure than equilibrium pressure of gas-liquid reactant system at reaction temperature from 10 to 110°C. High-stereospecific polybutylene obtained in this process is characterized by that it is 1-butene homopolymer or copolymer including up to 40 wt % α-C2-C20-olefins other than 1-butene and shows following properties: titanium does nor present in catalyst residues at the ppm level, stereospecificity expressed through content of isotactic pentads (mmmm%) and measured using 13C-NMR technique equals 96 or higher, and molecular mass distribution (Mw/Mn) is 3-6.

EFFECT: enabled effective process for production of high-stereospecific polybutylene essentially free of catalytic residues.

3 cl, 4 dwg, 11 ex

FIELD: polymer production.

SUBSTANCE: invention relates to high-stereospecific 1-butene (co)polymer and a high-activity process for producing the same. Process comprises polymerization of reactive monomer 1-butene in presence of catalyst including solid component containing titanium compound and in presence of inert gas, the latter being introduced into reactor together with hydrogen in order inert gas to be present in reactor during polymerization. This step is performed at elevated pressure in polymerization reactor owing to use inert gas at higher pressure than equilibrium pressure of gas-liquid reactant system at reaction temperature from 10 to 110°C. High-stereospecific polybutylene obtained in this process is characterized by that it is 1-butene homopolymer or copolymer including up to 40 wt % α-C2-C20-olefins other than 1-butene and shows following properties: titanium does nor present in catalyst residues at the ppm level, stereospecificity expressed through content of isotactic pentads (mmmm%) and measured using 13C-NMR technique equals 96 or higher, and molecular mass distribution (Mw/Mn) is 3-6.

EFFECT: enabled effective process for production of high-stereospecific polybutylene essentially free of catalytic residues.

3 cl, 4 dwg, 11 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to preparation of cellular polymer particles suited to be used in coating deposition compositions. Cellular polyesters-based polymer particle according to invention including spherical particles having numerous air hollows and long-chain aliphatic groups and/or spatially hindered branched-chain hydrophobic groups associated with surface of said spherical particles is proposed. A composition for preparing indicated cellular particles and a method of preparing the same are developed.

EFFECT: enlarged assortment of starting materials for polymeric coating compositions.

11 cl, 10 tbl, 17 ex

FIELD: chemistry of polymers.

SUBSTANCE: invention relates to emulsion method for co-polymerization of acrylic monomers. Invention proposes a method involving preliminary emulsification of mixture of butyl acrylate with (meth)acrylic and/or vinyl monomer in water in the following mass ratio co-monomer : water = 1:(0.2-0.3) in the presence of 3.4-4.0 wt.-% of sulfooxyethylated alkylphenol ammonium salt wherein (C8-C10)-alkyl has the alkylation degree 18-26 wt.-%, the following emulsion co-polymerization at temperature 78-82°C for 3-10 h at continuous dosing of preliminary prepared co-monomers emulsion and 0.3-0.6 wt.-% of ammonium or potassium persulfate in the total ratio to the reaction mass co-monomer : water = 1:(0.4-0.5) followed by additional polymerization of the reaction mixture in addition of 0.1 wt.-% of ammonium or potassium persulfate after keeping the reaction mixture for 0.5 and 1.5 h and its final temperature keeping for 2 h. Invention provides increasing concentration of acrylic copolymer aqueous dispersion at low content of coagulum and improving its adhesion properties. Invention provides the development of a method for preparing highly concentrated aqueous dispersion with the content of acrylic copolymer 60 wt.-%, not less, for glues showing sensitivity to pressure.

EFFECT: improved preparing method, improved and valuable properties of dispersion.

2 cl, 1 tbl, 13 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to technology for producing granules used in preparing ion-exchange resins. Invention describes a method for producing polymeric monodispersed particles by suspension polymerization and involves the following steps: preparing monodispersed drops by adding a drop-forming device for preparing an aqueous dispersion medium into a chamber that formed the continuous phase, ejection of monomer hydrophobic liquid to aqueous dispersion medium through draw plate holes up under effect of regular vibration to form monomer liquid drops of a equal size preferably in aqueous dispersion medium; carrying out preliminary polymerization by adding prepared monomer liquid drops in aqueous dispersion medium into the first reactor, carrying out the polymerization reaction in a quasi-liquid layer to prepared suspension of partially polymerized drops of monomer in aqueous dispersion medium to degree when drops can't fuse or break; carrying out the final suspension polymerization at intensive stirring in the second reactor; at step for preparing monodispersed drops an aqueous dispersion medium is added to the form-forming device chamber at temperature 60-90°C, and monomer hydrophobic liquid is added into the drop-forming device at temperature 5-25°C or at environment temperature. Invention provides expanding zone for monodispersing drops of hydrophobic monomeric liquid in the drop-forming device allowing to vary sizes of prepared monodrops, and technical and technological simplifying the unit device.

EFFECT: improved producing method.

13 cl, 7 dwg, 1 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to technology for producing granules used in preparing ion-exchange resins. Invention describes a method for producing polymeric monodispersed particles by suspension polymerization and involves the following steps: preparing monodispersed drops by adding a drop-forming device for preparing an aqueous dispersion medium into a chamber that formed the continuous phase, ejection of monomer hydrophobic liquid to aqueous dispersion medium through draw plate holes up under effect of regular vibration to form monomer liquid drops of a equal size preferably in aqueous dispersion medium; carrying out preliminary polymerization by adding prepared monomer liquid drops in aqueous dispersion medium into the first reactor, carrying out the polymerization reaction in a quasi-liquid layer to prepared suspension of partially polymerized drops of monomer in aqueous dispersion medium to degree when drops can't fuse or break; carrying out the final suspension polymerization at intensive stirring in the second reactor; at step for preparing monodispersed drops an aqueous dispersion medium is added to the form-forming device chamber at temperature 60-90°C, and monomer hydrophobic liquid is added into the drop-forming device at temperature 5-25°C or at environment temperature. Invention provides expanding zone for monodispersing drops of hydrophobic monomeric liquid in the drop-forming device allowing to vary sizes of prepared monodrops, and technical and technological simplifying the unit device.

EFFECT: improved producing method.

13 cl, 7 dwg, 1 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to technology for producing granules used in preparing ion-exchange resins. Invention describes a method for producing polymeric monodispersed particles by suspension polymerization and involves the following steps: preparing monodispersed drops by adding a drop-forming device for preparing an aqueous dispersion medium into a chamber that formed the continuous phase, ejection of monomer hydrophobic liquid to aqueous dispersion medium through draw plate holes up under effect of regular vibration to form monomer liquid drops of a equal size preferably in aqueous dispersion medium; carrying out preliminary polymerization by adding prepared monomer liquid drops in aqueous dispersion medium into the first reactor, carrying out the polymerization reaction in a quasi-liquid layer to prepared suspension of partially polymerized drops of monomer in aqueous dispersion medium to degree when drops can't fuse or break; carrying out the final suspension polymerization at intensive stirring in the second reactor; at step for preparing monodispersed drops an aqueous dispersion medium is added to the form-forming device chamber at temperature 60-90°C, and monomer hydrophobic liquid is added into the drop-forming device at temperature 5-25°C or at environment temperature. Invention provides expanding zone for monodispersing drops of hydrophobic monomeric liquid in the drop-forming device allowing to vary sizes of prepared monodrops, and technical and technological simplifying the unit device.

EFFECT: improved producing method.

13 cl, 7 dwg, 1 ex

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to copolymers consisting of monomers comprising acid groups with double bond and other hydrophobic monomeric component used in prophylaxis of inorganic and organic deposits in water-bearing systems. Invention describes a water-soluble copolymer comprising: (a) monoethylene-unsaturated monomers chosen from group consisting of monocarboxylic acids, dicarboxylic acids and sulfoacids that can be neutralized; (b) at least copolymerizable hydrophobic acrylic, monocyclic and/or bicyclic terpene comprising unsaturated double bond wherein terpene hydrocarbon is preferable, and copolymer is prepared by free-radical copolymerization of components (a) and (b) in an aqueous phase. Also, invention describes a method for synthesis of abovementioned copolymer and methods for its using. Invention provides synthesis of nontoxic copolymer used for prevention of deposits in water-bearing systems that can be easily prepared from available components and able to store for a long time without loss of activity.

EFFECT: improved preparing method, valuable properties of copolymers.

22 cl, 6 tbl, 6 ex

FIELD: polymer production.

SUBSTANCE: invention provides elastomeric polymer composition comprising at least polymers and copolymers obtained from substituted and unsubstituted vinylaromatic monomers and from diene monomers and including 15 to 85% copolymer containing (i) at least one block formed by 10 to 5000 mainly syndiotactic structural sequences of monomer units derived from at least one substituted or unsubstituted vinylaromatic monomer and (ii) at least one block formed by 10 to 4000 monomer units derived from at least one diene monomer with predominant 1,4-cis structure, wherein 15-85 wt % of polymer obtained from diene monomers has molecular weight between 6000 and 600000 with content of 1,4-cis monomer units constituting at least 90%, while up to 70% of polymer obtained from substituted and unsubstituted vinylaromatic monomers has molecular weight between 10000 and 500000 and degree of syndiotacticity (expressed through syndiotactic pentads) at least 95%, a part formed by monomer units derived from diene monomer is optionally partially or completely hydrogenised. Method of preparing such elastomeric composition is also described.

EFFECT: extended temperature range for elastomeric performance of composition.

42 cl, 5 tbl, 27 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to novel intermediate compounds and inmproved method for synthesis of compound of the formula (C): . Proposed method is based on using inexpensive parent substances and provides synthesis of intermediate compounds with the high yield and high purity degree being without carrying out procedures for chromatographic purification and can be realized in large-scale industry manufacture. Invention relates to improved methods for synthesis of compound of the formula (I): , compound of the formula (II): , compound of the formula (III): , compound of the formula (VIII): , compound of the formula (IX): , and to a reagent consisting of boron tribromide and 2,6-dimethylpyridine. Method is used for a sparing and selective splitting a methyl group in aromatic methyl ethers.

EFFECT: improved method of synthesis.

12 cl, 8 ex

FIELD: organic chemistry, perfumery.

SUBSTANCE: invention relates to an aromatizing composition containing at least compound of the formula (I): as an active component wherein values w, m, P, X, G, Q and n are given in claim 1 of the invention description, and one or more aromatizing component. Also, invention relates to a method for improving, enhancing or modifying odor, to a method for aromatizing surface, method for enhancing or prolonging the diffusion effect of component on surface and to novel compounds of the formula (I) with exception of compounds enumerated in claim 10 of the invention description and to invention relating to aromatizing article using compounds of the formula (I).

EFFECT: valuable cosmetic properties of compounds.

13 cl, 14 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to synthesis of 1,3-dicarbonyl compounds and to a new method for preparing 4-substituted alkyl-3-oxobutanoates of the formula: wherein: R is C6H5CH2, 2-F-6-ClC6H3CH2, 2,6-Cl2C6H3CH2, 1-C10H7CH2, Ph2CH; Alk is Me; R is 1-AdCH2; Alk is i-Pr that are used precursors of antiviral agents of pyrimidine order. Method involves acylation of 2,2-dimethyl-1,3-dioxane-4,6-dione with acyl chlorides in dichloromethane in the presence of triethylamine followed by alcoholysis of 5-(1-hydroxyethylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione wherein acylation is carried out with acyl chlorides in the presence of trimethylsilyl chloride in the mole ratio 2,2-dimethyl-1,3-dioxane-4,6-dione : acyl chloride : trimethylsilyl chloride : triethylamine = (1-2):1:1.1:3.5, respectively, with formation of an intermediate product 5-[1-(trimethylsilyloxy)ethylidene]-2,2-dimethyl-1,3-dioxane-4,6-dione that is subjected for hydrolysis with formation of 5-(1-hydroxyethylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione and its following alcoholysis and formation of the end product. Method provides enhancing yield and purity of claimed compounds.

EFFECT: improved method for preparing.

2 cl, 8 ex

FIELD: organic chemistry.

SUBSTANCE: invention relates to new method for production of m- or p-substituted α-arylalkanecarboxylic acids of general formula I

from respective α-hydroxylated derivatives using inexpensive reagents and without converting of any reducible groups such as ester or ketone ones in side chains. In formula R is hydrogen, C1-C6-alkyl; R1 is hydrogen, linear or branched C1-C6-alkyl, phenyl, p-nitrophenyl, alkali or earth-alkali cation or cation of pharmaceutically acceptable ammonia salt: A is C1-C4-alkyl, aryl, optionally substituted with one or more alkyl, hydroxy, etc., aryloxy, arylcarbonyl; A is in m- or p-sites; P - linear or branched C1-C6-flkyl, phenyl, nitrophenyl. Claimed method includes the next steps: a) converting of compounds of formula II to compound of formula III either by reaction of II with compound of formula in presence of organic or inorganic base or by reaction of II with thiophene of formula and followed by reaction of obtained product with HNRaRb, wherein Ra andRb are as defined above; b) thermal rearrangement of III to form IIIb ; c) catalytic dehydration of IIIb to form IIIc ; and d) optional hydrolysis of IIIc to obtain target compound of formula I. Also are disclosed new compounds of formulae III and IIIb.

EFFECT: new α-arylalkanecarboxylic acids and intermediates thereof.

6 cl, 5 ex

-ketocarboxylic acids" target="_blank">

The invention relates to an improved method of transesterification of esters-ketocarboxylic acid with the structural formula (I), the alcohol of formula (II) R3HE, and R1, R2, R3means a branched, unbranched or cyclic, saturated or unsaturated C1-C6is an alkyl group or benzyl group, and R1and R2are not the same, which are used as, for example, intermediates for biologically active substances for agro - and pharmaceutical industry, as solvents, and so on

The invention relates to an improved process for the preparation of ester 2-alkylidene-4-bromocatechol acid of the formula (3), where R1and R2each independently from each other represent a lower alkyl group with 1-5 carbon atoms, which is used as an intermediate connection upon receipt of the substances for pharmaceutical purposes, such as antibiotics
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