The composition and method of curing

 

The invention relates to basic-catalyzed curable compositions based on epoxy compounds. The composition includes: (A) 0.1 to 20% by weight of the composition of latent catalyst of the principal type --aminoacetophenone General formula (I)(C) an epoxy compound and at least one compound that can react with an epoxy compound selected from carboxyl-containing compounds or thiol, and (C) optionally from 0.01 to 5 wt.% sensitizer. The method of curing of the composition is as follows: the composition is irradiated with light having a wavelength of 200-700 nm, to obtain from the photosensitive-aminoacetophenone formula (I) catalyst basic type and consistently armatured obtained in the presence of photogenerated catalyst. The invention allows the use of known initiators fototerapia radical-curable compositions in basic-catalyzed reactions of epoxy compounds. These catalysts show excellent latency to exposure to ultraviolet light, have a high absorption in the UV region and a high catalytic activity posekim curable compositions, including-aminoketone compounds as latent bases, and also to a method of curing such compositions, inter alia, in combination with radically primaryservername components.

Among thermosetting resins epoxy resins have found very wide applications due to a wide range of chemical reactions and materials that can be used for curing, and many different properties that result. More specifically, their excellent mechanical and chemical properties, high adhesion strength, good thermal stability and high electrosocket made them extremely useful. They are widely used as adhesives, coatings, thermosetting materials or photoresists (see, for example, C. A. May, Epoxy Resins, Chemistry and Technology, 2nd Ed.Marcel Dekker, New York, 1988).

The curing of epoxy resins can be carried out by reaction of polyprionidae, which lead to the formation of ties and cross ties. The most widely used agents for these purposes are active hydrogen compounds such as polyamine, polyacid, polymercaptan, polyphenols, anhydrides, isocyanates, etc., These reactions are, in principle, stoichiometric reactions t usually in relatively high concentrations. These reactions politicoeconomic can, of course, to be catalyzed by appropriate catalysts. It is possible to use, for example, dicyandiamide, benzoguanamine or imidazole derivatives as catalysts for the reaction of epoxides with carboxylic acids.

Anionic and cationic polymerization of epoxides occurs with a variety of Lewis bases and acids, as well as with numerous salts and complex initiators. In the case of basic-catalyzed polymerization amines, such as benzilpenicillin or 2,4,6-Tris(dimethylaminomethyl)phenol and imidazole derivatives, which are first subjected to attach to the epoxy group through their labile hydrogens, and then function as initiators, were also used. In the case of cationic polymerization in a strong acid Bronsted, such as triftoratsetata, and a wide range of Lewis acids (most applicable of which are boron-triforine complexes can catalyze the cationic polymerization of epoxides.

A unique property of epoxides may be used in photos, if you have the proper light-sensitive composition. In principle, the epoxides can not be solidified topicalization, if suitable reactive groups, such as divinelvie esters or acrylates, are also present, but this is not always desirable. Svatojiricky initiated by the reaction of epoxy groups require photoinitiators that can generate appropriate initiating species. Cationic photoinitiator Navaho type, for example diarylethene salt or triarylsulfonium salts, are well known and can be used for polonizirovannaya cationic polymerization of epoxides. Although the mechanism of cationic photopolymerization has valid advantages such as insensitivity to oxygen, it cannot be used if the main material present in ultravioletabsorbing compositions. Therefore, there is a need for effective photoprotein basic catalysts which can be used for curing epoxydodecane photosensitive compositions. The aim of the present invention is, firstly, to offer a new way for photochemical obtain tertiary amine catalysts which can be used for basic catalysis of politicoeconomic to epoxides, and, secondly, the relevant structures.

Fitopolesye basic catalysis is(for example, EP-A 599571, JP-A 4330444 and EP-A 555749). Amines are the most used photoprocessing grounds, known to the present time. However, some known photogenerator amines such as substituted benzylarbutin (examples are disclosed in J.Org. Chem. 1990, 55, 5919), have the disadvantage of insufficient absorption at the site, close to the ultraviolet, which is a severe limitation for many applications.

Although photocatalysts producing amines with higher absorbance in the area between 300 and 400 nm, has already been proposed (see, for example, Polym. Mat. Sci. Eng. 1991, 64, 55, or Macromol. 1995, 28, 365), they cannot always be used due to the fact that may occur recombination of free amine and carbonyl by-product to obtain the imine depending on the acidity of the composition. In addition, they can generate only primary or secondary amines, which are not particularly effective catalysts for polyaddition to epoxides or epoxy anionic polymerization.

It is well known that tertiary amines are effective basic catalysts which can be used in reactions of epoxides, but described only a few attempts to get them photochemically. Bil. Eng. 1995, 72, 201). These connections require a long time exposure, have unfavorable absorption spectrum, and their structure can be changed only with some difficulty. Accordingly, there is a need for effective photogenerator tertiary amines. To use these compounds, they must exhibit a low reactivity with the composition prior to exposure to ultraviolet light. In particular, the stability during storage of light-sensitive compositions containing them, must be high, and they should not be less than shown after pre-drying phase, which is usually necessary to remove solvent. They should have a high absorption at the site, close to ultraviolet, to effectively generate free amine in exposure conditions usually used in the field of photographic images. And finally, after irradiation of the base should show high catalytic activity in thermal cure.

Photolytic decay of a specific-aminoketone compounds radicals, as well as the photopolymerization refinancing monomers and oligomers with said ketone compounds are well known and rysowanie latent bases in the hybrid systems, for example, in systems with radical and cation polymerizability components. U.S. patent 4943516 discloses a hybrid system that includes photoinitiator for radical polymerizing components and, among other things, curing agent for the epoxy component, and process for curing such compositions. (4-Methylthiophenyl)-1-methyl-1-morpholinoethyl named as an example of photoinitiator for polymerizing free radicals components.

It is now established that certain compounds (already known as initiators for fototerapia radical polymerizing compositions) can be used as basic-generating compounds, i.e. compounds that produce the Foundation under irradiation ("photosmovie generators") and, thus, can be applied in basic-catalyzed reactions.

Accordingly, the present invention relates to compositions, comprising: (A) as a latent catalyst ranging from 0.1 to 20 wt.%, at least one of the compounds of formula Iwhere Ar1group of the formula IVwhere R5group-OR17, -SR18, -N(R19)(R20, R7and R8is hydrogen or halogen,
R9is hydrogen,
Z is-O-, -S - or-N(R11)-,
R1and R2each independently of one another are
(a) C1-C6-alkyl,
(C) a radical of the formula

(d) a radical of the formula-CH(R13)-Ar2;
where Ar2radical of phenyl, which is unsubstituted or substituted with halogen,1-C4-alkyl, methylthio, methoxy or benzoyl;
R3and R4each independently of one another - C1-C12alkyl, C2-C4alkyl, substituted C1-C4alkoxy, -CN, or-COO(C1-C4-alkyl),
or R3and R4- allyl, cyclohexyl or benzyl,
or R3and R4together With4-C6alkylene, which may be interrupted by-O-;
R11- C1-C4alkyl, allyl, benzyl or2-C4alkanoyl;
R13, R14, Rl5and R16each independently of one another is hydrogen or methyl;
R17is unsubstituted or SH-substituted C1-C4alkyl, 2-hydroxyethyl, 2-methoxyethyl, 2-allyloxymethyl, allyl, cyclohexyl, phenyl or benzyl;
R18is hydrogen, unsubstituted or SH-substituted C1-C12alkyl, 2-hydroxyethyl, 2-meteko from one another - C1-C12alkyl, C2-C6alkoxyalkyl, acetyl, allyl or benzyl, or
R19and R20together With4-C6alkylene, which may be interrupted by-O-;
B) at least one epoxy compound and at least one compound able to react with epoxides in the presence of a base, and
(C) optionally from 0.01 to 5 wt.% sensitizer.

In accordance with the invention in the composition is at least one compound of the formula I. Accordingly, the composition can be a mixture of compounds of the formula I, preferably one or two connections.

C1-C4alkyl, R14, R15and R16may be, for example, stands, ethyl, propylene, isopropyl, bootrom, isobutyl, secondary or tertiary bootrom.

C1-C8alkyl, R2, R11and R13can also be, for example, Pentium, hexyl, heptyl, actilon, 2-ethylhexyl or 2,2,4,4-TETRAMETHYLBUTYL.

C1-C12alkyl, R3-R10, R17-R19and R20can also be nonilon, decyl, Isodecyl, undecim or dodecyl.

With3-C5alkenyl, R3, R4, R1R19and R20can also be ub>17and R18can also be, for example, hexenyl, oktanolom or decenium.

R2, R5, R6, R7, R8and R9as cycloalkyl, in particular, cyclohexyl.

C5-C12cycloalkyl, R3, R4, R19and R20can also be, for example, cyclooctyl or cyclododecyl.

Phenyl-C1-C3-alkyl, R3, R4, R17, R18, R19and R20in particular, benzyl.

C1-C6alkylen Y can be a methylene or di-, tri-, Tetra-, Penta - or hexamethylene.

C1-C7alkylen W can be a methylene, ethylene, 1,2-propylene or 1,2-hexylene.

Alkyliden is unbranched or branched alkyl chain having two free valencies on the same carbon atom

Accordingly, With2-C6alkyliden V and W can be, for example, ethylidene, propylidene, isopropylidene, butylidene, isobutylidene or hexylidene.

Examples AG2groups are phenyl, 1-naphthyl, 2-naphthyl, 2-furyl, 2-thienyl, 4-chlorophenyl, tolyl, 4-isopropylphenyl, 4-octylphenyl, 3-methoxyphenyl, 4-phenoxyphenyl, 4-phenylphenyl, 4-benzoylphenyl and 4-chloro-1-naphthyl.

Examples Samusenko the-chlorpropyl, 2-phenylethyl or 3-phenylpropyl.

Examples of substituted phenyl R2groups are 4-chlorophenyl, 3-methoxyphenyl, 4-tolyl or 4-butylphenyl.

Substituted alkyl, R3and R4may be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxyisobutyryl, 2-ethoxyethyl, 2-methoxypropyl, 2-butoxyethyl, 2-cyanoethyl, 2-ethoxycarbonylethyl or 2-methoxycarbonylethyl.

Substituted phenyl R4can be 3-chlorophenyl, 4-chlorophenyl, 4-tolyl, 4-tertbutylphenol, 4-dodecylphenyl, 3-methoxyphenyl or 3-ethoxycarbonylphenyl.

If R4(with R2is alkylene or fenilalanina, they preferably form together with the linking atom and atom N) 5 - or 6-membered heterocyclic ring.

If R3and R4together are alkylene or interrupted by alkylene, they preferably form together with the linking atom N) 5 - or 6-membered heterocyclic ring, such as pyrrolidine, piperidine, morpholine, thiomorpholine or piperidine ring which may be substituted by one or more alkyl, hydroxyl, alkoxy or ether groups.

C2-C8alkanoyl R10and R17may be, for example, propionyl, Boutillon, isobutyryl, hexanoyl or octanoyl, but preferably is 20 can be, for example, 2-hydroxyethyl, 2-hydroxypropyl or 4-hydroxybutyl.

Alkylen or broken alkylen R12may be, for example, ethylene, tri-, Tetra-, Penta-, hexa-, OCTA - or dodecanethiol, 2,2-dimethyltrimethylene, 1,3 .3m-trimethylmethanaminium, 3-examinationa, 3-oxaliplatin, 4,7-dioxymethylene, 4,9-dioxadodecane, 3,6,9,12-tetrachloroethylene or 4-telephonelines.

If C1-C6alkyl broken by one or more atoms Of he broken, for example, 1-3, or one or two atoms of O.

If R14and R15together are3-C7alkylene, they, in particular, 1,3 - or 1,4-alkylene, for example 1,3-propylene, 1,3-butylene, 2,4-pentile, 1,3-hexylen, 1,4-butylene, 1,4-pentile or 2,4-hexylen.

Substituted phenyl R17, R18, R19and R20may be, for example, 4-chlorophenyl, 3-chlorophenyl, 4-tolila, 4-tert-butylphenyl, 4-nonylphenyl, 4-dodecylphenyl, 3-methoxyphenyl or 4-ethoxyphenyl.

Substituted C1-C6alkyl R17may be, for example, 2-hydroxyethyl, 2-methoxyethyl or 2-allyloxymethyl.

Substituted C1-C6alkyl R18may be, for example, 2-mercaptoethanol, 2-hydroxyethyl, 2-hydrox the 3.

Alkoxyalkyl R19and R20may be, for example, methoxyethyl, amoxicillon, 2-ethoxypropanol, 2-butoxyethyl, 3-methoxypropyl or 2-hexyloxyethoxy.

With2-C3alkanoyl R19and R20are, in particular acetyl.

If R19and R20together are alkylene or broken alkylene, they form, together with the linking atom N) heterocyclic ring, preferably a 5 - or 6-membered ring which may be substituted by alkyl, hydroxyl, alkoxy or ether groups. Examples of such rings are pyrrolidine, piperidine, 4-hydroxypiperidine, 3-ethoxycarbonylpyrimidine, morpholine or 2,6-dimethylmorpholine rings.

All these compounds have at least one primary amino group and can therefore be converted into the corresponding salts by adding acids. These acids may be inorganic or organic acids. Examples of such acids are model HC1, NVG, N2SO4N3RHO4mono - or polycarboxylic acids, for example acetic acid, oleic acid, succinic acid, sabotinova acid, tartaric acid or CF3COOH and sulfonic acids, for example CH3SO3H, C1ub>N or CF3SO3N.

Preferred compounds of formula I are those in which Ar1is a group of formula IV, where
R5group-OR17, -SR18or-N(R19)(R20),
R6is hydrogen, chlorine or C1-C4alkyl or has one of the meanings indicated for R5,
R7and R8is hydrogen or chlorine,
R9is hydrogen or C1-C4alkyl,
R1(a) a radical of the formula

(b) a radical of the formula-CH2-Ar2where
Ar2a phenyl radical unsubstituted or substituted by halogen, C1-C4the alkyl, CH3S-, CH3O - or benzoyl,
R2has one of the meanings indicated for R1or is C1-C4the alkyl,
R3and R4each independently of one another C1-C6alkyl, 2-methoxyethyl, allyl or benzyl, or
R3and R4together - tetramethylene, pentamethylene or 3-oxapentane,
R14and R15is hydrogen or methyl,
R17is unsubstituted or SH-substituted C1-C4alkyl, 2-hydroxyethyl, 2-methoxyethyl or phenyl,
R18is unsubstituted or SH-substituted C1-C12alkyl, 2-hydroxyethyl, 2-methoxyacetyl, acetyl or allyl or
R19and R20together are4-C5alkylene, which may be interrupted by-O-.

Especially preferred is a compound of the formula I - (4-morpholinomethyl)-1-benzyl-1-dimethylaminopropane.

Further, those compounds of formula I, where A1group of the formula IV, are preferred, in which5is a group-SR18,
R1- benzyl or allyl radical;
R6is hydrogen or methoxy, and R7, R8and R9- hydrogen.

In addition, the compounds of formula I, where A1group of the formula IV, where R1and R2each independently of one another C1-C8alkyl, allyl or benzyl, and
R5group-OR17N(R20)(R19or-SR18are preferred, especially (4-methylthiophenyl)-1-methyl-1-morpholinoethyl.

Preferred are the compounds of formula I, in which
Ar1group of the formula IV, where
R1and R2each independently of one another - C1-C4alkyl or benzyl;
R3and R4each independently of one another - C1-C4alkyl or together - morpholino;
R5- morpholino or C1-C4alkylthio, and
R6, R7, R8b>19
)(R20), those compounds are preferred in which R7and R8is hydrogen, and those in which R6, R7, R8and R9is hydrogen, and those in which R1- allyl or benzyl.

Preferred compounds of formula I are also those in which Ar1group of the formula IV, where
R5is hydrogen, halogen or C1-C12alkyl, and
R6, R7, R8and R9is hydrogen,
R1- allyl or benzyl,
R2- C1-C6alkyl, allyl or benzyl,
R3and R4each independently of one another - C1-C12alkyl, C2-C4alkyl, which is substituted C1-C4alkoxy, -CN, or-COO(C1-C4by alkyl), or
R3and R4- allyl, cyclohexyl or benzyl, or
R3and R4together With4-C6alkylene, which may be interrupted by-O-.

Examples of individual compounds of formula I are disclosed in US patent 5077402.

Obtaining compounds of formula I are known and are disclosed, inter alia, in US 4582862, US 4992547 and US 5077402.

In accordance with the present invention the compounds of formula I can be used as a latent catalyst base, i.e. the generators of the grounds, which advance the content of inorganic fillers connection able to basically catalytic reactions, which can be, for example, by reaction substitution reaction accession or condensation reaction.

The basis photogenerated only in the illuminated areas of the composition and therefore, for example, vatoobraznaya thermosetting compositions, cured by fotonovel catalyst, can be easily obtained without any need for additional method of radical polymerization. The method according to the present invention therefore is applicable for curing compositions that do not necessarily contain Ethylenediamine double bonds, and provides new vatoobraznaya thermosetting compositions, cured anionic mechanism.

Component (C), subject to latent curing grounds, or in the described method, respectively, is in General a compound containing at least one epoxy group and at least one group which can react with epoxides in the presence of a base. Component (C) can also be a mixture of at least one epoxy compound and at least one compound that can react with epoxides in the presence of a base.

Connections, spone, such as carboxylic acids and anhydrides, and thiols. Alcohols, amines and amides in General compounds containing active H atoms, are also suitable.

Epoxy compounds that can be solidified latent main compounds in accordance with this invention are in General compounds containing epoxy groups, Monomeric or dimeric epoxides, as well as oligomeric and polymeric compounds having an epoxy group. Typical examples are epoxydecane acrylates, glycidyloxy ethers of bisphenol a, such as 2,2-bis[4-(2,3-epoxypropoxy)phenyl]propane, phenol and crenoline epoxy Novolac, glycidyloxy ethers of aliphatic diols, diglycidyl ether of hydrogenated bisphenol a, in particular 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl] propane, 1,1,2,2-tetrakis[4-(2,3-epoxypropoxy)phenyl]ethane, tripyridyltriazine and many other well-known experts in this field.

Preferred are compounds with at least two epoxy groups.

Epoxy compounds, among others, described in Ullmann''s Encyclopedia of Industrial Chemistry, 5th Edition, vol. A9, Weinheim, New York, 547-553 ("encyclopedia of Industrial Chemistry" Ulmann, S. 547-553).

In the context of the invention may be used is, is AutoRAE capable of reacting with the epoxide, as, for example, dicarboxylic acid or polymer acid. Specific examples include malonic acid, succinic acid, glutaric acid, adipic acid, sabotinova acid, phthalic acid, terephthalic acid, maleic acid, cyclohexanecarbonyl acid, polymeric acids, such as partially saponified the polyacrylates, as an example, resin Carboset from Goodrich, USA. Can also be used copolymers of unsaturated compounds with acid functionality or without them. Examples are partially esterified copolymers strolling anhydride, commercially available under the trade name Scripsit from the company Monsanto. In the context of the present invention may be used copolymers containing both epoxy and acid groups. Examples of suitable anhydrides can result from specific duotronic anhydrides. Specific examples are phthalic anhydride, methyltetrazolyl anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, maleic anhydride, itacademy anhydride and netonomy anhydride.

Examples, among others, are disclosed in the patent is mi transverse link.

Usually suitable thiols are Monomeric, oligomeric, aliphatic or aromatic thiols. Specific examples of such thiols are pentaerythritol(mercaptoacetate), pentaerythritol(mercaptopropionate), 4,4'-talibanzation, dithiothreitol, mercaptoethanol, dodecanthiol, thioglycolate acid, 3-mercaptopropionic acid or etilenvinilatsetata.

Further examples for systems that are suitable as component (B) in the present invention are disclosed, inter alia, in EP 706091, EP 747770, WO 96/41240 and DE 19622464. Additional examples of resins that can be solidified latent basis, in accordance with the invention, are disclosed, inter alia, in the patent US 4943516.

Important compounds are those in which component (B) presents catalyzed by bases, polimerizuet or curable organic material. The organic material may be in the form of mono - or polyfunctional monomers, oligomers or polymers. Preferred oligomeric/polymeric systems below.

Examples of such binder systems, which can be catalyzed by bases, are:
1) acrylate copolymers with alkoxysilane side groups, alkoxysilyl is poliakrilatov, containing hydroxyl groups, polyesters and/or polyethers and aliphatic or aromatic polyisocyanates;
3) two-component system functional polyacrylates and polyepoxides, polyacrylate containing carboxyl groups, anhydrite group, thiol group or an amino group;
4) two-component system thermodiffusion or siliconmotion polyacrylates which contain hydroxyl groups, polyesters and/or polyethers or aromatic polyisocyanates;
5) two-component system (poly)ketimines and aliphatic or aromatic polyisocyanates;
6) two-component system (poly)ketimines and unsaturated acrylate resins or acetoacetate resins or methylacrylamidoglycolate;
7) two-component system of polyacrylates containing anhydrite group and polyamine;
8) two-component system (poly)oxazolidines and polyacrylates containing anhydrite groups, or unsaturated acrylate resins or polyisocyanates;
9) two-component system of polyacrylates containing an epoxy group, and polyacrylate containing carboxyl group or amino group;
10) polymers, osnovaniem 1-3 is particularly preferred. Also suitable are any mixtures or combinations of the above compounds.

Catalyzed by base system components react at ambient or elevated temperatures to form a coating system with a cross-link, which is suitable for many applications.

Component (A) in a new composition is typically present in an amount of 0.1-20 wt.%, preferably 1-10%, for example 1-5%.

The sensitivity of the matter fotonovela generator to the radiation can be further improved by combining the above-mentioned substances with a suitable sensitizer (S).

Examples of such sensitizers include, in particular, sensitizers from the group of carbonyl compounds having a triplet energy in 225-310 kJ/mol. Examples of relevant sensibilisation compounds, moreover, are xanthones, thioxanthones, phthalimide, anthraquinones, acetophenone, propiophenone, benzophenone, aziraphale, 2-(allmetro)of thiazoline, 3-acicularis and 3,3'-carbonylmethyl. Preferred sensitizers are thioxanthone, 3-acicularis and 2-(koimeterion)of thiazoline, thioxanthone, and 3-acicularis especially preferred.

Examples of individual compounds that can be used is

These sensitizers component (C) increase the reactivity of the generated amine bases without reduction of the shelf life of the compositions.

The amount of the sensitizer (C) in the composition is from 0.01 to 5 weight. %, preferably from 0.025 to 2%.

The fact that the photodecomposition of compounds generator latent bases of formula I are also generates radicals, are particularly useful in dual curing systems ( hybrid systems), where required as a radical initiator, and the basic catalyst. Accordingly, the substances of the formula I can also be used as a latent base and at the same time as radical initiators in binary systems hardening.

The invention therefore also relates to systems which additionally contain radically paliperidonesee compounds (D) in addition to component (B).

Such compounds (D) are unsaturated compounds, which can include one or more olefinic double bonds. They can be low (Monomeric) or high (oligomeric) molecular weight. Examples of monomers containing a double bond are alkyl or hydroxyalkyl acrylates or methacrylates, such as methyl, ethyl, butyl, 2-ethylhexyl and 2-hydroxyethylacrylate, Isobar Vlada Acrylonitrile, acrylamide, methacrylamide, N-substituted (meth)acrylamide, complex, vinyl esters such as vinyl acetate, simple vinyl esters, such as isobutylphenyl ether, styrene, alkyl - and halogenation, N-vinyl pyrrolidone, vinyl chloride and vinylidenechloride.

Examples of monomers containing two or more double bonds, are diacrylate of ethylene glycol, propylene glycol, neopentyl glycol, hexamethyleneimine and bisphenol a, and 4,4'-bis(2-acryloyloxyhexyloxy)diphenylpropane, trimethylpropane, pentaerythritoltetranitrate or tetraacrylate, vinylacetat, divinylbenzene, divinylbenzene, diallylphthalate, triethylphosphate, triallylisocyanurate or Tris(2-acrylonitril)isocyanurate.

Examples of polyunsaturated compounds of relatively high molecular weight (oligomers) are calironia epoxy resin, calironia polyesters, polyesters containing vinyl ether or epoxy groups, and also polyurethanes and polyesters. Further examples of unsaturated oligomers are unsaturated polyester resins, which are usually obtained from maleic acid, phthalic acid and one or more diols and which have a molecular weight from about 500 to 3000. In addition, perhaps considering, polyurethane, simple polyester, polyvinylidine and epoxy the main chain. Particularly suitable are combinations of oligomers, which are vinylester group, and polymers, as described in WO 90/01512. However, the copolymers of vinyl ester and maleic cyclocephalini monomers are also suitable. Unsaturated oligomers of this type can also be attributed to prepolymers.

Particularly suitable are the esters Ethylenediamine carboxylic acids and polyols or polyepoxides, as well as polymers having ethyleneamine groups in the chain or in side groups, e.g. unsaturated polyesters, polyamides and polyurethanes and their copolymers, alkyd resins, polybutadiene and butadiene copolymers, branch, Rubezhnoe, Ukraine and isoprene copolymers, polymers and copolymers containing (meth)acrylic groups in side chains, and also mixtures of these 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. Acrylic and methacrylic acid are preferred.

Suitable polyols are areawise hydroquinone, 4,4'-dihydroxybiphenyl, 2,2-di(4-hydroxyphenyl)propane, and novolak and Cresols. Examples of polyepoxides are those based on the above-mentioned polyols, especially of aromatic polyols and epichlorohydrin. Other suitable polyols are polymers and copolymers containing hydroxyl groups in the polymer chain or in side groups, examples of which include polyvinyl alcohol and its copolymers, or polyhydroxyalkane the methacrylates or copolymers. Further suitable examples are oligoesters having hydroxyl end groups.

Examples of aliphatic and cycloaliphatic polyols are alkylenedioxy having preferably 2-12 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 molecular weights of preferably from 200 to 1500, 1,3-cyclopentanediol, 1,2-, 1,3 - or 1,4-cyclohexanediol, 1,4-dihydroxyphenylglycol, glycerol, Tris(-hydroxyethyl)amine, trimethylacetyl, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol.

The polyols may be partially or fully amerititle, and partial esters can be modified free of hydroxyl groups, for example tarifitsirovana to simple or complex esters other carboxylic acids.

Examples of esters:
trimethylolpropane, Triethylenetetramine, trimethylolpropane, trimethylenetrinitramine, tetramethylethylenediamine, triethyleneglycoldinitrate, Tetraethylenepentamine, pentaerythritoltetranitrate, pentaerythritoltetranitrate, pentaerythritoltetranitrate, dipentaerythritol, dipentaerythritol, dipentaerythritol, dipentaerythritol, dipentaerythritol, tripentaerythritol, pentaerythritoltetranitrate, pentaerythritoltetranitrate, dipentaerythritol, dipentaerythritol, tripentaerythritol, pentaerythritoltetranitrate, dipentaerythritol, dipentaerythritol, dipentaerythritol, etilenglikolevye, 1,3-potentialities, 1,3-potentialtheorie, 1,4-mutandaaldactone, arbitrarily, arbitratrary-modified pentaerythritol triacrylate, sorbitol cerametallic, sorbitol pentacrest, skilet, bicarinata and mimetically of polyethylene glycol having a molecular weight from 200 to 1500, or mixtures thereof.

Suitable components (D) are the amides of identical or different unsaturated carboxylic acids with 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-hexylaniline, octylaniline, dodecylamine, 1,4-diaminocyclohexane, ISOPHORONEDIAMINE, phenylenediamine, biphenylamine, di -- aminoacylase ether, Diethylenetriamine, Triethylenetetramine, di(-aminoethoxy)- or di(-aminopropoxy)ethane.

Other suitable polyamines are polymers and copolymers, preferably containing an additional amino group in the side chain, as well as oligoimide with aminobenzene group. Examples of such unsaturated amides are methylenebisacrylamide, 1,6-hexamethyleneamine, diethylenetriaminepentaacetate, bis(methacryloyloxy)ethane,-methacrylamidoethylene and N-[(the R, of maleic acid and diols or diamines. Some of maleic acid can be replaced by other dicarboxylic acids. They can be used together with Ethylenediamine copolymers, such as styrene. The polyesters and polyamides can also be produced from dicarboxylic acids and Ethylenediamine diols or diamines, especially from those that have a relatively long chain, for example from 6 to 20 carbon atoms. Examples of polyurethanes are those that include saturated or unsaturated diisocyanates and unsaturated or saturated diols, respectively.

Polybutadiene and polyisoprene, and their copolymers are known. Examples of suitable monomers are olefins such as ethylene, propylene, butylene and hexene, (meth)acrylates, Acrylonitrile, styrene or vinyl chloride. Polymers with (meth)acrylate groups in the side chain are also known. They may, for example, reaction products of epoxy resins based novolacs with (meth)acrylic acid or can be Homo - or copolymers of vinyl alcohol or hydroxyalkyl derivatives, which tarifitsirovana methacrylic acid, or may be Homo - or copolymers of methacrylates, which tarifitsirovana Hydra desired mixture. It is preferable to use a mixture of polyol(meth)acrylates.

The new compositions may also be added to the binder, and this is especially advisable when photopolymerizable compounds are liquid or viscous substances. The amount of binder may be, for example, 5-95%, preferably 10-90%, and particularly preferably 40-90% by weight on the total solids content. The choice of binder depends on the application and properties required for this area, such as the ability manifestations in water and organic solvents, adhesiveness to substrates and sensitivity to oxygen.

Examples of suitable binders are polymers having a molecular weight of about 5000 to 2000000, preferably from 10000 to 1000000. Typical examples are: Homo - and copolymers of acrylates and methacrylates, for example copolymers of methyl methacrylate/acrylate/methacrylic acid, poly(alkyl methacrylates), poly(alkylacrylate); pulp complex and ethers such as cellulose acetate, acetobutyrate cellulose, methylcellulose, ethylcellulose;
the butyral, polyvinylformal, cyklinowanie rubber, polyethers such as polyethylene oxide, polypropyleneoxide and polytetrahydrofuran the reed/vinylidenechloride, copolymers of vinylidenechloride with Acrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate, copoly(ethylene-vinyl acetate), polymers such as polycaprolactam and poly(hexamethylenediamine), and polyesters such as poly(etilenglikolevye) and poly(hexamethylenediisocyanate).

Unsaturated compounds can also be used as a mixture with photopolymerizable, film-forming components. They may, for example, physically drying polymers or their solutions in organic solvents, such as nitrocellulose or acetobutyrate cellulose. However, they can also be chemically and/or thermally curable (teplootdelenie) resin, examples of which are the polyisocyanates, polyepoxides and melamine resin. Use teplopoteryami resins accordingly, it is important for use in such systems (also called hybrid systems), which photopolymerizable in the first stage and then form cross-links through thermal processing in the second stage.

In hybrid systems (including anionic and radical curable components or including chemically and thermally curable components) photopolymerizable inhibitors, used to prevent premature polymerization, such as hydroquinone, hydroquinone derivatives, p-methoxyphenol,-naphthol or sterically protected phenols, such as 2,6-di-tert-butyl-p-cresol. To improve the stability during storage in the dark is possible, for example, to use copper compounds such as copper naphthenate, stearate or octoate; phosphorus compounds such as triphenylphosphine, triethylphosphite, triphenylphosphite or tribenzylphosphine. To exclude atmospheric oxygen during the polymerization in hybrid systems it is possible to add paraffin or similar wax-like substances with their inadequate solubility in the polymer migrates to the surface at the beginning of the polymerization and form a transparent surface layer which prevents the access of air. It is also possible to apply impermeable to oxygen layer. Light stabilizers that can be added in small quantity, are ultraviolet absorbers, for example hydroxyphenyltriazine, hydroxyflavanone, oxalate or type hydroxyphenyl-S-triazine. These compounds can be used individually or in mixtures with or without sterically obstructed amines (Naka ultraviolet absorbers or 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)benzotriazole; 2-(2'-hydroxy-5'-(1,1,3,3-TETRAMETHYLBUTYL)phenyl)benzotriazole, 2-(3', 5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-were)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazol, 2-(2'-hydroxy-4'-acetoxyphenyl) benzotriazol, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazol, 2-(3',5'-bis(,-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, a mixture of 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxyphenyl)phenyl-5-chlorobenzotriazol,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl] -2'-hydroxyphenyl)-5-chlorobenzotriazol,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazol,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxyphenyl)phenyl)benzotriazol,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl] -2'-hydroxyphenyl)benzotriazol,
2-(3'-dodecyl-2'-hydroxy-5'-were)benzotriazole and 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctylmercaptoacetate)phenylbenzothiazole,<-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]benzotriazole with polyethylene glycol 300;
[R-CH2CH2-COO(CH2)3]2-,
where R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-yl-phenyl.

2. 2-Hydroxybenzophenone, for example 4-hydroxy-, 4-methoxy-, 4-actoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2',4'-trihydroxy - and 2'-hydroxy-4,4'-dimethoxypropane.

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-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate and 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate.

4. Acrylates, such as isooctyl - or ethyl-- cyano-,-diphenylacetate, methyl-carbomethoxyamino, butyl or methyl-cyano--methyl-p-methoxycinnamate, methyl-carbomethoxy-p-methoxycinnamate and N-(-carbomethoxy-cyanovinyl)-2-methylindolin.

5. 2-(2-Hydroxyphenyl)-1,3,5-triazine, for example 2,4,6-T2,4-dihydroxyphenyl)-4,6-bis(2,4-dimetilfenil)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-proproxyphene)-6-(2,4-dimetilfenil)-1,3,5-triazine, 2-(2-hydroxy-4-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-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxyphenyl)phenyl] -4,6-bis(2,4-dimetilfenil)-1,3,5-triazine, 2-[4-dodecyl/tridecylamine-(2-hydroxypropyl)oxy-2-hydroxyphenyl] -4,6-bis(2,4-dimetilfenil)-1,3,5-triazine.

6. The phosphites and phosphonites, for example triphenylphosphite, diphenylacetate, phenyldichlorophosphine, Tris(nonylphenyl)FOSFA, trilaurylamine, trioctadecyl, distearyldimethylammonium, Tris(2,4-di-tert-butylphenyl)FOSFA, diisodecylphthalate, bis(2,4-di-tert-butylphenyl)pentaerythritoltetranitrate, bis(2,6-di-tert-butyl-4-were)pentaerythritoltetranitrate, bis-isodecyloxypropylamine, bis(2,4-di-tert-butyl-6-were)pentaerythritoltetranitrate, bis(2,4,6-tri-tert-butylphenyl)pentaerythritoltetranitrate, bis(2,4-di-tert-butyl-6-were)pentaerythritoltetranitrate, christianisatiori, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediisocyanate, 6-isooctane-2,4,8,10-Tetra-tert-butyl-N-dibenzo[d, g] dioxaphosphinan, 6-fluoro-tert-butyl-6-were)ethylphosphate.

Further conventional additives for compositions in accordance with the invention depending on the intended use are fluorescent whitening agents, fillers, pigments, colouring agents, moisturizing agents, agents that promote alignment, agents improving the flow and the adhesion promoters.

For curing thick and pigmented coatings should add glass beads or crushed glass, as described, for example, in patent US 5013768.

In certain cases, especially for systems containing components curable by different mechanisms, it may be preferential to add one or more other known photoinitiators (E) in addition to the component (A), for example, benzophenone, benzophenone derivatives, acetophenone derivatives of acetophenone, phenylglyoxylate, diketones (e.g., camphor quinone), anthraquinones, thioxanthones, acridine, the initiators of the electronic transition (e.g., system Borat/dye),-hydroxycyclohexanone, dialkoxybenzene,-hydroxyacetophenone, 4-aroyl-1,3-dioxolane, the benzoic alkylether and benzylacetone, monoacrylated, besatisfied, triazoles is iniciatorov: 1-(4-dodecylbenzyl)-1-hydroxy-1-mutilate, 1-(4-isopropylbenzyl)-1-hydroxy-1-mutilate, 1-benzoyl-1-hydroxy-1-mutilate, 1-[4-(2-hydroxyethoxy)benzoyl]-1-hydroxy-1-mutilate, 1-[4-acryloyloxyhexyloxy)benzoyl]-1-hydroxy-1-mutilate, diphenylmethane, phenyl-1-hydroxycyclohexyl, benzyldimethylamine, bis(cyclopentadienyl)bis(2,6-debtor-3-perispinal)titanium, complex salt of the cyclopentadienyl-ARIN-iron (II), for example6- isopropylbenzene) (5- cyclopentadienyl)iron(II)hexaflurophosphate, trimethylbenzenesulfonamide, bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-diphenoxybenzophenone or bis(2,4,6-trimethylbenzoyl)phenylphosphine.

Hence, the invention also provides for compositions which in addition to photoinitiator latent bases (A) also include at least one photoinitiator for radical polymerization (E) and/or other conventional additives.

The compounds of formula I are suitable as photosmovie generators. Accordingly, they can be used in the method for the implementation of the reactions catalyzed by bases. The method differs in that a composition as described above is irradiated with light having wavelengths of about maliciously polymerization, namely, the compound of formula I, as defined above, add as latent basis to the mixture to polymerization, and irradiated with light with a wavelength of from 200 to 700 nm to obtain a Foundation. The above method can be carried out in the presence of a sensitizer selected from the group of carbonyl compounds having a triplet energy 225-310 kJ/mol. Such sensitizers described above and is referred to as component (C) new song.

In some cases, it is preferable to heat the composition during or after irradiation. Reaction cross connection can often be accelerated, so in another of its aspects the invention relates to a method of curing compositions, including
(A) a compound of the formula I on p. 1,
(B) at least one epoxy compound and at least one compound able to react with epoxides in the presence of a base, and
(C) optionally a sensitizer, which
(1) said composition is irradiated with light having a wavelength of from 200 to 700 nm, for getting the basics of the catalyst of the photosensitive previous product of formula I and
(2) sequentially thermally utverjdayut using as CA is camping in the range of from about 200 to 700 nm. A suitable irradiation is, for example, in sunlight or light from artificial sources. Therefore, apply a large number of light sources of very different types. Suitable as point sources and the grid ("lamp carpets). Examples are coal arc lamps, xenon arc lamps, medium -, high-and low-pressure mercury lamps, possibly with the addition of the halide of the metal (metal-halogen lamps), lamps with pairs of metals microwave excitation lamp excitation, superactivity fluorescent tubes, fluorescent lamps, argon lamps with gas mantle grid, e-light, photographic lamps, electron beams and x-rays, produced by means of synchrotrons or laser plasma. The distance between the lamp and the substrate subject exposure, in accordance with the invention, may vary depending on the intended application, and the type and output of the lamp and can be from 2 to 150, see Laser light sources, for example laser excitation, are particularly suitable. Lasers in the visible area can also be used. In this case, the high sensitivity of the new materials is predominant in a high degree. Posrednie printing plates or relief printing plates, as well as photographic materials, fixing the image.

The temperature for thermal stage (2) can be in the range from ambient temperature (about 25o(C) to 180oC. the Preferred temperature range depends on the specific reaction catalyzed by bases. For example, acid/epoxy systems temperature range is from 70 to 160oFor epoxy/thiol reaction temperature range is from ambient temperature to 120oC.

The invention relates also to a method as described above, in which phase thermal curing (2) should the phase selection (3).

Selection means removing parts of the composition without cross-linking. Specialists in this field are familiar with the proper methods of allocation.

It is also possible to carry out the above method in such a way that for photochemical phase (1) should the phase selection (3) to phase thermal curing (2), or in such a way that the phases (1), (2) and (3) second phase thermal curing (4).

May be, of course, added additional basic catalyst, different from the compounds of formula I, or a predecessor product of such a catalyst composition as with the derivatives of triazine, derivatives of guanidine. Specific examples are 2PHZ, 2E4MZ-CNS (imidazole derivatives firm Shikoky Chemicals), acetogenin, benzoguanamine, dicyandiamide. The use of these thermal catalysts are described, for example, in patents US 4943516, JP 7-278266, JP 1-141904, JP 3-71137, JP 6-138655, JP 5-140251, JP 6-67430, JP 3-172317, JP 6-161108, JP 7-26183.

Since the compounds of formula I also apply as a radical photoinitiator, as mentioned above, the method can also be carried out in a hybrid system, namely a mixture of anionic and radical curable component. Accordingly, in this method, the composition may further include radically polimerizarii monomer, oligomer or polymer (D).

Generators fotonovelas, in accordance with the invention is particularly useful in applications that require high thermal stability and/or good solvent resistance, low electrical conductivity, good mechanical properties in the case of, for example, solder resists, conformational coating, wrapping devices, stereolithography, etc.

In addition, they are useful for photoformable compositions, using the mechanism, catalyzed by bases or dual curing (radical and anionic), where

The invention also provides for compositions comprising in addition to components (a) and (b) at least one ethyleneamine photopolymerization connection, which is emulsified, dispersion or dissolved in water.

Curing by irradiation of aqueous dispersion of prepolymers of this type are commercially available in numerous variants. The use of the term refers to the water dispersion and at least one prepolymer dispersed in it. The concentration of water in these systems is, for example, from 5 to 80% by weight, in particular from 30 to 60%. Cured by the irradiation of the prepolymers or a mixture of prepolymers are, for example, in concentrations of from 95 to 25% by weight, in particular from 70 to 40%. The total percentage specified for water and prepolymers in these compositions, in each case 100, to which add auxiliary materials and additives in different amounts depending on the intended application.

Curing radiation vododispersionnaya film-forming prepolymers which are also often dissolved to aqueous dispersions prepolymers presents monofunctional or polyfunctional prepolymers which are known and as such the s double bonds per 100 g of prepolymer, and have an average molecular weight of, for example, at least 400, in particular from 500 to 10000. However, depending on the intended use of the prepolymers having a large molecular weight, could also be suitable.

For example, the use of polyesters containing paliperidonesee double bond C-C and having a maximum acid number of 10, polyethers containing paliperidonesee double bonds, hydroxyl-containing reaction products of polyepoxide containing at least two epoxy groups per molecule, with at least one,-Ethylenediamine carboxylic acid; polyurethane (meth)acrylates and,-Ethylenediamine acrylic copolymers containing acrylic radicals, as described in published application for the European patent EP-A-12339. Mixtures of these polymers can also be used. Also suitable paliperidonesee the prepolymers described in EP-A-33896, which are thioester products attach polymerizing prepolymers having an average molecular weight of at least 600, and the content of carboxyl groups is from 0.2 the water dispersion on the basis of specific alkyl(meth)acrylate prepolymers described in EP-A-41125; suitable water-dispersible radiation-curable prepolymers obtained from urethaneacrylate, are disclosed in DE-A-2936039.

Soluble in water or present in the water resistnace compositions are described, for example in JP-A 4-169985, JP-A 4-169986, JP-A 4-169987 and JP-A 4-31361.

These radiation-curable aqueous dispersion of prepolymers can include as additional additives, auxiliary agents, dispersion, emulsifying agents, antioxidants, light stabilizers, dyes, pigments, fillers, such as talc, gypsum, silica, rutile, carbon clean, zinc oxide and iron oxides, reaction accelerators, leveling agents, lubricants, moisturizing agents, agents building, the agents to obtain a matte surface that devalues agents and other auxiliary materials that are conventional in coating technology. Suitable auxiliary substances in the dispersion are water-soluble organic compounds of high molecular weight that contain polar groups, such as polyvinylene alcohols, polyvinylpyrrolidone and cellulose ethers. Emulsifiers which can be used are nonionic emulsifiers and, probably, also ionic emulsifiers.

Compositions in accordance with from the Oia can be based on the described compositions of resins, including hybrid systems. Powder coating, UV-curable, can be formed by mixing polymers with carboxylic acid groups with epoxides and add vodoosnovnykh generators (or their mixtures). Hybrid powder coatings can also be formed by adding solid resins and monomers containing reactive double bonds, the polymer bearing groups of carboxylic acids and epoxides and photosmovie generators (alone or in combination with radical initiators). Resins and monomers containing reactive double bonds, represented, for example, maleate, vinyl ethers, acrylates, acrylamide and their mixtures. Powder coating can also include a binder, as described, for example, in DE-A-4228514 and in EP-A-636669. Powder coating can additionally include white or color pigments. For example, titanium dioxide, preferably rutelinae form of titanium dioxide, may be applied in concentrations up to 50% by weight to give otverzhdennom powder coating good covering ability. The procedure usually involves electrostatic or tribostatic powder on the substrate, for example metal or wood, rasplavlyaemymi light, using, for example, mercury lamps, medium-pressure, metal-Galenia lamp or a xenon lamp. The irradiation may be conducted when the coated product is still warm, to accelerate curing, but it is also possible irradiation after cooling and the second thermal treatment (in a separate section or after Assembly of the various parts). A particular advantage of powder coatings, radiation-curable, compared to their thermoset counterparts, is that the time elapsed after the melting of the powder particles may be delayed, if it is desirable to provide education of a smooth high-gloss coating. In contrast to thermoset systems, powder coatings, radiation-curable, can be left to melt at low temperatures without the undesirable effect of reducing their working life. For this reason, they are also suitable as coatings for heat-sensitive substrates, such as wood or plastics. In addition, the powder coating compositions may also include ultraviolet absorbers and other additives. Relevant examples are listed above.

Photopolymerizable compositions can be used for different purposes, which I of wood or metal, as a coating material, inter alia for paper, wood, plastic or metal, as powder coating, curing in daylight coverage for road markings and layouts of buildings, technologies for photographic reproduction, for holographic recording materials, for the technology to record images or for the production of printing plates, which can be manifested by organic solvents or aqueous alkalis, for producing masks for printing stencil can be used as compositions for dental fillings, as adhesives, including adhesives, pressure-sensitive, as the layer of resin, as resists etching or permanent resists, as well as the solder mask and otobrazhenii dielectrics for electronic circuits, for the production of bulk products by mass curing (curing UV transparent forms) or by the stereolithography technology for the production of composite materials and other thick-layered compositions, for coating or sealing electronic components or as coatings for optical fibers.

In the hybrid coating curing systems, the hour is correctly include monounsaturated monomer. It is prepolymer here sets the properties of the covering film, and by changing it, you can influence the properties utverzhdenii film. Polyunsaturated agent functions as a cross-linking agent, which makes the film insoluble. Monounsaturated monomer functions as a reactive diluent, which is used to reduce the viscosity without the use of solvent.

New fototerapia compositions are suitable, for example, as roofing materials for substrates of all kinds, for example wood, textiles, paper, ceramics, glass, plastics, such as etioplast, polyethylene terephthalate, polyolefins or cellulose acetate, especially in the form of films, and also metals such as A1, si, Ni, Fe, Zn, Mg or Co and GaAs, and Si or SiO2that is scheduled to apply a protective layer or by exposure with the image to obtain a reproduced image.

The coating substrate can be performed by applying on the substrate a liquid composition, solution or suspension. The choice of solvent and concentration depends in principle on the type of composition and technology coverage. The solvent should be inert, i.e. it must not undergo chemical reaction with the components and the debtor is th are ketones, the simple esters and complex esters such as ethyl ketone, isobutylmethylxanthine, Cyclopentanone, cyclohexanone, dioxane, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 1,2-dimethoxyethane, ethyl acetate, n-butyl acetate and ethyl-3-ethoxypropionate.

The solution is applied uniformly to a substrate by known coating technologies, such as spin coating, coating by dipping, knife coating, curtain coating, brush coating, spraying, especially by electrostatic spraying and reversal-Nakatomi coating and by electrophoretic deposition. It is also possible to apply the photosensitive layer to a temporary flexible framework and then to coat the final substrate, for example, for a circuit Board copper coating by means of the transfer layer through the application layer.

Applied amount (coating thickness) and the nature of the substrate (support layer) depends on the desired application. The range of coating thickness includes values from ~ 0.1 micron to over 100 microns.

New sensitive to irradiation compositions have been used as negative resists, having a very high sensitivity to light and can occur in aqueous alkaline medium without Viy, the solder resist), for the production of printing plates, such as offset, flexo and removable printing plate or stencil printing and/or production of dyes for use in chemical processing or as microresist in the manufacture of integrated circuits. Possible support layers and the processing conditions, the coated substrate is installed under the appropriate changes.

Compounds according to the invention also find application for production of single-layer or multi-layer materials for recording images or reproductions of images (copies, reprografia), which may be monochromatic or polychromatic. In addition, the materials are suitable for svetozaschitnyh systems. In these technologies, it is possible to apply formulations containing microcapsules, and to obtain images for curing irradiation may be followed by heat and/or pressure treatment.

The substrates used for recording photographic information, include, for example, polyester or acetate-cellulose film, or polymer coated paper substrates to form offset printing are specially treated aluminum substrates for the production of printed circuits AVL patterns. The layer thicknesses for photographic materials and forms of offset printing ranges from ~ 0.5 to 10 μm, while for printed circuits, they range from 1 to ~ 100 ám.

After the substrate is coated, the solvent is removed usually by drying to leave the photoresist on the substrate. Temperature range depends on the specific reaction with the catalyst and must be below the temperature neotlozhnoi reaction.

The term "exposure time to the image" includes both exposure through photomask including the predetermined pattern, for example a slide, the exposure by the light beam (e.g. laser beam, which is moved along the surface of the coated substrate under computer control, producing in this way the image and the irradiation by the electron beam under computer control.

After the exposure of the material and to the manifestations may be preferential to perform heat treatment in a short time. In this case, only the exposed areas of thermally otverzhdajutsja. The temperature of this range, baking after exposure range from ambient temperature (~ 25o(C) up to 200oWith and depend on the specific reaction catalyzed by base. Site is at ambient temperature to 120oC. the Period of heat treatment is generally from 0.25 to 10 minutes.

Fototerapia the composition may further be used in the method for the production of printing plates or photoresists, such as those described, for example, in DE-A-4013358.

After exposure and heat treatment, if used, the unexposed portions of the photosensitive coating is removed with a developer by a method known in the field.

As already mentioned, new songs, among others, may occur aqueous alkalis. Especially suitable solutions aqueous-alkaline developers are aqueous solutions tetraalkylammonium hydroxides or alkali metal silicates, phosphates, hydroxides and carbonates. If desired, small amounts of wetting agents and/or organic solvents can also be added to these solutions. Examples of typical organic solvents that can be added to liquids developers in small quantities, are cyclohexanone, 2-ethoxyethanol, toluene, acetone and mixtures of such solvents.

Another area where you apply vodootvedenie, is the coating of metals, such as coating of metal plates and the second floors or walls on the basis of polyvinylchloride. Examples of fototerapia of paper coatings are colorless polishing labels, magazines and book covers.

The compositions and compounds according to the invention can be used for the production of waveguides and optical switches, which use the advantage of manifestation of the difference in refractive index between the exposed and unexposed areas.

It is also important to use fototerapia compositions technologies for imaging and optical receiving media. In such applications, as already described above, the layer (wet or dry), deposited on a support, exposed through photomask ultraviolet or visible light and the unexposed portions of the layer are removed by a solvent (developer). Application vodootvedenija layer on the metal can be carried out by electrodeposition. The exposed areas of the polymer through the cross-link and therefore insoluble and remain on the support. A corresponding color creates a visible image. When the support is a metallic layer, the metal may after exposure and manifestation to vitrales in unexposed areas or be reinforced, elektropianino provides for the use of the described compositions to obtain pigmented and non-pigmented paints and varnishes, printing inks, powder coatings, printing plates, dental compositions, waveguides, optical switches, svetozaschitnyh systems, composites, coatings, fiber glass cables, templates, screen printing, resistin materials, for photographic reproductions, for the encapsulation of electrical and electronic components, for producing magnetic recording materials, for obtaining three-dimensional objects by means of stereolithography, and as the material for recording images, especially for holographic recordings. The composition is preferably used for the production resistin materials, pripojenych masks, conformational coatings, protective coatings, powder coatings, varnishes for printed materials, coatings, optical fiber, waveguides, printing plates, adhesives, ink, templates, screen printing, reinforced composite materials, optical switches, svetozaschitnyh systems, magnetic recording media, dental materials, in stereolithography or holographic technology, as well as in technological processes for the production of resistin materials, pripojenych masks, conformational coatings, protective coatings, powder coatings, arenas print reinforced composite materials, optical switches, svetozaschitnyh systems, magnetic recording media, dental materials, either way, held as stereolithography or holographic method.

The compounds of formula I are the generators of the grounds, which can be activated photochemically and show unexpectedly excellent latency to exposure to ultraviolet light. In addition, they have high absorption in the ultraviolet region and a high catalytic activity after photodecomposition component substituted benzoyl in the molecule.

The following examples illustrate the invention in more detail. Share and interest as in other parts of the description and in the formula are given by weight, unless otherwise specified. If alkyl radicals having more than three carbon atoms, are listed without mention of specific isomers, n-isomers are implied in each case.

Example 1. Fotonovela activity. Test latency-aminoketones before irradiation and catalytic activity after irradiation.

Composition 1(a)
The composition was prepared by mixing 200 parts of polyacrylate with 3-5% carboxyl function (brand nameoWith in a minute) shows the peak temperature in 242oC.

Composition 1(b)
The composition prepared by mixing 200 parts 3-5 percent carboxyl function (Carboset from Goodrich, USA) and 100 parts of epoxy-novolak novolak (GY 1180), and 6 parts of 4-(methylthiomethyl)-1-methyl-1-morpholinoethyl (Irgacure 907, Ciba). A sample of this composition is subjected to DSC (heating rate 10oC/min). The DSC curve shows the peak temperature in 243oC. a Second sample irradiated for 40 seconds metal-galinou lamp (ORC SMX3000, 3 kW), peak at 169oC.

Composition 1(C)
The composition prepared by mixing 200 parts of polyacrylate with 3-5% carboxyl function (Carboset from Goodrich, USA) and 100 parts of epoxy-novolak novolak (GY 1180, Ciba), and 6 parts of (4-morpholinomethyl)-1-benzyl-1-dimethylaminopropane (Irgacure 369, Ciba). A sample of this composition is subjected to DSC (heating rate 10oC/min). The DSC curve shows p the IR at 152oC.

Example 2.

Part 2(a)
The composition prepared by mixing 200 parts of polyacrylate with 3-5% carboxyl function (Carboset 525), 100 parts of epoxy-novolak novolak (GY 1180) and 9 parts of 4-(methylthiomethyl)-1-methyl-1-morpholinoethyl (Irgacure 907, Ciba), and 450 parts of acetone.

Part 2(b)
The composition prepared by mixing 200 parts of polyacrylate with 3-5% carboxyl function (Carboset 525), 100 parts of epoxy-novolak novolak (GY 1180) and 9 parts of (4-morpholinomethyl)-1-benzyldimethylamine (Irgacure 369, Ciba) and 450 parts of acetone.

Samples of the compositions applied to an aluminum plate by using a core with a winding of 100 μm wire and dried in air at 50oC for 15 minutes. Received resiste layers, having a thickness of about 25 μm, densely covered with polyester foil, as it is a standardized test negative with 21 degrees of different optical density (wedge of Stiffer), and last, the top is covered with a second polyester film, and the resulting layered structure is fixed on the metal in the first series of tests, within 160 seconds in the second row and 320 seconds in the third. After irradiation the samples heated for 5 minutes at 150oIn the case of composition (a) and at 130oIn the case of part (b). Then the samples shown in ethanol in an ultrasonic bath for 5 minutes. The highest degree of lack of adhesion of the resist is determined as a measure of the sensitivity of the resist. A higher number of degrees, a large reactivity is determined by the composition of the resist. The results are summarized in table. 1.

Example 3. Fotonovela activity: test latency-aminoketones before irradiation and catalytic activity after irradiation.

Part 3(a)
200 parts of epoxy-novolak novolak (GY 1180, from Asahi CIBA, Japan), 50 parts of 4,4'-talibanzation (from Sigma-Aldrich, Japan). The DSC curve (heating rate of 10oC/min) shows a peak at a temperature of 175oC.

Part 3(b)
200 parts of epoxy-novolak novolak (GY 1180, from Asahi CIBA, Japan), 50 parts of 4,4'-talibanzation (from Sigma-Aldrich, Japan) and 6 parts of 4-(methylthiomethyl)-1-methyl-1-morpholinoethyl (Irgacure 907, Ciba). The DSC curve (heating rate of 10oC/min) shows the peak temperature 167oWith no exposure. After exposed the/p> Part 3(C)
200 parts of epoxy-novolak novolak (GY 1180, from Asahi CIBA, Japan), 50 parts of 4,4'-talibanzation (from Sigma-Aldrich, Japan) and 6 parts of 4-(morpholinomethyl)-1-benzyl-1-dimethylaminopropane (Irgacure 369, Ciba). The DSC curve (heating rate of 10oC/min) shows the peak temperature of 172oWith no exposure. After irradiation of the sample for 40 seconds metal-galinou lamp (ORC SMX3000, 3 kW) DSC curve shows a peak at 44oC.

Example 4. Fotonovela activity: test latency-aminoketones before irradiation and catalytic activity after irradiation.

Part 4(a)
200 parts of epoxy kryzanowska (ECN 1299, Asahi CIBA), 50 parts of 4,4'-cialisgenericoa (from Sigma-Aldrich, Japan). The DSC curve (heating rate of 10oC/min) shows the peak temperature of 148oC.

Part 4(b)
200 parts of epoxy kryzanowska (ECN 1299, Asahi CIBA), 50 parts of 4,4'-cialisgenericoa (from Sigma-Aldrich, Japan), 6 parts of 4-(methylthiomethyl)-1-methyl-1-morpholinoethyl (Irgacure 907, Ciba). The DSC curve (heating rate of 10oC/min) shows the peak temperature of 149oC (initial temperature of 105oC) beacasue peak at 135o(Installation temperature 50oC).

Composition 4(C)
200 parts of epoxy kryzanowska (ECN 1299, Asahi CIBA), 50 parts of 4,4'-cialisgenericoa (from Sigma-Aldrich, Japan), 6 parts of 4-(morpholinomethyl)-1-benzyl-1-dimethylaminopropane (Irgacure 369, Ciba). The DSC curve (heating rate of 10oC/min) shows the peak temperature 145oWith no exposure. After irradiation of the sample for 40 seconds metal-galinou lamp (ORC SMX3000, 3 kW) DSC curve shows a peak at 87oC.

Example 5. Fotonovela activity: test latency-aminoketones before irradiation and catalytic activity after irradiation.

Part 5 (a)
200 parts of epoxy-novolak novolak (GY 1180, Asahi CIBA), 50 parts of DL-dithiothreitol (Tokyo Kasei, Japan). The DSC curve (heating rate of 10oC/min) shows the peak temperature in 121oC.

Part 5(b)
200 parts of epoxy-novolak novolak (GY 1180, Asahi CIBA), 50 parts of DL-dithiothreitol (Tokyo Kasei, Japan), 6 parts of 4-(morpholinomethyl)-1-benzyl-1-dimethylaminopropane (Irgacure 369, Ciba). The DSC curve (heating rate of 10oC/min) shows the peak temperature of 121oWith pokazyvaet peak at 69oC.

Example 6. Fotonovela activity: test latency-aminoketones before irradiation and catalytic activity after irradiation.

Part 6(a)
200 parts of epoxy kryzanowska (ECN 1299, Asahi CIBA), 50 parts of DL-dithiothreitol (Tokyo Kasei, Japan). The DSC curve (heating rate of 10oC/min) shows the peak temperature of 138oC.

Part 6(b)
200 parts of epoxy kryzanowska (ECN 1299, Asahi, SVA), 50 parts of DL-dithiothreitol (Tokyo Kasei, Japan), 6 parts of (4-morpholinomethyl)-1-benzyl-1-dimethylaminopropane (Irgacure 369, Ciba). The DSC curve (heating rate of 10oC/min) shows the maximum temperature 135oWith no exposure. After irradiation of the sample for 40 seconds metal-galinou lamp (ORC SMX3000, 3 kW) DSC curve shows a peak at 91oC.

Example 7. Fotonovela activity: test latency-aminoketones before irradiation and catalytic activity after irradiation.

Part 7(a)
200 parts of epoxy-novolak novolak (GY1180, Asahi CIBA), 100 parts pentaerythritol(mercaptoacetate) (Tokyo Kasei, Japan). The DSC curve (heating rate of 10oC/min) shows the maximum temperature is of the ETP(mercaptoacetate) (Tokyo Kasei, Japan), 6 parts of 4-(methylthiomethyl)-1-methyl-1-morpholinoethyl (Irgacure 907, Ciba). The DSC curve (heating rate of 10oC/min) shows the peak temperature of 243oWith no exposure. After irradiation of the sample for 40 seconds metal-galinou lamp (ORC SMX3000, 3 kW) DSC curve shows a peak at 161oC.

Part 7(C)
200 parts of epoxy-novolak novolak (GY1180, Asahi CIBA), 100 parts pentaerythritol(mercaptoacetate) (Tokyo Kasei, Japan), 6 parts of (4-morpholinomethyl)-1-benzyl-1-dimethylaminopropane (Irgacure 369, Ciba). The DSC curve (heating rate of 10oC/min) shows the peak temperature of 242oWith no exposure. After irradiation of the sample for 40 seconds metal-galinou lamp (ORC SMX3000, 3 kW) DSC curve shows a peak at 124oC.

Example 8. Fotonovela activity: test latency-aminoketones before irradiation and catalytic activity after irradiation.

Composition 8(a)
200 parts of epoxy kryzanowska (ECN 1299, Asahi CIBA), 50 parts pentaerythritol(mercaptoacetate) (Tokyo Kasei, Japan). The DSC curve (heating rate of 10oC/min) shows the peak temperatutre(mercaptoacetate) (Tokyo Kasei, Japan), 6 parts of 4-(methylthiomethyl)-1-methyl-1-morpholinoethyl (Irgacure 907, Ciba). The DSC curve (heating rate of 10oC/min) shows the maximum temperature 212oWith no exposure. After irradiation of the sample for 40 seconds metal-galinou lamp (ORC SMX3000, 3 kW) DSC curve shows a peak at 167oC.

Composition 8(C)
200 parts of epoxy kryzanowska (ECN 1299, Asahi CIBA), 50 parts pentaerythritol(mercaptoacetate) (Tokyo Kasei, Japan), 6 parts of 4-(morpholinomethyl)-1-benzyl-1-dimethylamino propane (Irgacure 369, Ciba). The DSC curve (heating rate of 10oC/min) shows the peak temperature 201oWith no exposure. After irradiation of the sample for 40 seconds metal-galinou lamp (ORC SMX3000, 3 kW) DSC curve shows a peak at 124oC.

Example 9. Fotonovela activity: test latency-aminoketones before irradiation and catalytic activity after irradiation.

The following compositions are prepared by mixing parts by weight.

Composition 9(a)
200 parts of epoxy kryzanowska (ECN 1299, Asahi CIBA), 50 parts of 4,4'-cialisgenerico (from Sigma-Aldrich, Japan), 6 parts of 4-(Mohali is tetrahydrofuran.

Composition 9(b)
200 parts of epoxy kryzanowska (ECN 1299, Asahi CIBA), 50 parts of DL-dithiothreitol (Tokyo Kasei, Japan), 6 parts of 4-(morpholinomethyl)-1-benzyl-1-dimethylaminopropane (Irgacure 369, Ciba), 250 parts of tetrahydrofuran.

Composition 9(C)
200 parts of epoxy kryzanowska (ECN 1299, Asahi CIBA), 50 parts pentaerythritol(mercaptoacetate) (Tokyo Kasei, Japan), 6 parts of (4-morpholinomethyl)-1-benzyl-1-dimethylaminopropane (Irgacure 369, Ciba), 250 parts of tetrahydrofuran.

Composition 9(d)
200 parts of epoxy-novolak novolak (GY1180, Asahi CIBA), 50 parts of 4,4'-cialisgenericoa (Sigma-Aldrich, Japan), 6 parts of 4-(morpholinomethyl)-1-benzyl-1-dimethylaminopropane (Irgacure 369, Ciba), 250 parts of tetrahydrofuran.

Part 9(e)
200 parts of epoxy-novolak novolak (GY1180, Asahi, SVA), 50 parts of 4,4'-cialisgenericoa (Sigma-Aldrich, Japan), 6 parts of (4-methylthiophenyl)-1-methyl-1-morpholinoethyl (Irgacure 907, Ciba), 150 parts of tetrahydrofuran.

Part 9(f)
200 parts of epoxy-novolak novolak (GY1180, Asahi, SVA), 50 parts of DL-dithiothreitol (Tokyo Kasei, Japan), 6 parts of (4-morpholinobutyrophenone.

Compounds 9(a)-9(f) applied to an aluminum plate covering the core with wire wound {a thickness of 50 μm in the wet state for compositions (a)-(C) and 36 μm for compounds (d) to(f)} and dried in air at 45oC for 10 minutes.

Received resiste layers of a thickness of about 23 μm and 18 μm for compounds (a)-(C) and (d)-(f) respectively cover piroplasmosis film and irradiated for 320 seconds 3-kW metal-galinou lamp that is installed at a distance of 60 cm

After irradiation the samples heated at different curing conditions after exposure (listed in table. 2). The samples show a mixture of ethanol and methyl ethyl ketone (1:1) in an ultrasonic bath.

The higher the degree, the better the efficiency of the curing composition. The resulting sensitivities are listed in table. 2.

Similar results are achieved when using compounds with radicals of different chemical nature, are presented in table. 3.


Claims

1. Composition, including
(A) 0.1 to 20% by weight of the composition, of at least one compound-aminoacetophenone as a latent curing catalyst �D/img_data/63/633360.gif">
where R5group-OR17, -SR18, -N(R19)(R20);
R6is hydrogen, halogen or C1-C4alkyl or has one of the meanings indicated for R5;
R7and R8is hydrogen or halogen;
R9is hydrogen;
R1and R2each independently of one another are
(a)1-C6the alkyl,
(b) a radical of the formula

(d) a radical of the formula - CH(R13)-AG2;
where AG2radical of phenyl, which is unsubstituted or substituted with halogen, C1-C4the alkyl, methylthio, methoxy or benzoyl;
R3and R4each independently of one another-C1-C12alkyl, C2-C4alkyl, substituted C1-C4alkoxy, -CN, or-COO(C1-C4alkyl), or R3and R4- allyl, cyclohexyl or benzyl; or R3and R4together With4-With6alkylene, which may be interrupted by-O-;
R13, R14, R15and R16each independently of one another is hydrogen or methyl;
R17is unsubstituted or SH-substituted C1-C4alkyl, 2-hydroxyethyl, 2-methoxyethyl, 2-allyloxymethyl, allyl, cyclohexyl, phenyl or benzyl;
R18is hydrogen, nezamedin, or p-tolyl or benzyl; and
R19and R20each independently of one another - C1-C12alkyl, C2-C6alkoxyalkyl, acetyl, allyl or benzyl, or R19and R20together With4-C6alkylene, which may be interrupted by-O-;
(B) at least one epoxy compound and at least one compound able to react with the epoxy compound in the presence of a base selected from a carboxyl-containing compound or thiol; and
(C) optionally from 0.01 to 5 wt. % calculated on the weight of the composition, of the sensitizer.

2. The composition according to p. 1, characterized in that component (A) is a compound of formula I where Ar1group of the formula IV in which R5group-OR17, -SR18, -N(R19)(R20); R6is hydrogen, chlorine or1-C4alkyl or has one of the meanings indicated for R5; R7and R8is hydrogen or chlorine; R9is hydrogen or C1-C4alkyl; R1or (a) a radical of the formula

(b) a radical of the formula - CH2-AG2where AG2is a radical of phenyl, which is unsubstituted or substituted with halogen, C1-C4the alkyl, CH3S-, CH3Or ub> and R4each independently of one another C1-C6alkyl, 2-methoxyethyl, allyl or benzyl; or R3and R4together With4-C6alkylene, which may be interrupted by-O-; R14and R15is hydrogen or methyl; R17is unsubstituted or SH-substituted C1-C4alkyl, 2-hydroxyethyl, 2-methoxyethyl or phenyl; R18is unsubstituted or SH-substituted C1-C12alkyl, 2-hydroxyethyl, 2-methoxyethyl, unsubstituted or SH-substituted phenyl or p-tolyl; and R19and R20- C1-C4alkyl, 2-methoxyethyl, acetyl or allyl; or R19and R20together are C4-C5alkylene, which may be interrupted by-O-.

3. The composition according to p. 1, characterized in that component (A) is a compound of formula I where Ar1group of the formula IV, where R1and R2each independently of one another are C1-C4the alkyl or benzyl; R3and R4each independently of one another are C1-C4the alkyl or together - morpholino; R5- morpholino or C1-C4alkylthio; R6, R7, R8and R9- hydrogen.

4. The composition according to p. 1, characterized in that it is used to obtain resistin materials, maskanah coatings, waveguides, printing plates, adhesives, printing inks, printing stencils, reinforced composite materials, optical switches svetozaschitnyh systems, magnetic recording media, dental materials, in stereolithography or holographic method.

5. The method of curing the composition of PP. 1-3, namely, that (1) the composition is irradiated with light having a wavelength of from 200 to 700 nm, to obtain from the photosensitive-aminoacetophenone formula I of the main catalyst type and (2) consistently armatured composition in the presence of photogenerated at the stage (1) main catalyst type.

6. The method according to p. 5, characterized in that the stage of heat (2) should stage selection (3).

7. The method according to p. 5, characterized in that at the stage of heat (2) additionally use the basic type catalyst or its predecessor product.

8. The method according to p. 5, characterized in that the stage of selection (3) after stage (1) to the stage of heat (2).

9. The method according to p. 6, characterized in that at stages (1), (2) and (3) followed by a second stage of heat (4).

10. The method according to p. 5, characterized in that the composition dopita fact, he used to get resistin materials, solder masks, conformational coatings, protective coatings, powder coatings, varnishes over print, fiberglass coatings, waveguides, printing plates, adhesives, printing inks, printing stencils, reinforced composite materials, optical switches svetozaschitnyh systems, magnetic recording media, dental materials or method carried out as stereolithography or holographic method.

 

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