JP2005154494A - Radical photopolymerization initiator and radical photopolymerizing composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly sensitive curing composition which can efficiently produce an active free radical by the irradiation of energy ray, especially light, to polymerize a free radical-curing substance in a short time. <P>SOLUTION: A radical photopolymerization initiator represented by general formula (1) (R1 and R2 are each independently a monovalent organic residue; R1 and R2 may integrally be bound to each other to form a cyclic structure; R3, R4 and R5 are each independently H or a monovalent organic residue). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polymerization initiator and a polymerizable composition using the same. In more detail, active radicals are efficiently generated by irradiation of energy rays, particularly light, and radical curable compounds are polymerized in a short time. For example, molding resins, casting resins, stereolithography resins, sealants, dental Polymerization resin, printing ink, paint, photosensitive resin for printing plate, color proof for printing, resist for color filter, resist for printed circuit board, photoresist for semiconductor, resist for microelectronics, hologram material, overcoat material, adhesive The present invention relates to a polymerization initiator for obtaining a cured product having good physical properties in the fields of adhesives, release agents, optical recording media, various devices, and the like, and a polymerizable composition using the same.

Conventionally, it is known that certain O, O′-diacylglyoximes function as photoradical polymerization initiators (see Non-Patent Documents 1 to 3). Furthermore, it is also known that certain oxime esters having a structure similar to O, O′-diacylglyoxime function as photoradical polymerization initiators (see Patent Documents 1 and 2). Further, α-ketoxime esters have been disclosed as photo radical polymerization initiators for positive or negative photosensitive polyimide precursor compositions (see Patent Document 3). Some benzophenone oxime ester compounds have been disclosed (see Patent Documents 4 and 5). Also, certain α, α-diketooxime ester compounds are disclosed (see Patent Documents 6 to 10).
In addition, certain O-acyloxime ester compounds have been disclosed (see Patent Documents 11 and 12). Also, certain O-sulfonyl oxime ester compounds and O-phosphoryl oxime ester compounds are disclosed (see Patent Document 13).
Any of these can function as a polymerization initiator, but in recent years, there has been a universal demand for higher sensitivity of the polymerization initiator in order to improve productivity and various newly proposed processes.

Journal of Polymer Science, Polymer Chemistry Edition, 1972, 10 (11), 3405-19 Journal of Polymer Science, Polymer Chemistry Edition, 1974, 12 (11), 2553-66 Sumyu Konghakhoe Chi, 1972, 9 (2), 97-110 U.S. Pat. No. 3,558,309 U.S. Pat. No. 4,255,513 JP-A-7-140,658 U.S. Pat. No. 4,590,145 JP 61-24,558 US Pat. No. 5,019,482 JP-A-62-184,056 JP-A-62-273,259 JP 62-286,961 A JP-A-62-201,859 JP 2001-233, 842 A JP 2000-80,068 Special table 2002-538, 241 gazette

  An object of the present invention is to propose a highly sensitive curable composition capable of efficiently generating active radicals by irradiation with energy rays, particularly light, and capable of polymerizing a radical curable substance in a short time. For example, industrially provide practical oligomers and polymers in the fields of inks, paints, photosensitive printing plates, proof materials, photoresists, hologram materials, sealants, overcoat materials, stereolithography resins, adhesives, etc. The object of the present invention is to provide a polymerization initiator and a polymerizable composition using the same to obtain a cured product having good characteristics.

As a result of intensive studies to solve the above problems, the present inventors have arrived at the present invention. That is, the present invention relates to a radical photopolymerization initiator represented by the following general formula (1), which has an O, O ′, O ″ -triacyltrioxime structure in which three oxime ester groups are adjacent.
General formula (1)

(However, in the formula, R 1 and R 2 each independently represents a monovalent organic residue, and R 1 and R 2 may be integrally bonded to each other. R 3, R 4 and R 5 may be Each independently represents a hydrogen atom or a monovalent organic residue.)

  Moreover, this invention relates to the polymeric composition which consists of the said radical photopolymerization initiator and a radically polymerizable compound.

  The present invention also relates to a polymerizable composition comprising the photo radical polymerization initiator, a radical polymerizable compound, and a sensitizer.

  The photoradical polymerization initiator represented by the general formula (1) of the present invention and having an O, O ′, O ″ -triacyltrioxime structure in which three oxime ester groups are adjacent is an energy ray, particularly irradiation with light. To generate active radicals efficiently. Therefore, the compound which has a remarkably favorable effect as a polymerization initiator of a polymeric substance was able to be provided.

  First, the radical photopolymerization initiator of the present invention will be described. The radical photopolymerization initiator of the present invention is characterized by having an O, O ′, O ″ -triacyltrioxime structure in which three oxime ester groups represented by the general formula (1) are adjacent. In the general formula (1), the substituents R1 and R2 represent a monovalent organic residue. The monovalent organic residue may have an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. Alkynyl group, optionally substituted alkoxy group, optionally substituted aryloxy group, optionally substituted acyloxy group, optionally substituted alkylsulfanyl group, substituted An arylsulfanyl group which may have a group, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, a substituent An arylsulfonyl group that may have, an acyl group that may have a substituent, an alkoxycarbonyl group that may have a substituent, a carbamoyl group that may have a substituent, and a substituent. Good sulfamoy Group, an optionally substituted amino group, an optionally substituted phosphinoyl group, heterocyclic group and the like may have a substituent.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Okudadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3-nitrophena Examples include a syl group.

  As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferable, and a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o- , M-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, Phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthra Nyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a ruvicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an oberenyl group.

  As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  The alkoxy group which may have a substituent is preferably an alkoxy group having 1 to 30 carbon atoms, for example, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec-butoxy group. Tert-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, ethoxycarbonylmethyl group, 2 -Ethylhexyloxycarbonylmethyloxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylaminocarbonylmethyloxy group Group, N- methyl -N- benzylaminocarbonyl methyloxy group, a benzyloxy group, and a cyanomethyloxy group.

  The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, such as a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenyloxy group, 2-methylphenyloxy group, 2-methoxyphenyloxy group, 2-butoxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3-nitrophenyloxy group, Examples include 4-fluorophenyloxy group, 4-cyanophenyloxy group, 4-methoxyphenyloxy group, 4-dimethylaminophenyloxy group, 4-methylsulfanylphenyloxy group, 4-phenylsulfanylphenyloxy group and the like.

  The acyloxy group which may have a substituent is preferably an acyloxy group having 2 to 20 carbon atoms, such as an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, or trifluoromethylcarbonyloxy. Group, benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group and the like.

  The alkylsulfanyl group which may have a substituent is preferably an alkylsulfanyl group having 1 to 20 carbon atoms. For example, a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, an isopropylsulfanyl group, a butylsulfanyl group, or a hexylsulfanyl group. Group, cyclohexylsulfanyl group, octylsulfanyl group, 2-ethylhexylsulfanyl group, decanoylsulfanyl group, dodecanoylsulfanyl group, octadecanoylsulfanyl group, cyanomethylsulfanyl group, methoxymethylsulfanyl group and the like.

  The arylsulfanyl group which may have a substituent is preferably an arylsulfanyl group having 6 to 30 carbon atoms, such as a phenylsulfanyl group, 1-naphthylsulfanyl group, 2-naphthylsulfanyl group, 2-chlorophenylsulfanyl group, 2-methylphenylsulfanyl group, 2-methoxyphenylsulfanyl group, 2-butoxyphenylsulfanyl group, 3-chlorophenylsulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-nitrophenylsulfanyl group, 4-fluorophenylsulfanyl group, 4-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, 4-phenylsulfanylphenylsulfuric group Aniru group, 4-dimethylamino-phenylsulfanyl group and the like.

  The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms. For example, a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, and a hexylsulfinyl group. Group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methoxymethylsulfinyl group and the like.

  The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, such as a phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfuric group Iniru group, 4-dimethylaminophenyl sulfinyl group and the like.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. For example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group. Group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group and the like.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminopheny Sulfonyl group, and the like.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl. Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyl. Oxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4- Phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group Group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group , 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group and the like.

  The carbamoyl group which may have a substituent is preferably a carbamoyl group having 1 to 30 carbon atoms, for example, an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N-propylcarbamoyl group, or an N-butylcarbamoyl group. N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N-2- Chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanophenyl A carbamoyl group, -4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N -Dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group and the like.

  The sulfamoyl group which may have a substituent is preferably a sulfamoyl group having 0 to 30 carbon atoms, for example, a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, N, N- Examples thereof include a dialkylsulfamoyl group, an N, N-diarylsulfamoyl group, and an N-alkyl-N-arylsulfamoyl group. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like.

The amino group which may have a substituent is preferably an amino group having 0 to 50 carbon atoms in total, for example, —NH ₂ , N-alkylamino group, N-arylamino group, N-acylamino group, N— Examples include sulfonylamino group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, N, N-disulfonylamino group, and the like. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, Nt-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino Group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3-cyanophenylamino group, N-3-trifluoromethylphenylamino group, -4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenylamino group, N-4-phenylsulfanylphenylamino group, N- 4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-dibutylamino group, N, N-diphenylamino group, N N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) amino group, N N- (dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group and the like.

  The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms, for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphinoyl group. Group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group and the like.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H- Quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group Group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

  Furthermore, the alkyl group which may have a substituent mentioned above, the aryl group which may have a substituent, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, a substituent An alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an acyloxy group which may have a substituent, an alkylsulfanyl group which may have a substituent, and a substituent An arylsulfanyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent. An arylsulfonyl group, an optionally substituted acyl group, an optionally substituted alkoxycarbonyl group, an optionally substituted carbamoyl group, an optionally substituted sulfamoyl group, Amino group which may have a group, hydrogen atom of the heterocyclic group which may have a substituent may be further substituted with other substituents.

  Examples of such substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryl groups such as phenoxy group and p-tolyloxy group. Alkoxy groups such as oxy group, methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, An acyl group such as a methoxalyl group, an alkylsulfanyl group such as a methylsulfanyl group or a tert-butylsulfanyl group, an arylsulfanyl group such as a phenylsulfanyl group or a p-tolylsulfanyl group, an alkylsulfuryl group such as a methylamino group or a cyclohexylamino group; Killamino, dimethylamino, diethylamino, morpholino, piperidino and other dialkylamino groups, phenylamino, p-tolylamino and other arylamino groups, methyl, ethyl, tert-butyl, dodecyl, etc. In addition to aryl groups such as alkyl groups, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, etc., hydroxy groups, carboxy groups, formyl groups, mercapto groups, sulfo groups, mesyl groups , P-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammoniumumyl group, dimethylsulfoniumumyl group, triphenylphenacylphospho And niumyl group.

  Furthermore, some of the substituents for R 1 and R 2 may be linked by a covalent bond.

  These substituents R1 and R2 preferably have an alkyl group which may have a substituent, an aryl group which may have a substituent, an acyl group which may have a substituent, and a substituent. Good heterocyclic groups and the like can be mentioned. More preferably, at least one of R 1 and R 2 is an aryl group. Specifically, methyl group, ethyl group, butyl group, 4-dimethylaminophenyl group, 4-phenylsulfanylphenyl group, 4-methoxy-1-naphthyl group, 4-phenylsulfanylbenzoyl group, 4-methoxy-1- Examples thereof include a naphthoyl group and an N-ethyl-3-carbazoyl group, but the present invention is not limited to these examples.

  The substituents R3, R4 and R5 in the general formula (1) each independently represent a hydrogen atom or a monovalent organic residue. Examples of the monovalent organic residue include those exemplified as the organic residues of R1 and R2. R3, R4 and R5 may be the same substituent or different substituents.

These substituents R3, R4 and R5 preferably have an alkyl group which may have a substituent, an aryl group which may have a substituent, an acyl group which may have a substituent, and a substituent. Phosphinyl group and the like, which may be included, more preferably methyl group, ethyl group, trifluoromethyl group, phenyl group, acetyl group, benzoyl group, diphenylphosphinyl group and the like. It is not limited to.
Therefore, as a specific example of the photo radical polymerization initiator corresponding to the present invention,

(R1 = alkyl, R2 = alkyl, R3, R4, R5 = no limitation)
O, O ′, O ″ -triacetyl-5,6,7-undecantrione trioxime, O, O ′, O ″ -triacetyl-5,10-diethyl-7,8,9-tetradecanetrione trioxime, O, O ′, O ″ -triacetyl-2,7-nonadiene-4,5,6-trione trioxime, O, O ′, O ″ -tripropionyl-1,2,3-cyclohexanetrione trioxime, O , O ′, O ″ -tribenzoyl-1,2,3-cycloheptanetrione trioxime,

(R1 = alkyl, R2 = aryl, R3, R4, R5 = no limitation)
O, O ′, O ″ -triacetyl-1-phenyl-1,2,3-butanetrione trioxime, O, O ′, O ″ -triacetyl-1- (1-naphthyl) -1,2, 3-butanetrione trioxime, O, O ′, O ″ -triacetyl-1-phenyl-1,2,3-pentanetrione trioxime, O, O ′, O ″ -triacetyl-1- (4-phenyl) Sulfanylphenyl) -1,2,3-butanetrione trioxime, O, O ′, O ″ -triacetyl-1- (4-methoxy-1-naphthyl) -1,2,3-pentanetrione trioxime, O, O ′, O ″ -tripropionyl-1-phenyl-1,2,3-butanetrione trioxime, O, O ′, O ″ -tributyryl-1-phenyl-1,2,3-butanetrione trioxime, O , O ′, O ″ -Triisobutyryl-1-phenyl-1,2,3-pentanthrio Trioxime, O, O ′, O ″ -trivaleryl-1- (4-phenylsulfanylphenyl) -1,2,3-pentanetrione trioxime, O, O ′, O ″ -trihexanoyl-1- (4 -Phenylsulfanylphenyl) -1,2,3-hexanetrione trioxime, O, O ′, O ″ -trioctanoyl-1- (4-phenylsulfanylphenyl) -1,2,3-butanetrione trioxime, O , O ′, O ″ -tridecanoyl-1- (4-ethoxy-1-naphthyl) -1,2,3-butanetrione trioxime, O, O ′, O ″ -trilauroyl-1- (4-ethoxy -1-naphthyl) -1,2,3-pentanetrione trioxime, O, O ′, O ″ -triacetyl-1- (9-anthryl) -1,2,3-butanetrione trioxime, O, O ′ , O ″ -triacetyl-1- (1-pyrenyl) -1 , 2,3-Butanetrione trioxime, O, O ′, O ″ -triacetyl-1- (4-biphenyl) -1,2,3-butanetrione trioxime, O, O ′, O ″ -triacetyl -1- (2-Naphtyl) -3-phenacyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -tripropionyl-1- (p-tolyl) -1,2,3-hexane Trione trioxime, O, O ′, O ″ -bis (trifluoromethylcarbonyl) -1- (4-phenylsulfanylphenyl) -1,2,3-butanetrione trioxime, O, O ′, O ″ -tri Acetyl-1- (2,4,6-trimethylphenyl) -1,2,3-butanetrione trioxime,

(R1 = aryl, R2 = aryl, R3, R4 = alkyl)
O, O ′, O ″ -triacetyl-1- (4-phenylsulfanylphenyl) -3-phenyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -triacetyl-1- (1-Naphtyl) -3-phenyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -triacetyl-1- (1-naphthyl) -3-biphenyl-1,2,3- Propanetrione trioxime, O, O ′, O ″ -triacetyl-1- (1-naphthyl) -3- (p-tolyl) -1,2,3-propanetrione trioxime, O, O ′, O ″ -Triacetyl-1- (4-methoxy-1-naphthyl) -3-phenyl-1,2,3-propanetrione trioxime, O, O ', O''-tripropionyl-1- (2-naphthyl)- 3- (2-Naphtyl) -1,2,3-propanetrione trioxime, O, O ′, O ″ -triacetyl- -(1-naphthyl) -3- (4-phenylsulfanylphenyl) -1,2,3-propanetrione trioxime, O, O ', O''-trioctanoyl-1- (4-methylsulfanylphenyl)- 3-phenyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -triacetyl-1- (4-methoxyphenyl) -3-phenyl-1,2,3-propanetrione trioxime, O , O ′, O ″ -triacetyl-1,3-bis (4-dimethylaminophenyl) -1,2,3-propanetrione trioxime,

(R1 = aryl, R2 = aryl, R3, R4, R5 = aryl)
O, O ′, O ″ -tribenzoyl-1- (4-phenylsulfanylphenyl) -3-phenyl-1,3-propanetrione trioxime, O, O ′, O ″ -tribenzoyl-1,2, 3-bis (1-naphthyl) -1,3-propanetrione trioxime, O, O ′, O ″ -tri (2-methylbenzoyl) -1,3-bis (4-dimethylaminophenyl) -1,2 , 3-propanetrione trioxime,

(R1 = aryl, R2 = aryl, R3, R4, R5 = acyl)
O, O ′, O ″ -tri (acetylcarbonyl) -1,2,3-diphenyl-1,2,3-ethanetrione trioxime, O, O ′, O ″ -tri (acetylcarbonyl) -1- (1-naphthyl) -2-phenyl-1,2,3-ethanetrione trioxime, O, O ′, O ″ -tri (acetylcarbonyl) -1- (4-methoxyphenyl) -2-phenyl-1, 2,3-ethanetrione trioxime, O, O ′, O ″ -tri (acetylcarbonyl) -1- (4-cyanophenyl) -2-phenyl-1,2,3-ethanetrione trioxime, O, O ′ , O ″ -tri (acetylcarbonyl) -1- (4-trifluoromethylphenyl) -2- (1-naphthyl) -1,2,3-ethanetrione trioxime, O, O ′, O ″ -tri (Acetylcarbonyl) -1- (4-dimethylaminophenyl) -2-phenyl-1,2,3-ethane Rion trioxime, O, O ′, O ″ -tri (acetylcarbonyl) -1- (4-phenylsulfanylphenyl) -2- (4-methoxyphenyl) -1,2,3-ethanetrione trioxime, O, O ', O ″ -tri (benzoylcarbonyl) -1- (4-phenylsulfanylphenyl) -2-phenyl-1,2,3-ethanetrione trioxime, O, O ′, O ″ -tri (acetylcarbonyl) -1- (4-Methoxy-1-naphthyl) -2- (4-biphenyl) -1,2,3-ethanetrione trioxime, O, O ′, O ″ -tri (acetylcarbonyl) -1- (4 -Phenylsulfanylphenyl) -2- (1-naphthyl) -1,2,3-ethanetrione trioxime,

(R1 = aryl, R2 = aryl, R3, R4, R5 = phosphinyl)
O, O ′, O ″ -tris (diphenylphosphinoyl) -1,3-diphenyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -tris (diethoxyphosphinoyl) -1- (1-naphthyl) -3-phenyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -tris (dimesitylphosphinoyl) -1- (4-methoxy-1 -Naphthyl) -3-phenyl-1,2,3-propanetrione trioxime, O, O ', O''-tris (diphenylphosphinoyl) -1- (4-phenylsulfanylphenyl) -3- (4- Diethylaminophenyl) -1,2,3-propanetrione trioxime, O, O ′, O ″ -tris (diphenylphosphinoyl) -1- (4-dimethylaminophenyl) -3- (1-naphthyl) -1 , 2,3-propanetrione trioxime, O, O ′, O ″ -tris ( Phenylphosphinoyl) -1- (4-cyanophenyl) -3- (2-naphthyl) -1,2,3-propanetrione trioxime, O, O ′, O ″ -tris (diphenylphosphinoyl)- 1- (3-cyanophenyl) -3-phenyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -tris (diphenylphosphinoyl) -1- (3-trifluoromethylphenyl) -3-phenyl-1,2,3-propanetrione trioxime,

(R1 = aryl, R2 = alkenyl, R3, R4, R5 = no limitation)
O, O ′, O ″ -triacetyl-1- (1-naphthyl) -3-vinyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -triacetyl-1- (4 -Butoxyphenyl) -3-allyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -triacetyl-1- (1-naphthyl) -3-styryl-1,2,3-propane Trione trioxime, O, O ′, O ″ -tribenzoyl-1- (4-methoxy-1-naphthyl) -3-allyl-1,2,3-propanetrione trioxime, O, O ′, O ″ — Tri (acetylcarbonyl) -1- (1-naphthyl) -3-allyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -tris (diphenylphosphinoyl) -1- (1- Naphthyl) -3-vinyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -tris (trifluoro Methylcarbonyl) -1- (2-naphthyl) -3-allyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -triacetyl-1- (4-phenylsulfanylphenyl) -3- Vinyl-1,2,3-propanetrione trioxime,

(R1 = aryl, R2 = alkynyl, R3, R4, R5 = no limitation)
O, O ′, O ″ -triacetyl-1- (4-phenylsulfanylphenyl) -3-ethynyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -triacetyl-1- (4-phenylsulfanylphenyl) -3-propynyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -triacetyl-1- (4-phenylsulfanylphenyl) -3-propargyl-1, 2,3-propanetrione trioxime, O, O ′, O ″ -tribenzoyl-1- (1-naphthyl) -3-ethynyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -Bis (acetylcarbonyl) -1- (4-methoxy-1-naphthyl) -3-propynyl-1,2,3-propanetrione trioxime, O, O ', O''-bis (diphenylphosphinoyl)- 1- (4-Cyanophenyl) -3-propa Lugyl-1,2,3-propanetrione trioxime,

(R1 = aryl, R2 = alkoxy, R3, R4, R5 = no limitation)
O, O ′, O ″ -triacetyl-1- (4-phenylsulfanylphenyl) -3-methoxy-1,2,3-propanetrione trioxime, O, O ′, O ″ -triacetyl-1- (4-phenylsulfanylphenyl) -3-ethoxy-1,2,3-propanetrione trioxime, O, O ′, O ″ -triacetyl-1- (4-phenylsulfanylphenyl) -3-propoxy-1, 2,3-propanetrione trioxime, O, O ′, O ″ -triacetyl-1- (4-phenylsulfanylphenyl) -3-butoxy-1,2,3-propanetrione trioxime, O, O ′, O '' -Triacetyl-1- (4-phenylsulfanylphenyl) -3-octyloxy-1,2,3-propanetrione trioxime, O, O ', O''-triacetyl-1- (4-phenylsulfanyl) Phenyl)- -Dodecyloxy-1,2,3-propanetrione trioxime, O, O ', O''-tribenzoyl-1- (4-phenylsulfanylphenyl) -3-methoxy-1,2,3-propanetrione trioxime, O, O ′, O ″ -tris (acetylcarbonyl) -1- (4-phenylsulfanylphenyl) -3-ethoxy-1,2,3-propanetrione trioxime, O, O ′, O ″ -bis ( Diphenylphosphinoyl) -1- (4-phenylsulfanylphenyl) -3-methoxy-1,2,3-propanetrione trioxime,

(R1 = aryl, R2 = aryloxy, R3, R4, R5 = no limitation)
O, O ′, O ″ -triacetyl-1- (4-phenylsulfanylphenyl) -3-phenoxy-1,2,3-propanetrione trioxime, O, O ′, O ″ -tribenzoyl-1- (4-Phenylsulfanylphenyl) -3-phenoxy-1,2,3-propanetrione trioxime, O, O ′, O ″ -bis (acetylcarbonyl) -1- (4-phenylsulfanylphenyl) -3-phenoxy -1,2,3-propanetrione trioxime, O, O ′, O ″ -tris (diphenylphosphinoyl) -1- (4-phenylsulfanylphenyl) -3-phenoxy-1,2,3-propanetrione Trioxime,

(R1 = aryl, R2 = acyloxy, R3, R4, R5 = no limitation)
O, O ′, O ″ -triacetyl-1- (4-phenylsulfanylphenyl) -3-benzoyloxy-1,2,3-propanetrione trioxime, O, O ′, O ″ -tribenzoyl-1 -(1-Naphthyl) -3-acetyloxy-1,2,3-propanetrione trioxime, O, O ', O''-triacetylcarbonyl-1- (4-methoxyphenyl) -3-propanoyloxy- 1,2,3-propanetrione trioxime, O, O ′, O ″ -bis (diphenylphosphinoyl) -1- (4-methoxy-1-naphthyl) -3-trifluoromethylcarbonyloxy-1,2 , 3-propanetrione trioxime,

(R1 = aryl, R2 = alkylsulfanyl, R3, R4, R5 = no limitation)
O, O ′, O ″ -triacetyl-1- (4-methoxyphenyl) -3-methylsulfanyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -tribenzoyl-1- (4-Phenylsulfanylphenyl) -3-ethylsulfanyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -triacetylcarbonyl-1- (1-naphthyl) -3-butylsulfanyl-1 , 2,3-propanetrione trioxime, O, O ′, O ″ -bis (diphenylphosphinoyl) -1- (4-phenylsulfanylphenyl) -3-methylsulfanyl-1,2,3-propanetrione trioxime ,

(R1 = aryl, R2 = arylsulfanyl, R3, R4, R5 = no limitation)
O, O ′, O ″ -triacetyl-1- (4-phenylsulfanylphenyl) -3-phenylsulfanyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -tribenzoyl-1 -(4-Methoxy-1-naphthyl) -3- (1-naphthylsulfanyl) -1,2,3-propanetrione trioxime, O, O ', O''-triacetylcarbonyl-1-phenyl-3- ( 2-methoxyphenylsulfanyl) -1,2,3-propanetrione trioxime, O, O ′, O ″ -bis (diethoxyphosphinoyl) -1- (1-naphthyl) -3- (3-cyanophenyl Sulfanyl) -1,2,3-propanetrione trioxime,

(R1 = aryl, R2 = alkylsulfinyl, R3, R4, R5 = no limitation)
O, O ′, O ″ -tripropanoyl-1- (4-phenoxyphenyl) -3-methylsulfinyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -tribenzoyl-1 -(4-Phenylsulfanylphenyl) -3-ethylsulfinyl-1,2,3-propanetrione trioxime, O, O ', O''-tripropanoylcarbonyl-1- (2-naphthyl) -3-butylsulfinyl -1,2,3-propanetrione trioxime, O, O ′, O ″ -tris (diphenylphosphinoyl) -1- (4-dimethylaminophenyl) -3-methylsulfinyl-1,2,3-propane Trion trioxime,

(R1 = aryl, R2 = arylsulfinyl, R3, R4, R5 = no limitation)
O, O ′, O ″ -triacetyl-1- (4-diethylaminophenyl) -3-phenylsulfinyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -tribenzoyl-1- Phenyl-3- (1-naphthylsulfinyl) -1,2,3-propanetrione trioxime, O, O ′, O ″ -triacetylcarbonyl-1- (4-phenylsulfanylphenyl) -3- (3-nitro Phenylsulfinyl) -1,2,3-propanetrione trioxime, O, O ′, O ″ -bis (dimesitylphosphinoyl) -1- (p-tolyl) -3- (2-naphthylsulfinyl)- 1,2,3-propanetrione trioxime,

(R1 = aryl, R2 = alkylsulfonyl, R3, R4, R5 = no limitation)
O, O ′, O ″ -tris (trifluoromethylcarbonyl) -1- (4-dibutylaminophenyl) -3-methylsulfonyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -Tribenzoyl-1- (2-naphthyl) -3-ethylsulfonyl-1,2,3-propanetrione trioxime, O, O ', O''-triacetylcarbonyl-1- (3-cyanophenyl) -3 -Butylsulfonyl-1,2,3-propanetrione trioxime, O, O ', O''-tris (diphenylphosphinoyl) -1- (4-methylsulfanylphenyl) -3-octylsulfonyl-1,2, 3-propanetrione trioxime,

(R1 = aryl, R2 = arylsulfonyl, R3, R4, R5 = no limitation)
O, O ′, O ″ -triacetyl-1-phenyl-3-phenylsulfonyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -tribenzoyl-1- (1-naphthyl) -3- (1-naphthylsulfonyl) -1,2,3-propanetrione trioxime, O, O ′, O ″ -tripropanoylcarbonyl-1- (4-methylsulfanylphenyl) -3-phenylsulfonyl-1 , 2,3-propanetrione trioxime, O, O ′, O ″ -tris (diphenylphosphinoyl) -1-phenyl-3- (4-cyanophenylsulfonyl) -1,2,3-propanetrione trioxime,

(R1 = aryl, R2 = acyl, R3, R4, R5 = no limitation)
O, O ′, O ″ -triacetyl-1- (4-phenylsulfanylphenyl) -3-acetyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -tribenzoyl-1- (4-Dimethylaminophenyl) -3- (1-naphthoyl) -1,2,3-propanetrione trioxime, O, O ′, O ″ -triacetylcarbonyl-1- (4-methoxy-1-naphthyl) -3-Benzoyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -tris (diethoxyphosphinoyl) -1- (4-cyanophenyl) -3- (4-dimethylaminobenzoyl) ) -1,2,3-propanetrione trioxime, O, O ′, O ″ -triacetyl-1- (4-phenylsulfanylphenyl) -3- (4-methoxy-1-naphthoyl) -1,2, 3-propanetrione trioxime, O, O ', O''-tri Cetyl-1- (4-phenylsulfanyl-phenyl) -3- (trifluoromethyl carbonyl) -1,2,3-propane trione Toriokishimu,

(R1 = alkyl, R2 = acyl, R3, R4, R5 = no limitation)
O, O ′, O ″ -triacetyl-1-benzoyl-1,2,3-pentanetrione trioxime, O, O ′, O ″ -tribenzoyl-1- (4-diphenylaminobenzoyl) -1, 2,3-hexanetrione trioxime, O, O ′, O ″ -triacetyl-1- (1-naphthoyl) -1,2,3-pentanetrione trioxime, O, O ′, O ″ -tris (di Benzoylphosphinoyl) -1- (3-cyanobenzoyl) -1,2,3-heptanetrione trioxime,

(R1 = aryl, R2 = alkoxycarbonyl, R3, R4, R5 = no limitation)
O, O ′, O ″ -triacetyl-1- (1-naphthyl) -3-methoxycarbonyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -tribenzoyl-1- ( 4-phenylsulfanylphenyl) -3-ethoxycarbonyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -triacetylcarbonyl-1- (4-diethylaminophenyl) -3-phenoxycarbonyl-1 , 2,3-propanetrione trioxime, O, O ′, O ″ -tris (diethoxyphosphinoyl) -1- (3-cyanophenyl) -3- (1-naphthyloxy) carbonyl-1,2, 3-propanetrione trioxime,

(R1 = aryl, R2 = carbamoyl, R3, R4, R5 = no limitation)
O, O ′, O ″ -tributanoyl-1- (4-phenylsulfanylphenyl) -3- (N, N-dimethylcarbamoyl) -1,2,3-propanetrione trioxime, O, O ′, O ″ -Tribenzoyl-1- (4-ethoxy-1-naphthyl) -3- (N, N-diphenylcarbamoyl) -1,2,3-propanetrione trioxime, O, O ', O''-tripropanoylcarbonyl -1-phenyl-3- (N-3-cyanophenylcarbamoyl) -1,2,3-propanetrione trioxime, O, O ′, O ″ -bis (dimesitylphosphinoyl) -1-phenyl- 3- (N, N-dimethylcarbamoyl) -1,2,3-propanetrione trioxime,

(R1 = aryl, R2 = sulfamoyl, R3, R4, R5 = no limitation)
O, O ′, O ″ -diacetyl-1- (1-naphthyl) -3- (N, N-dimethylsulfamoyl) -1,2,3-propanetrione trioxime, O, O ′, O ″ -Tribenzoyl-1- (4-biphenyl) -3- (N, N-diphenylsulfamoyl) -1,2,3-propanetrione trioxime, O, O ', O''-triacetylcarbonyl-1- (4-Phenylsulfanylphenyl) -3- (N-methyl-N-phenylsulfamoyl) -1,2,3-propanetrione trioxime, O, O ′, O ″ -bis (diethoxyphosphinoyl) -1- (4-dimethylaminophenyl) -3- (N, N-diethylsulfamoyl) -1,2,3-propanetrione trioxime,

(R1 = aryl, R2 = amino, R3, R4, R5 = no limitation)
O, O ′, O ″ -triacetyl-1-phenyl-3- (N, N-diphenylamino) -1,2,3-propanetrione trioxime, O, O ′, O ″ -tribenzoyl-1 -(2-Naphtyl) -3- (N, N-dimethylamino) -1,2,3-propanetrione trioxime, O, O ', O''-triacetylcarbonyl-1- (4-phenylsulfanylphenyl) -3- (N, N-ditolylamino) -1,2,3-propanetrione trioxime, O, O ', O''-tris (diphenylphosphinoyl) -1- (4-methylphenyl) -3- ( N, N-dibutylamino) -1,2,3-propanetrione trioxime,

(R1 = aryl, R2 = phosphinoyl, R3, R4, R5 = no limitation)
O, O ′, O ″ -triacetyl-1- (4-phenylsulfanylphenyl) -3- (dibenzoylphosphinoyl) -1,2,3-propanetrione trioxime, O, O ′, O ″ -Tribenzoyl-1- (1-naphthyl) -3- (diethoxyphosphinoyl) -1,2,3-propanetrione trioxime, O, O ', O''-triacetylcarbonyl-1-phenyl-3 -(Dimesitylphosphinoyl) -1,2,3-propanetrione trioxime, O, O ', O''-triacetyl-1- (4-dimethylaminophenyl) -3- (dibenzoylphosphinoyl ) -1,2,3-propanetrione trioxime,

(R1 = alkyl, R2 = phosphinoyl, R3, R4, R5 = no limitation)
O, O ′, O ″ -Tripropanoyl-1- (dibenzoylphosphinoyl) -1,2,3-pentanetrione trioxime, O, O ′, O ″ -triacetylcarbonyl-1- (di Mesitylphosphinoyl) -1,2,3-heptanetrione trioxime, O, O ′, O ″ -tribenzoyl-1- (diphenylphosphinoyl) -1,2,3-hexanetrione trioxime, O, O ′, O ″ -triacetyl-1- (diethoxyphosphinoyl) -1,2,3-pentanetrione trioxime,

(R1 = aryl, R2 = heterocycle, R3, R4, R5 = no limitation)
O, O ′, O ″ -triacetyl-1- (4-dimethylaminophenyl) -3- (2-thienyl) -1,2,3-propanetrione trioxime, O, O ′, O ″ -tri Benzoyl-1-phenyl-3- (N-ethyl-3-carbazolyl) -1,2,3-propanetrione trioxime, O, O ′, O ″ -triacetylcarbonyl-1-phenyl-3- (2- Thioxanthryl) -1,2,3-propanetrione trioxime, O, O ′, O ″ -triacetyl-1- (p-tolyl) -3- (N-ethyl-6-benzoyl-3-carbazolyl) -1,2,3-propanetrione trioxime,

(R1 = alkyl, R2 = heterocycle, R3, R4, R5 = no limitation)
O, O ′, O ″ -triacetyl-1- (N-ethyl-3-carbazolyl) -1,2,3-pentanetrione trioxime, O, O ′, O ″ -tribenzoyl-1- (N -Ethyl-3-phenothiazinyl) -1,2,3-nonanetrione trioxime, O, O ′, O ″ -triacetylcarbonyl-1- (N-ethyl-2-acridinyl) -1,2,3-pentane Trione trioxime, O, O ′, O ″ -bis (dibenzoylphosphinyl) -1- (N-ethyl-3-carbazolyl) -1,2,3-heptanetrione trioxime,

(R1 = acyl, R2 = heterocycle, R3, R4, R5 = no limitation)
O, O ′, O ″ -triacetyl-1- (N-ethyl-3-carbazolyl) -3-benzoyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -tribenzoyl- 1- (N-ethyl-3-phenothiazinyl) -3-acetyl-1,2,3-propanetrione trioxime, O, O ′, O ″ -triacetyl-1- (2-thioxanthryl) -3 -(1-Naphthoyl) -1,2,3-propanetrione trioxime, O, O ', O''-bis (dimesitylphosphinyl) -1- (3-phenoxathiinyl) -3-propanoyl -1,2,3-propanetrione trioxime,
However, the present invention is not limited to these examples.
Specific examples of the photoradical polymerization initiator of the present invention described above include the following compounds (wherein Me represents a methyl group and Et represents an ethyl group).

The starting material for synthesizing the photoradical polymerization initiator represented by the general formula (1) is a trioxime represented by the general formula (2).

(式中Ｒ１，Ｒ２は一般式（１）と同義である。) General formula (2)

(Wherein R1 and R2 have the same meanings as in general formula (1).)

  The trioxime represented by the general formula (2) is, for example, Chem. Ber., 50, <1917>, 952, Chem. Ber., 22, <1889>, 540, edited by The Chemical Society of Japan, 4th edition experiment. It can be obtained by various methods by applying the synthesis method of glyoxime described in Chemical Lecture, Vol. 14, p. 1326 (Maruzen). Furthermore, it can also be obtained from applications of oxime synthesis methods described in commercial chemistry texts (eg, J. March, Advanced Organic Organic Chemistry, 4th Edition, Wiley Interscience, 1992).

  One of the most convenient methods for synthesizing oximes is the reaction of ketones with hydroxylamine or salts thereof in a polar solvent such as ethanol or aqueous ethanol. In this case, it is well known to add a base such as sodium hydroxide or sodium acetate to adjust the pH of the reaction mixture. The rate of this reaction is pH dependent and the base can be added initially or continuously during the reaction. A basic solvent such as pyridine is used as the base and / or solvent or co-solvent. The reaction temperature is generally the boiling point temperature of the mixture, usually 60 to 120 ° C., but depending on the substrate, it reacts even at room temperature. Another convenient synthesis of oximes is nitrosation of active methylene groups with nitrous acid or alkyl nitrites. Both alkaline conditions are described for example in Organic Syntheses Coll. Vol. VI (J. Wiley & Sons, New York, 1988), pp 199 and 840, and acidic conditions are described for example in Organic Syntheses Coll. Vol. pp 32 and 373, Organic Syntheses Coll. Vol. III, pp 191 and 513, Organic Syntheses Coll. Vol. II, pp 202, 204 and 363, and is suitable for the production of oximes. Nitrous acid is usually produced from sodium nitrite. The nitrite alkyl ester is, for example, methyl nitrite, isopropyl nitrite, butyl nitrite, isoamyl nitrite.

  The radical photopolymerization initiator represented by the general formula (1) is prepared by using a trioxime represented by the general formula (2) as a starting material, for example, an oxime and an acyl chloride obtained by the above-described method, By reacting with an acid anhydride in an inert solvent such as tetrahydrofuran, benzene or dimethylformamide, in the presence of a base such as a tertiary amine such as triethylamine, or in a basic solvent such as pyridine. Manufactured.

  Such reactions are known to those skilled in the art and are generally carried out at -15 ° C to + 50 ° C, preferably 0-30 ° C.

All oxime ester groups exist in two configurations, (Z) or (E). The isomers can be separated by conventional methods, but mixtures of isomers can also be used as photoinitiating species. The invention therefore also relates to a mixture of configurational isomers of the compound of general formula (1).
The photoradical polymerization initiator represented by the general formula (1) of the present invention can be identified by elemental analysis values and ¹ H-NMR.

  Many of these photo-radical polymerization initiators of the general formula (1) usually do not exhibit absorption at wavelengths longer than the ultraviolet region, and thus are poor in activity from near ultraviolet to near infrared light. Absorption band in the visible region by introducing condensed polycyclic aromatic ring groups such as 4-methoxynaphthyl group, 4-phenylsulfanylphenyl group, anthranyl group, phenanthryl group, anthryl group, pyrenyl group and other suitable substituents It is possible to have activity even in the region of longer wavelength than visible.

  In addition, by combining with a sensitizer that absorbs light from ultraviolet to near infrared, the activity for light from the ultraviolet to the near infrared region is enhanced, and an extremely sensitive polymerizable composition is obtained. Is possible.

  Specific examples of such sensitizers include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, and fluorene derivatives. , Naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, Oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzopo Filin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives , Spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, etc. Other specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al. The dyes and sensitizers described in “Chemistry of Sexual Dyes” (1981, CMC), edited by Tadasaburo Ikemori, “Special Functional Materials” (1986, CMC), are not limited thereto. Without Other dyes and a sensitizer exhibiting absorbs light of over the near infrared region can be mentioned the ultraviolet, it may be used two or more in an arbitrary ratio, if these are required. Among the sensitizers described above, a thioxanthone derivative may be mentioned as a sensitizer that can particularly preferably sensitize the photopolymerization initiator of the present invention. More specific examples include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, and the like. However, it is not limited to these.

Further, the radical polymerizable compound in the polymerizable composition of the present invention is a compound having an ethylenically unsaturated bond capable of radical polymerization, and the compound having an ethylenically unsaturated bond capable of radical polymerization is contained in the molecule. Any compound may be used as long as it has at least one ethylenically unsaturated bond capable of radical polymerization, and it has a chemical form such as a monomer, an oligomer or a polymer. These may be used alone or may be a system in which two or more kinds are mixed at an arbitrary ratio in order to improve the intended characteristics.

  Examples of such a compound having an ethylenically unsaturated bond capable of radical polymerization include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and their salts, esters, Examples include urethane, amides and anhydrides, acrylonitrile, styrene, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes, and other radical polymerizable compounds, but the present invention is not limited thereto. It is not something.

  Specifically, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, butoxyethyl acrylate, carbitol acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, benzyl acrylate, bis (4-acryloxypolyethoxyphenyl) butane, neo Pentyl glycol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol diacrylate , Pentaerythritol triacrylate, pentaerythritol Acrylic acid derivatives such as tetraacrylate, dipentaerythritol tetraacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, N-methylolacrylamide, diacetoneacrylamide, epoxy acrylate, methyl methacrylate, N-butyl methacrylate, 2-hexyl methacrylate, benzyl methacrylate, dimethylaminomethyl methacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, trimethylolethane trimethacrylate , Trimethylol group Methacrylic acid derivatives such as pantrimethacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, and other derivatives of allyl compounds such as allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. More specifically, edited by Shinzo Yamashita et al., “Cross-linking agent handbook” (1981, Taiseisha), Kiyoto Kato, “UV / EB curing handbook (raw material)”, (1985, Polymer publication society) ), Radtech Study Group, “Application and Market of UV / EB Curing Technology”, 79, (1989, CMC), Akamatsu Kiyoshi, “New Technology for Photosensitive Resins”, (1987, C MC), written by Takiyama Shinichiro, “Polyester Resin Handbook”, (1988, Nikkan Kogyo Shimbun) Examples include radically polymerizable or crosslinkable monomers, oligomers, and polymers.

  The radical photopolymerization initiator represented by the general formula (1) of the present invention is preferably 0.01 to 30 parts by weight, more preferably 100 parts by weight of the compound having an ethylenically unsaturated bond capable of radical polymerization. Is 0.1 to 10 parts by weight.

  The polymerizable composition of the present invention can be used by mixing with a binder such as an organic polymer and applying it to a polymer film such as a glass plate, an aluminum plate, another metal plate, or polyethylene terephthalate.

  Examples of binders that can be used by mixing with the polymerizable composition of the present invention include polyacrylates, poly-α-alkyl acrylates, polyamides, polyvinyl acetals, polyformaldehydes, polyurethanes, polycarbonates, polystyrenes, Examples thereof include polymers and copolymers such as polyvinyl esters, and more specifically, polymethacrylate, polymethyl methacrylate, polyethyl methacrylate, polyvinyl carbazole, polyvinyl pyrrolidone, polyvinyl butyral, polyvinyl acetate, novolac resin, phenol resin, Epoxy resin, alkyd resin, etc., supervised by Kiyoshi Akamatsu, “New Photosensitive Resin Technology” (1987, CMC) and “10188 Chemical Products”, pages 657-767 (1988, Chemical Industries Day) Company) industry known organic polymer described, and the like.

  Furthermore, the polymerizable composition of the present invention may be used by adding the following carboxyl group-containing polymer for the purpose of use as a photoresist material for image formation. Since the carboxyl group-containing polymer has solubility in an alkaline aqueous solution, if the film prepared using the photopolymerizable composition of the present invention is partially cured, a so-called negative resist pattern is formed due to the difference in solubility in the alkaline aqueous solution. Can be formed. Here, the carboxyl group-containing polymer includes a copolymer of acrylic acid ester or methacrylic acid ester and acrylic acid, or a copolymer of methacrylic acid ester, methacrylic acid and a vinyl monomer copolymerizable therewith. . These copolymers may be used alone or in combination of two or more.

  Here, as the methacrylic acid ester, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, etc. Is mentioned.

  Methacrylic acid ester, methacrylic acid and vinyl monomers copolymerizable therewith include tetrahydrofurfuryl acrylate, dimethylaminoethyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, 2,2,3, Examples include 3-tetrafluoropropyl acrylate, tetrahydrfurfuryl methacrylate, dimethylaminoethyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, acrylamide, and styrene.

  The polymerizable composition of the present invention can be used in combination with other polymerization initiators for the purpose of further improving sensitivity.

  Examples of other polymerization initiators that can be used in combination with the polymerizable composition of the present invention include triazine derivatives described in JP-B-59-1281, JP-B-61-9621, and JP-A-60-60104. Organic peroxides described in JP-A-59-1504 and JP-A-61-243807, JP-B-43-23684, JP-B-44-6413, JP-B-47-1604 and USP No. 3567453, diazonium compound gazette, USP 2,848,328, USP 2,852,379 and USP 2,940,853, organic azide compounds, JP-B 36-22062, JP-B 37-13109 Disclosed in Japanese Patent Publication No. SHO 38-18015 and SHO 45-9610. Luto-quinonediazides, including iodonium compounds described in JP-B-55-39162, JP-A-59-140203 and “MACROMOLECULES”, Vol. 10, page 1307 (1977) Various onium compounds, azo compounds described in JP-A-59-142205, JP-A-1-54440, European Patent No. 1099851, European Patent No. 126712, “Journal of Imaging Science” (J.IMAG.SCI.), Vol. 30, page 174 (1986), titanocenes described in JP-A No. 61-151197, “COORDINATION CHEMISTRY REVIEW 84), 85-277 (1988) and JP-A-2- Transition metal complexes containing transition metals such as ruthenium described in 82701, Aluminate complexes described in JP-A-3-209477, Borate compounds described in JP-A-2-157760, JP-A-55-127550 And 2,4,5-triarylimidazole dimer described in JP-A-60-202437, carbon tetrabromide and organic halogen compounds described in JP-A-59-107344, JP-A-5-255347. Sulfonium complex or oxosulfonium complex described in JP-A No. 2001-264530, JP-A No. 2001-261661, JP-A No. 2000-80068, JP-A No. 2001-233842, US Pat. No. 3,558,309 (1971). ), USP 4202697 (1980) and special Examples include oxime ester compounds described in JP-A 61-24558, and these polymerization initiators are in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of a compound having an ethylenically unsaturated bond capable of radical polymerization. It is preferable to contain.

  In addition, a thermal polymerization inhibitor can be added to the polymerizable composition of the present invention for the purpose of preventing polymerization during storage.

  Specific examples of the thermal polymerization inhibitor that can be added to the polymerizable composition of the present invention include p-methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol, tert-butylcatechol, phenothiazine, and the like. The polymerization inhibitor is preferably added in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the compound having an ethylenically unsaturated bond capable of radical polymerization.

The polymerizable composition of the present invention can further contain a polymerization accelerator represented by amine, thiol, disulfide and the like, a chain transfer catalyst, etc. for the purpose of further promoting the polymerization.

Specific examples of the polymerization accelerator and chain transfer catalyst that can be added to the polymerizable composition of the present invention include, for example, amines such as N-phenylglycine, triethanolamine, N, N-diethylaniline, USP No. 4414312 Thiols described in the specification, JP-A No. 64-13144, disulfides described in JP-A No. 2-291561, thiones described in USP No. 3558322 and JP-A No. 64-17048, Examples include O-acylthiohydroxamate and N-alkoxypyridinethiones described in JP-A-2-291560.

  Further, the polymerizable composition of the present invention can be used depending on the purpose, such as dyes, organic and inorganic pigments, phosphine, phosphonate, phosphite and other oxygen scavengers and reducing agents, antifoggants, antifading agents, antihalation agents, fluorescent enhancers. Whitening agents, surfactants, colorants, extenders, plasticizers, flame retardants, antioxidants, UV absorbers, foaming agents, fungicides, antistatic agents, magnetic substances and other additives that impart various properties Further, it may be used by mixing with a diluting solvent or the like.

  In the polymerization reaction, the polymerizable composition of the present invention can be polymerized by application of energy such as ultraviolet rays, visible rays, near infrared rays, electron beams, etc. to obtain a desired polymer. The definitions of ultraviolet rays, near-ultraviolet rays, visible light, near-infrared rays, infrared rays, and the like referred to in this specification are based on “Iwanami Rikagaku Dictionary 4th Edition” (1987, Iwanami) edited by Ryogo Kubo et al.

Therefore, the polymerizable composition of the present invention includes a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an argon ion laser, a helium cadmium laser, and helium. Neon laser, krypton ion laser, various semiconductor lasers, YAG laser, light emitting diode, CRT light source, plasma light source, electron beam, gamma ray, ArF excimer laser, KrF excimer laser, F2 laser, etc. Polymer or cured product can be obtained.

  Therefore, various inks, various printing plate materials, photoresists, electrophotography, direct printing plate materials, photosensitive materials such as hologram materials and various recording media such as microcapsules, and adhesives, which are coated on a substrate together with a binder and the like, It can be applied to pressure-sensitive adhesives, adhesives, sealants and various paints.

(Function)
The photo-radical polymerization initiator represented by the general formula (1) of the present invention has a tris- (O-acyl) trioxime structure in which an oxime ester group is adjacent, and is excited and decomposed by irradiation with energy rays, particularly light. This is considered to generate free radicals efficiently. At the same time, crystallinity and solubility in organic solvents can be improved, thereby obtaining good stability.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated in detail, this invention is not limited only to the following.

Synthesis example 1
Synthesis of O, O ′, O ″ -triacetyl-1,3-diphenyl-1,2,3-propanetrione trioxime (compound (1)) 1,3-diphenyl-1,2,3-propanetrione trioxime To a stirred solution of 0.34 g (1.26 mmol) and 1.04 g (12.64 mmol) of sodium acetate in 10 ml of tetrahydrofuran, 0.52 g (5.056 mmol) of acetic anhydride was added and heated to reflux for 20 hours. Thereafter, the reaction solution was poured into 100 g of ice water, the crude product was extracted with ethyl acetate, dried over anhydrous magnesium sulfate and concentrated, and the residue was recrystallized with ethyl acetate / hexane to obtain 0.21 g as white crystals. . The structure was identified by ¹ H-NMR.
¹ H-NMR spectrum (DMSO-d6) δ [ppm]: 1.98 (s, 3H), 1.99 (s, 3H), 2.23 (s, 3H), 7.51-7.77 (m, 10H).

Synthesis Examples 2-20
Compounds (2) to (20) shown in Table 1 were produced from the corresponding trioxime according to the method described in Synthesis Example 1 using the corresponding acid anhydride or acyl chloride.

Examples 1-20
6 parts by weight of the radical photopolymerization initiator shown in Table 2, 100 parts by weight of pentaerythritol triacrylate which is a compound having an ethylenically unsaturated bond capable of radical polymerization, and 20 parts by weight of polymethyl methacrylate as a binder, A polymerizable composition comprising 1600 parts by weight of cyclohexanone as a solvent was blended to prepare a coating solution. This coating solution was applied to a glass plate using a spin coater and dried in an oven at 40 ° C. for 10 minutes. The film thickness after removing the solvent by drying was about 1.5 μm. The polymerizable composition layer was irradiated with light from a high pressure mercury lamp to give an energy of 200 mJ / cm ² . The results of evaluating the tack of the film after light irradiation are also shown in Table 2.

Table 2

Examples 21-40
6 parts by weight of a radical photopolymerization initiator shown in Table 3, 100 parts by weight of pentaerythritol triacrylate which is a compound having an ethylenically unsaturated bond capable of radical polymerization, and 20 parts by weight of polymethyl methacrylate as a binder, A polymerizable composition consisting of 1600 parts by weight of cyclohexanone as a solvent and 3 parts by weight of compound (21) shown in Table 4 as a sensitizer was blended to prepare a coating solution. This coating solution was applied to a glass plate using a spin coater and dried in an oven at 40 ° C. for 10 minutes. The film thickness after removing the solvent by drying was about 1.5 μm. The polymerizable composition layer was irradiated with light from a high-pressure mercury lamp through a band-pass filter that selectively transmits light of 350 to 380 nm, to give energy of 200 mJ / cm ² . Table 3 also shows the results of evaluating the tack of the film after light irradiation.

Table 3

Table 4

Examples 41-43, Comparative Examples 1-4
6 parts by weight of the radical photopolymerization initiator shown in Table 4, 100 parts by weight of pentaerythritol triacrylate which is a compound having an ethylenically unsaturated bond capable of radical polymerization, 100 parts by weight of polymethyl methacrylate as a binder, A polymerizable composition comprising 1600 parts by weight of cyclohexanone as a solvent was blended to prepare a coating solution. This coating solution was applied onto a stainless steel plate using a spin coater and dried in an oven at 40 ° C. for 10 minutes. The film thickness after removing the solvent by drying was about 1.5 μm. A polyvinyl alcohol aqueous solution was applied on the polymerizable composition layer and dried in an oven at 40 ° C. for 10 minutes. The film thickness of the polyvinyl alcohol layer after drying was about 5 μm. The IR spectrum of the polymerizable composition layer was applied to the coated material while irradiating light (5.0 mW / cm ² ) of a high-pressure mercury lamp through a bandpass filter that selectively transmits light of 350 to 380 nm. The (reflection) was measured and the intensity of 810 cm ⁻¹ , which is the characteristic absorption of the acrylic group, was monitored.
Based on the IR measurement results, Table 5 shows the results of calculating the ratio of acrylic groups consumed by polymerization at the time point 60 seconds after the start of light irradiation, based on the pre-light irradiation.

Table 5

Examples 44-46, Comparative Examples 5-7
6 parts by weight of the radical photopolymerization initiator shown in Table 4, 100 parts by weight of pentaerythritol triacrylate which is a compound having an ethylenically unsaturated bond capable of radical polymerization, 100 parts by weight of polymethyl methacrylate as a binder, A polymerizable composition consisting of 1600 parts by weight of cyclohexanone as a solvent and 3 parts by weight of the compound (25) as a sensitizer was blended to prepare a coating solution. This coating solution was applied onto a stainless steel plate using a spin coater and dried in an oven at 40 ° C. for 10 minutes. The film thickness after removing the solvent by drying was about 1.5 μm. A polyvinyl alcohol aqueous solution was applied on the polymerizable composition layer and dried in an oven at 40 ° C. for 10 minutes. The film thickness of the polyvinyl alcohol layer after drying was about 5 μm. The IR spectrum of the polymerizable composition layer was applied to the coated material while irradiating light (5.0 mW / cm ² ) of a high-pressure mercury lamp through a bandpass filter that selectively transmits light of 350 to 380 nm. The (reflection) was measured and the intensity of 810 cm ⁻¹ , which is the characteristic absorption of the acrylic group, was monitored.
Based on the IR measurement results, Table 6 shows the results of calculating the ratio of acrylic groups consumed by polymerization at the time point 60 seconds after the start of light irradiation, based on the pre-light irradiation.

Table 6

  In the case of using a photoradical polymerization initiator represented by the general formula (1) of the present invention and having an O, O ′, O ″ -triacyltrioxime structure in which three oxime ester groups are adjacent, known O, O ′ -It turns out that the sensitivity is improving all compared with the case where diacyl glyoxime and oxime ester are used as radical photopolymerization initiator.

Claims (3)

A radical photopolymerization initiator represented by the following general formula (1).
General formula (1)

(However, in the formula, R1 and R2 each independently represent a monovalent organic residue, and R1 and R2 may be bonded together to form a cyclic structure. R3, R4 and R5 may be Each independently represents a hydrogen atom or a monovalent organic residue.) 2. A polymerizable composition comprising the photo radical polymerization initiator according to claim 1 and a radical polymerizable compound. 2. A polymerizable composition comprising the photo radical polymerization initiator according to claim 1, a radical polymerizable compound, and a sensitizer.