JP3278307B2 - Photopolymerizable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photopolymerizable composition. More specifically, the present invention relates to a photopolymerizable composition comprising a photopolymerization initiation system having a novel composition having excellent photosensitivity to visible light.

[0002]

2. Description of the Related Art A photopolymerizable composition is a material which causes a change in physical properties of a composition as a result of a polymerization reaction caused by light irradiation.
It is used in a wide range of fields, such as paints, inks, hologram recording, and three-dimensional modeling, and its applications are expanding more and more. The composition basically comprises an addition-polymerizable ethylenically unsaturated compound and a photopolymerization initiator. Since this type of composition causes a polymerization reaction by light irradiation, and cures and becomes insoluble, a photosensitive composition obtained by further adding a binder resin having a film forming ability, a thermal polymerization inhibitor, and the like to the composition as necessary. Make an object into a suitable film, irradiate light through the desired negative image,
A desired cured image can be formed by removing only the non-irradiated portion with an appropriate solvent (hereinafter simply referred to as development). It is well known that such an image forming method is extremely useful as a method used when preparing a printing plate or the like.

As the photopolymerization initiator in the polymerizable composition, benzyl, benzoin ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone and the like have been used. However, the composition comprising these photopolymerization initiators has a low photosensitivity, and has a very low photopolymerization ability with respect to visible light having a wavelength of 400 nm or more as compared with the photopolymerization ability with respect to light in an ultraviolet wavelength region of 400 nm or less. Therefore, the application range of the conventional photopolymerizable composition comprising a photopolymerization initiator has been extremely limited.

[0004] Further, a photosensitive composition which can obtain high curing with a small amount of light irradiation has long been desired. that is,
For example, it is useful as a photosensitive material suitable for non-contact projection exposure. In recent years, an image forming technique using a visible laser has been put into practical use, and a photosensitive composition having a high photopolymerization ability with respect to visible light has been strongly desired. As the visible laser light, a method using 488 nm wavelength light of an Ar ⁺ laser, 532 nm wavelength light of a YAG-SHG laser, and the like is considered promising.

Several proposals have been made for a photopolymerization composition comprising a photopolymerization initiation system sensitive to visible light. For example, according to U.S. Pat. No. 2,850,445, certain photosensitive dyes such as Rose Bengal,
It has been reported that eosin, erythrosin, and the like have effective visible light sensitivity. Further, as an improved technique, a complex initiation system of a dye and an amine (Japanese Patent Publication No. 44-20189),
Hexaarylbiimidazole with a radical generator and a dye (JP-B-45-37377) and hexaarylbiimidazole with a p-dialkylaminobenzylidene ketone (JP-B-47-2528, JP-A-54-15)
No. 5292), a system of a 3-ketocoumarin compound and an active halogen compound (JP-A-58-15503), and a system of a substituted triazine and a merocyanine dye (JP-A-54-15102).
No.) have been proposed. While these techniques are effective for visible light, they are not sensitive enough from a practical standpoint. JP-A-2-244050 proposes a system comprising a dye having a 4-thiazolidinone skeleton and a radical generator as a highly sensitive starting system. Although this system was indeed highly sensitive, it was still not practical enough and improvements were desired. Further, with regard to the dye, its low compatibility with other components constituting the composition has been a major obstacle in practical use. That is, as a result, the concentration of the dye added to the light-sensitive material is limited to a low level, and the dye precipitates during storage of the material, which causes an undesirable change in characteristics such as deterioration of photosensitivity. .

[0006]

It is an object of the present invention to provide a highly sensitive photopolymerizable composition. That is,
It is an object of the present invention to broadly provide a photopolymerizable composition containing a photopolymerization initiator which generally increases the photopolymerization rate of a photopolymerizable composition containing an addition-polymerizable ethylenically unsaturated compound. Another object of the present invention is to include a photopolymerization initiator which has high sensitivity to visible light of 400 nm or more, especially to light near 488 nm and 532 nm corresponding to the output of an Ar ⁺ laser or a YAG-SHG laser. It is to provide a photopolymerizable composition. Still another object is to provide a photopolymerizable composition having excellent storage stability as a photosensitive material.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, the photopolymerizable composition containing a specific photopolymerization initiation system has an extremely high photopolymerization rate. The present invention has been found to exhibit high photosensitivity to visible light of 400 nm or more and to have excellent storage stability, and has reached the present invention.

That is, the present invention provides the following components (i) to (ii)
It is a photopolymerizable composition characterized by containing i). i) a compound having at least one ethylenically unsaturated bond capable of addition polymerization; ii) a general formula [I]

[0009]

Embedded image

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁹ ,
R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group,
Substituted aryl group, hydroxyl group, substituted oxy group, mercapto group, substituted thio group, amino group, substituted amino group, substituted carbonyl group, sulfo group, sulfonato group, substituted sulfinyl group, substituted sulfonyl group, phosphono group, substituted phosphono group, Represents a phosphonate group, a substituted phosphonate group, a cyano group or a nitro group, or represents R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² is may form an aliphatic or aromatic ring bonded to each other, R ⁵ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, R ⁶ is substituted, Or represents an unsubstituted alkenylalkyl group, an alkynylalkyl group, an alkenyl group, or an alkynyl group,
R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group or a substituted carbonyl group), and iii) the component ( An activator that generates an active radical by light irradiation in the presence of (ii).

Hereinafter, each component of the photopolymerizable composition of the present invention will be described in detail. The compound having at least one addition-polymerizable ethylenically unsaturated bond of the component (i) used in the present invention is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. For example, monomer, prepolymer, ie, 2
It has a chemical form such as a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof. Examples of monomers and copolymers thereof include esters of unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with aliphatic polyhydric alcohol compounds, and unsaturated esters. Examples include amides of carboxylic acids and aliphatic polyamine compounds.

Specific examples of the ester monomer of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3.
-Butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate , 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate , So Bi penta acrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer.

Examples of the methacrylate include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol. Dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3- Methacryloxy-2-hi Rokishipuropokishi) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Examples of the itaconic acid ester include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
There are 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, sorbitol tetritaconate and the like.

The crotonates include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate,
Sorbitol tetradicrotonate and the like. Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

The maleic acid ester includes ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate and the like. Furthermore, a mixture of the above-mentioned ester monomers can also be mentioned. Specific examples of the amide monomer of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis −
Examples include methacrylamide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, and xylylenebismethacrylamide.

As another example, see Japanese Patent Publication No. 48-417.
08 polyisocyanate compound having two or more isocyanate groups in one molecule described in
A vinyl urethane compound having two or more polymerizable vinyl groups in one molecule to which a hydroxyl group-containing vinyl monomer represented by the following formula (D) is added is exemplified.

CH ₂ ＣC (R) COOCH ₂ CH (R ′) OH (D) (where R and R ′ represent H or CH ₃ )
Also, urethane acrylates described in JP-A-51-37193, JP-A-48-64183.
No., JP-B-49-43191, JP-B-52-3049
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin and (meth) acrylic acid as described in JP-A Nos. 0-104, and 2005-122131 can be used. Further, those described as photocurable monomers and oligomers in the Journal of the Adhesion Society of Japan, Vol. 1, 20, No. 7, pages 300-308 (1984) can be used. In addition, the use amount of these is 5 to 50% by weight based on all components.
(Hereinafter abbreviated as%), preferably 10 to 40%.

The component (ii) used in the present invention is a compound represented by the aforementioned general formula [I].

In the general formula [I], R ¹ , R ² , R ³ ,
Examples of R ⁴ are shown below. Examples of the alkyl group include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group, undecyl group, dodecyl group, tridecyl group,
Hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, Examples include a cyclohexyl group, a cyclopentyl group, and a 2-norbornyl group. Among these, straight-chained from 1 to 12 carbon atoms, branched from 3 to 12 carbon atoms, and 5 to 5 carbon atoms
And from 10 to 10 cyclic alkyl groups are more preferred.

As a substituent of the substituted alkyl group, hydrogen is
A monovalent non-metallic atomic group excluding is used, and as a preferable example,
Represents a halogen atom (-F, -Br, -Cl, -I),
Droxyl group, alkoxy group, aryloxy group, merka
Group, alkylthio group, arylthio group, alkyldi
Thio group, aryldithio group, amino group, N-alkyl
Mino group, N, N-dialkylamino group, N-aryla
Mino group, N, N-diarylamino group, N-alkyl-
N-arylamino group, acyloxy group, carbamoyl
Oxy group, N-alkylcarbamoyloxy group, N-A
Reel carbamoyloxy group, N, N-dialkyl carb
Bamoyloxy group, N, N-diarylcarbamoylo
Xy group, N-alkyl-N-arylcarbamoyloxy
Groups, alkylsulfoxy groups, arylsulfoxy groups,
Silthio group, acylamino group, N-alkyl acylamido
Group, N-arylacylamino group, ureido group, N '
-Alkyl ureido group, N ', N'-dialkyl urea
Group, N'-arylureido group, N ', N'-diali
Ureido group, N'-alkyl-N'-aryluree
Id group, N-alkyl ureido group, N-aryl ureide
Group, N'-alkyl-N-alkylureido group, N '
-Alkyl-N-arylureido group, N ', N'-di
Alkyl-N-alkylureido group, N ', N'-dia
Alkyl-N-arylureido group, N'-aryl-N
-Alkyl ureido group, N'-aryl-N-aryl
Ureido group, N ', N'-diaryl-N-alkyl
RAID group, N ', N'-diaryl-N-aryluree
Id group, N'-alkyl-N'-aryl-N-alkyl
Luureido group, N'-alkyl-N'-aryl-N-
Arylureido group, alkoxycarbonylamino group,
Aryloxycarbonylamino group, N-alkyl alcohol
Xycarbonylamino group, N-alkylaryloxyca
Rubonylamino group, N-arylalkoxycarbonyl
Amino group, N-aryl aryloxycarbonylamino
Group, formyl group, acyl group, carboxyl group, alkoxy
Cicarbonyl group, aryloxycarbonyl group, carbamo
Yl group, N-alkylcarbamoyl group, N, N-dial
A kill carbamoyl group, an N-aryl carbamoyl group,
N, N-diarylcarbamoyl group, N-alkyl-N
-An arylcarbamoyl group, an alkylsulfinyl group,
Arylsulfinyl group, alkylsulfonyl group, ant
Sulfonyl group, sulfo group (—SO_ThreeH) and both
Role base group (hereinafter referred to as sulfonato group), alkoxys
Ruphonyl group, aryloxysulfonyl group, sulfinamo
Yl group, N-alkylsulfinamoyl group, N, N-di
Alkylsulfinamoyl group, N-arylsulfina
Moyl group, N, N-diarylsulfinamoyl group, N
-Alkyl-N-arylsulfinamoyl group, sulf
Amoyl group, N-alkylsulfamoyl group, N, N-
Dialkylsulfamoyl group, N-arylsulfamo
Yl group, N, N-diarylsulfamoyl group, N-A
Alkyl-arylsulfamoyl group, phosphono group (-
PO _ThreeH_Two) And its conjugated base group (hereinafter referred to as phosphonate group)
), A dialkylphosphono group (-PO_Three(alky
l)_Two), A diarylphosphono group (—PO_Three(aryl)_Two), A
Alkylarylphosphono group (-PO_Three(alkyl) (aryl))
 , A monoalkylphosphono group (-PO_ThreeH (alkyl)) and
And its conjugate base group (hereinafter referred to as alkylphosphonate group)
), Monoarylphosphono group (-PO_ThreeH (aryl))
And its conjugated base group (hereinafter referred to as arylphosphonate group)
), A phosphonooxy group (-OPO_ThreeH_Two) And its
Conjugate base groups (hereinafter referred to as phosphonatoxy groups),
Alkylphosphonoxy group (-OPO_Three(alkyl)_Two),
Diarylphosphonooxy group (-OPO_Three(aryl)_Two),
Alkylarylphosphonoxy group (-OPO_Three(alky
l) (aryl)), monoalkylphosphonooxy group (-OP
O_ThreeH (alkyl)) and its conjugated base group (hereinafter referred to as alkyl
Sulfonatooxy group), monoarylphosphono
Oxy group (-OPO_ThreeH (aryl)) and its conjugate base group
(Hereinafter referred to as arylphosphonatooxy group),
Group, nitro group, aryl group, alkenyl group
You. Specific examples of the alkyl group in these substituents
Examples of the above-mentioned alkyl group include specific examples of the aryl group.
Examples include phenyl, biphenyl, naphthyl,
Tolyl, xylyl, mesityl, cumenyl, chloro
Rophenyl group, bromophenyl group, chloromethylphenyi
Group, hydroxyphenyl group, methoxyphenyl group, d
Toxiphenyl group, phenoxyphenyl group, acetoxy
Phenyl group, benzoyloxyphenyl group, methylthiophene
Phenyl, phenylthiophenyl, methylaminophen
Nyl group, dimethylaminophenyl group, acetylaminophenyl
Phenyl, carboxyphenyl, methoxycarbonyl
Phenyl group, ethoxycarbonylphenyl group, phenoxy
Sicarbonylphenyl group, N-phenylcarbamoylph
Phenyl, phenyl, cyanophenyl, sulfo
Nyl group, sulfonatophenyl group, phosphonophenyl
Group, phosphonatophenyl group and the like. Ma
Examples of the alkenyl group include a vinyl group and 1-propene.
Nyl group, 1-butenyl group, cinnamyl group, 2-chloro-
A 1-ethenyl group, and the like;
Ethynyl group, 1-propynyl group, 1-butenyl
And a trimethylsilylethynyl group. Reed
Group (R¹³R in CO-)¹³As for hydrogen,
And the above-mentioned alkyl groups and aryl groups.
You. Of these substituents, still more preferred
Halogen atom (-F, -Br, -Cl, -I), alcohol
Xy, aryloxy, alkylthio, arylthio
O group, N-alkylamino group, N, N-dialkylamido
Group, acyloxy group, N-alkylcarbamoyloxy
Group, N-arylcarbamoyloxy group, acylamido
Group, formyl group, acyl group, carboxyl group, alcohol
Xycarbonyl group, aryloxycarbonyl group, carba
Moyl group, N-alkylcarbamoyl group, N, N-dia
Alkylcarbamoyl group, N-arylcarbamoyl group,
N-alkyl-N-arylcarbamoyl group, sulfo
Group, sulfonato group, sulfamoyl group, N-alkyls
Rufamoyl group, N, N-dialkylsulfamoyl
Group, N-arylsulfamoyl group, N-alkyl-N
-Arylsulfamoyl, phosphono, phospho
Nato group, dialkylphosphono group, diarylphospho
Group, monoalkylphosphono group, alkylphosphona
Group, monoarylphosphono group, arylphosphona
Groups, phosphonooxy groups, phosphonatoxy groups,
And a reel group and an alkenyl group. On the other hand,
As the alkylene group in the kill group, the above-mentioned one having 1 carbon atom
Any one of the hydrogen atoms on the alkyl group from 1 to 20
And a divalent organic residue.
Preferably a straight-chain, carbon source having 1 to 12 carbon atoms.
Branched from 3 to 12 carbon atoms and 5 carbon atoms
Up to 10 cyclic alkylene groups can be mentioned.
Specific examples of preferred substituted alkyl groups include chloromethyl
Group, bromomethyl group, 2-chloroethyl group, trifur
Oromethyl group, methoxymethyl group, methoxyethoxy
Tyl group, allyloxymethyl group, phenoxymethyl group,
Methylthiomethyl group, tolylthiomethyl group, ethylamido
Noethyl group, diethylaminopropyl group, morpholino
Propyl, acetyloxymethyl, benzoyloxy
Cimethyl group, N-cyclohexylcarbamoyloxye
Tyl group, N-phenylcarbamoyloxyethyl group,
Cetylaminoethyl group, N-methylbenzoylaminop
Ropyl group, 2-oxoethyl group, 2-oxopropyl
Group, carboxypropyl group, methoxycarbonylethyl
Group, allyloxycarbonylbutyl group, chlorophenoxy
Cicarbonylmethyl group, carbamoylmethyl group, N-meth
Tylcarbamoylethyl group, N, N-dipropylcarba
Moylmethyl group, N- (methoxyphenyl) carbamoy
Ruethyl group, N-methyl-N- (sulfophenyl) ca
Rubamoylmethyl group, sulfobutyl group, sulfonatob
Tyl group, sulfamoylbutyl group, N-ethylsulfa
Moylmethyl group, N, N-dipropylsulfamoylp
Ropyl group, N-tolylsulfamoylpropyl group, N-
Methyl-N- (phosphonophenyl) sulfamoyl
Group, octyl group, phosphonobutyl group, phosphonate
Xyl group, diethylphosphonobutyl group, diphenylpho
Sphonopropyl group, methylphosphonobutyl group, methyl
Ruphosphonatobutyl group, tolylphosphonohexyl
Group, tolylphosphonatohexyl group, phosphonooxy
Propyl group, phosphonateoxybutyl group, benzyl
Group, phenethyl group, α-methylbenzyl group, 1-methyl
-1-phenylethyl group, p-methylbenzyl group, syn
Namyl group, allyl group, 1-propenylmethyl group, 2-butane
Thenyl group, 2-methylallyl group, 2-methylpropenyl
Methyl group, 2-propynyl group, 2-butynyl group, 3-bu
And a tinyl group.

Examples of the aryl group include a group in which one to three benzene rings form a condensed ring, and a group in which a benzene ring and a 5-membered unsaturated ring form a condensed ring. And a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group and a fluorenyl group. Of these, a phenyl group and a naphthyl group are more preferred.

As the substituted aryl group, those having a monovalent nonmetallic atomic group other than hydrogen as a substituent on the ring-forming carbon atom of the aforementioned aryl group are used. Examples of preferred substituents include the aforementioned alkyl groups, substituted alkyl groups,
In addition, there can be mentioned those described above as the substituent in the substituted alkyl group. Preferred specific examples of these substituted aryl groups include biphenyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, fluorophenyl, chloromethylphenyl, trifluoromethylphenyl,
Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl, N-cyclohexylcarbamoyloxyphenyl, N-phenylcarbamoyloxyphenyl, acetylaminophenyl, N-methylbenzoylaminophenyl, carboxyphenyl, methoxycarbonylphenyl, allyloxycarbonylphenyl, chloro Phenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, - (methoxyphenyl) carbamoyl phenyl group, N- methyl -N- (sulfophenyl)
Carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N- Methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatophenyl group, tolyl Phosphonophenyl group, tolylphosphonatophenyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallylphenyl group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 3-butynylphenyl Group, 3-butynyl Eniru group, or the like can be mentioned.

As the substituted oxy group (R ¹⁴ O—), R ¹⁴
Is a monovalent non-metallic atomic group other than hydrogen. Preferred substituted oxy groups include an alkoxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, an N-alkylcarbamoyloxy group, an N-arylcarbamoyloxy group, an N, N-dialkylcarbamoyloxy group, and an N, N-diarylcarbamoyloxy group. Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group,
Examples include a phosphonooxy group and a phosphonatoxy group. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group, the substituted alkyl group, the aryl group, and the substituted aryl group. Further, as the acyl group (R ¹⁵ O—) in the acyloxy group, R ¹⁵ is the aforementioned alkyl group,
Examples include substituted alkyl groups, aryl groups and substituted aryl groups. Among these substituents,
Alkoxy, aryloxy, acyloxy and arylsulfoxy groups are more preferred. Specific examples of preferred substituted oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, Carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxy group, Phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group,
Mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyloxy group, bromophenyloxy group, acetyloxy group, benzoyloxy group, naphthyloxy group, phenylsulfonyloxy group, phosphonooxy group, phosphonate Oxy groups and the like.

As the substituted thio group (R ¹⁶ S-), those in which R ¹⁶ is a monovalent nonmetallic atomic group other than hydrogen can be used. Preferred examples of the substituted thio group include an alkylthio group, an arylthio group, an alkyldithio group, an aryldithio group, and an acylthio group. Alkyl group in these, the above-described alkyl group as the aryl group, a substituted alkyl group, and aryl group, it can be mentioned those shown as the substituted aryl group, R ¹⁵ of the acyl group (R ¹⁵ O-) in the acylthio group described above It is notori. Among these, an alkylthio group and an arylthio group are more preferred. Specific examples of preferred substituted thio groups include a methylthio group, an ethylthio group, a phenylthio group, an ethoxyethylthio group, a carboxyethylthio group, and a methoxycarbonylthio group.

A substituted amino group (R ¹⁷ NH—, (R ¹⁸ ) (R
¹⁹ ) As N-), those in which R ¹⁷ , R ¹⁸ and R ¹⁹ are monovalent non-metallic atomic groups other than hydrogen can be used. Preferred examples of the substituted amino group include an N-alkylamino group, N, N-
Dialkylamino group, N-arylamino group, N, N-
Diarylamino group, N-alkyl-N-arylamino group, acylamino group, N-alkylacylamino group,
N-arylacylamino group, ureido group, N'-alkylureido group, N ', N'-dialkylureido group,
N'-arylureido group, N ', N'-diarylureido group, N'-alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido Group, N'-
Alkyl-N-arylureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N-
Alkylureido group, N'-aryl-N-arylureido group, N ', N'-diaryl-N-alkylureido group, N', N'-diaryl-N-arylureido group, N'-alkyl-N ' -Aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkylalkoxycarbonylamino group, N-alkylaryloxycarbo Examples thereof include a diamino group, an N-arylalkoxycarbonylamino group, and an N-arylaryloxycarbonylamino group. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group, the substituted alkyl group, and the aryl group and the substituted aryl group, and include an acylamino group, an N-alkylacylamino group, and an N-arylacylamino. An acyl group (R
R ^{15 of 15} CO-) is as described above. Of these,
More preferred are N-alkylamino groups,
N, N-dialkylamino group, N-arylamino group,
An acylamino group. Specific examples of preferred substituted amino groups include a methylamino group, an ethylamino group,
Examples include a diethylamino group, a morpholino group, a piperidino group, a pyrrolidino group, a phenylamino group, a benzoylamino group, and an acetylamino group.

As the substituted carbonyl group (R ²⁰ —CO—), those wherein R ²⁰ is a monovalent nonmetallic atomic group can be used. Preferred examples of the substituted carbonyl group include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group and N-alkyl-N-arylcarbamoyl group are exemplified. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group, the substituted alkyl group, and the aryl group and the substituted aryl group. Of these, more preferred substituents include formyl, acyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, N-alkylcarbamoyl, N, N-
Examples thereof include a dialkylcarbamoyl group and an N-arylcarbamoyl group, and more preferred examples include a formyl group, an acyl group, a carboxyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. Specific examples of preferred substituents include formyl, acetyl, benzoyl, carboxyl, methoxycarbonyl, allyloxycarbonyl, N-methylcarbamoyl, N-phenylcarbamoyl, N, N-
Examples include a diethylcarbamoyl group and a morpholinocarbonyl group.

As the substituted sulfinyl group (R ²¹ -SO-), those wherein R ²¹ is a monovalent nonmetallic atomic group can be used. Preferred examples include an alkylsulfinyl group, an arylsulfinyl group, a sulfinamoyl group, an N-alkylsulfinamoyl group, an N, N-dialkylsulfinamoyl group, an N-arylsulfinamoyl group, and an N, N-diarylsulfinamoyl. And N-alkyl-N-arylsulfinamoyl groups. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group, the substituted alkyl group, and the aryl group and the substituted aryl group. Of these, more preferred examples include an alkylsulfinyl group and an arylsulfinyl group. Specific examples of such a substituted sulfinyl group include a hexylsulfinyl group,
Examples include a benzylsulfinyl group and a tolylsulfinyl group.

As the substituted sulfonyl group (R ²² —SO ₂ —), those in which R ²² is a monovalent nonmetallic atomic group can be used.
More preferred examples include an alkylsulfonyl group and an arylsulfonyl group. As the alkyl group and the aryl group in these, the above-mentioned alkyl group,
Examples of the substituted alkyl group, the aryl group, and the substituted aryl group can be given. like this,
Specific examples of the substituted sulfonyl group include a butylsulfonyl group and a chlorophenylsulfonyl group.

The sulfonato group (-SO ₃ ^-) the above Toh, means a conjugate base anion group of a sulfo group (-SO ₃ H), it is usually used preferably in combination with a counter cation. Such counter cations are generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ ,
Ca ²⁺ , Zn ^2+, etc.).

The substituted phosphono group means one or two of the hydroxyl groups on the phosphono group substituted by another organic oxo group. Preferred examples thereof include the above-mentioned dialkylphosphono group, diarylphosphono group, Examples include an alkylarylphosphono group, a monoalkylphosphono group, and a monoarylphosphono group. Among these, a dialkylphosphono group and a diarylphosphono group are more preferred. Specific examples include a diethylphosphono group, a dibutylphosphono group, a diphenylphosphono group, and the like.

[0032] phosphonato group (-PO ₃ ^2-, -PO
₃ H ^-) above and the Toh, phosphono group (-PO ₃ H ₂₎
Means a conjugate base anion group derived from acid first dissociation or acid second dissociation. Usually it is preferred to use it with a counter cation. Such counter cations include:
What is generally known, ie, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn ²⁺ etc.) Is raised.

The substituted phosphonate group is a conjugate base anion group obtained by substituting one hydroxyl group with an organic oxo group among the above-mentioned substituted phosphono groups, and specific examples thereof include a monoalkylphosphono group (-PO ₃ H (alkyl)) and a conjugate base group of a monoarylphosphono group (—PO ₃ H (aryl)). Usually it is preferred to use it with a counter cation. Such counter cations include:
Those generally known, that is, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), and metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.) ).

Of the above-mentioned examples of R ¹ , R ² , R ³ and R ⁴ , more preferred are a hydrogen atom, a halogen atom (—F, —Cl, —Br, —I), an alkyl group , A substituted alkyl group, an aryl group, a hydroxyl group (-OH),
Examples include a substituted thio group, a substituted amino group, a substituted carbonyl group, a sulfo group, a sulfonato group, a cyano group, and a nitro group. Still more preferably, the substituent on the substituted alkyl group is a halogen atom, -OR ⁵¹ (R ⁵¹ Is the alkyl mentioned above,
Substituted alkyl, aryl and substituted aryl).

Next, an example in which R ¹ and R ² , R ² and R ³ , and R ³ and R ⁴ are bonded to each other to form a ring will be described. R ¹ and R ² ,
Examples of the aliphatic ring formed by combining R ² and R ³ and R ³ and R ⁴ include a 5-membered ring, a 6-membered ring, a 7-membered ring, and an 8-membered aliphatic ring. Preferably, a 5- or 6-membered aliphatic ring can be mentioned. These may further have a substituent on the carbon atom constituting them (examples of the substituent include those mentioned as examples of the substituent on the alkyl group and the above-mentioned substituted alkyl group). May be substituted), and a part of the ring-constituting carbon atoms may be substituted with a hetero atom (an oxygen atom, a sulfur atom, a nitrogen atom, or the like). Preferred examples thereof include a benzocyclopentene ring, a benzocyclohexene ring, a benzocycloheptene ring, a benzocyclooctene ring, and a benzocyclopentene ring, a benzocyclohexene ring, a benzocyclooctene ring, in cooperation with a benzene ring containing a carbon atom to which they are bonded in formula [I]. And a 3-benzocyclohexadiene ring, a 1,3-dihydro-1,3-dioxaindene ring and a julolidine ring.

Examples of the case where R ¹ and R ² , R ² and R ³ , and R ³ and R ⁴ are bonded to each other to form an aromatic ring include, in cooperation with a benzene ring containing a carbon atom to which they are bonded, Naphthalene,
Can form an anthracene ring,
Preferred are those having a naphthalene ring. They may have a substituent on the carbon atom constituting them (examples of the substituent include an alkyl group and those described above as examples of the substituent on the substituted alkyl group). .

In the following, R ¹ , R ² ,
The most preferred examples of R ³ and R ⁴ are specifically shown.

[0038]

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[0039]

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[0040]

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Next, examples of R ⁵ in the general formula [I] are shown below. Alkyl group, substituted alkyl group, aryl group,
Examples of the substituted aryl group include those described above as examples of R ¹ , R ² , R ³ , and R ⁴ . Preferred specific examples of R ⁵ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group,
Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s
-Butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, allyl group, 1-propenylmethyl group,
2-butenyl group, 2-methylallyl group, 2-methylpropenyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenethyl Group, p-methylbenzyl group, cinnamyl group, hydroxyethyl group, methoxyethyl group, phenoxyethyl group, allyloxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, morpholinoethyl group, morpholinopropyl group, sulfopropyl Group, sulfonatopropyl group, sulfobutyl group, sulfonatobutyl group, carboxymethyl group,
Carboxyethyl group, carboxypropyl group, methoxycarbonylethyl group, 2-ethylhexyloxycarbonylethyl group, phenoxycarbonylmethyl group, methoxycarbonylpropyl group, N-methylcarbamoylethyl group, N, N-ethylaminocarbamoylmethyl group, N
-Phenylcarbamoylpropyl group, N-tolylsulfamoylbutyl group, p-trienesulfonylaminopropyl group, benzoylaminohexyl group, phosphonomethyl group, phosphonoethyl group, phosphonopropyl group, p-
Examples include a phosphonobenzylaminocarbonylethyl group, a phosphonatomethyl group, a phosphonatopropyl group, a phosphonatobutyl group, and a p-phosphonatobenzylaminocarbonylethyl group.

Next, examples of R ⁶ in the general formula [I] are shown below. R ⁶ is -R ²³ -C (R ²⁴ ) = C (R ²⁵ )
(R ^26), and represented by -R ²⁷ -C≡C-R ^28, a substituted or unsubstituted alkenyl group, alkynyl group, alkenyl group or alkynyl group, a. Here, R ²³ and R ²⁷ represent a covalent bond or a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, more preferably a covalent bond or a C 1 to C 6 alkylene group. A straight-chain, branched alkylene group having 2 to 8 carbon atoms, and a cyclic alkylene group having 5 to 10 carbon atoms. R ²⁴ , R ²⁵ , R
²⁶ and R ²⁸ represent a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group and a substituted aryl group (for example, R ¹ , R ² ,
Examples of R ³ and R ⁴ can be given). More preferred substituents for R ²⁴ , R ²⁵ , R ²⁶ and R ²⁸ include a hydrogen atom, a halogen atom and a group having 1 carbon atom.
To 10 linear, branched and cyclic alkyl groups. Preferred specific examples of R ⁶ include allyl, 2-butenyl, 3-butenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 5-hexenyl, 2-octenyl, and 7-octenyl. Group, 1
-Methylpropenyl group, 1,1-dimethylpropenyl group, 2-methylpropenyl group, 2-ethylpropenyl group, 3,3-dimethylpropenyl group, 2-cyclohexenyl group, geranyl group (7,7,3,3- Tetramethyl 2,6-heptadienyl group), citronenyl group (7,
7,3-trimethyl-5-peptenyl group), 2-chloro-2-propenyl group, 3-chloro-2-propenyl group,
2-propynyl group, 2-butynyl group, 3-butynyl group,
4-pentynyl group, 1,1-dimethylpropynyl group,
1,1-diethylpropynyl group, 4,4-dimethyl-2
-Butynyl group, vinyl group, chloroethynyl group, 1-propenyl group, 1-butenyl group, styryl group, ethynyl group,
And a 2-phenylethynyl group. The most preferred examples of R ⁶ include an allyl group, a 2-propynyl group, a vinyl group, and an ethynyl group.

Next, examples of R ⁷ and R ⁸ in the general formula [I] are shown below. Alkyl group, substituted alkyl group,
As examples of the aryl group and the substituted aryl group,
R ¹ , R ² , R ³ , and R ⁴ can be exemplified.

Next, R ⁹ , R ¹⁰ ,
Examples of R ¹¹ and R ¹² are shown below. As these substituents, those exemplified as R ¹ , R ² , R ³ and R ⁴ are preferable. Also, R ⁹ and R ¹⁰ , R ¹⁰ and R ¹¹ , R ¹¹ and R ¹²
Are bonded to each other to form a ring,
Examples of ^{1 to} R ⁴ can be given.

In the following, R ⁷ , R ⁸ ,
Specific examples of even more preferable examples of R ⁹ , R ¹⁰ , R ¹¹ and R ¹² will be specifically described.

[0046]

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[0047]

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[0048]

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Further, the partial skeleton (a) represented by the above (a-1) to (a-65) and the above (b-1) to (b-73)
The general formula [I] can be constituted by combining the partial skeleton (b) represented by The most preferable specific examples of the compound represented by the general formula [I] include the following.

[0050]

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[0051]

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[0052]

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[0053]

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The compound represented by the general formula [I] is called "Bul
l. Soc. Chimie. Belges, Vol. 57, 364-372
Page (1948) Abstract: Chemical Abstracts, No. 4
It can be synthesized by the method described in Vol. 4, columns 60c to 61d (1950). That is, for example, the compound (I
-1) is 3-allyl-5- [3-butyl-2 (3H)
-Benzothiazolylidene] -4,5-dihydro-2-
It is obtained by condensing (methylthio) -4-oxothiazolium 4-methylbenzenesulfonate with 1-indanone under basic conditions. In this case, as the base, generally used bases such as organic amines, pyridines (trialkylamine, dimethylaminopyridine, etc.), metal amides (lithium diisopropylamide, etc.), metal alkoxides (sodium methoxide, etc.), metals Hydrides (such as sodium hydride) can be suitably used. The method for synthesizing the compound of the general formula [I] is not limited to the above.

The compounds of the general formula [I] used in the photopolymerizable composition of the present invention are suitably used alone or in combination of two or more.

Next, the component (iii) used in the present invention will be described in detail. Any of the activators of the component (iii) in the present invention can be suitably used as long as they generate active radicals by light irradiation in the presence of the component (ii).
That is, a compound group that generates an active radical through some interaction (energy transfer, electron transfer, exciplex formation, etc.) with the component (ii) excited by light irradiation can be suitably used. Examples of preferred activators include (a) a compound having a carbon-halogen bond, (b) an aromatic onium salt compound, (c) an organic peroxide compound, (d) a thio compound,
(E) a hexaarylbiimidazole compound, (f) a ketoxime ester compound, (g) a borate compound,
(H) an azinium compound, (i) a metallocene compound,
(J) Active ester compounds and the like.

Preferred examples of the compound having a carbon-halogen bond as an example of the component (iii) include those represented by the following general formulas [II] to [VIII].

[0058]

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(Wherein X represents a halogen atom; Y ¹
Is _{-CX '3, -NH 2, -NHR} ', - NR '2, -O
Represents R '. Here, R 'represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. R is-
CX _{3 represents} an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group. ).

[0060]

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(Where R ²⁹ is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a substituted aryl group, a halogen atom, an alkoxy group, a substituted alkoxyl group, a nitro group or a cyano group; ′
Is a halogen atom, and n is an integer of 1 to 3. ).

Formula [IV]: R ³⁰ -Z-CH _(m-1) X ″ _m -R ³¹ [IV] (where R ³⁰ is an aryl group or a substituted aryl group, and R ³¹ is ^{C (= O) -NR 32 R} 33, -C (= S)
NR ³² R ³³ ,

[0063]

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Or Z is -C (＝ O)
—, —C (＝ S) — or —SO ₂ —, and R ³² , R ³³
Is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group;
³⁴ is the same as R 'in formula [II], X "is a halogen atom, and m is 1 or 2.)

[0065]

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Wherein R ³⁵ is an optionally substituted aryl group or a heterocyclic group, and R ³⁶ is
A trihaloalkyl or trihaloalkenyl group having three, and p is 1, 2 or 3.

[0067]

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(Where L is a hydrogen atom or a formula: CO—
^{_{(R 37) q (CX 3}} ) a substituent of _r, Q is sulfur, selenium or oxygen atom, a dialkyl methylene group, alkene -
A 1,2-ylene group, a 1,2-phenylene group or an NR group, M is a substituted or unsubstituted alkylene group or alkenylene group, or a 1,2-arylene group;
R ³⁸ is an alkyl group, an aralkyl group or an alkoxyalkyl group; R ³⁷ is a carbocyclic or heterocyclic divalent aromatic group; X is a chlorine, bromine or iodine atom;
q = 0 and r = 1 or q = 1 and r = 1 or 2
It is. A) a carbonylmethylene heterocyclic compound having a trihalogenomethyl group;

[0069]

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(Where X is a halogen atom, t is an integer of 1 to 3, s is an integer of 1 to 4, R ³⁸ is a hydrogen atom or a CH _{3-t Xt} group, ^{And 39} is an s-valent optionally substituted unsaturated organic group).
-Halogeno-5- (halogenomethyl-phenyl) -oxazole derivatives.

[0071]

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(Where X ′ is a halogen atom,
Is an integer of 1 to 3, u is an integer of 1 to 4, R ⁴⁰
Is a hydrogen atom or a CH _3-v X _v group, R ⁴¹ is an unsaturated organic group which may be substituted for u-valent. ), A 2- (halogenomethyl-phenyl) -4-halogeno-oxazole derivative.

Specific examples of such a compound having a carbon-halogen bond are described in, for example, Bull.
em. Soc. Japan, 42 , 2924 (1969), for example, 2-phenyl 4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl) -4,6-bis ( Trichloromethyl) -S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S -Triazine, 2- (2 ', 4'-dichlorophenyl) -4,6
-Bis (trichloromethyl) -S-triazine, 2,
4,6-tris (trichloromethyl) -S-triazine, 2-methyl-4,6-bis (trichloromethyl)-
S-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α, α, β-
Trichloroethyl) -4,6-bis (trichloromethyl) -S-triazine and the like. Other compounds described in GB 1388492, for example, 2
-Styryl-4,6-bis (trichloromethyl) -S-
Triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-
(Methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl)
Compounds described in JP-A-53-133428, such as -4-amino-6-trichloromethyl-S-triazine, for example, 2- (4-methoxy-naphth-1-yl) -4,6
-Bis-trichloromethyl-S-triazine, 2- (4
-Ethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl -S-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (acenaphth-5-yl) -4,6-bis- Compounds described in German Patent 3337024, such as trichloromethyl-S-triazine,
For example,

[0074]

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[0075]

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And the like. Also, FCScha
J. Org. Chem .; 29, 1527 (196
The compounds described in 4), for example, 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-
Tris (tribromomethyl) -S-triazine, 2,
4,5-tris (dibromomethyl) -S-triazine,
2-amino-4-methyl-6-tribromomethyl-S-
Triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine and the like can be mentioned.

Further, compounds described in JP-A-62-58241, for example,

[0078]

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[0079]

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And the like. Further, Japanese Patent Application Laid-Open
281728, for example,

[0081]

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And the like. Or even more
Journal of MPHutt, EFElslager and LMMerbel
Heterocyclic chemistry Vol.7 (No.3), 511
The following compound groups that can be easily synthesized by those skilled in the art according to the synthesis method described on pages 196 et seq. (1970).

[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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Alternatively, compounds such as those described in German Patent No. 2641100, for example 4- (4-methoxy-styryl) -6- (3,3,3-trichloropropenyl) -2-pyrone and 4- (3,4,5-trimethoxy-styryl) -6-trichloromethyl-2-pyrone or the compounds described in DE 33 33 450, for example,

[0090]

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[0091]

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[0092]

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The aromatic onium salt which is another example of the component (iii) includes elements of groups V, VI and VII of the periodic table, specifically N, P, As, Sb, Bi, O,
Includes aromatic onium salts of S, Se, Te, or I. Examples of such aromatic onium salts include the compounds disclosed in JP-B-52-14277, JP-B-52-14278, and JP-B-52-14279.

Specifically,

[0095]

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[0096]

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[0097]

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[0098]

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The organic peroxide which is another example of the component (iii) used in the present invention includes almost all organic compounds having one or more oxygen-oxygen bond in the molecule. Is methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy)-
3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 2,2-
Bis (tert-butylperoxy) butane, tert-butylhydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide,
Paramethane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,
1,3,3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, bis (te
rt-butylperoxyisopropyl) benzene, 2.5
-Dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide , Diisopropyl peroxydicarbonate, di-2
-Ethylhexyl peroxydicarbonate, di-2-
Ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, te
rt-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxy neodecanoate, tert-butyl peroxyoctanoate, tert-
Butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylaurate, tersyl carbonate, 3,3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, , 3 ',
4,4'-tetra- (t-aminoperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra-
(T-hexylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (t-octylperoxycarbonyl) benzophenone, 3,3', 4,4 '
-Tetra (cumylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyldi (t -Hexylperoxy dihydrogen diphthalate).

Among these, 3,3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone and 3,3', 4,4'-tetra- (t-aminoperoxycarbonyl) Benzophenone, 3,3 ', 4,4'
-Tetra (t-hexylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (t-octylperoxycarbonyl) benzophenone, 3,3',
4,4'-tetra (cumylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (p-isopropylcumylperoxycarbonyl) benzophenone,
Peroxide esters such as di-t-butyldiperoxyisophthalate are preferred.

The thio compound as component (iii) used in the present invention is represented by the following general formula [IX].

[0102]

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(Where R ⁴³ represents an alkyl group, an aryl group or a substituted aryl group, R ⁴⁴ represents a hydrogen atom or an alkyl group. R ⁴³ and R ⁴⁴ are bonded to each other to form oxygen, sulfur and A nonmetallic atom group necessary for forming a 5- to 7-membered ring which may include a hetero atom selected from a nitrogen atom is shown below.) The alkyl group of R ⁴³ in the above general formula [IX] is a carbon atom number. One to four is preferred. The phenyl as the aryl group of R ^44, carbon atoms, such as naphthyl 6
10 to 10 are preferable, and as the substituted aryl group,
The above aryl groups include those substituted with a halogen atom such as a chlorine atom, an alkyl group such as a methyl group, or an alkoxy group such as a methoxy group or an ethoxy group. ^R44 is preferably an alkyl group having 1 to 4 carbon atoms.

Specific examples of the thio compound represented by the general formula [IX] include the following compounds.

[0105]

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The hexaarylbiimidazole which is another example of the component (iii) used in the present invention includes 2,2.
2'-bis (o-chlorophenyl) -4,4 ', 5
5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl)- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2 '-Bis (o, o'-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4 ', 5,5'- Tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-trifluorophenyl) -4,4 ',
5,5'-tetraphenylbiimidazole and the like.

Examples of the ketoxime ester which is another example of the component (iii) used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one and 3-propionyloxy. Iminobutane
2-one, 2-acetoxyiminopentan-3-one,
2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyimiminobtan-2-one, 2-ethoxycarbonyloxyimino -1-phenylpropan-1-one and the like.

Examples of the borate salt as another example of the component (iii) in the present invention include a compound represented by the following general formula [X].

[0109]

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(Where R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ may be the same or different from each other, and each may be a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or a substituted or unsubstituted heterocyclic group,, R ^45,
R ⁴⁶ , R ⁴⁷ and R ⁴⁸ may combine two or more groups thereof to form a cyclic structure. However, at least one of R ⁴⁵ , R ⁴⁶ , R ⁴⁷ and R ⁴⁸ is a substituted or unsubstituted alkyl group. Z ⁺ represents an alkali metal cation or a quaternary ammonium cation).

The alkyl groups of R ^{45 to} R ⁴⁸ include linear, branched and cyclic alkyl groups, and preferably have 1 to 18 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, stearyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. As the substituted alkyl group, a halogen atom (for example, -Cl, Br or the like), a cyanami group, a nitro group, an aryl group (preferably a phenyl group), a hydroxy group,

[0112]

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(Where R⁴⁹, R⁵⁰Is independently a hydrogen atom,
Represents an alkyl group having 1 to 14 carbon atoms or an aryl group
You. ), -COOR⁵¹(Where R⁵¹Is hydrogen atom, carbon number
1 to 14 alkyl groups or aryl groups. ),-
OCOR⁵³Or -OR⁵³(Where R ⁵³Has 1 to 14 carbon atoms
Represents an alkyl group or an aryl group. ) As a substituent
Included.

The aryl group of R ^{45 to} R ⁴⁸ includes a 1 to 3 ring aryl group such as a phenyl group and a naphthyl group, and the substituted aryl group includes the above-mentioned substituted alkyl group Group substituent or carbon number of 1 to 1
The alkenyl group of R ^{45 to} R ⁴⁸ , including those having an alkyl group of 4, has 2 to 1 carbon atoms.
8, straight-chain, branched and cyclic ones, and examples of the substituent of the substituted alkenyl group include those described above as the substituent of the substituted alkyl group.

The alkynyl groups of R ^{45 to} R ⁴⁸ include:
It includes straight or branched ones having 2 to 28 carbon atoms, and examples of the substituent of the substituted alkynyl group include those described above as the substituent of the substituted alkyl group. In addition, R ^{45 to} R
⁴⁸ heterocyclic groups include at least one of N, S and O
And a 5- or 7-membered heterocyclic group, preferably a 5- to 7-membered heterocyclic group, which may contain a condensed ring. Further, it may have the substituents described above as the substituents of the substituted aryl group.

Specific examples of the compound represented by the general formula [X] include US Pat. Nos. 3,567,453 and 4,34.
3,891, EP 109,772, 1
No. 09,773 and the compounds shown below.

[0117]

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Examples of azinium salt compounds which are other examples of the component (iii) of the present invention include JP-A-63-13834.
5, JP-A-63-142345, JP-A-63-14
No. 2346, JP-A-63-143537 and JP-B-46-43363. Examples of the metallocene compound as another example of the component (iii) include JP-A-59-1523.
No. 96, JP-A-61-151197, JP-A-63-4
1484, JP-A-2-249, JP-A-2-4705
And a titanocene compound described in JP-A-1-3044
No. 53 and JP-A-1-152109.

Examples of the active ester compounds which are other examples of the component (iii) include imide sulfonate compounds described in JP-B-62-6223, active sulfonates described in JP-B-63-14340, and JP-A-59-174831. You can give a kind. More preferred examples of the component (iii) in the present invention include the compounds having a carbon-halogen bond described above, and the most preferred examples include a trihalomethyl-S-triazine compound represented by the general formula [II]. Can be given.

Component (iii) in the present invention is suitably used alone or in combination of two or more. These photopolymerization initiation systems in the composition of the present invention, ie, component (ii)
And the concentration of component (iii) is usually low. In addition, when the number is inappropriately large, undesired results such as blocking of the effective light beam occur.

In the present invention, the amount of the photopolymerization initiation system is 0.01% with respect to the total amount of the photopolymerizable ethylenically unsaturated compound and the linear organic polymer added as required.
To 60%, more preferably 1% to 30%. The ratio of the component (ii), which is a component of the photopolymerization initiation system used in the present invention, to the component (iii) is 0.01 to 50 parts by weight of the component (iii) per 1 part by weight of the organic dye of the component (ii). It is appropriate to use parts by weight, more preferably 0.02 to 2 parts by weight.
0 parts by weight, most preferably 0.05 to 10 parts by weight.

The photopolymerizable composition of the present invention may further contain a known compound having a function of further improving sensitivity or suppressing polymerization inhibition by oxygen as a co-sensitizer. Examples of such co-sensitizers include amines, such as those described by MRSander et al. In Journal of Polymer Societ.
y ", Volume 10, p. 3173 (1972), Shoko 44
-20189, JP-A-51-82102, JP-A-5-82102
2-134692, JP-A-59-138205, JP-A-60-84305, JP-A-62-18537,
JP-A-64-33104, Research Disclosure 33
No. 825, specifically, triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, p-methylthiodimethylaniline, and the like.

Other examples of the co-sensitizer include thiols and sulfides, for example, thiol compounds described in JP-A-53-705, JP-B-55-500806, and JP-A-5-142772; No. 56-75643, specifically, α-mercaptobenzothiazole, α-mercaptobenzoxazole, α-mercaptobenzimidazole, α-mercapdo-4 (3H) -quinazoline, β-mercaptonaphthalene And the like.

As another example, amino acid compounds (eg, N-phenylglycine, etc.) and JP-B-48-429 may be used.
No. 65, organometallic compounds (eg, tributyltin acetate, etc.), hydrogen donors described in JP-B-55-34414, sulfur compounds described in JP-A-5-91089 (eg,
Trithiane, etc.), phosphorus compounds (diethyl phosphite, etc.) described in JP-A-6-250389, and Japanese Patent Application No. 6-191.
No. 605, Si-H and Ge-H compounds.

As still another example, US Pat.
8,791, the aminoketone compounds described in EP 0284561 A1, for example,

[0126]

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[0127]

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And the like. When the above co-sensitizer is used, 0.1 part by weight of the compound of component (ii) is used.
It is suitably used in an amount of from 0.01 to 50 parts by weight, more preferably from 0.02 to 20 parts by weight, and most preferably from 0.05 to 50 parts by weight.
10 parts by weight. The photopolymerizable composition of the present invention preferably contains a linear organic polymer as a binder. As such a “linear organic polymer”, any linear organic polymer having compatibility with the photopolymerizable ethylenically unsaturated compound may be used. Absent. Preferably, a water-soluble or weakly alkaline water-soluble or swellable linear organic high molecular polymer that enables water development or weakly alkaline water development is selected. The linear organic high molecular polymer is appropriately selected and used depending on whether water, weakly alkaline water or an organic solvent is used as a developer as well as a film-forming agent of the composition. For example, when a water-soluble organic high molecular polymer is used, water development becomes possible. Examples of such a linear organic high molecular polymer include an addition polymer having a carboxylic acid group in a side chain, for example, Japanese Unexamined Patent Publication No.
-44615, JP-B-54-34327, JP-B-5
Nos. 8-12577, JP-B-54-25957, JP-A-54-92723, JP-A-59-53836 and JP-A-59-71048, that is, methacrylic acid copolymers, There are acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer and the like. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful. In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomers] copolymer and [allyl (meth) acrylate /
(Meth) acrylic acid / if necessary, other addition-polymerizable vinyl monomers] copolymer is preferred. In addition, polyvinyl pyrrolidone and polyethylene oxide are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble polyamide or 2,2
Polyethers of -bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful. These linear organic high molecular polymers can be mixed in any amount in the entire composition. However, if it exceeds 90% by weight, no favorable result is obtained in view of the strength of the formed image and the like.
Preferably it is 30 to 85%. The weight ratio of the photopolymerizable ethylenically unsaturated compound and the linear organic high molecular polymer is preferably in the range of 1/9 to 7/3. A more preferred range is 3/7 to 5/5.

In the present invention, in addition to the above basic components, a small amount of thermal polymerization inhibitor is used to prevent unnecessary thermal polymerization of a polymerizable ethylenically unsaturated compound during the production or storage of the photosensitive composition. It is desirable to add an agent. Suitable thermal polymerization inhibitors include hydroquinone, p-
Methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl −
6-t-butylphenol), cerium N-nitrosophenylhydroxyamine, aluminum salt of N-nitrosophenylhydroxylamine and the like. The amount of the thermal polymerization inhibitor to be added is about 0.5 to the weight of the whole composition.
Preferably from 01% to about 5%. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition by oxygen, and may be unevenly distributed on the surface of the photosensitive layer in a drying process after coating. . The added amount of the higher fatty acid derivative is about 0.5% to about 10% of the whole composition.
Is preferred.

In the present invention, a dye or pigment can be added for the purpose of coloring the photosensitive layer. The amount of the dye or pigment added is from 0.01% to 20% of the total composition, more preferably from 0.5 to 10%. Pigments are more preferable than dyes. As the pigment, commercially available pigments and known pigments described in various documents and the like can be used. For literature, the color index (C.I.
I. ) Handbook, "Latest Pigment Handbook" (edited by Japan Pigment Technology Association,
1977), “Latest Pigment Application Technology” (CMC Publishing,
1986), "Printing ink technology" (CMC Publishing, 1
984).

Examples of the types of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and polymer-bound pigments. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelated azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments , Quinophthalone pigments, dyed lake pigments,
Examples thereof include azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, and inorganic pigments. Among them, more preferred are insoluble azo pigments, azo lake pigments, phthalocyanine pigments, anthraquinone pigments and the like.

These pigments may be dispersed in the presence of a polymer. Examples of such a polymer include those represented by formulas (a) to (c) described in Japanese Patent Application No. 6-193357. ), A polymer having an aliphatic double bond in a main chain or a side chain.

[0133]

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Wherein R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R
⁵⁷ and R ⁵⁸ each independently represent a hydrogen atom, an alkyl group or an aryl group. X, Y and Z are each independently a divalent linking group. Q is an atomic group forming an aliphatic ring. As the alkyl group, an alkyl group having preferably 20 or less, more preferably 10 or less, and still more preferably 6 or less carbon atoms (eg, methyl, ethyl, propyl, butyl, hexyl, isopropyl, etc.) Is mentioned.

Examples of the aryl group include an aryl group having 6 to 22 carbon atoms (for example, a phenyl group, a naphthyl group, an anthryl group, etc.). The alkyl group and the aryl group may be substituted with an alkoxy group, an amide group, an alkoxycarbonyl group, or the like as a substituent. R ¹ ,
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each preferably a hydrogen atom or an alkyl group,
Particularly preferred is a hydrogen atom or methyl.

Examples of the divalent linking group represented by X and Y include an alkylene group, an arylene group, a carbonyl group,
Mention may be made of imino groups, oxygen atoms, sulfur atoms and combinations thereof. The divalent linking group may be substituted with an aryl group, a halogen atom, a hydroxyl group, a cyano group, or the like. As the alkylene group, the number of carbon atoms is preferably 10 or less, more preferably 6 or less,
More preferably, 3 or less alkylene groups (for example, -CH
₂ CH ₂ CH _2- , -CH ₂ CH _2- , -CH ₂ CH
(CH ₃ ) — and the like).

As the arylene group, an arylene group having 6 to 22 carbon atoms (for example,

[0138]

Embedded image

And the like). X is preferably an alkylene group. Y is preferably an alkylene group, a carbonyl group, an oxygen atom, or a combination thereof. The aliphatic ring formed by Q is preferably a 5- or 6-membered combined aliphatic ring having 5 to 30 carbon atoms (eg, a cyclohexane ring, a norbornenyl ring, a dicyclopentadiene ring). Aliphatic rings include bicyclic or tricyclic hydrocarbons having a bridgehead carbon atom. It is preferable that there be one double bond between carbon atoms in the aliphatic ring.

The photopolymerizable composition of the present invention may contain an inorganic filler or other known additives in order to improve the physical properties of the cured film. Further, it is preferable to add a surfactant in order to improve the surface state in coating. As the surfactant, a fluorine-based surfactant is preferable. When the photopolymerizable composition of the present invention is coated on a support, it is used after being dissolved in various organic solvents. Solvents used here include acetone, methyl ethyl ketone, cyclohexane,
Ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, Ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether , Diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N,
N-dimethylformamide, dimethyl sulfoxide, γ
-Butyrolactone, methyl lactate, ethyl lactate and the like. These solvents can be used alone or as a mixture. And the concentration of solids in the coating solution is 2
~ 50% by weight is suitable. The coating amount is suitably ranges from about 0.1 g / m ² ~ about 10 g / m ² in weight after drying.
More preferably, it is 0.5 to 5 g / m ² .

A dimensionally stable plate is used as the support. As the dimensionally stable plate,
Paper, plastic (for example, polyethylene, polypropylene, polystyrene, etc.) laminated paper,
For example, a metal plate such as aluminum (including an aluminum alloy), zinc, copper, etc., and further, for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene And plastic films such as polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc., and paper or plastic films on which the above-mentioned metals are laminated or vapor-deposited. Among these supports, the aluminum plate is particularly preferable because it is extremely dimensionally stable and inexpensive. Furthermore,
A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable.

In the case of a support having a metal surface, particularly an aluminum surface, a surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodizing treatment. Is preferably performed. As the graining treatment, brush grains or electrolytic grains are preferable. As the electrolytic solution of the electrolytic grains, an aqueous solution of nitric acid or hydrochloric acid is preferable, and nitric acid is particularly preferable.

Further, an aluminum plate which is grained and then immersed in an aqueous solution of sodium silicate can be preferably used. As described in JP-B-47-5125, an aluminum plate which is anodized and then immersed in an aqueous solution of an alkali metal silicate is preferably used. Anodizing treatment is performed, for example, in an electrolytic solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, boric acid, or an organic acid such as oxalic acid or sulfamic acid or an aqueous solution or a non-aqueous solution of a salt thereof alone or in combination of two or more. This is performed by flowing a current using an aluminum plate as an anode.

Further, silicate electrodeposition as described in US Pat. No. 3,658,662 is also effective. Further, Japanese Patent Publication No. 46-27481 and Japanese Patent Application Laid-Open No. 52-5860.
No. 2, JP-A-52-30503, and a surface treatment in which the above-described anodic oxidation treatment and sodium silicate treatment are combined are also useful. However, the sodium silicate treatment is not necessarily required.

[0145] Further, it is also preferable to sequentially perform mechanical surface roughening, chemical etching, electrolytic graining, anodizing treatment, and sodium silicate treatment as disclosed in JP-A-56-28893. Further, after performing these treatments, a water-soluble resin such as polyvinylphosphonic acid, a polymer and a copolymer having a sulfonic acid group in a side chain, polyacrylic acid, a water-soluble metal salt (eg, zinc borate) or Those coated with a yellow dye, an amine salt or the like are also suitable.

These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions of the photopolymerizable composition provided thereon and to adhere the photosensitive layer to the support. This is performed for the purpose of improving the performance. Further, it is preferable to apply a back coat described in JP-A-5-2271 or JP-A-6-35174 in order to prevent the elution of aluminum into the developing solution on the back surface of the support.

On the layer of the photopolymerizable composition provided on the support, for example, polyvinyl alcohol, in particular, having a saponification degree of 95, in order to prevent the polymerization inhibition effect by oxygen in the air.
% Or more of a protective layer made of a polymer having excellent oxygen barrier properties such as polyvinyl alcohol and acidic celluloses. Regarding the application method of such a protective layer,
For example, U.S. Pat. No. 3,458,311;
No. 49729. Application amount is 0.1
To 5.0 g is preferable, and 0.5 to 3 g is more preferable.

Further, the photopolymerizable composition of the present invention can be used for a usual photopolymerization reaction. Further, the present invention can be applied to various fields such as a photoresist for producing a printing plate, a printed board, and the like. Particularly, due to the high sensitivity and the wide spectral sensitivity characteristic up to the visible light region, which are characteristics of the photopolymerizable composition of the present invention,
When applied to a photosensitive material for a visible light laser such as an Ar ⁺ laser and a YAG-SHG laser, a good effect can be obtained.

Since the photopolymerizable composition of the present invention has high sensitivity and is sensitive to visible light, it can be particularly advantageously used for an image forming system using microcapsules. For use in an image forming system using microcapsules, see, for example, JP-A-57-197538.
No. 61-130945, No. 58-88739,
No. 58-88740, EP 223,587 A1
References can be referred to. In this image forming method, for example, a photopolymerization initiator composition composed of an ethylenic vinyl compound and a photopolymerization initiator and a microcapsule containing a dye precursor are coated on a support, and the photosensitive sheet is exposed by imagewise exposure. After hardening the microcapsules of the portion, the developer sheet is overlaid and pressed over the entire surface to break the microcapsules of the unexposed portion, and the color image forming substance (for example, dye precursor) is transferred to the image receiving element (for example, the developer). Layer) to form a color.

The photosensitive material using the photopolymerizable composition of the present invention may be heated after image exposure. Heating concentration is 6
0 to 160 ° is preferable, and 80 ° C to 13 is more preferable.
0 ° C. The heating time is preferably from 1 second to 5 minutes. Further, an unexposed portion of the photosensitive layer is removed with a developer to obtain an image.
Preferred developers for using these photopolymerizable compositions for preparing a lithographic printing plate include those described in JP-B-57-7427, such as sodium silicate and potassium silicate. Like sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. An aqueous solution of a suitable inorganic alkali agent or an organic alkali agent such as monoethanolamine or diethanolamine is suitable. The alkaline agent has a concentration of 0.1 to 10% by weight, preferably 0.5 to 5% by weight.
% By weight.

The alkaline aqueous solution may contain a small amount of a surfactant or an organic solvent such as benzyl alcohol, 2-phenoxyethanol or 2-butoxyethanol, if necessary. For example, US Pat.
No. 5,171 and 3,615,480. Further, Japanese Patent Application Laid-Open
No. 26601, No. 58-54341, Japanese Patent Publication No. 56-
The developing solutions described in JP-A-39464 and JP-A-56-42860 are also excellent.

However, when an organic solvent or the like is contained, problems such as toxicity at work, sanitary problems such as odor, safety problems such as flames, workability problems such as generation of bubbles, and problems such as pollution due to waste liquid, etc. Therefore, those containing substantially no organic solvent are preferred. As such an aqueous alkaline developer containing substantially no organic solvent, for example, a developer composition described in JP-A-59-84241 and JP-A-57-192952 can be used.

A commercially available developer preferably used is DP-
4 (Fuji Photo Film Co., Ltd.) with water 1/6 to 1/3
This solution was diluted to zero. The photosensitive lithographic printing plate using the photopolymerizable composition of the present invention is disclosed in JP-A-54-8002 and JP-A-54-8002.
Nos. 5-115045 and JP-A-59-58431, that is, after development, washing with water and then desensitizing, or directly using desensitizing, or an aqueous solution containing an acid. Or a desensitizing treatment after treatment with an aqueous solution containing an acid. Furthermore, in the development process of this type of photosensitive lithographic printing plate, the alkali aqueous solution is consumed depending on the processing amount, and the alkali concentration is reduced, or the alkali concentration is reduced by air due to long-time operation of the automatic developing solution. Processing capacity decreases,
JP-A Nos. 54-62004, 55-22759, 55-115039, 56-12645, and 58
-95349, 64-21451, JP-A-1-1-1
80548, a replenisher described in JP-A-2-3065,
In addition, the processing ability can be restored by the replenishment method.

The above-described plate making process is described in
It is preferably carried out using an automatic developing machine as described in JP-A-7054 and JP-A-2-32357. In addition, as the desensitized gum which is applied as required in the final step of the plate making process, JP-B-62-16834 and JP-B-62-25118.
No. 63-52600, JP-A-62-7595,
Those described in JP-A-62-11693 and JP-A-62-83194 are preferable.

Further, after the development processing, a burning heat treatment or a post-exposure can be performed to improve the printing durability during printing.

[0156]

The photopolymerizable composition of the present invention has high sensitivity to actinic rays in a wide range from ultraviolet to visible light. Therefore, ultra high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various visible and ultraviolet laser lamps, fluorescent lamps, tungsten lamps, sunlight, etc. are used as light sources. it can.

[0157]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. An aluminum plate having a thickness of 0.3 mm was etched by immersing it in 10% sodium hydroxide at 60 ° C. for 25 seconds, washed with running water, neutralized and washed with 20% nitric acid, and then washed with water. This was subjected to 30% in a 1% nitric acid aqueous solution using a sinusoidal alternating current.
Electrolytic surface-roughening treatment was performed at an anode charge of 0 coulomb / dm ² . Subsequently, 40% in 1% aqueous sodium hydroxide solution
Immersion in 30% sulfuric acid aqueous solution,
After desmutting at 40 ° C. for 40 seconds, anodizing was performed for 2 minutes in a 20% sulfuric acid aqueous solution at a current density of 2 A / dm ^{2 so} that the thickness of the anodized film became 2.7 g / m ² . When the surface roughness was measured, it was 0.3 μ (Ra display).

The following sol-gel reaction solution was coated on the back surface of the substrate treated in this manner with a bar coater, dried at 80 ° C. for 1 minute, and provided with a back coat layer having an applied amount of 70 mg / m ² after drying. Support A was prepared. (Preparation of sol-gel reaction liquid) Tetraethyl silicate 50 parts by weight Water 20 parts by weight Methanol 15 parts by weight Phosphoric acid 0.05 parts by weight When the above components were mixed and stirred, heat generation started in about 5 minutes. After reacting for 60 minutes, the following solution was added to prepare a backcoat coating solution.

Pyrogallol formaldehyde condensation resin (MW 2000) 4 parts by weight Dimethyl phthalate 5 parts by weight Fluorinated surfactant (N-butyl perfluorooctane 0.7 parts by weight) Sulfonamidoethyl acrylate / polyoxyethylene acrylate copolymer・ Molecular weight: 20,000) Methanol silica sol (manufactured by Nissan Chemical Industries, Ltd.) 50 parts by weight Methanol 30%) Methanol 800 parts by weight A photosensitive composition having the following composition is dry-coated on the surface of the aluminum plate thus treated. The composition was applied so as to have a weight of 1.4 g / m ² and dried at 80 ° C. for 2 minutes to form a photosensitive layer.

Pentaerythritol tetraacrylate 2.0 g Allyl methacrylate / methacrylic acid copolymer 2.0 g (copolymerization molar ratio 80/20) Component (ii) Xg Component (iii) Yg Fluorine-based nonionic surfactant (F -177 0.03 g Dainippon Ink Co., Ltd.) Thermal polymerization inhibitor N-nitrosophenyl 0.01 g Hydroxylamine aluminum salt

[0161]

[Table 1]

Methyl ethyl ketone 20 g Propylene glycol monomethyl ether 20 g Note that Table A below shows the contents of component (ii) and component (iii).
A 3% by weight aqueous solution of polyvinyl alcohol (degree of saponification: 98 mol%, degree of polymerization: 1000) is applied onto the photosensitive layer so that the dry coating weight is 2 g / m ^2, and dried at 100 ° C. for 2 minutes to form a protective layer. And

On the photosensitive material thus obtained, a Fuji PS step guide (ΔD =
(A gray scale in which the transmission density changes discontinuously at 0.15) was brought into close contact, and exposure was performed from above. A xenon lamp was used as a light source, and a Kenko optical filter BP-49 was used.
Illuminated with light. The energy on the PS step guide surface was 0.25 mJ / cm ² .

The exposed photosensitive material was heated at 120 ° C. for 20 seconds and developed. The sensitivity was indicated by the number of clear steps of the PS step guide after development. The higher the value of the number of stages, the higher the sensitivity. The development was performed at 25 ° C for 1 hour in the following developer.
The immersion was performed for 0 second. DP-4 (manufactured by Fuji Photo Film Co., Ltd.) 66.5 g Water 881.4 g Lipomin LA (20% aqueous solution) 52.1 g As a storage stability test, the photosensitive material prepared as described above was subjected to natural aging for one month. The presence or absence of a precipitate from the photosensitive layer was observed with an optical microscope. Similarly, the precipitate under the storage condition of 50 ° C. in an oven was traced.

[0165]

[Table 2]

The component (ii) in the present invention is superior to the compound of the comparative example in sensitivity to visible light. In addition, the component (ii) is clearly suppressed from precipitating from the photosensitive layer in the storage state with respect to the compound of the comparative example. That is, it is clear that the photopolymerizable composition containing the component (ii) is excellent in sensitivity and storage stability.

Continuation of the front page (72) Inventor Hiromichi Kurita 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Inside Fuji Photo Film Co., Ltd. (56) References JP-A-8-54735 (JP, A) JP-A-2-179643 (JP) JP-A-1-138204 (JP, A) JP-A-4-299350 (JP, A) JP-A-4-134456 (JP, A) JP-A-6-175553 (JP, A) 3-39747 (JP, A) JP-A-56-64335 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/004 503 C08F 2/50 G03F 7/00 501 G03F 7/027 502 G03F 7/028

Claims (1)

(57) [Claims] 1. A compound having at least one addition-polymerizable ethylenically unsaturated bond, ii) a compound represented by the general formula [I]: (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹²
Are each independently a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group,
Hydroxyl group, substituted oxy group, mercapto group, substituted thio group, amino group, substituted amino group, substituted carbonyl group, sulfo group, sulfonato group, substituted sulfinyl group, substituted sulfonyl group, phosphono group, substituted phosphono group, phosphonate group, substituted Represents a phosphonate group, a cyano group or a nitro group, or represents R ¹ and R ² , R ² and R ³ , R ³ and R ⁴ , R ⁹
And R ¹⁰ , R ¹⁰ and R ¹¹ , R ¹¹ and R ¹² may be bonded to each other to form an aliphatic or aromatic ring, and R ⁵ represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, Or a substituted aryl group, R ⁶ represents a substituted or unsubstituted alkenylalkyl group, an alkynylalkyl group, an alkenyl group, or an alkynyl group; R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, A compound represented by an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted carbonyl group), and iii) an activator that generates an active radical by light irradiation in the presence of the component (ii) A photopolymerizable composition comprising: