JPH02244050A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To ensure high sensitivity for a photopolymerizable compsn. by incorporating specified compds. CONSTITUTION:A polymerizable compd. having an addition-polymerizable unsatd. bond, a compd. represented by formula I and a compd. selected among a compd. having a carbon-halogen bond, arom. onium salt, org. peroxide, a thio compd. represented by formula II, etc., a hexaryl-biimidazole compd. and ketoxime ester are incorporated. In the formula I, each of R<1> and R<2> is H, alkyl, etc., A is O, S, etc., X is a group of nonmetallic atoms required to form an N-contg. 5-membered hetero ring, Y is substd. phenyl, a polynuclear arom. ring, etc., and Z is H, alkyl, acyl, etc. In the formula II, R<3> is alkyl or aryl and R<4> is H or alkyl. The rate of photopolymn. of the resulting compsn. remarkably is increased and high sensitivity even to visible light is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to photopolymerizable compositions. More specifically, it relates to a photopolymerizable composition containing a polymerizable compound having an addition-polymerizable unsaturated bond, a photopolymerization initiator having a novel composition, and optionally a linear organic polymer. , relates to a photopolymerizable composition useful for photosensitive layers of photosensitive printing plates etc. which are also sensitive to argon laser beams.

[Conventional technology]

A photosensitive composition is prepared by mixing a polymerizable compound having an addition-polymerizable unsaturated bond, a photopolymerization initiator, and, if necessary, a binder having an appropriate film-forming ability and a thermal polymerization inhibitor. Methods for duplicating images using manual techniques are currently known. That is, U.S. Patent No. 2,92
No. 7,022, No. 2.902.356 or No. 3,
As described in No. 870,524, this type of photosensitive composition undergoes photopolymerization, hardens, and becomes insolubilized by irradiation with light.
A desired cured image of the photopolymerizable composition can be formed by irradiating light through the desired negative image and removing only the unexposed areas using a suitable solvent (hereinafter simply referred to as development). It goes without saying that this type of photosensitive composition is extremely useful for making printing plates and the like.

Furthermore, conventionally, polymerizable compounds having addition-polymerizable unsaturated bonds alone do not have sufficient photosensitivity, and it has been proposed to add a photopolymerization initiator to increase photosensitivity. As such, benzyl, benzoin, benzoin ethyl ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone, 2-ethylanthraquinone, etc. have been used. However, when these photopolymerization initiators are used, the curing sensitivity of the photopolymerizable composition is low, so that image exposure during image formation requires a long time. For this reason, in the case of detailed images, if there is slight vibration during operation, the image will not be reproduced with good quality.
Furthermore, since the amount of energy emitted by the light source for exposure must be increased, it is necessary to consider the dissipation of a large amount of heat accompanying this increase. In addition, there are problems such as the composition film being easily deformed and deteriorated by heat.

Further, these photopolymerization initiators have a significantly lower photopolymerization ability with respect to a light source in the visible light region of 400 nm or more than that with a light source in the ultraviolet region of 400 nm or less. Therefore, the range of application of conventional photopolymerizable compositions containing photopolymerization initiators is extremely limited.

Several proposals have been made regarding photopolymerization systems sensitive to visible light. As such a proposal, U.S. Pat.
No. 850,445 reports that certain photoreductive dyes, such as rose bengal, eosin, and erythrosin, have effective visible light sensitivity. In addition, improved technologies include a composite initiation system of a dye and an amine (Japanese Patent Publication No. 44-20189), a system of hexaarylbiimidazole, a radical generator, and a dye (Japanese Patent Publication No. 45-373).
77), a system of hexaarylbiimidazole and P-dialkylaminobenzylidene ketone (Japanese Patent Publication No. 47-25
28, JP-A-54-155292), a system of 3-keto-substituted coumarin compounds and active halogen compounds (JP-A-58
15503) and a system of substituted triazine and merocyanine dyes (Japanese Patent Application Laid-Open No. 15102/1983). These techniques are certainly effective for visible light.

However, the photosensitive speed is still not fully satisfactory, and further improved technology has been desired.

In addition, in recent years, increased sensitivity to ultraviolet rays and methods of forming images using lasers have been studied, and UV projection exposure methods for printing plates, direct laser platemaking, laser facsimile, holography, etc. are already in practical use. Highly sensitive photosensitive materials are currently being developed to meet these needs. However, it cannot be said that it has sufficient sensitivity yet.

[Problem to be solved by the invention]

An object of the present invention is to provide a highly sensitive photopolymerizable composition.

That is, an object of the present invention is generally to provide a photopolymerizable composition containing a photopolymerization initiator that increases the photopolymerization rate of a photopolymerizable composition containing a polymerizable compound having an addition-polymerizable unsaturated bond. It is to be.

Another object of the present invention is to provide visible light of 400 nm or more,
In particular, 488 nm corresponds to the output of Ar” laser.
It is an object of the present invention to provide a photopolymerizable composition containing a photopolymerization initiator that is highly sensitive to nearby light.

[Means to solve the problem]

As a result of extensive research to achieve the above objectives, the inventors have discovered 1. It was discovered that a certain photopolymerization initiator system significantly increases the photopolymerization rate of a polymerizable compound having an addition-polymerizable unsaturated bond, and also shows high sensitivity to visible light of 400 nm or more, and the present invention has been reached.

That is, the present invention provides (1) (i) a polymerizable compound having an addition-polymerizable unsaturated bond (ii)-installation [I] (wherein R' and R2 are each independently a hydrogen atom, an alkyl group, Substituted alkyl group, alkokyl/'carbonyl group,
Represents an aryl group, substituted aryl group or aralkyl group. A represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, an alkyl- or aryl-substituted nitrogen atom, or a dialkyl-substituted carbon atom. X represents a nonmetallic atomic group necessary to form a nitrogen-containing five-membered heterocycle.

Y represents a substituted phenyl group, an unsubstituted or substituted polynuclear aromatic ring, or an unsubstituted or substituted heteroaromatic ring. Z is a hydrogen atom, an alkyl group, a substituted alkyl group,
represents an aryl group, substituted aryl group, aralkyl group, alkoxy group, alkylthio group, arylthio group, substituted amino group, acyl group, or alkoxycarbonyl group,
It may be combined with Y to form a ring. ), and (iii) (a) a compound having a carbon-halogen bond, (b) an aromatic onium salt, (c) an organic peroxide, (d) a thio compound represented by -setting [11] : It relates to a photopolymerizable composition characterized by containing at least one compound selected from the group consisting of (e) hexaarylbiimidazole compounds and (he) ketoxime esters.

The photopolymerizable composition of the present invention further includes the following components (iv).
) and/or component (V),
Furthermore, a highly sensitive photopolymerizable composition can be obtained.

(iv) -Installation [■]: (Here, R3 represents an alkyl group, an aryl group, or a substituted aryl group, and R4 represents a hydrogen atom or an alkyl group. Also, R3 and R" are bonded to each other to form an oxygen, Represents a group of nonmetallic atoms necessary to form a 5- to 7-membered ring that may contain a heteroatom selected from sulfur and nitrogen atoms. (Here, R5, R6, R' and R6 are the same as each other.) may also be different, each representing 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. , R5, RbR
Two or more groups of 7 and R8 may be bonded to form a cyclic structure. However, R5Rh, R7 and R1+
At least one of them is a substituted or unsubstituted alkyl group. Z' represents an alkali metal cation or a quaternary ammonium cation. ) Compound 9 represented by (v) -setting [■]: Here, Ar represents an aromatic group selected from one of the following general formulas, R9 and RIO represent a hydrogen atom or an alkyl group, Furthermore, RQ and R10 may be bonded to each other to represent an alkylene group.

(However, in formula 2, RI I and RI 5 may be the same or different from each other, and each represents a hydrogen atom and a halogen atom.
．． Alkyl group, alkenyl group, aryl group, substituted aryl group, hydroxyl group, alkoxy group, substituted alkoxy group, -3
-R17 group, -3o-R" group, or -3O2R" group, provided that at least one of the RI + and RI S groups is -S -R" group, -5on" group, or -SO□Rl' 7 groups, R17 represents an alkyl group or alkenyl group, and RI6 represents a hydrogen atom, an alkyl group or an acyl group.

represents. ).

Each component of the photopolymerizable composition of the present invention will be explained in detail below.

The polymerizable compound having an addition-polymerizable unsaturated bond as component (i) used in the present invention is selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds.

For example, they have chemical forms such as monomers, prepolymers, dimers, trimers, and oligomers, mixtures thereof, and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid,
Examples include esters of crotonic acid, isocrotonic acid, maleic acid, etc.) and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds.

Specific examples of monomers of esters of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol as acrylic esters. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropene tri(a-cryloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexane diol diacrylate, tetraethylene glycol diacrylate,
Pentaerythritol diacrylate-1, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, to sorbitol Examples include hexaacrylate, tri(acryloyloxyethyl)isocyanurate, and polyester acrylate oligomer.

Examples of methacrylic acid esters include te[latchlene gelicol dittaacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane 1-remethacrylate, ethylene glycol dimethacrylate, 1,3-butane diol dimethacrylate, hexanediol dimethacrylate-1, ben/querythritol dimethacrylate, penquerythritol trimethacrylate, pentaerythritol]-
Lutetra methacrylate, dipentaerythritol dimecryle [·, dipentaerythryl-1-1-l hexamethacrylate, sorbitol trimethacrylate-1·, sorbitol tetramethacrylate, bis(p-(3-methacryloxy-2-hydroxypropoxy)phenyl) ]
Examples include dimethylmethane, bis-(p-(acryloxyethoxy)phenyl)dimethylmethane, and the like.

As the itaconic acid ester, ethylene glycol shitaconate, propylene glycol shitaconate, 1
．． Examples include 3-butanediol diitaconate, 1,4-butanediol shiitaconate, tetramethylene glycol shiitaconate, penquerythritol shiitaconate, sorbitol tetrataconate, and the like.

Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, beni/querythritol dicrotonate, and sorbitol tetramaleate.

Isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, sorbitol tetraisocrotonate, and the like.

Examples of maleic esters include ethylene glycol simarate, triethylene glycol simarate, pentaerythritol simarate, and sorbitol tetramaleate.

Furthermore, mixtures of the aforementioned ester monomers may also be mentioned.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1.
Examples include 6-hexamethylenebisacrylamide, 1,6-hexamethylenebis-methacrylamide, diethylenetriamine trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like.

As another example, the following general formula (
Examples include vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule to which a vinyl monomer containing a hydroxyl group shown in A) is added.

CHz=C(R)Co○C82CH(R')OH(A
) (However, R and R' represent H or CH.

) Also, urethane acrylates as described in JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, JP-A-52-30490
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates prepared by reacting an epoxy resin with (meth)acrylic acid can be mentioned. Furthermore, those introduced as photocurable monomers and oligomers in Japan Adhesive Association Journal vol. 1.20, No. 7, 300-308 can also be used. The amount of these used is preferably 5 to 50% by weight (hereinafter referred to as %) based on the total components.
It is abbreviated as. ), more preferably 10 to 40%.

The component (11) used in the present invention is as follows - Installation [I
] It is a compound shown by.

(In the formula, R1 and R2 each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or an aralkyl group; A is an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, an alkyl or an alkyl group; Represents a nitrogen atom substituted with aryl or a carbon atom substituted with dialkyl.

X represents a nonmetallic atomic group necessary to form a nitrogen-containing five-membered heterocycle.

Y represents a substituted phenyl group, an unsubstituted or substituted polynuclear aromatic ring, or an unsubstituted or substituted heteroaromatic ring. Z is a hydrogen atom, an alkyl group, a substituted alkyl group,
It represents an aryl group, substituted aryl group, aralkyl group, alkoxyl group, alkylthio group, arylthio group, substituted amino group, acyl group, or alkoxycarbonyl group, and may be bonded with Y to form a ring. )-C
Examples of R1 and R2 in formula [11] are shown below. Examples of the alkyl group include linear, branched and cyclic alkyl groups having 1 to 18 carbon atoms,
Specific examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group. , isohexyl group, 5ec-butyl group, neopentyl group, tert-butyl group, terL-pentyl group, cyclopentyl group, cyclohexyl group, cyclohebutyl group,
A 2-norbornyl group can be mentioned. Among these, linear and branched alkyl groups having 1 to 10 carbon atoms and cyclic alkyl groups having 6 to 10 carbon atoms are preferred.

Examples of the substituent of the substituted alkyl group include a halogen atom (fluorine, chlorine, bromine, iodine), hydroxyl group, alkoxyl group, acyloxy group, acylamino group, alkoxycarbonyl group, and Nit-substituted carbamoyl group. On the other hand, as the alkyl group of the substituted alkyl group, the above-mentioned alkyl group having 1 to 18 carbon atoms, preferably the same (linear or branched alkyl group having 1 to 10 carbon atoms, and cyclic alkyl group having 6 to 10 carbon atoms) can be used. The most preferred alkyl group is a straight-chain or branched alkyl group having 1 to 4 carbon atoms.Specific examples of substituted alkyl groups include chloromethyl group, bromomethyl group, 2-chloroethyl group. group, 2,2゜2-trichloroethyl group, 2-chloropentyl group, 1-(chloromethyl)propyl group, 10-bromodecyl group, 18-methyloctadecyl group, chlorocyclohexyl group, hydroxymethyl group, 2-hydroquine Ethyl group, 2-hydroxybutyl group, 5-hydroxypentyl group, 10-hydroxydecyl group, 2-hydroquinoctadecyl group, 2-(hydroxymethyl)ethyl group, hydroxycyclohexyl group, 3-
Hydroxy-2-norbornyl group, methoxymethyl group, methoxyethyl group, methoxypropyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, methoxyethyl group, ethoxyethoxyethyl group, acetoxyethyl group, propionyloxyethyl group , hendiyloxyethyl group, benzoyloxypentyl group,
Examples include benzoyloxyethoxyethyl group, acetylaminoethyl group, propionylamino group, N-methylcarbamoylethyl group, and N,N-diethylcarbamoylethyl group.

Aryl groups include residues of one benzene ring (phenyl group), residues of two and three condensed benzene rings (naphthyl group, anthryl group, phenanthryl group), and residues of two benzene ring aggregates. group (biphenyl group) and residues of a condensed system of a benzene ring and a 5-membered unsaturated ring (indenyl group,
acenaphthynyl group, fluorenyl group).

The substituted aryl group includes a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an amino group, a substituted amino group (monoalkyl-substituted amino group (an example of an alkyl group), Methyl group, ethyl group,
propyl group, pentyl group, isopropyl group, 5ec-butyl group, isopentyl group), dialkylamino group (examples of alkyl groups are the same as examples of monoalkyl-substituted amino groups),
Monoacylamino group (examples of acyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group), cyano group,
Alkyl groups (straight, branched and cyclic alkyl groups having 1 to 18 carbon atoms, preferably 1 to 18 carbon atoms)
straight, branched and cyclic alkyl groups from up to 10, most preferably straight and branched alkyl groups having from 1 to 4 carbon atoms, specific examples of which have already been mentioned above. ), halogenalkyl groups (e.g., chloromethyl group,
2-chloroethyl group, 5-chloropentyl group, trifluoromethyl group), alkoxyl group (examples of alkyl groups, methyl group, ethyl group, butyl group, pentyl group, isopropyl group, isopentyl group, 2-methylbutyl group, 5ec-
butyl group), aryloxy group (examples of aryl group, phenyl group, 1-naphthyl group, 2-naphthyl group), alkoxycarbonyl group (examples of alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group) ), acyloxy group (examples of acyl group are the same as examples of monoacylamino group), alkoxysulfonyl group (examples of alkyl group are the same as examples of alkyl group of alkoxyl group), etc., with one or two substituents. Examples include residues substituted with two or more of the same substituents or mutually different substituents. Specific examples of these aryl groups and substituted aryl groups include phenyl group, chlorophenyl group, aminophenyl group, (methylamino)phenyl group, (ethylamino)phenyl group, (dimethylamino)phenyl group, acetylaminophenyl group,
Tolyl group, ethylphenyl L (chloromethyl)phenyl group, acetylphenyl group, phenoxyphenyl group,
Methoxycarbonylphenyl group, ethoxycarbonylphenyl group, acetoxyphenyl group, methoxysulfonylphenyl group, naphthyl group, 2amino-1-naphthyl group,
Examples include 1-dimethylamino-2-naphthyl group, chloronaphthyl group, methylnaphthyl group, anthryl group, phenanthryl group, indenyl group, biphenylyl group, chlorobiphenylyl group, aminobiphenylyl group, methylbiphenylyl group, and acenaphthynyl group. can. Among these, a phenyl group and a phenyl group substituted with one or more of the above-mentioned substituents, which are the same or different from each other, are preferred.

Examples of the aralkyl group include residues in which a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, is substituted with a phenyl group or a naphthyl group. Examples include benzyl group, phenethyl group, 3-phenylpropyl group, 3-phenylhexyl group, 10-phenyldecyl group, 4-phenylcyclohexyl group, l-naphthylmethyl group, 2-(1
-naphthyl)ethyl group and 2-naphthylmethyl group.

The alkoxycarbonyl group has 1 to 1 carbon atoms.
Examples include residues in which up to 0 linear, branched, and cyclic alkyl groups are bonded to an oxycarbonyl group, such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group. , SeC butoxycarbonyl group, and Ler t-butoxycarbonyl group.

Examples of the nitrogen-containing five-membered ring in which X cooperates with A, C and N in the general formula [+1] include the following.

The substituent E in formulas (a-1) to (a-4) has a Hammett's σ value in the range of -0.9 to +0.5. Examples include hydrogen atom, methyl group, isopropyl group, tert-butyl L phenyl group, trifluoromethyl group, acetyl group, ethoxycarbonyl group, carboxyl group, carboxylado group (-〇〇〇-), amino group, Methylamino group, dimethylamino group, ethylamino group, diethylamino group, acetylamino group, -PQ3
11 groups, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, phenoxy group, hydroxy group, acetoxy group, methylthio group,
Ethylthio group, isopropylthio group, mercapto group, acetylthio group, thiocyano group (-3CN), methylsulfinyl group, ethylsulfinyl group, methylsulfonyl group, ethylsulfonyl group, aminosulfonyl group, dimethylsulfonyl group, (-S-(co ,) z), sulfonate group, (-so!-), fluorine atom, chlorine atom, bromine atom, iodine atom, iodyl group, trimethylsilyl group (-S
i (C8:J) z ), triethylsilyl group, and trimethylstannyl group (-Sn (CH3) z). Among these substituents, preferred are a hydrogen atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a dimethylamino group, a diethylamino group, a chlorine atom, and a bromine atom.

-a An example of Y in formula [1] is shown below.

Examples of the substituent of the substituted phenyl group include the same ones as E mentioned above. Examples of the polynuclear aromatic ring include naphthyl group, anthryl group, and phenanthryl group, which are substituted with the above-mentioned substituents, and these may be substituted with the above-mentioned substituent E. Examples of heteroaromatic rings include 2-furyl group, 3-furyl group, 2-thienyl group, 3
-thienyl group, 2-pyrrolyl group, and 3-pyrrolyl group, which may be substituted with the above-mentioned substituent E.

Moreover, an example of Z in − installation [l] will be described below. Alkyl group 1. The substituted alkyl group, aryl group, and substituted aryl group ζ can be the same as those mentioned as examples of R1 and R2.

Examples of the aralkyl group include residues in which a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, is substituted with a phenyl group or a naphthyl group. Examples include benzyl group, phenethyl group, 3-phenylpropyl group, 3-phenylhexyl group, IO-phenyldecyl group, 4-phenylcyclohexyl group, 1-naphthylmethyl group, ■-(1-
(naphthyl)ethyl group and 2-naphthylmethyl group.

Examples of alkylthio groups include residues in which a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms is bonded to a thio group (sulfur atom); specific examples include methylthio group, ethylthio group, group, propylthio group, butylthio group, 5ec-butylthio group, ter L
-Butylthio group can be mentioned.

Examples of alkoxyl groups include residues in which a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms is bonded to an oxy group (oxygen atom); specific examples include methoxyl group, ethoxyl group, and ethoxyl group. group, propoxyl group, butoxyl group, 5ec--butoxyl group, tert
-butoxyl group.

Examples of the substituted amino group include amino groups substituted with linear, branched, and cyclic alkyl groups having 1 to 10 carbon atoms, and specific examples thereof include dimethylamino, diethylamino, Propylamino group can be mentioned.

Examples of the acyl group include a hydrogen atom, a residue in which a straight, branched or cyclic alkyl group, phenyl group or naphthyl group having carbon atoms from 1 to 0, preferably from 1 to 6, is bonded to a carbonyl group. Specific examples thereof include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, benzoyl group, and naphthoyl group.

The alkoxycarbonyl group has 1 to 1 carbon atoms.
Examples include residues in which up to 0 linear, branched or cyclic alkyl groups are bonded to an oxycarbonyl group, specific examples of which include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, Examples include 5eC-butoxycarbonyl group and tert-butoxycarbonyl group.

Further, examples of rings formed by bonding Y and Z to each other are shown below.

vinegar CH.

Li The compound group represented by the general formula [+] is "full.

Soc, Chimie Belgesj Vol. 57, pp. 364-372 (1948) Abstract: 'Chem
icalAbstracts J Magazine Volume 44 No. 60e~
61dMA (1950)).

Specific examples of the compound represented by general formula [I] are shown below.

<I-1> C811, 〈　1 5〉 < ■ 6〉 <1-7> <+-2> <+-3> <+-4> C@H+t 8〉 <+-9> 10〉 Cs1l+.

<1-1 1><+-12><1-13> CzLOC41L <1-17><1-18><+-19><■14><15> Ku■ 16>C11゜<l-20><1-22> As the compound having a carbon-halogen bond which is an example of component (iii) used in a preferred embodiment of the present invention, compounds represented by the following configurations (V) to (XI) are preferable.

In the general formula (V) 0, X' represents a halogen atom. Y3 is CX'
1, Nl! □, -N) IR'-NR'! , -O
Represents R'. Here, R' represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. Also, R is -
CX' , represents an alkyl group, substituted alkyl group, aryl group, substituted aryl group, or substituted alkenyl group. ).

- Installation [■]: (However, R+8 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 cyan group. , X' is a halogen atom, and n is an integer of 1 to 3.

General formula [■]: R"-Z-CIl, IX'-R" (
■) (However, RI9 is an aryl group or a substituted aryl group, and R2
In 1,l, 22 is an alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, aryl group or substituted aryl group, R21 is the same as R' in general formula (V), and X'' is a halogen atom. and m!! is 1 or 2).

General formula [~'III): However, in the formula, R24 is an optionally substituted aryl group or heterocyclic group, RlS is a trihaloalkyl group or trihaloalkenyl group having 1 to 3 carbon atoms, p is l, 2 or 3.

General formula [■]: (L is a hydrogen atom or a substituent of the formula: CO+R"), (CX), M is a substituted or unsubstituted alkylene group, and Q is a sulfur, selenium, or oxygen atom. , dialkylmethylene group, alkene-1,2-ylene group, 12-phenylene group or N-R
M is a substituted or unsubstituted alkylene group or alkenylene group, or a 1,2-arylene group, R2'' is an alkyl group, an aralkyl group or an alkoxyalkyl group, and R2'' is a carbocyclic group. is a divalent aromatic group of the formula or heterocyclic type, X is a chlorine, bromine or iodine atom, and q=O and r
=1 or q=l and r=1 or 2. ) A carbonylmethylene heterocyclic compound having a trihalogenomethyl group.

- Installation [X]: (However, X is a halogen atom, L is an integer from 1 to 3, and S
is an integer from 1 to 4, and R2'' is a hydrogen atom or C1h
4-halogen-5-(halogenomethyl-
phenyl)-oxazole derivatives.

- Installation [χl]: (where, X' is a halogen atom, V is an integer from 1 to 3, and U
is an integer from 1 to 4, R'' is a hydrogen atom or CL-vX
v group, and R3I is a U-valent optionally substituted unsaturated organic group. ) 2-(halogenomethyl-phenyl)=4-herogenoxazole derivative.

Compounds having such a carbon-halogen bond include, for example, Wakabu et al., Bull, Chew, So.
c.

Japan, 42.2924 (1969), such as 2-phenyl4,6-bis(trichloromethyl)-3-)riazine, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl) -3-1
-Ryazine, 2-(p-tolyl)-4゜6-bis(trichloromethyl)-3-triazine, 2-(p-methoxyphenyl)-'4.6-bis(trichloromethyl)-3
-triazine, 2-(2',4'-dichlorophenyl)
-4,6-bis(trichloromethyl)-3-triazine, 2゜4,6-tris(trichloromethyl)-3-triazine, 2-methyl-4,6-bis(trichloromethyl)-3-)riazine , 2-n-nonyl-4゜6-bis(trichloromethyl)-S-) riazine, 2-(α, α
, β-trichloroethyl)-4,6-bis(trichloromethyl)-3-)riazine, and the like. Other compounds described in British Patent No. 1388492, such as 2-styryl-46-bis(trichloromethyl)-3
-1-Ryazine, 2-(p-methylstyryl)-4,6
-bis(trichloromethyl)-3-triazine, 2-(
p-methoxystyryl)-4,6-bis(trichloromethyl)-3-)riazine, 2-(P-methoxystyryl)
-4-amino-6-dolychloronotyl-S-triazine, etc., compounds described in JP-A-53-133428, for example, 2-(4-methoxy-naphth-1-yl)-4,6
-bis-trichloromethyl-S-triazine, 2-(4
-ethoxy-naphth-1-yl)-4,6-bis-trictylmethyl-5-hlyazine, 2-(4-(2-ethoxyethyl)-naphth-1-yl)-4,6-pisdolychlor Methyl-S-)・Riazine, 2-(47-dimethoxy-naphthol-1-yl>, 1.G bis-trichloromethyl-S-triazi>・, 2(acenaphth-5-yl)-4,6-bis- Mention may be made of the compounds described in German Patent No. 3,337,024, such as 1-lychloromethyl-5-t-lyazine, and others such as C1.

Also, J, Or by F, C, 5chaefer et al.
g Chew, :9.1527 (1964), such as 2-methyl-4,6-bis(tribromomethyl)-3-1-riazine, 2,4.6-)lis(dobromomethyl)-5-1 -Riazine, 2,4. Examples include G tris(dibromomethyl)-5-triazine, amino-4-methyl-6-tribromomethyl-3-triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine, and the like.

Furthermore, compounds described in JP-A No. 62-58241, such as CC1! , 3, etc.

Or even M, P, l1utt, E, F
, Elslager and M. Werbel, Journal of l1eterocyclic
According to the synthesis method described in heIIstry Volume 7 (No. 3), pages 511 onward (1970),
The following compound groups, which can be easily synthesized by a person skilled in the art, or the following compound groups, or the compounds described in German Patent No. 2,641,100, such as 4-(4-methoxy-styryl) )-6-(3,3,3-)lychlorpropenyl)-
2-pyrone and 4-(3,4゜5-trimethoxy-
styryl)-6-t-lychloromethyl-2-pyrone, or a compound described in German Patent No. 3333450, for example Q=S; R1k=benzene ring or a compound described in German Patent No. 3021590 Group, No. Examples of the compound group described in Japanese Patent No. 3021599 include:

In addition, aromatic onium salts which are another example of component (iii) include elements of Groups ■, ■, and ■ of the periodic table, specifically N, P, As, Sb, Bi, ○, S .

Aromatic onium salts of Se, Te, or ■ are included.

Examples of such aromatic onium salts include
-14277, Special Publication No. 52-14278, Special Publication No. 14278, Special Publication No. 14278
Mention may be made of the compounds shown in No. 2-14279.

Specifically, we can give the following. Among these, the preferred one is
Compounds of BF4 salts or PF salts, more preferably aromatic iodonium salts of BF, salts, or PF6 salts.

Another example of component (iii) used in the present invention is “
"Organic peroxides" include almost all organic compounds that have one or more oxygen-oxygen bonds in the molecule; examples include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3.5-1- Limethyl cyclohexanone peroxide, methyl cyclohexanone peroxide, acetylacetone peroxide, 1,1-bis(tert-butyl peroxide)
-3,3,5-)dimethylcyclohexane, 1゜1-bis(tert-butylperoxy)cyclohexane,
2.2-Bis(tert-butylperoxy)butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramethane hydroperoxide, 2゜5-dimethylhexane-2,5-sibideroba -oxide, L L, 3.3-tetramethylbutyl hydroperoxide, di-tertiary butyl peroxide, tertiary-butyl cumyl peroxide,
Dicumyl peroxide, bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-
2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, acetyl peroxide,
Isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5.5-)limethyl-xanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4
-dichlorobenzoyl peroxide, meta-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-1-xyisopropylperoxycarbonate, di(3 -Methyl-3-methoxybutyl) peroxydicarbonate, t-butyl peroxyacetate, t-butyl peroxyvivalate, t-butyl peroxyneodecanoate, t-butyl peroxyoctanoate, t-butyl Peroxy-3,5,5-)limethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, di-tert-butyl diperoxyisophthalate, 2゜5-dimethyl- 2,5-di(benzoylperoxy)hexane, tert-butyl peroxymaleic acid, tert-butyl peroxyisopropyl carbonate, 3.3', 4.
4'-tetra(L-butylperoxycarbonyl)pentuphenone, 3.3', 4.4'-tetra-(L-amylperoxycarbonyl)benzophenone, 3°3'
4.4'-tetra(L-hexyloxycarbonyl)benzophenone, 3.3',4゜4'-tetra(
t-octylperoxycarbonyl)benzophenone,
3.3',4.4'-tetra(cumylperoxycarbonyl)benzophenone, 3.3',4.4'-tetra(p-isoprobylcumylperoxycarbonyl)
Examples include benzophenone, carbo, nildi(L-butylperoxydihydrogen diphthalate), carbonyldi(1-hexylyloxydihydrogen diphthalate), and the like.

Among these, 3.3', 4.4'-tera(L-butylperoxycarbonyl)benzophenone, 3.3'
, 4,4'-tetra-(t-amylbaroxycarbonyl)benzophenone, 3°3',4,4'-tetra(L
-hexyloxycarbonyl)benzophenone, 3
．． 3',4゜4'-tetra(L-octylperoxycarbonyl)benzophenone, 3.3',4.4'-tetra(cumylperoxycarbonyl)benzophenone,
Peroxide esters such as 3.3', 4.4'-tetra(p-isopropylcumylperoxycarbonyl)benzophenone and di-butylciberoxyisophthalate are preferred.

The thio compound as component (ji) used in the present invention is represented by the following configuration (II).

Indicates a rukyl group. Furthermore, R3 and R4 represent a group of nonmetallic atoms necessary for bonding with each other to form a 5- to 7-membered ring that may contain a heteroatom selected from oxygen, sulfur, and nitrogen atoms. ) The alkyl group for R3 in the above-mentioned setting (II) preferably has 1 to 4 carbon atoms. The aryl group for R3 is preferably one having 6 to 10 carbon atoms such as phenyl or naphthyl, and the substituted aryl group is preferably an aryl group such as the above aryl group, a halogen atom such as a chlorine atom, or a methyl group. It includes those substituted with an alkyl group, a methoxy group, and an alkoxy group such as an ethoxy group.

R4 is preferably an alkyl group having 1 to 4 carbon atoms.

Specific examples of thio compounds represented by general formula (n) include:
Examples include compounds shown below.

(Here, R3 represents an alkyl group, an aryl group, or a substituted aryl group, and R4 represents a hydrogen atom or another example of component (iii) used in the present invention, which is hexaarylbiimidazole, is 2.2 '-Bis(O-chlorophenyl)-4°/l', 5.5'-tetraphenylbiimidazole, 2,2'-bis(0-bromophenyl)-4,4'5.5'--tetraphenyl Biimidazole, 2゜2'-bis(o,p-dichlorophenyl)-4
゜4',5.5'-tetraphenylbiimidazole,
2.2'-bis(0-chlorophenyl)-4,4'5.
5'-tetra(m-methoxyphenyl)biimidazole, 2,2'-bis(o, ol-dichlorophenyl)
-4,4',5.5' -tetraphenylbiimidazole, 2,2'-bis(0-nitrophenyl)-4,4'
, 5,5'-tetraphenylbiimidazole, 2,2'
-bis(0-methylphenyl)-4,4',5.5'
-tetraphenylbiimidazole, 2,2'-bis(o
-trifluorophenyl)-4,4',5.5'-
Examples include tetraphenylbiimidazole.

Other examples of ketoxime esters as component (iii) used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxyiminobutan-2-one. 2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-
Examples include phenylpropan-1-one, 3-p-)luenesulfonyloxyiminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.

The component (1v) used in the present invention is as follows - Installation CI [I
] It is a compound shown by.

RS (Kokote, RS, R6, R7 and Rs are the same
- and may be different, each substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, or substituted or unsubstituted heterocyclic group , R5, R6, R
? and R8 may have two or more groups bonded together to form a cyclic structure; at least one of Tata L, R' SRh, R' and R8 is a substituted or unsubstituted alkyl group; be. Z゛ is an alkali metal cation or a quaternary
class ammonium cation).

The alkyl group of R'-R@ mentioned above includes straight chain, branched, and cyclic groups, and those having 1 to 18 carbon atoms are preferable. Specifically, methyl, ethyl, propyl, isopropyl, butyl, Includes pentyl, hexyl, octyl, stearyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.

Substituted alkyl groups include the above alkyl groups, halogen atoms (for example -α, -Br, etc.), cyano groups, nitro groups, aryl groups (preferably phenyl groups),
Indicates a hydroxy group, an atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group. ), -000RIS (where R3S is a hydrogen atom,
It represents an alkyl group or an aryl group having 1 to 14 carbon atoms.

'), -0COR3& or -OR'' (where R3b represents an alkyl group having 1 to 14 carbon atoms or an aryl group,
) as a substituent.

The aryl groups of R5 to R@ above include 1 to 3-ring aryl groups such as phenyl and naphthyl groups, and the substituted aryl groups include the above-mentioned substituted alkyl groups in addition to the aryl groups described above. or a substituent having 1 to 14 carbon atoms.

The alkenyl group of R5 to R6 above has 2 to 1 carbon atoms.
Examples of the substituent for the substituted alkenyl group include those listed above as the substituent for the substituted alkyl group.

The alkynyl group of R5 and R1 above has 2 to 2 carbon atoms.
8 straight chain or branched ones are included, and the substituents for the substituted alkynyl group include those listed as the substituents for the substituted alkyl group.

Further, the heterocyclic group for Rs and Rs is N.

A 5-membered or more, preferably 5- to 7-membered heterocyclic group containing at least one of S and 0 may be mentioned, and the heterocyclic group may include a fused ring. Further, as a substituent, it may have those listed as the substituent for the above-mentioned substituted aryl group.

- Specific examples of compounds represented by setting (III) include U.S. Patent No. 3,567.453 and U.S. Pat.
1, European Patent No. 109,772, European Patent No. 109.7
Compounds described in No. 73 and those shown below,
can be mentioned.

<I[[-1><I[[-2><I[I-3><lll-4>(III-5>) (nc4f(qter B-・N' (ncallq)
a(III-6><ll-7><ll-12><m-s><ll-13><lI[-9><I[1-10>) The photopolymerizable composition of the present invention includes: By containing the compound [component (V)] shown in - Installation (TV) below,
You can further increase your anger level.

In the general formula (rV), Ar represents an aromatic group selected from one of the following general formulas, R9 and R111 represent a hydrogen atom or an alkyl group, and Rq and Rto are bonded to each other. It may also represent an alkylene group.

2 units (in the formula, RII to RIS may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a substituted aryl group, a hydroxyl group, an alkoxy group, a substituted alkoxy group, S R+?
group, -5o-R" group or -So, R" group, provided that at least - of the R-th to RIS groups is -3BIt4, -5
o-R17 group or -5OZR'7 group, Rl? represents an alkyl group or an alkenyl group, and R16 represents a hydrogen atom, an alkyl group or an acyl group.

represents. ) In the above-setting (IV), the alkyl group of R9 and Rlo has 1 to 1 carbon atoms, such as methyl, ethyl, and propyl.
There are 20 examples. In addition, the alkylene group formed by combining Rq and RIG includes tetramethylene,
Examples include pentamethylene.

Examples of the alkyl group of R II to RIS in A" include those having 1 to 4 carbon atoms. Examples of the alkenyl group include those having 3 to 12 carbon atoms.

Furthermore, a phenyl group is mentioned as an aryl group of R1 to RI5. Furthermore, the alkoxy group has 1 to 1 carbon atoms.
Examples of the acyl group of R16 include acetyl, propionyl, acryloyl, and the like.

Specific examples of such compounds include: (IV-1> <■-2> <T'v'-3> <8r-4> (IV-8> <W9> ncall+.

Police station 4He etc.

Among these, preferred are <TV-1> and <rV-2
>(IV-8>, <TV-9>).

The concentration of these photopolymerization initiator systems in the composition of the invention is usually small. In addition, if the amount is inappropriately high, undesirable results such as blocking of effective light rays will occur. The amount of the photopolymerization initiator system in the present invention is determined by the amount of the photopolymerizable ethylenically unsaturated compound and the linear organic polymer added as necessary (TV-5><IV-6><IV-7> It is preferably used in a range of 0.01% to 60% based on the total amount with the polymer, and more preferably 1% to 30% to obtain good results.

The photopolymerization initiator used in the present invention and the component (ii) in j-
) and (iii), it is appropriate to use 0.01 to 50 parts by weight of component (iii) per 1 part by weight of the organic dye of component (11), more preferably 0.02 to 20 parts by weight.
parts by weight, most preferably from 0.05 to 10 parts by weight.

Furthermore, when component (iv) is used in combination, the amount of component (iv) is 0.05 to 1 part by weight of the organic dye of component (ii).
30 parts by weight, most preferably 0.2-5 parts by weight.

Furthermore, when the compound of component (V) is used in combination, the component (
Component (v) is added in an amount of 0.0% per part by weight of the organic dye (ii).
It is appropriate to use 0.01 to 50 parts by weight, more preferably 0.02 to 20 parts by weight, and most preferably 0.05 to 20 parts by weight.
It is 10 parts by weight.

The photopolymerizable composition of the present invention preferably contains (vi) a linear organic polymer as a binder. Any linear organic polymer may be used as the "linear organic polymer" as long as it is compatible with the photopolymerizable ethylenically unsaturated compound. do not have. Preferably, a linear organic polymer is selected which is soluble or swellable in water or weakly alkaline water and is capable of being developed in water or weakly alkaline water. The linear organic polymer is used not only as a film-forming agent in the composition, but also as a film-forming agent in the composition.
Selection is made depending on the use as a weakly alkaline water or organic solvent developer. For example, water development becomes possible when a water-soluble organic high molecular weight polymer is used. Examples of such linear organic polymers include addition polymers having carboxylic acid in the side chain, such as JP-A-59-44615 and JP-B-Sho 54-34.
327, Special Publication No. 5B-12577, Special Publication No. 5425
No. 957, JP-A-54-92723, JP-A-59-5
3836, JP-A No. 59-71048, namely, methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers,
Examples include maleic acid copolymers and partially esterified maleic acid copolymers.

Similarly, there are acidic cellulose derivatives having carboxylic acid in their side chains. In addition to these, addition polymers having hydroxyl groups to which a cyclic acid anhydride is added are useful. In particular, among these, copolymers (benzyl (meth)acrylate/(meth)acrylic acid/other addition-polymerizable vinyl monomers as required) and [allyl (meth)acrylate/(
A copolymer of meth)acrylic acid/other addition-polymerizable vinyl monomer if necessary is suitable. Other useful water-soluble linear organic polymers include polyvinylpyrrolidone and polyethylene oxide. Also useful are alcohol-soluble nylon and polyether of 2,2-bis-(4-hydroxyphenyl)-propane and shrimp chlorohydrin to increase the strength of the cured film. Any amount of these linear organic high molecular weight polymers can be mixed into the entire composition. However, if it exceeds 90% by weight, favorable results will not be obtained in terms of the strength of the image formed. Preferably it is 30-85%. In addition, the photopolymerizable ethylenically unsaturated compound and the linear organic polymer have a weight pressure of 1
It is preferable to set it as the range of /9 - 7/3. A more preferable range is 3/7 to 515.

In addition to the above-mentioned basic ingredients, in the present invention, a small amount of a thermal polymerization inhibitor is added to prevent unnecessary thermal polymerization of polymerizable ethylenically unsaturated compounds during the production or storage of the photosensitive composition. It is desirable to do so. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-butyl-p-cresol, pyrogallol,
1-Butylcatechol, benzoquinone, 4.4'-thiobis(3-methyl-6-t-butylphenol), 2
Examples include 2'-methylenebis(4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine cerous salt. The amount of the thermal polymerization inhibitor added is approximately 0.0% based on the weight of the entire composition. O1% to 1% to about 5%. If necessary, higher fatty acid derivatives such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition caused by oxygen, and may be unevenly distributed on the surface of the photosensitive layer during the drying process after coating. . The amount of the higher fatty acid derivative added is preferably about 0.5% to about 10% of the total composition.

Furthermore, dyes or pigments may be added for the purpose of coloring the photosensitive layer. The amount of dyes and pigments added is preferably about 0.5% to about 5% of the total composition. In addition, inorganic fillers and other known additives may be added to improve the physical properties of the cured film.

When applying the photopolymerizable composition of the present invention onto a support, it can be used after being dissolved in various organic solvents.

The 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 monotyl ether,
Propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene gelicol monoisopropyl ether, ethylene glycol motuptyl 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 , r-butyrolactone, methyl lactate,
Examples include ethyl lactate. These solvents can be used alone or in combination. The appropriate concentration of solids in the coating solution is 2 to 50% by weight.

The coating amount is approximately 0.1 g/m" to approximately 1 g/m" after drying.
A range of 0 g/m2 is suitable. More preferably, it is 0.5 to 5 g/m''.

As the support, a dimensionally stable plate-like material is used. Examples of the dimensionally stable plate-like material include paper, paper laminated with plastic (e.g., polyethylene, polypropylene, polystyrene, etc.), and materials such as aluminum (including aluminum alloys), zinc, copper, etc. sheets of metal such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. , paper or plastic film on which metals such as those mentioned above are laminated or vapor-deposited. Among these supports, aluminum plates are particularly preferred because they are extremely dimensionally stable and inexpensive. In addition, the special public official
Composite sheets of aluminum sheets bonded onto polyethylene terephthalate films, such as those described in No. 327, are also preferred.

In addition, in the case of a support having a metal surface, especially aluminum, surface treatments such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, etc., or anodization treatment are performed. Preferably.

Furthermore, an aluminum plate that has been grained and then immersed in an aqueous sodium silicate solution can be preferably used. As described in Japanese Patent Publication No. 47-5125, an aluminum plate which has been anodized and then immersed in an aqueous solution of an alkali metal silicate is preferably used. The above-mentioned anodizing treatment may be carried out by electrolysis using an aqueous or non-aqueous solution of an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, or boric acid, or an organic acid such as oxalic acid or sulfamic acid, or a salt thereof alone or in combination of two or more. This is carried out by passing an electric current through a liquid using an aluminum plate as an anode.

Also effective is silicate electrodeposition as described in US Pat. No. 3,658,662.

Furthermore, Japanese Patent Publication No. 46-27481, Japanese Patent Publication No. 52-586
Also useful is a surface treatment that combines a support coated with electrolytic grains with the above-mentioned anodic oxidation treatment and sodium silicate treatment as disclosed in No. 02 and JP-A-52-30503.

Also suitable are those which have been sequentially subjected to mechanical roughening, chemical treatment, electrolytic graining, anodic oxidation treatment, and sodium silicate treatment as disclosed in JP-A No. 56-28893.

Furthermore, after these treatments, water-soluble resins such as polyvinylphosphonic acid, polymers and copolymers having sulfonic acid groups in their side chains, polyacrylic acid, water-soluble metal salts (e.g. zinc borate), or Undercoating with yellow dye, amine salt, etc. is 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 improve the adhesion of the photosensitive layer. This is done for such purposes.

On the layer of photopolymerizable composition provided on the support, 1.
In order to prevent the polymerization inhibiting effect caused by oxygen in the air, a protective layer may be provided, for example, made of a polymer with excellent oxygen barrier properties such as polyvinyl alcohol, particularly polyvinyl alcohol with a degree of saponification of 99% or more, acidic cellulose, etc. . A method for applying such a protective layer is described in detail in, for example, US Pat. No. 3,458,311 and Japanese Patent Publication No. 55-49729.

Furthermore, since the photopolymerizable composition of the present invention is cured and gelled by polymerization and crosslinking reactions caused by light, it can be applied to a wide range of applications such as photoresists for producing printing plates, printed circuit boards, and the like. In particular, the photopolymerizable composition of the present invention has high sensitivity and a wide range of spectral sensitivity characteristics up to the visible light region, so that good effects can be obtained when applied to photosensitive materials for visible light lasers such as ^r゛ lasers. .

Further, since the photopolymerizable composition of the present invention is highly sensitive and sensitive to visible light, it can be particularly advantageously used for image forming systems using microcapsules.

For use in an image forming system using microcapsules, for example, Japanese Patent Laid-Open Nos. 57-197538 and 61-
No. 1.30945, No. 58-88739, No. 58-8
No. 8740, European Patent No. 223,587A1, etc. can be referred to. In this image forming method, for example, microcapsules containing a photopolymerization initiator composition consisting of an ethylenic vinyl compound and a photopolymerization initiator and a dye precursor are coated on a support, and this photosensitive sheet is exposed to light in an imagewise manner. After curing the microcapsules in the unexposed area, a developer sheet is placed over the entire surface and pressure is applied to destroy the microcapsules in the unexposed area. ) to develop color.

After imagewise exposure of a photosensitive material using the photopolymerizable composition of the present invention, unexposed areas of the photosensitive layer are removed with a developer to obtain an image. Preferred developing solutions for using these photopolymerizable compositions in preparing lithographic printing plates include those disclosed in Japanese Patent Publication No. 57-74
Examples include developing solutions such as those described in No. 27; ammonium triphosphate,
Aqueous solutions of inorganic alkaline agents such as ammonium diphosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, etc. and organic alkaline agents such as monoethanolamine or jetanolamine are suitable. The concentration of the cough alkaline solution is 0.1 to 10% by weight, preferably 0.
It is added in an amount of 5 to 5% by weight.

In addition, the alkaline aqueous solution may contain a surfactant, benzyl alcohol, 2-phenoxyethanol,
Small amounts of organic solvents such as 2-butoxyshetanol can be included. For example, those described in US Pat. No. 3,375,171 and US Pat. No. 3,615,480 may be mentioned.

Furthermore, JP-A-50-26601 and JP-A-58-54341
The developing solutions described in Japanese Patent Publication No. 56-39464 and Japanese Patent Publication No. 56-42860 are also excellent.

〔Effect of the invention〕

The photopolymerizable composition of the present invention has a high sensitivity to active light in a wide range from ultraviolet rays to visible light.

Therefore, light sources include ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon lights, xenon lamps, metal halide lamps, various visible and ultraviolet laser lamps, fluorescent lamps, tungsten lamps, and sunlight. can be used.

〔Example〕

The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Examples 1 to 43, Comparative Examples 1 to 29 After sanding the surface of an aluminum plate with a thickness of 0.30 ffll11 using a nylon brush and 400 mesh of bumiston water g < 1, the surface was thoroughly washed with water. did. 1
After etching by immersing in 0% sodium hydroxide at 70°C for 60 seconds, washing with running water, neutralizing with 20% nitric acid, and then washing with water. ■This.

= 12. Electrolytic surface roughening treatment was carried out in a 1% nitric acid aqueous solution using an alternating sinusoidal waveform current under TV conditions with an anode special electricity amount of 160 corons/dm2. When the surface roughness was measured, it was 0.6μ (expressed as Ra). Subsequently, after being immersed in a 30% sulfuric acid aqueous solution and desmutted at 55°C for 2 minutes, the current density was 2 A in a 20% sulfuric acid aqueous solution.
/dm2, the thickness of the anodic oxide film is 2.7 g/m
It was anodized for 2 minutes so that it became 2.

On the thus treated aluminum plate, a photosensitive composition having the composition shown below was coated at a dry coating weight of 1.4 g/m'' and dried at 80°C for 2 minutes to form a photosensitive layer.

Trimethylolpropane tri(acryloyloxypropyl)ethyl log Allyl methacrylate/methacrylic acid copolymer (copolymerization molar ratio 80/20) 2.0 g Photoinitiator Xg Fluorine-based nonionic surfactant 0.03 g Methyl ethyl ketone 20 g Propylene Glycol monomethyl ether acetate A 3% by weight aqueous solution of polyvinyl alcohol (degree of saponification 86.5-89 mol%, degree of polymerization 1000) was coated on a 20 μm photosensitive layer so that the dry coating weight was 2 g/m. and 100°C/
Allowed to dry for 2 minutes.

The photosensitivity test was conducted using visible light and laser light (wavelength = 4
88 nm) was used. For visible light, a tungsten lamp is used as the light source and a Kenko optical filter is used.
optical filter) BP-49. For photosensitivity measurements, a Tomiju PS stamp guide (manufactured by Fuji Photo Film Co., Ltd., with a transmission optical density of 0,
It was performed using a step tablet (step tablet with 15 steps in increments of 0.15 and up to 15 steps). The number of clear steps of the PS step guide is shown when the illumination intensity at the surface of the photosensitive material film is 25 and is exposed for 40 seconds with LIJX.

The larger the value of this stage number, the higher the sensitivity.

Note that the sensitivity to Ar'' laser light was also measured in the following manner.

The laser beam is an Ar' laser (Refcell Model 95).
-3) single line with a wavelength of 488 nm and a beam diameter of 2
The intensity of the Ar'' laser was changed and scanned (using an ND filter) at 5μ, the line width obtained after development was measured, and the intensity of the laser when a line width of 25μ was reproduced was defined as the sensitivity. .The lower this value, the higher the sensitivity. In the table, (-・) means extremely low sensitivity, specifically 4.
8IIJ/c or more.

Development was carried out by immersing the film in the following developer solution at 25"C5 for 1 minute.

, IK potassium silicate 1 potassium hydroxide 0 g 5 g = water 000 g (a) Example 1 of the invention comprising components (ii) and (iii)
Comparative Examples 1 to 15, which do not contain component (11), have high sensitivity to visible light and Ar'' laser light.
It can be seen that No. 7 has no sensitivity at all to either visible light or Ar'' laser light.

It can be seen that Examples 16 to 29, which further contain component (iv) in addition to components (ii) and (ij), have further improved sensitivity than Examples 1 to 7, which do not contain component (iv).

In addition to the components (ii), (iii), and (1v), the component (
It can be seen that Examples 30 to 43 containing component (V) have further improved sensitivity than Examples 16 to 29 that do not contain component (v).

Comparative Examples 8 to 15 containing component (iii) and/or (iv) but not containing component (11), component (i)
It can be seen that all of Comparative Examples 16 to 29, which do not contain ii), have no sensitivity or extremely low sensitivity.

Claims (3)

[Claims] (1) (i) Polymerizable compound having an addition-polymerizable unsaturated bond (ii) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, R^1 and R^2 are each independently a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxycarbonyl group,
Represents an aryl group, substituted aryl group or aralkyl group. A represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, an alkyl- or aryl-substituted nitrogen atom, or a dialkyl-substituted carbon atom. X represents a group of nonmetallic atoms necessary to form a nitrogen-containing five-membered heterocycle. Y represents a substituted phenyl group, an unsubstituted or substituted polynuclear aromatic ring, or an unsubstituted or substituted heteroaromatic ring. Z is a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group,
It represents a substituted amino group, acyl group, or alkoxycarbonyl group, and may be bonded to Y to form a ring. ), and (iii) (a) a compound having a carbon-halogen bond,
(b) Aromatic onium salts, (c) Organic peroxides, (d) Thio compounds represented by the general formula [II]: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼[II] (Here, R^3 represents an alkyl group, aryl group, or substituted aryl group, and R^4 represents a hydrogen atom or an alkyl group. Also, R^3 and R^4 are bonded to each other. Represents a group of nonmetallic atoms necessary to form a 5- to 7-membered ring that may contain a heteroatom selected from oxygen, sulfur, and nitrogen atoms. A photopolymerizable composition comprising at least one compound selected from the group consisting of ketooxime esters. (2) In claim (1), further (iv) General formula [III]: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] (Here, R^5, R^6, R^7 and R ^8 may be the same or different from each other, and each represents 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 alkynyl group. represents a heterocyclic group, R^5, R^6, R^
Two or more groups of 7 and R^8 may be bonded to form a cyclic structure. However, at least one of R^5, R^6, R^7 and R^8 is a substituted or unsubstituted alkyl group, and Z^+ represents an alkali metal cation or a quaternary ammonium cation. ) A photopolymerizable composition comprising a compound represented by: (3) In Claim 1 or 2, further (v) General formula [IV]: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [IV] Here, Ar is an aromatic aroma selected from one of the following general formulas. R^9 and R^1^0 represent a hydrogen atom or an alkyl group, and R^9 and R^1^0 may be bonded to each other to represent an alkylene group. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the formula, R^1^1 to R^1^5 may be the same or different, and each represents a hydrogen atom, halogen atom,
Alkyl group, alkenyl group, aryl group, substituted aryl group, hydroxyl group, alkoxy group, substituted alkoxy group, -S-
R^1^7 group, -SO-R^1^7 group or -SO_2R
^1^7 groups, provided that at least one of R^1^1 to R^1^5 groups is -S-R^1^7 group, -SO-R^
Represents 1^7 groups or -SO_2R^1^7 groups, R^1^
7 represents an alkyl group or an alkenyl group, and R^1^6 represents a hydrogen atom, an alkyl group, or an acyl group. Y^2 represents a hydrogen atom or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ) A photopolymerizable composition comprising a compound represented by: