JP2631143B2 - Photopolymerizable composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a photopolymerizable composition. For more information,
For a photopolymerizable composition containing a polymerizable compound having an addition-polymerizable unsaturated bond and a photopolymerization initiator having a novel composition, and if necessary, a flocculent organic high-molecular polymer,
The present invention relates to a photopolymerizable composition useful for a photosensitive layer of a sensitive printing plate which can be sensitive to an argon laser beam.

[Conventional technology]

Using a photosensitive composition obtained by mixing a polymerizable compound having an addition-polymerizable unsaturated bond, a photopolymerization initiator, and, if necessary, a binder having a suitable film-forming ability and a thermal polymerization inhibitor. A method of duplicating an image by a static method is currently known. That is, U.S. Pat.
No. 022, No. 2,902,356 or No. 3,870,524, this type of photosensitive composition undergoes photopolymerization by light irradiation, and is cured and insolubilized. By performing light irradiation through a desired negative image and removing only the unexposed portions with an appropriate solvent (hereinafter, simply referred to as development), a cured image of the desired photopolymerizable composition can be formed. . There is no doubt that this type of photosensitive composition is extremely useful as one used for preparing a printing plate or the like.

In addition, conventionally, only a polymerizable compound having an addition-polymerizable unsaturated bond does not have sufficient photosensitivity, and it has been proposed to add a photopolymerization initiator to enhance photosensitivity.
Such photopolymerization initiators include benzyl, benzoin, benzoin ethyl ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone, 2-benzophenone,
Ethyl anthraquinone and the like have been used. However, when these photopolymerization initiators are used, it takes a long time for image exposure in image formation because the photopolymerizable composition has low sensitivity to curing. Therefore, in the case of a fine image, if there is a slight vibration in the operation, a good quality image cannot be reproduced, and the energy emission amount of the exposure light source must be increased. It was necessary to consider heat dissipation. In addition, there has been a problem that the composition is easily deformed and deteriorated by heat.

Further, these photopolymerization initiators have remarkably low photopolymerization ability with respect to a light source in the visible light region of 400 nm or more as compared with light polymerization ability with respect to a light source in the ultraviolet region of 400 nm or less. Therefore, the application range of the photopolymerizable composition containing the conventional photopolymerization initiator has been extremely limited.

Several proposals have been made for photopolymerization systems sensitive to visible light. As such a proposal, U.S. Pat.
No. 850,445 reports that certain photoreducing dyes, such as rose bengal, eosin, erythrosine, etc., have an effective visible light sensitivity. As an improved technology, a dye-amine complex initiation system (JP-B-44-2018
No. 9), a system of hexaarylbiimidazole and a radical generator and a dye (JP-B-45-37377), and a system of hexaarylbiimidazole and P-dialkylaminobenzylidene ketone (JP-B-47-2528; −155292
), A system of a 3-keto-substituted coumarin 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) have been proposed. These techniques are certainly effective against visible light. However, the photospeed is still not satisfactory enough, and further improvement techniques have been desired.

In recent years, methods for increasing the sensitivity to ultraviolet light and forming an image using a laser have been studied, and the UV projection exposure method in printing plate preparation, laser direct plate making, laser facsimile, holography, etc. are already at the practical stage. High sensitive photosensitive materials corresponding to these are being developed. However, it cannot be said that it has sufficient sensitivity yet.

[Problems to be solved by the invention]

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

That is, an object of the present invention is to provide a photopolymerizable composition containing a photopolymerization initiator which generally 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 a photopolymerizable composition containing a photopolymerization initiator which is highly sensitive to visible light of 400 nm or more, particularly light near 488 nm corresponding to the output of an Ar ⁺ laser. It is in.

[Means for solving the problem]

The present inventors have conducted intensive studies to achieve the above object, and as a result, a specific photopolymerization initiator system significantly increases the photopolymerization rate of a polymerizable compound having an addition-polymerizable unsaturated bond, The inventors have found that they exhibit high sensitivity to the above visible light, and have reached the present invention.

That is, the present invention relates to (1) (i) a polymerizable compound having an addition-polymerizable unsaturated bond, and (ii) a general formula [I] (Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxycarbonyl group, an aryl group, a substituted aryl group or an aralkyl group.
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 atom group necessary to form a nitrogen-containing hetero five-membered ring.

Y represents a substituted phenyl group, an unsubstituted or substituted polynuclear aromatic ring, or an unsubstituted or substituted heteroaromatic ring. Z represents 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, a substituted amino group, an acyl group, or an alkoxycarbonyl group; To form a ring. And (iii) (a) a compound having a carbon-halogen bond, (b) an aromatic onium salt, (c) an organic peroxide, and (d) a thio compound represented by the general formula [II]. : (Where R ³ represents an alkyl group, an aryl group or a substituted aryl group, R ⁴ represents a hydrogen atom or an alkyl group, and R ³ and R ⁴ are bonded to each other and selected from oxygen, sulfur and nitrogen atoms. A non-metallic atom group which may contain a hetero atom or form a 5- to 7-membered ring.) (E) a hexaarylbiimidazole compound and (f) a ketoxime ester The present invention relates to a photopolymerizable composition containing at least one selected compound.

The photopolymerizable composition of the present invention further comprises the following components (i
By adding v) and / or component (v), a photopolymerizable composition with higher sensitivity can be obtained.

(Iv) General formula [III]: (Where R ⁵ , R ⁶ , R ⁷ and R ⁸ 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, wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are
Two or more groups may combine 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. Z ⁺ represents an alkali metal cation or a quaternary ammonium cation. ) The compound represented by these.

(V) General formula [IV]: Here, Ar represents an aromatic group selected from one of the following general formulas, R ⁹ and R ¹⁰ represent a hydrogen atom or an alkyl group,
R ⁹ and R ¹⁰ may be bonded to each other to represent an alkylene group.

(Wherein, R ^{11 to} R ¹⁵ 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 ¹⁷ groups, -SO-R
It represents the ¹⁷ group or -SO ₂ R ¹⁷ group, provided that at least one of R ¹¹ to R ¹⁵ group represents -S-R ¹⁷ group, group -SO-R ¹⁷ or -SO ₂ R ¹⁷ group, R ¹⁷ Represents an alkyl group, an alkenyl group, and R ¹⁶ represents a hydrogen atom, an alkyl group or an acyl group.

Y ² is a hydrogen atom or Represents ).

Hereinafter, each component of the photopolymerizable composition of the present invention will be described in detail.

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

For example, monomers, prepolymers, ie, dimers, 3
It has a chemical form such as a monomer 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 acrylates such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and 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, pen Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate,
Sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer and the like.

As methacrylic acid esters, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 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
-Hydroxypropoxy) phenyl] dimethylmethane,
Bis- [p- (acryloxyethoxy) phenyl] dimethylmethane;

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

The crotonic acid ester includes 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, methylenebis-methacrylamide, 1,
Examples include 6-hexamethylenebis-acrylamide, 1,6-hexamethylenebis-methacrylamide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide, and the like.

Other examples include a polyisocyanate compound having two or more isocyanate groups in one molecule described in JP-B-48-41708, etc.
And a vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule to which a hydroxyl-containing vinyl monomer is added.

CH ₂ ＣC (R) COOCH ₂ CH (R ′) OH (A) (where R and R ′ represent H or CH ₃ ) Further, as described in JP-A-51-37193. Urethane acrylates, JP-A-48-64183, JP-B-49
And polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid as described in JP-A-43191 and JP-B-52-30490. it can. Furthermore, Japan Adhesion Association magazine vol.20, No.7, 30
Those described as photocurable monomers and oligomers on pages 0 to 308 can also be used. The amount of these used is preferably 5 to 50% by weight (hereinafter abbreviated as%), more preferably 10 to 40% by weight based on all components.
It is.

Component (ii) used in the present invention has the following general formula [I]
It is a compound shown by these.

(Wherein R ¹ and R ² 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 represents an oxygen atom, a sulfur atom,
Represents a selenium atom, tellurium atom, alkyl or aryl substituted nitrogen atom, or dialkyl substituted carbon atom. X represents a nonmetallic atom group necessary to form a nitrogen-containing hetero five-membered ring.

Y represents a substituted phenyl group, an unsubstituted or substituted polynuclear aromatic ring, or an unsubstituted or substituted heteroaromatic ring. Z represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an alkoxyl group, an alkylthio group, an arylthio group, a substituted amino group, an acyl group, or an alkoxycarbonyl group; To form a ring. Examples of R ¹ and R ² in the general formula [I] are shown below.
As the alkyl group, a straight chain having 1 to 18 carbon atoms,
Examples thereof include branched and cyclic alkyl groups, and specific examples thereof include a methyl group, an ethyl group, a propyl group,
Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, isopentyl, isohexyl, sec-butyl, neopentyl, tert-butyl Group, tert-pentyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and 2-norbornyl group. Of these,
A linear or branched alkyl group having 1 to 10 carbon atoms and a cyclic alkyl group having 6 to 10 carbon atoms are preferred.

Examples of the substituent of the substituted alkyl group include a halogen atom (fluorine, chlorine, bromine, and iodine), a hydroxyl group, an alkoxyl group, an acyloxy group, an acylamino group, an alkoxycarbonyl group, and an N-substituted carbamoyl group. On the other hand, as the alkyl group of the substituted alkyl group, the aforementioned alkyl group having 1 to 18 carbon atoms, preferably 1
A straight-chain or branched alkyl group having 1 to 10 carbon atoms and a cyclic alkyl group having 6 to 10 carbon atoms, and most preferably a straight-chain or branched alkyl group having 1 to 4 carbon atoms. be able to. Specific examples of the substituted alkyl group include chloromethyl group, bromomethyl group, 2-chloroethyl group, 2,2,2-trichloroethyl group, 2-chloropentyl group, 1- (chloromethyl) propyl group, 10-
Bromodecyl group, 18-methyloctadecyl group, chlorocyclohexyl group, hydroxymethyl group, 2-hydroxyethyl group, 2-hydroxybutyl group, 5-hydroxypentyl group, 10-hydroxydecyl group, 2-hydroxyoctadecyl group, 2- ( (Hydroxymethyl) ethyl group, hydroxycyclohexyl group, 3-hydroxy-2-norbornyl group, methoxymethyl group, methoxyethyl group, methoxypropyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, methoxyethoxyethyl group,
Ethoxyethoxyethyl group, acetoxyethyl group, propionyloxyethyl group, benzoyloxyethyl group,
Examples include a benzoyloxypentyl group, a benzoyloxyethoxyethyl group, an acetylaminoethyl group, a propionylamino group, an N-methylcarbamoylethyl group, and an N, N-diethylcarbamoylethyl group.

The aryl group includes one benzene ring residue (phenyl group), two and three condensed benzene ring residues (naphthyl group, anthryl group, and phenanthryl group) and the remaining two benzene ring assembly systems. And a condensed residue of a benzene ring and a 5-membered unsaturated ring (indenyl group, acenaphthenyl group, fluorenyl group).

Examples of the substituted aryl group include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an amino group, and a substituted amino group (for example, a monoalkyl-substituted amino group (an alkyl group; Methyl group, ethyl group, propyl group, pentyl group, isopropyl group, sec-
Butyl group, isopentyl group), dialkylamino group (example of alkyl group is the same as example of monoalkyl-substituted amino group), monoacylamino group (example of acyl group, acetyl group, propionyl group, butyryl group, isobutyryl) Groups, valeryl groups), cyano groups, alkyl groups (linear, branched and cyclic alkyl groups having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms)
Up to linear, branched and cyclic alkyl groups, most preferably straight and branched alkyl groups having 1 to 4 carbon atoms, examples of which have already been mentioned above. ), A halogenalkyl group (eg, chloromethyl group, 2
-Chloroethyl group, 5-chloropentyl group, trifluoromethyl group), alkoxyl group (examples of alkyl group, methyl, ethyl, butyl, pentyl, isopropyl, isopentyl, 2-methylbutyl, sec-butyl) Group), aryloxy group (example of aryl group, phenyl group, 1-naphthyl group, 2-naphthyl group), alkoxycarbonyl group (example of alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group) An acyloxy group (an example of an acyl group is the same as an example of a monoacylamino group),
One or two substituents such as an alkoxysulfonyl group (an example of an alkyl group is the same as the example of an alkyl group of an alkoxyl group);
Residues substituted by two or more of the same substituents or different substituents may be mentioned. Specific examples of these aryl groups and substituted aryl groups include phenyl, chlorophenyl, aminophenyl, (methylamino)
Phenyl, (ethylamino) phenyl, (dimethylamino) phenyl, acetylaminophenyl, tolyl, ethylphenyl, (chloromethyl) phenyl, acetylphenyl, phenoxyphenyl, methoxycarbonylphenyl, ethoxy Carbonylphenyl group, acetoxyphenyl group, methoxysulfonylphenyl group, naphthyl group, 2-amino-1-naphthyl group, 1
-Dimethylamino-2-naphthyl group, chloronaphthyl group, methylnaphthyl group, anthryl group, phenanthryl group, indenyl group, biphenyl group, chlorobiphenylyl group, aminobiphenylyl group, methylbiphenylyl group, acenaphthenyl group. it can. Among these, a phenyl group and a phenyl group in which one or more of the above substituents are the same or two or more of the above substituents different from each other are substituted are preferred.

Examples of the aralkyl group include a residue 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. Benzyl, phenethyl, 3-phenylpropyl, 3-phenylhexyl, 10-phenyldecyl, 4-phenylcyclohexyl, 1-naphthylmethyl, 2- (1-
A naphthyl) ethyl group and a 2-naphthylmethyl group.

Alkoxycarbonyl groups include those having 1 to 1 carbon atoms.
Residues in which up to 10 straight-chain, branched and cyclic alkyl groups are bonded to an oxycarbonyl group can be given. Specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group. , Sec-butoxycarbonyl group and tert-butoxycarbonyl group.

Examples of the nitrogen-containing five-membered ring completed by X in cooperation with A, C and N in the general formula [I] include the following.

The substituent E in the formulas (a-1) to (a-4) may or may not be present, but when it is present, the Hammett's σ value of -0.9 to +0.5 Is in the range. Examples include methyl, isopropyl, tert
-Butyl group, phenyl group, trifluoromethyl group, acetyl group, ethoxycarbonyl group, carboxyl group, carboxylate group (—COO ⁻ ), amino group, methylamino group,
Dimethylamino group, an ethylamino group, a diethylamino group, an acetylamino group, -PO ₃ H group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group,
Pentyloxy, phenoxy, hydroxy, acetoxy, methylthio, ethylthio, isopropylthio, mercapto, acetylthio, thiocyano (-SCN), methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl Group, aminosulfonyl group, dimethylsulfonyl group, (-S ⁺ (C
H ₃ ) ₂ ), sulfonato group, (—SO ₃ ⁻ ), fluorine atom, chlorine atom, bromine atom, iodine atom, iosyl group, trimethylsilyl group (—Si (CH ₃ ) ₃ ), triethylsilyl group, trimethylstanyl can be named group _{(-Sn (CH 3) 3)} . Preferred among these substituents 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.

 Examples of Y in the general formula [I] are shown below.

Examples of the substituent of the substituted phenyl group include the same as those described above for E. Examples of the polynuclear aromatic ring include a naphthyl group, an anthryl group, and a phenanthryl group, and these may be substituted with the substituent E described above. Examples of the heteroaromatic ring include a 2-furyl group, a 3-furyl group, a 2-thienyl group, a 3-thienyl group, a 2-pyrrolyl group, and a 3-pyrrolyl group. These may be substituted with the substituent E described above. good.

Examples of Z in the general formula [I] are described below.
Examples of the alkyl group, the substituted alkyl group, the aryl group, and the substituted aryl group include the same as those described as examples of R ¹ and R ² .

Examples of the aralkyl group include a residue 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. Are benzyl, phenethyl, 3-phenylpropyl, 3-phenylhexyl, 10-phenyldecyl, 4-phenylcyclohexyl, 1-naphthylmethyl, 1- (1-
A naphthyl) ethyl group and a 2-naphthylmethyl group.

Examples of the alkylthio group include a residue 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 thereof include a methylthio group and an ethylthio group. Group, propylthio group, butylthio group, sec-butylthio group and tert-butylthio group.

Examples of the alkoxyl group include a residue 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 thereof include a methoxyl group and an ethoxyl group. Group, propoxyl group, butoxyl group, sec-butoxyl group and tert-butoxyl group.

Examples of the substituted amino group include an amino group substituted by a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms. Specific examples thereof include a dimethylamino group, a diethylamino group, and a dipropylamino group. Groups.

Examples of the acyl group include a hydrogen atom, a residue having 1 to 10 carbon atoms, preferably the same 1 to 6 linear, branched or cyclic alkyl group, phenyl group or naphthyl group bonded to carbonyl. Specific examples thereof include formyl, acetyl, propionyl, butyryl, valeryl, benzoyl, and naphthoyl groups.

Alkoxycarbonyl groups include those having 1 to 1 carbon atoms.
Up to 10 linear, branched or cyclic alkyl groups can be mentioned residues bonded to an oxycarbonyl group, specific examples of which include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, Examples thereof include a sec-butoxycarbonyl group and a tert-butoxycarbonyl group.

Examples of a ring formed by combining Y and Z with each other are shown below.

A group of compounds represented by the general formula [I] is “Bull. Soc. C
Hime Belges, Vol. 57, pages 364-372 (1948) Abstract: Chemical Abstracts, Vol. 44, columns 60e-61d (1
950)).

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

Examples of the compound having a carbon-halogen bond, which is an example of the component (iii) used in a preferred embodiment of the present invention, include:
Compounds represented by the following general formulas [V] to [Xl] are preferred.

General formula [V] (Wherein X ′ represents a halogen atom. Y ³ represents —CX ′ ₃ ,
_{-NH 2, -NHR ', - NR} ' 2, represent -OR '. Here, R 'represents an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group. The R is -CX _'3, alkyl group,
Represents a substituted alkyl group, an aryl group, a substituted aryl group, or a substituted alkenyl group. ).

General formula [VI]: (However, R ¹⁸ 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; X 'is a halogen atom; and n is an integer of 1 to 3. ) The compound represented by these.

General formula [VII]: R ¹⁹ -Z-CH _m-1 X ″ _m -R ²⁰ [VII] (where R ¹⁹ is an aryl group or a substituted aryl group, and R ²⁰ is Or halogen; Z is Or a -SO _2, R ^21, R ²² is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group, R ²³ is the same as the general formula (V) R 'in X ″ is a halogen atom, and m is 1 or 2.)

General formula [VIII]: Wherein R ²⁴ is an aryl group or a heterocyclic group which may be substituted, R ²⁵ is a trihaloalkyl group or a trihaloalkenyl group having 1 to 3 carbon atoms, and p is 1, 2 or 3.

General formula [IX]: (Where L is a hydrogen atom or a formula: COR ²⁶ ) _q (CX ₃ ) a substituent of _r , M is a substituted or unsubstituted alkylene group, Q is a sulfur, selenium or oxygen atom, a dialkylmethylene group, An alkene-1,2-ylene group, a 1,2-phenylene group or an NR group; and M is a substituted or unsubstituted alkylene group or alkenyl group, or a 1,2-arylene group; ²⁷ is an alkyl group, an aralkyl group or an alkoxyalkyl group, R ²⁶ 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 carbonylmethylene heterocyclic compound having a trihalogenomethyl group represented by the formula:

General formula [X]: (Where X is a halogen atom, t is an integer of 1 to 3,
Is an integer of 1 to 4, R ²⁸ is a hydrogen atom or a CH _{3 -tXt} group, and R ²⁹ is an s-valent optionally substituted unsaturated organic group. Halogeno-5- (halogenomethyl-
Phenyl) -oxazole derivative.

General formula [Xl]: (Where X 'is a halogen atom, v is an integer of 1 to 3,
u is an integer of from 1 to 4, R ³⁰ is a hydrogen atom or a CH _3-v X _v group, R ³¹ is an unsaturated organic group which may be substituted for u-valent. 2- (halogenomethyl-phenyl) -4 represented by
-A halogeno-oxazole derivative.

Compounds having such a carbon-halogen bond include, for example, Wakabayashi et al., Bull. Chem. Soc. Japan, 42 , 292.
4 (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, British patent 138849
No. 2, 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,
Compounds described in JP-A-53-133428, such as 2- (p-methoxystyryl) -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- (acetonaphth-5-yl) -4,6-bis-trichloromethyl-S-
Compounds described in German Patent 3337024, such as triazines, for example, Etc. and others And the like.

J. Org Chem .; 29, 1527 by FCSahaefer et al.
Compounds described in (1964), for example, 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-tris (tribromomethyl) -S-triazine, 2,4,6-
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, And the like.

Or even MPHutt, EFElslager and LMWe
rbel, Journal of Heterocyclicchemistry, Vol. 7 (No.
3), the following compound groups that can be easily synthesized by those skilled in the art according to the synthesis method described on page 511 et seq. (1970). Alternatively, the following compound group Alternatively, compounds as described in DE 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 3333450, for example, Q = S; R ²⁶ = benzene ring Alternatively, a compound group described in German Patent No. 3021590, Alternatively, the compounds described in German Patent No. 3021599, for example, Can be mentioned.

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

In particular, Can be given. Preferred of these are:
A compound of a BF ₄ salt or a PF ₆ salt is more preferably a BF ₄ salt or a PF ₆ salt of an aromatic iodonium salt.

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 bonds in the molecule. , Methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,
1-bis (tertiarybutylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tertiarybutylperoxy) cyclohexane, 2,2-bis (tertiarybutylperoxy) butane, tertiary Butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide,
Paramethane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, ditertiary 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, octa Noyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide, Diisopropyl peroxy dicarbonate, di-2-ethylhexyl peroxy dicarbonate, di-2-ethoxyethyl peroxy dicarbonate, dimethoxy isopropyl peroxy carbonate,
Di (3-methyl-3-methoxybutyl) peroxydicarbonate, tertiary butyl peroxy acetate, tertiary butyl peroxy pivalate, tertiary butyl peroxy neodecanoate, tertiary butyl peroxy octanoate, Tertiary butyl peroxy-3,5,5-trimethylhexanoate, tertiary butyl peroxy laurate, tertiary butyl peroxy benzoate, ditertiary butyl diperoxy isophthalate, 2,2-dimethyl-2, 5-di (benzoylperoxy) hexane, tertiarybutylperoxide maleic acid, tertiarybutylperoxyisopropylcarbonate, 3,3 ', 4,4'-tetra- (t
-Butylperoxycarbonyl) benzophenone, 3,
3 ', 4,4'-tetra- (t-amylperoxycarbonyl) 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-isopropylcumylper) (Oxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyldi (t-hexylperoxydihydrogenphthalate) and the like.

Among these, 3,3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3', 4,4 '
-Tetra- (t-amylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (t-octylper Oxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (cumylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (p-isopropylcumylperoxycarbonyl) benzophenone, di-t- Peroxide esters such as butyl diperoxyisophthalate are preferred.

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

(Here, R ³ represents an alkyl group, an aryl group or a substituted aryl group, and R ⁴ represents a hydrogen atom or an alkyl group.
R ³ and R ⁴ represent a group of non-metallic atoms necessary for bonding to each other to form a 5- to 7-membered ring which may contain a heteroatom selected from oxygen, sulfur and nitrogen atoms. The alkyl group of R ³ in the general formula (II) is preferably one having 1 to 4 carbon atoms. The aryl group for R ³ has 6 to 6 carbon atoms such as phenyl and naphthyl.
Ten substituents are preferred.As the substituted aryl group, a halogen atom such as a chlorine atom,
Examples include those substituted with an alkyl group such as a methyl group and an alkoxy group such as a methoxy group and an ethoxy group. R ⁴
Is preferably an alkyl group having 1 to 4 carbon atoms.

Specific examples of the thio compound represented by the general formula (II) include the following compounds.

Hexaarylvirimidazole which is another example of the component (iii) used in the present invention includes 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-propionyloxyimiminobtan- 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.

Component (iv) used in the present invention has the following general formula [III]
It is a compound shown by these.

(Where R ⁵ , R ⁶ , R ⁷ and R ⁸ 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, wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are
Two or more groups may combine 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. Z ⁺ represents an alkali metal cation or a quaternary ammonium cation).

The alkyl group of R ^{5 to} R ⁸ includes linear, branched and cyclic alkyl groups, and preferably has 1 to 18 carbon atoms.
Specifically, methyl, ethyl, propyl, isopropyl,
Butyl, pentyl, hexyl, octyl, stearyl,
Cyclobutyl, cyclopentyl, cyclohexyl and the like are included. As the substituted alkyl group, a halogen atom (for example, -Cl, -Br, etc.), a cyano group, a nitro group, an aryl group (preferably a phenyl group), a hydroxy group, (Here, R ³³ and R ³⁴ independently represent a hydrogen atom, an alkyl group having 1 to 14 carbon atoms, or an aryl group.), -COOR ³⁵ (where R ³⁵ is a hydrogen atom, 1 to 14 carbon atoms) An alkyl group or an aryl group). -OCOR ³⁶ or -OR ³⁶ (where R ³⁶
Represents an alkyl group having 1 to 14 carbon atoms or an aryl group. ) As a substituent.

The aryl group of R ^{5 to} R ⁸ 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 aryl group substituted with the above-mentioned substituted alkyl group. And those having an alkyl group having 1 to 14 carbon atoms.

Examples of the alkenyl group of R ^{5 to} R ⁸ include straight-chain, branched and cyclic ones having 2 to 18 carbon atoms.Examples of the substituent of the substituted alkenyl group include the substituents of the above-mentioned substituted alkyl group. Are included.

Examples of the alkynyl group of R ^{5 to} R ⁸ include straight-chain or branched ones having 2 to 28 carbon atoms.Examples of the substituent of the substituted alkynyl group include those described above as the substituent of the substituted alkyl group. included.

Examples of the heterocyclic group of R ^{5 to} R ⁸ include a 5- or more-membered ring, preferably a 5- to 7-membered heterocyclic group containing at least one of N, S and O. Condensed rings may be included. 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 (III) include the compounds described in U.S. Pat. Nos. 3,567,453 and 4,343,891, European Patents 109,772 and 109,773, and the following compounds.

The photopolymerizable composition of the present invention contains a compound [component (v)] represented by the following general formula [IV],
The sensitivity can be further increased.

In the general formula (IV), Ar represents an aromatic group selected from one of the following general formulas, R ⁹ and R ¹⁰ represent a hydrogen atom or an alkyl group, and R ⁹ and R ¹⁰ are mutually bonded To represent an alkylene group.

(Wherein, R ^{11 to} R ¹⁵ 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 ¹⁷ groups, -SO-R
It represents a ¹⁷ group or -SO ₂ R ¹⁷ group, provided that at least one of R ¹¹ to R ¹⁵ group represents -S-R ¹⁷ group, group -SO-R ¹⁷ or -SO ₂ R ¹⁷ group, R ¹⁷ Represents an alkyl group, an alkenyl group, and R ¹⁶ represents a hydrogen atom, an alkyl group or an acyl group.

Y ² is a hydrogen atom or Represents Examples of the alkyl group of R ⁹ and R ¹⁰ in the general formula [IV] include those having 1 to 20 carbon atoms such as methyl, ethyl and propyl. Examples of the alkylene group formed by combining R ⁹ and R ¹⁰ include tetramethylene and pentamethylene. Examples of the alkyl group of R ^{11 to} R ¹⁵ in Ar include those having 1 to 4 carbon atoms. Examples of the alkenyl group include those having 3 to 12 carbon atoms.
Further, the aryl group of R ^{11 to} R ¹⁵ includes a phenyl group. Examples of the alkoxy group include those having 1 to 4 carbon atoms. Acetyl as the acyl group for R ¹⁶
And propionyl and acryloyl.

Specific examples of such compounds include: And so on.

Of these, preferred are <IV-1>, <IV-2><IV
-8> and <IV-9>.

The concentration of these photoinitiator systems in the compositions of the present invention is usually low. In addition, when the number is inappropriately large, undesired results such as blocking of the effective light beam occur. The amount of the photopolymerization initiator system in the present invention is in the range of 0.01% to 60% with respect to the total of the photopolymerizable ethylenically unsaturated compound and the linear organic high molecular weight polymer added as required. It is preferred to use. More preferably, good results are obtained at 1% to 30%.

Component (ii) as a photopolymerization initiator used in the present invention
It is appropriate to use 0.01 to 50 parts by weight of component (iii) based on 1 part by weight of the organic dye of component (ii) of (iii).
More preferably 0.02 to 20 parts by weight, most preferably 0.05 to
10 parts by weight. Further, when the component (iv) is used in combination, the component (iv) is added in an amount of 0.
05 to 30 parts by weight, most preferably 0.2 to 5 parts by weight.
Further, when the compound of the component (v) is used in combination, the component (v) may be used in an amount of 0.01 to 1 part by weight of the organic dye of the component (ii).
It is appropriate to use 50 parts by weight, more preferably 0.02
-20 parts by weight, most preferably 0.05-10 parts by weight.

The photopolymerizable composition of the present invention preferably contains (vi) 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 used not only as a film forming agent of the composition,
Water, weakly alkaline water or an organic solvent is selected and used depending on the use as a developer. 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 addition polymers having a carboxylic acid in a side chain, for example, JP-A-59-44615, JP-B-54-34327,
JP-B-58-12577, JP-B-54-25957, JP-A-54-92
723, JP-A-59-53836, JP-A-59-71048, that is, methacrylic acid copolymer, 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 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 / optionally And other addition-polymerizable vinyl monomers] copolymers. In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. To increase the strength of the cured film, alcohol-soluble nylon or 2,2-bis- (4-hydroxyphenyl)
-Useful are, for example, polyethers of propane and epichlorohydrin. These linear organic high molecular polymers can be mixed in an arbitrary amount in the whole 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 30-85%. 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 a thermal polymerization inhibitor is added to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during the production or storage of the photosensitive composition. It is desirable to do. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol) ), 2,
2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine cerium salt and the like. The addition amount of the thermal polymerization inhibitor is
Preferred is from about 0.01% to about 5% by weight of the total composition.
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 addition amount of the higher fatty acid derivative is preferably about 0.5% to about 10% of the whole composition. Further, a dye or a pigment may be added for the purpose of coloring the photosensitive layer. The amount of dye and pigment added is preferably from 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 the photopolymerizable composition of the present invention is coated on a support, it is used after being dissolved in various organic solvents. As the solvent used here, 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, Ethylene 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 to 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. Examples of the dimensionally stable plate include paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), and aluminum (including aluminum alloy), zinc, copper, etc. Metal plates, further, for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, plastic films such as polyvinyl acetal, Paper or plastic film on which the above-mentioned metal is laminated or vapor-deposited may be used. Among these supports, the aluminum plate is particularly preferable because it is extremely dimensionally stable and inexpensive. Furthermore, Japanese Patent Publication No. 48-1832
A composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in No. 7 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 anodic oxidation treatment is performed. Is preferred.

Further, an aluminum plate that 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. The anodizing treatment is, for example, phosphoric acid, chromic acid, sulfuric acid, an inorganic acid such as 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 electrolytic solutions. It is carried out by passing a current through an aluminum plate as an anode.

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

Furthermore, a support provided with electrolytic grains as disclosed in JP-B-46-27481, JP-A-52-58602, and JP-A-52-30503 is combined with the above anodizing treatment and sodium silicate treatment. Surface treatments are also useful.

Further, those which are sequentially subjected to mechanical roughening, chemical etching, electrolytic graining, anodizing treatment and sodium silicate treatment as disclosed in JP-A-56-28893 are also suitable.

Furthermore, after performing these treatments, aqueous resins such as polyvinylphosphonic acid, polymers and copolymers having a sulfonic acid group in a side chain, polyacrylic acid, a water-soluble metal salt (for example, zinc borate) or yellow Those coated with a 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 improve the adhesion of the photosensitive layer. Etc.

On the layer of the photopolymerizable composition provided on the support,
In order to prevent the polymerization inhibiting action due to oxygen in the air, a protective layer made of a polymer having excellent oxygen barrier properties such as polyvinyl alcohol, particularly polyvinyl alcohol having a saponification degree of 99% or more, and acidic celluloses may be provided. .
The method of applying such a protective layer is described in detail, for example, in U.S. Pat. No. 3,458,311 and JP-B-55-49729.

Further, the photopolymerizable composition of the present invention is cured and gelled by a polymerization / crosslinking reaction by light, so that it can be applied to various fields such as a photoresist in 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, a good effect can be obtained when applied to a photosensitive material for a visible light laser such as an Ar ⁺ laser.

In addition, the photopolymerizable composition of the present invention has high sensitivity and is sensitive to visible light, so that 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 and JP-A-61-130945.
No. 58-88739, No. 58-88740, EP 223,58
Reference can be made to the specification of 7A1 and the like. 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 curing some of the microcapsules,
By overlapping the developer sheet and pressing the entire surface, the microcapsules in the unexposed areas are destroyed, and the color image forming substance (for example, a dye precursor) is transferred to an image receiving element (for example, a developer layer) to form a color. is there.

The photosensitive material using the photopolymerizable composition of the present invention is subjected to image exposure, and then an unexposed portion of the photosensitive layer is removed with a developer to obtain an image. Preferred developers when these photopolymerizable compositions are used for preparing a lithographic printing plate include JP-B-57-7427.
And sodium hydroxide, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, and tertiary phosphoric acid. Aqueous solutions of inorganic alkali agents such as ammonium, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia and organic alkali agents such as monoethanolamine or diethanolamine are suitable. It is added so that the concentration of the alkaline solution is 0.1 to 10% by weight, preferably 0.5 to 5% by weight.

The alkaline aqueous solution may further contain a surfactant, benzyl alcohol, 2-phenoxyethanol,
It can contain small amounts of organic solvents such as 2-butoxyethanol. For example, those described in U.S. Pat. Nos. 3,735,171 and 3,615,480 can be mentioned.

Furthermore, JP-A-50-26601, JP-A-58-54341, JP-B-56
The developers described in JP-A-39464 and JP-A-56-42860 are also excellent.

〔The invention's effect〕

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, and sunlight are used as light sources. it can.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Examples 1 to 43, Comparative Examples 1 to 29 A 0.30 mm thick aluminum plate was
The surface was sand-grained with an aqueous suspension of mesh pumistone, and then thoroughly washed with water. After etching by dipping in 10% sodium hydroxide at 70 ° C. for 60 seconds, the substrate was washed with running water, neutralized and washed with 20% nitric acid, and then washed with water. This is V _A
= 1% using a sinusoidal alternating current under the condition of 12.7V
Electrolytic surface roughening treatment was performed in a nitric acid aqueous solution at an anode electricity amount of 160 coulomb / dm ² . When the surface roughness was measured,
It was 0.6 μ (Ra display). After desmutting 2 minutes immersed 55 ° C. in a 30% aqueous solution of sulfuric acid successively, aqueous 20% sulfuric acid, so that the thickness of the anodized film in a current density of 2A / dm ² is 2.7 g / m ² 2 Anodized for minutes.

On the thus treated aluminum plate, a photosensitive composition having the following composition was applied so as to have a dry coating weight of 1.4 g / m ^2, and dried at 80 ° C. for 2 minutes to form a photosensitive layer.

Trimethylolpropane tri (acryloyloxypropyl) ether 2.0 g Allyl methacrylate / methacrylic acid copolymer (copolymer molar ratio 80/20) 2.0 g Photopolymerization initiator Xg Fluorinated nonionic surfactant 0.03 g Methyl ethyl ketone 20 g Propylene glycol Monomethyl ether acetate 20 g Polyvinyl alcohol (saponification degree 86.5
A 3% by weight aqueous solution of 8989 mol% and a degree of polymerization of 1000) was applied so as to have a dry application weight of 2 g / m ² and dried at 100 ° C. for 2 minutes.

The photosensitivity test was performed using visible light and Ar ⁺ laser light (wavelength = 4
(88 nm). The visible light uses a tungsten lamp as a light source and a Kenko optical filter.
filter) BP-49. The photosensitivity was measured using a Fuji PS step guide (manufactured by Fuji Photo Film Co., Ltd., a step tablet having a transmission optical density of 0.05 at the first stage and increasing sequentially by 0.15 to 15 stages). The illuminance on the light-sensitive material film surface was indicated by the number of clear steps of the PS step guide when exposed for 40 seconds at 25 LUX. The higher the value of the number of stages, the higher the sensitivity.

The sensitivity with Ar ⁺ laser light was also measured as follows.

The laser beam is an Ar ⁺ laser (Rexel model 95-
Using a single line of wavelength 488 nm of 3) with a beam diameter of 25 μ, the scanning was performed while changing the intensity of the Ar ⁺ laser (using an ND filter). The line width obtained after the development was measured, and the intensity of the Ar ⁺ laser when the line width of 25 μ was reproduced was regarded as the sensitivity. The lower the value, the higher the sensitivity. In the table, (-) means that the sensitivity is extremely low, specifically, 48 mJ / cm ² or more.

The development was performed by immersing in the following developer at 25 ° C. for 1 minute.

Examples 1 to 15 of the invention comprising components (ii) and (iii)
Have high sensitivity to visible light and Ar ⁺ laser light, whereas Comparative Examples 1 to 7, which do not contain the component (ii),
It can be seen that there is no sensitivity to any of the Ar ⁺ laser light.

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

Examples 30 to 43 which further contain the component (v) in the components (ii), (iii) and (iv) are the same as Examples 16 to 43 which do not contain the component (v).
It can be seen that the sensitivity is further improved from 29.

Containing component (iii) and / or (iv),
It can be seen that Comparative Examples 8 to 15 containing no component (ii) and Comparative Examples 16 to 29 containing no component (iii) have no or very low sensitivity.

 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-59-89303 (JP, A) JP-A-2-179643 (JP, A) JP-A-1-138204 (JP, A)

Claims (3)

(57) [Claims] (1) a polymerizable compound having an addition-polymerizable unsaturated bond; (ii) a compound represented by the general formula [I]: (Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxycarbonyl group, an aryl group, a substituted aryl group or an aralkyl group.
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 atom group necessary to form a nitrogen-containing hetero five-membered ring. 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, a substituted aryl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, a substituted amino group, an acyl group, or an alkoxycarbonyl group, which may be bonded to Y to form a ring. And (iii) (a) a compound having a carbon-halogen bond, (b) an aromatic onium salt, (c) an organic peroxide, and (d) a thio compound represented by the general formula [II]. : (Where R ³ represents an alkyl group, an aryl group or a substituted aryl group, R ⁴ represents a hydrogen atom or an alkyl group, and R ³ and R ⁴ are bonded to each other and selected from oxygen, sulfur and nitrogen atoms. A non-metallic atom group which may contain a hetero atom or form a 5- to 7-membered ring.) (E) a hexaarylbiimidazole compound, and A photopolymerizable composition comprising at least one selected compound. 2. The method according to claim 1, wherein (iv) a compound represented by the following general formula [III]: (Where R ⁵ , R ⁶ , R ⁷ and R ⁸ 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, wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are
Two or more groups may combine 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. Z ⁺ represents an alkali metal cation or a quaternary ammonium cation. A photopolymerizable composition comprising a compound represented by the formula: 3. The method according to claim 1, wherein (v) a compound represented by the general formula [IV]: Here, Ar represents an aromatic group selected from one of the following general formulas, R ⁹ and R ¹⁰ represent a hydrogen atom or an alkyl group,
R ⁹ and R ¹⁰ may be bonded to each other to represent an alkylene group. (Wherein, R ^{11 to} R ¹⁵ 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 ¹⁷ groups, -SO-R
It represents the ¹⁷ group or -SO ₂ R ¹⁷ group, provided that at least one of R ¹¹ to R ¹⁵ group represents -S-R ¹⁷ group, group -SO-R ¹⁷ or -SO ₂ R ¹⁷ group, R ¹⁷ Represents an alkyl group, an alkenyl group, and R ¹⁶ represents a hydrogen atom, an alkyl group or an acyl group. Y ² is a hydrogen atom or Represents A photopolymerizable composition comprising a compound represented by the formula: