JPH0699497B2 - Photopolymerizable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial field of use" The present invention relates to photopolymerizable compositions. More specifically, regarding a photopolymerizable composition containing a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator having a novel composition, and a linear organic high molecular polymer, if necessary, for example, The present invention relates to a photopolymerizable composition useful for a photosensitive layer of a photosensitive printing plate which is sensitive to an argon laser light source.

"Prior Art" A photosensitive composition prepared by mixing a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a binder having an appropriate film-forming ability, and a thermal polymerization inhibitor if necessary. A method of reproducing an image using a photographic method is currently known. That is, U.S. Pat.
No. 2,902,356 or 3,870,524, a photosensitive composition of this kind undergoes photopolymerization upon irradiation with light, and is cured and insolubilized. None, by performing light irradiation through a negative image of a desired image and removing only an unexposed portion with a suitable solvent (hereinafter, simply referred to as development), a cured image of a desired photopolymerizable composition can be formed. . It goes without saying that this type of photosensitive composition is extremely useful as a material used for producing printing plates and the like.

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

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

Several proposals have been made in the past regarding photopolymerization systems sensitive to visible light. As such a proposal, US Pat.
According to No. 445, it is reported that certain photo-reducing dyes such as rose bengal, eosin, and erythrosine have effective visible light sensitivity. As an improved technology, a complex initiation system of dye and amine (Japanese Patent Publication No. 44-2018
9), a system of hexaarylbiimidazole and radical generator and dye (Japanese Patent Publication No. 45-37377), a system of hexaarylbiimidazole and P-dialkylaminobenzylidene ketone (Japanese Patent Publication No. 47-2528, Japanese Patent Publication No. 54-155292 ), 3-
Proposals have been made such as a system of keto-substituted coumarin compounds and active halogen compounds (JP-A-58-15503) and a system of substituted triazines and merocyanine dyes (JP-A-54-151024).
These techniques are certainly effective for visible light.
However, the photosensitivity rate is not yet satisfactory, and further improvement techniques have been desired.

Further, in recent years, high sensitivity to ultraviolet rays, a method of forming an image using a laser has been studied, UV projection exposure method in printing plate making, laser direct plate making, laser facsimile, holography, etc. are already in the stage of practical use, Highly sensitive light-sensitive materials corresponding to these are being developed. However, it cannot be said that it still has sufficient sensitivity.

"Problems to be Solved by the Invention" The present invention is to provide a photopolymerizable composition having high sensitivity.

That is, an object of the present invention is to provide a photopolymerizable composition containing a photopolymerization initiator that increases the photopolymerization rate of a photopolymerizable composition containing a polymerizable compound having an ethylenically unsaturated bond widely. That is.

Another object of the present invention is visible light of 400 nm or more, particularly A
Another object of the present invention is to provide a photopolymerizable composition containing a photopolymerization initiator that is highly sensitive to light around 488 nm corresponding to the output of an r ⁺ laser.

"Means for Solving Problems" The present inventor has conducted extensive studies to achieve the above-mentioned object, and as a result, a certain photopolymerization initiator system has a photopolymerizable compound having an ethylenically unsaturated bond. The present invention has been accomplished by finding that the polymerization rate is remarkably increased and that high sensitivity is exhibited even for visible light of 400 nm or more.

That is, the present invention provides a photopolymerizable composition containing an addition-polymerizable compound having at least one ethylenically unsaturated double bond, a photopolymerization initiator, and, if necessary, a linear organic polymer. The photopolymerizable composition is characterized in that the photopolymerization initiator is a combination of at least the following compounds (a), (b) and (c).

(A) Compound of general formula (I) (In the formula, R _{1 to} R ₄ are independently of each other, a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a hydroxyl group, an alkoxy group, a substituted alkoxy group, an amino group, a substituted amino group. Represents a group, and R ₁ ~
R ₄ may form a ring composed of a non-metal atom together with the carbon atom to which it can bind.

R ₆ is R ₇ or -Z-R _7, Z represents a carbonyl group, a sulfonyl group, a sulfinyl group, or arylene group, R _5, R ₇ independently of one another, a hydrogen atom, an alkyl group, A substituted alkyl group, an aryl group, a substituted aryl group,
It represents a heteroaromatic group, a substituted heteroaromatic group, a cyano group, an alkoxy group, a substituted alkoxy group, a carboxy group, an alkenyl group or a substituted alkenyl group. R ₅ : R ₆ may form a ring composed of non-metal atoms. X represents O, S, NH, or a nitrogen atom having a substituent. Y is an oxygen atom, or And G ₁ and G ₂ may be the same or different, a hydrogen atom, a cyano group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, an aryloxycarbonyl group, a substituted aryloxycarbonyl group, an acyl group, a substituted acyl group,
It represents an arylcarbonyl group, a substituted arylcarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, and a fluorosulfonyl group. But G ₁ and G ₂ are not hydrogen atoms. Further, G ₁ and G ₂ may form a ring composed of a non-metal atom together with the carbon atom which can form it. ) (B) 2,4,6-substituted-1,3,5-represented by the general formula (II)
Triazine compound (In the formula, X, Y, and Z each represent an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or an aralkyl group, and they may be the same or different, but at least one of them is mono- , D or trihalogen-substituted methyl group) or an organic peroxide (C) general formula (III): [(R ⁸ ) (R ⁹ M)] ⁺ nYm ⁻ n (III) (wherein, m and n are integers of 1 or 2, R ⁸ is π-arene, R ⁹ is π-arene or π-arene anion, M is Ti, Cr, Co, Mn, W, Fe, Mo, S, Se, T
a cation selected from e, N, P, As, Bi and Sb, Y
Is B ▲ F ^- ₄ ▼, P ▲ F ^- ₆ ▼, As ▲ F ^- ₆ ▼, Sb ▲ F ^- ₆ ▼,
_{^{FeC ▲ l - 4 ▼, SnC}} ▲ l 2- 6 ▼, SbCl - and BiC ▲ l ^- ₆ ▼
Represents an anion selected from ) At least one compound selected from the compound represented by :, an aromatic onium salt, and an aromatic halonium salt.

The present invention also provides a photopolymerizable composition containing an addition-polymerizable compound having at least one ethylenically unsaturated double bond, a photopolymerization initiator, and, if necessary, a linear organic polymer. The present invention relates to a photopolymerizable composition, wherein the photopolymerization initiator is a combination of at least the following compounds (a), (b) and (d).

(A) Compound of general formula (I) (In the formula, R _{1 to} R ₄ are independently of each other, a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a hydroxyl group, an alkoxy group, a substituted alkoxy group, an amino group, a substituted amino group. Represents a group, and R ₁ ~
R ₄ may form a ring composed of a non-metal atom together with the carbon atom to which it can bind.

R ₆ is R ₇ or -Z-R _7, Z represents a carbonyl group, a sulfonyl group, a sulfinyl group, or arylene group, R _5, R ₇ independently of one another, a hydrogen atom, an alkyl group, A substituted alkyl group, an aryl group, a substituted aryl group,
It represents a heteroaromatic group, a substituted heteroaromatic group, a cyano group, an alkoxy group, a substituted alkoxy group, a carboxy group, an alkenyl group or a substituted alkenyl group. Both R ₅ and R ₆ may form a ring composed of a non-metal atom. X is O, S, NH,
Alternatively, it represents a nitrogen atom having a substituent. Y is an oxygen atom,
Or And G ₁ and G ₂ may be the same or different, a hydrogen atom, a cyano group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, an aryloxycarbonyl group, a substituted aryloxycarbonyl group, an acyl group, a substituted acyl group,
It represents an arylcarbonyl group, a substituted arylcarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, and a fluorosulfonyl group. But G ₁ and G ₂ are not hydrogen atoms. Further, G ₁ and G ₂ may form a ring composed of a non-metal atom together with the carbon atom which can form it. ) (B) 2,4,6-substituted-1,3,5-represented by the general formula (II)
Triazine compound (In the formula, X, Y, and Z each represent an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or an aralkyl group, and they may be the same or different, but at least one of them is mono- , Di or trihalogen-substituted methyl group.) (D) Morpholino compound of the general formula (IV) (In the formula, Ar represents an aromatic group selected from one of the following general formulas, R ₁₀ and R ₁₁ represent a hydrogen atom or an alkyl group, and R ₁₀ and R ₁₁ are bonded to each other. May represent an alkylene group.) General formula: (In the formula, R _{12 to} R ₁₃ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group,
Substituted aryl group, a hydroxyl group, an alkoxy group, substituted alkoxy group, -S-R ₁₇ group, represents an -SO-R ₁₇ group or -SO ₂ R ₁₇ group, provided that at least one of R ₁₂ to R ₁₆ group - S-R ₁₇ groups,
It represents -SO-R ₁₇ group or -SO ₂ R ₁₇ group, R ₁₇ represents an alkyl group having,
The alkenyl group and R ₁₈ represent a hydrogen atom, an alkyl group or an acyl group. Y ₁ is a hydrogen atom or Represents ) Hereinafter, the present invention will be described in detail.

The polymerizable compound having an ethylenically unsaturated bond used in the present invention is a compound having at least one ethylenically unsaturated bond in its chemical structure. For example, it has a chemical form such as a monomer, a prepolymer, that is, a dimer, a trimer and an oligomer, or a mixture thereof and a copolymer thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids and salts thereof, esters of unsaturated carboxylic acids with aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids with aliphatic polyvalent amine compounds. To be

Specific examples of the unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, and maleic acid.

Examples of the salts of unsaturated carboxylic acids include sodium salts and potassium salts of the aforementioned acids.

Further, specific examples of the monomer of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include ethylene glycol diacrylate as an acrylic acid ester,
Triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate,
Neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, penta Erythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate,
Dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate,
Examples include tri (acryloyloxyethyl) isocyanurate and polyester acrylate oligomer.

As the methacrylic acid ester, 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-methacryl Oxy-
2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p- (acryloxyethoxy) phenyl] dimethylmethane and the like.

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

Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate.

Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.

Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

Furthermore, a mixture of the above-mentioned ester monomers can also be mentioned.

Further, specific examples of the amide monomer of the aliphatic polyvalent amine compound and the unsaturated carboxylic acid include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6
-Hexamethylenebis-acrylamide, 1,6-hexamethylenebis-methacrylamide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like.

As another example, vinyl containing a hydroxyl group represented by the following general formula (A) in a polyisocyanate compound having two or more isocyanate groups in one molecule described in JP-B-48-41708. Examples thereof include vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule to which a monomer is added.

CH ₂ ═C (R) COOCH ₂ CH (R ′) OH (A) (wherein R and R ′ represent H or CH ₃ ). Also, as described in JP-A-51-37193. Urethane acrylates, JP-A-48-64183, JP-B-49-4
Polyfunctional acrylates and methacrylates such as polyester acrylates as described in Japanese Patent Publication No. 3191 and Japanese Patent Publication No. 52-30490, epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid can be mentioned. . Furthermore, Japan Adhesive Association Magazine Vol.20, No.7, 300-3
Those introduced as photocurable monomers and oligomers on page 08 can also be used. The amount of these used is 5 to 50% by weight (hereinafter abbreviated as%), preferably 10 to 40%, based on all components.

Next, the photopolymerization initiator which is a remarkable feature of the photopolymerizable composition of the present invention will be described.

General formula (I) used in the present invention In the compound represented by, those having 1 to 20 carbon atoms such as methyl, ethyl and t-butyl can be used as the alkyl groups of R _{1 to} R ₅ and R ₇ , and the aryl group can have 1 to 10 carbon atoms such as phenyl. Up to individual ones can be used. As the alkoxy group, those having 1 to 6 carbon atoms such as methoxy, ethoxy and butoxy can be used.

Further, as the substituted amino group for R _{1 to} R ₄ , an alkylamino or arylamino group having 1 to 20 carbon atoms such as methylamino, dimethylamino, diethylamino, diphenylamino, piperidino and morpholino can be used.

These alkyl group, aryl group, alkoxy group, alkylamino group, arylamino group may have a substituent, for example, a halogen atom such as fluorine, chlorine, bromine, an alkoxycarbonyl group such as an ethoxycarbonyl group, Examples include alkoxy groups such as methoxy and ethoxy, aryl groups such as phenyl, and cyano groups. When R _{1 to} R ₄ form a ring composed of a non-metal atom together with the carbon atom to which it is bound, examples of the structure containing the ring include those shown in (A), (B) and (C) below.

The alkenyl group of R ₅ and R ₇ has 2 carbon atoms such as a styryl group.
In the case of a heteroaromatic group, the following (D)
What is shown in (H) can be used.

These heteroaromatic groups may also have a substituent. As the substituent, a halogen atom such as fluorine, chlorine and bromine, an alkylamino group having 1 to 20 carbon atoms such as dimethylamino, diethylamino and diphenylamino, an arylamino group, an alkyl group having 1 to 20 carbon atoms, carbon There are several 1 to 6 alkoxy groups and the like. R ₅ and R ₆ may form a ring together with the carbon atom which can be bonded to it. Examples include the structure shown in (J) below.

When X is a nitrogen atom having a substituent, the substituent is R ₁ to
It is possible to use those having the same meanings as the alkyl group and aryl group mentioned for R ₅ and R ₇ .

Y is O or And G ₁ and G ₂ are the same or different hydrogen atom, cyano group,
An alkoxycarbonyl group having an alkyl group having 1 to 10 carbon atoms such as an ethoxycarbonyl group, an aryloxycarbonyl group having an aryl group having 6 to 10 carbon atoms such as a phenoxycarbonyl group, an acetyl group, a propionyl group, etc. 6 acyl groups, benzoyl groups, etc., C7-11 arylcarbonyl groups, methylthio groups, ethylthio groups, etc., C1-6 alkylthio groups, phenylthio groups, etc., C6-10 arylthio groups, phenyl It represents an arylsulfonyl group having 6 to 10 carbon atoms such as a sulfonyl group, an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group, an ethylsulfonyl group or a fluorosulfonyl group.

These alkoxycarbonyl group, aryloxycarbonyl group, acyl group, arylcarbonyl group, alkylthio group, arylthio group, arylsulfonyl group and alkylsulfonyl group may have a substituent. As the substituent, a halogen atom such as chlorine, an alkoxycarbonyl group having an alkyl group having 1 to 6 carbon atoms, a carboxy group, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, A cyano group may be mentioned. Furthermore, in the case of an aryloxycarbonyl group, an arylcarbonyl group, an arylthio group, and an arylsulfonyl group, an alkyl group having 1 to 6 carbon atoms such as a methyl group can be used in addition to the above substituents.

When G ₁ and G ₂ form a ring composed of a non-metal atom together with the carbon atom to which they are bound, the ring is usually used as an acidic nucleus in a merocyanine dye and includes the following.

(A) 1,3-dicarbonyl nucleus, such as 1,3-indandioneone, 1,3-cyclohexanedione, 5,5-dimethyl-1,
They are 3-cyclohexanedione and 1,3-dioxane-4,6-dione.

(B) Pyrazolinone nuclei, for example 3-methyl-1-phenyl-2-pyrazolin-5-one, 1-phenyl-2-
Pyrazolin-5-one, 1- (2-benzothiazoyl)
It is -3-methyl-2-pyrazolin-5-one.

(C) an isoxazolinone nucleus, such as 3-phenyl-
2-isoxazolin-5-one and 3-methyl-2-isoxazolin-5-one.

(D) Oxindole nuclei, for example 1-alkyl-2,
It is 3-dihydro-2-oxindole.

(E) 2,4,6-triketohexahydropyrimidine nucleus,
For example, barbituric acid or 2-thiobarbituric acid and its derivatives. The derivatives include 1-alkyl compounds such as 1-methyl and 1-ethyl, 1,3-dialkyl compounds such as 1,3-diethyl and 1,3-dibutyl, 1,3-diphenyl and 1,3-di (p -Chlorophenyl), 1,3-diaryl such as 1,3-di (p-ethoxycarbonylphenyl), 1-alkyl-3-aryl such as 1-ethyl-3-phenyl, and the like.

(F) 2-Thio-2,4-thiazolidinedione nuclei, such as rhodanine and its derivatives. 3 as a derivative
Examples thereof include 3-alkyl rhodanine such as ethyl rhodanine and 3-allyl rhodanine, and 3-aryl rhodanine such as 3-phenyl rhodanine.

(G) 2-thio-2,4-oxazolidinedione (2-
Thio-2,4- (3H, 5H) -oxazoledione) nuclei, for example 2-ethyl-2-thio-2,4-oxazolidinedione.

(H) thianaphthenone nuclei, such as 3 (2H) -thianaphthenone and 3 (2H) -thianaphthenone-1,1-dioxide.

(I) a 2-thio-2,5-thiazolidinedione nucleus, such as 3-ethyl-2-thio-2,5-thiazolidinedione.

(J) 2,4-thiazolidinedione nucleus, for example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione.

(K) Thiazolidione nuclei such as 4-thiazolidinone and 3-ethyl-4-thiazolidinone.

(L) 4-thiazolidinone nucleus, such as 2-ethylmercapto-5-thiazolin-4-one, 2-alkylphenylamino-5-thiazolin-4-one.

(M) 2-imino-2-oxazolin-4-one (coagulated hydantoin) nucleus.

(N) 2,4-imidazolidinedione (hydantoin)
A nucleus, for example, 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione.

(O) 2-thio-2,4-imidazolidinedione (2-
Thiohydantoin) nuclei, for example 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidinedione.

(P) 2-Imidazolin-5-one nucleus, for example 2-
It is n-propyl-mercapto-2-imidazolin-5-one.

(Q) Furan-5-one.

Specific examples of the compound represented by formula (I) used in the present invention are shown below.

Of these, (I-12), (I-13) and (I-1) are preferred.
6), (I-17), (I-21), (I-38), (I-3
9), (I-40), (I-41) and (I-42) compounds.

General formula (II) used in the present invention The 2,4,6-substituted-1,3,5-triazine compound represented by the formula is described in "Bulletin of the Chemical Society of Japan" by Wakabayashi et al.
ociety of Japan) 42 , 2924 (1969), for example, 2-phenyl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-acetylphenyl).
-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,
Examples include α, β-trichloroethyl) -4,6-bis (trichloromethyl) -S-triazine. In addition, compounds described in British Patent No. 1388492, for example, 2-
Styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4, 6-bis (trichloromethyl) -S-
Triazine, 2- (p-methoxystyryl) -4-amino-6-trichloromethyl-S-triazine, etc.
Compounds described in 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-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- (acenaphtho-5-yl) -4,6-bis-trichloromethyl-S-triazine, etc., compounds described in German Patent 3337024, for example, Etc. can be mentioned.

In addition, journals such as F, C, and FC Schaefer, organic, chemistry (J.Org.
Chem.); 29 , 1527 (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 etc. can be mentioned.

Furthermore, compounds described in Japanese Patent Application No. 60-198868, for example, Etc. can be mentioned.

Further, compounds described in Japanese Patent Application No. 61-186238 and Japanese Patent Application No. 61-227489, for example, Is.

Among these, 2-phenyl-4,6-bis (trichloromethyl) -S-triazine, 2- (P-acetylphenyl)
-4,6-bis (trichloromethyl) -S-triazine,
2- (P-chlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (P-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4, 6-Tris (trichloromethyl) -S-triazine is preferred.

The "organic peroxide" used in the present invention includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule, examples of which include 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, n-butyl-4,4-bis (tertiarybutylperoxy) valerate, 2,2-bis (tertiarybutylperoxy) butane, tertiary butyl hydroperoxide, Cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, 2,5-dimethylhexane-2,5
-Dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, ditertiary butyl peroxide, tertiary butyl cumyl peroxide, dicumyl peroxide, bis (tertiary butyl peroxyisopropyl) benzene, 2,5-Dimethyl-2,5-di (tertiarybutylperoxy) hexane, 2,5-Dimethyl-2,5-di (tertiarybutylperoxy) hexyne-3, acetyl peroxide, isobutyryl peroxide , Octanoyl peroxide, decanoyl peroxide, uraloyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, metatoluoyl peroxide Oxide, diisopropyl peroxy Carbonate,
Di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxycarbonate, di (3-
Methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxy neodecanoate, tert-butyl butyl peroxyoctanoate, tert-butyl per Oxy-3,5,5-trimethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, ditert-butyl diperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoyl) Baroxy) hexane, tert-butyl peroxymaleic acid, tert-butyl peroxyisopropyl carbonate, 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-octylperoxy) Carbonyl) benzophenone, 3,3 ', 4,4'-tetra (cumylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t- Butyl peroxy dihydrogen diphthalate), carbonyl di (t-hexyl peroxy dihydrogen diphthalate) 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-octylperoxy) Carbonyl) benzophenone, 3,3 ', 4,4'-tetra (cumylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (p-isopropylcumylperoxycarbonyl) benzophenone, di-t-butyl Peroxide ester systems such as diperoxyisophthalate are preferred.

Next, in the compound represented by the general formula (III), R ⁸ is an unsubstituted or substituted aromatic compound having 6 to 24 carbon atoms,
Or a π-arene of a heterocyclic aromatic compound having 3 to 30 carbon atoms, wherein R ⁹ is an unsubstituted or substituted 6 to 24 carbon atom
Represents an π-arene or π-arene anion of an organic aliphatic group which is an aromatic group having 3 to 30 carbon atoms, a heterocyclic aromatic group or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or a substituted alkyl. It may be mononuclear, bound polynuclear or non-bound polynuclear.

Further, as a compound represented by the general formula (III), JP
The metal arene compound described in the specification of 1-120827 can be mentioned.

Here, the metal arene compound is a compound in which π electrons of an aromatic or unsaturated compound and a metal are π-bonded, and is generally called a “π-bonded organometallic compound”. In most of the stable organometallic compounds of this kind, the sum of the π electron number of the aromatic or unsaturated compound and the electron number of the metal or ion is equal to the atomic number of the rare gas.

PF ₆ salt of - (cyclopentadienyl eta ⁵⁾ iron (II), specifically (eta ^{6-2-methylnaphthalene)} (eta ⁶ - cumene) (eta ⁵ - cyclopentadienyl) iron (II) PF
₆ salt, (η ⁶ -isopropylbenzene) (η ⁵ -cyclopentadienyl) iron (II) PF ₆ salt, (η ⁶ -toluene) (η ⁵ -indenyl) iron (II) PF ₆ salt, ( η ⁶ −
Toluene) (η ⁵ -cyclopentadienyl) iron (II)
PF ₆ salt, (η ⁶ -naphthalene) (η ⁵ -cyclopentadienyl) iron (II) AsF ₆ salt, (η ⁶ -benzene) (η ⁵
The BF ₄ salt of cyclopentadienyl) cobalt (II) may be mentioned.

As the aromatic onium salt, compounds shown in Japanese Patent Publication Nos. 52-14278 and 52-14279 can be cited.

In particular And so on.

Further, as the aromatic halonium salt, compounds shown in JP-B-52-14277 can be mentioned. In particular Can be raised. Of these, preferably BF ₄
Salts or compounds of PF ₆ salts, more preferably PF ₆ salts of metal arenes.

Next, the general formula (IV) used in the present invention Examples of the alkyl group represented by R ₁₀ and R ₁₁ in the compound represented by are those having 1 to 20 carbon atoms such as methyl, ethyl and propyl. Examples of the alkylene group formed by combining R ₁₀ and R ₁₁ include tetramethylene and pentamethylene. _Examples of the alkyl group represented by R _{12 to 17} in Ar include those having 1 to 4 carbon atoms. Further, examples of the alkenyl group include those having 3 to 12 carbon atoms. Furthermore, examples of the aryl group of R _{12 to} R ₁₆ include a phenyl group. Furthermore, examples of the alkoxy group include those having 1 to 4 carbon atoms. Examples of the acyl group of R ₁₈ include acetyl, propionyl, acryloyl and the like.

Specific examples of such general formula (IV) include: And so on.

Of these, (IV-1), (IV-2), (IV-
8) and (IV-9).

The content concentration of these photoinitiator systems in the composition of the present invention is usually low. On the other hand, if the amount is inappropriately large, undesired results such as the blocking of effective rays will 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 polymer optionally added. Preference is given to using. More preferably, 1% to 30% gives good results.

Further, in the photopolymerizable composition of the present invention, various organic amine compounds can be used in combination if necessary. Further, the photopolymerization initiation ability can be increased. Examples of these organic amine compounds include triethanolamine, dimethylamine, diethanolaniline, p-dimethylaminobenzoic acid ethyl ester, Michler's ketone, and the like. The amount of the organic amine compound added is preferably about 50% to 200% of the total amount of the photopolymerization initiator.

Further, the photopolymerization initiator used in the present invention may optionally contain N-phenylglycine, 2-mercaptobenzothiazole, N,
The photopolymerization initiation ability can be further enhanced by adding a hydrogen donating compound such as an N-dialkylbenzoic acid alkyl ester.

As the "linear organic high molecular weight polymer" that can be used in the present invention, any linear organic high molecular weight polymer which is compatible with the photopolymerizable ethylenically unsaturated compound can be used. May be used. Desirably, a linear organic high molecular polymer which is soluble or swellable in water or weak alkaline water, which enables water development or weak alkaline water development, should be selected. The linear organic high molecular polymer is used not only as a film-forming agent for the composition but also as a developer for water, weak alkaline water or an organic solvent. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic high molecular weight polymers include addition polymers having a carboxylic acid in the side chain, for example, JP-A-59-44615.
No. 54-34327, 58-12577, 54-54
-25957, JP-A-54-92723, JP-A-59-53836,
It is described in Japanese Patent Laid-Open No. 59-71048. That is, there are 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 to these, a product obtained by adding a cyclic acid anhydride to an addition polymer having a hydroxyl group is useful. In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / another addition-polymerizable vinyl monomer if necessary] copolymer and [allyl (meth) acrylate / (meth) acrylic acid / optionally And other addition-polymerizable vinyl monomers] copolymers are preferred. In addition, polyvinylpyrrolidone, polyethylene oxide, etc. are useful as the water-soluble linear organic polymer. To increase the strength of the cured film, alcohol-soluble nylon or 2,2-bis-
Polyethers of (4-hydroxyphenyl) -propane and epichlorohydrin are also useful. These linear organic high molecular weight polymers can be mixed in arbitrary amounts in the entire composition. However, if it exceeds 90% by weight, favorable results are not obtained in terms of the strength of the image formed. Preferably 30
~ 85%. The weight ratio of the photopolymerizable ethylenically unsaturated compound to the linear organic polymer is preferably 0.5 / 9.5 to 5/5. More preferable range is 1/9 to 4/6
Is the range.

Further, in the present invention, in addition to the above basic components, a small amount of a thermal polymerization inhibitor is added in order 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-t-butyl-P-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol). ), 2,
2'-methylenebis (4-methyl-6-t-butylphenol), 2-solcaptobenzimidazole, N-nitrosophenylhydroxyamine primary cerium salt and the like can be mentioned. The addition amount of the thermal polymerization inhibitor is preferably about 0.01% to about 5% based on the total weight of the composition. If necessary, a higher fatty acid derivative or the like may be added to the surface to prevent polymerization inhibition by oxygen. The addition amount of the higher fatty acid derivative is preferably about 0.5% to about 10% of the total composition amount. Further, a dye or a pigment may be added for the purpose of coloring the photosensitive layer. The addition amount of the dye and pigment is preferably about 0.5% to about 5% of the total composition amount. In addition, inorganic fillers and other known additives may be added to improve the physical properties of the cured film.

When applied, the photopolymerizable composition of the present invention is dissolved in various organic solvents before use. 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 monoethyl 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, etc. These solvents can be used alone or as a mixture. And, the concentration of the solid content in the coating solution is suitably 2 to 50% by weight.

The coating amount is preferably in the range of about 0.1 gm ² to about 10 g / m ² after dried. It is more preferably 0.5 to 5 g / m ² .

As the above support, a dimensionally stable plate-like material is used. Examples of the dimensionally stable plate-like material include paper, paper laminated with plastic (eg, polyethylene, polypropylene, polystyrene, etc.), and aluminum (including aluminum alloy), zinc, copper, etc. Metal plates, and further plastic films such as cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc. Examples include paper or plastic films laminated or vapor-deposited with the above metals. Of these supports,
Aluminum plates are particularly preferable because they are extremely dimensionally stable and inexpensive. Further, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable.

Further, in the case of a support having a surface of metal, particularly aluminum, it is subjected to surface treatment such as graining treatment, immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like, or anodization treatment. Is preferred.

Furthermore, an aluminum plate that has been grained and then immersed in an aqueous sodium silicate solution can be preferably used. As described in JP-B-47-5125, an aluminum plate subjected to anodizing treatment and then immersed in an aqueous solution of an alkali metal silicate is preferably used. The anodizing treatment is, for example, 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 an aqueous solution or a non-aqueous solution of these salts, or an electrolytic solution obtained by combining two or more kinds. It is carried out by passing an electric current through the aluminum plate as an anode.

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

Further, a support subjected to electrolytic graining as disclosed in JP-B-46-27481, JP-A-52-58602, JP-A-52-30503 and the anodizing treatment and sodium silicate Surface treatments that combine treatments are also useful.

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

Further, after these treatments, a water-soluble resin such as polyvinyl phosphonic acid, a polymer or copolymer having a sulfonic acid group in the side chain, polyacrylic acid, a water-soluble metal salt (eg zinc borate) or Those undercoated with a yellow dye, an amino salt or the like are also suitable.

These hydrophilization treatments, in addition to the treatment for rendering the surface of the support hydrophilic, prevent harmful reactions of the photopolymerizable composition provided thereon, and also improve the adhesion of the photosensitive layer. It is provided for improvement.

On the layer of the photopolymerizable composition provided on the support, in order to prevent the polymerization inhibiting action by oxygen in the air, for example, polyvinyl alcohol, a polymer having excellent oxygen barrier properties such as acidic celluloses. You may provide the protective layer which consists of. The coating method of 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 can be used in ordinary photopolymerization reaction. Further, it can be applied to various fields such as a photoresist when producing a printing plate, a printed circuit board and the like. In particular, the photopolymerizable composition of the present invention is characterized by high sensitivity and a wide range of spectral sensitivity characteristics up to the visible light region, so that when it is applied to a light-sensitive material for visible light laser such as Ar ⁺ laser, good effects can be obtained.

A printing plate using the photopolymerizable composition of the present invention is exposed to light, and the unexposed portion of the photosensitive layer is removed with a developer to obtain an image. Preferred developers for using these photopolymerizable compositions as lithographic printing plates include the developers described in JP-B-57-7427, sodium silicate, potassium silicate, Such as sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, ammonia water etc. Aqueous solutions of inorganic alcal agents and organic alkaline agents such as monoethanolamine or diethanolamine are suitable. The concentration of the alkaline solution is 0.1
~ 10 wt%, preferably 0.5 to 5 wt% is added.

In addition, the alkaline aqueous solution may optionally contain a surfactant, benzyl alcohol, 2-phenoxyethanol, or 2
-It may contain a small amount of an organic solvent such as butoxyethanol. For example, U.S. Pat. Nos. 3,375,171 and
The thing described in the 3,615,480 publication can be mentioned.

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

(Effect of the Invention) The photopolymerizable composition of the present invention has high sensitivity to actinic rays in a wide range from ultraviolet light to visible light. Therefore, as a light source, 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 sun rays can be used.

The present invention is described below with reference to examples, but the present invention is not limited thereto.

Examples 1 to 11 An aluminum plate having a thickness of 0.30 mm was grained on its surface using a nylon brush and an aqueous suspension of 400 mesh pumice, and then washed thoroughly with water. It was immersed in 10% sodium hydroxide at 70 ° C. for 60 seconds for etching, washed with running water, neutralized with 20% nitric acid, and then washed with water. This is V _A =
Electrolytic surface roughening treatment was carried out in a 1% nitric acid aqueous solution under a condition of 12.7 V in an aqueous 1% nitric acid solution at an anodic electricity of 160 clones / dm ² . When its surface roughness was measured, it was 0.
It was 6 μ (Ra indication). Next, after soaking in 30% sulfuric acid aqueous solution and desmutting at 55 ° C for 2 minutes, anodizing treatment in 20% sulfuric acid aqueous solution for 2 minutes at a current density of 2A / dm ^{2 to} a thickness of 2.7g / m ^2. did.

On the aluminum plate thus treated, the photosensitivity of the following composition was applied so that the dry coating weight would be 1.5 g / m ^2, and
A photosensitive layer was formed by drying at 0 ° C. for 2 minutes.

Trimethylolpropane tri (acryloyloxypropyl) ether 2.0g Allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 80/20) 2.0g Initiator Xg Copper phthalocyanine pigment 0.2g Fluorine nonionic surfactant 0.03g [3M Fluorad FC-430 (trade name)] 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 ˜89 mol% and a degree of polymerization of 1000) was applied so that the dry coating weight would be 2 g / m ^2, and dried at 100 ° C. for 2 minutes.

For the photosensitivity test with visible light, each monochromatic light of visible light (wavelength = 488 nm) and Ar ⁺ laser light (wavelength = 488 nm) was used.
Single-color visible light of 488 nm was obtained through a Kenko optical filter BP49 using a tungsten lamp as a light source. For sensitivity measurement, Fuji PS Step Guide (manufactured by Fuji Photo Film Co., Ltd., the transmission optical density of the first stage was 0.05, increasing by 0.15 15
It was carried out using a step tablet having steps. It is indicated by the number of clear steps of the PS step guide when the illuminance on the photosensitive film surface was exposed for 120 seconds at 25 LUX.

Laser light is Ar ⁺ laser (Rexel model 95-3)
Using a single line with a wavelength of 488 nm with a beam diameter of 100 μ
The intensity of Ar ⁺ laser was changed and scanned (using ND filter). The line width obtained after development was measured, and the intensity of the Ar ⁺ laser when the line width of 100 μ was reproduced was taken as the sensitivity.

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

Tables 1 to 3 show the results of sensitivity when the combination of photopolymerization initiators was changed.

Examples 12 to 18 In the production of the aluminum substrate of Example 1, instead of anodizing in a 20% sulfuric acid aqueous solution, the thickness becomes 0.8 g / m ² in a 5% phosphoric acid aqueous solution at a current density of 2 A / dm ² . Like 2
After anodizing for a minute, a substrate treated with a 3% aqueous sodium silicate solution at 70 ° C. for 10 seconds was used to prepare a photosensitive plate according to the following photosensitive solution formulation.

[Photosensitive solution formulation]

Pentaerythritol tetraacrylate 1.5g Benzylmethacrylate / methacrylic acid copolymer (copolymerization ratio 65/35) 3.0g Initiator Xg Copper phthalocyanine pigment 0.2g Fluorinated nonionic surfactant 0.03g [3M Fluorad FC -430 (trade name)] Methyl ethyl ketone 20 g Propylene glycol monomethyl ether acetate 20
g The dry coating weight of this photosensitive plate was 1.5 g / m ² . An oxygen barrier layer made of polyvinyl alcohol was provided on the photosensitive plate in the same manner as in Example 1, and exposure and development were carried out in the same manner as in Example 1 to develop the developer described in JP-B-56-42860. It was carried out by immersing at 25 ° C. for 1 minute to remove the unexposed portion.

The results of the sensitivity when the combination of the initiator system is changed are shown in Table 4 to
6 shows.

BTTB is 3,3 ', 4,4'-tetra (t-butylperoxylcarbonyl) bunzophenone, and PBIF is di-t-butyldiperoxyhighophthalate.

As is clear from Tables 1 to 3, the ternary initiator is a single-source initiator,
It shows higher sensitivity than the binary system.

As is clear from Tables 4 to 6, it is shown that the ternary initiator has a higher sensitivity than the ternary initiator and the binary initiator.

Claims (2)

[Claims] 1. At least one ethylenically unsaturated double bond.
In a photopolymerizable composition containing an addition-polymerizable compound and a photopolymerization initiator each having a linear organic high molecular polymer, the photopolymerization initiator is at least the following (a),
A photopolymerizable composition, which is a combination of the compounds (b) and (c). (A) Compound of general formula (I) (In the formula, R _{1 to} R ₄ are independently of each other, a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a hydroxyl group, an alkoxy group, a substituted alkoxy group, an amino group, a substituted amino group. Represents a group, and R ₁ ~
R ₄ may form a ring composed of a non-metal atom together with the carbon atom to which it can bind. R ₆ is R ₇ or -Z-R _7, Z represents a carbonyl group, a sulfonyl group, a sulfinyl group, or arylene group, R _5, R ₇ independently of one another, a hydrogen atom, an alkyl group, A substituted alkyl group, an aryl group, a substituted aryl group,
It represents a heteroaromatic group, a substituted heteroaromatic group, a cyano group, an alkoxy group, a substituted alkoxy group, a carboxy group, an alkenyl group or a substituted alkenyl group. Both R ₅ and R ₆ may form a ring composed of a non-metal atom. X is O, S, NH,
Alternatively, it represents a nitrogen atom having a substituent. Y is an oxygen atom,
Or And G ₁ and G ₂ may be the same or different, and are a hydrogen atom, a cyano group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, an aryloxycarbonyl group, a substituted aryloxycarbonyl group, an acyl group, a substituted acyl group. Represents an arylcarbonyl group, a substituted arylcarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, and a fluorosulfonyl group. But G ₁ and G ₂ are not hydrogen atoms. Also G ₁ , G ₂
May form a ring composed of a non-metal atom together with the carbon atom which it can form. ) (B) 2,4,6-substituted-1,3,5-represented by the general formula (II)
Triazine compound (In the formula, X, Y, and Z each represent an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or an aralkyl group, and they may be the same or different, but at least one of them is mono- , D or trihalogen-substituted methyl group) or an organic peroxide (C) general formula (III): [(R ⁸ ) (R ⁹ M)] ⁺ nYm ⁻ n (III) (wherein, m and n are integers of 1 or 2, R ⁸ is π-arene, R ⁹ is π-arene or π-arene anion, M is Ti, Cr, Co, Mn, W, Fe, Mo, S, Se, T
a cation selected from e, N, P, As, Bi and Sb, Y
Is B ▲ F ^- ₄ ▼, P ▲ F ^- ₆ ▼, As ▲ F ^- ₆ ▼, Sb ▲ F ^- ₆ ▼,
_{^{FeC ▲ l - 4 ▼, SnC}} ▲ l 2- 6 ▼, SbC ▲ l - 6 ▼ and BiC ▲
represents an anion selected from l ^- ₆ . ) At least one compound selected from the compound represented by :, an aromatic onium salt, and an aromatic halonium salt. 2. At least one ethylenically unsaturated double bond.
In a photopolymerizable composition containing an addition-polymerizable compound and a photopolymerization initiator each having a linear organic high molecular polymer, the photopolymerization initiator is at least the following (a),
A photopolymerizable composition, which is a combination of the compounds (b) and (d). (A) Compound of general formula (I) (In the formula, R _{1 to} R ₄ are independently of each other, a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a hydroxyl group, an alkoxy group, a substituted alkoxy group, an amino group, a substituted amino group. Represents a group, and R ₁ ~
R ₄ may form a ring composed of a non-metal atom together with the carbon atom to which it can bind. R ₆ is R ₇ or -Z-R _7, Z represents a carbonyl group, a sulfonyl group, a sulfinyl group, or arylene group, R _5, R ₇ independently of one another, a hydrogen atom, an alkyl group, A substituted alkyl group, an aryl group, a substituted aryl group,
It represents a heteroaromatic group, a substituted heteroaromatic group, a cyano group, an alkoxy group, a substituted alkoxy group, a carboxy group, an alkenyl group or a substituted alkenyl group. Both R ₅ and R ₆ may form a ring composed of a non-metal atom. X is O, S, NH,
Alternatively, it represents a nitrogen atom having a substituent. Y is an oxygen atom,
Or And G ₁ and G ₂ may be the same or different, and are a hydrogen atom, a cyano group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, an aryloxycarbonyl group, a substituted aryloxycarbonyl group, an acyl group, a substituted acyl group. Represents an arylcarbonyl group, a substituted arylcarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, and a fluorosulfonyl group. But G ₁ and G ₂ are not hydrogen atoms. Also G ₁ , G ₂
May form a ring composed of a non-metal atom together with the carbon atom which it can form. ) (B) 2,4,6-substituted-1, represented by the following general formula (II),
3,5-triazine compound (In the formula, X, Y, and Z each represent an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or an aralkyl group, and they may be the same or different, but at least one of them is mono- , Di or trihalogen-substituted methyl group.) (D) Morpholino compound of the general formula (IV) (In the formula, Ar represents an aromatic group selected from one of the following general formulas, R ₁₀ and R ₁₁ represent a hydrogen atom or an alkyl group, and R ₁₀ and R ₁₁ are bonded to each other. May represent an alkylene group. ) General formula: (In the formula, R _{12 to} R ₁₆ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group,
Substituted aryl group, a hydroxyl group, an alkoxy group, substituted alkoxy group, -S-R ₁₇ group, represents an -SO-R ₁₇ group or -SO ₂ R ₁₇ group, provided that at least one of R ₁₂ to R ₁₆ group - S-R ₁₇ groups,
It represents -SO-R ₁₇ group or -SO ₂ R ₁₇ group, R ₁₇ represents an alkyl group having,
The alkenyl group and R ₁₈ represent a hydrogen atom, an alkyl group or an acyl group. Y ₁ is a hydrogen atom or Represents )]