JPH0725921A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To obtain a photopolymerizable composition useful for a photosensitive layer for photosensitive lithographic printing plate, sensitive to visible light rays, a light source of argon laser, etc., comprising an addition polymerizable unsaturated compound, a specific benzthiazole derivative and a halomethyltriazine compound. CONSTITUTION:(A) A polymerizable compound containing an addition polymerizable unsaturated bond [e.g. trimethylolpropane tri(acryloyloxypropyl) ether] is mixed with (B) a compound of the formula [R<1> and R<2> are H, (substituted) alkyl, alkoxy, alkoxycarbonyl, (substituted) aryl or aralkyl; R<3> to R<6> are as shown for R'', alkylthio, arylthio or (substituted) amino; X is non- metallic atomic group required for forming 5- to 7-membered ring; Z is non-metallic atomic group required for forming (substituted) aromatic ring or (substituted) hetero aromatic ring and (C) a halomethyltriazine compound [e.g. 2-phenyl-4,6-bis(trichloromethyl)-S-triazine] to give the objective photopolymerizable composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to photopolymerizable compositions. More specifically, it relates to a photopolymerizable composition containing a polymerizable compound having an addition polymerizable unsaturated bond, a photopolymerization initiator having a novel composition, and, if necessary, a linear organic polymer, The present invention also relates to a photopolymerizable composition useful for a photosensitive layer of a photosensitive lithographic printing plate which is sensitive to an argon laser light source.

[0002]

2. Description of the Related Art A photosensitive composition in which a polymerizable compound having an addition-polymerizable unsaturated bond, a photopolymerization initiator, and if necessary, a binder having an appropriate film forming ability and a thermal polymerization inhibitor are mixed. A method of reproducing an image by a photographic method using is currently known. That is, U.S. Pat.Nos. 2,927,022, 2,902,356 or 3,870,
As described in No. 524, since a photosensitive composition of this type undergoes photopolymerization upon irradiation with light and is cured and insolubilized, the photosensitive composition is formed into an appropriate film, and a desired negative image is formed through it. A desired cured image of the photopolymerizable composition can be formed by irradiating light and removing only the unexposed portion with a suitable solvent (hereinafter, simply referred to as development). 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, a polymerizable compound having an addition polymerizable unsaturated bond alone does not have sufficient photosensitivity, and it has been proposed to add a photopolymerization initiator to enhance the photosensitivity. As such, 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 photopolymerization ability of 40 nm or less in the ultraviolet region of 40 nm or less.
The photopolymerization ability for a light source in the visible light region of 0 nm or more is remarkably low. 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, according to U.S. Pat. No. 2,850,445, certain photoreducing dyes such as rose bengal, eosin, and erythrosine are reported to have effective visible light sensitivity. As an improved technology,
Complex initiation system of dye and amine (Japanese Patent Publication No. 44-20189)
No.), a system of hexaarylbiimidazole and a radical generator and a dye (Japanese Patent Publication No. 45-37377), a system of hexaarylbiimidazole and P-dialkylaminobenzylidene ketone (Japanese Patent Publication No. 47-2528, Japanese Patent Laid-Open No. 5528/1985).
4-155292), a system of 3-keto-substituted coumarin compounds and active halogen compounds (JP-A-58-15503).
No.), a system of substituted triazine and merocyanine dye (JP-A-54-15102), and the like have been proposed. These techniques are certainly effective for visible light. However, the photosensitivity speed is not yet satisfactory,
Further improved techniques have been desired. In addition, in recent years, a method for forming an image using a laser and a high sensitivity to ultraviolet rays has been studied, and a UV projection exposure method, a laser direct plate making, a laser facsimile, in a printing plate making,
Holography and the like are already in the stage of practical use, and a highly sensitive light-sensitive material corresponding to them is being developed. However, it cannot be said that it still has sufficient sensitivity.

[0004]

An object of the present invention is to provide a photopolymerizable composition having high sensitivity. That is,
The 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 addition polymerizable unsaturated bond in general. is there. Another object of the present invention is 400 nm.
It is an object of the present invention to provide a photopolymerizable composition containing a photopolymerization initiator having high sensitivity to the above visible light, particularly light near 488 nm corresponding to the output of Ar ⁺ laser.

[0005]

Means for Solving the Problems As a result of earnest studies to achieve the above object, the present inventor has found that a specific photopolymerization initiator system is a photopolymerizable compound having an addition-polymerizable unsaturated bond. The present invention has been accomplished by finding that the polymerization rate is remarkably increased and that the composition has high sensitivity to visible light of 400 nm or more. That is, the present invention is a photopolymerizable composition containing the following components (i) to (iii). (i) A polymerizable compound having an addition-polymerizable unsaturated bond. (ii) A compound represented by the general formula (I).

[0006]

[Chemical 5] R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, an alkoxycarbonyl group,
It represents an aryl group, a substituted aryl group or an aralkyl group. R ³ , R ⁴ , R ⁵ and R ⁶ are each independently R ¹ and R ²
Represents an alkylthio group, an arylthio group, an amino group or a substituted amino group. X represents a nonmetallic atomic group necessary for forming a 5- to 7-membered ring. Z represents a non-metal atom group necessary for forming a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heteroaromatic ring. (iii) Halomethyltriazine compound. When the photopolymerizable composition of the present invention further contains a compound represented by the following formula (II) or (III), a photopolymerizable composition with higher sensitivity can be obtained.

[0007]

[Chemical 6] Here, Ar represents an aromatic group selected from one of the following general formulas, R ⁷ and R ⁸ represent a hydrogen atom or an alkyl group,
R ⁷ and R ⁸ may be bonded to each other to represent an alkylene group.

[0008]

[Chemical 7] (In the formula, R ^{9 to} R ¹³ may be the same or different from each other, and each is a hydrogen atom, a halogen atom, an alkyl group,
Alkenyl group, aryl group, substituted aryl group, hydroxyl group,
Alkoxy group, substituted alkoxy group, -S-R ¹⁵ group, -S
Represents an O-R ¹⁵ group or -SO ₂ R ¹⁵ group, where R ⁹ to R ¹³
At least one -S-R ¹⁵ group of radicals, represents -SO-R ¹⁵ group or -SO ₂ R ¹⁵ group, R ¹⁵ is an alkyl or alkenyl group, R ¹⁴ is a hydrogen atom, an alkyl group or an acyl group Represent Y is a hydrogen atom or

[0009]

[Chemical 8] (Wherein R ⁷ and R ⁸ are as defined above). ) R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, an alkoxycarbonyl group,
It represents an aryl group, a substituted aryl group, an aralkyl group, an alkylthio group, an arylthio group, an amino group or a substituted amino group. R ¹⁸ represents an alkyl group, a substituted alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, a substituted aryl group, an aralkyl group, an alkylthio group, an arylthio group, an amino group or a substituted amino group.

Hereinafter, each component of the photopolymerizable composition of the present invention will be described in detail. Component (i) used in the present invention
The polymerizable compound having an addition polymerizable unsaturated bond of
It is selected from compounds having at least one, and preferably two or more terminal ethylenically unsaturated bonds. 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 (for example,
Acrylic acid, methacrylic acid, itaconic acid, crotonic acid,
Isocrotonic acid, maleic acid and the like) and an ester of an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyhydric amine compound.

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

Methacrylic acid esters include 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-hi Rokishipuropokishi) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane. As the itaconic acid ester, ethylene glycol diitaconate,
Examples include propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetriconate. 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.

Specific examples of the amide monomer of an aliphatic polyvalent amine compound and an unsaturated carboxylic acid include methylenebis-acrylamide, methylenebis-methacrylamide, 1,6-hexamethylenebis-acrylamide, 1,6- Hexamethylene bis-methacrylamide,
Examples include diethylenetriamine tris acrylamide, xylylene bis acrylamide, and xylylene bis methacrylamide. Other examples include Japanese Examined Patent Publication No. 48-417.
In the polyisocyanate compound having two or more isocyanate groups in one molecule described in JP-A-08,
Examples thereof include vinyl urethane compounds having two or more polymerizable vinyl groups in one molecule to which a vinyl monomer having a hydroxyl group represented by the following general formula (A) 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
No. 4, Japanese Patent Publication No. 49-43191, Japanese Patent Publication No. 52-3049
Examples thereof include 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-0. Furthermore, those introduced as photocurable monomers and oligomers in Japan Adhesive Association magazine vol. 20, No. 7, pages 300 to 308 (1984) can also be used. The amount of these used is 5 to 50% by weight based on all components.
(Hereinafter abbreviated as “%”), preferably 10 to 40%.

The component (ii) used in the present invention is a compound represented by the above general formula (I). Examples of R ¹ and R ² in the general formula (I) are shown below. Examples of the alkyl group include linear, branched and cyclic alkyl groups having 1 to 18 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group. , Hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, isohexyl group, sec-butyl group, neopentyl group, tert-butyl group, tert-pentyl group Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and 2-norbornyl group. Among 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 preferable.

As the substituent of the substituted alkyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a hydroxyl group,
Examples thereof include an alkoxy 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 above-mentioned alkyl group having 1 to 18 carbon atoms, preferably a linear or branched alkyl group having 1 to 10 carbon atoms and a cyclic alkyl group having 6 to 10 carbon atoms are also used. The alkyl group is most preferably a linear or branched alkyl group having 1 to 4 carbon atoms. Specific examples of the substituted alkyl group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a 2,2,2-trichloroethyl group, a 2-chloropentyl group, a 1- (chloromethyl) propyl group, and a 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 group ) 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, benzoyloxypentyl group, benzoyloxyethoxyethyl group, acetylaminoethyl group, propionylamino acid, N-methylcarbamoylethyl group, An N, N-diethylcarbamoylethyl group can be mentioned. 1 as an aryl group
Benzene ring residue (phenyl group), 2 and 3 condensed benzene ring residues (naphthyl group, anthryl group,
Examples thereof include a phenanthryl group), two benzene ring assembly system residues (biphenyl group) and a condensed system residue of a benzene ring and a 5-membered unsaturated ring (indenyl group, acenaphthenyl group, fluorenyl group).

As the substituted aryl group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an amino group, a substituted amino group (monoalkyl substituted amino group (alkyl group) in the ring-forming carbon atom of the above-mentioned aryl group. , Methyl group, ethyl group, propyl group, pentyl group, isopropyl group, sec-butyl group, isopentyl group), dialkylamino group (examples of alkyl group are the same as examples of monoalkyl-substituted amino group), monoacylamino Groups (examples of acyl groups, acetyl groups, propionyl groups, butyryl groups, isobutyryl groups, valeryl groups), cyano groups, alkyl groups (straight, branched and 1 to 18 carbon atoms) Cyclic alkyl groups, preferably linear, branched and cyclic alkyl groups having from 1 to 10 carbon atoms, most preferably 1 carbon atom Linear and branched alkyl groups up al 4, these specific examples are already mentioned above.), Haloalkyl group (e.g., chloromethyl group, 2
-Chloroethyl group, 5-chloropentyl group, trifluoromethyl group), alkoxy group (examples of alkyl group, methyl group, ethyl group, butyl group, pentyl group, isopropyl group, isopentyl group, 2-methylbutyl group, sec-butyl) Groups), aryloxy groups (examples of aryl groups, phenyl groups, 1-naphthyl groups, 2-naphthyl groups), alkoxycarbonyl groups (examples of alkyl groups, methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups) , An acyloxy group (the example of the acyl group is the same as the example of the monoacylamino group),
A residue in which one or more substituents such as an alkoxysulfonyl group (the example of the alkyl group is the same as the example of the alkyl group of the alkoxy group) or the same or different substituents can be mentioned.

Specific examples of these aryl groups and substituted aryl groups include phenyl group, chlorophenyl group, aminophenyl group, (methylamino) phenyl group, (ethylamino) phenyl group, (dimethylamino) phenyl group and acetylamino. Phenyl group, tolyl group, ethylphenyl group, (chloromethyl) phenyl group, acetylphenyl group, phenoxyphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl 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,
Examples thereof include a biphenylyl group, a chlorobiphenylyl group, an aminobiphenylyl group, a methylbiphenylyl group, and an acenaphthenyl group. Among these, a phenyl group and a phenyl group in which one or more of the above-mentioned substituents are substituted with two or more of the same or different above-mentioned substituents are preferable. Aralkyl group has 1 to 1 carbon atoms
Examples thereof include a residue in which a phenyl group or a naphthyl group is substituted on a linear, branched or cyclic alkyl group of 0, preferably 1 to 6, and specific examples thereof include a benzyl group, a phenethyl group, Examples thereof include a 3-phenylpropyl group, a 3-phenylhexyl group, a 10-phenyldecyl group, a 4-phenylcyclohexyl group, a 1-naphthylmethyl group, a 2- (1-naphthyl) ethyl group and a 2-naphthylmethyl group. .

Examples of the alkoxycarbonyl group include residues in which a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is bonded to an oxycarbonyl group, and specific examples thereof include methoxycarbonyl group. Group, ethoxycarbonyl group, propoxycarbonyl group,
Butoxycarbonyl group, sec-butoxycarbonyl group,
A tert-butoxycarbonyl group can be mentioned. R
Examples of the alkylthio group of ³ , R ⁴ , R ⁵ and R ⁶ include residues in which a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is bonded to a sulfur atom. Examples thereof include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a sec-butylthio group, and a tert-butylthio group. Examples of the arylthio group include a residue in which an aromatic ring having 6 to 10 carbon atoms is bonded to a sulfur atom, and specific examples thereof include a phenylthio group, a naphthylthio group, and a p-tolylthio group. The substituted amino group has 1 to 10 carbon atoms.
Up to and including amino groups substituted with linear, branched, and cyclic alkyl groups, and specific examples thereof include dimethylamino group, diethylamino group, and dipropylamino group. In addition, the general formula (I)
Examples of the residue represented by the following formula (IV) are shown below.

[0019]

[Chemical 9]

[0020]

[Chemical 10]

[0021]

[Chemical 11]

[0022]

[Chemical 12] The compounds represented by the general formula (I) are represented by "Bull. Soc. C
himie Belges "Vol. 57, pages 364-372 (194
8 years) Abstract: "Chemical Abstracts", Vol. 44, No. 60
It can be synthesized according to the method described in columns c to 61d (1950). Specific examples of the compound represented by formula (I) are shown below.

[0023]

[Chemical 13]

[0024]

[Chemical 14]

[0025]

[Chemical 15]

[0026]

[Chemical 16]

[0027]

[Chemical 17]

[0028]

[Chemical 18] Examples of the compound of the component (iii) used in the present invention include Wakabayashi et al., Bull. Chem. Soc. Japan, 42 , 29.
24 (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. In addition, compounds described in British Patent No. 1388492, such as 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 JP-A-53-133428, such as 2- (4-methoxy-naphtho-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 and the like, compounds described in German Patent No. 3337024, for example, the following compounds can be mentioned.

[0029]

[Chemical 19]

[0030]

[Chemical 20] Also, FC Schaefer et al. J. Org Chem.
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 and the like can be mentioned. Further, the compounds described in JP-A-62-58241, such as the following compounds, can be mentioned.

[0031]

[Chemical 21]

[0032]

[Chemical formula 22] The photopolymerizable composition of the present invention, the general formula (II) or (II
By incorporating the compound represented by I), the sensitivity can be further increased. R in the general formula (II)
Examples of the alkyl group of ⁷ and R ⁸ include those having 1 to 20 carbon atoms such as methyl, ethyl and propyl. Examples of the alkylene group formed by combining R ⁷ and R ⁸ include tetramethylene and pentamethylene.
Further, the alkyl group of R ^{9 to} R ¹³ has 1 to 1 carbon atoms.
There are four. Further, as the alkenyl group,
Those having 3 to 12 carbon atoms can be mentioned. Examples of the acyl group of R ¹⁴ include acetyl, propionyl, acryloyl and the like. The alkyl group represented by R ¹⁶ and R ^{17 in} the general formula (III) has a carbon number of 1 to 1 such as methyl, ethyl and propyl.
Examples thereof include a phenyl group as an aryl group and a phenyl group as a substituted aryl group, a halogen atom, an amino group, a mono- or dialkylamino group (wherein the alkyl group has 1 to 6 carbon atoms). And a cyano group or an alkyl group (having 1 to 4 carbon atoms) as a substituent. Further, the aralkyl group may be a benzyl group. Further, examples of the alkyl group, substituted alkyl group, alkoxy group, alkoxycarbonyl group, aryl group, substituted aryl group and aralkyl group of R ¹⁸ include those listed for R ¹ in the general formula (I), and alkylthio group, arylthio group The amino group and the substituted amino group include those listed for R ³ in the general formula (I). Specific examples of such compounds include the following compounds.

[0033]

[Chemical formula 23]

[0034]

[Chemical formula 24]

[0035]

[Chemical 25] Among these, preferable ones are (II-1), (II-2), (II
-8), (II-9), and (III-1). 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 0.01% to 60% with respect to the total of the photopolymerizable ethylenically unsaturated compound and the linear organic high molecular polymer optionally added, More preferably,
It is in the range of 1% to 30%. The ratio of component (ii) and component (iii), which are components of the photopolymerization initiation system used in the present invention, is
Component (iii) is added to 1 part by weight of the organic dye of component (ii).
It is suitable to use 01 to 50 parts by weight, more preferably 0.02 to 20 parts by weight, most preferably 0.05 to 10 parts by weight.
Parts by weight. Further, when the compound represented by the general formula (II) or (III) is used in combination, it is suitable to use 0.01 to 50 parts by weight relative to 1 part by weight of the organic dye of the component (ii), The amount is more preferably 0.02 to 20 parts by weight, and most preferably 0.05 to 10 parts by weight.

The photopolymerizable composition of the present invention preferably contains a linear organic high molecular polymer as a binder. As such a "linear organic high molecular polymer",
Any linear organic high molecular polymer having compatibility with the photopolymerizable ethylenically unsaturated compound may be used. A linear organic polymer which is soluble or swellable in water or weak alkaline water, which enables water development or weak alkaline water development, is preferably selected. The linear organic high molecular polymer is not only used as a film forming agent for the composition,
The developer is appropriately selected and used depending on whether water, weak alkaline water or an organic solvent is used. For example, when a water-soluble organic polymer is used, water development becomes possible. As such a linear organic high molecular polymer, an addition polymer having a carboxylic acid group in its side chain, for example, JP-A-59-4
4615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-
No. 12577, Japanese Examined Patent Publication No. 54-25957, and Japanese Unexamined Patent Publication No. 54
-92723, JP-A-59-53836, JP-A-5-
9-71048, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer,
There are partially esterified maleic acid copolymers and the like. Similarly, there is an acidic cellulose derivative having a carboxylic acid group in its side chain. In addition to these, addition polymers having a cyclic acid anhydride to an addition polymer having a hydroxyl group are useful. In particular, among these, [benzyl (meth) acrylate / (meth) acrylic acid / and, if necessary, other addition-polymerizable vinyl monomer]
Copolymer and [allyl (meth) acrylate / (meth)
Acrylic acid / another addition-polymerizable vinyl monomer as required] copolymer is preferable. 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 polyamide 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, when it exceeds 90% by weight, favorable results are not obtained in terms of the strength of the formed image. It is preferably 30 to 85%. The weight ratio of the photopolymerizable ethylenically unsaturated compound and the linear organic high molecular polymer is 1/9.
It is preferably in the range of ˜7 / 3. A more preferable range is 3/7 to 5/5.

In the present invention, in addition to the above basic components, a small amount of thermal polymerization is prevented 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 add agents. Suitable thermal polymerization inhibitors include haloid quinone, 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), N-nitrosophenylhydroxyamine primary cerium salt and the like. The amount of the thermal polymerization inhibitor added is about 0.01% based on the weight of the entire composition.
~ About 5% is preferred. Further, 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 during the drying process after coating. . The amount of the higher fatty acid derivative added is preferably about 0.5% to about 10% of the total composition. 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 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 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 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, methoxymethoxy Ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N N- dimethylformamide, dimethyl sulfoxide, .gamma.-butyrolactone, methyl lactate and ethyl lactate. These solvents can be used alone or as a mixture. Then, the concentration of the solid content in the coating solution is appropriately 2 to 50% by weight. The coating amount is suitably ranges from about 0.1 g / m ² ~ about 10 g / m ² in weight after drying. It is more preferably 0.5 to 5 g / m ² .

As the support, a dimensionally stable plate is used. As the dimensionally stable plate-like material,
Paper, paper laminated with plastic (eg polyethylene, polypropylene, polystyrene, etc.),
Metal plates such as aluminum (including aluminum alloys), zinc, copper, etc., and further, for example, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene. Examples thereof include plastic films such as polystyrene, polypropylene, polycarbonate, and polyvinyl acetal, and papers or plastic films on which the above metals are laminated or vapor deposited. Among these supports, the aluminum plate is particularly preferable because it is dimensionally remarkably stable and inexpensive. Furthermore,
A composite sheet in which an aluminum sheet is bonded onto 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, especially aluminum, graining treatment, sodium silicate, potassium fluorozirconate,
It is preferable that a surface treatment such as an immersion treatment in an aqueous solution of a phosphate or the like or an anodization treatment is performed.

Furthermore, an aluminum plate which 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 non-aqueous solution of a salt thereof, 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. Furthermore, Japanese Patent Publication No.
27481, JP-A-52-58602, JP-A-52
A surface treatment in which an electrolytic grain as disclosed in -30503 is combined with the anodizing treatment and the sodium silicate treatment is also useful. Also, JP-A-56-28893
Those which are sequentially subjected to mechanical surface roughening, chemical etching, electrolytic graining, anodic oxidation treatment and sodium silicate treatment as disclosed in JP-A No. 1994-26187 are also suitable. Further, after these treatments, a water-soluble resin, for example, polyvinylphosphonic acid, a polymer or copolymer having a sulfonic acid group in the side chain, polyacrylic acid, a water-soluble metal salt (for example, zinc borate), or Those undercoated with a yellow dye, an amine salt or the like are also suitable. These hydrophilization treatments are performed in order to make the surface of the support hydrophilic, prevent the harmful reaction of the photopolymerizable composition provided thereon, and improve the adhesion of the photosensitive layer. And so on.

On the layer of the photopolymerizable composition provided on the support, for example, polyvinyl alcohol, particularly a saponification degree of 99% is used in order to prevent the polymerization inhibiting action of oxygen in the air.
A protective layer made of a polymer having an excellent oxygen barrier property such as the above polyvinyl alcohol and acidic celluloses may be provided. The coating method of such a protective layer is described in, for example, US Pat. No. 3,458,311 and JP-A-55-497.
It is described in detail in No. 29. 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. Further, since the photopolymerizable composition of the present invention has high sensitivity and is sensitive to visible light, it can be particularly advantageously used for an image forming system utilizing microcapsules. For use in an image forming system using microcapsules, see, for example, JP-A-57-197538 and JP-A-61-1.
30945, 58-88739, 58-887.
No. 40, European Patent No. 223,587A1 and the like can be referred to. This image forming method is, for example, coating a microcapsule containing a photopolymerization initiator composition comprising an ethylenic vinyl compound and a photopolymerization initiator and a dye precursor on a support, and exposing the photosensitive sheet imagewise for exposure. Part of the microcapsules is cured, and then a developer sheet is overlaid and pressed over the entire surface to destroy the unexposed parts of the microcapsules, thereby forming a color image forming substance (for example, a dye precursor).
Is transferred to an image receiving element (for example, a color developer layer) to develop a color.

The photosensitive material using the photopolymerizable composition of the present invention is subjected to imagewise exposure, and then the unexposed portion of the photosensitive layer is removed with a developing solution to obtain an image. Preferred developing solutions when these photopolymerizable compositions are used for preparing a lithographic printing plate are the developing solutions described in JP-B-57-7427, sodium silicate and potassium silicate. , Such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium phosphate tribasic, sodium phosphate dibasic, ammonium phosphate tribasic, ammonium phosphate dibasic, sodium metasilicate, sodium bicarbonate, aqueous ammonia etc. Aqueous inorganic alkaline agents and aqueous solutions of organic alkaline agents such as monoethanolamine or diethanolamine are suitable. The alkaline agent is added so as to have a concentration of 0.1 to 10% by weight, preferably 0.5 to 5% by weight. Further, the alkaline aqueous solution may contain a small amount of a surfactant and an organic solvent such as benzyl alcohol, 2-phenoxyethanol or 2-butoxyethanol, if necessary. For example, U.S. Pat. Nos. 3,375,171 and 3,
The thing described in 615,480 can be mentioned. Further, JP-A-50-26601 and 58-54.
No. 341, Japanese Patent Publication No. 56-39464, No. 56-428.
The developers described in JP-A No. 60 are also excellent.

[0043]

The photopolymerizable composition of the present invention has high sensitivity to actinic rays in a wide range from ultraviolet rays to visible rays. Therefore, as the 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, sunlight, etc. Can be used.

[0044]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. thickness
A 0.30 mm aluminum plate was grained on its surface with 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 was subjected to electrolytic surface-roughening treatment in an aqueous 1% nitric acid solution under the condition of V _A = 12.7 V in an aqueous 1% nitric acid solution at an anode electricity of 160 coulomb / dm ² . The surface roughness was measured and found to be 0.6 μ (Ra indication). Then, it was immersed in a 30% sulfuric acid aqueous solution and desmutted at 55 ° C. for 2 minutes, and then in a 20% sulfuric acid aqueous solution, the current density was 2 A / dm ^2.
Was anodized for 2 minutes so that the thickness of the anodized film was 2.7 g / m ² . On the thus treated aluminum plate, a photosensitive composition having the following composition was applied so that the dry coating weight was 1.4 g / m ^2, and dried at 80 ° C. for 2 minutes to form a photosensitive layer. Trimethylolpropane tri (acryloyl oxypropyl) ether 2.0 g Allyl methacrylate / methacrylic acid copolymer (copolymerization molar ratio 80/20) 2.0 g Photopolymerization initiator Xg Fluorine-based nonionic surfactant 0.03 g Methyl ethyl ketone 20 g Propylene glycol monomethyl ether acetate 20g

A 3% by weight aqueous solution of polyvinyl alcohol (saponification degree: 86.5 to 89 mol%, polymerization degree: 1000) was coated on the photosensitive layer so that the dry coating weight was 2 g / m ^2, and the temperature was 100 ° C. / Dried for 2 minutes. For the photosensitivity test, visible light and Ar ⁺ laser light (wavelength = 488 nm) of each monochromatic light were used. Visible light uses a tungsten lamp as a light source,
Kenko optical filter BP
Obtained through -49. For the photosensitivity measurement, a Fuji PS step guide (manufactured by Fuji Photo Film Co., Ltd., a step tablet in which the transmission optical density of the first stage is 0.05 and sequentially increases by 0.15 to 15 stages) was used. The sensitivity was indicated by the number of clear steps of the PS step guide when the illuminance on the surface of the photosensitive material film was exposed for 40 seconds at 25 LUX. The larger the number of steps, the higher the sensitivity. For development, use the following developer at 25 ℃
It was performed by immersing it for 1 minute. 1K potassium silicate 30 g potassium hydroxide 15 g C ₁₂ H ₂₅ -C ₆ H ₄ -OC ₆ H ₄ -SO ₃ Na 3 g water 1000 g The results are shown in Tables 1 and 2 below.

[0046]

[Table 1] Photopolymerization initiator (g) Example Component (ii) Component (iii) Formula (II) or (III) BP-49 Filter light Clear number of compounds 1 I-1 (a) 0.13 Compound ( a) 0.054 − 8.1 2 I-1 (d) 0.12 Compound (a) 0.054 − 8.3 3 I-2 0.13 Compound (a) 0.054 − 8.1 4 I-7 0.1 Compound (a) 0.054 − 7.7 5 I-1 (a ) 0.13 Compound (a) 0.054 (II-1) 0.4 9.2 6 I-1 (d) 0.12 Compound (a) 0.054 (II-1) 0.4 9.3 7 I-2 0.13 Compound (a) 0.054 (II-1) 0.4 9.1 8 I-7 0.1 Compound (a) 0.054 (II-1) 0.4 8.8 9 I-1 (a) 0.12 Compound (a) 0.054 (II-9) 0.8 9.2 10 I-1 (a) 0.12 Compound (a) 0.054 (III-1) 0.55 9.2

[0047]

[Table 2] Photopolymerization Initiator (g) Comparative Example Component (ii) Component (iii) Formula (II) or (III) BP-49 Filter Light Clear Number of Compounds 1 I-1 (a) 0.13 − − 0 2 I-1 (d) 0.12 − − 0 3 I-2 0.13 − − 0 4 I-7 0.1 − − 0 5 I-1 (a) 0.13 − (II-1) 0.4 0 6 I-1 (d ) 0.12-(II-1) 0.407 I-2 0.13-(II-1) 0.408 I-7 0.1- (II-1) 0.409-Compound (a) -0 0.054 10- (II -1) 0.4 0 11 − − (II-9) 0.8 0 12 − − (III-1) 0.55 0 13 I-1 (a) 0.13 − (II-9) 0.8 0 14 I-1 (a) 0.13 − (III-1) 0.55 0 15 Compound (b) Compound (a) − 7.1 0.13 0.054 16 Compound (b) Compound (a) (II-1) 0.4 8.2 0.13 0.054 17 Compound (c) Compound (a) − 4.7 0.142 0.054 18 Compound (c) Compound (a) (II-1) 0.4 5.8 0.142 0.054

[0048]

[Chemical formula 26] The above results indicate that the composition of the present invention containing the components (ii) and (iii) is highly sensitive to visible light, and the sensitivity is further improved by adding the compound of the formula (II) or (III). It shows that it is doing. Further, the compound represented by the formula (I) of the present invention has higher sensitivity than that having a naphthothiazole skeleton, and has good solubility in an organic solvent,
Excellent coating suitability.

[Procedure amendment]

[Submission date] July 1, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

[0023]

[Chemical 13]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G03F 7/028 7/038 501

Claims (2)

[Claims] 1. A photopolymerizable composition comprising the following components (i) to (iii). (i) A polymerizable compound having an addition-polymerizable unsaturated bond. (ii) A compound represented by the general formula (I). [Chemical 1] R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, an alkoxycarbonyl group,
It represents an aryl group, a substituted aryl group or an aralkyl group. R ³ , R ⁴ , R ⁵ and R ⁶ are each independently R ¹ and R ²
Represents an alkylthio group, an arylthio group, an amino group or a substituted amino group. X represents a nonmetallic atomic group necessary for forming a 5- to 7-membered ring. Z represents a non-metal atom group necessary for forming a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heteroaromatic ring. (iii) Halomethyltriazine compound. 2. The photopolymerizable composition according to claim 1, further comprising a compound represented by the general formula (II) or (III). [Chemical 2] Here, Ar represents an aromatic group selected from one of the following general formulas, R ⁷ and R ⁸ represent a hydrogen atom or an alkyl group,
R ⁷ and R ⁸ may be bonded to each other to represent an alkylene group. [Chemical 3] (In the formula, R ^{9 to} R ¹³ may be the same or different from each other, and each is a hydrogen atom, a halogen atom, an alkyl group,
Alkenyl group, aryl group, substituted aryl group, hydroxyl group,
Alkoxy group, substituted alkoxy group, -S-R ¹⁵ group, -S
Represents an O-R ¹⁵ group or -SO ₂ R ¹⁵ group, where R ⁹ to R ¹³
At least one -S-R ¹⁵ group of radicals, represents -SO-R ¹⁵ group or -SO ₂ R ¹⁵ group, R ¹⁵ is an alkyl or alkenyl group, R ¹⁴ is a hydrogen atom, an alkyl group or an acyl group Represent Y is a hydrogen atom or (Wherein R ⁷ and R ⁸ are as defined above). ) R ¹⁶ and R ¹⁷ are each independently a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group, an alkoxycarbonyl group,
It represents an aryl group, a substituted aryl group, an aralkyl group, an alkylthio group, an arylthio group, an amino group or a substituted amino group. R ¹⁸ represents an alkyl group, a substituted alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, a substituted aryl group, an aralkyl group, an alkylthio group, an arylthio group, an amino group or a substituted amino group.