JP2547613B2 - Photopolymerizable composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a photopolymerizable composition. For more information,
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 or the like of a photosensitive printing plate that can be sensitive to an argon laser light source.

[Conventional technology]

Using a photosensitive composition in which a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a binder having a proper film-forming ability as necessary, and a thermal polymerization inhibitor are mixed, A method of duplicating an image by the method is currently known. That is, US Patent 2,927,02
As described in No. 2, No. 2,902,356 or No. 3,870,524, this type of photosensitive composition causes photopolymerization upon irradiation with light, and is cured and insolubilized. 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 a phenomenon), a cured image of a desired photopolymerizable composition can be formed. it can. 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, there is not sufficient photosensitivity only with a polymerizable compound having an ethylenically unsaturated bond, and it has been proposed to add a photopolymerization initiator to enhance photosensitivity,
Such photopolymerization initiators include benzyl, benzoin, benzoin ethyl ether, Michler's ketone, anthraquinone, acridine, phenazine, benzophenone, 2-benzophenone,
Ethyl anthraquinone and the like have been used. However, when these photopolymerization initiators are used, 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 remarkably low photopolymerization ability with respect to a light source in the visible light region of 400 nm or more as compared with light polymerization ability with respect to a light source in the ultraviolet region of 400 nm or less. Therefore, the application range of the 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, U.S. Pat.
According to 50445, certain photoreducing dyes, for example, rose bengal, eosin, erythrosine, etc., are reported to have effective visible light sensitivity. As an improved technique, a complex initiation system of dye and amine (Japanese Patent Publication No.
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, JP-A No. No. 155292), 3
Proposals have been made such as a system of a keto-substituted coumarin compound and an active halogen compound (JP-A-58-15503) and a system of a substituted triazine and a merocyanine dye (JP-A-54-15102). These techniques are certainly effective for visible light. However, the photosensitivity rate is not yet satisfactory, and further improvement techniques have been desired.

In addition, in recent years, a method for forming an image using a laser with high sensitivity to ultraviolet rays has been investigated, and a UV projection exposure method in printing plate making, laser direct plate making, laser facsimile, holography and the like are already in a practical stage, 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]

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

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

[Means for solving the problem]

The present inventor has conducted extensive studies to achieve the above-mentioned object, and a certain photopolymerization initiator system markedly increases the photopolymerization rate of a polymerizable compound having an ethylenically unsaturated bond, and is 400 nm or more. The present invention has been found to exhibit high sensitivity to visible light, and has reached the present invention.

That is, the present invention includes a polymerizable compound having at least one ethylenically unsaturated bond capable of being photopolymerized by actinic rays, a photopolymerization initiator, and optionally a linear organic polymer. In the photopolymerizable composition, the photopolymerization initiator contains at least three kinds of compounds selected from the following groups A, B and C, respectively.

(A) (i) an organic boron compound anion salt of at least one organic cationic dye, or (ii) a combination of at least one organic cationic dye and an organic boron compound anion salt (B) (i) having a carbon-halogen bond Compound (ii) At least one of aromatic onium salt or aromatic halonium salt (iii) Organic peroxide (C) General formula (In the formula, Ar represents an aromatic group selected from one of the following general formulas, R ¹ and R ² represent a hydrogen atom or an alkyl group, and R ¹ and R ² are bonded to each other. May represent an alkylene group.) (In the formula, R ^{3 to} R ⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a substituted aryl group, a hydroxyl group, an alkoxy group, a substituted alkoxy group, a —SR ⁹ group, a —SO group. Represents -R ⁹ group or -SO ₂ R ⁹ group, provided that R ³
To at least one of R ⁷ groups are -SR ⁹ groups, -SO-R ⁹ groups, or -SO ₂ R
Represents ⁹ group, R ⁹ represents an alkyl group, an alkenyl group, R ⁸ represents a hydrogen atom, an alkyl group, an acyl group. Y ¹ is a hydrogen atom or Represents

The polymerizable compound having an ethylenically unsaturated bond used in the present invention is a compound having at least one, and more preferably at least two ethylenically unsaturated bonds 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 esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and the like.

Specific examples of the monomer of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate and tetramethylene glycol as acrylic acid ester. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pen Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate,
There are sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer and the like.

As methacrylic acid esters, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2
-Hydroxypropoxy) phenyl] dimethylmethane,
Bis- [p- (acryloxyethoxy) phenyl] dimethylmethane;

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

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.

The maleic acid ester includes ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramaleate and the like.

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

Further, 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-hexamethylenebis-methacrylamide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like.

As another example, a vinyl group containing a hydroxyl group represented by the following general formula (A) is added to 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-49-431
No. 91, Japanese Patent Publication No. 52-30490 and polyester acrylates, epoxy resins and (meth)
Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates reacted with acrylic acid. Furthermore, those introduced as photocurable monomers and oligomers in Japan Adhesive Association magazine Vol. 20, No. 7, pages 300 to 308 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.

An organic boron compound anion salt of an organic cationic dye that can be effectively used in the present invention, that is, component (A)-
(I) is represented by the following general formula (I), for example.

Where D ⁺ is an organic cationic dye; R ¹⁰ , R ¹¹ ,
R ¹² and R ¹³ may be the same or different, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, an alkaryl group, an alkenyl group, an alkynyl group, an alicyclic group, a heterocyclic group, It is a group selected from an allyl group and derivatives thereof; R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be a cyclic structure in which two or more groups are bonded.

In the present invention, as the organic cationic dye, for example, a cationic methine dye, preferably a polymethine dye, a cyanine dye, an azomethine dye, more preferably cyanine,
Carbocyanine, hemicyanine; carbonium dye, preferably triarylmethane dye, xanthene dye, acridine dye, more preferably rhodamine; quinoneimine dye, preferably azine dye, oxazine dye, thiazine dye; quinoline dye; thiazole dye, (thia) pyrylium One or a combination of dyes selected from dyes can be used.

In the present invention, commercially available products or the above-mentioned organic cationic dyes known in the art can be used. Examples of these pigments are, for example, the section on basic paints in the Handbook of Dyes edited by the Organic Chemistry Society and “The Theory of the Photographic P” by TH James.
rocess) "Macmillan Publishing C
o., Inc) 1977, 194-290 and "Chemistry of Functional Dyes", CMC Publishers, 1-32, 189-206, 401-413, and JP-A-59. -189340 publication can be referred to.

Among the above dyes, dyes particularly useful in the present invention are cyanine dyes and xanthene dyes. Specific examples of the cyanine dye useful in the present invention include dyes represented by the following general formula (II).

General formula (II) In the formula, Z ¹ and Z ² are heterocyclic nuclei usually used for cyanine dyes, particularly thiazole nucleus, thiazoline nucleus, benzothiazole nucleus, naphthothiazole nucleus, oxazole nucleus, oxazoline nucleus, beizoxazole nucleus, naphthoxazole nucleus, tetrazole nucleus , Pyridine nucleus, quinoline nucleus, imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, naphthimidazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus or indolenine nucleus, etc. Represents These nuclei have a lower alkyl group such as a methyl group, a halogen atom, a phenyl group, a hydroxyl group, and a carbon number of 1 to 1.
4 alkoxy group, carboxyl group, alkoxycarbonyl group, alkylsulfamoyl group, alkylcarbamoyl group, acetyl group, acetoxy group, cyano group, trichloromethyl group, trifluoromethyl group, nitro group, etc. .

L ¹ , L ² or L ³ represents a methine group or a substituted methine group.
Examples of the substituted methine group include a lower alkyl group such as a methyl group and an ethyl group, a phenyl group, a substituted phenyl group, a methine group substituted with an aralkyl group such as a methoxy group, an ethoxy group, and a phenethyl group.

When L ¹ and R ¹⁴ , L ³ and R ¹⁵ and ω = 3, L ² and L ² may be alkylene bridged to form a 5- or 6-membered ring.

R ¹⁴ and R ¹⁵ are lower alkyl groups (more preferably alkyl groups having 1 to 8 carbon atoms), carboxy groups, sulfo groups, hydroxy groups, halogen atoms, alkoxy groups having 1 to 4 carbon atoms, phenyl groups, substituted An alkyl group having a substituent such as a phenyl group (preferably the alkylene moiety is C _{1 to} C ₅ ), for example, β-sulfoethyl, γ-sulfopropyl, γ-sulfobutyl, δ-sulfobutyl, 2- [2-
(3-Sulfopropoxy) ethoxy] ethyl, 2-hydroxysulfopropyl, 2-chlorosulfopropyl, 2
-Methoxyethyl, 2-hydroxyethyl, carboxymethyl, 2-carboxyethyl, 2,2,3,3-tetrafluoropropyl, 3,3,3-trifluoroethyl; allyl (a
llyl) group and other substituted alkyl groups usually used for N-substituents of cyanine dyes. ω represents 1, 2 or 3. X ⁻ represents a boron compound anion of the above structural formula (I).

Specific examples of the xanthene dye useful in the present invention include dyes represented by the following general formula (III).

R ¹⁶ , R ¹⁷ , R ¹⁸ , and R ¹⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms, and X is the boron compound anion of the structural formula (I). And Y represents an alkyl group, an aryl group, a hydrogen atom or an alkali metal.

Examples of preferable organic boron compound anion salts of organic cationic dye compounds that can be used in the present invention are given below. However, the present invention is not limited to the following compounds.

As the component (A) used in the present invention, anion salts other than the organic boron compound anion of the organic cationic dye, for example, halogen anion salts such as Cl ⁻ , Br ⁻ and I ⁻ , BF ₄ ⁻ and PF _{6 are used. ^{-, ClO 4 -, 1 /}} 2SO 4 -, Anion salts such as; and cation salts other than organic dye cations of organic boron compound anions, such as N ⁺ (C
It is a mixture with quaternary ammonium cation salts such as H ₃ ) ₄ , N ⁺ (C ₂ H ₅ ) ₄ and N ⁺ (nC ₄ H ₉ ) ₄ and alkali metal cation salts such as Na ⁺ and K ^+. May be.

Examples of the compound include the above general formula (II) or (II
X in I) is a halogen ion (eg Cl ⁻ , Br ⁻ , I ^{−
_{Etc.), ClO 4 -, 1 /}} 2SO 4 -, Can be mentioned. Further, as other examples of the organic boron compound anion salt of the above compound, specifically, U.S. Pat.Nos. 3,567,453, 4,343,891, European Patents 109,772, compounds described in 109,773 and those shown below, Can be mentioned.

_{A-20 (nC 4 H 9} 4 B - · N + (nC 4 H 9) 4 Examples of the compound having a carbon-halogen bond used in the present invention include Wakabayashi et al., Bull. Chem. Soc. Ja.
pan, 42, 2924 (1969), for example, 2-phenyl 4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- S-triazine, 2- (p-tolyl)-
4,6-bis (trichloromethyl) -S-triazine, 2
-(P-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -S-triazine, 2,4,6-Tris (trichloromethyl) -S-
Triazine, 2-methyl-4,6-bis (trichloromethyl) -S-triazine, 2-n-nonyl-4,6-bis (trichloromethyl) -S-triazine, 2- (α,
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.
53-133428, for example, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphtho-
1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- [4- (2-ethoxyethyl) -naphtho-
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 3337024, for example, Etc. and others Etc. can be mentioned.

J. Org Chem .; 29, 1527 by FC Schaefer et al.
(1964), for example, 2-methyl-4,6-bis (tribromomethyl) -S-triazine, 2,4,6-tris (tribromomethyl) -S-triazine, 2,4,6-
Tris (dibromomethyl) -S-triazine, 2-amino-4-methyl-6-tribromomethyl-S-triazine, 2-methoxy-4-methyl-6-trichloromethyl-S-triazine and the like can be mentioned.

Further, compounds described in JP-A-62-58241, for example, Etc. can be mentioned.

Or even MPHutt, EFElslager and LMWe
rbel, Journal of Heterocyclic Chemistry Volume 7 (No.
3), the following compound groups that can be easily synthesized by those skilled in the art according to the synthesis method described on page 511 et seq. (1970). Alternatively, the following compound group Alternatively, compounds as described in German Patent No. 2641100, for example 4- (4-methoxy-styryl) -6- (3.3-3-trichloropropenyl) -2
-Pyrone and 4- (3,4,5-trimethoxy-styryl) -6-trichloromethyl-2-pyrone, or the compounds described in DE 3333450, for example Alternatively, a compound group described in German Patent No. 3021590, Alternatively, the compounds described in German Patent No. 3021599, for example, Can be mentioned.

The aromatic onium salt used in the present invention is disclosed in
The compounds shown in JP-B No. 52-14278 and JP-B No. 52-14279 can be mentioned.

In particular, And so on.

Further, as an aromatic halonium salt, Japanese Patent Publication No. 52-14277.
The compounds shown in No. 1 can be mentioned. In particular Can be raised. Preferred of these are:
A compound of a BF ₄ salt or a PF ₆ salt is more preferably a BF ₄ salt or a PF ₆ salt of an aromatic iodonium salt.

The "organic peroxide" used in the present invention includes almost all organic compounds having one or more oxygen-oxygen bonds in the molecule, and examples thereof 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 (tertiarybutyl) Peroxy) cyclohexane, 2,2-bis (tertiarybutylperoxy) butane, tertiarybutyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, 2,5-dimethylhexa -2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, ditertiary butyl peroxide, tertiary butyl cumyl peroxide, dicumyl peroxide, bis (tertiary butyl peroxide) (Oxyisopropyl) benzene, 2,5-dimethyl-2,5-
Di (tertiary butyl peroxy) hexane, 2,5-
Dimethyl-2,5-di (tertiary butyl peroxy)
Hexine-3, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,
5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, dicarbonate 2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-)
(Methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxy neodecanoate, tert-butyl peroxy octanoate, tert-butyl peroxy-3, 5,5-
Trimethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, ditertiary butyl diperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tert-butyl Maleic acid peroxide,
Tertiary butyl peroxy isopropyl carbonate, 3,3 ', 4,4'-tetra- (t-butyl peroxycarbonyl) benzophenone, 3,3', 4,4'-tetra-
(T-amylperoxycarbonyl) benzophenone,
3,3 ', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (t-octylperoxycarbonyl) benzophenone, 3,3 ',
4,4'-tetra (cumylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), Carbonyldi (t-hexylperoxydihydrogen 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-octylper) (Oxycarbonyl) benzophenone, 3,3 ', 4,4'-tetra (cumylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (p-isopropylcumylperoxycarbonyl) benzophenone, di-t- Peroxide ester systems such as butyldiperoxyisophthalate are preferred.

General formula (However, Ar is one of the following general formulas.

In the compound represented by, the alkyl group represented by R ¹ and R ² has a carbon number of 1 to 1 such as methyl, ethyl and propyl.
There are 20 things. Examples of the alkylene group formed by combining R ¹ and R ² include tetramethylene and pentamethylene. Examples of the alkyl group represented by R ^{3 to} R ⁷ in Ar include those having 1 to 4 carbon atoms. Examples of the alkenyl group include those having 3 to 12 carbon atoms.
Furthermore, examples of the aryl group of R ^{3 to} R ⁷ include a phenyl group. Furthermore, examples of the alkoxy group include those having 1 to 4 carbon atoms. Moreover, as the substituents of the substituted aryl group and the substituted alkoxy group of R ^{3 to} R ⁷ , an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, and 1 to 1 carbon atoms
Examples thereof include four alkoxy groups, cyano groups, halogen atoms, nitro groups and the like. Examples of the acyl group of R ⁸ include acetyl, propionyl, acryloyl and the like.
Furthermore, examples of the alkyl group of R ⁹ include those having 1 to 8 carbon atoms, and examples of the alkenyl group of R ⁹ include 2 to 8 carbon atoms.
I can give you one.

Specific examples of such compounds include: And so on.

Among these, preferred are C-1, C-2, C-8 and C-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 weight polymer added as required. It is preferred to use. More preferably, 1% to 30% gives good results. The weight ratio of component (A): component (B): component (C) used in the present invention is 1: 0.001 to 1
0: 0.001 to 10 is suitable, and preferably 1: 0.005 to 5: 0.00
It is 5 to 5, most preferably 1: 0.01 to 3: 0.01 to 3. When the component (B) is used in the form of (ii), the weight ratio of the component dye to the component boron compound is 1: 0.05-10.
0 is suitable, preferably 1: 0.1 to 10, most preferably
1: 0.2-5.

Further, in the photopolymerizable composition of the present invention, the photopolymerization initiating ability can be further increased by using together various organic amine compounds, if necessary. Examples of these organic amine compounds include triethanolamine, dimethylamine, diethanolaniline, p-dimethylamine benzoic 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 contain N-
Phenylglycine, 2-mercaptobenzothiazole,
The photopolymerization initiation ability can be further enhanced by adding a hydrogen-donating compound such as an N, N-dialkylbenzoic acid alkyl ester. Such a hydrogen donating compound is
It is preferable to add 1 to 30% of the total weight of the photopolymerizable composition of the present invention.

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 high molecular polymer is used, water development becomes possible. Examples of such a linear organic high molecular polymer include addition polymers having a carboxylic acid in the side chain, for example, JP-A-59-44615.
No. 54/34327/58/12577 / 54-2
5957, JP 54-92723, JP 59-53836, JP
59-71048, that is, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer There is coalescence etc. 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 polymer 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. In addition, alcohol-soluble nylon and polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful for increasing the strength of the cured film. 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 formed image. It is preferably 30 to 85%. Further, the weight ratio of the photopolymerizable ethylenically unsaturated compound and the linear organic polymer is preferably in the range of 1/9 to 7/3. A more preferred range is 3/7 to 5/5.

In the present invention, in addition to the above basic components, a small amount of a thermal polymerization inhibitor is added to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during the production or storage of the photosensitive composition. It is desirable to do. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol, di-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-mercaptobenzimidazole, 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 weight of the whole composition. Further, if necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to the surface of the photosensitive layer to prevent polymerization inhibition by oxygen. 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 about 0.
5% to about 5% is preferred. 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, methoxymethoxysiethanol, diethylene glycol monomethyl ether Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, ethyl lactate and so on. 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 suitably ranges from about 0.1 g / m ² ~ about 10 g / m ² in weight after drying. More preferably, it is 0.5 to 5 g / m ² .

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 alloys), zinc, steel, etc. Metal plates, 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. Among these supports, the aluminum plate is particularly preferable because it is dimensionally remarkably stable and inexpensive. In addition, Japanese Patent Publication Sho-48-183
Composite sheets in which an aluminum sheet is bonded onto a polyethylene terephthalate film as described in No. 27 are also preferred.

In the case of a support having a surface of a metal, particularly aluminum, a surface treatment such as graining, immersion in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate, or anodizing is performed. Is preferred.

Further, an aluminum plate that is grained and then immersed in an aqueous solution of sodium silicate can be preferably used.
As described in JP-B-47-5125, an aluminum plate subjected to anodizing treatment and then immersed in an aqueous solution of an alkali metal silicate is preferably used. The anodizing treatment is carried out, for example, with an inorganic acid such as phosphoric acid, chromic acid, sulfuric acid, boric acid, or an acid, an organic acid such as 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.

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

Furthermore, Japanese Patent Publication No. 46-27481, Japanese Patent Publication No. 52-58602, Japanese Patent Publication No.
A surface treatment in which a support subjected to electrolytic graining as disclosed in No. 52-30503 and the above anodizing treatment and sodium silicate treatment are combined is 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, 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,
In order to prevent the polymerization inhibiting action due to oxygen in the air, a protective layer made of a polymer having excellent oxygen barrier properties such as polyvinyl alcohol, particularly polyvinyl alcohol having a saponification degree of 99% or more, and acidic celluloses may be provided. .
The method of coating such a protective layer is described in detail, for example, in US Pat. No. 3,458,311 and JP-B-55-49729.

Further, the photopolymerizable composition of the present invention can be used for a usual 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.
Particularly, due to the high sensitivity and the wide spectral sensitivity characteristic up to the visible light region, which are characteristics of the photopolymerizable composition of the present invention, a good effect can be obtained when applied to a photosensitive material for a visible light laser such as an Ar ⁺ laser.

The photosensitive material using the photopolymerizable composition of the present invention is imagewise exposed, 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 developers as described in JP-B-57-7427, sodium silicate,
Potassium silicate, sodium hydroxide, potassium hydroxide,
Inorganic alkaline agents such as lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, tribasic ammonium phosphate, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia, monoethanolamine or Aqueous solutions of organic alkaline agents such as diethanolamine are suitable. The concentration of the alkaline solution is
It is added in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight.

Further, the alkaline aqueous solution, if necessary, a surfactant, benzyl alcohol, 2-phenoxyethanol,
A small amount of organic solvent such as 2-butoxyethanol may be included. For example, mention may be made of those described in U.S. Pat. Nos. 3,375,171 and 3,615,480.

Furthermore, JP-A-50-26601, JP-A-58-54341 and JP-B-56-
The developing solutions described in Japanese Patent Nos. 39464 and 56-42860 are also excellent.

〔The invention's effect〕

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

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. Example 1
9, Comparative Examples 1 to 5 An aluminum plate with a thickness of 0.30 mm and a nylon brush and 400
The surface was grained using an aqueous suspension of mesh pumice and then thoroughly washed 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
= 12.7% using a sinusoidal alternating current under the condition of 12.7V
The electrolytic surface roughening treatment was performed in an aqueous nitric acid solution at an electric quantity of 160 Coulomb / dm ^{2 at} the time of the anode. When the surface roughness was measured,
It was 0.6 μ (Ra display). After desmutting 2 minutes immersed 55 ° C. in a 30% aqueous solution of sulfuric acid successively, aqueous 20% sulfuric acid, so that the thickness of the anodized film in a current density of 2A / dm ² is 2.7 g / m ² 2 It was anodized for a minute.

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

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

The photosensitivity test was performed using visible light and Ar ⁺ laser light (wavelength = 4
(88 nm). Visible light uses a tungsten lamp as a light source and a Kenko optical filter.
filter) BP-49. The photosensitivity was measured using a Fuji PS step guide (manufactured by Fuji Photo Film Co., Ltd., a step tablet having a transmission optical density of 0.05 at the first stage and increasing sequentially by 0.15 to 15 stages).

Examples 10 to 15 On the photosensitive layer, instead of the above protective layer, a saponification degree of 99.3 to
Examples 1 and 8 except that 99.9% of polyvinyl alcohol having a polymerization degree of 1000 was used, and 1.4 parts by weight of a fluorosurfactant W1104 (manufactured by Asahi Glass Co., Ltd.) was used with respect to 100 parts by weight of this polyvinyl alcohol. The photosensitive lithographic printing plate obtained in the same manner as in No. 9 and No. 9 was subjected to photosensitivity measurement in the same manner as in the Example. Table 2 shows the results.

Continuation of the front page (56) Reference JP 62-150242 (JP, A) JP 62-143044 (JP, A) JP 63-32540 (JP, A) JP 59-211036 (JP , A) JP 62-10642 (JP, A) JP 52-14277 (JP, B2)

Claims (1)

(57) [Claims] 1. A polymerizable compound having at least one ethylenically unsaturated bond capable of being photopolymerized by actinic rays, a photopolymerization initiator, and optionally a linear organic polymer. In the photopolymerizable composition, the photopolymerization initiator contains at least three compounds selected from the following groups A, B and C, respectively. (A) (i) an organic boron compound anion salt of at least one organic cationic dye or (ii) a combination of at least one organic cationic dye and an organic boron compound anion salt (B) (i) having a carbon-halogen bond Compound (ii) At least one kind of aromatic onium salt or aromatic halonium salt (iii) Organic peroxide (C) General formula (In the formula, Ar represents an aromatic group selected from one of the following general formulas, R ¹ and R ² represent a hydrogen atom or an alkyl group, and R ¹ and R ² are bonded to each other. May represent an alkylene group.) (In the formula, R ^{3 to} R ⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a substituted aryl group, a hydroxyl group, an alkoxy group, a substituted alkoxy group, a —SR ⁹ group, a —SO group. Represents -R ⁹ group or -SO ₂ R ⁹ group, provided that R ³
To at least one of R ⁷ groups are -SR ⁹ groups, -SO-R ⁹ groups, or -SO ₂ R
Represents ⁹ group, R ⁹ represents an alkyl group, an alkenyl group, R ⁸ is a hydrogen atom, an alkyl group or an acyl group. Y ¹ is a hydrogen atom or Represents )