JPH08190192A - Phtosensitive composition and photosensitive planographic printing plate having layer of this composition - Google Patents

Abstract

PURPOSE: To obtain such a photosensitive compsn. that the photosensitive liquid has good storage property and when the compsn. is formed into a photosensitive layer of a photosensitive planographic printing plate or the like, the photosensitive layer has good storage property and can be developed with water, and to provide a photosensitive planographic printing plate having a photosensitive layer comprising this photosensitive compsn. CONSTITUTION: (1) This photosensitive compsn. contains a polymerizable compd., photopolymn. initiator, latex which can be dispersed in an org. solvent, and compd. having groups selected from phenol-type hydroxyl groups, amino groups and carbonyl groups. Further, the photosensitive planographic printing plate has a photosensitive layer comprising this photosensitive compsn. on a base body. (2) The photosensitive compsn. contains a polymerizable compd., borate complex of a cationic dye having absorbance for near infrared rays, and latex which can be dispersed in an org. solvent. Further, the photosensitive planographic printing plate has a photosensitive layer comprising this photosensitive compsn. on a base body.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photopolymerizable photosensitive composition and a photosensitive lithographic printing plate having a photosensitive layer comprising the composition on a support, and more particularly to a lithographic printing plate and a resin developable with water. The present invention relates to a photosensitive lithographic printing plate having a photopolymerizable photosensitive composition suitable for applications such as letterpress, a film for platemaking or a resist for preparing a printed circuit board, and a photosensitive layer comprising the photosensitive composition.

[0002]

2. Description of the Related Art Conventionally, various water-developable photopolymerizable compositions used as photoresists have been proposed. Japanese Patent Publication No. 46-42450 and 50-14162
The publication discloses a photopolymerizable composition in which a water-soluble one is used as a photopolymerization initiator or an ethylenically unsaturated compound and these are uniformly dissolved in a water-soluble polymer.
However, the photopolymerizable composition using such a water-soluble photopolymerization initiator or ethylenically unsaturated compound is generally less sensitive than the photopolymerizable composition using an oil-soluble one, and Since a water-soluble polymer is used, it must be highly photocured to provide sufficient film strength and water resistance even when wet, and to use it as a lithographic printing plate, an ink receiving image As a result, lipophilicity is insufficient. Further, JP-A-54-9585 proposes a photopolymerizable composition comprising a water-dispersible latex, a water-dispersible oligomer and a photopolymerization initiator. By using the latex, film strength and water resistance can be improved. Is improved, but the lipophilicity is not sufficient, a water-soluble photopolymerization initiator,
When the ethylenically unsaturated compound is used by dispersing it in water, the above disadvantages cannot be avoided. When a lipophilic photopolymerization initiator or an ethylenically unsaturated compound is used by dispersing it in water using a surfactant or the like, the compatibility with the latex is poor and the surface becomes sticky, and sufficient sensitivity can be obtained. Absent.

Accordingly, the present inventors have filed a patent application for a water-developable image-forming material containing a pre-softening polymer compound, an ethylenically unsaturated compound and a photopolymerization initiator and having high photosensitivity and strong film strength. Proposed as No. 56-119332. As a result of continuous research on this image forming material, the present inventors have found that it takes a long time to develop, and that it has problems in storage stability when used as a photosensitive layer of a photosensitive solution and a photosensitive lithographic printing plate.

As a result of intensive studies based on the above facts, the present inventors have found that an oil-soluble ethylenically unsaturated compound, an organic solvent-dispersible water-insoluble particulate dispersion and an oil-soluble photopolymerization initiator are contained. It was found that a resist obtained from the photopolymerizable composition described above can be developed with water in a short time and proposed (JP-A-58-174402, JP-A-5-249675).
However, these techniques cannot be said to be sufficiently improved, and there is a problem that the developability is deteriorated and stains occur when developed with water.

On the other hand, conventionally, an image-forming material having a layer of a photopolymerizable composition comprising a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, a colorant and, if necessary, an organic polymer binder is a color proof. It is used to create colored images. However, these polymerizable compositions have a photosensitive area only to ultraviolet light or visible light of 500 nm or less, and it is difficult to photopolymerize by writing with laser light, particularly semiconductor laser light, which has been developed significantly in recent years. Met. In order to overcome this problem, some photopolymerizable compositions capable of writing in long-wavelength visible light and near-infrared light have been proposed, and borate complex photopolymerization initiation having absorption ability in the near-infrared light region has been proposed. A system containing a photopolymerizable composition used as an agent has been disclosed (JP-A-62-143044).
Further, Japanese Patent Application Laid-Open No. 2-4804 discloses a photosensitive material having a photosensitivity at a wavelength of 600 to 900 nm which is compatible with a semiconductor laser by combining a cationic dye as a photopolymerization initiator and a borate compound. But to date, 600
A photopolymerization system using a dye having an absorptivity at ~ 900 nm could not be developed with water in a short time. Further, there is a problem in the preservability of the photosensitive solution after preparation and the preservability of the photosensitive lithographic printing plate after coating due to the influence of a photopolymerization initiator, a sensitizer and the like.

[0006]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide a photosensitive solution which has a good storage stability and has a good storage stability when used as a photosensitive layer of a photosensitive lithographic printing plate or the like and which can be developed with water. A photosensitive composition for forming a layer and a photosensitive lithographic printing plate having the photosensitive composition as a photosensitive layer.

[0007]

The constitutions of the present invention for achieving the above-mentioned objects of the present invention are as follows.

A photosensitive compound containing a polymerizable compound, a photopolymerization initiator, a latex dispersible in an organic solvent, and a compound having at least one group selected from a phenolic hydroxyl group, an amino group and a carbonyl group. Composition.

A photosensitive composition comprising a polymerizable compound, a photopolymerization initiator, a latex dispersible in an organic solvent and a photosensitive composition containing a compound having at least one group selected from a phenolic hydroxyl group, an amino group and a carbonyl group. A photosensitive lithographic printing plate having a layer on a support.

A photosensitive composition comprising a polymerizable compound, a borate complex of a cationic dye having a near-infrared absorbing ability, and a latex dispersible in an organic solvent.

A photosensitive layer comprising a photosensitive composition comprising a polymerizable compound, a borate complex of a cationic dye capable of absorbing near infrared rays and a latex dispersible in an organic solvent on a support. Sex lithographic printing plate.

The present invention will be described in detail below.

Examples of the polymerizable compound used in the photosensitive composition of the present invention include addition-polymerizable ethylenically unsaturated compounds. The ethylenically unsaturated compound used in the present invention is a monomer, a prepolymer, that is, a dimer, a trimer,
It includes tetramers and oligomers (polymers or polycondensates having a molecular weight of 10,000 or less), mixtures thereof, and copolymers thereof.

Suitable ethylenically unsaturated compounds for use in the present invention are acrylic acid esters of polyhydric alcohols and methacrylic acid esters, such as ethylene glycol, trierythrylene glycol, tetraethylene glycol, propylene glycol and trimethylolpropane. Examples thereof include acrylic acid such as pentaerythritol and neopentyl glycol, and methacrylic acid ester.

Acrylic acid or methacrylic acid ester modified from bisphenol A, for example, a reaction product of bisphenol A-epichlorohydrin type epoxy resin prepolymer and acrylic acid or methacrylic acid, an alkylene oxide adduct of bisphenol A or the Hydrogenated acrylic acid, methacrylic acid ester and the like can also be used.

Apart from these ester systems, methylenebisacrylamide, methylenebismethacrylamide and bisacryl or bismethacrylamide of diamines such as ethylenediamine, propylenediamine, butylenediamine and pentamethylenediamine are also useful.

Further, a reaction product of diol monoacrylate or diol monomethacrylate and diisocyanate, triacrylic formal or triallyl cyanurate is also suitable.

Apart from these monomeric compounds, a linear polymer compound having an acryloyloxy group or a methacryloyloxy group in its side chain, for example, a ring-opening copolymer of glycidyl methacrylate or a vinyl copolymer of glycidyl methacrylate. Acrylic acid and methacrylic acid addition reaction products can also be used.

As the ethylenically unsaturated compound used in the present invention, a water-soluble one can be used, but a water-insoluble one is preferable from the viewpoint of photosensitivity and water resistance of an image, and in particular, in terms of photosensitivity, penta Erythritol tetraacrylate and trimethylolpropane triacrylate are the preferred monomers.

The photopolymerization initiator used in the present invention is a generally known one which is effective in combination with an ethylenically unsaturated compound, and includes, but is not limited to, the following compounds.

Specific examples thereof include acyloin; benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether and other acyloin derivatives; decyl bromide,
Decyl chloride, decylamine and the like; ketones such as benzophenone, acetone phenone, benzyl and benzoylcyclobutanone; Michler's ketone, diethoxyacetone and substituted benzophenones such as halogenated aceto and benzophenone; thioxanthone, chlorothioxanthone, isopropylthioxanthone, diisopropylthioxanthone, methylthioxanthone. Derivatives such as thioxanthone derivatives, quinones and benzoquinones, polynuclear cyclic quinones such as anthraquinone and phenanthrenequinone; substituted polynuclear cyclic quinones such as chloranthraquinone, methylanthraquinone, octamethylanthraquinone, naphthoquinone, dichloronaphthoquinone; halogenated aliphatic, Alicyclic and aromatic hydrocarbons and mixtures thereof, provided that halogen is chlorine, bromine, fluorine, iodine And, for example, mono- and polychlorobenzene, mono- and polybromobenzene, mono- and polychloroxylene, mono- and polybromoxylene, dichloromaleic anhydride, 1- (chloro-2-methyl) naphthalene, 2,4 -Dimethylbenzene morphonyl chloride, 1-bromo-3- (m-phenoxyphenoxy) benzene, 2-bromoethyl methyl ether, chlorendeinic anhydride and its corresponding ester, chloromethylnaphthyl chloride, chloromethylnaphthalene, bromomethylphenanthrene, di Iodomethylanthracene, hexachlorocyclopentadiene, hexachlorobenzene, octachlorocyclopentene and their compounds, lophine dimer and N-methyl-2
-Benzoylmethylene-β-naphthothiazole, N-ethyl-
There are heterocyclic compounds represented by 2- (2-thenoyl) methylene-β-naphthothiazole. In the present invention, as a photopolymerization initiator, JP-B-59-42684, JP-B-6-76444 and 5-85562.
Coumarin derivatives such as 3-benzoyl-7-methoxycoumarin, 3,3'-carbonylbis
(7-Dimethylaminocoumarin), 3- (2'-oxadiazoyl-5'-phenyl) -7-diethylaminocoumarin and the like can also be used. As the photopolymerization initiator used in the present invention, a water-soluble one can be used, but a water-insoluble one is preferable from the viewpoint of photosensitivity and water resistance.

The latex dispersible in the organic solvent contained in the photosensitive composition of the present invention should be kept stable for several hours or longer without dissolving, aggregating or precipitating with a desired organic solvent as a dispersion medium. It is a dispersion system that can The latex useful in the present invention is not particularly limited in the type of dispersoid as long as it does not dissolve, aggregate or precipitate in a predetermined organic solvent. The latex may be used alone or in combination of two or more.

Examples of the dispersoid of the latex include polyacrylic acid ester or its copolymer, polyacrylonitrile or its copolymer, polystyrene or its copolymer, polyethylene or its copolymer, polyvinyl chloride or its copolymer, polyvinylidene chloride or its copolymer. , Polyvinyl acetate or its copolymer,
Resol resin or its copolymer, ionomer resin,
Examples thereof include polymethylmethacrylate or a copolymer thereof and polybutadiene or a copolymer thereof.

The polymer compound which is preferably used in the present invention and which forms the dispersoid of the latex dispersible in the organic solvent preferably has a quaternary nitrogen atom in the molecule, whereby the dispersibility in water is improved. In addition, a physical bond with the polymer of the ethylenically unsaturated compound occurs. The quaternary nitrogen atom is preferably contained in the side chain of the polymer molecule.

Typical examples of the monomer units constituting such a polymer include those represented by the following general formulas [1] to [5].

[0026]

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[0027]

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In the general formulas [1] to [5], X ⁻ represents an anion. That is, halogen ion, sulfate ion, phosphate ion, sulfonate ion, acetate ion, other BF ₄ containing fluorine _{^{-, PF 6 -, SiF 6}} 2-, SbF 6 -, include anions such as BeF ₄ ^2- Be done.

The R's attached to N ⁺ may be the same or different and each R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (eg methyl, ethyl, propyl, isobutyl, pentyl, hexyl). , Heptyl, decyl groups), alkenyl groups (eg propenyl, butynyl groups), or aryl groups having 6 to 20 carbon atoms (eg phenyl, naphthyl groups), aralkyl groups (eg benzyl, Phenethyl, naphthyl, methyl groups) or alkaryl groups (eg, tolyl, xylyl groups). Further, those having a polymerizable unsaturated ethylene group are also preferable. This is because if a polymerizable group is contained in the molecule, it polymerizes with the above-mentioned ethylenically unsaturated compound during photopolymerization to form a chemical bond. Z represents a group of non-metal atoms necessary for forming an unsaturated heterocycle, and is preferably an imidazole, pyridine, piperidine, pyrrole or morpholine ring. n represents an integer.

A latex polymer having a cationic group and having a monomer unit represented by the above-mentioned general formulas (1) to (5) has a polar group without a polar group because the main chain is a C--C bond and is hydrophobic. Therefore, it contributes to the hydrophobicity of the photosensitive layer when it is formed. When the latex polymer is, for example, a water-based latex polymer, it may have a water-soluble group to the extent that it can be dispersed in water, so that a relatively large number of hydrophobic groups can be introduced into the polymer molecule, resulting in a decrease in hydrophilicity. This is advantageous in that it can be used and that the dispersion liquid containing it has a low viscosity relative to the resin concentration and therefore has good coatability when forming the photosensitive layer, and that the dried film can be formed into a thick film. In order to adjust the water solubility by introducing a hydrophobic group into this terax polymer, it is sufficient to copolymerize a non-cationic monomer with the above-mentioned cationic monomer. Examples of this non-cationic monomer include acrylic acid ester and methacrylic acid. Ester, styrene, alkylene, vinyl acetate, acrylonitrile and the like can be mentioned. This latex polymer is preferably crosslinked with a monomer having two or more unsaturated groups such as divinylbenzene and dimethacrylate, and is preferably produced by emulsion polymerization. This reduces the hydrophilicity of the monomer,
This is because emulsion polymerization can be effectively performed, and as a result, it contributes to the improvement of film strength.

In order to produce a copolymer of the above-mentioned cationic monomer and non-cationic monomer, 5 to 5 cationic monomers are contained in the above latex polymer having a cationic group.
It is preferably contained in an amount of 95% by weight, more preferably 25 to 65.
% By weight. Further, the non-cationic monomer is preferably contained in an amount of 5 to 95%, and the crosslinking monomer such as divinylbenzene is preferably contained in an amount of 0.1 to 8% by weight.

As a synthesis example of the above-mentioned latex polymer having a cationic group, vinylbenzyl chloride is emulsion-polymerized with another monomer as described in Examples of JP-A-51-73440, and thereafter, A method of quaternizing with a tertiary amine can be adopted. Another preferred synthetic method is JP-A-55-2.
This is the method described in Japanese Patent No. 2766. Another preferable synthetic method is the method described in JP-A-56-17352.

The latex polymer having a cationic group used in the present invention has a quaternary nitrogen atom in the cationic group in the composition, and has an amine, particularly a tertiary amine, in its molecule. As a result of being dispersed in an aqueous solvent 4
It also includes the case where it is a cationic group having a primary nitrogen atom.

The particle size of the above latex polymer is 10 to 200 n.
m is preferable, and when it is smaller than 10 nm, it is difficult to manufacture and it is not practical. On the other hand, when it is larger than 200 nm, the resolution of the image is deteriorated when the image portion after the exposure of the photosensitive layer is formed.

Specific examples of the polymer having a cationic group of the present invention include the compounds shown below. In the parentheses, the molar ratio is shown.

[0036]

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[0037]

[Chemical 4]

[0038]

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[0039]

[Chemical 6]

[0040]

[Chemical 7]

[0041]

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[0042]

[Chemical 9]

[0043]

[Chemical 10]

As the latex dispersible in the organic solvent used in the present invention, a water-insoluble particulate dispersion described in JP-B-2-15056 and an organic solvent dispersible dispersion described in JP-A-58-174402. Water-insoluble particulate dispersion and JP-A-60-362
The latex polymer having a cationic group described in JP-A-3 can be preferably used.

The preferred composition ratio of the polymerizable compound, the photopolymerization initiator and the latex dispersible in the organic solvent in the photosensitive composition of the present invention is 0.01 to 50% by weight of the polymerizable compound and 0.01 to 50% by weight of the photopolymerization initiator. 20% by weight, 0.01 to 50% by weight of a latex dispersible in an organic solvent.

A compound having at least one group selected from a phenolic hydroxyl group, an amino group and a carbonyl group used in the photosensitive composition of the present invention according to claim 1 or 2 (hereinafter referred to as "the antioxidant of the present invention"). ) Is a compound having an antioxidant function, and examples of the compound having a phenolic hydroxyl group include 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-phenol and 2,4- Di-tert-butyl-
Phenol, butylhydroxyanisole, 2,2'methylenebis (4-methyl-6-tert-butylphenol), 4,4'-
Butylidene bis (3-methyl-6-tert-butylphenol),
4,4'-thiobis (3-methyl-6-tert-butylphenol),
Tetrakis [methylene-3 (3 ', 5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,1,3-tris (2
-Methyl-4-hydroxy-5-tert-butylphenyl) butane,
2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-
Examples thereof include ditertiary butylphenyl) benzotriazole and 2- (2'-hydroxy-5'-methylphenyl) benzotriazole.

Examples of the compound having an amino group include phenyl-β-naphthylamine, α-naphthylamine, N, N'-di-
Secondary butyl-p-phenylenediamine, 6-ethoxy-2,2,4-
Trimethyl-1,2-dihydroquinoline, phenothiazone,
Examples thereof include N, N'-diphenyl-p-phenylenediamine.

Examples of the compound having a carbonyl group include phenyl salicylate, monoglycol salicylate, p-
Tert-butyl phenyl salicylate, 2-hydroxy-4-methoxy benzophenyl, 2-hydroxy-4-octotexibenzophenone, resorcinol monobenzoate,
2'-ethylhexyl-2-cyano-3-phenyl cinnamate and the like can be mentioned.

The amount of the antioxidant of the present invention added to the photosensitive composition of the present invention according to claim 1 or 2 is preferably 0.001 to 10% by weight, more preferably 0.005 to 5% by weight.
Range.

In the photosensitive composition according to the first or second aspect of the present invention, the antioxidant of the present invention may be used in combination with other antioxidants such as sulfur type and phosphoric acid type which have an antioxidant effect.

As the borate complex of the cationic dye having a near-infrared absorbing ability used in the invention according to claim 3 or 4, those represented by the following general formula [6] or [7] are preferable.

[0052]

[Chemical 11]

In the formula, Dye ⁺ represents a cationic dye and M ^{k +} represents a transition metal coordination complex cation.

R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a heterocyclic group or a cyano group, and these alkyl groups, The aryl group, alkenyl group, alkynyl group and heterocyclic group may further have a substituent. However, R
_At least one of ₁ , R ₂ , R ₃ and R ₄ is an optionally substituted alkyl group. Two or more of R ₁ , R ₂ , R ₃ and R ₄ may combine with each other to form a ring.

R ₅ and R ₆ each represent a hydrogen atom, a halogen atom or a monovalent substituent.

X is a hydroxyl group or a --N (R ₇ ) (R ₈ ) group (R ₇ and R ₈ each represent a hydrogen atom or an optionally substituted alkyl group, and R ₅ , R ₆ or R ₇ are They may combine with each other to form a ring), and M represents a transition metal atom.

K is 1 to 3, j is 2 or 3, m is 1 to 5,
n represents an integer of 1 to 4, respectively.

Specific examples of the cationic dye represented by Dye ⁺ include JP-A Nos. 62-143044, 63-208036, and 64-842.
Nos. 45, 64-88444, JP-A 1-152108, and 3-202609 can be used. Specific examples of preferable compounds are shown in the compound group A.

<< Compound Group A >>

[0060]

[Chemical 12]

[0061]

[Chemical 13]

[0062]

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[0063]

[Chemical 15]

Specific examples of the transition metal coordination complex cation represented by M ^{k +} include those described in JP-A-4-261405, in addition to those listed in the following compound group B.

<< Compound Group B >>

[0066]

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M ^{k +} jk X R ₉ R ₁₀ R ₁ R ₂ R ₃ R ₄ Co ²⁺ 2 2 N (C ₂ H ₅ ) ₂ NHCOC ₃ H ₇ (i) CH ₃ Ph Ph Ph Bu Ru ²⁺ 2 2 N (C ₂ H ₅ ) ₂ NHCOC ₃ H ₇ (i) CH ₃ Ph Ph Ph Bu Ru ²⁺ 2 2 N (C ₂ H ₅ ) (C ₂ H ₄ NHSO ₂ CH ₃ ) Cl CH ₃ Ph Ph Ph Bu Ru ²⁺ 2 2 N (C ₂ H ₅ ) (C ₂ H ₄ NHCOCH ₃ ) H CH ₃ Ph Ph Ph Bu Fe ²⁺ 2 2 N (C ₂ H ₅ ) (C ₂ H ₄ OH) CH ₃ CH ₃ Ph Ph Ph Bu Ir ³⁺ 2 3 N (C ₂ H ₅ ) ₂ NHCOC ₃ H ₇ (i) CH ₃ Ph Ph Ph Bu Ru ²⁺ 2 2 N (C ₂ H ₅ ) ₂ CONHC ₄ H ₉ CH ₃ Ph Ph Ph Bu Ru ²⁺ 2 2 N (C ₂ H ₅ ) ₂ CONHC ₄ H ₉ CH ₃ Ph Ph Ph iPr Co ²⁺ 2 2 N (C ₂ H ₅ ) ₂ NHCOC ₃ H ₇ (i) H Ph Ph Ph Bu Ru ²⁺ 2 2 N (C ₂ H ₅ ) ₂ NHSO ₂ CH ₃ CH ₃ Ph Ph Ph Bu Ru ²⁺ 3 3 N (C ₂ H ₅ ) ₂ NHCOC ₃ H _{7
(I) CH 3 Ph Ph Ph} Bu Ru 2+ 2 2 N (C 2 H 5) 2 NHCO
_{C 3 H 7 (i) CH} 2 NHSO 2 CH 3 Ph Ph Ph Bu Co 2+ 2 2 N (C 2 H 5) 2 SO 2 N
_{(C 2 H 5) 2 CH} 3 Ph Ph Ph Bu Ru 2+ 2 2 N (C 2 H 5) 2 NHCO
_{C 3 H 7 (i) NHCOCH} 3 Ph Ph Ph Bu Ru 2+ 2 2 N (C 2 H 5) (C 2 H 4 NHSO 2 CH 3) Cl
^{_{CH 3 Ph Ph Ph Bu Fe 2+}} 2 2 N (C 2 H 5) 2 NHCO
_{NHC 3 H 7 (i) CH} 3 Ph Ph Ph Bu Ru 2+ 2 2 N (C 2 H 5) 2 NHCO
_{C 3 H 7 (i) CH} 3 Bu Bu Bu Bu Ru 2+ 2 2 N (C 2 H 5) 2 NHCO
_{C 3 H 7 (i) CH} 3 Ph Ph Ph Bz

[0068]

[Chemical 17]

Where Ph: phenyl Bu: buthyl iPr: i-
Propyl Bz: represents benzyl.

[0070]

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M ²⁺ R ₁₁ Ru ²⁺ Cl Ru ²⁺ NHCOC ₃ H ₇ (i) Co ²⁺ Cl The photopolymerization initiator represented by the above general formula [6] or [7] is a dye anion part in advance. In this example, a boronic acid compound represented by the following general formula [8] is allowed to coexist with a dye having an anion moiety. The same function can be exhibited even when the compound represented by the general formula [6] is produced by ion exchange in the photosensitive layer or in the coating liquid for the photosensitive layer.
Further, when using the photopolymerization initiator of the general formula [6] or [7], it is preferable to add the borate represented by the general formula [8] for the purpose of improving the sensitivity.

[0072]

[Chemical 19]

In the formula, R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as defined in the above general formula [6] or [7], and X ⁺
Is a counter cation (eg, an alkali metal cation,
(5) Group 5A onium compounds such as ammonium cations and phosphonium cations, and 6A group onium compounds such as sulfonium and telluronium. Specific examples of the compound are described in JP-A-64-13142 and JP-A-2-4804.

The dispersion medium or solvent of the photosensitive composition of the present invention may be only water, and in this case, there is no problem such as pollution as described above, but it is a support at the time of coating the photosensitive composition. A water-miscible organic solvent may be supplementarily used in order to improve the wettability and the drying property during drying. Examples of such substances include methanol, ethanol, methyl cellosolve, ethyl cellosolve, acetone, halogenated hydrocarbons, ethyl acetate and the like.

Various additives can be added to the photosensitive composition of the present invention as necessary. For example, an appropriate amount of hydroquinone and its analogues can be added to prevent thermal polymerization during storage. Other additives such as an adhesion improver, another polymer as a binder, and a matting agent for roughening the surface of the photosensitive layer can be added.

In order to produce the photosensitive composition of the present invention, the above-mentioned respective components may be mixed by stirring by an appropriate means.

To prepare a photosensitive image-forming material such as a lithographic printing plate, a resin relief plate, a plate-making film, or a metal etching photoresist for a printed wiring board using the photosensitive composition of the present invention, a support is used. A coating solution containing this photosensitive composition is applied onto the above and dried to form a photosensitive layer. This photosensitive layer may be provided as a single layer, but, for example, as in the case of making a photomask for blocking ultraviolet rays for a plate-making film, an undercoat layer is provided on a transparent support, and then this undercoat layer is formed. You may make it form the photosensitive layer which consists of the photosensitive composition of this invention on it. In this case, as the undercoat layer, a polymer compound is used as a coloring material for blocking ultraviolet rays (for example, 300
Dyes having absorption in the wavelength range of up to 700 nm or pigments such as copper phthalocyanine, carbon black and titanium dioxide). The thickness of the photosensitive layer thus provided is 0.1 to 2 as a dry coating film of the photosensitive composition.
A range of 0 g / m ² is suitable.

As a support for producing the photosensitive lithographic printing plate, a metal plate such as aluminum, iron, copper or an alloy thereof, a paper support, especially a synthetic paper (polypropylene,
Polyethylene laminated paper), a plastic support (eg, cellulose acetate, polyethylene terephthalate, polypropylene, polystyrene, vinylidene chloride, etc.) and the like. Such a support is preferably surface-treated electrically, chemically or mechanically for the purpose of improving the adhesion to the photosensitive layer. Further, an undercoat layer may be provided to improve the adhesiveness. Furthermore, in order to make the surface of the photosensitive layer formed as described above less slippery, a layer comprising the above matting agent may be provided, and in the case of a photosensitive image forming material using a flexible support, An anti-curl layer for preventing curl may be provided on the surface opposite to the photosensitive layer.

To produce a photosensitive lithographic printing plate using the photosensitive composition of the present invention, typical coating means such as wire bar coating, spin coating, brush coating, doctor blade coating or hopper coating is used. It is used, and after being applied by these means, it is dried by an appropriate means.

The photosensitive lithographic printing plate prepared as described above is first imagewise exposed to actinic rays. Here, as the actinic ray, any one can be used as long as it is exposed to the photopolymerization initiator contained in the photosensitive composition. For example, a mercury lamp, a xenon lamp, a laser, etc. are mentioned. The exposed photosensitive image-forming material is developed with normal tap water. In this case, if necessary, warm water may be added, or an alkali, an acid, or a solvent may be added. At this time, the development can be effectively performed by rubbing the surface with a suitable material such as a sponge.

[0081]

EXAMPLES Examples of the present invention will now be described, but the embodiments of the present invention are not limited to these.
In addition, in the following Examples and Comparative Examples, Examples 1 to 3 and Comparative Examples 1 to 2 relate to claim 1 or 2, and Examples 4 to 8
And Comparative Examples 3 to 6 relate to claim 3 or 4.

Preparation of support An aluminum plate having a thickness of 0.3 mm was immersed in a 20% sodium phosphate aqueous solution for degreasing, electrolytic polishing was performed, and then anodization was performed in sulfuric acid, followed by treatment with a sodium metasilicate aqueous solution. After washing with water and drying, it was used as a support for the photosensitive lithographic printing plates of the following Examples and Comparative Examples.

Example 1 A coating solution 1 of a photosensitive composition having the following composition was prepared.

Coating solution 1 of photosensitive composition 1,4′-butylidene bis (3-methyl-6-tert-butylphenol) 0.12 g 3,3′-carbonylbis (diethylaminocoumarin) 0.6 g 3,3 ′, 4, 4'-Tetrakis (t-butyldioxycarbonyl) benzophenone 0.8g Pentaerythritol triacrylate 5.0g Latex 1 5.0g dispersible in organic solvent

[0085]

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2-Methoxyethanol 64.6 g The above coating solution 1 was coated on a support using a wire bar so that the film thickness after drying was 1.5 μm and dried to prepare a photosensitive lithographic printing plate. Scanning speed of 9.8m / using Ar ⁺ laser beam (488μm) for this photosensitive lithographic printing plate
s, scan time (41 cm × 59 cm), and exposed for 9.7 min. A cylindrical exposure machine was used for scanning. The exposed photosensitive lithographic printing plate was immersed in water at 30 ° C. for 1 minute and then lightly rubbed with a sponge to develop to prepare a lithographic printing plate. The storability of the coating solution and the photosensitive lithographic printing plate were evaluated by the following evaluation methods.

Method for evaluating storability of coating liquid The coating liquid was sealed in a sample bottle so that air was not introduced, placed in a constant temperature bath at 30 ° C, and stored for 3 days, 5 days and 7 days. The sensitivity after storage was measured for the photosensitive lithographic printing plate prepared by coating on the support by the method described below.

Evaluation Method of Sensitivity The sensitivity was determined by the gray scale method and the spot exposure method. The former was obtained from the minimum exposure energy at which a light-sensitive lithographic printing plate was closely contacted with a gray scale and irradiated with a light having a wavelength of 490 nm taken out from an ultra-high pressure mercury lamp through a filter, and then developed by the above method to obtain a cured image. . The latter uses the Ar ⁺ laser 488 μm oscillation line, exposes the photosensitive lithographic printing plate at different irradiation times, then develops it in the same manner, and obtains a cured image equivalent to the laser beam diameter (1.36 nm) from the exposure energy I asked.

Method for evaluating storability of photosensitive lithographic printing plate After applying the coating liquid 1 and drying, the coating liquid was stored at 50 ° C. and 20% relative humidity for 5 days (DT-5), and the change in sensitivity after that was measured by the above method. It was measured at.

Example 2 The same experiment as in Example 1 was carried out except that the coating solution 1 of the photosensitive composition was changed to the following coating solution 2.

Coating solution of photosensitive composition 2 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline 0.12 g 3,3′-carbonylbis (diethylaminocoumarin) 0.6 g 3,3 ′, 4 4,4'-Tetrakis (t-butyldioxycarbonyl) benzophenone 0.8 g pentaerythritol triacrylate 5.0 g Latex 1 dispersible in an organic solvent 1 (above) 5.0 g 2-methoxyethanol 64.6 g Example 3 Application of Photosensitive Composition The same experiment as in Example 1 was conducted except that the liquid 1 was changed to the coating liquid 3 described below.

Photosensitive Composition Coating Liquid 3 2-Hydroxy-4-octoxybenzophenone 0.12 g 3,3′-carbonylbis (diethylaminocoumarin) 0.6 g 3,3 ′, 4,4′-tetrakis (t-butyl) Dioxycarbonyl) benzophenone 0.8 g Pentaerythritol triacrylate 5.0 g Latex 1 dispersible in organic solvent 5.0 g 2-methoxyethanol 64.6 g Comparative Example 1 Coating solution 1 of the photosensitive composition was changed to Coating solution 4 below. The same experiment as in Example 1 was carried out except that

Photosensitive Composition Coating Liquid 4 3,3′-Carbonylbis (diethylaminocoumarin) 0.6 g 3,3 ′, 4,4′-Tetrakis (t-butyldioxycarbonyl) benzophenone 0.8 g Pentaerythritol triacrylate 5.0 g Latex 1 dispersible in organic solvent (above) 5.0 g 2-methoxyethanol 64.6 g Comparative Example 2 The same experiment as in Example 1 was conducted except that the coating liquid 1 of the photosensitive composition was changed to the following coating liquid 5. It was

Coating solution 5 of photosensitive composition 4,4′-butylidene bis (3-methyl-6-tert-butylphenol) 0.12 g 3,3′-carbonylbis (diethylaminocoumarin) 0.6 g 3,3 ′, 4, 4'-tetrakis (t-butyldioxycarbonyl) benzophenone 0.8 g pentaerythritol triacrylate 5.0 g poly (methyl methacrylate) / (methacrylic acid) (90:10) 5.0 g 2-methoxyethanol 64.6 g Examples 1 to 4 above The results of No. 3 and Comparative Examples 1 and 2 are shown in Table 1 below.

[0095]

[Table 1]

(Note) 1. "Immediate sensitivity" is the sensitivity immediately after the photosensitive lithographic printing plate is prepared by coating the coating solution on the support immediately after preparation and drying.

2. The photosensitive lithographic printing plate of Comparative Example 2 could not be developed and its sensitivity could not be measured.

Example 4 A coating solution 6 of a photosensitive composition having the following composition was prepared.

Coating liquid 6 of photosensitive composition Organic boron salt TBA / BTPB (Tetrabutylammonium salt of butyltriphenylboron) 0.3 g Borate complex of cationic dye (IR-1) 0.15 g Pentaerythritol triacrylate 5.0 g Organic solvent Dispersible latex 1 (above) 5.0 g 2-methoxyethanol 64.6 g The above coating solution 6 was coated on a support in the same manner as in Example 1 to prepare a photosensitive lithographic printing plate. For this photosensitive lithographic printing plate, a semiconductor laser (LT090MD, 1 manufactured by Sharp Corp.)
00mW) Main wavelength 830nm, optical system efficiency 10μm, average energy density of light irradiated on photosensitive layer surface 5mJ / cm ² , beam diameter 15n
Exposure was performed at m and a scanning pitch of 10 μm, and the average exposure energy density (mJ / cm ² ) was determined. Development was carried out by immersing the plate in water at 30 ° C for 1 minute and then rubbing it lightly with a sponge to obtain a lithographic printing plate. The storability of the coating solution (photosensitive solution) of the above-mentioned photosensitive composition and the photosensitive lithographic printing plate were evaluated in the same manner as in Example 1.

Example 5 The same experiment as in Example 5 was conducted except that the coating solution 6 of the photosensitive composition was changed to the following coating solution 7.

Coating Solution 7 for Photosensitive Composition Organic Boron Salt TBA / BTPB (Tetrabutylammonium Salt of Butyltriphenylboron) 0.3 g Cationic Dye Borate Complex (IR-1) 0.15 g Mercaptobenzotetrazole 0.2 g Pentaerythritol Tritrate Acrylate 5.0 g Latex 1 dispersible in organic solvent (above) 5.0 g 2-methoxyethanol 64.6 g Example 6 The same experiment as in Example 5 except that the coating liquid 6 of the photosensitive composition was changed to the following coating liquid 8. I went.

Coating solution of photosensitive composition 8 4,4′-butylidene bis (3-methyl-6-tert-butylphenol) 0.12 g Organic boron salt TBA / BTPB (Tetrabutylammonium salt of butyltriphenylboron) 0.3 g Cationic Dye borate complex (IR-1) 0.15 g Mercaptobenzotetrazole 0.2 g Pentaerythritol triacrylate 5.0 g Latex 1 dispersible in organic solvent 5.0 g 2-methoxyethanol 64.6 g Example 7 Coating liquid of Example 5 The same experiment as in Example 5 was conducted except that the borate complex IR-1 of the cationic dye in the composition of Example 7 was changed to IR-2.

Example 8 Organic Boron Salt TBA · B in Composition of Coating Solution 7 of Example 5
The same experiment as in Example 5 was carried out except that TPB was changed to the organic boron salt TBA · BTAB (tetrabutylammonium salt of butyltrianisylboron).

Comparative Example 3 The same experiment as in Example 1 was conducted except that the coating solution 6 of the photosensitive composition was changed to the following coating solution 9.

Coating solution of photosensitive composition 9 3,3′-carbonylbis (diethylaminocoumarin) 0.6 g 3,3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone 0.8 g Pentaerythritol triacrylate 5.0 g poly (methyl methacrylate) / (methacrylic acid) (90:10) 5.0 g 2-methoxyethanol 64.6 g Comparative Example 4 Example 4 except that the coating solution 6 of the photosensitive composition was changed to the following coating solution 10. The same experiment was performed.

Coating Solution for Photosensitive Composition 10 Organic Boron Salt TBA / BTPB (Tetrabutylammonium Salt of Butyltriphenylboron) 0.3 g Borate Complex (IR-1) of Cationic Dye 0.15 g Mercaptobenzotetrazole 0.2 g Pentaerythritol Tritrate Acrylate 5.0 g Poly (methyl methacrylate) / (methacrylic acid) (90:10) 5.0 g 2-Methoxyethanol 64.6 g Comparative Example 5 Example except that the coating liquid 6 of the photosensitive composition was changed to the following coating liquid 11. The same experiment as in 4 was performed.

Coating solution of photosensitive composition 11 4,4′-butylidene bis (3-methyl-6-tert-butylphenol) 0.12 g Organic boron salt TBA / BTPB (Tetrabutylammonium salt of butyltriphenylboron) 0.3 g Cationic Dye borate complex (IR-1) 0.15 g Mercaptobenzotetrazole 0.2 g Pentaerythritol triacrylate 5.0 g Poly (methyl methacrylate) / (methacrylic acid) (90:10) 5.0 g 2-Methoxyethanol 64.6 g Comparative Example 6 Photosensitization The same experiment as in Example 1 was carried out except that the coating solution 6 of the volatile composition was changed to the following coating solution 12.

Coating solution of photosensitive composition 12 3,3′-Carbonylbis (diethylaminocoumarin) 0.6 g 3,3 ′, 4,4′-Tetrakis (t-butyldioxycarbonyl) benzophenone 0.8 g Pentaerythritol triacrylate 5.0 g Latex 1 dispersible in organic solvent (above) 5.0 g 2-methoxyethanol 64.6 g The results of Examples 4 to 8 and Comparative Examples 3 to 6 are shown in Table 2 below.

[0109]

[Table 2]

(Note) 1. "Immediate sensitivity" is the sensitivity immediately after the photosensitive lithographic printing plate is prepared by coating the coating solution on the support immediately after preparation and drying.

[0111] 2. The photosensitive lithographic printing plates of Comparative Examples 1 to 4 could not be developed and the sensitivity could not be measured.

[0112]

INDUSTRIAL APPLICABILITY According to the present invention, a sensitizer for forming a photosensitive layer which can be developed with water has good storability of a photosensitive solution and has good storability when used as a photosensitive layer of a photosensitive lithographic printing plate or the like. Provided is a photosensitive composition and a photosensitive lithographic printing plate having the photosensitive composition as a photosensitive layer.

Claims (4)

[Claims] 1. A polymerizable compound, a photopolymerization initiator, a latex dispersible in an organic solvent, and a compound having at least one group selected from a phenolic hydroxyl group, an amino group and a carbonyl group. Photosensitive composition. 2. A photosensitive composition containing a polymerizable compound, a photopolymerization initiator, a latex dispersible in an organic solvent, and a compound having at least one group selected from a phenolic hydroxyl group, an amino group and a carbonyl group. A photosensitive lithographic printing plate having the following photosensitive layer on a support. 3. A photosensitive composition comprising a polymerizable compound, a borate complex of a cationic dye having a near-infrared absorbing ability, and a latex dispersible in an organic solvent. 4. A photosensitive layer comprising a photosensitive composition containing a polymerizable compound, a borate complex of a cationic dye having a near-infrared absorbing ability and a latex dispersible in an organic solvent, on a support. Photosensitive lithographic printing plate.