JP2709532B2 - Photosensitive lithographic printing plate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive lithographic printing plate, and more particularly, to a white lithographic printing plate having improved adhesion between a support having a hydrophilic surface and a photosensitive layer provided thereon. The present invention relates to a photosensitive lithographic printing plate having a photopolymerizable or photocrosslinkable photosensitive layer with improved safety against light (hereinafter referred to as white light safety).

[0002]

2. Description of the Related Art There are many attempts to use a photopolymerizable composition and a photocrosslinkable composition as an image forming layer of a photosensitive layer of a photosensitive lithographic printing plate. As the photopolymerizable composition, a polymer as a binder as disclosed in JP-B-46-32714, a basic composition comprising a monomer and a photopolymerization initiator, and disclosed in JP-B-49-34041. A composition in which unsaturated double bonds are introduced into a polymer as such a binder to improve the curing efficiency, JP-B-48-38403
Nos. JP-B-53-27605 and British Patent No. 1388492
Compositions using a novel photopolymerization initiator as disclosed in the specification and the like are known.

As a photocrosslinkable composition, a polymer which crosslinks by a cycloaddition reaction is well known. As such a photocrosslinkable polymer, a polymer having a maleimide group in a side chain or a photocrosslinkable polymer adjacent to an aromatic ring is used. Polymers having a cinnamyl group, a cinnamoyl group, a cinnamylidene group, or a cinnamylideneacetyl group having a quantifiable unsaturated double bond in the side chain or main chain are useful. In particular, a polymer having a maleimide group in the side chain and a phenylenediacrylic acid or a polyester having a cinnamic acid skeleton in a molecular chain produced by condensation of an alkyl ester thereof with a glycol have been partially commercialized with high sensitivity. ing.

However, if these photosensitive layers are used as they are due to insufficient adhesion to the aluminum support, images may be peeled off or damaged by rubbing with a brush or the like during development. Sufficient image intensity cannot be obtained, and this tendency is remarkable especially at the time of low exposure, resulting in a problem such as low sensitivity. Many attempts have been made to improve this poor adhesion. For example, as a photopolymerizable composition, an attempt was made to use a negative-working diazo resin as an undercoat layer as disclosed in JP-A-54-72104 and U.S. Pat.
No. 3,389,389, JP-A-2-111948, and Japanese Patent Application No. 1-137890, a method of adding a diazo resin to a photosensitive composition is known. As the photocrosslinkable composition, JP-B-50-7481, JP-A-62-78544, JP-A-1-37891,
Japanese Patent Application No. 2-37786 discloses a method using a diazo resin.

However, the method of using a diazo resin in the photopolymerizable or photocrosslinkable photosensitive layer has a problem because the photosensitive wavelength range between the photopolymerization initiator or sensitizer and the diazo resin is displaced. Was. Specifically, for white fluorescent lamps,
Even when using a photopolymerization initiator or a sensitizer having no sensitivity, only the diazo resin is exposed, causing fog,
Problems such as thickening of halftone dots occurred.

[0006]

SUMMARY OF THE INVENTION Accordingly, the present invention provides excellent adhesion between a support and a photosensitive layer while maintaining excellent sensitivity, photosensitive area, and performance of the photosensitive layer, and furthermore, safety against a white fluorescent lamp. An object of the present invention is to provide a photosensitive lithographic printing plate excellent in lithographic printing.

[0007]

Means for Solving the Problems The present inventors have developed a lithographic printing plate having a photosensitive layer containing a photopolymerizable composition or a photocrosslinkable composition provided on a support having a hydrophilic surface. It has been found that the above object can be achieved by incorporating a diazo resin having the structural unit in the photosensitive layer or the intermediate layer, and the present invention has been accomplished based on this finding.

Namely, the present invention is, on a support having a hydrophilic surface, in the photosensitive lithographic printing plate having a photosensitive layer containing a photopolymerizable composition, the photosensitive layer is, by the following general formula (I) Aromatic diazonium compound shown, and phenoxyacetic acid or
Is a photosensitive lithographic printing plate comprising a co-condensed diazo resin containing benzoic acid as a constituent unit. Book
The invention also provides an intermediate layer on a support having a hydrophilic surface.
And a photosensitive lithographic plate provided with a photosensitive layer containing a photopolymerizable composition
In the printing plate, the intermediate layer is represented by the following general formula (I).
Aromatic diazonium compound and phenoxyacetic acid or
Including co-condensed diazo resin containing benzoic acid as a constituent unit
It relates to a photosensitive lithographic printing plate characterized by having .

[0009]

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[0010] R ¹ is an alkoxy group, an alkylamino group or a hydrogen atom, R ² represents a halogen atom, an alkyl group, hydroxy group, carboxy ester group, a carboxyl group, an alkoxy group, or a hydrogen atom, X ^- is Y represents -NH-, -O-, or -S-. However,
R ¹ and R ² are not hydrogen atoms at the same time. Less than,
The present invention will be described in detail.

The photopolymerizable composition of the present invention contains, as essential components, a polymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a polymer. A polymerizable compound having an ethylenically unsaturated bond is a compound having at least one ethylenically unsaturated bond in its chemical structure, and may be a monomer, a prepolymer, that is, a dimer, a trimer, or another compound. Oligomers, their mixtures, and their copolymers. Examples thereof are unsaturated carboxylic acids and salts thereof,
Examples include esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyamine compounds.

Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid and maleic acid. Salts of unsaturated carboxylic acids include the alkali metal salts of the aforementioned acids, for example, sodium and potassium salts. Specific examples of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylates such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, Propylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate,
1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate,
Examples include dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, and polyester acrylate oligomer. As methacrylic acid esters, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate,
Trimethylol propane trimethacrylate, trimethylol ethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate , Screw-
[P- (3-methacryloxy-2-hydroxypropoxy) phenyl] dimethylmethane, bis- [p- (methacryloxyethoxy) phenyl] dimethylmethane and the like. Examples of itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate,
Examples thereof include 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetritaconate. Examples of the crotonic acid ester include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, sorbitol tetracrotonate and the like. 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, pentaeristol dimaleate, and sorbitol tetramaleate. Furthermore, a mixture of the above-mentioned esters can also be mentioned.

Specific examples of the amide of the aliphatic polyamine compound and the unsaturated carboxylic acid include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-
Hexamethylenebis-acrylamide, 1,6-hexamethylenebis-methacrylamide, diethylenetriaminetrisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like.

As another example, a polyisocyanate compound having two or more isocyanate groups in one molecule described in JP-B-48-41708 may be added to a vinyl group containing a hydroxyl group represented by the following general formula. A vinyl urethane compound containing two or more polymerizable vinyl groups in one molecule to which a monomer has been added is exemplified. CH ₂ CC (R) COOCH ₂ CH (R ′) OH (where R and R ′ each represent a hydrogen atom or a methyl group.) The photopolymerization initiator used in the present invention is disclosed in US Pat. No. 2,367,660. Bicinal polyketaldonyl compounds disclosed in the specification, α-carbonyl compounds disclosed in U.S. Patent Nos. 2,367,661 and 2,367,670, and acyloin disclosed in U.S. Patent No. 2,448,828 Ethers, aromatic acyloin compounds substituted at the α-position with a hydrocarbon disclosed in U.S. Pat.No. 2,722,512, U.S. Pat.Nos. 3,046,127 and 2,955
The polynuclear quinone compound disclosed in U.S. Pat. No. 1,758, the combination of a triarylimidazole dimer / p-aminophenyl ketone disclosed in U.S. Pat. No. 3,549,367, and U.S. Pat. No. 3,870,524. Benzothiazole compounds, U.S. Pat.No.4,239,850
Benzothiazole compounds disclosed in
Trihalomethyl-s-triazine compounds, acridine and phenazine compounds disclosed in U.S. Pat.No. 3,751,259, oxadiazole compounds disclosed in U.S. Pat. Is about 0.5, based on the total weight of the photopolymerizable composition.
% By weight to about 15% by weight, preferably 2-10% by weight.

The high molecular weight polymer used in the present invention may be benzyl (meth) acrylate / (meth) acrylic acid / if necessary, other addition-polymerizable vinyl monomers as described in JP-B-59-44615. Copolymer;
-34327, methacrylic acid / methyl methacrylate or ethyl methacrylate / alkyl methacrylate copolymer having an alkyl group of C _{4 to} C ₁₅ ; other JP-B-58-12577, JP-B-54- No. 25957, JP-A-54-927
(Meth) acrylic acid copolymer as described in No. 23; allyl (meth) acrylate / (meth) acrylic acid as described in JP-A-59-53836 / optionally other Addition polymerizable vinyl monomer copolymer, maleic anhydride copolymer described in JP-A-59-71048, and pentaerythritol triacrylate added by half-esterification or vinyl methacrylate / methacrylic acid / necessary -COOH in the polymer, such as other addition polymerizable vinyl monomer copolymer _{according, -PO 3 H 2, -SO 3} H, -
An acidic vinyl copolymer having an SO ₂ NH ₂ , —SO ₂ NHCO — group and an acid value of 50 to 200 can be mentioned.

Particularly, among these, benzyl (meth) acrylate / (meth) acrylic acid / optionally other addition-polymerizable vinyl monomer copolymer and allyl (meth) acrylate / (meth) acrylic acid / optional Other addition-polymerizable vinyl monomer copolymers are preferred. These polymers can be used alone or as a mixture of two or more. The molecular weight of a high-molecular polymer can take a wide range of values depending on the type of the polymer, but in general,
5,000 to 1,000,000, preferably 10,000 to 500,000 are suitable. The amount of the polymer used is 10% by weight to 90% by weight, preferably 3% by weight, based on the entire photopolymerizable composition.
0 to 85% by weight.

In addition to the above, it is preferable to further add a thermal polymerization inhibitor to the photosensitive layer.
-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 and the like are useful, and in some cases, a dye or pigment for coloring the photosensitive layer and a pH as a printing agent.
An indicator, a fluorinated surfactant for improving coating properties, cellulose alkyl ether, and the like can also be added.

Further, malic acid, phosphorous acid, tartaric acid, citric acid, phosphoric acid, dipicolinic acid, polynuclear aromatic sulfonic acids and salts thereof, sulfosalicylic acid, etc. are added as necessary as stabilizers for the diazo resin. be able to. In addition, to prevent polymerization inhibition due to the effect of oxygen in the air,
A waxing agent can be added. What is used as a waxing agent is a material which is solid at room temperature but is dissolved in a coating solution and precipitates on the surface during a coating and drying process. Examples include higher fatty acids such as stearic acid and behenic acid, higher fatty acid amides such as stearic acid amide and behenic acid amide, and other higher alcohols.

In order to completely prevent the polymerization inhibition effect due to oxygen in the air, a protective layer made of a polymer having excellent oxygen barrier properties such as polyvinyl alcohol and acidic celluloses may be provided. The method of applying such a protective layer is described in detail, for example, in US Pat. No. 3,458,311 and Japanese Patent Publication No. 55-49729. The photocrosslinkable composition in the present invention has a photocrosslinkable polymer having a photodimerizable unsaturated bond and a sensitizer as essential components.

The photocrosslinkable polymer having an unsaturated bond capable of photodimerization used in the composition of the present invention includes a maleimide group, a cinnamyl group, a cinnamoyl group, a cinnamylidene group, a cinnamylideneacetyl group and a chalcone group. And other photosensitive groups having a functional group in the side chain or main chain. In particular, polymers having a maleimide group in the side chain and polyester resins having a cinnamic acid skeleton in the molecular chain have relatively high sensitivity.

Examples of such a polymer capable of photodimerization having a maleimide group in a side chain include JP-A-52-988 (corresponding to US Pat. No. 4,079,041) and German Patent 2,626,769.
And European Patent No. 21,019, European Patent 3,552 and Die Angewandte Makromoleku.
lare Chemie) 115 (1983), pp. 163-181, the following general formula (II):

[0022]

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Wherein R ³ and R ⁴ each independently represent an alkyl group having up to 4 carbon atoms, or R ³ and R ⁴ together form a 5- or 6-membered Or a polymer having a maleimide group in the side chain represented by the following formula:
No. 992, No. 49-128993, No. 50-5376, No. 50-5377
No. 50-5379, No. 50-5378, No. 50-5380, No. 53
-5298, 53-5299, 53-5300, 50-50107
No. 51-47940, No. 52-13907, No. 50-45076, No. 52
-121700, 50-10884, 50-45087, German Patent No.
Nos. 2,349,948 and 2,616,276 each having the following general formula (III):

[0024]

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(Wherein, R ⁵ represents an aromatic group, and R ⁶ represents a hydrogen atom, a halogen atom, an alkyl group or a cyano group). Can be done. The average molecular weight of these polymers is at least 1,000, preferably from 10,000 to 100,000. These polymers have an average of two or more maleimide groups per molecule in the side chain. Among these polymers having a maleimide group in the side chain, particularly a polymer having an acid group can use alkaline water at the time of development, which is advantageous from the viewpoint of preventing pollution. The acid value of the maleimide group-containing polymer having an acid group is 2
The range is preferably from 0 to 300, more preferably from 50 to 2
00 range. In particular, among polymers having these acid numbers, Die Angewandte Makromolekulare Chemie 1
N- [2- (methacryloyloxy) ethyl]-as described on pages 71-91 of No. 28 (1984).
A copolymer of 2,3-dimethylmaleimide and methacrylic acid or acrylic acid is useful. By synthesizing the vinyl monomer of the third component at the time of synthesizing the copolymer, a multi-component copolymer suitable for the purpose can be easily synthesized. For example, by using an alkyl methacrylate or an alkyl acrylate having a glass transition point of a homopolymer whose room temperature is equal to or lower than room temperature as a vinyl monomer of the third component, flexibility can be given to the copolymer.

In addition, as the photocrosslinkable polymer having an unsaturated bond capable of photodimerization used in the present invention, a polymer having at least two groups represented by the following general formula (IV) or (V) can be mentioned. Can be _{A- (CH = CH) n -CH} = C (X) -CO- (IV) B-CO-C (Y) = CH- (CH = CH) n -C 6 H 4 - (V) ( where A: aryl group, substituted aryl group, furyl group or thienyl group, B: alkoxy group, aryl group, substituted aryl group or alkyl group, X: H, CN, halogen atom, phenyl group or alkyl group, Y; H, CN , A halogen atom, a phenyl group or an alkyl group, n; an integer of 0 or 1).

Specific examples of the polymer having at least two groups represented by the general formula (IV) or (V) as side chains include acrylic acid containing the group represented by the general formula (IV) or (V). There are homopolymers of esters, methacrylic esters or vinyl ether compounds, copolymers of two or more of these, and copolymers copolymerized with other addition-polymerizable vinyl monomers as required. General formula (IV) or (V)
Examples of the acrylate, methacrylate or vinyl ether compound containing a group represented by the following formula are British Patent No. 949,919, JP-B-45-36755, JP-B-46-4603.
No., JP-A-47-34794, JP-B-49-14352, JP-B-49-2
No. 8122, JP-A-49-36794, JP-A-49-103975, JP-B-50-11283, JP-B-50-24621, JP-B-51-481, JP-B-55-44930, JP-B-56 -37244, Tokiko 56-52923
And Japanese Patent Publication No. 57-28488. Of these, preferred are polyacrylates, polymethacrylates, and polyvinyl ether compounds containing a cinnamate group in the side chain. The preferred molecular weight range of these photosensitive polymer compounds is from 2,000 to 1,000,000. More preferably, it is 10,000 to 200,000.

Other examples of the crosslinkable polymer having an unsaturated double bond capable of photodimerization in the main chain include phenylenediacrylic acid or a photosensitive polyester produced by condensation of an alkyl ester thereof with glycol. , Which have high photosensitivity. These polymers are
There have been many attempts to solubilize in an alkaline aqueous solution.For example, JP-A-60-191244 describes an alkali water developable photosensitive composition comprising a photosensitive polymer compound having a carboxyl group introduced into a side chain. ing. In addition, U.S. Pat.
No. 861,058 discloses a method of reacting a hydroxyl group of polyvinyl alcohol with cinnamic acid chloride and an acid anhydride to obtain a product which is provided with alkali water solubility simultaneously with photosensitivity.US Pat. No. 2,835,656 describes A method of reacting a copolymer of maleic anhydride and styrene with β-hydroxyethyl cinnamate, US Pat. No. 3,357,831
No. 3,702,765 discloses a method of introducing methacrylic acid into a cinnamic acid acrylic ester-based copolymer, and US Pat. Various methods such as a method of hydrolysis and a method of adding active mercaptocarboxylic acid to a part of unsaturated double bond are described in JP-A-63-218945.

The content of these photosensitive polymers is about 20 to 99% by weight, preferably 50 to 100% by weight, based on the total weight of the photosensitive layer.
~ 99% by weight is suitable. As the sensitizer used in the photocrosslinkable composition of the present invention, a triplet sensitizer having a maximum absorption that actually allows sufficient light absorption in a range of 300 nm or more is preferable. Such sensitizers include benzophenone derivatives, benzanthrone derivatives, quinones, anthraquinones, aromatic nitro compounds, naphthothiazoline derivatives, benzothiazoline derivatives, xanthones, naphthothiazole derivatives, ketocoumarin compounds, benzothiazole derivatives, naphthofuranone Compounds, benzoin compounds, acetophenone compounds, fluorenone compounds, pyrylium salts, thiapyrylium salts and the like can be mentioned. Specifically, Michler's ketone, N, N'-diethylaminobenzophenone, benzanthrone, (3-methyl-1,3-diaza-1,9-benz) anthronepiclamide, 5-nitroacenaphthene, 2-nitrofluorene, -Dibenzoylmethylene-3-methylnaphthothiazoline, 3,3-carbonyl-bis (7-diethylaminocoumarin), 2,4,6-triphenylthiapyrylium perchlorate, 2- (p-chlorobenzoyl) naphthothiazole, Benzoin, benzoin methyl ether, benzoin ethyl ether, 2,2-dimethoxy-
2-phenylacetophenone, 9-fluorenone, 2-
Chloro-9-fluorenone, 2-methyl-9-fluorenone, 9,10-anthraquinone, 2-ethyl-9,1
0-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, dibenzalacetone, p- (dimethylamino ) Phenylstyryl ketone, p- (dimethylamino) phenyl-p-methylstyryl ketone and the like.

Furthermore, thioxanthone derivatives such as 2-
Chlorthioxanthone, 2-isopropylthioxanthone, dimethylthioxanthone and the like, and German Patent No. 301889
Nos. 1 and 3117568, and EP 33720
It is preferred to use substituted thioxanthones as described in U.S. Pat. No. 2,075,506. Furthermore,
Merocyanine dyes, for example, 2- (heterocyclylcarbonylmethylene) benzo (or naphtho) thiazoline, 2- (diheterocyclecarbonylmethylene) benzo (or naphtho) thiazoline, 2-dibenzoylmethylenebenzo (or naphtho) thiazoline So, specifically,
Japanese Patent Publication No. 52-129791 discloses 2- [bis (2-
Furoyl) methylene] -3-methylbenzothiazoline,
2- [bis (2-thenoyl) methylene] -3-methylbenzothiazoline, 2- [bis (2-furoyl) methylene] -3-methylbenzothiazoline, 2- [bis (2-
Furyl) methylene] -3-methylnaphthothiazoline,
2- (2-furoyl) methylene-3-methylbenzothiazoline, 2-benzoylmethylene-3-methylbenzothiazoline, 2-bis (benzoylmethylene) benzothiazoline, 2-bis (benzoylmethylene) naphthothiazoline, and JP-B-45 -8832. Thiazole, benzothiazole, naphthothiazole and benzoselenazole sensitizing dyes having a thiobarbituric acid ring, sensitizers disclosed in Japanese Patent Application No. 1-190963, and the like are useful.

In addition, if necessary, a binder, a plasticizer, and the like can be contained. Specific examples of the binder include:
Chlorinated polyethylene, chlorinated polypropylene, alkyl polyacrylate, alkyl acrylate, acrylonitrile, copolymer with at least one kind of monomer such as vinyl chloride, styrene, butadiene, polyamide, methyl cellulose, polyvinyl formal, polyvinyl butyral Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer and the like.

Examples of the plasticizer include dialkyl phthalates such as dibutyl phthalate and dihexyl phthalate;
Oligoethylene glycol alkyl esters, phosphate plasticizers and the like can be used. In some cases, for the purpose of coloring the photosensitive layer, a dye or pigment, a pH indicator as a printing-out agent, a fluorinated surfactant for improving coating properties, a cellulose alkyl ether, or the like can be added.

Further, it is preferable to incorporate a thermal polymerization inhibitor and an antioxidant in the photosensitive layer, for example, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, t-butylcatechol. , Benzoquinone, 4,4'-thiobis (3-methyl-6-t-
Butylphenol), 2,2'-methylenebis (4-methyl-t-butylphenol), 2-mercaptobenzimidazole, and the like.

The diazo resin used in the present invention comprises:
The diazonium compound represented by the general formula (I) is contained as a constitutional unit, and the diazo monomer compound represented by the general formula (I) and, if necessary, an aromatic compound are converted by a known method, for example, Photo, Sci., Eng. Vol. 17, p. 33, (19
73), aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, benzaldehyde or ketone in sulfuric acid, phosphoric acid or hydrochloric acid according to the methods described in U.S. Pat. Nos. 2,063,631 and 2,679,498. Kind,
For example, it is obtained by polycondensation with acetone and acetophenone.

In the diazonium compound represented by the formula (I), R ¹ represents an alkoxy group, an alkylamino group or a hydrogen atom, and preferably represents an alkoxy group having 1 to 3 carbon atoms or an alkylamino group. R ² is a halogen atom, for example, each atom of chlorine, bromine, iodine or an alkyl or alkoxy group having 1 to 5 carbon atoms, a hydroxy group,
Represents a carboxyester group, a carboxyl group, or a hydrogen atom. However, R ¹ and R ² are not hydrogen atoms at the same time.

X ^- represents an anion, preferably pKa
Represents an anion of an inorganic acid or an organic acid of 4 or less, specifically, hydrohalic acid, for example, hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid (pentavalent phosphorus ),
In particular orthophosphoric acid, inorganic iso- and heteropolyacids such as phosphotungstic acid, phosphomolybdic acid, aliphatic or aromatic phosphonic acids or half esters thereof, arsonic acids,
Phosphinic acid, fluorocarboxylic acids such as trifluoroacetic acid, amidosulfonic acid, selenic acid, hydrofluoric acid, hexafluorophosphoric acid, perhydrochloric acid, and also aliphatic and aromatic sulfonic acids such as methanesulfonic acid, trifluoromethanesulfone Acids such as fluoroalkanesulfonic acid, laurylsulfonic acid, dioctylsulfosuccinic acid, dicyclohexylsulfosuccinic acid, camphorsulfonic acid, tolyloxy-3-propanesulfonic acid, nonylphenoxy-3-propanesulfonic acid, nonylphenoxy-4-butanesulfonic acid, Dibutylphenoxy-3-propanesulfonic acid, diamylphenoxy-3-propanesulfonic acid, dinonylphenoxy-3-propanesulfonic acid, dibutylphenoxy-4-butanesulfonic acid, dinonylphenoxy-4-bu Nsuruhon acid, benzenesulfonic acid, toluenesulfonic acid, mesitylene sulfonic acid, p-
Chlorobenzenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, p-acetylbenzenesulfonic acid,
-Nitro-o-toluenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-chloro-5-nitrobenzenesulfonic acid, butylbenzenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzene Sulfonic acid, butoxybenzenesulfonic acid, dodecyloxybenzenesulfonic acid, 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid, isopropylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, hexylnaphthalenesulfonic acid, octylnaphthalenesulfonic acid, Toshiquinaphthalenesulfonic acid, dodecyloxynaphthalenesulfonic acid, dibutylnaphthalenesulfonic acid, dioctylnaphthalenesulfonic acid, triisopropylnaphthalenesulfonic acid, Chill naphthalenesulfonic acid, 1-naphthol-5-sulfonic acid, naphthalene-1-sulfonic acid, naphthalene-2-sulfonic acid, 1,8-dinitro -
Naphthalene-3,6-disulfonic acid, 4,4'-diazido-stilbene-3,3'-disulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1,2-
Naphthoquinone-2-diazide-5-sulfonic acid and 1,
Includes the anion of 2-naphthoquinone-1-diazide-4-sulfonic acid or a mixture of these anions. Particularly preferred among these anions are those of hexafluorophosphoric acid, methanesulfonic acid, dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid.

Y represents -NH-, -O- or -S-;
It preferably represents -NH-. Specific examples of the diazo monomer compound include 3-methoxy-diphenylamine-4
-Diazonium salt, 3-dimethylamino-diphenylamine-4-diazonium salt, 2'-chloro-diphenylamine-4-diazonium salt, and 3-methoxy-2'-carboxy-diphenylamine-4-diazonium salt. Preferred is 3-methoxy-diphenylamine-4-diazonium salt.

The aromatic compound used as a cocondensate with the diazo monomer compound, if necessary, has an aromatic ring such as a phenyl group or a naphthyl group, and has a hydroxy group, a carbonyl group, an alkoxy group, a sulfonic acid group, halogen,
It may be substituted with an alkyl group or the like. Some of such co-condensed diazonium compounds are also described in JP-B-49-48001.

Specific examples of the diazo resin in the present invention include 2'-chloro-4-diazo-diphenylamine, methanesulfonate-formaldehyde resin, 3-methoxy-4-diazo-diphenylamine hexafluorophosphate- Formaldehyde resin, 3-methoxy-4-diazo-
Diphenylamine / dodecylbenzenesulfonate-formaldehyde resin, salicylic acid-3-methoxy-4-
Diazo-diphenylamine hexafluorophosphate-formaldehyde resin, P-hydroxybenzoic acid-3-methoxy-4-diazo-diphenylamine hexafluorophosphate-formaldehyde resin, gallic acid-3-methoxy-4
-Diazo-diphenylamine-formaldehyde resin,
2-benzenedicarboxylic acid-3-methoxy-4-diazo-diphenylamine.2-hydroxy-4-methoxybenzophenone-5-sulfonate-formaldehyde resin, P-phenoxybenzoic acid-3-methoxy-4-diazodiphenylamine.benzene Sulfonate-formaldehyde resin, 4-carboxydiphenylamine-3-
Methoxy-4-diazodiphenylamine dodecylbenzenesulfonate-formaldehyde resin, phenoxyacetic acid-3-methoxy-4-diazodiphenylamine dodecylbenzenesulfonate-formaldehyde resin,
Phenoxyacetic acid-3-methoxy-4-diazodiphenylamine / dibutylnaphthalenesulfonic acid-formaldehyde resin, 2,4-dimethoxybenzoic acid-3-ethylamino-4-diazodiphenylamine / methanesulfonic acid-formaldehyde resin, 4-anilino Benzoic acid
3-methylamino-4-diazodiphenylamine hexafluorophosphate-formaldehyde resin, phenoxyacetic acid-2'-chloro-4-diazodiphenylamine dodecylbenzenesulfonate-formaldehyde resin, and the like. Among them, particularly preferred are 3-methoxy-4-diazo-diphenylamine hexafluorophosphate-formaldehyde resin, salicylic acid-3-methoxy-4-diazo-diphenylamine hexafluorophosphate-formaldehyde resin, P-hydroxybenzoic acid Acid-3-methoxy-4-diazo-diphenylamine hexafluorophosphate-formaldehyde resin, P-phenoxybenzoic acid-
3-methoxy-4-diazodiphenylaminebenzenesulfonate-formaldehyde resin, phenoxyacetic acid-
3-methoxy-4-diazodiphenylamine / dodecylbenzenesulfonate-formaldehyde resin; phenoxyacetic acid-3-methoxy-4-diazodiphenylamine / dibutylnaphthalenesulfonate-formaldehyde resin.

The molecular weight of the diazo resin used in the present invention is 50
0-100,000 can be used, preferably about 800-
5,000 are appropriate. The content of the diazo resin in the photosensitive layer is 0.1 to 30% by weight, preferably 1 to 10% by weight. The diazo resin having these specific structures shortens or reduces the absorption wavelength due to the functional group substituted at the O-position of the diazo group, and rotates due to steric hindrance due to the substituent at the 2′-position. The absorption is sharpened and the sensitivity is reduced with respect to the white fluorescent line (436 nm). For this reason, it is considered that white light safety is improved.

On the other hand, the diazo resin having this structure is also partially described in JP-B-49-48001 and JP-A-1-102457. For example, the diazo resin disclosed in JP-A-1-102457 is A diazo resin having an alkoxy group at the 4'-position, which is intended to increase the sensitivity and is seen in Examples, has a contradictory deterioration in white light safety. The above-mentioned photosensitive layer is formed by mixing a photosensitive composition comprising the above components with, for example, 2-methoxyethanol, 2-methoxyethyl acetate, methyl cellosolve, propylene glycol monomethyl ether, 3-methoxypropanol, 3-methoxypropyl acetate, acetone , Methyl ethyl ketone, ethylene dichloride, methyl lactate, ethyl lactate, methanol, dimethylformamide, ethanol, methyl cellosolve acetate, etc., alone or in a suitable mixed solvent, and coated on a support. Formed by The coating amount is suitably in the range of about 0.1 g / m ² ~ about 10 g / m ² in weight after drying, preferably 0.5~5g
/ M ² .

In the present invention, an intermediate layer may be formed, if necessary, for the purpose of enhancing the adhesion between the support and the photosensitive layer, preventing the photosensitive layer from remaining after development, or preventing halation. It may be provided. In order to improve the adhesion, the intermediate layer is generally made of a diazo resin or a phosphoric acid compound adsorbed on aluminum, for example. Further, the intermediate layer composed of a substance having high solubility so that the photosensitive layer does not remain after development is generally composed of a polymer having good solubility or a water-soluble polymer. Generally contains dyes and UV absorbers. The thickness of the intermediate layer is arbitrary, and must be a thickness capable of performing a uniform bond-forming reaction with the upper photosensitive layer upon exposure. Usually, a dry solid has a good application rate of about 1 to 100 mg / m ² , with 5 to 40 mg / m ² being particularly good.

The use ratio of the diazo resin of the present invention in the intermediate layer is 30 to 100% by weight, preferably 60 to 10%.
0% by weight. In the intermediate layer, if necessary, a sensitizer,
Diazo stabilizer, polymer binder, antihalation agent,
In addition to the surfactant, various additives may be added. In order to provide an intermediate layer, the above compound may be dissolved in a desired solvent at a desired concentration, applied or dipped, and then dried.

The support having a hydrophilic surface used in the present invention is desirably a dimensionally stable plate. Such dimensionally stable plate-like materials include those conventionally used as supports for printed matter, and they can be suitably used in the present invention. Such supports include paper,
Paper laminated with plastics (eg, polyethylene, polypropylene, polystyrene, etc.), metal plates such as aluminum (including aluminum alloys), zinc, copper, etc., cellulose diacetate, cellulose triacetate,
Plastic films such as cellulose propionate, cellulose acetate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, and the like, paper or plastic film on which a metal as described above is laminated or vapor-deposited, etc. included. Among these supports, the aluminum plate is preferable because it is extremely stable in dimension, is inexpensive, and has particularly good adhesion to the photosensitive layer of the present invention. Further, a composite sheet in which an aluminum sheet is bonded on a polyethylene terephthalate film as described in JP-B-48-18327 is also preferable.

In the case of a metal, particularly an aluminum support, it is preferable that a surface treatment such as graining treatment or anodic oxidation treatment has been performed. In order to enhance the hydrophilicity of the surface, it is preferable to perform immersion treatment in an aqueous solution of sodium silicate, potassium fluorozirconate, phosphate or the like. As described in U.S. Pat. No. 2,714,066, an aluminum plate grained and then immersed in an aqueous solution of sodium silicate, and an anodized aluminum plate as described in JP-B-47-5125. After immersion, an immersion treatment in an aqueous solution of an alkali metal silicate is also preferably used.

Electrodeposition of silicate as described in US Pat. No. 3,658,662 is also effective. In addition, JP-B-46-27481, JP-A-52-58602, and electrolytic grains as disclosed in JP-A-52-30503, and a surface obtained by combining the above anodic oxidation treatment and sodium silicate treatment. Processing is also useful.

Further, it is also preferable to sequentially perform brush grain, electrolytic grain, anodizing treatment, and sodium silicate treatment as disclosed in JP-A-56-28893. After performing these treatments, a water-soluble resin,
For example, polyvinyl phosphonic acid, polymers and copolymers having a sulfonic acid group in the side chain, and those coated with polyacrylic acid or the like are also suitable.

These hydrophilic treatments are performed not only to make the surface of the support hydrophilic, but also to prevent harmful reactions with the photosensitive composition provided thereon, This is performed to improve the adhesion. The photosensitive lithographic printing plate of the present invention is image-exposed using a light source rich in ultraviolet rays such as a metal halide lamp, a high-pressure mercury lamp, and the like, and is treated with a developing solution to remove unexposed portions of the photosensitive layer. A lithographic printing plate is obtained by applying a gum solution.

As a developer for the photosensitive composition of the present invention, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium, dibasic sodium phosphate, tertiary phosphoric acid Aqueous solutions of inorganic alkaline agents such as ammonium, dibasic ammonium phosphate, sodium metasilicate, sodium bicarbonate, aqueous ammonia and aqueous solutions of organic amine compounds such as mono, di or triethanolamine are suitable. Is added in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight.

Further, an organic solvent such as a surfactant or alcohol can be added to the alkaline aqueous solution, if necessary. Preferred examples of the organic solvent include benzyl alcohol, 2-phenoxyethanol, 2-butoxyethanol, and n-propyl alcohol. Examples of the surfactant include anionic surfactants such as alkylnaphthalene sulfonate and sodium lauryl sulfate. In addition, diazo dissolving agents,
For example, it is also preferable to add a reducing substance such as a sulfite, methylresorcin, or a pyrazolone compound. Further, those described in the specifications of U.S. Pat. Nos. 3,475,171 and 3,615,480 can be mentioned. Further, the developing solutions described in JP-A-50-26601, JP-B-56-39464 and JP-B-56-42860 are also excellent as developing solutions for the photosensitive lithographic printing plate of the present invention.

As a method of developing a photosensitive lithographic printing plate image-exposed using the above-described developing solution, a developing solution is charged into a developing tank and the lithographic printing plate is immersed in the developing solution. A method of repeatedly using a developing solution such as a method of passing a developing solution through a developing tank or a method of spraying a developing solution in a developing tank, or one sheet of a developing solution as disclosed in JP-A-61-243455 and JP-A-62-2254. After applying an amount of developing solution necessary for developing the photosensitive lithographic printing plate to the plate surface and developing with only the applied developing solution, various methods such as a disposable developing method in which the developing solution is discarded and not reused are used. However, in the present invention, a method in which the developer is repeatedly used is preferable. In this case, it is preferable to add the developing replenisher continuously or in a blocking manner. The composition of the developer and replenisher of the developing method for performing such replenishment, and the replenishment method are described in JP-A-54-62004, JP-A-55-22759, and JP-A-55-115039.
No. 56-12645, No. 58-95349, No. 64-21451, JP-A-1-180548 and JP-A-2-3065 are described in detail, and development of the photosensitive lithographic printing plate of the present invention. Can be suitably used.

Examples of the desensitized gum include JP-B-56-30196.
No., JP-B-62-16834, JP-B-63-52600, JP-A-56-1
No. 33193, JP-A-62-995, JP-A-62-255190, JP-A-63-191693, JP-A-2-108595, and those described in JP-A-2-108594 are described. It is preferably used. After the development processing, if necessary, erasing, washing, and desensitizing steps may be performed, or post-exposure, burning processing, or the like may be performed for the purpose of increasing the strength of the image area.

[0053]

The photosensitive lithographic printing plate of the present invention has excellent adhesiveness between the support and the photosensitive layer while maintaining the excellent sensitivity and performance of the photosensitive layer, and furthermore, the work safety under a white fluorescent lamp. Sex is raised.

[0054]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. "%" Indicates% by weight unless otherwise specified. Reference Example 1 An aluminum plate having a thickness of 0.30 mm was coated with a nylon brush 400.
The surface was sand-grained using an aqueous suspension of mesh pumistone, and then thoroughly washed with water. After etching by immersing in a 10% aqueous sodium hydroxide solution at 70 ° C. for 60 seconds, the substrate was washed with running water, neutralized and washed with 20% NHO ₃ , and washed with water.
This was subjected to electrolytic surface roughening treatment in a 1% aqueous nitric acid solution at an anode electricity of 160 coulomb / dm ² using a sinusoidal alternating waveform current under the condition of V _A = 12.7 V. When the surface roughness was measured, it was 0.6 μ (Ra display). Subsequently, it is immersed in a 30% aqueous solution of H ₂ SO _{4 and} subjected to a desmutting treatment at 55 ° C. for 2 minutes. Then, in a 20% aqueous solution of H ₂ SO ₄ , the thickness is 2.7 g / m ² at a current density of 2 A / dm ² . For 2 minutes. The obtained aluminum support was
It was immersed in a 2.5% aqueous solution of sodium silicate at 0 ° C. for 1 minute, washed with water and dried.

Next, the following photopolymerizable photosensitive composition (1) was applied to a dry weight of 2.0 g / m ² using a spin coater, and dried at 80 ° C. for 2 minutes. A photosensitive layer was formed. Photosensitive composition (1) Poly (allyl methacrylate / methacrylic acid) copolymer 5.0 g Molar ratio 70/30 Pentaerythritol tetraacrylate 1.5 g The following photopolymerization initiator 0.3 g

[0056]

Embedded image

3-Methoxy-4-diazo-diphenylamine-hexafluoride 0.2 g Phosphate-formaldehyde resin p-methoxyphenol 0.01 g Oil Blue # 603 (manufactured by Orient Chemical Industries) 0.15 g Megafax F-177 (Dainippon) Ink Chemical Industry Co., Ltd., fluorine-based 0.05 g surfactant) ethylene glycol monomethyl ether 100 g methyl ethyl ketone 50 g methanol 50 g Finally, polyvinyl alcohol for the overcoat layer (saponification degree 86.5 to 89.0 mol%) , A polymerization degree of 1,000 or less) was applied to the surface of the photosensitive layer so as to have a dry weight of 1.5 g / m ² to produce a photosensitive lithographic printing plate [A]. Comparative Example 1 In place of the diazo resin of the photosensitive composition (1) of Reference Example 1 , 4
A photosensitive lithographic printing plate [B] was produced in the same manner as in Reference Example 1 , except that -diazo-diphenylamine-hexafluorophosphate-formaldehyde resin was used.

These photosensitive lithographic printing plates [A] and [B]
The white fluorescent lamp (Mitsubishi Neorumi Super FLR40SW)
(50 EDL-MNU) at a brightness distance of 400 Lux for 5 minutes each. After that, a gray scale tablet manufactured by Fuji Photo Film Co., Ltd. and a dot negative film are stacked, and a printer FT26V manufactured by Nuark, USA
5 with 2UPNS (light source; 2KW metal halide lamp)
The film was exposed to 0 count, immersed in the following developer at 25 ° C. for 1 minute, rubbed lightly with absorbent cotton, washed with water, and gummed. (Developer)-4.5 g of benzyl alcohol-4.5 g of a 38% aqueous solution of sodium salt of isopropylnaphthalenesulfonic acid-1.5 g of monoethanolamine-0.3 g of sodium sulfite-100 g of pure water The obtained printing plate was subjected to KOR- manufactured by Heidelberg. Printed on a D printing machine. The printing performance was as shown in Table 1.

Table 1 {Printing plate [A] Printing plate [B]}網 Thickness of halftone dot ^* No thickening Thickening Non-image portion dirt No dirt Light dirt printing durability 50,000 printing 100th ────────────────────────── * used in comparative example 1 reference example 1 of the plate that did not receive the fog under white light The following photopolymerizable photosensitive composition (2) was applied onto the prepared aluminum support in the same manner as in Reference Example 1 to a dry weight of 2.0 g / m ² and dried. [C] was produced. Photosensitive composition (2) poly (allyl methacrylate / benzyl methacrylate / 5.0 g) methacrylic acid (copolymerization molar ratio 60/20/20) trimethylolpropane triacrylate 2.0 g The following photopolymerization initiator 0.3 g

[0060]

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Behenamide 0.2 g Oil Blue # 603 (manufactured by Orient Chemical Co., Ltd.) 0.15 g Malic acid 0.05 g Dodecylbenzene sulfonate of formaldehyde cocondensation polymer of 3-methoxy-4-diazodiphenylamine and 0.15 g of phenoxyacetic acid Megafac F177 (manufactured by Dainippon Ink and Chemicals, Inc.) 0.05 g ethylene glycol monomethyl ether 100 g methyl ethyl ketone 50 g methanol 50 g Comparative Example In Example 1 , the diazo resin of the photosensitive composition (2) was
In the same manner as in Example 1 except that the formaldehyde cocondensate of 4'-methoxy-4-diazodiphenylamine and phenoxyacetic acid was replaced with dodecylbenzenesulfonate,
A photosensitive lithographic printing plate [D] was produced. Further, in Example 1 , the photosensitive lithographic printing plate [E] was coated in the same manner as in Example 1 except that the photopolymerizable composition containing no diazo resin was applied.
I got

These photosensitive lithographic printing plates [C] to [E]
Is treated under white light in the same manner as in Reference Example 1.
Exposure, development, and printing. Table 2 shows the results. Table 2 ─────────────────────────────────── [C] [D] [E] ────網 Thickness of halftone dots Thickness Without fatness Thickness Without fatness Non-image area dirt No dirt No dirt Printing durability 50000 printings 50000 printings Highlighted at 10000 printing ん だReference Example 2 The following photocrosslinkable photosensitive composition (3) was prepared. Photosensitive composition (3)・ Methyl methacrylate / N- [2- (methacryloyloxy) hexyl] -2,3-dimethylmaleimide / methacrylic acid = 10/60/30 (molar ratio) copolymer 5 g ・ The following structural formula 0.25g of sensitizer represented by

[0063]

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• Dibutylnaphthalenesulfonate of formaldehyde co-condensate of benzoic acid-3-methoxy-4-diazo-diphenylamine 0.15 g • Propylene glycol monomethyl ether 50 g • Methyl ethyl ketone 50 g • Megafac F-177 (large 0.03 g of a plasticizer of copper phthalocyanine pigment (CI Pigment Blue 15), 1.0 g of a 1.0% dispersion of the photosensitive composition as in Reference Example 1 . Using a spin coater on an aluminum support, the weight after drying was 1.
The composition was applied at ² g / m ² and dried at 80 ° C. for 2 minutes to obtain a photosensitive lithographic printing plate [F]. Comparative Example Instead of the diazo resin of the photosensitive composition (3), benzoic acid-4-
Diazo - Other using dibutyl naphthalene sulfonate formaldehyde co-condensation product of diphenylamine, reference
In the same manner as in Example 2 , a photosensitive lithographic printing plate [G] was obtained.

Further, a reference example was made except that dibutylnaphthalenesulfonic acid salt of formaldehyde cocondensate of benzoic acid-4'-methoxy-4-diazo-diphenylamine was used.
In the same manner as in Example 2 , a photosensitive lithographic printing plate [H] was obtained. These photosensitive lithographic printing plate [F], the [G] and [H] Reference
In the same manner as in Example 1 , the film was left standing under a white lamp and exposed, and then developed using the following developer, desensitized, and printed. Table 3 shows the results. (Developer) ・ 20 g of potassium silicate with SiO ₂ / K ₂ O molar ratio of about 1.1 ・ 1000 g of water ─────────── [F] [G] [H] ──────────────────────────────網 Thickness of halftone dots Thickness No thickness Thickness Thickness Non-image area dirt No dirt Light dirt Dirt generation Endurance 50,000 printing 50,000 printing 50,000 printing ─────── Reference Example 3 The following photocrosslinkable photosensitive composition (4) was prepared. Photosensitive composition (4) 5.0 g of a polymer having the following structure produced by condensation of p-phenylenediethoxy acrylate and 1,4-di-β-hydroxyethoxycyclohexane

[0066]

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· The following sensitizers
0.3 g

[0068]

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0.15 g of a PF ₆ salt of a formaldehyde condensate of 2'-chloro-4-diazodiphenylamine 0.1% of a plasticizer of a copper phthalocyanine pigment (CI Pigment Blue 15) 1.0 g of a 1.0% dispersion of diethyl phthalate 0.5 g of methyl ethyl ketone 20 g-propylene glycol monomethyl ether 30 g The photosensitive composition was dried on a similar aluminum support as in Reference Example 1 using a spin coater to give a weight after drying of 1.
The composition was applied so as to be 0 g / m ² and dried at 80 ° C. for 2 minutes to obtain a photosensitive lithographic printing plate [I].

Further, as a comparative example, a photosensitive lithographic printing plate [J] was obtained in the same manner except that the diazo resin was replaced with a formaldehyde condensate of 4'-methoxy-4-diazodiphenylamine. These photosensitive lithographic printing plates were left under a white fluorescent lamp, exposed, developed and printed in the same manner as in Reference Example 1 .
Table 4 shows the results.

[0071]

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-2868 (JP, A) JP-A-3-2867 (JP, A) JP-A-2-301761 (JP, A) JP-A-2-2 123361 (JP, A) JP-A-62-175730 (JP, A) JP-A-62-175729 (JP, A) JP-A-62-115150 (JP, A) JP-A-62-78544 (JP, A) JP-A-59-53836 (JP, A) JP-A-2-66 (JP, A) JP-A-1-254949 (JP, A) JP-A-1-102457 (JP, A) JP-A-59-196325 (JP, A) JP-A-53-33116 (JP, A) JP-A-3-250061 (JP, A)

Claims (2)

(57) [Claims] 1. Photopolymerization on a support having a hydrophilic surface
In a photosensitive lithographic printing plate provided with a photosensitive layer containing a hydrophilic composition, the photosensitive layer contains, as constituent units, an aromatic diazonium compound represented by the following general formula (I) and phenoxyacetic acid or benzoic acid. A photosensitive lithographic printing plate comprising a diazo resin. Embedded image In the formula, R ¹ represents an alkoxy group, an alkylamino group or a hydrogen atom, R ² represents a halogen atom, an alkyl group, hydroxy group, carboxy ester group, a carboxyl group, an alkoxy group or a hydrogen atom, X ^- is an anion Indicates that
Y represents -NH-, -O-, -S-. Where R ¹ and R ²
Are not simultaneously hydrogen atoms. 2. A photosensitive lithographic printing plate comprising an intermediate layer and a photosensitive layer containing a photopolymerizable composition provided on a support having a hydrophilic surface, wherein the intermediate layer comprises A photosensitive lithographic printing plate comprising a co-condensed diazo resin containing an aromatic diazonium compound represented by the formula (I) and phenoxyacetic acid or benzoic acid as constituent units.