JPH0996906A - Photosensitive composition, photosensitive planographic printing plate and image forming method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive compsn. and a photosensitive planographic printing plate hardly producing an insoluble material in a developer when the photosensitive material is developed with an alkaline developer substantially not containing org. solvent, capable of executing a large amt. of development with a specified amt. of the developer and having excellent storage property and printing durability and to provide the developing method therefor. SOLUTION: This photosensitive compsn. is a negative photosensitive compsn. containing a diazo compd., a polymerizable compd. having unsatd. bonds for addition polymn., a photopolymn. initiator, and a polymer compd. which can form a film, to which at least one kind of coupling agent selected from a silane coupling agent and a titanium coupling agent is added. The obtd. photosensitive compsn. is applied on a base body which is preliminarily subjected to hydrophilic treatment. Thus, a photosensitive planographic printing plate is obtd., and the obtd. planographic printing plate is developed with an alkali soln. of pH>=12 which substantially contains no org. solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition, a photosensitive plate printing plate and a developing method thereof, and more specifically, a photosensitive composition containing a compound having an addition polymerizable unsaturated bond, and a substantially organic compound. The present invention relates to a photosensitive lithographic printing plate that can be developed with a solvent-free alkaline aqueous solution and a developing method thereof.

[0002]

2. Description of the Related Art Conventionally, in an image forming method using a negative type photosensitive composition utilizing a photoreaction of a diazo compound,
During the development treatment after exposure, a method of eluting the unexposed portion of the photosensitive layer with an organic solvent or an alkaline aqueous solution containing the organic solvent to form an image was generally used. It is feared that the use will deteriorate the working environment of the plate making process due to the odor of the solvent and adversely affect the health of the worker. Therefore, some negative type lithographic printing plates that can be developed with an alkaline aqueous solution containing substantially no organic solvent have been proposed, and some of them have begun to be put into practical use.

However, since the developability of these is insufficient, a small number of plates can be processed with a fixed amount of the developing solution, or precipitates or insoluble matters are generated in the developing solution, resulting in a developing device. There is also a problem that it adheres to the plate surface of the planographic printing plate which has been subjected to development processing. Further, even if the developability is sufficient, there is a problem that the printing durability is insufficient when printed.

[0004]

It is an object of the present invention to produce an insoluble matter in a developing solution when it is developed with an alkali developing solution containing substantially no organic solvent, and to develop a large amount of a large amount with a fixed amount of the developing solution. It is an object of the present invention to provide a photosensitive composition which can be processed and is excellent in storage stability and printing durability, a photosensitive lithographic printing plate and a developing method thereof.

[0005]

The above-mentioned problems of the present invention are as follows. In a negative photosensitive composition containing a diazo compound, a polymerizable compound having an addition polymerizable unsaturated bond, a photopolymerization initiator, and a polymer compound capable of forming a film,
Of the silane coupling agent and titanium coupling agent,
A photosensitive composition comprising at least one coupling agent,

[0006] 2. The silane coupling agent is represented by the following general formulas (1) and (2), and the titanium coupling agent is represented by the following general formula (3).
The photosensitive composition described,

[0007]

Embedded image (In the formula, R ₁ , R ₂ , and R _{3 each} represent a hydroxyl group, a C1 to C5 alkyl group, or an alkoxy group, and R ₄ represents a C1 to C5 alkyl group, a C6 to C18 aryl group,
A vinyl group, an acryloyloxy group, a methacryloyloxy group, a glycidyl group, an amino group, a C1 to C5 aminoalkyl group or a thiol group, and R ₅ is C1 to C1.
C5 alkyl group, C6 to C18 aryl group, vinyl group, C1 to C5 aminoalkyl group,
-X- is -O-, -NH-, -COO-, -S-, -C.
It represents either O-NH-, and l represents 0 to 5. ) General formula _{(3) (R 6 O)} m -Ti (R 7) n ( wherein, _{R 6} O represents an alkoxy group, m represents a 1 to 4, _{R 7} is a fatty acid group, an alkoxy group, a phenol Group, phenoxy group, phosphite group, phosphate group,
n represents 1 to 5, and when n is 2 or more, R ₆ may be the same or different. )

[0008] 3. 3. The photosensitive composition according to 1 or 2 above, wherein the diazo compound is a co-condensation resin of diazodiphenylamine and an aromatic compound having at least one group selected from a carbonyl group and a sulfonyl group in the molecule. ,

4. The film-forming polymer compound is
The photosensitive composition according to any one of 1 to 3 above, which has a phenolic hydroxyl group in the molecule.

5. A film-forming polymer having a phenolic hydroxyl group in the molecule is represented by the following general formula (4)
5. The photosensitive composition as described in 4 above, which is a copolymer obtained by copolymerizing the addition-polymerizable monomer represented by

[0011]

Embedded image (In the formula, R ₇ represents a hydrogen atom or a methyl group, and R ₈ represents -C.
OO- and -CONH- are shown, and n is 0 or 1. )

6. On a support that has been subjected to hydrophilic treatment, 1 to
5. A photosensitive lithographic printing plate characterized by being coated with any one of the photosensitive compositions according to 5.

7. 7. The photosensitive lithographic printing method according to 6 above, wherein any one of sodium silicate treatment, carboxycellulose treatment, organic phosphonic acid treatment, organic sulfonic acid treatment, and amino acid treatment is used as a hydrophilic treatment method for the support. Edition,

8. The method for developing a photosensitive lithographic printing plate as described in 6 or 7 above, which comprises developing the photosensitive lithographic printing plate with an aqueous alkaline solution having a pH of 12 or more substantially containing no organic solvent.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The aluminum support used in the present invention includes a support made of pure aluminum and an aluminum alloy. Various aluminum alloys can be used, and for example, an alloy of a metal such as silicon, copper, manganese, magnesium, chromium, zinc, lead, bismuth, and nickel and aluminum is used.

The aluminum support is preferably subjected to a degreasing treatment prior to roughening to remove rolling oil on the aluminum surface. As the degreasing treatment, trichlene,
A degreasing treatment using a solvent such as a thinner, an emulsion degreasing treatment using an emulsion of kesilon and triethanol and the like are used. In the degreasing treatment, an aqueous solution of an alkali such as caustic soda can be used. When an aqueous solution of an alkali such as caustic soda is used for the degreasing treatment, dirt and oxide films that cannot be removed only by the above degreasing treatment can be removed.

The graining method performed to improve the adhesion to the photosensitive layer and improve the water retention is as follows.
There are a so-called mechanical surface roughening method in which the surface is mechanically roughened, and a so-called electrochemical surface roughening method in which the surface is electrochemically roughened. Examples of the mechanical surface roughening method include methods such as ball polishing, brush polishing, blast polishing, and buff polishing. As the electrochemical surface roughening method, for example, there is a method in which a support is electrolytically treated with an alternating current or a direct current in an electrolytic solution containing hydrochloric acid or nitric acid. Any one of these
By using one or two or more methods, the support can be grained.

Since smut is formed on the surface of the support obtained by the graining treatment as described above, it is generally necessary to appropriately perform washing with water or alkali etching to remove the smut. preferable. Examples of such treatment include an alkali etching method described in JP-B-48-28123 and JP-A-53-28123.
A processing method such as a sulfuric acid desmutting method described in US Pat.

The support usually has abrasion resistance, chemical resistance,
In order to improve water retention, an oxide film is formed by anodic oxidation. Generally, in this anodization, a method of electrolyzing at an electric current density of 1 to 10 A / dm ² using an aqueous solution containing sulfuric acid and / or phosphoric acid at a concentration of 10 to 50% is preferably used. Patent No. 1,41
There is a method of electrolyzing at high current density in sulfuric acid described in U.S. Pat. No. 2,768, and a method of electrolyzing using phosphoric acid described in U.S. Pat. No. 3,511,661.

After the anodizing treatment, the support is subjected to surface treatment such as treatment with alkali silicate, hot water or the like, or immersion in a water-soluble polymer compound such as polyvinylphosphonic acid or an aqueous solution of potassium fluorozirconate. Preferably.

Next, a photosensitive layer containing the photosensitive composition of the present invention (claims 1 to 5) described below is applied onto the surface-treated support to form the photosensitive lithographic printing plate of the present invention ( Claims 6 and 7) are obtained. The photosensitive substance used in the photosensitive layer is not particularly limited, and various substances usually used for photosensitive lithographic printing plates can be used. Hereinafter, this point will be described.

(Photosensitive layer) A photosensitive lithographic printing plate according to claims 6 and 7 is obtained by applying a photosensitive layer comprising the photosensitive composition according to any one of claims 1 to 5 on the surface-treated support. The photosensitive material used in this photosensitive layer is a photosensitive composition containing a known diazo compound, a polymerizable compound having an addition polymerizable unsaturated bond, a photopolymerization initiator, and a polymer compound capable of forming a film. Can be used.

(Diazo Compound) The diazo compound in this photosensitive composition is, for example, a diazo resin represented by a condensate of an aromatic diazonium salt and formaldehyde or acetaldehyde. Particularly preferably, a salt of a condensate of p-diazophenylamine and formaldehyde or acetaldehyde, such as hexafluoroborophosphate,
Diazo resin inorganic salt which is a reaction product of tetrafluoroborate, perchlorate or periodate and the condensate, and as described in US Pat. No. 3,300,309. Examples thereof include diazo resin organic salts, which are reaction products of the condensate and sulfonic acids. Furthermore, diazo resins are preferably used with binders. As the binder, various polymer compounds can be used, but preferably a monomer having an aromatic hydroxyl group as described in JP-A-54-98613,
For example, N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, o-, m-, or p-hydroxystyrene, o
Copolymers of-, m-, or p-hydroxyphenylmethacrylate with other monomers, U.S. Pat. No. 4,12.
No. 3,276, a polymer containing a hydroxyethyl acrylate unit or a hydroxyethyl methacrylate unit as a main repeating unit, a natural resin such as shellac, rosin, polyvinyl alcohol, US Pat. No. 3,751, 257 include linear polyurethane resins, phthalated resins of polyvinyl alcohol, epoxy resins condensed from bisphenol A and epichlorohydrin, and cellulose derivatives such as cellulose acetate and cellulose acetate phthalate as described in US Pat.

Further, the diazo compound is preferably the co-condensation resin of the above item 3, that is, a diazodiphenylamine and an aromatic compound having at least one group selected from a carbonyl group and a sulfonyl group in the molecule. There is. The co-condensation ratio is a molar ratio of diazodiphenylamine / aromatic compound = 30/70 to 95 /
5 and particularly preferably diazodiphenylamine and p
A co-condensation product with hydroxybenzoic acid and a molar ratio of 50 /
It is 50-80 / 20.

(Photocrosslinking-type photosensitive resin composition) The photosensitive component in the photocrosslinking-type photosensitive resin composition is composed of a photosensitive resin having an unsaturated double bond in the molecule. For example, US Pat. No. 030,208, No. 3,435,23
No. 7,322,320, etc., as a photosensitive group in the polymer main chain.

[0026]

Embedded image And a photosensitive resin having a photosensitive group in the side chain of the polymer, a photosensitive resin having a maleimide group in the side chain of the polymer as described in JP-A-62-294238, and the like. To be

(Compound having an addition polymerizable unsaturated bond)
A photopolymerizable composition containing an addition-polymerizable unsaturated compound, comprising a monomer having a double bond, or a monomer having a double bond and a polymer binder. A typical example is US Pat. No. 2,760,8.
No. 63 and No. 2,791,504.

As an example, a composition containing methyl methacrylate, a composition containing methyl methacrylate and polymethyl methacrylate, a composition containing methyl methacrylate, polymethyl methacrylate and polyethylene glycol methacrylate monomers, methyl methacrylate, an alkyd resin. A photopolymerizable composition such as a composition containing a polyethylene glycol dimethacrylate monomer is used.

(Photopolymerization Initiator) As the photopolymerization initiator,
Photopolymerization initiators commonly known in this technical field, for example, benzoin derivatives such as benzoin methyl ether, benzophenone derivatives such as benzophenone, thioxanthone derivatives, anthraquinone derivatives, acridone derivatives, and the like,
Can be raised.

(Polymer compound capable of forming a film) An alkali-soluble polymer is preferable, and a vinyl monomer copolymer is particularly preferable. The vinyl monomer copolymer preferably contains the following constituent monomers for the purpose of improving the solubility in an alkaline aqueous solution. That is, unsaturated carboxylic acids such as methacrylic acid, alcoholic OH-containing monomers such as 2-hydroxyethyl methacrylate, and phenolic OH-containing monomers such as p-hydroxyphenylmethacrylamide and p-hydroxystyrene.

(Alkali-Soluble Resin) As the alkali-soluble resin used in the photosensitive composition of the present invention, novolak resins, vinyl polymers having phenolic hydroxyl groups, and JP-A-55-57841 are described. Examples thereof include condensation resins of polyhydric phenol and aldehyde or ketone.

Examples of the novolac resin used in the present invention include phenol / formaldehyde resin, cresol / formaldehyde resin, JP-A-55-57841.
Phenol-cresol-formaldehyde copolymer resin as described in JP-A-55-127
No. 553, a copolymer resin of p-substituted phenol and phenol, or cresol and formaldehyde.

The novolak resin preferably has a number average molecular weight Mn of 3.00 × (polystyrene standard).
10 ^{2 to} 7.50 × 10 ³ , and a weight average molecular weight Mw of 1.
00 × 10 ^{3 to} 3.00 × 10 ⁴ , more preferably Mn
Is 5.00 × 10 ^{2 to} 4.00 × 10 ³ , and Mw is 3.0
It is 0 × 10 ^{3 to} 2.00 × 10 ⁴ . The novolak resins may be used alone or in combination of two or more. The proportion of the novolak resin in the photosensitive composition is preferably from 5 to 95% by weight. Further, the vinyl copolymer having a phenolic hydroxyl group preferably used in the present invention is a polymer having a unit having the phenolic hydroxyl group in the molecular structure, and is represented by the following general formula [I] to
Polymers containing at least one structural unit of [V] are preferred.

[0034]

[Chemical 6]

[In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or a carboxyl group, preferably a hydrogen atom. R ₃ represents a hydrogen atom, a halogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. R ₄ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, preferably a hydrogen atom. A represents an optionally substituted alkylene group connecting a nitrogen atom or an oxygen atom and an aromatic carbon atom, m represents an integer of 0 to 10, and B represents
Represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent. ]

The polymer used in the present invention preferably has a copolymer type structure, and is represented by the above general formula [I].
Examples of the monomer unit that can be used in combination with the structural unit represented by any one of formulas [V] to [V] include ethylenically unsaturated orylenes such as ethylene, propylene, isobutylene, butadiene, and isoprene; Styrenes such as methylstyrene, p-methylstyrene and p-chlorostyrene; for example, acrylic acids such as acrylic acid and methacrylic acid; for example, unsaturated aliphatic dicarboxylic acids such as itacone, maleic acid, and maleic anhydride;
For example, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, Α such as ethyl methacrylate
-Esters of methylene aliphatic monocarboxylic acid, for example, nitriles such as acrylonitrile and methacrylonitrile, for example, amides such as acrylamide, for example, acrylanilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide and the like Anilides such as vinyl acetate, vinyl propionate,
Vinyl esters such as vinyl benzoate and vinyl acetate;
For example, methyl vinyl ether, ethyl vinyl ether,
Vinyl ethers such as isobutyl vinyl ether and β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, for example, 1-methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1 Ethylene derivatives such as -dimethoxycarbonylethylene and 1-methyl-1-nitroethylene, for example, N-vinylpyrrole, N
-N-vinyl monomers such as vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidene and N-vinyl pyrrolidone. These vinyl monomers exist in a polymer compound in a structure in which an unsaturated double bond is cleaved.

Of the above-mentioned monomers, aliphatic monocarboxylic acid esters and nitriles are preferable because they exhibit excellent performance for the purpose of the present invention. These monomers may be bonded to the polymer used in the present invention in either a block or random state.

The proportion of the vinyl polymer used in the present invention in the photosensitive composition is preferably 5 to 95% by weight. As the vinyl polymer, the above polymers may be used alone or in combination of two or more. It can also be used in combination with other polymer compounds.

(Silane Coupling Agent) The silane coupling agent is preferably a silane coupling agent represented by the above general formula (1) or (2), and R ₁ ,
It is preferable that R ₂ and R ₃ are a C1 or C2 alkyl group or an alkoxy group, and that R ₄ has a radical or cationic polymerizable group such as a vinyl group, an acryl group, a methacryl group, or a glycidyl group.

Examples of preferred compounds include methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-aminopropyltriethoxysilane,
Examples thereof include N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane and γ-mercaptopropyltrimethoxysilane, preferably vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ.
-Methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane.

(Titanium Coupling Agent) The titanium coupling agent is preferably a titanium coupling agent represented by the above general formula (3), R ₆ O is an alkoxy group, m is 1 to 4, and R ₇ is R _7. Is a fatty acid group, an alkoxy group,
It is a phenol group, a phenoxy group, a phosphite group, or a phosphate group, n is 1 to 5, and when n is 2 or more, R ₆ may be the same or different. Specific examples of the compound are shown below.

[0042]

[Chemical 7]

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

(Organic Acid / Inorganic Acid / Anhydride) The photosensitive composition of the present invention may contain an organic acid / inorganic acid / anhydride. Examples of the acid used in the present invention include organic acids described in JP-A No. 60-88942 and Japanese Patent Application No. 63-293107, and "Chemical Handbook New Edition" edited by The Chemical Society of Japan, No. 92-158. The inorganic acids described on the page can be mentioned.
Examples of organic acids include p-toluenesulfonic acid, dodecylbenzenesulfonic acid, mesitylenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzensulfonic acid,
Sulfonic acids such as m-benzenedisulfonic acid, sulfinic acids such as p-toluenesulfinic acid, benzylsulfinic acid and methanesulfinic acid, phosphonic acids such as phenylphosphonic acid, methylphosphonic acid and chloromethylphosphonic acid,
Aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pentanoic acid, hexanoic acid and heptanoic acid, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, benzoic acid, o-, m-, p -Hydroxybenzoic acid,
o-, m-, p-methoxybenzoic acid, o-, m-, p-
Aromatic monocarboxylic acids such as methylbenzoic acid, 3,5-dihydroxybenzoic acid, phloroglysin carboxylic acid, gallic acid, and 3,5-dimethylbenzoic acid. Also,
Saturated or unsaturated aliphatic dicarboxylic acids such as malonic acid, methylmalonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, itaconic acid, malic acid, and tetrahydro Phthalic acid, 1,1-cyclobutanedicarboxylic acid,
1,1-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3
Examples thereof include alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid.

Among the above organic acids, more preferable one is p
-Toluenesulfonic acid, dodecylbenzenesulfonic acid,
Examples thereof include sulfonic acids such as mesitylenesulfonic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, and m-benzenedisulfonic acid, and cis-1,2-cyclohexanedicarboxylic acid and syringic acid. Examples of the inorganic acid include nitric acid, sulfuric acid, hydrochloric acid, silicic acid, phosphoric acid and the like, more preferably sulfuric acid and phosphoric acid.

When an acid anhydride is used, the type of the acid anhydride is also arbitrary, and those derived from aliphatic / aromatic monocarboxylic acids such as acetic anhydride, propionic anhydride and benzoic anhydride, and succinic anhydride , Maleic anhydride, glutaric anhydride, phthalic anhydride, etc., and those derived from aliphatic / aromatic dicarboxylic acids. Preferred acid anhydrides are glutaric anhydride and phthalic anhydride. These compounds can be used alone or in combination of two or more. The content of these acids is generally from 0.05 to 5% by weight, preferably from 0.1 to 3% by weight, based on the total solids of the entire photosensitive composition.

(Surfactant) The photosensitive composition of the present invention may contain a surfactant. As the surfactant, an amphoteric surfactant, an anionic surfactant, a cationic surfactant,
Nonionic surfactants, fluorinated surfactants and the like can be mentioned.

Examples of the amphoteric surfactant include lauryl dimethylamine oxide, lauryl carboxymethyl hydroxyethyl, imidazolinium betaine and the like.
Examples of anionic surfactants include fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfosuccinates,
Examples thereof include alkyl diphenyl ether disulfonate, alkyl phosphate, polyoxyethylene alkyl sulfate, polyoxyethylene alkyl allyl sulfate, naphthalene sulfonic acid formalin condensate, and polyoxyethylene alkyl phosphate. Examples of the cationic surfactant include an alkylamine salt, a quaternary ammonium salt, and an alkyl betaine. As the nonionic surfactant, polyoxyethylene alkyl ether,
Polyoxyethylene alkyl allyl ether, polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxy Examples include ethylene alkylamines and alkyl alkanolamides.

Examples of the fluorine-based surfactant include a copolymer of acrylate or methacrylate containing a fluoroaliphatic group and (polyoxyalkylene) acrylate or (polyoxyalkylene) methacrylate. These compounds can be used alone or in combination of two or more. Particularly preferred is FC-430.
(Sumitomo 3M Co., Ltd.) Fluorinated polyethylene glycol # -2000 (Kanto Chemical Co., Ltd.). The proportion occupying in the photosensitive composition is preferably 0.01 to 10% by weight, more preferably 0.01 to 5% by weight.

(Printout Material) A printout material for forming a visible image upon exposure can be added to the photosensitive composition. The printout material is composed of an organic dye that changes its color tone by interacting with a compound that generates an acid or a free radical upon exposure. O described in JP-A-36209
-Naphthoquinonediazide-4-sulfonic acid halogenide,
An ester compound or amide compound of o-naphthoquinonediazide-4-sulfonic acid chloride and an electron-withdrawing substituent phenol or aniline acid described in JP-A-53-36223, JP-A-55-
Examples include halomethylvinyloxadiazole compounds and diazonium salts described in 77742, JP-A-57-148784, and the like.

(Compound which produces an acid or a free radical upon exposure to light) As a compound which can be used in the photosensitive composition of the present invention to produce an acid or a free radical upon exposure, for example, a halomethyloxadiazole compound, A halomethyl-s-triazine compound or the like is used. A halomethyloxadiazole compound is a compound having a halomethyl group, preferably a trichloromethyl group, in oxadiazoles.

These compounds are known, for example, Japanese Patent Publication Nos. 57-6096 and 61-51788,
JP-B-1-28369, JP-A-60-13853
No. 9, JP 60-177340, and JP 60-24.
No. 1049, for example. In addition, the halomethyl-s-triazine compound is a compound having one or more halomethyl groups, preferably a trichloromethyl group, in the s-triazine ring.

In the photosensitive composition of the present invention, the addition amount of the compound which forms an acid or a free radical upon exposure to light is 0.
It is preferably from 0.1 to 30% by weight, more preferably from 0.1 to 30% by weight.
To 10% by weight, particularly preferably 0.2 to 3% by weight. These compounds can be used alone or in combination of two or more.

(Dye) A dye may be further used in the photosensitive composition of the present invention. The dye is used for the purpose of obtaining a visible image by exposure (exposed visible image) and a visible image after development.

As the dye, those which change color tone by reacting with free radicals or acids can be preferably used.
Here, "the color tone changes" includes both a change from colorless to a color tone, and a change from a colored to a colorless or different color tone. Preferred dyes are those which form a salt with an acid to change the color tone. For example, Victoria Pure Blue BOH (made by Hodogaya Chemical Co., Ltd.), Oil Blue #
603 (manufactured by Orient Chemical Industries), patent pure blue (manufactured by Sumitomo Mikuni Chemicals), crystal violet,
Brilliant Green, Ethyl Violet, Methyl Violet, Methyl Green, Erythrosin B, Paysic Fuchsin, Malachite Green, Oil Red, m
-Cresol purple, rhodamine B, auramine,
Triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthene-based, iminonaphthoquinone-based, azomethine-based or anthraquinone-based dyes represented by 4-p-diethylaminophenyliminaphthoquinone, cyano-p-diethylaminophenylacetanilide, etc. are colored to colorless Alternatively, it is mentioned as an example of a color changing agent that changes to a different color tone.

On the other hand, examples of the discoloring agent that changes from colorless to colored include leuco dyes and, for example, triphenylamine, diphenylamine, o-chloroaniline, 1,2,3-triphenylguanidine, naphthylamine, diaminodiphenylmethane, p, p. ′ -Bis-dimethylaminodiphenylamine, 1,2-dianilinoethylene, p, p ′,
p ″ -tris-dimethylaminotriphenylmethane,
p, p'-bis-dimethylaminodiphenylmethylimine, p, p ', p "-triamino-o-methyltriphenylmethane, p, p'-bis-dimethylaminodiphenyl-4-anilinonaphthylmethane, p, Examples thereof include primary or secondary arylamine dyes represented by p ′, p ″ -triaminotriphenylmethane. The proportion of the above-mentioned color changing agent in the photosensitive composition is preferably from 0.01 to 10% by weight, more preferably from 0.02 to 10% by weight.
Used at 5% by weight. These compounds can be used alone or in combination of two or more. Particularly preferred pigments are Victoria Pure Blue BOH and Oil Blue # 6.
It is 03.

(Oil Sensitizer) An oil sensitizer for improving the oil sensitivity of the image area (for example, a half-esterified product of an alcohol of a styrene-maleic anhydride copolymer described in JP-A-55-527). , Pt-butylphenol-
Novolak resins such as formaldehyde resins, or partially esterified products thereof with o-quinonediazide compounds, fluorine surfactants, p-hydroxystyrene
0% fatty acid ester) is preferably used. The amount of these additives varies depending on the object and purpose of use, but is generally 0.01 to 30% by weight based on the total solid content. Dissolve each of these components in the following solvent,
By coating on the surface of the support and drying, a photosensitive layer can be provided to produce the photosensitive lithographic printing plate of the invention. There is no special limitation on the usage of the solvent.

(Solvent) Solvents that can be used when dissolving the photosensitive composition used for the support produced by the present invention include methanol, ethanol, n-propanol, i-propanol, n-butanol, and n. -Aliphatic alcohols such as pentanol and hexanol, allyl alcohol, benzyl alcohol, anisole, phenetole, hydrocarbons such as n-hexane, cyclohexane, heptane, octane, nonane and decane, diacetone alcohol, 3-methoxy-1 -Butanol, 4-methoxy-1-butanol, 3-ethoxy-1-butanol, 3
-Methoxy-3-methyl-1-butanol, 3-methoxy-3-ethyl-1-pentanol-4-ethoxy-
1-pentanol, 5-methoxy-1-hexanol,
Acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, methyl hexyl ketone, ethyl butyl ketone, dibutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, γ-butyrolactone, 3-hydroxy-2-butanone , 4-hydroxy-
2-butanone, 4-hydroxy-2-pentanone, 5-
Hydroxy-2-pentanone, 4-hydroxy-3-pentanone, 6-hydroxy-2-hexanone, 3-methyl-3-hydroxy-2-pentanone, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, Ethylene glycol monoacetate, ethylene glycol diacetate, propylene glycol monoacetate, propylene glycol diacetate, ethylene glycol alkyl ethers and their acetates (methyl cellosolve, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol diethyl ether Glycol dibutyl ether, methyl cellosolve acetate, ethyl celloso Acetate), diethylene glycol monoalkyl ethers and their acetates (diethylene glycol monomethyl ether, monoethyl ether, mono i-propyl ether, monobutyl ether, diethylene glycol monomethyl ether acetate, etc.), diethylene glycol dialkyl ethers (DMDG, DEDG, DBDG, MEDG) , Triethylene glycol alkyl ethers (monomethyl ether, monoethyl ether, dimethyl ether, diethyl ether, methyl ethyl ether, etc.), propylene glycol alkyl ethers and their acetates (monomethyl ether, monoethyl ether, n-propyl ether, monobutyl ether, Dimethyl ether, diethyl ether, monomethyl ether Seteto, monoethyl ether acetate), dipropylene glycol alkyl ethers (mono methyl ether,
Monoethyl ether, n-propyl ether, monobutyl ether, dimethyl ether, diethyl ether),
Ethyl formate, propyl formate, butyl formate, amyl formate,
Methyl acetate, ethyl acetate, propyl acetate, butyl acetate,
Examples include carboxylic acid esters such as methyl propionate, ethyl propionate, methyl butyrate, and ethyl butyrate, dimethylformamide, dimethyl sulfoxide, dioxane, tetrahydrofuran, methyl lactate, ethyl lactate, methyl benzoate, ethyl benzoate, and propylene carbonate. . These solvents can be used alone or in combination of two or more.

(Coating Layer) In the photosensitive lithographic printing plate according to the present invention, a coating layer made of a water-insoluble organic solvent-soluble polymer compound capable of forming a film can be formed on the photosensitive layer. It is preferable to provide a mat layer on the surface of the photosensitive layer provided as described above in order to shorten the time for evacuation and prevent blurring during contact exposure using a vacuum printing frame. Specifically, JP-A-50-1258
No. 05, Japanese Patent Publication No. 57-6582, No. 61-28986
And a method of thermally fusing a solid powder as described in Japanese Patent Publication No. 62-33737. Further, on the surface of the photosensitive layer, for the purpose of preventing oxygen inhibition of photopolymerization, an overcoat layer made of a polymer having excellent oxygen barrier properties such as polyvinyl alcohol and acidic celluloses can be provided.

(Mat agent) The purpose of the matte layer is to improve the vacuum adhesion between the image film and the photosensitive lithographic printing plate during contact exposure, thereby shortening the vacuuming time, and further, the fine mesh during exposure due to poor adhesion. It is to prevent the dots from collapsing. As a method for applying the mat layer, Japanese Patent Application Laid-Open
No. 12974, a method of heat-sealing powdered solid powder, a method of spraying and drying polymer-containing water described in JP-A-58-182636, and the like. It is desirable that the mat layer itself be dissolved in the alkali developer or removed by this.

(Coating) The coating method used for coating the surface of the support with the photosensitive composition or the coating layer or the mat layer is a conventionally known method, for example, spin coating, wire bar coating, dip coating, air knife. Coating, roll coating,
Blade coating and curtain coating are used.

(Exposure) In using the photosensitive lithographic printing plate thus obtained, a conventionally used method can be applied. For example, a transparent original image having a line image, a halftone image or the like can be applied to the photosensitive surface. A relief image is obtained by exposing the film in close contact with it and then removing the photosensitive layer in the non-image area with a suitable developing solution. Light sources suitable for exposure include mercury lamps, metal halide lamps, xenon lamps,
Chemical lamps, carbon arc lamps and the like are used.

(Processing) In the present invention (claim 8), each of the developing solution and the developing replenishing solution used for the developing process of the photosensitive lithographic printing plate has a pH of 12 or more containing an alkali metal silicate. The alkali metal of the alkali metal silicate includes lithium, sodium, and potassium, and potassium is the most preferable. At the time of development, it is preferable that a development replenisher is appropriately replenished in accordance with the development processing amount of the photosensitive lithographic printing plate.

A preferred developing solution and developing replenishing solution are [SiO 2
₂ ] / [M] (in the formula, [SiO ₂ ] represents the molar concentration of SiO ₂ and [M] represents the molar concentration of alkali metal), and the SiO ₂ concentration is It is an aqueous solution of an alkali metal silicate that is 0.5 to 5.0% by weight based on the total weight.

The above developing solution and developing replenishing solution may contain water-soluble or alkali-soluble organic and inorganic reducing agents. Examples of the organic reducing agent include phenol compounds such as hydroquinone, methol and methoxyquinone, and amine compounds such as phenylenediamine and phenylhydrazine.Examples of the inorganic reducing agent include sodium sulfite and potassium sulfite. Sulfites such as ammonium sulfite, sodium bisulfite, potassium bisulfite, sodium phosphite, potassium phosphite, sodium hydrogen phosphite, potassium hydrogen phosphite, sodium dihydrogen phosphite, potassium dihydrogen phosphite Phosphites, hydrazine, sodium thiosulfate, etc.
And sodium dithionite. These water-soluble or alkali-soluble reducing agents can be contained in the developing solution and the developing replenisher at 0.05 to 10% by weight. Further, the developing solution and the developing replenishing solution may contain an organic carboxylic acid. These organic carboxylic acids include
It includes an aliphatic carboxylic acid having 6 to 20 carbon atoms and an aromatic carboxylic acid having a benzene ring or a naphthalene ring substituted with a carboxyl group.

The aliphatic carboxylic acid has 6 to 2 carbon atoms.
The alkanoic acid of 0 is preferable, and specific examples thereof include caproic acid, enantiic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, mystyric acid, palmitic acid,
Stearic acid and the like are particularly preferable.
~ 12 alkanoic acids. Further, the aliphatic carboxylic acid may be a fatty acid having a double bond in a carbon chain or a fatty acid having a branched carbon chain. The aliphatic carboxylic acid may be used as a sodium or potassium salt or an ammonium salt.

Specific examples of the aromatic carboxylic acid include benzoic acid, o-chlorobenzoic acid, p-chlorobenzoic acid, o-hydroxybenzoic acid, p-hydroxybenzoic acid, p-tert-butylbenzoic acid, o-aminobenzoic acid, p-aminobenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 3,5
-Dihydroxybenzoic acid, gallic acid, 1-hydroxy-
2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 2
-Hydroxy-1-naphthoic acid, 1-naphthoic acid, 2-
Naphthoic acid and the like.

The aromatic carboxylic acid may be used as a sodium or potassium salt or an ammonium salt. The content of the aliphatic carboxylic acid or aromatic carboxylic acid can be at least 0.1 to 30% by weight. The developer and development replenisher may contain various anionic, nonionic and cationic surfactants and organic solvents. Furthermore, the developer and development replenisher should be
Known additives can be added.

[0071]

EXAMPLES The present invention will be described more specifically with reference to the following examples. Example 1 Preparation of Support A The surface of an aluminum plate (material 1050, temper H16) having a thickness of 0.3 mm was degreased with a 3% sodium hydroxide aqueous solution, and this was degreased in a 2% hydrochloric acid bath at 25 ° C. and 50 A /. Electrolytic etching was performed at a current density of dm ² . After washing with water, an anodized film of 3 g / m ² was formed in a 30% sulfuric acid bath. Next, a support A was obtained by hydrophilic treatment with a 2% aqueous sodium metasilicate solution at 85 ° C. for 10 seconds.

On the obtained support A, a photosensitive composition coating liquid 1 having the following composition was applied using a wire bar and dried at 80 ° C. for 2 minutes to obtain a photosensitive lithographic printing plate sample. At this time, the coating amount of the photosensitive composition coating liquid was set to be 1.6 g / m ² as a dry weight. Further, the obtained photosensitive lithographic printing plate sample was subjected to development processing using a developer having the following composition, and evaluated for developability, storability, printing durability and fatigue developer deposit amount by the following evaluation methods. Table 1 shows the evaluation results.
Shown in

Photosensitive Composition Coating Liquid 1 Acrylic polymer compound A {HyPMA / MAA / AN / EA (15/10/20/55: molar ratio) Mw. 80,000} 7.0 g trimethylolpropane triacrylate 3.0 g 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.2 g p-dimethylaminobenzoic acid ethyl ester 0 .2 g diazo compound {diazodiphenylamine PF ₆ salt / p-hydroxybenzoic acid (60/40: molar ratio) Mw. 2,000} 0.2 g vinyltriethoxysilane 0.2 g octylphenol novolac {p-octylphenol / phenol (80/20: molar ratio) Mw. 5,000} 0.1 g Polyacrylic acid (Jurimer AC10L manufactured by Nippon Pure Chemical Co., Ltd.) 0.1 g Fluorine-based surfactant (FC430 manufactured by Sumitomo 3M) 0.03 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 2 g 2-methoxyethanol 200 ml HyPMA: p-hydroxyphenyl methacrylamide MAA: methacrylic acid AN: acrylonitrile EA: ethyl acrylate

Developer A Potassium silicate (1160 g), caustic potash (133 g),
Water (5133 ml): (pH = 12.7)

Evaluation Method Developability Evaluation The prepared lithographic printing plate was image-exposed through a film original (2 kW metal halide lamp, 8 mW / cm ² for 30 minutes).
Second exposure), and after the development treatment at the dilution ratios of the developing solution of × 1, × 2, and × 4, printing was performed, and stains on non-image areas were visually evaluated. Judgment criteria ○: No stain ○ △: Slightly observed to the extent that there is no problem in practical use △: Slight stain X: Stain

Evaluation of storability The prepared lithographic printing plate was allowed to stand for 3 days at a temperature of 50 ° C. and a humidity of 50%, and then imagewise exposed through a film original (2
After exposure with a kW metal halide lamp at 8 mW / cm ² for 30 seconds), the development solution was developed at dilution ratios of × 1, × 2, and × 4, printing was performed, and stains on non-image areas were visually evaluated.
The criterion was the same as the criterion for the above-mentioned developability evaluation.

Evaluation of Printing Durability The lithographic printing plate thus prepared was imagewise exposed through a film original (2 kW metal halide lamp, 30 mW at 8 mW / cm ²⁾ .
Second exposure), and after development processing with the above-mentioned developing solution, printing was carried out, and the number of prints until defects appeared in the printed image was evaluated.

Evaluation of Fatigue Developer Precipitate Amount An unexposed photosensitive lithographic printing plate of 5 m ² was treated with 1 liter of the above developer, and the precipitate produced in the developer was collected by filtration and dried to measure the amount of the precipitate.

Example 2 The same as Example 1 except that the photosensitive composition coating liquid 1 of Example 1 was replaced with the photosensitive composition coating liquid 2 of the following composition, and the support A was replaced with the support B described below. Thus, a photosensitive lithographic printing plate sample was obtained, and the obtained photosensitive lithographic printing plate sample was evaluated for developability, storability, printing durability, and fatigue developer deposit amount in the same manner as in Example 1. Table 1 shows the evaluation results.

Photosensitive composition coating liquid 2 Acrylic polymer compound B {HyPMA / MAA / AN / EA / EMA (25/3/20/27/25: molar ratio) Mw. 35,000} 7.0 g trimethylolpropane triacrylate 3.0 g 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.2 g p-dimethylaminobenzoic acid ethyl ester 0 .2 g diazo compound {diazodiphenylamine PF ₆ salt / p-hydroxybenzoic acid (60/40: molar ratio) Mw. 2,000} 0.5 g γ-methacryloxypropyltrimethoxysilane 0.2 g octylphenol novolac {p-octylphenol / phenol (80/20: molar ratio) Mw. 5,000} 0.1 g Polyacrylic acid (Jurimer AC10L manufactured by Nippon Pure Chemical Co., Ltd.) 0.1 g Fluorine-based surfactant (FC430 manufactured by Sumitomo 3M) 0.04 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 2 g 2-methoxyethanol 200 ml EMA: ethyl methacrylate

Preparation of Support B The surface of an aluminum plate (material 1050, temper H16) having a thickness of 0.3 mm was degreased with a 3% sodium hydroxide aqueous solution, and this was degreased in a 2% nitric acid bath at 25 ° C. and 50 A /. Electrolytic etching was performed at a current density of dm ² . After washing with water, an anodized film of 3 g / m ² was formed in a 30% sulfuric acid bath. Next, 75pp
A support B was obtained by hydrophilizing at 85 ° C. for 10 seconds with an aqueous m-carboxymethyl cellulose solution.

Example 3 Same as Example 1 except that the photosensitive composition coating liquid 1 of Example 1 was replaced with the photosensitive composition coating liquid 3 of the following composition, and the support A was replaced with the support C described below. Thus, a photosensitive lithographic printing plate sample was obtained, and the obtained photosensitive lithographic printing plate sample was evaluated for developability, storability, printing durability, and fatigue developer deposit amount in the same manner as in Example 1. Table 1 shows the evaluation results.

Photosensitive composition coating liquid 3 Acrylic polymer compound B {HyPMA / MAA / AN / MMA (30/5/20/45: molar ratio) Mw. 35,000} 7.0 g trimethylolpropane triacrylate 3.0 g 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.2 g p-dimethylaminobenzoic acid ethyl ester 0 .2 g diazo compound {diazodiphenylamine PF ₆ salt / p-hydroxybenzoic acid (60/40: molar ratio) Mw. 2,000} 0.5 g vinyltriethoxysilane 0.2 g octylphenol novolac {p-octylphenol / phenol (80/20: molar ratio) Mw. 5,000} 0.1 g Polyacrylic acid (Jurimer AC10L manufactured by Nippon Pure Chemical Co., Ltd.) 0.1 g Fluorine-based surfactant (FC430 manufactured by Sumitomo 3M) 0.04 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 2 g 2-methoxyethanol 200 ml MMA: methyl methacrylate

Preparation of Support C The surface of a 0.3 mm thick aluminum plate (material 1050, temper H16) was degreased with a 3% aqueous sodium hydroxide solution, and this was degreased in a 2% nitric acid bath at 25 ° C. and 50 A /. Electrolytic etching was performed at a current density of dm ² . After washing with water, an anodized film of 3 g / m ² was formed in a 30% sulfuric acid bath. Next, 50pp
Hydrophilic treatment was carried out at 85 ° C. for 10 seconds to obtain a support C.

Example 4 The same as Example 1 except that the photosensitive composition coating liquid 1 of Example 1 was replaced with the photosensitive composition coating liquid 4 of the following composition and the support A was replaced with the support D described below. Thus, a photosensitive lithographic printing plate sample was obtained, and the obtained photosensitive lithographic printing plate sample was evaluated for developability, storability, printing durability, and fatigue developer deposit amount in the same manner as in Example 1. Table 1 shows the evaluation results.

Photosensitive composition coating liquid 4 Acrylic polymer compound A {HyPMA / MAA / AN / EA (15/10/20/55: molar ratio) Mw. 80,000} 7.0 g trimethylolpropane triacrylate 3.0 g 2,4-bis (trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.2 g p-dimethylaminobenzoic acid ethyl ester 0 .2 g diazo compound {diazodiphenylamine PF ₆ salt / p-hydroxybenzoic acid (60/40: molar ratio) Mw. 2,000} 0.5 g isopropyl tris (dioctyl pyrophosphate) titanate 0.2 g octylphenol novolac {p-octylphenol / phenol (80/20: molar ratio) Mw. 5,000} 0.1 g Polyacrylic acid (Jurimer AC10L manufactured by Nippon Pure Chemical Co., Ltd.) 0.1 g Fluorine-based surfactant (FC430 manufactured by Sumitomo 3M) 0.03 g Victoria Pure Blue BOH (manufactured by Hodogaya Chemical Co., Ltd.) 2 g 2-methoxyethanol 200 ml EMA: ethyl methacrylate

Preparation of Support D The surface of an aluminum plate (material 1050, temper H16) having a thickness of 0.3 mm was degreased with a 3% aqueous sodium hydroxide solution, and this was degreased in a 2% nitric acid bath at 25 ° C. and 50 A /. Electrolytic etching was performed at a current density of dm ² . After washing with water, an anodized film of 3 g / m ² was formed in a 30% sulfuric acid bath. Next, 1% β-
Support D was obtained by hydrophilizing treatment at 85 ° C. for 10 seconds with an alanine aqueous solution.

Comparative Example 1 Photosensitive lithographic printing was performed in the same manner as in Example 1 except that 1.0 g of the diazo compound was used in the composition of the photosensitive composition coating liquid 1 of Example 1 and vinyltriethoxysilane was removed. A plate sample was obtained, and the obtained photosensitive lithographic printing plate sample was evaluated for developability, storability, printing durability, and fatigue developer deposit amount in the same manner as in Example 1. Table 1 shows the evaluation results.

Comparative Example 2 The procedure of Example 2 was repeated except that the composition of the photosensitive composition coating liquid 2 of Example 2 contained 1.0 g of the diazo compound and γ-methacryloxypropyltrimethoxysilane was omitted. A photosensitive lithographic printing plate sample was obtained, and the obtained photosensitive lithographic printing plate sample was processed in the same manner as in Example 2 with respect to developability, storability, printing durability,
And the amount of fatigue developer precipitate. Table 1 shows the evaluation results.

Comparative Example 3 Photosensitive lithographic printing was performed in the same manner as in Example 3 except that 1.0 g of the diazo compound was used in the composition of the photosensitive composition coating liquid 3 of Example 3 and vinyltriethoxysilane was removed. A plate sample was obtained, and the obtained photosensitive lithographic printing plate sample was evaluated for developability, storability, printing durability, and fatigue developer deposit amount in the same manner as in Example 3. Table 1 shows the evaluation results.

Comparative Example 4 Example 4 was repeated except that in the composition of the photosensitive composition coating liquid 4 of Example 4, the diazo compound was 1.0 g and isopropyl tris (dioctyl pyrophosphate) titanate was removed.
Similarly to the above, a photosensitive lithographic printing plate sample was obtained, and the obtained photosensitive lithographic printing plate sample was developed in the same manner as in Example 4,
The storability, printing durability, and amount of fatigue developer precipitate were evaluated. Table 1 shows the evaluation results.

Comparative Example 5 A photosensitive lithographic printing plate sample was obtained in the same manner as in Example 1 except that the support A in Example 1 was replaced with the following support E, and the obtained photosensitive lithographic printing plate sample was carried out. In the same manner as in Example 1, the developability, storability, printing durability, and fatigue developer deposit amount were evaluated. Table 1 shows the evaluation results.

Preparation of support E The surface of an aluminum plate (material 1050, temper H16) having a thickness of 0.3 mm was degreased with a 3% sodium hydroxide aqueous solution, and this was degreased in a 2% nitric acid bath at 25 ° C. and 50 A /. Electrolytic etching was performed at a current density of dm ² . After washing with water, a 3 g / m ² anodized film was provided in a 30% sulfuric acid bath to obtain a support E.

[0094]

[Table 1]

[0095]

According to the present invention, when developing with an alkaline developer containing substantially no organic solvent, it is difficult to form insoluble matter in the developer, and a large amount of developing treatment can be carried out with a fixed amount of developer. It is also possible to provide a photosensitive composition having excellent storage stability and printing durability, a photosensitive lithographic printing plate and a developing method thereof.

Claims (8)

[Claims] 1. A negative photosensitive composition containing a diazo compound, a polymerizable compound having an addition-polymerizable unsaturated bond, a photopolymerization initiator, and a polymer compound capable of forming a film. A photosensitive composition comprising at least one coupling agent among titanium coupling agents. 2. The silane coupling agent is represented by the following general formulas (1) and (2), and the titanium coupling agent is represented by the following general formula (3). Photosensitive composition. Embedded image (In the formula, R ₁ , R ₂ , and R _{3 each} represent a hydroxyl group, a C1 to C5 alkyl group, or an alkoxy group, and R ₄ represents a C1 to C5 alkyl group, a C6 to C18 aryl group,
A vinyl group, an acryloyloxy group, a methacryloyloxy group, a glycidyl group, an amino group, a C1 to C5 aminoalkyl group or a thiol group, and R ₅ is C1 to C1.
C5 alkyl group, C6 to C18 aryl group, vinyl group, C1 to C5 aminoalkyl group,
-X- is -O-, -NH-, -COO-, -S-, -C.
It represents either O-NH-, and l represents 0 to 5. ) General formula _{(3) (R 6 O)} m -Ti (R 7) n ( wherein, _{R 6} O represents an alkoxy group, m represents a 1 to 4, _{R 7} is a fatty acid group, an alkoxy group, a phenol Group, phenoxy group, phosphite group, phosphate group,
n represents 1 to 5, and when n is 2 or more, R ₆ may be the same or different. ) 3. The diazo compound is a co-condensation resin of diazodiphenylamine and an aromatic compound having at least one group selected from a carbonyl group and a sulfonyl group in the molecule. The photosensitive composition described. 4. The photosensitive composition according to claim 1, wherein the polymer compound capable of forming a film has a phenolic hydroxyl group in the molecule. 5. A film-forming polymer compound having a phenolic hydroxyl group in the molecule is obtained by copolymerizing an addition-polymerizable monomer represented by the following general formula (4) with another addition-polymerizable vinyl group-containing monomer. 5. The photosensitive composition according to claim 4, wherein the photosensitive composition is a copolymer. Embedded image (In the formula, R ₇ represents a hydrogen atom or a methyl group, and R ₈ represents -C.
OO- and -CONH- are shown, and n is 0 or 1. ) 6. The method according to any one of claims 1 to 5 on the support which has been subjected to hydrophilic treatment.
A photosensitive lithographic printing plate comprising the photosensitive composition according to claim 1. 7. The method for hydrophilizing a support is any one of sodium silicate treatment, carboxycellulose treatment, organic phosphonic acid treatment, organic sulfonic acid treatment and amino acid treatment. The photosensitive lithographic printing plate described. 8. A method for developing a photosensitive lithographic printing plate, which comprises developing the photosensitive lithographic printing plate according to claim 6 or 7 with an alkaline aqueous solution having a pH of 12 or more and substantially containing no organic solvent.