JPH03296755A - Image forming method - Google Patents

Abstract

PURPOSE:To obtain an image free from printing stain and having superior printing resistance by imagewise exposing a photosensitive layer contg. alkali- soluble diazo resin and developing the exposed layer with a developer contg. at least one kind of alkali agent and water as essential components. CONSTITUTION:A photosensitive layer contg. alkali-soluble diazo resin having anions of an F-contg. org. acid as counter anions and a high molecular compd. is imagewise exposed and developed with a developer contg. at least one kind of alkali agent and water as esential components to form an image. The alkali- soluble diazo resin is diazo resin contg. alkali-soluble groups, preferably arom. hydroxy, arom. thiol, carboxylid acid, sulfonic acid or oxyacid of phosphorus. An image free from printing stain and having superior printing resistance can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an image forming method suitably used in the manufacture of lithographic printing plates, IC circuits, and photomasks.

[Conventional technology]

Generally, photosensitive printing plates are produced by coating a photosensitive composition on a support such as an aluminum plate, irradiating it with active light such as ultraviolet rays through a negative image, polymerizing or crosslinking the irradiated areas, and applying a developer. Insolubilize and elute the non-irradiated areas into a developer, making each area an image area that repels water and accepts oil-based ink, and a non-image area that accepts water and repels oil-based ink. It is obtained by

As photosensitive compositions in this case, diazo resins such as condensates of p-diazodiphenylamine and formaldehyde have been widely used.

Conventionally, the method for linking diazonium salt skeletons in such diazo resins is to condense an aromatic diazonium compound and a reactive carbonyl group-containing organic condensing agent, particularly aldehydes or acetals such as formaldehyde and acetaldehyde, in an acidic medium. The method was used to

The most typical example is a formaldehyde condensate of 4-diazodiphenylamine. A method for producing a diazo resin using the coupling method is described, for example, in U.S. Pat. No. 2.679.498.
No. 3.050.502, No. 3.311.60
No. 5, and the specification of No. 3.277, 074.

In the diazo resin linked by the reactive carbonyl group, when the counter anion of the diazonium salt is a mineral acid such as hydrochloric acid, hydrobromic acid, sulfuric acid, and phosphoric acid, or an inorganic anion such as a double salt with zinc chloride, water-soluble There is a problem that it becomes unstable against moisture and its storage stability deteriorates. Therefore,
In order to improve storage stability, there is a method in which a water-soluble diazo resin is reacted with an organic coupling agent such as a phenolic hydroxyl group-containing aromatic compound, an acidic aromatic compound, or an acidic aliphatic compound and used as a water-insoluble resin. Special Public Service 1977-
No. 1167 and US Pat. No. 3,300,309.

However, this type of diazo resin does not have sufficient solubility in organic coating solvents such as alcohols, ketones, and glycol ethers. Therefore, in order to make the diazo resin water-insoluble and organic solvent-soluble, halogenated Lewis acids such as tetrafluoroboric acid and hexafluorophosphoric acid,
and JP-A-54-98 on the use of diazo resins with perhalogen acids such as perchloric acid and periodic acid as counter anions.
It is described in Japanese Patent No. 613 and Japanese Patent No. 56-121031.

However, these diazo resins do not have sufficient solubility in organic solvents.

Further, regarding the use of anionic surfactants, that is, diazo resins in which a sulfonic acid having a long-chain alkyl group is used as a counter anion, JP-A-58-209733 and JP-A-62
It is described in JP-175731 and JP-63-262643.

However, since these diazo resins are essentially insoluble in alkaline water, the diazo resins are not sufficiently removed during alkaline development, resulting in a residual film in unexposed areas. the result,
There was a problem that printing stains occurred.

Therefore, attempts have been made to increase the solubility of the diazo resin itself in alkaline water by introducing an alkali-soluble group into the diazo resin.

As such examples, co-condensed diazo resins containing an aromatic compound having a carboxyl group and an aromatic diazo compound as constituent units are disclosed in JP-A-1-102457, JP-A-2-66, and JP-A-2-29650. JP-A No. 1-2 discloses a co-condensed diazo resin containing an aromatic compound having a sulfonic acid group and an aromatic diazo compound as constituent units.
It is described in No. 45246.

However, since these diazo resins have alkali-soluble groups, when the non-image areas are developed with alkali after image exposure, the developer penetrates into the image areas and causes them to swell.

As a result, there was a problem in that image strength and printing durability were poor.

In addition, regarding the use of diazo resins in which an anion having a long chain fluorinated alkyl group is used as a counter anion,
This is proposed in the specifications of Japanese Patent No. 12029, Japanese Patent No. 51-141003, and British Patent No. 1501128.

When these diazo resins are applied onto a support and exposed to light, the exposed areas exhibit oil repellency due to the fluorine contained in the diazo resin and thus repel ink. That is, these diazo resins are used as dryographic plates, that is, waterless planographic plates. However, since the diazo resin is essentially hydrophilic, the ink repellency of the exposed area is not sufficient and print stains are likely to occur.

[Problem to be solved by the invention]

Accordingly, an object of the present invention is to provide an image forming method that provides an image that is free from printing stains and has excellent printing durability even when a photosensitive layer is imagewise exposed after long-term storage and developed with alkaline water. .

[Means to solve the problem]

As a result of intensive studies to achieve the above object, the present inventors discovered that the above object could be achieved by using a novel photosensitive composition, and thus arrived at the present invention.

That is, in the present invention, after imagewise exposure of a photosensitive layer containing a polymer compound and an alkali-soluble diazo resin whose counter anion is an anion of an organic acid having a fluorine atom, the photosensitive layer contains at least one alkaline agent and water as essential components. The object of the present invention is to provide an image forming method, which is characterized in that development is performed using a developing solution.

In the present invention, the organic acid refers to an acid having at least one carbon atom.

The present invention will be explained in detail below.

That is, the present invention is based on Japanese Patent Application Laid-open No. 50-12029,
After imagewise exposure, a photosensitive layer containing an alkali-soluble diazo resin having an anion of an organic acid having a fluorine atom as a counter anion and a polymer compound as described in Japanese Patent Publication No. 51-141003 is mixed with at least one kind of water. An image is formed by aqueous development with a developer containing an alkaline agent as an essential component.

The alkali-soluble diazo resin in the present invention is a diazo resin containing an alkali-soluble group.

Preferred examples of the alkali-soluble group include, but are not limited to, aromatic hydroxyl groups, aromatic thiol groups, carboxylic acid groups, sulfonic acid groups, and phosphorus oxygen acid groups. Moreover, the above-mentioned alkali-soluble groups may be used alone or in combination of two or more types.

Examples of the phosphorus oxygen acid group include groups represented by the following formulas (I) to (VT).

-P-OR' (V) - 3 -P-OR' (VI)3 [In the formula, R1 represents a hydrogen atom, R2 represents a hydrogen atom, an alkyl group, or an aryl group, and R3 represents a hydrogen atom, an alkyl group Or represents an aryl group. Preferably, R2 represents a hydrogen atom, and R3 represents a hydrogen atom or an alkyl group having 12 or less carbon atoms. ] Among the above general formulas, particularly preferred phosphorus oxygen acid groups are (1) and (III).

As a method for introducing an alkali-soluble group into the diazo resin, any method possible in terms of organic synthesis can be used, but the following methods can be cited as main methods, for example.

(i) Condensation reaction of an aromatic diazonium compound containing an alkali-soluble group with an aldehyde or ketone or an equivalent of an active carbonyl compound thereof.

(i) A condensation reaction between an aromatic diazonium compound and an aldehyde or ketone containing an alkali-soluble group or an equivalent of an active carbonyl compound thereof.

(iii) A cocondensation reaction between an aromatic diazonium compound, an aromatic compound containing an alkali-soluble group, and an aldehyde or ketone or an equivalent of an active carbonyl compound thereof.

Specific examples of the counter anion of the diazo resin used in the present invention, that is, the anion of an organic acid having a fluorine atom, include fluoroalkyl carboxylic acids such as trifluoroacetic acid, and fluoroalkylsulfonic acids such as trifluoromethanesulfonic acid. , fluoroarylsulfonic acids such as pentafluorobenzenesulfonic acid, fluoroalkylbenzenesulfonic acids such as trifluoromethylbenzenesulfonic acid, anions of fluoroalkylnaphthalenesulfonic acids such as trifluoromethylnaphthalenesulfonic acid,
and bis(fluoroalkylsulfonyl)methides such as bis(trifluoromethylsulfonyl)methide. Preferably, a perfluoroalkyl sulfonic acid having 4 to 20 carbon atoms, an anion of perfluoroalkylbenzenesulfonic acid, and a fluoroalkyl group having 4 to 20 carbon atoms are preferable.
12, such as bis(barfluoroalkylsulfonyl methide).

Further, these anions of organic acids having a fluorine atom can be freely combined with each other, and two or more types may be used in combination. Further, anions other than those mentioned above may be mixed in order to further adjust the fluorine atom content of the diazo resin to be produced. Specific examples of such anions include, for example, hydrohalic acids, such as hydrochloric acid, hydrobromic acid; sulfuric acid, nitric acid, phosphoric acid (pentavalent phosphorus), especially orthophosphoric acid, inorganic iso- and heteropolymer Acids such as phosphotungstic acid, phosphomolybdic acid, aliphatic or aromatic phosphonic acids or their half esters, arsonic acids, phosphinic acids,
Amidosulfonic acid, selenic acid, perchloric acid, as well as aliphatic and aromatic sulfonic acids, such as methanesulfonic acid, laurylsulfonic acid, dioctylsulfosuccinic acid, dicyclohexylsulfosuccinic acid, camphorsulfonic acid, trioxy-3-propanesulfonic acid , nonylphenoxy-propanesulfonic acid, nonylphenoxy-4-butanesulfonic acid, dibutylphenoxy-3-propanesulfonic acid, diaminophenoxy-3-propanesulfonic acid, dinonylphenoxy-3-propanesulfonic acid, dibutylphenoxy-4- Butanesulfonic acid, dinonylphenoxy-4-butanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, mesitylenesulfonic acid, p-chlorobenzenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, sulfosalicylic acid, 2,5-dimethylbenzene Sulfonic acid, p-acetylbenzenesulfonic acid, 5-nitro-
〇-Toluenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-chloro-5-nitrobenzenesulfonic acid, butylbenzenesulfonic acid, butoxybenzenesulfonic acid, 2 -Methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid, isopropylnaphthalenesulfonic acid, butylnaphthalenesulfonic acid, hexylnaphthalenesulfonic acid, butoxynaphthalenesulfonic acid, dodecyloxynaphthalenesulfonic acid, dibutylnaphthalenesulfonic acid, triisopropylnaphthalenesulfonic acid ,
Tributylnaphthalene sulfonic acid, 1-naphthol-5
-Sulfonic acid, naphthalene-1-sulfonic acid, naphthalene-2-sulfonic acid, 1,8-dinitronaphthalene-3
, 6-disulfonic acid, 4,4-diazidostilbene-3
, 3'-disulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, 1゜2-naphthoquinone-2-
Diazido-5-sulfonic acid, 1,2-naphthoquinone-1
-diazide-4-sulfonic acid, octylbenzenesulfonic acid, dioctylbenzenesulfonic acid, nonylbenzenesulfonic acid, dinonylbenzenesulfonic acid, decylbenzenesulfonic acid, undecylbenzenesulfonic acid, dodecylbenzenesulfonic acid, bis-dodecylbenzenesulfonic acid acids, tridecylbenzenesulfonic acid, undecyloxybenzenesulfonic acid, undecyloxybenzenesulfonic acid, doboxybenzenesulfonic acid, bis-
Dobyloxybenzenesulfonic acid, dodecyltoluenesulfonic acid, tetradecylbenzenesulfonic acid, bentatecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, heptadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid, nonadecylbenzenesulfonic acid,
Eicosadecylbenzenesulfonic acid, octylnaphthalenesulfonic acid, dioctylnaphthalenesulfonic acid, nonylnaphthalenesulfonic acid, dibutylnaphthalenesulfonic acid, decylnaphthalenesulfonic acid, bis-decylnaphthalenesulfonic acid, undecylnaphthalenesulfonic acid, dodecylnaphthalenesulfonic acid, Anions such as tridecylnaphthalene sulfonic acid or mixtures of these anions are included.

Furthermore, the diazo resin used in the present invention can also be used in combination with a conventional diazo resin that does not contain an anion of an organic acid having a fluorine atom as a counter anion. Representative examples include U.S. Patent No. 2,679,498;
There are condensates of 4-diazodiphenylamine and formaldehyde described in the specifications of 3050502, 3311065, and 3277074. Also, JP-A-1-102456, JP-A-1-1024
No. 57, No. 1-245246, No. 2-66 and No. 2
Examples thereof include a diazo resin having an alkali-soluble group and a diazo resin having a phosphorus oxygen acid group described in Japanese Patent No. 29650. The mixing molar ratio of the sum total of diazo resins having anions having fluorine atoms to the sum total of diazo resins having anions having no fluorine atoms is 1:0 to 20, preferably 1:0 to 10.

The weight average molecular weight of the diazo resin used in the present invention is approximately 5
A range of 00 to 100.000 is suitable, preferably a range of about 1000 to 10.000.

Next, a synthesis example of the diazo resin used in the present invention will be shown.

Synthesis Example 1 (Diazo resin 1 of the present invention) 4-diazodiphenylamine (0,0600mof>・
Hydrogen sulfate of a condensate of phenoxyacetic acid (0,0400 moβ) and formaldehyde (0,100 mof) (synthesized by a conventional method, weight average molecular weight: 2340) 32. 6
g of potassium perfluorooctane sulfonate (0,0720 moA) was dissolved in 400 g of water.
) in 600 mg of water was added with vigorous stirring.

The produced yellow precipitate was collected by filtration and dried to obtain 33.3 g of perfluorooctane sulfonate of a condensate of 4-diazodiphenylamine/phenoxyacetic acid and formaldehyde (diazo resin 1 of the present invention).

The obtained diazo resin was converted into 1-phenyl-3-methyl-5-
After coupling with parazolone, the weight average molecular weight (polystyrene standard) was measured using gel permeation chromatography (GPC) and found to be 2,340.

Synthesis Example 2 (Synthesis of Diazo Resins 2 to 5 of the Present Invention) The following diazo resins were synthesized in the same manner as in Synthesis Example 1.

Perfluorooctane sulfonate of the condensate of 4-diazodiphenylamine (0,0750 mo1) benzylphosphonic acid (0,0250 mo'll) and formaldehyde (0,100 mo'll) (diazo resin 2 of the present invention, weight average molecular weight: 2080>.

4-Diazo-3-methoxy-diphenylamine (0,0
700moj! ) ・7 enyl phosphate (0,03
00mo Il ) and formaldehyde (0,100m
perfluorooctanoate of the condensate with o1) (diazo resin 3 of the invention, weight average molecular weight: 1960).

4-Diazo-4'-sulfonylmethylphenylamine (
0,0400 moj ・4-diazodiphenylamine (0,0600 moj) and formaldehyde (0,10 moj
bis(perfluorooctylsulfonyl)methide salt of the condensate (diazo resin 4 of the present invention, weight average molecular weight: 1880).

Perfluorooctane sulfonate (diazo resin 5 of the present invention, weight average molecular weight: 1890) of a condensate of 4-diazodiphenylamine (0,100 mo1) and glyoxylic acid (0,0500 moj2) and formaldehyde (0,0500 mo!) .

The alkali-soluble diazo resin used in the present invention is desirably used in combination with an alkali-soluble or swellable polymer compound as a binder resin.

This polymer compound usually has 2 to 2 units of structure having 1,000 units selected from the group shown in (1) to α below.
A copolymer having a molecular weight of 0,000,000,000 is mentioned.

(1) Acrylamides, methacrylamides, acrylic esters, methacrylic esters, and hydroxystyrenes having an aromatic hydroxyl group, such as 1fN-(4
-hydroxyphenyl)acrylamide or N-(4-
hydroxyphenyl) methacrylamide, o+, m-,
p-hydroxyphenylacrylate or methacrylate, o-, m+, p-hydroxystyrene, (2) m-
aminosulfonylphenyl methacrylate), N-(p-
aminosulfonylphenyl) methacrylamide, N-'
(p-aminosulfonylphenyl)acrylamide, N
unsaturated sulfonamides such as -(p-)luenesulfonyl)methacrylamide, (3) acrylic esters and methacrylic esters having aliphatic hydroxyl groups, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, ( 4) Acrylic acid, methacrylic acid, maleic anhydride,
Unsaturated carboxylic acids such as itaconic acid, (5) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate,
Substituted acrylates such as hexyl acrylate, octyl acrylate, benzyl acrylate, phenyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, N-dimethylaminoethyl acrylate, (6) methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, phenyl methacrylate, 4-
Substituted methacrylates such as hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate, (7) acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N -cyclohexyl acrylamide, N-
Acrylamides or methacrylamides such as hydroxyethyl acrylamide, N-phenylacrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenylacrylamide, (8) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, Vinyl ethers such as butyl vinyl ether, octyl vinyl ether, phenyl vinyl ether, (9) vinyl acetate, vinyl chloroacetate, vinyl butyrate, vinyl benzoate, etc.
Jl/esters, αQ Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, αD Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone, beaten ethylene, propylene, Olefins such as isobutylene, butadiene, isoprene, (3N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine,
Acrylonitrile, methachloronitrile, etc., (b)maleimide, N-acryloyl acrylamide,
Unsaturated imides such as N-acetylmethacrylamide, N-propionylmethacrylamide, and N-(p-chlorobenzoyl)methacrylamide.

Furthermore, a monomer that can be copolymerized with the above monomer may be copolymerized. It also includes, but is not limited to, copolymers obtained by copolymerizing the above monomers and modified with glycidyl methacrylate, glycidyl acrylate, and the like.

Particularly suitable polymer compounds include copolymers containing acrylic acid, methacrylic acid, crotonic acid, or maleic acid as an essential component, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl acrylate as described in JP-A-50118802. A multicomponent copolymer of hydroxyethyl methacrylate, acrylonitrile or methachloronitrile, acrylic acid or methacrylic acid and optionally other copolymerizable polymers, as described in JP-A-53-120903. acrylic acid or methacrylic acid which has a hydroxyl group at the end and is esterified with a group containing a dicarboxylic acid ester residue; a multicomponent copolymer of acrylic acid or methacrylic acid and, if necessary, other copolymerizable monomers; Polymers, monomers having aromatic hydroxyl groups as described in JP-A-54-98614 (for example, N-
(4-hydroxyphenyl) methacrylamide, etc.),
Multi-component copolymer of acrylic acid or methacrylic acid and optionally other copolymerizable monomers, JP-A-56-41
A multi-component copolymer of alkyl acrylate, acrylonitrile or methacrylatetrile and an unsaturated carboxylic acid as described in Publication No. 44, EP-330
Examples include multi-component copolymers having sulfonamide groups described in 239(^2). In addition, acidic polyvinyl alcohol derivatives and acidic cellulose derivatives are also useful. In addition, Japanese Patent Publications No. 54-19773, Japanese Patent Publication No. 57-94747, Japanese Patent Application Publication No. 60-182437, Japanese Patent Application Publication No. 62-58242, Japanese Patent Application Publication No. 62-123452, Japanese Patent Publication No. 62-123453 disclose polyvinyl acetal and polyurethane solubilized with alkali. , Japanese Patent Application No. 1-171734 are also useful.

Examples of solvents used when synthesizing such polymeric compounds include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1- Methoxy-2-propertool, 1-
Examples include methoxy 2-propylacetate), N,N-dimethylformamide, toluene, ethyl acetate, methyl lactate, and ethyl lactate.

These solvents may be used alone or in combination of two or more.

These polymer compounds may be used alone or in combination.

Further, if necessary, polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin, novolac resin, natural resin, etc. may be added.

The polymer compound used in the present invention is usually contained in the solid content of the photosensitive composition in an amount of 40 to 99% by weight, preferably 50 to 95% by weight. Further, the photosensitive diazo resin used in the present invention is usually contained in an amount of 1 to 60% by weight, preferably 3 to 30% by weight.

Next, a synthesis example of the above polymer compound will be shown.

(Synthesis of Polymer Compound 1) 170.2 g of p-aminobenzenesulfonamide was placed in a 11-three flask equipped with a stirrer, a cooling tube, and a dropping funnel.
(1.0 mol) and 700% of tetrahydrofuran were added, and the mixture was stirred in an ice-water bath. 52.3 g (0.5 moj2) of methacrylic acid chloride was added dropwise to this mixture over a period of about 1 hour using a dropping funnel. After the dropwise addition was completed, the ice water bath was removed, and the mixture was stirred at room temperature for 30 minutes, and further stirred for 1 hour while being heated to 60° C. using an oil bath. After the reaction was completed, the reaction mixture was poured into water 31 with stirring, stirred for 30 minutes, and then filtered to obtain a white solid of N-(p-aminosulfonylphenyl) methacrylamide. This white solid can be purified by recrystallization from a mixed solvent of ethanol and acetone (yield: 39
．． 3g).

Next, 4.57 g (0,0192 mof) of N-(p-aminosulfonylphenyl)methacrylamide, 2.55 g (0,0480 mof) of acrylonitrile,
Methacrylic acid 1.66 g (0,0192 mojri)
, ethyl acrylate 11°36g (0,1136
rno1), α, α'-azobisisobutyronitrile 0
．． 41 g and 25 g of N,N-dimethylformamide were placed in a 100-Mitsuro flask equipped with a stirrer and a cooling tube, and stirred for 5 hours while warming to 64°C. This reaction mixture was poured into water 21 with stirring, stirred for 30 minutes, filtered, and dried to obtain 16 g of polymer compound 1.

By GPC, the weight average molecular weight (
Polystyrene standard) was measured and found to be 35,000.

(Synthesis of polymer compound 2) N-(p-aminosulfonylphenyl)methacrylamide 4.57 g (0,0192 moi), 2-hydroxyethyl methacrylate 6.25 g (0,0
480 moj, 1.66 g methacrylic acid (0,0
192 mo1), ethyl acrylate 11.36 g
(0.41g of α,α'-azobisisobutyronitrile and 29g of N,N-dimethylformamide were placed in a 100-meter flask equipped with a stirrer and a cooling tube, and heated to 64°C. Stirred for 5 hours.

This reaction mixture was poured into water 21 with stirring, stirred for 30 minutes, filtered, and dried to obtain 20 g of lipophilic polymer compound 2. The weight average molecular weight (polystyrene standard) of this polymer compound 2 was measured by GPC and found to be 44.000.

(Synthesis of polymer compound 3) N-(4-hydroxyphenyl) methacrylamide 18
g1 Acrylonitrile 13g1 Benzyl acrylate 6
6 g of methacrylic acid, 8.6 g of azobisisobutyronitrile and 1.642 g of azobisisobutyronitrile were dissolved in 112 g of a 1:1 mixed solution of acetone and methanol, and the mixture was purged with nitrogen and heated at 60° C. for 8 hours.

After the reaction was completed, the reaction solution was poured into water 51 with stirring, and the resulting white precipitate was filtered and dried to obtain 88 g of polymer compound 3.

When the molecular weight of this polymer compound 3 was measured by GPC, the weight average molecular weight (polystyrene standard) was 75.
It was 000.

(Synthesis of polymer compound 4) 50.0 g of 2-hydroxyethyl methacrylate.

Acrylonitrile 20g 1 Methyl methacrylate 25g
A mixture of 5 g of methacrylic acid and 1.2 g of benzoyl peroxide was added dropwise over 2 hours to 300 g of ethylene glycol monomethyl ether heated to 100°C. After the dropwise addition was completed, 300 g of ethylene glycol monomethyl ether and 0.3 g of benzoyl peroxide were added, and the mixture was allowed to react for 4 hours. After the reaction was completed, the mixture was diluted with methanol and poured into 5 Il of water with stirring, and the resulting white precipitate was collected by filtration and dried to obtain 90 g of polymer compound 4.

When the molecular weight of this polymer compound 4 was measured by GPC, the weight average molecular weight (polystyrene standard) was 65.
It was 000.

(Synthesis of Polymer Compound 5) 40 g of 2,2-bis(hydroxymethyl)propionic acid (0,298 moj) and 100 g of acetic anhydride were placed in a 500-meter flask equipped with a stirrer, a cooling tube, and a dropping funnel.
- and stirred in an ice water bath. 1 pyridine in this mixture
00- was added dropwise using a dropping funnel over about 30 minutes. After the addition was completed, the ice water bath was removed, and the mixture was stirred for 2 hours while being heated to 60° C. in an oil bath. After the reaction is complete, add hydrochloric acid to make the mixture acidic, and use a separating funnel to
Extracted with chloroform. After washing the chloroform layer with water, it was dehydrated with anhydrous sodium sulfate.

By distilling off the solvent from this chloroform solution under reduced pressure, 57 g of a white solid of 2,2-bis(acetoxymethyl)propionic acid was obtained.

Next, 30 g (0,137 mo1) of 2,2-bis(acetoxymethyl)propionic acid and 20-thionyl chloride were added to a 30-ml reactor equipped with a stirrer, a cooling tube, and a dropping funnel.
The mixture was placed in a Mitsuro flask and stirred for 2 hours while heating to 80°C.

After the reaction was completed, unreacted thionyl chloride and the like were sufficiently removed by distillation under reduced pressure, and then the reaction product was sufficiently cooled by placing it in an ice water bath. This reaction product contains 46.6 g (0,274 mo1) of p-aminobenzenesulfonamide and 150 stl of tetrahydrofuran! The mixture was added dropwise through a dropping funnel over a period of about 1 hour. After the addition was completed, the mixture was stirred in an oil bath for 2 hours while being heated to 60°C. After the reaction, the reaction mixture was poured into 2 Il of water with stirring, stirred for 30 minutes, and filtered to obtain a white solid of p-(1,1-bis(acetoxymethyl)ethylcarbonylamino)benzenesulfonamide. Obtained. This white solid can be purified by recrystallization from ethanol (yield: 26
g).

Next, 22 g of p-(1,1-bis(acetoxymethyl)ethylcarbonylamino)benzenesulfonamide
(0.06 mo1), 4°8 g of sodium hydroxide (
0.12 mojiri, ethanol 50- and water 50-
The mixture was placed in a 300-Mitsuro flask equipped with a stirrer and a condenser, and heated under reflux for 2 hours. This reaction mixture was mixed with 11 parts of water.
After stirring for 30 minutes, the mixture was filtered to obtain a white solid of p-(1,1-bis<hydroxymethyl)ethylcarbonylamino)benzenesulfonamide. This white solid can be purified by recrystallization from ethanol (yield: 11 g).

Next, 3.44 g of p-(1,1-bis(hydroxymethyl)ethylcarbonylamino)benzenesulfonamide
(0,012mof), 2. 2-dihydroxymethylpropionic acid 1.07. g (0,008rnoβ
), 4.4'-diphenylmethane diisocyanate 5,
26 g (0,021 rnof) and 18 g of N,N-dimethylacetamide were placed in a 10-liter tube equipped with a stirrer and a cooling tube.
0mf! The mixture was placed in a Mitsuro flask and stirred for 4 hours while heating to 100°C. The reaction mixture was cooled and methano4
Add 500+ytl' of water and stir for a while.
A stirring bar was added to the solution, and the mixture was stirred for 30 minutes.

The precipitate was filtered and dried to obtain 9 g of white solid polymer compound 5. The weight average molecular weight (polystyrene standard) of this polymer compound 5 was measured by GPC and found to be 64.000.

Synthesis Example 6 98.5 g of 0-aminobenzyl alcohol (0
, 8rnof) and acetone 500-, and NaCl
- Stirred under water bath. In this flask were 27.5 g of m-benzenedisulfonyl chloride (0, IIffIo!
A solution of 200% of acetone was added dropwise through a dropping funnel over a period of about 1 hour. After the dropwise addition was completed, the NaCl water bath was removed, and the mixture was stirred at room temperature for 2 hours. After the reaction was completed, most of the acetone was distilled off under reduced pressure, and the mixture was poured into 1.beta. of water with a stirring bar, and further acidified with hydrochloric acid. The precipitate was collected by filtration and dissolved in an aqueous sodium hydroxide solution. After filtering off insoluble materials, the filtrate was placed in a separating funnel and washed twice with ethyl acetate. The aqueous layer was made acidic by adding hydrochloric acid, and the precipitate was collected by filtration. After washing thoroughly with water and drying, the nori,
To obtain a solid N,N'-bis(0-hydroxymethylphenyl)benzene-m-disulfonamide, the yield was 30.
．． 6g>.

Next, 6.28 g of N,N'-bis(0-hydroxymethylphenyl)benzene-m-disulfonamide was placed in a 100 Inl three-way flask equipped with a stirrer and a condenser.
(0,014 moj?), 2. 2-dihydroxymethylpropionic acid 0.80 g (0,006 mo
f), 4,4'-diphenylmethane diisocyanate 5
．． 26 g (0,021 mol) and 18 g of N,N-dimethylacetamide were added and stirred for 3 hours while heating to 100°C. After the reaction was completed, 10 g of methanol was added and stirred for a while, and then the mixture was poured into 500 ml of water with a stir bar and stirred for 30 minutes. The precipitate was filtered and dried to obtain 12 g of white solid. The weight average molecular weight of this polymer compound 60 (polystyrene standard) was measured by GPC and found to be 55,000.

Various additives can be further added to the photosensitive composition used in the present invention.

For example, alkyl ethers (e.g. ethyl cellulose, methyl cellulose), surfactants (e.g. JP-A-62-170950, JP-A-62-2) to improve coating properties.
26143, fluorosurfactants such as those described in U.S. Pat. No. 3,787,351), membrane flexibility,
Plasticizers to impart wear resistance (e.g. tricresyl phosphate, dimethyl phthalate, dibutyl phthalate, trioctyl phosphate, tributyl phosphate, tributyl citrate, polyethylene glycol, polypropylene glycol, etc.), making the image area of the developer visible Pigments such as acridine dyes, cyanine dyes, styryl dyes, triphenylmethane dyes, and phthalocyanines are used as coloring substances for imaging, and other common stabilizers for diazo resins (phosphoric acid, phosphorous acid, birophosphoric acid, oxalic acid, Boric acid, p-toluenesulfonic acid, benzenesulfonic acid, p-hydroxybenzenesulfonic acid, 2-methoxy-4-hydroxy-5
-benzoylbenzenesulfonic acid, malic acid, tartaric acid,
Dipicolinic acid, polyacrylic acid and its copolymers, polyvinylphosphonic acid and its copolymers, polyvinylsulfonic acid and its copolymers, 5-nitronaphthalene-1=phosphonic acid, 4-chlorophenoxymethylphosphonic acid, sodium phenyl- Methyl-pyrazolone sulfonate,
2-phosphonobutane-1,2,4-tricarboxylic acid, 1
-phosphonoethane-1,2゜2-tricarboxylic acid, 1-
Hydroxyethane-1°1-disulfonic acid, etc.) can be added.

The amount of these additives added varies depending on the purpose of use, but is generally 0.1 to 3% of the total solid content of the photosensitive layer.
It is 0% by weight.

The photosensitive composition used in the present invention is dissolved in a suitable organic solvent and coated on a support having a lipophilic surface to a dry coating weight of 0.
．． A photosensitive lithographic printing plate can be obtained by applying the photosensitive composition at a concentration of 2 to 10 g/rn''.The concentration of the photosensitive composition at the time of coating is preferably in the range of 1 to 50% by weight.

The coating solvents used include methyl cellosolve, ethyl cellosolve, 1-methoxy-2-propanol, dimethoxyethane, diethylene glycol methyl ether, diethylene glycol dimethyl ether, methyl cellosolve acetate, acetone, methyl ethyl ketone, methanol, dimethyl formamide, dimethyl acetamide, and dimethyl. Examples include sulfoxide, methyl lactate, ethyl lactate, ethylene dichloride, cyclohexanone, dioxane, and tetrahydrofuran. A mixed solvent of these or a mixed solvent obtained by adding a small amount of water or a solvent such as toluene that does not dissolve the diazo resin or the polymer compound to these solvents or mixed solvents is also suitable. When applying a photosensitive liquid dissolved in these solvents to a support and drying it, 50
It is desirable to dry at a temperature of 120°C to 120°C. The drying method may be performed by starting at a low temperature and drying at a high temperature after preliminary drying, or by selecting an appropriate solvent and concentration, it may be directly dried at a high temperature.

Various materials such as paper, plastic, and metal can be used as the support to which the photosensitive composition used in the present invention is coated, but when used in photosensitive lithographic printing plates, aluminum that has been made hydrophilic is particularly suitable. A plate is preferred. The surface of the aluminum plate can be prepared using mechanical methods such as wire brush danishing, brush danishing in which the surface is roughened with a nylon brush while pouring a slurry of abrasive particles, boulder aining, etc., or HF.
Ya A1C1! ,) After the surface is grained by chemical daining using Ici as an etchant, electrolytic graining using nitric acid or hydrochloric acid as an electrolyte, or composite graining performed by combining these roughening methods, as necessary. The aluminum surface is etched with an acid or alkali, and then anodized in sulfuric acid, phosphoric acid, oxalic acid, boric acid, chromic acid, sulfamic acid, or a mixed acid thereof using a DC or AC power source to form a strong bond on the aluminum surface. Those provided with a dynamic film are preferred. Although the aluminum surface is made hydrophilic by such a passive film itself, if necessary, the method described in U.S. Pat. No. 2.714.066 and U.S. Pat.
181.461, the silicate treatment (
sodium silicate, potassium silicate), US Patent No. 2.
946.638; phosphomolybdate treatment as described in U.S. Pat. No. 3,201.247; British Patent No. 1.108.559. The alkyl titanate treatment described in German Patent No. 1,091.433, the polyacrylic acid treatment described in German Patent No. 1, 091.433,
．． 134.093 specification and British patent jlG 1,23
Polyvinylphosphonic acid treatment described in Japanese Patent Publication No. 44-6409, phytic acid treatment described in U.S. Pat. No. 3,307,951. Processing, JP-A-58-1
Treatment with a salt of a hydrophilic organic polymer compound and a divalent metal as described in JP-A-58-18291 and JP-A-58-18291; Particularly preferred are those which have been subjected to hydrophilic treatment by undercoating with a water-soluble polymer having sulfonic acid groups.

Other hydrophilic treatment methods include U.S. Patent No. 3,658
．． Mention may also be made of the silicate electrodeposition described in No. 662.

Moreover, it is also preferable to perform a sealing treatment after graining and anodizing. Such a sealing treatment is performed by immersion in hot water and a hot aqueous solution containing an inorganic or organic salt, a steam bath, and the like.

The photosensitive composition coated on the support is exposed to light through a transparent original having a line image, halftone image, etc., and then developed with an aqueous alkaline developer to give a negative relief image to the original.

Light sources suitable for exposure include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, strobes,
Examples include ultraviolet rays and laser beams.

The developer used in the development of the photosensitive layer in the present invention contains at least one alkaline agent and water as essential components.

The alkaline agents contained as essential components in the developer include sodium silicate, potassium silicate, potassium hydroxide,
Inorganic alkaline agents such as sodium hydroxide, lithium hydroxide, sodium or ammonium salts of secondary or tertiary phosphoric acid, sodium metasilicate, sodium carbonate, ammonia,
Mono, di or trimethylamine, mono, di or triethylamine, mono or diisopropylamine, n-butylamine, mono, di or triethanolamine, mono,
di- or triisopropanolamine, ethyleneimine,
Examples include organic amine compounds such as ethylenediimine. These alkaline agents may be used alone or in combination of two or more.

The content of these alkaline agents in the developer is 0.0
It is 5 to 10% by weight, preferably 0.5 to 5% by weight. If it is less than 0.05% by weight, development will be poor, and 10
Exceeding this percentage by weight will have an adverse effect on the printing performance of the lithographic printing plate.

The developer used in the present invention may contain a specific organic solvent, if necessary.

Such an organic solvent can dissolve or swell the non-exposed area (non-image area) of the above-mentioned photosensitive composition layer when contained in the developer, and is resistant to water at room temperature (20°C). An organic solvent with a solubility of 10% by weight or less. Any organic solvent may be used as long as it has such characteristics, and examples include, but are not limited to, the following. That is,
Examples include carboxylic acid esters such as ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate, ethylene glycol monobutyl acetate, butyl lactate, butyl levulinate; ethyl butyl ketone, methyl isobutyl ketone, and cyclohexanone. Ketones such as ethylene glycol monobutyl ether, ethylene glycol benzyl ether, ethylene glycol monophenyl ether, benzyl alcohol, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol; alcohols such as xylene; alkyl-substituted aromatics such as xylene; Group hydrocarbons include halogenated hydrocarbons such as methylene dichloride, ethylene dichloride, and monochlorobenzene. These organic solvents may be used alone or in combination of two or more. Among these organic solvents, ethylene glycol monophenyl ether and benzyl alcohol are particularly effective. Further, the content of these organic solvents in the developing solution is generally 0 to 20% by weight, and particularly preferable results are obtained when the content is 2 to 10% by weight.

Further, the developer used in the present invention may contain a water-soluble sulfite as necessary. Such water-soluble sulfites are preferably alkali or alkaline earth metal salts of sulfite, such as sodium sulfite, potassium sulfite, lithium sulfite, and magnesium sulfite. The content of these sulfites in the developer composition is 0.
-4% by weight, preferably 0.1-1% by weight.

Further, instead of the water-soluble sulfite, an alkali-soluble pyrazolone compound, an alkali-soluble thiol compound, or a hydroxy aromatic compound such as methylresorcinol may be contained. Of course, these compounds and water-soluble sulfites can also be used together.

Certain solubilizers may also be included to aid in the dissolution of the organic solvents mentioned above in water.

As such a solubilizing agent, in order to achieve the desired effect of the present invention, it is preferable to use low-molecular alcohols and ketones that are more water-soluble than the organic solvent used.

Furthermore, anionic activators, amphoteric activators, etc. can also be used. Examples of such alcohols and ketones include methanol, ethanol, propatool, butanol,
Acetone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methoxybutanol, ethoxybutanol, 4-
It is preferable to use methoxy-4-methylbutanol, N-methylpyrrolidone, and the like. In addition, examples of the activator include sodium isopropylnaphthalene sulfonate,
Preferred are sodium n-butylnaphthalenesulfonate, sodium N-methyl-N-pentadecylaminoacetate, sodium lauryl sulfate, and the like. The amount of solubilizers such as alcohols and ketones used is generally preferably about 30% by weight or less based on the entire developer.

However, if it contains organic solvents, it may cause hygiene problems such as toxicity and odor during work, and safety problems such as fire and gas explosion.
Workability problems such as foam formation, pollution problems due to waste liquid, etc.
Since problems such as cost arise, it is preferable to use one that does not substantially contain an organic solvent.

Note that "substantially free of organic solvent" means that it does not contain organic solvent to the extent that it causes inconvenience in terms of environmental health, safety, workability, etc., and in the present invention, This means that the proportion of the substance in the composition is 2% by weight or less, preferably 1% by weight or less.

〔Effect of the invention〕

The image forming method of the present invention can provide images with no printing stains and excellent printing durability even when the photosensitive layer is subjected to imagewise exposure and aqueous development after long-term storage.

Example Work The surface of an aluminum plate having a thickness of 0.24 mm was grained using a nylon brush and 400 mesh of an aqueous suspension of pumice stone, and then thoroughly washed with water. This is 1
After etching by immersing in a 0% sodium hydroxide aqueous solution at 70°C for 60 seconds, washing with running water and neutralizing with 20% nitric acid, the electrochemical surface roughening method described in JP-A-53-67507, That is, VA=12.7VSVc=9. 160°C in a 1% nitric acid aqueous solution using a sinusoidal alternating waveform current of IV.
Electrolytic surface roughening treatment was performed using a special anode electricity amount of 1 chlorine/dm2. Subsequently, it was immersed in a 30% sulfuric acid aqueous solution and heated to 55°C.
After desmutting for 2 minutes in a 7% aqueous solution of sulfuric acid, anodizing was performed in a 7% aqueous solution of sulfuric acid so that the coating amount of aluminum oxide was 2.0 g/m''.Then, the product was desmutted in a 3% aqueous solution of sodium silicate at 70°C for 1 minute. The aluminum plate obtained as described above was coated with the following photosensitive solution using a wheeler and dried for 2 minutes at 80°C.The dry weight was 2.0g/g. Ta.

Further, the diazo resin and polymer compound used in the photosensitive solution shown below are shown in Table 1.

(Photosensitive liquid) Next, as a comparative example, a photosensitive liquid using the following diazo resin was applied to the above photosensitive liquid and dried. Dry weight is 2゜Og/
It was Go.

(Diazo resin used in Comparative Examples 1 to 3) Comparative Example 1 Dodecylbenzenesulfonic acid salt of a condensate of 4-diazodiphenylamine (0,100 mol) and formaldehyde (0,100 mol).

Comparative Example 2 4-diazodiphenylamine (0,060 moJL/) phenoxyacetic acid (0,040 mole) and formaldehyde (
0,100 mol) dodecylbenzenesulfonate.

Comparative Example 3 4-Diazodiphenylamine (0,075 mol), benzylphosphonic acid (0,025 mol) and formaldehyde (
0,100 mol) dodecylbenzenesulfonate.

[Evaluation of printing stain and rigidity resistance]

Each of the photosensitive lithographic printing plates thus obtained was subjected to image exposure for 1 minute from a distance of 1 m using a PS light manufactured by Fuji Photo Film ■, immersed in the following developer for 1 minute at room temperature, and then surfaced with absorbent cotton. was lightly rubbed to remove the unexposed areas to obtain lithographic printing plates (I) to (X) with bright blue images.

(Developer) Each printing plate was printed on high-quality paper with a commercially available ink using a KOR printing machine manufactured by Heidelberg.

The printing stains and printing durability of the lithographic printing plates (I) to (X) were examined, and the results were as shown in Table 1.

On the other hand, each of the obtained photosensitive lithographic printing plates (I) to (X) was subjected to forced fatigue at a temperature of 45° C. and a humidity of 75% for one week, and then subjected to image exposure, development, and printing in the same manner. The printing stains and printing durability of the lithographic printing plates (I) to (X) subjected to forced fatigue in this manner were examined, and the results were as shown in Table 1.

As can be seen from Table 1, the lithographic printing plate (
1) to (■) give an image with no printing stains and excellent rigidity resistance before forced fatigue, but comparative example (■)
There is no noticeable difference compared to ~(X). However, the lithographic printing plates (I) to (■) of the present invention do not cause printing stains during printing and give images without deterioration in printing durability even when subjected to image exposure and aqueous development after forced fatigue. This is significantly superior to Comparative Examples (■) to (X).

That is, the image forming method of the present invention is very excellent in that even when the printing plate is subjected to forced fatigue and then processed, printing stains do not occur during printing and images are produced without deterioration in printing durability.

Example 2 Each of the photosensitive planographic printing plates obtained in Example 1 was image-exposed for 1 minute from a distance of 1 m using a PS light manufactured by Fuji Photo Film ■, and then immersed in the following developer at room temperature for 1 minute, and then exposed to absorbent cotton. The surface was lightly rubbed with a cloth to remove the unexposed areas, and lithographic printing plates (I) to (X) with bright blue images were obtained.

(Developer) In the same manner as in Example 1, each printing plate was used to print on high-quality paper using a commercially available ink using a KOR type printer manufactured by Heidelberg.

The printing stains and printing durability of the lithographic printing plates (r) to (X) were examined, and the results were as shown in Table 2.

On the other hand, each of the obtained photosensitive lithographic printing plates (I) to (X) was subjected to forced fatigue at a temperature of 45° C. and a relative humidity of 75% for one week.
Image exposure, development, and printing were performed in the same manner. The printing stains and stiffness resistance of the lithographic printing plates (1) to (X) subjected to forced fatigue in this manner were examined, and the results were as shown in Table 2.

As can be seen from Table 2, the lithographic printing plate (
I) to (■) give images with no printing stains and excellent printing durability before forced fatigue, but comparative example (■)
) to (X), no significant difference is observed. but,
The lithographic printing plates (I) to (■) of the present invention do not cause printing stains during printing and give images with no decrease in rigidity even when subjected to image exposure and aqueous development after forced fatigue. It is significantly superior to the examples (■) to (X).

That is, the image forming method of the present invention is very excellent in that even when the printing plate is subjected to forced fatigue and then processed, printing stains do not occur during printing and images are produced without deterioration in printing durability.

Claims (1)

[Claims] After image exposure of a photosensitive layer containing a polymer compound and an alkali-soluble diazo resin whose counter anion is an anion of an organic acid having a fluorine atom, the photosensitive layer is developed with a developer containing at least one alkaline agent and water as essential components. An image forming method characterized by: