JPH0229749A - Preparation of photosensitive planographic printing plate - Google Patents

Abstract

PURPOSE:To obtain a photosensitive planographic printing plate contg. no uneveness in coating film by dissolving a compsn. contg. a photosensitive material and an F-contg. surfactant expressed by the specified structural formula in a solvent and coating the soln. on a base plate and drying. CONSTITUTION:An F-contg. surfactant expressed by the formula I is added to a compd. prepd. from o-naphthoquinonediazide sulfonic acid and a polycondensation resin of a phenol or a phenolic deriv. with an aldehyde. In the formula I, R<1> is an alkyl group; R<2> is an alkylene group and/or a fluorinated alkylene group; R<3> is an alkylenoxy group and/or a fluorinated alkylenoxy group; (a) is 1-10; (b) is 1-30; R<3> contains at least one fluorinated alkylenoxy group. The compsn. is dissolved in ethyleneglycol monomethyl ether, ethylene cellosolve acetate, etc., and the soln. is coated on an Al plate having a roughened surface and dried. By this constitution, a photosensitive planographic printing plate having a photosensitive layer having superior coatability and a uniform film thickness is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a photosensitive lithographic printing plate, and more particularly to a method for producing a photosensitive lithographic printing plate without causing coating unevenness.

[Prior Art] A photosensitive lithographic printing plate is obtained by dissolving a photosensitive composition containing a photosensitive substance in an appropriate solvent, coating it on a support, and drying it. Unevenness,
The formation of an uneven photosensitive layer with pinholes, citrus unevenness, wavy unevenness, etc. not only impairs the value of the product in terms of appearance, but also impairs characteristics such as sensitivity, halftone dot reproducibility, and printing durability. Causes instability. To address this problem, JP-A-57-178242 discloses that streak-like unevenness was improved by adding a relatively low concentration of fluorine-containing surfactant to a specific coating solvent. Are listed. Also, in Japanese Patent Application Laid-open No. 60-24545,
It is described that streak-like unevenness was improved by using a mixed solvent of two types of solvents with different boiling points as a coating solvent. Furthermore, JP-A No. 62-36657 describes that streak-like unevenness was improved by adding a fluorine-containing surfactant to a specific coating solvent.

[Problems to be Solved by the Invention] However, although the technique described in JP-A-57-178242 is effective in improving streak-like unevenness, it is not effective in improving the above-mentioned wavy density unevenness. Increasing the concentration of the fluorine-based surfactant will improve the density unevenness to some extent, but on the other hand, the foaming properties of the photosensitive coating solution will increase, and depending on the coating method, this foam can cause streak-like unevenness. There are cases.

The technique described in Japanese Patent Application Laid-Open No. 60-24545 was also completely ineffective in improving the above-mentioned wavy density unevenness.

Furthermore, the technique described in Japanese Patent Application Laid-Open No. 62-36657 was also ineffective in improving the wavy unevenness of light and shade. or,
The above-mentioned streak-like unevenness caused by bubbles generated in the coating liquid has not been improved.

[Means for Solving the Problems] Accordingly, an object of the present invention is to eliminate uniform, especially wavy, unevenness in density and lightness in the coating solution when a photosensitive composition is dissolved in a coating solvent and applied and dried on a support. An object of the present invention is to provide a manufacturing method capable of obtaining a coated surface without streak-like unevenness caused by bubbles.

According to the present invention, this purpose is achieved by dissolving a photosensitive composition containing at least a photosensitive substance and a fluorine-containing surfactant represented by the following structural formula [I] in a solvent, and then coating the composition on a support. This is achieved by a method for producing a photosensitive lithographic printing plate, which is characterized by drying the photosensitive lithographic printing plate.

R' -5-(R2)-r-H Coo-(R3+F-H...(■) (In the formula, R1 represents an alkyl group, R2 represents an alkylene group and/or a fluorinated alkylene group, and R3 represents an alkyleneoxy group and/or a fluorinated alkyleneoxy group, a represents a number from 1 to 10, and b represents a number from 1 to 30.
represents the number of (However, R3 contains at least one fluorinated alkyleneoxy group.) The present invention will be described in detail below.

The fluorosurfactant used in the present invention has the following structural formula [
I].

R'-S-(R2)7-HCOO-(R''h-H-CI) Here, in the formula, R1 represents an alkyl group having 1 to 1O1 carbon atoms, preferably 4 to 8 carbon atoms.

R2 represents an alkylene group or a fluorinated alkylene group, preferably an ethylene group or a fluorinated ethylene group. As the fluorinated ethylene group, 1 to 4 hydrogen atoms, preferably 1 to 2 hydrogen atoms of the ethylene group are substituted. Things can be mentioned. Further, R2 may represent an alkylene group and a fluorinated alkylene group at the same time, and the alkylene group unit is 1-
The number of fluorinated alkylene groups is 10, preferably 1 to 4, and the fluorinated alkylene group units are selected from the range of 0 to 9, preferably 0 to 3.

R3 represents an alkyleneoxy group or a fluorinated alkyleneoxy group. However, R3 contains at least one fluorinated alkyleneoxy group. The alkyleneoxy group is preferably an ethyleneoxy group or an isopropyleneoxy group, and the fluorinated alkyleneoxy group is preferably a fluorinated ethyleneoxy group or a fluorinated isopropyleneoxy group.

Examples of the fluorinated ethyleneoxy group include ethyleneoxy groups in which 1 to 4, preferably 1 to 3, hydrogen atoms have been substituted. In addition, as the fluorinated isopropyleneoxy group, 1 to 7 hydrogen atoms of the isopropyleneoxy group,
Preferred examples include those with 1 to 4 substitutions. Also,
R3 may represent an alkyleneoxy group and a fluorinated alkyleneoxy group at the same time, the alkyleneoxy group unit has a number of 0 to 29, preferably 0 to 18, and the fluorinated alkyleneoxy group unit has a number of 1 to 3o. number, preferably 2~
Selected from a range of 20 numbers.

a in structural formula [I] is 1 to 10, preferably 1 to 6
b represents a number from 1 to 30, preferably from 2 to 20.

Specific examples of the fluorosurfactant of the present invention include the following compounds.

(Hereinafter, blank space) ^ = oO, SIE O t% JL1-Flash Photosensitivity of the fluorine-based surfactant used in the present invention! ll
The amount in adult cows is preferably 0.05 to 5% by weight, particularly preferably 0.1 to 1% by weight.

The photosensitive material of the present invention includes 0-
It can contain a quinonediazide compound. The O-quinonediazide compound is preferably an ester compound of a polycondensation resin of O-naphthoquinone cyatosulfonic acid, phenol, and aldehyde or ketone.

Examples of phenols include dihydric phenols such as phenol, O-cresol, m-cresol, p-cresol 3,5-xylenol, carvacrol, and thymol; dihydric phenols such as catechol, resorcin, and hydroquinone; pyrogallol, phloroglucin, etc. Examples include trihydric phenols. Among them, dihydric phenols are preferred. Formaldehyde is an aldehyde,
Examples include benzaldehyde, acetaldehyde, crotonaldehyde, and furfural. Among these, formaldehyde and benzaldehyde are preferred. Furthermore, examples of the ketone include acetone, methyl ethyl ketone, and the like.

Specific examples of the polycondensation resin include phenol/formaldehyde resin, m-cresol/formaldehyde resin, m-, p-mixed cresol/formaldehyde resin, resorcinol/benzaldehyde resin, and pyrogallol/formaldehyde resin.
Examples include acetone resin.

The condensation rate of 0-naphthoquinone cyatosulfonic acid with respect to the OH group of the phenol in the 0-naphthoquinone cyatosulfonic acid (reaction rate with respect to one OH group) is preferably 15 to 80%, more preferably 20 to 45%.

Further, as the quinonediazide compound used in the present invention, the following compounds described in JP-A-58-43451 can also be used. That is, for example, 1.2-penzoquinone diazitosulfonic acid ester, 1.2-naphthoquinone cyasitosulfonic acid ester, 1.2-penzoquinone diazitosulfonic acid amide, 1.2-naphthoquinonediazide sulfonic acid amide Known 1,2-quinonediazide compounds such as, more specifically, J. Kosar (J.

Kosar) 7 r light sensitive system”
("Light-3ensistive Systems
'') pp. 339-352 (1965), John Wiley & Sons
5ons) (New York) and W Varnish Day Forest (W, S.).

"Photoresist" by De Fores L) (Ph.
1,2-penzoquinone diazito 4-sulfonic acid phenyl ester, 1,2-benzoquinone diazito 4-sulfonic acid phenyl ester, described in McGraw-Hill (1+Ic to rB-11i11), New York), Volume 50 (1975) .l',
2'-di(penzoquinonediazito-4-sulfonyl)-dihydroxybiphenyl, l,2-penzoquinonediazito-4-(N-ethyl-N-β-naphthyl)-sulfonamide, 1,2-naphthoquinone Cyacyto-5-sulfonic acid cyclohexyl ester, 1-(1,2-naphthoquinonecyacyto-5-sulfonyl)-3,5-dimethyl and lazole, l,2-naphthoquinone cyazito-5-sulfonic acid-4'' hydroxydiphenyl -4″-azo-β-
Naphthol ester, N,N-cy(l,2-naphthoquinonecyato-5-sulfonyl)-aniline, 2'-
(1,2-naphthoquinone cyacito-5-sulfonyloxy)-1-hydroxy-anthraquinone, 1,2-naphthoquinone cyacito-5-sulfonic acid-2,4-dihydroxybenzophenone ester, 1,2-naphthoquinone cyacito-5-sulfonic acid 5-sulfonic acid-2,3,4-trihydroxybenzophenone ester, 1,2-naphthoquinone condensate of 2 moles of cyasito-5-sulfonic acid chloride and 1 mole of 4,4'-diaminobenzophenone, 1,2-naphthoquinone 2 moles of cyacyto-5-sulfonic acid chloride and 4.4'
- a condensate of 1 mol of dihydroxy-1,1'-diphenylsulfone, a condensate of 1 mol of 1,2-naphthoquinone cyato-5-sulfonic acid chloride and 9921 mol of purpuro,
Examples include 1,2-quinone diazide compounds such as 1,2-naphthoquinone cyato-5-(N-dihydroabiethyl)-sulfonamide. In addition, the special public service
No. 1953, No. 37-3627, No. 37-13109
No. 40-26126, No. 40-3801, No. 4
No. 5-5604, No. 45-27345, No. 51-13
No. 013, JP-A-48-96575, JP-A No. 4B-638
02, No. 4B-63803, as described in each publication,
Mention may also be made of 2-naphthoquinone diazito compounds.

As the 0-naphthoquinone cyacyto compound of the present invention, each of the above compounds may be used alone, or two or more thereof may be used in combination.

The proportion of the naphthoquinone cyacyto compound used in the present invention in the photosensitive composition is preferably from 5 to 60 parts by weight, particularly preferably from 10 to 50 parts by weight.

Further, as the photosensitive substance used in the present invention, a diazo resin typified by a condensate of an aromatic diazonium salt and formaldehyde is also used.

Particular preference is given to salts of condensates of p-diazodiphenylamine and formaldehyde or acetaldehyde, such as reaction products of hexafluorophosphates, tetrafluoroborates, perchlorates or periodates with said condensates. Certain diazo resin inorganic salts and U.S. Pat.
The reaction product Jli! of the above condensate and sulfonic acids, as described in the specification of No. 309, Jli! , diazo resin organic salts, and the like. Furthermore, the diazo resin is preferably used together with a binder. Various polymer compounds can be used as such a binder, but monomers having an aromatic hydroxyl group such as those described in JP-A No. 54-98613, such as N-(4 -Hydroxyphenyl)acrylamide, N-(4-hydroxyphenyl)methacrylamide, o-, m-, or p-hydroxystyrene, o-, m-, or p-hydroxyphenyl methacrylate, etc. in combination with other monomers. polymer,
Polymers containing hydroxyethyl acrylate units or hydroxyethyl methacrylate units as the main repeating unit as described in U.S. Pat. No. 4,12:1,276, natural resins such as shellac and rosin, polyvinyl alcohol, Patent No. 3,751,25
Polyamide described in U.S. Pat. No. 7, U.S. Pat.
．． Included are linear polyurethane resins described in No. 660.097, phthalated polyvinyl alcohol resins, epoxy resins condensed from bisphenol A and epichlorohydrin, celluloses such as cellulose acetate and cellulose acetate phthalate.

The photosensitive substances used in the present invention mainly include photosensitive polymers such as polyesters, polyamides, and polycarbonates containing -CH=CH-C- as a photosensitive group in the polymer main chain or side chain. Also suitable are those used as ingredients. for example.

Photosensitive polyester obtained by condensation of phenylene diethyl acrylate with hydrogenated bisphenol A and triethylene glycol, as described in JP-A-55-40415, US Pat. No. 2,956.8
Photosensitive polyesters derived from (2-probeliden) malonic acid compounds such as cinnamylidene malonic acid and Ninomiya glycols as described in No. 78 can be mentioned.

Furthermore, as the photosensitive substance used in the present invention, aromatic azide compounds in which an azide group is bonded to an aromatic ring directly or via a carbonyl group or a sulfonyl group are also used.
For example, boriasitostyrene, polyvinyl-p as described in U.S. Pat. No. 3,095,311;
-Azidobenzoate, polyvinyl-p-azidobenzal, the reaction product of azidoarylsulfanyl chloride and unsaturated hydrocarbon polymer described in Japanese Patent Publication No. 45-9613, and Japanese Patent Publication No. 43-21067, 44
No.-229, No. 44-22954, No. 45-2491
Polymers having sulfonyl azide or carbonyl azide as described in each publication of No. 5 can be mentioned.

Furthermore, as the photosensitive substance used in the present invention, a photopolymerizable composition comprising an addition polymerizable unsaturated compound is also used. Furthermore, photosensitive compositions used in electrophotographic photosensitive lithographic printing plates can also be used. An example of such a composition is a photosensitive composition comprising a phthalocyanine pigment, an electron-donating compound, and a phenol resin, which is used in a printing original plate using electrophotography, as described in JP-A-55-161250.

Among the photosensitive compounds used in the present invention, particularly preferred are 0-naphthoquinone cyacyto compounds.

The photosensitive composition used in the present invention preferably contains various alkali-soluble resins. Any known alkali-soluble resin can be used, but novolak resin, Japanese Patent Publication No. 50-8658
A vinyl copolymer having a phenolic hydroxyl group as described in JP-A-58-122533
An acrylic copolymer having a unit having a carboxyl group and an ester group of the carboxyl group in its molecular structure as described in the above publication is preferred.

As the novolak resin, a resin obtained by copolycondensing formaldehyde with at least one selected from phenol, m-cresol, O-cresol, and p-cresol is used. Cresol/formaldehyde resins and m-cresol/p-cresol/formaldehyde resins are preferred.

Furthermore, the vinyl polymer having a phenolic hydroxyl group (hereinafter referred to as the polymer of the present invention) is a polymer having a unit having the phenolic hydroxyl group in its molecular structure, and is a polymer having the following general formulas (a) to Polymers containing at least one structural unit of (d) are preferred.

(Hereafter, blank space) General formula (a) →CR4R, -CR6+ C0NR7(Ah.B-OH General formula (b) -GCR,R, -CR6-)- COO(A+, B-OH General formula (c) * CRA Rs CR& + -0R General formula (d) OH In the formula, R1 and R2 each represent a hydrogen atom, an alkyl group, or a carboxyl group, preferably a hydrogen atom. R3 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. R4 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and is preferably an aryl group. A represents a nitrogen atom or an oxygen atom and an aromatic group. represents an alkylene group or alkyleneoxy group that may have a substituent that connects to a group carbon atom, m represents an integer from 0 to 1O, and B represents a phenylene group or a substituent that may have a substituent. Represents a naphthylene group that may be present.The polymer of the present invention preferably has a copolymer-type structure, and can be used in combination with the structural units represented by the general formulas (a) to (d). Examples of monomer units that can be used include ethylene, propylene, isobutylene,
Ethylenically unsaturated olefins such as butadiene and isoprene; styrenes such as styrene, α-methylstyrene, p-methylstyrene, and p-chlorostyrene; acrylic acids such as acrylic acid and methacrylic acid; e.g. itaconic acid and maleic acid. acids, unsaturated aliphatic dicarboxylic acids such as maleic anhydride, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-chloro Esters of α-methylene aliphatic monocarboxylic acids such as methyl acrylate, methyl methacrylate, ethyl methacrylate, and ethyl ethacrylate 1 Nitriles such as acrylonitrile and methacrylonitrile Amides such as acrylamide, such as acrylanilide, Anilides such as p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide, etc., vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl acetate, e.g. methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, vinyl ethers such as β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanite,
For example l-methyl-1-methoxyethylene, l, 1
-dimethoxyethylene, 1,2-dimethoxyethylene,
1.1-dimethoxycarbonylethylene, l-methyl-
Ethylene derivatives such as 1-nitroethylene, e.g.
There are vinyl intermediates such as N-vinyl compounds such as vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone, and N-vinylpyrrolidone. These vinyl monomers exist in polymer compounds with a structure in which unsaturated double bonds are cleaved.

Among the above monomers, esters of aliphatic monocarboxylic acids and nitriles are preferred.

These monomers may be bound in the polymer of the present invention in either a block or random manner.

The above alkali-soluble resins may be used alone or in combination of two or more.

The appropriate proportion of such alkali-soluble resin in the photosensitive composition is 30 to 95 weight Z, preferably 5
0-85 weight 2.

In addition to the above-mentioned materials, the photosensitive composition used in the present invention can contain other additives as necessary. Examples include plasticizers of various low molecular weight compounds (for example, phthalates, triphenyl phosphates, maleates, etc.) and printout materials for forming visible images upon exposure to light. The printout material is composed of a compound that generates an acid or a free radical when exposed to light, and an organic dye that changes its color tone by interacting with the compound. Kaisho 50-36
O-naphthoquinone cyato-4-sulfonic acid halide described in JP-A No. 209, JP-A-53-3622
Trihalomethyl-2-pyrone and trihalomethyl-triazine described in Publication No. 3, JP-A-55-6244
0-naphthoquinone cyasito-4 described in the publication No.
- Ester compounds of sulfonic acid chloride and phenols or anilines having electron-withdrawing substituents, helomethyl-vinyl-oxadiazole compounds and diazonium salts described in JP-A-55-77742, etc. Can be mentioned.

Among these, helomethyl-vinyl-oxadiazole compounds are preferred, and are particularly described in JP-A-60-138539. 2 having an oxygen-containing heterocyclic group such as a benzofuryl group directly or via a vinyl group at the 5-position
-Heromethyl-1,3,4-oxadiazole compounds are more preferred.

Examples of the organic dyes include Victoria Pure Blue BOH [Odugaya Chemical Co., Ltd.] and Oil Blue Ii 60.
3 [Orient Chemical], Patent and True Blue [Sumitomo Mikuni Chemical], Crystal Violet, Brilliant Green, Ethyl Violet, Methyl Green, Erythrosin B, Peisic Fuchsin, Malachite Green,
Oil red, m-cresol purple, Rhodamine B
, auramine, 4-p-diethylaminophenylimino-naphthoquinone, cyano-p-diethylaminophenyl acetanilide, etc.; triphenylmethane-based, diphenylmethane-based, oxazine-based, xanthine-based, iminonaphthoquinone-based, azomethine-based or anthraquinone-based pigments; can be mentioned. Among these, triphenylmethane dyes are preferred.

Furthermore, in order to improve the oil sensitivity of the photosensitive composition used in the present invention, a condensate of substituted phenols and aldehydes represented by the following general formula (II) is added as an oil sensitizing agent. and/or 0 of the resin.
- It is preferable to contain a naphthoquinone siasitosulfonic acid ester compound.

General formula (II) H (wherein R1 and R2 are each hydrogen atom, alkylno,
(or represents a halogen atom, R3 represents an alkyl group or a cycloalkyl group having 2 or more carbon atoms) The content of the fat-sensitizing agent in the photosensitive composition is 0.05
-15% by weight is preferred, particularly preferably 0.5-1.
s% by weight.

Further, a sensitizer for improving sensitivity can also be added to the photosensitive composition. Such sensitizers include
Gallic acid derivatives described in JP-A No. 57-118237, 5-membered cyclic acid anhydrides such as those described in JP-A-52-80022, such as phthalic anhydride,
Tetrahydrophthalic anhydride, maleic anhydride, succinic anhydride, pyrometic acid, itaconic acid, etc., and JP-A-58-
Examples include 6-membered cyclic acid anhydrides such as those described in Japanese Patent No. 11932, such as glutaric anhydride and its derivatives. Among these, cyclic acid anhydrides are preferred, and 6-membered cyclic acid anhydrides are particularly preferred.

In the present invention, a photosensitive lithographic printing plate can be obtained by dissolving the above-mentioned photosensitive composition in various coating solvents and coating the solution on the surface of a suitable support and drying it.

Coating solvents that can be used in the present invention include glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; Cellosolve esters such as ethyl cellosolve acetate, methyl cellosolve acetate, and propylene glycol methyl ether acetate; ketones such as methyl ethyl ketone, acetone, and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; Examples include ethylene dichloride, dichloromethane, N,N-dimethylformamide, dioxane, γ-butyrolactone, dimethyl sulfoxide, and tetrahydrofuran.

These solvents can be used alone or as a mixed solvent of two or more. Among these, preferred are those mainly containing glycol ethers and cellosolve esters.

The coating method of the photosensitive layer coating solution in the present invention includes dip coating, roll coating, reverse roll coating, air doctor coating, blade coating, rod coating, knife coating, squeeze coating, gravure coating, cast coating, curtain coating, and extrusion coating. A known method is used, and the coating film thickness is 0.1 to
5 gem” is preferable, the drying temperature is 20 to 150°C,
Preferably it is in the range of 30 to 100°C.

In the present invention, the support used for the photosensitive planographic printing plate includes metal plates such as aluminum, zinc, copper, and steel, and metals plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, iron, etc. Examples include board, paper, plastic film, paper coated with resin, paper covered with metal foil such as aluminum, and plastic film treated with wood. Among these, aluminum plates are preferred. When an aluminum plate is used as a support, it is preferably subjected to surface treatments such as graining, anodizing, and, if necessary, sealing. Known methods can be applied to these treatments.

Examples of the graining treatment include a mechanical method and an electrolytic etching method. Examples of mechanical methods include ball polishing, brush polishing, liquid honing, and puff polishing. The various methods described above can be used alone or in combination depending on the composition of the aluminum material. A preferred method is electrolytic etching.

Electrolytic etching is carried out in a bath containing one or a mixture of two or more inorganic acids such as phosphoric acid, sulfuric acid, hydrochloric acid, and nitric acid. After the graining process, desmutting is performed using an alkali or acid aqueous solution as necessary to neutralize the material, followed by washing with water.

The anodic oxidation treatment is performed by electrolyzing using an aluminum plate as an anode using a solution containing one or more of sulfuric acid, chromic acid, oxalic acid, phosphoric acid, malonic acid, etc. as an electrolytic solution. The amount of anodic oxide film formed was 1 to 5 (lag/dm”
is appropriate, preferably 10 to 40 g/da2. The amount of anodized film can be determined, for example, by immersing an aluminum plate in a phosphoric acid chromic acid solution (85% phosphoric acid solution: 35%, prepared by dissolving 20 g of chromium (VI) oxide in 1 cup of water). It is determined by dissolving the film and determining the constant change in weight of the plate before and after the film is dissolved.

Specific examples of the sealing treatment include boiling water treatment, steam treatment, sodium silicate treatment, and dichromate aqueous solution treatment. In addition, the aluminum plate support can also be subjected to a subbing treatment using an aqueous solution of a water-soluble polymer compound or a metal salt such as fluorinated zirconate.

The photosensitive lithographic printing plate produced according to the present invention can be used in a conventional manner. For example, a transparent positive film is exposed to light from a light source such as an ultra-high pressure mercury lamp, a metal halide lamp, a xenon lamp, a tungsten lamp, etc., and then developed with various alkaline developers, so that only the unexposed areas remain on the surface of the support. A positive relief image is formed.

Examples of the alkaline developer include S sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Examples include aqueous solutions of alkali metal salts such as sodium metasilicate, potassium metasilicate, sodium diphosphate, and trisodium tertiary phosphate. The concentration of alkali metal salt is o,
i-io weight percent is preferred. Further, an anionic surfactant, an amphoteric surfactant, or an organic solvent such as alcohol can be added to the developer as required.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these embodiments.

(Example 1) After degreasing an aluminum plate with a thickness of 0.24 mm in a 5% by weight aqueous sodium hydroxide solution, it was degreased in a 0.5 molar hydrochloric acid aqueous solution at a temperature of 25°C and a current density of 60 A/
d■2. Electrolytic etching treatment was performed under conditions of treatment time: 30 seconds. Next, a desmut treatment was performed with a 5% by weight aqueous sodium hydroxide solution, and then an anodization treatment was performed in a sulfuric acid solution. The amount of anodic oxide film was 20 g/d2. Next, it was immersed in a hot aqueous solution at 90°C to seal the holes. Subsequently, a photosensitive coating solution having the following composition was applied to this aluminum support using a roll coater, and the coating solution was coated at 100°C for 4 hours.
The plate was dried for a minute to obtain a photosensitive planographic printing plate (A).

(Photosensitive coating liquid composition) Teinaphthoquinone-(1,2)-diazide-(2)-5-
Ester compound of sulfonic acid chloride and pyrogallol/acetone resin 5/pt: 1.20g ・Copolycondensation resin of phenol, ■-5p-mixed cresol and formaldehyde (phenol during synthesis, ■-cresol and p-cresol) Each charging molar ratio is 20
: 48 : 32, weight average molecular weight Mw = 140
0, number average molecule Fjl M n=1400) 10.
75g・Fluorine surfactant (exemplified compound (2)) 0.
07g ・Novolak resin synthesized from p-tert-octylphenol and formaldehyde and naphthoquinone-(
Ester compound with 1,2)-diazide-(2)-5-sulfonic acid chloride <Wa association rate 0-f nyl%, Mw -1700)
, 0.140g・Victoria Blue BOH [manufactured by Odogaya Chemical ■] 0.122
g・Ethyl cellosolve・Methylcarpitol 511! l
The coating weight after drying was approximately 22 mg/dm2.

The obtained photosensitive lithographic printing plate (A) was free from streak-like unevenness and wavy density unevenness caused by the above-mentioned bubbles, had good coating properties, and had a photosensitive layer with a uniform thickness.

(Example 2) A photosensitive coating solution having the following composition was coated on an aluminum support treated in the same manner as in Example 1 in the same manner as in Example 1, and when dried, wavy unevenness in density was observed. A photosensitive lithographic printing plate having excellent coating properties and a photosensitive layer having a uniform thickness was obtained.

(Photosensitive coating liquid composition) 2,3.4-trihydroxybenzophenone (1.
2)-Naphthoquinone cyasito-5-sulfonic acid triester 3.50g・N- (
A copolymer consisting of 4-hydroxyphenyl) methacrylamide, acrylonitrile, and methyl methacrylate.
The molar ratio of each charge is 30: 30: 401, and the weight average molecular weight Mw = 2. O x 10' number average molecular weight M port = 1. OxlQ3 11.0g・Fluorine surfactant (exemplified compound (4)) 0.05g・p −
LerL-novolak resin synthesized from octylphenol and formaldehyde and naphthoquinone-(1.2
)-diazide-(2)-esterification with 5-sulfonic acid chloride & (condensation rate 5.

son Mw = 1700)
0.16g Victoria Pure Blue BOH [manufactured by Odugaya Chemical] 0.10
g. Ethyl cellosolve 1001 coats The coating weight after drying was approximately 22 g/dws2.

The resulting photosensitive lithographic printing plate had no streak-like unevenness or wavy density unevenness caused by the above-mentioned bubbles, had good coating properties, and had a photosensitive layer with a uniform thickness.

(Comparative Example 1) A photosensitive lithographic plate was prepared in the same manner as in Example 1, except that the fluorine-based surfactant (exemplified compound (2)) in the photosensitive coating solution of Example 1 was changed to the following fluorine-based surfactant. Got the print version.

The resulting photosensitive lithographic printing plate had streak-like unevenness caused by the above-mentioned bubbles, had poor coating properties, and was unable to obtain a uniform photosensitive layer.

Fluorine surfactant CF: I (CFt): + 0C2H4S03 N- (Comparative Example 2) Except for excluding the fluorine surfactant (exemplified compound ¥k (2)) in the photosensitive coating liquid of Example 1. A photosensitive lithographic printing plate was obtained in the same manner as in Example 1.

The resulting photosensitive lithographic printing plate had wavy density unevenness,
A photosensitive layer with uniform thickness could not be obtained.

(Comparative Example 3) A photosensitive lithographic plate was prepared in the same manner as in Example 2, except that the fluorine-based surfactant (exemplified compound (4)) in the photosensitive coating liquid of Example 2 was changed to the fluorine-based surfactant shown below. Got the print version.

The resulting photosensitive lithographic printing plate had streak-like unevenness caused by the above-mentioned bubbles, and a photosensitive lithographic printing plate with a uniform film thickness could not be obtained.

Fluorine surfactant CF, SO2NC2H, N◆(C2Hs)2C1 (Comparative Example 4) The fluorine surfactant (exemplified compound ¥IIJ (4)) in the photosensitive coating liquid of Example 2 was mixed with the following fluorine surfactant. A photosensitive lithographic printing plate was obtained in the same manner as in Example 2 except that the activator was changed.

The resulting photosensitive lithographic printing plate had streak-like unevenness caused by the above-mentioned bubbles, and a photosensitive lithographic printing plate with a uniform film thickness could not be obtained.

Fluorine surfactant CF: +(CF2)tsOJ(CJs) (CH2CH
20) toH (Comparative Example 5) Same as Example 2 except that the fluorine-based surfactant (exemplary compound (4)) in the photosensitive coating liquid of Example 2 was removed.
A photosensitive lithographic printing plate was obtained.

The obtained photosensitive lithographic printing plate had wavy density unevenness, and a photosensitive layer with a uniform thickness could not be obtained.

(Example 3) An aluminum plate having a thickness of 0.24I was grained by electrolytic etching, then anodized, and then sealed with an aqueous sodium metasilicate solution.The following composition was applied to an aluminum support. When the photosensitive coating liquid was applied in the same manner as in Example 1 and dried, a photosensitive lithographic printing plate was obtained which had a photosensitive layer with a uniform thickness and no wavy density unevenness or streaks caused by wrinkles. Obtained.

(Photosensitive coating liquid composition) - N-(4-hydroxyphenyl) methacrylamide,
Copolymer consisting of acrylonitrile, methyl methacrylate and methacrylic acid (described in JP-A-54-98614, Example 2) 5 g Berchlorate salt of a condensate of p-diazophenylamine and formaldehyde 0.5 g・Oil Blue #503 [Manufactured by Orient Chemical Industry Co., Ltd.] 0.1g
・Fluorine surfactant (exemplary compound (3)) 0.0:l
g ・Methyl cellosolve 98 mm ・Butyl cellosolve 2 m thick (Example 4) A photosensitive coating liquid with the following composition was applied on the same 0.24 mm thick aluminum plate as in Example 1 in the same manner as in Example 1, and dried. As a result, a photosensitive lithographic printing plate having a photosensitive layer with no uneven coating and a uniform thickness was obtained.

(Photosensitive coating liquid composition) - β-type copper phthalocyanine pigment chromophthal blue-4O
N (manufactured by Ciba Geigy) 3.3 g・Oxadiazole compound (compound described in JP-A-55-161250, Example 1) 2.31 g
l-cresol formadehyde resin 19.8 g
Fluorine surfactant (exemplary compound (1)) o, os
g - Ethyl cellosolve 90 ■ text - Butyl cellosolve 10 ■ (Example 5) A photosensitive coating liquid with the following composition was applied on the same 0.24 m5 thick aluminum plate as in Example 1 in the same manner as in Example 1. When dried, a photosensitive lithographic printing plate having a photosensitive layer with no uneven coating and a uniform thickness was obtained.

(Photosensitive coating liquid composition) - Photosensitive polyester which is a composite of phenylene diethyl acrylate, hydrogenated bisphenol and triethylene glycol (compound described in Example 1 of 41\Kaikai Publication No. 1983-40415) 4g.2 -dibenzoylmethylene-3-methylnaphthothiazoline
0.2g・phthalocyanine pigment
0.8g・Fluorine surfactant (exemplary compound (2)) 0.02g・Cyclohexanone
100 TA [Effect of the Invention] As explained above, according to the manufacturing method of the present invention, a photosensitive layer having a uniform thickness without coating unevenness such as streak-like unevenness or wavy density unevenness due to generation of bubbles can be obtained. A lithographic printing plate can be obtained.

Claims (1)

[Claims] (1) A photosensitive composition containing at least a photosensitive substance and a fluorosurfactant of the following structural formula [I] is dissolved in a solvent, and then applied onto a support and dried. A method for producing a photosensitive lithographic printing plate. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (In the formula, R^1 represents an alkyl group, R^2 represents an alkylene group and/or a fluorinated alkylene group, and R^
3 represents an alkyleneoxy group and/or a fluorinated alkyleneoxy group, a represents a number from 1 to 10, and b is 1
Represents the number ~30. However, R^3 contains at least one fluorinated alkyleneoxy group. )