JPH05181266A - Photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive compsn. ensuring improved appliability and preservability of a photosensitive soln., giving an excellent visible image by exposure and having excellent solubility in a solvent. CONSTITUTION:This photosensitive compsn. contains a fluorine-contg. surfactant made of a copolymer of acrylate or methacrylate (A) contg. a 6-20C fluoro- aliphatic group having >=30wt.% fluorine content with (polyoxyalkylene) acrylate or (polyoxyalkylene) methacrylate (B). The copolymer has 1,000-6,000mol.wt. and contains 10-25wt.% of the monomer A. The fluoro-aliphatic group is preferably a perfectly fluorinated aliphatic group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition containing a fluorine-containing surfactant, and more specifically, not only the coating property is improved, but also the storage stability of the photosensitive solution is improved and the exposure visible image property is improved. And a photosensitive composition excellent in solvent solubility.

[0002]

BACKGROUND OF THE INVENTION A photosensitive composition is dissolved in a suitable solvent and then coated and dried on a support to produce, for example, a lithographic printing plate. Conventionally, in order to improve the coating property, the photosensitive composition is improved. A surfactant has been added to a solution in which is dissolved in JP-A-57-40249 and JP-A-57-178242.
Japanese Patent Laid-Open Publication No. 2003-242242 discloses that a uniform film thickness can be obtained by adding a fluorine-based surfactant to a photosensitive coating liquid and coating and drying the coating liquid without causing coating unevenness.

Further, for example, JP-A-54-135004,
In JP 62-170950 A and JP 62-226143 A, a uniform film thickness is obtained by using a photosensitive composition containing a high molecular acrylic surfactant containing a fluoroaliphatic group. No. 3, that is, improving the coating property of the photosensitive solution is disclosed.

However, this technique has a problem that the coating property is good but the storage property is poor, that is, the solvent solubility of the photosensitive composition is not sufficient, and a gel-like substance is generated after coating,
Further, when the generation is remarkable, there is a problem that it appears as a precipitate in the photosensitive solution. Further, the conventional fluorine-based surfactant has good coatability, but on the other hand, there is a problem that the exposure visible image property is deteriorated.

Therefore, as a result of various studies on the above problems, the present inventors have found that the initial purpose can be achieved by defining the number of carbon atoms of the fluoroaliphatic group and the fluorine content of the group. The present invention has been completed.

[0006]

OBJECTS OF THE INVENTION Accordingly, an object of the present invention is to provide a photosensitive composition which not only improves the coating property but also improves the storage stability of the photosensitive solution and is excellent in the visible image visibility and the solvent solubility. It is in.

[0007]

The above object of the present invention is to provide a photosensitive composition containing a fluorosurfactant, wherein the fluorosurfactant is a copolymer of 1) and 2) below. The average weight molecular weight of the polymer is 1000 to 6000, and the content of 1) is 10 to 25% by weight based on the weight of the copolymer.
This is achieved by a photosensitive composition having the above characteristics. 1) Acrylate or methacrylate containing a fluoroaliphatic group having 6 to 20 carbon atoms and a fluorine content of 30% by weight or more 2) (polyoxyalkylene) acrylate or (polyoxyalkylene) methacrylate

The present invention will be described in more detail below. The present invention not only improves the coatability by using a fluorine-based surfactant that satisfies the above conditions, but also improves the storability of a photosensitive solution, and is a photosensitive composition excellent in exposure visibility and solvent solubility. Is obtained.

The fluorosurfactant used in the present invention is a copolymer of 1) and 2) shown below, which has a weight average molecular weight of 1000 to 6000 and occupies 1) of the copolymer. A compound having a content of 10 to 25% by weight is used. Here, 1) is an acrylate or methacrylate having 6 to 20 carbon atoms and a fluoroaliphatic group having a fluorine content of 30% by weight or more,
2) is (polyoxyalkylene) acrylate or (polyoxyalkylene) methacrylate.

Next, 1) and 2) will be described in detail. The higher the degree of fluorination, the more preferable the fluoroaliphatic group contained in 1) is, and the most preferable one is a fat having completely fluorinated --C _n F _{2n + 1} (n is an integer of 6 or more and 20 or less). It is a family group. If the fluorine content is less than 30% by weight, the effect of improving the coatability may be poor, or the effect may not be seen. Also,
If the number of carbon atoms is 5 or less, the effect of coating is weak even if the alkyl group is completely fluorinated. If the number of carbon atoms is 21 or more, the solvent solubility is poor, and precipitation occurs when the photosensitive solution is left for a long time. Not preferable. More preferably, it has 8 to 14 carbon atoms.

Further, the copolymer may contain a mixture of monomers having fluoroaliphatic groups having different carbon numbers. Also in this case, the number of carbon atoms of the fluoroaliphatic group contained in the structural unit represented by 1) in the copolymer is 6 or more and 2
It is necessary to be less than 0, and it is most preferable to contain only 8 or more and 14 or less.

The fluoroaliphatic group preferably has an ester bond or an amide bond with the main chain when the copolymer is formed. Therefore, a preferred example of the structural unit represented by 1) is the above-mentioned fluoroaliphatic group represented by Rf
Then, it is expressed as follows.

[0013]

[Chemical 1]

Although the case of acrylate is shown above, the case of methacrylate is also preferably used. Next, the carbon number of the polyoxyalkylene group contained in 2) copolymerizable with 1) is preferably 2 or 3.
Those having different carbon numbers may be mixed in the two polyoxyalkylene groups.

When the content of 1) contained in the copolymer is 10% by weight or less, the effect of improving the coatability is poor,
If it exceeds 25% by weight, the visible image quality upon exposure deteriorates, which is not preferable. Further, the weight average molecular weight of the copolymer is 1000
If it is less than the above range, the effect of improving the coatability is weak, and if it is more than 6000, the storability of the photosensitive solution is deteriorated, which is not preferable. The fluorosurfactant of the present invention is 0.1 to 0.1 in the solid content of the photosensitive composition.
The content is 1.0% by weight, preferably 0.2 to 0.5% by weight.

The photosensitive composition of the present invention can include either a positive type photosensitive composition or a negative type photosensitive composition. The positive type photosensitive composition contains an orthoquinonediazide group. A polymer compound containing mainly is used, and the polymer compound containing an orthoquinonediazide group here is a condensation product of a compound containing an orthoquinonediazide group and an alkali-soluble resin or a compound containing an orthoquinonediazide group and a phenolic hydroxyl group. Used to mean either or both of the condensation products with low molecular weight compounds including.

The typical ones will be described below. Examples of the polymer compound containing an orthoquinone diazide group include ester compounds of o-naphthoquinone diazide sulfonic acid and a polycondensation resin of phenols and aldehydes or ketones.

Examples of the above-mentioned phenols include monophenols such as phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, carvacrol and thymol, catechol, resorcin, hydroquinone and the like. Examples thereof include trihydric phenols such as dihydric phenol, pyrogallol, and phloroglucin. Examples of the aldehyde include formaldehyde, benzaldehyde, acetaldehyde, crotonaldehyde, furfural and the like. Preferred of these aldehydes are formaldehyde and benzaldehyde.

Further, examples of the above-mentioned ketone include acetone and methyl ethyl ketone. Specific examples of the polycondensation resin include phenol / formaldehyde resin, m-cresol / formaldehyde resin, m-, p-
Mixed cresol / formaldehyde resin, resorcin /
Examples thereof include benzaldehyde resin and pyrogallol / acetone resin.

The condensation rate of o-naphthoquinonediazide sulfonic acid with respect to the OH group of the phenol of the o-naphthoquinonediazide compound (reaction rate with respect to one OH group) is 15 to 8
0% is preferable, and 20 to 45% is more preferable.
Further, as the o-quinonediazide compound used in the present invention, the compounds described in JP-A-58-43451 can also be used.

Of the above o-quinonediazide compounds, 1,2
-Benzoquinonediazide sulfonyl chloride or 1, 2
Most preferred is an o-quinonediazide ester compound obtained by reacting naphthoquinonediazidesulfonyl chloride with a pyrogallol-acetone condensation resin or 2,3,4-trihydroxybenzophenone.

As the o-quinonediazide compound used in the present invention, each of the above compounds may be used alone,
You may use combining 2 or more types of compounds. The polymer compound containing o-quinonediazide used in the present invention is
Considering coatability, those having a weight average molecular weight of 1500 or more are preferable, and those having a molecular weight of 2000 or more are more preferable.

The above-mentioned o-quinonediazide compound is preferably used as a mixture with an alkali-soluble resin. Examples of the alkali-soluble resin include novolac resins, vinyl polymers having a phenolic hydroxyl group, condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-55-57841, and the like. Examples of the novolac resin include phenol / formaldehyde resin, cresol / formaldehyde resin, JP-A-55-5784.
Phenol / cresol / formaldehyde copolycondensation resin as described in JP-A-55-12.
Examples thereof include a copolycondensation resin of p-substituted phenol and phenol or cresol and formaldehyde as described in Japanese Patent No. 7553.

Further, the vinyl polymer having a phenolic hydroxyl group is a polymer having a unit having the phenolic hydroxyl group in the molecular structure, and at least one of the following general formulas [1] to [5] Polymers containing one structural unit are preferred.

[0025]

[Chemical 2]

[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 is a hydrogen atom, an alkyl group,
It represents an aryl group or an aralkyl group, preferably a hydrogen atom. A represents an alkylene group which may have a substituent which connects a nitrogen atom or an oxygen atom and an aromatic carbon atom, m represents an integer of 0 to 10, and B may have a substituent. It represents a good phenylene group or a naphthylene group which may have a substituent. ]

As the polymer used in the photosensitive composition according to the present invention, those having a copolymer type structure are preferable, in combination with the structural units represented by the above general formulas [1] to [5]. Examples of the monomer unit that can be used include ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene, for example, styrene, α-methylstyrene, p-
Styrenes such as methylstyrene and p-chlorostyrene,
For example, acrylic acid, acrylic acid such as methacrylic acid, for example, itaconic acid, maleic acid, unsaturated aliphatic dicarboxylic acids such as maleic anhydride, such as methyl acrylate, ethyl acrylate, acrylic acid-n-butyl, isobutyl acrylate, Dodecyl acrylate, -2-chloroethyl acrylate,

Phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate,
Esters of α-methylene aliphatic monocarboxylic acids such as ethyl ethacrylic acid, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide, such as acrylanilide, p-chloroacrylamide, m-nitroacrylanilide, m -Anilides such as methoxyacrylanilide, for example vinyl acetate, vinyl propionate, vinyl benzoate,

Vinyl butyrate and other vinyl esters, such as methyl vinyl ether, ethyl vinyl ether, isobuty vinyl ether, β-chloroethyl vinyl ether and other vinyl ethers, vinyl chloride, vinylidene chloride, vinylidene cyanide, such as 1-methyl-1-
Methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene,
Ethylene derivatives such as 1-methyl-1-nitroethylene, such as N-vinylpyrrole, N-vinylcarbazole,
There are N-vinyl type monomers such as N-vinylindole, N-vinylpyrrolidene and N-vinylpyrrolidone. These vinyl-based monomers are present in the polymer compound with a structure in which the unsaturated double bond is cleaved.

Of the above monomers, aliphatic monocarboxylic acid esters and nitriles are preferable because they exhibit excellent performance for the purpose of the present invention. These alkali-soluble resins preferably have a molecular weight of 1500 or more, more preferably 2000 or more, in consideration of coatability.

In addition to the above-mentioned materials, these photosensitive compositions may contain dyes such as dyes and pigments, dyes, sensitizers, plasticizers, surfactants, organic acids, acid anhydrides and, if necessary, light exposure. A compound capable of generating an acid can be added. There are various negative photosensitive materials used in the present invention,
A typical one will be described as described below.

(1) Photosensitive Composition Containing Diazo Resin The diazo resin represented by the condensation product of p-diazodiphenylamine and formaldehyde may be water-soluble or water-insoluble, but is preferably JP-B-47. -116
Water-insoluble and ordinary organic solvent-soluble substances such as those described in JP-A No. 7 and 57-43890 are used. Particularly preferred is a diazo resin represented by the following general formula [6].

[0033]

[Chemical 3]

[In the formula, R ¹ , R ² and R ³ represent a hydrogen atom, an alkyl group or an alkoxy group, and R ⁴ represents a hydrogen atom, an alkyl group or a phenyl group. X represents a PF ₆ or BF _4, Y is -NH -, - shows S- or -O-. ]

The diazo resin is preferably used as a mixture with a film-forming resin, particularly a lipophilic polymer compound having a hydroxyl group. As such a lipophilic polymer compound, in addition to those listed above, a monomer having an aliphatic hydroxyl group in its side chain, such as 2-hydroxyethyl acrylate or 2
-Hydroxyethyl methacrylate and other copolymerizable monomers. Besides these,
If necessary, polyvinyl butyral resin, polyurethane resin, polyamide resin, epoxy resin, novolac resin, natural resin and the like may be added.

As the binder used in combination with the diazonium salt, various polymer compounds can be used, but preferably a monomer having an aromatic hydroxyl group as described in JP-A-54-98613. , N- (4-hydroxyphenyl) acrylamide, N- (4-hydroxyphenyl) methacrylamide, o-, m-, or p-, for example.
Copolymers of hydroxystyrene, o-, m-, or p-hydroxyphenyl methacrylate with other monomers,

Polymers containing a hydroxyethyl acrylate unit or a hydroxyethyl methacrylate unit as a main repeating unit as described in US Pat. No. 4,123,276, natural resins such as shellac and rosin, polyvinyl alcohol, US Patent No. 3,7
51,257 polyamide resin, US Pat. No. 3,660,097 linear polyurethane resin, polyvinyl alcohol phthalated resin, bisphenol A and epichlorohydrin condensed Contains celluloses such as epoxy resin, cellulose acetate, and cellulose acetate phthalate.

Examples of the alkali-soluble resin include novolac resins, vinyl polymers having phenolic hydroxyl groups, condensation resins of polyhydric phenols and aldehydes or ketones described in JP-A-55-57841. .. Examples of the novolak resin include phenol / formaldehyde resin, cresol / formaldehyde resin, phenol / cresol / formaldehyde copolycondensation resin as described in JP-A-55-57841, and JP-A-55-127553. P-substituted phenol and phenol as described, or
Examples thereof include copolymer resins of cresol and formaldehyde.

These binders are contained in the solid content of the photosensitive composition in an amount of 40 to 99% by weight, preferably 50 to 95% by weight. The diazo resin is contained in an amount of 1 to 60% by weight, preferably 3 to 30% by weight. In addition to the above materials, these photosensitive compositions may further contain dyes such as dyes and pigments, sensitizers, plasticizers, surfactants, organic acids, acid anhydrides, and acids by exposure, if necessary. Generating compounds can be added.

(2) --CH.dbd.C in the main chain or side chain of the polymer
Photosensitive Composition Containing Polymer Compound Having H—CO— Group As such a polymer compound, polyesters containing —CH═CH—CO— as a photosensitive group in the main chain or side chain of the polymer, Those containing a photosensitive polymer such as polyamides and polycarbonates as a main component (for example, described in U.S. Pat. Nos. 3,030,208, 3,707,373 and 3,453,237). Such compounds);

Photosensitive polyesters derived from (2-properidene) malonic acid compounds such as cinnamylidene malonic acid and bifunctional glycols as main components (eg, US Pat. No. 2,956,878 and Same 3rd
173,787 to a photosensitive polymer as described in each specification);

Cinnamic acid esters of hydroxyl-containing polymers such as polyvinyl alcohol, starch, cellulose and the like (eg, US Pat. No. 2,690,966,
Polymers such as those described in each specification of No. 2,752,372, No. 2,732,301 and the like. These photosensitive compositions may contain other sensitizers, stabilizers, plasticizers, pigments, dyes and the like.

(3) Photopolymerizable Composition Comprising Addition-Polymerizable Unsaturated Compound This composition preferably comprises (a) a monomer having at least two terminal vinyl groups, and (b) a photopolymerization initiator. And (c) a polymer compound as a binder.

As the vinyl monomer of this component (a),
Japanese Patent Publication Nos. 35-5093, 35-14719, 4
It is described in each publication of 4-28727. For example, acrylic acid or methacrylic acid ester of polyol, that is, diethylene glycol (meth) acrylate, triethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, or methylenebis (meth) acrylamide. , Bis (meth) acrylamides such as ethylene bis (meth) acrylamide,
Or an unsaturated monomer containing a urethane group,

For example, a diol mono (meth) acrylate such as di- (2'-methacryloxyethyl) -2,4-tolylenediurethane, di- (2-acryloxyethyl) trimethylenediurethane and a diisocyanate. Examples include reaction products. As the photopolymerization initiator of the component (b), the compound represented by the general formula [6] can be used, but other types can also be used.

For example, the above-mentioned J. There are carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes as described in Chapter 5 of "Light Sensitive Systems" by Kosar. More specifically, it is disclosed in British Patent No. 1,459,563.

The following can be used as the photopolymerization initiator. Benzoin methyl ether, benzoin isopropyl ether, α, α-dimethoxy-
Benzoin derivatives such as α-phenylacetophenone, benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone Benzophenone derivative,

Thioxanthone derivatives such as 2-chlorothioxanthone and 2-isopropylthioxanthone, anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone, acridone derivatives such as N-methylacridone and N-butylacridone, α and α -Diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compounds, halogen compounds and the like.

Further, as the binder of the component (c),
Various known polymers can be used. Specific binder details are described in US Pat. No. 4,072,527.
No. In addition, the binder used when used in combination with the above-mentioned diazonium salt is used. These photopolymerizable compositions may contain a thermal polymerization inhibitor, a plasticizer, a dye, a pigment and the like.

(4) Photosensitive Composition Containing Azide Group As the photosensitive azide compound, an aromatic azide compound in which an azido group is bonded to an aromatic ring directly or through a carbonyl group or a sulfonyl group is preferably used. ..

For example, polyazidostyrene, polyvinyl-p-azidobenzoate, polyvinyl-p- as described in US Pat. No. 3,096,311.
Azidobenzal, a reaction product of an azidoarylsulfonyl chloride with an unsaturated hydrocarbon polymer described in JP-B-45-9613, and JP-B-43-2101.
No.7, No.44-229, No.44-22954, No.4
Examples thereof include polymers having a sulfonyl azide or a carbonyl azide as described in JP-A Nos. 5-24915.

An oil sensitizer added to the photosensitive composition,
Additives such as surfactants, sensitizers, stabilizers, thermal polymerization inhibitors, plasticizers, and dyes such as dyes and pigments are generally contained in the photosensitive coating liquid, although the addition amount varies depending on the type. 0.01 to 20% by weight, preferably 0.05 to 10% by weight, is suitable for the photosensitive composition.

In the present invention, various compounds are used as an oil sensitizer, but a resin obtained by condensing a substituted phenol and an aldehyde represented by the following general formula [7] and an orthonaphtho of the resin are used. A quinonediazide sulfonic acid ester compound is preferably used.

[0054]

[Chemical 4]

[In the formula, R ₁ and R ₂ represent a hydrogen atom, an alkyl group or a halogen atom, and R ₃ represents an alkyl group having 2 or more carbon atoms or a cycloalkyl group. The alkyl group of R ₁ and R ₂ represented by the general formula [7] is an alkyl group having 1 to 3 carbon atoms, and an alkyl group having 1 or 2 is particularly preferable. R ₃ is preferably an alkyl group having 15 or less carbon atoms or a cycloalkyl group, and particularly preferably an alkyl group having 3 to 8 carbon atoms or a cycloalkyl group.

Examples of the substituted phenols represented by the general formula [7] include isopropylphenol, t-butylphenol, t-amylphenol, hexylphenol, octylphenol, cyclohexylphenol,
3-methyl-4-chloro-5-t-butylphenol,
Isopropylcresol, t-butylcresol, t-
Amylcresol, hexylcresol, octylcresol, cyclooctylcresol and the like, of which octylphenol and t-butylphenol are particularly preferable.

Examples of the aldehydes include aliphatic and aromatic aldehydes such as formaldehyde, benzaldehyde, acetaldehyde, acrolein, crotonaldehyde and furfural, which have 1 to 7 carbon atoms.
Aldehydes are preferred. Particularly preferred are formaldehyde and benzaldehyde.

The resin obtained by condensing the above-mentioned substituted phenols and aldehydes used in the present invention can be obtained by polycondensing these under an acidic catalyst. Further, the orthonaphthoquinonediazide sulfonic acid ester of the resin is esterified by dissolving the condensed resin in a suitable solvent, adding orthonaphthoquinone diazide sulfonic acid chloride to this, and adding an alkali to the equivalent point while heating and stirring. can get.

The dyes preferably used in the present invention include basic dyes and oil-soluble dyes. In particular,
Victoria Pure Blue BOH, Victoria Blue BH, Methyl Violet, Aizen Malachite Green (above, Hodogaya Chemical Co., Ltd.), Patent Pure Blue VX, Rhodamine B, Methylene
Basic dyes such as blue (above, manufactured by Sumitomo Chemical Co., Ltd.), as well as Sudan Blue II, Victoria Blue F4
R (above, BASF) Oil Blue # 60
3, oil blue BOS, oil blue IIN
(Above, manufactured by Orient Chemical Industry) and the like oil-soluble dyes.

A positive type photosensitive lithographic printing plate can be formed by dissolving the photosensitive composition of the present invention in a solvent capable of dissolving the above components and coating and drying the solution on a suitable support surface. .. Examples of the solvent that can be used include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butanol, isobutanol, t-butanol, 1-pentanol, 2-pentanol and 1-hexanol, Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl iso

Ketones such as butyl ketone, cyclopentanone, cyclohexanone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Ethylene glycols such as ethylene glycol-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol isopropyl ether acetate, diethylene glycol monomethyl ether,
Diethylene glycol monoethyl ether, diethylene glycol isopropyl ether, diethylene glycol phenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether

Ether, diethylene glycols such as diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycols such as propylene glycol isopropyl ether, ethyl acetate, n-propyl acetate, Acetates such as isopropyl acetate and butyl acetate, other water, methyl lactate, ethyl lactate, diethyl ether, dioxane, dimethylformamide, dimethylsulfoxide, γ-butyrolactone, 3-methoxy-1-butanol, 3-methyl-3-butane.
Methoxy-1-butanol, tetrahydrofuran, methylene chloride and the like can be mentioned.

As the support suitable for producing the photosensitive printing plate by applying the photosensitive coating solution of the present invention, various supports can be used. For example, metal plates such as aluminum, zinc, copper and steel can be used. , And metal plates plated or vapor-deposited with chromium, zinc, copper, nickel, aluminum, etc., hydrophilized paper and plastics, and papers and plastic films vapor-deposited with metal, glass plates, resin-coated paper, aluminum, etc. Examples thereof include paper covered with metal foil. Among these, an aluminum plate is preferable.

Particularly in the case of an aluminum plate support,
Surface treatment such as graining treatment, anodizing treatment and, if necessary, sealing treatment is preferably performed. As the method for graining, a technique of degreasing the surface of an aluminum plate or the like and then applying a brush polishing method, a ball polishing method, a chemical polishing method, an electrolytic etching method, or the like is adopted.

The above anodic oxidation treatment is carried out, for example, in an inorganic salt such as phosphoric acid, chromic acid, boric acid, sulfuric acid, etc., or oxalic acid, sulfamic acid, etc. alone or in an aqueous solution or a non-aqueous solution in which two or more kinds of these acids are mixed. , An aluminum plate or the like as an anode and an electric current is passed through.

Further, the sealing treatment is carried out with an aqueous solution of sodium silicate,
It is carried out by dipping in hot water and a hot aqueous solution of some inorganic or organic salt, or by a steam bath. In the present invention,
The coating amount of the photosensitive coating liquid on the support varies depending on the use, but generally, a solid content of 0.5 to 3.5 g / m ² is suitable.

The coating solution of the present invention can be applied by dip coating, roll coating, reverse roll coating, air doctor coating, blade coating, rod coating, knife coating, squeeze coating, gravure coating, cast coating, curtain coating, extrusion. The coating film thickness is 0.1.
~ 5 g / m ² is preferred. The drying temperature is 20 to 150.
C., preferably 30 to 100.degree.

[0068]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto. Example 1 A photosensitive solution having the following composition was prepared, and a solid content was prepared by using a roll coater on a grained aluminum plate.
After coating so as to have a coating amount of ² g / m ² , it was dried to obtain a sample of a photosensitive lithographic printing plate.

[Photosensitive solution] Ester compound of pyrogallol-acetone resin and naphthoquinone- (1,2) -diazide-5-sulfonic acid chloride (weight average molecular weight 2500) 2.3 parts by weight Phenol and m-, p- Copolymer resin of mixed cresol (each molar ratio 48:32:20) and formaldehyde (average molecular weight 8000) 6.7 parts by weight 2-trichloromethyl-5- (β-benzofurylvinyl) -1,3 4-Oxadiazole 0.05 part by weight Victoria Pure Blue BOH 0.07 part by weight Fluorosurfactant (shown in Table 1) 0.003 part by weight Ethylene glycol monomethyl ether 45.0 parts by weight

Table 1 shows the results of evaluation of the coating property and the visible image quality of this photosensitive lithographic printing plate sample. The conditions for evaluating the visibility of exposure are as follows. Exposure: Idle Fin 2000 (manufactured by Iwasaki Electric Co., Ltd.) Measurement: Sakuradensitometer (manufactured by Konica) After measuring the reflection density with a red filter, calculate the difference (ΔD) between the exposed and unexposed areas

Next, the photosensitive solution was placed in a closed container,
After storing at 30 ° C. for 7 days, the presence or absence of precipitation of the photosensitive solution and the exposed and visible image quality of the sample after coating were evaluated in the same manner as in the case of no storage. The results of these evaluations are also shown in Table 1.
Shown in.

[Evaluation Rank] (Applicability) A: No coating unevenness is observed. B: Slight uneven coating is observed. C: Coating unevenness is remarkably generated.

(Precipitation) A: No precipitation. B: Precipitation is observed when filtered through filter paper. (No precipitation is visually observed.) C: Precipitation is clearly observed visually. The fluorosurfactants used in Tables 1 and 2 are copolymers obtained by polymerizing the following monomers in the composition ratios (weight ratios) shown in Tables 1 and 2.

[0074]

[Chemical 5]

[0075]

[Table 1]

Example 2 A sensitizing solution having the following composition was prepared, and these were coated on a grained aluminum plate using a roll coater so that the coating amount of the solid content was 1.6 g / m ² , and then dried. Then, a sample of a photosensitive lithographic printing plate was obtained.

[Photosensitive liquid] Charged monomer molar ratio: N- (4-hydroxyphenyl) methacrylic acid / acrylonitrile / ethyl acrylate / methacrylic acid / n-butyl acrylate = 8/32/40/10/10 Copolymer (Mw = 55000) obtained by the method described in Synthesis Example 1 described in JP-A-62-7045 6.0 parts by weight p-diazodiphenylamine and paraformaldehyde (molar ratio 1: 0.9 ) And a condensation resin hexafluorophosphate (Mw = 2400) 0.48 parts by weight Jerimer AC-10L (Nippon Pure Chemicals) 0.36 parts by weight Victoria Pure Blue BOH 0.09 parts by weight Fluorine-based surfactant (Shown in Table 2) 0.003 parts by weight Ethylene glycol monomethyl ether 45.0 parts by weight

The light-sensitive lithographic printing plate sample was evaluated for coatability, exposure visibility and presence / absence of precipitation of a photosensitive solution after storage at 30 ° C. for 7 days in a closed container, and exposure visibility of the coated sample. The results obtained are shown in Table 2. Note that these evaluation methods and evaluation criteria are exactly the same as in Example 1.

[0079]

[Table 2]

[0080]

INDUSTRIAL APPLICABILITY According to the present invention, by containing a specific fluorine-containing surfactant in the photosensitive composition, the coating property is improved and the solubility and storability of the photosensitive solution are improved. Excellent results are obtained.

Claims (1)

[Claims] 1. A photosensitive composition containing a fluorosurfactant, wherein the fluorosurfactant is the copolymer of 1) and 2) below, and the weight average molecular weight of the copolymer is 1000. To 6000, and the content of 1) is 10 to 25% by weight or more based on the weight of the copolymer. 1) Acrylate or methacrylate containing a fluoroaliphatic group having 6 to 20 carbon atoms and a fluorine content of 30% by weight or more 2) (polyoxyalkylene) acrylate or (polyoxyalkylene) methacrylate