JPH08160611A - Photosensitive composition and photosensitive lithographic printing plate - Google Patents

Abstract

PURPOSE: To provide a photosensitive composition preventing such problems as sensitivity reduction and deterioration of developing property and having high plate wear resistance by containing a o-quinone diazide compound and using a specific binder. CONSTITUTION: This photosensitive composition contains a polymer compound with the side chain having the repetitive structural unit expressed by the formula and a o-quinone diazide compound. In the formula, R<1> and R<2> indicate the hydrogen atom or the alkyl group or phenyl group having the carbon number of 1-12, and (m) indicates an integer of 1-5. The usable ortho-quinone azide compound is not limited in particular, and an ester compound with a condensation polymerization resin having the ortho-quinone azide group, e.g. the condensation polymerization resin made of o-naphthoquinone diazide sulfonic acid, phenols, and aldehyde or ketone, may be used. A polymer compound copolymerized with a macromonomer having polymerization unsaturated bond on one terminal of polypropylene glycol or polyethylene glycol and another vinyl monomer may be used for the polymer compound, for example.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive composition and a photosensitive lithographic printing plate, and more specifically, it has no problems such as reduction in sensitivity and deterioration in developability and has excellent printing durability. It relates to a photosensitive composition and a photosensitive lithographic printing plate.

[0002]

BACKGROUND OF THE INVENTION A photosensitive lithographic printing plate is one in which a photosensitive layer is provided on a hydrophilic support. For example, in a positive type photosensitive lithographic printing plate, an actinic ray such as ultraviolet rays is provided on the hydrophilic support. An ink-receptive photosensitive layer that is solubilized by exposure to is formed.

In such a positive-working photosensitive lithographic printing plate, when the photosensitive layer is imagewise exposed and then developed, the ink-receptive photosensitive layer in the exposed area is removed to expose the surface of the hydrophilic support. On the other hand, the unexposed portion of the photosensitive layer which is ink-receptive remains on the support to form an ink-receptive layer. In lithographic printing, the difference in the property that the exposed portion is hydrophilic and the unexposed portion is lipophilic is used.

The orthoquinonediazide compound forms a carboxylic acid upon irradiation with actinic rays and becomes soluble in an aqueous alkaline developing solution. Therefore, this property is utilized as a photosensitive material for a positive type photosensitive lithographic printing plate.

Usually, a positive-working photosensitive lithographic printing plate using an orthoquinonediazide compound has a photosensitive layer containing the orthoquinonediazide compound formed on a roughened and anodized aluminum support.

These photosensitive lithographic printing plates are required to have high printing durability.

Generally, as a technique for improving the printing durability, there are generally known techniques such as (1) increasing the molecular weight of the binder in the photosensitive composition and (2) increasing the molecular weight of the photoconductor. However, if the printing durability is improved by these techniques, problems such as a decrease in sensitivity and deterioration of developability will occur.

Then, the inventors of the present invention have studied and found that o
-In a photosensitive composition containing a quinonediazide compound, it has been found that by using a specific binder, there is no problem such as sensitivity deterioration and deterioration of developability, and the printing durability can be improved. .

[0009]

OBJECTS OF THE INVENTION Accordingly, an object of the present invention is to provide a photosensitive composition and a photosensitive lithographic printing plate which have no problems such as sensitivity deterioration and deterioration of developability and have high printing durability. is there.

[0010]

The above objects of the present invention are as follows: (1) Containing a polymer compound having a side chain having a repeating structural unit represented by the following general formula [I] and an o-quinonediazide compound. A photosensitive composition comprising:

[0011]

Embedded image [In formula, R < ¹ > and R < ² > represents a hydrogen atom, a C1-C12 alkyl group, or a phenyl group, and m represents the integer of 1-5. (2) A photosensitive lithographic printing plate comprising a support having a hydrophilic surface and a photosensitive layer comprising the photosensitive composition according to (1) above. Achieved by

The present invention will be described below.

The orthoquinonediazide compound used in the photosensitive composition of the present invention is a compound having an orthoquinonediazide group in the molecule, and the orthoquinonediazide compound which can be used in the present invention is particularly limited. Instead, for example, a polycondensation resin having an orthoquinonediazide group, for example, an ester compound of an o-naphthoquinonediazide sulfonic acid and a polycondensation resin of a phenol and an aldehyde or a ketone, and the like can be mentioned.

Examples of the phenols in the polycondensation resin with the above phenols and aldehydes or ketones include phenol, o-cresol, m-cresol,
Examples include monohydric phenols such as p-cresol, 3,5-xylenol, carvacrol, thymol, dihydric phenols such as catechol, resorcin, and hydroquinone, and trihydric phenols such as pyrogallol and phloroglucin. Examples of the aldehyde include formaldehyde,
Examples thereof include benzaldehyde, acetaldehyde, crotonaldehyde, furfural and the like. Of these, preferred are formaldehyde and benzaldehyde. Examples of ketones include acetone and methyl ethyl ketone.

Specific examples of polycondensation resins with phenols and aldehydes or ketones include phenol-formaldehyde resin, m-cresol-formaldehyde resin, m-, p-mixed cresol-formaldehyde resin, resorcin-benzaldehyde resin, Examples include pyrogallol / acetone resin.

In the o-naphthoquinonediazide compound, the condensation rate of o-naphthoquinonediazide sulfonic acid with respect to the OH group of phenols (reaction rate with respect to one OH group) is preferably 15% to 80%, more preferably 2%.
It is 0% to 45%.

Further, as the orthoquinonediazide compound used in the present invention, the following compounds described in JP-A-58-43451 can also be mentioned. That is, for example, 1,2-benzoquinone diazide sulfonic acid ester, 1,2-naphthoquinone diazide sulfonic acid ester, 1,2-benzoquinone diazide sulfonic acid amide,
Known 1,2-quinonediazide compounds such as 1,2-naphthoquinonediazide sulfonic acid amide, and more specifically, J. Kosar "Light-Sensitive Systems" No. 339. Pp. 352 (1965), John Willie
And Sons (John Willey & Sons) (New York) and W S De Forest (WSDe F)
1,2-benzoquinonediazide-4-sulfonic acid phenyl ester, 1, described in "Photoresist", Vol. 50 (1975), McGraw Hill, Inc. (New York).
2,1 ′, 2′-di- (benzoquinonediazide-4-sulfonyl) -dihydroxybiphenyl, 1,2-benzoquinonediazide-4- (N-ethyl-N-β-naphthyl) -sulfonamide, 1,2- Naphthoquinonediazide-5-sulfonic acid cyclohexyl ester, 1- (1,
2-naphthoquinonediazide-5-sulfonyl) -3,5
-Dimethylpyrazole, 1,2-naphthoquinonediazide-5-sulfonic acid-4'-hydroxydiphenyl-4 '
-Azo-β-naphthol ester, N, N-di- (1,
2-naphthoquinonediazide-5-sulfonyl) -aniline, 2 '-(1,2-naphthoquinonediazide-5-sulfonyloxy) -1-hydroxy-anthraquinone,
1,2-naphthoquinonediazide-5-sulfonic acid-2,
4-dihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid-2,3,4-trihydroxybenzophenone ester, 1,2-naphthoquinonediazide-5-sulfonic acid chloride 2 mol and 4,
Condensate with 1 mol of 4'-diaminobenzophenone, 1,
2-naphthoquinonediazide-5-sulfonic acid chloride 2
, A condensate of 1,4'-dihydroxy-1,1'-diphenylsulfonic acid 1 mol, a condensate of 1,2-naphthoquinonediazide-5-sulfonic acid chloride 1 mol and purpurogallin 1 mol, 1,2 -Naphthoquinone diazide-
A 1,2-quinonediazide compound such as 5- (N-dihydroabietyl) -sulfonamide can be exemplified. In addition, Japanese Examined Patent Publications No. 37-1953 and 37-3627
Nos. 37-13109, 40-26126, 40-3801, 45-5604, 45-27.
No. 345, No. 51-13013, JP-A-48-965.
The 1,2-quinonediazide compounds described in JP-A No. 75, 48-63802 and 48-63803 can also be mentioned.

Of the above orthoquinonediazide compounds,
An o-quinone diazide ester compound obtained by reacting 1,2-benzoquinone diazide sulfonyl chloride or 1,2-naphthoquinone diazide sulfonyl chloride with pyrogallol-acetone condensation resin or 2,3,4-trihydroxybenzophenone is particularly preferable.

In the present invention, as the orthoquinonediazide compound, the above compounds may be used alone or in combination of two or more kinds.

The content of the orthoquinonediazide compound in the photosensitive composition is preferably 5 to 60% by weight, and particularly preferably 10 to 50% by weight.

Next, a polymer compound having a side chain having a repeating structural unit represented by the general formula [I] (hereinafter referred to as a polymer compound of the present invention) will be described.

[0022]

Embedded image [In formula, R < ¹ > and R < ² > represents a hydrogen atom, a C1-C12 alkyl group, or a phenyl group, and m represents the integer of 1-5. The polymer compound of the present invention may be any polymer compound having a side chain having a repeating structural unit represented by the general formula [I], and specific examples thereof include polypropylene glycol and polyethylene glycol. There can be mentioned a polymer compound obtained by copolymerizing a macromonomer having a polymerizable unsaturated bond at one of its terminals with another vinyl monomer.

Examples of macromonomers having a polymerizable unsaturated bond at one of the terminals of polypropylene glycol and polyethylene glycol include polypropylene glycol and polyethylene glycol, and acrylic acid, methacrylic acid, maleic acid, itaconic acid and the like. Can be mentioned.

Examples of the other vinyl-based monomers include (a) acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate. (B) α, β-unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic anhydride, and itaconic acid, (c) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, acrylic Hexyl acid, octyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, N
-(Substituted) alkyl acrylates such as dimethylaminoethyl acrylate, (d) methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N-dimethylaminoethyl methacrylate, etc. (Substituted) alkylmethacrylate, (e) acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-
Acrylamide or methacrylamide such as hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide, (f) ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, Vinyl ethers such as butyl vinyl ether, octyl vinyl ether and phenyl vinyl ether, (g) vinyl acetate, vinyl chloroacetate, vinyl butyrate,
Vinyl esters such as vinyl benzoate, (h) styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, (i) methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, phenyl vinyl ketone, etc. Vinyl ketones, (j) olefins such as ethylene, propylene, isobutylene, butadiene and isoprene, (k) N-vinylpyrrolidone, N
-Vinylcarbazole, 4-vinylpyridine, acrylonitrile, methacrylonitrile, etc. (l) vinyl monomer having an aromatic hydroxyl group, specifically, o, m, p-hydroxyphenyl (meth) acrylamide, o, m, p
-Hydroxystyrene, o, m, p-hydroxyphenyl (meth) acrylate, o, m, p-hydroxyphenyl maleimide and the like.

Further, the polymer compound of the present invention may be copolymerized with another monomer copolymerizable with the above-mentioned monomer.

As the polymer compound of the present invention, a vinyl monomer having an aromatic hydroxyl group as mentioned in (l) above,
In particular, a polymer compound having a phenolic hydroxyl group in the molecule obtained by copolymerizing with a vinyl monomer having a phenolic hydroxyl group is preferable.

The preferred molecular weight of the polymer compound of the present invention is 20,000 to 200,000, more preferably 30,000 to 130,000, and the preferred acid value is 100 or less.

In the side chain having the repeating structural unit represented by the general formula [I], the repeating number of the repeating structural unit represented by the general formula [I] is preferably 2 to 20, more preferably 3 to. Twelve.

The polymer compound of the present invention is preferably soluble in alkali. Here, the alkali-soluble not only refers to those that are soluble in alkaline water, but also includes those that are swellable in alkaline water.

Specific examples of the polymer compound of the present invention will be given below.

[0031]

[Chemical 4] The polymer compound of the present invention may be blended with another polymer compound.

Other alkali-soluble polymer compounds can be added to the photosensitive composition of the present invention.

The alkali-soluble resin that can be used is not particularly limited, and conventionally known ones can be used. Examples thereof include novolac resins, vinyl polymers having a phenolic hydroxyl group, and JP-A-55-57841.
Examples thereof include condensation resins of polyhydric phenols and aldehydes or ketones, which are described in Japanese Patent Laid-Open Publication No. 2003-242242.

Examples of the novolak resin which can be used in the present invention include phenol / formaldehyde resin, cresol / formaldehyde resin, JP-A-55.
-57841, a phenol-cresol-formaldehyde copolymer resin, as described in JP-A-55-127553.
Copolymer resins of substituted phenol and phenol or cresol and formaldehyde can be used.

The molecular weight (polystyrene standard) of the novolak resin is preferably 3.00 × 10 in terms of number average molecular weight Mn.
^{2 to} 7.50 × 10 ³ , weight average molecular weight Mw of 1.00 ×
10 ^{3 to} 3.00 × 10 ⁴ , more preferably Mn of 5.0
0 × 10 ^{2 to} 4.00 × 10 ³ , Mw of 3.00 × 10 ^3.
˜2.00 × 10 ⁴ .

The above novolak resins may be used alone or in combination of two or more kinds.

The vinyl polymer having a phenolic hydroxyl group is a polymer having a unit having the phenolic hydroxyl group in its molecular structure and is represented by the following general formula [II] to general formula [VI]. Polymers containing at least one structural unit are preferred.

[0038]

Embedded image

In the general formulas [II] to [VI], R
₁ and R ₂ each represent a hydrogen atom, an alkyl group or a carboxyl group, and preferably a hydrogen atom. R
₃ represents a hydrogen atom, a halogen atom or an alkyl group,
A hydrogen atom or an alkyl group such as a methyl group or an ethyl group is preferable. R ₄ and R ₅ represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and preferably a hydrogen atom. A represents an optionally substituted alkylene group that connects a nitrogen atom or an oxygen atom and an aromatic carbon atom, m represents an integer of 0 to 10, and B represents a substituent. Represents a phenylene group which may be substituted or a naphthylene group which may have a substituent.

The vinyl polymer having a phenolic hydroxyl group used in the present invention preferably has a copolymer type structure having the structural units represented by the general formulas [II] to [VI]. As the monomer to be copolymerized,
For example, ethylenically unsaturated olefins such as ethylene, propylene, isobutylene, butadiene and isoprene, for example, styrenes such as styrene, α-methylstyrene, p-methylstyrene and p-chlorostyrene, for example, acrylic acid and methacrylic acid. Acrylic acid, such as
For example, unsaturated aliphatic dicarboxylic acids such as itaconic acid, maleic acid and maleic anhydride, for example, methyl acrylate, ethyl acrylate, acrylic acid-n-butyl, isobutyl acrylate, dodecyl acrylate, acrylic acid-2- Chloroethyl, phenyl acrylate, α-methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, esters of α-methylene aliphatic monocarboxylic acid such as ethyl ethacrylate, for example, acrylonitrile, nitriles such as methacrylonitrile, for example. ,
Amides such as acrylamide, for example, acrylic anilide, p-chloroacrylanilide, m-nitroacrylanilide, m-methoxyacrylanilide, and other anilides, such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl acetate, etc. Vinyl esters,
For example, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, β-chloroethyl vinyl ether, vinyl chloride, vinylidene chloride, vinylidene cyanide, for example, 1
-Methyl-1-methoxyethylene, 1,1-dimethoxyethylene, 1,2-dimethoxyethylene, 1,1-dimethoxycarbonylethylene, 1-methyl-1-nitroethylene and other ethylene derivatives such as N-vinylpyrrole , N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidene and N-vinylpyrrolidone. These monomers are present in the polymer compound in a structure in which the unsaturated double bond is cleaved.

Of the above-mentioned monomers, aliphatic monocarboxylic acid esters and nitriles are preferable because they exhibit excellent performance for the purpose of the present invention.

These monomers may be bonded to the polymer used in the present invention in either a block or random state.

As the vinyl polymer having a phenolic hydroxyl group, the above polymers may be used alone or in combination of two or more kinds.

Further, a printout material capable of forming a visible image by exposure can be added to the photosensitive composition of the present invention. The printout material is composed of a compound that generates an acid or a free radical upon exposure to light and an organic dye that changes its color tone by interacting with the generated acid or a free radical. Examples of the compound include, for example, JP-A-50-3.
O-naphthoquinonediazide-4 described in Japanese Patent No. 6209
-Sulfonic acid halogenide, trihalomethyl-2-pyrone and trihalomethyl-triazine described in JP-A-53-36223, and o-naphthoquinonediazide-4-sulfonic acid chloride described in JP-A-55-6244. Ester compound or amide compound with phenols or aniline having an electron-withdrawing substituent, JP-A-55-55
-77742, JP-A-57-148784 and the like may be mentioned halomethylvinyloxadiazole compounds and diazonium salts. Examples of organic dyes include Victoria Pure Blue BOH.
(Hodogaya Chemical Co., Ltd.), Patent Pure Blue (Sumitomo Mikuni Chemical Co., Ltd.), Oil Blue # 603 (Orient Chemical Co., Ltd.), Sudan Blue II (BA
SF), crystal violet, malachite green, fuchsin, methyl violet, ethyl violet, methyl orange, brilliant green, congo red, eosin, rhodamine 66 and the like.

In addition to the above materials, a plasticizer, a surfactant, an organic acid, an acid anhydride and the like can be added to the photosensitive composition layer of the present invention, if necessary.

Further, in order to improve the oil sensitivity of the photosensitive composition, the photosensitive composition layer of the present invention contains, for example, p.
-Tert-butylphenol formaldehyde resin, p-
It is also possible to add an n-octylphenol formaldehyde resin or a resin in which these resins are partially esterified with an o-quinonediazide compound.

The photosensitive composition layer of the present invention can be formed by applying a coating solution prepared by dissolving or dispersing a photosensitive composition comprising each of these components in a solvent onto a support and drying it. .

Examples of the solvent that can be used for dissolving the photosensitive composition include, for example, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl. Ether, diethylene glycol diethyl ether, diethylene glycol monoisopropyl ether, propylene glycol, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether,
Dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-1-butanol, ethyl formate, propyl formate, butyl formate, amyl formate, methyl acetate, ethyl acetate, Propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, ethyl lactate, dimethylformamide, dimethyl sulfoxide, dioxane,
Acetone, methyl ethyl ketone, cyclohexanone, methyl cyclohexanone, diacetone alcohol, acetylacetone, γ-butyrolactone, diethyl ketone, 4
-Hydroxy-2-butanone and the like can be mentioned. These solvents may be used alone or in admixture of two or more.

As a coating method used for coating the surface of the support with the photosensitive composition, conventionally known methods such as spin coating, wire bar coating, dip coating, air knife coating, spray coating, air spray coating, Methods such as electrostatic air spray coating, roll coating, blade coating and curtain coating are used. At this time, the coating amount varies depending on the use, but, for example, 0.05 to 5.0 g as solid content.
A coating amount of / m ² is preferred.

Next, the support used for forming the photosensitive lithographic printing plate of the present invention will be described.

The support preferably has flexibility so that it can be set in an ordinary printing machine and can withstand a load applied during printing. For example, a metal plate of aluminum, magnesium, zinc, chromium, iron, copper, nickel, or the like, An alloy plate of these metals, or a metal plate coated with chromium, zinc, copper, nickel, aluminum, iron or the like by plating or vapor deposition can be used. Of these, the support is preferably one using aluminum or its alloy.

Various kinds of aluminum alloys can be used, for example, silicon, copper, manganese, magnesium,
Examples include alloys of metals such as chromium, zinc, lead, bismuth, and nickel with aluminum.

The support made of aluminum or its alloy or the like is usually subjected to a degreasing treatment in order to remove oil and fat components such as rolling oil adhering to the surface of the support before graining. As the degreasing treatment, degreasing treatment using a solvent such as trichlene and thinner, emulsion degreasing treatment using an emulsion of kesilon and triethanol, and the like are used. In addition, an alkaline aqueous solution such as caustic soda can be used for the degreasing treatment. When an alkaline aqueous solution such as caustic soda is used for the degreasing treatment, it is possible to remove stains and oxide films which cannot be removed only by the above degreasing treatment.

The graining treatment of the present invention is carried out by a so-called mechanical surface-roughening method in which the surface is mechanically roughened, a so-called chemical surface-roughening method in which the surface is chemically selectively dissolved and roughened, and an electrochemical method. The surface can be roughened by a known method such as a so-called electrochemical roughening method.

Mechanical surface roughening methods include, for example, ball polishing, brush polishing, blast polishing, buff polishing, etc., and electrochemical surface roughening methods include hydrochloric acid, nitric acid, etc. There is a method of electrolytically treating with an alternating current or a direct current in an electrolytic solution containing the same.

The graining treatment of the present invention can be carried out by any one of these methods or by using two or more methods in combination.

Since smut is formed on the surface of the support obtained by the graining treatment, it is generally preferable to appropriately perform washing with water or alkali etching in order to remove the smut. Examples of such a treatment include the alkali etching method described in Japanese Patent Publication No. 48-28123 and JP-A No. 53-12739.
Examples thereof include a treatment method such as a sulfuric acid desmutting method described in Japanese Patent Publication No. 1994-242242.

The support treated as described above is then anodized. Wear resistance due to anodizing treatment,
The chemical resistance and water retention can be improved. A known method can be used for the anodizing treatment. For example, a method of electrolyzing with an aqueous solution containing sulfuric acid and / or phosphoric acid or the like at a concentration of 10 to 50% at a current density of 1 to 10 A / dm ² is used. It is preferably used, but is not limited to US Pat.
No. 4,511,66, and a method of electrolyzing in sulfuric acid at a high current density described in US Pat. No. 3,511,66.
It is also possible to use the method of electrolyzing with phosphoric acid described in No. 1 specification.

The anodized support may be subjected to a sealing treatment if necessary. These sealing treatments can be carried out by using known methods such as hot water treatment, boiling water treatment, steam treatment, sodium silicate treatment, dichromate aqueous solution treatment, nitrite treatment and ammonium acetate treatment.

The support is preferably provided with a hydrophilic layer. Water-soluble polymers, alkali metal silicates described in U.S. Pat. No. 3,181,461, JP-A-60-149491, and JP-A-63149 are used for forming the hydrophilic layer.
-165183 gazette amino acid and its salt,
Hydroxyl group-containing amines and salts thereof described in JP-A-60-232998, phosphates described in JP-A-62-19494, and monomers having a sulfo group described in JP-A-59-101651. A polymer compound containing a unit can be used, but in the present invention, the following compounds are preferably used. Water-soluble polymer Specific examples thereof include vinyl resins such as PVA (polyvinyl alcohol), modified PVA, PVAP (polyvinylphosphonic acid), polyvinylpyrrolidone, and polyvinylimidazoline, and derivatives thereof; polyacrylic acid, polyacrylamide, polyhydroxyethyl acrylate. Acrylic acid-based copolymers such as; polyethyleneimine; maleic acid copolymers; polyethylene glycol; polypropylene glycol; polyurethane resin; polyhydroxymethylurea;
Polyhydroxymethyl melamine resin; soluble starch;
CMC (carboxymethyl cellulose); hydroxyethyl cellulose; guar gum; tragacanth gum; xanthan gum; sodium alginate; gelatin and the like. At least one amino group and two or more

[0061]

[Chemical 6] A compound having a group selected from the following or a salt thereof: Examples of the compound having a phosphonic acid group or a salt thereof include 1-aminoethane-1,1-diphosphonic acid and 1-amino-1-phenylmethane-1,1. -Diphosphonic acid, 1-dimethylaminoethane-1,1-diphosphonic acid, 1-dimethylaminobutane-1,1-diphosphonic acid, 1-dimethylaminomethane-1,1-diphosphonic acid, 1-propylaminoethane-1 , 1-diphosphonic acid, 1-butylaminomethane-1,1-diphosphonic acid,
Aminotrimethylenephosphonic acid, ethylenediaminopentamethylenephosphonic acid, ethylenediaminotetramethylenephosphonic acid, diethylenetriaminopentamethylenephosphonic acid, aminotri (2-propylene-2-phosphonic acid) and hydrochlorides, formates, and oxalates of these compounds Examples of the compound having a phosphinic acid group or a salt thereof include a compound in which the phosphonic acid group of the compound having a phosphonic acid group is changed to a phosphinic acid group, or a salt of these compounds, for example, aminotrimethylene. Phosphinic acid and the like, and as the compound having a phosphoric acid group or a salt thereof, a compound in which the phosphonic acid group of the compound having a phosphonic acid group is changed to a phosphoric acid group or a salt of these compounds,
For example, aminotrimethylene phosphoric acid and the like can be mentioned. A compound having at least one amino group and a carboxyl group or a sulfone group or a salt thereof, specific examples thereof include aminoacetic acid, lysine, threonine, serine, aspartic acid, parahydroxyphenylglycine, dihydroxyethylglycine, anthranilic acid, tryptophan, Examples include amino acids such as arginine, aliphatic amino sulfonic acids such as sulfamic acid and cyclohexyl sulfamic acid, and hydrochlorides, formates and oxalates of these compounds. Compounds having at least one amino group and at least one hydroxyl group or salts thereof. Specific examples thereof include monoethanolamine, diethanolamine, trimethanolamine, tripropanolamine, triethanolamine and hydrochlorides and formates of these compounds. , Oxalate and the like. Alkanes having at least two amino groups or salts thereof Alkanes include linear, branched, and cyclic ones.

Particularly preferred is NH _2- (CH ₂ ) _n
Is -NH ₂ (n is an integer of 2 to 10).

As a specific example, ethylenediamine, 1,
3-diaminopropane, 1,4-diaminobutane, 1,
2-diaminopropane, 1,2-diamino-2-methylpropane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,2-diaminocyclohexane, 1,8-diaminooctane , 1,
Examples include 9-diaminononane, 1,10-diaminodecane and their compounds such as hydrochlorides, formates and oxalates.

The photosensitive lithographic printing plate of the present invention can be made into a plate by exposing and developing it in a usual manner. For example, a transparent original image having a line image, a halftone dot image, etc. is brought into close contact with the photosensitive surface for exposure, and then the photosensitive layer in the non-image area is removed using an appropriate developing solution to obtain a relief image. .

Suitable light sources for exposure include mercury lamps, metal halide lamps, xenon lamps, chemical lamps,
Examples include carbon arc lamps. Further, as the developing solution and the developing replenishing solution used for the development, an alkaline aqueous solution is preferable, and examples thereof include alkali metal silicates such as sodium silicate and potassium silicate, sodium hydroxide, potassium hydroxide, trisodium phosphate, An alkaline aqueous solution such as an aqueous solution of sodium diphosphate, sodium carbonate, potassium carbonate or the like can be used.

In the present invention, the developing solution and the developing replenishing solution used for developing the photosensitive lithographic printing plate are preferably those containing an alkali metal silicate. The alkali metals of alkali metal silicates include lithium, sodium,
Potassium is included, of which potassium is most preferred.

At the time of development, it is preferable that the development replenisher is appropriately replenished in accordance with the development processing amount of the photosensitive lithographic printing plate.

The preferred developing solution and developing replenishing solution are [SiO 2
₂ ] / [M] (wherein [SiO ₂ ] indicates the molar concentration of SiO ₂ and [M] indicates the molar concentration of alkali metal) is 0.15 to 1.0, and the SiO ₂ concentration is It is an aqueous solution of an alkali metal silicate that is 0.5 to 5.0% by weight based on the total weight. Further, it is particularly preferable that the developing solution [SiO
₂ ] / [M] is 0.25 to 0.75, the SiO ₂ concentration is 1.0 to 4.0% by weight, and the development replenisher [SiO ₂ ] /
[M] is 0.15 to 0.5, and the SiO ₂ concentration is 1.
It is 0 to 3.0% by weight.

The pH of the developing solution and the developing replenishing solution is preferably 12 to 13.8.

The above-mentioned developers and development replenishers may contain water-soluble or alkali-soluble organic and inorganic reducing agents.

Examples of the organic reducing agent include phenol compounds such as hydroquinone, metol and methoxyquinone, amine compounds such as phenylenediamine and phenylhydrazine, and examples of the inorganic reducing agent include:
For example, sodium sulfite, potassium sulfite, ammonium sulfite, sodium hydrogen sulfite, sulfite salts such as potassium hydrogen sulfite, sodium phosphite, potassium phosphite, sodium hydrogen phosphite, potassium hydrogen phosphite,
Examples thereof include phosphites such as sodium dihydrogen phosphite and dipotassium hydrogen phosphite, hydrazine, sodium thiosulfate, and sodium dithionite.

The water-soluble or alkali-soluble reducing agent can be contained in the developing solution and the developing replenishing solution in an amount of 0.05 to 10% by weight.

The developer and development replenisher may contain an organic carboxylic acid.

These organic carboxylic acids have 6 carbon atoms.
To 20 aliphatic carboxylic acids, and aromatic carboxylic acids in which a benzene ring or a naphthalene ring is substituted with a carboxyl group.

The fat-proof carboxylic acid has 6 to 2 carbon atoms.
Alkanoic acid of 0 is preferable, and specific examples thereof include caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and the like, and particularly preferable are: It is an alkanoic acid having 6 to 12 carbon atoms. The fat-proof carboxylic acid may be a fatty acid having a double bond in the carbon chain or a fatty acid having a branched carbon chain.
The aliphatic carboxylic acid may be used as a sodium or potassium salt or an ammonium salt.

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

The above aromatic carboxylic acid may be used as a sodium or potassium salt or an ammonium salt.

The content of the aliphatic carboxylic acid and the aromatic carboxylic acid may be at least 0.1 to 30% by weight.

The developer and development replenisher may contain the following anionic, nonionic and cationic surfactants and organic solvents.

As the anionic surfactant, higher alcohol (C ₆ -C ₂₂ ) sulfate ester salts [for example, sodium salt of lauryl alcohol sulfate, sodium salt of octyl alcohol sulfate, ammonium salt of lauryl alcohol sulfate, "Τeepol"
-81 "(trade name, manufactured by Shell Chemical Co., Ltd., secondary sodium alkylsulfate, etc.), aliphatic alcohol phosphate ester salts (for example, sodium salt of cetyl alcohol phosphate ester), alkylaryl sulfonates ( For example, dodecylbenzene sulfonic acid sodium salt, isopropyl naphthalene sulfonic acid sodium salt, dinaphthalene disulfonic acid sodium salt, metanitrobenzene sulfonic acid sodium salt, etc., alkyl amide sulfonates (eg, C ₁₇ H ₃₃ CON
(CH ₃ ) CH ₂ SO ₃ Na and the like, sulfonates of dibasic fatty acid ester (for example, dioctyl sodium sulfosuccinate, dihexyl sodium sulfosuccinate, etc.). Among these, sulfonates are particularly preferably used.

As the nonionic surfactant, both polyethylene glycol type and polyhydric alcohol type can be used.

As the nonionic surfactant, for example,
Examples thereof include compounds represented by the following general formulas [1] to [8].

[0083]

[Chemical 7] In the general formulas [1] to [8], R is a hydrogen atom or 1
Represents a valent organic group, and a, b, c, m, n, x and y each represent an integer of 1 to 40.

The organic group represented by R is, for example, a linear or branched alkyl group having 1 to 30 carbon atoms, an alkyl group having a substituent [for example, an aryl group (phenyl etc.)], or an alkyl moiety. Straight or branched carbon number 1-3
Examples thereof include an alkylcarbonyl group which is an alkyl group of 0, a phenyl group which may have a substituent (for example, a hydroxyl group, the above-mentioned alkyl group and the like) and the like.

Specific examples of the nonionic surfactant are shown below.

Polyethylene glycol, polyoxyethylene lauryl ether, polyoxyethylene nonyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether,
Polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene behenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene stearyl amine, polyoxyethylene oleyl amine, polyoxyethylene stearic acid amide, Polyoxyethylene oleic acid amide, polyoxyethylene castor oil, polyoxyethylene abiethyl ether, polyoxyethylene lanolin ether, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene glyceryl monooleate, polyoxyethylene Glyceryl monostearate, polyoxyethylene propylene glycol monostearate, oxyethyl Oxypropylene block polymer, distyrenated phenol polyethylene oxide adduct, tribenzylphenol polyethylene oxide adduct, octylphenol polyoxyethylene polyoxypropylene adduct, glycerol monostearate, sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, etc. .

The weight average molecular weight of the nonionic surfactant is preferably in the range of 300 to 10,000. The concentration of the nonionic surfactant in the developer is at least 0.001-10.
It can be wt%.

Cationic surfactants are roughly classified into amine type and quaternary ammonium salt type, and any of these can be used.

Examples of the amine type include polyoxyethylene alkylamine, N-alkyl propylene amine, N
-Alkyl polyethylene polyamine, N-alkyl polyethylene polyamine dimethyl sulfate, alkyl biguanide, long-chain amine oxide, alkyl imidazoline, 1-
Hydroxyethyl-2-alkylimidazoline, 1-acetylaminoethyl-2-alkylimidazoline, 2-
Alkyl-4-methyl-4-hydroxymethyloxazoline and the like can be mentioned.

Examples of the quaternary ammonium salt type are long-chain primary amine salt, alkyltrimethylammonium salt, dialkyldimethylethylammonium salt, alkyldimethylammonium salt, alkyldimethylbenzylammonium salt, alkylpyridinium salt, and alkylquinone. Norinium salt, alkylisoquinolinium salt, alkylpyridinium sulfate, stearamidomethylpyridinium salt, acylaminoethyldiethylamine salt, acylaminoethylmethyldiethylammonium salt, alkylamidopropyldimethylbenzylammonium salt, fatty acid polyethylene polyamide, acylamino Ethylpyridinium salt, Acylcholaminoformylmethylpyridinium salt, Stearooxymethylpyridinium salt, Fatty acid triethanolamine, Fat Acid triethanolamine formate, trioxyethylene fatty acid triethanolamine,
Examples thereof include fatty acid dibutylaminoethanol, cetyloxymethylpyridinium salt, and p-isooctylphenoxyethoxyethyldimethylbenzil ammonium salt. ("Alkyl" in the examples of the above compounds has 6 carbon atoms.
~ 20 straight chain or partially substituted alkyl,
Specifically, straight chain alkyl such as hexyl, octyl, cetyl, stearyl is preferably used. ) Further, a cationic surfactant of a polymer having a cation component as a repeating unit, for example, a polymer containing a quaternary ammonium salt obtained by copolymerization with a lipophilic monomer can be contained.

The amount of the cationic surfactant added to the developer may be at least 0.001 to 10% by weight.

The weight average molecular weight is at least 300-
Those in the range of 50,000 can be used.

As the surfactant, it is preferable to use a fluorine-containing surfactant containing a perfluoroalkyl group in the molecule. As such a fluorine-based surfactant,
Perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, anion type such as perfluoroalkyl phosphate, amphoteric type such as perfluoroalkyl betaine, cation type such as perfluoroalkyltrimethylammonium salt and perfluoroalkylamine oxide, Perfluoroalkyl ethylene oxide adduct, oligomer containing perfluoroalkyl group and hydrophilic group, oligomer containing perfluoroalkyl group and lipophilic group, oligomer containing perfluoroalkyl group, hydrophilic group and lipophilic group, perfluoroalkyl group and parent A nonionic type such as an oily group-containing urethane may be mentioned.

The above surfactants can be used alone or in combination of two or more kinds.

Further, the developer and the development replenisher may contain an organic solvent.

As the organic solvent, those having a solubility in water at 20 ° C. of not more than 10% by weight are preferable, and examples thereof include ethyl acetate, propyl acetate, butyl acetate, benzyl acetate, ethylene glycol monobutyl acetoate, butyl lactate and levulinic acid. Carboxylic acid esters such as butyl;
Ketones such as ethyl butyl ketone, methyl isobutyl ketone, cyclohexanone; 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; alkyl-substituted aromatic hydrocarbons such as xylene; halogenated hydrocarbons such as methylene dichloride, ethylene dichloride and monochlorobenzene.

These organic solvents can be used alone or in combination of two or more kinds.

Further, the following additives may be added to the developer and the development replenisher in order to enhance the developing performance. Examples of these additives include, for example, JP-A-58-7.
Neutral salts such as NaCl, KCl and KBr described in JP-A-5152, EDT described in JP-A-59-190952
Chelating agents such as A and NTA, JP-A-59-121336
[Co (NH ₃ )] ₆ , Cl _{3 and} other complexes described in JP-A-56-142528, amphoteric polymer electrolytes such as copolymers of vinylbenzyltrimethylammonium chloride and sodium acrylate described in JP-A-56-142528, and Kaisho 58-59
Inorganic lithium compounds such as lithium chloride described in Japanese Patent Publication No. 444,444, Organic lithium compounds such as lithium benzoate described in Japanese Patent Publication No. 50-34442, JP-A-59-75255
Organometallic surfactants containing Si, Ti, etc.,
The organic boron compounds described in JP-A-59-84241 are mentioned.

[0099]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example [Preparation of support] An aluminum plate (material 1050, temper H16) having a thickness of 0.3 mm was degreased for 1 minute in a 5% aqueous sodium hydroxide solution kept at 65 ° C. Then, it was washed with water, immersed in a 10% sulfuric acid aqueous solution kept at 25 ° C. for 1 minute for neutralization, and further washed with water. The aluminum plate was electrolytically surface-roughened with an alternating current in a 1.0 wt% hydrochloric acid aqueous solution under the conditions of a temperature of 25 ° C., a current density of 100 A / dm ² , and a treatment time of 60 seconds. Then, desmut treatment is performed at 60 ° C. for 10 seconds in a 5% aqueous sodium hydroxide solution, and then anodization is performed in a 20% sulfuric acid solution at a temperature of 20 ° C., a current density of 3 A / dm ² , and a treatment time of 1 minute. Processed. Then, it was immersed in a 1% sodium nitrite aqueous solution kept at 80 ° C. for 30 seconds, washed with water, and dried at 80 ° C. for 3 minutes. Furthermore, the support was prepared by immersing the carboxymethyl cellulose aqueous solution (concentration 0.1% by weight) kept at 85 ° C. for 30 seconds and then drying at 80 ° C. for 5 minutes.

[Preparation of photosensitive lithographic printing plate sample] Coating solution A below was coated on the above support using a wire bar, and 8
It was dried at 0 ° C. for 1 minute to prepare a photosensitive lithographic printing plate sample 1. Further, the following coating liquid B was coated on the support using a wire bar and dried at 80 ° C. for 1 minute to prepare a photosensitive lithographic printing plate sample 2.

(Photosensitive Solution A) Novolac resin (molar ratio of phenol / m-cresol / p-cresol of 10/54/36, weight average molecular weight 4000) 6.7 g of pyrogallolacetone resin (weight average molecular weight 3000) and o -Condensation product of naphthoquinone di azido-5-sulfonyl chloride (esterification rate 30%) 1.5 g Polyethylene glycol # 2000 0.2 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis ( Trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.15 g FC-430 (manufactured by Sumitomo 3M Ltd.) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.2 g Polymer compound 1 below 0.2 g methyl ethyl ketone / diethyl carbitol = 50/50 100 millili Turtle

[0103]

Embedded image

(Photosensitive Solution B) Novolac resin (phenol / m-cresol / p-cresol molar ratio 10/54/36, weight average molecular weight 4000) 6.7 g pyrogallolacetone resin (weight average molecular weight 3000) and o -Condensation product of naphthoquinone di azido-5-sulfonyl chloride (esterification rate 30%) 1.5 g Polyethylene glycol # 2000 0.2 g Victoria Pure Blue BOH (Hodogaya Chemical Co., Ltd.) 0.08 g 2,4-bis ( Trichloromethyl) -6- (p-methoxystyryl) -s-triazine 0.15 g FC-430 (Sumitomo 3M Ltd.) 0.03 g cis-1,2-cyclohexanedicarboxylic acid 0.2 g methyl ethyl ketone / diethyl carbitol = 50/50 100 ml

The sensitivity and printing durability of the obtained photosensitive lithographic printing plate samples 1 and 2 were evaluated by the following evaluation methods. The results obtained are shown in Table 1. (Evaluation method) = Sensitivity = A step tablet for sensitivity measurement (No. 2 manufactured by Eastman Kodak Co., 21-step gray scale with 0.15 density difference) was adhered to the sample, and a 4 kW metal halide lamp (Dainippon Screen ( Exposure was performed from a distance of 90 cm using a light source manufactured by Bio Quick Co., Ltd. as a light source. Next, this sample was developed for 20 seconds at 27 ° C. with a developer obtained by diluting SDR-1 (manufactured by Konica Corp.) developer 6 times with water. The sensitivity was defined as the exposure time at which 3.0 steps of the step tablet was completely cleared.

= Printing durability = A step tablet for sensitivity measurement (No. 2 manufactured by Eastman Kodak Co., 21 levels of gray scale with 0.15 density difference) was adhered to the sample, and a 4 kW metal halide lamp (Dainippon Screen) was used. Exposure was performed from a distance of 90 cm with a light source (Bio Quick Co., Ltd.) as a light source.

Next, this sample was treated at 27 ° C. with a developer obtained by diluting SDR-1 (manufactured by Konica Corporation) developer 6 times with water.
And developed for 20 seconds.

The lithographic printing plate thus obtained was applied to a printing machine GTO manufactured by Heidelberg Co., Ltd., and coated paper, printing ink (New Bright Red manufactured by Toyo Ink Mfg. Co., Ltd.) and fountain solution (SEU-3 manufactured by Konica Co., Ltd.) were used. , 2.5%) is used for printing, and printing is continued until defective solidification of the image of the printed matter appears or ink is non-printed on the non-printing area, and the number of printed sheets at that time is counted. The number of sheets was used as the printing durability.

[0109]

[Table 1]

[0110]

EFFECT OF THE INVENTION The photosensitive composition and the photosensitive lithographic printing plate of the present invention have high printing durability, but do not suffer from sensitivity deterioration or deterioration of developability.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Shinichi Matsubara 1 Sakura-cho, Hino-shi, Tokyo Konica Stock Company

Claims (2)

[Claims] 1. A photosensitive composition comprising a polymer compound having a side chain having a repeating structural unit represented by the following general formula [I] and an o-quinonediazide compound. Embedded image [In formula, R < ¹ > and R < ² > represents a hydrogen atom, a C1-C12 alkyl group, or a phenyl group, and m represents the integer of 1-5. ] 2. A photosensitive lithographic printing plate comprising a support having a hydrophilic surface and a photosensitive layer comprising the photosensitive composition according to claim 1 provided on the support.