JP2002006437A - Silver halide photosensitive material, original plate of photosensitive planographic printing plate and relief image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a relief image suitable for utilization as a planographic printing plate using a silver halide photosensitive material. SOLUTION: A phenolic compound (I) having 2-6 benzenediol or benzenetriol rings bonded through a combining group and a phenolic compound (II) having a 5-40C aliphatic substituent or a 7-40C aromatic substituent introduced into a benzenediol or benzenetriol ring are added as tanning developers to a silver halide photosensitive material with a silver halide-gelatin emulsion layer on the base.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photosensitive material, a photosensitive lithographic printing plate precursor, and a method for forming a relief image by tanning the plate.

[0002]

2. Description of the Related Art Tanning development is a phenomenon that has long been known in the art of silver halide photography (for example,
TH James, The Theory of the Photographic Proces
s, 4thedition, pages 326-327). Pyrogallol,
When a silver halide photosensitive material is developed using a phenolic developing agent such as hydroquinone or catechol, the gelatin contained in the silver halide emulsion layer hardens in the exposed areas. This tanning effect occurs because the oxidation product of the phenolic developing agent has a hardening effect on gelatin. Tanning development has the effect of softening the image of a normal silver halide photograph. That is, since the gelatin in the exposed area is hardened, the penetration of the developing solution in the exposed area is suppressed, whereby the progress of development is suppressed.

A method has been proposed in which the hardening of gelatin in an exposed portion is used for forming a relief image. If the uncured gelatin in the unexposed area is eluted, a relief image of the cured gelatin can be formed. The relief image of hardened gelatin can be used as a lithographic printing plate.
If a relief image of hardened gelatin is formed on a hydrophilic support (aluminum plate), the surface of the support exposed by removal functions as a hydrophilic region, and the relief image functions as a lipophilic region. In lithographic printing, an image is printed by dampening water adhering to a hydrophilic area and oil-based ink adhering to a lipophilic area. A method of utilizing a relief image of hardened gelatin as a lithographic printing plate is described in JP-A-53-135.
No. 702, No. 54-49202, No. 54-15250
No. 2, No. 55-12625, JP-A-4-324866
And JP-A-5-289228.

[0004]

The method of using a relief image of hardened gelatin as a lithographic printing plate is that silver halide, which is an optical sensor, has higher sensitivity than other lithographic printing plate making methods, There is an advantage that plate making can be performed with simple processing. When a relief image of hardened gelatin is used as a lithographic printing plate, the exposed surface of the support functions as a hydrophilic region and the relief image functions as a lipophilic region. Hardened gelatin is not strongly lipophilic, even though it is relatively lipophilic compared to the support surface (hardened gelatin is
It is more common to treat them as hydrophilic substances). In lithographic printing using a fountain solution, the hardened gelatin easily absorbs the fountain solution and swells or softens. For the above reasons, when a relief image of hardened gelatin is used as a lithographic printing plate, the hardened gelatin has problems of insufficient lipophilicity (ink receptivity) and low strength (press life).

JP-A-53-135702 and JP-A-54-4
Nos. 9202, 54-152502, 55-126
No. 25, JP-A-4-324866 and 5-28922
The method described in each publication of No. 8 proposes to perform a treatment (heating treatment, light irradiation treatment, chemical treatment) on the hardened gelatin after image formation in order to improve ink receptivity and printing durability. However, when post-processing is performed after image formation, the advantage that plate making can be performed with simple processing is lost. In addition, the heat treatment has a problem that the adhesiveness between the hardened gelatin and the support decreases. In the light irradiation process, a powerful light irradiation device is required. The chemical treatment has a problem that the toxicity of the chemical substance used and the treatment effect are insufficient. The purpose of the present invention is
An object of the present invention is to provide a silver halide photosensitive material capable of forming a relief image suitable for use as a lithographic printing plate. It is also an object of the present invention to form a relief image having high lipophilicity and high strength.

[0006]

The above objects have been attained by the following silver halide photosensitive materials (1) to (5) and a relief image forming method (6). (1) A silver halide photosensitive material having a silver halide gelatin emulsion layer on a support, wherein the silver halide gelatin emulsion layer or an optional hydrophilic layer is a phenol represented by the following formula (I): A silver halide photosensitive material comprising a compound and a phenol compound represented by the following formula (II):

[0007]

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Wherein L is a divalent to hexavalent aliphatic group;
Divalent to hexavalent aromatic group, divalent to hexavalent heterocyclic group,-
O -, - S -, - CO -, - NH -, - N <, - SO 2
N selected from-, -SO- and a combination thereof.
A divalent linking group, wherein the aliphatic group, the aromatic group and the heterocyclic group may have a substituent; the benzene ring may have a substituent other than hydroxy; , 2 or 3; and n is an integer from 2 to 6]

[0009]

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Wherein p is 1 or 2; and R is an aliphatic group having 5 to 40 carbon atoms, an aromatic group having 7 to 40 carbon atoms, and 5 To 40
Aliphatic acyl groups, aromatic acyl groups having 7 to 40 carbon atoms, aliphatic oxycarbonyl groups having 5 to 40 carbon atoms, aromatic oxycarbonyl groups having 7 to 40 carbon atoms, carbon atoms Is an aliphatic acyloxy group having 5 to 40, an aromatic acyloxy group having 7 to 40 carbon atoms,
An aliphatic substituted carbamoyl group having 5 to 40 carbon atoms or an aromatic substituted carbamoyl group having 7 to 40 carbon atoms].

(2) The silver halide light-sensitive material according to (1), wherein the silver halide gelatin emulsion layer contains a phenol compound represented by the formula (I) and a phenol compound represented by the formula (II). (3) A support, a silver halide emulsion layer, and a hydrophilic layer are laminated in this order. The silver halide gelatin emulsion layer contains the phenolic compound represented by the formula (I), and the hydrophilic layer has the formula (I) The silver halide light-sensitive material according to (1), comprising the phenol compound represented by II). (4) a support, a silver halide emulsion layer, a first hydrophilic layer, and a second hydrophilic layer, which are laminated in this order, wherein the first hydrophilic layer contains a phenol compound represented by the formula (I). , Second
The silver halide photosensitive material according to (1), wherein the hydrophilic layer contains a phenol compound represented by the formula (II). (5) A support, a first hydrophilic layer, a silver halide emulsion layer, and a second hydrophilic layer are laminated in this order, wherein the first hydrophilic layer contains a phenol compound represented by the formula (I). , Second
The silver halide photosensitive material according to (1), wherein the hydrophilic layer contains a phenol compound represented by the formula (II).

(6) A photosensitive lithographic printing plate precursor having a silver halide gelatin emulsion layer on a hydrophilic support, wherein the silver halide gelatin emulsion layer or the optional hydrophilic layer is of the formula (I) A photosensitive lithographic printing plate precursor comprising a phenol compound represented by the formula (II) and a phenol compound represented by the formula (II). (7) a step of imagewise exposing a silver halide light-sensitive material having a support and a silver halide gelatin emulsion layer, a step of tanning developing the silver halide light-sensitive material to harden gelatin in exposed portions, and A step of eluting the hardened gelatin to form a relief image of the hardened gelatin,
A relief image forming method carried out in this order, wherein the phenol compound represented by the formula (I) and the phenol compound represented by the formula (II)
Tanning development using a phenol compound represented by formula (I) as a tanning developer.

[0013]

The present inventor has started to improve the tanning developer instead of adding post-processing as proposed in the prior art. As a result of the study, two to six benzenediol rings or benzenetriol rings corresponding to conventional tanning developers (eg, pyrogallol, hydroquinone, catechol) were linked with a phenol compound (I) linked by a linking group. A phenol compound (II) having an aliphatic substituent having 5 to 40 carbon atoms or an aromatic substituent having 7 to 40 carbon atoms introduced into a benzenediol ring or a benzenetriol ring. Has successfully formed a hardened gelatin having high lipophilicity and high strength. The improved lipophilicity and strength of the hardened gelatin has substantially made it possible to utilize the relief image of the hardened gelatin as a lithographic printing plate.

[0014]

DETAILED DESCRIPTION OF THE INVENTION [Tanning developer] In the present invention, a phenol compound represented by the formula (I) and a phenol compound represented by the formula (II)
Is used in combination as a tanning developer.

[0015]

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In the formula (I), L represents a divalent to hexavalent aliphatic group, a divalent to hexavalent aromatic group, a divalent to hexavalent heterocyclic group, —O—, —S—, -CO-, -NH-, -N
_{<, - SO 2 -, -} SO- and a n-valent linking group selected from their combinations. The aliphatic group, aromatic group, and heterocyclic group may have a substituent. The aliphatic group preferably has 1 to 60 carbon atoms, and preferably has 1 to 60 carbon atoms.
It is more preferably from 30 to 30, still more preferably from 1 to 20, and most preferably from 1 to 10. The aliphatic group may be unsaturated (having a double bond or a triple bond). The aliphatic group may have a cyclic structure or a branch. The aromatic group preferably comprises a benzene ring or a naphthalene ring, more preferably a benzene ring. The heterocyclic group is 3
It preferably has a 10 to 10 membered heterocyclic ring, more preferably has a 4 to 8 membered heterocyclic ring, and most preferably has a 5 or 6 membered heterocyclic ring. The hetero atom of the heterocyclic ring is preferably a nitrogen atom, an oxygen atom or a sulfur atom. An aliphatic ring, an aromatic ring, or another hetero ring may be condensed or spiro-bonded to the hetero ring. Examples of the heterocycle include a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, a tetrahydrofuran ring, a tetrahydropyran ring, a tetrahydrothiophene ring, a dioxane ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a triazine ring, and a furan ring. , A thiophene ring and an isocyanuric ring.

Examples of the substituent of the aliphatic group, aromatic group and heterocyclic group include hydroxyl, halogen atom (eg, chlorine atom), cyano, amino, substituted amino group, heterocyclic group, acyl group and acyloxy group. Is included. The substituent of the substituted amino group is preferably an alkyl group or an aryl group. The aromatic group and the heterocyclic group may have an alkyl group as a substituent. L is a divalent to tetravalent aliphatic group, a divalent to tetravalent aromatic group, a divalent to tetravalent heterocyclic group, -O-, -CO-, -NH-, -N <,- SO ₂ −
And a divalent to tetravalent linking group selected from a combination thereof and a divalent to tetravalent aliphatic group, a divalent to tetravalent aromatic group, and a divalent to tetravalent heterocyclic group. , -O-, -CO-, -NH-, -N <and -SO
More preferably, the compound is a divalent to tetravalent linking group in which at least two _2- are combined, and most preferably, a divalent to tetravalent linking group in which at least three are combined. Hereinafter, examples of the linking group (L) are shown.

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[0026]

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In the formula (I), the benzene ring may have a substituent other than hydroxy (eg, an alkyl group, an alkoxy group, an aralkyl group). However, it is preferable that a substituent other than hydroxy is not bonded to the benzene ring. In the formula (I), m is 2 or 3.
In the formula (I), n is an integer of 2 to 6. n
Is preferably an integer of 2 to 4, preferably 2 or 3.
Is more preferably, and most preferably 2. Hereinafter, examples of the tanning developer represented by the formula (I) will be described.

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The tanning developer represented by the formula (I) is
Known (for example, Biophysical Jounal Vol. 71, 1966, pag
es 3261-3277) can be synthesized.

[0048]

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In the formula (II), p is 1 or 2. When p is 1, the relationship between the two hydroxyl groups is preferably ortho (catechol derivative) or para (hydroquinone derivative). When p is 2, the three hydroxyl groups are preferably adjacent (pyrogallol derivative).

In the formula (II), R represents 5 carbon atoms.
To 40 aliphatic groups, aromatic groups having 7 to 40 carbon atoms, aliphatic acyl groups having 5 to 40 carbon atoms, aromatic acyl groups having 7 to 40 carbon atoms, and 5 carbon atoms To 40 aliphatic oxycarbonyl groups, aromatic oxycarbonyl groups having 7 to 40 carbon atoms, aliphatic acyloxy groups having 5 to 40 carbon atoms, and 7 to 4 carbon atoms
0 aromatic acyloxy group, aliphatic substituted carbamoyl group having 5 to 40 carbon atoms, or 7 to 4 carbon atoms.
0 is an aromatic substituted carbamoyl group. The aliphatic group preferably has 6 to 35 carbon atoms, more preferably 7 to 30 carbon atoms, further preferably 9 to 25 carbon atoms, and most preferably 11 to 22 carbon atoms. The aliphatic group may be unsaturated (having a double bond or a triple bond). The aliphatic group may have a cyclic structure or a branch. The aliphatic group may have a substituent (eg, a halogen atom, an aromatic group).
The aromatic group preferably has 7 to 35 carbon atoms, more preferably 8 to 30 carbon atoms, furthermore preferably 9 to 25 carbon atoms, and most preferably 10 to 22 carbon atoms. The aromatic group may have a substituent (eg, a halogen atom, an aliphatic group).

The aliphatic acyl group preferably has 6 to 35 carbon atoms, more preferably 7 to 30 carbon atoms, further preferably 9 to 25 carbon atoms, and more preferably 11 to 22 carbon atoms. Most preferred. The aliphatic acyl group may be unsaturated (having a double bond or a triple bond). The aliphatic acyl group may have a cyclic structure or a branch. The aliphatic acyl group may have a substituent (eg, a halogen atom, an aromatic group). The number of carbon atoms of the aromatic acyl group is preferably from 7 to 35, more preferably from 8 to 30, further preferably from 9 to 25, and most preferably from 10 to 22. The aromatic acyl group is
It may have a substituent (eg, a halogen atom, an aliphatic group). The number of carbon atoms of the aliphatic oxycarbonyl group is
It is preferably from 6 to 35, more preferably from 7 to 30, still more preferably from 9 to 25, and most preferably from 11 to 22. The aliphatic oxycarbonyl group may be unsaturated (having a double bond or a triple bond). The aliphatic acyl group may have a cyclic structure or a branch. The aliphatic oxycarbonyl group may have a substituent (eg, a halogen atom, an aromatic group). The aromatic oxycarbonyl group preferably has 7 to 35 carbon atoms, more preferably 8 to 30 carbon atoms, and more preferably 9 to 25 carbon atoms.
Is more preferable, and most preferably 10 to 22. The aromatic oxycarbonyl group may have a substituent (eg, a halogen atom, an aliphatic group).

The number of carbon atoms of the aliphatic acyloxy group is preferably from 6 to 35, more preferably from 7 to 30, further preferably from 9 to 25, and more preferably from 11 to 22. Most preferred. The aliphatic acyloxy group may be unsaturated (having a double bond or a triple bond). The aliphatic acyloxy group may have a cyclic structure or a branch. The aliphatic acyloxy group may have a substituent (eg, a halogen atom, an aromatic group). The aromatic acyloxy group preferably has 7 to 35 carbon atoms,
It is more preferably from 30 to 30, further preferably from 9 to 25, and most preferably from 10 to 22. The aromatic acyloxy group may have a substituent (eg, a halogen atom, an aliphatic group). The aliphatic substituted carbamoyl group preferably has 6 to 35 carbon atoms, more preferably 7 to 30 carbon atoms, further preferably 9 to 25 carbon atoms, and most preferably 11 to 22 carbon atoms. . The aliphatic substituted carbamoyl group may be unsaturated (have a double or triple bond). The aliphatic acyl group may have a cyclic structure or a branch. The aliphatic substituted carbamoyl group may have a substituent (eg, a halogen atom, an aromatic group). The number of carbon atoms of the aromatic-substituted carbamoyl group is preferably from 7 to 35, more preferably from 8 to 30, further preferably from 9 to 25, and most preferably from 10 to 22. . The aromatic-substituted carbamoyl group may have a substituent (eg, a halogen atom, an aliphatic group).

Catechol, hydroquinone or pyrogallol derivatives represented by the following formulas (IIa), (IIb), (IIc) or (IId) are particularly preferred tanning developers.

[0054]

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In the formulas (IIa), (IIb), (IIc) and (IId), R represents an aliphatic group having 5 to 40 carbon atoms, an aromatic group having 7 to 40 carbon atoms, or a carbon atom. An aliphatic acyl group having 5 to 40 carbon atoms, an aromatic acyl group having 7 to 40 carbon atoms, an aliphatic oxycarbonyl group having 5 to 40 carbon atoms, and an aromatic oxycarbonyl having 7 to 40 carbon atoms Group, an aliphatic acyloxy group having 5 to 40 carbon atoms, an aromatic acyloxy group having 7 to 40 carbon atoms, an aliphatic substituted carbamoyl group having 5 to 40 carbon atoms, or an aliphatic acyloxy group having 5 to 40 carbon atoms It is an aromatic substituted carbamoyl group. The definition and examples of each group are the same as those in formula (II). Hereinafter, examples of the tanning developer represented by the formula (II) will be described.

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The tanning developer represented by the formula (I) and (I)
The ratio with the tanning developer represented by (I) is (I):
The molar ratio of (II) is preferably from 1:99 to 99: 1, more preferably from 2:98 to 98: 2, even more preferably from 5:95 to 95: 5. : 90 to 90:10 is most preferable. Three or more tanning developers may be used in combination.
A tanning developer represented by formulas (I) and (II);
Known tanning developers (eg, hydroquinone, t-butylhydroquinone, catechol, phenylcatechol, pyrogallol, nordihydrguaiaretic acid,
3,3′3′-tetramethyl-5,6,5 ′, 6′-tetrahydroxyspiro-bis-indane). When used in combination, the tanning developers represented by the formulas (I) and (II) are used in an amount of 5% of the total amount of the tanning developers.
It is preferably 0 to 99 mol%, and 55 to 95 mol%.
More preferably, it is more preferably 60 to 90 mol%. The tanning developer is used by adding it to a silver halide photosensitive material or a tanning developer. The tanning developers represented by formulas (I) and (II) are preferably added to a silver halide photosensitive material.

When a tanning developer is added to the silver halide light-sensitive material, a silver halide gelatin emulsion layer or a coating liquid for an optional hydrophilic layer (eg, a hydrophilic undercoat layer, a hydrophilic protective layer) may be added to the silver halide emulsion layer. The tanning developer may be dissolved, emulsified or dispersed. The tanning developer can be generally dissolved in a coating solution for a silver halide gelatin emulsion layer or a hydrophilic layer. The amount added to the silver halide photosensitive material (total amount of all the developing agents) is 0.01 to 10 mol /
Mol Ag, preferably 0.03 to 2 mol / mol.
More preferably, it is molar Ag. When added to the tanning developer, the tanning developer may be dissolved, emulsified or dispersed in the developer. The amount added to the developer is preferably 10 ^{-5 to} 10 ^-1 mol / l.

When a tanning developer is added to the silver halide light-sensitive material, the arrangement of the tanning developer in the layer structure of the silver halide light-sensitive material is not particularly limited. However, the tanning developer represented by the formula (II) is preferably added to the uppermost layer (the layer farthest from the support) of the silver halide photosensitive material in principle. It is also preferable that the tanning developer represented by the formula (I) and the tanning developer represented by the formula (II) are added to different layers. In addition to the tanning developer, an auxiliary developer can be used. Examples of auxiliary developing agents include amidole, metol and aminophenol. Metol is particularly preferred. The auxiliary developing agent can be added to a tanning developer or a silver halide photosensitive material. The amount of the auxiliary developer is 5 to 200 mol% of the amount of the tanning developer.
It is preferred that

FIG. 1 is a schematic sectional view of a preferred embodiment of the silver halide photosensitive material. The silver halide photosensitive material shown in FIG. 1 has a silver halide gelatin emulsion layer (2) provided on a hydrophilic support (1). The silver halide gelatin emulsion layer (2) comprises silver halide grains (21), gelatin (22), a tanning developer (I) represented by the formula (I) and a tanning developer represented by the formula (II) (I
I).

FIG. 2 is a schematic sectional view of another preferred embodiment of the silver halide light-sensitive material. The silver halide photosensitive material shown in FIG. 2 has a silver halide gelatin emulsion layer (2) and a hydrophilic layer (3) provided in this order on a hydrophilic support (1). The silver halide gelatin emulsion layer (2)
It contains silver halide grains (21), gelatin (22) and a tanning developer (I) represented by the formula (I). The hydrophilic layer (3) comprises a hydrophilic polymer (31) and a compound represented by the formula (II):
And a tanning developer (II) represented by

FIG. 3 is a schematic sectional view of still another preferred embodiment of the silver halide photosensitive material. In the silver halide light-sensitive material shown in FIG. 3, a first hydrophilic layer (4), a silver halide gelatin emulsion layer (2) and a second hydrophilic layer (5) are formed on a hydrophilic support (1). They are provided in order. The first hydrophilic layer (4) contains gelatin (41) and a tanning developer (I) represented by the formula (I). The silver halide gelatin emulsion layer (2) contains silver halide grains (21) and gelatin (22). The second hydrophilic layer (5) contains a hydrophilic polymer (51) and a tanning developer (II) represented by the formula (II).

FIG. 4 is a schematic sectional view of still another preferred embodiment of the silver halide photosensitive material. The silver halide light-sensitive material shown in FIG. 4 has a silver halide gelatin emulsion layer (2), a first hydrophilic layer (4) and a second hydrophilic layer (5) on a hydrophilic support (1). They are provided in order. The silver halide gelatin emulsion layer (2) contains silver halide grains (21) and gelatin (22). The first hydrophilic layer (4) contains gelatin (41) and a tanning developer (I) represented by the formula (I). Second hydrophilic layer (5)
Contains a hydrophilic polymer (51) and a tanning developer (II) represented by the formula (II).

[Support] As the support, paper, synthetic paper,
Paper laminated with synthetic resin (eg, polyethylene, polypropylene, polystyrene), plastic film (eg, polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate), metal plate (eg, aluminum, aluminum alloy,
Zinc, iron, copper), and paper or plastic film on which these metals are laminated or deposited can be used. Aluminum plates, plastic films, paper and synthetic paper are preferred. Further, a composite sheet in which an aluminum sheet is laminated on a polyethylene terephthalate film is also preferable. Aluminum plates and plastic films are more preferred, and aluminum plates are particularly preferred. For use in a lithographic printing original plate, it is preferable to use a hydrophilic support. Even when a hydrophobic material such as a plastic film is used, it can be used as a hydrophilic support by providing a hydrophilic undercoat layer (described later).

The case where an aluminum plate is used as a support will be further described. The aluminum support is subjected to a surface treatment such as a surface roughening treatment (graining treatment) or a surface hydrophilic treatment as necessary. The surface roughening treatment may be performed by an electrochemical sanding method (for example, a method of sanding an aluminum plate by passing an electric current in a hydrochloric acid or nitric acid electrolyte) and / or a mechanical sanding method. (For example, a wire brush grain method in which the aluminum surface is scratched with a metal wire, a ball grain method in which the aluminum surface is sanded with a polishing ball and an abrasive, a brush grain in which the surface is sanded with a nylon brush and an abrasive) Method). Next, the grained aluminum plate is chemically etched with acid or alkali. An industrially advantageous method is etching using an alkali. Examples of the alkaline agent include sodium carbonate, sodium aluminate, sodium metasilicate, sodium phosphate, sodium hydroxide, potassium hydroxide and lithium hydroxide. The concentration of the alkaline solution is preferably in the range of 1 to 50% by weight. The temperature of the alkali treatment is preferably in the range of 20 to 100 ° C. Further, it is preferable to adjust the processing conditions so that the amount of aluminum dissolved is 5 to 20 g / m ² .

Normally, after the alkali etching, the aluminum plate is washed with an acid to remove dirt (smut) remaining on the surface. Preferred acids are nitric acid, sulfuric acid,
Phosphoric acid, chromic acid, hydrofluoric acid and borofluoric acid. The smut removal treatment after the electrochemical graining treatment can be performed by a known method such as a method of contacting with sulfuric acid at a concentration of 15 to 65% by weight at 50 to 90 ° C. The aluminum plate subjected to the surface roughening treatment as described above can be subjected to an anodic oxidation treatment or a chemical conversion treatment, if necessary. The anodic oxidation treatment can be performed by a known method. Specifically, an anodic oxide film is formed on the aluminum surface by passing a direct current or an alternating current through an aluminum plate in an acid solution. Examples of acids include sulfuric acid, phosphoric acid, chromic acid, oxalic acid, sulfamic acid and benzenesulfonic acid. Anodizing conditions vary depending on the electrolyte used. Generally, the concentration of the electrolyte is 1 to 80% by weight, the temperature of the electrolyte is 5 to 70 ° C., and the current density is 0.5%.
To 60 amps / dm ^2, a voltage of ^from 1 to 100v, and electrolysis time is preferably in the range of 10 to 100 seconds. Particularly preferred anodic oxidation methods are a method of performing anodization at a high current density in sulfuric acid and a method of performing anodization using phosphoric acid as an electrolytic bath. After the anodizing treatment, the aluminum plate may be subjected to an alkali metal silicate treatment (for example, a treatment of immersing the aluminum plate in an aqueous solution of sodium silicate). In order to improve the adhesion between the aluminum support and the curable layer and the printing characteristics, an undercoat layer may be provided on the support surface.

[Undercoat Layer] The undercoat layer is provided as a hydrophilic layer not only on the aluminum support described above but also on a support whose surface is not sufficiently hydrophilic (eg, a plastic film). Components constituting the undercoat layer include polymers (eg, gelatin, casein, polyvinyl alcohol, ethyl cellulose, phenolic resin, styrene-maleic anhydride resin, polyacrylic acid); amines (eg, monoethanolamine, diethanolamine, triethanolamine) , Tripropanolamine) and their hydrochlorides, oxalates or phosphates; monoaminomonocarboxylic acids (eg, aminoacetic acid, alanine); oxyamino acids (eg, serine, threonine, dihydroxyethylglycine); sulfur-containing amino acids (Eg, cysteine, cystine); monoaminodicarboxylic acid (eg, aspartic acid, glutamic acid); diaminomonocarboxylic acid (eg, lysine); amino acid having an aromatic nucleus (eg, p-hydroxyphenylglycine, phenylalanine, ant) Sulfonyl); aliphatic amino acid (e.g., sulfamic acid, cyclohexylsulfamic acid); and (poly) aminopolyacetic acid (e.g.,
Ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, hydroxyethylethylenediamineacetic acid, ethylenediaminediacetic acid, cycloethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid). A compound in which some or all of the acid groups of the above compounds have become salts (eg, sodium salt, potassium salt, ammonium salt) can also be used. The above components can be used in combination of two or more. When a plastic film is used as the support, it is preferable to add hydrophilic fine particles (eg, silica powder) to the hydrophilic undercoat layer instead of the graining treatment of the aluminum support.

[Silver halide emulsion layer] The silver halide emulsion layer generally contains gelatin as a binder. In tanning development, a relief image can be formed by hardening gelatin. Besides gelatin,
Tanning development can be performed on a hydrophilic polymer having an amide bond or a primary amino group (eg, a protein other than gelatin, polyacrylamide). However, tanning development is usually performed on gelatin. Gelatin may be used in combination with another hydrophilic polymer (eg, polyvinylpyrrolidone, starch, albumin, polyvinyl alcohol, gum arabic, hydroxyethyl cellulose). The amount of silver halide applied is
It is preferably 0.01 to 5 g / m ² , more preferably 0.03 to 1 g / m ² , and most preferably 0.05 to 0.3 g / m ² in terms of silver. The thickness of the silver halide emulsion layer is from 0.07 to 13
μm, more preferably 0.2 to 5 μm.

As silver halide, silver chloride, silver bromide,
Any grain of silver iodide, or silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide can be used. The shape of the silver halide grains is preferably cubic or tetradecahedral, but is not limited to those having a regular crystal form, and may be those having an irregular crystal form or a complex form thereof. Potato-shaped,
Spherical, plate-like and plate-like crystal forms are included. In the case of tabular grains, the grain size is generally at least five times the grain thickness.
There is no particular limitation on the grain size of the silver halide.
Fine particles of 0.01 μm or less can also be used. Meanwhile, 1
Large particles of about 0 μm can also be used. With respect to grain size distribution, monodisperse grains are preferred over polydisperse emulsions.
Monodispersed emulsions are described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748. The crystal structure of silver halide grains is
It may be uniform or the inside and the outside may have different halogen compositions. It may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining. Further, it may be bonded to a compound other than silver halide. Examples of compounds other than silver halide include silver rhodan and lead oxide.

The silver halide grains may contain salts of other elements. Examples of other elements include copper, thallium, lead, bismuth, cadmium, zinc, chalcogens (eg, sulfur, selenium, tellurium), gold and VI.
Group II noble metals (eg, rhodium, iridium, iron, platinum, palladium) can be mentioned. Salts of these elements can be added during or after the formation of silver halide grains and included in the grains. Specific methods are described in U.S. Patent Nos. 1195432 and 1951933,
No. 2448060, No. 2628167, No. 2950
No. 972, No. 3488709, No. 3737313,
Nos. 3772031 and 4269927, and Research Disclosure (RD), No. 13,
No. 4, No. 13452 (June 1975). By adding an aqueous solution of an iridium compound to the emulsion during the preparation of the silver halide emulsion, iridium ions can be introduced into the silver halide grains. Examples of water-soluble iridium compounds include hexachloroiridium (II
I) acid salts and hexachloroiridium (IV) salts. Similarly, rhodium ions may be introduced into silver halide grains by adding an aqueous solution of a rhodium compound to the emulsion. Examples of the water-soluble rhodium compound include rhodium ammonium chloride, rhodium trichloride and rhodium chloride.

An iridium compound or a rhodium compound may be used by dissolving it in an aqueous solution of a halide for forming silver halide grains. Further, the aqueous solution of the iridium compound or the rhodium compound may be added before the particles are formed, or may be added during the formation of the particles. Further, it may be added during the period from grain formation to chemical sensitization treatment. It is particularly preferred to add while the particles are being formed. The iridium ion or the rhodium ion is preferably used in an amount of 10 ^{-8 to} 10 ^-3 mol, more preferably 10 ^{-7 to} 10 ^-5 mol, per 1 mol of silver halide. Two or more silver halide grains having different halogen compositions, crystal habits and grain sizes can be used in combination. Silver halide is preferably used as an emulsion. Silver halide emulsions are described in Research Disclosure (RD) Magazine, No. 17643 (December 1978), pp. 22-23, "I. Emulsion Production (Emulsion p.
reparation and types) "and No. 18716
(November 1979), page 648.

The silver halide emulsion is usually subjected to chemical sensitization after physical ripening. It is preferable to use silver halide grains having a relatively low fog value. Additives used in such a process are described in Research Disclosure Magazine, No. 1
No. 7643 and the same No. 18716. Regarding chemical sensitizers, 17643 (p. 23) and
No. 18716 (page 648, right column). Known additives other than those described above are also described in the above two Research Disclosures. For example, as for the sensitivity enhancer, 18716 (648
In the right column of the page), for the antifoggant and the stabilizer, N
o. No. 17643 (pages 24 to 25) and no. 18716
(From page 649, right column).

The silver halide emulsion is usually used after spectral sensitization. As the sensitizing dye used in the light-sensitive material, a silver halide sensitizing dye known in the photographic art can be used. Examples of sensitizing dyes include cyanine dyes,
Examples include merocyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Spectral sensitizing dyes are used to adjust the spectral sensitivity of photosensitive materials to different light source wavelengths such as various lasers (eg, semiconductor laser, helium neon laser, argon ion laser, helium cadmium laser, YAG laser) and light emitting diodes. Can also be used. For example, applying a plurality of spectral sensitizing dyes having different spectral wavelengths to silver halide in the same or different photosensitive layers to enable writing on the same photosensitive material using light sources having different wavelengths. Can also. In addition to the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization (supersensitizer) can be added to the emulsion. Good. Spectral sensitizing dyes are described in Research Disclosure Magazine, No. 17643 (197
December, 8), pp. 23-24, for supersensitizers
No. 18716 (November 1979), p. 649,
Each is listed.

Fine particles of a lipophilic resin can be added to the silver halide emulsion layer to increase the lipophilicity of the relief image. The fine particles of the lipophilic resin also have the effect of increasing the mechanical strength of the relief image. Examples of lipophilic resins include polyester, polyamide, phenol-aldehyde resin, polyvinyl chloride, polyurethane, epoxy resin, silicon resin, alkylphenol resin, ketone resin, alkyd resin, polyamine, polystyrene, polyacrylate, and rosin-modified maleic resin. , Rosin-modified fumaric acid resin, polyvinyl acetate, hydroxypropyl methylcellulose,
Rosin modified phenolic resin and hexahydrophthalate are included. Polystyrene, polyacrylate, polyvinyl acetate, polyurethane, hydroxypropyl methylcellulose and hexahydrophthalate are preferred.
Further, a photosensitive resin (a photopolymerizable polymer or a photocrosslinkable polymer) may be used as the lipophilic resin. Two or more types of lipophilic resins may be used in combination. The fine particles of the lipophilic resin preferably have an average particle size of 0.01 to 5 μm. There is no particular limitation on the shape of the fine particles.

In order to improve photographic characteristics, additives such as an antifogging agent, a silver development accelerator for accelerating silver development, and a stabilizer may be added to the silver halide emulsion layer. Examples thereof include mercapto compounds (JP-A-59-111636).
Azoles and azaindenes (Research Disclosure No. 17643, 24-25)
Page (1978)), carboxylic acids and phosphoric acids containing nitrogen (described in JP-A-59-168442),
Cyclic amide (described in JP-A-61-151841),
Thioethers (described in JP-A-62-151842), polyethylene glycol derivatives (JP-A-62-1)
No. 51843), thiols (JP-A-62-15)
No. 1844), acetylene compounds (Japanese Unexamined Patent Publication No. Sho 62)
-87957) and sulfonamide (described in JP-A-62-178232). As a silver development accelerator or an antifoggant, an aromatic ring (carbon ring or heterocyclic) mercapto compound (Japanese Patent Laid-Open No.
-313967) is particularly preferred. Aromatic heterocyclic mercapto compounds, particularly mercaptotriazole derivatives, are more preferred. The mercapto compound may be added to the light-sensitive material as a mercapto silver compound (silver salt).
The amount of these compounds used is 1 to 1 mole of silver halide.
It is in the range of ^0-7 mol to 1 mol.

A known surfactant may be added to the silver halide emulsion layer. Any of a nonionic activator, an anionic activator, a cationic activator and a fluorine activator can be used. The surfactant is described in JP-A-2-195356. Sorbitans, polyoxyethylenes and fluorinated surfactants are particularly preferred.

[Arbitrarily Provided Layer] The layer optionally provided in the silver halide light-sensitive material is preferably a layer containing a hydrophilic polymer as a binder similarly to the silver halide emulsion layer. It is further preferable that the layer is a layer that is formed. A tanning developer can be added to an optional hydrophilic layer (eg, a hydrophilic protective layer).

A back layer containing a matting agent or an overcoat layer containing a matting agent for the purpose of reducing the tackiness of the front or back surface of the silver halide light-sensitive material and preventing adhesion when the silver halide light-sensitive materials are stacked. Can be provided on the silver halide photosensitive material. As the matting agent, inorganic or organic solid particles that can be dispersed in a water-soluble polymer are used. Examples of materials for the matting agent include oxides (eg, silicon dioxide), alkaline earth metal salts, natural polymers (eg, starch, cellulose) and synthetic polymers. The particle size of the matting agent is preferably in the range of 0.5 to 50 μm. The application amount of the matting agent is 0.
It is preferably in the range of 1 to 1 g / m ² .

A protective layer is provided on the silver halide emulsion layer,
The lipophilic resin fine particles described above may be added to the protective layer.
The protective layer containing the lipophilic resin fine particles is 0.01 to 5 μm
Preferably, it has a thickness of 0.2 to 2 μm. The protective layer preferably has voids between the lipophilic resin particles to such an extent that the developer can penetrate. To the optional layer, the above-mentioned antifoggant, silver development accelerator for accelerating silver development, stabilizer and surfactant may be added.

[Exposure Step] Image exposure is performed with light having a wavelength corresponding to the spectral sensitivity of silver halide. The wavelength is visible light,
Near-ultraviolet light and near-infrared light are generally used, but X-rays and electron beams may be used. Examples of light sources include lamps such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, carbon arc lamps, and various lasers (eg, semiconductor lasers, helium neon lasers, argon ion lasers, helium cadmium lasers, YAG laser), light emitting diode, cathode ray tube and the like. Exposure doses generally range from 0.001 to 1000 μJ / cm ² , preferably from 0.01 to 100 μJ / cm ² . If the support is transparent, it can be exposed through the support from the back side of the support.

[Tanning Development Step] The tanning development of the silver halide photosensitive material is carried out using a developing solution. A tanning developer can be added to the developer. The developer is generally an alkaline solution. The pH of the developer is
It is preferably 9 or more. Examples of the alkaline substance used for adjusting the pH include sodium hydroxide, potassium hydroxide, sodium phosphate, potassium phosphate, lithium phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, and ammonia. As a solvent for the developer, water is preferable. If necessary, an organic solvent may be added to water. The temperature of the developer is
The temperature is preferably from 5 to 40 ° C, more preferably from 20 to 35 ° C. Development time is 10 seconds to 1
The time is preferably 0 minutes, more preferably 20 seconds to 3 minutes.

After the development, the image area may be treated with a solution containing a mercapto compound to increase the lipophilicity of the image area.
-324866). Further, an acidic treatment or a fixing treatment may be performed.

[Elution Step] The silver halide photosensitive material after the tanning development is immersed in hot water and rubbed on the surface to elute the uncured gelatin in the unexposed area to form a relief image of the cured gelatin. Can be. The temperature of the hot water is preferably 40 to 70 ° C. The surface of the photosensitive material may be rubbed with a sponge or a brush. The formed relief image can be used as a lithographic printing plate by drying. As the post-treatment, heat treatment, light irradiation treatment, or chemical treatment may be performed.

[0126]

[Example 1] "Preparation of aluminum support" JI having a thickness of 0.24 mm
The surface of the aluminum plate according to SA-1050 was grained with a nylon brush and an aqueous suspension of pamistone (400 mesh), and then thoroughly washed with water. Next, the film was immersed in a 10% by weight aqueous solution of sodium hydroxide at 70 ° C. for 60 seconds for etching, and then washed with running water. 20% by weight
And then washed with water. The obtained aluminum plate was subjected to a square wave alternating current (condition:
The voltage at the time of the anode is 12.7 V, the ratio of the amount of electricity at the cathode to the amount of electricity at the anode is 0.9, and the amount of electricity at the anode is 160 coulomb / dm.
^{Using 2} ), electrolytic surface roughening treatment was performed in a 1% by weight nitric acid aqueous solution containing 0.5% by weight of aluminum nitrate. The surface roughness of the obtained plate was 0.6 μm (Ra indication). Subsequent to this treatment, the substrate was immersed in a 1% by weight aqueous solution of sodium hydroxide at 40 ° C. for 30 seconds, and then treated in a 30% by weight aqueous solution of sulfuric acid at 55 ° C. for 1 minute. Next, when the thickness is 2.
Anodizing treatment was carried out in a 20% by weight aqueous sulfuric acid solution using a direct current at a current density of 2 A / dm ^{2 so} as to obtain 5 g / dm ² . This was washed with water and dried to prepare a support. The prepared support was used as a No. 3 sodium silicate (SI
O _2: 28 to 30 wt%, Na ₂ O: 9 to 10 wt%,
Fe: 0.02% by weight or less 2.5% by weight aqueous solution (p
H: 11.2) at 70 ° C. for 13 seconds and washed with water.
The amount of silicate measured by X-ray fluorescence analysis was 10 mg / m
^{Was 2} .

"Preparation of silver halide emulsion" In a vessel containing gelatin, potassium bromide and water and heated to 55 ° C, the following thioether compound was further added in an amount of 2.0 × 10 ^-3 mol based on the added amount of silver nitrate. A considerable amount was added. Reaction vessel p
While maintaining the Ag value at 9.2, an aqueous solution of silver nitrate and an aqueous solution of potassium bromide containing rhodium ammonium chloride in a molar ratio of rhodium to the total amount of potassium iodide and silver nitrate of 4 × 10 ⁻⁸ mol were used. With pAg
Silver iodobromide grains were formed by the control double jet method. Subsequently, 55 ° C., pAg = 8.
In step 9, a double-stage double jet method was used to add a silver nitrate aqueous solution and a potassium bromide solution to which hexachloroiridate (III) was added in a molar ratio of iridium to silver of 1.0 × 10 ⁻⁷ mol. Thus, a core / shell type silver iodobromide emulsion having the following composition was prepared.

[0128]

Embedded image

Core: silver iodobromide (silver iodide content: 7.5 mol%) Shell: pure silver bromide Core / shell: 3/7 (silver molar ratio) Average silver iodide content: 2.3 Mol% average particle size: 0.28 μm

The obtained emulsion grains were monodispersed and contained 98% of all grains within ± 40% of the average grain size. Then, after desalting the emulsion, a methanol solution of a spectral sensitizing dye A below (5 × 10 ^- 3M / l) and a spectral sensitizing dye B in methanol in the following (5 × 10
^- The 3M / l), with respect to emulsion per mole of silver nitrate equivalent, respectively 100ml added, 6.2 pH, pAg
Was adjusted to 8.7. Further, gold / sulfur sensitization was performed using sodium thiosulfate and chloroauric acid to prepare an aqueous silver halide emulsion. Solid concentration of emulsion: 29.6% by weight Gelatin concentration of emulsion: 3.5% by weight

[0131]

Embedded image

[0132]

Embedded image

[Formation of a silver halide gelatin emulsion layer] The following coating solution was prepared and coated on an aluminum support.
After drying, a silver halide gelatin emulsion layer having a dry film thickness of 1.5 μm was provided.

<< Coating Solution for Silver Halide Gelatin Emulsion Layer >> ───────────────────────────────── The above silver halide emulsion 5 g Gelatin 10% by weight aqueous solution 24 g Compound (I 2.3 g of a 20 wt% DMF solution of -11) 2.3 g of a 10 wt% methanol solution of compound (II-2) 5.8 g Methol 0.14 g 10 wt% aqueous solution of citric acid 1 g 0.4 g 0.5 wt% methanol solution of the following additive B 1 g water 34 g ────

[0135]

Embedded image

"Preparation of alkaline developer" An alkaline developer having the following composition was prepared.

────────────────────────────────────Alkali developer 液カ リ ウ ム Potassium carbonate 200g Potassium iodide 1g Water 1000g ───────────── ───────────────────────

(Image formation) A light of 670 nm was separated from a silver halide photosensitive material by a sharp cut interference filter with a light emission time of 10 ^-4 sec by xenon flash, and the energy on the photosensitive material surface was 2 μJ / cm ² . Control wedge (Fuji Photo Film Co., Ltd.)
Was brought into close contact with each other to perform image exposure. The image-exposed silver halide photosensitive material was immersed in the prepared alkaline developer for 30 seconds. Next, the silver halide photosensitive material was washed with running water at 45 ° C. for 15 seconds. The surface of the silver halide light-sensitive material was lightly rubbed with a sponge to remove unexposed portions and dried, whereby a relief image having a uniform film surface on an aluminum support was obtained. This was used as a lithographic printing plate. Wet the lithographic printing plate with water and use PI Ink (Fuji Photo Film Co., Ltd.)
Was rubbed to examine the ink receptivity. as a result,
The image area (relief image) received the ink well.
A lithographic printing plate is offset by a printing press (RYOBI3200C).
CD, Ryobi Co., Ltd.), and printing was performed to check the printing durability. As a result, printing of 15,000 or more sheets was possible.

[Example 2] "Formation of silver halide gelatin emulsion layer" The following coating solution was prepared, coated on the aluminum support prepared in Example 1, and dried. A 5 μm silver halide gelatin emulsion layer was provided.

{Coating Solution for Silver Halide Gelatin Emulsion Layer}銀 Silver halide emulsion used in Example 1 5 g 10% by weight aqueous solution of gelatin 24 g 20% by weight DMF solution of compound (I-11) 3.1 g Methol 0.14 g 10% by weight aqueous solution of citric acid 1 g 1% by weight aqueous solution of Additive A used in Example 1 0.4 g For Example 1 1 g of a 0.5% by weight methanol solution of the added additive B 1 g of water 34 g ─

"Formation of hydrophilic layer" The following coating solution was prepared, coated on a silver halide gelatin emulsion layer, and dried to form a hydrophilic layer having a dry film thickness of 0.3 µm.

<< Hydrophilic Layer Coating Solution >> １０ 10% by weight aqueous solution of polyvinyl alcohol (PVA-405, manufactured by Kuraray Co., Ltd.) 12 0.5 g 1% by weight aqueous solution of Additive A used in Example 1 0.7 g Methanol 30 g Water 4 g Compound (II-2) 0.6 g ──────────────────

(Image formation) Light of 670 nm was separated by a sharp cut interference filter with a light emission time of 10 ^-4 seconds by a xenon flash using a silver halide photosensitive material, and the energy on the photosensitive material surface was 2 μJ / cm ² . Control wedge (Fuji Photo Film Co., Ltd.)
Was brought into close contact with each other to perform image exposure. The silver halide photosensitive material subjected to image exposure was added to the alkali developing solution prepared in Example 1 for 3 hours.
Dipped for 0 seconds. Next, 45 parts of the silver halide photosensitive material were used.
Washed for 15 seconds with running water at ℃. The surface of the silver halide light-sensitive material was lightly rubbed with a sponge to remove unexposed portions and dried, whereby a relief image having a uniform film surface on an aluminum support was obtained. This was used as a lithographic printing plate. The lithographic printing plate was wetted with water and rubbed with a PI ink (manufactured by Fuji Photo Film Co., Ltd.) to examine the ink receptivity. As a result, the image area (relief image) received the ink well. The lithographic printing plate is converted to an offset printing machine (RYO
BI3200 CCD, Ryobi Co., Ltd.)
When printing was performed and the printing durability was checked, printing of 15,000 or more sheets was possible.

Examples 3 to 7 Instead of the compound (I-11) added to the silver halide gelatin emulsion layer and the compound (II-2) added to the hydrophilic layer, the compounds shown in Table 1 were replaced by A silver halide photosensitive material was prepared and evaluated in the same manner as in Example 2 except that the same amount was used. The results are shown in Table 1.

[0145]

[Table 1] Table 1-Silver halide tanning developer exposure Material Emulsion layer Hydrophilic layer Ink receptivity Printing durability ──────────────────────────────────── Example 2 (I-11) (II-2) Good 15,000 or more Example 3 (I-11) (II-1) Good 15,000 or more Example 4 (I-8) (II-90) Good 15,000 or more Example 5 (I-18) (II-92) Good 15,000 sheets or more Example 6 (I-23) (II-42) Good 15,000 sheets or more Example 7 (I-28) (II-44) Good 15,000 sheets or more ────────────────────────────────────

[Example 8] "Formation of silver halide gelatin emulsion layer" The following coating solution was prepared, coated on the aluminum support used in Example 1, and dried to obtain a dried film having a dry film thickness of 1. A 2 μm silver halide gelatin emulsion layer was provided.

<< Coating Solution for Silver Halide Gelatin Emulsion Layer >>銀 Silver halide emulsion used in Example 1 12 g 10% by weight aqueous solution of gelatin 40 g 10 wt% aqueous solution of citric acid 2.5 g Methol 0.3 g 1 wt% aqueous solution of additive A used in Example 1 0.8 g 0.5 wt% methanol solution of additive B used in Example 1 60g of water

[Formation of First Hydrophilic Layer] The following coating solution was prepared, coated on a silver halide gelatin emulsion layer, and dried to form a first hydrophilic layer having a dry film thickness of 1.0 μm. Was.

<< Coating Liquid for First Hydrophilic Layer >> １０ Gelatin 10% by weight aqueous solution 50g Compound (I-23) 20% by weight DMF Solution 10 g 10 wt% aqueous solution of citric acid 1 g 1 wt% aqueous solution of additive A used in Example 1 1 g Water 50 g ─────────────

[Formation of Second Hydrophilic Layer] The following coating solution was prepared, applied on the first hydrophilic layer, and dried to provide a second hydrophilic layer having a dry film thickness of 0.3 μm. .

塗布 Coating solution for second hydrophilic layer──── １０ 10% by weight aqueous solution of polyvinyl alcohol (PVA-405, manufactured by Kuraray Co., Ltd.) Liquid 12.5 g 1 wt% aqueous solution of Additive A used in Example 1 0.7 g Methanol 30 g Water 4 g Compound (II-91) 0.6 g ────────────────────

(Image formation) Light of 670 nm was separated from the silver halide photosensitive material by a sharp cut interference filter with a light emission time of 10 ^-4 seconds by xenon flash, and the energy on the photosensitive material surface was 2 μJ / cm ² . Control wedge (Fuji Photo Film Co., Ltd.)
Was brought into close contact with each other to perform image exposure. The silver halide photosensitive material subjected to image exposure was added to the alkali developing solution prepared in Example 1 for 3 hours.
Dipped for 0 seconds. Next, 45 parts of the silver halide photosensitive material were used.
Washed for 15 seconds with running water at ℃. The surface of the silver halide light-sensitive material was lightly rubbed with a sponge to remove unexposed portions and dried, whereby a relief image having a uniform film surface on an aluminum support was obtained. This was used as a lithographic printing plate. The lithographic printing plate was wetted with water and rubbed with a PI ink (manufactured by Fuji Photo Film Co., Ltd.) to examine the ink receptivity. As a result, the image area (relief image) received the ink well. The lithographic printing plate is converted to an offset printing machine (RYO
BI3200 CCD, Ryobi Co., Ltd.)
When printing was performed and the printing durability was checked, printing of 15,000 or more sheets was possible.

[Embodiment 9]

[Formation of First Hydrophilic Layer] The following coating solution was prepared, coated on the aluminum support used in Example 1, and dried to obtain a first hydrophilic layer having a dry film thickness of 1.0 μm. Layers were provided.

<< Coating Liquid for First Hydrophilic Layer >> １０ 50% aqueous solution of gelatin at 50% by weight 20% DMF of compound (I-19) Solution 10 g 10% by weight aqueous solution of citric acid 1 g 1% by weight aqueous solution of additive A used in Example 1 0.8 g Water 50 g ───────────────

[Formation of silver halide gelatin emulsion layer] The following coating solution was prepared, coated on the first hydrophilic layer, and dried to form a silver halide gelatin emulsion layer having a dry film thickness of 1.2 µm. Provided.

塗布 Coating solution for silver halide gelatin emulsion layer───銀 Silver halide emulsion used in Example 1 12 g 10% by weight aqueous solution of gelatin 40 g 10% by weight aqueous solution of citric acid 2.5 g Methol 0.3 g 1% by weight aqueous solution of additive A used in Example 1 1 g 0.5% by weight methanol solution of additive B used in Example 1 2 g Water 60 g ────────────────────────────────────

[Formation of Second Hydrophilic Layer] The following coating solution was prepared, coated on a silver halide gelatin emulsion layer, and dried to form a second hydrophilic layer having a dry thickness of 0.3 μm. Was.

<< Coating Liquid for Second Hydrophilic Layer >> １０ 10% by weight aqueous solution of polyvinyl alcohol (PVA-405, manufactured by Kuraray Co., Ltd.) Liquid 12.5 g 1 wt% aqueous solution of Additive A used in Example 1 0.7 g Methanol 30 g Water 4 g Compound (II-91) 0.6 g ────────────────────

(Image formation) The light of 670 nm was separated from the silver halide photosensitive material by a sharp cut interference filter with a light emission time of 10 ^-4 seconds by a xenon flash, and the energy on the photosensitive material surface was 2 μJ / cm ² . Control wedge (Fuji Photo Film Co., Ltd.)
Was brought into close contact with each other to perform image exposure. The silver halide photosensitive material subjected to image exposure was added to the alkali developing solution prepared in Example 1 for 3 hours.
Dipped for 0 seconds. Next, 45 parts of the silver halide photosensitive material were used.
Washed for 15 seconds with running water at ℃. The surface of the silver halide light-sensitive material was lightly rubbed with a sponge to remove unexposed portions and dried, whereby a relief image having a uniform film surface on an aluminum support was obtained. This was used as a lithographic printing plate. The lithographic printing plate was wetted with water and rubbed with a PI ink (manufactured by Fuji Photo Film Co., Ltd.) to examine the ink receptivity. As a result, the image area (relief image) received the ink well. The lithographic printing plate is converted to an offset printing machine (RYO
BI3200 CCD, Ryobi Co., Ltd.)
When printing was performed and the printing durability was checked, printing of 15,000 or more sheets was possible.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of a preferred embodiment of a silver halide photosensitive material.

FIG. 2 is a schematic cross-sectional view of another preferred embodiment of a silver halide photosensitive material.

FIG. 3 is a schematic sectional view of still another preferred embodiment of a silver halide photosensitive material.

FIG. 4 is a schematic cross-sectional view of still another preferred embodiment of the silver halide photosensitive material.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 hydrophilic support 2 silver halide gelatin emulsion layer 21 silver halide grains 22 gelatin 3 hydrophilic layer 31 hydrophilic polymer 4 first hydrophilic layer 41 gelatin 5 second hydrophilic layer 51 hydrophilic polymer I Formula (I) Tanning developer represented by formula II Tanning developer represented by formula (II)

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) G03F 7/06 G03F 7/06 7/11 501 7/11 501 F term (reference) 2H016 AA01 AD04 AG01 2H023 CD06 2H025 AA01 AA04 AB03 AC01 AD01 BB00 CB03 CC20 DA03 2H096 AA06 BA17 EA02 GA09 GA60

Claims (7)

[Claims] 1. A silver halide photosensitive material having a silver halide gelatin emulsion layer on a support, wherein the silver halide gelatin emulsion layer or an optional hydrophilic layer is represented by the following formula (I). Phenol compound and the following formula (II)
And a phenolic compound represented by the following formula: [Wherein L is a divalent to hexavalent aliphatic group, a divalent to hexavalent aromatic group, a divalent to hexavalent heterocyclic group, -O-, -S
-, - CO -, - NH -, - N <, - SO 2 -, - SO
And an n-valent linking group selected from-and combinations thereof, wherein the aliphatic group, the aromatic group and the heterocyclic group may have a substituent; the benzene ring may have a substituent other than hydroxy. M is 2 or 3; and n is an integer from 2 to 6. Wherein p is 1 or 2; and R is an aliphatic group having 5 to 40 carbon atoms, 7 to 4 carbon atoms.
0 aromatic groups, aliphatic acyl groups having 5 to 40 carbon atoms, aromatic acyl groups having 7 to 40 carbon atoms, aliphatic oxycarbonyl groups having 5 to 40 carbon atoms, and carbon atoms having 5 to 40 carbon atoms. An aromatic oxycarbonyl group having 7 to 40 carbon atoms, an aliphatic acyloxy group having 5 to 40 carbon atoms, an aromatic acyloxy group having 7 to 40 carbon atoms, and 5 carbon atoms;
To 40 aliphatic substituted carbamoyl groups or aromatic substituted carbamoyl groups having 7 to 40 carbon atoms]. 2. The silver halide light-sensitive material according to claim 1, wherein the silver halide gelatin emulsion layer contains a phenol compound represented by the formula (I) and a phenol compound represented by the formula (II). 3. A silver halide emulsion layer comprising a support, a silver halide emulsion layer, and a hydrophilic layer, wherein the silver halide gelatin emulsion layer comprises a phenol compound represented by the formula (I):
The silver halide light-sensitive material according to claim 1, wherein the hydrophilic layer contains a phenol compound represented by the formula (II). 4. A phenolic compound comprising a support, a silver halide emulsion layer, a first hydrophilic layer, and a second hydrophilic layer which are laminated in this order, wherein the first hydrophilic layer is a phenolic compound represented by the formula (I) The silver halide photosensitive material according to claim 1, wherein the second hydrophilic layer contains a phenol compound represented by the formula (II). 5. A laminate comprising a support, a first hydrophilic layer, a silver halide emulsion layer, and a second hydrophilic layer in this order, wherein the first hydrophilic layer is a phenolic compound represented by the formula (I) The silver halide photosensitive material according to claim 1, wherein the second hydrophilic layer contains a phenol compound represented by the formula (II). 6. A photosensitive lithographic printing plate precursor having a silver halide gelatin emulsion layer on a hydrophilic support, wherein the silver halide gelatin emulsion layer or an optional hydrophilic layer is provided. A photosensitive lithographic printing plate precursor comprising a phenol compound represented by the formula (I) and the phenol compound represented by the formula (II) according to claim 1. 7. A step of imagewise exposing a silver halide light-sensitive material having a support and a silver halide gelatin emulsion layer,
A step of tanning the silver halide photosensitive material to harden the gelatin in the exposed areas, and a step of eluting the unhardened gelatin in the unexposed areas to form a relief image of the hardened gelatin, in this order. A relief image forming method comprising performing tanning development using a phenol compound represented by the following formula (I) and a phenol compound represented by the following formula (II) as a tanning developer. : [Wherein L is a divalent to hexavalent aliphatic group, a divalent to hexavalent aromatic group, a divalent to hexavalent heterocyclic group, -O-, -S
-, - CO -, - NH -, - N <, - SO 2 -, - SO
And an n-valent linking group selected from-and combinations thereof, wherein the aliphatic group, the aromatic group and the heterocyclic group may have a substituent; the benzene ring may have a substituent other than hydroxy. M is 2 or 3; and n is an integer from 2 to 6. Wherein m is 1 or 2; and R is an aliphatic group having 5 to 40 carbon atoms, and 7 to 4 carbon atoms.
0 aromatic groups, aliphatic acyl groups having 5 to 40 carbon atoms, aromatic acyl groups having 7 to 40 carbon atoms, aliphatic oxycarbonyl groups having 5 to 40 carbon atoms, and carbon atoms having 5 to 40 carbon atoms. An aromatic oxycarbonyl group having 7 to 40 carbon atoms, an aliphatic acyloxy group having 5 to 40 carbon atoms, an aromatic acyloxy group having 7 to 40 carbon atoms, and 5 carbon atoms;
To 40 aliphatic substituted carbamoyl groups or aromatic substituted carbamoyl groups having 7 to 40 carbon atoms].