JPH10186597A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the method for processing the silver halide sensitive material capable of maintaining high contrast even in ultrahigh speed processing and not hindering film hardening and reducing residual dye stains. SOLUTION: The silver halide photographic sensitive material containing a hydrazine derived uncleator having a nonionic group forming an intramolecular hydrogen bond with an anionic group or an H atom of the hydrazine near the hydrazine group and a polymer latex is processed in an automatic developing machine in the total processing time of 20-60sec, and at that time, the total gelatin among (G) is <=2.5g/m<2> and a weight ratio of the total gelatin amount (G) to the total polymer latex (PL) PL/G of 0.1-0.33.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly to a method for processing a silver halide photographic light-sensitive material which forms a high-contrast silver image and is excellent in rapid processing.

[0002]

2. Description of the Related Art Among photographic plate making processes in the field of printing plate making, silver halide photographic light-sensitive materials (hereinafter referred to as "light-sensitive materials") which are used particularly for plate-collecting and turning-back work are used for reproducing line drawings and halftone images. In order to make good, the image part and the non-image part have a high blackening density that is clearly distinguished, and what is called a super-hard photographic characteristic is required,
Further, in the plate making process, particularly in the bright room plate collecting process, since the amount of processing of the photosensitive material is very large, ultra-rapid processing is strongly desired.

As a method for imparting ultra-high contrast photographic characteristics to a light-sensitive material, a method of incorporating a hydrazine derivative into a light-sensitive material and the like have been known. No. 60-140338,
No. 61-238049. However, conventional hydrazine derivatives cause dura inhibition,
For this reason, there has been a problem that the film of the light-sensitive material constituting layer is loosened, the water content is increased, and drying is delayed, so that ultra-rapid processing becomes difficult. Furthermore, during processing, additives in the photosensitive material such as hydrazine derivatives elute into the processing solution, deteriorating the running stability of the processing. To prevent this, polymer latex was added and trapped to prevent elution. . However, the polymer latex has been an obstacle to performing ultra-rapid processing to deteriorate the drying property.

On the other hand, an antistatic layer provided on a support is necessary to prevent problems due to static electricity in operation. However, a water-soluble polymer or metal oxide is dispersed and applied to a hydrophilic binder such as gelatin. For this reason, the drying property deteriorates, which is not preferable in terms of ultra-rapid processing.

[0005] Furthermore, in the case of ultra-rapid processing, a large amount of dye remains, but polymer latex is not preferred in this respect.

When a hydrazine derivative is used as a high contrast agent, the pH of the developer is 11 or more. However, since the developer having a pH of 11 or more is easily oxidized by air and is unstable, the pH of the developer is high.
Efforts have been made to reduce the processing, and processing with an ascorbic acid-based developing agent has been studied, but in combination with a conventional hydrazine derivative, high contrast and ultra-rapid processing suitability cannot be said to be sufficient.

[0007]

SUMMARY OF THE INVENTION In view of the above-mentioned problems, an object of the present invention is to provide a silver halide which maintains high contrast even in ultra-rapid processing, does not cause hardening inhibition, and has little residual color. An object of the present invention is to provide a method for processing a photographic material.

[0008]

The above object of the present invention is achieved by the following means.

A silver halide photographic light-sensitive material containing a hydrazine-based nucleating agent having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine near a hydrazine group and a polymer latex is automatically developed. The total amount of gelatin (G) on the side having the silver halide emulsion layer is 2.5 g / m ² or less, and the total amount of gelatin (G) is Latex (PL) weight ratio of 0.1
≦ PL / G ≦ 0.33, a method for processing a silver halide photographic material.

The silver halide photograph as described in the above item, which is processed with a developing solution containing a compound represented by the following general formula [A] and containing substantially no p-dihydroxybenzene compound. Processing method of photosensitive material.

[0011]

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[In the formula, R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group. And R ₁ and R ₂ may combine with each other to form a ring.

K represents 0 or 1, and when k = 1, X represents -CO- or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal. The method for processing a silver halide photographic light-sensitive material as described in the above item or item, wherein the silver halide photographic light-sensitive material has an antistatic layer.

Hereinafter, the present invention will be described specifically.

The hydrazine nucleating agent according to the present invention will be described. The hydrazine-based nucleating agent according to the present invention is a hydrazine-based nucleating agent characterized by having an anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine near a hydrazine group.

More specifically, examples of the anionic group include carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid and salts thereof. Here, the vicinity of the hydrazine group means a bond formed by 2 to 5 atoms selected from a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom between a nitrogen atom close to the anionic group of hydrazine and the anionic group. It means that the chain is interposed. Among them, a case where a bond chain formed of 2 to 5 atoms selected from a carbon atom and a nitrogen atom is preferred, and a case where a bond chain formed of 2 to 3 carbon atoms is more preferred It is.

The nonionic group forming an intramolecular hydrogen bond with the hydrogen atom of hydrazine has a lone electron pair of 5 to 7
It is a group that forms a hydrogen bond with a hydrogen atom of hydrazine in a member ring and has at least one of an oxygen atom, nitrogen hydrogen, sulfur atom, and phosphorus atom. Examples of the nonionic group include an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group, an alkoxycarbonyl group, a urethane group, a ureido group, an acyloxy group, and an acylamino group. Of these, anionic groups are preferred,
Further, as the anionic group, carboxylic acids and salts thereof are most preferred.

Preferred hydrazine-based nucleating agents according to the present invention are those represented by the following formulas (1) to (3).

General formula (1)

[0020]

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[In the formula, R ¹ represents an alkyl group, an aryl group or a heterocyclic group, and L ¹ represents 2 having an electron-withdrawing group.
Y ¹ represents an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine. General formula (2)

[0022]

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[0023] wherein, R ² represents an alkyl group, an aryl group or a heterocyclic group, L ² represents a divalent linking group, Y ²
Represents an anionic group or a nonionic group which forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine. General formula (3)

[0024]

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[0025] represents wherein, X ³ is a group substitutable on the benzene ring, R ³ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group or an amino group, Y ³ is It represents an anionic group or a nonionic group that forms an intramolecular hydrogen bond with a hydrogen atom of hydrazine. m ³ is an integer of 0 to 4, and n ³ is 1 or 2. When n ³ is 1, R ³ has an electron-withdrawing group. The general formulas (1) to (3) will be described in more detail.

The alkyl group of R ¹ and R ² has 1 to 1 carbon atoms.
16, preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, t-butyl, allyl, propargyl, 2-butenyl, 2-hydroxyethyl, Benzyl, benzhydryl, trityl, 4-methylbenzyl,
2-methoxyethyl, cyclopentyl and 2-acetamidoethyl.

The aryl group is an aryl group having 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms, for example, phenyl, naphthyl, p-alkoxyphenyl, p-sulfonamidophenyl, p-ureidophenyl, p-amidophenyl It is.

The heterocyclic group is a 5- or 6-membered saturated or unsaturated heterocyclic ring having at least one oxygen atom, nitrogen atom or sulfur atom having 1 to 5 carbon atoms, which is a heteroatom constituting the ring. May be one or more in number, for example, 2-furyl, 2-thienyl,
-Pyridyl.

R ¹ and R ² are preferably an aryl group, an aromatic heterocyclic group or an aryl-substituted methyl group, and more preferably an aryl group (eg, phenyl, naphthyl).

R ¹ and R ² may be substituted with a substituent. Examples of the substituent include an alkyl group, an aralkyl group, an alkoxy group, an alkyl or aryl substituted amino group, an amide group, a sulfonamide group and a ureido group. , Urethane group, aryloxy group, sulfamoyl group, carbamoyl, aryl group, alkylthio group, arylthio group,
A sulfonyl group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, and a phosphoric acid amide group.

These groups may be further substituted.
Of these, a sulfonamide group, a ureido group, an amide group, an alkoxy group, and a urethane group are preferred, and a sulfonamide group and a ureido group are more preferred. When possible, these groups may be linked to each other to form a ring.

The alkyl group of R ^3, aryl group, heterocyclic group include those described in R ^1. The alkenyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, such as vinyl and 2-styryl. The alkynyl group has 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, such as ethynyl and phenylethynyl. The alkoxy group is a linear, branched or cyclic alkoxy group having 1 to 16, preferably 1 to 10 carbon atoms, such as methoxy, isopropoxy and benzyloxy. The amino group has 0 to 16 carbon atoms, preferably 1 to 10 carbon atoms, and includes ethylamino, benzylamino and phenylamino. When n ³ = 1, R ³ is preferably an alkyl group, an alkenyl group, or an alkynyl group. When n ³ = 2, R ³ is preferably an amino group or an alkoxy group.

The electron-withdrawing group possessed by R ³ has a Hammett's σ _m of 0.2 or more, preferably 0.3
In the above, for example, a halogen atom (fluorine, chlorine,
Bromine), cyano group, sulfonyl group (methanesulfonyl,
Benzenesulfonyl), sulfinyl group (methanesulfinyl), acyl group (acetyl, benzoyl), oxycarbonyl group (methoxycarbonyl), carbamoyl group (N-methylcarbamoyl), sulfamoyl group (methylsulfamoyl), halogen-substituted alkyl group ( Trifluoromethyl), a heterocyclic group (2-benzoxazolyl, pyrrolo) and a quaternary onium group (triphenylphosphonium, trialkylammonium, pyridinium). Examples of R ³ having an electron-withdrawing group include trifluoromethyl, difluoromethyl, pentafluoroethyl, cyanomethyl, methanesulfonylmethyl, acetylethyl, trifluoromethylethynyl, and ethoxycarbonylmethyl.

L ¹ and L ² each represent a divalent linking group, and include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent heterocyclic group, and those represented by —O—, —S—,
-NH -, - CO -, - it is the concatenation in made from one or a combination of such groups - SO _2. L ¹ and L ² are R ¹
May be substituted with the groups described as the substituents. Examples of the alkylene group include methylene, ethylene, trimethylene, propylene, 2-buten-1,4-yl,
-Butin-1,4-yl. The alkenylene group is, for example, vinylene. The alkynylene group is ethynylene. The arylene group is, for example, phenylene. The divalent heterocyclic group is, for example, furan-1,4-diyl. L ¹ is preferably an alkylene group, an alkenylene group, an alkynylene group, or an arylene group, and more preferably an alkylene group. Further, an alkylene group having a chain length of 2 to 3 carbon atoms is most preferable. L The ² alkylene group, an arylene group, -NH- alkylene -, - O-alkylene -, - NH- arylene - are preferred, -NH- alkylene -, - O-alkylene - is more preferable.

Examples of the electron-withdrawing group of L ¹ include those described as the electron-withdrawing group of R ³ . L
Examples of ¹ include tetrafluoroethylene, fluoromethylene, hexafluorotrimethylene, perfluorophenylene, difluorovinylene, cyanomethylene, and methanesulfonylethylene.

Y ¹ to Y ^{3 are} as described above, and are anionic groups or nonionic groups in which a lone electron pair forms a hydrogen bond with hydrazine hydrogen in a 5- to 7-membered ring. More specifically, examples of the anionic group include carboxylic acid, sulfonic acid, fulphinic acid, phosphoric acid, phosphonic acid, and salts thereof. Examples of the salt include alkali metal ions (sodium and potassium), alkaline earth metal ions (calcium and magnesium), ammonium (ammonium, triethylammonium, tetrabutylammonium, pyridium) and phosphonium (tetraphenylphosphonium). As the nonionic group, an oxygen atom, a nitrogen atom, a group having at least one of a sulfur atom and a phosphorus atom, an alkoxy group, an amino group, an alkylthio group, a carbonyl group, a carbamoyl group, an alkoxycarbonyl group, a urethane group, a ureido group, An acyloxy group and an acylamino group are exemplified. Y ¹ to Y ³ are preferably anionic groups, and more preferably carboxylic acids and salts thereof.

Examples of the group capable of substituting on the benzene ring of X ³ and preferable ones include those described as the substituent of R ^{1 in the} general formula (1). When m ³ is 2 or more, they may be the same or different.

R ¹ to R ³ or X ³ may have a diffusion-resistant group used in photographic couplers or may have a group promoting adsorption to silver halide. The diffusion-resistant group has 8 to 30 carbon atoms, and preferably has 12 to 25 carbon atoms. As the adsorption-promoting group for silver halide, thioamides (for example, thiourethane,
Thioureido, thioamide), mercaptos (for example,
5-mercaptotetrazole, 3-mercapto-1,
2,4-triazole, 2-mercapto-1,3,4-
Heterocyclic mercapto such as thiadiazole, 2-mercapto-1,3,4-oxadiazole, alkyl mercapto, aryl mercapto) and imino silver 5
And a 6-membered nitrogen-containing heterocycle (eg, benzotriazole). Examples of those having a silver halide adsorption promoting group include those having a structure in which the adsorptive group is protected and the protective group is removed at the time of development to increase the adsorptivity to silver halide.

In the general formulas (1) to (3), the radicals of each of the two compounds from which the hydrogen atoms have been removed may combine to form a bis-type. In the general formulas (1) to (3), the general formulas (1) and (2) are preferable, and the general formula (1) is more preferable. Furthermore, general formula (1)
In formulas (3) to (3), the following general formulas (4) to (6) are more preferable, and general formula (4) is most preferable.

General formula (4)

[0041]

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[Wherein, R ⁴ , X ⁴ and m ⁴ have the same meanings as R ³ , X ³ and m ^{3 in the} general formula (3), respectively, and L ⁴ and Y ⁴ represent L ^{1 in the} general formula (1). , Y ¹ . General formula (5)

[0043]

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[Wherein, R ⁵ , X ⁵ and m ⁵ have the same meanings as R ³ , X ³ and m ^{3 in the} general formula (3), respectively, and L ⁵ and Y ⁵ are L ^{2 in the} general formula (2). , Y ² . General formula (6)

[0045]

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[Wherein R ⁶¹ , R ⁶² , X ⁶ , m ⁶ , n ⁶ , Y
Has the same meaning as R ³ , X ³ , m ³ , n ³ , and Y ^{3 in} formula (3). Hereinafter, specific examples of the hydrazine-based nucleating agent according to the present invention will be shown, but the present invention is not limited thereto.

[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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The hydrazine-based nucleating agent according to the present invention may be any suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl It can be used by dissolving it in sulfoxide, methylcellosolve and the like. Also, by the well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate,
It can be dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone to mechanically prepare and use an emulsified dispersion. Alternatively, by a method known as a solid dispersion method, hydrazine derivative powder is ball milled in water,
It can be dispersed and used by a colloid mill or an ultrasonic wave.

The hydrazine nucleating agent according to the present invention may be added to any layer of the silver halide emulsion layer or another hydrophilic colloid layer on the side of the silver halide emulsion layer with respect to the support. It is preferable to add to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto. The addition amount of the nucleating agent of the present invention is 1 × 10 ⁻⁶ to 1 mol of silver halide.
1 × 10 ⁻² mol is preferable, 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol is more preferable, and 5 × 10 ⁻⁵ to 1 × 10 ⁻³ mol is most preferable.

In the present invention, an amine derivative, an onium salt, a disulfide derivative or a hydroxymethyl derivative can be used as a nucleation promoting agent. Examples of the amine derivative include, for example, JP-A-60-140340,
No. 50829, No. 62-222241, No. 62-25
No. 0439, No. 62-280733, No. 63-124
Nos. 045, 63-133145, 63-2868
No. 40 and the like. More preferably, the amine derivative is disclosed in JP-A-63-12404.
No. 5, 63-133145, 63-386840
Or a compound having a group that adsorbs to silver halide described in JP-A-62-222 or a compound having a total of 20 or more carbon atoms described in JP-A-62-222241.

As the onium salt, an ammonium salt or a phosphonium salt is preferable. Preferred ammonium or phosphonium salts are preferred. Examples of preferred ammonium salts are described in Japanese Patent Application No. 5-97866,
Compounds described in 2-250439, 62-280733 and the like can be mentioned. Examples of preferred phosphonium salts are described in JP-A-61-16793.
9 and 62-280733. Examples of the disulfide derivative include compounds described in JP-A-61-198147. Examples of the hydroxymethyl derivative include, for example, U.S. Pat.
777,118, EP231,850, JP-A-62
Compounds described in -50829 and the like can be mentioned, and a diarylmethanol derivative is more preferable.

Next, specific examples of the nucleation accelerator will be shown. However, the present invention is not limited to the following compounds.

[0058]

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The polymer latex used in the present invention will be described. The polymer latex used in the present invention preferably has an active methylene group from the viewpoint of trapping the hydrazine-based nucleating agent in a small amount.

Having an active methylene group means having a repeating unit derived from an ethylenically unsaturated monomer having an active methylene group. Hereinafter, the ethylenically unsaturated monomer containing an active methylene group will be described in detail.

The ethylenically unsaturated monomer containing an active methylene group used in the present invention is represented by the following general formula (IV).

[0062]

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Wherein R ¹ is a hydrogen atom and has 1 to 4 carbon atoms.
(Eg, methyl, ethyl, n-propyl, n-butyl) or a halogen atom (eg, chlorine atom, bromine atom), preferably a hydrogen atom, a methyl group, or a chlorine atom. L represents a single bond or a divalent linkage, and is specifically represented by the following formula.

[0064]

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L ¹ is —CON (R ² ) — (R ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a substituted alkyl group having 1 to 6 carbon atoms), —COO—, and —NHCO—. ,
-OCO-,

[0066]

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(R ² and R ⁴ each independently represent hydrogen, hydroxyl, halogen atom or substituted or unsubstituted alkyl, alkoxy, acyloxy or aryloxy), and L ² is a link connecting L ¹ and X. Represents a group, m represents 0 or 1, and n represents 0 or 1. L
^The linking group represented by ² is specifically represented by the following general formula.

[0068]

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J ¹ , J ² , and J ³ may be the same or different, and include —CO—, —SO ₂ —, and —CON (R ⁵ ) — (R ⁵
Hydrogen atom, an alkyl group (1-6 carbon atoms), a substituted alkyl group (having 1 to 6 carbon _{atoms), - SO 2 N (R} 5) - (R 5 is as defined above), - N (R ⁵⁾ -R ⁶ - (R ⁵ is as defined above, R ⁶
Alkylene group) 1 to about 4 carbon ^{atoms, - N (R 5) -R} 6
—N (R ⁷ ) — (R ⁵ and R ⁶ are as defined above, and R ⁷ represents a hydrogen atom, an alkyl group (1 to 6 carbon atoms), a substituted alkyl group (1 to 6 carbon atoms)), or —. O-, -S-, -N
(R ⁵ ) —CO—N (R ⁷ ) — (R ⁵ and R ⁷ are as defined above), —N (R ⁵ ) —SO ₂ —N (R ⁷ ) — (R ⁵ and R ⁷ are as defined above. synonymous), - COO -, - OCO -, - N (R 5)
—CO ₂ — (R ⁵ is as defined above), —N (R ⁵ ) CO—
(R ⁵ is as defined above).

P, q, r represent 0 or 1. X ¹ ,
X ² and X ³ may be the same or different from each other and represent an unsubstituted or substituted alkylene group, aralkylene group or phenylene group having 1 to 10 carbon atoms, and the alkylene group may be linear or branched. Examples of the alkylene group include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, aralkylene groups such as benzylidene, and phenylene groups such as p-phenylene and m- Examples include phenylene and methylphenylene.

X represents a monovalent group containing an active methylene group, and preferred examples thereof include R ⁸ —CO—CH ₂ —CO
_{^{O-, R 8 -NHCO-CH 2}} -COO-, R 8 -CO-
CH ₂ —CO—, R ⁸ —CO—CH ₂ —CON (R ⁵ ) — and the like can be mentioned. R ⁸ is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms (eg, methyl, ethyl,
n-propyl, n-butyl, t-butyl, n-nonyl,
2-methoxyethyl, 4-phenoxybutyl, benzyl, 2-methanesulfonamidoethyl and the like, substituted or unsubstituted aryl groups (for example, phenyl, p-methylphenyl, p-methoxyphenyl, o-chlorophenyl and the like), alkoxy Groups (eg, methoxy, ethoxy, methoxyethoxy, n-butoxy, etc.), cycloalkyloxy groups (eg, cyclohexyloxy), allyloxy (eg, phenoxy, p-methylphenoxy, o-chlorophenoxy, p-cyanophenoxy, etc.) , An amino group, or a substituted amino group (eg, methylamino, ethylamino, dimethylamino, butylamino, etc.).

Hereinafter, the general formula (IV) used in the present invention will be described.
Examples of the monomer represented by are, but are not limited to, ethylenically unsaturated monomers having an active methylene group.

M-1 2-acetoacetoxyethyl methacrylate M-2 2-acetoacetoxyethyl acrylate M-3 2-acetoacetoxypropyl methacrylate M-4 2-acetoacetoxypropyl acrylate M-5 2-acetoacetoxyamidoethyl methacrylate M -6 2-acetoacetoxyamidoethyl acrylate M-7 2-cyanoacetoxyethyl methacrylate M-8 2-cyanoacetoxyethyl acrylate M-9 N- (2-cyanoacetoxyethyl) acrylamide M-10 2-propionylacetoxyethyl acrylate M -11 N- (2-propionylacetoxyethyl)
Methacrylamide M-12 N-4- (acetoacetoxybenzyl) phenylacrylamide M-13 ethyl acryloyl acetate M-14 acryloylmethyl acetate M-15 N-methacryloyloxymethyl acetoacetoxyamide M-16 ethyl methacryloyl acetoacetate M-17 N -Allyl cyanoacetamide M-18 Methyl acryloylacetoacetate M-19 N- (2-methacryloyloxymethyl) cyanoacetamide M-20 p- (2-acetoacetyl) ethylstyrene M-21 4-acetoacetyl-1-methacryloylpiperazine M-22 Ethyl-α-acetoacetoxymethacrylate M-23 N-butyl-N-acryloyloxyethylacetoacetoxyamide M-24 p- (2-acetoacetate (Ethoxy) ethylstyrene An ethylenically unsaturated monomer other than the above-mentioned ethylenically unsaturated monomer containing an active methylene group may be copolymerized in the polymer latex used in the present invention. Examples of such a monomer include acrylic acid esters, methacrylic acid esters, vinyl esters, acrylamides, methacrylamides, olefins, styrenes, vinyl ethers, and the monomers constituting the core particles as specific examples. Among them, acrylic esters, methacrylic esters,
Vinyl esters and styrenes are particularly preferred.

Preferred compounds of the polymer latex used in the present invention are shown below.

The values in parentheses indicate the weight percentage of each component in the copolymer. However, the present invention is not limited to these.

Po-1 ethyl acrylate / M-1 /
Acrylic acid copolymer (85/10/5) Po-2 n-butyl acrylate / M-1 / 2-acrylamide-2-methylpropane sodium sulfonic acid copolymer (85/10/5) Po-3 n- Butyl acrylate / M-1 / methacrylic acid copolymer (85/5/10) Po-4 2-ethylhexyl acrylate / M-2 /
2-acrylamide-2-methylpropanesulfonic acid sodium copolymer (75/20/5) Po-5-9 n-butyl acrylate / M-1 / acrylic acid copolymer (x / y / z) Po-5 x / y / z = 95/2/3 Po-6 x / y / z = 92/5/3 Po-7 x / y / z = 89/8/3 Po-8 x / y / z = 81 / 16/3 Po-9 x / y / z = 72/25/3 Po-10 n-butyl acrylate / styrene / M-
1 / methacrylic acid copolymer (65/20/5/10) Po-11 methyl acrylate / M-4 / methacrylic acid copolymer (80/15/5) Po-12 n-butyl acrylate / M-5 / Acrylic acid copolymer (85/10/5) Po-13 n-butyl acrylate / M-7 / methacrylic acid copolymer (85/10/5) Po-14 2-ethylhexyl acrylate / M-9
Copolymer (75/25) Po-15 n-butyl acrylate / M-13 / sodium styrene sulfonate copolymer (85/10/5) Po-16 n-butyl acrylate / M-14 / potassium styrene sulfinate Copolymer (75/20/5) Po-17 n-hexyl acrylate / methoxyethyl acrylate / M-2 copolymer (70/20/10) Po-18 2-ethylhexyl acrylate / M-1
5 / methacrylic acid copolymer (90/5/5) Po-19 n-butyl acrylate / M-1 / M-1
7 / acrylic acid copolymer (75/5/15/5) Po-20 octyl methacrylate / M-20 / sodium styrene sulfonate copolymer (80/15/5) A polymer latex which is separated and contains an ethylenically unsaturated monomer having an active methylene group in a shell portion is also preferably used.

Preferred examples of the core / shell latex used in the present invention are shown below, but the present invention is not limited thereto. The structure of each of the following latex compounds is described in the order of the core polymer structure, the structure of the shell polymer, and the core / shell ratio, and the copolymer composition ratio and the core / shell ratio in each polymer are all expressed by weight percentage.

P-1 to 12 Core: Styrene / butadiene copolymer (37/63) P-1 shell = styrene / M-1 (98/2) Core / shell = 50/50 P-2 Shell = styrene / M-1 (96/4) core / shell = 50/50 P-3 shell = styrene / M-1 (92/8) core / shell = 50/50 P-4 shell = styrene / M-1 (84 / 16) Core / Shell = 50/50 P-5 Shell = Styrene / M-1 (68/32) Core / Shell = 50/50 P-6 Shell = Styrene / M-1 (84/16) Core / Shell = 67/33 P-7 shell = styrene / M-1 (84/16) core / shell = 85/15 P-8 shell = n-butyl acrylate / M-1 (9
6/4) core / shell = 50/50 P-9 shell = n-butyl acrylate / M-1 (9
2/8) core / shell = 50/50 P-10 shell = n-butyl acrylate / M-1
(84/16) core / shell = 50/50 P-11 shell = methyl acrylate / M-7 (84
/ 16) core / shell = 50/50 P-12 shell = styrene / methyl acrylate / M-
3 (21/63/16) core / shell = 50/50 P-13, 14 core: styrene / butadiene copolymer (22/78) P-13 shell = styrene / M-2 (84/16) core / Shell = 50/50 P-14 Shell = n-butyl acrylate / M-8
(84/16) core / shell = 50/50 P-15-20 core: polybutadiene homopolymer (1
00) P-15 shell = styrene / M-1 (84/16) core / shell = 50/50 P-16 shell = ethyl acrylate / M-7 / methacrylic acid (65/15/20) core / shell = 75 /
25 P-17 shell = n-butyl acrylate / M-1
(84/16) core / shell = 50/50 P-18 shell = n-butyl acrylate / M-2
(84/16) core / shell = 50/50 P-19 shell = 2-ethylhexyl acrylate /
M-2 (84/16) core / shell = 50/50 P-20 shell = n-butyl acrylate / M-18
(84/16) core / shell = 50/50 P-21-23 core: polyisoprene homopolymer (1
00) P-21 shell = styrene / acrylonitrile / M-
1 (63/21/16) core / shell = 90/10 P-22 shell = methyl methacrylate / ethyl acrylate / M-2 / 2-acrylamide-2-methylpropanesulfonic acid sodium (15/65/15/5) Core / shell = 75/25 P-23 Shell = styrene / M-1 (84/16) Core / shell = 20/80 P-24-26 Core: Styrene / butadiene copolymer (49/51) P-24 Shell = styrene / butyl acrylate / M
-1 (25/60/15) core / shell = 50/50 P-25 shell = M-1 (100) core / shell =
90/10 P-26 shell = lauryl methacrylate / butyl acrylate / M-7 (30/55/15) core / shell = 40/60 P-27 core: acrylonitrile / styrene / butadiene copolymer (25/25/50) Shell: butyl acrylate / M-1 (92/8) Core / shell = 50/50 P-28 Core: ethyl acrylate / butadiene copolymer (50/50) Shell: styrene / divinylbenzene / M-1 ( 79 /
5/16) core / shell = 50/50 P-29 to 33 Core: poly (n-dodecyl methacrylate) homopolymer P-29 shell = styrene / M-1 (95/8) core / shell = 50/50 P-30 shell = styrene / M-1 (84/16) core / shell = 50/50 P-31 shell = ethyl acrylate / M-1 (96
/ 4) core / shell = 50/50 P-32 shell = ethyl acrylate / M-1 (92
/ 8) core / shell = 50/50 P-33 shell = styrene / methyl acrylate / M
-3 (21/63/16) core / shell = 50/50 P-34 core: poly (n-butyl acrylate) homopolymer Shell: styrene / M-2 (84/16) core / shell = 50/50 P-35, 36 core: poly (ethylene glycol dimethacrylate / n-butyl acrylate) copolymer (1
0/90) P-35 shell = styrene / M-1 (84/16) core / shell = 50/50 P-36 shell = methyl acrylate / M-7 / methacrylic acid (65/15/20) core / shell = 75 /
25 P-37-40 core: poly (ethylene glycol dimethacrylate / n-butyl acrylate) copolymer (2
0/80) P-37 Shell = Styrene / M-1 (84/16) core / shell = 50/50 P-38 Shell = Styrene / M-1 (84/16) Core / shell = 75/25 P- 39 shell = methyl acrylate / M-8 / 2-
Acrylamido-2-methylpropanesulfonic acid sodium (80/15/5) core / shell = 75/25 P-40 shell = n-butyl acrylate / M-1
(84/16) core / shell = 50/50 P-41 to 43 core: polyvinyl acetate homopolymer (1
00) P-41 shell = styrene / M-1 (84/16) core / shell = 50/50 P-42 shell = styrene / divinylbenzene / M-
24 (79/5/16) core / shell = 50/50 P-43 shell = n-dodecyl methacrylate / butyl acrylate / M-7 (30/55/15) core /
Shell = 40/60 P-44-46 Core: Poly (divinylbenzene / 2-
Ethylhexyl acrylate) copolymer (10/90) P-44 shell = methyl acrylate / M-1 (84
/ 16) core / shell = 50/50 P-45 shell = methyl acrylate / styrene / M
-1 (74/10/16) core / shell = 50/50 P-46 shell = M-1 (100) core / shell =
90/10 P-47-49 Core: Poly (divinylbenzene / styrene / 2-ethylhexyl acrylate) copolymer (1
0/23/67) P-47 shell = methyl acrylate / M-1 (84
/ 16) core / shell = 50/50 P-48 shell = methyl acrylate / styrene / M
-1 (74/10/16) core / shell = 50/50 P-49 shell = ethyl acrylate / 2-hydroxyethyl methacrylate / M-5 (65/15/20)
Core / shell = 85/15 P-50 core: poly (ethylene glycol dimethacrylate / vinyl palmitate / n-butyl acrylate) copolymer (20/20/60) shell: ethylene glycol dimethacrylate / styrene / n-butyl Methacrylate / M-1 (5/40/4
0/15) core / shell = 50/50 P-51 core: poly (trivinylcyclohexane / n)
-Butyl acrylate / styrene) copolymer (10/5
5/35) Shell: methyl acrylate / M-1 / 2-acrylamido-2-methylpropanesulfonic acid sodium (88/7
/ 5) core / shell = 70/30 P-52, 53 core: poly (divinylbenzene / styrene / methyl methacrylate) copolymer (10/45 /
45) P-52 shell = n-butyl acrylate / M-1
(84/16) core / shell = 50/50 P-53 shell = n-dodecyl acrylate / ethyl acrylate / M-21 (60/30/10) core /
Shell = 50/50 P-54, 55 Core: Poly (p-vinyltoluene / n
-Dodecyl methacrylate) copolymer (70/30) P-54 shell = methyl methacrylate / n-butyl methacrylate / M-2 / acrylic acid (30/55/1)
0/5) core / shell = 50/50 P-55 shell = n-butyl acrylate / M-19
(84/16) core / shell = 70/30 The polymer latex used in the present invention is disclosed in
No. 152112.

As a binder or a protective colloid of the silver halide emulsion according to the present invention, a hydrophilic colloid is used, and among them, gelatin is preferably used. As gelatin, lime-processed gelatin and acid-processed gelatin are preferably used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used.

In one preferred embodiment of the present invention, the total amount of gelatin contained in the constituent layers of the silver halide photographic material is 1 g or more and 7 g or less per 1 m ^{2 of the} silver halide photographic material. Is 1 g or more and 6 g or less.

In the present invention, the constituent layer refers to any of the layers coated on the support, and specifically includes a light-sensitive silver halide emulsion layer, a non-light-sensitive emulsion layer, and an emulsion protection layer. Layers, intermediate layers, backing layers and backing protective layers. Gelatin may be added to any of the above constituent layers, and the total amount of gelatin on the side having the silver halide emulsion layer is 2.5 g / m ² or less.

The silver halide emulsion in the silver halide photographic light-sensitive material according to the present invention may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide. But silver chloride 6
A silver halide emulsion containing 0 mol% or more is preferred. Specifically, an emulsion containing a silver halide emulsion having a composition of silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride, or silver chloroiodobromide containing 60 mol% or more of silver chloride. Is preferred.

The average grain size of silver halide is 1.2 μm.
m, particularly 0.5 to 0.1 μm
Is preferred. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined as the particle size. For details of the method for determining the average particle size, see Mies, James: The Theory of the Photographic Process (CE.
Mees & T. H. By James: The theor
y of the photographic pro
ses), Third Edition, pp. 36-43 (1966, published by McMillan "Mcmillan").

The shape of the silver halide grains is not limited.
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, it is preferable that the particle size distribution is narrower, and in particular, a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of particles falls within a particle size range of ± 40% of the average particle size is preferable.

At the time of physical ripening or chemical ripening, metal salts such as zinc, lead, thallium, iridium, rhodium, ruthenium, osmium, palladium and platinum can coexist. It is frequently used in silver halide emulsions to add iridium in the range of 10 ^-9 mol to 10 ^-3 mol per mol of silver halide to obtain high illuminance characteristics. In the present invention, rhodium, ruthenium, osmium and / or rhenium are contained in the silver halide emulsion in an amount of 10 ^-8 mol to 10 ^-2 per mol of silver halide in order to obtain an optimum high contrast emulsion as a photographic material for printing plate making.
It is preferable to add in a molar range. As the addition position, there is a method of distributing uniformly in the particles, a method of forming a core-shell structure, and a method of localizing a large amount in the core portion or the shell portion.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (Res)
(Earth Disclosure) 176 No. 1764
3, pages 22 to 23 (December, 1978).

The silver halide emulsion according to the present invention may or may not be chemically sensitized.

Examples of the chemical sensitizer include sulfur sensitizers (eg, thiosulfates, thioureas, rhodanines, polysulfide compounds, etc.), selenium sensitizers, tellurium sensitizers, and noble metal sensitizers (eg, gold, Palladium, platinum, iridium, etc.),
Reduction sensitizers (eg, sodium nitrite, hydrazines,
Polyamine, amine borane, etc.) can be used.

The silver halide photographic light-sensitive material according to the present invention may contain various silver halide photographic light-sensitive materials in order to prevent fog during the production process, storage or photographic processing, or to stabilize photographic performance. Compounds can be included.

As the binder or protective colloid of the silver halide emulsion according to the present invention, at least gelatin is preferably used, but other hydrophilic colloids, so-called hydrophilic polymers, can also be used. For example, gelatin derivatives, graft polymers of gelatin and other macromolecules, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sodium alginate, starch, glucose, dextrin, dextran, cyclodextrin Sugar derivatives such as dextrin, sucrose, maltose, xanthan gum, carrageenan, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N
-Various kinds of synthetic hydrophilic high-molecular substances such as homo- or copolymers such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole can be used.

In order to make the effect of the present invention more remarkable, it is necessary to have at least one hydrophilic colloid layer on the opposite side of the silver halide emulsion layer and at least one hydrophobic polymer layer on the outside thereof. Is preferred. here,
The hydrophilic colloid layer on the opposite side of the silver halide emulsion layer
Including a so-called back layer.

In the present invention, a configuration having at least one hydrophobic polymer layer outside the back layer is preferable.

In the present invention, the compounds described below are preferably contained in the constituent layers of the silver halide photographic light-sensitive material.

(1) Solid-dispersed fine particles of a dye JP-A-7-5629, page (3) [0017] to (1)
6) Compound described on page [0042] (2) Compound having an acid group Compound described in JP-A-62-237445, page 292 (8), lower left column, line 11 to page 309 (25), lower right column, line 3 (3) Acidic polymer JP-A-6-186659, page (10) [0036]
(4) Sensitizing dye JP-A-5-224330, page (3) [0017] to (17)
(13) Compound described on page [0040] JP-A-6-194777 (page 11) [0042]
Compound described in [0094] to page (22) [0015] to page (2) in JP-A-6-242533
(8) Compound described on page [0034] JP-A-6-337492 (3) page [0012]-
(34) Compound described on page [0056] JP-A-6-337494 (4) page [0013]-
(14) Compound described on page [0039] (5) Supersensitizer JP-A-6-347938 (3) page [0011] to
(16) Compound described on page [0066] The above-mentioned additives and other known additives are described in, for example, Research Disclosure No. 176
No. 43 (December 1978), ibid. 18716 (19
No. 1979) and the same No. 308119 (December 1989). The compound types and locations described in these three research disclosures are described below.

Additives RD-17643 RD-18716 RD-308119 page classification page classification page classification chemical sensitizer 23 III 648 upper right 996 III sensitizing dye 23 IV 648-649 996-8 IVA desensitizing dye 23 IV 998 IVB dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right antifoggant / stabilizer 24 IV 649 Upper right 1006-7 VI Brightener 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surface activity Agents 26-7 XI 650 right 1005-6 XI plasticizer 27 XII 650 right 1006 XII sliding agent 27 XII matting agent 28 XVI 650 right 1008-9 XVI binder 26 XXII 1003-4 IX support 28 XVII 1009 XVII The developing agent of the developer used in the development processing of the silver halide photographic material is Known compounds can be used. In a preferred embodiment, the silver halide photographic light-sensitive material of the present invention is processed with a developing solution containing ascorbic acid and its derivative as a developing agent.

Ascorbic acid and its derivatives are known as developing agents and are described, for example, in US Pat.
No. 548, No. 2,688,549, No. 3,022,1
Nos. 68, 3,512,981, 4,975,35
No. 4, No. 5,326,816 and the like can be used. Among them, the compound represented by the general formula [A] can be preferably used.

In the compound represented by the general formula [A],
The following general formula [A] wherein R ₁ and R ₂ are bonded to each other to form a ring
-A] is preferred.

[0098]

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In the formula, R ₃ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxyl group, a sulfo group, a carboxyl group, Represents an amide group or a sulfonamide group, Y ₁ represents O or S, and Y ₂ represents O, S or NR ₄
Represents R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal.

The alkyl group in the formula [A] or [Aa] is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group. Alternatively, an amino group substituted with a lower alkyl group is preferable, an alkoxyl group is preferably a lower alkoxy group, and an aryl group is preferably a phenyl group or a naphthyl group, and these groups may have a substituent. Well, as a group which can be substituted, a hydroxyl group, a halogen atom, an alkoxyl group,
Preferred substituents include a sulfo group, a carboxyl group, an amide group and a sulfonamide group.

Specific examples of the compound represented by formula (A) or (Aa) used in the present invention are shown below, but the present invention is not limited thereto.

[0102]

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[0103]

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These compounds are typically ascorbic acid or erythorbic acid or derivatives derived therefrom, and are commercially available or can be easily synthesized by a known synthesis method.

In the present invention, the developing agent represented by the general formula [A] used in the present invention and 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 1-phenyl-4
-Methyl-3-pyrazolidone, 1-phenyl-4,4-
Dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3
-Pyrazolidone, etc.) and aminophenols (for example, o-
Developing agents such as aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, and dihydroxybenzenes (eg, hydroquinone, hydroquinone monosulfonate) Can be used in combination. When used in combination, the developing agents such as 3-pyrazolidones, aminophenols and dihydroxybenzenes are usually used in an amount of 0.0
It is preferably used in an amount of 1 to 1.4 mol.

The silver halide photographic light-sensitive material of the present invention is preferably subjected to photographic processing by an automatic developing machine having at least four processes of exposure, development, fixing, washing (or stabilizing bath) and drying.

In the present invention, the developing solution contains an alkaline agent (eg, sodium hydroxide, potassium hydroxide, etc.) and a pH buffer (eg, carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine). And the like are preferably added. The pH buffer is preferably a carbonate, and the amount of the carbonate added is preferably 0.5 mol or more and 2.5 mol or less per liter, more preferably 0.75 mol or more and 1.5 mol or less.
Molar range. If necessary, dissolution aids (eg, polyethylene glycols, esters thereof, alkanolamines, etc.), sensitizers, surfactants, defoamers,
Antifoggants (for example, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (for example, ethylenediaminetetraacetic acid or its alkali) Metal salts, nitrilotriacetates, polyphosphates, etc.), development accelerators (for example, US Pat. No. 2,304,025, JP-B-47)
-Hardening agent (for example, glutaraldehyde or a bisulfite adduct thereof), and the like.

The sulfite and metabisulfite used as a preservative in the present invention include sodium sulfite, potassium sulfite, ammonium sulfite and sodium metabisulfite. The sulfite is preferably at least 0.25 mol / l. Particularly preferably, it is at least 0.4 mol / liter.

The pH of the developer used in the present invention is preferably adjusted to 8 or more and less than 11. More preferably, the pH is at least 8.5 and less than 10.5.

As the fixing solution, those having a commonly used composition can be used. Fixers generally have a pH of 3
８8. As a fixing agent, sodium thiosulfate, potassium thiosulfate, thiosulfates such as ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate,
In addition to thiocyanates such as ammonium thiocyanate, organic sulfur compounds capable of forming a soluble stable silver complex salt and known as a fixing agent can be used.

The fixing solution contains a water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum, an aldehyde compound (for example, glutaraldehyde or a glutaraldehyde sulfite adduct).
Etc. can be added.

The fixing solution may contain, if desired, a preservative (eg, a sulfite or a bisulfite), a pH buffer (eg, acetic acid, citric acid, tartaric acid, malic acid, succinic acid, etc., and salts thereof, and optical salts thereof. Compounds such as isomers), pH adjusters (for example, sulfuric acid and the like and salts thereof), and chelating agents capable of softening water.

After the fixing treatment, it is preferable to carry out the treatment with a washing and / or stabilizing bath. As a stabilizing bath, for the purpose of stabilizing an image, inorganic and organic acids and salts thereof, or alkali agents and salts thereof for adjusting the film pH (to adjust the film surface pH after treatment to 3 to 8) ( For example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, citric acid, oxalic acid, malic acid,
Acetic acid, etc.), aldehydes (eg, formalin, glyoxal, glutaraldehyde, etc.),
Chelating agents (e.g., ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetic acid salt, polyphosphate, etc.), and anti-bacterial agents (e.g., phenol, 4-chlorophenol, cresol, o-phenylphenol, chlorophen, dichlorophen, formaldehyde) , P-hydroxybenzoic acid ester, 2- (4-thiazoline) -benzimidazole, benzoisothiazolin-3-one, dodecyl-
Benzyl-methylammonium chloride, N- (fluorodichloromethylthio) phthalimide, 2,4
4'-trichloro-2'-hydroxydiphenyl ether, etc., a color tone adjuster and / or a residual color improver (for example, a nitrogen-containing heterocyclic compound having a mercapto group as a substituent; specifically, 2-mercapto-5-sulfone) Sodium benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole,
2-mercapto-5-propyl-1,3,4-triazole, 2-mercaptohypoxanthine, etc.). Among them, it is preferable that the stabilizing bath contains an anti-binder. These may be replenished in liquid or solid form.

In the present invention, the total processing time (Dry to Dry) from the insertion of the leading end of the film to the automatic developing machine until it comes out of the drying zone when processing using the automatic developing machine is 20 in order to reduce the developing time. Seconds to 60 seconds. The term "total processing time" as used herein includes the total process time required for processing the black-and-white photosensitive material, and specifically includes processing, such as development, fixing, bleaching, washing, stabilization, and drying. Time including all process times, that is, Dry to Dr
It is the time of y. If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dry) is 15 to 60 seconds. In order to stably process a large amount of photosensitive material of 100 m ² or more, the developing time is 35 seconds or less.
It is preferably at least seconds.

In the present invention, an automatic developing machine having a method and a mechanism described below can be preferably used.

(1) Deodorizing device: JP-A-64-37560
No. 544 (2), upper left column to page 545 (3), upper left column (2) Washing water regeneration purifying agent and apparatus: JP-A-6-2503
No. 52, page 3 (0011) to (8), page 0058 (3) Waste liquid treatment method: JP-A-2-64638 388
(2) Lower left column of page 391 (5) Lower left column of page (4) Rinse bath between developing bath and fixing bath: JP-A-4-31
No. 3749, page 18 [0054] to page (21) [00]
65 "(5) Water replenishment method: JP-A-1-281446 250
(2) Lower left column to lower right column of page (6) Method of detecting outside air temperature and humidity to control drying air of automatic developing machine: JP-A-1-315745, page 496 (2) Lower right column to page 501 (7) Lower right column and JP-A-2-10805
No. 1, page 588 (2), lower left column to page 589 (3), lower left column (7) Method for recovering silver of fixing waste liquid: JP-A-6-27623, page (4), "0012" to page (7), "0071".

Next, the antistatic layer will be described. The antistatic layer used in the present invention is not particularly limited, but is preferably composed of a water-soluble polymer, hydrophobic polymer particles, a reactant of a curing agent, or a metal oxide.

Examples of the water-soluble polymer include polymers having at least one conductive group selected from sulfonic acid groups, sulfate groups, quaternary ammonium salts, tertiary ammonium salts, and carboxyl groups. The conductive groups require at least 5% by weight per polymer molecule. In the water-soluble polymer, hydroxy group, amino group, epoxy group, aziridine group, active methylene group, sulfinic acid group,
It may contain an aldehyde group and a vinyl sulfone group.

The number average molecular weight of the polymer is 3000 to 1
00000, preferably 3500 to 50,000.

The compounds of the water-soluble polymer include A-1 to A-A described in JP-A-4-39651, pp. 6-11.
The following are typical examples, but the present invention is not limited thereto.

[0121]

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[0122]

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[0123]

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In the above P-1 to P-10, Mn
Represents an average molecular weight (in the present specification, the average molecular weight indicates a number average molecular weight), and is a value measured by GPC in terms of polyethylene glycol.

The hydrophobic polymer particles contained in the antistatic layer are composed of a so-called latex which is substantially insoluble in water. The hydrophobic polymer is styrene,
It can be obtained by polymerizing a monomer selected in any combination from styrene derivatives, alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives, vinyl ester derivatives, acrylonitrile and the like. Especially styrene derivatives, alkyl acrylates,
It is preferable that the content of the alkyl methacrylate is at least 30 mol%. In particular, 50 mol% or more is preferable.

Specific examples of these hydrophobic latexes are described in JP-A-4-39651, pp. 13-19.
-1 to L-26, and representative examples thereof will be given below.

[0127]

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[0128]

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[0129]

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Next, as the metal oxide when the antistatic layer is made of a metal oxide, any of indium oxide, tin oxide, metal oxide doped with antimony atoms, or a combination thereof can be used.

As the indium oxide, first indium oxide (In ₂ O) and second indium oxide (In ₂ O ₃ )
However, in the present invention, it is preferable to use indium oxide.

Further, as tin oxide, stannous oxide (S
nO) and stannic oxide (SnO ₂ ) are known,
Stannous oxide is preferably used in the present invention.

Examples of the metal oxide doped with an antimony atom include tin oxide and iridium oxide. To dope the metal oxide with antimony, a tin or indium halide, an alkoxylate or a nitrate compound and an antimony halide or a nitrate compound and an antimony halide, an alkoxylate or a nitrate chloride are mixed and oxidized and calcined. Can be obtained. These metal compounds can be easily obtained from metal compound manufacturers such as Japan Yttrium Corporation. Further, the preferable content when antimony is doped is preferably 0.5 to 10% by weight with respect to tin or indium. It is preferable to add these inorganic compounds by dispersing them in a hydrophilic colloid such as gelatin or dispersing them in a polymer compound such as acrylic acid or maleic acid. The loading ratio per binder is preferably 1 to 100% by weight.

Film pH of antistatic layer used in the present invention
Is preferably 8.0 or less, but too low is not preferred because of the stability of the film. Particularly preferably, 3.0 to 7.5.
It is.

The antistatic layer used in the present invention may be provided on the support side of the photosensitive layer, or may be provided on the opposite side of the support with respect to the photosensitive layer, that is, on the back side.

[0136]

EXAMPLES The effects of the present invention will now be illustrated by examples.

Example 1 <Preparation of Emulsion> (Emulsion A) 1.5% of pH = 2.0 containing sodium chloride kept at 40 ° C. and 3 × 10 ^-5 mol of sodium benzenethiosulfonate per mol of silver. % Gelatin aqueous solution and an aqueous sodium chloride solution containing 3.5 × 10 ⁻⁵ mol of (NH ₄ ) ₂ Ru (NO) Cl ₅ per mol of silver at a potential of 95 mV by a double jet method.
In 30 minutes, half of the silver content of the final particles was simultaneously added to prepare 0.12 μm of core particles. Thereafter, an aqueous silver nitrate solution was added to 10.5 × 10 ⁻⁵ mol of (NH ₄ ) ₂ R per mol of silver.
A sodium chloride aqueous solution containing uCl ₅ was added by a double jet method over 7 minutes to prepare cubic silver chloride particles having an average particle size of 0.15 μm.

Thereafter, the resultant was washed with water by a flocculation method well known in the art to remove soluble salts, and then gelatin was added to adjust the pH to 5.7 and the pAg to 7.5.
Further, 2 × 10 ⁻⁵ mol of sodium thiosulfate and 4 × 10 ⁻⁵ mol of chloroauric acid were added per mol of silver, and the mixture was heated at 60 ° C. for 60 minutes to perform chemical sensitization. A and phenoxyethanol were added in an amount of 50 mg / mol of silver, and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer was added in an amount of 3 × 10 ⁻³ mol / mol of silver.

(Emulsion B) Prepared in the same manner as Emulsion A, except that the amount of (NH ₄ ) ₂ Ru (NO) Cl ₅ was 1.0 × 10 ^−5.
mol.

<Preparation of Emulsion Underlayer Coating Solution> The following compounds were added to Emulsion B, and a silver halide emulsion layer was prepared on a support containing an undercoat layer by using the gelatin coating amount of the emulsion layer shown in Table 1 and the emulsion to be used. Was applied.

4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 5 mg / m ² N-oleyl-N-methyltaurine sodium salt 17 mg / m ² Compound-B 5 mg / m ² Compound-C 10 mg / m ² polymer latex Compound-D (hardener) shown in Tables 1 and 5 5 mg / m ² hydrazine compound Nucleation accelerator (Z) shown in Table 1 10 mg / m ² <Preparation of emulsion upper layer> Emulsion A The emulsion was prepared in the same manner as in the lower layer of the emulsion.

The amount of silver applied was 2.5 g / m 2 including the upper and lower layers.
^The amount of gelatin and the amount of polymer latex were the same for the upper layer and the lower layer.
The total of the upper layer and the lower layer of the emulsion protective film was shown.

<Preparation of Emulsion Protection Lower Layer Coating Solution> The following compounds were added to an aqueous gelatin solution.

Gelatin (Ca ⁺⁺ content 2700 ppm) Sodium p-dodecylbenzenesulfonate shown in Table 1 15 mg / m ² Compound-A 5 mg / m ² Compound-E 10 mg / m ² Compound-F 20 mg / m ² <Emulsion Preparation of Coating Solution for Protective Upper Layer> The following compounds were added to an aqueous gelatin solution.

Gelatin (Ca ⁺⁺ content 2700 ppm) Amorphous silica matting agent shown in Table 1 40 mg / m ² (average particle size 3.5 μ, pore diameter 25 °, surface area 700 m ² / g) Amorphous silica matting agent 10 mg / M ² (average particle size 2.5 μ, pore diameter 170 °, surface area 300 m ² / g) N-perfluorooctanesulfonyl-N-propylglycinepotassium 5 mg / m ² Sodium dodecylbenzenesulfonate 30 mg / m ² Compound-A 5 mg / m ² solid disperse dye-G ₁ 100 mg / m ² solid disperse dye-G ₂ 50 mg / m ^{2 When} the protective layer is formed as one layer, the above-mentioned protective lower additive is added to one layer. The amount of gelatin was as shown in Table 1 and applied onto a support having an undercoat layer described below. Then, on the opposite side of the silver halide emulsion layer with respect to the support,
The following conductive layer and back layer were simultaneously coated.

<Application of Antistatic Layer> (1) Polymer Antistatic Layer (Po) After corona discharge at an intensity of 10 W / (m ² · min),
After a corona discharge at a strength of 10 W / (m ² · min) again on the polyethylene terephthalate support treated with vinylidene chloride undercoat, an antistatic layer having the following composition was applied.

Water-soluble conductive polymer (P-3) 0.7 g / m ² Hydrophobic polymer latex (L-3) 0.2 g / m ² Ammonium sulfate 20 mg / m ² Curing agent (E-6) 0.1 g / m ² polyethylene glycol (molecular weight: 600) 5 mg / m ² (2) Metal oxide antistatic layer (M) A metal oxide antistatic layer having the following composition was applied in the same manner as the polymer antistatic layer.

Gelatin 0.2 g / m ² Styrene-maleic acid copolymer 50 mg / m ² Polyethylene glycol 2 mg / m ² Metal oxide (tin oxide-antimony doped) 0.1 g / m ² Hardener (E-2) 50 mg / m ² <Preparation of back layer coating solution and its coating> The following compound was added to an aqueous gelatin solution to give a gelatin coating amount of 2.50 g / m 2.
² was applied.

Gelatin (Ca ⁺⁺ content 30 ppm) 2.50 g / m ² Polymethyl methacrylate fine particles (average particle size 3.4 μ) 54 mg / m ² compound-H 140 mg / m ² compound-I 140 mg / m ² compound- J 40 mg / m ² Sodium dodecylbenzenesulfonate 75 mg / m ² Sodium dihexyl-α-sulfosuccinate 20 mg / m ² Compound-K 5 mg / m ² N-Perfluorooctanesulfonyl-N-propylglycine potassium 5 mg / m ² Sulfate Sodium 50 mg / m ² Sodium acetate 85 mg / m ² (Support, undercoat layer) On both sides of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm), the first and second undercoat layers having the following composition were applied. .

<One layer of undercoat layer> Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25 g Polystyrene fine particles (average particle size 3 μm) 0.05 g Compound-L 0.20 g Colloidal silica (Snowtex ZL; particle size 70-100 μm, manufactured by Nissan Chemical Co., Ltd.) 0.12 g 100 g with water added Further, 10 wt% KOH was added, and the coating solution adjusted to pH = 6 was dried. At a temperature of 180 ° C. for 2 minutes, a dry film thickness of 0.
It was applied to 9 μm.

<Second Layer of Undercoat Layer> Gelatin 1 g Methylcellulose 0.05 g Compound-M 0.02 g C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g Compound-A 3.5 × 10 ^-3 g Acetic acid 0.2 g Water was added and 100 g This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness became 0.1 μm.

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The following evaluation was performed using the samples shown in Table 1 thus obtained.

<Evaluation method> [Photo characteristics] The thus obtained sample was exposed through an optical wedge with a P-627FM printer manufactured by Dainippon Screen Co., Ltd., and treated with a processing solution described below using GX680 (manufactured by Konica Corporation). Processing was performed at a developing temperature of 35 ° C. for a developing time shown in Table 1, and the following items were evaluated.

Γ: (concentration 1.5-0.1) / ｛log
(Exposure amount giving a density of 1.5) -log (exposure amount giving a density of 0.1)}.

Sensitivity: Sample No. Relative evaluation with 1 as 100 (Running evaluation) Sensitivity, γ: 100 samples of each sample having a size of 508 mm × 610 mm were continuously processed. The replenishment rate was 50 ml / m ² . Furthermore, it is left for 2 days after running treatment (air oxidation)
After that, the sensitivity and γ were evaluated.

Residual color: The unexposed sample was treated with a new solution, and the sample N
o. Table 1 shows the number of sheets having the same level as that obtained by stacking seven 1s. The larger the number, the better the residual color.

Drying property: When the automatic developing machine is placed in an environment of 30 ° C. and 80% and the drying temperature is 45 ° C., the drying property is 508 mm ×
10 sheets of 610 mm were continuously processed at 5 cm intervals with the emulsion surface facing downward. The emulsion surface side when it came out of the drying section was evaluated for its tactile sensation.

<Developer 1 (using p-hydroxybenzene)> Diethylenetriamine-pentaacetic acid 2.0 g Sodium metabisulfite 40.0 g Hydroquinone 25.0 g 5-methylbenzotriazole 0.08 g 4-hydroxymethyl-4-methyl- 1-phenyl-3-pyrazolidone 0.45 g 2,3,5,6,7,8-hexahydro-2-thioxo-4- (1H) -quinazolinone 0.04 g 2-mercaptobenzimidazole-5-sulfonic acid sodium 0 .15 g sodium sorbate 3.0 g potassium hydroxide / sodium hydroxide and potassium carbonate / sodium carbonate to adjust the amount of potassium ions as shown in Tables 1-4, and to 1 liter so that the pH becomes 10.3 Finished.

<Fixing solution> Ammonium thiosulfate 359.1 g Ethylenediaminetetraacetic acid 2Na dihydrate 2.26 g Sodium thiosulfate pentahydrate 32.8 g Sodium sulfite 64.8 g NaOH 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Glucone Sodium acid 6.6 g Aluminum sulfate 25.3 g pH (adjusted with sulfuric acid or sodium hydroxide) 4.85 g 1 liter with water 2 liters of water was added to 1 liter of the above fixing solution.

<Processing Conditions> The automatic developing machine used was GX680 (manufactured by Konica Corporation) modified so that the processing time could be changed, and both the developing solution and the fixing solution were processed at 35 ° C.

Processing time Insertion Current image 2 seconds 4 seconds Fix 15 seconds 30 seconds Rinse 6 seconds 12 seconds Dry 11 seconds 22 seconds Total 45 seconds 90 seconds The results of the above evaluation are shown in Tables 1 and 2.

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[Table 1]

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[Table 2]

From the results shown in Tables 1 and 2, it can be seen that the sample of the present invention was excellent in photographic performance, running performance, residual color and drying property in ultra-rapid processing.

Example 2 A similar experiment was conducted using the sample of Example 1 using the following developer 2.

<Developer 2 (using general formula [A])> Diethylenetriamine-pentaacetic acid 4.0 g Sodium sulfite 15.76 g KBr 2.5 g Potassium carbonate 40 g / l Potassium hydrogen carbonate 25 g / l 8-mercaptoadenine 0.06 g Diethylene glycol 50 g 5-Methylbenzotriazole 0.5 g 1-Phenyl-5-mercaptotetrazole 0.02 g Dimezone S 2.7 g Compound A-17 of the general formula [A] 60 g Finished to 1 liter according to the above formula. The pH of the working solution was 9.80.

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[Table 3]

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[Table 4]

As is clear from the results shown in Tables 3 and 4, in the case of the present invention, even in a developer containing substantially no p-hydroxybenzene, excellent photographic performance, running performance, residual color and drying property in ultra-rapid processing were obtained. You can see that it is.

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According to the present invention, it is possible to provide a method for processing a silver halide photographic light-sensitive material which maintains high contrast even in ultra-rapid processing, does not cause hardening inhibition, and has little residual color.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI G03C 5/26 G03C 5/26 5/30 5/30

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material containing a hydrazine-based nucleating agent having an anionic group or a nonionic group forming an intramolecular hydrogen bond with a hydrogen atom of hydrazine in the vicinity of a hydrazine group, and a polymer latex, In the processing time of 20 to 60 seconds in the automatic processor,
The total gelatin amount (G) on the side having the silver halide emulsion layer is 2.5 g / m ² or less, and the weight ratio of the total gelatin amount (G) to the polymer latex (PL) is 0.1 ≦ PL / G
≦ 0.33, a method for processing a silver halide photographic light-sensitive material. 2. The halogen according to claim 1, wherein the halogen is treated with a developing solution containing a compound represented by the following general formula [A] and containing substantially no p-dihydroxybenzene compound. Processing method of silver halide photographic light-sensitive material. Embedded image [Wherein, R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group; ₁ and R ₂ may combine with each other to form a ring.
k represents 0 or 1, and when k = 1, X represents -CO- or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal. ] 3. The method for processing a silver halide photographic material according to claim 1, wherein the silver halide photographic material has an antistatic layer.