JP2000258874A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve color stain and image preservability and to considerably reduce contamination in the washing tank of an automatic processing machine by imagewise exposing a silver halide photographic sensitive material containing a specified compound and fixing it with a developing solution containing a specified developing agent and having a specified concentration of sulfurous acid. SOLUTION: A silver halide photographic sensitive material containing at least one of compounds of formulae I-III is imagewise exposed and fixed with a developing solution containing a developing agent of formula IV and having <=0.4 mol/l concentration of sulfurous acid. The sensitive material is then washed with washing water containing an oxidizing agent. In the formula I, R1 is an atomic group of the formula -OX, X is H or the like, R2 and R3 are each halogen or the like and R4 is carboxyl or the like. In the formula II, R11 and R12 are each alkyl or the like and R13 and R14 are each H or the like. In the formula III, R1-R4 are each alkyl or the like and R5 and R6 are each sulfonic acid or the like. In the formula IV, R1 and R2 are each substituted alkyl or the like and M1 and M2 are each H or the like.

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.
The present invention relates to a processing method for developing a silver halide photographic light-sensitive material having a dye with an automatic developing machine (automatic developing machine).

[0002]

2. Description of the Related Art A silver halide black-and-white photographic light-sensitive material is processed by an automatic developing machine after imagewise exposure in the steps of developing, fixing, washing and drying. In recent years, dyes and dyes often cause stains on photosensitive materials in the course of low replenishment and speeding up of processing solutions. In particular, the problem is serious because the photosensitive material for printing plate making has a large size and a large amount of processing.

On the other hand, photosensitive materials having ultra-high contrast photographic characteristics are widely used as photosensitive materials used in plate making.
In order to obtain such a high contrast image, US Pat.
No. 29, JP-A-60-258537, JP-A-5-23
As disclosed in No. 2616 or the like, a photosensitive material containing a hydrazine derivative can be treated with an MQ developer (a developer using a combination of p-aminophenols and hydroquinone) or a PQ developer (1-phenyl-3-pyrazolidones and hydroquinone). An image forming method for processing with a developer used in combination is known. However, in these image forming methods, since hydroquinone is used as a developing agent, there is a concern that the method is unfavorable from an ecological and toxicological point of view, and a method for obtaining a high contrast image with a developing solution containing no hydroquinone has been desired.

In contrast, US Pat. No. 5,236,816
No. 5,264,323, a system using ascorbic acids as a developing agent is known. Further, in this system using ascorbic acids as a developing agent, it is not necessary to use sulfite which has been used as a preservative for hydroquinones, and it is possible to reduce silver stain due to dissolution of silver halide in a processing solution.

[0005] However, when the content of sulfites is reduced, various dyes and dyes are used for the purpose of spectral sensitization or prevention of halation and irradiation.
Usually, such dyes and dyes are decomposed and decolored by the sulfite in the processing solution.However, when processed with a developing solution having a low sulfite concentration using ascorbic acid, the dye or dye adheres to the photosensitive material or There is a problem that coloring occurs over time. Further, when specific ascorbic acids are used as a developing agent, there is a problem of deterioration of halftone dot quality, and improvement thereof has been desired.

On the other hand, there is known a method of treating with an washing water containing an oxidizing agent for the purpose of reducing the washing water of the automatic developing machine and preventing stains such as scales and algae in the washing tank, for example, Konica Corporation. A purifying agent MB-1 (containing an oxidizing agent; anti-scale kit) manufactured by the company is used. However, when the treatment is carried out with washing water containing an oxidizing agent, there is a problem that the oxidizing agent remaining in the photographic constituent layer of the light-sensitive material deteriorates the long-term image storability, and improvement thereof has been desired.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object the problem of coloring over time and the improvement of image preservability, and the contamination in a washing tank of an automatic machine. It is an object of the present invention to provide a method for processing a silver halide photographic light-sensitive material, which has improved the maintainability while significantly reducing the amount of silver halide. Another object of the present invention is to provide a method for processing a silver halide photographic material using a specific ascorbic acid as a developing agent, having improved dot quality. In particular, it is an object of the present invention to provide a processing method in which the color stain and image storability of a silver halide photographic light-sensitive material after processing by an automatic developing machine have been remarkably improved.

[0008]

The above object of the present invention is attained by the following constitutions.

1. After imagewise exposing a silver halide photographic light-sensitive material containing at least one of the compounds represented by the following general formulas [1] to [3] on the side having a silver halide emulsion layer with respect to the support, the following general formula: A silver halide photographic light-sensitive method comprising: fixing with a developing solution containing a developing agent represented by (A) and having a sulfurous acid concentration of 0.4 mol / l or less, and further washing with washing water containing an oxidizing agent. Material treatment method.

[0010]

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In the general formula [1], R ₁ is an atomic group represented by —OX or —N (X) (Y);
Is a hydrogen atom, an alkyl group, cyanoalkyl group, carboxyalkyl group, sulfoalkyl group, hydroxyalkyl group, halogenated alkyl group, or an optionally substituted alkyl group or a sodium-potassium salt thereof, R ₂
And R ₃ are a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an alkylthio group, or-
OX represents the same group as above, and Q represents at least one halogen atom, a carboxyl group, a sulfo group, a sulfoalkyl group or a phenyl group, a sulfoalkyl group, a sulfoalkoxyalkyl group, or a sulfoalkylthio group substituted with a sodium or potassium salt thereof. L represents an alkyl group, and L represents an optionally substituted methine group. R ₄ represents an alkyl group, a carboxyl group, an alkyloxycarbonyl group or an acyl-substituted or unsubstituted amino group. m is an integer 1 or 2,
n shows the integer 0 or 1 respectively. In the general formula [2], R ₁₁ and R ₁₂ represent an alkyl group, a substituted alkyl group, an aryl group, an alkoxycarbonyl group, or a carboxyl group, and R ₁₃ and R ₁₄ represent a hydrogen atom, an aliphatic group, or an aromatic group. L represents a methine group which may be substituted. M represents a sodium, potassium or hydrogen atom, and 1 represents 0 or 1
Represents In the general formula [3], R _{1 to} R ₄ represent an alkyl group, a hydroxyalkyl group, a cyano group, an alkylcyano group, an alkoxy group and a sulfoalkyl group. R ₅ and R ₆ represent a sulfonic acid group or an alkylsulfonic acid group.
In the general formula (A), 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. . R ₁ and R ₂ may combine with each other to form a ring. k represents 0 or 1, and when k = 1, X is -C
Represents O- or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal.

2. After imagewise exposing a silver halide photographic light-sensitive material containing at least one compound represented by the following general formula [4] to the support having a silver halide emulsion layer on the side having the silver halide emulsion layer, A method for processing a silver halide photographic light-sensitive material, comprising fixing with a developing solution containing a developing agent represented by the formula and having a sulfurous acid concentration of 0.4 mol / l or less, and further washing with washing water containing an oxidizing agent. .

[0013]

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In the formula, Z is a thiazoline nucleus, a thiazolidine nucleus, a selenazoline nucleus, a selenazolidine nucleus, a pyrrolidine nucleus, a dihydropyridine nucleus, an oxazoline nucleus, an oxazolidin nucleus, an imidazoline nucleus, an indoline nucleus, a tetrazoline nucleus, a benzothiazoline nucleus, a benzoselenazoline nucleus, A non-metal atom group necessary for completing a benzimidazoline nucleus, a benzoxazoline nucleus, a naphthothiazoline nucleus, a naphthoselenazoline nucleus, a naphthooxazoline nucleus, a naphthoimidazoline nucleus or a dihydroquinoline nucleus. Q represents an atomic group necessary to complete a rhodanine nucleus, a 2-thiooxazoline-2,4-dione nucleus, a 2-thiohydantoin nucleus, a barbituric acid nucleus or a 2-thiobarbituric acid nucleus. R ₁
And R ₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. p represents 0 or 1.

[0015] 3. After imagewise exposing a silver halide photographic material containing at least one compound represented by the following general formula [5] to the support having a silver halide emulsion layer on the side having the silver halide emulsion layer, A method for processing a silver halide photographic light-sensitive material, comprising fixing with a developing solution containing a developing agent represented by the formula and having a sulfurous acid concentration of 0.4 mol / l or less, and further washing with washing water containing an oxidizing agent. .

[0016]

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In the formula, R ₁ and R ₂ each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, a sulfo group or a carboxyl group. , R ₁ and R ₂ may combine to form a 6-membered ring. R ₃ represents an alkyl group, an alkenyl group or an alkynyl group. R ₄ represents an alkyl group having 1 to 12 carbon atoms, and the alkyl group has —O—,
-OCO-, -NH- and -N <are included. R ₅ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.

4. After imagewise exposing a silver halide photographic light-sensitive material containing at least one polyhydroxybenzene-based compound on the side having a silver halide emulsion layer with respect to the support,
Fixing treatment with a developer containing a developing agent represented by the above general formula (A) and a sulfurous acid concentration of 0.4 mol / l or less,
A method for processing a silver halide photographic light-sensitive material, further comprising washing with water containing an oxidizing agent.

5. 5. The silver halide photograph as described in any one of the above items 1 to 4, wherein the oxidizing agent-supplying means supplies the oxidizing agent-containing concentrated solution or solid agent while mixing with water in a washing tank of an automatic developing machine. Processing method of photosensitive material.

6. 6. The method for processing a silver halide photographic light-sensitive material according to any one of the above items 1 to 5, wherein the oxidizing agent is hydrogen peroxide.

7. 7. The method for processing a silver halide photographic light-sensitive material according to any one of the above items 1 to 6, wherein the capacity of the washing tank is 20 l or less.

8. 8. The method for processing a silver halide photographic light-sensitive material according to any one of the above items 1 to 7, wherein the washing water contains a bactericide.

9. 9. The method for processing a silver halide photographic light-sensitive material according to any one of the above items 1 to 8, wherein the washing water contains a compound having a polyalkylene oxide chain represented by the following general formula (B).

General formula (B) HO (C ₂ H ₄ O) _a- (C ₂ H ₄ O) _b- (C ₂ H ₄ O) _c H In the formula, a, b and c represent positive integers. .

10. (1) The washing water contains salicylic acid, a derivative thereof, and a salt thereof.
10. The method for processing a silver halide photographic light-sensitive material according to any one of items 1 to 9,

11. 11. The method for processing a silver halide photographic material according to any one of the above items 1 to 10, wherein the washing water contains a silver sludge inhibitor represented by the following general formula (C).

Formula (C) Z ¹ -SM ^{1 In the} formula, Z ¹ represents an alkyl group, an aromatic group or a heterocyclic group, and M ¹ represents a hydrogen atom, an alkali metal atom, a substituted or unsubstituted amidino group. Represent.

12. 12. The silver halide photographic light-sensitive material as described in any one of items 1 to 11, wherein the washing water contains a chelating agent having a chelate stability constant of 0.8 to 5.0 with calcium ions. Method.

Hereinafter, the silver halide photographic light-sensitive material of the present invention (hereinafter, simply referred to as a light-sensitive material) according to the present invention will be described in detail with reference to the above general formula [1] on the side having a silver halide emulsion layer on a support. Or at least one of the compounds represented by [5] or a polyhydroxybenzene-based compound. After imagewise exposing these photosensitive materials, they are fixed with a developing solution containing a developing agent represented by the above general formula (A) and having a sulfurous acid concentration of 0.4 mol / l or less, and further washed with water containing an oxidizing agent. By washing with water, the image storability of the photosensitive material can be improved, and while the dot quality is improved, the dirt in the washing tank when processed by an automatic processing machine can be greatly reduced, and maintenance is easy. Is obtained.

First, a specific compound group contained in the light-sensitive material will be described.

(Compounds represented by the general formulas [1] to [3]) In the general formula [1], R ₁ is -OX or -N
(X) An atomic group represented by (Y), wherein X and Y are a hydrogen atom, an alkyl group, a cyanoalkyl group, a carboxyalkyl group, a sulfoalkyl group, a hydroxyalkyl group,
A halogenated alkyl group, an alkyl group which may be substituted or a sodium / potassium salt thereof, wherein R ₂ and R ₃
Is a hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an alkylthio group, or -OX
And Q represents at least one halogen atom, a carboxyl group, a sulfo group, a sulfoalkyl group or a phenyl group substituted with a sodium or potassium salt thereof, a sulfoalkyl group, a sulfoalkoxyalkyl group,
L represents a sulfoalkylthioalkyl group, and L represents an optionally substituted methine group. R ₄ represents an alkyl group, a carboxyl group, an alkyloxycarbonyl group or an acyl-substituted or unsubstituted amino group. m is an integer 1 or 2, n
Represents an integer 0 or 1, respectively.

In the general formula [2], R ₁₁ and R ₁₂ represent an alkyl group, a substituted alkyl group, an aryl group, an alkoxycarbonyl group, or a carboxyl group, and R ₁₃ and R ₁₄
Represents a hydrogen atom, an aliphatic group or an aromatic group, and L represents an optionally substituted methine group. M represents a sodium, potassium or hydrogen atom, and l represents 0 or 1. R ₁₃ and R ₁₄ represent a hydrogen atom, an aliphatic group, or an aromatic group, and are preferably an alkyl group substituted with a sulfonic acid group or a carboxyl group, a sulfonic acid group or a carboxyl group, or a sulfonic acid group. Represents an aryl group or a sodium / potassium salt thereof.

In the general formula [3], R _{1 to} R ₄ represent an alkyl group, a hydroxyalkyl group, a cyano group, an alkylcyano group, an alkoxy group and a sulfoalkyl group. R ₅
And R ₆ represents a sulfonic acid group or an alkylsulfonic acid group.

Specific examples of the compounds represented by the general formulas [1] to [3] are shown below, but the invention is not limited thereto.

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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The compounds represented by the general formulas [1] to [3] may be water-soluble or water-insoluble. The water-insoluble dye is preferably added in the form of solid dispersion of fine particles. When a water-insoluble dye is used, it is desirable that the dye be decolorized by a pH or an oxidation-reduction reaction or eluted into a processing solution so that the dye does not remain in the processed photosensitive material. The compounds represented by the general formulas [1] to [3] are contained in the silver halide emulsion layer side, particularly preferably in the silver halide emulsion layer or its protective layer.

In the present invention, when the compounds represented by the general formulas [1] to [3] are contained in the photographic constituent layer of the light-sensitive material to obtain sufficient safelight properties as a light-sensitive material, it is required to be 400 to 4%.
The maximum value of the absorbance at 50 nm is preferably from 2.0 to 5.0, and particularly preferably from 3.0 to 4.2. The absorbance as used herein refers to the absorbance of a photographic component layer after the compounds represented by the general formulas [1] to [3] are applied using a gelatin binder and dried.

(Compound represented by the general formula [4]) In the general formula [4], Z represents a thiazoline nucleus, a thiazolidine nucleus,
Selenazoline nucleus, selenazolidine nucleus, pyrrolidine nucleus, dihydropyridine nucleus, oxazoline nucleus, oxazolidine nucleus, imidazoline nucleus, indoline nucleus, tetrazoline nucleus,
Benzothiazoline nucleus, benzoselenazoline nucleus, benzimidazoline nucleus, benzoxazoline nucleus, naphthothiazoline nucleus, naphthoselenazoline nucleus, naphthoxazoline nucleus,
Represents a group of non-metallic atoms necessary to complete a naphthoimidazoline nucleus or a dihydroquinoline nucleus. Q is the rhodanine nucleus,
It represents an atomic group necessary for completing a 2-thiooxazoline-2,4-dione nucleus, a 2-thiohydantoin nucleus, a barbituric acid nucleus or a 2-thiobarbituric acid nucleus. R ₁ and R ₂ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. p represents 0 or 1.

Here, the alkyl groups represented by R ₁ and R ₂ in the general formula [4] include unsubstituted and substituted alkyl groups.

As the unsubstituted alkyl group, the number of carbon atoms is preferably 18 or less, particularly preferably 8 or less.
Examples include an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, and an n-octadecyl group. The substituted alkyl group has 6 carbon atoms in the alkyl portion.
The following are preferable, and those having 4 or less carbon atoms are particularly preferable. For example, an alkyl group substituted with a sulfo group (a sulfo group may be bonded via an alkoxy group, an aryl group, or the like. 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2- (3-sulfopropoxy) ethyl group, 2-
[2- (3-sulfopropoxy) ethoxy] ethyl group,
2-hydroxy-3-sulfopropyl group, p-sulfophenethyl group, p-sulfophenylpropyl group, etc., and an alkyl group substituted with a carboxyl group (the carboxyl group is bonded via an alkoxy group, an aryl group, etc. For example, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, etc., hydroxyalkyl group (eg, 2-hydroxyethyl group, 3-hydroxypropyl group, etc.),
Acyloxyalkyl group (for example, 2-acetoxyethyl group, 3-acetoxypropyl group, etc.), alkoxyalkyl group (for example, 2-methoxyethyl group, 3-methoxypropyl group, etc.), alkoxycarbonylalkyl group (for example, 2- A methoxycarbonylethyl group, a 3-methoxycarbonylpropyl group, a 4-ethoxycarbonylbutyl group, a vinyl-substituted alkyl group (eg, an allyl group), a cyanoalkyl group (eg, a 2-cyanoethyl group), a carbamoylalkyl group (eg, -Carbamoylethyl group, etc.), aryloxyalkyl group (for example, 2
-Phenoxyethyl group, 3-phenoxypropyl group, etc., aralkyl group (for example, 2-phenethyl group, 3-phenylpropyl group, etc.), or aryloxyalkyl group (for example, 2-phenoxyethyl group, 3-phenoxypropyl group, etc.) ).

The heterocyclic ring formed by Z in the general formula [4] may be substituted with at least one substituent, and the substituent may be a halogen atom (for example, fluorine, chlorine, bromine,
Iodine), nitro group, alkyl group (preferably having 1 to
4, for example, a methyl group, an ethyl group, a trifluoromethyl group, a benzyl group, a phenethyl group), an aryl group (for example, a phenyl group), an alkoxy group (preferably having 1 carbon atom)
To 4, for example, methoxy, ethoxy, propoxy, butoxy), carboxyl, alkoxycarbonyl (preferably 2 to 5, for example ethoxycarbonyl), hydroxy, cyano and the like. Can be.

Here, Z represents a thiazoline nucleus (for example, thiazoline, 4-methylthiazoline, 4-phenylthiazoline, 4,5-dimethylthiazoline, 4,5-diphenylthiazoline, etc.), a benzothiazoline nucleus (for example, benzothiazoline, 4-chlorobenzothiazoline, 5-chlorobenzothiazoline, 6-chlorobenzothiazoline, 7
-Chlorobenzothiazoline, 5-nitrobenzothiazoline, 6-nitrobenzothiazoline, 4-methylbenzothiazoline, 5-methylbenzothiazoline, 6-methylbenzothiazoline, 5-bromobenzothiazoline, 6-bromobenzothiazoline, 5-iodo Benzothiazoline,
5-methoxybenzothiazoline, 6-methoxybenzothiazoline, 5-ethoxybenzothiazoline, 5-propoxybenzothiazoline, 5-butoxybenzothiazoline, 5-carboxybenzothiazoline, 5-ethoxycarbonylbenzothiazoline, 5-phenethylbenzothiazoline, 5 -Fluorobenzothiazoline, 5-chloro-
6-methylbenzothiazoline, 5-trifluoromethylbenzothiazoline, 5,6-dimethylbenzothiazoline, 5-hydroxy-6-methylbenzothiazoline, tetrahydrobenzothiazoline, 4-phenylbenzothiazoline, 5-phenylbenzothiazoline, etc.), Naphthothiazoline nucleus (for example, naphtho [2,1-d] thiazoline, naphtho [1,2-d] thiazoline, naphtho [2,3
-D] thiazoline, 5-methoxynaphtho [1,2-d]
Thiazoline, 7-ethoxynaphtho [2,1-d] thiazoline, 8-methoxynaphtho [2,1-d] thiazoline,
5-methoxynaphtho [2,3-d] thiazoline and the like),
Thiazolidine nucleus (eg, thiazolidine, 4-methylthiazolidine, 4-nitrothiazolidine, etc.), oxazoline nucleus (eg, oxazoline, 4-methyloxazoline, 4-nitrooxazoline, 5-methyloxazoline, 4-phenyloxazoline, 4,5-diphenyl) Oxazoline, 4-ethyloxazoline, etc.), benzoxazoline nucleus (benzoxazoline, 5-chlorobenzoxazoline, 5-methylbenzoxazoline, 5-bromobenzoxazoline, 5-fluorobenzoxazoline, 5-phenylbenzoxazoline, 5-methoxybenz) Oxazoline, 5-nitrobenzoxazoline,
5-trifluoromethylbenzoxazoline, 5-hydroxybenzoxazoline, 5-carboxybenzoxazoline, 6-methylbenzoxazoline, 6-chlorobenzoxazoline, 6-nitrobenzoxazoline,
6-methoxybenzoxazoline, 6-hydroxybenzoxazoline, 5,6-dimethylbenzoxazoline, 5-ethoxybenzoxazoline and the like, naphthooxazoline nucleus (for example, naphtho [2,1-d] oxazoline, naphtho [1,2- d] oxazoline, naphtho [2,3-d] oxazoline, 5-nitronaphtho [2
1-d] oxazoline, etc.), oxazolidine nucleus (eg, 4,4-dimethyloxazolidine), selenazoline nucleus (eg, 4-methyl selenazoline, 4-nitro selenazoline, 4-phenyl selenazoline, etc.), selenazolidine nucleus (eg, Selenazolidine, 4-methylselenazolidine, 4-phenylselenazolidine, etc.), benzoselenazoline nucleus (e.g., benzoselenazoline, 5-chlorobenzoselenazoline, 5-nitrobenzoselenazoline, 5-methoxybenzoselenazoline, 5-hydroxybenzoselenazoline, 6-nitrobenzoselenazoline,
5-chloro-6-nitrobenzoselenazoline, etc.), naphtho selenazoline nucleus (for example, naphtho [2,1-d] selenazoline, naphtho [1,2-d] selenazoline etc.), 3,3-dialkylindoline nucleus ( For example, 3,3
-Dimethylindoline, 3,3-diethylindoline,
3,3-dimethyl-5-cyanoindoline, 3,3-dimethyl-6-nitroindoline, 3,3-dimethyl-5
-Nitroindoline, 3,3-dimethyl-5-methoxyindoline, 3,3-dimethyl-5-methylindoline, 3,3-dimethyl-5-chloroindoline, etc.),
Imidazoline nucleus (eg, 1-alkyl imidazoline,
1-alkyl-4-phenylimidazoline, 1-arylimidazoline, etc.), benzimidazoline nucleus (for example, 1-alkylbenzimidazoline, 1-alkyl-5-
Chlorobenzimidazoline, 1-alkyl-5,6-dichloro-benzimidazoline, 1-alkyl-5-methoxybenzimidazoline, 1-alkyl-5-cyanobenzimidazoline, 1-alkyl-5-fluorobenzimidazoline, 1-alkyl -5-trifluoromethylbenzimidazoline, 1-allyl-5,6-dichlorobenzimidazoline, 1-allyl-5-chlorobenzimidazoline, 1-arylbenzimidazoline, 1-aryl-5-chlorobenzimidazoline, 1-aryl −
5,6-dichlorobenzimidazoline, 1-aryl-
5-methoxybenzimidazoline, 1-aryl-5-
Cyanobenzimidazoline, etc.), naphthoimidazoline nucleus (for example, 1-alkylnaphtho [1,2-d] imidazoline, 1-arylnaphtho [1,2-d] imidazoline, etc.), and the above-mentioned alkyl is particularly preferably a carbon atom having 1 to 8 carbon atoms. For example, an unsubstituted alkyl group such as methyl, ethyl, propyl, isopropyl, and butyl, and a hydroxyalkyl group (eg, 2-hydroxyalkyl, 3-hydroxypropyl, etc.) are desirable. The aforementioned aryl groups represent phenyl, halogen (eg, chloro) substituted phenyl, alkyl (eg, methyl) substituted phenyl, alkoxy (eg, methoxy) substituted phenyl, and the like. A pyrrolidine nucleus (e.g., 2-pyrrolidine, etc.), a dihydropyridine nucleus (e.g., 1,4-dihydropyridine, 5-methyl-1,2-dihydropyridine, 3-methyl-1,4-dihydropyridine, etc.), a dihydroquinoline nucleus (e.g., 1, 4-dihydroquinoline, 3-methyl-1,2-dihydroquinoline, 5-ethyl-1,2-dihydroquinoline, 6-methyl-1,2-dihydroquinoline, 6-nitro-1,2-
Dihydroquinoline, 8-fluoro-1,2-dihydroquinoline, 6-methoxy-1,2-dihydroquinoline, 6
-Hydroxy-1,2-dihydroquinoline, 8-chloro-1,2-dihydroquinoline, 6-ethoxy-1,4-
Dihydroquinoline, 6-nitro-1,4-dihydroquinoline, 8-chloro-1,4-dihydroquinoline, 8-fluoro-1,4-dihydroquinoline, 8-methyl-1,
4-dihydroquinoline, 8-methoxy-1,4-dihydroquinoline, dihydroisoquinoline, 6-nitro-1,
2-isoquinoline, 6-nitro-2,3-dihydroisoquinoline, etc.) and non-metal atoms necessary to complete the tetrazoline nucleus.

Of these, Z is preferably a thiazoline nucleus, a benzothiazoline nucleus, a thiazolidine nucleus, a benzoxazoline nucleus, a naphthooxazoline nucleus, a selenazoline nucleus, a selenazolidine nucleus, a benzoselenazoline nucleus, a benzimidazoline nucleus, a pyrrolidine nucleus, a dihydropyridine nucleus,
This is the case with a tetrazoline nucleus.

R ₁ and R ₂ are each a hydrogen atom or an unsubstituted alkyl group (an alkyl group having 1 to 18, preferably 1 to 8 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, hexyl, dodecyloctadecyl) Such),
Substituted alkyl groups [eg, aralkyl groups (eg, benzyl, β-phenylethyl, etc.), hydroxyalkyl groups (eg, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxyethoxyethyl, etc.), carboxyalkyl groups (eg, carboxy Methyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl and the like, and an alkyl group substituted with a sulfo group (the sulfo group may be bonded to the alkyl group via an alkoxy group, an aryl group, or the like. For example, 2-sulfoethyl, 3
-Sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 2- [2- (3-sulfopropoxy) ethoxy] ethyl, p-sulfophenethyl ), A sulfate alkyl group (eg, 3-sulfate propyl, 4-sulfate butyl, etc.), a mercapto group, a vinyl group-substituted alkyl group (eg, an allyl group),
Acyloxyalkyl group (for example, 2-acetoxyethyl group, 3-acetoxypropyl group, etc.), alkoxyalkyl group (for example, 2-methoxyethyl group, 3-methoxypropyl group, etc.), alkoxycarbonylalkyl group (for example, 2- A methoxycarbonylethyl group, a 3-methoxycarbonylpropyl group, a 4-ethoxycarbonylbutyl group, a cyanoalkyl group (eg, a 2-cyanoethyl group), a carbamoylalkyl group (eg, 2
-Carbamoylethyl group, etc.), aryloxyalkyl group (for example, 2-phenoxyethyl group, 3-phenoxypropyl group, etc.), aryloxyalkyl group (for example,
2-phenoxyethyl group, 3-phenoxypropyl group, etc.), mercaptoalkyl group (eg, 2-mercaptoethyl group, 3-mercaptopropyl group, etc.), alkylthioalkyl group (eg, 2-methylthioethyl group, etc.)], or Represents an aryl group (for example, a phenyl group, a tolyl group, a naphthyl group, a methoxyphenyl group, a chlorophenyl group, etc.). R ₂ is preferably a hydrogen atom or an allyl group.

Q represents a rhodanine nucleus, a 2-thiooxazoline-2,4-dione nucleus, a 2-thioselenazoline-2,
4-dione nucleus, barbituric acid nucleus or thiobarbituric acid nucleus [for example, a 1-alkyl group (eg, 1-methyl, 1-methyl
Ethyl, 1-propyl, 1-heptyl and the like), 1,3-
Dialkyl groups (eg, 1,3-dimethyl, 1,3-diethyl, 1,3-dipropyl, 1,3-diisopropyl,
1,3-dicyclhexyl, 1,3-di (β-methoxyethyl) and the like, 1,3-diaryl group (for example, 1,
3-diphenyl, 1,3-di (p-chlorophenyl),
1,3-di (p-ethoxycarbonylphenyl), etc.), 1-sulfoalkyl group (for example, 1- (2-sulfoethyl), 1- (3-sulfopropyl), 1- (4-sulfobutyl)), 1 , 3-disulfoalkyl group (for example, 1,3-di (2-sulfoethyl), 1,3-di (3-sulfopropyl), 1,3-di- (4-sulfocyclohexyl, etc.), 1,3- Barbitur nucleus or thio containing di- (sulfoaryl group (eg, 1,3-di- (4-sulfophenyl) etc.) or 1-sulfoaryl group (eg, 1- (4-sulfophenyl) etc.) Barbituric acid nucleus] or thiohydantoin nucleus (provided that the substituent at the 1-position is the same as that at the 3-position (R ₂ ), but both may be the same or different) Represents

The heterocycle formed by Q is preferably a rhodanine nucleus or a thiohydantoin nucleus, more preferably a rhodanine nucleus. p represents 0 or 1.

The compound represented by the general formula [4] is contained in a silver halide emulsion in an amount of 10 ^-5 to 10 ^-1 mol per mol of silver.
(Preferably 10 ⁻⁴ to 10 ⁻² mol), and when these are added, the emulsion is dissolved in alcohols such as methanol and ethanol, ethers, ketones, ethylene glycol and diethylene glycols. Can be added inside. In general, the sensitizing dye may be used alone, or a combination thereof may be used, and the combination of the sensitizing dyes is often used particularly for supersensitization.

The following are specific examples of the compound represented by the general formula [4].

[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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(Compound represented by the general formula [5]) Next, the compound represented by the general formula [5] will be described.

In the formula, R ₁ and R ₂ each represent a hydrogen atom, a halogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, an alkoxy group optionally having 1 to 8 carbon atoms, phenyl Represents a group, a naphthyl group, a sulfo group or a carboxyl group, and R ₁ and R ₂ may combine to form a 6-membered ring, and a halogen atom, a lower alkyl group, a hydroxy group, a hydroxyalkyl group, It may be substituted with a phenyl group, an alkoxy group, a carboxyl group or the like. R ₃
Represents an optionally substituted alkyl group, alkenyl group or alkynyl group. R ₄ represents an optionally substituted alkyl group having 1 to 12 carbon atoms, wherein the alkyl group has —O—, —OCO—, —NH— and — between its carbon chains.
N <includes intervening ones. R ₅ is an optionally substituted alkyl group, alkenyl group, alkynyl group,
Represents an aryl group or a heterocyclic group.

In the formula, R ₁ and R ₂ each represent a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom, etc.), an optionally substituted alkyl group having 1 to 8 carbon atoms (eg, a methyl group,
An ethyl group, a hydroxyethyl group and the like, an optionally substituted alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group,
Ethoxy group), a phenyl group, a naphthyl group, a sulfo group or a carboxyl group, and R ₁ and R ₂ may combine to form a 6-membered ring, and a halogen atom, lower alkyl group, hydroxy Group, a hydroxyalkyl group, a phenyl group, an alkoxy group, a carboxyl group and the like.

R ₃ represents an alkyl group which may be substituted (for example, a methyl group, an ethyl group, a sulfoethyl group, a sulfopropyl group, a sulfamidoethyl group, a sulfobutyl group, etc.) or an optionally substituted alkenyl group or alkynyl group Represents an allyl group.

R ₄ has 1 carbon atom which may be substituted
To 12, and the substituent is preferably a hydroxy group, a carbamide group, a cyano group or the like, and the alkyl group has -O-, -OCO-, -NH-
And -N <.

R ₅ is an optionally substituted alkyl group,
Represents an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, particularly preferably a pyridyl group (the pyridyl group is a halogen atom (eg, a chlorine atom, a bromine atom, etc.), a lower alkyl group (eg, a methyl group, an ethyl group, etc.) , A hydroxy group, a hydroxyalkyl group (eg, a hydroxyethyl group), an alkoxy group (eg, a methoxy group, an ethoxy group, etc.), a sulfo group or a carboxyl group.

Specific examples of the compound represented by the general formula [5] include, but are not limited to, the following compounds.

(5-1) 1- (cyanoethyl) -3-
(Pyridin-2-yl) -5-[(3-sulfoethyl-
2-benzoxazolinidene) ethylidene] -2-thiohydantoin sodium salt (5-2) 1- (cyanoethyl) -3- (pyridine-
2-yl) -5-[(3-ethyl-2-benzoxazolinidene) ethylidene] -2-thiohydantoin sodium salt (5-3) 1- (2-diethylaminoethyl) -3-
[(Ethylnaphtho [2,1-d] oxazoline-2-ylidene) ethylidene] -3- (pyridin-2-yl)-
2-thiohydantoin (5-4) 1- (2-diethylaminoethyl) -3-
(Pyridin-2-yl) -5- [3-ethyl-2-benzoxazolinidene) ethylidene] -2-thiohydantoin (5-5) 1- (2-hydroxyethyl) -3- (4
-Sulfobutyl-pyridin-2-yl) -5-[(3-
Sulfopropyl-2-benzoxazolinidene) ethylidene] -2-thiohydantoin sodium salt (5-6) 1- (2-acetylbutyl) -3- (pyridin-2-yl) -5-[(3- Sulfoethyl-2-benzoxazolinidene) ethylidene] -2-thiohydantoin sodium salt (5-7) 1- (2-hydroxyethyl-3- (pyridin-2-yl) -5-[(3-sulfopropyl -2-
Benzoxazolinidene) ethylidene] -2-thiohydantoin sodium salt (5-8) 1- (2,3-dihydroxypropyl)-
3- (pyridin-2-yl) -5-[(3-sulfamidoethyl-2-benzoxazolinidene) ethylidene]
-2-thiohydantoin sodium salt (5-9) 1- (2-hydroxyethoxyethyl)-
3- (pyridin-2-yl) -5-[(3-sulfobutyl-5-chloro-2-benzoxazolinidene) ethylidene] -2-thiohydantoin sodium salt (5-10) 1- [2- ( 2-Diethylaminoethoxy) ethyl] -3- (pyridin-2-yl) -5- [ethyl-2-benzoxazonylidene) ethylidene] -2
-Thiohydantoin (5-11) 1- (2-hydroxyethoxyethoxyethyl) -3- (pyridin-2-yl) -5-[(3-
Sulfobutyl-5-chloro-2-benzoxazolinidene) ethylidene] -2-thiohydantoin sodium salt (5-12) 1- (2-propanone) -3-methyl-
5-[(3-Sulfobutyl-5-methoxy-2-benzoxazolinidene) ethylidene] -2-thiohydantoin sodium salt (5-13) 1- (acetonitrile) -3-methyl-
5-[(3-sulfobutyl-5-methoxy-2-benzoxazolinidene) ethylidene] -2-thiohydantoin sodium salt (5-14) 1- (2-hydroxyethoxyethyl)
-3- (p-ethoxypyridin-2-yl-5-[(3
-Sulfobutylnaphtho [2,1-d] oxazoline-2
-Ylidene) ethylidene] -2-thiohydantoin sodium salt (5-15) 1- (2-carbamidoethyl) -3-
(4-methylpyridin-3-yl) -5-[(3-sulfobutylnaphtho [2,1-d] oxazoline-2-ylidene) ethylidene] -2-thiohydantoin sodium salt represented by the general formula [5] Compounds are disclosed in JP-A-55-450.
No. 15, the method described in US Pat. No. 2,742,833,
Nos. 2,756,148, 3,567,458, 3,575,704, 3,615,517, 3,615,519 and 3,632,340. A person skilled in the art can easily synthesize by referring to the synthesis method described above.

The compound represented by the general formula [5] is usually contained in the silver halide emulsion in an amount of 10 ^-5 to 10 ^-1 mol per mol of silver.
l, preferably 10 ^-4 to 10 ^-2 mol, is suitably added to alcohols such as methanol and ethanol, ethers, ketones, and glycols such as ethylene glycol and diethylene glycol. After dissolution, it can be added to the emulsion.

(Polyhydroxybenzene Compound) In the present invention, it is effective to use a polyhydroxybenzene compound in order to improve the dot quality deterioration.

The polyhydroxybenzene compound is preferably a compound having any one of the following structures.

[0072]

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In the formula, X and Y are each a hydrogen atom, a hydroxy group, a halogen atom, an -OM group (M is an alkali metal ion), an alkyl group, a phenyl group, an amino group, a carbonyl group, a sulfone group, and a sulfonated phenyl group. , A sulfonated alkyl group, a sulfonated amino group, a sulfonated carbonyl group, a carboxyphenyl group, a carboxyalkyl group,
A carboxyamino group, a hydroxyphenyl group, a hydroxyalkyl group, an alkyl ether group, an alkylphenyl group, an alkylthioether, or a phenylthioether group. Among these are preferably a hydrogen atom, hydroxy group, -Cl, -Br, -COOH, -CH 2 CH 2 C
_{OOH, -CH 3, -CH 2 CH} 3, -CH (CH 3) 2,
—C (CH ₃ ) ₃ , —OCH ₃ , —CHO, —SO ₃ Na,
-SO ₃ H, -SCH ₃ or

[0074]

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And so on. X and Y may be the same or different. Preferred specific compound examples are shown below.

[0076]

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These polyhydroxybenzene compounds may be added to an emulsion layer or a layer other than the emulsion layer in the light-sensitive material. The addition amount is 10 ^{-5 to} 1 mol per 1 mol of silver.
Is effective, and the range of 10 ^-3 mol to 10 ^-1 mol is particularly effective.

The compound represented by formula (A) contained in the developer used in the present invention will be described.

(Compound represented by Formula (A)) In Formula (A), R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted amino group. It represents an unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, or R ₁ and R ₂ may combine with each other to form a ring. k represents 0 or 1, and when k = 1, X is -CO
-Or -CS-. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal.

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 particularly preferred.

[0081]

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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 alkoxy group, a sulfo group, a carboxyl group, It represents an amide group or a sulfonamide group, Y ₁ represents O or S, and Y ₂ represents O, S or NR ₄ . 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 general formula (A) or the general formula [A-a] 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 or an unsubstituted amino group. An amino group substituted with a lower alkyl group is preferable, an alkoxy 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. Examples of the group that can be substituted include a hydroxyl group, a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, and a sulfonamide group.

Specific examples of the compound represented by formula (A) or [A-a] are shown below, but the present invention is not limited thereto.

[0085]

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[0086]

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

The preferable addition amount of the compound represented by formula (A) is 0.05 to 1.0 mol / l, particularly preferably 0.1 to 0.5 mol / l.

In the present invention, in order to form a high-contrast image suitable for a photosensitive material for printing plate making (printing light-sensitive material), it is preferable to use a high-contrast agent. The high contrast agent refers to a compound that promotes high contrast, and more specifically, a compound that increases γ of the characteristic curve due to the presence of the high contrast agent. As γ of the silver halide photographic light-sensitive material for plate making, a light-sensitive material of 10 or more and 100 or less is preferably used.

Hereinafter, preferred hydrazine derivatives or high-contrast agents comprising a 5- or 6-membered nitrogen-containing heterocycle will be described.

The hydrazine derivative is a compound represented by the following general formula (H).

[0092]

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In the general formula (H), A is an aryl group,
Or a heterocyclic ring containing at least one sulfur atom or oxygen atom, and G represents a — (CO) _n — group, a sulfonyl group, a sulfoxy group, a —P (＝ O) R ₂ — group, or an iminomethylene group. , N represents an integer of 1 or 2, A ₁ and A _{2 each} represent a hydrogen atom or one of which is a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted acyl group; Represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group, amino group, carbamoyl group, or oxycarbonyl group. R ₂ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group, amino group and the like.

Among the compounds represented by the general formula (H), more preferred are the compounds represented by the following general formula (Ha).

[0095]

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In the formula, R ¹ is an aliphatic group (eg, octyl group, decyl group), an aromatic group (eg, phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or a heterocyclic group (eg, pyridyl group, thienyl group, Furyl group),
These groups are preferably further substituted with an appropriate substituent. Further, R ¹ preferably contains at least one ballast group or silver halide adsorption promoting group.

As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, an alkyl group having a carbon number of 8 or more which is relatively inert to photographic properties, for example, an alkyl group Alkenyl group, alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like.

Examples of the silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

In the general formula (Ha), X represents a group that can be substituted for a phenyl group, m represents an integer of 0 to 4, and when m is 2 or more, Xs may be the same or different.
A ₃ and A ₄ have the same meanings as A ₁ and A ₂ in formula (H), and are preferably both hydrogen atoms. G is-(C
O) _n -group, sulfonyl group, sulfoxy group, -P (=
O) R ₂ - group or iminomethylene group (n, R ₂ is Formula (H) is n in G of the R ₂ respectively the same).
Wherein a carbonyl group is preferred. R ² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group, a carbamoyl group, or an oxycarbonyl group. The most preferred R ² includes a fluorine-substituted alkyl group, a —COOR ₃ group and a —CON (R ₄ ) (R ₅ ) group (R ₃ represents an alkynyl group or a saturated heterocyclic group, R ₄ represents a hydrogen atom, Represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₅ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group).

Next, specific examples of the compound represented by formula (H) are shown below, but the present invention is not limited thereto.

[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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Specific examples of other preferable hydrazine derivatives include (1) to (252) described in US Pat. No. 5,229,248, columns 4 to 60.

The above hydrazine derivative can be synthesized by a known method. For example, US Pat.
No. 248, column 59 to column 80, can be synthesized by the method as described.

In the present invention, the hydrazine derivative can be used in any photographic constituent layer on the side of the silver halide emulsion layer. Preferably, a silver halide emulsion layer and / or
Alternatively, it is used for at least two or more of the hydrophilic colloid layers adjacent thereto. The optimum amount to be added varies depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, and the like.
The range of 10 ^-6 to 10 ^-1 mol per mol is preferable,
Particularly, a range of 10 ⁻⁵ to 10 ⁻² mol is preferable. And
The amount of the hydrazine derivative contained in the photographic component layer closest to the support among the hydrazine derivative-containing photographic component layers was 0.2% of the total amount of the hydrazine derivative contained in the photographic component layer farther from the support. 0.8 mol equivalent. Preferably it is 0.4 to 0.6 times mol equivalent. The hydrazine derivatives used in the present invention may be used alone or in combination of two or more.

As the 5- or 6-membered nitrogen-containing heterocyclic derivative of the present invention, the following general formula (Pa), (Pb) or (P
It is a compound represented by c).

[0110]

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In the present invention, the above general formula (Pa):
By using a specific nitrogen-containing heterocyclic compound represented by (Pb) or (Pc) as a toning agent, completely dry printing that exhibits excellent storage stability, high sensitivity, high Dmax, and high contrasting photographic characteristics. A photographic light-sensitive material for plate making and an image forming method can be provided.

In the general formula (Pa), (Pb) or (Pc), A ₁ , A ₂ , A ₃ , A ₄ or A ₅ is a non-metal for completing a 5- to 6-membered nitrogen-containing heterocycle. Represents a group of atoms,
The hetero ring may contain an oxygen atom, a nitrogen atom and a sulfur atom, and the hetero ring may be condensed with a benzene ring. The _5- to 6-membered nitrogen-containing heterocycle composed of A ₁ , A ₂ , A ₃ , A ₄ or A ₅ may further have a substituent, and the substituent may be an alkyl group, an aryl group, an aralkyl group. , Alkenyl group, alkynyl group, halogen atom, acyl group, alkoxycarbonyl group, aryloxycarbonyl group,
Sulfo group, carboxyl group, hydroxy group, alkoxy group, aryloxy group, amide group, sulfamoyl group,
Represents a carbamoyl group, a ureido group, an amino group, a sulfonamide group, a sulfonyl group, a cyano group, a nitro group, a mercapto group, an alkylthio group, or an arylthio group.

Examples of the 5- or 6-membered nitrogen-containing heterocycle composed of A ₁ , A ₂ , A ₃ , A ₄ or A ₅ include pyridine,
Imidazole, thiazole, oxazole, pyrazine,
Examples thereof include a pyrimidine ring, and a pyridine ring is preferable.

In the general formulas (Pa) and (Pb), Bp
Represents a divalent linking group, and m is 0 or 1. The divalent linking group includes alkylene, arylene, alkenylene, -S
O _2- , -SO-, -O-, -S-, -CO-, -N
(R ₆ ) — and (R ₆ represents an alkyl group, an aryl group, or a hydrogen atom) alone or in combination. Preferred examples of Bp include an alkylene group, an alkenylene group, and an alkyleneoxy group.

In the general formulas (Pa) and (Pc),
R _1, R ₂ and R ₅ each represent an alkyl group or an aryl group of saturated and unsaturated having 1 to 20 carbon atoms, and these groups may have a substituent, examples of the substituent A ₁ , A ₂ , A ₃ , A ₄ or A ₅ may be the same as those mentioned above.

Preferred examples of R ₁ , R ₂ and R ₅ are each an alkyl group having 4 to 10 carbon atoms or a substituted or unsubstituted aryl group. More preferred examples are a substituted or unsubstituted phenyl group and an unsaturated group. Represents an alkyl group or a phenyl-substituted alkyl group.

[0117] In Formula (Pa), (Pb) or (Pc), X _p ^- is a counter ion necessary to neutralize the charge of the whole molecule, such as chlorine ions, bromine ions, iodine ions, nitrate ions , Sulfate ion, p-toluenesulfonate, oxalate, n _p represents the number of counter ions required to neutralize the charge of the whole molecule, and n _p is 0 in the case of an internal salt. Specific examples of the compounds are shown below.

[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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As more preferred embodiments of the present invention, general formula (I) described in quaternary salt compounds described in US Pat. No. 3,719,494, general formula (I) described in US Pat. No. 4,115,122, Heterocyclic quaternary salt compounds described in U.S. Pat. No. 4,877,723, general formula (I) described in JP-A-4-437, and general formula (I) described in JP-A-8-220706.
(II) (III) and nicotinamide derivatives described in JP-A-7-92598 are preferably used.

General formulas (Pa) and (Pb) in the present invention
Alternatively, the amount of the compound represented by (Pc) is 1 m of silver.
It is preferably contained in an amount of 1 × 10 ⁻⁶ mol to 1 × 10 ⁻¹ mol, particularly 1 × 10 ⁻⁵ mol to 5 × 1 per mol.
The preferable addition amount is in the range of 0 ^-2 mol.

The compound represented by the general formula (Pa), (Pb) or (Pc) of the present invention may be any suitable organic solvent such as alcohols (methanol, ethanol, propanol,
It can be used by dissolving in fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like. Also, by an already well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, the powder of the compound represented by the general formula (Pa), (Pb) or (Pc) can be dispersed and used by a ball mill, a colloid mill, or an ultrasonic wave by a method known as a solid dispersion method.

The light-sensitive material may be used in combination with a compound represented by the general formula (Pa), (Pb) or (Pc) to form a hydrazine derivative, an amine derivative, an onium salt compound, a disulfide derivative, a hydroxyamine derivative, or the like. It is preferable to add a nucleus accelerator. Examples of the compound of the nucleation accelerator include paragraph No. [0062] of JP-A-8-314066.
To [0077] and examples (2-1) to (2-20) and (3) described in JP-A-6-258755.
-1) to (3-6), compounds of the general formula I in JP-A-7-104420, JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, lines 4 and lower right The thiosulfonic acid compounds described in the first to fifth rows of the column and further described in JP-A-1-237538 are preferably used. Particularly preferably, the compounds described in JP-A-8-314066 are used.

In the present invention, it is preferable to use a nucleation accelerator in order to effectively promote high contrast by hydrazine or a 5- or 6-membered nitrogen-containing heterocyclic derivative.

As a preferred nucleation accelerator, a compound represented by the following formula (Na) or (Nb) is preferably used.

[0129]

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In the general formula (Na), R ₃₁ , R ₃₂ , R
₃₃ is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group,
Represents a substituted aryl group, and R ₃₁ , R ₃₂ and R ₃₃ can form a ring. Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is particularly preferable. Preferred adsorbing groups include a heterocyclic ring, a mercapto group, a thioether group,
Examples include a selenoether group, a thione group, and a thiourea group. Particularly preferred as the general formula (Na) are compounds having at least one thioether group as a halogen adsorbing group in the molecule.

Specific examples of the nucleation accelerator (Na) will be described below.

[0132]

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[0133]

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[0134]

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[0135]

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In the above formula (Nb), Ar represents a substituted or unsubstituted aromatic or heterocyclic group. R ₃₄ is a hydrogen atom, an alkyl group, an alkynyl group, an aryl group,
Ar and R ₃₄ may be linked by a linking group to form a ring.
These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Preferred examples of the silver halide adsorption group include groups having the same meaning as the silver halide adsorption group of the compound represented by formula (Ha).

Specific compounds of the general formula (Nb) include the following.

[0138]

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[0139]

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Specific examples of other preferred nucleation promoting compounds include the compounds (2-1) to (2-20) and 6-2587 described in JP-A-6-258571.
No. 51, (3-1) to (3-6), JP-A-7-27
No. 0957, onium salt compounds described in JP-A-7-104
No. 420, a compound of the formula I, JP-A-2-103536.
No. 19, page 19, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5;
No. 8 thiosulfonic acid compound.

The nucleation accelerator used in the present invention can be used in any photographic constituent layer on the side of the silver halide emulsion layer, but is preferably used in the silver halide emulsion layer or a layer adjacent thereto. Is preferred. The optimum amount of addition depends on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., but is generally 10 ^-6 to 10 ^-1 mol per mol of silver halide. Is particularly preferable, and a range of 10 ⁻⁵ to 10 ⁻² mol is particularly preferable.

The halogen composition of the silver halide in the silver halide emulsion used in the present invention is not particularly limited, but when the processing is carried out with a small amount of replenishment or when rapid processing is carried out,
Silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride, 6
It is preferable to use a silver halide emulsion having a composition of silver chloroiodobromide containing 0 mol% or more of silver chloride.

The average grain size of silver halide is 1.2 μm.
m or less, particularly 0.8 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 Macmillan "Mcmillan")).

There are no restrictions on the shape of the silver halide grains.
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.

In the present invention, the method of reacting a soluble silver salt with a soluble halide salt may be any of a one-side mixing method, a simultaneous mixing method, and a combination thereof. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. To obtain a silver halide emulsion having a nearly uniform grain size.

In order to remarkably exert the effects of the present invention, at least one of the silver halide emulsions in the silver halide emulsion layer contains tabular grains, and the entirety of the emulsion layer in which the tabular grains are used is used. Preferably, tabular grains having an aspect ratio of 2 or more account for 50% or more of the total projected area of the grains. Particularly, the ratio of tabular grains is 60 to 70%, and further 80%.
The more favorable the result, the better the result. The aspect ratio represents the ratio of the diameter of a circle having the same area as the projected area of a tabular grain to the distance between two parallel planes.

Among these tabular grains, silver chloride of 50 m
ol% or more of tabular grains having a (100) plane as a main plane are preferably used, and these are described in US Pat.
No. 4,337, No. 5,314,798, No. 5,32
No. 0,958, and the like, and intended tabular grains can be easily obtained. In the tabular grains, silver halides having different compositions can be epitaxially grown or shelled at specific surface portions. In order to control the photosensitive nucleus, a transition line can be provided on the surface or inside of the tabular grains. In order to provide a transition line, fine grains of silver iodide can be present during chemical sensitization or can be formed by adding iodine ions. The preparation of particles is carried out by an acidic
A neutral method, an ammonia method, or the like can be appropriately selected. When doping a metal, it is particularly preferable to form particles under acidic conditions of pH 1 to 5. As a silver halide solvent, for example, ammonia, a thioether, a thiourea compound, a thione compound, or the like can be used to control the growth of the grains during the formation of tabular grains. As thioether compounds, 3,6,9,15,18,21-hexoxa-12-thiatricosan, 3,9,15-trioxa-6,12- described in German Patent 1,147,845.
Dithiaheptadecane; 1,17-dioxy-3,9-1
5-trioxa-6,12-dithiaheptadecane-4,
14-dione; 1,20-dioxy-3,9,12,1
8-Tetroxa-6,15-dithiaeicosan-4,1
7-dione; 7,10-dioxa-4,13-dithiahexadecane-2,15-dicarboxamide;
Oxathioether compounds described in JP-A-94347, JP-A-1-121847, JP-A-63-259563,
And cyclic oxathioether compounds described in JP-A-63-301939. Especially as thiourea,
What is described in -82408 is useful. Specifically, tetramethylthiourea, tetraethylthiourea, dimethylpiperidinothiourea, dimorpholinothiourea; 1,3-dimethylimidazole-2-thione;
3-dimethylimidazole-4-phenyl-2-thione; tetrapropylthiourea and the like.

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. In order to obtain high illuminance characteristics, 10
Doping in the range of ^-9 to 10 ^-3 is often used in silver halide emulsions. In the present invention, in order to obtain a high-contrast emulsion, it is preferable to dope rhodium, ruthenium, osmium and / or rhenium in the range of 10 ^-9 mol to 10 ^-3 mol per mol of silver halide.

When the metal compound is added to the particles,
Metals include halogen, carbonyl, nitrosyl, thionitrosyl, amine, cyan, thiocyan, ammonia, tellurocyan, selenocyan, dipyridyl, tripyridyl,
Phenanthroline or a combination of these compounds can be coordinated. The oxidation state of the metal can be arbitrarily selected from the highest oxidation level to the lowest oxidation level. Preferred ligands are described in JP-A-2-208.
No. 2, No. 2-20853, No. 2-20854, No. 2
As the hexadentate ligand and alkali complex described in JP-A-208555, there are general sodium, potassium, cesium and primary, secondary and tertiary amine salts. Further, a transition metal complex salt can be formed in the form of an aquo complex. Examples of these include, for example, K ₂ [RuC
l ₆ ], (NH ₄ ) ₂ [RuCl ₆ ], K ₂ [Ru (NO)
Cl ₄ (SCN)], K ₂ [RuCl ₅ (H ₂ O)], and the like. Ru is Rh, Os, R
e, Ir, Pd, and Pt.

Rhodium, ruthenium, osmium and / or
Alternatively, the rhenium compound is preferably added during the formation of silver halide grains. 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.

Often, better results are obtained when a large amount is present in the shell portion. In addition, instead of being localized in a discontinuous layer configuration, a method of increasing the abundance as the particles are continuously outside the particles may be used. The addition amount can be appropriately selected from the range of 10 ⁻⁹ mol to 10 ⁻³ mol per mol of silver halide.

The silver halide emulsion and its preparation method are described in detail in Research Disclosure (Res).
ear Disclosure (hereinafter referred to as RD)
176: 17643, pp. 22-23 (Dec. 1978
Mon)) or in the literature cited.

The silver halide emulsion may or may not be chemically sensitized. Known methods of chemical sensitization include sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization, and any of these methods may be used alone or in combination. As the sulfur sensitizer, known sulfur sensitizers can be used. Preferred sulfur sensitizers include, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, Rhodanins, polysulfide compounds and the like can be used. As the selenium sensitizer, a known selenium sensitizer can be used. For example, U.S. Pat. No. 1,623,499, JP-A-50-7132
No. 5, JP-A-60-150046 and the like can be preferably used.

The light-sensitive material used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. . That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles,
Bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (particularly 1-
Phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines and mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes and tetrazaindenes (especially 4-hydroxy-substituted-1,3,3). 3a, 7-tetrazaindenes), pentazaindenes and the like; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like can be added. it can.

It is advantageous to use gelatin as a binder or protective colloid of the photographic emulsion according to the present invention, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic high-molecular substances such as mono- or copolymers such as polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be.

As gelatin, in addition to lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

The photographic emulsion may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (eg, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or acrylic acid, A polymer having a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid or the like as a monomer component can be used.

To the photographic emulsion and the non-photosensitive hydrophilic colloid layer, an inorganic or organic hardener is added as a crosslinking agent for the hydrophilic colloid such as gelatin. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-
Methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxy dioxane, etc.), active vinyl compounds (1,
3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N,
N'-methylenebis- [β- (vinylsulfonyl) propionamide], etc., active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalic acids (mucochloric acid, phenoxymucochloric acid, etc.) ) Isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, carboxyl group-activated hardeners and the like can be used alone or in combination. These hardeners are RD 176, 176
43 (issued in December 1978), page 26, paragraphs A to C.

The photosensitive material used in the present invention contains various other additives. For example, desensitizers, plasticizers, slip agents, development accelerators, oils, and the like can be used.

The support used in the present invention may be either permeable or non-permeable. For the purpose of the present invention, a permeable plastic support is preferred. For the plastic support, a polyethylene compound (eg, polyethylene terephthalate, polyethylene naphthalate, etc.),
A support made of a triacetate compound (for example, triacetate cellulose or the like), a polystyrene compound, or the like is used.

The thickness of the support is preferably 50 to 2
It is 50 μm, particularly preferably 70 to 200 μm.

In order to further improve the curl and curl of the support, it is preferable to perform a heat treatment after film formation. The most preferable time is after film formation and after emulsion coating, but may be after emulsion coating. The heat treatment is preferably performed at a temperature of 45 ° C. or higher and a glass transition temperature of 1 second to 10 days. It is preferable to set the time within one hour from the viewpoint of productivity.

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), pages [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 in [0066] (6) Redox compound JP-A-4-245243, pages 235 (7) to 250
(22) Compound described on page (7) SPS support Support described in JP-A-3-54551 The above-mentioned additives and other known additives are described, for example, in RDNo. 17643 (December 1978), N
o. No. 18716 (November 1979) and the same No. 30
8119 (December 1989). The following table shows the types and locations of the compounds shown in these three research disclosures.

[0165]

[Table 1]

In the present invention, a treatment liquid having an oxidizing agent and water are supplied to a washing tank.

The oxidizing agent used in the present invention includes a metal or nonmetal oxide, an oxyacid or a salt thereof,
Examples include peroxides and compounds containing organic acid systems. From the viewpoint of discharging to the drainage pipe, the oxyacid is preferably sulfuric acid, nitrous acid, nitric acid, hypochlorous acid and the like, and the peroxide is particularly preferably hydrogen peroxide solution or fentonic acid. Among them, hydrogen peroxide is particularly preferable.

These oxidizing agents are preferably supplied in the form of a concentrated liquid or a solid agent from the viewpoint of physical distribution. As a preferred form, a concentrated solution is preferable, and a concentrated solution having an oxidizing agent component of 0.5 to 5 mol / l is preferable. Particularly preferably, it is 1-2 mol / l.

The oxidizing agent may be supplied in such a manner that the oxidizing agent-containing concentrated liquid or solid agent is once diluted with water and then replenished into a washing tank, or the oxidizing agent-containing concentrated liquid or solid agent is supplied while being mixed with water. Although a method or the like is used, it is preferable to supply the concentrated liquid or solid agent containing the oxidizing agent while mixing it with water. As used herein, the term "while mixing with water" refers to a form in which the concentrated liquid and the water are separately supplied to the washing tank or a form in which the water and the concentrated liquid are mixed immediately before being supplied to the washing tank. The term "immediately before" as used herein means a form in which the washing liquid is introduced into the washing tank within 2 minutes after the concentrated liquid and water are mixed and diluted to the concentration that is finally introduced into the washing tank.

The replenishment timing of the oxidizing agent-containing concentrated solution and water may be replenished at a constant rate every unit time, or replenished according to the processing amount by detecting the processing amount of the photosensitive material.

The amount of the oxidizing agent added to the washing tank is 槽 to 10 mol based on the thiosulfate brought in by the photosensitive material.
The equivalent range is preferable, and particularly preferably, 1/2 to 3 m
ol equivalent.

Oxidizing agent-containing concentrated liquid (hereinafter referred to as purifying agent)
In a preferred embodiment, coexist with a compound such as a preservative or a bactericide in order to make the oxidizing agent act effectively.

In the present invention, the washing time is preferably less than 20 seconds, more preferably less than 15 seconds, from the viewpoint of color contamination. In addition, from the viewpoint of water washability, it is preferably at least 1 second, more preferably at least 2 seconds. The washing tank capacity is 20 l
The following cases are preferred, and 15 l or less are particularly preferred.

The preservative used in the present invention is used as a stabilizer for an oxidizing agent such as hydrogen peroxide. Examples thereof include phosphoric acid, barbituric acid, urea, acetanilide, oxyquinoline,
Tetrasodium pyrophosphate, phenacetin, salicylic acid,
Dipicolinic acid, quinolinic acid, pyridinecarboxylic acid, ED
TA, ethylenediaminetetra (methylenephosphonic acid)
And the like. The amount of the preservative used varies depending on the substance, but is, for example, 10 ^-7 to 1 times, more preferably 10 ^{-5 to} 0.5 times the weight of hydrogen peroxide. In the case of an acid, the pH does not become 5.7 or less. Should be added in range.

The bactericide used in the present invention may be any as long as it does not adversely affect the photographic performance. Specific examples include thiazolylbenzimidazole compounds, isothiazolone compounds, chlorophenol compounds, and bromophenol compounds. Compounds, thiocyanic acid and isothianoic acid compounds, acid azide compounds, diazines and triazine compounds, thiourea compounds, alkylguanidine compounds,
Active halogen compounds such as quaternary ammonium salts, organic tin and organic zinc compounds, cyclohexylphenol compounds, imidazole and benzimidazole compounds, sulfamide compounds, sodium chlorinated isocyanurate, chelating agents, sulfite compounds, and penicillins. There are various antibacterial agents and fungicides such as antibiotics.
Other L. E. FIG. West. “Water Quali
ty Criteria "Photo.Sci.and
Eng,. Vol 9 No. 6 (1965); Japanese Unexamined Patent Publication (Kokai) Nos. 57-8542 and 58-105145.
Nos. 59-126533 and 55-111942
And the various anti-binder agents described in JP-A-57-157244;
"The Chemistry of Bactericidal and Fungicide Protection" by Hiroshi Horiguchi, Sankyo Publishing (Showa 57),
Chemicals and the like described in the "Handbook of Bactericidal and Fungicide Technology", Japan Society of Bactericidal and Fungus Protection and Technical Information (Showa 61) can be used.

Specific examples are shown below, but the present invention is not limited to these examples.

[0177] 1. 1. 5-chloro-2-methyl-4-isothiazolin-3-one 2. 2- (4-thiazolyl) -benzimidazole 3. methyl isothiocyanate 3,5-dichloro-4'-fluoro-thiocarbanilide 4-chloro-3,5-dimethylphenol 2,4,6-trichlorophenol 7. 7. Sodium dehydroacetate 8. Sulfanilamide 3,4,5-tribromosalicylanilide Potassium sorbate 11. 11. Benzalkonium chloride 1-Bromo-3-chloro-5,5-dimethylhydantoin Monochloroacetamide 14. Monobromoacetamide 15. Monoiodoacetamide 16. Benzimidazole 17. Cyclohexylphenol 18. 19. 2-octyl-isothiazolin-3-one Ethylenediaminetetraacetic acid 20. Nitrilo-N, N, N-trimethinephosphonic acid 21. 1-hydroxyethane-1,1-diphosphonic acid 18. ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 23. chlorinated sodium isocyanurate 2-methyl-4-isothiazolin-3-one 25. 10,10'-oxybisphenoxyarsine 1,2-Benzisothiazolin-3-one These exemplary compounds are described in U.S. Pat. No. 2,767,
172, 2,767,173, 2,767,1
74, 2,870,015, British Patent 848,
No. 130, French Patent No. 1,555,416
In each of the specifications, the synthesis method and examples of application to other fields are described. There are also those commercially available, such as Predentol ON, Permachem PD, Topside 800, Topside EG5, Topside 300, Topside 600 (all manufactured by Permachem Asia), and Fineside J-700 (manufactured by Tokyo Fine Chemical). ) Prozel
It can be obtained under the trade name of GXL (manufactured by ICI).

The disinfectant is preferably 0.01 to 50 g / l, and more preferably 0.1 to 50 g / l when supplied into washing water.
It is preferably from 0.5 to 20 g / l. When contained as a purifying agent, the amount is 0.1 to 50 g / l, more preferably 1 to 20 g / l, based on the purifying agent.

The washing water according to the present invention preferably contains a compound having a polyalkylene oxide chain (s).

The compound having a polyalkylene oxide chain (s) is not particularly limited, but a compound represented by the following general formula (B) in which propylene glycol is added as a hydrophobic group to ethylene oxide is particularly preferably used.

General formula (B) HO (C ₂ H ₄ O) _a- (C ₂ H ₄ O) _b- (C ₂ H ₄ O) _c H wherein a, b and c are positive integers.

In the present invention, the average molecular weight is from 2000 to 85.
00, polypropylene glycol (PPG) molecular weight of 1
400 to 2400, weight% of ethylene oxide in total molecule
Is preferably about 40 to 85%, particularly preferably, in the general formula, a + c is about 150 and b is about 30.

Examples of the compound having a polyalkylene oxide chain include commercially available nonionic surfactants such as "Pluronic Series" manufactured by Asahi Denka Co., Ltd.

In the present invention, the following are specifically preferred.

[0185]

[Table 2]

The amount of the compound having a polyalkylene oxide chain is from 1 to 1000 ppm, preferably from 10 to 100 ppm, based on the washing water, and when it is contained as a purifying agent, from 0.01 to 10% based on the purifying agent. , More preferably 0.1 to 5%.

The washing water according to the present invention has the following general formula (C)
It is preferable that the compound represented by

Formula (C) Z ¹ -SM ^{1 In the} formula, Z ¹ represents an alkyl group, an aromatic group or a heterocyclic group, wherein the alkyl group, aromatic group or heterocyclic group is a hydroxyl group, -SO ₃ M ² group, -COOM ² group (M ² represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted ammonium ion), a substituted or unsubstituted amino group, a substituted or unsubstituted ammonio group, or ( A substituent having at least one group selected from the group consisting of a hydroxyl group, a —SO ₃ M ² group, a —COOM ² group, a substituted or unsubstituted amino group, and a substituted or unsubstituted ammonium group)
Has been replaced by M ¹ represents a hydrogen atom, an alkali metal atom, a substituted or unsubstituted amidino group (which may form a hydrohalide or a sulfonate).

In the general formula (C), the alkyl group represented by Z ¹ preferably has 1 to 30 carbon atoms, particularly a straight-chain, branched or cyclic alkyl group having 2 to 20 carbon atoms. And may have a substituent in addition to the above substituents.

The aromatic group represented by Z ¹ is preferably a monocyclic or condensed ring having 6 to 32 carbon atoms, and may have a substituent in addition to the above substituents.

The heterocyclic group represented by Z ¹ is preferably a monocyclic or condensed ring having 1 to 32 carbon atoms,
It is a 5- or 6-membered ring having 1 to 6 heteroatoms in one ring independently selected from oxygen and sulfur, and may have a substituent in addition to the above. However, when the heterocyclic group is tetrazole, it does not have a substituted or unsubstituted naphthyl group as a substituent.

The substituted or unsubstituted ammonium group preferably has 20 or less carbon atoms, and the substituted or unsubstituted ammonium group may be a branched or cyclic alkyl group (for example, methyl,
An ethyl group, a benzyl group, an ethoxypropyl group, a cyclohexyl group), a substituted or unsubstituted phenyl group, a naphthyl group and the like.

Of the compounds represented by the general formula (C), a compound in which Z ¹ is a heterocyclic group having two or more nitrogen atoms is more preferable, and a compound represented by the following general formula (Ca) is more preferable. It is a compound represented by these.

[0194]

Embedded image

In the formula, Z is a group necessary for forming an unsaturated 5- or 6-membered heterocyclic ring having a nitrogen atom (for example, pyrrole, imidazole, pyrazole, pyrimidine, pyridazine, pyrazine and the like). Yes, R ¹¹ , R
¹² is a hydrogen atom, a —SM ¹ group, a halogen atom, an alkyl group (including a group having a substituent), an alkoxy group (including a group having a substituent), a hydroxyl group, —COOM
Group, -SO ₃ M group, an alkenyl group (including those having a substituent), amino group (including those having a substituent), (including those having a substituent) carbamoyl group, a phenyl group (the substituent and those in the containing) having, at least one -SM group or thione group in the formula, and a hydroxyl group, -COOM group, -SO ₃ M group, a substituted or unsubstituted amino group, a substituted or unsubstituted Has at least one substituent selected from the group consisting of: In the formula, R ¹¹ and R ¹² may form a ring. The ring that can be formed is a 5- or 6-membered ring, and is preferably a nitrogen-containing heterocycle. M ¹ is the same as M ¹ defined for the compound represented by formula (C). Preferably Z
Is a group forming a heterocyclic compound containing two or more nitrogen atoms, and may have a substituent other than the above-described -SM group or thione group. As the substituent, a halogen atom (for example, fluorine , Chlorine, bromine), lower alkyl groups (including those having a substituent, preferably those having 5 or less carbon atoms such as methyl and ethyl groups), and lower alkoxy groups (including those having a substituent; methoxy, Preferred are those having 5 or less carbon atoms such as ethoxy and butoxy, etc., lower alkenyl groups (including those having a substituent, and those having 5 or less carbon atoms), carbamoyl groups and phenyl groups. Further, in the general formula (Ca), the following general formula A
To F are particularly preferred. M represents a substituent.

[0196]

Embedded image

In the formula, each of R ₁ , R ₂ , R ₃ , and R ₄ represents a hydrogen atom, a —SM ₁ group, a halogen atom, a lower alkyl group (including those having a substituent, and a carbon atom such as a methyl group or an ethyl group). Those having a number of 5 or less are preferred), lower alkoxy groups (including those having a substituent, and those having 5 or less carbon atoms are preferred), hydroxy groups, -COOM ₂ , -SO ₃ M ₃ groups,
A lower alkenyl group (including a group having a substituent, preferably a group having 5 or less carbon atoms), an amino group, a carbamoyl group and a phenyl group, at least one of which is a -SM ₁ group. M ₁ , M ₂ and M ₃ each represent a hydrogen atom, an alkali metal atom or an ammonium group and may be the same or different. In particular, -SM ₁ substituent other than The hydroxy group, -COOM _2, -SO ₃ M ₃ group, it preferably has a water-soluble group such as an amino group. The amino group represented by R ₁ , R ₂ and R ₃ represents a substituted or unsubstituted amino group, and a preferable substituent is a lower alkyl group. The ammonium group is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.

Specific examples of the compound represented by the general formula (C) as a silver sludge inhibitor are shown below, but the present invention is not limited thereto.

[0199]

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[0200]

Embedded image

[0201]

Embedded image

[0202]

Embedded image

[0203]

Embedded image

[0204]

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The amount of the compound represented by the general formula (C) of the present invention is preferably 10 ^-6 to 10 ^-1 mol, and more preferably 10 ^-5 to 10 ^-2 mol per liter of washing water. It is preferred that

The chelate stability constant with calcium is the logarithm of the formation constant when one chelating agent binds to one calcium ion, and is measured at a temperature of 20 ° C. and an ionic strength of 0.2. It was done.

The washing water preferably contains a chelating agent compound having a chelate stability constant of 0.8 to 5.0 with calcium ions. Specific examples of the chelating agent compound having a chelating stability constant of 0.8 to 5.0 with calcium include maleic acid, glycolic acid, gluconic acid, glucoheptanoic acid, tartaric acid, citric acid, salicylic acid, and ascorbic acid. Organic acids such as erythorbic acid, glycine,
Aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and nitrilotriacetic acid, and derivatives and salts thereof. Among organic acids, gluconic acid and citric acid are preferred, and for aminopolycarboxylic acids, ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid are preferred. These compounds are used in an amount of about 0.005 to 0.2 mol / l, preferably 0.1 to 0.1 mol / l of washing water.
It is used at 005 to 0.1 mol / l.

The light-sensitive material according to the present invention can be developed,
The photographic processing is preferably carried out in an automatic processor having at least four processes of fixing, washing (or stabilizing bath) and drying.

As the developer used in the present invention, known developing agents can be used. Specifically, dihydroxybenzenes (e.g., hydroquinone, hydroquinone monosulfonate, etc.), 3-pyrazolidones (e.g., 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.), aminophenols (eg, o-aminophenol, p-aminophenol, N-methyl-
o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc., ascorbic acids (ascorbic acid, sodium ascorbate, erythorbic acid, etc.) and metal complex salts (EDTA iron salt, DTPA)
Iron salt, DTPA nickel salt, etc.) can be used alone or in combination. Among them, it is preferable to use a developer containing ascorbic acid and its derivative. Ascorbic acid and its derivatives are known as developing agents and are described, for example, in US Pat. No. 2,688,548.
Nos. 2,688,549 and 3,022,168
Nos. 3,512,981, 4,975,354 and 5,326,816 can be used.

The developer used in the present invention contains the developing agent represented by the general formula (A) and has a sulfurous acid concentration of 0.4 mol / l or less.

In the present invention, a developing agent of ascorbic acid or a derivative thereof and a 3-pyrazolidone (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-aminophenol, p-aminophenol, N-methyl-o-
Aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol and the like and dihydroxybenzenes substituted with a hydrophilic group (for example, hydroquinone monosulfonate, sodium salt of hydroquinone monosulfonic acid, 2,5-hydroquinone disulfone) It is more preferable to use a developing agent such as a potassium salt of an acid in combination. When used in combination, the developing agent of 3-pyrazolidones, aminophenols or dihydroxybenzenes substituted with a hydrophilic group is usually used in an amount of 0.01 or more and less than 0.2 mol per liter of a developing solution. preferable. In particular, ascorbic acid and its derivatives and 3-
Combinations of pyrazolidones, and combinations of ascorbic acid and derivatives thereof, 3-pyrazolidones, and dihydroxybenzenes substituted with a hydrophilic group are preferably used.

In the present invention, the developing solution contains an alkali agent (eg, sodium hydroxide, potassium hydroxide, etc.) and a pH buffer (eg, carbonate, phosphate, borate, boric acid, acetic acid, citric acid, alkanolamine, etc.). ) Is 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, more preferably 0.75 mol or more and 1.5 m / l.
ol or less. If necessary, dissolution aids (eg, polyethylene glycols, esters thereof, alkanolamines, etc.), sensitizers (eg, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, Antifoaming agents, antifoggants (for example, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (for example, ethylenediamine tetraethylene) Acetic acid or an alkali metal salt thereof, nitrilotriacetate, polyphosphate, etc.), a development accelerator (for example, compounds described in U.S. Pat. No. 2,304,025, JP-B-47-45541, etc.), a hardener (for example, Glutaraldehyde or its bisulfite adduct, etc.) or antifoam Etc. can be added. The pH of the developer is 7.5 or more.
Preferably, it is adjusted to less than 5. More preferably,
pH 8.5 or more and 10.4 or less.

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 sulfurous acid adduct of glutaraldehyde).
Etc. can be added.

The fixing solution may contain, if desired, a preservative (eg, sulfite or bisulfite), a pH buffer (eg, acetic acid or citric acid), a pH adjuster (eg, sulfuric acid), a chelating agent capable of softening water. A compound such as an agent can be included.

In the present invention, the concentration of ammonium ion in the fixing solution is preferably 0.1 mol or less per liter of the fixing solution.

The ammonium ion concentration is particularly preferably in the range of 0 to 0.05 mol per liter of the fixing solution. Sodium thiosulfate may be used instead of ammonium thiosulfate as the fixing agent, or ammonium thiosulfate and sodium thiosulfate may be used in combination.

In the present invention, the concentration of acetate ions in the fixing solution is preferably less than 0.33 mol / l. The type of acetate ion is arbitrary, and the present invention can be applied to any compound that dissociates acetate ion in the fixing solution, but acetic acid and lithium, potassium, sodium, and ammonium salts of acetic acid are preferably used. Salts and ammonium salts are preferred. The acetate ion concentration is more preferably at most 0.22 mol, particularly preferably at most 0.13 mol, per liter of the fixing solution, whereby the acetic acid gas generation can be greatly reduced. Most preferred are those that are substantially free of acetate ions.

The fixing solution includes citric acid, tartaric acid, malic acid,
Salts such as succinic acid and optical isomers thereof are included. Examples of the salts of citric acid, tartaric acid, malic acid, succinic acid and the like include lithium salts, potassium salts, sodium salts, and ammonium salts thereof, such as lithium hydrogen tartaric acid, potassium hydrogen, sodium hydrogen, ammonium hydrogen, ammonium potassium tartaric acid, and tartaric acid. May be used. Among these, citric acid, isocitric acid, malic acid, succinic acid and salts thereof are more preferred. Most preferred are malic acid and its salts.

The silver halide photographic light-sensitive material of the present invention can be processed using a developing and fixing replenisher prepared from a solid processing agent.

The solid processing agent used in the present invention is a powder processing agent, a solid processing agent such as tablets, pills, granules, etc., which has been subjected to a moisture-proof treatment as required. Pastes and slurries are semi-liquid, have poor storage stability, and exclude those having shapes that are regulated with the danger of transportation, and are not included in the solid processing agent of the present invention.

The powder as used in the present invention refers to an aggregate of fine crystal. The term “granules” as used in the present invention refers to granules having a particle diameter of 50 to 5000 μm, which are obtained by adding a granulation step to powder. The tablet referred to in the present invention refers to a tablet obtained by compressing powder or granules into a certain shape.

Among the above solid processing agents, tablets are preferred
It is preferably used because of high replenishment accuracy and easy handling.

To solidify the photographic processing agent, a concentrated solution or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the surface of the temporarily molded photographic processing agent is mixed with a water-soluble binder. Any means can be adopted such as forming a coating layer by spraying on the substrate (Japanese Patent Application Nos. 2-135887 and 2-20).
No. 3165, No. 2-203166, No. 2-20316
No. 7, 2-203168 and 2-300409).

A preferred tablet production method is a method of granulating a powdered solid processing agent and then performing a tableting step to form the tablet. There is an advantage that the solubility and storage stability are improved and the photographic performance becomes stable as compared with a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet.

The granulation method for tablet formation is to use known methods such as tumbling granulation, extrusion granulation, compression granulation, pulverization granulation, stirring granulation, fluidized bed granulation, and spray drying granulation. Can be done.
For tablet formation, the average particle size of the obtained granulated product is 100 to 800 μm in that, when the granulated product is mixed and compressed under pressure, the components become non-uniform, so-called segregation is unlikely to occur.
It is preferred to use
７750 μm. Further, the particle size distribution is
% Is preferably within a deviation of ± 100 to 150 μm. Next, when the obtained granules are compressed under pressure, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a briquetting machine can be used. The solid processing agent obtained by pressurizing and compression can take any shape, but from the viewpoint of productivity, handleability, or the problem of dust when used on the user side, a cylindrical, so-called tablet is used. preferable.

More preferably, at the time of granulation, the above effect is further remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a preservative and the like.

The method for producing the tablet processing agent is described, for example, in JP-A-51-61837, JP-A-54-155038, and JP-A-52-55038.
-88025, British Patent 1,213,808, etc., and can be produced by a general method.
For example, Japanese Unexamined Patent Publication Nos.
No. 3, 3-39735, 3-39939 and the like. Further, powder processing agents are disclosed, for example, in JP-A-54-133332, British Patent
No. 25,892, 729,862 and German Patent No. 3,733,861 and the like, and can be produced by a general method.

The bulk density of the above-mentioned solid processing agent is preferably 1.0 to 2.5 g / cm ³ in the case of a tablet from the viewpoint of the solubility and the effect of the object of the present invention, and is preferably 1.0 g / cm ^{3. If it is} larger than ³ , the strength of the obtained solid material is 2.5 g / c.
If it is smaller than m ³ , it is more preferable in view of the solubility of the obtained solid. When the solid processing agent is a granule or powder, the bulk density is preferably from 0.40 to 0.95 g / cm ³ .

The solid processing agent used in the present invention is used at least for a developer and a fixing agent, but can be used for other photographic processing agents such as other rinsing agents. In addition, the developer and the fixing agent can be excluded from the regulation of liquid dangerous substances.

According to the embodiments of the present invention, it is most preferable that all the processing agents are solidified, but it is preferable that at least the developer and the fixing agent are solidified. That is, the effects of the present invention are most remarkably exhibited because the developer / fixer component contains a large number of components that cause a mutual chemical reaction and also contains harmful components.

It is within the scope of the present invention that the solid processing agent used in the present invention can solidify only one part of a certain processing agent, but it is preferable that all the components of the processing agent be solidified. is there. It is desirable that each component is molded as a separate solid processing agent and is mounted in the same unit. It is also desirable that the separate components are packaged in the order in which they are periodically and repeatedly placed in a package.

In the case of solidifying the developer, it is preferred that all of the alkali agent and the reducing agent be solid-processed, and in the case of tablets, at least three or less, and most preferably one agent is used in the present invention. It is a preferred embodiment of the agent. When the solid processing agent is divided into two or more agents, it is preferable that these tablets and granules are packaged in the same manner.

When the fixing agent is solidified, the main agent, a hardener such as aluminum salt as a preservative, and all are solid-treated and, in the case of tablets, at least 3 agents or less, preferably 1 or 2 agents. Is preferred. When the solid treatment is performed by dividing into two or more agents, it is preferable that these tablets and granules are packaged in the same manner. In particular, it is preferable in terms of handling that the aluminum salt be solid.

As the package of the solid processing agent, polyethylene (either high-pressure method or low-pressure method), polypropylene (either unstretched or stretched), polyvinyl chloride, polyvinyl acetate, nylon (stretched or unstretched) , Polyvinylidene chloride, polystyrene, polycarbonate, vinylon, eval, polyethylene terephthalate (PE
T), other polyesters, hydrochloride rubber, acrylonitrile butadiene copolymer, epoxy-phosphate resin (polymers described in JP-A-63-63037,
Synthetic resin materials such as polymers described in US Pat. No. 3,295,952) and pulp.

[0236] These are preferably made of a single material. When used as a film, the films are laminated and bonded, but may be used as a coating layer or a single layer.

Further, for example, an aluminum foil or an aluminum vapor-deposited synthetic resin is used between the above synthetic resin films.
It is more preferable to use various gas barrier films.

Further, in order to preserve the solid processing agent and prevent the generation of stain, the oxygen permeability of these packaging materials is 50 ml / ml.
m224 hr · atm or less (at 20 ° C. and 65% RH), more preferably 30 ml / m224 hr · atm or less.

The total thickness of these laminated films or single layers is 1 to 3000 μm, more preferably 10 to 2000 μm.
μm, more preferably 50 to 1000 μm.

The above synthetic resin film may be a one-layer (polymer) resin film or two or more laminated (polymer) films.
It may be a resin film.

When the treating agent is wrapped or bound or covered with a water-soluble film or binder, the water-soluble film or binder may be a polyvinyl alcohol-based, methyl cellulose-based,
Polyethylene oxide type, starch type, polyvinylpyrrolidone type, hydroxypropylcellulose type, pullulan type, dextran type and gum arabic type, polyvinyl acetate type, hydroxyethylcellulose type, carboxyethylcellulose type, carboxymethylhydroxyethylcellulose sodium salt type, poly (alkyl ) Oxazoline-based, polyethylene glycol-based substrate film or binder is preferably used, among these,
In particular, polyvinyl alcohol-based and pullulan-based ones are more preferably used in view of the effect of coating or binding.

The thickness of the above water-soluble film is preferably from 10 to 120 μm in view of the storage stability of the solid processing agent, the dissolution time of the water-soluble film and the precipitation of crystals in an automatic developing machine. Is particularly preferred, and especially those having a size of 20 to 60 μm are preferably used.

The water-soluble film is preferably thermoplastic. This is because not only the heat sealing process and the ultrasonic welding process are facilitated, but also the covering effect is more excellent.

Further, the tensile strength of the water-soluble film was 0.5.
5 × 10 ⁶ to 50 × 10 ⁶ kg / m ² is preferable, and
It is preferably from × 10 ^{6 to} 25 × 10 ⁶ kg / m ² , and particularly preferably from 1.5 × 10 ⁶ to 10 × 10 ⁶ kg / m ² . These tensile strengths are measured by a method described in JIS Z-1521.

The photographic processing agent packaged or bound or coated with the water-soluble film or binder can be used during storage, transportation, and handling to prevent atmospheric humidity such as high humidity, rain, and fog.
It is preferable that the film is packaged with a moisture-proof packaging material in order to prevent damage from sudden contact with water due to splashing or wet hands, and the moisture-proof packaging material is preferably a film having a film thickness of 10 to 150 μm. Polyethylene film such as polyethylene terephthalate, polyethylene, polypropylene, moisture-proof packaging material, kraft paper, wax paper, moisture-resistant cellophane, glassine, which can have moisture-proof effect with polyethylene,
It is preferably at least one selected from polyester, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polycarbonate, acrylonitrile-based and metal foils such as aluminum, and metalized polymer films, and a composite material using these. There may be.

In the practice of the present invention, it is also preferable to use a decomposable plastic, particularly a biodegradable or photodegradable plastic, as the moisture-proof packaging material.

Examples of the biodegradable plastic include those composed of natural polymers, microorganism-produced polymers, synthetic polymers having good biodegradability, and the incorporation of biodegradable natural polymers into plastics. And those in which a group which is excited by ultraviolet rays and is linked to cleavage is present in the main chain. Further, in addition to the polymers listed above, those having both functions of photodegradability and biodegradability can be used favorably.

The specific representative examples are as follows.

Examples of biodegradable plastics include natural polymer polysaccharides, cellulose, polylactic acid, chitin, chitosan, polyamino acids, and modified products thereof. Of “Bio”) as a component
pol ", microbial-produced cellulose, etc. Synthetic polymers with good biodegradability Polyvinyl alcohol, polycaprolactone, etc., or copolymers or mixtures thereof Mixing of biodegradable natural polymers into plastics As natural polymers with good biodegradability , Starch and cellulose, which have shape disintegration in addition to plastics.As photodegradable plastics, the introduction of carbonyl groups for photodisintegration, etc. is there.

For such degradable plastics,
"Science and Industry", Vol. 64, No. 10, pp. 478-484 (1990), "Functional Materials", July, 1990, No. 23
~ 34 pages and the like can be used.
Biopol (ICI), E
co (eco) (manufactured by Union Carbide), E
colite (Eco Plastic)
Co., Ltd.), Ecostar (St. Law)
Commercially available decomposed plastics such as R. Starch (product of R. Starch) and Knuckle P (product of Nippon Unicar) can be used.

The moisture-proof packaging material preferably has a moisture permeability coefficient of 10 g · mm / m ^2, 24 hr or less, more preferably 5 g · mm / m ² , 24 hr or less.

In view of the demand for reducing the amount of waste liquid, the present invention is processed while replenishing a fixed amount of fixing in proportion to the area of the photosensitive material. The fixing replenishment amount is 300 ml or less per m ² . Preferably 30 to 250 per m ² each
ml.

Due to the demand for reduction of the waste liquid amount, the replenishment amount of the development is 1
preferably m is ² per 250ml or less, more preferably 30~200ml per 1 m ^2, respectively. The fixing replenishing amount and the developing replenishing amount referred to herein indicate the replenishing amounts. Specifically, it is the replenishing amount of each of the developing mother liquor and the fixing mother liquor when the same liquor is replenished. And the total amount of water, and the total amount of the solid processing agent and the volume of water when the solid developing agent and the solid fixing agent are replenished with a solution prepared by dissolving in water. And the total volume of each solid processing agent and water when the solid fixing agent and water are separately replenished. When replenished with a solid processing agent, it is preferable to express the total amount of the volume of the solid processing agent directly charged into the processing tank of the automatic developing machine and the volume of the replenishing water added separately. The developing replenisher and the fixing replenisher may be the same as the developing mother liquor and the fixing mother liquor in the tank of the automatic developing machine, or different liquids or solid processing agents, respectively.

The temperature of the developing, fixing, washing and / or stabilizing baths is preferably in the range of 10 to 45 ° C., and each may be separately adjusted.

According to the present invention, the total processing time (Dry to Dry) from the insertion of the leading end of the film into the automatic developing machine to the emergence from the drying zone when processing with the automatic developing machine is 60 due to the demand for shortening the developing time. It is preferably 10 to 10 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 time, ie Dr
It is the time of y to Dry. 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 50 seconds. In order to stably process a large amount of photosensitive material of 100 m ² or more, the development time is preferably 2 to 18 seconds.

In order to remarkably exert the effects of the present invention, a heat transfer material (for example, 60 to 60 ° C.) having a temperature of at least 60 ° C.
130 ° C heat roller etc.) or radiant object above 150 ° C (for example, tungsten, carbon, nichrome, a mixture of zirconium oxide, yttrium oxide, thorium oxide, silicon carbide, etc.) Those that transmit energy to a radiator such as copper, stainless steel, nickel, and various ceramics to generate heat or emit infrared rays) and have a drying zone are preferably used.

Examples of the heat transfer material having a temperature of 60 ° C. or higher include:
A heat roller is mentioned as an example. The heat roller preferably has an aluminum hollow roller whose outer peripheral portion is covered with silicon rubber, polyurethane, or Teflon. Both ends of this heat roller are preferably disposed inside the vicinity of the transport port of the drying unit by bearings made of a heat-resistant resin (for example, Lulon) and are rotatably supported on the side wall.

Further, it is preferable that a gear is fixed to one end of the heat roller, and the heat roller is rotated in the transport direction by a drive unit and a drive transmission unit. A halogen heater is inserted in the roller of the heat roller, and the halogen heater is preferably connected to a temperature controller provided in the automatic developing machine.

The temperature controller is connected to a thermistor arranged in contact with the outer peripheral surface of the heat roller, and the temperature controller controls the temperature detected by the thermistor to 60 to 150 ° C., preferably 70 to 130 ° C. In addition, it is preferable that the halogen heater be turned on and off.

The following examples are given as radiating objects emitting a radiation temperature of 150 ° C. or higher. (Preferably 250 ° C
Tungsten, carbon, tantalum, nichrome, a mixture of zirconium oxide, yttrium oxide, and thorium oxide, silicon carbide, molybdenum disilicide, and lanthanum chromate are directly heated and radiated to control the radiation temperature or resistance. There is a method to control by transmitting heat energy from the heating element to the radiator, but copper,
Examples include stainless steel, nickel, and various ceramics.

In the present invention, a heat transfer body of 60 ° C.
Radiating objects having the above reflection temperatures may be combined. or,
You may combine the conventional warm air of 60 degrees C or less.

In the present invention, an automatic developing machine having the following method and mechanism 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) Waste liquid treatment method: JP-A-2-6463
No. 8, 388 (2) lower left column to 391 (5) lower left column.

(3) Rinse bath between the developing bath and the fixing bath: JP-A-4-313949, page (18), "0054" to (2)
1) Page "0065".

(4) Water replenishment method: JP-A-1-28144
No. 6, page 250 (2), lower left column to lower right column.

(5) Method of controlling the drying air of an automatic developing machine by detecting the outside air temperature and humidity: Japanese Patent Laid-Open No. 1-315745 / 49
6 (2) lower right column to 501 (7) lower right column and
No. 108051 No. 588 (2), lower left column to 589 (3)
The lower left column of the page.

(6) Method for recovering silver from fixing waste liquid:
No. 27623, page (4) “0012” to page (7) “00”
71 ".

[0269]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 (Claim 1) [Preparation of silver halide photosensitive material] A conductive layer having the following composition and a back layer were simultaneously formed on one side of a polyethylene terephthalate film support having an undercoat of a moisture-proof layer containing vinylidene chloride. Applied.

(Conductive layer) SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μ) 250 mg / m ² gelatin (Ca ²⁺ content 3000 ppm) 100 mg / m ² Compound a (Proxel (UK I.K. CI company)) 7 mg / m ² Dodecylbenzenesulfonic acid sodium salt 20 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 20 mg / m ² Polystyrenesulfonic acid sodium salt 20 mg / m ² (back layer) Gelatin (Ca ²⁺ content 3000ppm) 2.0g / m ² compound -1 3 mg / m ² compound -2 40 mg / m ² compound -3 40 mg / m ² compound -4 155 mg / m ² compound -5 150 mg / m ² dodecylbenzenesulfonate Sodium 7 mg / m ² dihexyl-α-sulfosuccinate sodium 30 mg / m ² 1,2-bis ( Vinylsulfonylacetamide) ethane 140 mg / m ² Sodium sulfate 180 mg / m ² C ₈ F ₁₇ SO ₃ Li 5 mg / m ² Fine particles of polymethyl methacrylate (average particle size 4.7 μm) 10 mg / m ²

[0272]

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[0273]

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Next, the first and second emulsion layers and the lower and upper protective layers having the following compositions were simultaneously coated on the opposite side of the support.

(Emulsion Layer First Layer) Gelatin aqueous solution containing 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (5 × 10 ⁻³ mol per mol of silver) kept at 40 ° C. Silver nitrate aqueous solution and 2 × per mol of silver
An aqueous sodium chloride solution containing 10 ^-5 mol of (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ was simultaneously added in 7 minutes, and the potential between them was controlled at 95 mV to reduce the core particles to 0.12 μm. Prepared. Thereafter, 1.2 × 10 ⁻⁴ mol of (NH ₄ ) ₂ Rh per mol of silver nitrate aqueous solution and 1 mol of silver.
An aqueous solution of sodium chloride containing (H ₂ O) Cl ₅
Silver chloride cubic grains having an average grain size of 0.15 μm were prepared by adding for 4 minutes and controlling the potential during the addition to 95 mV. The hydrazine derivative H was added to this emulsion.
-16 was 0.5 × 10 ⁻⁵ mol / m ² , 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was 30 mg / m ² , and the following compound-6 and compound-7 were used. 40 mg / m ² , 10 mg / m ² , 0.6 g / m ^{2 of} polymer latex were added, and 1,1-bis (vinylsulfonyl) methane was added as a hardening agent in an amount of 55 mg / g of gelatin on the side having an emulsion layer. The first emulsion layer was coated so that the amount of silver was 1.6 g / m ² and gelatin was 0.6 g / m ² .

[0276]

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(Second Emulsion Layer)
Cyclopentane-4-hydroxy-1,3,3a, 7-
Tetrazaindene (5 × 10 ^-3 mol per mol of silver)
Silver nitrate aqueous solution and silver 1mo in gelatin aqueous solution containing
4 × 10 ⁻⁵ mol of (NH ₄ ) ₂ Rh (H ₂ O) C per liter
was added sodium chloride aqueous solution containing l ₅ simultaneously 3.5 minutes, the particles 0.08μm core portion was prepared by controlling therebetween potential to 95mV. Thereafter, 1.2 × 10 ⁻⁴ mol of (N
An aqueous sodium chloride solution containing H ₄ ) ₂ Rh (H ₂ O) Cl ₅ was added simultaneously over 7 minutes, and the potential during that time was controlled to 95 mV, whereby the average particle size was 0.10 μm.
Was prepared. Except that this emulsion was used, the same emulsion layer as the first layer of the above-mentioned emulsion layer was formed in an amount of 1.0 g / m 2 of silver.
^2. Gelatin was applied so as to be 0.4 g / m ² .

(Lower Layer of Protective Layer) Gelatin 0.60 g / m ² 1-hydroxy-2-benzaldoxime 15 mg / m ² Compound-8 80 mg / m ² Compound-9 10 mg / m ²

[0279]

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(Upper layer of protective layer) Gelatin 0.40 g / m ² Amorphous matting agent (SiO ₂ , average particle size 4.4 μm) 30 mg / m ² Liquid paraffin (gelatin dispersion) 50 mg / m ² N-perfluorooctane Sulfonyl-N-propylglycine potadium 5 mg / m ² Sodium dodecylbenzenesulfonate 10 mg / m ² Dye Described in Table 3 In addition, the dye described in Table 3 is added as an aqueous solution in the case of a water-soluble dye, and is added in an insoluble state. Prepared and added a fine particle dispersion by a dispersion preparation method having the following formulation.

The preparation method of the present invention is described in JP-A-63-197.
No. 943. That is, 434 ml of water and Tr
iton X-200R surfactant (TX-200R)
A 6.7% solution of 53 g (Rohm & Haas) was placed in a 1.5 l screw cap bottle. 20 g of dye and zirconium oxide (ZrO ₂ ) beads (2 mm diameter) 8
00 ml was added, the bottle lid was tightly placed in a mill and the contents were ground for 4 days. 12.5 contents
% Of an aqueous gelatin solution, and put on a roll mill.
Leave for 0 minutes to reduce foam. The resulting mixture was filtered to remove the ZrO ₂ beads. Average particle size is about 0.3μ
m, but still contains coarse particles, so that it was classified by centrifugation to make the maximum particle size 1 μm or less.

[Development processing] Processing was performed using a developer and a development replenisher having the following formulations.

(Developer Start Solution) (per liter of working solution) Diethyltriaminepentaacetic acid 1 g Sodium sulfite 30 g Potassium carbonate 53 g Potassium hydrogen carbonate 17 g 1-phenyl-4-methyl-4'-hydroxymethyl-3-pyrazolidone 1.5 g Na erythorbic acid monohydrate 40 g 1-phenyl-5-mercaptotetrazole 0.025 g Potassium bromide 4 g 5-methylbenzotriazole 0.21 g Gallic acid 5 g 8-Mercaptoadenine 0.07 g KOH is used at pH 10.1 And finished to 1 liter.

(Development replenisher) The inside of the solid processing agent package D having the following formulation was taken out by cutting an aluminum pillow.
It is poured into 9 liters of tap water stirred with a commercially available stirrer, and approximately 40
After stirring for 10 minutes, 10 l of replenisher solution DR was obtained. The pH of the obtained replenisher was 10.2.

(Preparation of Solid Developer Kit, 10 L of Working Solution)
1) Preparation of main drug granules DA Pretreatment of raw material 8-Mercaptoadenine was pulverized with the same pulverizer at a mesh of 8 mm and a rotation speed of 50 Hz. KBr was sized using a commercially available sizing machine with a mesh of 0.25 mm.

Mixing of Materials Using a commercially available V-type mixer (capacity: 200 l), the following formulation was mixed for 15 minutes.

Sodium erythorbate (manufactured by Pfizer) 84.3 kg 1-phenyl-4-methyl-4′-hydroxymethyl-3-pyrazolidone 2.31 kg gallic acid 11.32 kg 8-mercaptoadenine (the above ground product) 0.20 kg 7.09 kg of DTPA 5H KBr (the above sized product) 3.55 kg of benzotriazole 0.51 kg of sorbitol 3.14 kg The obtained mixture was sampled and analyzed at 50 g points from arbitrary points (5 places), and each component was analyzed. The concentration had a concentration within ± 5% of the above prescribed value, and was sufficiently homogeneously mixed.

Molding Step The above mixture was molded using a compression granulator Briquetter BSS-IV manufactured by Shinto Kogyo Co., Ltd. to form a pocket having a shape of 5.0 mmΦ.
× 1.2 mm (Depth), roller rotation speed 15 rp
m at a feeder rotation speed of 24 rpm. The obtained plate-like molded product was crushed by a classifier, and was 2.4 to 7.0 mm.
And fine powder having a size of 2.4 mm or less (fractions having a size of 7.0 mm or more were crushed). The fine powder having a size of 2.4 mm or less was mixed with the above mixture and returned to the compression molding machine to be molded. As a result, about 90 kg of granules DA was obtained.

2) Preparation of Alkaline Granule DB Preparation of Raw Materials The following raw materials were prepared and pretreated. 56.6 g of 1-phenyl-5mercaptotetrazole was dissolved in 400 ml of ethyl alcohol. The resulting solution was added dropwise little by little to 20 kg of anhydrous sodium carbonate being rotated by a mixer, and the rotation was continued until the solution was sufficiently dried. As a result of sampling and analyzing 10 g each from an arbitrary point (five places) of the obtained mixture, 1-phenyl-5mercaptotetrazole was sufficiently homogeneously mixed. Let the obtained mixture be M-1.

Mixing of Potassium Carbonate / M-1 The following formulation was mixed for 10 minutes using a commercially available V-type mixer (capacity: 200 l).

Potassium carbonate 34.95 kg M-1 11.44 kg Anhydrous sodium sulfite 17.85 kg D-mannitol 4.63 kg D-sorbitol 1.86 kg After mixing, MIKRO-P manufactured by Hosokawa Micron Corp.
4m mesh with ULVERIZERAP-B crusher
Then, 1.37 kg of sodium 1-octanesulfonate pulverized at a rotation speed of 60 Hz was added thereto, and the mixture was further mixed for 5 minutes.

Molding Step The above mixture was molded using a compression granulator Briquetta BSS-IV manufactured by Shinto Kogyo Co., Ltd. to form a pocket of 5.0 mmΦ.
× 1.2 mm (Depth), roller rotation speed 15 rp
m, at a feeder rotation speed of 44 rpm. The obtained plate-like molded product was crushed by a classifier, and was 2.4 to 7.0 mm.
And fine powder having a size of 2.4 mm or less (fractions having a size of 7.0 mm or more were crushed). The fine powder having a size of 2.4 mm or less was mixed with the above mixture and returned to the compression molding machine to be molded. As a result, about 71 kg of alkaline granules DB was obtained.

Packing step (10 liters of liquid used) The formed granules were filled in the following order, and nitrogen was further added to the inside.
After the blowing, the opening was sealed with an aluminum pillow with a heat sealer to obtain a solid processing agent package D.

1) DB 1174.9 g 2) DA 355.2 g (Fixing solution start solution) Sodium thiosulfate 200 g Sodium sulfite 22 g Na gluconate 5 g Citric acid 3Na.2H ₂ O 12 g Citric acid 12 g Sulfuric acid pH Was adjusted to 5.4 and finished to 1 l.

(Fixing solution replenisher (2-fold concentrated solution)) Sodium thiosulfate 200 g Sodium sulfite 22 g Na gluconate 5 g Citric acid 3Na · 2H ₂ O 12 g Citric acid 12 g The pH of the working solution becomes 5.2 with sulfuric acid. And finished to 0.5 l.

(Washing Water) Condition 1: Tap water was flowed at a flow rate of 3 l / min. At this time, the water temperature in the washing tank was 18 ° C.

Condition 2: Each time 1.5 m ^{2 of the} light-sensitive material was processed, 2.3 l / m ² of tap water was supplied, and a purifying agent of the following formulation was supplied at 20 ml / m ² to prepare washing water.

(Preparation of Purifying Agent) Pure water 800 g Salicylic acid 0.1 g 35% by weight aqueous hydrogen peroxide 171 g Pluronic F68 3.1 g Hoksite F-150 15 g DTPA · 5Na 10 g Finish with pure water to 1 liter (replenishing amount of treatment liquid) ) The developing and fixing replenishers of the above formula were directly replenished to the developing tank and the fixing tank, respectively, under the following conditions.

Replenishing amount of developer 130 ml / m ² Replenishing amount of fixing agent Concentrate 65 ml / m ² Replenishing amount of fixing agent Dilution water 65 ml / m ² (Processing conditions) Temperature Processing time Development 38 ° C. for 15 seconds Fixing 37 ° C. for 15 seconds Water washing 20 15 ° C. Drying 50 ° C. 12 seconds (Blackening ratio of photosensitive material) 8% —Evaluation— Sensitivity, gamma (γ), dot quality, recoloration after processing, and scale were evaluated as follows. . Table 3 shows the results.

(Measurement of Sensitivity and γ) The obtained sample was subjected to a light room printer FPA-800 manufactured by Fuji Photo Film Co., Ltd.
Exposure was performed through an optical wedge with FX (using a Fresnel lens), and an automatic developing machine AP-560 was used using the above processing solution.
(Fuji Photo Film Co., Ltd.) to determine the sensitivity. At this time, the sensitivity of the sample 101 was set to 100 and expressed as a relative value. Further, γ was determined from the slope of the characteristic curve giving densities 1 and 3.

(Dot Quality) A 175 l, 50% flat screen was exposed with an appropriate exposure, processed in the same manner as in the sensitivity measurement, and the dot quality was visually observed using a 100-fold loupe and evaluated according to the following criteria. did.

5: No fringe is seen at all, smooth dot quality 4: No fringe is seen, but the border of the dot is slightly rough 3: The fringe is slightly, and the border of the halftone is rough The lower limit level in practical use 2: fringe is clearly visible level 1: fringe is severe, fogging silver is visible between halftone dots.

[0303] In addition, the recoloring and the scale were evaluated by changing the method of supplying the purifying agent.

(Recoloring after Processing) The same developing processing as in the measurement of the sensitivity was performed without exposing the sample. The obtained sample was 4
It was allowed to stand for 12 hours in an environment of 0 ° C. and 80% RH, and then the recoloring was visually evaluated according to the following criteria.

：: No change at all before the deterioration test was performed. Δ: Slight change in color tone compared to before the deterioration test was performed, but there was no practical problem as a level of color contamination. X: The deterioration test was not performed. The color tone has changed compared to before performing
There is a practical problem.

(Washing Tank Dirt) 200 sheets of photosensitive material were processed per day for 5 days, left unprocessed for 1 day with the automatic developing machine running, and stopped for 10 hours. Was visually evaluated. Rank 3 or higher is a level that can withstand practical use.

1: Rollers and rinsing tank walls are slimy due to scale, and scales are floating in the liquid. 2: Rollers and rinsing tanks are slimy due to scales, but there are no floating substances in the liquid. The roller is slimy, but the rinsing tank wall is not slimy. 4: Part of the roller is slimy. 5: No scale is generated.

[0308]

[Table 3]

[0309]

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As is clear from Table 3, when the treatment method according to claim 1 of the present invention was employed, evaluation items such as sensitivity, γ, dot quality, water stain in a washing tank, and residual color after treatment were evaluated. It can be seen that this is also excellent. However, if it is out of the range, any of these items is deteriorated, and it can be seen that it is not practical.

Example 2 (Claim 2) (Preparation of silver halide emulsion A) Aqueous solution of silver nitrate B and Na
A water-soluble halide solution C composed of Cl and KBr is adjusted to pH 3.
0, 40 ° C., constant flow rate, added in solution A for 30 minutes by the simultaneous mixing method, and added 0.20 μm AgCl 70 mol%, AgBr
30 mol% of cubic crystals were obtained. At this time, silver potential (EAg)
Is 160 mV at the start of mixing and 100 mV at the end of mixing
It was V. After this, unnecessary salts were removed by ultrafiltration, and then 15 g of gelatin was added per 1 mol of silver to adjust the pH to 5.7 and dispersed at 55 ° C. for 30 minutes. After dispersion, chloramine T is added in an amount of 4 × 10 ⁻⁴ mol per mol of silver.
Was added. The silver potential of the resulting emulsion was 190 mV (4
0 ° C).

Solution A Ossein gelatin 25 g Nitric acid (5%) 6.5 ml Ion exchange water 700 ml Na [RhCl ₅ (H ₂ O)] 0.02 mg Solution B Silver nitrate 170 g Nitric acid (5%) 4.5 ml Ion exchange water 200 ml Solution C 47.5 g of NaCl 51.3 g of KBr 6 g of ossein gelatin 0.15 mg of Na ₃ [IrCl ₆ ] 200 ml of ion-exchanged water 200 ml of 4-hydroxy-6 per mol of silver in the obtained emulsion
1-methyl-1,3,3a, 7-tetrazaindene.
5 × 10 ^-3 mol, 8.5 × 10 ^-4 mol of potassium bromide
The pH was adjusted to 5.6 and the EAg to 123 mV by adding 1 l. Sulfur dispersed in the form of fine particles is converted into a sulfur atom as 2 × 1
After adding 0 ^-5 mol and 1.5 × 10 ^-5 mol of chloroauric acid and performing chemical ripening at a temperature of 50 ° C. for 80 minutes, 4-hydroxy-6-methyl-1,3,3a, 7- 2 × 10 ⁻³ mol of tetrazaindene, 3 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole and 1.5 × 10 ⁻³ mol of potassium iodide were added per 1 mol of silver. 40
After the temperature was lowered to 0 ° C., the sensitizing dyes shown in Table 4 (Comparative Compound 2,
4-17, 4-20, 4-43, 4-50) and S-1
Was added.

[0313]

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Using the emulsion thus obtained, 1 m ²
The following first layer, second layer, and
The third layer was simultaneously coated in multiple layers and cooled and set. Thereafter, the following backing layer was applied on the undercoating layer having the antistatic layer on the opposite side, cooled and set at -1 ° C, and both sides were simultaneously dried to obtain Samples 201 to 206.

(Support, Undercoat Layer) After a corona discharge of 30 W / (m ² · min) was applied to both sides of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm), an undercoat layer having the following composition was applied to both sides. And dried at 100 ° C. for 1 minute.

2-Hydroxyethyl methacrylate (25) -butyl acrylate (30) -t-butyl acrylate (25) -styrene (20) copolymer (numbers are by weight) 0.5 g / m ² surfactant A 3 1.6 mg / m ² Hexamethylene-1,6-bis (ethylene urea) 10 mg / m ² Antistatic layer One layer was applied to a polyethylene terephthalate support provided with an undercoat layer.
After a corona discharge of 0 W / (m ² · min), an antistatic layer having the following composition was applied on one side at a speed of 70 m / min using a roll-fit coating pan and an air knife, and dried at 90 ° C. for 2 minutes. Then, heat treatment was performed at 140 ° C. for 90 seconds.

Water-soluble conductive polymer B 0.6 g / m ² Hydrophobic polymer particles C 0.4 g / m ² Polyethylene oxide compound (Mw600) 0.1 g / m ² Curing agent E 0.01 g / m ² First layer Gelatin 0.30 g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 0.005 g sodium-iso-amyl-n-decylsulfosuccinate 0.005 g sodium dodecylbenzenesulfonate 0.02 g polystyrenesulfonic acid (Mw 500,000) 0.02 g Second layer (emulsion layer) Gelatin 1.0 g Silver halide emulsion A 3.3 g as silver amount Hydrazine derivative Ha 0.015 g Hydrazine derivative Hb 0.020 g Nucleation promoter AM 0 .15 g 5-nitroindazole 0.01 g 2-mercaptohypoxanthine 0.02 g 1.7 g of a suspension polymer of 75% by weight of toroidal silica, 12.5% by weight of vinyl acetate, and 12.5% by weight of vinyl pivalinate 1.7 g of polymer latex L1 (particle size: 0.10 μm) 0.5 g dextran (average molecular weight of 40,000) 0.1 g Surfactant (SU-1) 0.09 g 4-mercapto-3,5,6-fluorophthalic acid 0.05 g Sodium polystyrene sulfonate (average molecular weight 50
10,000) The coating solution pH was 5.2.

Third layer (protective layer) Gelatin 0.50 g Dextran (average molecular weight 40,000) 0.2 g Colloidal silica 0.10 g Surfactant (SU-2) 0.02 g Dihydroxybenzenes Table 4 Sodium dihexyl sulfosuccinate Nate 0.010 g Fungicide Z 0.005 g Hardener (1) 0.07 g Polymethyl methacrylate latex (size 3 μm) 0.01 g Backing layer Gelatin 2.0 g Dye F-1 90.0 mg Dye F-2 90.0 mg Dye F-3 25.0mg Sodium dihexyl sulfosuccinate 0.020g Suspension polymer of colloidal silica 75% by weight, vinyl acetate 12.5% by weight, and vinyl pivalinate 12.5% by weight 0.7g Polystyrene sulfone Sodium acid salt 0.010 g Matting agent: simple having an average particle size of 3 μm Dispersed polymethyl methacrylate 0.045 g Hardener (1) 0.05 g Hardener (2) 0.07 g

[0319]

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[0320]

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[0321]

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[0322]

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-Evaluation- (Sensitivity) The obtained sample was closely adhered to a step wedge,
Automatic developing machine GR-27 using the developing solution and the fixing solution used in Example 1 after exposing with tungsten light of 200 ° K for 3 seconds.
(Konica Corporation) under the above conditions. The blackened density of the developed sample thus obtained was measured with a PDA-65 (Konica Digital Densitometer). The reciprocal of the exposure amount that gives a blackening density of 1.0 is defined as 100 and expressed as relative sensitivity.

The others were evaluated in the same manner as in Example 1. The results obtained are shown in Table 4 below.

[0325]

[Table 4]

As is evident from Table 4, the treatment method according to claim 2 of the present invention is excellent in any of the evaluation items of sensitivity, γ, washing tank stain, and recoloring after treatment. That is, the above effects are best exhibited by processing a photosensitive material containing the compound represented by the general formula [4].

Example 3 (Claim 3) Samples 301 to 307 were prepared in the same manner as in Example 2 except that the sensitizing dye was changed as shown in Table 5.

-Evaluation- (Sensitivity) The obtained sample was closely adhered to a step wedge,
Automatic developing machine GR-27 using the developing solution and the fixing solution used in Example 1 after exposing with tungsten light of 200 ° K for 3 seconds.
(Konica Corporation) under the above conditions. The blackened density of the developed sample thus obtained was measured with a PDA-65 (Konica Digital Densitometer). The reciprocal of the exposure amount that gives a blackening density of 1.0 is expressed as a relative sensitivity, with 100 being the reciprocal.

(Confirmation of Rolling Performance) He made by Konica Corporation
5% and 95% at 400 liters with SG747 manufactured by Dainippon Screen Co., Ltd. using scanner film SH-3 for Ne.
Is output as a document, and the enlargement magnification is set to 120% using a fine zoom C-880F manufactured by Dainippon Screen Co., Ltd., so that 95% of the document becomes 5%. Exposure was performed by changing the exposure amount as described above, and the same processing as the measurement of sensitivity was performed.

The obtained developed sample was subjected to X-Ri
The dot% is measured by te361T, and 95% of the original is 5%.
At the exposure amount (appropriate exposure) of 5%, the crushing of halftone dots of 5% of the original was visually evaluated.

A completely crushed object was ranked as 1 rank, a practically non-crushed final level was rated at 3 ranks, and a level at which a document was considered to be reproduced was rated at 5 ranks.

The other conditions were evaluated in the same manner as in Example 1. The results obtained are shown in Table 5 below.

[0333]

[Table 5]

[0334]

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As is clear from Table 5, the treatment method according to the third aspect of the present invention is excellent in all of the evaluation items such as sensitivity, γ, stains in a washing tank, recoloring after treatment and elongation performance. You can see that there is. That is, the above effects are best exhibited by processing a photosensitive material containing the compound represented by the general formula [5].

Example 4 (Claim 4) The compounds (sensitizing dyes) represented by the general formulas [4] and [5] in Examples 2 and 3 were changed as shown in Table 6, and polyhydroxybenzene was used. Samples 401 to 4 were prepared in the same manner except that dihydroxybenzene was added as a system compound as shown in Table 6.
06 was prepared and evaluated in the same manner as in Example 1.

[0337]

[Table 6]

As is clear from Table 6, the processing method according to the fourth aspect of the present invention is excellent in any of evaluation items of sensitivity, γ, washing tank stain, recoloration after processing, and halftone dot quality. You can see that. That is, the above effects are best exhibited by processing a photosensitive material containing a polyhydroxybenzene compound. It can also be seen that when the compounds represented by the general formulas [4] and [5] are simultaneously contained, the effect is superior to the case where the polyhydroxybenzene-based compound is added alone.

[0339]

According to the present invention, the coloring of the photosensitive material over time and the image storability can be improved, and the dirt in the washing tank of the automatic developing machine can be greatly reduced to improve the maintainability. It has excellent effects. Specifically, in a system in which a photosensitive material is processed with a processing solution using a specific ascorbic acid as a developing agent, the photosensitive material itself is a specific sensitizing dye (general formulas [1] to [5]) defined in the present invention. In the case of containing a compound represented by formula (1)) or a polyhydroxybenzene compound, an image excellent in sensitivity, γ, recoloration after processing and halftone dot quality can be obtained, and stains in the washing tank of the automatic processing machine are greatly reduced. In addition, the present invention has an excellent effect that the problems on the image surface and the device side are greatly improved, for example, the effect on maintenance can be greatly reduced.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) G03C 1/42 G03C 1/42 1/83 1/83 5/30 5/30 5/305 5/305 11 / 00 11/00

Claims (12)

[Claims] 1. A silver halide emulsion layer is provided on a support.
On the side of the compound represented by the following general formulas [1] to [3]
Image of silver halide photographic material containing at least one kind
After exposure, contains a developing agent represented by the following general formula (A)
And a developer with a sulfurous acid concentration of 0.4 mol / l or less
Rinsing treatment and washing with washing water containing an oxidizing agent.
A method for processing a silver halide photographic light-sensitive material. Embedded image(In the general formula [1], R₁Is -OX or -N (X)
An atomic group represented by (Y), wherein X and Y are hydrogen atoms
, Alkyl group, cyanoalkyl group, carboxyalkyl
Group, sulfoalkyl group, hydroxyalkyl group, halo
Genated alkyl group or alkyl group which may be substituted or
Or its sodium or potassium salt, R _TwoAnd R_ThreeIs water
Element atom, halogen atom, alkyl group, hydroxy group,
Alkoxy group, alkylthio group, or the same as the above-described -OX group.
Q represents at least one halogen atom,
Ruboxyl group, sulfo group, sulfoalkyl group or the like
Phenyl group substituted with sodium or potassium salt, sulf
Hoalkyl group, sulfoalkoxyalkyl group, sulfoa
Represents a alkylthioalkyl group, and L may be substituted
Represents a methine group. R_FourIs an alkyl group, a carboxyl group,
Alkyloxycarbonyl group or acyl substituted, unsubstituted
Represents an amino group. m is an integer 1 or 2, n is an integer 0 or
Represents 1 respectively. In the general formula [2], R₁₁as well as
R₁₂Represents an alkyl group, a substituted alkyl group, an aryl group,
Represents a oxycarbonyl group or a carboxyl group;₁₃
And R₁₄Represents a hydrogen atom, an aliphatic group or an aromatic group, and L represents
Represents an optionally substituted methine group. M is sodium, mosquito
Represents a lithium or hydrogen atom, and 1 represents 0 or 1. General
In equation [3], R₁~ R_FourIs an alkyl group, hydroxy
Alkyl group, cyano group, alkyl cyano group, alkoxy
And a sulfoalkyl group. R_FiveAnd R₆Is sulfone
It represents an acid group or an alkylsulfonic acid group. In general formula (A)
And R₁And R_TwoAre each independently a substituted or unsubstituted alkyl
Group, substituted or unsubstituted amino group, substituted or unsubstituted
Represents a alkoxy group or a substituted or unsubstituted alkylthio group.
R₁And R_TwoMay combine with each other to form a ring. k is 0
Or 1 and when k = 1, X is -CO- or -CS-
Represents M₁, M_TwoRepresents a hydrogen atom or an alkali metal, respectively.
You. ) 2. A silver halide photographic light-sensitive material containing at least one compound represented by the following general formula [4] on the side having a silver halide emulsion layer with respect to a support, and after imagewise exposing the same, A silver halide photograph characterized by being fixed with a developer containing a developing agent represented by the formula (A) and having a sulfurous acid concentration of 0.4 mol / l or less, and further washed with washing water containing an oxidizing agent. Processing method of photosensitive material. Embedded image (Where Z is a thiazoline nucleus, thiazolidine nucleus, selenazoline nucleus, selenazolidine nucleus, pyrrolidine nucleus, oxazoline nucleus, oxazolidine nucleus, imidazoline nucleus, indoline nucleus, tetrazoline nucleus, benzothiazoline nucleus, benzoselenazoline nucleus, benzimidazoline Q represents a nonmetallic atomic group necessary for completing a nucleus, a benzoxazoline nucleus, a naphthothiazoline nucleus, a naphthoselenazoline nucleus, a naphthooxazoline nucleus, a naphthoimidazoline nucleus or a dihydroquinoline nucleus, and Q represents a rhodanine nucleus, a 2-thiooxazoline- R ₁ and R ₂ each represent a hydrogen atom, a substituted or unsubstituted nucleus, which is necessary to complete a 2,4-dione nucleus, a 2-thiohydantoin nucleus, a barbituric acid nucleus or a 2-thiobarbituric acid nucleus; A substituted alkyl group or a substituted or unsubstituted aryl group And p represents 0 or 1.) 3. A silver halide photographic light-sensitive material containing at least one compound represented by the following general formula [5] on a side having a silver halide emulsion layer with respect to a support, after imagewise exposure, A silver halide photograph characterized by being fixed with a developer containing a developing agent represented by the formula (A) and having a sulfurous acid concentration of 0.4 mol / l or less, and further washed with washing water containing an oxidizing agent. Processing method of photosensitive material. Embedded image (Wherein R ₁ and R ₂ each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, a sulfo group or a carboxyl group; R ₁ and R ₂ may combine to form a 6-membered ring, R ₃ represents an alkyl group, an alkenyl group or an alkynyl group, and R ₄ represents an alkyl group having 1 to 12 carbon atoms. Represents -O-, -OC between its carbon chains.
O-, -NH- and -N <are included. R ₅ is an alkyl group, an alkenyl group, an alkynyl group,
Represents an aryl group or a heterocyclic group. ) 4. A method according to claim 1, wherein at least one polyhydroxybenzene compound is provided on the side of the support having the silver halide emulsion layer.
After the silver halide photographic light-sensitive material containing the seeds is imagewise exposed, it is fixed with a developing solution containing a developing agent represented by the above general formula (A) and having a sulfurous acid concentration of 0.4 mol / l or less, and further oxidized. A method for processing a silver halide photographic light-sensitive material, characterized by washing with washing water containing an agent. 5. The oxidizing agent supply means according to claim 1, wherein the oxidizing agent-containing concentrated liquid or solid agent is supplied while being mixed with water in a washing tank of an automatic developing machine. The method for processing a silver halide photographic light-sensitive material described in the above. 6. The method for processing a silver halide photographic material according to claim 1, wherein the oxidizing agent is hydrogen peroxide. 7. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the capacity of the washing tank is 20 l or less. 8. The processing method for a silver halide photographic light-sensitive material according to claim 1, wherein a bactericide is contained in the washing water. 9. The silver halide photograph according to claim 1, wherein the washing water contains a compound having a polyalkylene oxide chain represented by the following general formula (B). Processing method of photosensitive material. General formula (B) HO (C ₂ H ₄ O) _a- (C ₂ H ₄ O) _b- (C ₂ H ₄ O) _c H (where a, b, and c represent positive integers) 10. The washing water contains salicylic acid and its derivatives and salts thereof.
10. The method for processing a silver halide photographic light-sensitive material according to any one of items 1 to 9, 11. The silver halide photographic material according to claim 1, wherein said washing water contains a silver sludge inhibitor represented by the following general formula (C). Processing method. General formula (C) Z ¹ -SM ¹ (wherein, Z ¹ represents an alkyl group, an aromatic group or a heterocyclic group, and M ¹ represents a hydrogen atom, an alkali metal atom, a substituted or unsubstituted amidino group. ) 12. The halogenation according to claim 1, wherein the washing water contains a chelating agent having a chelate stability constant of 0.8 to 5.0 with calcium ions. Processing method of silver photographic photosensitive material.