JPH03158851A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance stability of a processing solution and an image and to reduce occurrence of stains by adding silver ions and a compound addable to hydrogen sulfite in a fixing solution containing thiosulfate. CONSTITUTION:The imagewise exposed silver halide photographic sensitive material is processed with the processing solution having fixing ability containing as a fixing agent the thiosulfate and further the silver ions in a concentration of 0.005 - 0.1 time that of a fixing agent and the compound addable to the hydrogen sulfite and/or a hydrogen sulfite adduct of the compound, and the compounds represented by general formulae (A) - (D) are preferable as the addable compound. The addition of the compound makes it difficult to rinse a color developing agent mixed into the photosensitive material out of it in the following fixing step or fixing step, but the presence of the silver ions in the concentration facilitates rinsing of the color developing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides excellent liquid stability of a processing solution having fixing ability and stability of the resulting image when continuous processing of silver halide photographic light-sensitive materials is attempted. The present invention relates to a method for processing silver halide photographic materials that have excellent properties and are less likely to cause staining.

(Prior Art) In the processing of silver halide photographic materials, it has become an important issue to provide better photographic images more stably than before. Especially now that there is a strong demand for speeding up processing and reducing the amount of replenishment to reduce waste liquid, it is becoming more difficult to achieve the above-mentioned problems.

In order to provide stable and good photographic images, the most important issue is that the photographic processing solution is stable against deterioration over time due to air oxidation and the like. In particular, in current photographic processing where reducing the amount of washing water or stabilizing processing is widely carried out, it is an extremely important issue to improve the stability over time of the processing solution that has fixing ability and the subsequent washing solution or stabilizing solution. .

As a means for improving the stability of such a processing liquid having a fixing ability, a carbonyl compound bisulfite adduct has been provided as a preservative for a processing liquid having a fixing ability.

Regarding these carbonyl compound bisulfite adducts, please refer to JP-A Nos. 48-42733, 50-51326, and 5
No. 6-107244, West German Patent No. 2102713, etc. describe a method of using it as a bleach-fixing solution or a fixing solution preservative. However, although carbonyl compound bisulfite adducts have excellent performance as preservatives for processing solutions with fixing ability, they have various problems.
However, it was not put into practical use until now [1]. In particular, when conventional photographic materials were processed with a bleach-fix solution that uses a bisulfite adduct of a carbonyl compound as a preservative, a problem arose in that the image storage stability of the photographic materials deteriorated. That is, as processed photosensitive materials are stored over time, a problem arises in that the minimum 11 degrees (D+win >) of uncolored areas of the photosensitive materials increases. There is a strong demand for a method for processing silver halide color photographic materials that has excellent stability and does not deteriorate image storage stability.

On the other hand, it has been proposed to perform bleaching or bleach-fixing using a bleaching agent with stronger oxidizing power instead of the ferric complex salt of ethylenediaminetetraacetic acid that has been conventionally used as a bleaching agent. As a result, it has become possible to shorten processing time or reduce the amount of photographic processing waste liquid discharged. In other words, by using a strong oxidizing agent as a bleaching agent, the bleaching reaction rate in the bleaching or bleach-fixing process can be increased and the above processing steps can be accelerated, or the bleaching solution or bleach-fixing solution can be used as an oxidizing agent over time. By maintaining excellent bleaching performance even when the amount of bleaching agent (bleaching agent) or preservative is reduced, it is possible to reduce the amount of replenishment of the processing solution. be. However, when a strong oxidizing agent (bleaching agent) is used as described above, the stability of the subsequent fixing solution over time decreases due to the bleaching solution carried over during the bleaching process. It has become clear that in some cases, the stability of the bleach-fix solution itself over time is significantly reduced, resulting in delayed bleaching and desilvering reactions. Therefore, even more? & It has become clear that the stability over time of subsequent washing baths or stabilization baths also deteriorates. Therefore, there has been a growing demand for techniques to improve the stability of bleaching solutions or fixing solutions over time.

As a means of increasing the stability of such processing liquid over time,
A method has been proposed in which a carbonyl bisulfite adduct and a compound having an amino group as a functional group are used in a bleach-fix solution (Japanese Unexamined Patent Publication No. 1-267540).

However, these methods do not improve the stability of processed color images, and especially when the photosensitive material is stored after processing, there is a problem in that magentastin is generated. For this reason, there has been a demand for means for improving the stability of bleach-fixing solutions or fixing solutions over time, increasing the stability of images, and preventing the formation of magentastin.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to provide a method for processing silver halide photographic materials in which the fixing solution or bleach-fixing solution is excellent in stability. The second object is to provide a processing method that provides excellent image preservation of the obtained color photographic images.

A third object of the present invention is to provide a processing method that allows rapid desilvering processing.

(Means for Solving the Problems) As a result of intensive studies, the present inventors have found that, in an attempt to improve the stability of bleach-fix solutions and/or fix solutions, compounds that can form adducts with bisulfites have been developed. For example, when a carbonyl compound or the like is contained in the bleach-fixing solution and/or the fixing solution, the color developing agent incorporated into the light-sensitive material in the color development processing step is more likely to be absorbed into the light-sensitive material in the subsequent bleach-fixing step or fixing step than when the carbonyl compound or the like is contained in the bleach-fixing solution and/or the fixing solution. It was found that silver became difficult to wash out from the photosensitive material during the process, and even in the subsequent water washing process, it remained in the photosensitive material without being washed out sufficiently.As a result of re-examining this, we found that silver is difficult to wash out from the photosensitive material in the bleach-fixing solution and fixing solution. The present invention was based on the discovery that the presence of ions facilitates the washing out of the developing agent from the photosensitive material.

That is, in a processing method comprising a step of treating an imagewise exposed silver halide photographic light-sensitive material with a processing liquid having a fixing ability, the processing liquid having a fixing ability has at least the following (1) to
(3) A method for processing a silver halide photographic material t4, which is characterized by having the composition.

■ Naosulfate as a fixing agent, ■ Fixing agent l; 0.005 to 0.1 l; silver ions in degrees, ■ at least one biITi sulphate and a compound capable of addition 6J and/or at least One of said 11 (an adduct of a 6A acid, a compound capable of addition, and a bisulfite).

First, compounds that can be added to the heavy H1i sulfate of the present invention will be explained.

Compounds having the bisulfite and addition=J ability are preferably compounds represented by the following formulas (A) to (D).

General formula (A) 1 r? , -C-R.

In the formula, R represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, an allyl group, a heterocyclic group, a carboxylic acid group, an ester group, an acyl group, or a carbamoyl group, and R6 represents a hydrogen atom or an alkyl group. R and R6 may be combined to form a ring.

General formula (A) will be explained in detail below.

R1 is a hydrogen atom, a substituted or unsubstituted alkyl group (e.g., methyl group, ethyl group, methoxyethyl group, carboxymethyl group, sulfomethyl group, sulfoethyl group, etc.), an alkenyl group (e.g., allyl group, etc.), Aralkyl groups (e.g. benzyl group, phenethyl group, 4-
methquinohensyl group, 4-sulfohensyl group, etc.), cycloalkyl group (e.g., nclohexyl group, etc.), Aryl 71: (e.g., phenyl group, naphthyl group, 3-
sulfobutoxyphenyl group, 4-N-methyl N-sulfopropylaminophenyl group, 3-sulfopropylphenyl group, 3-carboxyphenyl group, etc.), heterocyclic group (
For example, pyridyl group, thienyl group, pyrrolyl group, indolyl group, furyl group, furfuryl group, morpholinyl group, imidazolyl group, etc.), ester group (for example, methoxycarbonyl group, ethoxycarbonyl group, etc.), acyl group (
For example, acetyl group, methoxypropionyl group, etc.)
Substituted or unsubstituted alkyl group, alkenyl group, aralkyl group, cycloalkyl group, aryl group represented by Rt, which represents a carbamoyl group (e.g., unsubstituted carbamoyl group, dimethylcarbamoyl group, etc.), carboxylic acid group or a salt thereof; Examples of groups or heterocyclic groups are the same as those for R. Also, R and Rt are integrated and are 5 to 7
A saturated or unsaturated ring of members may be formed.

- during formation (A), preferably R+, R1 is a hydrogen atom,
Each represents a substituted or unsubstituted alkyl group, aryl group or heterocyclic group.

- In the formation (A), R1 more preferably represents a hydrogen atom, and R3 represents a substituted or unsubstituted aryl group or a heterocyclic group, provided that when the aryl group has a substituent, the substituent The sum of the substituent constants (α value) of the formula (Hame-/) is -1.2 to 1.0, and at least one of the substituents is a sulfo group, a carboxyl group, a sulfino group, a phosphono group, or an ammonio group. It is preferable to have the following. The term Panot's alpha value here refers to the Journal on Medicinal Chemistry (J, Med, Chew, ).
16, 1207 (1973) and 20, 30
4 (1977).

General formula (B) Ra Rs In the formula, R3, R4, and R2 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a carboxylic acid group, an ester group, and an acyl group. group, halogen atom, ether group, sulfo group, sulfinyl group, sulfonyl group, cyano group, nitro group, carbamoyl group or sulfamoyl group, and R4 represents an electron-withdrawing group.

Further, R1 and R, , R, and Rs, Rs and R4, and R6 and R1 may be combined to form a ring.

General formula (B) will be explained in detail below.

7f 10 or N W 10 alkyl group, alkenyl group, aralkyl group, cycloalkyl group, aryl group, heterocyclic group represented by R1, R4, R1, respectively;
Ester group, acyl group, carbamoyl group S have the same meaning as each of R7, and furthermore, halogen atom (e.g. chlorine atom, etc.), sulfono λ or its salt, substituted or unsubstituted ether group (e.g. methocino) phenoquine group, etc.), sulfinyl group (e.g. methanesulfinyl group, etc.), sulfonyl) L (e.g. methanesulfonyl)S, benzenesulfonyl group, 4-methylhenzenesulfonyl group, etc.), sulfamoyl group (e.g. , an unsubstituted sulfamoyl group, a dimethylsulfamoyl group, etc.), and R6 is an electron-withdrawing group (+ii+ preferably has a Hamefto α value of 0 to 1.0; for example, a nitro group, a cyano group). , sulfonyl group, acyl group, ester group, etc.).

- In formation (B), preferably R, R, Rs represent a hydrogen atom, a carboxylic acid group, a cyano group, a substituted or unsubstituted alkyl group, an aryl group, a hetero radical, an ester group or an acyl group, R& is a nitro group, a cyano group,
Each represents a substituted or unsubstituted acyl group or ester group.

-Formation (C) R, -C-R.

In the formula, Rv, Rs, Re each independently represent a hydrogen atom,
represents an alkyl group, an alkenyl group, a cycloalkyl group, an aralkyl group, an aryl group, a hetero q3, an amino group, a carboxylic acid group, an ester group, an acyl group, an ether group, a hydroxyl group, a 1,000-onythyl group, and X represents an anion; n is 0
Or not represent 1.

Furthermore, R1 and R, R, and Rq, and Re and R7 may be combined to form a ring.

General formula (C) will be explained in detail below.

The substituted or unsubstituted alkyl group, alkenyl group, cycloalkyl group, aralkyl group, aryl group, heterocyclic group, ester group, acyl group, and ether group represented by Rv, Re, and R9 have the same meaning as R9, respectively. , further substituted or unsubstituted amino groups (e.g., unsubstituted amino group, dimethylamino group, carboxymethylamino group, etc.), substituted or unsubstituted thioether groups (
For example, methylthio group, methylthiomethylthio group, etc.)
X represents an anion (eg, chloride ion, bromide ion, p-toluenesulfonate ion, verchlorate ion, etc.).

- In formation (C), preferably Ry, Rs, R9 are hydrogen atoms, each substituted or unsubstituted alkyl group,
Represents an aryl group, a heterocyclic group, or an amino group.

General formula (D) Z-6 In the formula, Re represents an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, a ring group, a heterocyclic group, and Z is a carbon atom, a nitrogen atom, an oxygen atom, Represents a petero ring composed of a sulfur atom and a selenium atom, Y represents an anion, m represents 0 or l, and R1° represents Z
It may be combined with other atoms to form a ring.

General formula (D) will be explained in detail below.

R1° is a W-substituted or unsubstituted alkyl group (e.g., methyl group, ethyl group, sulfoethyl group, sulfobutyl group, sulfopropyl group, carboxyethyl group, dimethylaminoethyl group, 2,2°2-trifluoroethyl group) , etc.), alkenyl groups (e.g., allyl groups, etc.), aralkyl groups (e.g., benzyl groups, phenethyl groups, etc.),
cycloalkyl group (e.g. cyclohexyl group, etc.),
Aryl group (e.g., phenyl group, naphthyl group, 4methoxyphenyl group, 3-sulfopropylphenyl group, etc.)
, represents a heterocyclic group (e.g., pyridyl group, pyrazolyl group, imidazolyl group, etc.), and Z is a 5- to
Represents a 6-membered heterocycle (eg, pyridinium ring, imidazolium ring, quinolinium ring, oxacillium ring, thiazolium ring, hendimidanolium ring, etc.).

Z may have a substituent, and Y represents an anion (eg, chloride ion, bromide ion, p-toluenesulfonate ion, etc.).

-a formula (in DJ, preferably each R1° represents a substituted or unsubstituted alkyl W, and Z represents an imidazolium ring, a henzimidazolium ring, a quinolinium ring, or a quinolinium ring.

Specific examples of the compounds of general formulas (A) to (D) used in the present invention are shown below, but the present invention is not limited thereto.

A-I A-2C110CII
O 0ONa 03Na SO,Na 1 2 110 IIO 3 C) 10 4 HO -15 6- 8 -27 ■ 9 0 CL/NCHz)zsOJa -22 -26 -28 29 0 6 7 C1!0 HO OHC(C)It ) 4cli0 Cl 1 j] Cl1tCCIIzCIIzSOJa 8 9 110 2 0 1 CII3CCII! O1+ 3 cll, 0CII□Cll0 0 110 1 4 5 2 C) 10 CI+.

OJa -1 -3 -7 -7 C2115 D-10 -1 tHS (CI(2) n5OJa C,H.

-5 C2H4 Many of these compounds are commercially available and can be used as they are. Other compounds can also be synthesized using known organic synthesis reactions.For example, organic synthesis (Org, Syn,)
Co11active Vol, I 537 (1
941), Co11ective Vol. I [[5
64 (1955), Organic Reaction (Or
g.

Reaction) ■, 1 (1968),
Organic Functional Group Preparations (Org) by S. R., Sandra-W.
anicFunctinalgroup Prepar
ations) Volume 2, page 291 (1986), Volume 3
It can be synthesized according to the method described in Vol. 205, p. 1972.

The processing liquid having fixing ability in the present invention refers to a bleach-fixing liquid or a fixing liquid.

The amount of these compounds added to the bleach-fixing solution and/or fixing solution is 1Xl0-'mol-5 per liter of the processing solution.
Moles are preferred, particularly l x 10-'' moles - 1 mole.

In addition, when using compounds that can be added to these bisulfites, it is preferable that the bleach-fix solution or fixer contains sulfites, bi+sulfates, or metabisulfites and total salts. is preferably thorium sulfite, ammonium sulfite, potassium sulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, etc., and 1Xl0-' mol-5 mol per 11 of the treatment liquid,
Preferably, 1XIO-''mol-1 mol is added.

The compound that can be added to bisulfite of the present invention is one that can easily react to form an lj bisulfite adduct when sulfite or bisulfite coexists in a bleach-fix solution or a fix solution. . These reactions are represented by -C as follows.

1) X+ISO,-;=>X-3O.

2) X+SO, +l+':=;;≧X-5O.

In the formula, X is a compound that can be added with bisulfite, X-503"
represents an isoadduct.

F (These reactions are rThe Chemistry or
LheCarbonyl Groupj Volume 2, (I
published by interscience Publishers) 3
Although it is described in many books on organic chemistry including 3rd page, 1970), the addition of bisulfite to the compounds represented by the general formulas (8) to ([)) of the present invention is Explain the reaction.

)-formation (A) 011 1 SOL For example, for exemplary compound A-1, Ru.

II) - Compound 03 represented by formation (B) iii) - Compound 5O1 represented by formation (C) iv) -%i Compound represented by formula (D) The amounts of these bisulfite adducts to be added to the bleach-fix solution are: , preferably from 10-' to 5 mol of I x per 11 of the treatment liquid;
More preferably Xl0-'' to 1 mol.

The processing liquid having fixing ability of the present invention contains thiosulfate as a fixing agent. These thiosulfates include ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate,
Examples include calcium thiosulfate and magnesium periosulfate, but ammonium thiosulfate is preferred because it has good solubility and has the highest fixing speed. One amount of thiosulfuric acid added is O, 1 mol/1 to 3 mol/1,
0.3 mol/l-2 mol/l is preferred.

In addition to the above-mentioned thiosulfates, thiocyanic acid compounds (especially ammonium salts), thioureas, thioethers, ureas, etc. can be used as fixing agents or fixing accelerators for the bleach-fix solution and/or fix solution of the present invention. The concentration of these auxiliary fixing agents or fixing accelerators, including the thiosulfate, is 1.11 to 3.0 mol/1, preferably 1.4 to 2.8 mol/1.

The processing liquid having fixing ability of the present invention has a 0%
．． It contains silver ions in an amount of 0.005 to 0.1 times, preferably 0.001 to 0.1 times.

The silver ions to be contained in the processing liquid having these fixing abilities will be explained. As a method for incorporating silver ions into the processing liquid having the fixing ability, silver nitrate, silver thionoanate, thioether in IN is added to the processing liquid having the fixing ability.
A method of adding a water-soluble F-R salt such as fff salt, silver thiohAr acid 2B salt, etc. may be used, or a method in which the silver halide inside is dissolved and replenished in a processing solution having a fixing ability in one exposure process along with continuous processing. However, especially at the start of i! subsequent processing, water-soluble root salts should be added to the bleach-fix solution or fixer mother solution, and no i1z salt should be added to the hi solution, and the photosensitive material t' should be added during continuous processing. of silver halide is dissolved and replenished into the bleach-fix solution or fix solution, and the 4 degrees of silver salt (silver ion) in the bleach-fix solution or fix solution is maintained constant.
Most preferred, silver ion 1: If the degree is too low, the effect of the present invention will be diminished, and if it is too high, the fixing ability will be reduced.

The material having the fixing ability of the present invention t'! ! When the solution is a bleach-fix solution, it is preferred to use a ferric aminopolycarboxylic acid complex salt as the bleaching agent. Examples of the aminopolycarboxylic acids of these ferric complex salts include, but are not limited to, the following compounds.

α-1: 1.3-Noaminopropanetetraacetic acid α-2 = glycol ether diamine tetraacetic acid α-3; 2-propylenediaminetetraacetic acid α-6: thioglycoletherdiaminetetraacetic acid α-7 1.3-butylenediaminetetraacetic acid α-8: ethylenediaminetetraacetic acid In the present invention, the amount of bleach added to the bleach-fix solution is as follows: 0.05 to 1 mol, preferably 0.1 to 1 mol per 11 bleach-fix solution
It is 0.5 mole. Further, the ferric complex salts of aminopolycarboxylic acids α-1 to α-7 and the ferric complex salt of ethylenedi7minetetraacetic acid ferric complex salt α-8 can be used in combination as a bleaching agent. . In this case, the mixing ratio of both is 1:1
The ratio is preferably 0 to 10:1, and the total amount of both iron complex salts is 0.05 to 1 mol, preferably 0.1 to 0.5 mol, per 1 liter of treatment solution.

The bleach-fix solution or fixing solution of the present invention preferably contains an aminopolycarboxylic acid.

The amount added is preferably from 0.0001 mol to 0.1 mol/l, more preferably from 0.003 to 0.05 mol/l.

Aminopolycarboxylic acids and their ferric complex salts are usually preferably used in the form of alkali metal salts or ammonium salts, and ammonium salts are particularly preferred because they have excellent solubility and bleaching properties.

Further, the above bleaching solution and/or bleach-fixing solution containing the ferric complex salt may contain tH salts of metal ions such as cobalt and copper other than iron.

Further, the bleach-fix solution of the present invention and its pre-bath may contain a bleach accelerator.

Such bleach accelerators are described, for example, in US Pat. No. 3,893,858, German Patent No. 1,290.
．． Compounds having a mercapto group or a disulfide group described in Specification No. 812, British Patent No. 1 138.842, JP-A-53-95630, Research Disclosure No. 17129 (July 1978 issue) , thiazolidine derivatives described in JP-A-50-140129, 1,000-urea derivatives described in U.S. Pat. No. 3,706,561, iodides described in JP-A-58-16235, and German patents. Polyethylene oxides described in specification No. 2,748.430, Japanese Patent Publication No. 1974-
Polyamine compounds described in Japanese Patent No. 8836 can be used. Particularly preferred is British Patent No. 1,138.
Mercapto compounds such as those described in '842 are preferred.

The amount of bleaching accelerator added is 0.000000000000000000 for 110000. O
lg to 20g, preferably 0.1g to 10g.

In addition to the bleaching agent and the above-mentioned compounds, the bleach-fixing solution and/or fixing solution in the present invention may contain bromides, such as potassium bromide, sodium bromide, ammonium bromide, or chlorides, such as potassium chloride, sodium chloride, ammonium chloride. can include rehalogenating agents such as. The concentration of rehalogenating agent is between 0.1 and 5 mol per bleach I&11, preferably between 0.5 and 3 mol. In addition, 61'l salts such as sodium nitrate and ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, hydroquinoacetic acid, lactic acid, sodium acetate, sodium carbonate, potassium carbonate, boronphosphoric acid, phosphoric acid, sodium phosphate, citric acid, One or more kinds of inorganic acids having p-buffering capacity such as sodium citrate and tartaric acid, organic acids and salts thereof, and other known additives that can be used in conventional bleaching solutions can be added.

The bleach constant tI solution and/or fixing solution of the present invention can contain 1F sulfate as a preservative, such as sodium sulfite, potassium sulfite, ammonium sulfite, hydroquinolamine, hydrazine, and the like. Furthermore, various optical brighteners? i'i Foaming agents, surfactants, polyvinylpyrrolidone, methanol, and other WiS agents can be included, but in particular, as a preservative, JP-A-62
It is preferable to use the sulfinic acid compound described in Japanese Patent No.-143048.

Further, for the purpose of stabilizing the liquid, it is preferable to add an organic phosphonic acid, and in particular, 1-hydroxyethylidene-1,1-diphosphonic acid is effective. The amount of these additions is 0. O1～
0.3 mol/e, preferably 0.05-0.2 mol/1
It is particularly effective in fixing solutions.

The pH of the bleach-fix solution and/or fix solution of the present invention is 9 to 1.
is common, but 7. is preferable as a bleach-fix solution.
5 to 1.5, more preferably 7.0 to 2.0.

The pH of the fixer of the present invention is generally 9.0 to 5.0, particularly preferably 7.5 to 5.5.

The amount of replenishment of the bleach-fixing solution and/or fixing solution of the present invention is 50M+Z to 3000M per 11 photosensitive materials! Preferably 100
-~1000-.

The amount of replenishment of the fixing solution is as follows: 1. (300m per
1 to 3000d is preferred, more preferably 300d
- to 1000+d.

However, the above-mentioned replenishment amount can be reduced to a smaller amount if, for example, a regeneration treatment is performed, such as oxidation regeneration of the processing solution and silver recovery treatment.

The color developer used in the present invention contains a known aromatic primary amine color developing agent.

Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

ρ-IN, N-diethyl-p-)unilenediamine 13-2 2-amino-5-diethylaminotoluene β-32-amino-5-(N-ethyl-N-laurylamino)toluene β-44-(N- Ethyl-N-(β-hydroxyethyl)amino)aniline β-52-methyl-4-(N-ethyl-N-(β-hydroxyethyl)amino)aniline β-64-amino-3-methyl-N=ethyl −N−(β
-(methanesulfonamido)ethyl]-aniline β-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide ρ-8N,N-dimethylnyl-phenylenediamine β-94-amino-3-methyl-N- Ethyl-N-methoxyethylaniline A-104-amino-3-methyl-N-ethyl-N-β
-ethoxyethylaniline β-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, particularly preferred are exemplified compounds β-2, 1s-4, β-5 and β-6.

In addition, these p-phenylenediamine = i-forms may be salts such as sulfate, hydrochloride, gnitrate, p-)luenesulfonate, etc. The usage amount of the aromatic-grade amine developing agent is preferably about 0.1 g to about 20 g per developer solution 11,
More preferred is a concentration of about 0.5g-10g.

In addition, the color developer contains sulfites such as sodium sulfite, potassium sulfite, sodium bigrite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and the carbonyl compound sulfite adduct of the present invention as a preservative. can be added as needed.

The preferable addition amount is 0.5 g to 1.0 g per 11 color developing solutions.
0g, more preferably 1g to 5g.

In addition, as compounds that directly preserve the color developing agent, various hydroxylamines, Japanese Patent Application No. 61-18655
Hydroxamic acids described in No. 9, hydrazines described in No. 61-170756, hydrazines, No. 61-188
Phenols described in No. 742 and No. 61-203253, α-hydroxyketones and α-aminoketones described in No. 61188741, and/or No. 61-180
It is preferable to add various sugars described in No. 616, and
In combination with the above compounds, Japanese Patent Application No. 61-147823,
Monoamines described in No. 61-166674, No. 61-165621, No. 61-164515, No. 61-170789, No. 61-168159, etc.;
No. 1-173595, No. 61-16.4515, No. 6
Diamines described in No. 1-186560, etc., No. 61-1
65621 and polyamines described in 61-169789, polyamines described in 61-188619, nitroxy radicals described in 61-197760, alcohols described in 61-186561 and 61-197419. It is preferable to use the oximes described in Japanese Patent No. 61-198987, and the tertiary amines described in Japanese Patent No. 61-265149.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
Polyethyleneimines described in US Pat. No. 349, US Pat.
If necessary, the aromatic polyhydroxy compound described in No. 746.544 may be contained, and addition of an aromatic polyhydroxy compound is particularly preferred.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use each Enoki buffer.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, 0-
Sodium hydroxybenzoate (sodium satylylate), potassium O-hydroxybenzoate, 5-sulfo-2
Examples include sodium hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/I.
It is preferably t or more, especially 0.1 mol/j! ~
0.4 mol/Ii! It is particularly preferable that

In addition, various chelating agents can be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer.

As the chelating agent, sea-containing compounds are preferred, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids.

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

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N.

N゛, N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1, 2,4-
Tricarboxylic acid, 1-hydroxyethylidene-1,1-
Diphosphonic acid, N,N-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, and two or more of these chelating agents may be used in combination as necessary.

The amount of these chelating agents added may be sufficient as long as the amount is sufficient to sequester metal ions in the color developer. For example, 11
It is about 0.1 g-Log per unit.

Any development accelerator can be added to the color developer if necessary. However, the color developer of the present invention preferably does not substantially contain benzyl alcohol from the viewpoints of pollution, formulation properties, and prevention of color staining. Here, "substantially" means 2. - Hereinafter, it means preferably not containing at all.

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 38-7826, No. 44-
No. 12380, No. 45-9019 and U.S. Patent No. 3.
813,247, p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B-Sho 44-3 '0074 No., JP-A-56-156826 and JP-A No. 52-43429
Quaternary ammonium salts represented by U.S. Patent Nos. 2,494.903, 3,128°182, and 4
, 230,796, 3,253.919, Japanese Patent Publication No. 41-11431, U.S. Pat. No. 2,482.546, 2. 596. No. 926 and No. 3,582.3.
Amine compounds described in No. 46 etc., Japanese Patent Publication No. 37-160
No. 88, No. 42-25201, U.S. Patent No. 3.128
, No. 183, Special Publication No. 41-11431, No. 42-23
Polyalkylene oxides such as those disclosed in No. 883 and US Pat. No. 3,532,501, l-phenyl-3-pyrazolidones, imidazoles, etc. may be added as necessary.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Typical examples include nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention may contain a fluorescent whitening agent. As the fluorescent brightening agent, 4゜4゛-diamino-2,2'-disulfostilbene compounds are preferred. , the amount added is 0 to 5 g/l, preferably 0.1 g to 4 g/l
It is.

Furthermore, various surfactants such as alkylsulfonic acid, phosphonic acid, aliphatic carboxylic acid, aromatic carboxylic acid, etc. may be added as necessary.

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 40°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. The replenishment amount is preferably small, but it is 100 to 1500 layers per photosensitive material, preferably 100 to 800, more preferably 100
-~40 (llR1.

Further, the color developing bath may be divided into two or more baths as necessary, and the color developing replenisher may be replenished from the first bath or the last bath, thereby shortening the developing time and reducing the amount of replenishment.

The processing method of the present invention can also be used for color reversal processing. In the present invention, the black and white developer used at this time is commonly known as the black and white first developer used for the reversal processing of color photographic light-sensitive materials, or Those used for processing black and white photosensitive materials can be used. In addition, various well-known additives that are generally added to black and white developers can be included.

Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, and accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. ,
Examples include inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, and methylbenzothiazole, water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds. be able to.

A processing step, a desilvering step, and a water washing step are performed on the silver halide photosensitive material of the present invention.

As the derailment process, instead of the bleaching process using a bleach solution and the process using a fixing solution, a bleach-fixing process may be performed using a bleach-fixing solution, or a bleaching process, a fixing process, and a bleaching process using a fixing solution may be performed. The fixing treatment steps may be arbitrarily combined.

Examples of the desilvering step of the present invention include, but are not limited to, the following steps.

■ Bleach-fixing ■ Bleach-bleach-fixing ■ Bleach-bleach-fixing ■ Bleach-washing constant-fixing ■ Bleach-constant fixing ■ Bleach-fixing ■ Bleach-fixing - bleach-fixing The color photosensitive material of the present invention is subjected to bleaching treatment or bleaching treatment after color development. Bleach-fixing processing is performed, but these processings may be performed immediately after color development without going through other processing steps, or
In order to prevent unnecessary post-development and air fog, and to reduce the carry-over of color developer into the desilvering process, it is also impregnated into sensitive material components such as sensitizing dyes and dyes contained in photographic light-sensitive materials and in photographic light-sensitive materials. In order to wash out the color developing agent and render it harmless, the color developing agent may be subjected to processing steps such as stopping, adjusting, and washing with water, and then subjected to a bleaching treatment or a bleach-fixing treatment.

Examples of bleaching agents that can be used in bleaching solutions include:
Iron (■), Cobalt (■), Chromium (IV), Copper (■)
Polyvalent metal compounds such as peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (fit), e.g. Aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or citric acid, tartaric acid,
Complex salts such as malic acid; persulfates; bromates; permanganates; nitrohenzenes, etc. can be used. Among these, aminopolycarboxylic acid iron (Ill) complex salts including ethylenediaminetetraacetic acid iron ([[I) complex salts] and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron ([I) complex salts are particularly useful in both bleach and bleach-fix solutions.

In particular, 1M salt of iron(III) 1,3-diaminopropanetetraacetate is preferable from the viewpoint of bleaching ability in the bleaching solution for negative light-sensitive materials for imaging.
I) A bleaching solution using a complex salt can be used at a pH of 2.8 to 6.8.

In addition, the bleaching solution includes chelating agents such as the above-mentioned aminopolycarboxylic acids and aminopolyphosphonic acids that can be contained in the bleach-fixing solution, rehalogenating agents, pH buffering agents, corrosion inhibitors, pH adjusting agents, and bleaching accelerators. It is possible to contain agents such as agents.

In addition, as a replenishment method for the desilvering step, it is common to replenish each processing bath with the corresponding replenisher and discard the overflow liquid as waste. A forward replenishment system or a self-flow replenishment system in which the overflow liquid of the subsequent bath is led to the preceding bath can also be applied. For example, the wash water or overflow liquid of the stabilizing bath can be conducted to a fixing bath or a bleach-fixing bath.

Regarding the total time of the desilvering step of the present invention, the effects of the water-sprinkling invention can be significantly obtained. The preferred time is 1 minute to 10 minutes, more preferably 1 minute to 6 minutes. In addition, the processing temperature is 25℃~
The temperature is 50°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step of the present invention, it is preferable that the stirring be as strong as possible in order to more effectively exhibit the effects of the present invention.

A specific method for strengthening t1 stirring is disclosed in Japanese Patent Application Laid-Open No. 62-1834.
No. 60, No. 62-183461, U.S. Patent No. 4,75
8.858, a method of impinging a jet of processing liquid on the emulsion surface of a light-sensitive material, and JP-A-62-183461.
A method of increasing the 1jlf'l' effect using a rotating means as described in No. 1, and a stirring effect by moving the photosensitive material without bringing the emulsion surface into contact with a wiper blade installed in the liquid to create turbulence on the emulsion surface. Examples include methods of increasing the circulation flow rate of the entire processing liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleaching agent and fixing agent into the emulsion film, and as a result increases the desilvering rate.

Further, the agitation improving means is more effective when a bleach accelerator is used, and can significantly increase the acceleration results and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The automatic developing machine used in the present invention is JP-A-60-191
No. 257, No. 60-191258, No. 60-1912
No. 59, Re5earch DisclosureIt
Em I'h29118 (July 1988), the above-mentioned Japanese Patent Application Laid-Open No. 1983-1970, which preferably has the photosensitive material conveying means described in U.S. Pat. No. 4,758,858,
As described in No. 191257, such a conveying means can significantly reduce the carry-over of the processing liquid from the front bath to the after bath, and is highly effective in preventing deterioration of the performance of the processing liquid.The means described in the above RD is also preferable. , such effects are particularly effective in shortening the processing time in each process and reducing the amount of processing solution replenishment. ・These methods of strengthening stirring are also effective in addition to the desilvering process, and are useful in the water washing process and developing process. It is desirable to apply this method to shorten processing time and reduce the amount of replenishment.

The processing method of the present invention comprises processing steps such as color development, bleaching, bleach-fixing, and fixing as described above.

Here, after the bleach-fixing or fixing process, processing steps such as water washing and stabilization are generally performed, but after a bath with fixing ability, stabilization processing is performed without substantial water washing. A simple treatment method can also be used.

The rinsing water used in the rinsing process may contain known additives as needed; for example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid;
Bactericidal agents and antifungal agents (for example, isothiazolones, organochlorine disinfectants, benzotriazole, etc.) that prevent the growth of various bacteria and algae, surfactants that prevent drying load and unevenness, and the like can be used. Or L, E,
West.

"Water Quality Cr1teria'+
PhoL, Sci, and Eng, +vol1.9.
Na6. Compounds described in Pages 344-359 (1965) and the like can also be used.

As the stabilizing solution used in the stabilization step, a processing solution that stabilizes the dye image is used. For example, a solution having a buffering capacity of pH 3 to 6, a solution containing an aldehyde (for example, gel tar aldehyde), etc. are used. be able to. Formalin is preferable in terms of pollution, and the stabilizing liquid may contain ammonium compounds, metal compounds such as Bi, At', etc. as necessary.
Optical brighteners, chelating agents (for example, EDTA I-hydroxyethylidene-1,1-diphosphonic acid), fungicides, fungicides, hardeners, surfactants, and the like can be used. Thiazolone compounds such as 5-chloro-2-methyl-isothiazolin-3-one and 1°2-benzisothiazolin-3-one are effective as anti-spores.

Further, as the surfactant, a silicone compound represented by the following general formula is preferable because it has an effect of preventing water droplet unevenness and defoaming.

CCHX), -0-fcH1cHo÷T-10CH!
CHt O÷, R where a, b + d s e is 5
An integer of ~30, C is an integer of 2 to 5, or R is an integer of 3 to 5 carbon atoms.
6 alkyl group.

Further, it is preferable to add an alkanolamine to the stabilizing solution in order to prevent sulfurization of thiosulfate ions introduced by the photosensitive material. The use of alkanolamine is described in US Pat. No. 4,786,583.

Also, - For boat fishing, the stabilizing liquid contains formalin.
It is preferable not to use it in the present invention.

The pH of the stabilizer of the present invention is 3-8, preferably 5-7.

The temperature of the stabilizing liquid is preferably 5°C to 45°C, more preferably 10°C to 40°C.

In addition, the water washing step and the stabilization step are preferably carried out in a multi-stage countercurrent system, and the number of stages is preferably 2 to 4. Two or more types of stabilizing solutions may be used in multiple stages, and the replenishment amount is from the pre-bath per unit area. The amount is 1 to 50 times, preferably 2 to 30 times, and more preferably 2 to 15 times the amount brought in.

The effect of the water-sprinkling invention is that the processing time of the water-washing and stabilization steps is short, and from the viewpoint of rapid processing, the total processing time of the water-washing and stabilization steps is preferably 10 to 50 seconds, and the effect is particularly remarkable when the processing time is 10 to 30 seconds.

In addition, the effect of the water-washing invention, which requires only a small amount of replenishment during washing and stabilization processes, is great for photosensitive materials. It is preferably 50 to 400 d, particularly preferably 50 to 200 d.

The water used in these washing steps or stabilization steps includes tap water, as well as Ca
It is preferable to use water that has been deionized to have an Mg concentration of 5.71 or less, water that has been sterilized with halogen, an ultraviolet sterilizing concave lamp, or the like.

In each of the above processing steps for photosensitive materials, when continuous processing is performed using an automatic processor, concentration of the processing solution due to evaporation may occur, especially when the processing amount is small or the opening area of the processing solution is large. becomes. In order to correct 411 of the processing liquid, it is preferable to replenish an appropriate amount of water or correction liquid.

Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid from the water washing step or the stabilization step flows into a pre-bath having a fixing ability.

The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number of layers and the number of non-photosensitive layers, and as a typical example, a plurality of silver halides having substantially the same color sensitivity but different photosensitivity may be formed on the support. Consists of an emulsion layer (
It is a halogenated radical photographic material having at least one 5 photosensitive layer, and the 3g5 photosensitive layer is a unit photosensitive layer sensitive to any of blue light, green light and red light, and is a multilayer photosensitive material. In a silver halide color photographic material, the unit photosensitive layers are generally arranged in the following order from the support: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that different toe-sensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide toe-sensitive layers, the bottom layer, and the bottom layer.

For cough intermediate layer, JP-A-61-43748 and JP-A-59-1
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

The plurality of silver halide emulsion layers constituting each of the toe layers are high-temperature, high-temperature and low-temperature layers, as described in West German Patent No. 1,121,470 or British Patent No. 923.045. A two-layer structure of the milkweed layer can be preferably used0
Usually, it is preferable to arrange the halogen emulsion in a keychain pattern in which the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer.
No. 112751, No. 62200350, No. 62-20
As described in No. 6541, No. 62-206543, etc., a low density emulsion layer may be provided on the side away from the support, and a high density emulsion layer may be provided on the side close to the support.

As a specific example, starting from the farthest side from the support, the following layers are: low-grade blue toe layer (8L) / high-sensitivity blue photosensitive layer (B) I) / high-grade blue photosensitive layer (Gl() / low-grade green toe layer) Geriatric layer (GL)
/High Plague Red Photosensitive Layer 11i (RH) /Low Plague Red Photosensitive Layer (RL), or Bit/BL/GL/G
H/R) I/RL order or 88/8L/GW/GL
/RL/RH, etc.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/R
They can also be arranged in the order of H/GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/RH can be arranged in this order from the farthest side from the support. .

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, a medium-speed emulsion layer/high-speed emulsion layer/low-speed emulsion layer may be arranged in this order from the side remote from the support.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

When the photographic light-sensitive material of the present invention is a color negative film or a color reversal film, preferred silver halide contained in the photographic emulsion layer is silver iodobromide, silver iodobromide, containing about 30 mol% or less of silver iodide. Silver chloride or silver iodochlorobromide. Particularly preferred are silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

When the photographic light-sensitive material of the present invention is a color photographic paper, the silver halide contained in the photographic emulsion layer is composed of silver chlorobromide or silver chloride that does not substantially contain silver iodide. It can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. Regarding the halogen composition of these silver chlorobromide emulsions, Any silver bromide/silver chloride can be used. Although this ratio can vary widely depending on the purpose, those having a silver chloride ratio of 2 mol % or more are preferably used. For light-sensitive materials suitable for rapid processing, so-called high silver chloride emulsions containing a high silver chloride content are preferably used. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more, more preferably 95 mol% or more.For the purpose of reducing the amount of replenishment of the development processing solution, the silver chloride content is 98 to 99.9. Emulsions of approximately pure silver chloride, such as mole percent, are also preferably used.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. It may also be a trapezoid having multiple crystal defects.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (hereinafter referred to as RD) Nα
17643 (December 1978), pp. 22-23″1
．． Emulsion preparation
n and Lypes)'', and the same N(L 1B71
6 (November 1979), 648 pages, "Physics and Chemistry of Photography" by Grafkide, published by Beaumontel (P, G
lafkides, Chemic et Ph1si
que PhoLograph-1que, Paul
Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duff
in, Photographic Emulsion
Chesistry (Focal Press,
1966)), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V.

L, Zelilvan et al, + Makin
g and Coating Photogr-aph
ic Emulsion, Focal Press+
(1964) and others.

U.S. Patent No. 3,574.628, U.S. Patent No. 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering)
, Vol. 14, pp. 248-257 (1970);
U.S. Patent Nos. 4,434,226 and 4,414.31
No. 0, No. 4,433,048, No. 4,439,520
and British Patent No. 2,112.157.

The crystal structure may be -like, the inside and outside may have different halogen compositions, it may be a layered structure, and silver halides of different compositions may be joined by epitaxial bonding. Alternatively, it may be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical sensitization, and spectral sensitization. During the physical ripening process, various polyvalent metal ion impurities (cadmium, zinc,
It is also possible to introduce salts or complex salts of lead, copper, thallium, iron, ruthenium, rhodium, palladium, osmium, iridium, platinum, etc.). Compounds used for chemical sensitization include those described in the lower right column on page 18 to the upper right column on page 22 of the specification of JP-A-62-215272. Additionally, additives used in such processes include RD Nct 17643 and RD Nct N1118716.
The known photographic additives that can be used in the present invention are also listed in the above two RDs, and the relevant parts are summarized in the table below. Indicated.

1 plate 1 Chemical sensitizer 2 Sensitivity enhancer 3 Spectral sensitizer, supersensitizer 4 Brightener 24 pages 5 Anti-fogging agent 24-25 pages 649 right column ~ and stabilizer 6 Light Absorbent, Filter dye, pages 25-26 Page 649 right column - Page 650 left column [uLllLufi Page 23 Page 648 right column Same as above Page 23-24 Page 648 right column - Page 649 right column Ultraviolet absorber Stain inhibitor Page 25 right IKA page 650 left to right column Dye image stabilizer page 25 Hardener page 26 page 651 left column binder page 26 Same as above Plastic agent, lubricant page 27 page 650 right column coating aid,
Pages 26 to 27 Page 650 Right column Surfactant 13 Static 7ri Page 27 Same as above Patch In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 435,503.

Various color couplers can be used in the present invention, and specific examples thereof include the above-mentioned RD Nα [643, ■-C-
It is described in the patent described in G.

As a yellow coupler, for example, U.S. Patent No. 4, 29
No. 6.200, No. 2,369.929, No. 2,801
．． No. 171, No. 2,772,162, No. 2,895,
No. 826, No. 3,772.002, No. 3,758,3
No. 08, No. 4,334,011, No. 4,327゜17
3, West German Patent Publication No. 3.329.729, European Patent No. 121,365A, European Patent No. 249.453A, US Pat. No. 4,451,559, No. 4
, No. 427,767, No. 4.690.889, No. 4,
254. Preferred are those described in No. 212, No. 4,296.199, JP-A-61-42658, and the like.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in Section 1-C of RD Floor 17643, U.S. Pat.
．． 163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929, U.S. Pat. U.S. Pat. No. 4,774.181 describes a coupler that corrects unnecessary absorption of a coloring dye using a fluorescent dye released during coupling, and U.S. Patent No. 4,777
It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye, as described in No. 120, Vol.

3.933.501, 4,022,620, 4
, No. 326.024, No. 4,401,752, No. 4,
No. 248.961, Special Publication Showa 5a-t.

739, British Patent No. 1,425,020, British Patent No. 1,4
Preferably, those described in US Pat. No. 76,760, US Pat. No. 3,973,968, US Pat. No. 4,314,023, US Pat.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0.619, No. 4,351,897, European Patent No. 7
No. 3.636, U.S. Patent No. 3,061,432, No. 3
, No. 725.064, RD Hidden 24220 (June 1984), JP-A No. 60-33552, RD Ritsu 2423
0 (June 1984), Japanese Patent Publication No. 60-43659,
No. 61-72238, No. 60-35730, No. 55
-118034, US Pat. No. 60-185951, US Pat. No. 4.500.630, US Pat. No. 4,540.654, US Pat.
Particularly preferred are those described in No. 95 and the like.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Patent No. 4.052.212.
No. 4,146,396, No. 4,228,233; as a coupler in which the coloring dye has appropriate diffusivity, U.S. Patent No. 4,366,237, British Patent No. 2,1
Preference is given to those described in No. 25,570, European Patent No. 96,570 and German Patent Publication No. 3,234,533.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
It is described in 4°367.282, 4,409,320, 4,576.910, British Patent 2.102.173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD 17643.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
No. 63-37346, U.S. Patent No. 4,248,96
No. 2, No. 4°782.012 is preferred.

As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2.097.140;
Those described in JP-A No. 2,131,188, JP-A-59-157638, and JP-A-59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130.427, U.S. Pat. 4,310.618, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR couplers described in JP-A-60-185950, JP-A-62-24252, etc.
R-Coupler-Releasing Redox Compound, European Patent No. 173. 30
RDNα11449, RDNα11449, RDNα11449, RDNα11449, RDNα11449, RDNα11449, RDNα11449, RDNα11449, RDNα11449, RDNα11449, RDNα11449, RDNα11449, RDNα11449, RDNα11449, RDNα2424+, JP-A-61.2
Bleach accelerator releasing couplers described in US Pat. No. 01247, Gantt releasing couplers described in US Pat. , 774.181, etc., which emit a fluorescent dye.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high-boiling point solvents used in the oil-in-water dispersion method are described in U.S. Patent No. 2,322.027, etc.; Specific examples of boiling point organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl tslate,
Di-2-ethylhexyl tucrate, decyl phthalate, bis(2,4-di-amylphenyl) phthalate,
bis(2,4-di-t-amyl phenyl) isophthalate, bis(1,1-noethylprobyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl) Phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tryptoquine ethyl phosphate, trichloropropyl phosphate, di-2
-ethylhexyl phenylphosphonate, etc.), ammonium, se, folic acid esters (2. ethylhexylbenzoate,
dodecylbenzoate, 2-ethylhexyl p-hydroxybenzoate, etc.), amide i (N,N-diethyldodecaneamide, N.N-diethyllaurylamide,
N. alcohols or phenols (isostearyl alcohol, 2,4-
(di-LerL-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N- dibutyl-2-butoxy-5-terL-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like.

As the auxiliary solvent, a solvent having a boiling point of about 30"C or more, preferably about 50"C or more and about 160"C or less can be used. Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, Examples include cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

The process and effects of latex dispersion and specific examples of latex for impregnation are described in US Pat. No. 4,199,363 and West German Patent No. 1! Jl (OLS) Nos. 2.541.274 and 2,541.

It is described in No. 230, etc.

These couplers can also be impregnated into rhodapulu latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling solvents described above.
Alternatively, it can be dissolved in a water-insoluble but organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO88100723 are used, and the use of acrylamide polymers is particularly preferred from the viewpoint of color image stabilization.

The present invention can be applied to various color photosensitive materials☆IP
S-0 general or movie color negative film,
Typical examples include color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, Nα17643, page 28, and same page 18716, 6
It is described from the right column on page 47 to the left column on page 648.

In the photosensitive material of the present invention, the total film thickness of the entire aqueous colloid layer on the side having the emulsion layer is preferably 28 #ll or less, and the film swelling rate T178 is preferably 30 seconds or less.
Denotes the film thickness measured at a relative temperature of 55°C (2 days), film swelling rate T, 7. can be measured according to techniques known in the art. For example, as described in Photographic Science and Engineering by AJreen et al.
ogr, Sci, Eng,), Volume 19, Issue 2, 12
It can be measured by using a swellometer (swelling membrane) of the type described on pages 4 to 129, and T I/2 can be measured using a color developer.
Maximum swelling gt reached when treated at 0°C for 13 minutes and 15 seconds
90% of the thickness is defined as the saturated film thickness, and is defined as the time required to reach the film thickness A.

Membrane swelling rate T, 7! can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. In addition, the swelling rate is preferably 150 to 400%, and the swelling rate refers to the maximum swelling under the conditions mentioned above. r+! From the film thickness, the formula: (maximum swelling film thickness - film thickness)/II! It can be calculated according to J thickness.

(Examples) The present invention will be explained in more detail below using Examples, but the present invention is not limited thereto.

Example 1 Back layer contains cellulose noacetate and low boiling point R/8
An E cellulose acetate film prepared by the manufacturing method described in JP-A-62-115035, which is undercoated with a dispersion of silica and methyl methacrylate/todenyl methacrylate copolymer using a solvent. on the support,
Sample 101, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(!!!, composition of the optical layer) The coating weight is for silver halides and colloidal silver in g/r+ of silver, and for coupler additives and gelatin in g/rrr. and sensitizing dyes are shown in moles per mole of silver halide in the same layer.The symbols indicating additives have the meanings shown below.However, if they have multiple effects, one of them I have posted this as a representative.

Uv; ultraviolet absorber, 5olvH high boiling point organic solvent, Ex
F: dye, ExS H sensitizing dye, ExC: uncoupler, ExM: magenta coupler ExY: yellow coupler, Cpd, additive 1st layer (antihalation layer) black colloidal primate 0.15 gelatin 2.9UV-10, 03 UV-20,06 UV-30,07 Solv-20,08 ExF-10,01 ExF-20,01 2nd layer (low red blush emulsion layer) Silver iodobromide emulsion (Ag 14 mol%, uniform Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 37%, plate-like particles,
Diameter/thickness ratio 3.0) Coated silver amount 0.4 Gelatin 0.8ExS-12
,3X10-'ExS-21,4X10-'ExS-52,3xl(1'ExS-78,0xlO-' ExC-30,13 3rd layer (mid-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol %, internal Agl type with a core-shell ratio of 2:1, equivalent sphere diameter 0.65 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter/thickness ratio 2.0) Coated silver amount 0.65 Iodobromide Silver emulsion (Ag 14 mol%, uniform-Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 37%, plate-like particles,
Diameter/thickness ratio 3.0) Coated silver amount 0. 1 Gelatin 1.0ExS-I ExS-2 ExS-5 ExS-7 2X10-' i, zxto-'2X10-'7X10-" ExC-20,01 ExC-30,06 4th Stone (High Level Red Angry Milk Rule) Layer) Silver iodobromide emulsion (Ag 16 mol%, internal high Agl type with core-shell ratio 2:l, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 2.5) ) Coated silver amount 0.9 0.8 1.6X10-'1.6X10-'1.6X10-'6X10-' 0,07 0,05 Gelatin ExS-I ExS-2 ExS-5 ExS-7 ExC-I ExC-4 Solv-10,07 Solv-20,20 Cpd-74,6X10-' 5th layer (middle layer) Gelatin 0.6UV-4Q,
Q3 tJV-50,04 Cpd-10・1 Polyethyl acrylate Latex 0.08Solv-1
0,O5 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag 14 mol%, uniform-Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 37%, plate-like grains,
Diameter/thickness ratio 2.0) Coated silver it 0.18 Gelatin 0.4ExS-32
X10-'ExS-47xto-'ExS-5txto-' xM-5 xM-7 xY-8 o1v-1 Solv-4 7th layer (medium pestilence green emulsion layer) Silver iodobromide emulsion (Ag [4 mol% , surface height Agl type with core-shell ratio tit, equivalent sphere diameter 0.5 μm, coefficient of variation of equivalent sphere diameter 20%, plate-shaped particles, diameter/thickness ratio 4.0) Coated silver amount 0, 27 0.6 2X10-' 7 8th layer (high sensitivity green emulsion layer) Silver iodobromide emulsion (Ag 18.7 mol%, silver ratio 3:4:2
Multi-layer structured particles, Ag+ content of 24 mol, 0 mol, 3 mol% from the inside, equivalent sphere diameter 0.7 μm, coefficient of variation of 1 sphere equivalent diameter 25%, plate-shaped particles, diameter/thickness ratio 1.6) Coated silver amount 0.7 0.8 5.2X10-'lXl0-'0.3xlO-' 0.1 0, 03 0, 02 0, 02 0, OI Ol 25 0, 06 0, 01 1 X 10-' Gelatin ExS- 4 ExS-5 ExS-8 xM-5 xM-6 xY-8 XC-I ExC-4 Solv-I Solv-2 Solv-4 pd-7 9th Old (Intermediate N) Gelatin 0.6cpd-t
o, 04 Polyethyl acrylate Latex 0.12Solv-1
0,02 10th layer (donor layer for interlayer effect on the Red Angry layer) Silver iodobromide emulsion (Ag + 6 mol%, internal high Agl type with core nonyl ratio 2:l, equivalent sphere diameter 0.7 μm, variation in equivalent sphere diameter) coefficient 2
5%, plate-like grains, diameter/intensity ratio 2.0) Coating amount 0, 68 Silver iodobromide emulsion (Ag 14 mol%, uniform Agl type, equivalent sphere diameter 0.4 μm, variation in equivalent sphere diameter Coefficient 37%, plate-shaped particles,
Diameter/thickness ratio 3. O) Coated silver i1 0.19 Gelatin 1.0ExS-36x
to-' ExM-100,19 Solv-10,20 1st I layer (yellow filter layer) Yellow colloidal silver 0.06 gelatin 0.8Cpd-20,13 Solv-10,13 Cpd-10-07 cpd-6o, 002 H-10,13 12th layer (low-frequency front window emulsion layer) Silver iodobromide emulsion (Ag+4.5 mol%, uniform-Agl type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 15%, Platy grains, diameter/thickness ratio 7.0) Coated silver i10.3 Silver iodobromide emulsion (Ag+3 mol%, uniform-Agl type, equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 30%, plate shape particle,
Diameter/yL ratio 7.0) Application line 1 0.15 Gelatin 1.8ExS-69
xlO-' ExC-10,06 xC-4 xY-9 0,03 0,l 4 13th layer (middle N) Gelatin 0.7ExY-12
0,20 Solv-10,34 14th layer (highly blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag 110 mol%, internal high AgI type, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 25%, Multiple twinned plate-like particles, diameter/thickness ratio 2.0) Coated silver amount
0.5 gelatin 0.5Ex
S-6txxo-' ExY-90,01 Solv-1 0,11 15th layer (first protective layer) Fine grain silver iodobromide emulsion (Ag + 2 mol%, homogeneous-Agl type,
Equivalent sphere diameter 0.07μm) Coated silver amount 0.12 Gelatin 0.9UV-40,
11 UV-50,16 Solv-50,02 ) (-10,13 Cpd-50,10 Polyethyl acrylate Latex 0.09 16th layer (2nd protection ff1N) Fine grain silver iodobromide emulsion (AgT2 mol%, Uniform-Agl type,
Equivalent ball diameter 0.07. cam) Coated silver amount 0.36 Gelatin 0.55 Polymethyl methacrylate particles (1.5 μm in diameter) 0.2) (-10
, 17 In addition to the above components, emulsion stabilizer Cpd-3 (0°07g/m) and surfactant Cp V-4-4 (0°03g/m) were added as coating aids to each layer. .

V ! H x:y-70:30 (wt%) V-5 (tic-He V-2 H olv-1 tricresyl phosphate olv-2 Diptyl phthalate (t)CaL olv-4 V H (t)CoH9 o1v-5 trihexyl phosphate ExF-1 xS-1 N(CJs)z ExF-’1 xS-4 N　(C*Hs)　z EXS-6 EXS-7 xC-3 H OCHzClhO xC-4 H (i)CJqOCONH OCHzCHzSCHzC(hH xC-1 H xC2 H XC-13 H xY 4 CI! EXM-5 ExM xY-8 xY-9 xY-11 C, Fl.

CH.

ExM-7 ExM-10 xY-12 pd-7 CH 1 CuI2 thHI3 (pd 2 pd-6 pd-5 pd-3 CH.

-1 fjl□-Ctl Sow C1h C0NH-
CtltCI+□-++CII 5Ch-C1h
C0Nfl-(Jlt made these samples $4101 is 3
Cut and process into 5mm width, leaving one sample unexposed.
In another trial 4, the exposure amount was adjusted to give 4 degrees of gray and 1 degree of 2.0, and an automatic developing machine was used with the processing steps and processing solution composition shown below. T:
The treatment was carried out in an amount of 1. However, the samples to be evaluated for performance were processed after Trial 4 in which imagewise n-light was applied until the cumulative replenishment and withdrawal of the color developer reached three times the capacity of the mother liquor tank.

Processing process Processing time Processing temperature Color development 3 minutes 15 seconds 37.8! bleaching
40 seconds 38.0℃ Refill amount° Tank capacity 237 10RI 5-51 Young 1 minute 30 seconds 38.0℃ 3QaZ
lOj'(1) 30 seconds 38.0℃
51 (30d at 2130 seconds 38.0
51 constant 30 seconds 38.0℃
20d! M'dry 1 second 5
5°C They were 2.5 to 12.0 - per meter of length of photosensitive material in width.

Further, the crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

The contact area between the treatment liquid and air in each treatment tank was 50M.

The composition of the treatment liquid is shown below.

(Color developer) Mother solution (8) Replenisher (g
) Diethylenediaminepentaacetic acid 1.0 1.11-Hydroxyethyl Washed with constant water Washed with water and dried Ten-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-[N-Ethyl-N -β-Hydroxyethylamino]-2- Add methylaniline sulfate and H (bleaching solution) 1.3-diaminopropanetetraacetic acid ferric ammonium hydrate 3.0 4.0 30.0 1.4 1 .5■ 3.2 4゜9 30.0 2.4 3.6 4.5 6.4 1.0f 10.05 1.0! 10.10 Mother liquor (g) Replenisher solution (g) (1,3-DPTA Fe (Ill)) 1.3-Diaminopropanetetraacetic acid Ammonium bromide Ammonium nitrate Acetic acid (98%) Add water and pl ((Ammonia water ( (27%) (Constant?7 liquid) Add ethylenediaminetetraacid niummonium salt preservative ammonium 1000 sulfate ammonium sulfite nitrate FII silver water H 144,0 2,8 84,0 90,0 63,0 1, Oe 4.0 Mother liquor (g) 206.0 4.0 +20.0 125.0 90.0 1.01! 3.2 Replenisher (g) 1.7 See Table 1 2.0 mol 0. 3 mol Refer to Table 1 f 7.0 1.7 2.0 mol 0.3 mol Same as on the left 1 7.0 (Washing water) Mother liquor, replenisher common tap water to FI type strongly acidic cation exchange resin (Rohm and Haas Co., Ltd.) Amberlite IR-120B) and OH type strong basic anion exchange resin (Amberlite rRA-
Water is passed through a mixed bed column packed with 400) to reduce calcium and magnesium ions to 3/l or less,
Subsequently, 20 μ/l of sodium isocyanurate dichloride and 150 μ/l of sodium sulfate were added.

1)11 of this liquid was in the range of 6.5-7.5.

(Stable liquid) Both mother liquid and replenisher iJ! ! (Unit: g
) Formalin (37%) 1.2d Surfactant 0.4 (C1oll
t10 + CHtCHtO → -1゜■] Ethylene glycol 1.0 Add water
1.01 pH 5.0-7.0 The silver ion concentration in the fixer at the start and end of continuous processing was converted into nitrate flI silver and measured by X-ray fluorescence analysis. In addition, unexposed samples were processed and stored under the following conditions, and the magenta image density before storage and the magenta image density after storage were measured and the magentastins were compared. The results obtained are shown in Table 1.

Storage conditions: 60°C, 70% RH, 35 days Magentastin (△DG) = (Magenta image density before storage) - (Magenta image density after storage Upon checking, no precipitate was observed in any of the solutions, and it was confirmed that the stability of the solutions due to silver ions had not decreased.

Example 2 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support which was laminated on both sides with polyethylene and coated with colloidal silica and colloidal alumina on the bank surface. The coating solution was prepared as follows.

Preparation of Coating Solution for Layer-20-Coupler (ExY) 19.1g and color image stabilizer (Cpd-H4, 4g and color image stabilizer (Cpd-7>
0.7g to 27.2cc of ethyl acetate and solvent (Sol
v-3) Add and dissolve 8.2 g, and add this solution to 10% sodium dodecylbenzenesulfonate containing 13 cc.
0% gelatin water? '8'/11185cc was emulsified and dispersed. On the other hand, silver chlorobromide emulsion (cubic average grain size 0.8
8μ, particle size distribution coefficient of variation 0.08, silver bromide 0.2
(containing mol % on the grain surface), the following blue-sensitizing jS dyes were added in an amount of 2.0 x 10-' mol per mol of silver, and then sulfur sensitized! Made by PI. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-5-) riazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue sensitive emulsion layer Green sensitive emulsion layer (Halogenation!! 4゜ per mole oxto-’mol) and 5 (h SOJ-N(CJs)3 (7° per mole of halogenated 0XIO″5 moles) red sensitive emulsion layer C□H,1 C,H.

(0.9XIO-' mol per 1 mol of silver halide)
2.6 x 10-'' moles were added per mole.

In addition, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the pre-malignant emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer at 8.5×10°5 mol and 7.7×to per mole of halogenated primate, respectively. -'Mole, 2.5
X10-' moles were added.

The following dyes were added to the emulsion layer to prevent irradiation.

SO7 and SO3 (Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/d). Silver halide emulsions represent the coating amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiO□) and a bluish dye (ulmarine blue)] -th layer (front window layer) Silver chlorobromide emulsion (the above emulsion) 0.30 gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1
) 0.19 Solvent (Solv-3)
0.35 color image stabilizer (Cpd-7)
0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Solv-1
) 0.16 Solvent (Solv-4)
0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (l:3 mixture (Ag mole ratio) of one with a cubic average grain size of 0.55μ and one with a cubic average grain size of 0.39μ) 0
Coefficient of variation of particle size distribution 0.10.0.08 each, Ag
(0.8 mol% of Br was locally contained on the particle surface) 0, 12 Gelatin 1.24 Magenta coupler (ExM) 0, 24 Color image stabilizer (Cpd-3) o, 15 Color image stabilizer (Cpd-8 ) 0.02 color image stabilizer (Cp
d-9) 0.03 solvent (Solv-2)
0.46 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (LIV-1) 0.47 Color mixture prevention agent (C
pd-5) 0.05 solvent (Solv-5)
0.24 Fifth N (red anger layer) Silver chlorobromide emulsion (1=4 mixture of cubic average grain size 0.58 μ and 0.45 μ (Ag molar ratio) 0 Coefficient of variation of grain size distribution each 0,09.0.11,ΔgB
ro, 6 mol% was locally contained in a part of the particle surface)0
．． 23 1.34 0.32 0.17 0.04 0.40 0.15 Gelatin cyan coupler (Ex C) Color image stabilizer (Cpd-6) Color image stabilizer (Cpd-1o) Color image stabilizer ( Cpd-7) 2 medium (Solv-6) 6th N (ultraviolet absorption layer) Gelatin 0, 53 Ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-5) 8 medium (Solv-5) 7th Layer (protective layer) Acrylic modified copolymer of gelatin polyvinyl alcohol (degree of modification 17%) Liquid paraffin (Ex Y) Yellow coupler 902 0, 03 (ExM) Magenta coupler (Cpd-1) Color image stabilizer (Cpd- 3) Color image stabilizer (E x C) Cyan coupler l 0) R= CzHs C4H? (Cpd-5) A 2:4:4 mixture by weight of color mixing inhibitor H I (Cpd-6) A 2:4:4 mixture of color image stabilizer c4H9(t) c, Hv(t) (weight ratio ) (UV-1) Ultraviolet absorber, (t) Cod9 (t) CeH* (t) 4:4 mixture (weight ratio) (Solv-1) Solvent (Cpd-7) Color image stabilizer 1,000 H1-CH+-.

C0NHC, Hq(t) average molecular weight 00 (Cpd-8) Color image stabilizer ((pd-9) color image stabilizer ((:pd-10) Color image stabilizer H (Solv-2) Solvent 2: l mixture (capacity ratio) (SOIV 3) Solvent 0=P+OCwH+v(iso))i (3o1v-4) solvent (3o1v-5) solvent C00CIHI? (CHri 1 C00CsH+.

(Solv-5) Solvent The prepared sample is referred to as sample 201.

The sample 201 prepared above was cut and processed, exposed to image Jffii light, and then processed using a paper processing machine.
After performing continuous processing (running test) until three times the color development tank capacity is replenished in the following processing steps,
One part of the sample was left unexposed, and the other sample was uniformly exposed by adjusting the exposure amount so that the gray density was 2.0.

Shuko LL Ken i skin color development 38℃ bleach fixing 35℃ rinse ■ 35℃ rinse ■ 35℃ Mugu 11 17' 71 O1 o1 109 30 seconds 364d lO
A Drying 80℃ 60 seconds *The amount of replenishment is per 1% of the toe material *The bleach-fixing solution contains bleach-fixing replenisher and rinse solution (1
21d) is replenished.

The contact area between the air and the treatment liquid in each treatment tank was 170cj.

The composition of each treatment liquid is as follows.

water Ethylenediamine-N.

N, N, N-tetramethylenephosphonic acid triethanolamine potassium chloride potassium bromide potassium carbonate hydrazinoniacetic acid 00- 80〇- 3,0g 5.0g 3,1g 0.015g 5g 5.0g 3.0g 5. 0g 5g 7.0g N-Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline ) Ammonium hydrothiosulfate Ammonium sulfite preservative (Table 2) Iron(III) ethylenediaminetetratate Ammonium ethylenediamine quadruplicate 5.0g 1.0g 000m 10.05 600+d 0.5 mol 0.2 mol 0.2 5g mole 9.5g 2.5g 000w 10.60 150- 2,0 mole 0.5 mole 0.5 mole 35g 611 3.0g 8.
0g ammonium bromide 30g 75
g Nitric acid (67%) 27g 68
g Silver nitrate (see Table 2) Add water
1000m 100kpH5,50
5,20-Moxibustion (tank solution and replenisher are the same) Ion-exchanged water (calcium, magnesium each 3 ppm or less) Unexposed samples were treated in the same manner as in Example 1, and magentastin was compared. The results obtained are shown in Table 2.

At the end of the continuous processing, all of the bleach-fix solutions of 1K11 to 1K20 had a silver ion gamma ratio of 0.02 mol/l, giving good results with little magentastin. In Example 2 as well, good results were obtained by the treatment method of the present invention.

(Effects of the Invention) According to the present invention, it is possible to process a silver halide color photographic light-sensitive material that has excellent stability of a processing solution that improves fixing ability and has excellent image storage stability.

Claims (1)

[Scope of Claims] A processing method comprising a step of treating an imagewise exposed silver halide photographic light-sensitive material with a processing liquid having fixing ability, wherein the processing liquid having fixing ability comprises at least the following (1) to
(3) A method for processing a silver halide photographic material, characterized by having the composition. (1) thiosulfate as a fixing agent, (2) silver ions at a concentration of 0.005 to 0.1 times the fixing agent concentration, (3) at least one bisulfite-addable compound and/or at least an adduct of one of said bisulfite-addable compounds and bisulfite;