JPH03210556A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain excellent image stability by incorporating a specific yellow coupler into the photosensitive material and incorporating a preservative such as bisulfite adduct of the compd. which enables addition with a bisulfite to a processing liquid having fixability. CONSTITUTION:The yellow coupler expressed by formula I is incorporated into the photosensitive material in the case of color development processing after imagewise exposing then processing with the processing liquid having the fixability and the compd. selected from a thiosulfate, the bisulfite adduct of the compd. which enable addition with the bisulfite and/or the compd. which enables addition with the bisulfite and the bisulfite, sulfite or metabisulfite are incorporated into the processing liquid having the fixability. In the formula I, R<1> denotes a tertiary alkyl group or aryl group. R<2> denotes a halogen atom or alkoxy group; R<3> denotes an alkyl group or aryl group; Y<1> denotes a bivalent combination group; X denotes a coupling elimination group. The color images with which yellow stains are less generated and have the excellent image stability are obtd. in this way.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and in particular to a method for processing a silver halide color photographic light-sensitive material that yields an image with improved image storage stability. Regarding the method.

[Conventional technology]

There are two types of photographic processing: color development processing and black-and-white development processing, but basically it consists of a process of development, silver removal, and water washing.Specifically, the desilvering process in color development processing involves bleaching. It consists of constant fixing, bleach-fixing, bleach-bleach-fixing, and bleach-bleach-fixing constant fixing. For bleaching, ED
A bleaching solution containing organic acid ferric salts such as TA4e (DI), chelating agents such as EDTA, bromide salts such as NH, Br, etc. is used for fixing.
thiosulfates like zos, preservatives like sulfites,
A fixing solution containing a chelating agent, etc. has been used, and a bleach-fixing solution containing an organic acid ferric salt, a thiosulfate, a preservative, a chelating agent, etc. has been used for bleach-fixing. As described above, in bleach-fixing solutions and fixing solutions, the aforementioned sulfites, bisulfites, and metabisulfates have conventionally been used as decomposition inhibitors of thiosulfate, which is a fixing agent, or as preservatives.

The above-mentioned thiosulfate has the property of being very stable in the presence of sulfite and the like. However, these sulfites are easily oxidized by oxygen in the air or by the bleaching agent in the bleach-fixing solution, and are particularly susceptible to oxidation in the bleach-fixing solution due to the coexistence of organic acid ferric complexes, which are oxidizing bleaches. easy. In addition, EDTiFe, which has a weak oxidizing power, is used in both fixing and bleaching solutions.
When (III) is used, there is little effect, but when 1,3-PDTA, which has recently been used, is used, it has a strong oxidizing power, so it adheres to photosensitive materials and is carried over. The bleaching solution will cause oxidation to proceed.

When sulfites and the like are decomposed and consumed by oxidation, the thiosulfates in each of the above-mentioned treatment solutions are decomposed, and silver salts are present as silver ions in the solutions. Silver sulfide is likely to be formed with the sulfur produced by decomposition, and silver sulfide or sulfur is likely to precipitate. These particles exist in the liquid as fine particles, which cause staining on the photosensitive material. Furthermore, consumption of bleach and decomposition of thiosulfate, which is a fixing agent, causes deterioration in desilvering performance. Therefore, it has been desired to develop a more stable thiosulfate decomposition inhibitor.

Carbonyl bisulfite adducts have attracted attention as such stable thiosulfate decomposition inhibitors, and patent applications have been filed for carbonyl bisulfite adducts (Japanese Patent Application Laid-Open No. 48-488).
No. 2733, No. 50-51326, No. 5610724
No. 4, Japanese Patent Application Publication No. 1-267540, West German Patent No. 21027
No. 13).

The carbonyl bisulfite adduct partially dissociates in the solution, releasing the carbonyl compound and bisulfite ion, which are in an equilibrium relationship and have a small dissociation constant, so the minimum amount necessary to prevent the decomposition of thiosulfate is In addition to maintaining the maximum concentration of sulfite (bisulfite), even if sulfite is oxidized and consumed, it is replenished through an equilibrium relationship, so that concentration is always maintained, and the apparent sulfite concentration is low. In addition, since the decomposition rate is lower than when sulfite is added alone, the decomposition prevention effect of thiosulfate lasts for a long time. This adduct itself is also resistant to oxidation by oxygen in the air and bleaching agents.

In addition, when a carbonyl bisulfite adduct is used as a preservative in a bleach-fix solution, the reaction between the bleach and sulfite is less likely to occur, so the bleach is not consumed, the desilvering property is improved, and The reduced form of bleach (Fe(I) produced by the reaction
There is an advantage that I)) is less likely to accumulate in the bleach-fixing solution, and the bleaching ability and color recovery properties are improved.

[Problem to be solved by the invention]

The use of carbonyl bisulfite adducts has the above-mentioned advantages, but when processing is actually performed with a bleach-fix solution or fixer solution containing this adduct as a preservative,
There are problems such as staining (minimum image density becomes higher on average) in processed photosensitive materials due to several reasons.

The color of stain that occurs varies depending on the cause. One of the causes of staining is that stains mainly in magenta are formed due to poor washing out of the developing agent incorporated into the photosensitive material during the development process. Since the free sulfite concentration in the bleach-fix solution or fixer solution is lower, the developing agent incorporated into the photosensitive material reacts with the sulfite in the bleach-fix solution or fixer solution, increasing its solubility and preventing washing. This is believed to be due to a decrease in the effect exerted, and this developing agent develops color non-imagewise during or after processing, forming stains. Another cause of staining is the formation of magenta-based stains due to a decrease in the washing out of dyes (filter dyes) and sensitizing dyes contained in photosensitive materials, which is also caused by bleaching. This is believed to be because the concentration of free sulfite in the fixing agent or fixing solution decreases, resulting in a decrease in the washing out of the dye and the like from the photosensitive material.

Furthermore, there is a problem in that compounds that can effectively act as carbonyl compounds used in this adduct are limited. This is because the preservation effect when using this adduct is determined by the delicate equilibrium relationship described above, so only carbonyl compounds that have a specific equilibrium constant in the processing solution can be used as the adduct. For example, when using an adduct of a volatile carbonyl compound, the equilibrium shifts to the right as the carbonyl compound evaporates, and the preservative effect does not last long. The product has a terrible odor and is not suitable for practical use.

In addition, some carbonyl compounds are carcinogenic and are therefore unsuitable for practical use due to safety concerns.

Due to the problems listed above, carbonyl bisulfite adducts have not been put into practical use, and a solution to these problems is desired.

The present invention provides a method for color-developing a silver halide color photographic light-sensitive material after imagewise exposure and processing it with a processing solution having a fixing ability containing an adduct such as a carbonyl bisulfite adduct. It is an object of the present invention to provide a method for processing a silver halide color photographic light-sensitive material, which has sufficient advantages of stabilization of thiosulfate based on thiosulfate and which does not cause the above-mentioned problems.

[Means to solve the problem]

The present invention provides a method for processing a silver halide color photographic material, which comprises imagewise exposure, color development, and treatment with a processing solution having fixing ability.
The silver halide color photographic light-sensitive material has the following general formula (I):
A processing solution containing at least one yellow coupler represented by the formula and having the fixing ability contains thiosulfate and at least one bisulfite adduct of a compound that can be added to bisulfite and/or at least one yellow coupler. At least one compound selected from bisulfite, sulfite, or metabisulfite is achieved.

General Formula (I) In the formula, ill represents a tertiary halogen atom or an aryl group.

R2 represents a tertiary alkyl group or an aryl group.

R3 represents a halogen atom or an aryl group.

The Y plate represents a divalent linking group.

X represents a Karapringmi m group.

The yellow coupler represented by the general formula (I) is already known (for example, in JP-A-52-115219
It is known that photosensitive materials using this coupler can reduce the amount of coated silver, have better sharpness, can be processed quickly, and have good stability. The yellow dye produced by the color developing agent and the color developing agent has the drawback of being weak in implicit color fading and photofading.

In order to improve image storage stability, several measures have been proposed to prevent fading, and British Patent No. 1.
No. 326,889 discloses the use of a certain kind of anti-fading agent, and JP-A No. 63-313155 discloses that fading can be prevented by increasing the amount of washing water and washing thoroughly. However, these methods were not sufficiently effective.

However, in the present invention, excellent image stability can be obtained by combining the yellow coupler represented by the general formula (I) with a preservative such as a bisulfite adduct of a compound that can be added to bisulfite. This is what we discovered.

This yellow coupler represented by general formula (I) has never been combined with a processing solution having a fixing ability using a preservative such as the above-mentioned bisulfite adduct, and the above objective has not been achieved. This combination is not known to have such an effect and is not suggested in the prior art.

The preservative added to the processing solution having fixing ability is not limited to the carbonyl bisulfite adduct mentioned in the prior art section, but a wide range of bisulfites can be used to achieve the purpose. In addition to the use of bisulfite adducts of addable compounds, it is also possible to use bisulfites, addable compounds and compounds selected from bisulfites, sulfites or metabisulfites. This latter combination can easily combine with the former bisulfite in a processing solution having fixing ability to form a bisulfite adduct of the addable compound, thereby achieving the object of the present invention. .

This bisulfite adduct of a compound that can be added to bisulfite is partially dissociated in the treatment solution and is in an equilibrium state, but the minimum amount of sulfite ion necessary to prevent the decomposition of thiosulfate is The same applies to the latter combination, which preferably has an equilibrium constant that can maintain a sufficient concentration and prevent the ion concentration from becoming unnecessarily large in order to maintain its maintenance effect over a long period of time. I can say that.

The former bisulfite adduct and the latter combination may be used in combination.

The present invention will be explained in more detail below.

First, the yellow coupler represented by the general formula (I) used in the present invention will be described in detail.

In the general formula (I), the tertiary halogen atom represented by R1 includes unsubstituted (e.g. t-butyl group) and substituted halogen atoms. As the substituent introduced into the halogen atom, halogen atoms (e.g. , fluorine, chlorine,
bromine, etc.), alkoxy groups (e.g. methoxy, ethoxy groups, etc.), aryloxy groups (e.g. phenoxy group, 4
-chlorophenoxy group, etc.), alkylthio group (e.g., methylthio, n-butylthio group, etc.), arylthio group (e.g., phenylthio group, etc.), alkylsulfonyl group (e.g., benzenesulfonyl group, 4-methoxyhenzenesulfonyl group, etc.), Acylamino group (e.g. acetylamino group), amino group (e.g. diethylamino group)
Examples include cyano group. The aryl group represented by R1 is preferably a phenyl group, and may have a substituent. Examples of the substituent for the aryl group include the same groups as halogen atoms, but also halogen atoms (eg, methyl, ethyl, t-butyl groups, etc.).

R1 represents a chlorine atom or an alkoxy group (eg, methoxy, ethoxy, etc.).

The halogen atom represented by R3 includes unsubstituted (for example, n-octyl group, n-dodecyl group, n-heptadecyl group, etc.) and substituted halogen atoms, and the substituents introduced into the halogen atom include those represented by R1. Examples include substituents.

The aryl group represented by R3 is preferably a phenyl group, including unsubstituted and substituted phenyl groups.

Examples of the substituent to be introduced into the phenyl group include the same groups as halogen atoms, and other examples include halogen atoms (eg, methyl, ethyl groups, etc.).

Yl represents a divalent linking group, and represents an alkylene group, an arylene group, an aralxine group, or a divalent organic group represented by the following general formula (I-a).

-A-V-B-General formula (T-a) (wherein A and B are an alkylene group, an arylene group, or an aralkylene group, each of which may have a substituent,
represents a divalent crosslinking group,) the substituents of A and B are lI
The same groups as in the case of are mentioned. Examples of (2) include oxy, thio, carboxide, and sulfonamide groups.

The coupling-off group of X is a coupling-off group forming a 2-equivalent yellow coupler, for example, the following general formula (a),
) or (C).

(a) (b) (wherein 714 IS is a hydrogen atom, a halogen atom, a carboxylic acid ester group, an amino group, a halogen atom,
Represents an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, an unsubstituted or substituted phenyl group, or a heterocycle, and these groups may be the same or different.) Ring, 5-membered It represents a nonmetallic atom required to form a ring or a 6-membered ring.) It is more preferably represented by the following formulas (b) to (f).

111v In the formula, R19 and R1 are each a hydrogen atom, a halogen atom,
R1+, H** and RIm each represent a hydrogen atom, a halogen atom, an aryl group, an aracyl group, or an acyl group; -8 represents an oxygen or sulfur atom; represent

Next, specific examples of couplers used in the present invention will be listed, but the couplers of the present invention are not limited to these.

X "The yellow coupler compound represented by the general formula (I) is
It can be synthesized according to the description in Japanese Patent Publication No. 56-44420.

The yellow coupler represented by the general formula (I) may be used in combination of two or more or with other yellow couplers. When the coupler of the present invention is used in combination with other couplers, it is preferable among the yellow couplers. It is 30 mol% or more, more preferably 80 mol% or more.

As the yellow coupler that may be used in combination, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used in combination are U.S. Pat. Nos. 2,875,057 and 3,265,50.
No. 6, No. 3,408.194, No. 3,551,155
No. 3,582.322, No. 3.725.072, No. 3,891,445, West German Patent No. 1,547,86
No. 8, West German Application No. 2,219,917, No. 2,26
No. 1,361, No. 2,414,006, British Patent 1.
425.020, JP 51-10783, JP 47-26133, JP 4B-73147, JP 51-
No. 102636, No. 50-634.1, No. 50-12
No. 3342, No. 50-130442, No. 51-218
No. 27, No. 50-87650, No. 52-82424, No. 52-115219, etc.

The content of the yellow coupler represented by the general formula (I) in the light-sensitive material may be approximately the same as the amount normally contained.

In addition, in the present invention, regarding the bisulfite adduct of a compound that can be added to bisulfite to be contained in a processing solution having a fixing ability (specifically, a bleach-fix solution, a fixing solution), it is necessary to form the above-mentioned adduct. Examples of the above-mentioned compounds used together with "compounds that can be added to bisulfites" or compounds selected from bisulfites, sulfites, or metabisulfites include the following general formulas (A), (B), (C) or (
A compound represented by D) is preferably used.

General formula (A) 1 R go C-R' In the formula, R3 is a hydrogen atom, a halogen atom, an alkenyl group,
represents an aralkyl group, a cyclohalogen atom, an aryl group, a heterocyclic group, a carboxylic acid group, an ester group, an acyl group, or a carbamoyl group, R4 is a hydrogen atom, a halogen atom, an alkenyl group, an aralkyl group, a cyclohalogen atom,
It represents an aryl group or a heterocyclic group, and e and R4 may be combined to form a ring, provided that R3 and R4 are not hydrogen atoms at the same time.

General formula (B) In the formula, R5, Rh, and R7 each independently represent a hydrogen atom, a halogen atom, an alkenyl group, an aralkyl group, a cyclohalogen atom, an aryl group, a heterocyclic group, a carboxylic acid group, an ester group, and an acyl group. , represents a halogen atom, ether group, sulfo group, sulfinyl group, sulfonyl group, cyano group, nitro group, erbamoyl group or sulfamoyl group,
R8 represents an electron-withdrawing group, and R8, R-1R- and Rf, R7 and R@, R'', and !-R' may be combined to form a ring.

General formula (C) In the formula, R9, R1@, and R11 each independently represent a hydrogen atom, a halogen atom, an alkenyl group, a cyclohalogen atom,
represents an aralkyl group, an aryl group, a heterocyclic group, an amino group, a carboxylic acid group, an ester group, an acyl group, an ether group, a hydroxyl group, a thioether group, and X represents an anion;
n represents 0 or 1, and R9 and R1., R1. and R1, or R1 and R drop may be combined to form a ring.

General formula (D) If, where Rlt is a halogen atom, an alkenyl group, an aralkyl group, a cyclohalogen atom, an aryl group, a heterocyclic group,
Represents a hydrogen atom, R13 is a halogen atom, alkenyl group, aralkyl group, cyclohalogen atom, aryl group, heterocyclic group, hydrogen atom, halogen group, ether group, carboxyl group, acyl group, cyano group, sulfo group, carbamoyl group group, nitro group, dialkylamino group, or ester group, Z represents a petero ring composed of a carbon atom, nitrogen atom, oxygen atom, sulfur atom, or selenium atom, Y represents an anion, and m represents 0 or Represents 1. Also Rl
t may combine with an atom in Z to form a ring.

One or more kinds of compounds represented by the above general formulas (A), (B), (C), or (D) can be used. To achieve the objective, these compounds preferably have properties such that the bisulfite adduct thereof provides the above-mentioned state.

The general formula (^) will be explained in detail below.

R3 is a hydrogen atom, a substituted or unsubstituted halogen atom (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
-methoxybenzyl group, 4-sulfobenzyl group, etc.),
Cyclohalogen atom (e.g. cyclohexyl group, etc.)
, aryl group (e.g. phenyl group, naphthyl group, 3-
sulfobutoxyphenyl group, 4-N-methyl-N-sulfopropylaminophenyl group, 3-sulfopropylphenyl group, 3-carboxyphenyl group, etc.), heterocyclic group (e.g. pyridyl group, thienyl group, pyrrolyl group, indolyl group, furyl group, furfuryl group, morpholinyl group,
(imidazolyl group, etc.), ester group (e.g., methoxycarbonyl group, ethoxycarbonyl group, etc.), acyl group (e.g., acetyl group, methoxypropionyl group, etc.)
It represents a carbamoyl group (eg, unsubstituted carbamoyl group, dimethylcarbamoyl group, etc.), a carboxylic acid group, or a salt thereof. Examples of substituted or unsubstituted halogen atom, alkenyl group, aralkyl group, cyclohalogen atom, aryl i or heterocyclic group represented by R4 are R
It is similar to that of 3.

Further, R3 and R4 may be combined to form a 5- to 7-membered saturated or unsaturated ring.

In general formula (A), preferably R3 and R4 represent a hydrogen atom, each substituted or unsubstituted halogen atom, aryl group, or heterocyclic group, provided that R3 and R4 are not hydrogen atoms at the same time. .

In general formula (A), R3 more preferably represents a hydrogen atom, and R4 represents a substituted or unsubstituted aryl group or heterocyclic group. However, when the aryl group has a substituent, the sum of Hammett's substituent constants (σ value) of the substituent is -1.2 to 1.0, and at least one sulfo group, carboxyl Those having a sulfino group, a phosphono group, or an ammonio group are preferable. What is Hammett's σ value here? Journal of Medicinal Chemistry (J, Med, Che+++,) l
jz, 1207 (I973) and samebetsu 304 (
1977).

Next, general formula (B) will be explained in detail. R5, R
6. Each substituted or unsubstituted halogen atom, alkenyl group, aralkyl group, cyclohalogen atom, aryl group, heterocyclic group, ester group, acyl group, and carbamoyl group represented by R7 has the same meaning as each of R3, Furthermore, halogen atoms (e.g., chlorine atoms, etc.), sulfo groups or salts thereof, substituted or unsubstituted ether groups (e.g., methoxy groups, phenoxy groups, etc.), sulfinyl groups (e.g., methanesulfinyl groups, etc.),
Sulfonyl group (e.g. methanesulfonyl group, benzenesulfonyl group, 4-methylbenzenesulfonyl group, etc.)
, represents a sulfamoyl group (eg, unsubstituted sulfamoyl group, dimethylsulfamoyl group, etc.). Also R8
represents an electron-withdrawing group (preferably those having the aforementioned Hammett's σ value of 0 to 1.0, such as a nitro group, a cyano group, a sulfonyl group, an acyl group, an ester group, etc.).

In general formula (B), R5, R6, and R7 preferably represent a hydrogen atom, a carboxylic acid group, a cyano group, a substituted or unsubstituted halogen atom, an aryl group, a heterocyclic group, an ester group, or an acyl group, and R8 represents It represents a nitro group, a cyano group, a substituted or unsubstituted acyl group, and an ester group, respectively.

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

Substituted or unsubstituted halogen atoms, alkenyl groups, cyclohalogen atoms, aralkyl groups, aryl groups, heterocyclic groups, ester groups, carboxylic acid groups, acyl groups, and ether groups represented by R9, RIG, and IJI+ are R1
have the same meaning as each of the above, and furthermore, substituted or unsubstituted amino groups (e.g., unsubstituted amino group, dimethylamino group, carboxymethylamino group, etc.), substituted or unsubstituted thioether groups (e.g., methylthio group, methylthio group, etc.) X represents an anion (e.g., chloride ion, bromide ion, P-)luenesulfonate ion, verchlorate ion, etc.).

In general formula (C), preferably R9,1710, R1+
represents a hydrogen atom, a substituted or unsubstituted halogen atom, an aryl group, a heterocyclic group, or an amino group.

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

R12 is a substituted or unsubstituted halogen atom (
For example, methyl group, ethyl group, sulfoethyl group, sulfobutyl group, sulfopropyl group, carboxymethyl group, dimethylaminoethyl group, 2,2.2-) IJ fluoroethyl group, etc.), alkenyl group (e.g. allyl group, etc.) ), aralkyl groups (e.g. benzyl group, phenethyl group, etc.), cyclohalogen atoms (e.g. cyclohexyl group, etc.), aryl groups (e.g. phenyl group, naphthyl group, 4-methoxyphenyl group, 3-sulfopropylphenyl group) RI3 represents a heterocyclic group (e.g., pyridyl group, pyrazolyl group, imidazolyl group, etc.), and RI3 is
Each substituent of substituted or unsubstituted acyl group (e.g., acetyl group, benzoyl group, butanoyl group, etc.), substituted or unsubstituted carbamoyl group (e.g., ethylcarbamoyl group, dimethylcarbamoyl group, etc.), substituted or unsubstituted acyl group (e.g., acetyl group, benzoyl group, butanoyl group, etc.) represents a dialkylamino group (e.g. dimethylamino group, dihydroxyethylamino group, etc.), a substituted or unsubstituted ester group (e.g. methoxycarbonyl group, acetoxy group, etc.), and Z represents a carbon atom, nitrogen atom, oxygen source -
a 5- to 6-membered heterocycle composed of a sulfur atom, a selenium atom, a sulfur atom, and a selenium atom (e.g., pyridinium ring, imidazolium ring,
Quinolinium ring, oxacillium ring, thiazolium ring,
Z may have a substituent, and Y represents an anion (eg, chlorine ion, bromide ion, p-toluenesulfonate ion, etc.).

In the general formula (D), preferably R represents a substituted or unsubstituted halogen atom, QI3 represents a substituted or unsubstituted halogen atom, and a hydrogen atom, and Z represents an imidazolium ring, benzimidazolium ring, quinolinium Represents a 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-26 NaOiSCHzCHzCHO -27 (CHs)zclhcHtcLcH0 -31 1 CHaCCHxCHzSOiNa -32 1 CHiCCHtOH -33 CH,0C82CHO -34 1 CH3CCOOH -37 OHC(CH z) 4CH0 ^-38 OHC (CM 2) zcHo -42 C) 10 GO! =CH-CN CHi=CHN (h NCCl=CH5OJa CHz"COSOsNa OzNC) I=CH5OsNa D-1 ■ Js -2 -3 (CH,) n5OsNa (CHt) asO2 C!Is ■ (Cut) 3SO3- -6 CL 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. )
” Colective Vol, I 537 (I94
1) + Co11ective Vol, n[564(
I955), 'Organic Reaction (Org
, Reaction) J H, H1968).

S, R, Sandra-1H1 Rikiro, Organink.
Functional Group Preparations (Or
ganic Functinal group Prep
arations) J Vol. 2, p. 291 (I986),
It can be synthesized according to the method described in Volume 3, page 205 (I972).

If the method of the present invention uses a color developer,
It can be applied to any processing step. For example, it can be used to process color paper, color reversal paper, color positive film, color negative film, color reversal film, color direct positive photosensitive material, and the like. In particular, application to photosensitive materials for printing such as color paper and color reversal paper is preferred.

The silver halide emulsion of the light-sensitive material used in the present invention may be of any halogen composition, such as silver iodobromide, silver bromide, silver chlorobromide, or silver chloride.

When performing rapid processing or low replenishment processing, a silver chlorobromide emulsion or a silver chloride emulsion containing 60 mol% or more of silver chloride is preferable, and a silver chloride content of 80 to 100 mol% is more preferable. Particularly preferred is 90 to 99.9 mol%. In addition, when high sensitivity is required and capri during production, storage, and/or processing must be kept particularly low, silver chlorobromide emulsions containing 50 mol% or more of silver bromide or Silveride emulsions are preferred, and more preferably 70 mol% or more. If silver bromide exceeds 90 mol%, rapid processing becomes difficult, but if means for promoting development are used, such as using a development accelerator such as a silver halide solution, a caplace agent, or a developer during processing, Development can be accelerated to some extent without being limited by the content of silver bromide, which may be preferable. In either case, it is not preferable to contain a large amount of silver iodide, and it is sufficient to contain 3 mol % or less of silver iodide.These silver halide emulsions are preferably used mainly in photosensitive materials for printing such as color paper.

Silver iodobromide and silver chloroiodobromide are preferable for color photosensitive materials for imaging (negative films, reversal films, etc.), and the silver iodide content is preferably 3 to 15 mol %.

The silver halide grains used in the photosensitive materials processed in the present invention may have different phases inside and on the surface (core/shell grains), may have a multiphase structure such as a bonded structure, or may have a uniform grain as a whole. It may consist of phases, or they may be mixed.

The average grain size of the silver halide grains used in the photosensitive material processed in the present invention (in the case of spherical or near-spherical grains, the grain diameter is the grain size; in the case of cubic grains, the grain size is the spike length, and the average grain size is based on the projected area. (also expressed in terms of spheres in the case of tabular grains) is 0 below 2.11 m.
．． It is preferably 1- or more, but particularly preferably 1.5- or less and 0.1511 m or more.

The particle size distribution can be narrow or wide, but
The value (variation rate) obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size is preferably within 20%, more preferably within 15%, particularly preferably 10%.
It is preferable to use so-called monodisperse silver halide emulsions of up to % in the present invention.

In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are used in an emulsion layer having practically the same color sensitivity (monodispersity is defined as ) can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The silver halide grains used in the light-sensitive material processed in the present invention have a regular crystalline shape of a cube, an octahedron, a rhombidodecahedron, a dodecahedron, or a combination thereof. Grains may have irregular crystal shapes such as spherical, or may have composite shapes of these crystal shapes, or may be tabular grains, especially those with a length An emulsion may be used in which tabular grains having a /thickness ratio of 5 or more, particularly 8 or more account for 50% or more of the total projected area of the grains, or an emulsion consisting of a mixture of these various crystal forms. These various emulsions may be either a surface latent image type in which a latent image is formed mainly on the surface or an internal latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the light-sensitive material processed in the present invention is Research Disclosure (RD) vol.

176 Item No., 17643 (I, II,
ml) (December 1978).

The emulsion used in the light-sensitive material processed in the present invention is usually
Use materials that have undergone physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are researched and
Disclosure Volume 176, No. 17643 (
December 1978) and Volume 187, No.

18716 (November 1979),
The relevant locations are summarized in the table below.

Known photographic additives that can be used in the photosensitive materials processed in the present invention are also listed in the above two Research Disclosures, and their locations are shown in the table below.

Additive type Chemical sensitizer Sensitivity enhancer RD17643 Page 23 Same as above RD1B716 648 Purchase Right column Same as above Super sensitizer Brightener Same as above 24 Page Coupler Organic solvent 25 Page 25 Same as above Ultraviolet absorber Stain inhibitor Dye Image stabilizer Hardener Binder Plasticizer, lubricant Same as above, page 25, right column, page 25, 26 True, page 26, page 27, page 650, left to right column, same as above, 651, left column, page 650, right column 7 Static inhibitor, page 27, same as above In the present invention In addition to the yellow coupler represented by general formula (I), various color couplers can be used. Here, the term "color coupler" refers to a compound that can generate a dye through a force/7-pulling reaction with the oxidized form of an aromatic primary amine developer. Typical examples of useful color couplers include naphthol or phenolic compounds. , pyrazolone or pyrazoloazole compounds, and open-chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that may be used in the present invention are provided in Research Disclosure (RD) 17643 (I
18717 (December 1978) ■-D section and 18717 (I97
It is described in the patent cited in November 1999). However, the yellow coupler is used in combination with the yellow coupler represented by general formula N).

The color coupler incorporated in the anti-glare material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent color coupler substituted with a leaving group is better than a two-equivalent color coupler in which the coupling active position is a hydrogen atom. Color couplers or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in combination with the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2.40
7.210, 2.875.057 and 3.2
The use of two-equivalent yellow couplers is preferred in the present invention, as described in U.S. Pat.
, No. 408.194, No. 3,447,928, No. 3.
933,501 and 4.022.620, etc., Japanese Patent Publication No. 10739/1986, and U.S. Patent No. 4,401,7
No. 52, No. 4.326,024, I? D18053
(April 1979), British Patent No. 1,425,020, West German Published Application No. 2,219,917, 2.261
．． 361, 2.329.587, and 2.4
A typical example thereof is the nitrogen atom separation type yellow coupler described in No. 33,812. α-pivaloylacetanilide couplers have excellent color fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is monosubstituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and a representative example thereof is U.S. Pat. , 2.34
3.703, 2,600,788, 2.908
．． No. 573, No. 3,062,653, No. 3,152,
No. 896 and No. 3,936,015, etc. As the leaving group for the two-equivalent 5-pyrazolone coupler, a nitrogen atom leaving group as described in US Pat. No. 4,310,619 or an arylthio group as described in US Pat. No. 4,351,897 is preferred. Also European Patent No. 7
The 5-pyrazolone coupler having a ballast group described in No. 3,636 provides high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
369,879, preferably the pyrazolo[5,1-cl[1,2,4] triazoles described in U.S. Pat. No. 3,725,067, Research Disclosure 24220 (
Pyrazolotetrazoles described in June 1984) and Research Disclosure 24230 (June 1984)
Examples include the pyrazolopyrazoles described in
Imidazo[1,
2-b] Pyrazoles are preferred, as described in European Patent No. 119,
Pyrazolo [1,5-bl [1,2,
4] Triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol couplers and phenolic couplers, such as the naphthol couplers described in U.S. Pat. No. 2,474,293 and preferably U.S. Pat. No. 4,052.
, No. 212, No. 4,146,396, No. 4.228,
Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 233 and No. 4,296,200. Further, specific examples of phenolic couplers include U.S. Patent Nos. 2,369,929 and 2.801.1.
No. 71, No. 2.772.162, No. 2,895.82
It is stated in issue 6 etc. Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is a halogen atom having an ethyl group or more at the meta position of a phenol nucleus described in U.S. Pat. No. 3,772,002. Phenolic cyan couplers having U.S. Patent No. 2.772.162, U.S. Pat. No. 3,758,308, U.S. Pat.
No. 4,327.173, West German Patent Publication No. 3,329.
2,5-diacylamino-substituted phenolic couplers described in No. 729 and JP-A-59-166956, and U.S. Pat. Nos. 3,446,622 and 4,33
No. 3.999, No. 4,451,559 and No. 4.4
These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, as described in No. 27,767.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such dye-diffusive couplers are magenta couplers in U.S. Pat. .234.533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and specialty couplers described above may form dimers or more polymers; typical examples of polymerized dye-forming couplers are described in U.S. Pat. No. 3,451,82.
No. 0 and No. 4,080,211.

A specific example of a polymerized magenta coupler is described in British Patent No.
．． 102.173 and U.S. Pat. No. 4.367.28
It is stated in No. 2.

The various couplers used in the present invention can be used in combination in two or more layers in the same photosensitive layer, or in two or more different layers using the same compound, in order to satisfy the characteristics required for the photosensitive material. It can also be introduced into

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. An example of a high boiling point organic solvent used in the oil-in-water dispersion method is U.S. Pat. No. 2,322,027.
It is written in the number etc. Further, the process and effects of latex dispersion as one of the polymer dispersion methods, and specific examples of latex for impregnation are disclosed in U.S. Patent No. 4,199.363.
West German Patent Application III (OLS) No. 2.541.274 and OLS No. 2,541.230 describe dispersion methods using organic solvent-soluble polymers in PC? Application number JP8
It is described in the specification of No. 7100492.

Examples of organic solvents used in the above-mentioned oil-in-water dispersion method include phthalic acid alkyl esters (dibutyl phthalate,
dioctyl phthalate), phosphate esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate) , alkylamides (e.g. diethyl laurylamide), fatty acid esters It (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc., or organic solvents with a boiling point of 30°C to 150°C, e.g. Lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc. may be used in combination.

Typical usage amounts for color couplers range from 0.001 to 1 mole per mole of photosensitive silver halide, preferably from 0.01 to 0.1 mole for yellow couplers.
5 mole, 0.003 to 0.3 for magenta coupler
moles, and for cyan couplers 0.002 to 0.3
It is a mole.

The photographic material used in the present invention is coated on a commonly used plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), a flexible support such as paper, or a rigid support such as glass. For details on supports and coating methods, see Research Disclosure 176Sltem 17643X
V term (P, 27) X1 term (P.

28) (December 1978 issue).

In the present invention, a reflective support is preferably used.

A "reflective support" is a material that increases the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Such a reflective support includes titanium oxide, zinc oxide, Examples include those coated with a hydrophobic resin containing dispersed light-reflecting substances such as calcium carbonate and calcium sulfate, and those using a hydrophobic resin containing dispersed light-reflecting substances as a support.

The color developing solution used in the development processing performed prior to the processing with the processing solution having fixing ability in the method of processing a photosensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. It is. As this color developing agent, amine phenol compounds are also useful, but p-phenylenediamine compounds are preferably used, typical examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-diethylaniline, Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N- Mention may be made of ethyl-N-β methoxyethylaniline and its sulfates, hydrochlorides or P-)luenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, hendithiazoles or mercapto compounds are generally included. In addition, if necessary, 1 g of hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (I,4-diazabicyclo[2,2,2]octane) Various preservatives such as ethylene glycol,
Organic solvents such as diethylene glycol, hensyl alcohol, voluteylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, phenyl-3- Auxiliary developing agents such as pyrazolidone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, Diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, ■-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N'
, N'-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black-and-white developer contains known black-and-white developing agents such as dihydroxyhenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. It can be used alone or in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but it is generally less than 31 per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be reduced to less than 500. It can also be done. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The photographic emulsion layer after color development is processed with a processing solution having fixing ability in the present invention, but is usually bleached. The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process), or separately (bleach-fixing process), or in order to speed up the process, it may be possible to perform a bleach-fixing process after the bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents include iron (■), cobalt (■),
Compounds of polyvalent metals such as chromium (■) and copper (II), oxidants, quinones, nitro compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate; iron (
III) or organic complex salts of cobalt (II[), such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1°3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, etc. Alternatively, complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates; bromates; manganates; nitrobenzenes, etc. can be used. Among these, aminopolycarboxylic acid iron (I [[) complex salts and persulfates, including ethylenediaminetetraacetic acid iron (III) complex salts, are preferable from the viewpoint of rapid processing and environmental pollution prevention. ) Complex salts are particularly useful in both bleach and bleach-fix solutions. The pi of the bleach or bleach-fix solution using these aminopolycarboxylic acid iron (II) complex salts is usually 5.5 to 8, but in order to speed up the processing, it can be processed at an even lower pi. .

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893.858, German Pat.
, No. 290.812, JP-A-53-95.630, Research Disclosure No. 17.129 (I9
Compounds having a mercapto group or a disulfide bond described in JP-A-50-140.129 (July 1978), etc.
Thiazolidine derivatives described in US Pat. No. 3,706
．． Thiourea derivatives described in No. 561; JP-A-58-16
, 235; West German Patent No. 2.748,
Polyoxyethylene compounds described in Japanese Patent Publication No. 430, polyamine compounds described in Japanese Patent Publication No. 45-8836, bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly described in U.S. Pat. Preference is given to the compounds described in U.S. Patent No. 4.55.
The compounds described in No. 2.834 are also preferred. These bleach accelerators may be added to light-sensitive materials. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Thiosulfate is always used as a fixing agent, but examples of fixing agents that can be used in conjunction with it include thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts. Among the thiosulfates, ammonium thiosulfate is the most widely used.

Silver halide color photographic materials are generally subjected to water washing and/or stabilization steps after desilvering treatment. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
l of the 5ociety of Motion
Picture and TelevisionE
ngineers Vol. 64, P, 248-253 (
It can be determined by the method described in May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288,838 can be used very effectively. Also, patent application No. 57-8,542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, "Microbial It is also possible to use the fungicides described in "Sterilization, Disinfection, and Anti-Mildew Techniques" and "Encyclopedia of Antibacterial and Antifungal Agents" published by Japan Antibacterial and Antifungal Science.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. A range is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization processing, Japanese Patent Application Laid-Open No. 578.54
No. 3, No. 58-14,834, No. 60-220.34
All known methods described in No. 5 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. U.S. Patent No. 3.342.59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14.850
Schiff base-type compounds described in No. and No. 15.159, aldol compounds described in No. 13,924, U.S. Patent No. 3
, 719,492, JP-A-53-1
Examples include urethane compounds described in No. 35,628.

The silver halide color light-sensitive material of the present invention may optionally contain various types of 1-phenyl-3-
It is also possible to incorporate birapritons. Typical compounds are JP-A No. 56-64,339, JP-A No. 5714.4547,
and No. 58-115,438.

Various processing solutions in the present invention are used at 10°C to 50'C. Normally, a temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. can be achieved.

In addition, West German Patent No. 2,226,7
70 or U.S. Pat. No. 3,674.499 using cobalt or hydrogen peroxide intensification.

(Example) Hereinafter, the present invention will be explained in detail based on examples.

Example 1 As described in Table 1, the first layer (bottom layer) to the seventh layer (
A color photographic paper sample 1-A was prepared by sequentially applying and forming the uppermost layer). The coating solution for each layer was prepared as follows. The details of the structural formulas of the couplers, color image stabilizers, etc. used in the coating solution will be described later.

The coating liquid for the first layer was prepared as follows. i.e. 200g of yellow coupler, 93.3g of anti-fading agent
After heating and dissolving a mixture of 10 g of high boiling point solvent (p) and 5 g of solvent (q) to which 600 m of ethyl acetate was added as an auxiliary solvent to 60°C, Alkanol B (trade name, alkylnaphthalene sulfonate, manufactured by DuPont) was dissolved. 5% aqueous solution of gelatin containing 330 ad
This solution was then emulsified using a colloid mill to prepare a coupler dispersion.

Ethyl acetate was leaked from this dispersion under reduced pressure, and a sensitizing dye for a blue-sensitive emulsion layer and 1-ethyl-2-mercapto-5-acetylamino-1,3,4-triazole were added to emulsion 1.
, 400g (96.7g as 8g, gelatin 1
70g) and further add 10% gelatin aqueous solution 2
．． A coating solution was prepared by adding 600 g. The coating liquids for the second to seventh layers were prepared according to the compositions shown in Table 1 and in the same manner as for the first layer.

1 Table 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole p di(2-ethylhexyl) phthalate q dibutyl phthalate r2.5-di-ter t-amylphenyl-3,5-
Di-tert-butyl hydroxybenzoate s2,5
-ter t-octylhydroquinone t1,4-
Di-tert-amyl-2,5-dioctyloxybenzene 2,2'-methylenebis(4-methyl-6-te
rt-butylphenol) The following were used as sensitizing dyes for each emulsion layer.

Pre-malignant emulsion layer; Green-sensitive emulsion layer; Anhydro-5-methoxy-5'methyl-3,3'-disulfoprobyl selenacyanine hydroxide anhydro-9-ethyl-5,5'-diphenyl-3,3 '-Disulfoethyloxacarbocyanine hydroxide red-sensitive emulsion layer, 3.3'-diethyl-5-methoxy-9
, 9'-(2,2-dimethyl-1,3-propano)thiadicarbocyanine iodide The following substances were also used as stabilizers for each emulsion layer.

1-Methyl-2-mercapto-5-acetylamino-1
, 3,4-) The following dyes were used as lyazole and irradiation-preventing dyes.

4-(3-carboxy-5-hydroxy-4-(3-(
3-Carboxy-5-oxo-1-(4-sulfonatophenyl)-2-pyrazolin-4ylidene)-propenyl)-1-pyrazolyl)benzenesulfonate-di-potassium salt N, N' -(4,8 -dihydroxy-9,10-dioxo3,7-cissulfonatoanthracene-1,5-diyl)bis(aminomethanesulfonate)-tetrasodium salt or using 1,2-bis(vinylsulfonyl)ethane as a hardening agent. there was.

The couplers used are as follows.

yellow coupler magenta coupler cyan coupler and (1:1 molar ratio) Next, the yellow coupler of sample 1-A was mixed with the following IB-1-
Sample 1-B, IC, ID, I- with equimolar replacement with G
E, I-F, and r-G were created.

■ Shii3 -C ■ ■ Coupler No. of the present invention, 6 -F Coupler No. of the present invention, 11 ■ Coupler No. of the present invention, 12 Next, the color photographic paper 1-A was exposed imagewise, and the following processing steps were carried out. The process was continued until four times the tank capacity of the color developer was replenished. However, the bleach-fix preservative was used under different conditions as shown in Table 2.

1M color development 41°C 1 minute 40 seconds 200d bleach fixing 35°C 50 seconds 170af stable ■ 3
0~35℃ Stable for 35 seconds ■ 3
Stable for 5 seconds ■ 35 seconds See Table 2 70
℃ 1 The stabilization process was carried out in a 3-tank countercurrent flow direction from stabilization ■→■→■. Also, the amount brought in from the front bath is 40d/n? Met. The composition of each treatment liquid used is as follows.

h--' LL! JLMffJL Hensyl Aryl 15 d 20 d
diethylene glycol 10 d 10
id hydroxyethyliminodiacetic acid 2.0g 2
．． 0g Catechol-2,4-disulfonic acid 0.2g Sodium sulfite 1.7g Hydroxyamine sulfate 3.0g Potassium bromide
0.90g4-amino-3-methyl-N
5.0 g-ethyl-N-(β-(methanesulfonamido)ethyl) ~ aniline sulfate 4-amino-3-methyl-N 1. Og-ethyl-
N-Hydroxyethylaniline sulfate Potassium carbonate 30 g Optical brightener (4,4'-diamino 1.5 g 0.2 g 2.3 g 4.5 g 8.0 g 1.5 g 5 g 2.5 g Add water 1000 dpH 10, 2
5 1 standing i! (Tank fluid and refill fluid are the same) EDTAFe
(I[[)NH4・28zOEDTA・2Na ・'
2HtO Ammonium thiosulfate (70χ) 000d1 10.80 0g g 20d Add preservative glacial acetic acid water and adjust pH fl (tank solution and replenishment solution are the same) 5-chloro-2-methyl-4-isothiazolin-3-one 2- Methyl-4-isothiazolin-3-one 2-octyl-4-isothiazolin-3-one Bismuth chloride (40χ) Nitrilo-N,N,N-)rimethylenephosphonic acid (40χ) 1-Hydroxyethylidene-1,1 diphosphonic acid (60% optical brightener (4,4'-diaminostilbene type) ammonia water (26χ) Add water to make 0.1 mol 7g 000ad 5.5 0 g 0 g 10 ■ 0.5g 1.0g 2.5g 1.0g 2.0m 000d At KOH, samples 1-A to I-G were processed after wedge-shaped exposure to each of the Laninda liquids at pH 7 and 5, and the yellow density was measured.The minimum yellow density at this time was Let it be Dsin.

In addition, these treated samples were irradiated with 8500 Lux xenon light at 25°C with a distance of 50 C11, and after 20 days, the density change (ΔDminsΔDI-15) at the stain part (Dsin part) and the yellow density point of 1.5 was measured. did. In addition, these treated samples were stored for 4 weeks at 60°C and 170% RH, and the yellow density change (ΔD
□, ) were measured.

These results are shown in Table 2.

Table 1 Based on the present invention, there is little increase in yellow stain, and yellow photobleaching is also improved.

Example 2 A multilayer photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene.

The coating solution was prepared as follows.

(Preparation of coating solution for the first layer) Add 27.2 c of ethyl acetate to 19.1 g of yellow coupler (ExY-1) and 4.4 g of color image stabilizer (Cpd-1).
c and high boiling point solvent (Solv-1) 7.7cc (8
. This emulsified dispersion and emulsions EM7 and EM8 were mixed and dissolved, and the gelatin concentration was adjusted to have the following composition to prepare a first layer coating solution.

Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. 1-oxy-3,5-dichloro-8-triazine sodium salt was used as the gelatin hardening agent for each layer.

Moreover, (Cpd-11) was used as a thickener.

(Layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/bo). The silver halide emulsion represents the coating amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiOx) and a bluish dye. ] th layer (blue layer) Monodisperse silver chlorobromide emulsion (EM7) spectrally sensitized with a sensitizing dye (ExS-1) 0.15 sensitizing dye (ExS-1)
Monodisperse silver chlorobromide emulsion (EA8) spectrally sensitized with S-1)
) Gelatin yellow coupler (ExY-1) Color image stabilizer (Cpd-2) Solvent (Solv-1) Second layer (color mixing prevention layer) Gelatin color mixing prevention agent (Cpd-1) Third layer (green sensitive layer) Monodisperse silver chlorobromide emulsion (E?I9) spectrally sensitized with sensitizing dyes (ExS-2, 3) Monodisperse silver chlorobromide emulsion spectrally sensitized with sensitizing dyes (ExS-2, 3) Emulsion (EMIO) Gelatin magenta coupler (Ex-1) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) N1111 Medium (S01 Sea 2) Fourth layer (ultraviolet absorbing layer) 0.15 1.86 0.82 0.19 0.35 0.99 0.08 0.12 0.24 1.24 0.39 0.25 0.12 0.25 Gelatin ultraviolet absorber (Cpd-6/Cpd- 7/Cpd-8・
3/2/6: Weight ratio) Color mixing inhibitor (Cpd-9) Solvent (Sol Sea 3) Fifth layer (red sensitive layer) Monodisperse spectrally sensitized with sensitizing dye (Ext-4, 5) Silver chlorobromide emulsion (El'1ll) Sensitizing dye (ExS-4,5
) Spectrally sensitized monodisperse silver chlorobromide emulsion (2M12) Gelatin cyan coupler (ExC-1) Cyan coupler (ExC-2) Color image stabilizer (Cpd-7/Cpd-8/Cpd-10=
3/4/2: (weight ratio) Polymer for dispersion (Cpd-11) Medium (Sol Sea 1) Sixth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (Cpd-6/Cpd-8/1.60 0.70 0.05 0.42 0.07 0.16 0.92 1.46 1.84 0.17 0.14 0.20 0.54 Cpd-10=115/3: Weight ratio)
0.21 solvent (Solv-4)
0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Liquid paraffin 0.03 In addition, at this time, as an irradiation prevention dye, (Cpd-
12, Cpd-13) was used.

Furthermore, each layer contains Alkanol
xF-120 (manufactured by Dainippon Ink Co., Ltd.) was used. (Cpd-14,15) was used as a silver halide stabilizer.

Details of the emulsion used are as follows.

M8 EM9 MIO Mll M12 cube cube cube cube cube 0.8 0.45 0.34 0.45 0.34 0.10 0.09 0.09 0.09 0.10 The structural formula of the compound used is as follows.

Y-1 1 to E! XM-1t! xC-1 xC-2 H f'xs-1 5OJN(CtHs)s 3OsHN(CJs)s xS-5 pd-2 Cpd-3 Cpd-7 Cpd-9 0 Cpd 1 Cpd-12 Cpd-13 Cpd-15 Sol Sea 1 Diptyl phthalate 5olv-2 Trioctyl phosphate 5OIV-3 Trinonyl phosphate 5olv-4) Recresyl phosphate All gelatin used was alkali-treated gelatin with an isoelectric point of 5.0. This sample was designated as 2-A.

Next, sample It
-B, II-C, I[-D.

-B I 2-CNo, 11 2-DNo, 12 Next, after imagewise exposing sample 2-A, the benzyl alcohol concentration in the color developer and the preservation of the bleach-fixer were adjusted in the following processing steps. Continuous processing was carried out under conditions that were changed as shown in Table 3.

Processing ■ 1 time Single plate 1Ll*Zekuro I color development 35℃ 45 seconds 161 d 17
4! Bleach fixing 30-36℃ 45 seconds 1611d
171 Rinse■ 30-37℃ 20 seconds □
Ioj! Rinse ■ 30-37℃ 20 seconds □
1OIl rinse■ 30-37℃ 20 seconds □
10i Rinse ■ 30~37℃ 30 seconds See Table 3 1Ol drying 70~80℃ 60 seconds *Per photosensitive material 1 point (Rinse ■→■ 4 tank countercurrent system was used.) (The amount brought in was 30d/pot. ) The composition of each treatment solution is as follows.

Sadate Niri l Oka LIL Oka Sarainu Sprinkling Water
800jd
800d Benzyl Alcohol Table 3 81 Diethylene Glycol 10allon Ethylenediamine-N.

N,N,N-tetramethylenephosphonic acid 1.5g 1.5g triethylenediamine (I,4-diazabicyclo[2,2,21 octane> 5.0g) 5.
0g Sodium chloride 1.4g Potassium carbonate 25g 25g N-ethyl-
N-(β-methanesulfonamidoethyl)-3 methyl-4-aminoaniline sulfate 5.0 g 7.0 g Diethylhydroxylamine 4.2 g 6.0 g Optical brightener (add 4,4'-diamino water 1000d 1000m1 00O (25℃) 10.05 10.45 1 target Jllll (tank fluid and replenishment fluid are the same) water
4001d Ammonium thiosulfate (70χ) 10G1
11 Preservative 0.1 mol ethylenediaminetetraacetic acid iron(I) Ammonium 55g ethylenediaminetetraacetic acid disodium 5g ammonium bromide 40g glacial acetic acid
Add 9g water
1000111pH (25℃)
5.40 yen (tank fluid and refill fluid are the same) Ion exchange water (calcium, magnesium each app-
Below) Samples 2-A, 2-B, and 2-C were prepared in the same manner as in Example 1 for each of the obtained running completion liquids.

2-D was treated and irradiated with a 95,000 Lux fluorescent lamp from a 30 cm beam for 40 days, and changes due to photobleaching of 0□1n, Dml, and 5 were determined in the same manner as in Example 1. The results are shown in Table 3.

TABLE 1 In accordance with the present invention, yellow stain increase and photobleaching were improved, and the cure was similar with or without benzyl alcohol.

〔Effect of the invention〕

According to the processing method of the present invention, a color image with less yellow stain and excellent image stability can be obtained. The image stability is much better than that obtained with a light-sensitive material using a commonly used yellow coupler, and the stability of the image is superior to that obtained with a light-sensitive material using a commonly used yellow coupler. Through synergy,
That effect can be obtained.

Claims (1)

[Scope of Claims] A method for processing a silver halide color photographic light-sensitive material, which comprises imagewise exposing the silver halide color photographic light-sensitive material, subjecting it to color development treatment, and treating it with a processing solution having fixing ability, comprising: The photographic light-sensitive material contains at least one kind of yellow coupler represented by the following general formula (I), and the processing liquid having the fixing ability contains thiosulfate and at least one compound that can be added to bisulfite. characterized by containing a bisulfite adduct and/or at least one compound capable of adding to bisulfite and at least one compound selected from bisulfite, sulfite or metabisulfite A method for processing silver halide color photographic materials. General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R^1 represents a tertiary alkyl group or an aryl group. R^2 represents a halogen atom or an alkoxy group. R^3 represents an alkyl group or an aryl group. Y^1 represents a divalent linking group. X represents a coupling-off group.