JPH0296142A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the generation of a fogging in the subject material by being comprised a silver halide emulsion layer composed of silver chloride and a layer contg. a specified compd. in the photosensitive material, and by specifying the total amount of a coated silver contd. in the emulsion layer and the contents of a chlorine ion and a bromine ion contd. in a color developer, respectively. CONSTITUTION:The photosensitive material comprises the silver halide emulsion layer composed of >=80mol% of silver chloride and the layer contg. the compd. shown by formula I, and the total amount of the coated silver contd. in the emulsion layer is specified to <=0.75g/m<2>. The color developer contains the chlorine ion of 3.5X10<-2> - 1.5X10<-1>mol/l and the bromine ion of 3.0X10<-5> - 1.0X10<-3>mol/l. In formula I, R1 is alkyl, alkenyl, aryl or a heterocyclic ring group, R2 - R6 are each hydrogen or halogen atom or alkyl, alkenyl, aryl or a heterocyclic ring group and the like. Thus, the fluctuation of the photographic characteristic, especially the generation of the fogging in the material at the time of continuously processing it are prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a rapid and/or simple processing method for silver halide color photographic materials.

More specifically, the present invention relates to a method for processing a silver halide color photographic light-sensitive material, which has improved processability, processing dependence, and image fastness in rapid and/or simple processing.

(Prior Art) In recent years, in the photographic processing of color photographic materials, it has been desired to shorten the processing time due to the shortening of the finishing delivery time and the reduction of laboratory work.

Increasing the temperature and increasing the amount of replenishment are common methods for shortening the time of each treatment step, but many other methods have been proposed, such as increasing stirring or adding various accelerators.

In particular, for the purpose of speeding up color development and/or replenishing the amount of replenishment, color photographic materials containing silver chloride emulsions in place of the conventionally widely used silver bromide emulsions or silver iodide emulsions are processed. There are known ways to do this. for example,
International Publication Patent No. WO 37-04534 discloses that a silver halide color photographic material with a high silver chloride content (hereinafter referred to as a high silver chloride color photographic material) is a color material substantially free of sulfite ions and benzyl alcohol. A method of rapid processing with a developer is described.

However, it has been found that there are unexpected problems such as increased fog due to pressure sensitization when developing processing is performed based on the above method.

Furthermore, during continuous processing, fluctuations in photographic properties, poor desilvering, staining of the white background (residual color), and deterioration of image storage stability were observed. As a method for reducing fluctuations in photographic properties (especially fog) caused by The prevention effect was insufficient, and it was difficult to suppress the minimum density due to increased residual color during continuous processing.

In addition, JP-A-61-70552 discloses a method for reducing developer replenishment by using a high silver chloride color photographic light-sensitive material and adding a replenishing amount to the developing bath during development in an amount that does not cause overflow. Are listed.

Furthermore, in JP-A No. 63-106655, for the purpose of stabilizing processing, a silver halide emulsion layer contains a silver halide color photographic light-sensitive material having a high silver chloride content and a hydroxyamine compound at a predetermined concentration or higher. A method of developing with a color developing solution containing chloride is disclosed. However, these methods have problems in that variations in photographic properties (especially variations in photographic properties due to the influence of developer components, pH, temperature, etc.) have been observed, and improvements have been sought.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to provide a rapid development process using a high-silver chloride color photographic light-sensitive material and which can prevent the occurrence of fog.

A second object of the present invention is to provide a color photographic light-sensitive material and a development processing method using a high-silver chloride color photographic light-sensitive material, which is quick and simple, and which exhibits less fluctuation in photographic properties.

A third object of the present invention is a method for forming an image on a color photographic light-sensitive material using a high-silver chloride color photographic light-sensitive material, which is quick, simple, and has good image storage stability (reduction in fa degree and increase in density in white background areas). The goal is to provide the following.

(Means for Solving the Problem) The present inventors investigated various antifading agents and compositions of treatment liquids, and as a result, found that the problem could be solved by the following means.

That is, in a method in which a silver halide color light-sensitive material is processed with a color developer containing at least one aromatic primary amine color developing agent, the silver halide color light-sensitive material contains 80 mol% or more of silver chloride. It has at least one layer of a silver halide emulsion consisting of the following general formula (
has a layer containing at least one kind of compound represented by I), and has a total coating silver amount of 0.75 g/m or less,
The color developer contains 3.5X10-2 to 1 chloride ions.
．． Contains 5X10-' mol/l and 3.
The problem was solved by a method for processing a silver halide color photographic material characterized by containing 0.times.10@-5 to 1.0.times.10@-' mol/l.

General Formula (I) In the formula, R1 represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.

R2, R3, Ra, Rs and R6 may be the same or different (a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, respectively)\Rogen atom, -OR
"l, SR'l, Ngu, sulfonyl group,
It represents a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, and a formyl group.

R't represents the same meaning as R. R1 and R8 may be the same or different, and each represents a hydrogen atom, an alkyl group, an alkenyl group, an ary)IiM, a heterocyclic group,
Represents an acyl group, a carbamoyl group and a sulfonyl group.

Among OR1, R2, R3, Ra, Rs, and R6, the groups at ortho positions may be bonded to each other to form a 5- to 7-membered ring, or R7 and R8 may be bonded to each other to form a 5- to 7-membered ring. may be formed.

The present invention will be explained in detail below. The silver halide emulsion of the present invention has a silver chloride content of 80 mol % or more, preferably 95 mol % or more, and more preferably 98 mol % or more based on the total amount of silver halide. From the viewpoint of rapidity, the higher the silver chloride content, the more preferable.

The coating silver amount of the silver halide photosensitive material of the present invention is 0°75
It is necessary that it is less than or equal to g/nj. Coated silver amount is 0.
If it exceeds 75 g/m, there will be a lot of variation in photographic properties, and the object of the present invention will not be achieved.

In the present invention, 3 chloride ions are added to the color developer.
．． It is necessary to contain 5X10-2 to 1.5X10-mol/l. Preferably 4×10 −2 to I×1
0-'mol/β. Chlorine ion concentration is 1.5X10
-'mol/7! If the amount is more, it has the disadvantage of retarding the development and does not achieve the object of the present invention of rapid development and high maximum density.

Moreover, if it is less than 3.5×10 to 2 mol/p, the object of the present invention cannot be achieved due to large fluctuations in photographic properties due to processing fluctuations.

In the present invention, 3.0% bromine ion is added to the color developer.
It is necessary to contain X10-' mol/Il to 1.0X10-' mol/β. Preferably 5°oxio-5~
5.0×10 −′ mol/l. Bromine ion concentration is l
If it is more than 0XIO-'mol/l, the development will be delayed and the purpose of rapid processing will not be achieved.

On the other hand, if it is less than 3.0 x 10-5 mol/p, processing fluctuations (particularly processing liquid components and pH fluctuations) will be so large that the object of the present invention will not be achieved.

Here, chloride ions and bromine ions may be added directly to the developer and/or may be eluted from the photosensitive material in the developer.

When added directly to a color developer, examples of the chloride ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, among which preferred ones are preferred. are sodium chloride and potassium chloride.

It may also be supplied from a fluorescent brightener added to the developer. As a supply material for bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among these, preferred are potassium bromide and sodium bromide.

When eluting from the photosensitive material in the developer, both chlorine ions and bromine ions may be supplied from the emulsion or may be supplied from a source other than the emulsion.

-i The compound represented by formula (I) will be explained in detail.

R1 is an alkyl group (a linear, branched or cyclic alkyl group such as methyl, ethyl, propyl, butyl, 5ec-
butyl, tert-hexyl, benzyl, cyclohexyl, octyl, isooctyl, decyl, dodecyl, hexadecyl, octadecyl), alkenyl groups (e.g. vinyl, allyl), aryl groups (e.g. phenyl, naphthyl), heterocyclic groups (carbon atoms, oxygen atoms) , sulfur atom or nitrogen atom, such as 2-pyridyl, 2-piperidyl, 2morpholinyl, 4-chromanyl).

R2+ R:1. R4+ R5 and R6 may be the same or different, and each represents a hydrogen atom, an alkyl group (a linear, branched or cyclic alkyl group such as methyl, ethyl, propyl, butyl, 5ee-butyl, tert-hexyl, benzyl, cyclohexyl) , octyl, isooctyl, decyl, dodecyl, hexadecyl, octadecyl), alkenyl groups (e.g. vinyl, allyl), aryl groups (e.g. phenyl, naphthyl), heterocyclic groups (carbon, oxygen, sulfur or nitrogen atoms) A heterocyclic ring composed of atoms such as 2-pyridyl,
2-piperidyl, 2-morpholinyl, 4chromanyl),
Halogen atom (eg fluorine atom, chlorine atom, bromine atom), -OR', -3R'R7N', sulfonyl group (eg methanesulfonyl, toluenesulfonyl), -3R'.

R1 N', sulfonyl group (e.g. methanesulfonyl, toluenesulfonyl), sulfinyl group (e.g. dodecanesulfinyl, benzenesulfinyl), alkoxycarbonyl group (e.g. methoxycarbonyl, octyloxycarbonyl, octadecyloxycarbonyl), It represents an oxycarbonyl group (eg phenyloxycarbonyl, naphthyloxycarbonyl), an acyl group (eg acetyl, benzoyl), a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group and a formyl group. Rt1 represents the same meaning as R3. R9 and R
8 may be the same or different, and each represents a hydrogen atom, an alkyl group (a linear, branched or cyclic alkyl group, such as methyl, ethyl, propyl, butyl, 5eC-butyl, t
ert-hexyl, hensyl, cyclohexyl, octyl, isooctyl, decyl, dodecyl, hexadecyl,
octadecyl), alkenyl groups (e.g. vinyl, allyl), aryl groups (e.g. phenyl, naphthyl), heterocyclic groups (heterocyclic rings composed of atoms selected from carbon atoms, oxygen atoms, sulfur atoms, or nitrogen atoms, such as 2-
pyridyl, 2-piperidyl, 2-morpholinyl, 4-chromanyl), acyl groups (e.g. acetyl, benzoyl)
, carbamoyl group, and sulfonyl group (eg, benzenesulfonyl, methanesulfonyl, dodecanesulfonyl).

OR+, Rt, R3, R4+ Groups in the ortho positions of Rs and R6 may be bonded to each other to form a 5- to 7-membered ring, and R9 and R8 may be bonded to each other to form a 5- to 7-membered ring. You may.

Among the compounds represented by the general formula (I), preferred compounds from the viewpoint of the effects of the present invention are those in which at least one of R2-R6 is -OR', -3R', -3R', -R2-R6.

This is the case when the group is selected from N.

Rs More preferable compounds have the following general formulas (I a) (Ib)
, (Ic), (Id), (Ie) and (In).

l5- CH.

CH3 In the formula, R+, R2, Rs, R4, Rs, Rb and R'1 have the same meanings as in general formula (I). RII and R″1 have the same meaning as R′ +. R5°.

R, -・R12・R13・R14・RIS・RI6・R
IOR11' may be the same or different, and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. R14 and RIS further represent an alkoxy group, an aryloxy group, a substituted or unsubstituted or cyclic amino group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, or an aryloxy group. R'2 and R's have the same meaning as R+.

The compounds of the present invention are specifically illustrated below, but the present invention is not limited thereby.

CH3 LJL;Hz UH2L;Hz 2 US(M
)C,H,,/”ゝC3HI7(I''shi83shiH
.

+13 CHt CHCa Hq’ga)zHs shih3shins CH.

These compounds can be easily synthesized according to the literature method described in Japanese Patent Application No. 62-158342. .

The compound represented by the general formula (I) of the present invention may be used in any layer of the photosensitive material. Preferably used in layers containing couplers.

The compound represented by general formula (I) of the present invention is coupler 1
per mole I
The range is from X 10-' to 5 moles.

The processing liquid will be explained in more detail below.

In the present invention, from the viewpoint of processing stability and fog prevention, it is preferable that the color developer contains substantially no sulfite ions, but in order to suppress the deterioration of the developer, it is recommended not to use the developer for a long time, and to avoid air oxidation. In order to suppress the effects of this, physical measures such as using a floating pig or reducing the opening of the developer tank, and chemical measures such as lowering the developer temperature and adding organic preservatives are used. Can be used. Among these, the method using an organic preservative is advantageous in terms of simplicity.

The organic preservative according to the present invention refers to any organic compound that reduces the deterioration rate of an aromatic primary amine color developing agent when added to a processing solution for a color photographic light-sensitive material. In other words, organic compounds that have the function of preventing color developing agents from being oxidized by air, etc., include hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals,
Particularly effective organic preservatives include alcohols, oximes, diamide compounds, and fused ring amines. These are Japanese Patent Application No. 61-147823 and Japanese Patent Application No. 61-1735.
No. 95, No. 61-165621, No. 61-18861
No. 9, No. 61197760, No. 61-186561, No. 61-198987, No. 61-201861,
No. 61-18.6559, No. 61-170756,
6m-188742, 61188741, US Pat.
It is disclosed in No. 6, etc.

The general formulas of the preferred organic preservatives are listed below, but the organic preservatives that can be used in the present invention are not limited to these.

In addition, the amount of the following compounds added to the color developing solution is 0.00
5 mol/2 to 0.5 mol/ffi, preferably 0.0
It is desirable to add it to a concentration of 3 mol/It-0.1 mol/l.

Particularly preferred is the addition of hydroxylamine derivatives and/or hydrazine derivatives.

The hydroxylamine derivative is preferably one represented by the following general formula (II).

General formula (n) R11N RI2 H In the formula, R11 and RI2 represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or a heteroaromatic group. The R'th and R'2 do not become hydrogen atoms at the same time, and may be linked to each other to form a heterocycle together with the nitrogen atom. The ring structure of the heterocycle is a 5- to 6-membered ring composed of carbon atoms, hydrogen atoms, halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, etc., and may be saturated or unsaturated.

As the hydrazines and hydrazides, the following are preferred.

General formula (II [) where R31, R32, and R33 represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, and R34 represents a hydroxy group, a hydroxyamino group, a substituted or unsubstituted represents an alkyl group, aryl group, heterocyclic group, alkoxy group, monoloxy group, carbamoyl group, or amino group. It is composed of N, S, and halogen atoms, and may be either saturated or unsaturated. x31 represents 100-, and n is O or 1. In particular, when n=Q, R34 represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and R33 and R34 may jointly form a heterocyclic group.

The combined use of the compound represented by the general formula (II> or (III)) and the amine represented by the following general formula (IV) or (V) improves the stability of the color developer,
This is particularly preferred from the viewpoint of improving stability during continuous processing.

General formula (TV) R71N R? 3 In the formula, R7+, R72, R? 3 represents a hydrogen atom, an alkyl group, an alkenyl group, an aral group, an aralkyl group, or a heterocyclic group. Here, R", R72R" and Rff3
Alternatively, R'' and R?3 may be linked to form a nitrogen-containing heterocycle.

Here, R'', R72 and R73 may have a substituent. R'71, R'' and Rff3 are particularly preferably a hydrogen atom or an alkyl group. Examples of the substituent include a hydroxyl group, a sulfo group, a carboxyl group, a halogen atom, a nitro group, and an amino group.

General formula (V) In the formula, X represents a trivalent atomic group necessary to complete the condensed ring, and R1 and RZ are an alkylene group, an arylene group,
Represents an alkenylene group or an aralkylene group.

Here, R1 and RZ may be the same or different.

The organic preservatives mentioned above can be prepared by hand using commercially available products;
It can also be synthesized by the method described in No. 74 and the like.

The color developer used in the present invention will be explained below.

The color developer used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is p-phenylenediamine, and representative examples are shown below, but the invention is not limited thereto.

I) -1N,N-diethyl-p-phenylenediamine D-24-(N-ethyl-11-(β-hydroxyethyl)amine coaniline D-32-methyl-4-[N-ethyl-N-[β -hydroxyethyl)aminocoaniline D-44-amino-3-methyl-N-ethyl N-[β-
(Methanesulfonylamide)ethylcoaniline These p-phenylenediamine derivatives may also be salts such as sulfate, hydrochloride, p-toluenesulfonate, and the like. The amount of the aromatic-grade amine developing agent used is preferably about 0.1 g to 20 g, more preferably about 0.5 g to about 10 g, per 11 of the developer solution.

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 various buffers. Buffers 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 salicylate), potassium 0-hydroxybenzoate, 5-sulfo-
Examples include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfol-2hydroxybenzoate (potassium 5-sulfosalicylate).

The amount of the buffer added to the color developer is 0. 1 mole/
It is preferably I1 or more, especially 0.1 mol/7!
~0.4 mol/7! It is particularly preferable that

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

Specific examples are shown below, but the invention is not limited to these. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid,
N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N'N'-tetramethylenephosphonic acid, 1
．． 3-Diamino-2-propatoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediamine orthoacetic acid Hydroxyphenylacetic acid, 2-butane-1,2,
4-1-licarboxylic acid, 1-hydroxyethylidene-1,
1-diphosphonic acid, N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, catechol 3.4.6-trisulfonic acid, catechol-3゜5
-disulfonic acid, 5-sulfosalicylic acid, 4-sulfosalicylic acid. Two or more of these chelating agents may be used in combination as necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example 11
It is about 0.1g to 10g per serving.

Any development accelerator can be added to the color developer if necessary.

As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 3B-7826, No. 41-123
No. 80, No. 45-9019 and U.S. Patent No. 3,813
, p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554;
No. 137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 1977
Quaternary ammonium salts shown in No. 6-156826 and No. 52-43429, etc., U.S. Patent No. 2,610
, 122 and 4,119°462; U.S. Pat. No. 2,494,903;
No. 3,128,182, No. 4,230,796, No. 3. No. 253゜919, Special Publication No. 11431-1973,
U.S. Patent Nos. 2,482,546 and 2,596,92
Amine compounds described in No. 6 and No. 3,582,346, etc., Japanese Patent Publication No. 37-16088, No. 4225201
No., U.S. Patent No. 3.128.183, Japanese Patent Publication No. 4111
No. 431, No. 42-23883 and U.S. Pat.
Polyalkylene oxides such as those represented by No. 532.501, 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, and the like can be added as necessary.

Preferably, the color developer is substantially free of benzyl alcohol. Substantially means 2 per 1 e of color developer.
．． 0 mj2 or less, more preferably no content at all. When it is not substantially contained, fluctuations in photographic properties during continuous processing are smaller, and more preferable results can be obtained.

In the present invention, an arbitrary antifoggant can be added in addition to chloride ions and bromide ions, if necessary. As antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6
-Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2
Representative examples include nitrogen-containing heterocyclic compounds such as -thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, imidazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention preferably contains a fluorescent brightener. As a fluorescent whitening agent, 4.4'-
Diamino-2,2'-disulfostilbene compounds are preferred. The amount added is 0 to 10 g/l, preferably 0.1 to 1.
It is 6g/β.

Moreover, various surfactants such as alkylsulfonic acid, alkylphosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid 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. Processing time is 20 seconds to 5 minutes.
The preferred time is 30 seconds to 2 minutes.

Usually, in color development, the developer is replenished.

The amount of replenishment depends on the photosensitive material to be processed, but is generally about 180 to 10,100 O per square meter of the photosensitive material. Replenishment is a means for keeping the components of the color developer constant in a development processing method in which a large amount of light-sensitive material is continuously processed using an automatic developer or the like in order to avoid changes in development finish characteristics due to changes in component concentration. Replenishment inevitably generates a large amount of overflow liquid, and from economic and pollution standpoints, it is preferable that the amount of replenishment be small. This preferred replenishment amount is 20 to 150 m7 per 1M of photosensitive material! It is.

Although it varies somewhat depending on the photosensitive material, the replenishment amount of 20 ml per 1 d of photosensitive material is an amount where the amount of processing liquid taken out by the photosensitive material and the replenishment amount are approximately equal, and overflow is substantially eliminated. The present invention is effective even in such low replenishment processing.

In the present invention, desilvering treatment is performed after color development. The desilvering step generally consists of a bleaching step and a fixing step, but it is particularly preferable that they are carried out simultaneously.

The bleach or bleach-fix solutions used in the present invention may contain bromides (e.g., potassium bromide, sodium bromide, ammonium bromide), or chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride), or iodine. monster(
For example, a rehalogenating agent such as ammonium iodide) may be included.

If necessary, one or more types of materials having pH buffering ability such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Inorganic acids, organic acids and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate, guanidine, etc. can be added.

The fixing agent used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, namely sodium thiosulfate,
Thiosulfates such as ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; thioether compounds such as ethylene bisthioglycolic acid and 3,6-cythia-1,8-octanediol; These are silver halide solubilizers, and these can be used alone or in combination of two or more. It is also possible to use a special bleach-fix solution made of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354. In the present invention, preference is given to using thiosulfates, especially ammonium thiosulfates. The amount of fixing agent per 11 is preferably in the range of 0.3 to 2 moles, more preferably in the range of 0.5 to 1.0 moles.

The pl (range) of the bleach-fix solution or fixer in the present invention is preferably 3 to 10, and more preferably 5 to 9. If the pH is lower than this, the desilvering property improves, but the deterioration of the solution and the cyan dye On the other hand, if the pH is higher than this, desilvering is delayed and staining is more likely to occur.

In order to adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary.

Further, the bleach-fix solution may contain various other optical brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fix solution and fixer solution used in the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite,
ammonium sulfite, etc.), bisulfites (e.g. ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfites (e.g. potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) ) and other sulfite ion-releasing compounds. These compounds are approximately 0.0 in terms of sulfite ion.
The content is preferably 2 to 0.50 mol/l, more preferably 0.04 to 0.40 mol/l.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Sulfinic acids, carbonyl compounds, sulfinic acids, etc. may be added.

Furthermore, buffering agents, fluorescent brighteners, chelating agents, antifungal agents, etc. may be added as necessary.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization process after fixing or desilvering treatment such as bleach-fixing.

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 (the number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. this house,
The relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal on the Society on Motion.
Picture and Television Engineers (
Journal of the 5ociety of
Motion Picture and Te1evi
sion Engineers) Volume 64, p. 248
-253 (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. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium and magnesium described in Japanese Patent Application No. 61-131632 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds and thiabendazoles, chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A No. 57-8542, "Chemistry of antibacterial and antifungal agents" by Hiroshi Horiguchi, It is also possible to use disinfectants described in Sanitary Technology Wire Mesh "Sterilization, Disinfection, and Anti-Mold Technology of Microorganisms" and "Encyclopedia of Antibacterial and Anti-Mold Agents" by Japan Antibacterial and Anti-Mold Science Wire Mesh.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 1.
0, 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 25 to 45°C.
A range of 30 seconds to 5 minutes at ~40°C 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 treatment, Japanese Patent Application Laid-Open Nos. 57-8543 and 5B-1
No. 4834, No. 59-184343, No. 60-220
No. 345, No. 60-238832, No. 60-2397
No. 84, No. 60239749, No. 61-4054,
All known methods described in 61118749 and the like can be used. Especially l-hydroxyethylidene-
A stabilizing bath containing 1,1-diphosphonic acid, 5-chloro-2methyl-4-isothiazolin-3-one, a bismuth compound, an ammonium compound, etc. is preferably used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, and an example of this is used as a final bath for color photosensitive materials for photographing. Stabilizing baths containing formalin and surfactants may be mentioned.

The processing time of the present invention is defined as the time from when the photosensitive material comes into contact with the color developer until it exits the final bath (generally water washing or stabilization bath).
The effects of the present invention can be significantly exhibited in a rapid treatment process in which the processing time is 30 minutes or less, preferably 4 minutes or less.

Next, the silver halide color photographic material used in the present invention will be explained in detail.

The silver halide emulsion of the present invention has a silver chloride content of 80 mol % or more, preferably 95 mol % or more, and more preferably 98 mol % or more based on the total amount of silver halide. From the point of view of rapidity, the higher the silver chloride content, the better. Further, the high silver chloride composition of the present invention may contain a small amount of silver bromide or silver iodide. This may have many useful benefits in terms of photosensitivity, such as increasing the amount of light absorption, strengthening the adsorption of spectral sensitizing dyes, or weakening desensitization caused by spectral sensitizing dyes.

The silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may have a uniform grain structure as a whole. It may consist of phases. Moreover, they may be mixed.

Silver halide grains in photographic emulsions include those with regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

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 (RD), No. 17643.
(December 1978), pp. 22-23, “1. Emulsion preparation and
It can be prepared using the method described in "Types".

U.S. Special Kitsuki No. 3,574.628, No. 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Tokukitsuki 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 in Cutoff, Photographic Science and Engineering.
engineering), 1st
Volume 4, pp. 248-257 (I970); US Special Kitsuki 4
．． No. 434226, No. 4,414.310-, No. 4,
It can be easily prepared by the method described in No. 433.048, No. 439,520, and British Tokukitsuki No. 2,112.157.

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

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 ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure Section 17.
643 and No. 18716, and the relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Addition Type 1 Chemical sensitizer 2 Sensitivity enhancer 3 Spectral sensitizer, super sensitizer 4 Brightener 5 Anti-fogging agent and stabilizer 6 Light absorber, filter dye Ultraviolet absorber Anti-stain agent Dye image stabilization Hardener Binder Plasticizer, Lubricant Coating Aid, Surface Active Agent 13 Static Inhibitor RD17643 Page 23 Page 23-24 Page 24 Page 24-25 Page 25-26 Page 25 Page Right Column Page 25 Page 26 Page 26 Page 27 26-27 True 27 pages RD18716 648 pages right column Same as above 648 pages right column ~ 649 pages right column 649 pages right column ~ 649 right column ~ 650 pages left column 650 pages left to right 651 pages left column Same as above 650 pages right column Same as above Same as above Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) Na17643, described in the patents listed in ■-C to G.

As a yellow coupler, for example, U.S. Patent Tube 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4.401752, Special Publication Show 5B
-1,0739, British Patent No. 1,425,020,
Same 1st. 476, 760, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0,619, No. 4,351°897, European Patent No. 73,636, US Patent No. 3.061.432, No. 3. 725. No. 064, Research Disclosure 11h24220 (June 1984), Japanese Unexamined Patent Publication No. 6
(No. I-33552, Research Disclosure N
124230 (June 1984), Japanese Patent Application Publication No. 6 (I436)
No. 59, U.S. Patent No. 4,500,630, U.S. Patent No. 4.5
No. 40.654, No. 4,556,630, WO(P
CT) 88104795 and the like are particularly preferred.

Examples of cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Patent No. 4052.212, U.S. Patent No. 4,146,396, and U.S. Patent No. 4,228,233.
No. 4,296,200, No. 2,369,92
No. 9, No. 2,801.171, No. 2,772.1
No. 62, No. 2,895,826, No. 3,772,
No. 002, No. 3.758,308, No. 4.334
．． No. 011, No. 4.327.173, West German Patent Publication No. 3,329,729, European Patent No. 121.365A
No. 3,446,622, U.S. Patent No. 4,333
, No. 999, No. 4.451.559, No. 4.42
No. 7,767, No. 4,690,889, No. 4,2
Preferred are those described in No. 54,212, No. 4,296,199, European Patent No. 161.626A, Japanese Patent Application Laid-Open No. 61-42658, and the like.

Colored couplers for correcting unnecessary absorption of coloring dyes are recommended in Research Disclosure 17643.
- Section G, U.S. Patent No. 4,163゜670, Special Publication No. 1983
-39413, U.S. Patent No. 4.0.04,929,
Same No. 4. 138. No. 258, British Patent No. 1.146
, No. 368 is preferred.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2.125.
．． 570, European Patent No. 96.570 and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820; U.S. Pat. No. 4,080.211; U.S. Pat.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
■-Patent listed in Section F, JP-A-57-151944
Preferred are those described in No. 5'1154234, No. 60-184248, and U.S. Pat.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097.140;
No. 2.131.188, JP 59-157638
No. 59-170840 is 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. , the multi-light coupler described in JP-A No. 4,310,618, etc., JP-A-185950
Examples thereof include DIR redox compound-releasing couplers described in No. 1, No. 1, and European Patent No. 173,302A, and couplers that release night-colored dyes after separation, as described in European Patent No. 173,302A.

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-ice dispersion method are described in US Pat. No. 2,322.027 and the like.

Examples of latex dispersion process steps, effects, and latex for impregnation include U.S. Pat. It is described in.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of 17643 and 1lkL1871G
It is written from the right side of page 647 to the left column of page 648.

(Examples) Examples of the present invention will be specifically shown below, but the present invention is not limited thereto.

Example 1 A multilayer color photographic paper (01) 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.

150 c of ethyl acetate was added to 60.0 g of yellow coupler (ExY) and 28.0 g of antifading agent (Cp, d-1) to prepare the coating solution for the first layer.
c and 1.0 cc of solvent (Solv-3) and solvent (So
1v-4) 3.0 cc was added and dissolved, and this solution was added to 450 cc of a 10% gelatin aqueous solution containing sodium dodecylbenzenesulfonate, and then dispersed using an ultrasonic homogenizer. Silver chlorobromide emulsion containing sensitizing dye (silver bromide 0.7 mol%) 42
A first layer coating solution was prepared by mixing and dissolving 0g. Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. 1.2bis(vinylsulfonyl)ethane was used as the gelatin hardening agent for each layer.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer; anhydro-5-5'-dichloro 3.3
'-Disulfoethyl thiacyanine hydroxide green-sensitive emulsion layer; anhydro-9-ethyl-5,5'diphenyl-3,3'-disulfoethyl oxacarbocyanine hydroxide red-sensitive emulsion layer; 3,3'-diethyl -5-methoxy-9
, 9'-(2,2'-dimethyl-1,3-propano)thiatribocyaniodide The following substances were also used as stabilizers for each emulsion layer.

-disulfonatophenyl)-2-pyrazolin-4yritene)-1-propenyl)-1-pyrazolyl]benzene-2,5-disulfonate-disodium salt N,N'-(4,8-dihydroxy-9,10dioxo -3,7-cissulfonathanethracene 1,5-diyl)bis(minomethanesulfonate)-tetrasodium salt [3-cyano-5-hydroxy-4-(3(3-cyano-5-oxo-1 -(4-sulfonatophenyl)-2-
Pyrazolin-4-ylidene)1-pentanyl)-1-pyrazolylubenzene 4-sulfonato sodium salt and the following were used as anti-irradiation dyes.

[3-Carboxy-5-hydroxy-4-(3(3-carboxyl5-oxo-1-(2,5 (layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/durability) .Silver halide emulsion represents the coating amount in terms of silver.

Support Paper laminated on both sides with polyethylene Support Layer (blue sensitive layer) Silver halide emulsion (AgBr: 0.7 mol%, cubic average grain size 0.9μ) 0.27 Gelatin 1.80 Yellow coupler (ExY ) 0.61 Anti-fading agent (Cpd
-1) 0.28 solvent (So 1v-3)
0.015 solvent (Solv-4)
0.03 Second layer (color mixing prevention layer) Gelatin 0.80 Color mixing prevention agent (Cpd-2) 0.055 Solvent (Sol
v-1 > 0.03 solvent (So 1v-
2) 0.015 Third layer (green sensitive layer) Silver halide emulsion (AgBr: 1.2 mol%, cubic grain size 0.45μ) 0.28 Gelatin 1.40 Magenta coupler (EXM) 0.65 Anti-fading Agent (Cpd
-3) 0.14 solvent (Solv-1)
0.20 Solvent (Solv-2) Fourth layer (color mixing prevention layer) Gelatin color mixing prevention agent (Cpd-2) Ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) Solvent (Solv-1) Solvent ( Solv-2) Fifth layer (red-sensitive layer) Silver halide holes 1f'l (AgBr: 2 mol%,
Size 0. 5μ) Gelatin cyan coupler (ExC-1) Cyan coupler (ExC-2) Antifading agent (Cpd-1) Solvent (Solv-1) Solvent (Solv-2) Compound (Cpd-4) Sixth layer (ultraviolet absorption layer) ) Gelatin 0,02 1,70 0.085 0,45 0,23 0,05 0,05 Cubic particles 0.19 1.80 0.26 0.13 0.23 0.14 0.10 0.13 0 , 70 Ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) Solvent (Solv-1) Solvent (Solv-2) Seventh layer (protective layer) Gelatin 1,07 Noxy)-3-methylbutyramidephenol (ExC
-2) Cyan coupler 2,4-dichloro-3-methyl-6-[α(2,4-di-tert-amylphenoxy)butyramide]phenol (Ex Y) yellow coupler α-pivalyl α-(3-benzyl- 1-hydantoinyl)-2-chloro-5-[β-(dotecylsulfonyl)
Butylamitocoacetanilide (Cpd-1) Antifading agent 2,5-di-tert-amylphenyl-3゜5-te-tert-7' hydroxybenzoate (ExM) Mazenk coupler 1- (2,4,6-di chlorophenyl)-3[2-
Chloro-5(3-ocdadecenylsuccinimide)anilino]-5-pyrazolone (ExC-1) Cyan coupler 2-pentafluorohenzamide 4-chloro (Cpd-2) Color mixing inhibitor 2.5-Z-tert- Octylhydroquinone (Cpd-3) Antifading agent 5 [1-(2,4-di-tert-amylphene (Cp
d-4) Di(2-ethylhexyl) phthalate p-(p-dodecylphenylsulfonamide) toluene (Solv-3) Solvent di(i-nonyl) phthalate (Solv-4) Solvent N,N-diethylcarbonamidomethoxy- 2゜4-di-monoamylbenzene (UV-1) UV absorber 2-(2-hydroxy-3,5-di-tert-amyl phenyl)benzotriazole (UV-2) UV absorber 2-(2-hydroxy -3,5-dibutylphenyl)benzotriazole ert (Solv-1) Solvent (Solv-2) Solvent dibutyl slate (Preparation of color photographic paper 02) In the third layer of color photographic paper 01, as an anti-fading agent, Color photographic paper 02 was prepared in the same manner as color photographic paper 01 except that 0.25 g/I of the following comparative compound (A) was added.

(Preparation of color photographic paper 03) The amount of silver halide emulsion in the first layer of color photographic paper 01 was set to 0.
．． 31 g/n (in which the amount of silver halide emulsion in the third layer was 0)
．． The amount of silver halide emulsion in the fifth layer was 0.34 g/m.
21g/%, and further added 0.25g/n of the following comparative compound (A) as an anti-fading agent.
Color photographic paper 03 was produced in the same manner as in Example 2.

(Preparation of Color Photographic Paper 04) In the third layer of Color Photographic Paper 03, the compound of the present invention (A-48) was added as an antifading agent instead of the comparative compound (A) below.
Color photographic paper 04 was produced in the same manner as color photographic paper 03 except that 0.23 g/duration was used.

(Preparation of Color Photographic Paper 05) In the third layer of Color Photographic Paper 01, 0.0% of the compound of the present invention (A-48) was added as an anti-fading agent. 23 g/
Color photographic paper 05 was produced in the same manner as color photographic paper 01 except that n( was added.

(Preparation of color photographic papers 06 to 14) In the same manner as color photographic paper 05, compounds of the present invention (A-
2), (A-7), (A-21), (A27), (A-
39), (A-42), (A50), (A-54), and (A-72) were added at 0°23 g/m to color photographic paper 06 to 14 in the same manner as color photographic paper 05. was created.

(Preparation of color photographic paper 15 and 16) Color photographs were made except that the silver halide emulsion compositions of the silver halide emulsions in the first, third and fifth layers of the color photographic paper 14 were changed as shown in Table 1. Color photographic papers 15 and 16 were produced in the same manner as paper 14.

(Preparation of color photographic paper 17) A color print was made in the same manner as color photographic paper 01 except that 0.23 g/M of the following comparative compound (B) was further added to the third layer of color photographic paper 01 as an antifading agent. Paper 17 was produced.

Comparative Compound (A) Comparative Compound (B) The following experiments were conducted on the above color photographic papers (01) to (I8).

First, using a photosensitive needle (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3200K) on the coated sample,
Provided gradation exposure for sensitometry. The exposure at this time was carried out at an exposure time of 1/1O second and an exposure amount of 250 CMS.

Next, the above sample was subjected to the following treatment process and the following treatment liquid composition (A
) was processed. Further, the same treatment was performed using the treatment liquid composition (B). However, the chlorine ion concentration and bromide ion concentration of the color developer were changed as shown in Table 1 below.

Yellow maximum color density (Y
-DIIla×) is summarized in Table 1 as an index of color development. In addition, as an index of processing dependence, the decrease in density (△Dy) when processing with the processing liquid composition (B) at the exposure amount that gives a yellow density of 1.0 with the processing liquid composition (A)
are summarized in Table 1.

In addition, after treatment with the treatment liquid composition (A), irradiation was performed for 450 hours with a xenon fade meter (45,000 Lux), and the increase in yellow density of the white background area (△d
y) and the image survival rate (△D, ) at Mazenk initial density = 2.0, and the image survival rate (△D, ) at cyan initial density DC = 2.0 when left in a dark room at 90°C for 150 hours. DC) are summarized in Table 1 as an index of image storage stability.

1 temperature Color development 38℃ Bleach fixing 30-36℃ Rinse■ 30~37"C Rinse■ 30-37°C Rinse■　　　30~37℃ Dry 70-80℃ Ridge-hard 45 seconds 45 seconds 30 seconds 30 seconds 30 seconds 60 seconds The composition of each treatment liquid is as follows.

Left support and two bellies Shu Bingsui 800m
7! Ethylenediamine-N,N.

N,N-tetramethylenephosphonic acid 3.0 g diethylhydroxylamine Sodium chloride as below
See Table 1 Potassium bromide
See Table 1 Potassium carbonate 19
．． 0 g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0 g triethanolamine 10.0 g Fluorescent brightener (4,
4'-diaminostilbene type) 2.0g sodium sulfite 0.13g water added
1000mApH (25℃)
10.05 Bleach-fix solution water 400m
Ammonium 6thiosulfate (70%) 100mj!
Sodium sulfite 17g Iron (I) ethylenediaminetetraacetate Ammonium 55g Ethylenediaminetetraacetic acid disodium 5g Ammonium bromide 40g Glacial acetic acid
Add 9g water
1000ml pH (25℃)
5.40 units of ion exchange water (3 ppm each of calcium and magnesium)
(below) However, the amount of diethylhydroxylamine in the color developer is 3.1 g/β for A treatment and 5.7 g/β for B treatment.
j! shall be.

It can be seen from Table 1 that by specifying the halogen composition, antifading agent, coating silver amount, and halogen ion of the present invention, color development, processing dependence, and image storage stability can all be solved.

As can be seen from the comparison of A and Z when no anti-fading agent is used and when a comparative anti-fading agent is used, as well as the comparison of B, C, and D, the chlorine ion concentration and bromide ion concentration are Even within the scope of the invention, the processing dependence (ΔDy) can be improved (the range of variation becomes smaller) without significantly lowering the color development property (yellow maximum color density; ΔDmax). However, an increase in staining (increase in Δdy) due to light is observed, which is a problem. This is because the amine compound used for comparison as an anti-fading agent worsens when added (B, C, D), but it is reduced when the compound of the present invention is used. , it can also be seen from the comparison of I. This light stain is A, B, ZXD
As can be seen from the comparison of . I understand. Furthermore, when the combinations of the present invention (■ and others) were used, the treatment dependence, which could not be sufficiently improved with the comparative antifading agents, could be significantly improved.

This effect was unexpected.

Example 2 A multilayer color photographic paper (51) 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.

19.7 g of yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1) and 0.7 g of (Cpd-7)
27.2 cc of ethyl acetate and solvent (Solv-3
) was added and dissolved.

This solution was emulsified and dispersed in 18°5 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. - A force field silver bromide emulsion (cubic average grain size 0.88μ, grain size distribution coefficient of variation 0.08, containing 0.2% mol of silver bromide on the grain surface) was coated with the blue-sensitive sensitizing dye shown below. Sulfur sensitization was prepared after addition of 2.0 x 10-' moles per mole of each. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below. The gelatin hardening agent for each layer is 1-oxy-3,5-dichloro-3-
Triazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer 5O5 SO,H (CH2)4 (CH2)3 o3 o3H (2.0 x 10 mol each per mol of silver halide)
(4.0X10-' moles per mole of silver halide) and SOs S03 H-N (Cz Hs)i (
7.0 x 10-' mol per mol of silver halide)
-(5-methylureidophenyl)5-mercaptotetrazole at 8.5X per mole of silver halide, respectively.
10-5 mol, 7.7XIO-' mol, 2.5X10-
'Mole added.

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

For the C2H5 Cs HI (halogen (0.9X10-' mole per mole of IJII) red-sensitive emulsion layer, 2.6X10-3 moles of the following compound was added per mole of silver genide.

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

Support polyethylene laminated paper [white pigment (T i O□) on the polyethylene on the first layer side
and bluish dye (ulmarine)] Layer 1 (blue-sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-
1) 0.19? Container (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 (Sol
v-1) 0.16? Container (Solv
-4) 0. 08 Fifth layer (green sensitive layer) Silver chlorobromide emulsion (1:3 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).

Coefficient of variation of particle size distribution 0.10.0.08, A
0.8 mol % of g B r was locally contained on the particle surface. 0.12 gelatin
1.24 Magenta Coupler (ExM) 0.
23 color image stabilizer (Cpd-3) 0.13
Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Volume (So
lv-2) 0.54 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixture prevention agent (
Cpd-5) 0.05 Solvent (Solv-5
) 0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (1=4 mixture of one with a cubic average grain size of 0.58μ and one with a cubic average grain size of 0.45μ (Ag molar ratio). Coefficient of variation of grain size distribution 0.09.0.11 each, AgB
0.6 mol % of r was locally contained in a part of the particle surface.

0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (
Cpd-6) 0.17 color image stabilizer (Cp
d-10) 0. 04 color image stabilizer (Cp
d-7) 0.40 solvent (Solv-6)
0.15 Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixture prevention agent (
Cpd-5) 0.02 Solvent (Solv-5
) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic of polyvinyl alcohol 0.17 Modified copolymer (degree of modification 17%) Liquid paraffin 0.03 (ExY
) Yellow coupler (ExM) Magenta coupler R=H, C2H5, Cs Hq 1:3:6 mixture by weight, respectively (Cpd ■) Color image stabilizer (Cpd Color mixture prevention agent (Cpd Color image stabilizer (Cpd Color image stabilizer) agent (compound A of the present invention (Cpd color image stabilizer (Cpd color image stabilizer -eCH2-CHh CONHCa He(t) average molecular weight 60.000 (Cpd color image stabilizer (Cpd color image stabilizer Solvent (Preparation of color photographic paper 52) Anti-fading agent (Cpd-3) for the third layer of color photographic paper 51
Color photographic paper 52 was produced in the same manner as color photographic paper 51 except that .

(Production of color photographic paper 53) Antifading agent (Cpd-3) in the third layer of color photographic paper 51
Color photographic paper 53 was produced in the same manner as color photographic paper 51, except that the same weight of Comparative Compound (A) of Example 1 was substituted.

(Preparation of color photographic papers 54 to 60) Antifading agent (Cpd-3) in the third layer of color photographic paper 51
Compounds (A-4), (A-19), (A-2) of the present invention
5) Color photographic papers 54 to 60 were produced in the same manner as color photographic paper 51 except that equal weights were replaced with (A-27), (A-31), (A-50), and (A-66). did.

The following experiments were conducted on the above color photographic papers (51) to (60).

In addition, regarding the color photographic paper (51), a photosensitive needle (FWH type manufactured by Fuji Photo Film Co., Ltd., light source color temperature 3200°)
K) to give gradation exposure for sensitometry,
Processing was carried out according to the following processing steps until the amount of color developer replenished was twice the tank capacity. Thereafter, the color photographic papers (51) to (60) are processed using the processing solution after running (Processing A). However, the chlorine concentration and bromide ion concentration of the color developer were changed as shown in Table 2.

After treatment, xenon fade meter (45,000Lu
x), after 450 hours of irradiation, the increase in yellow density (△Dy) in the white area and the initial magenta? Table 2 shows the color image density residual rate (△D,) at a density of 2.0.
summarized in.

In addition, the pH of the color developer after the running was adjusted to 9.8.
0 and processed the color photographic papers (51) to (60) (processing B). Magenta density decreased in processing A, -2,
The magenta density (D
M2. . ) are summarized in Table 2 as indicators of treatment dependence.

lW No Kai 11” Tank capacity 73+n 1 4 (I 2L5+n e 41 2ρ 2ρ 250m A 2fl Shoka process　■　　neck Color development 38℃ 45 seconds Bleach fixing 30-36℃ 45 seconds Stable ■ 30-37°C 0 seconds Stable ■ 30-37℃ 0 seconds Stable ■ 30-37°C 0 seconds Drying 70-85℃ 60 seconds *Photosensitive material 1rI? Refill amount per (It was a 4-tank countercurrent force type to stabilize ■-■.

The composition of each treatment liquid is as follows.

Water ethylenediaminetetraacetic acid 5.6-cyhydroxybenzene-1. 2. 4 Trisulfonic acid triethanolamine sodium chloride 00m A 5.0g 800ml 5.0g 0.3g 0.3g 8.0g 8.0g Potassium bromide, see Table 2 Potassium carbonate, see Table 2 25 g 25 gN-Ethyl -N-(β-methanesulfonamidoethyl) 3-methyl-4-aminoaniline sulfate 5.0g 15.0g
Diethylhydroxylamine 0.03mol 0.
05mol Sodium sulfite 0.1g
0.2g optical brightener 1. Og
Add 3.0g water and 1000m
l11000m 12pH (25℃)
10.05 10.65 Bleach-fix solution (tank solution and replenisher are the same) water
400mβ1000 ammonium sulfate (70%>
LOOmk Sodium Sulfite 17
gEthylenediaminetetraacetic acid iron(I) ammonium 55gethylenediaminetetraacetic acid disodium 5g glacial acetic acid
Add 9g of water to pT ((25~℃) Kosadatatsu (tank solution and replenisher are the same) Formalin (37%) Formalin-sulfite adduct 5-chloro-2-methyl-4 Isothiaprin-3-one 2 -Methyl-4-isothiazolino-3-one Cupric ammonium sulfate water (28%) Add water to pH (25°C) 1 000 mn 5, 40 0, 1 g 0, 7 g 0.02 g 0.01 g 0.005 g 2, 0 mρ 1000 m7! 4.0 As can be seen from the comparison between the experiment and E in Table 2, even if the chlorine ion concentration and bromide ion concentration were within the range of the present invention, no particular effect on color development (YDmax) was observed. ,DM,
,. The fact that the value of is close to 2.0 also indicates that the processing dependence tends to improve. However, in that case, an increase in stain (ΔDy) due to light is observed. On the other hand, when the combination of the present invention is used, it is recognized that both processing dependence and image storage stability are good.

Claims (1)

Scope of Claims: A method of processing a silver halide color light-sensitive material with a color developer containing at least one aromatic primary amine color developing agent, wherein the silver halide color light-sensitive material contains 80 mol%. having at least one layer of a silver halide emulsion made of the above silver chloride, and a layer containing at least one compound represented by the following general formula (I),
and the total coating silver amount is 0.75 g/m^2 or less, and the color developer has a chloride ion concentration of 3.5 x 10^-^2 to 1
．． Contains 5 x 10^-^1 mol/l and bromine ion at 3.0 x 10^-^5 to 1.0 x 10^-^3 mol/l
A method for processing a color photographic material containing silver halide. General Formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, R_1 represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. R_2, R_3, R_4, R_5 and R_6 may be the same or different, and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a halogen atom,
-OR'_1, -SR'_1, ▲Mathematical formulas, chemical formulas, tables, etc.▼, sulfonyl group, sulfinyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, cyano group, nitro group, carbamoyl group, sulfamoyl group and formyl group. R'_1 represents the same meaning as R_1. R_7 and R
--8 may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a carbamoyl group, and a sulfonyl group. OR_1, R_2, R_3, R_4, R_5 and R_
The groups at ortho positions of 6 may be bonded to each other to form a 5- to 7-membered ring, or R_7 and R_8 may be bonded to each other to form a 5- to 7-membered ring.