JPH01187554A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable rapid processing and to obviate bleach fogging by incorporat ing a specific compd. into a color developing agent for processing high-chloride silver halide and specifying the pH of a bleach-fixing bath. CONSTITUTION:The compd. expressed by the formula I is incorporated into the color developing soln. to be used for color development of a silver halide emulsion layer contg. silver halide particles consisting of >=80mol.% silver chloride and the pH of the bleach-fixing bath is specified to a 4.5-6.8 range. In the formula I, R<1>-R<3> respectively independently denote a hydrogen atom, alkyl group, etc.; R<4> denotes a hydrogen atom, hydroxy group, etc.; X<1> denotes a bivalent group, n denotes 0 or 1. R<4> denotes an alkyl group, aryl group or heterocyclic group when n=0. The processing of the silver halide color photo graphic sensitive material which has the rapid developability and is less fogged in the bleach-fixing bath is thereby enabled.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and more specifically, it enables rapid processing and has improved processing stability in the rapid processing. The present invention relates to a method for processing silver halide color photographic materials.

(Prior Art) In recent years, there has been a growing desire in the industry for a technology that enables rapid processing of silver halide color photographic materials, has excellent processing stability, and provides stable photographic quality. ,
In particular, a method for processing silver halide color photographic materials that can be processed quickly is desired.

In other words, silver halide color photographic materials are subjected to running processing in automatic processing machines installed in each laboratory, but as part of an effort to improve service to users, processing is carried out on the same day that processing is received. In recent years, there has been a demand for refunds to be returned to the user within a few hours of receipt, and there is an urgent need to develop technology that can process items more quickly.

Looking at the conventional techniques for rapid processing of silver halide color photographic materials, (I) technology based on improvement of silver halide color photographic materials, (2) technology using physical means during phenomenon processing, (3) (1) Techniques by improving the composition of the processing solution used in the current processing; microparticle technology and JP-A-5R-IT3) Hiroλ,
technology for reducing the silver bromide of silver halide as described in Shikosho J.
-1≠A technique for adding /-aryl-3-pyrazolidone having a defined structure as described in No. 332 to a silver halide color photographic light-sensitive material and JP-A-Sho! 7-7≠≠! Hiro 7,
Same 3l-jOj? 3≠ issue, 3l-4033j, 5
r-tθj'36 (technique for adding /-ary-rubi-2-zolidones into silver halide color photographic light-sensitive materials), ■ technology using fast-reactive couplers (for example, Japanese Patent Publication No. Shoj/-8071rJ, Japanese Patent Publication No. 70-/λ33II2
2. Thinning of photographic constituent layers (for example, thinning of photographic constituent layers described in JP-A-62-TZO≠θ) Regarding (2) above, there are processing liquid stirring techniques (for example, the processing liquid stirring technique described in JP-A-62-/r03t), etc., and regarding (3) above, there are processing liquid stirring techniques. , (2) A technique using a development accelerator, (2) A technique for concentrating a color developing agent, (2) A technique for reducing the concentration of halogen ions, especially bromide ions, etc. are known.

Processing of light-sensitive materials basically consists of two steps: color development and desilvering, and desilvering consists of bleaching and fixing steps or bleach-fixing steps. In addition to this, additional processing steps such as rinsing treatment, stabilization treatment, washing with water or stabilization treatment as an alternative to washing with water, etc. are added. That is, in color development, the exposed silver 780 is reduced to silver, and at the same time the oxidized aromatic primary amine developing agent reacts with the coupler to form a dye. During this process, halogen ions generated by reduction of silver halide are eluted into the developer and accumulated.

Additionally, components such as inhibitors contained in the light-sensitive material are also eluted into the color developer and accumulated. In the desilvering step, silver produced by development is bleached with an oxidizing agent, and then all silver salts are removed from the photosensitive material as soluble silver salts with a fixing agent. Furthermore, this -! − Bleaching process and fixing process? A one-bath bleach-fixing method is also known in which all the components are treated simultaneously.

Among the rapid processing techniques mentioned above (fl), techniques using halogenated light-sensitive materials containing silver halide grains made of high concentration silver chloride (for example, Japanese Patent Application Laid-Open No. 1983-1999-YR Jat No. 60-/9/1999) No. 440, R-23736, etc.) provides excellent speed-up performance for poetry. However, it has been found that when such photosensitive materials containing high silver chloride are used, so-called bleaching edge blur tends to occur.

Recently, due to the recent demand for low pollution and cost reduction, there is a trend towards low replenishment or high regeneration rate of bleach-fix solutions, and in such cases, the amount of color developer accumulated in the bleach-fix solution is decreasing. are increasing. In other words, if the bleach-fix solution is refilled at a low rate or regenerated at a high rate, the effects of evaporation and regeneration operations, or differences in the throughput of photographic light-sensitive materials (for example, the difference between the beginning of the week when the number of orders is high and the weekend when the number of orders is low) may be affected. The amount of color developer in the bleach-fix solution increases due to the difference in processing amount or the difference in processing amount between high season and off season, etc.).

Under such circumstances, the photographic properties deteriorate significantly, such as bleaching blade blur becoming even larger, and conventionally known techniques (for example, Japanese Patent Application Laid-Open No. 31.03/1999, British Patent No. 1,
/3/, No. 333, U.S. Pat.

Another problem is that photosensitive materials containing high silver chloride, which is an extremely effective speed-up technology, contain hydroxylamines (usually used as preservatives for color developing agents) in color developers. When it is included, a silver development reaction occurs and a sufficient dye density cannot be obtained. However, although sufficient dye density can be obtained by removing the preservative hydroxylamine from the color developer, the color developer becomes extremely unstable, and the color developer is followed by a bleach-fixer. When processing with bleach, the disadvantage is that it is extremely easy to cause burrs. They are in a relationship of arising.

Furthermore, World Publication Patent W01780≠1317 and Shokai Sho t2-241tO≠ No. 3 disclose a technique in which all N,N-dialkylhydroxylamines are used in order to solve the above problem. The effect cannot be said to be sufficient.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to provide a silver halide color that uses high chloride silver halide to provide rapid development properties and has less fog in a bleach-fix solution. The purpose of the present invention is to provide a method for processing photographic materials. A third object of the present invention is to provide a method for processing a silver halide color photographic material in which staining is less likely to occur even when a bleach-fix solution is replenished at a low level (even when a large amount of a color developer is mixed in). . A third object of the present invention is to provide a method for processing silver halide color photographic materials in which fluctuations in maximum density of a processing solution over time are improved.

Other objects of the invention will be apparent from the description herein.

(Means for Solving the Problems) As a result of various studies, the above objective is to provide at least a color development step and
In the method for processing a silver halide color photographic light-sensitive material, which includes a bleach-fixing step following the color development step, the silver halide emulsion layer contains halogenated silver halide grains consisting of 80 moles or more of silver chloride. The silver emulsion layer contains a color developing solution used in the color development step, which contains a compound represented by the following general formula (I), and further contains a pn of the bleach-fix solution used in the bleach-fix step.
≠, t-, g, r.

General formula (I) In the formula, R, R and R each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R is a hydrogen atom, a hydroxy group, a hydrazino group, an alkyl group, an aryl group, It represents a heterocyclic group, an alkoxy group, an aryloxy group, a carbamotyl group or an amine group, Xl represents a covalent group, and n represents O or /. However, when n=O, R4 represents an alkyl group, an aryl group, or a heterocyclic group. R
3 and R4 may jointly form a heterocycle.

IO- The compound of the general formula (I) used in the present invention, that is, the hydrazine analogs consisting of hydrazides and hydrazides, will be explained in detail below.

R1, R2 and R3 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group (preferably a carbon number of 1 to 2
0, such as methyl group, ethyl group, sulfopropyl group, carphokidibutyl group, droxyethyl group, cyclohexyl group, hensyl group, phenethyl group, etc.), substituted or unsubstituted aryl group (preferably 6 to 20 carbon atoms, e.g. phenyl group) , 2,5-dimethoxyphenyl group, 4-hydroxyphenyl group, .2-carboxyphenyl group, etc.) or a substituted or unsubstituted heterocyclic group (preferably a carbon number of 1 to 20, preferably a 5 to 6-membered ring) and contains at least one of oxygen, nitrogen, sulfur, etc. as a hetero atom, such as pyridin-4-yl group, N-acetylbiheridin-4-yl group, etc.).

R4 is a hydrogen atom, a hydroxy group, a substituted or unsubstituted hydrazino group (e.g. hydrazino group, methylhydrazino group, phenylhydrazino group, etc.), a substituted or unsubstituted alkyl group (preferably a carbon number of 1 to 20, e.g. methyl group, ethyl group, sulfopropyl group, carboxybutyl group, hydroxyethyl group, cyclohexyl group, benzyl group, 1-butyl group, n-octyl group, etc.), substituted or unsubstituted aryl group (preferably 6 to 20 carbon atoms) , such as phenyl group, 2,5-dimethoxyphenyl group, 4-
Hydroxyphenyl group, 2-carboxyphenyl group, 2
-carboxyphenyl group, 4-sulfophenyl group, etc.)
, a substituted or unsubstituted heterocyclic group (preferably a carbon number of 1 to 20, preferably a 5 to 6 membered ring, containing at least one of oxygen, nitrogen, and sulfur as a hetero atom. For example, pyridine-4 -yl group, imidazolyl group, etc.) Substituted or unsubstituted alkoxy group (preferably 1 to 20 carbon atoms, such as methoxy group, ethoxy group, methoxyethoxy group, hensyloxy group, cyclohexyloxy group, octyloxy group, etc.), substituted or unsubstituted aryloxy group (preferably 6 to 20 carbon atoms, such as phenoxy group, p-methoxyphenoxy group, p-carboxyphenyl Lp-sulfophenoxy group), substituted or unsubstituted carbamoyl group (preferably 1 carbon number) ~20
゜For example, unsubstituted carbamoyl group, N,N-diethylcarbamoyl group, phenylcarbonyl group, etc.) or substituted or unsubstituted amino group (preferably 0 to 20 carbon atoms)
, for example, an amino group, a hydroxyamino group, a methylamino group, a hexylamino group, a methoxyethylamino group, a carboxyethylamino group, a sulfoethylamino group, an N-phenylamino group, a p-sulfophenylamino group).

Further substituents for R1, R2, R3 and R4 include halogen atoms (chlorine, bromine, etc.), hydroxy groups, carboxy groups, sulfo groups, amino groups, alkoxy groups, amide groups, sulfonamide groups, carbamoyl groups, sulfamoyl groups. groups, alkyl groups, aryl groups, aryloxy groups, alkylthio groups, arylthio groups, nitro groups, cyano groups, sulfonyl) U+:, sulfinyl groups, etc. are preferred, and they may be further substituted.

Xl is preferably a divalent organic residue, specifically, for example, -C0-1-so. -1 and H -C~ are not represented. n is O or 1. However, n=O
In the case, R4 represents a group selected from a substituted or unsubstituted alkyl group, an aryl group, and a heterocyclic group. R
1 and R2 and R3 and R4 may jointly form a heterocyclic group.

When n is 0, at least one of R1 to R4 is preferably a substituted or unsubstituted alkyl group. In particular, R
It is preferable that 1, R2, R3 and R4 are hydrogen atoms or substituted or unsubstituted alkyl groups. (However, R1,
R2, R3, and R4 are never hydrogen atoms at the same time.

) Especially when R1, R2 and R3 are hydrogen atoms and R4 is a substituted or unsubstituted alkyl group, R
When 1 and R3 are hydrogen atoms and R2 and R4 are substituted or unsubstituted alkyl groups, or when R' and R2 are hydrogen atoms and R3 and R4 are substituted or unsubstituted alkyl groups ( At this time, R3 and R4 may jointly form a heterocycle) is preferred.

When n=1, Xl is preferably 100-, and R4
R is preferably a substituted or unsubstituted amino group, and R
1-R3 is preferably a substituted or unsubstituted alkyl group.

The alkyl group represented by R1-R4 preferably has 1 to 80 carbon atoms, more preferably 1 to 80 carbon atoms.
~7. Further, preferable substituents for the alkyl group include a hydroxyl group, a carboxylic acid group, a sulfonic acid group, and a phosphonic acid group. When there are two or more substituents, they may be the same or different.

The compound of general formula (I) includes R', R", R3, R4
may form a bis body, a tris body, or a polymer linked with .

(Specific examples of the compound represented by general formula (I) are listed below, but the present invention is not limited thereto.

(I-1) CH3NHNHCH.

HOOCCH2NHNHCH2C○0HNH2NH(-
CH,)i-NHNH2NH2NHCH2CH20H NH2NH-(CH2)3-3○3H NH,NH-(CH2)4-3O3H NH2NH-(CH2)3-COOH (I-18) NaOOCCHNHNHCHCOONaCH3CH3 NH2NHCH2CH2 COONa NH2NHCH2C○0Na H2NNHCH2CH2SO3Na ■ H2NNHCHC○OH ■ H2NNHCHCOOH "H2NN+cHc○o11)z H2NN+CHCOOH)z H2NNHCHCOOH (I-29) (I-30) (I-31) (C12-N-CH2CH2)- X: y-60= 40 Average molecular weight Approximately 20,000 NH2NH 3O3H2 NHHz NHCNH2 NHZ NHCONI(NH2 NH2NH3O3H NH2NH30□N1(NH2 CH3NHNH3O2NHNHCH3 (I-40) NH2NH3O3H-(CH2)3-NHCONHNH
2(I-42) NH,NHCOCONHNH2 NH,COCONHNH2 (I-54) (I-55) H2NNHCNH-(CH2)6-NHCNHNH2(
I-59) Nap3SCH2CH, NHCNHNH2HOOCCH
2CH2NHCNHNH2NH2NHCOOC2H1 N H2N HCOCH3 (I-66) NH,NHCH2PO3H2 (T-71) (CH3)3CCONHNH2 (CH3) 3 COCN HN H2 (I-77) HOCH,CH25o2NHNH2 (I~ 81) Nap3SCH2CH2C0NHNH□ (I~82) H2NC0NHCH2CHz So □NHNH2H2N
NHCH2CH2PO, H2 -(CH2NCH2CH-)- H2 Specific examples other than the above include pages 11 to 24 of Japanese Patent Application No. 61-170756, pages 12 to 22 of Japanese Patent Application No. 61-171682, and pages 12 to 22 of Japanese Patent Application No. 61-173468. Specification page 9~
Examples of the compounds described on page 19 and the like can be mentioned.

Many of the compounds represented by the general formula (I) are available as commercial products, and are also available from "Organic Syntheses J",
Co11°Vol, 2+ pp 208-213;
Jour, Amer, Chem, Soc.

36.1747 (I914); Oil Chemistry, Dan, 31 (
I975); Jour, Org, Chem, 2
5. 44 (I960); Pharmaceutical Journal, Vol. 1, 112
7 (I971); rOrganic Synthesis j
(OrganicSyntheses)+Co11.
Vol, 1+p450 i 'New Experimental Chemistry Course', 1
Volume 4, I, p1621-1628 (round neck); Be1
1. ．． 2. 559;Be11. ．． 3. 117;
E., BoMohr et al., Inorg.
Syn,, 4. 32 (I953); F,
J. Wilson, E. CoPicker
ing.

J, Chem, Soc,, 123. 394 (I9
23) ;N.

J., Leonard, J.H., Boyer, J.
Org, Chem, +L42 (I950);
``Organic Synthesis'' (Organic 5
yntheses), Co11. Vol.5. p
8055; P, A, S, Sm1th +
rDerwaitives of hydrazine
and other hydrogentro-gens
hav:ngn-n-bonds J.

P120-124. p130-131; THE BIE
NJAMIN/CUMMINGS COMPANY
, (I983); 5taniey R, 5an
dier Waif Xaro, rorganic
Functional Group Preparation
ons”, Vol, 1,5econd Edition
It can be synthesized according to general synthesis methods such as n, p457, etc.

-i The hydrazine or hydrazide represented by formula (I) is preferably 0°01 to 50% per color developer 11.
g, more preferably 0. It is used in an amount of 1 to 30 g, particularly preferably 0.5 to 80 g.

Next, each step of the process of the present invention will be explained.

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

Preferred examples include p-phenylenediamine derivatives, representative examples are shown below, but the invention is not limited thereto.

D-/N, N-diethyl-p-phenylenediamine D-2J-amino-yo-diethylamine toluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl -N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-(β-hydroquinethyl)aminecoaniline D-64-amino-3-methyl-N-ethyl −N−[β
-(methanesulfonamide)ethylcouaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide' D-8N,N-dimethyl-p-phenylenediamine D-94-amino-3-methyl- N-ethyl-N-methoxyethylaniline D-804-amino-3-methyl-N-ethyl-N-β
-ethoxyshetylani-phosphorus D-114-amino-3-methyl-N-ethyl-N-β
-phthoxyethylaniline These p-phenylenediamine derivatives may also be salts such as sulfate, hydrochloride, sulfite, and p-1 luenesulfonate. The amount of the mosquito aromatic-grade amine developing agent to be used is preferably about 0, iy to about 2 of, per developer retentate.
More preferably the concentration is from about 00sr to about ioy.

In addition, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts are added to the color developer as preservatives as necessary. be able to.

However, in order to improve the color development properties of the color developer, it is preferable that the amount of sulfite ion added be small.

In addition, as compounds that directly preserve the color developing agent, various hydroxylamines,
Hydroxamic acids described in No. 1, j/-/It74Aλ
No. and 7 enols described in No. t/-20323, 3,
It is preferable to add α-hydroxyketones and α-ruaminoketones described in the same No. 6/-/117 Hiro/No. 1, and/or various saccharides described in the same No. 6/-/804 It. In addition, in combination with the above compounds, Shigansho t/-/4A71r23, A/-04A
No. 7, same A/-/l! &2/ issue, same J/-/4≠jl
j, A/-/707t, and 4/-/61/
Monoamines described in No. J, etc., No. 4/-/731-5
No., same t/-/ 4 Hirot/ No. 5, same t/-/It
, diamines described in No. j60, etc., A/-/l, jt
λ1, and the polyamines described in the same J/-/A 7t, the polyamines described in the same t/-/11r6/, the nitroxy radicals described in the same 7/-/1, and the same 77tO, the same + Alcohols described in /-1rtzt1 and A/-/27≠/ri, oximes described in AI-/ritt7, and tertiary amines described in 4/-2tj/data. It may be added if necessary.

Other preservatives include various metals described in JP-A-17-41171171 and J7-JJ74L, salicylic acids described in JP-A-17-41171171 and J7-JJ74L;
Alkanolamines described in No.-3332, JP-A-56
It is preferable to use all of the polyethyleneimines described in No.-2≠3≠R, the aromatic polyhydroxy compounds described in U.S. Pat. Aromatic polyhydroxy compound, triethanolamine, and Akira T/-
2Ajl≠Addition of the compound described in the number is preferred.

The color developer used in the present invention preferably has a pH of ~/2, more preferably 2~//0, and the color developer solution contains other known developer component compounds. can be included.

Above pH? For retention, it is preferable to use various buffers in all phases. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glyfur salt,
N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, j,44-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, coamino-methyl=/, 3-propanediol salt, valine salt, proline Salts, trishydroxyamine methane salts, lysine salts, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates have low solubility and pH 9.
These buffers have the advantage of having excellent buffering ability in the high pH range of 0 or higher, having no adverse effects on photographic performance (fogging, etc.) even when added to color developers, and being inexpensive. It is particularly preferable.

Specific examples of these buffers include carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate,
Trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium O-hydroxybenzoate (salicylic acid) sodium), potassium o-hydroxybenzoate, 5
Examples include sodium -sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/β
It is preferably at least 0.1 mol/l-0, particularly 0.1 mol/l-0,
Particularly preferred is 4 mol/β.

In addition, various caloric acid agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or for improving the stability of the color developer.

The chelating agent is preferably an organic acid compound, such as the aminopolycarboxylic acids described in Japanese Patent Publication No. 48-30496 and Japanese Patent Publication No. 44-30232, Japanese Patent Publication No. 56-97347, Japanese Patent Publication No. 56-39359, and West German Patent No. 2. 227
．． Organic phosphonic acids described in No. 639, JP-A-52-80
No. 2726, No. 53-42730, No. 54-1211
Phosphonocarboxylic acids described in JP-A No. 27, No. 55-126241, No. 55-659506, etc., and others such as JP-A-58-195845 and JP-A No. 58-203440.
Examples include compounds described in 3 g- of Japanese Patent Publication No. 53-40900 and the like. Specific examples are shown below, but the invention is not limited to these.

・Nitrilotriacetic acid, ・Diethylenetriaminepentaacetic acid, ・
Ethylenediaminetetraacetic acid, ・N, N, N-trimethylenephosphonic acid, ・ethylenediamine-N, N, N'
, N'-tetramethylenephosphonic acid, ・trans-cyclohexanediaminetetraacetic acid, ・1゜2-diaminopropanetetraacetic acid, ・glycol ether diaminetetraacetic acid, ・
Ethylenediamine orthohydroxyphenylacetic acid, ・2
-boshoptan-1,2,4-)licarboxylic acid, ・1
-Hydroquinethylidene-1,1-diphosphonic acid, ・N
, N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic 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 80g per serving.

Any development accelerator can be added to the color developer if necessary. However, the color developer of the present invention preferably does not substantially contain benzyl alcohol for the purpose of improving staining that occurs on a white background during continuous processing or after processing. The term "substantially" as used herein refers to the developer, and means that it does not contain more than 2,000, preferably no developer at all. The foregoing compounds used in the present invention provide significant benefits in processing steps using color developers that are substantially free of benzyl alcohol.

Other viscosity accelerators include Shokosho J7-/joirt
No. r, No. 37-j9F7, No. 31-7126, No. 1
717-/, ZJrO No. F, t-20IP No. and American Poetry License No. 3. lr/3. Thioether compounds represented by Cog No. 7, etc., JP-A Showa λ-I/-Tar2 No. and 30-/! p-phenylenediamine compound represented by No. 11
t4t-3007 Hiro issue, JP-A-ShojA-/3 & 126 issue and the same! No. 3.1
No. 28.182, No. 4.230.796, No. 3.25
3.919, Japanese Patent Publication No. 41-11431, U.S. Patent No. 2.482.546, U.S. Pat. No. 42-25201, U.S. Patent No. 3.128.183, Japanese Patent Publication No. 41-11431, No. 42-2388.3 and U.S. Patent No. 3.532.
Polyalkylene oxide represented by No. 501, other 1-phenyl-3-pyrazolidones, imidazoles, etc. can be added as necessary.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of anti-fogging agents include benzotriazole, 6-nitroindazole, 5-nitroindazole,
5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, -Hiroshi /
- Representative examples include nitrogen-containing heterocyclic compounds such as 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, 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 θ~5g/β, preferably 0.1g~
It is 4g/l.

Furthermore, various surfactants such as alkylsulfonic acids, arylphosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 40°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. The replenishment amount is preferably small, but is 20 to 600 ml, preferably 50 to 300 mJ!, more preferably 800 ml per 1 m of photosensitive material.
mA' to 200 mjl'.

1g 2- Desilvering process Next, the desilvering step in the present invention will be explained.

In the present invention, the effect of the present invention becomes more pronounced when the process time of the desilvering step is shortened. That is, less than 2 minutes, preferably /! seconds to seconds.

The effect of the method of the invention becomes even more pronounced when the amount of bleach-fix replenishment is reduced. For example, photosensitive material/7F12
It is preferable that the replenishment amount of the bleach-fixing solution is 80-/-01 per unit.

Furthermore, the effects of the present invention are similarly improved when the amount of color developer brought into the bleach-fix solution increases. For example, the color developer mixing ratio (vo1%) is /j-, tOvo1
%, it is remarkable in the case of tOvo1%.

A complete explanation of the bleach-fix solution used in the desilvering process.

As the bleaching agent used in the bleach-fix solution, any bleaching agent can be used, but organic complex salts of iron (III) (e.g., aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, aminopolyphosphonic acid) , complex salts such as phosphonocarboxylic acids and organic phosphonic acids) or organic acids such as ecunic acid, tartaric acid, and malic acid; persulfates; hydrogen peroxide, and the like are preferred.

Among these, organic complex salts of iron(I) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, organic phosphonic acids, or salts thereof useful for forming organic complex salts of iron(III) include ethylenediaminetetraacetic acid, diethyleneditriaminepentaacetic acid, 1. 3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid,
Cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,
Examples include iminodiacetic acid, glycol ether diamine tetraacetic acid, and the like.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, iron (I
Complex salts are preferred because they have a high bleaching edge.

These ferric ion complex salts may be used in the form of complex salts, and ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, -≠ j - A ferric ion complex salt may be formed in a solution using ferric phosphate or the like and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. Further, the chelating agent may be used in excess of the amount required to form the ferric ion complex. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0
Mol/I is preferably 0.05 to 0.50 mol/l. Bleach solutions, bleach-fix solutions and/or their pre-baths include:
Various compounds can be used as bleach accelerators.

For example, U.S. Pat.
Publication No. 5630, Research Disclosure No. 171
No. 29 (July 1978 issue), compounds having a mercapto group or disulfide bond, and
No. 506, JP-A-52-20832, JP-A No. 53-327
Thiourea-based compounds, such as those described in No. 35 and US Pat.

-+ 6- In addition, the bleach-fix solution used in the present invention contains bromide (
(e.g., potassium bromide, sodium bromide, ammonium bromide) or may contain rehalogenating agents such as chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride) or iodides (e.g., ammonium iodide). Can be done. If necessary, the pH buffering capacity of 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. One or more types of inorganic acids, organic acids, alkali gold W4 or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can all be added.

The fixing agent conveniently used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, namely, a thiosulfate such as sodium thiosulfate or ammonium thiosulfate; a thiocyanate such as sodium thiocyanate or ammonium thiocyanate; Ethylene bisthioglycolic acid, j, A-dithia-/
, thioether compounds such as lr-octanediol, and water-soluble silver halide solubilizers such as thioureas, these materials or a mixture of λ or more types thereof can be used. Furthermore, a bleach-fixing solution containing a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-31-/jj3j≠ may also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of the fixing agent per liter is preferably from 7 to 2 moles, more preferably from 0 to 0 mole.

The pH of the bleach-fix solution of the present invention is p, t-+, r, preferably 1.0-+, 0. Fog is likely to occur regardless of whether the CpH is higher or lower than this range.

Here, the above-mentioned pH is the pH of the bleach-fixing solution in the state of use. pH of replenisher 1 p at the start of continuous treatment
H does not necessarily have to fall within the above pn range.

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

The bleach-fix solution in the present invention contains sulfite (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfite (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as a preservative. ), metabisulfites (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds have approximately 0.0λ to 0.0λ in terms of sulfite ions.
It is preferable to contain jO mol/, more preferably 0.0 h to 0. ≠θmol/l.

As a preservative, fM salt is commonly added, but
In addition, ascorbic acid, carbonyl bisulfite adducts, carbonyl compounds, etc. may be added.

Furthermore, buffering agents, fluorescent whitening agents, chelating agents, antifoaming agents, etc. A fungicide, a fungicide, etc. may be added as necessary.

In the aqueous solution and/or stabilization process of the present invention, after desilvering treatment such as bleach-fixing,
It is common to perform washing with water and/or stabilization treatment.

The amount of water used in the washing process depends on the nature of the photosensitive material (e.g., depending on the material used for use, such as couplers), the intended use, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and other factors. It can be set over a wide range depending on the conditions. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture Ant Television Engineers.
of Motion Picture and Te1
(Evi-sion Engineers) Volume 64, P
, 248-253 (May 1955 issue). Generally, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, from 0.5A to 11A per m' of photosensitive material, and the effect of the present invention is remarkable. The increased residence time causes problems such as bacteria propagation and the resulting floating matter adhering to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such problems, the method for reducing calcium and magnesium described in Japanese Patent Application No. 131632/1988 can be used very effectively. In addition, chlorine-based disinfectants such as inthiazolone compounds and thiabendazoles described in JP-A No. 57-8542, chlorinated sodium incyanurate described in JP-A No. 61-120145, and Japanese Patent Application No. 60-80548
Benzo described in No. 7) IJ Azonope Copper Ion Others by Hiroshi Horiguchi ``Chemistry of Antibacterial and Antifungal Agents'' Sanitation Technique Complete Edition ``Sterilization of Microorganisms, Disinfection, and Antifungal Technology'' Japanese Antibacterial and Antifungal Society Cotton ``Antibiotics'' It is also possible to use fungicides listed in the "Encyclopedia of Antifungal Agents".

Further, in the washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.

The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing liquid, such as an aldehyde compound such as formalin, or a film suitable for stabilizing the dye.
Examples include buffering agents and ammonium compounds for adjusting to H. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.

Furthermore, a surfactant, a fluorescent brightener, and a hardening agent can also be added. In the processing of the photosensitive material of the present invention, when stabilization is performed directly without passing through a water washing step, JP-A No. 57
-8543, 58-14834, 60-22034
All known methods described in No. 5 and the like can be used.

In addition, it is also a preferable embodiment to use chelating agents such as 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetemethylenephosphonic acid, and magnesium and bismuth compounds.

In the present invention, a so-called rinsing solution is also used as a washing solution or a stabilizing solution used after the desilvering treatment.

The pH of the water washing step or stabilization step of the present invention is 4 to 80, preferably 5 to 8. Temperature depends on the use of photosensitive materials,
Although various settings can be made depending on the characteristics, etc., the temperature is generally 15 to 45°C, preferably 20 to 40°C.

The time can be set arbitrarily, but the shorter the time, the more effective the present invention is.
- The effect is more pronounced, preferably from 30 seconds to 4 minutes, more preferably from 30 seconds to 2 minutes. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduced emissions, ease of handling, etc., and the effects of the present invention are also greater.

A specific preferable replenishment amount is 0.5 to 50 times, preferably 3 to 40 times, the amount brought in from the previous bath per unit area of the photosensitive material. or 11 or less per m' of photosensitive material,
Preferably 500+nj! It is as follows. Further, replenishment may be performed continuously or intermittently.

The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is to flow the overflow of washing water, which has been reduced by a multi-stage countercurrent system, into a bleach-fixing bath, which is a pre-bath, and replenishing the bleach-fixing bath with concentrated liquid to reduce the amount of waste liquid. .

The method of the invention can be applied to any processing step. For example, color paper, color reversal paper, color direct positive photosensitive material, color positive film, color negative film, color reversal film, etc. -s4+! − It can be applied to the processing of
-, preferably applied to color inversion benches.

Next, the silver halide color photographic light-sensitive material processed according to the present invention will be explained.

As the silver halide emulsion of the light-sensitive material used in the present invention, a silver chlorobromide emulsion or a silver chloride emulsion containing at least 20 moles of silver chloride is used, and furthermore, the silver chloride content is from 20 to 20%! The case of morchi is most preferable. The effects of the present invention are particularly remarkable when rapid processing or low replenishment processing is performed using the emulsion sound described above.

Do the silver halide grains used in the present invention have different phases inside and on the surface? The particle may have a multiphase structure such as a bonded structure, or the entire particle may consist of a uniform phase. Moreover, they may be mixed.

Average grain size of silver halide grains used in the present invention (
In the case of spherical or nearly spherical particles, the particle diameter is used, and in the case of cubic particles, the principal is the particle size, and the particle size is expressed as an average based on the projected area.

In the case of tabular grains, it is expressed in yen. ) is 0. The diameter is preferably 1 μm or more, and particularly preferred is 1.
It is 5 μm or less and 0.15 μm or more.

The particle size distribution can be narrow or wide, but
A so-called monodisperse silver halide emulsion in which 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 within 20%, particularly preferably within 15%, is used in the present invention. It is preferable. 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 substantially the same color sensitivity (monodispersity is defined as the above-mentioned type). (preferably one with a variable rate) 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 shape of the silver halide grains used in the present invention is regular (cubic, octahedral, rhombidodecahedral, dodecahedral, etc.).
r) crystals or coexistence of these crystals, or irregular (irregular) crystals such as spherical
ular) crystals, or a composite form of these crystal forms.

Tabular grains may also be used (especially when the length/thickness ratio is 5).
~8 or more tabular grains account for 5 of the front projected area of the grains
An emulsion containing 0% or more may also be used. An emulsion consisting of a mixture of these various crystal forms may also be used. These various emulsions may be of the surface latent image type that forms latent images mainly on the surface;
Any type of internal latent image formed inside the particles may be used.

The photographic emulsion used in the present invention is described in Research Disclosure (RD) vol. 170 Item No.
It can be prepared using the method described in Section 17643 (L II, ■) (I978j 7-December). ``The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization.

Additives used in such processes are listed in Research Disclosure Vol. 176, No. 17643 (I97
8) and Volume 187, No. 18716
(November 1979), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.゛Additive type R
D17643 RD187161 Chemical sensitizer
Page 23 Page 648 Right 1 Close 2 Sensitivity enhancer
Same as above 5 Brightener Page 24 -j and - 8 Organic solvent Page 25 80 Ultraviolet absorber 11 Anti-stain agent Page 25 right column Page 650 left to right column 12 Dye image stabilizer Page 25 13 Hardener Page 26 Page 651 left Column 1
4 Bai Ndar page 26 Same as above 15
Plasticizer, lubricant Page 27 Page 650 Right column 17
Prevention of sphutic, page 27 Same as above agent Various color couplers can be used in the present invention. The term "color coupler" as used herein refers to a compound capable of producing a dye through a coupling reaction with an oxidized product of an aromatic primary amine developer. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolones 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.
(December 1978)■-D Section and 18717
(November 1979).

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent color coupler substituted with a leaving group can reduce the amount of silver coated than a two-equivalent color coupler in which the coupling active position is a hydrogen atom. Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, or DIR couplers that release a phenomenon 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 the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent Box 2,40
No. 7,280, No. 2.875.057 and No. 3
, No. 265.506, etc. The use of two-equivalent yellow couplers is preferred for the present invention; U.S. Pat.
Same No. 3.933,501 and No. 4,022゜62
0, etc., or Japanese Patent Publication No. 55-80739, U.S. Patent Box 4,
No. 401,752, No. 4,326.024, RD1
8053 (April 1979), British Patent Box L 42
5. o26, West German Application Publication Box No. 2,219,917,
Same 2nd. 261. No. 361, No. 2,329,58
Typical examples include the nitrogen atom separation type yellow couplers described in No. 7 and No. 24'33,812. α-pivaloylacetanilide couplers have excellent color fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

Examples of magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone-Otsu/- and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye.
No. 82, No. 2゜343.703, No. 2,600,
No. 788, No. 2,908,573, No. 3. 06
2. No. 653, No. 3,152,896, and No. 3936.015. The leaving group of the two-equivalent 5-pyrazolone coupler is preferably a nitrogen atom leaving group as described in U.S. Pat. No. 4,380,619 or an arylthio group as described in U.S. Pat. No. 4,351,897; The 5-pyrazolone coupler having a ballast group described in European Patent No. 73.636 provides high color density.

As pyrazoloazole couplers, U.S. Patent Box 3,
369,879, preferably pyrazolo(5,1-C)(I
, 2, 4)) Liazoles, pyrazolotetrazoles and Research Disclosure 2 described in Research Disclosure 24220 (June 1984)
4230 (June 1984). The imidazo(I,2-b) pyrazole film described in European Patent Box No. 119.741 is preferable from the viewpoint of low yellow side absorption of the coloring dye and light fastness, and the pyrazole film described in European Patent Box No. 119,860 is preferable. (I°5-b)(I,2,4))riazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenolic couplers, such as the naphthol-based couplers described in U.S. Pat. No. 2,474°293, preferably U.S. Pat.
．． No. 212, No. 4゜146.396, No. 4.2'
Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 28.233 and No. 4.296.200. Specific examples of phenolic couplers include U.S. Patent No. 2,369,929;
No. 801.171, No. 2. 772. No. 162, No. 2.895.826, etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention, exemplified by U.S. Pat.
772,002, a phenolic cyan coupler having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus, U.S. Pat.
．． No. 758,308, No. 4,126,396, No. 4,334,011, No. 4. 327゜173, West German Patent Publication No. 3,329,729 and JP-A-59-
2,5-diacylamino substituted phenolic couplers such as those described in US Pat. No. 166,956 and US Patent Box 3,44.
No. 6,622, No. 4,333,999, No. 4.
451. These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, which are described in No. 559 and No. 4,427,767.

Is it possible to create graininess by using a coupler with moderately diffusive color pigment? It can be improved. Such dye-diffusive couplers are described in US Pat. No. 4, JAA.

No. 237 and British Enemy No. 2. /2! A specific example of a magenta coupler is shown in No. 70, and European patent box t, 3
No. 70 and West German Application Publication No. 3,234A.

No. 333 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the above-mentioned special couplers may be entirely formed into dimers or higher polymers. Typical examples of polymerized dye-forming couplers are shown in U.S. Patent No. 3. ≠zi, r2
No. o and No. ≠, oro.

It is described in No. 271. Specific examples of polymerized magenta couplers are given in British Patent No. 1, 802,173 and U.S. Patent No. 1, JA7. -2f, No. 2.

6 j- Two or more of the various couplers used in the present invention can be used together in the same photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or the same compound can be used in different combinations. It can also be introduced into two or more layers.

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 for oil-in-water dispersion is U.S. Patent Box 2,322,027.
It is written in the number etc.

Further, the process, effects, and specific examples of latex for impregnation of latex dispersion methods are described in U.S. Patent No. 4,199°363, O.L.S. It is described in No. 230, etc.

Typical usage amounts for color couplers range from o,ooi to 1 mole per mole of photosensitive silver halide, preferably from 0.01 to 0.00 mole for yellow couplers.
5 moles, 0.003 to 0.00 for magenta couplers.
3 mol, and for cyan couplers 0.002 to 0.
It is 3 moles.

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 the support and coating method, please refer to Research Disklory+-1F Volume 6 Item 1764
3 XV term (p, 27) X ■ term (T), 2B) (I9
(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.

(Examples) Hereinafter, specific examples of the present invention will be shown and the present invention will be explained in further detail. However, the present invention is not limited to the following examples.

Example 1 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene.

The coating solution is prepared by mixing and dissolving an emulsion, various chemicals, and an emulsified dispersion of a coupler, and the respective preparation methods are shown below.

(Preparation of coupler emulsion) 19.1 g of yellow coupler (ExY) and 4.4 g of color image stabilizer (Cpd-1) were mixed with 27.2 cc of ethyl acetate and a solvent (Solv-1). , 7CC were added and dissolved, and this solution was emulsified and dispersed in 185 cc of an 80% aqueous gelatin solution containing 8 cc of 80% sodium dodecylhenzenesulfonate.

Thereafter, emulsions for magenta, cyan, and intermediate layers were prepared in the same manner.

Next, a method for preparing the emulsion used in this example will be described.

Blue sensitive emulsion (I liquid) (2 liquids) Sulfuric acid (IN) 24 cc (3 liquids) Compound A (I%) below 3 ccH3 Chang 3 (4 liquids) (5 liquids) -6 ter (6 liquids) (7 liquids) ( Liquid I) was heated to 76°C, and liquids (2) and (3) were added.

Thereafter, (liquid 4) and (liquid 5) were added simultaneously over a period of 80 minutes.

After a further 80 minutes, (6 liquids) and (77 liquids) were added simultaneously over a period of 35 minutes. After 5 minutes of addition, the temperature was lowered and desalted. Add water and dispersed gelatin to adjust the pH to 6°3, and prepare monodisperse cubic silver chloride with an average particle size of 1.1 μm and a coefficient of variation (standard deviation divided by average particle size: S/d) of 0.80. An emulsion was obtained.

To 1.0 kg of this emulsion, add blue spectral sensitizing dye (S-1).
Add 26cc of 0.6% solution of
The AgBr ultrafine grain emulsion was added at a ratio of 0.5 mol% to the Phos)AgC1 emulsion, and mixed and aged at 58°C for 80 minutes. After that, sodium thiosulfate was added to optimally chemically sensitize the stabilizer (Stb-1) to 80-4
One mole of Ag was added.

Green-sensitive emulsion (8 liquids) (9 liquids) Sulfuric acid (IN) 24rr+/! (I0
Liquid) Compound A (I%) 3mj2 (Liquid I1) (Liquid I2) Add lH,o and heat 200mf (Liquid I3) (Liquid I4) (Liquid 8) to 52°C, and (Liquid 9) and ( Solution I0) was added. Thereafter, (Liquid I1) and (Liquid I2) were added simultaneously for 14 minutes. After a further 80 minutes, (Liquid I3) and (Liquid I4) were added simultaneously over a period of 15 minutes.

A sensitizing dye (S-2) was added to this emulsion in an amount of 1 mo of silver halide.
4×80-' mol per portion was added, and then the following (liquid I5) was added over 80 minutes, and 5 minutes after the addition, the temperature was lowered and desalted.

Add water and dispersed gelatin, adjust the pH to 6.2, -7,2- (liquid I5), add sodium thiosulfate at 58°C, perform optimal chemical sensitization, and average particle size of 0.48 μm. , coefficient of variation (standard deviation divided by average particle size; s/d) 0.80
A monodisperse cubic temperature silver emulsion was obtained.

In addition, 1 m of silver halide (Stb-1) was added as a stabilizer.
5XIO-'mol was added per 1 o.

For the red-sensitive emulsion, the sensitizing dye used was changed to (S-3) in the preparation method for the green-sensitive emulsion, and the amount added was changed to halogen a!
It was prepared in exactly the same manner except that the amount was 1.5×80-' moles per mole.

(Layer structure) The composition of each layer in the sample is shown below. The numbers are the amount of coating (
g/m"). Silver halide emulsions are expressed in silver equivalent coating amount.

Support polyethylene laminate paper [white pigment (T 80 z) on the polyethylene on the first layer side
and bluish dye (ulmarine blue)] Layer (blue-sensitive layer) Silver halide emulsion 0.30 gelatin
1.86 yellow coupler (E
xY) 0.82 color image stabilizer (Cpd'-1)
0.19 solvent (Solv-1)
0.35 Second layer (color mixing prevention N) Gelatin 0.99 Color mixing prevention (
Cp d-2) 0. 08 Third layer (green sensitive layer) Silver halide emulsion 0.36 Gelatin
1.24 magenta coupler (E
xMl) 0.31 color image stabilizer (Cpd-3)
0.25 color image stabilizer (Cpd-4) o
, 12 solvent (Solv-2) 0.42
Fourth layer (ultraviolet absorbing layer) Gelatin 1.58-74'- Ultraviolet absorber (UV-1) 0. 62 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv
-3) 0.24 Fifth layer (red sensitive layer) Silver halide emulsion 0.23 Gelatin
1.34 cyan coupler (Ex
Cl) 0.34 color image stabilizer (Cpd-6)
o, 17 polymer (Cpd-7)
0.40 Solvent (Solv-4) 0.
23 Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.21? Container (Solv
-3) 0. 08 Seventh N (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 17%) 0.17 Liquid paraffin 0.03 As a hardening agent for each layer,
1-oxy-3,5-dichloro-s-triazine sodium salt was used.

The compounds used in each case are as follows.

(ExY) Yellow coupler (ExMl) Magenta coupler e (ExCl) Cyan coupler (Cpd-2) Color mixing inhibitor (Cpd-6) Color image stabilizer H -7 and -0H (Cpd-7) Polymer (UV-1 ) Ultraviolet absorber-g 0= (Solv-1)? Vehicle (Solv-3) Solvent (Solv-4) Solvent -g/- The following dyes were added to the emulsion layer to prevent irradiation.

-J', 2- For the red-sensitive emulsion layer, Lycium per mole of the following compounded silver halide. Added 4X80-3 moles.

(S-/) Sensitizing dye (S-2) Sensitizing dye (stb-1) Stabilizer After exposing the silver halide color photographic light-sensitive material obtained as above through a wedge-shaped wedge,
It was processed using the following processing steps.

Processing process Temperature Time color development 1t'c III second bleach fixing
3Q~Jj'C 30 second rinse■ 30~Jj0C 20 second rinse■ 30~3!0C, 20 second rinse■ 30~3j0C, 2θ second rinse■ 30~3s0c 3o second dry 'y
o-ro0c to seconds (a 3-tank countercurrent flow system from rinsing ■ to ■) was used. The composition of each treatment solution is as follows.

Color developer water 800
m1 Ethylenediamine-N,N,N.

N-tetramethylenephosphonic acid i, rt triethylenediamine (/, ≠ diazabicyclo[co, λ, 2] octane) j, oy-r! - Sodium chloride 1. μ is potassium carbonate Coj1 fluorescent brightener (UD
ITEX CK (manufactured by Ciba Geigy) 3゜oyN-ethyl-N-(β-methanesulfonamidoethyl)-3 methyl-hiro-aminoaniline sulfate s, ztpH (,2
7'c) /θ,i.

Bleach-fix halide and fluorescent brightener additions were varied as shown in Table 1.

Water visit
omt.

Ammonium thiosulfate (70%) /θO sodium gosulfite ivy ethylenediaminetetraacetic acid iron acetate II) ammonium ssyg 6
Monoethylenediaminetetraacetic acid disodium 31 Color developer /jOnl ice vinegar rRrt water? In addition, 80800O YuZ prison liquid ion exchange water (calcium, magnesium 3pp each
Dmax (maximum density area) of the processed light-sensitive material was measured for residual silver amount using fluorescent X-rays. Further, Dmin (minimum density part) was measured by measuring yellow reflection density using a Macbeth densitometer. The results are shown in Table 1.

-7- However, in the bleach-fix solution, the bleach-fix solution/l and the color developing solution are mixed at /jOrtrl and 30θ, and after being stored at 3j 0C for lj days, the entire development process is carried out. went. The color developer was similarly stored at 3J0C for 1J days. Using a Macbeth reflection densitometer for the sample after processing, we measured the Dmin (minimum density of magenta dye density where the coupling speed is fast and fog becomes a problem) in the unexposed area and the color density where the development speed is slow and the color density is low. The highest density part (DBmax) of the yellow density that is difficult to appear was measured.

DBmax was expressed as the amount of change (ΔDBmax) when processing was performed before and after the color developer was completely stored. Results first
Shown in the table.

-ttar-g♂- According to the present invention, magenta fogging (stain) is significantly prevented even in a bleach-fix solution mixed with a color developer, and photographic changes due to bone fracture over time (△DBmax
) will also be improved. Is benzyl alcohol effective? This is particularly noticeable when it is not substantially contained.

(Example λ) The experiment was conducted in the same manner as in Example 1, except that the silver halide composition of the blue-sensitive layer in the color light-sensitive material was changed as shown in Clothing 2 below, and the other conditions were the same as in Example 1. The same experiment was conducted.

result? A summary is shown in Table 2.

However, DBmax represents the minimum density of yellow, and the amount of change when processing before and after storing the color solution. ΔD
Bmin is shown in Table 2.

-Ta/- Based on the present invention, changes in photographic properties (ΔDBmax and ΔDBmin) of color developers over time are significantly reduced.

(Example 3) After imagewise exposure of the color photographic material prepared in Example 1,
Continuous processing in the following processing steps by changing the bleach-fix solution OpH? I did it.

Color development 3j0C≠j seconds 1tirnt
/71 Bleach fixing 30~368C Hiroj seconds /20
111 /7 as stabilizer ■ 30-37°C20
seconds -80t stabilizer■ 30~37°C2C seconds
-io1 stabilizer■ 30-378C20 seconds λj
(hl 80t dry 70~Irj0
C *Photosensitive material/TrL2 heating (Hiro tank countercurrent method from stable to ■) The composition of each processing solution is as follows.

Color developer tank liquid replenisher water 1rooy
rooy ethylenediaminetetraacetic acid J-,Of
2.0fj, t-dihydroxybenzene-/, 2°≠-trisulfone I! 0.3t O,J
f triethanolamine r, oy r,
oy sodium chloride /, gf −
potassium carbonate, 2j f, 2
j fN-ethyl-N-(β methanesulfonamidoethyl)-3-methyl-≠-aminiline sulfate j, Of 7.0f
fl-7 (compound of the present invention) 7.0f 80
．． Of fluorescent brighteners (≠, μ′ monodiaminostilbene) 2. oy ko,
Add zy water 8000tnl
8000wtlp800O'C) lo, or
io, 4tz Bleach Bleach solution (tank solution and refill solution are the same) Water 00ml Ammonium thiosulfate (70%) 80
0ynl sodium sulfite /7
fEthylenediaminetetraacetate iron(II) ammonium! If sodium iron ethylenediaminetetraacetate Jf glacial acetic acid
TaVpH (2t'C)
Refer to Table 3 Stabilizing liquid (tank liquid and refill liquid are the same)! -Hydroxyethylidene mono/, l-diphosphonic acid/, Jf bismuth chloride/, olj-chloro-2-
Methyl-guinthiazolin-3-one o,o,212-Methyl-hiro-isothiazolin-3-one 0,0/f sulfuric acid steel
0.00jt ammonia water (,2
1r water)/, θg water added 8000rrtl-
Table 3 shows the pn at the start and end of running.

Also, do color photographic materials use wedge-shaped exposure? After that, process with each processing solution at the end of the run to determine the minimum density (Dmin) and maximum density (Dmin) of yellow, magenta, and cyan.
Dmax)i was measured and shown in Table 3.

-y 7- According to the invention, in particular l) min is low and Dm
A friend with high ax and excellent photographic characteristics. (Rinko, 3, ≠
) Also, in A/, floating matter was generated in the stable solution (■), which is not preferable.

(Effects of the Invention) The method of the present invention provides a processing method with less fog in a bleach-fix solution. Further, it is possible to improve fluctuations in the maximum concentration of the treatment liquid over time or during continuous treatment.

Here, in addition to the agenta density in the unexposed area, the cyan density and yellow density can also be reduced, and in addition to improving the variation in the maximum painter's density of yellow, cyan and magenta can also be improved in the same way.

Furthermore, the above-mentioned effects can be further achieved under processing conditions in which a large amount of color developer is mixed into the bleach-fix bath.

Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendment Date of 1986 Pleasure

Claims (1)

[Scope of Claims] After imagewise exposing a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer, a process including at least a color development step and a bleach-fixing step following the color development step is performed. In the method for processing a silver halide color photographic light-sensitive material, the silver halide emulsion layer comprises 8
A silver halide emulsion layer containing silver halide grains consisting of 0 mol% or more of silver chloride, and a color developer used in the color development step containing a compound represented by the following general formula (I). . A method for processing a silver halide color photographic light-sensitive material, further characterized in that the pH of the bleach-fix solution used in the bleach-fix step is in the range of 4.5 to 6.8. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1, R^2 and R^3 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ^4 represents a hydrogen atom, hydroxy group, hydrazino group, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group, or amino group, X^1 represents a divalent group, and n is 0 or 1. However, when n=0, R^4 represents an alkyl group, an aryl group, or a heterocyclic group. R^3 and R^4 may jointly form a heterocycle.)