JPH03271734A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce occurrences of stains due to processing and storage by using a photosensitive material containing a specified compound and as a processing solution having bleaching ability a processing solution containing an oxidant having an oxidation reduction potential of >= 150 mV at the time of processing the photosensitive material with a processing solution having bleaching ability after color development. CONSTITUTION:This photosensitive material to be used at the time of processing the photosensitive material with a processing solution contains at least one of the photosensitive compounds represented by formula I in which R<1> is alkyl, alkenyl, or the like; X is a simple bond, -O-, or the like; R<2> is a group substitutable on the benzene ring; l is an integer of 0 - 4; R<3> is aryl; and Z is H or a group to be released by coupling. The processing solution to be used as the processing solution having bleaching ability contains at least one of the oxidants having an oxidation reduction potential of >= 150 mV, thus permitting occurrences of stains due to processing and storage to be restrained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a color photographic light-sensitive material, and in particular, processing staining by speeding up and/or reducing replenishment after the desilvering step, The present invention relates to an image forming method of a color photographic light-sensitive material for photographing in which an increase in staining during storage after processing is suppressed.

(Prior Art) Generally, the basic steps in processing color photosensitive materials are a color development step and a desilvering step. In the color development step, the exposed silver halide is reduced by a color developing agent to produce silver, and the oxidized color developing agent reacts with a color former (coupler) to provide a dye image. In the next desilvering process,
By the action of an oxidizing agent (commonly referred to as a bleaching agent), the silver produced in the color development process is oxidized and then dissolved by a silver ion complexing agent, commonly referred to as a fixing agent. By going through this desilvering step, only a dye image is created on the color photosensitive material.

The above desilvering process is carried out in two baths, a bleaching bath containing a bleaching agent and a fixing bath containing a fixing agent, or in one bath using a bleach-fixing bath containing both a bleaching agent and a fixing agent. There is.

In addition to the above-mentioned basic steps, actual development processing includes various auxiliary steps to maintain the photographic and physical quality of the image or to improve the storage stability of the image. Examples include a hardening bath, a stop bath, an image stabilization bath, and a water washing bath.

In recent years, with the spread of small in-store processing service systems called minilabs, efforts have been made to shorten the time required for the above processing in order to quickly respond to customer processing requests and to reduce the maintenance work of these processing machines. , there is a strong demand for low replenishment.

In particular, the highest demand was to shorten the desilvering step, which conventionally occupied most of the processing time.

However, if the time of the desilvering process (bleaching process, fixing process, bleach-fixing process, etc.) or washing process is shortened or the replenishment rate is reduced, various problems such as those described below occur.

First, an increase in residual silver after processing (defective desilvering); Second, an increase in the minimum density area immediately after processing (processing stain); and third, an increase in the minimum density during storage of the sample after processing. In order to improve desilvering defects, use bleaching agents with strong oxidizing power, such as red blood salt, dichromate, ferric chloride,
It is known to use persulfates, bromates, etc.
Each of them has drawbacks from the viewpoint of environmental protection, handling safety, metal corrosion, etc., and the second and third problems mentioned above have not been solved.

Among these, pH containing ferric complex salt of 1,3-diaminopropanetetraacetic acid described in JP-A No. 62-222252.
The bleaching solution of about 6 has higher oxidizing power than the bleaching solution containing ferric ethylenediaminetetraacetic acid complex salt and enables faster silver bleaching, but it does not bleach directly after color development without using a bath. Although desilvering defects can be improved by treatment, the increase in the minimum density area immediately after treatment (processing stain) as described above
Moreover, it had the disadvantage that there was a significant deterioration in the increase in the minimum concentration part during storage (staining over time).

As a method to solve these problems, a method of improving the treatment stain using a specific high-boiling point organic solvent is disclosed in Japanese Patent Application Laid-open No. 1-2322.
No. 7, and JP-A-64-37556 discloses a method of improving processing stain using a specific cyan coupler.

However, the effect of improving treatment stains by these methods is still not sufficient.

Furthermore, the improvement effect on stain increase during storage after treatment is small.

(Problems to be Solved by the Invention) It is an object of the present invention to reduce the occurrence of processing stains and stains during storage even when processing is performed by a desilvering process that is accelerated and requires low replenishment.

(Means for solving the problem) As a result of various studies to solve the above problems,
It has been found that the problem can be solved by using the following image forming method for color photographic materials.

That is, a red-sensitive silver halide emulsion layer containing a cyan coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a blue-sensitive silver halide emulsion layer containing a yellow coupler are formed on a support. , each at least 1
When a silver halide color photographic light-sensitive material having a layer is processed with a processing solution having bleaching ability after color development, the light-sensitive material contains at least one compound represented by the following general formula [I]. An image forming method for a silver halide color photographic light-sensitive material, characterized in that a processing solution containing at least one kind of oxidizing agent having a redox potential of 150 mV or more is used as the processing solution having bleaching ability. I found that it was solved by

General formula [I] H (wherein R1 is an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, or aryl group, X is a single bond, -0-1-S-1-SO-SO, -1 -COO--
CON 6 -3O□0-1-3o, N-1 or -N-, R6R
' R2 represents a group that can be substituted on the benzene ring, 4 represents an integer of O to 4, R3 represents an aryl group, and Z represents a hydrogen atom or a coupling-off group. However, R6 is a hydrogen atom, an acyl group, or a group having the same meaning as R1, and R7 is a hydrogen atom or a group having the same meaning as R1. ) In this specification, the above groups R'' to R'' are meant to include not only unsubstituted groups but also those having substituents. Also, in the definition of general formula [I], the exemplified X Ga-
In the case of COO-1-CON-6 SO20-1-3O2N-, it means that atoms on either side may be bonded to the benzene nucleus.

For example, -CON- has 6 in the benzene nucleus whether it is C or N. Can be combined.

The cyan dye-forming coupler represented by the general formula [I] will be explained in detail below.

In the formula [■], R1 preferably represents the total number of carbon atoms (
(hereinafter referred to as C number) 1 to 36 (more preferably 6 to 24)
Straight-chain or branched alkyl group, C2-36 (
More preferably 6-24) linear or branched alkenyl group, C number 2-36 (more preferably 6-24)
linear or branched alkynyl group, C number 3-3
6 (more preferably 6 to 24) 3- to 12-membered cycloalkyl group or C number 6 to 36 (more preferably 6 to 24)
) represents a substituent (e.g. halogen atom, hydroxyl group, carboxyl group, sulfo group, cyano group, nitro group, amino group, alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group,
Arylthio group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group,
It may be substituted with a sulfamoylamino group, an alkoxysulfonyl group, an imide group, or a heterocyclic group (hereinafter referred to as substituent group A). R1 is preferably linear, branched, or a substituent (alkoxy group, alkylthio group, aryloxy group, arylthio group, alkylsulfonyl group, arylsulfonyl group, aryl group, alkoxycarbonyl group, epoxy group, cyano group, or halogen atom)
an alkyl group [e.g. n-octyl, n-decyl, n-dodecyl, n-hexadecyl, 2-ethylhexyl, 3.5.5-trimethylhexyl, 3,5.5-trimethylhexyl, 2-ethyl-4- methylpentyl,
2-decyl, 2-hexyldecyl, 2-hebutylundecyl, 2-octyldodecyl, 2.4.6-1-limethylhebutyl, 2,4,5°8-tetramethylnonyl, benzyl, 2-phenethyl , 3-(t-octylphenoxy)propyl, 3-(2,4-di-t-pentylphenoxy)propyl, 2-(4-biphenylyloxy)ethyl, 3-dodecyloxypropyl, 2-dodecylthioethyl , 9.10-epoxyoctadecyl, dodecyloxycarbonylmethyl, 2-(2-naphthyloxy)ethyl], unsubstituted or substituted (e.g. halogen atom,
an alkenyl group having an aryl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, or an alkoxycarbonyl group [e.g. allyl, 10-undecenyl, oleyl, citronellyl, cinnamyl],
A cycloalkyl group that is unsubstituted or has a substituent (for example, a halogen atom, an alkyl group, an alkoxy group, or an aryloxy group) [for example, cyclopentyl, cyclohexyl, 3,5-dimethylcyclohexyl, 4-t-butylcyclohexyl 1, or unsubstituted or Aryl groups having a substituent (halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, aryl group, carbonamide group, alkylthio group or sulfonamide group) [e.g. phenyl, 4-dodecyloxyphenyl, 4-biphenyl, 4- Dodecanesulfonamidophenyl, 4-t
-octylphenyl, 3-pectylphenyl], and particularly preferably the linear, branched or substituted alkyl group.

In general formula CI), X is a single bond, -0--S-5-
so--5o2-1-COO- represents -N-. Here, R6 is a hydrogen atom, an acyl group having 7 1 to 36 (preferably 2 to 24) carbon atoms (e.g., acetamide, butanamide, benzamide, dodecanamide, methylsulfonyl, p-tolylsulfonyl, dodecylsulfonyl, 4-methoxyphenylsulfonyl) ) or a group having the same meaning as R', preferably a hydrogen atom,
It is a linear, branched or substituted alkyl group, or a substituted or unsubstituted aryl group. R7 is a hydrogen atom or a group having the same meaning as R', and is preferably a hydrogen atom or a linear, branched or substituted alkyl group. X
One COO-, -CON-6 may be bonded to R'. X is preferably 10--S-
1-3 O2- or -COO- (bonded to R' with 0), particularly preferably -O- or -COO-(O
).

In general formula CI), R2 is a group that can be substituted on the benzene ring, preferably a group selected from the above substituent group A, and when 4 is plural, R2 can be the same or different. Good too. R2 is more preferably a halogen atom (F, Cβ, Br, I), an alkyl group having 1 to 24 carbon atoms (
For example, methyl, butyl, t-butyl, t-octyl, 2
-dodecyl), cycloalkyl groups having 3 to 24 carbon atoms (e.g. cyclopentyl, cyclohexyl), alkoxy groups having 1 to 24 carbon atoms (e.g. methoxy, butoxy, dodecyloxy, benzyloxy, 2-ethylhexyloxy, 3
-dodecyloxypropoxy, 2-dodecylthioethoxy, dodecyloxycarbonylmethoxy), C number 2-2
4 carbonamide groups (for example, acetamide, 2-ethylhexanamide, trifluoroacetamide) or C1-24 sulfonamide groups (for example, methanesulfonamide, dodecanesulfonamide, toluenesulfonamide).

In formula CI], C is preferably an integer of 0 to 2, more preferably an integer of 0 or 1.

In the general formula [Engine], R3 preferably has a C number of 6 to 36,
More preferably, it represents an aryl group of 6 to 15, and may be substituted with a substituent selected from the above-mentioned substituent group A, or may be a fused ring. Here, preferred substituents include halogen atoms (F, C°C, Br, ■), cyano groups, nitro groups, acyl groups (e.g. acetyl, benzoyl), alkyl groups (e.g. methyl, t-butyl, trifluoromethyl,
trichloromethyl), alkoxy groups (e.g. methoxy,
ethoxy, butoxy, trifluoromethoxy), alkylsulfonyl groups (e.g. methylsulfonyl, propylsulfonyl, butylsulfonyl, benzylsulfonyl),
Arylsulfonyl groups (e.g. phenylsulfonyl, p
-tolylsulfonyl, p-chlorophenylsulfonyl)
, alkoxycarbonyl groups (e.g. methoxycarbonyl, butoxycarbonyl), sulfonamide groups (e.g. methanesulfonamide, trifluoromethanesulfonamide, toluenesulfonamide), carbamoyl groups (e.g. N,N-dimethylcarbamoyl, N-phenylcarbamoyl) or sulfamoyl groups such as N,N-diethylsulfamoyl, N-phenylsulfamoyl. R1 is preferably a phenyl group having at least one substituent selected from a halogen atom, a cyan group, a sulfonamido group, an alkylsulfonyl group, an arylsulfonyl group, and a trifluoromethyl group,
More preferably 4-cyanophenyl, 4-cyano-3
-halogenophenyl, 3-cyano-4-halogenophenyl, 4-alkylsulfonylphenyl, 4-alkylsulfonyl-3-halogenophenyl, 4-alkylsulfonyl-3-alkoxyphenyl, 3-alkoxy-4-
Alkylsulfonylphenyl, 3.4-dihalogenophenyl, 4-halogenophenyl, 3.4.5-)dihalogenophenyl, 3.4-dicyanophenyl, 3-cyano-
4,5-dihalogenophenyl, 4-trifluoromethylphenyl or 3-sulfonamidophenyl, particularly preferably 4-cyanophenyl, 3-cyano-4halogenophenyl, 4-cyano-3-halogenophenyl, 3
, 4-dicyanophenyl or 4-alkylsulfonylphenyl.

In the general formula +Jl, Z represents a hydrogen atom or a coupling-off group (including a leaving atom; the same applies hereinafter). Preferred examples of coupling-off groups include halogen atoms, -
OR'-SR'Aryl azo group having 6 to 30 carbon atoms, C
number 1 to 30, and the coupling active position (2
heterocyclic group (e.g., succinimide, phthalimide, hydantoinyl, pyrazolyl,
2-benzotriazolyl) and the like. Here R
4 is C@1-36 alkyl group, C2-36 alkenyl group, C3-36 cycloalkyl group, C6-3
6 aryl group or a C2-36 heterocyclic group, and these groups may be substituted with a substituent selected from Group A. Z is more preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, or an alkylthio group, particularly preferably a hydrogen atom, a chlorine atom,
A group represented by the following general formula (n) or the following general formula [m
) is a group represented by the general formula (n) R11 and R'' are each a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, or a substituted or unsubstituted group [wherein, RS is a halogen atom, cyano group, nitro group, alkyl group, alkoxy group, alkylthio group, alkylsulfonyl group, arylsulfonyl group, carbonamide group, sulfonamide group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group or carboxyl group, m is 0 to 5 represents an integer of.Here, when m is plural, R5 may be the same or different.] General formula (Il (In the formula, R6 and R7 may each be a hydrogen atom or , R5 is preferably a halogen atom, an alkyl group (e.g. methyl, t-butyl, t-octyl, pentadecyl), an alkoxy group (e.g. methoxy,
n-butoxy, n-octyloxy, benzyloxy,
methoxyethoxy), carbonamide groups (e.g. acetamide, 3-carboxypropanamide) or sulfonamide groups (e.g. methanesulfonamide, toluenesulfonamide, p-dodecyloxybenzenesulfonamide), particularly preferably alkyl or alkoxy groups. It is. m is preferably an integer of O to 2, more preferably an integer of O or 1.

In general formula [111), when R6 and/or R7 represents a monovalent group, preferably an alkyl group (e.g. methyl, ethyl, n-butyl, ethoxycarbonylmethyl, benzyl, n-decyl, n-dodecyl), Aryl groups (e.g. phenyl, 4-chlorophenyl, 4-methoxyphenyl), acyl groups (e.g. acetyl, decanoyl, benzoyl, pivaloyl) or carbamoyl groups (e.g. N-ethylcarbamoyl, N-phenylcarbamoyl)
R6 and R7 are more preferably a hydrogen atom, an alkyl group or an aryl group, and 1 is a substituted or unsubstituted amine group.

In the general formula [m], n preferably represents an integer of 1 to 3, more preferably 1.

There is. In the general formula LII[), R6 is preferably an alkyl group, an alkoxy group, an alkenyloxy group, an aryloxy group, or a substituted or unsubstituted amino group, more preferably an alkoxy group or a CH3 CH3 6H13 CH3 6H13 C2H5 The following formula CI ) shows an example of R3 that can be pressed.

6H13 Examples of Z in general formula (I) are shown below.

H 1 0CCH3 -O502CH.

1 0COC2H5 1 0CNHC2H5 -OCH2COOCH3 OCH2CH2COOCH3 OCH2CHzSO2CHg 0 CHzCONt(CHzCHzOt(-OCH2C
ONHCH2CH20CH3-OCR2CH H2 -OCH2CH2SCH2COOH -OCH2CH2NH3O2CH3 -5CH2COOC2H5 -5CI(2COOH -5CH2CH2COOH -5CHCOOH H3 -S CI(2CH20H 3C)12CHC t(20H CH2CH2COOH Specific examples of the cyan dye-forming coupler represented by the general formula (I) are shown below.

General formula) %Formula% A typical synthesis route for the cyan dye-forming coupler of the present invention represented by the general formula (1) is shown below.

H (I) Compound a can be easily derived from salicylic acids, thiosalicylic acids, phthalic anhydrides, anthranilic acids, etc. by known methods.

Induction from a to b uses thionyl chloride, phosphorus oxychloride, phosphorus pentachloride, oxalyl chloride, etc. without solvent or
Methylene chloride, chloroform, carbon tetrachloride, dichloroethane, toluene, N,N-dimethylformamide, N,
The reaction is carried out in a solvent such as N-dimethylacetamide. The reaction temperature is usually -20°C to 150°C, preferably -10°C to 80°C.

Compound C is disclosed in U.S. Patent No. 4,333,999 and Japanese Patent Application Publication No. 6
No. 0-35731, No. 61-2757, No. 61-42
It can be synthesized by the synthesis method described in No. 658, Japanese Patent Application Laid-Open No. 63-208562, and the like.

The reaction between b and C can be carried out without a solvent or in acetonitrile, ethyl acetate, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, N
, N'-dimethylimidacylin-2-one, etc., usually from -20°C to 150°C, preferably from -10°C to 80°C.
It is carried out in a temperature range of ℃. At this time, a weak base such as pyridine, imidazole, N,N-dimethylaniline, etc. may be used. The cyan coupler represented by general formula (I) is a
It can also be synthesized by a direct dehydration condensation reaction between and C, using N as a condensing agent.

No-dicyclohexylcarbodiimide, carbonyldiimidazole, etc. are used.

8 - Coupler 1-50 Luo 2-hexyldodecanol 24.2g and pyridine 7.
9 g was dissolved in 100 d of ethyl acetate, and 14.8 g of phthalic anhydride was added with a stirrer at room temperature.

After stirring at 50° C. for 3 hours, the reaction solution was transferred to a separating funnel, washed twice with diluted hydrochloric acid, and drained.

Dissolve the concentrate in 50 columns of methylene chloride and add N.

0.3 d of N-dimethylformamide was added, and 13 g of oxalyl chloride was added dropwise over about 30 minutes while stirring at room temperature.

After stirring for about 1 hour, the mixture was concentrated to obtain an oily substance of 2-dodecyloxycarbonylbenzoyl chloride.

24.2 g of 5-amino-2-[3-(4-cyanophenyl)ureido]phenol synthesized according to the synthesis method described in U.S. Pat. No. 4,333,999 was
The solution was dissolved in rrM of N,N-dimethylacetamide, and 2-dodecyloxycarbonylbenzoyl chloride was added dropwise to the solution over about 30 minutes while stirring at room temperature. Stir for 2 hours after dropping,
The reaction solution was transferred to a separating funnel. 500 d of ethyl acetate was added, and the mixture was washed twice with dilute hydrochloric acid and then with an aqueous sodium bicarbonate solution, and then dried with sodium sulfate. Approximately 1/2 of the ethyl acetate solution
By concentrating, filtering and drying the precipitated crystals,
36.9 g of the desired example coupler 1-5 was obtained. The melting point of this compound is 185-189°C and the structure is 'HN
Confirmed by MR spectrum, mass spectrum and elemental analysis.

In the present invention, the cyan coupler is generally used in an amount of 0.002 to 0.3 mol, preferably 0.01 to 0.2 mol, per mol of photosensitive silver halide. The coating amount per square meter is 0.01 to 5.
mmol, preferably 0.1 to 2 mmol.

A treatment step having bleaching ability and an oxidizing agent having a redox potential of 150 mV or more in the present invention will be described in detail.

In the method for processing a silver halide color photographic light-sensitive material (hereinafter also referred to as light-sensitive material) of the present invention, the light-sensitive material after imagewise exposure is subjected to a color development process, and then a desilvering process is performed.

In this desilvering process, a fixing solution and a bleach-fixing solution are used after bleaching. A typical desilvering treatment process including treatment with such a treatment liquid is as follows.

■Constant Bleach ■Bleach → Bleach-Fix ■Bleach - Wash with Water ■Constant Rinse Bleach ■Constant Bleach → Continuous Bleach-Fix ■Wash - Bleach-Fix ■Bleach-Fix ■Fix → Bleach-Fix Especially, among the above steps, (1), (2), and (2) are preferable, and for process (1), for example, Japanese Patent Application Laid-Open No. 61-75352
Disclosed in the issue.

In addition, the tank configuration of processing baths such as bleaching baths and fixing baths applied to the above process may be one tank or two tanks, but two or more tanks (
For example, it may be 2 to 4 tanks (in which case a countercurrent system is preferred).

In the present invention, the processing solution having a bleaching ability and containing a high potential oxidizing agent having a redox potential of 150 mV or higher (hereinafter simply referred to as a high potential oxidizing agent) means the bleaching solution i1 and the bleach-fixing solution.

In the present invention, a process in which desilvering treatment is performed immediately after the color development process using a processing solution having bleaching ability is preferred, and in this case, the processing solution containing a high potential oxidizing agent and having bleaching ability is It is preferable that it is a liquid, and a remarkable effect can be achieved in such a process.

Therefore, it is preferable to perform a bleaching process immediately after the color development process, and such a bleaching process will be described below as a representative example.

In the bleaching process in the present invention, it is preferable to perform replenishment by supplying water equivalent to the evaporated content of the bleaching solution.

In the present invention, the bleaching agent, which is an oxidizing agent contained in the processing solution having bleaching ability, has an oxidation-reduction potential of 150 mV or more, and the higher the oxidation-reduction potential, the better the desilvering property is. However, if the redox potential is too high, the stability of the processing liquid having bleaching ability may decrease. Therefore,
The redox potential is preferably 150 mV or more and 400 mV
Below, it is more preferably 180 mV or more and 300 mV or less.

Considering these points, the redox potential is 250 m
Particularly preferred is 1,3-diaminopropanetetraacetic acid iron (m) complex salt V.

The redox potential of the oxidizing agent in the above is based on the Transactions of the Faraday Society.
actions of the Faraday
5ociety), Volume 55 (1959), 131
It is defined by the redox potential measured by the method described on pages 2 to 1313.

The redox potential in this case was obtained by the above-mentioned method under the condition of pH 6.0.

Like this p)! The reason why the potential determined at pH 6.0 is adopted is that pH around 6.0 is a guideline for the occurrence of bleaching blade burr.

In other words, the present inventors have actually found that when the color development process is completed and the photosensitive material enters the bleaching solution, p in the film of the photosensitive material is
H decreases, but if the pH decreases quickly at this time, the bleach fog will be small, but if the decrease in PO is slow or the pH of the bleaching solution
It has been confirmed that the bleaching blade burr becomes larger when the temperature is high.
From these facts, po6. o is the standard.

The reason why a high-potential oxidizing agent having a redox potential of 150 mV or more is used is that such an oxidizing agent can provide sufficient oxidizing power and can perform a rapid bleaching process.

When rapid processing is performed using such a high-potential oxidizing agent, the reduction in processing performance due to evaporation and concentration of the bleaching solution becomes a serious problem, so evaporation correction is particularly effective.

Such high potential oxidizing agents include inorganic compounds such as red blood salts, ferric chloride, dichromates, persulfates, bromates, and some organic compounds such as aminopolycarboxylic acid iron (m) complex salts. Examples include type compounds.

In the present invention, it is preferable to use an aminopolycarboxylic acid iron(III) complex salt from the viewpoints of environmental protection, handling safety, metal corrosivity, and the like.

Below, aminopolycarboxylic acid iron (II) in the present invention will be described.
I) Specific examples of complex salts will be given, but the invention is not limited to these. In addition, the redox potential in the above definition will be described.

Compound no.

Redox potential (oV vs, NHE, pH*6) 1, N-(2-acetamido)iminodiacetic acid iron (II [) salt 2, methyliminodiacetic acid (m) complex salt 3, iminodiacetic acid elephant (m) complex salt 4 , 'l+ 4-Butylenediaminetetraacetic acid (I[I) complex salt 5, diethylenethionityldiaminetetraacetic acid (DI) complex salt 6, glycol ether diamine tetraacetic acid ferric salt ([[[)♀ salt 7.1. 3-propylene diamine, Ill rust salt 80 00 10 30 30 40 50 Among these, particularly preferred are compound No.
7 1,3-propylenediaminetetraacetic acid iron(III)
fit″A (hereinafter referred to as l,3-PDTA-Fe(tn)
(This is the same compound as the 1,3-diaminopropanetetraacetic acid complex salt (III) disclosed in JP-A-62-222252 and JP-A-64-24253).

Aminopolycarbonate Note (nl) GW salts are used in conjunction with sodium, potassium, ammonium, etc., but ammonium salts are preferred because they bleach the fastest.

On the right, ethylenediaminetetraacetic acid ua (m) yH solution (EDTA-F e (I), which is widely used in the industry)
II) is IIc) eV, and diethylenetriaminepentaacetic acid e(II[) complex salt, trans-1,2-cyclohexanediaminetetraacetic acid iron(III) salt, etc. are 80 mV, and from those in 3 of the present invention. are excluded.

The amount of oxidizing agent used in the bleaching solution according to the present invention is as follows: bleaching solution I
It is preferably 0.17 mol or more per n, and 0.25 mol or more is preferable from the viewpoint of speeding up the processing and reducing bleaching blade blur and stain, and particularly preferably 0.30 mol or more. However, since the use of an excessively high concentration solution will actually inhibit the bleaching reaction, the upper limit of the concentration is preferably about 0.7 mol.

Further, in the present invention, the oxidizing agent may be used alone or in combination of two or more.

When two or more types are used together, the total concentration may be within the above range.

Furthermore, according to the present invention, the redox potential is 150 mV.
In addition to the above oxidizing agents, oxidizing agents with an oxidation-reduction potential of less than 150 mV may be used in combination; however, the amount used is 0.5 per mole of the oxidizing agent with an oxidizing potential of 150 mV or more.
It is preferable to set it to about molar or less.

Examples of such substances include ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, especially when used in combination with aminopolycarboxylic acid iron (111) rust and salt, which have an oxidation-reduction potential of 150 mV or more.

Examples include ferric complex salts of cyclohexanediaminetetraacetic acid.

By the way, when using aminopolycarboxylic acid iron (III) complex salt in a bleaching solution, it can be added in the form of a complex salt as mentioned above, but it can also be added in the form of a complex salt such as aminopolycarboxylic acid, which is a box-forming compound, and a secondary salt (e.g. , anti-acid ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate) may be allowed to coexist to form a complex salt in the bleaching solution.

In the case of this brim formation, the aminopolycarboxylic acid may be added in a slightly excess amount than the amount required for complex formation with the second Shishi ion, and when added in excess, it is usually 0.01
It is preferable to use an excess in the range of 10% to 10%.

Bleaching solutions as described above are used - numerically at a pH of 2 to 8. In order to speed up the treatment, the pH should be adjusted to 2.5 to 4.
．． 2. Preferably 2-5 to 4, preferably 2 to O,rr
．． 5 to 3.5, and the replenisher is usually 1.0.
~4. It is better to use it as O.

In the present invention, known acids can be used to adjust p)I to the above range.

As such an acid, an acid with a pKa of 2 to 5.5 is preferable. In the present invention, pKa represents the logarithm of the reciprocal of the acid dissociation constant, and the ionic strength is 0.1 mol/! , shows the value determined at 25°C.

In the present invention, it is preferable to use a bleaching solution containing 1.2 mol/or more of a metal having a pKa of 2.0 to 5.5 in the desilvering step.

By containing 1.2 mol/1 or more of an acid with a pKa of 2.0 to 5.5 in the bleaching solution, it is possible to further eliminate bleaching blade blur and improve the increase in stain in uncolored areas after treatment. .

The acid with a pKa of 2.0 to 5.5 may be any inorganic acid such as phosphoric acid, acetic acid, malonic acid, citric acid, etc.;
Acids with a2.0 to 5.5 are organic acids. Among organic acids, talic acids having a carboxyl group are particularly preferred.

The organic acid with a pKa of 2.0 to 5.5 may be a monobasic acid or a polybasic acid. In the case of a polybasic acid, its pKa should be in the above range of 10 to 5.5. It can be used as metal salts (e.g. sodium and potassium salts) and ammonium salts. In addition, organic acids with pKa of 2.0 to 5.5 are
It is also possible to use a mixture of more than one species. However, aminopolycarbon M 8 and its Fe main salt are excluded.

Preferred specific examples of organic acids with a pKa of 2.0 to 5.5 used in the present invention include formic acid, acetic acid, monochloroacetic acid,
Aliphatic-based acids such as monobromoacetic acid, glycolic acid, propionic acid, monochloropropionic acid, lactic acid, hiruhic acid, acrylic acid, butyric acid, isobutyric acid, bibaric acid, aminohydric acid, valeric acid, isovaleric acid; Amino acid compounds such as asparagine, alanine, arginine, ethionine, glycine, glutamine, cysteine, serine, methionine, and leucine; aromatic compounds such as benzoic acid and monosubstituted benzoic acids such as chloro and hydroxy, and nicotinic acid. basic acid;
Aliphatic tribasic acids such as oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid, glutaric acid, adipic acid: aspartic acid, glutamic acid, glutaric acid, cystine, ascorbic acid Various organic acids can be listed, such as amino acid tribasic acids such as; aromatic tribasic acids such as phthalic acid and terephthalic acid; and polybasic acids such as citric acid.

In the present invention, among these, monobasic acids having a carboxyl group are preferred, with acetic acid and glycolic acid being most preferred.

In the present invention, the appropriate amount of these acids to be used is 0.5 mol or more per 11 in the bleaching solution. Preferably it is 1.2 to 2.5 mol/l. More preferably, it is 1.5 to 2.0 mol/l.

, the pH of the bleaching solution is adjusted to the above range, the acid and alkaline agents (e.g. aqueous ammonia, KOH, NaOH,
(imidazole, monoethanolamine, jetanolamine) may be used in combination. Among them, aqueous ammonia is preferable. Also, as an alkaline agent, it can be used as a bleach starter when preparing the bleaching mother liquor from the bleach replenisher. ,
Preferably, imidazole, monoethanolamine or jetanolamine is used.

According to the present invention, various bleach accelerators can be added to the bleach solution or its pre-bath. Such bleach accelerators are described, for example, in U.S. Pat. No. 3,893,858.
Specification of German Patent No. 1,290,812,
British Patent No. 1,138,842, JP-A-53-
Publication No. 95630, Research Disclosure No. 1
Compounds having mercaptobenzene or disulfide groups described in No. 7129 (July 1978 issue), JP-A-1988-1
Thiazolidine derivatives described in US Pat. No. 40129, thiourea derivatives described in US Pat. No. 3,706,561, iodides described in JP-A-58-16235, German Patent No. 2,748.430. Polyethylene oxides described in the specification, polyamine compounds described in Japanese Patent Publication No. 45-8836, etc. can be used. Particularly preferred are mercapto compounds as described in Japanese Patent No. 1,138,842.

In addition to the oxidizing agent (bleaching agent) and the above-mentioned compounds, the bleaching solution suitable for the present invention includes bromides such as potassium bromide, sodium bromide, ammonium bromide, or compounds such as potassium chloride, sodium chloride, ammonium chloride, etc. rehalogenating agents. The concentration of the rehalogenating agent is 0.1 to 5 mol per 11 in the bleaching solution,
Preferably it is 0.5 to 3 mol.

Moreover, it is preferable to use ammonium nitrate as the metal layer 1c inhibitor.

In the present invention, as mentioned above, it is preferable to adopt the replenishment method, and the amount of replenishment of the bleaching solution is per 11 of the photosensitive materials.
20-0w1 or less, preferably 140-1Om! It is.

Further, the bleaching treatment time is 120 seconds or less, preferably 50 seconds or less, and more preferably 40 seconds or less. The present invention is effective due to such shortened processing time.

However, during treatment, iron aminopolycarboxylate (m) =
= It is preferable to add Aireshimin to the bleach solution using salt to oxidize the aminopolycarboxylic acid number (n)i salt produced.

This regenerates the oxidizing agent and keeps photographic performance extremely stable.

In a preferred desilvering process of the present invention, the light-sensitive material that has been bleached with the above-mentioned bleaching solution is treated with a processing solution having runner ability.

In this case, the processing liquid having the runner ability is specifically a fixing liquid and a bleach-fixing liquid, and after the bleaching process, a bleach-fixing process and/or a fixing process are performed.

These processing solutions contain a constant IF agent.

As fixing agents, thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, potassium thiosulfate, thiocyanates (Rodan fences) such as sodium thiocyanate, ammonium thiocyanate, potassium thiocyanate, thiourea, Thioethers and the like can be used.

Among these, it is preferable to use ammonium thiosulfate.
．． The amount is 3 to 3 mol, preferably 0.5 to 2 mol.

In addition, from the viewpoint of promoting fixation, the above-mentioned ammonium thiocyanate (rhodan ammonium), thiourea, thioether (for example, 3,6-cythia-1,8-octanediol)
It is also preferable that the amount of these compounds used in combination is 0.01 to 0.0% per fixer or bleach-fixer.
The amount is generally about 1 mol, but in some cases, the fixing promoting effect can be greatly enhanced by using 1 to 3 mol.

As the runner agent in the fixing solution or bleach-fixing solution, in order to speed up the processing, it is particularly preferable to use thiosulfate and thiocyanate in combination. Preferably for valves.

In this case, the amount of thiosulfate is 0.3 to 3 mol/1 as mentioned above, and the amount of thiocyanate is 1 to 3 mol/1. Preferably, it may be used in an amount of 1 to 2.5 mol/1.

Other compounds other than thiocyanate that can be used in combination with thiosulfate (particularly ammonium thiosulfate) include thiourea and thioether (for example, 3,6-cythia-1,8-octanediol).

The amount of these compounds to be used in combination is generally about 0.01 to 0.1 mol per lt of the runner solution or bleach-fix solution, but in some cases it may be 1 to 3 mol.

The runner solution or bleach runner solution contains sulfur salts as preservatives (e.g. sodium sulfate, potassium sulfite, ammonium sulfate) and hydroxylamine, hydrazine,
In addition, various room light brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, methanol, etc. Although it is possible to contain a sulfinic acid compound, it is particularly preferable to use a sulfinic acid compound described in Japanese Patent Application No. 283881/1983, Meiwa Sho, as a preservative.

The bleach-fix solution may contain the above-mentioned known oxidizing agent (bleaching agent), and is preferably an aminopolycarboxylic acid.

Similarly to the bleaching process described above, it is preferable to carry out the bleach-fixing process while replenishing the processing solution and with water.

The amount of bleaching agent added to the bleaching agent solution per solution 11 is 0.01 to 0.5 mol, preferably O.
-0.3 mol, particularly preferably 0.02-0.2
It is a mole.

In the present invention, the bleach-fix solution (mother liquor) at the start of processing is
The bleach-fix solution described above is prepared by dissolving the compound used in water, but it may also be prepared by mixing an appropriate amount of separately prepared bleach solution and fix solution.The pH of the fix solution is 5 to 5.
The pH of the bleach-fix solution is preferably 9, more preferably 7 to 8. The pH of the bleach-fix solution is preferably 6 to 8.5, and more preferably 6.5 to 8.0.

When using the replenishment method, the amount of cleaning solution of the runner solution or bleach-fixing solution is 300 to 3000 m per 11 pieces of light-sensitive material!
is preferable, and more preferably 300 to 10,100O.

Furthermore, it is preferable to add various aminopolycarbon MWMs and organic phosphonic acids to the runner liquid and bleach runner liquid for the purpose of stabilizing the liquid.

Further, in the present invention, the total processing time of the runner processing or bleach-fixing processing performed after the cleansing process is preferably 0.5 to 2 minutes, particularly 1 to 1.5 minutes.

The present invention is effective when applied to such short processing times.

The shorter the total treatment time of the desilvering step of the present invention, the more remarkable the effects of the present invention can be obtained.6 The preferred time is 1 to 4 minutes;
More preferably, the time is 1 minute 30 seconds to 3 minutes. The treatment temperature is 25-50°C, preferably 35-45°C. When the temperature is within the preferred temperature range, the desilvering rate is improved and staining after treatment is effectively prevented.

In the above description, 4, which is a preferred desilvering process in the present invention, in which a bleaching process is performed immediately after the color development process, has been explained. The present invention can also be applied to treatment step (2).

The solution composition of the bleach-fix solution used in the above bleach-fix treatment is as follows: is basically the same thing.

The present invention is applicable not only to bleaching or bleach-fixing immediately after the above-mentioned color development process, or to bleach-fixing that follows bleaching, but also to bleaching or bleach-fixing, such as bleaching using a stop bath, etc. It can be applied to the Sakai in general.

8. In the bleaching, bleach-fixing, and fixing processes of the present invention, the desilvering process requires that stirring be as advanced as possible.
This is preferable in order to more effectively exhibit the effects of the present invention.

A specific method of stirring evolution is described in Japanese Patent Application Laid-Open No. 62-18346.
No. 0, No. 62-183461, the method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material, and the method of colliding a jet of a processing liquid on the emulsion surface of a photosensitive material, as described in JP-A No. 62-183-1.
A method of increasing the stirring effect using the rotating means of No. 83461, and further improving the stirring effect by moving the light-sensitive material while bringing the emulsion surface into contact with a wiper blade that has been submerged in the liquid, and making the emulsion surface irregular. For example, methods for increasing the circulation flow rate of the entire processing liquid may be mentioned. Such agitation improvement means are effective for any of the bleaching liquid, the bleaching window S liquid, and the F@ liquid. It is thought that improved stirring speeds up the supply of bleaching agent and runner agent into the emulsion film, and as a result increases the desilvering rate.

Further, the agitation enhancement means is more effective when a bleaching accelerator is used, and can significantly increase the bleaching accelerating effect and eliminate the effects of bleaching accelerators.

The present invention is usually carried out by speed reading processing using an automatic developing machine. It is preferable to have the light-sensitive material fine transport means described in the above-mentioned JP-A-60-19125.
As stated in No. 7, such a conveyance means can significantly reduce the carry-over of processing liquid from the front bath to the rear bath, and is highly effective in preventing deterioration in the performance of the processing liquid. This is particularly effective in shortening processing time and reducing the amount of processing liquid replenishment.

The effect of the present invention (particularly the effect of reducing staining over time after processing) is achieved over the entire processing time (excluding drying time).
This is noticeable when the total processing time is short, specifically when the total processing time is 8 minutes or less, and when the total processing time is 7 minutes or less, the difference from the conventional processing method becomes even more remarkable. Therefore, in the present invention, the total treatment time is preferably 8 minutes or less, particularly preferably 7 minutes or less.

This is because am is marou.

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

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene 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-hydroxyethyl)aminocoaniline D-64-amino-3-methyl-N-ethyl-N −[β
-(methanesulfonamido)ethyl]aniline p-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phuninylenediamine D-94-amino-3-methyl- N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above-mentioned -phnynylenediamine derivatives, Exemplified Compound D-5 is particularly preferred.

In addition, these p-hunynylenediamine derivatives may be salts such as sulfates, sulfates, succinates, p-toluenesulfone sulfates, etc. Use of aromatic primary amine color developing agents The amount is preferably about 0.1 per 11 parts of color developer.
to about 20 g, more preferably from about 0.5 to about 10 g.

In addition, color developing solutions require preservatives such as sulfates such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium sulfate, sodium metasulfite, potassium metasulfite, and carbonyl succinic acid adducts. You can add it according to your needs.

The preferable amount of preservative added is 0.5 per 11 parts of color developer.
-10g, more preferably 1-5g.

In addition, 1 loss of the aromatic primary amine color developing agent,
Examples of the preserving compound include various hydroxylamines, hydroxamic acids described in JP-A No. 63-43138, and JP-A No. 63-43138.
Hydrazines and hydrazides described in No. 3-146041, phenols described in No. 63-14640 and 63-58443, α-hydroxyketones and a-aminoketones described in No. 63-44656 and/or It is preferable to add saccharides described in JP-A No. 63-36244.
-4235, 63-24254, 53-216
No. 47, No. 63-146040, No. 63-27841
Monoamines described in No. 63-25654, No. 63-30845, No. 63-14640, No. 6
Diamines described in No. 3-43139, etc., No. 63-21
No. 647, No. 53-21647 right and No. 63-146
Polyamines of No. 040, nitroxy radicals described in No. 63-53551, alcohols described in No. 63-14640 right and No. 63-53549, No. 63-56
Oximes described in No. 654 and No. 63-239447
It is preferable to use the tertiary amines described in No.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
- Salicylic acids described in No. 180588, JP-A-54-3
Alkanolamines described in No. 582, JP-A-56-9
No. 4349! The polyethyleneimine described in No. 2, the aromatic polyhydroxy compound described in U.S. Pat.

The color developing solution used in the present invention preferably has a pH of 9 to
12, more preferably 9 to 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.

Specific examples of E buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium phonate, and potassium borate. , Sodium Tetraborate (Borax) Potassium Tetraborate, 0-
Sodium hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate, 5-sulfo-2
Examples include sodium -hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), etc. However, the present invention is limited to these compounds. It's not Rumo-no.

The amount of buffering agent added to the color developing solution is preferably 0.1 mol/l or more, particularly preferably 0.1 to 0.4 mol/l.

In addition, various chelating agents may be added to the color developer to act as anti-settling agents for calcium and magnesium, or to improve the 5U properties of the color developer.

The chelating agent is preferably an organic compound, such as aminopolycarboxylic acid, organic phosphonic acids, or phosphonocarboxylic acids. Specific examples are shown below, but the chelating agent is not limited to these.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1.2 -diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid i2, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1°2.4-tricarboxylic acid,
1-hydroxyethylidene-1,1-diphosphonic acid, N
, N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid.

Two or more of these chelating agents may be used in combination, if necessary.

The amount of these chelating agents added may be an amount sufficient to sequester metal ions in the developing solution, for example, 0.1 to Log per 12.

Any development accelerator can be added to the color developing solution if necessary. However, the color developing solution according to the present invention has some drawbacks in terms of pollution, solution stability, and color stain prevention.
Preferably, it does not contain substantially benzyl alcohol, and "substantially" here means that it contains not more than 2 ml per developer, preferably not at all.

In addition, as a development accelerator, Japanese Patent Publication No. 37-16088
No. 37-5987, No. 38-7826, No. 44
-12380, 45-9019, U.S. Patent No. 3,
Thioether compounds described in No. 818,247 Jinshin; p-phenylenediamine compounds described in JP-A-52-49829 and JP-A-50-15554;
No. 137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 1977
6-156826, 4-string ammonium fences described in 52-43429, etc., U.S. Patent No. 2,494,903
No. 3,128,182, No. 4,230゜79
No. 6, No. 3,253,919, Special Publication No. 41-114
No. 31, U.S. Patent No. 2,482゜546, U.S. Patent No. 2,546
96,926, amine compounds described in Japanese Patent Publication No. 37-16088, Japanese Patent Publication No. 37-16088, No. 42-
No. 25201-1 Polyalkylene oxide described in U.S. Patent No. 3,128,183, Japanese Patent Publication No. 11431-1983, Japanese Patent Publication No. 42-23883, U.S. Patent No. 3,532,501, etc., and other 1-phenyl-3-pyrazolidones. kind,
Imidazole and the like can be added as necessary.

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

The color developing solution used in the present invention may contain a photonic brightener. Examples of the room photonic brightener include 4,4°-diamino-2,2°-disulfostilbene compounds. Preferably, the amount added is O~5 g/l, preferably 0.1 g~4
g/! It is.

In addition, if necessary, alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, aromatic carboxylic acid M? Various surfactants may be added.

The processing temperature in the color developing solution in the present invention is 20 to 50°C.
, preferably 30 to 45°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes and 20 seconds. East 1
As shown in the figure, when using the replenishment method, the smaller the replenishment amount is, the better;
1500a+1, preferably 100-800m1. More preferably 100-400m! It is.

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

The processing method of the present invention uses a color reversal process, and the black-and-white developer used at this time is a so-called black-and-white first developer used in the commonly known reversal process of color photosensitive materials. Various well-known additives which are added to the black and white developer used after processing black and white silver halide light-sensitive materials can be incorporated into the developer for color reversal light-sensitive materials.

Typical additives include 1-phenyl-3-pyrazolidone, developing agents such as metol and hydroquinone, preservatives such as silicate, sodium hydroxide, sodium carbonate, and potassium carbonate. A developer consisting of an accelerator consisting of an alkali, an inorganic or organic inhibitor such as potassium bromide, 2-methylbenzimidazole or methylbenzithiazole, a water softener such as a polyphosphate, and trace amounts of iodide or mercapto compounds. I can give you a suppressant.

The processing method of the present invention includes processing steps such as color development, bleaching, bleach-fixing, and fixing as described above. Here, after the bleach-fixing W or runner step, as shown in Figure -i1, processing steps such as water washing S and stabilization are generally performed, but a processing solution with fixing ability is After treatment, it is also possible to use a more advanced treatment method that does not require substantial washing with water and then performs support treatment.

The rinsing water used in the rinsing process may contain known additives, if necessary.

For example, inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphate water softeners, fungicides and fungicides that prevent the growth of bacteria and lacquer (e.g., isothiazolone, organic fungicide, benzotriazole) etc.), drying load, surfactant to prevent unevenness, etc. can be used. Or, L, E, Wast, “1 master
QualityCrite, ria”, Photo, S
ci, and Eng,, vol, 9°No,
6. Compounds described in p. 344-359 (1965) and the like can also be used.

As the stabilizing liquid used in the stabilization step, a processing liquid that stabilizes the pentagonal image is used. For example, pH 3-6,
i! aldehydes (e.g. formalin)
The stabilizing solution may contain an ammonium compound, a metal compound such as Bi or An, a room light brightener, a chelating agent (for example, 1-hydroxyethylidene-1), if necessary. , 1-diphosphonic acid), bactericides, fungicides, hardeners, surfactants, alkanolamines, etc.

In addition, for the water washing process and the turf spreading process, a multistage countercurrent method is preferable, as in the water washing process shown in Figure 1, and the number of stages is preferably 2 to 4.The replenishment amount is from the pre-bath per unit area. 1 to 50, preferably 2 to 30 times the amount brought in,
More preferably it is 2 to 15 times.

In addition to tap water, the water used in these washing steps or stabilization steps is
a. It is preferable to use water that has been deionized to a Mg concentration of 5 mg 71 or less, and water that has been sterilized using halogen and ultraviolet garlic sterilization lamps.

In addition, tap water may be used as the water for correcting the evaporation content, but it is preferable to use deionized water or sterilized water for use in the above-mentioned washing process or turf treatment process. .

*As shown in Figure 1, we asked Yamei not only for bleaching solutions and bleaching solutions containing high-potential bleaching agents, but also for other processing solutions by correcting concentration through evaporation. In order to do this, it is preferable to add an appropriate amount of water, correction liquid, or processing liquid.

In addition, as shown in Figure 1, the overflow liquid from the washing process or support or fixing process is allowed to flow into the pre-bath, which has a fixing ability, thereby reducing the amount of waste liquid. You can also let them do it.

The light-sensitive material according to the third aspect of the present invention may be provided with at least one silver halide emulsion layer of a noble color-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support, There are no particular restrictions on the number of layers and the order of the silver halide emulsion layers and non-light-sensitive layers.A typical example is to place silver halide emulsion layers and non-light-sensitive layers on a support with substantially the same color sensitivity but with different light sensitivities. It is a silver halide color photographic light-sensitive material having a photosensitive layer consisting of a plurality of silver halide emulsion layers, and the photosensitive layer is a positional photosensitive material that is sensitive to blue light, T2E light, and red light. In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layers are generally arranged in the following order from the support side: a red-sensitive layer, a green-sensitive layer, and a fiF-sensitive layer. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that the color-sensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various spatial layers may be provided between the silver halide photosensitive layers 3, the uppermost layer, and the lowermost layer.

For the middle class, JP-A-61-43748 and JP-A-59-11
No. 3438, No. 59-113440, No. 61-200
No. 37, No. 61-20038, the coupler DIR compound may be included, and it may also contain a color mixing inhibitor, an ultraviolet absorber, an anti-stinting agent, etc. as commonly used. You can stay there.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are
West German Patent No. 1,121,470 or certain country Patent No. 9
As described in No. 23,045, a two-layer structure consisting of a high pressure sensitive emulsion layer and a low pressure sensitive emulsion layer can be preferably used.
Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between the winter halogen emulsion layers.

Also, JP-A-57-112751, JP-A No. 62-2003
No. 50, No. 62-206541, No. 62-20654
As described in No. 3, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the most used side of the support, low-sensitivity blue-sensitive layer (BL) / high-sensitivity blue-sensitive layer (BH) / high-sensitivity Lc
The order of photosensitive layer (GH) / low sensitivity blue sensitive layer (GL) / high sensitivity red sensitive layer (RH) / low sensitivity red sensitive layer (RL) / or B H / B L / GL / GH/RH/RL
or B H/B L/G H/G L/RL/
They can be installed in the order of RH, etc.

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

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is a silver halide emulsion layer with higher sensitivity than the middle layer. One example is an arrangement consisting of three layers with different sensitivities, in which a silver halide emulsion layer with low sensitivity is arranged and the sensitivities are successively lowered toward the support.
Even in a case where the layer is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464, the medium-sensitivity emulsion layer/ They may be arranged in the order of high-speed emulsion layer/low-speed emulsion layer.

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

Any of these original arrangements can be used in the color light-sensitive material of the present invention, but in the present invention, the dry film thickness of all the constituent layers of the color light-sensitive material excluding the right side of the support, the right undercoat layer of the support, and the back layer is 20. It is preferable that it is 0μ or less in order to quickly achieve the object of the present invention, more preferably 1
It is 8.0μ or less.

These film thickness regulations are determined by the color developing agent that is incorporated into these layers of the color photosensitive material during and after processing. By making a big impact. In particular, the increase in color of magenta, which is thought to be caused by the green-sensitive color layer, is greater than the increase in color of other cyan and yellow colors.

On the other hand, it is desirable that the lower limit of the film thickness regulation be reduced to the extent that it does not significantly impair the performance of the photosensitive material based on the above regulations.The structure of the photosensitive material excluding the support and the undercoat layer of the support. The lower limit of the company-wide i2 film thickness of the layer is 12.0
μ, and the lower limit of the dry film thickness of the constituent layer provided between the photosensitive layer closest to the support and the undercoat layer of the support is 1.
It is 0μ.

Further, the film thickness may be reduced in either the photosensitive layer or the non-photosensitive layer.

The film thickness of the multilayer color photosensitive material in the present invention is measured by the following method.

The photosensitive material to be measured is stored at 25° C. and 50% RH for 7 days after its preparation. First, measure the total thickness of this photosensitive material, then remove the coated layer on the support, measure the thickness again, and use the difference to determine the total thickness of the photosensitive material excluding the support. The film thickness shall be . The thickness can be measured using, for example, a film thickness measuring device using a contact type electric conversion element (Anritus Electric Co., Lt.
d.

K-40285tand, ). Incidentally, the coating layer on the support can be removed using an aqueous sodium hypochlorite solution.

Next, using a scanning electron microscope, take a cross-sectional photograph of the photosensitive material (magnification is preferably 3,000 times or more), measure the thickness of the layer and the @ layer on the support, and measure the thickness of the layer on the support. Measured value of thickness using a thickness measuring device (absolute M of actual thickness)
The thickness of each layer can be calculated by comparing the

Swelling rate of the photosensitive material according to the present invention [(25°C, H2,0
Equilibrium swelling film thickness in -25°C, 55% RH dry total film thickness/25°C, 55% RH drying II! Thickness)X100
] is preferably 50 to 200%, more preferably 70 to 150%.

If the swelling ratio deviates from the above-mentioned value, the amount of color developing agent remaining will increase, and this will have an adverse effect on photographic performance, image quality such as desilvering properties, and film properties such as film strength.

Furthermore, the swelling rate of the photosensitive material in the present invention is defined as 90% of the maximum swollen film thickness that reaches Bl when processed in a developing solution (38°C, 3 minutes and 15 seconds), and this 1
When the time required to reach a film thickness of /2 is defined as the swelling rate Tl/2, T1/2 is preferably 15 seconds or less, more preferably T1/2 is 9 seconds or less. .

The silver halide contained in the photographic emulsion layer of the color light-sensitive material used in the present invention may be any of silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver bromide, and silver chloride. Preferred silver halides are silver iodobromide, silver iodochloride, or silver iodochlorobromide containing up to about 30 mole percent silver iodide; particularly preferred are silver halides containing up to about 2 to about 25 mole percent iodide. It contains silver iodobromide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and dodecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. It may be one having crystal defects or a composite form thereof.

Even if the grain size of silver halide is about 0.2 microns or less, the projected area diameter is about 10 microns. .

The emulsion 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. 1.
7643 (December 1978), pp. 22-23, Emulsion preparation
nand types)” S and same No. 18716
(November 1979) 648 pages, Grafkide, “
"Physics and Chemistry of Photography", published by Paul Montell, CP, Gl.
afkides.

Chimie at Physique Photo
graphique Paul Montel, 196
7), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffin.

Photographic Ea+ulsion Ch
emistry (FocalPress, 1966
), Zelikman et al., “Manufacture and Application of Photohole IL+1”
Published by Focal Press (V, L, Zelikman e
tal, Making and CoatingP
photographic emulsion, Foc
Al Press, 1964).

U.S. Patent No. 3,574,628, U.S. Patent No. 3°655.3
Monodisperse emulsions such as those described in No. 94 and British Patent No. 1,413.748 are also preferred.

Further, tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are described in the book by Gutoff, Photographic Science and Engineering.
c5science and engineering
), Vol. 14, pp. 248-257 (1970): U.S. Pat. No. 4,434,226, U.S. Pat. No. 4,414.310
No. 4,430,048, No. 4,439,52
0 and British Patent No. 2.112.157.

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

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

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure No.
, No. 17643 and No. 18716, both of which 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 both relevant entries are shown in the table below.

-Additional 8" l Chemical sensitizer 2 Sensitivity enhancer 4 Brightener 5 Antifoggant, stabilizer coupler 7 Organic thermal medium external radiation absorber stain inhibitor dye image stabilizer hardener binder hardening agent, lubricant Coating aid, 3-sided active agent 15 Staticto RD 17643 23 pages 24 pages 24-25 pages 25 pages 25 pages 25 pages Right comb 25 pages 26 pages 26 pages 27 pages 26-27 pages 27 pages RD 18716 648 pages Migiri same as above 649 Page right Fm Page 650 Page 651 Left column Same as above Page 650 Right Kiri Same as above Same as above Various color couplers can be used in the present invention, and specific examples thereof include the above-mentioned RD No.

17643, ■-〇-G.

As a yellow coupler, for example, U.S. Patent No. 3,93
No. 3,501, Broom No. 4,022,620, No. 4,32
No. 6,024, No. 4,401.752, No. 4,2
48,961, Special Publication No. 5g-10739, British Patent System No. 1,425.020, Same Proposal No. 1,476.760,
US Pat. No. 3,973,968, No. 4.314.
No. 023, No. 4,511,649, European Patent No. 24
Those described in No. 9,473A and the like are preferred.

As the magenta coupler, 5-pyrazolone type 3 and pyrazoloazole type compounds are preferable, and US Pat.
No. 10,619, No. 4.351,897, European Patent No. 73,636, US Patent No. 3.061,432,
No. 3.725,064, RD No. 24220 (1
June 984), JP-A No. 60-33552, RD No.
, 24230 (June 1984) JP-A-60-436
No. 59, No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951,
U.S. Patent No. 4,500,630, 4,540゜6
No. 54, same proposal No. 4,556,630, WO (PCT) 8
Particularly preferred is 0 described in No. 8104795.

Cyan couplers include phenolic 3 and naphthol couplers, and are disclosed in U.S. Patent No. 4,052,21.
2, Proposal No. 4,146,396, Proposal No. 4,228,2
No. 33, same proposal No. 4゜296.200, same proposal No. 2,369,
No. 929, No. 2,801,171, No. 2,772
．． No. 162, No. 2,895,826, No. 3,77
No. 2,002, same passenger No. 3,758,308, same proposal 4,3
No. 34,011, No. 4327.173, West German Patent Publication No. 3,329.729, European Patent No. 121,365
No. A, No. 249,453A, U.S. Patent Series 3°446
．． No. 622, No. 4,333,999, No. 4,75
No. 3,871, No. 4.451.559, No. 4,4
No. 27,767, No. 4,690,889, No. 4,
254,212, 4,296,199, JP-A-61-42658, etc., may be used in combination with the coupler represented by the general formula (I) of the present invention.

Colored couplers for correcting unnecessary absorption of coloring dyes are disclosed in RD No. 17643, Item ■-G, US Patent Series 4,
No. 163,670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,004゜929, U.S. Patent No. 4,138,258, and certain country patent No. 1, 146, 368 are preferred; A coupler that corrects unnecessary absorption of the proton by a room light pigment released into the coupling pupil described in U.S. Patent No. 4,774,181, and U.S. Patent No. 4,
It is also preferred to use a coupler having as a leaving group a dye precursor group which reacts with a developing agent to form a dye as described in No. 777.120.

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 West German Patent Publication No. 3,234.533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4,576.910, British Patent Series 2,102
, No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is the aforementioned RD No.-17.
643, the patent described in Sections Vii to F, JP-A-57-
No. 151944, No. 57-154234, No. 60-1
No. 84248, No. 63-37346, U.S. Patent No. 4.
248,962 and M4.782.012 are preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2097.140;
No. 2,131,188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the light-sensitive material of the present invention include the trochanteric coupler described in U.S. Pat. No. 4,130,427; 393, the multi-equivalent coupler described in No. 4,310,618 No. 0, the DIR redox compound releasing coupler described in JP-A No. 60-185950, JP-A No. 62-24252, etc. DIR coupler-releasing coupler DI
R coupler releasing redox compound or DIR redox releasing redox compound, European patent series 173,302
Coupler R that releases a dye that recovers color after separation as described in item A
DNo. 11449, 24241, JP-A-61-20
Bleach accelerator-releasing couplers described in US Pat. No. 1247, etc., ligand-releasing couplers described in US Pat. Examples include couplers that emit room light pigments as described in No. 774,181.

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

An example of high boiling point melting used in the oil-in-ice dispersion method is the US Pat.
'F plan 2,322,027 and other numbers are listed,
Specific examples of high-boiling organic solvents with a dropping point of 175°C or higher at normal pressure used in the oil-in-ice dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , bis(2,4-di-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1°1-diethylpropyl) phthalate, etc.), monononic acid or phosphonic acid Acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphonate, etc.)
, fuzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-
hydroxybenzoate, etc.), amide fi (N, N-
Diethyldodecaneamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (stearyl alcohol, 2
．． 4-tart-amylfuninol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N.

N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.).
Preferably, an organic solvent having a temperature of 50° C. or more and about 160° C. or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

Specific examples of the latex dispersion process, effects and latex for impregnation are disclosed in U.S. Pat.
No. 541,230, etc.

These couplers can also be prepared by impregnation into rhodapulu latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high point organic solvents mentioned above, or by making them horizontally soluble and having a It can be dissolved in a solvent-soluble polymer and emulsified and dispersed in an aqueous hydrophilic colloid solution.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. W08 B100723 are used. In particular, the use of acrylamide-based polymers is preferred from the viewpoint of color image stabilization.

The present invention can be applied to various color photosensitive materials, and is particularly preferably applied to color negative films for general use or movies, and color reversal films for slides or televisions.

Suitable supports that can be used in the present invention include, for example, the R
D No. 17643 page 28 and same No. 18716
It is described from the right column on page 647 to the left column on page 648.

(Effects of the Invention) According to the method of the present invention, processing is performed through a desilvering process that is faster and requires less replenishment, and desilvering defects do not occur, and the occurrence of processing stains and stains during storage is suppressed. It has excellent functions and effects.

(Example) Next, the present invention will be explained based on the example.
A multilayer color photosensitive material II ($4101) was prepared, which is a multilayer color photosensitive material consisting of each layer of m precepts as shown below.

(Composition of the photosensitive layer) The coating amount is the amount expressed in g/n (units) of silver for silver halide and colloidal silver, and the amount expressed in g/n (units) for coupler additives and gelatin. The amount
Regarding sensitizing dyes, the number of moles is expressed per mole of silver halide in the same layer.

1st JW (Anti-halation N) Black colloid i 0.15 gelatin 1.50ExM-8
0.02 21st'i (intermediate layer) Gelatin 1.50UV-1
0,03 UV-20,06 UV-30,07 EχF-10,004 5olv-20,07 3rd layer (low sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgT 2 mol%, internal high Agl type,
Equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 29%, normal crystal, twin crystal mixed particles, diameter/thickness ratio 2.5) Coated silver I
0.50 gelatin 16
0゜EχS-11,0XIO-'ExS-23,0XIO-'ExS-31,0XIO-' ExC~3 0.22EχC-4
Q.
Equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 20%, normal crystal, twin crystal mixed particles, diameter/thickness ratio I) Coated silver 1
0.85 gelatin 1.2
6EχS-11,0XIO-' xS-2 ExC-3 ExC-3 3,0X10-'1,0xlO-' 0,33 ExY-14 ExY-13 ExC-2 pd-10 Solv-1 5th layer (high sensitivity Red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high Agl type,
Equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 30%, twinned mixed particles, diameter/thickness ratio 2) Coated silver ff1
0.70 gelatin 1.00
EχS-11,0XIO-'EχS-23,0XIO-'EχS-31,0XIO-' EχC-50,t.

ExC-6o,. 5 0,01 0,02 0,08 1.0X10-' 0,10 Solv-10,15 Solv-20,08 6th layer (middle layer) Gelatin 1.00P-20
, 17 Cpd-10. 3 μm, coefficient of variation of equivalent sphere diameter 28%, normal crystal,
Twinned mixed grains, diameter 10 ratio 2.5) Coated silver amount,
0.30 gelatin 0.40E
xS-45,0XIO-'ExS-60,3XIO-'EXS-52,0XIO-' ExM-90,2 ExY-130,03 ExM-80,03 Solv-10,20 Shi0JM (medium-sensitivity green-sensitive emulsion layer ) Silver iodobromide emulsion (Ag 14 mol%, internal high Agl type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 20%, normal crystal, mixed twin grains, diameter/thickness ratio 4) Amount of coated silver
0.70 gelatin 1.00
EχS-45,0XIO-'EχS-52,OXl,O-'EχS-60,3X1o-' EχM-90,25 EχM-80,03 EχM-100,015 EχY-130,04 Solv-10,20 9th Layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Agl 10 mol%, internal high Agl type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 30%, normal crystal, mixed twin grains, diameter /thickness ratio 2.0) Coated silver! lit O,50 Gelatin Eχ5-4 Eχ5-5 EχS-6 xS-7 xM-1 EχM-1 EχM-8 Cpd-2 Cpd-9 Cpd-10 olv-1 olv-2 10th layer (yellow filter layer) Gelatin Yellow colloidal silver Cpd-1 olv-1 11N (low-range blue emulsion layer) Silver iodobromide emulsion (Ag 14 mol%, 0, 80 2.0X10 2.0xlO-' 0, 2X10 3, 0XIQ-' 0 , 06 0, 02 0, 02 0, O1 2, 0XIO 2,0X10-' 0, 20 0, 05 0, 60 0, 05 0, 20 0, 15 Internal height Agl type, equivalent sphere diameter 0.5 μm, sphere Coefficient of variation of equivalent diameter 1
5%, octahedral particles) Coated silver amount 0.40 Gelatin 1.00EχS-
82.0 , equivalent sphere diameter 1.3 μm, coefficient of variation of equivalent sphere diameter 25%, normal crystal, twin crystal mixed particles, diameter/thickness ratio 4.5) Coated silver amount 0.50 gelatin
0.60EχS-81,oXlo-' EχY-150,12 CPd-20,001 Cpd-52,0XIO-' 5olv-10,04 13th N (first protection Ji) Fine grain silver iodobromide (average grain size 0. 07 μm, AglI mol%) o, 2° gelatin
. , 8゜UV-20,10 UV-30,1O LIV-40,20 Solv-30,04 14th N (second protective layer) Gelatin 0.90 polymethyl methacrylate particles (diameter 1.5 μ'') 0 .20)(-1
0,40 Furthermore, in order to improve storage stability, processability, pressure resistance, anti-mold/bacterial properties, antistatic properties, and applicability, the following (7) Cp
d-3, Cpd-5, cpd-6, Cpd-,7, cp
d-13, P-LP-2, W-1° W-2, w-3 were added.

UV Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

4: 5olv-1 ni Li acid to of cresyl Sol-2: dibutyl phthalate o lv 3: Non-acid tri (2-ethylhexyl) EχF-1: C, H, 030 Yu ExC 2: ExM-8: ExC-4: ExC-5: ExC-6= C-6=Ex: S　-CHC○○CH.

ExY-14: ExY-15: Cpd-1: ExS-4: ExS-5: ExS-6: ExS-7: CH.

Cb　H+3(n) C=　H+ff(n) ExS-3: ExS-8: H-1= CH, =CH-3o□-CH, -CONH-CH.

CHz = CH-S Oz CH, -CONH-CH.

Cpd-3: Cpd-4 11 cpa-5: Cpd-6 Cpd-7 Cpd-8 Cpd-9 Cpd-10 -2 -3 -t -2 CJ+J02N (CxllJCHtCOOK Copolymer of vinyl pyrrolidone and vinyl alcohol (copolymer ratio -70
:30 volume ratio J) Polyethyl acrylate (preparation of sample 102) Cyan coupler ExC- in the third and fourth layers of sample 101
Exemplary coupler (I)-5 in place of 3, respectively 0
．． Sample 102 was prepared by adding 16 g/m" and 0.24 g/m".

The sample 102 was cut and processed into a width of 35 mm, subjected to imagewise exposure, and then processed using an automatic processor according to the following processing steps.

Treatment process Treatment time Treatment temperature Replenishment amount ° Tank capacity Coloring phenomenon 2 minutes 30 seconds 38℃ 20m11 10
I2 bleaching 25 seconds 38℃ 4.5 seconds
4℃ bleach fixing 40 seconds 38℃ -4
℃ fixation 40 seconds 38℃ 14m1
4-nin water washing (1) 30 seconds 38℃ -2℃
Washing with water (2) 20 seconds 38℃ 30 buildings
212 Stable 20 seconds 38℃ 201
2 minutes (drying 1 minute at 55℃) *Replenishment amount is the amount per 35 mm width and 1 meter length.Washing is (2)
(1), and all the overflows from the bleaching tank and the fixing tank were allowed to flow into the bleaching and fixing tank. Further, all the overflow from the water washing (1) tank was allowed to flow into the fixing tank.

The bleaching tank, bleach-fixing tank, and fixing tank each had an aperture ratio of 0.02.

The amount of color developing solution brought into the bleaching tank for a photosensitive material of 35 m x 111 m in width and 1 m in length was 2.5171 ii, and the amount of bleaching solution taken out was 2.4 yen.

The above photosensitive materials 101 and 102 were heated at 20 m/day (
The treatment was continued for one month at a rate of 0.7 rrr).

In the bleaching tank, the bleaching solution was aerated only during processing of the photosensitive material.

The composition of the treatment liquid is shown below.

(Color developer) Mother solution (g) Replenisher (g)
Diethylenetriaminepentaacetic acid 1.0 1.11-hydroxyethylideno1.1-diphosphonic acid 3.8 3.2 Sodium sulfite 4.0 4.9 Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 2-methyl- Add 4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline sulfate and H (bleach solution) 1.3-Propylenediaminetetraacetic acid ferric ammonium hydrate aqueous ammonia (28%) Odor ammonium chloride ammonium nitrate hydroxyacetic acid 30.0 1.4 1.5 mg 2.4 4.5 1.0°C 10.05 30.0 3.6 6.0 1.0°C 10.15 Mother liquor (g) Replenisher ( g) 138.0 3.4 80.0 20.0 50.0 207,0 5.1 120.0 30.0 75.0 Acetic acid (98%) Add water to pH [adjust with jetanolamine] 50 .0 1.04 3.3 (Fixer) Mother liquor (g) Ethylenediaminetetraacetic acid ammonium salt 12.0 Ammonium sulfite 20.0 Imidazole 30.0 Ammonium thiosulfate aqueous solution (700g/I2) 280.0 Add water 1.0°C pH 7.4 (bleach-fix solution) <Mother liquor> A bleach solution and a fix solution were combined at 1=8 (volume) to adjust the pH (pH 6.8).

75.0 1.0I2 2.8 Replenisher (g) 840m! Mix the common tap water of mother liquor and replenisher at a ratio of 1.0°C and 7.45 °C (washing water) with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion. Replacement resin (Amberlite IRA-4
Water was passed through a mixed bed column packed with 00) to reduce the concentration of calcium and magnesium ions to 3 mg/ff or less, followed by 20 mg of sodium incyanurate dichloride.
150 mg/I2 of sodium sulfate was added. The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to mother solution and replenisher solution (unit: g) Formalin (
37%) 2.0 m [l Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water
1.0βpH 5.8 to 8.0 Such treatment is referred to as treatment IA.

Subsequently, in Process 1A, the same process was carried out except that the formulation of the bleaching solution was changed as shown below, and the amount of replenishment was changed from 4.5 ml to 15 ml. This process is referred to as 1B.

1B Bleach Solution Formula Mother Liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid ferric ammonium ammonium bromide ammonium nitrate acetic acid (98%) Add water to pH [adjust with jetanolamine] 140.0 220.0 1&0 .0 250.0 20.0 30.0 10 15 1, O121, 0°C 5.5 4.5 The following tests and evaluations were conducted using each of the running liquids of treatments IA and IB described above.

A continuous glass wedge was passed through the violet samples 101 and 102.
Immediately after applying a short exposure of 00 lux and 17100 seconds and performing treatments IA and IB, the density was measured. Bleaching fog was evaluated based on the density value of the lowest density portion of the characteristic curve obtained here. The results are shown in Table 1.

Stin's! ... The samples evaluated for bleaching blade burr were left for one week at 60°C and 70%, and after a forced test, the concentration was measured. The aging stain was evaluated based on the concentration value obtained by subtracting the concentration value before the forced test from the concentration value obtained in this measurement (ie, the increase in concentration due to the forced test). Results first
Shown in the table.

Pass the glass stair wedge through the Pigeonfish specimens 101 and 102.
000 lux and 1/100 second exposure was given to perform processing LA and IB. Thereafter, the amount of residual silver in the maximum density portion was determined by fluorescent X-ray measurement. Desilvering properties were evaluated based on the amount of residual silver determined in this way. The results are shown in Table 1.

As is clear from the results in Table 1 below, when Sample 101 was treated with Treatment IA, the bleaching edge burr and aging stain increased (Experiment No. 1). However, when processing IB is performed, the amount of residual silver increases significantly, and the staining over time also increases (Experiment No.

2).

Next, even if sample 102 is treated with treatment B, the bleached blade burr and staining over time are reduced, but the amount of residual silver is significantly large (Experiment N
o, 4). On the other hand, when sample 102 was treated with treatment 1A, both bleaching edge blur and aging stain were reduced, and the amount of residual silver was extremely small.
- instead of -5, equimolar cyan coupler (I) -
1 was added.

This was designated as sample 103. The same tests and evaluations as in Example 1 were conducted using the treatment liquid prepared in Example 1. The results are shown in Table 1 as Experiment No. 5.6. As a result, in sample 103 (cyan coupler (I)-1), the effect of improving bleaching fog, aging stain, and residual silver amount was observed by performing treatment 1A, as in the case of cyan coupler (I)-5. Experiment No. 5).

Example 3 Sample 102 prepared in Example 1 was treated with the bleaching solution of 1A or the bleaching solution in which the oxidizing agent 1.3-propylenediaminetetraacetic acid ferric ammonium hydrate was replaced with an equimolar amount of another oxidizing agent. A treatment test was conducted in the same manner as in Example 1 using the liquid. The results are shown in Table 2. This result shows that the desilvering property is significantly improved when the redox potential of the oxidizing agent is 150 mV or higher.

Claims (1)

[Scope of Claims] A red-sensitive silver halide emulsion layer containing a cyan coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a blue-sensitive silver halide emulsion layer containing a yellow coupler on a support. at least one silver emulsion layer each
When a silver halide color photographic light-sensitive material having a layer is processed with a processing solution having bleaching ability after color development, the light-sensitive material contains at least one compound represented by the following general formula [I]. An image forming method for a silver halide color photographic light-sensitive material, characterized in that a processing solution containing at least one kind of oxidizing agent having a redox potential of 150 mV or more is used as the processing solution having bleaching ability. . General formula [I] ▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, R^1 is an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, or aryl group, -S-, -SO-, -SO_2-, -C
OO-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -SO_2O-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
Or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R^2 is a group that can be substituted on the benzene ring, l is an integer from 0 to 4,
R^3 represents an aryl group, and Z represents a hydrogen atom or a coupling-off group. However, R^6 is a hydrogen atom, an acyl group, or a group having the same meaning as R^1, and R^7 is a hydrogen atom or a group having the same meaning as R^1. )