JPH025044A - Method of processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance photographic characteristics, more particularly the sensitivity and max. density of a magenta color forming layer and to lower the min. density by incorporating at least one kind of specific silver halide emulsions and magenta couplers into the above material and incorporating at least one kind of org. preservatives into a color developing soln. CONSTITUTION:At least one kind of the silver halide emulsions contg. >=80mol% silver chloride and at least one kind of the magenta couplers expressed by the formula I are incorporated into at least one layers and at least one kind of the org. preservatives are incorporated into the color developing soln. The amt. of the color developing soln. to be replenished at the time of continuous processing is so determined as to be in a 20-150ml range per 1m<2> silver halide color photographic sensitive material. In the formula I, R1, R3 denote a substd. or unsubstd. phenyl group; R2 denotes a hydrogen atom, aliphat. or arom. acyl group, etc.; Y denotes a hydrogen atom or a group which can be eliminated at the time of coupling reaction with the oxidant of the developing agent. The photographic characteristics, more particularly the sensitivity and max. density of the magenta color forming layer are enhanced and the min. density is lowered in the continuous processing.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for processing silver halide color light-sensitive materials, and in particular to silver halide color light-sensitive materials in which the amount of replenishment of color developer is significantly reduced. This relates to a processing method.

(Prior art) The processing of silver halide color photographic materials basically consists of two steps: color development (in the case of color reversal materials, the preceding black and white first development) and desilvering. The method consists of a bleaching and fixing step or a single bath bleach-fixing step used in combination with or alone. If necessary, additional treatment steps such as water washing, stopping treatment, stabilization treatment, and pretreatment for accelerating development may be added.

Among silver halide color photographic light-sensitive materials, especially light-sensitive materials such as color photographic paper, in recent years there has been a strong demand for completing large quantities of prints within a short delivery time. To achieve this, it is necessary not only to use photosensitive materials that exhibit high color development in a limited processing time, but also to obtain excellent photographic performance even when a large amount of color photographic paper is processed continuously, and to maintain stable performance. What you are required to do. However, at present, these requirements cannot be met, and there are various problems such as coloring of the white background of color photographic paper due to deterioration of the color developing agent during long-term continuous processing;
There are problems such as variations in photographic performance (sensitivity or contrast) depending on the amount of processing. The main cause of deterioration of color developing agents is oxidation of the color developing agents by air and metals.

It is well known that various antioxidants (preservatives) are added for the purpose of preventing oxidation of these main ingredients. However, hydroxylamines, which are well-known preservatives and are used in various color developers, have the property of reducing the color development of couplers, and are easily decomposed by iron and copper ions. Decomposition products are not necessarily preferred preservatives because they tend to cause fog and have the disadvantage of affecting photographic properties.

Further, the dialkylhydroxylamines described in International Publication No. WO-87-04534 and JP-A No. 63-106655 have the same performance and are not necessarily preferred preservatives.

Sulfite ions are also well-known preservatives, but they act on the competing compounds of the coupler and reduce the color development of the coupler, or they act as a solvent for silver halide and cause a decrease in color density. So it's definitely not a desirable preservative.

In order to improve the stability of color developers, various preservatives and chelating agents have been studied. For example, as a preservative, JP-A-51-49828, JP-A-59-1
No. 60142, No. 56-47038, and U.S. Patent No. 3
Aromatic polyhydroxy compounds described in No. 746544 etc., US Patent No. 3615503 and British Patent No. 1306176
Hydroxycarbonyl compound described in JP-A-52-1
α-aminocarbonyl compounds described in JP-A Nos. 43020 and 53-89425, alkanolamines described in JP-A-54-3532, JP-A-57-44148 and JP-A-5
Examples include the metal salts described in No. 7-53749. In addition, as a chelating agent, Japanese Patent Publication No. 4B-03049
Aminopolycarboxylic acids described in No. 6 and No. 44-30232, JP-A No. 56-97347, JP-B No. 56-39
Organic phosphonic acids described in No. 359 and West German Patent No. 2227639, JP-A Nos. 52-102726 and 51-42
No. 730, No. 54-121) No. 27, No. 55-1262
Examples include phosphonocarboxylic acids described in JP-A-58-195845, JP-A-58-203440, JP-B No. 53-40900, etc. .

However, even when these compounds are used alone or in combination, sufficient preservative performance cannot be obtained, and they do not have a sufficient effect on stabilizing photographic properties during continuous processing as in the present invention. Ta.

Furthermore, in color development, the exposed silver halide is reduced and turned into a dye, 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 decomposition of silver halide are eluted into the developer and accumulated. On the other hand, the color developing agent is consumed by reaction with the coupler mentioned above. Furthermore, other components are also diffused into the photographic light-sensitive material, retained, and taken out, and the concentration of the components in the developer decreases. Therefore, in a development method in which a large amount of silver halide photographic light-sensitive material is continuously processed using an automatic processor, etc., the components of the color developer are kept within a constant concentration range in order to avoid changes in development finish characteristics due to changes in component concentration. We need a means to do so.

For example, consumable components such as developing agents and preservatives are generally kept at a high concentration in the replenisher when the effect of concentration is small.

In addition, eluates such as halogens that have the effect of inhibiting development are
In some cases, its concentration in the replenisher may be reduced or it may not be included. Additionally, certain compounds may be included in the replenisher to eliminate the effects of eluates. Also pH
In some cases, the concentration of the alkali or chelating agent may be adjusted. As such a method, a method of replenishing a replenisher for supplementing the missing components and diluting the increasing components is usually used. This replenisher is usually replenished once per IM of the photosensitive material.
Since this process is carried out for about 80 to 1000 mβ, a large amount of overflow liquid is inevitably generated, which poses a major economic and pollution problem.

In recent years, there has been a strong desire to reduce the amount of color developer replenishment for the purpose of speeding up the development process, saving resources, and reducing pollution. However, simply reducing the amount of color developer replenishment results in
Accumulation of eluates from light-sensitive materials, particularly bromine ions, which are strong development inhibitors, and various organic compounds, causes problems in that development activity is reduced and speed is impaired.

As a solution to this problem, there is a development acceleration technique, and many speed-up techniques for reducing the amount of developer replenishment are being studied.

For example, one known method is to accelerate development by increasing the pH and processing temperature of the color developer. However, this method causes serious problems such as high fog, poor stability of the developer, and increased fluctuations in photographic properties during continuous processing. Further, as another acceleration technique, a method of adding various development accelerators has been described, but the accelerating effect thereof is insufficient and unsatisfactory.

For the purpose of reducing the accumulation of bromide ions, which are strong inhibitors of development, and speeding up development, Japanese Patent Application Laid-Open No. 5895345 and 5895345
No. 9-23234.2, No. 61-70552, International Publication No. WO 37-04534, and JP-A No. 63-106655 disclose a method using a silver halide photosensitive material with a high silver chloride content. It is considered an effective means to reduce the amount of liquid replenishment. However, when continuous processing was actually performed with a reduced amount of developer replenishment, the speed was not impaired, but the photographic characteristics, especially the sensitivity minimum density and maximum density of the magenta coloring layer, changed significantly due to continuous processing. However, a new problem arose in terms of image storage stability after processing, particularly that staining in white areas increased significantly, and it was found that this method could not be put to practical use.

Also, JP-A-62-247369, JP-A No. 6224914
No. 7, No. 62-249148, No. 63-1)939 and No. 63-100454 disclose silver halide photosensitive materials made of silver chloride or silver chlorobromide containing a magenta coupler represented by general formula (I). A processing method is disclosed, which enables rapid processing, provides a high maximum density of the magenta coloring layer, and provides low fog. However, there is no description regarding continuous processing, and furthermore, there is no description of the aforementioned problems that occur when the amount of developer replenishment is drastically reduced and how to solve them, so it is not possible to make an analogy.

Furthermore, JP-A No. 63-106655 describes a low replenishment continuous processing method for silver halide color photographic light-sensitive materials made of silver chloride or silver chlorobromide containing a magenta coupler represented by the general formula (1), which enables rapid processing. Similarly, a technology has been disclosed in which the maximum density of the magenta coloring layer is high and fog is low, but dialkylhydroxylamines are used as preservatives in color developing solutions, and as mentioned above, However, the disadvantages of dialkyl hydroxylamines such as decreasing the color-forming properties of couplers and causing decomposition by metal ions and fogging due to decomposition products have not been fully resolved. The processing stability was insufficient and unsatisfactory.

(Problems to be Solved by the Present Invention) Currently, the amount of replenishment of the color developer varies somewhat depending on the photosensitive material to be processed, but generally about 180 to 1000 mρ is required per photosensitive material In to be processed. If you try to further reduce the amount of replenishment to the detriment of speed, during continuous processing, the photographic properties, especially the sensitivity of the magenta coloring layer, the maximum density, and the minimum density may fluctuate greatly, and the image storage stability after processing, especially for white backgrounds, may change significantly. A very serious problem arises in that the sting of the part increases.

There has been a strong desire for technology that can fundamentally solve these problems.

(Objective of the present invention) The first object of the present invention is to maintain photographic properties in continuous processing, especially the sensitivity and maximum density of the magenta coloring layer, and to maintain the minimum density (fogging) even if the replenishment amount of color developing solution is significantly reduced. ) is low, processing fluctuations are small, and processing speed is not impaired.

A second object of the present invention is to provide a processing method that improves image storage stability after processing, particularly preventing an increase in staining in white background areas, even when processing is performed in which the amount of replenishment of a color developing solution is significantly reduced.

(Means for Solving the Problems) The object is to provide a method for continuously processing a silver halide color photographic light-sensitive material with a color developing solution containing at least one aromatic primary amine color developing agent. At least one layer of the silver color photographic light-sensitive material contains a silver halide emulsion containing 80 mol% or more of silver chloride and at least one magenta coupler represented by the following general formula (T).
The silver halide color photographic material 1 contains seeds, the color developer contains at least one kind of organic preservative, and the amount of replenishment of the color developer during continuous processing is
This was achieved by a method for processing a silver halide color photographic light-sensitive material, which is characterized in that the amount per M is in the range of 20 to 150 mff.

General Formula (I) R, -R3 and Y represented by -i formula (1) will be explained in detail below.

In general formula (1), when Y represents a coupling-off group (hereinafter referred to as a leaving group), the leaving group connects to the coupling active carbon via oxygen, nitrogen, sulfur, or a carbon atom, an aliphatic group, an aromatic group, etc. groups, heterocyclic groups, aliphatic/aromatic or heterocyclic sulfonyl groups, groups that bond to aliphatic diaromatic or heterocyclic carbonyl groups, nitrogen-containing heterocyclic groups that connect with a nitrogen atom at the camping position , a halogen atom, an aromatic ab group, etc., and the aliphatic, aromatic, or heterocyclic group contained in these leaving groups may be substituted with a substituent allowed by R (described later). When there are two or more substituents, they may be the same or different, and these substituents may further have a substituent allowed for R+.

Specific examples of coupling-off groups include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.), alkoxy groups (e.g. ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, 3-(methanesulfonamide) ) propyloxy group, carboxypropyloxy group, methylsulfonylethoxy group), aryloxy group (e.g. 4-chlorophenoxy group, 4-methoxyphenoxy group, 3-sulfonamidophenoxy group)
- (N,N'-diethylsulfamoyl)phenoxy group, 4-carboxyphenoxy group, etc.), acyloxy group (e.g. acetoxy group, tetrazocallyoxy group,
benzoyloxy group, etc.), aliphatic or aromatic sulfonyloxy group (e.g., methanesulfonyloxy group, toluenesulfonyloxy group, etc.), acylamino group (e.g., dichloroacetylamino group, heptafluorobutyrylamino group, etc.), aliphatic or Aromatic sulfonamide groups (e.g., methanesulfonamino group, p-toluenesulfonylamino group, etc.), alkoxycarbonyloxy groups (e.g., ethoxycarbonyloxy group, hensyloxycarbonyloxy group, etc.), aryloxycarbonyloxy groups (e.g., phenoxycarbonyloxy group, etc.)
, aliphatic/aromatic or heterocyclic thio groups (e.g. ethylthio group, phenylthio group, tetrazolylthio group, etc.),
Carbamoylamino group (e.g. N-methylcarbamoylamino group, N-phenylcarbamoylamino group, etc.),
5- or 6-membered nitrogen-containing heterocyclic groups (e.g., imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl, etc.), imide groups (e.g., succinimide, hydantoinyl) group, etc.), aromatic azo groups (eg, phenylazo group, etc.), and these groups may be further substituted with a group allowed as a substituent for R1. Furthermore, there are bis-type couplers obtained by condensing a four-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. The leaving group of the present invention may contain photographically useful groups such as development inhibitors and development accelerators. Preferred combinations of leaving groups in each general formula will be described later.

In general formula (I), R and R3 are each an aliphatic group having 1 to 36 carbon atoms, preferably an aromatic group having 6 to 36 carbon atoms (e.g., phenyl group, naphthyl group, etc.), a heterocyclic group ( (e.g., 3-pyridyl group, 2-furyl group, etc.) or an aromatic or heterocyclic amino group (e.g., anilino group, naphthylamino group, 2-benzothiazolylamino group, 2-pyridylamino group, etc.). The group further includes an alkyl group, a teryl group, a heterocyclic group, an alkoxy group (e.g., methoxy group, 2-methoxyethoxy group, etc.), an aryloxy group (e.g., 2,4-dite
r t-amylphenoxy group, 2-chlorophenoxy group, 4-cyanophenoxy group, etc.) alkenyloxy group (
For example, 2-propenyloxy group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), ester group (
For example, butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (for example, acetylamino group, ethylcarbamoyl group, dimethylcarbamoyl group, methanesulfonamide group) , N, N-dibutylsulfamoyl group, 3- (2,4
-di-tert-amylphenoxy)propylsulfamoyl group, benzenesulfonamide group, 2-butoxy-
5-tert-octylhenzensulfonamide group, dodecanesulfonamide group, butylsulfamoyl group, etc.), butylsulfamoyl group), sulfamide group (
(e.g., dipropylsulfamoylamino), imide groups (e.g., succinimide, hydantoinyl, etc.), ureido groups (e.g., phenylureido, dimethylureido, etc.), aliphatic or aromatic sulfonyl groups (e.g., methanesulfonyl), group, phenylsulfonyl group, 2-butoxy5-1ert-octylphenylsulfonyl group, etc.), aliphatic or aromatic thio group (e.g., ethylthio group, phenylthio group, etc.), hydroxy group, cyano group, carboxy group, nitro group, It may be substituted with a group selected from a sulfo group, a halogen atom, etc.

When there are two or more substituents, they may be the same or different.

As used herein, the term "aliphatic group" refers to a linear, branched, or cyclic aliphatic hydrocarbon group, and includes saturated and unsaturated groups such as alkyl, alkenyl, and alkynyl groups. Typical examples include methyl group, ethyl group, butyl group, dodecyl group, octadecyl group, alkynyl group, is.

Examples include propyl group, tert-butyl group, tert-octyl group, tert-dodecyl group, cyclohexyl group, cyclopentyl group, allyl group, vinyl group, 2-hexadecenyl group, and propargyl group.

It is known in the art that the magenta coupler represented by general formula (I) has the following keto-enol tautomerism when R2 is a hydrogen atom. Therefore, the structure on the left side is equivalent to the structure on the right side.

(M-1) R2 in general formula (I) is preferably a hydrogen atom, an aliphatic acyl group or an aliphatic sulfonyl group, and particularly preferably R2 is a hydrogen atom. Preferred Y is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, with sulfur leaving groups being particularly preferred.

The magenta coupler represented by the general formula (I) is disclosed in JP-A-49-74027, JP-A-49-74028, and JP-A-49-74028.
It is synthesized by the method described in No. B-27930, No. 53-33846, and US Pat. No. 3,519,429.

Specific examples of these magenta couplers are listed below, but the more preferred magenta couplers in the present invention are not limited to these.

C7! (tvl-J) (Haig) (+n-7) α e α (M , 3') (IXE l ) (M-4) α α α (M-ta) (M-70) (1νS −/ J ) (M-/μ) (M-// α α (M-/, 2) α (MCβ) Two or more of the above couplers, etc. are used in combination in the same layer to satisfy the characteristics required for photosensitive materials. It is also possible to add the same compound to two or more different layers.
Of course it doesn't matter.

Here, the emulsion layer is preferably a green-sensitive emulsion layer consisting of a high silver chloride emulsion.

To introduce the coupler into the silver halide emulsion layer, known methods such as those described in US Pat. No. 2,322.027 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.),
Phosphate esters (trioctyl phosphate, triphenyl phosphate, tricresyl phosphate,
dioctylbutyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate) ), trimesic acid esters (e.g. tributyl trimesate), etc., or organic solvents with a boiling point of about 30"C to 150°C, such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl After dissolving in ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid.The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

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 organic solvent used in the oil-in-ice dispersion method is U.S. Pat. No. 2,322,027.
It is written in the number etc.

Further, the process, effects, and specific examples of latex for impregnation as one of the polymer dispersion methods are described in U.S. Patent No. 4,199,363, West German Patent TB (OLS)
No. 2.541.274 and No. 2.54.1.23
No. 0, etc., and a dispersion method using an organic solvent-soluble polymer is described in PCTJP No. 87100492.

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

The range of replenishment amount of color developer in the present invention, which is 20 to 150 mff per silver halide photosensitive material, will be explained. The replenishment amount here indicates the amount of so-called color developer replenisher to be replenished. In the prior art, it is unrealistic to reduce the amount of developer replenishment to less than 150 ml of photosensitive material due to the problem Q mentioned above. That is, the replenishment amount of 150 mβ/1% of photosensitive material is a value located at the boundary between the range made possible by the present invention and the range made possible by the combination of the prior art techniques subsequent to the present invention. Also, although it varies somewhat depending on the photosensitive material, the amount of developer replenishment is 2Q m
12/photosensitive material IM or less, the amount of processing liquid carried out by the photosensitive material exceeds the amount of replenishment, the processing liquid decreases, and continuous processing becomes practically impossible. Replenishment amount 20mβ
/Photosensitive material 1. (Although it differs somewhat depending on the photosensitive material, it indicates the amount at which the amount of processing liquid carried out by the photosensitive material and the amount refilled are approximately equal, and is the amount at which overflow is substantially eliminated. Preferably, the amount per m2 of the photosensitive material 3
0mj! ~100ml.

The color developer replenisher may contain additives for correcting deterioration over time and concentration.

The additives mentioned here include, for example, water for diluting the concentrate, preservatives that tend to deteriorate over time, or alkaline agents that increase the pH.

The developer used in the present invention preferably does not substantially contain benzyl alcohol in order to reduce fluctuations in photographic properties during continuous processing. Here, "substantially not containing" preferably means a concentration of 2 mj2/l or less, more preferably 0.5 mj2/ffm or less, and most preferably no benzyl alcohol at all.

It is more preferable that the developer used in the present invention does not substantially contain sulfite ions. The sulfite ion functions as a preservative for the developing agent, and at the same time has the effect of dissolving silver halide and reacting with the oxidized product of the developing agent to reduce the dye formation efficiency.

Such an effect is presumed to be one of the causes of increased fluctuations in photographic characteristics that occur when the amount of color developer replenishment is reduced. Here, "substantially not containing" preferably means 5
．． The sulfite ion concentration is below 0.times.10@-3 mol/l, and most preferably no sulfite ions are contained. However, in the present invention, a very small amount of sulfite ion used to prevent oxidation in a processing agent kit in which the developing agent is concentrated before being mixed into a solution for use is excluded.

The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. This is because hydroxylamine functions as a preservative for the developing solution and also has silver developing activity itself, and it is believed that fluctuations in the concentration of hydroxylamine greatly affect photographic properties.

The expression "substantially not containing hydroxylamine" as used herein means preferably a hydroxylamine concentration of 5.0.times.10@-3 mol/.beta. or less, and most preferably no hydroxylamine at all.

The developer used in the present invention contains an organic preservative in place of the hydroxylamine and sulfite ions. This is preferable in terms of stability of photographic properties during continuous processing and image storage stability after processing.

The term "organic preservative" as used herein refers to any organic compound that reduces the rate of deterioration of an aromatic primary amine color developing agent when added to a processing solution for a color photographic light-sensitive material. In other words, they are organic compounds that have the function of preventing color developing agents from being oxidized by air, among others, hydroxylamines (excluding hydroxylamine), hydroxamic acids, hydrazines, hydrazides, phenols, and α-hyperoxygenates. 10
Xyketones, α-aminoketone neck, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, dil-lodoxy radicals, alcohols, oximes,
Particularly effective organic preservatives include diamide compounds and fused amines. These are patent application No. 61-147823.
No. 61-173595, No. 6m-165621, No. 61) No. 88619, No. 61-197760, No. 61-186561, No. 6 ], No. -198987, No. 61-2'01861, No. 61 ) No. 86559,
No. 6m-170756, No. 61-188742, No. 61-188741, U.S. Pat.
No. 18-30496, etc.

Regarding the preferred organic preservative, its general formula and specific compounds are listed below, but the present invention is not limited thereto.

In addition, the amount of the following compounds added to the color developing solution is 0.00
5 mol/p to 0.5 mol/p, preferably 0.03 mol/p! It is desirable to add it to a concentration of l-0.1 mol/l.

As the hydroxamic acids, the following are preferred.

General formula (I[I) A:lI
Substituted or unsubstituted aryl group, substituted or unsubstituted amine group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted carbamoyl group , substituted or unsubstituted sulfamoyl group, acyl group,
Represents a carboxy group, hydroxyamino group, or hydroxyaminocarbonyl group. As a substituent, a halogen atom,
Examples include an aryl group, an alkyl group, an alkoxy group, and the like.

Preferably A3+ is a substituted or unsubstituted alkyl group, aryl group, amine group, alkoxy group, or aryloxy group. Particularly preferred examples include substituted or unsubstituted amino groups, alkoxy groups, and aryloxy groups. The number of carbon atoms is preferably 1 to 1o.

Represents 180-. Preferably X31 is 10-.

R3+ is a hydrogen atom, a substituted or unsubstituted alkyl group,
Represents a substituted or unsubstituted aryl group.

At this time, A3I and R31 may be linked to form a ring structure. The substituents are the same as those listed for A31. Preferably R31 is a hydrogen atom.

'l, /31 represents a hydrogen atom or a group that can become a hydrogen atom through a hydrolysis reaction.

Compound example II[-5 CH.

C)1. -C-1t-OH The following are preferred as the hydrazines and hydrazides.

General formula (IV) CH3CN)l-OH C+H7OC-NHOH In the formula, R41, R42, and R42 represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, and R44 is a hydroxy group. , hydroxyamino group,
Substituted or unsubstituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group,
Represents an amino group. The heterocyclic group is a 5- to 6-membered ring, composed of C, H, 0, N, S, and halogen atoms, and may be saturated or unsaturated. X41 is 10
It represents a divalent group selected from SO2H or -C-, and n is O or 1. In particular, when n=o, R44 represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and R44 and R44 may jointly form a heterocyclic group.

In the general formula (IV), R41, R4Z, R, and 43 are preferably hydrogen atoms or 01 to C1° alkyl groups, and most preferably R4+ and R42 are hydrogen atoms.

In general formula (1v), R44 is an alkyl group, an aryl group,
Preferably, it is an alkoxy group, a carbamoyl group, or an amino group. Particularly preferred are alkyl groups and substituted alkyl groups. Preferred substituents for the alkyl group here include a carboxyl group, a sulfo group, a nitro group, an amino group, a phosphono group, and the like. x'1 is preferably -co- or -5ol-, most preferably -CO-.

IV-2 NH2NH-(-CH2÷,,So3+1V-3 NHJ)I +CH2÷20H IV-6 NH2NHCOCH3 IV-7 NHJI(COOCJs N)IJHCONHz NHzNH5OJ ■-13 N)I NHzNHCNH z ■-14 NH2NHCOCONHN)12 ■-15 NHzNHCHzCHzCHzSOJ As the phenols, the following are preferable: Ao general formula (V) NHJHCHCOOH C4H9(n) ■-18 NHJHCHzCHzCOOH In the formula, R9+ is a hydrogen atom, a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, 71 noroxy group, carboxyl group, sulfo group, carnoslmoyl group, sulfamoyl group, amido group, sulfonamide group, ureido group, ryokylthio group, alkylthio group, nitro group, cyano group, amino group, formyl group, acyl group, sulfonyl group,
When R51 representing an alkoxycarbonylsulfonyl group and an aryloxysulfonyl group is further substituted, examples of the substituent include a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, and the like. Furthermore, when there are two or more R51's, their types may be the same or different, and when they are adjacent, they may be bonded to each other to form a ring. The ring structure is a 5- to 6-membered ring, composed of carbon atoms, hydrogen atoms, halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, etc., and may be saturated or unsaturated.

R 52 represents a hydrogen atom or a hydrolyzable group. Moreover, m% n is an integer from 1 to 5, respectively.

In formula (V,), preferred RSIs include an alkyl group, a halogen group, an alkoxy group, an alkylthio group, a carboxyl group, a sulfo group, a carbamoyl group, a sulfamoyl group, an amino group, a ryomido group, a sulfonamide group, and a nitro group. , Ohishiano i. Among these, an alkoxy group, an alkylthio group, an amino group, and a nitro group are particularly preferred, and these are more preferably located at the ortho or para position of the (O R '') group.The number of carbon atoms in R51 is from 1 to 1.
0 is preferred, and 1 to 6 are particularly preferred.

Preferred R52 is a hydrogen atom or a hydrolyzable group having 1 to 5 carbon atoms. Also, (OR”)
When there are two or more groups, it is more preferable that they are located at ortho or para positions with respect to each other.

HV-5 ■-10 OH ■■-1) So, ) I OH ■ OH OH OJa OOH As the α-hydroxyketones and α-aminoketones, the following are preferable.

General formula (■) R61 R” -C-C)(-R” In the formula, RCl represents a hydrogen atom, a substituted or unsubstituted furkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group, and R62 is Represents a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group, and R61 and R62
may jointly form a carbocycle or a heterocycle. R61
represents a hydroxyl group or a substituted or unsubstituted amino group.

In general formula (Vl), R61 is preferably a hydrogen atom, an alkyl group, an aryl group, or an alkoxy group;
Gt is preferably a hydrogen atom or an alkyl group.

T-1 C) 13ccI120)1 Vl-6 I-8 CH3CCHCH3 V’i-3 OH C) +30c cncJs ■-10 I-4 CHsCCHJHCJs I-5 1C-CHzOH Sugars are also preferred organic preservatives.

Sugars (also called carbohydrates) consist of monosaccharides and polysaccharides.
Many have general 2〇,, H2107. Monosaccharides generally refer to aldehydes or ketones of polyhydric alcohols (called aldoses and ketoses, respectively), their reduced derivatives, oxidized derivatives, cross-linked derivatives, and a wider range of derivatives such as amino sugars and thiosaccharides. . Moreover, polysaccharide refers to a product obtained by dehydration condensation of two or more of the above-mentioned monosaccharides.

More preferred among these saccharides are aldoses having a reducing aldehyde group and derivatives thereof, and particularly preferred among these are those corresponding to monosaccharides.

■-I D-Oxylose ■-2L-Arabinose ■-3D-Ribose ■-4D-Deoxyribose ■-5D-Glucose ■-6D-Galactose"!'I [-7D-Mannose ■-8 Glucosamine ■-9L-Sorbose (2)-10D-Sorbitol monoamines include the following.

General formula (■) ReI-N pg3 In the formula, Rst, Rpz, and Re each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group. Here, RRl, R&2R2+ and 8g
3 or Rf2 and Bz'' may be connected to form a nitrogen-containing heterocycle.

Here, Rffil, R22, and R23 may have a substituent. Rffl, Rt2, and R13 are particularly preferably a hydrogen atom or an alkyl group. Further, examples of the substituent include a hydroxyl group, a sulfone group, a carboxyl group, a halogen atom, a nitro group, an amino group, and the like.

V[-1N+C)12c)120)1n.

Vy12 HJCHzCHzOH■-3HN(-
CH2CH20H) 2■-4 H CJ+sN+CHzCHCHzOH)zH2 ■-6 ■-8 HOCHzCHCOOH N)12 ■-10 (HOC) 12CH! -)-ZNCH2CH2SO□C
H.

VlIl, -1) HN+　CHzCOOH)　z ■-19 1X The following diamines are preferred.

General formula (1x) X (+10cH2cH2÷2NC1hCIIzN+CHz
CHzOH) 2H In the formula, RQl, R1)2, Rqs, and R+'' represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group.

RQS represents a divalent organic group, specifically an alkylene group, an arylene group, an aralkylene group, an alkenylene group, or a heterocyclic group.

R1)1, R'12, R43, and RQl are particularly preferably a hydrogen atom or an alkyl group, and BqS is particularly preferably an alkylene group.

X-1 HJCHzCllzN + CHzCHzOH) 2H
JCHzCHCHJlh H X H +X-10 As the polyamines, the following are preferred.

general formula Specifically, it has the same meaning as Bq5 in the general formula (TX).

l0a X101 and X102 are -N--0--3--CO-8
○t Represents a linking group composed of So- or a combination of these linking groups, R″6 is R1))l1a2
, RIOI and R10' have the same meaning. mba0 or 1
represents an integer greater than or equal to

(The upper limit of m is not particularly limited, and it may be a high molecular weight as long as the compound is water-soluble, but usually m is preferably in the range of 1 to 3) H3 HzNCHzCHJCHzCLliL (HOClhCHz÷JCHzCHzOCHzCHJ+
CH2CH20H) In formula 2, R101, R102,
RI02 and 'RI04 represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group.

R105, R106, and R1° represent divalent organic groups, and the following are preferred as the quaternary ammonium salt.

General formula (n) represents. At least two of R1), RN:+, and RI+4 may be bonded to form a heterocycle containing a quaternary ammonium atom. n is an integer of 1 or more,
Xo represents a counter anion. ) 8 mouths 2, R1) 1 and R
A particularly preferable uvalent group in I+' is a substituted or @substituted alkyl group, and at least one of 8-unit R1)3 and R1)4 is a hydroxyalkyl group, an alkoxydialkyl group, or a carboxyalkyl group. Most preferred.

n is preferably an integer of 1 to 3, more preferably 1 or 2
It is.

(In the formula, R1)l represents a monovalent organic group, R1)2R
Ili and R++4 represent a monovalent organic group. The organic group here refers to a group having one or more carbon atoms, specifically an alkyl group, an aryl group, a heterocyclic group, etc.
/2sO+2l-3 N+CJ40H)4, Br-I-4 (CJs+J+CJ,,OH)2, CI
t eXI=5 I-8 I-9 CJs O0 R+21 and R+22 each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Further, these alkyl groups, aryl groups or heterocyclic groups may have a substituent. Such substituents include hydroxy group,
Examples include oxo group, carbamoyl group, alkoxy group, sulfamoyl group, carboxy group, and sulfo group. Examples of the heterocyclic group include a pyridyl group and a piperidyl group.

Preferably, R121 and R122 are substituted or unsubstituted aryl groups or tertiary alkyl groups (eg, t-butyl group, etc.).

(Compound example) As the nitroxy radicals, the following are preferred.

XI[-2 General formula (Xr[l) XI-5 The following alcohols are preferred.

R132C-X+3 In the formula, RI3+ represents a hydroxy-substituted alkyl group, and R132 represents an unsubstituted alkyl group or the same group as R13+. R133 represents a hydrogen atom or a group similar to R232. X131 represents a hydroxy group, a carboxyl group, a sulfo group, a nitro group, an unsubstituted or hydroxy-substituted alkyl group, an unsubstituted or substituted amide group, or a sulfonamido group.

In the -I'M formula (XI[), ×1 is preferably a hydroxy group, a carboxyl group, or a hydroxyalkyl group.

疋-I　　　　C83CH.

FO-C-C-0f( CH, CI.

X[1l-2, CH.

HO-CHCH2C0H CHs Cll.

XI[l-3 nl-4 EI-5 XI[I-6 Goose-7 XI[[-8 )to -CH2CHtOH)2 ()10 CL+5COO)1 C+CHzOH+t (HOCHz÷, C-CH.

(HOCH!÷sC-NHCOC) represents 13 atoms or an alkyl group, and n represents a positive integer up to 500.

The alkyl group represented by RI41, R12 and R143 preferably has 5 or less carbon atoms, more preferably 2 or less carbon atoms. R141, R144RL4
3 is very preferably a hydrogen atom or a methyl group, most preferably a hydrogen atom.

n is preferably a positive integer of 3 or more and 100 or less, more preferably 3 or more and 30 or less.

X! '17-1 HO+CHzCIhO÷, 0H XI[[-9 (HOCH!÷2C-3O,H Report 10 HOC)l CHiCHzOH H20H The following alcohols are preferred.

General formula (XIV R"' -0-C-CH-CH, -0÷ p+42I4
4 In the formula, R"', R14", R14"hasoh('t
L hydrogen TV-4 XIV-5 XIV26 CHpO+ CHzCHzO+zOCH3HO+ CH
CH20÷, OH L HOCHzCHzOCHs C2H5O-(-CH2CH20-)-20H Average molecular length: about 300 Average molecular weight: about 800 Average molecular weight: about 3000 Average molecular weight: about 8000 The following are preferred as the oximes.

Moreover, these groups may be connected.

In general formula (XV), R1! Preferred as + and R152 are alkyl groups substituted with halogen groups, hydroxyl groups, alkoxyl groups, amino groups, carboxyl groups, sulfo groups, homephonic acid groups, and nitro groups, and unsubstituted alkyl groups.

Further, the total number of carbon atoms in general formula (X'v) is preferably 30 or less, and more preferably 20 or less.

XV-1 -OH ■ CH, -C-C-C1l:1 -OH XV-2 In the formula, RI! + and R1ff21i-1 each represent a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted 7-aryl group. Also, B+sI−
g and R152 may be the same or different, N-0)
1 ■ HO-(-CH2÷, C-C+CH2÷30)1-OH

General formula % formula %) In the formula, XHI, XIc2 are -CO-1 or 5
02-, R51, R1(2, R1g3Rte4
, R1 (S and]: ilf & ha represents a hydrogen atom, an unsubstituted or substituted alkyl group, and RI'7 represents an unsubstituted or substituted alkylene group, an unsubstituted or substituted arylene group, and an unsubstituted or substituted aralkylene group.m'
, m2, n represent O or 1. -5 VI) 12Nso□NH30zNHz The following are preferred as the condensed cyclic amines.

In the formula, χ represents a trivalent atomic group necessary to complete the condensed ring, and R171 and R172 represent an alkylene group, an arylene group, an alkenylene group, or an aralkylene group.

Here, R and R may be the same or different.

Among general formulas (XVI[), particularly preferred are compounds represented by general formulas (1-a) and (1-b).

In the formula, X″1 represents ≧N or shiCH.R171R1
72 is defined in the same way as in the general formula (XVl[),
R represents R, a group similar to R, or -CH2C-.

In the general formula (1-a>, X171 is preferably '-+H. The number of carbon atoms in R1'+l, RI72, and R1'+3 is preferably 6 or less, more preferably 3 or less, The most preferred case is 2.

R171, R172, and R173 are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

In the formula, R17+ , , R171 are defined as in the general formula (XVM).

In general formula (1-b), the number of carbon atoms in R171 and R172 is 6
It is preferable that it is below. R"' and R"' are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

- Among the compounds of formulas (1-a) and (1-b), especially -
Compounds represented by the linear formula (1-a) are preferred.

81-6 Abuse-7 XVI [-4 XVI! -10 -12 -16 Many compounds of general formulas (II) to (J) according to the present invention can be easily obtained as commercial products.

Two or more of the above organic preservatives may be used in combination. A preferred combination is at least one compound of general formulas (I) to (■) and (■
) to (XW).

A more preferable combination is at least one of the general formula (IV) and at least one of the general formulas (■) and (X1)I).

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

D-IN, N-diethyl-p-phenylenediamine D-24-(N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-32-methyl-4-[N-ethyl-N-(β- hydroxyethyl) aminocoaniline D-44-amino-3-methyl-N-ethyl-N-(β
Methanesulfonamidoethyl)aniline, particularly D-4, is preferably used.

Further, these p-phenylenediamide 7g8 bodies may be a salt such as a sulfate, a hydrochloride, or a p-toluenesulfonate. The amount of aromatic-grade amine developing agent used is preferably in a concentration of about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g, per developer solution 1).

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-1),0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate,
Sodium tetraborate (borax), potassium tetraborate, 0
-Sodium hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate, 5-sulfo-
Examples include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

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

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

Specific examples are shown below, but the invention is not limited to these. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid,
N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N'N'-tetramethylenephosphonic acid, 1
, 3-diamino-2-propatol 4H>H, Trauss cyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-diaminopropane 45%a, hydroxyethyliminoni 5'FUR, glycol ether diamine tetraacetic acid , hydroxyethylenediaminetriacetic acid, ethylenediamineorthohydroxyphenylacetic acid, 2-phosphonobutane-1,24-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.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example, IE
It is about 0.1g to Log per unit.

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

As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 38-782'6, No. 44-12
No. 380, No. 45-9019 and U.S. Patent Section 3,81
3,247, etc., p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-Sho 50
-137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 56-156.826 and Japanese Patent Publication No. 52-43429, etc., U.S. Patent Sections 2 and 6
No. 10,122 and No. 4,1) p- described in No. 9.462
Aminophenols, U.S. Patent Sections 2,494,903, 3,128,182, 4,230,796
No. 3,253,919, Special Publication No. 41-1) No. 431,
U.S. Pat.
Amine compounds described in No. 26 and No. 3,582,346, etc., Japanese Patent Publication Nos. 37-16088 and 42-2520
No. 1, U.S. Patent Section 3,128,183, Special Publication No. 1973-
1) No. 431, No. 42-23883 and U.S. Patent Section 3
, 532, 501, etc., 1-phenyl-3-pyrazolidone, hydrazine, mesoion type compounds, ionic type compounds, imidazole, etc. can be added as necessary.

Any antifoggant can be added to the color developer used in the present invention, if necessary.

As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidropenzimitasole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5
-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine,
A typical example is a nitrogen-containing heterocyclic compound such as adenine.

The color developer used in the present invention preferably contains an optical brightener. As an optical brightener, 4,4'-
Diamino-2,2'-disulfostilbene compounds are preferred. The amount added is 0 to 5 g/l, preferably 0.1 to 4
g/R.

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.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents include iron (■), Kobal) (I
Compounds of polyvalent metals such as II), chromium (■), and copper (II), peracids, quinones, nitro compounds, and the like are used.

Typical bleaching agents include ferricyanide; dichromate; iron(1) or kohal) (III) complex salt;
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid; Sulfates; bromates; permanganates; nitrohenzenes, etc. can be used. Among these, aminopolycarboxylic acid iron(III) complex salts and persulfates, including ethylenediaminetetraacetic acid iron(III) complex salts, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (IIT) complex salts is usually 5.5 to 8, but in order to speed up the processing, it can be processed at an even lower pH. .

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

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3.893.858, German Pat.
, No. 290.812, Japanese Patent Publication No. 5395.630, Research Disclosure No. 17.129 (1978
Compounds having a mercapto bond or a disulfide group as described in JP-A No. 50-140,129; U.S. Patent No. 3,706.5
Thiourea derivatives described in No. 61; JP-A-58-16.2
Iodide salts described in No. 35; West German Patent No. 2°748.4.
Polyoxyethylene compounds described in No. 30;
．． Polyamine compounds described in No. 5-8836; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly described in U.S. Pat. The compounds described are preferred. Additionally, U.S. Patent No. 4.55
Also preferred are the compounds described in No. 2.834. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for Preservatives for the bleach-fix solution are preferably sulfites, bisulfites, sulfinic acids, or carbonyl bisulfite adducts.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnalof the 5ociety of Mo
tion Picture and Televisi
onEngineers Vol. 64, P, 248-253
(May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 61-131.632 can be used very effectively. Also, JP-A-57-8.542
Chlorine-based disinfectants such as isothiazolone compounds, thiahendazole, chlorinated sodium isocyanurate, and other chlorinated disinfectants listed in the issue, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, "Microbial It is also possible to use disinfectants described in "Sterilization, Disinfection, and Anti-Mildew Techniques" and "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Japan Antibacterial and Antifungal Society.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4.
-9, preferably 5-8. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
Generally, the temperature is selected in the range of 20 seconds to 10 minutes at 15-45°C, preferably 30 seconds and 5 minutes at 25-40°C. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8,543 and 58-148
All known methods described in No. 34, No. 60-220,345 can be used.

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

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

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

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342.59
Indoaniline compounds described in No. 7, No. 3,342.
No. 599, Research Disclosure 14.850
Schiff base-type compounds described in No. 15.159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
, 719,492, JP-A-53-1
Examples include urethane compounds described in No. 35,628.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-
Pyrazolidones may also be incorporated. Typical compounds are described in JP-A Nos. 56-64,339, 57-144,547, and 581) 5.438.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, a temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. can be achieved. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in West German Patent No. 2.226.770 or US Pat. No. 3,674.499 may be carried out.

The method of the present invention can be applied to processing color paper, color reversal paper, color direct positive paper, etc.

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

The silver halide emulsion of the present invention has a silver chloride content of 80 mol% or more, preferably 95 mol% or more, more preferably 9
It is 8 mol% or more. From the viewpoint of rapidity, the higher the silver chloride content, the more preferable. Further, the high silver chloride composition of the present invention may contain a small amount of silver bromide or silver iodide. This may have many useful benefits in terms of photosensitivity, such as increasing the amount of light absorption, strengthening the adsorption of spectral sensitizing dyes, or weakening desensitization caused by spectral sensitizing dyes. Preferably, the halogen composition of the silver halide in all the photosensitive emulsion layers is 80 mol % or more.

The silver halide grains used in the present invention may have different inner and surface layers (core/shell grains), may have a multiphase structure such as a bonded structure, or may have a uniform phase throughout the grain. Good too. Moreover, they may be mixed.

Average grain size of silver halide grains used in the present invention (
In the case of spherical or near-spherical particles, the particle size is the particle diameter, and in the case of cubic particles, the particle size is the ridge length, and it is the average based on the projected area.

The average particle is also expressed in sphere terms. ) is preferably 2 μm or less and 0.1 μm or more, and particularly preferably 1.
It is 5 μm or less and 0.15 μm or more. The grain size distribution may be narrow or wide, but the value obtained by dividing the standard deviation value of the grain size distribution curve of the silver halide emulsion by the average grain size (variation rate) is within 20%, particularly preferably 15%.
It is preferable to use so-called monodisperse silver halide emulsions of up to % in the present invention. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are used in an emulsion layer having 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
It may have a crystalline form (ular), or it may have a composite form of these crystalline forms.

Tabular grains may also be used, especially when the length/thickness ratio is 5.
In particular, tabular grains of 8 or more account for 5% of the total projected area of the grain.
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 amount of silver coated in the silver halide emulsion of the photosensitive material used in the method of the present invention is - 1°5 g / for boat fishing.
E rl or less but preferably o, 8g/m or less 0.
3g/n? That's all. A coating silver amount of 0.8 g/m or less is very preferable in terms of rapidity, processing stability, and post-processing image storage stability (especially suppression of yellow stain).

The photographic emulsion used in the present invention is described in Research Disclosure+-(RD) vol, 176 Item N.
o, 17643 (1, ■, m) (December 2978).

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 described in Research Disclosure Vol. 176, No. 17643 (197
18716) and Volume 187, No. 18716
(January 1979)), and the relevant sections 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 R0176431? D187161
Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity enhancers
Same as above 4 Whitening agent page 24 5 Antifogging agent 24-25 True page 649 right column - 6 Coupler page 25 7 Organic solvent page 25 Dye image stabilizer page 25 Hardener page 26 Page 651 left column binder page 26 Same as above plasticizer Agents, lubricants Page 27 Page 650 Right column In addition to the coupler of general formula (I), various color couplers can be used in the present invention. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazoline 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) - Section D and 1
8717 (January 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 development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2,40
No. 7,210, 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.
No. 3,933.501 and No. 4,022゜62
The oxygen atom separation type yellow coupler described in No. 0, etc. or Japanese Patent Publication No. 55-1. Q 739, U.S. Patent No. 4. ．． No. 401.752, No. 4,326.024,
RD-18053 (April 1979), British Patent No. 1.
No. 4.25.020, West German Application No. 2,219.91
No. 7, No. 2.261361, No. 2,329,58
The nitrogen atom separation type yellow couplers described in No. 7 and No. 2,433,812 are cited as typical examples. α-pivaloylacetanilide couplers have excellent color fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

Specific examples of these yellow couplers are described below, but preferred yellow couplers in the present invention are not limited to these.

(Y (Y (Y (Y (Y (Y (Y) -CH (Y (Y (Y Cyan couplers that can be used in the present invention include oil-protected naphthol couplers and phenolic couplers, such as the naphthol couplers described in U.S. Pat. No. 2.4.74293 and preferably U.S. Pat.
, No. 212, No. 4146.396, No. 4,228
．． Typical examples include two-equivalent naphthol couplers of the oxygen atom elimination type described in No. 233 and No. 4,296,200. Further, specific examples of phenolic couplers are given in U.S. Patent Nos. 2,369,929 and 2,80.
1.171, same No. 2. 772. No. 162, No. 2
, No. 895, 826, etc.

Among these, in the present invention, it is more preferable to use the cyan coupler of general formula (C) in the red-sensitive emulsion layer from the viewpoint of stability of photographic properties during continuous processing.

General formula (C) H (wherein R1 represents an alkyl group, cycloalkyl group, aryl group, amine group, or heterocyclic group. R2 represents an acylamino group or an alkyl group. R3 represents a hydrogen atom, a halogen atom, or an alkyl group. group or an alkoxy group. R3 may also be combined with R2 to form a ring. Zl
represents a hydrogen atom, a halogen atom, or a group capable of leaving in reaction with an oxidized product of an aromatic primary amine color developing agent. )-C In formula (C), the alkyl group for R1 is preferably an alkyl group having 1 to 32 carbon atoms, for example,
Examples of the allyl group include a methyl group, a butyl group, a tridecyl group, a cyclohexyl group, and an allyl group.
Examples of the heterocyclic group include a phenyl group and a naphthyl group, and examples of the heterocyclic group include a 2-pyridyl group and a 2-furyl group.

In the case of the amine group for R1, a phenyl-substituted amino group which may have a substituent is particularly preferred.

R1 further represents an alkyl group, an aryl group, an alkyl or aryloxy group (eg, a methoxy group, a dodecyloxy group, a methoxyethoxy group, a phenyloxy group, 2.
4-tert-amylphenoxy group, 3-tert
-butyl-4-hydroxyphenyloxy group, naphthyloxy group), carbonitosy group, alkyl or arylcarbonyl group (e.g. acetyl group, tetradecanoyl group, hendiyl group), alkyl or aryloxycarbonyl group (e.g. methoxycarbonyl group) , phenoxycarbonyl group), acyloxy group (e.g. acetyl group, hendiyloxy group), sulfamoyl group (e.g. N-ethylcarbamoyl group, N-octadecylsulfamoyl group), carbamoyl group (e.g. N-ethylcarbamoyl group) , N-methyl-dodecylcarbamoyl group),
Sulfonamide group (e.g. methanesulfonamide group,
henzensulfonamide group), acylamino group (e.g., acetylamino group, henzamide group, ethoxycarbonylamino group, phenylaminocarbonylamino group),
imide groups (e.g. succinimide group, hydantoinyl group), sulfonyl groups (e.g. methanesulfonyl group),
It may be substituted with a substituent selected from a hydroxy group, a cyan group, a nitro group, and a halogen atom.

- In the linear formula (C), 71 represents a hydrogen atom or a coupling-off group, such as a halogen atom)
For example, fluorine atom, chlorine atom, bromine atom), alkoxy group (e.g. dodecyloxy group, methoxycarbamoylmethoxy group, carboxypropyloxy group, methylsulfonylethoxy group), aryloxy group (e.g. 4
-chlorophenoxy group, 4-methoxyphenoxy group),
Acyloxy groups (e.g., acetoxy, tetrazocallyloxy, hendiyloxy), sulfonyloxy groups (e.g., methanesulfonyloxy, toluenesulfonyloxy), amide groups (e.g., dichloroacetylamino, methanesulfonyl) amino group, toluenesulfonylamine group), alkoxycarbonyloxy group (
For example, ethoxycarbonyloxy group, benzyloxycarbonyloxy group), aryloxycarbonyloxy group (e.g., phenoxycarbonyloxy group), aliphatic or aromatic thio group (e.g., phenylthio group, tetrazolylthio group), imide group (e.g., Examples include succinimide group, hydantoinyl group) N-heterocycle (eg, 1-pyrazolyl group, -hentriazolyl group, etc.), aromatic azo group (eg, phenylazo group), and the like. These leaving groups may include photographically useful groups.

-R1 or R2 in the -linear formula (C) may form a dimer or a multimer of more than that.

Specific examples of the cyan coupler represented by the above-mentioned -line formula (C) are listed below, but the more preferred cyan coupler in the present invention is not limited thereto.

■ (C C7! (C C, A (C-6) H j2 (C 491) No. 572 and the like.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such dye-diffusive couplers include magenta couplers in US Pat. The issue includes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451.82.
No. 0 and No. 4.08021).

Specific examples of polymerized maze:/tacouplers are described in British Patent No. 2.102,173 and U.S. Patent No. 4,367.2.
It is described in No. 82.

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

The coupler used in the present invention can be introduced into the light-sensitive material by the above-mentioned known dispersion method.

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

The photographic material used in the present invention is coated on a commonly used plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), a flexible support such as paper, or a rigid support such as glass. For details on the support and coating method, please refer to Research Disclone +-1F Volume 6 Item 17643XV
It is described in Section (P, 27) Ka Section (P, 2B) (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 silver halide emulsion (1) of a blue-sensitive silver halide emulsion layer was prepared as follows.

(1 liquid) (4 liquids) (5 liquids) (6 liquids) (2 liquid) Sulfuric acid (IN) (3 liquid) Compound below (1%) CH.

0cc cc (7f() (1st part) was heated to 60°C, (2nd part) and (3rd part) were added. Then (4 part) and (5 part) were added for 60 minutes. They were added simultaneously. 10 minutes after the completion of the addition of liquids (4) and (liquid 5), liquids (6) and (liquid 7) were added simultaneously over a period of 25 minutes. Five minutes after the addition, the temperature was lowered and desalted. Add water and dispersed gelatin, adjust the pH to 6.0, average particle size 1.0 μm coefficient of variation (standard deviation divided by average particle size; s/d) o, 1), silver bromide 1 A monodisperse cubic silver chlorobromide emulsion of mol % was obtained.Triethylthiourea was added to this emulsion and optimal chemical sensitization was performed.Furthermore, the following spectral sensitizing dye (Sen-1) was halogenated. silver emulsion 1
7X10-' moles were added per mole.

Silver halide emulsion (2) in the green-sensitive silver halide emulsion layer and silver halide emulsion (3) in the red-sensitive silver halide emulsion layer.
) were also prepared in the same manner as above by changing the amount of chemicals, temperature, and addition time.

A spectral sensitizing dye (Sen) was added to silver halide emulsion (2).
-2) was added at 5XIF' mol per 1 mol of the emulsion, and for silver halide emulsion (3), a spectral sensitizing dye (Sen-
3) was added in an amount of 0.9 x 10-' mol per mol of emulsion.

The shapes, average grain sizes, helocene compositions and coefficients of variation of the silver halide emulsions (1) to (3) are as shown below.

(1) Cube (2) Cube (3) Cube (Sen-1) (μm) 1.00 0.45 0.34 (CH2)4 (([1000%) 99.0 99.0 98.2 0 .1) 0.09 0.10 (CH2) 4SO3)1-N (C2H5) 3(S
en (Sen-3) ■ C3HI+ zHs Using the prepared silver halide emulsions (1) to (3), a multilayer color photographic material having the layer structure shown below was prepared.

The coating solution was prepared as follows.

First layer coating solution preparation Example Yellow coupler (Y-8) 19.1g, ethyl acetate 27.2cc and solvent (Solv-1) 3.8cc
Add and dissolve this solution, and add 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate.
It was emulsified and dispersed in 85 cc.

On the other hand, a blue-sensitive sensitizing dye (Sen) was added to the silver halide emulsion (1).
-1) was added in an amount of 5.0XIO-' mol per 1 mol. The above emulsified dispersion and this emulsion layer were mixed and dissolved to prepare a first layer coating solution having the composition shown below.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer.

As the gelatin hardening agent for each layer, 1-oxy3.5-dichloro-3-triazine sodium salt was used.

For the red-sensitive emulsion layer, the following compound was added in an amount of 1.9 x 10-' moles per mole of silver rhodanide.

In addition, for the blue-sensitive emulsion layer, 4-hydroxy-6methyl-1.3.3a,7-chitrazaindene was added to silver halide 1
1.0 x 10-'' moles were added per mole.

In addition, 1-(5
-methylureidophenyl)-5-mercaptotetrazole at 1.0 x 10 per mole of silver halide, respectively.
-3 moles, 1.5X10-' moles added.

Further, 2.5.times.10@-' mol of 2-amino-5mercapto-1,3,4-thiadiazole was added to the red-sensitive emulsion layer per mol of silver halide.

The composition of each layer is shown below.

(Layer structure) Paper support laminated on both sides with polyethylene support [white pigment: TiO□ (2.7 g/m
) and a bluish dye (ulmarine blue)] Layer 1 (blue-sensitive layer) Silver halide emulsion (1) Gelatin yellow coupler (Y=8) ? Container (Solv-1) Second layer (color mixing prevention layer) Gelatin color mixing prevention agent (Cpd-1) Solvent (Solv 1) Solvent (3o1v 2) Dye (T-1> Third layer (green sensitive layer) Halogenation Silver emulsion (2) Gelatin Magenta coupler of the present invention (M) Color image stabilizer (Cpd-2) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) 0 , 89 0, 08 0, 20 0, 20 0.005 0, 29 0, 99 Solvent (Solv-2) Solvent (Solv-3) Fourth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-1 ) Color mixing inhibitor (Cpd-1) Solvent (Solv 4) Dye (T-2) Fifth layer (red-sensitive layer) Silver halide emulsion (3) Gelatin cyan coupler ((,-1) (C-2) Color Image stabilizer (Cpd-6) Color image stabilizer (Cpd-7) Solvent (Solv-4) Solvent (Solv-5> Solvent (Solv-6) Sixth layer (ultraviolet absorbing layer) Gelatin 0, 19 0, 15 1,42 0,52 0,06 0,26 0.015 Ultraviolet absorber (UV-1) Solvent (3o1v 4) Dye (T-2) Seventh layer (protective layer) Acrylic modified copolymer of gelatin polyvinyl alcohol (Degree of modification 17%) Liquid paraffin 0, 48 0, 18 0, 08 0.005 1, 33 0, 05 0, 03 The structures of the compounds used are as follows.

(Cpd-1) Color mixing prevention agent 0 ■ (Cpd color image stabilizer H (Cpd color image stabilizer (Cpd color image stabilizer (Cpd-3) Color image stabilizer H (Cpd-6) Color image stabilizer (C1h-CH7 C0NHC,H,(t) Average molecular weight; 60 H3 (Cpd color image stabilizer (Solv ? container (S.

solvent (Solv solvent (Solv solvent C00CII□CHC,,H.

tsu (CL)e　C2H3 COOCIlzCHCtll.

2H5 (UV UV absorber C41) 9(t) 5H 1(t) CalL(t) 12 of 3 mixture (weight ratio) (So 1 1)? container (S.

Solvent (T ■) (T Hz CI+2 The silver halide multilayer color photographic light-sensitive material produced as described above is referred to as Sample 01. Next, Sample 01 was used except that the magenta coupler in Sample 01 was changed as shown in Table 1. Samples 02 to 08 were prepared in exactly the same manner.

Table 1 * Comparative coupler 吋 In order to investigate the photographic properties of these coated samples, the following experiment was conducted.

First, the coated sample was subjected to gradation exposure for sensitometry using a sensitometer (Model FWH manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200°K). The exposure at this time was carried out so that the exposure time was 1/10 second and the exposure amount was 250 CMS.

Next, continuous processing (running test) was carried out using the following processing steps and the following processing solution composition until twice the tank capacity of the color developer was replenished. However, the composition of the color developer was varied as shown in Table 2, and a running test was conducted for each of them.

``Flame'' 1) Field 1 degree Tomo Sarashishi 1 Se 1 Inokami color developer 38℃ 55 seconds 65mR61! Bleach fixing 30-36℃ 45 seconds 161mf 86 phosphorus
■ 30~37℃ 20 seconds -41 Rinse ■ 30~37℃ 20 seconds -4! Rinse
■ 30~37℃ 20 seconds -4β rinse ■
30~37℃ 30 seconds 200mJ! 41 dry
Drying: 70 to 80°C for 60 seconds (the amount of replenishment is per 1 M of photosensitive material. Replenishment in the rinsing step was carried out in a 4-tank countercurrent system to rinses ①-②).

The composition of each treatment liquid is as follows.

Left Bunji anti-statue teaching l Makaresa dog liquid water
800mβ 800mf Benzyl alcohol See Table 2 Ethylenediamine-N.

N,N',N'-tetramethylenephosphonic acid organic preservative A (IV Sodium chloride potassium carbonate N-ethyl-N-(β methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate organic preservative Add constant agent B (IV optical brightener (4,4 diaminostilhene) 2.0g water
1000 pH (25°C) 10.05 Bleach-fix solution (
Tank fluid and replenisher are the same) Water 5.0g R 1) 0.05mol 3.5g 19) 0.04mo1 4゜6g 5g 6゜5g 0.08mo1 5g 12.0g 0.05mo1 4.0g 1000+++ff 10. 85 4 0 0 ml Ammonium thiosulfate (70%) 100mn Sodium sulfite 17g Ammonium iron(I) ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 5g Ammonium bromide 40g Glacial acetic acid
Add 9g water
1000mlp100℃)
5.40 Rinse solution (tank solution and refill solution are the same)
Ion exchange water (3 ppm each of calcium and magnesium
(below) Process the sensitometry at the start and end of the run to determine the maximum density (Dmax), minimum density (Dmin), and sensitivity (lo representing density 0°5) of green (G).
The amount of change in gE value) due to continuous treatment was measured using a Macbeth densitometer, and the results are shown in Table 2. In the sensitivity change, + represents the direction of increasing sensitivity and the symbol + represents the direction of decreasing sensitivity.

At the same time, an unexposed sample of each sample was processed at the end of the run to evaluate the stain after processing, and each sample after processing was stored at 60°C and 70% relative humidity for 20 days. Changes in stain concentration in blue (B)? Jff degree was measured and evaluated. These results are shown in Table 2.

/ From Table 2, it was observed that in the comparative coupler (sample 08), the photographic properties, Dmin, Dmax, and sensitivity varied greatly immediately after the start and at the end of the run, and furthermore, the increase in stain was also large.

In contrast to this comparative coupler, samples 01 to 07 containing the magenta coupler represented by the general formula (1) of the present invention,
Even with continuous processing with a reduced replenishment amount of color developing solution, the fluctuations in photographic properties due to running are clearly small, and there is no increase in staining even when stored under high temperature and high humidity conditions after processing. Less than the comparison coupler was observed.

In addition, sample 07, which is a magenta coupler represented by formula (1') and has a leaving group, and so-called 4, which does not have a leaving group.
Comparing equivalent magenta coupler samples 01 to 06, the variation in photographic properties during continuous processing is slightly larger in sample 07, which has a leaving group, but regarding the stain after processing, so-called 4, which does not have a leaving group. It was found that it is smaller than the equivalent coupler.

In addition, the replenishment amount of color developer in this continuous process is 55 m
l/%, the amount of liquid discharged is approximately 35 mff/M
Met.

Example 2 Using the samples 01 to 08 prepared in Example 1, continuous processing (running test) was performed using the following processing steps and the following processing solution composition until twice the tank capacity of the color developer was replenished. However, The composition of the color developer was varied as shown below, and a running test was conducted for each of them.

Processing wedge Direct skin Tomo Replenishment amount Kakukuki 1 color developer 37℃ 60 seconds 65% 6ββ30 before bleaching
~36°C 45 seconds 161 8β rinse ■ 3
0~37°C 20 seconds -4β rinse ■ 30
~37℃ 20 seconds -4β rinse ■ 30~
37°C 20 seconds -4β rinse ■ 30~3
7°C, 30 seconds, 200 mfl, 4Il drying, 70-80°C, 60 seconds (the amount of replenishment is per 1 M of photosensitive material. Replenishment in the rinsing step was carried out in a 4-tank countercurrent system to rinses ① and ②).

) Color developer A Tank liquid Replenisher water
800mβ 800mj
! Ethylenediamine-N N,N,N-tetramethylenephosphonic acid organic preservative A (IV-19) Sodium chloride potassium carbonate N-ethyl-N-(β methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfuric acid Salt organic preservative B (■-1) Fluorescent whitening agent (4,4' diaminostilhene type) Add water to pH (25°C) Zuo Punili Zhu Kandan water 3.5 g 0.04 mo1 5. 0g 5g 5.0g 0.06mol 2.0g 000ml 10.25 Tank liquid 800 parts 8.0g 0.09mol 5g 1). 0g 0.09mol Ethylenediamine-N NN, N-tetramethylenephosphonic acid Sodium sulfite Sodium chloride Potassium carbonate N-ethyl-N-(β methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate Hydroxylamine sulfate 3 .5g 2.0g 5.0g 5g 5.0g 2.0g 8.0g 2.5g 5g 1). 0g 2.5g Fluorescent brightener (4,4' 4.0g Diaminostilhene type) 2.0g 4.0g 000mf 10.90 Adjustment amount 00mE Add water to pH (25°C) 000mf 10.25 000m1 10.90 The bleach-fix solution used in Example 1 was used as is.

The sensitometry was processed at the start and end of the run, and the minimum density (Dmin) and maximum density (Dmax) of the blue-sensitive layer and the sensitivity (log representing density 0.5) were calculated.
The amount of change in E value) due to continuous treatment was measured using a Macbeth densitometer, and the results are shown in Table 3. In the sensitivity change, + indicates an increasing direction of sensitivity, and - indicates a direction of decreasing sensitivity.

Table 3 shows that samples 01 to 07 of color window materials using the magenta coupler shown by the general formula (1) of the present invention clearly show the general formula (1) of the present invention when compared with sample 09 of the comparative coupler.
It is clear that the magenta coupler shown in 1) exhibits small fluctuations in photographic properties, Dmin, Dmax, and sensitivity due to running.

Next, the preservatives in the color developing solution were a developer using the organic preservative of the present invention and a developer using a combination preservative of hydroxylamine-sodium sulfite immediately before and at the end of the run. Comparing the changes in photographic characteristics after
Clearly less variation in min, Dmax, and sensitivity was observed in the practice of the present invention using organic preservatives.

In addition, the replenishment amount of color developer during continuous processing is 40ml/
m, the amount of eruption fluid was approximately 10 m/1.

Example 3 Using samples 01.07 and 08 prepared in Example 1,
A color developer was prepared by replacing the organic preservatives A and B in the color developer A of Example 2 with the combinations of organic preservatives of the present invention as shown in Table 4. The processing steps, bleach-fix solution, washing with water, etc. are exactly the same as in Example 2.

Immediately before the start and end of the run, under the same exposure conditions as described in Example 1, separation exposure was applied using a three-color separation filter to obtain photographic characteristics.

Maximum density (Dmax) associated with continuous processing of the green-sensitive layer at this time
Table 4 shows the amount of change.

As a result of Table 4, the use of the organic preservative of the present invention is 1 to 1 sulfite.
Compared to the use of a lium-hydroxylamine preservative and the compound described in JP-A-63-106655, continuous processing with reduced replenishment clearly improves photographic properties, Dm
It is clear that the processing variation in ax is small. Furthermore, it is clear from comparison with comparative couplers that when using the magenta coupler of the present invention, stable processing is possible with low replenishment processing using the organic preservative of the present invention.

Example 4 Both sides were laminated with polyethylene. Samples were prepared using multilayer silver halide color photographic paper having the layer structure shown below on a paper support with varying amounts of coated silver. These sample numbers are 1)~
19.

As an example, a coating solution was prepared as follows.

(Preparation of coating solution for the first layer) Yellow coupler (Y-8>19.1 g and color image stabilizer (Cpd-1) 4.4 g, ethyl acetate 27.2 cc and high boiling point solvent (Solv-1) 7°7 cc ( 8.0g
) was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% Seratin aqueous solution containing 8 cc of 10% sodium dodecylhenzenesulfonate. This emulsion dispersion and emulsions EM7 and EM8 were mixed and dissolved, and the gelatin concentration was adjusted to have the following composition to prepare a first layer coating solution. The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. The gelatin hardening agent for each layer is 1oxy-3
, 5-dichloro-5-) riazine sodium salt was used.

Moreover, (Cpd-2) was used as a thickener.

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

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiO7) and a bluish dye. ] th layer (blue-sensitive layer) Monodisperse silver chlorobromide emulsion (EM-7) spectrally sensitized with a sensitizing dye (Sen-1) 0,13 Spectral sensitization with a sensitizing dye (Sen-1) Monodispersed silver chlorobromide emulsion (EM-8) Third layer (green-sensitive layer) Monodispersed silver chlorobromide emulsion (EM-9) spectrally sensitized with a sensitizing dye (Sen-2) 0, 14 Monodisperse silver chlorobromide emulsion spectrally sensitized with a sensitizing dye (Sen-2) (EM-10) Gelatin yellow coupler (Y-8) Color image stabilizer (Cpd-10) ? Container (Solv-1) Second layer (color mixing prevention layer) Gelatin color mixing prevention agent (Cpd-1) ? Container (Solv-1) Solvent (Solv-2) Dye (T-1) 0, 89 0, 08 0, 20 0, 20 o, oos Gelatin magenta coupler (M-25) Color image stabilizer (Cpd-2 ) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4> Color image stabilizer (Cpd-5) Solvent (Solv-2) Solvent (Solv-3) Fourth layer (ultraviolet absorbing layer) Gelatin ultraviolet rays Absorber (UV-1) Color mixture prevention agent (Cpd-1) ?Vehicle (Solv-4) Dye (T-2) 0.015 Fifth layer (red sensitive layer) Spectroscopy with sensitizing dye (Sen-3) Sensitized monodisperse silver chlorobromide emulsion (EM-1)) 0,08 Monodisperse silver chlorobromide emulsion spectrally sensitized with a sensitizing dye (Sen-3) (EM-12) 0,14 Gelatin 1.06 cyan coupler (C-1) 0.13 (C-2)
0.16 Color image stabilizer (Cpd-5) 0.32 Color image stabilizer (Cpd-7) 0.18) Vehicle (
Solv-4) 0.10? Container (S
olv-5) 0. 1
0? Container (So 1v-6)
0. 1 1 6th layer (ultraviolet absorption layer) Gelatin 0.48 Ultraviolet absorber (UV-1) 0.18? Container (So
lv-4) 0.
08 Dye (T-2) Seventh layer (protective layer) Acrylic modified copolymer of gelatin polyvinyl alcohol (degree of modification 17%) The structure of the compound using liquid paraffin is as follows.

(Cpd-1) Color mixing prevention agent H (Cpd-4) Color image stabilizer H (Cpd-2) Color image stabilizer (Cpd-5) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-6) Color image stabilizer →Go to CH2-C1) C0NHCaH7(t) Average molecular weight; 60 (Cpd color image stabilizer ca++q(t) c4nq(t) CaI2(t) 4;2:5 mixture (weight ratio) (Solv 1) Solvent (Sol container (Sol 2 medium (Sol container (U■ 1) Ultraviolet absorber CaHl(t) CsH+ + (t) 12:10:3 mixture (weight ratio) of (Solv solvent C00CHZCHC41)q (CH2)8 C2H3 COOCLCtlCtHq 21)S (SOIV ? container (T SO,K to S03 (T was used in a red-sensitive emulsion.

Details of the emulsion used are as follows.

Further, in each layer, as an emulsifying dispersant and a coating aid, Alkanol
cxF-120 (manufactured by Dainippon Ink Co., Ltd.) was used. M M M M M M Cube Cube Cube Cube Cube Cube 1.1 0.8 0.45 0.34 0.45 0.34 99.0 99.0 98.5 98.5 98.5 98.4 0.10 0 .10 0.09 0.09 0.09 0.10 Next, samples were prepared by changing the amount of silver applied in the green-sensitive layer as shown in Table 5. Furthermore, macenta coupler (M-1) (M-14)
Samples were also prepared by replacing the comparative couplers used in Example 1.

1-(5-methylureidophenyl)-5-mercaptotetrazole was used as a green-sensitive emulsion, and 2-amino 5-mercapto-1,3,4-thiadiazole Table 5 After imagewise exposure of the above sample, a paper processing machine was used to process the sample. Continuous processing (running test) was performed using the following processing steps and processing solution until twice the tank capacity for color development was replenished.

Processing process: Direct skin, replenishment amount*, 1 color development, 38°C, 60 seconds, 30mR4
7! Bleach fixing 30-36℃ 45 seconds 215mf
47! Stable ■ 30-37°C 20 seconds 2β
Stable ■ 30-37°C 20 seconds 2p stable ■ 3
0~37°C 30 seconds 250mf 27! dry
Drying 70-85℃ 60 seconds *The amount of replenishment is 1. (
This is the amount of Replenishment in the stabilization process is by tank countercurrent method to stabilize ①-②.The composition of each processing solution is as follows.

Color developer tank liquid replenisher water
800mff
800mj! Ethylenediamine-tetraacetic acid 5.0g
5.0g5.6-Sihydroxybenzene-1+ 2゜4-trisulfonic acid 0゜3g 0.3g
Exemplary compound of the present invention (■-1) 8.0g 9.
0g Sodium chloride 8.4g Potassium carbonate 25g 25g N-ethyl-N-(β methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0g Exemplary compound of the present invention (IV-19) 4.2g Fluorescence Brightener (4,4' diaminostylhene type) Add 2.0g water to 1000mffp100O°C),
10.25 Bleach-fix solution (tank solution and replenisher are the same) water
400mR ammonium thiosulfate 15.0g 000mf 5.0g 10.0g 1). 00 (70%) Sodium sulfite 00mf 7g Ethylenecyaminetetraacetic acid et (I[l) ammonium 5g Ethylenediaminetetraacetic acid diacetic acid 9g Add water 1000mfp1000℃)
5.40 Chlorine (tank solution and replenisher are the same) Formalin (37% > 0.1g formalin-sulfite adduct 0.7g 5-chloro-
2-Methyl-4 isothiaprin-3-one
0.02g 2-methyl-4-isothiazolin-3-one 0.01g copper sulfate
0.005g ammonium water (2
8%) Add 2.0ml water
1000mffp100O℃) 4.0 In the same manner as in Example 1, changes in maximum concentration, minimum concentration, and sensitivity due to running treatment, and staining occurring 10 days after storage under high temperature and high humidity after treatment were measured, and the results are as follows. Table 6
It was shown to.

Thorium g From Table 6, in the case of comparative couplers (samples 17 to 19), magenta coloring layer (GL) at the start and end of running.
The fluctuations in Dmin, Dmax and sensitivity were clearly larger than those of the magenta coupler represented by the general formula (1) of the present invention, and when stored for 10 days at 60°C and 70% relative humidity after processing. It was also observed that the comparison coupler had a higher stain increase in the white background area, while the magenta coupler of the present invention had a lower stain increase.

Furthermore, when comparing Samples 12.13 and 1) and Samples 15.16 and 14, it is clear that in Samples 1) and 14, in which the coated silver amount exceeded 0.80 g/m, there were differences at the start and end of the run. It was observed that the variation difference in photographic performance during processing and the increase in stain after processing were large. On the other hand, sample 12.
No. 13 and Samples 15 and 16 have small differences in photographic performance variation. From this, the amount of coated silver on the sample was reduced within a range that does not impair photographic performance, and by reducing it to 0.80 g/m or less, the use of the magenta coupler of the present invention reduced the amount of color developer replenishment. It is clear that stable processing is possible and that the image storage stability after processing is excellent even under high temperature and high humidity conditions.

In addition, the replenishment amount of color developer during this continuous processing is 30 mfl.
/ m, the volume of aneurysmal fluid was almost non-discharged.

Example 5 In the preparation of the silver halide emulsion described in Example 1, 1
．． C! by changing the amount of NaCρ and KBr in liquids 4 and 6. Monodispersed cubic silver chlorobromide emulsions having different contents were prepared for a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, respectively. Although the halogen composition was changed, the shape, average particle size, and coefficient of variation were the same as those described in Example 1. These are shown in Table 7.

Table 7 Maximum density of yellow in blue-sensitive layer (Dm
ax ), the amount of change in the minimum density (Dmin) and sensitivity (log E value giving a density of 0.5) due to continuous processing was investigated using a Maches densitometer. The results are shown in Table 8.

/ A multilayer silver halide color light-sensitive material shown in Table 8 was prepared in exactly the same manner as in Example 1 using the above emulsions having different halogen compositions.

In order to investigate the photographic properties of these prepared samples, the method described in Example 1 was carried out in the same manner as before, and the general formula (1 ) Samples 21 to 30 using magenta couplers shown in AgBrC/! In sample 21.26 whose halogen composition had a 0° C. content of 70 mol %, large fluctuations in sensitivity and Dmax were observed in the photographic characteristics immediately before and after the start of running. On the other hand, the 01 content is 80
Above mol%, this fluctuation becomes small. From this, it has become clear that the silver halide emulsion used is preferably a silver chlorobromide emulsion having a CI content of 80 mol% or more.

It is also clear that the comparison coupler has larger fluctuations during continuous processing than the coupler of the present invention, as is clear from the previous examples.

(Effects of the Invention) By implementing the present invention, fluctuations in photographic characteristics during continuous processing are small and stable processing is possible. It is also recognized that the obtained color image has storage stability with respect to temperature and humidity, and in particular, has a sharp characteristic with little increase in staining in white background areas. In addition, the generation of a large amount of overflow liquid due to replenishment of the replenisher, which had been a problem in the past, could be reduced.

Claims (2)

[Claims] (1) A method in which a silver halide color photographic light-sensitive material is continuously processed with a color developing solution containing at least one aromatic primary amine color developing agent, in which at least one layer of the silver halide color photographic light-sensitive material is is silver chloride 8
A silver halide emulsion containing 0 mol% or more and the following general formula (
I) contains at least one magenta coupler represented by I), the color developer contains at least one organic preservative, and the replenishment amount of the color developer during continuous processing is Silver color photosensitive material 1m^
A method for processing a silver halide color photographic light-sensitive material, characterized in that the amount of silver halide color photographic material is in the range of 20 to 150 ml per 2 ml. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ R_1 and R_3 represent substituted or unsubstituted phenyl groups, R_2 is a hydrogen atom, an aliphatic or aromatic acyl group,
represents an aliphatic or sulfonyl group, Y represents a hydrogen atom or a group capable of leaving during the oxidation and coupling reaction of the developing agent (hereinafter referred to as a leaving group), and R_1, R_2, R_3 or Y represents a dimer or more. may form a multimer. The aliphatic group mentioned here refers to a linear, branched or cyclic alkyl, alkenyl or alkynyl group. (2) The color developing solution contains at least one compound selected from the group consisting of hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones, α-aminoketones, and sugars, and monoamines and diamines. Contain at least one organic preservative selected from the group consisting of compounds, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and fused cyclic amines. A processing method according to claim 1, characterized in that: