JPH01207746A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To inexpensively obtain the title material superior in stability, having improved image preservability after processing by developing the sensitive material incorporated with a coupler capable of inactivating an aromatic primary amine color developing main agent by chemically binding thereto in the photographic layer of the sensitive material mounted on a supporting body, with a specified color developer. CONSTITUTION:The sensitive material contains the coupler capable of inactivating the aromatic primary amine color developing main agent by chemically binding thereto in at least one layer of the sensitive material mounted on the supporting body, and is developed with the color developer prepared by diluting the condensed composition of the developer for the sensitive material which contains benzyl alcohol of 90-500ml/l and an aromatic primary amine color developing main agent of 0.07-0.4mol./l. Thus, the inexpensive sensitive material with the excellent stability is obtd., and the image preservability of the sensitive material already processed, is improved.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a processing method using a concentrated developer composition for silver halide color photographic light-sensitive materials, and more specifically, the present invention relates to a processing method using a concentrated developer composition for silver halide color photographic light-sensitive materials. The present invention also relates to a developer concentrate composition for silver halide color photographic materials, which has excellent stability and improved image storage properties of processed color photographic materials, and a processing method.

(Prior art) In general, silver halide color photo X5 optical material developer has reduced costs during transportation, convenience of handling, and packaging material F41ii.
It is provided as an 8I reduced composition for the purpose of reducing the li rating, etc., and is diluted with water before use.

Further, the developer concentrate composition is divided into several parts for each component in order to improve concentration and stability.

Conventional developer concentrate compositions for color printing have four parts: alkaline agent/preservative/benzyl alcohol/
Generally, it is divided into parts, each containing a developing agent as its main component. However, in recent years, for the purpose of cost reduction, benzyl alcohol and developing agent are made into the same part, and developer solution temperature compositions having a three-part structure and one part have become common.

However, in the case of a three-part structure, benzyl alcohol and a developing agent react in the part where both coexist, producing compounds that affect photographic properties, and the image storage stability of the color photosensitive material is significantly reduced.

Conceivable. This phenomenon is particularly noticeable when the composition is stored for a long period of time.

It is presumed that such a compound is produced, for example, by the following reaction.

<7-) kayayo2 NH2D-3 (Object of the present invention) The present invention relates to a concentrated developer composition and a processing method for silver halide color photographic light-sensitive materials.More specifically, the concentrated developer composition is inexpensive. It is an object of the present invention to provide a developer concentrate composition for a silver halide color photographic light-sensitive material and a processing method, which has excellent stability and improved image storage stability of the processed color photographic light-sensitive material.

(Structure of the invention) The objects of the invention were achieved in the manner described below.

(1) In the processing method for silver halide color photographic light-sensitive materials, benzyl alcohol is added at 90 m1/L to 500 m1/L.
1/L and an aromatic primary amine color developing agent from 0.07 mol/L to 0.4 mol/L. A silver halide color containing a coupler in at least one of the photographic layers on a support, which has the function of chemically bonding with an aromatic primary amine color developing agent to inactivate it in a developer. A method for processing a silver halide color photographic material, the method comprising processing a photographic material.

(2) The second-order reaction rate constant of the coupler with p-anisidine (80°C) is 0 to 1. A method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the OX10 is in the range of 11 mol·sec.

In the coupler of the present invention, a reaction product of a color developing agent represented by the above-mentioned compound A and benzyl alcohol remains in the processed color photographic material, and then reacts with unreacted coupler to form a stain. It also has the function of preventing yellow stain from being generated due to thermal and photodecomposition of itself.

This function is to chemically inactivate the reaction product between the color developing agent and benzyl alcohol.As a result of extensive research, we have found that the aromatic amine light color developing agent is chemically inactivated by a substitution reaction tower addition reaction. It was discovered that this is synonymous with the function of inactivation, and this led to the present invention.

In other words, couplers, which have the function of chemically bonding with aromatic amine color developing agents and making them chemically inactive, are effective in principle, but they do not have sufficient effects in practice. , the second-order reaction rate constant of the coupler with p-anisidine (at 80°C) is 1.0 to 1.0
Preferably, it is in the range of 11 mol·sec.

A concentrated developer composition for silver halide color photographic light-sensitive materials is a developer concentrate for silver halide color photographic light-sensitive materials that is concentrated for the purpose of reducing transportation costs, convenience in handling, and lowering the cost of packaging materials. It is divided into three to five J) for concentration and stability improvement. When used, the above-mentioned parts 3 to 3 are diluted with water and used as a developer for silver halide color photographic light-sensitive materials. By the method of the present invention, J, e) can be achieved, and improvements in convenience and the like can be achieved.

As mentioned above, the developer concentrate composition for silver halide color photographic light-sensitive materials of the present invention is a part containing benzyl alcohol and a developing agent as main components, and has a concentration ratio of 5 to 5.
It is made about 30 times, preferably about 10 to 30 times. A high concentration rate is unfavorable from the viewpoint of solubility and low-temperature crystallization.
When it is low, not only is there little cost advantage, but also convenience in handling is low.

The hardness of the benzyl alcohol used in the present invention is 90m
1/L to 500a+I/L, preferably 250 fl/L
~45018, and 1 degree of color developing agent is 0.07
mol/L -0, 4t3/L preferably 0.15 mol/L
L to 0.35 mol. If the concentration of benzyl alcohol or developing agent is higher than the above range, it will be difficult to dissolve the compound, and even if it can be dissolved, the amount of compound A produced will increase.

If it is low, not only is there little cost advantage;
Convenience in handling is also reduced.

Representative examples of known aromatic primary amine color developing agents used in the present invention are shown below, but the invention is not limited thereto.

D-I N,N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N-ethyl -N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-64-amino-3-methyl-N-ethyl- N-(β
-(methanesulfonamide)ethylcoaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl-N -ethyl-N-methoxyetheraniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-buenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N-(β-(
methanesulfonamido)ethyl]-aniline (exemplified compound D-6). Reasons why it is preferable include color development hue and image storage stability.

Further, these p-fuynylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and fluorenesulfonates.

The pH of the concentrated developer composition for silver halide color photographic materials of the present invention is 0. /, j is preferably /, in the range of 0 to da. The pH range commonly used is 0.3-0. However, at such a low pH, the above-mentioned compound A
The generation of this phenomenon is noticeable, and the image storage stability may be impaired. Also, DH! If this is the case, the color developing agent deteriorates significantly during storage of the concentrate.

Generally, in developer concentrate compositions for silver halide color photographic materials, sulfites are used to prevent oxidation of the developing agent. The concentration usually used is 0 in molar ratio to the developing agent.
．． The range is /~/, J.

The sulfite O@degree castle of the present invention is preferably 0. Reference ~/, 0
1, more preferably in the range o, t-o, r. At -a degrees upwind of the present invention, sulfite does not dissolve and has no effect on photographic properties. At concentrations below the present invention, the formation of the aforementioned compound mA is dominated by IgI, which significantly impairs image storage stability. Become.

The sulfites mentioned in the present invention specifically include sodium sulfite, potassium sulfite, and more! Preferred are sodium sulfite, potassium bisulfite, sodium metasulfite, and potassium metasulfite.

Developer solution for silver halide color photographic light-sensitive materials of the present invention'I
! It is preferable that the A-condensation composition contains alkanolamines and/or glycols for the purpose of dissolving benzyl alcohol in high concentration, and the content is 70ml/
L~400m18 is preferable.

Preferred specific examples of alkanolamines and glycols include monoethanolamine, jetanolamine, triethanolamine, ethylene glycol, diethylene glycol, and triethylene glycol.
Particularly preferred are triethanolamine and diethylene glycol.

Number fJ for silver halide color photographic light-sensitive materials of the present invention
I image solution FIA3i! Various chelating agents can be added to the composition as needed.

As the chelating agent, RH compounds are preferred, such as those disclosed in Japanese Patent Publication Nos. 48-39'496 and 44-3023.2°
7 minoboricarboxylic acid neck described in No. 7, JP-A-56-973
No. 47, Special Publication No. 5.6-39359 and West German Patent Tube 2
．． 2. Phosphonic acids described in No. 27.639, JP-A No. 52-102726, No. 53-42730, No. 54
-121127, 55-126241 and 55
Phosphonocarbon a neck described in -659506, etc., and other JP-A-58-195045, JP-A-511-2034
No. 40 and Special Publication No. 53. Examples include compounds described in Japanese Patent No. '-40900. Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, diethylenetriamine 5! ):acid,
Ethylenediamine 4giI? Acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,
N',N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid,
Ethylenediamine orthohydroxyphenylacetic acid, 2
-phosphonobutane-1,2,4-1-licarboxylic acid,
l-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 as necessary. good.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer.

A fluorescent brightener may be added to the concentrated developer composition for silver halide color photographic materials of the present invention, if necessary. As the optical brightener, 4゜4'-diamino-2,
2'-disulfostilbene compounds are preferred.

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

Developer solution am for silver halide color photographic light-sensitive materials of the present invention
The temperature at which the product is stored is preferably room temperature or lower, but
Particularly preferred is θ°C to lO°C. At temperatures higher than this, the above-mentioned compound A is more likely to be formed than B, and image storage stability is significantly impaired. Further, a temperature lower than this is not preferable from the viewpoint of crystallization properties.

Furthermore, the developer for silver halide color photographic light-sensitive materials, which is prepared by diluting the developer solution swam composition for silver halide color photographic IK and light-sensitive materials with water, contains various compounds as necessary. can be added.

For example, as a compound that directly preserves the color developing agent, various hydroxylamine compounds, Japanese Patent Application No. 61-186
Hydroxam 8 described in No. 559, No. 61-17075
The hydrazines described in No. 6, the hydrazide neck, and No. 61. −
Phenols described in No. 188742 and No. 61-203253, α-hydroxyketone neck and/or α-7 minoketone described in No. 61-188741, and/or G1-18061
Various zeros listed in issue 6! It is preferable to add Zhao, also 2
．． In combination with the above compounds, Japanese Patent Application No. 61-147823, No. 61-166674, No. 61-165621,
Monoamine lff described in No. 61-164515, No. 61-170789, No. 61-168159, etc.
, No. 61-173595, No. 61-164515,
Diamines described in No. 61-186560, etc., 6t
-ts5G21, polyamines described in 61-169789, polyamines described in 61-180619, nitroxy radicals described in 61-1-7760, 61-1065G1, and 61-19741
Alcohol neck described in No. 9, oxime octopus described in No. 61-265149, and 3 described in No. 61-265149.
Preference is given to using grade amines.

As other preservatives, JP-A No. 57-44148 Et.
Hido 57-5374 '9 No. 2E each fm gold vAt
f[, salicylic acids described in JP-A No. 5.9-180588, JP-A-Sho! ≠-3!Lamines described in Al6 described in No. 32, polyethyleneimines described in JP-A-5' J4C, aromatic polyhydroxy compounds described in U.S. Patent Nos. J, 74c, G, J4AII, etc. may be included as necessary. Especially aromatic polyhydroxy compounds alkanolamines and patent application 1986-Colo 4A/! Addition of No. 2 is preferred.

The color developer used in the present invention is preferably DH2
-No, more preferably -ii, o.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, west borate, hydroxybenzoate, glycyl salt,
N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3, μm dihydroxyphenylalanine salt, alanine salt, aminobutyrate, λ-amino-2-
Methyl/, J-10 pandiol salt, valine salt, florin salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. Especially charcoal & salt, sulfate, tetraborate, hydroxybenzoate are soluble, pH 9.0
The buffering capacity in the above pH range is great! Even if it is added to the developer, it will have an adverse effect on the photographic performance! It is particularly preferable to use these warm fJi agents because they have the advantages of being free from iIC fog (such as iIC fog) and being inexpensive.

Specific examples of these laxatives include sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), tetraboron potassium acid, sodium O-hydroxybenzoate (sodium salicylate)%0-potassium hydroxybenzoate, 5-
Examples include sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention
It is not limited to these compounds.

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

Appetizer + j L Lf As a development accelerator, Tokuko Sho 37-1
6088, No. 37-5987, No. 38-7826, No. 44-12380, No. 45-901!3, and U.S. Pat. -49829 and 50-
14554, JP-A-50-137726, JP-B-Sho 44-30
．． No. 074, Japanese Unexamined Patent Publication No. 1983. -156826 and 52
-43429, etc., and the quaternary ammonium salt neck represented by U.S. Patent No. 2.494. ．． No. 903, No. 3,128°182, No. 4,230.796, No. 3,253.9
No. 19, Japanese Patent Publication No. 41-11431, United States, ' \, ・ \ /' Patent No. 2.482.546, 2. 59s, 9
Amine compounds described in No. 26 and No. 3,582.346, etc., Japanese Patent Publication No. 37-16088, No. 42-2520
No. 1, U.S. Patent No. 3,128.183, Special Publication No. 1973-
No. 11431, No. 42-23883 and U.S. Patent No. 3
．． Polyalkylene oxide represented by No. 532.501, other 1-phenyl-3-pyrazolidones, imidazole, etc. can be added as necessary.

In the present invention, any anti-capri agent can be added as required. 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-nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Typical examples include nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

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 1 minute. It is preferable that the amount of replenishment is small, but it is 20 to 600 - preferably 50 to 300. It is e.

More preferably, it is 100.47 to 200d.

Next, the desilvering step in the present invention will be explained.

In the present invention, any process such as a bleaching process, a fixing process, a fixing process, a bleaching process, a bleaching process, a bleaching process, a bleaching process, and a clean fixing process may be used. The effect of the present invention becomes more pronounced when the desilvering step is shortened, that is, 2 minutes or less, more preferably 15 seconds to 90 seconds.

The cleaning solution, bleach-fix solution, and fixing solution used in the present invention will be explained below.

As the bleaching agent used in the bleaching solution or bleach-fixing solution used in the present invention, any bleaching agent can be used, but in particular organic complex salts of iron (III) (e.g., aminopolymers such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid) can be used. complex salts with carbon FIIET, aminopolyphosphonic acids, phosphonocarboxylic acids and 1rja phosphonic acids) or citric acid, tartaric acid, malic acid, etc.
Acids; persulfate salts; hydrogen peroxide and the like are preferred.

Among these, the *R complex salt of iron (m) is particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution.
1': Aminopolycarboxylic acids, aminopolyphosphonic acids, or phosphonic acids used to form salts or their salts are listed as ethylenediaminetetraacetic acid,
Examples include diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid, and the like.

These compounds may be sodium, potassium, 1f thium or ammonium salts. Among these compounds, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid 1.1.3-diaminopropanetetraacetic acid, methyliminodiacetic acid iron (m)
Complex salts are preferred because they have a high bleaching edge.

These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate. Ferric ion fit Ju may be formed in a solution using a chelating agent such as aminopolycarboxylic acid, 7-minopolyphosphonic acid, phosphonocarboxylic acid, etc. Among the iron complexes, aminopolycarboxylic acid iron (f), which may be used in excess to form a complex salt, is preferable, and the amount added is 0.01 to 1.0 mol/1, preferably 0.05 to 0. .50 mol/j.ff White waves, bleach constant Mtfl and/or their pre-baths may contain various compounds as bleach accelerators.For example, U.S. Pat. German Patent No. 1.290.812 [iF, JP-A-53
-95630 Publication, Research Disclosure No. 1
No. 7129 (July 1978 issue), compounds having a mercapto group or disulfide bond, and
5-8506, JP-A No. 52-20832, JP-A No. 53-
No. 32735, U.S. Patent 3. ．． Thiourea compounds described in No. 706.561, etc., or halides such as iodine and bromide ions are preferred because they have excellent bleaching blades.

In addition, the bleach or bleach-fix solution used in the present invention may contain bromides (e.g., potassium bromide, sodium bromide, ammonium bromide), chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride), or iodides. (
For example, a rehalogenating agent such as ammonium iodide (ammonium iodide) can be included. If necessary, one or more types with pH buffering ability such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, ia acid, phosphoric acid, sodium 3B acid, citric acid, sodium citrate, tartaric acid, etc. Corrosion inhibitors such as non-acid, acid and alkali metal or ammonium salts thereof, ammonium rifate, guanidine, etc. can be added.

The fixing agent used in the bleach-fixing solution or fixing solution according to the present invention is a known fixing agent, namely, thioTERM salts such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene Water-soluble silver halide solubilizers such as bisthioglycolic acid, thiourea compounds such as 3,6-cythia-1,8-octanediol, and thioureas, and these are used alone or in combination of 211 or more. In addition, a special bleach-fixing solution consisting of a combination of a fixing agent described in No. 155354/1986 and a halide such as potassium iodide in a large quantity can also be used. In the present invention, it is preferable to use thiosulfates, especially ammonium thiosulfates, and the amount of fixing agent per 11 is preferably 0.3 to 2 mol, more preferably 0.5 to 1.0 mol ff1l! It is four. The p11f+i range of bleach constant @ solution or fixer is 113 to 10
is preferable, and 5 to 9 are particularly preferable.

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

The bleach-fixing solution and fixing solution in the present invention can be used as a preservative! I
N! Sulfates (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (e.g., ammonium sulfite, sodium bisulfite, llt
potassium metabisulfite, etc.), metabisulfite (e.g., potassium metabisulfite, meta 1! sodium sulfite,
Contains sulfite ion-releasing compounds such as ammonium metabisulfate, etc.). The content of these compounds in sulfite ions is preferably about 0.02 to 0.50 mol/l, more preferably 0.04 to 0.40 mol/l, calculated as fA.

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

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

The silver halide color photographic material used in the present invention is generally washed with water and/or stabilized after desilvering treatment such as fixing or bleach-fixing.

The amount of water used in the washing process depends on the characteristics of the Nijoko material (for example, depending on the material used, such as turnip bows), the purpose, 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 flushing tanks and the amount of water in the multi-stage countercurrent method was determined by the Journal Op.
alor th@5occlety or MoEion
Picture and T@levisionEn
gln@ers) 'is volume 64, r', 248
253 (May 1955 issue), the number of stages in the itm regular multistage countercurrent system is preferably 2 to 6, and particularly preferably 2 to 4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, 0.51 to 11 or less per ld of the irradiating material. Due to the increased residence time of water, problems such as bacteria propagation and floating matter adhering to the photosensitive material occur.In the processing of the color photosensitive material of the present invention, as a solution to such problems, special ffJ [? The method of reducing calcium and magnesium described in No. 61-131632 can be used very effectively. Also, JP-A-57-8542
isothiazolone compounds and thiabendazoles described in No. 61-120145, chlorine-based fungicides such as chlorinated sodium isocyanurate described in No. 61-120145,
Benzotriazole described in No. 05487, Copper ion +1!1 Hiroshi Horiguchi, "Chemistry of anti-mildew agents", Sanitary Technology Society, Inc., "Microorganism destruction, step surface, anti-mildew technology", Japan Anti-fungal It is also possible to use the corrugating agents described in the Society Hato's "Encyclopedia of Antifungal Agents."

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

Following the water washing process described above, it is also possible to directly process with a stabilizing liquid without going through the water washing process.A compound having an image stabilizing function is added to the stabilizing liquid.
Examples include aldehyde compounds typified by , buffers for adjusting membrane pH suitable for dye stabilization, and ammonium compounds. Further, in order to prevent the proliferation of bacteria in the liquid and to impart antifungal properties to the photographic material after processing, the various contagious agents and antifungal agents described above can be used.

Furthermore, a surfactant 2, a fluorescent whitening agent, and a hardening agent may be added.In the processing of the photosensitive material of the present invention, stabilization is performed without going through a water washing step (if it is directly carried out, as described in Japanese Patent Application Laid-Open No.
-t! 4CI issue, same! r-74 (!3≠ issue, same 60-2
All known methods described in Ko03daj and the like can be used.

Others, l-hydroxyethylidene! , /-diphosphonic acid, chelating agents such as ethylenediaminetemethylenephosphonic acid, and magnesium and bismuth compounds are also preferred embodiments.

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

The pH of the water washing step or stabilization step of the present invention is μ~IO), preferably! ~l. Temperature depends on the use of photosensitive materials.
Various settings can be made depending on the characteristics, etc., but in general /! ~4Cj'C
, preferably 10-UO°C. The time can be set arbitrarily, but the shorter the better, preferably 30 seconds to 3 minutes,
More preferably, the time is 75 seconds to 2 minutes. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduced emissions, ease of handling, and the like.

A specific preferred amount of replenishment is 0.5 to 50 times, preferably 3 to 40 times, the amount brought in from the previous bath per unit area of the photosensitive material. or 11 or less, preferably 500. It is less than or equal to e.

Further, replenishment may be performed continuously or intermittently.

The liquid used in the water washing and/or stabilization step can also be used in the previous step.・As an example of this, the overflow of washing water reduced by the multi-stage countercurrent method is made to flow into the bleach-fixing bath, which is the pre-bath, and the bleach-fixing bath is filled with tfA.
It is possible to replenish the condensed liquid and reduce the amount of waste liquid.

A preferred coupler having the function of chemically bonding with an aromatic amine developer to inactivate the developer in the present invention can be represented by the following general formula (I).

General formula (I) CP+Z ) i In the formula, Cp represents a coupler residue, including dimeric, oligomeric, and polymeric couplers, and 2 represents a group that chemically bonds with an aromatic amine developer.

Alternatively, it represents an integer of 1 or more, and when it is 2 or more, Z may be the same or different.

The coupler residue represented by Cp may be substituted with other substituents in addition to the substituent represented by 2. CP may be colorless, but it is preferable that it forms a dye. , Cp may react with the oxidized product of the aromatic amine developer to release photographically useful groups (e.g., development inhibitors, dyes, ligands, bleach accelerators, etc.), but Cp may not release. I prefer things.

Preferred examples of the coupler residue Cp include phenolic and naphthol cyan couplers as the cyan coupler ε;
Examples of magenta couplers include 5- and lazolone, pyrazoloazole, indacylon, and cyanoacetyl magenta couplers, and examples of yellow couplers include α-pivaloylacetanilide and α-benzoylacetonide anilide couplers.

2 represents a group that reacts with an aromatic amine developer, and is substituted by at least one group on the coupler residue Cp.

Z may be a group capable of leaving during the coupling reaction with the oxidized aromatic amine developer (hereinafter referred to as a leaving group), but is preferably substituted at a position other than the coupling active position.

A more preferred coupler used in the present invention is represented by the following general formula (II).

General formula (n) (R1(h+-R2→, Cp+R3÷ApH4).

In the general formula (n), Cp has the same meaning as the coupler residue CP in the general formula (I).

R-+A-)-R- and R-+A-1R3-1p
2 4 represents Z in the general formula (CI); 0m and n represent an integer of 0 or more such that the sum is the expression in the general formula (I); R1 is an aliphatic group, an aromatic group, or a hetero group; Represents a ring group.

Rj5 and R3 represent a group connecting the coupler residues Cp and A, among which R2 represents a group that reacts with an aromatic amine developer and leaves.

R4 represents a group that reacts with an aromatic amine developer and leaves the group.

A represents a group that reacts with an aromatic amine developer to form a chemical bond; p represents 1 or 0;

Although q is synonymous with P, it is not necessary that p=q.

Here, R1 and R2 and R3 and R4 may be bonded to each other to form a cyclic structure.

Each group in general formula (n) will be explained in more detail.

The aliphatic group referred to in R1 preferably has 1 to 32 carbon atoms,
It represents an aliphatic hydrocarbon, and represents a linear, branched, or cyclic alkyl group, aralkyl group, alkenyl group, or alkynyl group, and may be further substituted with a substituent.

The aromatic group referred to in R1 is a carbocyclic aromatic group (having 6 to 6 carbon atoms).
20 (preferably 0, for example phenyl, naphthyl) and heterocyclic aromatic groups (preferably 0 having 4 to 10 carbon atoms, such as furyl, thienyl, pyrazolyl, pyridyl, indolyl), monocyclic These aromatic rings may have a substituent.

The heterocyclic group referred to in R1 is a carbon atom, an oxygen atom, i!
A group having a 3- to 10-membered ring structure composed of a nitrogen atom, a sulfur atom, or a hydrogen atom is preferable, and the petro ring itself may be a saturated ring or an unsaturated ring, and further substituents may be substituted with (e.g., coumanyl group, pyrrolidyl group, pyrrolinyl group, morpholinyl group).

R2 represents a group that connects the coupler residue Cp and (A), and represents a group that reacts with an aromatic amine developer and leaves, R2 represents -( A) A group that bonds with - (for example, an aminoalkylene group, an aminoarylene group, an oxyalkylene group, an oxyarylene group, a thioalkylene group, and a thioarylene group. The number of carbon atoms thereof is the same as in the case of R3 below.) is preferred.

(A) with the coupler residue Cp represented by R3.

The group connecting these groups may be any group commonly used in the art, such as an alkylene group having 1 to 3 carbon atoms, an arylene group having 6 to 16 carbon atoms,
Aralkylene group having 7 to 17 carbon atoms, 3 to 17 carbon atoms
a peterocyclene group having 10 atoms, an oxygen atom, a sulfur atom, an amino group, a carbonamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a ureido group, a sulfamoylamino group, a carbamoyloxy group, an oxycarbonamide group, It includes an acyl group, an alkoxy group, a carboxy group, a sulfone group, and a linking group formed by a combination of these linking groups.

R4 represents a group that reacts with an aromatic amine developer and leaves -(A
) a group bonding with - (e.g. 3- and lazolyloxy,
3H-1,2,4-oxadiazolin-5-oxy, aryloxy, alkoxy.

cy, alkylthio, arylthio, and substituted N-oxy, and the number of carbon atoms thereof is the same as in the case of R3. ) or a herogen atom is preferred.

A represents a group that reacts with an aromatic amine developer to form a chemical bond, and contains an atom with a low electron density. Here, L is a group that bonds with R1 or R3, and is an alkylene group, -〇- 1-S-.

Represents a single bond, where L' and L' are the same or different; Rlm represents a hydrogen atom, an aliphatic group (e.g. methyl, isobutyl, t-butyl, vinyl, benzyl, octadecyl, cyclohexyl), aromatic group groups (eg, phenyl, pyridyl, naphthyl), heterocyclic groups (eg, piperidyl, pyranyl, furanyl, chromanyl), acyl groups (eg, acetyl, benzoyl), and sulfonyl groups (eg, methanesulfonyl, benzenesulfonyl).

Preferably, L is an alkylene group, -0-1R' and R
# may be the same or different, and each represents R1 or L'
Of these, a group represented by R is particularly preferred.

Y is an aromatic amine developer represented by R in general formula (II)
+A+ R-S and R7EA9R3- R
2 Table 03 lists the groups that promote addition to the groups to be added to, such as hydrogen atoms, aliphatic groups, aromatic groups, heterocyclic groups, acyl groups,
It represents a sulfonyl group and includes specific examples of each group exemplified in %Reag, and G2 and 03 may be bonded to each other to form a cyclic structure.

Particularly preferred Y is an oxygen atom or a sulfur atom.

Y' represents the same meaning as Y.

A more preferable example of A is -alkylene-〇-1 general formula (
When p=o in II), R2 represents a linking group that is electron-withdrawing to R1, for example, R-03O□R2
1 is preferred, where 10SOR' represents -R2.

In the general formula (II), when q=Q, R4 represents a group that is electron-withdrawing to R3, such as a halogen atom,
-R-0SO2-R4° etc. are preferred, where -0SO2-R4' represents R4.

In general formula (If), q is preferably 1.

More preferred couplers used in the invention are represented by the following general formulas (m) to -general formula (2).

General formula (I[I) H General formula (rV) H Rg+ General formula (V) General formula (VI) General formula (■) R5. R6, R, and Yl
, R8. in general formula (IV). R4, R9° and R
10, R11, R12, R13 and Y3 in general formula (V), R14 in general formula (VI), substituents on Za and zb, and Y4. Q and Y in general formula (■) (hereinafter referred to as substituents on general formulas (m) to (■))
At least one of them is a group represented by Z in general formula (1).

General formula (III) ~ (■
) Each substituent group above is defined as follows.

R5, R8 and R9 represent an aliphatic, aromatic or heterocyclic group.

R6, R7 and Rlo represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, an alkoxy group or an acylamino group.

R9' is a hydrogen atom or has the same meaning as R9. r represents 0 or l.

R13 represents a phenyl group.

R1□ has the same meaning as an acyl group or R13.

R1□ is a hydrogen atom, an aliphatic or aromatic acyl group,
represents an aliphatic or aromatic sulfonyl group; R14 represents a hydrogen atom or a substituent;

Za and zb are methine, substituted methine, -N= or -
Represents NH-.

Q represents a substituted N-7enylcarbamoyl group.

Yl, Y2. Y3. Y4 and Y5 represent a hydrogen atom or a leaving group.

In general formula (III) and general formula (IV), R6 and R7 and R9 and R10 may each form a 5.6- or 7-membered ring.

The substituents in the above general formulas (m) to (■) may further have a substituent, and such optionally substituted substituents include an alkyl group, an aryl group, a heterocyclic group, Alkoxy groups (e.g. methoxy, 2-methoxyethoxy, tetradecyloxy, aryloxy groups (e.g. 2
, 4-di-tert-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy, 4-butanesulfonamidophenoxy), acyl groups (e.g. acetyl, benzoyl), ester groups (e.g. ethoxycarbonyl,
, 2.4-di-tert-amylphenoxycarbonyl, acetoxy, benzoyloxy, butoxysulfonyl, toluenesulfonyloxy), amide groups (e.g. acetylamino, butanesulfonamide, dodecylbenzenesulfonamide, dipropylsulfamoylamino)
, carbamoyl groups (e.g. dimethylcarbamoyl, ethylcarbamoyl), sulfamoyl groups (e.g. butylsulfamoyl), imido groups (e.g. succinimit, hydantoynyl), ureido groups (e.g. phenylureido, dimethylureido), sulfonyl groups (e.g. , methanesulfonyl, carboxymethanesulfonyl, phenylsulfonyl), aliphatic or aromatic thio groups (e.g. butylthio, phenylthio), hydroxyl groups,
Examples include groups selected from cyano groups, carboxyl groups, nitro groups, sulfo groups, halogen atoms, and the like. In addition, when two or more such substituents are present, they may be the same or different from each other.

Furthermore, R5% Ra, R7 or Yl: R8°R, R or Y2; R1□, R1□, R13 or Y3; R1
4, substituents on Za and zb or Y4. Q or Y
5 may form a dimer or more multimer.

Unless otherwise specified herein, the number of carbon atoms in an aliphatic group (alkyl group, alkoxy group, alkenyl group, etc.) is preferably 1 to 22, and the number of carbon atoms in an aromatic group (aryl group, aryloxy group, etc.) is preferably 1 to 22. is preferably 5 to 16.

Each group of general formula (III) to general formula VII) in the case where Z does not apply will be explained in detail.

Yl, Y2, Y3 in general formula (m) ~ - general formula ■)
, Y4 and Y5 represent a leaving group, the leaving group is an aliphatic group, aromatic group, heterocyclic group, aliphatic/aromatic group, or Heterocyclic sulfonyl groups, aliphatic/aromatic groups or groups that bond with m-carbonyl groups, halogen atoms, aromatic azo groups, etc., and aliphatic, aromatic, or heterocyclic groups included in these leaving groups. The ring group may be substituted with R5 permissible substituents, and when there are two or more of these substituents, they may be the same or different,
These substituents may broadly include substituents permissible for R5.

Specific examples of coupling-off groups include halogen atoms (eg fluorine atom, chlorine atom, bromine atom), alkoxy groups (eg ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy).

carboxylpropyloxy, methylsulfonylethoxy), aryloxy groups (e.g. 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy), acyloxy groups (e.g. acetoxy, tetrazocatyloxy, benzoyloxy), aliphatic or aromatic sulfonyloxy groups (e.g. methanesulfonyloxy, toluenesulfonyloxy), acylamino groups (e.g. dichloroacetylamino, heptafluorobutyrylamino), aliphatic or aromatic sulfonamide groups (e.g. methanesulfonamino, p-toluenesulfonylamino) ), alkoxycarbonyloxy groups (e.g. ethoxycarbonyloxy, benzyloxycarbonyloxy)
, aryloxycarbonyloxy groups (e.g. phenoxycarbonyloxy), aliphatic, aromatic or heterocyclic thio groups (e.g. ethylthio, phenylthio, tetrazolylthio), carbamoylamino groups (e.g. N-methylcarbamoylamino%N-phenylcarbamoylamino)
% 5- or 6-membered nitrogen-containing heterocyclic group (e.g. imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1
．． 2-dihydro-2-oxo-1-pyridyl), imide groups (e.g. succinimide, hydantoinyl), aromatic azo groups (e.g. phenylazo), etc., and these groups can be further substituted with a group allowed as a substituent for R5. The leaving group of the present invention may also be a bis-type coupler obtained by condensing a four-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. Although they may contain photographically useful groups such as , development accelerators, etc., it is preferable that they do not contain them. Preferred combinations of leaving groups in each general formula will be described later.

Examples of aliphatic groups for R, R and R9 in general formula (m) and general formula (ff).

Examples of the aryl group include phenyl group, naphthyl group, etc., and examples of the heterocyclic group include 2-pyridyl group and 2-imidazolyl group. basis,
Examples include 2-furyl group and 6-quinolyl group. These groups may be further substituted as described above.

When R6 in the general formula (m) and Rlo in the general formula (■) are substitutable groups, they may be substituted with the optional substituents described for R5.

R6 in general formula (m) is preferably an aliphatic group, such as a methyl group, ethyl group, propyl group, butyl group, pentadecyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, phenylthiomethyl group. group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, methoxymethyl group, and the like.

In the general formula (m) and the general formula (ff), Yl and Y2 are hydrogen atoms or the aforementioned coupling-off groups (those mentioned for Y1 to Y5 in the general formulas (m) to (VII)).

These leaving groups may contain photographically useful groups, but it is preferred that they do not.

Preferred examples of the cyan coupler represented by the general formula (III) or (ff) are as follows.

In general formula (III), R5 is preferably a substituted or S-substituted alkyl group or an aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In general formula (m), R6 is preferably an alkyl group having 2 to 15 carbon atoms and a methyl group having a substituent having 1 or more carbon atoms, and examples of the N substituent include an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, Alkyloxy groups are preferred.

In general formula (II[), R6 is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

In general formula (m), R7 is preferably a hydrogen atom or a halogen atom, with chlorine and fluorine atoms being particularly preferred.

In general formula (IV), R8 is preferably an aryl group or a heterocyclic group, including a herogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group,
Sulfonyl group, sulfamide group, oxycarbonyl group,
More preferably, it is an aryl group substituted with a cyano group.

In general formula (ff), when Rlo and R9 do not form a ring, R9 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group.

R1 (l is preferably a hydrogen atom.

In general formulas (m) and (ff), preferable Y and Yl are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In general formula (m), Yl is preferably a halogen atom, particularly preferably a chlorine atom or a fluorine atom.

When r=o in the general formula (ff), Yl is more preferably a halogen atom, particularly preferably a chlorine atom or a fluorine atom.

The substituents in general formula (V) will be explained. Rt□ represents an acyl group or a substituted or unsubstituted phenyl group.

To explain R1□ in detail, the acyl group of R1□ is an aliphatic acyl group or an aromatic acyl group.

Examples include heterocyclic acyl groups, which may be substituted with the optional substituents described for R5.

The substituent on the substituted or unsubstituted phenyl group of R1□ may be any of the optional substituents mentioned for R5, and the number of substituents on the phenyl group is 1 to 5.
can take any number of substituents, and each substituent may be the same or different.

R1□ particularly preferably represents a substituted phenyl group.

R1□ is a hydrogen atom, an aliphatic or aromatic acyl group,
It represents an aliphatic or aromatic sulfonyl group, and if R1□ is a substitutable substituent, it may be substituted with the optional substituent mentioned for R5.

R1□ particularly preferably represents a hydrogen atom.

R13 represents a substituted or unsubstituted phenyl group, and these are synonymous with the substituted or S-substituted phenyl group of FL1□.

Y3 in general formula (V) each represents a hydrogen atom or a coupling-off group, examples of which include a halogen atom (e.g. fluorine atom, chlorine atom), an alkoxy group (
For example, methoxy, ethoxy, dodecyloxy, methoxyethylcarbamoyl medoxy, methylsulfonylethoxy), aryloxy groups (e.g. phenoxy, 4-
Methylphenoxy, 4-methoxyphenoxy%4-t-
Butylphenoxy, 4-carboethoxyphenoxy%4
-cyanophenoxy, 2,4-dichlorophenoxy),
Acyloxy groups (e.g., acetoxy, tetrazocallyloxy), amide groups (e.g., dichloroacetamide, benzenesulfonylamide, trifluoroacetamide), imide groups (e.g., cohelic acid imide, phthalimide, 5,5-dimethyl-2 , 4-dioxoxazolidinyl, 1-benzyl-5-ethoxyhydantoinyl),
Nitrogen heterocyclic groups (e.g. pyrazole, 4-chloropyrazole, 3.5-dimethyl-1゜2.4-triazol-2-yl, imidazole, 3-chloro-1,2,4-
triazol-2-yl), alkylthio groups (e.g.
Ethylthio, dodecylthio, 1-ethoxycarbonyldodecylthio, 3-phenoxypropylthio, 2-(2,
4-di-tert-amylphenoxy)ethoxy), arylthio groups (e.g. phenylthio, 2-butoxy-
5-tert-octylphenylthio, 4-dodecyloxyphenylthio, 2-(2-ethoxyethoxy)-5
-tert-octylphenylthio, 3-pentadecyl phenylthio, 3-octyloxyphenylthio%3-
(N,N-didodecylcarbamoyl)phenylthio, 2
-cutyloxo-5-chloro-7enylthio), peterocyclic thio group (e.g. l-phenyltetrazole-5-
thio, l-ethyltetrazole-5-thio, l-dodecyl-1,2,4-triazole-5-thio).

Among these leaving groups, preferred are a hydrogen atom, an arylthio group, an alkylthio group, and a group that leaves at a nitrogen heteroprime, and particularly preferred are an arylthio group and a nitrogen heterocyclic group.

Among the magenta couplers represented by the general formula (V), particularly preferred couplers are the following general formula % formula % General formula (vA) In the general formula (vA), Ml is a linear chain having 5 to 29% carbon atoms, preferably 7 to 23 carbon atoms. or branched or cyclic alkyl groups (e.g. heptyl, nonyl, undecyl, tridecyl,
heptadecyl, 2-ethylhexyl, 2-hexyldodecyl, 4-hexylcyclohexyl, 3-pentadecylcyclohexyl, norbornyl, 7.7-dialkylnorbornyl, etc.).

Ml represents an alkoxy group having 1 to 18 carbon atoms or a halogen atom (eg, fluorine, chlorine, bromine), preferably a halogen atom.

M3 is a halogen atom (e.g. fluorine, chlorine, bromine),
An alkyl group or an alkoxy group, M4 and M5 may be the same or different, and each is a hydrogen atom, a herogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aralkoxycarbonyl group, a carboxy group, It represents a cyano group, a nitro group or an acylamino group, preferably a halogen atom.

The substituents in general formula (VI) will be explained. R14 represents a hydrogen atom and a substituent. To explain R14 in detail, R14 represents a hydrogen atom, an aliphatic group (e.g., straight chain aliphatic, aralkyl, alkynyl, cycloalkyl, cycloalkenyl), an aryl group (e.g., phenyl, naphthyl), heterocyclic groups (e.g. 2-furyl, -2-thienyl, 2-, rimidinyl, 2-benzothiazoyl), which are further substituted with the optional substituents mentioned in R5. Examples of aliphatic groups include methyl, propyl, t-butyl, trifluoromethyl, tridecyl, and 2-methanesulfonylethyl.

3-(3-pentadecylphenoxyl)propyl, 3-
(4-(2-[4-(4-hydroxyphenylsulfonyl)phenoxy]dodecanamido)phenyl)propyl, 2-ethoxytridecyl, cyclopentyl, 3-
(2,4-di-t-amylphenoxy)propyl, and examples of the aryl group include phenyl, 4-t-
Butylphenyl, 2,4-di-t-amylphenyl, 4
-tetradecanamidophenyl, and examples of the heterocyclic group include 2-furyl, 2-thienyl, 2-pyrimidyl, and 2-benzothiazoyl.

R14 can also be a cyano group, an alkoxy group (e.g. methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy), an aryloxy group (e.g. phenoxy,
2-methylphenoxy, 4-t-butylphenoxy),
Acylamino groups (e.g. acetamide, benzamide,
Tetradecanamide, α-(2,4-di-t-amylphenoxy)butyramide, δ-(3-t-butyl-4-
hydroxyphenoxy)butyramide, α-[4-(4
-hydroxyphenylsulfonyl)phenoxy]decanamide)% anilino groups (e.g. phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanamideanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino) -Chloro-5-[α-
(3-t-butyl-4-hydroxyphenoxy)dodecanamido]anilino), ureido groups (e.g. phenylureido, methylureido, N,N-dibutylureido)
, sulfamoylamino groups (e.g. N,N-dipropylsulf-1moylamino, N-methyl-N-decylsulfamoylamino)% alkylthio groups (e.g. methylthio, -octylthio, tetradecylthio, 2-phenoxyethylthio%) 3-phenoxypropylthio, 3-(
4-t-butylphenoxy)propylthio), arylthio groups (e.g. phenylthio, 2-butoxy-5-t-
octylphenylthio% 3-pentadecylphenylthio, 2-carboxylphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino group (
methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide groups (e.g. methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-butylbenzenesulfonamide) , carbamoyl group (e.g. N-
Ethylcarbamoyl, N,N-dibutylcarbamoyl,
N-(2-dodecyloxyethyl)carbamoyl%N-
Methyl-N-dodecylcarbamoyl, N-(3-(2
, 4-di-t-amylphenoxy)propyl)carbamoyl), sulfamoyl group (N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl, N-ethyl-N −
dodecylsulfamoyl, N,N-diethylsulfamoyl), sulfonyl group (methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl)
, alkoxycarbonyl groups (methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), heterocyclic oxy groups (e.g. l-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), acyloxy groups (e.g. acetoxy ), carbamoyloxy groups (e.g. N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy groups (e.g. trimethylsilyloxy,
dibutylmethylsilyloxy), aryloxycarbonylamino groups (e.g. phenoxycarbonylamino),
imide groups (e.g. N-succinimide, N-7talimide, 3-octadecylsuccinimide), peterocyclic thio groups (e.g. benzothiazolylthio, 2,4-diphenoxy-1,3,5'-triazole-6-thio, 2-pyridyl), sulfinyl groups (e.g. dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl groups (e.g. phenoxyphosphonyl, octyloxyphosphonyl,
phenylphosphonyl), aryloxycarbonyl group (
For example, phenoxycarbonyl), and acyl groups (for example, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl).

Among these groups represented by R14, preferable groups include aliphatic groups, alkoxy groups, aryloxy groups, alkoxycarbonylamino groups, and carbamoylamino groups, and more preferable groups include aliphatic groups, alkoxy groups,
It is an aryloxy group.

Y4 in general formula 1) each represents a hydrogen atom or a coupling-off group, and examples thereof are the same as those for Y3 in general formula (V).

Among these leaving groups, preferred are those that leave at a halogen atom 3 or a mercapto group, and particularly preferred are a fluoro group, a chloro group, a bromo group, and an arylthio group.

Za and Zb in general formula (VI) are methine, substituted methine-N
Among the magenta couplers of general formula (VI) representing = or -NH- group, particularly preferred couplers are represented by the following general formula (
VIA) to (■,).

General formula (VIA) General formula (vX8
) General formula (■,) General formula (■,) Among these, particularly preferred couplers are (VIB)S and (V
IC), in the general formula (VIA), N1 and N2 may be the same or different, and the general formula (VI'
) to (VIC), N1S and N2 are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group,
Heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imido group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group group, alkoxycarbonylamino group, aryloxycarbonylamino group,
Represents a sulfonamide group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group, and aryloxycarbonyl group.

FL14, N1, N2 or Y4 may be a divalent group to form a bis body.

For more details, RN and N2 are each 14'
1 Hydrogen atom, halogen atom (e.g. chlorine atom, bromine atom), alkyl group (e.g. methyl, propyl, t-butyl, trifluoromethyl, tridecyl, 3-(2,4
-di-t-amylphenoxy)propyl, allyl, 2-
Dodecyloxyethyl.

3-phenoxypropyl, 2-hexylsulfonyl-ethyl, cyclopentyl, benzyl), aryl groups (e.g. phenyl, 4-t-butylphenyl, 2,4-di-t
-amylphenyl, 4-tetradecanamidophenyl)
, heterocyclic groups (e.g., 2-furyl, 2-thienyl, 2
-pyrimidinyl, 2-benzothiazolyl), cyano group,
Alkoxy groups (e.g. methoxy, ethoxy, 2-methoxyethoxy, 2-dodecyloxyethoxy, 2-methanesulfonylethoxy), aryloxy (e.g. phenoxy, 2-methylphenoxy, 4-t-butylphenoxy), peterocyclic oxy groups (e.g. 2-benzimidazolyloxy), acyloxy groups (e.g. acetoxy, hexadecanoyloxy), carbamoyloxy groups (e.g. N-phenylcarbamoyloxy, N-ethylcarbamoyloxy), silyloxy groups (e.g. trimethylsilyloxy) ), sulfonyloxy groups (e.g. dodecylsulfonyloxy), acylamino groups (e.g. acetamide, benzamide, tetradecanamide, α-(2,4-di-t-amylphenoxy)butylamide% r-(3-t-butyl- 4-hydroxyphenoxy)butyramide, α-(4-(4-hydroxyphenylsulfonyl)phenoxy)decaneamide), anilino group (e.g. phenylamino, 2-chloroanilino,
2-chloro-5-tetradecanamide anilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5-(α-(3-t-butyl-4-hydroxyphenoxy) dodecanamido)anilino), ureido groups (e.g., puenylureido, methylureido, N,N-dibutylureido), imido groups (e.g., N-succinimide, 3-benzylhydantoynyl, 4-(2-ethylhexanoylamino) tutarimide), sulfamoylamino group (e.g., N, N-
dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), alkylthio groups (e.g. methylthio).

Octylthio, tetradecylthio, 2-)Futsukidiethylthio, 3-phenoxypropylthio.

3-(4-t-butylphenoxy)propylthio),
Arylthio groups (e.g. phenylthio, 2-butoxy-5-t-octylphenylthio).

3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), heterocyclic thio groups (e.g., 2-benzothiazolylthio), alkoxycarbonylamino groups (e.g., methoxycarbonylamino, tetradecyl oxycarbonylamino),
Aryloxycarbonylamino groups (e.g., phenoxycarbonylamino%2,4-di-tert-butylphenoxycarbonylamino), sulfonamide groups (e.g., methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecane sulfonamide, 2-methyloxy-5-t-butylbenzenesulfonamide), carbamoyl groups (e.g., N-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl, N-methyl- N-dodecylcarbamoyl% N-(3-(2,4-di-tert-amylphenoxy)propyl)carbamoyl), acyl group (e.g.
acetyl, (2゜4-di-tert-amylphenoxy)acetyl, benzoyl), sulfamoyl group (e.g., N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl,
N,N-diethylsulfamoyl), sulfonyl groups (e.g. methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), sulfinyl groups (e.g. octanesulfinyl, dodecylsulfinyl, phenylsulfinyl), alkoxycarbonyl (
For example, methoxycarbonyl, butyloxycarbonyl, dodecylcarbonyl, octadecylcarbonyl), aryloxycarbonyl group (eg, phenyloxycarbonyl, 3-pentadecyloxycarbonyl).

Among these groups represented by N1 and N2, particularly preferred are an alkyl group and an aryl group.

In general formula (VIE), the substituent of the phenyl group of the N-phenylcarbamoyl group Q can be arbitrarily selected from the group of substituents permissible for R5, and there are two or more substituents. The times may be the same or different.

Preferred examples of Q include the following general formula (■A).

General formula (■A) (In the formula, G4 represents a halogen atom or an alkoxy group, and G represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent.

G6 represents an alkyl group that may have a substituent,
) Substituents for G5 and G6 in general formula (■) include, for example, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, amino groups, dialkylamino groups, heterocyclic groups (e.g. N-morpholino, N-piperidino, Typical examples thereof include 2-furyl), a halogen atom, a nitro group, a hydroxy group, a carboxyl group, a sulfo group, and an alkoxycarbonyl group.

Preferred leaving groups Y include groups represented by the following general formulas (WB) to (■H).

General formula (■8) 0G.

G7 represents an optionally substituted aryl group or heterocyclic group.

General formula (■,) General formula (W,) G8, G
g is a hydrogen atom, a herogen atom, a carboxylic ester, an amino group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group,
Carboxylic acid group, sulfonic acid group, unsubstituted or substituted,
It represents a phenyl group or a heterocycle, and these groups may be the same or different.

General formula (■E) w2t“′”ho. YNYO°J1ce4j[,5
Represents a nonmetallic atom required to form a 116 or 6jiIl ring.

Among the general formula (■), (■ρ to (■H)) are preferably mentioned.

General formula (VIIF) General formula (■,) General formula (■)l) In the formula, Glo and G11 each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or a hydroxy group, and G12. , GlB and GHI+ each represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or an acyl group, and W3 represents an oxygen or sulfur atom.

The coupler, which has the function of chemically bonding with the aromatic primary amine color developing agent of the present invention to make it inactive, chemically reacts with the aromatic primary amine color developing agent to make it inactive. A typical method for this is substitution reaction, which is carried out when m=1. Taking the case where n=o as an example, in reaction formula (1), and m=0, n=1
Taking the case as an example, it can be expressed by reaction formula (2), but it is not limited to this.

Reaction formula (1) Reaction formula (2) The general formula for examination is shown.

Among the couplers represented by the general formula (1), which have the function of chemically bonding with the aromatic primary amine color developing agent to inactivate the developing agent, preferred ones are those disclosed in Japanese Patent Application No. 1982-18
2 (80°C) is 1.0-1.0xl in the second-order reaction rate constant with p-anisidine measured by the method described in No. 3919.
A coupler having a value in the range of O-'11 molar seconds is more preferable, and in general, if 2 is too large, the coupler itself becomes unstable and will react with gelatin or water and decompose.On the other hand, if 2 is too small, , unable to perform its functions to its fullest.

Measurement of the second-order reaction rate constant 2 can be performed as follows.

P-7 Nisidine and the coupler of the present invention are dissolved in phosphoric acid trinonyl ester so that each concentration is 0.03 mol/L. Next, 10 ml of this mixed solution is heated in a constant temperature bath at 80°C to induce a reaction. Tracked using high performance liquid chromatography,
Obtain the second-order reaction rate constant.

Representative examples of the group represented by (→A-iR1) in general formula (n) are shown below, but the invention is not limited thereto.

/'' /゛(Any 1) (Any 2) (Any 3) (Any 4) (Any 5) (Any 6) (Any 7+ (Any 8) (Any 9) (Any 10) (I Any 11) 10 〇〇3H7(n' (Any12) (Any13) (Any14) -COC18H37(n1 (Any15) rO (Any16) (Any17) (XI-18) (Any20) -COCBH17(n' ( Any 21) (Any 22) (Any 23) (Any 24) (Any 25) -coc5H11'n+ (Any 26) -cc4H9(t) (Any 27) (Any 28) C Any 29) ○ (Any 301 -5OC4H9 Representative examples of %R4 of the group represented by (-+A+TR4) in general formula (n) are shown below, but the present invention is not limited thereto.

(Any32) (Any34) (Any35) (Any36) (Any37) (Any38) (I knee 39) (Any41) CR3 (Any42) (Eng. 1-43) (Any44) (Engineering X-46) (Any47) (II-48) (I knee 49) (Any50) (Any51) (Any53) n.

``121-n 3 (Any54) (Any56) (Xnie57) is C:L (Any58) (Any59) (Any61) (Any621 (Iero3) (Any64) (Any65) (Any 66) (Any 67) (Any 68) (Any 69) (Any 70) 10C exemption (Any 72) (Any 73) (Any 74) (Any 75) 〇- (Any 76) 〇- (I Ni771 (Any78) (Any791 (Any80) (Any81) (Any82) (Any83) C Yu (Any84) (Iny85) (Any86) (Any87) (Any88) (Any 89) (Eng 1-90) (Eny 91) 〇- C standing (Eny 92) 〇- (Eny 93) 〇- (Eny 94) 〇- (Eny 95) (Eng 1-96) (Eny 97) ○- (Eng. 1-98) (Any99) 〇- 02CH3 (Any100) 〇- (Any101) 〇- 5O3H-N(C2H5)3 (Any102) (Any103) (Any104) (Any105) ■ M3 C Any 106) (Any 107) (Any 109) (Any 112) (Any 113) (Any 114) (I Any 115) (Any 116) (Any 118) (Any 119) Below, in the general formula (IF) ( Representative examples of R4 in the group represented by +A+T-R4) are shown below, but the invention is not limited thereto.

(Any121) -cQ.

(Any 122) Br (Any 123) Ikko (Any 124) (Any 125) -O502CH3 (II-126) (Eng. 1-127) Specific examples of couplers represented by the general formula (l) are shown below. It is not limited by.

(I[-1) (III-2) Jl (I[[-3) Su (I-9) I (I-10) (II-11) H (II-13) (wt ratio) (I-u ) x/)'/z=55/4015 (1[-16) (I[-17) (IN-18) I (i[-20) or (I-21) I (I-22) (]! l-23) (In-24) (1[-25) H Specific examples of the coupler represented by the general formula (IV) are shown below, but the invention is not limited thereto.

(ff-1) Su (ff-2) (■-3) (ff-4) (III-5) (IV-6) (■-7a) (N-7b) (■-8) (IV-9 ) (IV-10) (ff-11) (N-t2) (IV-13) (ff-14) (IV-15) k (If-16) 0 sweet (IV-17) Cwt ratio) (IV- 18) (wt ratio) (IV-19) (IV-20) <wt ratio) (IV-21) (III-22) (N-z4) (IV-25) (IV-26) (IV-27 ) (mV-28) (IV-29) H (■-3t) (IV-32) (ff-33) (■-34) (N-35m) (IV-35b) H3 (IV-36) (IV -38) (IV-40) (■-n) (nl(,,H3,s8beSC+gHx3'(IV-4
2) (IV-43) (wt ratio) (fV-4s) CN-46) (ill-47) Specific examples of the coupler represented by general formula (V) are shown below, but are not limited by these. do not have.

(V-1) C base (v-4) CI (V-5) (V-7) a (V-8) (V-10) (wt ratio) (V-11> (V-13) (V -15) (V-17) Ct (V-20) I (V-21) (V-22) Su (V-23) (wt ratio) Below are specific examples of couplers represented by general formula (VI). However, it is not limited to these.

(Vl-1) vinegar (W-2) CH.

(W-4) (W-8) (W-10) (W-11) (■-12) (W-ts) (W-x+) (M-15) (11-ts) (W-18) (wt ratio) (W-20) (wt ratio) (M-21) (F23) (■-25) (W-27) C control (W-28) CVI-31) (■-33) (Vl- 34) (Vl-35) (VI-37) (wt ratio) (■-38) (wt ratio) (Vl-39) x/ )'= 50150 (wt ratio) Below is the general formula (
Specific examples of the coupler represented by 2) are shown below, but the invention is not limited thereto.

(■-1) (■-2) (■-3) (h3 (ti-4) (■-5) I+rL3 (■-7) (■-8) (■-9) (■-10) (■-11) (■-12) (■-13) (■-14) (■-15) (■-16) (■-17) (■-18) (■-19) h (■-20) (■-21) (■-22) (■-23) (■-24) (■-25) (■-26) (■-27) (IN-28) (■-29) (■-30) (■-31) (■-32) (■-33) (■-34) (■-35) (■-36) (tI-37) (■-38) 1-1'13 (Xl-39) Ko 0-L) (■-42) (■-43) Synthesis examples of typical compounds of the present invention are shown below.

Synthesis example 1. (Synthesis of Exemplified Compound VI-3) A
BCD E
G Synthesis of 4-t-octylphenyl hexadecanoate (F) 4-t-octylphenol (E) 20g (0,099
Add 200 id of acetonitrile and 17 d of triethylamine (0.12 mol) to the mixture and dissolve.

Stirred at 0°C. To this, chlor hexadecanoate 32,
6 g (0,119 mol) were added dropwise. 11 at 25℃
After stirring for an hour, the acetonitrile was distilled off.

Ethyl acetate and water were added to the residue to separate the layers. The ethyl acetate layer was washed once with saturated brine and dried over Glauber's salt. After filtering out Glauber's salt, ethyl acetate was distilled off, and the residue was purified by column chromatography. White crystals, yield 44 g, yield 100% Synthesis of 2-hexadecanoyloxy-4-t-octyl-benzenesulfonic acid chloride (G) Hexadecanoic acid 4
-t-cutylphenyl (F) (0,090-11
z) 2 ooml of methylene dichloride was added and dissolved, and the mixture was stirred at 0°C. To this, chlorsulfonic acid 6 + 58Tnl
! (0.99 mol) was added dropwise. After stirring at 25°C for 7 hours, methylene chloride was distilled off, and 120ml of dimethylacetamide and 120ml of acetonitrile were added to the residue and dissolved at 25°C. 27.6ml of phosphorus oxychloride (0
, 30 mol) was added dropwise. After stirring for 3 hours, the mixture was poured into ice water, extracted twice with chloroform, and the chloroform layer was washed once with saturated brine and dried over Glauber's salt. Glauber's salt was purified by column chromatography after distilling off chloroform. Oily substance.

Yield 30.2g, yield 61.8% Synthesis of C Mixture of A and phthalhydrazide (content of A 54%) 25
0 g (A: 0.63 mol) in dimethylacetamide 50
Add 0ml and dissolve, and at 6℃ 8280g (0,79
Triethylamine 88d (0,6 mol) was added dropwise to the
3 mol) was added dropwise. After stirring at 10°C for 30 minutes,
750 d of ethyl acetate, 750 ml of water, and 50 ml of concentrated hydrochloric acid were added, and insoluble matter was filtered off, and the mixture was separated into one liquid. Add 200ml of hexane to ethyl acetate, wash 4 times with 5% saturated saline,
Hexane and ethyl acetate were distilled off. This was crystallized from ethyl acetate-hexane. Light brown crystals, yield 261g,
Yield 78, 4% Synthesis of reduced iron χ, 8 g (0,14 mol), ammonium chloride 0,75 (0,014 mol), acetic acid o, 5 oy
n! ! (0,0142 mol), 39 d of water, and 195 ml of isopropanol was heated under reflux and stirred for 30 minutes, then 5 g (0,028 mol) of CI was added, and a further 4 ml of isopropanol was added.
The mixture was heated under reflux for 5 minutes. After filtering this using Celite as a filter aid and washing the filtrate with isopropanol,
The filtrate and washing liquid were combined, isopropanol was distilled off, and the mixture was recrystallized from acetonitrile-ethyl acetate. Wl brown crystals, yield 11.7 g, yield 84.5% Synthesis of Exemplary Compound Vl-3 11, Og (0,022 mol), 55 ml of tetrahydrofuran, 33 ml of dimethylacetamide, 2.0 ml of pyridine! ? (0,024 mol) was added, dissolved, and
13 g (0,024 mol) of G was added dropwise at ℃, and 2
After stirring at 5°C for 18 hours, tetrahydrofuran was distilled off, ethyl acetate was added, the mixture was washed 22 times with saturated brine, and dried over Glauber's salt. Glauber's salt was filtered off, ethyl acetate was distilled off, and the product was purified using column chromatography. Light yellow solid, yield 18.
0g, yield 81.1% Synthesis Example 20 Synthesis of Exemplified Compound W-6 HI J K3
．． Synthesis of 5-dichloro-4-hydroxybenzoic acid (I) 3. Ethyl 5-dichloro-4-hydroxybenzoate (H
) (manufactured by Tokyo Kasei Kogyo ■) 25 g (0.11 mol)
360 g of methanol and 36 g of potassium hydroxide (0,6
4 mol) was added and dissolved, and the mixture was heated under reflux and stirred for 6 hours, and then added to ice water and 12N hydrochloric acid solution for neutralization, and the crystals were filtered.

This was recrystallized from methanol. Colorless crystals, yield 13
．． 2g, yield 59, 7% Synthesis of 4-carboxyl-2,6-dichlorophenyl carbonic acid hexadecyl ester (J,) 3.5-dichloro-4
-Hydroxybenzoic acid (I”) 19 g (0,09
27 mg (0.19 mol) of triethylamine and 190 ml of tetrahydrofuran were added and dissolved, and this was added dropwise to 63 d (0.19 mol) of hexadecyl chloroformate dissolved in 320 ml of tetrahydrofuran and heated to 0°C. After stirring at 25°C for 1 hour, 170ml of water was added, and the mixture was further stirred at 25°C for 3 hours. Thereafter, ethyl acetate and water were added to separate the layers, and the ethyl acetate layer was washed once with saturated brine and dried over sodium sulfate. Glauber's salt was filtered out, ethyl acetate was distilled off, the residue was purified by column chromatography, and further recrystallized from methanol. Colorless crystals, yield 31.2 g, yield 7
1.3% Synthesis of Exemplified Compound Vl-6 4-Carboxyl-2,6-dichlorophenyl carbonate hexadecyl ester (J) 8.4 g (0,018 mol)
1.5 d (0,021 mol) of thionyl chloride and 42 ml of benzene were added and dissolved, and after heating and stirring under reflux for 1 hour,
Benzene was distilled off. D8.0g (0,016
40 ml of tetrahydrofuran, 1 mol of pyridine,
47r1ii (0,018 mol) was added dropwise to the dissolved solution while stirring at 0°C, and the mixture was stirred at 25°C for 24 hours.

Tetrahydrofuran was distilled off, and ethyl acetate was added to the residue, which was washed twice with saturated brine and dried over Glauber's salt. Glauber's salt was filtered off, ethyl acetate was distilled off, and 0g yellow solid was purified using column chromatography, yield 8-26g, yield 49.2%. The coupler represented by the general formula (1) used in the present invention is as follows: Although it is preferable to add it to a silver halide photographic light-sensitive layer, it can be added to a non-light-sensitive photographic layer depending on the purpose.

Silver halide color photographic light-sensitive materials to be used in the present invention include color papers, color reversal vapors, color negative films, color positive films, etc., and it is particularly preferred to use color vapors and color reversal papers.

The magenta coupler of the present invention and the combination couplers described below can be introduced into the light-sensitive material by various known dispersion methods, such as solid dispersion method, alkaline dispersion method, preferably latex dispersion method, and more preferably oil-in-water dispersion method. This can be cited as an example. In the oil-in-water dispersion method, the boiling point is 17
After dissolving either a high-temperature organic solvent of 5°C or higher and a low-boiling point so-called auxiliary solvent, either alone or in a mixture of both, finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. do. Examples of high point organic solvents include U.S. Patent No. 2,322,027, representative examples are described in later sections.
Further, if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

Specific examples of high S point organic solvents include phthalate esters (e.g. dibutyl phthalate, di-37-dimethyloctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, dodecyl phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2
-ethylhexyl phenylphosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecanamide, N-tetradecylpyrrolitone, etc.) ), alcohols or phenols (isostearyl alcohol, 2,
4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), anilines (N,N-dibutyl-2-butoxy- 5-tart-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene,
diisopropylnaphthalene, etc.), and as the auxiliary solvent, organic solvents having a temperature of about 30°C to about 160°C can be used, typical examples being ethyl acetate,
Butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone-2-ethoxyethyl acetate,
Examples include dimethylformamide.

Specific examples of latex dispersion process steps, effects, and latex for impregnation are disclosed in U.S. Pat. No. 4,199.363, West German Patent Application No.
, No. 230, etc.

The couplers of the invention are preferably added within the light-sensitive silver halide emulsion layer. The addition amount range is 1 of silver halide.
0.002 to 0.5 mol per mole can be used, preferably 0.01 to 0.5 mol is added.

The coupler in the present invention is the blue-sensitive layer of the photosensitive material, green!
! It may be used for all layers, the red-sensing layer, or it may be used for any 2M of the three layers, preferably for only one of the three layers, and especially for the green-sensing layer. It is particularly preferable to use it in terms of the effects of the present invention.

Further, the coupler in the present invention may be used in combination with a yellow coupler, a magenta coupler, or a cyan coupler, and in this case, the proportion of the coupler of the present invention may be arbitrary, and preferably 5 to 400% of the coupler used in combination. mol%, more preferably 10 to 50 mol%
added.

The coupler used in combination with the coupler in the present invention may have an amount of 4 equivalents or 2 equivalents relative to silver ions.

Couplers that are preferably used in combination with the couplers in the present invention are shown below.

As a phenolic cyan coupler, US patents 2 and 3
No. 69,929, No. 4,518,687, No. 4,51
There are products (including polymer couplers) that have an acylamino group at the 2-position of the phenol nucleus and an alkyl group at the 5-position, as described in No. 1,674 and No. 3,772,002, etc., and representative specific examples thereof. As for Canadian Patent 625,8
Coupler of Example 2 described in US Pat. No. 3,7
Compound (1) described in No. 72.002, No. 4°564.
Compounds (I-4) and (I-5) described in No. 590, compounds (1) and (2) described in JP-A-61-39045,
(3) and (24), as well as the compound (C-2) described in No. 62-70846.

Phenolic cyan couplers include U.S. Pat. No. 2,772,162, U.S. Pat.
, 334,011, 4,500,635, and JP-A-59-164555, representative examples include U.S. Pat. , No. 826 (
V), the compound (17) described in No. 4,557,999
, compound (2) and (1) described in No. 4,565,777.
2), the compound (4) described in No. 4,124,396,
Compound (I-19) described in No. 4,613,564 and the like can be mentioned. Phenolic cyan couplers include U.S. Pat.
No. 564.586, No. 4,430,423, Japanese Unexamined Patent Publication No. 6
1-390441 and Japanese Patent Application No. 61-100222, in which a nitrogen-containing heterocycle is condensed with a phenol nucleus, typical examples include U.S. Pat.
Coupler (1) and (3) described in , No. 173, No. 4, 5
Compounds (3) and (16) described in No. 64,586, No. 4
Examples include compounds (1) and (3) described in No. 430゜423, and the following compounds.

Other examples of phenolic cyan couplers include U.S. Pat. No. 4,333,999, U.S. Pat.
, 444,872, 4,427.767, 4,
No. 579,813, European Patent (EP) 067.689B
There are ureido couplers described in U.S. Pat. ), the coupler (14) described in 4,444,872, the coupler (3) described in 4,427,767, the couplers (6) and (24) described in 4,609°619 , 4.579,813, couplers (1) and (11), European Patent (EP) 067.6
In addition to the coupler (45) and (SO) described in No. 89B1, the coupler (3) described in JP-A-61-42658,
The couplers shown below can be mentioned (C-54) (C-55) (C-56) As the magenta coupler, it is preferable to use couplers represented by the following general formula (VIA) and general formula (IX) in combination.

General Formula (■) General Formula (■) In the formula, R18 represents a substituted or unsubstituted phenyl group, and R16 has the same meaning as an acyl group or R18. R1
7 represents a hydrogen atom, an aliphatic or aromatic acyl group, or an aliphatic or aromatic sulfonyl group.

R19 represents a hydrogen atom or a substituent, Zc and Z
d represents methine, substituted methine, -N- or -NH-, Y and Y7 are hydrogen atoms or the above general formula (m
) to ('911[), where R, RR or Y6.16 17'''' 18 R, Zc, Zb or Y7 represents a dimer or more multimer It may be formed.

Preferred specific examples of couplers represented by general formula ([)g and general formula (II) are shown below, but the invention is not limited thereto.

(M-1) (IL (M-2) Su (M-6) (M-9) (M-13) (M-15) CaHrtC
IH17ftl Shil (M-19) Cwt ratio) (M-20) Shil (M-21) (M-22) (W Jin-nii) (M-23) (M-24) (wt ratio) General formula (■ ) and other exemplary compounds or synthetic methods of couplers represented by formula (EX) are listed below.

The magenta coupler represented by the general formula ([) was published in Japanese Patent Application Publication No. 4
No. 9-74027, No. 49-74028, Special Publication No. 1973
-27930, US Pat. No. 53-33846, and US Pat. No. 3,519,429.

The magenta coupler represented by the general formula (IK) is disclosed in JP-A-59-162548 and US Pat. No. 3,72, respectively.
No. 5,067, JP-A-59-171956, and U.S. Pat. No. 4,540,654.

JP-A-60-33552 and JP-A-62-2094
It is synthesized by the method described in No. 57, etc.

As the yellow coupler, it is preferable to use a coupler represented by the following general formula (X).

General formula (X) In the formula, Y8 represents a hydrogen atom or a leaving group, R represents a diffusion-resistant group having a total of 8 to 32 carbon atoms, R21 is a hydrogen atom, and one or more halogen atoms. , a lower alkyl group, a lower alkoxy group, or a diffusion-resistant group having a total of 8 to 32 carbon atoms.

For details on the coupler represented by general formula (X),
U.S. Patent No. 4,622,287, lines 3015 to 8a39 of the specification, and U.S. Pat.
It is described from line 4a50 to line 191i41.

Specific examples of couplers represented by general formula (X) include:
No. 37 of the aforementioned U.S. Pat. No. 4,622,287.
Compound examples (Y-1) to (Y-39) described in column ~54g
can be mentioned.

Among them, (Y-1), (Y-4), (Y-6) & (Y-
7), (Y-15), (Y-21).

(Y-22), (Y-23), (Y-26).

(Y-35), (Y-36), (Y-37).

(Y-38), (Y-39), etc. are preferred.

In addition, examples of the compounds (Y-1) to (Y-33) of column 19 to 24 of the above-mentioned U.S. Patent No. 4,623,616 can be mentioned, among which (Y-2), (Y-7),
(Y-8), (Y-12), (Y-20), (Y=21
), (Y-23), (Y-29), etc. are preferred.

Other preferred examples include U.S. Patent No. 3.408
, No. 194 specification, column 6 (34
), compound examples (16) and (19) described in No. 89 of Specification No. 3,933,501, and example compounds (9) described in columns 7 to 8 of Specification No. 4,046,575 , 4, 13
Examples of compounds described in Nos. 5 to 6a of Specification No. 3958 (1
), Compound Example 1 described in column 5 of Specification No. 4,401,752, and the following compounds a) to g).

A chemically inert and substantially colorless compound is chemically bonded with the aromatic amine color developer remaining after the color development process in Japanese Patent Application No. 158642/1982 into the sensitive material of the present invention. It is possible to use the resulting storage-improving compounds in combination.

A compound represented by the general formula (X[) is exemplified as a storage-improving compound which is preferable in terms of increasing the effect of the present invention, and whose combination is particularly preferable.

General formula (XI) In the formula, 1M is inorganic (for example, Li, Na, K.

Ca, Mg, etc.) or organic salts (eg triethylamine, methylamine, ammonia).

Here, R27 and R28 may be the same or different, and each represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group.
R2□, R30'R3□ and R33, which may form a membered ring, may be the same or different, and each represents a hydrogen atom,
It represents an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, a sulfonyl group, a ureido group, and a urethane group.

However, at least one of R2□ and R30 and at least one of R3□ and R33 are hydrogen atoms. R3 and R34 represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group; R3 further represents an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, and an aryl group; represents an oxycarbonyl group, where R2g, R3
o, R3□, at least two groups may be bonded to each other to form a 5-7 negative ring, and R3□, R33, R
At least two groups of 34 are bonded to each other to form 5-7
may form a membered ring, R35 is a hydrogen atom, an aliphatic group,
Represents an aromatic group or a heterocyclic group, and R36 is a hydrogen atom.

R37 represents an aliphatic group, aromatic group, halogen atom, acyloxy group or sulfonyl group, and represents a hydrogen atom or a hydrolyzable group.

R2□, R23, R24' R25 and R26 may be the same or different, and each represents a hydrogen atom, an aliphatic group (e.g. methyl group, isopropyl group, t-butyl group, vinyl group, benzyl group, octadecyl group, cyclohexyl group) ), aromatic groups (e.g. phenyl, pyridyl, naphthyl), heterocyclic groups (e.g. piperidyl, pyranyl, furanyl, chromanyl), halogen atoms (e.g. clodiyl), alkoxycarbonyl groups (e.g. methoxycarbonyl) group, butoxycarbonyl group, cyclohexylcarbonyl group, octyloxycarbonyl group),
Aryloxycarbonyl groups (eg, phenyloxycarbonyl, naphthyloxycarbonyl groups), sulfonyl groups (eg, methanesulfonyl groups, benzenesulfonyl groups), sulfonamide groups (eg, methanesulfonamide groups).

benzenesulfonamide group), sulfamoyl group, ureido group, urethane group, carbamoyl group, sulfo group, carboxyl group, nitro group, cyano group, alkoxy group (
For example, methoxyxalyl group, isobutoxyxalyl group, octyloxyxalyl group, penzoyloxyxalyl group).

represents an allylxalyl group (e.g. phenoxyxalyl group, naphthoxyxalyl group), a sulfonyloxy group (e.g. methanesulfonyloxy group, he-P(OR,8)3) and a formyl group, where "18 and R3□ are hydrogen Of these, representing an atom, an aliphatic group, an alkoxy group or an aromatic group.

-502M group, the sum of Hamset values is o, s
The above is preferable in terms of the effects of the present invention.

Preferred specific examples of the compound represented by general formula (U) are shown below.

(XI-1) (XI-2) (XI-3) (XI-4) (XI-s) (XI-7) (U-8) (X[-9) (N-11) (Summer-12) r (XI-13) (XI-15) (XI-18) (XI-19) (]-20) (X[-30) (XI-31) (Xi-32) (X[-34) (XI-38) (XI-39) (XI-40) (X[-41)　　　　　　　　　　　　　　.

(XI-42) (U-43) (X[-44) C0CH5(XI-4
5).

(XI-47) (XI-48) (Xi-49) (XI-50) (XI-s+) ltlcsHty (XI-53) (Xi-54) (X[-5s) (Summer-56) (Summer -57) (![-58) (XI-59) Synthesis methods of these compounds are described in Japanese Patent Application No. 60-295466, No. 61-23467, No. 61-36416, No. 6
It can be synthesized by the method described in No. 1-183919, No. 61-183920 or a method analogous thereto.

If the compound represented by the general formula (XI) has a low molecular weight or is easily dissolved in water, it may be added to the processing solution and incorporated into the photosensitive material during the development process, preferably at the stage of producing the photosensitive material. This is a method of adding it to a photosensitive material. The latter method is usually performed by dissolving a high boiling point solvent (oil) with a boiling point of 170°C or higher at atmospheric pressure alone, a low boiling point solvent alone, or a mixed solvent of the above oil and a low boiling point solvent, and then adding gelatin, etc. to this solution. It is prepared by emulsifying and dispersing it in an aqueous hydrophilic colloid solution. The compound represented by general formula (XI) is preferably dissolved in a high boiling point organic solvent. The particle size of the emulsified dispersion particles is not particularly limited, but is preferably o, 05=~o, 5jL, particularly 0. 1 Torr is preferably 0.3 JL. In particular, in terms of the effects of the present invention, it is preferable that the compound represented by the general formula (X[) is co-emulsified with the coupler. In this case, the oil/coupler ratio is 0.3 JL by weight. It is preferable that it is 00-2.0.

The proportion of the compound represented by formula (Xl) is 1X10-2 to 10 mol, preferably 3X10' to 5 mol, per mol of coupler.

Specific examples of the oil include phthalic acid alkyl esters (dibutyl phosphate, dioctyl phthalate, diisodecyl phthalate, dimethoxyethyl phthalate, etc.), phosphoric acid esters, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, etc. phate, dioctyl phosphate, monophenyl-p-t-butylphenyl phosphate),
Citric acid esters (eg acetyl tributyl citrate), benzoic acid esters (eg octyl benzoate), alkylamides (eg diethyl laurylamide, dibutyl laurylamide), fatty acid emethers iii<eg dibutoxyethyl succinate.

diethyl azelate), trimesate esters (e.g. tributyl trimesate), compounds containing epoxy rings (
Examples include compounds described in US Pat. No. 4,540,657), phenols (e.g. Examples of solvents include organic solvents having a boiling point of 30° C. to 150° C. at atmospheric pressure, such as lower alkyl acetates such as ethyl acetate, isopropyl acetate, butyl acetate, ethyl propionate, and methanol.

Ethanol, secondary butyl alcohol 9, cyclohexanol, fluorinated alcohol, methyl isobutyl ketone, β
-Ethoxyethyl acetate, methyl cellosolve acetate, acetone, methyl acetone, acetonitrile, dioxane, dimethyl formamide, dimethyl sulfoxide, chloroform, cyclohexane and the like.

In addition, instead of high boiling point organic solvents, not only oil-based solvents (including those that are solid at room temperature such as wax) for additives such as couplers, but also latex polymers can be used, or couplers, color mixing inhibitors, and ultraviolet rays can be used. For absorption, etc., the additive itself may also serve as an oily solvent.

Latex polymers include acrylic acid, methacrylic acid and their esters (e.g. methyl acrylate, ethyl acrylate, butyl methacrylate, etc.), acrylamide, methacrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate, etc.).
Acrylonitrile, styrene, divinylbenzene, vinyl alkyl ethers (e.g. vinyl ethyl ether),
Manufactured using 1,000 types of maleic acid esters (e.g. maleic acid methyl ester), N-vinyl-2-pyrrolidone, N-vinylpyridine, 2- and 4-vinylpyridine alone or in combination of two or more. Latex polymers are used.

Examples of surfactants used when dispersing a solution of the compound represented by general formula (XI) alone or together with a coupler in an aqueous protective colloid solution include saponin, alkyl sodium lefuosuccinate, and alkyl sodium lebenzene. Examples include sodium J lefonate.

The compound represented by the general formula (X[) can be used in combination with any of the yellow couplers, magenta couplers, or cyan couplers according to the present invention. Among these, it is particularly preferable to use it in combination with the magenta coupler of the present invention in terms of the effects of the present invention.

The coupler used in combination with the compound represented by the general formula (X The coupler used in the invention may be a single coupler according to the present invention, or a mixture of two or more types including at least one coupler according to the present invention.

The compound of the present invention may be used in combination with a known anti-fading agent, and particularly preferred anti-fading agents include (i) general formula (
An aromatic compound represented by X[[].

(1i) an amine compound represented by the general formula (Xlll); or (1ii) an organic ligand having a central metal of copper, cobalt, nickel, palladium, or platinum and having a bidentate or more conformation; It is a metal complex with

General formula (X[[) In the formula, R4o is a hydrogen atom, an alkyl group, an alkenyl group,
Aryl group, heterocyclic group, or R may be the same or different from each other and each represents an alkyl group, alkenyl group, aryl group, alkoxy group, alkenoxy group, or aryloxy group, R44, R4□'R43''
R44 and R45 may be the same or different from each other,
Each hydrogen atom, alkyl group, alkenyl group, aryl group, acylamino group, alkylamino group, alkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, halogen atom or 10-R
', where "40" represents a group represented by R4o, R4o and R41 may be combined with each other to form a 5-membered ring, a 6-membered ring, or a spiro ring, R and R or R4
□ and R43 may be bonded to each other to form a 5-membered ring, a 6-membered ring, or a spiro ring.

General 2〇! i) In the formula, R49 is a hydrogen atom, an alkyl group, an alkenyl group,
Representing an alkynyl group, acyl group, sulfonyl group, sulfinyl group, oxy radical group or hydroxyl group,
R, R, R and R53 may be the same or different and each represents a hydrogen atom or an alkyl group, and B represents a group of nonmetallic atoms necessary to form a 5-membered, 6-negative or 7-membered ring.

General formula (X[r), General formula (Xlll) (7) Among each group, the group containing even a partial alkyl, aryl or heterocycle may be further substituted with a substituent.

Representative examples of these specific compounds include the patent application 1986-
Compounds A-1 to A-60 described on pages 49 to 63 of Specification No. 233869 and other compounds listed below can be mentioned.

A-goko A-B People! A-Got A-6/ A-gori CH2=CH20C□4H29(n) The compound represented by the general formula (X[[), (M) is.

10 to 400 mol%, preferably 3 to coupler
It is added in an amount of 0 to 300 mol%. On the other hand, the metal complex is added in an amount of 1 to 100 mol%, preferably 3 to 40 mol%, based on the coupler.

The light-sensitive material produced using the present invention may contain a hydroquinone rust conductor, an aminophenol rust conductor, a gallic acid rust conductor, an ascorbic acid derivative, etc. as a color antifoggant.

As other dye image stabilizers, for example, JP-A-59-1
Catechol visiting conductors described in JP-A No. 25732 and JP-A-60-262159 can also be used.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the wood-philic colloid layer. ), 4-thiazolidone compounds (e.g. those described in U.S. Pat. No. 3,314,794 and U.S. Pat. No. 3,352.681), benzophenone compounds (e.g. those described in JP-A-46-2784), Cinnamate ester compounds (e.g. U.S. Pat. No. 3,
Nos. 705,805 and 3,707,375), butadiene compounds (e.g., U.S. Pat. No. 4,045,
229) or benzoxidole compounds (eg, those described in US Pat. No. 3,700,455). Ultraviolet absorbing couplers (for example, α-naphthol cyan dye-forming couplers), ultraviolet absorbing polymers, and the like may be used, and these ultraviolet absorbers may be mordanted in specific layers.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation.

Included are oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the gelatin production method can be found in The Macromolecular Chemistry of Gelatin, written by Arthur Vuis. Published by Academic Press, 1964).

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention.

The average grain size of silver halide grains in a photographic emulsion (the grain size is the grain diameter in the case of spherical or approximately spherical grains, and the ridge length in the case of cubic grains, expressed as an average based on the projected area) is particularly important. Although it does not matter, it is preferably 2 JL or less.

The grain size may be narrow or wide, but it is preferable to use a monodispersed emulsion with a variation rate of 15% or less.

The silver halide grains in the photographic emulsion layer may have a regular crystal structure such as a cube or hexagonal, or may have an irregular crystal structure such as a spherical shape or a plate shape, or may have an irregular crystal structure such as a spherical shape or a plate shape. It is preferable to use a normal crystal emulsion.

Further, an emulsion may be used in which tabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area.

The silver halide grains may have different phases inside and on the surface, and may be grains in which latent images are mainly formed on the surface, or grains in which latent images are mainly formed inside the grains.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a thallium salt, a lead salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

Silver halide emulsions are usually chemically sensitized.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles 1 such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole, etc.), mercaptopyrimidines, mercaptotriazines, etc.: thioketo compounds such as oxadorinthion; azaindanes, e.g. Triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1°3.3a, 7) tetraazaindene), pentaazaindene, etc.: benzenethiosulheptanoic acid.

Many compounds known as antifoggants or stabilizers can be added, such as benzenesulfinic acid, benzenesulfonamide, and the like.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as required. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The supports used in the present invention are usually cellulose nitrate films, cellulose acetate films, cellulose acetate butyrate films, cellulose acetate propionate films, polystyrene films, polyethylene terephthalate films, polycarbonate films, which are used in photographic materials. In addition, there are laminates of these materials, thin glass films, paper, etc. Baryta or α-olefin polymers, especially polyethylene,
Paper coated with or laminated with a polymer of α-olefin having 2 to 10 carbon atoms, such as polypropylene or ethylene butene copolymer, vinyl chloride resin containing a reflective material such as TiO□, as shown in Japanese Patent Publication No. 19068/1983 Supports such as plastic films whose surfaces are roughened to improve adhesion to other polymeric substances also give good results. Further, an ultraviolet curable resin can also be used.

These supports are selected to be transparent or opaque depending on the purpose of the photosensitive material. It is also possible to add dyes or pigments to make it colored and transparent.

Opaque supports include those that are inherently opaque, such as paper, and
Transparent film with pigments such as dyes and titanium oxide added, or plastic films surface-treated by the method shown in Japanese Patent Publication No. 447-/RIOTR, and carbon black, dyes, etc. It also includes light-shielding paper or plastic films. The support usually has a gold undercoat layer. In order to further improve the adhesion, the surface of the support may be subjected to preliminary treatment such as corona discharge, ultraviolet irradiation, flame treatment, etc.

To prevent fading, for example,
JP-A No. 1987-417177 describes a technique for surrounding a dye image with an enzyme-blocking layer made of a substance with low oxygen permeability, and JP-A No. 14-417177 describes a technology for enclosing a color image forming layer of a color photographic light-sensitive material. Oxygen permeability on the support side is 201117m2・hr
It is disclosed that a layer of -810 m or less is provided and is applicable to the present invention.

Other photographic additives used in car inventions are Research Disclosure Vol. 774% & 176 Hiro J (/ri7ri, July) and Vol. 117, Mu/17/bu (/p7
(November), and the relevant parts are summarized in the table below.

Additive type RD17643 RD18716
1 Chemical aggravating agents Page 23 Page 648 Right column 2 Sensitivity increasing agents
Same as above 3 Spectral sensitizers pages 23-24 Page 648 right column ~ 4 Superchromatic sensitizers Page 649 right side 5 Brighteners page 24 7 Coupler - page 25 8 Icubator solvent page 25 10 Ultraviolet absorber 12 Dye image stabilizer page 25 13 Hardener page 26 page 651 left column 1
4 Binder page 26 Same as above 15 Plasticizer, lubricant page 27 Page 650 right column (
Examples) Hereinafter, the present invention will be explained in detail based on examples.

(Example-1) Multilayer color copy with the layer structure shown below on a paper support laminated on both sides with polyethylene! A photosensitive phase material (A) was prepared.

The coating solution was prepared as follows.

19.1 g of FA yellow coupler (ExY) and 1.44 g of antifoggant (Cpd-2) were added to 27.2 c of ethyl acetate.
c and solvent (Soly-1) 7°5cc, ffl medium (
Add and dissolve 7.5 cc of Solv-2, and add 8 cc of 10% sodium dodecylbenzenesulfonate to this solution.
The mixture was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution. The following blue-sensitive sensitizing dye was added to the cubic silver halide emulsion 1) in an amount of 2.6×10'+ mol per mol of silver to give !I!l.

The above-mentioned emulsified dispersion and this emulsion were mixed with bacteria Wl 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 for the first layer.

The silver halide emulsion used is as shown below.

The gelatin hardening agent for each layer is l-oxy-3,5-
Dikukoro-5-) riazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer; (2.6X10 moles per mole of emulsion) Green-sensitive emulsion layer; (4.8X10-4 moles per mole of emulsion) (5.5X10 moles per mole of emulsion) for red-sensitive emulsion layer For example, the following compound should be added at 2.6X per mole of silver halide.
10-3 mol was added.

Further, for the hit-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added at 1.2×10 mol per mol of silver halide and 1. 1X10-'' moles were added.

In addition, for the red-sensitive emulsion layer, 2-amino-6-mercap)
-1,3,4-thiadiazole was added at 3.0 x 10 -10 moles per 81 moles of halogenation, and the following dye was used as an irradiation-preventing dye.

The composition of each layer is shown below, the numbers are coating amount (g/, x
), and the silver halide emulsion is expressed in silver equivalent coating amount) Support Paper support laminated on both sides with polyethylene [white #FI ('r 1O2) and bluish dye (on the polyethylene on the first layer side) 0.33 gelatin 1.2 yellow coupler (ExY) 0.53 second layer (color mixture prevention l
7A) Gelatin 0.83 Color mixture prevention agent (Cpd-2) 0.024? a medium (S
o 1v-1) 0.06 solvent (
So 1v-3) 0.06 Third layer (green sensitive layer) Silver halide emulsion (2) 0.17 Gelatin 1.12 Magenta coupler (ExM-1) 0.27 Color image stabilizer (C
r) d -3) O, O6 color image stabilizer (C
p d -4) 0, 08 Stain inhibitor' (Cpd-5) 0.15 Solvent (Solv)
3) 0.19 solvent (Sol v-4
) 0.08 Fourth layer (UV absorption PA) Gelatin 0.96 Ultraviolet absorber (tlV-1) 0.36 Color mixing prevention agent (
Cpd-2) 0.05 Solv-2
) 0.16 5th P! (Red-sensitive layer) Silver halide emulsion (3) 0.20 gelatin 0.82 cyan coupler (ExC-1) o, 15 cyan coupler (E
xC-2) O,lf1 color image stabilizer (C:Pd-
6) 0.14 antifoggant (Cpd-2)
0.01 solvent (SOIV-1)
0.22 6th F! (Ultraviolet absorption FT) Gelatin 0.96 Ultraviolet absorber (UV-1) 0.3G solvent (Solv
-2) 0.16 Seventh layer (protective layer) Gelatin 1.25 Acrylic of polyvinyl alcohol 0.05 Modified copolymer (degree of modification 17%) Liquid paraffin 0.02 (Ex
Y) Yellow coupler C- (ExM-1) Magenta coupler t (EXC-1) Cyan coupler (Ex C-2) Cyan coupler 6 (Cpd-1) Antifoggant (Cpd-2) Color mixing inhibitor (Cpd- 3) Color image stabilizer (Cpd-4) Color image stabilizer ゛ (Cpd-5) Anti-stinting agent C4Hi\/C4H9 (Cpd-6) Color image stabilizer 4:2:51 hardware (Usha ratio) ( UV-1) Ultraviolet absorber! 2:lo:3 mixture ((quantity ratio) (Solv-1) Solvent (Soly-2) Solvent (Solv-3) Solvent (Solv-4) Third layer of solvent multilayer color photographic feed (A) (green color Table 1 shows the magenta coupler of layer) and the compound of general formula (XI).
Samples Nos. 1 to 4 were prepared as shown in .

[Magenta coupler is equimolar! [L change] Using a sensitometer (Model FWH manufactured by Fuji Photo Film Co., Ltd., color section rt3200K of the light source), the above photosensitive material was subjected to gradation exposure for sensitometry through a three-color separation filter.

The exposure at this time was carried out at an exposure time of 0.1 seconds and an exposure amount of 2500M5.After ann, the following processing steps were carried out.

Treatment [temperature - compensation - time.

Color development m 3B℃ 3 minutes 30 seconds Bleach fixing 33℃ 1 minute 30 seconds Washing ■ 30
～34℃ Wash for 60 seconds ■ 30～34℃
Wash with water for 60 seconds■ 30-34℃ 60
Dry for 70-80℃ for 50 seconds (wash with water)
→■ A 3-tank countercurrent system was adopted. ) Color fJl solution A concentrated color developer composition was prepared by separating into parts as follows.

Part A Hydroxylamine sulfate 290g Lithium chloride 135 sr Add water
1000rnlpi (8,0 Bart B 4-amino-3-methyl-N-[β-(methanesulfonamide) ethylgoaniline sulfate 200g Fluorescent brightener (4,4-diaminostilbene series') 15g Benzyl alcohol 550 ml Diethylene glycol 300 rrt 1 Sodium northern sulfate 26g Add water
1000 ml pH 0,60 Part C Sodium Fftite 25 g Potassium carbonate 500 g 1-Hydroxyethylidene-1,1-diphosphonic acid 40 Toy caustic potash 100 g Add water
1000 m 11)8
12.0 Starter Potassium Bromide 55g Potassium Carbonate 42g Potassium Carbonate
Add 180g water
1000m100Oa, 5 Place the above Part A, Part B, Part C and ° starter in a plastic container; - After 3 months at 35°C, use the color F31 image solution as follows.
It was night.

Water 700 ml per)A
14m1 Part 8 28m1 Bar) C40n11 Starter 24m1 Add water 1000 tn 1 pH 10,10 Bleach, white fixing) α Water 400
．． ml ThioMM ammonium (70%) 200m
1 Sodium sulfite 20g Iron ethylenediaminetetraacetate (1■) Ammonium 60g Disodium ethylenediaminetetraacetate 5g Add water
l Q Q O1111p)i
'6.70 Each treated sample was left at 80° C. for one month, and the amount of increase in minimum density of yellow and magenta (ΔDBmin, ΔDGn+in) was measured using a Macbeth densitometer. In addition, the minimum yellow color after irradiation with 8500 Lux xenon light for 20 days
The amount of increase in temperature (ΔD8IIIin) was also determined at the same time. The results are shown in Table-2.

Table 2 It can be seen that according to the present invention, yellow stains caused by heat, magenta stains, and yellow stains caused by light are significantly improved.

(Practical Example-2) Using the same machine as Example-1, a multilayer color photographic material (B) having the layer structure shown below was produced.

(Layer structure) Support No.-F same as (A)! (Blue gFl) Silver halide emulsion (1) 0.26 gelatin 1.20 yellow coupler (ExY) 0.66 antifoggant (Cpd
-1) o, 02° solvent (Solv-1)
0.28 Second F' (color mixture prevention N) Gelatin 0.89 Color mixture prevention agent (Cpd-2) 0.03 Sonic solvent (Sol v-2) 0.07 Solvent (S'ol v-3) 0 .07 Third N (green sensitive layer) Silver halide emulsion (2) 0.33 Gelatin 1.11 Magenta coupler (EXM-2) 0.27 Color image stabilizer (Cpd-
7) 0.05 color image stabilizer (Cpd-8)
0.01 color image stabilizer (Cpd-4)
0.11 color image stabilizer (Cpd, -9)
0.08 Solvent (Sol v-3) 0
．． 21 Solvent (Solv-4) 0.17
Fourth F! (9 External ray absorption J! gelatin 1.44 Ultraviolet absorber (UV-1) 0.53 Color mixing prevention agent (C
pd-2) 0.05 Solvent (Sol v-
5) 0.26 fifth rA (red fk silver halide emulsion (3) 0.20 gelatin 0.82 cyan coupler (EXC-1) 0.15 cyan coupler (Ex
C-2) 0.19 antifoggant (Cpd-1)
0.01 color image stabilizer'(Cpd-6)'
0.14 solvent (So 1v-1)
0.22 Sixth layer ('#external ray absorption layer) Gelatin 0.48 Ultraviolet absorber (UV-1) 0.18 Solvent (So 1
v-5) 0.0≦3 7th layer (protective layer)
The same gelatin hardener, emulsion additive and anti-irradiation dye as in (A) are the same as in (A).

L! 1.0×10 −5 mol of 1-(5-methylureidophenyl)-5-mercaptotetrazole per mol of silver halide was added to the photosensitive emulsion layer.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer; Same as (A) (5.UXlo moles per mole of emulsion) (2.8810-+ moles per mole of emulsion) (6 moles per mole of emulsion)
．． (5X10 moles) red-sensitive emulsion layer; (1.1X10-4 moles per mole of emulsion) (ExM-
2) Magenta coupler (Cpd-8)' color image stabilizer (Cpd-9) color image stabilizer (Solv-6) solvent multilayer color copying/Ill photosensitive material N (B) third layer (green sensitivity ff) Samples Nos. 21 to 30 were prepared using magenta couplers and compounds of the general formula (X) as shown in Table 3. [The couplers were replaced with equimolar acids] The above photosensitive materials were prepared in the same manner as in Example 1. The samples were exposed to light and developed. Each of the processed samples was evaluated in the same manner as in Example 1 for the generation behavior of heat-induced staining and light-induced staining. The results are shown in Table 4.

It can be seen that the steering wheel has been significantly improved on the same aircraft as in Example-1.

(Example 3) A multilayer color photographic material (C) having an N configuration as shown below was produced.

(Layer structure) Support Same as (A) -N < blue-sensitive layer) Silver halide emulsion (1) 0.26 gelatin L, 2.0 yellow coupler (ExY) o, 66 color image stabilizer (Ct)
d-10) 0.07 antifoggant (Cpd-
1) 0.01 solvent (Solv-2)
o, 13 solvent (Solv-6)
0.13 second F! (Color mixture prevention layer) Gelatin 1.34 Color mixture prevention agent (Cr) d-2) 0.06 Solvent (Sol
v-1) 0.10 solvent (Solv-3
) 0.10 3rd rH! (Green Sensation M') Silver Halide Emulsion (2) 0.14 Gelatin 1.30 Magenta Coupler (EXM-3) 0.27 Color Image Stabilizer (Cpd-
4) 0.1 (3 solvent (Solv-3)
0.21 solvent (So'l v-4)
0.33 Fourth pA (UV absorption Pi) Gelatin 1.44 Ultraviolet absorber (tJV-1) 0.53 Color mixing inhibitor (Cpd-2) 0.04 Solvent (So 1v
-5) 0.26 Fifth layer (red G layer) Silver halide emulsion (3) 0.20 Gelatin 0.89 Cyan coupler (II, cc-3) 0. 13 cyan coupler (EzC-4) O, 16 color image stabilizer (Cpd-
10) 0.27 color image stabilizer (Cpd-(3)
0.07 Antifoggant (Cpd-1)
'0.01 solvent (Sol v-6)
0.143 Sixth layer (ultraviolet absorption layer) Gelatin 0.47 Ultraviolet absorber (UV-1) 0.17 Solvent (So
1v-5) 0. 0
8 Seventh layer (protection Fj) The same gelatin hardener and emulsion additive as in (A) are the same as in (B) 8.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer; same as (A) 10 (5. ; The following dyes were used as anti-irradiation dyes.

and (ExM-3) magenta coupler (EXC-3) cyan coupler (ExC-4) cyan coupler L (Cpd-10) color image stabilizer average molecular weight; 60,000 (Solv-6) fa medium multilayer color photographic sensitization Sample No. 31 was prepared by adding the magenta coupler in the third layer of material (C), the cyan coupler in the fifth layer, and the compound of general formula (XI) as shown in Table 5.
~37 were produced.

[The coupler change was an equimolar replacement, and trial F! I
Cyan coupler at No. 36 and 37 is l:1
(molar ratio). ] Next, Par) B of the concentrated color developer composition used in Example-1 was changed as follows to prepare an H bath solution.

Part Bl tank liquid No.

4-7 Minnow 3-Mekoto N- [β -20020020
0 (Metathistle Honshi7miF)ethyl n]-1 dilysulfate (g) Fluorescent brightener Cg> 15 15 1
5 Benzyl alcohol (ml) 550 550 55
0 diethylene glycol (1) 300 300 300
Sodium sulfite <g> 26 26 3
9 The above 5Tla liquid composition was prepared in the same manner as in Example-1.
After 3 months at 5°C, a color developer was prepared in the same manner as in Example-1, and after processing the multilayer color photosensitive material (C) and samples Nos. 31 to 37, at 80°C for 1 month. The amount of increase in the minimum density of magenta and cyan (ΔDGm
in, ΔDRmin) and the increase in minimum yellow density ff1 (ΔD Bmin) 20 days after xenon light irradiation. The results are shown in Table-6.

Table 6 According to the present invention, the occurrence of staining over time is significantly improved, and in particular, the pH value of Bad B is within the preferable range.
The improvement effect in Nos. 2 and 3 was large, and No. 3, which had a high degree of sulfite ion-a, showed the most excellent improvement effect.

Claims (2)

[Claims] (1) In the processing method for silver halide color photographic light-sensitive materials, benzyl alcohol is added in an amount of 90 ml/l to 500 ml.
/l and aromatic primary amine color developing agent at 0.07
A color developer prepared by diluting a concentrated developer composition for silver halide color photographic light-sensitive materials containing from 0.4 mol/l to 0.4 mol/l is chemically mixed with the aromatic primary amine color developing agent. A silver halide color photographic light-sensitive material, which comprises processing a silver halide color photographic light-sensitive material containing a coupler in at least one of the photographic layers on a support, which has the function of binding to and inactivating the coupler. How materials are processed. (2) The second-order reaction rate constant k_2 (80°C) of the coupler with p-anisidine is 1.0 to 1.0×10^-^6
A method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the processing rate is in the range of 1/mol·sec.