JPS62249152A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce occurrence of fog due to rapid processing by processing a photographic sensitive material specified in silver chloride content and containing a specified cyan coupler with a liquid color developer specified in sulfite concentration and with a bleach-fixing solution specified in pH. CONSTITUTION:The photographic sensitive material has an emulsion layer containing silver halide grains composed of >=80mol% silver chloride, and at least one of the cyan couplers represented by formulae I and II in which R13 is a ballasting group; Z is H or a group to be released by the coupling reaction with the oxidation product of a color developing agent; Y is -COR14, -CONHCOR14, or the like; and R14 is alkyl, alkenyl, or the like. This photosensitive material is processed with the liquid color developer containing the sulfite in an amount of <=4X10<-3>mol per l of the developer and with the bleach-fixing solution adjusted to 4.5-6.8, thus permitting the photosensitive material to be rapidly developed while reducing occurrence of fog.

Description

[Detailed Description of the Invention] Industrial Application Field] The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, a method for processing a silver halide color photographic light-sensitive material, which enables rapid processing and has improved processing stability in the rapid processing. Halo.

The present invention relates to a method for processing a silver germide color photographic material.

[Background of the Invention] In recent years, there has been a desire in the art for a technology that enables rapid processing of silver halide color photographic materials, and that also provides excellent processing stability and stable photographic properties.
In particular, a method for processing silver halide color photographic materials that can be processed quickly is desired.

In other words, silver halide color photographic light-sensitive materials are subjected to running processing in automatic processing machines installed in each laboratory, but as part of an effort to improve service to users, processing is carried out on the same day that processing is received. There is a need to process and return the item to the user, and recently there has been a demand for the item to be returned within a few hours of receiving it, so there is an urgent need to develop technology that can process the item quickly.

Looking at the conventional technologies for rapid processing of silver halide color photographic light-sensitive materials, [1] technology based on improvements in silver halide color photographic light-sensitive materials, [2] technology using physical means during development processing, [3] development processing. Regarding the above [1], there are the following: (1) Improvement of the silver halide composition (for example, techniques for making silver halide fine grains as described in JP-A-51-77223, 1) Use of additives (for example, JP-A-58-184142 and JP-B-56-18939);
64339, a technique of adding 1-aryl-3-pyrazolidone having a specific structure to a silver halide color photographic light-sensitive material, and JP-A-57-144547, JP-A-57-57-50534, and JP-A-5B-50535. , same 5B-
(Technology for adding 1-arylpyrazolidones as described in No. 50536 into silver halide color photographic light-sensitive materials)
, ■Technology using fast-reactive couplers (for example,
-10783, JP-A-50-123342, JP-A No. 51
-102636 (a technique using a fast-reacting yellow coupler), (51) technology for forming photographic constituent layers vf1 (for example, a technique for thinning photographic constituent layers described in Japanese Patent Application No. 60-204992), etc. Regarding [2] above, there are techniques for stirring the processing liquid (for example, the stirring technique for processing liquid described in Japanese Patent Application No. 61-23334), and regarding [3] above, there is ■ a technique using a development accelerator. , (2) technology for enriching color developing agents, and (2) technology for lowering halogen ions, particularly bromide ions, by 1 degree.

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

During this process, halogen ions generated by reduction of silver halide are eluted into the developer and accumulated. Additionally, components such as inhibitors contained in the light-sensitive material are also eluted into the color developing solution and accumulated. In the desilvering step, silver produced during development is bleached with an oxidizing agent, and then all silver salts are removed from the photosensitive material as soluble silver salts with a fixing agent. In addition,
A one-bath bleach-fixing method is also known in which the bleaching step and the fixing step are performed simultaneously.

Among the rapid processing techniques described in [1] above, techniques using silver halide photosensitive materials containing silver halide grains made of highly concentrated silver chloride (e.g., JP-A-58-95345, JP-A-Sho 60- No. 19140, JP-A No. 58-95736, etc. (described in Mei I8) provide particularly excellent speed-up performance. However, when such a light-sensitive material containing high silver chloride is used, a physical development reaction occurs due to the sulfite normally contained in the color developing solution, which has the disadvantage that the dye density becomes insufficient. For this reason, photosensitive materials containing high silver chloride have no choice but to be used in a concentration range where sulfite is extremely low. However, if a photosensitive material containing high silver chloride is developed using a color developing solution with a low sulfite concentration, sufficient speed can be obtained, but if the bleach-fixing process is subsequently performed, the preservatives in the color developing solution It has been found that due to the low concentration of certain sulfites, the main coloring agent is oxidized, which tends to cause so-called bleaching edge blur.

In particular, due to recent demands for low pollution and cost reduction, there is a trend toward low replenishment or high regeneration rates of bleach-fix solutions, and the amount of color developing solution accumulated in bleach-fix solutions is increasing. In other words, when reducing the replenishment rate or increasing the regeneration rate of the bleach-fix solution, there may be a difference in the effects of evaporation or regeneration operations, or differences in the throughput of photographic light-sensitive materials (for example, the difference between the beginning of the week when the number of orders is high and the weekend when the number of orders is low). Differences in processing amount, differences in processing role between high season and off season, etc.) increase the amount of color developing solution in the bleach-fix solution. Under such circumstances, the photographic properties deteriorate significantly, such as bleaching blade burrs becoming large, and conventionally known techniques (for example, JP-A No. 50-136031,
British Patent No. 1,131,335M, U.S. Patent No. 3,29
3,036, etc.), the reality is that it is becoming impossible to compensate.

Another problem with high-silver chloride-containing photosensitive materials, which is an extremely effective speed-up technique, is that when a fixing agent (for example, thiosulfate, which is commonly used in bleach-fixing solutions) is mixed into the color developing solution. It has been found that physical development occurs and significant cyan fog occurs. In particular, color developing solutions in recent years have tended to have lower replenishment rates due to demands for lower pollution and lower costs. The amount of salt tends to increase, and the situation is becoming increasingly severe for photosensitive materials containing high silver chloride.

[Object of the Invention] Therefore, the first object of the present invention is to provide a silver halide color photographic light-sensitive material which uses high chloride silver halide, provides rapid developability, and has improved fogging in a bleach-fix solution. The purpose is to provide a processing method. A second object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material in which fog is less likely to occur even when a bleach-fix solution is refilled at low levels. A third object of the present invention is to provide a method for processing silver halide color photographic materials with improved processing stability. A fourth object of the present invention is to provide a method for processing silver halide color photographic materials in which less fog occurs even when a bleach-fix solution is mixed into a color developing solution.

[Structure of the Invention] As a result of various studies by the present inventors, the above-mentioned object of the present invention is to
A silver halide color photographic material having at least one silver halide emulsion layer is imagewise exposed and then subjected to processing including at least a color development step and a bleach-fixing step following the color development step. In the processing method, at least one layer of the silver halide emulsion layer is a silver halide emulsion layer containing tI4 grains having a chloride content of 80 mol % or more; At least one of the silver 1 ganide emulsion layers contains at least 61 cyan couplers represented by the following general formulas [C-Ll and [C-2], and the color developer used in the color development step is , sulfite, 8 of the sulfite
The bleach-fixing solution used in the bleach-fixing step has a pH in the range of 4.5 to 6.8. In doing so, the inventors have found a way to achieve the desired effects of the present invention, and have come up with the present invention.

General formula [C-1] [In the formula, R13 represents a ballast group, Z represents a hydrogen atom or a group that can be separated by coupling with an oxidized product of an aromatic primary amine color developing agent, -CON HCO
R14 or -CONH8O2R++ (R14 represents an alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group, R+s is a hydrogen atom, an alkyl group,
represents an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and R++ and Rls are bonded to each other and 5
or may form a six-membered ring. ). ] [Specific structure of the present invention] In the method for processing a silver halide color photographic light-sensitive material of the present invention, in order to enable rapid development processing, the silver halide emulsion layer consists of 80 mol% or more of silver chloride. Contains silver halide grains.

In the present invention, the concentration of sulfite used as a preservative is 4X10-3 per color developer to prevent the decrease in dye density due to silver development reaction, which is likely to occur when such high silver chloride-containing photosensitive materials are used. This was prevented by keeping the amount below mol.

Furthermore, in the present invention, one of the problems caused by using a photosensitive material containing high silver chloride, that is, bleach edge blur, that is, stain that occurs in the bleach-fix solution, can be solved by adjusting the pH of the bleach-fix solution to 4.5 to 6. .

The color developer used in the present invention has a sulfite concentration of 4×10 −3 mol or less, preferably 2×10 −3 to 0 mol per color developer.

In conventional color developing solutions, sulfite is added as one of the preservatives, usually at a concentration of 8 x 10-3 to 4 x 1 per 12 parts of the color developing solution.
Although an amount of about 0-2 mol was used, when the conventional system was applied to the present invention, a decrease in color density occurred, which was considered to be caused by dissolution physical development of silver chloride. The present invention solves the above problem by using a combination of lowering the sulfite concentration to a specific range, using a specific cyan coupler in the light-sensitive material, and using a bleach-fix solution with a specific pH as described above. It is resolved.

Examples of the sulfite used in the present invention include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and the like.

As the color developing agent used in the color developer used in the present invention, p-phenylenediamine compounds having a water-soluble group are preferred from the viewpoint of the desired effects of the present invention.

A p-phenylenediamine compound having a water-soluble group is
Compared to paraphenylenediamine compounds that do not have water-soluble groups such as N,N-diethyl-p-phenylenediamine,
Not only does it not cause contamination of photosensitive materials (and does not cause skin irritation), it also has the advantage that the object of the present invention can be achieved efficiently by combining it with the compound represented by the general formula [I]. can be achieved.

Examples of the water-soluble group include those having at least one on the amino group or benzene nucleus of the p-phenylenediamine compound, and specific examples of the water-soluble group are as follows.

-(CH2)n -CH208゜-(CH2)In -NH3O2-(CH2)n-C
H3, -(CH2)I O(CH2)n -CH3, -(
CH2CH20) n Cal 8 2m+1 (m
and n each represent an integer of 0 or more. ), -CO
Preferred examples include OH group and -8O3H group.

Specific examples of color developing agents preferably used in the present invention are shown below.

Margin below L1 no 7. +.

Exemplary color development agent (A-1) (A-2) H,C2C2H,OH \, / (A-3) (A-4> HsC2C2H-OCH:+ (A-5) H, C2C, H, SO, H (A-6) H, CC, H, OH (A-7) HOH4C2C2H4OH (A-8) HIO2C, HISO, H (A-9) H, C, C, H, SO, H (A-10) HC82COOH (A-1]> (A-12) H2 (A-13) H6 large CH2CH, 0qC2H.

(A-14) H) CH2CH20 juice C, H.

(A-15) HsC2C2H4NH8O2CH3 \N/ H2 (A-16) 85C2C,H,OH Below margin No. 1 1-~ Among the color developing agents exemplified above, preferred for use in the present invention are exemplification No., (A- 1), (A-2), (A-
3), (A-4), (A-6), (A-7) and (A
-15), particularly preferably (A-
1).

The color developing agents mentioned above are usually used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate and the like.

The color developing agent having a water-soluble group used in the present invention is
IX 10-2 to 2X10 per 12 ordinary color developer
It is preferable to use a molar range of 1.5X 10' to 2X per liter of color developer from the viewpoint of rapid processing.
A range of 10-1 mol is more preferred.

In the present invention, when a triazylstilbene fluorescent brightener represented by the following general formula [XV] is used in the color developing solution according to the present invention, the desired effects of the present invention can be better achieved.

Margin below -1]

General formula [XV] In the formula, X+, etc.), aryl groups (e.g., phenoxy, p-sulfophenyl, etc.).

Alkyl groups (e.g. methyl, ethyl, etc.), aryl groups (
(e.g., phenyl, methoxyphenyl, etc.), amino groups, alkylamino groups (e.g., methylamino, ethylamino,
Propylamine, dimethylamino, cycloheledylamino, β-hydroxyl tylamino, di(β-hydroxyethyl)amino, β-sulfoethylamino, N-(β-
sulfonidel)-N'-methylamino, N-(β- and droxyethyl-N'-methylamino, etc.), arylamino groups (e.g. anilino, 0-1+1-1p-sulfoanilino, o-1m-1p-chloroanilino, 0- 1m-1
p-Toluidino, 0-1m-1p-carboxyanilino, 0-1m-1p-hydroxyanilino, sulfonaphthylamino, 0-1m-1p-aminoanilino, 0-1I
-1p-anilino, etc.). M represents a hydrogen atom, sodium, potassium, ammonium or lithium.

Specifically, the following compounds may be mentioned, but the invention is not limited thereto.

Hereinafter, the following is below:
=^
-=C-0 Koku Kuku < Kuku Yama The triazylstilbene-based brightener of the present invention is described, for example, in the Chemical Products Industry Association line, "Fluorescent Brighteners" (published in August 1976), page 8. It can be synthesized by conventional methods.

These triazylstilbene type brighteners are preferably used in an amount of 0.2 to 6 g, particularly preferably 0.4 to 3 g, per color developer 1 of the present invention.

The color developing solution of the present invention can contain the following developer components in addition to the above components.

As alkaline agents other than the above carbonates, for example, sodium hydroxide, potassium hydroxide, silicates, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, etc. alone or in combination, They can be used together as long as the above-mentioned effects of the present invention, that is, no precipitation occurs and the pH stabilizing effect is maintained. In addition, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, borates, etc. are used for purposes such as pharmaceutical needs or to increase ionic strength. be able to.

Additionally, inorganic and organic anti-capri agents can be added as required.

Furthermore, a development accelerator can also be used if necessary.

As a development accelerator, U.S. Pat. No. 2,648,604;
3.671,24γ and Japanese Patent Publication No. 44-9503, other cationic compounds, cationic dyes such as phenosafranin, neutral salts such as thallium nitrate, Patent No. 2, 5
No. 33,990, No. 2.531.832, No. 2,
950,970, No. 2,577.127, and nonionic compounds such as polyethylene glycol and derivatives thereof, polythioethers described in Japanese Patent Publication No. 44-9504, and organic solvents described in Japanese Patent Publication No. 44-9509. and organic amines such as ethanolamine, ethylenediamine, jetanolamine, and triethanolamine. In addition to benzyl alcohol and phenethyl alcohol, which are described in US Pat. .

In the above, when using a poorly soluble organic solvent such as benzyl alcohol, tar is likely to be generated due to long-term use of the color developing solution, especially during running processing in a low replenishment system. Proximity to the paper sensitive material to be processed may even lead to serious malfunctions that significantly impair its commercial value.

In addition, poorly soluble organic solvents are bad solvents for water, so
Not only is it troublesome that a stirring device is required to prepare the color developing solution itself, but also the use of such a stirring device
Due to its poor solubility, there is a limit to its development accelerating effect.

Furthermore, poorly soluble organic solvents require biochemical oxygen! (
The pollution load value such as BOD) is large, and it is impossible to dispose of it in sewers or rivers, etc., and treatment of the waste liquid has problems such as requiring a large amount of labor and cost.
It is preferable to use 5t12 or less per 12 color developing solutions, more preferably 1- or less. Particularly, staining generated in the bleach-fix solution is also reduced when it is not used at all, which is preferable in the present invention.

In the color developing solution used in the present invention, the following general formula [
When the compound represented by I] is used, the desired effects of the present invention are better exhibited, and the storage stability of the color developing solution is also improved from deterioration. Since silver development does not occur due to hydroxylamine, it is particularly preferably used in the present invention.

General formula [I] (In the formula, R1 and R2 each represent an alkyl group having 1 to 3 carbon atoms.) In general formula [I], R1 and R2 each represent an alkyl group having 1 to 3 carbon atoms, The alkyl groups having 1 to 3 carbon atoms represented by R1 and R2 may be the same or different, and include, for example, a methyl group, an ethyl group, an n-propyl group, a 1so-propyl group, and the like.

R1 and R2 are preferably both ethyl groups.

Specific examples of the compound of the present invention represented by the general formula [I] are shown below, but the present invention is not limited thereto.

Below is the margin ゛・Rizu---;.

(I-1) C2Hs' C2H2 -OH 1so-CcoH7 kXT all 2 white, 2 These compounds of the present invention are usually hydrochloride, sulfate, o-toluenesulfonate, oxalate, phosphoric acid. It is used in the form of salts such as salt and acetate.

The concentration of the compound of the present invention in the color developing solution is preferably the same as that of hydroxylamine commonly used as a preservative, for example, 0.5 (+, 1 to 50 g/ffi, more preferably 10/ffi). /!~30(1/ffi), more particularly preferably 5C1/(1~20g/j!
It is.

The color developing solution used in the present invention has the following general formula [B-
At least one compound selected from the compound represented by [I] and the compound represented by the general formula [B-n] (hereinafter,
When containing organic acid iron complex salts (referred to as compounds of the present invention) in the bleach-fix solution, the desired effects of the present invention can be better achieved, and organic acid iron complex salts (e.g.,
Ethylenediaminetetraacetic acid iron (III) complex salt) is particularly preferably used because it has the effect of stabilizing the color developing solution of the present invention even when it is mixed into the color developing solution.

General formula CB-II General formula [B-I[] In general formula [B-1], [B-1], R3, R4,
Rs a and R6 are each a hydrogen atom, a halogen atom,
Sulfonic acid group, alkyl group having 1 to 7 carbon atoms, -0R
7, -GOOR8, R7, Ra, Rs and RIG each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.

However, if R4 represents 10H or a hydrogen atom,
R3 is a halogen atom, a sulfonic acid group, and has 1 to 7 carbon atoms.
represents an alkyl group, -0R7.

Examples of the alkyl group represented by R3, R4, Rs and R6 include methyl group, ethyl group, 1so-propyl group, n-propyl group, t-butyl group, n-butyl group, hydroxymethyl group, hydroxyethyl group, Examples include methylcarboxylic acid group, benzyl group, and R7, Ra
, Rs and Rh.

The alkyl group represented by is as defined above, and further includes an octyl group.

Furthermore, the phenyl group represented by R3, Rh, Rs and R6 is a phenyl group, 2-hydroxyphenyl group, 4
-aminophenyl group and the like.

Typical specific examples of the chelating agent of the present invention are listed below, but the invention is not limited thereto.

(B-I-1) 4-isopropyl-1,2-dihydroxybenzene (B-I-2) 1.2-dihydroxybenzene-3,5-disulfonic acid ゛(B-I-3) 1.2.3 -Trihydroxybenzene-5-carboxylic acid (B-I-4) 1.2.3-trihydroxybenzene-5-carboxymethylnisder (B-I-5) 1.2.3-trihydroxybenzene-5 -Carboxy-〇-butyl ester (B-I-6) 5-t-butyl-1,2,3 trihydroxybenzene (B-II-1) 2,3-dihydroxynaphthalene-6-sulfonic acid (B-II -2> 2.3.8-trihydroxynaphthalene-6-sulfonic acid (B-I[-3) 2.3-dihydroxynaphthalene-6-carboxylic acid (B-II-4> 2.3-dihydroxy-8 -isopropyl-naphthalene (B-II-5) 2.3-dihydroxy-8-chloro-naphthalene-6-
Among the above-mentioned sulfonic acid compounds, compounds particularly preferably used in the present invention include 1,2-dihydroxybenzene-3,
Examples include 5-disulfonic acid, and it can also be used as alkali metal salts such as sodium salt and potassium salt.

In the present invention, the compound of the present invention is used in a color developing solution 12.
It can be used in a range of 5 mg to 20 g, preferably 101] g to 10 g, more preferably 201Q
Good results are obtained by adding ~3g.

The compounds of the present invention may be used alone or in combination. Furthermore, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane-1,2
, 4-tricarboxylic acid, polyphosphoric acid such as tripolyphosphoric acid or hexametaphosphoric acid, and other chelating agents may be used in combination.

When the color developer according to the present invention contains a compound represented by the following general formula [D], it not only improves the effects of the present invention but also prevents air oxidation of the color developer. Since it also shows an improvement effect, it is more preferably used.

General formula [D] (In the formula, R2] is a hydroxyalkyl group having 2 to 6 carbon atoms, R22 and R23 are each a hydrogen atom, and 1 to 6 carbon atoms.
an alkyl group, a hydroxyalkyl group having 2 to 6 carbon atoms,
The benzyl group or the integers X' and 2' in formula 6 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 2 to 6 carbon atoms. ) Preferred specific examples of the compound represented by the general formula [0] are as follows.

(D-1) Ethanolamine, (D-2) Jetanolamine, (D-3) Triethanolamine, (D-4) Di-isopropanolamine, (D-5) 2
-Methylaminoethanol, (D-6) 2-ethylaminoethanol, (D-7) 2-dimethylaminoethanol, (D-8) 2-diethylaminoethanol, (D-
9) 1-diethylamino-2-probanol, <D-10) 3-diethylamino-1-propanol, (D-1]) 3-dimethylamino-1-propanol, (D-12) Isopropylaminoethanol , (D-
13) 3-amino-1-propanol, (D-14>2
-amino-2-methyl-1,3-propanediol, (D-15) ethylenediaminetetraisopropanol, (D-16) benzyljetanolamine, (D-1
7) 2-amino-2-(hydroxymethyl)-1,3
-Propanediol.

These compounds represented by the general formula [D] should be used in an amount of 3 to 10% per 12 color developing solution from the viewpoint of the desired effect of the present invention.
It is preferably used in the range of 0g, more preferably 6g~
It is used in a range of 50g.

Furthermore, the color developing solution of the present invention may contain ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other ingredients as required.
The compounds described in the specification can be used as organic solvents to increase the solubility of developing agents.

Furthermore, auxiliary developers can also be used with the developing agents. These auxiliary developers include, for example, N-methyl-p-aminephenol hexulfate (methol).
, phenidone, N,N'-diethyl-p-aminephenol hydrochloride, N,N.

N',N'-tetramethyl-p-phenylenediamine hydrochloride is known, and the amount added is usually o.
, oig ~ 1.0 (1/4 is preferred. In addition,
If necessary, a competitive coupler, a fogging agent, a colored coupler, a development inhibitor-releasing coupler (so-called DIR coupler), a development inhibitor-releasing compound, or the like may be added.

Furthermore, other anti-stain agents, anti-sludge agents,
Various additives such as a multilayer effect accelerator can be used.

Each component of the above-mentioned color developing solution can be prepared by sequentially adding and stirring to a certain amount of water. In this case, the component with low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. More generally, a concentrated aqueous solution or a solid state of a plurality of components that can coexist stably in a small container is added to water and stirred to prepare the color developing material of the present invention. It can be obtained as a liquid.

In the present invention, the above color developing solution can be used in any pH range, but from the viewpoint of rapid processing, the pH is 9.5 to 13.0.
preferably p)l 9.8, more preferably p)l 9.8
~13.0.

In the present invention, the processing temperature for color development is 30
C. or more and 50.degree. C. or less, the higher the temperature, the faster the processing can be performed in a short time, which is preferable.However, from the viewpoint of image storage stability, it is better not to be too high, and it is preferable to process at 33.degree. C. or more and 45.degree. C. or less.

Conventionally, the color development time has generally been about 3 minutes and 30 seconds, but in the present invention, it can be reduced to within 2 minutes, and it can also be carried out in the range of 30 seconds to 1 minute and 30 seconds. be.

A bleaching agent that can be preferably used in the bleach-fix solution used in the present invention is goldffl!, an organic acid. 1 salt.

Applicable! The i-salt is one in which a metal ion such as iron, cobalt, or copper is coordinated with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid. The most preferred compounds used to form such gold is salts of organic acids include polycarboxylic acids.

These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N, N', N
' -Triacetic acid [41 Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [61 Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycine citric acid (or tartaric acid) [9] Ethyl ether diamine tetraacetic acid [10 ] Glycol ether diamine tetraacetic acid [1]] Ethylene diamine tetraprobionic acid [12]
Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N -(β-oxyethyl)
-N,N',N'-Triacetic acid sodium salt [18] Propylene diamine tetraacetic acid sodium salt [191 Nitriloacetic acid sodium salt] [20] Cyclohexanediamine tetraacetic acid sodium salt These bleaches have a concentration of 5 to 450 (1/ffi, More preferably, it is used at 20 to 150 (+/ffi).The bleach-fix solution contains a silver halide fixer in addition to the above-mentioned bleaching agent, and optionally contains sulfite as a preservative. Alternatively, a bleach-fix solution consisting of an ethylenediaminetetraacetate iron (III) complex salt bleach and a small amount of a halide such as ammonium bromide other than the above-mentioned silver halide fixer may be applied, or vice versa. Bleach-fix solutions containing a large amount of halides such as ammonium bromide, and iron ethylenediaminetetraacetate (Ill).
A special bleach-fix solution having a composition consisting of a combination of a complex salt bleach and a large amount of a halide such as ammonium bromide can also be used. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can.

The silver halide fixing agents contained in the bleach-fixing solution include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and thiosulfate, which are used in ordinary fixing processes. Typical examples thereof include thiosulfates such as ammonium sulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium ocyanate, thioureas, thioethers, and the like. These fixing agents are used in an amount of 5a/f1 or more, within the range that can be dissolved, but generally 30g to 150g/f1.
Use with l.

The bleach-fix solution contains boric acid, borax, sodium hydroxide,
Various pH buffering agents such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide can be contained alone or in combination of two or more.

Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as human Oxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, methanol, dimethylsulfamide, dimethylsulfoxide, etc. An organic solvent or the like can be appropriately contained.

The bleach-fix solution used in the present invention includes JP-A-48-280, JP-B No. 45-8506, JP-B No. 46-556, Belgian Patent No. 770.910, JP-B No. 454-836, JP-B No. 53-9854, JP-A No. 54-71634 and No. 4
Various bleaching accelerators such as those described in No. 9-42349 can be added.

The processing temperature is 80° C. or lower, which is 3° C. or more, preferably 5° C. or more lower than the temperature of the processing solution in the color developing tank, but preferably 55° C. or lower to prevent evaporation.

The pH of the bleach-fix solution used in the present invention is in the range of 4.5 to 6.8. This is because if the pH is below 4.5, the bleach-fix solution itself becomes unstable and stratification is likely to occur, and if the I)H of the bleach-fix solution is above 6.8, magentastin cannot be prevented. This is because it becomes possible. However, in the present invention, the pH of bleach-fixing is 5.
The range of 5 to 6.5 is particularly preferable, and the desired effects of the present invention can be achieved.

I will explain about it.

The silver halide grains used in the silver halide color photographic light-sensitive material applied to the present invention contain at least 80% silver chloride.
Silver halide grains containing mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more.

The silver halide emulsion containing silver halide grains consisting of 80 mol% or more of silver chloride may contain silver bromide and/or silver iodide as a silver halide composition in addition to silver chloride,
In this case, silver bromide is at most 20 mol%, preferably at most 10 mol%, more preferably at most 5 mol%, and when silver iodide is present, it is at most 1 mol%, preferably 0.5 mol%. It is as follows. Such silver halide grains substantially consisting of silver chloride according to the present invention contain 80% or more by weight of all the silver halide grains in the silver halide emulsion layer containing the silver halide grains. It is preferable that the ratio is 100%, and more preferably 100%.

The crystals of the silver halide grains used in the present invention may be normal products, twin crystals, or other crystals, and have [1007 planes and [1]1 crystals.
] Any aspect ratio can be used.

Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core-shell type) in which the inside and outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. In addition, tabular silver halide grains
1] No. 3934 and Japanese Patent Application No. 59-170070) may also be used.

The silver halide grains used in the present invention may be obtained by any of the acidic method, neutral method, and ammonia method.

Alternatively, for example, seed particles may be produced using an acidic method, and then grown using an ammonia method, which has a high growth rate, to grow to a predetermined size. pH in the reaction vessel when growing silver halide grains.

By controlling pAQ etc., for example, JP-A-54-485
It is preferable to sequentially and simultaneously implant and mix silver ions and halide ions commensurate with the growth rate of silver halide grains as described in No. 2].

Preferably, the silver halide grains according to the present invention are prepared as described above. A composition containing the silver halide grains is referred to herein as a silver halide emulsion.

These silver halide emulsions are composed of activated gelatin: sulfur sensitizer, such as allylthiocarba, mido, thiourea, cystine, etc.: selenium sensitizer: reduction sensitizer, such as primary
Tin salts, thiourea dioxide, polyamines, etc. = jl Metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, etc., or, for example, ruthenium, Sensitizers with water-soluble groups such as palladium, platinum, rhodium, and iridium, specifically ammonium chlorovaladate, potassium chloroaurate, and sodium chlorovaladate (these types can be sensitized depending on the size of the cell). ), alone or in appropriate combinations (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.). may be sensitized.

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and contains a small amount (both of which have one type of hydroxytetrazaindene and a mercapto group) before, during, or after the chemical ripening. It may also contain at least one nitrogen heterocyclic compound.

The silver halide used in the present invention is mixed with an appropriate sensitizing dye in an amount of 5 x 10-3 to 3
Optical sensitization may be achieved by adding 3 moles. Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of sensitizing dyes that can be advantageously used in the present invention include the following.

That is, as sensitizing dyes used in blue-sensitive silver halide emulsions, for example, West German Patent No. 929.080, US Pat. No. 2,231,658, US Pat. No. 2,493.748,
Same No. 2,503,776, Same No. 2,519,001, Same No. 2,912゜329, Same No. 3,656,959
No. 3,672,897, No. 3,694,2]
No. 7, No. 4.025.349, No. 4,046.5
No. 72, British Patent No. 1,242,588, Special Publication No. 1972
Examples include those described in No. 14030, No. 4322884, and the like. In addition, as a sensitizing dye used in a green-sensitive silver halide emulsion, for example, US Pat.
, No. 939.201, No. 2,072,908, No. 2,739.149, No. 2,945,763, British Patent No. 505,979, etc.; Typical examples include merocyanine dyes and complex cyanine dyes. moreover,
Sensitizing dyes used in red-sensitive silver halide emulsions include, for example, U.S. Pat. Nos. 2,269,234 and 2,2
70°378, same No. 2,442.710, same No. 2,
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in Japanese Patent No. 454,629 and No. 2.776.280.

Furthermore, U.S. Pat. No. 2,2] 3,995, U.S. Pat.
No. 93.748, German Patent No. 2.519.001, West German Patent No. 929.080, etc., cyanine dyes, merocyanine dyes or composite cyanine dyes are used as green-sensitive silver halide emulsions or red-sensitive silver halide emulsions. It can be advantageously used in emulsions.

These sensitizing dyes may be used alone or in combination.

The photographic material of the present invention may be optically sensitized in a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes alone or in combination, if necessary.

A typical particularly preferred spectral sensitization method is, for example, Japanese Patent Publication No. 43-493 concerning the combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 6, No. 43-22884, No. 45-18433,
No. 47-37443, No. 48-28293, No. 49
No.-6209, No. 53-12375, JP-A-52-2
No. 3931, No. 52-51932, No. 54-801]
No. 8, No. 58-153926, No. 59-1] 6646
No. 59-1] No. 6647 and the like.

Regarding the combination of carbocyanine having a benzimidazole nucleus and other cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831 and 47-1]
1] No. 4, No. 47-25379, No. 48-38406
No. 48-38407, No. 54-34535, No. 55-1569, JP-A-50-33220, No. 5
No. G-38526, No. 51-107127, No. 51
-1] No. 5820, No. 51-135528, No. 52-
No. 104916, No. 52-104917, and the like.

Furthermore, regarding combinations of benzoxazolocarbocyanine (oxa-carbocyanine) and other carbocyanines, for example, Japanese Patent Publication Nos. 44-32753 and 46
-1] No. 627, JP-A No. 57-1483, and regarding merocyanine, for example, JP-A No. 48-38408.
No. 48-41204, No. 5G-40682, JP-A No. 56-25728, No. 58-10753, No. 5
No. 8-91445, No. 59-1] No. 6645, No. 5G
-33828 etc. are mentioned.

Regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publication Nos. 43-4932, 43-4933, 45-26470, 4
No. 6-18107, No. 47-8741, JP-A-59-
1] No. 4533, and the method described in Japanese Patent Publication No. 49-6207 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine, and styryl dye can be advantageously used.

In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or fluorinated alcohol described in Japanese Patent Publication No. 40659/1984 is used in advance. It is used by dissolving it in a hydrophilic organic solvent.

The addition may be made at any time such as at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening, and in some cases, it may be added at a step immediately before coating the emulsion.

The photographic constituent layer of the silver halide color photographic light-sensitive material of the present invention may contain a water-soluble dye or a dye (AI dye) that can be decolorized with a color developing solution. Examples of the AI dye include oxonol dye, hemioxonol dye, Dyes, merocyanine dyes and azo dyes are included. Among them, oxonol dyes, hemioxonol dyes, merocyanine dyes, and the like are useful.

Examples of AI dyes that can be used include British Patent No. 584.6
No. 09, No. 1,277.429, Japanese Unexamined Patent Publication No. 1985-85
No. 130, No. 49-99620, No. 49-1]4
No. 420, No. 49-129537, No. 52-10
81] No. 5, No. 59-25845, No. 59-1]
No. 1640, No. 59-1] No. 1641, U.S. Patent No. 2
．． 274,782, 2,533,472, 2,956,079, 3,125,448, 3.148.187, 3,177.078,
3,247.127, 3,260.601, 3.540.887, 3.575.704
No. 3,653,905, No. 3,718,47
No. 2, No. 4.078.312, No. 4,070,3
Examples include those described in No. 52.

These AI dyes are generally used at a concentration of 2 per mole silver in the emulsion layer.
It is preferable to use X10-3 to 5
Use moles.

Next, general formula [C-1] or [C
-2] will be explained. In the general formulas [C-1] and [C-2], Rn3
represents a ballast group, and Z represents a hydrogen atom or a group that can be separated by coupling with an oxidized product of an aromatic primary amine color developing agent. -CONHCORt+ or -〇〇NH3
O2R1to (Rn represents an alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group, R+
s represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and Rn and R
15 may be combined with each other to form a 5- or 6-membered ring. ).

The above [C-1] and [C-2] will be explained in more detail. In the general formulas [C-1] and [C-2], Y is -COR1
It is a group represented by 4. Here, R14 is an alkyl group,
Preferably an alkyl group having 1 to 20 carbon atoms (e.g. methyl, ethyl, t-butyl, dodecyl group), an alkenyl group preferably an alkenyl group having 2 to 20 carbon atoms (e.g. allyl group, heptadecenyl group, etc.), a cycloalkyl group, Preferably 5- to 7-membered rings (e.g., cyclohexyl, etc.), aryl groups (e.g., phenyl, tolyl, naphthyl, etc.), heterocyclic groups, preferably containing 1 to 41 nitrogen, oxygen, or sulfur atoms. It represents a 5- to 6-membered heterocyclic group (eg, furyl group, chenyl group, benzothiazolyl group, etc.). R15 represents a hydrogen atom or a group represented by R14. R14 and Rn5 may be bonded to each other to form a 5- to 6-membered heterocycle containing a nitrogen atom. Note that any substituent can be introduced into R13, such as an alkyl group having 1 to 10 carbon atoms (for example, ethyl,
i-propyl, i-butyl, [-butyl, t-octyl, etc.), aryl groups (e.g. phenyl, naphthyl, etc.), halogen atoms (fluorine, chlorine, bromine, etc.), cyano, nitro, sulfonamide groups (e.g. methanesulfone) amide, butanesulfonamide, p-toluenesulfonamide, etc.)
, sulfamoyl groups (e.g. methylsulfamoyl, phenylsulfamoyl, etc.), sulfonyl groups (e.g. methanesulfonyl, p-toluenesulfonyl, etc.), fluorosulfonyl, carbamoylenylcarbamoyl, etc.), oxycarbonyl groups (e.g. ethoxycarbonyl, phenoxycarbonyl) ), acyl groups (eg, acetyl, benzyi, etc.), heterocyclic groups (eg, pyridyl, pyrazolyl, etc.), alkoxy groups, aryloxy groups, acyloxy groups, and the like.

In the general formulas [C-1] and [C-2], R13 imparts diffusion resistance to the cyan coupler represented by the general formulas [C-1] and [C-2] and the cyan dye formed from the cyan coupler. Represents the ballast group necessary for imparting. Preferred are alkyl groups, aryl groups, and heterocyclic groups having 4 to 30 carbon atoms. Examples include linear or branched alkyl groups (eg, thi-butyl, n-octyl, t-octyl, n-dodecyl, etc.), alkenyl groups, cycloalkyl groups, 5- or 6-membered heterocyclic groups, and the like.

In the general formulas [0-1] and [C-2], 2 represents a hydrogen atom or a group that can be separated during a coupling reaction with an oxidation product of a color developing agent.

For example, halogen atoms (e.g. chlorine, bromine, fluorine, etc.)
, substituted or unsubstituted alkoxy group, aryloxy group,
Examples include heterocyclic oxy groups, acyloxy groups, carbamoyloxy groups, sulfonyloxy groups, alkylthio groups, arylthio groups, heterocyclic thio groups, and sulfonamide groups.
No. 563, JP-A No. 47-37425, Equity No. 48
-36894, JP-A No. 50-10135, JP-A No. 5
No. 0i17422, No. 50-130441, No. 5
No. 1-108841, No. 50-120343, No. 52-18315, No. 53-105226, No. 55-14736, No. 54-48237, No. 5
No. 5-32071, No. 55-65957, No. 56
-1938, 56-12643, 56-2
No. 7147, No. 59-1413050, No. 59-
No. 166956, No. 60-24547, No. 60-
35731 and 60-37557.

In the present invention, the following general formulas [C-3], [C-4]
Or, a cyan coupler represented by [C-51] is more preferable.

General formula [C-3] General formula [C-4] General formula [C-5] In general formula [C-3], R3M is a substituted or unsubstituted aryl group (particularly preferably a phenyl group). When the aryl group has a substituent, the substituent is -3C
hR31, halogen atom (e.g. fluorine, bromine, chlorine, etc.), -CF3, -・N02, -CN, -COR37, -
At least one substituent selected from G OOR37, -8O20Rs7, is included.

Here, R37 is an alkyl group, preferably having 1 to 2 carbon atoms.
0 alkyl groups (e.g. methyl, ethyl, tert-butyl, dodecyl groups), alkenyl groups, preferably alkenyl groups having 2 to 20 carbon atoms (e.g. allyl groups, heptadecenyl groups, etc.), cycloalkyl groups, preferably 5~
7-membered ring group (e.g. cyclohexyl group etc.), aryl group (
For example, phenyl group, tolyl group, naphthyl group, etc.), and R3a is a hydrogen atom or a group represented by R37 above.

A preferred compound of the phenolic cyan coupler represented by the general formula [0-31 is one in which R37 is a substituted or unsubstituted phenyl group, and the substituent to the phenyl group is cyano,
These are compounds such as nido O, -302R39 (R39 is an alkyl group), a halogen atom, and trifluoromethyl.

In the general formula [C-41 and [0-51, R35,
R36 is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (such as methyl, ethyl, tert-butyl, dodecyl, etc.), or an alkenyl group, preferably having 2 to 20 carbon atoms.
Flukenyl M (e.g., furyl, oleyl, etc.), cycloalkyl group, preferably 5- to 7-membered ring group (e.g., cyclohexyl, etc.), aryl group (e.g., phenyl group, tolyl group, naphthyl group, etc.), heterocyclic group (nitrogen atom) , oxygen atom,
Alternatively, a 5- to 6-membered heterocyclic group containing 1 to 4 sulfur atoms is preferable, such as a furyl group, a chenyl group, a benzothiazolyl group, etc.).

R37, R31] and the general formula [C-4co and [
Further, arbitrary substituents can be introduced into R35 and R36 of [0-5], and specifically, such substituents can be introduced into R15 of the general formula %.

As substituents, halogen atoms (chlorine atoms,
fluorine atoms, etc.) are preferred.

In the general formulas [C-31, [C-4] and [C-5], Z and R13 are the general formulas [C-1] and [C-2], respectively.
] has the same meaning. A preferred example of the ballast group represented by R13 is a group represented by the following general formula [C-6].

General formula [C-6] In the formula 1, `` represents an oxygen atom, a sulfur atom, or a sulfonyl group, K represents an integer of 0 to 4, ri represents O or 1, and when K is 2 or more, 2 The above R41s may be the same or different, the R phrase represents a linear or branched alkylene group having 1 to 20 carbon atoms, and a substituted alkylene group such as an aryl group, and R4I represents a monovalent cloud, preferably Hydrogen atoms, halogen atoms (e.g. chromium, bromine), alkyl groups, preferably linear or branched alkyl groups having 1 to 20 carbon atoms (e.g. medyl, t-butyl, 1-pendel, t
-octyl, dodecyl, pentadecyl, benzyl, phenethyl, etc.), aryl groups (e.g. phenyl group),
Heterocyclic groups (preferably nitrogen-containing heterocyclic groups), alkoxy groups, preferably linear or branched alkoxy groups having 1 to 20 carbon atoms (e.g. methoxy, ethoxy, t-butyloxy, A-ctyloxy, decyloxy, dodecyloxy) etc.), aryloxy groups (e.g. phenoxy groups)
, hydroxy, acyloxy group, preferably alkylcarbonyloxy group, arylcarbonyloxy group (e.g. acetoxy group, benzoyloxy group), carboxy,
Alkyloxycarbonyl group, preferably having 1 to 2 carbon atoms
o straight or branched alkyloxycarbonyl group, aryloxycarbonyl group, preferably phenoxycarbonyl, alkylthio group, preferably acyl group having 1 to 20 carbon atoms, preferably IN chain or branched alkyl group having 1 to 20 carbon atoms Carbonyl group, acylamino group, preferably a straight chain or branched alkylcarboxamide group having 1 to 20 carbon atoms, benzenecarboxamide, sulfonamide group, preferably a straight chain or branched alkylsulfonamide group having 1 to 20 carbon atoms, or benzene Sulfonamide group, carbamoyl group, preferably a linear or branched fulkylaminocarbonyl group having 1 to 20 carbon atoms, or phenylaminocarbonyl group, sulfamoyl group, preferably having 1 to 20 carbon atoms
represents a linear or branched alkylaminosulfonyl group or phenylaminosulfonyl group.

Next, specific examples of cyan couplers represented by the general formula [C-1] or [C-2] will be shown, but the invention is not limited thereto.

Margin below , -8 ma (t)C5H1t C2H5 C-33 C4H9 ,C4H9 zMs C4Hg (t) CsH.

NH30zCH3 2H5 C-7701 (CI5I(31(n+ and =' ctCN N) These cyan couplers can be synthesized by various methods, for example, Komebo 1 Patent No. 2.772.162, No. 3.7! i-po 1.3 old - issue, same number 3,880,6
No. 61, No. 4.424.3.96, No. 3.222
．． 176 Bow, U.S. Pat. No. 97'+, 773, U.S. Patent No. 8.
+1] No. 1,693, No. 8,01], No. 694, i?
Ima Sho No. 47-2] No. 139, No. 50-1] 2038
No., same No.', +! +-163537, same number 56-29
No. 235, No. 55-99341, No. '+6-1
] No. 6030, No. 52-69329, No. 56-5
No. 5945, No. 56-80045, No. 50-13
4644, as well as U.S. Pat. No. 1,01], 940
No. 3.446, 622@, U.S. Patent No. 3.996
．． No. 253, JP-A-56-65134, JP-A No. 57-2
No. 04543, No. 57-204544, No. 57-
No. 204545, Japanese Patent Application No. 56-131312, No. 5
5-131313, 56-131314, 56-131309, 56-13131], 57-149791, 56-130459,
JP-A-59-146050, JP-A No. 166956,
It can be synthesized by the synthesis methods described in Japanese Patent Nos. 60-24547, 60-35731, and 60-37557.

In the present invention, the cyan coupler represented by the general formula [C-1] or [C-2] can be used in combination with a conventionally known cyan coupler to the extent that it does not contradict the purpose of the present invention. In addition, the general formula, [C-1] and [C
-2] cyan coupler can also be used together.

When the cyan coupler according to the present invention represented by the general formula [C-1] or [C-2] is contained in a silver halide emulsion, it is usually about o, oo per mole of silver halide.
It is used in a range of s ~2 mol, preferably 0.01 to 1 mol.

l+i'* Photographic magenta couplers used in the silver halide color photographic light-sensitive material according to the present invention include compounds such as pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indasilone. As a pyrazolone magenta coupler, U.S. Patent No. 2,600
．． No. 788, No. 3,062.653, No. 3,127
, No. 269, No. 3, 31], No. 476, No. 3.41
No. 9,391, No. 3,519,429, No. 3.5
No. 58.318, No. 3,684,514, No. 3.88
8.680, JP-A-49-29639, JP-A No. 49-1
] No. 1631, No. 49-129538, No. 50-13
No. 041, Special Publication No. 53-47167, No. 54-104
Compounds described in No. 91 and No. 55-30615; as pyrazolotriazole magenta couplers,
U.S. Patent No. 1.247,493, Belgian Patent No. 792.
As the diffusion-resistant colored magenta coupler, a compound in which the coupling position of a colorless magenta coupler is substituted with arylazo is generally used. For example, the coupler described in U.S. Pat.
No. 71, No. 2,983,608, No. 3,005,71
No. 2, No. 3.684,514, British Patent No. 937.62
]@, JP-A-49-123625, JP-A No. 49-3144
Examples include the compounds described in No. 8.

Furthermore, colored magenta couplers of the type described in U.S. Pat. No. 3,419,391, in which the dye flows out into the processing solution by reaction with an oxidized product of a developing agent, can be used.

As photographic yellow couplers, open-chain ketomethylene compounds have conventionally been used, and generally widely used benzoylacetanilide type yellow couplers and pivaloylacetanilide type yellow couplers can be used. Further, a two-order yellow coupler in which the carbon atom at the coupling position is substituted with a substituent capable of forming tltQl'2 during the coupling reaction is also advantageously used.

Examples of these are U.S. Pat. No. 2.875.057, 3.2
65.506++, 3.664.841, 3.4
08.194, 3,277, 155, 3,44
No. 7.928, No. 3.415.652, Special Publication Showa 4Qi
No. 3576, IFtl No. 43-29432, No. 48
-68834, 49-40736, 49-12
No. 2335, No. 50-28834, No. 50-1329
26, etc., along with the synthesis method.

The amount of the above-mentioned diffusion-resistant coupler used in the present invention is generally 0.05 molar per mole of silver in the light-sensitive silver halide emulsion layer.
~2.0 mol.

In the present invention, DLR compounds are preferably used in addition to the above-mentioned diffusion-resistant couplers.

Furthermore, in addition to DIR compounds, compounds that release development inhibitors during development are also included in the present invention; for example, U.S. Pat.
No., West German patent ratio Iff (OLS) 2,417
, 914q, JP-A-52-15271, JP-A No. 53-9
1] No. 6, No. 59-123838, No. 59-127
Examples include those described in No. 038 and the like.

The DIR compound used in the present invention is a compound capable of reacting with an oxidized product of a color developing agent to release a development inhibitor.

A typical example of such an IR compound is a DIR coupler in which a group capable of forming a compound having a development-inhibiting effect when separated from the active site is introduced into the coupler active site; for example, British Patent No. 935 .454, U.S. Patent No. 3.227.554, U.S. Patent No. 4,095,
No. 984, No. 4,149.886, etc.

The above-mentioned DIR coupler has the property that, when subjected to a coupling reaction with an oxidized form of a color developing agent, the coupler NFT= forms a dye while releasing a phenomenon inhibitor. In addition, the present invention is disclosed in U.S. Pat. No. 3,652,345 and U.S. Pat.
No. 28,041, No. 3,958,993, No. 3,
961.959, 4,052,2]3, JP-A-53-1]0529, 54-13333, 55
Also included are compounds that release a development inhibitor but do not form a dye upon coupling reaction with an oxidized form of a coloring agent, such as those described in No. 161237.

Furthermore, JP-A-54-145135 and JP-A-56-1
] 4946 and 57-154234, the core forms a dye or a colorless compound, while! The released timing group may undergo an intramolecular nucleophilic substitution reaction or theory.
Also included in the present invention are so-called timing DIR compounds, which are compounds that release development inhibitors upon reaction.

Also, JP-A-58-160954, JP-A No. 58-162')
Timing D in which a timing group as described above is bonded to a coupler core that produces a completely diffusible dye when reacted with an oxidized color developing agent described in No. 49.
It also includes IR compounds.

The amount of the DIR compound contained in the light-sensitive material is preferably in the range of 1.times.10@-gin mole to 10.times.10' mole per mole of silver.

The silver halide color photographic light-sensitive material used in the present invention may contain various other photographic additives, such as antifoggants, stabilizers, and ultraviolet absorbers described in Research Disclosure No. 17643. Agents, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents, and the like can be used.

In the silver halide color photographic light-sensitive material used in the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, and proteins such as albumin and casein. , hydroxyethylcellulosenyl alcohol, polyvinylimidazole, polyacrylamide, and other single or copolymer synthetic water-based polymers.

Examples of the support for the silver halide color photographic light-sensitive material used in the present invention include baryta paper, polyethylene-coated paper, etc.
1 paper, polypropylene synthetic paper, a transparent support with a reflective material or a reflective material, such as a glass plate, a polyester film such as cellulose acetate, cellulose nitrate or polyethylene terephthalate, a polyamide film, a polycarbonate film, a polystyrene film, etc. The substrate may be a conventional transparent support. These supports are appropriately selected depending on the intended use of the photosensitive material.

For coating the silver halide emulsion layer and other photographic constituent layers used in the present invention, a number of coating methods can be used, such as single coating, air doctor coating, curtain coating, and hopper coating. Also, Yoneda Special S1 2nd.
761,791 and 2,941,898, in which two or more layers are coated simultaneously, can also be used.

In the present invention, the coating position of each emulsion layer can be determined at will. For example, in the case of a full-color photosensitive material for photographic paper, it is preferable to sequentially arrange a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer from the support side. . Each of these photosensitive silver halide emulsion layers may consist of two or more layers.

In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as constituent layers. Hydrophilic colloids that can be used as a binder in the emulsion layer as described above can be similarly contained in these constituent layers, and can also be contained in the emulsion layer as described above. Various photographic additives can be included.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, if the light-sensitive material is processed by the so-called internal ring image method containing a coupler in the light-sensitive material, the following steps are necessary: It can be applied to any silver halide color photographic material such as color paper, color negative film, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, and reversal color paper.

[Specific Effects of the Invention 1] As explained above, according to the processing method of the present invention, the color development solution has excellent storage stability, is immersed in the photographic characteristics of staining and maximum color density caused by bleach-fixing, and can be processed particularly quickly. A method for processing silver halide color photographic materials suitable for processing could be provided.

[Specific Examples of the Invention] Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention are not limited thereby.

[Example 1] On a paper support laminated with polyethylene.

The following layers were sequentially coated from the support side to prepare comparative light-sensitive material samples.

? ? 1...1.19/12 gelatin, 0. 35(
] / blue-sensitive silver chlorobromide emulsion (A
95 mol% as IJ Cl) and Q. 1. dissolved in 60 Q/v' of dioctyl phthalate. OXlo-:! A layer containing the following yellow coupler (Y-1) in mole (J/f).

Layer 2: Intermediate layer consisting of 0.52 Mf gelatin.

Layer 3...1.20/m2 gelatin, 0.2U/m'
green-sensitive silver chlorobromide emulsion (97 mol % as ΔgC2) and 1.2X 10-3 mole g/i12 of the following magenta coupler (M- A layer containing 1).

Layer 4...1.2! Intermediate layer consisting of gelatin of It /f.

Layer 5...gelatin of 1.2(1/f), 0.24(1
/v' red-sensitive silver chlorobromide emulsion (98 mol% as silver chloride)
) and 1,2X 10-3 mole CI/m' of the following cyan coupler (C'-13) dissolved in dibutyl phthalate of 0.22 (]/m'.

Layer 6... 0 dissolved in U cyan of 12s/'2 and dioctyl phthalate of (2)s/''I',
32! J, '+1' Tinuvin 328 (Abagai 1
1. A layer containing 7...Q, 4Sg/n' cyanide.

IrO, 1 stool 1] As a tA agent, 2,1]-diku[]
1-1-5-e Droxy-5-1-riazyptrium was added to 1 m2,1] and 7 m of J:0015 per Uf-on, respectively.

C'-1 C! Create color paper for comparison as described above and see 3.
In the same manner, the above cyan coupler (C'-1) was changed to a cyan coupler as shown in Table 1 below, and experimental samples defined as inventive samples and comparative samples were prepared and used.

Next, these samples were subjected to wedge-shaped exposure using a conventional method, and then subjected to the following treatment (1).

Processing 1 culm Processing temperature Processing time 1] Color development 35°C/15 seconds [2] Bleach-fixing 35″C; 45 seconds [3] Washing 30
℃-100 seconds [4] Drying 60-80℃-to seconds The color developing solution and bleach-fixing solution used had the following composition.

(Color developer) - Potassium chloride 2.0 g - Potassium sulfite (listed in Table 1) - Sodium polyphosphate 2.0 (1) Color developing agent (Exemplary compound A-1>5.f3q - Potassium carbonate
30 (] Add water to make 1y, and adjust to CIH 10.15 with potassium hydroxide and 50% i acid.

[Bleach-fix solution 1 ethylenediaminetetraacetic acid M ferric ammonium 2 water J:A 60. O
.

Ethylenediaminetetraic acid 'fIi 3.0 (] Ammonium diosulfate (70% solution M) 100.0.1 Ammonium sulfite (40% solution) 27.5d Add water to bring the total volume to 1], and adjust the pH with potassium carbonate or glacial acetic acid. are adjusted as described in Table 1.

However, in the color developing solution, the bleaching constant @ solution is added at 0.31Q and CO2' per 12 parts of the color developing solution. (1])l)I
II) was added, and 25QvQ of the color developing solution was mixed into the bleach-fixing solution, and after storage at 45° C. for 3 days, development was performed.

Using a Sakura Photoelectric Yodometer PDA-65 (manufactured by Roku Konishi Photography 2] 1) of the sample after the development process, the cyan density in the unexposed area and the magenta density in the unexposed area where the coupling speed is fast and fogging is a problem are measured. The density and yellow density of the highest density area where the developing speed is slow and it is difficult to develop color density were measured.

The results are summarized in Table 1.

Margin below 1. As is clear from 2-4 and 1, the 3g degree of sulfite in the coloring phenomenon liquid is in the range of 4X10-3 mol,/'1 or less, and the light-sensitive material contains the general formula [C- 1] and [C-II], and the pH of the bleach-fixing solution is 4.5 to 6.8.
It can be seen that when the color development time is within the range of 45 seconds, sufficient yellow color M density is obtained, and cyan fog and magentastin occur less in unexposed areas. . However, the sub-1aW1 salt concentration in the color developing solution, the presence or absence of the cyan coupler represented by the general formula [C-1] or [Q-II] in the photosensitive material phase, the presence or absence of the cyan coupler according to the present invention, or the bleach-fixing solution When the pH is outside the scope of the present invention, the yellow dye concentration is insufficient,
It can be seen that problems such as excessive magentastin and cyan fog occur, reducing commercial value.

[Example 2] Color developing agent (A-1) in the color developer used in Example 1
) was changed to (B-1) or (B-2) below and a similar experiment was conducted, and the magentastin in the unexposed area deteriorated by 0.02 in both cases.

Similarly, the same experiment as in Example 1 was carried out by changing the color developing agent (Δ-1) in Example 1 to exemplified compounds (A-2), (A-4), and (8-15), respectively. As a result, similar results were obtained.

([3-1) (B-2) [Example 3] The silver halide composition of the blue-sensitive layer in the silver-genride color photosensitive material rl used in Example 1, Experiment N086 is shown in Table 2 below.
The same experiment was carried out in the same manner as in Example 1 except for the following changes. The results are summarized and shown in Table 2.

Below is the margin (μ, +- Table 2 As is clear from Table 2, when the silver halide composition of the silver halide color photographic light-sensitive material contains 80 mol% or more of silver chloride, the yellow dye concentration becomes almost sufficient. However, it can be seen that sufficient dye density cannot be obtained when the silver chloride content is lower than this.

Furthermore, when the content is 90 mol % or more, a better dye density is obtained, and when it is 95 mol % or more, it is found that the concentration is particularly good. This effect was obtained by similarly changing the silver halide composition of the red-sensitive layer and the green-sensitive layer, and the same results were obtained for the cyan dye density and magenta dye density. Above all,
It has been found that when the silver chloride content of the total silver halide emulsion is 80 mol % or more, especially 90 mol % or more, especially 95 mol % or more, all layers give a preferable dye density and give a complete black color. .

[Example 4] Exemplary compound (A'-2) was added to the color developing solution used in Example 1.
), (A'-4) and (A'-9) (all triadylstilbene fluorescent brighteners) at 2 (J/L;
When an experiment was carried out in the same manner as in Example 1 except that the magenta tin was added to the
2, or 20% to 40%.

[Example 5] Exemplary compounds (I-1), (I-5) and (I-2) were added to the color developing solution used in Example 1 and Experiment N006.
2(]/Il was added and a similar experiment was conducted, but when the remaining amount of color developing agent in the color developing solution after storage was measured, the decomposition rate was improved by 3 to 4%. The magenta density (stain) also decreased roughly by about 0°01, or about 20%.

[Example 6] Exemplary compounds (B-I-2), (B-■-3) and (B-II-3) were added to the color developing solution used in Example 1 and Experiment N096.
When a similar experiment was carried out by adding O and Sa/fl, respectively, an improvement was observed in which the magentastin density in the unexposed area was roughly reduced by 0.01 to 0.02.

[Example 7] Exemplary compounds (D-3) and (D-7) were added to the color developer used in Example 1 and Experiment No. 6 at 12v/ffi, respectively.
When a similar experiment was conducted with Magentastin, the degree of coloring of the color developing solution was improved, and Magentastin et al.
It decreased by 1.

[Example 81 The exemplary cyan couplers (C'-1> of the photosensitive material used in Example 1, Experiment No. 016) were replaced with (C-72), (C-2),
When (C-10) and (C-16) were changed and experiments were carried out using the same #snatant, almost the same results were obtained.

Revision Applicant Roku Konishi Photo Industry Co., Ltd. Agent Patent Attorney Miyao Ichinose Lρt+L:i' Procedure Nef1] Formal Form (Method) % Formula % 1, Indication of Case 1985 Patent Application No. 92937 2, Invention Name Processing method for silver halide color photographic light-sensitive materials 3, Relationship with the case of the person making the amendment Patent originator Address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo Name
(127) Representative Director of Konishiroku Photo Industry Co., Ltd.
Keio Benko 4, Agent 102 Address 1-1 Kudankita 4-chome, Chiyoda-ku, Tokyo (Shipping date) June 24, 1986 6, Subject to amendment

Claims (1)

[Claims] (1) After imagewise exposing a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer, a silver halide color is subjected to a process including at least a color development step and a bleach-fixing step following the color development step. In the method for processing a photographic light-sensitive material, at least one of the silver halide emulsion layers is a silver halide emulsion layer containing silver halide grains consisting of 80 mol% or more of silver chloride, and the silver halide emulsion layer At least one layer of the following general formula [C
-1] and [C-2], and the color developer used in the color development step contains a sulfite, and the concentration of the sulfite is equal to or less than the color developer. The bleach-fixing solution used in the bleach-fixing step has a pH in the range of 4.5 to 6.8. A method for processing silver halide color photographic materials. General formula [C-1] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [C-2] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1_3 represents a ballast group, and Z is a hydrogen atom or Represents a group that can be separated by coupling with an oxidized product of an aromatic primary amine color developing agent, and in the formula,
Y is -COR_1_4, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -SO_2R_4
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CONHCOR_1_4 or -CONHSO_2R_
1_4 (R_1_4 represents an alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group, R_
1_5 represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and R_
1_4 and R_1_5 may be combined with each other to form a 5- or 6-membered ring. ). ]