JPS6314148A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable quick development and to improve fogging by consisting a silver halide emulsion layer of specific silver halide particles, magenta coupler and compd. contg. a specific alkyl group. CONSTITUTION:The silver halide emulsion layer is the silver halide emulsion layer contg. the silver halide particles consisting of >=80mol% silver chloride. The magenta coupler expressed by formula I is incorporated into at least one silver halide emulsion layer. The concn. of sulfite in the liquid color developer is <=17X10<-3>mol per l of the liquid color developer and the compd. expressed by formula II is incorporated therein. The pH of a bleach-fix bath is specified to a 4.5-6.8 range. In formula, Z denotes a nonmetallic atom group necessary for forming a nitrogenous heterocycle, X denotes a hydrogen atom of substituent which can be eliminated by the reaction with the oxidant of the color developing agent, R denotes a hydrogen atom or substituent, R1 denotes an alkyl group of 1-3 which may have a substituent. The photosensitive material suitable for the quick processing is thus obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for processing silver halide color photographic light-sensitive materials. The present invention relates to a method for processing silver halide color photographic material X1 with improved properties.

[Background of the Invention] In recent years, there has been a desire in the industry 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 our efforts to improve our services to users, we develop them on the same day that we receive a complaint. 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, and there is an urgent need to develop technology that can process the item more quickly.

Looking at the conventional technologies for rapid processing of silver halide color photographic light-sensitive materials, there are: [1] technology based on improvements in silver halide color photographic light-sensitive materials, [2] technology using physical means during development processing, and [3] development processing. For improving the composition of processing liquids used. ! Regarding [1] above, there are two main techniques: (1) Improvement of silver halide composition (for example, silver halide fine graining technology as described in JP-A-51-77223, and JP-A-58-184142). (1) use of additives (for example, technology for reducing silver bromide of silver halide as described in Japanese Patent Publication No. 56-18939);
The technique of adding 1-aryl-3-pyrazolidone having a specific structure as described in No. 4339 to a silver halide color photographic light-sensitive material, and the technique of adding 1-aryl-3-pyrazolidone having a specific structure as described in JP-A-57-144547 and JP-A-57-144547;
B-50534, 5B-50535, 58-5
Technology of adding 1-arylpyrazolidones as described in No. 0536 into a silver halide color photographic light-sensitive material),
■Technology using fast-reactive couplers (for example,
107834, JP-A-50-123342, JP-A No. 51-
102636 (a technique using a high-speed reactive yellow coupler), (2) a technique for thinning a photographic constituent layer (for example, a technique for thinning a photographic constituent layer described in Japanese Patent Application No. 60-204992), etc. Regarding [2], the processing liquid stirring technique (for example, FI4, the processing liquid stirring technique described in Japanese Patent Application No. 61-23334)
Regarding the above-mentioned item [3], 1) a technique using a development accelerator, 2) a technique for concentrating a color developing agent, and 2) a technique for reducing the concentration of halogen ions, especially bromide ions, etc. are known.

Processing of light-sensitive materials basically consists of two steps: color development and desilvering, and desilvering consists of bleaching and fixing steps or bleach-fixing steps. In addition to this, additional processing steps such as rinsing treatment, stabilization treatment, washing with water or stabilization treatment as an alternative to washing with water, etc. are added. That is, in color development, the exposed silver 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 the reduction of silver halide are eluted and accumulated in the current a'a. In addition, components such as inhibitors contained in the photosensitive material mist are also eluted into the color developing liquid and accumulated. In the desilvering step, silver produced by development is bleached with an oxidizing agent, and then all silver salts are removed from the photosensitive material as soluble silver salts with a fixing agent. A one-bath bleach-fixing method is also known in which the bleaching step and the fixing step are carried out simultaneously.

Among the rapid processing techniques described in [1] above, technique Ii (for example, JP-A No. 58-95345,
JP-A-60-19140, JP-A-58-95136, etc. (described in Japanese Patent Application Laid-open Nos. 1987-19140 and 1989-95136, etc.) provide particularly excellent speed-up performance. However, when such high silver chloride-containing photosensitive materials are used, the ram
s causes a physical development reaction, which has the disadvantage that the dye density becomes insufficient. For this reason, high silver chloride-containing photosensitive materials are forced to be used in a concentration range where ilI salt 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 performed subsequently, the preservative in the color developing solution will be removed. It was found that due to the low concentration of sulfite, the main coloring agent was oxidized, and so-called bleaching edge blur was likely to occur.

In particular, due to recent demands for low pollution and cost reduction, there is a trend toward low replenishment or high regeneration rates for bleach-fix solutions, and in such cases, much of the color developing solution accumulates in the bleach-fix solution. It has become. 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 materials (for example, between the beginning of the week when there are many orders and the weekend when there are fewer orders). The amount of color developing solution in the bleach-fix solution increases due to differences in processing ships, differences in processing amount between high season and off season, etc.). Under such circumstances, the photographic properties deteriorate significantly, such as the bleaching blade blur becoming even more severe, and conventionally known techniques (for example, JP-A-1988-1999-1)
136031, British Patent No. 1.131,335, U.S. Patent No. 3,293,036, etc.), etc.), etc.) are no longer able to compensate.

Another problem is that high-silver chloride-containing photosensitive materials, which are extremely effective as speed-up techniques, can be used over time if heavy metal ions (for example, ferric ions or copper ions) are mixed into the color developing solution. It was found that the occurrence of magentastin during bleach-fixing became more pronounced. Particularly in recent years, there has been a trend toward low replenishment of color developing solutions due to demands for lower pollution and lower costs. Along with this, the amount of heavy metal ions accumulated in color developing solutions also tends to increase.
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 when processed with 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 silver halide color photographic materials in which less fogging occurs even when a bleach-fixing solution is refilled at a low level. 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 a silver halide color photographic light-sensitive material in which the generation of magentastin in unexposed areas due to bleach-fix solution treatment is improved even when heavy metal ions are mixed into the color developing solution. It is in.

[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, the silver halide emulsion layer is a silver halide emulsion layer containing 80 mol % or more of silver halide S1 grains made of silver chloride, and at least one layer of the silver halide emulsion layer has the following general The color developing solution containing the magenta coupler represented by the formula [M] and used in the color developing step has a sulfite concentration of 17 per 12 of the color developing solution.
The bleach-fixing solution used in the bleach-fixing step contains 1) a silver halide in which H is in the range of 4,5 to 6,8; The present inventors have discovered that the present invention can also be achieved by a method for processing color photographic material H.

[In the formula, 2 represents a non-metallic atomic group necessary to form a nitrogen-containing heterocycle, and the 4' ring formed by Z may have a substituent.

X represents a hydrogen atom or a substituent that can be removed by reaction with an oxidant in the color development process.

Further, R represents a hydrogen atom or a substituent. ] General formula [I
] R1-NH-Of-1 (In the formula, R1 represents an alkyl group having 1 to 3 carbon atoms which may have a substituent, 1°) [Specific structure of the invention] Halogenation of the present invention In the processing method for silver color photographic materials, in order to enable rapid development processing, the silver halide emulsion layer contains 80 mol% or more of j3! Halogenated m consisting of silver oxide
contained particles.

In the present invention, the preservative is used to reduce the dye density due to the silver enamel reaction, which tends to occur when using such photosensitive materials containing high silver chloride! ll! The amount of sulfate was prevented by reducing the amount of sulfate to 17×10 −3 mol or less per 12 of the color developing solution, and by using specific hydroxylamines, and the deterioration of the preservative in the color developing solution was also improved.

Furthermore, in the present invention, one of the problems caused by using a photosensitive material containing high silver chloride, namely, the occurrence of magentastin during bleach-fixing processing, which occurs when heavy metal ions are mixed into the color developing solution and over time, is solved. This can be prevented by using a specific magenta coupler, and in addition, in the present invention, the occurrence of bleaching edge blur, that is, staining in the bleach-fix solution, can be prevented by using a specific magenta coupler. By keeping the range within this range, it can be more completely prevented.

The color developing solution used in the present invention has a sulfite concentration of 17 x 10 -3 mol or less, preferably 7 x 10 -3 mol or less, particularly preferably 4 x 10 -3 to 0 mol per 12 of the color developing solution. It is a mole.

In conventional color developing solutions, sulfite is added as one of the preservatives, usually at a concentration of 2X10-2 to 4X1 per liter of color developer.
Although scratches of about 0-2 mol were used, when the conventional system was applied to the present invention, a decrease in color density occurred, which was thought to be caused by dissolution of silver chloride. The present invention solves the above problems by lowering the sulfite concentration to a specific range, using specific hydroxylamines, using a specific magenta coupler in the light-sensitive material, and furthermore, by using a specific I)H bleach-fix solution. This problem was solved by using a combination of .

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

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 phenylenediamine-based compounds that do not have water-soluble groups such as N,N-diethyl-p-phenylenediamine,
Not only does it have the advantage of not causing contamination of photosensitive materials and does not cause rashes on the skin, but especially in the present invention, by combining it with the compound represented by the general formula [E], the object of the present invention can be efficiently achieved. 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 include -(CH2) n -CH20f-1°-(CH2 )I
ll -NHSO2-(CH2)n-CHa, -(CH2)51 0- (CH2)n -CH3
, -(CH201-120> n Cm H2a++1
(m and hin each represent an integer greater than or equal to 0.)
Preferred examples include -COOH group and -3O3H group.

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

Exemplary color development agent (A-1) HsCz CtH, NHSO, CH.

(A-2) Hs　C2C2H-OH (A-3) H, C, CtH, OH (A-4) H5C2C, H40CH.

(A-5) H, C2C, H, 5O3H (A-6> H, CC, H, OH N.H.

(A-7) HOH4C2C2H4OH (A-8) HIC4C<HsS03H (A-9) H, C, C, H, S○, H (A-10) HC82COOH (A-11) (A-12) NH7 (A -13) HS C< )CH, CH, 0-)-C2H% (A-1
4) Hs C< 7) CHz CH20fC2Hs (A-1
5) H%C2C2H4N HS 01 CHs\N/ (A-16) H2O2C,+(,OH Among the color developing agents exemplified above, preferred for use in the present invention are exemplification No., (A-1), and (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 coloring agent having a water-soluble group used in the present invention is:
Usually 0.3X per 11 coloring liquids 10-2 to 3X1
It is preferable to use the amount in the range of 0" mol, but from the viewpoint of rapid processing, the amount is 0.8
A range of 2 x 10'' moles is more preferred.

In the present invention, when a triazylstilbene fluorescent bottle whitening agent 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.

[General formula
oxy, etc.), aryloxy groups (e.g. phenoxy, p-
sulfophenoxy, 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, cyclohexylamino, β-hydroxyedylamino, di(β-hydroxyethyl)amine, β-sulfoethylamino, N-(β-sulfoethyl)-N'-methylamino, N-(β- and droxyethyl-N'-methylamino, etc. ), arylamino groups (e.g. anilino, 0-1
l-1p-sulfoanilino, 0-, toll-chloroanilino, 0-1ta-, p-toluidino, 0-1l-1p
-carboxyanilino, O+, l-1p-hydroxyanilino, sulfonaphthylamino, o+, l-1p-aminoanilino, 0-1o-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.

＝ ＝＝
=^
＾ Engineering＞
a co I kuku kuku
Ku<<
2. The triadylstilbene-based brightener represented by the general formula [XV] can be synthesized by the usual method described in, for example, "Fluorescent Brighteners" edited by Japan Chemical Industry Association (published in August 1976), page 8. can do.

These triazylstilbene type brighteners are preferably used in an amount of 0.2 to 6 g, particularly preferably 0.4 to 3 g, per 12 of the color developing solution of the present invention.

The color developer used in the present invention can contain the following developer components in addition to the above components.

Examples of alkaline agents include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, silicates,
Sodium metaborate, potassium metaborate, phosphoric acid 3
Potassium, tripotassium phosphate, borax, etc. can be used alone or in combination within a range that maintains the pH stabilizing effect.

Furthermore, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, and borates are used for purposes such as preparation needs or to increase ionic strength. can do.

Additionally, inorganic 13J and organic antifoggants can be added as necessary.

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

Development accelerators are described in U.S. Patent No. 2. (149, 604
No. 3,671,247, Equity Ill 44-9
Various pyridinium compounds as typified by Publication No. 503, other cationic compounds, cationic dyes such as 71 nozafuranine, and medium+'IJ! compounds such as thallium nitrate. ,
U.S. Patent No. 2.533.990@, U.S. Patent No. 2.531.8
No. 32, No. 2,950,970, No. 2,577.
No. 127 and nonionic compounds such as polyethylene glycol, its derivatives, and polythioethers described in Japanese Patent Publication No. 44-9504, solvents and organic amines, ethanolamine, ethylenediamine, and These include tanolamine, l-jetanolamine, and the like. Also, U.S. Patent No. 2,304,92
In addition to benzyl alcohol and phenethyl alcohol described in No. 5, acetylene glycol,
Examples include medyl edyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, and amines.

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, since organic solvents with poor solubility have poor solubility in water, they not only require a stirring device to prepare the color developing solution itself, but are also troublesome. Due to the poor quality, there is a limit to the development promotion effect.

Furthermore, poorly soluble organic solvents reduce the biochemical oxygen demand ff
The pollution load value such as i (BOD) is large, and it is impossible to dispose of it in sewers or rivers, etc., and there are problems such as requiring a large amount of labor and cost to treat the waste liquid. Therefore, it is preferable to reduce or eliminate its use as much as possible.

In the color developing solution used in the present invention, the following general formula [
The compound represented by 1F (hereinafter referred to as the compound of the present invention).

) is used.

In the general formula [I], R1 is an alkyl group having 1 to 3 carbon atoms which may have a substituent (for example, a methyl group, an ethyl group,
n-propyl group, 1so-propyl group); substituents for the alkyl group include sulfonic acid group, hydroxy group, alkoxy group (methoxy group, ethoxy group, propyloxy group, etc.) carboxyl group, amino group, etc. can be mentioned.

Regarding the compound of the present invention represented by general formula [I], for example, U.S. Pat.
Examples include hydroxylamines described in No. 4, No. 3,287,124, and the like.

Preferred specific examples of the compound of the present invention represented by the general formula [I] are shown below.

(I-1) CH3-NH-OH(I-2)
C2R5-NH-OH(I-3)! 5o-C
3R7-NH-OH(I-4) n-03H7
-NH-OH(I-5) HO-CH2-NH-
OH(I-6) CH3-OC; LH4N H
-OH (I-7) HO-02H4-NH-OH(I-
8) HOOC-02H4-NH-OH (I-9) HO35-C2H4-NH-OH (I-10) H2N-C5Hs -NH-0H
(I-11) C2H5-0-C2H4-NH0
H (I-12) HO-C2H4-0-C2H4N
H-OH These compounds of the present invention are usually used in the form of salts such as hydrochloride, sulfate, D-toluenesulfonate, oxalate, phosphate, and acetate.

The compound III of the present invention in the color developing solution is preferably used at a concentration similar to that of hydroxylamine commonly used as a preservative, for example 0.2Q714 to 50a/i, more preferably l/l-30a. /l, more preferably 2 g/l to 20 a/l.

The coloring phenomenon liquid used in the present invention has the following general formula [8-
When containing at least one compound selected from the compound represented by II and the compound represented by the general formula [B-I[], the desired effects of the present invention can be better achieved, and the automatic phenomenon can be prevented. Organic acid iron complex salts (e.g. iron ethylenediaminetetraacetate (I
II) complex salt) is particularly preferably used because it also has the effect of stabilizing the color developing solution of the present invention even when it is mixed into the color developing solution.

In general formula [8-II, [B-11, R1, R2,
R3, R4, R5 and R6 are each a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -OR? , -COORa, R7, Ra, Rs and Rlo are each a hydrogen atom or a carbon atom number of 1 to 18
represents an alkyl group.

However, when R1 and R2 represent -OH or a hydrogen atom, R3 represents a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -0R7, IG.

Examples of the alkyl groups represented by R1, R2, R3, R4, R5 and R6 include methyl group, ethyl group, 1s
o-propyl group, n-propyl group, [-butyl group, n-
Butyl group, hydroxymethyl group, hydroxyethyl group,
Examples include methyl carbon MM, benzyl group, and R
The alkyl group represented by 7, Ra, Rs and Rlo has the same meaning as above, and further includes an octyl group.

Further, the phenyl group represented by R1, R2, R3, R+, R5 and R6 includes a phenyl group, a 2-hydroxyethyl group, a 4-aminophenyl group, and the like. Representative specific examples of the compounds represented by the general formulas [8-II and [8-III] are listed below, but the compounds are 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-carboxymethyl ester (B-I-5) 1.2.3-trihydroxybenzene-5-carboxy -〇-Butyl ester (B-I-6) 5-t-Tublu 1.2.3 trihydroxybenzene (B-I-7) 1.2-Dihydroxybenzene-3,4,5-trisulfonic acid (B -I-8> 1.2-dihydroxybenzene-3,5,6-trisulfonic acid (B-1t-1) 2.3-dihydroxynaphthalene-6-sulfonic acid (B-II-2) 2.3. 8-trihydroxynaphthalene-6-sulfonic acid (B-II-3) 2.3-dihydroxynaphthalene-6-carboxylic acid (B-I-4) 2.3-dihydroxy-8-isopropyl-naphthalene (B-1 [-5) 2,3-dihydroxy-8-chloro-naphthalene-6-
Among the above 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 above-mentioned compound is added at 5% per 1 part of the color developing solution.
It can be used in the range of 1 g to 20 g, preferably 10 mo to 10 g, and preferably 20 mo to 3 g to give good results.

The above compounds 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-
Other chelating agents such as phosphonocarboxylic acids such as tricarboxylic acids, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid may be used in combination.

When the color developer according to the present invention contains a compound represented by the following general formula [0], it not only exhibits the effects of the present invention better, but also prevents air oxidation of the color developer. It is more preferably used because it shows an improvement effect.

General formula [D] (wherein, R1 is a hydroxyalkyl group having 2 to 6 carbon atoms,
R2 and R3 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group, or an integer of the formula, X and 2 are each a hydrogen atom, and 1 to 6 carbon atoms.
represents an alkyl group or a hydroxyalkyl group having 2 to 6 carbon atoms. ) Preferred specific examples of the compound represented by the general formula [D] are as follows.

(D-1) Ethanolamine, (0-2) Jetanolamine, (D-3) Triethanolamine, (D-4) Di-isopropanolamine, (D-5) 2
-Methylaminoethanol, (D-6) 2-ethylaminoethanol, (D-7) 2-diethylaminoethanol, (D-8) 2-diethylaminoethanol, (D-
9>1-diethylamino-2-propanol, (D-10) 3-diethylamino-1-propanol, (D-11) 3-dimethylamino-1-propanol, (D-12) Isopropylamino Ethanol, (D-1
3) 3-amino-1-propatol, (D-14)2-
Amino-2-methyl-1,3-propanediol, (D-15) Ethylenecyamine titreitsbrobanol, (D-16) Benzyljetanolamine, (D-1
7) 2-amino-2-(hydroxymethyl)-1,3
-Propanediol.

From the viewpoint of the desired effect of the present invention, these compounds represented by the general formula [0] should be used in an amount of 3 to 1 per 111 color developing solutions.
Preferably used within the range of 009, more preferably 6g
It is used in the range of ~50g.

In general, the color developing solution of the present invention may contain ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other components as required.
The compounds described in each publication can be used as a solvent for increasing the solubility of a developing agent.

Furthermore, auxiliary developers can also be used with the developing agent. These auxiliary developers include, for example, N-methyl-p-7 minophenol hexalphate (methol).
, phenidone, N,N'-diethyl-p-aminophenol hydrochloride, N,N.

N',N'-tetramethyl-p-phenylenediamine hydrochloride is known, and the amount added is usually 0.
．． 01 (preferably 1 to 1.OQ/l. In addition, if necessary, a competitive coupler, a fogging agent, a colored coupler, a development inhibitor-releasing coupler (so-called DIR coupler), or a development inhibitor-releasing compound may be added. etc. can also be added.

Zaranimata, other anti-stain agents, anti-sludge agents,
Various additives such as multilayer effect promoters can be used.

Each component of the above-mentioned color developing solution can be prepared by sequentially adding and stirring a certain amount of water. In this case, components with low solubility in water can be added by mixing with the above-mentioned wired solvent such as ethylene glycol. Also, more generally,
A concentrated aqueous solution of multiple components, each of which can coexist stably,
Alternatively, the color developing solution of the present invention can be obtained by preparing a solid state in a small container in advance by adding it to water and stirring it.

In the present invention, the above color developing solution can be used at any pH, but from the viewpoint of rapid processing, the color developer can be used at pl-19.5 to pl-13.
．． 0, more preferably pH 9.8
~13.0.

In the present invention, the processing temperature for color development is preferably higher than 30°C and lower than 50°C, as it enables rapid processing in a short time, but on the other hand, it is better not to be too high in terms of image storage stability. , it is preferable to process at a temperature of 33°C or higher and 45°C or lower.

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

Bleaching agents that can preferably be used in the bleach-fix solution used in the present invention are metal complex salts of organic acids.

The complex 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 organic acids used to form such organic acid metal salts 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 [31 Ethylenediamine-N-(β-oxyethyl)-N, N', N
' -Triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycincitric acid (or tartaric acid) [9] Ethyl ether diamine tetraacetic acid [10] Co-glycol ether diamine tetraacetic acid [11] Ethylenediamine tetrabrobionic acid [12]
Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriamine pentaacetic acid bentanatri-light salt [17] Ethylenediamine diacetic acid N-(β-oxyethyl)
-N, N', N' - Sodium triacetate [18] Sodium propylene diamine tetraacetate [19] Sodium nitriloacetate [20] Sodium salt of hexane diamine tetraacetate These bleaches are 5 to 450 Q/fl , more preferably 20 to 150 Ω/l. The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. In addition, a bleach-fix solution consisting of an ethylenediaminetetraacetate iron (I[[) complex salt bleach and a small amount of a halide such as ammonium bromide other than the silver halide fixing agent mentioned above, or conversely, a bleach-fix solution such as ammonium bromide, etc. A bleach-fix solution with a composition containing a large amount of a halide, and a special bleach-fix solution with a composition consisting of a combination of ethylenediaminetetraacetic acid iron (III) complex salt bleach and a large amount of a halide such as ammonium bromide, etc. 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 agent contained in the bleach-fixing solution is a compound that reacts with silver halide to form a water-soluble complex salt, such as potassium thiosulfate, thio Ift!, which is used in ordinary fixing processing. Typical examples include thiosulfates such as sodium and ammonium thiocyanate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, and thioethers. Are these fixatives 5M? ! The above is used in the amount that can be dissolved, but generally 30o~150Q
/12 is used.

The bleach-fix solution contains 8 acids, borax, sodium hydroxide,
Various pH 1lili agents such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. Also, hydroxylamine, hydrazine, aldehyde compound heavy sodium 5A
Preservatives such as acid adducts, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, organic solvents such as methanol, dimethylsulfamide, dimethylsulfoxide, etc. can be included as appropriate.

The bleach-fix solution used in the present invention includes JP-A No. 46-280, JP-A No. 4s-asoe@, JP-A No. 46-556, Belgian Patent No. 770,910, JP-A No. 45-8836,
Various bleach accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 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.

l1Hlj of the bleach-fix solution according to the present invention 4.5-6.
Used in a range of 8. This is because if the pH of the bleach-fix solution is lower than 4.5, the bleach-fix solution itself becomes unstable and becomes susceptible to stone formation, and if the pH of the bleach-fix solution is higher than 6.8, it is difficult to prevent magentastin. This is because it becomes impossible. In particular, in the present invention, it is particularly preferable that the E)H of the bleach-fix solution is in the range of 5.5 to 6.5, and the desired effects of the present invention are achieved.

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, more preferably 90 mol% or more, still more preferably 95 mol%
It contains the above.

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 less than 1 mol %, preferably 0.
It is 5 mol% or less. 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 crystals, twin crystals, or other crystals, and have [100] planes and [111
Any ratio of the three sides 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. Further, tabular silver halide grains (JP-A-58-
No. 113934 and Japanese Patent Application No. 170070/1983) may also be used.

The silver halide grains used in the present invention may be those obtained by any vA manufacturing method, such as an acidic method, a neutral method, or an 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 implant and mix silver ions and halide ions in amounts commensurate with the growth rate of silver halide grains, either sequentially or simultaneously, as described in No. 21.

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 as a silver halide emulsion in this specification 1111.

These silver halide emulsions consist of active gelatin: sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; double reduction sensitizers such as primary
Tin salts, thiourea dioxide, polyamines, etc.=jI Metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, etc., or e.g. Sensitizers with water-soluble groups such as ruthenium, palladium, platinum, rhodium, and iridium, specifically ammonium chloroparadate, potassium chlorooleate, and sodium chlorovaladate (the types of these substances differ depending on the amount). (acts as a sensitizer or fog suppressant, etc.) 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.). It may also be chemically sensitized.

The silver halide emulsion according to the present invention is subjected to chemical ripening by adding a sulfur-containing compound, and the silver halide emulsion containing at least one kind of human O-oxytetrazaindene and a mercapto group is prepared 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 at a rate of 5 x 10-3 to 3 x 10°3 per mole of silver halide in order to impart photosensitivity to the desired wavelength range. Optical sensitization may be achieved by adding molar amounts. Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of the sensitizing dyes advantageously used in the present invention include the following.

That is, examples of sensitizing dyes used in blue-sensitive silver halide emulsions include West German Patent No. 929.080, US Pat. No. 2.231, US Pat. No. 658, US Pat. No. .776, No. 2.519.001
No. 2,912゜329, No. 3,656,95
No. 9, No. 3,672,897, No. 3,694,2
No. 17, No. 4,025,349, No. 4,046.
No. 572, British Patent No. 1,242,588, Special Publication No. 4
Examples include those described in No. 4-14030 and No. 52-24844. Further, as sensitizing dyes used in green-sensitive silver halide emulsions, for example, U.S. Pat.
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes such as those described in Patent No. 2.739°149, Patent No. 2,945,763, and British Patent No. 505.979. Can be done. Furthermore, there is a sense of redness.

Examples of sensitizing dyes used in silver halide emulsions include, for example, U.S. Pat.
No. 378, No. 2,442.710, No. 2,45
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in Japanese Patent No. 4,629 and No. 2,776.280.

Furthermore, U.S. Patent Nos. 2,213,995 and 2,4
No. 93,748, 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. 54-8011
No. 8, No. 5B-153926, No. 59-116646
No. 59-116647 and the like.

Further, regarding the combination of carbocyanine having a benzimidazole nucleus with other cyanine or merocyanine, for example, Japanese Patent Publication No. 45-25831! , 47-1
No. 1114, No. 47-25379, No. 48-3840
No. 6, No. 48-38407, No. 54-34535,
No. 55-1569, No. 50-33220, No. 5G-38526, No. 51-107127, No. 5
No. 1-115820, No. 51-135528, No. 52
-104916, No. 52-104917, and the like.

Further, regarding combinations of benzoxazolocarbocyanine (oxa-carbocyanine) and other carbocyanines, for example, Japanese Patent Publication No. 32153/1986, No. 4
No. 6-11627, JP-A-57-1483, and regarding merocyanine, for example, JP-B No. 48-3840.
No. 8, No. 48-41204, No. 50-40662,
JP 56-25728, JP 58-10753, JP 58-91445, JP 59-116645, JP 5
No. 0-33828 and the like.

Regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publications Nos. 43-4932, 43-4933, 45-26470, 4
No. 6-18107, No. 47-8741, JP-A-59-
No. 114533, etc., and the method described in Japanese Patent Publication No. 114533, which uses 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 a fluorinated alcohol described in Japanese Patent Publication No. 40659/1984 is prepared in advance. It is used after being dissolved in a hydrophilic 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 is decolorized by 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.
No. 84, 609, No. 1,277.429, JP-A-4
No. 8-85130, No. 49-99620, No. 49
-114420, same No. 49-129537, same No. 5
No. 2-108115, No. 59-25845, No. 5
9-111640, U.S. Patent No. 59-111641, U.S. Patent No. 2,274.782, U.S. Patent No. 2.533.472
No. 2,956.079, No. 3,125,44
No. 8, No. 3.148.187, No. 3,177.0
No. 78, No. 3,247.127, No. 3.260.
No. 601, No. 3,540,887, No. 3.575
．． No. 704, No. 3.653.905, No. 3.71
8'', No. 472, and No. 4,070, No. 352.

These AI dyes are generally used at a concentration of 2 per mole silver in the emulsion layer.
It is preferable to use X 10-3 to 5X10-1 mol.

The photographic coupler used in the present invention is preferably a phenolic compound or a naphthol compound as the cyan coupler, for example, as disclosed in U.S. Pat. No. 2,369,929.
No. 2,434,272%, No. 2.474.29
No. 3, No. 2,895,826, No. 3,253,9
No. 24, No. 3.034.892, No. 3,311,
No. 476, No. 3.3868301, No. 3.419
．． No. 390, No. 3,458,315, No. 3,47
6.563, 3.531, 383, etc., and methods for synthesizing these compounds are also described in the same publication.

Hereinafter, the magenta coupler represented by the general formula [M] used in the silver halide emulsion layer of the present invention will be described.
In the magenta coupler represented by general formula CM), Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing (bromine) group, and the ring formed by Z is a substituent. It is good to have.

X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a coloring agent.

Moreover, R represents a hydrogen atom or a substituent.

Examples of the substituent represented by R include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group,
Acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group,
Spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, 'acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureido group group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group,
Examples include an alkylthio group, an arylthio group, and a heterocyclic thio group.

Examples of the halogen atom include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred.

Examples of the alkyl group represented by R include charcoal T, those with 1 to 32 carbon atoms, alkenyl groups, and alkynyl groups having 2 to 32 carbon atoms.
32, nocroalkyl group, and cycloalkenyl group preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms,
The alkyl group, alkenyl group, and alkynyl group may be linear or branched.

In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents [e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, and indigenous hydrocarbon compounds] In addition to those substituted through a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, those substituted through a hetero atom (specifically, hydroxy, alkoxy, and acyloxy , heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, which are substituted via an oxygen atom, nitro, amino (including dialkylamino, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino,
Acylamino, sulfonamide, imide, ureide substituted through the nitrogen atom, alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl, sulfamoyl, etc., substituted with W through the sulfur atom, phosphorus atom of phosphonyl, etc. )].

Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, hebcudecyl group, 1
-hexylnonyl group, 1.1′-dipe/thylnonyl group,
2-chloro-1-butyl group, trifluoromethyl group, l
-Engineering 1-oxytridenyl group, l-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-amylphenoxymethyl group, anilino group, l-phenylisopropyl group, 3-m-butanesulfonaminophenoquinpropyl group - group, 3-4.-(α-[4..(p-hydroxybenzenesulfonyl)phenoxyfudodecanoylamino)phenylpropyl group, 3-(4.-[α-(2.
・, 4...-Diamylphenoxy)butanamido]phenyl)-propyl group, 4-[α-(O-chlorophenoxy)tetradecanamidophenoxy]propyl group, allyl group, cyclopentyl group, cyclohexyl group, etc. .

The aryl group represented by R is preferably a phenyl group, and may have a substituent (eg, an alkyl group, an alkoxy group, an acylamino group, etc.).

Specifically, phenyl group, 4-(-butylphenyl group,
2.4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4.
-[α-(4...-t-butylphenoxy)tetradecanamidophenyl group and the like.

The heterocyclic group represented by R is preferably 5- to 7-membered, and may be substituted or fused.

Specific examples include 2-furyl group, 2-chenyl group, 2-pyrimidinyl group, and 2-benzothiazolyl group.

Examples of the acyl group represented by R include acetyl group, phenylacetyl group, dodecanoyl group, α-2,4-di-
Examples include alkylcarbonyl groups such as t-amylphenoxybutanoyl group, arylcarbonyl groups such as benzoyl group, 3-pentadecyloxybenzoyl group, and p-chlorobenzoyl group.

The sulfonyl group represented by R includes an alkylsulfonyl group such as a methylsulfonyl group and a dodecylsulfonyl group,
Examples include arylsulfonyl groups such as benzenesulfonyl group and p-toluenesulfonyl group.

Examples of the sulfinyl group represented by R include an ethylsulfinyl group, an octylsulfinyl group, an alkylsulfinyl group such as a 3-phenoxybutylsulfinyl group, an arylsulfinyl group such as a phenylsulfinyl group, and a m-pentadecylphenylsulfinyl group. can be mentioned.

The phosphonyl group represented by R is an alkylphosphonyl group such as a butyloctylphosphonyl group.

Examples include alkoxyphosphonyl groups such as octyloxyphosphonyl groups, sulfonyl groups, aryloxyphosphonyl groups such as phenoxyphosphonyl groups, and arylphosphonyl groups such as phenylphosphonyl groups.

The carbamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-methylcarbamoyl group, N,N-dibdelcarbamoyl group, N-(2-pentadecylocdylezyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N-(3-(2,4 -di-t-amylphenoxy)propyl)carbamoyl group, and the like.

The sulfamoyl group represented by white R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc.
For example, N-propylsulfamoyl group, N,N-diethylsulfamoyl group, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-7enylsulfamoyl group, Examples include moyl group.

Examples of spiro compound residues represented by R include spiro [
3,3]hebutan-1-yl and the like.

Examples of the bridged carbonized compound residue represented by R include bicyclo[2,2,1]heptan-1-yl, tricyclo[3
, 3,1,M°7]decane-1-yl, 7,7-dimethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.

The alkoxy group represented by R may be further substituted with the substituents listed above for the alkyl group, such as a methoxy group, a propoxy group, a 2-ethoxyethoxy group,
Examples include pentadecyloxy group, 2-dodecyloxyethoxy group, phenethyloxyethoxy group, and the like.

The aryloxy group represented by R is preferably phenyloxy, and the aryl group may be further substituted with any of the substituents or atoms listed for the aryl group in tiQ, such as phenoxy group, p-L- Examples include a butylphenoxy group, a pentadecylphenoxy group, and the like.

The heterocyclic oxy group represented by R preferably has a 5- to 7-membered heterocycle, and the heterocycle may further have a substituent, for example, 3゜4.5.6- Examples include tetrahydropyranyl-2-oxy group and 1-phenyltetrazol-5-oxy group.

The siloxy group represented by R may be further substituted with an alkyl group, and examples thereof include a trimethylsiloxy group, a triethylsiloxy group, a dimethylbutylsiloxy group, and the like.

The acyloxy group represented by R includes, for example, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc., and may further have a substituent, and specifically, an acedeloxy group, an α-chloroacedeloxy group, etc. group, benzoyloxy group, and the like.

The carbamoyloxy group represented by R may be substituted with an alkyl group, an aryl group, etc., such as an N-ethylcarbamoyloxy group, an N,N-diethylcarbamoyloxy group, an N-7enylcarbamoyloxy group, etc. Can be mentioned.

The amino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as ethylamino group, anilino group, -chloroanilino group,
Examples include 3-pentadecyloxycarbonylanilino group, 2-chloro-5-hexadecaneamide anilino group, and the like.

Examples of the acylamino group represented by R include an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group), and may further have a substituent, specifically an acetamido group, an α- Ethylpropanamide group, N-phenylacetamide group,
Examples include dodecanamide group, 2,4-di-t-amylphenoxyacetamide group, and α-3-L-butyl 4-hydroxyphenoxybutanamide group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group, which may further have a substituent.

Specific examples include a methylsulfonylamino group, a pentadecylsulfonylamino group, a benzenesulfonamide group, a p-toluenesulfonamide group, and a 2-methoxy-5-t-amylbenzenesulfonamide group.

The imide group represented by R may be open-chain or cyclic, and may have a substituent, for example, a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, a glutaric acid group. Examples include imide groups.

The ureido group represented by R is an alkyl group, an aryl group (
Preferred examples include N-ethylureido group, N-methyl-N-decylureido group, N-phenylureido group, and N-p-)dylureido group.

The sulfamoylamino group represented by R is an alkyl group,
It may be substituted with an aryl group (preferably a phenyl group), etc., such as N,N-dibutylsulfamoylamino group, N-methylsulfamoylamino group, N-phenylsulfamoylamino group, etc. .

As the alkoxycarbonylamino group represented by R,
It may further have a substituent, for example, a methoxycarbonylamino group, a methoxyethoxycarbonylamino group,
Examples include octadecyloxycarbonylamino group.

The aryloxycarbonylamino group represented by R may have a substituent, and examples thereof include a phenoxycarbonylamino group and a 4-methylphenoxycarbonylamino group.

The alkoxycarbonyl group represented by R may further have a substituent, such as a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloquinecarbonyl group, an octadecyloquinecarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxy Examples include carbonyl group.

The aryloquine carbonyl group represented by R may further have a substituent, such as a phenoxycarbonyl group,
Examples include p-chlorophenoxycarbonyl group and m-pentadecyloxyphenoxycarbonyl group.

The alkylthio group represented by R may further have a substituent, and examples thereof include an ethylthio group, a dodecylthio group, an octadecylthio group, a phenethylthio group, and a 3-phenoxypropylthio group.

The arylthio group represented by R is preferably a phenylthio group and may further have a substituent, for example, a phenylthio group,
Examples include p-methoxyphenylthio group, 2-L-octylphenylthio group, 3-octadecylphenylthio group, 2-carboxyphenylthio group, and p-acetaminophenylthio group.

The heterocyclic thio group represented by R is preferably a 5- to 7-shell heterocyclic thio group, which may further have a condensed ring or a substituent. Examples include 2-pyridylthio group, 2-benzothiazolylthio group, and 2,4-diphenoxy-1,3,5-)liapur-6-thio group.

Examples of the substituent that can be separated by reaction with the oxidized product of the coloring agent represented by X include a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.), an oxygen atom, a sulfur atom, or a fluorine atom. Examples include groups substituted via .

In addition to the carboxyl group, examples of the group substituted via a carbon atom include the general formula (R, . is the same as the above R, Z is the same as the above Z, R, . and R3 are a hydrogen atom, (representing an aryl group, an alkyl group, or a heterocyclic group), a hydroxymethyl group, and a triphenylmethyl group.

Examples of groups substituted via an oxygen atom include alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, alkyloxalyloxy groups, and alkoxyoxalyloxy groups. can be mentioned.

The alkoxy group may further have a substituent, for example,
Examples include ethoxy group, 2-phenoxyethoxy group, 2-cyanoethoxy group, phenethyloxy group, and p-chlorobenzyloxy group.

The aryloxy group is preferably a phenoxy group, and the aryl group is more! ! It may have a substituent.

Specifically, phenoxy group, 3-methylphenoxy group, 3
-dodecylphenoxy group, 4-methanesulfonamidophenoxy group, 4-[α-(3-pentadecylphenoxy)butanamide]phenoxy group, hequinadecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group , 1-naphthyloxy M,
l)-methoxyphenoquine group and the like.

The heterocyclic oxy group is preferably a 5-7R heterocyclic oxy group, which may be a condensed ring or may have a substituent. Specific examples include 1-phenyltetrazolyloxy group, 2-benzothiazolyloxy group, and the like.

The acyloxy group includes, for example, an acetoxy group, an alkylcarbonyloxy group such as a butazuroxy group, an alkenylcarbonyloxy group such as a cinnamoyloxy group,
Examples include arylcarbonyloxy groups such as benzoyloxy groups.

Examples of the sulfonyloxy group include a butanesulfonyloxy group and a methanesulfonyloxy group.

Examples of the alkoxycarbonyloxy group include ethoxycarbonyloxy group and benzyloxycarbonyloxy group.

Examples of the alkyloxalyloxy group include a methyloxalyloxy group.

Examples of the alkoxyoxalyloxy group include ethoxyoxalyloxy group.

Examples of the group substituted via a sulfur atom include an alkylthio group, an arylthio group, a heterocyclic thio group, and an alkyloxythiocarbonylthio group.

Examples of the alkylthio group include a butylthio group, a 2-cyanoethylthio group, a phenethylthio group, a benzylthio group, and the like.

The arylthio group includes phenylthio group, 4-methanesulfonamidophenylthio group, 4-dodecylphenethylthio group, 4-nonafluorobentanamidophenethylthio group, 4-carboxyfuvonylthio group, 2-ethoxy-5-L -butylphenylthio group and the like.

Examples of the heterocyclic thio group include l-phenyl-1,
Examples include 2,3,4-tetrazolyl-5-thio group and 2-benzothiazolylthio group.

Examples of the alkyloxythiocarbonylthio group include a dodenyloxythiocarbonylthio group and the like.

Examples of the group substituted via the nitrogen atom include those represented by the general formula -N.
' Here, R4' and R3 are hydrogen atoms, alkyl groups,
Represents an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, and R4 and 1
1s. may be combined to form a petero ring. However, R4
Both ・ and Rs・ are never hydrogen atoms.

The alkyl group may be linear or branched, and preferably has 1 to 22 carbon atoms. Further, the alkyl group may have a substituent, and examples of the substituent include an aryl group, an alkoxy group, an aryloxy group, an alkylthio group,
Arylthio group, alkylamino group, arylamino group, anrulamino group, sulfonamide group, imi/I, acyl group, alkylsulfonyl group, arylsulfonyl group,
Examples include carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkyloxycarbonylamino group, aryloxycarbonylamino group, hydroquinyl group, carboxyl group, cyano group, and halogen atom.

Specific examples of the alkyl group include ethyl group, octyl group, 2-ethylhexyl group, and 2-chloroethyl group.

The aryl group represented by R4 or R1 has preferably 6 to 32 carbon atoms, particularly a phenyl group or a naphthyl group,
The nucleol group may have a substituent, and examples of the substituent include those listed as substituents for the alkyl group represented by R4 or R6 above, and an alkyl group. Specific examples of the aryl group include phenyl group, l-naphthyl group, and 4-methylsulfonylphenyl group.

The heterocyclic group represented by R4 or R1 is preferably 5- to 6-membered, may be a fused ring, and may have a substituent. Specific examples include 2-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-benzodeazolyl group,
Examples include 2-bilinol group.

The sulfamoyl group represented by R1 or Rs' includes N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-arylsulfamoyl group,
, N-diarylsulfamoyl group, etc., and these alkyl groups and aryl groups may have the substituents listed for the alkyl groups and aryl groups. Specific examples of the sulfamoyl group include N,N-diethylsulfamoyl group, N-methylcarbamoyl group, N-
Examples include dodecylsulfamoyl group and N-p-1-norsulfamoyl group.

The carbamoyl group represented by R4 or R1 is,
Examples include N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, 8-arylcarbamoyl group, N,N-diarylcarbamoyl group, etc., and these alkyl groups and aryl groups can be substituted with the substituents listed above for the alkyl groups and aryl groups. Specific examples of the carbamoyl group which may have a group include N,N-diedyylcarbamoyl group, N-methylcarbamoyl group, N-dodenylcarbamoyl group, N-1)-cyanophenylcarbamoyl group,
N-p-t-norcarbamoyl group is mentioned.

Examples of the acyl group represented by R4 or R5 include an arylsulfonyl group, an arylcarbonyl group, and a peterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group have an it substituent. It's okay. Specific examples of the acyl group include hexafluorobutanoyl group, 2゜3.4.5.6-pentafluorobenzoyl group, acedel group, benzoyl group, naphthonyl group, 2-furylcarbonyl group, etc. It will be done.

Examples of the sulfonyl group represented by R4' or Rs. include an alkylsulfonyl group, an arylsulfonyl group, and a hetero!
Examples include Il sulfonyl group, which may have a substituent,
Specific examples include ethanesulfonyl group, benzenesulfonyl group, octanesulfonyl group, naphthalenesulfonyl group, p-chlorobenzenesulfonyl group, and the like.

The aryloxycarbonyl group represented by R1 or R5 may have any of the substituents listed above for the aryl group, and specific examples include phenoxycarbonyl and the like.

The alkoxycarbonyl group represented by R4 or R3 may have the substituents listed above for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, a benzyloxycarbonyl group, etc. Can be mentioned.

The heterozygote formed by combining R4 and R1 is preferably 5- to 6-membered, may be saturated or unsaturated, and may or may not have aromaticity, or,
Examples of the heterocycle, which may be a condensed ring, include N-7 thalimide group, N-succinimide group, 4-N-urazolyl group, t-S-hydantoynyl group, 3-N-2,4-dioxoxa Zolidinyl group, 2-N-1,1-dioxo-
3-(2H)-oxo-1,2-benzthiazolyl group,
1-pyrrolyl group, 1-pyrrolidinyl group, 1-pyrazolyl group, 1-pyrazolidinyl group, l-piperidinyl group,! −
Pyrrolinyl group, 1-imidazolyl group, 1-imidazolinyl group, l-indolyl group, l-isoindolinyl group, 2
-isoindolyl group, 2-isoindolinyl group, t-benzotriazolyl group, 1-benzimidazolyl group, I
-(1,2,4-1-riazolyl) group, IL(1,2
,3-)riazolyl) group, 1-(1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1.2.3.4-
Tetrahydroquinolyl group, 2-oxo-1-pyrrolidinyl group, 2-I H-pyridone group, phthaladione group, 2
Examples of these heterocyclic groups include alkyl groups, aryl groups, alkyloxy groups, aryloxy groups, acyl groups, sullafnyl groups, alkylamino groups, arylamino groups, acylamino groups, and sulfone groups. Amino group, carbamoyl group, sulfamoyl group,
It may be substituted with an alkylthio group, an arylthio group, a ureido group, an alkoxycarbonyl group, an aryloxycarbonyl group, an imido group, a nido a group, a cyano group, a carboxyl group, a halogen atom, or the like.

Examples of the nitrogen-containing T:chlorine ring formed by Z or Z include a pyrazole ring, imidazole ring, triazole ring, or tetrazole ring, and examples of substituents on which the ring may be present include those for the above R. The ones mentioned above are mentioned.

In addition, general formula [L1] and general formulas CM-1) to (M
-7), substituents on the heterocycle (e.g., R9R1 to
R1) is! When it has a moiety (R..., X and Z... have the same meanings as R, X and Z in the general formula []), it forms a so-called screw-type coupler, which is of course included in the present invention. In addition, the ring formed by z, Z., Z... and Zl in 7 below can further be a pond ring (for example, a 5- to 7-membered cycloalkene).
may be condensed, fPI has the general formula [H-cow]
In the formula, Rs and Ro are bonded to each other, and in the general formula [H--], R7 and R6 are bonded to each other! (eg, 5- to 7-membered cycloalkene, benzene) may also be formed.

What is represented by the general formula [bar] may be more specifically represented by, for example, the following general formulas CM-1) to [h-et al.].

General formula (M-1) General formula CM-2) General formula (M-3) HHII+ General formula [H-H] General formula [8-di] General formula between 88□ (M-g) H-N -74 In the general formulas (M-1) to (M-4), Rl'-n
* and X have the same meanings as R and X above.

Also, among the general formulas CM), the following general formulas [
h-ri].

General formula (?1-7) N N,,' where R,, X and 2. is the general formula CM)
and Z.

nri iia B Formula (M-1) ~ (M-6)
Among the magenta couplers represented by TE, a magenta coupler represented by general formula (M-1) is particularly preferred.

Also, in general formulas (M) to (M-'7))! Regarding the substituents on the elementary ring, in the general formula (t'l), R
However, in general formulas (M-1) to (M-7), R6
It is preferable that the following condition 1 is satisfied, more preferable is the case that the following conditions 1 and 2 are satisfied, and particularly preferable is the case that the following conditions 1.2 and 3 are satisfied.

Condition 1: The root atom directly connected to the abdominal ring is a carbon atom.

Condition 2: Only 10 hydrogen atoms are bonded to the carbon atom, or no hydrogen atoms are bonded to the carbon atom.

Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds.

The most preferable substituents R and R1 on the search ring are those represented by the following general formula (M-ff).

General formula (M-8) Ro R1°-C- II where n*, r<,. and R1 are each a hydrogen atom,
Halogen atom, alkyl group, cyclo, alkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro Compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloquine group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureido group, Sulfamoylamine/Jet
.

It represents an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, or a heterocyclic thio group, and at least two of R1°R1 and R8 are not hydrogen atoms.

Further, two of the above Re, Rle and fl II, for example R1 and R1°, may be combined to form a saturated or unsaturated ring (for example, cycloalkane, cycloalkene, heteroff1), and furthermore, the ring Ro may be bonded to to constitute a bridged hydrocarbon compound residue.

The group represented by R1 to R11 may have a substituent, and specific examples of the group represented by R1 to R0 and the substituents that the group may have include those in the general formula (M) above. Specific examples of the group represented by R and substituents are listed.

Also, for example, a ring formed by combining R1 and R8゜ and R1
Specific examples of the hydrocarbon compound residue formed by ~RIt and its optional substituents include cycloalkyl, cycloalkenyl, and heterocyclic group bridged groups represented by R in the above general formula (M). Specific examples of hydrocarbon compound residues and their it substituents are listed.

Among general formulas (M-8), (i) Re-
When two of R1 are alkyl groups, (ii) Rs~
111+, for example, when r(II is a hydrogen atom and Ike's 2Ro and R2° combine to form a cycloalkyl with the root carbon atom, the following is true.

Further preferred among (i) is the case where two of R1 to r (11) are alkyl groups and one of the atoms is a hydrogen atom or an alkyl group.

Here, the alkyl and cycloalkyl may further have a substituent, and specific examples of the alkyl, the cycloalkyl, and the substituent thereof include the alkyl, cycloalkyl, and its substituent represented by R in the general formula (M). Specific examples of t substituents are listed.

In addition, substituents in which the ring formed by Z in the general formula [Seki] and the ring formed by Zl in the general formula CM-'7), and the general formula (Ml) ~[:t'
As R7-R1 that can be ζ in l-"i), the following general formula C
Those represented by M-'l) are preferred.

General formula CM-'l ) -R'-So! -R'' In the formula, R1 represents alkylene, and R1 represents alkyl, cycloalkyl or aryl.

The alkylene represented by R1 preferably has 2 or more carbon atoms in the straight chain portion, more preferably 3 to 6 carbon atoms, and has 0 straight chain carbon atoms.
Regardless of branching. Moreover, this alkylene may have a substituent.

Examples of the substituent include R in the general formula (M) described above.
is an alkyl group, the alkyl group may have fil
List the ones shown as the ta group.

Preferred substituents include phenyl. .

Preferred specific examples of alkylene represented by R1 are shown below.

-clItcIl+c11knee+ -CIICII
+CII+-, (IICII+Cilnee,
-CII+Cl5C1hCIls Cd
The alkyl group represented by "1s C9II+ 1R" may be a straight chain or monobranched.

Specific examples include methyl, ethyl, propyl, 1so-propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, octadacil, and 2-hexyldecyl.

The cycloalkyl group represented by R1 is preferably a 5- to 6-membered one, such as cyclohexyl.

The alkyl and cycloalkyl represented by R'' may have a substituent, and examples thereof include those exemplified as the substituent for R1 above.

Specific examples of the aryl represented by R1 include phenyl and naphthyl. The aryl group may have a substituent. Examples of the substituent include Vsl, which is a linear or branched alkyl group, and those exemplified as the substituent for RI described above.

Moreover, when there are two or more substituents, those substituents may be the same or different.

Among the compounds represented by the general formula [t't+], those represented by the following general formula (t'1-IQ) are particularly preferred.

General formula (M-1o) In the formula, R and X have the same meanings as R and X in general formula CM), and RI, n 2 is n in general formula CM-'l)
l.

It has the same meaning as R1.

However, the numbers in the table represent the following groups.

-F -CI-
Br-CHs-CFs
-C* Hs14 15
1B-Cs H--(i)C-Ht-
(1)C,H嘗L@tIIttt) -(CH,)riOC+*Hts -CHtCH*CH30□C1IH11Cvl(Is -CH,CH,CH,SO*C)i,cH! 5OIC,
, H□-CHICH*CH*CH9OtCaH+tC@
HIs -CH-CH*CHtSO*C1*H*sCH.

（、；４　j’l　＊ CH.

CH.

161 1 (i2 C# -NHCOCFs -NHCOC3F,
-NHCO(Crt)IH-OCH,C0NHCH,C
H, OCH, -0038%215
21G-OCOC,,H,,-08O*C
Hs-SC, H,, -8C,, H□ - S Om C+ s Hs t The magenta coupler according to the present invention may be used alone or in combination with other magenta couplers outside the present invention. good.

Photographic magenta couplers that may be used in combination include pyrazolone, pyrazolinobenzimidazole,
Examples include compounds such as indacylons. As a pyrazolone magenta coupler, US Patent No. 2.600.
No. 788, No. 3,062,653, No. 3,127
, No. 269, No. 3,311,476, No. 3,41
9.391, 3.519.429, 3.5
No. 58,318, No. 3,684,514, No. 3,8
No. 88,680, JP-A No. 49-29639, l! l
No. 49-111631, No. 49-129538, No. 5
No. 0-13041, Special Publication No. 53-47167, No. 54
-10491 and No. 55-30615, and compounds in which colorless magenta couplers are substituted with arylazo at the coupling position are generally used as diffusion-resistant colored magenta couplers, such as those described in U.S. Pat. No. 2,801,171, No. 2,983,6
No. 08, No. 3.005.712, No. 3,684,5
14, British Patent No. 937.621, and JP-A-49-123625 and JP-A-49-31448.

Furthermore, a colored magenta coupler of the type described in US Pat. No. 3.4i9,391, in which the dye flows out into the processing solution by reaction of the oxidized product of the developing agent, can also be used.

As photographic yellow couplers, open-chain ketomethylene compounds have conventionally been used, and generally widely used benzoylacetanilide type yellow couplers and hibaloylacetanilide type yellow couplers can be used. Furthermore, 2-equivalent yellow couplers in which the carbon atom at the coupling position is substituted with a substituent that can be removed during the coupling reaction are also advantageously used.

Examples of these are U.S. Pat.
．． 26's, soG No. 3,664,841, No. 3,408.194, No. 3,277.155, No. 3,447,928, No. 3,415゜652 , Japanese Patent Publication No. 49-13576, Japanese Patent Publication No. 48-29”43
No. 2, 48-68834%, Mukai No. 49-10736,
Synthesis methods are described in 49-122335, 5G-28834, and Kuzu 50-132926.

The amount of the above-mentioned diffusion-resistant coupler used in the present invention is generally 0.0000.000.00% per mole of silver in the light-sensitive silver halide emulsion layer.
05 to 2.0 mol.

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

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. 3,297,145, U.S. Pat.
West German Patent Application (OLS) 2,417.91-4
No., JP-A-52-15271, JP-A No. 53-9116,
Examples include those described in No. 59-123838 and No. 59-127038.

The DIRIR compound used in the present invention is a compound capable of reacting with an oxidized form 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 active site of the coupler.For example, British Patent No. 935 .454, U.S. Patent No. 3,227,554, U.S. Patent No. 4,095,98
No. 4, No. 4.149.886, etc.

When the above DIR coupler undergoes a coupling reaction with an oxidized color developing agent, the coupler core forms a dye,
On the other hand, it has the property of releasing a development inhibitor. Further, in the present invention, US Pat. No. 3,652,345 and US Pat.
．． No. 041, No. 3.958,993, No. 3.96
No. 1,959 1. No. 4.052,213, Japanese Unexamined Patent Publication No. 5
3-11 (No. 1529, No. 54-13333, No. 55
It also includes compounds that release a development inhibitor but do not form a dye when subjected to a coupling reaction with an oxidized form of a color developing agent, such as those described in No. 161237.

Furthermore, JP-A-54-145135 and JP-A-56-1
When reacted with oxidized color developing agents such as those described in No. 14946 and No. 57-154234, the mother nucleus forms a dye or a colorless compound, while the departing timing group undergoes an intramolecular nucleophilic substitution reaction. Also included in the present invention are so-called timing DIR compounds, which are compounds that release development inhibitors by multi- or elimination "reactions."

Also, JP-A No. 58-160954, No. 58-16294
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 form of a color developing agent described in No. 9;
It also includes IR compounds.

The DIR compound contained in the light-sensitive material is preferably used in a range of 1 x 10-mol to 1 oxio-t mol per mol 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, hydrophilic colloids used for mlJ of the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein. , hydroxyethyl cellulose derivatives, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinylimidazole,
Any single or copolymer synthetic hydrophilic polymer such as polyacrylamide is included.

Examples of the support for the silver halide color photographic light-sensitive material used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or a reflective material, such as a glass plate, Examples include cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, etc., and other ordinary transparent supports may also be used. be selected accordingly.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the silver halide emulsion layer and other photographic constituent layers used in the present invention. Also, U.S. Patent Nos. 2 and 7
61,791 and 2,941,898 can also be used.

In the present invention, the coating position of each emulsion layer can be determined arbitrarily. For example, in the case of a full-color photosensitive material for printing abrasive, 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 a medium &11 layer with an appropriate thickness depending on the purpose, and furthermore, a filter layer, an anti-curl layer, and a protective layer II! , antihalation layers, and the like can be used in appropriate combinations as constituent layers. Hydrophilic colloids that can be used in the emulsion layers as described above can be used as binders in these constituent layers, and various types of colloids that can be contained in the emulsion layers as described above can be used in these layers. Photographic additives may be included.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, if the silver halide color photographic light-sensitive material is a light-sensitive material that is processed by a so-called internal development method containing a coupler in the light-sensitive material, a color vapor is used. The present invention can be applied to any silver halide color photographic light-sensitive material such as color negative film, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, and reversal color vapor.

[Specific Effects of the Invention] As explained above, according to the processing method of the present invention, the color developing solution has excellent storage stability, excellent photographic properties such as staining caused by bleach-fixing and maximum color density, and particularly rapid processing. 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 a comparative photosensitive material sample.

Layer 1 ・1.3g/v gelatin, 0.2oO,/f(
Blue-sensitive silver chlorobromide emulsion <Ao
96 mol % as C1) and 1, OX 10' mol (J/f) dissolved in 0.501; l/f dioctyl phthalate.

Layer 2: Intermediate layer consisting of 0.56 Mf gelatin.

Layer 3...1. (1/f gelatin, 0.30 (1/f)
f green-sensitive silver chlorobromide emulsion (AIJ Cff1 as 9
8 mol %) and 10-3 mol g/f of 1,IX dissolved in 0.361 J/n2 dioctyl phthalate of the following comparative magenta coupler (M-i).

Layer 4: Intermediate layer consisting of 1.517/l' gelatin.

Layer 5...1.30/f gelatin, 0.26 g/n
' red-sensitive silver chlorobromide emulsion (98 mol % as silver chloride) and 0.20! A layer containing 1,4X 10-3 moles Q/f of the following comparative cyan coupler (C-1>) dissolved in dibutyl phthalate of It/n'.

Layer 6...1.10/f gelatin and 0.220 (
0,34C dissolved in 1/12 dioctyl phthalate
A layer containing I/l' Tinuvin 328 (ultraviolet absorber manufactured by Ciba Geigy).

Layer 7: A layer containing gelatin of 0.48Q/f.

In addition, as a hardening agent, 2,4-dichloro-6-hydroxy-S-triazine sodium was added in layers 2.4 and 7.
Each was added in an amount of 0.012 g per 1 g of gelatin.

M'-1 Cj' Color paper for comparison was prepared in the manner described above. In the same way, a comparative magenta coupler (M'-1) was used as a magenta coupler as shown in Table 1 below (the silver matrix of the third layer was also 0).
．． 200/n') to prepare and use experimental samples for the present invention sample and comparative sample.

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

Processing process Processing temperature Processing time [1] Color development 35℃ 45 seconds [2] Bleach constant @
35℃ 45 seconds [3] Wash with water 30℃
100 seconds [4] Drying 60 to 80°C for 90 seconds The color developer and bleach-fix solution used had the following compositions.

(Color developing solution) - Potassium chloride 2.0 g - Potassium sulfite (listed in Table 1) - Sodium polyphosphate 2.09 - Color developing agent (Exemplary compound A-1) 5.6a - Hydroxylamines (Exemplary compound l- 1) 5.0 (1.Potassium carbonate 30Q Add water and make 12
I) H10,Is with potassium hydroxide and 50% sulfuric acid
Adjust to.

[Bleach-fix solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60. OQ ethylenediaminetetraacetic acid @ 3.0 (ammonium 1 thioate (70% solution) 100.0tffi Ammonium sulfite (40% solution) 27.51g Add water to bring the total m to 12, and adjust the pH with potassium carbonate or glacial acetic acid. Adjust as described in Table 1.

However, the coloring solution contains Fe 3+ (2,5p
pm) and C1l 2''(1,51)Dffl> were added, and 250 d of the color developing solution was roughly mixed into the bleach-fixing solution, and after storage at 45° C. for 3 days, development processing was performed. .

The developed sample was measured using a Sakura photoelectric densitometer PDA-65 (manufactured by Konishi Roku Photo Industry Co., Ltd.) to determine the magenta density (magenta coupler) in the unexposed area, where the coupling speed is fast and fog is a problem, and the development process. The yellow density was measured at the highest density area where the speed was slow and the color density was difficult to develop.

As is clear from Table 1, the sulfite concentration in the color developing solution is in the range of 17X10-3 morph2 or less, and the magenta of the present invention represented by the general formula [M] according to the present invention is contained in the light-sensitive material. Contains a coupler, and also contains p of the bleach-fix solution.
When H is in the range of 4.5 to 6.8, sufficient yellow dye density can be obtained despite the extremely short color development time of 45 seconds, and magentastin can be produced in unexposed areas. It turns out that there are few. However, if the sulfite concentration in the color developing solution, the presence or absence of the magenta coupler represented by the general formula [M] according to the present invention in the light-sensitive material, or the pH of the bleach-fix solution is outside the scope of the present invention, yellow Problems such as insufficient pigment concentration or too much magentastin occur, which can reduce commercial value.2 Especially sulfur! A more sufficient yellow density can be obtained when the degree is less than 7 x 10-3 mol/y, especially from 0 to 4
It turns out that particularly good results are obtained when X10-3 mol/l.

[Example 2] Color developing drug (A-1) in the color developing solution used in Example 1
) was changed to (B-1) or <8-2) below and a similar experiment was conducted, and the magentastin in the unexposed area deteriorated by 0.02 in both cases.

Similarly, the coloring agent (A-1) of Example 1 was
Exemplary compounds (A-2), (A-/I) and (8-15)
When the same experiment as in Example 1 was carried out with each change, the same results were obtained.

(B-1) (B-2) [Example 3] The silver halide composition of the blue-sensitive layer in the silver halide color light-sensitive material used in Example 1 Example 1 @ N 0.9 is shown in Table 2 below. The same experiment was conducted in the same manner as in Example 1 except for the following changes. The results are summarized in Table 2.

Table 2 As is clear from Table 2, the yellow dye concentration is almost sufficient when the silver halide composition of the silver halide color photographic light-sensitive material contains silver chloride of 80 mol% or more, but when the silver chloride content is lower than this, the yellow dye concentration is almost sufficient. It can be seen that sufficient dye density cannot be obtained when the content is low.

Furthermore, it can be seen that when the content is 90 mol % or more, better dye density is obtained, and when it is 95 mol % or more, the density 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. In particular, when the silver chloride content of all the silver halide emulsion layers is 80 mol % or more, especially 90 mol % or more, especially 95 mol % or more, the entire circumference provides a preferable dye density and can give a complete black color. understood.

[Example 4] Exemplary compound (A'-2) was added to the color developer used in Example 1.
), (A'-4) and (A'-9) (all triadylstilbene optical brighteners), 2o each! When the experiment was carried out in the same manner as in Example 1, the occurrence of magentastin was 0.01 to 0.02 in all cases.
In other words, there was an improvement of 20% to 40% reduction.

[Example 5] Exemplary compounds (I-1), (I-5), and (I-2) were added to the color developer used in Experiment N099 of Example 1 in amounts of 1 each.
20/4 was added and a similar experiment was conducted, and when the amount of color developing agent in the color developing solution after storage was measured, the decomposition rate was improved by 3 to 4%. Stin) also decreased roughly by about 0.01.

[Example 61 Exemplary compounds (B-I-2>, (B-I-3) and (B-11-3) were added to the color developer used in Experiment No. 9 of Example 1.
) 0.5g each #! When a similar experiment was conducted with the addition of magenta tin, the unexposed area magentastin also increased by 0.01.
It was improved by decreasing by ~0.02.

[Example 7] Exemplary compounds (D-3) and (D-7) were added at 12 g/l each to the color developer used in Experiment No. 099 of Example 1, and a similar experiment was conducted. The degree of coloration was improved, and magentastin was further reduced by 0.01.

[Example 8] The example magenta coupler (Example No., -5) of the photosensitive material used in Experiment No. 009 of Example 1 was replaced with (Example No., -7>
, C example No. -22>, (example No. 104), (
Example No. -127), (Example No. -152)
, (Example No., -171), and (Example No., -1), and similar experiments were conducted, and almost the same results as Experiment No. 9 of Example were obtained.

[Example 9] Hydroxylamines of Experiment No. 009 of Example 1 are shown in Table 3.
By changing each to the hydroxylamines shown in
An experiment similar to Example 1 was conducted.

From Table 3, it can be seen that only when the hydroxylamines according to the present invention are used, there is less occurrence of magentastin and less decrease in yellow density.

Claims (1)

[Scope of Claims] After imagewise exposing a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer, a process including at least a color development step and a bleach-fixing step following the color development step is performed. In the method for processing a silver halide color photographic light-sensitive material, the silver halide emulsion layer 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 The color developer used in the color development step contains a magenta coupler represented by the following general formula [M] in at least one layer of the color developer, and has a sulfite concentration of 17× per liter of color developer.
The bleach-fixing solution used in the bleach-fixing step contains a compound represented by the following general formula [I] in an amount of 10^-^3 mol or less, and has a pH in the range of 4.5 to 6.8. A method for processing a silver halide color photographic material. General formula [M] ▲ Numerical formulas, chemical formulas, tables, etc. You may. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Further, R represents a hydrogen atom or a substituent. ] General formula [
I ] R_1-NH-OH (In the formula, R_1 represents an alkyl group having 1 to 3 carbon atoms which may have a substituent.)