JPS61251853A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To make washing water unnecessary and to reduce a load of environmental pollution by color-processing a silver halide color photographic sensitive material contg. a specified magenta coupler and by incorporating thiosulfate into the processed silver halide color photographic sensitive material. CONSTITUTION:Thiosulfate remaining in a processed sensitive material deteriorates the shelf stability of an image. When the thiosulfate is left in a processed sensitive material contg. a magenta coupler represented by formula I, the fading property of a magenta dye image by the effects of light and storage is improved. The desired thiosulfate is ammonium thiosulfate, the thiosulfate is especially effective when the surface pH of the emulsion films of the processed sensitive material is 2.5-9.0, and the effect of the thiosulfate is especially remarkably when the amount of the thiosulfate remaining in the processed sensitive material is 0.5-50mug/cm<2>. The magenta coupler is used by 1X10<-3>-1mol, preferably 1X10<-2>-8X10<-1>mol per 1mol silver halide.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for processing silver halide color photographic materials (hereinafter referred to as "photosensitive materials"), and more specifically, the present invention relates to a method for processing silver halide color photographic materials (hereinafter referred to as "photosensitive materials"), and more specifically, for long-term storage after processing by omitting the water washing step. The present invention relates to a method for processing silver halide color photographic materials capable of forming dye images with excellent storage stability. [Prior Art] Generally, after image exposure, a photosensitive material is processed through processing steps such as color development, bleaching, fixing, stabilization, bleach-fixing, and water washing. And 1. In recent years, the depletion of water resources and the increased cost of washing due to rising crude oil prices have become increasingly serious problems in such treatment processes. For this reason, as a method of omitting the washing process or extremely reducing the amount of washing water, a multi-stage counter-current stabilization treatment technique such as that described in JP-A No. 57-8543 and JP-A No. 58-134636 have been proposed. A treatment technique using a washing alternative treatment liquid containing a bismuth complex salt, as described in the publication, has been proposed. These techniques reduce the amount of water washing substitute stabilizer replenishment and reduce pollution, but the photographic images obtained by using these techniques have extremely poor shelf life over time. 1. A technique has been proposed to improve this problem, and as a technique to improve the fading of cyan dye images under high temperature and high humidity, the final treatment is performed in the presence of a soluble iron complex salt to prevent leucoization of the cyan dye. The technology to
It is known as No. 14834. However, most of the discoloration of actual photographic images is due to light and aging, and there is a desire to develop a technology that prevents discoloration due to the effects of both light and storage over time, and Mazeng dyes naturally suffer from such discoloration. There is a need for technology to prevent this. OBJECTS OF THE INVENTION Accordingly, an object of the present invention is to provide a method for processing photosensitive materials that substantially does not use washing water, has low energy costs, and has low pollution loads. Another object of the present invention is to provide a method for processing photosensitive materials that can form color photographic images that are stable during long-term storage without substantially using washing water.

[Structure of the invention]

As a result of extensive research, the present inventor has found that the following general formula (I)
After color-processing a silver halide color photographic light-sensitive material containing a magenta coupler represented by
It has been found that the above object can be achieved by a method for processing a color photographic material containing silver halide containing 112 or more. General formula (1) In the formula, Z represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a substituent that can be dissociated by reaction with an oxidized product of a color developing agent. Moreover, R represents a hydrogen atom or a substituent. The present invention will be explained in detail below. In the case of a continuous process in which stabilization treatment that substantially omits the water washing process is performed directly from treatment with a fixing or bleach-fixing solution, it is necessary to use the fixing solution or bleach-fixing solution components, soluble silver complex salts, and their like in the previous stage. Large amounts of decomposition products are carried into the stabilizing liquid, which primarily degrades the long-term stability of the photographic image. Therefore, in order to maintain the long-term stability of color images, processing must be carried out so that no fixing solution or bleach-fixing solution components, soluble silver complex salts, or their decomposition products remain in the photosensitive material, and generally sufficient washing with water should be carried out. In the case of stabilization treatment without washing with water, methods of increasing the number of tanks or replenishing a large amount of stabilizing liquid are used. However, as mentioned above, these methods contradict the objectives of cost reduction and low pollution, and cannot be said to be preferable methods. is considered to be an antinomic relationship, and although many studies have been conducted, sufficient results have not yet been obtained.The inventors of the present invention will solve this antinomic property. As a result of intensive research, it was found that the magenta coupler represented by the general formula CI) of the present invention contains thiosulfate, which is known to deteriorate image storage stability when remaining in photographic materials after processing. Surprisingly, it has been found that when left in a light-sensitive material, the fading resistance of magenta dye images due to the effects of both light and storage over time is improved. In addition, the general formula [double], [XIII], [snake, (
The present inventors have discovered that the objects of the present invention can be achieved to a higher degree when the compound represented by XV') or (XI) is contained in a light-sensitive material. Further, for the purpose of the present invention, the thiosulfate is preferably an ammonium salt, and the present invention is particularly effective when the emulsion surface PTR of the processed light-sensitive material is in the range of 2.5 to 9.0. The effects of the present invention are particularly apparent when the thiosulfate remaining in the processed photographic material is in the range of 0.65 μg/ca+2 to 50 μg/cm 2.The present invention will now be described in detail. In the magenta coupler represented by the general formula [I] according to the present invention, examples of the substituent represented by R include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group,
Cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sul77moyl group, cya7 group, spiro compound residue, bridged hydrocarbon compound residue , alkoxy group, aryloxy group, heterocyclic oxy group, sykoxy group, acyloxy group, carbamoyloxy group, amine 7 group, acyl 7 group, sulfonamide group, imide group, ureido group, sulfonyl 7 group , alkoxycarbonylamide 7 groups, aryloxycarbonylamide 7 groups, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, and heterocyclic thio group. Examples of the halogen atom include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred. The alkyl group represented by R has 1 to 32 carbon atoms, and the alkenyl group and alkynyl group have 2 to 3 carbon atoms.
2, cycloalkyl groups and cycloalkenyl groups preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the furkyl groups, alkenyl groups and alkynyl groups may be linear or branched. In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups include substituents [e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, and aromatic hydrocarbon compound residues. In addition to groups, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via a hetero atom (1) Physically, hydroxy, alkoxy, and aryloxy , heterocyclic oxy,
Those substituted via an oxygen atom such as siloxy, acyloxy, carbamoyloxy, nitro, amino (including dialkyl 7mino, etc.), sulfonyl 7mino, alkoxycarbonyl 7mino, aryloxy-carbonylamino, acylamino, sulfone 7 Those substituted via a nitrogen atom such as mido, imide, and ureido; those substituted via a sulfur atom such as alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl, and sulfamoyl;
(e.g., those substituted via a phosphorus atom such as phosphonyl)]. Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, 1
-hexylnonyl group, 1.1'-nobentyl7yl group,
2-chloro-t-2-thyl group, to-I-nofluoromethyl group,
1-ethoxytridecyl group, 1-4 methoxyisopropyl group, methanesulfonylethyl group, 2,4-cy7-7
Mil7eth7oxymethyl group, Aeri7 group, 1-7unylisopropyk1M, 3-m-butanesulfonaminophenoxypropyl group, 3-4'-((t-(4''(p-
hydroxybenzenesulfonyl) phenoxyfudodecanoylamino) phenylpropyl group, 3-(4'-(ff
-(2”,4”-not-t-amylphenoxy)butane 7
Examples include mido]phenyl)-propyl group, 4-[α-(〇-chlorophenoxy)tetradecanamidophenoxy]propyl group, allyl group, ncrobentyl group, and cyclohexyl group. R'? The aryl group represented is preferably a 7enyl group, which may have a substituent (for example, an alkyl group, an alkoxy group, an acylamide 7 group, etc.). Specifically, phenyl group, 4-L-butylphenyl group,
2,4-di-amylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4
J (a-(4J/t-butylphenoxy)tetradecanamidophenyl group, etc.) The heterocyclic group represented by R is preferably a 5 to 7 ring group, and may be substituted or fused. You can also
i4: 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, a-2,4-di-
Examples thereof include a furkylcarbonyl group such as a t-7mil7e/xybuta/yl group, a 7lylcarbonyl group such as a benzoyl group, a 3-pentadecyloxybenzoyl group, and a 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-)luenesulfonyl group. Examples of the sulfinyl group represented by R include, +ethylsulfinyl group, octylsulfinyl group, alkylsulfinyl group such as 3-phenoxydibutylsulfinyl group, phenylsulfinyl group, +*-pentadecyl 7enylsulfinyl group. Examples include a chiarylsulfinyl group and the like. The phosphonyl group represented by R includes butyloctylphosphonyl group! lfurkylphosphonyl group, alkoxyphosphonyl group such as octyloxyphosphonyl group, aryloxyphosphonyl group such as phenoxyphosphonyl group,
Examples include 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-dibutylcarbamoyl group, N-(2-pentadecyloctylethyl)carbamoyl f, N-ethyl-N-dodecylcarbamoyl group, N-13-(2,4-note -7milphenoxy)propyl) The sulfamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N-propylsul77moyl, N,N-diethylsul77moyl group, N-(2-pentadecyloxyethyl)sul77moyl group, N-ethyl-N-dodecylsulfamoyl group, N-phenylsulfamoyl group, and the like. Examples of spiro compound residues represented by R include subic+
Examples include [3,3]heptane-1-yl and the like. Examples of the aritsuru carbonized compound residue represented by R include bicyclo[2,2,1]heptan-1-yl, tricyclo[3
, 3,1,1'°7J decane-1-yl, 7,7-nomethyl-bicyclo[2,2,1]hebuta. No. 1-yl and the like can be mentioned. The alkoxy group represented by R'1' may be further substituted with the substituents listed above for the alkyl group, such as methoxy group, propoxy group, 2-ethoxyethoxy group, pentadecyloxy group, -dodecyloxyethoxy group, 7enethyloxyethoxy group, etc. The aryloxy group represented by R is preferably 7enyloxy, and the aryl nucleus may be further substituted with the substituents or atoms listed above for the aryl group,
For example, phenoxy group, pt-butylphenoxy group, I
-pentadecylphenoxy group and the like. The heterocyclic oxy group represented by R preferably has 5 to 7 heterocycles, and the heterocycle may further have a substituent, for example, 3゜4.5.6-. Examples include tetrahydrobilanyl-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. Examples of the acyloxy group represented by R include an alkylcarbonyloxy group, an arylcarbonyloxy group, etc., and may further have a substituent, and specifically, a nacetyloxy group, an α-chloroacetyloxy group, Examples include benzoyloxy group. The carbamoyloxy group represented by R may be substituted with an alkyl group, an aryl group, etc., such as N-ethylcarbamoyloxy, N,N-diethylcarbamoyloxy, N-phenylcarbamoyloxy, etc. Can be mentioned. The amide group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an ethylamino group, an anilino group, a chlorine group,
Examples thereof include a 3-pentadecyloxy group, a 2-chloro-5-hexadecane group, and a 2-chloro-5-hexadecane group. Examples of the acylamino group represented by R''1' include 7 alkylcarbonylamide groups, 7 arylcarbonylamide groups (preferably 7 phenylcarbonylamide groups),
It may further have a substituent, specifically an acetamide group,
α-ethylpropanamide group, N-phenylacecyamide group, dodecanamide group, 2,4-di-t-7milphenoxyacetamide group, α-3-t-butyl 4-hydroxy 72/xybutanamide group Examples include groups. Examples of the sulfonamide group represented by R include an alkylsulfonylamino group, an arylsulfonylamino group, and may further have a substituent. Specifically, 7 methylsulfonylamide groups, 7 pentadecylsulfonylamide groups, benzenesulfonylamine)' group, p-
) Luenesulfonamide group, 2-methoxy-5-t-7
Examples include milbenzenesulfone 7-mido group. The imide group represented by R may be open-chain or cyclic, and may have a substituent, such as a succinimide group, a 3-heptadecylsuccinimide group, a 7-talimide group, Examples include glutarimide group. The ureido group weakened by R is an alkyl group, a 7-aryl group (
(preferably phenyl group) etc. may be substituted (
, for example, N-ethylureido group, N-methyl-N-decylureido group, N-phenylureido group, N-p-tolylureido group, and the like. The sul 7 amoylami 7 group represented by R is a furkyl group,
It may be substituted with an aryl group (preferably a phenyl group), and examples thereof include N,N-butylsulfo-7-amoylami groups, N-methylsulfo-T-moylami/groups, and N-phenylsul-7-amoylami groups. The alkoxycarbonylamide 7 group represented by R is,
It may further have a substituent, for example, 7 methoxycarbonylamide groups, 7 methoxyethoxycarbonylamide groups,
Examples include octadecyloxycarbonylamino group. R? The 7 aryloxycarbonylamide groups represented may have a substituent, such as 7 7-enoxycarbonylamide groups and 7 4-methylphenoxycarbonylamide groups. The alkoxycarbonyl group represented by R may further have a substituent, for example, a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group. etc. The aryloxycarbonyl group represented by R may further have a substituent, such as a phenoxycarbonyl group,
Examples include p-chlorophenoxycarbonyl group and -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 7enethylthio 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-7cetaminophenylthio group. The heterocyclic thio group represented by R is preferably a 5- to 7-membered 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-)lyazole-6-thio group. Examples of the substituent which can be separated by reaction with the oxidized product of the color developing agent represented by X include a halogen atom (chlorine atom, bromine atom, hexasol atom, etc.), an oxygen atom, a sulfur atom, or a nitrogen atom. Examples include groups substituted via. Groups substituted via a carbon atom include, in addition to carboxyl groups, for example, those of the general formula (R6' is the same as the above R, Z' is the same as the above Z, R2' and R3' are a hydrogen atom, an aryl group , which represents an alkyl group or a heterocyclic group, a hydroxymethyl group, and a tri722ylmethyl 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 thereof include a nidoxy group, a 2-phenoxyethoxy group, a 2-cyanoethoxy group, a 7enethyloxy group, and a p-chlorobenoloxy group. The aryloxy group is preferably a phenoxy group, and the aryl group may further have a substituent.
Dodecyl 72/oxy group, 4-methanesulfonamidophenoxy group, 4-(α-(3'-pentadecylphenoxy)butanamido]phenoxy group, hexydecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonyl 72/oxy group, 1-su7tyloxy group, p-
Examples of the heterocyclic oxy group include methoxy72/oxy groups, etc.6 The heterocyclic oxy group is preferably a 5 to 7 shell heterocyclic oxy group, which may be a fused ring or may have a substituent. . Specifically, 1-phenyltetrazolyloxy group, 2
-benzothiazolyloxy group and the like. Examples of the acyloxy group include acetoxy group, fulkylcarbonyloxy group such as butanoloxy group, alkenylcarbonyloxy group such as 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 an ethoxycarbonyloxy group and a benzyloxycarbonyloxy group. Examples of the aryloxycarbonyl group include a phenoxycarbonyloxy group. Examples of the alkyloxalyloxy group include a methyloxalyloxy group. - Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group. Examples of groups substituted via a sulfur atom include alkylthio groups, arylthio groups, heterocyclic thio groups, and flukyloxythiocarbonylthio groups. Examples of the alkylthio group include a butylthio group, a 2-cyanoethylthio group, a 7enethylthio group, a bennorthio group, and the like. The arylthio group includes phenylthio group, 4-7thanesulfonamidophenylthio group, 4-dodecyl7enethylthio group, 4-7sufluoropentane7mido7enethylthio group, 4-carboxyphenylthio group, 2-ethoxy-5 Examples include -t-butylphenylthio group. Examples of the heterocyclic thio group include 1-phenyl-1,
Examples include 2,3,4-tetrazolyl-5-thio group and 2-benzothiazolylthio group. Examples of the alkyloxythiocarbonylthio group include a dodecyloxythio-carbonylthio group. Examples of the group substituted via the nitrogen atom include those represented by the general formula -N, such as aryl group, heterocyclic group, sulfamoyl group, carbamoyl group, acyl group, sulfonyl group, aryloxycarbonyl group, etc. represents an alkoxycarbonyl group, and R, 7 and R, 7 may be combined to form a heterocycle. However, R4' and RS
' cannot both be 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, 7 alkylamides, 7 arylamides, 7 acylamides, sulfonamide group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group,
Examples thereof include a carbamoyl group, a sulfazoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkyloxycarbonylamino group, an aryloxycarbonylamino group, a hydroxyl group, a carboxyl group, a cyano group, and a halogen atom. Specific examples of the alkyl group include ethyl group, oxytyl group, 2-ethylhexyl group, and 2-chloroethyl group. The aryl group represented by R, J or R5' has 6 to 32 carbon atoms, preferably a phenyl group or a naphthyl group,
The aryl group may have a substituent, and examples of the substituent include those listed above as a substituent for the alkyl group represented by R4' or R, and an alkyl group. Specific examples of the aryl group include a phenyl group, a 1-su7tyl group, and a 4-methylsulfonylphenyl group. The heterocyclic group represented by R4' or R5' is 5 to 6
Shellfish are preferred, and may be a condensed ring or have a substituent. Specific examples include 2-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-benzothiazolyl group, and 2-pyridyl group. The sulf77moyl group represented by R4' or R5' includes N-furkylsulfamoyl group, N,N-noalkylsulfamoyl group, N-arylsulf77moyl group, N-
, 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-noethylsulfamoyl group, N-methylsulfamoyl group, N
-dodecylsulfamoyl Ii, N-p-) rilusul 7
An example is an amoyl group. The carbamoyl group represented by R4' or R5' is
Examples include N-furkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-7arylcarbamoyl group, N,N-diarylcarbamoyl group, etc., and these alkyl groups and aryl groups are the same as those mentioned above for the alkyl group and aryl group. It may have a substituent. Specific examples of the carbamoyl group include N,N-noethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, N-p-cyanophenylcarbamoyl group, N-
-p-)lylcarbamoyl group. Examples of the acyl group represented by R% or R5' include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group have a substituent. It's okay. Specific examples of the acyl group include hexafluorobutanoyl group, 2゜3.4.5.6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthonyl group, 2-7lylcarbonyl group, etc. It will be done. Examples of the sulfonyl group represented by R4' or R5' include an alkylsulfonyl group, an arylsulfonyl group, and a heterocyclic sulfonyl group, which may have a substituent, and specific examples include an ethanesulfonyl group, Examples include a benzenesulfonyl group, an octanesulfonyl group, a naphthalenesulfonyl group, and a p-90 rubenzenesulfonyl group. The aryloxycarbonyl group represented by R4' or R5' may have any of the substituents listed above for the aryl group, and specific examples thereof include a 7enoxycarbonyl group and the like. The alkoxycarbonyl group represented by R4' or R5' may have a substituent listed for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, a benzyloxycarbonyl group, etc. Can be mentioned. The heterocycle formed by bonding R, / and 1R5' is preferably a 5- to 6-true heterocycle, and may be saturated or unsaturated, and may or may not have aromaticity. ,or,
It may be a condensed ring. Examples of the heterocycle include N-7 talimide group, N-succinimide group, 4-N-urazolyl group, 1-N-hydantoinyl group, 3-N-2,4-dioxoxazolidinyl group, 2 -N-1,1-dioxo-
3-(2H)-oxo-1,2-benzthiazolyl group,
1-pyrrolyl group, 1-pyrrolinonyl group, 1-pyrazolyl group, 1-pyrazolinonyl group, 1-piperidinyl group, 1-
Pyrrolinyl group, 1-imidazolyl group, 1-imidazolinyl group, 1-indolyl group, 1-isoindolinyl group, 2
-isoindolyl group, 2-isoindolinyl group, 1-benzotriazolyl group, 1-benzimidazolyl group, 1-
(1,2,4-)riazolyl) group, 1-(1,2,3-
) riazolyl) group, 1-(1,2,3,4-tetrazolyl) group, N-morpholinyl f, , 1,2.3.4-tetrahydroquinolyl group, 2-oxo-1-pyrrolidinyl group, 2- IH-pyridone group, 7-thalassion group, 2-oxo-1-piperidinyl group, etc., and these heterocyclic groups include alkyl groups (aryl group, alkyloxy group, aryloxy group, acyl group, sulfonyl group, alkyl 7 Mino group, 7 arylamide groups, 7 acylamide groups, 7 sulfonamide groups, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group, aryloxycarbonyl group, imido group, nitro group, cyano group, carboxyl group , a halogen atom, etc. Examples of the nitrogen-containing heterocycle formed by Z or Z'- include a pyrazole ring, an imidazole ring, a triazole ring, or a tetrazole ring. Examples of substituents that may be used include those mentioned above for R. In addition, substituents on bicyclic rings in general formula CI) and general formulas (II) to [■] described below (for example, R2H, - When R,) has a moiety (here, R'', X and Z II have the same meanings as R, X and Z in general formula (1)), it forms a so-called screw-type coupler, but is of course included in the present invention. In addition, the ring formed by z, z', z'' and 21 described below may be further fused with another ring (for example, a cycloalkene with 5 to 7 shells) 6 For example, the ring formed by the general formula (V ), R5 and R6 may be bonded to each other, or Rf and R8 may be bonded to each other to form a complete ring (for example, a 5- to 7-shell cycloalkene, benzene). More specifically, what is represented by the general formula [1] is represented by, for example, the following general formulas (II) to [■]. General formula (II) General formula CI [l] N -N -N General formula [■) -N-NH General formula [V] General formula [■] N -N -NH General formula [■] Said general formula (II ) ~ [■] R, -R, and X
has the same meaning as R and X above. Also, among the general formula (1), the following general formula [
■]. General formula [■] In the formula, R, , X and Z have the same meanings as RlX and Z in the general formula (1). Among the magenta tough couplers represented by the general formulas (II) to [■], particularly preferred is the magenta coupler represented by the general formula [II]. Regarding the substituents on the heterocycle in general formulas (1) to [■], R in general formula CI) and R1 in general formulas (I[) to [■] satisfy the following condition 1. It is preferable that the following conditions 1 and 2 are satisfied, and more preferable.
The following conditions 1 and 1 are particularly preferred.
This is a case where conditions 2 and 3 are satisfied. Condition 1 The root atom directly connected to the heterocycle is a carbon atom. Condition 2: Only one hydrogen atom or no hydrogen atom is bonded to the carbon atom. Condition 3 All bonds between the carbon atom and adjacent atoms are single bonds. The most preferred substituents R and R on the heterocycle are those represented by the following general formula (IX). General formula (IX) R8 R9゜-〇- R1 In the formula, R1ffR1o and R11 each represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, or an acyl group. group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, endowed hydrocarbon compound residue, alkoxy group, aryloxy group, beterocyclic oxy group, siloxy group, acyloxy group, Carbamoyloxy group, amine 7 group, acylami 7 group, sulfonamide group, imide group, ureido group, sulfonamide 7 group, alkoxycarbonylamino group, 7lyloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, R represents an alkylthio group, an arylthio group, or a heterocyclic thio group. At least two of R1゜ and (/R, , are not hydrogen atoms. Also, two of the above R, , R, . and R1+, for example, R5
and RIG may be bonded to form a saturated or unsaturated ring (e.g., cycloalkane, cycloalkene, heterocycle), and R11 may be bonded to the ring to form an endowed hydrocarbon compound residue. good. The group represented by R3 to RII may have a substituent, and specific examples of the group represented by R1 to R1+ and the substituent that the group may have include the above-mentioned general formula (1). Specific examples of the group represented by R and substituents are listed. Also, for example, a ring formed by combining R3 and R1° and R1
Specific examples of the bridged hydrocarbon compound residue formed by -R1 and its optional substituents include cycloalkyl, cycloalkenyl, and heterocyclic groups represented by R in the above-mentioned general formula (1). Specific examples of hydrocarbon compound residues and their substituents are listed. Among the general formulas [ff], (i) Rs-R
When two of 11 are alkyl groups, (ii) R@~R
One of the eyes, for example R1+, is a hydrogen atom, and the other two
When R1 and RIo combine to form a cycloalkyl together with the root carbon atom, the following is true. Furthermore, among (i), preferred are 2 of Rs to R.
One is an alkyl group, and the other 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 their substituents include the alkyl, cycloalkyl, and cycloalkyl represented by R in the general formula (1); Z in (1,)
The ring formed by the general formula [■] and the substituent that the ring formed by ZI in the general formula [■] may have, and the general formula (
R2-R8 in II) to (Vl) are preferably those represented by the following general formula (X). General formula [X] -R'-3O2-R2 In the formula, R1 represents alkylene, and R2 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 the straight chain portion has 1 or more carbon atoms.
Regardless of branching. Moreover, this alkylene may have a substituent. Examples of the substituent include R in the above-mentioned general formula (1)
When is an alkyl group, the substituents that the alkyl group may have include those shown below. Preferred substituents include phenyl. Preferred specific examples of fullkylene represented by R1 are shown below. The alkyl group represented by R2 has 9 straight chain branches and 1°, specifically methyl, ethyl, propyl, 1so=propyl, butyl, 2-ethylhexyl, octyl, dodecyl, tetradecyl, hexadecyl, oftagyl, 2-to Examples include xyldecyl. The cycloalkyl group represented by R2 is preferably one with 5 to 6 shells, such as cyclohexyl. The alkyl and cycloalkyl represented by R2 may have a substituent, examples of which include those exemplified as the substituent for R1 mentioned above.Specifically, the aryl represented by R2 includes: Phenyl and Nasi 4 are held up. The aryl group may have a substituent. Examples of the substituent include linear or branched alkyl, as well as the above-mentioned R
Examples of the substituents for ' include those exemplified. Moreover, when there are two or more substituents, those substituents may be the same or different. Among the compounds represented by the general formula [I], those represented by the following general formula [revised] are particularly preferred. General formula [revised] In the formula, R and X have the same meanings as R and X in general formula CI), and Rl and R2 are Rl in general formula (X). It has the same meaning as R2. Hi C1°CH. H3 CH3 ■ CH3 CH3CH3 C4t+. CH3 CH3 CH3 CI. tH1s CJ? 2Hq CH. CH. CH. CH. 7HI 5CI. CJ (+s H3 CH. OC1hCONHCH2CH20CHi0CH2CH2
SO2CH3 2H5 C2H. 21st 5th H3 CH3 21st 5th 12H25 10fcs) lta 0C2H3 CH. I3 C8■+ 7(1) L CH3Cs Hl 7 (t) CI. CH3 C? H 5th 2H50 CI H Yo CCH. B)Q0(CH2)20C12H25N-N-N-N-N-NHN2H5 195
theChemical Society)
Perkin 1 (1977),
2047-2052, U.S. Patent 3,725,067
No., Ryukai No. 59-99437, Japanese Patent Publication No. 58-4204
No. 5, JP-A-197-162548, JP-A-59-17
1956, JP-A-80-13552 and JP-A-60-
Synthesis was carried out with reference to No. 43659 and the like. The couplers of the invention typically contain 1Xl per mole of silver halide.
It can be used in the range of 0-' mole to 1 mole, preferably 1X10-" mole to 8X10-' mole. The coupler of the present invention can also be used in combination with other types of magenta couplers. The photosensitive material has the following general formula [river] or [x
(2) It is preferable to contain a compound represented by [2]. In general formulas (XI [) to [X , such as methyl, ethyl,
benol, etc.), an aryl group (eg, phenyl), or an alkoxy group (eg, methoxy, ethoxy, benzyloxy, etc.). Rlj to R2° may be the same or different and represent a hydrogen atom or a substituted or unsubstituted alkyl group (having 1 to 20 carbon atoms, such as methyl, ethyl, dotecyl, octadecyl, etc.). Y is a hydrogen atom, an acyl group (e.g., acetyl, stearoyl, benzoyl, chloroacetyl, etc.), an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, etc.), a carbamoyl group (e.g., N, N-dimethylcarbamoyl, N, N-trimethylcarbamoyl, etc.) or a sulfonyl group (eg, methanesulfonyl, benzenephonyl, etc.), and each may be the same or different. Stand represents an integer of 1.2 or 3, m represents an integer of O to 2, provided that Q+m is 4 or less. Each group listed above may have an appropriate substituent,
Examples of the substituent include an alkoxy group, an aryloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarponyl group, a halogen atom, a carboxyne group, a sulfo group, a sia7 group, an alkyl group, an alkenyl group, an aryl group, and an alkylamino group. group, arylami 7 group, carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, acyl group, sulfonyl group, acyloxy group and acylami 7 group. B-7B-8 n B-11B-12 B-13B-14 B-161g
B-17 However, R2□ represents a hydrogen atom, an alkyl group, a ring group, or a heterocyclic group, and R22, F123, R2
4 and R2° represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, or an acylamide group, and R24 represents an alkyl group, an aryl group, a phenoxy group, or an alkoxy group. Furthermore, R21 and 822 may be ring-closed to form a methylenedioxy ring. These compounds include: U.S. Patent No. 3,935.016, U.S. Patent No. 3,982.944, U.S. Patent No. 4,254,216
specification, JP-A-55-21004, JP-A-54-1
Publication No. 45530, British Patent Publication W112,077.45
No. 5, No. 2,062,888, U.S. Patent No. 3,
No. 764,337, No. 3,432,300, No. 3,
No. 574,627, specification No. 3, 573, 050, JP-A-52-52225, JP-A No. 53-20327
No. 53-17729, No. 55-6321,
British Patent No. 1,347,556, British Patent Publication No. 2゜066.975, Japanese Patent Publication No. 54-12337,
Publication No. 45-31625, U.S. Patent No. 3,700,4
It also includes the compounds described in No. 55. Specific examples of the compound of general formula (XV) are as follows. B-23 In the above formula, G is a hydroxy group or its alkali-labile precursor; each R29 is individually an alkyl group (preferably having 1 to 30 carbon atoms), an aryl group (preferably having 6 carbon atoms) ~30) or a heterocyclic group (preferably having 5 to 30 carbon atoms) having one or more heteroatoms selected from nitrogen, oxygen, sulfur and selenium; R1°, R
3I and Rff2 are each a hydrogen atom, a halogen atom,
an alkyl group (preferably 1 to 30 carbon atoms), an alkoxy group (preferably 1 to 30 carbon atoms), an aryl group (preferably 6 to 30 carbon atoms), or an aryloxy group (preferably 6 to 30 carbon atoms); be. Is the compound represented by the general formula [XVI] sufficient to be non-diffusive in the layer of the photosensitive material?':! : (bulk) is preferable. Preferably, R31 is alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms, and Rs. and R12 is a hydrogen atom. As mentioned above, G is a hydroxy group or an alkali-labile precursor of a hydroxy group. In an alkali-labile precursor, the hydrogen atom of the hydroxy group is replaced with a blocking group that is removed upon contact with chlorine. Typical blocking groups can be removed by hydrolysis or intermolecular nucleophilic substitution. Typical groups that can be removed by hydrolysis are acyl groups, such as aliphatic and aromatic carbonyl and sulfonyl groups. Typical groups that can be removed by intermolecular nucleophilic substitution are described in US Pat. No. 4,310,612. The aforementioned alkyl, alkoxy, aryl and aryloxy substituents are subject to further substitution. Representative of such substituents include den, nitro, alkyl, aryl, alkenyl, alkoxy, aryloxy, alkenyloxy, heterocycle, alkylcarbonyl, arylcarbonyl, alkenylcarbonyl,
Examples include alkylsulfonyl, arylsulfonyl, alkersulfonyl, amino, ami7carbonyl, ami/sulfonyl, carboxy, alkoxycarbonyl, aryloxycarbonyl and alkenyloxycarbonyl. Thus, alkyl includes, for example, arylalkyl and aryloxyalkyl, aryl includes, for example, alkaryl and alkoxyaryl, and alkenyl includes, for example, aralkenyl. The amine moieties of these additional substituents include primary, secondary and V-tertiary amines and acylated amines. H The above general formula used in the present invention [■] or) f■]
Among the compounds represented by the above, those which are water-soluble are added as an aqueous solution, and those which are sparingly soluble in water are added as an emulsion to the non-emulsion layer and/or the emulsion layer. The amount added is lXl0'5~5X 10-'+o
Q/l112, preferably 1. OX 10-4-
1. :llX 10moQ/m". The pH of the emulsion film surface of the processed light-sensitive material in the present invention is 2.
．． It is preferably in the range of 5 to 9.0, and most preferably in the range of 3.2 to 6.2. In order to adjust the pH of the emulsion film surface, any of various alkaline agents or acid agents can be used as the stabilizing solution. The above pH of the emulsion film surface refers to the common logarithm of the reciprocal of the hydrogen ion molar concentration when the dye-containing layer of the light-sensitive material is swollen with a small amount of pure water.The pH can be measured using an ordinary pH meter. Measurement is performed using a glass electrode with a calomel electrode as a reference electrode. Lowest surface coating pn with pure water
A 7-rat type composite single electrode is generally used to measure . The thiosulfate of the present invention can be incorporated into the processed photosensitive material by immersing the photosensitive material in a solution containing thiosulfate at the final stage of processing, or by adding thiosulfate to the fixing solution as a fixing agent. There is a method in which the thiosulfate in the fixer remains in the photosensitive material by performing a stabilization treatment without substantially washing with water after the fixing treatment. It is preferable to cause the photosensitive material to remain in the photosensitive material by carrying out a stabilization treatment instead of washing with water. Thiosulfates include sodium salts, potassium salts, quaternary ammonium salts, etc. In the present invention, the type of cation is not particularly limited, but ammonium salts are preferred. In the present invention, the amount of thiosulfate contained in the processed photographic material is 0.1 μgram, preferably 0.2 μgram.
μg/cm"-100μg/am", most preferably 0.5μg/cm2 to 50/J
This is within the range of G/C theory 2. For measuring the amount of thiosulfate contained in the above-mentioned processed photographic material, 8NSI pi 14.8 (1978) or P
, S.E. 10(2)86 (1966) can be used. In the present invention, processing with a processing solution having fixing ability after color development refers to a process using a fixing bath or a bleach-fixing bath for the purpose of fixing the light-sensitive material after processing with a normal color developer. . Details of the color developing solution, fixing solution, and bleach-fixing solution will be described later. In the present invention, when processing with a processing solution having a fixing ability and subsequently processing with a washing substitute stabilizing solution without substantially washing with water, the fixing bath or bleach-fixing bath is directly followed by processing with the washing substitute stabilizing solution. This process is completely different from the conventional process of washing with water and treating with a stabilizing solution after a fixing bath or a bleach-fixing bath. In , the treatment with a water-washing alternative stabilizing solution refers to a stabilization treatment that is performed immediately after the treatment with a treatment solution having fixing ability and does not substantially require a water-washing treatment, and is used for the stabilization treatment. The treatment liquid is called a washing substitute stabilizing solution, and the treatment tank is called a stabilizing bath or a stabilizing tank.The washing substitute stabilizing solution of the present invention preferably contains a fungicide.Preferably, the fungicide used is hydroxybenzoin. Acid compounds, alkyl 7-ether compounds, thiazole compounds, birinone compounds, guanidine compounds, carbamate compounds, morpholine compounds, quaternary phosphonium compounds, ammonium compounds, urea compounds, inxazome compounds , propatoolamine type compounds, sulfumide derivatives and cyamino acid type compounds. The hydroxybenzoic acid type compounds +!t, hydroxybenzoic acid and hydroxybenzoic acid ester compounds include methyl ester, ethyl ester, propyl ester,
Although there are butyl esters and the like, n-butyl ester, isobutyl ester, and propyl ester of hydroxybenzoic acid are preferable, and a mixture of the three types of hydroxybenzoic acid esters is more preferable. In the alkylphenol compound, the alkyl group is C1-6
A compound having an alkyl group as a substituent, preferably orthocyclohexy7e7
- It is le. The thiazole compound is a compound having a nitrogen atom and a sulfur atom in a five-membered ring, and preferably 1゜2-benzisothiazolin 3-one, 2-methyl-4-isothiazolin 3-one, 2-octyl-4-isothiazolin 3-one, 5-chloro-2-methyl-4isothiazolin 3-one, 2-(4-thiazolyl)benzimidazole. Specific examples of pyrinone compounds include 2,6-diumethylpyridine, 2,4.6-)limethylpyridine, and sodium-2-pyridinethiol-1-oxide, but preferably sonorum-2-pyridinethiol. -1-oxado. Specific examples of the guanidine-based compound include cyclohexidine, polyhexamethylene biguaninone hydrochloride, dotesylguanidine hydrochloride, and preferably dotesylgutunisin and its salts. Specific examples of carbame and isotype compounds include methyl-1-(butylcarbamoyl)-2-penzimiguzole carbamate and methylimidazole carbamate. Specific examples of morpholine compounds include 4-(2-nitrobutyl)morpholine and 4-(3-nitrobutyl)morpholine. Quaternary phosphonium compounds include tetrafurkylphosphonium salts, tetraalkoxyphosphonium salts, etc., but tetrafurkylphosphonium salts are preferred, and more specific preferred compounds are tri-n-butylute-F-radecylphosphonium chlorite and triphenyl. - Nitrophenylphosphonium chloride. Specific examples of quaternary ammonium compounds include benzalkonium salts, benzethonium salts, tetraalkyl ammonium salts, and furkylpyridinium salts, and more specific examples include dodecyldimethylbennolammonium chloride, didecyldimethylammonium chloride, and lauryl. Examples include pyridinium chloride. Specific examples of urea compounds include N-(3,4-cyclophenyl)-N'-(4-chlorophenyl>ii). Specific examples of inxazole compounds include 3-hydroxy-
Examples include 5-methyl-isoxa and sol. Propertool amine compounds include n-propertools and inpropertools, specifically DL-2-bencyl7minor-1-propatol, 3-diethyl7minor-1-propatol, 2-dimethylamino -2-methyl-
1-propatur, 3-7 minnow 1-propatur, idopropaturamine, diisopropaturamine, N
Examples include N-methyl-isopropanolamine. Sulfumide derivatives include fluorinated sulf-7 amide, 4-chloro-3,5-dinitrobenzene sulf-7 amide, sulf-7 anilamide, acetosulfamine, sulf-77
pyridine, sulfaguanidine, sulfa thiazole,
These include sul 7 adiazine, sul 7 amelazine, sul 7 ametazine, sul 7 isoxazole, homosulfamine, sulfisomicin, sul 77 herring, sul 7 amethizole, sul 7 avirazine, sul 7 isosul 7 atizole, succinylsul 7 thiazole, etc. . A specific example of the amino acid compound is N-lauryl-β-alanine. Among the above-mentioned antifungal agents, compounds preferably used in the present invention are pyridine compounds, guanidine compounds, and quaternary ammonium compounds. The amount of antifungal agent added to the water washing alternative treatment solution is as follows: Water washing alternative treatment I
It is used in a range of 0.002 g to 50 g per Q, preferably in a range of 0.005 g to 10 g. Preferred compounds to be added to the water-washing substitute stabilizer used in the present invention include ammonium compounds. These are supplied by ammonium salts of various inorganic organic compounds, specifically ammonium hydroxide, ammonium bromide, ammonium carbonate, heptammonium chloride,
Ammonium hypophosphite, ammonium phosphate, ammonium phosphite, ammonium 7), acidic ammonium heptatide, ammonium fluoroborate, ammonium -e acid, ammonium bicarbonate, water 7)
7A, ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, 7 ammonium dibate, ammonium lauric tricarboxylate, benzoic 1! ! ! 7
ammonium, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate,
Ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium hydrogen heptatarate, ammonium hydrogen tartrate, ammonium thiosulfate, sulfite 7
ammonium, ethylenediaminetetraacetic acid ammonium, 1
-Hydroxyethylidene-1,1-diphosphonate ammonium, ammonium lactate, heptammonium malate, ammonium mannate, ammonium oxalate, ammonium heptalate, ammonium picrate, ammonium pyrroliscinthiocarbamate, ammonium salicylate , ammonium succinate, ammonium sul77nylate, ammonium tartrate, ammonium licorice, 2,4,6. -) linitrophenol ammonium, etc. These may be used alone or in combination of two or more. The amount of ammonium compound added is 90.
001 mol to 1.0 mol, and preferably the pH of the water washing substitute stabilizing solution in the present invention is preferably in the range of 2.5 to 12.0 in order to more effectively achieve the present invention, More preferably the pH is in the range of 4.0 to 10.0, and most preferably the pH is in the range of 4.0 to 9.0. The water washing alternative stabilizer used in the present invention includes organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pH
Conditioners (phosphates, borates, hydrochloric acid, sulfates, etc.), optical brighteners, polyvinylpyrrolidone, polyethylene glyfur, activators, hardeners, or metal chelating agents, surfactants, preservatives, Bi . HBr Znt Niy^l, Sn, Ti, Zr
Metal salts such as, etc. can be added. The amount of these compounds to be added should be determined in any combination that is necessary to maintain the PU of the water-washing alternative stabilizing bath according to the present invention and that does not adversely affect the stability of color photographic images during storage and the occurrence of precipitation. It is safe to use. It is important that the time, amount of replenishment, and temperature in the treatment with the water-washing alternative stabilizing solution do not disturb the residual thiosulfate in the photosensitive material, and generally the time is in the range of 10 seconds to 5 minutes, and the amount of replenishment is is 10aQ/a2-2! l/m" and the temperature is in the range of 5°C to 50°C. In the present invention, the effect of the present invention is greatest when the number of stabilizing tanks is 1 to 5, and particularly preferably 1 to 3. It is preferable that the number of tanks is at most 9 or less. That is, if the amount of replenisher is the same, the more tanks there are, the lower the thiosulfuric acid concentration in the final stabilizing bath, and the weaker the effect of the present invention. The light-sensitive material to which the method of the invention is applied is one in which a silver halide emulsion layer and a non-light-sensitive layer (non-emulsion layer) are coated on a support, and the silver halide emulsion includes silver chloride, silver bromide, Any silver halide such as silver iodide, silver chlorobromide, silver chloroiodide silver iodobromide, silver chloride iodobromide may be used. , any couplers and additives known in the photographic industry, such as yellow dye-forming couplers, magenta dye-forming couplers, cyan dye-forming couplers, stabilizers, etc.
Sensitizing dyes, gold compounds, high-boiling organic solvents, antifoggants,
An agent for preventing dye image fading, an agent for preventing color staining, a fluorescent whitening agent, an antistatic agent, a hardening agent, a surfactant, a plasticizer, a wetting agent, an ultraviolet absorber, and the like can be contained as appropriate. In the photographic material to which the method of the present invention is applied, constituent layers such as an emulsion layer and a non-photosensitive layer containing various photographic additives as described above may be treated by corona discharge treatment, flame treatment or It is produced by coating on a support that has been subjected to ultraviolet irradiation treatment or via a subbing layer or a coating layer. Advantageously used supports include, for example, baryta paper,
Polyethylene coated paper, polybropine synthetic paper, transparent support combined with a reflector, glass plate, polyester film such as cellulose acetate, cellulose nitrate or polyethylene terephthalate, polyamide film,
There are polycarbonate films, polystyrene films, etc. Most of the silver halide emulsion layers and non-photosensitive layers are usually hydrophilic colloid layers containing a hydrophilic binder. This hydrophilic binder includes gelatin,
Alternatively, gelatin derivatives such as acylated gelatin, guanidylated gelatin, phenylcarbamylated gelatin, heptadated gelatin, cyanoethanolated gelatin, and esterified gelatin are preferably used. Examples of hardening agents for hardening this hydrophilic colloid layer include chromium salts (chromium alum, chromium acetate, etc.)
, aldehydes (formaldehyde, glyoxal,
geltaraldehyde, etc.), N-methylol compounds (
dimethylolurea, methyloldimethylhydantoin, etc.) dioxane derivatives (2,3-nohydroxydioxane), active vinyl compounds (1,3,5-)lyacryloyl-hexahydro-5-)lyazine, 1,3-vinylsulfonyl -2-proper tools, etc.),? l Halogen compound (2,4-fuchloro-6-hydroxy-S-)
riazine, etc.), mucohalogen acids (mucochloric acid, muco7enoxychloroic acid, etc.), etc., are used alone or in combination. Further, the present invention is particularly effective when the photosensitive material is of the so-called oil-protected type, which contains a coupler dispersed in a high-boiling organic solvent. Examples of the high-boiling organic solvent include organic acid amides, carbamates, esters, ketones, urea derivatives, etc., especially dimethyl heptatarate, dimethyl heptatarate, dipropyl heptatarate,
Nobutyl 7-thaletate, di-n-octyl 7-thaletate,
Diisooctyl 7-talate F1 7-talic acid esters such as cyamyl 7-thale, tunnonyl 7-thale, diisodecyl sebacate, tricrendyl 7-os 7-ate,
Tori 7 Enil 7 years old Su 7 Eto, Tori (2-ethylhexyl) 7 Male 7
Phosphate esters such as ethate, trisononyl 7-o-7ate, sebacic acid esters such as dioctyl sepacate, no (2-ethylhexyl) sebacate, diisodecyl sebacate, glycerin esters such as glycerol tripropionate, glycerol tributyrate,
Others: adipate ester, geltar acid ester,
The effects of the present invention are great when using phenol derivatives such as succinate, maleate, 7-malate, citric ester, di-tcrt-amyl 7-ester, and n-octylphenol. Aromatic primary amine color developing agents are used for color development in the present invention, and the developing agents include known ones that are widely used in various color photographic processes. These developers include 7 minol/p-7 ester and p-7 unilene diamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Additionally, these compounds are generally present in a concentration of about 0.1 g to about 30 g per liter of color developer, preferably about 1 g per liter of color developer.
g to about 1.5 g. Examples of aminophenol-based developers include 0-7 min 7 el/-, p-7 mil/7 el/-, 5-7 min/-2-
Oxytoluene, 2-7 minnow 3-oxytoluene, 2
-Oxy-3-7 minnow 1°4-tmethylbenzene and the like are included. Particularly useful aromatic primary amine color developers are N, N'
-Dialkyl-p7z is a nylenediamine-based compound, and the alkyl group and phenyl group may be substituted with any substituent (1, among them, a particularly useful compound example is N-N'-diethyl-p7z nylenediamine). salt rl & salt, N-/f ru p-phenylenediamine salt R salt, N 9 N-si/f ru p7x nylennoamine hydrochloride [,2-7mi/-5-(N-ethyl-N-dodecylamino>-toluene , N-ethyl-N-β-methanesulfone 7midoethyl-3-methyl-4-7minoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-7mino3-methyl-N,N'- Examples include noethylaniline, 4-7minor N-(2-nodoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate, etc. The color developer includes the aromatic primary amine mentioned above. In addition to color developing agents, various components that are usually added to color developing solutions, such as alkaline agents such as sodium hydroxide, sodium carbonate, and potassium carbonate, alkali metal thiocyanates, alkali metal halides, and benol alcohol. , a water softener, a thickening agent, etc. may be optionally contained.The pH value of a color developing solution using an aromatic primary amine color developing agent as a color developing agent is usually 7 or higher, and is the most common color developing agent. The processing liquid having a fixing ability in the present invention has a fixing agent such as thiosulfate (described in JP-A No. 57-185435), thiocyanate (British Patent No. 565135). Description in the specification, JP-A No. 54-137143), /
'10 denide (described in JP-A-52-130639), thionythyl (described in Belgian Patent No. 626970), thiourea (described in British Patent No. 1189416), etc. can be used. Among these fixing agents, the effect of the present invention is effectively exerted on thiosulfate. Further, the effect of the present invention is particularly remarkable when the processing liquid having fixing ability is a bleach-fixing liquid. -Described in Publication No. 500704, JP-A-56-527
48 and 59-149358) can be used. Furthermore, when the processing solution having fixing ability used in the present invention is a processing solution for the purpose of fixing processing, any bleaching agent can be used when bleaching is performed in the preceding step. , red blood salt, iron chloride (British patent 736
persulfuric acid (described in the specification of German Patent No. 2141199);
Hydrogen peroxide (described in Japanese Patent Publication No. 58-11617, 5
B-11618), organic acid t7IIi diiron complex salt (described in JP-A-57-705:113, JP-A-57-705:113, 58-
43454, Japanese Patent Application No. 58-40633), etc. can be used. Silver may be recovered by known methods from processing solutions containing soluble silver complex salts, such as fixing solutions and bleach-fixing solutions, as well as washing substitute stabilizing solutions used in the processing method of the present invention. For example, the electrolysis method (French patent 2,299,667), precipitation method (described in JP-A-52-73037, German Patent 2,
331,220), ion exchange method (described in JP-A-51-17114, German Patent No. 2,548.2)
37) and metal substitution method (British Patent No. 1, 35)
3,805) can be effectively used. [Example I] The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto. Example 1 5.0 g each of the exemplary magenta couplers of the present invention shown in Table 1 and the following comparative couplers (1) to (3), 3.0 g of high-boiling organic solvent tricresyl phosphate (hereinafter referred to as TCP), and 20 g of ethyl acetate. The mixed solution, to which the required amount of dimethylformamide was added as necessary, was heated to 60°C to dissolve it, and then mixed with alkanol B (alkylnaphthalene sulfonate, a 5% aqueous solution of DuPont It 10+).
*It was mixed with 100 mQ of a 5% aqueous gelatin solution containing uI and dispersed with an ultrasonic disperser to obtain a dispersion. Next, the dispersion liquid was added to a silver chlorobromide emulsion (containing 30 mol% silver chloride) so that the magenta coupler shown in Table 1 was 10 mol % based on silver, and Exemplary compound (general formula (Xl) to XVI) at 1.5×10
-'mo/mt, if used in combination, add 1.5 12 mg of silver coated on a polyethylene cochioid paper support of 10+H/
It was applied to a total area of 100 cm2. In this way, samples No. 1 to No. 5 shown in Table 1 were created. These samples were exposed and processed according to the following steps. Standard - Processing process [1] Color development 38°C 3 minutes 30 seconds [
2] Bleach fixing 33°C 1 minute 30 seconds [3]
Stabilization treatment 25°C to 35°C for 3 minutes [4] Drying 75°C to 100°C for approximately 2 minutes Processing solution composition Color developing tank solution Benzyl alcohol 5th meter ethylene diglycol Potassium sulfite
2.0g potassium bromide
1.3g sodium chloride
0.2g potassium carbonate
30.0g3, -methyl-4-7 minnow N-ethyl-
N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescent brightener (trianonylstilbene type) 1.0g Hydroxyamine sulfate 3.0g 1-hydroxyethylidene-1,1-niphosphonic acid 0.4g Human axyethyl iminonoacetic acid 5.0 g Magnesium chloride hexahydrate 0.7 g 1.2-dihydroxybenzene-3,5-disulfonic acid disodium salt 0.2 g Add water and make I
Q, and adjust the pH to 10.20 with KO)1 and H2SO. <Bleach-fix tank solution> Ferric ammonium ethylene diamino tetraacetate dihydrate eog ethylenediaminetetraacetic acid 3g ammonium thiosulfate (
) 0% dissolved) 100mQ ammonium sulfite (4
Adjust the pH to 7.1 with 27.5mQ potassium carbonate or glacial acetic acid and add water to bring the total volume to I
Q: Close. <Water wash alternative stable tank liquid> 5-chloro-2-methyl-4-inchazolin-3-one 0.02g 2-methyl-4-inchazolin-3-one 0.0
2g ethylene glycol 1.0g
2-octyl-4-isothiazolin-3-one' 0,
01g1-Hydroxyethylidene-1,1-niphosphonic acid (60% aqueous solution>
3. OgBiC, (45% aqueous solution)
0.65g ammonium thiosulfate
Add 10.0g water to make the whole amount into one part, and mix KOH and H2S.
Adjust the pH to 7.2 with O. For comparison, a water washing treatment was also performed in which the stabilization treatment was changed to submerged water washing at 30°C. Next, the developed sample was replaced every day in a light resistance tester using a constant temperature thermostat at 70° C. and 70% RFI (relative humidity) and a xenon arc lamp, and stored for one month. The transmission density of the highest density part of the sample after storage was determined using a Sakura optical densitometer PD^-65 (Konishiroku Photo Industry Co., Ltd. GL),
The rate of decrease in magenta dye density (fading rate) after storage was determined as a percentage. The results are shown in Table-1. In addition, when the residual thiosulfate TNS degree in the photographic material after processing was measured by the methylene blue method, all samples treated with water washing for comparison were zero, and all samples treated with a washing substitute stabilizing solution were 4.1 to 5.2 μg. The pH at the surface of the emulsion film was between 6°3 and 6.8 for all of the samples that had been washed with water, and 4° for the samples that had been treated with water washing as a comparative coupler (1). Comparative coupler (2) U comparison coupler (3) From the results in Table 1, samples using couplers other than the present invention as magenta couplers (No. 1 to No. 4) and samples using the magenta coupler of the present invention The samples that do not contain thiosulfate in the processed light-sensitive materials of the present invention have a uniformly high magenta dye fading rate, and compared to these,
It can be seen that the fading of the magenta dye in the sample according to the present invention is extremely low. Furthermore, general formula (XI) or XV
It can be seen that when the compound I) is used in combination, the fading of the magenta dye is even less. Example 2 Sample No. 10 of Example 1 was treated in the same manner as Example 1, except that the pH of the water washing alternative stabilizing solution was changed with KOH, H, and SO as shown in Table 2. The processing was carried out in a step that involved direct stabilization treatment after bleach-fixing, without washing with water. The storage conditions for the sample after treatment were the same as in Example 1.
As shown in Table 2, the emulsion film surface pH of the present invention is Z, 5.
-9.0 is preferred, particularly preferably 3.2-6.
．． It is within the range of 2. Example 3 After exposure of Sakura-Baber (manufactured by Konishi Roku Photo Industry Co., Ltd.) to photoprinting, continuous processing was performed using the following processing steps and processing solution. Standard processing step [1] Color development 38°C 3 minutes 30 seconds [
2] Bleach fixing 33℃ 1 minute 30 seconds [
3] Stabilization treatment 25℃~35℃ 3 minutes [4]
Drying 75℃～io'c
About 2 minutes Processing liquid composition Tank liquid> Color developer replenisher> Bleach-fixing tank liquid> Ethylenenoaminetetodiacetate diiron ammonium dihydrate
eog ethylenecyaminetetraacetic acid 3g ammonium thiosulfate (7096 dissolved) 100IIIQ ammonium sulfite (40% dissolved >27.5g
Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to bring the total volume to IQ. Bleach-fix replenisher A> Bleach-fix replenisher B Water-washing alternative stable tank solution and replenisher solution)
3.0gB1Cu3(
45% water: liquid a) 0.65g
Ammonia water (ammonium hydroxide 25% aqueous solution) 4.
Og Automatic developing machine with the above color developing tank solution and bleach fixing tank! A running test was carried out by filling the stability tank liquid and replenishing the color developer replenisher, bleach-fixing replenisher IA, B, and stability replenisher through a metering cup every 3 minutes while processing the color vapor. The amount of replenishment is 1901IIQ to replenish the color developing tank per 12 color paper, 5011 each of bleach-fixing replenisher A and B to the bleach-fixing tank, and 5011 each of bleach-fixing replenisher A and B to the stabilization bath. 50all were replenished. The stabilization processing baths of the automatic processor are the first to third stabilization baths in the direction of the flow of the photosensitive material, and replenishment is performed from the final bath, and over 70- is transferred from the final bath to the previous tank. The multi-tank countercurrent direction was made such that the over 70-liquid also flowed into the preceding tank. Sample No. 12 of Example-1 was processed from the start of the continuous treatment until the total replenishment amount of the water-washing substitute stabilizing solution reached 2.0 times the capacity of the stabilizing tank, and the same experiment as in Example-1 was carried out. From the results of residual thiosulfate concentration and magenta dye regression-3, the present invention is effective when the thiosulfate contained in the processed light-sensitive material is 0.1 μg/Cm2 or more, and is especially effective when the thiosulfate content is 0.5 μg/Cm2 or more.
/c+e2 or more is preferable, most preferably 1.0 μg
It can be seen that it is ram2. [Effects of the Invention] The method of the present invention does not require the use of washing water for color development processing, and therefore does not require the energy cost of adjusting the temperature of washing water. To provide a color photographic image with improved fading resistance of a magenta dye image when stored for a long period of time under irradiation.

Claims (6)

[Claims] (1) After color-processing a silver halide color photographic material containing a magenta coupler represented by the following general formula [I], 0.1 μg/cm of thiosulfate was added to the processed silver halide color photographic material. A method for processing a silver halide color photographic material, characterized by containing ^2 or more. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. It's okay. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. R represents a hydrogen atom or a substituent. ] (2) The method of containing 0.1 μg/cm^2 or more of thiosulfate in the above-mentioned processed silver halide color photographic light-sensitive material is carried out after color development of the silver halide color photographic light-sensitive material.
A silver halide color photograph according to claim 1, which is a method of processing with a fixing solution containing thiosulfate and subsequently processing with a water washing substitute stabilizing solution without substantially washing with water. How to process photosensitive materials. (3) The above silver halide color photographic light-sensitive material has the general formula [
XII], [XIII], [XIV], [XV] or [XVI]
The method for processing a silver halide color photographic light-sensitive material according to claim 1 or 2, characterized in that it contains at least one compound represented by the following. General formula [XII] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [XIV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [
XIII] ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1_2 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or an alkoxy group. R_1_3 to R_2_0 may be the same or different and each represents a hydrogen atom or an alkyl group. Y_1 represents a hydrogen atom, an acyl group, an alkoxycarbonyl group, a carbamoyl group, or a sulfonyl group, and each may be the same or different. l represents an integer of 1, 2 or 3, and m represents an integer of 0 to 2. However, l+m is 4 or less. ] General formula [XV]
▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_2_1 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R_2_2, R_2_3, R_
2_4 and R_2_5 each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, or an acylamino group, and R
_2_4 represents an alkyl group, an aryl group, a phenoxy group, or an alkoxy group; furthermore, R_2_1 and R_2
_2 may be closed to form a ring. ] General formula [XVI] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, G represents a hydroxy group or its alkali-labile precursor; Represents a heterocyclic group having a heteroatom selected from oxygen, sulfur and selenium; R_3_0, R_3_1 and R_3_2 each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group or an aryloxy group. (4) Claim 1, 2 or 3, wherein the thiosulfate is ammonium thiosulfate.
A method for processing a silver halide color photographic light-sensitive material as described in . (5) Claims 1, 2, and 3, characterized in that the pH of the emulsion film surface of the processed silver halide color photographic light-sensitive material is in the range of 2.5 to 9.0. A method for processing a silver halide color photographic light-sensitive material according to item 1 or 4. (6) The amount of thiosulfate remaining in the processed silver halide color photographic light-sensitive material is 0.5 μg/cm^2 to 50 μg.
A method for processing a silver halide color photographic light-sensitive material according to claim 1, 2, 3, 4 or 5, characterized in that the silver halide color is in the range of /cm^2.