JPS62196660A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To unit a rinsing stage and stabilizing stage by incorporating at least one kind of specific 2-equiv. magenta coupler into a silver halide color photographic sensitive material and providing specified conditions thereto. CONSTITUTION:The silver halide color photographic sensitive material contains at least one kind of the 2-equiv. magenta coupler expressed by formula I or formula II. The concn. of the aldehyde compd. in the final rinse liquid is <=1.0X10<-3>mol/l and the amt. of the final rinsing bath to be replenished is 2-50 times the amt. of carry over from the previous bath per unit area of the photosensitive material to be processed. In formula II, R1 denotes a carbonamide group or ureide group, R2 denotes a phenyl group, and X denotes a group which can be eliminated by the coupling reaction with the oxidant of an arom. primary amine developing agent. The couplers expressec by formulas I, II are generally added to the emulsion layer at 2X10<-3>-5X10<-1>mol, more preferably 1X10<-2>-5X10<-1>mol per mol of the silver in said layer. The stages for the rinsing bath and stabilizing bath are thereby simplified and are united to one stage.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for processing silver halide color photographic light-sensitive materials for photographing, and more specifically, to a photographing method that integrates a conventional water washing process and a stabilizing process. This invention relates to a simple processing method for silver halide color photographic materials.

(Prior Art) In recent years, in the processing steps of silver halide color photographic light-sensitive materials, simplification of the processing by reducing the number of processing baths has become one of seven important issues. Reducing the number of processing baths means that when processing with an automatic processor,
This leads to making the developing machine smaller and simpler.

Furthermore, the advantage of reducing the number of processing baths in this way, which leads to the complete elimination of the number of processing agents required, is extremely large.

Conventionally, the formation of dye images and desilvering processing of silver halide color photographic materials for photography have been completed by color development, bleaching, fixing or bleach-fixing, and further washing with water, but the uniformity of drying after processing is important. In order to ensure the storage stability of the dye image, it is often necessary to use a stabilizing bath as a final step.

Among the dye images of color photographic materials, magenta dyes (azomethi/pigments) are particularly discussed in the Journal American Chemical Society (J.

Am, Chem, Soc, ) Volume 72, No. 1!
As described in page Jt to page JI (/'?j01), there is a known problem in which the dye image reacts with residual pyrazolone coupler and fades, significantly impairing the storage stability of the dye image.

Of course, many improvement methods have been proposed in the past for such problems, for example, U.S. Patent No. J/4 (11
No. 7/77 Mei Wi discloses a method for preventing fading of the magenta dye by treating it with a stabilizing bath containing formaldehyde or acetaldehyde and an organic acid such as citric acid. Further, U.S. Pat. No. 3,474,136 discloses a stabilizing bath containing an adduct of aldehyde and bisulfite; U.S. Pat.
rYt specification discloses a method of treatment in a stabilizing bath containing aldehyde and a surfactant, and U.S. Patent No. Methods for improving storage stability of images and improving drying uniformity have been proposed.

The aldehydes contained in these stabilizing baths are
Applied Photographic Engineering (J
, Appl, Photo, Eng, l-r [Hiro]ko0
As described on pages 0 to λ07 (page 197), it is extremely effective in preventing fading of magenta dye images.

(Problem to be Solved by the Invention) However, aldehyde compounds used in the stabilizing bath, especially formaldehyde, may evaporate from the stabilizing bath of an automatic processor, evaporate in the drying zone, or be removed when the stabilizing solution is dissolved. There was a problem with the gas generated.

Aldehyde compounds are harmful to the human body, so in photo processing laboratories (hereinafter referred to as ``photo labs''), it is necessary to provide ventilation by installing local exhaust around automatic processing machines. The current situation is to prevent deterioration of the working environment due to aldehyde compounds.

Therefore, it is preferable to remove aldehyde compounds from the stabilizing bath in order to improve the working environment in photographic laboratories.However, since conventional ≠equivalent pyrazolone couplers are used as magenta dye-forming couplers, the above-mentioned image storage problems arise. Therefore, it was extremely difficult to remove aldehyde compounds in the stabilizing bath.

In addition, in order to simplify the processing of silver halide color photographic light-sensitive materials for photographing, a stabilizing bath containing a washing bath and a stabilizing bath containing an aldehyde compound is used, which has two functions: washing with water and stabilizing the image. It is easy to think of trying to fulfill two roles. However, when continuous processing is actually carried out in this manner, the pre-bath fixer or bleach-fixer is brought into the stabilizing bath, and in the stabilizing bath, the fixer or bleach-fixer contains A problem arises in that the thiosulfate ions contained in the stabilizer are decomposed and precipitates form in the stabilizing bath. This is because the sulfite ion contained in the fixer or bleach-fixer as a preservative for thiosulfate ions is consumed by reacting with the aldehyde compound in the stabilizing bath, and the aldehyde compound When formaldehyde is used as the solvent, this reaction is extremely likely to occur. When the thiosulfate ions brought into the stabilizing bath decompose and precipitate, the precipitates adhere to the photosensitive material, causing unevenness or scratches on the photosensitive material and increasing the minimum density of the photosensitive material. A phenomenon occurs.

This problem of precipitate formation is also pointed out in Example 1Pc of Japanese Patent Application Laid-Open No. 2463.1. On the other hand, in order to completely prevent the decomposition of thiosulfate in the stabilizing bath, if the sulfite ions in the stabilizing bath are present in excess of the aldehyde compounds in the stabilizing bath, the aldehyde compounds will be consumed. The effect of improving image storage stability due to the aldehyde compound is lost.

Furthermore, the problem of stability of the fixing bath components or bleach-fixing bath components in the stabilizing bath becomes even more pronounced as the replenishment amount of the stabilizing bath process decreases.

The first object of the present invention is to provide a method for processing silver halide color photographic light-sensitive materials for photographing, without substantially using such aldehyde compounds that are harmful to the human body, and to improve image storage stability after processing. Our goal is to provide you with an excellent processing method.

A second object of the present invention is to provide a simple treatment method that simplifies the conventional two steps of washing bath and stabilizing bath and integrates them into one step.

(Means for Solving All Problems) The above object is a method of directly processing an imagewise colored silver halide color photographic light-sensitive material in a final rinsing bath after a fixing process or a white fixing process. , the silver halide color photographic light-sensitive material has the following general formula [I] or [■
], the final rinsing bath contains at least one 2-equivalent magenta coupler, the aldehyde compound concentration in the final rinsing bath is /, 0x10 mol/ or less, and the replenishment amount of the final rinsing bath is a unit of the photosensitive material to be processed. This was achieved by a method for processing silver halide color photographic light-sensitive materials, which is characterized in that the amount brought in from the front bath per area is 2 to 10 times.

In the general formula [I] (general formula CI), R1 represents a hydrogen atom or a substituent, and X represents a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. Za,z
b and Zc are methine, substituted methine, =N- or -N
In the H-gold representation, one of the Za-zb bond and Zb-Zc bond is a double bond, and the other is a single bond. zb-Z
The case where c is a carbon-carbon double bond includes the case where it is part of an aromatic ring. Furthermore, the case where R1 or X forms a multimer of λ-mer or more is also included. In addition, when Za, zb or Zc is a substituted methine, this is included if the substituted methine forms a dimer or more multimer. ) General formula CI[] (wherein, R1 is a carbonamide group or a ureido group, R2 is a phenyl group, and X is a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. ) By the processing method of the present invention, the storage stability of magenta images after processing was significantly improved, and the water-washing process and stabilization process could be simplified to the final rinsing process. In particular, the processing method of the present invention has been able to significantly improve the light fastness of the processed image compared to the conventional processing method using cornice.

This third effect was completely unpredictable.

Specification of JP-A No. 7-4J Guco, JP-A No. 37-/3 Ko Iμ, specification of JP-A No. 17-11 AlrJ.

1f-/rl, 3/specification, 1.0-2397!
In the specification of No. O, each inthiazoline derivative.

A method of treatment with a stabilizing bath containing a benzisothiazoline derivative, a polycarboxylic acid, a soluble iron complex salt, an organic phosphonic acid, or a chelate compound and a compound that releases hydrogen ions after treatment is described. However, the above specification mainly relates to a method for processing color print materials, and does not suggest anything about the structure and effects of the present invention.

Also, JP-A No. 231132, No. 61-≠O
r1 specification, same/-μ0! λ specification, Voice IG/-
In UOyo No. 3 specification and A/-11-03 specification, 2-equivalent magenta couplers in which the linking group between the coupler core and the diffusion-resistant group is an anilino group were fixed or bleach-fixed. A method for subsequent treatment with a final rinsing bath is described.

The above magenta coupler is generally not used in silver halide color photographic materials due to its hue characteristics. In the co-equivalent magenta coupler of the present invention, those in which the linking group is an anilino group are excluded, and the processing method described in the above specification and the processing method of the present invention are completely different in structure. Furthermore, there is no suggestion whatsoever regarding the effects of the present invention.

Next, general formula [I] will be explained in detail.
In I″I, R1 represents a hydrogen atom or a substituent,
X represents a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. Za, Zb and Z
c represents methine, substituted methine, =N- or -NH-', one of the Za-zb bond and the Zb-Ze bond is a double bond, and the other is a single bond. The case where Zb-Zc is a carbon-carbon double bond includes the case where it is part of an aromatic ring. Furthermore, the case where R1 or X forms a multimer of λ-mer or more is also included. Furthermore, when Za, Zb, or Zc is a substituted methine, it also includes the case where the substituted methine forms a multimer of two or more molecules.

In the general formula rI), a multimer means one having λ or more groups represented by the general formula [I] in one molecule, and includes bis forms and polymer couplers. Here, the polymer coupler is a monomer having a moiety represented by the general formula [I] (preferably one having a vinyl group,
It may be a homopolymer consisting only of (hereinafter referred to as a vinyl monomer), or a copolymer may be prepared with a non-color-forming ethylene-like monomer that does not couple with the oxidation product of the aromatic-grade amine developer.

The compound represented by the general formula CI) is j@ring-! It is a membered ring condensed nitrogen heterocyclic coupler, and its coloring mother nucleus exhibits aromaticity similar to naphthalene, and has a chemical structure generally referred to as azapentalene. Among the couplers represented by the general formula [I], preferred compounds include iH-imidazo[/, J-b]pyrazoles, /)(-pyrazolo[/, j-b)pyrazoles, iH-pyrazolo[j,
/-c] [/, ko, μ] triazoles, iH-pyrazolo (/, j-b] [/, ko, hiro] triazoles, iH-pyrazolo C1, j-d] tetrazoles and lH-pyrazolo l :/, j-a) benzimidazoles, each having the general formula CI)-2(I)-J(I)
-da[:I"1-Ill-4 and [I]-7. Among these, particularly preferred compounds are CI)-λ,
CI]-μ, [:I)-1.

[I]-2CI)-3 [I)-Hiro CI)-, t [I]-A CI)-7 Substituents R2, R3 of general formulas [I]-2 to CI)-7
and R4 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group, an acylamino group , anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group,
Alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group, aryloxycarbonyl group, , X is a halogen atom, a carboxy atom,
Alternatively, it represents a group that bonds to carbon at the coupling position via an oxygen atom, nitrogen atom, or sulfur atom, and is a group that undergoes coupling and decoupling.

The case where R2, R3, R4 or X becomes a monovalent group and forms a bis body is also included. Also, the general formula CI)-J~C
When the moiety represented by [I]-7 is present in the vinyl monomer, R2, R3, or R4 represents a mere bond or linking group, and through this, the moiety represented by the general formula CI"]-1 to r
I) The moiety represented by -7 and the vinyl group are bonded.

More specifically, R2, R3, and R4 are hydrogen atoms, halogen atoms (e.g., chlorine atom, bromine atom, etc.), alkyl groups (e.g., methyl group, propyl group, t-butyl group, trifluoromethyl group, tridecyl group). , J-12, Hiro-di-t-amylphenoxy)propyl group, codedecyloxyethyl group, 3-phenoxypropyl group, cohexylsulfonyl-ethyl group, cyclo is methyl group, Hanzyl group, etc.), aryl groups (e.g. phenyl group, ≠−
t-i tylphenyl group, 21 μm di-t-amylphenyl group, ≠-tetradecanamidophenyl group, etc.), heterocyclic group (e.g., caufuryl group, cochenyl group, copyrimidinyl group, λ-benzothiazolyl group, etc.), cyanogen group, alkoxy group (e.g. methoxy group, ethoxy group,
comethoxyethoxy group, codedecyloxyethoxy group, comethanesulfonyl ethoxy group, etc.), aryloxy group (e.g. phenoxy group, comethylphenoxy group, 4(-t-butylphenoxy group, etc.), heterocycle Oxy group (e.g. -1penzimidazolyloxy group,
etc.), acyloxy groups (e.g., acetoxy groups, hexadecanoyloxy groups, etc.).

Carbamoyloxy group (e.g., N-phenylcarbamoyloxy group, N-ethylcarbamoyloxy group, etc.)
, silyloxy group (e.g., trimethylsilyloxy group, etc.), sulfonyloxy group (e.g., dodecylsulfonyloxy group, etc.), acylamino group (e.g., acetamido group, benzamide group, tetradecaneamide group, α
-(2゜μm di-t-amylphenoxy)butyramide group, r-(J-t-7" t-hydroxyphenoxy)butyramide group, α-(≠-(≠-hydroxyphenylsulfonyl)phenoxy)decaneamide group, lIl
, anilino group (e.g. phenylamino group, λ-chloroanilino group, λ-chloro-2-tetradecanamideanilino group, cochrochloride-dodecyloxycarbonylanilino group, N-acetylanilino group, 2-chloro-!-(
α-(3-t-butyluda-hydroxyphenoxy)dodecanamido)anilino group, etc.), ureido group (e.g., phenylureido group, methylureido group, N.

N dibutylureido group, etc.), imide group (e.g. N
-succinimide group, 3-penzylhydantoynyl group,
≠-(J-ethylhexanoylamino)phthalimide group, etc.), sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, etc.) ), alkylthio group (
For example, methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3-(≠-t-butylphenoxy)propylthio group, etc.), arylthio group (for example, phenylthio group, λ-butoxyj-t-octylphenylthio group, 3-interdecylphenylthio group, cocarboxyphenylthio group, Hiro-tetradecanamidophenylthio group, etc.), heterocyclic thio group (e.g. copenzo thiazolylthio group, etc.), alkoxycarbonylamino group (e.g., methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino group (e.g., phenoxycarbonylamino group, co,≠-di-tert- (butylphenoxycarmenyl ryomino group, etc.), sulfonamide group (e.g., methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group, λ-methyloxyj) -t-butylbenzenesulfonamide group, etc.), carbamoyl group (e.g., N-ethylcarbamoyl group, N
, N-Schiff'ylcarbamoyl group, N-(λ-dodecyloxyethyl)carbamoyl group, N-methyl-N-dodecylcarbamoyl group, N-(j-(2, Hiro-jite
rt-amylphenoxy)propyl)carbamoyl group,
etc.), acyl groups (e.g., acetyl group, (λ,lA-di-tert-amylphenoxy)acetyl group, benzoyl i, etc.), sulfamoyl groups (e.g., N-ethylsulfamoyl group, N,N-dipropylsulfamoyl group), moyl group,
N-(J-dodecyloxyethyl)sulfamoyl group,
N-ethyl-N-dodecylsulfamoylit, N,N
-diethylsulfamoyl group, etc.), sulfonyl group (e.g. methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, l, sulfinyl group (e.g. Eva, octanesulfonyl group, dodecylsulfinyl group, phenylsulfinyl group) , etc.), alkoxycarbonyl groups (e.g., methoxycarbonyl group, phthyloxycarbonyl group, dodecylcarbonyl group,
Octadecylcarbonyl group, l, aryloxycarbonyl group NFIJ tf, phenyloxycarbonyl group,
3-pentadecyloxy-carbonyl group, etc.), and X represents a halogen atom (e.g., chlorine atom, bromine atom, iodine atom, etc.), a carboxyl group, or a group linked with an oxygen atom (e.g., acetoxy group, propane atom, etc.). Noyloxy group, benzoyloxy group, λ, Hiro-dichlorobenzyloxy group, ethoxyoxaroyloxy group, bilbinyloxy group, cinnamoyloxy group, phenoxy group, darcyanophenoxy group, μm methanesulfonamide phenoxy group , μm methanesulfonylphenoxy group, α-naphthoxy group, 3-tadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, λ-cyanoethoxy group, benzyloxy group, λ-7enethyloxy group,
λ-phenoxyethoxy group,! -phenyltetrazolyloxy group, λ-benzothiazolyloxy group, etc.), groups linked via a nitrogen atom (for example, benzenesulfonamide group, N-ethyltoluenesulfonamide group, heptafluorobutanamide group, etc.).

3, ≠, j, 4--! -ntafluorobenzamide group, octane sulfonamide group, p-cyanophenylureido group, N,N-diethylsulfamoylamino group, l-pi is lysyl group,! ,! -dimethyl-2.4cm dioxo-3-oxazolidinyl group, /-benzyl-ethoxy-3-hydantoinyl group, 2N-/, /-dioxo-j (JHI-oxo-11,2-benzisothiazolyl group, 2-oxo -/, 2-dihydro-7-pyridinyl group, imidazolyl group, pyrazolyl group, 3.!-diethyl group.

Co, 4cm) Riazol-7-yl,! - or t-promobenzotriazol-/-yl,! -Methyl-/
, 2. J,! -) lyazol-7-yl group, (nzuimidazolyl group, 3-benzyl-/-hydantoinyl group, l
-Benzil-! -hexadecyloxy-3-hydantoynyl group, j-methyl-7-tetrazolyl group, Hiro-methoxyphenylazo group, ≠-piparoylaminophenylazo group, cohydroxy≠-protunoylphenylazo group, etc.), sulfur atom (e.g., phenylthio group, 2-carboxyphenylthio group, comethoxyt)
-t-octylphenylthio group, ≠-methanesulfonylphenylthio group, goo-octanesulfonamidophenylthio group, coptoxyphenylthio group, 2-<2-hexanesulfonylethyl)-j-tert-octylphenylthio group, benzylthio group group, cocyanoethylthio group.

l-ethoxycarbonyltridecylthio i, t-phenyl-J, J, g, j-tetrazolylthio group, cobenzothiazolylthio group, codedecylthio-r-thiophenylthio group, 2-phenyl-3-dodecyl- /, J, 4c
m) Riazolyl-! -thio group, etc.).

When R2, R3, R4 or X becomes a divalent group to form a bis body, this divalent group is described in more detail as follows:
Substituted objects include unsubstituted alkylene groups (e.g., methylene group, ethylene group, /, 10-decylene group, -CH2CH2
0-CH2CH2-1, etc.), a substituted or unsubstituted phenylene group (for example, l.

μm phenylene g, /, i-7 enylene group, -NHCO-R2-CONH- group of CH3 (R2 is a substituted or unsubstituted alkylene group or a phenylene group).

When those represented by general formulas [I]-2 to [:I]-7 are present in the vinyl monomer, the linking group represented by R2, R3, or R4 is an alkylene group (substituted or unsubstituted Alkylene group, for example, methylene group, ethylene group,
1. IO-decylene group, -CH2CH20CH2CH2
-1, etc.), phenylene group (substituted or unsubstituted phenylene group, such as /, ≠-phenylene 7a, 1.!-phenylene group, -NHCO-1-CONH-1-〇-1-O
It includes groups formed by combining CO- and aralkylene groups (eg, α, etc.).

The vinyl group in the vinyl monomer has the general formula CI]-
-2 to [''I) This also includes cases where the substituent is present in addition to those represented by -7. Preferred substituents are hydrogen atoms, chlorine atoms, or lower alkyl groups having l-μ carbon atoms. be.

Acrylic acid, α
- Chloroacrylic acid, α-alacrylic acid (e.g. methacrylic acid, etc.) and esters or amides derived from these acrylic acids (e.g. acrylamide,
n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propylacryle), n-7thyl acrylate, t-butylacrylate, 1so-butylacrylate, 2-ethyl hexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), methylene dibis acrylamide, vinyl esters (e.g. vinyl acetate, vinyl f-ropionate and vinyl laut). ), 7crylonitrile, methacrylateril, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyltoluene,
divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid,
Examples include vinylidene chloride, vinyl alkyl ether (eg, vinyl ethyl ether)% maleic acid, m-hydric maleic acid, maleic acid ester, N-vinyl-pyrrolidone, N-vinylpyridine, and -λ and ≠-hinylpyridine. It also includes cases where two or more of the non-color-forming ethylenically unsaturated monomers used herein are used together.

Compound examples and synthesis methods of the couplers represented by the general formulas CI]-J to (:I]-7 are described in the documents listed below.

The compound of general formula [I]-2 is obtained from patent application Sho sr-λ34c3.
Hiroshi et al., the compound of the general formula (I:l-j)
IJ-/Jj≠, etc., the compound of the general formula [I)-μ is the patent application Sho 7-27≠l/etc.K, and the compound of the general formula (:I)-j is the patent application Sho 1! -4c! ! /λ and the same! Day 277
≠j, etc., the compound of the general formula [I]-B is a special application! ! r
-/17210/ etc., and compounds of the general formula CI)-7 are described in US Pat.

Maku, Tokukai Akira! ♂−μ−〇Hiroshi! , special request show jr-r r
y e o, same jr-Ji292J, same, tl-! 2 2 ≠ and the same j zaichi! The highly color-forming palaste group described in Kota 27 etc. has the above general formula [:I]-λ~CI]
-7 compounds.

Specific examples of the pyrazoloazole coupler used in the present invention are shown below, but the invention is not limited thereto.

Σ 〉 2 2
Σρ8ρ 2 2
2! Next, the general formula CI[] will be explained in detail. In the formula, R1 is a carbonamide group, a sulfonamide group, or a ureido group, R2 is a phenyl group, and A group capable of leaving by a coupling reaction (hereinafter referred to as a leaving group) f: represents.

X is an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom coupled to an activated carbon and an aliphatic group, an aromatic group,
Groups that bond with heterocyclic groups, aliphatic/aromatic or heterocyclic sulfonyl groups, aliphatic aromatic or heterocyclic carbonyl groups, carbamoyl groups, alkoxycarbonyl groups and aryloxycarbonyl groups, halogen atoms, aromatic groups These include an azo group and a heterocyclic group. Aliphatics included in XK,
The aromatic or heterocyclic groups R1 and R2 may be further substituted, such as halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.), alkyl groups (e.g. methyl group, t-octyl group, dodecyl group). group, trifluoromethyl group, etc.), alkenyl group (e.g. allyl group, octadecenyl group, etc.), aryl group (e.g. phenyl group, p
-) lyl group, naphthyl group, etc.), alkoxy group (e.g. methoxy group, benzyloxy group, methoxyethoxy group, etc.)
, aryloxy group (e.g. phenoxy group, 2.≠-di-tart-amylphenoxy group, J-tert-butyl-μm hydroxyphenoxy group, etc.), acyl group (e.g. acetyl group, benzoyl group, etc.), sulfonyl group (fl
l, tJ-j' methanesulfonyl group, toluenesulfonyl group, etc.), carboxy group, sulfo group, cyano group, hydroxy group, amino group (e.g. eva-amino group, dimethylamino group, etc.), carbonamide group (e.g. acetamide group, trimethylamino group, etc.) Fluoroacetamide group, tetradecanamide group, benzamide group, etc., sulfonamide group (e.g., methanesulfonamide group, hexadecanesulfonamide group, p-toluenesulfonamide group, etc.), aldioxy group (e.g., a7toxy, etc.), sulfonyloxy group ( For example, methanesulfonyloxy group, etc.], alkoxycarbonyl group (for example, dodecyloxycarbonyl group, etc.), oxycarbonyl group (for example, phenoxycarbonyl group, etc.), carbamoyl group (for example, dimethylcarbamoyl group, tetradecylcarbamoyl group, etc.) ), sulfamoyl groups (e.g. methylsulfamoyl group, hexadecylsulfamoyl group, etc.), imide groups (e.g. succinimide group, phthalimide group, octadecenylsuccinimide group, etc.), heterocyclic groups (λ
-pyridyl group, λ-furyl group, 2-naenyl group, etc.), alkylthio groups (flJ, methylthio group, etc.), and arylthio groups (eg, phenylthio group, etc.). Specific examples of etc.), acyloxy groups (e.g. acetoxy group, tetrazocallyoxy group, indiyloxy group, etc.), aliphatic or aromatic sulfonyloxy groups (e.g. methanesulfonyloxy group, toluenesulfonyloxy group, etc.), carbonamide group ( (e.g., dichloroacetamide group, trifluoroacetamide group, etc.), aliphatic or aromatic sulfonamide group (e.g., methanesulfonamide group, p-)luenesulfonamide group, etc.), alkoxycarbonyloxy group (e.g., ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), oriroxycarbonyloxy group (eg.

(e.g., phenoxycarbonyloxy group, etc.), aliphatic/aromatic or heterocyclic thio group (e.g., ethylthio group, hexadecylthio group, ≠-dodecylphenylthio group, pyridylthio group, etc.), ureido group (e.g., methylureido group, phenylureido group, etc.) ).

! membered or 6-membered nitrogen-containing heterocyclic group (e.g., imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, 7,2-dihydro-2-oxo-/-pyridyl group, etc.), imide group (e.g., succinimide group, phthalimide group, etc.) group, hydantoinyl group, etc.), aromatic azo group (eg, phenylazo group, etc.), and the like. Furthermore, there are so-called bis-type couplers obtained by condensing a reference coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom.

Either R1, R2 or A coupler may also be formed.

It is also known in the art that the coupler represented by the general formula [■] has the following keto-enol tautomerism.

Examples of the compound represented by the general formula [■], synthesis methods, etc., can be found in, for example, JP-A Show Data ///63/, same j → t! ≠
O1 same j! -42≠! ≠, same jj-//r03+, same J
-4-310143, 77-roo4Lz, 74-
/2tlrJJ%sameJ-7-ao4La,same! -7-J
! I! r, same j7-tahiro 7!2, same 11-/7≠4! O
1 same rr-j0337, same! ? -4! ≠32, same jlr
-/ /7! lit, same! r-/24!30. Same 5r-
itizqua, same 11-20! / jl, Tokuko Akij!
-770, same jp-10149/, same j hiro-2/2! r
,same! 3-IAAIA! 2, 13-17 @jJ, 1
7-34!77, special application Shoj1-I10J-'? t, same j
1-/3 13μ, same! Tar λt7 kota, rice 1i411
j u27111A, 3μj 212 /, Dohiro, 3
104/r, ≠311127, etc.

In the present invention, those having an azole compound leaving group are particularly preferred.

Hereinafter, represented by the general formula [''I[]!-Pyrazolone 2
Examples of preferred compounds among equivalent magenta couplers are shown below, but the invention is not limited thereto.

(M-Hiroko) α (M-μ3) (M-4'4'1 α (M-4'jl (M-≠t) (M-μ7) α (M-dat) (M-μri ) (M-70) (M-jJ) (M-tt) (M-j6) (M-1) (M-12) α (M-123 (M-131 (M-A≠) (M-1jl (M-141 (M-173 (M-6ri) CM-70) a (M-7/) +M-721 (M-731 (M-7j) (M-74> (M-77) (JL; fi) 15 (M-72) Cε (M-j/) (M-rul α (M-1rJ) (M-4≠) (M-rj) - Ding 1111 The coupler of the present invention is in the same layer The same compound may be contained in two or more different layers.

The couplers of the present invention generally have a wavelength of λ per mole of silver in the emulsion layer.
3 moles of XIO"" to J-x10" moles, preferably 1 xio-2% to JXlo" moles. When used in combination with the above couplers, the total amount of couplers that produce the same color is added. is preferably within the above range.

The above-mentioned coupler can be introduced into the silver halide emulsion layer by a known method, such as the method described in US Pat. No. 6,322,027. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate,
triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), or organic solvents with a boiling point of about 30°C to 1zo0c, such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketones,
After being dissolved in β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

Tokko Akira again! l-3rit! 3. Tokukai Shozi-t Tata μ3
It is also possible to use the polymer dispersion method described in .

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

Photographic emulsions made using the present invention may contain color image-forming couplers other than those of the present invention. The coupler is preferably a non-diffusive coupler having a hydrophobic group called a ballast group in its molecule. The coupler may be either μ-equivalent or monoequivalent to silver ions.

It may also contain a colored coupler that has a color correction effect or a coupler that releases a development inhibitor upon development (so-called DIR coupler).The coupler may be a coupler in which the product of the coupling reaction is colorless.

As the yellow coloring coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide and piparoylacetanilide compounds are advantageous.

As the cyan color-forming coupler, phenolic compounds, naphthol compounds, etc. can be used. Especially Akira Tokgan! Tar 1023! Preferred are phenolicyan couplers in which the 3-position is substituted with an acylamino group and the 2-position is substituted with a ureido group, as described in item ≠.

In addition, colored couplers and DIR couplers (particularly DIR couplers that release highly diffusive development inhibitors) can be used in combination. may be included in the material, for example, US Pat. No. 3,297. μ≠
! Issue ~ 3/37, J-27, West German patent issue (OL
S) Those described in λ, μ/7, 9/μ, JP-A-12-/J-Core/, and JP-A-1973-//1 can be used.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. (e.g. benzene substituted with an aryl group) +1 azoyl compounds (e.g. those described in U.S. Pat. 3.3!ko.

61/), benzophenone compounds (e.g., those described in JP-A-Sho μt-271rlt), cinnamic acid ester compounds (e.g., U.S. Pat. No. 3,70!, 1)
0! No. J, 707.37j), butadiene compounds (e.g. those described in U.S. Pat.
For example, U.S. Patent No. 3.700. ≠! ! (mentioned in the issue)
can be used. Additionally, U.S. Patent 3.4A9,
No. 762, Tokukai Sho! Those described in IL-411!131 can also be used. A UV-absorbing coupler (for example, an α-naphthol-based cyan dye-forming coupler) or a UV-absorbing polymer may be used all around. These UV absorbers may be mordanted into certain layers.

The photographic emulsion used in the present invention is P, Glafkide.
Chimie et Physique Photo by i
ographique (published by Paul Monte1,
/ri 67 years 1, G, F.

Duffin￥F Photographic Emu
lsionCbemistry [The Focal
Published by Press, 1st year of 1st year, V, L, Zel
Making and C by ikman et al
oating Photographic Emulsi
It can be adjusted using the method described in On (published by The Focal Press, / 6 Kou).

In the present invention, silver halide emulsions with regular crystal shapes and nearly uniform grain sizes can also be used.

It is also possible to use a mixture of two or more silver halide emulsions formed separately.

The coupler of the present invention has tabular grains, especially grains with a grain size/thickness ratio of t or more, and especially grains on rlJ, which have a total projected area of ro
It may be used in combination with an emulsion that occupies qb or more.

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

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used.

The photographic emulsion used in the present invention has photographic properties that prevent fog during the manufacturing process, storage, or photographic processing of light-sensitive materials. ? Various compounds can be included for stabilizing purposes. That is, azoles such as nzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzodiazoles, etc. Triazoles, nitrobenzotriazoles, mercaptotetrazoles (especially /-phenyl-!-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxazolinthione; azaindenes,
For example, triazaindenes, tetraazaindenes (
Especially known as antifoggants or stabilizers such as μm hydroxy-substituted (/, J, Ja, 71 tetrazaindenes), hantaazaindenes; Many compounds can be added. For example, U.S. Pat. ri12
, No. 9447, Tokko Akira! The book described in λ-λr, tto issue can be used.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or accelerating development, for example, t is polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, and thiomorpholines. , quaternary ammonium salt compounds, urethane derivatives,
It may also contain urea conductors, imidazole derivatives, 3-pyrazolidones, and the like.

The photographic emulsions used in this invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be applied to these dyes as basic heteronuclear nuclei. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.: a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of
S-hbchi, indolenine nucleus, benzindolenine nucleus,
Applicable are indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes contain pyrazoline-! as a core having a ketomethylene structure. -on nucleus, thiohydantoin nucleus, nithioxazolidine-2
, 4L-dione nucleus, thiazolidine-2, Hiro-dione nucleus,
Rhodanine nucleus, thiobarbyl acid root, etc.! ~6-membered heteroartic ring nuclei can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

In the photographic material produced using the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener. These may be water-soluble,
A water-insoluble brightener may also be used in the form of a dispersion.

In carrying out the present invention, the following known antifading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more.

Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, bisphenols, and the like.

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

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The concentration of the aldehyde compound in the final rinsing bath (hereinafter abbreviated as rinsing bath) of the present invention is preferably 0.times.10@-3 mol/or less, particularly 0.0. j×lO mol/1. It is preferable that it is below.

Examples of aldehyde compounds include the following compounds, but the present invention is not limited to these compounds.

Formaldehyde Acetaldehyde Propionaldehyde Isodutyraldehyde n-Butyraldehyde Aldol Propiolaldehyde Acrolein Crotonaldehyde Salicylaldehyde Glyoxalic acid Mucochloric acid Mucobromic acid Furfural Diglycolaldehyde Glyoxal Salicylaldehyde Glutaraldehyde α-Methylglutaraldehyde Cyclo-tanthanedicarboxaldehyde these Among the compounds, it is preferable to use formaldehyde as the aldehyde compound.

In addition to the above-mentioned compounds, the rinsing bath of the present invention may contain various surfactants in order to prevent uneven water droplets when drying the photosensitive material after processing. These surfactants include polyethylene glycol type nonionic surfactants, polyhydric alcohol type nonionic surfactants, alkylbenzenesulfonate type anionic surfactants,
Higher alcohol sulfate ester salt type anionic surfactants, alkylnaphthalene sulfonate type anionic surfactants, grade ammonium salt type cationic surfactants, amine salt type cationic surfactants, amino acid type amphoteric surfactants There are betaine-type amphoteric surfactants, but ionic surfactants may combine with various ions mixed in during processing to produce insoluble substances, so it is not recommended to use nonionic surfactants. are preferred, and alkylphenol ethylene oxide adducts are particularly preferred. Alkylphenols include octyl, nonyl, dodecyl,
Dinonylphenol is preferred, and the number of moles of ethylene oxide added is particularly 1/C1! −/reference mole is preferable.

The rinsing bath of the present invention may contain an antibacterial agent or an antifungal agent in order to prevent the formation of water scale and mold on the photosensitive material after processing. Examples of these antibacterial and antifungal agents are listed in JP-A-Sho 7-/J-
72 Kosan No. and the same t-10! /4c! Thiazolylbenzimidazole compounds, as shown in the issue, or JP-A-Sho! Inthiazolone compounds as shown in No. 7-414Lλ, lolophenol compounds such as trichlorophenol, bromophenol compounds, organotin and organozinc compounds, thiocyanic acid and inthiocyanic acid. type compounds, acid amide type compounds, diazine and triazine type compounds, or benzotriazole type compounds.

Thiourea compounds, alkylguanidine compounds, μ-class ammonium salts such as benzalkonium chloride, antibiotics such as penicillin, etc., are included in the Journal Antibacteria and Antifungus. Agent (J, A
ntibact.

Antifung, Agents) Voll, &j.
It is also possible to use the general-purpose anti-spill agent Q/species or more described in p-207 to λ23 (1913) in combination.

Furthermore, various fungicides described in Japanese Patent Application Laid-Open No. 2002-120003-r3gλO can also be used.

In addition, various compounds may be added to the rinse bath of the present invention. For example, metal salts typified by magnesium salts, aluminum salts, zinc salts, nickel salts, and bismuth salts, or hardening agents for reducing drying load may be added as necessary. Father, L, E, West ``Water Quality Criteria'' (WaterQuaLtt7Cr1t
eria”) Photographic Science and Engineering Link (Photo.

Set, and Eng, 1. vol ta, 4A(/
Compounds described in 4j1 etc. may be added.

Further, various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate, etc. can be added as a membrane pH adjusting agent after treatment.

The rinsing bath of the present invention is used with P HJ to fKJ adjusted,
For pH adjustment, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, ammonia, mineral acids such as sulfuric acid and hydrochloric acid, and organic acids such as acetic acid, tartaric acid and citric acid can be used.

In particular, it is preferable to add a chelating agent to the rinsing liquid of the present invention from the viewpoint of liquid stability. As a chelating agent,
Examples include inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, and phosphonocarboxylic acid. Specific examples of typical chelating agents are shown below, but the invention is not limited thereto.

p −/ Na4P4012 F-2Na6P4013 F−≠ CH2C0OH -s -t F-ta 1:'-i.

)'-// F-/ ko)'-/J F-/φ F-/j F-/4 F-/7 )'-/r F-/riCH3 H2O5P-C-PO3H2 CH F-20CH2CH3 H2O5P -C-PO3H2 CH F-2/ C) (zcOOH H2O5P-C-COOH CH2 CH2C0OH CH2-COOH CH(PO3H212 p-2sF-244 CH2COOH F-2zF-26 CH3shiH21,U(Jti F, 27 F -21rF -2ta
1'-30 薯CH2 CH2COOH F+ 37 F -32F-33 CH3COO)1 C(P03H2>2 CH2C0OH The carboxylic acid and phosphonic acid groups of these chelating agents are magnesium, calcium, bismuth, lithium, sodium, potassium, ammonium and iron. , may form a salt with metal ions such as zinc.

The chelating agent used in the present invention is
The above-mentioned chelating agent, which can be contained in the range of 10' to 1xio' moles, preferably at a concentration of 10' to 10' moles, may be added to the rinse bath or may be added to the rinsing bath. It may be supplied by being brought in from the previous bath by being included in the developer, bleach, fixer, or bleach-fix solution in the bath.

The rinsing bath of the present invention is preferably a multi-stage countercurrent water washing with one or more tanks, and particularly preferably one to three tanks.

The amount of washing water or stabilizing solution to be replenished is o, z-to times the amount brought in from the previous bath (fixing bath, bleach-fixing bath) per unit area of the photosensitive material to be processed, but preferably 3 to 3 times the amount brought in from the previous bath (fixing bath, bleach-fixing bath). It is 0 times more.

The above relationship between the amount of replenishment and the amount brought in from the pre-bath only needs to hold true at least in the tank closest to the pre-bath, but it is important that all types of multi-tiered tanks have this ratio relationship. is preferred.

The temperature of the water washing bath or stabilization bath may be arbitrary, but it is between j00 and +j.
'C1 is preferably 10°c to ao0c.

The processing method of the present invention can be applied to any processing of color light-sensitive materials for halogenated photography, such as color negative films and color reversal films. It can also be applied to processing color X-ray films.

Typical processing steps in the present invention are shown below, but it goes without saying that the process is not limited thereto.

A, Color development - Bleach - Washing and fixing - Rinse - Drying B6 Color development - Bleach and fixing - Rinse - Drying C, Color development - Bleach - Bleach-fixing - Rinse-drying, Color development - Bleach-fixing - Rinse - Drying E. Color development - Bleach - Bleach fixing - Constant fixing - Rinse - Drying F, Color development - Water washing - Bleach fixing - Rinse drying G, First development (black and white development) - Water washing - Reversal - Color development - Adjustment - Bleach - Constant fixing - Rinse - Drying H0 - Development - Washing - Reversing - Color development - Adjustment - Bleaching - Bleach fixing - Rinse Drying -Water wash - Reversal - Color development - Bleach constant - Rinse and dry, 1st development - Water wash - Reversal - Color development - Bleach - Bleach fix - Rinse - Dry, 1st development - Water wash - Reversal - Color development - Bleach fixing - Rinse - Drying M, 1st development - Water washing - Color development - Bleach-fix solution -
Drying N, 1st development - Water washing - Color development - Bleach - Bleach fixing - Rinse Drying 0, 1st development - Water washing 1 Color development - Bleach fixing - Rinse drying No. 7 aromatic compound used in the color developing solution in the present invention Amine-based color developers include known ones that are widely used in various color photographic processes. These developers include amine phenolic and p-phenylene diamine derivatives. Preferred examples are p-phenylenediamine derivatives, and representative examples are shown below, but the invention is not limited thereto.

D-/N,N-diethyl-p-)nisediamine])-2J-amino-j-diethylaminetoluene D-32-amino-j-(N-ethyl-N-laurylamino)toluene D-Hiroshi ≠- [N-Ethyl-N-(β-hydroxyethyl)aminocoaniline Dt comethyl-≠-[N-ethyl-N-(β-
hydroxyethyl) aminocoaniline D-A N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-≠-aminoaniline D-7N-(J-amino-!-diethylaminophenylethyl)methanesulfonamide D-1r N, N-dimethyl-p-funisenediamine D-tahiro-amino-3-methyl-N-ethyl-N-methoxyethylaniline])-104cm7 minnow 3-mef # -N -ethyl-N -β-ethoxyethylaniline 1)-//μmamino-3-methyl-N-ethyl-
N-β-Butoxyethylaniline These p-phunisenediamine derivatives may also be in the form of sulfate, hydrochloride, sulfite, p-toluenesulfonate, and other salts. The above compounds are described in U.S. Patent λ, 15'
J, 0/J issue, same 2. jj2゜λhiro 1, same λ, jAj
, λ71, same, jri λ, 36≠, same j, jjj,
It is described in Ta JO No. 3゜691, J21, etc. The amount of the aromatic-grade amine herbal medicine to be used is about 0.1 to about 20 liters per developing solution. , more preferably about o
The concentration is from 3t to about 10f.

As is well known, the color developer used in the present invention may contain hydroxylamines.

The amount of hydroxylamine added is 0 per lt of color developer.
? , /Of is preferable, and more preferably 0, j
It is f. If the stability of the color developer is to be maintained, it is preferable that the amount added be small.

As a preservative, it is preferable to contain sulfites such as sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts. These additives are preferably 0f-209/l, more preferably op,! f/l, and the smaller the better if the stability of the color developer is maintained.

Other preservatives include Tokukai Sho! λ−≠rir, Zt,
Same j6-μ7031, same j6-321 reference θ, same! Aromatic polyhydroxy compounds described in US Pat. No. 11aO/It and US Pat.
, J03 and British Patent I.

! 04. /Hydroxyacetones described in No. 74; JP-A-Sho! Kota3o Koo issue and the same! α-aminocarbonyl compounds described in 3-Tri μ21; various metals described in JP-A No. 7-J7-μ≠1-Hiro and 17-J37-μ2, etc.; Each sugar; same! 2-2
Hydroxamic acids described in No. 763r;
α,α'-dicarbonyl compound described in iμ/ issue - same! Salicylic acids described in Tarlorgy; same j≠-3j3
Alkanolamines described in No. 2;
Poly(alkyleneimine)s described in No. A2; jA-7
Examples include gluconic acid derivatives described in No. 1Aμ7. Two or more of these preservatives may be used in combination if necessary.

The color developer used in the present invention preferably has a pH of ~1, more preferably ~0, and the color developer may contain other known developer components. be able to.

In order to maintain the above pH, it is preferable to use various buffers.

Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt, N,N dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3. Hiro-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-λ-methyl-7,
3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt-lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates have a high solubility and pH value.
These buffering agents have the advantage of having excellent buffering ability in the area, no adverse effects on photographic performance (fogging, etc.) even when added to color imaging solutions, and being inexpensive. Particularly preferred.

Specific examples of these ** agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, trisodium phosphate, dipotassium phosphate, sodium borate, and boron. Potassium acid, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate,! -Sodium sulfo-2-hydroxybenzoate (sodium 1-sulfosalicylate),! -Potassium sulfo λ-hydroxybenzoate (!-potassium sulfosalicylate) and the like can be mentioned. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is preferably 0.1 mol/or more, particularly 0.1 mol/1.0.
Particular preference is given to II mol/l.

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

The chelating agent is preferably an organic acid compound, for example,
Special Publication Show μIr-0304I94 and μμm3023
Aminopolycarboxylic acids described in No. 2, JP-A-Sho! 6-ta 7
3μ7, special public show j6-3ri3! No. and West German Patent Co., Ltd.
Organic phosphonic acids described in No. 227.6J, JP-A-Sho! Co 102721. Same issue! 3-≠, No. 2730, Oka! Hiro-l/core issue, time! ! -/2624c1 and same j
Phosphonocarboxylic acids described in J-Atri J6, etc., and other JP-A-Sho! One minute! Hiroshi! No., PIjr-203μ
Compounds described in No. 33-≠oyoo and the like can be mentioned. Specific examples are shown below, but the book is not limited to these.

O Nitrilotriacetic acid 0 Diethylenetriamine Pentaacetic acid 0 Triethylene Tetramine Hexaacetic acid ON,N,N-trimethylenephosphonic acid 0 Ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid 07,3-Diamino-copro A nor- μ acetic acid o transcyclohexanediaminetetraacetic acid 0 nitrilotripropionic acid OL, 2-diaminoprononetetraacetic acid 0 hydroxyethyliminodiacetic acid O glycol ether diamine western acetic acid 0 hydroxyethylenediamine triacetic acid 0 ethylenediamine orthohydroxyphenylacetic acid 0 λ-phosphonobutane-1 , co, μ-tricarboxylic acid O7-hydroxyethane-/,/-diphosphonic acid ON, N'-bis(2-hydroxy(andyl)ethylenediamine-N,N'-diacetic acid) These chelating agents may be used as necessary. Two or more types of chelating agents may be used in combination.The amount of these chelating agents added may be sufficient as long as it is sufficient to sequester metal ions in the color developer.For example, it is about O/f-10t/lt.

Any development accelerator can be added to the color developer if necessary. However, benzyl alcohol does not substantially contain
The amount added is 0.00% per color developer. ! d/l or less, preferably not at all. Other current power promoters include Tokko No. 37-76011, No. 37-1917, No. 3t-711, l'fl$44-12310,
No. 446-901 and U.S. Patent 3♂/32μ7-j
! Thioether compounds described in JP-A No. 2-≠Rikota, and JP-A No. 10-/! 11μ, JP-A-60-/3772, JP-A-Sho μμm No. 3007μ, JP-A-Sho! t-16612
μ-class ammonium salts described in No. 6 and No. 6 and No. L of the same, U.S. Patent No. 2.610, /
/ri, p-amine phenols described in μz2; U.S. Patent No. 2. ≠ri4! , No. 903, same j, /21. / No. 12, μ.

Ko3Q, 7riwo issue, same j, 2!3. R/RI issue, special public official Aki U
/-/1uJ1, US Patent 2.4412゜j≠6,
Ibid., No. 19&, 226 and Ibid. J, j12.341
Amine compounds described in No. 6 etc.; Tokko Sho J7-itor
No. r, No. 82-21201, U.S. Patent J, /21. /
No. 13, Tokuko Akihiro/-/1tA37, Doko Akihiro 2-231
No. 113 and U.S. Patent J,! 32. ! Polyalkylene oxide described in No. 0/ etc., others/-Phenyl-3-
Pyrazolidones, hydrazines, mesoionic compounds,
Thione type compounds, imidazoles, etc. can be added as necessary. In particular, thioether compounds and l-
Phenyl-3-pyrazolidones are preferred.

In the present invention, an arbitrary antifoggant can be added to the color developer, if necessary. As antifoggants, alkali metal halides such as potassium bromide, sodium bromide, potassium iodide, and organic antifoggants can be used.

Examples of organic antifoggants include benzotriazole, nitrobenzimidazole, and j-nitroisoindazole. -Methylbenzotriazole,! -Nitrogen-containing heterocyclic compounds such as nitropenzotriazole, j-chlorobenzotriazole, coachazolyl-benzimidazole, λ-thiazolylmethyl-benzimidazole, hydroxyazaindolizine, and/-phenyl-
! -Mercapto-substituted heterocyclic compounds such as mercaptotetrazole, co-mercaptobenzimidazole, co-mercaptobenzothiazole, adenine, and also mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. Particularly preferred are nitrogen-containing heterocyclic compounds. These antifoggants may be eluted from the color light-sensitive material during processing and accumulate significantly in the color developer.

In particular, it is common to contain bromine ions, and as long as fogging does not occur, it is preferable that the amount added be small from the viewpoint of promoting development. For example jxlo '~' X/O
It is preferable to add an amount of rnot/l, especially from x10-4 to
jxlO-3 mot/l is preferred.

The nitrogen atom of the dilamines may be substituted with an alkyl group.

The color developer used in the present invention preferably has a pH of ~1-1, more preferably ~//, 0, and the color developer may contain other known developer component compounds. I can do it.

For example, as the alkaline agent and pH buffering agent, caustic soda, caustic potash, sodium carbonate, potassium carbonate, sodium chloride, tertiary potassium phosphate, potassium metaborate, borax, etc. may be used alone or in combination.

In addition, for the purpose of providing buffering capacity, for convenience in formulation, or to increase ionic strength, sodium chloride (conodium or potassium hydrogen phosphate, potassium λ hydrogen phosphate, or potassium phosphate) may be added.
Various salts are used, such as IJum, sodium bicarbonate or potash, boric acid, alkali nitrate, alkali sulfate, and the like.

In addition, various chelate shavings can be used in color developing solutions to prevent precipitation of calcium and magnesium. For example, polyphosphates, aminopolycarmenic acids,
Phosphonocarboxylic acids, aminopolyphosphonic acids, /-
Examples include hydroxyl-kylidene/,/-diphosphonic acids.

Any development accelerator can be added to the color developer if necessary. For example, US Pat.
Various birimidium compounds and other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate and potassium nitrate, Japanese Patent Publication No. 4 Hiroshi-9 JOIA, U.S. Patent Publication No. 33.290.
No. λ.

No. 131.132, No. 2,9jO, No. 970, No. 3
Nonionic compounds such as polyethylene glycol and its derivatives described in No. 77.127, polythioethers, and thioether compounds described in U.S. Pat.

Additionally, sodium sulfite, potassium sulfite, potassium bisulfite, or sodium bisulfite, which are commonly used as preservatives, can be added.

In the present invention, the color developer may be used as necessary.

Any antifoggant can be added. Antifoggant The color developer of the present invention preferably contains a fluorescent brightener. As a fluorescent brightener, ≠, ≠′-diamino! ,,
2'-disulfostilbene compounds are preferred. The amount added is 0-79//=, preferably 0. /l～ノf/l
It is.

Various surfactants such as alkylphosphonic acid, alkylphosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as necessary.

The processing temperature of the color developer of the present invention is preferably 2.0-JOoC, more preferably 30-JOo'C. The processing time is preferably 20 seconds to j minutes, more preferably 30 minutes.
It is from seconds to 2 minutes. The replenishment amount is 20~t of photosensitive material/m2.
oo- is preferred, and more preferably jO-3ooml. Particularly preferred is OO penalty to λθOml.

In the present invention, a bleach-fixing process is performed after color development.

The process time of whitening fixing treatment in the present invention is preferably 1
The process time of normal bleach-fixing process (approximately 7 minutes)
30 seconds). Here, the bleach-fix process time (hereinafter simply referred to as "bleach-fix time") is the time from when the photosensitive material comes into contact with the bleach-fix solution until it comes into contact with the washing water of the primary bath, In addition to the time the photosensitive material is immersed in the bleach-fixing bath, it is calculated by adding the time it takes to move from one place to another, that is, the time it stays in the air. In the present invention, the preferred bleach-fixing time is 30 seconds to 60 seconds.

The bleach-fix solution of the present invention may contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfite, etc. as preservatives. Sulfites (e.g. potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.)4
Contains 4 sulfite ion-releasing compounds. It is preferable that these compounds contain approximately 0.02 to 0.30 mol/concentration in terms of sulfite ion, more preferably o, 1
oo, 2o mol/l.

Other preservatives that can be used in the present invention include hydroxylamine, hydrazine, and bisulfite compounds of aldehyde compounds (e.g., acetaldehyde sodium bisulfite).
etc. can be mentioned.

The bleaching agent used in the bleach-fixing bath of the present invention is iron tI.
Organic complex salts of I[) (e.g. ethylenediamine 4ffE1
1! , aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, complex salts of aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acid) or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; hydrogen peroxide etc. can be mentioned. Among these, iron (II
The organic complex salt I) is preferable from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming an organic complex salt of iron (ITS) are listed below.

Ethylenediaminetetraacetic acid.

diethylenetriaminepentaacetic acid, ethylenediamine-N-tβ-oxyethyl)-N,N
',N'-triacetic acid, /,2-diaminopronotetracetic acid, triethylenetetraminehexaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid.

Cyclohexanediaminetetraacetic acid, l 3-diaminorcopronoqnoltetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, hydroxylaminodiacetic acid, dihydroxyethylglycine ethyl ether diaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, ethylenediamine Nipropionic acetic acid, phenylenediamide/tetraacetic acid, λ-phosphonobutane-7,2, Hiroshi-triacetic acid,/,3-diaminopropanol-N,N,N'.

N'-tetramethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid, 7.3-propylenediamine-N,N,N'.

N'-tetramethylenephosphonic acid, l-hydroxyethylidene-/, l'-diphosphonic acid, etc. can be mentioned.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1. λ-diaminopronoξonetetraacetic acid, methyliminodiacetic acid iron (III
) Complex salts are preferred because of their high bleaching strength.The amount of these bleaching agents per lt of bleach-fix solution is 0. /J, preferably 0.1 mol, more preferably O, co-o, p mol.

The fixing agent used in the bleach-fixing solution of the present invention is a known fixing agent, i.e., thiosulfate such as thiosulfate or ammonium thiosulfate; thiocyanate such as sodium thiocyanate or ammonium thiocyanate; Thioglycolic acid, J.

These are water-soluble silver halide solubilizers such as thioether compounds such as t-dithia-l and r-octanediol, and thioureas, and two or more of these compounds can be used in combination. Also, Tokukai Akira! J--
1113! A special bleach-fixing solution consisting of a combination of the fixing agent described in No. φ and a large amount of a halide such as potassium iodide can also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred.

The amount of fixing agent per liter of bleach-fix solution is preferably 0.3 to λ mol, more preferably 0.3 to λ mol. jr~/.

It is in the range of 0 mol.

The pI (range) of the bleach-fix solution in the present invention is preferably Hiroshi to 1, more preferably ! to 7.!.

If the pH is lower than this, the desilvering performance is improved, but the deterioration of the solution and the leucoization of the cyan dye are accelerated. On the other hand, if the pH is higher than this, desilvering is delayed and staining is likely to occur.

To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added to K as necessary.

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

Further, a bleach accelerator can be used in the bleach-fixing solution, if necessary. Examples of useful bleach accelerators include:
U.S. Patent No. 3. ruri J, ejr number, West German Patent No. 1,29
No. 0,111, same J, 01? .

rirr, JP-A No. 33-32734, J3-37r
3/No., 371A/I, jtJ-41732,
Same number J-3-72423, same number J-3-J630, same number! -93-4J/44-1 jJ-10tl-23λ, j3-/ko4'! JIA issue, same jJ-/da 1623
Same issue! Compounds having a mercapto group or a disulfide group as described in No. 3-λraxt, Research Disclosure No. I6/7/2 (July/9'7r), etc.;
Thiazolidine derivatives such as those described in JP-A Sho-to-i4coi No. 2;
λ-2013λ issue, same! J-3273J-, thiourea derivatives as described in US Pat. No. 3,704.14/; West German Patent No. 1. /Core, 7/! No., Tokukai Akira! ! -7423j
Iodides described in West German Patent Nos. A4.1A10, 2.7≠t, ≠30; Polyamine compounds described in Japanese Patent Publication No. Shoμt-grJb No.y; Others Tar 4 (u da 3, same μ tar j?A
μ≠ issue, same j3-ta μ octopus 7, same 71-31727, same! ! Examples include the compounds described in No.-2trot and No.2-/63≠θ, as well as iodine and bromine ions. Among these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and are particularly preferred as described in US Pat. Preferred are the compounds described in λrio, xiλ, and JP-A-Sho J3-Ta J430.

Additionally, the bleach-fix solution of the present invention may contain bromides (e.g. potassium bromide, sodium bromide, ammonium bromide) or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride) or iodides (e.g. ammonium iodide).
rehalogenating agents. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, as required
Inorganic acids, organic acids, and their alkali metal or ammonium salts having pH buffering ability such as sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, and tartaric acid; Corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The processing temperature in this bleach-fixing step is preferably 1O0 to 100c, more preferably 20'' to 100c.The replenishment amount is preferably λOml to 600ml, more preferably JOml-Jooml.

(Examples) Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.

Example/ On a subbed cellulose triacetate film support,
Sample A' was prepared as a multilayer color photosensitive material consisting of each layer having the composition shown below.

(Composition of photosensitive layer) First layer (antihalation layer) Black colloidal silver ・・・・・・・・・・・・・・・・・・
・・・・・・・・・ 0.3 gelatin ・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・ 1. O UV absorber UV-/...
・・・・・・・・・・・・ 0. / Same as above UV-co ・・・・・・・・・・・・・・・ 0. / Same as above
'[JV-j ・・・・・・・・・・・・・・・ o
, i Same as above UV-≠ ・・・・・・・・・・・・・・・
・・ 0. /Dispersion oil Oil −/ ・・・・・・
・・・・・・・・・ 0.2 Same as above 0il-ko
・・・・・・・・・・・・・・・ 0. /λth layer (middle layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・ /, 0 Colored coupler C-/ ・・・・・・・・・ 0.02 Dispersion oil Oil −/ ・・・・・・・・・ 00O1 3rd Layer (first red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide! molar, average grain size 0.2
μ)・・・・・・・・・・・・・・・・・・ o, r Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・ O0! Sensitizing dye processing...
・・・・・・・・・・・・・・・・・・・・・・・・
...j X / 0-'sensitizing dye■ ...
・・・・・・・・・・・・・・・・・・・・・2×1
0'Coupler C-/・・・・・・・・・・・・
・・・・・・・・・ 0.3 coupler C-2...
・・・・・・・・・・・・・・・・・・ O0O≠Coupler C-j ・・・・・・River・・・・・・・・・
・・ o, oj coupler C-≠ ・・・・・・・・・
・・・・・・・・・・・・ o, oi Dispersion oil 0i
l-j...Old...0.03 Dispersion oil 0il-μ...Old...0
．． 03th μ Hiro (middle layer) Gelatin ・・・・・・1 Old・・・・・・・・・・・・
... Reason... 1. O compound A ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
0. /j [(first green-sensitive emulsion, 1) Monodisperse silver iodobromide emulsion (silver iodide comol, average grain size O0r)
μ)・・・・・・・・・・・・・・・−0, Tagelatin ・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・ O3r sensitizing dye■ ・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・3
×lO sensitizing dye■ ・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・／×10-4 Same as above ■
・・・・・・・・・・・・・・・・・・・・・・・・
.../×10-' coupler M-3t, 100
1030060010391.0.7 Coupler C-6
・・・・・・・・・・・・・・・・・・・・・ 0. /
Coupler C-7・・・・・・・・・・・・・・・
...0. /Coupler C-r・・・・・・・・・
・・・・・・・・・・・・ o, or coupler C-
2・・・・・・・・・・・・・・・・・・・・・ 0.
Oco dispersion oil 0il-J...Old...
... 0. /Second layer (Intermediate Ii!+ Fine grain silver bromide (average particle size 0.07μ) ・・・・・・・・・・・・ 0, /Gelatin ・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・ 1. 7th layer (first blue-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 1 mol, average grain size 0.7
μ)・・・・・・・・・・・・・・・・・・ 0. ≠Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・ /, 0 sensitizing dye ■ ・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・CoX10”' Same as above ■［・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・CoX / 0-
'Coupler C-/θ・・・・・・・・・・・・・・・
・・・・・・ 1. λ coupler C-//・・・・・・
・・・・・・・・・・・・・・・ 0.2 dispersion oil
Oil -7・・・・・・・・・・・・・・・ 0. /
1st rJim (middle layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・ 0.0! Compound B...
・・・・・・・・・・・・・・・・・・・・・・・・
...Oil -7 for o, i dispersion...
・・・・・・・・・・・・・・・・・・ o, or the second layer (
2nd blue-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 12 molar ratio, average grain size/, !μ)・・・・・・・・・・・・・・・・・・
・・／、jgelatin ・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・ /, 2 sensitizing dye I ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・J×10−' Same as above and ・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
3×10-4 coupler C-saw ・・・・・・・・・
・・・・・・・・・・・・ O9l coupler C-/
・・・・・・・・・・・・・・・・・・・・・ 0.
3 coupler C-J... Old... Old...
... 0.02 dispersion oil 0il-≠ ...
・・・・・・・・・・・・ 0.2 7th O1 woman (middle layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・ /, O coupler C-7
...... Old... Old... 0.2 Compound A
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・ 0. /Dispersion oil Oil-j
・・・・・・・・・・・・・・・ 0.0j 11th
Layer (second green-sensitive layer) Tabular silver iodobromide emulsion (silver iodide 10 molar ratio, average aspect ratio 10, average grain size λμ) ・・・・・・・・・・・・ /, J 'S' Gelatin ・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・ /, 0 force 15-C-/J ・
Old...... Yodan... 0.2 force 15-C-r
・・・・・・・・・・・・1 Old・Original・00O-2 Dispersion oil Oil −/・・・・・・・・・・・・
・・・O,g 1st λ layer (yellow filter layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・ /, 2 yellow colloidal silver
・・・・・・・・・・・・・・・・・・・・・・・・
0.2 Compound B・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・ 0.2 Dispersion oil 0il-/ ・・・・・・・・・・・・・・・ 0
．． 2 73rd layer (second blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 3 molar ratio, average ascent ratio l!, average grain size 2.J'μ)...・・・・・・
・Ol is a fine grain silver iodobromide emulsion (average grain size 0.02μ)...
−・・・・・・ 0.2 Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・ /, +2 sensitizing dye ■ ・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・3×10−' Same as above ■ ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・／x10”-'
Coupler C-10・・・・・・・・・・・・・・・
・・・ 0.3 coupler C-tt ・・・・・・・・・
・・・・・・・・・・・・ 0. ! Dispersion oil Oil -
/ ・・・・・・・・・・・・・・・ o, o6 1st
≠Layer (7th protective layer) Fine grain silver bromide emulsion (average grain size 0.07μ)...
・・・・・・・・・ 0.2 UV absorber UV-/
・・・・・・・・・・・・ o, or same as above U
V-2・・・・・・・・・・・・ 0.0! Same as above
UV-j ・・・・・・・・・・・・ 0.0! Same as above Uv-Hiroshi ・・・・・・・・・・・・ 0.0!
Same as above UV-j ・・・・・・・・・・・・ 0
．． 02 Gelatin ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・ Oil for dispersing Ol 0il−≠・・・・・・・・・・・・・・・ 0. /
1st! Layer (second protective layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・ 0. J′ polymethyl methacrylate particles (diameter/, jμ)・・・・・・・・・・・・・・・・・・
...0.2 In addition to the above ingredients, each layer contains a surfactant W.
-/4 Added as a coating aid. Additionally, formalin scavenger was added.

Compounds used in Examples C-j C-hiroα -t C-taC-// C-/2 C-73 Sensitizing dye work Same as above ■ Sensitizing dye ■ Same as above ■ Same as above V (shiH2J4 bu3- (( -'H2)4
SO3Na sensitizing dye■ Same as above■ UV-/UV-2 t-Bu t-t$u UV-JUV-μ UV-j Oil -/Oil -2i
l-j Oll -μ I 2H5 Oil -! Compound containing compound B OL'12H25 -l <Rinse solution> The following formulation was used in both treatment steps A and B.

Tank fluid Replenisher formaldehyde Listed in Table 1 Listed in Table 1 Drywell r, omtz, omi Ethylenediaminetetraacetic acid disodium A 2! Om9 λrorn
9. The formalin concentration in the rinsing bath was changed as shown in Table 1, and at the end of continuous processing, the color temperature of the photosensitive material was 2ar using a filter using a tungsten light source and sound.

Exposure of xtcMs adjusted to OoK was applied through a staircase filter and then processed.

Each sample after treatment was divided into two equal parts, and one part was divided into 12 parts at to 0c.
The other was left for 3 weeks under conditions of ≠00C/04RH, and the changes in photographic properties immediately after processing and after time (ΔDB
min, ΔD,) are shown in Table 1.

Here, ΔDGmin indicates the change in the minimum density of yellow immediately after processing, ΔD0haj indicates the change in density of magenta at point D=/,j immediately after processing, and the minus sign indicates the change over time. The plus sign indicates the opposite change, meaning that the concentration is lower than immediately after treatment. These numbers are close to O, ie.

The smaller the difference in density between immediately after processing and after time, the better the image storage stability is.

At the same time, the presence or absence of precipitation in the stabilizing bath was visually confirmed. The results are shown in Table 1.

As shown in Table 1, by performing the processing of the present invention (processing B-■, ■, It can be seen that good image preservation properties equivalent to those of the stabilizing bath treatment (treatment A) can be obtained. Even in the treatment BIC, the formalin concentration in the rinsing bath is outside the scope of the claims of the present invention (treatment B-■).

Precipitation occurs in the rinse bath.

Example 2 A method similar to that used for photosensitive material A made from 1111 in Example 1.

Magenta coupler M-j4t-change sample B%C1D
, E, and F were created.

Samples A, B, C, D, E and Ft-1 were treated with treatment B-■ in the same manner as in Example 1, and the image preservation properties of each sample were compared in the same manner as in Example. The results are shown in Table 2.

As is clear from Table 2, when using the λ equivalent magenta coupler of the present invention, it is possible to obtain color photographic images with clearly improved image storage stability compared to when using the reference magenta coupler. Ta.

Patent applicant: Fuji Photo Film Co., Ltd. Showa Otsu/March the day, /゛

Claims (1)

[Scope of Claims] A method of processing an imagewise exposed silver halide color photographic light-sensitive material in a final rinsing bath directly after fixing or bleach-fixing, the method comprising: contains at least one 2-equivalent magenta coupler represented by the following general formula [I] or [II], and the aldehyde compound concentration in the final tank of the final rinsing step is 1.0 x 10^-^2 mol/l. A method for processing a silver halide color photographic material, wherein the amount of replenishment of the final rinsing bath is 0.5 to 60 times the amount brought in from the previous bath per unit area of the photosensitive material to be processed. . General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the general formula [I], R_1 represents a hydrogen atom or a substituent, and Represents a group that can be separated by Za
, Zb and Zc represent methine, substituted methine, =N- or -NH-, and one of the Za-Zb bond and the Zb-Zc bond is a double bond and the other is a single bond. Zb
The case where -Zc is a carbon-carbon double bond includes the case where it is part of an aromatic ring. Furthermore, the case where R_1 or X forms a dimer or more multimer is also included. Furthermore, when Za, Zb or Zc is a substituted methine, it also includes the case where the substituted methine forms a dimer or more multimer. ) General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 is a carbonamide group, sulfonamide or ureido group, R_2 is a phenyl group, and X is an aromatic primary amine developer oxidized. (Represents a group that can be separated by a coupling reaction with the