JP2540057B2 - Silver halide color-processing method of photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a processing method of a silver halide color photographic light-sensitive material, and more particularly to a processing method excellent in processing property, color developing property and fading property, and further, It is to provide a color developing solution having excellent stability.

(Prior Art) Conventionally, magenta couplers represented by the general formula (I) have been disclosed in JP-A-59-162548, JP-A-60-43659, and JP-A-59-17195.
No. 6, No. 60-172982, No. 60-33552 and U.S. Pat.
It is known from No. 1,432 and the like, and various studies have been made because of its excellent hue.

(Problems to be Solved by the Invention) However, the magenta coupler of the general formula (I) has a low color forming property when processed with a conventional color developing solution, and the fluctuation of photographic properties is significantly large. It was found to have a serious drawback that stains are easily generated.

First of all, it has been clarified that fluctuations in the concentration of sulfite ions, which have been conventionally added to color developers, have a significant effect on fluctuations in photographic properties. Therefore, various preservatives and chelating agents were added to keep the sulfite ion concentration stable, but no effective means was found.
Next, when the sulfite ion was removed, the concentration fluctuations of hydroxylamines and color developing agents became large, which also adversely affected the photographic properties. Therefore, a preservative that changes to sulfite ion is required, but U.S. Pat.
Even if the triethanolamines described in No. 478 or the poly (ethyleneimine) s described in No. 4,252,892 were added, a sufficient effect could not be obtained.

On the other hand, regarding the generation of magenta stain after processing,
Conventional fading prevention technology and stain prevention technology (for example, US Pat. Nos. 2,360,290 and 2,418,613 are known as fading prevention technology.
No., No. 2,675,314, No. 2,701,197, No. 2,704,713,
2,728,659, 2,732,300, 2,735,765, 2,7
No. 10,801, No. 2,816,028, British Patent No. 1,363,291, hydroquinone derivatives described in JP-A-58-24141, U.S. Pat. P-alkoxyphenols described in JP-B Nos. 49-20977 and 52-6623, U.S. Pat. Nos. 3,432,300 and 3,573,0
No. 50, No. 3,574,627, No. 3,764,337, JP-A-52-3563
No. 3, p. 52-147434, p. 52-152225
-Technologies such as oxyphenol derivatives and bisphenols described in US Pat. No. 3,700,455. Examples of stain prevention techniques include Japanese Patent Laid-Open Nos. 49-11330, 50-57223, and 56-8574.
No. 7, and Japanese Patent Publication No. 56-8346) cannot be used to obtain a sufficient effect.

As described above, it has been desired to develop a technique for overcoming the drawbacks of the magenta coupler represented by the general formula (I).

(Means for Solving Problems) As a result of various studies, the present inventors have found that the object of the present invention can be effectively achieved by using the following means. That is, a silver halide color photographic light-sensitive material containing at least one of pyrazoloazole-based magenta couplers represented by the following general formula (I) is exposed, and after exposure, an aromatic primary amine color developing agent is contained. Contains at least one selected from hydrazines and hydrazides represented by the general formula (II),
This has been solved based on a processing method of a silver halide color photographic light-sensitive material, which is characterized by processing with a color developer containing no sulfite ion.

General formula (I) (In the formula, R ₁₁ represents a hydrogen atom or a substituent, X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of an aromatic primary amine developer. Za, Zb and Zc represent methine, A substituted methine, = N- or -NH-, wherein one of a Za-Zb bond and a Zb-Zc bond is a double bond and the other is a single bond, wherein Zb-Zc is a carbon-carbon double bond. In this case, it includes a case where it is a part of an aromatic ring, and further includes a case where R ₁₁ or X forms a dimer or higher multimer, and when Za, Zb or Zc is a substituted methine, , Including the case where the substituted methine forms a dimer or higher multimer.) General formula (II) (In the formula, R ¹ , R ² and R ³ are each independently a hydrogen atom,
Represents an alkyl group, an aryl group or a heterocyclic group, R ⁴
Represents a hydrogen atom, a hydroxy group, a hydrazino group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group or an amino group, X ¹ represents a divalent group, and n represents 0 or 1 Represent. However, n
When = 0, R ⁴ represents an alkyl group, an aryl group or a heterocyclic group. R ³ and R ⁴ may together form a heterocycle. ) In particular, a compound represented by the general formula (II) (that is, at least one selected from hydrazines and hydrazides) is used as a compound replacing sulfite, and
It was totally unexpected that the drawbacks of the couplers of the general formula (I) could be solved by processing with a color developer containing substantially no benzyl alcohol.

The magenta coupler represented by formula (I) will be described in detail below.

In formula (I), R ₁₁ represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. 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. When Zb-Zc is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring. It also includes the case where R ₁₁ or X forms a dimer or higher multimer. Further, when Za, Zb or Zc is a substituted methine, it also includes the case where the substituted methine forms a dimer or higher multimer.

In the general formula (I), the multimer means one having two or more groups represented by the general formula (I) in one molecule, and a bis form and a polymer coupler are also included therein.
Here, the polymer coupler may be a homopolymer consisting only of a monomer having a portion represented by the general formula (I) (preferably having a vinyl group, hereinafter referred to as vinyl monomer), or an aromatic primary amine developing agent. Copolymers may be made with non-color forming ethylene-like monomers that do not couple with the oxidation products of.

The compound represented by the general formula (I) is a 5-membered-5-membered fused nitrogen heterocyclic type coupler, and its coloring mother nucleus shows isoelectronic aromaticity with naphthalene and is generally called azapentalene. It has a structure. Among the couplers represented by formula (I), preferred compounds are 1H-imidazo [1,2-b] pyrazoles, 1H-pyrazolo [1,5-b].
Pyrazoles, 1H-pyrazolo [5,1-c] [1,2,4] triazoles, 1H-pyrazolo [1,5-b] [1,2,4] triazoles, 1H-pyrazolo [1,5 -D] tetrazoles and 1H-pyrazolo [1,5-a] benzimidazoles, which are represented by the general formulas (Ia) (Ib) (Ic) (Id) (Ie) and (If), respectively. Of these, particularly preferred compounds (Ia), (Ic) and (Id). A more preferred compound is (Id).

Substituents R ₁₂ , R ₁₃ and R _{14 in the} general formulas (Ia) to (If)
Are each independently 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. 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, It represents an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, and X is a hydrogen atom, a halogen atom, a carboxy group, or an oxygen atom, a nitrogen atom, or a sulfur atom. It represents a group Kapurringu leaving with a group bonded to the ring position carbon.

It also includes the case where R ₁₂ , R ₁₃ , R ₁₄ or X becomes a divalent group to form a bis form. In addition, general formulas (Ia) to (If)
When the part represented by is in the vinyl monomer, R
₁₂ , R ₁₃ or R ₁₄ represents a mere bond or linking group,
Through this, the vinyl groups are bonded to the moieties represented by the general formulas (Ia) to (If).

More specifically, R ₁₂ , R ₁₃ and R ₁₄ are each a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, propyl group, i-propyl group, t-butyl group, Trifluoromethyl group, tridecyl group, 3- (2,4-di-t-amylphenoxy) propyl group, 2-dodecyloxyethyl group, 3-phenoxypropyl group, 2-hexylsulfonyl-ethyl group, cyclopentyl group, benzyl Group, etc.), aryl group (eg, phenyl group, 4-t-butylphenyl group, 2,4-di-t-)
Amylphenyl group, 4-tetradecanamidophenyl group, etc.), hetyrocyclic group (eg, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.), cyano group, alkoxy group (eg, , Methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecyloxyethoxy group, 2-phenoxyethoxy group, 2-
Methanesulfonylethoxy group, etc.), aryloxy group (eg, phenoxy group, 2-methylphenoxy group, 4
-T-butylphenoxy group, etc.), heterocyclic oxy group (eg, 2-benzimidazolyloxy group, etc.), acyloxy group (eg, acetoxy group, hexadecanoyloxy group, etc.), carbamoyloxy group (eg, N
-Phenylcarbamoyloxy group, N-ethylcarbamoyloxy group, etc.), silyloxy group (eg, trimethylsilyloxy group, etc.), sulfonyloxy group (eg, dodecylsulfonyloxy group, etc.), acylamino group (eg, acetamide group, Benzamide group, tetradecanamide group, α- (2,4-di-t-amylphenoxy) butyramide group, γ- (3-t-butyl-4-hydroxyphenoxy) butyramide group, α- {4- (4-
Hydroxyphenylsulfonyl) phenoxy} decanamide group, etc.), anilino group (for example, phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecaneamidoanilino group, 2-chloro-5-dodecyloxycarbonylanilino group) , N-acetylanilino group, 2
-Chloro-5- {α- (3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino group, etc.), ureido group (eg, phenylureido group, N-butyl-
N'-methylureido group, methylureido group, N, N-dibutylureido group, etc.), imide group (for example, N-succinimide group, 3-benzylhydantoinyl group, 4-
(2-ethylhexanoylamino) phthalimide group,
Etc.), a sulfamoylamino group (eg, N, N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, etc.), a carbamoylamino group (eg, carbamoylamino group, N, N-dimethylcarbamoylamino group, etc.), alkylthio group (eg, methylthio group, octylthio group, tetradecylthio group, 2
-Phenoxyethylthio group, 3-phenoxypropylthio group, 3- (4-t-butylphenoxy) propylthio group, etc.), arylthio group (for example, phenylthio group,
2-butoxy-5-t-octylphenylthio group, 3-
Pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group,
Etc.), heterocyclic thio group (eg, 2-benzothiazolylthio group, etc.), alkoxycarbonylamino group (eg, methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino group (eg, , Phenoxycarbonylamino group, 2,
4-di-tert-butylphenoxycarbonylamino group,
Etc.), sulfonamide group (eg, methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group, 2-methyloxy-5-t-butylbenzenesulfonamide group) , Etc.), carbamoyl group (for example, N-ethylcarbamoyl group, N, N-dibutylcarbamoyl group, N- (2-dodecyloxyethyl) carbamoyl group, N-methyl-N-dodecylcarbamoyl group, N- {3- (2,4-di-tert-amylphenoxy)
Propyl} carbamoyl group, etc.), acyl group (eg,
Acetyl group, (2,4-di-tert-amylphenoxy) acetyl group, benzoyl group, etc.), sulfamoyl group (for example, N-ethylsulfamoyl group, N, N-dipropylsulfamoyl group, N- ( 2-dodecyloxyethyl)
Sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N, N-diethylsulfamoyl group, etc.), sulfonyl group (for example, methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.) ), A sulfinyl group (for example, octansulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, etc.), an alkoxycarbonyl group (for example, methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, etc.), Represents an aryloxycarbonyl group (eg, phenyloxycarbonyl group, 3-pentadecylphenyloxy-carbonyl group, etc.).

X is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom, etc.), a carboxyl group, or a group linked by an oxygen atom (for example, an acetoxy group, a propanoyloxy group, a benzoyloxy group, 2,4- Dichlorobenzoyloxy group, ethoxyoxaloyloxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenoxy group, 4-methanesulfonamidophenoxy group, 4-methanesulfonylphenoxy group,
α-naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-phenethyloxy group, 2-phenoxyethoxy group, 5-phenyltetrazolyloxy group Group, 2-benzothiazolyloxy group,
Etc.), groups linked by nitrogen atoms (for example, benzenesulfonamide group, N-ethyltoluenesulfonamide group, heptafluorobutanamide group, 2,3,4,5,6, -pentafluorobenzamide group, octanesulfonamide group) Group, p-
Cyanophenylureido group, N, N-diethylsulfamoylamino group, 1-piperidyl group, 5,5-dimethyl-2,4
-Dioxo-3-oxazolinyl group, 1-benzyl-ethoxy-3-hydantoinyl group, 2N-1,1-dioxo-
3 (2H) -oxo-1,2-benzisothiazolyl group, 2
-Oxo-1,2-dihydro-1-pyridinyl group, imidazolyl group, pyrazonyl group, 3,5-diethyl-1,2,4-triazol-1-yl group, 5- or 6-bromo-benzotriazole-1 -Yl group, 5-methyl-1,2,3,4-triazol-1-yl group, benzimidazolyl group, 3-
Benzyl-1-hydantoinyl group, 1-benzyl-5-
Hexadecyloxy-3-hydantoinyl group, 5-methyl-1-tetrazolyl group, 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, 2-hydroxy-4-propanoylphenylazo group, etc.), Groups linked by sulfur atoms (eg, phenylthio group, 2-carboxyphenylthio group, 2-butoxy-5-t-octylphenylthio group, 4-methanesulfonamidophenylthio group, 2,5-dibutoxyphenylthio group , 4-methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group, 2-butoxyphenylthio group, 4-
Dodecyloxyphenylthio group, 2- (2-hexanesulfonyltyl) -5-tert-octylphenylthio group,
Benzylthio group, 2-cyanoethylthio group, 1-ethoxycarbonyltridecylthio group, 5-phenyl-2,3,4,
5-tetrazolylthio group, 2-benzothiazolylthio group, 2-dodecylthio group, 2-dodecylthio-5-thiophenylthio group, 2-phenyl-3-dodecyl-1,2,4
-Triazolyl-5-thio group).

When R ₁₂ , R ₁₃ , R ₁₄ or X is a divalent group to form a bis form, the divalent group is described in more detail as follows.
Substituted or unsubstituted alkylene group (e.g., methylene group, ethylene group, 1,10-decylene group, -CH ₂ CH ₂ -O-CH
₂ CH _2- , etc.), a substituted or unsubstituted phenylene group (e.g., 1,4-phenylene group, 1,3-phenylene group, Etc.), —NHCO—R ₅ —CONH— group (R ₅ represents a substituted or unsubstituted alkylene group or phenylene group), and the like.

When the one represented by the general formulas (Ia) to (If) is in the vinyl monomer, the linking group represented by R ₁₂ , R ₁₃ or R ₁₄ is an alkylene group (a substituted or unsubstituted alkylene group, For example, methylene group, ethylene group, 1,10-decylene group, —CH ₂ CH ₂ OCH ₂ CH ₂ —, etc.), phenylene group (substituted or unsubstituted phenylene group, for example, 1,4-phenylene group, 1,3-phenylene group, Etc.), —NHCO—, —CONH—, —O—, —OCO—, and aralkylene groups (eg, Etc.) and groups that are established by combining those selected from the above.

The vinyl group in the vinyl monomer has the general formula (Ia)
Including cases where a substituent is included in addition to those represented by (If). Preferred substituents are a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms.

Non-color-forming ethylene-like monomers that do not couple with the oxidation products of aromatic primary amine developers include acrylic acid,
α-chloroacrylic acid, α-alkacrylic acid (for example,
Methacrylic acid, etc.) and esters or amides derived from these acrylic acids (eg, acrylamide, n-butyl acrylamide, t-butyl acrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n -Butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, ularyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), methylenedibisacrylamide, Vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate),
Acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg, styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg, vinyl Ethyl ether), maleic acid, maleic anhydride, maleic ester, N-vinyl-2-
Pyrrolidone, N-vinylidyne, and 2- and 4
-Vinyl pyridine and the like. It also includes the case where two or more non-color-forming ethylenically unsaturated monomers used here are used together.

Examples of compounds of the couplers represented by the general formulas (Ia) to (If), synthetic methods, and the like are described in the following documents.

The compound of the general formula (Ia) is disclosed in JP-A-59-162548, the compound of the general formula (Ib) is disclosed in JP-A-60-43659, and the compound of the general formula (Ic) is disclosed in JP-B-47-27411. , The general formula (I
The compounds of d) are disclosed in JP-A-59-171956 and JP-A-60-172982.
The compounds of general formula (Ie) are described in JP-A-60-33552, and the compounds of general formula (If) are disclosed in US Pat. No. 3,061,432.
Etc., respectively.

Also, JP-A-58-42045, JP-A-59-214854, JP-A-59-17755
The highly chromogenic ballast groups described in 3, 59-177544, 59-177557 and the like are applicable to any of the compounds represented by the general formulas (Ia) to (If).

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

These couplers are generally used in an amount of 2 × 10 ^-3 mol to 5 × 10 ^-1 mol, preferably ¹ × 10 ^-1 mol, per mol of silver in the emulsion layer.
^-2 mol to 5 × 10 ^-1 mol is added.

The above couplers and the like can be used in combination in two or more kinds in the same layer in order to satisfy the characteristics required for the light-sensitive material, and it is of course possible to add the same compound in two or more different layers.

To introduce the coupler into the silver halide emulsion layer, known methods such as the method described in US Pat. No. 2,322,027 are used. For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphonate, triphenyl phosphonate, tricresyl phosphonate, dioctyl butyl phosphonate), citric acid ester (for example, Acetyl citrate tributyl), benzoic acid esters (eg octyl benzoate), alkyl amides (eg diethyl lauryl amide), fatty acid esters (eg dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (eg tributyl trimesate). ), Or an organic solvent having a boiling point of about 30 ° C. to 150 ° C., for example, lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxide. After being dissolved in cyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

The compound of the general formula (II) used in the present invention, that is, the hydrazine chloroplast composed of hydrazines and hydrazides will be described in detail below.

R ¹ , R ² and R ³ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group (preferably having 1 to 20 carbon atoms, for example, a methyl group, an ethyl group, a sulfopropyl group, a carboxybutyl group, a hydroxyethyl group, Cyclohexyl group,
Benzyl group, phenethyl group, etc.), substituted or unsubstituted aryl group (preferably having 6 to 20 carbon atoms, for example, phenyl group, 2,5-dimethoxyphenyl group, 4-hydroxyphenyl group, 2-carboxyphenyl group) Group) or a substituted or unsubstituted heterocyclic group (preferably having a carbon number of 1 to 1).
20, preferably a 5- or 6-membered ring, containing at least one of oxygen, nitrogen, sulfur and the like as a hetero atom,
For example, a pyridin-4-yl group, an N-acetylpiveridin-4-yl group, etc.).

R ⁴ is a hydrogen atom, a hydroxy group, a substituted or unsubstituted hydrazino group (for example, a hydrazino group, a methylhydrazino group, a phenylhydrazino group, etc.), a substituted or unsubstituted alkyl group (preferably having 1 to 20 carbon atoms, For example, methyl group, ethyl group, sulfopropyl group, carboxybutyl group, hydroxyethyl group, cyclohexyl group, benzyl group, t-butyl group, n-octyl group, etc., substituted or unsubstituted aryl group (preferably having 6 carbon atoms). To 20, for example, phenyl group, 2,5-dimethoxyphenyl group, 4-hydroxyphenyl group, 2-carboxyphenyl group, 2-carboxyphenyl group, 4-sulfophenyl group, etc.), substituted or unsubstituted hetero Cyclic group (preferably having from 1 to
It is a 20-, preferably 5- or 6-membered ring, and contains at least one of oxygen, nitrogen and sulfur as a hetero atom. For example, pyridin-4-yl group, imidazolyl group and the like), substituted or unsubstituted alkoxy group (preferably having 1 to 20 carbon atoms, for example, methoxy group, ethoxy group, methoxyethoxy group, benzyloxy group, cyclohexyloxy group, octyloxy group) Etc.), a substituted or unsubstituted aryloxy group (preferably having a carbon number of 6 to 20, for example, a phenoxy group, a p-methoxyphenoxy group, a p-carboxyphenyl group, a p-sulfophenoxy group, etc.), a substituted or unsubstituted carbamoyl group. A group (preferably having a carbon number of 1 to 20, for example, an unsubstituted carbamoyl group, an N, N-diethylcarbamoyl group, a phenylcarbonyl group, etc.) or a substituted or unsubstituted amino group (preferably having a carbon number of 0 to 20, such as an amino group , Hydroxyamino group, methylamino group, hexylamino group, methoxyethyl Amino represents group, carboxyethyl group, sulfoethyl amino group, N- Fueniruamino group, a p- sulfo-phenylalanine amino group).

Examples of the further substituents of R ¹ , R ² , R ³ and R ⁴ include a halogen atom (chlorine, bromine, etc.), a hydroxy group, a carboxy group, a sulfo group, an amino group, an alkoxy group, an amide group, a sulfonamide group, Carbamoyl group, sulfamoyl group,
An alkyl group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, a nitro group, a cyano group, a sulfonyl group, a sulfinyl group and the like are preferable, and they may be further substituted.

X ¹ is preferably a divalent organic residue, specifically, for example, —CO—, —SO ₂ —, and Represents n is 0 or 1. However, when n = 0,
R ⁴ represents a group selected from a substituted or unsubstituted alkyl group, an aryl group and a heterocyclic group. R ¹ and R ² and
R ³ and R ⁴ may together form a heterocyclic group.

When n is 0, at least one of R ^{1 to} R ⁴ is preferably a substituted or unsubstituted alkyl group. In particular, R ¹ ,
It is preferred that R ² , R ³ and R ⁴ are hydrogen atoms or substituted or unsubstituted alkyl groups. (However, R ¹ , R ² , R ³ , and R ⁴ are not hydrogen atoms at the same time.) Among them,
When R ¹ , R ² and R ³ are hydrogen atoms and R ⁴ is a substituted or unsubstituted alkyl group, R ¹ and R ³ are hydrogen atoms and R ² and R ⁴ are substituted or unsubstituted When it is an alkyl group, or when R ¹ and R ² are hydrogen atoms and R ³ and R ⁴ are substituted or unsubstituted alkyl groups (at this time,
R ³ and R ⁴ may together form a heterocycle).

When n = 1, X ¹ is preferably —CO—, R ⁴ is preferably a substituted or unsubstituted amino group, and R ¹ to
R ³ is preferably a hydrogen atom or a substituted or unsubstituted alkyl group.

The alkyl group represented by R ^{1 to} R ⁴ preferably has 1 to 10 carbon atoms, and more preferably has 1 to 7 carbon atoms.
Is. In addition, examples of preferable substituents on the alkyl group include a hydroxyl group, a carboxylic acid group, a sulfone group and a phosphonic acid group. When there are two or more substituents, they may be the same or different.

The compound of the general formula (II) may form a bis body, a tris body or a polymer linked by R ¹ , R ² , R ³ and R ⁴ .

Specific examples of the compound represented by the general formula (II) are shown below, but the present invention is not limited thereto.

(II-2) CH ₃ NHNHCH ₃ (II-8) HOOCCH ₂ NHNHCH ₂ COOH (II-9) NH ₂ NHCH _{2 3} NHNH ₂ (II-10) NH ₂ NHCH ₂ CH ₂ OH _{(II-12) NH 2 NH-} (CH 2) 3 -SO 3 H (II-13) NH 2 NH- (CH 2) 4 -SO 3 H (II-14) NH 2 NH- (CH 2) 3 −COOH (II-19) NH ₂ NHCH ₂ CH ₂ COONa (II-20) NH ₂ NHCH ₂ COONa (II-21) H ₂ NNHCH ₂ CH ₂ SO ₃ Na (II-25) H ₂ NHCH ₂ CH ₂ SO ₃ Na) ₂ (II-26) H ₂ NHCH ₂ CH ₂ CH ₂ SO ₃ Na) ₂ (II-34) NH ₂ NHCONH ₂ (II-36) NH ₂ NHCONHNH ₂ (II-37) NH ₂ NHSO ₃ H (II-38) NH ₂ NHSO ₂ NHNH ₂ (II-39) CH ₃ NHNHSO ₂ NHNHCH ₃ (II-40) NH ₂ NHCONH- (CH _{2) 3} -NHCONHNH ₂ (II-42) NH ₂ NHCOCONHNH ₂ (II-46) NH ₂ COCONHNH ₂ (II-63) NH ₂ NHCOOC ₂ H ₅ (II-64) NH ₂ NHCOCH ₃ (II-67) NH ₂ NHCH ₂ PO ₃ H ₂ (II-73) (CH ₃ ) ₃ CCONHNH ₂ (II-80) HOCH ₂ CH ₂ SO ₂ NHNH ₂ (II-81) NaO ₃ SCH ₂ CH ₂ CONHNH ₂ (II-82) H ₂ NCONHCH ₂ CH ₂ SO ₂ NHNH ₂ (II-85) H ₂ NNHCH ₂ CH ₂ PO ₃ H ₂ Other specific examples are described in Japanese Patent Application No. 61-170756.
Pp. 11-24, pp. 61-171682, pp. 12-22, pp. 61-171682
Examples of the compounds described on pages 9 to 19 of the specification of 173468 can be given.

Many of the compounds represented by the general formula (II) are available as commercial products, and "Organic Syntheses", Coll. Vol.2, pp 208-2
13; Jour.Amer.Chem.Soc., 36 , 1747 (1914); Oil Chemistry, 2
4 , 31 (1975); Jour. Org. Chem., 25 , 44 (1960); Pharmaceutical Journal, 91 , 1127 (1971); "Organic Synthesis"
(Organic Syntheses), Coll.Vol.1, p 450; "New Experimental Chemistry Course", Volume 14, III, p1621-1628 (Maruzen); Beil., 2 , 5
59; Beil., 3 , 117; EB Mohr et al., Inorg.Syn., 4 , 32
(1953); FJ Wilson.EC Pickering, J.Chem.Soc., 123 ,
394 (1923); NJLeonard, JHBoyer, J.Org.Chem., 15 , 4
2 (1950); "Organic Synthesis" (Organic
Syntheses), Coll. Vol. 5, p 1055; PASSmith, `` Derwa
itives of hydrazine and other hydronitro−gen
s having n-n-bonds ", p120-124, p130-131; THE B
ENJAMIN / CUMMINGS COMPANY, (1983); Staniey R. Sand
ier Waif Karo, `` Organic Functional Group Prep
arations ”, Vol.1, Second Edition, p457 and the like.

The addition amount of the compound of the general formula (II) is 0.01 g to 50 g, preferably 0.1 g to 30 g, and more preferably 1 g per 1 l of the color developing solution.
It is 0.5g-10g.

Hereinafter, the color developer used in the present invention will be described.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, and typical examples thereof are shown below, but the invention is not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-3 2-methyl-4- [N-ethyl-N -(Β-Hydroxyethyl) amino] aniline D-4 4-amino-3-methyl-N-ethyl-N-
[Β- (Methanesulfonamido) ethyl] aniline Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g per developing solution,
More preferably, the concentration is about 0.5 g to about 10 g.

In particular, when the color developing agent of D-4 is used in the presence of the compound of the general formula (I), it is preferable in that the fog increase is small and good photographic characteristics are obtained.

Further, as a compound that directly preserves the color developing agent, various hydroxylamines, hydroxamic acids described in Japanese Patent Application No. 61-186559, 61-188742 and 61-2032 are described.
No. 53 phenols, α-hydroxyketones and α-aminoketones described in 61-188741, and / or
It is preferable to add various sugars described in JP-A-61-180616. Also, in combination with the above compound, Japanese Patent Application No. 61-147823,
Nos. 61-166674, 61-165621, 61-164515,
Monoamines described in 61-170789, 61-168159, etc., 61-173595, 61-164515, 61-186560
No. 61-165621 and No. 61-165621.
Polyamines described in No. 169789, polyamines described in No. 61-1888619, nitroxy radicals described in No. 61-197760, No. 61-186561, and alcohols described in No. 61-197419, No. 61-198987. The described oximes, and 61-26
The tertiary amines described in No. 5149 may be added if necessary.

As other preservatives, JP-A-57-44148 and 57-5
Various metals described in 3749, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat. It is preferable to use an aromatic polyhydroxy compound described in 3,746,544 in combination. In particular, aromatic polyhydroxy compounds, triethanolamine, and Japanese Patent Application No. 61
The addition of the compound described in -265149 is preferable.

It is preferable that the color developer of the present invention does not substantially contain benzyl alcohol in terms of fog and increase in stain after processing. That is, the term "substantially free" means that the color developer is not more than 5.0 ml, preferably not more than 2 ml, and more preferably not contained at all.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developing solution may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers. As the buffer, carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt,
N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, amino acid salt, 2-amino-2-methyl-1,3-propanediol salt, valine salt, Proline salt,
Trishydroxyaminomethane salt, lysine salt and the like can be used. Especially carbonates, phosphates, tetraborate,
Hydroxybenzoate has excellent solubility and buffering ability in the high pH range of pH 9.0 or higher, and even if added to a color developer, it does not adversely affect photographic performance (fog etc.) and is inexpensive. It is particularly preferable to use these buffers.

Specific examples of these buffers include sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), tetraborate Potassium acid, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
And so on. However, the invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol /
It is preferably at least above, and particularly preferably 0.1 mol / to 0.4 mol /.

In addition, various chelating agents can be used in the color developing solution as a precipitation preventing agent for calcium and magnesium, or for improving the stability of the color developing solution.

As the chelating agent, an organic acid compound is preferable, for example, aminopolycarboxylic acids described in JP-B-48-30496 and JP-B-44-30232, JP-A-56-97347, JP-B-56-39359 and West German Patent No. 2,227,639. Organic phosphonic acids described,
JP-A-52-102726, JP-A-53-42730, JP-A-54-121127
Nos. 55-126241 and 55-6559506, and phosphonocarboxylic acids described in JP-A-58-195845 and JP-A-58-195845.
Examples thereof include compounds described in 203440 and Japanese Patent Publication No. 53-40900. Specific examples are shown below, but the present invention is not limited thereto.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid,
1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid,
N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid and the like.

Two or more of these chelating agents may be used in combination, if necessary.

The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. For example, it is about 0.1 g to 10 g per one.

If necessary, any development accelerator can be added to the color developing solution. However, it is preferable that the color developing solution of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, liquid preparation and fog prevention.

The compounds of the above-mentioned general formulas (II) to (X) used in the present invention have a remarkable effect also on the stability of the color developing solution containing substantially no benzyl alcohol.

Other development accelerators include Japanese Patent Publication No. 37-16088 and No. 3
7-5987, 38-7826, 44-12380, 45-9019
Thioether compounds disclosed in U.S. Pat. No. 3,813,247 and US Pat. No. 3,813,247; p-phenylenediamine compounds disclosed in JP-A-52-49829 and JP-A-50-15554;
-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429, and the like, quaternary ammonium salts, U.S. Patents 2,494,903, 3,128,182, and 4,23.
0,796, 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Patent Nos. 2,482,546, 2,596,926 and 3,582,346, etc., amine compounds described in Japanese Patent Publication Nos. 37-16088, 42-2.
No. 5201, U.S. Pat.No. 3,128,183, JP-B-41-11431,
No. 42-23883 and U.S. Pat.No. 3,532,501, polyalkylene oxides and other 1-phenyl-3
-Pyrazolidones, imidazoles, etc. can be added as required.

In the present invention, any antifoggant can be added if necessary. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole and 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples thereof include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

The color developer used in the present invention preferably contains a fluorescent whitening agent. As the fluorescent whitening agent, a 4,4'-diamino-2,2'-disulfostilbene compound is preferable. The addition amount is 0 g to 5 g / preferably 0.1 g to 4 g /.

Further, various surfactants such as alkylsulfonic acid, arylphosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as needed.

The processing temperature of the color developer of the present invention is from 20 to 50 ° C, preferably from 30 to 40 ° C. Processing time is 20 seconds to 5 minutes, preferably 30
Seconds to 2 minutes. The replenishment amount is preferably small, but it is ^{20 to} 600 ml, preferably 50 to 300 ml, per 1 m ^{2 of} the light-sensitive material. More preferably, it is 100 ml to 200 ml.

Next, the bleaching solution, the bleach-fixing solution and the fixing solution used in the present invention will be described.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution used in the present invention, any bleaching agent can be used, but especially organic complex salts of iron (III) (for example, aminopolyamines such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid). Carboxylic acids, 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 and the like are preferable.

Of these, organic complex salts of iron (III) are particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution. Examples of aminopolycarboxylic acids, aminopolyphosphonic acids, or organic phosphonic acids or salts thereof useful for forming organic complex salts of iron (III) include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and 1,3-diamino. Proban tetraacetic acid, propylene diamine tetraacetic acid, nitrilotriacetic acid, cyclohexane diamine tetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid, etc. can be mentioned.

These compounds may be sodium, potassium, lithium or ammonium salts. Among these compounds, the iron (III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid and methyliminodiacetic acid are preferred because of their high bleaching power.

These ferric ion complex salts may be used in the form of complex salts, and ferric iron solutions such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid or phosphonocarboxylic acid may be used to form a ferric ion complex salt in a solution. In addition, the chelating agent may be used in excess of forming a ferric ion complex salt.
Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and the addition amount thereof is 0.01 to 1.0 mol / preferably 0.05 to
It is 0.50 mol /.

The bleaching solution, the bleach-fixing solution and / or the pre-bath of these,
Various compounds can be used as the bleaching accelerator.
For example, U.S. Pat. No. 3,893,858, German Patent No.
1,290,812, JP-A-53-95630, Research Disclosure No. 17129 (July 1978), compounds having a mercapto group or a disulfide bond, JP-B-45-8506 and JP-A-52 -20832, 53-327
Thiourea compounds described in U.S. Pat. No. 35, U.S. Pat. No. 3,706,561 and the like, or hageronides such as iodine and bromine ions are preferable because of their excellent bleaching power.

In addition, the bleaching solution or bleach-fixing solution used in the present invention contains a bromide (for example, potassium bromide, sodium bromide,
Ammonium bromide) or chlorides (eg, potassium chloride, sodium chloride, ammonium chloride) or iodides (eg, ammonium iodide) and the like can be added, and boric acid, borax, metaboric acid as required. Sodium, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid,
Has a pH buffering capacity for sodium citrate, tartaric acid, etc. 1
More than one kind of inorganic acids, organic acids and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The bleach-fixing solution or the fixing agent used in the fixing solution according to the present invention includes known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiochianate; ethylene. Bisthioglycolic acid, 3,6-dithia-1,8
A thioether compound such as octanediol and a water-soluble silver halide solubilizer such as thioureas, and these may be used alone or in admixture of two or more. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used.
In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of fixer per 1 is 0.
It is preferably 3 to 2 mol, more preferably 0.5 to 1.0 mol.

The pH range of the bleach-fixing solution or the fixing solution is preferably 3-10, and more preferably 5-9.

Further, the bleach-fixing solution may contain various other fluorescent whitening agents, defoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like.

The bleach-fixing solution or the fixing solution according to the present invention may be a sulfite (for example, sodium sulfite, potassium sulfite,
Ammonium sulfite, etc.), bisulfite (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfite (eg, potassium metabisulfite, sodium methyl bisulfite, ammonium metabisulfite, etc.) ) And the like, which contains a sulfite ion-releasing compound. These compounds are converted to sulfite ions by about 0.02
˜0.50 mol / content is preferred, and more preferably 0.04 to 0.40 mol / content.

As a preservative, it is common to add sulfite,
In addition, ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, or the like may be added.

Further, a buffer, an optical brightener, a chelating agent, an antifoaming agent, a fungicide, and the like may be added as necessary.

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

The amount of rinsing water in the rinsing process varies widely depending on the characteristics of the light-sensitive material (for example, depending on the functional material such as coupler) and the application, the rinsing water temperature, the number of rinsing tanks (the number of stages), the replenishment system such as countercurrent and forward flow, and various other conditions. Can be set. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and Television Engineers (Journa
l of the Society of Motion Picture and Tel
evision Engineers) Volume 64, P.248-253 (May 1955 issue). Usually, the number of stages in the multi-stage countercurrent system is preferably 2 to 6, and particularly 2 to 4
Is preferred.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced,
For example, 0.5 to 1 or less per 1 m ^{2 of the} light-sensitive material is possible, but due to the increase in the residence time of water in the tank, bacteria grow and the suspended matter generated adheres to the light-sensitive material. In the processing of the color light-sensitive material of the present invention,
As a solution to such a problem, the method of reducing calcium and magnesium described in Japanese Patent Application No. 61-131632 can be used very effectively. Also, JP-A-57-8542
Compounds and isothiazolone compounds described in No. 61-120145, chlorine-based fungicides such as chlorinated sodium isocyanurate described in Japanese Patent Application No. 60-105487, besozotriazole, copper ions that Sterilization as described in Hiroshi Tahoriguchi's "Chemistry of Antibacterial and Antibacterial Agents", "Sterilization, Sterilization and Antibacterial Technology of Microorganisms" edited by Hygiene Engineering Society, "Encyclopedia of Antibacterial and Antiviral Agents" edited by Japan Society for Antibacterial and Antiviral Agents Agents can also be used.

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

The pH of the washing water in the processing of the light-sensitive material of the present invention is 4 to
9 and preferably 5 to 8. The washing water temperature and washing time can be variously set depending on the characteristics of the photosensitive material, the application, etc.
Generally, 15 seconds to 45 degrees Celsius for 20 seconds to 10 minutes, preferably 25 to 40 degrees Celsius
The range from 30 seconds to 5 minutes is selected with.

It is also possible to carry out treatment with the stabilizing solution directly after the above washing step or without going through the washing step. A compound having an image stabilizing function is added to the stabilizing solution. For example, an aldehyde compound typified by formalin or a film suitable for stabilizing a dye is used.
Examples thereof include a buffering agent for adjusting the pH and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and to impart antifungal properties to the processed light-sensitive material, the above-mentioned various bactericides and antifungal agents can be used.

Further, a surfactant, an optical brightener and a hardener may be added. In the processing of the light-sensitive material of the present invention, when the stabilization is directly carried out without a water washing step, the method disclosed in JP-A-57-
Nos. 8543, 58-14834, 59-184343, 60-220345, 6
0-238832, 60-239784, 60-239749, 61-4054
And known methods described in JP-A-61-118749 can be used.

In addition, it is also a preferred embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.

The liquid used in the washing and / or stabilizing step can be further used in the previous step. As an example of this, it is possible to reduce the amount of waste liquid by flowing the over-flow of the washing water reduced by the multi-stage countercurrent method into the bleach-fixing bath of the preceding bath and supplementing the bleach-fixing bath with a concentrate.

The method of the present invention can be applied to any processing step using a color developer. For example, it can be applied to the processing of color paper, color reversal paper, color direct positive light-sensitive material, color positive film, color negative film, color reversal film, etc., but it is particularly preferably applied to color paper and color reversal paper.

The silver halide emulsion of the light-sensitive material used in the present invention is
Any halogen composition such as silver iodobromide, silver bromide, silver chlorobromide and silver chloride can be used. For example, when performing rapid processing or low replenishment processing of a color paper or the like, a silver chlorobromide emulsion or a silver chloride emulsion containing 60 mol% or more of silver chloride is preferable, and furthermore, a silver chloride content of 80 to 100 is preferable. Molar% is particularly preferred. In addition, high sensitivity is required, and at the time of manufacturing,
When it is necessary to suppress the fog during storage and / or processing to a particularly low level, a silver chlorobromide emulsion or a silver bromide emulsion containing 50 mol% or more of silver bromide (3 mol% or less of silver iodide) May be contained), and more preferably 70 mol% or more. Silver bromoiodide and silver chloroiodobromide are preferable for the color light-sensitive material for photography, and the silver iodide content is preferably 3 to 15 mol%.

The silver halide grains used in the present invention may have different phases in the inside and the surface layer, may have a multi-phase structure having a junction structure, or may have a uniform phase as a whole. Moreover, they may be mixed.

The average grain size of the silver halide grains used in the present invention is represented by the grain diameter (in the case of spherical grains or grains close to spheres) and the ridge length in the case of cubic grains, which is the average based on the projected area. Is expressed in terms of yen) is preferably 2 μm or less and 0.1 μm or more, and particularly preferably 1.5 μm or less and 0.15 μm or more. The grain size distribution may be narrow or wide, but the value (variation rate) obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average size is within 20%, particularly preferably 15%. The so-called monodisperse silver halide emulsions within are preferably used in the present invention. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in the emulsion layers having substantially the same color sensitivity (the above-mentioned monodispersity is the same). Those having a variation rate are preferable) can be mixed in the same layer or multilayer-coated in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be used as a mixture or as a mixture.

The silver halide grains used in the present invention have a regular shape such as a tetrahedron, an octahedron, a rhodohedron and a tetradecahedron.
It may be a compound having different crystal forms or a coexistent form thereof, may have an irregular crystal form such as a spherical shape, or may have a composite form of these crystal forms. Further, tabular grains may be used, and in particular, an emulsion in which tabular grains having a length / thickness ratio value of 5 to 8 or 8 or more account for 50% or more of the total projected area of grains may be used. It may be an emulsion composed of a mixture of these various crystal forms. These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

The photographic emulsion used in the present invention is Research Disclosure (RD) vol.170 Item No.17643 (I, II, II
It can be prepared using the method described in Section I) (December 1978).

The emulsion used in the present invention is usually one that has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are Research Disclosure Vol. 176, No. 17643 (December 1978) and Vol. 187,
No. 18716 (November 1979), and the relevant locations are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures,
The points described in the table below are shown.

Various color couplers can be used in the present invention. Here, the color tumbler refers to a compound capable of forming a dye by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Typical examples of useful color couplers include:
There are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and open-chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are Research Disclosure (RD) 17643 (197).
(December 8) VII-D and the patent cited in 18717 (November 1979).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. The amount of coated silver can be reduced in the case of a two-equivalent color coupler in which a coupling active position is substituted by a leaving group, rather than a four-equivalent color coupler in which a hydrogen atom is present. A coupler in which the color-forming dye has a suitable diffusibility, a colorless coupler, or a DIR coupler which releases a development inhibitor upon coupling reaction or a coupler which releases a development accelerator can also be used.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is U.S. Pat.
No. 210, No. 2,875,057 and No. 3,265,506. In the present invention, the use of a 2-equivalent yellow coupler is preferable, and U.S. Pat. Nos. 3,408,194 and 3,44 are used.
No. 7,928, No. 3,933,501 and No. 4,022,620 oxygen atom desorption type yellow couplers described in JP-B-55-10739, U.S. Pat.No. 4,401,752, No. 4,
326,024, RD18053 (April 1979), British Patent 1,425,
No. 020, West German Application Publication No. 2,219,917, No. 2,261,361
No. 2,329,587, No. 2,433,812 and the like, nitrogen atom-releasing yellow couplers described in JP-A No. 2,329,587 and No. 2,433,812 are typical examples. The α-pivaloyl acetanilide type coupler is excellent in the fastness of the color forming dye, especially the light fastness, while the α-besoyl acetanilide type coupler can obtain a high color density.

As the magenta coupler which can be used in the present invention, a pyrazoloazole type coupler such as an oil protect type isodazolone type or cyanoacetyl type, preferably 5-pyrazolone type may be used in combination as required. 5-
The pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and typical examples thereof are U.S. Pat.Nos. 2,311,082, 2,343,703, and Second 2,600,78
No. 8, No. 2,908,573, No. 3,062,653, No. 3,152,8
No. 96 and No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, a nitrogen atom leaving group described in US Pat. No. 4,310,619 or an arylthio group described in US Pat. No. 4.351,897 is preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

Cyan couplers that can be used in the present invention include oil-protection type naphthol-based and phenol-based couplers, naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.
Representative examples are the oxygen atom-elimination type two-equivalent naphthol couplers described in 4,146,396, 4,228,233 and 4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Patent Nos. 2,369,929 and 2,801,1.
No. 71, No. 2,772,162, No. 2,895,826 and the like. Cyan couplers that are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus described in U.S. Pat.No. 3,772,002. Cyan couplers, U.S. Pat.Nos. 2,772,162 and 1
3,758,308, 4,126,396, 4,334,011, 4,327,173, West German Patent Publication 3,329,729 and 2,5-diacylamino-substituted phenol couplers and U.S. Pat. Third 3,446,622
Nos. 4,333,999, 4,451,559 and 4,42
Nos. 7,767 and the like include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such dye-diffusing couplers are described in U.S. Patent No. 4,366,237 and British Patent No.
Specific examples of magenta couplers are described in 2,125,570, and specific examples of yellow, magenta or cyan couplers are described in EP 96,570 and German Offenlegungsschrift 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in US Pat. No. 2,102,173 and US Pat. No. 4,367,282.

The various couplers used in the present invention can be used in combination of two or more kinds in the same layer of the light-sensitive layer in order to satisfy the properties required for the light-sensitive material, and the same compound can be used in two or more different layers. Can also be introduced.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point organic solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Also, the process of latex dispersion method,
An example of an effect, latex for impregnation is described in US Pat.
No. 9,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the photosensitive silver halide,
Preferably 0.01 to 0.5 moles for yellow couplers,
It is 0.003 to 0.3 mol for the magenta coupler and 0.002 to 0.3 mol for the cyan coupler.

The photographic light-sensitive material used in the present invention is coated on a commonly used plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), a flexible support such as paper or a rigid support such as glass. See Research Disclosure Vol. 176, Item 17643 XV (P.2)
7) Section XVII (P.28) (December 1978 issue).

In the present invention, a reflective support is preferably used. The "reflective support" is one which enhances the reflectivity and makes the dye image formed on the silver halide emulsion layer clear, and such a reflective support includes titanium oxide, zinc oxide, Examples include those coated with a hydrophobic resin containing a light reflecting substance such as calcium carbonate and calcium sulfate dispersed therein, and those using a hydrophobic resin containing a light reflecting substance dispersed therein as a support.

Examples of preferred embodiments of the present invention are shown below. However, it is not limited to the following.

(1) The method for processing a silver halide color photographic light-sensitive material according to claim (1), wherein the color developer contains substantially no sulfite ion.

(2) The method for processing a silver halide color photographic light-sensitive material according to claim (1), wherein the color developing solution contains substantially no benzyl alcohol.

(Examples) Hereinafter, the present invention will be described in more detail by showing specific examples of the present invention. However, the present invention is not limited to the following examples.

Example 1 A multi-layer color photographic paper having the layer constitution shown in Table A was prepared on a paper support laminated on both sides with polyethylene by changing each magenta coupler. The coating liquid was prepared as follows.

Preparation of coating solution for the first layer: 19.1 g of yellow coupler (a) and 4.4 g of color image stabilizer (b), 27.2 ml of ethyl acetate and 7.7 ml of solvent (c).
Was added and dissolved, and this solution was emulsified and dispersed in 185 ml of a 10% gelatin aqueous solution containing 8 ml of 10% sodium dodecylbenzenesulfonate. On the other hand, a blue sensitizing dye shown below was added to a silver chlorobromide emulsion (containing 90.0 mol% of silver bromide and 70 g of Ag / kg) as silver 1.
It was prepared by adding 5.0 × 10 ⁻⁴ mol per mol. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a coating solution for the first layer so as to have the composition shown in Table A. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as the spectral sensitizing dye for each layer.

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mol of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1.2 × 10 ^-2 mol, 1.1 × 10 ^-2
Mole was added.

The following dyes were added to the emulsion layer to prevent irradiation.

and Structural formulas of compounds such as couplers used in this example are as follows.

(E) Refer to Table 1 for magenta coupler (K) Solvent O = P—O—C ₉ H ₁₉ (iso)) ₃ As shown in Table 1, color photographic papers were prepared, each containing a different magenta coupler. The resulting color photographic paper was exposed through an optical wedge and then processed in the next step. Processing temperature Time Color development 38 ° C 1 minute 40 seconds Bleaching and fixing 30-34 ° C 1 minute 00 seconds Rinse 30-34 ° C 20 seconds Rinse 30-34 ° C 20 seconds Rinse 30-34 ° C 20 seconds Drying 70-80 ℃ 50 seconds (Rinse → 3 tank countercurrent method) The composition of each processing solution is as follows.

Color developer Water 800 ml Compound A of the present invention See Table 1 Triethanolamine 8.0 g Diethylenetriaminepentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid (60
%) 2.0 g Nitrilotriacetic acid 2.0 g Benzyl alcohol See Table 1 Diethylene glycol 10 ml Sodium sulfite See Table 1 Potassium bromide 0.5 g Potassium carbonate 30 g 4-Amino-3methyl-N-ethyl-N- [β- (methanesulfone Amido) ethyl] aniline sulfate 5.5g Optical brightener (WHITEX 4B, Sumitomo Chemical Co., Ltd.) 1.5g Add water 1000ml pH 10.25 Bleach fixer Water 400ml Ammonium thiosulfate (70%) 200ml Sodium sulfite 20g Ethylenediaminetetraacetic acid iron ( III) Ammonium 60g Ethylenediaminetetraacetic acid disodium 10g Water added 1000ml pH (25 ℃) 7.00 Rinse solution Benzotriazole 1.0g Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 0.3g Water added 1000ml pH (25 ° C) 7.50 On the other hand, part of the above color developing solution was placed in a beaker 1 and left at 40 ° C for 30 days in an open system, after which time It was treated in the above process steps used.

The treatment using the color developing solution (aging solution) left for 30 days was referred to as the aging solution test, and the treatment using the color developing solution (fresh solution) before being left was referred to as the fresh solution test.

Photographic properties obtained by the fresh liquid test and the aged liquid test are shown in Table 1.

The photographic property is represented by two points, that is, Dmin at magenta density and gradation.

Dmin represents the minimum density, and gradation represents the density change from the point where the density is 0.5 to the density point on the high exposure side of 0.3 at log E.

* 2: Comparative color developer additive (II-a) H ₂ NOH From Table 1, in the comparative example, Dmin in the aged liquid
Increase and change in gradation are large (No. 1 to 6). Even when the coupler of the present invention is used, when a color developing solution other than the present invention is used, the change in Dmin is large (No. 7, 8).

According to the present invention, the change in the above photographic characteristics is suppressed to be extremely small even when the aged solution is used as compared with the case where a fresh solution is used (No. 9 to 20).

Example 2 Under the conditions of No. 9 in Example 1, magenta coupler M-37 was changed to M-58, M-70, M-71, M-72, and M-74, and a similar experiment was conducted. As a result, favorable results were obtained as in Example 1.

Example 3 On a paper support laminated on both sides with polyethylene,
Multilayer printing papers having the following layer constitution were prepared by changing each magenta coupler. The coating liquid was prepared as follows.

(Preparation of coating solution for the first layer) 19.2 g of yellow coupler (ExY-1) and 4.4 g of color image stabilizer (Cpd-1) were mixed with 27.2 cc of ethyl acetate and 7.7 cc (8.0 g) of high boiling solvent (Solv-1). Add and dissolve, and add this solution to 1
10% containing 8% sodium dodecylbenzene sulfonate 10
% Gelatin aqueous solution was emulsified and dispersed in 185 cc. The emulsified dispersion and the emulsions EM7 and EM8 were mixed and dissolved, and the gelatin concentration was adjusted so as to have the following composition to prepare a first layer coating solution.
The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer.

 (Cpd-1) was used as a thickener.

(Layer Configuration) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains a white content (TiO ₂ ) and a bluish dye. ] First layer (blue-sensitive layer) Monodisperse spectrally sensitized with sensitizing dye (ExS-1) Silver chlorobromide emulsion (EM7) 0.15 Monodisperse spectrally sensitized with sensitizing dye (ExS-1) Silver chlorobromide emulsion (EM8) 0.15 Gelatin 1.86 Yellow coupler (ExY-1) 0.82 Color image stabilizer (Cpd-2) 0.19 Solvent (Solv-1) 0.35 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor ( Cpd-3) 0.08 Third layer (green sensitive layer) Monodisperse silver chlorobromide emulsion (EM9) spectrally sensitized with sensitizing dye (ExS-2,3) 0.12 Sensitizing dye (ExS-2,3) Dispersion-sensitized silver chlorobromide emulsion (EM10) 0.24 Gelatin 1.24 Magenta coupler See Table 2 Color image stabilizer (Cpd-4) 0.25 Dye stabilizer (Cpd-5) 0.12 Solvent (Solv-2) 0.25 Fourth layer (UV absorption layer) Gelatin 1.60 UV absorber (Cpd-6 / Cpd-7 / Cpd-8 = 3/2/6: weight ratio) 0.70 Color mixture inhibitor (Cpd-9) 0.05 Solvent (Solv- 3) 0.42 Fifth layer ( Sensitive layer) Monodisperse silver chlorobromide emulsion (EM11) spectrally sensitized with sensitizing dye (ExS-4,5) 0.07 Monodisperse chloroodorous spectrally sensitized with sensitizing dye (ExS-4,5) Silver halide emulsion (EM12) 0.16 Gelatin 0.92 Cyan coupler (ExC-1) 1.46 Cyan coupler (ExC-2) 1.84 Color image stabilizer (Cpd-7 / Cpd-8 / Cpd-10 = 3/4/2: weight ratio )
0.17 Dispersing polymer (Cpd-11) 0.14 Solvent (Solv-1) 0.20 Sixth layer (UV absorbing layer) Gelatin 0.54 UV absorber (Cpd-6 / Cpd-8 / Cpd-10 = 1/5/3: weight Ratio) 0.21 Solvent (Solv-4) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (Modification degree
17%) 0.17 Liquid paraffin 0.03 At this time, (Cpd-12, Cpd-13) was used as the dye for preventing irradiation.

Further, in each layer, alkanol XC (Dupont), sodium alkylbenzenesulfonate, succinate, and MagefacxF-120 (manufactured by Dainippon Ink) were used as emulsifying dispersants and coating aids. (Cpd-14, 15) was used as a stabilizer for silver halide.

 Details of the emulsion used are as follows.

The structural formulas of the compounds used are as follows.

Solv-1 dibutyl phthalate Solv-2 trioctyl phosphate Solv-3 trinonyl phosphate Solv-4 tricresyl phosphate The magenta couplers used are as follows.

Sample A: Magenta Coupler M-I (See Example 1) B: M-R (〃) C: C-M-37 D: M-42 E: M-43 F-: F: M-57 Using Samples A to F, running was performed in the following steps while changing the composition of the color developing solution. The processing steps are as follows. The daily throughput was 15 m ² and the treatment was carried out for 30 days. Processing temperature Temperature Time Replenishment amount ^* Tank capacity Color development 35 ℃ 45 seconds 140ml 17 Bleach fixing 30-36 ℃ 45 seconds 215ml 17 Stable 30-37 ℃ 20 seconds -10 Stable 30-37 ℃ 20 seconds -10 Stable 30-37 ℃ 20 seconds 200 ml 10 Dry 70 to 85 ℃ 60 seconds * per 1 m ^{2 of} photosensitive material (3 tank counter-current system from stable to) The composition of each processing solution is as follows.

Compound B of the invention See Table 2 Bleach-fixing agent (tank solution and replenisher are the same) Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ethylenediaminetetraacetic acid iron (III) ammonium 55g Ethylenediaminetetraacetate disodium 5g Glacial acetic acid 7g Add water 1000ml pH (25 5.6) Stabilizer (same as tank solution and replenisher) Formalin (37%) 0.1 g Formalin-sulfite adduct 0.7 g 5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-Methyl-4 -Isothiazolin-3-one 0.01 g Copper sulphate 0.005 g Water is added to 1000 ml pH (25 ° C) 4.0 Continuous processing (running test) is performed under each condition until replenishing with 3 times the tank capacity (17) of color developer. I went to. Then, changes in the G (green) concentration of the stain and the control portion at the start of the running process and at the end of the running process were measured by a Fuji type densitometer. Furthermore, the sample at the end of the running process is 4 ° C at 60 ° C (5-10RH).
After left for a month, the change in G concentration in the stain part was measured again.

The following magenta photographic characteristic values at the start and end of the running test are shown in Table 2.

* 1: Comparative magenta coupler M used for samples A and B
-See Example 1 for a and m-ro.

* 2: See Example 1 for Comparative Color Developer Additive II-B.

* 3: Increase in Dmin at the end of running relative to Dmin (stain) at the start of running.

* 4: Increase in the G concentration in the gradation part at the end of running with respect to the G concentration in the gradation part during running.

* 5: 60 ° C against Dmin of the sample at the end of running 4
Increase in Dmin after the elapse of months.

From Table 2, in the comparative example, when II-B was used as the color developer additive (Compound B), the increase of Dmin (ΔDm
in), an increase in gradation (Δ gradation) and an increase in Dmin after aging (ΔDmin after aging) are extremely large. Further, when A or B (containing a magenta coupler other than the present invention) is used as a sample, ΔDmi is obtained even when the color developing solution of the present invention is used.
There are large changes in n, Δ gradation, and ΔDmin after aging.

According to the present invention, the fluctuation of the photographic property is significantly reduced.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Morio Yagihara 210 Nakanuma, Minamiashigara City, Kanagawa Fuji Shashin Film Co., Ltd. (56) References JP-A-62-194252 (JP, A) JP-A-62-175749 (JP, A) JP-A-55-110245 (JP, A) JP-A-63-55547 (JP, A)

Claims (1)

(57) [Claims] 1. A silver halide color photographic light-sensitive material containing at least one of pyrazoloazole-based magenta couplers represented by the following general formula (I), which, after exposure, contains an aromatic primary amine color developing agent. , The following general formula (II)
A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a color developer containing at least one selected from hydrazines and hydrazides represented by the formula (1) and containing no sulfite ion. General formula (I) (In the formula, R ₁₁ represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developer. Za, Zb and
Zc represents 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. When Zb-Zc is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring. further
R ₁₁ or X also includes the case of forming a dimer or higher multimer. When Za, Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer is also included. ) General formula (II) (In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ⁴ represents a hydrogen atom, a hydroxy group, a hydrazino group, an alkyl group,
It represents an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group or an amino group, X ¹ represents a divalent group, and n represents 0 or 1. However, n = 0
At this time, R ⁴ represents an alkyl group, an aryl group or a heterocyclic group. R ³ and R ⁴ may together form a heterocycle. )