JP2627070B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color light-sensitive material, and more particularly to a method for processing a silver halide color light-sensitive material in which the replenishment amount of a color developer is remarkably reduced. About.

(Prior art) The processing of silver halide color photographic light-sensitive materials basically consists of two steps of color development (in the case of a color reversal material, the first black and white first development) and desilvering. Consists of a bleaching and fixing step or a single-bath bleach-fixing step used together or alone. If necessary, additional processing steps such as water washing, stop processing, stabilizing processing, and pre-processing for promoting development are added.

In color development, the exposed silver halide is reduced to silver while the oxidized aromatic primary amine developing agent reacts with the coupler to form a dye. In this process, halogen ions generated by the decomposition of silver halide are eluted and accumulated in the developer. On the other hand, the color developing agent is consumed by the reaction with the coupler described above. Further, other components are carried out by being held in the photographic light-sensitive material, and the concentration of the components in the developer decreases. Therefore, in a development processing method in which a large amount of silver halide photographic light-sensitive material is continuously processed by an automatic processor or the like, the components of the color developing solution are kept within a certain concentration range in order to avoid a change in development finish characteristics due to a change in the component concentration. Means is needed.

For example, when the effect of concentration of a consumable component such as a developing agent or a preservative is small, the concentration in a replenisher is generally increased. In some cases, the eluate having an effect of suppressing development, such as halogen, is reduced in concentration or not contained in the replenisher. Further, a compound may be contained in the replenisher to remove the influence of the eluate. Also
In some cases, the pH or the concentration of the alkali or chelating agent is adjusted. As such means, a method is usually employed in which a replenisher for replenishing the insufficient component and diluting the increased component is replenished. The replenishment of the replenisher inevitably generates a large amount of overflow, which is a serious problem in terms of economy and pollution.

In recent years, a reduction in the replenishment amount of the color developer has been strongly desired for the purpose of saving resources and reducing pollution as well as speeding up the development processing. However, simply reducing the replenishment amount of the color developer reduces the development activity due to the accumulation of elutes from the light-sensitive material, particularly bromine ions, which are strong development inhibitors, and various organic compounds, and impairs rapidity. Problems arise.

As a solution to this, a development accelerating technique is required, and many speeding-up techniques for reducing the replenishment amount of the developer are being studied. For example, as one of the methods, there is known a speeding-up means for increasing the pH and the processing temperature of a color developer to promote development. However, this method has a serious problem that fog is high, the stability of the developing solution is deteriorated, and the fluctuation of photographic characteristics is increased during continuous processing. As another accelerating technique, a method of adding various development accelerators is disclosed, but the accelerating effect is insufficient and is not satisfactory.

For the purpose of reducing the accumulation of bromide ion, which is a strong development inhibitor, and speeding up the development, JP-A-58-95345 and JP-A-55-295
Nos. 32342, 61-70552 and WO 87-04534 disclose a method of using a silver halide photosensitive material having a high silver chloride content, which is effective for reducing the replenishment amount of a developer without impairing the speed. Is considered a means. However, when the continuous processing was actually performed by reducing the replenishing amount of the developer, the photographic characteristics associated with the continuous processing, particularly the sensitivity, the minimum density and the maximum density of the magenta color-forming layer, were not significantly impaired. Fluctuates, and furthermore, a new problem that the image storability after processing, particularly yellow stain increases remarkably,
It turned out to be unsuitable for practical use.

On the other hand, JP-A-62-30250, JP-A-62-246054, JP-A-62-24914
Nos. 9 and 62-257156 describe a method for processing a silver halide photosensitive material comprising silver chloride or silver chlorobromide containing a pyrazoloazole-based magenta coupler represented by the general formula [I], which enables rapid processing. A technique is disclosed in which the maximum density of the magenta coloring layer is high, the fog is low, and the color reproducibility is excellent. However, there is no description about continuous processing, and much less of the above-described problem and its solution caused when the replenishment amount of the developer is significantly reduced. I can't.

Currently, the replenishment rate of the color developing solution is slightly different depending on the photosensitive material to be developed, processed photosensitive material 1 m ² per
About 80-1000 ml is generally required. This is because if the replenishment rate is further reduced without impairing the speed, the photographic characteristics, especially the sensitivity, the maximum density and the minimum density of the magenta color developing layer greatly change during continuous processing as described above, and the image storage after processing. This is because a very serious problem of increasing the properties, especially yellow stain, occurs, and no technology has been found that can fundamentally solve these problems.

(Problems to be Solved by the Invention) Accordingly, a first object of the present invention is to provide a photographic property, particularly magenta color development, in a continuous process that does not impair the rapidity even if the replenishment amount of the color developer is significantly reduced. An object of the present invention is to provide a developing method in which the sensitivity, the maximum density, and the minimum density of the layer are small. The second object of the present invention is to provide an image preservability after processing even if the replenishment amount of the color developer is significantly reduced.
In particular, the present invention provides a processing method in which an increase in yellow stain is prevented.

(Means for Solving the Problem) As a result of various studies, the present inventors were able to achieve the above object by the method described below. That is, in a method of processing a silver halide color photographic light-sensitive material with a color developer containing at least one kind of aromatic primary amine color developing agent, a high silver chloride emulsion comprising 80 mol% or more of silver chloride is prepared. A silver halide color photographic light-sensitive material containing at least one layer and having a coated silver amount of 0.70 g / m ² or less and containing at least one pyrazoloazole-based magenta coupler represented by the following general formula (I): method for processing a silver halide color photographic material replenishing amount of the color developing solution comprises treating with color developer is the silver halide photographic material 1 m ² per 30 to 100.

General formula (I) (Wherein, R ₁ represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized aromatic primary amine developer. Za, Zb, and Zc
Represents methine, substituted methine, = N- or -NH-,
One of a Za-Zb bond and a Zb-Zc bond is a double bond,
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, the case where a multimer of dimer or more is formed by R ₁ or X is also included. When Za, Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer is also included. In the present invention, using a high silver chloride color photographic light-sensitive material having a silver chloride content of 80 mol% or more, without impairing the speed,
Method of reducing the replenishing amount of color developer to the photosensitive material 1 m ² per 20~120ml conventionally, during the continuous processing, photographic characteristics, fluctuate particularly sensitive magenta color forming layer, the maximum concentration and minimum concentration is significantly, yet, A new problem that the image storability after processing, especially yellow stain increases, occurs.
It was not practical.

However, as in the present invention, a high silver chloride color photosensitive material containing a pyrazoloazole-based magenta coupler represented by the general formula [I] and having a silver chloride content of 80 mol% or more is used, and the coated silver amount (total coated silver) the means the amount) with 0.70 g / m ² or less, the replenishing amount of color developer, the photosensitive material 1 m ² per 30 to 1
Even if it is reduced to 00 ml, the fact that the sensitivity maximum density and the variation of the maximum density of the magenta color-forming layer are very small, and that the image storability after processing, especially yellow stain is remarkably prevented, is completely unexpected. Was.

The rapid processing method using a high silver chloride photosensitive material comprising 80 mol% or more of silver chloride in the present invention is disclosed in JP-A-58-9534.
5, WO 59-232342, WO 61-070552
However, these are treatments in the absence of the coupler of the general formula [I], and do not disclose any of the above-mentioned problems and their solutions caused when the replenishment amount for development is significantly reduced. However, the technique of the present invention cannot be analogized. Also, JP-A-62-30250, JP-A-62-246054, JP-A-62-249
149, 62-249149 and 62-257156 have the general formula (I)
A method for processing a silver halide light-sensitive material comprising silver chloride or silver chlorobromide containing a coupler represented by is described, but there is no description about the problem when the light-sensitive material is continuously processed. There is no description about the problem when continuous processing is carried out with the replenishment amount of the developer significantly reduced. Furthermore, it does not disclose whether the above-mentioned problem can be solved or not, and does not reach the analogy of the technology of the present invention.

The compound represented by formula (I) will be described in detail.

In the general formula [I], the term "multimer" means a compound having two or more groups represented by the general formula [I] in one molecule, and includes a bis-isomer and a polymer coupler.
Here, the polymer coupler may be a homopolymer composed of only a monomer having a moiety represented by the general formula [I] (preferably having a vinyl group, hereinafter referred to as a vinyl monomer), or an aromatic primary amine developer. Copolymers may be made with non-chromogenic 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 coupler whose color-forming nucleus exhibits isoelectronic aromaticity with naphthalene, and is generally referred to as azapentalene. It has a structure. Preferred compounds among the couplers represented by the general formula [I] are 1H-imidazo [1,2-b] pyrazoles and 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] tetrazole and 1H-pyrazolo [1,5-a] benzimidazole, each having the general formula [II] [III] [IV] [V] [VI]
And [VII]. Of these, particularly preferred compounds are [II] and [V].

The substituents R ₂ , R ₃ and R ₄ in the general formulas (II) to (VII) are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, and a heterocyclic ring. Oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, An alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamide group, a carbamoyl group, an amino group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and X represents a hydrogen atom, a halogen atom, Group, or oxygen atom, nitrogen atom Properly represents a group of the coupling-off with a group bonded to the carbon of the coupling position through a sulfur atom.

R ₂ , R ₃ , R ₄ or X may be a divalent group to form a bis-form. Further, when the moiety represented by the general formulas (II) to (VII) is in the vinyl monomer, R ₂ ,
R ₃ or R ₄ represents a simple bond or a linking group, through which the moieties represented by the general formulas [II] to [VII] and the vinyl group are bonded.

More specifically, R ₂ , R ₃ or R ₄ is a hydrogen atom, a halogen atom (eg, a chlorine atom, a bromine atom), an alkyl group (eg, a methyl group, a propyl group, a t-butyl group, a trifluoromethyl group, a tridecyl group) , 3- (2,4-di-t-amylphenoxy) propyl group, 2-dodecyloxyethyl group, 3-phenoxypropyl group, 2-hexylsulfonyl-ethyl group, cyclopentyl group, benzyl group), aryl group (for example, Phenyl group, 4-t-butylphenyl group, 2,4-di-t-aminophenyl group, 4-tetradecanamidophenyl group), heterocyclic group (for example, 2-furyl group, 2-thienyl group, Pyrimidinyl group, 2-benzothiazolyl group), cyano group, alkoxy group (for example, methoxy group, ethoxy group, 2-methoxyethoxy group,
-Dodecyloxyethoxy group, 2-methanesulfonylethoxy group), aryloxy group (for example, phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group), heterocyclic oxy group (for example, 2-benzimidazolyloxy) Group), acyloxy group (for example, acetoxy group, hexadecanoyloxy group), carbamoyloxy group (for example, N-phenylcarbamoyloxy group, N
-Ethylcarbamoyloxy group), silyloxy group (for example, trimethylsilyloxy group), sulfonyloxy group (for example, dodecylsulfonyloxy group), acylamino group (for example, acetamido group, benzamido group, tetradecanamido group, α- (2,4 -Di-t-amylphenoxy) butylamide group, γ- (3-t-butyl-4-
(Hydroxyphenoxy) butyramide group, α- ｛4-
(4-hydroxyphenylsulfonyl) phenoxydidecamide group), anilino group (for example, phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecanamidoanilino group, 2-chloro-5-dodecyloxycarbonylanilino Group, N-acetylanilino group, 2
-Chloro-5- {α- (3-t-butyl-4-hydroxyphenoxy) dodecaneamide} anilino group), ureido group (for example, phenylureido group, methylureido group, dibutylureido group of N, N), imide Group (for example,
N-succinimide group, 3-benzylhindantoinyl group, 4- (2-ethylhexanoylamino) phthalimide group), sulfamoylamino group (for example, N, N-dipropylsulfamoylamino group, N-methyl -N-decylsulfamoylamino group), alkylthio group (for example, methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3- (4-t-butylphenoxy group) ) Propylthio group, arylthio group (for example, phenylthio group,
2-butoxy-5-t-octylphenylthio group, 3-
Pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetrodecaneamidophenylthio group), heterocyclic thio group (for example, 2-benzothiazolylthio group), alkoxycarbonylamino group (for example, methoxycarbonylamino group , Tetradecylcarbonylamino group), aryloxycarbonylamino group (for example, phenoxycarbonylamino group, 2,4-di-tert-butylphenoxycarbonylamino group), sulfonamide group (for example, methanesulfonamide group, hexadecanesulfonamide) Group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group,
2-methyloxy-5-t-butylbenzenesulfonamide group), 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-t
ert-amylphenoxy) propyl @ carbamoyl group), acyl group (eg, acetyl group, (2,4-di-ter
t-amylphenoxy) acetyl group, benzoyl group),
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), sulfonyl group (for example, methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group,
Toluenesulfonyl group), sulfinyl group (eg, octanesulfinyl group, dodecylsulfinyl group, phenylsulfinyl group), alkoxycarbonyl group (eg, medoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group), aryloxy X represents a carbonyl group (for example, a phenyloxycarbonyl group or a 3-pentadecyloxy-carbonyl group), and X is connected by a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), a carboxyl group, or an oxygen atom. Groups (e.g., acetoxy, propanoyloxy, benzoyloxy, 2,4
-Dichlorobenzoyloxy group, ethoxyoxaloyloxy group, pyrpinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenoxy group, 4-methanesulfonamidophenoxy group, 4-methanesulfonylphenoxy group, α-naphthoxy group, 3 Pentadecylphenoxy, benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy, benzoloxy, 2
-Phenethyloxy group, 2-phenoxyethoxy group, 5
-Phenyltetrazolyloxy group, 2-benzothiazolyloxy group), a group linked by a nitrogen atom (for example, benzesulfonamide group, N-ethyltoluenesulfonamide group, heptafluorobutanamide group, 2,3 , 4,5,6-heptafluorobenzamide group, octanesulfonamide group, p-cyanophenylureido group, N, N-diethylsulfamoylamino group, 1-piperidyl group, 5,5-dimethyl-2,4- Dioxo-3-oxazolidinyl group, 1-
Benzyl-ethoxy-3-hydantoinyl group, 2N-1,1
-Dioxo-3 (2H) -oxo-1,2-benzisothiazylyl group, 2-oxo-1,2-dihydro-1-pyridinyl group, imidazolyl group, pyrazolyl group, 3,5-diethyl-1,2 , 4-Triazol-1-yl, 5- or 6-bromo-benzotriazol-1-yl, 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), a group linked by a sulfur atom (for example, phenylthio group, 2-
Carboxyphenylthio group, 2-methoxy-5-t-octylphenylthio group, 4-methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group,
2-butoxyphenylthio group, 2- (2-hexanesulfonylethyl) -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-5-thiophenylthio group, 2-
Phenyl-3-dodecyl-1,2,4-triazolyl-5
Thio group). When R ₂ , R ₃ , R ₄ or X is a divalent group to form a bis-form, the divalent group may be further described in detail as a substituted or unsubstituted alkylene group (eg, a methylene group, an ethylene group). Group, 1,10-decylene group, -CH
₂ CH ₂ —O—CH ₂ CH ₂ —, etc.), substituted or unsubstituted phenylene groups (for example, 1,4-phenylene group, 1,3-phenylene group, —NHCO—R ₂ —CONH— group (R ₂ represents a substituted or unsubstituted alkylene group or phenylene group.

When those represented by the general formulas [II] to [VII] are present in the vinyl monomer, the linking group represented by R ₂ , R ₃ or R ₄ is an alkylene group (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 (a substituted or unsubstituted phenylene group, for example, 1,4-phenylene group , 1,3-phenylene group, -NHCO-, -CONH-, -O-, -OCO- and aralkylene groups (for example, Etc.) are included.

The vinyl group in the vinyl monomer has the general formula (II)
To [VII] include those having a substituent. Preferred substituents are a hydrogen atom, a chlorine atom,
Alternatively, it is 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-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n -Butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), methylene dibisacrylamide, Vinyl esters (eg, vinyl acetate, vinyl propionate and vinyl urarate),
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-vinylpyridine, and 2- and 4
-Vinyl pyridine and the like. The case where two or more of the non-color-forming ethylenically unsaturated monomers used herein are used together is also included.

Examples of compounds of the couplers represented by the general formulas [II] to [VII] and synthetic methods thereof are described in the following documents.

The compound of the general formula (II) is disclosed in JP-A-59-162548, the compound of the general formula (III) is disclosed in JP-A-60-43659, and the compound of the general formula (IV) is disclosed in JP-B-47-27411. For example, compounds of the general formula [V] are disclosed in JP-A-59-171956 and JP-A-60-1729.
82, the compound of the general formula [VI] is described in JP-A-60-33552, and the compound of the general formula [VII] is described in U.S. Pat.
32 etc.

Also, JP-A-58-42045, JP-A-59-214854, JP-A-59-17755
3, high-color-forming ballast groups described in 59-177554 and 59-177557, etc., are represented by the above general formulas (II) to (VII)
Applies to any of the compounds

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 couplers and the like can be used in combination of two or more in the same layer in order to satisfy the characteristics required for the light-sensitive material, and the same compound can be added to two or more different layers.

Here, the emulsion layer is preferably a green-sensitive emulsion layer composed of a high silver chloride emulsion.

For introducing the coupler into the silver halide emulsion layer, a known method, for example, a method described in US Pat. No. 2,322,027 is used. For example, alkyl phthalates (such as dibutyl phthalate and dioctyl phthalate), phosphates (such as diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, and dioctyl butyl phosphate), citrates (such as tributyl acetyl citrate), 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), and the like, or a compound having a boiling point of about Organic solvent at 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-ethoxy After being dissolved in ethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high-boiling organic solvent and low-boiling organic solvent may be used as a mixture.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling organic solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like. Further, the steps and effects of the latex dispersion method as one of the polymer dispersion methods and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363 and West German patent application (O.
LS) Nos. 2,541,274 and 2,541,230, etc., dispersing methods using organic solvent-soluble polymers are described in PCT JP87 / 00.
No. 492.

Examples of the organic solvent used in the above-described oil-in-water dispersion method include alkyl phthalates (such as dibutyl phthalate and dioctyl phthalate) and phosphates (such as diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, and dioctyl butyl phosphate). Fate), citrate (eg, acetyl tributyl citrate), benzoate (eg, octyl benzoate), alkyl amide (eg, diethyl lauryl amide), fatty acid esters (eg, dibutoxyethyl succinate, diethyl azelate), trimesine Acid esters (eg, tributyl trimesate) and the like, or an organic solvent having a boiling point of about 30 ° C. to 150 ° C., for example, ethyl acetate;
A lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate and the like may be used in combination.

The color developer used in the present invention will be described in detail.

In the present invention, it will be described silver halide light-sensitive material 1 m ² per 30~100ml ranges replenishing amount of color developer. It is impractical in the prior art to reduce the replenishment amount of the developing solution to 100 ml or less due to the above-mentioned problems, and it has been made possible by the present invention for the first time. Replenishment amount 100ml / photosensitive material 1m
² is a value located at the boundary between a range that can be achieved by the present invention for the first time and a range that can be achieved by a combination of conventional techniques other than the present invention. Although somewhat different depending photosensitive material, when the replenishing amount of the developing solution is not more than 30ml / photosensitive material 1 m ^2, take-out amount by the light-sensitive material of the processing solution exceeds the replenishing amount, realistically treatment liquid is reduced Makes continuous processing impossible. The amount of replenishment of 30 ml / m ² of the photosensitive material is an amount that makes the amount of the processing liquid brought out by the photosensitive material and the amount of replenishment substantially equal to each other, depending on the photosensitive material.

It is more preferable that the developer used in the present invention does not substantially contain benzyl alcohol for the purpose of reducing fluctuations in photographic characteristics during continuous processing. Here, substantially not containing, preferably 2 ml / or less, more preferably 0.5 m
A benzyl alcohol concentration of 1 / l or less, most preferably no benzyl alcohol at all.

More preferably, the developer used in the present invention does not substantially contain sulfite ions. Sulfite ions have a function of dissolving silver halide and reacting with an oxidized form of the developing agent, and at the same time, function as a preservative of the developing agent to reduce the dye-forming efficiency. Such an effect occurs when the replenishment amount of the color developer is reduced. It is presumed to be one of the causes of the increase in the fluctuation of the photographic characteristics. Here, "substantially not containing" means preferably having a sulfite ion concentration of 5.0 × 10 ^-3 mol / or less, and most preferably containing no sulfite ion at all. However, in the present invention, a very small amount of sulfite ion used for preventing oxidation of a processing agent kit in which a developing agent is concentrated before preparing a working solution is excluded.

The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. this is,
This is because hydroxylamine itself has a silver developing activity at the same time as functioning as a preservative of the developer, and fluctuations in the concentration of hydroxylamine are considered to greatly affect photographic characteristics. The term "substantially free of hydroxylamine" as used herein means that the hydroxylamine concentration is preferably 5.0 × 10 ⁻³ mol / or less, and most preferably contains no hydroxylamine at all.

It is more preferable that the developer used in the present invention contains an organic preservative in place of the hydroxylamine and the sulfite ion in view of stability of photographic properties during continuous processing and image storability after processing.

Here, the organic preservative refers to any organic compound that reduces the deterioration rate of an aromatic primary amine color developing agent by being added to a processing solution of a color photographic light-sensitive material. That is, organic compounds having a function of preventing oxidation of a color developing agent by air or the like, among which hydroxylamines (excluding hydroxylamine), hydroxamic acids,
Hydrazines, hydrazides, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds And condensed amines are particularly effective organic preservatives. These are Japanese Patent Application No. 61-147823,
No. 61-173595, No. 61-165621, No. 61-188619, No.
61-197760, 61-186561, 61-198987, 61
-201861, 61-186559, 61-170756, 61-
Nos. 188742, 61-188741, U.S. Pat.
No. 4903, JP-A-52-143020, and JP-B-48-30496.

With respect to the preferred organic preservatives, general formulas and specific compounds are shown below, but the present invention is not limited thereto.

The amount of the following compounds added to the color developer is 0.005
Mol / ~ 0.5 mol /, preferably 0.03 mol / ~
It is desirable to add so as to have a concentration of 0.1 mol /.

 The following are preferred as the hydroxyamines.

General formula (VIII) In the formula, R ¹¹ and R ¹² represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or a heteroaromatic group.
R ¹¹ and R ¹² are not hydrogen atoms at the same time and may be linked to each other to form a heterocyclic ring together with the nitrogen atom.

The ring structure of the hetero ring is a 5- to 6-membered ring and is constituted by a carbon atom, a hydrogen atom, a halogen atom, a nitrogen atom, a sulfur atom and the like, and may be saturated or unsaturated.

It is preferred that R ¹¹ and R ¹² are an alkyl group or an alkenyl group, and the number of carbon atoms is preferably 1 to 10, particularly preferably 1 to 5. Examples of the nitrogen-containing hetero ring formed by linking R ¹¹ and R ¹² include a piperidyl group, a pyrrolidyl group, an N-alkylpiperazyl group, a morpholyl group, an indolinyl group, and a benzotriazole group.

Preferred substituents of R ¹¹ and R ¹² are hydroxy group, an alkoxy group, an alkyl or arylsulfonyl group, an amido group, a carboxy group, a cyano group, a sulfo group, a nitro group and an amino group.

Compound example The following are preferred as the hydroxamic acids.

General formula (IX) In the formula, A ²¹ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxy group, Or an unsubstituted aryloxy group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, an acyl group, a carboxy group, a hydroxyamino group, or a hydroxyaminocarbonyl group. Examples of the substituent include a halogen atom, an aryl group, an alkyl group, an alkoxy group, and the like.

Preferably, A ²¹ is a substituted or unsubstituted alkyl group, aryl group, amino group, alkoxy group, aryloxy group. Particularly preferred examples are a substituted or unsubstituted amino group, an alkoxy group, and an aryloxy group. The number of carbon atoms is preferably 1 to 10.

X ²¹ is Or, represents -SO-. Preferably X ²¹ is It is.

R ²¹ is a hydrogen atom, a substituted or unsubstituted alkyl group,
Represents a substituted or unsubstituted aryl group. At this time,
A ²¹ and R ²¹ may be linked to form a ring structure. The substituent is the same as the substituents mentioned in A ^21. Preferably R ²¹
Is a hydrogen atom.

Y ²¹ represents a hydrogen atom or a group that can be converted to a hydrogen atom by a hydrolysis reaction.

Compound example The following are preferred as hydrazines and hydrazides.

General formula (X) In the formula, R ³¹ , R ³² , and R ³³ represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, and R ³⁴ is a hydroxy group, a hydroxyamino group, a substituted or unsubstituted group, Represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group, or an amino group. The heterocyclic group is a 5- to 6-membered ring,
It is composed of C, H, O, N, S and a halogen atom and may be saturated or unsaturated. X ³¹ is -CO-, -SO _2- , or And n is 0 or 1. In particular, when n = 0, R ³⁴ represents a group selected from an alkyl group, an aryl group and a heterocyclic group, and R ³³ and R ³⁴ may form a heterocyclic ring together.

In the general formula (X), R ³¹ , R ³² and R ³³ represent a hydrogen atom or C ₁ -C
_It is preferably an alkyl group of ₁₀ , particularly preferably R ³¹ and R ³² are hydrogen atoms.

In the general formula (X), R ³⁴ is preferably an alkyl group, an aryl group, an alkoxy group, a carbamoyl group, or an amino group. Particularly, the case of an alkyl group or a substituted alkyl group is preferable. Here, preferable substituents of the alkyl group include a carboxyl group, a sulfo group, a nitro group, an amino group, a phosphono group and the like. X ³¹ is preferably —CO— or —SO ₂ —, and most preferably —CO—.

_{X-2 NH 2 NHCH 2 4} SO 3 H X-3 NH 2 NHCH 2 2 OH _{X-6 NH 2 NHCOCH 3 X} -7 NH 2 NHCOOC 2 H 5 X-10 NH ₂ NHCONH ₂ X-12 NH ₂ NHSO ₃ H X-14 NH ₂ NHCOCONHNH ₂ X-15 NH ₂ NHCH ₂ CH ₂ CH ₂ SO ₃ H X-18 NH ₂ NHCH ₂ CH ₂ COOH The following phenols are preferred.

General formula (XI) In the formula, R ⁴¹ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, a carbamoyl group, a sulfamoyl group, an amide group, a sulfonamide group, a ureido group, an alkylthio group, Represents an arylthio group, a nitro group, a cyano group, an amino group, a formyl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxysulfonyl group, and an aryloxysulfonyl group. When R ⁴¹ is further substituted, examples of the substituent include a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, and the like. When there are two or more R ⁴¹ , the types may be the same or different, and when they are adjacent to each other, they may be bonded to each other to form a ring. The ring structure is a 5- to 6-membered ring and is constituted by a carbon atom, a hydrogen atom, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom and the like, and may be saturated or unsaturated.

R ⁴² represents a hydrogen atom or a hydrolyzable group. Further, m and n are integers from 1 to 5, respectively.

In formula (XI), preferred R ⁴¹ is an alkyl group, a halogen group, an alkoxy group, an alkylthio group, a carboxyl group, a sulfo group, a carbamoyl group, a sulfamoyl group, an amino group, an amide group, a sulfonamide group, a nitro group, and It is a cyano group. Among them, an alkoxy group, an alkylthio group, an amino group, and a nitro group are particularly preferable, and these are more preferably in the ortho position or the para position of the (OR ⁴² ) group. Further, the carbon number of R ⁴¹ is preferably from 1 to 10, particularly preferably from 1 to 6.

Desirable R ⁴² is a hydrogen atom or a hydrolyzable group having 1 to 5 carbon atoms. When there are two or more (OR ⁴² ) groups, it is more preferable that they are located at the ortho or para position with respect to each other.

The following are preferred as α-hydroxyketones and α-aminoketones.

General formula (XII) In the formula, R ⁵¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, an aryloxy group or an amino group, and R ⁵² represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group. And R ⁵¹ and R ⁵² may form a carbocyclic or heterocyclic ring together. R ⁵¹ represents a hydroxyl group or a substituted or unsubstituted amino group.

In the general formula (XII), R ⁵¹ is a hydrogen atom, an alkyl group, an aryl group, when an alkoxy group is preferred, and R ⁵²
Is preferably a hydrogen atom or an alkyl group.

Sugars are also preferred organic preservatives.

(Also referred to as carbohydrate) saccharide comprises monosaccharide and polysaccharide, many have the general formula C _n H _2m O _m. Monosaccharides generally refer to aldehydes or ketones of polyhydric alcohols (referred to as aldoses and ketoses, respectively) and their reduced derivatives, oxidized derivatives, dehydrated derivatives, and a wider range of derivatives such as amino sugars and thio sugars. The polysaccharide refers to a product obtained by dehydrating and condensing two or more of the aforementioned monosaccharides.

Of these saccharides, more preferred are aldoses having a reducing aldehyde group, and derivatives thereof, and particularly preferred are those corresponding to monosaccharides.

XIII-1 D-okilose XIII-2 L-arabinose XIII-3 D-ribose XIII-4 D-deoxyribose XIII-5 D-glycose XIII-6 D-calactose XIII-7 D-mannose XIII-8 Glucosamine XIII-9 L-sorbose XIII-10 D-sorbitol (sorbitol) Examples of the monoamines include the following.

General formula (XIV) In the formula, R ⁷¹ , R ⁷² and R ⁷³ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group. Where R ⁷¹ and R ⁷² , R ⁷¹ and R ⁷³ or R ⁷² and R
⁷³ may be linked to form a nitrogen-containing heterocyclic ring.

Here, R ⁷¹ , R ⁷² and R ⁷³ may have a substituent. As R ⁷¹ , R ⁷² and R ⁷³ , a hydrogen atom and an alkyl group are particularly preferred. Examples of the substituent include a hydroxyl group, a sulfo group, a carboxyl group, a halogen atom, a nitro group, an amino group, and the like.

XIV-1 NCH ₂ CH ₂ OH) ₃ XIV-2 H ₂ NCH ₂ CH ₂ OH XIV-3 HNCH ₂ CH ₂ OH) ₂ XIV-10 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ SO ₂ CH ₃ XIV-11 NHCH ₂ COOH) ₂ XIV-13 H ₂ NCH ₂ CH ₂ SO ₂ NH _{2 XIV-14 H 2 N-CCH} 2 OH) 2 The following are preferred as the diamines.

General formula (XV) In the formula, R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group.

R ⁸⁵ represents a divalent organic group, specifically, an alkylene group, an arylene group, an aralkylene group, an alkenylene group, or a heterocyclic group.

R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ are particularly preferably a hydrogen atom and an alkyl group, and R ⁸⁵ is particularly preferably an alkyl group.

XV-2 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ NCH ₂ CH ₂ OH) ₂ XV-4 H ₂ NCH ₂ CH ₂ NCH ₂ CH ₂ OH) ₂ The following are preferred as polyamines.

General formula (XVI) In the formula, R ⁹¹ , R ⁹² , R ⁹³ and R ⁹⁴ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic ring.

R ⁹⁵ , R ⁹⁶ , and R ⁹⁷ represent a divalent organic group, and have the same meaning as R ^{85 in} formula (XV).

X ⁹¹ and X ⁹² -O -, - S -, - CO -, - SO 2 -, - SO- or represents a linking group composed of a combination of these linking radical, R
⁹⁸ has the same ^meaning as R ⁹¹ , R ⁹² , R ⁹³ and R ⁹⁴ . m represents 0 or an integer of 1 or more.

(The upper limit of m is not particularly limited and may be a high molecular weight as long as the compound is water-soluble, but m is usually preferably in the range of 1 to 3.) XVI-2 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ OCH ₂ CH ₂ NCH ₂ CH ₂ OH) ₂ The following are preferable as the quaternary ammonium salt.

General formula (XVII)(Where R¹⁰¹Represents an n-valent organic group;¹⁰², R¹⁰³And R
¹⁰⁴Represents a monovalent organic group. The organic group here is carbon
Represents a group of formula 1 or more, specifically, an alkyl group, an aryl
And a heterocyclic group. R¹⁰², R¹⁰³And R¹⁰⁴Horse
At least two groups are bonded to form a quaternary ammonium source.
It may form a heterocyclic ring containing a child. n is one or more integers
A number, X Represents a counter anion. ) R¹⁰², R¹⁰³And R¹⁰⁴In the above, a particularly preferred monovalent group is substituted
Or an unsubstituted alkyl group, R¹⁰², R¹⁰³And R¹⁰⁴of
At least one is a hydroxyalkyl group, an alkoxyl
Most preferably a alkyl group or a carboxyalkyl group.
Good. n is preferably an integer of 1 to 3, more preferably
1 or 2.

The following are preferred as nitroxy radicals.

General formula (XVIII) R ¹¹¹ and R ¹¹² each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Further, these alkyl group, aryl group or heterocyclic group may have a substituent. Examples of such a substituent include a hydroxy group, an oxo group, a carbamoyl group, an alkoxy group, a sulfamoyl group, a carboxy group, and a sulfo group. Examples of the heterocyclic group include a pyridyl group and a piperidyl group.

Preferably, R ¹¹¹ and R ¹¹² are a substituted or unsubstituted aryl group or a tertiary alkyl group (for example, a t-butyl group).

(Compound example) The following are preferred as alcohols.

General formula (XIX) Wherein R ¹²¹ represents a hydroxy-substituted alkyl group;
¹²² represents an unsubstituted alkyl group or the same group as ^R121 . R
¹²³ represents a hydrogen atom or a group similar to ^R122 . X ¹²¹ is a hydroxy group, a carboxyl group, a sulfo group, a nitro group,
Represents an unsubstituted or hydroxy-substituted alkyl group, an unsubstituted or substituted amide group or a sulfonamide group.

In the general formula (XIX), X ¹²¹ is preferably a hydroxy group, a carboxyl group, or a hydroxyalkyl group.

XIX-4 HO-CHCH ₂ OH) ₂ XIX-5 (HO-CH _{2 3} COOH XIX-6 CCH ₂ OH ₄ XIX-7 (HOCH _{2 3} C-CH ₃ XIX-8 (HOCH _{2 3} C-NHCOCH ₃₎ The following are preferred as alcohols.

General formula (XX) In the formula, R ¹³¹ , R ¹³² and R ¹³³ each represent a hydrogen atom or an alkyl group, and n represents a positive integer up to 500.

The alkyl group represented by R ³¹ , R ¹³² and R ¹³³ preferably has 5 or less carbon atoms, more preferably 2 or less carbon atoms. R ¹³¹ , R ¹³² and R ¹³³ are very preferably a hydrogen atom or a methyl group, most preferably a hydrogen atom.

n is preferably a positive integer of 3 or more and 100 or less, and more preferably 3 or more and 30 or less.

XX-1 HOCH ₂ CH ₂ O ₄ OH XX-2 CH ₃ OCH ₂ CH ₂ O ₃ OH XX-3 CH ₃ OCH ₂ CH ₂ O ₂ OCH _{3 XX-5 HOCH 2 CH 2 OCH} 3 XX-6 C 2 H 5 OCH 2 CH 2 O 2 OH XX-7 HOCH 2 CH 2 O n H average molecular weight of about _{300 XX-8 HOCH 2 CH 2} O n H average molecular weight of about the following are preferred as _{800 XX-9 HOCH 2 CH 2} O n H average molecular weight of about _{3000 XX-10 HOCH 2 CH 2} O n H average molecular weight of about 8000 oximes.

General formula (XXI) In the formula, R ¹⁴¹ and R ¹⁴² represent a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group, respectively. Further, R ¹⁴¹ and R ¹⁴² may be the same and different, and these groups may be connected to each other.

In Formula (XXI), R ¹⁴¹ and R ¹⁴² are preferably an alkyl group substituted by a halogen group, a hydroxyl group, an alkoxyl group, an amino group, a carboxyl group, a sulfo group, a phosphonic acid group, and a nitro group, and unsubstituted Is an alkyl group.

The total number of carbon atoms in the general formula (XXI) is preferably 30 or less, more preferably 20 or less.

The following are preferred as polyamines.

General formula (XXII) In the formula, X ¹⁵¹ and X ¹⁵² represent -CO- or -SO _2- , and R ¹⁵¹ , R ¹⁵² , R ¹⁵³ , R ¹⁵⁴ , R ¹⁵⁵ and R ¹⁵⁶ represent a hydrogen atom, an unsubstituted or substituted alkyl group. And R ¹⁵⁷ represent an unsubstituted or substituted alkylene group, an unsubstituted or substituted arylene group and an unsubstituted or substituted aralkylene group. m ¹ , m ² and n represent 0 or 1.

The following are preferred as _{XXII-6 H 2 NSO 2 NHSO} 2 NH 2 condensed ring amines.

General formula (XXIII) In the formula, X represents a trivalent atom group necessary for completing a condensed ring, and R ¹ and R ² represent an alkylene group, an arylene group, an alkenylene group, or an aralkylene group.

Here, R ¹ and R ² may be the same or different from each other.

Among the general formulas (XXIII), particularly preferred are the compounds represented by the general formulas (1-a) and (1-b).

In the formula, X ¹ represents N or CH. R ¹ and R ² are defined as in general formula (XXIII), and R ³ is the same group as R ¹ and R ² , or Represents

In the general formula (1-a), X ¹ is preferably N. The carbon number of R ¹ , R ² , and R ³ is preferably 6 or less, more preferably 3 or less, and most preferably 2.

R ¹ , R ² and R ³ are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

In the formula, R ¹ and R ² are defined as in the general formula (XXIII).

In the general formula (1-b), it is preferable that R ¹ and R ² have 6 or less carbon atoms. R ¹ and R ² are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

Among the compounds of the general formulas (1-a) and (1-b), the compound represented by the general formula (1-a) is particularly preferable.

Many of the compounds of the general formulas (VIII) to (XXIII) according to the present invention can be easily obtained as commercial products.

Two or more kinds of the organic preservatives may be used in combination. Preferred combinations are at least one compound of the general formulas (VIII) to (XIII) and at least one compound of the formulas (XIV) and (XXIII).

More preferred combined use is at least one of the general formulas (VIII) and (X) and at least one of the general formulas (XIV) and (XXIII).

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 p-phenylenediamine, representative examples of which are shown below, but are 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-methanesulfonamidoethyl) -aniline The use of D-4 is particularly preferred.

Further, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride and p-toluenesulfonic acid salt. The amount of the aromatic primary amine developing agent to be used is preferably about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g, per developing solution.

The color developer used in the present invention is preferably pH 9
To 12, more preferably 9 to 11.0, and the color developer may further contain a compound of a known developer component.

In order to maintain the above pH, it is preferable to use various buffers. 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), potassium tetraborate, o
-Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

The amount of the buffer added to the color developer was 0.1 mol / mol.
It is preferably at least 0.1 mol / -0.4 mol / m.

In addition, various chelating agents can be used in the color developer as a precipitation inhibitor for calcium or magnesium, or for improving the stability of the color developer.

Specific examples are shown below, but the present invention is not limited thereto. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, N, N, N-triethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, 1,3- Diamino-2-propanoltetraacetic acid, Trauscyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-
Diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediamineorthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1- Diphosphonic acid, N, N'-bis (2-hydroxybenzyl), ethylenediamine-N, N'-diacetic acid These chelating agents may be used in combination of two or more as necessary.

These chelating agents may be added in an amount sufficient to block the metal ions in the color developer. For example, 1
It is about 0.1g to 10g per unit.

An optional development accelerator can be added to the color developer as needed.

As development accelerators, JP-B-37-16088 and JP-B-37-598
No. 7, No. 38-7826, No. 44-12380, No. 45-9919, and thioether compounds represented by U.S. Pat. p-phenylenediamine compound, JP-A-50-1377
No. 26, JP-B-44-30074, JP-A-56-156826 and 5
Quaternary ammonium salts represented by 2-43429, etc .; p-aminophenols described in U.S. Pat. Nos. 2,610,122 and 4,119,462;
Nos. 4,230,796 and 3,253,919, JP-B-41-11431
Nos. 2,482,546, 2,596,926 and 3,582
Amine compounds described in 2,346, etc., JP-B-37-16088
No. 42-25201, U.S. Pat.No. 3,128,183, Japanese Patent Publication No. 41
-11431, 42-23883 and U.S. Pat.
Phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, and the like can be added as necessary.

An optional antifoggant can be added to the color developer used in the present invention, 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 organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole,
Nitrogen-containing heterocyclic compounds such as 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiozolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be mentioned as typical examples.

The color developer used in the present invention preferably contains a fluorescent whitening agent. 4,4'-
Diamino-2,2'-disulfostilbene compounds are preferred. The amount of addition is 0-5 g / preferably 0.1-4 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.

Replenishing amount of color developer of the present invention per photosensitive material 1 m ² 30
~ 100ml. The replenishing amount referred to here indicates the amount of replenishment of a so-called color developing replenisher, and the amount of an additive or the like for correcting deterioration with time or concentration is outside the replenishing amount of the present invention.

The additive herein refers to, for example, water for diluting the concentration, a preservative that easily deteriorates with time, or an alkali agent that increases the pH.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing processing before bleach-fixing processing or bleaching processing after bleach-fixing processing can be arbitrarily performed according to the purpose.
Examples of the bleaching agent include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used. Representative bleaches include ferricyanide; dichromate; iron (II
Organic complex salts of I) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Use of aminopolycarboxylic acids such as diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid; persulfates; bromates; permanganates; it can. Among these, iron aminopolycarboxylates (II) including iron (III) complex salts of ethylenediaminetetraacetate
I) Complex salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. In addition, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching and bleach-fixing solutions. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-812.
No. 95,630, Research Disclosure No. 17,129 (July, 1978), etc .; compounds having a mercapto bond or a disulfide group; thiazolidine derivatives described in JP-A-50-140,129; US Pat. No. 3,706,561. Thiourea derivatives; iodide salts described in JP-A-58-16,235; polyoxyethylene compounds described in West German Patent No. 2,748,430; polyamine compounds described in Japanese Patent Publication No. 45-836; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and particularly preferred are the compounds described in U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95,630. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether-based compounds, thioureas, and a large amount of iodide.The use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. As a preservative of the bleach-fixing solution, a sulfite, a bisulfite, a sulfinic acid or a carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the application, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers, Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, calcium ion described in Japanese Patent Application No. 61-131,632,
The method of reducing magnesium ions can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-5-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Bactericidal and Fungicide Chemistry" It is also possible to use bactericides described in "Sterilization, Sterilization and Antifungal Techniques of Microorganisms" edited by the Society of Sanitary Engineers, and "Encyclopedia of Antifungal and Antifungal Agents" edited by the Japan Society of Antifungals and Fungi.

In the processing of the photosensitive material of the present invention, the pH of the washing water is 4-
9, preferably 5-8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, application, etc., but generally, the temperature is 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds-5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such a stabilization process, Japanese Unexamined Patent Application Publication No.
Known methods described in Nos. 57-8,543, 58-14,834, and 60-220,345 can all be used.

Further, after the above-mentioned water washing treatment, a stabilization treatment may be further carried out. For example, a stabilizing bath containing formalin and a surfactant used as a final bath of a color light-sensitive material for photography can be mentioned. . Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline-based compounds described in U.S. Pat. Salt complexes and urethane compounds described in JP-A-53-135,628 can be mentioned.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64,339, JP-A-57-144,547, and JP-A-58-144,547.
No. 115,438 and the like.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to. Further, in order to save silver of the light-sensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

The method of the present invention can be applied to processing of color paper, color reversal paper, color direct positive paper and the like.

Next, the silver halide color photographic light-sensitive material used in the present invention will be described in detail.

Regarding the halogen composition of the silver halide emulsion used in the present invention, 80 mol% or more is silver chlorobromide containing substantially no silver iodide, which is composed of silver chloride. preferable. Here, "substantially free of silver iodide" means that the silver iodide content is 1.0 mol% or less, preferably 0.2 mol% or less. If the silver chloride content is lower than this or the silver iodide content is higher than the above range, the developing speed is too slow to apply to rapid processing. Therefore, a higher silver chloride content is preferred. That is, it is preferably at least 90 mol%, more preferably at least 95 mol%. It is also preferable to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, the silver chloride content is 98 mol% or more.
An almost pure silver chloride emulsion having a content of 99.9 mol% is also preferably used. However, the use of a pure silver chloride emulsion may be disadvantageous in obtaining high sensitivity and preventing fogging caused when pressure is applied to the photosensitive material.

In the silver halide grains used in the present invention, most of the remaining composition other than silver chloride consists of silver bromide. In this case, the silver bromide may be uniformly contained in the silver halide grains (one grain is formed by a uniform solid solution of silver chlorobromide) or forms different phases in the silver bromide content. It may be contained in the form. In the latter case, the core (core) inside the particle,
So-called laminated grains in which the halogen composition is different from one or more shells surrounding the shell may be used, or the silver bromide content may be different (preferably the silver bromide content is high).
The localized phase may be a particle formed discontinuously on the surface and / or inside of the particle. These localized phases having a high silver bromide content can be present inside the grains, at the edges of the grains, at the corners or on the faces.As one preferred example, those having an epitaxy junction at the corners of the grains are preferred. Can be mentioned.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is calculated) is from 0.1 μm to 2 μm. preferable.

The particle size distribution is preferably a so-called monodisperse coefficient of variation (a standard deviation of the particle size divided by the average particle size) of 20% or less, and preferably 15% or less. At this time, it is also preferable to use the above monodispersed emulsion by blending it in the same layer or to apply a multilayer coating in order to obtain a wide latitude.

The formation of silver halide grains contained in photographic emulsions has a regular (regula-like) cubic, tetradecahedral or octahedral shape.
r) Those having a crystal form, those having an irregular crystal form such as a sphere or a plate, or those having a complex form thereof can be used. Also,
It may be composed of a mixture of those having various crystal forms. In the present invention, among these, the particles having the above-mentioned regular crystal form should be contained in 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition, emulsions in which tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, as projected area exceeds 50% of all grains can be preferably used.

The silver chlorobromide emulsion used in the present invention is described in Chemi by P. Glafkides.
e et Phisique Photographique (published by Paul Montel, 196
7) Photographic Emulsion Chemistry by GFDuufin
(Focal Press, 1966), M by VLZelikman et al
aking and Coating Photographic Emulsion (Focal Pre
ss, 1964), Research Disclosure (R
D) vol.176 Item No. 17643 (I, II, III) (December 1978
) Can be prepared. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halide, any method such as a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. May be used. A method of forming particles in an atmosphere containing excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of keeping pAg constant in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced during the process of forming emulsion grains or physical ripening. Examples of the compound to be used include salts of cadmium, zinc, lead, copper, thallium and the like, or salts or complex salts of Group VIII element iron, ruthenium, rhodium, palladium, osmium, iridium and platinum. it can. Especially above VI
Group II elements can be preferably used. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol based on silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

As the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used.

Silver coating amount of silver halide emulsion of the photosensitive material used in the method of the present invention as a silver amount, but is generally at 1.5 g / m ² or less, preferably 0.70 g / m ² or less 0.3 g / m ² or more It is.
When the coated silver amount is 0.70 g / m ² or less, it is very good in terms of rapidity, processing stability, and image storage stability after processing (particularly suppression of yellow stain).

The photographic emulsion used in the present invention is Research Disclosure (RD) vol. 176 Item No. 17643 (I, II, III)
It can be prepared using the method described in section (December 1978).

The emulsion used in the present invention is usually subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such a process are described in Research Disclosure Vol. 176, No. 17643 (December 1978) and Vol.
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, and their locations are shown in the table below.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole, etc.), mercaptopyrimidines, mercaptotriazines Thioketo compounds such as oxadolinthione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindene), pentaazaindenes and the like Many compounds known as antifoggants or stabilizers, such as benzenethiosulfonate, benzenesulfinate, benzenesulfonamide, and the like, can be added.

Of these, mercaptoazoles are preferably added to the coating solution of the silver halide emulsion.

As a specific example, And the like.

The addition amount is 1 × 10 ⁻⁵ per mol of silver halide.
5 × 10 ^-2 mol is preferred. Furthermore, 1 × 10 ⁻⁴ to 10 ⁻² mol is particularly preferred.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the intended spectral sensitivity—a spectral sensitizing dye. As the spectral sensitizing dye used at this time, for example, Heterocyclic compo by FH Harmer
unds-Cyanine dyes and related compounds (John Wil
ey & Sons [New York, London], 1964). As specific examples of the compounds, those described in JP-A-62-215272, page 22, upper right column to page 38, are preferably used.

 Particularly preferred specific examples are described below.

In the present invention, the new aqueous colloid layer in the light-sensitive material may contain a water-soluble dye as a filter dye or for various purposes such as prevention of irradiation.

Such dyes include, for example, GB 506,385.
Nos. 1,177,429, 1,311,884, 1,338,799,
1,385,371, 1,467,214, 1,433,102, 1,5
No. 53,516, JP-A-48-85,130, JP-A-49-114,420, and
Nos. 5-161,233 and 59-111,640, U.S. Pat.
No. 3,469,985, oxonol dye having a pyrazolone nucleus or barbituric acid nucleus described in 4,078,933 and the like,
Hemioxonol dyes, U.S. Pat.Nos. 2,843,486 and 32,945
Cyanine dyes, merocyanine dyes, styryl dyes, and azo dyes described in No. 39 and the like. Preferred specific examples include: And the like.

Various color couplers can be used in the present invention. Here, the color coupler refers to a compound capable of forming a dye by a coupling reaction with an oxidized aromatic primary amine developing agent. Typical examples of useful color couplers include:
There are naphthol or phenolic 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 described in Research Disclosure (RD) 17643 (197
(December 8), and in the patents cited in Section VII-D and 18717 (November 1979).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is diffusion-resistant by being polymerized. A two-equivalent color coupler in which the coupling active position is substituted with a leaving group can reduce the amount of coated silver than a four-equivalent color coupler of a hydrogen atom. Couplers in which the color-forming dye has an appropriate diffusibility, colorless couplers, or DIR couplers which release a development inhibitor or a coupler which releases a development accelerator upon coupling reaction can also be used.

Typical examples of the yellow coupler that can be used in the present invention include oil-protected acylacetamide couplers. Specific examples thereof are described in U.S. Pat.
No. 210, No. 2,875,057 and No. 3,265,506. In the present invention, the use of a two-equivalent yellow coupler is preferred, and U.S. Patent Nos. 3,408,194 and 3,44
7,928, 3,933,501 and 4,022,620, etc., described as oxygen couplers yellow couplers or JP-B-55-10739, U.S. Pat.No. 4,401,752,
No. 326,024, RD-18053 (April 1979), British Patent No. 1,42
No. 5,020, West German Application Publication No. 2,219,917, No. 2,261,361
And nitrogen atom-elimination type yellow couplers described in JP-A Nos. 2,329,587 and 2,433,812. α-pivaloylacetanilide couplers are excellent in the fastness of coloring dyes, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

The magenta coupler usable in the present invention in addition to the coupler of the general formula (I) includes oil-protected indazolone-based or cyanoacetyl-based magenta couplers,
-Pyrazolone-based couplers. The 5-pyrazolone-based 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 a coloring dye.
Nos. 2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896, and 3,936,015. As a leaving group of a 2-equivalent 5-pyrazolone-based coupler, US Pat.
Preferred are a nitrogen atom leaving group described in 4,310,619 or an arylthio group described in US Pat. No. 4,351,897. Further, a 5-pyrazolone-based coupler having a ballast group described in European Patent No. 73,636 can obtain a high color density.

Cyan couplers that can be used in the present invention include oil-protected naphthol couplers and phenol couplers, and naphthol couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.Nos. 4,052,212 and 4,146,396, Nos. 4,228,233 and 4,296,200
The representative examples are the oxygen-equivalent double-equivalent naphthol couplers described in the above publication. Specific examples of phenol couplers are described in U.S. Pat.Nos. 2,369,929 and 2,80
Nos. 1,171, 2,772,162, and 2,895,826.

Among these, in the present invention, it is more preferable to use a cyan coupler of the general formula (C) in the red-sensitive emulsion layer from the viewpoint of stability of photographic characteristics during continuous processing.

General formula (C) (In the formula, R ¹ represents an alkyl group, a cycloalkyl group, an aryl group, an amino group or a heterocyclic group. R ² represents an acylamino group or an alkyl group having 2 or more carbon atoms. R ³ represents a hydrogen atom or a halogen atom. , An alkyl group or an alkoxy group, and R ³ may combine with R ² to form a ring.
Z ¹ represents a hydrogen atom, a halogen atom, or a group capable of leaving upon reaction with an oxidized form of an aromatic primary amine color developing agent. In formula (C), the alkyl group represented by R ¹ is preferably an alkyl group having 1 to 32 carbon atoms, such as a methyl group, a butyl group, a tridecyl group, a cyclohexyl group, and an allyl group. Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the heterocyclic group include a 2-pyridyl group and a 2-furyl group.

When the amino group of R ¹ is the phenyl substituted amino group optionally particular a substituent group.

R ¹ further represents an alkyl group, an aryl group, an alkyl or aryloxy group (for example, a methoxy group, a dodecyloxy group, a methoxyethoxy group, a phenyloxy group, a 2,4
-Di-tert-amylphenoxy group, 3-tert-butyl-
4-hydroxyphenyloxy group, naphthyloxy group), carboxy group, alkyl or arylcarbonyl group (for example, acetyl group, tetradecanoyl group, benzoyl group), alkyl or aryloxycarbonyl group (for example, methoxycarbonyl group, phenoxycarbonyl) Group), acyloxy group (eg, acetyl group, benzoyloxy group), sulfamoyl group (eg, N-ethylsulfamoyl group, N-octadecylsulfamoyl group), carbamoyl group (eg, N-ethylcarbamoyl group, N -Methyl-dodecylcarbamoyl group), a sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group), an acylamino group (eg, acetylamino group, benzamide group, ethoxycarbonylamino group, phenyla Roh carbonylamino group), an imido group (e.g., succinimido group, hydantoinyl group), a sulfonyl group (e.g., methanesulfonyl group),
It may be substituted with a substituent selected from a hydroxy group, a cyano group, a nitro group and a halogen atom.

In the general formula (C), Z ¹ represents a hydrogen atom or a coupling-off group, and examples thereof include a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), and an alkoxy group (for example, a dodecyloxy group, Methoxycarbamoylmethoxy group, carboxypropyloxy group, methylsulfonylethoxy group), aryloxy group (for example,
4-chlorophenoxy group, 4-methoxyphenoxy group), acyloxy group (for example, acetoxy group, tetradecanoyloxy group, benzoyloxy group), sulfonyloxy group (for example, methanesulfonyloxy group, toluenesulfonyloxy group), amide Group (for example, dichloroacetylamino group, methanesulfonylamino group, toluenesulfonylamino group), alkoxycarbonyloxy group (for example, ethoxycarbonyloxy group, benzyloxycarbonyloxy group), aryloxycarbonyloxy group (for example, phenoxycarbonyloxy group) Group), an aliphatic or aromatic thio group (eg, phenylthio group, tetrazolylthio group), an imide group (eg, succinimide group, hydantoinyl group), an N-heterocyclic ring (eg, 1-pyrazolyl group, - such as benztriazolyl group), an aromatic azo group (e.g., phenylazo group) and the like. These leaving groups may include photographically useful groups.

R ¹ or R ² of the general formula (C) may form a dimer or a multimer thereof.

Specific examples of the cyan coupler represented by the general formula (C) are shown below, but in the present invention, a more preferable cyan coupler is not limited thereto.

The cyan coupler represented by the general formula (C-1) can be synthesized based on the description in JP-A-59-166696 and JP-B-49-11572.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such dye-diffusing couplers are disclosed in U.S. Pat.
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.

Dye-forming couplers and the above-mentioned special couplers may form polymers of dimers or more. Typical examples of polymerized dye-forming couplers are described in U.S. Patent Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and US Patent No. 4,367,282.

Various couplers used in the present invention can be used in combination of two or more in the same layer of the photosensitive layer, or different two or more layers of the same compound in order to satisfy the characteristics required for the photosensitive material. Can also be introduced.

The coupler used in the present invention can be introduced into a light-sensitive material by the above-mentioned known dispersion method.

Typical amounts of color coupler used range from 0.001 to 1 mole per mole of photosensitive silver halide,
Preferably 0.01 to 0.5 mol for a yellow coupler,
The amount is 0.003 to 0.3 mol for the magenta coupler and 0.002 to 0.3 mol for the cyan coupler.

In the present invention, the following compounds are preferably used together with the above-mentioned coupler. In particular, combination use with a pyrazoloazole coupler is preferred.

That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product and the coupler remaining in the film.

Preferred as the compound (F) is a compound having a secondary reaction rate constant k2 (in trioctyl phosphate at 80 ° C.) of 1.0 / mol · sec to 1 × 10 ⁻⁵ / mol · sec with p-anisidine. Compound. The secondary reaction rate constant can be measured by the method described in JP-A-63-158545.

If k2 is larger than this range, the compound itself becomes unstable, and may react with gelatin or water and decompose. On the other hand, if k2 is smaller than this range, the reaction with the remaining aromatic amine-based developing agent is slow, and as a result, the side effect of the remaining aromatic amine-based developing agent, which is the object of the present invention, may not be prevented.

More preferable compound (F) can be represented by the following general formula (FI) or (F II).

General formula (FI) R1- (A) nx General formula (F II) In the formula, R1 and R2 each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group which forms a chemical bond by reacting with an aromatic amine-based developer, and X represents a group which is eliminated by reacting with an aromatic amine-based developer. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents that an aromatic amine-based developing agent is added to the compound of the general formula (F II). Represents a promoting group. Here, R1 and X, or Y and R2 or B may be bonded to each other to form a cyclic structure.

Representative methods of chemically bonding with the residual aromatic amine-based developing agent are a substitution reaction and an addition reaction.

Specific examples of the compounds represented by formulas (FI) and (F II) are described in JP-A-63-158545, JP-A-62-283338,
Those described in the specifications such as Japanese Patent Application Nos. 62-158342 and 63-18439 are preferred.

On the other hand, the compound (G) which forms a chemically inactive and colorless compound by chemically bonding to an oxidized form of an aromatic amine-based developing agent remaining after the color development treatment is more preferably represented by the following general formula (GI) ).

Formula (GI) RZ In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group which decomposes in the light-sensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z is a nucleophilic ⁿ CH ₃ I value of Pearson (RGPearso
n, et al., J. Am Chem, Soc., 90 , 319 (1968)), or a group derived therefrom is preferred.

Specific examples of the compound represented by the general formula (GI) are described in EP-A-255722, JP-A-62-143048 and JP-A-62-143048.
-229145, Japanese Patent Application Nos. 63-18439, 63-136724, 6
What is described in 2-214681, 62-158342, etc. is preferable.

The details of the combination with the compound (G) and the compound (F) are described in Japanese Patent Application No. 63-18439.

The photographic light-sensitive material used in the present invention is coated on a commonly used plastic film (eg, cellulose nitrate, cellulose acetate, polyethylene terephthalate), a flexible support such as paper, or a rigid support such as glass. For details on the support and the coating method, refer to Research Disclosure, Vol. 176, Item 17643, Item XV (P.27) XV
It is described in Section II (P.28) (December 1978).

In the present invention, a reflective support is preferably used. "Reflective support" enhances reflectivity to sharpen a dye image formed in a silver halide emulsion layer. Such a reflective support includes titanium oxide, zinc oxide, Examples include those coated with a hydrophobic resin dispersedly containing a light reflecting substance such as calcium carbonate and calcium sulfate, and those coated with a hydrophobic resin dispersedly containing a light reflecting substance as a support.

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

Reference Example 1 A multilayer color photographic paper A having the following layer constitution was produced on a paper support laminated on both sides with polyethylene. The coating solution is prepared by mixing and dissolving an emulsion, various chemicals, and an emulsified dispersion of a coupler. The respective preparation methods are described below.

Preparation of coupler emulsifier; 19.1 g of yellow coupler (ExY)
27.2cc of ethyl acetate in 4.4g of color image stabilizer (Cpd-1)
And 7.7 cc of a solvent (Solv-1) were added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate.

Thereafter, each emulsion for magenta, cyan and intermediate layers was prepared in the same manner. The compounds used for each emulsion are shown below.

(ExM) Magenta coupler: Table 1 (CxC1) C-1 (ExC2) C-9 (Cpd-5) Color mixing inhibitor Same as Cpd-2, except that R = C ₈ H ₁₇ (t) (Cpd-6) Color image stabilizer 6a: 6b: 6c = 5: 8: 9 mixture (weight ratio) (UV-1) UV absorber Cpd-6a: 6b: 6c = 2: 9: 8 mixture (weight ratio) (Solv-2) solvent O = PO-C ₈ H ₁₇ (iso)) ₃ (Solv-3) solvent O = PO-C ₉ H ₁₉ (iso)) ₃ The following dyes were added to the emulsion layer for preventing irradiation.

Green sensitive layer: Same as Dye-R. However, n = 1.

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.

Next, the emulsion used in this example will be described.

Blue-sensitive emulsion: average particle size 1.1 μm, coefficient of variation (standard deviation divided by average particle size = s / d) 0.1 according to a conventional method
A monodisperse cubic silver chloride emulsion (containing K ₂ IrCl ₆ , 1,3-dimethylimidazoline-2-thione) was prepared.
A 0.6% solution of the spectral sensitizing dye for blue (S-1) was added to 1.0 kg of 26 kg.
cc and further a 0.05 .mu.m silver bromide fine grain emulsion was added at a ratio of 0.5 mol% with respect to the host silver chloride emulsion. After ripening, sodium thiosulfate was added to perform optimal chemical sensitization to obtain a stabilizer (stb-1). ) Was added by adding 10 ^-4 mol / mol Ag.

Green-sensitive emulsion: After preparing silver chloride particles containing K ₂ IrCl ₆ and 1,3-dimethylimidazoline-2-thione by a conventional method, sensitizing dye of 4 × 10 ^-4 mol / mol Ag (S-2) And KB
After ripening and ripening, sodium thiosulfate was added for optimal chemical sensitization, and a stabilizer (stb-1) was added at 5 × 10 ⁻⁴ mol / mol Ag to give an average particle size of 0.48 μm and a variation coefficient of 0.10 μm.
Was prepared.

Red-sensitive emulsion: prepared in the same manner as the green-sensitive emulsion. However, S-
1.5 × 10 ^-4 mol / mol A of sensitizing dye (S-3) instead of 2
g was used.

 Next, the compounds used are shown.

(Layer Structure) The composition of each layer in the sample is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support: polyethylene-laminated paper [polyethylene on the first layer side contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive layer) Silver halide emulsion 0.25 gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture prevention (Cpd-2) 0.08 Third layer (green sensitive layer) Silver halide emulsion 0.31 Gelatin 1.24 Magenta coupler (ExM) Reference 1 Color image stabilizer (Cpd-3) 0.25 Color image stabilizer (Cpd-4) 0.12 Solvent (Solv-2) 0.42 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorber ( UV-1) 0.62 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv-3) 0.24 Fifth layer (red-sensitive layer) Silver halide emulsion 0.21 Gelatin 1.34 Cyan coupler (Blend of ExC1 and C2, 1: 1) 0.34 Color image stabilizer (Cpd-6) 0.17 Polymer (Cpd-7) 0.40 Solvent (Sol v-4) 0.23 sixth layer (ultraviolet absorbing layer) gelatin 0.53 ultraviolet absorber (UV-1) 0.21 solvent (Solv-3) 0.08 seventh layer (protective layer) gelatin 1.33 acrylic modified copolymer of polyvinyl alcohol (modified) Every time
17%) 0.17 Flow rate paraffin 0.03 1-oxy-3,5-dichloro-s-triazine sodium salt was used as a hardening agent for each layer.

Samples A to G were prepared by changing the magenta coupler as shown in Table 1 in the same manner as in Sample A.

The following experiment was conducted to examine the photographic characteristics of these coated samples.

First, a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source 3200 ゜ K) was applied to the above coated sample.
Tonal exposures for sensitometry were provided. The exposure at this time was performed so that the exposure amount was 250 CMS with an exposure time of 1/10 second.

Next, after imagewise exposure of the coated sample, continuous processing (running test) was performed in the following processing step and the following processing solution composition until replenishment was twice the tank capacity of the color developer.
However, the composition of the color developer was changed as shown in Table 2 and a running test was performed for each of them.

The composition of each processing solution is as follows.

Bleach-fix solution (same as tank solution and replenisher) Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Iron (III) ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 5g Ammonium bromide 40g Glacial acetic acid 9g Add water 1000ml PH (25 ℃) 5.40 Rinse solution (same as tank solution and replenisher) Ion-exchanged water (calcium and magnesium 3ppm or less each) At the start and end of running, process the sensitometry and maximize green (G) The density (Dmax), the minimum density (Dmin), and the sensitivity (the log E value representing density 0.5) due to continuous processing were measured using a Macbeth densitometer,
The results are shown in Table 2. In the sensitivity change, + indicates a direction of increasing sensitivity, and-indicates a direction of decreasing sensitivity.

At the same time, the unexposed samples are processed at the end of running to evaluate the yellow stain after processing, and each processed sample is processed.
The samples were stored at 80 ° C. and 70% relative humidity for 10 days, and the changes after storage were examined. The results are shown in Table 2.

According to Table 2, when a photosensitive material containing no magenta coupler represented by the general formula (I) is used, the minimum density of the magenta coloring layer (GL) at the start and end of the running as shown in processing steps 1 to 3 , The maximum density and the sensitivity fluctuated very much, and the increase in yellow stain after processing was very large.

When the photosensitive material containing the magenta coupler represented by the general formula (I) according to the present invention is used, the processing step
As shown in the figure, when the fluctuation of the photographic characteristics of the magenta coloring layer (GL) clearly accompanied by running is reduced, the yellow stain after processing is extremely suppressed, and the replenishment amount of the color developer is significantly reduced. In addition, it has become possible to achieve both good processing stability and image storability.

Further, as shown in the processing step, the benzyl alcohol is not contained in the color developer in terms of stability of photographic characteristics during continuous processing and image stability after processing,
It turns out that it is more preferable in the present invention.

Reference Example 2 In the same manner as Reference Example 1, except that M-3 and M-
Using 13, M-23, M-39, M-42 and M-54, respectively, similarly preferred results were obtained.

Reference Example 3 Using the same photosensitive materials A to G as in Reference Example 1, continuous processing (running test) was performed in the following processing step and the following processing solution composition until the color developing solution was replenished with twice the tank capacity. However, the running test was performed for each of the compositions of the color developers while changing the compositions as shown in Table 3.

The composition of each processing solution is as follows.

The sensitometry is performed at the start and the end of the running, and the change in the minimum density (Dmin) and the maximum density (Dmax) and the sensitivity (log E value representing density 0.5) of each layer are continuously measured. The measurement was performed using a densitometer, and the results are shown in Table 3. In the sensitivity change, + indicates a direction of increasing sensitivity, and-indicates a direction of decreasing sensitivity.

At the same time, the unexposed samples were processed at the end of running for evaluation of the yellow stain after processing,
The sample was stored for 10 days at 70 ° C. and a relative humidity of 70%, and the change after storage was examined. The results are shown in Table 3.

According to Table 3, when a photosensitive material containing no magenta coupler represented by the general formula (I) is used, the minimum density, the maximum density and the sensitivity at the start and end of the running as shown in the processing steps 1 to 3 It was observed that the variation was very large and the increase in yellow stain after treatment was very large.

When the light-sensitive material containing the magenta coupler represented by the general formula (I) is used, as shown in the processing steps (1) to (4), the fluctuation of the photographic characteristics accompanying the running clearly decreases, and the yellow stain after the processing is reduced. Is extremely suppressed, and when the replenishment amount of the color developer is significantly reduced,
It has become possible to achieve both good processing stability and image storability.

Further, it is more preferable that the color developing solution does not contain a sulfite as shown in the processing step, and it is more preferable that the color developing solution does not contain hydroxylamine as shown in the processing step. I understand. Among them, as shown in the processing step, the color developer does not contain sulfite and hydroxylamine, and contains an organic preservative, which leads to processing stability and image preservation after processing. It can be seen that this is more preferable.

Reference Example 4 In the same manner as in Reference Example 3, except that
VIII-2, IX-7, instead of VIII-1 of the organic preservative A,
When X-15, XI-5, XII-1, and XIII-5 were used, similarly favorable results were obtained. In the processing step, instead of XIV-1 of organic preservative B, XV-5, XV-8, XV-5
VI-1, XVI-3, XVII-1, XVII-3, XVIII-1, XV
III-2, XVIII-3, XIV-10, XX-8, XXI-1, XXII
When -1, XXII-6 and XXIII-1 were used, similarly favorable results were obtained.

Example 1 On a paper support laminated on both sides with polyethylene,
Samples (1) to (4) were prepared by changing the amount of silver applied, the magenta coupler and the cyan coupler on a multilayer photographic paper having the following layer structure. As an example, a coating solution was prepared as follows.

(Preparation of coating solution for first layer) 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) In 4.4 g, 27.2 cc of ethyl acetate and a high boiling solvent (Sol
v-1) 7.7 cc (8.0 g) was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. 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. 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.

 (Cpd-2) was used as a thickener.

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

Support Polyethylene laminated paper [The polyethylene on the first layer side contains white pigment (TiO ₂ ) and blue dye. First layer (blue-sensitive layer) Monodisperse silver chlorobromide emulsion (EM7) spectrally sensitized with sensitizing dye (ExS-1) 0.15 Monodisperse spectrally sensitized with sensitizing dye (ExS-1) Silver chlorobromide emulsion (EM8) 0.15 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-2) 0.19 Solvent (Solv-1) 0.35 Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture 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 Spectroscopy with sensitizing dye (ExS-2,3) Sensitized monodispersed silver chlorobromide emulsion (EM10) 0.24 Gelatin 1.24 Magenta coupler (ExY) See Table 4 Color image stabilizer (Cpd-4) 0.25 Color image stabilizer (Cpd-5) 0.12 Solvent (Solv-) 2) 0.25 Fourth layer (ultraviolet ray absorbing layer) Gelatin 1.60 Ultraviolet ray absorbent (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 Red-sensitive layer) Monodisperse silver chlorobromide emulsion (EM11) spectrally sensitized with sensitizing dye (ExS-4,5) 0.07 Monodisperse salt spectrally sensitized with sensitizing dye (ExS-4,5) Silver bromide emulsion (EM12) 0.16 Gelatin 0.92 Cyan coupler (ExC-1) See Table 4 Cyan coupler (ExC-2) See Table 4 Color image stabilizer (Cpd-7 / Cpd-8 / Cpd-10 = 3) / 4/2: weight ratio)
0.17 Polymer for dispersion (Cpd-11) 0.14 Solvent (Solv-1) 0.20 Sixth layer (ultraviolet absorbing layer) Gelatin 0.54 Ultraviolet 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 (degree of modification)
(17%) 0.17 Liquid paraffin 0.03 At this time, (Cpd-12, Cpd-13) was used as a 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. As a silver halide stabilizer, ^10-4 mol / mol Ag of stb-1 of Example 1 was added.

 The details of the emulsion used are as follows.

The structural formula of the compound used is as follows.

ExM See Table 4 ExC-1 See Table 4 ExC-2 See Table 4 Solv-1 dibutyl phthalate Solv-2 trioctyl phosphate Solv-3 trinonyl phosphate Solv-4 tricresyl phosphate Sample B was prepared as described above.

Further, Samples A, C and D were prepared in exactly the same manner as Sample B, except that the amount of coated silver (g / m ² ) was changed as shown in the following table.

After imagewise exposure of the above photosensitive material, continuous processing (running test) using a paper processing machine until the following processing steps and processing liquid are used to replenish the color developing tank twice as large as the tank capacity
Was done.

The composition of each processing solution is as follows.

Bleach-fix solution (same as tank solution and replenisher) Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ammonium iron (III) ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 5g Glacial acetic acid 9g Add water 1000ml pH (25 ℃) 5.40 Stabilizer (Tank solution and replenisher are the same) 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 Ammonium water (28%) 2.0 ml Add water 1000 ml pH (25 ° C) 4.0 As in Reference Example 1, maximum concentration, minimum concentration, sensitivity with running process And the yellow stain after the treatment were measured, and the results are shown in Table 4.

According to Table 4, when the photosensitive material containing no magenta coupler represented by the general formula (I) is used, the minimum of the magenta coloring layer (GL) at the start and end of the running as shown in processing steps 1 to 3 is shown. It was observed that the variations in density, maximum density and sensitivity were very large, and that the increase in yellow stain after processing was very large.

When a light-sensitive material containing no magenta coupler represented by the general formula (I) according to the present invention is used, processing steps
As shown in the figure, when the fluctuation of the photographic characteristics of the magenta color-forming layer (GL) apparently due to running is reduced, the yellow stain after processing is extremely suppressed, and the replenishment amount of the color developer is significantly reduced. In addition, it has become possible to achieve both good processing stability and image storability.

Further, in the present invention, as shown in the light-sensitive material, it is more preferable that the amount of the light-sensitive material and the coated silver is 0.70 g / m ² or less in terms of stability of photographic characteristics during continuous processing and image stability after processing. You can see that.

Further, in the present invention, as shown in (1) to (3), the light-sensitive material contains a cyan coupler represented by the general formula (C) in terms of stability of photographic properties during continuous processing, particularly processing stability of RL. It turns out that it is more preferable.

Example 2 In the same manner as in Example 1, except that M-3, M-13, and M were used instead of the magenta coupler M-37 in the light-sensitive material.
When -23, M-37, M-39, M-43, M-45 and M-61 were used, similarly favorable results were obtained.

Example 3 In the same manner as in Example 1, except that C-9 and C- were used instead of the cyan couplers C-1 and C-3 in the light-sensitive material.
When 10 was used, similarly favorable results were obtained.

Claims (3)

(57) [Claims] 1. A method of processing a silver halide color photographic light-sensitive material with a color developer containing at least one aromatic primary amine color developing agent, comprising a high silver chloride comprising at least 80 mol% of silver chloride. A silver halide color photograph having at least one emulsion of the formula (I) and having a coated silver amount of 0.70 g / m ² or less and containing at least one pyrazoloazole-based magenta coupler represented by the following general formula (I): the light-sensitive material, method for processing a silver halide color photographic material replenishing amount of the color developing solution comprises treating with color developer is the silver halide photographic material 1 m ² per 30 to 100. General formula (I) (Wherein, R ₁ represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized aromatic primary amine developer. Za, Zb, and Zc
Represents methine, substituted methine, = N- or -NH-,
One of a Za-Zb bond and a Zb-Zc bond is a double bond,
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. In addition, R ₁
Or, the case where X forms a dimer or more multimer is also included.
When Za, Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer is also included. ) 2. The processing method according to claim 1, wherein said color developer contains substantially no hydroxylamine. 3. The processing method according to claim 1, wherein said color developer contains an organic preservative.