DE69031531T2 - Use of purple couplers to reduce color spots - Google Patents

Description

The present invention relates to the use of dye-forming couplers represented by the formula (I) or (II) for suppressing magenta stain in a silver halide color photographic material.

Among the silver halide color photographic materials, the most common ones are those containing three types of color couplers which form yellow, magenta or cyan colors upon coupling with an oxidation product of an aromatic primary amine color developing agent.

As magenta couplers used therein, pyrazolo-triazole type magenta couplers, e.g. those disclosed in U.S. Patent 3,725,067, are preferred in view of color reproduction because they form azomethine dyes having better subsidiary absorption in the region around 430 nm. They are also preferred because the occurrence of stains in the uncolored areas of the photographic material due to heat or humidity is reduced.

It is important to reduce the thickness of the dry layer of color photographic light-sensitive materials in order to improve image quality, especially sharpness.

Couplers are usually dissolved in an organic solvent having a high boiling point and their emulsified dispersion is coated on a support to form the color photographic light-sensitive material. Therefore, reducing the amount of the organic solvent having a high boiling point is important to reduce the layer thickness. Since the amount of the organic solvent having a high boiling point is related to the mechanical strength of the layer, reducing the amount of the organic solvent having a high boiling point results in a reduction in the amount of gelatin used.

However, when pyrazoloazole-type couplers are used, a serious problem arises in that when the amount of the high boiling point organic solvent is reduced, a strong subsidiary absorption is generated on the short wavelength side due to the occurrence of aggregation of the dyes formed by processing. The generation of subsidiary absorption leads to a decrease in color reproducibility. Therefore, it has been desirable to develop pyrazoloazole-type magenta couplers whose use does not lead to aggregation of the dyes formed by processing.

In JP-A-63-321426 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"), various additives are disclosed for eliminating such aggregation. However, the introduction of additives results in an increased layer thickness, which in turn leads to a reduction in sharpness. It is also feared that the preservability of the photographic material is adversely affected.

Combinations of pyrazolotriazole-type couplers and high boiling point organic solvents are described, for example, in JP-A-61-28948, JP-A-61-267760, JP-A-62-79451, JP-A-62-86363, JP-A-62-91 946, JP-A-62-98352, JP-A-62-148951 and JP-A-63-10454. However, the particular combination of couplers and high boiling point organic solvents according to the present invention is not disclosed in these references. In addition, there is no discussion therein regarding prevention of aggregation of the dyes formed.

The Journal of The Society of Photographic Science and Technology of Japan, vol. 52, p.162 (1989) describes a connection between the size of an alkyl group present at the 6-position of the pyrazolotriazole coupler and the absorption spectrum and light fading of the dye formed therefrom in a liquid phase. However, it is impossible to predict a practical system using an organic solvent with a high boiling point from this experiment because the experiment reported was carried out in a dilute, uniform solution.

EP-A-031 9985 and EP-A-0399541, which are included in the prior art under Article 54(3) EPC, disclose photographic materials comprising pyrazolotriazole couplers satisfying the present formulas (I) and (II). The magenta couplers may be incorporated into the photographic materials by using a high boiling point organic solvent.

Due to the poor light resistance of pyrazolotriazole-type couplers, their use requires the addition of large amounts of color-fading agents. In addition, their light resistance tends to decrease as the amount of the organic solvent with a high boiling point is reduced.

Therefore, methods for preventing the aggregation of dyes and improving the light resistance while reducing the amount of the high boiling point organic solvent by modifying the coupler structures have been investigated.

In addition, magenta stains tend to appear after development processing when pyrazolotriazole-type couplers are used. This tendency is particularly pronounced when rapid processing is carried out or when processing is carried out with a low level of a replenisher. To solve these problems, it was proposed to add an anti-staining agent to couplers containing oil droplets. As a result, however, it is difficult to reduce the thickness of the dry layer.

Therefore, it is an object of the present invention to provide a color photographic light-sensitive material using a pyrazoloazole-type coupler having improved color tone and sharpness.

It is a further object of the present invention to provide a silver halide color photographic material comprising a reflective support having thereon a layer containing a pyrazolotriazole-type coupler and a reduced amount of an organic solvent having a high boiling point, The material has improved color reproducibility and lightfastness.

It is a further object of the present invention to provide a silver halide color photographic material comprising a pyrazolotriazole-type coupler and a reduced amount of an organic solvent having a high boiling point, which material has improved color reproducibility and light resistance when processed through processing steps comprising black-and-white development and color development.

It is still another object of the present invention to provide a color photographic light-sensitive material which is improved in the formation of stains and has excellent color reproduction even when subjected to rapid processing or processing with a low level of replenishment.

Other objects of the present invention will become apparent from the following detailed description and examples.

As a result of various investigations, it has been found that the objects of the present invention can be achieved by using at least one dye-forming coupler represented by the formula (I) or (II) described below, optionally in combination with an organic solvent having a high boiling point, having a solvent to coupler weight ratio of not more than 1, for suppressing magenta stains in a silver halide color photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer and at least one light-insensitive layer, at least one layer of the light-sensitive silver halide emulsion layer containing the at least one dye-forming coupler represented by the general formula (I) or (II) and optionally the organic solvent having a high boiling point:

wherein R₁ represents a branched alkyl group or an aryl group; R₂ represents a hydrogen atom or a substituent; X represents a hydrogen atom or a substituent released upon a coupling reaction with an oxidation product of an aromatic primary amine developing agent; A represents an oxygen atom, a nitrogen atom or a sulfur atom; and n represents 0 or 1.

Figures 1(A) to 1(D) are graphs showing the reflection spectra of color images obtained when Samples 101 to 120 were exposed to green light and subjected to development processing.

Figures 2(A) to 2(D) are graphs showing transmission spectra of color images obtained when only the green-sensitive layers of Samples 201 to 216 were subjected to color formation.

The pyrazolotriazole magenta couplers represented by the general formulas (I) and (II) are described in detail below.

In the general formulas (I) and (II), R₁ represents a substituted or unsubstituted branched alkyl group or a substituted or unsubstituted aryl group.

The unsubstituted branched alkyl group includes a branched alkyl group having 3 to 24 carbon atoms. Suitable examples of substituents for the substituted branched alkyl group include a halogen atom (e.g. fluorine, chlorine and bromine), a hydroxy group, a cyano group, a carboxy group, a sulfo group, an alkoxy group (e.g. methoxy, ethoxy, isopropyloxy and butoxy), an aryloxy group (e.g. phenoxy, 2,4-di-tert-amylphenoxy, p-tert-octylphenoxy and o-methoxyphenoxy), an alkylthio group (e.g. methylthio, ethylthio, butylthio, octylthio and hexadecylthio), an arylthio group (e.g. phenylthio, 2-butoxy-5-tert-octylphenylthio and 2-pivaloylaminophenylthio), an acylamino group (e.g. acetylamino, pivaloylamino, 2-ethylhexanoylamino and tetradecanoylamino), a Sulfonamido group (e.g. methanesulfonamido, hexadecanesulfonamido and p-toluenesulfonamido), a carbamoyl group (e.g. N-butylcarbamoyl and N,N-diethylcarbamoyl), a sulfamoyl group (e.g. N-ethylsulfamoyl and N,N-diisopropylsulfamoyl), an alkoxycarbonyl group (e.g. methoxycarbonyl, ethoxycarbonyl and 2-ethylhexyloxycarbonyl), an alkylamino group (e.g. ethylamino, isopropylamino, tert-octylamino and dodecylamino), an anilino group, a carbamoylamino group, an alkoxycarbonylamino group, an acyloxy group and a sulfonyl group.

The unsubstituted aryl group includes a phenyl group and a naphthyl group. Suitable examples of substituents of the substituted aryl group include a halogen atom (e.g. fluorine, chlorine and bromine), a hydroxy group, a cyano group, a carboxy group, a sulfo group, an alkyl group (e.g. methyl, ethyl, tert-butyl and tert-octyl), an alkoxy group (e.g. methoxy, ethoxy, isopropyloxy and butoxy), an aryloxy group (e.g. phenoxy, p-tert-octylphenoxy and o-methoxyphenoxy), an alkylthio group (e.g. methylthio, ethylthio, butylthio and hexadecylthio), an arylthio group (e.g. phenylthio, 2-butoxy-5-tert-octylphenylthio and 2-pivaloylaminophenylthio), an acylamino group (e.g. acetylamino, pivaloylamino, 2-ethylhexanoylamino and tetradecanoylamino), a sulfonamido group (e.g. methanesulfonamido, hexadecanesulfonamido, p-toluenesulfonamido and 2-octyloxy-5-tert-octylbenzenesulfonamido), a carbamoyl group (e.g. N-methylcarbamoyl, N-butylcarbamoyl, N, N-diethylcarbamoyl and N, N-diisopropylcarbamoyl), a sulfamoyl group (e.g. N-methylsulfamoyl, N-ethylsulfamoyl, N,N-diethylsulfamoyl and N,N-diisopropylsulfamoyl), an alkoxycarbamoyl group (e.g. methoxycarbamoyl, ethoxycarbamoyl, 2-ethylhexyloxycarbamoyl and dodecyloxycarbamoyl), an alkylamino group (e.g. ethylamino, isopropylamino, butylamino, dodecylamino and N,N-dibutylamino), an anilino group, a carbamoylamino group, an alkoxycarbonylamino group and a sulfonyl group.

In the general formulas (I) and (II), R₂ represents a hydrogen atom or a substituent. Suitable examples of the substituent include a linear or branched, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms (e.g., methyl, ethyl, isopropyl, tert-butyl, 2-ethylhexyl, cyclohexyl and adamantyl), an aryl group (e.g., phenyl, p-tolyl, 2-methoxyphenyl, 2-pivaloylamidophenyl, 2,4-dimethoxyphenyl, naphthyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl and 2-methanesulfonamidophenyl), a heterocyclic group (e.g., 4-pyridyl and 2-furyl), an alkoxy group (e.g., methoxy, ethoxy, isopropyloxy, 2-phenoxyethoxy and 2-methoxyethoxy), an aryloxy group (e.g., phenoxy, 2-methoxyphenoxy, 2,4-dimethoxyphenoxy, 2-chlorophenoxy and 2,5-di-tert-amylphenoxy), a heterocyclic oxy group (e.g. furyloxy), an amino group (e.g. N-methylamino and N,N-dibutylamino), an anilino group (e.g. 2-methoxyanilino and 2,4-dichloroanilino), a heterocyclic amino group (e.g. 4-pyridylamino), an amido group (e.g. acetamido and benzamido), a methane group (e.g. N-hexylurethane and N,N-dibutylurethane), a ureido group (e.g. N,N-dimethylureido and N-phenylureido), a sulfonamido group (e.g. butanesulfonamido and p-toluenesulfonamido), an alkylthio group (e.g. ethylthio and octylthio), an arylthio group (e.g. phenylthio and 4-dodecyloxyphenylthio), a sulfinyl group (e.g. benzenesulfinyl), a sulfonyl group (e.g. methanesulfonyl, octanesulfonyl and p-toluenesulfonyl), a sulfo group, a cyano group and a nitro group.

R₂ preferably represents a substituted or unsubstituted, linear or branched alkyl group or an aryl group.

In the general formulas (I) and (II), X represents a hydrogen atom or a substituent which can be released upon coupling with an oxidation product of an aromatic primary amine developing agent. Suitable examples of the substituent include an aryloxy group (e.g., p-methylphenoxy, p-carboxyphenoxy, 2,4-di-tert-amylphenoxy, 2-pivaloylaminophenoxy, 2-methanesulfonamidophenoxy and 2-methoxyphenoxy), a heterocyclic oxy group (e.g. furyloxy), an alkylthio group (e.g. dodecylthio, 2-hydroxyethylthio, carboxymethylthio and 1-ethoxycarbonyltridecylthio), an arylthio group (e.g. 2-pivaloylaminophenylthio and 2-butoxy-5-tert-octylphenylthio), a heterocyclic thio group, a halogen atom (e.g. fluorine, chlorine and bromine) and a nitrogen-containing heterocyclic group bonded to the nitrogen atom therein (e.g. triazolyl, pyrazolyl and imidazolyl).

In the general formulas (I) and (II), A represents an oxygen atom, a nitrogen atom or a sulfur atom, and n represents 0 or 1.

Among the couplers represented by the general formulas (I) and (II), those represented by the general formula (I) are preferred. in particular, couplers represented by the general formula (I) are preferred, and wherein R₁ is a branched alkyl group and n is 0, wherein R₁ is a branched alkyl group, A is an oxygen atom and n is 1, and wherein R₁ represents an aryl group, A represents an oxygen atom and n is 1.

A monomer containing the pyrazoloazole coupler component represented by the general formula (I) or (II) can form a copolymer together with a non-color-forming ethylenic monomer which does not couple with the oxidation product of an aromatic primary amine developing agent.

Examples of non-color forming ethylenic monomers which do not undergo coupling with the oxidation product of an aromatic primary amine developing agent include an acrylic acid such as acrylic acid, α-chloroacrylic acid and α-alkylacrylic acid (e.g. methacrylic acid), an ester or amide derived from an acrylic acid (e.g. acrylamide, n-butylacrylamide, tert-butylacrylamide, diacetoneacrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate or β-hydroxymethacrylate), methylenedibisacrylamide, a vinyl ester (e.g. vinyl acetate, vinyl propionate or vinyl laurate) acrylonitrile, methacrylonitrile, an aromatic vinyl compound (e.g. styrene and a derivative thereof, vinyltoluene, divinylbenzene, vinylacetophenone or sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chionide, a vinyl alkyl ether (e.g. vinyl ethyl ether), maleic acid, maleic anhydride, a maleic acid ester, N-vinyl-2-pyrrolidone, N-vinylpyridine or 2- or 4-vinylpyridine.

Two or more kinds of non-dye-forming ethylenically unsaturated monomers can be used together. For example, a combination of n-butyl acrylate and methyl acrylate, a styrene and methacrylic acid, methacrylic acid and acrylamide, or methyl acrylate and diacetone acrylamide can be used.

As is known in the art of polymeric color couplers, the non-dye-forming ethylenically unsaturated monomer which is copolymerized with a solid, water-insoluble monomer coupler can be selected such that the resulting copolymer has good physical properties and/or chemical properties (e.g., solubility), compatibility with a binder such as gelatin in a photographic colloidal composition, flexibility, and heat stability.

The polymer couplers used in the present invention may be water-soluble couplers or water-insoluble couplers, but polymer coupler latexes are particularly preferred as such polymer couplers.

In addition, the couplers represented by the general formula (I) or (II) can form a dimer through R₁, R₂ or X.

Specific examples of the pyrazoloazole couplers used in the present invention are listed below, but the present invention should not be construed as being limited thereto.

The couplers represented by the general formulas (I) and (II) can be prepared by a method known in the art, for example, 1H-pyrazolo[1,5-b]-1,2,4-triazole of the formula (I) is prepared by a method according to U.S. Patent 4,621,046 or 4,540,654, and 1H-pyrazolo[5,1-c]-1,2,4-triazole is prepared by a method according to U.S. Patent 3,725,067, Research Disclosure, Item No. 12443 or J. Chem. Soc., Perkin I, p. 2047 (1977).

Of the couplers represented by the general formulas (I) and (II) used in the present invention, those couplers represented by the general formula (I) are preferred for the purpose of the present invention because the decrease in light resistance is small when the amount of the organic solvent having a high boiling point is reduced. In addition, when R₁ is a branched alkyl group in the pyrazolotriazole coupler according to the present invention, the effect of the present invention increases as the size of the alkyl group increases. In particular, a substituted or unsubstituted isopropyl group and a substituted or unsubstituted tert-butyl group are particularly preferred as R₁.

When R1 is an aryl group, an aryl group having a large group at the ortho position is preferred, and an aryl group having substituents at the 2- and 6-positions is particularly preferred in view of the effect of the present invention. The amount of the pyrazolotriazole coupler used in the present invention is usually 0.01 mmol or more, preferably 0.1 mmol to 1.5 mmol per m2 of the light-sensitive material.

The couplers used in the present invention may be dissolved in an organic solvent having a high boiling point and then emulsified and dispersed, or may be emulsified and dispersed without using an organic solvent having a high boiling point. Couplers dispersed in the form of a latex may be mixed with a photographic emulsion as they are, or may be mixed with a binder such as gelatin and then mixed with a photographic emulsion.

Methods for dispersing the oleophilic couplers of this invention in high boiling point organic solvents that can be used in the present invention are described in detail below.

In order to incorporate oleophilic photographic organic compounds such as couplers into light-sensitive materials, various known dispersion methods can be used in the present invention.

For example, oleophilic photographic organic compounds can be dissolved in (i) an organic solvent having a high boiling point of above about 175°C at normal pressure, e.g., a phthalic acid ester, a phosphoric acid ester, a benzoic acid ester, a fatty acid ester, an amide, a phenol, an alcohol, a carboxylic acid, an N,N-dialkylaniline, a hydrocarbon, an oligomer and a polymer, and/or (ii) an organic solvent having a low boiling point of about 30°C to about 160°C at normal pressure, e.g., an ester (e.g., ethyl acetate, butyl acetate, ethyl propionate, p-ethoxyethyl acetate and methyl cellosolve acetate), a alcohol (e.g. secondary butyl alcohol), a ketone (e.g. methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone), an amide (e.g. dimethylformamide and N-methylpyrrolidone) and an ether (e.g. tetrahydrofuran and dioxane) and they can then be emulsified and dispersed in a hydrophilic colloid such as gelatin.

The methods and effects of latex dispersion processes and specific examples of latexes for loading are described, for example, in U.S. Patent 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230, and European Patent 294,104A.

The high boiling point organic solvent or latex not only acts as a dispersion medium, but can also have various additional functions, such as improving the physical properties of the gelatin layer, accelerating color formation, controlling the color tone of the formed color image, and improving the durability of the color image.

The high boiling point organic solvent can be used in any liquid, waxy or solid form.

The high boiling point organic solvent used in the present invention is preferably represented by the following general formula (S-1), (S-2), (S-3), (S-4), (S-5), (S-6), (S-7), (S-8) or (S-9):

(Ar-COO)bR₇ (S-3)

(R�8-COO)cR�9 (S-4)

R₁₀(COO-R₁₁)d (S-5)

wherein R₁, R₂ and R₃ of the formula (S-1) each represent an alkyl group, a cycloalkyl group or an aryl group; R₄ and R₅ each represent an alkyl group, a cycloalkyl group or an aryl group; R₆ represents a halogen atom (e.g. F, Cl, Br and I), an alkyl group, an alkoxy group, an aryloxy group or an alkoxycarbonyl group; a represents an integer of 0 to 31; when a represents 2 or 3, two or three of R G may be the same or different; Ar represents an aryl group; b represents an integer of 1 to 6; R₇ represents a b-valent hydrocarbon group or a hydrocarbon group linked via an ether group; R₈ represents an alkyl group or a cycloalkyl group; c represents an integer of 1 to 6; R₄ represents a c-valent hydrocarbon group or a hydrocarbon group linked through an ether bond; d represents an integer of 2 to 6; R₁₀ represents a d-valent hydrocarbon group provided that an aromatic group is excluded; R₁₁ represents an alkyl group, a cycloalkyl group or an aryl group; R₁₂, R₁₃ or R₁₄ each represents an alkyl group, a cycloalkyl group or an aryl group, or R₁₂ and R₁₃ or R₁₃ and R₁₄ may combine with each other to form a ring; R₁₅ represents an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryl group or a cyano group; R₁₆ represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group or an aryloxy group; e represents an integer of 0 to 3, when e represents 2 or 3, two or three of R₁₆ may be the same or different; R₁₇ and R₁₇ each represents an alkyl group, a cycloalkyl group or an aryl group; R₁₇ represents a halogen atom, a cycloalkyl group, an alkyl group, an aryl group, a alkoxy group or an aryloxy group; f represents an integer of 0 to 4, when f represents 2, 3 or 4, 2, 3 or 4 of R₁₉ may be the same or different; A₁, A₂, ... and An each represent a polymer unit formed from a non-color-forming ethylenic monomer, which are different from each other; a₁, a₂, ... and an each represent a weight ratio of the polymer unit; and n represents an integer of 1 to 30.

Specific examples of the organic solvent having a high boiling point used in the present invention are listed below, but the present invention should not be construed as being limited thereto. Dielectric constant: 7.33 Dielectric constant: 4.80 Dielectric constant: 6.45 Dielectric constant: 6.45 Dielectric constant: 13.45 Dielectric constant: 2.76

S-24 Polymethyl methacrylate (average molecular weight 20,000)

S-25 Poly(N-t-butylacrylamido) (average molecular weight 60,000)

S-26 Chlorinated Paraffin (average composition: C₁₂H₁₈Cl₈)

Other examples of high boiling point organic solvents that can be used in the present invention and/or synthesis methods therefor are described, for example, in US Patents 2,322,027, 2,533,514, 2,772,163, 2,835,679, 3,676,137, 3,912,515, 3,936,303, 4,080,209, 4,127,413, 4,193,802, 4,239,851, 4,278,757, 4,363,873, 4,483,918 and 4,745,049, European Patent 276,319A, JP-A-48-47335, JP-A-51-149028, JP-A-61-84641, JP-A-62-118345, JP-A-62-247364, JP-A-63-1 67357, JP-A-64-68745 and JP-A-1-101543.

In the present invention, the effect of the present invention becomes particularly significant when the weight ratio of the organic solvent having a high boiling point to the coupler is not more than 1. On the other hand, when couplers other than those of the present invention are used, the aggregation of the dyes formed during processing can be significantly reduced by increasing the amount of the organic solvent having a high boiling point. The weight ratio of the organic solvent having a high boiling point to the coupler is preferably not more than 0.7, more preferably not more than 0.5, and even more preferably not more than 0.2. When the weight ratio becomes small, the difference between the couplers according to the present invention and couplers outside the scope of the present invention in terms of color tone becomes large due to aggregation of the dyes.

In addition, of the organic solvents having a high boiling point used in the present invention, those having a dielectric constant of 5 or more are preferred because they have a high coupling activity when their amount is reduced. The dielectric constant can be measured by the bridge method using a TRS-1 OT instrument (manufactured by Ando Denki Co.) under conditions of 25°C and 10 MHz.

The color photographic light-sensitive material according to the present invention may comprise at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer on a support. The number of silver halide emulsion layers and light-insensitive layers and their order is not particularly limited. A typical example is a silver halide photographic material comprising a support having thereon at least one light-sensitive layer group consisting of a plurality of silver halide emulsion layers having substantially the same spectral sensitivity but different sensitivities. The light-sensitive layer group is a unit light-sensitive layer having a spectral sensitivity to either blue, green or red light. In a multilayer silver halide color photographic material, unit light-sensitive layers are generally provided on the support in the order of a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer from the support side. The order of these layers may vary depending on the purpose. Furthermore, a layer structure in which a light-sensitive layer having a different spectral sensitivity is interposed between two layers having the same spectral sensitivity may be used.

Between the above-described light-sensitive silver halide layers or as an uppermost layer or lowermost layer, various light-insensitive layers, such as an intermediate layer, can be provided.

In such an intermediate layer, couplers and DIR compounds as described in JP-A-61-43748, JP-A-59-113438, JP-A-59-113440, JP-A-61-20037 and JP-A-61-20038 may be incorporated. In addition, the intermediate layer may contain conventionally used color mixing preventing agents.

The plurality of silver halide emulsion layers constituting the unit photosensitive layer preferably has a two-layer structure consisting of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer, for example, as described in West German Patent No. 1,121,470 and British Patent No. 923,045. It is preferred that these layers are arranged in an order of increasing sensitivity from the support side. In addition, a light-insensitive layer may be provided between silver halide emulsion layers. In addition, a low-sensitivity emulsion layer may be provided further away from the support and a high-sensitivity emulsion layer may be provided in place. which is closest to the support, as described in JP-A-d57-112751, JP-A-62-200350, JP-A-62-206541 and JP-A-62-206543.

Specific examples of the layer construction include an order of a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / a high-sensitivity red-sensitive layer (RH) / a low-sensitivity red-sensitive layer (RL) from the side farthest from the support and an order of BH/BL/GL/GH/RH/RL or an order of BH/BL/GH/GL/RL/RH.

Further, an order of a blue-sensitive layer /GH/RH/GL/RL from the side farthest from the support may be used as described in JP-B-55-34932 ("JP-B" as used herein means an "examined Japanese patent publication"). In addition, an order of a blue-sensitive layer IGL/RL/GH/RH from the side farthest from the support may be used as described in JP-A-56-25738 and JP-A-62-63936.

In addition, a layer structure of three layers having different sensitivities may be used, consisting of an upper silver halide emulsion layer having the highest sensitivity, an intermediate silver halide emulsion layer having a sensitivity lower than that of the upper layer, and a lower silver halide emulsion layer having a sensitivity lower than that of the intermediate layer in the order of increasing sensitivity from the support side, as described in JP-B49-15495. In cases where the unit photosensitive layer of the same spectral sensitivity consists of three layers having different sensitivities, an order of a medium-sensitive emulsion layer / a high-sensitive emulsion layer / a low-sensitive emulsion layer as viewed from the side farthest from the support may be used, as described in JP-A-59-202464.

In addition, the sequence of a high-sensitivity emulsion layer / a less sensitive emulsion layer / an emulsion layer with medium sensitivity or a sequence of a less sensitive emulsion layer / an emulsion layer with medium sensitivity / a high-sensitivity emulsion layer.

When the unit photosensitive layers consist of four layers or more, the order can be varied as described above.

In order to improve color reproducibility, it is preferred that an inter-image effect donor layer (CL) having a spectral sensitivity distribution different from that of the main photosensitive layer, such as BL, GL or RL, is provided adjacent to or near the main layer, as described, for example, in U.S. Patents 4,663,271, 4,705,744 and 4,707,436, JP-A-62-160448 and JP-A-63-89580.

As described above, various layer constructions and dispositions can be appropriately selected depending on the purpose of the photographic light-sensitive material.

In cases where the color photographic light-sensitive material of the present invention is a color negative film or a color reversal film, the silver halide preferably used in the photographic emulsion layers thereof is silver iodobromide, silver iodochloride or silver iodochlorobromide, each containing about 30 mol% or less of silver iodide. Silver iodobromide or silver iodochlorobromide, each containing about 2 mol% to about 25 mol% of silver iodide, are particularly preferred.

In cases where the color photographic light-sensitive material of the present invention is a color printing paper, the silver halide preferably used in the photographic emulsion layer is silver chlorobromide or silver chloride, each of which contains substantially no silver iodide. The terminology "containing substantially no silver iodide" as used herein means that the silver iodide content of the emulsion is not more than 1 mol%, preferably not more than 0.2 mol%.

With regard to the halogen composition of the silver chlorobromide emulsion, any silver bromide/silver chloride ratio can be used. The ratio can be varied in a wide range depending on the purpose, but emulsions having a silver chloride content ratio of 2 mol% or more are particularly preferably used.

In the photographic light-sensitive materials suitable for rapid processing, a so-called high silver chloride emulsion having a high silver chloride content ratio is preferably used. The silver chloride content ratio in such high silver chloride emulsions is preferably 90 mol% or more, and particularly preferably 95 mol% or more.

In addition, for the purpose of reducing the amount of the replenisher for the developing solution, a nearly pure silver chloride emulsion is used, such as one in which the silver chloride content is 98 mol% to 99.9 mol%.

The silver halide grains in the silver halide emulsion may have a regular crystal structure, e.g. a cubic, octahedral or tetradecahedral structure, an irregular crystal structure, e.g. a spherical or tabular structure, a crystal defect, e.g. a twin intergrowth, or a composite structure thereof.

The particle size of the silver halide can be varied and the emulsion can contain fine grains having a projected area diameter of about 0.2 µm or less to large grains having a projected area diameter of about 10 µm. In addition, a polydisperse emulsion or a monodisperse emulsion can be used.

The silver halide photographic emulsion which can be used in the present invention can be prepared using known methods, for example, those described in Research Disclosure, No. 17643 (December, 1978), pp. 22 to 23, "I. Emulsion Preparation and Types" and ibid., No. 18716 (November, 1979), p. 648, P. Glafkides, Chimie et Physique Photographique, Paul Montel (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press (1966), and VL Zelikman et al., Making and Coating Photographic Emulsion, The Focal Press (1964).

Monodisperse emulsions, such as those described in US Patents 3,574,628 and 3,655,394 and in British Patent 1,413,748, are preferably used in the present invention.

In addition, tabular silver halide grains having a ratio of about 5 or more can be used in the present invention. The tabular grains can be easily prepared by a method such as described in Gutoff, Photographic Science and Engineering, Vol. 14, pp. 248 to 257 (1970), U.S. Patents 4,434,226, 4,414,310, 4,433,048 and 4,439,520 and British Patent 2,112,157.

The crystal structure of the silver halide grains may be uniform, or may consist of different halide compositions between the inner part and the outer part, or may have a layered structure.

In addition, silver halide emulsions in which silver halide grains having different compositions are bonded together via epitaxial bonds or silver halide emulsions in which silver halide grains are bonded together with compounds other than silver halide, such as silver thiocyanate or lead oxide, can also be used.

In addition, a mixture of grains with different crystal structures can be used.

The silver halide emulsions used in the present invention are usually subjected to physical ripening, chemical ripening and spectral sensitization. Various types of additives can be used in these steps and are described in Research Disclosure, No. 17643 (December 1978) and ibid No. 18716 (November 1979), and relevant points therefrom are summarized in the table shown below.

In addition, known photographic additives which can be used in the present invention are described in the above-mentioned publications, and relevant points thereof are summarized in the table below.

In the color photographic light-sensitive material according to the present invention, various color fading-preventing agents can be used. Specifically, representative examples of organic color fading-preventing agents for cyan, magenta and/or yellow images are hindered phenols (e.g., hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols or bisphenols), bile acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines or ether or ester derivatives thereof derived from any of these compounds by silylation or alkylation of their phenolic hydroxy group. In addition, metal complexes representatively represented by (bis-salicylaldoxymate) nickel complexes and (bis-N,N,-dialkyldithiocarbamate) nickel complexes can be used.

Specific examples of the organic color fading preventing agents are described in the following patents or patent applications:

Hydroquinones: US Patents 2,360,290, 2,418,613, 2,700,453, 2,701,197, 2,728,659, 2,732,300, 2,735,765, 3,982,944 and 4,430,425, British Patent 1,363,921, US Patents 2,710,801 and 2,816,028; 6-hydroxychromans, 5-hydroxycoumarans and spirochromans: US Patents 3,432,300, 3,573,050, 3,574,627, 3,698,909 and 3,764,337, JP-A-52-152225; spiroindanes: US Patent 4,360,589; p-alkoxyphenols: US Patent 2,735,765, British Patent 2,066,975, JP-A-59-10539, JP-B-57-19765; sterically hindered phenols: US Patent 3,700,455, JP-A-52-72224, US Patent 4,228,235, JP-B-52-6623; bile acid derivatives, methylenedioxybenzenes and aminophenols: US Patents 3,457,079 and 4,332,886, JP-B-56-2 1144; sterically hindered amines: US patents 3,336,135 and 4,268,593, British patents 1,326,889, 1,354,313 and 1,410,846, JP-B-51-1420, JP-A-58-114036, JP-A-59-53846, JP-A-59-78344.

Furthermore, specific examples of the metal complexes are described in US Patents 4,050,938 and 4,241,155 and British Patent 2,027,731A.

The color fading preventing agents are emulsified with the corresponding color coupler in an amount of 5 to 100% by weight of the color coupler and incorporated into the light-sensitive layer to achieve their effects.

Furthermore, in order to prevent deterioration of photographic properties due to formaldehyde gas, it is preferred to add a compound capable of reacting with formaldehyde to fix it to the photographic light-sensitive material, as described in U.S. Patents 4,411,987 and 4,435,503.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents cited in Research Disclosure, No. 17643, "VII-C" to "VII-G".

As the yellow couplers used in the present invention, for example, those described in the following patents are preferred: U.S. Patents 3,933,501, 4,022,620, 4,326,024, 4,401,752 and 4,248,961, JP-B-58-10739, British Patents 1,425,020 and 1,476,760, U.S. Patents 3,973,968, 4,314,023 and 4,511,649 and European Patent 249,473A.

As magenta couplers used in the present inventions, 5-pyrazolone-type and 5-pyrazoloazole-type compounds are preferred. Magenta couplers are described, for example, in U.S. Patents 4,310,619 and 4,351,897, European Patent 73,636, U.S. Patents 3,061,432 and 3,725,067, Research Disclosure, No. 24220 (June 1984), JP-A-60-33552, Research Disclosure, No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, JP-A-60-185951, and U.S. Patents 4,500,630, 4,540,654 and 4,556,630 and WO(PCT) 88/04795 are particularly preferred.

Cyan couplers used in the present invention are exemplified by phenol-type and naphthol-type couplers. Cyan couplers are described, for example, in US patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011 and 4,327,173, West German patent application (OLS) No. 3,329,729, European patents 121,365A and 249,453A, US patents 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4,690,889, 4,254,212 and 4,296,199, and JP-A-61-42658 and particularly preferred.

As colored couplers for correcting undesirable absorptions of dyes formed during processing, those described in Research Disclosure, No. 17643, "VII-G," U.S. Patent 4,163,670, JP-B-57-39413, U.S. Patents 4,004,929 and 4,138,258, and British Patent 1,146,368 are particularly preferred. It is also preferred to use couplers for correcting undesirable absorptions of dyes formed by a fluorescent dye which is released after coupling, as described, for example, in U.S. Patent No. 4,774,181, or couplers having a dye precursor group capable of forming a dye after reaction with a developing agent, such as a release group, as described, for example, in U.S. Patent No. 4,777,120.

As couplers capable of forming suitable diffusible dyes, for example, those described in US Patent 4,366,237, British Patent 2,125,570, European Patent 96,570 and West German Patent Application (OLS) No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are described, for example, in US Patents 3,451,820, 4,080,211, 4,367,282, 4,409,320 and 4,576,910 and British Patent 2,102,173.

Couplers capable of releasing a photographically useful component during the course of coupling can also be preferably used in the present invention. As DIR couplers capable of releasing a development inhibitor, for example, those cited in Research Disclosure, No. 17643, "VII-F" described above, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, JP-A-63-37350 and U.S. Patents 4,248,962 and 4,782,012 are preferred.

As couplers which imagewise release a nucleating agent or a development accelerator at the time of acceleration, those described, for example, in British Patents 2,097,140 and 2,131,188, JP-A-59-157638 and JP-A-59-170840 are preferred.

In addition, competing couplers such as those described in U.S. Patent 4,130,427; polyequivalent couplers such as those described in U.S. Patents 4,283,472, 4,338,393 and 4,310,618; DIR redox compounds or DIR coupler-releasing couplers or DIR couplers or DIR redox compounds releasing redox compounds such as those described, e.g. as described in JP-A-60-185950 and JP-A-62-24252; couplers capable of releasing a dye which changes to its colored form upon release, such as those described in European Patent 173,302A; Bleach accelerator-releasing couplers such as those described in, for example, Research Disclosure, No. 11449, ibid., No. 24241 and JP-A-61-201247; ligand-releasing couplers such as those described in, for example, US Patent No. 4,553,477; couplers capable of releasing a leuco dye such as those described in JP-A-63-75747 and couplers capable of releasing a fluorescent dye such as those described in, for example, U.S. Patent No. 4,774,181 are employed in the photographic light-sensitive material of the present invention.

The couplers used in the present invention can be introduced into the photographic light-sensitive material according to various dispersion methods as described above.

It is preferable to add various kinds of antiseptic agents or antifouling agents to the color photographic light-sensitive material of the present invention, for example, 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol or 2-(4-thiazolyl)benzimidazole as described in, for example, JP-A-63-257747, JP-A-62-272248 and JP-A-1-80941.

The present invention can be applied to various color photographic light-sensitive materials, and typical examples thereof include color negative films for general use or cinema, color reversal films for slides or television, color papers, color positive films and color reversal papers.

Suitable supports that can be used in the present invention are described, for example, in Research Disclosure, No. 17643, p. 28 and ibid No. 18716, p. 647, right column to page 648, left column, as mentioned above.

The term "reflective support" which can be used in the present invention means a support having an enhanced reflection property for the purpose of making the color images formed in the silver halide emulsion layer clear. Examples of reflective supports include supports having thereon a hydrophobic resin having a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate or calcium sulfate dispersed therein and supports consisting of a hydrophobic resin having a light-reflecting substance dispersed therein. Specifically, they include barium oxide-coated paper; polyethylene-coated paper; polypropylene-type synthetic paper; transparent supports such as glass plates; polyester films such as polyethylene terephthalate film, cellulose triacetate film. or cellulose nitrate film, polyamide film, polycarbonate film, polystyrene film or vinyl chloride resin, with a reflective layer or with an incorporated reflective substance.

Other examples of the reflective support that can be used are supports having a metal surface with a specular reflectivity or a secondary diffusion reflectivity. The metal surface preferably has a spectral reflectance of 0.5 or more in the visible wavelength region. The metal surfaces are preferably prepared by roughening or by imparting a diffusion reflectivity using metal powders. Suitable examples of metals include aluminum, tin, silver, magnesium or their alloys. The metal surfaces include metal plates, metal foils or thin metal layers obtained by rolling, vacuum evaporation or coating. Among these, a metal surface obtained by vacuum evaporation of the metal on a substrate is preferably used.

On the metal surface, a waterproof resin layer is preferably provided, especially a thermoplastic resin layer. On the side of the support opposite to the metal surface according to the present invention, an antistatic layer is preferably provided. Details of these supports are described in, for example, JP-A-61-210346, JP-A-63-24247, JP-A-63-24251 and JP-A-63-24255.

It is preferred that the total layer thickness of all the hydrophilic colloid layers provided on the emulsion layer side of the photographic light-sensitive material according to the present invention be not more than 28 µm, more preferably not more than 23 µm, and even more preferably not more than 20 µm. In addition, the layer swelling rate of T½ should preferably be not more than 30 s, and more preferably not more than 20 s. The layer thickness means the thickness of the layer measured after preservation under conditions of 25°C and a relative humidity of 55% for 2 days. The layer swelling rate of T½ is determined according to methods known in the art. For example, the degree of swelling can be measured by a swelling measuring device of the type described in A. Green, Photogr. Sci. Eng., Vol. 19, No. 2, pp.124 to 129, and T½ is defined as the in A. Green, Photogr. Sci. Eng., Vol. 19, No. 2, pp. 124 to 129, and T½ is defined as the time necessary to reach a saturated layer thickness which is 90% of the maximum swelling layer thickness obtained when treated in a colour developing solution at 30ºC for 3 min 15 s.

The film swelling rate of T½ can be controlled by adding a hardener to the gelatin binder or by changing the aging condition after coating.

The swelling rate is preferably 150 to 400%. The swelling rate can be determined by a formula of (maximum swelling layer thickness - layer thickness)/layer thickness, where the maximum swelling layer thickness has the same meaning as defined above.

The color photographic light-sensitive material according to the present invention may be subjected to development processing in a conventional manner as described, for example, in Research Disclosure No. 17643, pp. 28 to 29 and ibid., No. 18716, p. 651, left column to right column, as mentioned above.

The color developing solution which can be used in the development processing of the color photographic light-sensitive material according to the present invention is an alkaline aqueous solution which preferably contains an aromatic primary amine type color developing agent as a main component. As the color developing agent, a p-phenylenediamine type compound is preferably used, while an aminophenol type compound is also useful. Suitable examples of the p-phenylenediamine type compound include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-p-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-p-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, or the sulfates, hydrochlorides or p-toluenesulfonates thereof. Among these compounds, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred.

Two or more types of color developing agents can be used in combination depending on the purpose.

The color developing solution may typically contain pH buffering agents such as carbonates, borates or phosphates of alkali metals; and development inhibitors or anti-fogging agents such as chlorides, bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. In addition, if necessary, the color developing solution may contain various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine or catecholsulfonic acids; organic solvents such as ethylene glycol or diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts or amines; dye-forming couplers; competing couplers; auxiliary developing agents such as ethyl acetate, ... B. 1-phenyl-3-pyrazolidone; agents that impart viscosity; and various chelating agents, represented by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids or phosphonocarboxylic acids. Representative examples of the chelating agents include ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, ethylenediaminedi(o-hydroxyphenylacetic acid) and their salts.

Processing solutions other than the color developing solutions and processing steps for the color reversal photographic material are described in detail below.

Of the processing steps for color reversal photographic materials, the steps from black and white development to color development are as follows:

1) Black and white development - washing with water - colour reversal development

2) Black and white development - washing with water - light reversal - colour development

3) Black and white development - washing with water - colour development

The steps in 1) to 3) regarding washing with water can be replaced by a rinsing step as described in US Patent 4,804,616 to simplify processing and reduce waste.

The steps after color development are described below.

4) Color development - conditioning - bleaching - fixing - washing with water - stabilization

5) Color development - washing with water - bleaching - fixing - washing with water - stabilization

6) Colour development - conditioning - bleaching - washing with water - Fixation - washing with water - stabilisation

7) Colour development - washing with water - bleaching - washing with water - fixing - washing with water - stabilisation

8) Colour development - bleaching - fixing - washing with water - stabilisation

9) Color development - bleaching - bleach-fixation - fixation - washing with water - stabilization

10) Colour development - bleaching - bleach-fixing - fixing - washing with water - stabilisation

11) Colour development - bleaching - washing with water - fixing - washing with water - stabilisation

12) Colour development - conditioning - bleaching - fixing - washing with water - stabilisation

13) Colour development - washing with water - bleaching - fixing - washing with water - stabilisation

14) Colour development - bleaching - fixing - washing with water - stabilisation

15) Color development - Fixation - Bleach-fixation - Washing with water - Stabilization

The water washing steps immediately preceding the stabilization steps in 4) to 15) may be omitted, and the final stabilization steps may also be omitted.

The color reversal steps consist of one of the steps from 1) to 3) and one of the steps from 4) to 15) as described above.

Processing solutions for color reversal processing steps are described below.

In the black-and-white developing solution used in the present invention, known black-and-white developing agents can be used, including, for example, dihydroxybenzenes (e.g., hydroquinone), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone), aminophenols (e.g., N-methyl-p-aminophenol), 1-phenyl-3-pyrazolines, ascorbic acid, heterocyclic compounds in which a 1,2,3,4-tetrahydroquinoline ring is fused to an indole ring as described in U.S. Patent No. 4,067,872, and the like, which can be used alone or in combination.

The black-and-white developing solution used in the present invention may, if desired, contain preservatives (e.g., sulfites or bisulfites), buffers (e.g., carbonates, boric acid, borates, or alkanolamines), alkaline agents (e.g., hydroxides or carbonates), dissolving agents (e.g., polyethylene glycols or their esters), pH control agents (e.g., organic acids such as acetic acid), sensitizing agents (e.g., quaternary ammonium salts), development accelerators, surfactants, defoaming agents, hardeners, or agents that impart viscosity.

In the black-and-white developing solution used in the present invention, a compound that functions as a silver halide solvent should be incorporated. Usually, the sulfites added as preservatives described above also function as solvents. Specific examples of the sulfites and other silver halide solvents that can be used include KSCN, NaSCN, K₂SO₃, Na₂SO₃, K₂S₂O₅, Na₂S₂O₅, K₂S₂O₃ and Na₂S₂O₃.

Although an appropriate amount of the silver halide solvent should be used, since too little amount causes a delay in development and too much amount causes fogging of the silver halide emulsion, the appropriate amount can be easily determined by one skilled in the art.

For example, it is preferred to use SCN⁻ in a range of 0.005 to 0.02 mol, particularly 0.01 to 0.015 mol, and SO₃²⁻ in a range of 0.05 to 1 mol, particularly 0.1 to 0.5 mol, per liter of the developing solution.

In order to accelerate the development, a development accelerator may be used. In particular, organic thioether compounds as described in JP-A-57-63580 may be used.

When these compounds are added to the black-and-white developing solution used in the present invention, their preferred amount is in the range of 5x10-6 mol to 5x10-1 mol, more preferably 1x10-4 mol to 2x10-1 mol per liter of the developing solution.

In the black-and-white developing solution used in the present invention, various chelating agents can be used for the purpose of water softening. Preferably used chelating agents are aminopolycarboxylic acids, organic phosphonic acids and phosphonocarboxylic acids as described with respect to the color developing solution.

Furthermore, in the black-and-white developing solution used in the present invention, various compounds can be used as described with respect to the color developing solution, and they are added as preservatives in addition to the above-described sulfites.

Preferred antifoggants are alkali metal halides such as potassium bromide, sodium bromide and potassium iodide and organic antifoggants. Suitable examples of organic antifoggants include nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylmethylbenzimidazole and hydroxyazaindolidine; mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole and 2-mercaptobenzothiazole; and mercapto-substituted aromatic compounds (such as thiosalicylic acid). The antifoggant may be separated from the color reversal photographic materials during processing and accumulated in the developing solution.

The pH of the developing solution prepared as described above is selected to impart the desired density and contrast, but it is preferred that it be in the range of about 8.5 to about 11.5.

To perform sensitization processing with the black and white developing solution, the processing time is extended to at most about 3 times the standard processing time. In this case, if the processing temperature is raised, longer processing times for sensitization processing can be shortened.

The reversal bath used after black-and-white development in the present development may contain known fogging agents including tin ion complex salts such as tin ion-organophosphoric acid complex salt (as described in U.S. Patent 3,617,282), tin ion-organic phosphonocarboxylic acid complex salt (as described in JP-B-56-3261 6), tin ion-aminopolycarboxylic acid complex salt (as described in British Patent 1,209,050), and boron compounds such as borohydride compounds (as described in U.S. Patent 2,984,567) and heterocyclic amine borane compounds (as described in British Patent 1,011,000).

The veil bath (reversal bath) can have a pH that varies within a wide range, from acidic to alkaline, i.e. in the range from 2 to 12, preferably 2.5 to 10, particularly preferably 3 to 9.

The light reversal treatment can be used instead of a reversal bath. In addition, the reversal step can be omitted by adding a fogging agent to the color developing bath.

The pH of the color developing solution or the black and white developing solution is usually in the range of 9 to 12. In addition, the amount of replenishment for the developing solution may vary depending on the color photographic light-sensitive materials to be processed, but is usually not more than 3 liters per m² of the photographic light-sensitive material. The amount of replenishment can be reduced to not more than 500 ml by adjusting the bromide diion concentration. in the replenisher. When the amount of replenishment is reduced, it is preferable to prevent evaporation and air oxidation of the processing solution by reducing the area of the processing tank in contact with air.

The contact area of the photographic processing solution with the air in the processing tank can be represented by the opening rate as defined below.

Opening rate = contact area of the processing solution with the air (cm²)/volume of the processing solution (cm³)

The opening rate described above is preferably not more than 0.1, more preferably 0.001 to 0.05. Means for reducing the opening rate include a method using a movable cover as described in JP-A-82033, a slip development processing method as described in JP-A-63-216050, and a method in which a cover such as a floating cover is provided on the surface of the photographic processing solution in the processing tank. It is preferable to apply the reduction in the opening rate not only to the steps of color development and black-and-white development, but also to all of the following steps, e.g., bleaching, bleach-fixing, water washing, and stabilization.

In addition, the amount of replenishment can be reduced by using agents that reduce accumulation of bromide ions in the developing solution.

The processing time for color development is usually chosen in a range of 2 to 5 minutes. However, it is possible to further reduce the processing time by performing color development at high temperature and high pH, using a high concentration of color developing agent.

After color development, the photographic emulsion layers are usually subjected to bleaching. Bleaching can be carried out simultaneously with Fixation may be carried out (bleach-fixing processing), or it may be carried out independently of the fixation processing. In addition, for the purpose of rapid processing, a processing method in which, after the bleaching processing, bleach-fixing processing is carried out may be adopted. In addition, depending on the purpose of the process, a continuous bleach-fixing bath having two tanks may be suitably used to carry out fixation before bleach-fixing, or to carry out the bleaching step after bleach-fixing.

Examples of bleaching agents that can be used in bleaching processing or bleach-fixing include compounds of multivalent metals such as iron(III); peracids; quinones; and nitro compounds. Representative examples of bleaching agents include organic complex salts of iron(III), e.g. complex salts of aminopolycarboxylic acids (e.g. ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid or glycol ether diaminetetraacetic acid) or complex salts of organic acids (such as citric acid, tartaric acid or malic acid). Of these compounds, iron(III) complex salts of aminopolycarboxylic acids, represented by iron(III) complex salts of ethylenediaminetetraacetic acid and iron(III) complex salts of 1,3-diaminopropanetetraacetic acid, are particularly preferred in view of rapid processing and low environmental pollution. In addition, iron(III) complex salts of aminopolycarboxylic acids are particularly useful in both bleaching solutions and bleach-fixing solutions.

The pH of the bleaching solution or the bleach-fixing solution containing a ferric complex salt of aminopolycarboxylic acid is usually in the range of 4 to 8. For the purpose of rapid processing, it is possible to process at a lower pH than that described above.

In the bleaching solution, the bleach-fixing solution or a pre-bath therefor, a bleach accelerating agent may be used if desired. Specific examples of suitable bleach accelerating agents include compounds having a mercapto group or a disulfide bond as described in, for example, U.S. Patent 3,893,858, West German Patents 1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-3741 8, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631, JP-A-53-104232, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426 and Research Disclosure, No. 17129 (July 1978); thiazoline derivatives as described in JP-A-50-140129; thiourea derivatives as described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735 and US Patent 3,706,561; Iodides such as described in West German Patent 1,127,715 and JP-A-58-16235; polyoxyethylene compounds such as described in West German Patents 966,410 and 2,748,430; polyamine compounds such as described in JP-B-45-8836; compounds such as described in JP-A-49-42434, JP-A-49-59644, JP-A-53-94927, JP-A-54-35727, JP-A-55-26506 and JP-A-58-163940; and bromide ions. Of these compounds, the compounds having a mercapto group or a disulfide bond are preferred in view of their strong bleaching-accelerating effects. In particular, the compounds as described in U.S. Patent 3,893,858, West German Patent 1,290,812 and JP-A-53-95630 are preferred. Furthermore, the compounds as described in U.S. Patent 4,552,834 are also preferred. These bleach accelerating agents may be incorporated into the color photographic light-sensitive material. These bleach accelerating agents are particularly effectively used when color photographic light-sensitive materials are subjected to bleach-fixing for photography.

An organic acid is preferably incorporated into the bleaching solution or the bleach-fixing solution to prevent bleach stains. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5 and include in particular, for example, acetic acid and propionic acid.

Fixing agents that can be used in the fixing solution or bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas or a large amount of iodide. Of these compounds, thiosulfates are generally used. In particular, ammonium thiosulfate is particularly widely used. Combinations of thiosulfates with thiocyanates, thioether compounds or thioureas are also preferably used. It is preferable to use sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds as described in European Patent 294769A as preservatives in the fixing solution or bleach-fixing solution. In addition, it is preferable to use various Add aminopolycarboxylic acids and organic phosphonic acids to the fixing or bleach-fixing solution for the purpose of stabilizing the solution.

Shorter total times for the desilvering step are preferably provided so that insufficient desilvering does not occur. Therefore, the processing time for the desilvering step is preferably between 1 minute and 3 minutes, more preferably between 1 minute and 2 minutes. The processing temperature is between 25 and 50°C, preferably 35 to 45°C. In the preferred processing temperature range, the desilvering rate increases and the occurrence of stains after processing is effectively prevented.

In the desilvering step, it is preferable to stir as vigorously as possible.

Specific examples of methods for improving stirring include a method in which a jet of the processing solution is directed against the emulsion surface of the photosensitive material as described in JP-A-62-183460 and JP-A-62-183461, a method for enhancing the stirring effect using rotating devices as described in JP-A-62-183461, a method for enhancing the stirring effect by transferring the photosensitive material while bringing the emulsion surface into contact with a scraper provided in the solution to form a turbulent flow on the emulsion surface, and a method for enhancing the circulation flow of the entire processing solution. These devices for improving stirring are effective in the bleaching solution, the bleach-fixing solution and the fixing solution. It is believed that the intensification of stirring assists the supply of the bleaching agent and the fixing agent to the emulsion layer and thereby increases the desilvering rate.

In addition, the stirring intensifying devices described above are more effective when a bleach accelerator is used. They significantly enhance its accelerating effect and eliminate the fixation hindrance resulting from the use of bleach accelerators. Automatic developing machines for processing in this context for the present invention are preferably equipped with a transfer device for the light-sensitive material as described in JP-A-60-191257, JP-A-60-191258 and JP-A-60-191259. As described in JP-A-60-191257, such a transfer device can significantly reduce the amount of the processing solution transferred from the precursor bath to the following bath, and the degradation of the processing solutions is effectively prevented. Such an effect is particularly useful for reducing the processing time in each step and reducing the replenishment amount of the processing solution in each step.

After the desilvering step, the silver halide photographic material according to the present invention is generally subjected to a water washing step and/or a stabilizing step.

The amount of water required for the washing step can vary widely depending on the properties of the photographic light-sensitive materials (due to the elements used therein, e.g., couplers), their use, the temperature of the washing water, the number of water washing tanks (stages), the replenishment system such as a countercurrent or cocurrent system, and other various conditions. The relationship between the number of water washing tanks and the amount of washing water in a multi-stage countercurrent system can be determined based on the method described in Journal of the Society of Motion Picture and Television Engineers, Vol. 64, pp. 248 to 253 (May 1955).

According to the multi-stage countercurrent system described in the above publication, the amount of water for the washing step can be significantly reduced. However, the increase in the residence time of the water in the tank leads to proliferation of bacteria and problems such as adhesion of suspended matter to the photographic materials. In the method for processing the silver halide color photographic material according to the present invention, a method for reducing the amounts of calcium ions and magnesium ions as described in JP-A-62-288838 can be used particularly effectively to solve these disadvantages. In addition, sterilizers, e.g. isothiazolone compounds such as described in JP-A-57-8542, thiabendazoles, chlorine-type sterilizers such as sodium chloroisocyanurate, benzotriazoles, sterilizers as described in Hiroshi Horiguchi, Bokin-Bobai No Kagaku (Sankyo Shuppan, 1986), Biseibutsu No Mekkin-, Sakkin-, Bobai-Gijutsu, edited by Eiseigijutsu Kai (Kogyogijutsu Kai 1982) and Bokin- Bobaizai Jiten, edited by Nippon Bokin-Bobai Gakkai (1986).

The pH of the washing water used in processing the photographic light-sensitive materials according to the present invention is preferably 4 to 9, more preferably 5 to 8. The temperature of the washing water and the time for the water washing step can be adjusted depending on the properties or uses of the photographic light-sensitive materials. Typically, however, a range of 15 to 45°C and a period of 20 seconds to 10 minutes are selected, and preferably a range of 25 to 40°C and a period of 30 seconds to 5 minutes are selected.

The photographic light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of the above-described water washing step. In such a stabilizing process, any known method can be used, for example, as described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345.

It is also possible to carry out the stabilization process following the water washing process described above. An example of this is a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath in the processing of color photographic light-sensitive materials for photography. Examples of the dye stabilizers include aldehydes such as formalin or glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts. Various chelating agents and antifouling agents can be added to such a stabilization bath.

Overflow solutions resulting from the replenishment of the wash water and/or stabilization solution described above can be reused in other steps, such as the desilvering step.

When processing using an automatic developing machine, the concentration of the processing solution in each step tends to occur due to evaporation. To compensate for this concentration of the processing solution, it is preferable to replenish with the appropriate amount of water.

In order to simplify and speed up processing, a color developing agent may be incorporated into the silver halide color photographic material according to the present invention. To incorporate the color developing agent, it is preferred to use various color developing agent precursors. Suitable examples of developing agent precursors include indoaniline-type compounds as described in U.S. Patent 3,342,597, Schiff base compounds as described in U.S. Patent 3,342,599 and Research Disclosure No. 14850 and ibid. No. 15159, aldol compounds as described in Research Disclosure No. 13924, metal salt complexes as described in U.S. Patent 3,719,492, and urethane-type compounds as described in JP-A-53-135628.

Furthermore, the silver halide color photographic material according to the present invention may, if desired, contain various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development. Typical examples of these compounds include those described in, for example, JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.

In the present invention, various types of processing solutions can be used in a temperature range of 10 to 50°C. Although a standard temperature is in the range of 33 to 38°C, it is possible to carry out processing at higher temperatures to accelerate processing, thereby shortening processing time, or at lower temperatures to improve image quality and maintain stability of processing solutions.

In addition, photographic processing can be carried out using color intensification to reduce the amount of silver used in the color photographic light-sensitive material, using cobalt or hydrogen peroxide as described in West German Patent 2,226,770 or US Patent 3,674,499.

In addition, the silver halide color photographic material according to the present invention can be used for heat-developable light-sensitive materials as described, for example, in U.S. Patent 4,500,626, JP-A-60-133449, JP-A-59-218443, JP-A-61-238056 and European Patent 210660A2.

The present invention will be described in detail with reference to the following examples, but should not be construed as limited thereto.

EXAMPLE 1

On a paper support having both surfaces laminated with polyethylene, layers were stacked as shown below to produce a multilayered color printing paper, which was designated as Sample 101. The coating solutions were prepared in the following manner.

Preparation of the coating solution for the first layer:

19.1 g of the yellow coupler (ExY), 4.4 g of the color image stabilizer (Cpd-1) and 0.7 g of the color image stabilizer (Cpd-7) were dissolved in a mixture of 27.2 ml of ethyl acetate and 8.2 g of solvent (Solv-1), and the resulting solution was emulsified and dispersed in 185 ml of a 10% aqueous gelatin solution containing 8 ml of a 10% aqueous solution of sodium dodecylbenzenesulfonate. Separately, to a silver chlorobromide emulsion (cubic grains, mixture of two emulsions with average grain sizes of 0.88 mµ and 0.70 mµ in 3:7 molar ratio to silver, coefficient of variation of grain size: 0.08 and 0.10, respectively, 0.2 mol% of silver bromide localized on the surface of the grains based on the total of the grains) were added two blue-sensitive sensitizing dyes as shown below in an amount of 2.0x10⁻⁴ mol each per mol of silver in the case of the emulsion with the larger grains and in an amount of 2.5x10⁻⁴ mol each per mol of silver in the case of the emulsion with the smaller grains, and the emulsion was then subjected to sulfur sensitization. The emulsified Dispersion was mixed with the silver chlorobromide emulsion while controlling the concentration of the resulting mixture to form the composition shown below, thereby preparing the coating solution for the first layer.

Coating solutions for the second to seventh layers were prepared in a similar manner as described for the coating solution for the first layer.

1-Oxy-3,5-dichloro-s-triazine sodium salt was used as gelatin hardener in each layer.

The following spectral sensitizing dyes were used in the emulsion layers. Blue-sensitive emulsion layer:

(Amount added: 2.0x10⁻⁴ mol per mol of silver halide in the emulsion with the larger grains and 2.5x10⁻⁴ mol per mol of silver halide in the emulsion with the smaller grains.)

Green-sensitive emulsion layer:

(Amount added: 4.0x10⁻⁴ mol per mol of silver halide in the larger grain emulsion and 5.6x10⁻⁴ mol per mol of silver halide in the smaller grain emulsion.)

and

(Amount added: 7.0x10⁻⁵ mol per mol of silver halide in the larger grain emulsion and 1.0x10⁻⁵ mol per mol of silver halide in the smaller grain emulsion.) Red-sensitive emulsion layer:

(Amount added: 0.9x10⊃min;⊃4; mole per mole of silver halide in the larger grain emulsion and 1.1x10⊃min;⊃4; mole per mole of silver halide in the smaller grain emulsion.)

The compound shown below was added to the red-sensitive emulsion layer in an amount of 2.6x10⊃min;³ moles per mole of silver halide.

To the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer was added 1-(5-methylureidophenyl)-5- mercaptotetrazole in an amount of 8.5x10⁻⁵ mol, 7.7x10⁻⁴ mol, and 2.5x10⁻⁴ mol, respectively, per mol of silver halide.

In addition, 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1x10⁻⁴ mol and 2x10⁻⁴ mol, respectively, per mol of silver halide.

In addition, the following dyes were added to the emulsion layers to prevent irradiation. and

Layer structure

The composition of each layer is shown below. The numerical values indicate the coating amounts of the components in g/m² units. The coating amount of the silver halide emulsion is indicated in terms of the silver coating amount.

carrier

Polyethylene laminated paper (the polyethylene coating contained a white pigment (TiO2) and a bluish dye (ultramarine) on the first layer side

First layer (blue-sensitive layer)

Silver chlorobromide emulsion, as described above 0.30

Gelatin 1.86

Yellow coupler (ExY) 0.82

Color Image Stabilizer (Cpd-1) 0.19

Solvent (Solv-1) 0.35

Color Image Stabilizer (Cpd-7) 0.06

Second layer (layer that prevents color mixing)

Gelatin 0.99

Color mixing preventive agent (Cpd-5) 0.08

Solvent (Solv-1) 0.16

Solvent (Solv-4) 0.08

Third layer (green sensitive layer)

Silver chlorobromide emulsion (cubic grains, mixture of two 0.12 emulsions with an average grain size of 0.55 µm and 0.39 µm in a molar ratio of 1:3 of silver, coefficient of variation of grain size: 0.1 and 0.08 respectively, 0.8 mol% of silver bromide based on the total number of grains located on the surface of the grains respectively)

Gelatin 1.24

Magenta coupler (ExM) 0.20

Color Image Stabilizer (Cpd-2) 0.03

Color Image Stabilizer (Cpd-3) 0.15

Color Image Stabilizer (Cpd4) 0.02

Color Image Stabilizer (Cpd-9) 0.02

Organic solvent with a high boiling point (S-3) 0.40

Fourth layer (ultraviolet light absorption layer)

Gelatin 1.58

Ultraviolet light absorber (UV-1) 0.47

Color mixing preventive agent (Cpd-5) 0.05

Solvent (Solv-5) 0.24

Fifth layer (red-sensitive layer)

Silver chlorobromide emulsion (cubic grains, mixture of two 0.23 emulsions with an average grain size of 0.58 µm and 0.45 µm in a 1:4 molar ratio to silver, coefficient of variation of grain size: 0.09 and 0.11, respectively, 0.6 mol% silver bromide based on the totality of grains located on a part of the surface of the grains)

Gelatin 1.34

Cyan coupler (ExC) 0.32

Color Image Stabilizer (Cpd-6) 0.17

Color Image Stabilizer (Cpd-7) 0.40

Color Image Stabilizer (Cpd-8) 0.04

Solvent (Solv-5) 0.15

Sixth layer (ultraviolet light absorption layer)

Gelatin 0.53

Ultraviolet light absorber (UV-1) 0.16

Color mixing preventive agent (Cpd-5) 0.02

Solvent (Solv-5) 0.08

Seventh layer (protective layer)

Gelatin 1.33

Acrylic-modified polyvinyl alcohol copolymer (modification level: 17%) 0.17

Liquid paraffin 0.03

The compounds used in the layers described above have the chemical structures shown below.

Yellow Coupler (ExY)

A mixture of and

in a molar ratio of 1:1. Magenta coupler (ExM)

Cyan coupler (ExC)

A mixture of and

in a weight ratio of 2:4.4. Color Image Stabilizer (Cpd-1) Color Image Stabilizer (Cpd-2) Color Image Stabilizer (Cpd-3) Color Image Stabilizer (Cpd-4) Color Mixing Preventer (Cpd-5)

Color Image Stabilizer (Cpd-6)

A mix of

and

in a weight ratio of 2:4:4. Color image stabilizer (Cpd-7) (average molecular weight: 60,000) Color image stabilizer (Cpd-8) Color Image Stabilizer (Cpd-9)

Ultraviolet light absorbers (UV-1)

A mixture of

and

in a weight ratio of 4:2:4. Solvent (Solv-1) Solvent (Solv-4) Solvent (Solv-5) Solvent (Solv-6)

Samples 102 to 105 were prepared in the same manner as described for Sample 101, except that the amount of the high boiling point organic solvent (S-3) added to the third layer of Sample 101 was changed to 0.5 times, 0.2 times, and 0.1 times the amount added to Sample 101, respectively.

Samples 106 to 110 were prepared in the same manner as described for Samples 101 to 105, except that the magenta coupler ExM was replaced with an equimolar amount of the coupler M-6 used in the third layer according to the present invention, and the amount of the organic solvent having a high boiling point was adjusted to 2 times, 1 time, 0.4 times, 0.2 times and 0 times the amount of the coupler. Such adjustment of the weight ratio was also carried out in the following examples.

Samples 111 to 120 were prepared in the same manner as described for Samples 101 to 105, except that the magenta coupler ExM was replaced with an equimolar amount of the coupler M-12 or the coupler M-24 and that the amount of the organic solvent having a high boiling point was adjusted as described above in the third layer, respectively.

The thus prepared Sample 101 was exposed in an average manner and then subjected to continuous processing according to the processing step 1 as shown below until the amount of the replenisher added to the color developing solution reached twice the volume of the tank for color development.

Then, each of Samples 101 to 120 was exposed wedgewise through a green filter and processed according to the processing step (I) using the processing solutions after the continuous processing.

The hue of magenta color obtained in each sample was measured by a reflection spectrophotometer in a region having an optical density of 1.5. The results obtained are shown in Fig. 1.

As is clear from the results shown in Fig. 1, aggregation of dyes occurred when a coupler other than those of the present invention was used, and further, a large subsidiary absorption in the short wavelength region occurred, resulting in a shift of the magenta color toward red when the amount of the solvent was reduced to half or less of the coupler by weight. In contrast, formation of aggregations was reduced in the couplers according to the present invention, and color reproducibility was not affected even when the amount of the solvent was reduced.

Then, the obtained samples were irradiated with xenon light intermittently for 10 days and the light resistance of the magenta image was checked. The results are shown in Table 1 below. It is clear that when a coupler according to the present invention was used, the decrease in light resistance was only was minimal and excellent color image preservability was obtained when the amount of solvent was reduced.

Further, development processing was carried out except that the amount of the rinsing replenisher (3) was reduced from 350 ml in processing step (I) to 200 ml. This was referred to as processing step (II). The amount of the rinsing solution discharged through the photosensitive material was 30 ml per m².

In order to determine the occurrence of stains in the samples obtained by the above-described processing, each of the samples was stored at 80°C and 70% RH for 10 days, and the magenta density of the samples was measured using a color density meter manufactured by Macbeth Co. The results are also shown in Table 1 below. From these results, it is clear that in the samples containing the coupler and the high boiling point organic solvent according to the present invention, the occurrence of magenta stains was minimal even when the amount of the replenisher for the rinse solution was reduced.

In addition, it is clear that the effect of the present invention increases as the amount of the high boiling point organic solvent used is reduced.

In addition, samples were prepared in the same manner as Samples 101 to 104 except that the coupler in the third layer was replaced with Coupler M-42. The samples were subjected to processing step (I). The spectral absorption characteristics and light resistance of the obtained magenta images were determined. As a result, it was found that although the spectral absorption characteristics were satisfactorily maintained, fading due to light was much greater than in the samples using Couplers M-6, M-12 and M-24 when the amount of the high boiling point organic solvent was reduced. Processing step (I):

* The amount of replenishment per m² of the photographic light-sensitive material.

The flushing steps were performed using a countercurrent system with three tanks from flush (3) to flush (1).

The composition of each processing solution used is shown below.

Bleach-fixing solution: (both tank solution and replenisher)

Water 400ml

Ammonium thiosulfate (70%) 100 ml

Sodium sulphite 17 g

Ammonium iron(III)ethylenediaminetetraacetate 55 g

Disodium ethylenediaminetetraacetate 5 g

Ammonium bromide 40 g

Water to make 1000 ml

pH (at 25ºC) 6.0

Flushing solution: (both tank solution and refill agent)

Ion exchange water (calcium and magnesium content: not more than 3 ppm each) TABLE 1

* In the area with an optical density of 1.0.

EXAMPLE 2

A cellulose triacetate film support (thickness: 127 µ) with an interlayer was coated to prepare a multilayer color photographic light-sensitive material, each layer having the composition shown below. This photographic material was designated as Sample 201. The numerical values indicate the amounts added per m². It should be noted that the effects of the added compounds are not limited to the uses described.

First layer: anti-halation layer

Black colloidal silver 0.25 g

Gelatine 1.9g

Ultraviolet light absorber U-1 0.04 g

Ultraviolet light absorber U-2 0.1 g

Ultraviolet light absorber U-3 0.1 g

Ultraviolet light absorber U-6 0.1 g

Organic solvent with a high boiling point S-1 0.1 g

Second layer: intermediate layer

Gelatine 0.40g

Compound Cpd-D 10 mg

Organic solvent with a high boiling point Oil-3 40 mg

Third layer: intermediate layer

Veiled fine grain silver iodobromide emulsion (average 0.05 g grain size: 0.06 µm, Agl content: 1 mol%) (in terms of silver)

Gelatine 0.4g

Fourth layer: Less sensitive, red-sensitive emulsion layer

Silver iodobromide emulsion [a 1:1 mixture of a monodisperse cubic emulsion (average grain size: 0.4 µm, Agl content: 4.5 mol%) and a monodisperse cubic emulsion (average grain size: 0.3 µm, Agl content: 4.5 mol%)], spectrally sensitized with sensitizing dyes ES-1 and ES-2

Gelatine 0.8g

Coupler C-1 0.20 g

Compound Cpd-D 5.0 mg

Organic solvent with a high boiling point S-1 0.20 g

Fifth layer: Medium-sensitive red-sensitive emulsion layer

Silver iodobromide emulsion (monodisperse cubic grains, average grain size: 0.5 µm, Agl content: 4 mol%), spectrally sensitive with the sensitizing dyes ES-1 and ES-2 0.4 g silver)

Gelatine 0.8g

Coupler C-1 0.2 g

Coupler C-2 0.2 g

Organic solvent with a high boiling point S-1 0.4 g

Sixth layer: Highly sensitive, red-sensitive emulsion layer

Silver iodobromide emulsion (monodisperse twin grains, average grain size: 0.7 µm, Agl content: 2 mol%), spectrally sensitive with the sensitizing dyes ES-1 and ES-2 silver)

Gelatine 1.1g

Coupler C-3 1.0 g

Organic solvent with a high boiling point S-1 1.1 g

Seventh layer: intermediate layer

Gelatine 0.6g

Dye D-1 0.02 g

Eighth layer: intermediate layer

Veiled silver iodobromide emulsion (average grain size: 0.06 µm, Agl content: 0.3 mol%)

Gelatine 10g

Colour mixing inhibitor Cpd-A 0.2 g

Ninth layer: Low-sensitivity, green-sensitive emulsion layer

Silver iodobromide emulsion (a 1:1 mixture of a first emulsion 0.5 g (in (monodisperse cubic grains, average grain size: 0.4 µm, Agl content: 4.5 mol%) and a second emulsion silver) (monodisperse cubic grains, average grain size: 0.2 µm, Agl content: 4.5 mol%)], spectrally sensitized with sensitizing

Dyes ES-3 and ES-4

Gelatine 0.5g

Coupler C-8 0.15 g

Compound Cpd-D 5.0 mg

Compound Cpd-B 0.01 g

Compound Cpd-E 0.01 g

Compound Cpd-F 0.01 g

Compound Cpd-G 0301 g

Compound Cpd-H 0.01 g

Organic solvent with a high boiling point S-1 0.3 g

Tenth layer: Medium-sensitive, green-sensitive emulsion layer

Silver iodobromide emulsion (monodisperse cubic grains, average grain size: 0.5 µm, Agl content: 3 mol%), spectrally sensitized with the sensitizing dyes ES-3 and ES-4 silver)

Gelatine 0.6g

Coupler C-8 0.2 g

Compound Cpd-B 0.03 g

Compound Cpd-E 0.01 g

Compound Cpd-F 0.01 g

Compound Cpd-G 0.01 g

Compound Cpd-H 0.01 g

Organic solvent with a high boiling point S-1 0.4 g Eleventh layer: High-sensitivity, green-sensitive emulsion layer Silver iodobromide emulsion (monodisperse tabular grains, average grain size (with respect to a sphere): 0.6 µm, mol%), spectrally sensitized with sensitizing dyes ES-3 and

ES-4

Gelatine 1.0g

Coupler C-8 0.6 g

Compound Cpd-B 0.01 g

Compound Cpd-E 0.01 g

Compound Cpd-F 0.01 g

Compound Cpd-G 0.01 g

Compound Cpd-H 0.01 g

Organic solvent with a high boiling point S-1 1.2 g

Twelfth layer: intermediate layer

Gelatine 0.6g

Dye D-2 0.05 g

Thirteenth layer: yellow filter layer

Yellow colloidal silver 0.1 g (in regard to silver)

Gelatine 1.1g

Colour mixing inhibitor Cpd-A 0.01 g

Fourteenth layer: intermediate layer

Gelatine 0.6g

Fifteenth layer: Low-sensitivity, blue-sensitive emulsion layer

Silver iodobromide emulsion [a 1:1 mixture of a first monodisperse cubic emulsion (average grain size: 0.4 µm, AgL content: 3 mol%) and a second monodisperse cubic emulsion (average grain size: 0.2 µm, AgL content: 3 mol%)] sensitized with sensitizing dyes ES-5 and ES-6

Gelatine 0.8g

Coupler C-5 0.6 g

Sixteenth layer: Medium-sensitive, blue-sensitive emulsion layer

Silver iodobromide emulsion (monodisperse cubic grains, average grain size: 0.5 µm, Agl content: 2 mol%), sensitized with respect to silver sensitizing dyes ES-5 and ES-6)

Gelatine 0.9g

Coupler C-5 0.3 g

Coupler C-6 0.3 g

Seventeenth layer: Highly sensitive, blue-sensitive emulsion layer

Silver iodobromide emulsion (tabular grains, average value 0.4 9 (in the diameter/thickness of 7, average grain size of 0.7 µm with respect to a sphere, Agl content: 1.5 mol%), sensitized with silver) the sensitizing dyes ES-5 and ES-6

Gelatine 1.2g

Coupler C-6 0.7 g

Eighteenth layer: First protective layer

Gelatine 0.7g

Ultraviolet light absorber U-1 0.04 g

Ultraviolet light absorber U-3 0.03 g

Ultraviolet light absorber U-4 0.03 g

Ultraviolet light absorber u-5 0.05 g

Ultraviolet light absorber U-6 0.05 g

Formalin radical scavenger Cpd-C 0.8 g

Dye D-3 0.05 g

Nineteenth layer: Second protective layer

Veiled fine grain silver iodobromide emulsion (average 0.1 g (in grain size: 0.06 µm, AgI content: 1 mol%) in terms of silver)

Gelatine 0.4g

Twentieth layer: Third layer of protection

Gelatine 0.4g

Polymethyl methacrylate (average particle size 1.5 µm) 0.1 g

Methyl methacrylate-acrylic acid copolymer (4:6) (average particle size: 1.5 µm) 0.1 g

Silicone oil 0.03 g

Surfactant W-1 3.0 mg

In addition to the composition described above, a gelatin hardener H-1 and surfactants for coating and emulsification were added to each layer.

The compounds used in the layers described above are shown below. Coupler C-8 Oil-3

Samples 202 were prepared in the same manner as described for Sample 201, except that the amount of the high boiling point organic solvent S-1 used in the ninth, tenth and eleventh layers of Sample 201 was changed to 0.5 times the respective amounts used in Sample 201.

Samples 203 were prepared in the same manner as Sample 201, except that the amount of the high boiling point organic solvent S-1 used in the ninth, tenth and eleventh layers of Sample 201 was changed to 0.1 times the respective amounts used in Sample 201.

Samples 204 to 206 were prepared in the same manner as described for Samples 201 to 203, except that the coupler C-8 added to the ninth, tenth and eleventh layers of Samples 201 to 203 was replaced with an equimolar amount of the coupler M-1 according to the present invention and that the amount of the organic solvent was adjusted to establish the same weight ratio of organic solvent to each coupler.

Samples 207 to 212 were prepared in the same manner as described for Samples 201 to 203, except that Coupler C-8 added to the ninth, tenth and eleventh layers of Samples 201 to 203 was replaced with an equimolar amount of Coupler M-14 or Coupler M-20 and the amount of organic solvent was adjusted as described above, respectively.

The magenta coupler and the weight ratio of the organic solvent to the coupler used in the ninth, tenth and eleventh layers of Samples 201 to 212 are summarized in Table 2 below. TABLE 2

Samples 201 to 212 were uniformly exposed through a red filter and a blue filter and further through a green filter in a wedge-wise manner and then subjected to development processing according to the processing step (II) described below.

The visible absorption spectrum of each sample was measured by a spectrophotometer. The results obtained are shown in Figure 2.

As is clear from the results shown in Figure 2, when a comparative coupler other than those of the present invention was used, aggregation of the dyes occurred when the amount of the high boiling point solvent was reduced. In contrast, almost no formation of aggregation was observed when the couplers according to the present invention were used, even when the amount of the high boiling point organic solvent was reduced.

Furthermore, these samples were cut into a 35 mm wide strip, loaded into a camera, used to photograph ordinary objects, and processed. In these samples, the color reproducibility of the red series color was particularly observed. The samples according to the present invention showed only minimal changes in hue from low density areas to high density areas. They also showed high saturation and excellent color reproducibility. Processing step (II):

Each processing solution had the following composition.

The pH was adjusted with hydrochloric acid or potassium hydroxide.

Reverse solution: (both tank solution and refill agent)

Pentasodium salt of nitrilo-N,N,N-trimethylenephosphonic acid 3.0 g

Tin chloride (dihydrate) 1.0 g

p-Aminophenol 0.1 g

Sodium hydroxide 8 g

Glacial acetic acid 15 ml

Water to make 1000 ml

pH6.00

The pH was adjusted with hydrochloric acid or sodium hydroxide.

The pH was adjusted with hydrochloric acid or potassium hydroxide.

Conditioning solution: (both tank solution and replenisher)

Disodium ethylenediaminetetraacetate (dihydrate) 8.0 g

Sodium sulphite 12 g

1-Thioglycerol 0.4 ml

Sorbitan ester* 0.1 g

Water to make 1000 ml

pH6.20

The pH was adjusted with hydrochloric acid or sodium hydroxide. Sorbitan ester:

The pH was adjusted with hydrochloric acid or sodium hydroxide.

Fixing solution: (both tank solution and replenisher)

Ammonium thiosulfate 8.0 g

Sodium sulphite 5.0 g

Sodium bisulfite 5.0 g

Water to make 1000 ml

pH6.60

The pH was adjusted with hydrochloric acid or aqueous ammonia.

Stabilizing solution: (both tank solution and replenisher)

Formalin (37%) 5.0 ml

Polyoxyethylene p-monononylphenyl ether (average degree of 0.5 ml polymerization)

Water to make 1000 ml

pH not adjusted

EXAMPLE 3

On a cellulose triacetate film support provided with an interlayer, each layer having the composition shown below was coated to prepare a multilayer color photographic light-sensitive material, which was designated as Sample 301.

With respect to the compositions of the layers, the coating amounts of the silver halide and colloidal silver are expressed in units of g/m² in terms of silver, the coating amounts of the couplers, additives and gelatin are expressed in units of g/m², and the coating amounts of the sensitizing dyes are expressed in terms of moles per mole of the silver halide present in the same layer.

The symbols denoting additives used in this example have the meanings described below. If the additive has two or more functions, one of these functions is shown as representative.

UV: Ultraviolet light absorber

Solv: Organic solvent with a high boiling point

ExF: dye

ExS: Sensitizing dye

ExC: Cyan coupler

ExM: Magenta coupler

ExY: Yellow coupler

Cpd: Additive

First layer: anti-halation layer

Black colloidal silver 0.15

Gelatin 2.0

ExM-6 0.2

UV-1 0.03

UV-2 0.06

UV-3 0.07

S-1 0.3

Solv-2 0.08

ExF-1 0.01

ExF-2 0.01

ExF-3 0.005

Cpd-6 0.001

Second layer: Low-sensitivity, red-sensitive emulsion layer

Silver iodobromide emulsion (Agl: 4 mol%, uniform Agl type, 0.37 Diameter corresponding to a sphere: 0.4 µm, coefficient of variation (with respect to diameter, corresponding to a silver sphere: 30%, tabular grain, diameter/thickness ratio: 3.0)

Silver iodobromide emulsion (Agl: 6 mol%, internal high Agl type, 0.19 with a core/shell ratio of 2:1, diameter, (with respect to corresponding to sphere: 0.45 µm, coefficient of variation (on silver) of diameter, corresponding to sphere: 23%, tabular grain, diameter/thickness ratio: 2.0)

Gelatin 0.8

ExS-1 2.3x10⊃min;⊃4;

ExS-2 1.4x10-25;

ExS-5 2.3x10⊃min;⊃4;

ExS-7 4.2x10⊃min;⊃6;

ExC-1 0.17

ExC-2 0.03

ExC-3 0.009

Third layer: Medium-sensitive, red-sensitive emulsion layer

Silver iodobromide emulsion (Agl: 6 mol%, internal high Agl type, 0.65 with a core/shell ratio of 2:1, diameter, (with respect to silver) corresponding to sphere: 0.65 µm, coefficient of variation of diameter, corresponding to sphere: 23%, tabular grain, diameter/thickness ratio: 2.0)

Gelatin 1.0

ExS-1 2.3x10⊃min;⊃4;

ExS-2 1.4x10-25;

ExS-5 2.3x10⊃min;⊃4;

ExS-7 4.2x10⊃min;⊃6;

ExC-1 0.31

ExC-2 0.01

ExC-3 0.10

Fourth layer: Highly sensitive, red-sensitive emulsion layer

Silver iodobromide emulsion (Agl: 6 mol%, multilayered 1.5 structure grain with a silver content of 3:4:2, (in terms of Agl content: 24 mol, 0 mol, 6 mol from inside, diameter on silver) corresponding to the sphere: 0.75 µm, coefficient of variation of diameter, corresponding to the sphere: 23%, tabular grain, diameter/thickness ratio: 2.5)

Gelatin 1.4

ExS-1 1.9x10⊃min;⊃4;

ExS-2 1.2x10⊃min;⊃4;

ExS-5 1.9x10⊃min;⊃4;

ExS-7 8.0x10⊃min;⊃6;

ExC-1 0.08

ExC-4 0.09

S-1 0.08

Solv-2 0.20

Cpd-7 4.6x10⊃min;⊃4;

Fifth layer: intermediate layer

Gelatin 0.6

Cpd-1 0.1

Polyethylene acrylate latex 0.08

S-1 0.08

Sixth layer: Low-sensitivity, green-sensitive emulsion layer

Silver iodobromide emulsion (Agl: 4 mol%, uniform Agl type, 0.18 Diameter corresponding to sphere: 0.33 µm, coefficient of variation (with respect to silver) sphere: 37%, tabular grain, diameter/thickness ratio: 2.0)

Gelatin 0.4

ExS-3 1.6x10⊃min;⊃4;

ExS-4 4.8x10⊃min;⊃4;

ExS-5 1x10⊃min;⊃4;

ExM-5 0.10

ExM-7 0.03

ExY-8 0.01

S-1 0.15

Seventh layer: Medium-sensitive, green-sensitive emulsion layer

Silver iodobromide emulsion (Agl: 4 mol%, uniform Agl type, 0.27 diameter, corresponding to sphere: 0.55 µm, variation (with respect to coefficient of diameter, corresponding to the silver) sphere: 15%, tabular grain, diameter/thickness ratio: 4.0)

Gelatin 0.6

ExS-3 2x10⊃min;⊃4;

ExS-4 7x10⊃min;⊃4;

ExS-5 1.4x10⊃min;⊃4;

ExM-5 0.17

ExM-7 0.04

ExY-8 0.02

S-1 0.25

Eighth layer: Highly sensitive, green-sensitive emulsion layer

Silver iodobromide emulsion (Agl: 8.8 mol%, multilayered 0.5 structure grain with a silver content of 3:4:2, (in terms of Agl content: 24 mol, 0 mol, 3 mol from inside, diameter, on silver) corresponding to sphere: 0.75 µm, coefficient of variation of diameter, corresponding to sphere: 23%, tabular grain, diameter/thickness ratio: 1.6)

Gelatin 0.6

ExS-4 5.2x10-25;

ExS-5 1x10⊃min;⊃4;

ExS-8 0.3x10⊃min;⊃4;

ExM-5 0.08

ExM-6 0.03

ExY-8 0.02

ExC-1 0.01

ExC-4 0.01

S-1 0.15

Solv-2 0.05

Cpd-7 1x10⊃min;⊃4;

Cpd-8 0.01

Ninth layer: intermediate layer

Gelatin 0.6

Cpd-1 0.04

Polyethylene acrylate latex 0.05

S-1 0.02

UV-4 0.03

UV-5 0.04

Tenth layer: Donor layer for an intermediate image effect to the red-sensitive layer

Silver iodobromide emulsion (Agl: 8 mol%, internal high Agl type, 0.72 with a core/shell ratio of 2:1, diameter, (with respect to silver) corresponding to sphere: 0.65 µm, coefficient of variation of diameter, corresponding to sphere: 25%, tabular grain, diameter/thickness ratio: 2.0)

Silver iodobromide emulsion (Agl: 4 mol%, uniform Agl type, 0.21 Diameter corresponding to sphere: 0.4 µm, coefficient of variation (with respect to silver) sphere: 30%, tabular grain, diameter/thickness ratio: 3.0)

Gelatin 1.0

ExS-3 6x10⊃min;⊃4;

ExM-10 0.19

S-1 0.30

Solv-6 0.03

Eleventh layer: yellow filter layer

Yellow colloidal silver 0.06

Gelatin 0.8

Cpd-2 0.13

S-1 0.13

Cpd-1 0.07

Cpd-6 0.002

H-1 0.13

Twelfth layer: Low-sensitivity, blue-sensitive emulsion layer

Silver iodobromide emulsion (Agl: 4.5 mol%, uniform Agl type, 0.45 diameter, corresponding to sphere: 0.7 µm, coefficient of variation (with respect to silver) diameter, corresponding to sphere: 15%, tabular grain, diameter/thickness- Ratio: 7.0)

Silver iodobromide emulsion (Agl: 3 mol%, uniform Agl type, 0.25 Diameter corresponding to sphere: 0.3 µm, coefficient of variation (with respect to silver) sphere: 30%, tabular grain, diameter/thickness ratio: 7.0)

Gelatin 2.1

ExS-6 9x10⊃min;⊃4;

ExC-1 0.13

ExC-4 0.03

ExY-9 0.16

ExY-11 1.04

S-1 0.51

Thirteenth layer: intermediate layer

Gelatin 0.4

ExY-12 0.20

S-1 0.19

Fourteenth layer: Highly sensitive, blue-sensitive emulsion layer

Silver iodobromide emulsion (Agl: 10 mol%, internal high Agl type, 0.4 diameter corresponding to sphere: 1.0 µm, coefficient of variation (with respect to silver) 25%, multiple tabular twin intergrowth grains, diameter/thickness ratio: 2.0)

Gelatin 0.5

ExS-6 1x10⊃min;⊃4;

ExY-9 0.01

ExY-11 0.20

ExC-1 0.01

S-1 0.10

Fifteenth layer: First protective layer

Fine grain silver iodobromide emulsion (Agl: 2 mol%, 0.12 uniform Agl type, diameter, corresponding (with respect to sphere: 0.07 µm) on silver)

Gelatin 0.7

UV4 0.11

UV-5 0.16

Solv-5 0.02

H-1 0.13

Cpd-5 0.10

Polyethylene acrylate latex 0.09

Sixteenth layer: Second protective layer

Fine grain silver iodobromide emulsion (Agl: 2 mol%, 0.36 uniform Agl type, diameter, corresponding (with respect to sphere: 0.07 µm) on silver)

Gelatin 0.85

Polymethyl methacrylate particles (diameter: 1.5 µm) 0.2

Cpd-4 0.04

W-4 0.02

H-1 0.17

Each of the layers described above further contained an emulsion stabilizer (Cpd-3: 0.07 g/m²) and surfactants (W-1: 0.006 g/m², W-2: 0.33 g/m², W-3: 0.10 g/m²) as coating aids or emulsifiers or dispersants in addition to the compounds described above.

The compounds used to prepare the photosensitive material are shown below.

Solv-2 Dibutylphthalate

Solv-5 Tricresyl Phosphate

Samples 302 and 303 were prepared in the same manner as described for Sample 301, except that the amount of the high boiling point organic solvent (S-1) added to the sixth, seventh and eighth layers of Sample 301 was changed to 2/3 times and 1/10 times the amount used in Sample 301. The ratio of oil-soluble components to gelatin used was kept constant. "Oil-soluble components" means all compounds present in oil droplets.

Samples 304 to 306 were prepared in the same manner as described for Samples 301 to 303, except that the magenta coupler ExM-5 used in the sixth, seventh and eighth layers was replaced with an equimolar amount of the coupler M-6 according to the present invention and that the amount of the high boiling point organic solvent was adjusted to keep the weight ratio of organic solvent to coupler exactly the same as in Samples 301 to 303.

Samples 307 to 309 were prepared in the same manner as described for Samples 304 to 306, except that Coupler M-6 was replaced with an equimolar amount of Coupler M-14 and the amount of high boiling point organic solvent was adjusted to maintain the same weight ratio of organic solvent to coupler.

The thus prepared samples 301 to 309 were exposed in a conventional manner and subjected to development processing according to the processing step (III) described below. Then, the transmission spectral absorption curve of each sample was measured. The results showed that in samples other than those of the present invention, the subsidiary absorption in the short wavelength region became large and the shapes of the absorption curves at low density and high density changed when the amount of the high boiling point organic solvent was reduced.

Furthermore, these samples were photographed in practice with different exposure amounts. Prints were made from under-exposed and over-exposed negatives using an automatic printing device, manufactured by Fuji Photo Film Co., Ltd. The overexposed samples had a greenish color.

In addition, the MTF of each sample was measured to determine the pungency. The results are shown in Table 3 below. The results indicate that the pungency is good when the oil-soluble content is low. These results support the conventional wisdom that good pungency is obtained when the dry layer thickness is low.

From these results, it is clear that only the combination of the couplers with high boiling point organic solvents according to the present invention results in minimal color changes and excellent sharpness when pyrazolotriazole couplers are used. This fact could not be expected from the known methods. Processing step (III):

* Amount of refill per 1 meter of a 35 mm wide strip.

The fixing tank of the automatic developing machine was equipped with a jet stirring device as described in JP-A-62-183460, p. 3, and the light-sensitive material was processed in such a way that a jet of the fixing solution was directed against the Each material was processed in such a way that a jet of the fixing solution was directed against the surface of the photosensitive material. The composition of each processing solution used is shown below.

The pH was adjusted with acetic acid and aqueous ammonia.

The pH was adjusted with ammonium acetate.

Stabilizing solution: (both starting solution and replenisher)

Formalin (37%) 1.2 ml

5-Chloro-2-methyl4-isothiazolin-3-one 6.0 mg

2-Methyl-4-isothiazolin-3-one 3.0 mg

Surfactant 0.49

C₁₀₋H₂₁-O(CH₂CH₂O)₁₀₋H

Ethylene glycol 1.0g

Water to make 1.0 l

pH 5.0 to 7.0 TABLE 3

EXAMPLE 4

Samples 213 to 221 were prepared in the same manner as described for Samples 204 to 212 of Example 2, except that the high boiling point organic solvent (S-1) added to the ninth, tenth and eleventh layers according to the present invention was replaced with the same weight of a high boiling point organic solvent (S-6).

In the same manner as above, samples 222 to 230 were prepared, using the same weight of (S-4) instead of (S-1).

Samples 204 to 230 were exposed to white light in a wedge-like manner and processed in the same manner as in Example 2. The results showed that higher maximum density and higher gamma were obtained when the dielectric constant of the high boiling point organic solvent used was higher. For the samples using the high boiling point organic solvent (S-4), the gradation was soft and Dmax was a little low.

EXAMPLE 5

The following first to fourteenth layers were coated on the front side of a paper support (100 µm thick) both surfaces of which were laminated with polyethylene, and the following fifteenth and sixteenth layers were coated on the back side of the paper support to prepare a color photographic light-sensitive material designated as Sample 501. The polyethylene laminated on the first layer side of the support contained titanium dioxide (4 g/m²) as a white pigment and a small amount (0.003 g/m²) of ultramarine as a bluish dye (chromaticity of the surface of the support was 88.0, -0.20 and -0.75 in an L*, a* and b* system, respectively).

Structure of the layers

The composition of each layer is shown below. The coating amounts of the components are described in g/m² units. With regard to silver halide, the coating amount is indicated in terms of the silver coating amount. The emulsion used in each layer was prepared according to the method for preparing emulsion EM-1. The emulsion used in the 14th layer was a Lippmann emulsion which was not chemically sensitized on the surfaces of the grains.

First layer: anti-halation layer

Black colloidal silver 0.10

Gelatin 0.70

Second layer: intermediate layer

Gelatin 0.70

Third layer: Low sensitivity, red-sensitive layer

Silver bromide emulsion, spectrally sensitized with the red-0.04 sensitizing dyes (ExS-1, 2, 3) (average grain size: 0.25 µm, size distribution (coefficient of variation): 8%, octahedral)

Silver chlorobromide emulsion, spectrally sensitized with the 0.08 red sensitizing dyes (ExS-1, 2, 3) (silver chloride: 5 mol%, average grain size: 0.4 µm, size distribution 10%, octahedral)

Gelatin 1.00

Cyan coupler (ExC-1, 2, 3, mixing ratio: 0.30 1/1/0.2 by weight)

Color Fading Preventive Agent (Cpd-1, 2, 3, 4, 0.18 Mixing ratio: 1/1/1/1 by weight

Stain preventive agent (Cpd-5) 0.003

Coupler dispersion medium (Cpd-6) 0.03

Coupler solvent (Solv-1, 2, 3, mixing ratio: 0.12 1/1/1 by weight)

Fourth layer: Highly sensitive, red-sensitive layer

Silver bromide emulsion, spectrally sensitized with the red-0.14 sensitizing dyes (ExS-1, 2, 3) (average grain size: 0.6 µm, size distribution (coefficient of variation): 15%, octahedral)

Gelatin 1.00

Cyan coupler (ExC-1, 2, 3, mixing ratio: 0.30 1/1/0.2 by weight)

Color Fade Preventive Agent (Cpd-1, 2, 3, 4, 0.18 Mixing ratio: 1/1/1/1 by weight)

Coupler dispersion medium (Cpd-6) 0.03

Coupler solvent (Solv-1, 2, 3, mixing ratio: 0.12 1/1/1 by weight)

Fifth layer: intermediate layer

Gelatin 1.00

Color mixing preventive agent (Cpd-7) 0.08

Color Mixing Preventing Agent Solvent 0.16 (Solv-4, 5, Mixing Ratio: 1/1 by weight)

Polymer latex (Cpd-8) 0.10

Sixth layer: Low sensitivity, green sensitive layer

Silver bromide emulsion, spectrally sensitized with green 0.04 sensitizing dye (ExS-4) (average grain size: 0.25 µm, size distribution 8%, octahedral)

Silver chlorobromide emulsion spectrally sensitized with the green 0.06 sensitizing dye (ExS-4) (silver chloride: 5 mol%, average grain size: 0.4 µm, size distribution: 10%, octahedral)

Gelatin 0.80

Magenta coupler (ExM-1) 0.11

Color Fade Preventive Agent (Cpd-9, 26, 0.15 Mixing ratio: 1/1 by weight)

Stain preventive agent (Cpd-10, 11, 12, 13, 0.025 Mixing ratio: 10/7/7/1 by weight)

Coupler solvent (Solv-4, 6, mixing ratio: 0.15 1/1 by weight)

Seventh layer: Highly sensitive, green-sensitive layer

Silver bromide emulsion, spectrally sensitized with the green 0.10 sensitizing dye (ExS-4) (average grain size: 0.65 µm, size distribution 16%, octahedral) sensitizing dye (ExS-4) (average grain size: 0.65 µm, size distribution: 16%, octahedral)

Gelatin 0.80

Magenta coupler (ExM-1) 0.11

Color Fade Preventive Agent (Cpd-9, 26, 0.15 Mixing ratio: 1/1 by weight)

Stain preventive agent (Cpd-10, 11, 12, 13, 0.025 Mixing ratio: 10/7/7/1 by weight)

Coupler solvent (Solv-4) 0.15

Eighth layer: intermediate layer

The same as the fifth layer

Ninth layer: yellow filter layer

Yellow colloidal silver (average grain size: 100 Å) 0.12

Gelatin 0.70

Color mixing inhibitor (Cpd-7) 0.03

Color Mixing Preventer Solvent 0.10 (Solv-4, 5, Mixing Ratio: 1/1 by weight)

Polymer latex (Cpd-8) 0.07

Tenth layer: intermediate layer

The same as the fifth layer

Eleventh layer: Low sensitivity, blue-sensitive layer

Silver bromide emulsion, spectrally sensitized with the blue 0.07 sensitizing dyes (ExS-5, 6) (average grain size: 0.4 µm, size distribution 8%, octahedral)

Silver chlorobromide emulsion, spectrally sensitized with the blue 0.14 sensitizing dyes (ExS-5, 6) (silver chloride: 8 mol%, average grain size: 0.6 µm, size distribution 11%, octahedral)

Gelatin 0.80

Yellow coupler (ExY-1, 2, mixing ratio: 1/1 by weight) 0.35

Color Fade Preventing Agent (Cpd-1 4) 0.10

Stain preventive agent (Cpd-5, 15, mixing ratio: 0.007 1/5 by weight)

Coupler dispersion medium (Cpd-6) 0.05

Coupler solvent (Solv-2) 0.10

Twelfth layer: Highly sensitive, blue-sensitive layer

Silver bromide emulsion, spectrally sensitized with the blue 0.15 sensitizing dyes (ExS-5, 6) (average grain size: 0.85 µm, size distribution 18%, octahedral)

Gelatin 0.60

Yellow coupler (ExY-1, 2, mixing ratio: 1/1 by weight) 0.30

Color Fade Preventing Agent (Cpd-1 4) 0.10

Stain preventive agent (Cpd-5, 15, mixing ratio: 0.007 1/5 by weight)

Coupler dispersion medium (Cpd-6) 0.05

Coupler solvent (Solv-2) 0.10

Thirteenth layer: ultraviolet light absorption layer

Gelatin 1.00

Ultraviolet light absorber (Cpd-2, 4.16, 0.50 Mixing ratio: 1/1/1 by weight)

Color mixing preventive agent (Cpd-7, 17, 0.03 Mixing ratio: 1/1 by weight)

Dispersion medium (Cpd-6) 0.02

Ultraviolet light absorber solvent 0.08 (Solv-2, 7, mixing ratio: 1/1 by weight)

Irradiation Preventing Agent (Cpd-18, 19, 20, 21, 27, 0.05 Mixing ratio: 10/10/13/15/20 by weight)

Fourteenth layer: protective layer

Silver chlorobromide fine particles (silver chloride: 97 mol%, 0.03 average grain size: 0.1 µm)

Acrylic-modified copolymer of polyvinyl alcohol 0.01 (average molecular weight: 50,000)

Polymethyl methacrylate particles (average 0.05 particle size: 2.4 µm) and silicon oxide (average particle size 5 µm, mixing ratio: 1/1 by weight)

Gelatine 1.80

Gelatin hardener (H-1, 2; mixing ratio: 1/1 by weight) 0.18

Fifteenth layer: back layer

Gelatine 2.50

Ultraviolet light absorbers (Cpd-2, 4,16, 0.50

Mixing ratio: 1/1/1 per weight)

Dye (Cpd-18, 19, 20, 21, 27, Mixing ratio: 0.06 1/1/1/1/1 by weight)

Sixteenth layer: back protection layer

Polymethyl methacrylate particles (average particle size: 2.4 µm) and silicon oxide (average particle size: 5 µm), mixing ratio: 1/1 by weight

Gelatin 2.00

Gelatin hardener (H-1, 2, mixing ratio: 1/1 by weight) 0.14

Preparation of emulsion EM-1

An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to an aqueous gelatin solution at 75°C over a period of 15 min with vigorous stirring to obtain an octahedral silver bromide emulsion with an average grain diameter of 0.35 µm. At this time, 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thione per mol of silver was added. Then, 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) were added to the emulsion per mol of silver in this order, and the emulsion was heated at 75°C for 80 min to be chemically sensitized. The thus prepared silver bromide grains were used as cores and further grown under the same precipitation conditions as above to finally obtain a monodisperse octahedral core/shell type silver bromide emulsion with an average grain diameter of 0.7 µm. The coefficient of variation of the grain size was approximately 10%.

1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) were added to the emulsion per mol of silver, and the emulsion was heated at 60°C for 60 min to be chemically sensitized, so that a latent image type internal silver halide emulsion was obtained.

To each photosensitive layer, ExZK-1 in an amount of 10⁻³ wt% and ExZk-2 in an amount of 10⁻² wt% based on the silver halide were added as a nucleating agent, and Cpd-22 was added as a nucleation accelerator in an amount of 10⁻² wt% based on the silver halide.

In addition, Alkanol XC (manufactured by Dupont) and sodium alkylbenzenesulfonate were added to each layer as emulsifiers and dispersion aids, and succinic acid ester and Megafac F-120 (manufactured by Dai Nippon Ink and Chemical Co, Ltd.) as coating aids. In addition, Cpd-23, 24 and 25 were added to the layers containing silver halide or colloidal silver as stabilizers.

The connections used in this example are listed below.

Solv-1 Di(2-ethylhexyl)sebacate

Solv-2 Trinonyl Phosphate

Solv-3 Di(3-methylhexyl)phthalate

Solv-4 Tricresyl Phosphate

Solv-5 Dibutylphthalate

Solv-6 Trioctyl Phosphate

Solv-7 Di(2-ethylhexyl)phthalate

H-1 1,2-bis(vinylsulfonylacetamido)ethane

H-2 4,6-dichloro-2-hydroxy-1,3,5-triazine sodium salt

ExZK-1 7-(3-Ethoxythiocarbonylaminobenzamido)-9-methyl-10-propargyl-1,2,3,4- tetrahydroacridinium trifluoromethanesulfonate

ExZK-2 2-[4-{3-[3-{3-[5-{3-[2-chloro-5-(1-dodecyloxycarbonylethoxycarbonyl)phenylcarbamoyl]-4-hydroxy-1-naphthylthio}tetrazol-1-yl]- phenyl}ureido]benzenesulfonamido}phenyl]-1-formylhydrazine

Samples 502 and 503 were prepared in the same manner as described for Sample 501, except that the amount of coupler solvent added to the sixth and seventh layers of Sample 501 was changed to 0.1 and 0.2 g/m2, respectively.

Samples 504 and 506 were prepared in the same manner as described for Samples 501 to 503, except that an equimolar amount of the coupler M-16 according to the present invention was used in place of the magenta coupler (ExM-1) in Samples 501 to 503.

Samples 507 to 509 were prepared in the same manner as described for Samples 501 to 503, except that an equimolar amount of the coupler M-41 according to the present invention was used in place of the magenta coupler (ExM-1) in Samples 501 to 503.

The thus prepared Sample 501 was imagewise exposed and then continuously processed in accordance with the processing method described below by an automatic developing machine until the total amount of the replenisher, added to the color developing solution was three times the volume of the color developing tank.

The replenishment system for the washing water was a countercurrent replenishment system in which a replenisher was added to the water washing bath (3), the overflowing solution from the water washing bath (3) was introduced into the water washing bath (2), and the overflowing solution of the water washing bath (2) was introduced into the water washing bath (1). In the processing process, the amount of the bleach-fixing solution carried along with the photographic material being processed from the bleach-fixing bath to the water washing bath (1) was 35 mum², and the volume of the replenisher of the washing water to the amount of the bleach-fixing solution carried along was 9.1 times.

The compositions of the processing solutions used were as follows.

Bleach-fixing solution: (both starting solution and replenisher)

Disodium ethylenediaminetetraacetate dihydrate 4.0 g

Ammonium iron(III)ethylenediaminetetraacetate dihydrate 46.0 g

Ammonium thiosulfate (700 g/l) 155 ml

Sodium p-toluenesulfinate 20.0 g

Sodium bisulfite 12.0 g

Ammonium bromide 50.0 g

Ammonium nitrate 30.0 g

Water to make 1000 ml

pH (at 25ºC) 6.20

Wash water (both starting solution and replenisher)

City water was passed through a mixed bed column filled with a strongly acidic H-type cation exchange resin (Amberlite IR-1208, manufactured by Rohm & Haas Co.) and an OH-type anion exchange resin (Amberlite IR-400, manufactured by Rohm & Haas Co.) to prepare water containing not more than 3 mg/L of calcium ions and magnesium ions. To the thus-treated water were added sodium dichloroisocyanurate in an amount of 20 mg/L and sodium sulfate in an amount of 1.5 g/L. The pH of the solution was in the range of 6.5 to 7.5.

Thereafter, Samples 502 to 509 were imagewise exposed to green light and then processed according to the processing steps described above using the processing solutions after continuous processing.

A spectral absorbance of magenta color obtained for each sample was measured, and the magenta color spots after preservation of each sample under conditions of 80ºC and 70% RH for 6 days were determined.

As a result, it was found that in Samples 505, 506, 508 and 509 in which a coupler according to the present invention was used, the formation of aggregation of dyes was very small, a color tone of the image appeared sharp, and the occurrence of magenta stain was also small.

EXAMPLE 6

On a paper support having both surfaces laminated with polyethylene, the first through twelfth layers were coated as shown below to prepare a multilayer color photographic light-sensitive material designated as Sample 601. The polyethylene on the first layer side contained titanium white as a white pigment and a small amount of ultramarine as a bluish dye.

Structure of the layers

The components and the amounts coated thereon in g/m² are shown below. The coated amounts of silver halide are shown in terms of silver.

First layer: gelatin layer

Gelatine 1.30

Second layer: anti-halation layer

Black colloidal silver 0.10

Gelatin 0.70

Third layer: Low sensitivity, red-sensitive layer

Silver chloroiodobromide emulsion EM1 (silver chloride: 1 mol%; 0.06 silver iodide: 4 mol%; average grain size: 0.3 µm; size distribution 10%; cubic iodide core-like core/shell grains), spectrally sensitized with red sensitizing dyes (ExS-1, 2 and 3)

Silver iodobromide emulsion EM2 (silver iodide: 5 mol%; average grain size: 0.45 µm; size distribution 20%; tabular grains) (ratio: 5), spectrally sensitized with the red sensitizing dyes (ExS-1, 2 and 3)

Gelatin 1.00

Cyan coupler (ExC-1) 0.14

Cyan coupler (ExC-2) 0.07

Color Fade Preventing Agents (Cpd-2, 3, 4 and 9 0.12 in equal amounts)

Coupler dispersion medium (Cpd-5) 0.03

Coupler solvent (Solv-1, 2 and 3) 0.06

Fourth layer: Highly sensitive, red-sensitive layer

Silver iodobromide emulsion EM3 (silver iodide: 6 mol%; average grain size: 0.75 µm; size distribution 25%; tabular iodide core grains) (ratio: 8), spectrally sensitized with the red sensitizing dyes (ExS-1, 2 and 3)

Gelatin 1.00

Cyan coupler (ExC-1) 0 20

Cyan coupler (ExC-2) 0.10

Color Fade Preventing Agent (Cpd-2, 3, 4 and 9 0.15 in equal amounts)

Coupler dispersion medium (Cpd-5) 0.03

Coupler solvent (Solv-1, 2 and 3) 0.10

Fifth layer: intermediate layer

Magenta colloidal silver 0.02

Gelatin 1.00

Color mixing preventive agents (Cpd-6 and 7) 0.08

Paint Mixing Preventer Solvent (Solv-4 and 5) 0.16

Polymer latex (Cpd-8) 0.10

Sixth layer: Low sensitivity, green sensitive layer

Silver chloroiodobromide emulsion EM4 (silver chloride: 1 mol%; 0.04

Silver iodide: 2.5 mol%; average grain size: 0.28 µm;

Size distribution 12%; cubic nuclear iodide type core/shell grains), spectrally sensitized with the green sensitizing dye (ExS-4)

Silver iodobromide emulsion EM5 (silver iodide: 2.8 mol%; average grain size: 0.45 µm; size distribution 12%; tabular grains) (ratio: 5), spectrally sensitized with the green sensitizing dye (ExS-4)

Gelatin 0.80

Magenta coupler (ExM-1) 0.10

Color Fade Preventing Agent (Cpd-9) 0.10

Stain preventive agent (Cpd-10) 0.01

Stain preventive agent (Cpd-11) 0.001

Stain preventive agent (Cpd-12) 0.01

Coupler dispersion medium (Cpd-5) 0.05

Coupler solvent (Solv-4) 0.15

Seventh layer: Highly sensitive, green-sensitive layer

Silver iodobromide emulsion EM6 (silver iodide: 3.5 mol%; average grain size: 0.9 µm; size distribution 23%; tabular, uniform, iodide-like grains (ratio: 9), spectrally sensitized with the green sensitizing dye (ExS-4)

Gelatin 0.80

Magenta coupler (ExM-1) 0.10

Color Fade Preventing Agent (Cpd-9) 0.10

Stain preventive agent (Cpd-10) 0.01

Stain preventive agent (Cpd-11) 0.001

Stain preventive agent (Cpd-12) 0.01

Coupler dispersion medium (Cpd-5) 0.05

Coupler solvent (Solv-4 and 6) 0.15

Eighth layer: yellow filter layer

Yellow colloidal silver 0.20

Gelatin 1.00

Color mixing inhibitor (Cpd-7) 0.06

Color Mixing Preventer Solvent (Solv-4) 0.15

Polymer latex (Cpd-8) 0.10

Ninth layer: Low sensitivity, blue-sensitive layer

Silver chloroiodobromide emulsion EM7 (silver chloride: 2 mol%; 0.07 silver iodide: 2.5 mol%; average grain size: 0.35 µm; size distribution: 8%; cubic, iodide-nucleated core/shell grains, spectrally sensitized with the blue sensitizing dye (ExS-5)

Silver iodobromide emulsion EM8 (silver iodide: 2.5 mol%; average grain size: 0.45 µm; size distribution 16%; tabular grains (aspect ratio: 6), spectrally sensitized: with the blue sensitizing dye (ExS-5)

Gelatin 0.50

Yellow coupler (ExY-1) 0.20

Stain preventive agent (Cpd-11) 0.001

Color Fade Preventing Agent (Cpd-6) 0.10

Coupler dispersion medium (Cpd-5) 0.05

Coupler solvent (Solv-2) 0.05

Tenth layer: Highly sensitive, blue-sensitive layer

Silver iodobromide emulsion EM9 (silver iodide: 2.5 mol%; average grain size: 1.2 µm; size distribution: 21%; tabular grains (aspect ratio: 14), spectrally sensitized with the blue sensitizing dye (ExS-5))

Gelatin 1.00

Yellow coupler (ExY-1) 0.40

Stain preventive agent (Cpd-11) 0.002

Color Fade Preventing Agent (Cpd-6) 0.10

Coupler dispersion medium (Cpd-5) 0.15

Coupler solvent (Solv-2) 0.10

Eleventh layer: ultraviolet light absorption layer

Gelatine 1.50

Ultraviolet light absorbers (Cpd-1, 3 and 13) 1.00

Color mixing preventive agents (Cpd-6 and 14) 0.06

Dispersion medium (Cpd-5)

Ultraviolet light absorber solvent (Solv-1 and 2) 0.15

Anti-irradiation dye (Cpd-15 and 16) 0.02

Anti-irradiation dye (Cpd-17 and 18) 0.02

Twelfth layer: protective layer

Fine silver chlorobromide grains (silver chloride: 97 mol%; 0.07 average grain size: 0.2 µm)

Modified Poval 0.02

Gelatine 1.50

Gelatin hardener H-1 0.17

Each of the layers contained Alkanol XC (manufactured by Dupont) and sodium alkylbenzenesulfonate as emulsification and dispersion aids and a succinic acid ester and Magefac F-120 (manufactured by Dai Nippon Ink and Chemical Co. Ltd.) as coating aids. In the layers containing silver halide or colloidal silver, stabilizers (Cpd-19, 20 and 21) were used.

The connections used in this example are shown below.

Solv-1 Di(2-ethylhexyl)phthalate

Solv-2 Trinonyl Phosphate

Solv-3 Di(3-methylhexyl)phthalate

Solv4 Tricresyl Phosphate

Solv-5 Dibutylphthalate

Solv-6 Trioctyl Phosphate

H-1 1,2-bis(vinylsulfonylacetamido)ethane

Samples 602 to 609 were prepared in the same manner as described for Sample 601, except that the amounts of the coupler solvent (Solv-4) and the magenta coupler (ExM-1) used in the sixth and seventh layers were changed to those used in Samples 502 to 509 of Example 5.

The thus obtained Samples 601 to 609 were uniformly exposed to blue and red light and further exposed to green light in a wedge-wise manner and then subjected to development processing according to the processing steps described below.

In the same manner as described in Example 3, the color tone and magenta stains were examined. Similar results to those of Example 5 were obtained.

The processing solutions used had the following compositions.

First development solution:

Pentasodium nitrilo-N,N,N-trimethylenephosphonate 0.6 g

Pentasodium diethylenetriamine pentaacetate 4.0 g

Potassium sulphite 30.0 g

Potassium thiocyanate 1.2 g

Potassium carbonate 35.0 g

Potassium hydroquinone monosulfonate 25.0 g

Diethylene glycol 15.0 ml

1-Phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 2.0 g

Potassium bromide 0.5 g

Potassium iodide 1.0 mg

Water to make 1 l (pH 9.70)

Color developing solution:

Benzyl alcohol 15.0 ml

Diethylene glycol 12.0 ml

3,6-Dithia-1,8-octanediol 0.2 g

Pentasodium nitrilo-N,N,N-trimethylenephosphonate 0.5 g

Pentrasodium diethylenetriaminepentaacetate 210 g

Sodium sulphite 2.0 g

Potassium carbonate 25.0 g

Hydroxylamine sulfate 3.0 g

N-Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4- 5.0 g aminoaniline sulfate

Potassium bromide 0.5 g

Potassium iodide 1.0 mg

Water to make 1 l (pH 10.40)

Bleach-fixing solution:

2-Mercapto-1,3,4-triazole 1.0 g

Disodium ethylenediaminetetraacetate dihydrate 5.0 g

Ammonium iron(III)ethylenediaminetetraacetate monohydrate 80.0 g

Sodium sulphite 15.0 g

Sodium thiosulfate (700 g/l solution) 160.0 ml

Glacial acetic acid 5.0 ml

Water to make 1 l

As described in detail above, when couplers according to the present invention were used, the magenta colors remained sharp even when the amount of the high boiling point organic solvent was reduced. Such an effect has not been known until now, and the present invention can achieve improvements in color reproducibility when pyrazolotriazole couplers are used, a decrease in staining when rapid processing is used, and improvement in sharpness due to a reduction in the amount of the high boiling point organic solvent.

Claims (15)

1. Use of at least one dye-forming coupler represented by the formula (I) or (II) as described below, optionally in combination with a high-boiling organic solvent having a weight ratio of the solvent to the coupler of not more than 1, to suppress magenta staining in a silver halide color photographic material comprising a support carrying at least one light-sensitive silver halide emulsion layer and at least one light-insensitive layer, wherein at least one layer of the light-sensitive silver halide emulsion layers contains the at least one dye-forming coupler represented by the general formula (I) or (II) and optionally the high-boiling organic solvent: wherein R₁ represents a branched alkyl group or an aryl group; R₂ represents a hydrogen atom or a substituent; X represents a hydrogen atom or a substituent released upon a coupling reaction with an oxidation product of an aromatic primary amine developing agent; A represents an oxygen atom, a nitrogen atom or a sulfur atom; and n represents 0 or 1. 2. Use according to claim 1, wherein a substituent for the branched alkyl group represented by R₁ is selected from a halogen atom, a hydroxy group, a cyano group, a carboxy group, a sulfo group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acylamino group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an alkylamino group, an anilino group, a carbamoylamino group, an alkoxycarbonylamino group, an acyloxy group and a sulfonyl group. 3. Use according to claim 1, wherein a substituent for the aryl group represented by R₁ is selected from a halogen atom, a hydroxy group, a cyano group, a carboxy group, a sulfo group, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acylamino group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkoxycarbamoyl group, an alkylamino group, an anilino group, a carbamoylamino group, an alkoxycarbonylamino group and a sulfonyl group. 4. Use according to claim 1, wherein the substituent represented by R₂ is a straight-chain or branched-chain alkyl group having 1 to 30 carbon atoms, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a Amino group, an anilino group, a heterocyclic amino group, an amido group, a urethane group, a ureido group, a sulfonamido group, an alkylthio group, an arylthio group, a sulfinyl group, a sulfonyl group, a sulfo group, a cyano group or a nitro group. 5. Use according to claim 4, wherein R₂ is a straight-chain or branched-chain alkyl group or an aryl group. 6. Use according to claim 1, wherein the substituent which can be released after the coupling reaction is selected from an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, a halogen atom and a nitrogen-containing heterocyclic group bonded to the nitrogen atom. 7. Use according to claim 1, wherein the dye-forming coupler is a compound as represented by the general formula (I). 8. Use according to claim 7, wherein R₁ is a branched alkyl group and n is 0. 9. Use according to claim 7, wherein R₁ is a branched alkyl group, A is an oxygen atom and n is 1. 10. Use according to claim 7, wherein R₁ is an aryl group, A is an oxygen atom and n is 1. 11. Use according to claim 1, wherein R₁ is a substituted or unsubstituted isopropyl group or a substituted or unsubstituted tert-butyl group. 12. Use according to claim 1, wherein R₁ is an aryl group having substituents at its 2- and 6-positions. 13. Use according to claim 1, wherein the dielectric constant of the organic solvent has a high boiling point of 5 or more. 14. Use according to claim 1, wherein the light-sensitive silver halide emulsion layer containing the dye-forming coupler is a green-sensitive silver halide emulsion layer and the color photographic light-sensitive silver halide material further contains at least one blue-sensitive silver halide emulsion layer containing at least one yellow coupler and at least one red-sensitive silver halide emulsion layer containing at least one cyan coupler. 15. Use according to claim 1, wherein the carrier is a reflective carrier.