JPH07175179A - Method for forming silver halide color rversal image - Google Patents

Abstract

PURPOSE:To provide the method for forming the color reversal image restrained from occurrence of streaks due to development processing accompanied by color reproduction improvement under rapid processing conditions. CONSTITUTION:The silver halide photographic sensitive material contains the compound represented by the formula in which R1 is aryl or tertiary alkyl; R2 is F, alkyl, aryl, alkoxy, aryloxy, dialkylamino, alkylthio, or arylthio; R3 is a group substitutable on the benzene ring; X is H or a group to be released by coupling with the oxidation product of an aromatic primary amine color developing agent; and p is an integer of 0-4, but when p is plural, each of plural R1 may be same or different. The photo-sensitive material has at least 3 protective layers, and the layers except the outermost and lowest layers of them contain nonphotosensitive silver halide grains in an amount of >=0.001mg/m<2>, and at least one layer lower than the group of the protective layers a scavenger for the oxidation product of the developing agent in an amount of 0.01mg/m<2>. The photosensitive material is subjected to black-and-white development within 80 sec and to reversal processing to form a color reversal image.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color reversal image forming method, and in particular, it has excellent rapid processability, good color reproducibility, and has reduced unevenness in density due to development processing. The present invention relates to a silver color reversal image forming method.

[0002]

2. Description of the Related Art How faithfully a finished color image can be reproduced with respect to an original photograph is largely dependent on the performance of a silver halide color photographic light-sensitive material. Therefore, studies on silver halide color photographic light-sensitive materials excellent in color reproduction have been conducted from various viewpoints. For example, when reproducing lemon yellow or bright green, they often have an orange or brownish green taste. The present inventors have continued to study a silver halide color photographic light-sensitive material improved in this respect.

The wide range of colors that can be reproduced in the finished color image depends on the used yellow, magenta,
And the absorption properties of cyan dyes. If the light absorption profile of the dye is broad or there is unwanted side absorption, color turbidity occurs. For example, in a yellow dye-forming coupler, attempts have been made to make the light absorption profile of the dye sharper and shorter, as disclosed in JP-A-63-123047 and JP-A-63-231451.
JP-A-63-241547, JP-A-1-213648,
And JP-A-1-250944. It has been found that the techniques described therein can produce a clear yellow dye image without turbidity, and remarkably improve the color reproduction of lemon yellow and bright green.

On the other hand, in recent years, there has been a strong demand to make the development process as simple and quick as possible. Therefore, some of the development steps are combined to reduce the processing bath. It accelerates the permeation of the processing solution by raising the development temperature or enhancing the stirring to accelerate the reaction, reduce the film thickness of the emulsion layer of the light-sensitive material and the coating silver amount. Alternatively, devises such as using a silver halide grain having a fast reaction and a coupler have been made. However, these measures for speeding up may adversely affect the image quality of the photographic light-sensitive material. For example, density unevenness and stains may easily occur.

The present inventor can improve the color reproduction by using the compound of the general formula [I], but at the same time, the rapid processing, that is, the black and white development time is 80%.
It was also found that the density unevenness and the stain are aggravated when the process is performed within seconds. Various attempts have been made to reduce this undesirable unevenness. For example, in a processing machine, in order to reduce temperature distribution and uneven stirring, a temperature control method, a liquid circulation method, a blowing direction and strength, and a shape of a roller and a guide have been actively made. Further, in light-sensitive materials as well, various measures have been taken such as incorporating a non-light-sensitive fine grain silver halide grain in the protective layer to incorporate a mechanism for capturing a substance that suppresses development.

A method of incorporating non-photosensitive fine grain silver halide grains into the protective layer is described in, for example, French Patent 912.
605, U.S. Patents 3,892,572 and 3,96.
1,963, 4607004, JP-A-63-30
1946, JP-A-1-107256 and 1-167.
No. 752 and No. 1-205163. The purpose of the non-photosensitive fine grain silver halide grains in these patents is to use a development inhibiting substance, particularly a halogen ion or a development inhibiting compound (D) which comes out from the photosensitive material during development.
It is intended to prevent the release group of the IR compound and the like) from being released into the developing solution and prevent the processing solution from being contaminated.

Further, JP-A-62-174755 and JP-A-6-174755.
No. 3-80248 and No. 63-80249, by using a specific additive in combination, the adverse effects that occur when non-photosensitive fine grain silver halide grains are used in a protective layer or the like for the same purpose as in the above patent are disclosed. It discloses that it can be reduced.
U.S. Pat. No. 3,737,317, JP-A-62-240963.
No. 63-281156, No. 63-304248 or JP-A No. 2-18550, the use of colloidal silver in any one of the protective layer groups in addition to the non-photosensitive fine grain silver halide grains provides the above-mentioned effects. In addition, it discloses that the release of silver ions can be suppressed. It is described that this makes it possible to prevent silver ions from accumulating in the treatment liquid and to reduce the generation of fogging and stains.

Further, JP-A-61-39043 discloses that when 75 mol% or more of non-photosensitive silver chlorobromide is used in the protective layer, stirring dependence during processing is improved and a preferable photographic gradation is obtained. There is disclosure. However, an experiment using the technology disclosed in these shows that some types of treatment unevenness are effective, but others have no effect, and that a failure that has never occurred until now occurs. , It was not enough to get a sufficient improvement effect.

[0009]

The object of the present invention is accompanied by a rapid process in which the black and white development time is within 80 seconds while improving the color reproduction, particularly lemon yellow and bright green color reproduction. It is to improve development processing streaks and the like. Further, it is to reduce the change in sensitivity even if a bleaching accelerator is mixed in the black and white developer, and to reduce the stirring dependency during development.

[0010]

The above-mentioned problems are solved by having a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer on a support, In the method of forming a color reversal image after black-and-white development of a silver halide color photographic light-sensitive material containing at least one yellow dye-forming coupler represented by the formula I], the light-sensitive material is farthest from the support. Having at least three non-image forming protective layers outside the forming layer,
At least one layer other than the outermost layer and the lowermost layer of the protective layer group contains 0.001 mg / m ² or more of non-photosensitive silver halide grains, and the non-photosensitive silver halide grain of the protective layer group is further contained. Halogen characterized by containing 0.01 mg / m ² or more of an oxidant scavenger of a developing agent in at least one layer lower than the layer containing, and having a black and white development processing step within 80 seconds after exposing the light-sensitive material. It has been found that this is achieved by a silver halide color reversal image forming method. General formula [I]

[0011]

[Chemical 2]

The compound represented by the general formula [I] used in the present invention will be described in more detail. In the general formula [I], R ₁ is preferably an aryl group having 6 to 24 carbon atoms (eg, phenyl, p-tolyl, o-tolyl, 4-methoxyphenyl, 2-methoxyphenyl, 4-butoxyphenyl, 4- Octyloxyphenyl, 4-hexadecyloxyphenyl, 1-naphthyl) or a tertiary alkyl group having 4 to 24 carbon atoms (for example, t-butyl, t-pentyl, t-hexyl, 1,1,3,3-tetra). Methylbutyl, 1-adamantyl, 1,1-dimethyl-2-chloroethyl, 2-phenoxy-2-propyl, bicyclo [2,2,2] octane-1-yl).

In the general formula [I], R ₂ is preferably a fluorine atom or an alkyl group having 1 to 24 carbon atoms (for example, methyl, ethyl, isopropyl, t-butyl, cyclopentyl, n-octyl, n-hexadecyl, benzyl). ), An aryl group having 6 to 24 carbon atoms (eg, phenyl, p-tolyl, o-tolyl, 4-methoxyphenyl), an alkoxy group having 1 to 24 carbon atoms (eg, methoxy, ethoxy, butoxy, n-octyloxy). , N-
Tetradecyloxy, benzyloxy, methoxyethoxy), an aryloxy group having 6 to 24 carbon atoms (for example, phenoxy, p-tolyloxy, o-tolyloxy, p
-Methoxyphenoxy, p-dimethylaminophenoxy, m-pentadecylphenoxy), 2 to 2 carbon atoms
A dialkylamino group of 4 (eg dimethylamino, diethylamino, pyrrolidino, piperidino, morpholino),
An alkylthio group having 1 to 24 carbon atoms (for example, methylthio, butylthio, n-octylthio, n-hexadecylthio) or an arylthio group having 6 to 24 carbon atoms (for example, phenylthio, 4-methoxyphenylthio, 4-t)
-Butylphenylthio, 4-dodecylphenylthio).

In the general formula [I], R ₂ is preferably a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) or an alkyl group having 1 to 24 carbon atoms (eg methyl, t-butyl, n-). Dodecyl), 6 to 24 carbon atoms
Aryl group (eg phenyl, p-tolyl, p-dodecyloxyphenyl), an alkoxy group having 1 to 24 carbon atoms (eg methoxy, n-butoxy, n-octyloxy, n-tetradecyloxy, benzyloxy, methoxy). Ethoxy), aryloxy groups having 6 to 24 carbon atoms (eg, phenoxy, pt-butylphenoxy, 4
-Butoxyphenoxy), an alkoxycarbonyl group having 2 to 24 carbon atoms [eg, ethoxycarbonyl, dodecyloxycarbonyl, 1- (dodecyloxycarbonyl) ethoxycarbonyl],

Aryloxycarbonyl group having 7 to 24 carbon atoms (for example, phenoxycarbonyl, 4-t-octylphenoxycarbonyl,, 2,4-di-t-pentylphenoxycarbonyl), carbonamide having 1 to 24 carbon atoms. Groups such as acetamide, pivaloylamino, benzamide, 2-ethylhexanamide, tetradecanamide, 1- (2,4-di-t-pentylphenoxy) butanamide, 3- (2,4-di-t-pentylphenoxy) butanamide, 3-dodecylsulfonyl-
2-Methylpropanamide], a sulfonamide group having 1 to 24 carbon atoms (for example, methanesulfonamide, p-toluenesulfonamide, hexadecanesulfonamide), a carbamoyl group having 1 to 24 carbon atoms (for example, N
-Methylcarbamoyl, N-tetradecylcarbamoyl, N, N-dihexylcarbamoyl, N-octadecyl-N-methylcarbamoyl, N-phenylcarbamoyl), an alkylsulfonyl group having 1 to 24 carbon atoms (for example, methylsulfonyl, benzylsulfonyl, Hexadecylsulfonyl),

Arylsulfonyl groups having 6 to 24 carbon atoms (eg phenylsulfonyl, p-tolylsulfonyl, p-dodecylsulfonyl, p-methoxysulfonyl), ureido groups having 1 to 24 carbon atoms (eg 3-methylureido, 3-phenylureido, 3,3-dimethylureido, 3-tetradecylureido), a sulfamoylamino group having 0 to 24 carbon atoms (for example, N, N-dimethylsulfamoylamino), and 2 to 24 carbon atoms. An alkoxycarbonylamino group of (eg, methoxycarbonylamino, isobutoxycarbonylamino, dodecyloxycarbonylamino),

A nitro group, a heterocyclic group having 1 to 24 carbon atoms (for example, 4-pyridyl, 2-thienyl, phthalimide,
Octadecylsuccinimide), cyano group, acyl group having 1 to 24 carbon atoms (eg acetyl, benzoyl, dodecanoyl), acyloxy group having 1 to 24 carbon atoms (eg acetoxy, benzoyloxy, dodecanoyloxy), 1 carbon atom To 24 alkylsulfonyloxy groups (for example, methylsulfonyloxy, hexadecylsulfonyloxy) or arylsulfonyloxy groups having 6 to 24 carbon atoms (for example, p-toluenesulfonyloxy, p-dodecylphenylsulfonyloxy).

In the general formula [I], p is preferably 1
Alternatively, it is an integer of 2. In the general formula [I], X is preferably a group capable of leaving by a coupling reaction with an oxidation product of an aromatic primary amine developing agent (referred to as a leaving group), specifically, a halogen atom (fluorine, chlorine). , Bromine, iodine), a heterocyclic group having 1 to 24 carbon atoms bonded to the coupling active position, an aryloxy group having 6 to 24 carbon atoms, an arylthio group having 6 to 24 carbon atoms (eg, phenylthio). , P-t-butylphenylthio, p-
Chlorophenylthio, p-carboxyphenylthio),
An acyloxy group having 1 to 24 carbon atoms (for example, acetoxy, benzoyloxy, dodecanoyloxy),

Alkylsulfonyloxy groups having 1 to 24 carbon atoms (eg methylsulfonyloxy, butylsulfonyloxy, dodecylsulfonyloxy), arylsulfonyloxy groups having 6 to 24 carbon atoms (eg benzenesulfonyloxy, p-chlorophenylsulfonyl). Oxy) or a heterocyclic oxy group having 1 to 24 carbon atoms (for example, 3-pyridyloxy, 1-phenyl-1,2,
3,4-tetrazol-5-yloxy), and more preferably a heterocyclic group or an aryloxy group bonded to the coupling active position with a nitrogen atom.

When X represents a nitrogen ring group bonded to the coupling active position by a nitrogen atom, X contains a hetero atom selected from oxygen, sulfur, nitrogen, phosphorus, selenium and tellurium in addition to the nitrogen atom. It may be a 5- to 7-membered optionally substituted monocyclic or condensed-ring heterocycle, examples of which include succinimide, maleimide, phthalimide, diglycolimide, pyrrole, pyrazole,
Imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2,4-dione, thiazolidine-2,4-dione, imidazolidine -2-on

Oxazolin-2-one, thiazoline-2
-One, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-
Pyrrolin-5-one, 2-imidazolin-5-one, indoline-2,3-dione, 2,6-dioxypurine,
Parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone,
There are 6-pyridazone, 2-pyrazone and the like, and these heterocyclic groups may be substituted. Examples of the substituent include a hydroxyl group, a carboxyl group, a sulfo group, an amino group (for example, amino, N-methylamino, N, N-dimethylamino, N, N-diethylamino, anilino, pyrrolidino,
In addition to (piperidino, morpholino), there are the substituents mentioned as examples of R ₃ .

When X represents an aryloxy group, X is an aryloxy group having 6 to 24 carbon atoms, and when X is a heterocyclic group, it is substituted with a group selected from the above-mentioned substituent group. May be. As the substituent, a carboxyl group, a sulfo group, a cyano group, a nitro group, an alkoxycarbonyl group, a halogen atom, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkyl group, an alkylsulfonyl group, an arylsulfonyl group or an acyl group. Is preferred.

Next, examples of the substituents particularly preferably used in the present invention for each of the substituents R ₁ , R ₂ , R ₃ and X described above will be described. In the general formula [I], R ₁ is particularly preferably a 2 or 4-alkoxyaryl group (for example, 4-methoxyphenyl, 4-butoxyphenyl, 2-methoxyphenyl) or t-butyl group, and t-butyl group is Most preferred.

In the general formula [I], R ₂ is particularly preferably a methyl group, an ethyl group, an alkoxy group, an aryloxy group or a dialkylamino group, and a methyl group, an ethyl group, an alkoxy group, an aryloxy group or dimethylamino. Most preferred are groups. In the general formula [I], R ₃
Is particularly preferably an alkoxy group, a carbonamido group or a sulfonamide group.

In the general formula [I], X is particularly preferably a heterocyclic group or an aryloxy group which is bonded to the coupling active position with a nitrogen atom. When X represents the above heterocyclic group, X is preferably represented by the following general formula [III].

[0026]

[Chemical 3]

Here, R ₈ , R ₉ , R ₁₂ and R ₁₃ are hydrogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkylsulfonyl groups, arylsulfonyl groups or amino groups. R ₁₀ and R ₁₁ represent a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group or an alkoxycarbonyl group, and R ₁₄ and R ₁₅ represent a hydrogen atom, an alkyl group or an aryl group. R ₁₄ and R ₁₅ may combine with each other to form a benzene ring.

R ₈ and R ₉ , R ₉ and R ₁₀ , R ₁₀ and R ₁₁ or R ₈ and R ₁₂ combine with each other to form a ring (eg cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine, piperidine). May be. Among the heterocyclic groups represented by the general formula [III], a particularly preferred one is Z in the general formula [III].

[0029]

[Chemical 4]

Is a heterocyclic group which is The total number of carbon atoms of the heterocyclic group represented by the general formula [III] is 2 to 24, preferably 4 to 20 and more preferably 5 to 16. General formula
Examples of the heterocyclic group represented by [III] include succinimide group, maleinimide group, phthalimido group, 1-methylimidazolidin-2,4-dione-3-yl group, 1-benzylimidazolidine-2,4-dione. -3-yl group,
5,5-dimethyloxazolidine-2,4-dione-3
-Yl group, 5-methyl-5-propyloxazolidine-
2,4-dione-3-yl group, 5,5-dimethylthiazolidin-2,4-dione-3-yl group, 5,5-dimethylimidazolidin-2,4-dione-3-yl group, 3-
A methylimidazolidintrion-1-yl group,

1,2,4-triazolidine-3,5-dione-4-yl group, 1-methyl-2-phenyl-1,
2,4-triazolidine-3,5-dione-4-yl group, 1-benzyl-2-phenyl-1,2,4-triazolidine-3,5-dione-4-yl group, 5-hexyloxy-1 -Methylimidazolidine-2,4-dione-
3-yl group, 1-benzyl-5-ethoxyimidazolidin-2,4-dione-3-yl group, 1-benzyl-5-
Dodecyloxyimidazolidine-2,4-dione-3-
There is an yl group.

Among the above heterocyclic groups, imidazolidine-
The 2,4-dione-3-yl group (eg, 1-benzyl-imidazolidin-2,4-dione-3-yl group) is the most preferred group.

When X represents an aryloxy group, 4-
Carboxyphenoxy group, 4-methylsulfonylphenoxy group, 4- (4-benzyloxyphenylsulfonyl) phenoxy group, 4- (4-hydroxyphenylsulfonyl) phenoxy group, 2-chloro-4- (3-chloro-4-hydroxy) Phenylsulfonyl) phenoxy group,
4-methoxycarbonylphenoxy group, 2-chloro-4
-Methoxycarbonylphenoxy group,

2-acetamido-4-methoxycarbonylphenoxy group, 4-isopropoxycarbonylphenoxy group, 4-cyanophenoxy group, 2- [N- (2-hydroxyethyl) carbamoyl] phenoxy group, 4-nitrophenoxy group, 2,5-dichlorophenoxy group,
The 2,3,5-trichlorophenoxy group, the 4-methoxycarbonyl-2-methoxyphenoxy group, and the 4- (3-carboxypropanamide) phenoxy group are the most preferable examples.

The coupler represented by the general formula [I] has substituents R ₁ , X or

[0036]

[Chemical 5]

In the above, a dimer or a multimer having a valence of two or more may be bonded to each other to form a multimer or more. In this case, the number of carbon atoms shown in each of the above substituents may be out of the specified range.

When the coupler represented by the general formula [I] forms a multimer, an addition polymer having a yellow dye-forming coupler residue is a homopolymer or copolymer of an ethylenically unsaturated compound (yellow color-forming monomer). Here is an example. In this case, the multimer contains a repeating unit represented by the general formula [IV], and one or more kinds of yellow color-forming repeating units represented by the general formula [IV] may be contained in the multimer, and the repeating unit is a non-copolymerizing component. It may be a copolymer containing one kind or two or more kinds of color forming ethylene type monomers.

[0039]

[Chemical 6]

In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, and A represents -CONH-, -C.
OO- or a substituted or unsubstituted phenylene group, B represents a substituted or unsubstituted alkylene group, a phenylene group or an aralkylene group, L represents -CONH-,
-NHCONH-, -NHCOO-, -NHCO-,-
OCONH-, -NH-, -COO-, -OCO-,-
CO -, - O -, - S -, - SO 2 -, - NHSO 2 -
Or it represents a -SO ₂ NH-. a, b, and c represent 0 or 1. Q is R ₁ , X of the compound represented by the general formula [I] or

[0041]

[Chemical 7]

A yellow coupler residue from which a hydrogen atom has been removed is shown. As the multimer, a copolymer of a yellow color-forming monomer represented by the coupler unit of the general formula [IV] and the following non-color-forming ethylene-like monomer is preferable.

As the non-color forming ethylene type monomer which is not coupled with the oxidation product of the aromatic primary amine developing agent,
Acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (for example, methacrylic acid) An amide or ester derived from these acrylic acids (for example, acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, dimethacrylate) Acetone acrylamide, methyl acrylate, ethyl acrylate,
n-propyl acrylate,

N-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), vinyl ester (Eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citracone Acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg vinyl ethyl ether), maleic acid ester, N Vinyl-2-pyrrolidone, is N- vinylpyridine and 2- and 4-vinylpyridine.

Acrylic acid esters, methacrylic acid esters and maleic acid esters are particularly preferred. Two or more kinds of non-color-forming ethylene type monomers used here can be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

As well known in the field of polymer couplers, the ethylenically unsaturated monomer for copolymerization with the vinyl monomer corresponding to the above-mentioned formula [IV] has physical properties of the copolymer and / or Or a chemical property, such as solubility, compatibility of the photographic colloid composition with a binder such as gelatin,
It can be chosen such that its flexibility, thermal stability, etc. are positively affected.

The yellow polymer coupler used in the present invention is obtained by dissolving a lipophilic polymer coupler obtained by polymerization of a vinyl-type monomer which gives the coupler unit represented by the above general formula [IV] in an organic solvent to prepare an aqueous gelatin solution. It may be emulsified and dispersed in the form of latex therein, or may be directly emulsified by an emulsion polymerization method.

A method of emulsion-dispersing a lipophilic polymer coupler in an aqueous gelatin solution is described in US Pat. No. 3,451,820, and an emulsion polymerization is described in US Pat. Nos. 4,080,211 and 3,370,952. The method described in the publication can be used. Specific examples of the yellow dye-forming couplers R ₃ and X represented by the general formula [I] are shown below, but the invention is not limited thereto. Specific examples of X are shown below.

[0049]

[Chemical 8]

[0050]

[Chemical 9]

[0051]

[Chemical 10]

[0052]

[Chemical 11]

Specific examples of R ³ are shown below.

[Chemical 12]

[0054]

[Chemical 13]

The yellow coupler represented by the general formula [I] is preferably a compound represented by the following general formula [II]. General formula (II)

[0056]

[Chemical 14]

[In the formula, R ₄ represents an alkyl group, a cycloalkyl group, an acyl group or an aryl group, and R ₅ represents a group capable of substituting on the benzene ring. n represents 0 or 1. R
₆ represents an organic group containing one bonding group having a carbonyl or sulfonyl unit, and J is

[0058]

[Chemical 15]

In the general formula [II], the alkyl group and cycloalkyl group represented by R ₄ include the same groups as R _1, and the aryl group includes, for example, a phenyl group. The alkyl group, cycloalkyl group, and aryl group represented by R ₄ include those having the same substituents as R ₁ . Moreover, examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a hexanoyl group, and a benzoyl group. R ₄ is preferably an alkyl group or an aryl group, and more preferably an alkyl group.

In the general formula [II], the group capable of substituting on the benzene ring represented by R ₅ includes a halogen atom (eg chlorine atom), an alkyl group (eg ethyl group, i-propyl group, t-butyl group). ), Alkoxy group (eg methoxy group), aryloxy group (eg phenyloxy group), acyloxy group (eg methylcarbanyloxy group, benzoyloxy group), acylamino group (eg acetamide group, phenylcarbonylamino group), carbamoyl group (Eg N-methylcarbamoyl group, N-phenylcarbamoyl group), alkylsulfonamide group (eg ethylsulfonylamino group), arylsulfonamide group (eg phenylsulfonylamino group), sulfamoyl group (eg N-propylsulfamoyl group) , N
-Phenylsulfamoyl group) and imide group (for example, succinimide group, glutarimide group) and the like. n represents 0 or 1.

In the general formula [II], R ₆ represents an organic group containing one bonding group having a carbonyl or sulfonyl unit. Examples of the group having a carbonyl unit include an ester group, an amide group, a carbamoyl group, a ureido group, and a urethane group.
Examples thereof include a sulfone group, a sulfonamide group, a sulfamoyl group and an aminosulfonamide group. J is

[0062]

[Chemical 16]

[0063] represents, R ₇ is a hydrogen atom, an alkyl group,
It represents an alkyl group, an aryl group or a heterocyclic group. Examples of the alkyl group represented by R ₇ include a methyl group, an ethyl group, an isopropyl group, a t-butyl group and a dodesyl group. Examples of the aryl group represented by R ₇ include a phenyl group and a naphthyl group. The alkyl group, aryl group or heterocycle represented by R ₇ includes those having a substituent. R ₁ and X are the same as in the general formula [I]. Specific examples of the yellow dye-forming coupler represented by the formula [I] are shown below. Specific examples are represented by the methods specifically shown in Tables 1 and ₂ for R ₁ , R ₂ , (R ₃ ) _p and X in the following general formula [I].

[0064]

[Chemical 17]

[0065]

[Table 1]

[0066]

[Table 2]

In the table, the numbers in parentheses are the same as those of X and R above.
_It represents the number given to the specific example of ₃ , and the number in [] represents the substitution position on the anilide group. The couplers of the present invention may be used alone or in combination of two or more, or may be used in combination with a known yellow dye-forming coupler. The coupler of the present invention can be used in any layer of the light-sensitive material, but is preferably used in the light-sensitive silver halide emulsion layer or its adjacent layer, and most preferably used in the light-sensitive silver halide emulsion layer.

The coupler of the present invention can be synthesized by a conventionally known synthesis method, and a specific example thereof is the synthesis method described in JP-A-63-123047. The amount of the coupler of the present invention used in the light-sensitive material is 1 × 10 ^-5 mol to 10 ^-2 mol per m ² , preferably 1
× 10 ^-4 mol to 5 × 10 ^-3 mol, more preferably 2 × 1
It is 0 ⁻⁴ mol to 10 ⁻³ mol.

The non-photosensitive silver halide grains contained in the protective layer of the present invention may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide or silver iodobromide. Silver or silver chlorobromide is preferred. Further, silver chlorobromide or silver chloride containing 70 mol% or more of silver chloride is particularly preferable. The grain shape of the silver halide may be any of cubic, tetradecahedral, octahedral, spherical, tabular or amorphous, and particularly cubic, tetrahedral,
Regular grains such as octahedron or tabular grains having an aspect ratio of 5 or more are preferred. The grain size distribution may be either monodisperse or polydisperse, but a monodisperse emulsion having a grain size distribution of 20% or less is preferable. The particle size distribution referred to here is "Theory of Photographic Processes," James, 4th.
Edition, Chapter 3, page 102.

The non-photosensitive silver halide refers to grains having extremely low sensitivity or uniformly developed regardless of exposure amount. The term "sensitivity is extremely low" as used herein means a silver halide grain having a photosensitivity of less than 1/10 of the minimum sensitivity of the photosensitive silver halide grain contained in the image forming layer of the light-sensitive material. To tell.

Silver halide having extremely low sensitivity to light can be prepared by the following three methods. The first method is a method of preparation without chemical sensitization treatment after grain formation. The second method is to cover the inside of the silver halide grain. For example, such particles can be prepared by dividing the particle formation into two or more steps, and subjecting the surface of the core particle to a fogging treatment such as a strong action of a reducing agent, followed by shell formation. The third method is a method in which a heavy metal salt is allowed to act during the formation of particles. The water-soluble rhodium salt is most preferably used as the metal salt. As the water-soluble rhodium salt, rhodium chloride, rhodium trichloride, rhodium ammonium chloride or the like is used, but a complex salt can also be used. The addition amount of the rhodium salt in the present invention is preferably 1 × 10 ⁻⁶ mol or more per mol of silver,
Further, the range of 5 × 10 ⁻⁵ to 1 × 10 ⁻³ mol is particularly preferable. Each of these three methods may be used alone or 2
It is also possible to use three kinds of methods together.

Particles which are uniformly developed regardless of the amount of light and the amount of exposure can be prepared by strongly reducing the surface of the particles. For example, particles with high pH or low pAg
Method of heating under the conditions of, method of adding reducing agent or gold salt,
Alternatively, it can be prepared by a method of giving uniform exposure. As the reducing agent, stannous chloride, a hydrazine compound, ethanolamine, thiourea dioxide or the like can be used.

In the present invention, a sensitizing dye may be adsorbed on the surface of the silver halide grain, or various compounds may be adsorbed as additives to stabilize the performance. A useful sensitizing dye is German Patent 929,0.
80, U.S. Pat. Nos. 2,493,748 and 2,50
3,776, 2,519,001, 2,91
No. 2,329, No. 3,656,959, No. 3,67
2,897, 3,694,217, 4,02
5, 349, 4,046, 572, and the like. As additives, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles; heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles , Mercaptothiazoles, mercaptotetrazoles, mercaptopyrimidines: the above-mentioned heterocyclic mercapto compounds having a carboxyl group or a sulfone group; thioketo compounds such as oxazoline thione; azaindenes such as tetrazaindenes (especially 4-hydroxy substitution (1, Compounds known as stabilizers such as 3,3a, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; and the like can be used.

The coating amount of the silver halide contained in the protective layer is preferably 0.001 g / m ² to 0.5 g / m ^2, more preferably 0.01 g / m ² to 0.2 g / m ^{2 in} terms of silver amount. Is particularly preferable. The grain size of the silver halide is 0.0
2 to 0.5 μm is preferable, and further 0.05 to 0.
3 μm is particularly preferable. The total dry thickness of the protective layers is preferably 6 μm or less, more preferably 3 μm or less. Particularly, 2.5 to 1.5 μm is preferable. The dry film thickness of the layer containing the silver halide grains in the protective layer group is preferably 30% or less, more preferably 15% or less of the total film thickness of the protective layer. The thickness of the layer located below the layer containing the silver halide grains in the protective layer group and containing the oxidant scavenger of the developing agent is preferably 20% or more and more preferably 40% of the total thickness of the protective layer. The above is preferable.

In the present invention, the protective layer means a non-image forming layer outside the photosensitive image forming layer farthest from the support in the photosensitive material. When the number of non-image forming layers is 2 or more, the whole is called a protective layer group. The representative constitution of the protective layer group according to the present invention is composed of three layers. When the support side is the A layer, the B layer and the C layer, the B layer contains silver halide grains and the A layer is an oxidant scan of the developing agent. It contains a venger and the C layer consists of a protective colloid layer. Each of the A, B, and C layers may be a single layer or a plurality of layers. An intermediate layer made of protective colloid may be provided between the layers.

It is preferable that the layer A contains an ultraviolet absorber in addition to an scavenger of an oxidized product as a developing agent. In addition to silver halide grains, layer B can contain an ultraviolet absorber and an oxidant scavenger of a developing agent. The C layer may contain a matting agent to prevent adhesion, a surfactant (fluorine-based surfactant or the like) to prevent static electricity, and a polymer (modified Poval or the like) to improve film quality.

The oxidant scavenger of the developing agent (hereinafter referred to as "ND compound") which can be used in the present invention can donate at least one electron to (A) the oxidant (T ⁺ ) of the color developing agent. An electron donor (ED), such as
(B) Colorless couplers which form a colorless compound by coupling with T ⁺ . A preferred ED compound has a partial structure represented by the following general formula.

[0078]

[Chemical 18]

Here, n is an integer of 1 to 4, preferably 1 or 2, and Z ¹⁰¹ and Z ¹⁰² are independently -O.
^{_{H, -NH 2, -NHR 101,}} -NR 102 R 103, -N
Represents HSO ₂ R ¹⁰⁴ . R ¹⁰¹ is an alkyl group, R ¹⁰²
And R ¹⁰³ represents an alkyl group or an atomic group forming a heterocycle containing nitrogen together with R ¹⁰² and R ¹⁰³ ;
¹⁰⁴ represents an alkyl group or an aryl group. N here
When is 1,> C = C <may represent a partial structure of a benzene ring or a naphthalene ring.

The alkyl group represented by R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ may be substituted, and examples of the substituent include a halogen atom and an alkoxy group. The alkyl group includes straight-chain or branched alkyl groups and preferably has 1 to 5 carbon atoms. The aryl group represented by R ¹⁰⁴ also includes those having a substituent, and examples thereof include phenyl, alkoxy-substituted phenyl, and alkyl-substituted phenyl. Examples of the nitrogen-containing heterocycle formed by R ¹⁰² and R ¹⁰³ in combination include morpholino, piperidino and piperazino groups.

Preferred among the EDs represented by the general formula [XI] are hydroquinone compounds, catechol compounds, o-aminophenol compounds and p-aminophenol compounds. The hydroquinone compound that can be used as the ED compound in the present invention is preferably incorporated into the photosensitive layer and has low diffusivity. Such a hydroquinone compound is widely used as a color mixture preventing agent or a color fog preventing agent, usually in a color sensitive material or a diffusion transfer color sensitive material.

US Pat. Nos. 2,728,659 and 2,
732,300 and 3,243,294, the linear alkyldi-substituted hydroquinones described in US Pat.
732, 300, 3,243, 294, 3,700, 453, JP-A-52-4819, 5
The branched alkyldi-substituted hydroquinones described in 4-29637 are preferred hydroquinones because of their low potential and high activity as T ⁺ scavengers.

Mono-linear alkylhydroquinones described in US Pat. Nos. 2,728,659 and 3,960,570, US Pat.
9-106329 and 50-156438, monobranched alkyl hydroquinones, JP-A-56-109.
344, U.S. Pat. Nos. 4,345,616 and 4,27.
The hydroquinones described in No. 7,553 are also EDs of the present invention.
Can be used as

Specific examples of preferred dialkylhydroquinones that can be used in the present invention are shown below. Q-1 2,5-di-n-octyl hydroquinone Q-2 2,5-di-n-dodecyl hydroquinone Q-3 2,6-di-n-octyl hydroquinone Q-4 2,5-di-t- Pentadecyl hydroquinone Q-5 2,5-di-sec-dodecyl hydroquinone Q-6 2,5-di-t-dodecyl hydroquinone Q-7 2,5-di-sec-octyl hydroquinone Q-8 2,5-di -T-octylhydroquinone Q-9 2,6-di-t-octylhydroquinone The preferred ED for use in the present invention is represented by the following general formula [X1
It is represented by I] and [XIII].

[0085]

[Chemical 19]

Alkyl ester of gallic acid represented by the formula (wherein R ²⁰¹ is a straight-chain or branched-chain alkyl group having 1 to 18 carbon atoms): One example thereof is as follows. A1 gallic acid methyl ester A2 gallic acid ethyl ester A3 gallic acid n-propyl ester A4 gallic acid isopropyl ester A5 gallic acid n-butyl ester A6 gallic acid isoamyl ester A7 gallic acid d-amyl ester A8 gallic acid n-hexyl ester

A9 gallic acid n-heptyl ester A10 gallic acid n-octyl ester A11 gallic acid n-nonyl ester A12 gallic acid n-decyl ester A13 gallic acid n-hendecyl ester A14 gallic acid n-dodecyl ester A15 gallic acid n -Tetradecyl ester A16 Gallic acid n-hexadecyl ester A17 Gallic acid n-octadecyl ester

[0088]

[Chemical 20]

Here, R ³⁰¹ and R ³⁰² each represent a hydrogen atom, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted heterocycle. Further, R ³⁰¹ and R ³⁰² may form a ring. R ³⁰¹ and R ³⁰² do not simultaneously take a hydrogen atom. In the general formula [XIII],
^Examples of the aliphatic group of R ³⁰¹ and R ³⁰² include a linear or branched alkyl group, a linear or branched alkenyl group, a cycloalkyl group, and a linear or branched alkynyl group.

The linear or branched alkyl group has 1 to 30, preferably 1 to 20 carbon atoms. For example, methyl, ethyl, propyl, n-butyl, sec-butyl,
t-butyl, n-hexyl, 2-ethylhexyl, n-
Examples thereof include octyl, t-octyl, n-dodecyl, n-hexadecyl, n-octadecyl, isostearyl or eicosyl.

The linear or branched alkenyl group has 2 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and examples thereof include allyl, butynyl, prenyl, octenyl, dodecenyl and oleyl. The cycloalkyl group has 3 to 12 members, preferably 5 to
7-membered ones, such as cyclopropyl, cyclopentyl,
Examples thereof include cyclohexyl, cycloheptyl and cyclododecyl.

The linear or branched alkynyl group has 3 to 30 carbon atoms, preferably 3 to 22 carbon atoms,
Examples include propargyl or butynyl. R
^Examples of the aromatic group of ³⁰¹ and R ³⁰² include phenyl and naphthyl. Examples of the hetero ring of R ³⁰¹ and R ³⁰² include thiazolyl, oxazolyl, imidazolyl, furyl, thienyl, tetrahydrofuryl, piperidyl, thiadiazolyl, oxadiazolyl, benzothiazolyl, benzoxazolyl and benzimidazolyl.

Examples of the ring formed by R ³⁰¹ and R ³⁰² include those having a member number of 3 to 12, preferably 5 to 12, such as ethylene, tetramethylene, pentamethylene, hexamethylene or dodecamethylene.

Further, each of these groups may have an appropriate substituent, and examples of the substituent include an alkoxy group, an aryloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom and a carboxy group. Group, sulfo group, cyano group, alkyl group, alkenyl group, aryl group, alkylamino group, arylamino group, carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, acyl group, sulfonyl group, acyloxy group and acylamino group. To be

Specific examples of the compound represented by the general formula [XIII] are shown below, but the invention is not limited thereto. Compound example

[0096]

[Chemical 21]

[0097]

[Chemical formula 22]

[0098]

[Chemical formula 23]

[0099]

[Chemical formula 24]

[0100]

[Chemical 25]

[0101]

[Chemical formula 26]

[0102]

[Chemical 27]

[0103]

[Chemical 28]

[0104]

[Chemical 29]

[0105]

[Chemical 30]

Particularly preferred ED compounds for use in the present invention are the compounds of the following general formula [XIV].

[0107]

[Chemical 31]

In the formula, R ⁴⁰¹ and R ⁴⁰² each represent a hydrogen atom or a group hydrolyzable by an alkali and may be the same or different. R ⁴⁰³ , R ⁴⁰⁴ and R ⁴⁰⁵ represent a hydrogen atom, a sulfo group, a carboxyl group, a sulfoalkyl group, a carboxyalkyl group and an alkyl group, respectively.
At least one of R ⁴⁰³ , R ⁴⁰⁴ , and R ⁴⁰⁵ is a group selected from a sulfo group, a carboxyl group, a sulfoalkyl group, and a carboxyalkyl group, and at least one is an alkyl group.

In the above general formula [XIV], R ⁴⁰¹ ,
When R ⁴⁰² is a group that can be hydrolyzed by an alkali, examples thereof include an acetyl group, a trichloroacetyl group, an ethoxycarbonyl group and a benzoyl group. Also R
^{When 403} , R ⁴⁰⁴ and R ⁴⁰⁵ are sulfoalkyl groups, examples thereof include a 1,1-dimethyl-2-sulfoethyl group,
When it is a carboxyalkyl group, it is a 5-carboxypentyl group, and when it is an alkyl group, it is a methyl group, ethyl group, t-octyl group, n-octyl group, sec-dodecyl group, n-pentadecyl group. , Sec-octadecyl group and the like.

In formula [XIV], hydrogen atoms are preferred as R ⁴⁰¹ and R ⁴⁰² , and R ⁴⁰³ , R ⁴⁰⁴ and R ⁴⁰² are preferred.
^{As 405} , a sulfo group and an alkyl group are preferable. Furthermore,
R ⁴⁰⁵ represents a sulfo group or a carboxyl group, and R ⁴⁰³ ,
More preferably, one of R ⁴⁰⁴ is an alkyl group and the other is a hydrogen atom.

Most preferably, R ⁴⁰³ is a hydrogen atom,
^This is the case where ⁴⁰⁴ is an alkyl group and R ⁴⁰⁵ is a sulfo group. Compounds of general formula [XIV] are described in British Patent 891,1
No. 58, US Pat. No. 2,701,197 and the like, and methods analogous thereto. The specific examples of the compounds of the general formula [XIV] used in the present invention are shown below, but the present invention is not limited thereto.

[0112]

[Chemical 32]

[0113]

[Chemical 33]

[0114]

[Chemical 34]

[0115]

[Chemical 35]

[0116]

[Chemical 36]

The non-color-forming coupler used as the ND compound in the present invention means that a colored dye, which is coupled with an oxidized product of a color developing agent but remains in a leuco form, is once formed, As a result, it is a coupler that does not form a colored dye in the light-sensitive material layer due to the reasons that it decomposes in the after-treatment bath and becomes colorless, and that the formed colored elements are dissolved in the processing solution due to its water solubility.

These colorless couplers are disclosed in the following documents. Couplers in which the hydrogen atom of the active methylene, such as pyrazolone, benzoyl acetate, benzoyl acetate anilide, acetoacetanilide, etc., is substituted with a substituted alkyl or substituted allyl group, as described in British Patent 914,145; 1,28
4-649 of pyrazolones as described in US Pat.
A coupler in which the position is substituted with a methyl group, an ethyl group, or a cyanoethyl group; the 4-position is substituted with an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, as described in JP-A-50-83031. , 3-position substituted with a substituted acylamide, improved coupling activity,
All 5-pyrazolone type couplers belong to the above type.

Further, as belonging to the above, an acyclic ketone type non-coloring DIR coupler as described in JP-B-46-22514 or JP-B-51-16.
141, a cyclic ketone type colorless D
There are IR couplers, and those belonging to
There are couplers described in US Pat. No. 2,742,832. The ND compound is contained in the protective layer below the layer containing the non-photosensitive silver halide grains, but the addition amount is preferably 0.01 mg / m ² or more, more preferably 0.1 mg / m ² or more.

Preferred silver halides contained in the photosensitive emulsion layer of the photographic light-sensitive material used in the present invention are silver iodobromide, silver iodochloride, silver iodochlorobromide, silver bromide and silver chlorobromide. It may be any of silver chloride. However, silver iodobromide, silver iodochloride or silver iodochlorobromide containing less than about 30 mol% silver iodide is preferred.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, and irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof. The grain size of silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No1.
7643 (Dec. 1978), pp. 22-23, "I.
(Emulsion preparation and types), and No. 18716 (November 1979), p.648, "The Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Glafkides, Chemie et Phisique Photographique, Pa.
ul Montel, 1967), "Photoemulsion Chemistry" by Duffin,
Published by Focal Press (GFDuffin, Photographic Emul
sion Chemistry (Focal Press, 1966)), "Manufacturing and coating of photographic emulsions" by Zelikman et al., published by Focal Press (VLZelikman et al., Making and Coating Photogr
aphic Emulsion, Focal Press, 1964) and the like.

US Pat. Nos. 3,574,628 and 3,
655,394 and British Patent 1,413,748.
The monodisperse emulsions described in JP-A No. 1989-2000 are also preferable. Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutof, Photographic Science and Engineering (Gutof
f, Photographic Science and Engineering), 14th
Volume 248-257 (1970); U.S. Pat. No. 4,
No. 434, 226, No. 4,414, 310, No. 4, 4
It can be easily prepared by the method described in 33,048, 4,439,520 and British Patent 2,112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and silver halide having different compositions may be bonded by epitaxial bonding. May be
Further, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide.

Further, a mixture of grains having various crystal forms may be used. As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such a process are described in Research Disclosure No. 17643 and No. 18716, and the corresponding portions are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table. Additive type RD17643 RD18716 1 Chemical sensitizer Page 23 Page 648 Right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, Page 23 to 24 Page 648 Right column to Supersensitizer page 649 Right column 4 Whitening agent 24 Page 5 Antifoggant, pages 24 to 25, page 649, right column ~ and stabilizer 6 Light absorber, pages 25 to 26, page 649, right column ~ Filter dye, page 650, left column UV absorber 7 Stain inhibitor, page 25, right column Page 650 Left to right column 8 Dye image stabilizer page 25 9 Hardener 26 page 651 Page left column 10 Binder page 26 Same as above 11 Plasticizer, lubricant 27 page 650 Right column 12 Coating aid, pages 26 to 27 Same as above Surfactant 13 Antistatic agent Page 27 Same as above

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,98
It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with the formaldehyde described in No. 7 and No. 4,435,503. Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure (RD) No. 17643, VII-mentioned above.
It is described in the patents described in C to G.

The yellow coupler is represented by the general formula [I]
With a compound represented by, for example, US Pat.
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401,752, No. 4,
No. 248,961, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020 and 1,476,760.
U.S. Pat. Nos. 3,973,968 and 4,31
Those described in 4,023, 4,511,649, European Patent 249,473A and the like may be used.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No 24220 (June 1984),
JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-4
No. 3659, No. 61-72238, No. 60-3573.
No. 0, No. 55-118034, No. 60-185951
U.S. Pat. Nos. 4,500,630 and 4,54
0,654, 4,556,630, International Publication W
Those described in O88 / 04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, No. 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
Issue No. 4,775,616, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable.

Colored couplers for correcting unwanted absorption of color forming dyes are Research Disclosure No. 1
7643, Section VII-G, U.S. Pat. No. 4,163,670.
No. 57/39413, U.S. Pat. No. 4,000
Those described in 4,929, 4,138,258 and British Patent 1,146,368 are preferable. Also,
The coupler described in US Pat. No. 4,774,181 which corrects unnecessary absorption of a coloring dye by the fluorescent dye released during coupling, and the reaction with the developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable. Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910 and British Patent 2,102,173.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler which releases the development inhibitor is the above-mentioned R
Patents described in D17643, VII to F, JP-A-5
7-151944, 57-154234, 60
-184248, 63-37346, 63-3
7350, U.S. Pat. Nos. 4,248,962 and 4,7.
Those described in No. 82,012 are preferable. As couplers that release a nucleating agent or a development accelerator imagewise during development, British Patents 2,097,140 and 2,2
131,188, JP-A-59-157638 and JP-A-5-157638.
Those described in 9-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,42.
Competitive couplers described in US Pat.
No. 472, No. 4,338,393, No. 4,31
Multiequivalent couplers described in JP-A No. 0,618, JP-A-60-
No. 185950, JP-A No. 62-24252, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent Nos. 173,302A, 313,308A. A coupler which releases a dye which returns color after the separation described in No. D.
No. 11449, No. 24241, JP-A-61-20124
No. 7, etc., a bleaching accelerator releasing coupler, a ligand-releasing coupler as described in US Pat. No. 4,553,477, etc., a leuco dye-releasing coupler as described in JP-A-63-75747, US Pat. Examples thereof include couplers that release the fluorescent dye described in 4,774,181.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,222.
No. 027 and the like.

Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used for the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate,
Decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or Esters of phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate,
Tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate, etc.),

Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide, N, N-diethyllaurylamide, N-tetradecyl) Pyrrolidone),
Alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.),
Aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-butoxy-5-) tert-octylaniline) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like.

The auxiliary solvent may be an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower. Typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone. , 2-ethoxyethyl acetate, dimethylformamide and the like.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230.

In the color light-sensitive material of the present invention, Japanese Patent Laid-Open No.
No. 3,257,747, No. 62-272248, and 1,2-benzisothiazolin-3-one, n-butyl, p-hydroxybenzoate, phenol, 4-chloro-3,5 described in JP-A-1-80941. -It is preferable to add various antiseptics or antifungal agents such as dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole.

The present invention can be applied to various color reversal light-sensitive materials. When the present invention is applied to color reversal paper, the effect of the present invention becomes remarkable. Suitable supports that can be used in the present invention include, for example, RD, No176 described above.
No. 43, page 28, and No. 18716, page 647, right column to page 648, left column.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 20 μm or less.
m or less is more preferable. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness is
Means the film thickness measured under the condition of 25 ° C. and 55% relative humidity (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art.

For example, A. Green et al., Photographic Science and Engineering (Photogr.Sci.Eng.), Vol. 19, No. 2, 124-.
It can be measured by using a swellometer (swelling meter) of the type described on page 129, and T _1/2 is 30 in a color developer.
The maximum swollen film thickness reached when treated at 3 ° C for 15 minutes
The saturation film thickness is defined as 0%, and is defined as the time required to reach the film thickness of T _1/2 .

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

Next, the processing solutions and processing steps for the color reversal photosensitive material of the present invention will be described. The black and white development process of the color reversal light-sensitive material of the present invention is carried out in 80 seconds or less. The time is preferably 60 seconds or less, and the effect of the present invention becomes remarkable in such rapid black and white development. Among the processing steps of the color reversal light-sensitive material of the present invention, the steps from black and white development to color development are as follows.

1) Black and White Development-Washing-Reversal-Color Development 2) Black-White Development-Water Wash-Photo Reversal-Color Development 3) Black-White Development-Water Wash-Color Development Steps 1) to 3) are all US patents. 4,8
In place of the rinse process described in No. 04,616, it is possible to simplify the process and reduce waste liquid.

Next, the steps after color development will be described. 4) Color development-adjustment-bleach-fixing-washing-stable 5) Color development-washing-bleaching-fixing-washing-stable 6) Color development-adjusting-bleaching-washing-fixing-washing-stable 7) Color development-washing -Bleaching-washing-fixing-washing-stable 8) Color development-bleaching-fixing-washing-stable 9) Color development-bleaching-bleach-fixing-washing-stable 10) Color development-bleaching-bleach-fixing-fixing-washing-stable

11) Color developing-bleaching-washing-fixing-washing-stable 12) Color developing-adjusting-bleach-fixing-washing-stable 13) Color-developing-washing-bleach-fixing-washing-stable 14) Color developing-bleach-fixing -Washing-Stable 15) In the processing steps of color development-fixing-bleach-fixing-water washing-stable 4) to 15), the washing step immediately before the stabilizing step may be eliminated, or conversely, the stabilizing step of the final step may be It does not have to be done. The color reversal process is formed by connecting any one of the processes 1) to 3) and any one of the processes 4) to 15).

Next, the processing liquid in the color reversal processing step of the present invention will be described. Known developing agents can be used in the black and white developing solution used in the present invention. Examples of developing agents include dihydroxybenzenes (for example, hydroquinone) and 3-pyrazolidones (for example, 1-phenyl-).
3-pyrazolidone), aminophenols (eg N
-Methyl-p-aminophenol), 1-phenyl-3
-Pyrazolines, ascorbic acid and US Pat.
The heterocyclic compounds such as 1,2,3,4-tetrahydroquinoline ring and indrene ring described in No. 67,872 can be used alone or in combination.

In the black-and-white developer used in the present invention, if necessary, preservatives (eg, sulfite, bisulfite), buffers (eg, carbonate, boric acid, borate, alkanolamine), alkaline agents ( For example, hydroxides, carbonates, dissolution tablets (eg polyethylene glycols, their esters), water softeners (eg aminopolycarboxylic acids, organic phosphonic acids), pH adjusters (eg organic substances such as acetic acid). Acid), a sensitizer (for example, a quaternary ammonium salt),
A development accelerator, a surfactant, an antifoaming agent, a film hardener, an antifoggant (eg, potassium iodide, potassium bromide, benzotriazole), a viscosity imparting agent and the like can be contained.

The black-and-white developing solution used in the present invention must contain a compound acting as a silver halide solvent.
The sulfite, which is usually added as a preservative, plays the role. The sulfite and other silver halide solvents that can be used are specifically KSCN, NaSCN, K
₂ SO ₃ , Na ₂ SO ₃ , K ₂ S ₂ O ₅ , Na ₂ S ₂ O
₅ , K ₂ S ₂ O ₃ , Na ₂ S ₂ O _{3 and the} like can be mentioned. The pH value of the black-and-white developer is appropriately selected to give a desired density and contrast, but it is about 8.5 to about 1.
It is in the range of 1.5.

The reversal bath used after black and white development may contain a known fogging agent. That is, stannous ion-organic phosphoric acid complex salt (US Pat. No. 3,617,282), stannous ion organic phosphonocarboxylic acid complex salt (Japanese Patent Publication No. 56-32616), stannous ion-
Aminopolycarboxylic acid complex salt (UK Patent No. 1,209,0
50), stannous ion complex salts, borohydride compounds (US Pat. No. 2,984,567),
Heterocyclic amine borane compounds (UK Patent No. 1,011,0
No. 00 specification) and the like, and the like.

The fogging bath (inversion bath) has a wide pH range from the acidic side to the alkaline side.
The range is 2, preferably 2.5 to 10, and particularly preferably 3 to 9. A light reversal process by re-exposure may be performed instead of the reversal bath, and the reversal step may be omitted by adding the fogging agent to the color developing solution.

The aromatic primary amine color developing agent used in the color developing solution of the present invention is preferably a p-phenylenediamine derivative, and representative examples thereof are shown below, but the invention is not limited thereto. D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [ N-ethyl-N- (β-hydroxyethyl) amino] aniline

D-5 2-methyl-4- [N-ethyl-
N- (β-hydroxyethyl) amino] aniline D-6 4-amino-3-methyl-N-ethyl-N-
[Β- (Methanesulfonamido) ethyl] -aniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine

D-9 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline D-10 4-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Of the above p-phenylenediamine derivatives, the exemplified compounds D-2, D-4, D-5 and D-6 are particularly preferable.

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g per liter of the developing solution.
Is about 20 g, more preferably about 0.5 g to 15 g.

In the present invention, the color developing solution containing substantially no benzyl alcohol means a color developing solution having a benzyl alcohol concentration of 3 × 10 ⁻² mol or less per liter of the developing solution, preferably no benzyl alcohol.

The sulfite contained in the color developing solution of the present invention means sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite,
It shows potassium metabisulfite and the like. The preferable addition amount of sulfite is, in terms of sodium sulfite, the color developer 1.
It is 1 × 10 ⁻⁵ mol to 5 × 10 ⁻² mol per liter, more preferably 1 × 10 ⁻⁴ mol to 5 × 10 ⁻² mol, and further preferably 1 × 10 ⁻⁴ mol to 2 × 10. ^-2 mol.

Other preservatives are disclosed in JP-A-57-441.
Various metals described in No. 48 and No. 57-53749,
Salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, and aroma described in US Pat. No. 3,746,544. A group polyhydroxy compound or the like may be contained if necessary. It is particularly preferable to add an aromatic polyhydroxy compound.

The color developing solution used in the present invention preferably has a pH of 9 to 14, more preferably 9 to 13, and the color developing solution may contain other known color developing solution component compounds. You can In order to maintain the above pH, it is preferable to use various buffers.

Specific examples of the buffering agent include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate and borophosphate. Potassium salt, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (5-sulfosalicylic acid) Sodium), 5-sulfo-2
-Potassium hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned. However, the present invention is not limited to these compounds.

The amount of the above-mentioned buffer added to the color developer is
It is preferably 0.1 mol / l or more, particularly 0.1
It is particularly preferable that it is from mol / l to 0.4 mol / l.
In addition, various chelating agents can be used in the color developing solution as a calcium or magnesium precipitation preventing agent or for improving the stability of the color developing solution.

The chelating agent is preferably an organic acid compound, and examples thereof include aminopolycarboxylic acids, organic phosphonic acids and phosphonocarboxylic acids. Specific examples are shown below, but the present invention is not limited thereto.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ',
N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, ethylenediamineorthohydroxyphenylacetic acid, 2-phosphonobutane-1,2, 4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid, two kinds of these chelating agents may be used, if necessary. You may use together above.

The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. For example, it is about 0.1 g to 10 g per liter. An optional development accelerator can be added to the color developing solution, if necessary.
P-phenylenediamine compounds represented by JP-A-15554, JP-A-50-137726, and JP-B-44-3.
No. 0074, JP-A Nos. 56-156826 and 52-
No. 43429, quaternary ammonium salts represented by

US Pat. Nos. 2,494,903 and 3,
128,182, 4,230,796, 3,2
53,919, Japanese Patent Publication No. 41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926 and 3,582,346, and the like, Japanese Patent Publication No. 37-16088. No. 42-25201, U.S. Pat. No. 3,128,183, Japanese Patent Publication No. 41-11431.
No. 42-23883 and U.S. Pat. No. 3,532,
If necessary, polyalkylene oxides represented by No. 501 and the like, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added.

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

The color developing solution used in the present invention may contain a fluorescent whitening agent. The fluorescent brightening agent is 4,
A 4'-diamino-2,2'-disulfostilbene compound is preferred. The addition amount is 0 to 5 g / l, preferably 0.
It is 1 g to 4 g / l. If necessary, various surfactants such as alkylsulfonic acid, arylphosphonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added.

The processing temperature of the color developing solution of the present invention is 20 to
It is 50 ° C., preferably 30 to 40 ° C. Processing time is 2
It is 0 second to 8 minutes, preferably 30 seconds to 6 minutes. It is preferable that the replenishment amount is small, but 100 to 30 per 1 m ^{2 of} light-sensitive material
The amount is 00 ml, preferably 100 to 2500 ml, and more preferably 100 to 2000 ml.

If necessary, the color developing bath is divided into two or more baths, and the color developing replenisher is replenished from the foremost bath or the last bath to shorten the developing time or reduce the replenishing amount. Is also good. Further, the color developing solution of the present invention contains a so-called competitive compound such as citrazinic acid, J acid, or H acid which produces a colorless compound by reacting with an oxidant of the color developing agent for the purpose of gradation control. Can be included.

The light-sensitive material of the present invention is subjected to bleaching treatment or bleach-fixing treatment after color development. These treatments may be carried out immediately after the color development without any other treatment process, or after the color development treatment and after undergoing a treatment process such as stopping, adjusting or washing.

In the above-mentioned preparation liquid, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid; sulfite salts such as sodium sulfite and ammonium sulfite; and thioglycerin, aminoethanethiol and sulfoethanethiol. Bleaching accelerators can be included. Further, for the purpose of preventing scum, sorbitan esters of fatty acids substituted with ethylene oxide described in U.S. Pat. No. 4,839,262, U.S. Pat. No. 4,059,446 and Research Disclosure 191, 19104 (1980). It is preferable to include the polyoxyethylene compound or the like.

As the bleaching agent used in the bleaching solution and / or the bleach-fixing solution, a ferric complex salt of aminopolycarboxylic acid, a peroxide (eg sodium persulfate) and the like can be used. Complex salts are preferred. As the aminopolycarboxylic acid of such ferric complex salt, ethylenediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, cyclohexanediaminetetraacetic acid, 1,4-diaminobutanetetraacetic acid,
1,2-Propylenediaminetetraacetic acid, thioglycoletherdiaminetetraacetic acid, 1,3-butylenediaminetetraacetic acid and methyliminodiacetic acid are preferred.

The addition amount of the above-mentioned bleaching agent is 0.05 mol to 1 mol, preferably 0.1 mol to 0.5 mol, per liter of the bleaching solution or the bleach-fixing solution. In the bleaching solution and / or the bleach-fixing solution of the present invention, the aforementioned aminopolycarboxylic acid iron [I
II] In addition to the complex, an aminopolycarboxylic acid salt can be added.

The preferred addition amount is 0.0001 mol to 0.
It is 1 mol / l, and more preferably 0.003 to 0.05 mol / l. The aminopolycarboxylic acid and its ferric iron complex salt are usually preferably used in the form of an alkali metal salt or an ammonium salt, and an ammonium salt is particularly preferable in view of its excellent solubility and bleaching power. Various bleaching accelerators can be added to the bleaching solution and / or the bleach-fixing solution of the present invention.

Examples of such a bleaching accelerator include, for example, US Pat. No. 3,893,858, German Patent 1,290,812, and British Patent 1,13.
8,842, JP-A-53-95630,
Research Disclosure No. 17129 (197)
The compound having a mercapto group or a disulfide group described in the July 8 issue) is preferable. The amount of the bleaching accelerator added is 0.01 to 20 g, preferably 0.1 to 10 g, per liter of the bleaching solution.

In the bleaching solution and / or the bleach-fixing solution constituting the present invention, in addition to the bleaching agent and the above compound, bromide such as potassium bromide, sodium bromide, ammonium bromide or chloride such as potassium chloride, Rehalogenating agents such as sodium chloride, ammonium chloride and the like can be included. The concentration of the rehalogenating agent is 0.1 to 1 liter of the bleaching solution.
It is 5 mol, preferably 0.5 to 3 mol. Besides, pH of sodium nitrate, ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc.
It is possible to add known additives which can be usually used in a bleaching solution, such as one or more kinds of inorganic acids, organic acids and salts thereof having a buffering ability.

A thiosulfate can be used as a fixing agent in the bleach-fixing solution and / or the fixing solution of the present invention. The amount of thiosulfate added is 0.1 mol / l to 3 mol / l, preferably 0.3 mol / l to 2 mol / l. Examples of the thiosulfate compound include ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, calcium thiosulfate, magnesium thiosulfate, and the like, and ammonium thiosulfate is preferred because of its good solubility and the highest fixing rate.

In addition to the above-mentioned thiosulfate compound, a thiocyanate compound (particularly ammonium salt), thiourea, thioether, urea or the like is used as the fixing agent or fixing accelerator of the bleach-fixing solution and / or the fixing solution of the present invention. You can The concentration of these auxiliary fixing agents or fixing accelerators is 1.11 to 3.0 mol / total including the thiosulfate compound.
1 and preferably 1.4 to 2.8 mol / l.

The bleach-fixing solution and / or the fixing solution of the present invention may contain a sulfite as a preservative, for example, sodium sulfite, potassium sulfite, ammonium sulfite, hydroxylamine and hydrazine. Further, various fluorescent whitening agents, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol can be contained, and as a preservative, in particular, JP-A-62-143048 can be used. It is preferable to use the described sulfinic acid compounds.

Further, for the purpose of stabilizing the liquid, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids.
Particularly, 1-hydroxyethylidene-1,1-diphosphonic acid is effective. The addition amount of these is 0.01 to
0.3 mol / l, preferably 0.05-0.2 mol / l
And is particularly effective for a fixing solution.

PH of the bleaching solution and / or the bleach-fixing solution of the present invention
Is generally 9 to 1, but preferably 7.5 to 1.
5, most preferably 7.0-2.0. In the bleaching solution, 5.0 to 2.0 is particularly preferable. In the preferred pH range, there is little bleaching fog and the desilvering performance is excellent.
The pH of the fixing solution of the present invention is generally 9.0 to 5.0, but 7.5 to 5.5 is particularly preferable.

The washing water used in the washing step may contain known additives, if necessary. For example, hard water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, bactericides and antifungal agents that prevent the growth of various bacteria and algae (eg, isothiazolone, organochlorine bactericides, benzotriazole, etc.) , A drying load, and a surfactant for preventing unevenness can be used. Or LEWest, "WaterQuality Criteria", Phot.Sci.a
nd Eng., vol.9, No6, pages 343-359 (196
The compounds described in 5) and the like can also be used.

As the stabilizing solution used in the stabilizing step, a processing solution for stabilizing the dye image is used. For example, pH3
A liquid having a buffering capacity of ˜6, a liquid containing an aldehyde (eg, glutaraldehyde), or the like can be used. Formalin is not preferable in terms of pollution. If necessary, the stabilizing solution may include an ammonium compound, a metal compound such as Bi or Al, a fluorescent whitening agent, and a chelating agent (for example, EDTA).
1-hydroxyethylidene-1,1-diphosphonic acid),
A bactericidal agent, an antifungal agent, a hardener, a surfactant and the like can be used. Thiazolone compounds such as 5-chloro-2-methyl-isothiazolin-3-one and 1,2-benzisothiazolin-3-one are effective as anti-fungal agents.

Further, it is preferable to add an alkanolamine to the stabilizing solution in order to prevent sulfurization of thiosulfate ions brought into the photosensitive material. The pH of the stabilizing solution of the present invention is 3-8.
However, it is preferably 5 to 7. The temperature of the stabilizing solution is preferably 5 ° C to 45 ° C, more preferably 10 ° C to 40 ° C.
℃.

The washing process and the stabilizing process are preferably a multi-stage countercurrent system, and the number of stages is preferably 2 to 4. You may carry out two or more types of stabilizing solutions in multiple steps. The amount of replenishment is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times the amount carried in from the previous bath per unit area. The shorter the treatment time of the washing and stabilizing steps, the more the effect of the present invention appears. From the viewpoint of rapid treatment, the total treatment time of the washing and stabilizing steps is preferably 10 to 50 seconds, and particularly 10 to 30 seconds, the effect is remarkable.

As the water used in these washing or stabilizing steps, in addition to tap water, water deionized to a Ca and Mg concentration of 5 mg / l or less with an ion exchange resin, halogen, an ultraviolet germicidal lamp, etc. It is preferred to use water sterilized by.

[0189]

【Example】

Example 1 A substantially light-insensitive silver halide emulsion E of the present invention
M-1 to 4 were prepared. The emulsion is prepared by the usual neutral double jet method after preparing silver halide grains.
An excess ion was washed by a precipitation method to obtain an emulsion. After washing, gelatin was added and pH was adjusted for redispersion, and surface chemical ripening was not performed. The emulsion obtained is shown in Table 3.

[0190]

[Table 3]

Next, a color photographic light-sensitive material was prepared by coating the following first to twelfth layers on a paper support laminated on both sides with polyethylene, and designated as sample No. 101. The polyethylene-containing side of the first layer contains 15% by weight of anatase-type titanium oxide as a white pigment and a trace amount of ultramarine as a bluish dye. (Composition of photosensitive layer) The components and the coating amounts shown in g / m ² are shown below. For silver halide, the coating amount in terms of silver is shown.

First Layer (Gelatin Layer) Gelatin 1.30 Second Layer (Antihalation Layer) Black Colloidal Silver 0.10 Gelatin 0.70

Third Layer (Low Sensitivity Red Sensitive Layer) Silver chloroiodobromide (1 mol% silver chloride / iodinated) spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3 equivalent amounts) Silver 4 mol%, average particle size 0.3 μ, particle size distribution 10%, cubic, core iodide type core shell) 0.06 Spectral sensitized with red sensitizing dye (ExS-1, 2, 3 equivalent amounts) Silver iodobromide (silver iodide 4 mol%, average grain size 0.5 μ, grain size distribution 15%, cube) 0.10

Gelatin 1.00 Cyan coupler (ExC-1) 0.14 Cyan coupler (ExC-2) 0.07 Anti-fading agent (Cpd-2, 3, 4 each equivalent) 0.12 Coupler dispersion medium (Cpd) -6) 0.03 Coupler solvent (Solv-1, 2, 3 each equivalent) 0.06 Development accelerator (Cpd-13) 0.05

Fourth Layer (Highly Sensitive Red Sensitive Layer) Silver iodobromide (6 mol% silver iodide, average grain size) spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3 equivalent amounts) 0.8μ, grain size distribution 20%, flat plate (aspect ratio = 8, core iodine) 0.15 gelatin 1.00 cyan coupler (ExC-1) 0.20 cyan coupler (ExC-2) 0.10 Anti-fading agent (Cpd-2, 3, 4 each equivalent) 0.15 Coupler dispersion medium (Cpd-6) 0.03 Coupler solvent (Solv-1, 2, 3 each equivalent) 0.10

Fifth layer (intermediate layer) Magenta colloidal silver 0.02 Gelatin 1.00 Color mixing inhibitor (Cpd-7, 16 equivalents) 0.08 Color mixing inhibitor solvent (Solv-4, 5 equivalents) 0.16 Polymer latex (Cpd-8) 0.10

Sixth Layer (Low Sensitivity Green Sensitive Layer) Silver chloroiodobromide spectrally sensitized with a green sensitizing dye (ExS-4) (silver chloride 1 mol%, silver iodide 2.5 mol%, average) Grain size 0.28μ, grain size distribution 8%, cubic, core iodide type core shell) 0.04 Silver iodobromide (silver iodide 2) spectrally sensitized with a green sensitizing dye (ExS-4) 0.5 mol% -average particle size 0.48μ, particle size distribution 12%, cubic) 0.06 gelatin 0.80

Magenta coupler (ExM-1, 2 equivalents) 0.10 Anti-fading agent (Cpd-9) 0.10 Anti-staining agent (Cpd-10, 11 equivalents) 0.01 Anti-staining agent (Cpd) -5) 0.001 Anti-staining agent (Cpd-12) 0.01 Coupler dispersion medium (Cpd-5) 0.05 Coupler solvent (Solv-4, 6 each equivalent) 0.15

Seventh Layer (High-Sensitivity Green Sensitive Layer) Silver iodobromide spectrally sensitized with a green sensitizing dye (ExS-4) (silver iodide 3.5 mol%, average particle size 1.0 μ, particles Size distribution 21%, flat plate (aspect ratio = 9, uniform iodine type) 0.10 Gelatin 0.80 Magenta coupler (ExM-1, 2 equivalents) 0.10

Anti-fading agent (Cpd-9) 0.10 Anti-staining agent (Equivalent amounts of Cpd-10, 11, 22) 0.01 Anti-staining agent (Cpd-5) 0.001 Anti-staining agent (Cpd-12) ) 0.01 coupler dispersion medium (Cpd-6) 0.05 coupler solvent (Solv-4, 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 Inhibitor Solvent (Solv-4, 5 Equivalents) 0.15 Polymer Latex (Cpd-8) 0.10

Ninth Layer (Low Sensitivity Blue Sensitive Layer) Silver chloroiodobromide (2 mol% silver chloride / silver iodide 2.) spectrally sensitized with a blue sensitizing dye (Equivalent of ExS-5 and 6). 5 mol%, average particle size 0.38 μ, particle size distribution 8%, cubic, core iodide type core shell)) 0.07 Spectral sensitized with blue sensitizing dye (ExS-5, 6 each equivalent) Silver iodobromide (Silver iodobromide 2.5 mol%, average grain size 0.55 μ, grain size distribution 11%, cubic) 0.10.

Gelatin 0.50 Yellow coupler (ExY-1, 2 equivalents) 0.20 Anti-staining agent (Cpd-5) 0.001 Anti-fading agent (Cpd-14) 0.10 Coupler dispersion medium (Cpd-) 6) 0.05 coupler solvent (Solv-2) 0.05

10th layer (high-sensitivity blue-sensitive layer) Silver iodobromide spectrally sensitized with a blue sensitizing dye (Equivalent of ExS-5 and 6) (2.5 mol% silver iodobromide / average grain) Size 1.4 μ, particle size distribution 21%, flat plate (aspect ratio = 14)) 0.25 gelatin 1.00 yellow coupler (ExY-1, 2 each equivalent) 0.40 anti-staining agent (Cpd-5) 0.002 Anti-fading agent (Cpd-14) 0.10 Coupler dispersion medium (Cpd-6) 0.15 Coupler solvent (Solv-2) 0.10

Eleventh layer (UV absorber-containing protective layer) Gelatin 1.50 UV absorber (Equivalent amounts of Cpd-1, 2, 4, and 15) 1.00 Color mixing inhibitor (Cpd-7, 16) 06 Dispersion medium (Cpd-6) UV absorber solvent (Solv-1, 2 each equivalent) 0.15 Anti-irradiation dye (Cpd-17, 18 equivalent) 0.02 Anti-irradiation dye (Cpd-19) , 20 each equivalent) 0.02

Twelfth Layer (Protective Layer) EM-3 0.13 (shown by silver halide weight) Modified Poval 0.02 Gelatin 1.50 Gelatin hardening agent (H-1, 2 equivalents) 0.17

Further, for each layer, alkanol XC (Du Pont) as an emulsification / dispersion aid and sodium alkylbenzene sulfonate were used, and succinate and Magefac F-120 (manufactured by Dainippon Ink and Chemicals) were used as coating aids. I was there. In the layer containing silver halide or colloidal silver, (Cpd-21, 22, 23) was used as a stabilizer. The compounds used in the examples are shown below.

[0208]

[Chemical 37]

[0209]

[Chemical 38]

[0210]

[Chemical Formula 39]

[0211]

[Chemical 40]

[0212]

[Chemical 41]

[0213]

[Chemical 42]

[0214]

[Chemical 43]

[0215]

[Chemical 44]

[0216]

[Chemical formula 45]

[0217]

[Chemical formula 46]

[0218]

[Chemical 47]

Solv-1 Di (2-ethylhexyl) phthalate Solv-2 Trinonyl Phosphate Solv-3 Di (3-methylhexyl) phthalate Solv-4 Tricresyl Phosphate

Solv-5 dibutyl phthalate Solv-6 trioctyl phosphate H-2 4,6-dichloro-2-hydroxy-
1,3-5-triazine Na salt

This sample is referred to as sample 101. Next, in this sample, the yellow coupler of the ninth and tenth layers, the first
The amount of the color mixing inhibitor (Cpd-7, 16) for one layer, the type and amount of the emulsion for the twelfth layer, and the eleventh-b layer between the eleventh layer and the twelfth layer are newly provided. Samples 102 to 109 were prepared as shown in Table 4.

[0222]

[Table 4]

The obtained sample is subjected to practical exposure or 3200
Exposure for sensitometry was carried out with a light source of ° K, and then reversal processing described later was carried out to obtain an image. The processing steps and processing solutions used here are as follows.

Processing Steps Black development 38 ° C. 75 seconds Water washing 38 ° C. 90 seconds Reverse exposure 100 Lux or more 60 seconds or more Color development 38 ° C. 135 seconds Water washing 38 ° C. 45 seconds Bleach fixing 38 ° C. 120 seconds Water washing 38 ° C. 135 seconds Dry

Composition of Processing Solution (Black and White Developer) Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 0.6 g Diethylenetriaminepentaacetic acid pentasodium salt 4.0 g Potassium sulfite 30.0 g Potassium thiocyanate 1. 2g Potassium carbonate 35.0g Hydroquinone monosulfonate / potassium salt 25.0g

Diethylene glycol 15.0 ml 1-Phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 2.0 g Potassium bromide 0.5 g Potassium iodide 5.0 mg Water was added to 1 l (pH 9.70).

(Color Developer) Benzyl alcohol 15.0 ml Diethylene glycol 12.0 ml 3,6-Dithia-1,8-octanediol 0.2 g Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 5g Diethylenetriamine pentaacetic acid pentasodium salt 2.0g Sodium sulfite 2.0g Potassium carbonate 25.0g

Hydroxylamine sulfate 3.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g potassium bromide 0.5 g potassium iodide 1.0 mg Add water 1 liter (pH 10.40)

(Bleach-fixing solution) 2-mercapto-1,3,4-triazole 1.0 g Ethylenediaminetetraacetic acid / sodium dihydrate 5.0 g Ethylenediaminetetraacetic acid / Fe (III) / ammonium monohydrate 80. 0 g Sodium sulfite 15.0 g Sodium thiosulfate (700 g / l solution) 160.0 ml Glacial acetic acid 5.0 ml Water was added 1 l (pH 6.50) The results obtained are shown in Table 5.

[0230]

[Table 5]

In Table 5, regarding reproduction of lemon yellow, a subject containing lemon yellow was photographed using a commercially available color reversal film, and then the sample was printed. This was processed using a sheet processor HOPE2010V for reversal paper to obtain a color image. From the samples thus obtained, the lemon yellow color-developed portion was selected, and the yellow (Y) density and the magenta (M) density of the same portion were measured for all the samples 101 to 109. The Y concentration of the selected portion was within the range of 1.20 ± 0.04 for all the samples. The M density at this time is shown as the degree of M color mixing in the lemon yellow color development portion.

In addition to the above density measurement, a subject containing lemon yellow was photographed and sensory evaluation was performed. This is indicated by O (excellent), Δ, and X (inferior). The treated streaks were subjected to a running treatment for 1 month using the above-mentioned HOPE2010V processor, and then the exposed sample was treated so as to be gray with a density of 0.7, and the generation of streaks was visually judged. ◯ indicates no occurrence, Δ indicates slight occurrence, and x indicates strong occurrence.

Yellow stain is the minimum density value (Dmin (B)) when a sample processed by sensitometric exposure is measured with a blue filter. This value is
0.11 or less is preferable, and if it exceeds 0.13, it is not practically desirable. "Bleaching agent" is a bleaching accelerator 2
-Development inhibition that occurs when 1 mg / l of mercapto-1,3,5-triazole is erroneously mixed in a black-and-white developing solution is shown by the change value (ΔD _0.6 (B)) of the sensitivity of the blue sensitive layer. . The closer to 0 this value is, the more desirable.

The "stirring dependency" indicates the stability of photographic properties against stirring of the processing solution during black and white development. This is indicated by the sensitivity change value (ΔS _0.6 (R)) of the red-sensitive layer when a black-and-white developing bath of 2 liters was used and stirring was completely stopped as compared with stirring with nitrogen gas. This is also desirable as it approaches 0. Samples 103, 104, 106-108 according to the invention
It turns out that is satisfied with all items. It can be seen that among these, the samples 103 and 106 are the best.

Claims (2)

[Claims] 1. A yellow dye formation represented by the following general formula [I] having a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer on a support. A method of forming a color reversal image after black-and-white development of a silver halide color photographic light-sensitive material containing at least one coupler, wherein the light-sensitive material is non-image forming outside the light-sensitive image forming layer farthest from the support. At least three protective layers are contained, and at least one layer other than the outermost layer and the lowermost layer of the protective layer group contains 0.001 mg / m ² or more of non-photosensitive silver halide grains, and the protective layer is further contained. At least one layer below the layer containing non-photosensitive silver halide grains of the group contains 0.01 mg / m ² or more of an oxidant scavenger as a developing agent, and the photosensitive material is subjected to black and white development within 80 seconds after exposure. Processor The silver halide color reversal image forming method characterized by having a. General formula [I] 2. The silver halide color reversal image forming method according to claim 1, wherein the non-photosensitive silver halide grains contain silver chloride in an amount of 70 mol% or more.