JP2558479B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a large amount of silver halide color photographic light-sensitive material, and provides a color photographic light-sensitive material having excellent color reproducibility and improved processability. It is a thing.

(Prior Art) In recent years, the technology of color photography has made remarkable progress. Sharpness / granularity, color reproducibility, color image storability, proper exposure light source,
In many respects such as processing stability, color photographic light-sensitive materials have been provided with various improvements accumulated in a state of the art.

With regard to sharpness and color reproducibility, a compound that releases a development inhibitor or its precursor (hereinafter abbreviated as DIR compound)
Is important, and various DIR couplers have been developed to this day.

For example, British Patent No. 935,454, United States Patent No. 3,227,554,
No. 4,095,984, No. 4,149,886, and the coupler mother nucleus forms a dye when subjected to a coupling reaction with a color developing agent as described in JP-A-57-151944. DIR couplers which release an inhibitor and exhibit a development inhibitory action are mentioned. U.S. Patent 3,652,3
45, 3,928,041, JP53-110529, 54-133.
No. 33, No. 55-161237, etc., and a DIR coupler which releases a development inhibitor but does not form a dye when subjected to a coupling reaction with an oxidized product of a color developing agent. Further, JP-A-54-145135, JP-A-56-114946 and JP-A-57
-154234, when reacted with an oxidant of a color developing agent, the mother nucleus forms a dye or a colorless compound, while the leaving timing group is developed by an intramolecular nucleophilic substitution reaction or a leaving reaction. So-called DI releasing inhibitor
R coupler is also included.

Further, the DIR coupler developed so that the effect of the developing bath formulation acts between layers from the layer containing the nuclear coupler in the color light-sensitive material to the other layer is a so-called diffusive property that releases a highly diffusible development inhibitor. A DIR coupler, which is disclosed in JP-A-57-151944.
No. 57-154234. Especially JP-A-57-
The development inhibitor of No. 151944 exhibits development inhibitory property when released from the coupling reaction, deactivates the development inhibitory effect when it appears in the development processing solution, and is an excellent DIR coupler having a function of preventing processing solution contamination. Is.

By using these DIR couplers, sharpness,
Although the color reproducibility has been improved considerably, on the other hand, these DI
When a large amount of R coupler is used, it causes a decrease in color development sensitivity, and when a directional development process is performed, an unnecessary development suppressing effect in the layer of the light-sensitive material is tailed in the opposite direction of the process. However, there is a defect that the image is generated in shape and an inconvenient image is formed. Directional development processing means processing such as 135-size photographic sensitive material that is endlessly joined at a developing station or a simple rapid processing machine called minilab that has become popular in recent years. It refers to processing such as roller transport method and clip method.

In designing a color light-sensitive material, it is desired to fully use such a diffusible DIR coupler in each color-sensitive layer to improve sharpness and color reproducibility, but the amount used is limited due to the reasons described above. There has been a demand for a method of improving.

JP-A-62-177557 mentions improvement of storage stability and development processing characteristics by diffusible DIR compound and non-photosensitive silver halide fine particles in a protective layer. In such a low speed yellow coupler, the diffusible DIR compound could not be used sufficiently, and the color reproducibility and sensitivity were insufficient.

(Problems to be Solved by the Invention) An object of the present invention is to provide a multilayer silver halide color photographic material which has stable processability without impairing color reproducibility and sensitivity.

(Means for Solving the Problems) The inventors of the present invention have found that the following method can be achieved as a result of earnest efforts for the above purpose. That is, in a silver halide color photographic light-sensitive material having a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer on a support,
A yellow dye-forming color coupler containing at least one compound represented by the following general formula [I], and
In the same color-sensitive layer farthest from the support, a compound that reacts with an oxidant of the color developing agent to release a diffusible development inhibitor or a diffusible precursor of the development inhibitor and / or a color developing agent The diffusible compound cleaved after the reaction with the oxidant further reacts with another molecule of the color developing agent to develop a development inhibitor, and the compound contains 1 mol% or more based on the photosensitive silver halide of the color sensitive layer. And has a protective layer of a non-photosensitive hydrophilic colloid layer on the side farther from the support than the color-sensitive layer, and the non-photosensitive fine grain silver halide is contained in the protective layer with respect to the above compound. This has been achieved by a multi-layer silver halide color photographic light-sensitive material characterized by containing at least twice the molar amount.

General formula [I] The yellow coupler represented by formula (I) used in the present invention will be described in detail.

Examples of M and M ′ are a halogen atom (fluorine atom, chlorine atom, bromine atom), an aliphatic group having 1 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an aliphatic oxy group having 1 to 20 carbon atoms. , An aromatic oxy group having 6 to 20 carbon atoms, a carbonamido group having 2 to 24 carbon atoms, a sulfonamide group having 0 to 20 carbon atoms, and 1 carbon atom
A carbamoyl group having 24 carbon atoms, a sulfamoyl group having 0 to 20 carbon atoms, an acyloxy group having 2 to 20 carbon atoms, an aliphatic oxycarbonyl group having 2 to 20 carbon atoms, a substituted amino group having 2 to 24 carbon atoms, and 1 to 1 carbon atoms. 24 aliphatic thio groups, 0-20 carbon ureido groups, 0-20 carbon sulfamoylamino groups, cyano groups, 2-20 carbon aliphatic oxycarbonylamino groups, 4-20 carbon atoms Examples thereof include an imide group, an aliphatic sulfonyl group having 1 to 20 carbon atoms, an aromatic sulfonyl group having 6 to 20 carbon atoms, and a heterocyclic group having 1 to 20 carbon atoms. L is a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom) or an aliphatic oxy group having 1 to 24 carbon atoms. X is a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developer, and is represented by the following general formulas [II], [III] and [IV].

General formula [II] -OR 'General formula [III] -SR "General formula [IV] In the general formula [II], R'is an aromatic group having 2 to 30 carbon atoms, a heterocyclic group having 1 to 28 carbon atoms, an acyl group having 2 to 28 carbon atoms, an aliphatic sulfonyl group having 1 to 24 carbon atoms, or a carbon atom. Number 6
~ 24 aromatic sulfonyl groups.

In the general formula [III], R ″ represents an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or a heterocyclic group having 1 to 28 carbon atoms.

In the general formula [IV], Y represents a group of non-metallic atoms necessary for forming a monocyclic or condensed 5- to 7-membered heterocyclic ring together with N. Examples of heterocycles formed by N and Y include pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, tetraazaindene, succinimide, phthalimide , Saccharin, oxazolidine-2,4-dione, imidazolidine-2,4-dione, thiazolidine-2,4-dione, urazole, parabanic acid, maleinimide, 2-pyridone, 4
-Pyridone, 6-pyridazone, 6-pyrimidone, 2-pyrazone, 1,3,5-triazin-2-one, 1,2,4-triazin-6-one, 1,3,4-triazin-6-one , 2-
Oxazolone, 2-thiazolone, 2-imidazolone, 3
-Isoxazolone, 5-tetrazolone, 1,2,4-triazo-5-one and the like, which may be substituted, and examples of the substituent include a halogen atom, a hydroxy group,
Nitro group, cyano group, hydroxy group, aliphatic group, aromatic group, heterocyclic group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic oxycarbonyl group,
Examples include a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a ureido group, a sulfamoylamino group, an aliphatic oxycarbonylamino group, and a substituted amino group.

In the present invention, the aliphatic group represents a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group, which may be substituted. Examples of the aliphatic group include a methyl group, an ethyl group, an isopropyl group, an n-butyl group, t
-Butyl group, t-amyl group, n-hexyl group, cyclohexyl group, n-octyl group, 2-ethylhexyl group, n
-Decyl group, n-dodecyl group, n-tetradecyl group, n
-Hexadecyl group, 2-hexyldecyl group, n-octadecyl group, allyl group, benzyl group, phenethyl group, undecenyl group, octadecenyl group, trifluoromethyl group, chloroethyl group, cyanoethyl group, 1- (ethoxycarbonyl) ethyl group, There are methoxyethyl group, butoxyethyl group, 3-dodecyloxypropyl group, phenoxyethyl group and the like. In the present invention, the heterocyclic group means a substituted or unsubstituted monocyclic or condensed ring heterocyclic group, for example, 2-furyl group, 2-thienyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-quinolyl group, oxazole-
2-yl group, thiazol-2-yl group, benzoxazol-2-yl group, benzothiazol-2-yl group, 1,
There are a 3,4-thiadiazol-2-yl group, a 1,3,4-oxadiazol-2-yl group and the like. In the present invention, the aromatic group is a substituted or unsubstituted monocyclic or condensed ring aryl group, and examples thereof include a phenyl group, a tolyl group, a 4-chlorophenyl group, a 4-methoxyphenyl group, a 1-naphthyl group and a 2- There are naphthyl group, 4-t-butylphenoxy group and the like.

Next, examples of preferred substituents in the coupler represented by the general formula [I] used in the present invention will be described. M is preferably an aliphatic group (methyl group, ethyl group, n-propyl group, t-butyl group, etc.), aliphatic oxy group (methoxy group,
Ethoxy group, n-butoxy group, n-dodecyloxy group, etc.), halogen atom (fluorine atom, chlorine atom, bromine atom), carbonamide group (acedamide group, n-butanamide group, n-tetradecaneamide group, benzamide group, etc.) ) Or a sulfonamide group (methyl sulfonamide group, n-butyl sulfonamide group, n-octyl sulfonamide group, n-dodecyl sulfonamide group, toluene sulfonamide group, etc.). L is preferably a chlorine atom or an aliphatic oxy group (methoxy group, ethoxy group, methoxyethoxy group, n-octyloxy group, 2-methylhexyloxy group, n-tetradecyloxy group, etc.).

M'is preferably an aliphatic oxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, n-
Hexaoxycarbonyl group, 2-ethylhexyloxycarbonyl group, 1- (ethoxycarbonyl) ethyloxycarbonyl group, 3-dodecyloxypropyloxycarbonyl group, n-decyloxycarbonyl group, n-dodecyloxycarbonyl group, phenethyloxycarbonyl group Etc.) or a carbamoyl group (dimethylcarbamoyl group, dibutylcarbamoyl group, dihexylcarbamoyl group, di-2-ethylhexylcarbamoyl group, n-dodecylcarbamoyl group, etc.). m is preferably 0-2 and n is preferably 0-2. X is preferably a group in which R'is an aromatic group in the general formula [II] (4-methoxycarbonylphenoxy group, 4-methylsulfonylphenoxy group, 4-cyanophenoxy group, 4-dimethylsulfamoylphenoxy group, 2 -Acetamido-4-ethoxycarbonylphenoxy group, 4-ethoxycarbonyl-2-methylsulfonamidophenoxy group, etc.) is a group represented by the general formula [IV], and the latter is represented by the following general formula [V]. More preferred are groups.

General formula [V] In the general formula [V], V represents a substituted or unsubstituted methylene group or a substituted or unsubstituted imino group, and W represents an oxygen atom, a sulfur atom, a substituted or unsubstituted methylene group or an unsubstituted imino group. However, when V is an imino group, W is neither an oxygen atom nor a sulfur atom. Examples of the group represented by the general formula [V] include a succinimide group,
Phthalimide group, 1-methyl-imidazolidine-2,4
-Dione-3-yl group, 1-benzyl-imidazolidin-2,4-dione-3-yl group, 5-ethoxy-1-methylimidazolidin-2,4-dione-3-yl group, 5-methoxy -1-Methylimidazolidine-2,4-dione-3
-Yl group, 5,5-dimethyloxazolidinii-2,4-dione-3-yl group, thiazolidin-2,4-dione-3-yl group, 1-benzyl-2-phenyltriazolidine-3,
5-dione-4-yl group, 1-n-propyl-2-phenyldriazolidin-3,5-dione-4-yl group, 5-
Examples include ethoxy-1-benzyl-imidazolidin-2,4-dione-3-yl group.

In the yellow coupler represented by the general formula [I], any one of the substituents M, M ', L or X may be a divalent to tetravalent linking group to form a yellow coupler to 2 to 4 parts by weight. , Monomers or dimers are preferred. When the yellow coupler represented by the general formula [I] is a dimer to a tetramer, the carbon number range mentioned above for M, M ', L or X does not apply.

Specific examples of the yellow coupler represented by the general formula [I] used in the present invention are shown below, but the coupler used in the present invention is not limited thereto.

The yellow coupler used in the present invention is synthesized by a conventionally known method. For example, U.S. Pat.
7,554, 3,408,194, 3,415,652, 3,447,928
No. 4,401,752, UK Patent 1,040,710, JP 47-26
No. 133, No. 47-37736, No. 48-733147, No. 48-94432
No. 48-68834, No. 48-68835, No. 48-68836,
No. 50-34232, No. 51-50734, No. 51-102636, No. 55
-598, 55-161239, 56-95237, 56-1615
No. 43, No. 56-153343, No. 59-174839 and No. 60-3573
It can be synthesized by the synthetic method described in the specification of No. 0.

Compounds that react with the oxidant of the color developing agent according to the present invention to release a diffusible development inhibitor or a diffusible precursor of the development inhibitor, and a diffusible compound cleaved after the reaction with the oxidant of the color developing agent are described below. Further, a compound that cleaves a development inhibitor by reacting with another molecule of a color developing agent will be described. The compound (hereinafter referred to as diffusible development inhibitor compound) is represented by the following general formulas [VI] to [IX].

General formula [VI] A-TIME-Z ₂ General formula [VII] A-Z ₁ General formula [VIII] B-Z ₁ General formula [IX] A (or B) -P-Z ₂ [where A is a color It represents a coupling component capable of reacting with an oxidant of a developing agent, and is a component capable of releasing a -TIME-Z ₂ group or a -P-Z ₂ group by reacting with an oxidant of a color developing agent. B represents a redox moiety which undergoes a redox reaction with the oxidant of the color developing agent and subsequently undergoes alkaline hydrolysis to release Z. TIME represents a timing group. Z ₁ represents the following diffusible development inhibitor.

-P-Z ₂ represents a group which, after being cleaved from A or B, reacts with an oxidized product of a developing agent to form a development inhibitor.

Z ₂ may be a diffusible development inhibitor or a development inhibitor having a small diffusivity. If -TIME-Z ₂ or -P-Z ₂ exhibits diffusibility, A-TIME-Z ₂ and A (or B) -P-Z ₂ will diffuse.
It is a DIR compound. ] The development inhibitor represented by Z ₁ or Z ₂ is Research Disclosure (Researc Disclosure) Volume 176, No. 17643,
(December 1978) development inhibitors are included, preferably mercaptotetrazole, selenotetrazole, mercaptobenzothiazole, selenobenzothiazole, mercaptobenzoxazole, selenobenzoxazole, mercaptobenzimidazole, selenobenzimidazole. , Benzotriazole mercaptotriazole, mercaptooxadiazole, mercaptothiadiazole, and derivatives thereof.

Among the development inhibitors represented by Z ₂ , preferred ones are those represented by the following general formula.

Or In the general formulas [Z-1] and [Z-2], R ₁₁ and R ₁₂ are an alkyl group, an alkoxy group, an acylamino group, a halogen atom, an alkoxycarbonyl group, a thiazolilideneamino group, an aryloxycarbonyl group, an acyloxy group, Carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, nitro group, amino group, N-arylcarbamoyloxy group, sulfamoyl group, sulfonamide group, N-alkylcarbamoyloxy group, ureido group, hydroxy group, Alkoxycarbonylamino group, aryloxy group, alkylthio group, arylthio group, anilino group, aryl group, imide group, heterocyclic group,
Represents a cyano group, an alkylsulfonyl group or an aryloxycarbonylamino group.

n represents 1 or 2, and when n is 2, R ₁₁ and R ₁₂ may be the same or different, and the total number of carbon atoms contained in n R ₁₁ and R ₁₂ is 0. Is ~ 20.

General formulas [Z-3], [Z-4], [Z-5], [Z-
In 6], R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , and R ₁₇ represent an alkyl group, an aryl group, or a heterocyclic group.

When R _{11 to} R ₁₇ represent an alkyl group, they may be substituted or unsubstituted, linear or cyclic. The substituent is a halogen atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group,
A carbamoyl group, a hydroxy group, an alkanesulfonyl group, an arylsulfonyl group, an alkylthio group or an arylthio group.

When R _{11 to} R ₁₇ represent an aryl group, the aryl group may be substituted. As a substituent, an alkyl group, an alkenyl group, an alkoxy group, an alkoxy arbonyl group, a halogen atom, a nitro group, an amino group, a sulfamoyl group, a hydroxy group, a carbamoyl group, an aryloxycarbonylamino group, an alkoxycarbonylamino group, an acylamino group, Examples thereof include a cyano group and an ureido group.

When R _{11 to} R ₁₇ represent a heterocyclic group, they represent a 5-membered or 6-membered monocyclic or condensed ring containing a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom, and a pyridyl group, a quinolyl group or a furyl group. Group, benzothiazolyl group, oxazolyl group, imidazolyl group, thiazolyl group, triazolyl group,
These selected from a benzotriazolyl group, an imide group, an oxazine group and the like may be further substituted with the substituents listed for the aryl group.

In the general formulas [Z-1] and [Z-2], the number of carbon atoms contained in R ₁₁ and R ₁₂ is 1 to 20. More preferably 7 to 20
Is.

General formulas [Z-3], [Z-4], [Z-5], [Z-
6], the total number of carbon atoms contained in R _{13 to} R ₁₇ is 1
Is ~ 20. More preferably, it is 4-20.

Preferred as the development inhibitor in the present invention is the case where the development inhibitor released by the reaction with the oxidized product of the developing agent is a compound which diffuses from the layer contained at the time of development to another layer and exhibits a development inhibitory effect. .

The coupler component represented by A is a dye forming agent such as acylacetanilides, malon diesters, malon diamides, benzoylmethanes, pyrazolones, pyrazolotriazoles, pyrazolobenzimidazoles, indazolones, phenols and naphthols. A coupler component such as a coupler and acetophenones, indanones, oxazolones, etc. which does not substantially form a dye.

Preferred coupler components include the general formulas [X] to [XI
II] can be mentioned.

General formula [X] General formula (XI) General formula (XII) General formula (XIII) In the formula, R ₃₀ represents an aliphatic group, an aromatic group, an alkoxy group or a heterocyclic group, and R ₃₁ and R ₃₂ each represent an aromatic group or a heterocyclic group.

The aliphatic group represented by R ₃₀ preferably has 1 to 20 carbon atoms and may be substituted or unsubstituted chain or cyclic. Preferable substituents on the alkyl group are alkoxy, aryloxy and acylamino groups.

When R ₃₀ , R ₃₁ or R ₃₂ is an aromatic group, it represents a phenyl group, a naphthyl group or the like, but a phenyl group is particularly useful, and this phenyl group may have a substituent. Examples of the substituent include an alkyl group having 30 or less carbon atoms, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an alkylamide group and the like. Further, the phenyl group represented by R ₃₀ , R ₃₁ and R ₃₂ may be substituted with an alkyl group, an alkoxy group, a cyano group or a halogen atom.

R ₃₃ represents a hydrogen atom, an alkyl group, a halogen atom, a carboxamide group, a sulfonamide group, or the like, and l is an integer of 1 to 5. R ₃₄ and R ₃₅ represent a hydrogen atom, an alkyl group or an aryl group, and the aryl group is preferably a phenyl group. The alkyl group and the aryl group may have a substituent, and examples of the substituent include a halogen atom, an alkoxy group, an aryloxy group, a carboxy group and the like. R ₃₄ and R ₃₅ may be the same or different.

The general formula [VIII] is a compound (hereinafter, referred to as DI which releases a development inhibitor or a precursor thereof by subjecting an oxidation product of an aromatic primary amine developing agent to a redox reaction and subsequently undergoing alkali hydrolysis.
R redox compound), and B represents a redox moiety. More specifically, it is represented by the following general formula [XIV].

General formula (XIV) In the formula, G and G'represent a hydrogen atom or a protecting group for a phenolic hydroxyl group that can be deprotected during a photographic processing step, and representative examples include a hydrogen atom, an acyl group, a sulfonyl group, an alkoxycarbonyl group, a carbamoyl group, Examples thereof include an oxalyl group.

R ₁₈ , R ₁₉ and R ₂₀ may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a cyano group, an alkoxycarbonyl group or carbamoyl. Represents a group, a sulfamoyl group, a carboxyl group, a sulfo group, a sulfonyl group, an acyl group, a carbonamido group, a sulfonamide group, or a heterocyclic group.

R ₁₈ and R ₁₉ , R ₁₈ may be G, R ₁₉ may be G ′, and R ₂₀ and G may be bonded to each other to form an aromatic or non-aromatic ring. At least one of R ₁₈ , R ₁₉ and R ₂₀ has 10 to 20 carbon atoms
Containing a number of nondiffusible groups.

 Z is the same development inhibitor as described above.

As the development inhibitor in the present invention, P is A
Or a group which becomes a redox group after cleaving from B or a group which becomes a coupler.

A development inhibitor released by reaction with an oxidized product of a developing agent can be used as a compound exhibiting a development inhibiting effect by diffusing from a layer contained during development to another layer.

These compounds according to the present invention are described in U.S. Pat.
No. 4, No. 3,617,291, No. 3,933,500, No. 3,958,9
No. 93, No. 4,149,886, No. 4,234,678, JP-A-51-
13239, 57-56837, British Patents 2,070,266, 2,072,363, Research Disclosure 1981 1
February 21228, Japanese Patent Sho 58-9942, Japanese Patent Sho 51-16141
JP-A-52-90932, U.S. Pat.No. 4,248,962, JP-A-56-114946, 57-154234, 58-98728, 5
8-209736, 58-209737, 58-209738, 58
-209740, Japanese Patent Application No. 59-278,853, JP-A-61-255342
Can be easily synthesized by the method described in JP-A No. 62-24252.

Specific representative examples of the diffusible development inhibitor releasing compound used in the present invention are shown below, but the invention is not limited thereto.

Next, the non-photosensitive fine grain silver halide relating to the present invention will be described.

The non-photosensitive fine grain silver halide is not exposed to light during imagewise exposure to obtain a dye image, is not substantially developed in the development process, and may be fogged in advance, but is preferably It is a silver halide fine grain without fog.

The fine grain silver halide has a silver bromide content of 0 to 100 mol%. As long as the silver halide contains silver bromide in such a ratio, it has various compositions. Good. You may contain silver chloride and / or silver iodide as needed. Preferred is silver iodobromide containing 0.5 to 10 mol% of silver iodide.

The fine grain silver halide has an average grain size of 0.01 to 0.5 μ.
m, and more preferably 0.02 to 0.2 μm. The average grain size of silver halide grains means the average value of the diameters of circles corresponding to the projected areas of individual silver halide grains, and this measurement is, for example, "Basics of Photographic Engineering-Silver Salt Photographs-" (Japan. The Photographic Society, published January 30, 1979) 22nd
It can be determined by the method described on pages 7 to 228.

The fine grain silver halide can be obtained by a method similar to that for preparing an ordinary photosensitive silver halide emulsion, or according to a case of preparing an ordinary photosensitive silver halide emulsion. In this case, the surface of the silver halide grain does not need to be optically sensitized and spectral sensitization is unnecessary. However,
Prior to adding the fine silver halide grains to the coating solution, a known stabilizer such as a triazole compound, an azaindene compound, a benzothiazolium compound mecalpto compound, or a zinc compound should be added in advance. Is preferred.

Such fine grain silver halide is contained in at least one of the non-photosensitive hydrophilic colloid layers provided on the side of the color-sensitive layer farthest away from the support of the light-sensitive material of the present invention from the side of the support.
Added to the layer. The non-photosensitive hydrophilic colloid layer may be composed of one layer or a plurality of layers of two or more layers, and the fine grain silver halide is contained in at least one layer of the layer,
The layer containing the fine grain silver halide grains may or may not be adjacent to the color-sensitive layer farthest from the support.

The amount of fine grain silver halide added to the non-photosensitive hydrophilic colloid layer is influenced by factors such as the composition of fine grain silver halide, the grain size, and the amount of the diffusible development inhibitor contained in the outermost color-sensitive layer. However, when the diffusible development inhibitor-releasing compound is contained in the color-sensitive layer farthest from the support of the present invention in an amount of 1 mol% or more based on the light-sensitive silver halide of the same layer, the diffusible development inhibitor is used. It is more than 15 times the molar amount of the release compound. It is preferably 15-fold to 1000-fold moles, more preferably 20-fold to 500-fold moles.

The same color-sensitive layer farthest from the support as used in the present invention is composed of at least one photosensitive layer, and is composed of a plurality of photosensitive layers and / or a plurality of photosensitive layers having substantially the same color sensitivity but different sensitivities. A layer group consisting of a plurality of layers such as a substantially non-photosensitive intermediate layer sandwiched between substantially the same photosensitive layers. In the case where another photosensitive layer having different color sensitivity is inserted between a plurality of substantially the same color-sensitive layers and the above-mentioned substantially the same color-sensitive layer is separated into a plurality of units, it is supported. Substantially the same color-sensitive layer group of the unit farthest from the body.

Preferred embodiments of the present invention will be described below. The present invention is particularly effective when a large amount of the compound capable of releasing the diffusion development inhibitor of the present invention is used in the photosensitive layer farthest from the support in the same color-sensitive layer farthest from the support. The outermost photosensitive layer in this case may or may not be the highest sensitivity layer in the same color-sensitive layer, but is preferably the highest sensitivity layer. It is particularly effective in a system in which the compound releasing the diffusible development inhibitor in the highest sensitivity layer is contained in an amount of 0.1 mol% or more based on the photosensitive silver halide in the same layer. Further, the protective layer containing fine grain silver halide is composed of a plurality of hydrophilic colloid layers, more preferably contained in the hydrophilic colloid layer on the side farther from the support than the outermost color-sensitive layer. Is preferred. Further, according to the present invention, the traveling direction of the photographic material in the developing solution is parallel to the sample surface, or as a result of the sample moving in the developing solution, the developing solution flows from the front end to the rear end in the traveling direction of the sample. It has an effect when such processing is performed. It is particularly effective when the moving speed of the treatment liquid is 30 cm / min to 300 cm / min in linear velocity. Examples of such a treatment method include a treatment usually called cine-gen, and a case of applying a roller-conveying treatment machine. A simple rapid processor (minilab), which has been rapidly increasing in recent years, is a typical example of a roller transport system.

Preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide containing from about 2 mol% to about 25% silver iodide.

Silver halide grains in photographic emulsions are cubic, octahedral,
It may have a regular crystal such as a tetradecahedron, an irregular crystal form such as a sphere or a plate, a crystal defect such as a twin plane, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 micron or less or large grains having a projected area diameter of up to about 10 microns, 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), No. 17643 (1978).
December 23, p. 22-23, "I. Emulsion production (Emulsion prepara
and types) ”, and No. 18716 (November 1979)
Mon), p.648, Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chemic et Phisique P
hotographique Paul Motel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photo
graphjc Emulsion Chmistry (Focal Press, 1966)),
"Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VLZelikman et al, Making and Coating
It can be prepared using the method described in Photographic Emulsion. Focal Press, 1964) and the like.

Monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferred.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineerin.
g), 14: 248-257, (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,433,048, 4,439,520
It can be easily prepared by the method described in Japanese Patent No. 2,112,157 and the like.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and may have a different composition by epitaxial bonding. It may be bonded with a compound other than silver halide such as silver rhodanide and lead oxide.

 Also, a mixture of particles 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. The additive used in such a process is Research Disclosure No. 1
7643 and No. 18716, the relevant parts 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.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG.

As the yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
1,752, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020
No. 1,476,760, etc. are preferable.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
619, 4,351,897, European Patent 73,636, U.S. Patent 3,061,432, 3,752,067, Research Disclosure No. 24220 (June 1984), JP-A-60-3355.
2, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, US Pat. No. 4,500,630,
Those described in No. 4,540,654 and the like are particularly preferable.

Examples of cyan couplers include phenol-based and naphthol-based couplers, and U.S. Pat.
4,146,396, 4228,233, 4,296,200, 2,36
No. 9,929, No. 2,801,171, No. 2,772,162, No. 2,89
5,826, 3,772,002, 3,758,308, 4,3
34,011, 4,327,173, West German Patent Publication 3,329,729
No., European Patent No. 121,365A, U.S. Patent No. 3,446,622,
No. 4,333,999, No. 4,451,559, No. 4,427,767
And those described in EP 161,626A are preferred.

Colored couplers to correct unwanted absorption of colored dyes are VII of Research Disclosure No. 17643.
-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57-39413,
U.S. Patent Nos. 4,004,929, 4,138,258, British Patent No.
Those described in No. 1,146,368 are preferable.

As a coupler in which the coloring dye has an appropriate diffusibility,
Those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570 and 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, 4,080,211 and 4,367,282.
No. 2,102,173 and the like.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,1.
Those described in 31,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472, and 4,338,393,
Multi-equivalent couplers described in No. 4,310,618 and the like, couplers containing dyes that recolor after separation according to European Patent No. 173,302A,
RD Nos. 11449 and 24241, bleaching accelerator releasing couplers described in JP-A-61-201247 and the like, and ligand releasing couplers described in U.S. Pat. No. 4,553,477 and the like.

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. 2,322,027.

The steps of the latex dispersion method, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Suitable supports that can be used in the present invention are, for example, those mentioned above.
RD.No. 17643, page 28, and RD.No. 18716, page 647 From the right column
See page 648, left column.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD.No.
17643, pages 28 to 29, and No. 18716, 651, left column to right column, can be developed by a usual method.

The color developer used for the development processing of the light-sensitive material of the present invention,
It is preferably an alcal aqueous solution containing an aromatic primary amine color developing agent. Although aminophenol compounds are useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino N, N-diethylaniline and 3-methyl. -4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates, etc. may be mentioned. Two or more of these compounds can be used in combination depending on the purpose.

Color developers include carbonates of alkali metals, ph buffers such as borate or phosphate, bromide salts, iodide salts,
It is common to include a development inhibitor such as benzimidazoles, benzothiazoles or mercapto compounds, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazavirocyclo [2,2,2] octane)
Preservatives such as bisphenols, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, current promoters such as ammines, dye-forming couplers, and fogging agents such as sodium boron hydride. Agents, auxiliary developing agents such as 4-phenyl-3-pyrazolidone, viscosity imparting agents,
Various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodine. Acetic acid,
1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N'N'-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid ) And their salts can be mentioned as representative examples.

When the reversal process is performed, black and white development is usually performed before color development. This black and white developer contains dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black-and-white developing agents such as 3-pyrazolidones such as pyrarizone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally 3 or less per square meter of the light-sensitive material, and 500 ml can be obtained by reducing the bromide ion concentration in the replenishing solution.
It can also be: When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.
Examples of bleaching agents include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones and nitro compounds are used. Typical bleaching agents are ferricyanide; dichromate; iron (II
I) or cobalt (III) organic complex salts, for example, aminopolycarboxylic acids such as ethyleneditetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid Or citric acid,
Complex salts of tartaric acid, malic acid, etc .; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Of these, ethylenediaminetetraacetic acid iron (III)
Aminopolycarboxylic acid iron (III) complex salts such as complex salts and persulfates are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the aminofolicarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,98.
No. 8, JP-A-53-32,736, JP-A-53-57,831 and JP-A-53-37,
418, 53-72,623, 53-95,630, 53-95,63
No. 1, No. 53-10,4232, No. 53-124,424, No. 53-141,6
No. 23, No. 53-28,426, Research Disclosure
No. 17,129 (July 1978) and other compounds having a mercapto group or a disulfide group; JP-A-50-140,12
No. 9 thiazolidine derivative; JP-B-45-8,506;
JP-A-52-20832, JP-A-53-32,735, U.S. Pat.
Thiourea derivatives described in 6,561; West German Patent No. 1,127,715
And iodide salts described in JP-A-58-16235; West German Patent No.
Polyoxyethylene compounds described in 966,410 and 2,748,430; polyamine compounds described in JP-B-45-8836;
Other JP-A-49-42,434, JP-A-49-59,644, JP-A-53-9
No. 4,927, No. 54-35,727, No. 55-26,506 No. 58-163,9
Compounds described in No. 40; bromide ions and the like can be used.

Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, U.S. Patent No. 3,893,858, West Patent No. 1,290,812, JP-A-53-9.
The compounds described in 5,630 are preferred. In addition, US Patent No.
The compounds described in 4,552,832 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

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

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used such as the coupler), the application, and the rinsing water temperature
It can be set in a wide range depending on the number of washing tanks (the number of stages), a replenishment-holding type such as countercurrent and forward flow, and various other conditions. Of these, the relationship between the washing tank and water volume in the multistage countercurrent method is as follows:
Journal of the Society of Motion Picture and Telev
It can be determined by the method described in ision Enginees Volume 64, P.248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In processing the color light-sensitive material of the present invention, as a solution to such a problem,
The method of reducing calcium and magnesium ions described in Japanese Patent Application No. 61-131,632 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated fungicides such as chlorinated sodium isocyanurate, polybenzotriazoles thereof, etc., Hiroshi Horiguchi, "Chemistry of antibacterial and antifungal agents". It is also possible to use the bactericides described in "Microbial Sterilization, Sterilization, and Antifungal Technology" edited by the Society of Hygiene Technology, and "Encyclopedia of Anti-proliferation and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can be variously designed depending on the characteristics of the light-sensitive material, application, etc., but in general, it is 20 to 10 minutes at 15 to 45 ° C, preferably 30 to 30 at 25 to 40 ° C.
A range of seconds-5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed by a stabilizer instead of the above washing with water. In such a stabilization process, Japanese Unexamined Patent Publication No.
All known methods described in -8,543, 58-14,834 and 60-220,345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. .

Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution that accompanies the washing and / or replenishment of the stabilizing solution can be reused in other steps such as the desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline compounds described in U.S. Pat.No. 3,342,597, No. 3,342,599, Schiff's base type compounds described in Research Disclosures 14,850 and 15,159, aldol compounds described in No. 13,924, metals described in U.S. Pat. Examples thereof include salt complexes and urethane compounds described in JP-A-53-135,628.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-containing compounds, if necessary, for the purpose of promoting color development.
You may incorporate 3-pyrazolidones. Typical compounds include JP-A-56-65,339, JP-A-57,144,547, and JP-A-58-65,339.
No. 115,438 is listed.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

Further, the silver halide light-sensitive material of the present invention is described in US Pat.
500,626, JP-A-60-133449, JP-A-59-218443, No. 6
It can also be applied to the photothermographic materials stored in 1-238056 and European Patent 210,660A2.

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

The structural formulas of the compounds other than the present invention used in the examples and the development processing methods for the samples are collectively shown at the end of the examples.

Example 1 In order to evaluate the effectiveness of the present invention, a multi-layer color light-sensitive material 101 composed of each layer having the following composition was prepared on a cellulose triacetate film support which was subjected to an undercoating process.

The amount (101 samples) coating amount represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin expressed in units of g / m ^2, also increasing The dyes are shown by the number of moles per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver 0.37 Gelatin 2.81 UV absorber UV-1 0.03 UV absorber UV-2 0.05 UV absorber UV-3 0.06 High boiling organic solvent for dispersion SOLV-1 0.07 2nd layer (intermediate) Layer) Gelatin 1.52 UV absorber UV-1 0.03 Same as above UV-2 0.05 Same as above UV-3 0.06 High boiling organic solvent for dispersion SOLV-1 0.07 Third layer (high sensitivity red color sensitive layer) Silver iodobromide emulsion (AgI Spherical particles having a content of 10 mol% and a particle size of 0.7 μm) 0.90 Silver iodobromide emulsion (spherical particles having an AgI content of 2 mol% and a particle size of 0.25 μm) 0.45 Gelatin 2.05 Producing dye I 7.0 × 10 ^-4 coupler EX-1 0.04 Same as above EX-2 0.19 Same as above EX-3 0.20 Same as above EX-4 0.10 Same as above EX-5 0.11 High boiling organic solvent for dispersion SOLV-2 0.10 Same as above SOLV-3 0.20 4th layer (low sensitivity red color sensitive layer) Iodine Silver bromide emulsion (3.5 mol% AgI content, uniform cubic emulsion 0.09 μm on each side) 0.60 Gelatin 1.93 Sensitizing dye D -1 9.0 x 10 ^-4 Coupler EX-1 0.03 Same as above EX-2 0.23 Same as above EX-3 0.24 Same as above EX-4 0.03 High boiling organic solvent for dispersion SOLV-2 0.10 Same as above SOLV-3 0.20 Fifth layer (intermediate layer) Gelatin 0.90 Anti-color mixing agent EX-6 0.09 High boiling organic solvent for dispersion SOLV-2 0.05 Dye F-1 0.04 Same as above F-2 0.04 6th layer (low sensitivity green color sensitive layer) Silver iodobromide emulsion (AgI content 3.5 mol %, Uniform cubic emulsion of 0.14 μm on each side) 0.46 Gelatin 0.93 Sensitizing dye D-II 6.0 × 10 ^-4 Coupler EX-7 0.36 Same as above EX-8 0.07 High boiling organic solvent for dispersion SOLV-2 0.32 7th layer (medium sensitivity) Green color-sensitive layer) Silver iodobromide emulsion (spherical particles having AgI content of 4 mol% and particle size of 0.40 μm) 0.67 Gelatin 0.86 Sensitizing dye D-II 9.0 × 10 ^-4 Same as above D-III 1.0 × 10 ^-4 Same as above D-IV 5.0 × 10 ^-5 Coupler EX-7 0.22 Same as above EX-8 0.10 Same as above EX-5 0.04 Same as above EX-9 0.09 High boiling organic solvent for dispersion SOLV-2 0.20 8th layer (high sensitivity green) Color-sensitive layer) Silver iodobromide emulsion (spherical particles with AgI content of 10 mol% and particle size of 0.7 μm) 0.48 Gelatin 0.46 Sensitizing dye D-II 5.0 × 10 ^-4 Coupler EX-7 0.04 Same as EX-5 0.01 Dispersion High-boiling organic solvent SOLV-2 0.04 9th layer (yellow filter layer) Gelatin 1.19 Yellow colloidal silver 0.11 Anti-color mixing agent EX-6 0.28 High-boiling organic solvent for dispersion Solv-2 0.15 10th layer (low sensitivity blue color sensitivity) Layer) Silver chloroiodobromide emulsion (cubic grains having AgI content of 1 mol%, AgCl5 mol% and side of 0.17 μm) 0.73 Gelatin 1.31 Sensitizing dye D-V1.0 × 10 ^-2 Coupler EX-10 0.74 Same as above EX-11 0.04 High boiling organic solvent for dispersion SOLV-2 0.25 11th layer (high sensitivity blue color sensitive layer) Silver chloroiodobromide emulsion (AgI content 8 mol%, AgCl content 6 mol%, equivalent circle diameter 0.60 μm, average aspect ratio) Ratio of 7 tabular grains) 0.10 Silver chloroiodobromide emulsion (Agl content 4 mol%, AgCl content 7 mol%, circle equivalent diameter 0.38 μm, average aspect ratio) Tabular grain with a ratio of 6) 0.20 gelatin 1.54 sensitizing dye DV 2.0 × 10 ^-3 coupler EX-10 0.28 same as EX-9 0.08 high boiling organic solvent for dispersion SOLV-2 0.09 12th layer (1st protective layer) Gelatin 0.60 UV absorber UV-4 0.11 Same as above UV-5 0.17 High boiling organic solvent for dispersion SOLV-4 0.02 Dye F-3 0.05 13th layer (2nd protective layer) Fine grain silver halide emulsion (AgI content 1 mol%, Spherical silver iodobromide with a circle equivalent diameter of 0.07 μm) 0.74 Gelatin 1.87 Polymethylmethacrylate particles (diameter 1.5 μm) 0.15 Hardener H-1 0.50 In addition to the above components, a surfactant is added as a coating aid to each layer. did.

 The sample manufactured as described above was designated as Sample 101.

(Preparation of Samples 102 and 103) A sample in which the DIR compound in the 11th layer of Sample 101 was removed was prepared as Sample 102. Similarly, for the 10th and 11th layers of Sample 101
A sample from which the DIR compound was removed was prepared and designated as sample 103.

(Preparation of Samples 104 to 106) By changing the coating amount of the fine grain silver halide of the 13th layer of Sample 101, samples of 0 g / m ² , 0.10 g / m ² and 0.37 g / m ² were prepared, Samples 104 to 106 were used.

(Preparation of Samples 107 and 108) Yellow coupler EX-10 of the 10th and 11th layers of Samples 106 and 105
Samples 107 and 108 were prepared in the same manner as Samples 106 and 105 except that (the coupler of the present invention) was replaced with Comparative Yellow Coupler EX-12 in an equimolar amount.

(Preparation of Sample 109) Sample 10 except that the DIR compound in the 11th layer of Sample 108 was removed.
Sample 109 was prepared in the same manner as 8.

(Preparation of Sample 110) Sample 110 was prepared in the same manner as Sample 108 except that the diffusible DIR compound of the present invention in the 10th and 11th layers of Sample 108 was replaced with a comparative DIR compound (diffusion resistance) in an equimolar amount. .

(Preparation of samples 111 and 112) Yellow coupler EX-12 of the 10th and 11th layers of samples 107 and 108
Samples 111 and 112 were prepared in the same manner as Samples 107 and 108 except that EX-13 (comparative coupler) was replaced with an equimolar amount.

(Preparation of Sample 113) Sample 110 except that the yellow coupler EX-12 of the 10th and 11th layers of Sample 110 was replaced with the coupler EX-10 of the present invention in an equimolar amount.
Sample 113 was prepared in the same manner as 110.

(Preparation of Sample 114) The coating amount of the fine grain silver halide in the 13th layer of Sample 113 was 0.3.
Sample 114 was prepared in the same manner as sample 113, except that the amount was 7 g / m ² .

(Preparation of Sample 115) Sample 115 was prepared in the same manner as in Sample 113 except that the DIR compound Cp-1 in the 10th and 11th layers of Sample 113 was replaced with Cp-2 in an equimolar amount.

(Preparation of sample 116) The DIR compound of the 11th layer of sample 114 was changed from EX-9 to EX-11 30
Replaced by mol% and 0.20 of fine grain silver halide in the 13th layer
Sample 116 was prepared in the same manner as sample 114, except that g / m ^{2 was} applied.

(Preparation of Samples 117 and 118) Samples were prepared in the same manner as Sample 101, except that the yellow couplers EX-10 of the 10th and 12th layers of Sample 101 were replaced with the yellow couplers EX-14 and EX-15 of the present invention in equimolar amounts. Created 117 and 118.

The above samples were subjected to white imagewise exposure, and the sensitivities of the blue color-sensitive layers after passing through the color development processing shown below are shown in Table 1.

<Processing-1> Color development processing was carried out at 38 ° C according to the following processing steps.

Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Settling 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stability 1 minute 05 seconds The processing solution composition used in each step is as follows. It was

Color developer Diethylenetriamine pentaacetic acid 1-Hydroxyethylden-1,1, -diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide 1.3mg Hydroxylamine sulfate 2.4g 4- (N-ethyl -N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5g Water added 1.0 pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate 10.0 g Water-added 1.0 pH 6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 175.0 ml Sodium bisulfite 4.6 g Water-added 1.0 pH 6.6 Stabilizer Formalin (40 %) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (flat Shown below as a measure representative of the degree of polymerization 10) was added to 0.3g water 1.0 Color reproducibility was evaluated by the color separation.

Imagewise wedge exposure with blue light and color development of the above-mentioned composition gave a yellow image shown in FIG. The density of the yellow component (D _B ) and the density of the magenta component (D _G ) obtained by the density measurement through the blue filter and the green filter are calculated as D _G / D _{B at the} exposure amount when D _B is 2.5.
Was taken as the color separation degree of the blue-sensitive layer and used as a scale showing the color reproducibility of the blue-sensitive layer. The results are summarized in Table 1.

The stability with respect to the processing direction was evaluated as follows.

After irradiating the sample with a rectangular irradiation of X-rays and performing the following processing A and processing B, the density of the rectangular is measured to determine the degree of deformation of the corner (that is, the edge) of the rectangular (processing B) /
The stability with respect to the processing direction was evaluated in comparison with (Treatment A).

Treatment A: A rectangular (35 mm × 12 mm) sample is vertically moved up and down while being kept perpendicular to the liquid surface of the color developing treatment solution having the above-mentioned composition, and the sample is passed through the treatment step. Processing B: The sample above is moved in the color developer having the above composition so that the surface of the sample is parallel to the traveling direction of the sample, and the sample is passed through the processing step. (Linear velocity 100 cm / min) That is, the image obtained after the process B having the process directionality by performing the X-ray irradiation as shown in FIG. 2 has a symmetrical shape as in the process A having no process directionality. If there is (0 ≤ x /
X ≦ 0.15) is good, and some slight deformation is recognized (0.0
5 <x / X ≤ 0.15) is possible, when the shape is significantly deformed after processing A with good symmetry and the density of the rear part in the processing direction is reduced (processing tailing phenomenon) (0.15 <x / X) I made it impossible. It is presumed that such image deformation due to the processing direction occurs because the diffusible development inhibitor generated in the image portion (photosensitive portion) moves to an undesired portion and causes a decrease in density.

 The above results are summarized in Table 1.

X is the density difference obtained by subtracting the background density of the unirradiated part of the sample from the maximum density of the X-ray irradiated part of the sample. x is the concentration difference between the maximum concentration and the minimum concentration of the X-ray irradiated portion of the sample. If x / X is small, the processability is good, and if it is large, the unevenness depending on the processing direction is large.

As is clear from Table 1, the samples of the present invention have no sensitivity deterioration, good processing stability, and excellent color reproducibility.

The structural formulas of the compounds used in the examples are shown below.

(Example 2) A sample was prepared by providing the following layers in order from the support on a support made of a cellulose triacetate film subjected to an undercoating process.
Created 101 to 108.

(In the following examples, silver halide emulsion and colloidal silver are shown in terms of silver (g / m ² ). Materials used are also shown in coating amount (g / m ² ).) (Preparation of Sample 201) 1st layer (antihalation layer) Black colloidal silver 0.2 Gelatin 3.0 Ultraviolet absorber UV-1 0.2 High boiling organic solvent OIL-1 0.02 Film thickness 2.40 μm 2nd layer (Intermediate layer) Gelatin 0.9 Film thickness 0.7 μm 3rd layer ( First red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (5 mol% silver iodide, average grain size 0.3 μ) 1.5 Gelatin 3.0 Sensitizing dye A 1.0 × 10 ⁻⁴ Sensitizing dye B 2.0 × 10 ⁻⁴ Sensitizing dye C 1.0 × 10 ^-4 coupler C-1 0.1 coupler C-2 0.4 coupler C-3 0.2 coupler C-4 0.03 coupler C-5 0.1 high boiling organic solvent OIL-1 0.1 high boiling organic solvent OIL-2 0.1 film Thickness 2.5 μm 4th layer (2nd red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (4 mol% silver iodide, average grain size 0.7 μm) 1.7 Gelatin 2 .5 Sensitizing dye A 3 × 10 ^-4 Sensitizing dye B 2 × 10 ^-4 Sensitizing dye C 1 × 10 ^-4 Coupler C-1 0.01 Coupler C-2 0.02 Coupler C-3 0.03 Coupler C-5 0.04 Coupler C-4 0.02 High-boiling organic solvent OIL-2 0.1 Film thickness 1.7 μm Fifth layer (intermediate layer) Gelatin 0.5 Compound Cpd-A 0.05 High-boiling organic solvent OIL-2 0.05 Film thickness 0.4 μm Sixth layer (first green color) Emulsion layer) Monodisperse silver iodobromide emulsion (3 mol% silver iodide, average grain size 0.3 μ) 0.4 Monodisperse silver iodobromide emulsion (6 mol% silver iodide, average grain size 0.5 μ) 0.8 Gelatin 3.0 increase Sensitizing dye D 3 × 10 ^-4 Sensitizing dye E 2 × 10 ^-4 Sensitizing dye F 1 × 10 ^-4 Coupler C-8 0.1 Coupler C-9 0.4 Coupler C-10 0.03 High boiling point organic solvent OIL-2 0.05 Membrane Thickness 1.7 μm Seventh layer (second green sensitive layer) Monodisperse silver iodobromide emulsion (silver iodide 4 mol%, average grain size 0.8 μ) 0.9 Gelatin 1.5 Sensitizing dye D 2 × 10 ⁻⁴ Sensitizing dye E 1.5 × 10 ^-4 Sensitizing dye F 1 × 10 ^-4 coupler C-6 0.10 coupler C-7 0.02 coupler C-10 0.01 high boiling organic solvent OIL-1 0.08 high boiling organic solvent OIL-3 0.03 film thickness 2.0 μm 8th layer (intermediate layer) gelatin 0.5 compound Cpd-A 0.6 High-boiling organic solvent OIL-1 0.3 Thickness 0.4 μm 9th layer (yellow filter layer) Yellow colloidal silver 0.05 Gelatin 1.5 Compound Cpd-A 0.2 High-boiling organic solvent OIL-1 0.1 Thickness 0.5 μm 10th layer (First blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 7 mol%, average grain size 0.3 μ) 0.3 Monodisperse silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.6 μ) ) 0.3 Gelatin 2.0 Sensitizing dye E 2 × 10 ^-4 Coupler C-11 0.1 Coupler C-12 0.4 Coupler C-4 0.08 High boiling point organic solvent OIL-3 0.30 Film thickness 1.6 μm 11th layer (2nd blue-sensitive emulsion layer) ) Monodisperse silver iodobromide emulsion (silver iodide 7 mol%, average grain size 1.5 μ) 0.8 gelatin 1.5 Sensitizing dye E 1 × 10 ^-4 coupler C-1 1 0.1 Coupler C-12 0.08 Coupler C-4 0.05 High boiling point organic solvent OIL-3 0.07 Thickness 1.3 μm 12th layer (first protective layer) Fine grain silver bromide emulsion (silver iodide 4 mol%, average grain size 0.07 μ) 0.1 Gelatin 1.0 UV absorber UV-2 0.1 UV absorber UV-3 0.2 High boiling organic solvent OIL-3 0.01 0.8 μm 13th layer (2nd protective layer) Gelatin 1.0 Polymethylmethacrylate particles (diameter 1.5μ) 0.2 Formaldehyde scavenger S-1 0.5 Film thickness 1.1 μm In addition, surfactant W-1 and hardener H-1 were added.

 The sample coated with the above layer structure is referred to as sample 101.

The dry film thickness between the surface of the photosensitive layer closest to the support defined in the present invention, which is closer to the support, and the surface of the protective layer, which is farther than the support and sandwiches the photosensitive layer, from the side remote from the support, It is 17 μm in the above sample.

 The structural formulas of the materials used in the examples are shown below.

Hardener H-1 CH ₂ = CHSO ₂ CH ₂ CH ₂ SO ₂ CH = CH ₂ (Preparation of Sample 202) Sample 202 and the twelfth layer of fine grain silver halide are coated at 0.5
A sample having 0 g / m ² was prepared and used as sample 202.

In the same manner as in Example 1, the results of examining the stability of the samples 201 and 202 against the processing direction are shown in Table 2.

(Example 3) Sample 301, which is a multilayer color light-sensitive material having the following composition, was prepared on an undercoated cellulose triacetate film support.

The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer.

First layer (antihalation layer) Black colloidal silver 0.2 Gelatin 1.0 ExM-9 0.06 UV-1 0.03 UV-2 0.06 UV-3 0.06 Sol-1 0.15 Sol-2 0.15 Sol-3 0.05 Second layer (intermediate layer) Gelatin 1.0 UV-1 0.03 ExC-4 0.02 ExF-1 0.004 Sol-1 0.1 Sol-2 0.1 Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent spherical diameter 0.5) μ, coefficient of variation of equivalent sphere diameter 20%, plate-like grain, diameter / thickness ratio 3.0) Coating amount of silver 1.2 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3 μ, variation of equivalent sphere diameter Coefficient 15%, spherical particles, diameter / thickness ratio 1.0) Coating silver amount 0.6 Gelatin 1.0 ExS-1 4 × 10 ^-4 ExS-2 5 × 10 ^-5 ExC-1 0.05 ExC-2 0.50 ExC-3 0.03 ExC-4 0.12 ExC-5 0.01 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, internal high AgI type with 1: 1 core-shell ratio, equivalent sphere diameter 0.7μ, variation coefficient of equivalent sphere diameter 15 %, Plate-like particles, Diameter / thickness ratio 5.0) coating silver amount 0.7 Gelatin ^{1.0 ExS-1 3 × 10 -4} ExS-2 2.3 × 10 -5 ExC-6 0.11 ExC-7 0.05 ExC-4 0.05 Sol-1 0.05 Sol-3 0.03 5 Layer (intermediate layer) Gelatin 0.5 Cpd-1 0.1 Sol-1 0.05 Sixth layer (low-sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core-shell ratio 1: 1 surface high AgI type, equivalent spherical diameter) 0.5μ, variation coefficient of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 4.0) Coating silver amount 0.35 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3μ, equivalent sphere diameter) Coefficient of variation 25%, granular particles, diameter / thickness ratio 1.0) Silver coating amount 0.20 Gelatin 1.0 ExS-3 5 × 10 ^-4 ExS-4 3 × 10 ^-4 ExS-5 1 × 10 ^-4 ExM-8 0.4 ExM -9 0.07 ExM-10 0.02 ExY-11 0.03 Sol-1 0.3 Sol-4 0.05 7th layer (high-sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core-shell ratio 1: 3, internal high AgI type) , Sphere equivalent diameter 0.7μ, coefficient of variation of sphere equivalent diameter 20%, plate-like particles Diameter / thickness ratio 5.0) coating silver amount 0.8 Gelatin ^{0.5 ExS-3 5 × 10 -4} ExS-4 3 × 10 -4 ExS-5 1 × 10 -4 ExM-8 0.1 ExM-9 0.02 ExY-11 0.03 ExC- 2 0.03 ExM-14 0.01 Sol-1 0.2 Sol-4 0.01 Eighth layer (intermediate layer) Gelatin 0.5 Cpd-1 0.05 Sol-1 0.02 Ninth layer (donor layer having a multilayer effect on the red-sensitive layer) Silver iodobromide emulsion (AgI ₂ mol%, core / shell ratio 2: 1, internal high AgI type, sphere equivalent diameter 1.0μ, variation coefficient of sphere equivalent diameter 15%, plate-shaped particles, diameter / thickness ratio 6.0) Silver coating amount 0.35 Silver iodobromide Emulsion (AgI 2 mol%, internal high AgI type with 1: 1 core-shell ratio, spherical equivalent diameter 0.4 μ, coefficient of variation of spherical equivalent diameter 20%, plate-shaped particles, diameter / thickness ratio 6.0) Silver coating amount 0.20 Gelatin 0.5 ExS- 3 8 × 10 ^-4 ExY-13 0.11 ExM-12 0.03 ExM-14 0.10 Sol-1 0.20 10th layer (yellow filter layer) Yellow colloidal silver 0.05 Gelatin 0.5 Cpd-2 0.13 Sol-1 0.13 Cpd-1 0.10 11th Layer (low sensitivity Emulsion-sensitive layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI type, equivalent sphere diameter 0.7 μ, variation coefficient of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 7.0) coating silver amount 0.4 iodide Silver bromide emulsion (AgI 3 mol%, uniform AgI type, sphere equivalent diameter 0.3μ, coefficient of variation of sphere equivalent diameter 25%, plate-shaped particles, diameter / thickness ratio 7.0) Silver coating amount 0.2 Gelatin 1.6 ExS-6 2 × 10 ^-4 ExC-16 0.05 ExC-2 0.10 ExC-3 0.02 ExY-13 0.07 ExY-15 1.0 Sol-1 0.20 Layer 12 (high sensitivity blue emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal AgI) Type, equivalent sphere diameter 1.0μ, variation coefficient of equivalent sphere diameter 25%, multiple twin plate particles, diameter / thickness ratio 2.0) Coating silver amount 0.5 Gelatin 0.5 ExS-6 1 × 10 ^-4 ExY-15 0.20 ExY- 13 0.01 Sol-1 0.10 13th layer (1st protective layer) Gelatin 0.8 UV-4 0.1 UV-5 0.15 Sol-1 0.01 Sol-2 0.01 14th layer (2nd protective layer) Fine grain silver bromide emulsion (AgI 2 mol) %, Uniform AgI type, sphere equivalent diameter 0.07μ) 0.05 Chin 0.45 polymethylmethacrylate particles diameter 1.5μ 0.2 H-1 0.4 Cpd-5 0.5 Cpd-6 0.5 each stabilizer emulsion in addition to the above components in Cpd-3
(0.04 g / m ² ) surfactant Cpd-4 (0.02 g / m ² ) was added as a coating aid.

Sol-1 tricresyl phosphate Sol-2 dibutyl phthalate (Preparation of Sample 302) The coating amount of the fine grain silver halide in the 14th layer of Sample 301 is 0.5
A sample having g / m ² was prepared and used as sample 302.

Table 3 shows the results of examining the stability of Samples 301 and 302 against the processing direction in the same manner as in Example 1.

[Brief description of drawings]

FIG. 1 shows the characteristic curve of the light-sensitive material of the present invention.
The horizontal axis shows the logarithmic value (log E) of the exposure amount (E), and the vertical axis shows the density (D). (A) shows a yellow characteristic curve, and (B) shows a magenta characteristic curve. FIG. 2 shows a method of evaluating the processing directionality during development. FIG. 2 is a schematic diagram of rectangular irradiation with X-rays, and is a view of the exposed surface from above. E is the rectangular exposure area,
Represents a non-exposed area. 2 and 2 represent the density profiles when the sample after rectangular exposure as shown in FIG. 2 was measured in the direction a to b with a microdensitometer. 2 is a symmetrical shape with no processing direction, and FIG. 2 is a profile with processing direction.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A 61-42656 (JP, A) JP-A 61-282841 (JP, A) JP-A 50-23228 (JP, A)

Claims (1)

(57) [Claims] 1. A silver halide color photographic light-sensitive material having a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support, which is represented by the following general formula [I] as a yellow dye-forming color coupler. A diffusible development inhibitor or a diffusible precursor for a developing bath preparation which reacts with an oxidant of a color developing agent in the same color-sensitive layer farthest from the support, containing at least one of the compounds shown. A compound which releases a compound and / or a compound which cleaves after development reaction with an oxidant of a color developing agent and cleaves a developing bath preparation by reacting with another molecule of a color developing agent is added to the photosensitive layer of the color-sensitive layer. It contains 1 mol% or more of silver halide and has a protective layer of a non-photosensitive hydrophilic colloid layer on the side farther from the support than the color-sensitive layer, and the non-photosensitive fine-grain halogen is contained in the protective layer. 15 times more silver halide than the above compounds The silver halide color photographic light-sensitive material characterized by containing more than Le. General formula [I]