JP2630494B2 - Silver halide color photographic materials - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material, and more particularly, to a silver halide color photographic material using a novel acylacetamide type yellow dye-forming coupler. It relates to a photosensitive material.

(Prior Art) A silver halide color photographic light-sensitive material (hereinafter simply referred to as a color photographic material) comprises an aromatic primary amine developing agent oxidized by subjecting the material to exposure and color development. A color image is formed by reaction with a dye-forming coupler (hereinafter, referred to as a coupler).

Generally, in this method, a color reproduction method using a subtractive color method is used, and in order to reproduce blue, green, and red, color images of yellow, magenta, and cyan, which have complementary colors, respectively, are formed. Among them, acylacetamide couplers and malondianilide couplers are generally used as yellow dye-forming couplers (hereinafter referred to as yellow couplers) for forming a yellow color image.

Yellow dyes obtained from these couplers are generally formed in a silver halide emulsion layer or a layer adjacent thereto which is color-sensitive to radiation having a complementary relationship to the radiation absorbed by the dye. It is a target.

Incidentally, yellow couplers, particularly acylacetamide couplers such as benzoylacetoanilide couplers and pivaloylacetoanilide couplers, are generally used for image formation. The former generally has a high coupling activity with an oxidized aromatic primary amine developing agent during development, and a color light-sensitive material for photography that requires high sensitivity because the molecular extinction coefficient of the generated yellow dye is large,
Particularly, it is mainly used for color negative films, and the latter is mainly used for color paper and color reversal films because of its excellent spectral absorption characteristics and fastness of yellow dye.

However, in the benzoylacetanilide type coupler, although the coupling reactivity with the oxidized form of the aromatic primary amine developer during color development is high and the molecular absorption coefficient of the generated yellow azomethine dye is large, the yellow image The pivaloyl acetanilide type coupler has the disadvantage of poor spectral absorption characteristics, and although it has excellent spectral absorption characteristics for yellow images, it has a coupling reactivity with the oxidized aromatic primary amine developer during color development. And the molecular extinction coefficient of the resulting yellow azomethine dye is low.

Here, the high coupling reactivity of the coupler and the large molecular extinction coefficient of the produced element enable high sensitivity, high gamma value and high color density, resulting in so-called high color developability. Further, the excellent spectral absorption characteristics in the yellow image means, for example, absorption characteristics in which the long wavelength side of the spectral absorption is good and the unnecessary absorption in the green region is small.

Therefore, the development of a yellow coupler having both advantages, that is, high color developing property (high coupling reactivity of coupler and large molecular extinction coefficient of dye) and excellent spectral absorption characteristics of a color image has been desired.

As an acyl group of an acylacetanilide type coupler,
U.S. Pat. No. 3,265,506 (U.S. Pat. No. Re. 27,848) discloses a pivaloyl group, a 7,7-dimethylnorbornane-1-carbonyl group, a 1-methylcyclohexane-1-carbonyl group and the like in JP-A-47-26133. Is cyclopropane-1
-Carbonyl group, cyclohexane-1-carbonyl group and the like are disclosed. However, these couplers were inferior in any point, such as poor coupling reactivity, low molecular extinction coefficient of the dye, or poor spectral absorption characteristics of color images.

In addition, benzoylacetanilide type and pivaloylacetoanilide type couplers, which represent acylacetanilide type couplers, are prepared by mixing and dissolving a coupler having an oil-soluble diffusion-resistant group in a molecule with a high boiling point organic solvent, and dispersing the finely dispersed dispersion. When a color light-sensitive material is prepared by mixing with silver halide, if the amount of the high-boiling organic solvent added is low with respect to the unit weight of the coupler, there is a disadvantage that the sensitivity and the color density are lowered.

Also, U.S. Pat.No. 3,265,506 which describes the aforementioned acylacetanilide type coupler, and JP-A-47-26133.
And JP-A Nos. 62-54257, 56-87041, and 54.
-99433, West German Patent 2,757,380, etc., wherein the acyl group described in the specification of an acylacetanilide-type coupler containing an alkylcarbonyl or cycloalkylcarbonyl includes a layer containing these yellow couplers and a layer containing these yellow couplers. There is no description or specific example of color development and color image fastness relating to the definition of the film thickness of the color photographic material containing a coupler. When actually examining photosensitive materials using these conventional couplers, it was found that there was a problem that the color developing property and color image fastness were inferior to the reduction of the film thickness, and that the amount of the high-boiling organic solvent added to the coupler was high. It has been found that the above problems are exacerbated by the reduction of.

(Problem to be Solved by the Invention) Therefore, the first problem to be solved by the present invention is as follows.
Provides a color photosensitive material that provides high activity, high color density, small changes in these excellent characteristics due to changes in the amount of high boiling organic solvent added per unit weight of coupler, and robust color images. Is to do. Second,
The first object of the present invention is achieved by reducing the dry film thickness of the color light-sensitive material, particularly the dry film thickness of the blue light-sensitive emulsion layer, and to provide a color light-sensitive material having improved image quality, particularly sharpness. It is in.

(Means for Solving the Problems) In order to solve the above-mentioned problems, the present inventors have conducted various studies, and as a result, have found that a yellow dye-forming coupler represented by the following general formula (I) is used in a blue-sensitive emulsion layer. , The thickness of the layer
The present inventors have found that the object can be satisfied by regulating the diameter to 5.0 μm or less, and have accomplished the present invention based on this finding.

That is, the present invention relates to a silver halide color photograph comprising at least one blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer and a non-light-sensitive layer on a support. In a light-sensitive material, at least one of the blue-sensitive silver halide emulsion layers contains at least one acylacetamide type yellow dye-forming coupler having an acyl group represented by the following general formula (I); An object of the present invention is to provide a silver halide color photographic material characterized in that the total dry film thickness of all silver halide emulsion layers is 5.0 μm or less.

General formula (I) (Wherein R ₁ represents a monovalent group. Q together with C is 3 to 5)
A non-metallic atomic group necessary for forming a 3- to 5-membered heterocyclic ring having at least one heteroatom selected from N, O, S, and P in the ring. However, R ₁ is not a hydrogen atom and does not combine with Q to form a ring. Hereinafter, the present invention will be described in more detail.

The acylacetamide type yellow coupler of the present invention is preferably represented by the following general formula [Y].

Formula [Y] In the formula [Y], R ₁ represents a monovalent substituent excluding hydrogen;
Represents a 3 to 5 membered hydrocarbon ring together with C or a 3 to 5 membered ring containing at least one hetero atom selected from N, S, O and P in the ring.
R ₂ represents a hydrogen atom, a halogen atom (F, Cl, Br, I ₀ , the same applies to the description of the formula [Y] below), an alkoxy group, and an aryl group. R ₃ represents a group capable of substituting an oxy group, an alkyl group or an amino group on the benzene ring, and X represents a group capable of leaving by a coupling reaction with a hydrogen atom or an oxidized form of an aromatic primary amine developer (hereinafter referred to as “X”). And l represents an integer of 0 to 4, respectively. However, when 1 is plural, plural R ₃ may be the same or different.

Here, examples of R ₃ include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, and an alkylsulfonyl group. , Ureido group, sulfamoylamino group, alkoxycarbonylamino group, alkoxysulfonyl group, acyloxy group, nitro group, heterocyclic group, cyano group, acyl group, acyloxy group,
There are an alkylsulfonyloxy group and an arylsulfonyloxy group, and examples of the leaving group include a heterocyclic group, an aryloxy group, an arylthio group, an alkylsulfonyloxy group, an arylsulfonyloxy group, and a heterocyclic group that are bonded to a coupling active site with a nitrogen atom. There are an oxy group and a halogen atom.

When the substituent in the formula [Y] is an alkyl group or contains an alkyl group, unless otherwise specified, the alkyl group may be a linear, branched or cyclic, even if substituted, unsaturated bond. An alkyl group which may contain (for example,
Methyl, isopropyl, t-butyl, cyclopentyl,
t-pentyl, cyclohexyl, 2-ethylhexyl,
1,1,3,3-tetramethylbutyl, dodecyl, hexadecyl, allyl, 3-cyclohexenyl, oleyl, benzol, trifluoromethyl, hydroxymethylmethoxyethyl, ethoxycarbonylmethyl, phenoxyethyl)
Means

When the substituent in the formula [Y] is an aryl group or contains an aryl group, unless otherwise specified, the aryl group may be a monocyclic or condensed ring aryl group which may be substituted (eg, phenyl, 1-naphthyl) , P-tolyl, o-
Tolyl, p-chlorophenyl, 4-methoxyphenyl,
8-quinolyl, 4-hexadecyloxyphenyl, pentafluorophenyl, p-hydroxyphenyl, p-cyanophenyl, 3-pentadecylphenyl, 2,4-di-
t-pentylphenyl, p-metalsulfonamidophenyl, 3,4-dichlorophenyl).

When the substituent in the formula (Y) is a heterocyclic group or contains a heterocyclic ring, unless otherwise specified, the heterocyclic group is O, N, S, P,
A 3- to 8-membered optionally substituted monocyclic or fused-ring heterocyclic group containing at least one heteroatom selected from Se and Te in the ring (for example, 2-furyl, 2-pyridyl, 4-
Pyridyl, 1-pyrazolyl, 1-imidazolyl, 1-benzotriazolyl, 2-benzotriazolyl, succinimide, phthalimide, 1-benzyl-2,4-imidazolidindion-3-yl).

Hereinafter, the substituents preferably used in the formula [Y] will be described.

In the formula [Y], R ₁ is preferably a halogen atom, a cyano group, or a monovalent group having 1 to 30 carbon atoms (hereinafter abbreviated as C number) which may be substituted (for example, alkyl group, alkoxy group) Or a monovalent group having 6 to 30 carbon atoms (eg, an aryl group or an aryloxy group), and examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, a nitro group, an amino group, a carbonamido group, There are a sulfonamide group and an acyl group.

In the formula [Y], Q is preferably a heterocyclic group selected from a hydrocarbon ring having 3 to 30 carbon atoms and optionally at least one of N, S, O and P, which may be substituted with any of 3 to 5 members together with C. It represents a group of nonmetallic atoms necessary for forming a heterocyclic ring having 2 to 30 carbon atoms containing atoms in the ring. Further, the ring formed by Q together with C may contain an unsaturated bond in the ring. Examples of the ring Q forms with C include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, an oxetane ring, an oxolane ring, a 1,3-dioxolane ring, a thietane ring, a thiolane ring,
There is a pyrrolidine ring. Examples of the substituent include a halogen atom,
Hydroxyl group, alkyl group, aryl group, acyl group,
There are an alkoxy group, an aryloxy group, a cyano group, an alkoxycarbonyl group, an alkylthio group, and an arylthio group.

In the formula [Y], R ₂ is preferably a halogen atom, an optionally substituted C 1-30 alkoxy group, a C 6-30 aryloxy group, a C 1-30 alkyl group or It represents an amino group having 0 to 30 carbon atoms, and examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group.

In the formula [Y], R ₃ is preferably a halogen atom, any of which may be substituted, an alkyl group having 1 to 30 carbon atoms,
An aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, C
An alkoxycarbonyl group having 2 to 30 carbon atoms, an aryloxycarbonyl group having 7 to 30 carbon atoms, a carbonamide group having 1 to 30 carbon atoms, a sulfonamide group having 1 to 30 carbon atoms, a carbamoyl group having 1 to 30 carbon atoms, Sulfamoyl group of numbers 0 to 30, C number 1
An alkylsulfonyl group of 30; an arylsulfonyl group of 6 to 30 carbon atoms; a ureido group of 1 to 30 carbon atoms; a sulfamoylamino group of 0 to 30 carbon atoms; an alkoxycarbonylamino group of 2 to 30 carbon atoms; A heterocyclic group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, an alkylsulfonyloxy group having 1 to 30 carbon atoms, and an arylsulfonyloxy group having 6 to 30 carbon atoms. , An alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group,
Heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, acyl group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonylamino group, sulfamoylamino Group, ureido group, cyano group, nitro group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyloxy group, and arylsulfonyloxy group.

In the formula [Y], l preferably represents an integer of 1 or 2, and the substitution position of R ₃ is The meta position or the para position with respect to is preferred.

In the formula [Y], X preferably represents a heterocyclic group or an aryloxy group bonded to the coupling active site with a nitrogen atom.

When X represents a heterocyclic group, X is preferably a 5- to 7-membered monocyclic or condensed heterocyclic group which may be substituted, and examples thereof include succinimide, maleimide, phthalimide and diglycol. Imide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2,4-dione, thiazolidine-
2,4-dione, imidazolidine-2-one, oxazolidine-2-one, thiazolidine-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, 6-pyridazone-2-pyrazone, 2-amino-1 , 3,4-thiazolidine, 2-imino-
There are 1,3,4-thiazolidine-4-one and the like, and these heterocycles may be substituted. Examples of the substituent of these heterocycles include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a sulfo group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and an alkyl group. Sulfonyl group, arylsulfonyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, acyl group, acyloxy group, amino group, carbonamide group, sulfonamide group,
There are a carbamoyl group, a sulfamoyl group, a ureido group, an alkoxycarbonylamino group, and a sulfamoylamino group. When X represents an aryloxy group, X preferably represents an aryloxy group having 6 to 30 carbon atoms, and may be substituted with a group selected from the substituent group mentioned above when X is a heterocyclic ring. . Examples of the substituent of the aryloxy group include a halogen atom, a cyano group, a nitro group, a carboxyl group, a trifluoromethyl group, an alkoxycarbonyl group,
A carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group or an arylsulfonyl group is preferred.

Next, substituents particularly preferably used in the formula [Y] will be described.

R ₁ is particularly preferably a halogen atom or an alkyl group, most preferably a methyl group. Q is particularly preferably a group of non-metallic atoms in which a ring formed together with C forms a 3- to 5-membered hydrocarbon ring. It is. Here, R represents a hydrogen atom, a halogen atom or an alkyl group. However, a plurality of Rs may be the same or different.

Q most preferably forms a three-membered ring with the C to which it is attached It is.

R ₂ is particularly preferably a chlorine atom, a fluorine atom, and a C number of 1
To 6 alkyl groups (e.g., methyl, trifluoromethyl, ethyl, isopropyl, t-butyl);
(E.g., methoxy, ethoxy, methoxyethoxy, butoxy), or an aryloxy group having 6 to 24 carbon atoms (e.g., phenoxy, p-tolyloxy, p-
Methoxyphenoxy) and most preferably a chlorine atom,
It is a methoxy group or a trifluoromethyl group.

R ₃ is particularly preferably a halogen atom, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group or a sulfamoyl group, and most preferably an alkoxy group, an alkoxycarbonyl group, or a carbonamide group. Group or a sulfonamide group.

X is particularly preferably a group represented by the following formula [Y-1], [Y-2] or [Y-3].

Formula [Y-1] In the formula [Y-1], Z is Represents Here, R ₄ , R ₅ , R ₈ , and R ₉ represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or an amino group, R ₆ and R ₇ are a hydrogen atom, an alkyl group, an aryl group,
It represents an alkylsulfonyl group, an arylsulfonyl group or an alkoxycarbonyl group, and R ₁₀ and R ₁₁ represent a hydrogen atom, an alkyl group or an aryl group. R ₁₀ and R ₁₁ may combine with each other to form a benzene ring. R ₄ and R ₅ ,
R ₅ and R ₆ , R ₆ and R ₇ or R ₄ and R ₈ may combine with each other to form a ring (eg, cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine, piperidine).

Particularly preferred among the heterocyclic groups represented by the formula [Y-1] are those wherein Z in the formula [Y-1] Is a heterocyclic group. The C number of the heterocyclic group represented by the formula [Y-1] is 2 to 30, preferably 4 to 20, and more preferably 5 to 16.

Formula [Y-2] In the formula [Y-2], at least one of R ₁₂ and R ₁₃
One is a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, an alkoxycarbonyl group,
A group selected from a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group or an acyl group,
The other may be a hydrogen atom, an alkyl group or an alkoxy group. R ₁₄ represents a group having the same meaning as R ₁₂ or R _13, and m represents an integer of 0 to 2. The aryloxy group represented by the formula [Y-2] has a C number of 6 to 30, preferably 6 to 2.
4, more preferably 6 to 15.

Formula [Y-3] In the formula [Y-3], W represents a group of nonmetal atoms necessary for forming a pyrrole ring, a pyrazole ring, an imidazole ring or a triazole ring together with N. here, The ring represented by may have a substituent, examples of preferred substituents include a halogen atom, a nitro group, a cyano group,
It is an alkoxycarbonyl group, an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group or a carbamoyl group. The C number of the heterocyclic group represented by the formula [Y-3] is 2 to 30, preferably 2 to 24, more preferably 2 to
It is 16.

X is most preferably a group represented by the formula [Y-1].

The coupler represented by the formula (Y) has a substituent R ₁ , Q, X, or May form a dimer or a multimer which bonds to each other through a divalent or higher valent group. In this case, the number of carbon atoms may be out of the specified range for each substituent.

 Specific examples of each substituent in the formula [Y] are shown below.

R ₁ and Q make with C Is shown below.

Examples of R ₂ F, Cl, Br, I, CH ₃ O−, _{CH 3 -, C 2 H 5} -, i-C 3 H 7 -, t-C 4 H 9 -, CH 3 OCH 2 CH 2 O-, CF 3 -, N- (CH 3) 2, _{n-C 4 H 9 O-,} n-C 14 H 29 O-, n-C 16 H 33 O-, Examples of _{n-C 12 H 25 O- R} 3 F, Cl, Br, I, CH 3 O-, C 2 H 5 O-, n-C 12 H 25 O-, CH 3, t-C 4 H 9 −, −COOCH ₃ , COOC ₂ H ₅ , −COOC ₄ H ₉ ⁻ⁿ , −COOC ₁₂ H ₂₅ ⁻ⁿ , −SO ₂ NHCOC ₂ H ₅ , −SO ₂ NHC ₁₆ H ₃₃ ⁻ⁿ , −NHCOC ₁₃ H ₂₇ ⁻ⁿ , −NHCOC ₁₅ H ₃₁ ⁻ⁿ , −NHCOC ₁₇ H ₃₅ ⁻ⁿ −NHSO ₂ C ₁₂ H ₂₅ ^-n , −NHSO ₂ C ₁₆ H ₃₃ ^-n , −SO ₂ NHCH ₃ , −OSO ₂ C ₁₂ H ₂₅ ^-n , −NHCOOC ₁₂ H ₂₅ ^-n , X Specific examples of the yellow coupler represented by the formula [Y] are shown below.

The yellow coupler of the present invention represented by the formula [Y] can be synthesized by the following synthesis route.

Here, the compound a is represented by J. Chem. Soc. (C), 1968, 254.
8, J. Am. Chem. Soc., 1934, 56 , 2710, Synthesis, 1971, 25
8, synthesized by the method described in J. Org. Chem., 1978, 43 , 1729, CA, 1960, 66 , 18533y.

Compound b is synthesized using thionyl chloride, oxalyl chloride or the like without solvent or methylene chloride, chloroform, carbon tetrachloride, dichloroethane, toluene, N, N-
The reaction is performed in a solvent such as dimethylformamide or N, N-dimethylacetamide. The reaction temperature is usually -20 ° C to 150 ° C, preferably -10 ° C to 80 ° C.

Compound c is synthesized by converting ethyl acetoacetate to an anion using magnesium methoxide or the like, and adding b to the anion. The reaction is carried out without solvent or using tetrahydrofuran, ethyl ether or the like, and the reaction temperature is usually -20
C. to 60C, preferably -10C to 30C. Compound d is synthesized by reacting compound c with a base such as aqueous ammonia, an aqueous solution of NaHCO _{3, an} aqueous solution of sodium hydroxide, or the like, without solvent or in a solvent such as methanol, ethanol, or acetonitrile. Reaction temperature is usually -20
C. to 50C, preferably -10C to 30C.

Compound e is synthesized by reacting compounds d and g without solvent. The reaction temperature is usually 100 to 150 ° C, preferably 100 to 120 ° C. When X is not H, compound f is synthesized by introducing a leaving group X after chlorination or bromination. Compound e is chloro-substituted with sulfuryl chloride, N-chlorosuccinimide or the like, or bromo-modified with bromine or N-bromosuccinimide in a solvent such as dichloroethane, carbon tetrachloride, chloroform, methylene chloride or tetrahydrofuran. At this time, the reaction temperature was-
The temperature is from 20C to 70C, preferably from -10C to 50C.

Next, the chloro-substituted or bromo-substituted product and the leaving group protonated product H-X are combined with methylene chloride, chloroform, tetrahydrofuran, acetone, acetonitrile, dioxane, N-methylpyrrolidone, N, N'-dimethylimidazolidin-2- On, N, N'-dimethylformamide,
In a solvent such as N, N-dimethylacetamide, the reaction temperature is -20.
The coupler f of the present invention can be obtained by reacting at a temperature of from 150C to 150C, preferably from -10C to 100C. At this time, triethylamine, N-ethylmorpholine, tetramethylguanidine, potassium carbonate, sodium hydroxide,
A base such as sodium bicarbonate may be used.

 Hereinafter, synthesis examples of the coupler of the present invention will be described.

Synthesis Example 1 Synthesis of Exemplified Compound Y-30 25 g of 1-methylcyclopropanecarboxylic acid synthesized by the method described in Gotkis, D. et al., J. Am. Chem. Soc., 1934, 56 , 2710, chloride In a mixture of 100 ml of methylene and 1 ml of N, N-dimethylformamide, 38.1 g of oxalyl chloride was added dropwise at room temperature over 30 minutes. After the dropwise addition, the mixture was reacted at room temperature for 2 hours, and methylene chloride and excess oxalyl chloride were removed under reduced pressure of an aspirator to obtain an oil of 1-methylcyclopropanecarbonyl chloride.

In a mixture of 6 g of magnesium and 2 ml of carbon tetrachloride, 100 ml of methanol is added dropwise at room temperature over 30 minutes. After heating under reflux for 2 hours, 32.6 g of ethyl 3-oxobutanoate is added dropwise over 30 minutes while heating under reflux. After the dropwise addition, the mixture is heated under reflux for another 2 hours, and methanol is completely distilled off under reduced pressure of an aspirator. 100 ml of tetrahydrofuran is added to the reaction mixture for dispersion, and the 1-methylcyclopropanecarbonyl chloride obtained above is added dropwise at room temperature. After reacting for 30 minutes, the reaction solution was extracted with 300 ml of ethyl acetate and diluted sulfuric acid, washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off to remove 2- (1-methylcyclopropanecarbonyl) -3-oxobutane. 55.3 g of ethyl acid oil was obtained.

2- (1-methylcyclopropanecarbonyl) -3-
A solution of 55 g of ethyl oxobutanoate and 160 ml of ethanol is stirred at room temperature, and 60 ml of 30% aqueous ammonia is added dropwise thereto over 10 minutes. Thereafter, the mixture was stirred for 1 hour, extracted with 300 ml of ethyl acetate, diluted with hydrochloric acid, neutralized and washed with water. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain an oil of (1-methylcyclopropanecarbonyl) ethyl acetate. 43 g were obtained.

(1-methylcyclopropanecarbonyl) ethyl acetate
34 g and N- (3-amino-4-chlorophenyl) -2-
(2,4-di-t-pentylphenoxy) butanamide 44.
5 g is heated and refluxed at an internal temperature of 100 to 120 ° C. under reduced pressure of an aspirator. After reacting for 4 hours, the reaction solution was purified by column chromatography using a mixed solvent of n-hexane and ethyl acetate to give Exemplified Compound Y-30.
49 g were obtained as a viscous oil. The structure of the compound was confirmed by MS spectrum, NMR spectrum and elemental analysis.

Synthesis Example 2 Synthesis of Exemplified Compound Y-1 22.8 g of Exemplified Compound Y-30 was dissolved in 300 ml of methylene chloride, and 5.4 g of sulfuryl chloride was added dropwise over 10 minutes while cooling with ice.
After reacting for 30 minutes, the reaction solution was thoroughly washed with water, dried over anhydrous sodium sulfate and concentrated to obtain a chloride of Exemplified Compound Y-30. 1-
In a solution of 18.7 g of benzyl-5-ethoxyhydantoin, 11.2 ml of triethylamine and 50 ml of N, N-dimethylformamide, the chloride of Exemplified Compound Y-30 previously synthesized was converted into N, N
-Dissolve in 50 ml of dimethylformaldehyde dropwise at room temperature over 30 minutes.

Then, after reacting at 40 ° C. for 4 hours, the reaction solution was diluted with
After extracting and washing with 0 ml, the mixture is washed with 300 ml of a 2% aqueous solution of triethylamine and then neutralized with dilute hydrochloric acid. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and the resulting oil was crystallized from a mixed solvent of n-hexane and ethyl acetate. The precipitated crystals were filtered, washed with a mixed solvent of n-hexane and ethyl acetate, and dried to obtain 22.8 g of crystals of the exemplary compound Y-1.

The structure of the compound was confirmed by MS spectrum, NMR spectrum and elemental analysis. The melting point was 132-3 ° C.

The yellow coupler represented by formula (I) of the present invention can be used in the range of 1.0 to 1.0 × 10 ^-3 mol per mol of silver halide. Preferably 5.0 × 10 ^{-1 to} 5.0 ×
10 ^-2 mol, more preferably 4.0 × 10 ^{−1 to} 2.0 × 10 ⁻²
Range of moles.

Two or more yellow couplers represented by the general formula (I) of the present invention can be used in combination, or can be used in combination with other known couplers.

The coupler represented by formula (I) of the present invention can be introduced into a color light-sensitive material by various known dispersion methods.

In the oil-in-water dispersion method, a low-boiling organic solvent (for example,
Ethyl acetate, butyl acetate, methyl ethyl ketone, isopropanol, etc.)
A method in which substantially no low-boiling organic solvent remains in the dry film may be used. When a high-boiling organic solvent is used, any of those having a boiling point at normal pressure of 175 ° C. or higher (specific examples thereof will be described later) may be used, or one or more of them may be arbitrarily mixed and used. it can. The ratio of the couplers of the invention to these high-boiling organic solvents can vary widely, but is in the range of a weight ratio of 5.0 or less per gram of coupler. It is preferably from 0 to 2.0, and more preferably from 0.01 to 1.0.

Further, a latex dispersion method described below can also be applied.

Further, it can be used by mixing or coexisting with various couplers and compounds described later.

The light-sensitive material of the present invention comprises at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer of a silver halide emulsion layer on a support.
The number of layers and the order of the silver halide emulsion layer and the non-photosensitive layer are not particularly limited as long as the layers are provided. The blue-sensitive layer of the present invention has photosensitivity in substantially the same wavelength region of 400 to 500 nm. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light and red light or infrared light. In a multilayer silver halide color photographic light-sensitive material, a unit photosensitive layer is generally used. The arrangement of the light-sensitive layers is provided in the order of the red color-sensitive layer, the green color-sensitive layer, and the blue color-sensitive layer from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer is described in JP-A-61-43748 and JP-A-59-113438.
No. 59-113440, No. 61-20037, couplers as described in the specification of JP 61-20038, DIR compounds and the like may be contained, and contains a color mixing inhibitor as usually used. You may go out.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045.
No. 2 of the high-speed emulsion layer and the low-speed emulsion layer
A layer configuration can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also, JP-A-57-112751, 62-127
As described in 200350, 62-206541, 62-206543, etc., a low-speed emulsion layer may be provided on the side remote from the support and a high-speed emulsion layer may be provided on the side near the support.

As specific examples, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL) or BH / BL /
They can be installed in the order of GL / GH / RH / RL or BH / BL / GH / GL / RL / RH.

Also, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL / RL is selected from the side farthest from the support.
Can be arranged in this order. JP-A-56-25738
As described in JP-A-62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the less sensitive silver halide emulsion layer, and the lower layer is more sensitive than the middle layer. A silver halide emulsion layer having a low degree is arranged,
There is an array composed of three layers having different sensitivities in which the sensitivities are sequentially decreased toward the support. Even in the case of three layers having different sensitivities, Japanese Patent Application Laid-Open No.
As described in JP-A-202464, a medium-speed emulsion layer / a high-speed emulsion layer / a low-speed emulsion layer may be arranged in the same color-sensitive layer from the side remote from the support.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.

The arrangement may be changed as described above even in the case of four or more layers.

No. 4,663,271 to improve color reproduction
No. 4,705,744, 4,707,436, JP-A-62-16
No. 4,448,63-89850, a donor layer (CL) having a multilayer effect having a different spectral sensitivity distribution from the main photosensitive layer such as BL, GL, RL is disposed adjacent to or close to the main photosensitive layer. Is preferred.

Preferred silver halide contained in the blue-sensitive silver halide emulsion layer of the silver halide color photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride or silver iodochloride having an average silver iodide content of 2.0 mol% or more. It is silver iodochloride. Preferred are silver iodobromide or silver iodochloride having an average silver iodide content of 2.0 to 25.0 mol%, and particularly preferred is iodobromide having an average silver iodide content of 3.0 to 20.0 mol%. It is silver bromide or silver iodochloride.

The blue-sensitive silver halide emulsion layer in the present invention is a silver halide emulsion layer having a spectral absorption maximum wavelength of preferably from 410 to 480 nm, wherein the silver halide emulsion layer contains at least one yellow dye-forming coupler. Refers to the emulsion layer contained. However, the yellow dye-forming coupler does not consist solely of the functional coupler. Functional couplers are couplers that release a photographically useful residue upon coupling as described below, such as development inhibitor releasing (DIR) couplers, nucleating agents or development accelerator releasing (DAR) couplers,
Bleach accelerator releasing (BAR) couplers, dyes (leuco dyes,
Fluorescent dyes and the like) emission couplers and the like.

In the present invention, the dry film thickness of all the blue-sensitive silver halide emulsion layers is 5.0 μm or less, regardless of the number of layers and the layer constitution described above. By setting the dry film thickness, high color density with high activity can be provided, and the obtained color image can maintain the robust property, and the image quality, particularly sharpness, can be improved.

The dry thickness of all the blue-sensitive silver halide emulsion layers is preferably 4.0 μm or less. More preferred is 3.0 μm or less. The lower limit of the dry film thickness can be reduced within a range that satisfies the function of the blue-sensitive silver halide emulsion layer of the color light-sensitive material, but the value is about 1.0 μm.

On the other hand, in the light-sensitive material of the present invention, irrespective of the dry thickness of the above-described all-blue-sensitive silver halide emulsion layer, the dry thickness of all the layers except for the support and the undercoat layer of the support is 25.0 μm or less. In some cases, it has been found that the object of the present invention can be achieved. The dry film thickness of all the layers is preferably 21.0 μm or less, and more preferably 18.0 μm or less. As the lower limit, the thickness can be reduced within a range that satisfies the intended performance of the light-sensitive material, but the value is approximately 8.0 μm.

The film thickness of the light-sensitive material of the present invention can be measured by the following method. The photosensitive material to be measured is stored at 25 ° C. and 55% relative humidity (2 days). Thereafter, the total thickness of the photosensitive material was measured, and then the coating layer on the support was removed. After that, the thickness was measured again, and the difference was used to calculate the total coating thickness of the photosensitive material excluding the support. It can be a film thickness. To measure the thickness, for example, a film thickness measuring device provided with a contact-type piezoelectric transducer (Anritsu Electric Co. Led., K-402B St.
and.) can be measured. The removal of the pressure of the coating film on the support can be performed using, for example, an aqueous solution of sodium hypochlorite.

Subsequently, using a scanning electron microscope, a cross-sectional photograph of the photosensitive material was taken (preferably at a magnification of 3,000 or more), and the total thickness and the thickness of each layer on the support were measured. The thickness of each layer can be calculated by comparing the measured value of the total thickness (the absolute value of the thickness).

Silver halide grains in photographic emulsions are cubic, octahedral,
It may be one having regular crystals such as tetradecahedron, one having irregular crystal forms such as spherical or plate-like, one having crystal defects such as twin planes, or a complex form thereof.

The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion that can be used in the present invention is described, for example, in Research Disclosure (RD) No. 17643 (1978).
December, p. 22-23, "I. Emulsion preparatio
n and types) ”, and No. 18716 (November 1979), 64
8, Grafkid, "Physics and Chemistry of Photography," published by Paul Montell (P. Glafkides, Chemie et Phisique Photograp
hique, Paul Montel, 1967), Duffin's "Photoemulsion Chemistry", published by Focal Press (GFDuffin, Photographi).
c Emulsion Chemistry (Focal Press, 1966)), "Manufacture and coating of photographic emulsions" by Zerikman et al., published by Focal Press (VLZelikman et al., Making and Coating Phot).
ographic Emulsion, Focal Press, 1964).

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

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described in Gatoff, Gutoff, Photographic Science and Engineerin.
g), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4,434,2
No. 26, 4,414,310, 4,433,048, 4,439,520 and British Patent No. 2,112,157 can be easily prepared.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, the inside may have a plurality of layered structures, and the halogenation having a different composition due to an epitaxial junction. Silver may be bonded, or may be bonded to a compound other than silver halide, such as, for example, silver rhodan or lead oxide.

 Also, a mixture of particles of various crystal forms may be used.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additive used in such a process is Research Disclosure No. 1
7643 and No. 18716, and the relevant portions are summarized in the table below.

Known photographic additives which 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.

Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Patent Nos. 4,411,987 and 4,435,5
It is preferable to add a compound which can react with formaldehyde described in No. 03 and can be fixed to the photosensitive material.

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

Examples of the yellow coupler that can be used in combination with the yellow coupler represented by formula (I) of the present invention include, for example, U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024,
No. 4,401,752, No. 4,248,961, Japanese Patent Publication No. 58-10739
Nos., UK Patent Nos. 1,425,020, 1,476,760, U.S. Pat.Nos. 3,973,968, 4,314,023, and 4,511,649
And those described in EP 249,473A and the like are preferred.

As the magenta coupler, 5-pyrazolone-based and other pyrazoloazole-based compounds are preferable, and U.S. Pat.Nos. 4,310,619 and 4,351,897, and EP 73,636.
No. 3,061,432, U.S. Pat. No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 2423
0 (June 1984), JP-A-60-43659 and JP-A-61-72238.
No. 60-35730, No. 51-118034, No. 60-185951
No. 4,500,630, US Pat. No. 4,540,654, US Pat.
556,630 and WO88 / 04795 are particularly preferable.

Cyan couplers include phenolic and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200,
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, No. 249,453
A, U.S. Pat.Nos. 3,446,622, 4,333,999,
No. 4,775,616, No. 4,451,559, No. 4,427,767, No. 4,690,889, No. 4,254,212, No. 4,296,199,
Preferred are those described in JP-A-61-42658. Also,
Imidazole couplers, for example, JP-A-1-250953,
No. 1-250945, No. 2-141744, European Patent No. 354,549A
The described couplers can also be used.

Colored couplers for correcting unwanted absorption of coloring dyes are described in Research Disclosure No. 17643 VII.
Section G, U.S. Pat.No. 4,163,670, JP-B-57-39413,
U.S. Pat.Nos. 4,004,929 and 4,138,258; British Patent No.
Preferred are those described in Japanese Patent Application No. 1,146,368 and Japanese Patent Application No. 2-75916. Further, a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181 and a dye that can form a dye by reacting with a developing agent described in U.S. Pat.No.4,777,120 It is also preferable to use a coupler having a precursor group as a leaving group.

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are 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 (Published) No. 3,234,533.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 4,409,320, No. 4,576,910, UK Patent No. 2,
No. 102,137, etc.

Couplers which release a photographically useful residual gas upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are described in RD17643, VII-F above.
Patents, JP-A-57-151944 and JP-A-57-1542
No. 34, No. 60-184248, No. 63-37346, No. 63-37350
And those described in U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include UK Patent Nos. 2,097,140 and 2,1
No. 31,188, JP-A Nos. 59-157638 and 59-170840 are preferred.

In addition, as couplers that can be used in the light-sensitive material of the present invention, competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472 and 4,338,393,
No. 4,310,618 and the like, multi-equivalent couplers described in
185950, JP-A-62-24252, etc., DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR
Coupler releasing redox compounds or DIR redox releasing redox compounds, EP 173,302A, EP 31
No. 3,308A, couplers releasing dyes that recolor after release, RD Nos. 11449, 24241, bleaching accelerator releasing couplers described in JP-A-61-201247, U.S. Pat.No. 4,555,477
And the couplers releasing ligands described in JP-A-63-75.
No. 747, a coupler releasing a leuco dye, and a coupler releasing a fluorescent dye described in US Pat. No. 4,774,181.

The coupler used in the present invention can be introduced into a 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.

Specific examples of high-boiling organic solvents having a boiling point at normal pressure of 175 ° C. or higher used in 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 and the like, esters of phosphoric acid or phosphonic acid ( Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, dichloropropyl phosphate 2
-Ethylhexylphenylphosphonate, etc.), benzoic esters (2-ethylhexylbenzoate, dodecylbenzoate, etc.), amides (N, N-diethyldodecaneamide, N, N-diethyllaurylamide) , N-tetradecylpyrrolidone), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-
Amylphenol, 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, etc.), hydrocarbons (paraffin,
Dodecylbenzene, diisopropylnaphthalene, etc.). The auxiliary solvent has a boiling point of about 30 ° C.
Above, preferably 50 ° C. or more and about 160 ° C. or less of an organic solvent can be used, typical examples are ethyl acetate, butyl acetate,
Examples include ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

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

In the color light-sensitive material of the present invention, JP-A-63-257747 is used.
No. 62-272248 and JP-A-1-80941, 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, It is preferable to add various preservatives or fungicides such as 2-phenoxyethanol and 2- (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. Preference is given to color negative films for general use or movies and color reversal films for slides or televisions.

Suitable supports that can be used in the present invention include, for example, those described above.
From page 28 of RD.No.17643, and from the right column of page 647 of No.18716
It is described in the left column on page 648.

In the light-sensitive material of the present invention, the film swell speed T1 / 2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film swelling speed T1 / 2 is
It can be measured according to a method known in the art. For example, a swellometer of the type described by A. Green et al. In Photographic Science and Engineering (Photogr. Sci. Eng.), Vol. 19, No. 2, pp. 124-129. ) Can be measured, and T1 / 2 is 90% of the maximum swollen film thickness reached when the color developer is processed at 30 ° C for 3 minutes and 15 seconds, and the saturated film thickness is defined as T1 / 2. Is defined as the time to reach.

The film swelling speed T1 / 2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is 15
0-400% is preferred. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness−film thickness) /
It can be calculated according to the film thickness.

The color photographic light-sensitive material according to the present invention is described in RD.No.
The development can be carried out by the usual methods described in 17643, pp. 28-29, and No. 18716, 615 left column to right column.

The color developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as this color developing agent, but p-
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. These compounds can be used in combination of two or more depending on the purpose.

Color developing solutions include pH buffers such as alkali metal carbonates, borates or phosphates, chlorides, bromides,
It generally contains a development inhibitor or an antifoggant such as an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. If necessary, hydroxylamine, diethylhydroxylamine, bis (β-carboxyethyl) hydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, catecholsulfone Various preservatives such as acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-phenyl-3 -An auxiliary developing agent such as pyrazolidone, a viscosity-imparting agent, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrile Triacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N , N-tetramethylenephosphonic acid,
Ethylenediamine-di (o-hydroxyphenylacetic acid)
And their salts can be mentioned as typical examples.

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

The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 or less per square meter of the photographic material, and 500 ml by reducing the bromide ion concentration in the replenishing solution.
It can also be: When the replenishment amount 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.

The ratio of the contact area with air to the volume of the photographic processing solution in the processing tank (unit: cm ⁻¹ , aperture ratio) is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method of reducing the aperture ratio as described above, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, Japanese Patent Laid-Open No.
No. 033, the method using a movable lid,
The slit development method described in No. 050 can be exemplified. The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the subsequent steps, for example, all the steps of bleaching, bleach-fixing, fixing, washing and stabilization. Further, the amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the current liquid.

The time for the color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing processing before bleach-fixing processing or bleaching processing after bleach-fixing processing can be arbitrarily performed according to the purpose.
As the bleaching agent, known compounds can be used. Among them, ethylenediaminetetraacetate (III) complex salt and 1,3-
Iron (III) complex salts of aminopolycarboxylic acid such as iron (III) complex salt of diaminopropanetetraacetate are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these iron (III) complex salts of aminopolycarboxylic acid is usually 4.0 to 8, but a lower pH value is required for speeding up the processing.
H can also be processed.

Known bleaching accelerators can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acids have an acid dissociation constant (pKa) of 2
-5, specifically, acetic acid, propionic acid,
Hydroxyacetic acid and the like are preferred.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, a large amount of iodides, and the like. In particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative for fixer and bleach-fixer,
Sulfites, bisulfites, carbonyl bisulfite adducts or the sulfinic acid compounds described in EP-A-294769A are preferred. Furthermore, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution. The total time of the desilvering step is preferably shorter as long as the desilvering failure does not occur. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C. In a preferred temperature range, the desilvering speed is improved,
In addition, the occurrence of stain after processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening stirring,
JP-A-62-183460 describes a method of impinging a jet of a processing solution on an emulsion surface of a light-sensitive material, JP-A-62-183461, a method of increasing a stirring effect by using a rotating means, A method in which the photosensitive material is moved while connecting the provided wiper blade to the emulsion surface to make the emulsion surface turbulent, thereby improving the stirring effect, and a method for increasing the circulation flow rate of the entire processing solution. .

The automatic developing machine used for the light-sensitive material of the present invention is disclosed in
It is preferable to have the photosensitive material conveying means described in JP-A-60-191257, JP-A-60-191258 and JP-A-60-191259. As described in the above-mentioned JP-A-60-191257, such a transfer means can significantly reduce the special treatment of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing solution from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

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

In the processing of the color light-sensitive material of the present invention,
The method for reducing calcium ions and magnesium ions described in 288, 838 can be used very effectively. Further, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Bactericidal and Fungicide Chemistry" (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology"
(1982) The Fungicide described in "Encyclopedia of Bactericidal and Fungicides" (ed. 1986) edited by the Japan Society of Industrial Technology, Japan Society of Bacteria and Fungi.

In the processing of the light-sensitive material of the present invention, the pH of the washing water is from 4 to
9, preferably 5 to 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but in general, 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, Japanese Unexamined Patent Application Publication No.
Known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can all be used.

Further, after the water washing treatment, a stabilization treatment may be further carried out. As an example, a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography, is exemplified. be able to. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

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

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

In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline-based compounds described in U.S. Pat. And urethane compounds described in JP-A-53-135628.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-1444547, and JP-A-58-144547.
No. 15438.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to.

The silver halide light-sensitive material of the present invention is disclosed in U.S. Pat.
No. 500,626, JP-A-60-133449, JP-A-59-218443, JP-A-6
It is also applicable to the photothermographic materials described in 1-238056, European Patent 210,660A2, and the like.

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

Example 1 On a cellulose triacetate film support having an undercoat, layers having the following compositions were applied in a multi-layered manner to prepare a multilayer color photosensitive material, Sample 101.

(Composition of photosensitive layer) The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, for the sensitizing dye, the coating amount is shown in mol units with respect to 1 mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.75 Second layer (Intermediate layer) 2,5-Di-t-pentadecylhydroquinone 0.18 EX-1 0.070 EX-3 0.020 EX-12 2.0 × 10 ^-3 U-1 0.060 U-2 0.080 U-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.58 Third layer (first red-sensitive emulsion layer) Emulsion A silver 0.25 Emulsion B silver 0.25 Sensitizing dye I 6.9 × 10 ^-5 sensitizing dye II 1.8 × 10 ^-5 sensitizing dye III 3.1 × 10 ^-4 EX-2 0.170 EX-14 0.170 EX-10 0.020 EX-15 0.035 U-1 0.070 U-2 0.050 U-3 0.070 HBS-1 0.060 Gelatin 1.40 4th layer (second red-sensitive emulsion layer) Emulsion G Silver 1.00 Sensitizing dye I 5.1 × 10 ^-5 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.3 × 10 ^-4 EX- 2 0.30 EX-14 0.10 EX-3 0.050 EX-10 0.015 EX-15 0.040 U-1 0.070 U-2 0.050 U-3 0.070 Gelatin 1.95 Fifth layer (third red-sensitive emulsion layer) Emulsion D Silver 1.60 Sensitizing dye I 5.1 × 10 ^-5 sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.4 × 10 ^-4 EX-2 0.097 EX-3 0.010 EX-4 0.080 EX-15 0.010 HBS-1 0.22 HBS-2 0.10 Gelatin 2.25 6th layer (intermediate layer) EX-5 0.040 HBS-1 0.020 gelatin 1.13 7th layer (first green-sensitive emulsion layer) Emulsion A silver 0.15 Emulsion B silver 0.15 sensitizing dye IV 3.0 × 10 ^-5 sensitizing dye V 1.0 × 10 ^-4 sensitizing dye VI 3.8 × 10 ^-4 EX-1 0.021 EX-6 0.16 EX-7 0.030 EX-8 0.025 EX-9 0.14 HBS-1 0.30 HBS-3 0.005 Gelatin 1.22 Eighth layer (second green-sensitive emulsion layer) Emulsion C Silver 0.45 Sensitization Dye IV 2.1 × 10 ^-5 Sensitizing dye V 7.0 × 10 ^-5 Sensitizing dye VI 2.6 × 10 ^-4 EX-6 0.064 EX-7 0.026 EX-8 0.018 EX-9 0.042 HBS-1 0.225 HBS-3 5.0 × 10 ^-3 gelatin 0.90 9th layer (third green-sensitive emulsion layer) Emulsion E silver 1.20 sensitizing dye IV 3.5 × 10 ^-5 sensitizing dye V 8.0 × 10 ^-5 sensitizing dye VI 3.0 × 10 ^-4 EX-1 0.025 EX-11 0.10 EX-13 0.015 HBS-1 0.25 HBS-2 0.10 Gelatin 2.25 Layer 10 (Yellow filter Layer) yellow colloidal silver silver 0.050 EX-5 0.080 HBS-1 0.030 gelatin 1.14 11th layer (first blue-sensitive emulsion layer) Emulsion A silver 0.080 Emulsion B silver 0.070 Emulsion F silver 0.070 Sensitizing dye VII 3.5 × 10 ^-4 EX -8 0.042 Y-48 0.70 HBS-1 0.28 Gelatin 2.15 12th layer (2nd blue-sensitive emulsion layer) Emulsion G Silver 0.45 Sensitizing dye VII 2.1 × 10 ^-4 Y-48 0.15 EX-10 7.0 × 10 ^-3 HBS -1 0.050 Gelatin 1.33 13th layer (3rd blue-sensitive emulsion layer) Emulsion H silver 0.77 Sensitizing dye VII 2.2 × 10 ^-4 Y-48 0.20 HBS-1 0.070 Gelatin 1.20 14th layer (first protective layer) Emulsion I Silver 0.20 U-4 0.11 U-5 0.17 HBS-1 5.0 × 10 ^-2 gelatin 1.47 15th layer (second protective layer) H-1 silver 0.61 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (Diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.90 In order to improve the preservability, processing property, pressure resistance, fungicidal and antibacterial properties, antistatic property and coatability of all layers, W −
1, W-2, W-3, W-4, B-4, B-5, F-
1, F-2, F-3, F-4, F-5, F-6, F-
7, F-8, F-9, F-10, F-11, F-12, F-1
3, F-14 and iron, lead, gold, platinum, iridium and rhodium salts.

HBS-1 Tricresyl phosphate HBS-2 Di-n-butyl phthalate The thickness of the blue-sensitive emulsion layer and the total dry film thickness of the support and the undercoat layer of the support of Sample 101 prepared as described above were
They were 5.2 μ and 25.4 μ, respectively (see Table 1).

Preparation of Samples 102 to 110 Next, based on Sample 101, only the amount of gelatin was changed so that the dry thicknesses of the blue-sensitive emulsion layer and the other layers became the values shown in Table 1A. The samples were made without change. However, only the hardener H-1 was prepared based on the amount of H-1 relative to the amount of gelatin in Sample 101, and adjusted so that the amount of gelatin added per unit weight was constant.

Preparation of Samples 111 to 120 The yellow coupler Y-48 represented by the general formula (I) of the present invention used for the eleventh to thirteenth layers of the samples 101 to 110 was replaced with a comparative yellow coupler shown below in an equimolar amount. Were prepared in exactly the same manner as 101 to 110.

These prepared samples were cut and processed and used in the following experiments.

* 111 to 120 are the yellow couplers of the present invention used in the 11th to 13th layers of 101 to 110, and samples in which Y-4 was replaced by the following coupler in an equimolar amount.

Comparative coupler A coupler having the following leaving group introduced into compound example (30) described in U.S. Pat. No. 3,265,506 according to the synthesis method described in JP-A-47-26133. (1-1) Wedge exposure of white light (color temperature of light source: 4800 ° K) is performed, and the cumulative replenishment amount of the color developing solution is replenished by an automatic developing machine by the method described below by three times the mother liquor tank capacity. Until the sample was separately subjected to imagewise exposure, the sample was processed.

The sample obtained by processing was subjected to density measurement, and from the characteristic curve measured with blue light, one of the photographic characteristic values was the logarithmic value of the reciprocal of the exposure amount giving the density of minimum density (Dmin) + 0.2. I asked. This is defined as sensitivity (S _B ). The other was to read the density (D _B ) at the exposure amount of log E = 1.0 from the exposure amount giving the density of minimum density + 0.2 to the higher exposure side.

These resultant S _B and D _B, taking as a reference the value of sample 110, obtains the difference ([Delta] S _B) for S _B, was determined the ratio (percentage) for D _B. [Delta] S _B indicates that it is a high sense of the larger value of +, D _B represents the high concentration value exceeding 100.

(1-2) The density of the sample treated by white wedge exposure was measured, and then the density was measured at 80 ° C. and 70% RH.
After storage for a day, the concentration was measured again.

From these characteristic curves, read the density after storage at an exposure that gives the minimum density +1.5 density on the characteristic curve measured with blue light before storage under high temperature and high humidity conditions, The ratio (D%) was calculated on the basis of the minimum density of 1.5 and the density of 1.5.

As a numerical value, the larger the value, the more robust the color image.

 The results are summarized in Table 1B.

The washing water was of a countercurrent type from (2) to (1), and the overflow of the washing water was all introduced into the fixing bath. The bleach-fix bath is replenished by connecting the top of the bleach tank and the bottom of the bleach-fix tank of the automatic processor and the top of the fix tank with the bottom of the bleach-fix tank by pipes, and supplying replenisher to the bleach tank and the fix tank. All of the generated overflow liquid was allowed to flow into the bleach-fix bath. Incidentally, the amount of carryover of the developing solution into the bleaching step, the amount of carryover of the bleach-fixing step of the bleaching solution, bring volume to the washing step of the amount carried and fixing solution to the fixing step of the bleach-fixing solution photosensitive material 1 m ² respectively per 65ml, 50ml, 50ml, 50m
l Also, the crossover time is 5
Seconds, and this time is included in the processing time of the previous step.

 The composition of the treatment liquid is shown below.

(Bleaching fixer mother liquor) A mixture of the above bleaching solution mother liquor and the following fixing solution mother liquor in a ratio of 15 to 85. (Washing water) Common for mother liquor and replenisher Tap water is H-type strongly acidic cation exchange resin (Rohm and Haas Amberlite IR-120B) and OH-type strong basic anion exchange resin (Amberlite IRA-400) Water is passed through the packed mixed-bed column to reduce the calcium and magnesium ion concentration to 3 mg / or less, followed by sodium diisocyanurate 20 mg / sodium sulfate 150 mg.
/ Was added. The pH of this solution was in the range of 6.5-7.5.

(Stabilizing solution) Common to mother liquor and replenisher (unit g) Formalin (37%) 1.2 ml Sodium p-toluenesulfinate 0.3 g Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 Add water 1.0 pH 7.2 From Table 1B, Sample 102 was prepared using the yellow coupler represented by the general formula (I) and reducing the dry film thickness of the blue-sensitive emulsion layer and the total dry film thickness excluding the support and the undercoat layer of the support.
~ 110 are the corresponding samples 112-120 and sample 10 of the comparative samples.
It can be seen that, compared with 1, 111, the color appearance density is clearly higher and higher, and the color image fastness under high temperature and high humidity conditions is excellent. In particular, it can be seen that the coupler of the general formula (I) is greatly improved by the above-mentioned effect of improving the characteristics by reducing the dry film thickness.

Example 2 In Example 1, the color light-sensitive material of Sample No. 107 was used as a basic constitution, and the yellow couplers Y-4 of the eleventh to thirteenth layers were variously changed as shown in Table 2 to obtain an equimolar amount of Y-4. A sample was prepared with the replacement.

These prepared samples in accordance with the method described in Example 1, exposure, followed by development, photographic characteristic values were determined [Delta] S _B and D _B. Table 2 shows the results together. At this time, each comparative sample was used as a reference sample as shown in Table 2.

From Table 2, the results of replacing the coupler species by an equimolar amount when the dry film thickness is within the range satisfying the constitutional requirements of the present invention are as follows:
It can be seen that all of the couplers have a higher sensitivity and a higher color density as compared with the conventional couplers. The active position is represented by the formula [Y-1]
A coupler substituted with a leaving group represented by the formula [Y-
2] and higher sensitivity and higher color density than the leaving group represented by [Y-3].

Since the coupler of the present invention gives a high color density, the coating amount of the coupler (mol / m) is higher than that of the conventional coupler.
² ] can be clearly reduced.

Example 3 A sample 301, which is a multilayered color light-sensitive material comprising the following layers, was prepared on an undercoated cellulose triacetate film support.

(Composition of photosensitive layer) The coating amount is g / g for silver halide and colloidal silver.
The amount of silver expressed in m ² units, the amount expressed in g / m ² for couplers, additives and gelatin, and the number of moles per mole of silver halide in the same layer for sensitizing dyes Indicated by

First layer: Antihalation layer Black colloidal silver Silver coating amount 0.20 Gelatin 2.02 UV-1 0.11 UV-2 0.20 Cpd-1 4.0 × 10 ^-2 Cpd-2 1.9 × 10 ^-2 Solv-1 0.30 Solv-2 1.2 × 10 ^-2 Second layer: Intermediate layer Fine grain silver iodobromide (AgI 1.0 mol%, equivalent sphere diameter 0.07 μm) Silver coating amount 0.15 Gelatin 1.00 ExC-4 6.0 × 10 ^-2 Cpd-3 2.0 × 10 ^-2 Third Layer: 1st red-sensitive emulsion layer Silver iodobromide emulsion (AgI 5.0 mol%, surface high AgI type, equivalent sphere diameter 0.9 μm, coefficient of variation of equivalent sphere diameter 21%, tabular grains, diameter / thickness ratio 7.5) Silver coating amount 0.42 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent spherical diameter 0.4 μm, coefficient of variation of equivalent spherical diameter 18%, tetradecahedral particles) Silver coating amount 0.40 Gelatin 1.77 ExS− 1 4.5 × 10 ^-4 mol ExS-2 1.5 × 10 ^-4 mol ExS-3 4.0 × 10 ^-5 mol ExC-1 0.65 ExC-3 1.0 × 10 ^-2 ExC-4 2.3 × 10 ^-2 Solv-1 0.32 Four layers: Second red-sensitive emulsion layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high Ag Type I, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter / thickness ratio 3.0) Silver coating amount 0.85 Gelatin 0.86 ExS-1 3.0 × 10 ^-4 mol ExS-2 1.0 × 10 ^{− 4} mol ExS-3 3.0 × 10 ^-5 mol ExC-1 0.13 ExC-2 6.2 × 10 ^-2 ExC-4 4.0 × 10 ^-2 Solv-1 0.10 Fifth layer: Third red-sensitive emulsion layer Silver iodobromide emulsion (AgI11.3 mol%, internal high AgI type, sphere-corresponding diameter 1.4 [mu] m, a variation coefficient of 28% of the sphere-equivalent diameter, the plate-like particles, diameter / thickness ratio 6.0) silver coverage 1.50 gelatin 1.02 ExS-1 2.0 × 10 ^{- 4} mol ExS-2 6.0 × 10 ^-5 mol ExS-3 2.0 × 10 ^-5 mol ExC-2 8.5 × 10 ^-2 ExC-5 7.3 × 10 ^-2 Solv-1 0.12 Solv-2 0.12 6th layer: middle layer Gelatin 0.96 Cpd-4 8.0 × 10 ^-2 Solv-1 8.0 × 10 ^-2 Seventh layer: First green-sensitive emulsion layer Silver iodobromide emulsion (AgI 5.0 mol%, surface high AgI type, equivalent sphere diameter 0.9 μm) , Coefficient of variation of equivalent sphere diameter 21%, plate-like particles, diameter / thickness ratio 7.
0) Silver coating amount 0.28 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent spherical diameter 0.4 μm, coefficient of variation of equivalent spherical diameter 18%, tetradecahedral particles) Silver coating amount 0.16 Gelatin 1.10 ExS-4 5.0 × 10 ^-4 mol ExS-5 2.0 × 10 ^-4 mol ExS-6 1.0 × 10 ^-4 mol ExM-1 0.50 ExM-2 0.10 ExM-5 3.5 × 10 ^-2 Solv-1 0.20 Solv-3 3.0 × 10 ^-2 Eighth layer: Second green-sensitive emulsion layer Silver iodobromide emulsion (AgI 8.5 mol%, internal high AgI type, equivalent spherical diameter 1.0 μm, coefficient of variation of equivalent spherical diameter 25%, tabular grains , Diameter / thickness ratio 3.0) Silver coating amount 0.57 Gelatin 0.40 ExS-4 3.5 × 10 ^-4 mol ExS-5 1.4 × 10 ^-4 mol ExS-6 7.0 × 10 ^-5 mol ExM-1 0.12 ExM-2 7.1 × 10 ^-3 ExM-3 3.5 × 10 ^-2 Solv-1 0.15 Solv-3 1.0 × 10 ^-2 Ninth layer: Intermediate layer Gelatin 0.50 Solv-1 2.0 × 10 ^-2 Tenth layer: Third green-sensitive emulsion layer Silver halide emulsion (AgI 11.3 mol%, internal high AgI type, equivalent spherical diameter 1.4 μm, coefficient of variation of equivalent spherical diameter 28%, plate-like particles, Diameter / thickness ratio 6.0) silver coverage 1.30 Gelatin 1.03 ExS-4 2.0 × 10 ^-4 mol ExS-5 8.0 × 10 ^-5 mol ExS-6 8.0 × 10 ^-5 mol ^{ExM-4 4.5 × 10 -2 ExM} -6 1.0 × 10 ^-2 ExC-2 4.5 × 10 ^-3 Cpd-5 1.0 × 10 ^-2 Solv-1 0.25 Layer 11: Yellow filter layer Gelatin 0.45 Cpd-6 5.2 × 10 ^-2 Solv-1 0.12 Layer 12: Intermediate layer Gelatin 0.40 Cpd-3 0.10 13th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 2 mol%, uniform AgI type, sphere equivalent diameter 0.55 μm, sphere equivalent diameter variation coefficient 25%, tabular grains , Diameter / thickness ratio 7.0) Silver coating amount 0.20 gelatin 1.13 ExS-7 3.0 × 10 ^-4 mol ExY-1 0.60 Y-60 2.0 × 10 ^-2 Solv-1 0.48 14th layer: 2nd blue-sensitive emulsion layer Silver halide emulsion (AgI 19.0 mol%, internal high AgI type, equivalent sphere diameter 1.0 μm, variation coefficient of equivalent sphere diameter 16%, octahedral grains) Silver coating amount 0.19 Gelatin 0.39 ExS-7 2.0 × 10 ^-4 mol ExY -1 0.22 Solv-1 0.22 15th layer: Intermediate layer Silver (AgI 12 mol%, uniform AgI type, equivalent sphere diameter 0.13 μm) Silver coating amount 0.20 Gelatin 0.35 16th layer: Third blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 14.0 mol%, internal high AgI type, spherical 1.7 μm equivalent diameter, coefficient of variation of equivalent spherical diameter 28%, plate-like particles, diameter / thickness ratio 5.0) Silver coating amount 0.15 Gelatin 0.97 ExS-8 1.5 × 10 ^-4 mol ExY-1 0.21 Solv-1 0.21 17th layer : First protective layer Gelatin 1.65 UV-1 0.13 UV-2 0.21 Solv-1 1.0 × 10 ^-2 Solv-2 1.0 × 10 ^-2 18th layer: Second protective layer Fine grain silver chloride (equivalent sphere diameter 0.07 μm) Silver Coating amount 0.36 Gelatin 0.70 B-1 (1.5 μm in diameter) 2.0 × 10 ^-2 B-2 (1.5 μm in diameter) 0.15 B-3 3.0 × 10 ^-2 W-1 2.0 × 10 ^-2 H-1 0.35 Cpd-7 1.00 This sample contains 1,2-benzisothiazolin-3-one (average 200 ppm based on gelatin), n-butyl-p-
Hydroxybenzoate (about 1,000 ppm), and 2-
Phenoxyethanol (about 10,000 ppm) was added. Further, B-4, B-5, W-2, W-3, F-1,
F-2, F-3, F-4, F-5, F-6, F-7, F
-8, F-9, F-10, F-11, F-12, F-13 and iron, lead, gold, platinum, iridium and rhodium salts.

Next, Solv-1 used in the blue emulsion layers of the thirteenth layer, the fourteenth layer and the sixteenth layer was changed as shown in Table 3A to obtain a sample 30.
2 and 303 were produced.

Subsequently, Samples 304 to 306 were prepared without replacing the yellow coupler ExY-1 in the blue-sensitive emulsion layer of Samples 301 to 303 with an equimolar amount of the coupler Y-48 of the present invention, and changing the other components in the same manner. The dry film thickness at this time is also shown in Table 3A.

The samples 301 to 306 produced as described above were cut and processed, and their performance was evaluated by the same method as the experiments (1-1) to (1-2) described in Example 1.

The processing steps and the composition of the processing solution at this time are shown below. The sample used in the experiment was a sample to which imagewise exposure was separately applied until the cumulative replenishment amount of the color developing solution was replenished by three times the capacity of the mother liquor tank. After the treatment, the treated sample was used.

Incidentally, photographic performance [Delta] S _B and [Delta] D _B calculated the sample 301 for reference.

Subsequently, the coating amount of the blue-sensitive emulsion layer of Sample 302 and Samples 304 to 306 was adjusted so as to match the gradation of the characteristic curve measured with blue light of Sample 301 to prepare a sample. Using this sample, the MTF pattern was exposed to white light, the above-described processing was performed, and the MTF value of the magenta color image was measured to evaluate the sharpness. MTF is measured in TH James edition, “The Theory of the Photographi
c Process "(4th Ed., McMillan).

 These results are summarized in Table 3B.

Next, the composition of the treatment liquid will be described.

As apparent from the samples Nos. 304 to 306 in the above table, the yellow couplers of the general formula (I) have a dry film thickness of all layers except the blue emulsion layer and the support and the undercoat layer of the support within the range of the present invention. When compared to the comparative sample, the sample gives higher sensitivity and higher density, has excellent color image fastness, and gives good results in image quality and sharpness.

Further, in the sample using the coupler of the general formula (I), even when the amount of the high boiling point organic solvent added per unit weight of the coupler is small, the change in sensitivity and color density is small, and the so-called oil dependence is small. It is also evident that the couplers can be used to provide high color density and thus reduce the amount of coupler coating.

In sample 301, so-called oil seepage and sweating were observed on the coating film surface of the sample on which the color image fastness test was performed, but no abnormality was observed in the other samples. . This indicates that the coupler of the general formula (I) has excellent compatibility with a high-boiling organic solvent, and that a sample using the coupler has excellent stability of a dispersion in a coating film.

(Effect of the Invention) Using the acetamide type yellow coupler represented by the above general formula (I), the dry thickness of the blue-sensitive emulsion layer is 5.0 μm or less, and all the layers except the support and the undercoat layer of the support are used. The color light-sensitive material having a dry film thickness of 25.0 μ or less gives high sensitivity and color density, and the obtained yellow image is robust.
Excellent image quality. In particular, it is possible to provide a color light-sensitive material which can provide a high color density and can reduce the amount of the yellow coupler applied. Even when the amount of the high-boiling organic solvent added to the coupler is reduced, the above-described excellent performance, in particular, the fluctuation of the photographic performance is small, and in this respect, the amount of the high-boiling organic solvent added can be reduced. And a color light-sensitive material capable of further reducing the dry film thickness can be provided.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-55-598 (JP, A) JP-A-1-182848 (JP, A) JP-A-63-118157 (JP, A) 33773 (JP, B2) JP-B 60-46425 (JP, B2) JP-B 62-55651 (JP, B2) European publication 447969 (EP, A1)

Claims (2)

(57) [Claims] An at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer,
In a silver halide color photographic light-sensitive material comprising a red-sensitive silver halide emulsion layer and a non-light-sensitive layer, at least one of the blue-sensitive silver halide emulsion layers has an acyl group represented by the following general formula (I): A silver halide color photographic material comprising at least one type of yellow dye-forming coupler and having a total dry film thickness of not more than 5.0 μm of all the blue-sensitive silver halide emulsion layers. General formula (I) (Wherein R ₁ represents a monovalent group. Q together with C is 3 to 5)
A non-metallic atomic group necessary for forming a 3- to 5-membered heterocyclic ring having at least one heteroatom selected from N, O, S, and P in the ring. However, R ₁ is not a hydrogen atom and does not combine with Q to form a ring. ) 2. The silver halide color photographic light-sensitive material according to claim 1, wherein a dry film thickness of all layers except a support and an undercoat layer of the support is 25.0 μm or less. Silver halide color photographic material.