JP2676282B2 - Silver halide color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, more specifically, image quality,
In particular, the present invention relates to a color photographic light-sensitive material having improved sharpness and remarkably improved fading (dark fading) of a color image during dark storage.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material containing three kinds of color couplers capable of forming yellow, magenta and cyan by coupling with an oxidation product of an aromatic primary amine color developing agent. Is generally used. Among them, as the yellow coupler, an acylacetamide coupler represented by a benzoylacetanilide coupler and a pivaloylacetanilide coupler is generally used. Benzoylacetamide type couplers generally have high coupling activity with an aromatic primary amine developing agent at the time of development, and have excellent characteristics such that the generated yellow dye has a large molecular extinction coefficient. It has the disadvantage of low color image fastness. The pivaloylacetamide type coupler is excellent in color image fastness, but since the coupling reactivity at the time of development is low and the molecular extinction coefficient is small, more color forming couplers are required to obtain a sufficient dye concentration. It had to be used, which was disadvantageous in terms of image quality and cost.

Therefore, it has been desired to develop a yellow coupler which has the advantages of both, that is, high color developability (high coupling activity of coupler and high molecular extinction coefficient of dye formed) and color image fastness.

From the above viewpoint, studies have been made on the acyl group of the acylacetamide type yellow coupler. For example, U.S. Pat. No. Re 27,848 describes a modification of the pivaloyl group as 7,7-dimethylnorbornane-
1-carbonyl group and 1-methylcyclohexane-1-
Couplers having a carbonyl group are disclosed. However, these couplers have a low coupling activity, and the dyes produced have a low molecular extinction coefficient. In addition, JP
No. 7-26133 discloses a coupler having a cyclopropane-1-carbonyl group and a cyclohexane-1-carbonyl group. However, these couplers were unsatisfactory due to the low fastness of the dye formed.

On the other hand, in a color photographic light-sensitive material, it is important to reduce the dry film thickness of the light-sensitive material from the viewpoint of improving image quality, particularly sharpness. In particular, the blue-sensitive silver halide layer using a yellow coupler is often placed on the uppermost layer of the photosensitive silver halide layers of the photographic material, so the sharpness of the lower green-sensitive and red-sensitive layers is improved. It is believed to have a significant impact on

Usually, the coupler is dissolved in a high-boiling point organic solvent and is applied on the support after being emulsified and dispersed. Therefore, in order to realize a thin layer, it is effective to reduce the amount of the high-boiling point organic solvent used. Can be. However, when the benzoylacetamide type yellow coupler with high color development that has been used conventionally is used, reducing the amount of the high-boiling organic solvent used causes a remarkable decrease in activity, and this method has a limit to thinning. It was

Further, the pivaloylacetamide type coupler, which has a low coupling activity and a small molecular extinction coefficient, is naturally limited in thinning. Thinning by reducing only the amount of gelatin without reducing the amount of high-boiling organic solvent is not practical because it causes a remarkable deterioration in film quality. In general, the film quality is greatly affected by the ratio of oil soluble components such as couplers and high boiling point organic solvents to gelatin. Therefore, on the assumption that the film quality is kept constant, it means that reducing the oil-soluble content also enables reducing the gelatin content. Therefore, it can be said that the reduction of the high boiling point organic solvent which occupies a considerable part of the oil-soluble matter is extremely effective for thinning. For the above reasons,
It has been desired to develop a coupler that gives a sufficient color density even when the amount of the high boiling point organic solvent used is reduced.

[0008]

Accordingly, the first aspect of the present invention is as follows.
It is an object of the invention to provide a silver halide color photographic light-sensitive material exhibiting sufficient color forming property even when the amount of the high boiling point organic solvent coexisting with the yellow coupler is reduced.

A second object of the present invention is to provide a color photographic light-sensitive material excellent in color image storability.

[0010]

The object of the present invention has been solved by the following method. That is, in a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, at least one light-sensitive silver halide emulsion layer has an acyl group represented by the following general formula (I). Containing at least one acylacetamide type yellow dye-forming coupler, and the weight ratio of the high boiling point organic solvent to the dye-forming coupler contained in the layer is 0.3.
The following was achieved by a silver halide color photographic light-sensitive material characterized by being preferably 0.1 or less.

General formula (I)

Embedded image (In the formula, R ₁ represents a monovalent group. Q represents C together with 3
Represents a non-metallic atomic group necessary to form a 5- to 5-membered hydrocarbon ring or a 3- to 5-membered heterocycle 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. )

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

Formula (Y)

Embedded image In formula (Y), R ₁ is a monovalent substituent that is not hydrogen,
Q is a 3- to 5-membered hydrocarbon ring together with C or at least 1
R ₂ is a hydrogen atom, a halogen atom (F) or a non-metal atom group necessary for forming a 3- to 5-membered heterocyclic ring containing a heteroatom selected from N, S, O, and P in the ring. , Cl, Br,
Say I. The same applies to the description of the formula (Y) below. ), An alkoxy group, an aryloxy group, an alkyl group or an amino group, R ₃ is a group capable of substituting on the benzene ring, X is a hydrogen atom or an aromatic primary amine developing agent by a coupling reaction. A group capable of leaving (hereinafter referred to as a leaving group)
And s represents an integer of 0 to 4, respectively. However, when s is plural, plural R ₃ may be the same or different.

Examples of R ₃ are halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, Alkylsulfonyl group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, alkoxysulfonyl group, acyloxy group, nitro group, heterocyclic group, cyano group, acyl group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group Examples of the leaving group include a heterocyclic group bonded to the coupling active position at a nitrogen atom, an aryloxy group, an arylthio group, an acyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, a heterocyclic oxy group, a halogen. There is a child.

When the substituent in formula (Y) is an alkyl group or contains an alkyl group, the alkyl group may be linear, branched or cyclic, unless otherwise specified. An alkyl group which may contain an unsaturated bond (for example, methyl, isopropyl, t-butyl, cyclopentyl, t-pentyl, cyclohexyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl, dodecyl, hexadecyl, Allyl, 3-cyclohexenyl,
Oleyl, benzyl, trifluoromethyl, hydroxymethylmethoxyethyl, ethoxycarbonylmethyl, phenoxyethyl).

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

When the substituent in the formula (Y) is a heterocyclic group or contains a heterocyclic group, the heterocyclic group is at least 1 selected from O, N, S, P, Se and Te unless otherwise specified. Optionally substituted 3- to 8-membered monocyclic or condensed-ring heterocyclic group containing 4 heteroatoms in the ring (for example, 2-furyl, 2-pyridyl, 4-pyridyl, 1-pyrazolyl, 1
-Imidazolyl, 1-benzotriazolyl, 2-benzotriariazolyl, succinimide, phthalimide, 1
-Benzyl-2,4-imidazolidindione-3-yl).

The substituents preferably used in formula (Y) will be described below. In the formula (Y), R ₁ is preferably a halogen atom, a cyano group, or the total number of carbon atoms which may be substituted (hereinafter abbreviated as C number) 1 to 30.
A monovalent group (for example, an alkyl group or an alkoxy group) or a monovalent group having a C number of 6 to 30 (for example, an aryl group or an aryloxy group), and the substituent thereof is, for example, a halogen atom, an alkyl group or an alkoxy group. Group, nitro group, amino group, carbonamido group, sulfonamide group, acyl group.

In the formula (Y), Q is preferably a C number having 3 to 5 members, as well as C, of 3 to 3 which may be substituted.
It represents a group of non-metal atoms necessary to form a hydrocarbon ring of 0 or a heterocycle having a C number of 2 to 30 containing at least one hetero atom selected from N, S, O and P in the ring. Also,
The ring formed by Q together with C may contain an unsaturated bond in the ring. Examples of the ring formed by Q together with C include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclopropene ring, cyclobutene ring, cyclopentene ring, oxetane ring, oxolane ring, 1,3-dioxolane ring, thietane ring, thiolane ring, pyrrolidine There is a ring. Examples of the substituent include a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an acyl group, an alkoxy group, an aryloxy group,
Cyano group, alkoxycarbonyl group, alkylthio group,
There is an arylthio group.

In the formula (Y), R ₂ is preferably a halogen atom, which may be substituted, and has a C number of 1 to 30.
Alkoxy group, aryloxy group having 6 to 30 C, C
It represents an alkyl group having 1 to 30 or 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 C atoms, an aryl group having 6 to 30 C atoms, or 1 to 30 C atoms.
An alkoxy 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, and 1 to 30 carbon atoms Carbamoyl group, C number 0-3
0 sulfamoyl group, C 1-30 alkylsulfonyl group, C 6-30 arylsulfonyl group, C 1
A ureido group of up to 30; a sulfamoylamino group of 0 to 30 carbon atoms; an alkoxycarbonylamino group of 2 to 30 carbon atoms; a heterocyclic group of 1 to 30 carbon atoms; an acyl group of 1 to 30 carbon atoms; Represents an alkylsulfonyloxy group having 1 to 30 carbon atoms, or an arylsulfonyloxy group having 6 to 30 carbon atoms, and examples of the substituent include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, Ring 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, cyano, nitro, acyloxy, alkoxycarbonyl, aryl Oxycarbonyl group, an alkylsulfonyloxy group, an arylsulfonyloxy group.

In the formula (Y), s preferably represents an integer of 1 or 2, and the substitution position of R ₃ is

Embedded image 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-ring heterocyclic group which may be substituted, and examples thereof include succinimide, maleinimide and phthalimide. , Diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, indazole,
Benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2,4-dione, thiazolidine-2,4-dione, imidazolidin-
2-one, oxazolidine-2-one, thiazolidine-
2-one, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one,
-Pyrolin-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,
There are 3,4-thiazolidine, 2-imino-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, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group, sulfamoyl There is an amino group. When X represents an aryloxy group, X preferably has 6 carbon atoms.
It represents an aryloxy group of 30 to 30 and may be substituted with a group selected from the substituent group mentioned when X is a heterocycle. 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 carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group. Groups or cyano groups are preferred.

Substituents particularly preferably used in formula (Y) are described below. R ₁ is particularly preferably a halogen atom, a linear or branched alkyl group having a C number of 1 to 5, most preferably a methyl group, an ethyl group or n.
A propyl group. Q is particularly preferably a nonmetallic group in which the ring formed with C forms a 3- to 5-membered hydrocarbon ring, for example,

Embedded image It is. Here, R represents a hydrogen atom, a halogen atom or an alkyl group. However, a plurality of R may be the same or different. Q most preferably forms a three-membered ring with the C to which it is attached

Embedded image It is.

R ₂ is particularly preferably a chlorine atom, a fluorine atom, an alkyl group having a C number of 1 to 6 (eg methyl, trifluoromethyl, ethyl, isopropane, t-butyl),
Alkoxy group having 1 to 8 C numbers (eg, methoxy, ethoxy, methoxyethoxy, butoxy), or 6 to 2 C numbers
4 aryloxy groups (eg, phenoxy group, p-tolyloxy, p-methoxyphenoxy), most preferably chlorine atom, methoxy group or trifluoromethyl group.

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

X is particularly preferably the following formula (Y-1),
It is a group represented by (Y-2) or (Y-3).

Formula (Y-1)

Embedded image

In the formula (Y-1), Z is

Embedded image 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 represent a hydrogen atom, an alkyl group, an aryl group, 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).

Among the heterocyclic groups represented by the formula (Y-1), particularly preferred one is Z in the formula (Y-1).

Embedded image 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)

Embedded image

In the formula (Y-2), at least one of R ₁₂ and R ₁₃ is a halogen atom, a cyano group, a nitro group,
A group selected from a trifluoromethyl group, a carboxyl group, an alkoxycarbonyl group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group or an acyl group, and the other is a hydrogen atom, It may be 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 formula (Y−
The C number of the aryloxy group represented by 2) is 6 to 30,
Preferably it is 6-24, More preferably, it is 6-15.

Formula (Y-3)

Embedded image In the formula (Y-3), W represents a non-metal atom group necessary for forming a pyrrole ring, a pyrazole ring, an imidazole ring or a triazole ring together with N. here,

Embedded image The ring represented by may have a substituent, and examples of the substituent are preferably a halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group, an alkyl group, an aryl group, an amino group, an alkoxy group and an aryloxy group. Alternatively, it is 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 16. X is most preferably of the formula (Y-
It is a group represented by 1).

The coupler represented by the formula (Y) has a substituent R ₁ , Q, X, or

Embedded image In, a dimer or a multimer having a valence of 2 or more may be bonded to each other. 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

Embedded image Examples of groups are shown below.

[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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Specific examples of the yellow coupler represented by the formula (Y) are shown below.

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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The yellow coupler of the present invention represented by the formula (Y) can be synthesized by the following synthetic route.

[0081]

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Here, the compound a is J. Chem. Soc. (C), 1
968, 2548, J. Am. Chem. Soc., 1934, 56 , 2710, Synt
hesis, 1971, 258, J. Org. Chem., 1978, 43 , 1729, C
A, 1960, 66 , 18533y and the like.

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

The compound c is synthesized by converting ethyl acetoacetate into an anion using magnesium methoxide or the like and adding b into the anion. The reaction is carried out without solvent or using tetrahydrofuran, ethyl ether or the like, and the reaction temperature is generally -20 ° C to 60 ° C, preferably -10 ° C to 30 ° C.
It is. The compound d is synthesized by reacting the compound c with ammonia as a base, an aqueous solution of NaHCO ₃ or an aqueous solution of sodium hydroxide, without solvent or in a solvent such as methanol, ethanol or acetonitrile. The reaction temperature is generally -20 ° C to 50 ° C, preferably -1.
0 ° C to 30 ° C.

Compound e is synthesized by reacting compounds d and g in the absence of solvent. The reaction temperature is usually 100-
The temperature is 150 ° C, preferably 100 to 120 ° C. X
Is not H, the leaving group X is introduced after chlorination or bromination to synthesize the compound f. Compound e is converted to a chloro substitution product with sulfuryl chloride, N-chlorosuccinimide or the like in a solvent such as dichloroethane, carbon tetrachloride, chloroform, methylene chloride or tetrahydrofuran, or bromine,
A bromo-substituted product is obtained with N-bromosuccinimide or the like. At this time, the reaction temperature is -20 ° C to 70 ° C, preferably -10 ° C to 50 ° C.

Next, the chloro-substituted product or the bromo-substituted product and the proton adduct of the leaving group, H-X, were combined with methylene chloride, chloroform, tetrahydrofuran, acetone, acetonitrile, dioxane, N-methylpyrrolidone, N, N'-dimethylimidazolidine. Reaction temperature in a solvent such as 2-one, N, N-dimethylformamide, N, N-dimethylacetamide, -20 ° C to 150 ° C, preferably -10 ° C.
By reacting at 〜100 ° C., the coupler f of the present invention can be obtained. At this time, triethylamine, N
Bases such as -ethylmorpholine, tetramethylguanidine, potassium carbonate, sodium hydroxide, sodium hydrogen carbonate and the like may be used.

The synthesis examples of the coupler of the present invention are shown below. Synthesis Example 1 Synthesis of Exemplified Compound Y-30 Gotkis, D. et al, J. Am. Chem. Soc., 1934, 56 , 2710
25 g of 1-methylcyclopropanecarboxylic acid synthesized by the method described in 1., 100 ml of methylene chloride, N, N-
38.1 g of oxalyl chloride was added dropwise to a mixture of 1 ml of dimethylformamide 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.

100 ml of methanol was added dropwise to a mixture of 6 g of magnesium and 2 ml of carbon tetrachloride at room temperature over 30 minutes and then heated under reflux for 2 hours, and then 32.6 g of ethyl 3-oxobutanoate was added over 30 minutes under reflux under heating. To do. 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. Tetrahydrofuran 1
00 ml was added to the reaction product to disperse, and 1-
Methylcyclopropane carbonyl chloride is added dropwise. After reacting for 30 minutes, the reaction solution was extracted with 300 ml of ethyl acetate and diluted sulfuric acid water, washed with water, the organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off to give 2- (1-methylcyclopropanecarbonyl) -3-oxobutane. Ethyl acid oil 5
5.3 g were obtained.

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

(1-methylcyclopropanecarbonyl)
34 g of ethyl acetate and N- (3-amino-4-chlorophenyl) -2- (2,4-di-t-pentylphenoxy)
44.5 g of butanamide 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 with a mixed solvent of n-hexane and ethyl acetate to obtain 49 g of Exemplified Compound Y-30 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 added to 300 ml of methylene chloride.
It is dissolved in ml and 5.4 g of sulfuryl chloride is added dropwise over 10 minutes under ice cooling. After reacting for 30 minutes, the reaction solution was washed well with water, dried over anhydrous sodium sulfate, and concentrated to obtain a chloride of Exemplified Compound Y-30. 1-benzyl-5-ethoxyhydantoin 18.7 g, triethylamine 11.2 ml, N, N-
A solution of the chloride of Exemplified Compound Y-30 synthesized above in 50 ml of dimethylformamide dissolved in 50 ml of N, N-dimethylformaldehyde is added dropwise at room temperature over 30 minutes.

Thereafter, after reacting at 40 ° C. for 4 hours, the reaction solution is extracted with ethyl acetate (300 ml), washed with water, washed with 2% triethylamine aqueous solution (300 ml), and then neutralized with diluted 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 then dried to obtain 22.8 g of crystals of Exemplified compound Y-1. The structure of the compound was confirmed by MS spectrum, NMR spectrum and elemental analysis. The melting point was 132 to 133 ° C.

The amount of the coupler of the present invention used is preferably 1 × 10 ⁻³ to 2 mol per mol of silver halide in the light-sensitive layer in which the coupler of the present invention is used. More preferably, it is 2 × 10 ^{-2 to} 0.6 mol.

Various known methods are available for incorporating the coupler represented by formula (I) of the present invention, the coupler which can be used in the light-sensitive material of the present invention described below, and other lipophilic photographic organic compounds into the light-sensitive material. A dispersion method is used.

In the oil-in-water dispersion method described in US Pat. No. 2,322,027, a high-boiling organic solvent having a boiling point of about 175 ° C. or higher under normal pressure, such as phthalic acid esters, phosphoric acid esters, benzoic acid esters. , Fatty acid esters, amides, phenols, alcohols, carboxylic acids, N,
N-dialkylanilines, hydrocarbons, oligomers or polymers and / or low boiling organic solvents having a boiling point of about 30 ° C. to about 160 ° C. under normal pressure, such as esters (eg ethyl acetate, butyl acetate, ethyl propionate, β -Ethoxyethyl acetate, methyl cellosolve acetate), alcohols (e.g. secondary butyl alcohol), ketones (e.g. methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone),
Amides (eg dimethylformamide, N-methylpyrrolidone), ethers (eg tetrahydrofuran,
The lipophilic photographic organic compound is dissolved with dioxane or the like and then emulsified and dispersed in a hydrophilic colloid such as gelatin.

The steps and effects of the latex dispersion method and specific examples of latex for impregnation are described in US Pat. No. 4,199,363.
No., West German Patent Application (OLS) No. 2,541,274,
No. 2,541,230 and European Patent No. 294,10
No. 4A. These high-boiling organic solvents and latices not only function as a dispersion medium, but the physical properties of the gelatin film are improved, the color development is accelerated, the color image is adjusted, and the color image fastness is improved by selecting the structure. It is possible to add various functions such as. The high boiling point organic solvent may be in any form such as liquid, wax and solid, and is preferably represented by the following formulas (S-1) to (S-9).

[0097]

Embedded image In formula (S-1), R ₁ , R ₂ and R ₃ each independently represent an alkyl group, a cycloalkyl group or an aryl group.

In the formula (S-2), R ₄ and R ₅ each independently represent an alkyl group, a cycloalkyl group or an aryl group, and R ₆ is a halogen atom (F, Cl, Br,
I the same shall apply hereinafter), an alkyl group, an alkoxy group, an aryloxy group or an alkoxycarbonyl group, and a is 0
Represents an integer of ~ 3. When a is plural, plural R ₆ may be the same or different.

In the formula (S-3), Ar represents an aryl group, b represents an integer of 1 to 6, and R ₇ represents a b-valent hydrocarbon group or a hydrocarbon group bonded to each other by an ether bond.

In the formula (S-4), R ₈ represents an alkyl group or a cycloalkyl group, c represents an integer of 1 to 6, R ₉ represents a c-valent hydrocarbon group or a hydrocarbon bonded to each other by an ether bond. Represents a group.

In the formula (S-5), d represents an integer of 2 to 6, R ₁₀ represents a d-valent hydrocarbon group (excluding an aromatic group), R ₁₁ represents an alkyl group, a cycloalkyl group or Represents an aryl group.

In the formula (S-6), R ₁₂ , R ₁₃ and R ₁₄
Each independently represents an alkyl group, a cycloalkyl group or an aryl group. R ₁₂ and R ₁₃ or R ₁₃ and R ₁₄ may combine with each other to form a ring.

In the formula (S-7), R ₁₅ is an alkyl group,
A cycloalkyl group, an alkoxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryl group or a cyano group; R ₁₆ represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group or an aryloxy group; Represents an integer of 0 to 3. When e is plural, plural R ₁₆ may be the same or different.

In the formula (S-8), R ₁₇ and R ₁₈ each independently represent an alkyl group, a cycloalkyl group or an aryl group, and R ₁₉ is a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group or It represents an aryl group oxy group, and f represents an integer of 0 to 4. f
When R is plural, plural R ₁₉ may be the same or different.

In the formula (S-9), A ₁ , A ₂ , ...
., A _n represent polymerized units provided by different non-color-forming ethylene-like monomers, and are a ₁ , a ₂ , ...
·, A _n represents the weight fraction of each polymer units, n
Represents an integer of 1 to 30. Specific examples of the high boiling point organic solvent used in the present invention are shown below.

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Examples of compounds other than the above high boiling point organic solvents used in the present invention and / or methods for synthesizing these high boiling point organic solvents are described in, for example, US Pat. No. 2,322,027.
No. 2,533,514, No. 2,772,16
No. 3, No. 2,835,579, No. 3,676,1
No. 37, No. 3,912, 515, No. 3,936,
No. 303, No. 4,080,209, No. 4,12
No. 7,413, No. 4,193,802, No. 4,2
39,851, 4,278,757, 4,
363,873, 4,483,918, 4,745,049, European Patent 276,319A.
JP-A-48-47335 and 51-149028.
No. 61-84641, No. 62-118345,
Nos. 62-247364, 63-167357, 64-68745 and JP-A-1-101543.

The amount of the high boiling point organic solvent used in the present invention is 0.3 in terms of weight ratio to the coupler used in each photosensitive layer.
It is as follows. From the viewpoint of the effect of improving sharpness, 0.1 or less is more preferable. Of course, it is not necessary to use the high boiling point organic solvent at all. In the present invention, reducing the high-boiling organic solvent has a great effect on thinning. For example, roughly speaking, if the high boiling point organic solvent / coupler ratio (weight ratio) is reduced from 1.0 to 0.3, the film thickness becomes 2.9.
The thickness can be reduced to about 2/3 with μm being 1.9 μm.

The light-sensitive material of the present invention may have at least one layer of a silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. 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. Wherein the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to any of red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit light-sensitive layers is generally such that the red-sensitive layer, green The color-sensitive layer and the blue color-sensitive layer are provided in this order.
However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers. Non-light-sensitive layers such as various intermediate layers may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
Couplers, DIR compounds and the like described in JP-A Nos. 61-20037 and 61-20038 may be contained, and a color mixture inhibitor may be contained as usually used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers 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. JP-A-57-112751, JP-A-62-20035
No. 0, 62-206541, 62-206543
As described in Japanese Patent Application Laid-Open No. H10-284, 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 a specific example, from the side farthest from the support,
Low-sensitivity blue-sensitive layer (BL) / High-sensitivity blue-sensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
And so on.

Further, as described in JP-B-55-34932, layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. JP-A-56-25738 and JP-A-62-6393.
As described in the specification of JP-A No. 6, the blue light-sensitive layer / GL / RL / GH / RH may be arranged in this order from the farthest side from the support.

Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Further, an arrangement in which a silver halide emulsion layer having a lower photosensitivity is disposed and three layers having different sensitivities in which the sensitivities are sequentially lowered toward the support are provided can be mentioned. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order. 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.
Also, in the case of four or more layers, the arrangement may be changed as described above. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
It is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing the following silver iodide. Particularly preferred is about 2 mol%
Silver iodobromide or silver iodochlorobromide containing from 1 to about 10 mol% of silver iodide.

The silver halide grains in the photographic emulsion include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystalline forms such as spherical and plate-like,
It may have a crystal defect such as a twin plane or a composite form thereof. The grain size of silver halide is about 0.2 μm
The following fine particles or large-sized particles having a projected area diameter of about 10 μm may be used, and a polydisperse emulsion or a monodisperse emulsion may be used.

The silver halide photographic emulsion usable in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23,
"I. Emulsion preparation and type
s) ”, and No. 18716 (November 1979),
No. 307105 (November 1989), 648 pages,
Pp. 863-865 and "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glafkides, Chemie et P.)
hisique Photographique, Paul Montel, 1967), Photographic Emulsion Chemistry by Duffin, published by Focal Press (G.
F. Duffin, Photographic Emulsion Chemistry (Focal P
ress, 1966)), "Production and coating of photographic emulsions" by Zerikman et al., published by Focal Press (VL Zelikman et al.,
Making and CoatingPhotographic Emulsion, Focal Pr
ess, 1964) and the like.

US Pat. Nos. 3,574,628;
Monodisperse emulsions described in, for example, 655,394 and British Patent 1,413,748 are also preferable. Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described in Photographic Science and Engineering (Gutoff,
Photographic Science and Engineering), Volume 14,
248-257 (1970); U.S. Pat.
4,226, 4,414,310, 4,43
It can be easily prepared by the methods described in 3,048, 4,439,520 and British Patent 2,112,157.

The crystal structure may be uniform, the inside and the outside may have different halogen compositions, or may have a layered structure. Also, silver halides having different compositions are joined by epitaxial junction. May be
Further, it 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.

The above-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed, or a type having a latent image on both the surface and the inside. Must be a type of emulsion. Of the internal latent image type, the core / core described in JP-A-63-264740 is used.
It may be a shell type internal latent image type emulsion. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-13.
No. 3542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additives used in such a process are Research Disclosure Nos. 17643, 18716 and 30.
7105, and the relevant portions are summarized in the table below.

The light-sensitive material of the present invention comprises a photosensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more types of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used for the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. A silver halide grain having a grain inside or a surface fogged is
It is a silver halide grain that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material.
A method for preparing silver halide grains having the inside or the surface of the grains fogged is described in U.S. Pat. No. 4,626,498;
-214852.

The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.75 μm.
m, particularly preferably 0.05 to 0.6 μm. The grain shape is not particularly limited, and may be regular grains or polydisperse emulsions, but may be monodisperse (at least 95% of the weight or the number of silver halide grains is ± 40% of the average grain size). %).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the development process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average value of circle equivalent diameters of projected areas) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grains is
There is no need for optical sensitization, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing fine silver halide grains. The coated silver amount of the light-sensitive material of the present invention is preferably not more than 6.0 g / m ² , and is 4.5.
g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above-mentioned three Research Disclosures, and the related portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 (December 1978) (November 1979) (November 1978) 1 Chemical sensitizer page 23 648 right column page 866 2 Sensitivity enhancer page 648 right column 3 Spectral sensitization Agent, pages 23 to 24, page 648, right column to pages 866 to 868, supersensitizer, page 649, right column 4 whitening agent, page 24, page 647, right column, page 868, 5 antifoggant, pages 24 to 25, page 649, right column, 868 to Page 870 and Stabilizer 6 Light absorber, Page 25-26 Page 649 Right column-Page 873 Filter dye, Page 650 Left column UV absorber 7 Anti-staining agent Page 25 Right column Page 650 Left column-Right column Page 872 8 Dye Image stabilizer page 25 page 650 left column page 872 9 film hardening agent page 26 651 page left column 874 to 875 page 10 binder 26 page same as above 873 to 874 page 11 plasticizer and lubricant page 27 650 page right column 876 page 12 coating Auxiliaries, pages 26-27 ibid. 875-876 pages Surfactant 13 antistatic agents p. 27 pages ibid. 876-877 pages 14 matting agents pages 878-879

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,9
It is preferable to add a compound capable of reacting with formaldehyde described in JP-A No. 87 or 4,435, 503 and immobilizing the same to the light-sensitive material. In the light-sensitive material of the present invention, U.S. Patent Nos. 4,740,454 and 4,788,132 are used.
JP-A-62-18539, JP-A-1-28355
It is preferable to include the mercapto compound described in No. 1 above. Compounds which release a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof irrespective of the amount of developed silver produced by the development processing described in JP-A-1-106052. Is preferably contained. The light-sensitive material of the present invention may be added to International Publication WO88 / 04.
Nos. 794 and 317, 308A, U.S. Pat. No. 4,420,555, and JP-A-1-259358.
It is preferable to include the dye described in (1).

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure (RD) No. 17643, VII-C to G, and No. 307105, VII-C. To the patents listed in G.

Examples of yellow couplers other than those represented by the general formula (I) of the present invention which can be used in combination include, for example, US Pat. Nos. 3,933,501 and 4,022,620.
No. 4,326,024 and 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107
No. 39, British Patent Nos. 1,425,020 and 1,4
No. 76,760; U.S. Pat. Nos. 3,973,968; 4,314,023; 4,511,649;
Those described in EP 249,473A and the like are preferred.

As the magenta coupler, various pyrazolone type magenta couplers and pyrazoloazole type magenta couplers are preferably used. As a pyrazolone-based magenta coupler, US Pat. No. 4,310,619,
No. 4,351,897, European Patent 73,636
No. 3,061,432 and US Pat. No. 3,72.
5,067, JP-A-60-35730, 55-1.
No. 18034, No. 60-185951, U.S. Pat. No. 4,556,630, International Publication WO88 / 04795.
And the like are particularly preferable.

Pyrazoloazole-based magenta couplers preferably used in the present invention are represented by the following general formula (I
Examples include magenta couplers represented by I). General formula (II)

Embedded image (In the formula, R ₁ represents a hydrogen atom or a substituent, Y represents a hydrogen atom or a leaving group. Za, Zb and Zc represent methine, substituted methine, = N- or -NH-, and Za-
One of the Zb bond and the Zb-Zc bond is a double bond and the other is a single bond. In the case of Zb-Zc bond or carbon-carbon double bond, it includes the case where it is a part of aromatic ring.
When R ₁ or Y forms a dimer or higher multimer, and when Za, Zb, or Zc is a substituted methine, the case where the substituted methine forms a dimer or higher multimer is included. )

The pyrazoloazole-based coupler represented by the above general formula (II) is a known coupler, but among the pyrazoloazole-based couplers, there are few yellow sub-absorptions of color forming dyes and light fastness. 4,500,63
The imidazo [1,2-b] pyrazoles described in No. 0 are preferable, and the pyrazolo [1,5-b] [1,2,4] triazoles described in US Pat. No. 4,540,654 are particularly preferable.

Other Pyrazolotriazole couplers having a branched alkyl group directly bonded to the 2, 3 or 6-position of the pyrazolotriazole ring as described in JP-A-61-65245, described in JP-A-61-65246. Are pyrazoloazole couplers containing a sulfonamide group in the molecule, and pyrazoloazole couplers having an alkoxyphenyl sulfonamide ballast group described in JP-A-61-147254 are European Patent Nos. 226,849 and 294,785. It is preferable to use the pyrazolotriazole coupler having the 6-position alkoxy group or aryloxy group described in 1. Specific examples of the coupler represented by formula (II) are shown below.

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Examples of cyan couplers include phenol type and naphthol type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
Nos. 228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826,
No. 3,772,002 and No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
No. 4,775,616, No. 4,451,55
No. 9, No. 4,427,767, No. 4,690, 8
No. 89, No. 4,254,212, No. 4,296,
199 and JP-A-61-42658 are preferred. Among them, the ureido type cyan coupler represented by the general formula (III) and the 5-amidonaphthol type cyan coupler represented by the general formula (IV) are particularly preferable. General formula (III)

Embedded image (In the formula, R ₁ is a substituted or unsubstituted aryl group,
₂ represents a substituted or unsubstituted alkyl group, aryl group, cycloalkyl group and heterocyclic residue, and Z represents a hydrogen atom or a coupling-off group. )

Specific examples of the cyan coupler represented by formula (III) are shown below, but the invention is not limited thereto.

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Embedded image (In the formula (IV), R ₁ is —CONR ₄ R ₅ , —SO
₂ represents NR ₄ R ₅ . R ₂ represents a group capable of substituting on the naphthalene ring, and l is an integer of 0 to 3. R ₃ represents an alkyl group, an aralkyl group, an acyl group, an alkoxycarbonyl group, an alkylaminocarbonyl group or an alkylsulfonyl group, and these groups further include a halogen atom,
It may be substituted with an alkoxy group or the like. X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. However, R ₄ and R ₅ may be the same or different and each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. When _two or more l's are present, R _2's may be the same or different and may be bonded to each other to form a ring. R ₂ and R ₃ , or R ₃ and X may combine with each other to form a ring. In addition, in R ₁ , R ₂ , R ₃ or X, a dimer or a multimer having a valence of 2 or more and bound to each other via a divalent or higher valent group may be formed. )

Specific examples of the coupler represented by formula (IV) are shown below, but the coupler is not limited to these.

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Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
Nos. 09,320, 4,576,910, British Patent 2,102,137, and European Patent No. 341,188A.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent 96,570,
Those described in West German Patent (Published) No. 3,234,533 are preferred.

Colored couplers for correcting unnecessary absorption of color forming dyes are described in Research Disclosure No.
VII-G of 17643, VII-G of No. 307105
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 1,146,368.
Those described in the above item are preferred. Also, U.S. Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in No. 4,181,
It is also preferable to use a coupler having a dye precursor group capable of forming a dye by reacting with a developing agent described in US Pat. No. 4,777,120 as a leaving group.

Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention.
The DIR coupler releasing the development inhibitor is the RD1 described above.
No. 7643, Section VII-F and No. 307105, VII-
Patent described in section F, JP-A-57-151944,
Those described in U.S. Pat. Nos. 57-154234, 60-184248, 63-37346, 63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

As a coupler capable of releasing a nucleating agent or a development accelerator imagewise upon development, there are described in British Patent No. 2,093.
7,140,2,131,188, JP-A-59
Preferred are those described in JP-A-157638 and JP-A-59-170840. Also, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1-44940.
Also preferred are compounds capable of releasing a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A-45687.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
No. 4,283,4.
No. 72, No. 4,338,393, No. 4,310,
No. 618, etc .;
No. 5950, Japanese Patent Application Laid-Open No. 62-24252, and the like.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. 173,302A and 313,308A , RD. No.1
1449, 24241, and bleaching accelerator releasing couplers described in JP-A-61-201247, U.S. Pat.
55,477, etc., couplers releasing leuco dyes described in JP-A-63-75747, couplers releasing fluorescent dyes described in U.S. Pat. No. 4,774,181, and the like. Can be

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-257747 are used.
272248 and 1,2-benzisothiazolin-3-one, n-butyl, p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol described in JP-A No. 1-80941. It is preferable to add various antiseptics or antifungal agents such as 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.

Suitable supports that can be used in the present invention are, for example, those described in RD. No. 17643, page 28, and No. 18
No. 716, from the right column on page 647 to the left column on page 648;
07105, page 897. In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, and 23 μm or less.
Or less, more preferably 18 μm or less,
Particularly preferably, it is 16 μm or less. Also, the film swelling speed T _1/2
Is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness means a film thickness measured under humidity control at 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering (Phot) by A. Green et al.
Sci. Eng.), Vol. 19, No. 2, pp. 124-129, and can be measured by using a swellometer (swelling meter) of the type, and T _1/2 is 30 ° C. in a color developing solution. 3 minutes 1
90% of the maximum swollen film thickness reached when the treatment is performed for 5 seconds is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling ratio is preferably from 150 to 400%. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the following formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.
The light-sensitive material of the present invention preferably has a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent, and the like. The swelling ratio of this back layer is 150 to 500%.
Is preferred.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pp. 28-29, No. 18
716, pages 880 to 881 of No. 307105.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 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-N-β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferred. These compounds can be used in combination of two or more depending on the purpose.

The color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole compound, a benzothiazole compound or a mercapto compound. It is common to include such a development inhibitor or an antifoggant. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cycloalkyl Hexane diamine tetraacetic 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 salts thereof can be mentioned as typical examples.

When the reversal processing is carried out, black and white development is usually carried out and then color development is carried out. A known black-and-white developing agent such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol is used alone in the black-and-white developer. Alternatively, they can be used 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 is generally 3 liters or less per square meter of the photographic material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. 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.

The area of contact between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [area of contact between treatment liquid and air (cm ² )] / [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, more preferably 0. 0.001 to 0.05. As a method of reducing the aperture ratio in this manner, in addition to providing a shield such as a floating lid on the surface of the photographic processing solution in the processing tank, Japanese Patent Application Laid-Open No.
No. 033, a method using a movable lid,
And a slit developing method described in JP-A-216050. Reducing the aperture ratio is not only in both the color development and black-and-white development steps, but also in the subsequent steps,
For example, it is preferably applied in all steps such as bleaching, bleach-fixing, fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

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

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. Furthermore, processing in two continuous bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Representative bleaching agents include organic complex salts of iron (III) such as amino diamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Among these, iron (III) complex salts of aminopolycarboxylic acid such as iron (III) complex salt of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate are preferred from the viewpoint of rapid treatment and prevention of environmental pollution. . Further, the aminopolycarboxylic 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 bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but the processing can be carried out at a lower pH 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 specification: U.S. Pat. No. 3,893,858, West German Patent Nos. 1,290,812, 2,059,988, JP Nos. 53-32736, 53-57831, 53
No. 37418, No. 53-72623, No. 53-95
No. 630, No. 53-95731, No. 53-10423
No. 2, No. 53-124424, No. 53-141623
Compounds having a mercapto group or a disulfide group described in Research Disclosure No. 17129 (July, 1978); thiazolidine derivatives described in JP-A-50-140129; -8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5
No. 61; thiourea derivative; West German Patent No. 1,12
7,715; iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,748,4.
Polyoxyethylene compounds described in No. 30;
Polyamine compounds described in JP-A-5-8836; and JP-A-49-40943, JP-A-49-59644 and JP-A-53-96444
No. 94927, No. 54-35727, No. 55-265
Nos. 06 and 58-163940; bromide ions and the like. Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and in particular, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95630.
Are preferred. Further, U.S. Pat.
Compounds described in 552,834 are also preferred. 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.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid is a compound having an acid dissociation constant (p K a) of 2 to 5, specifically, acetic acid,
Propionic acid and the like are preferred.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Use of thiosulfates Are generally used, and ammonium thiosulfate is most widely used. 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 of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in EP-A-294769A is preferable. Further, 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.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, or 2 for adjusting the pH. -It is preferable to add 0.1 to 10 mol / liter of imidazoles such as methylimidazole.

[0177] The total time of the desilvering step is preferably as short as possible, as long as the desilvering failure does not occur. Preferred time is 1 minute to 3
Minutes, more preferably 1 minute to 2 minutes. Further, the processing temperature is 25 ° C to 50 ° C, preferably 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 process, it is preferable that the stirring is strengthened as much as possible. As a specific method for strengthening the stirring, a method of causing a jet of a processing solution to collide with the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461. Method to increase the effect, further moving the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the solution, to improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such stirring improving means include bleaching solution, bleach-fixing solution,
It is effective in any of the fixing solutions. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. The agitation improving means is more effective when a bleaching accelerator is used,
It is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator.

The automatic developing machine used in the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
No. 8, No. 60-191259. JP-A-60-1
As described in JP-A-91257, such a transporting means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid 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 is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Of these, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in the Journal of the Society of Motion Pictur.
e and Television Engineers Vol. 64, p. 248-
253 (May, 1955).

According to the multi-stage countercurrent method described in the above document,
Although the amount of washing water can be greatly reduced, the increase in the residence time of the water in the tank causes a problem that bacteria proliferate and generated floating substances adhere to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, a method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also, Japanese Patent Application Laid-Open No.
No. 8542, isothiazolone compounds, thiabendazoles, chlorinated bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles. "Sterilization, Sterilization, and Mold Prevention Technology of Microorganisms" edited by the Sanitation Technology Society (1982
The fungicide described in "Encyclopedia of Bactericidal and Fungicides" (ed. 1986), edited by the Japan Society of Bacteria and Fungi.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, application, and the like, but are generally in the range of 15 to 45 ° C for 20 seconds to 10 minutes, preferably in the range of 25 to 40 ° C for 30 seconds to 5 minutes. Is done. Further, the light-sensitive material of the present invention may be replaced with the above-mentioned water washing,
It can also be treated directly with a stabilizing solution. In such a stabilization process, JP-A-57-8543 and JP-A-5-8543 describe the same.
All known methods described in JP-A Nos. 8-14834 and 60-220345 can be used.

In addition, there is a case where the washing treatment is further followed by a stabilizing treatment. As an example of the stabilizing treatment, a stabilizing agent containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing, is used. You can mention the bath. 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 accompanying the above washing with water and / or replenishment of the stabilizing solution can be reused in other steps such as the 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 correct the concentration by adding water.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, U.S. Pat.
Nos. 342,597; 3,342,599; Schiff base compounds described in Research Disclosure Nos. 14850 and 15159; and aldol compounds described in No. 13924. And metal salt complexes described in U.S. Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628.

The silver halide color light-sensitive material of the present invention comprises
If necessary, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339 and JP-A-57-14.
Nos. 4547 and 58-115438.

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° 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 a lower temperature achieves an improvement in the image quality and an improvement in the stability of the processing solution. be able to.

The silver halide light-sensitive material of the present invention is described in US Pat. No. 4,500,626 and JP-A-60-1334.
No. 49, 59-218443, 61-23805
No. 6, EP 210,660 A2 and the like.

[0189]

The present invention will be described in more detail with reference to examples, but the invention is not limited thereto. The following couplers were used in Examples 1 to 5 as comparative couplers.

[0190]

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[0191]

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Example 1 On a subbed cellulose triacetate film support,
Two layers having the compositions shown below were applied to prepare Sample 001, which is a single-layer color light-sensitive material for evaluation test.

(Photosensitive layer composition) The numbers corresponding to the respective components are
The coating amount is shown in units of g / m ² . However, for the sensitizing dye, the coating amount is expressed in mol per mol of silver halide in the same layer. (Sample 001) First layer (blue-sensitive emulsion layer) Emulsion silver 0.43 Average AgI content: 8.9% Average particle size: 0.73 μm (variation coefficient) (14%) Core / shell = 3/7 Heavy structure particles (AgI content = 25% / 2%) Sensitizing dye 3.6 × 10 ⁻⁴ YC-1 0.75 HBS-1 0.75 W-1 0.10 F-1 0.004 B- 1 0.014 B-2 0.010 Gelatin 2.00

Second layer (protective layer) H-1 0.18 W-2 0.10 B-2 0.01 B-3 (diameter 1.7 μ) 0.05 B-4 (diameter 1.7 μ) 0 .10 B-5 0.10 Gelatin 1.20

[0195]

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[0196]

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[0197]

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Samples 002 to 036 are YC-of sample 001.
1 was prepared so as to have an equimolar amount with the coupler shown in Table 1. At this time, the amount of the high boiling point organic solvent was also adjusted as shown in Tables 1 and 2. These samples were imagewise exposed through an optical wedge and processed as described below.

Treatment method Process Treatment time Treatment temperature Color development 2 minutes 45 seconds 38 ° C. Bleach 6 minutes 30 seconds 38 ° C. Water wash 2 minutes 10 seconds 24 ° C. fixation 4 minutes 20 seconds 38 ° C. water wash (1) 1 minute 05 Second 24 ℃ Wash with water (2) 1 minute 00 seconds 24 ℃ Stability 1 minute 05 seconds 38 ℃ Dry 4 minutes 20 seconds 55 ℃

Next, the composition of the treatment liquid is shown. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 mg Hydroxylamine sulfate 2.4 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 Water was added to 1.0 liter pH 10.05

(Bleaching Solution) (Unit g) Ethylenediaminetetraacetic acid ferric sodium trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6 Add 0.5 ml water 1.0 liter pH 6.0

(Fixer) (Unit: g) Ethylenediaminetetraacetic acid disodium salt 0.5 Sodium sulfite 7.0 Sodium bisulfite 5.0 Ammonium thiosulfate aqueous solution (70%) 170.0 ml Water is added to 1.0 liter pH 6.7

(Stabilizing Solution) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononyl phenyl ether (average degree of polymerization: 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Water was added. 1.0 liter pH 5.0-8.0

After the processing, the characteristics of the light-sensitive material were measured with blue light, and the maximum density (Dm) and the tangent slope (γ) of the characteristic curve at 1/3 of the maximum density were obtained. Further, the processed sample was stored for 3 months under a heat and humidity condition of 60 ° C.-70%, and then the residual ratio of the color image observed at the highest density was obtained. These data are summarized in Tables 1 and 2.

[0205]

[Table 1]

[0206]

[Table 2]

As is clear from Tables 1 and 2, the comparative coupler YC-1 shows a large decrease in activity when the amount of the high boiling organic solvent is reduced, and the color fading is poor. On the other hand, comparison coupler YC
-2 shows a small decrease in activity when the amount of the high-boiling organic solvent is reduced, but the molecular extinction coefficient is small, so that it is insufficient as a color density. On the other hand, the coupler of the present invention, of course, gives a high Dm in the range of the weight ratio of the high boiling point organic solvent to the coupler of 1 to 0.5. The activity decrease is small and sufficient color density (Dm) and gradation (γ) are given.

Further, the decrease in the color image density during storage under moist heat is about 1/2 of that of the comparative coupler, and this characteristic is maintained even when the high boiling point organic solvent is reduced. On the other hand, a known comparative coupler YC-3 having a structure similar to that of the coupler of the present invention.
Has markedly poor discoloration during storage under moist heat. Further, the absorption spectrum of the dye formed by this coupler is broad, and it cannot be said that the performance is comparable to that of the coupler of the present invention. Further, the comparative coupler YC-4 is excellent in wet heat discoloration property, but the decrease in color development property when the high boiling point organic solvent is reduced is extremely large.

From the above, it can be said that the coupler of the present invention is an excellent coupler which exhibits a high color-forming property even when the amount of the high-boiling organic solvent is reduced, and causes little discoloration during storage under moist heat.

Example 2 On a subbed cellulose triacetate film support,
Each layer having the composition as shown below was applied in multiple layers to prepare Sample 100, which is a multilayer color light-sensitive material.

(Composition of Photosensitive Layer) The numbers corresponding to the respective components represent the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 100) First layer (antihalation layer) Black colloidal silver 0.18 gelatin 1.40

Second layer (intermediate layer) 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.070 EX-3 0.020 EX-11 2.0 × 10 ^-3 U-10 .060 U-2 0.080 U-3 0.10 HBS-1 0.10 HBS-2 0.020 gelatin 1.04

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 0.34 EX-9 0.020 U-1 0.070 U-2 0.050 U-3 0.070 HBS-1 0.060 Gelatin 0.87

Fourth 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 0.40 EX-3 0.050 EX-9 0.015 U-1 0.070 U-2 0.050 U-3 0.070 Gelatin 1.30

Fifth layer (third red-sensitive emulsion layer) Emulsion D Silver 1.60 Sensitizing dye I 5.4 × 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 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63

Sixth Layer (Intermediate Layer) EX-5 0.040 HBS-1 0.020 Gelatin 0.80

Seventh 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 0.26 EX-7 0.030 EX-8 0.025 HBS-1 0.10 HBS-3 0.010 Gelatin 0.63

Eighth Layer (Second Green Sensitive Emulsion Layer) Emulsion C Silver 0.45 Sensitizing Dye IV 2.1 × 10 ⁻⁵ Sensitizing Dye V 7.0 × 10 ⁻⁵ Sensitizing Dye VI 2.6 × 10 ⁻⁴ EX-6 0.094 EX-7 0.026 EX-8 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ⁻³ Gelatin 0.50

Ninth 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-10 0.10 EX-12 0.015 HBS-1 0.25 HBS-2 0.10 Gelatin 1.54

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.050 EX-5 0.080 HBS-1 0.030 Gelatin 0.95

Eleventh 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 YC -1 0.71 HBS-1 0.28 Gelatin 1.10

Twelfth Layer (Second Blue Sensitive Emulsion Layer) Emulsion G Silver 0.45 Sensitizing Dye VII 2.1 × 10 ⁻⁴ YC-1 0.16 EX-9 7.0 × 10 ⁻³ HBS-1 0.050 Gelatin 0.78

Thirteenth Layer (Third Blue Sensitive Emulsion Layer) Emulsion H Silver 0.77 Sensitizing Dye VII 2.2 × 10 ⁻⁴ YC-1 0.22 HBS-1 0.070 Gelatin 0.69

Fourteenth Layer (First Protective Layer) Emulsion I Silver 0.20 U-4 0.11 U-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ⁻² B-2 (diameter 1.7 μm) 0.10 B-30 .10 S-1 0.20 Gelatin 1.20

Further, in order to improve the storability, processability, pressure resistance, antifungal / bacteriostatic property, antistatic property and coating property of all layers, W-1, W-2, W-3, 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-13 and iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt are contained.

[0228]

[Table 3]

[0229]

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[0230]

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[0231]

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[0232]

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[0233]

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[0234]

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[0235]

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[0236]

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[0237]

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[0238]

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[0239]

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[0240]

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[0241]

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Further, the eleventh layer, the twelfth layer of the sample 100,
Samples 101 to 120 were prepared by changing the amounts of the comparative coupler YC-1 and the high boiling point organic solvent in the 13th layer as shown in Table 4. However, in Samples 117 to 120, HBS-2 was used as the high boiling point organic solvent.

These samples were exposed and processed in the same manner as in Example 1. The density | concentration of the obtained sample was measured through the blue filter. Table 4 shows the results. In Table 4, the amount of the coupler in the high boiling point organic solvent / coupler ratio does not include the DIR coupler.

[0244]

[Table 4]

From Table 4, the comparative coupler YC-1 shows a decrease in color density when the high boiling point organic solvent is reduced,
, A high concentration cannot be obtained regardless of the amount of the high-boiling organic solvent, whereas the coupler of the present invention shows a very small decrease in the color density even when the amount of the high-boiling organic solvent is reduced and a sufficient color density can be obtained. Has been. Furthermore, the couplers of the present invention are superior in color image storability to the comparative couplers, and this property is not lost even when the amount of the high boiling point solvent used is reduced.

Example 3 In Samples 101, 102, 109 to 116 of Example 2, the first ratio was adjusted so that the ratio of the weight of the coupler used and the weight of the high boiling point organic solvent and the weight of gelatin used in the same layer was constant.
Samples 201 and 20 were prepared by adjusting the amount of gelatin in layers 1 to 13
2,209-216 were produced. However, at this time, the coating amount of the coupler of each sample was also adjusted so as to give the same gradation.

The obtained sample was exposed to white light through a pattern for MTF measurement and developed according to Example 2. After the treatment, the MTF value at a spatial frequency of 25 cycles / mm was measured using red light in order to evaluate the sharpness of each sample. Table 5 shows the results.

[0248]

[Table 5]

As is clear from Table 5, the yellow coupler of the present invention reduces the amount of the high boiling point organic solvent used, and
It is possible to improve the sharpness when the amount of gelatin is reduced correspondingly. Of course, at this time, the film quality did not significantly decrease.

Example 4 In samples 201, 202 and 209 to 212 of Example 3, the ninth layer comparative couplers EX-10 and EX-12 were respectively used as EX-13 (amount used 0.07) and EX-14 (. The amount used is 0.015), and the high-boiling organic solvent HBS-1,
Samples 301, 302, 309 to 312 were prepared in which the amounts of HBS-2 used were changed to 0.14 and 0.06. At this time, the amount of gelatin was adjusted so that the weight ratio of the sum of the coupler of the 9th layer of each sample and the high boiling point organic solvent to gelatin was constant.

The obtained sample was exposed to white light through a pattern for MTF measurement and developed according to Example 2. After the treatment, red light was used to evaluate the sharpness of each sample, and the MTF value at a spatial frequency of 25 cycles / mm was measured. Table 6 shows the results.

[0252]

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[0253]

[Table 6]

0.0 in the MTF value in Table 6 above
The difference of 2 is a difference that can be visually recognized as a difference in image quality. Therefore, the difference of 0.05 can be said to be a very large difference.

As can be seen from Table 6, the coupler of the present invention provides a greater improvement in sharpness when used in combination with a pyrazoloazole type coupler represented by EX-13 and EX-14. You can

Example 5 A multilayer color light-sensitive material having each layer having the following composition was prepared on a 127 μm-thick cellulose triacetate film support having an undercoat, and was used as a sample 401. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the use described.

First layer: antihalation layer Black colloidal silver 0.25 g Gelatin 1.9 g UV absorber U-1 0.04 g UV absorber U-2 0.1 g UV absorber U-3 0.1 g UV absorber U-4 0.1 g Ultraviolet absorber U-6 0.1 g High boiling organic solvent Oil-1 0.1 g

Second layer: intermediate layer Gelatin 0.40 g Compound Cpd-D 10 mg High boiling point organic solvent Oil-3 0.1 g Dye D-4 0.4 mg

Third layer: intermediate layer Fine grain silver iodobromide emulsion with fogged surface and inside (average grain size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) silver amount 0.05 g gelatin 0.4 g

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.2 g Emulsion B Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.15 g Coupler C-2 0.05 g Coupler C-7 0 .05g Compound Cpd-D 10mg High boiling point organic solvent Oil-2 0.1g

Fifth Layer: Medium Sensitivity Red Sensitive Emulsion Layer Emulsion B Silver amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-30 0.2 g High boiling point organic solvent Oil-2 0.1 g

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.3 g Coupler C-3 0.7 g Additive P-1 0.1 g

Seventh Layer: Intermediate Layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd-K 2.6 mg UV absorber U-1 0.1 g UV absorber U-6 0.1 g Dye D -1 0.02g

Eighth layer: intermediate layer Silver iodobromide emulsion with fogged surface and inside (average grain size 0.06 μm, coefficient of variation 16%, AgI content 0.3 mol%) 0.02 g Gelatin 1.0 g added Product P-1 0.2 g Color mixing inhibitor Cpd-J 0.1 g Color mixing inhibitor Cpd-A 0.1 g

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion E Silver amount 0.3 g Emulsion F Silver amount 0.1 g Emulsion G Silver amount 0.1 g Gelatin 0.5 g Coupler C-5 0.05 g Coupler C-60 .20 g Compound Cpd-B 0.03 g Compound Cpd-D 10 mg Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-H 0.02 g High boiling point organic solvent Oil-10 0.1 g High boiling point organic solvent Oil-2 0.1 g

10th layer: Medium-speed green-sensitive emulsion layer Emulsion G Silver amount 0.3 g Emulsion H Silver amount 0.1 g Gelatin 0.6 g Coupler C-5 0.2 g Coupler C-6 0.1 g Compound Cpd-B 0 0.03 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.05 g Compound Cpd-H 0.05 g High boiling point organic solvent Oil-2 0.01 g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.3 g Coupler C-6 0.1 g Compound Cpd-B 0.08 g Compound Cpd-E 0 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-H 0.02 g High boiling point organic solvent Oil-1 0.02 g High boiling point organic solvent Oil-2 0.02 g

Twelfth layer: intermediate layer Gelatin 0.6 g Dye D-1 0.1 g Dye D-2 0.05 g Dye D-3 0.07 g

Thirteenth layer: Yellow filter layer Yellow colloidal silver Silver amount 0.1 g Gelatin 1.1 g Color mixing inhibitor Cpd-A 0.01 g High boiling point organic solvent Oil-1 0.01 g

The 14th layer: Intermediate layer Gelatin 0.6 g

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.4 g Emulsion K Silver amount 0.15 g Emulsion L Silver amount 0.05 g Gelatin 0.8 g Coupler YC-5 0.55 g

16th layer: Medium sensitivity blue-sensitive emulsion layer Emulsion L Silver amount 0.15 g Emulsion M Silver amount 0.35 g Gelatin 0.9 g Coupler YC-5 0.35 g Coupler YC-6 0.35 g

Seventeenth layer: High-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.4 g Gelatin 1.2 g Coupler YC-6 0.65 g

Eighteenth layer: First protective layer Gelatin 0.7 g Ultraviolet absorber U-1 0.04 g Ultraviolet absorber U-2 0.01 g Ultraviolet absorber U-3 0.03 g Ultraviolet absorber U-4 0. 03g UV absorber U-5 0.05g UV absorber U-6 0.05g High boiling point organic solvent Oil-1 0.02g Formalin scavenger Cpd-C 0.2g Cpd-I 0.4g Dye D-3 0.05g

19th layer: 2nd protective layer Colloidal silver Silver amount 0.1 mg Fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI content 1 mol%) Silver amount 0.1 g Gelatin 0.4 g

20th layer: 3rd protective layer Gelatin 0.4 g Polymethylmethacrylate (average particle size 1.5 μ) 0.1 g Methyl methacrylate / acrylic acid 4: 6 copolymer (average particle size 1.5 μ) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g

In addition to the above composition, additives F-1 to F-8 were added to all emulsion layers. Furthermore, in each layer,
In addition to the above composition, gelatin hardener H-1 and surfactants W-3 and W-4 for coating and emulsification were added. Further, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol and phenethyl alcohol were added as antiseptic and antifungal agents. The silver iodobromide emulsion used for Sample 101 is as follows.

[0278]

[Table 7]

[0279]

[Table 8]

[0280]

Embedded image

[0281]

Embedded image

[0282]

Embedded image

[0283]

Embedded image

[0284]

Embedded image

[0285]

[Chemical formula 106]

[0286]

Embedded image

[0287]

Embedded image

[0288]

Embedded image

[0289]

Embedded image

[0290]

[Chemical 111]

[0291]

[Chemical 112]

[0292]

[Chemical 113]

Comparative yellow couplers of the fifteenth to seventeenth layers of the above sample were used as couplers Y-8, Y-53 and Y- of the present invention.
After replacing with 57 and exposing in the same manner as in Example 2, the following processing was performed. Also in this case, as in Example 2, it was confirmed that the coupler of the present invention gave a high color density even if the amount of the high boiling point organic solvent was small.

Treatment process Treatment process Time Temperature First development 6 minutes 38 ° C Water wash 2 minutes 〃 Reversal 2 minutes 〃 Color development 6 minutes 〃 Adjustment 2 minutes 〃 Bleach 6 minutes 〃 Fixed 4 minutes 〃 Water wash 4 Min. Stabilization 1 min. Normal temperature dry treatment Use the following composition of the treatment liquid.

First developer water 700 ml Nitrilo-N, N, N-trimethylene phosphonic acid pentasodium salt 2 g sodium sulfite 20 g hydroquinone monosulfonate 30 g sodium carbonate (monohydrate) 30 g 1-phenyl-4-methyl -4-Hydroxymethyl-3-pyrazolidone 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Water was added to 1000 ml

Inversion liquid water 700 ml Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3 g Stannous chloride (dihydrate) 1 g p-amylphenol 0.1 g sodium hydroxide 8 g glacial acetic acid 15 ml Water In addition 1000 ml

Color developer water 700 ml Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3 g Sodium sulfite 7 g Sodium triphosphate (12-hydrate) 36 g Potassium bromide 1 g Potassium iodide (0.1 % Solution) 90 ml sodium hydroxide 3 g citrazinic acid 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / sulfate 11 g 3,6-dithiaoctane-1,8 -Diol 1 g Water added 1000 ml

Preparation liquid Water 700 ml Sodium sulfite 12 g Sodium ethylenediaminetetraacetate (dihydrate) 8 g Thioglycerine 0.4 ml Glacial acetic acid 3 ml Water was added to 1000 ml

Bleaching liquid Water 800 ml Sodium ethylenediaminetetraacetate (dihydrate) 2 g Iron (III) ammonium ethylenediaminetetraacetate (dihydrate) 120 g Potassium bromide 100 g Water was added to 1000 ml.

Fixer Water 800 ml Sodium thiosulfate 80.0 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to 1000 ml.

Stabilized water 800 ml Formalin (37% by weight) 5.0 ml Fuji Dry Well (surfactant manufactured by FUJIFILM Corporation) 5.0 ml Water is added to 1000 ml

Example 6 In the sample 001 of Example 1, the coupler YC-1 was changed to Y-.
A color light-sensitive material sample 601 was prepared in exactly the same manner except that the number was changed to 65.

Next, the yellow coupler (YC
-1) and high boiling point organic solvents (HBS-1) are shown in Table 9 and Table 1.
Samples 602-640 modified as shown in FIG. These samples were also exposed and processed in the same manner as the sample 601. The treated sample was subjected to sensitometric measurement to evaluate the color developability of the coupler. Further, the above sample was stored under the condition of 60 ° C.-70% for 3 months, and sensitometric measurement was performed again to evaluate the fastness of the color image. The results are shown in Tables 9 and 10.

[0304]

[Table 9]

[0305]

[Table 10]

Here, the maximum color density indicates the difference between the color density and the density of the fog portion when the color density becomes flat regardless of the exposure amount in the region where the exposure amount is sufficiently large. It can be said that the higher the maximum color density is, the smaller the coating amount required for practical use and the more excellent the coupler.

Further, in order to show the oil amount dependency of the color developability of the coupler, the color density ratio (expressed in%) based on the maximum color density when the high boiling point organic solvent / coupler ratio of each coupler is 1.0. ) Is also shown in Tables 9 and 10. It can be said that a coupler whose value does not significantly decrease even when the amount of the high-boiling organic solvent is reduced is an excellent coupler because the dependency on the amount of oil is small. By using such a coupler, the light-sensitive material can be thinned and the sharpness can be improved.

As is apparent from Tables 9 and 10, the couplers Y-53, Y-65, Y-68, Y-69, and
Y-70, Y-66, Y-67, Y-73 and Y-75 are excellent couplers having a high maximum color density. In particular, when the high boiling point organic solvent / coupler ratio is 0.3 or less, the comparative coupler YC-1 has a remarkably low color density, whereas the above-mentioned coupler of the present invention has a small decrease in density and is an excellent coupler. Recognize.

The coupler of the present invention is also excellent in color image fastness. The fastness of the color image was evaluated by the residual ratio of the color image in the Dm portion after storage for 3 months under the condition of 60 ° C.-70%. As is clear from Table 9 and Table 10,
The couplers of the present invention are all comparative couplers YC-1, YC.
Less likely to fade than -2. Particularly, Y in which the 1-position of cycloalkanecarbonyl is substituted with ethyl or propyl
-65, Y-69, Y-70, Y-66, Y-67, Y
-73 and Y-75 are more robust and can be said to be excellent couplers.

Example 7 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photographic material composed of each layer having the following composition, was prepared.

(Composition of photosensitive layer) The coating amount was the amount expressed in g / m ² of silver for silver halide and colloidal silver, and g / m for couplers, additives and gelatin.
The amount was expressed in m ² , and the sensitizing dye was expressed in moles per mole of silver halide in the same layer. The symbols indicating the additives have the following meanings. However, when there is more than one utility, only one of them is listed as a representative. UV: UV absorber, Solv: High boiling organic solvent, ExF: Dye, ExS: Sensitizing dye, ExC: Cyan coupler, ExM: Magenta coupler, ExY: Yellow coupler, Cpd: Additive

First Layer (Antihalation Layer) Black Colloidal Silver 0.15 Gelatin 2.33 ExM-2 0.11 UV-1 3.0 × 10 ^-2 UV-2 6.0 × 10 ^-2 UV-3 7.0 × 10 ⁻² Solv-1 0.16 Solv-2 0.10 ExF-1 1.0 × 10 ⁻² ExF-2 4.0 × 10 ⁻² ExF-3 5.0 × 10 ⁻³ Cpd -6 1.0 x 10 ^-3

Second Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, sphere equivalent diameter 0.4 μm, variation coefficient of sphere equivalent diameter 30%, plate-like grain , Diameter / thickness ratio 3.0) coating amount of silver 0.35 silver iodobromide emulsion (AgI 6.0 mol%, core / shell ratio 1: 2, internal high AgI type, sphere equivalent diameter 0.45 μm, sphere equivalent diameter Coefficient of variation 23%, plate-like particles, diameter / thickness ratio 2.0) Coating silver amount 0.18 Gelatin 0.77 ExS-1 2.4 × 10 ^-4 ExS-2 1.4 × 10 ^-4 ExS-5 2.3 × 10 ⁻⁴ ExS-7 4.1 × 10 ⁻⁶ ExC-1 9.0 × 10 ⁻² ExC-2 2.0 × 10 ⁻² ExC-3 4.0 × 10 ⁻² ExC-4 2.0 x 10 ^-2 ExC-5 8.0 x 10 ^-2 ExC-6 2.0 x 10 ^-2 ExC-9 1.0 x 10 ^-2

Third Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 6.0 mol%, core-shell ratio 1: 2, internal high AgI type, sphere equivalent diameter 0.65 μm, variation of sphere equivalent diameter) Coefficient 23%, plate-like particles, diameter / thickness ratio 2.0) Silver coating amount 0.80 Gelatin 1.46 ExS-1 2.4 × 10 ⁻⁴ ExS-2 1.4 × 10 ⁻⁴ ExS-52 .4 × 10 ⁻⁴ ExS-7 4.3 × 10 ⁻⁶ ExC-1 0.19 ExC-2 1.0 × 10 ⁻² ExC-3 2.5 × 10 ⁻² ExC-4 1.6 × 10 ^-2 ExC-5 0.19 ExC-6 2.0x10 ^-2 ExC-7 3.0x10 ^-2 ExC-8 1.0x10 ^-2 ExC-9 3.0x10 ^-2

Fourth Layer (High Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 9.3 mol%, core-shell ratio 3: 4: 2 multi-structured grains, AgI content from the inside of 24, 0, 6 mol %, Equivalent sphere diameter 0.75 μm, variation coefficient of equivalent sphere diameter 23%, plate-like particles, diameter / thickness ratio 2.5) Coating silver amount 1.05 Gelatin 1.38 ExS-1 2.0 × 10 ^-4 ExS-2 1.1x10 ^-4 ExS-5 1.9x10 ^-4 ExS-7 1.4x10 ^-5 ExC-1 8.0x10 ^-2 ExC-4 9.0x10 ^-2 ExC-6 2.0 × 10 ^-2 ExC-9 1.0 × 10 ^-2 Solv-1 0.20 Solv-2 0.53

Fifth Layer (Intermediate Layer) Gelatin 0.62 Cpd-1 0.13 Polyethylacrylate Latex 8.0 × 10 ⁻² Solv-1 8.0 × 10 ⁻²

Sixth Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, sphere equivalent diameter 0.45 μm, variation coefficient of sphere equivalent diameter 15%, plate-like particles , Diameter / thickness ratio 4.0) coating amount of silver 0.13 gelatin 0.31 ExS-3 1.0 × 10 ^-4 ExS-4 3.1 × 10 ^-4 ExS-5 6.4 × 10 ^-4 ExM -1 0.12 ExM-3 2.1x10 ^-2 Solv-1 0.09 Solv-4 7.0x10 ^-3

Seventh Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, sphere equivalent diameter 0.65 μm, variation coefficient of sphere equivalent diameter 18%, tabular grains , Diameter / thickness ratio 4.0) amount of coated silver 0.31 gelatin 0.54 ExS-3 2.7 × 10 ⁻⁴ ExS-4 8.2 × 10 ⁻⁴ ExS-5 1.7 × 10 ⁻⁴ ExM -1 0.27 ExM-3 7.2 × 10 -2 ExY-1 5.4 × 10 -2 Solv-1 0.23 Solv-4 1.8 × 10 -2

Eighth Layer (High Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (multi-structured grains having AgI of 9.8 mol%, silver amount ratio 3: 4: 2, AgI content of 24, 0, 3 from the inside). Mol%, equivalent sphere diameter 0.81 μm, coefficient of variation of equivalent sphere 23%, multiple twinned plate-like particles, diameter / thickness ratio 2.5) Coating amount of silver 0.49 Gelatin 0.61 ExS-4 4.3 × 10 ^-4 ExS-5 8.6 × 10 ^-5 ExS-8 2.8 × 10 ^-5 ExM-2 1.0 × 10 ^-2 ExM-5 1.0 × 10 ^-2 ExM-6 3.0 × 10 ^-2 ExY-1 1.5 × 10 ^-2 ExC-1 0.4 × 10 ^-2 ExC-4 2.5 × 10 ^-3 ExC-6 0.5 × 10 ^-2 Solv-1 0.12 Cpd-8 1.0 × 10 ^-2

Ninth layer (intermediate layer) Gelatin 0.56 Cpd-1 4.0 × 10 ^-2 Polyethyl acrylate latex 5.0 × 10 ^-2 Solv-1 3.0 × 10 ^-2 UV-4 3. ^{0x10 -2} UV-5 4.0x10 ^-2

10th layer (donor layer having a multilayer effect on the red-sensitive layer) Silver iodobromide emulsion (AgI 8.0 mol%, core-shell ratio 1: 2, internal high AgI type particles, sphere equivalent diameter 0.72 μm, sphere Coefficient of variation of equivalent diameter 28%, multiple twin plate-like grains, diameter / thickness ratio 2.0) Coating amount 0.67 Silver iodobromide emulsion (AgI 10.0 mol%, core-shell ratio 1: 3) AgI-type particles, sphere equivalent diameter 0.40 μm, variation coefficient of sphere equivalent diameter 15%, normal crystal particles) Silver coating amount 0.20 Gelatin 0.87 ExS-3 6.7 × 10 ⁻⁴ ExM-4 0.06 ExM-8 0.10 Solv-1 0.30 Solv-6 3.0 × 10 ^-2

Eleventh layer (yellow filter layer) Yellow colloidal silver 9.0 × 10 ⁻² gelatin 0.84 Cpd-2 0.13 Solv-1 0.13 Cpd-1 5.0 × 10 ⁻² Cpd-6 2.0 x 10 ^-3 H-1 0.25

Twelfth Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 9.0 mol%, multi-structured grain, spherical equivalent diameter 0.70 μm, variation coefficient of spherical equivalent diameter 20%, tabular grain , Diameter / thickness ratio of 7.0, and 200 kv observed by a transmission electron microscope, 50% or more of all grains have 10 or more dislocation lines inside the grains.) Coating amount of silver 0.50 Silver iodobromide Emulsion (AgI 2.5 mol%, uniform AgI type, equivalent sphere diameter 0.50 μm, coefficient of variation of equivalent sphere diameter 30%, tabular grains, diameter / thickness ratio 6.0) coated silver amount 0.30 gelatin 2. 18 ExS-6 9.0 × 10 ^-4 ExC-1 0.05 ExC-2 0.10 ExY-2 0.05 ExY-3 1.09 Solv-1 0.55

Thirteenth Layer (Intermediate Layer) Gelatin 0.30 ExY-4 0.14 Solv-1 0.14

Fourteenth Layer (High Sensitivity Blue Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type grain, spherical equivalent diameter 1.2 μm, variation coefficient of spherical equivalent diameter 25%, multiplex Twinned plate-like particles, diameter / thickness ratio 2.0) Coating amount of silver 0.40 Gelatin 0.59 ExS-6 2.6 × 10 ⁻⁴ ExY-2 1.0 × 10 ⁻² ExY-3 0.20 ExC-1 1.0 × 10 ^-2 Solv-1 0.10.

Fifteenth Layer (First Protective Layer) Fine grain silver iodobromide emulsion (AgI 2.0 mol%, uniform AgI type, sphere equivalent diameter 0.07 μm) Silver coating amount 0.12 Gelatin 0.63 UV-4 0.11 UV-5 0.18 Solv-5 2.0 × 10 ^-2 Cpd-5 0.10 Polyethyl acrylate latex 9.0 × 10 ^-2

Sixteenth Layer (Second Protective Layer) Fine grain silver iodobromide emulsion (AgI 2.0 mol%, uniform AgI type, sphere equivalent diameter 0.07 μm) Silver coating amount 0.36 Gelatin 0.85 B-1 (Diameter 2.0 μm) 8.0 × 10 ^-2 B-2 (Diameter 2.0 μm) 8.0 × 10 ^-2 B-3 2.0 × 10 ^-2 W-4 2.0 × 10 ^-2 H -1 0.18

In addition to the above, the samples thus prepared were
1,2-benzisothiazolin-3-one (average 200 ppm relative to gelatin), n-butyl-p-hydroxybenzoate (about 1000 ppm the same), and 2-phenoxyethanol (about 10,000 ppm the same) were added. 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 and iron salts, lead salts, gold salts, platinum salts, iridium salts, and rhodium salts.

In addition to the above components, each layer contains a surfactant W.
-1, W-2 and W-3 were added as coating aids and emulsifying dispersants.

[0330]

Embedded image

[0331]

[Chemical 115]

[0332]

Embedded image

[0333]

[Chemical 117]

[0334]

Embedded image

[0335]

[Chemical formula 119]

[0336]

Embedded image

[0337]

[Chemical 121]

[0338]

[Chemical formula 122]

[0339]

Embedded image

[0340]

Embedded image

[0341]

Embedded image

[0342]

[Chemical formula 126]

[0343]

Embedded image

[0344]

[Chemical 128]

[0345]

[Chemical formula 129]

[0346]

Embedded image

[0347]

Embedded image

Sample 702 was prepared by replacing the yellow coupler ExY-3 in the 12th and 14th layers with the couplers of the present invention shown in Tables 11, 12, 13 and 14 in equimolar amounts. ~ 735 were made. At this time, the amounts of the high boiling point solvents used are also shown in Table 11, Table 12, Table 13 and Table 14. However, if you replace the yellow coupler as it is, the gradation of the green and red photosensitive layers will change, so
At the same time, the amount of the DIR coupler ExY-2 used was changed as shown in Table 11, Table 12, Table 13 and Table 14 to adjust the gradations of the green photosensitive layer and the red photosensitive layer to be substantially the same. Regarding the high boiling point organic solvent / coupler ratio of 0.30, a sample in which the amount of DIR coupler was not changed was also prepared for reference.

The above sample was imagewise exposed using an optical wedge and then subjected to the following treatment.

Processing step Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 37.8 ° C. 20 ml 10 liters Bleach 45 seconds 38.0 ° C. 5 ml 5 liters Settling (1) 45 seconds 38.0 ° C. − 5 liters fixed (2) 45 seconds 38.0 ° C 30ml 5 liters stable (1) 20 seconds 38.0 ° C-5 liters stable (2) 20 seconds 38.0 ° C-5 liters stable (3) 20 Seconds 38.0 ° C 40ml 5 liters Dry 1 min 55 ° C Replenishment amount per 35mm width 1m ² Fixing Countercurrent method from (2) to (1) Stability Countercurrent method from (3) to (1) The amount of the developing solution brought into the bleaching step and the amount of the fixing solution brought into the stabilizing step were 2.5 ml and 2.0 ml per 1 m length of the light-sensitive material having a width of 35 mm.

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 5.0 6.0 Sodium sulfite 4.0 5.0 Potassium carbonate 30.0 37.0 Potassium bromide 1.3 0.5 0.5 Iodine Potassium iodide 1.2 mg-Hydroxylamine sulfate 2.0 3.6 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.7 6.2 Water was added to 1.0 liter. 1.0 liter pH 10.00 10.15

(Bleaching Solution) Tank Solution (g) Replenishing Solution (g) 1,3-Diaminopropanetetraacetic Acid Ferric Ammonium Monohydrate 144.0 206.0 1,3-Diaminopropanetetraacetic Acid 2.8 4 0.0 Ammonium bromide 84.0 120.0 Ammonium nitrate 17.5 25.0 Ammonia water (27%) 10.0 1.8 Acetic acid (98%) 51.1 73.0 Potassium carbonate 10.0-Add water 1.0 liter 1.0 liter pH 4.3 3.4

(Fixing Solution) Tank Solution and Replenishing Solution Common (g) Ethylenediaminetetraacetic acid disodium salt 1.7 Sodium sulfite 14.0 Sodium bisulfite 10.0 Ammonium thiosulfate aqueous solution (700 g / liter) 210.0 ml Ammonium thiocyanate 163.0 Thiourea 1.8 Add water 1.0 liter pH 6.5

(Stabilizer) Tank liquid, replenisher common (unit: g) Surfactant [C ₁₀ H ₂₁ -O- (CH ₂ CH ₂ O) ₁₀ -H] 0.2 Polymaleic acid (average molecular weight 2000) 0 0.11,2-Benzisothiazolin-3-one 0.05 Hexamethylenetetramine 5.5 Water was added to 1.0 liter pH 8.5

The results are shown in Table 11, Table 12, Table 13 and Table 14.
Shown in

[0356]

[Table 11]

[0357]

[Table 12]

[0358]

[Table 13]

[0359]

[Table 14]

As is clear from Table 11, Table 12, Table 13 and Table 14, the comparative coupler ExY-3 markedly lowers the B color density when the amount of the high boiling point solvent used is small.
On the other hand, the G color density is rather increased, indicating that the layering effect on the green photosensitive layer is reduced. This means that the graininess is significantly deteriorated. (Samples 701 to 70
4) If the amount of the DIR coupler used is reduced, the yellow color density can be restored, but at the same time, the layering effect is also reduced, and it is thought that the graininess is also deteriorated.
(Samples 702, 705 to 707)

The couplers of the present invention, such as Y-53, are outside the scope of the claims and have a high boiling point organic solvent / coupler ratio of 0.
At 50, it goes without saying that a high yellow color density is exhibited, but even if the amount of the high-boiling organic solvent is small, the decrease in yellow color density is extremely small, and a sufficient color density can be provided. (Samples 708 to 711, when the amount of DIR coupler was changed so that the magenta color density was about the same)

For reference, the case where the amount of DIR coupler was not changed (Sample 712) was added. In this case, although the yellow color density is decreased, the magenta color density is also decreased, and therefore, the multi-layer effect is caused. You can see that it takes too much.

The couplers Y-65, Y-69 and Y of the present invention
Similar results are obtained for -70, Y-66, Y-67, Y-68, and Y-75.

Table 11, Table 12, Table 13 and Table 14 also show fading data of yellow color images. It can be said that the coupler of the present invention is an excellent coupler in terms of color image fastness. Among them, Y-65, Y-69, Y-70, Y-6
It can be said that 6, Y-67 and Y-75 are more excellent couplers.

[0365]

INDUSTRIAL APPLICABILITY The silver halide color photographic light-sensitive material of the present invention forms an image of high color development even if the amount of the high boiling organic solvent for the yellow coupler is reduced, and it is possible to form a thin layer, and an image with high sharpness is obtained. can get. It also has excellent color image storability.

[57]

Claims (1)

(57) [Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein at least one light-sensitive silver halide emulsion layer has an acyl group represented by the following general formula: A halogen containing at least one acylacetamide type yellow dye-forming coupler represented by (I), and having a weight ratio of the high-boiling organic solvent to the dye-forming coupler contained in the layer is 0.3 or less. Silver halide color photographic light-sensitive material. General formula (I) (In the formula, R ₁ represents a monovalent group. Q represents C together with 3
Represents a non-metallic atomic group necessary to form a 5- to 5-membered hydrocarbon ring or a 3- to 5-membered heterocycle 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. )