JP2709232B2 - 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 containing a novel acylacetamide type yellow dye-forming coupler, and more particularly to a silver halide color photographic material having reduced color at a yellow coloring site. It relates to a photosensitive material.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material is exposed to light and then subjected to color development, whereby an oxidized aromatic primary amine developing agent and a dye-forming coupler (hereinafter referred to as a coupler) are formed. The reaction forms a color image.

Generally, in this method, a color reproduction method based on a subtractive color method is used, and in order to reproduce blue, green, and red, yellow, magenta, and cyan color images having complementary colors are formed. For forming a yellow color image, a yellow dye-forming coupler (hereinafter referred to as a yellow coupler)
As acylacetamide couplers and malondianilide couplers, 5-pyrazolone couplers and pyrazolotriazole couplers as magenta couplers for forming magenta color images, and phenol couplers and naphthol couplers as cyan couplers for forming cyan color images, respectively. Commonly used.

The yellow dye, magenta dye and cyan dye obtained from these couplers are generally formed in a silver halide emulsion layer which is sensitive to radiation absorbed by the dye or an adjacent layer thereof. It is a target.

By the way, yellow couplers, particularly acylacetamide couplers such as benzoylacetoanilide couplers and pivaloylacetoanilide couplers are generally used for image formation. The former generally has a high coupling activity with an oxidized aromatic primary amine developing agent during development, and has a large molecular extinction coefficient of a yellow dye to be generated. It is mainly used for color negative films, and the latter is mainly used for color paper and color reversal films because of its excellent spectral absorption characteristics and fastness of yellow dye.

However, benzoylacetanilide type couplers have high coupling reactivity with an oxidized form of an aromatic primary amine developing agent at the time of color development and have a large molecular extinction coefficient of a generated yellow azomethine dye. There is a disadvantage that the spectral absorption characteristics of the yellow image are inferior,
Pivaloylacetanilide type couplers have excellent spectral absorption characteristics for yellow images, but have low coupling reactivity with oxidized aromatic primary amine developing agents during color development, and generate yellow azomethine dyes. There is a disadvantage that the molecular extinction coefficient is small.

[0007] Here, the high coupling reactivity of the coupler and the large molecular extinction coefficient of the dye formed result in high sensitivity,
It enables a high gamma value and a high color density, and has a so-called high color developability. Further, the excellent spectral absorption characteristics in the yellow image means, for example, absorption characteristics in which the long wavelength side of the spectral absorption is good and the unnecessary absorption in the green region is small.

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

US Pat. No. 3,265,506 discloses acyl groups of acylacetanilide type couplers such as pivaloyl group, 7,7-dimethylnorbornane-1-carbonyl group and 1-methylcyclohexane-1-carbonyl group. No. 26133, Shirokupropane-1
-Carbonyl group, cyclohexane-1-carbonyl group and the like are disclosed. However, these couplers were inferior in any point, such as poor coupling reactivity, low molecular extinction coefficient of the dye, and poor spectral absorption characteristics of color images.

On the other hand, a method of using a water-insoluble polymer together with a coupler in a high boiling organic solvent is described in, for example, US Pat. Nos. 3,619,195, 4,201,589, 4,120,725 and the like. Is known to. In addition, International Patent Publication WO / 00723 and US Patent 5,006,4
No. 53 describes an example of co-dispersing with a water-insoluble polymer to improve the color image preservability of a cyan coupler or a magenta coupler. In addition to the above-mentioned U.S. patent, it is described in JP-A-64-50049 that the use of a water-insoluble polymer and an epoxy compound in combination improves the color image fastness.

Incidentally, in the silver halide color photographic light-sensitive material, it is not only the spectral absorption characteristics of the generated yellow dye that contribute to the color reproduction of yellow. Even if the dyes to be formed have the same structure, the degree of the red light varies depending on the combination of the structure of the leaving group of the coupler, the composition of the light-sensitive material and the composition of the developing solution. Has undesired absorption in the green and green light regions,
Giving a dirty color image (hereinafter referred to as "color stain")
There is. Due to the discoloration of the color, there is a problem that when used in a light-sensitive material, the color is reproduced as a dull yellow with a gray tint despite excellent absorption of the coloring dye itself.

[0012] The causes include residual silver images due to poor desilvering in the desilvering step, color mixing resulting from interlayer movement of the oxidized base during development, and coloring components generated by side reactions of the oxidized base. Conceivable. However, its detailed contents and contribution ratio are not well known. Further, in the acylacetamide type yellow coupler represented by the general formula (I) of the present invention, the stability of the formed color image to light and heat is insufficient, and thus an improvement is required.

[0013]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and a first object of the present invention is to provide a silver halide color photographic material having good spectral absorption characteristics and excellent color reproducibility. In particular, it is an object of the present invention to provide a silver halide color photographic light-sensitive material in which the color of a yellow-colored portion is reduced.

A second object of the present invention is to provide a silver halide color photographic material having improved color image storability.

[0015]

Means for Solving the Problems The objects described above are as follows: (1) a yellow-color-forming silver halide emulsion layer on a support,
In a multilayer silver halide color photographic light-sensitive material having a magenta color-forming silver halide emulsion layer and a cyan color-forming silver halide emulsion layer, the yellow color-forming silver halide emulsion layer has an acyl group represented by the following general formula (I). A silver halide color photographic light-sensitive material comprising at least one acylacetamide-type yellow coupler represented by formula (I) and at least one water-insoluble polymer.

[0016]

Embedded image (In the general formula (I), R ₁ represents a monovalent group, and Q together with C contains a 3- to 5-membered hydrocarbon ring or at least one heteroatom selected from N, S, O, P in the ring. Have 3 ~
Represents a group of non-metallic atoms necessary for forming a 5-membered plural ring. However, R ₁ is not a hydrogen atom and does not combine with Q to form a ring. (2) a yellow-color-forming silver halide emulsion layer on a support,
In a multilayer silver halide color photographic light-sensitive material having a magenta color-forming silver halide emulsion layer and a cyan color-forming silver halide emulsion layer, the yellow color-forming silver halide emulsion layer has an acyl group represented by the above general formula (I). A silver halide color photographic light-sensitive material comprising at least one acylacetamide-type yellow coupler represented by the formula (I) and at least one water-insoluble polymer in the cyan coloring silver halide emulsion layer; and (3) The silver halide color photographic light-sensitive material as described in (1) above, wherein the cyan-color-forming silver halide emulsion layer contains at least one water-insoluble polymer.

The acylacetamide type yellow coupler having an acyl group represented by formula (I) used in the present invention will be described in more detail below.

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

[0019]

Embedded image In the formula (Y), R ₁ represents a monovalent substituent excluding hydrogen,
Q is a 3- to 5-membered hydrocarbon ring together with C or at least 1
Number of N, S, O, a non-metallic atomic group necessary to form a 3-5 membered heterocyclic ring containing a heteroatom selected from P in the ring, R ₂ is a hydrogen atom, a halogen atom (F , Cl, Br,
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 is represented by R
₃ represents a group capable of being substituted on a benzene ring, X represents a group capable of leaving by a coupling reaction with a hydrogen atom or an oxidized form of an aromatic primary amine developer (hereinafter referred to as a leaving group), Represents an integer of 0 to 4, respectively. However, when 1 is plural, plural R ₃ may be the same or different. R
₁ is preferably an organic residue containing no metal atom,
More preferably, it is a hydrocarbon group which may have a substituent.

Here, examples of R ₃ include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, Alkylsulfonyl, ureido, sulfamoylamino, alkoxycarbonylamino, alkoxysulfonyl, acyloxy, nitro, heterocyclic, cyano, acyl, acyloxy, alkylsulfonyloxy, arylsulfonyloxy Examples of the leaving group include a heterocyclic group, an aryloxy group, an arylthio group, an acyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, a heterocyclic oxy group, and a halogen atom, which are bonded to a coupling active site with a nitrogen atom. 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, and may be substituted 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 contains an aryl group, unless otherwise specified, the aryl group may be a monocyclic or composite ring aryl group which may be substituted (for example, phenyl, 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 ring, the heterocyclic group is at least one selected from O, N, S, P, Se and Te, unless otherwise specified. A 3- to 8-membered optionally substituted monocyclic or condensed-ring heterocyclic group containing two heteroatoms in the ring (for example, 2-
Furyl, 2-pyridyl, 4-pyridyl, 1-pyrazolyl, 1-imidazolyl, 1-benzotriazolyl, 2-
Benzotriazolyl, succinimide, phthalimide,
1-benzyl 2,4-imidazolidindion-3-yl).

Hereinafter, the substituents preferably used in the formula (Y) will be described.

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

In the formula (Y), Q is preferably a C number of 3 to 3 which may be substituted with any of 3 to 5 members together with C.
It represents a group of nonmetallic atoms necessary for forming a hydrocarbon ring of 0 or a heterocyclic ring having 2 to 30 carbon atoms containing at least one heteroatom selected from N, S, O and P in the ring. Also,
The ring formed by Q and C may have an unsaturated bond in the ring. Examples of the ring formed by Q 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, a cyano group, an alkoxycarbonyl group, an alkylthio group, and an arylthio group.

In the formula (Y), R ₂ is preferably a halogen atom, any of which may be substituted.
An alkoxy group, an aryloxy group having 6 to 30 carbon atoms, C
It represents an alkyl group having 1 to 30 amino groups 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, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, each of which may be substituted. An alkoxycarbonyl group having 2 to 30 carbon atoms, an aryloxycarbonyl group having 7 to 30 carbon atoms, a carbonamide group having 1 to 30 carbon atoms, a sulfonamide group having 1 to 30 carbon atoms, and a carbamoyl group having 1 to 30 carbon atoms , C number 0-3
0 sulfamoyl group, alkylsulfonyl group having 1 to 30 carbon atoms, arylsulfonyl group having 6 to 30 carbon atoms, 1 carbon atom
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), 1 preferably represents an integer of 1 or 2, and the substitution position of R ₃ is a meta position or a para position with respect to the group represented by the formula (Ya) in Chemical formula 4. Position is preferred.

[0030]

Embedded image 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 an optionally substituted monocyclic or condensed 5- to 7-membered heterocyclic group, and examples thereof include succinimide, maleimide 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-1,3,4
-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 represents an aryloxy group having 6 to 30 carbon atoms, and may be substituted with a group selected from the group of substituents when X is a heterocyclic ring. .
Examples of the substituent of the aryloxy group include a halogen atom, a cyano group, a nitro group, a carboxyl group, a trifluoromethyl group, an alkoxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group,
An alkylsulfonyl group, an arylsulfonyl group, or a cyano group is preferred.

Next, substituents particularly preferably used in the formula (Y) will be described.

R ₁ is particularly preferably a halogen atom,
A substituted or unsubstituted alkyl group, more preferably an α-position, an alkyl group having no branched chain at the β-position,
More preferably, it is a linear alkyl group having 1 to 4 carbon atoms,
Most preferably, it is an ethyl group. Q is particularly preferably C
The ring formed therewith is a group of non-metallic atoms forming a _3- to 5-membered hydrocarbon ring, for example,-(CR ₂ ) ₂ -,-(CR ₂ ) ₃ -,-(CR ₂ ) ₄
-. Here, R represents a hydrogen atom, a halogen atom or an alkyl group. However, a plurality of R and CR ₂ may be the same or different.

Q is most preferably — (CR ₂ ) ₂ — which forms a three-membered ring with C to be bonded. R ₂ is particularly preferably chlorine atom, fluorine atom, and C 1
To 6 alkyl groups (e.g., methyl, trifluoromethyl, ethyl, isopropyl, t-butyl);
An alkoxy group (e.g., methoxy, ethoxy, methoxyethoxy, butoxy), or an aryloxy group having 6 to 24 C (e.g., phenoxy group, p-tolyloxy,
p-methoxyphenoxy), most preferably a chlorine atom, a methoxy group or a trifluoromethyl group.

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

X is particularly preferably chemical formula 5, chemical formula 6, or chemical formula 7
Formula (Y-1), (Y-2), or (Y-3) described in
Is a group represented by

[0037]

Embedded image In the formula (Y-1), Z represents —O—CR ₄ (R ₅ ) —,
_{S-CR 4 (R 5)} -, NR 6 -CR 4 (R 5) -, -
_{NR 6 -NR 7 -, NR 6} -C (0) -, - CR 4 (R
_{5) -CR 8 (R 9)} - or CR ₁₀ = CR ₁₁ - represent.

Here, R ₄ , R ₅ , R ₈ and R ₉ are 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. Wherein R ₆ and R ₇ are a hydrogen atom, an alkyl group,
Represents 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).

Particularly preferred among the heterocyclic groups represented by the formula (Y-1) are those represented by the formula (Y-1) wherein Z is -O-
CR ₄ (R ₅ ) —, NR ₆ —CR ₄ (R ₅ ) or —N
It is a heterocyclic group represented by R ₆ —NR ₇ —. The C number of the heterocyclic group represented by the formula (Y-1) is 2 to 30, preferably 4 to
20, more preferably 5 to 16.

[0040]

Embedded image In the formula (Y-2), at least one of R ₁₂ and R ₁₃
One is a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, an alkoxycarbonyl group,
A group selected from a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group or an acyl group,
The other may be a hydrogen atom, an alkyl group or an alkoxy group. R ₁₄ represents a group having the same meaning as R ₁₂ or R _13, and m represents an integer of 0 to 2. The C number of the aryloxy group represented by the formula (Y-2) is 6 to 30, preferably 6 to 24, and more preferably 6 to 15.

[0041]

Embedded image In the formula (Y-3), W represents a group of nonmetal atoms necessary for forming a pyrrole ring, a pyrazole ring, an imidazole ring or a triazole ring together with N. Here, the ring represented by the formula (Y-3) 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, an aryloxy group or a carbamoyl group. The C number of the heterocyclic group represented by the formula (Y-3) is 2 to 30, preferably 2 to 24,
More preferably, it is 2-16.

X is most preferably a group represented by the formula (Y-1).

The coupler represented by the formula (Y) is a compound represented by the formula (Yb), which is a substituent R ₁ , Q, X or a group represented by the formula (Yb). Multimers or higher multimers may be formed. in this case,
The number of carbon atoms may be out of the specified range for each substituent.

[0044]

Embedded image Formulas 9 to 18 show specific examples of each substituent in the formula (Y).

[0045]

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[0046]

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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]

Embedded image Formulas 19 to 37 show specific examples of the yellow coupler represented by the formula (Y).

[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]

Embedded image The yellow coupler of the present invention represented by the formula (Y) is
8 can be synthesized.

[0074]

Embedded image In the reaction formula of Chemical formula 38, compound a is, for example,
J. Chem. Soc. (C), 1968, 2548; Am. Chem. So
c., 1934, 56, 2710, Synthesis, 1971, 258, J. Or
g. Synthesized by the method described in Chem., 1978, 43, 1729, CA, 1960, 66, 18533y.

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

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

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

Next, the chloro-substituted or bromo-substituted product and the leaving group protonated product HX are combined with methylene chloride, chloroform, tetrahydrofuran, acetone, acetonitrile, dioxane, N-methylpyrrolidone, N, N'-dithymimidazo. In a solvent such as lysine-2-one, N, N-dimethylformamide, N, N-dimethylacetamide, the reaction temperature is -20C to 150C, preferably -10C.
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 following is a synthesis example of the coupler of the present invention. Synthesis Example 1 Synthesis of Exemplified Compound Y-25 Gotkis, D. etal, J, Am. Chem. Soc., 1934, 56, 27
25. 1-methylcyclopropanecarboxylic acid synthesized by the method described in 10 above, 100 ml of methylene chloride, N,
38.1 in a mixture of 1 ml of N-dimethylformamide
g of oxalyl chloride was added dropwise at room temperature over 30 minutes. After the dropwise addition, the mixture was reacted at room temperature for 2 hours to remove methylene chloride and excess oxalyl chloride under reduced pressure of an aspirator to obtain an oil of 1-methylcyclopropanecarbonyl chloride.

To a mixture of 6 g of magnesium and 2 ml of carbon tetrachloride, 100 ml of methanol was added dropwise at room temperature over 30 minutes, and the mixture was refluxed for 2 hours, and then 32.6 g of ethyl 3-oxobutanoate was added dropwise over 30 minutes under heating and reflux. did. After the dropwise addition, the mixture was heated under reflux for another 2 hours, and methanol was completely distilled off under reduced pressure of an aspirator. 100 ml of tetrahydrofuran was added to and dispersed in the reaction product, and the 1-methylcyclopropanecarbonyl chloride obtained earlier was added dropwise at room temperature. After reacting for 30 minutes, the reaction solution was diluted with 300 ml of ethyl acetate,
After extraction with dilute sulfuric acid and washing with water, the organic layer was dried over anhydrous sodium sulfate and the solvent was distilled off to obtain 55.3 g of ethyl 2- (1-methylcyclopropanecarbonyl) -3-oxobutanoate as an oil. .

Ethyl 2- (1-methylcyclopropanecarbonyl) -3-oxabutanoate 55 g, ethanol 1
60 ml of the solution was stirred at room temperature, and 60 ml of 30% aqueous ammonia was added dropwise thereto over 10 minutes. Thereafter, the mixture was stirred for 1 hour, extracted with 300 ml of ethyl acetate, diluted hydrochloric acid, neutralized and washed with water. The organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off (1-methylcyclopropanecarbonyl).
43 g of ethyl acetate oil 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 using a mixed solvent of n-hexane and ethyl acetate to obtain 49 g of the exemplified compound Y-25 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-25 was mixed with 300 m of methylene chloride.
and 5.4 g of sulfuryl chloride was added dropwise over 10 minutes under ice-cooling. After reacting for 30 minutes, the reaction solution is thoroughly washed with water, dried over anhydrous sodium sulfate and concentrated, and then the exemplified compound Y-25 is prepared.
Was obtained. 18.7 g of 1-benzyl-5-ethoxyhydantoin, 11.2 ml of triethylamine, N,
A solution prepared by dissolving the chloride of Exemplified Compound Y-25 previously synthesized in 50 ml of N, N-dimethylformaldehyde was added dropwise at room temperature over 30 minutes to a solution of 50 ml of N-dimethylformamide.

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

The structure of the compound was confirmed by MS spectrum, NMR spectrum and elemental analysis. The melting point is 132
３3 ° C.

The use amount of the acylacetamide type yellow coupler of the present invention in a silver halide color light-sensitive material is preferably 0.01 to 5 mmol / m ² , more preferably 0.1 to ² mmol / m ² .

The polymer of the present invention is disclosed in International Publication No. WO88 /
No. 00723 and JP-A-63-44658 can be used.

Among them, the polymer used in the present invention may be any polymer as long as it is water-insoluble, but a vinyl polymer and a polyester polymer having a repeating unit having a-(C = 0)-bond Are preferred in terms of preventing cyan from being smeared.

As the vinyl monomer preferably used in the polymer of the present invention, two or more kinds of monomers are used as a comonomer for various purposes (for example, improvement of solubility). Further, a monomer having an acid group may be used as a comonomer as long as the copolymer does not become water-soluble for the purpose of controlling color development and solubility. In addition, a monomer having two or more crosslinkable ethylenically unsaturated components can be used. As such a monomer, for example, those described in JP-A-60-151636 can be preferably used.

When a hydrophilic monomer (here, a monomer which becomes water-soluble when made into a homopolymer) is used as a comonomer in the vinyl monomer used in the present invention, the copolymer becomes water-soluble. The ratio of the hydrophilic monomer in the copolymer is not particularly limited as long as it does not occur, but is usually preferably 40 mol% or less, more preferably 20 mol% or less.
Mol% or less, more preferably 10 mol% or less.
When the hydrophilic comonomer to be copolymerized with the monomer of the present invention has an acid group, the proportion of the comonomer having an acid group in the copolymer is usually 20 mol% or less from the viewpoint of image storability. Preferably, it is at most 10 mol%, most preferably when no such comonomer is present.

The monomers used in the present invention in the polymer are preferably methacrylates, acrylamides and methacrylamides. Particularly preferred are acrylamide and methacrylamide.

The number average molecular weight of the polymer usable in the present invention is preferably from 5,000 to 150,000, more preferably from 10,000 to 100,000.

The water-insoluble polymer in the present invention is 10
The solubility of the polymer in 0 g of distilled water (25 ° C.) is 3 g
The polymer is preferably 1 g or less.

Some specific examples of the polymer used in the present invention are described below, but the present invention is not limited to these. The copolymerization ratio of the copolymer in the specific examples shown below is
It is a molar ratio.

P-1) Polymethyl methacrylate P-2) Polyethyl methacrylate P-3) Polyisopropyl methacrylate P-4) Polymethyl chloroacrylate P-5) Poly (2-tert-butylphenyl acrylate) P-6 ) Poly (4-tert-butylphenyl acrylate) P-7) Ethyl methacrylate-n-butyl acrylate copolymer (70:30) P-8) Methyl methacrylate-acrylonitrile copolymer (65:35) P- 9) Methyl methacrylate-styrene copolymer (9
0:10) P-10) N-tert-butyl methacrylamide-methyl methacrylate-acrylic acid copolymer (60: 3)
0:10) P-11) Methyl methacrylate-styrene-vinylsulfonamide copolymer (70:20:10) P-12) Methyl methacrylate-cyclohexyl methacrylate copolymer (50:50) P-13) Methyl methacrylate Acrylic acid copolymer (95: 5) P-14) Methyl methacrylate-n-butyl methacrylate copolymer (65:35) P-15) Methyl methacrylate-N-vinyl-2-pyrrolidone copolymer (90:10) P-16) Poly (N-sec-butylacrylamide) P-17) Poly (N-tert-butylacrylamide) P-18) Polycyclohexyl methacrylate-methyl methacrylate copolymer (60:40) P-19) n -Butyl methacrylate-methyl methacrylate-acrylamide Copolymer (20:70:10) P-20) Diacetone acrylamide-methyl methacrylate copolymer (20:80) P-21) N-tert-butylacrylamide-methyl methacrylate copolymer (40:60) P -22) Poly (Nn-butylacrylamide) P-23) Tert-butyl methacrylate-N-te
rt-butyl acrylamide copolymer (50:50) P-24) tert-butyl methacrylate-methyl methacrylate copolymer (70:30) P-25) poly (N-tert-butyl methacrylamide) P-26) N -Tert-butylacrylamide-methyl methacrylate copolymer (60:40) P-27) methyl methacrylate-acrylonitrile copolymer (70:30) P-28) methyl methacrylate-styrene copolymer (75:25) P- 29) Methyl methacrylate-hexyl methacrylate copolymer (70:30) P-30) Poly (4-biphenyl acrylate) P-31) Poly (2-chlorophenyl acrylate) P-32) Poly (4-chlorophenyl acrylate) P -33) Poly (pentachlorophenyla) Acrylate) P-34) poly (4-ethoxycarbonylphenyl acrylate) P-35) poly (4-methoxycarbonylphenyl acrylate) P-36) poly (4-cyanophenyl acrylate) P-37) poly (4 -Methoxyphenyl acrylate) P-38) Poly (3,5-dimethyladamantyl acrylate) P-39) Poly (3-dimethylaminophenyl acrylate) P-40) Poly (2-naphthyl acrylate) P-41) Poly (Phenyl acrylate) P-42) Poly (N, N-dibutylacrylamide) P-43) Poly (isohexylacrylamide) P-44) Poly (isooctylacrylamide) P-45) Poly (N-methyl-N-) Phenylacrylamide) P-46) poly (adamantyl methacrylate) P-47) poly (sec-butyl methacrylate) P-48) N-tert-butylacrylamide-acrylic acid copolymer (97: 3) P-49) poly (2-chloroethyl methacrylate) P-50) poly (2-cyanoethyl methacrylate) P-51) poly (2-cyanomethylphenyl methacrylate) P-52) poly (4-cyanophenyl methacrylate) P-53) poly (cyclohexyl methacrylate) P-54) poly (2- (Hydroxypropyl methacrylate) P-55) poly (4-methoxycarbonylphenyl methacrylate) P-56) poly (3,5-dimethyladamantyl methacrylate) P-57) poly (phenyl methacrylate) P-58) poly (4- Butoxycarbonylphenyl methacrylamide) P-5 9) Poly (4-carboxyphenyl methacrylamide) P-60) Poly (4-ethoxycarbonylphenyl methacrylamide) P-61) Poly (4-methoxycarbonylphenyl methacrylamide) P-62) Poly (cyclohexylchloro) Acrylate) P-63) Poly (ethylchloroacrylate) P-64) Poly (isobutylchloroacrylate) P-65) Poly (isopropylchloroacrylate) P-66) Poly (phenylacrylamide) P-67) Poly (cyclohexylacrylamide) P-68) Poly (phenylmethacrylamide) P-69) Poly (cyclohexylmethacrylamide) P-70) Poly (butylene adipate) In the present invention, the amount of the water-insoluble polymer used in the silver halide color light-sensitive material is as follows. The feeling The weight ratio is preferably 0.01 to 2.0, more preferably 0.1 to 1.0, and still more preferably 0.2 to 1.0 with respect to the yellow or cyan coupler contained in the photosensitive layer of the material. It is.

In the present invention, cyan couplers advantageously used from the viewpoint of color reproducibility include the general formulas (IVa) and (IVb) described in Chemical formulas (39) and (40).
The compound represented by these is mentioned. The cyan coupler of the present invention is preferably an oil-soluble cyan coupler.

[0097]

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[0098]

Embedded image In the general formulas (IVa) and (IVb), R ₁ , R ₂ and R ₄ represent a substituted or unsubstituted aliphatic, aromatic or heterocyclic group, R ₃ , R ₅ and R ₆ represent a hydrogen atom,
It represents a halogen atom, an aliphatic group, an aromatic group or an acylamino group, and R ₃ may represent a group of non-metallic atoms forming a nitrogen-containing 5- or 6-membered ring together with R ₂ . Y ₁ and Y _{2 each} represent a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent, and n represents 0 or 1.

Formula (IVa) and Formula (IVb)
Preferred examples of the aliphatic group for R ₁ , R ₂ and R ₄ include methyl, butyl, tridecyl, cyclohexyl and allyl having 1 to 32 carbon atoms, and the aryl group includes phenyl and naphthyl. Examples of the heterocyclic group include 2-pyridyl, 2-imidazolyl, 2-furyl and 6-quinolyl. These groups further include an alkyl group, an aryl group, a heterocyclic group,
Alkoxy group (for example, methoxy, 2-methoxyethoxy), aryloxy group (2,4-di-tert-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy), alkenyloxy group (2-propenyloxy), acyl group (Eg, acetyl, benzoyl), ester groups (eg, butoxycarbonyl, phenoxycarbonyl, acetoxy, benzoyloxy, butoxysulfonyl, toluenesulfonylexyl), amide groups (eg, acetylamino, methanesulfonamide, dipropylsulfamoylamino) Carbamoyl groups (eg, dimethylcarbamoyl, ethylcarbamoyl), sulfamoyl groups (eg, butylsulfamoyl), imide groups (eg, succinimide, hydantoinyl), ureido groups (eg, phenylurei) Dimethylurei), an aliphatic or aromatic sulfonyl group (eg, methanesulfonyl, phenylsulfonyl), an aliphatic or aromatic thio group (eg, ethylthio, phenylthio), a hydroxy group, a cyano group, a carboxy group, a nitro group, It may be substituted with a group selected from a sulfo group, a halogen atom and the like.

In the general formula (IVa), when R ₃ and R ₅ are a substitutable substituent, they may be substituted with the substituent described for R ₁ .

In formula (IVb), R ₅ is preferably an aliphatic group, and is preferably methyl, ethyl, propyl, butyl, pentadecyl, tert-butyl, cyclohexyl, cyclohexylmethyl, phenylthiomethyl, dodecyloxyphenyl. Luthiomethyl, butanamidomethyl, methoxymethyl and the like can be mentioned.

Formula (IVa) and Formula (IVb)
In the above, Y ₁ and Y ₂ each represent a hydrogen atom or a coupling-off group (including a coupling-off group; the same applies hereinafter). Examples thereof include a halogen atom (for example, fluorine, chlorine, bromine) and an alkoxy group (for example, ethoxy). , Dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy), aryloxy group (eg, 4-chlorophenoxy, 4-methoxyphenoxy group, 4-carboxyphenoxy), acyloxy group (eg, acetoxy) , Tetradecanoyloxy, benzoyloxy), a sulfonyloxy group (eg, methanesulfonyloxy, toluenesulfonyloxy), an amide group (eg, dichloroacetylamino, heptafluorobutylamino, methanesulfonylamino, toluenesulfonyl) Nylamino), an alkoxycarbonyloxy group (eg, ethoxycarbonyloxy, benzyloxycarbonyloxy), an aryloxycarbonyloxy group (eg, phenoxycarbonyloxy), an aliphatic or aromatic thio group (eg, ethylthio, phenylthio, tetrazolylthio), imide Groups (eg, succinimide, hydantoinyl) and aromatic azo groups (eg, phenylazo). These leaving groups may include photographically useful groups.

In formula (IVa), R ₁ is preferably an aryl group or a heterocyclic group, and is preferably a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamide group, or a sulfamoyl group. , A sulfonyl group, a sulfamide group, an oxycarbonyl group, and an aryl group substituted with a cyano group.

When R ₃ and R ₂ do not form a ring in formula (IVa), R ₂ is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group. And R
₃ is preferably a hydrogen atom.

In the formula (IVb), preferred R ₄ is a substituted or unsubstituted alkyl group or aryl group.
Particularly preferred is a substituted aryloxy-substituted alkyl group.

In the general formula (IVb), preferred R ₅ is an alkyl group having 1 to 15 carbon atoms and a methyl group having a substituent having 1 or more carbon atoms, and examples of the substituent include an arylthio group, an alkylthio group, an acylamino group and an aryl group. An oxy group and an alkyloxy group are preferred.

In the general formula (IVb), R ₅ has 1 carbon atom
It is more preferably an alkyl group having from 15 to 15, particularly preferably an alkyl group having 2 to 4 carbon atoms.

Most preferably, it is ethyl.

In formula (IVb), preferred R
₆ is a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred.

In formulas (IVa) and (IVb), preferred Y ₁ and Y ₂ are each a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group.

In formula (IVb), Y ₂ is preferably a halogen atom, particularly preferably a chlorine atom or a fluorine atom.

When n = 0 in the general formula (IVa),
Y ₁ is more preferably a halogen atom, and particularly preferably a chlorine atom or a fluorine atom.

Formulas 41 to 52 show specific examples of the cyan coupler of the present invention represented by formula (IVa) or (IVb), but the present invention is not limited thereto.

[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

Embedded image The amount of the cyan coupler of the present invention used in the silver halide color light-sensitive material is preferably 0.01 to 5 mmol /
m ² , more preferably 0.05 to ² mmol / m ² .

Next, a method for incorporating the yellow coupler or cyan coupler of the present invention and a water-insoluble polymer in the same layer will be described.

In the present invention, the coupler and the water-insoluble polymer are preferably coexistent and finely dispersed. More preferably, the coupler and the water-insoluble polymer are in the same oil droplet. For example, the latex of the polymer of the present invention can be impregnated using a so-called loadable latex method (US Pat. No. 4,203,716). A more preferred method is described in International Patent W088 / 0072.
No. 3 and U.S. Pat. No. 5,006,453 can be used. That is, after completely dissolving the polymer of the present invention, the high-boiling coupler solvent, and the coupler together in an auxiliary organic solvent, dispersing the solution in water, preferably in an aqueous hydrophilic colloid solution, more preferably in an aqueous gelatin solution. This is a method of dispersing in the form of fine particles using an ultrasonic wave, a colloid mill or the like with the help of

In the silver halide color light-sensitive material of the present invention, the yellow color-forming layer and the cyan color-forming layer can be arranged at any positions.
It is preferable to provide a yellow coloring layer on the side near the incident light.

As the silver halide used in the present invention, silver chloride, silver bromide, silver (iodo) chlorobromide, silver iodobromide and the like can be used. It is preferable to use a silver chlorobromide or silver chloride emulsion having a silver chloride content substantially free of silver of 90% mol or more, more preferably 95% or more, and particularly 98% or more.

In the light-sensitive material according to the present invention, a dye capable of being decolorized by the treatment described in European Patent EPO, 337, 490A2, pp. 27-76, is applied to the hydrophilic colloid layer in order to improve the sharpness of the image. (Of which oxonol dyes are particularly preferred) so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, or a divalent to tetravalent alcohol (for example, It is preferable to contain 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with trimethylolethane) or the like.

In the light-sensitive material according to the present invention, it is preferable to use a color image preservability improving compound as described in European Patent EPO, 277,589A2 together with a coupler. In particular, combination use with a pyrazoloazole coupler is preferred.

That is, a compound which is chemically bonded to an aromatic amine-based developing agent remaining after the color developing process to form a chemically inert and substantially colorless compound and / or an aromatic compound remaining after the color developing process. It is possible to simultaneously or alone use a compound which chemically binds to an oxidized compound of an aromatic amine color developing agent to form a chemically inert and substantially colorless compound, for example, remaining in a film after storage after processing. It is preferable in order to prevent the generation of stain and other side effects due to the formation of a color dye due to the reaction between the color developing agent or its oxidized product and the coupler.

The light-sensitive material according to the present invention is provided with a fungicide such as that described in JP-A-63-271247 to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. It is preferred to add an agent.

The support used for the light-sensitive material according to the present invention is preferably a transparent support such as a polyester (for example, polyethylene terephthalate) or an acetate (for example, triacetyl cellulose). For a display, a white polyester-based support or a support in which a layer containing a white pigment is provided on a support having a silver halide emulsion layer may be used. In order to further improve the sharpness, it is preferable to coat an antihalation layer on the silver halide emulsion coating material or the back surface of the support. In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light.

The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure. In the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds is preferred.

In the exposure, US Pat.
It is preferable to use the band stop filter described in No. 0,726. This removes light mixing,
The color reproducibility is significantly improved.

The exposed light-sensitive material is preferably subjected to bleach-fixing after color development for the purpose of rapid processing. In particular, when the high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less for the purpose of accelerating desilvering.
Further, it is preferably about 6 or less.

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material according to the present invention, and the processing method applied for processing this light-sensitive material Examples of the processing additives include the patent publications listed in Table A, particularly European Patent EPO, 355,660A2.
Those described in (Japanese Patent Application No. 1-107011) are preferably used.

(Table A) Photographic components JP-A-62-215272 JP-A-2-33144 EPO, 355,660 A2 Silver halide emulsion page 10, upper right column, line 6 to page 28, upper right column, line 16 to page 45, line 53 to 47 page 12, lower left column line 5, page 29 lower right column line 11, page 3 line 47 Page 12 Bottom right column 4 from bottom line 30 Lines 2 to 5 Line 20 to Line 22 Line to Page 13 Top left column Line 17 Silver halide solvent Page 12 Lower left column Line 6 to − − 14 Line and page 13, upper left column From bottom line 3 to page 18 Last line in lower left column Chemical sensitizer Page 12 From lower left column 3 From page 29 Lower right column lines 12 to 47 Lines 4 to 9 From the lower right column, from the bottom right to the last line, line 5 and the lower right column on page 18, line 1 to the upper right column, page 22 line 9 from the bottom Spectral sensitizer From the upper right column, page 22, lower line 830, the upper left column, line 1 Page 47, Lines 10 to 15 (Spectral sensitization method) Lines to Page 38, End lines to Line 13 Lines Emulsion stabilizers Page 39, Upper left column, Line 1 to Page 30, Upper left column, Lines 14 to 47, 16 Lines to 19 Line 72 of the upper right column at the end of the upper right column Line 11 of the upper right column Development accelerators Line 72 to the lower left column of the page 1 to-Line 91 of the upper right column of the page 91 Hardening agent Line 8 to the upper right column of the page 146 − − 〜Page 155, lower left column, line 4 Developing agent precursor, page 155, lower left column, line 5 − − Sir 〜page 155, lower right column, line 2 Development inhibitory release compound 155 page, lower right column, lines 3 to 9 − − Support 155 page lower right column line 19 page 38 upper right column line 18 to page 66 line 29 to 67 to 156 page upper left column line 14 page 39 upper left column line 3 page 13 line Sensitive material layer composition page 156 Upper left column, line 15 page 28 upper right column, line 1 to page 45, line 41 to 52 to 156, lower right column line 14, line 15 line dye Dye 156, lower right column line 15, line 38, upper left column line 12 From page 66, line 18 to 22 to 184, lower right column, last line, upper right column, line 7 Line color mixing inhibitor 185, upper left column, line 1, page 36 upper right column, line 8 to page 64, line 57 to 65 184 page lower right column 3rd line 11th page 1st line Tone adjuster 188 page lower right column 4th to 8th lines--Stain inhibitor 188 page 188 right lower column 9th line 37 page upper left column last line Eyes ~ 65 pages 32 lines ~ 66 ~ 193 pages lower right column line 10 lower right column line 13 page 17 line Columns 4th to 3rd upper right column 14th line to 4th page 15th line to 4 (cyan, magenta 121 page upper left column 6th line 18 page upper left column last line and page 15th to 27th line, yellow 30 Upper right column of the page, 6th line to 5th line, 5th page, 30th line coupler) 35th lower right column, 11th line to 28th line, 45th page, 29th line to 31st line, 47th page, 23rd line to 63rd page, 50 Line Color development enhancer, page 121, upper left column, line 7 − − 〜page 125, upper right column, line 1 UV absorber 125 page, upper right column, line 37, page 37 lower right column, line 14 to page 65, lines 22 to 31 to 127 Page lower left column last line page 38 upper left column line 11 line anti-fading agent page 127 lower right column line 1 36 page upper right column line 12 to 4 line 30 to 5 (image stabilizer) to page 137 Lower left column 8 lines Page 37 Upper left column line 19 Page 23 line, page 29 Line 1 to page 45 line 25, page 45 line 33 to line 40, page 65 line 2 to line 21 High boiling point And / or page 137, lower left column, line 9, page 35, lower right column, lines 14 to 64, lines 1 to 51 are low boiling organic solvents, page 144, upper right column, last line, page 36, upper left column, bottom 4 Item Line Line 144 of the lower left column of the photographic additive Line 1 of the lower right column of page 27 Line 10 to Line 63 of the lower right column of page 63-64 Dispersion method-Line 7 of the upper right column of page 146 The last line of the upper left column of page 28 Page 56, line 35, lower right column, line 12 to page 36, upper right column, line 7 Surfactant 201 page lower left column, line 1, page 18 upper right column, line 1 to ---, page 210, upper right column last line, page 24, lower right Bottom line and line from page 27, bottom left column, bottom line 10 to bottom right column, line 9 Fluorine-containing compounds (as antistatic agent, coating aid, lubricant, anti-adhesive, etc.)-Page 210, bottom left column, one line Item 25, upper left column, 1st line-~ 222 page, lower left column, 5th line, 27 page, lower right column, 9th line Binder (hydrophilic 222 page, lower left column, 6th line, 38 page, upper right column, 8th line-66 pages, 23rd line -28 225 pages, upper left column, last line, line 18 line, thickener 225 pages, upper right column, first line----227 upper right column, second line, antistatic agent 227 pages, upper right column, third line---230 Upper left column of the page, 1st line Polymer Latec 230 Upper left column of 2nd page, 2nd line − − Line at the end of page Matting agent Line 1 at the upper left of page 240--~ Line at the end of the upper right column at page 240 ~ Process, additives, etc.) Page 5 upper right column, line 5 42 page left upper column, last line 69 pages 28 line In Table A, the quotes of JP-A-62-215272
In the place, March 1, 1987 published at the end of this gazette
Includes amendments made by the Procedure Amendment on 6th.

Among the above color couplers, yellow couplers are described in JP-A-63-231451,
Nos. 63-123047 and 63-241547 and JP-A Nos. 1-173499, 1-213648 and 1
It is also preferable to use a so-called short-wave yellow coupler described in -250944.

Further, as a cyan coupler, JP-A-2-
In addition to the diphenylimidazole-based cyan couplers described in JP-A-33144, European Patent EPO, 333,185A2
3-Hydroxypyridine cyan couplers described above in (No. 4 of couplers (42) listed as specific examples)
Equivalent couplers having a chlorine leaving group to give two equivalents, couplers (6) and (9) are particularly preferred) and cyclic active methylene cyan couplers described in JP-A-64-32260 (in particular, The use of the coupler examples 3, 8, 34 listed as examples is particularly preferred).

[0142]

【Example】

Example 1 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further applied to form a layer structure shown below. Was prepared (sample 101). After the application, it was prepared as follows.

Preparation of Coating Solution for Fifth Layer 32.0 g of a cyan coupler (ExC), a color image stabilizer (C
pd-2) 3.0 g, color image stabilizer (Cpd-4) 2.0
g, 18.0 g of the color image stabilizer (Cpd-6) and 5.0 g of the color image stabilizer (Cpd-8), and 50.0 c of ethyl acetate.
c and 14.0 g of a solvent (Solv-6) were added and dissolved. This solution was added to 500 cc of a 20% aqueous gelatin solution containing 8 cc of sodium dodecylbenzenesulfonate, and then emulsified and dispersed by an ultrasonic homogenizer to obtain an emulsified dispersion. Prepared. On the other hand, a silver chlorobromide emulsion (cubic, 1: 4 mixture of a large-sized emulsion having an average grain size of 0.58 μm and a small-sized emulsion having a mean grain size of 0.45 μm (Ag molar ratio), and the coefficient of variation of the grain size distribution was 0.1%). 09 and 0.11, and in each size emulsion, 0.6 mol% of AgBr was locally contained in a part of the grain surface). In the large-size emulsion and small-size emulsion used here, the red-sensitive sensitizing dye E shown in Table 3 was contained in an amount of 0.9 × 10 ^-4 mol per mol of silver per mol of silver, and in the small-size emulsion. In contrast, 1.
1 × 1.0 ^-4 mol is added. The emulsion was chemically ripened by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion and the red-sensitive silver chlorobromide emulsion were mixed and dissolved to prepare a fifth layer coating solution.

Coating solutions for the first to fourth, sixth, and seventh layers were prepared in the same manner as the coating solution for the fifth layer. H-1 and H-2 were used as gelatin hardeners in each layer.

Each layer has Cpd-10 and Cpd-11.
Are 25.0 mg / m ² and 50.0 mg / m ² respectively.
² was added.

Tables 1 and 2 show the spectral sensitizing dyes used for the silver chlorobromide in the blue-sensitive emulsion layer and the green-sensitive emulsion layer.

[0147]

[Table 1]

[0148]

[Table 2]

[0149]

[Table 3] Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer in an amount of 8.5 × 10 ^-5 mol per mol of silver halide. 7.7 × 10 ^-4 mol, 2.5 × 1
^0-4 moles were added.

The blue-sensitive emulsion layer and the green-sensitive emulsion layer were treated with 4-hydroxy-6-methyl-1.3,3a, 7-
Tetrazaindene was added in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol, respectively, per mol of silver halide.

In order to prevent irradiation, four kinds of dyes described in Chemical formula 53 (the coating amount is shown in parentheses) were added to the emulsion layer.

[0152]

Embedded image (Layer Structure) Tables 4 to 7 show the compositions of the respective layers. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. The chemical structural formulas or names of the compounds used for each layer are shown in Chemical formulas 54 to 61.

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[Table 4]

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[Table 5]

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[Table 6]

[0156]

[Table 7]

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Embedded image Next, the yellow coupler of the first layer of the sample 101 is shown in Table 11.
Comparative examples shown in Table 13 or the couplers of the present invention, and when the polymers shown in Tables 11 to 13 are added to the first layer, 20% by weight of the yellow coupler is added to the fifth layer, The samples 102 to 138 were prepared by adding 50% by weight of a cyan coupler.

At this time, the polymer was dissolved in the oil phase together with the coupler, and added by emulsifying and dispersing.

At this time, the coupler used is Y-1, Y
In the case of -29, Y-41, and Y-42, the coating amount of the first layer was changed to 80% and 80% without changing the composition of the coating solution.
%, 90%, and 95%.

Sensitometry was performed on these samples 101 to 138 as follows. First, each sample was subjected to gradation exposure of a sensitometric three-color separation filter using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K). The exposure at this time was performed such that the exposure amount was 250 CMS with an exposure time of 0.1 second.

The exposed samples were subjected to continuous processing (running test) using a paper processor using the processing steps and processing compositions shown in Table 8 until the replenishment was twice the tank capacity of color development. Was carried out.

[0169]

[Table 8] Tables 9 and 10 show the composition of each processing solution.

[0170]

[Table 9]

[0171]

[Table 10] The maximum yellow color density D _B (max) and yellow color density of the yellow color portion of the processed sample were 2.0
, The cyan density D _R (D _B = 2) was measured. However, for Samples 105 to 108, since the yellow color density was 2.0 or less, the same measurement was performed at a color density of 1.5.

The results are shown in Tables 11 to 13. * In the table indicates
This indicates that the cyan density is at a yellow color density of 1.5. Further, the present inventions (1), (2), and (3) in the table indicate that they correspond to the inventions described in claims 1, 2, and 3, respectively.

As can be seen from Tables 11 to 13, when the water-insoluble polymer was added to the blue-sensitive emulsion layer in the comparative coupler, the color density decreased, whereas the coupler of the present invention did not exhibit this concentration decrease or did not. Is also slight.

Next, the color D _R (D
_B = 2) increases rather slightly with the addition of the polymer in the comparative coupler, whereas it clearly decreases in the coupler of the invention. The degree of the increase is greatest when the polymer is added to both the blue-sensitive emulsion layer and the red-sensitive emulsion layer, and then when the polymer is added only to the blue-sensitive emulsion layer and then when the polymer is added only to the red-sensitive emulsion layer.

At the same time, a fading test was performed on the processed sample prepared. In the light fading test, light irradiation was performed for 12 days under a xenon fade meter of about 80,000 lux. The heat fading test was carried out at 80 ° C. and a relative humidity of 70% for 20 days.
In all cases, when the maximum color density before the color fading test was defined as 100%, the decrease in density after the test was expressed as a percentage in Tables 11 to 1.
3 is shown.

The improvement in light and thermal fading by adding a water-insoluble polymer is observed for the comparative coupler. The effect is greater when a polymer is added to the blue-sensitive emulsion layer. Similar effects are observed with the couplers of the present invention. It can be said that the improvement effect at this time is clearly larger for the coupler of the present invention. Although the coupler of the present invention is not necessarily said to have excellent color image fastness,
It is greatly improved by adding the polymer of the present invention,
It is possible to make it within the practical range.

As is evident from the above, silver halide color photosensitive materials having good color reproducibility and excellent color image fastness can be obtained by using the acylacetamide type yellow coupler of the present invention in combination with a water-insoluble polymer. Materials can be provided.

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[Table 11]

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[Table 12]

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[Table 13] Example 2 In the color photographic light-sensitive material of Example 2 described in JP-A-1-158431, the yellow couplers of the eleventh and twelfth layers were replaced with the couplers Y-1 and Y-2 of the present invention.
9, Y-41, and Y-42 were replaced so that the coating amounts were 80 mol%, 80 mol%, 90 mol%, and 95 mol%, respectively, and the coating amount of silver halide was also changed at the above ratio. Was prepared. Further, a sample was prepared in which the water-insoluble polymer P-17 was added to the eleventh and twelfth layers in an amount of 20 mol% based on the yellow coupler.

The above sample was exposed and processed by the method described in the above publication, and evaluated by the method described in Example 1 of the present invention. In this case, substantially the same effects as in the first embodiment were obtained.

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Claims (3)

(57) [Claims] 1. A multilayer silver halide color photographic light-sensitive material having a yellow-color-forming silver halide emulsion layer, a magenta-color-forming silver halide emulsion layer, and a cyan-color-forming silver halide emulsion layer on a support, A silver halide color photographic light-sensitive material characterized in that the color-forming silver halide emulsion layer contains at least one acylacetamide-type yellow coupler represented by the following general formula (I) and at least one water-insoluble polymer. material. Embedded image (In the general formula (I), R ₁ represents a monovalent group, and Q together with C contains a 3- to 5-membered hydrocarbon ring or at least one heteroatom selected from N, S, O, P in the ring. Have 3 ~
Represents a group of non-metallic atoms necessary for forming a 5-membered plural ring. However, R ₁ is not a hydrogen atom and does not combine with Q to form a ring. ) 2. A multilayer silver halide color photographic light-sensitive material having a yellow-color-forming silver halide emulsion layer, a magenta-color-forming silver halide emulsion layer, and a cyan-color-forming silver halide emulsion layer on a support, The color-forming silver halide emulsion layer contains at least one acylacetamide-type yellow coupler whose acyl group is represented by the following general formula (I), and the cyan-color-forming silver halide emulsion layer contains at least one water-insoluble polymer. A silver halide color photographic light-sensitive material comprising: Embedded image (In the general formula (I), R ₁ represents a monovalent group, and Q together with C contains a 3- to 5-membered hydrocarbon ring or at least one heteroatom selected from N, S, O, P in the ring. Have 3 ~
Represents a group of non-metallic atoms necessary for forming a 5-membered plural ring. However, R ₁ is not a hydrogen atom and does not combine with Q to form a ring. ) 3. A silver halide color photographic light-sensitive material according to claim 1, wherein said cyan color-forming silver halide emulsion layer contains at least one water-insoluble polymer.