JPH05188544A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color reproduction performance and sharpness by incorporating a specified yellow coupler in a blue-sensitive emulsion layer, a specified magenta coupler in a green-sensitive layer, and a specified cyan coupler in a red-sensitive layer. CONSTITUTION:The blue-sensitive emulsion layer contains the yellow dyestuff- forming coupler represented by formula I or II, the green-sensitive emulsion layer contains the magenta coupler represented by formula III, and the red- sensitive emulsion layer contains the cyan coupler represented by formula IV. In formulae I-III, each of X1 and X2 is alkyl, aryl, or the like; X3 is an an organic group necessary to form an N-containing heterocyclic group; Y is an aryl or heterocyclic group Z is a group to be released by coupling with the oxidation product of a developing agent; each of R1 and R2 is H or a substituent: and X is same as Z. In formula IV. R1 is H, halogen, or the like; Z is same as in formulae I and II: each of X1 and X2 is H or halogen.

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, and more particularly to a light-sensitive material excellent in color reproducibility, sharpness and color development.

[0002]

The formation of a dye image in a silver halide color photographic light-sensitive material usually involves reducing the silver halide grains in the silver halide color photographic light-sensitive material exposed to an aromatic primary amine color developing agent. It is oxidized at this time, and this oxidant is subjected to a coupling reaction with a coupler previously contained in the silver halide color photographic light-sensitive material. In a silver halide color photographic light-sensitive material, three types of couplers that form dyes of yellow, magenta and cyan are usually used in order to perform color reproduction by a subtractive method.

Color reproducibility tends to be impaired because the coloring dyes formed by the yellow, magenta and cyan couplers used in conventional silver halide color photographic light-sensitive materials have unnecessary sub-absorption. Therefore, as a technique for improving color reproducibility, a coupler that forms an image dye with less side absorption has been studied.

As a yellow coupler, an acylacetanilide type coupler having an active methylene (methine) group is generally known. These couplers have drawbacks such as a low absorption coefficient and broad spectral absorption and poor color reproducibility. Further, as a coupler similar to the yellow coupler of the present invention, for example, malondianilide yellow couplers described in U.S. Pat. Nos. 4,149,886, 4,059,984, 4,477,563 and British Patent 1,204,680 are known. These couplers had broad spectral absorption and had a long-wave end tailing, which was problematic in color reproducibility.

As the magenta coupler, attention has been paid to the improvement of the hue of magenta by using a pyrazoloazole type magenta coupler instead of the 5-pyrazolone type coupler. Regarding these couplers, for example, U.S. Pat. No. 3725067 and JP-A-60-172982.
No. 60-33552, No. 61-72238, U.S. Pat. Nos. 4,500,630, 4,540,654 and others.

Examples of cyan couplers are those described in US Pat. Nos. 2,367,531 and 2,423,730.
-Acylaminophenol couplers, U.S. Pat. No. 377.
2002, JP-A 61-3142, 61-965.
2-Acylaminophenol cyan couplers described in US Pat. No. 4,333,999, JP-A-57-207.
No. 593, No. 57-204544, No. 58-1186.
The ureidophenol cyan couplers described in JP-A No. 3 and JP-A Nos. 60-237448, 61-153640 and 61-145557 have been conventionally used.

[0007] In recent years, means for achieving high image quality in a small format have been developed one after another, but it is not sufficient yet, and further technical improvement is required. It is currently common practice to use DIR compounds to improve sharpness and interimage effects. What is usually used is a DIR coupler which releases a development inhibitor imagewise to form a coloring dye by a coupling reaction with an oxidation product of a color developing agent, but the dye produced by the coupling reaction is a main coupler. When it is different from the dye obtained from (1), color turbidity occurs, which is not preferable for color reproduction. From these things, a colorless DIR compound has been demanded.

Colorless DIR compounds are classified into two types, a coupling type and a redox type, depending on the reaction mode with an oxidant of a color developing agent. Of these, the coupling type compounds are described in, for example, JP-B-51-16141 and 51-16142, U.S. Pat. Nos. 4,226,943 and 4,171,223, and the redox compounds are, for example, U.S. Pat. No. 3,379,529. Issue 36
39417, JP-A-49-129536, 64-64
DIR hydroquinone compounds described in JP-A No. 546/1989, or JP-A-61-213847 and 64-88451.
And US Pat. No. 4,684,604 are DIR hydrazide compounds. These DIR compounds can improve image sharpness and color reproducibility by the edge effect and the inter-image effect, but they are still insufficient and further improvement has been strongly desired.

[0009]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a color light-sensitive material having high color saturation, less color turbidity or color contamination, and excellent color reproducibility.

The second object of the present invention is to provide a color light-sensitive material excellent in sharpness. The third object of the present invention is to provide a color light-sensitive material excellent in color developability.

[0011]

The objects of the present invention have been solved by the following means.

That is, the present invention provides a silver halide color photographic light-sensitive material having at least one blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support as a means for achieving the above object. In the emulsion layer, at least one yellow dye-forming coupler represented by the following formula (Ya) and / or (Yb); in the green-sensitive layer, at least one magenta dye-forming coupler represented by the following formula (M); The sensitive layer contains at least one cyan dye-forming coupler represented by the following formula (C) and at least one compound represented by the following formula (I) or (II) in at least one layer constituting the light-sensitive material. The present invention provides a silver halide color photographic light-sensitive material characterized by: Formula (Ya)

[0013]

[Chemical 7] Formula (Yb)

[0014]

[Chemical 8] Formula (M)

[0015]

[Chemical 9] Formula (C)

[0016]

[Chemical 10] Formula (I)

[0017]

[Chemical 11] Formula (II)

[0018]

[Chemical 12] In formulas (Ya) and (Yb), X ₁ and X ₂ each represent an alkyl group, an aryl group or a heterocyclic group, and X ₃
Represents an organic residue forming a nitrogen-containing heterocyclic group together with> N-, Y represents an aryl group or a heterocyclic group, and Z is released when the coupler represented by the general formula reacts with an oxidized product of a developing agent. In the formula (M), R ₁
And R ₂ represents a hydrogen atom or a substituent, X represents a hydrogen atom or a group which is released upon reaction with an oxidized product of a developing agent; in the formula (C), R _{1 is an} aliphatic group, an aromatic group or a heterocycle. represents a group, R ₂ represents a hydrogen atom, a halogen atom, an aliphatic group, an acylamino group, an aliphatic oxy group or an aromatic oxy group, R ₁ and R ₂ are joined to form a 5- to 7-membered ring together And Z represents a hydrogen atom or a group which leaves when it reacts with an oxidized product of a developing agent,
X ₁ and X _{2 each} represent a hydrogen atom or a halogen atom, and n represents an integer of 0 to 18;
R ₁₁ is R ₁₄ —N (R ₁₆ ) CON (R ₁₅ ) —, R ₁₄ OCO
_{N (R 15) -, R} 14 SO 2 (R 15) -, R 14 -N
(R ₁₆ ) SO ₂ N (R ₁₅ ) — or R ₁₇ CONH—, wherein R ¹⁴ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₁₅
And R ₁₆ represents a hydrogen atom, an alkyl group or an aryl group, R ₁₇ is an alkyl group having 2 or more carbon atoms in which a carbon atom adjacent to the carbonyl group is not substituted with a hetero atom,
An alkenyl group, an alkynyl group, an aryl group or a heterocyclic group; R ₁₂ and R ₁₃ each represent a hydrogen atom or a substituent having a Hammett's substituent constant σ _p of 0.3 or less;
B represents a group that releases X after leaving from the hydroquinone mother nucleic acid product, X represents a development inhibitor, k represents an integer, and A and A'represent a hydrogen atom or a group removable by an alkali; In (II), Q ¹ contains at least one heteroatom and, together with the carbon atom to which it is bonded, 5
Represents a group of atoms necessary to form a heterocyclic ring having at least one member ring,
R ²¹ represents a group capable of substituting for the hydroquinone nucleus,
B, X, k, A and A ′ have the same meanings as described in the general formula (I).

First, the couplers represented by the formulas (Ya) and (Yb) will be described in detail below.

When X ₁ and X ₂ represent an alkyl group,
A straight chain, branched chain, having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms,
It is a cyclic, saturated, unsaturated, substituted or unsubstituted alkyl group. Examples of alkyl groups include methyl, ethyl, propyl, butyl, cyclopropyl, allyl, t-octyl,
Examples thereof include i-butyl, dodecyl and 2-hexyldecyl.

When X ₁ and X ₂ represent a heterocyclic group, 3 to 12, preferably at least one hetero atom having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as nitrogen atom, oxygen atom or sulfur atom, is preferable. It is a 5- or 6-membered, saturated or unsaturated, substituted or unsubstituted, monocyclic or condensed heterocyclic group. Examples of the heterocyclic group include 3-pyrrolidinyl, 1,2,4-triazole-3
-Yl, 2-pyridyl, 4-pyrimidinyl, 3-pyrazolyl, 2-pyrrolyl, 2,4-dioxo-1,3-imidazolidin-5-yl or pyranyl.

When X ₁ and X ₂ represent an aryl group,
It represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. Typical examples of the aryl group are phenyl and naphthyl.

When X ₃ represents a nitrogen-containing heterocyclic group formed together with> N-, the heterocyclic group has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, and a hetero atom other than a nitrogen atom, for example, an oxygen atom. Alternatively, it may contain a sulfur atom, 3 to 12
It is a substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed-ring heterocyclic group having a membered ring, preferably a 5- or 6-membered ring. Examples of this heterocyclic group include pyrrolidino, piperidino, morpholino, 1-piperazinyl, 1-
Indolinyl, 1,2,3,4-tetrahydroquinolin-1-yl, 1-imidazolidinyl, 1-pyrazolyl,
1-pyrrolinyl, 1-pyrazolidinyl, 2,3-dihydro-1-indazolyl, 2-isoindolinyl, 1-indolyl, 1-pyrrolyl, 4-thiazin-S, S-dioxo-4-yl or benzoxazin-4-yl Is mentioned.

When X ₁ and X ₂ each represent an alkyl, aryl or heterocyclic group having a substituent, and when the nitrogen-containing heterocyclic group formed with X ₃ with> N- has a substituent, The following are mentioned as an example of those substituents. Halogen atom (eg fluorine atom, chloro atom), alkoxycarbonyl group (C2-3)
0, preferably 2-20. For example, methoxycarbonyl,
Dodecyloxycarbonyl, hexadecyloxycarbonyl), an acylamino group (having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as acetamide, tetradecane amide,
2- (2,4-di-t-amylphenoxy) butanamide, benzamide), sulfonamide group (having 1 to 3 carbon atoms)
0, preferably 1-20. For example, methanesulfonamide, dodecanesulfonamide, hexadecylsulfonamide, benzenesulfonamide), a carbamoyl group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, N-butylcarbamoyl, N, N-diethylcarbamoyl), N-
Sulfonylcarbamoyl group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, N-mesylcarbamoyl group, N-dodecylsulfonylcarbamoyl), sulfamoyl group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, N-butylsulfur) Famoyl, N-dodecylsulfamoyl, N
-Hexadecylsulfamoyl, N-3- (2,4-di-t-amylphenoxy) butylsulfamoyl, N,
N-diethylsulfamoyl), an alkoxy group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, methoxy, hexadecyloxy, isopropoxy), an aryloxy group (having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms). For example, phenoxy, 4-methoxyphenoxy, 3-t-butyl-4-
Hydroxyphenoxy, naphthoxy), aryloxycarbonyl group (C7-21, preferably 7-11.
For example, phenoxycarbonyl), an N-acyl sulfamoyl group (having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, such as N-propanoylsulfamoyl, N-tetradecanoylsulfamoyl), a sulfonyl group (having 1 carbon atom). ~ 30,
Preferably 1-20. For example, methanesulfonyl, octanesulfonyl, 4-hydroxyphenylsulfonyl, dodecanesulfonyl), alkoxycarbonylamino group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, ethoxycarbonylamino), cyano group, nitro group, carboxyl group, hydroxyl group. Group, sulfo group, alkylthio group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, methylthio, dodecylthio, dodecylcarbamoylmethylthio), ureido group (having 1 to 30 carbon atoms, preferably 1 to 2 carbon atoms)
0. For example, N-phenylureido, N-hexadecylureido), an aryl group (having 6 to 20 carbon atoms, preferably 6 carbon atoms).
~ 10. For example, phenyl, naphthyl, 4-methoxyphenyl), heterocyclic group (having 1 to 20 carbon atoms, preferably 1 to 1 carbon atoms)
0. A monocyclic or condensed ring having 3 to 12, preferably 5 or 6 membered rings containing at least one or more nitrogen atom, oxygen atom or sulfur atom as a hetero atom. For example, 2-pyridyl, 3-pyrazolyl, 1-pyrrolyl, 2,4
-Dioxo-1,3-imidazolidin-1-yl, 2-
Benzoxazolyl, morpholino, indolyl), alkyl group (having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, linear, branched, cyclic, saturated, unsaturated, for example, methyl, ethyl, isopropyl, cyclopropyl, t-). Pentyl, t
-Octyl, cyclopentyl, t-butyl, s-butyl, dodecyl, 2-hexyldecyl) acyl group (having 1 to 30 carbon atoms, preferably 2 to 20. For example, acetyl, benzoyl), acyloxy group (having 2 to 30 carbon atoms, Preferably 2 to 20. For example, propanoyloxy, tetradecanoyloxy), an arylthio group (having 6 to 20 carbon atoms, preferably 6 to 10. For example, phenylthio, naphthylthio), a sulfamoylamino group (having 0 to 30 carbon atoms, Preferably 0 to 20. For example, N-butylsulfamoylamino, N-dodecylsulfamoylamino, N-phenylsulfamoylamino) or N-sulfonylsulfamoyl group (having 1 to 30 carbon atoms, preferably 1 to 30 carbon atoms). 20. For example, N-mesylsulfamoyl, N-ethanesulfonylsulfamoyl, N- Decane acylsulfamoyl, N- hexadecane sulfonylsulfamoyl) and the like. The above substituents may further have a substituent. Examples of the substituent include the substituents mentioned here.

Preferred substituents among the above are an alkoxy group, a halogen atom, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a nitro group, an alkyl group or an aryl group. Be done.

When Y in the formulas (Ya) and (Yb) represents an aryl group, it has 6 to 20 carbon atoms, preferably 6 to 20 carbon atoms.
And 10 substituted or unsubstituted aryl groups. Phenyl and naphthyl groups are typical examples.

In formulas (Ya) and (Yb), when Y represents a heterocyclic group, it has the same meaning as described when X ₁ or X ₂ represents a heterocyclic group.

When Y represents a substituted aryl group or a substituted heterocyclic group, examples of the substituent include, for example, the substituents enumerated above when X ₁ has a substituent. As a preferred example, one of the substituents is a halogen atom, an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group, a sulfonyl group, an N-sulfonylsulfamoyl group, an N-acylsulfamoyl group, an alkoxy group, an acylamino group. When it is a group, an N-sulfonylcarbamoyl group, a sulfonamide group or an alkyl group.

A particularly preferred example of Y is a phenyl group in which at least one substituent is in the ortho position.

The group represented by Z in formulas (Ya) and (Yb) may be any conventionally known coupling-off group. Preferable Z is a nitrogen-containing heterocyclic group bonded to a coupling position at a nitrogen atom, an aryloxy group, an arylthio group, a heterocyclic oxy group, a heterocyclic thio group, an acyloxy group, a carbamoyloxy group, an alkylthio group or a halogen atom. Can be mentioned.

These leaving groups are non-photographic useful groups or photographically useful groups or their precursors (eg, development inhibitors,
Development accelerator, desilvering accelerator, fogging agent, dye, hardener,
Coupler, developing agent oxidant scavenger, fluorescent dye,
Either a developing agent or an electron transfer agent).

When Z is a photographically useful group, those conventionally known are useful. For example, US Pat. No. 42489
No. 62, No. 4409323, No. 4438193, No. 4421845, No. 4618571, No. 46525.
No. 16, No. 4861701, No. 4782012, No. 4857440, No. 4847185, No. 44775.
No. 63, No. 4438193, No. 4628024, No. 4618571, No. 4741994, European Patent Publication No. 193389A, No. 348139A, or No. 272573A, or a leaving group for releasing it (for example, timing). Group) is used.

When Z represents a nitrogen-containing heterocyclic group bonded to the coupling position at the nitrogen atom, it preferably has 1 to 1 carbon atoms.
5, preferably 1-10, 5- or 6-membered, substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed ring heterocyclic group. The hetero atom may contain an oxygen atom or a sulfur atom in addition to the nitrogen atom. Preferred specific examples of the heterocyclic group are 1-pyrazolyl, 1
-Imidazolyl, pyrrolino, 1,2,4-triazol-2-yl, 1,2,3-triazol-1-yl, benzotriazolyl, benzimidazolyl, imidazolidin-2,4-dione-3-yl, Oxazolidine-2,
4-dione-3-yl, 1,2,4-triazolidine-
3,5-dione-4-yl, imidazolidin-2,4
5-trion-3-yl, 2-imidazolinone-1-yl, 3,5-dioxomorpholino or 1-indazolyl. When these heterocyclic groups have a substituent, examples of the substituent include the substituents listed as the substituents which the group represented by the above X ₁ group may have. As a preferred substituent, one of the substituents is an alkyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an acylamino group, a sulfonamide group, an aryl group, a nitro group, a carbamoyl group, a cyano group or This is when it is a sulfonyl group.

When Z represents an aromatic oxy group, it is preferably a substituted or unsubstituted aromatic oxy group having 6 to 10 carbon atoms. A substituted or unsubstituted phenoxy group is particularly preferable. When it has a substituent, examples of the substituent include:
Examples of the substituent which the group represented by X ₁ may have include the substituents listed above. Among them, a preferred substituent is a case where at least one substituent is an electron-withdrawing substituent, and examples thereof include a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom, a carbamoyl group, a nitro group and a cyano group. Alternatively, an acyl group can be used.

When Z represents an aromatic thio group, it is preferably a substituted or unsubstituted aromatic thio group having 6 to 10 carbon atoms. Particularly preferred is a substituted or unsubstituted phenylthio group. When it has a substituent, examples of the substituent include the substituents enumerated as the substituents which the group represented by X ₁ may have. Among them, preferable substituent is when at least one substituent is an alkyl group, an alkoxy group, a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom, a carbamoyl group or a nitro group.

When Z represents a heterocyclic oxy group, the portion of the heterocyclic group contains at least one hetero atom having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as a nitrogen atom, an oxygen atom or a sulfur atom. It is a substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed-ring heterocyclic group having from 1 to 12, preferably 5 or 6 members. Examples of the heterocyclic oxy group include a pyridyloxy group, a pyrazolyloxy group, or a furyloxy group. When it has a substituent, examples of the substituent include the substituents enumerated as the substituents which the group represented by X ₁ may have. Among them, a preferable substituent is an alkyl group, an aryl group, a carboxyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an acylamino group, a sulfonamide group, a nitro group. , A carbamoyl group, or a sulfonyl group.

When Z represents a heterocyclic thio group, the portion of the heterocyclic group contains 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and contains at least one or more hetero atom such as nitrogen atom, oxygen atom or sulfur atom. It is a substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed-ring heterocyclic group having from 1 to 12, preferably 5 or 6 members. Examples of the heterocyclic thio group include a tetrazolylthio group, 1,3,4
-Thiadiazolylthio group, 1,3,4-oxadiazolylthio group, 1,3,4-triazolylthio group, benzimidazolylthio group, benzothiazolylthio group, or 2
A pyridylthio group. When it has a substituent,
Examples of the substituent include the substituents enumerated as the substituents which the group represented by X ₁ may have. Among them, preferred substituents include at least one alkyl group, aryl group, carboxyl group, alkoxy group, halogen atom, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group,
This is when it is an acylamino group, a sulfonamide group, a nitro group, a carbamoyl group, a heterocyclic group or a sulfonyl group.

When Z represents an acyloxy group, it is preferably a monocyclic or condensed ring substituted or unsubstituted aromatic acyloxy group having 6 to 10 carbon atoms, or 2 to 2 carbon atoms.
30 are preferably 2 to 20 substituted or unsubstituted aliphatic acyloxy groups. When these have a substituent,
Examples of the substituent include the substituents enumerated as the substituents which the group represented by X ₁ may have.

When Z represents a carbamoyloxy group, it is an aliphatic, aromatic, heterocyclic, substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Examples thereof include N, N-diethylcarbamoyloxy, N-phenylcarbamoyloxy, 1-imidazolylcarbonyloxy or 1-pyrrolocarbonyloxy. When these have a substituent, examples of the substituent include the substituents enumerated as the substituents which the group represented by X ₁ may have.

When Z represents an alkylthio group, it has 1 carbon atom.
It is a linear, branched, cyclic, saturated, unsaturated, substituted or unsubstituted alkylthio group of ˜30, preferably 1 to 20. When it has a substituent, examples of the substituent include the substituents enumerated as the substituents which the group represented by X ₁ may have.

Next, particularly preferred ranges of the couplers represented by the formulas (Ya) and (Yb) will be described below.

The group represented by X ₁ in formula (Ya) is
Preferred is an alkyl group. Particularly preferably 1 carbon atom
10 to 10 alkyl groups.

The group represented by Y in formulas (Ya) and (Yb) is preferably an aromatic group. Particularly preferred is a phenyl group having at least one substituent at the ortho position. As the explanation of the substituent, those explained as the substituent which may be possessed when Y is an aromatic group are mentioned. The explanation of the preferable substituents is also the same.

The group represented by Z in the formulas (Ya) and (Yb) is preferably a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling position at a nitrogen atom, an aromatic oxy group,
A 5- or 6-membered heterocyclic oxy group or a 5- or 6-membered heterocyclic thio group can be mentioned.

Preferred couplers in the formulas (Ya) and (Yb) are represented by the following formulas (Yc), (Yd) or (e). Formula (Yc)

[0046]

[Chemical 13] Formula (Yd)

[0047]

[Chemical 14] Formula (Ye)

[0048]

[Chemical 15] In the formula, Z has the same meaning as described in formula (Ya), X ₄ represents an alkyl group, X ₅ represents an alkyl group or an aromatic group, and Ar has at least one substituent at the ortho position. Represents a phenyl group, X ₆ is -C (R ₁ R
₂₎ -N <in conjunction with nitrogen-containing Hajime Tamaki (represents a monocyclic or condensed) organic residue forming a, X ₇ is -C (R ₃₎ =
Represents an organic residue forming a nitrogen-containing heterocyclic group (monocyclic or condensed ring) together with C (R ₄ ) -N <, and R ₁ , R ₂ , R ₃
And R ₄ represents a hydrogen atom or a substituent.

In formulas (Yc) to (Ye), X ₄ to
The detailed description and the preferable range of the groups represented by X ₇ , Ar and Z have the same meanings as those described in the corresponding ranges in the description of the formulas (Ya) and (Yb). When R _{1 to} R ₄ represent a substituent, the examples of the substituent that X ₁ may have are listed.

Particularly preferred couplers in the above general formula are the couplers represented by formula (Yd) or (Ye).

The couplers represented by the formulas (Ya) to (Ye) are the same as those represented by X _{1 to} X ₇ , Y, Ar, R _{1 to} R ₄ and Z via a divalent or more divalent group. Dimers or higher multimers (eg telomers or polymers) that combine may be formed. In this case, the number of carbon atoms shown in each of the above substituents may be out of the specified range.

The couplers represented by the formulas (Ya) to (Ye) are preferable examples when they are diffusion resistant couplers.
The diffusion-resistant type is a coupler having a group in the molecule that makes the molecular weight sufficiently large in order to immobilize it in the layer to which the molecule is added. Usually, an alkyl group having a total carbon number of 8 to 30, preferably 10 to 20 or an aryl group having a substituent having a total carbon number of 4 to 20 is used. These diffusion resistant groups may be substituted in any of the molecules, or may have a plurality of groups.

Specific examples of the yellow couplers represented by the formulas (Ya) to (Ye) are shown below, but the invention is not limited thereto.

[0054]

[Chemical 16]

[0055]

[Chemical 17]

[0056]

[Chemical 18]

[0057]

[Chemical 19]

[0058]

[Chemical 20]

[0059]

[Chemical 21]

[0060]

[Chemical formula 22]

[0061]

[Chemical formula 23]

[0062]

[Chemical formula 24]

[0063]

[Chemical 25]

[0064]

[Chemical formula 26]

[0065]

[Chemical 27]

[0066]

[Chemical 28]

[0067]

[Chemical 29]

[0068]

[Chemical 30]

[0069]

[Chemical 31]

[0070]

[Chemical 32]

[0071]

[Chemical 33]

[0072]

[Chemical 34]

[0073]

[Chemical 35]

[0074]

[Chemical 36] The yellow couplers of the present invention represented by the general formulas (Ya) to (Ye) can be synthesized according to the following rules. Synthesis example-1

[0075]

[Chemical 37] Synthesis of Intermediate B Compound A357.5 g (3.0 mol), Compound B39
6.3 g (3.0 mol) was dissolved in 1.21 of ethyl acetate and 0.61 of dimethylformamide. While stirring, a solution of 631 g (3.06 mol) of dicyclohexylcarbodiimide in acetonitrile (400 ml) was added at 15 to 35 ° C.
It was dripped at. After reacting at 20 to 30 ° C. for 2 hours, the precipitated dicyclohexylurea was filtered off. 500 ml of ethyl acetate and 11 of water were added to the filtrate, and the aqueous layer was removed. next,
The organic layer was washed with water 11 twice. The organic layer was dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure to obtain 629 g (98.9%) of intermediate A as an oil.

692 g (2.97 mol) of Intermediate A was dissolved in ethyl alcohol 31 and stirred at 75-80.
At 30 ° C., 430 g of 30% sodium hydroxide was added dropwise. After dropping, the mixture was reacted at the same temperature for 30 minutes, and the precipitated crystals were collected by filtration. (Yield 658 g) The crystals were suspended in water 51 and 300 ml of concentrated hydrochloric acid was added dropwise at 40 to 50 ° C. with stirring. After stirring for 1 hour at the same temperature, the crystals were collected by filtration to obtain 579 g (95%) of intermediate B. (Decomposition point 127 ° C.) Synthesis of intermediate D 45.1 g (0.22 mol) of intermediate B, compound C86.
6 g (0.2 mol) was dissolved in 400 ml of ethyl acetate and 200 ml of dimethylacetamide. While stirring, a solution of 66 g (0.32 mol) of dicyclohexylcarbodiimide in acetonitrile (100 ml) was added dropwise at 15 to 30 ° C. After reacting at 20 to 30 ° C. for 2 hours, the precipitated dicyclohexylurea was collected by filtration.

400 ml of ethyl acetate and 600 ml of water were added to the filtrate, the aqueous layer was removed, and the organic layer was washed twice with water. The organic layer was dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain 162 g of an oily substance.

This oily substance was crystallized from 100 ml of ethyl acetate and 300 ml of n-hexane to give 108 g of intermediate D.
(87.1%) was obtained. (Melting point 132-134 ° C)

[0079]

[Table 1] Synthesis of Exemplified Coupler Y-7 49.6 g (0.08 mol) of Intermediate D was dissolved in 300 ml of dichloromethane. Sulfuryl chloride 11.
4 g (0.084 mol) was added dropwise with stirring at 10 to 15 ° C.

After reacting for 30 minutes at the same temperature, 200 ml of a 5% aqueous sodium bicarbonate solution was added dropwise to the reaction mixture. The organic layer was separated, washed with 200 ml of water and dried over anhydrous sodium sulfate. Dichloromethine was distilled off under reduced pressure to obtain 47 g of an oily substance.

47 g of this oily substance was added to 200 ml of acetonitrile.
It was dissolved in ml and 28.4 g (0.22 mol) of compound D and 22.2 g (0.22 mol) of triethylamine were added thereto with stirring. After reacting at 40 to 50 ° C for 4 hours, the mixture was poured into 300 ml of water, and the precipitated oily substance was extracted with 300 ml of ethyl acetate. The organic layer was washed with 200 g of a 5% aqueous sodium hydroxide solution and then twice with 300 ml of water. The organic layer was acidified with dilute hydrochloric acid, washed twice with water, and concentrated under reduced pressure to give a residue. (Yield 70 g) The obtained oily substance was mixed with 50 ml of ethyl acetate and 100 parts of n-hexane.
Crystallization was performed with a mixed solvent of ml, and the exemplary coupler Y-7 was mixed with 4
7.8 g (80%) was obtained. (Melting point 145-7 ° C)

[0082]

[Table 2] The yellow couplers represented by formulas (Ya) to (Ye) of the present invention are 1.0 to 10 × 1 per mol of silver halide.
It can be used in the range of 0 ^-3 mol. Preferably,
It is 5.0 × 10 ^{−1 to} 2.0 × 10 ⁻² mol, and more preferably 4.0 × 10 ^{−1 to} 5.0 × 10 ⁻² mol.

The yellow couplers represented by the formulas (Ya) to (Ye) of the present invention may be used in combination of two or more kinds, or may be used in combination with other known couplers.

Next, the formula (M) in the present invention will be described in detail.

In the formula (M), R ₁ and R ₂ each represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent.

R ₁ , R ₂ and X will be described in detail.

R ₁ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, an amino group, an alkoxy group, an aryloxy group, an acylamino group, an alkylamino group. , Anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group,
Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxy It represents a carbonyl group, an acyl group or an azolyl group, and R ₁ may be a divalent group to form a bis form.

More specifically, R ₁ is each a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom), an alkyl group (eg, a straight chain or branched chain alkyl group having 1 to 32 carbon atoms, an aralkyl group, Alkenyl group, alkynyl group,
A cycloalkyl group or a cycloalkenyl group, more specifically,
For example, methyl, ethyl, propyl, isopropyl, t-
Butyl, tridecyl, 2-methanesulfonylethyl, 3
-(3-Pentadecylphenoxy) propyl, 3- {4
-{2- [4- (4-hydroxyphenylsulfonyl)
Phenoxy] dodecanamide} phenyl} propyl, 2
-Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), aryl groups (e.g. phenyl, 4-t-butylphenyl, 2,4-di-t-). Amylphenyl, 4-
Tetradecanamidophenyl), a heterocyclic group (for example,
2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxy group, amino group, alkoxy group (for example,
Methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2-methanesulfonylethoxy), an aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-). Butyloxycarbamoylphenoxy, 3
-Methoxycarbamoyl), an acylamino group (for example,
Acetamide, benzamide, tetradecanamide, 2
-(2,4-di-t-amylphenoxy) butanamide, 4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide), alkylamino A group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino),
Anilino group (for example, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino,
2-chloro-5-dodecyloxycarbonylanilino,
N-acetylanilino, 2-chloro-5- {α- (3-
t-butyl-4-hydroxyphenoxy) dodecanamide} anilino), ureido group (eg, phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (eg, N, N-dipropylsulfamoyl) Amino, N-methyl-N-decylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-)
t-butylphenoxy) propylthio), an arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio,
2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methyloxy-5-t-
Butylbenzenesulfonamide), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N-
{3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), sulfamoyl group (for example, N-
Ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N
-Diethylsulfamoyl), a sulfonyl group (for example,
Methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), heterocyclic oxy group (eg, 1-phenyltetrazole-5-oxy) , 2-tetrahydropyranyloxy), an azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), an acyloxy group (for example, acetoxy). A carbamoyloxy group (eg, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), aryl Oxy carbonylamino group (e.g., phenoxycarbonylamino), an imido group (e.g., N- succinimido, N- phthalimido, 3
-Octadecenylsuccinimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-
Pyridylthio), a sulfinyl group (for example, dodecanesulfinyl, 3-pentadecylphenylsulfinyl,
3-phenoxypropylsulfinyl), phosphonyl group (for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), acyl group (for example, acetyl, 3-phenylpropanoyl, Benzoyl, 4-dodecyloxybenzoyl) and an azolyl group (eg, imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl, triazolyl). Among these substituents, the group capable of further having a substituent may further have an organic substituent or a halogen atom linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom.

Of these substituents, preferred R ₁ is alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, ureido group, urethane group,
An acylamino group can be mentioned.

R ₂ is a group having the same meaning as the substituent exemplified for R ₁ , and is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group,
It is an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group, or an acyl group, more preferably an alkyl group, an aryl group, a heterocyclic group, an alkylthio group or an arylthio group.

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine color developing agent, and the splitting off group is described in detail. A halogen atom, an alkoxy group, an aryloxy group, an acyloxy group. Group, alkyl or aryl sulfonyloxy group, acylamino group, alkyl or aryl sulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl, aryl or heterocyclic thio group, carbamoylamino group, 5-membered or 6-membered group There are a nitrogen heterocyclic group, an imide group, an arylazo group and the like, and these groups may be further substituted with a group acceptable as the substituent for R ₁ .

More specifically, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkoxy group (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy), aryl An oxy group (for example, 4-methylphenoxy, 4-
Chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (for example, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or aryl. Sulfonyloxy groups (eg, methanesulfonyloxy, toluenesulfonyloxy), acylamino groups (eg, dichloroacetylamino, heptafluorobutyrylamino), alkyl or aryl sulfonamide groups (eg, methanesulfonamino, trifluoromethanesulfonamino, p-toluenesulfonylamino), an alkoxycarbonyloxy group (eg, ethoxycarbonyloxy, benzyloxycarbonyloxy), aryl Oxycarbonyl group (e.g., phenoxycarbonyloxy), alkyl, aryl or heterocyclic thio group (e.g., dodecylthio,
1-carboxydodecylthio, phenylthio, 2-butoxy-5-t-octylphenylthio, tetrazolylthio), carbamoylamino group (for example, N-methylcarbamoylamino, N-phenylcarbamoylamino),
5- or 6-membered nitrogen-containing heterocyclic group (for example, imidazolyl, pyrazolyl, triazolyl, tetrazolyl,
1,2-dihydro-2-oxo-1-pyridyl), an imide group (eg, succinimide, hydantoinyl), an arylazo group (eg, phenylazo, 4-methoxyphenylazo), and the like. In addition to these, X may take the form of a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. Further, X may contain a photographically useful group such as a development inhibitor or an accelerator. Preferred X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom.

Specific examples of the compound represented by the formula (M) of the present invention are shown below, but the invention is not limited thereto.

[0094]

[Chemical 38]

[0095]

[Chemical Formula 39]

[0096]

[Chemical 40]

[0097]

[Chemical 41]

[0098]

[Chemical 42]

[0099]

[Chemical 43]

[0100]

[Chemical 44]

[0101]

[Chemical 45]

[0102]

[Chemical 46]

[0103]

[Chemical 47]

[0104]

[Chemical 48]

[0105]

[Chemical 49]

[0106]

[Chemical 50]

[0107]

[Chemical 51]

[0108]

[Chemical 52]

[0109]

[Chemical 53]

[0110]

[Chemical 54]

[0111]

[Chemical 55]

[0112]

[Chemical 56]

[0113]

[Chemical 57]

[0114]

[Chemical 58]

[0115]

[Chemical 59]

[0116]

[Chemical 60]

[0117]

[Chemical formula 61]

[0118]

[Chemical formula 62]

[0119]

[Chemical 63]

[0120]

[Chemical 64]

[0121]

[Chemical 65] Next, a general method for synthesizing the coupler of the present invention will be described. 1H-pyrazolo (5,1-represented by formula (M)
c) Synthesis of -1,2,4-triazole skeleton is described in U.S. Pat.
48-30,895, JP-A-54-145,135.
No., Research Disclosure 12443, J. Am.
Chem. Soc. Perkin I. It can be synthesized by the method described on page 2047 (1977).

Further, it can be synthesized according to the method described in JP-A-2-134354.

A general method for introducing a coupling-off group will be described. (1) Method of introducing halogen atom

[0124]

[Chemical 66] The halogenation at the coupling active position is carried out by adding 1 equivalent of bromine, N-bromosuccinimide, sulfuryl chloride, or N-chlorosuccinimide to a 4 equivalent coupler (A) in an inert solvent such as dichloromethane. It can be easily obtained by acting. (2) Method of connecting oxygen atoms (a) Substitution of halogen atom of coupler having halogen atom at active position with phenoxy group

[0125]

[Chemical 67] The halogenated compound (B) was converted to dimethylformamide (DM
F), dimethyl sulfoxide (DMSO), hexamethylphosphoric triamide (HMPA), N-methyl-
In an aprotic polar solvent such as 2-pyrrolidone,
Suitable _{R 5 -OM, (R 5 -O} ) 2 M ' or (R ₅ -
O) ₃ M ″ (R ₅ represents an aryl group, M, M ′ and M ″ represent monovalent, divalent and trivalent metal ions, respectively) to give the desired coupling activity. (C) in which an aryloxy group is introduced at the position is obtained. Preferably, the halogenated compound (B) is used in an amount of 50 to 50.
It is desirable to react with an equivalent to 20 times amount (molar ratio) of a suitable sodium salt or potassium salt of phenol in a double amount (weight) of the above solvent at a temperature of 50 ° C to 150 ° C. Further, in this reaction, the reaction may be accelerated by the addition of a quaternary ammonium salt such as tetrabutylammonium bromide or an alkali metal halide such as cesium bromide.

(B) After introducing an aryloxy group into the active methylene of β-ketonitrile, 1H-pyrazolo [5,5]
A method of forming a 1-c] -1,2,4-triazole skeleton.

[0127]

[Chemical 68] The halogenated compound (E) obtained by treating 3-oxonitrile (D) with a halogenating agent such as bromine or sulfuryl chloride in an inert solvent such as dichloromethane is converted to a suitable R _{5 in} the presence of a tertiary amine. The aryloxy derivative (F) can be obtained by treating with —OH or a metal salt such as R ₅ —OM described in (1) above. Aminopyrazole obtained by reacting this with foamed water hydrazine in a solvent such as ethanol, a diazonium salt is synthesized using sodium nitrite or isoamyl nitrite and an acid (for example, hydrochloric acid or sulfuric acid), and this diazonium salt is Treatment with a reducing agent such as stannous chloride, sodium sulfite, and sodium hydrosulfite gives a hydrazinopyrazole body (H). The target coupler can be synthesized from this (H) form according to the above-mentioned skeleton synthesis method.

3-oxonitrile (D) is described in US Pat. No. 4,411,753, German Patent Publication DE 3,209,
472 and Synthesis, 472 (1
977) and the like. (3) Method of linking sulfur atom A coupler having an aromatic mercapto or heterocyclic mercapto group substituted at the 7-position is a method described in US Pat. No. 3,227,554, that is, an aryl mercaptan, a heterocyclic mercaptan and its corresponding disulfide. Can be synthesized by dissolving it in a halogenated hydrocarbon solvent and adding chlorine or sulfuryl chloride as a sulfenyl chloride to a 4-equivalent coupler dissolved in an aprotic solvent.
As a method for introducing an alkylmercapto group at the 7-position, a method described in US Pat. No. 4,264,723, that is, introducing a mercapto group at the coupling active position of a coupler,
A method of allowing a halide to act on this mercapto group and S-
A method of synthesizing in one step with (alkylthio) isothiourea or a hydrochloride (or bromine hydrochloride) is effective. (4) Method of connecting nitrogen atoms (a) Method of introducing amino group into coupling active position and modifying the amino group.

The introduction of an amino group into the coupling active position is carried out by the method shown in US Pat. No. 3,419,391, that is, the coupling active position is nitrosated and reduced by an appropriate method to modify the resulting amino compound. Can be easily obtained. Further, by coupling a diazonium salt derived from, for example, aniline anthranilic acid, and sulfanilic acid to the coupling active site to obtain an azo dye, which is then reduced with a suitable reducing agent such as hydrosanphyto soda. It can be easily obtained by modifying the resulting amino compound.

(B) A method in which a halogen atom is introduced at the coupling active position and the halogen atom is substituted with an R ₈ (R ₉ ) N-group.

R ₈ or R ₉ is an alkyl group, an aryl group, a heterocyclic group, and R ₈ and R ₉ are bonded to each other,
A nitrogen heterocyclic group capable of forming a 5-membered ring or a 6-membered ring with a nitrogen atom, wherein R ₈ (R ₉ ) N- and the halogen-substituted compound (B) are alcohol-based at a temperature range of 0 ° C to 180 ° C It can be obtained by dissolving in a solvent aprotic polar solvent or halogenated hydrocarbon solvent and reacting in the presence of a suitable base.

The coupler represented by formula (M) in the present invention is preferably added to the green-sensitive emulsion layer, but may be added to the non-photosensitive intermediate layer. The amount added is 1 silver in the emulsion layer.
0.001 mol to 2 mol per mol, preferably 0.0
It is generally used in the range of 1 mol to 0.5 mol.
When it is used in the non-photosensitive layer, the addition amount per unit area is the same as that in the emulsion layer.

The coupler represented by formula (M) in the present invention may be used together with the compound represented by formula (A).

[0134]

[Chemical 69] In the formula, at least one of R ₁ , R ₂ and R ₃ represents a substituted or unsubstituted alkyl group or alkenyl group, and R 1
The total carbon number of ₁ , R ₂ and R ₃ is 10 or more.
The substituent which may have an alkyl group and an alkenyl group is a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, an acylamino group, an alkylamino group, anilino. Group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, A substituent such as a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphonyl group, an aryloxycarbonyl group, an acyl group or an azolyl group, and preferably a halogen atom or an alkyl group. Group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonamido group, a sulfonyl group, an alkoxycarbonyl group, an acyloxy group or an acyl group. or,
The amount of the compound represented by the general formula (A) used is determined by the formula (M)
The molar ratio of the coupler represented by
It is twice, preferably 0.1 to 2 times.

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

[0136]

[Chemical 70]

[0137]

[Chemical 71]

[0138]

[Chemical 72] Next, the coupler represented by the formula (C) will be described in detail below.

In the formula (C), the "aliphatic group" means a linear, branched or cyclic aliphatic hydrocarbon group, and includes saturated and unsaturated alkyl, alkenyl and alkynyl groups. Is. Typical examples are methyl group, ethyl group, butyl group, dodecyl group, octadecyl group, eicosenyl group, iso-propyl group, tert-group.
Butyl group, tert-octyl group, tert-dodecyl group, cyclohexyl group, cyclopentyl group, allyl group,
There are vinyl group, 2-hexadecenyl group, propargyl group and the like.

In the formula (C), R ₁ is preferably an aliphatic group having 1 to 36 carbon atoms, preferably an aromatic group or heterocyclic group having 6 to 36 carbon atoms, and these may be further substituted with another substituent. You may have.

In the formula (C), R ₂ is a hydrogen atom, a halogen atom (fluorine, chlorine, bromine), an aliphatic ring, an aromatic group, an acylamino group (eg acetylamino, benzoylamino), an aliphatic oxy group (eg Methoxy, butoxy), and an aromatic oxy group (for example, phenoxy), and the substitutable group thereof may further have another substituent.

In formula (C), Z represents a hydrogen atom or a coupling-off group, and examples thereof include a halogen atom (eg fluorine, chlorine, bromine), an alkoxy group (eg ethoxy, dodecyloxy, methoxyethylcarbamoyl). Methoxy, carboxypropyloxy, methylsulfonyl, ethoxy), aryloxy group (eg 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy), acyloxy group (eg acetoxy, tetradecanoyloxy, benzoyloxy), sulfonyloxy Group (eg methanesulfonyloxy, toluenesulfonyloxy), amide group (eg dichloroacetylamino, heptafluorobutyrylamino, methanesulfonylamino, toluenesulfonylamino), alkoxycarbonyl Xy groups (eg ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy groups (eg phenoxycarbonyloxy), aliphatic or aromatic thio groups (eg ethylthio, phenylthio, tetrazolylthio), imide groups (eg succinimide, hydantoinyl). , Aromatic azo groups (eg phenylazo). These leaving groups may include photographically useful groups.

In formula (C), Z is preferably a hydrogen atom, a halogen atom, an alkyloxy group or an aryloxy group.

In the formula (C), R ₁ and R ₂ may form a ring, in which case 5-membered and 6-membered rings are preferable, and 5-membered ring is most preferable.

In the formula (C), X ₁ and X ₂ represent a hydrogen atom or a halogen atom, and a fluorine atom is particularly preferable.

N represents an integer of 0 to 18, preferably 0 to 6, and most preferably 2 to 6.

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

[0148]

[Chemical formula 73]

[0149]

[Chemical 74]

[0150]

[Chemical 75]

[0151]

[Chemical 76]

[0152]

[Chemical 77]

[0153]

[Chemical 78]

[0154]

[Chemical 79]

[0155]

[Chemical 80]

[0156]

[Chemical 81]

[0157]

[Chemical formula 82] The cyan coupler represented by the formula (C) of the present invention is silver 1
0.01 to 2 mol per mol, preferably 0.02 to
It can be used in the range of 0.5 mol.

The formula (I) of the present invention will be described in more detail.

R ¹¹ is R ¹⁴ --N (R ¹⁶ ) CON (R ¹⁵ ).
^{-, R 14 OCON (R 15} ) -, R 14 SO 2 N (R 15)
^{-, R 14 -N (R 16} ) SO 2 N (R 15) - or R ¹⁷ C
Represents ONH-. Here, R ¹⁴ is a substituted or unsubstituted alkyl group (having 1 to 30 carbon atoms, for example, methyl, ethyl,
Isopropyl, decyl, hexadecyl, t-butyl, cyclohexyl, benzyl), a substituted or unsubstituted alkenyl group (having 2 to 30 carbon atoms, for example, 1-butenyl, 1-
Octadecenyl), a substituted or unsubstituted alkynyl group (having 2 to 30 carbon atoms, for example, ethynyl, 1-octynyl), a substituted or unsubstituted aryl group (having 6 to 3 carbon atoms).
0, for example, phenyl, naphthyl, 3-dodecaneamidophenyl, 3-hexadecanesulfonamidophenyl, 4
-Dodecyloxyphenyl), or a heterocyclic group (N,
5- to 20-membered compounds containing at least one hetero atom of O, S and Se, for example, 4-pyridyl, 2-furyl, pyrrolo, 2-thiazolyl, 2-oxazolyl, 2-
Imidazolyl, triazolyl, tetrazolyl, benzotriazolyl, morpholinyl). The substituent which R ¹⁴ has is an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a carboxylic acid amide group, a sulfonic acid amide group, an alkoxycarbonylamino group, a ureido group, a carbamoyl group, an alkoxy group. Examples thereof include carbonyl group, sulfamoyl group, sulfonyl group, cyano group, halogen atom, acyl group, hydroxyl group, carboxyl group, sulfo group, nitro group and heterocyclic group.

R ¹⁵ and R ¹⁶ may be the same or different, and examples thereof include a hydrogen atom and R ¹⁴ . R ¹⁵ is preferably a hydrogen atom.

R ¹⁷ is a substituted or unsubstituted alkyl group having 2 or more carbon atoms in which a carbon atom adjacent to the carbonyl group is not substituted with a hetero atom (preferably 2 to 30 carbon atoms,
For example, ethyl, nonyl, pentadecyl, isopropyl,
t-butyl, 1-hexylnonyl, 3- (2,5-di-
t-pentylphenoxy) propyl, cyclohexyl,
Benzyl), a substituted or unsubstituted alkenyl group (having 2 to 30 carbon atoms, such as vinyl, 1-octenyl, 2-phenylvinyl), a substituted or unsubstituted alkynyl group (having 2 to 30 carbon atoms, such as ethynyl, phenylethynyl) ,
A substituted or unsubstituted aryl group (having 6 to 30 carbon atoms, such as phenyl, naphthyl, 3,5-bis (octadecaneamido) phenyl, 2-hexadecanesulfonamidophenyl, 4-dodecyloxyphenyl), or a heterocyclic group (N , 5-, 20-membered ones containing at least one hetero atom of O, S, Se, for example 3-pyridyl,
2-furyl, 3-thiazolyl, benzotriazolyl, benzimidazolyl).

Examples of the substituent of R ⁷¹ include those mentioned as the substituent of R ¹⁴ .

R ₁₂ and R _{13 in the} formula [I] have a hydrogen atom or Hammett's substituent constant σ _p of 0.3.
The following substituents are represented, and examples thereof include an alkyl group (having 1 to 30 carbon atoms, for example, methyl, ethyl, isopropyl, t-butyl, decyl, hexadecyl, cyclohexyl, benzyl, t-octyl), an aryl group (having a carbon number of 6
To 30, for example, phenyl, naphthyl, an alkoxy group (having 1 to 30 carbon atoms, for example, methoxy, hexyloxy,
Hexadecyloxy, 2-dodecyloxy, benzyloxy), aryloxy groups (C6-30, such as phenoxy, naphthoxy), alkylthio groups (C1-C1).
30, for example, methylthio, hexylthio, dodecylthio, benzylthio), an arylthio group (having 6 to 3 carbon atoms).
0, for example, phenylthio, naphthylthio, 2-butyloxy-5-t-octylphenyl), amide group (having 1 to 30 carbon atoms, such as acetamide, butanamide, hexadecanamide, benzamide), sulfonamide group (having 1 to 30 carbon atoms, for example, Methanesulfonamide, octanesulfonamide, hexadecanesulfonamide, benzenesulfonamide), ureido group (having 1 to 30 carbon atoms, for example, 3-methylureido, 3-dodecylureido, 3-
Phenylureido), urethane group (having 2 to 30 carbon atoms, such as methoxycarbonylamino, decyloxycarbonylamino, phenoxycarbonylamino), sulfamoylamino group (having 30 or less carbon atoms, such as 3-methylsulfamoylamino, 3- Phenylsulfamoylamino), a halogen atom (for example, chlorine, bromine, fluorine), a hydroxy group or-(B) _k- X.

R ¹² and R ¹³ may have a substituent,
Examples of those substituents include those mentioned as the substituents possessed by R ¹⁴ .

Next, the formula (II) will be described in detail.

Q ^{1 in the} formula (II) is a divalent group containing at least one hetero atom, examples of which include an amide bond, a divalent amino group, an ether bond, a thioether bond and an imino bond. , A sulfonyl group, a carbonyl group, an alkylene group, an alkenylene group, and the like, which may be a group in which a plurality of them are combined, and which may further have a substituent. However, when Q ¹ contains an ether bond, it is not a 5-membered ring.

Examples of the heterocyclic ring completed with Q ¹ are as follows.

[0168]

[Chemical 83]

[0169]

[Chemical 84] R ²¹ is a group capable of substituting for the hydroquinone nucleus, and specifically, in addition to the group described for R ¹³ in the formula (I), a substituted or unsubstituted acyl group (preferably having a carbon number of 1 to 30) Yes, examples include acetyl, octanoyl, benzoyl, chloroacetyl, 3-carboxypropionyl, octadecanoyl), substituted and unsubstituted alkoxycarbonyl groups (preferably having 2 to 30 carbon atoms, and examples include methoxycarbonyl and octyl). Oxycarbonyl, phenoxycarbonyl, octadecyloxycarbonyl, methoxyethoxycarbonyl), a substituted or unsubstituted carbamoyl group (preferably having 1 to 30 carbon atoms, examples being carbamoyl,
N-propylcarbamoyl, N-hexadecylcarbamoyl, N- {3- (2,4-di-tert-pentylphenoxy) propyl}, N-phenylcarbamoyl, N
-(3-dodecyloxybutyl), pyrrolidinocarbonyl), substituted or unsubstituted sulfamoyl group (preferably having 0 to 30 carbon atoms, examples include sulfamoyl, dibutylsulfamoyl), substituted or unsubstituted sulfonyl group (Preferably having 1 to 30 carbon atoms, methanesulfonyl, benzenesulfonyl, p-dodecylbenzenesulfonyl) or a heterocyclic group (5 to 20-membered one containing at least one of N, O, S and Se, For example, 5-tetrazolyl, 2-benzoxazolyl, 2-thiazolyl, 2-imidazolyl, 2-pyridyl, morpholino) can be mentioned.

A, A'in the formulas (I) and (II),
B and X will be described in detail.

In formulas (I) and (II), when A and A'represent a group which can be removed by an alkali (hereinafter referred to as a precursor group), preferably an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Hydrolyzable groups such as carbamoyl group, imidoyl group, oxalyl group and sulfonyl group, US Pat.
Precursor group utilizing reverse Michael reaction described in US Pat. No. 9,029, and precursor utilizing anion generated after ring opening reaction described in US Pat. No. 4,310,612 as an intramolecular nucleophilic group. , U.S. Pat. No. 3,67
No. 4,478, No. 3,932,480 or No. 3,
A precursor group in which the anion described in US Pat. No. 993,661 causes electron transfer through a conjugated system to thereby cause a cleavage reaction, and a cleavage by the electron transfer of the reacted anion after ring cleavage described in US Pat. No. 4,335,200. Precursor groups for reacting or US Pat. No. 4,363,865
No. 4,410,618, and precursor groups utilizing an imidomethyl group.

The groups represented by B in the formulas (I) and (II) are-(B) _k --X after the hydroquinone mother nucleus is oxidized by the oxidized form of the developing agent during development to form a quinone form.
Represents a divalent group capable of releasing X and then X, and may have a timing adjusting function. Further, it becomes a coupler which releases X by reacting with another molecule of the oxidized developing agent. It may be a group or a redox group. Here, when k is 0, it means that X is directly bonded to the hydroquinone mother nucleus, and when k is 2 or more, the same or different combinations of two or more B's are represented.

When B is a group having a timing adjusting function, for example, US Pat. Nos. 4,248,962 and 4,409,323 and British Patent 2,096,783 are used.
U.S. Pat. No. 4,146,396, JP-A-51-
146,828, JP-A-57-56,837 and the like. The Time may be a combination of two or more selected from those described in these.

Preferred examples of the timing control group include:
The following are listed.

(1) Group utilizing cleavage reaction of hemiacetal: For example, it is described in US Pat. No. 4,146,396, JP-A-60-249148 and 60-249149.

(2) A group which causes a cleavage reaction by utilizing an intramolecular nucleophilic substitution reaction: For example, US Pat. No. 4,248,9.
Some of the timing groups described in No. 62 are mentioned.

(3) A group which causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system: for example, US Pat. No. 4,4.
09,323 or 4,421,845.

(4) Group utilizing cleavage reaction by hydrolysis of ester: For example, West German Laid-Open Patent No. 2,626,31
It is a linking group described in No. 5.

(5) Group utilizing cleavage reaction of imino ketal: For example, a linking group described in US Pat. No. 4,546,073.

Examples of the group represented by B which is a coupler or a redox group include the following.

As the coupler, for example, in the case of a phenol type coupler, the one bonded to the hydroquinone nucleus at the oxygen atom excluding the hydrogen atom of the hydroxyl group. In the case of a 5-pyrazolone type coupler,
It is bonded to a hydroquinone nucleus at an oxygen atom obtained by removing a hydrogen atom from a hydroxy group of a tautomerism of hydroxypyrazole.

Each of these functions as a coupler only after leaving the hydroquinone nucleus, and reacts with an oxidized product of a developing agent to release X bonded to their coupling positions.

Preferred examples of the case where B is a coupler include the following formulas (C-1) to (C-4).

[0184]

[Chemical 85] In the formula, V ₁ and V ₂ represent a substituent, and V ₃ , V ₄ ,
V ₅ and V ₆ represent a nitrogen atom or a substituted or unsubstituted methine group, V ₇ represents a substituent, x represents an integer of 0 to 4, and when x is plural, V ₇ is the same or different. And two V _7's may be linked to each other to form a cyclic structure. V ₈ is a —CO— group, —SO ₂ —
Group, an oxygen atom or a substituted imino group, and V ₉ is -V
₈ -N-C = C-together represents a nonmetallic atom group for forming a 5- to 8-membered ring, V ₁₀ represents a hydrogen atom or a substituent. Where * is to the hydroquinone nucleus, and *
* Means to bond to X.

In the formulas (I) and (II), when the group represented by B is a redox group, it is preferably represented by the following formula (R-1).

Formula (R-1)

[0187]

[Chemical formula 86] In the formula, P and Q each independently represent an oxygen atom or a substituted or unsubstituted imino group, at least one of n X ′ and Y represents a methine group having —X as a substituent, and other X ′ And Y represent a substituted or unsubstituted methine group or a nitrogen atom, and n is 1 to 3
Represents an integer (n X ′ and n Y are the same or different), A represents a hydrogen atom or a group removable by an alkali, and A in the formula (I)
Has the same meaning as. Here, the case where any two substituents of P, X ', Y, Q and A are combined into a divalent group to form a cyclic structure is also included. For example, (X '= Y) _n forms a benzene ring, a pyridine ring, or the like.

Among the groups represented by the formula (R-1), particularly preferred groups are those represented by the following formula (R-2) or (R-3).

[0189]

[Chemical 87] In the formula, the * mark represents the position of bonding to the hydroquinone mother nucleus, and the ** mark represents the position of bonding to X.

R ₆₄ represents a substituent, and q represents an integer of 0, 1 or 3. When q is 2 or more, two or more R _{64 s} may be the same or different, and when two R _{64 s} are substituents on adjacent carbons, they are each a divalent group to form a ring structure. It also includes the case of representing.

As R ⁶⁴ , those mentioned for R ²¹ in the formula (II) can be mentioned.

X means a development inhibitor. As a preferable example of X, a compound having a mercapto group bonded to the heterocycle represented by the formula (X-1), or a compound represented by the formula (X-
An example thereof is a heterocyclic compound capable of forming imino silver represented by 2).

[0193]

[Chemical 88] In the formula, Z ₁ represents a nonmetallic atom group necessary for forming a monocyclic ring or a condensed ring heterocycle, and Z ₂ represents a nonmetallic atomic group necessary for forming a monocycle or a condensed ring heterocycle with N. Represents. These heterocycles may have a substituent, and * represents a position bonded to B. The hetero ring formed by Z ₁ and Z ₂ is more preferably a 5-membered to 8-membered hetero ring containing at least one of nitrogen, oxygen, sulfur and selenium as a hetero atom, and most preferably 5 member or It is a 6-membered heterocycle.

Examples of the heterocycle represented by Z ₁ include azoles (tetrazole, 1,2,4-triazole, 1,2,3-triazole, 1,3,4-thiadiazole, 1,3,4 -Oxadiazole, 1,3-thiazole, 1,3-oxazole, imidazole, benzothiazole, benzoxazole, benzimidazole, pyrrole, pyrazole, indazole), azaindenes (tetrazaindene, pentazaindene, triazaindene) , Azines (pyrimidine, triazine, pyrazine, pyridazine).

Examples of the heterocycle represented by Z ₂ include triazoles (1,2,4-triazole, benzotriazole, 1,2,3-triazole), indazole, benzimidazole, azaindenes (tetrazaindene). , Pentazaindene), and tetrazole.

The preferred substituents contained in the development inhibitors represented by formulas (X-1) and (X-2) are as follows.

That is, R ₇₇ group, R ₇₈ O— group, R ₇₇ S—
Group, R ₇₇ OCO— group, R ₇₇ OSO ₂ — group, halogen atom, cyano group, nitro group, R ₇₇ SO ₂ — group, R ₇₈ CO—
Group, R ₇₇ COO-group, R ₇₇ SO ₂ N (R ₇₈ ) -group, R ₇₈
N (R ₇₉ ) SO ₂ — group, R ₇₈ N (R ₇₉ ) CO— group, R ₇₇
C (R ₇₈ ) = N-group, R ₇₇ N (R ₇₈ ) -group, R ₇₈ CON
(R ₇₉ ) -group, R ₇₇ OCON (R ₇₈ ) -group, R ₇₈ N (R
₇₉₎ CON (R ₈₀₎ - group, or include R ₇₇ SO ₂ O- group. Here, R ₇₇ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₇₈ , R ₇₉ and R ₈₀ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. R in one molecule
When there are two or more of ₇₇ , R ₇₈ , R ₇₉ and R _80, these may be linked to form a ring (for example, a benzene ring).

Examples of the compound represented by the formula (X-1) include, for example, substituted or unsubstituted mercaptoazoles (eg 1-phenyl-5-mercaptotetrazole,
1-propyl-5-mercaptotetrazole, 1-butyl-5-mercaptotetrazole, 2-methylthio-5
-Mercapto-1,3,4-thiadiazole, 3-methyl-4-phenyl-5-mercapto-1,2,4-triazole, 1- (4-ethylcarbamoylphenyl)-
2-mercaptoimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-
Mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-phenyl-5-mercapto-1,3
4-oxadiazole, 1- {3- (3-methylureido) phenyl} -5-mercaptotetrazole, 1-
(4-Nitrophenyl) -5-mercaptotetrazole, 5- (2-ethylhexanoylamino) -2-mercaptobenzimidazole), and substituted or unsubstituted mercaptoazaindenes (for example, 6-methyl-4-mercapto- 1,3,3a, 7-tetraazaindene,
4,6-Dimethyl-2-mercapto-1,3,3a, 7
-Tetraazaindene) substituted or unsubstituted mercaptopyrimidines (eg 2-mercaptopyrimidine, 2
-Mercapto-4-methyl-6-hydroxypyrimidine).

Examples of the heterocyclic compound capable of forming an imino silver include substituted or unsubstituted triazoles (eg, 1,2,4-triazole, benzotriazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5 -Bromobenzotriazole, 5-n
-Butylbenzotriazole, 5,6-dimethylbenzotriazole), substituted or unsubstituted indazoles (eg, indazole, 5-nitroindazole, 3-
Nitroindazole, 3-chloro-5-nitroindazole), and substituted or unsubstituted benzimidazoles (for example, 5-nitrobenzimidazole and 5,6-dichlorobenzimidazole).

Further, X is substantially separated from B of the formulas (I) and (II) to become a compound having a development inhibitory property, and then it undergoes a certain chemical reaction with a developer component to substantially give a substantial effect. It may be a compound which does not have development inhibitory property or is significantly reduced. Examples of the functional group that undergoes such a chemical reaction include an ester group, a carbonyl group, an imino group, an immonium group, a Michael addition accepting group, and an imide group.

Examples of such a deactivating type development inhibitor include, for example, US Pat. No. 4,477,563 and JP-A-6-26.
0-218644, 60-221750, 60
The development inhibitor residues described in No. 233650, No. 61-11743 and the like are mentioned.

Of these, those having an ester group are particularly preferable. Specifically, for example, 1- (3-phenoxycarbonylphenyl) -5-mercaptotetrazole, 1- (4-phenoxycarbonylphenyl) -5.
-Mercaptotetrazole, 1- (3-maleimidophenyl) -5-mercaptotetrazole, 5-phenoxycarbonylbenzotriazole, 5- (4-cyanophenoxycarbonyl) benzotriazole, 2-phenoxycarbonylmethylthio-5-mercapto-1,
3,4-thiadiazole, 5-nitro-3-phenoxycarbonylimidazole, 5- (2,3-dichloropropyloxycarbonyl) benzotriazole, 1- (4
-Benzoyloxyphenyl) -5-mercaptotetrazole, 5- (2-methanesulfonylethoxycarbonyl) -2-mercaptobenzothiazole, 5-cinnamoylaminobenzotriazole, 1- (3-vinylcarbonylphenyl) -5-mercaptotetrazole , 5-
Succinimidomethylbenzotriazole, 2- {4-
Succinimidophenyl} -5-mercapto-1,3,3
4-oxadiazole, 6-phenoxycarbonyl-2
-Mercaptobenzoxazole, 2- (1-methoxycarbonylethylthio) -5-mercapto-1,3,4
-Thiadiazole, 2-butoxycarbonylmethoxycarbonylmethylthio-5-mercapto-1,3,4-thiadiazole, 2- (N-hexylcarbamoylmethoxycarbonylmethylthio) -5-mercapto-1,3
Examples include 4-thiadiazole and 5-butoxycarbonylmethoxycarbonylbenzotriazole.

Preferred as X are mercaptoazoles and benzotriazoles. As the mercaptoazole, mercaptotetrazole, 5-mercapto-1,3,4-thiadiazole and 5-mercapto-1,3,4-oxadiazole are more preferable.

Most preferably X is 5-mercapto-
1,3,4-thiadiazoles.

In formulas (I) and (II), k is preferably 0, 1 or 2.

Among the compounds represented by the formula (I), preferred compounds are the compounds represented by the formula (IA).

Formula (IA)

[0208]

[Chemical 89] In formula (IA), R ¹¹ , B, X, A, A ′ and k
Have the same meaning as those of formula (I).

In formula (IA), preferred R ¹¹ is R ¹⁴ —
N (R ¹⁶ ) CON (R ¹⁵ )-and R ¹⁴ OCON
(R ¹⁵⁾ - a and, R ^14, R ¹⁵ and R ¹⁶ have the same meanings as described above. Moreover, in formula (IA), preferable k is 0 or 1.

In formula (I) and formula (II), A and A'are preferably hydrogen atoms.

In formula (II), Q ¹ is preferably -N
It is represented by (R ²⁸ ) -CO-Q ^2- , and examples of Q ² include a divalent amino group, an ether bond, a thioether bond, an alkylene group, an ethylene bond, an imino bond, a sulfonyl group, a carbonyl group, and an arylene group. , A divalent heterocyclic group,
The group which combined these two or more is mentioned.

R ²⁸ is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, which may have a substituent. R ²⁸ is preferably a hydrogen atom.

R ²¹ is preferably a hydrogen atom or a substituent having a Hammett's substituent constant σ _p of 0 or more.

The number of ring members of the heterocycle containing Q ¹ is preferably a 5- to 7-membered ring, and among them, a compound represented by the following formula (IIA) is more preferable.

General formula (IIA)

[0216]

[Chemical 90] In the formula (IIA), Q ² has the same meaning as described above and R 2
²¹ , A, A ', B, X and k have the same meaning as in formula (II).

When R ^{11 in} formula (IA) is R ¹⁷ CONH-, the following formulas (IB) and (IC) are preferred.

Formula (IB)

[0219]

[Chemical Formula 91] Expression (IC)

[0220]

[Chemical Formula 92] In the formula, R ³⁴ and R ³⁵ each represent a substituent, n ′ represents an integer of 2 or more, m represents an integer of 1 to 5, and when m is 2 or more,
R ³⁵ may be the same or different.
A, A ′, B, X and k have the same meanings as those in formula (I).

Examples of R ³⁴ and R ³⁵ include compounds represented by the formula (I)
Those mentioned as the substituent which R ¹⁴ has.
Moreover, these substituents may be further substituted.

In the formula (IB), preferred R ³⁴ is a substituent having 5 to 30 carbon atoms, and n ′ is preferably 2 to 5. In formula (IC), R ³⁵ preferably has 5 to 30 carbon atoms.

In order to more specifically arrange the contents of the present invention, specific examples of the compounds represented by the formulas (I) and (II) are shown below, but the compounds usable in the present invention are not limited thereto. is not.

[0224]

[Chemical formula 93]

[0225]

[Chemical 94]

[0226]

[Chemical 95]

[0227]

[Chemical 96]

[0228]

[Chemical 97]

[0229]

[Chemical 98]

[0230]

[Chemical 99]

[0231]

[Chemical 100]

[0232]

[Chemical 101]

[0233]

[Chemical 102]

[0234]

[Chemical 103]

[0235]

[Chemical 104]

[0236]

[Chemical 105]

[0237]

[Chemical formula 106]

[0238]

[Chemical formula 107]

[0239]

[Chemical 108]

[0240]

[Chemical 109]

[0241]

[Chemical 110]

[0242]

[Chemical 111]

[0243]

[Chemical 112]

[0244]

[Chemical 113]

[0245]

[Chemical 114]

[0246]

[Chemical 115]

[0247]

[Chemical formula 116]

[0248]

[Chemical 117]

[0249]

[Chemical 118]

[0250]

[Chemical 119]

[0251]

[Chemical 120]

[0252]

[Chemical 121]

[0253]

[Chemical formula 122]

[0254]

[Chemical 123]

[0255]

[Chemical formula 124]

[0256]

[Chemical 125]

[0257]

[Chemical formula 126] The compounds represented by formulas (I) and (II) of the present invention are disclosed in JP-A-49-129536, JP-A-52-57828, JP-A-60-21044, JP-A-60-233642 and JP-A-60-233642.
No. 233648, No. 61-18946, No. 61-1
No. 56043, No. 61-213847, No. 61-23
No. 0135, No. 61-236549, No. 62-623.
52, 62-103639, U.S. Pat.
No. 29, No. 3620746, No. 4332828, No. 4377634, No. 4684604 and the like.

When the compounds represented by formulas (I) and (II) of the present invention are used in a multilayer color photographic light-sensitive material, a silver halide emulsion layer or a yellow filter layer, an antihalation layer or an intermediate layer adjacent to the emulsion layer is used. It is contained in at least one layer such as a layer or a protective layer, but is preferably contained in a silver halide emulsion layer or an intermediate layer adjacent to the emulsion layer.

The compounds of the present invention represented by formulas (I) and (II) are generally present in the same layer or adjacent layers, although they vary depending on the properties of the silver halide photographic light-sensitive material to be applied, the purpose or the processing method. The amount is 1 to 10 ^-7 mol, and preferably 3 x 10 ^-2 mol, relative to 1 mol of silver halide.
Is about 3 × 10 ⁻⁵ mol.

The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-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. As a typical example, a silver halide photographic light-sensitive material having at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. And the photosensitive layer is blue light, green light,
And a unit photosensitive layer having a color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layers are generally arranged in order from the support side to the red-sensitive layer and green. The color-sensitive layer and the blue color-sensitive layer are installed 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 photosensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive 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
Nos. 61-20037 and 61-20038 may contain a coupler and the like, and may contain a color mixing inhibitor as commonly 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 structure of emulsion layers can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
JP-A-57-112751, JP-A-62-200350
No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
Can be installed in order.

Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest 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. Another example is an arrangement in which a halogenated emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. 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. It may be arranged in the order of layer / high-speed emulsion layer / low-speed emulsion layer.

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, 4
In the case of more than one layer, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448 are used.
No. 63-89850, BL, G
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as L and RL, adjacent to or in proximity to the main photosensitive layer.

As described above, various layer structures 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 silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. .. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in a photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof.

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

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pages 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid. 187
16 (November 1979), p.648, ibid. 3071
05 (Nov. 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by P. Glafkides, Chemie et Ph.
isique Photographie, Pau
L Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press, Inc. (G.F. Duffi).
n, Photographic Emulsion C
chemistry (Focal Press, 196)
6)), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating P
photographic Emulsion, Foca
l Press, 1964).

For example, US Pat. No. 3,574,628,
No. 3,665,394 and British Patent No. 1,413.
The monodisperse emulsion described in No. 748 is also preferable.

Also, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff, Photograph).
ic Science and Engineering
g), 14: 248-257 (1970); U.S. Pat. Nos. 4,434,226 and 4,414,310.
No. 4,433,048, No. 4,439,520 and British Patent No. 2,112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and silver halides having different compositions may be bonded by epitaxial bonding. May be
Further, it may be bonded with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above 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 the latent image is formed inside the grain, or a type having a latent image on both the surface and the inside. Must be a type of emulsion. Among the internal latent image types, the cores described in JP-A-63-264740 /
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.
3542. The shell thickness 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.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No. 17643, ibid. 18716 and ibid.
No. 307105, the relevant parts are summarized in the table below.

The light-sensitive material of the present invention comprises a light-sensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having different characteristics of at least one 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 in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer.
The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed portion and exposed portion of the light-sensitive material. .. A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain 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 0.7.
It is preferably 5 μm, particularly preferably 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited and may be regular grains or polydisperse emulsion, but monodisperse grains (at least 95% of the weight or the number of silver halide grains are within ± 40% of the average grain size). It is preferable that the particles have a particle size of

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that the fog is not fogged in advance. ..

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and if necessary, silver chloride and / or
Alternatively, it may contain silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine grain silver halide can be prepared in the same manner as in ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized,
Also, spectral sensitization is not necessary. 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, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in the layer containing the fine grain silver halide grains.

The silver coating amount of the light-sensitive material of the present invention was 6.0 g.
/ M ² or less is preferable, and 4.5 g / m ² or less is most preferable.

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 1. Chemical sensitizer page 23 648 page right column 866 page 2. Sensitivity enhancer page 648 right column 3. Spectral sensitizer, supersensitizer page 23-24 648 Page right column 866-868 page-649 page right column 4. Whitening agent page 24 647 page right column 868 page 5. Antifoggants, stabilizers 24-25 page 649 page right column 868-870 page 6. Light absorber , Filter dyeing page 25-26 page 649 right column 873 material, UV absorber ~ page 650 left column 7. Stain inhibitor page 25 right column 650 page left column 872 page ~ right column 8. Dye image stabilizer page 25 650 Page left column 872 Page 9 Hardener 26 page 651 Page left column 874 to 875 10. Binder page 26 651 Page left column 873 to 874 page 11. Plasticizers and lubricants Page 27 650 Page right column 876 Page 12. Coating aids, surface active agents Pages 26-27 Page 650 Right column 875-876 Page 13. Antistatic agent Page 27 650 Page Right column 876-877 Page 14. Matting agent Page 878-879 Prevent deterioration In order, by reacting with formaldehyde as described in U.S. Patent 4,411,987 No. and Nos 4,435,503, it is preferable to add a compound capable of immobilizing the photosensitive material.

The light-sensitive material of the present invention can be prepared according to US Pat.
0,454, 4,788,132, JP-A-62.
It is preferable to incorporate the mercapto compounds described in JP-A-18539 and JP-A-1-283551.

The light-sensitive material of the present invention can be used as described in JP-A-1-1060.
It is preferable to contain a compound which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, as described in No. 52, regardless of the amount of developed silver produced by the development processing.

International Publication WO88 /
No. 04794, dyes dispersed by the method described in JP-A-1-502912 or EP317,308A,
U.S. Pat. No. 4,420,555, Japanese Patent Laid-Open No. 1-25935.
It is preferable that the dye described in No. 8 is contained.

Various color couplers can be used in the light-sensitive material of the present invention. Specific examples thereof are described in Research Disclosure No. 17643, VII-C to G,
And the same No. 307105, VII-C to G.

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
09,320, 4,576,910, British Patent 2,102,137, and European Patent 341,188A.

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

Colored couplers for correcting unnecessary absorption of color forming dyes are described in Research Disclosure No.
17643, Item VII-G, ibid. VII of 307105-
Section G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-
39413, U.S. Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,146,368.
Those described in No. 10 are preferable. Also, US Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 4,181,
It is also preferable to use a coupler described in U.S. Pat. No. 4,777,120 having a dye precursor group capable of reacting with a developing agent to form a dye as a leaving group.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are RD1 described above.
7643, section VII-F and ibid. 307105, VII-
Patents described in paragraph 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.

R. D. No. 11449, 24241,
The bleaching accelerator releasing coupler described in JP-A No. 61-201247 is effective for shortening the processing time having a bleaching ability, and is particularly added to a light-sensitive material using tabular silver halide grains described above. If you do, the effect is great. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent 2,097,140.
No. 2,131,188, JP-A-59-1576.
Nos. 38 and 59-170840 are preferable. Also, JP-A-60-107029 and JP-A-60-25
2340, JP-A-1-44940, and 1-4568.
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 product of a developing agent described in No. 7 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618, a multi-equivalent coupler described in JP-A-60-185.
950, DIR described in JP-A-62-24252, etc.
Redox compound releasing coupler, DIR coupler releasing coupler, EP 173,302A, EP 313,
No. 308A, a coupler that releases a dye that recolors after release, a ligand-releasing coupler described in U.S. Pat. No. 4,555,477, and a leuco dye-releasing coupler described in JP-A-63-75747. Patent No. 4,774,
Examples thereof include couplers that release the fluorescent dye described in No. 181.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in the oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate,
Decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), phosphoric acid or phosphone Acid esters (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate,
Tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (eg N, N-diethyl). Dodecanamide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert-amylphenol),
Aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (for example N,
N-dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene).
As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-ethoxy. Examples include ethyl acetate and dimethylformamide.

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

In the color light-sensitive material of the present invention, 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.

Suitable supports which can be used in the present invention are described in, for example, RD. No. 17643, page 28, ibid. 18
716, page 647, right column to page 648, left column, and the same No.
307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
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 a humidity condition of 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, A Green (A. Gr
een, et al., Photographic Science and Engineering (Photogr. Sci. E)
ng. ), Vol. 19, No. 2, pp. 124-129, can be measured by using a swellometer (swelling meter) of the type, and T _1/2 is treated with a color developer at 30 ° C. for 3 minutes 15 seconds. 90% of the maximum swollen film thickness reached at that time 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 hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The light-sensitive material of the present invention is preferably provided with 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. This 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.
~ 500% is preferred.

The color developing solution used for 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-β-methoxyethylaniline and their sulphates, hydrochlorides or p-toluenesulphonates. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt,
It generally contains a development inhibitor such as a bromide salt, an iodide salt, benzimidazoles, benzothiazoles or a mercapto compound, or an antifoggant. If necessary, the color developer may contain hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides,
Various preservatives such as triethanolamine and catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers and competitive couplers. , Chelating agents represented by auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, for example, ethylenediamine. Tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenedia It may be mentioned di (o-hydroxyphenylacetic acid) and salts thereof as a typical example - emissions -N, N, N, N-tetramethylene phosphonic acid, ethylenediamine.

Next, the processing solutions and processing steps for the color reversal light-sensitive material of the present invention other than the color developing solution will be described.

Among the processing steps of the color reversal photosensitive material of the present invention, the steps from black development to color development are as follows.

1) Black-white development-washing-reversal-color development 2) Black-white development-water washing-light reversal-color development 3) Black-white development-water washing-color development Steps 1) to 3) are all performed in US patents. 4,8
In place of the rinse process described in No. 04,616, it is possible to simplify the process and reduce waste liquid.

4) Color development-adjustment-bleaching-fixing-washing-stable 5) Color development-washing-bleaching-fixing-washing-stable 6) Color development-adjusting-bleaching-washing-fixing-washing-stable 7) Color development Development-washing-bleaching-washing-fixing-washing-stable 8) Color development-bleaching-fixing-washing-stable 9) Color development-bleaching-bleaching fixing-washing-stable 10) Color development-bleaching-bleaching fixing-fixing- Washing-stable 11) Color development-bleaching-washing-fixing-washing-stable 12) Color development-adjusting-bleach-fixing-washing-stable 13) Coloring development-washing-bleach-fixing-washing-stable 14) Color development-bleach-fixing -Washing-Stable 15) Color development-Fixing-Bleach-fixing-Water washing-Stable In the processing steps of 4) to 15), the washing step immediately before the stabilizing step may be removed, or conversely, the stabilizing step of the final step is It does not have to be done. Any one of the above steps 1) to 3) and any one of steps 4) to 15) are connected to form a color reversal step.

Next, the processing liquid in the color reversal processing step of the present invention will be described.

Known developing agents can be used in the black and white developing solution used in the present invention. As a developing agent,
Dihydroxybenzenes (eg hydroquinone),
3-Pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p-aminophenol), 1-phenyl-3-pyrazolines, ascorbic acid and U.S. Pat. No. 4,067,8.
The heterocyclic compounds such as 1,2,3,4-tetrahydroquinoline ring and indrene ring described in No. 72 can be used alone or in combination.

In the black-and-white developing solution used in the present invention, if necessary, preservatives (eg, sulfite, bisulfite), buffers (eg, carbonate, boric acid, borate, alkanolamine), alkaline agents ( For example, hydroxides, carbonates, dissolving tablets (eg polyethylene glycols, their esters), pH adjusters (eg organic acids such as acetic acid),
Sensitizer (for example, quaternary ammonium salt), development accelerator,
A surfactant, a defoaming agent, a film hardening agent, and a viscosity imparting agent can be contained.

The black-and-white developing solution used in the present invention must contain a compound acting as a silver halide solvent.
The sulfite, which is usually added as a preservative, plays the role. The sulfite and other silver halide solvents that can be used are specifically KSCN, NaSCN, K
₂ SO ₃ , Na ₂ SO ₃ , K ₂ S ₂ O ₅ , Na ₂ S ₂ O
₅ , K ₂ S ₂ O ₃ and Na ₂ S ₂ O ₃ can be mentioned.

The pH value of the developer thus adjusted is selected to an extent sufficient to give a desired density and contrast, but is in the range of about 8.5 to about 11.5.

In order to perform the sensitizing process using such a black-and-white developing solution, it is usually necessary to extend the time up to about 3 times the standard process. At this time, if the processing temperature is increased, the extension time for the sensitization processing can be shortened.

The pH of these color developing solution and black-and-white developing solution is generally 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air.

The contact area between the photographic processing liquid and the air in the processing tank can be expressed by the aperture ratio defined below.

That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably It is preferably 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-82
No. 033, a method using a movable lid, JP-A-63-63
-216050 can be mentioned as a slit developing treatment method. To reduce the aperture ratio, not only the steps of color development and black and white development, but also the subsequent steps,
For example, it is preferably applied in all steps such as bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The reversal bath used after black and white development may contain a known fogging agent. That is, stannous ion-organic phosphoric acid complex salt (US Pat. No. 3,617,282), stannous ion organic phosphonocarboxylic acid complex salt (Japanese Patent Publication No. 56-32616), stannous ion-
Aminopolycarboxylic acid complex salt (US Pat. No. 1,209,0
50), stannous ion complex salts, borohydride compounds (US Pat. No. 2,984,567),
Heterocyclic amine borane compounds (UK Patent No. 1,011,0
No. 00 specification) and the like, and the like. The fogging bath (reversal bath) has a wide pH range from the acidic side to the alkaline side, and is pH 2 to 12, preferably 2.5 to 10, and particularly preferably 3 to 9. Instead of the reversal bath, a light reversal treatment by re-exposure may be performed, and the reversal step may be omitted by adding the fogging agent to the color developing solution.

The silver halide color photographic light-sensitive material of the present invention is subjected to bleaching treatment or bleach-fixing treatment after color development. These treatments may be carried out immediately after the color development without passing through other processing steps, in order to prevent unnecessary post-development and air fog, and to reduce the carry-in of the color developing solution to the desilvering process. In addition, in order to wash out and detoxify the sensitizing dyes and dyes contained in the photographic light-sensitive material and the color-developing agent impregnated in the photographic light-sensitive material, stop, adjust, and wash with water after color development processing. A bleaching treatment or a bleach-fixing treatment may be carried out after the treatment steps such as.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. As a typical bleaching agent, organic complex salt of iron (III),
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or other aminopolycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. Etc. can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. .. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8, but a lower pH can be used for speeding 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 bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. No. 17129 (July 1978), a compound having a mercapto group or a disulfide group; a thiazolidine derivative described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832, 53-53. -32735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent No. 1,127,71.
5, the iodide salt described in JP-A-58-16,235;
Polyoxyethylene compounds described in West German Patent Nos. 966,410 and 2,748,430; JP-B-45-8
No. 836, a polyamine compound;
40,943, 49-59,644, 53-9
4,927, 54-35,727, 55-2.
Compounds described in Nos. 6,506 and 58-163,940; bromide ions can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, US Pat. No. 3,893,858.
, West German Patent No. 1,290,812, JP-A-53-9
The compounds described in 5,630 are preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable.
These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing.

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. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specifically, acetic acid, propionic acid and hydroxyacetic acid 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 Is most commonly used, with ammonium thiosulfate being the most widely used. Further, it is also preferable to use a combination of thiosulfate, thiocyanate, thioether compound and thiourea. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved and the stain generation after the processing is effectively prevented.

In the desilvering step, 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 contacting the emulsion surface 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 includes a bleaching solution, a bleach-fixing solution,
It is effective with 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, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect or 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.
It is preferable to have the photosensitive material conveying means described in No. 8 and No. 60-191259. JP-A-60-1
As described in No. 91257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to washing and / or stabilizing steps after desilvering. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the rinsing water, the number of rinsing tanks (the number of stages), the replenishment method such as countercurrent and forward flow, and various other conditions. It can be set in a wide range.
Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the Societ
y of Motion Picture and T
Evolution Engineers Volume 64,
P. 248 to 253 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate and the suspended matter produced adheres to the photosensitive material. Problems arise. In the processing of the color light-sensitive material of the present invention, such a problem is solved by a method disclosed in JP-A-62-288,838.
The method of reducing calcium ion and magnesium ion described in No. 10 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and benzotriazole are also described by Hiroshi Horiguchi in "Bacterial and Antifungal Agents". Chemistry "(1986)
Sankyo Publishing Co., Ltd., Sanitary Technology Society, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982), Industrial Technology Association, Japan Antibacterial and Antifungal Society, "Antibacterial and Antifungal Encyclopedia," (1986) Can also be used.

Rinsing water in processing the light-sensitive material of the present invention
The pH is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but are generally in the range of 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes. To be selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and 58-58
All known methods described in Nos. 14834 and 60-220345 can be used.

In addition, there is a case where a stabilizing treatment is further carried out after the water washing treatment. As an example, a stabilizing treatment containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing, is included. You can mention the bath. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, US Pat.
Indoaniline compounds described in No. 342,597, No. 3,342,599, Schiff base type compounds described in Research Disclosures 14,850 and 15,159, aldol compounds described in No. 13,924, USA The metal salt complexes described in Japanese Patent No. 3,719,492 and the urethane compounds described in JP-A No. 53-135628 can be mentioned.

The silver halide color light-sensitive material of the present invention comprises
In order to accelerate color development, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are disclosed 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 is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

[0338]

【Example】

(Embodiment 1) Hereinafter, the present invention will be specifically described with reference to embodiments, but the present invention is not limited thereto. Preparation of Sample 101 Sample 101 was prepared by preparing a multilayer color light-sensitive material composed of each layer having the following composition on a cellulose triacetate film support having a thickness of 127 μ, which was undercoated. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use.

First layer: antihalation layer Black colloidal silver 0.20 g Gelatin 1.9 g UV absorber U-1 0.1 g UV absorber U-3 0.04 g UV absorber U-4 0.1 g High boiling organic Solvent Oil-1 0.1 g Microcrystalline solid dispersion of Dye E-1 0.1 g Second layer: Intermediate layer Gelatin 0.40 g High boiling organic solvent Oil-3 0.1 g Dye D-4 0.4 mg Third layer : Intermediate layer Surface and internal fogged fine grain silver iodobromide emulsion (average grain 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 0.1 g Emulsion B Silver amount 0.4 g Gelatin 0.8 g Coupler C- (2) 0.15 g Coupler C- (1) 0.05 g Coupler C- (3) 0.05 g Coupler K -9 0.0 g High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g 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- (2) 0.2 g Coupler C- (1) 0.05 g Coupler C- (3) 0.2 g High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g Sixth layer: High sensitivity red sensitivity Emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C- (2) 0.3 g Coupler C- (1) 0.1 g Coupler C- (3) 0.7 g Additive P-1 0.1 g No. 7 Layer: Intermediate layer Gelatin 0.6g Additive M-1 0.3g Color mixing inhibitor Cpd-I 2.6mg UV absorber U-1 0.01g UV absorber U-2 0.002g UV absorber U-50 0.01 g Additive D-1 0.02 g High boiling point organic solvent Oil- 0.02 g Eighth layer: intermediate layer Silver iodobromide emulsion with fogged surface and inside (average grain 0.06 μm, coefficient of variation 16%, AgI content 0.3 mol%) silver amount 0.02 g gelatin 1.0 g Additive P-1 0.2 g Color mixing inhibitor Cpd-A 0.1 g Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion E Silver amount 0.1 g Emulsion F Silver amount 0.2 g Emulsion G Silver amount 0.2 g Gelatin 0 0.8g Coupler K-4 0.2g Coupler K-7 0.05g Compound Cpd-B 0.03g Compound Cpd-D 0.02g Compound Cpd-E 0.02g Compound Cpd-F 0.02g Compound Cpd-G 0. 02g High-boiling point organic solvent Oil-1 0.1g High-boiling point organic solvent Oil-2 0.1g 10th layer: Medium sensitivity green sensitive emulsion layer Emulsion G Silver amount 0.3g Emulsion H Silver amount 0.1g Gelatin 0.6g Coupler K-4 0.1 g Coupler K-7 0.3 g Compound Cpd-B 0.03 g Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.05 g Compound Cpd-G 0.05 g High boiling point organic solvent Oil -0.01g Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.5g Gelatin 1.0g Coupler K-4 0.3g Coupler K-7 0.2g Compound Cpd-B 0.08g Compound Cpd- D 0.02g Compound Cpd-E 0.02g Compound Cpd-F 0.02g Compound Cpd-G 0.02g High boiling point organic solvent Oil-1 0.02g High boiling point organic solvent Oil-2 0.02g 12th layer: Intermediate Layer Gelatin 0.6 g Thirteenth layer: Yellow filter layer Yellow colloidal silver Silver amount 0.07 g Gelatin 1.1 g Color mixing inhibitor Cpd-A 0.01 High boiling organic solvent Oil-1 0.01 g Microcrystalline solid dispersion of dye E-2 0.05 g 14th layer: Intermediate layer gelatin 0.6 g 15th layer: Low sensitivity blue sensitive emulsion layer Emulsion J Silver amount 0.2 g Emulsion K Silver amount 0.3 g Emulsion L Silver amount 0.1 g Gelatin 0.8 g Coupler K-5 0.6 g Coupler K-6 0.1 g 16th layer: Middle speed blue-sensitive emulsion layer Emulsion L Silver amount 0.1 g Emulsion M silver amount 0.4 g gelatin 0.9 g coupler K-5 0.4 g coupler K-6 0.1 g 17th layer: high-sensitivity blue-sensitive emulsion layer emulsion N silver amount 0.4 g gelatin 1.2 g coupler K-50 .3g Coupler K-6 0.7g 18th layer: 1st protective layer Gelatin 0.7g UV absorber U-1 0.2g UV absorber U-2 0.05g UV absorber U-5 0.3g Formalin scavenger Cpd-H .4 g Dye D-1 0.1 g Dye D-2 0.05 g Dye D-3 0.1 g 19th layer: second protective layer Colloidal silver Silver amount 0.1 mg Fine grain silver iodobromide emulsion (average grain size: 06 μm, AgI content 1 mol%) Silver amount 0.1 g Gelatin 0.4 g 20th layer: Third protective layer Gelatin 0.4 g Polymethyl methacrylate (average particle size 1.5 μ) 0.1 g Methyl methacrylate and acrylic acid 4 : Copolymer of 6 (average particle size 1.5 μ) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg In addition to the above composition, an additive F-
1-F-8 were added. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-2, W-3 and W-4 were added to each layer.

Further, as an antiseptic and antifungal agent, phenol, 1,
2-Benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol were added.

[0341]

[Table 3]

[0342]

[Table 4]

[0343]

[Table 5]

[0344]

[Chemical 127]

[0345]

[Chemical 128]

[0346]

[Chemical formula 129]

[0347]

[Chemical 130]

[0348]

[Chemical 131]

[0349]

[Chemical 132]

[0350]

[Chemical 133]

[0351]

[Chemical 134]

[0352]

[Chemical 135]

[0353]

[Chemical 136]

[0354]

[Chemical 137]

[0355]

[Chemical 138]

[0356]

[Chemical 139]

[0357]

[Chemical 140]

[0358]

[Chemical 141] (Preparation of Samples 102 to 120) Second Layer and Fourth Layer of Sample 101
Comparative compound A was added to the layers, the seventh layer, the ninth layer, and the eleventh layer.
Sample 102 was prepared in the same manner except that 10 mg per ² was added.

Further, as shown in Table 6, instead of the comparative compound A, the compounds of the present invention of the formulas (I) and (II) were replaced by equimolar amounts and added to the ninth layer, the tenth layer and the eleventh layer. Instead of the couplers K-4 and K-7, an equimolar amount of the compound of the present invention represented by the formula (M) is substituted, and further, the 15th layer, the 1st layer
Couplers K-5 and K-6 added to Layer 6 and Layer 17
In the same manner as in Samples 103 to 12 except that the compounds of the present invention represented by formulas (Ya) and (Yb) were replaced by equimolar amounts.
0 was produced.

Comparative Compound A

[0361]

[Chemical 142]

[0362]

[Table 6] The samples 101 to 120 produced in this manner were processed into a 35 mm size Patrone form and photographed by a practical technique. The subject was subjected to the following development processing using a color checker manufactured by Macbeth. The color reproducibility of the obtained practical sample was evaluated by a plurality of evaluators in five stages. The average value of these evaluation values is shown in comparison with Table 7 as a value showing color reproducibility.

[0363]

[Table 7] Process step Time Temperature Tank Capacity replenishment amount W developing 6 minutes 38 ℃ 12l 2.2 l / m ² for first wash 2〃 38〃 4〃 7.5 〃 inversion 2〃 38〃 4〃 1.1 〃 color developing 6〃 38〃 12 〃 2.2 〃 Adjust 2 〃 38 〃 4 〃 1.1 〃 Bleach 6 〃 38 〃 12 〃 0.22 〃 Fixed arrival 4 minutes 38 ℃ 8 〃 1.1 〃 Second water wash 4 〃 38 〃 8〃 7.5 〃 Cheap 2〃 1.1〃 The composition of each processing solution was as follows.

Black-and-white development mother liquor replenisher nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 g 2.0 g sodium sulfite 30 g 30 g hydroquinone potassium monosulfonate 20 g 20 g potassium carbonate 33 g 33 g 1-phenyl -4-Methyl-4-hydroxymethyl-3-pyrazolidone 2.0 g 2.0 g Potassium bromide 2.5 g 1.4 g Potassium thiocyanate 1.2 g 1.2 g Potassium iodide 2.0 mg-Add water 1000 ml 1000 ml pH 9.60 9.60 pH was adjusted with hydrochloric acid or potassium hydroxide.

Inversion solution Mother liquor Replenisher Nitrilo-N, N, N-trimethylenephosphonic acid / 5-sodium salt 3.0 g Same as mother liquor Stannous chloride dihydrate 1.0 g p-Aminophenol 0.1 g Water Sodium oxide 8 g Glacial acetic acid 15 ml Water was added to 1000 ml pH 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide.

Color developing solution Mother liquor Replenishing solution Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 g 2.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate 12-hydrate 36 g 36 g Potassium bromide 1.0 g-potassium iodide 90 mg-sodium hydroxide 3.0 g 3.0 g citrazinic acid 1.5 g 1.5 g N-ethyl- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline Sulfate 11 g 11 g 3,6-dithia-1,8-octanediol 1.0 g 1.0 g Water was added to 1000 ml 1000 ml pH 11.80 12.00 pH was adjusted with hydrochloric acid or potassium hydroxide.

Adjustment liquid Mother liquor Replenishing liquid Ethylenediaminetetraacetic acid ・ 2 sodium salt ・ Dihydrate 8.0 g Same as mother liquor Sodium sulfite 12 g 1-Thioglycerin 0.4 ml Sorbitan ester 0.1 g

[0368]

[Chemical 143] Water was added to 1000 ml pH 6.20 pH was adjusted with hydrochloric acid or sodium hydroxide.

Bleaching solution Mother liquor Replenishing solution Ethylenediaminetetraacetic acid ・ 2 sodium salt ・ Dihydrate 2.0 g 4.0 g Ethylenediaminetetraacetic acid ・ Fe (III) ・ Ammonium ・ dihydrate 120 g 240 g Potassium bromide 100 g 200 g Ammonium nitrate 10 g 20 g Water 1000 ml 1000 ml pH 5.70 5.50 pH was adjusted with hydrochloric acid or potassium hydroxide.

Fixer Mother liquor Replenisher Ammonium thiosulfate 8.0 g The same sodium sulphite 5.0 g Sodium bisulfite 5.0 g Water was added to 1000 ml pH 6.60 pH was adjusted with hydrochloric acid or aqueous ammonia.

Stabilizer Mother liquor Replenisher Formalin (37%) 5.0 ml Same as mother liquor Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.5 ml Water was added to 1000 ml pH was not adjusted. It can be seen that the light-sensitive material of the present invention is particularly excellent in color reproducibility. (Example 2) The edge effects of the samples 101 to 120 produced in Example 1 were measured. The edge effect was obtained by exposing the sample with a soft X-ray through a slit having a line width of 1 mm and 20 μm, followed by developing treatment in the same manner as in Example 1, measuring with a micro densitometer through a blue filter, and taking a ratio of 20 μm / 1 mm. The value is the edge effect value.

The results are shown in Table 8.

[0373]

[Table 8] Table 8 shows that the light-sensitive material of the present invention has a large edge effect and is excellent in sharpness. (Example 3) Samples 101 and 103 produced in Example 1
104, 108-110 9th layer, 10th layer and 1st
Sample 1 was prepared by adding the compound (A-4) of the present invention to one layer in an amount equal to that of the coupler added to each layer.
21-126 were produced.

Samples 101, 103 produced in this way,
The samples 104, 108 to 110 and 121 to 126 were exposed and developed, and the maximum color density (Dmax) of each sample was measured and shown in Table 9.

[0375]

[Table 9] From Table 9, it can be seen that the light-sensitive material in which the magenta coupler of the present invention and the compound (A-4) of the present invention are used together has an excellent maximum color density. (Example 4) In the sample 126 described in Example 3, the compound (A-4) was replaced with (A-1), (A-7), (A-1).
5), sample 12 except that (A-23) was replaced by equimolar amounts
Samples 127 to 130 were prepared in the same manner as in No. 6. When the same tests as in Examples 1 and 3 were performed on these samples 127 to 130, the same results as in Examples 1 and 3 were obtained.
It was preferable.

[0376]

According to the present invention, the color saturation is high, the color turbidity or the color contamination is small, the color reproducibility is excellent, and the sharpness,
A color light-sensitive material having excellent color developability can be obtained.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 21, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Chemical 1] Formula (Yb)

[Chemical 2] Formula (M)

[Chemical 3] Formula (C)

[Chemical 4] Formula (I)

[Chemical 5] Formula (II)

[Chemical 6] In formulas (Ya) and (Yb), X ₁ and X ₂ each represent an alkyl group, an aryl group or a heterocyclic group, and X ₃
Represents an organic residue forming a nitrogen-containing heterocyclic group together with> N-, Y represents an aryl group or a heterocyclic group, and Z is released when the coupler represented by the general formula reacts with an oxidized product of a developing agent. R ₁ in formula (M)
And R ₂ represents a hydrogen atom or a substituent, X represents a hydrogen atom or a group which leaves upon reaction with an oxidized product of a developing agent; in the formula (C), R ₁ represents an aliphatic group, an aromatic group or a hetero group. Represents a ring group, R ₂ represents a hydrogen atom, a halogen atom, an aliphatic group, an acylamino group, an aliphatic oxy group or an aromatic oxy group, and R ₁ and R ₂ are bonded to each other to form a 5- to 7-membered ring. Optionally, Z represents a hydrogen atom or a group capable of leaving when reacted with an oxidized product of a developing agent, X ₁ , X ₂ represent a hydrogen atom or a halogen atom, and n represents an integer of 0 to 18. In the formula (I), R ₁₁ is R ₁₄ -N (R ₁₆ ) CON (R ₁₅ ).
_{-, R 14 OCON (R 15} ) -, R 14 SO 2 N (R
_{15) -, R 14 -N (} R 16) SO 2 N (R 15) -
Or R ₁₇ CONH-, wherein R ₁₄ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, R ₁₅ and R ₁₆ represent a hydrogen atom, an alkyl group or an aryl group, and R _{15 17} represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group having 2 or more carbon atoms in which a carbon atom adjacent to the carbonyl group is not substituted with a hetero atom,
R ₁₂ and R ₁₃ represent a hydrogen atom or a substituent having a Hammett's substituent constant σ _P of 0.3 or less, and B represents a group which releases X after being separated from the hydroquinone mother nucleic acid product,
X represents a development inhibitor, k represents an integer, A and A'represent a hydrogen atom or a group capable of being removed with an alkali; in formula (II), Q ¹ contains at least one heteroatom and is a bond. Represents a group of atoms necessary for forming a 5- or more-membered heterocyclic ring together with the carbon atom, R ²¹ represents a group capable of substituting for a hydroquinone nucleus, and B, X,
k, A and A'have the same meanings as described in the general formula (I).

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

[0018]

[Chemical formula 12] In formulas (Ya) and (Yb), X ₁ and X ₂ each represent an alkyl group, an aryl group or a heterocyclic group, and X ₃
Represents an organic residue forming a nitrogen-containing heterocyclic group together with> N-, Y represents an aryl group or a heterocyclic group, and Z is released when the coupler represented by the general formula reacts with an oxidized product of a developing agent. R ₁ in formula (M)
And R ₂ represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group which leaves upon reaction with an oxidized product of a developing agent; in the formula (C), R _{1 is an} aliphatic group, an aromatic group or a heterocycle. R ₂ represents a hydrogen atom, a halogen atom, an aliphatic group, an acylamino group, an aliphatic oxy group or an aromatic oxy group, and R ₁ and R ₂ are bonded to each other to form a 5- to 7-membered ring. And Z represents a hydrogen atom or a group which leaves when it reacts with an oxidized product of a developing agent,
X ₁ and X _{2 each} represent a hydrogen atom or a halogen atom, and n represents an integer of 0 to 18;
R ₁₁ is R ₁₄ -N (R ₁₆ ) CON (R ₁₅ )-, R
₁₄ OCON (R ₁₅ )-, R ₁₄ SO ₂ N (R ₁₅ ).
_{-, R 14 -N (R 16} ) SO 2 N (R 15) - or represents _R 17 CONH-, wherein ^{R 14} represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, R ₁₅ and R ₁₆ represent a hydrogen atom, an alkyl group or an aryl group, and R ₁₇ is an alkyl group, an alkenyl group, an alkynyl group or an aryl group having 2 or more carbon atoms in which a carbon atom adjacent to the carbonyl group is not substituted with a hetero atom. A group or a heterocyclic group, R ₁₂
And R ₁₃ is a hydrogen atom or Hammett's substituent constant σ
_P represents a substituent of 0.3 or less, B represents a group which releases X after leaving from the hydroquinone mother nucleic acid product, X represents a development inhibitor, k represents an integer, and A and A ′ represent hydrogen. Represents a group capable of being removed with an atom or an alkali; in the formula (II), Q ¹ contains at least one hetero atom, and represents a group of atoms necessary for forming a 5- or more-membered heterocyclic ring with the carbon atom to which it is bonded. R ²¹ represents a group capable of substituting on the hydroquinone nucleus, and B, X, k, A and A ′ have the same meanings as described in the general formula (I).

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0100

[Correction method] Change

[Correction content]

[0100]

[Chemical 44]

[Procedure correction 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0109

[Correction method] Change

[Correction content]

[0109]

[Chemical 53]

[Procedure amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0127

[Correction method] Change

[Correction content]

[0127]

[Chemical 68] The halogenated compound (E) obtained by treating 3-oxonitrile (D) with a halogenating agent such as bromine or sulfuryl chloride in an inert solvent such as dichloromethane is converted into a suitable R _{5 in} the presence of a tertiary amine. Treatment with —OH or treatment with a metal salt such as R ₅ —OM described in (1) above gives the aryloxy form (F). Aminopyrazole obtained by reacting this with foamed water hydrazine in a solvent such as ethanol, a diazonium salt is synthesized using sodium nitrite or isoamyl nitrite and an acid (for example, hydrochloric acid or sulfuric acid), and this diazonium salt is Treatment with a reducing agent such as stannous chloride, sodium sulfite and sodium hydrosulfite gives a hydrazinopyrazole body (H). The target coupler can be synthesized from this (H) form according to the above-mentioned skeleton synthesis method.

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0162

[Correction method] Change

[Correction content]

Examples of the substituent of R ¹⁷ include those mentioned as the substituent of R ¹⁴ .

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0226

[Correction method] Change

[Correction content]

[0226]

[Chemical 95]

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0236

[Correction method] Change

[Correction content]

[0236]

[Chemical 105]

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0244

[Correction method] Change

[Correction content]

[0244]

[Chemical 113]

[Procedure Amendment 10]

[Document name to be amended] Statement

[Name of item to be corrected] 0357

[Correction method] Change

[Correction content]

[0357]

[Chemical 140]

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one blue-sensitive emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer on a support, wherein the blue-sensitive emulsion layer has the following formula (Ya) and / Or (Yb) at least one yellow dye-forming coupler, at least one magenta dye-forming coupler represented by the formula (M) below in the green-sensitive emulsion layer, and at least one of the following formula (C) in the red-sensitive emulsion layer. ) A silver halide comprising at least one cyan dye-forming coupler represented by the formula (1) and at least one compound represented by the following formula (I) or (II) in at least one layer constituting the light-sensitive material. Color photographic light-sensitive material. Formula (Ya) Formula (Yb) Formula (M) Formula (C) Formula (I): Formula (II): In formulas (Ya) and (Yb), X ₁ and X ₂ each represent an alkyl group, an aryl group or a heterocyclic group, and X ₃
Represents an organic residue forming a nitrogen-containing heterocyclic group together with> N-, Y represents an aryl group or a heterocyclic group, and Z is released when the coupler represented by the general formula reacts with an oxidized product of a developing agent. In the formula (M), R ₁
And R ₂ represents a hydrogen atom or a substituent, X represents a hydrogen atom or a group which is released upon reaction with an oxidized product of a developing agent; in the formula (C), R _{1 is an} aliphatic group, an aromatic group or a heterocycle. represents a group, R ₂ represents a hydrogen atom, a halogen atom, an aliphatic group, an acylamino group, an aliphatic oxy group or an aromatic oxy group, R ₁ and R ₂ are joined to form a 5- to 7-membered ring together And Z represents a hydrogen atom or a group which leaves when it reacts with an oxidized product of a developing agent,
X ₁ and X _{2 each} represent a hydrogen atom or a halogen atom, and n represents an integer of 0 to 18;
R ₁₁ is R ₁₄ —N (R ₁₆ ) CON (R ₁₅ ) —, R ₁₄ OCO
_{N (R 15) -, R} 14 SO 2 (R 15) -, R 14 -N
(R ₁₆ ) SO ₂ N (R ₁₅ ) — or R ₁₇ CONH—, wherein R ₁₄ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₁₅
And R ₁₆ represents a hydrogen atom, an alkyl group or an aryl group, R ₁₇ is an alkyl group having 2 or more carbon atoms in which a carbon atom adjacent to the carbonyl group is not substituted with a hetero atom,
Represents an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, R ₁₂ and R ₁₃ represent a hydrogen atom or a substituent having a Hammett's substituent constant σ _p of 0.3 or less,
B represents a group which releases X after leaving from the hydroquinone mother nucleic acid product, X represents a development inhibitor, k represents an integer, and A and A'represent a hydrogen atom or a group removable by an alkali; In (II), Q ¹ contains at least one heteroatom and, together with the carbon atom to which it is bonded, 5
Represents a group of atoms necessary to form a heterocyclic ring having at least one member ring,
R ²¹ represents a group capable of substituting in the hydroquinone nucleus,
B, X, k, A and A'have the same meanings as described in the general formula (I).