JP2879488B2 - Silver halide color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic material and, more particularly, to a photographic material excellent in sharpness and processability.

[0002]

2. Description of the Related Art In recent years, in color photographic light-sensitive materials,
In order to respond to the needs of users, the sensitivity of photosensitive materials has been increased,
Higher image quality is being promoted. Of the latter, improvement in sharpness has been developed as a central issue for improving color reproducibility and graininess and improving image quality in color photographic light-sensitive materials. On the other hand, improvements in development processing stability, handling properties, and color image fastness of photosensitive materials are expected,
Requests for improvement are increasing.

[0003] In order to improve the sharpness, it is necessary to reduce the light scattering of incident light. For materials other than silver halide, use a dye-forming coupler having high color-forming properties from the viewpoint of minimizing the amount of the oil-soluble additive and reducing the thickness of the hydrophilic colloid layer on the support. In addition, measures have been taken, such as developing materials capable of forming photosensitive materials without using high-boiling organic solvents. Further, for the purpose of the same thinning, a method of increasing the reactivity of an anti-fading agent, which is mainly used in the non-photosensitive layer, with an oxidized developing agent per unit area has been proposed. More recently, it has become common practice to use DIR compounds to improve the apparent sharpness, especially by improving the edge effect.

The anti-fading agent will be described. The formation of a dye image in a silver halide photographic light-sensitive material is usually oxidized when an aromatic primary amine color developing agent reduces silver halide grains in the light-sensitive light-sensitive material. The reaction is carried out by causing a coupling reaction with a coupler contained in advance. At this time, it is well known that when the generated oxidized developing agent diffuses into a different color-sensitive layer to form a color, undesirable color turbidity (inter-layer color mixing) occurs, which adversely affects color reproducibility. It is also known that color fogging occurs during color development due to air oxidation of a developing agent, fog of an emulsion, and the like. In the following,
The color turbidity and the color fog are collectively referred to as color contamination.

[0005] As a means for preventing these, a compound for reducing an oxidized developing agent is generally added, and the compound for preventing color contamination is called a color mixture inhibitor. Color mixing inhibitors are described, for example, in US Pat.
Nos. 4,977,553 and 4,277,553, and the like, and U.S. Pat. No. 4,198,239, JP-A-59-202465, and the like, using a hydroquinone into which a substituent is introduced for improving the ability to prevent color mixing. Alternatively, a method using a hydrazine-based compound has been proposed in JP-A-1-147455 or the like. Although these compounds do have some effect in preventing color contamination, these compounds diffuse themselves into the adjacent silver halide emulsion layer, especially under high-temperature and high-humidity storage, while the compounds themselves diffuse, There has been a problem of increasing the fluctuation of photographic properties. To prevent diffusion in the light-sensitive material film, measures have been taken to introduce an oil-soluble substituent into the reduced nucleus and to add a high-boiling organic solvent. However, an increase in film thickness was inevitable.

JP-A-1-206337 discloses a method in which a polymer compound obtained by polycondensation is further used as a color-mixing inhibitor by further connecting a hydroquinone skeleton to a polymer by a covalent bond. No. 2710801, JP-A-57-17949, JP-A-57-17949
No. 169844, which shows that the material has the ability to prevent color contamination with a small amount of addition.

However, when the above-mentioned polymer compound is used in combination with a conventionally known acylacetanilide type yellow coupler, there is a problem in processing stability that photographic properties vary greatly due to a variation in the amount of sodium sulfite in a color developer. There is a need for a solution. Further, depending on the developing sites located in various parts of the world, the preservation state of the processing solution is poor, and the problem of processing stability has recently attracted attention as one of the performances required for photosensitive materials.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a color photographic material having excellent sharpness. Second, it is to provide an excellent color photographic light-sensitive material having little change in photographic properties with respect to a change in the composition of a color developing solution when used in a color photographic light-sensitive material.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide having at least one blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support. In a color photographic light-sensitive material, at least one layer constituting the light-sensitive material has the following general formula (Y)
a) or at least one of the yellow dye-forming couplers represented by the general formula (Yb), and at least one layer constituting the light-sensitive material further contains at least one compound represented by the following general formula (H) This was achieved by a silver halide color photographic light-sensitive material characterized by the following. General formula (Ya)

[0010]

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General formula (Yb)

[0012]

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Wherein X ₁ and X ₂ are each an alkyl group,
X ₃ represents an organic residue that forms a nitrogen-containing heterocyclic group together with> N—, Y represents an aryl group or a heterocyclic group, and Z represents a coupler represented by the general formula. Represents a group which is released when reacted with an oxidized developing agent. General formula (H)

[0014]

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Wherein X is -N (R ¹ ) R ³ or -OR ⁴
Wherein R ¹ is a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R ³ and R ⁴ are a hydrogen atom or a group removed under alkaline conditions. R ² is a hydrogen atom,
It is an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a nitro group or a hydrazino group, and X and R ² may be linked to form a ring. R ⁵ represents a hydrogen atom, an alkyl group or a group removed under alkaline conditions. R ¹ , R ² or R
^In part ⁵ , two or more formulas (H) may combine to form an oligomer or polymer. G is -CO-, -CO
_{CO -, - SO 2 -,} - SO -, - CON (R 6) -, -
^{COO -, - COCON (R 7} ) -, - COCOO -, -
PO (R ⁸⁾ -, - represents a CS- or iminomethylene group wherein R ^6, R ⁷ is a hydrogen atom, an alkyl group or an aryl group, R ⁸ is an alkyl group or an aryl group. m is 0, 1 or 2, and when it is 2, G may be the same or different.

First, the couplers represented by formulas (Ya) and (Yb) will be described in detail below. When X ₁ and X ₂ represent an alkyl group, it is a linear, branched, cyclic, saturated, unsaturated, substituted or unsubstituted alkyl group having 1 to 30, preferably 1 to 20 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, butyl, cyclopropyl, allyl, t-octyl, i-butyl, dodecyl,
2-hexyldecyl is mentioned.

When X ₁ and X ₂ represent a heterocyclic group, the heteroatom having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, contains at least one nitrogen atom, oxygen atom or sulfur atom, and preferably 3 to 12, preferably 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. X
_{When 1} and X ₂ represent an aryl group, they have 6 to ₂ carbon atoms.
Represents 0, preferably 6 to 10 substituted or unsubstituted aryl groups. Representative examples of the aryl group include phenyl and naphthyl.

When X ₃ represents a nitrogen-containing heterocyclic group formed with> N—, the heterocyclic group has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, and other than a nitrogen atom as a hetero atom, for example, an oxygen atom Or 3 to 12 which may contain a sulfur atom.
A membered ring, preferably a 5- or 6-membered, substituted or unsubstituted, saturated or unsaturated, monocyclic or fused ring heterocyclic group. 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-pyrazidinyl, 2,3-dihydro-1-indazolyl, 2-isoindolinyl, 1-indolyl, 1-pyrrolyl, 4-thiazine-S. Examples include S-dioxo-4-yl or benzoxazin-4-yl.

When X ₁ and X ₂ represent an alkyl, aryl or heterocyclic group having a substituent, and when X ₃ has a substituent, the nitrogen-containing heterocyclic group formed with> N— Examples of such substituents include the following. Halogen atom (for example, fluorine atom, chloro atom), alkoxycarbonyl group (having 2 to 3 carbon atoms)
0, preferably 2-20. For example, methoxycarbonyl,
Dodecyloxycarbonyl, hexadecyloxycarbonyl), acylamino group (2 to 30, preferably 2 to 20 carbon atoms. For example, acetamido, tetradecanamido,
2- (2,4-di-t-amylphenoxy) butanamide, benzamide), sulfonamide group (1 to 3 carbon atoms)
0, preferably 1-20. For example, methanesulfonamide, dodecanesulfonamide, hexadecylsulfonamide, benzenesulfonamide), carbamoyl group (1 to 30 carbon atoms, preferably 1 to 20; for example, N-butylcarbamoyl, N, N-diethylcarbamoyl), N-
Sulfonylcarbamoyl group (1 to 30 carbon atoms, preferably 1 to 20; for example, N-mesylcarbamoyl group, N-dodecylsulfonylcarbamoyl), sulfamoyl group (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 (1 to 30 carbon atoms, preferably 1 to 20; for example, methoxy, hexadecyloxy, isopropoxy), and an aryloxy group (6 to 20 carbon atoms, preferably 6 to 10 carbon atoms). For example, phenoxy, 4-methoxyphenoxy, 3-t-butyl-4-
Hydroxyphenoxy, naphthoxy), aryloxycarbonyl group (7-21 carbon atoms, preferably 7-11 carbon atoms);
For example, phenoxycarbonyl), N-acylsulfamoyl group (2 to 30, preferably 2 to 20 carbon atoms; for example, N-propanoylsulfamoyl, N-tetradecanoylsulfamoyl), sulfonyl group (1 carbon atom) ~ 30,
Preferably 1-20. For example, methanesulfonyl, octanesulfonyl, 4-hydroxyphenylsulfonyl, dodecanesulfonyl), alkoxycarbonylamino group (1 to 30, preferably 1 to 20 carbon atoms; for example, ethoxycarbonylamino), cyano group, nitro group, carboxyl group, hydroxyl Group, sulfo group, alkylthio group (1 to 30 carbon atoms, preferably 1 to 20; for example, methylthio, dodecylthio, dodecylcarbamoylmethylthio), ureido group (1 to 30 carbon atoms, preferably 1 to 2 carbon atoms)
0. For example, N-phenylureide, N-hexadecylureide), an aryl group (C6-20, preferably 6)
-10. For example, phenyl, naphthyl, 4-methoxyphenyl), a heterocyclic group (C1-20, preferably 1-1)
0. A 3-12, preferably 5- or 6-membered, monocyclic or condensed ring containing at least one 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 (1-30 carbon atoms, preferably 1-20 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 (1 to 30 carbon atoms, preferably 2 to 20; for example, acetyl, benzoyl) acyloxy group (2 to 30 carbon atoms, preferably Is 2 to 20. For example, propanoyloxy, tetradecanoyloxy), an arylthio group (6 to 20, preferably 6 to 10 carbon atoms, for example, phenylthio, naphthylthio),
A sulfamoylamino group (having 0 to 30, preferably 0 to 20 carbon atoms; for example, N-butylsulfamoylamino, N
-Dodecylsulfamoylamino, N-phenylsulfamoylamino) or N-sulfonylsulfamoyl group (C1-30, preferably 1-20, e.g. N)
-Mesylsulfamoyl, N-ethanesulfonylsulfamoyl, N-dodecanesulfonylsulfamoyl,
N-hexadecanesulfonylsulfamoyl). The above substituents may further have a substituent. Examples of the substituent include the substituents mentioned here.

Preferred examples of the substituents include 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 and an aryl group. Can be The formula (Y
When Y represents an aryl group in a) and (Yb), it is a substituted or unsubstituted aryl group having 6 to 20, preferably 6 to 10 carbon atoms. For example, a phenyl group and a naphthyl group 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 listed as examples when X ₁ has a substituent. For example, when one of the substituents is a halogen atom, an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group, a sulfonyl group, an N-
It is a sulfonylsulfamoyl group, an N-acylsulfamoyl group, an alkoxy group, an acylamino 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 formula (Y
The groups represented by Z in a) and (Yb) include:
Any of conventionally known coupling-off groups may be used. Preferred Z is a nitrogen-containing heterocyclic group, 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 bonded to the coupling position at a nitrogen atom. No. These leaving groups may be a non-photographic useful group or a photographically useful group or a precursor thereof (for example, a development inhibitor, a development accelerator, a desilvering accelerator, a fogging agent,
Dye, hardener, coupler, oxidized scavenger of developing agent, fluorescent dye, developing agent or electron transfer agent).

When Z is a photographically useful group, conventionally known groups are useful. For example, U.S. Pat.
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 No. 193389A, No. 348139A or No. 272573A or a leaving group for releasing the same. Group) is used.

When Z represents a nitrogen-containing heterocyclic group bonded to the coupling position by a nitrogen atom, it preferably has 1 to 1 carbon atoms.
5, preferably 1 to 10 5- or 6-membered, substituted or unsubstituted, saturated or unsaturated, monocyclic or fused-ring heterocyclic groups. The hetero atom may include an oxygen atom or a sulfur atom in addition to the nitrogen atom. Preferred specific examples of the heterocyclic group include 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, imidazolidine-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 that the group represented by X ₁ 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. Particularly preferred is a substituted or unsubstituted phenoxy group. When having 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, preferred substituents are those in which 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. Or an acyl group.

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 listed as the substituent which the group represented by X ₁ may have. Among them, preferred substituents are those in which 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 part of the heterocyclic group has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and contains at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom, for example, 3 to 12; It is preferably a 5- or 6-membered, substituted or unsubstituted, saturated or unsaturated, monocyclic or fused-ring heterocyclic group. Examples of the heterocyclic oxy group include a pyridyloxy group, a pyrazolyloxy group, and a furyloxy group. When it has a substituent, examples of the substituent include the substituents listed as the substituent which the group represented by X ₁ may have. Among them, preferred substituents include 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, and a nitro group. , A carbamoyl group or a sulfonyl group.

When Z represents a heterocyclic thio group, the part of the heterocyclic group has 1 to 20, preferably 1 to 10 carbon atoms and contains at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom. To 12, preferably a 5- or 6-membered, substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed heterocyclic group. Examples of the heterocyclic thio group include a tetrazolylthio group, 1,3,4
-Thiadiazolylthio, 1,3,4-oxadiazolylthio, 1,3,4-triazolylthio, benzimidazolylthio, benzothiazolylthio, or 2
-Pyridylthio groups. When having a substituent,
Examples of the substituent include those exemplified as the substituent which the group represented by X ₁ may have. Among them, preferred substituents include at least one alkyl group of substituent, aryl group, carboxyl group, alkoxy group, halogen atom, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group,
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, substituted or unsubstituted aromatic acyloxy group having 6 to 10 carbon atoms, or 2 to 2 carbon atoms.
30 and preferably 2 to 20 substituted or unsubstituted aliphatic acyloxy groups. When these have a substituent,
Examples of the substituent include those exemplified as the substituent which the group represented by X ₁ may have. When Z represents a carbamoyloxy group, it has 1 carbon atom;
-30, preferably 1-20, aliphatic, aromatic, heterocyclic, substituted or unsubstituted carbamoyloxy groups. For example, N, N-diethylcarbamoyloxy, N-
Examples include phenylcarbamoyloxy, 1-imidazolylcarbonyloxy or 1-pyrrolocarbonyloxy. When these have a substituent, examples of the substituent include the substituents listed as the substituent which the group represented by X ₁ may have.

When Z represents an alkylthio group, it has 1 carbon atom
To 30, preferably 1 to 20, linear, branched, cyclic, saturated, unsaturated, substituted or unsubstituted alkylthio groups. When it has a substituent, examples of the substituent include the substituents listed as the substituent which the group represented by X ₁ may have. Next, particularly preferred ranges of the couplers represented by formulas (Ya) and (Yb) will be described below. The group represented by X ₁ in the formula (Ya) is preferably an alkyl group. Particularly preferred is an alkyl group having 1 to 10 carbon atoms.

The group represented by Y in the formulas (Ya) and (Yb) is preferably an aromatic group. Particularly preferred is a phenyl group having at least one substituent at the ortho position. The description of the substituent includes those described as the substituent which may be possessed when Y is an aromatic group. The description of the preferred substituent is the same. Formulas (Ya) and (Y
The group represented by Z in b) is preferably a 5- to 6-membered nitrogen-containing heterocyclic group, an aromatic oxy group, a 5- to 6-membered heterocyclic oxy group, which is bonded to the coupling position by a nitrogen atom, or And a 6-membered heterocyclic thio group. Preferred couplers in formulas (Ya) and (Yb) are those of the following formula (Y
c), (Yd) or (e). Formula (Yc)

[0030]

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Formula (Yd)

[0032]

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Formula (Ye)

[0034]

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In the formula, Z represents the same meaning as described in the formula (Ya), X ₄ represents an alkyl group, X ₅ represents an alkyl group or an aromatic group, and Ar represents at least one substituent at the ortho position. X ₆ represents an organic residue which forms a nitrogen-containing heterocyclic group (monocyclic or condensed ring) together with —C (R ₁ R ₂ ) —N <, and X ₇ represents —C
_{(R 3) = C (R} 4) represents an organic residue forming a -N <with a nitrogen-containing Hajime Tamaki (monocyclic or condensed), R _1,
R ₂ , R ₃ and R ₄ represent a hydrogen atom or a substituent.
In the formulas (Yc) to (Ye), the detailed description and the preferred range of the groups represented by X _{4 to} X ₇ , Ar and Z are described in the description of formulas (Ya) and (Yb). Has the same meaning as described above. When R _{1 to} R ₄ represent a substituent, those exemplified as the substituent which X ₁ may have may be mentioned as examples. Particularly preferred couplers in the above general formula are those represented by formula (Yd) or (Ye). The couplers represented by formulas (Ya) to (Ye) are represented by X ₁ to
X ₇ , Y, Ar, R _{1 to} R _4, and two groups bonded to each other via a divalent or higher group in the group represented by Z.
Heavy or higher multimers (eg, telomers or polymers) may be formed. In this case, the number of carbon atoms may be out of the specified range for each substituent. The couplers represented by the formulas (Ya) to (Ye) are preferred examples when they are diffusion-resistant couplers. The diffusion resistant type is a coupler having a group having a sufficiently large molecular weight in the molecule to immobilize the layer to which the molecule is added. Usually, the total carbon number is 8 to 30, preferably 10 to 2
An alkyl group having 0 or an aryl group having a substituent having 4 to 20 carbon atoms is used. These non-diffusible groups may be substituted in any of the molecules, and may have a plurality. Specific examples of the yellow couplers represented by formulas (Ya) to (Ye) are shown below, but the invention is not limited thereto.

[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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The yellow couplers of the present invention represented by formulas (Ya) to (Ye) can be synthesized according to the following rules. Synthesis Example-1

[0058]

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Synthesis of Intermediate B Compound A 357.5 g (3.0 mol), Compound B39
6.3 g (3.0 mol) of 1.2 liter of ethyl acetate,
Dissolved in 0.6 liter of dimethylformamide. While stirring, 631 g of dicyclohexylcarbodiimide
A solution of (3.06 mol) in acetonitrile (400 ml) was added dropwise at 15-35 ° C. After reacting at 20 to 30 ° C. for 2 hours, the precipitated dicyclohexylurea was collected by filtration.
500 ml of ethyl acetate and 1 liter of water were added to the filtrate, and the aqueous layer was removed. Next, the organic layer was washed twice with 1 liter of water. After the organic layer was dried over anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure, and 629 g of Intermediate A was obtained as an oil.
(98.9%). 692 g (2.97 mol) of intermediate A are dissolved in 3 liters of ethyl alcohol and, with stirring, 430 g of 30% sodium hydroxide at 75-80 ° C.
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 5 liters of water, and concentrated hydrochloric acid was added at 40 to 50 ° C.
0 ml was added dropwise with stirring. After stirring at the same temperature for 1 hour, 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. Ethyl acetate 400 in the filtrate
and 600 ml of water. After removing the aqueous layer, the organic layer was
Washed twice. After the organic layer was dried over anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure to obtain 162 g of an oil.
This oily substance was diluted with 100 ml of ethyl acetate and 300 ml of n-hexane.
crystallized from 108 ml, 108 g (87.1%) of intermediate D
Obtained. (Melting point 132-134 ° C)

[0060]

[Table 1]

Synthesis of Illustrative Coupler Y-7 49.6 g (0.08 mol) of intermediate D were dissolved in 300 ml of dichloromethane. Sulfuryl chloride was added to this solution.
4 g (0.084 mol) was added dropwise while stirring at 10 to 15 ° C. After reacting at the same temperature for 30 minutes, 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 oil. 47 g of this oil was dissolved in 200 ml of acetonitrile, and 28.4 g of compound D (0.2 g) was added thereto.
2 mol) and 22.2 g (0.22 mol) of triethylamine were added with stirring. After reacting at 40-50 ° C for 4 hours, the reaction mixture was poured into 300 ml of water, and the precipitated oil 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.
And washed with water. The organic layer was acidified with dilute hydrochloric acid, washed twice with water, and concentrated under reduced pressure to obtain a residue. (Yield 70 g) The obtained oily substance was crystallized from a mixed solvent of 50 ml of ethyl acetate and 100 ml of n-hexane to obtain 47.8 g of the exemplified coupler Y-7.
(80%). (Melting point 145-7 ° C)

[0062]

[Table 2]

The yellow couplers represented by the formulas (Ya) to (Ye) of the present invention are used in an amount of 1.15 per mole of silver halide.
It can be used in the range of 0 × 10 × 10 ⁻³ mol.
Preferably, it is 5.0 × 10 ^{-1 to} 2.0 × 10 ^-2 mol, and more preferably, it is in the range of 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, or may be used in combination with other known couplers. The general formula (H) will be described in more detail.
The aliphatic group for R ¹ and R ² has 1 to 30 carbon atoms, and is a linear, branched or cyclic alkyl group, aralkyl group,
An alkenyl group or an alkynyl group, wherein the alkyl group is
It is a straight-chain, branched-chain or cyclic one having 1 to 30 carbon atoms, such as methyl, cyclohexyl, 2-octyl, and octadecyl. The aralkyl group has 7 to 30 carbon atoms, such as benzyl, phenethyl and trityl.
The alkenyl group has 2 to 30 carbon atoms and is, for example, vinyl or 1-dodecenyl. The alkynyl group has 2 to 30 carbon atoms, for example, ethynyl, octynyl,
Phenylethynyl. The aromatic group for R ¹ and R ² is an aryl group having 6 to 30 carbon atoms, such as phenyl and naphthyl. The heterocyclic group of R ¹ and R ² may be saturated or unsaturated, and may be a single ring or a condensed ring, and examples thereof include pyridyl, imidazolyl, thiazolyl, quinolyl, morpholino, and thienyl.

The hydrazino group for R ² is represented by the general formula (H)
R ¹ N (R ³ ) —N (R ⁵ ) —. R ³ ,
Examples of the group to be removed under alkaline conditions for R ⁴ and R ⁵ include:
It has 20 or less carbon atoms, and examples thereof include an alkylsulfonyl group, an arylsulfonyl group, an acyl group, a dialkylaminomethyl group, and a hydroxymethyl group. R ⁵
The alkyl of R ¹ is as described for R ¹ , and R ^{3 to} R
⁵ is preferably a hydrogen atom. The alkyl group for R ⁶ , R ⁷ and R ⁸ has 1 to 20 carbon atoms and includes methyl,
Cyclohexyl and dodecyl. R ⁶ , R ⁷ ,
The aryl group for R ⁸ has 6 to 20 carbon atoms,
Phenyl and naphthyl. If possible, the groups described above may have a substituent, and as the substituent, an alkyl group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group, an alkoxy group, an aryloxy group, a hydroxy group, a carboxyl group , An aryl group, a carbamoyl group, a sulfamoyl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group, an acyl group, a halogen atom, a cyano group, a heterocyclic group or a sulfo group.

When R ¹ is an aromatic group, the substituent is preferably an electron-donating group, and examples thereof include an acylamino group, a sulfonylamino group, a ureido group, a urethane group and an alkoxy group. That the general formula (H) is resistant to diffusion means that it contains a ballast group or a group that enhances adsorption to silver halide. Examples of the ballast group include ballast groups commonly used in immobile photographic materials such as couplers. In that case, it is more preferable that the compound has a polar group as a substituent. As a polar group,
Groups in which the π value is less than -1.0 in combination, such as hydroxy, sulfonamide, amino, carboxy, carbamoyl, sulfamoyl, ureido, and heterocyclic groups. When a ballast group is contained, the molecular weight of the general formula (H) is 30.
0 to 1500, preferably 450 to 1500, more preferably 500 to 800. Examples of the group that enhances the adsorption to the silver halide surface include a thiourea group, a mercaptoheterocyclic group, and an azole group. As the diffusion resistant group, it is more preferable to have a ballast group than a silver halide adsorption group.

G in the general formula (H) is -CO-,-
_{COCO -, - SO 2 -,} - CON (R 6) - , or -CO
O- is preferable, and -CO-, -COCO-, and -CON are preferable.
(R ⁶ ) — and —COO— are more preferred, and —CO— is most preferred. Among the compounds represented by the general formula (H), those represented by the following general formulas (HI) to (HV) are preferable.

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In the formula, R ¹¹ and R ²¹ represent R ^{1 in the} general formula (H)
G ¹¹ , G ³¹ , G ⁴¹ , G ⁵¹ are the same as G, R ¹³ , R
^23, R ³³ is R ³ as defined, R ⁴⁴ is R ⁴ as defined, R ^15,
R ²⁵ , R ³⁵ , R ⁴⁵ and R ⁵⁵ have the same meanings as R ⁵ , m ¹ , m ⁴ and m
⁵ and m, X ⁵¹ is as defined X. R ¹² is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, or a hydrazino group, and R ²² is a cyano group, a nitro group, a perfluoroalkyl group (having 1 to 30 carbon atoms, and Methyl, perfluorooctyl) or a heterocyclic group;
⁴² is an aliphatic group, an aromatic group, or a heterocyclic group. Z ^{31 in the} general formula (H-III) includes methylene, ethylene, trimethylene, -CO-, 1,2-phenylene, -O-,-
Examples include a divalent linking group composed of S-, -NH-, -NHNH-, and a combination thereof, and the ring is preferably a 5- to 8-membered ring. In the general formula (HV), R ⁵¹ is a hydrogen atom, a halogen atom or an alkyl group, and L ⁵¹ is —CO—,
It is a divalent linking group consisting of SO ₂ —, —NH—, —O—, —S—, phenylene, alkylene and a combination thereof, and L ⁵² has a hydrogen atom removed from R ¹ of the general formula (H). It is a divalent group, and r and t are 0 or 1. Among the general formulas (HI) to (HV), the following general (H-VI)
Is more preferred.

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In the formula, R ⁶¹ represents an aromatic group, R ⁶² represents an aliphatic group, an aromatic group or a heterocyclic group, and G ⁶¹ represents —CO—, —C
^{OCO -, - CON (R 66} ) - or -COO- in which.
Here, R ⁶⁶ has the same meaning as R ^{6 in} formula (H). R ⁶¹ or R ⁶⁶ contains a ballast group. Further, the following general formula (H-VII) is most preferred.

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In the formula, R ⁷¹ is a substituent of a benzene ring,
For example, those described as the substituent of R ^{1 in} the general formula (H) can be mentioned, and electron-donating ones (acylamino, ureido, sulfonylamino, alkoxy) are particularly preferable. R
⁷² is an aliphatic group or an aromatic group. Either R ⁷¹ or R ⁷² has a ballast group having 8 or more carbon atoms. Preferably, R ⁷¹ or R ⁷² has a polar group. Hereinafter, specific examples of the compound represented by Formula (H) are shown, but the present invention is not limited thereto.

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The synthesis of the compound represented by formula (H) of the present invention is described in, for example, JP-A-3-164735 and JP-A-3-154.
051, 3-150560, 3-150562, and 1-315573. The compound represented by formula (H) of the present invention can be used in the range of 1 × 10 ^{−4 to} 2.0 g / m ² . It is preferably from 2 × 10 ^{−4 to} 1.5 g / m ² , and more preferably from 1 × 10 ^{−3 to} 1.2 g / m ² .

The light-sensitive material of the present invention may be provided with at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive silver halide emulsion layer on a support. There is no particular limitation on the number and order of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. Wherein the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to any of red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit light-sensitive layers is generally such that the red-sensitive layer, green The color-sensitive layer and the blue-sensitive layer are provided in this order. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. Non-light-sensitive layers such as various intermediate layers may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer, JP-A-61-43748, 59-113
No. 438, 59-113440, 61-20037, couplers as described in the specification of 61-20038, DIR compounds and the like may be contained. May be included. The plurality of silver halide emulsion layers constituting each unit light-sensitive layer preferably employ a two-layer structure of a high-speed emulsion layer and a low-speed emulsion layer as described in German Patent No. 1,121,470 or British Patent No. 923,045. be able to. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. In addition,
57-112751, 62-200350, 62-206541, 62-2
As described in JP-A-06543 and the like, a low-speed emulsion layer may be provided on the side remote from the support, and a high-speed emulsion layer may be provided on the side near the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / In the order of the low-sensitivity red photosensitive layer (RL), or in the order of BH / BL / GL / GH / RH / RL, or BH / BL / GH /
They can be installed in the order of GL / RL / RH. Also Tokunoaki
As described in JP-A-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. JP-A-56-25738, 62-63
As described in U.S. Pat. No. 936, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. Also, as described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the less sensitive silver halide emulsion layer, and the lower layer is more sensitive than the middle layer. An arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and three layers having different sensitivities are sequentially reduced in sensitivity toward a support, may be mentioned. Even when such three layers having different sensitivities are used, as described in JP-A-59-202464, a medium-speed emulsion in the same color-sensitive layer from the side away from the support is used. Layers / high-speed emulsion layers / low-speed emulsion layers. 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
The arrangement may be changed as described above even in the case of more than layers.

In order to improve color reproducibility, US Pat.
Nos. 663,271, 4,705,744, 4,707,436, and JP-A Nos. 62-160448 and 63-89850.
It is preferable that a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, or RL is disposed adjacent to or close to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material. 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. Silver halide grains in photographic emulsions include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystalline forms such as spheres and plates, twin planes, etc. Or a composite form thereof. The grain size of silver halide is about
Fine particles having a diameter of 0.2 μm or less or large particles having a projected area diameter of about 10 μm may be used, and a polydisperse emulsion or a monodisperse emulsion may be used. Silver halide photographic emulsions which can be used in the present invention are described, for example, in Research Disclosure (RD) No. 17643 (December 1978), pp. 22-23, "I. Emulsion preparation and types", and the like.
No.18716 (November 1979), p.648, No.307105 (1989
Nov.), pp. 863-865, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chemie)
et Phisique Photographique, PaulMontel, 1967), Duffin's Photographic Emulsion Chemistry, published by Focal Press (G.
F. Duffin, Photographic Emulsion Chemistry (Focal P
ress, 1966)), "Production and Coating of Photographic Emulsion" by Zelikman et al., Published by Focal Press (VL Zelikman et al.,
Making and Coating Photographic Emulsion, Focal Pr
ess, 1964). Monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Further, 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, Photographic Science and E).
14, 248-257 (1970); U.S. Patent Nos. 4,434,226, 4,414,310, 4,433,048,
It can be easily prepared by the methods described in JP-A-4,439,520 and British Patent No. 2,112,157. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, and may have a layered structure.
Further, silver halides having different compositions may be joined by an epitaxial junction.
It may be bonded to a compound other than silver halide such as lead oxide. Also, a mixture of particles of 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, or an internal latent image type in which a latent image is formed inside a grain, or a type having a latent image on both the surface and the inside.
It must be a negative emulsion. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. A method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm. As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additives used in such a process are Research Disclosure N
o. 17643, No. 18716 and No. 307105, and the relevant locations 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 emulsions differing in at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer. U.S. Pat. It can be preferably used for a light-sensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. The term “silver halide particles having a fogged inside or surface” refers to silver halide grains that can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. . The preparation of silver halide grains having a grain interior or surface fog is described in U.S. Pat.
No. 98 and JP-A-59-214852. The silver halides forming the internal nuclei of the core / shell type silver halide grains whose insides are fogged may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain covered,
Any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used. The size of the fogged silver halide grains is not particularly limited, but the average grain size is preferably 0.01 to 0.75 μm, particularly preferably 0.05 to 0.6 μm. There is no particular limitation on the particle shape,
Regular grains or polydisperse emulsions may be used,
It is preferably monodisperse (a silver halide grain in which at least 95% of the weight or the number of grains has a grain size within ± 40% of the average grain size). In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. .

The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide, if necessary. Preferably silver iodide is 0.5
-10 mol%. The fine grain silver halide has an average grain size (average value of the circle equivalent diameter of the projected area) of 0.01.
To 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be chemically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing fine silver halide grains. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred. Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table.

Types of Additives RD17643 RD18716 RD307105 1. Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer page 648, right column 3. Spectral sensitizer, page 23-24, page 648, right column 866- Page 868 Supersensitizer 〜 Right column of page 649 4. Brightener 24 page 647 right column of page 868 5. Fogging prevention 24-25 page 649 right column of 868-870 agent, stabilizer 6. Light absorber Pages 25-26 page 649 right column page 873 filter ~ page 650 left column Dyes, UV absorbers 7.Stain 25 page right column 650 page left column 872 Inhibitors ~ right column 8. Column 872 Stabilizer 9. Hardener page 26 Page 651 left column 874-875 10. Binder page 26 page 651 left column 873-874 11. Plasticizer, page 27 650 page right column 876 Lubricant 12. Coating aids, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactants 13. Static, page 27, page 650, right column, pages 876 to 877 Inhibitors 14.

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add a compound which can react with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503 and can be fixed to the photosensitive material. . U.S. Pat.No. 4,740,454
No. 4,788,132, JP-A-62-18539, JP-A-1-28
It is preferable to include a mercapto compound described in No. 3551. In the light-sensitive material of the present invention, compounds described in JP-A-1-06052, which release a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof irrespective of the amount of developed silver produced by development processing Is preferably contained. In the light-sensitive material of the present invention, International Publication WO88 / 04794, dyes dispersed by the method described in
EP 317,308A, U.S. Pat.No. 4,420,555, JP-A 1-2593
The dye described in No. 58 is preferably contained. Various color couplers can be used in the light-sensitive material of the present invention, and specific examples thereof are described in Research Disclosure Nos. 17643, VII-CG and VII-CG, and 307105, VII
-Described in the patents described in CG. As the yellow coupler, for example, U.S. Pat.Nos. 3,933,501, 4,022,620, 4,326,024, and 4,401,752
No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476,760, U.S. Patent No. 3,97
Preferred are those described in 3,968, 4,314,023, 4,511,649 and European Patent 249,473A.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferred, and US Pat. Nos. 4,310,619 and 4,351,897, and European Patent 73,63.
No. 6, U.S. Patent Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984),
JP-A-60-33552, Research Disclosure No.2
4230 (June 1984), JP-A-60-43659, JP-A-61-72238
No. 60-35730, No. 55-118034, No. 60-185951,
U.S. Patents 4,500,630, 4,540,654, 4,5
No. 56,630 and WO 88/04795 are particularly preferable. Cyan couplers include phenolic and naphthol couplers and are described in U.S. Pat.
No. 12, No. 4,146,396, No. 4,228,233, No. 4,2
No. 96,200, No. 2,369,929, No. 2,801,171, No.
No. 2,772,162, No. 2,895,826, No. 3,772,002,
No. 3,758,308, No. 4,334,011, No. 4,327,173
No., West German Patent Publication No. 3,329,729, European Patent No. 121,365
A, No. 249,453A, U.S. Pat.No. 3,446,622, No.
No. 4,333,999, No. 4,775,616, No. 4,451,559,
No. 4,427,767, No. 4,690,889, No. 4,254,212
And No. 4,296,199, and JP-A-61-42658. Furthermore, JP-A Nos. 64-553 and 64-554
And the pyrazoloazole couplers described in US Pat. Nos. 64-555 and 64-556 and the imidazole couplers described in US Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are described in U.S. Pat.
No. 20, No. 4,080,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, UK Patent 2,102,137,
It is described in European Patent No. 341,188A and the like. As a coupler in which a coloring dye has an appropriate diffusibility, U.S. Pat.
4,366,237; UK Patent 2,125,570; European Patent 9
No. 6,570 and West German Patent (Publication) No. 3,234,533 are preferred.

The colored coupler for correcting the unnecessary absorption of the coloring dye is Research Disclosure No. 1
No. 307105, No. 307105, U.S. Pat.No. 4,163,670, JP-B-57-39413, U.S. Pat.
Preferred are those described in 4,929, 4,138,258 and British Patent 1,146,368. Further, a coupler described in U.S. Pat.No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling, and a U.S. Pat.
It is also preferable to use a coupler having, as a leaving group, a dye precursor group capable of forming a dye by reacting with a developing agent described in 4,777,120. Compounds that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are:
RD 17643, VII-F and 307105, VII-
Patents described in section F, JP-A-57-151944, JP-A-57-1542
No. 34, No. 60-184248, No. 63-37346, No. 63-37350
And those described in U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred. RD No. 11449, 24241, JP-A-61
The bleaching accelerator releasing couplers described in -201247 and the like are effective in shortening the time of processing steps having bleaching ability,
In particular, the effect is great when added to a light-sensitive material using the above-mentioned tabular silver halide grains. As the coupler capable of releasing a nucleating agent or a development accelerator imagewise during development, those described in British Patent Nos. 2,097,140 and 2,131,188, JP-A-59-157638 and JP-A-59-170840 are preferred. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940, by the redox reaction with the oxidized form of the developing agent described in JP-A-1-45687, a fogging agent, a development accelerator ,
Compounds that release a silver halide solvent or the like are also preferred.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and the like, US Pat.
Nos. 38,393, 4,310,618, etc., multi-equivalent couplers described in JP-A-60-185950, DIR redox compound releasing couplers described in JP-A-62-24252, etc., DIR coupler releasing couplers, DIR coupler releasing redox compounds Or a DIR redox-releasing redox compound, a coupler releasing a dye capable of recoloring after detachment described in European Patent Nos. 173,302A and 313,308A, a ligand releasing coupler described in U.S. Pat. -75747 Leuco dye releasing couplers, U.S. Pat.
No. 181 which emits a fluorescent dye.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in U.S. Pat. No. 2,322,027. Specific examples of high-boiling organic solvents having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl)
Esters of isophthalate, bis (1,1-diethylpropyl) phthalate, etc., phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, dichloropropyl
2-ethylhexylphenylphosphonate, etc.), benzoates (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctylase) Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate), aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline); and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). As the auxiliary solvent, the boiling point is about 30 ℃ or more, preferably 50 ℃
An organic solvent having a temperature of about 160 ° C. or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate,
Examples include methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363 and West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol and JP-A-63-257747, JP-A-62-272248,
And JP-A-1-80941, 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate,
It is preferable to add various preservatives or fungicides such as phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole. Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643, page 28, No. 18716, page 647, right column to page 648, left column, and No. 307105, page 879. In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and particularly preferably 16 μm or less. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness is controlled at 25 ° C and relative humidity of 55% (2 days)
And the film swelling speed T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering by A. Green et al.
(Photogr.), 19 vol., No. 2, by using a 124 type described on pages to 129 Swellometer (swelling meter) can be measured, T _1/2 in color developer 30 90% of the maximum swelling film thickness reached when treated at ℃, 3 minutes and 15 seconds is defined as the saturated film thickness, and it is defined as the time 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 by changing the aging conditions after coating. The swelling ratio is 1
50-400% is preferred. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness-film thickness).
/ Can be calculated according to the film thickness. The photosensitive material of the present invention has a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
It is preferable to provide a hydrophilic colloid layer (referred to as a back layer) of μm. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent, and the like. The swelling ratio of the back layer is preferably from 150 to 500%.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine-based color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used. Representative examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 3-methylaniline. -4-Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl -β-methoxyethylaniline, 4-amino-3-methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N-
(3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (2-hydroxypropyl) aniline, 4-
Amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-
Hydroxypropyl) aniline, 4-amino-3-propyl
-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-methyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-ethyl-N -(4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl
-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-
Hydroxypentyl) aniline, 4-amino-3-methyl-N
-(5-hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-N, Examples include N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and sulfates, hydrochlorides or p-toluenesulfonates thereof. Among them, in particular, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl)
Aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, and their hydrochlorides, p-toluenesulfonates or sulfates are preferred. These compounds can be used in combination of two or more depending on the purpose. The color developing solution may be a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It generally contains an inhibitor or an antifoggant. Also, if necessary,
Various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, catecholsulfonic acid,
Organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-phenyl-3-
Auxiliary developing agents such as pyrazolidone, viscosity-imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, Diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-
Hydroxyethylidene-1,1-diphosphonic acid, nitrilo-
N, N, N-trimethylenephosphonic acid, ethylenediamine-N,
N, N, N-tetramethylenephosphonic acid, ethylenediamine-
Di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as typical examples.

Next, processing solutions and processing steps of the color reversal photosensitive material of the present invention other than the color developing solution will be described. The steps from black development to color development in the processing steps of the color reversal photosensitive material of the present invention are as follows. 1) Black-and-white development-water washing-reversal-color development 2) Black-white development-water washing-light reversal-color development 3) Black-white development-water washing-color development All of the washing steps 1) to 3) are described in US Pat.
Instead of the rinsing step described in JP-A No. 04,616, simplification of treatment and reduction of waste liquid can be achieved. Next, steps after the color development will be described. 4) Color development-Adjustment-Bleaching-Fixing-Rinse-Stable 5) Color development-Water washing-Bleaching-Fixing-Rinse-Stable 6) Color development-Adjustment-Bleaching-Rinse-Fix-Rinse-Stable 7) Color development-Rinse -Bleaching-Washing-Fixing-Washing-Stable 8) Color development-Bleaching-Fixing-Washing-Stable 9) Color development-Bleaching-Bleaching-Washing-Stable 10) Color development-Bleaching-Bleaching-Fixing-Washing-Stable 11) Color development-Bleaching-Rinse-Fix-Rinse-Stable 12) Color development-Adjustment-Bleach fix-Rinse-Stable 13) Color development-Rinse-Bleach fix-Rinse-Stable 14) Color development-Bleach fix-Rinse- Stable 15) Color development-fixing-bleach-fixing-rinsing-stabilizing In the processing steps 4) to 15), the washing step immediately before the stabilizing step may be omitted, and conversely, the stabilizing step of the final step is not performed. You may. Any one of the above steps 1) to 3) and one of the 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 for the black-and-white developer used in the present invention. As a developing agent, dihydroxybenzenes (for example, hydroquinone) and 3-pyrazolidones (for example, 1-phenyl-
3-pyrazolidone), aminophenols (for example, N
-Methyl-p-aminophenol), 1-phenyl-3
Pyrazolines, ascorbic acid and U.S. Pat.
Heterocyclic compounds in which a 1,2,3,4-tetrahydroquinoline ring and an indole ring described in JP-A-67,872 are condensed or the like can be used alone or in combination. The black-and-white developer used in the present invention may further include a preservative (eg, sulfite, bisulfite, etc.), a buffer (eg, carbonate, boric acid, borate, alkanolamine), an alkali agent (eg, Hydroxides, carbonates), dissolving tablets (eg, polyethylene glycols, esters thereof), pH adjusters (eg, organic acids such as acetic acid),
Sensitizers (eg, quaternary ammonium salts), development accelerators,
A surfactant, an antifoaming agent, a hardening agent, a viscosity imparting agent and the like can be contained. The black-and-white developer used in the present invention must contain a compound that acts as a silver halide solvent, and the sulfite usually added as a preservative serves the role. Examples of the sulfite and other silver halide solvents that can be used include KSCN, NaSC
N, 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 , Na ₂ S ₂ O _{3 and the} like. The pH value of the developer thus adjusted is selected to be sufficient to provide the desired density and contrast, but is in the range of about 8.5 to about 11.5. In order to perform sensitization processing using such a black-and-white developer, it is usually sufficient to extend the time up to about three times the standard processing. At this time, if the processing temperature is increased, the extension time for the sensitization processing can be reduced.

The color developing solution and the black-and-white developing solution generally have a pH of 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed.
Generally, the amount is 3 liters or less per square meter of the light-sensitive material, and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenisher. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [capacity of treatment liquid (cm ³ )] The above-mentioned aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. It is. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, 63-216050 can be mentioned. Reducing the aperture ratio is not only in both the color development and black-and-white development steps, but also in the subsequent steps, for example, bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer. The reversal bath used after black-and-white development can contain a known fogging agent. That is, stannous ion-organic phosphoric acid complex salt (U.S. Pat. No. 3,617,282), stannous ion organic phosphonocarboxylic acid complex salt (JP-B-56-32616), stannous ion-
Aminopolycarboxylic acid complex salt (US Pat. No. 1,209,0
No. 50), stannic ion complex salts, borohydride compounds (US Pat. No. 2,984,567),
Heterocyclic amine borane compounds (British Patent No. 1,011,0)
No. 00) and the like. The pH of the fogging bath (reversal bath) ranges from an acidic side to an alkaline side, and is in a range of pH 2 to 12, preferably 2.5 to 10, and particularly preferably 3 to 9.
Light reversal treatment by re-exposure may be performed instead of the reversal bath, and the reversal step can 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 or bleach-fixing after color development. These processes may be performed immediately after the color development without going through other processing steps,
In order to prevent unnecessary post-development and air fogging, to reduce the amount of color developing solution brought into the desilvering process, and to use in photographic materials such as sensitizing dyes and dyes contained in photographic materials and photographic materials. In order to wash out and detoxify the impregnated color developing agent, the color developing process may be followed by a bleaching process or a bleach-fixing process after processing steps such as stopping, adjusting, and washing with water.

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two successive bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of a polyvalent metal such as iron (III), peracids, quinones, and nitro compounds are used. Typical bleaching agents are organic complex salts of iron (III),
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid Etc. can be used. Of these, ethylenediaminetetraacetate (III) complex salt and 1,3-diaminopropanetetraacetate (I
II) Iron (III) aminopolycarboxylate complex salts such as complex salts are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but the processing can be carried out at a lower pH for speeding up the processing. Bleach,
A bleaching accelerator can be used in the bleach-fixing solution and the prebath thereof, if necessary. Specific examples of useful bleach accelerators are described in the following specification: US Pat.
No. 3,858, West German Patent Nos. 1,290,812, 2,059,988,
JP-A Nos. 53-32736, 53-57831, 53-37418, 53
-72623, 53-95630, 53-95631, 53-104232
No. 53-124424, No. 53-141623, No. 53-28426,
Research Disclosure No.17129 (July 1978
Compounds having a mercapto group or a disulfide group described in JP-A-50-140129; Japanese Patent Publication Nos. 45-8506 and 52-20832, 53
-32735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715, iodide salts described in JP-A-58-16,235; West German Patents 966,410, 2,748,430
No. 45-883
Polyamine compound described in No. 6; Other JP-A-49-40,943
Nos. 49-59,644, 53-94,927, 54-35,727
Compounds described in Nos. 55-26,506 and 58-163,940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and particularly preferred are the compounds described in U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95,630. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, specifically acetic acid, propionic acid, hydroxyacetic acid and the like.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodides. Is common, and in particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, an adduct of carbonyl bisulfite or a sulfinic acid compound described in European Patent No. 294769A is preferable. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution. The total time of the desilvering step is preferably shorter as long as the desilvering failure does not occur. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. Further, the processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to
45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented. In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening the stirring, a method of impinging a jet of a processing solution on an emulsion surface of a photosensitive material described in JP-A-62-183460, or a method of stirring using a rotating means described in JP-A-62-183461. A method for improving the effect, a method for moving the photosensitive material while bringing the wiper blade provided in the solution into contact with the emulsion surface, and making the emulsion surface turbulent to improve the stirring effect, and a circulation of the entire processing solution. There is a method of increasing the flow rate. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator. Automatic developing machines used in the light-sensitive material of the present invention are described in JP-A-60-191257, JP-A-60-191258 and JP-A-60-1912.
It is preferable to have the photosensitive material conveying means described in No. 59. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing solution from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (the number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely.
Of these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture a.
nd Television Engineers, Vol. 64, pp. 248-253 (May, 1955). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, such a problem is solved by
The method for reducing calcium ions and magnesium ions described in JP-A-62-288,838 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8,542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology"
(1982) The Fungicide described in "Encyclopedia of Bactericidal and Fungicides" (ed. 1986) edited by the Japan Society of Industrial Technology, Japan Society of Bacteria and Fungi. The pH of the washing water in the processing of the photosensitive material of the present invention is 4
-9, preferably 5-8. Washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, application, etc.
In general, 20 seconds to 10 minutes at 15 to 45 ° C, preferably 25 to 40 ° C
Selects a range of 30 seconds to 5 minutes. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization treatment, any of the known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be used. Further, after the water washing treatment, a stabilization treatment may be further carried out. As an example, a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography, is exemplified. be able to. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.
The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step. In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, U.S. Pat.
Indoaniline compounds described in No. 42,597, No. 3,342,5
No. 99, Research Disclosure No. 14,850 and 1
Examples thereof include Schiff base compounds described in 5,159, aldol compounds described in 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628. The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones as necessary for the purpose of accelerating color development.
Typical compounds are JP-A-56-64339, JP-A-57-144547,
And No. 58-115438. The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to.

[0122]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. (Example) Preparation of Sample 101 A multilayer color photosensitive material comprising the following layers was prepared on an undercoated cellulose triacetate film support having a thickness of 127 µm to prepare Sample 101. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the use described.

First layer: Antihalation layer Black colloidal silver 0.20 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 Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 3 mg High boiling organic solvent Oil-3 0.1 g Dye D-4 0.4 mg

Third layer: Intermediate layer A fine-grain silver iodobromide emulsion whose surface and inside are fogged (average particle size: 0.06 μm, variation coefficient: 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-1 0.15 g coupler C-2 0.05 g coupler C-30 0.05g Coupler C-9 0.05g Compound Cpd-C 10mg High boiling organic solvent Oil-2 0.1g Additive P-1 0.1g

Fifth layer: Medium-speed red-sensitive emulsion layer Emulsion B Silver amount 0.2 g Emulsion C silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-30 0.2 g High boiling organic solvent Oil-2 0.1 g Additive P-1 0.1 g

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.3 g Coupler C-2 0.1 g Coupler C-3 0.7 g Additive P-1 0.1g

Seventh layer: Intermediate layer Gelatin 0.6 g Additive M-1 0.3 g Color-mixing inhibitor Cpd-I 2.6 mg Ultraviolet absorber U-1 0.01 g Ultraviolet absorber U-2 0.002 g Ultraviolet absorption Agent U-5 0.01 g Dye D-1 0.02 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 5 mg High boiling organic solvent Oil-1 0.02 g

Eighth layer: Intermediate layer A silver iodobromide emulsion whose surface and inside are fogged (average particle size: 0.06 μm, variation coefficient: 16%, AgI content: 0.3 mol%) Silver amount: 0.02 g Gelatin: 1 0.0g Additive P-1 0.2g Color mixture inhibitor Cpd-A 0.1g

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 0.5 g Coupler C-4 0.1 g Coupler C-70 0.05g Coupler C-8 0.20g Compound Cpd-B 0.03g Compound Cpd-C 10mg Compound Cpd-D 0.02g Compound Cpd-E 0.02g Compound Cpd-F 0.02g Compound Cpd-G 0.02g High Boiling organic solvent Oil-1 0.1 g High boiling organic solvent Oil-2 0.1 g

Tenth Layer: Medium-Sensitive Green-Sensitive Emulsion Layer Emulsion G Silver Amount 0.3 g Emulsion H Silver Amount 0.1 g Gelatin 0.6 g Coupler C-4 0.1 g Coupler C-7 0.2 g Coupler C-80 .1 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 organic solvent Oil-2 0.01 g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.5 g Gelatin 1.0 g Coupler C-4 0.3 g Coupler C-7 0.1 g Coupler C-8 0.1 g Compound Cpd-B0 0.08 g Compound Cpd-C 5 mg Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-J 5 mg Compound Cpd-K 5 mg High boiling organic solvent Oil -1 0.02 g High boiling organic solvent Oil-2 0.02 g

The twelfth layer: the middle layer gelatin 0.6 g

Thirteenth layer: Yellow filter layer Yellow colloidal silver Amount of silver 0.07 g Gelatin 1.1 g 0.01 g of color mixture inhibitor Cpd-A 0.01 g of high boiling organic solvent Oil-1 0.01 g of fine crystalline solid dispersion of dye E-2 Thing 0.05g

Fourteenth layer: middle layer gelatin 0.6 g

Fifteenth 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 C-5 0.6 g Coupler C-60 .1g

Sixteenth layer: Medium-sensitivity blue-sensitive emulsion layer Emulsion L silver amount 0.1 g Emulsion M silver amount 0.4 g gelatin 0.9 g coupler C-5 0.4 g coupler C-6 0.1 g

17th layer: High-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.4 g Gelatin 1.2 g Coupler C-5 0.3 g Coupler C-6 0.6 g

Eighteenth layer: First protective layer Gelatin 0.7 g UV absorber U-1 0.2 g UV absorber U-2 0.05 g UV absorber U-5 0.3 g Formalin scavenger Cpd-H 0.4 g Dye D-1 0.1 g Dye D-2 0.05 g Dye D-3 0.1 g

Nineteenth layer: Second protective layer Colloidal silver Silver content 0.1 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver content 0.1 g Gelatin 0.4 g

Twentieth layer: Third protective layer Gelatin 0.4 g Polymethyl methacrylate (average particle size 1.5 μ) 0.1 g Copolymer of methyl methacrylate and acrylic acid 4: 6 (average particle size 1.5 μ) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g

To all the emulsion layers, additives F-1 to F-8 were added in addition to the above composition. Further, in addition to the above composition, gelatin hardener H-1 and surfactants W-3, W-4, W-5 and W-6 for coating and emulsification were added to each layer. Further, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and butyl p-benzoate were added as preservatives and fungicides.

[0144]

[Table 3]

[0145]

[Table 4]

[0146]

[Table 5]

[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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[0155]

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[0156]

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[0157]

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[0158]

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[0159]

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[0160]

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(Preparation of Samples 102 to 114) Sample 101
In place of the couplers C-5 and C-6 added to the fifteenth, sixteenth, and seventeenth layers, the couplers of the present invention shown in Table 6 were equimolarly replaced. Sample 1 was prepared in the same manner except that the compound of the present invention shown in Table 6 was replaced by an equimolar amount instead of the added color mixing inhibitor CpdA.
Nos. 02 to 114 were produced.

[0162]

[Table 6]

After the obtained samples 101 to 114 were cut into strips, they were exposed to wedges and subjected to the following development processing steps. The MTF value was measured to evaluate the sharpness of the blue-sensitive layer, the red-sensitive layer, and the green-sensitive layer. The MTF value is described in detail in TH James, "Theory of Photographic Processing", 4th edition, Macmillan. Further, as an evaluation of the processing factor dependence of these samples, the dependence of the amount of sodium sulfite in the color developing solution in the following processing steps was examined. Prepare a color developing solution in which the amount of sodium sulfite was changed to 5.4 g and 7.7 g in 1 liter, and leave the other processing solutions in the following processing steps to develop strips exposed to wedge exposure with white light. The blue-sensitive layer obtained after the treatment was processed, and the width of change in sensitivity at a density of fog + 1.5 in the characteristic curve of the blue-sensitive layer was measured. The results are summarized in Table 7.

[0164]

[Table 7]

As is evident from Table 7, the sharpness is improved when the conventional known yellow coupler is used in combination with the color mixture inhibitor of the present invention, but the dependency on the amount of sodium sulfite is increased. In contrast, when the yellow coupler of the present invention was used, it was found that the sharpness was further improved and the dependence on the amount of sodium sulfite was reduced.
In particular, the sample 107 was small in processing dependency and could obtain good results. These results were obtained only with the combination of the present invention. (Development processing step) Processing step Time Temperature First development 6 minutes 38 ° C Rinse 2 minutes 38 ° C Inversion 2 minutes 38 ° C Color development 6 minutes 38 ° C Adjustment 2 minutes 38 ° C Bleaching 6 minutes 38 ° C Fixed 4 minutes 38 ° C Rinse 4 minutes 38 ° C Stable 1 minute 25 ° C

The composition of each processing solution was as follows. [First developer] Nitrilo-N, N, N-trimethylenephosphonic acid · pentasodium salt 1.5 g diethylenetriaminepentaacetic acid · pentasodium salt 2.0 g sodium sulfite 30 g hydroquinone potassium monosulfonate 20 g potassium carbonate 15 g bicarbonate Sodium 12g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide 2.0mg Diethylene glycol 13g Add water 1000ml pH 9 .60 pH was adjusted with hydrochloric acid or potassium hydroxide.

[Inversion liquid] Nitrilo-N, N, N-trimethylenephosphonic acid · pentasodium salt 3.0 g stannous chloride · dihydrate 1.0 g p-aminophenol 0.1 g sodium hydroxide 8 g glacial acetic acid 15 ml Water was added and 1000 ml pH 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide.

[Color developing solution] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 2.0 g Sodium sulfite 7.0 g Trisodium phosphate dodecahydrate 36 g Potassium bromide 1.0 g Potassium iodide 90 mg sodium hydroxide 3.0 g citrazic acid 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 11 g 3,6- Dithiaoctane-1,8-diol 1.0 g Water was added, 1000 ml pH 11.80 The pH was adjusted with hydrochloric acid or potassium hydroxide.

[Preparation Solution] Ethylenediaminetetraacetic acid disodium salt dihydrate 8.0 g sodium sulfite 12 g 1-thioglycerol 0.4 g formaldehyde sodium bisulfite adduct 30 g Water was added to add 1,000 ml, and the pH was 6.20. Adjusted with hydrochloric acid or sodium hydroxide.

[Bleaching Solution] Ethylenediaminetetraacetic acid / disodium salt / dihydrate 2.0 g Ethylenediaminetetraacetic acid / Fe (III) / ammonium / dihydrate 120 g Potassium bromide 100 g Ammonium nitrate 10 g 5.70 pH was adjusted with hydrochloric acid or sodium hydroxide.

[Fixing solution] Ammonium thiosulfate 80 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to the mixture, and the pH was adjusted with hydrochloric acid or aqueous ammonia.

[Stabilizing Solution] Benzoisothiazolin-2-one 0.02 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 g 1000 ml with water added, pH 7.0

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 7/36 G03C 7/392

Claims (1)

(57) [Claims] 1. A silver halide color photographic material having at least one blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. At least one of the yellow dye-forming couplers represented by the following formula (Ya) or (Yb), and at least one layer constituting the photosensitive material is represented by the following formula (H): A silver halide color photographic light-sensitive material comprising at least one compound selected from the group consisting of: General formula (Ya) General formula (Yb) In the formula, X ₁ and X ₂ each represent an alkyl group, an aryl group or a heterocyclic group, X ₃ represents an organic residue forming a nitrogen-containing heterocyclic group together with> N—, and Y represents an aryl group or a heterocyclic group. Z represents a group which is released when the coupler represented by the general formula reacts with an oxidized developing agent. General formula (H) In the formula, X represents —N (R ¹ ) R ³ or —OR ⁴ , wherein R ¹ is a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R ³ and R ⁴ are hydrogen atoms Or a group which is removed under alkaline conditions. R ² is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a nitro group or a hydrazino group, and X and R ² may be linked to form a ring. R ⁵ represents a hydrogen atom, an alkyl group or a group removed under alkaline conditions. Two or more formulas (H) may be bonded to each other at the R ¹ , R ² or R ⁵ portion to form an oligomer or a polymer. G is -CO-, -COCO-, -S
O _2- , -SO-, -CON (R ⁶ )-, -COO-,-
COCON (R ⁷ )-, -COCO-, -PO (R ⁸ )
-, -CS- or iminomethylene group, wherein R
⁶ , R ⁷ are a hydrogen atom, an alkyl group or an aryl group, and R ⁸ is an alkyl group or an aryl group. m is 0, 1 or 2, and when it is 2, G may be the same or different.