JPH0519426A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To offer a silver halide color photographic sensitive material imparting higher coloring density and with the color image fastness the, color reproducibility, the graininess and aging preservability of the material improved. CONSTITUTION:At least one photosensitive silver halide emulsion layer is provided on the substrate of a silver halide color photographic sensitive material. A coupler shown by formula I or II is incorporated into the material, and a substantially non-photosensitive particulate silver halide is incorporated into the emulsion layer and/or the adjacent layer close to the substrate. In the formulas, X1 and X2 are respectively alkyls, aryls or heterocyclic rings, X3 is an org. group constituting a nitrogen-contg. heterocyclic ring along with >N-, Y is aryls or heterocyclic rings, and Z is a group to be detached when the coupler reacts with an oxidized developing agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and in particular, in addition to improving color image fastness and color reproducibility by a novel coupler, it further imparts high color density and high sensitivity to improve graininess. The present invention relates to an improved silver halide color photographic light-sensitive material for photography.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material (hereinafter simply referred to as a light-sensitive material), particularly a color light-sensitive material for photographing, gives a high sensitivity and a high color density to obtain an image quality (color reproducibility, There is a demand for a photosensitive material that is excellent in graininess, sharpness) and color image storability.

As a yellow coupler for forming a color photographic image, an acylacetanilide type coupler having an active methylene (methine) group, for example, a benzoylacetanilide type coupler or a pivaloylacetanilide type coupler is generally known. These couplers are known. Since the molecular extinction coefficient of the color-developing dye obtained from (1) is low, the color-developing density is low, so that there is a problem that the coating amount per unit area of the light-sensitive material must be increased. Furthermore, it is not possible to satisfy all of these, such as coupling activity, color image fastness, and hue, and there has been a demand for the development of a coupler that combines these.

As a malondiamide type coupler similar to the yellow coupler of the present invention, in contrast to the above-mentioned acylacetanilide type coupler, for example, French Patent No. 1,558,4.
No. 52, the coupler disclosed in the patent is a so-called O-cleavable two-equivalent coupler in which the active position has a group capable of leaving via an oxygen atom, and is diffusible. It is mainly a coupler. Further, as a malondiamide type coupler and a functional coupler, a development inhibitor releasing type (DIR) coupler is disclosed in, for example, JP-A-52-52.
69624, US Pat.
149,886, 4,477,563, and JP-A-1-250950. However, US Pat. Nos. 4,149,886 and 4,477,563 do not describe specific compounds relating to the present invention. Further, in this, there is no description of specific effects in Japanese Patent Laid-Open No. 52-69624. Moreover, regarding the couplers described in each of the above-mentioned patents, although the effect of some improvement can be seen when used, the image storability, particularly when stored under high temperature and high humidity, the deterioration of fastness is still large. There is a problem that the absorption density of the yellow dye on the long wavelength side (green region) is high and the color reproducibility is deteriorated. It was also found that there is a problem that the coupling activity is low and that it is difficult to use.

On the other hand, it has been disclosed that a layer containing a non-color sensitive fine grain silver halide grain is provided in a light-sensitive material to improve sensitivity or improve graininess and processing stability, and obtain high color density. ing. For example, JP-A-59-16013
No. 5 has at least two emulsion layers having the same color sensitivity and different sensitivities, and each of the two emulsion layers is adjacent to each emulsion layer and contains a non-photosensitive silver halide grain. It is described to install layers. JP-A-60-194
In No. 450, the layer arrangement of each light-sensitive layer is defined, and a non-light-sensitive hydrophilic colloid layer is provided closer to the support of the most sensitive blue-sensitive emulsion layer. It is described that the colloid layer is provided with a layer containing non-color-sensitive fine grain silver halide. In addition, JP-A-61
No. 77848 contains an acylacetanilide type 2-equivalent yellow coupler and contains non-photosensitive fine silver halide grains on the side close to the support, close to the emulsion layer containing monodisperse silver halide grains. It is described that a non-photosensitive colloid layer is provided. Furthermore, JP-A-62-1
No. 187839 discloses a blue-sensitive emulsion layer and a non-light-sensitive layer which is closer to the support than a blue-sensitive emulsion layer or an emulsion layer having a different color sensitivity, and a silver halide emulsion layer which is a non-light-sensitive layer. It is proposed to install.

However, the yellow couplers disclosed in these publications are the above-mentioned benzoylacetanilide type or pivaloylacetanilide type couplers,
As described above, these couplers have low color density,
It is not a coupler that simultaneously satisfies coupling activity, color image fastness, hue and the like. Further, the functional DIR coupler is also a yellow coupler mother nucleus described above, or one using a malondianilide type or indanone type compound, and there are problems in color reproducibility and coupling activity.

Moreover, from these cited publications, no description by which the coupler according to the present invention can be analogized can be found.

[0008]

As described above, in the conventional yellow coupler, the color extinction coefficient of the coloring dye obtained is small, so that the coloring density is low, and the coupling activity, the color image fastness and the hue are high. It was not a coupler that could satisfy all of the above. Further, functional couplers also have problems in color image fastness and hue. Even if these couplers are used to provide a layer containing non-color-sensitive fine silver halide grains to improve the sensitivity or improve graininess and processing stability, the above-mentioned problems cannot be solved. .

Accordingly, the present invention provides a silver halide color photographic light-sensitive material having improved color image fastness and color reproducibility, higher color density, graininess and storability of the light-sensitive material. Especially.

[0010]

The above-mentioned problems can be solved by the means described below.

The silver halide color photographic light-sensitive material according to the present invention is a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support and is represented by the following general formula (I). Alternatively, a substantially non-photosensitive fine grain containing a coupler represented by the following general formula (II) represented by the following chemical formula 8 and being provided in the light-sensitive silver halide emulsion layer and / or the layer adjacent to the support near the support. It is characterized by containing silver halide grains.

[0012]

[Chemical 7] In the formula, X ₁ and X ₂ each represent an alkyl group, an aryl group or a heterocyclic group, Y represents an aryl group or a heterocyclic group, and Z is an oxidized product of a developing agent as the coupler represented by the general formula (I). Represents a group that leaves when reacted with.

[0013]

[Chemical 8] In the formula, X ₃ represents an organic residue forming a nitrogen-containing heterocycle with> N-, Y represents an aryl group or a heterocyclic group,
Z represents a group which leaves when the coupler represented by the general formula (II) reacts with an oxidized product of a developing agent.

The photosensitive silver halide emulsion layer is preferably a blue-sensitive silver halide emulsion layer.

The layer adjacent to the support of the light-sensitive silver halide emulsion layer is preferably a non-light-sensitive layer or a color-sensitive layer other than blue-sensitive.

The silver halide color photographic light-sensitive material according to the present invention is a silver halide color photographic light-sensitive material having two or more silver halide emulsion layers having the same color sensitivity and different sensitivities on a support. It has a layer containing substantially non-photosensitive fine grain silver halide grains adjacent to two halogenated emulsion layers at the same time, and has a coupler represented by the general formula (I) or the general formula (II). It is characterized by containing.

The layer containing the substantially non-photosensitive fine grain silver halide grains is allowed to be non-photosensitive.

Further, the silver halide color photographic light-sensitive material of the present invention has two or more red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers each having different sensitivity on a support. The light-sensitive material is characterized by satisfying all the following conditions (1) to (4) and containing a coupler represented by the general formula (I) or the general formula (II).

(1) The light-sensitive silver halide emulsion layer provided on the side farthest from the support is the most sensitive blue-sensitive silver halide emulsion layer (BH), and (2) the most sensitive. The green-sensitive silver halide emulsion layer (GH) and the most sensitive red-sensitive silver halide emulsion layer (RH) are the same as those described in B above.
Between H and the blue-sensitive silver halide emulsion layer (Bh), which has a lower sensitivity than BH, and (3) with respect to Bh, the farthest side from the support has the lowest sensitivity to red and green. Sensitive and blue sensitive silver halide emulsion layers (RL, respectively)
GL and BL) are absent, and (4) a non-photosensitive layer is provided adjacent to the BH, and the BH and / or the non-photosensitive layer are provided with substantially non-photosensitive fine silver halide grains. contains.

Next, the couplers represented by the general formulas (I) and (II) will be described in detail.

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

When X ₁ and X ₂ represent a heterocyclic group, the heterocyclic group has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms.
And 3 to 12, preferably 5 or 6-membered, saturated or unsaturated, substituted or unsubstituted, and monocyclic or condensed ring containing at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom. Is a heterocyclic group. Examples of the heterocyclic group include 3-pyrrolidinyl,
1,2,4-triazol-3-yl, 2-pyridyl,
4-pyrimidinyl, 3-pyrazolyl, 2-pyrrolyl,
2,4-dioxo-1,3-imidazolidin-5-yl or pyranyl can be mentioned.

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

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

When X ₁ and X ₂ represent an alkyl, aryl or heterocyclic group having a substituent, and when the nitrogen-containing heterocyclic group formed with X ₃ with> N- has a substituent, The following are mentioned as an example of those substituents. A halogen atom (for example, fluorine, chlorine), an alkoxycarbonyl group (having 2 to 30 carbon atoms, preferably 2 to 20. For example, methoxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl),
Acylamino group (having 2 to 30 carbon atoms, preferably 2 to 2 carbon atoms)
0. For example, acetamide, tetradecanamide, 2-
(2,4-di-t-amylphenoxy) butanamide,
Benzamide), sulfonamide group (having 1 to 30 carbon atoms,
Preferably 1-20. For example, methanesulfonamide, dodecanesulfonamide, hexadecylsulfonamide,
Benzenesulfonamide), carbamoyl group (C1
-30, preferably 1-20. For example, N-butylcarbamoyl, N, N-diethylcarbamoyl), N-sulfonylcarbamoyl group (having 1 to 30 carbon atoms, preferably 1 to 30 carbon atoms)
20. For example, N-mesylcarbamoyl, N-dodecylsulfonylcarbamoyl), sulfamoyl group (having 1 carbon atom)
-30, preferably 1-20. For example, N-butylsulfamoyl, N-dodecylsulfamoyl, N-hexadecylsulfamoyl, N-3- (2,4-di-t-amylphenoxy) butylsulfamoyl, N, N-diethylsulfate Famoyl), an alkoxy group (having 1 to 30 carbon atoms,
Preferably 1-20. For example, methoxy, hexadecyloxy, isopropoxy), aryloxy group (C6
-20, preferably 6-10. For example, phenoxy, 4-
Methoxyphenoxy, 3-t-butyl-4-hydroxyphenoxy, naphthoxy), aryloxycarbonyl group (having 7 to 21, preferably 7 to 11 carbon atoms, for example, phenoxycarbonyl), N-acylsulfamoyl group (having 2 carbon atoms). -30, preferably 2-20. For example, N-propanoylsulfamoyl, N-tetradecanoylsulfamoyl), a sulfonyl group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, methanesulfonyl, octanesulfonyl, 4-hydroxyphenylsulfonyl, dodecanesulfonyl), alkoxycarbonylamino group (C1-C1)
30, preferably 1-20. For example, ethoxycarbonylamino), cyano group, nitro group, carboxyl group, hydroxyl group, sulfo group, alkylthio group (having 1 to 3 carbon atoms).
0, preferably 1-20. For example, methylthio, dodecylthio, dodecylcarbamoylmethylthio), a ureido group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, N-phenylureido, N-hexadecylureido), an aryl group (having 6 to 20 carbon atoms, preferably 6 carbon atoms). -10. For example, phenyl, naphthyl, 4-methoxyphenyl), a heterocyclic group (having 1 to 20 carbon atoms, preferably 1 to 10. As a hetero atom, for example, at least one nitrogen, oxygen or sulfur is included 3 to 12, Preferably a 5- or 6-membered monocyclic or condensed ring such as 2-pyridyl, 3-pyrazolyl, 1-pyrrolyl, 2,4-dioxo-1,3-imidazolidin-1-yl, 2-benzoxazoli. Group, morpholino, indolyl), alkyl group (1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, straight chain, branched chain or ring) , And saturated or unsaturated alkyl, such as methyl, ethyl,
Isopropyl, cyclopropyl, t-pentyl, t-octyl, cyclopentyl, t-butyl, s-butyl, dodecyl, 2-hexyldecyl), acyl group (having 1 to 1 carbon atoms)
30, preferably 2-20. For example, acetyl, benzoyl), an acyloxy group (having 2 to 30 carbon atoms, preferably 2 carbon atoms)
~ 20. For example, propanoyloxy, tetradecanoyloxy), an arylthio group (having 6 to 20 carbon atoms, preferably 6 to 10. For example, phenylthio, naphthylthio), a sulfamoylamino group (having 0 to 30 carbon atoms, preferably 0).
~ 20. For example, N-butylsulfamoylamino, N-
Dodecylsulfamoylamino, N-phenylsulfamoylamino) or N-sulfonylsulfamoyl group (having 1 to 30, preferably 1 to 20 carbon atoms, for example N-
Mesyl sulfamoyl, N-ethanesulfonyl sulfamoyl, N-dodecanesulfonyl sulfamoyl, N
-Hexadecanesulfonylsulfamoyl). The above substituents may further have a substituent. Examples of the substituent include the substituents mentioned here.

Preferred substituents in the above are alkoxy group, halogen atom, alkoxycarbonyl group, acyloxy group, acylamino group, sulfonyl group, carbamoyl group, sulfamoyl group, sulfonamide group, nitro group, alkyl group or aryl group. To be taken.

In formulas (I) and (II), when Y represents an aryl group, Y is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. Phenyl and naphthyl groups are typical examples.

When Y represents a heterocyclic group in the general formulas (I) and (II), Y has the same meaning as described above 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, X ₁
The examples of the substituents having a substituent include the substituents listed above. Preferred examples of the substituent of Y include:
One of the substituents is a halogen atom, an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group, a sulfonyl group, an N-sulfonylsulfamoyl group, an N-acylsulfamoyl group, an alkoxy group, an acylamino group, N-
This is when it is a sulfonylcarbamoyl group, a sulfonamide group or an alkyl group.

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

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

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

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

When Z represents a nitrogen-containing heterocyclic group bonded to the coupling position at a nitrogen atom, the nitrogen-containing heterocyclic group has a carbon number of 1 to 15, preferably 1 to 10 and has 5 or 6 members. It is preferably a cyclic, substituted or unsubstituted, saturated or unsaturated, and monocyclic or condensed heterocyclic group. The hetero atom may contain an oxygen atom or a sulfur atom in addition to the nitrogen atom. Specific preferred examples of the heterocyclic group are 1-pyrazolyl, 1-imidazolyl, pyrrino, 1,2,3-triazol-2-yl,
1,2,3-triazol-1-yl, benzotriazolyl, benzimidazolyl, imidazolidine-2,4-
Dione-3-yl, oxazolidin-2,4-dione-
3-yl, 1,2,4-triazolidine-3,5-dione-4-yl, imidazolidin-2,4,5-trion-3-yl, 2-imidazolinone-1-yl, 3,5-
Examples include dioxomorpholino or 1-indazolyl. When these heterocyclic groups have a substituent, examples of the substituent include the substituents listed as the substituents which the group represented by 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,
Aryloxycarbonyl group, alkylthio group, acylamino group, sulfonamide group, aryl group, nitro group,
This is when it is a carbamoyl group, a cyano group or a sulfonyl group.

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

When Z represents a heterocyclic oxy group, the heterocyclic group part has at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. It is a substituted or unsubstituted, saturated or unsaturated, and monocyclic or condensed-ring heterocyclic group containing 3 to 12 or more, preferably 5 or 6-membered rings. Examples of the heterocyclic oxy group include a pyridyloxy group, a pyrazolyloxy group, or a furyloxy group. When it has a substituent, examples of the substituent include the substituents listed as the substituents which the group represented by X ₁ may have. Among them, as a preferable substituent, one substituent is an alkyl group, an aryl group, a carboxyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group,
Alkylthio group, acylamino group, sulfonamide group,
When it is a nitro group, a carbamoyl group, or a sulfonyl group.

When Z represents a heterocyclic thio group, the heterocyclic group moiety has at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Examples of the heterocyclic thio group which is a substituted or unsubstituted, saturated or unsaturated, and monocyclic or condensed-ring heterocyclic group having 3 to 12, preferably 5 or 6 membered rings, include a tetrazolylthio group,
Examples include 1,3,4-thiadiazolylthio group, 1,3,4-oxadiazolidylthio group, 1,3,4-triazolylthio group, benzimidazolylthio group, benzothiazolylthio group, and 2-pyridylthio group. To be When it has a substituent, examples of the substituent include the substituents listed as the substituents which the group represented by X ₁ may have. Among them, preferred substituents are
At least one of the substituents is an alkyl group, an aryl group, a carboxyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an acylamino group, a sulfonamide group, a nitro group, a carbamoyl group, a heterocyclic group or This is when it is a sulfonyl group.

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

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

When Z represents an alkylthio group, the alkylthio group has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
A straight-chain, branched, saturated or unsaturated, and substituted or unsubstituted alkylthio group. When it has a substituent, examples of the substituent include the substituents listed as the substituents which the group represented by X ₁ may have.

Next, particularly preferred ranges of the couplers represented by the general formulas (I) and (II) will be described below.

The group represented by X ₁ in formula (I) is preferably an alkyl group. Particularly preferably, it is an alkyl group having 1 to 10 carbon atoms.

The group represented by Y in the general formulas (I) and (II) is preferably an aromatic group. Particularly preferred is a phenyl group having at least one substituent at the ortho position. The explanation of the substituents includes those enumerated as the substituents which Y may have when it is an aromatic group. The example of a preferable substituent is also the same.

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

Among the couplers represented by formula (I) or (II), preferred couplers are represented by the following chemical formulas 9 to 9:
A coupler represented by the general formula (III), (IV) or (V) of Chemical formula 11.

[0047]

[Chemical 9]

[0048]

[Chemical 10]

[0049]

[Chemical 11] In the formula, Z has the same meaning as described in the general formula (I),
X ₄ represents an alkyl group, X ₅ represents an alkyl group or an aromatic group, Ar represents a phenyl group having at least one substituent at the ortho position, and X ₆ represents —C (R ₁ R ₂ ).
It represents an organic residue forming a -N <with a nitrogen-containing Hajime Tamaki (monocyclic or condensed), X ₇ is _{-C (R 3) = C (} R
₄ ) represents an organic residue forming a nitrogen-containing heterocyclic group (monocycle or condensed ring) together with -N <, and R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or a substituent.

In the general formulas (III) to (V), X ₄ to
The detailed description and the preferred range of the groups represented by X ₇ , Ar and Z have the same meanings as those of the corresponding groups in the descriptions of the general formulas (I) and (II). When R _{1 to} R ₄ represent a substituent, the examples of the substituent that X ₁ may have are listed.

Among the above-mentioned general formulas (III) to (V), particularly preferred couplers are the couplers represented by the general formula (IV) or (V).

The couplers represented by the general formulas (I) to (V) have a divalent or higher valent group in the groups represented by X _{1 to} X ₇ , Y, Ar, R _{1 to} R ₄ and Z. Dimers or higher multimers (eg telomers or polymers) that bind to each other may also be formed. In this case, the number of carbon atoms shown in each of the above substituents may be out of the specified range.

The couplers represented by formulas (I) to (V) are preferably non-diffusion type couplers. The diffusion-resistant coupler is a coupler having a group (diffusion-resistant group) in the molecule that increases the molecular weight sufficiently in order to immobilize the molecule in the added layer. As the diffusion resistant group, an alkyl group having a total carbon number of 8 to 30, preferably 10 to 20 or an aryl group having a substituent having a total carbon number of 4 to 20 is usually used. These diffusion resistant groups may be substituted in any of the molecules, or may have a plurality of groups.

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

[0055]

[Chemical 12]

[0056]

[Chemical 13]

[0057]

[Chemical 14]

[0058]

[Chemical 15]

[0059]

[Chemical 16]

[0060]

[Chemical 17]

[0061]

[Chemical 18]

[0062]

[Chemical 19]

[0063]

[Chemical 20]

[0064]

[Chemical 21]

[0065]

[Chemical formula 22]

[0066]

[Chemical formula 23]

[0067]

[Chemical formula 24]

[0068]

[Chemical 25]

[0069]

[Chemical formula 26]

[0070]

[Chemical 27]

[0071]

[Chemical 28]

[0072]

[Chemical 29]

[0073]

[Chemical 30]

[0074]

[Chemical 31]

[0075]

[Chemical 32]

[0076]

[Chemical 33] Note that Y-56 and Y-57 in Chemical formula 30,
In Y-58 in and the Y64 in Chemical formula 33, "}" indicates that the substituent is substituted at the 5-position or 6-position of the benzotriazolyl group.

The yellow couplers represented by the general formulas (I) to (V) used in the present invention can be synthesized by the following routes. Synthesis example-1

[0078]

[Chemical 34] Synthetic Compound A 357.5 g (3.0 mol) of Intermediate B, Compound B39
1.2 g of ethyl acetate was added to 6.3 g (3.0 mol),
It was dissolved in 0.6 liter of dimethylformamide. 631 g of dicyclohexylcarbodiimide with stirring
A solution of (3.06 mol) in acetonitrile (400 ml) was added dropwise at 15 to 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. The organic layer was dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure to obtain 692 g of Intermediate A as an oily substance.
(98.9%) was obtained.

692 g (2.97 mol) of intermediate A was dissolved in 3 liters of ethyl alcohol, and the mixture was stirred at 75
430 g of 30% sodium hydroxide was added dropwise at -80 ° C. 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 3 at 40 to 50 ° C. with stirring.
00 ml was added dropwise. After stirring for 1 hour at the same temperature, the crystals were collected by filtration to obtain 579 g (95%) of intermediate B. (Decomposition point 127 ° C.) Synthesis of Intermediate D 45.1 g (0.22 mol) of Intermediate B, Compound C86.
6 g (0.2 mol) was dissolved in 400 ml of ethyl acetate and 200 ml of dimethylacetamide. While stirring, 66 g (0.32 mol) of dicyclohexylcarbodiimide
Acetonitrile solution (100 ml) was added dropwise at 15 to 30 ° C. After reacting at 20 to 30 ° C. for 2 hours, the precipitated dicyclohexylurea was collected by filtration.

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

This oily matter was mixed with 100 ml of ethyl acetate and n-
Crystallization from 300 ml of hexane gave 108 of Intermediate D.
g (87.1%) was obtained. The melting point of this intermediate D is 132
˜134 ° C., and its elemental analysis values are as shown in Table 1 below.

[0082]

[Table 1] 49.6 g (0.08 mol) of a synthetic intermediate D of the exemplified coupler Y-7 was dissolved in 300 ml of dichloromethane. Sulfuryl chloride 1 in this solution
1.4 g (0.084 mol) was added dropwise with stirring at 10 to 15 ° C.

After reacting for 30 minutes at the same temperature, 200 g 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. Dichloromethane was distilled off under reduced pressure to obtain 47 g of an oily substance.

47 g of this oily substance was added to 200 g of acetonitrile.
It was dissolved in ml and 28.4 g (0.22 mol) of compound D and 22.2 g (0.22 mol) of triethylamine were added thereto with stirring. After reacting for 4 hours at 40 to 50 ° C., the mixture was poured into 300 ml of water, and the precipitated oily substance was extracted with 300 ml of ethyl acetate. The organic layer was washed with 200 g of a 5% aqueous sodium hydroxide solution, and then twice more with 300 ml of water.
Washed with water. The organic layer was acidified with dilute hydrochloric acid, washed twice with water, and concentrated under reduced pressure to give a residue. (Yield 70 g) The obtained oily substance was mixed with 50 ml of ethyl acetate and 100 m of n-hexane.
Crystallization with a mixed solution of 1
7.8 g (80%) was obtained. This exemplary coupler Y-7 is
The melting point is 145 to 147 ° C., and the elemental analysis values are as shown in Table 2 below.

[0085]

[Table 2] Synthesis example-2

[0086]

[Chemical 35] Synthesis of Intermediate E 90.3 g (0.44 mol) of Intermediate B, Compound E187
g (0.4 mol) was dissolved in 500 ml of ethyl acetate and 300 ml of dimethylformamide. While stirring, a solution of 131.9 g (0.64 mol) of dicyclohexylcarbodiimide in 15 to 30 of acetonitrile (200 ml) was added.
Dropwise at ° C.

After reacting at 20 to 30 ° C. for 2 hours, the precipitated dicyclohexylurea was collected by filtration. After 500 ml of ethyl acetate and 600 ml of water were added to the filtrate to remove the aqueous layer, the organic layer was washed twice with water. The organic layer was dried over anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure, and an oily substance was added to the residue.
81 g was obtained.

This was dissolved by heating with 1.5 l of n-hexane, and the insoluble matter was removed by filtration. The n-hexane solution was cooled with water, and the precipitated intermediate E was collected by filtration. This intermediate E
Has a yield of 243.4 g (93%) and a melting point of 103-105.
C., and its elemental analysis values are as shown in Table 3 below.

[0089]

[Table 3] 39.3 g (0.06 mol) of the synthetic intermediate E of the exemplified coupler Y-16 was dissolved in 200 ml of dichloromethane. Sulfuryl chloride 8.
7 g (0.064 mol) was added dropwise with stirring at 10 to 15 ° C.

After reacting for 30 minutes at the same temperature, 200 g of a 4% aqueous sodium hydrogencarbonate 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. Dichloromethane was distilled off under reduced pressure to obtain 41.3 g of an oily substance.

41.3 g of this oily substance was added to acetonitrile 1
Dissolve in 00 ml, 200 ml of dimethylacetamide,
With stirring, 20.8 g (0.16 mol) of compound D and 16.2 g of triethylamine were added. 3 at 30-40 ° C
After reacting for time, it was poured into 400 ml of water, and the precipitated oily substance was extracted with 300 ml of ethyl acetate. 2% organic layer
After washing with 300 g of aqueous sodium hydroxide solution, 2 more
It was washed with water twice. The organic layer was acidified with diluted hydrochloric acid, washed twice with water, and concentrated under reduced pressure to obtain 42 g of a residue.

This was crystallized with 200 ml of methanol to obtain 39.8 g (85%) of Exemplified coupler Y-16. This exemplary coupler Y-16 has a melting point of 110-112.
And the elemental analysis values are as shown in Table 4 below.

[0093]

[Table 4] Synthesis example-3

[0094]

[Chemical 36] Synthesis of Intermediate F 104.7 g (0.51 mol) of Intermediate B, Compound F18
7.5 g (0.5 mol) was dissolved in 1 liter of ethyl acetate and 400 ml of dimethylformamide. While stirring, 107.3 g of dicyclohexylcarbodiimide
(0.525 mol) of dimethylformamide (100 m
l) The solution was added dropwise at 15-30 ° C. 1 at 20-30 ° C
After reacting for an hour, 500 ml of ethyl acetate was added,
It was heated to ~ 60 ° C and the dicyclohexylurea was filtered off.

After adding 500 ml of water to the filtrate and removing the aqueous layer, the filtrate was washed twice with water. The organic layer was dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure to give an oily substance (29%).
0 g was obtained. This oily substance was heated with 1 liter of ethyl acetate and 2 liters of methanol, insoluble matter was removed by filtration, and the filtrate was water-cooled, and crystals of Intermediate F were precipitated, and were collected by filtration. The intermediate F had a yield of 267 g (95%) and a melting point of 1.
63 to 164 ° C., and the elemental analysis values thereof are shown in Table 5 below.
As shown in.

[0096]

[Table 5] Synthesis of Intermediate G 114.0 g (0.2 mol) of Intermediate F was dissolved in 500 ml of dichloromethane. Sulfuryl chloride 2 in this solution
8.4 g (0.21 mol) was added dropwise with stirring at 10 to 15 ° C.

After reacting for 30 minutes at the same temperature, 500 g of a 6% aqueous sodium hydrogencarbonate solution was added dropwise to the reaction mixture. The organic layer was separated, washed with 500 ml of water, and dried over anhydrous sodium sulfate. When dichloromethane was distilled off under reduced pressure, intermediate G was precipitated as crystals and was collected by filtration. Yield 108.6 g (91%) 29.8 g (0.05 mol) of a synthetic intermediate G of Exemplified Coupler Y-12 was dissolved in 80 ml of dimethylformamide to obtain 12.9 g (0.1%) of compound D.
Mol) and then 10.1 g of triethylamine (0.
10 mol) was added dropwise with stirring at 20 to 30 ° C. Four
After reacting at 0-45 ° C for 1 hour, ethyl acetate 300m
1 and 200 ml of water were added. The organic layer was washed twice with 400 g of a 2% aqueous sodium hydroxide solution and then washed once with water. The organic layer was acidified with diluted hydrochloric acid, washed twice with water, and concentrated under reduced pressure to obtain 34 g of a residue. This is ethyl acetate 50m
Crystallization with a mixed solvent of 1, n-hexane 150 ml,
19 g of exemplary coupler Y-12 was obtained.

This crystal was mixed with ethyl acetate / n-hexane = 1
Recrystallization with 120 ml of a mixed solvent having a volume ratio of / 3 gave 15 g (43.5%) of Exemplified coupler Y-12. The exemplified coupler Y-12 has a melting point of 135 to 136 ° C., and its elemental analysis values are as shown in Table 6 below.

[0099]

[Table 6] Synthesis example-4

[0100]

[Chemical 37] 27.0 g (0.15 mol) of a synthetic compound G of the exemplified coupler Y-49 and 15.2 g (0.15 mol) of triethylamine were dissolved in 50 ml of dimethylformamide. 29.8 g of intermediate G in this mixture
(0.05 mol) dimethylformamide (30 ml)
The solution was added dropwise with stirring.

After reacting at 30 to 40 ° C. for 4 hours, 400 ml of ethyl acetate was added to 300 ml of water. 2 organic layers
After washing with 400 g of an aqueous sodium hydroxide solution at 40%, it was washed twice with water. The organic layer was acidified with dilute hydrochloric acid, washed twice with water, and dried over anhydrous sodium sulfate. The ethyl acetate was distilled off under reduced pressure to obtain 54 g of a residue.

This was crystallized with 300 ml of a mixed solvent of ethyl acetate / methanol (1/2 volume ratio), and the exemplified coupler Y-49 was collected by filtration. The obtained crystals were recrystallized from 200 ml of a mixed solvent of ethyl acetate / methanol (1/2 volume ratio) to give 28.8 g (77.8%) of Exemplified coupler Y-49.
Obtained. This exemplary coupler Y-49 has a melting point of 190-19.
It was 1 ° C., and its elemental analysis values are as shown in Table 7 below.

[0103]

[Table 7] In the present invention, the yellow couplers represented by the general formulas (I) to (V) have a ratio of 1.0 per mol of silver halide.
It can be used in the range of up to 1.0 × 10 ⁻³ mol.
It is preferably 5.0 × 10 ^{−1 to} 2.0 × 10 ⁻² mol, and more preferably 4.0 × 10 ^{−1 to} 5.0 × 10 ⁻² mol.

In the present invention, the yellow couplers represented by formulas (I) to (V), when used as the main coupler, are preferably added to the blue-sensitive silver halide emulsion layer or the non-photosensitive layer adjacent thereto. When the coupler releases a photographically useful group, it is added to the silver halide photosensitive layer or the non-photosensitive layer according to the purpose.

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

In the present invention, the couplers represented by the general formulas (I) to (V) can be prepared by various known dispersion methods.
It can be incorporated into a color light-sensitive material.

In the oil-in-water dispersion method, which is one of the known dispersion methods, a low-boiling organic solvent (eg, ethyl acetate, butyl acetate, methyl ethyl ketone, isopropanol) is used to apply a fine dispersion and dry it. A method in which the low boiling point organic solvent does not substantially remain in the film can be used. When a high-boiling organic solvent is used, any of those having a boiling point of 175 ° C. or higher under normal pressure may be used, and one kind or two or more kinds may be arbitrarily mixed and used. The ratio of the couplers represented by the general formulas (I) to (V) to these high-boiling organic solvents can be in a wide range, but 1 g of the coupler is used.
The range is 5.0 or less per weight ratio. Preferably 0
To 2.0, and more preferably 0.01 to 1.0.

The latex dispersion method described below can also be applied.

Further, various couplers and compounds described later can be mixed or used together.

Next, the layer structure of the light-sensitive material of the present invention will be described.

The light-sensitive material of the present invention preferably has three light-sensitive layers: a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer. Further, a yellow filter layer for reducing the blue sensitivities of the green-sensitive emulsion layer and the red-sensitive emulsion layer, and for reducing color mixture during development between photosensitive layers having different color sensitivities or between the same color-sensitive layers. The intermediate layer may have a non-photosensitive layer such as an antihalation layer for preventing halation,
In order to improve color reproducibility, for example, US Pat.
No. 3,271, No. 4,705,744, No. 4,7
07,436, JP-A-62-160448, 63.
No. 89890, a donor layer having a multilayer effect having a spectral sensitivity distribution different from that of a main photosensitive layer such as a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer is arranged adjacent to or in proximity to the main photosensitive layer. Good.

A plurality of silver halide emulsion layers constituting each unit light-sensitive layer are composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
JP-A-57-112751, JP-A-62-200350
Nos. 62-206541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support.

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

Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

Further, as described in JP-B-49-15495, a silver halide emulsion layer having the highest photosensitivity in the upper layer, a silver halide emulsion layer having a lower photosensitivity in the middle layer, and a lower layer from the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, 4
In the case of more than one layer, the arrangement may be changed as described above.

In the present invention, various layer structures and layer arrangements can be selected as described above according to the purpose of each light-sensitive material.

In the present invention, the above various layer constitutions
In the layer arrangement, at least one light-sensitive silver halide emulsion layer and / or a layer adjacent to the light-sensitive silver halide emulsion layer and close to the support are provided with substantially non-light-sensitive fine grain silver halide. It contains particles.

Substantially non-photosensitive fine silver halide grains are provided in at least one light-sensitive silver halide emulsion layer of the present invention and / or a layer adjacent to the support adjacent to the light-sensitive silver halide emulsion layer. The content will be described in more detail.

Of the various layer configurations and layer arrangements described above,
Representative basic preferred examples are listed in Table 8 below.

[0121]

[Table 8] In the representative basic layer structure and layer arrangement shown in Table 8, each color-sensitive layer is shown as a two-layer structure of high sensitivity and low sensitivity, but three layers such as high sensitivity, medium sensitivity and low sensitivity. The above configuration may be adopted. In this case, for example, RH may be RH-1 and RH-2, and RL may be RL.
It may be -1 and RL-2. At this time, it is preferable to arrange the low-sensitivity layer, the medium-sensitivity layer, and the high-sensitivity layer from the side closer to the support. RH-1 and RH-2, RL-1 and RL-
If necessary, an intermediate layer M may be provided between the two. Further, RH and RH, GL and GH in Example 1 and Example 2 in Table 8,
An intermediate layer M may be provided between BL and BH. Furthermore, A
An intermediate layer may be provided between H and RL or on the side of the YF close to the support or on the side far from the support, and two or more of these non-photosensitive layers including a protective layer are required to be adjacent to each other. It can be provided accordingly.

The present invention will be described in accordance with the representative basic layer constitution and layer arrangement shown above. The photosensitive silver halide emulsion layers are BH, BL, GH, GL, RH and RL. At least one light-sensitive silver halide emulsion layer and / or a layer adjacent to the light-sensitive silver halide emulsion layer and adjacent to the support contains substantially non-light-sensitive fine silver halide grains.

The layers adjacent to the support, which are adjacent to the light-sensitive silver halide emulsion layer, including the layers adjacent to the support shown in Table 8, can be provided as necessary as described above. It also includes a non-photosensitive layer such as an intermediate layer.

In the present invention, the light-sensitive silver halide emulsion layer is preferably a blue-sensitive emulsion layer (BH and B in Table 8).
L), the highest sensitivity layer of the green-sensitive emulsion layer (GH in Table 8), and the highest sensitivity layer of the red-sensitive emulsion layer (RH in Table 8). More preferably, it is a blue-sensitive emulsion layer (BH and BL in Table 8).
Most preferred is the most sensitive layer of the blue sensitive emulsion layer.

The layer adjacent to the support adjacent to the light-sensitive silver halide emulsion layer is preferably a non-light-sensitive layer. The intermediate layer described above is more preferable, and the hydrophilic colloid layer containing no coupler or other compound is most preferable.

The present invention comprises, in the above-described embodiment, at least one light-sensitive silver halide emulsion and / or a layer adjacent to the light-sensitive silver halide emulsion layer, which is close to the support, and is substantially light-insensitive. It contains fine grain silver halide grains.

Next, the substantially non-photosensitive fine grain silver halide grain of the present invention will be described.

The substantially non-photosensitive property of the substantially non-photosensitive fine grain silver halide grain of the present invention means that the sensitivity is 0.5 or more in log unit lower than the sensitivity of the lowest sensitive layer among the adjacent photosensitive silver halide grains. To do. More preferably, it is lower than 1.0.

The substantially non-photosensitive fine grain silver halide grain of the present invention may be pure silver chloride, pure silver bromide, pure silver iodide, silver chlorobromide, silver iodobromide or silver chloroiodobromide. Since it is preferable that these silver halide grains are not dissolved at the time of development, it is desirable that the silver chloride content is low.
The following are preferred. On the other hand, it is desirable that the content of silver bromide is high, and 60 mol% or more is preferable. The silver iodide content is 40 mol% or less, preferably 10 mol% or less. Particularly, silver iodobromide grains having a silver iodide content of 10 mol% or less are preferable.

The particle size is not particularly limited, but is preferably 0.6 μm or less. More preferably 0.0
It is in the range of 4 to 0.4 μm. When the layer containing the substantially non-photosensitive fine grain silver halide grains is a blue-sensitive emulsion layer, a blue-sensitive emulsion layer or a layer of the lowest-sensitivity blue-sensitive emulsion layer on the side close to the support, it is preferably 0. It is in the range of 08 to 0.25 μm. When the layer containing the substantially non-photosensitive fine grain silver halide grains is a green-sensitive emulsion layer, a green-sensitive emulsion layer or a layer of the lowest-sensitivity green-sensitive emulsion layer closer to the support, it is preferably 0.1 to When the content layer is in the range of 0.3 μm and the layer is on the side closer to the support of the red-sensitive emulsion layer, the red-sensitive emulsion layer or the red-sensitive emulsion layer having the lowest sensitivity, it is preferably 0.1 to 0. Four
It is in the range of μm. The substantially non-photosensitive fine grain silver halide grains used in the present invention can have a relatively wide grain size distribution, but preferably have a narrow grain size distribution, especially in terms of weight or number of silver halide grains. It is preferable that the size of the particles occupying 90% is within ± 40 of the average particle size.

The coating amount of the substantially non-photosensitive fine grain silver halide grain of the present invention is 0.03 to 5.0 g, and preferably 0.05 to 1.0 g per 1 m ³ . When the layer containing the substantially non-photosensitive fine grain silver halide grains is a non-photosensitive layer other than the photosensitive emulsion layer, the binder of this layer may be any hydrophilic polymer, but gelatin is particularly preferable. The binder amount is preferably less than 250 g per 1 mol of fine grain silver halide.

The substantially non-photosensitive fine grain silver halide grain used in the present invention can be prepared by a known method. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method for reacting the soluble silver salt and the soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. . As one of the simultaneous mixing methods, p in the liquid phase where silver halide is produced
A method of holding Ag constant, that is, a control double jet method can be used. Since this method has a narrow grain size distribution, it is preferable as a method for preparing the substantially non-photosensitive fine grain silver halide grain of the present invention.

The substantially non-photosensitive fine grain silver halide grain of the present invention may have a regular crystal form such as a cube, octahedron, dodecahedron and tetradecahedron, and may have a spherical or tabular shape. It may be crystalline particles. The inside and the surface of the silver halide grains may have different halogen compositions or may have a uniform halogen composition. The substantially non-photosensitive fine grain silver halide grain may contain cadmium ion, lead ion, iridium ion, rhodium ion and the like as impurities.

The substantially non-photosensitive fine grain silver halide grain may be of a surface latent image type or an internal latent image type, and may have a fog nucleus inside.

The substantially non-photosensitive fine grain silver halide grains may be subjected to usual chemical sensitization, that is, sulfur sensitization, gold sensitization and reduction sensitization, but it is desirable to restrain the degree of chemical sensitization as much as possible. .. Emulsions which are not chemically sensitized (so-called unripened) are preferred as the fine grain silver halide grains of the present invention.
The method for preparing these silver halide grains, the shape and the like will be described in more detail later.

The substantially non-photosensitive fine grain silver halide grains of the present invention include spectral sensitization, that is, cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holopolar cyanine dye, hemicyanine dye, styrene dye and hemioxonol. A known dye such as a dye may be included. Further, desensitizing dyes which have a large desensitization and which are not preferable in a normal negative emulsion can be used.

The substantially non-photosensitive fine grain silver halide grains may contain known antifoggants and stabilizers. For example, antifoggants or stabilizers such as azoles, heterocyclic mercapto compounds, thioketo compounds, azaindenes, benzenethiosulfonic acids and benzenesulfinic acid can be added.

Dyes may be added to the layer containing the substantially non-photosensitive fine grain silver halide grains of the present invention, and a dispersion of a hardly soluble synthetic polymer may be contained.

In the present invention, at least one light-sensitive silver halide emulsion layer of a silver halide color photographic light-sensitive material containing at least one coupler represented by formula (I) or (II). And / or represented by the general formula (I) or (II) by incorporating a substantially non-photosensitive fine grain silver halide grain in a layer adjacent to the support adjacent to the light sensitive silver halide emulsion layer. It is possible to give a higher color density to the high color density of the coupler, and to increase the density compared to the acylacetanilide type 2-equivalent yellow coupler described in, for example, JP-A-61-77848. Is big. Moreover, in the constitution of the present invention, the stability of the photographic material over time is high. Further, it also improves the graininess.

Next, the silver halide of the photosensitive silver halide emulsion layer used in the light-sensitive material of the present invention will be described.

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

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

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

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types) ”, and ibid. No. 1871
6 (November 1979), p. 648, ibid. 30710
5 (Nov. 1989), pp. 863-865, and "Graphide's Physics and Chemistry," published by Paul Montel, P. Glafkides, Chemie et Phi.
sine Photographie, Paul
Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin,
Photographic Emulsion Che
mistry (Focal Press, 196
6)), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating P
photographic Emulsion, Foca
l Press, 1964) and the like.

US Pat. Nos. 3,574,628 and 3,
655,394 and British Patent 1,413,748.
The monodisperse emulsions described in JP-A No. 1989-2000 are also preferable.

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

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

The above-mentioned emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain or a type which has a latent image on both the surface and the inside. Must be a type of emulsion. Among the internal latent image types, the cores described in JP-A-63-264740 /
It may be a shell type internal latent image type emulsion. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-13.
3542. The 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.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are Research Disclosure No. 17643, ibid. 18716 and No.
No. 307105, and the relevant parts are summarized in the table below. Regarding the above-mentioned preparation method of these silver halide grains and the like, they can be applied to the above-mentioned substantially non-photosensitive fine grain silver halide grains except for the grain size.

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

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer.
The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner core of the fogged core / shell type silver halide grain may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.01 to 0.7.
5 μm, particularly 0.05 to 0.6 μm is preferable. Also,
The grain shape is not particularly limited, and may be regular grains or polydisperse emulsion, but monodisperse (at least 95% of the weight or the number of silver halide grains is within ± 40% of the average grain size). (Having a particle size of 1).

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

Known photographic additives that can be used in the present invention are also described in the above-mentioned three Research Disclosures, and the relevant portions are shown in the following table.

Types of additives RD17643 RD18716 RD307105 1 Chemical sensitizer page 23 648 page right column 866 page 2 Sensitivity enhancer page 648 right column 3 Spectral sensitizer, page 23-24 page 648 right column-866-868 page Supersensitizer 649 page right column 4 whitening agent page 24 647 page right column 868 page 5 antifoggant, page 24 to 25 page 649 right column 868 to 870 page stabilizer 6 light absorber, page 25 to 26 Page 649 Right column to page 873 Filter dye, page 650 Left column UV absorber 7 Anti-staining agent Page 25 Right column Page 650 Left column to page 872 Right column 8 Dye image stabilizer page 25 650 Page left column Page 872 9 Hard film Agents Page 26 651 Left column 874 to 875 Page 10 Binder page 26 651 Page left column 873 to 874 Page 11 Plasticizer and lubricant page 27 650 Page right column 876 Page 12 Coating aid, Page 26 to 650 page 650 Right column 875-876 pages Surfactant 13 Static page 27 650 page Right column 876-877 page Anti-agent 14 Matt agent 878-879 pages To prevent deterioration of photographic performance due to formaldehyde gas, It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde described in U.S. Pat. Nos. 4,411,987 and 4,435,503.

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

The light-sensitive material of the present invention can be incorporated into Japanese Patent Laid-Open No. 1-1060.
No. 52, it is preferable to include a compound which releases a fog agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing.

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

Various color couplers can be used in the present invention, specific examples of which are described in Research Disclosure No. 17643, VII-CG, and N
o. 307105, VII-C to G.

Yellow coupler (in the general formula (I) of the present invention)
Or a coupler that can be used in combination with the coupler represented by the general formula (II)) is, for example, US Pat. No. 3,933,50.
No. 1, No. 4,022,620, No. 4,326,0
No. 24, No. 4,401,752, No. 4,248,
961, Japanese Patent Publication No. 58-10739, British Patent No. 1,
425,020, 1,476,760, U.S. Pat. Nos. 3,973,968, 4,314,023.
No. 4,511,649, European Patent 249,4.
Nos. 73A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A Nos. 60-43659, 61-72238, and 60-.
No. 35730, No. 55-118034, No. 60-18.
Those described in US Pat. No. 5951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630 and International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-based and naphthol-based couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, No. 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
Issue No. 4,775,616, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable. Further, JP-A 64-553 and 64-5.
54, 64-555 and 64-556, and pyrazoloazole couplers described in US Pat. No. 4,811.
The imidazole couplers described in No. 8,672 can also be used.

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

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

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

Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention.
The DIR coupler which releases a development inhibitor is, in addition to the DIR coupler represented by the formula (I) or (II) of the present invention, the above-mentioned RD17643, VII-F and N.
o. 307105, Patents described in Section VII-F, JP-A Nos. 57-151944, 57-154234, 60-184248, 63-37346, and 63.
Those described in U.S. Pat. No. 3,773,350, U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

R. D. No. 11449, 24241,
The bleaching accelerator releasing coupler described in JP-A-61-2201247 is effective for shortening the processing time having a bleaching ability, and is particularly added to a light-sensitive material using tabular silver halide grains. In that case, the effect is great. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patents 2,097,140 and 2,131,188, JP-A-59-157638.
Nos. 59-170840 and No. 59-170840 are preferable.
Further, JP-A-60-107029 and JP-A-60-2523.
Compounds releasing a fog agent, a development accelerator, a silver halide solvent, etc. by an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A No. 40, JP-A-1-44940 and JP-A-1-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Competitive couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after separation described in European Patent Nos. 173,302A and 313,308A , A ligand releasing coupler described in US Pat. No. 4,555,477, a coupler releasing a leuco dye described in JP-A-63-75747, and a fluorescent dye described in US Pat. No. 4,774,181. Examples thereof include releasing couplers.

The coupler used in the present invention can be introduced into the 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 US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher include phthalic acid esters (eg, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl)). Phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2
-Ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate), benzoic acid esters (for example, 2-ethylhexylbenzoate, dodecylbenzoate, 2
-Ethylhexyl-p-hydroxybenzoate), amides (e.g., N, N-diethyldodecane amide,
N, N-diethyllaurylamide, N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert)
-Amylphenol), aliphatic carboxylic acid esters (for example, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate),
Examples thereof include aniline derivatives (eg, N, N-dibutyl-2-butoxy-5-tert-octylaniline) and hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene). The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C or higher and about 16 ° C.
An organic solvent at 0 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

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

The color light-sensitive material of the present invention contains phenethyl alcohol, JP-A-63-257747 and JP-A-62-1257.
272248, and 1,2-benzisothiazolin-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol described in JP-A No. 1-80941. It is preferable to add various antiseptics or antifungal agents such as 2- (4-thiazolyl) benzimidazole.

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

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

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable.
The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T
_1/2 can be measured according to a method known in the art. For example, A Green (A. Gre
en) et al. in Photographic Science and Engineering (Photogr. Sci. En.
g. ), Vol. 19, No. 2, pp. 124-129, and can be measured by using a swellometer (swelling meter) of the type. T _1/2 was treated with a color developer at 30 ° C. for 3 minutes 15 seconds. 90% of the maximum swollen film thickness that reaches at times is defined as the saturated film thickness, and is defined as the time until it reaches 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150.
~ 500% is preferred.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, ibid. 18
716, page 651, left column to right column, and the same No. 30710
No. 5, 880-881 can be developed.

The color developing solution used for developing the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-.
N, N-diethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-
Mention may be made of N-ethyl-β-methoxyethylaniline and their sulphates, hydrochlorides or p-toluenesulphonates. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains, for example, a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole,
It is common to include development inhibitors or antifoggants such as benzothiazoles or mercapto compounds. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents. Agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclo Hexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--
1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N
-Tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts can be mentioned as representative examples.

When the reversal processing is carried out, black and white development is usually carried out and then color development is carried out. This black-and-white developer contains known black-and-white developing agents, for example, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. The classes can be used alone or in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air.

The contact area between the photographic processing liquid and the air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, more preferably 0. 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, JP-A-1-82 is available.
A method using a movable lid described in Japanese Patent No.
-216050 can be mentioned as a slit developing treatment method. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps,
For example, it is preferably applied in all steps of bleaching, bleach-fixing, fixing, washing with water, stabilization and the like. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

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

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. As a typical bleaching agent, an organic complex salt 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 of citric acid, tartaric acid, malic acid, etc. Can be used. Of these, aminodicarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are included.
II) Complex salts are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but it may be processed at a lower pH in order to speed up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. 17129 (July 1978) and the like, a compound having a mercapto group or a disulfide group; a thiazolidine derivative described in JP-A No. 50-140129;
JP-B-45-8506, JP-A-52-20832,
53-32735, U.S. Pat. No. 3,706,561.
Derivatives described in Japanese Patent No. 1,127,7
15, iodide salts described in JP-A-58-16235;
West Germany Patent Nos. 966,410 and 2,748,430; polyoxyethylene compounds; JP-B-45-8
No. 836, polyamine compounds; Others JP-A-49-
40943, 49-59644, 53-949.
No. 27, No. 54-35727, No. 55-26506.
No. 58-163940, bromide ions and the like can be used. Of these, compounds having a mercapto group or a disulfide group are preferred because of their large accelerating effect, and are particularly described in U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95630. Compounds are preferred. Further, US Pat. No. 4,55
The compounds described in No. 2,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

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

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. The use of salt is common,
In particular, ammonium thiosulfate can be used most widely. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

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

The total time of the desilvering process is preferably as short as possible in the range where desilvering failure does not occur. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method for strengthening the stirring, a method of causing a jet of a processing solution to collide with an emulsion surface of a light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461. Method to improve the effect, further moving the photosensitive material while contacting the emulsion surface with the wiper blade provided in the solution, to improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective with any of the fixing solutions. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator.

The automatic developing machine used in the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19125.
It is preferable to have the photosensitive material conveying means described in No. 8 and No. 60-191259. JP-A-60-1
As described in No. 91257, such a conveying means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as coupler), the application, and further the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward current, and various other types. It can be set in a wide range depending on the conditions. Among them, the relationship between the number of washing tanks and the water amount in the multi-stage countercurrent system is described in the Journal of the Soc.
yety of Motion Picture an
d Television Engineers No. 6
Volume 4, P. 248 to 253 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention,
As a solution to such a problem, Japanese Patent Laid-Open No. 62-2888
The method of reducing calcium ion and magnesium ion described in No. 38 can be used very effectively.
Also, isothiazolone compounds, siabendazoles, chlorine-based bactericides such as chlorinated sodium isocyanurate described in JP-A-57-8542, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986)
Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982), Industrial Technology Association, Japan Antibacterial and Antifungal Society, Ed., "Encyclopedia of Antibacterial and Antifungal Agents" (1986) Agents can also be used.

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

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

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

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

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

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

Various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

The silver halide light-sensitive material of the present invention comprises
For example, U.S. Pat. No. 4,500,626, JP-A-60
-133449, 59-218443, 61-
It can also be applied to the photothermographic materials described in 238056 and European Patent 210,660A2.

[0201]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 On a subbed cellulose triacetate film support,
A sample 101, which is a multi-layer color light-sensitive material having the following composition, was prepared. The amount coated amount (Composition of photosensitive layer) for Harogenha halide and colloidal silver are represented in units of g / m ² of silver and coupler, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer. The symbols indicating additives have the following meanings. However, when there are multiple utilities, one of them is listed as a representative.

UV; UV absorber, Solv; high boiling organic solvent, ExS; sensitizing dye, ExC; cyan coupler;
ExM: Magenta coupler, ExY: Yellow coupler, Cpd: Additive, W: Surfactant, H: Curing agent,
F: Stabilizer.

The additives are listed in Chemical Formulas 38 to 52 below.

[0204]

[Chemical 38]

[0205]

[Chemical Formula 39]

[0206]

[Chemical 40]

[0207]

[Chemical 41]

[0208]

[Chemical 42]

[0209]

[Chemical 43]

[0210]

[Chemical 44]

[0211]

[Chemical formula 45]

[0212]

[Chemical formula 46]

[0213]

[Chemical 47]

[0214]

[Chemical 48]

[0215]

[Chemical 49]

[0216]

[Chemical 50]

[0217]

[Chemical 51]

[0218]

[Chemical 52] First layer (antihalation layer) Black colloidal silver 0.15 Gelatin 1.90 ExM-1 5.0 × 10 ^-3 Second layer (intermediate layer) Gelatin 2.10 UV-1 3.0 × 10 ^-2 UV -2 6.0 x 10 ^-2 UV-3 7.0 x 10 ^-2 ExF-1 4.0 x 10 ^-3 Solv-2 7.0 x 10 ^-2 Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, sphere equivalent diameter 0.3 μm, variation coefficient of sphere equivalent diameter 29%, normal crystal, twin mixed grains, diameter / thickness ratio 2.5) Silver coating Quantity 0.50 Gelatin 1.50 ExS-1 1.0 × 10 ^-4 ExS-2 3.0 × 10 ^-4 ExS-3 1.0 × 10 ^-5 ExC-1 0.11 ExC-3 0.11 ^{ExC-4 3.0 × 10 -2 ExC} -7 1.0 × 10 -2 ExC-8 2.0 × 10 -2 Solv-1 7.0 × 10 -3 fourth layer (medium Red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, spherical equivalent diameter 0.55 μm, variation coefficient of spherical equivalent diameter 20%, normal crystal, twin crystal mixed particles, diameter / thickness ratio 1.0) Silver coating amount 0.85 Gelatin 2.00 ExS-1 1.0 × 10 ^-4 ExS-2 3.0 × 10 ^-4 ExS-3 1.0 × 10 ^-5 ExC-1 0.16 ExC-2 8.0 × 10 ⁻² ExC-3 0.17 ExC-7 1.5 × 10 ⁻² ExC-8 1.5 × 10 ⁻² Comparison coupler (a) 3.0 × 10 ⁻² Cpd− 10 1.0 × 10 ⁻⁴ Solv-1 0.10 Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, spherical equivalent diameter 0.7 μm, spherical equivalent) Diameter variation coefficient 30%, twin mixed particles, diameter / thickness ratio 2.0) Silver coating amount 0.70 Gelatin 1.60 ExS-1 1.0 × 1 0 ^-4 ExS-2 3.0x10 ^-4 ExS-3 1.0x10 ^-5 ExC-5 7.0x10 ^-2 ExC-6 8.0x10 ^-2 ExC-7 1.5x 10 ^-2 Solv-1 0.10 Solv-2 8.0 x 10 ^-2 Solv-4 5.0 x 10 ^-2 6th layer (intermediate layer) Gelatin 1.10 P-2 0.17 Cpd-10 .10 Cpd-4 0.17 Solv-1 5.0 × 10 ^-2 Seventh layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, equivalent spherical diameter 0. 3 μm, variation coefficient of equivalent spherical diameter 28%, normal crystal, twin mixed particles, diameter / thickness ratio 2.5) Silver coating amount 0.30 Gelatin 0.50 ExS-4 5.0 × 10 ^-4 ExS-5 ^{2.0 × 10 -4 ExS-6 0.3} × 10 -4 ExM-1 3.0 × 10 -2 ExM-2 0.15 ExM-7 5.0 × 10 -2 Comparative coupler ^{(A) 3.0 × 10 -2 Cpd} -11 7.0 × 10 -3 Solv-4 0.20 Eighth Layer (medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, equivalent sphere diameter 0.55 μm, variation coefficient of equivalent sphere diameter 20%, normal crystal, twin crystal mixed particles, diameter / thickness ratio 4.0) Silver coating amount 0.70 Gelatin 1.00 ExS-4 5. ^{0 × 10 -4 ExS-5 2.0} × 10 -4 ExS-6 3.0 × 10 -5 ExM-1 3.0 × 10 -2 ExM-2 0.20 ExM-3 1.5 × 10 - ² ExM-6 8.0 × 10 ⁻² Comparative coupler (a) 4.0 × 10 ⁻² Cpd-11 9.0 × 10 ⁻³ Solv-1 0.20 9th layer (high sensitivity green sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, sphere equivalent diameter 0.7 μm, variation coefficient of sphere equivalent diameter 30%, normal crystal, twin mixed grains, diameter / Viewed ratio 2.0) silver coverage 0.50 Gelatin ^{0.90 ExS-4 2.0 × 10 -4} ExS-5 2.0 × 10 -4 ExS-6 2.0 × 10 -5 ExS-7 3 0.0 × 10 ^-4 ExM-1 1.0 × 10 ^-2 ExM-4 3.9 × 10 ^-2 ExM-5 2.6 × 10 ^-2 Cpd-2 1.0 × 10 ^-2 Cpd-9 2 0.0x10 ^-4 Cpd-10 2.0x10 ^-4 Solv-1 0.15 Solv-2 5.0x10 ^-2 Solv-4 5.0x10 ^-2 10th layer (yellow filter layer) Gelatin 0.90 Yellow colloid 5.0 × 10 ^-2 Cpd-1 0.20 Solv-1 0.15 11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI) Type, equivalent sphere diameter 0.5 μm, variation coefficient of equivalent sphere diameter 15%, octahedral grain) Silver coating amount 0.40 Gelatin 1.00 ExS- 2.0 × 10 ^-4 Comparative Coupler (a) 9.0 × 10 ^-2 Comparative Coupler (1) 0.90 Cpd-2 1.0 × 10 -2 Solv-1 0.20 Solv-4 0.10 second 12 layers (intermediate layer) Gelatin 0.50 13th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, sphere equivalent diameter 1.3 μm, variation coefficient of sphere equivalent diameter) 25%, normal crystal, twin crystal mixed particles, diameter / thickness ratio 4.5) Silver coating amount 0.50 Gelatin 0.60 ExS-8 1.0 × 10 ^-4 Comparative coupler (1) 0.12 Cpd-2 1.0 × 10 ⁻³ Solv-1 4.0 × 10 ⁻² 14th layer (first protective layer) Fine grain silver iodobromide emulsion (average grain size 0.07 μm, AgI 1 mol%) 0.20 Gelatin 0 .80 UV-2 0.10 UV-3 0.10 UV-4 0.20 Solv-3 4.0 × 10 ^{− 2} P-2 9.0 × 10 ^-2 15th layer (second protective layer) Gelatin 0.90 B-1 (diameter 1.5 μm) 0.10 B-2 (diameter 1.5 μm) 0.10 B- 3 2.0 × 10 ^-2 H-1 0.40 Further, in order to improve storage stability, processability, pressure resistance, antifungal / antibacterial property, antistatic property, and coating property, Cpd-3, C
pd-5, Cpd-6, Cpd-7, Cpd-8, P-
1, W-1, W-2, W-3, W-4 were added.

In addition to the above, n-butyl-p-hydroxybenzoate was added. Furthermore, B-4, F-1,
F-4, F-5, F-6, F-7, F-8, F-9, F
-10, F-11, and iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt are contained. (Sample 102) As a non-photosensitive fine silver halide grain in the twelfth layer (intermediate layer) of Sample 101, an average grain size of 0.25 μm was obtained by a double jet method in which pAg was controlled when silver halide grains were prepared. Sample 10 was prepared by preparing an unripened silver iodobromide (silver iodide 2 mol%) emulsion and coating this emulsion at a silver coating amount of 0.50 g / m ^2.
2 was produced. At this time, the gelatin coating amount of the same layer is Sample 1
01 and the other layers were the same as those of sample 101. (Sample 103) For the tenth layer (yellow filter layer) and the eleventh layer (low-sensitivity blue-sensitive emulsion layer) of the sample 101, the non-photosensitive fine grain silver halide emulsion used for the twelfth layer of the sample 102 was used. Silver coating amount is 0.50 g / m ² , respectively
Sample 103 was prepared such that the coating amount was 0.25 g / m ² , the gelatin coating amount was the same, and the others were unchanged. (Samples 104 to 106) Fourth Layer, Seventh Sample 101
The comparative coupler (a) used in the layers, the eighth layer, the eleventh layer and the thirteenth layer was replaced with the coupler Y-63 of the present invention so that the coating amount was 90%, and the comparative coupler (1) was the coupler of the present invention. Sample 104 with Y-16 replaced by equimolar amounts
~ 106 were produced. However, sample 104 is sample 101
Sample 105 is sample 102, sample 106 is sample 10
It was produced in the same manner as in 3.

The prepared samples 101 to 106 have a size of 35 mm.
The samples were cut into widths and processed, and these samples were evaluated for the following performance. (1) Minimum density + from the characteristic curve measured with blue (B) light of the sample which was subjected to wedge exposure of photographic white light (4800 ° K)
The logarithmic value of the reciprocal of the exposure amount giving a density of 0.2 was obtained, and this was taken as the sensitivity (S), and the relative value (S _rel ) was calculated with reference to the sample 101. The higher the value, the higher the feeling.

Further, the density value (D) at which the exposure amount of log E = 1.5 is given from the exposure amount at the sensitivity point to the high exposure amount side is read, and the density percentage (D ₁ %) was calculated. (2) Color image fastness Using the samples used for evaluation of photographic properties,
Store for 15 days under conditions of 0 ° C and 70% RH, measure the concentration again, read the concentration value given the minimum concentration + 2.0 before the test start measured with B light, read the concentration value, and start the test The ratio of the remaining concentration value to the previous concentration (D ₂
%) Was determined and defined as the residual ratio of the color image. It is shown that a higher numerical value gives higher color image fastness. (3) Stability of sensitive material with time Two sets of each of the prepared samples were prepared, and one set was 50
Stored under the conditions of 60 ° C and 60% RH for 5 days, and the other set was stored at 5 ° C for the same period. After the storage, these two sets of samples were subjected to grayscale exposure with white light as before, and the treatments were simultaneously performed. The processed sample is subjected to concentration measurement, and the sensitivity point on the characteristic curve measured with B light is obtained in the same manner as in (1), and the difference (ΔS
₁ ) was calculated. The smaller the value, the smaller the fluctuation in sensitivity and the better the storage stability. (4) Image quality Color turbidity After each sample was uniformly exposed with green light for 0.5 Lux · sec, it was processed with gradation exposure of B light, and the yellow density was adjusted to a minimum density of +1.5. The value obtained by subtracting the magenta density value at the minimum yellow density from the magenta density value at the given exposure amount was taken as the color turbidity and used as a scale for color reproducibility. The smaller the value, the lower the density in the green color range, and the higher the color saturation.

Granularity The RMS value at the minimum yellow density +0.7 density measured with an aperture having a diameter of 48 μm is shown. The smaller the value, the better the graininess.

The processing executed to perform the above performance evaluation is as follows.

The sample to be evaluated for performance was subjected to a running process on a sample separately image-wise exposed to sample 101 until the cumulative replenishing amount of the color developing solution became three times the mother liquor tank capacity. After that, the treatment was carried out.

Processing process Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 05 seconds 38.0 ° C 600ml 5 liters Bleach 50 seconds 38.0 ° C 140ml 3 liters Bleach fixing 50 seconds 38.0 ° C-3 liters Fixed 50 seconds 38.0 ℃ 420 ml 3 liters Water wash 30 seconds 38.0 ℃ 980 ml 2 liters Stability (1) 20 seconds 38.0 ℃ −2 liters Stability (2) 20 seconds 38.0 ℃ 560 ml 2 liters Dry 1 minute 60 ℃ * Replenishment amount is 1m of photosensitive material the amount washing water per ² is a countercurrent system from (2) to (1), the overflow solution of washing water was entirely introduced to the fixing bath. To replenish the bleach-fixing bath, connect the upper part of the bleaching tank of the automatic processor and the lower part of the bleach-fixing tank and the upper part of the fixing tank and the lower part of the bleach-fixing tank with a pipe, All the overflow liquid generated by the supply was allowed to flow into the bleach-fixing bath. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the rinsing process were each 1 m ² of the light-sensitive material. 65ml, 50ml,
It was 50 ml and 50 ml. The crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the treatment liquid is shown below. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 3.0 1-Hydroxyethylidene-1,1 3.3 3.3-diphosphonic acid Sodium sulfite 3.9 5.2 Carbonic acid Potassium 37.5 39.0 Potassium bromide 1.4 0.4 Potassium iodide 1.3 mg-Hydroxylamine sulfate 2.4 3.3 2-Methyl-4- [N-ethyl-4.5 6.0 N- (β-hydroxyethyl) amino] aniline sulphate Add water 1.0 liter 1.0 liter pH 10.05 10.05 (bleaching solution) Mother liquor (g) Replenisher (g) 1,3- Propylenediaminetetraacetic acid 144.0 206.0 Ferric ammonium monohydrate Ammonium bromide 84.0 120.0 Ammonium nitrate 17.5 25.0 Hydroxyacetic acid 63.0 80.0 Vinegar Acid 54.2 80.0 Add water 1.0 liter 1.0 liter pH [adjusted with ammonia water] 3.80 3.60 (bleach-fixing solution mother liquor) 15 pairs of the bleach-fixing solution and the following fixing solution mother liquor Mixed solution of 85 (fixing solution) Mother liquor (g) Replenishing solution (g) Ammonium sulfite 19.0 57.0 Ammonium thiosulfate aqueous solution 280 ml 840 ml (700 g / liter) Imidazole 28.5 85.5 Ethylenediaminetetraacetic acid 12. 5 Add 37.5 water 1.0 liter 1.0 liter pH [Adjust with ammonia water and acetic acid] 7.40 7.45 (Wash water) Mother liquor and replenisher common tap water is H type strong acid cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite IRA-4)
00) packed in a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then 20 mg of sodium isocyanurate dichloride /
L and 150 mg / L of sodium sulfate were added. The pH of this liquid was in the range of 6.5-7.5. (Stabilizer) Common to mother liquor and replenisher (Unit: g) Formalin (37%) 1.2 ml Sodium p-toluenesulfinate 0.3 g Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization: 10) Ethylenediaminetetraacetic acid disodium salt 0.05 Water was added to 1.0 liter pH 7.2 The evaluation results of the above samples 101 to 106 are summarized in Table 9 below.

[0227]

[Table 9] It can be seen from Table 9 that the sample 104 using the coupler of the present invention shows excellent color developing properties (sensitivity, color density) as compared with the sample 101 using the corresponding comparative coupler, although the coating amount was reduced to 90%. In addition, it shows that the color image fastness is good, the color turbidity is small, and the color reproducibility is excellent.

Twelfth of Sample 101 and Sample 104
The samples in which the non-photosensitive fine grain silver halide was added to the layers or the 10th and 11th layers showed an improvement in color developability, but the samples 105 and 10 using the coupler of the present invention were used.
It is apparent that the sample No. 6 has a greater degree of improvement in color developability than the corresponding samples 102 and 103, and has a large effect of adding the non-photosensitive fine grain silver halide. Further, the coupler of the present invention retains an excellent effect of improving color image fastness and color turbidity even when a non-photosensitive fine grain silver halide is used, and improves color developability, stability of sample with time and granularity. It is clear from Table 9. Example 2 Based on the sample 105 prepared in Example 1, the couplers Y-63 and Y-16 used in the 11th and 13th layers were replaced by equimolar amounts as shown in Tables 10 and 11 below. Was produced.

The samples thus produced were cut and processed into a width of 35 mm, and the same performance evaluation as in Example 1 was carried out. For comparison, Samples 101 and 102 were run simultaneously.

The processing was carried out by using the following processing steps and solutions having the composition of the processing solution, using an automatic developing machine, and carrying out the same running processing as in Example 1.

Treatment Process Process Treatment time Treatment temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ℃ 33ml 20 liters Bleach 6 minutes 30 seconds 38 ℃ 25ml 40 liters Water wash 2 minutes 10 seconds 24 ℃ 1200ml 20 liters 4 minutes 20 seconds 38 ℃ 25 ml 30 liters Water wash (1) 1 minute 05 seconds 24 ℃ (2) to (1) 10 liters Countercurrent piping water wash (2) 1 minute 00 seconds 24 ℃ 1200 ml 10 liters Stability 1 minute 05 seconds 38 ℃ 25ml 10 liter Dry 4 minutes 20 seconds 55 ℃ Replenishment amount per 35mm width 1m length The composition of the processing liquid is described below. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1 3.0 3.2-Diphosphonic acid Sodium sulfite 4.0 4.4 Carbonic acid Potassium 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydro 4.5 5. 5 Xylethylamino] -2-methyl aniline sulfate Add water 1.0 liter 1.0 liter pH 10.05 10.10 (bleaching solution) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid second Iron 100.0 120.0 Sodium trihydrate Ethylenediaminetetraacetic acid 10.0 10.0 Disodium salt Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35 0.0 Ammonia water (27%) 6.5 ml 4.0 ml Water was added 1.0 liter 1.0 liter pH 6.0 5.7 (fixer) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid 0.5 0.7 Disodium salt Sodium sulfite 7.0 8.0 Sodium bisulfite 5.0 5.5 Ammonium thiosulfate aqueous solution 170.0 ml 200.0 ml (70%) Add water 1.0 liter 1.0 Liter pH 6.7 6.6 (Stabilizing liquid) Mother liquor (g) Replenishing liquid (g) Formalin (37%) 2.0 ml 3.0 ml Polyoxyethylene-p-monononyl 0.3 0.45 Phenyl ether (average) Degree of Polymerization 10) Ethylenediaminetetraacetic acid 0.05 0.08 Disodium salt water is added to 1.0 liter 1.0 liter pH 5.0-8.0 5.0-8.0 Implementation as above The evaluation results of the sample of Example 2 are shown in Table 10 below.
It is also shown in Table 11.

[0232]

[Table 10]

[0233]

[Table 11] However, the comparative coupler (b) ^{* in} Table 10 is a compound represented by the following chemical formula 53.

[0234]

[Chemical 53] From Tables 10 and 11, samples 201 to 211 using the non-photosensitive fine grain silver halide using the coupler represented by the general formula (I) or the general formula (II) of the present invention,
Comparative samples 101 and 1 of Example 1 which were treated simultaneously
When compared with No. 02, it is clear that various properties such as color developability (sensitivity and color density), stability of sample with time, color image fastness, and image quality (color reproducibility, graininess) are excellent.

Further, the sample 20 which satisfies the constitutional requirements of the present invention.
When closely comparing 1-211, Sample 209 and Sample 209 are samples 209 using a so-called O-elimination type coupler in which an aryloxy group is bonded to the active position of the coupler.
Is a little lower than the so-called N-dissociative coupler having a heterocyclic leaving group bonded to the active position with a nitrogen atom, which is slightly lower in performance such as color development, stability of sample with time, color image fastness, and graininess. It can be seen that so-called N-disengagement type couplers are preferred.

Further, when comparing the samples 201, 210 and 211, in the coupler of the present invention, the coupler represented by the general formula (II) has the above-mentioned various performances as compared with the coupler represented by the general formula (I). It is also clear from the comparison between the sample 201 and the samples 210 and 211 that they are excellent. Example 3 On a subbed cellulose triacetate film support,
A sample 301, which is a multi-layer color light-sensitive material consisting of layers having the compositions shown below, was prepared.

The addition amount in the light-sensitive material is shown in grams per m ² , and the silver halide emulsion and colloidal silver are shown in terms of silver. The ratio is shown.

The compound used in Example 3 was converted to the following compounds
Chemical formula 63

[0239]

[Chemical 54]

[0240]

[Chemical 55]

[0241]

[Chemical 56]

[0242]

[Chemical 57]

[0243]

[Chemical 58]

[0244]

[Chemical 59]

[0245]

[Chemical 60]

[0246]

[Chemical formula 61]

[0247]

[Chemical formula 62]

[0248]

[Chemical formula 63] (Composition of photosensitive layer) First layer (antihalation layer) Black colloidal silver 0.3 Gelatin 1.0 Ultraviolet absorber UV-1 0.1 Ultraviolet absorber UV-2 0.1 Ultraviolet absorber UV-3 0. 1 Dispersion Oil Oil-1 0.2 Dispersion Oil Oil-2 0.1 Second Layer (Intermediate Layer) Gelatin 1.0 Coupler C-2 0.02 Dispersion Oil Oil-1 0.01 Third Layer (Low Sensitivity Red) Sensitive emulsion layer) Monodisperse silver iodobromide emulsion 1.8 (3 mol% silver iodide, average grain size 1.0 μm) Gelatin 1.2 Sensitizing dye I 1.4 × 10 ⁻⁴ Sensitizing dye II 7 × 10 ^-5 coupler C-1 0.5 coupler C-2 0.05 coupler C-11 0.05 compound D 0.1 dispersed oil Oil-3 0.03 dispersed oil Oil-4 0.03 4th layer (intermediate Layer) Gelatin 1.0 Compound A 0.1 Fifth layer (low sensitivity green sensitivity) Agent layer) Monodisperse silver iodobromide emulsion 1.4 (3 mol% silver iodide, average grain size 1.0 μm) Monodisperse silver iodobromide emulsion 0.3 (3 mol% silver iodide, average grain size 0) .3 μm) Gelatin 0.8 Sensitizing dye III 3 × 10 ⁻⁴ Sensitizing dye IV 1 × 10 ⁻⁴ Sensitizing dye V 1 × 10 ⁻⁴ Coupler C-3 0.7 Coupler C-4 0.1 Coupler C -5 0.1 Coupler C-11 0.1 Compound C 0.1 Dispersion Oil Oil-3 0.3 Sixth Layer (Intermediate Layer) Gelatin 1.0 Compound A 0.1 Seventh Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Monodisperse silver iodobromide emulsion 0.7 (3 mol% silver iodide, average grain size 1.0 μm) Monodisperse silver iodobromide emulsion 0.2 (3 mol% silver iodide, average grain size 0. 3 [mu] m) 1.0 sensitizing gelatin dye VI 2 × 10 ^-4 sensitizing dye VII 2 × 10 ^-4 coupler C-6 0.9 coupler C-10 0.2 coupler C-11 0.1 minutes Oil Oil-1 0.15 Eighth layer (intermediate layer) Gelatin 1.0 Compound B 0.1 Ninth layer (high-sensitivity red-sensitive emulsion layer) Polydisperse silver iodobromide emulsion 2.3 (6 mol of silver iodide) %, Average particle size 2.0 μm) Gelatin 1.2 Sensitizing dye I 7 × 10 ⁻⁵ Sensitizing dye II 2 × 10 ⁻⁵ Coupler C-8 0.1 Coupler C-1 0.2 Compound D 0.1 Dispersion oil Oil-4 0.2 10th layer (intermediate layer) Gelatin 1.0 Coupler C-5 0.2 Compound A 0.1 11th layer (high-sensitivity green-sensitive emulsion layer) Polydisperse silver iodobromide emulsion 2 0.0 (silver iodide 5 mol%, average particle size 2.0 μm) Gelatin 1.0 Sensitizing dye III 1 × 10 ⁻⁴ Sensitizing dye IV 3 × 10 ⁻⁵ Sensitizing dye V 3 × 10 ⁻⁵ Coupler C -9 0.2 Compound C 0.1 Dispersed oil Oil-1 0.4 12th layer (intermediate layer) Gelatin 1.2 Compound A 0.1 13th layer (High-sensitivity blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion 1.8 (3 mol% silver iodide, average grain size 2.1 μm) Monodisperse silver iodobromide emulsion 0.5 (3 mol% silver iodide) , Average particle size 1.2 μm) Monodisperse silver iodobromide emulsion 0.2 (3 mol% silver iodide, average particle size 0.3 μm) Gelatin 1.2 Sensitizing dye VI 3 × 10 ⁻⁴ Sensitizing dye VII 1 × 10 ⁻⁴ Coupler C-6 0.3 Dispersion oil Oil-1 0.1 14th layer (first protective layer) Coupler C-7 0.1 UV absorber UV-1 0.05 UV absorber UV- 2 0.05 UV absorber UV-3 0.05 UV absorber UV-4 0.05 UV absorber UV-5 0.05 Gelatin 0.6 Dispersion oil Oil-4 0.1 Fifteenth layer (second protection Layer) Gelatin 0.5 Polymethylmethacrylate particles (diameter 1.5 μm) 0.2 In addition to the above components, each layer has a boundary. Active agent W-1, a hardening agent H-
1 was added. In addition, formalin scavenger was added. (Sample 302) A non-photosensitive fine grain silver halide emulsion having a grain size of pure silver bromide having an average grain size of 0.15 μm was applied to the twelfth layer (intermediate layer) of Sample 301 in an amount of 0.8 g of coated silver. It was applied so as to be / m ² . At this time, the amount of coated gelatin was adjusted to be the same as that of sample 301. (Sample 303) The thirteenth layer (high-sensitivity blue-sensitive emulsion layer) of Sample 302 has a non-photosensitive fine grain silver halide emulsion of silver iodobromide (silver iodide 2 mol%) and an average grain size of 0.20 μm. Sample 303 was prepared by adding silver halide so that the coating amount of silver was 0.2 g / m ² . (Sample 304) The thirteenth layer of the sample 301 is replaced with the sample 303.
Sample 304 was prepared by making the same as the 13th layer of No. 3 and without changing the other. (Samples 305 to 308) Couplers used for the third layer, the fifth layer, and the seventh layer corresponding to Samples 301 to 304, C-
11 into the coupler of the invention, Y-64; 7th layer, 13th
The coupler used in the layer, C-6, is the coupler of the present invention, Y-
14 the coating amount was reduced to 90%; the coupler C-10 used in the seventh layer was the coupler of the present invention, and the coating amount was 90% on Y-42.
% To replace each, and samples 305 to 308 were produced.

The samples 301 to 308 thus produced were subjected to the treatment described in Example 2 and subjected to the same performance evaluation. The results are shown in Table 12 below.

[0250]

[Table 12] From Table 12, the sample using the coupler of the present invention exhibits high color developability (sensitivity, color density) despite the coating amount being reduced to 90% with respect to the comparative coupler, and is also excellent in stability over time of the sample. It is clear that the color image fastness is also high and the image quality (color reproducibility and graininess) is excellent. By using non-photosensitive fine grain silver halide grains for the sample containing the coupler of the present invention, it is possible to further improve the color developability, the stability of the sample over time, and the graininess of the image quality.
It can be seen from the comparison with Samples 06 to 308, and from the comparison between Samples 302 to 304 and Samples 306 to 308, the improvement effect of Samples 306 to 308 using the coupler of the present invention is larger than that of Comparative samples. I also understand. Example 4 Based on the sample 306 of Example 3, a non-photosensitive fine-grain silver halide having a grain size of pure silver bromide having an average grain size of 0.20 μm was applied to the intermediate layer of the tenth layer. 0.0 g
A sample 401 was prepared by coating so as to have a thickness of / m ² . (Sample 402) Non-photosensitive fine grain silver halide having a grain size of pure silver bromide having an average grain size of 0.30 was applied to the middle layer of the eighth layer of Sample 306 of Example 3 to coat 1.2 g of silver. A sample 402 was prepared by coating so as to have a thickness of m ² .

The prepared samples 401 and 402 are replaced with sample 306.
The photographic properties (relative sensitivity) of the samples 306 and 401 are the same as those of the magenta color image measured with green light.
402 examined the cyan image measured with red light.
In addition, the processing described in Example 1 was performed. The results are shown in Table 13 below.

[0252]

[Table 13] From Table 13, as in the case of the previous example, by incorporating a non-photosensitive fine grain silver halide grain in the adjacent layer on the side closer to the support of the green-sensitive emulsion layer or the red-sensitive emulsion layer, good photographic property was obtained. It turns out that

When the graininess was also examined, it was confirmed that the grain size was improved.

Further, based on the sample 105 of Example 1, the same amount of silver halide having the same grain size was used in the sixth intermediate layer as in the case of sample 401 and in the second intermediate layer in the same manner as in the case of sample 402. When the coating was applied and the photographic properties and graininess were examined, it was found that similar improvement effects were obtained.

[0255]

INDUSTRIAL APPLICABILITY In a light-sensitive material containing at least one coupler represented by formula (I) or (II), at least one light-sensitive silver halide emulsion layer and / or the silver halide emulsion is used. By incorporating substantially non-photosensitive fine grain silver halide grains in the layer adjacent to the side closer to the support of the layer, excellent color forming properties of the coupler represented by the general formula (I) or the general formula (II), Further enhance color development without impairing color image fastness and color reproducibility,
It is possible to stabilize the storability of the light-sensitive material over time and improve the graininess. Therefore, it is possible to provide a silver halide color photographic light-sensitive material excellent in color developability, color image fastness, image quality and storability of the light-sensitive material over time.

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[Procedure amendment]

[Submission date] January 10, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

When X ₁ and X ₂ represent an alkyl, aryl or heterocyclic group having a substituent, and when the nitrogen-containing heterocyclic group formed with X ₃ with> N- has a substituent, The following are mentioned as an example of those substituents. A halogen atom (for example, fluorine, chlorine), an alkoxycarbonyl group (having 2 to 30 carbon atoms, preferably 2 to 20. For example, methoxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl),
Acylamino group (having 2 to 30 carbon atoms, preferably 2 to 2 carbon atoms)
0. For example, acetamide, tetradecanamide, 2-
(2,4-di-t-amylphenoxy) butanamide,
Benzamide), sulfonamide group (having 1 to 30 carbon atoms,
Preferably 1-20. For example, methanesulfonamide, dodecanesulfonamide, hexadecylsulfonamide,
Benzenesulfonamide), carbamoyl group (C1
-30, preferably 1-20. For example, N-butylcarbamoyl, N, N-diethylcarbamoyl), N-sulfonylcarbamoyl group (having 1 to 30 carbon atoms, preferably 1 to 30 carbon atoms)
20. For example, N-mesylcarbamoyl, N-dodecylsulfonylcarbamoyl), sulfamoyl group (having 1 carbon atom)
-30, preferably 1-20. For example, N-butylsulfamoyl, N-dodecylsulfamoyl, N-hexadecylsulfamoyl, N-3- (2,4-di-t-amylphenoxy) butylsulfamoyl, N, N-diethylsulfate Famoyl), an alkoxy group (having 1 to 30 carbon atoms,
Preferably 1-20. For example, methoxy, hexadecyloxy, isopropoxy), aryloxy group (C6
-20, preferably 6-10. For example, phenoxy, 4-
Methoxyphenoxy, 3-t-butyl-4-hydroxyphenoxy, naphthoxy), aryloxycarbonyl group (C7-21, preferably 7-11. Phenoxycarbonyl), N-acylsulfamoyl group (C2). -30, preferably 2-20. For example, N-propanoylsulfamoyl, N-tetradecanoylsulfamoyl), a sulfonyl group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, methanesulfonyl, octanesulfonyl, 4-hydroxyphenyl sulfonyl, dodecane sulfonyl), an alkoxycarbonylamino group (having a carbon number of 2 to
30, preferably 2-20. For example, ethoxycarbonylamino), cyano group, nitro group, carboxyl group, hydroxyl group, sulfo group, alkylthio group (having 1 to 3 carbon atoms).
0, preferably 1-20. For example, methylthio, dodecylthio, dodecylcarbamoylmethylthio), a ureido group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, N-phenylureido, N-hexadecylureido), an aryl group (having 6 to 20 carbon atoms, preferably 6 carbon atoms). -10. For example, phenyl, naphthyl, 4-methoxyphenyl), a heterocyclic group (having 1 to 20 carbon atoms, preferably 1 to 10. As a hetero atom, for example, at least one nitrogen, oxygen or sulfur is included 3 to 12, Preferably a 5- or 6-membered monocyclic or condensed ring such as 2-pyridyl, 3-pyrazolyl, 1-pyrrolyl, 2,4-dioxo-1,3-imidazolidin-1-yl, 2-benzoxazoli. Group, morpholino, indolyl), alkyl group (1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, straight chain, branched chain or ring) , And saturated or unsaturated alkyl, such as methyl, ethyl,
Isopropyl, cyclopropyl, t-pentyl, t-octyl, cyclopentyl, t- butyl, s- butyl, dodecyl, 2-hexyl decyl), an acyl group (2 carbon atoms
30, preferably 2-20. For example, acetyl, benzoyl), an acyloxy group (having 2 to 30 carbon atoms, preferably 2 carbon atoms)
~ 20. For example, propanoyloxy, tetradecanoyloxy), an arylthio group (having 6 to 20 carbon atoms, preferably 6 to 10. For example, phenylthio, naphthylthio), a sulfamoylamino group (having 0 to 30 carbon atoms, preferably 0).
~ 20. For example, N-butylsulfamoylamino, N-
Dodecylsulfamoylamino, N-phenylsulfamoylamino) or N-sulfonylsulfamoyl group (having 1 to 30, preferably 1 to 20 carbon atoms, for example N-
Mesyl sulfamoyl, N-ethanesulfonyl sulfamoyl, N-dodecanesulfonyl sulfamoyl, N
-Hexadecanesulfonylsulfamoyl). The above substituents may further have a substituent. Examples of the substituent include the substituents mentioned here.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

[0035] When Z represents an aryloxy group, preferably a substituted or unsubstituted aryl Oki <br/> sheet group having 6 to 10 carbon atoms. A substituted or unsubstituted phenoxy group is particularly preferable. When it has a substituent, examples of the substituent include the substituents enumerated as the substituents that the group represented by X ₁ may have. Among them, a preferable substituent is a case where at least one substituent is an electron-withdrawing group, and examples thereof include a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group,
Examples thereof include a halogen atom, a carbamoyl group, a nitro group, a cyano group and an acyl group.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction content]

[0036] When Z represents an aryl thio group, preferably a substituted or unsubstituted aryl thio group having 6 to 10 carbon atoms. Particularly preferred is a substituted or unsubstituted phenylthio group. When it has a substituent, examples of the substituent include the substituents enumerated as the substituents that the group represented by X ₁ may have. Among them, preferred substituents are when at least one substituent is an alkyl group, an alkoxy group, a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom, a carbamoyl group, or a nitro group.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

[0039] When Z represents an acyloxy group, this acyloxy group is preferably a carbon number 6 to 10, a monocyclic or condensed ring, substituted or unsubstituted aryl
Le acyloxy group or the number of carbon atoms, 2 to 30, preferably a substituted or unsubstituted 2-20 alkyl acyl <br/> group. When these have a substituent, examples of the substituent include the substituents enumerated as the substituents which the group represented by X ₁ may have.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0040

[Correction method] Change

[Correction content]

When Z represents a carbamoyloxy group, this carbamoyloxy group is an alkyl , aryl , heterocycle, substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. For example N,
Mention may be made of N-diethylcarbamoyloxy, N-phenylcarbamoyloxy, 1-imidazolylcarbonyloxy or 1-pyrrolocarbonyloxy. When these have a substituent, examples of the substituent include the substituents enumerated as the substituents which the group represented by X ₁ may have.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction content]

The group represented by Y in the general formulas (I) and (II) is preferably an aryl group. Particularly preferred is a phenyl group having at least one substituent at the ortho position. As the explanation of the substituent, those enumerated as the substituents which may be possessed when Y is an aryl group can be mentioned. The example of a preferable substituent is also the same.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0045

[Correction method] Change

[Correction content]

The group represented by Z in the general formula (I) and (II), preferably 5-6 membered, nitrogen-containing heterocyclic group bonded to the coupling site via a nitrogen atom, an aryloxy group, 5-6 And a 5- or 6-membered heterocyclic thio group.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction content]

[0049]

[Chemical 11] In the formula, Z has the same meaning as described in the general formula (I),
X ₄ represents an alkyl group, _{X 5} is alkyl or A
Represents a reel group, Ar represents a phenyl group having at least one substituent in the ortho position, and X ₆ represents —C (R
₁ R ₂ ) -N <represents an organic residue that forms a nitrogen-containing heterocyclic group (monocycle or condensed ring), and X ₇ represents -C (R ₃ ).
Represents an organic residue forming a nitrogen-containing heterocyclic group (monocycle or condensed ring) together with C (R ₄ ) -N <, and R ₁ , R ₂ and R
₃ and R ₄ represent a hydrogen atom or a substituent.

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0075

[Correction method] Change

[Correction content]

[0075]

[Chemical 32]

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0076

[Correction method] Change

[Correction content]

[0076]

[Chemical 33] Note that Y-56 and Y-57 in Chemical formula 30,
Y-58 in Chemical formula 3, Y-63 in Chemical formula 32 and Chemical formula 3
In Y64 in 3, "}" indicates that the substituent is substituted at the 5- or 6-position of the benzotriazolyl group.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0103

[Correction method] Change

[Correction content]

[0103]

[Table 7] In the present invention, the yellow couplers represented by the general formulas (I) to (V) are added in the case of a layer to be added or a non-photosensitive layer.
1.0 mol / mol of silver halide in adjacent layers
It can be used in the range of 1.0 × 10 ⁻⁴ mol.
It is preferably 5.0 × 10 ^{−1 to} 2.0 × 10 ⁻³ mol, and more preferably 4.0 × 10 ^{−1 to} 5.0 × 1.
It is in the range of 0 to ³ mol.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0121

[Correction method] Change

[Correction content]

[0121]

[Table 8] In the representative basic layer structure and layer arrangement shown in Table 8, each color-sensitive layer is shown as a two-layer structure of high sensitivity and low sensitivity, but three layers such as high sensitivity, medium sensitivity and low sensitivity. The above configuration may be adopted. In this case, for example, RH may be RH-1 and RH-2, and RL may be RL.
It may be -1 and RL-2. At this time, it is preferable to arrange the low-sensitivity layer, the medium-sensitivity layer, and the high-sensitivity layer from the side closer to the support. RH-1 and RH-2, RL-1 and RL-
If necessary, an intermediate layer M may be provided between the two. Further, RL and RH, GL and GH in Example 1 and Example 2 in Table 8,
An intermediate layer M may be provided between BL and BH. Furthermore, A
An intermediate layer may be provided between H and RL or on the side of the YF close to the support or on the side far from the support, and two or more of these non-photosensitive layers including a protective layer are required to be adjacent to each other. It can be provided accordingly.

[Procedure Amendment 13]

[Document name to be amended] Statement

[Name of item to be corrected] 0133

[Correction method] Change

[Correction content]

The substantially non-photosensitive fine grain silver halide grain of the present invention may have a regular crystal form such as a cube, octahedron, dodecahedron and tetradecahedron, and may have a spherical or tabular shape. It may be crystalline particles. Preferably aspe
The tabular grains have a cut ratio of 2.0 or more. The inside and the surface of the silver halide grains may have different halogen compositions or may have a uniform halogen composition. The substantially non-photosensitive fine grain silver halide grain may contain cadmium ion, lead ion, iridium ion, rhodium ion and the like as impurities.

[Procedure Amendment 14]

[Document name to be amended] Statement

[Name of item to be corrected] 0225

[Correction method] Change

[Correction content]

[0225] The washing water was a countercurrent system from (2) to (1), and the overflow of washing water was all introduced into the fixing bath. To replenish the bleach-fixing bath, connect the upper part of the bleaching tank of the automatic processor and the lower part of the bleach-fixing tank and the upper part of the fixing tank and the lower part of the bleach-fixing tank with a pipe, All the overflow liquid generated by the supply was allowed to flow into the bleach-fixing bath. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the bleach-fixing process, the amount of bleach-fixing solution brought into the fixing process, and the amount of fixing solution brought into the water washing process were each per 1 m ² of the light-sensitive material. 65ml, 50ml,
It was 50 ml and 50 ml. The crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

Claims (7)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, which is represented by the following general formula (I) or general formula (II). A light-sensitive silver halide emulsion layer and / or an adjacent layer on the side closer to the support of the light-sensitive silver halide emulsion layer, which contains substantially non-light-sensitive fine silver halide grains. A silver halide color photographic light-sensitive material. [Chemical 1] In the formula, X ₁ and X ₂ each represent an alkyl group, an aryl group or a heterocyclic group, Y represents an aryl group or a heterocyclic group, and Z is an oxidized product of a developing agent as the coupler represented by the general formula (I). Represents a group that leaves when reacted with. [Chemical 2] In the formula, X ₃ represents an organic residue forming a nitrogen-containing heterocycle with> N-, Y represents an aryl group or a heterocyclic group,
Z represents a group which leaves when the coupler represented by the general formula (II) reacts with an oxidized product of a developing agent. 2. The photosensitive silver halide emulsion layer is a blue-sensitive silver halide emulsion layer.
The described silver halide color photographic light-sensitive material. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein the adjacent layer on the side closer to the support of the light-sensitive silver halide emulsion layer is a non-light-sensitive layer. 4. A silver halide color photographic light-sensitive material according to claim 2, wherein the layer adjacent to the support of the light-sensitive silver halide emulsion layer is a color-sensitive layer other than blue-sensitive. . 5. A silver halide color photographic light-sensitive material having, on a support, two or more silver halide emulsion layers having the same color sensitivity and different sensitivities, and the two silver halide emulsion layers therein are simultaneously adjacent to each other. Characterized by having a layer containing substantially non-photosensitive fine grain silver halide grains, and containing a coupler represented by the general formula (I) of the following chemical formula 3 or the general formula (II) of the following chemical formula 4. A silver halide color photographic light-sensitive material. [Chemical 3] In the formula, X ₁ and X ₂ each represent an alkyl group, an aryl group or a heterocyclic group, Y represents an aryl group or a heterocyclic group, and Z is an oxidized product of a developing agent as the coupler represented by the general formula (I). Represents a group that leaves when reacted with. [Chemical 4] In the formula, X ₃ represents an organic residue forming a nitrogen-containing heterocyclic group with> N-, Y represents an aryl group or a heterocyclic group, and Z represents a coupler represented by the general formula (II) as a developing agent. Represents a group that leaves when it reacts with an oxidant. 6. The silver halide color photographic light-sensitive material according to claim 5, wherein the layer containing the substantially non-photosensitive fine grain silver halide grains is non-photosensitive. 7. A silver halide color photographic light-sensitive material having two or more red-sensitive, green-sensitive, and blue-sensitive silver halide emulsion layers each having different sensitivity on a support, and the following (1) to (4): A silver halide color photographic light-sensitive material characterized by satisfying all the above conditions and containing a coupler represented by the following general formula (I) or the following general formula (II). (1) The photosensitive silver halide emulsion layer provided on the side farthest from the support is the most sensitive blue-sensitive silver halide emulsion layer (BH), and (2) the most sensitive green-sensitive halogen. Silver halide emulsion layer (G
H) and the most sensitive red-sensitive silver halide emulsion layer (RH) between the BH and the blue-sensitive silver halide emulsion layer (Bh) less sensitive than BH, (3) the Bh (4) In the BH, the red-sensitive, green-sensitive, and blue-sensitive silver halide emulsion layers (RL, GL, and BL, respectively) having the lowest sensitivity are not present on the side farther from the support. BH having a non-photosensitive layer adjacent thereto
And / or the non-photosensitive layer contains substantially non-photosensitive fine grain silver halide grains. [Chemical 5] In the formula, X ₁ and X ₂ each represent an alkyl group, an aryl group or a heterocyclic group, Y represents an aryl group or a heterocyclic group, and Z is an oxidized product of a developing agent as the coupler represented by the general formula (I). Represents a group that leaves when reacted with. [Chemical 6] In the formula, X ₃ represents an organic residue forming a nitrogen-containing heterocycle with> N-, Y represents an aryl group or a heterocyclic group,
Z represents a group which leaves when the coupler represented by the general formula (II) reacts with an oxidized product of a developing agent.