JPH052249A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve stability with the passage of time, fastness of color image, and picture quality by incorporating a malon diamide-type yellow coupler and a compd. which can scavenge the oxidized product of developing agent into a photographic sensitive material. CONSTITUTION:The silver halide color photographic sensitive material has at least one photosensitive emulsion layer and at least one insensitive emulsion layer on a supporting body and contains couplers expressed by formula I and formula II and a compd. or its precursor which can scavenge the oxidized product of the developing agent. Where, X1 and X2 are alkyl groups, aryl groups, or heterocyclic groups respectively, X3 is an org. residue which forms a nitrogen-contg. heterocyclic group with > N-, Y is an aryl group or heterocyclic group, and Z is a group which isolates when the couplers expressed by formulae react with the oxidized product of the developing agent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention provides high color density,
The present invention relates to a silver halide color photographic light-sensitive material having improved storability, color image fastness and image quality of the light-sensitive material.

[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 high sensitivity and high color density, and the photographic performance varies during storage of the light-sensitive material. Therefore, there is a demand for a light-sensitive material excellent in image quality (color reproducibility, sharpness, graininess) and color image storability of the obtained color image. In the subtractive method, 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. Although the color extinction coefficient of the color-developing dye obtained from (3) is low, the color-developing density is low, so that there has been 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.

On the other hand, a malondiamide type coupler similar to the yellow coupler of the present invention is described in, for example, Japanese Patent No. 1,558,452, but the coupler disclosed in the patent has an active position. Is a so-called O-elimination type 2-equivalent coupler having a group capable of leaving via an oxygen atom, and is mainly a diffusible coupler. Further, as a functional coupler in the malondiamide type coupler, a development inhibitor releasing type (DIR) coupler is disclosed in, for example, JP-A-52-69624, and a malondianilide type coupler in US Pat. Nos. 4,149,886 and 4,4. 477, 56
3 and JP-A-2-250053.
However, U.S. Pat. Nos. 4,149,886 and 4,4
No. 77,563 does not describe a specific compound. Among them, Japanese Patent Application Laid-Open No. 52-69624 does not describe a concrete effect. Moreover, the couplers described in each of the above patents have a problem that the image storability when used, particularly the deterioration of the fastness when stored under high temperature and high humidity, is large. There is a problem that the absorption density in the (green range) is high and the color reproducibility is deteriorated. In addition, it was also found that there are problems that the coupling activity is low and that it is difficult to use, and that the storability of the light-sensitive material is poor.

On the other hand, a compound capable of scavenging an oxidized product of a developing agent or a compound capable of releasing a precursor thereof is called an anti-color mixing agent or an anti-staining agent and is used as one means for preventing undesired color contamination. It has been put to practical use as a photosensitive material. As a compound used for this kind of means, a hydroquinone compound can be mentioned and many have been proposed. For example, US Pat.
60,290, 2,419,613, 2,40
No. 3,721, No. 3,960,570, etc.
-Alkyl hydroquinones are described in U.S. Pat.
0,453, JP-A-49-106329, and JP-A-50-
No. 156438, West German Patent Publication No. 2,149,789, etc., mono-branched alkyl hydroquinones include US Patent Nos. 2,728,659, 2,732,300, 3,243,294 and 3,3. 700,453, British Patent 752,146, JP-A-50-156438,
No. 53-9528, No. 54-29637, and Japanese Patent Publication No. 5
No. 0-21249 describes dialkyl-substituted hydroquinones, and US Pat. No. 2,418,613 describes aryl hydroquinones.

Further, a hydroquinone compound having a nucleus substituted with an electron-withdrawing group such as an acyl group, a nitro group, a cyano group, a formyl group and a halogenated alkyl group is disclosed in JP-A-57-22.
No. 237 is proposed. U.S. Pat. No. 4,198,2
No. 39 discloses hydroquinones substituted with an aliphatic acylamino group, a ureido group, a urethane group and the like.
No. 202465 proposes hydroquinones substituted with a sulfonamide group, and US Pat. No. 2,701,197 proposes hydroquinones substituted with an acylamino group and having a sulfonic acid group.

Further, a compound having a hydroquinone residue and a coupler residue in the same molecule is disclosed in JP-B-55-75.
No. 78 shows a coupler such as a compound which is a group whose leaving group upon color development does not adversely affect the photographic properties, and which is a coupler residue capable of moving the color forming dye formed from the coupler in the film. Related compounds are JP-A-6
No. 3,311,252. Certainly, these compounds have the ability to prevent color contamination and are used in various light-sensitive materials.However, they produce colored products after they exhibit the effect of preventing color contamination, and their performance during the production or storage of photosensitive materials. There is a problem of degrading or fogging the silver halide emulsion, and these are depending on the intended performance of the light-sensitive material, or other materials used even if they are the same kind of light-sensitive material, for example,
When a coupler is newly introduced, a compound capable of scavenging an oxidized product of a developing agent and an anti-color mixing agent are optimized accordingly, and they are not uniformly used.

Although the above-mentioned JP-A-52-69624 certainly describes the use of a hydroquinone compound capable of scavenging an oxidized product of a developing agent, there is no study on the scavenging ability of the oxidized product of a developing agent. Bulgarian Patent No. 1,
No. 558,452 does not describe a compound capable of scavenging an oxidized product of a developing agent.

[0008]

As described above, when a coupler having a high color density, an excellent spectral absorption characteristic and an excellent color image fastness is used, the stability of the light-sensitive material with time is further improved, and There is a strong demand for further improvement in image robustness and color reproducibility. Accordingly, the first object of the present invention is to provide a silver halide color photographic light-sensitive material which gives a high color density and has improved temporal stability of the light-sensitive material having excellent spectral absorption characteristics. The second object is to provide a silver halide color photographic light-sensitive material having improved color image fastness. The third object is to provide a silver halide color photographic light-sensitive material having further improved image quality.

[0009]

The above-mentioned problems have been solved by the means described below. That is, a silver halide color photographic light-sensitive material having at least one light-sensitive emulsion layer and at least one non-light-sensitive emulsion layer on a support is represented by the general formula (I) and / or the general formula (II). And a compound capable of scavenging an oxidized product of a developing agent, or a precursor thereof, which can be achieved by a silver halide color photographic light-sensitive material. General formula (I)

[0010]

[Chemical 3] General formula (II)

[0011]

[Chemical 4] In the formula, X ₁ and X ₂ each represent an alkyl group, an aryl group or a heterocyclic group, X ₃ represents an organic residue forming a nitrogen-containing heterocyclic group with> N-, and Y represents an aryl group or a heterocyclic group. Represents a group, and Z represents a group which leaves when the coupler represented by the general formula reacts with an oxidized product of a developing agent. The couplers represented by formula (I) and formula (II) of the present invention are described below.

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 number of carbon atoms is 1-2.
0, preferably 1 to 10, as a hetero atom, for example, at least one nitrogen atom, oxygen atom or sulfur atom, and 3 to 12, preferably a 5- or 6-membered ring, saturated or unsaturated, substituted or unsubstituted, It is a monocyclic or condensed-ring 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, pyranyl and the like. When X ₁ and X ₂ represent an aryl group, they represent a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. Typical examples of the aryl group are phenyl and naphthyl. When X ₃ represents a nitrogen-containing heterocyclic group formed together with> N-, the heterocyclic group has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms and is a hetero atom other than a nitrogen atom, such as an oxygen atom or a sulfur atom. May be a substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed-ring heterocyclic group having a 3- to 12-membered ring, preferably a 5- or 6-membered ring. 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-thiazine-s. s-Dioxo-4-yl or benzoxazin-4-yl may be 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. Halogen atom (eg fluorine atom, chloro atom), alkoxycarbonyl group (C2-3)
0, preferably 2-20. For example, methoxycarbonyl,
Dodecyloxycarbonyl, hexadecyloxycarbonyl), an acylamino group (having 2 to 30 carbon atoms, preferably 2 to 20. For example, acetamide, tetradecanamide,
2- (2,4-di-t-amylphenoxy), butanamide, benzamide), sulfonamide group (C1-C1)
30, preferably 1-20. For example, methanesulfonamide, dodecanesulfonamide, hexadecylsulfonamide, benzenesulfonamide), a carbamoyl group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, N-butylcarbamoyl, N, N-diethylcarbamoyl), N-
Sulfonylcarbamoyl group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, N-mesylcarbamoyl, N-dodecylsulfonylcarbamoyl), sulfamoyl group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, N-butylsulfafa Moyl, N-dodecylsulfamoyl, N-hexadecylsulfamoyl, N-3- (2,4-di-t
-Amylphenoxy) butylsulfamoyl, N, N-
Diethylsulfamoyl), alkoxy group (C1-C1)
30, preferably 1-20. For example, methoxy, hexadecyloxy, isopropoxy), aryloxy group (having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, such as phenoxy, 4-methoxyphenoxy, 3-t-butyl-4-hydroxyphenoxy, naphthoxy), aryl Oxycarbonyl group (C7-21, preferably 7-11. For example, phenoxycarbonyl), N-acylsulfamoyl group (C2-30, preferably 2-20. For example, N
-Propanoylsulfamoyl, N-tetradecanoylsulfamoyl), sulfonyl group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, methanesulfonyl, octanesulfonyl, 4-hydroxyphenylsulfonyl, dodecanesulfonyl), alkoxy. Carbonylamino group (having 2 to 30 carbon atoms, preferably 2 to 20. For example, ethoxycarbonylamino), cyano group, nitro group, carboxyl group, hydroxyl group, sulfo group, alkylthio group (having 1 to 30 carbon atoms, preferably 1 to 30 carbon atoms) 20. For example, methylthio,
Dodecylthio, dodecylcarbamoylmethylthio), ureido group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, N-phenylureido, N-hexadecylureido), aryl group (having 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms)
0. For example, phenyl, naphthyl, 4-methoxyphenyl, a heterocyclic group (having 1 to 20 carbon atoms, preferably 1 to 1 carbon atoms)
0. A monocyclic or condensed ring having 3 to 12, preferably 5 or 6 membered rings containing at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom. Eg 2
-Pyridyl, 3-pyrazolyl, 1-pyrrolyl, 2,4-
Dioxo-1,3-imidazolidin-1-yl, 2-benzoxazolyl, morpholino, indolyl), alkyl group (C 1-30, preferably 1-20, straight chain,
Branched, cyclic, saturated, unsaturated. For example, methyl, ethyl, isopropyl, cyclopropyl, t-pentyl, t-octyl, cyclopentyl, t-butyl, s-butyl, dodecyl, 2-hexyldecyl), an acyl group (having 2 to 3 carbon atoms).
0, 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.

Among the above substituents, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a nitro group, an alkyl group or an aryl group is preferable. Can be mentioned. When Y represents an aryl group in the general formulas (I) and (II), it 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. In the general formulas (I) and (II), when Y represents a heterocyclic group, X ₁ or X
_It has the same meaning as explained when ₂ represents a heterocyclic group.
When Y represents a substituted aryl group or a substituted heterocyclic group, examples of the substituent include the substituents listed as examples when X ₁ has a substituent. As a preferred example of the substituent which Y has, 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,
This is when it is an alkoxy group, an acylamino group, an N-sulfonylcarbamoyl group, a sulfonamide group or an alkyl group.

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 photographic useful groups or their precursors (for example, development inhibitors, development accelerators, desilvering accelerators, fogging agents, dyes, hardeners, couplers, oxidized developing agents). Scavenger, fluorescent dye, developing agent or electron transfer agent). When Z is a photographically useful group, those conventionally known are useful. For example, U.S. Pat. Nos. 4,248,962, 4,409,323, 4,438,193, 4,421,845 and 46,185.
No. 71, No. 4652516, No. 4861701, No. 4782012, No. 4857440, No. 48471.
No. 85, No. 4477563, No. 4438193, No. 4628024, No. 4618571, No. 47419.
94, European Published Patent No. 193389A, 3
The photographically useful group described in 48139A or 272573A or a leaving group (for example, a timing group) for releasing the group is used. When Z represents a nitrogen-containing heterocyclic group bonded to the coupling position at a nitrogen atom, preferably
5 or 6 having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms
It is a substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed-ring heterocyclic group having a member ring. 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 include 1-
Pyrazolyl, 1-imidazolyl, pyrrino, 1,2,4
-Triazol-2-yl, 1,2,3-triazol-3-yl, benzotriazolyl, benzimidazolyl, imidazolidin-2,4-dione-3-yl, oxazolidin-2,4-dione-3- Ill, 1, 2, 4-
Examples include triazolidine-3,5-dione-4-yl, 2-imidazolinone-1-yl, 3,5-dioxomorpholino or 1-imidazolyl. When these heterocyclic groups have a substituent, the substituent may be the above X ₁
Examples thereof include the substituents enumerated as the substituents which the group represented by the group may have. As a preferable substituent, one of the substituents is an alkyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an acylamino group, a sulfonamide group, an aryl group, a nitro group, a carbamoyl group, or a sulfonyl group. It is when

When Z represents an aryloxy group, it is preferably a substituted or unsubstituted aryloxy 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 listed as the substituents which the group represented by X ₁ may have. Among them, a preferred substituent is a case where at least one substituent is an electron-withdrawing substituent, and examples thereof include a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom, a carboxyl group, a carbamoyl group and a nitro group. , A cyano group or an acyl group. When Z represents an arylthio group, it is preferably a substituted or unsubstituted arylthio group having 6 to 10 carbon atoms. Particularly preferably, it 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, preferable substituent is when at least one substituent is an alkyl group, an alkoxy group, a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom, a carbamoyl group, or a nitro group.

When Z represents a heterocyclic oxy group, the portion of the heterocyclic group contains at least one 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, monocyclic or condensed-ring heterocyclic group having 1 to 12, preferably 5 or 6 membered ring. 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, a preferable substituent is an alkyl group, an aryl group, a carboxyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an acylamino group, a sulfonamide group, a nitro group. , A carbamoyl group or a sulfonyl group.
When Z represents a heterocyclic thio group, the portion of the heterocyclic group has from 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and as a hetero atom, for example, at least one nitrogen atom, oxygen atom or sulfur atom, 3 to 12, Preferably a 5- or 6-membered ring,
It is a substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed ring heterocyclic group. Examples of the heterocyclic thio group include tetrazolylthio group, 1,3,4-thiadiazolylthio group, 1,3,4-oxadiazolylthio group, 1,
Examples thereof include a 3,4-triazolylthio group, a benzimidazolylthio group, a benzothiazolylthio group, and a 2-pyridylthio 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, preferable substituents include at least one of the substituents such as an alkyl group, an aryl group, a carboxyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an acylamino group, a sulfonamide group and a nitro group. When it is a group, a carbamoyl group, a heterocyclic group or a sulfonyl group.

When Z represents an acyloxy group, it is preferably a monocyclic or condensed ring, substituted or unsubstituted arylacyloxy group having 6 to 10 carbon atoms, or 2 carbon atoms.
-30, preferably 2-20, substituted or unsubstituted alkylacyloxy groups. When these have a substituent, examples of the substituent include the substituents enumerated as the substituents which the group represented by X ₁ may have. When Z represents a carbamoyloxy group, it is an alkyl, aryl, heterocycle, or substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Examples thereof include N, N-diethylcarbamoyloxy, N-phenylcarbamoyloxy, 1-imidazolylcarbonyloxy or 1-pyrrolocarbonyloxy. When these have a substituent, examples of the substituent include the substituents enumerated as the substituents which the group represented by X ₁ may have. Z
Represents an alkylthio group, it is a linear, branched, cyclic, saturated, unsaturated, substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. 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. Y in the general formulas (I) and (II)
The group represented by 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 mentioned as the substituent which may be possessed when Y is an aryl group can be mentioned. The description of the preferable substituents is also the same. General formula (I)
And the group represented by Z in (II) is preferably 5
And a 6-membered nitrogen-containing heterocyclic group bonded to the coupling position at a nitrogen atom, an aryloxy group, a 5- or 6-membered heterocyclic oxy group, or a 5- or 6-membered heterocyclic thio group.

Preferred couplers in the general formulas (I) and (II) are represented by the following general formulas (III), (IV) or (V). General formula (III)

[0021]

[Chemical 5] General formula (IV)

[0022]

[Chemical 6] General formula (V)

[0023]

[Chemical 7]

In the formula, Z has the same meaning as described in formula (I), X ₄ represents an alkyl group, X ₅ represents an alkyl group or an aromatic group, and Ar represents at least one ortho-position. Represents a phenyl group having a substituent, X ₆
Is -C (R ₁ R ₂₎ represents an organic residue forming a -N <with a nitrogen-containing Hajime Tamaki (monocyclic or condensed), X ₇ -
Represents an organic residue forming a nitrogen-containing heterocyclic group (monocycle or condensed ring) together with C (R ₃ ) = C (R ₄ ) -N <,
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} X ₇ , Ar
The detailed description and the preferred range of the groups represented by and Z have the same meanings as those described in the corresponding ranges in the description 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. Particularly preferred couplers in the above general formula 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 preferable examples when they are diffusion resistant couplers.
The diffusion-resistant type is a coupler having a group in the molecule that sufficiently increases the molecular weight in order to immobilize it in the layer to which the molecule is added. Usually, an alkyl group having a total carbon number of 8 to 30, preferably 10 to 20 or an aryl group having a substituent having a total carbon number of 4 to 20 is used. These diffusion resistant groups may be substituted in any of the molecules, or may have a plurality of groups. Specific examples of the yellow couplers represented by formulas (I) to (V) are shown below, but the invention is not limited thereto.

[0026]

[Chemical 8]

[0027]

[Chemical 9]

[0028]

[Chemical 10]

[0029]

[Chemical 11]

[0030]

[Chemical 12]

[0031]

[Chemical 13]

[0032]

[Chemical 14]

[0033]

[Chemical 15]

[0034]

[Chemical 16]

[0035]

[Chemical 17]

[0036]

[Chemical 18]

[0037]

[Chemical 19]

[0038]

[Chemical 20]

[0039]

[Chemical 21]

[0040]

[Chemical formula 22]

[0041]

[Chemical formula 23]

The yellow coupler of the present invention is preferably added to the light-sensitive silver halide emulsion layer or its adjacent layer in the light-sensitive material, and particularly preferably to the light-sensitive silver halide emulsion layer. The total amount added to the sensitive material is
When the leaving group Z contains a photographically useful group component, it is 0.
0001 to 0.80 g / m ² , preferably 0.00
05 to 0.50 g / m ^2, more preferably 0.02 to 0.
It is 30 g / m ² . When the leaving group Z does not contain a photographically useful group component, its addition amount is 0.001 to 1.2.
0 g / m ² , preferably 0.01 to 1.00 g / m ²
More preferably, it is 0.10 to 0.80 g / m ² . The yellow coupler of the present invention can be added in the same manner as a usual coupler as described later. Synthesis Example (1) Synthesis of Exemplified Coupler (1) It was synthesized by the following synthesis route.

[0043]

[Chemical formula 24]

Step N, N-Dimethylformamide 10
In a mixed solvent of 0 ml and 100 ml of acetonitrile (a)
3.5 g of 2 and 13 g of 2 were dissolved. 40 ml of an acetonitrile solution in which 6 g of N, N'-dicyclohexylcarbodiimide was dissolved was added dropwise to this solution at room temperature. After reacting for 2 hours, the N, N'-dicyclohexylurea that had come off was filtered off. The solution was poured into 500 ml of water, and ethyl acetate was added to 500
extracted with ml. After moving to a separating funnel and washing with water, an oil layer was separated. The solvent was distilled off under reduced pressure, and hexane was added to the residue for crystallization. 16.1 g of (c) was obtained.

16 g of step (c) was added to dichloromethane 1
Mix to 50 ml. A solution of bromine (4.8 g) in dichloromethane (10 ml) was added dropwise under ice cooling (5 ° C to 10 ° C). 10
After reacting for a minute, the mixture was transferred to a separating funnel and washed with water. The oil layer (including (d)) was removed and this solution was used in the next step. 8.2 g of step (e) and 8.8 ml of triethylamine
Was added to 160 ml of N, N-dimethylformamide. The dichloromethane solution of 4 obtained above was added dropwise to this solution at room temperature. After reacting for 1 hour, 500 ml of ethyl acetate was added, and the mixture was transferred to a separating funnel and washed with water. It was neutralized with dilute hydrochloric acid and washed with water again. The oil layer was separated and the solvent was distilled off under reduced pressure. The residue was separated and purified by column chromatography. Silica gel was used as the packing material, and ethyl acetate / hexane (1/1) was used as the eluent. Fractions containing the target compound were collected and the solvent was distilled off under reduced pressure to obtain 16.3 g of Wax-like Exemplified Coupler (1).

Synthesis Example (2) Synthesis of Exemplified Coupler (2) Synthesis was carried out in the same manner as Synthesis Example (1). However, instead of (b) above, (f) and (e) are replaced with (g) in equimolar amounts, and the same operation is performed in the same manner as the above, and the desired exemplary coupler (2)
15.4 g of a waxy product was obtained.

[0047]

[Chemical 25] Synthesis Example (3) Synthesis of Exemplified Coupler (6) It was synthesized by the reaction shown in the following scheme.

[0048]

[Chemical formula 26]

4.42 g of compound (i) and 1.8 of triethylamine were added to 50 ml of N, N-dimethylformamide.
7 g was added and stirred for 10 minutes. A solution of 6.23 g of compound (h) in 20 ml of methylene chloride was added dropwise to this solution over 15 minutes at room temperature. After reacting for 1 hour at room temperature, the reaction solution was poured onto water and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the solvent was distilled off under reduced pressure. 3. Purified by silica gel column chromatography, and the desired exemplary coupler (6) 4.
7 g was obtained as a white powder.

Next, the compound or its precursor capable of scavenging the oxidized product of the developing agent of the present invention will be explained.
The above compound used in the present invention has the following general formula [S-
I] to [S-II]. General formula [SI]

[0051]

[Chemical 27]

In the formula [SI], R ² to R ⁶ may be the same or different and each is a hydrogen atom or a group capable of substituting for a benzene ring. However, at least one of R ² and R ⁴ is a hydroxy group, a sulfonamide group or a carbonamide group. Z is a hydrogen atom or a protective group that can be deprotected under alkaline conditions. R ² to R ⁶ , OZ
May jointly form a ring.

General formula [S-II] (Coup)-(Time) _a- (Sc) In the formula [S-II], Coup is-(Time) _a- (Sc) due to reaction with an oxidized color developing agent. Represents a coupler residue capable of releasing Sc, Time represents a timing group capable of releasing Sc after being released from Coup, and Sc represents substantially a color developing process after being released from Coup or the timing group. It represents a scavenger of an oxidized color developing agent capable of scavenging an inactive residue or an oxidized color developing agent by a redox reaction or a coupling reaction, and a represents 0 or 1.

The formula [SI] will be described in more detail below. Preferred examples of the substituent represented by R ² to R ⁶ in the formula [SI] include a halogen atom (for example, chlorine and bromine), a hydroxy group, a sulfo group, a carboxy group, a cyano group, an alkyl group (having 1 carbon atom). To 30 straight, branched or cyclic ones, for example methyl, sec
-Octyl, t-octyl, hexadecyl, cyclohexyl), alkenyl group (having 2 to 30 carbon atoms,
For example, allyl, 1-octenyl), alkynyl group (having 2 to 30 carbon atoms, for example, propargyl), aralkyl group (having 7 to 30 carbon atoms, for example, 1,1
-Dimethyl-1-phenylmethyl, 3,5-di-t-butyl-2-hydroxyphenylmethyl), aryl groups (having 6 to 30 carbon atoms, such as phenyl and naphthyl), heterocyclic groups (oxygen, nitrogen) 3 to 12 containing at least one of sulfur, sulfur, phosphorus, selenium or tellurium
Membered rings such as furfuryl, 2-pyridyl, morpholino, 1-tetrazolyl, 2-selenazolyl), alkoxy groups (having 1 to 30 carbon atoms, such as methoxy, methoxyethoxy, hexadecyloxy, isopropoxy, allyloxy). ), An aryloxy group (having 6 to 30 carbon atoms, for example, phenoxy, 4-nonylphenoxy), an alkylthio group (having 1 to 30 carbon atoms,
For example, butylthio, dodecylthio, 2-hexyldecylthio, benzylthio), arylthio group (having 6 to 30 carbon atoms, for example, phenylthio), carbonamide group (having 2 to 30 carbon atoms, for example, acetamide, 2- (2 , 4-di-t-pentylphenoxy) butanamide, benzamide, 3,5-bis (2-hexyldecanamido) benzamide), sulfonamide group (having 1 to 30 carbon atoms, for example, methanesulfonamide, 4- (2 , 4-di-t-pentylphenoxy) butanesulfonamide, benzenesulfonamide, 4-dodecyloxybenzenesulfonamide), a ureido group (having 2 to 30 carbon atoms, for example, N'-octadecylureido, N'- [3- (2,4-di-t-pentylphenoxy) propyl] Raid, N '-(4-cyanophenyl) ureido, N'-(2-tetradecyloxyphenyl) ureido), an alkoxycarbonylamino group (having 2 to 30 carbon atoms, for example, benzyloxycarbonylamino, ethoxycarbonylamino) ), An aryloxycarbonylamino group (having 7 to 30 carbon atoms such as phenoxycarbonylamino), an acyloxy group (having 2 to 30 carbon atoms such as acetoxy, dichloroacetoxy, 4-oxopentanoyloxy, 2-
(2,4-di-t-pentylphenoxy) hexanoyloxy, benzoyloxy, nicotinoyloxy), sulfamoylamino group (having 1 to 30 carbon atoms,
For example, N'-benzyl-N'-methylsulfamoylamino, N'-phenylsulfamoylamino), a sulfonyloxy group (having 1 to 30 carbon atoms, for example, methanesulfonyloxy, benzenesulfonyloxy),
Carbamoyl group (having 1 to 30 carbon atoms, such as N-dodecylcarbamoyl, N- [3- (2,4-di-
t-pentylphenoxy) propyl] carbamoyl, N
-[2-chloro-5- (1-dodecyloxycarbonylethyloxycarbonyl) phenyl] carbamoyl), a sulfamoyl group (having 0 to 30 carbon atoms, for example, ethylsulfamoyl, hexadecylsulfamoyl, 4;
-(2,4-di-t-pentylphenoxy) butylsulfamoyl, phenylsulfamoyl), acyl group (having 2 to 30 carbon atoms, for example, acetyl, octadecanoyl, benzoyl), sulfonyl group (carbon Those having a number of 1 to 30, such as methanesulfonyl, octadecanesulfonyl, benzenesulfonyl, 4-dodecylbenzenesulfonyl), alkoxycarbonyl groups (having 2 carbon atoms)
To 30, for example, ethoxycarbonyl, dodecyloxycarbonyl, benzyloxycarbonyl), aryloxycarbonyl groups (having 7 to 30 carbon atoms,
For example, phenoxycarbonyl). These groups may be further substituted with the groups mentioned above.

Next, Z in the formula [SI] will be described. Z is a hydrogen atom or a protective group that can be deprotected under alkaline conditions. Examples of the protecting group for Z include an acyl group (eg, acetyl, chloroacetyl, cycloloacetyl, benzoyl, 4-cyanobenzoyl, 4-oxopentanoyl), an oxycarbonyl group (eg, ethoxycarbonyl, phenoxycarbonyl, 4-methoxy). Benzyloxycarbonyl), a carbamoyl group (for example, N-methylcarbamoyl, N- (4-nitrophenyl) carbamoyl, N- (2-pyridyl) carbamoyl, N- (1-imidazolyl) carbamoyl, and JP-A-59-197.
No. 037, No. 59-201057, No. 59-1087.
76 and the protecting groups described in U.S. Pat. No. 4,473,537. When OZ and R ² to R ⁶ together form a ring, preferably OZ and R ² , R ²
And R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ or R ⁶
And OZ are bonded to each other to form a saturated or unsaturated 4- to 8-membered carbon ring or hetero ring. In this case, for example, the following may be mentioned. Here, the * mark represents the position bonded to the benzene ring of the formula [SI].

[0056]

[Chemical 28]

[0057]

[Chemical 29]

[0058]

[Chemical 30]

The compound represented by the formula [SI] may form a bis form, a tris form, an oligomer or a polymer. The total number of carbon atoms contained in R ² to R ⁶ of the formula [SI] is preferably 8 or more.

The compound represented by the formula [SI] according to the present invention can be synthesized by the methods described in the following patents and the patents cited therein and the methods analogous thereto. Monoalkyl-substituted hydroquinones are disclosed in U.S. Pat. Nos. 2,360,290, 2,419,613, 2,403,721, 3,960,570, and 3,700,453. 49-106329,
No. 50-156438, dialkyl-substituted hydroquinones are described in US Pat. Nos. 2,728,659 and 2,73.
2,300, 3,243,294, 3,70
0,453, JP-A-50-156438, 53-
No. 9528, No. 53-55121, No. 54-2963.
No. 7, 60-55339, hydroquinone sulfonates are disclosed in U.S. Pat. No. 2,701,197, JP-A-60-172040, 61-48855, 61.
-48856, amidohydroquinones are disclosed in U.S. Pat. Nos. 4,198,239 and 4,732,845;
JP-A-62-150346 and JP-A-63-309949 disclose hydroquinones having an electron-withdrawing group, JP-A-55-43521, JP-A-56-109344 and 57.
No. 222237 and No. 58-21249.

Others, US Pat. No. 4,447,523
Issue No. 4,525,451 Issue 4,530,899
No. 4, ibid. 4,584, 264, ibid. 4,717, 651
No. 59-220733, 61-16984.
5, Japanese Patent Publication No. 62-1386, West German Patent No. 2,73
2,971 and U.S. Pat. Nos. 4,474,874 and 4,476,219, JP-A-59-133544, and U.S. Pat. Nos. 2,710,801 and 2,816.
No. 028, 4,717,651, JP-A-57-17.
949, 61-169844 and JP-A-1-134.
No. 448, No. 1-134449, No. 1-206337.
No. 2-64631, No. 2-90153, etc. The alkali precursor of hydroquinone is described in US Pat. No. 4,443,537 and JP-A-59-108776.

Of the formula [SI], the following formula [SI] is preferred. General formula [S-IA]

[0063]

[Chemical 31]

In the formula, R _a and R _b are hydrogen atom, halogen atom, sulfo group, carboxyl group, alkyl group, acylamino group, alkoxy group, aryloxy group, alkylthio group, arylthio group, sulfonyl group, acyl group, carbamoyl. Group, a sulfamoyl group, and R _a and R
_b may together form a carbocycle. X is -CO- or -SO ₂ - represent. R _c represents an alkyl group, an aryl group, a heterocyclic group, a cycloalkyl group, an alkoxy group, an aryloxy group or an amino group. R _a, R _b, the total number of carbon atoms of R _c is 10 or more. The compound of the general formula [S-IA] is substantially colorless and does not form a color image by the coupling reaction with the developing agent.

The compound represented by formula [S-IA] will be described in more detail. In the formula, R _a and R _b are hydrogen atoms, halogen atoms (eg chlorine, bromine etc.), sulfo groups, carboxyl groups, alkyl groups (eg methyl, pentadecyl, t-hexyl), acylamino groups (eg acetylamino, benzoylamino). ), Alkoxy groups (eg methoxy, butoxy) aryloxy groups (eg phenoxy), alkylthio groups (eg octylthio, hexadecylthio), arylthio groups (eg phenylthio), sulfonyl groups (eg dodecanesulfonyl, p-
Toluenesulfonyl), an acyl group (eg acetyl, benzoyl), a carbamoyl group (eg N, N-dibutylcarbamoyl), a sulfamoyl group (eg N, N-diethylsulfamoyl), and R _a and R _b are jointly represented. To form a carbocycle. X is -CO- or-
Represents SO ₂ −. R _c is an alkyl group (for example, heptadecyl, 1-hexylnonyl, 1- (2,4-di-t-amylphenoxy) propyl), an aryl group (for example, phenyl, 3,5-bis (2-hexyldecanamido) phenyl, 3,4-bis (hexadecyloxycarbonyl) phenyl, 2,4-bis (tetradecyloxy) phenyl), heterocyclic group (eg 2,6-dihexyloxypyridin-4-yl, N-tetradecylpyrrolidine- 2-yl, N-octadecylpiperidin-3-yl), a cycloalkyl group (for example, 3-decanamidocyclohexyl,
3-{(2,4-di-t-amylphenoxy) butanamide} cyclohexyl), an alkoxy group (eg hexadecyloxy), an aryloxy group (eg 4-t-octylphenoxy), an amino group (eg octadecylamino) Represent. The total carbon number of R _a , R _b and R _c is 1
It is 0 or more.

The compound of the general formula [S-IA] may form a bis body, a tris body, a polymer or the like. In the general formula [S-IA], preferred substituents for R _a and R _b are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group and an alkylthio group, and among these, a hydrogen atom, a halogen atom and an alkyl group. Is more preferable,
Most preferably, it is a hydrogen atom. General formula [SI
X in A] is relatively preferably —CO—. In the general formula [S-IA], preferred substituents for R _c are an alkyl group and an aryl group, and among these, an aryl group is most preferred. General formula [S
-IA], when R _c is an aryl group, the substituent to be further substituted on the aryl group is not particularly limited as long as it is a commonly known substituent on an aryl ring, but the substituents described below Is relatively preferable. That is, a halogen atom, an alkyl group, an amide group, a sulfonamide group, an alkoxy group, an alkoxycarbonyl group, and a carbamoyl group. Further, it is preferable that the substituent further substituted on the aryl group is a group containing no sulfo group, carboxyl group or the like. The presence of these water-soluble groups may adversely affect the storage stability of the light-sensitive material.

The compound used in the present invention is also used as an agent for preventing color contamination and color fogging of a photographic light-sensitive material. Therefore, the compound itself is colored, or a color image is formed during the development processing. Doing so interferes with good color reproduction of the photographic light-sensitive material and defeats the purpose. Therefore, first, the compounds of the present invention are substantially colorless. Substantially colorless means here 400 nm to 700 n
It has no absorption with a molar extinction coefficient of 5000 or more in the visible wavelength range up to m. Secondly, the compound used in the present invention is a coupler residue (eg, acylacetanilide residue, 5 or 5) which is known to form a color image in the molecule by a coupling reaction with an oxidized product of a color developing agent. -Pyrazolone residue, 1-naphthol residue) and does not form a color image by the coupling reaction during the development process.

The alkali labile precursor of the compound represented by the general formula [S-IA] of the present invention is represented by the general formula [S-
IA] refers to a compound in which the hydroxyl groups at the 1-position and 4-position of the hydroquinone skeleton have a protective group that can be cleaved under alkaline conditions. Examples of the protecting group include an acyl group (eg, acetyl group, chloroacetyl group, benzoyl group, ethoxycarbonyl group, etc.), a β-eliminating group (eg, 2-cyanoethyl group, 2-methanesulfonylethyl group, 2- A typical example is a toluenesulfonylethyl group, etc.). These general formulas of the present invention [SI
The compound represented by A] and its alkali-labile precursor are easily prepared according to the methods described in US Pat. No. 2,701,197, JP-B-59-37497, JP-A-59-202465, and the like. Can be synthesized. Hereinafter, specific examples of the compound represented by the general formula [SI] will be shown, but the present invention is not limited thereto.

[0069]

[Chemical 32]

[0070]

[Chemical 33]

[0071]

[Chemical 34]

[0072]

[Chemical 35]

[0073]

[Chemical 36]

[0074]

[Chemical 37]

[0075]

[Chemical 38]

[0076]

[Chemical Formula 39]

[0077]

[Chemical 40]

[0078]

[Chemical 41]

[0079]

[Chemical 42]

[0080]

[Chemical 43]

[0081]

[Chemical 44]

[0082]

[Chemical formula 45]

[0083]

[Chemical formula 46]

[0084]

[Chemical 47]

[0085]

[Chemical 48]

[0086]

[Chemical 49]

[0087]

[Chemical 50]

[0088]

[Chemical 51]

[0089]

[Chemical 52]

[0090]

[Chemical 53]

[0091]

[Chemical 54]

[0092]

[Chemical 55]

[0093]

[Chemical 56]

[0094]

[Chemical 57]

[0095]

[Chemical 58]

[0096]

[Chemical 59]

[0097]

[Chemical 60]

[0098]

[Chemical formula 61]

[0099]

[Chemical formula 62]

Next, the formula [S-II] will be described in more detail. The coupler residue represented by Coup in the formula [S-II] is a known color coupler which can be used in subtractive color photography, and these are yellow coupler residue, magenta coupler residue, cyan coupler residue or It is a substantially colorless coupler residue. Preferred are coupler residues represented by the following general formulas [KI] to [KX]. General formula [KI]

[0101]

[Chemical formula 63]

General formula [K-II]

[0103]

[Chemical 64]

General formula [K-III]

[0105]

[Chemical 65]

General formula [K-IV]

[0107]

[Chemical formula 66]

General formula [KV]

[0109]

[Chemical formula 67]

General formula [K-VI]

[0111]

[Chemical 68]

General formula [K-VII]

[0113]

[Chemical 69]

General formula [K-VIII]

[0115]

[Chemical 70]

General formula [K-IX]

[0117]

[Chemical 71]

General formula [K-X]

[0119]

[Chemical 72]

R ₁₀₁ in the above general formula [KI] represents an alkyl group, an aryl group or an arylamino group, and R _101
102 represents an aryl group or an alkyl group. R ₁₀₃ in the above general formula [K-II] represents an alkyl group or an aryl group, and R ₁₀₄ represents an alkyl group, an acylamino group, an arylamino group, a phenylureido group, an alkylureido group or a heterocyclic group. R ₁₀₄ in formula [K-III] has the same meaning as R ₁₀₄ in formula [K-II], R ₁₀₅ is an acylamino group, a sulfonamido group, an alkyl group, an alkoxy group, an alkylthio group, a carbamoyl group, a sulfamoyl Represents a group, an alkoxycarbonyl group, and a halogen atom. The above general formulas [K-IV] and [K-
R ₁₀₆ is an alkyl group of V, an aryl group, an acylamino group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an acyl group, a sulfonyl group, a cyano group, R ₁₀₇ represents an alkyl group, an aryl group, an acylamino group, a sulfonamide Represents a group, arylamino group, alkoxy group, aryloxy group, alkylureido group, arylureido group, carbamoyl group, sulfamoyl group, acyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group. The above general formula [K
-VI], R ₁₀₈ represents a halogen atom, an alkyl group, an alkoxy group, an acylamino group or a sulfonamide group, R ₁₀₉ represents an acylamino group, an alkylureido group or an arylureido group, and Q ₁ represents a 5- to 7-membered hetero group. Represents an atom that may form a ring.

R ₁₀₉ in the above general formula [K-VII] represents a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and R ₁₁₀ represents an amino group, an acylamino group, an alkoxycarbonylamino group or an aryloxycarbonylamino group. Group, a sulfonamide group. R ₁₁₁ in the above general formula [K-VIII]
Represents an aryl group, R ₁₁₂ represents an alkyl group, an aryl group, a heterocyclic group, an acyl group, a carbamoyl group, a sulfamoyl group, an acylamino group, a sulfonamide group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, An alkoxycarbonylamino group,
It represents an aryloxycarbonylamino group, an ureido group, an anilino group, an amino group, an alkoxy group, or an aryloxy group. R ₁₁₃ in the above general formula [K-IX] is a nitro group,
It represents an acylamino group, a succinimide group, a sulfonamide group, an alkoxy group, an alkyl group, an aryl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₁₁₄ in the above general formula [K-X] represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acylamino group, a sulfonamide group, an alkoxycarbonyl group, an alkylureido group, an arylureido group, a carbamoyl group or a sulfamoyl group. , R ₁₁₅ represents a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, an acylamino group or a sulfonamide group, and Q ₂ is 5 to 5.
Represents an atom that may form a 7-membered ring. Further, n in the general formulas [K-VI], [K-IX] and [K-X] represents an integer of 0 to 2, and m in the general formula [K-VII].
Represents an integer of 0 or 1.

Further, each of the above-mentioned groups includes both unsubstituted groups and those having a substituent, and when having a substituent, preferable substituents are a halogen atom, a nitro group, a cyano group, a hydroxyl group and a carboxyl group. , Sulfonic acid group, alkyl group, alkoxy group, carbonyloxy group, alkoxycarbonyl group, acylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, amino group, aryl group, alkylthio group, arylthio group, heterocyclic group, etc. Is a group selected for. In each of the above general formulas, R _{101 to} R ₁₁₅ can be arbitrarily selected to impart diffusion resistance or diffusivity according to the purpose of use, but in the case of an ordinary image forming coupler having diffusion resistance, R ₁₀₁ The total number of carbon atoms of to R ₁₁₅ is preferably 10 to 60, more preferably 15 to 40. on the other hand,
In the case of a diffusible dye-forming coupler in which the dye produced by color development moves appropriately in the light-sensitive material during processing, R
The total number of carbon atoms of _{101 to} R ₁₁₅ is preferably 15 or less, more preferably 10 or less, and further preferably 8 or less. In this case, as the substituent of R _{101 to} R ₁₁₅ , at least one carboxyl group, sulfonic acid group,
It is preferable to have an alkylsulfonamide group or an arylsulfonamide group.

Incidentally, the substantially colorless coupler residue means
After forming a dye in color development, the dye flows out from the light-sensitive material into the processing solution, or the dye reacts with components in the processing solution to bleach the dye, or a coupling reaction occurs with an oxidant of a color developing agent. , A dye which remains substantially leuco or gives a substantially colorless product because the dye formed by coupling with the oxidation product of the color developing agent has a low molecular extinction coefficient in the visible region. These are known as efflux dye-forming couplers, bleaching dye-forming couplers, Weiss type couplers and colorless couplers, respectively. * Represents a position for bonding to-(Time) _a- (Sc). In the present invention, the coupler residue represented by Coup is preferably a diffusible, efflux dye-forming coupler.

In the above general formula [S-II],-(Ti
The timing group represented by me) _a − will be described. A known timing group can be used as the timing group, but the timing groups represented by (T-1) to (T-7) can be preferably used. * Is (Cou
p) and ** bind to (Sc), respectively.

[0125]

[Chemical formula 73]

R ₁₀ and R ₁₂ are hydrogen atom, halogen atom, alkyl group, alkenyl group, aralkyl group, alkoxy group, alkoxycarbonyl group, anilino group, acylamino group, ureido group, cyano group, nitro group, sulfonamide group, Represents a sulfamoyl group, a carbamoyl group, an aryl group, a carboxy group, a sulfo group, a cycloalkyl group, an alkanesulfonyl group, an arylsulfonyl group or an acyl group, and R ₁₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group or a cycloalkyl group. Or represents an aromatic group, t represents 1 or 2, and when t is 2, R ₁₀
The fused rings may be formed with each other. a is an integer of 0 or 1. In the present invention, a is preferably 0.
Therefore, at this time, the general formula [S-II] is (Coup)-
It is represented by (Sc). Next,-(Sc) in the general formula [S-II] will be described. Sc is a scavenger of an oxidized color developing agent capable of scavenging a residue or an oxidized color developing agent which is substantially inactive in the color developing process by a redox reaction or a coupling reaction after being released from Coup or a timing group. Represent. A residue that is substantially inactive in the color development process means that one of the active hydrogen atoms of the yellow coupler, magenta coupler, and cyan coupler, which is a color coupler applicable to subtractive color photography, is a coloring atom Examples thereof include known leaving groups that can be released during a coupling reaction with the body.
Although these leaving groups can be used even if they have diffusibility as long as they have no effect on the photographic properties, these leaving groups are preferably those imparting diffusion resistance.

The leaving group having diffusion resistance has a total number of carbon atoms of the leaving group of 8 or more, preferably 10 to 40. Known leaving groups include an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, a heterocyclic oxy group, a heterocyclic thio group, and a heterocyclic group bonded by a nitrogen atom. Can be mentioned.

Sc, a scavenger capable of scavenging the oxidized product of the color developing agent by a redox reaction, is a group capable of reducing the oxidized product of the color developing agent. For example, "The Theory of
thePhotographic Process "Chapter 11 (4 th Ed., Mac
millan company. 1977), Angew. Chem. Int. Ed., V
No. 17,875-886 (1978) and the like are preferable, and a precursor capable of releasing these reducing agents during development may be used. Specifically, when reacting with an oxidized product of a color developing agent, at least 2 of a hydroxyl group, a sulfonamide group, an amino group, a mono- or di-substituted amino group (such as a substituent is an alkyl, cycloalkyl, alkenyl or aryl group) is used. The aryl group and heterocyclic group each having one are preferable, and among them, the aryl group is preferable, and a phenyl group is particularly preferable. The Sc diffusivity and diffusion resistance of Sc at this time can be arbitrarily selected according to the purpose like the couplers represented by the above general formulas [KI] to [KX], but are preferably It is desirable to impart diffusion resistance, and the total number of carbon atoms is 6 to 40, more preferably 8 to 30. When a redox scavenger is used as Sc, Sc can be reused in this case by reducing the oxidized product of the color developing agent. When a scavenger capable of scavenging an oxidized color developing agent by a coupling reaction, Sc is a coupler residue and represents the above-mentioned efflux dye-forming coupler or a colorless coupler residue. In the present invention, Sc
Is preferably a residue which, after being released from Coup or a timing group, becomes a compound which is substantially inactive in the color development process. Therefore, the general formula [S-II] of the present invention is
The scavenger of the oxidized color developing agent represented by
Preferably, it is represented by the following general formula [S-IIA]. General formula [S-IIA]

[0129]

[Chemical 74]

In the formula, Coup ₁ is Co of the above [S-II].
Synonymous with up. Examples of the diffusion resistance imparting group represented by Ball include -O-, -S-, -OCO-, -OSO.
_2- , or -OCONH- is an optionally substituted alkyl group having 8 to 40 carbon atoms, an aryl group or a heterocyclic group bonded to the Coup coupling active position, and a nitrogen atom is bonded to the coupling active position. Total number of carbon atoms 1
There are 0 to 40 optionally substituted heterocyclic groups. Ball
Preferred examples of the alkoxy group having 8 to 40 carbon atoms, aryloxy group, alkylthio group, arylthio group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, heterocyclic oxy group, heterocyclic thio group and nitrogen atom. A heterocyclic group bonded with (for example, pyrrole, pyrazole, imidazole, triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, succinimide, maleinimide, phthalimide, 2-pyridone, 4-pyridone, imidazolidine-2,4- Dione, oxazolidine-2,
4-dione, thiazolidine-2,4-dione, triazolidine-3,5-dione, imidazolidine-2,4,5
-A group derived from trione or the like). These groups represented by Ball may be bound to each other by a divalent or higher polyvalent group, or may be pendantly bound to the ethylenic polymer main chain. In this case, the number of carbon atoms may be outside the above range.

The solubilizing group represented by Sol is a group containing a dissociable hydroxyl group, a carboxyl group, a sulfo group or an aminosulfonyl group, and the dissociable hydroxyl group, a carboxyl group, a sulfo group or an aminosulfonyl group is a direct group. Even if bound to the coupler residue, or bound to the coupler residue via a divalent group such as alkylene or arylene, or alkylene, arylene,
O -, - S -, - SO -, - SO 2 -, - CONH-,
_{-SO 2 NH -, - CONH -} , - COO -, - SO 2
You may couple | bond with a coupler group through the bivalent group which compounded O-, -CO-, -NH- etc. Multiple Sols may be attached to the uncoupling group of the coupler residue. S
As ol, a group containing a carboxyl group or a sulfo group is preferable. An example of a preferable Sol will be shown. However, the carboxyl group is a carboxylate group (for example, -COONa,-
May be COOK), sulfo group may be a sulfonate group (e.g. _{-SO 3 Na, -SO 3 K)} .
_{-COOH -SO 3 H -SO 2 NH 2} ,

[0132]

[Chemical 75]

[0133]

[Chemical 76]

[0134]

[Chemical 77]

[0135]

[Chemical 78]

[0136]

[Chemical 79]

[0137]

[Chemical 80]

In addition, the following can be mentioned. _{-CH 2 COOH, -CH 2 CH 2} COOH, -CH 2 CH 2 SO 3 H, -OCH 2 COO
H, -OCH ₂ CH ₂ COOH, -SCH ₂ COOH, -SCH ₂ CH ₂ COOH, -S
O ₂ CH ₂ CH ₂ COOH, -CONHCH ₂ CH ₂ COOH, -CONHCH ₂ COOH. The compound represented by the general formula [S-IIA] is preferably the following general formulas [QS-II], [QS-III] and [QS-I].
V], [QS-V], [QS-VI] or [QS-VII]
] It is a compound represented by these. General formula [QS-II]

[0139]

[Chemical 81]

General formula [QS-III]

[0141]

[Chemical formula 82]

General formula [QS-IV]

[0143]

[Chemical 83]

General formula [QS-V]

[0145]

[Chemical 84]

General formula [QS-VI]

[0147]

[Chemical 85]

General formula [QS-VII]

[0149]

[Chemical 86]

General formulas [QS-II], [QS-III],
[QS-IV], [QS-V], [QS-VI] and [QS
-VII], R ₂₀₁ represents an alkyl group having 1 to 8 carbon atoms (eg, methyl, t-butyl), 1 to 8 carbon atoms.
Alkoxy groups (eg methoxy, ethoxy)

[0151]

[Chemical 87]

A group represented by: or an aryl group having 6 to 10 carbon atoms (eg phenyl, 4-methoxyphenyl)
Represents R ₂₀₂ represents a halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom), an alkyl group having 1 to 8 carbon atoms (eg methyl, ethyl, hydroxymethyl), an alkoxy group having 1 to 8 carbon atoms (eg methoxy). , Ethoxy, methoxyethoxy, hydroxyethoxy), carbonamide groups having 1 to 10 carbon atoms (eg formamide, acetamide, benzamide), sulfonamide groups having 1 to 10 carbon atoms (eg methanesulfonamide, ethanesulfonamide, p -Toluenesulfonamide) or an aryloxy group having 6 to 10 carbon atoms (eg, phenoxy, p-methoxyphenoxy). R ₂₀₃ is a group having the same meaning as R ₂₀₂ and having 1 to 10 carbon atoms.
An amino group (for example, diethylamino, pyrrolidino, anilino, 2-chloroanilino) or having 6 to 10 carbon atoms
An aryl group of (for example, phenyl, 4-chlorophenyl,
3-acetamidophenyl, 2-methoxyphenyl).

R ₂₀₄ , R ₂₀₅ , R ₂₀₆ and R ₂₀₇ are each a group having the same meaning as R ₂₀₃ , a hydrogen atom, an alkylthio group having 1 to 8 carbon atoms (eg methylthio, benzylthio),
It represents an arylthio group having 6 to 10 carbon atoms (eg phenylthio, p-tolylthio) or an alkoxycarbonylamino group having 2 to 10 carbon atoms (eg methoxycarbonylamino, ethoxycarbonylamino). R
₂₀₈ is a group having the same meaning as R ₂₀₂ , a sulfamoyl group having 0 to 10 carbon atoms (eg, sulfamoyl, methylsulfamoyl, butylsulfamoyl, phenylsulfamoyl), an alkoxycarbonyl group having 2 to 10 carbon atoms (eg, Methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl) or a carbamoyl group having 1 to 10 carbon atoms (eg carbamoyl, methylcarbamoyl,
Butylcarbamoyl, phenylcarbamoyl). Each group described above may further have a substituent, and as the substituent, various groups described in the above R _{201 to} R ₂₀₈ can be substituted. b represents an integer of 1 or 2, m and n represent an integer of 0-4, p represents an integer of 0-2, q represents an integer of 1 or 2, and r represents 0-.
Represents an integer of 3. However, when m, n, p or r is plural, plural R ₂ may be the same or different, and when b or q is 2, plural Sol may be the same or different.

The above general formulas [QS-II] to [QS-VII]
Among the QS couplers represented by the general formula [QS-VI]
Alternatively, a QS coupler represented by [QS-VII] is preferable, and a QS coupler represented by the general formula [QS-VII] is particularly preferable. The following is used in the present invention [S
Specific examples of -II] are shown below, but the invention is not limited thereto.

[0155]

[Chemical 88]

[0156]

[Chemical 89]

[0157]

[Chemical 90]

[0158]

[Chemical Formula 91]

[0159]

[Chemical Formula 92]

[0160]

[Chemical formula 93]

[0161]

[Chemical 94]

[0162]

[Chemical 95]

[0163]

[Chemical 96]

[0164]

[Chemical 97]

[0165]

[Chemical 98]

[0166]

[Chemical 99]

[0167]

[Chemical 100]

[0168]

[Chemical 101]

[0169]

[Chemical 102]

[0170]

[Chemical 103]

[0171]

[Chemical 104]

[0172]

[Chemical 105]

[0173]

[Chemical formula 106]

[0174]

[Chemical formula 107]

[0175]

[Chemical 108]

The method of synthesizing the compound represented by the general formula [S-II] and other specific examples of the compound are described in, for example, JP-A-59-171955, JP-A-62-49349 and JP-A-63-311252. , JP-A-1-131560, etc. Formulas [SI] and [S-II] of the present invention
The compound represented by the formula (1) is a layer in a light-sensitive material such as a light-sensitive emulsion layer (blue-sensitive layer, green-sensitive layer and red-sensitive layer) or an adjacent layer thereof (for example, an intermediate layer adjacent to different color-sensitive emulsion layers and The emulsion layers may be contained in, for example, an intermediate layer sandwiched between substantially the same photosensitive emulsion layers), a protective layer, an antihalation layer, and other non-photosensitive layers, but preferably different emulsion layers. It is contained in the intermediate layer sandwiched between them. The compounds represented by the formulas [SI] and [S-II] of the present invention may be used by mixing two or more kinds of compounds in the same layer.
When a mixture of two or more kinds is used, the mixing ratio can be arbitrarily selected according to the purpose. Also, the same compound can be used in two or more layers. The formula [S-
The compound represented by I] and [S-II] can be added after being dissolved in a high-boiling point organic solvent and / or a low-boiling point organic solvent described later, emulsified and dispersed in a hydrophilic colloid medium or an aqueous solution. . Further, it can be added by dissolving it in a solvent such as water or alcohol at an appropriate concentration or by dispersing it in a latex which does not adversely affect the silver halide color light-sensitive material. The time of addition may be selected at any time during the manufacturing process, but in general, a method of adding immediately before coating is preferable.

The amount of the compound of the present invention added is 1 × 10 ⁻⁷ to 10 in the case of the intermediate layer, antihalation layer and protective layer.
1 × 10 ^-2 mol / m ² , preferably 1 × 10 ^-6 ~
5 × 10 ⁻³ mol / m ² , more preferably 1 × 10 ⁻⁵ to 2
× 10 ⁻³ mol / m ² . In the case of a silver halide emulsion layer, it is 1 per mol of silver halide contained in the layer.
× 10 ^{-4 to 1} mol, preferably 3 × 10 ^{-4 to} 5 × 10
⁻¹ mol, more preferably 1 × 10 ^{−3 to} 3 × 10 ⁻¹ mo
It is l. The compounds represented by the formulas [SI] and [S-II] of the present invention are excellent in the ability to prevent color mixing (color fog), and produce colored products during storage, during development or after development.
Side effects such as fog, sensitivity change, and color image fading are small. Further, it is effective with a small amount of addition, and a thin layer can be formed.
Furthermore, the general formula (I) and / or the general formula (I
The combined use of the coupler represented by I) and the compound represented by the formula [SI] and / or the formula [S-II] maintains a high color density, and the raw storability of the light-sensitive material before color development processing, particularly In addition, it exhibits excellent effects that the fluctuation of photographic properties is small, the effect of improving image quality such as color turbidity, graininess, and sharpness is enhanced, and the fastness of a color image is improved. Particularly, in the general formula [SI], [S
-IA] and the compound represented by [S-IIA] in the general formula [S-II] are preferable.

Next, the compound of the present invention capable of scavenging formaldehydes (compound which reacts with formaldehydes to fix it) will be described in detail. Preferred compounds capable of scavenging formaldehyde include the following general formulas [FI] to [F-III]. General formula [FI]

[0179]

[Chemical 109]

General formula [F-II]

[0181]

[Chemical 110]

General formula [F-III]

[0183]

[Chemical 111]

In the general formula [FI], R ₃₀₁ , R ₃₀₂ and R ₃₀₃ may be the same or different and each represents a hydrogen atom, an alkyl group (methyl group, ethyl group, n-propyl group, Isopropyl group, n-butyl group, hydroxymethyl group, 2-hydroxyethyl group, methoxymethyl group, chloromethyl group, carboxymethyl group, cyanoethyl group, etc., alkenyl group (aryl group, 2-butenyl group, 2
-Chloroallyl group, etc.), aralkyl group (benzyl group, phenethyl group, p-methoxybenzyl group, etc.), aryl group (phenyl group, p-tolyl group, p-methoxyphenyl group, o-chlorophenyl group, m-hydroxyphenyl group) Etc.) or an acyl group (acetyl group, propionyl group, trifluoroacetyl group, chloroacetyl group, acryloyl group, methacryloyl group, etc.). R ₃₀₄ and R
Each ₃₀₅ represents a hydrogen atom or an alkyl group (examples are the same as those described for R ₃₀₁ to R ₃₀₃ ). The glycoluril compound includes a polymer compound linked to a polymer chain (for example, polyethylene chain, polypropylene, etc.) via the groups R ₃₀₁ to R ₃₀₃ . Further, in this case, as the linking group, —CO—, —COO—, —CONH— and the like include groups linking the group of R ₃₀₁ to R ₃₀₃ to the polymer chain.

In formula [F-II], R ₃₀₆ and R ₃₀₇ represent hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group or an amino group, R ₃₀₆ and R ₃₀₇
May form a ring, and at least one of R ₃₀₆ and R ₃₀₇ is an acyl group, an alkoxycarbonyl group, a carbamoyl group or an amino group. _Xa is -CH =, or -N
Represents =. In formula [F-III], R ₃₀₈ represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and may form a bicycle with a phenyl ring. n is 2
Represents the above integers. In addition, the following general formula [F-IV-
1] to [F-IV-7] and [F-V-1], [F-V]
The compound represented by the general formula [-2] is also preferable as the compound capable of scavenging formaldehyde used in the present invention. Compounds that can change into enol form by tautomerism are
This is also included. [F-IV-1]

[0186]

[Chemical 112]

[F-IV-2]

[0188]

[Chemical 113]

[F-IV-3]

[0190]

[Chemical 114]

[F-IV-4]

[0192]

[Chemical 115]

[F-IV-5]

[0194]

[Chemical formula 116]

[F-IV-6]

[0196]

[Chemical 117]

[F-IV-7]

[0198]

[Chemical 118]

[FV-1]

[0200]

[Chemical formula 119]

[FV-2]

[0202]

[Chemical 120]

Here, R _{309 to} R ₃₃₀ represent hydrogen, an alkyl group, a substituted alkyl group, an aryl group and a substituted aryl group, and any one of R ₃₁₆ , R ₃₁₇ , R ₃₁₈ and R ₃₁₉ and R _324. Any one of ~ R ₃₂₈ must be hydrogen. R ₃₀₉ and R ₃₁₀ , R ₃₁₁ and R ₃₁₂ , R ₃₂₉ and R ₃₃₀ may form a ring, and R ₃₁₃
To R ₃₁₅ , R _{316 to} R ₃₁₉ , R _{320 to} R ₃₂₃ and R
₃₂₄ to R ₃₂₈ is one or two substituents in each group may form a ring. y represents an integer of 3 to 6, and z represents an integer of 2 or more.

Hereinafter, the above general formulas [FI] to [F-III] will be described.
] And [F-IV-1 to 7] and [F-V-1,2], specific examples of the compounds are shown below, but are not limited by the following examples.

[0205]

[Chemical 121]

[0206]

[Chemical formula 122]

[0207]

[Chemical 123]

[0208]

[Chemical formula 124]

[0209]

[Chemical 125]

[0210]

[Chemical formula 126]

[0211]

[Chemical 127]

[0212]

[Chemical 128]

[0213]

[Chemical formula 129]

[0214]

[Chemical 130]

The above compound can be synthesized by various methods. For example, compounds FS- (1) to FS- (31)
United Kingdom Patent No. 717,287, US Patent No. 2,731,
472, 3,187,004, H. Pauly, "Hemisch der Berichte" (Chem.Be
r.) 63B, 2063 (1930), FB Slezak "Journal of Organic Chemistry" 27, 2181 (1).
962), J. Nematollahl, "Journal of Organic Chemistry" (J. Org.
Chem.) 28, 2378 (1963) and the like, and is synthesized from carbon or substituted urea and an α-diketo compound (glyoxal, methylglyoxal, diacetyl, etc.) by the following reaction route.

[0216]

[Chemical 131]

Alkyl, acyl, hydroxymethyl, alkoxymethyl and halomethyl derivatives can be obtained by subjecting glycoluril to alkylation, acylation, hydroxymethylation, alkoxymethylation, halomethylation and the like by a conventional method. . Compound FS- (4
1) is an oligomer or polymer having n repeating units. Compounds FS- (32) to FS- (37) and FS- (4 which can scavenge formaldehydes
3) to FS- (54) are usually commercially available compounds, and FS- (38) to FS- (42) are Bulletin of the Chemical Society of Japan. Soiety of Japan, Vol. 39, pp. 1559-1567, pp. 1734-1738 (196)
6), Hemisch der Berichte (Chemische der Be
richte) 54, B 1802-1833, 2441
~ 2479 (1921), Beilstein Huntbuch der Organizer Chemie (Beilstein
Handbuch der Organischer Chemie) Hp 98 (192
It can be easily synthesized according to the method described in 1). FS- (55) is Beilstein Huntbuch der Organissen Chemie (Beilst
ein Handbuch der Organischen Chemie) 1st supplement version 4th
Vol. 354, Vol. 3, Vol. 63, etc.

In the present invention, the above compounds may be used alone or in combination of two or more, or one or more compounds capable of scavenging formaldehydes other than the above general formulas may be used. The compounds of the general formula may be used in combination with other compounds capable of scavenging formaldehydes. Examples of compounds capable of scavenging formaldehydes other than the above-exemplified compounds include, for example, JP-A Nos. 50-87028, 57-133450, 58-150950, and U.S. Pat. Nos. 2,895,827 and 3,3. 652,278
No. 3,811,891 and 4,003,748
Issue No. 4,411,987, No. 4,144,309
Issue No. 4,418, 142 Issue No. 4,464, 463
U.S. Patent No. 900,028, West German Patent No. 3,
223,699, 3,227,961, 3,2
27,962, Research Disclosure (Rese
Arch Disclosure) No. 10133 and the like can be used.

In the present invention, the layer containing at least one compound capable of scavenging formaldehyde is optional, and a layer of interest for preventing the influence of formaldehyde gas, a layer adjacent to the layer, or a layer closer to the layer. It can be contained in the outer layer. For example, it can be contained in the magenta coupler-containing layer, the other coupler-containing layer, or the layer outside thereof. Examples of these layers include silver halide emulsion layers, subbing layers, protective layers, intermediate layers, filter layers, antihalation layers,
Other auxiliary layers may be mentioned. Further, when it is desired to prevent the influence of formalin gas in the camera, a layer containing a compound capable of scavenging the formaldehydes can be formed at an arbitrary position of the light-sensitive material (film) (the back of the film is also acceptable).

The compound capable of scavenging formaldehyde used in the present invention can be added to these layers by adding the compound capable of scavenging formaldehyde to the coating solution for forming the layer as it is, or A solvent that does not adversely affect the silver halide color light-sensitive material,
For example, it can be added after being dissolved in water, alcohol or the like at an appropriate concentration. Alternatively, a compound capable of scavenging formaldehydes may be dissolved in a high boiling organic solvent and / or a low boiling organic solvent, emulsified and dispersed in an aqueous solution, and then added. As the high-boiling point organic solvent and the low-boiling point organic solvent used in this case, any of the solvents exemplified as those usable for forming the silver halide emulsion described below can be used. The compound capable of scavenging formaldehydes may be added at any time during the manufacturing process, but it is generally preferred to be added immediately before coating.
The addition amount is 1 m ^{2 of} silver halide photographic color light-sensitive material.
Is suitably 0.01 g to 10 g, but is preferably 0.05 g to 5 g.

The compound capable of forming a formaldehyde of the present invention is used in combination with the coupler represented by the general formula (I) or (II) of the present invention and a compound capable of scavenging an oxidized product of a developing agent or a precursor thereof. In addition to having the original scavenging ability of formalin gas, it exhibits an excellent effect of further improving desilvering and improving the raw storage stability of the light-sensitive material and the fastness of the obtained color image.

In the present invention, it is particularly preferable to add the compound represented by the general formula (B) and / or phenoxyethanol from the viewpoint of improving storage stability. General formula (B)

[0223]

[Chemical 132]

R ₀ represents an alkyl group having 1 to 5 carbon atoms. R ₀ is a methyl group, an ethyl group, an n-propyl group,
It represents an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, preferably an n-propyl group or an n-butyl group, and particularly preferably an n-butyl group. .

The light-sensitive material of the present invention may have at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer of a silver halide emulsion layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light. In a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red-color-sensitive layer and green. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-113.
No. 438, No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound and the like as described in the specification, and an anti-color mixing agent may be used as usual. May be included. The plural silver halide emulsion layers constituting each unit light-sensitive layer preferably have a two-layer constitution 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. be able to. 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. In addition,
57-112751, 62-200350, 62-206541, 62-2
As described in No. 06543, 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 (GL) / High sensitivity red photosensitive layer (RH) / Low sensitivity red photosensitive layer (RL) order, or BH / BL / GL / GH / RH / RL order, or BH / BL / GH /
It can be installed in the order of GL / RL / RH. In addition,
As described in JP-A-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. In addition, JP-A-56-25738 and 62-63936
It is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support, as described in the specification. Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and the layer is composed of three layers having different sensitivities in which the sensitivities are gradually 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, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four or more layers, the arrangement may be changed as described above. In order to improve color reproducibility, U.S. Pat.Nos. 4,663,271 and 4,70
5,744, 4,707,436, JP-A-62-160448, 6
3- 89850, it is preferable to arrange a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, RL, adjacent to or in proximity to the main photosensitive layer. . As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention contains silver iodobromide, silver iodochloride, or iodochlorobromide containing about 30 mol% or less of silver iodide. It is silver. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. The silver halide grains in a photographic emulsion are those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal shapes such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about
It may be fine particles of 0.2 μm or less or large-sized 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) N.
o.17643 (December 1978), pp. 22-23, "I. Emulsion production (Emu
lsion preparation and types) ”, and the same No.18716
(November 1979), p. 648, ibid. No. 307105 (November 1989), 863.
-865, and Graphide, Physics and Chemistry of Photography, published by Paul Montel (P.Glafkides, Chemie et P
hisique Photographique, PaulMontel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF D
uffin, Photographic Emulsion Chemistry (Focal Pres
s, 1966)), "Production and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (VL Zelikman et al.,
Making and Coating Photographic Emulsion, Focal Pr
ess, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff, PhotographicScience
and Engineering), Vol. 14, pp. 248-257 (1970);
U.S. Pat.Nos. 4,434,226, 4,414,310, 4,433,0
It can be easily prepared by the method described in 48, 4,439,520 and British Patent 2,112,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, 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 emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which forms a latent image inside the grain, or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The shell thickness of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the relevant portions are summarized in the table below. The light-sensitive material of the present invention comprises two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion.
It can be used by mixing in the same layer. US Patent No.
No. 4,082,553, the surface of which is covered with silver halide grains, U.S. Pat. No. 4,626,498, JP-A No. 59-214852, the inside of which is covered with silver halide particles, and colloidal silver are light-sensitively halogenated. It can be preferably used for the silver emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface is a silver halide grain that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat.
It is described in No. 9-214852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but as the average grain size,
0.01 to 0.75 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 grains (at least 95% of the weight or number of silver halide grains are within ± 40% of the average grain size) (Having a particle size of 1).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that it is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be optically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above-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, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23 to 24, page 648, right column 866 to 868 Color sensitizer: page 649, right column 4. Brightening agent: page 24, page 647, right column 868, fogging prevention 24: 25, page 649, right column 868: 870, stabilizer: light absorber, 25: Page 26 Page 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7. Stain 25 Page Right column 650 Page Left column 872 Inhibitor ~ Right column 8. Dye image Page 25 650 Page Left column 872 Stabilizer 9. Hardener 26 pages 651 left column 874 to 875 pages 10. Binder page 26 651 pages left column 873 to 874 pages 11. Plasticizers, page 27 650 pages right column 876 lubricants 12. Coating aids , Pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. static, page 27, page 650, right column, pages 876 to 877, inhibitor 14. matting agents, pages 878 to 879

The light-sensitive material of the present invention can be incorporated into US Pat. No. 4,740,4
54, No. 4,788,132, JP-A-62-18539, JP-A-1-
It is preferable to contain the mercapto compound described in No. 283551. A compound which, in the light-sensitive material of the present invention, releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof as described in JP-A 1-106052, irrespective of the amount of developed silver produced by development processing. Is preferably contained. In the light-sensitive material of the present invention, a dye dispersed by the method described in International Publication WO88 / 04794 or JP-A-1-502912 or
EP 317,308A, U.S. Pat.No. 4,420,555, JP 1-2593
It is preferable to include the dye described in No. 58. Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 1764 mentioned above.
3, VII-CG, and No. 307105, VII-CG
Are described in the patents listed in. Examples of the yellow coupler include, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,
No. 401,752, No. 4,248,961, No. 58-10739,
British Patents 1,425,020, 1,476,760, U.S. Patents 3,973,968, 4,314,023, 4,511,649
And those described in European Patent No. 249,473A, etc. are preferred.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,63 are preferred.
6, U.S. Pat.Nos. 3,061,432 and 3,725,067,
Research Disclosure No. 24220 (June 1984
Month), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A 61-7.
No. 2238, No. 60-35730, No. 55-118034, No. 60-185951
U.S. Pat.Nos. 4,500,630, 4,540,654, and
Those described in 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.
52,212, 4,146,396, 4,228,233, and
4,296,200, 2,369,929, 2,801,171,
No. 2,772,162, No. 2,895,826, No. 3,772,002
No. 3, No. 3,758,308, No. 4,334,011, No. 4,32
7,173, West German Patent Publication 3,329,729, European Patent 12
1,365A, 249,453A, U.S. Pat.No. 3,446,622
No. 4, No. 4,333,999, No. 4,775,616, No. 4,45
1,559, 4,427,767, 4,690,889, and
Those described in 4,254,212, 4,296,199 and JP-A-61-42658 are preferable. Furthermore, JP-A-64-553,
Pyrazoloazole couplers described in JP-A Nos. 64-554, 64-555 and 64-556 and imidazole couplers described in US Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are described in US Pat.
3,451,820, 4,080,211 and 4,367,282,
No. 4,409,320, No. 4,576,910, British patent 2,1
No. 02,137 and European Patent No. 341,188A.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,125,
570, European Patent 96,570, West German Patent (Publication) 3,
Those described in No. 234,533 are preferable. Colored couplers to correct unwanted absorption of colored dyes are
Disclosure No.17643, Item VII-G, No.30710
Item VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-3
9413, U.S. Pat.Nos. 4,004,929, 4,138,258,
Those described in British Patent 1,146,368 are preferred. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181, and a dye capable of reacting with a developing agent described in U.S. Pat.No. 4,777,120 to form a dye. It is also preferable to use a coupler having a precursor group as a leaving group. Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the above-mentioned RD 17643, VII-F and 307105 and VII-F patents, JP-A-57-151944, 57-154234 and 57-154234. 60-184248, 6
3-37346, 63-37350, U.S. Patents 4,248,962, 4,
Those described in No. 782,012 are preferable. RD No.1144
The bleaching accelerator releasing couplers described in JP-A No. 24241/1987, JP-A No. 61-201247, etc. are effective for shortening the processing time having a bleaching ability, and particularly, the tabular silver halide grains described above. The effect is great when it is added to the photosensitive material using. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent 2,097,140.
No. 2,131,188, JP-A-59-157638, and 59-170.
Those described in No. 840 are preferable. In addition, JP 60-1070
No. 29, No. 60-252340, Japanese Unexamined Patent Publication No. 1-4940, No. 1-45687
By the redox reaction with the oxidant of the developing agent described in No.
Compounds that release a fogging agent, a development accelerator, a silver halide solvent and the like are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,3.
38,393, 4,310,618 and the like, multi-equivalent couplers, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds described in JP-A-60-185950 and JP-A-62-24252. Alternatively, DIR redox-releasing redox compounds, couplers that release dyes that undergo color restoration after separation described in European Patents 173,302A and 313,308A, ligand-releasing couplers described in U.S. Pat. -75747 couplers releasing leuco dyes, U.S. Pat.
Examples thereof include couplers that release the fluorescent dye described in No. 181.

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

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-272248,
And 1,2-benzisothiazolin-3-one described in JP-A-1-80941, n-butyl p-hydroxybenzoate,
It is preferable to add various preservatives or antifungal agents such as phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole. The present invention can be applied to various color light-sensitive materials. Typical examples are 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 include, for example, the above-mentioned R
D. No.17643, page 28, No.18716, page 647 From right column 648
It is described on the left column of the page and on page 879 of the same No. 307105. 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, further preferably 18 μm or less, and particularly preferably 16 μm or less. Also, the film swelling speed T
_1/2 is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness means a film thickness measured under a humidity condition of 25 ° C. and 55% relative humidity (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 et al., Photographic Science and Engineering (Photog
r.Sci.Eng.), No. 19, No. 2, pages 124 to 129 can be measured by using a swellometer (swelling meter) of the type described, and T _1/2 is 30 ° C. in a color developer. , 90% of the maximum swollen film thickness reached after treatment for 3 minutes and 15 seconds is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness. Membrane swelling speed T
_1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (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.
In this back layer, the above-mentioned light absorber, filter dye,
It is preferable to contain an ultraviolet absorber, an antistatic agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid, a 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 to 29, No. 18716, 651 left column to right column, and No. 307105, pages 880 to 881 can be developed by a usual method. The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As this color developing agent,
Aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N diethylaniline and 3-methyl-4-amino-N-. Ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, especially 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline sulfate is preferred. Two or more of these compounds can be used in combination depending on the purpose. The color developer is an alkali metal carbonate,
It contains a pH buffer such as borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a development inhibitor such as a benzimidazole, a benzothiazole or a mercapto compound, or an antifoggant. It is common. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, Organic solvent such as diethylene glycol, benzyl alcohol,
Development accelerators such as polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphones. Acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene- 1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid,
Representative examples include ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

When the reversal processing is carried out, black and white development is usually carried out and then color development is carried out. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the light-sensitive material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When the replenishment 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 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, and more preferably 0.001 to 0.05. Is. As a method for reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the surface of the photographic processing liquid in the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit development processing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. 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 color developing agent at a high concentration.

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, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents include organic complex salts of iron (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. . Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patent 1,290,812.
No. 2,059,988, JP-A-53-32736, and JP-A-53-57831
No. 53, No. 53-37418, No. 53-72623, No. 53-95630, No. 53
-95631, 53-104232, 53-124424, 53-141
623, 53-28426, Research Disclosure
Compounds having a mercapto group or a disulfide group described in No. 17129 (July 1978), etc .; JP-A-50-140129
Thiazolidine derivatives described in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735, and US Pat. No. 3,706,561.
Thiourea derivative described in Japanese Patent No. 1,127,715, West German Patent
Iodide salts described in JP-A-58-16,235; West German Patent No. 966,
Polyoxyethylene compounds described in JP-A Nos. 410 and 2,748,430; polyamine compounds described in JP-B-45-8836; Other JP-A-49-40,943, 49-59,644, 53-94,92
No. 7, No. 54-35,727, No. 55-26,506, No. 58-163,940
Compounds described in No. 1; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, US Pat.
3,858, West German Patent 1,290,812, JP-A-53-95,630
Compounds described in US Pat. Further, U.S. Pat.
The compounds described in No. 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. Particularly preferred organic acid has an acid dissociation constant (pKa) of 2
A compound of -5, specifically acetic acid, propionic acid,
Hydroxyacetic acid and the like are preferred. Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts, but the use of thiosulfates 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. Preservatives for fixers and bleach-fixers include sulfites, bisulfites, carbonyl bisulfite adducts or European Patent No. 294
The sulfinic acid compounds described in No. 769A are preferable. Furthermore,
For the purpose of stabilizing the solution, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution. In the present invention, the fixer or the bleach-fixer has a pH of
For adjustment, a compound having a pKa of 6.0 to 9.0, preferably an imidazole such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole.
It is preferable to add 1 to 10 mol / l.

The total time of the desilvering process is preferably as short as possible so long as desilvering failure does not occur. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The treatment 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 process, it is preferable that the stirring is strengthened as much as possible.
As a specific method for strengthening stirring, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461 Method to increase the effect, further moving the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the solution to further 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 is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, 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 processor used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
No. 60-191258 and No. 60-191259. The above-mentioned JP-A-6
As described in No. 0-191257, 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 process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, and further, the rinsing water temperature, the number of rinsing tanks (the number of stages), the replenishment system such as countercurrent and forward flow, and various other conditions. It can be set in a wide range.
Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is as follows.
nd Tele-vision Engineers Volume 64, P. 248 ~ 253 (195
It can be obtained by the method described in the May 5 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, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively as a solution to such a problem. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" (1986)
Sankyo Publishing, Sanitary Technology Society, "Microbial sterilization, sterilization, antifungal technology" (1982), Industrial Technology Association, Japan Antibacterial and Antifungal Society edited, "Antibacterial and Antifungal Encyclopedia" (1986) Can also be used. 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 the washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but in general, it is 20 seconds to 10 minutes at 15 to 45 ° C., preferably
A range of 30 seconds to 5 minutes at 25-40 ° C is 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 stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used. Further, there is a case where further stabilizing treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. be able to. As a dye stabilizer,
Aldehydes such as formalin and glutaraldehyde,
Examples thereof include N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.
Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the washing with water and / or the replenishment of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline-based compounds described in U.S. Pat. Metal salt complexes described, JP-A-53-135
The urethane compound described in No. 628 can be mentioned.
The silver halide color light-sensitive material of the present invention contains various 1-phenyl-3-methyl-3-phenyl-3-(-3-phenyl) -3-phenyl-3- (phenyl-3-phenyl) -3- (phenyl-3-phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3- (phenyl) -3-(-3-phenyl-3-phenyl-3- (cyclohexyl) -3- (phenyl-3-phenyl-3-methyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3-phenyl-3- (3-phenyl-3-phenyl-3- (3-phenyl-3- (phenyl-phenyl--3-one-
You may incorporate pyrazolidones. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, JP-A-58-115438 and the like. Various treatment liquids in the present invention are 10 ℃
Used at ~ 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, the silver halide light-sensitive material of the present invention includes U.S. Pat. No. 4,500,626, JP-A-60-133449, JP-A-59-218443, and JP-A-61-238056.
It can also be applied to the photothermographic material described in European Patent No. 210,660A2.

[0244]

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 of silver coverage (Composition of photosensitive layer) The silver halide and colloidal silver, expressed in units of g / m ^2, also a 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. First layer: antihalation layer Black colloidal silver Silver coverage 0.20 Gelatin 2.20 UV-1 0.11 UV-2 0.20 Cpd-1 4.0 × 10 ^-2 Cpd-2 1.9 × 10 ^-2 Solv-1 0.30 Solv-2 1.2x10 ^-2 Second layer: intermediate layer Fine grain silver iodobromide (AgI 1.0 mol%, sphere equivalent diameter 0.07 µm) Silver coating amount 0.15 Gelatin 1.00 ExC-4 6.0 × 10 ^-2

Third Layer: First Red Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 5.0 mol%, surface high AgI type, sphere equivalent diameter 0.9 μm, variation coefficient of sphere equivalent diameter 21%, tabular grains , Diameter / thickness ratio 7.5) Silver coating amount 0.42 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, sphere equivalent diameter 0.4 μm, variation coefficient of sphere equivalent diameter 18%, 10 Tetrahedral grains) Silver coating amount 0.40 Gelatin 1.90 ExS-1 4.5 × 10 ^-4 mol ExS-2 1.5 × 10 ^-4 mol ExS-3 4.0 × 10 ^-5 mol ExC- 1 0.40 ExC-7 0.32 ExC-3 1.0 × 10 ^-2 ExC-4 2.3 × 10 ^-2 Solv-1 0.32 Fourth layer: second red-sensitive emulsion layer Silver iodobromide Emulsion (AgI 8.5 mol%, internal high AgI type, sphere equivalent diameter 1.0 μm, variation coefficient of sphere equivalent diameter 25%, plate-like particles, diameter / thickness ratio 3.0) The coating amount 0.85 Gelatin 0.91 ExS-1 3.0 × 10 ^-4 mol ExS-2 1.0 × 10 ^-4 mol ExS-3 3.0 × 10 ^-5 mol ExC-1 0.06 ExC- 7 0.09 ExC-2 6.2 × 10 ^-2 ExC-4 4.0 × 10 ^-2 ExC-6 3.0 × 10 ^-2 Solv-1 0.10 Fifth layer: third red-sensitive emulsion layer Silver iodobromide emulsion (AgI 1 1.3 mol%, internal high AgI type, sphere equivalent diameter 1.4 μm, variation coefficient of sphere equivalent diameter 28%, plate-like grain, diameter / thickness ratio 6.0) Silver coating amount 1.50 Gelatin 1.20 ExS-1 2.0 × 10 ⁻⁴ mol ExS-2 6.0 × 10 ⁻⁵ mol ExS-3 2.0 × 10 ⁻⁵ mol ExC-2 8.5 × 10 ⁻² ExC-5 7.3 × 10 ^-2 ExC-6 1.0 × 10 ^-2 Solv-1 0.12 Solv-2 0.12

Sixth Layer: Intermediate Layer Gelatin 1.00 Solv-1 8.0 × 10 ^-2 Seventh Layer: First Green Sensitive Emulsion Layer Silver iodobromide emulsion (AgI 5.0 mol%, surface high AgI type) , Sphere equivalent diameter 0.9 μm, variation coefficient of sphere equivalent diameter 21%, tabular grain, diameter / thickness ratio 7.0) Silver coating amount 0.28 Silver iodobromide emulsion (AgI 5.0 mol%, internal height) AgI type, sphere equivalent diameter 0.4 μm, variation coefficient of sphere equivalent diameter 18%, tetradecahedral grain) Silver coating amount 0.16 Gelatin 1.20 ExS-4 5.0 × 10 ^-4 mol ExS-52 .0 × 10 ^-4 mol ExS-6 1.0 × 10 ^-4 mol ExM-1 0.50 ExM-2 0.10 ExM-5 3.5 × 10 -2 mol Solv-1 0.20 Solv-3 3.0 × 10 ^-2 8th layer: 2nd green-sensitive emulsion layer silver iodobromide emulsion (AgI 8.5 mol%, internal high AgI type, sphere-corresponding diameter 1.0 m, a variation coefficient of 25% equivalent spherical diameter, tabular grain, diameter / thickness ratio 3.0) silver coverage 0.57 Gelatin 0.45 ExS-4 3.5 × 10 ^-4 mol ExS-5 1.4 X10 ^-4 mol ExS-6 7.0 x10 ^-5 mol ExM-1 0.12 ExM-2 7.1 x10 ^-3 ExM-3 3.5x10 ^-2 Solv-1 0.15 Solv- 3 1.0 x 10 ^-2

Ninth layer: Intermediate layer Gelatin 0.50 Solv-1 2.0 × 10 ^-2 Tenth layer: Third green emulsion layer Silver iodobromide emulsion (AgI 1 1.3 mol%, internal high AgI) Type, equivalent sphere diameter 1.4 μm, variation coefficient of equivalent sphere diameter 28%, plate-like particles, diameter / thickness ratio 6.0) Silver coating amount 1.30 Gelatin 1.20 ExS-4 2.0 × 10 ^-4 Mol ExS-5 8.0 × 10 ⁻⁵ mol ExM-4 5.8 × 10 ⁻² ExM-6 5.0 × 10 ⁻³ ExC-2 4.5 × 10 ⁻³ Solv-1 0.25

11th layer: Yellow filter layer Gelatin 0.50 Cpd-3 5.2 × 10 ^-2 Solv-1 0.12 12th layer: Intermediate layer Gelatin 0.45 13th layer: 1st blue sensitive emulsion layer Silver iodobromide emulsion (AgI 2 mol%, uniform AgI type, sphere equivalent diameter 0.55 μm, variation coefficient of sphere equivalent diameter 25%, tabular grains, diameter / thickness ratio 7.0) Silver coating amount 0.20 Gelatin 1.00 ExS-7 3.0 × 10 ^-4 mol Comparative coupler (a) 0.60 Comparative coupler (b) 2.7 × 10 ^-2 Solv-1 0.15 14th layer: second blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 19.0 mol%, internal high AgI type, sphere equivalent diameter 1.0 μm, variation coefficient of sphere equivalent diameter 16%, octahedral grains) Silver coating amount 0.19 Gelatin 0.35 ExS- 7 2.0 × 10 ^-4 mol comparative coupler (a) 0.22 Solv 1 7.0 × 10 ^-2

Fifteenth layer: intermediate layer Fine grain silver iodobromide (AgI 2 mol%, uniform AgI type, equivalent spherical diameter 0.13 μm) Silver coating amount 0.20 Gelatin 0.36 16th layer: Third blue sensitive emulsion Layer Silver iodobromide emulsion (AgI 14.0 mol%, internal high AgI type, sphere equivalent diameter 1.7 μm, variation coefficient of sphere equivalent diameter 28%, plate-like grains, diameter / thickness ratio 5.0) Silver coating amount 1.55 Gelatin 1.00 ExS-8 1.5 × 10 ^-4 mol Comparative coupler (a) 0.21 Solv-1 7.0 × 10 ^-2 17th layer: 1st protective layer Gelatin 1.80 UV- 1 0.13 UV-2 0.21 Solv-1 1.0x10 ^-2 Solv- ² 1.0x10 ^-2 18th layer: 2nd protective layer Fine particle silver chloride (sphere equivalent diameter 0.07 μm) Silver The coating amount 0.36 gelatin 0.70 B-1 (diameter ^{1.5μm) 2.0 × 10 -2 B-} 2 ( diameter .5μm) 0.15 B-3 3.0 × 10 -2 W-1 2.0 × 10 -2 H-1 0.35

In addition to the above, the samples thus prepared include
1,2-benzisothiazolin-3-one (average 200 ppm relative to gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm the same), and 2-
Phenoxyethanol (about 10,000 ppm) was added. Furthermore, B-4, B-5, W-2, W-3, F
-1, F-2, F-3, F-4, F-5, F-6, F-
7, F-8, F-9, F-10, F-11, F-12,
F-13 and iron salt, lead salt, gold salt, platinum salt, iridium salt and rhodium salt are contained. The structural formulas of the compounds used are shown below.

[0252]

[Chemical 133]

[0253]

[Chemical 134]

[0254]

[Chemical 135]

[0255]

[Chemical 136]

[0256]

[Chemical 137]

[0257]

[Chemical 138]

[0258]

[Chemical 139]

[0259]

[Chemical 140]

[0260]

[Chemical 141]

[0261]

[Chemical 142]

[0262]

[Chemical 143]

[0263]

[Chemical 144]

[0264]

[Chemical 145]

[0265]

[Chemical 146]

[0266]

[Chemical 147]

Samples 102 to 112 are the thirteenth sample of Sample 101.
The comparative coupler (a) and the comparative coupler (b) used in the layers, 14th and 16th layers were changed as shown in Table 1 and replaced by equimolar amounts, and the Solv-1 / total coupler weight ratio was changed to Sample 101. A sample was prepared according to. Sample 113-
124 corresponds to each of the samples 101 to 112, and
The compound (3) capable of scavenging the oxidized product of the developing agent of the present invention is contained in the second layer, the first layer and the intermediate layer of the second layer, the sixth layer and the twelfth layer.
0.02, 0.10 g / m ² and (20) were added to the 2nd layer so as to be 0.08 g / m ² to the 6th layer, and (17) to the 8th and 10th green-sensitive emulsion layers. 0.015, 0.035 g /
A sample was prepared by adding it to m ² .

The samples thus prepared were cut and processed, and then subjected to white light gradation exposure, and then the cumulative replenishment amount of the color developing solution replenisher was determined by the method described below using an automatic developing machine. The sample was separately imagewise exposed to a volume three times the volume, and the treatment was carried out when the running equilibrium was reached. 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 fixed 4 minutes 20 seconds 38 ℃ 25ml 30 liters Water wash (1) 1 minute 05 seconds 24 ℃ 10 liters from (2) to (1) Countercurrent piping system water wash (2) 1 minute 00 seconds 24 ℃ 1200ml 10 liter stability 1 minute 05 Second 38 ℃ 25ml 10 liter dry 4 minutes 20 seconds 55 ℃ Replenishment amount is 35mm width 1m per length

Next, the composition of the treatment liquid will be described. (Color developer) Mother liquor (g) Replenisher (g)   Diethylenetriamine pentaacetic acid 1.0 1.1   1-Hydroxyethylidene-1,1 3.0 3.2     -Diphosphonic acid   Sodium sulfite 4.0 4.4   Potassium carbonate 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     Xyethylamino] -2-methyl     Aniline sulfate   Add water 1.0 liter 1.0 liter   pH 10.05 10.10

[0270] (Bleach) Mother liquor (g) Replenisher (g)   Ferric ethylenediaminetetraacetic acid 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   Ammonia water (27%) 6.5 ml 4.0 ml   Add water 1.0 liter 1.0 liter   pH 6.0 5.7

[0271] (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     (700 g / liter)   Add water 1.0 liter 1.0 liter   pH 6.7 6.6

[0272] (Stabilizer) Mother liquor (g) Replenisher (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 disodium salt 0.05 0.08   Add water 1.0 liter 1.0 liter   pH 5.0-8.0 5.0-8.0

The samples obtained by the treatment were subjected to density measurement of B, G and R three colors to obtain their characteristic curves, and the performances shown below were evaluated. Further, depending on the purpose of performance evaluation, the exposure was separately performed and the above treatment was performed. A sample was prepared by using the reference coupler (f) instead of the comparative coupler (a), but the coupler was deposited, and the above treatment was performed, but the color development was not possible and the performance evaluation could not be performed. (1) From the characteristic curve measured with photographic blue (B) light, the minimum density +0.3
The logarithm of the reciprocal of the exposure dose that gives the density of is determined as sensitivity (S), and the difference (ΔS
₁ ) was calculated. The larger the value of +, the higher the feeling, and the larger the value, the lower the feeling. Further, from the exposure amount at the sensitivity point to the high exposure amount side, logE = 1.
Read the density value (D) at which the exposure amount of 5 is given,
Similarly, based on sample 101, the percentage (D ₁ %)
Was calculated.

(2) Color image fastness Using the samples of (1), these samples were tested at 60 ° C. and 70% R
Store under H condition for 15 days, measure concentration again, and
The density value obtained by giving a density of +2.0, which is the minimum density before the start of the test, measured by light is read, and the ratio (D ₂ %) of the remaining density value to the density before the start of the test is obtained to obtain the color image residual rate. And It is shown that a higher numerical value gives higher color image fastness. (3) Stability of Sensitive Material with Time (A) Two sets of each of the prepared samples were prepared, one set was stored at 50 ° C. and 60% RH for 5 days, and the other set was stored for the same period. Stored at 5 ° C. After saving these 2
The samples of the set were subjected to grayscale exposure with white light as before, and the above-mentioned treatments were simultaneously performed. For the processed sample, measure the concentration and
The sensitivity point on the characteristic curve measured by light was determined in the same manner as in (1), and the difference (ΔS ₂ ) was calculated based on the sensitivity of the samples stored at 5 ° C. between the same samples. (B) As an evaluation of the stability of the latent image with time, two sets of each sample were prepared and exposed in the same manner as in (1), and one set of sample was 50
After storing for 10 days under the conditions of 30 ° C and 30% RH, another set was stored under the same conditions of 5 ° C, and then these two sets were simultaneously subjected to the above-mentioned treatment. The density of the processed sample is measured, and the sensitivity is obtained from the characteristic curve of B light in the same manner as (1).
The sensitivity difference (ΔS ₃ ) from the sample stored at 50 ° C. was calculated with reference to the value of the sample stored at 0 ° C. The smaller the numerical values of (A) and (B), the smaller the fluctuation of sensitivity and the better the storage stability. -The sign represents desensitization.

(4) Image quality (C) Color turbidity After each sample was uniformly exposed with green light for 1 Lux · sec,
After the gradation exposure of B light is applied, the above-described processing is performed, and the magenta density value at the minimum yellow density is subtracted from the magenta density value at the exposure amount that gives the minimum yellow density of +1.5. The value obtained was taken as the color turbidity and used as a measure of color reproducibility. The smaller the value, the lower the density in the green color range, and the higher the color saturation. (D) Granularity The RMS value at the minimum yellow density +0.5 density measured with an aperture having a diameter of 48 μm is shown. The smaller the value, the better the graininess. (E) The MTF value of a yellow color image at a sharpness of 25 cycles / mm was determined. Measurement of MTF value is The Theory of the Photographic
It was carried out according to the method described in Process, 3rd Ed., (Published by Macmillan, written by Mies).

The results obtained in these (1) to (4) are summarized in Table 1 and Table 2. The structural formulas of the comparative couplers and the reference couplers shown in Tables 1 and 2 are shown below.

[0277]

[Table 1]

[0278]

[Table 2]

[0279]

[Chemical 148]

[0280]

[Chemical 149]

From the table, samples 101 to 112 and sample 113
When the comparative sample in each block of 124 to 124 and the sample satisfying the constitutional requirements of the present invention are compared, the sample of the present invention shows color turbidity and stability of the light-sensitive material with time without changing the photographic property. It is clear that the image quality is improved, and the color image fastness, graininess, and sharpness are also improved. It is also clear that even in the sample satisfying the constitutional requirements of the present invention, the reference coupler is superior to the reference coupler, and the coupler of the present invention is superior to the reference coupler. When the samples satisfying the constituent requirements of are compared with each other (Samples 115 and 116 and Sample 11).
It can also be seen from the table that the combination of 9, 120 and Samples 121 to 124) and the coupler according to the present invention is the most excellent. As described above, in the case of the reference coupler (f), the produced sample had coupler deposits, and its performance could not be evaluated even if the treatment was carried out due to defective coloring. This indicates that in the present invention, it is necessary to have a hydrophobic diffusion resistant group in the coupler molecule.

Example 2 Based on the sample 124 prepared in Example 1, the 13th and 1st
The couplers (3) and (3 of the present invention used for 4 and 16 layers
(3) is replaced with another coupler of the present invention in an equimolar amount, the weight ratio of Solv-1 / all couplers is adjusted, and the oxidized developer of the present invention is further used in the second, sixth, eighth, tenth and twelfth layers. A sample was prepared by substituting equimolar amounts for the compound capable of scavenging. These modified couplers and compounds are shown in Tables 3 and 4. These samples are from Example 1.
The performance was similarly evaluated according to the method described in 1. The processing steps and the composition of the processing solution at this time are as follows. Similar to Example 1, imagewise exposure was separately performed until the cumulative replenishing amount of the color developing solution replenishing solution became three times the mother solution tank capacity. The samples were run and then processed. For comparison, Sample 101 manufactured in Example 1
Were processed simultaneously.

Treatment Process Process Treatment time Treatment temperature Replenishment amount Tank capacity Color development 3 minutes 05 seconds 38.0 ° C 600 ml 5 liters Bleach 50 seconds 38.0 ° C 140 ml 3 liters Bleach fixing 50 seconds 38.0 ° C -3 liters fixed 50 seconds 38.0 ℃ 420ml 3 liters Water wash 30 seconds 38.0 ℃ 980ml 2 liters stable (1) 20 seconds 38.0 ℃ ─ 2 liters stable (2) 20 seconds 38.0 ℃ 560ml 2 liters dry 1 minute 60 ℃ * Replenishment amount per 1m ² of photosensitive material The amount of washing water was a countercurrent method 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 are respectively per 1 m ² of the light-sensitive material. 65ml, 50ml, 50m
l, 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 processing liquid is shown below. (Color developer) Mother liquor (g) Replenisher (g)   Diethylenetriamine pentaacetic acid 2.0 3.0   1-Hydroxyethylidene-1,1 3.3 3.3     -Diphosphonic acid   Sodium sulfite 3.9 5.2   Potassium carbonate 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-N 4.5 6.0     -(Β-hydroxyethyl) ami     No] aniline sulfate   Add water 1.0 liter 1.0 liter   pH 10.05 10.05

[0285] (Bleach) Mother liquor (g) Replenisher (g)   1,3-Propylenediaminetetraacetic acid 144.0 206.0     Ferric ammonium-hydrate   Ammonium bromide 84.0 120.0   Ammonium nitrate 17.5 25.0   Hydroxyacetic acid 63.0 80.0   Acetic acid 54.2 80.0   Add water 1.0 liter 1.0 liter   pH [adjusted with ammonia water] 3.80 3.60

(Bleaching / fixing solution mother liquor) A 15:85 mixture of the above bleaching solution mother liquor and the following fixing solution mother liquor.

[0287] (Fixer) Mother liquor (g) Replenisher (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 37.5   Add water 1.0 liter 1.0 liter   pH [adjusted with aqueous ammonia and acetic acid] 7.40 7.45

(Washing Water) Common tap water for mother liquor and replenisher was prepared by using H type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type strongly basic anion exchange resin (Amberlite IRA-type). Four
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.

[0289] (Stabilizer) Common for 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   1.0 liter with water   pH 7.2

[0290]

[Table 3]

[0291]

[Table 4]

The results obtained are summarized in Table 5.

[0293]

[Table 5]

From Table 5, the sample produced in this example satisfying the constitutional requirements of the present invention has a coloring property when compared with the sample 101 of Example 1 and the data of the comparative sample of Example 1. It is clear that the photosensitive material is excellent in stability over time, color image fastness, and image quality. However, even in the samples satisfying the constitutional requirements of the present invention, the couplers represented by the general formula (II) are superior to the couplers represented by the general formula (I) in the samples 201 to 209 and the sample 213.
It can be seen from the comparison of ~ 215. Also, in the coupler represented by the general formula (I), among the non-functional leaving groups, the N-leaving group is better than the O-leaving group in Samples 201 to 209 and Sample 210. It can be seen from the comparison of ~ 212.

Example 3 First of Samples 114, 116 and 124 prepared in Example 1
In the eight layers, 1.00 of (FS- (2)) shown in the specific examples of the compound of the present invention capable of scavenging formaldehydes is shown.
A sample was prepared by adding so as to have g / m ² . Let these samples be 301, 302, and 303. Subsequently, Example 2
Samples 209, 210, 215, 216 and 22 prepared in
Similarly, for 0, (FS- (2)) was added to the same layer in the same amount to prepare a sample. These sample numbers are 304, 305, 3
06, 307, 308. Furthermore, the first of sample 303
As shown in Table 6 in the eight layers, a sample was prepared by substituting the compound capable of scavenging the formaldehydes of the present invention (FS- (2)) with another compound in an equimolar amount. The produced sample was cut and processed to have a width of 35 mm, the treatment described in Example 2 was performed, and the same performance evaluation was performed. In addition to these performance evaluations, uniform white light exposure was applied so that 90% of the total coated silver amount was developed silver, and processing was performed, and the amount of silver remaining in the photosensitive material after processing was quantified by the fluorescent X-ray method. did. Further, in the processing shown in Example 2, a sample subjected to gradation exposure of white light before and after the running processing was processed, and the fluctuation of the photographic property due to the running processing of the yellow color image was examined. The evaluation was based on the sensitivity difference before and after the running process (ΔS ₄ ) based on the sensitivity before the start of running. Of the obtained results, the photographic properties and image quality (color turbidity, graininess, sharpness) were not different between the corresponding samples such as Sample 114 and Sample 301, and therefore omitted. The results of stability, continuous processability, color image fastness, and desilvering property are summarized in Table 6. In addition, for comparison, samples 114, 116, 124, and 20 are used.
9, 210, 215, 216 and 220 are also described.

[0296]

[Table 6]

From the table, it is possible to scavenge formaldehydes into a light-sensitive material using the coupler represented by the general formula (I) and / or the general formula (II) and the compound capable of scavenging the oxidized product of the developing agent, which is the constitution of the present invention. It is understood that the use of such a compound further improves the temporal stability, the color image fastness, the fluctuation of the photographic property (sensitivity) in continuous processing, and the desilvering property. The improvement effect is that of samples 114 and 3.
It is also clear that the effect of the present invention is greater than that of 01.

[0298]

The light-sensitive material using the coupler represented by the general formula (I) and / or the general formula (II) and the compound capable of scavenging the oxidized product of the developing agent or its precursor has high color density and high sensitivity. The absorption of long wavelength is small, the stability of the light-sensitive material with time and the latent image are excellent, the graininess and the sharpness are improved, and the color image is robust and excellent. Therefore, it is possible to provide a silver halide color photographic light-sensitive material which gives high color developability and is excellent in stability over time and image quality. Furthermore, by using a compound that can scavenge formaldehydes (a compound that reacts with formaldehydes and fixes it), stability over time, color image fastness, continuous processability, and improvement in image quality by reducing the amount of residual silver It is possible to provide a silver halide color photographic light-sensitive material having further excellent performance.

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive emulsion layer and at least one non-light-sensitive emulsion layer on a support, wherein the formula (I) and / or the formula (I) A silver halide color photographic light-sensitive material comprising a coupler represented by II) and a compound capable of scavenging an oxidized product of a developing agent or a precursor thereof. General formula (I) General formula (II) In the formula, X1 and X2 each represent an alkyl group, an aryl group or a heterocyclic group, X3 represents an organic residue forming a nitrogen-containing heterocyclic group with> N-, and Y represents an aryl group or a heterocyclic group. , Z represents a group which leaves when the coupler represented by the general formula reacts with an oxidized product of a developing agent. 2. A silver halide color photographic light-sensitive material according to claim 1, which contains a compound capable of scavenging formaldehydes.