JP2672208B2 - Silver halide color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material using a novel yellow coupler which gives a high color density and improves color image storability and image quality.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material (hereinafter abbreviated as light-sensitive material), particularly a color light-sensitive material for photographing, gives high color density with high sensitivity to obtain an image quality (color reproducibility, A photosensitive material excellent in sharpness, graininess, etc.) and color image fastness is desired. 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. When these two couplers are compared, the benzoylacetanilide type couplers give high color development due to high coupling activity and high molecular extinction coefficient of the color forming dye, but the absorption of the color forming dye on the super wavelength side (green region) It is slightly large and has some difficulties in the robustness of color images. On the other hand, although the pivaloylacetanilide-based coupler has somewhat better spectral absorption characteristics and color image fastness than the benzoylacetanilide-based coupler, it has low coupling activity and also has a low molecular extinction coefficient of the coloring dye. In order to obtain the density, it is necessary to increase the coating amount of the coupler, and when the coating amount is increased, there is a problem that the image quality of the lower layer, particularly the sharpness is deteriorated. Further, there is a problem that it is difficult to obtain a photosensitive material having high sensitivity.

On the other hand, a malondiamide type coupler similar to the yellow coupler of the present invention is described, for example, in French Patent No. 1,558,452. The coupler disclosed in the patent is a so-called O-elimination type 2-equivalent coupler having an active site having a group capable of leaving via an oxygen atom, and is mainly a diffusible coupler. Further, development inhibitor releasing (DIR) couplers as malondiamide type couplers as functional couplers are disclosed in US Pat. Nos. 4,149,886 and 4,477,563.
No. 2,250,950 and the like. However, U.S. Pat. Nos. 4,149,886 and 4,47
No specific compound is described in 7,563. 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 color image storability when used, particularly, the durability is greatly deteriorated when stored under high temperature and high humidity. JP-A-2-250950 proposes to improve the color image fastness,
Although the effect is recognized, it is not yet satisfactory. It was also found that there is a problem that the absorption density of the yellow dye on the long wavelength side (green region) is high and the color reproducibility is deteriorated, and that there is a problem that the photographic property greatly varies when processed with a tired color developing solution. It was Further, it has been found that some of the above couplers have a problem that they have low coupling activity and are difficult to use.

On the other hand, many techniques have been developed or proposed for improving image quality. One of them is improvement of DIR coupler. That is, DIR
The coupler is used for the purpose of improving sharpness by the edge effect and improving color reproducibility by the multilayer effect. Many DIR couplers are known. Among them, as highly reactive yellow color forming DIR couplers, the above-mentioned US Pat. No. 4,149,886 and JP-A-2-2509 are mentioned.
The coupler described in No. 50 is known.

The compound cleaved from the coupler is a development inhibitor precursor, which is a type of DIR coupler which cleaves a development inhibitor under alkaline conditions, for example, US Pat. Nos. 4,248,962 and 4; , 409, 3
No. 23, and No. 4,421,845.

Further, as a DIR coupler of the type in which the compound cleaved from the coupler is further oxidized to cleave the development inhibitor, for example, US Pat. No. 4,618,571, JP-A-61-233741 and 61-238057. The couplers described in No. 1 are known.

Further, when the DIR coupler including the above is used, two or more kinds of DIR couplers are used in combination with the layer to be added, instead of using only one kind, for example, JP-A-56-137353 and 61-61. -255342, 6
The techniques described in JP-A 1-267047 and JP-A-2-262656 are known.

However, in recent color negative photosensitive materials, higher image quality (higher sharpness, more faithful color reproducibility) is particularly required, and when the above-mentioned DIRs are used alone or in combination, a larger amount and more kinds than before are available. DIR couplers tend to be used, and therefore, the fastness of color images and the processing dependence of photosensitive materials, which have been problems in the past, have become more important issues to be solved.

[0009]

SUMMARY OF THE INVENTION A yellow coupler having high color development, high color image fastness and excellent color reproducibility is used. When required, as described above, the problems of color image fastness and photographic variation due to processing of the light-sensitive material must be solved.

Therefore, an object of the present invention is to provide a light-sensitive material having excellent color forming property and stable processability, and the obtained color image is a silver halide color photographic light-sensitive material exhibiting high fastness and excellent image quality. To provide.

[0011]

In order to solve the above-mentioned problems, the present inventors have found that the following means can be achieved.

That is, in a silver halide color photographic light-sensitive material having at least one light-sensitive emulsion layer on a support, the following general formula (1) below reacts with an oxidized product of a developing agent to form a diffusion resistant dye. ) Or at least one coupler represented by the following general formula (2) which reacts with an oxidized product of a developing agent to form a diffusion resistant dye, and at least a compound represented by the following general formula [I]: A silver halide color photographic light-sensitive material containing one kind.

General formula (1)

[0014]

Embedded image General formula (2)

[0015]

Embedded image 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 that forms a nitrogen-containing heterocyclic group with>N—; and Y represents an aryl group or a heterocyclic group. Z represents a group which is released when the coupler represented by the general formula reacts with an oxidized developing agent.

General formula [I]

[0017]

Embedded image In the formula, A reacts with an oxidant of an aromatic primary amine developing agent to produce {(L1) _a- (B) _m } _p- (L2) _n- DI.
Represents a group that cleaves L, and L1 represents L represented by the general formula [I].
1 represents a group in which after the bond on the left side of 1 is cleaved, the bond on the right side (bond with (B) _m ) is cleaved, and B reacts with an oxidized product of a developing agent to form B of the formula [I]. The bond on the right side represents a group that is cleaved, L2 represents a group in which the bond on the right side (bond with DI) is cleaved after the bond on the left side of L2 represented by the general formula [I] is cleaved, and DI is development inhibition. Represents an agent, a, m and n each represent 0 or 1, and p represents an integer of 0 to 2. Here, when p is plural, p (L1) _a −
(B) _m represents the same or different.

Next, the couplers represented by the general formulas (1) and (2) will be described in detail.

When X ₁ and X ₂ represent an alkyl group,
C1-C30, preferably C1-C20, linear, branched,
It is a cyclic, saturated, unsaturated, substituted or unsubstituted alkyl group. Examples of alkyl groups include methyl, ethyl, propyl, butyl, cyclopropyl, allyl, t-octyl,
i-butyl, dodecyl, 2-hexyldecyl.

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

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

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

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

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

When Y represents an aryl group in the general formulas (1) and (2), Y is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. For example, a phenyl group and a naphthyl group are typical examples.

When Y represents a heterocyclic group in the general formulas (1) and (2), Y has the same meaning as described above when X ₁ or X ₂ represents a heterocyclic group.

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

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

The group represented by Z in the general formulas (1) and (2) may be any conventionally known coupling-off group. Preferred Z is a nitrogen-containing heterocyclic group, an aryloxy group, an arylthio group, a heterocyclic oxy group, a heterocyclic thio group, an acyloxy group, a carbamoyloxy group, an alkylthio group, or a halogen atom bonded to the coupling position with a nitrogen atom. No.

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

When Z is a photographically useful group, those conventionally known are useful. For example, U.S. Pat.
8,962, 4,409,323, 4,43
8,193, 4,421,845, 4,61
8,571, 4,652,516, 4,86
1,701, 4,782,012, 4,85
7,440, 4,847,185, 4,47
7,563, 4,438,193, 4,62
Nos. 8,024, 4,618,571, 4,74
1,994, European Published Patent No. 193,389A
No. 348,139A or No. 272,573A, or a leaving group (for example, a timing group) for releasing the photographically useful group is used.

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

[0033] When Z represents an aryloxy group, preferably a substituted or unsubstituted aryl Oki <br/> sheet group having 6 to 10 carbon atoms. Particularly preferred is a substituted or unsubstituted phenoxy group. When it has a substituent, examples of the substituent include the substituents enumerated as the substituents that the group represented by X ₁ may have. Among them, a preferable substituent is a case where at least one substituent is an electron-withdrawing group, and examples thereof include a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group,
Examples thereof include a halogen atom, a carbamoyl group, a nitro group, a cyano group and an acyl group.

[0034] When Z represents an aryl thio group, preferably a substituted or unsubstituted aryl thio group having 6 to 10 carbon atoms. Particularly preferred is a substituted or unsubstituted phenylthio group. When it has a substituent, examples of the substituent include the substituents enumerated as the substituents that the group represented by X ₁ may have. Among them, preferred substituents are when at least one substituent is an alkyl group, an alkoxy group, a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom, a carbamoyl group, or a nitro group.

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

When Z represents a heterocyclic thio group, the portion of the heterocyclic group has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom. It is a substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed-ring heterocyclic group having 3 to 12, preferably 5 or 6 membered rings. Examples of the heterocyclic thio group include tetrazolylthio group, 1,3,4-thiadiazolylthio group, 1,3,4-
Examples thereof include an oxadiazolylthio group, a 1,3,4-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 substituent which the group represented by X ₁ may have. Among them, a preferable substituent is at least one of an alkyl group, an aryl group, a carboxyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group,
Alkylthio group, acylamino group, sulfonamide group,
When it is a nitro group, a carbamoyl group, a heterocyclic group or a sulfonyl group.

[0037] When Z represents an acyloxy group, this acyloxy group is preferably a carbon number 6 to 10, a monocyclic or condensed ring, substituted or unsubstituted aryl
Le acyloxy group or the number of carbon atoms, 2 to 30, preferably a substituted or unsubstituted 2-20 alkyl acyl <br/> group. When these have a substituent, examples of the substituent include the substituents enumerated as the substituents which the group represented by X ₁ may have.

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

When Z represents an alkylthio group, the alkylthio group has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
Which are linear, branched or cyclic, saturated or unsaturated, and substituted or unsubstituted alkylthio groups. When it has a substituent, examples of the substituent include the aforementioned X
_The substituents listed as the substituents that the group represented by ₁ may have are mentioned as examples.

Next, a particularly preferred range of the couplers represented by the general formulas (1) and (2) will be described below.

The group represented by X ₁ in the general formula (1) is preferably an alkyl group. Particularly preferred is an alkyl group having 1 to 10 carbon atoms.

The group represented by Y in the general formulas (1) and (2) is preferably an aryl group. Particularly preferred is a phenyl group having at least one substituent at the ortho position. As the explanation of the substituent, those enumerated as the substituents which may be possessed when Y is an aryl group can be mentioned. The example of a preferable substituent is also the same.

The group represented by Z in the general formula (1) and (2), preferably 5- to 6-membered, nitrogen-containing heterocyclic group bonded to the coupling site via a nitrogen atom, an aryloxy group, 5-6 And a 5- or 6-membered heterocyclic thio group.

Among the couplers represented by the general formula (1) or (2), the preferred coupler is the following general formula (3):
It is a coupler represented by (4) or (5).

General formula (3)

[0046]

Embedded image General formula (4)

[0047]

Embedded image General formula (5)

[0048]

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

In the general formulas (3) to (5), X ₄ to
The detailed description and the preferred range of the groups represented by X ₇ , Ar and Z have the same meanings as those of the corresponding groups in the descriptions of the general formulas (1) and (2). When R _{1 to} R ₄ represent a substituent, those exemplified as the substituent which X ₁ may have may be mentioned as examples.

Among the above-mentioned general formulas, particularly preferred couplers are the couplers represented by the general formula (4) or (5).

The couplers represented by the general formulas (1) to (5) 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 may be out of the specified range for each substituent.

The couplers represented by the general formulas (1) to (5) are diffusion resistant couplers which react with oxidized developing agent to form a diffusion resistant dye. The diffusion resistant coupler is a coupler having a group (diffusion resistant group) in the molecule that increases the molecular weight sufficiently in order to immobilize the molecule in the added layer. As the diffusion resistant group, the total carbon number is usually 8 to 3
An alkyl group having 0, preferably 10 to 20 or an aryl group having a substituent having a total carbon number of 4 to 20 is used. These non-diffusible groups may be substituted in any of the molecules, and may have a plurality.

Specific examples of the yellow couplers represented by the general formulas (1) to (5) are shown below, but the invention is not limited thereto.

[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

Embedded image Note that Y-56 and Y-57 in Chemical formula 30,
Y-58 in Chemical formula 3, Y-63 in Chemical formula 32 and Chemical formula 3
In Y-64 in 3 , "}" indicates that the substituent is substituted at the 5- or 6-position of the benzotriazolyl group.

The yellow couplers represented by the general formulas (1) to (5) and used in the present invention can be synthesized by the following routes.

Synthesis Example-1

[0078]

Embedded image Synthesis of Intermediate B Compound A357.5 g (3.0 mol), Compound B39
1.2 g of ethyl acetate was added to 6.3 g (3.0 mol),
It was dissolved in 0.6 liter of dimethylformamide. 631 g of dicyclohexylcarbodiimide with stirring
A solution of (3.06 mol) in acetonitrile (400 ml) was added dropwise at 15 to 35 ° C. After reacting at 20 to 30 ° C. for 2 hours, the precipitated dicyclohexylurea was collected by filtration.
500 ml of ethyl acetate and 1 liter of water were added to the filtrate, and the aqueous layer was removed. Next, the organic layer was washed twice with 1 liter of water. The organic layer was dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure to obtain 692 g of Intermediate A as an oily substance.
(98.9%) was obtained.

692 g (2.97 mol) of intermediate A was dissolved in 3 liters of ethyl alcohol, and the mixture was stirred at 75
At -80 ° C, 430 g of 30% sodium hydroxide hydrate was added dropwise. After dropping, the mixture was reacted at the same temperature for 30 minutes, and the precipitated crystals were collected by filtration (yield 658 g).

The crystals were suspended in 5 liters of water, and 300 ml of concentrated hydrochloric acid was added dropwise at 40 to 50 ° C. with stirring. 1
After stirring for the same time at the same temperature, the crystals were collected by filtration to obtain 579 g (95%) of intermediate B (decomposition point 127 ° C.).

Synthesis of Intermediate D 45.1 g (0.22 mol) of Intermediate B, Compound C86.
6 g (0.2 mol) was dissolved in 400 ml of ethyl acetate and 200 ml of dimethylacetamide. While stirring, 66 g (0.32 mol) of dicyclohexylcarbodiimide
Acetonitrile solution (100 ml) was added dropwise at 15 to 30 ° C. After reacting at 20 to 30 ° C. for 2 hours, the precipitated dicyclohexylurea was collected by filtration.

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

This oily matter was mixed with 100 ml of ethyl acetate and n-
Crystallization from 300 ml of hexane gave 108 of Intermediate D.
g (87.1%) was obtained (melting point 132-134 ° C.).

[0084]

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

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

47 g of this oily substance was added to 200 g of acetonitrile.
It was dissolved in ml and 28.4 g (0.22 mol) of compound D and 22.2 g (0.22 mol) of triethylamine were added thereto with stirring. After reacting for 4 hours at 40 to 50 ° C., the mixture was poured into 300 ml of water, and the precipitated oily substance was extracted with 300 ml of ethyl acetate. The organic layer was washed with 200 g of a 5% aqueous sodium hydroxide solution, and then twice more with 300 ml of water.
Washed with water. The organic layer was acidified with dilute hydrochloric acid, washed twice with water, and concentrated under reduced pressure to give a residue (yield 70 g).

50 ml of ethyl acetate was added to the obtained oily substance,
Crystallization was performed using a mixed solvent of 100 ml of n-hexane to obtain 47.8 g (80%) of Exemplified coupler Y-7 (melting point 145.
~ 7 ° C).

[0088]

[Table 2] Synthesis example-2

[0089]

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

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

This was dissolved by heating with 1.5 l of n-hexane and the insoluble matter was removed by filtration. The n-hexane solution was water-cooled and the precipitated intermediate E was collected by filtration. Yield 243.4
g (93%), melting point 103-5 [deg.] C.

[0092]

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

After reacting for 30 minutes at the same temperature, 200 g of a 4% aqueous sodium hydrogencarbonate solution was added dropwise to the reaction mixture. The organic layer was separated, washed with 200 ml of water, and dried over anhydrous sodium sulfate. Dichloromethane was distilled off under reduced pressure to obtain 41.3 g of an oily substance.

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

This was crystallized with 200 ml of methanol to obtain 39.8 g (85%) of Exemplified coupler Y-16 (melting point: 110 to 112 ° C.).

[0096]

[Table 4] Synthesis example-3

[0097]

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

500 ml of water was added to the filtrate, the aqueous layer was removed, and the mixture was washed twice more with water. The organic layer was dried over anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure, and an oily substance was added to
0 g was obtained. This oily substance was heated with 1 liter of ethyl acetate and 2 liters of methanol, the insoluble matter was filtered off, and the solution was cooled with water, whereby crystals of intermediate F were precipitated, and thus collected. Yield 267 g (95%), mp 163-4 ° C.

[0099]

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

After reacting for 30 minutes at the same temperature, 500 g of a 6% aqueous sodium hydrogencarbonate solution was added dropwise to the reaction mixture. The organic layer was separated, washed with 500 ml of water, and dried over anhydrous sodium sulfate. When dichloromethane was distilled off under reduced pressure, intermediate G was precipitated as crystals, which was collected by filtration. Yield 108.6 g (91%).

Synthesis of Exemplified Coupler Y-12 Intermediate G 29.8 g (0.05 mol) was dissolved in dimethylformamide 80 ml to give compound D 12.9 g (0.1 mol).
Mol) and then 10.1 g of triethylamine (0.
10 mol) was added dropwise with stirring at 20 to 30 ° C. 4
After reacting at 0-45 ° C for 1 hour, ethyl acetate 300m
1 and 200 ml of water were added. The organic layer was washed twice with 400 g of a 2% aqueous sodium hydroxide solution and then washed once with water. The organic layer was acidified with diluted hydrochloric acid, washed twice with water, and concentrated under reduced pressure to obtain 34 g of a residue. This is ethyl acetate 50m
Crystallization with a mixed solvent of 1, n-hexane 150 ml,
19 g of exemplary coupler Y-12 was obtained.

This crystal was mixed with ethyl acetate / n-hexane = 1
The crystals were recrystallized from 120 ml of a mixed solvent of 3/3 volume ratio to obtain 15 g (43.5%) of Exemplified coupler Y-12 (melting point: 135
~ 6 ° C).

[0103]

[Table 6] Synthesis example-4

[0104]

Embedded image Synthesis of Exemplified Coupler Y-49 Compound G (27.0 g, 0.15 mol) and triethylamine (15.2 g, 0.15 mol) were dissolved in dimethylformamide (50 ml). 29.8 g of intermediate G in this mixture
(0.05 mol) dimethylformamide (30 ml)
The solution was added dropwise with stirring.

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

This was crystallized with 300 ml of a mixed solvent of ethyl acetate / methanol (1/2 volume ratio), and the exemplified coupler Y-49 was collected by filtration. The obtained crystals were recrystallized from 200 ml of a mixed solvent of ethyl acetate / methanol (1/2 volume ratio) to give 28.8 g (77.8%) of Exemplified coupler Y-49.
Obtained. Melting point 190-191 [deg.] C.

[0107]

[Table 7] In the present invention, the yellow couplers represented by the general formulas (1) to (5) are added in the case of a layer to be added or a non-photosensitive layer.
1.0 to 1.0 × per mol of silver halide in the adjacent layer
It can be used in the range of 10 ⁻⁴ mol. It is preferably 5.0 × 10 ⁻¹ to 2.0 × 10 ⁻³ mol,
More preferably, it is in the range of 4.0 × 10 ⁻¹ to 5.0 × 10 ⁻³ mol.

In the present invention, when the yellow couplers represented by the general formulas (1) to (5) are used as the main coupler, they should be added to the blue-sensitive silver halide emulsion layer or the non-photosensitive layer adjacent thereto. Is preferred. When the coupler releases a photographically useful group, it is added to the silver halide photosensitive layer or the non-photosensitive layer depending on the purpose.

In the present invention, the yellow couplers represented by the general formulas (1) to (5) may be used in combination of two or more kinds, or may be used in combination with other known couplers.

In the present invention, the couplers represented by the general formulas (1) to (5) can be prepared by various known dispersion methods.
It can be incorporated into a color light-sensitive material.

In the oil-in-water dispersion method, which is one of the known dispersion methods, a low-boiling organic solvent (eg, ethyl acetate, butyl acetate, methyl ethyl ketone, isopropanol) is used to apply a fine dispersion and dry it. A method in which the low boiling point organic solvent does not substantially remain in the film can be used. When a high-boiling organic solvent is used, any of those having a boiling point of 175 ° C. or higher under normal pressure may be used, and one kind or two or more kinds may be arbitrarily mixed and used. The ratio of the couplers represented by the general formulas (1) to (5) to these high boiling point organic solvents can be in a wide range, but 1 g of the coupler can be used.
The range is 5.0 or less per weight ratio. Preferably 0
To 2.0, and more preferably 0.01 to 1.0.

The latex dispersion method described below can also be applied.

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

Next, the compound represented by the general formula [I] will be described.

The reaction process in which the compound represented by the general formula [I] releases DI during development is represented by, for example, the following reaction formula. An example when p = 1 is shown.

[0116]

Embedded image In the formula, A, L1, a, B, m, L2, n and DI have the same meanings as described in the general formula [I], and QD
I ⁺ means an oxidized product of a developing agent.

In the general formula [I], A represents a coupler residue or a redox group.

Examples of the coupler residue represented by A include yellow coupler residues (eg, open-chain ketomethylene type coupler residues such as acylacetanilide and malondianilide), magenta coupler residues (eg 5-pyrazolone type, pyrazolotriazole). Type or an imidazopyrazole type coupler residue), a cyan coupler residue (for example, phenol type, naphthol type, imidazole type or the same type as described in European Patent Publication 249,453).
Coupler residues such as pyrazolopyrimidine type described in U.S. Pat. No. 4,001) and colorless coupler residues (e.g., coupler residues such as indanone type or acetophenone type). Also, U.S. Pat. Nos. 4,315,070, 4,183,752, 4,174,969, 3,961,959, 4,171,223 or JP-A-52-82423. It may be a heterocyclic coupler residue described in No.

When A represents a redox group, the redox group is a group which can be cross-oxidized by an oxidized product of a developing agent, and examples thereof include hydroquinones, catechols, pyrogallols, 1,4-naphthohydroquinones, 1 , 2-naphthohydroquinones, sulfonamide phenols,
Hydrazides or sulfonamido naphthols are exemplified. These groups are specifically described in, for example, JP-A-61-2.
No. 30135, No. 62-251746, No. 61-27
No. 8852, U.S. Pat. Nos. 3,364,022, 3,
379,529, 3,639,417, 4,6
No. 84,604 or J.P. Org. Chem. , 29 ,
588 (1964).

A preferred example of A is the following general formula (Cp-
1), (Cp-2), (Cp-3), (Cp-4),
(Cp-5), (Cp-6), (Cp-7), (Cp-
8), (Cp-9), (Cp-10) or (Cp-
11) when it is a coupler residue. These coupler residues are preferred because of their high coupling rate.

[0121]

Embedded image

[0122]

Embedded image

[0123]

Embedded image

[0124]

Embedded image

[0125]

Embedded image

[0126]

Embedded image

[0127]

Embedded image

[0128]

Embedded image

[0129]

Embedded image

[0130]

Embedded image

[0131]

Embedded image The asterisk * derived from the coupling position in the above formula represents the bonding position of-{(L1) _a- (B) _m } _p- (L2) _n- DI.

In the above equation, R₅₁, R₅₂, R₅₃, R₅₄,
R₅₅, R₅₆, R₅₇, R₅₈, R₅₉, R ₆₀, R₆₁, R₆₂, R
₆₃, R₆₄Or R₆₅If contains a diffusion resistant group, it is carbon
Total number is 8-40, preferably 10-30
Otherwise, the total number of carbons is
It is preferably 15 or less.

R _{51 to} R ₆₅ , r, d, e and f will be described in detail below. Hereinafter, R ₄₁ represents an aliphatic group, an aromatic group, or a heterocyclic group, R ₄₂ represents an aromatic group or a heterocyclic group, and R ₄₃ , R _44, and R ₄₅ represent a hydrogen atom, an aliphatic group, or an aromatic group. Represents a group or a heterocyclic group.

R ₅₁ has the same meaning as R ₄₁ . R ₅₂ and R ₅₃ have the same meanings as R ₄₂ . r represents 0 or 1. R ₅₄ represents a group having the same meaning as _{R 41, R 41 CON (R} 43) -
Group, (R ₄₁ ) (R ₄₃ ) N-group, R ₄₁ SO ₂ N (R ₄₃ )-
Group, R ₄₁ S-group, R ₄₃ O-group, (R ₄₃ ) (R ₄₅ ) NCO
It represents an N (R ₄₄ )-group or an N 3 C-group. R ₅₅ is R ₄₁
Represents a group having the same meaning as. R ₅₆ and R ₅₇ each have the same meaning as the R ₄₃ group, R ₄₁ S— group, R ₄₃ O— group, R ₄₁ CON
It represents a (R ₄₃ )-group or an R ₄₁ SO ₂ N (R ₄₃ )-group. R ₅₈ represents a group having the same meaning as R ₄₁ . And R ₅₉ groups of the same meaning as _{R 41, R 41 CON (R} 43) - group, R ₄₁ OCON
(R ₄₃ ) -group, R ₄₁ SO ₂ N (R ₄₃ ) -group, (R ₄₃ ).
_{(R 44) NCON (R 45} ) - group, R ₄₁ O-group, R ₄₁ S-
Represents a group, a halogen atom, or a (R ₄₁ ) (R ₄₃ ) N-group. d represents 0 to 3. When d is plural, plural R
₅₉ represents the same substituent or a different substituent. Further, each R ₅₉ may be linked as a divalent group to form a cyclic structure. Examples of forming a cyclic structure include a pyridine ring and a pyrrole ring. R ₆₀ represents a group having the same meaning as R ₄₁ . R ₆₁ represents a group having the same meaning as R ₄₁ .
R ₆₂ is a group of the same meaning as R _41, R ₄₁ OCONH- group, R ₄₁
SO ₂ NH- _{radical, (R 43) (R 44} ) NCON (R 45) -
Group, (R ₄₃ ) (R ₄₄ ) NSO ₂ N (R ₄₅ ) -group, R ₄₃ O
-Group, R ₄₁ S-group, halogen atom or (R ₄₁ ).
(R ₄₃ ) represents an N-group. R ₆₃ is a group having the same meaning as R ₄₁ , R
₄₃ CON (R ₄₅ ) -group, (R ₄₃ ) (R ₄₄ ) NCO-group,
R ₄₁ SO ₂ N (R ₄₄ ) — group, (R ₄₃ ) (R ₄₄ ) NSO ₂
- group, R ₄₃ SO ₂ - group, R ₄₁ OCO- group, R ₄₃ O-SO
_2- group, halogen atom, nitro group, cyano group or R ₄₃
Represents a CO- group. e represents an integer of 0 to 4. Each represents a same or different when there are a plurality of R ₆₂ or R _63. R ₆₄ and R ₆₅ are each (R ₄₃ ) (R ₄₄ ).
NCO- group, R ₄₁ CO- group, (R ₄₃ ) (R ₄₄ ) NSO ₂
- represents group, a nitro group or a cyano group - group, R ₄₁ OCO- group, R ₄₁ SO _2. Z ₁ is a nitrogen atom or-(R ₆₆ ) C
Represents a group (R ₆₆ represents a hydrogen atom or a group having the same meaning as R ₆₃ ). Z ₂ represents a sulfur atom or an oxygen atom.
f represents 0 or 1.

In the above, the aliphatic group has 1 to 3 carbon atoms.
2, preferably 1 to 22 saturated or unsaturated, linear or cyclic, linear or branched, substituted or unsubstituted aliphatic hydrocarbon groups. Representative examples include methyl, ethyl, propyl, isopropyl, butyl, (t) -butyl, (i) -butyl, (t) -amyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, 1,1,
3,3-tetramethylbutyl, decyl, dodecyl, hexadecyl, or octadecyl.

The aromatic group is a phenyl group having 6 to 20 carbon atoms, preferably a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted naphthyl group.

The heterocyclic group is a substituted or unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably selected from nitrogen atom, oxygen atom or sulfur atom as a hetero atom, preferably a 3- to 8-membered ring. It is a cyclic group. Typical examples of the heterocyclic group are 2-pyridyl, 2-furyl, 2-imidazolyl, 1-indolyl, 2,4-dioxo-1,3-
Imidazolidine-5-yl, 2-benzoxazolyl,
Examples include 1,2,4-triazol-3-yl or 4-pyrazolyl.

When the aliphatic hydrocarbon group, aromatic group and heterocyclic group have a substituent, typical substituents are:
Halogen atom, R ₄₇ O-group, R ₄₆ S-group, R ₄₇ CON
(R ₄₈₎ - _{group, (R 47) (R 48} ) NCO- group, R ₄₆ OC
ON (R ₄₇ )-group, R ₄₆ SO ₂ N (R ₄₇ )-group,
(R ₄₇ ) (R ₄₈ ) NSO ₂ — group, R ₄₆ SO ₂ — group, R ₄₇
OCO- _{group, (R 47) (R 48} ) NCON (R 49) - group,
Group having the same meaning as R _46, R ₄₆ COO- groups, R ₄₇ OSO ₂ -
Groups, cyano groups or nitro groups. Where R
₄₆ represents an aliphatic group, an aromatic group, or a heterocyclic group,
R ₄₇ , R ₄₈ and R ₄₉ each represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. The meaning of the aliphatic group, the aromatic group or the heterocyclic group is the same as defined above.

Next, preferred ranges of R _{51 to} R ₆₅ , r, d, e and f will be described.

R ₅₁ is preferably an aliphatic group or an aromatic group. R ₅₂ and R ₅₅ are preferably an aromatic group. R ₅₃ is preferably an aromatic group or a heterocyclic group.

In the general formula (Cp-3), R ₅₄ is R ₄₁
CONH- group or _{(R 41), (R 43} ) N- group. R ₅₆ and R ₅₇ are an aliphatic group, an aromatic group, R ₄₁ O-
The group R ₄₁ S— is preferred. R ₅₈ is preferably an aliphatic group or an aromatic group. In formula (Cp-6), R ₅₉ is preferably a chloro atom, an aliphatic group or an R ₄₁ CONH-group. d is preferably 1 or 2. R ₆₀ is preferably an aromatic group. In the general formula (Cp-7), R ₅₉ is R ₄₁ CONH
-Groups are preferred. In the general formula (Cp-7), d is 1
Is preferred. R ₆₁ is preferably an aliphatic group or an aromatic group. In the general formula (Cp-8), e is preferably 0 or 1. R ₆₂ is R ₄₁ OCONH- group, R ₄₁ CONH
- preferably a group or R ₄₁ SO ₂ NH- group, these substituent positions 5 position of a naphthol ring. General formula (Cp
-9), R ₆₃ is R ₄₁ CONH-group, R ₄₁
SO ₂ NH- _{radical, (R 41) (R 43} ) NSO 2 - group, R ₄₁
SO ₂ - _{group, (R 41) (R 43} ) NCO- group, a nitro group, or a cyano group. In the general formula (Cp-10), R ₆₃ is (R ₄₃ ) (R ₄₃ ) NCO— group, R ₄₃ OCO—
Groups or R ₄₃ CO— groups are preferred. General formula (Cp-1
In 1), R ₅₄ is an aliphatic group, an aromatic group or R ₄₁ CO
NH- groups are preferred.

The linking groups represented by L1 and L2 in the general formula [I] are, for example, US Pat. No. 4,146,396.
No. 4,652,516 or 4,698,29
No. 4,248,962, and 4,857, U.S. Pat.
440 or 4,847,185, a timing group for causing a cleavage reaction using an intramolecular nucleophilic reaction, U.S. Pat. No. 4,409,323 or U.S. Pat.
No. 421,845, a timing group for causing a cleavage reaction by utilizing an electron transfer reaction, U.S. Pat.
No. 46,073, a group which causes a cleavage reaction by utilizing the hydrolysis reaction of imino ketal, or a cleavage reaction utilizing a hydrolysis reaction of an ester which is described in German Patent Publication No. 2,626,317. Groups that cause L1 and L2 are heteroatoms contained therein,
Preferably, at an oxygen atom, a sulfur atom or a nitrogen atom, they are respectively bonded to A or A- (L1) _a- (B) _m .

When the groups represented by L1 and L2 are used, preferable groups include the following.

(1) A group which utilizes a cleavage reaction of hemiacetal.

For example, US Pat. No. 4,146,396, JP-A-60-249148 and 60-249149.
And a group represented by the following general formula. Here, * indicates L1 or L of the compound represented by the general formula [I].
2 represents the bond on the left side, and the ** mark represents the bond on the right side of L1 or L2 of the compound represented by the general formula [I].

Formula (T-1) *-(W-C ( _R65 ) ( _R66 )) _t -In the formula, W is an oxygen atom, a sulfur atom or -N ( _R67 )-.
Represents a group, R ₆₅ and R ₆₆ represent a hydrogen atom or a substituent, R ₆₇ represents a substituent, and t represents 1 or 2. When t is 2 the two _{-W-C (R 65) (} R 66) - represents the same or different. When R ₆₅ and R ₆₆ represent a substituent and typical examples of R ₆₇ are R ₆₉ group and R ₆₉ C, respectively.
O- group, R ₆₉ SO ₂ - _{group, (R 69) (R 70} ) NCO-
Group, and (R ₆₉ ) (R ₇₀ ) NSO ₂ — group.
Here, R ₆₉ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₇₀ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. Each of R ₆₅ , R ₆₆ and R ₆₇ represents a divalent group and is also included when they are linked to each other to form a cyclic structure. Specific examples of the group represented by the general formula (T-1) include the following groups.

[0147]

Embedded image (2) A group that causes a cleavage reaction using an intramolecular nucleophilic substitution reaction.

For example, US Pat. No. 4,248,962,
Examples thereof include timing groups described in JP-A-4,857,440 or JP-A-4,847,185. It can be represented by the following general formula.

General formula (T-2) * -Nu-Link-E-** In the formula, the * mark and ** mark have the same meanings as described in the general formula (T-1), and Nu is obtained. Represents a nuclear group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, E represents an electrophilic group, and is a group capable of undergoing a nucleophilic attack from Nu to cleave the bond with **, and Link is Nu. And E represent a linking group sterically related to each other so that they can undergo an intramolecular nucleophilic substitution reaction. Specific examples of the group represented by formula (T-2) are as follows.

[0150]

Embedded image (3) A group that causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system.

For example, it is described in US Pat. Nos. 4,409,323 and 4,421,845 and is a group represented by the following general formula.

General formula (I-3) * -W- (V ₁ = V ₂ ) _t -CH ₂ -** In the formula, * mark, ** mark, W and t are described for (T-1). Has the same meaning as. V ₁ and V ₂ are each a nitrogen atom, or-(R ₆₅ ) C = or-(R ₆₆ ) C =
Represents However, when t is plural, plural V ₁ = V ₂
Represents the same or different. Specific examples include the following groups.

[0153]

Embedded image (4) A group utilizing a cleavage reaction due to hydrolysis of an ester.

For example, West German Published Patent No. 2,626,315
And the following groups.
In the formula, * and ** have the same meanings as described for the general formula (T-1).

General formula (T-4) * -O-CO-** General formula (T-5) * -S-CS-** (5) A group utilizing the cleavage reaction of imino ketal.

For example, it is a linking group described in US Pat. No. 4,546,073, and is a group represented by the following general formula.

General formula (T-6)

[0158]

Embedded image In the formula, * mark, ** mark and W have the same meaning as described in formula (T-1), and R ₆₈ has the same meaning as R ₆₇ . Specific examples of the group represented by the general formula (T-6) include the following groups.

[0159]

Embedded image The group represented by B in the general formula [I] is A- (L1) _a.
A group that becomes a redox group or a group that becomes a coupler after further cleavage, and has the same meaning as described above for A. The group represented by B has a group capable of leaving by reacting with an oxidized product of a developing agent (that is, a group bonded to the right side of B in the general formula [I]). The group represented by B is, for example, the group represented by B in U.S. Pat. No. 4,824,772 and COUP in U.S. Pat. No. 4,438,193.
The group represented by (B) or US Pat. No. 4,618,57.
The group represented by RED in No. 1 is mentioned. B is preferably bonded to A- (L1) _{a at} a hetero atom contained therein, preferably an oxygen atom or a nitrogen atom.

When the group represented by B is used, preferable groups include the following.

(B-1)

[0162]

Embedded image In the formula, a * mark represents a position bonded to the left side of B in the general formula [I], and a ** mark represents a position bonded to the right side of B in the general formula [I]. X ₁ and X ₄ each represent an oxygen atom or ═N—SO ₂ R ₇₁ (R ₇₁ represents an aliphatic group, an aromatic group or a heterocyclic group), and X ₂ and X ₃ each represent a methine group or a nitrogen atom. And b represents an integer of 1 to 3. However, at least one of b X ₂ and b X ₃ represents a methine group having a bond represented by ** mark. When b is plural, b X ₂ and b X ₃ each represent the same or different. When X ₂ and X ₃ are a methine group having a substituent, they include a case where they are linked to each other to form a cyclic structure (for example, a benzene ring or a pyridine ring) and a case where they are not formed. General formula (B-
The group represented by 1) is cleaved at the bond marked with * and then Ken
dall-Pelz rule (T. J. James, “The
Theory of the Photograph
ic Process ”, 4th ed., Macmi
llan Publishing Co. , Inc. 2
(See the description on page 99) and becomes a compound that reacts with the oxidized product of the developing agent to be oxidized.

Specific examples of the group represented by (B-1) include the following groups.

[0164]

Embedded image (B-2)

[0165]

Embedded image (B-3)

[0166]

Embedded image In the formula, * and ** have the same meanings as described in (B-1), and R ₇₂ , R ₇₃ , and R ₇₄ are groups represented by (B-2) and (B-3), respectively. However, after cleaving at * mark, *
It represents a group for functioning as a coupler having a coupling-off group in the * mark. d represents an integer of 0 to 4, and d
When R is plural, plural R _72's are the same or different. In addition, they may combine to form a cyclic structure (for example, a benzene ring). Examples of R ₇₂ include an acylamino group, an alkyl group and a halogen atom, examples of R ₇₄ include an acylamino group, an alkyl group, an anilino group, an amino group and an alkoxy group, and R ₇₃
Examples thereof include a phenyl group and an alkyl group.

Specific examples of the groups represented by (B-2) and (B-3) include the followings.

[0168]

Embedded image (B-4)

[0169]

Embedded image In the formula, * and ** have the same meanings as described in (B-1), and R ₇₅ , R ₇₆ , and R ₇₇ each represent a substituent,
Two cases are included: when R ₇₇ and R ₇₆ are linked to form a nitrogen-containing heterocycle, or when R ₇₇ and R ₇₅ are linked to form a nitrogen-containing heterocycle. The group represented by (B-4) becomes a coupler having a coupling-off group at the ** mark after cleavage at the * mark.

Specific examples of the group represented by (B-4) include the followings.

[0171]

Embedded image The group represented by DI in the general formula [I] is, for example, a tetrazolylthio group, a thiadiazolylthio group, an oxadiazolylthio group, a triazolylthio group, a benzimidazolylthio group, a benzthiazolylthio group, a tetrazolylseleno group, Examples thereof include a benzoxazolylthio group, a benzotriazolyl group, a triazolyl group, and a benzimidazolyl group. These groups are described, for example, in US Pat. No. 3,227,
No. 554, No. 3,384,657, No. 3,615, 5
No. 06, No. 3,617, 291 and No. 3,733, 20
No. 1, No. 3,933,500, No. 3,958,993
No. 3,961,959, 4,149,886
Issue 4,259,437, Issue 4,095,984
Nos. 4,477,563 and 4,782,012
European Patent Nos. 348,139A and 35
No. 4,532A or British Patent No. 1,450,479.

Specific examples of the group represented by DI include the following. In the following, * indicates general formula [I]
Represents the position of bonding to the left side of the group represented by DI.

[0173]

Embedded image

[0174]

Embedded image Next, the preferable range of the compound represented by the formula [I] will be described.

In the formula, p is preferably 0 or 1.

The compound represented by the general formula [I] is preferably a diffusion resistant type, particularly preferably the diffusion resistant group is A,
This is the case when it is included in L1 or B.

A particularly preferred compound in the general formula [I] is when A represents a coupler residue.

Particularly preferred compounds in the general formula [I] are a = 1, m = 0, p = 1 and n = 0, a = 0,
When m = 1, p = 1 and n = 0, or a = 1, m =
0, p = 1 and n = 1. These compounds are particularly excellent in color reproducibility due to the layering effect and sharpness due to the edge effect.

For examples of the compound represented by the general formula [I] and a synthesis method, A, L1,
Known patents or references cited for explaining B, L2, and DI are disclosed in JP-A-63-37346 and JP-A-61-156127.

Examples of compounds represented by the general formula [I] are shown below.

[0181]

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[0182]

Embedded image

[0183]

Embedded image

[0184]

Embedded image

[0185]

Embedded image

[0186]

Embedded image

[0187]

Embedded image

[0188]

Embedded image

[0189]

Embedded image

[0190]

Embedded image

[0191]

Embedded image

[0192]

Embedded image The compound represented by the general formula [I] of the present invention is mainly applied for the purpose of improving image quality (color reproducibility, sharpness, graininess) and improving color image fastness.

The compound represented by the general formula [I] of the present invention can be used in either a photosensitive layer or a non-photosensitive layer, but is preferably adjacent to the photosensitive layer or the photosensitive layer. It is a non-photosensitive layer. The addition amount depends on the performance required for the light-sensitive material, but the silver halide present in the light-sensitive layer or the adjacent layer to which the compound of the general formula [I] is added 1
It is in the range of 1.0 × 10 ^{−6 to} 0.5 mol per mol. Particularly preferably, it is 1.0 × 10 ^{−5 to} 1.0 × 10 ⁻¹ mol.

Two or more kinds of the compounds represented by the general formula [I] can be used in combination in the same layer, or one kind can be used in two or more layers. The addition method of the compound represented by the general formula [I] is as follows.
It can be added according to the method of adding the coupler represented by (5).

Next, the cyan coupler represented by the general formula (C) will be described. General formula (C)

[0196]

Embedded image In the formula (C), R ₂₁ is -CONR ₂₄ R ₂₅ , -SO ₂ N
_{R 24 R 25, -NHCOR 24,} -NHCOOR 26, -NH
SO ₂ R ₂₆ , —NHCONR ₂₄ R ₂₅ or —NHSO ₂
NR ₂₄ R ₂₅ , R ₂₂ represents a group capable of being substituted on a naphthalene ring,
p represents an integer of 0 to 3, R ₂₃ represents a substituent, and X ₂₁ represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. However,
R ₂₄ and R ₂₅ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₂₆ represents an alkyl group, an aryl group or a heterocyclic group. When p's are plural, R _22's may be the same or different and may combine with each other to form a ring. R ₂₂ and R ₂₃ or R ₂₃
And X ₂₁ may combine with each other to form a ring.

The cyan coupler represented by the formula (C) is a dimer or a multimer of R ₂₁ , R ₂₂ , R ₂₃ or X _{21 which} is bonded to each other via a divalent or divalent or more group ( (Including a polymer in which a coupler is bound to a polymer main chain) may be formed.

In the present invention, the alkyl group may be linear, branched or cyclic, and may have a substituent (eg halogen atom, aryl group, heterocyclic group, Alkoxy group, aryloxy group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, acyloxy group, acyl group).

Even if the aryl group is a condensed ring (for example, a naphthyl group), a substituent (for example, a substituent of the above alkyl group, an alkyl group, a cyano group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group) , An ureido group, an alkoxycarbonylamino group).

The heterocyclic group is O, N, S, P, Se or T.
a 3- to 8-membered monocyclic or condensed-ring heterocyclic group containing at least one heteroatom of e in the ring, wherein a substituent (for example, a substituent of the aryl group, a hydroxyl group, a carboxyl group, Nitro group, amino group, aryloxycarbonyl group).

R ₂₁ is preferably a carbamoyl group having 1 to 30 total carbon atoms (hereinafter referred to as C number) (for example, Nn-butylcarbamoyl, Nn-hexadecylcarbamoyl, N- [3- (2,4) -Di-t-pentylphenoxy) propyl] carbamoyl, N- (3-n-dodecyloxypropyl) carbamoyl, N- (3-n-dodecyloxy-2-methylpropyl) carbamoyl, N-
[3- (4-t-octylphenoxy) propyl] carbamoyl) or a sulfamoyl group having 0 to 30 carbon atoms (for example, N- (3-n-dodecyloxypropyl) sulfamoyl, N- [4- (2,4-di -T-pentylphenoxy) butyl] sulfamoyl), and particularly preferably a carbamoyl group.

P is preferably 0 or 1, particularly preferably 0. R ₂₂ is preferably a halogen atom (F, C
1, Br, I, and so on. ), Cyano group, C number of 1 to 12
Is an alkyl group, an alkoxy group, a carbonamido group or a sulfonamido group.

R ₂₃ is preferably --COR ₂₇ , --SO ₂ R
_{28, -CO 2 R 28, -PO} (OR 28) 2 or -PO
(R ₂₈ ) ₂ wherein R ₂₇ is R ₂₄ and R ₂₈ is R
₂₆ has the same meaning. R ₂₃ is particularly preferably C
-COR _{27 of the} number 1 to 30 (eg, acetyl, trifluoroacetyl, pivaloyl, benzoyl), C number 1 to 30
-SO ₂ R ₂₈ (e.g., methylsulfonyl, n- butylsulfonyl, p- tolyl sulfonyl), or a C number of 2 to 3
0 is —CO ₂ R ₂₈ (eg methoxycarbonyl, isobutoxycarbonyl, 2-ethylhexylcarbonyl), with —CO ₂ R ₂₈ being more preferred.

X ₂₁ is preferably a hydrogen atom, a halogen atom, an alkoxy group having a C number of 1 to 30 (eg 2-hydroxyethoxy, 2- (carboxymethylthio) ethoxy,
3-carboxyethoxy, 2-methoxyethoxy), C
An aryloxy group having the number of 6 to 30 (eg, 4-methoxyphenoxy, 4- (3-carboxypropanamido) phenoxy), an alkylthio group having the number of C 2 to 30 (eg, carboxymethylthio, 2-carboxyethylthio, 2-hydroxyethyl) Thio, 2,3-dihydroxypropylthio) or an arylthio group having 6 to 30 carbon atoms (e.g., 4-
t-butylphenylthio, 4- (3-carboxypropanamide) phenylthio), and particularly preferably hydrogen atom, chlorine atom, alkoxy group or alkylthio group.

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

[0206]

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[0207]

Embedded image

[0208]

Embedded image

[0209]

Embedded image

[0210]

Embedded image Specific examples of the cyan coupler represented by the general formula (C) other than the above and / or methods for synthesizing these compounds are described in, for example, U.S. Pat. No. 4,690,889 and JP-A-60-23744.
No. 8, No. 61-153640, No. 61-145557.
No. 63-208042 and West German Patent No. 3,82.
3,049A.

The total addition amount of the cyan coupler represented by the general formula (C) is 30 mol% or more of all the cyan couplers,
Preferably 50 mol% or more, more preferably 70 mol%
Or more, more preferably 90 mol% or more.

The cyan coupler represented by the general formula (C) is preferably used in combination of two or more kinds, and when the same color-sensitive layer is divided into two or more layers having different sensitivities, it is the highest sensitivity layer. It is preferable to use a 2-equivalent cyan coupler and a 4-equivalent cyan coupler in the lowest sensitivity layer. It is preferable to use one or both of them for the other color-sensitive layers having the same color sensitivity.

For the cyan coupler represented by the general formula (C), as described in JP-A-62-269958, it is preferable to use a small amount of a high-boiling organic solvent for dispersion in sharpness and after treatment. It is more preferable for improving the image storability.

The coupler represented by the general formula (C) improves the balance of image storability by using it in the same light-sensitive material as the yellow coupler represented by the general formulas (1) to (5) described above. . Further, by using the compound represented by the general formula [I], the color image fastness and the image quality can be improved.

Next, the coupler represented by formula (A) will be described in more detail.

As examples of M and Q, a halogen atom (fluorine, chlorine, bromine), an aliphatic group having 1 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an aliphatic oxy group having 1 to 20 carbon atoms, Aromatic oxy group having 6 to 20 carbon atoms, 2 to 24 carbon atoms
Carbonamide group, C0-20 sulfonamide group, C1-24 carbamoyl group, C0-20
Sulfamoyl group, an acyloxy group having 2 to 20 carbon atoms, an aliphatic oxycarbonyl group having 2 to 20 carbon atoms, a substituted amino group having 2 to 24 carbon atoms, an aliphatic thio group having 1 to 24 carbon atoms, and 1 to 1 carbon atoms 20 ureido group, C0-20 sulfamoylamino group, cyano group, C2-20 aliphatic oxycarbonylamino group, C4-20 imide group, C1-20 aliphatic Examples thereof include a sulfonyl group, an aromatic sulfonyl group having 6 to 20 carbon atoms, and a heterocyclic group having 1 to 20 carbon atoms. L is a hydrogen atom, a halogen atom (fluorine,
Chlorine, bromine), or an aliphatic oxy group having 1 to 24 carbon atoms. X is a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Specifically, in the following general formulas [B-1], [B-2] and [B-3], expressed.

General formula [B-1] -OR 'General formula [B-2] -SR "General formula [B-3]

[0218]

Embedded image In formula [B-1], R'is an aromatic group having 2 to 30 carbon atoms, a heterocyclic group having 1 to 28 carbon atoms, an acyl group having 2 to 28 carbon atoms, and an aliphatic sulfonyl group having 1 to 24 carbon atoms. Alternatively, it is an aromatic sulfonyl group having 6 to 24 carbon atoms.

In the general formula [B-2], R ″ has 1 carbon atom.
Represents an aliphatic group having 30 to 30, an aromatic group having 6 to 30 carbon atoms, or a heterocyclic group having 1 to 28 carbon atoms.

In the general formula [B-3], Y represents a non-metal atom group necessary for forming a monocyclic ring or a condensed 5- to 7-membered heterocycle with N. Examples of heterocycles formed by N and Y include pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, tetraazaindene, succinimide, phthalimide. , Saccharin, oxazolidine-2,4-dione, imidazolidine-2,4-dione, thiazolidine-2,4-dione, urazole, parabanic acid, maleinimide, 2-pyridone, 4-pyridone, 6-pyridazone, 6- Pyrimidone, 2-pyrazone, 1,3,5-triazin-2-one, 1,2,4-triazin-6-one, 1,3,4-triazin-6-one, 2-oxazolone, 2-thiazolone, 2-imidazolone, 3-isoxazolone, 5-tetrazolone, 1,2,4-tri Zo-5-one and the like may be substituted, and examples of the substituent may include a halogen atom, a hydroxy group, a nitro group, a cyano group, an aliphatic group, an aromatic group, a heterocyclic group and an aliphatic oxy group. Group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic oxycarbonyl group, carbonamido group,
Examples include sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, sulfamoylamino group, aliphatic oxycarbonylamino group, and substituted amino group.

In the present invention, the aliphatic group represents a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group, which may be substituted. Examples of aliphatic groups include methyl, ethyl, isopropyl, n-butyl, t
-Butyl, t-amyl, n-hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, n-decyl,
n-dodecyl, n-tetradecyl, n-hexadecyl,
2-hexyldecyl, n-octadecyl, allyl, benzyl, phenethyl, undecenyl, octadecenyl, trifluoromethyl, chloroethyl, cyanoethyl, 1-
(Ethoxycarbonyl) ethyl, methoxyethyl, butoxyethyl, 3-dodecyloxypropyl, phenoxyethyl and the like. In the present invention, the heterocyclic group is a substituted or unsubstituted monocyclic or condensed ring heterocyclic group, for example, a compound represented by the following formula:

[0222]

Embedded image 2-furyl in addition to the group derived from the compound represented by
2-thienyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-quinolyl, oxazol-2-yl, thiazol-2-yl, benzoxazol-2-yl, benzothiazol-2-yl, 1,3,3. 4-thiadiazol-2-yl, 1,3,4-oxadiazol-2-yl and the like. In the present invention, the aromatic group is a substituted or unsubstituted monocyclic or condensed ring aryl group, for example, phenyl, tolyl, 4-chlorophenyl, 4-methoxyphenyl, 1-naphthyl, 2-naphthyl, 4-t. -Butylphenoxy and the like.

Next, examples of preferred substituents in the coupler represented by formula (A) which is preferably used in the invention will be described. M is preferably an aliphatic group (methyl, ethyl,
n-propyl, t-butyl etc.), aliphatic oxy group (methoxy, ethoxy, n-butoxy, n-dodecyloxy etc.), halogen atom (fluorine, chlorine, bromine), carbonamide group (acetamide, n-butanamide, n-tetradecane amide, benzamide, etc.) or a sulfonamide group (methyl sulfonamide, n-butyl sulfonamide, n-octyl sulfonamide, n-dodecyl sulfonamide, toluene sulfonamide, etc.). L is preferably a chlorine atom or an aliphatic oxy group (methoxy, ethoxy, methoxyethoxy, n-octyloxy, 2-
Ethylhexyloxy, n-tetradecyloxy, etc.).

Q is preferably an aliphatic oxycarbonyl group (methoxycarbonyl, ethoxycarbonyl, n-butoxycarbonyl, n-) in addition to the substituents mentioned above in M.
-Hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, 1- (ethoxycarbonyl) ethyloxycarbonyl, 3-dodecyloxypropyloxycarbonyl, n-decyloxycarbonyl, n-dodecyloxycarbonyl, phenethyloxycarbonyl, etc.) or carbamoyl group ( (Dimethylcarbamoyl, dibutylcarbamoyl, dihexylcarbamoyl, di-2-ethylhexylcarbamoyl, n-dodecylcarbamoyl, etc.)
It is. m is preferably 0 to 2, and n is preferably 0 to 2. X is preferably a group in which R'is an aromatic group in the general formula [B-1] (4-methoxycarbonylphenoxy, 4-methylsulfonylphenoxy, 4-cyanophenoxy, 4-dimethylsulfamoylphenoxy, 2-acetamido. -4-ethoxycarbonylphenoxy, 4-ethoxycarbonyl-2-methylsulfonamidophenoxy, etc.) or a group represented by the general formula [B-3], of which the latter is represented by the following general formula [B-4]. More preferred are groups represented by

General formula [B-4]

[0226]

Embedded image In the general formula [B-4], V represents a substituted or unsubstituted methylene group or a substituted or unsubstituted imino group, and W represents an oxygen atom, a sulfur atom, a substituted or unsubstituted methylene group or an unsubstituted imino group. However, when V is an imino group, W is neither an oxygen atom nor a sulfur atom. Examples of the group represented by the general formula [B-4] include succinimide,
Phthalimide, 1-methylimidazolidine-2,4-
Dione-3-yl, 1-benzylimidazolidine-2,
4-dione-3-yl, 5-ethoxy-1-methylimidazolidin-2,4-dione-3-yl, 5-methoxy-1-methylimidazolidin-2,4-dione-3-yl, 5, 5-dimethyloxazolidin-2,4-dione-3-yl, thiazolidin-2,4-dione-3-yl, 1-benzyl-2-phenyltriazolidine-3,
5-dione-4-yl, 1-n-propyl-2-phenyltriazolidine-3,5-dione-4-yl, 5-ethoxy-1-benzylimidazolidin-2,4-dione-3-yl Etc.

In the yellow coupler represented by the general formula (A), any of the substituents M, Q, L or X becomes a divalent to tetravalent linking group to give a yellow coupler dimer to tetramer. However, a monomer or a dimer is preferable. When the yellow coupler represented by the general formula (A) is a dimer to a tetramer, the carbon number range mentioned above for M, Q, L or X does not apply.

Specific examples of the yellow coupler represented by formula (A) used in the present invention are shown below, but the coupler used in the present invention is not limited thereto.

[0229]

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[0230]

Embedded image

[0231]

Embedded image

[0232]

Embedded image

[0233]

Embedded image

[0234]

Embedded image

[0235]

Embedded image The yellow coupler preferably used in the present invention is synthesized by a conventionally known method. For example, U.S. Pat. Nos. 3,227,554, 3,408,194, 3,415,652, 3,447,928, 4,401,752, and British Patent 1,040,710.
JP-A-47-26133 and JP-A-47-37736.
No. 48-733147, No. 48-94432,
48-68834, 48-68835, 48
No. 68836, No. 50-34232, No. 51-50
No. 734, No. 51-102636, No. 55-598.
No. 55-161239, No. 56-95237,
It can be synthesized by the synthetic methods described in the specifications of Nos. 56-161543, 56-153343, 59-174839 and 60-35730.

The coupler represented by formula (A) of the present invention is preferably added to the light-sensitive silver halide emulsion layer in the light-sensitive material or its adjacent layer, and is added to the light-sensitive silver halide emulsion layer. Is particularly preferable. The total amount added to the light-sensitive material is 1 × 10 ^{−3 to} 1.20 g / m ² , preferably 1 × 10 ^{−2 to} 1.00 g / m ² , and more preferably 1 × 10 ^−1. Is about 0.80 g / m ² . When it is added to the photosensitive silver halide emulsion layer, it is calculated to be 1 × 10 ⁻³ to 1 mol per mol of silver halide.
2 mol, preferably 1 × 10 ^-2 to 1 mol,
More preferably, it can be used in the range of 2 × 10 ^{-2 to} 5 × 10 ^-1 mol.

The coupler represented by formula (A) of the present invention can be used in combination with the yellow coupler represented by formulas (1) to (5) described above. When the same photosensitive layer comprises, for example, a high-sensitivity layer, a medium-sensitivity layer and a low-sensitivity layer, the coupler represented by the general formula (A) and the general formula (1) to
The couplers represented by (5) may be mixed and used,
It is also possible to separately add and use each of the high-, medium-, and low-sensitivity layers, and these usages are selected according to the performance required by the light-sensitive material.

When the couplers represented by the general formula (A) and the general formulas (1) to (5) are mixed and used, the mixing ratio of these couplers can be arbitrarily selected. Further, when the mixture is used, the addition amount is such that the total addition amount is within the same range as described above.

The coupler represented by formula (A) is preferably used when the photosensitive material is required to have particularly high sensitivity. The combined use with the couplers represented by the general formulas (1) to (5) is preferable for maintaining the high sensitivity and enhancing the color image storability, and the same light-sensitive material as the cyan coupler represented by the general formula (C). The balance of color image storability is improved by using Further, use with the compound represented by the general formula [I] is preferable from the viewpoint of improving image quality and color image storability.

The method of adding the coupler represented by the general formula (A) can be carried out according to the method of adding the coupler represented by the general formulas (1) to (5) of the present invention.

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, green,
And a unit light-sensitive layer having color sensitivity to any of red light and a multilayer silver halide color photographic light-sensitive material. In general, the arrangement of the unit light-sensitive layers is, in order from the support side, a red light-sensitive layer, The color-sensitive layer and the blue-sensitive layer are provided in this order. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
Couplers, DIR compounds and the like described in JP-A Nos. 61-20037 and 61-20038 may be contained, and a color mixture inhibitor may be contained as usually used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high sensitivity emulsion layer and a low sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer constitution of emulsion layers can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also,
JP-A-57-112751, 62-200350
As described in JP-A Nos. 62-206541 and 62-206543, a low-speed emulsion layer may be provided on the side farther from the support and a high-speed 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-sensitive layer (BL) / High-sensitivity blue-sensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
And so on.

Further, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. JP-A-56-25738 and JP-A-62-6393.
As described in the specification of JP-A No. 6, the blue light-sensitive layer / GL / RL / GH / RH may be arranged in this order from the farthest side from the support.

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

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

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,774, 4,707,436 and JP-A-62-160448 are used.
And BL and G described in the specification of JP-A-63-89850.
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as L and RL, adjacent to or in proximity to the main photosensitive layer.

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

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
It is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing the following silver iodide. Particularly preferred is about 2 mol%
Silver iodobromide or silver iodochlorobromide containing from 1 to about 10 mol% of silver iodide.

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

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

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types) ", and No. 18 of the same.
716 (November 1979), p. 648, ibid. 30
7105 (November 1989), pp. 863-865, and "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glafkides, Chemieet).
Physique Photographique, P
aulMontel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.F. Duffi).
n, Photographic Emulsion C
hemistry (Focal Press, 196)
6)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating Ph
autographic Emulsion, Focal
Press, 1964) and the like.

US Pat. Nos. 3,574,628 and 3,
655,394 and British Patent 1,413,748.
Monodisperse emulsions described in Nos. 1 and 2 are also preferred.

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

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

The above-mentioned emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain, or a type which has a latent image on both the surface and the inside. It must be a negative emulsion. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. A method for preparing this core / shell type internal latent image type emulsion is disclosed in
No. 133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

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

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

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer.
The term "silver halide particles having a fogged inside or surface thereof" means silver halide grains which can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. . A method for preparing silver halide grains having the inside or the surface of the grains fogged is described in U.S. Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner core of the fogged core / shell type silver halide grain may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain 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 the average grain size is 0.01 to 0.7.
5 μm, particularly preferably 0.05 to 0.6 μm, is preferred. Also,
The grain shape is not particularly limited, and may be regular grains or polydispersed emulsions, but may be monodispersed (at least 95% of the weight or the number of silver halide grains is within ± 40% of the average grain size). Having a particle size of 1).

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 silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that it is not fogged in advance. .

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

The fine grain silver halide preferably has an average grain size (average value of equivalent circle diameters of projected areas) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized,
Also, spectral sensitization is not necessary. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing fine silver halide grains.

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

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

Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer 23 pages 648 pages right column 866 pages 2. Sensitivity enhancer page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, page 866 to 868, supersensitizer, to page 649, right column 4. Whitening agent 24 pages 647 pages right column 868 pages 5. Fogging prevention pages 24 to 25 pages 649 right column 868 to 870 pages agents and stabilizers 6. Light absorber, pages 25 to 26, page 649, right column, page 873, filter to page 650, left column, dyes, ultraviolet absorbers 7. Stain 25 pages right column 650 pages left column 872 pages Inhibitor to right column 8. Dye image Page 25 Page 650 Page left column Page 872 Stabilizer 9. Hardener 26 pages 651 pages left column 874-875 pages 10. Binder 26 pages 651 pages left column 873 to 874 pages 11. Plasticizer, page 27, page 650, right column, page 876, lubricant 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. Static 27 pages 650 pages right column 876-877 pages Inhibitor 14. Matting agent pp. 878-879 Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, immobilization by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add a compound capable of being added to the light-sensitive material.

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

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

International Publication WO88 /
No. 04794, a dye dispersed by the method described in JP-A No. 1-502912 or EP 317,308A,
U.S. Pat. No. 4,420,555;
It is preferable that the dye described in No. 8 be contained.

Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure No. Nos. 17643, VII-CG and No. 307105, VII-CG.

As the yellow couplers, in addition to those represented by the above general formulas (1), (2) and (A), for example, US Pat. Nos. 3,933,501 and 4,022,
No. 620, No. 4,326,024, No. 4,40
No. 1,752, No. 4,248,961, and Japanese Patent Publication Sho 58
-10739, British Patents 1,425,020, 1,476,760, U.S. Patent 3,973,96.
No. 8, No. 4,314, 023, No. 4,511, 6
Those described in No. 49, European Patent 249,473A, etc. are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No. 3,073,636; U.S. Pat.
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-72238.
-35730, 55-118034, 60-1
No. 85951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, and WO88 / 04795 are particularly preferable.

Examples of the cyan coupler include phenol-type and naphthol-type couplers other than those represented by the general formula (C). US Pat. No. 4,052,212,
Nos. 4,146,396 and 4,228,233
No. 4,296,200 and No. 2,369,92
No. 9, No. 2,801,171, No. 2,772,1
No. 62, No. 2,895,826, No. 3,772
No. 002, No. 3,758,308, No. 4,33
No. 4,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365.
A, No. 249,453A, U.S. Pat.
No. 6,622, No. 4,333, 999, No. 4,7
No. 75,616, No. 4,451,559, No. 4,
Preferred are those described in 427,767, 4,690,889, 4,254,212, 4,296,199, and JP-A-61-42658. Further, Japanese Patent Application Laid-Open Nos. 64-553, 64-554,
Pyrazoloazole couplers described in 4-555 and 64-556 and imidazole couplers described in U.S. Pat. No. 4,818,672 can also be used.

Typical types of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
Nos. 09,320, 4,576,910, British Patent 2,102,137, 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, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Published) No. 3,234,533 are preferred.

Colored couplers for correcting unnecessary absorption of color forming dyes are available from Research Disclosure N.
o. No. 17643, section VII-G; Of 307105
Section VII-G, U.S. Pat. No. 4,163,670, JP-B-57-39413, U.S. Pat. No. 4,004,929.
No. 4,138,258 and British Patent No. 1,14.
Those described in 6,368 are preferable. In addition, a coupler described in U.S. Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling, or reacting with a developing agent described in U.S. Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
The DIR coupler which releases a development inhibitor is, in addition to the DIR coupler represented by the general formula [I] of the present invention, the aforementioned RD1764.
3, VII-F section and No. 307105, Patents described in Section VII-F, JP-A-57-151944, 5
Nos. 7-154234, 60-184248, 63
-37346, 63-37350, U.S. Pat.
Preferred are those described in 248,962 and 4,782,012.

R. D. No. 11449, 2424
1, the bleaching accelerator releasing coupler described in JP-A-61-2201247 is effective for shortening the processing time having a bleaching ability, and is particularly useful for a light-sensitive material using tabular silver halide grains. When added, its effect is great. Examples of couplers which release a nucleating agent or a development accelerator in an image-like manner during development include British Patent 2,097,140.
No. 2,131,188, JP-A-59-1576.
Nos. 38 and 59-170840 are preferred. Also, JP-A-60-107029 and JP-A-60-25
No. 2340, JP-A-1-44940 and 1-4568.
Compounds which release a fogging agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in No. 7 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
No. 4,283,4.
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multi-equivalent couplers, European Patent No. 17
Nos. 3,302A and 313,308A, couplers for releasing dyes that recover color after separation, US Pat.
55,477, etc., couplers releasing leuco dyes described in JP-A-63-75747, couplers releasing fluorescent dyes described in U.S. Pat. No. 4,774,181, and the like. Can be

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

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

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

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-257747 are used.
272248, and JP-A-1-80941, 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, It is preferable to add various preservatives or fungicides such as-(4-thiazolyl) benzimidazole.

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

Suitable supports usable in the present invention are described in, for example, RD. No. No. 17643, page 28;
No. 18716, from the right column on page 647 to the left column on page 648; 307105, page 879.

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

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

The photosensitive 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 surfactant, and the like. The swelling ratio of this back layer is 150 to
500% is preferred.

The color photographic light-sensitive material according to the present invention has the RD. No. No. 17643, pages 28 to 29;
No. 18716, page 651, left column to right column; 30
The development can be carried out by a usual method described on pages 880 to 881 of No. 7105.

The color developing solution used in 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. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-
N, N-diethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-
N-ethyl-β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof are exemplified. Among these, in particular, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. These compounds can be used in 2
More than one species may be used in combination.

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

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. The black-and-white developer includes a known black-and-white developing agent, for example, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or N-methyl-p-.
Aminophenols such as aminophenol can be used alone or in combination. The color developing solution and the black-and-white developing solution generally have a pH of 9 to 12. The 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 500 ml by reducing the bromide ion concentration in the replenishing solution.
It can also be: To reduce the amount of replenishment,
It is preferable to prevent evaporation of liquid and air oxidation by reducing the contact area of the treatment tank with air.

The contact area between the photographic processing liquid and the air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = contact area between treatment liquid and air (cm ² ) / volume of treatment liquid (cm ³ ). The above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0. .05. As a method of reducing the aperture ratio in this manner, in addition to providing a shield such as a floating lid on the surface of the photographic processing solution in the processing tank, Japanese Patent Application Laid-Open No.
No. 033, a method using a movable lid,
And a slit developing method described in JP-A-216050. Reducing the aperture ratio is not only in both the color development and black-and-white development steps, but also in the subsequent steps,
For example, it is preferably applied in all steps such as bleaching, bleach-fixing, fixing, washing with water, and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer.

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

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two successive bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. Examples of the bleaching agent include compounds of polyvalent metals such as iron (III), peracids, quinones, and nitro compounds. Typical bleaching agents are organic complex salts of iron (III), such as amino acids 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 and malic acid can be used. Of these, iron (III) aminopolycarboxylates including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts
Complex salts are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually from 4.0 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution, and their pre-bath.
Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent Nos. 1,290,812, 2,059,988, JP Nos. 53-32736, 53-57831, 53
No. 37418, No. 53-72623, No. 53-95
No. 630, No. 53-95731, No. 53-10423
No. 2, No. 53-124424, No. 53-141623
No. 53-28426, Research Disclosure No. Compounds having a mercapto group or a disulfide group described in No. 17129 (July, 1978);
Thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5
No. 61; thiourea derivative; West German Patent No. 1,12
7,715; JP-A-58-16235; West German Patent Nos. 966,410 and 2,748,
No. 430; polyamine compounds described in JP-B-45-8836; and JP-A-49-40,943; JP-A-49-59,644; JP-A-53-94,927; 54-35,727, 5
Compounds described in Nos. 5-26,506 and 58-163,940; bromide ions and the like can be used. Of these, compounds having a mercapto group or a disulfide group are preferred because of their large accelerating effect, and in particular, US Pat.
58, West German Patent 1,290,812, JP-A-53
Compounds described in -95,630 are preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic 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 preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, and specifically, for example, acetic acid, propionic acid, hydroxyacetic acid and the like are preferable.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Is most commonly used, with ammonium thiosulfate being the most widely used. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in EP-A-294769A is preferable. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

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

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

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of enhancing stirring, a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on the emulsion surface of a photosensitive material, or a method using a rotating means described in JP-A-62-183461, is used. A method for improving the effect, a method for moving the photosensitive material while bringing the wiper blade provided in the liquid into contact with the emulsion surface, and making the emulsion surface turbulent to improve the stirring effect, and a circulation of the entire processing solution. There is a method of increasing the flow rate. Such a stirring improving means includes a bleaching solution, a bleach-fixing solution,
It is effective in any of the fixing solutions. It is considered that the improved stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. The means for improving the stirring is more effective when a bleaching accelerator is used, and can remarkably increase the accelerating effect or eliminate the fixing inhibition effect of the bleaching accelerator. DETAILED DESCRIPTION OF THE INVENTION The automatic developing machine used in the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-1.
It is preferable to have the photosensitive material conveying means described in No. 91258 and No. 60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath and has a high effect of preventing the deterioration of the performance of the treatment liquid. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention 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 light-sensitive material (for example, depending on the material used, such as a coupler), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment system such as countercurrent, forward flow, etc. It can be set in a wide range depending on the conditions. Of these, the relationship between the number of washing tanks and the water amount in the multi-stage countercurrent system is as follows.
yety of Motion Picture an
d Television Engineers 6
4, p. 248-253 (May, 1955). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention,
As a solution to such a problem, JP-A-62-288,
The method for reducing calcium ions and magnesium ions described in No. 838 can be used very effectively. Also, chlorinated fungicides such as isothiazolone compounds, thiabendazoles, chlorinated sodium isocyanurate, etc., and benzotriazoles described in JP-A-57-8542, Hiroshi Horiguchi, "Antibacterial and antifungal agents" Chemistry "(198
6 years) Sankyo publishing, Sanitation Technical Society edition "microbial sterilization, sterilization,
It is also possible to use the fungicide described in "Antifungal Technology" (1982) Industrial Technology Association, "Encyclopedia of Antifungal Agents" (1986) edited by Japan Society for Antibacterial and Antifungal Agents.

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

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

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

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

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

The silver halide color light-sensitive material of the present invention comprises
If necessary, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339 and JP-A-57-14.
4547 and 58-115438.

The various processing solutions used in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature promotes the processing and shortens the processing time, and a lower temperature achieves an improvement in the image quality and an improvement in the stability of the processing solution. be able to.

The silver halide light-sensitive material of the present invention comprises
For example, U.S. Pat. No. 4,500,626;
-133449, 59-218443, 61-
It is also applicable to the photothermographic materials described in US Pat. No. 2,380,56 and EP 210,660 A2.

[0314]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photographic material composed of each layer having the following composition, was prepared.

(Composition of photosensitive layer) The coating amount is the amount expressed in g / m ² of silver for silver halide and colloidal silver, and g for couplers, additives and seratin.
/ M ² , and the sensitizing dye was represented by the number of moles per mole of silver halide in the same layer. The symbols indicating the additives have the following meanings. However, when there are multiple utilities, only one of them is listed as a representative.

UV; UV absorber, Solv; high boiling organic solvent, ExF; dye, ExS; sensitizing dye, ExC; cyan coupler, ExM; magenta coupler, ExY; yellow coupler, Cpd; additive.

First Layer (Antihalation Layer) Black Colloidal Silver 0.15 Gelatin 2.33 ExM-2 0.11 UV-1 3.0 × 10^-2  UV-2 6.0 x 10^-2  UV-3 7.0 x 10^-2  Solv-1 0.16 Solv-2 0.10 ExF-1 1.0 × 10^-2  ExF-2 4.0 × 10^-2  ExF-3 5.0 × 10^-3  Cpd-6 1.0 x 10^-3  Second layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, sphere equivalent diameter 0.4 μm, variation coefficient of sphere equivalent diameter 30%, plate-like grain, diameter / thickness Ratio 3.0) amount of coated silver 0.35 silver iodobromide emulsion (AgI 6.0 mol%, internal high Agl type with core-shell ratio 1: 2, sphere equivalent diameter 0.45 μm, sphere equivalent diameter variation coefficient 23%, Plate-like particles, diameter / thickness ratio of 2.0) Coating amount of silver 0.18 Gelatin 0.77 ExS-1 2.4 × 10^-4  ExS-2 1.4 x 10^-4  ExS-5 2.3 × 10^-4  ExS-7 4.1 × 10^-6 (C-4) 0.06 Compound example (3) of the general formula [I] 6.0 × 10^-2  ExC-1 8.0 × 10^-2  (C-3) 0.06 ExC-3 0.06 Third layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6.0 mol%, core-shell ratio 1: 2, internal high AgI type, sphere equivalent) Diameter 0.65 μm, variation coefficient of spherical equivalent diameter 23%, plate-like particles, diameter / thickness ratio 2.0) Coating amount of silver 0.75 Gelatin 1.46 ExS-1 2.4 × 10^-4  ExS-2 1.4 x 10^-4  ExS-5 2.4 × 10^-4  ExS-7 4.3 × 10^-6  (C-4) 0.15 Compound example of the general formula [I] (3) 3.0 × 10^-2  ExC-1 0.10 (C-3) 0.15 ExC-2 2.0x10^-2  ExC-3 0.09 ExM-3 2.0x10^-2  UV-2 5.7 x 10^-2  UV-3 5.7 x 10^-2  Fourth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (9.3 mol% of AgI, multi-structured grains having a core-shell ratio of 3: 4: 2, AgI content of 24,0.6 mol% from the inside, sphere equivalent) Diameter 0.75 μm, variation coefficient of spherical equivalent diameter 23%, plate-like particles, diameter / thickness ratio 2.5) Coating amount of silver 1.09 Gelatin 1.38 ExS-1 2.0 × 10^-4  ExS-2 1.1 × 10^-4  ExS-5 1.9 × 10^-4  ExS-7 1.4 × 10^-5  (C-4) 8.0 × 10^-2  (C-9) 9.0 x 10^-2  ExC-2 2.0 x 10^-2  Solv-1 0.20 Solv-2 0.53 Fifth layer (intermediate layer) Gelatin 0.62 Cpd-1 0.13 Polyethyl acrylate latex 8.0 × 10^-2  Solv-1 8.0 × 10^-2  Sixth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, sphere equivalent diameter 0.33 μm, variation coefficient of sphere equivalent diameter 37%, plate-like particles, diameter / thickness Ratio 2.0) Coating amount of silver 0.19 Gelatin 0.44 ExS-3 1.5 × 10^-4  ExS-4 4.4 × 10^-4  ExS-5 9.2 × 10^-5  ExM-1 0.10 ExM-5 0.09 ExM-3 3.0 × 10^-2 Solv-1 0.13 Solv-2 0.6 × 10^-2  7th layer (medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, sphere equivalent diameter 0.55 μm, variation coefficient of sphere equivalent diameter 15%, tabular grains, diameter / thickness Ratio 4.0) Silver coating amount 0.24 Gelatin 0.54 ExS-3 2.1x10^-4  ExS-4 6.3 × 10^-4  ExS-5 1.3 x 10^-4  ExM-1 0.10 ExM-4 0.10 ExM-3 4.0 × 10^-2 Example of compound of general formula [I] (19) 5.9 × 10^-2  Solv-1 0.23 S0lv-4 0.7x10^-2  Eighth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 8.8 mol%, multi-structured grains with a silver amount ratio 3: 4: 2, AgI content from the inside of 24,0.3 mol%, spheres Equivalent diameter 0.75 μm, variation coefficient of spherical equivalent diameter 23%, plate-like particles, diameter / thickness ratio 1.6) Coating silver amount 0.49 Gelatin 0.61 ExS-4 4.3 × 10^-4  ExS-5 8.6 × 10^-5  ExS-8 2.8 × 10^-5  ExM-1 8.0 × 10^-2  ExM-2 3.0 x 10^-2 Example of compound of general formula [I] (19) 5.9 × 10^-2  (C-4) 1.0 x 10^-2  (C-9) 1.0 x 10^-2  Solv-1 0.23 Solv-2 5.0x10^-2  Solv-4 1.0 x 10^-2  Cpd-8 1.0 x 10^-2  Ninth layer (intermediate layer) gelatin 0.56 Cpd-1 4.0 × 10^-2  Polyethyl acrylate latex 5.0 × 10^-2  Solv-1 3.0 x 10^-2  UV-4 3.0 x 10^-2  UV-5 4.0 x 10^-2  10th layer (donor layer having a multi-layer effect on the red-sensitive layer) Silver iodobromide emulsion (AgI 8.0 mol%, internal high AgI type with core-shell ratio 1: 2, sphere equivalent diameter 0.65 μm, sphere equivalent diameter variation coefficient) 25%, tabular grains, diameter / thickness ratio 2.0) Coating silver amount 0.67 Silver iodobromide emulsion (AgI 4.0 mol%, uniform AgI type, sphere equivalent diameter 0.4 μm, variation coefficient of sphere equivalent diameter 30%, plate-like particles, diameter / thickness ratio 3.0) Coating amount of silver 0.20 Gelatin 0.87 ExS-3 6.7 × 10^-4  Example of compound of general formula [I] (19) 0.16 Solv-1 0.30 Solv-6 3.0 × 10^-2 Eleventh layer (yellow filter layer) Yellow colloidal silver 9.0 × 10^-2  Gelatin 0.84 Cpd-2 0.13 Solv-1 0.13 Cpd-1 8.0 × 10^-2  Cpd-6 2.0 x 10^-3  H-1 0.25 12th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI type, sphere equivalent diameter 0.7 μm, variation coefficient of sphere equivalent diameter 15%, plate -Shaped grains, diameter / thickness ratio of 7.0) coating amount of silver 0.50 silver iodobromide emulsion (AgI 3.0 mol%, uniform AgI type, sphere equivalent diameter 0.3 μm, variation coefficient of sphere equivalent diameter 30%, plate Particles, diameter / thickness ratio 7.0) Coating amount of silver 0.30 Gelatin 2.18 ExS-6 9.0 × 10^-4  (C-4) 0.14 (A-3) 1.09 Solv-1 0.54 13th layer (intermediate layer) Gelatin 0.40Example of compound of general formula [I] (18) 0.20 Solv-1 0.19 14th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, spherical equivalent diameter 1.0 μm, variation coefficient of spherical equivalent diameter 25%, Multiple twinned plate-like grains, diameter / thickness ratio 2.0) Coating amount of silver 0.40 Gelatin 0.49 ExS-6 2.6 × 10^-4  (A-3) 0.20 (C-4) 1.0 × 10^-2  Solv-1 9.0 x 10^-2  Fifteenth layer (first protective layer) Fine grain silver iodobromide emulsion (AgI 2.0 mol%, uniform AgI type, sphere equivalent diameter 0.07 μm) Coating silver amount 0.10 Gelatin 0.63 UV-4 0.11 UV -5 0.18 Solv-5 2.0x10^-2  Cpd-5 0.10 Polyethyl acrylate latex 9.0 × 10^-2  Sixteenth layer (second protective layer) Fine grain silver iodobromide emulsion (AgI 2.0 mol%, uniform AgI type, sphere equivalent diameter 0.07 μm) Coating silver amount 0.20 Gelatin 0.85 B-1 (diameter 1. 5 μm) 8.0 × 10^-2  B-2 (diameter 1.5 μm) 8.0 × 10^-2  B-3 2.0 x 10^-2  W-4 2.0 x 10^-2  H-1 0.18 In addition to the above, 1,2-ben
Diisothiazolin-3-one (average 2 for gelatin)
00 ppm), n-butyl-p-hydroxybenzoate
(About 1,000 ppm) and 2-phenoxy
Tanol (about 10,000 ppm) was added. Sa
B-4, B-5, F-1, F-2, F-3, F-
4, F-5, F-6, F-7, F-8, F-9, F-1
0, F-11, F-12 and iron salt, lead salt, gold salt, platinum
It contains salt, iridium salt and rhodium salt.

In addition to the above components, surfactants W-1, W-2 and W-3 were added to each layer as coating aids and emulsion dispersants.

The structural formulas of the compounds used to prepare the samples are shown below.

[0321]

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[0322]

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[0323]

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[0324]

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[0325]

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[0326]

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[0327]

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[0328]

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[0329]

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[0330]

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[0331]

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[0332]

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[0333]

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[0334]

Embedded image Next, in Samples 102 to 109, the couplers used in the seventh and eighth layers of the green-sensitive emulsion layer and the blue-sensitive emulsion layer and the twelfth to fourteenth layers of the intermediate layers thereof were changed to the couplers shown in Table 8, respectively. Substituting equimolar amount , 1.5 layers of DIR coupler are used for the 12th and 14th layers.
× 10 ⁻⁴ mol / m ² , 1.0 × 10 ⁻⁵ mol / m ² added
In addition, a sample was prepared without changing the others.

[0335]

[Table 8] These prepared samples were cut and processed into a width of 35 mm, exposed imagewise, and processed by an automatic developing machine until the cumulative replenishment amount of the color developing solution was three times the mother liquor tank capacity by the method described below. And then white light (4800K) on each sample.
Processing was performed by applying a wedge exposure of.

Treatment Method Process Treatment Time Treatment Temperature Replenishment Amount Tank Capacity [mL] [L] Color development 3 minutes 15 seconds 38 ° C. 33 10 Bleach 6 minutes 30 seconds 38 ° C. 25 10 Water wash 2 minutes 10 seconds 24 ° C. 1200 10 Settling 4 minutes 20 seconds 38 ° C 25 10 Washing (1) 1 minute 05 seconds 24 ° C (2) to (1) 10 Countercurrent piping method Washing (2) 1 minute 00 seconds 24 ° C 1200 10 Stability 1 minute 05 seconds 38 ° C. 25 10 dry 4 minutes 20 seconds 55 ° C. Replenishment amount per 35 mm width 1 m length Next, the composition of the treatment liquid is described.

(Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 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-hydroxyethylamino] -2-Methylaniline sulfate 4.5 5.5 Add water 1.0 L 1.0 L pH 10.05 10.10 (bleaching solution) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid Sodium ferric iron Trihydrate 100.0 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 10.0 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 3 0.0 Ammonia water (27%) 6.5 ml 4.0 ml Add water 1.0 L 1.0 L pH 6.0 5.7 (Fixer) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid disodium salt 0.5 0.7 Sodium sulfite 7.0 8.0 Sodium bisulfite 5.0 5.0 Ammonium thiosulfate aqueous solution (700 g / L) 170.0 ml 200.0 ml Water was added to 1.0 L 1.0 L pH 6. 7 6.6 (Stabilizing liquid) Mother liquor (g) Replenishing liquid (g) Formalin (37%) 2.0L 3.0L Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 0.45 Ethylenediaminetetraacetic acid disodium salt 0.05 0.08 Water was added to 1.0 L 1.0 L pH 5.0-8.0 5.0-8.0 The obtained treated sample had a solid color image. To examine the, 7
Store for 10 days in the dark at 0 ° C. and 80% RH, determine the exposure amount that gives the yellow density of minimum density +1.0 before the test start, and determine the yellow density at the same exposure amount after the test. After reading, the density difference (ΔD _Y ) before the start of the test and after the end of the test was determined. The smaller the value, the more robust the color image. The results are shown in Table 9.

Next, in order to examine the sharpness as one of the evaluations of the image quality, the sample was exposed to an MTF pattern with white light, and after the above treatment, the MTF value of the yellow color image was measured by a conventional method. Table 9 shows the values at 25 [cycles / mm].

As another evaluation of image quality, each sample is uniformly exposed to 1.0 Lux · sec of green light, and then gradation exposure of blue light is performed. The value obtained by subtracting the magenta density value at the minimum density of the yellow density from the magenta density value at the exposure amount giving the density of the minimum density +1.7 is defined as the color turbidity (T _B ) of the yellow color image, and is used as a scale for color reproduction. evaluated. The smaller the value, the smaller the density in the green color range, and the higher the color saturation. The results are also shown in Table 9.

[0340]

[Table 9] From the table, Samples 103 to 109 containing the yellow coupler of the present invention and the compound represented by the general formula [I] of the present invention
It is clear that, in comparison with Samples 101 to 102 , the color image fastness and the sharpness under the condition of dark and humid heat can be improved . Further, it is clear from the comparison with the comparative sample that the use of the yellow coupler of the present invention and the compound represented by the general formula [I] of the present invention reduces the color turbidity, and the sharpness and color reproducibility are improved. It turns out that it is excellent.

[0341] In general formula [I] is preferably used in the same layer of the compound represented by also the yellow coupler and the invention of the present invention, particularly Sample 106-109 and the sample
It can be seen from the comparison with 103 and 104 .

Example 2 Based on the sample 108 of Example 1, used as the seventh and eighth layers of the green sensitive layer (Y-58), the blue sensitive layer and the twelfth to fourteenth layers of the intermediate layer thereof. Used in (Y-7), (Y-58),
A sample was prepared by substituting each of (14) with the compound represented by the general formula (1) or (2) and the general formula [I] of the present invention in equimolar amounts as shown in Table 10. .

[0343]

[Table 10] These prepared samples were cut and processed to have a width of 35 mm as in Example 1, and each sample was subjected to imagewise exposure every day using an automatic developing machine, and a total length of 20 m per day was processed to obtain a color developer. The running treatment was carried out until the cumulative replenishing amount of the replenishing liquid of was 3 times the mother liquor tank capacity. After that, the same exposure as in Example 1 was applied, and the performance evaluation of color image fastness and sharpness was performed in the same manner. In addition, the logarithm of the reciprocal of the exposure amount which gives the density of the minimum density + 0.2 as the sensitivity of the photographic property was obtained from the characteristic curve obtained by measuring the density with blue light when the color image fastness was evaluated. Sample 1 prepared in Example 1 for comparison
No. 01 was processed at the same time, and the difference was obtained using this sample 101 as a reference.

The processing steps and the composition of the processing solution used are as follows.

Processing Steps Processing Time Processing Temperature Replenishment Amount Tank Capacity [mL] [L] Color development 3 minutes 05 seconds 38.0 ° C 600 5 Bleach 50 seconds 38.0 ° C 140 3 Bleach fixing 50 seconds 38.0 ° C −3 Settling 50 seconds 38.0 ° C. 420 3 Washing with water 30 seconds 38.0 ° C. 980 2 Stable (1) 20 seconds 38.0 ° C. −2 Stable (2) 20 seconds 38.0 ° C. 560 2 Dry 1 minute 60 ° C. * Replenishment amount per 1 m ² of light-sensitive material The washing water was a countercurrent system from (2) to (1), and the overflow of washing water was all introduced into the fixing bath. To replenish the bleach-fix bath, connect the upper part of the bleach tank and the lower part of the bleach-fix tank of the automatic processor and the upper part of the fix tank with the lower part of the bleach-fix tank with pipes. All of the overflow generated by the supply was allowed to flow into the bleach-fix 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,
It was 50 ml and 50 ml. The crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the treatment liquid is described below.

(Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 3.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.3 3.3 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- (β -Hydroxyethyl) amino] aniline sulfate 4.5 6.0 Water was added to 1.0 L 1.0 L pH 10.05 10.05 (bleaching solution) Mother liquor (g) Replenishing solution (g) 1,3-propylene Diamine tetraacetic acid Ferric ammonium monohydrate 144.0 206.0 Ammonium bromide 84.0 120.0 Ammonium nitrate 17.5 25.0 Hydroxyacetic acid 63.0 80.0 Acetic acid 54.2 80.0 Water was added to 1.0 L 1.0 L pH [adjusted with ammonia water] 3.80 3.60 (bleach-fixing solution mother liquor) Mixture (fixer) Mother liquor (g) Replenisher (g) Ammonium sulfite 19.0 57.0 Ammonium thiosulfate aqueous solution (700 g / l) 280 ml 840 ml Imidazole 28.5 85.5 Ethylenediaminetetraacetic acid 12.5 37.5 Water 1.0L 1.0L pH [adjusted with ammonia water and acetic acid] 7.40 7.45 (wash water) mother liquor and replenisher common tap water is H type strong acid cation exchange resin (Amber manufactured by Rohm and Haas) Light IR-120B) and OH type strongly basic anion exchange resin (Amberlite IRA-4
00) is passed through a mixed bed type column to treat calcium and magnesium ions at a concentration of 3 mg / L or less,
Subsequently, sodium isocyanurate dichloride 20 mg / L
And 150 mg / L of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizer) Mother liquor and replenisher common (unit: g) Formalin (37%) 1.2 ml Sodium p-toluenesulfinate 0.3 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0 0.2 ethylenediaminetetraacetic acid disodium salt 0.05 Water was added to obtain 1.0 L pH 7.2 The results obtained are shown in Table 11.

[0349]

[Table 11] From the table, samples 201 to 210 using the coupler represented by the general formula (1) or the general formula (2) of the present invention and the coupler represented by the general formula [I] are clearly color images as compared with the comparative sample 101. It is clear that it has excellent fastness and image quality (sharpness). Further, it is clear that the photographic sensitivity is also excellent.

In the coupler represented by the general formula (1) or the general formula (2) of the present invention, the coupler represented by the general formula (2) is more preferable than the coupler represented by the general formula (1). , Sample 20 that is excellent in the above-mentioned various performances
It can be seen from the comparison between 1,202 and samples 204,205. Further, in the couplers represented by the general formula (2) of the present invention, coupler samples 201 and 202 in which a leaving group is bonded to an active position via a nitrogen atom are bonded to an active position to which a leaving group is bonded via an oxygen atom. It is also understood that the above-mentioned various performances are superior to those of the coupler sample 203.

Example 3 Based on the sample 108 prepared in Example 1, a cyan coupler (C-) which was used for the second to fourth layers of the red-sensitive emulsion layer was used.
3), (C-4), (C-9) and Exc-3 and yellow couplers (Y-7) used for the 12th and 14th layers of the blue-sensitive emulsion layer were changed as shown in Table 12. Then, an equimolar amount was replaced to prepare a sample.

[0352]

[Table 12]

[0353]

[Chemical formula 106]

[0354]

Embedded image In the table, the same layers in which couplers are listed from the top to the bottom of two to three correspond to the order described from the top to the bottom of the sample 108 as a base, and the top is the top and the bottom is the bottom. Indicates that the equimolar amount was substituted corresponding to the lower row.

The produced sample was cut and processed into a width of 35 mm as in the previous example, subjected to gradation exposure with white light (4800K), and subjected to the treatment described in Example 1. At this time, however, the replenishing amount of the bleaching solution was 20 ml per 1 m of the width of 35 mm, and the pH of the mother liquor and the replenishing solution of the bleaching solution were adjusted to 5.7 and 5.35, respectively. First, this treatment was performed, and subsequently, a running treatment was continuously performed until a replenisher solution having a volume three times as much as the mother liquor tank volume of the bleaching solution was replenished, and then, the same exposed sample was treated again.

The treated samples were immediately subjected to density measurement, and the sensitivity points were determined from the characteristic curves measured with red light and blue light according to the method described in Example 2 for each sample. Also, from the sensitivity point to the high exposure amount side,
The density at which an exposure amount of ogE = 1.5 was given was read.

From these values, the sensitivity difference (ΔS _R , ΔS _B ) and the concentration difference (ΔD _R , ΔD) with respect to the value after the running process were set for each sample with the value before the running process as a reference.
_B ) asked. On the other hand, with respect to the value before the start of running, the sensitivity difference (ΔS _r , ΔS _b ) with each sample was obtained with the value of the sample 108 as a reference.

The results are summarized in Table 13.

[0359]

[Table 13] From the table, even in the present invention, the couplers used in the red-sensitive emulsion layer are the naphthol type, 2-phenylureido-5-acylaminophenol type, and the couplers represented by the general formula (C) used for comparison. Of Samples 108, 304 to 306 and Samples 301 to 303 are superior overall in terms of photographic properties (sensitivity), sensitivity due to processing variations, variation in color density, etc., as compared with 5,5-diacylaminophenol type couplers. You can see from the comparison.

On the other hand, as the yellow coupler, the coupler represented by the general formula (A) is similar to the cyan coupler in comparison with the pivaloylacetanilide type coupler, but the photographic properties, the sensitivity due to the process variation, and the color density are similar to those of the cyan coupler. Sample 108, 309 to 315 and Sample 3 are good in terms of fluctuations and the like.
It is clear from the comparison with 07,308.

[0361]

INDUSTRIAL APPLICABILITY A silver halide color photographic light-sensitive material having at least one light-sensitive emulsion layer on a support, reacts with an oxidized product of a developing agent to form a diffusion-resistant dye, represented by the general formula (1). Alternatively, it contains at least one coupler represented by the above general formula (2) which reacts with an oxidized product of a developing agent to form a diffusion resistant dye, and at least one compound represented by the general formula [I]. By doing so, it is possible to provide a silver halide color photographic light-sensitive material excellent in color image fastness, sharpness and color reproducibility, and in processing dependence.

Claims (3)

(57) [Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive emulsion layer on a support, which reacts with an oxidized product of a developing agent to form a diffusion resistant dye. Or a coupler represented by the following general formula (2) which reacts with an oxidized product of a developing agent to form a diffusion resistant dye, and a compound represented by the following general formula [I] Silver halide color photographic light-sensitive material. General formula (1) General formula (2) 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 that forms a nitrogen-containing heterocyclic group with>N—; and Y represents an aryl group or a heterocyclic group. Z represents a group which is released when the coupler represented by the general formula reacts with an oxidized developing agent. General formula [I] In the formula, A reacts with an oxidant of an aromatic primary amine developing agent to produce {(L1) _a- (B) _m } _p- (L2) _n- DI.
Represents a group that cleaves L, and L1 represents L represented by the general formula [I].
1 represents a group in which after the bond on the left side of 1 is cleaved, the bond on the right side (bond with (B) _m ) is cleaved, and B reacts with an oxidized product of a developing agent to form B of the formula [I]. The bond on the right side represents a group that is cleaved, L2 represents a group in which the bond on the right side (bond with DI) is cleaved after the bond on the left side of L2 represented by the general formula [I] is cleaved, and DI is development inhibition. Represents an agent, a, m and n each represent 0 or 1, and p represents an integer of 0 to 2. Here, when p is plural, p (L1) _a −
(B) _m represents the same or different. 2. The silver halide color photographic light-sensitive material according to claim 1, which contains a cyan coupler represented by the following general formula (C). General formula (C): In the formula (C), R ₂₁ is -CONR ₂₄ R ₂₅ , -SO ₂ N
_{R 24 R 25, -NHCOR 24,} -NHCOOR 26, -NH
SO ₂ R ₂₆ , —NHCONR ₂₄ R ₂₅ or —NHSO ₂
NR ₂₄ R ₂₅ , R ₂₂ represents a group capable of being substituted on a naphthalene ring,
p represents an integer of 0 to 3, R ₂₃ represents a substituent, and X ₂₁ represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. However,
R ₂₄ and R ₂₅ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₂₆ represents an alkyl group, an aryl group or a heterocyclic group. When p's are plural, R _22's may be the same or different and may combine with each other to form a ring. R ₂₂ and R ₂₃ or R ₂₃
And X ₂₁ may combine with each other to form a ring. 3. The silver halide color photographic light-sensitive material according to claim 1, which contains a yellow coupler represented by the following general formula (A). General formula (A) In the general formula (A), M and Q are groups (including atoms) that can be substituted on the benzene ring, L is a hydrogen atom, a halogen atom or an aliphatic oxy group, m is an integer of 0 to 5, and n is 0. ~
In the integer of 4, X represents a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. However, when m is plural, (M) _m may be the same or different, and when n is plural, (Q) _n may be the same or different. Further, M, Q, L or X may be a divalent to tetravalent linking group to form a dimer to tetramer of the yellow coupler represented by the general formula (A).