JPH06130594A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve sharpness, graininess, color reproduction performance and preservation stability by incorporating a compound for releasing a specified photographic useful group. CONSTITUTION:The silver halide color photographic sensitive material contains the compound to be allowed to release the photographic useful group or its precursor but substantially not to form a color image and represented by formula in which R1 is a group to be allowed to release the compound produced by the reaction between the compound of the formula I and the oxidation product of a developing agent into a processing solution; R2 is H or a substituent; n1 is 0-4; X1 is O or S; W1 is C or S; X2 is O, S, or =NR4; R3 is alkyl, aryl, a hetero-cyclic group, or the like; R4 is H, alkyl, aryl, or the like; each of X3 and X4 is H or a substituent; TIME is a timing group; n3 is O or 1; PUG is a photographic useful group; and at least one of R3, X3 and/or X4 is a diffusion- resisting group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material, more specifically, a sharpness,
The present invention relates to a silver halide color photographic light-sensitive material having improved graininess, color reproducibility and storage stability.

[0002]

2. Description of the Related Art In a subtractive color photographic light-sensitive material,
Conventionally, development inhibitor releasing couplers (DIR couplers) have been used for the purpose of improving photographic performance such as sharpness, graininess or color reproducibility. For the photographic function of DIR couplers, see "The Theory of Photographic Pr" edited by TH James.
ocess ", 4th ed., pp610-611 and p344 (1977, MACMILLANP
UBLISHING Co., New York) and the like. By the way, the DIR couplers are roughly classified into those of the type which, during development, release a development inhibitor or its precursor by a coupling reaction with an oxidized product of a developing agent and simultaneously form a dye, and a coupling reaction with an oxidized product of a developing agent. Are known to produce a compound which releases a development inhibitor or its precursor but does not substantially participate in the formation of a color image. Since an ordinary silver halide color photographic light-sensitive material is composed of a light-sensitive layer which develops yellow, magenta and cyan, when a DIR coupler of the former type is used, a color image-forming coupler of the light-sensitive layer to be added is used. It is desirable to use those that form dyes of the same color, in that color turbidity does not occur. However, since a compound that exhibits sufficient performance as a DIR coupler that produces a magenta dye has not been found in practice, a DIR coupler that produces a yellow dye in a green photosensitive layer is currently used. is there. On the other hand, the latter type D
Since the IR coupler does not substantially participate in the formation of a color image, it can be used in a photosensitive layer that develops any color without causing color turbidity. U.S. Pat. No. 4,482,629 is a DIR coupler of the type which produces a compound which releases a development inhibitor or its precursor by a coupling reaction with an oxidized product of a developing agent but does not substantially participate in the formation of a color image. , JP-A-63-37350, US Pat. No. 5,026,628, European Patent Publication Nos. 0443530 and 0514869, and the like are known. However, the compounds known so far have the performance requirements required for this type of DIR coupler, that is, they do not cause color turbidity, can sufficiently improve the color reproducibility and sharpness, and It is difficult to say that all of them are stable in the light-sensitive material during storage, and further improvement was necessary.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material having improved sharpness, graininess, color reproducibility and storage stability.

[0004]

The object of the present invention has been achieved by a silver halide color photographic light-sensitive material containing a compound represented by the following general formula (I). General formula (I)

[0005]

[Chemical 2]

(In the formula, R ₁ represents a group which allows the compound formed by the reaction of the compound represented by the general formula (I) and the oxidized product of the developing agent to flow out into the processing solution,
R ₂ represents a hydrogen atom or a substituent, n1 represents 0 to 4, and when n1 is 2 or more, two or more R ₂ may be the same or different. X ₁ represents an oxygen atom or a sulfur atom, W ₁ represents a carbon atom or a sulfur atom, and X ₂ represents an oxygen atom, a sulfur atom or = NR ₄ . N2 is 1 when W ₁ is a carbon atom, and n is when W ₁ is a sulfur atom
2 is 1 or 2. R ₃ is an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group,
Represents an aryloxycarbonyl group, a carbamoyl group, a sulfonyl group or a sulfamoyl group, R ₄ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group,
It represents an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfonyl group or a sulfamoyl group. X ₃ and X ₄ each represent a hydrogen atom or a substituent, TIME represents a timing group, n3 represents 0 or 1, and PUG represents a photographically useful group.
At least one of R ₃ , X ₃ and / or X ₄ represents a diffusion resistant group. )

Since the compound represented by the general formula (I) has a fast coupling reaction with an oxidized product of a developing agent, PUG can be efficiently released at the initial stage of development. General formula (I)
The compound represented by is highly stable to heat. In these respects, the compound represented by the general formula (I) is superior to the known compounds described in the above-mentioned patents.

The compound represented by formula (I) of the present invention will be described in detail below. R ₂ represents a hydrogen atom or a substituent, and the substituent is a halogen atom (for example,
Fluorine atom, chlorine atom, aliphatic group (straight chain, branched chain or cyclic alkyl group having 10 or less carbon atoms, alkenyl group, alkynyl group, such as methyl, ethyl, isopropyl,
1-butyl, t-butyl, 2-methanesulfonylethyl, trifluoromethyl, 3-phenyl-1-propyl, 2-phenyl-1-butyl, benzyl, cyclopentyl), aryl group (aryl group having 10 or less carbon atoms) ,
For example, phenyl, p-tolyl, 4-t-butylphenyl, 4-chlorophenyl, 4-nitrophenyl, 4-ethoxyphenyl, 1-naphthyl), a heterocyclic group (a group having 6 or less carbon atoms, such as 2- Thienyl, 4-pyridyl, 2
-Furyl, 2-pyrimidinyl, 1-pyridyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (groups having 6 or less carbon atoms, such as methoxy, ethoxy, 1-butoxy), aryloxy group (10 carbon atoms) In the following groups, for example, phenoxy, 4-methoxyphenoxy, 4-nitrophenoxy, 3-butanesulfonamidophenoxy, 2-naphthoxy), heterocyclic oxy group (for example, 2-furyloxy in groups having 6 or less carbon atoms), Acyloxy groups (groups having 10 or less carbon atoms such as acetoxy,
Pivaloyloxy, benzoyloxy), an alkoxycarbonyloxy group (a group having 6 or less carbon atoms, such as ethoxycarbonyloxy, t-butoxycarbonyloxy), an aryloxycarbonyloxy group (having 10 carbon atoms).
The following groups include, for example, phenoxycarbonyloxy), carbamoyloxy groups (groups having 10 or less carbon atoms, for example,
N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy), sulfamoyloxy group (having 1 carbon atom)
A group having 0 or less, for example, N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), a sulfonyloxy group (a group having 10 or less carbon atoms, for example, methanesulfonyloxy, benzenesulfonyloxy), an acyl group (A group having 10 or less carbon atoms such as acetyl, pivaloyl, benzoyl), an alkoxycarbonyl group (having 6 carbon atoms)
The following groups are, for example, ethoxycarbonyl, aryloxycarbonyl groups (for groups having 10 or less carbon atoms, for example, phenoxycarbonyl), carbamoyl groups (for groups having 10 or less carbon atoms, for example, N, N-dimethylcarbamoyl, N-propyl). Carbamoyl), an amino group (a group having 6 or less carbon atoms, for example, amino, N-methylamino, N, N-dimethylamino), an anilino group (a group having 10 or less carbon atoms, for example,
N-methylanilino), heterocyclic amino groups (groups having 6 or less carbon atoms, for example, 4-pyridylamino), amide groups (groups having 10 or less carbon atoms, such as acetamide, benzamide, trifluoroacetamide), alkoxycarbonylamino groups (C6 or less groups such as isobutyloxycarbonylamino, ethoxycarbonylamino), aryloxycarbonylamino groups (C10 or less groups such as phenoxycarbonylamino), ureido groups (C10 or less groups For example, N-phenylureido, N, N-dimethylureido), a sulfonamide group (a group having 10 or less carbon atoms, for example, methanesulfonamide), a sulfamoylamino group (a group having 10 or less carbon atoms, for example, N, N-dimethylsulfamoylamino), alkylthio group (6 carbon atoms For example a group of the lower, ethylthio), for example an arylthio group (having 10 or less of group carbon,
Phenylthio), a sulfinyl group (a group having 10 or less carbon atoms such as benzenesulfinyl), a sulfonyl group (a group having 10 or less carbon atoms such as methanesulfonyl, p-toluenesulfonyl), a sulfamoyl group (a group having 10 or less carbon atoms). For example, N, N-dimethylsulfamoyl, N
-Ethylsulfamoyl) and sulfo groups. Preferably, R ₂ represents a hydrogen atom, a halogen atom, an amide group, an alkoxycarbonylamino group, a sulfonamide group, a sulfo group, a sulfamoyl group or a carboxyl group.

R ₁ represents a group which allows a compound produced by a coupling reaction between the compound represented by the general formula (I) and an oxidized product of a developing agent to flow out into a processing solution, and specifically, _{SO 2 R 11, -CO 2 R} 12, -CN, -
CONHR ₁₃ or a group represented by the following general formula (II). General formula (II)

[0010]

[Chemical 3]

R ₁₁ is a hydroxyl group, an alkoxy group (alkoxy group having 6 or less carbon atoms, for example, methoxy, ethoxy, 1-butoxy), an aryloxy group (aryloxy group having 10 or less carbon atoms, for example, phenoxy, 4- Methoxyphenoxy, 4-nitrophenoxy, 3-butanesulfonamidophenoxy, 2-naphthoxy), a heterocyclic oxy group (a heterocyclic oxy group having 6 or less carbon atoms, for example,
2-furyloxy), an amino group (an amino group having 6 or less carbon atoms, such as amino, N-methylamino, N, N-dimethylamino), an anilino group (an anilino group having 10 or less carbon atoms, such as N-methylanilino). ), A heterocyclic amino group (a heterocyclic amino group having 6 or less carbon atoms, for example, 4-pyridylamino), an alkylthio group (an alkylthio group having 6 or less carbon atoms, for example, ethylthio), or an arylthio group (an arylthio group having 10 or less carbon atoms). Represents, for example, phenylthio). R ₁₂ is a hydrogen atom, an alkyl group (having 1 carbon atom
A straight chain, branched chain or cyclic alkyl group of 6 to 6 such as methyl, ethyl, isopropyl, 1-butyl, t-butyl, 2-methanesulfonylethyl, trifluoromethyl, cyclopentyl), an aryl group (having 10 or less carbon atoms). An aryl group such as phenyl, p-tolyl, 4-t-
Butylphenyl, 4-chlorophenyl, 4-nitrophenyl, 4-ethoxyphenyl, 1-naphthyl) or a heterocyclic group (a heterocyclic group having 6 or less carbon atoms, such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl).

R ₁₃ represents a hydrogen atom, an alkyl group having 4 or less carbon atoms, or a group represented by the general formula (III). General formula (III)

[0013]

[Chemical 4]

Examples of the alkyl group having 4 or less carbon atoms represented by R ₁₃ include methyl, ethyl, propyl, isopropyl, butyl, 2-butyl and isobutyl. These alkyl groups may further have a substituent,
Preferred substituents are a halogen atom (eg, fluorine atom, chlorine atom), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (alkoxy group having 1 to 3 carbon atoms, eg, methoxy, ethoxy), acyloxy group ( A group having 10 or less carbon atoms, for example, acetoxy, chloroacetoxy, benzoyloxy), an alkoxycarbonyloxy group (for example, methoxycarbonyloxy for a group having 6 or less carbon atoms), a carbamoyloxy group (6 carbon atoms).
The following groups include, for example, N, N-dimethylcarbamoyloxy), sulfamoyloxy groups (for example, N, N-diethylsulfamoyloxy for groups having 6 or less carbon atoms), sulfonyloxy groups (having 6 or less carbon atoms). A group such as methanesulfonyloxy), an acyl group (a group having 6 or less carbon atoms such as acetyl), an alkoxycarbonyl group (a group having 6 or less carbon atoms such as methoxycarbonyl), an aryloxycarbonyl group (having 10 or less carbon atoms). Groups such as phenoxycarbonyl), carbamoyl groups (groups having 6 or less carbon atoms such as carbamoyl and N-methylcarbamoyl),
Amino group (for example, amino or N-methylamino having 6 or less carbon atoms), amide group (for example, acetamido for 10 or less carbon atoms), alkoxycarbonylamino group (for example, methoxy for 6 or less carbon atoms) Carbonylamino), ureido group, sulfonamide group (for example, methanesulfonamide having 10 or less carbon atoms), sulfamoylamino group (for example, N, N-dimethylsulfamoylamino for 6 or less carbon atoms) , Sulfonyl group (C1
Examples of groups of 0 or less include methanesulfonyl). Particularly preferred as the alkyl group represented by R ₁₃ are methyl group and ethyl group, and particularly preferred as the substituent of the alkyl group represented by R ₁₃ are halogen atom, cyano group, hydroxyl group, nitro group, alkoxy group, Acyloxy group, alkoxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group,
Sulfonyloxy group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, amide group, ureido group, sulfonamide group, sulfamoylamino group, sulfonyl group, cyano group, amide group, sulfone group Amido group, sulfo group, sulfamoyl group, carbamoyl group, alkoxycarbonyl group, carboxyl group, hydroxyl group and sulfonyl group are more preferred. In particular, sulfonamide group, sulfo group,
Sulfamoyl group, carbamoyl group, carboxyl group,
The alkoxycarbonyl group and the hydroxyl group are preferable in that the compound represented by the general formula (I) reacts with the oxidized product of the developing agent to enhance the outflow property of the dye.

In the group represented by the general formula (III), W
₂ -CON (R ₂₅₎ - or -CO ₂ - represents a. R ₂₁ ,
R ₂₂ , R ₂₃ and R ₂₄ each represent a group having the same meaning as the group represented by R ₂ , R ₂₅ represents a hydrogen atom or an alkyl group (eg methyl, ethyl, propyl), and these groups are further substituted. It may have a group, and preferable substituents are those mentioned as the group represented by R ₂ . R ₂₆ represents an alkyl group having 3 or less carbon atoms (for example, methyl, ethyl, propyl, trifluoromethyl, trichloromethyl, trifluoroethyl), and n6 and n7 each represent 1, 2 or 3. Of these, R ₂₁ , R ₂₂ , and R
₂₃ , R ₂₄ and R ₂₅ are each a hydrogen atom or a carbon atom of 3
The following alkyl groups are preferable, and a hydrogen atom or a methyl group is most preferable. n6 and n7 are preferably 1 or 2. R ₂₆ is preferably a methyl group or an ethyl group.

In the group represented by the general formula (II), R
₃₁ represents a hydrogen atom or an alkyl group having 4 or less carbon atoms (eg, methyl, ethyl, propyl, butyl), and preferably a hydrogen atom, a methyl group or an ethyl group. R ₃₃ represents an organic group having 1 to 10 carbon atoms, preferably R ₃₃ is an alkyl group (an alkyl group having 6 or less carbon atoms such as methyl,
Ethyl), aryl groups (aryl groups having 10 or less carbon atoms, for example, phenyl, p-tolyl), hydroxyl groups, alkoxy groups (alkoxy groups having 6 or less carbon atoms, for example, methoxy, ethoxy, 1-butoxy), aryloxy A group (an aryloxy group having 10 or less carbon atoms, such as phenoxy, 4-methoxyphenoxy, 4-nitrophenoxy,
3-butanesulfonamidophenoxy, 2-naphthoxy), heterocyclic oxy group (for example, 2-furyloxy for a heterocyclic oxy group having 6 or less carbon atoms), amino group (for example, amino for an amino group having 6 or less carbon atoms, N-methylamino, N, N-dimethylamino), anilino group (carbon number 1
An anilino group of 0 or less, such as N-methylanilino),
Heterocyclic amino group (for example, 4-pyridylamino for a heterocyclic amino group having 6 or less carbon atoms), alkylthio group (for example, ethylthio for an alkylthio group having 6 or less carbon atoms) or arylthio group (for example, an arylthio group having 10 or less carbon atoms) , Phenylthio). A ₁ and A ₂ each represent —CO— or —SO ₂ —. n4 represents 0, 1 or 2, and preferably 0 or 1. R ₃₂ is 1,
2-phenylene, 1,3-phenylene, 1,4-phenylene group or _{- [C (R 34) R} 35] n5 - represents a. R ₃₂ is 1,2-phenylene, 1,3-phenylene or 1,4
In the case of a -phenylene group, these phenylene groups are -N
(R ₃₁₎ - and -A ₁ - may have a substituent in addition, the preferred substituents are the same as those mentioned as the group represented by R _2. R ₃₄ and R ₃₅ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, propyl), and these alkyl groups are a hydroxyl group, an alkoxy group (eg, methoxy, ethoxy), an alkylthio group. It may have a substituent such as (for example, methylthio) or an alkoxycarbonyl group (for example, methoxycarbonyl), and n5 represents an integer of 1 to 3. Preferred as R ₃₂ are a methylene group, an ethylene group, a 1,2-phenylene group, a 1,3-phenylene group and a 1,4-phenylene group.

X ₁ represents an oxygen atom or a sulfur atom,
W ₁ represents a carbon atom or a sulfur atom, and X ₂ represents an oxygen atom, a sulfur atom or = NR ₄ . When W ₁ is a carbon atom, n2 is 1, and when W ₁ is a sulfur atom, n2 is 1 or 2.

R ₃ is an alkyl group (a linear, branched or cyclic alkyl group having 1 to 32 carbon atoms such as methyl,
Ethyl, isopropyl, 1-butyl, t-butyl, 2-
Methanesulfonylethyl, trifluoromethyl, cyclopentyl, 1-octyltridecyl, 3- (3-pentadecylphenoxy) propyl, 3- {4- {2- [4-
(4-Hydroxyphenylsulfonyl) phenoxy] dodecanamide} phenyl} propyl, 2-ethoxytridecyl, 3- (2,4-di-t-amylphenoxy) propyl, 3-dodecyloxypropyl, allyl), aryl group ( An aryl group having 6 to 32 carbon atoms, for example, phenyl, p-tolyl, 4-t-butylphenyl, 2,4
-Di-t-amylphenyl, 4-nitrophenyl, 4-
Ethoxyphenyl, 1-naphthyl), a heterocyclic group (a group having 1 to 32 carbon atoms, such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl),
Acyl group (C1-C32 group such as acetyl, pivaloyl, benzoyl, tetradecanoyl, octadecanoyl), alkoxycarbonyl group (C1-C2 group such as ethoxycarbonyl, dodecyloxycarbonyl), Aryloxycarbonyl group (for example, phenoxycarbonyl, 4-t-octylphenoxycarbonyl), carbamoyl group (a group having 1 to 32 carbon atoms, such as N, N-dibutylcarbamoyl, N-ethyl-N-).
Octylcarbamoyl, N-dodecylcarbamoyl),
Sulfonyl group (group having 1 to 32 carbon atoms, such as hexadecanesulfonyl, octanesulfonyl, p-toluenesulfonyl, 2-octyloxy-5-t-octylbenzenesulfonyl), sulfamoyl group (having 1 to 32 carbon atoms)
Groups such as N, N-dimethylsulfamoyl, N-
Tetradecylsulfamoyl), and these groups may further have a substituent. Preferred substituents are those mentioned as the group represented by R ₂ .

R ₄ represents a hydrogen atom or a group having the same meaning as R ₃ . X ₃ and X ₄ each represent a hydrogen atom or a substituent, and examples of the substituent include an alkyl group, an aryl group and an acyl group, and the details are the same as those mentioned in the description of R ₃ . X ₃ and X ₄ may combine with each other to form a 5- to 7-membered ring. R _3, X ₃ and / or at least one of X ₄ represents a nondiffusible group, R ₃ is an alkyl group having 10 or more carbon atoms when R ₃ represents a non-diffusible group, an aryl group, a heterocyclic group , An acyl group, an alkoxycarbonyl group,
Represents an aryloxycarbonyl group, a carbamoyl group, a sulfonyl group or a sulfamoyl group, and when X ₃ and / or X ₄ represents a diffusion resistant group, X ₃ and / or X
₄ represents an alkyl group having 10 or more carbon atoms, an aryl group or an acyl group. Of these, X ₁ is preferably an oxygen atom, W ₁ is preferably a carbon atom, and X ₂ is preferably an oxygen atom. R ₃ is preferably an alkyl group, an aryl group, an acyl group or a sulfonyl group. R ₃ is preferably a diffusion resistant group, and X ₃ and X ₄ are preferably hydrogen atoms.

The photographically useful group represented by PUG in the compound represented by formula (I) is specifically described as a development inhibitor, a dye, a fogging agent, a developer, a coupler, a bleaching accelerator, a development accelerator, a fixing accelerator and the like. Is. Examples of preferred photographically useful groups are those described in U.S. Pat. No. 4,248,962 (the ones represented by the general formula PUG in the patent) and JP-A-62-49353. Dyes (part of the leaving group released from the coupler in the specification), development inhibitors described in U.S. Pat. No. 4,477,563, and JP-A-61-201247 and JP-A-2-55. And other bleaching accelerators (in the specification, the part of the leaving group released from the coupler). In the present invention, a development inhibitor is particularly preferable as the photographically useful group.

Preferred as the development inhibitor are groups represented by the following general formulas (INH-1) to (INH-13).

[0022]

[Chemical 5]

[0023]

[Chemical 6]

[0024]

[Chemical 7]

In the formula, * represents a position to be bonded to a residue of the general formula (I) excluding PUG. In addition, ** represents a position at which a substituent described below is bonded.

Preferred substituents are alkoxycarbonyl groups (eg ethoxycarbonyl, 1,4-dioxo-2,5-dioxadecyl, 1,4-dioxo-).
2,5-dioxa-8-methylnonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), alkylthio group (for example, methylthio, propylthio, hexylthio), alkoxy group (for example, methoxy, propyloxy), sulfonyl group (for example, Methanesulfonyl), carbamoyl group (eg ethylcarbamoyl), sulfamoyl group (eg ethylsulfamoyl), cyano group, nitro group, amido group (eg acetamide), alkyl group (eg methyl, ethyl, propyl, butyl) , Hexyl, decyl, isobutyl, t-butyl, 2-ethylhexyl, benzyl, 4-methoxybenzyl, phenethyl, propyloxycarbonylmethyl, 2- (propyloxycarbonyl) ethyl, butyloxycarbonylmethyl Pentyloxycarbonyl methyl, 2-cyano ethyloxycarbonylmethyl, 2,
2-dichloroethyloxycarbonylmethyl, 3-nitropropyloxycarbonylmethyl, 4-nitrobenzyloxycarbonylmethyl, or 2,5-dioxo-3,6-dioxadecyl), an aryl group (eg, phenyl, naphthyl, 4-methoxy) Carbonylphenyl,
3-methoxycarbonylphenyl, 4- (2-cyanoethyloxycarbonyl) phenyl), a heterocyclic group (for example, 4-pyridyl, 3-pyridyl, 2-pyridyl, 2-
Furyl, 2-tetrahydropyranyl) and the like.

Of these, the substituent is preferably a substituted or unsubstituted alkoxycarbonyl group, aryloxycarbonyl group, alkyl group or aryl group.
More preferably, an alkoxycarbonyl group having a substituent, an unsubstituted alkyl group having 2 to 7 carbon atoms, and 2 to 10 carbon atoms.
A substituted alkyl group or a substituted or unsubstituted phenyl group.

Of these, INH is particularly preferably (INH-1), (INH-2), (INH-3),
(INH-4), (INH-9), (INH-10),
(INH-12) and (INH-13), more preferably (INH-1), (INH-3) and (INH-12).

Next, the group represented by TIME will be described. The group represented by TIME is P after the bond on the left side of TIME in the general formula (I) is cleaved during development processing.
Any linking group capable of cleaving the bond with UG may be used. For example, U.S. Pat. No. 4,146,396
No. 4,652,516 or 4,698,29
A group utilizing the cleavage reaction of hemiacetal described in US Pat. Nos. 4,248,962 and 4,847,
185 or 4,857,440, a timing group for causing a cleavage reaction utilizing an intramolecular nucleophilic substitution reaction, US Pat. Nos. 4,409,323 or 4,421,845. A timing group that causes a cleavage reaction by using the described electron transfer reaction, a group that causes a cleavage reaction by using the hydrolysis reaction of iminoketal described in US Pat. No. 4,546,073, or published in West Germany Examples thereof include groups capable of causing a cleavage reaction by utilizing a hydrolysis reaction of an ester described in Japanese Patent No. 2,626,317. TIME is a heteroatom contained in it,
It is preferably bonded to —C (X ₃ ) X ₄ — at an oxygen atom, a sulfur atom or a nitrogen atom. As preferable TIME, the following general formulas (T-1), (T-2) or (T-
3) is mentioned.

General formula (T-1) * -W _3- (Y ₁ =
_{Y 2) j -C (R 51} ) R 52 - ** Formula _{(T-2) * -W 3} -CO - ** Formula _{(T-3) * -W 3} -LINK-E - **

In the formula, * represents -C in the general formula (I).
(X ₃₎ X ₄ - and represents a position bonding, and ** represents the position which binds to PUG, W ₃ represents an oxygen atom, a sulfur atom or -N (R ₅₃₎ - represents, Y ₁ and Y ₂ are Each represents methine or a nitrogen atom, j represents 0, 1 or 2, R ₅₁ ,
R ₅₂ and R ₅₃ each represent a hydrogen atom or a substituent. Here, when Y ₁ and Y ₂ represent a substituted methine, the substituent and any two substituents of R ₅₁ , R ₅₂ and R ₅₃ are linked to form a cyclic structure (for example, a benzene ring or a pyrazole ring). It may be either formed or not formed. In formula (T-3), E represents an electrophilic group, and LINK represents a linking group that sterically relates W ₃ and E so that they can undergo an intramolecular nucleophilic substitution reaction. Specific examples of TIME represented by the general formula (T-1) are as follows.

[0032]

[Chemical 8]

Specific examples of TIME represented by the general formula (T-2) are as follows.

[0034]

[Chemical 9]

Specific examples of TIME represented by the general formula (T-3) are as follows.

[0036]

[Chemical 10]

Specific examples of the compound of the present invention are shown below.
The present invention is not limited by these.

[0038]

[Chemical 11]

[0039]

[Chemical 12]

[0040]

[Chemical 13]

[0041]

[Chemical 14]

[0042]

[Chemical 15]

[0043]

[Chemical 16]

[0044]

[Chemical 17]

[0045]

[Chemical 18]

[0046]

[Chemical 19]

[0047]

[Chemical 20]

[0048]

[Chemical 21]

[0049]

[Chemical formula 22]

[0050]

[Chemical formula 23]

[0051]

[Chemical formula 24]

Synthetic Examples Specific synthetic examples of the compound of the present invention are shown below, but the present invention is not limited thereto. The structures of the intermediates used in the synthesis examples are shown below.

[0053]

[Chemical 25]

Synthesis Example 1 [Synthesis of Exemplified Compound (1)] (Synthesis of Intermediate B) 280 g (1.00 mol) of Intermediate A was converted into N, N-dimethylacetamide (DMAC) 300.
ml and 700 ml of acetonitrile, and the mixture was stirred at room temperature under a nitrogen atmosphere. Β-alanine 9
8.0 g (1.10 mol) and sodium hydroxide 4
A solution prepared by dissolving 7.3 g (1.10 mol) in 200 ml of water was added, and the mixture was heated under reflux on a steam bath for 2 hours. After cooling the reaction mixture, it was added to 3 liters of stirred ice water,
125 ml of concentrated hydrochloric acid was added, and the mixture was stirred for 1 hour. The precipitated crystals were collected by filtration and washed with water. The dried crystals were added to 1.2 liters of acetonitrile and heated under reflux on a steam bath for 1 hour. After cooling with stirring, the crystals were collected by filtration and washed with acetonitrile. Drying gave 190.2 g (69%) of intermediate B.

(Synthesis of Intermediate D) 95.0 g of Intermediate B
(0.345 mol) was added to 500 ml of acetonitrile,
It was cooled with ice water under a nitrogen atmosphere. In addition to this, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU)
206 ml (1.38 mol) was added and stirred for 30 minutes.
To this, 142 g (0.345 mol) of Intermediate C was added,
The mixture was stirred with cooling for 1 hour and further at room temperature for 1 hour. To this reaction mixture was added 1.0 liter of ethyl acetate and 1 part of concentrated hydrochloric acid.
Extraction was performed by adding 1.5 liters of water containing 20 ml. The organic layer was washed with 1 liter of water and then with 1 liter of saturated saline and dried over anhydrous magnesium sulfate. After concentration, n-
Crystallization was performed from a mixed solvent of hexane and ethyl acetate. The precipitated crystals were collected by filtration, washed with a mixed solvent of n-hexane and ethyl acetate, and dried to give 150.6 g (74%) of intermediate D.
Got Melting point 164-166 ° C. 1HNMR [CDCl ₃ , δ ppm] 13.8 (br, 1H), 8.42 (dd, 1H),
8.9 to 7.5 (m, 4H), 7.18 (d, 1H),
7.07 (dd, 1H), 6.75 (d, 1H), 5.
70 (t, 1H), 4.03 (t, 2H), 3.62
(M, 2H), 3.51 (dt, 2H), 2.68 (b
rt, 2H), 2.10 (m, 2H), 1.82 (q,
2H), 1.60 (q, 2H), 1.31 (s, 6
H), 1.23 (s, 6H), 0.64 (t, 3H),
0.59 (t, 3H)

[Synthesis of Exemplified Compound (1)] Intermediate D3
0.0 g (50.6 mmol), paraformaldehyde 1.52 g (50.6 mmol) and intermediate E14.
7 g (50.6 mmol) was added to 200 ml of toluene,
Stir at 42 ° C. 5.65 g of copper (II) bromide
(25.3 mmol) was added, and the mixture was stirred at the same temperature for 8 hours. 500 ml of ethyl acetate and 1N were added to the reaction mixture.
Hydrochloric acid (500 ml) was added for extraction, and the organic layer was added to 1N hydrochloric acid (400).
ml, water (400 ml) and saturated saline (400 ml) successively, and dried over anhydrous magnesium sulfate. After concentration, the product was purified by silica gel column chromatography (eluent: a mixed solvent of n-hexane and ethyl acetate containing 0.1% acetic acid), and further a mixed solvent of n-hexane and ethyl acetate (4
It was crystallized from / 1). The precipitated crystals were collected by filtration, washed with a mixed solvent of n-hexane and ethyl acetate, and then dried to obtain 28.5 g (63%) of Exemplified compound (1) as colorless crystals. Melting point 118-130 ° C

Synthesis Example 2 [Synthesis of Exemplified Compound (37)] (Synthesis of Intermediate F) 15.8 g (0.150 mol) of aminoacetonitrile 1/2 sulfate was added to 80 ml of DMAC, and 22.4 ml of DBU ( 0.150 mol) was added and the mixture was stirred under a nitrogen atmosphere at room temperature for 30 minutes. to this,
14.0 g (50.0 mmol) of Intermediate A was added, and the mixture was heated with stirring on a steam bath for 2 hours. After cooling, the reaction mixture was mixed with ethyl acetate (350 ml), water (400 ml) and concentrated hydrochloric acid (13).
ml was added for extraction. The organic layer was washed with 300 ml of water and then with 300 ml of saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude product of intermediate F. This was used as a raw material for the next step without purification.

(Synthesis of Intermediate G) The crude product of the intermediate F obtained above was added to 80 ml of DMAC, and the mixture was stirred under a nitrogen atmosphere.
It was cooled with ice water and stirred. To this, 15.0 ml of DBU
(0.100 mol) was added and stirred for 15 minutes. To this, 20.6 g (50.0 mmol) of Intermediate C was added,
The mixture was stirred with cooling for 10 minutes and further at room temperature for 2 hours.
300 ml of ethyl acetate and 13 ml of concentrated hydrochloric acid were added to this reaction mixture.
It was extracted by adding 450 ml of water containing. The organic layer is water 300
The extract was washed with 300 ml of saturated saline and then with 300 ml of saturated saline, and dried over anhydrous magnesium sulfate. After concentration, the product was purified by silica gel column chromatography (eluent: mixed solvent of n-hexane and ethyl acetate), and then crystallized from a mixed solvent (4/1) of n-hexane and ethyl acetate. The precipitated crystals are collected by filtration,
It was washed with a mixed solvent of n-hexane and ethyl acetate and dried to obtain 11.2 g (36% based on Intermediate A) of Intermediate G. 1H NMR [CDCl ₃ , δ ppm] 13.40 (s, 1H), 8.47 (d, 1H), 7.
76 (d, 1H), 7.7-7.5 (m, 3H), 7.
2-7.1 (m, 3H), 6.84 (d, 1H), 5.
63 (t, 1H), 4.14 (t, 2H), 3.63
(Dd, 2H), 2.68 (d, 2H), 2.20
(M, 2H), 1.87 (q, 2H), 1.61 (q,
2H), 1.38 (s, 6H), 1.26 (s, 6)
H), 0.66 (dt, 6H)

[Synthesis of Exemplified Compound (37)] Intermediate G
8.50 g (15.2 mmol), paraformaldehyde 0.55 g (18 mmol) and intermediate E5.24.
g (18.0 mmol) was added to 60 ml of toluene, and 42
Stirred at ° C. To this, 2.01 g of copper (II) bromide (9.
(00 mmol) was added and the mixture was stirred at the same temperature for 5 hours. 150 ml of ethyl acetate and 2N of 1N hydrochloric acid were added to the reaction mixture.
00 ml was added for extraction, the organic layer was washed successively with 150 ml of 1N hydrochloric acid, 150 ml of water and 150 ml of saturated saline, and dried over anhydrous magnesium sulfate. After concentration, the product was purified by silica gel column chromatography (eluent: a mixed solvent of dichloromethane and ethyl acetate containing 0.1% acetic acid),
10.3 g (78.5%) of Exemplified compound (37) was obtained as a pale green-yellow solid.

The compound represented by the above formula (I) of the present invention can be used in any layer in a light-sensitive material. That is, a light-sensitive layer (a blue-sensitive emulsion layer, a green-sensitive emulsion layer, a red-sensitive emulsion layer, a donor layer having a multilayer effect having a spectral sensitivity distribution different from those of the main photosensitive layer), a non-photosensitive layer (for example, a protective layer, a yellow layer). It can be used for any of a filter layer, an intermediate layer, and an antihalation layer). When the same color-sensitive layer is divided into two or more layers having different sensitivities, it may be added to any of the highest-sensitivity layer, the lowest-sensitivity layer and the intermediate-sensitivity layer, and to all layers. It can also be added. It is preferably used in the photosensitive layer and / or the non-photosensitive layer adjacent to the photosensitive layer.

The amount of the compound represented by the formula (I) used in the light-sensitive material is a coating amount in the range of 5 × 10 ^{-4 to 2} g / m ² . Preferably in the range of ^{1 × 10 -3 ~1g / m 2} , more preferably from ^{5 × 10 -3 ~5 × 10 -1} g / m 2. Regarding the use of the development inhibitor-releasing compound represented by the formula (I) in the light-sensitive material, any known dispersion method can be used depending on the compound. For example, when it is alkali-soluble, it may be added as an alkaline aqueous solution or as a solution dissolved in an organic solvent miscible with water, or an oil-in-water dispersion method using a high-boiling organic solvent, or a solid dispersion method. You can

The compound represented by the formula (I) may be used alone or in combination of two or more kinds. Also, the same compound can be used in two or more layers. further,
It can be used in combination with other known development inhibitor releasing compounds and development inhibitor precursor releasing compounds, or can be used together with the couplers and other additives described below. These are appropriately selected according to the performance required of the photosensitive material.

The compound represented by the formula (I) of the present invention is
Coupling reaction with the oxidant of the developing agent releases the development inhibitor, and its mother nucleus forms a dye. The formed dye is described in, for example, the Journal of the Photographic Society of Japan, Volume 52 (1989).
2) 150-155 (Kida et al) or 198
Proceedings of 9th Annual Meeting of the Photographic Society of Japan 2A0-22 (Kida)
As described in (1), the color solution is discharged during the color development process or the dye is bleached and erased. Therefore, the formed dye does not remain on the photosensitive material as a dye after color development processing. Therefore, the compound represented by the formula (I) of the present invention has the performance required for a light-sensitive material regardless of any layer constituting the light-sensitive material, for example, a red-sensitive emulsion layer, a green-sensitive emulsion layer or a blue-sensitive emulsion layer. There is the advantage that the compound can be used accordingly. Furthermore, since the formed dye does not remain as a dye, it has an advantageous effect on color reproducibility.
Further, the color image fastness may be improved in some cases.

The light-sensitive material of the present invention may have at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive 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 consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red color-sensitive layer and the green color. The color-sensitive layer and the blue color-sensitive layer are installed in this order.
However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound and the like, and a color mixture inhibitor as commonly used. You can leave. The plural silver halide emulsion layers constituting each unit light-sensitive layer preferably use a two-layer constitution of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. be able to. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. In addition,
57-112751, 62-200350, 62-206541, 62-20
As described in 6543, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support. As a specific example, from the side farthest from the support, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL
/ RL / RH can be installed in this order. See also
As described in JP-A-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, blue-sensitive layers / GL / RL / GH / RH may be arranged in this order from the side farthest from the support. Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. Place a silver halide emulsion layer of low degree,
An example of the arrangement includes three layers having different sensitivities in which the sensitivities are sequentially decreased toward the support. Even in the case of being composed of three layers having different sensitivities as described above, JP-A-59-2
As described in JP-A-02464, the medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer may be arranged in this order from the side distant from the support in the same color-sensitive layer. In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four or more layers, the arrangement may be changed as described above. In order to improve color reproducibility, US Pat. Nos. 4,663,271 and 4,705,744, and 4,
No. 707,436, JP-A Nos. 62-160448 and 63-89850, the main photosensitive layer is a donor layer (CL) having a multilayer effect different in spectral sensitivity distribution from the main photosensitive layer such as BL, GL, and RL. It is preferable to arrange them adjacent to or close to. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or iodochlorobromide containing about 30 mol% or less of silver iodide. It is silver. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide is about 0.
It may be fine particles of 2 μm or less or large-sized grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No. 17
643 (December 1978), pp. 22-23, "I. Emulsion production (Emulsion
preparation and types) ”, and No. 18716 (1979)
November), p. 648, ibid. 307105 (November 1989), 863-865
Page, and Graphide, "Physics and Chemistry of Photography", published by Paul Montel (P. Glafkides, Chimie et Physique Photo
graphique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Phot
ographic Emulsion Chemistry (Focal Press, 1966)),
Zelikman et al., "Manufacturing and Coating of Photographic Emulsions", published by Focal Press (VL Zelikman et al., Making and Coat
ing Photographic Emulsion, Focal Press, 1964) and the like.

Monodispersed emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. The tabular grains are
Gatov, Photographic Science and
Engineering (Gutoff, Photographic Science and
Engineering, 14: 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048,
It can be easily prepared by the method described in U.S. Pat. No. 4,439,520 and British Patent No. 2,112,157. The crystal structure may be uniform, may have a different halogen composition between the inside and the outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the corresponding portions are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion,
It can be used by mixing in the same layer. US Patent No.
4,082,553 grain surface-fogged silver halide grains, U.S. Pat. It can be preferably used in the silver emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer.
The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,498, JP-A-59-21.
It is described in No. 4852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. Examples of the silver halide whose inside or surface is fogged include silver chloride, silver chlorobromide,
Both silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is 0.
01 to 0.75 μm, particularly preferably 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited, and may be regular grains or polydisperse emulsion, but monodisperse (at least 95% of the weight or 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 of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the developing treatment, and it is preferable that it is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23 to 24, page 648, right column, page 866 to 868 Color sensitizer ~ page 649 right column 4.whitening agent page 24 647 page right column 868 5.fogging prevention page 24 ~ 25 page 649 right column 868 ~ 870 agent, stabilizer 6.light absorber, 25 ~ Page 26 Page 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7. Stain 25 Page Right column 650 Page Left column 872 Inhibitor ~ Right column 8. Dye image Page 25 650 Page Left column 872 Stabilizer 9. Hardener 26 pages 651 left column 874 to 875 pages 10. Binder page 26 651 pages left column 873 to 874 pages 11. Plasticizer, page 27 650 pages right column 876 lubricants 12. Coating aids , Page 26-27 page 650 right column 875-876 surfactant 13. static page 27 page 650 right column 876-877 inhibitor 14. matting agent page 878-879

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add to the light-sensitive material a compound capable of being immobilized by reacting with formaldehyde described in 4,435,503. In the light-sensitive material of the present invention, U.S. Pat.
No. 4,788,132, JP-A-62-18539, JP-A 1-28355.
It is preferable that the mercapto compound described in No. 1 is contained. A compound which, in the light-sensitive material of the present invention, releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof as described in JP-A 1-106052, irrespective of the amount of developed silver produced by development processing. Is preferably contained. In the light-sensitive material of the present invention, dyes dispersed according to the method described in International Publication WO88 / 04794 and Japanese Patent Publication No. 1-502912 or European Patent No. 317,308A, U.S. Pat. It is preferable to include the dyes described in No. Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 17643, VII-CG, and No. 307105, VII-C.
To the patents listed in G. Examples of yellow couplers include U.S. Pat.Nos. 3,933,501 and 4,023.
2,620, 4,326,024, 4,401,752, 4,248,961
No. 58, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020, 1,4
76,760, U.S. Pat.Nos. 3,973,968, 4,314,023, and
Those described in 4,511,649, 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, 4,351,897, and European Patent 73,636,
U.S. Pat. Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-3
3552, Research Disclosure No. 24230 (1984
June), JP-A-60-43659, 61-72238, 60-357.
No. 30, No. 55-118034, No. 60-185951, U.S. Pat.
0,630, 4,540,654, 4,556,630, international publication WO8
Those described in 8/04795 and the like are particularly preferable. Cyan couplers include phenol-based and naphthol-based couplers, U.S. Pat.Nos. 4,052,212 and 4,146,396,
4,228,233, 4,296,200, 2,369,929, 2,8
01,171, 2,772,162, 2,895,826, 3,772,00
No. 2, No. 3,758,308, No. 4,334,011, No. 4,327,173,
West German Patent Publication No. 3,329,729, European Patent No. 121,365A,
No. 249,453A, U.S. Pat.Nos. 3,446,622 and 4,333,999.
No., No. 4,775,616, No. 4,451,559, No. 4,427,767,
Those described in, for example, 4,690,889, 4,254,212, 4,296,199, and JP-A-61-42658 are preferable. Furthermore, the pyrazoloazole couplers described in JP-A-64-553, 64-554, 64-555 and 64-556, and U.S. Pat.
The imidazole couplers described in No. 672 can also be used. Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,
282, 4,409,320, 4,576,910, British Patent 2,10
2,137, European Patent No. 341,188A and the like.

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,125,5.
70, European Patent 96,570, West German Patent (Publication) 3,234,
Those described in No. 533 are preferable. Colored couplers for correcting unnecessary absorption of color forming dyes are Research Disclosure No. 17643, Item VII-G, and No. 307105, V.
Section II-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413
Nos. 4,004,929, 4,138,258 and British Patent 1,146,368 are preferred. Further, a coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in U.S. Pat.No. 4,774,181, and a dye capable of reacting with a developing agent described in U.S. Pat. It is also preferable to use a coupler having a precursor group as a leaving group. Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention. DI releasing development inhibitor
The R coupler is not limited to the one represented by the general formula (I) of the present invention, but also includes the above-mentioned RD No. 17643, VII-F item and RD No. 307105, V.
Patents described in paragraph II-F, JP-A-57-151944, 57-
154234, 60-184248, 63-37346, 63-37350
Nos. 4,248,962 and 4,782,012 are preferable. The bleaching accelerator releasing couplers described in RD No. 11449, No. 24241, JP-A-61-201247 and the like are
It is effective in shortening the time of the processing step having a bleaching ability, and its effect is particularly large when it is added to the light-sensitive material using the tabular silver halide grains described above. As couplers that release a nucleating agent or a development accelerator imagewise during development, those described in British Patent Nos. 2,097,140 and 2,131,188, and JP-A-59-157638 and 59-170840 are preferable. In addition, JP-A-60-107029, JP-A-60-252340, JP
Compounds which release a fogging agent, a development accelerator, a silver halide solvent and the like by a redox reaction with an oxidized product of a developing agent described in 1-44940 and 1-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,338,3.
93, 4,310,618 and the like, multiequivalent couplers, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds or D
IR redox-releasing redox compounds, EP 173,
Nos. 302A and 313,308A, couplers that release dyes that recolor after separation, ligand-releasing couplers described in U.S. Pat.No. 4,555,477, and couplers that release leuco dyes described in JP-A-63-75747. , A coupler releasing a fluorescent dye described in U.S. Pat. No. 4,774,181.

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

In the color light-sensitive material of the present invention, phenethyl alcohol, 1,2-benzisothiazolin-3-one described in JP-A-63-257747, JP-A-62-272248 and JP-A-1-80941 are used. Add various preservatives or mildewcides such as n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2- (4-thiazolyl) benzimidazole. Is preferred. The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.
Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D. No. 17643, page 28, No. 18716, page 647, right column to page 648, left column, and No. 307105, page 879. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less,
It is more preferably 23 μm or less, further preferably 18 μm or less, particularly preferably 16 μm or less. Also, the film swelling speed T _1/2
Is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and 55% relative humidity (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, A. Green et al. Photographic Science and Engineering (Photogr. Sci.
& Eng.), No. 19, No. 2, pp. 124-129, and can measure by using a swellometer of the type described in
_1/2 is 90% of the maximum swollen film thickness reached when processed with color developer at 30 ° C for 3 minutes and 15 seconds, and the saturated film thickness is 1/2 of the saturated film thickness.
It is defined as the time to reach. Membrane swelling speed T
_1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness. The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is 150-5
00% is preferable.

The color photographic light-sensitive material according to the present invention is described in RD No. 17643, pages 28 to 29, RD No. 18716, 651 left column to right column, and RD No. 307105, pages 880 to 881. Development can be carried out by a conventional method. The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3- Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N- ethyl-
β-methoxyethylaniline, 4-amino-3-methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3
-Methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (2-hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl -N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino
-3-propyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-methyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N -Ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-
Ethyl-N-ethyl-N- (3-hydroxy-2-methylpropyl)
Aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3- Methyl-N- (5
-Hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N-
Examples thereof include (4-hydroxybutyl) aniline, and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4
-Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl)
Aniline and their hydrochlorides, p-toluenesulphonates or sulphates are preferred. Two or more of these compounds can be used in combination depending on the purpose. The color developer is a pH buffer such as alkali metal carbonate, borate or phosphate, chloride salt, bromide salt, iodide salt, benzimidazole, benzothiazole or mercapto compound. It is common to include an inhibitor or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, N, N-
Hydrazines such as biscarboxymethylhydrazine,
Various preservatives such as phenylsemicarbazides, triethanolamine, catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye formation Couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, various chelating agents represented by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids , Can be added. Examples of such chelating agents include ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N. Typical examples thereof include, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

When the reversal process is carried out, the black and white development is usually carried out before the color development. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. Is. As a method of reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit development processing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a color developing agent at a high concentration.

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

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleach accelerators are described in the following publications: U.S. Patent No. 3,893,858, West German Patent No. 1,290,812,
2,059,988, JP-A-53-32736, 53-57831, 5
3-37418, 53-72623, 53-95630, 53-95631
No. 53, 104-232, 53-124424, 53-141623,
53-28426, Research Disclosure No. 17129
Compounds having a mercapto group or a disulfide group described in JP-A No. 1978/1978; the thiazolidine derivatives described in JP-A No. 50-140129; JP-B-45-8506 and JP-A-52-20.
832, 53-32735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent No. 1,127,715, JP-A-58-16.
Iodide salt described in 235; West German Patent Nos. 966,410 and 2,74
Polyoxyethylene compounds described in No. 8,430; Japanese Patent Publication No. 4
Polyamine compounds described in 5-8836; Others JP-A-49-409
No. 43, No. 49-59644, No. 53-94927, No. 54-35727, No.
Compounds described in 55-26506 and 58-163940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, U.S. Patent No. 3,893,858 and West German Patent No. 1,290,8.
Compounds described in JP-A No. 12 and JP-A-53-95630 are preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specifically acetic acid, propionic acid, hydroxyacetic acid and the like are preferable. Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but the use of thiosulfates is common. In particular, ammonium thiosulfate can be used most widely. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent 294,769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the fixing solution or the bleach-fixing solution has a pKa of 6.0 to 9.
It is preferable to add 0.1 to 10 mol / liter of a compound of No. 0, preferably imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methylimidazole.

The total time of the desilvering process is preferably short as long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. In the desilvering process, it is preferable that the stirring is strengthened as much as possible.
As a specific method for strengthening stirring, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461 Method to increase the effect, further moving the photosensitive material while contacting the emulsion surface with the wiper blade provided in the solution, to improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator. The automatic processor used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257.
No. 60-191258 and No. 60-191259. JP-A-60-1
As described in No. 91257, such a transportation means can significantly reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to washing and / or stabilizing steps after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range.
Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and
Television Engineers Volume 64, pp. 248-253 (May 1955)
It can be obtained by the method described in (Month issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, such a problem is solved as a solution.
The method of reducing calcium ion and magnesium ion described in No. 62-288838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" (1986) Sankyo Publishing Co., Ltd., Hygiene Engineering Society, "Microbial sterilization, sterilization, and antifungal technology"
(1982) The sterilizing agent described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal can also be used. In the processing of the light-sensitive material of the present invention, the washing water has a pH of 4 to
9, and preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such a stabilizing process, the method disclosed in
All known methods described in Nos. 57-8543, 58-14834, and 60-220345 can be used. In addition, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. be able to. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution resulting from the washing with water and / or the replenishment of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline compounds described in U.S. Pat. Metal salt complex described in JP-A-53-135628
The urethane-based compounds described in No. 1 can be mentioned. The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. Typical compounds are JP-A-56
-64339, 57-144547 and 58-115438. The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

The silver halide color photographic light-sensitive material of the present invention, when applied to a lens-fitted film unit described in JP-B-2-32615, JP-B-3-39784, etc.,
It is more effective and more effective.

[0084]

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

Example 1 On a subbed cellulose triacetate film support,
A sample 101, which is a multi-layer color light-sensitive material composed of each layer having the composition shown below, was prepared. The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer. The symbols indicating additives have the following meanings. However, when there are multiple utilities, one of them is listed as a representative. UV: UV absorber, Solv: High boiling organic solvent, Ex
F: 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 2.00 UV-1 3.0 × 10 ^-2 UV-2 6.0 × 10 ^-2 UV-3 7.0 × 10 ^-2 ExF-1 1.0 × 10 ^-2 ExF -2 4.0 x 10 ^-2 ExF-3 5.0 x 10 ^-3 ExM-3 0.11 Cpd-5 1.0 x 10 ^-3 Solv-1 0.16 Solv-2 0.10

Second layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A Coating amount 0.35 Silver iodobromide emulsion B Coating silver amount 0.18 Gelatin 0.77 ExS-1 2.4 × 10 ^-4 ExS-2 1.4 × 10 ^-4 ExS-5 2.3 x 10 ^-4 ExS-7 4.1 x 10 ^-6 ExC-1 9.0 x 10 ^-2 ExC-2 5.0 x 10 ^-3 ExC-3 4.0 x 10 ^-2 ExC-5 8.0 x 10 ^-2 ExC-6 2.0 x 10 ^-2 ExC-9 2.5 x 10 ^-2 Cpd-4 2.2 x 10 ^-2

Third Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Coating amount 0.55 Gelatin 1.05 ExS-1 2.4 × 10 ^-4 ExS-2 1.4 × 10 ^-4 ExS-5 2.4 × 10 ^-4 ExS-7 4.3 × 10 ^-6 ExC-1 0.19 ExC-2 1.0 × 10 ^-2 ExC-3 1.0 × 10 ^-2 ExC-4 1.6 × 10 ^-2 ExC-5 0.19 ExC-6 2.0 × 10 ^-2 ExC- 7 2.5 x 10 ^-2 ExC-9 3.0 x 10 ^-2 Cpd-4 1.5 x 10 ^-3

The fourth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Coating amount 1.05 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 x 10 ^-5 ExC-1 2.0 x 10 ^-2 ExC-3 2.0 x 10 ^-2 ExC-4 9.0 x 10 ^-2 ExC-5 5.0 x 10 ^-2 ExC-8 1.0 x10 ^-2 ExC- 9 1.0 x 10 ^-2 Cpd-4 1.0 x 10 ^-3 Solv-1 0.70 Solv-2 0.15

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 E Coated silver amount 0.10 Silver iodobromide emulsion F Coated silver amount 0.28 Gelatin 0.31 ExS-3 1.0 × 10 ^-4 ExS-4 3.1 × 10 ^-4 ExS-5 6.4 x 10 ^-5 ExM-1 0.12 ExM-7 2.1 x 10 ^-2 Solv-1 0.09 Solv-3 7.0 x 10 ^-3

Seventh Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion G Coating amount 0.37 Gelatin 0.54 ExS-3 2.7 × 10 ^-4 ExS-4 8.2 × 10 ^-4 ExS-5 1.7 × 10 ^-4 ExM-1 0.27 ExM-7 7.2 x 10 ^-2 ExY-1 5.4 x 10 ^-2 Solv-1 0.23 Solv-3 1.8 x 10 ^-2

Eighth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion H Coating amount 0.53 Gelatin 0.61 ExS-4 4.3 × 10 ^-4 ExS-5 8.6 × 10 ^-5 ExS-8 2.8 × 10 ^-5 ExM-2 5.5 x 10 ^-3 ExM-3 1.0 x 10 ^-2 ExM-5 1.0 x 10 ^-2 ExM-6 3.0 x 10 ^-2 ExY-1 1.0 x 10 ^-2 ExC-1 4.0 x10 ^-3 ExC- 4 2.5 × 10 ^-3 Cpd-6 1.0 × 10 ^-2 Solv-1 0.12

Ninth layer (intermediate layer) Gelatin 0.50 UV-4 4.0 × 10 ^-2 UV-5 3.0 × 10 ^-2 Cpd-1 4.0 × 10 ^-2 Polyethyl acrylate latex 5.0 × 10 ^-2 Solv-1 3.0 × 10 ^-2

The tenth layer (donor layer having a multilayer effect on the red-sensitive layer) Silver iodobromide Emulsion I coating amount 0.40 Silver iodobromide emulsion J coating amount 0.20 Silver iodobromide emulsion K coating silver amount 0.39 Gelatin 0.87 ExS ^{-3 6.7 × 10 -4 ExM-2} 0.16 ExM-4 3.0 × 10 -3 ExM-5 5.0 × 10 -2 ExM-6 4.0 × 10 -2 ExY-2 2.5 × 10 -3 ExY-5 2.0 × 10 - ² Comparative compound A 2.5 × 10 ^-2 Solv-1 0.30 Solv-5 3.0 × 10 ^-2

Eleventh layer (yellow filter layer) Yellow colloidal silver 9.0 × 10 ^-2 gelatin 0.60 Cpd-1 5.0 × 10 ^-2 Cpd-2 5.0 × 10 ^-2 Cpd-5 2.0 × 10 ^-3 Solv-1 0.13 H -1 0.25

12th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Coating amount 0.50 Silver iodobromide emulsion M Coating silver amount 0.40 Gelatin 1.50 ExS-6 9.0 × 10 ^-4 ExY-1 8.5 × 10 ^-2 ExY-2 5.5 x 10 ^-3 ExY-3 6.0 x 10 ^-2 ExY-5 1.00 ExC-1 5.0 x 10 ^-2 ExC-2 8.0 x 10 ^-2 Solv-1 0.54

13th layer (intermediate layer) Gelatin 0.30 ExY-4 0.14 Solv-1 0.14

14th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion N Coating amount of silver 0.40 Gelatin 0.95 ExS-6 2.6 × 10 ^-4 ExY-2 1.0 × 10 ^-2 ExY-3 2.0 × 10 ^-2 ExY-5 0.18 ExC-1 1.0 × 10 ^-2 Solv-1 9.0 × 10 ^-2

Fifteenth layer (first protective layer) Fine grain silver iodobromide emulsion O Coating amount 0.12 Gelatin 0.63 UV-4 0.11 UV-5 0.18 Cpd-3 0.10 Solv-4 2.0 × 10 ^-2 Polyethyl acrylate latex 9.0 × 10 ^-2

Sixteenth layer (second protective layer) Fine grain silver iodobromide emulsion O Coating amount of silver 0.36 Gelatin 0.50 B-1 (diameter 2.0 μm) 8.0 × 10 ⁻² B-2 (diameter 2.0 μm) 8.0 × 10 ^{− 2} B-3 2.0 x 10 ^-2 W-5 2.0 x 10 ^-2 H-1 0.18

In addition to the above, the samples thus prepared include
1,2-benzisothiazolin-3-one (average 200 ppm relative to gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm) and 2-phenoxyethanol (about 10,000 ppm) were added. Furthermore, in order to improve the storage stability, processability, pressure resistance, antifungal / bacteriostatic property, antistatic property and coating property of each layer, W-1 to W-6,
B-1 to B-6, F-1 to F-16 and iron salts, lead salts,
It contains gold salt, platinum salt, iridium salt, and rhodium salt.

[0103]

[Table 1]

In Table-A, (1) Emulsions A to N were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) Emulsions A to N were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. It has been subjected. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope. (5) Emulsions A to N are BH Carroll, Photographic Scien
Ce and Engineering, 24, 265 (1980) and the like contain iridium inside the particles.

[0105]

[Chemical formula 26]

[0106]

[Chemical 27]

[0107]

[Chemical 28]

[0108]

[Chemical 29]

[0109]

[Chemical 30]

[0110]

[Chemical 31]

[0111]

[Chemical 32]

[0112]

[Chemical 33]

[0113]

[Chemical 34]

[0114]

[Chemical 35]

[0115]

[Chemical 36]

[0116]

[Chemical 37]

[0117]

[Chemical 38]

[0118]

[Chemical Formula 39]

[0119]

[Chemical 40]

[0120]

[Chemical 41]

[0121]

[Chemical 42]

(Samples 102 to 111) First of Sample 101
Samples 102 to 111 were prepared by replacing the comparative compound A added to the layer 0 with other comparative compounds or compounds of the present invention in equimolar amounts as shown in Table-B.

After these samples were uniformly exposed in red so that the cyan density was approximately 1.0, the maximum transmittance was 52%.
Imagewise exposure was performed through a 0 nm interference filter, color development processing described below was performed, and density was measured. The value obtained by subtracting the cyan density in the magenta fog density from the cyan density at the point where the magenta density was 1.5 was defined as the layering effect on the red sensitive layer. Also, white exposure is performed through the MTF measurement pattern,
After development, the MTF value of the cyan image in 25 cycles was measured. Further, each sample was exposed to two white images, and 1
Book at 7 ℃, 55% RH for 1 week, the other one at 50 ℃,
After storage in a dark room at 80% RH for 1 week, development was carried out, and fluctuation of reciprocal of exposure amount giving density of magenta density (fog + 0.2) was determined as relative sensitivity change under forced deterioration condition.

[0124]

[Chemical 43]

[0125]

[Chemical 44]

The color development processing was performed under the following conditions using an automatic developing machine. The treatment process and the treatment liquid composition are shown below.

(Processing process) Process processing time Treatment temperature Replenishment amount ^* Tank capacity Color development 3 minutes 5 seconds 38.0 ℃ 23 ml 17 liter Bleach 50 seconds 38.0 ℃ 5 ml 5 liter Bleach fixing 50 seconds 38.0 ℃ -5 liter fixed 50 seconds 38.0 ℃ 16 ml 5 liters Water wash 30 seconds 38.0 ℃ 34 ml 3 liters Stability (1) 20 seconds 38.0 ℃ ― 3 liters Stability (2) 20 seconds 38.0 ℃ 20 milliliters 3 liters Dry 1 minute 60 ℃ * Replenishment amount per 35 m width of photosensitive material 1.1 m (equivalent to 24 Ex. 1)

The stabilizing solution was a countercurrent system from (2) to (1), and the overflow solution of washing water was all introduced into the fixing bath. When replenishing the bleach-fixing bath, a cutout is provided on the bleaching tank of the automatic processor and on the top of the fixing tank so that all of the overflow solution generated by supplying the replenishing solution to the bleaching tank and the fixing tank is added to the bleach-fixing bath. I was allowed to flow in. The amount of developing solution brought into the bleaching step, the amount of bleaching solution brought into the bleach-fixing step, the amount of bleach-fixing solution brought into the fixing step, and the amount of fixing solution brought into the washing step were as follows. 2.5 ml, 2.0 ml per 1 m,
It was 2.0 ml and 2.0 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. Further, each replenisher was replenished with the same liquid as the respective tank liquids.

The composition of the processing liquid is shown below.

[0130]

(Bleaching Fixing Solution) A 15:85 (volume ratio) mixture of the above bleaching solution and the following fixing solution. (PH 7.0)

[0132]

(Rinsing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
/ Liter or less, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 150
mg / l was added. The pH of this liquid is 6.5 to 7.
It was in the range of 5.

[0134]

[0135]

[Table 2]

From Table B, it can be seen that the sample containing the compound of the present invention has a large layering effect on the red photosensitive layer, is excellent in the sharpness represented by the MTF value, and has little change in photographic performance during storage. it is obvious.

Example 2 Seventh layer and eighth layer of sample 110 of JP-A-4-340544
The compounds (2), (3) and (6) of the present invention were added to the layer and the ninth layer in an amount of 0.010 g / m ² and evaluated according to Example 1 of the present invention. It was recognized that the sample to which these compounds were added had a significantly larger layering effect and excellent sharpness, as compared with the sample 110 of the patent in which the compound was not added. Here, for imagewise exposure for evaluation of the interlayer effect, the 520 nm interference filter was changed to a 550 nm interference filter.

[0138]

According to the present invention, the sharpness, graininess, color reproducibility and storage stability of a silver halide color photographic light-sensitive material can be improved.

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[Procedure amendment]

[Submission date] March 31, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

[0046]

[Chemical 19]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0111

[Correction method] Change

[Correction content]

[0111]

[Chemical 32]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (31) Priority claim number Japanese Patent Application No. 4-253473 (32) Priority date Hei 4 (1992) August 31 (33) Country of priority claim Japan (JP) (31) Priority Claim number Japanese patent application No. 4-258909 (32) Priority date Hei 4 (1992) September 3, (33) Priority claiming country Japan (JP) (72) Inventor Keiji Mibayashi 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Within Film Co., Ltd.

Claims (1)

[Claims] 1. A compound represented by the following general formula (I) which reacts with an oxidized product of a developing agent to release a photographically useful group or its precursor group and does not substantially form a color image. A silver halide color photographic light-sensitive material characterized by: General formula (I) (In the formula, R ₁ represents a group that allows a compound formed by the reaction of the compound represented by the general formula (I) and an oxidized product of a developing agent to flow out into the processing solution, and R ₂ represents a hydrogen atom. Or represents a substituent, n1 represents 0 to 4, and n1 represents 2
In the above case, two or more R ₂ may be the same or different. X ₁ represents an oxygen atom or a sulfur atom, W ₁ represents a carbon atom or a sulfur atom, and X ₂ represents an oxygen atom, a sulfur atom or = NR ₄ . N when W ₁ is a carbon atom
2 is 1 and n2 is 1 or 2 when W ₁ is a sulfur atom. R ₃ represents an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfonyl group or a sulfamoyl group, and R ₄ represents a hydrogen atom, an alkyl group, an aryl group, a heterocycle. Represents a group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfonyl group or a sulfamoyl group. X
₃ and X ₄ each represent a hydrogen atom or a substituent,
TIME represents a timing group, n3 represents 0 or 1, and PUG represents a photographically useful group. R ₃ , X ₃ and /
Alternatively, at least one of X ₄ represents a diffusion resistant group. )