JP3112211B2 - Silver halide color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material.
The present invention relates to a silver halide color photographic 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, granularity or color reproducibility. See "The Theory of Photographic Pr" edited by THJames for the photographic effects of DIR couplers.
ocess ", 4th ed., pp610-611 and p344 (1977, MACMILLANP
UBLISHING Co., New York). Now, the DIR coupler is roughly classified into a type that releases a development inhibitor or a precursor thereof by a coupling reaction with an oxidized developing agent at the time of development and simultaneously forms a dye, and a coupling reaction between the DIR coupler and an oxidized developing agent. A compound which releases a development inhibitor or a precursor thereof, but generates a compound which does not substantially contribute to the formation of a color image is known. Since a normal silver halide color photographic light-sensitive material is composed of a light-sensitive layer that 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 a dye that forms a dye 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 of D
Since the IR coupler does not substantially participate in the formation of a color image, it can be used for a photosensitive layer which develops any color without causing color turbidity. US Pat. No. 4,482,629 discloses 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 developing agent but does not substantially participate in the formation of a color image. And JP-A-63-37350, U.S. Pat. No. 5,026,628, and European Patent Nos. 0443530 and 0514869 are known. However, the compounds known hitherto are required for the performance requirements of this type of DIR coupler, that is, they do not cause color turbidity, that they can obtain a sufficient effect of improving color reproducibility and sharpness, and It cannot be said that all of the stability in the photosensitive material during storage is satisfied, and further improvement is required.

[0003]

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

[0004]

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

[0005]

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(Wherein R ₁ represents a group capable of allowing a compound formed by the reaction between the compound represented by the general formula (I) and an oxidized form of the developing agent to flow out into a processing solution;
R ₂ represents a hydrogen atom or a substituent, n1 represents 0 to 4, two or more R ₂ when n1 is 2 or more 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 ＮＲNR ₄ . W ₁ is n2 is 1 when the carbon atom, when W ₁ is a sulfur atom n
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, and R ₄ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group,
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 non-diffusible group. )

The compound represented by the general formula (I) can efficiently release PUG in the early stage of development because the coupling reaction with the oxidized developing agent is fast. General formula (I)
Is highly stable to heat. In these respects, the compounds represented by the general formula (I) are 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,
A fluorine atom, a chlorine atom), an aliphatic group (linear, branched or cyclic alkyl group, alkenyl group, or alkynyl group having 10 or less carbon atoms, for example, methyl, ethyl, isopropyl,
1-butyl, t-butyl, 2-methanesulfonylethyl, trifluoromethyl, 3-phenyl-1-propyl, 2-phenyl-1-butyl, benzyl, cyclopentyl), an aryl group (an 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 (group having 6 or less carbon atoms, for example, methoxy, ethoxy, 1-butoxy), aryloxy group (10 carbon atoms) In the following groups, for example, phenoxy, 4-methoxyphenoxy, 4-nitrophenoxy, 3-butanesulfonamidophenoxy, 2-naphthoxy), a heterocyclic oxy group (for example, a group having 6 or less carbon atoms, for example, 2-furyloxy), Acyloxy group (a group having 10 or less carbon atoms such as acetoxy,
Pivaloyloxy, benzoyloxy), alkoxycarbonyloxy group (having 6 or less carbon atoms, for example, ethoxycarbonyloxy, t-butoxycarbonyloxy), aryloxycarbonyloxy group (having 10 carbon atoms)
In the following groups, for example, phenoxycarbonyloxy), carbamoyloxy group (in the group having 10 or less carbon atoms, for example,
N, N-dimethylcarbamoyloxy, N-butylcarbamoyloxy), a 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 (E.g., acetyl, pivaloyl, benzoyl in groups having 10 or less carbon atoms), alkoxycarbonyl groups (6 carbon atoms)
The following groups are, for example, ethoxycarbonyl), an aryloxycarbonyl group (a group having 10 or less carbon atoms, for example, phenoxycarbonyl), a carbamoyl group (a group having 10 carbon atoms or less is, for example, N, N-dimethylcarbamoyl, N-propyl) Carbamoyl), an amino group (for example, a group having 6 or less carbon atoms such as amino, N-methylamino, N, N-dimethylamino), an anilino group (for example, a group having 10 or less carbon atoms,
N-methylanilino), a heterocyclic amino group (a group having 6 or less carbon atoms, for example, 4-pyridylamino), an amide group (a group having 10 carbon atoms or less, for example, acetamido, benzamide, trifluoroacetamide), alkoxycarbonylamino group (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 such as methanesulfonamide), and a sulfamoylamino group (a group having 10 or less carbon atoms such as N, N-dimethylsulfamoylamino), an alkylthio group (having 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 and p-toluenesulfonyl), and a sulfamoyl group (a group having 10 or less carbon atoms) For example, N, N-dimethylsulfamoyl, N
-Ethylsulfamoyl) and a sulfo group. 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 capable of allowing a compound formed by a coupling reaction between the compound represented by the general formula (I) and an oxidized developing agent to flow out into a processing solution. _{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]

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R ₁₁ is a hydroxyl group, an alkoxy group (alkoxy group having 6 or less carbon atoms such as methoxy, ethoxy, 1-butoxy), an aryloxy 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, a heterocyclic oxy group having 6 or less carbon atoms,
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 (C 1
To 6 linear, branched or cyclic alkyl groups such as methyl, ethyl, isopropyl, 1-butyl, t-butyl, 2-methanesulfonylethyl, trifluoromethyl and cyclopentyl), and aryl groups (having 10 or less carbon atoms) Aryl groups 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]

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

In the group represented by the general formula (III),
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 , and 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 preferred substituents are those described as the group represented by R ₂ . R ₂₆ represents an alkyl group having 3 or less carbon atoms (eg, methyl, ethyl, propyl, trifluoromethyl, trichloromethyl, trifluoroethyl), and n6 and n7 each represent 1, 2 or 3. Of these, R ₂₁ , R ₂₂ , R
₂₃ , R ₂₄ and R ₂₅ are each a hydrogen atom or a carbon atom 3
The following alkyl groups are preferred, and a hydrogen atom or a methyl group is most preferred. 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 is 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, for example, methyl,
Ethyl), an aryl group (an aryl group having 10 or less carbon atoms such as phenyl and p-tolyl), a hydroxyl group, an alkoxy group (an alkoxy group having 6 or less carbon atoms such as methoxy, ethoxy, 1-butoxy), and aryloxy Groups (aryloxy groups having 10 or less carbon atoms, such as phenoxy, 4-methoxyphenoxy, 4-nitrophenoxy,
3-butanesulfonamidophenoxy, 2-naphthoxy), heterocyclic oxy group (heterocyclic oxy group having 6 or less carbon atoms such as 2-furyloxy), amino group (amino group having 6 or less carbon atoms such as amino, N-methylamino, N, N-dimethylamino), anilino group (1 carbon atom)
0 or less anilino group, for example, N-methylanilino),
Heterocyclic amino group (heterocyclic amino group having 6 or less carbon atoms such as 4-pyridylamino), alkylthio group (for example, alkylthio group having 6 or less carbon atoms such as ethylthio) or arylthio group (for example, 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 represents 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
-Phenylene groups, these phenylene groups are -N
It may have a substituent other than (R ₃₁ )-and -A _1- , and preferred substituents are the same as those described 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 (E.g., methylthio) and an alkoxycarbonyl group (e.g., methoxycarbonyl) may have a substituent, and n5 represents an integer of 1 to 3. Preferred as R ₃₂ include a methylene group, an ethylene group, a 1,2-phenylene group, a 1,3-phenylene group and 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 ＮＲNR 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] dodecaneamide {phenyl} propyl, 2-ethoxytridecyl, 3- (2,4-di-t-amylphenoxy) propyl, 3-dodecyloxypropyl, allyl), aryl group ( Aryl groups having 6 to 32 carbon atoms such as phenyl, p-tolyl, 4-t-butylphenyl, 2,4
-Di-t-amylphenyl, 4-nitrophenyl, 4-
Ethoxyphenyl, 1-naphthyl), a heterocyclic group (for example, a group having 1 to 32 carbon atoms such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl),
An acyl group (a group having 1 to 32 carbon atoms such as acetyl, pivaloyl, benzoyl, tetradecanoyl, octadecanoyl), an alkoxycarbonyl group (a group having 1 to 32 carbon atoms such as ethoxycarbonyl and dodecyloxycarbonyl), Aryloxycarbonyl group (for example, phenoxycarbonyl, 4-t-octylphenoxycarbonyl), carbamoyl group (for example, a group having 1 to 32 carbon atoms such as N, N-dibutylcarbamoyl, N-ethyl-N-
Octylcarbamoyl, N-dodecylcarbamoyl),
A sulfonyl group (having 1 to 32 carbon atoms such as hexadecanesulfonyl, octanesulfonyl, p-toluenesulfonyl, 2-octyloxy-5-t-octylbenzenesulfonyl), and a sulfamoyl group (having 1 to 32 carbon atoms)
For example, 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 are the same as those described for 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 , Acyl group, alkoxycarbonyl group,
An aryloxycarbonyl group, a carbamoyl group, a sulfonyl group or a sulfamoyl group, 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. Preferably, R ₃ is 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 the general formula (I) includes a development inhibitor, a dye, a fogging agent, a developing agent, a coupler, a bleaching accelerator, a development accelerator, a fixing accelerator and the like. It is. Examples of preferable photographically useful groups include certain photographically useful groups described in U.S. Pat. No. 4,248,962 (in the patent, those represented by the general formula PUG) and those described in JP-A-62-49353. Dyes (the 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 the like (the part of the leaving group released from the coupler in the specification). In the present invention, particularly preferred as a photographically useful group is a development inhibitor.

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

[0022]

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[0023]

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[0024]

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

Preferred substituents include an alkoxycarbonyl group (for example, ethoxycarbonyl, 1,4-dioxo-2,5-dioxadecyl, 1,4-dioxo-
2,5-dioxa-8-methylnonyl), an aryloxycarbonyl group (eg, phenoxycarbonyl), an alkylthio group (eg, methylthio, propylthio, hexylthio), an alkoxy group (eg, methoxy, propyloxy), a sulfonyl group (eg, Methanesulfonyl), carbamoyl group (eg, ethylcarbamoyl), sulfamoyl group (eg, ethylsulfamoyl), cyano group, nitro group, amide group (eg, acetamido), 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 (for example, phenyl, naphthyl, 4-methoxy) Carbonylphenyl,
3-methoxycarbonylphenyl, 4- (2-cyanoethyloxycarbonyl) phenyl), a heterocyclic group (e.g., 4-pyridyl, 3-pyridyl, 2-pyridyl, 2-
Furyl, 2-tetrahydropyranyl) and the like.

Among them, 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
Or a substituted or unsubstituted phenyl group.

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

Next, the group represented by TIME will be described. The group represented by TIME is converted to a group represented by P
Any linking group that can cleave the bond with UG may be used. For example, U.S. Pat. No. 4,146,396
No. 4,652,516 or 4,698,29
7, a group utilizing a hemiacetal cleavage reaction, described in U.S. Pat. Nos. 4,248,962 and 4,847,
No. 4,409,323 or U.S. Pat. No. 4,421,845. A timing group for causing a cleavage reaction using an intramolecular nucleophilic substitution reaction described in US Pat. A timing group for causing a cleavage reaction using an electron transfer reaction as described, a group for causing a cleavage reaction using a hydrolysis reaction of imino ketal described in US Pat. No. 4,546,073, or published in West Germany Japanese Patent No. 2,626,317 discloses a group that causes a cleavage reaction by utilizing an ester hydrolysis reaction. TIME is the heteroatom contained therein,
Preferably an oxygen atom, in a sulfur atom or a nitrogen _{atom, -C (X 3) X 4} - binds to. Preferred TIMEs include the following general formulas (T-1), (T-2) or (T-
3).

General formula (T-1) * -W _3- (Y ₁ =
Y ₂ ) _j -C (R ₅₁ ) R ₅₂ -** General formula (T-2) * -W ₃ -CO-** General formula (T-3) * -W ₃ -LINK-E-**

In the formula, * represents -C in the general formula (I).
(X ₃ ) represents a position bonding to X ₄ —, ** represents a position bonding to PUG, W ₃ represents an oxygen atom, a sulfur atom or —N (R ₅₃ ) —, and Y ₁ and Y ₂ represent Each represents a methine or 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, any two of the substituents, 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 performed or not formed. In formula (T-3) E represents an electrophilic group, LINK represents a sterically relations characterize linking group so that it can be the W ₃ and E intramolecular nucleophilic substitution reaction. The following are specific examples of the TIME represented by the general formula (T-1).

[0032]

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The following are specific examples of the TIME represented by the general formula (T-2).

[0034]

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The following are specific examples of the TIME represented by the general formula (T-3).

[0036]

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The specific examples of the compounds of the present invention are shown below.
The present invention is not limited by these.

[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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

[0053]

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Synthesis Example 1 [Synthesis of Exemplified Compound (1)] (Synthesis of Intermediate B) 280 g (1.00 mol) of Intermediate A was converted to N, N-dimethylacetamide (DMAC) 300
It was added to a mixed solvent of 700 ml of acetonitrile and stirred at room temperature under a nitrogen atmosphere. Β-alanine 9
8.0 g (1.10 mol) and sodium hydroxide 4
A solution of 7.3 g (1.10 mol) dissolved in 200 ml of water was added, and the mixture was heated and refluxed 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 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 and refluxed for 1 hour on a steam bath. After cooling under stirring, the crystals were collected by filtration, and the crystals were washed with acetonitrile. Drying yielded 190.2 g (69%) of intermediate B.

(Synthesis of Intermediate D) Intermediate B 95.0 g
(0.345 mol) in 500 ml of acetonitrile,
The mixture was cooled with ice water under a nitrogen atmosphere. To this, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU)
206 ml (1.38 mol) were added and stirred for 30 minutes.
To this was added 142 g (0.345 mol) of intermediate C,
The mixture was stirred for 1 hour while cooling, and further for 1 hour at room temperature. 1.0 liter of ethyl acetate and 1 portion of concentrated hydrochloric acid were added to the reaction mixture.
1.5 liters of water containing 20 ml was added for extraction. The organic layer was washed with 1 liter of water, then with 1 liter of saturated saline, and dried over anhydrous magnesium sulfate. After concentration, n-
Crystallized 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 obtain 150.6 g (74%) of Intermediate D
I got Melting point 164 to 166 ° C 1H NMR [CDCl ₃ , δ ppm] 13.8 (br, 1H), 8.42 (dd, 1H),
8.9-7.5 (m, 4H), 7.18 (d, 1H),
7.07 (dd, 1H), 6.75 (d, 1H),
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
0.0g (50.6 mmol), 1.52 g (50.6 mmol) of paraformaldehyde and intermediate E14.
7 g (50.6 mmol) are added to 200 ml of toluene,
Stirred 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. The reaction mixture was mixed with 500 ml of ethyl acetate and 1N
The mixture was extracted by adding 500 ml of hydrochloric acid.
The mixture was washed successively with 400 ml of water, 400 ml of water and 400 ml of saturated saline, and dried over anhydrous magnesium sulfate. After concentration, the mixture was purified by silica gel column chromatography (eluent: a mixed solvent of n-hexane and ethyl acetate containing 0.1% acetic acid), and further purified by a mixed solvent of n-hexane and ethyl acetate (4.
/ 1). The precipitated crystals were collected by filtration, washed with a mixed solvent of n-hexane and ethyl acetate, and 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 were added to 80 ml of DMAC, and 22.4 ml of DBU were added. 0.150 mol), and the mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere. to this,
14.0 g (50.0 mmol) of the intermediate A was added, and the mixture was heated and stirred on a steam bath for 2 hours. After cooling, the reaction mixture was mixed with 350 ml of ethyl acetate, 400 ml of water and 13 ml of concentrated hydrochloric acid.
ml was added for extraction. The organic layer was washed with 300 ml of water and subsequently with 300 ml of saturated saline, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure to obtain a crude intermediate F. This was used as a raw material in the next step without purification.

(Synthesis of Intermediate G) The crude product of Intermediate F obtained above was added to 80 ml of DMAC, and the mixture was added under a nitrogen atmosphere.
The mixture was cooled with ice water and stirred. To this, DBU15.0ml
(0.100 mol) was added and stirred for 15 minutes. To this was added 20.6 g (50.0 mmol) of intermediate C,
The mixture was stirred for 10 minutes while cooling, and further for 2 hours at room temperature.
300 ml of ethyl acetate and 13 ml of concentrated hydrochloric acid were added to the reaction mixture.
The mixture was extracted by adding 450 ml of water containing. Organic layer with water 300
Then, the mixture was washed with 300 ml of saturated saline, and dried over anhydrous magnesium sulfate. After concentration, the residue was purified by silica gel column chromatography (eluent: mixed solvent of n-hexane and ethyl acetate), and then crystallized from a mixed solvent of n-hexane and ethyl acetate (4/1). The precipitated crystals are collected by filtration,
The precipitate was washed with a mixed solvent of n-hexane and ethyl acetate, and dried to obtain 11.2 g (36% based on the intermediate A) of the 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), 0.55 g (18 mmol) of paraformaldehyde and intermediate E5.24
g (18.0 mmol) was added to 60 ml of toluene.
Stirred at ° C. 2.01 g of copper (II) bromide (9.
00 mmol) and stirred at that temperature for 5 hours. The reaction mixture was mixed with 150 ml of ethyl acetate and 2N hydrochloric acid.
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, purification 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 the exemplary compound (37) was obtained as a pale green yellow solid.

The compound represented by the formula (I) of the present invention can be used in any layer in a light-sensitive material. That is, a photosensitive 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) Any of a filter layer, an intermediate layer, and an antihalation layer can be used. When the same color-sensitive layer is divided into two or more layers having different sensitivities, it may be added to any one of the highest sensitivity layer, the lowest sensitivity layer and the intermediate sensitivity layer. It can also be added. It is preferably used for 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 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 a light-sensitive material, any known dispersion method can be used depending on the compound. For example, when the compound is alkali-soluble, it may be added as an aqueous alkaline solution or as a solution dissolved in an organic solvent miscible with water, or may be added using an oil-in-water dispersion method using a high-boiling organic solvent, a solid dispersion method, or the like. Can be.

The compounds represented by the formula (I) may be used alone or in combination of two or more. Further, 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 or precursor-releasing compounds of the development inhibitor, or can be used in combination with couplers and other additives described later. These are appropriately selected according to the performance required for the photosensitive material.

The compound represented by the formula (I) of the present invention is
A coupling reaction with an oxidized form of the developing agent releases a development inhibitor, and the mother nucleus forms a dye. The dye thus formed is described in, for example, The Photographic Society of Japan, Vol. 52 (1989).
Year 2 No. 150-155 (Kida et al) or 198
Abstracts of 9th Annual Meeting of the Photographic Society of Japan 2A0-22 (Kida)
During the color development processing, the colorant is discharged into the processing solution or the dye is bleached and decolored. Therefore, the formed dye does not remain on the photosensitive material as a dye after color development processing. Therefore, the compounds represented by the formula (I) of the present invention can be used in any layer constituting the light-sensitive material, for example, regardless of the red-sensitive emulsion layer, the green-sensitive emulsion layer and the blue-sensitive emulsion layer. Has the advantage that the compound can be used depending on Further, since the formed dye does not remain as a dye, it has an advantageous effect on color reproducibility.
In some cases, color image fastness is improved.

The light-sensitive material of the present invention may be provided with at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive silver halide emulsion layer on a support. There is no particular limitation on the number and order of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. Wherein the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to any of red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit light-sensitive layers is generally such that the red-sensitive layer, green The color-sensitive layer and the blue color-sensitive layer are provided in this order.
However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. Non-light-sensitive layers such as various intermediate layers may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. In the intermediate layer, JP-A-61-43748, JP-A-59-1
No. 13438, No. 59-113440, No. 61-20037, couplers such as those described in No. 61-20038, DIR compounds and the like may be contained, and a color mixing inhibitor is used as usually used. You may go out. The plurality of silver halide emulsion layers constituting each unit photosensitive layer preferably employ a two-layer structure of a high-speed emulsion layer and a low-speed emulsion layer as described in German Patent No. 1,121,470 or British Patent No. 923,045. be able to. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. In addition,
57-112751, 62-200350, 62-206541, 62-20
As described in No. 6543, a low-speed emulsion layer may be provided on the side farther from the support, and a high-speed emulsion layer may be provided on the side closer to the support. As specific examples, from the side farthest from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL
/ RL / RH and so on. In addition, Tokuno Sho 55
As described in JP-A-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, the layers can be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. Also, as described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the less sensitive silver halide emulsion layer, and the lower layer is more sensitive than the middle layer. A silver halide emulsion layer having a low degree is arranged,
There is an array composed of three layers having different sensitivities in which the sensitivities are sequentially decreased toward the support. Even in the case where the light emitting device is composed of three layers having different sensitivities, Japanese Patent Application Laid-Open No.
As described in Japanese Patent Application Laid-Open No. 02464, a medium-speed emulsion layer / a high-speed emulsion layer / a low-speed emulsion layer may be arranged in the same color-sensitive layer from the side remote from the support. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. The arrangement may be changed as described above even in the case of four or more layers. In order to improve color reproducibility, U.S. Pat. Nos. 4,663,271, 4,705,744,
No. 707,436, JP-A-62-160448 and JP-A-63-89850, a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of a main photosensitive layer such as BL, GL, RL is used as a main photosensitive layer. It is preferable to dispose it adjacent to or close to. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

Preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or 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 include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystalline forms such as spheres and plates, twin planes, etc. Or a composite form thereof. The grain size of silver halide is about 0,0.
Fine particles having a diameter of 2 μm or less or large particles having a projected area diameter of about 10 μm may be used, and a polydispersed emulsion or a monodispersed emulsion may be used. The silver halide photographic emulsion usable 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, No. 307105 (November 1989), 863-865
Page and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chimie et Physique Photo
graphique, Paul Montel, 1967), Photographic Emulsion Chemistry by Duffin, Focal Press (GF Duffin, Phot)
ographic Emulsion Chemistry (Focal Press, 1966)),
"Manufacture and Coating of Photographic Emulsion", by Zelikman et al., Published by Focal Press (VL Zelikman et al., Making and Coat
ing Photographic Emulsion, Focal Press, 1964).

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

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are described in Research Disclosure Nos. 17643, 18716 and 307105, and the relevant portions are summarized in the table below. The light-sensitive material of the present invention comprises two or more types of emulsions having at least one characteristic different from each other in the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion.
They can be mixed and used in the same layer. U.S. Patent No.
No. 4,082,553, silver halide grains having a fogged surface described in U.S. Pat. It can be preferably used for a silver emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer.
The term "silver halide particles having a fogged inside or surface thereof" means silver halide grains which can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. . The method for preparing silver halide grains having the inside or the surface of the grains fogged is described in U.S. Pat.
No. 4852. The silver halides forming the internal nuclei of the core / shell type silver halide grains having the inside of the grains fogged may have the same halogen composition or different halogen compositions. Silver chloride, silver chlorbromide,
Both silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but the average grain size is 0.
It is preferably from 01 to 0.75 μm, particularly preferably from 0.05 to 0.6 μm. Also,
The grain shape is not particularly limited, and may be regular grains or polydisperse emulsions. Having a particle size of 1).

In the present invention, it is preferable to use non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide. Fine grain silver halide, average grain size (average value of projected area equivalent circle diameter)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be chemically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing fine silver halide grains. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23-24, page 648, right column, page 866-868 Strong Color sensitizer 〜Page 649 right column 4. Brightener 24 page 647 page right column 868 5. Fogging prevention page 24-25 page 649 right column 868-870 agent, stabilizer 6.Light absorber, 25- Page 26 649 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 25 Page 650 Page Left column 872 Stabilizer 9. Hardener page 26 page 651 left column 874-875 10. Binder page 26 page 651 left column 873-874 11. Plasticizer, page 27 page 650 right column page 876 Lubricant 12. Coating aid Pp. 26-27 650 right column 875-876 Surfactant 13. Static 27 page 650 right column 876-877 Inhibitor 14. Matsuto 878-879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,987 and US Pat.
It is preferable to add a compound capable of being fixed by reacting with formaldehyde described in 4,435,503 to the photosensitive material. U.S. Pat.No. 4,740,454
No. 4,788,132, JP-A-62-18539, JP-A 1-28355
It is preferable to contain the mercapto compound described in Item 1. In the light-sensitive material of the present invention, compounds described in JP-A-1-06052, which release a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof irrespective of the amount of developed silver produced by development processing Is preferably contained. In the light-sensitive material of the present invention, WO88 / 04794, dyes dispersed by the method described in JP-A-1-502912 or European Patent No. 317,308A, U.S. Pat. It is preferable to include the dye described in (1). Various color couplers can be used in the present invention.
-G are described in the patents. As a yellow coupler, for example, U.S. Patent Nos. 3,933,501 and 4,02
No. 2,620, No. 4,326,024, No. 4,401,752, No. 4,248,961
No., JP-B-58-10739, UK Patent No. 1,425,020, 1,4
No. 76,760; U.S. Pat.Nos. 3,973,968; 4,314,023;
Nos. 4,511,649 and EP 249,473A are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
U.S. Pat. Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-3
No. 3552, Research Disclosure No. 24230 (1984
June), JP-A-60-43659, JP-A-61-72238, JP-A-60-357
No. 30, No. 55-118034, No. 60-185951, U.S. Pat.
Nos. 0,630, 4,540,654, 4,556,630, International Publication WO8
What is described in 8/04795 etc. is especially preferable. Examples of cyan couplers include phenolic and naphthol 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, 3,758,308, 4,334,011, 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, 4,333,999
Nos. 4,775,616, 4,451,559, 4,427,767,
Nos. 4,690,889, 4,254,212, 4,296,199, and JP-A-61-42658 are preferred. Further, JP-A 64-553, JP-A 64-554, JP-A 64-555, pyrazoloazole couplers described in JP-A 64-556, and U.S. Pat.
No. 672 can also be used. Typical examples of polymerized dye-forming couplers are described in U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,
No. 282, No. 4,409,320, No. 4,576,910, UK Patent 2,10
2,137, EP 341,188A and the like.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237 and British Patent 2,125,5
No. 70, European Patent No. 96,570, West German Patent (Published) No. 3,234,
Those described in No. 533 are preferred. Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure No. 17643, Sections VII-G, and No. 307105, V.
Section II-G, U.S. Patent No. 4,163,670, JP-B-57-39413
And those described in U.S. Pat. Nos. 4,004,929 and 4,138,258 and British Patent 1,146,368 are preferred. Further, a coupler that corrects 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 that can form a dye by reacting with a developing agent described in U.S. Pat.No.4,777,120 It is also preferable to use a coupler having a precursor group as a leaving group. Compounds that release a photographically useful residue upon coupling can also be preferably used in the present invention. DI that releases development inhibitors
R couplers other than those represented by the general formula (I) of the present invention include those described in RD Nos. 17643, VII-F and 307105, V.
Patents described in section II-F, JP-A-57-151944,
154234, 60-184248, 63-37346, 63-37350
And those described in U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred. RD No. 11449, No. 24241, and bleaching accelerator releasing couplers described in JP-A-61-201247, etc.
This is effective for shortening the time of the processing step having bleaching ability, and particularly when the above-mentioned tabular silver halide grains are added to a light-sensitive material, the effect is great. As the coupler which releases a nucleating agent or a development accelerator imagewise during development, those described in British Patent Nos. 2,097,140 and 2,131,188, JP-A-59-157638 and JP-A-59-170840 are preferred. Also, JP-A-60-107029, JP-A-60-252340,
Compounds which release a fogging agent, a development accelerator, a silver halide solvent, and the like by an oxidation-reduction reaction with an oxidized form of a developing agent described in 1-444940 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
No. 93, 4,310,618, etc., multi-equivalent couplers described in JP-A-60-185950, DIR redox compound releasing couplers described in JP-A-62-24252, etc., DIR coupler releasing couplers, DIR coupler releasing redox compounds or D
IR redox releasing redox compounds, EP 173,
Nos. 302A and 313,308A, couplers releasing dyes that recolor after release, ligand releasing couplers described in U.S. Pat.Nos. 4,555,477, and couplers releasing leuco dyes described in JP-A-63-75747. And couplers releasing fluorescent dyes described in U.S. Pat. No. 4,774,181.

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

In the color light-sensitive material of the present invention, phenethyl alcohol and 1,2-benzisothiazolin-3-one described in JP-A-63-257747, JP-A-62-272248 and JP-A-1-80941 may be used. Adding various preservatives or fungicides 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 aforementioned 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 the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less,
23 μm or less is more preferable, 18 μm or less is further preferable, and 16 μm or less is particularly preferable. The film swelling speed T _1/2
Is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness means a film thickness measured under humidity control at 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, A. Green et al., Photographic Science and Engineering (Photogr. Sci.
& Eng.), Vol. 19, No. 2, pp. 124-129, and can be measured by using a type of serometer (swelling meter).
_{As for 1/2} , 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds is defined as a saturated film thickness.
Is defined as the time to reach. Film swelling speed T
_{The 1/2} can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling ratio is preferably from 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above according to the formula: (maximum swelling film thickness-film thickness) / film thickness. The light-sensitive material of the present invention preferably has 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. The back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent, and the like. The swelling ratio of this back layer is 150 ~ 5
00% is preferred.

The color photographic light-sensitive material according to the present invention is described in RD No. 17643, pp. 28-29, RD No. 18716, pp. 651 left-right column, and RD No. 307105, pp. 880-881. The development can be carried out by the usual method. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 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-
(4-hydroxybutyl) aniline, and sulfates, hydrochlorides or p-toluenesulfonates thereof. 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-toluenesulfonates or sulfates are preferred. These compounds can be used in combination of two or more depending on the purpose. The color developing solution may be a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It generally contains an inhibitor or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, N, N-
Hydrazines such as biscarboxymethylhydrazine,
Various preservatives such as phenylsemicarbazides, triethanolamine, catecholsulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, and dye formation Couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, various chelating agents represented by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids Can be added. Such chelating agents include, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N , N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid), and salts thereof.

When the reversal process is performed, color development is usually performed after black and white development. 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 in the black-and-white developer. Alternatively, they can be used in combination. The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the photographic material. You can also When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [capacity of treatment liquid (cm ³ )] The above-mentioned aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. It is. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, 63-216050 can be mentioned. Reducing the aperture ratio is not only in both the color development and black-and-white development steps, but also in the subsequent steps, for example, bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer. The time for the color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent.

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two successive bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. Examples of the bleaching agent include compounds of a polyvalent metal such as iron (III), peracids, quinones, and nitro compounds. Typical bleaching agents are organic complex salts of iron (III),
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid Etc. can be used. Of these, iron (III) complex salts of ethylenediaminetetraacetate and iron (1,3-diaminopropanetetraacetate (II)
Iron (III) aminopolycarboxylate complex salts such as (I) complex salts are preferred from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but the processing can be carried out at a lower pH to speed up the processing.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following publications: U.S. Pat. No. 3,893,858, West German Patent 1,290,812,
2,059,988, JP-A-53-32736, JP-A-53-57831, and 5
3-37418, 53-72623, 53-95630, 53-95631
No. 53-104232, No. 53-124424, No. 53-141623,
No. 53-28426, Research Disclosure No. 17129
Having a mercapto group or a disulfide group described in JP-A No. (July 1978); a thiazolidine derivative described in JP-A-50-140129;
No. 832, No. 53-32735, U.S. Pat. No. 3,706,561; thiourea derivatives; West German Patent No. 1,127,715, JP-A-58-16
Iodide salts described in No. 235; West German Patent Nos. 966,410 and 2,741
Polyoxyethylene compounds described in No. 8,430;
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 Nos. 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 in view of a large accelerating effect, and in particular, U.S. Pat.
No. 12, JP-A-53-95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, specifically acetic acid, propionic acid, hydroxyacetic acid and the like. Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodides, and thiosulfates are generally used. In particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct or a sulfinic acid compound described in EP 294,769A is preferable. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution. In the present invention, the 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 / l of a compound of the formula (1), preferably imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methylimidazole.

The total time of the desilvering step is preferably shorter as long as the desilvering failure does not occur. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented. In the desilvering step, it is preferable that the stirring is strengthened as much as possible.
Specific methods of strengthening the stirring include a method of impinging a jet of a processing solution on an emulsion surface of a photosensitive material described in JP-A-62-183460, and a method of stirring using a rotating means described in JP-A-62-183461. A method of increasing the effect, a method of moving the photosensitive material while bringing the wiper blade provided in the liquid into contact with the emulsion surface, and improving the stirring effect by making the emulsion surface turbulent, and a circulation of the entire processing solution. There is a method of increasing the flow rate. Such a stirring improving means is effective for any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-described means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator. The automatic developing machine used for the light-sensitive material of the present invention is described in JP-A-60-191257.
It is preferable to have the photosensitive material conveying means described in JP-A Nos. 60-191258 and 60-191259. JP-A-60-1
As described in JP-A-91257, such a conveying means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing solution from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely.
Among them, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picture and
Television Engineers Vol. 64, pp. 248-253 (5 May 1955)
Month) can be obtained. According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be significantly reduced, but bacteria increase due to an increase in the residence time of water in the tank, and the generated floating substances adhere to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, such a problem is solved by
The method for reducing calcium ions and magnesium ions described in 62-288838 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. (1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology"
(1982) The Fungicide described in "Encyclopedia of Bactericidal and Fungicides" (ed. 1986) edited by the Japan Society of Industrial Technology, Japan Society of Bacteria and Fungi. The pH of the washing water in the processing of the light-sensitive material of the present invention is 4 to 4.
9, preferably 5 to 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but in general, 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 processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, Japanese Unexamined Patent Application Publication No.
Known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can all be used. Further, after the water washing treatment, a stabilization treatment may be further carried out. As an example, a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography, is exemplified. be able to. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step. In processing using an automatic developing machine or the like, when each of the above processing solutions is 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 speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline-based compounds described in U.S. Pat. No. metal salt complex described in JP-A-53-135628
The urethane-based compounds described in (1) can be cited. The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones as needed for the purpose of accelerating color development. A typical compound is disclosed in
-64339, 57-144547 and 58-115438. The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to.

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

[0084]

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

Example 1 On an undercoated cellulose triacetate film support,
Sample 101, which is a multilayer color photographic material composed of each layer having the following composition, 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 dyes are shown in terms of moles per mole of silver halide in the same layer. The symbols indicating the additives have the following meanings. However, when there is more than one utility, only 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;

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 × 10 ^-2 ExF-3 5.0 × 10 ^-3 ExM-3 0.11 Cpd-5 1.0 × 10 ^-3 Solv-1 0.16 Solv-2 0.10

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

Third layer (medium-speed red-sensitive emulsion layer) Silver iodobromide emulsion C Silver 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 × 10 ^-2 ExC-9 3.0 × 10 ^-2 Cpd-4 1.5 × 10 ^-3

Fourth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 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 × 10 ^-5 ExC-1 2.0 × 10 ^-2 ExC-3 2.0 × 10 ^-2 ExC-4 9.0 × 10 ^-2 ExC-5 5.0 × 10 ^-2 ExC-8 1.0 × 10 ^-2 ExC- 9 1.0 × 10 ^-2 Cpd-4 1.0 × 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 Silver coating 0.10 Silver iodobromide emulsion F Silver coating 0.28 Gelatin 0.31 ExS-3 1.0 × 10 ^-4 ExS-4 3.1 × 10 ^-4 ExS-5 6.4 × 10 ^-5 ExM-1 0.12 ExM-7 2.1 × 10 ^-2 Solv-1 0.09 Solv-3 7.0 × 10 ^-3

Seventh layer (medium-speed green-sensitive emulsion layer) Silver iodobromide emulsion G Silver 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 × 10 ^-2 ExY-1 5.4 × 10 ^-2 Solv-1 0.23 Solv-3 1.8 × 10 ^-2

Eighth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion H Silver 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 × 10 ^-3 ExM-3 1.0 × 10 ^-2 ExM-5 1.0 × 10 ^-2 ExM-6 3.0 × 10 ^-2 ExY-1 1.0 × 10 ^-2 ExC-1 4.0 × 10 ^-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

Tenth layer (donor layer of multilayer effect on red-sensitive layer) Silver iodobromide emulsion I Silver coating amount 0.40 Silver iodobromide emulsion J Silver coating amount 0.20 Silver iodobromide emulsion K Silver coating 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

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

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

Fourteenth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion N Silver coating amount 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

15th layer (first protective layer) Fine grain silver iodobromide emulsion O Silver 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 Silver coating amount 0.36 Gelatin 0.50 B-1 (2.0 μm in diameter) 8.0 × 10 ^-2 B-2 (2.0 μm in diameter) 8.0 × 10 ^{− 2} B-3 2.0 × 10 ^-2 W-5 2.0 × 10 ^-2 H-1 0.18

[0103] In addition to the above,
1,2-Benzisothiazolin-3-one (average 200 ppm based on gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm), and 2-phenoxyethanol (about 10,000 ppm) were added. Furthermore, W-1 to W-6 to improve the storage property, processing property, pressure resistance, antifungal / antibacterial properties, antistatic property and coatability of each layer as appropriate.
B-1 to B-6, F-1 to F-16 and iron salts, lead salts,
Contains gold, platinum, iridium and rhodium salts.

[0103]

[Table 1]

In Table A, (1) Emulsions A to N were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-19938. (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 preparing tabular grains, low molecular weight gelatin was 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 using a high-pressure electron microscope. (5) Emulsions A to N were prepared using BHCarroll, Photographic Scien
Ce and Engineering, 24, 265 (1980), etc., contains iridium inside the particles.

[0105]

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[0106]

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[0110]

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[0111]

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[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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(Samples 102 to 111) First sample 101
Samples 102 to 111 were prepared by replacing Comparative Compound A added to Layer 0 with another comparative compound or the compound of the present invention in an equimolar amount as shown in Table-B.

After subjecting these samples to red uniform exposure so that the cyan density becomes approximately 1.0, the maximum transmittance was 52%.
Imagewise exposure was performed through a 0 nm interference filter, color development processing described later was performed, and density measurement was performed. The value obtained by subtracting the cyan density at 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 through the MTF measurement pattern,
After the development, the MTF value of the cyan image in 25 cycles was measured. Further, each sample was exposed twice in a white imagewise manner,
One book at 7 ° C, 55% RH for one week, the other one at 50 ° C,
After storage in a dark room at 80% RH for 1 week, development was performed, and the change in the reciprocal of the exposure amount that gave the density of magenta density (fog + 0.2) was determined as the relative sensitivity change under the forced deterioration condition.

[0124]

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[0125]

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The color development was carried out using an automatic developing machine under the following conditions. The processing steps and the composition of the processing solution are shown below.

(Processing step) Process Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 5 seconds 38.0 ° C 23 ml 17 liter Bleaching 50 seconds 38.0 ° C 5 ml 5 liter Bleaching and fixing 50 seconds 38.0 ° C-5 liter 50 seconds 38.0 ℃ 16 ml 5 liters Washing water 30 seconds 38.0 ℃ 34 ml 3 liters stable (1) 20 seconds 38.0 ℃-3 liters stable (2) 20 seconds 38.0 ℃ 20 ml 3 liters drying 1 minute 60 ℃ * The amount of replenishment is 35 mm of photosensitive material and 1.1 m width (equivalent to 24 Ex. 1 bottle).

The stabilizing solution was of a countercurrent type from (2) to (1), and the overflow of the washing water was all introduced into the fixing bath. For replenishment to the bleach-fixing bath, a cut is provided at the top of the bleaching tank and the fixing tank of the automatic processor, and all the overflow liquid generated by supplying the replenisher to the bleaching tank and the fixing tank is transferred to the bleach-fixing bath. It was made to flow in. The amount of the developer brought into the bleaching step, the amount of the bleached liquid brought into the bleach-fixing step, the amount of the bleach-fixed liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 35 mm width of the photosensitive material. 2.5 ml, 2.0 ml, respectively, per meter
2.0 ml, 2.0 ml. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step. Each replenisher was replenished with the same liquid as the respective tank liquid.

The composition of the processing liquid is shown below.

[0130]

(Bleach-fixing solution) A mixture of the above bleaching solution and the following fixing solution in a ratio of 15:85 (by volume). (PH 7.0)

[0132]

(Washing water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Company).
120B) and a mixed bed column packed with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentration to 3 mg.
Per liter or less, followed by 20 mg / liter of sodium diisocyanurate and 150 mg of sodium sulfate.
mg / l was added. The pH of this solution is 6.5 to 7.
5 range.

[0134]

[0135]

[Table 2]

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

Example 2 The seventh and eighth layers of the sample 110 of JP-A-4-340544 were used.
The compound (2), (3) and (6) of the present invention were added to the layer and the ninth layer at a rate of 0.010 g / m ² , respectively, and evaluated according to Example 1 of the present invention. Compared to the sample 110 of the patent where no compound was added, the sample to which these compounds were added was clearly observed to have a large overlay effect and excellent sharpness. Here, in the imagewise exposure for evaluating the multilayer effect, a 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.

──────────────────────────────────────────────────続 き Continued on front page (31) Priority claim number Japanese Patent Application No. 4-253473 (32) Priority date August 31, 1992 (1992.8.31) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 4-258909 (32) Priority date September 3, 1992 (1993.9.3) (33) Priority claim country Japan (JP) (72) Inventor Mibayashi Keiji 210 Nakanuma, Minamiashigara-shi, Kanagawa Fujisha Shin Film Co., Ltd. , A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03C 7/305

Claims (1)

(57) [Claims] 1. A compound represented by the following general formula (I) which reacts with an oxidized form of a developing agent to release a photographically useful group or a precursor group thereof and does not substantially form a color image. A silver halide color photographic light-sensitive material comprising: General formula (I) (Wherein, R ₁ represents a group capable of allowing a compound formed by the reaction between the compound represented by the general formula (I) and the oxidized form of the developing agent to flow out into the processing solution, and R ₂ represents a hydrogen atom Or a substituent, n1 represents 0 to 4, and n1 is 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 ＮＲNR ₄ . N when W ₁ is a carbon atom
2 is 1, W ₁ is the n2 when the sulfur atom is 1 or 2. 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 heterocyclic group. 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 / or
Alternatively, at least one of X ₄ represents a diffusion-resistant group. )