JP2000292892A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide color photographic sensitive material less liable to a change in sensitivity in running processing by incorporating at least one specified compound into at least one of photographic constituent layers and at least one specified magenta coupler into at least one of the photographic constituent layers. SOLUTION: At least one compound of formula I is incorporated into at least one of photographic constituent layers and at least one magenta coupler of formula II is incorporated into at least one of the photographic constituent layers. In the formula I, Y is the residue of a yellow coupler capable of reacting with the oxidized body of a color developing agent, T is a 1,2,4-triazole skeleton bonding to the coupling position of Y by way of a nitrogen atom and optionally having a substituent or the like, S is a sulfur atom bonding to a carbon atom of T, R0 is substituted phenyl or the like, R1 is a hydrogen atom, alkyl or the like and R2 is alkyl optionally having a substituent or the like. In the formula If, R21 is alkylthio or the like, R22 is aryl, R23 is a substituent and n2 is an integer of 1-5.

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, and more particularly to a silver halide color photographic light-sensitive material having high sensitivity, excellent storage stability over time, and little fluctuation in sensitivity during running processing.

[0002]

2. Description of the Related Art In recent years, demands for performance improvement of silver halide color photographic light-sensitive materials (hereinafter, also simply referred to as light-sensitive materials) have become increasingly severe, and development of light-sensitive materials having high sensitivity, excellent sharpness, and excellent color reproducibility has been developed. Is desired.

[0003] In response to such demands, as a means for improving sharpness, a DIR compound which reacts with an oxidized form of a color developing agent and releases a development releasing agent is known. It is well known that by including this in an emulsion, sharpness is improved by the edge effect. However, these DIR compounds have the disadvantage that the development inhibitor released during color development diffuses into the processing solution from the photosensitive material and accumulates, resulting in the processing solution exhibiting development inhibiting properties.

[0004] Couplers for solving such problems are disclosed in JP-A-57-151944 and JP-A-58-20515.
No. 0, No. 60-218644, No. 60-221750
No. 61-11743 and U.S. Pat.
012, etc.

These couplers exhibit a development inhibiting property when released from the coupling position, and have a property of being decomposed into compounds which do not affect photographic properties after flowing out into the processing solution. It is a coupler having a group. Certainly, even when the photosensitive material is subjected to a large amount of running processing, the sensitivity is small and the contamination of the developer is reduced by these couplers.

On the other hand, in response to the demand for higher sensitivity, a technique for providing highly reactive 2-equivalent pyrazolone couplers or naphthol couplers has been disclosed in JP-A-8-171186 and JP-A-8-171186.
-95212. A technique for introducing dislocation lines into tabular silver halide grains is disclosed in U.S. Pat.
56,269, JP-A-63-220238 and JP-A-1-201649.

[0007] However, although the influence on the processing solution can be improved by the DIR technique, recently the tendency of the replenishment of the processing solution has been increasing, so that the contamination of the developing solution is further reduced. On the other hand, development of a photosensitive material having higher sensitivity and excellent storage stability with time has been desired in response to a high level requirement required for the photosensitive material.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material having high sensitivity, excellent storage stability over time, and little fluctuation in sensitivity during running processing.

[0009]

The above object of the present invention has been attained by the following constitutions.

1) A silver halide color photographic material having a photographic structure comprising at least one blue-sensitive layer, a green-sensitive layer, a red-sensitive layer, and a non-light-sensitive layer on a support. A magenta coupler represented by the following general formula (2), wherein at least one of the photographic constituent layers contains at least one compound represented by the following general formula (1), and at least one of the photographic constituent layers is represented by the following general formula (2) A silver halide color photographic material comprising at least one of the following.

[0011]

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(Wherein, Y represents a yellow coupler residue capable of undergoing a coupling reaction with an oxidized form of a color developing agent, and T may have a substituent bonded to the coupling position of Y with a nitrogen atom. Represents a 1,2,4-triazole skeleton or a 1,2,3-triazole skeleton which may have a substituent.
Represents a sulfur atom bonded on the carbon atom of T. R ⁰ represents a substituted phenyl group or a substituted alkyl group. R ¹ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent; R ² represents an alkyl group which may have a substituent; Represents a good aryl group. )

[0013]

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(Wherein, R ²¹ represents an arylthio group or an alkylthio group, R ²² represents a substituted or unsubstituted aryl group. R ²³ represents a substituent, and n ² represents an integer of 1 to 5.) When n ² is 2 or more, R ²³ may be the same or different.) 2) At least one blue-sensitive layer on the support,
In a silver halide color photographic light-sensitive material having a photographic structure comprising a green light-sensitive layer, a red light-sensitive layer, and a non-light-sensitive layer, at least one of the photographic layers is at least one of the compounds represented by the general formula (1). A silver halide color photographic light-sensitive material comprising at least one of the photographic constituent layers and at least one cyan coupler represented by the following general formula (3).

[0015]

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(Wherein, R ³¹ represents an alkyl group or a cycloalkyl group, and R ³² represents a group that can be substituted on a benzene ring.
n ³ represents an integer of 1-4. X ³ represents a group capable of leaving by reaction with an oxidized form of the color developing agent. 3) on the support, at least one blue-sensitive layer each,
In a silver halide color photographic light-sensitive material having a photographic structure comprising a green light-sensitive layer, a red light-sensitive layer, and a non-light-sensitive layer, at least one of the photographic layers is at least one of the compounds represented by the general formula (1). A silver halide color photographic material comprising at least one photosensitive layer and at least one of the following light-sensitive layers containing the following silver halide emulsion 1.

(Silver halide emulsion 1) The coefficient of variation of the grain size of all silver halide grains is 25% or less, and 50% or more of the projected area of the silver halide grains is a halogen on a flat plate having an aspect ratio of 5 or more. Silver halide grains, wherein the silver iodide content of the surface of the tabular silver halide grains is larger than the average silver iodide content of the grains, and 30% of the tabular silver halide grains
The above (number ratio) has dislocation lines in the center region and the outer peripheral region of the main plane, and the dislocation lines in the outer peripheral region are 2
A silver halide emulsion having 0 or more grains.

(4) The silver halide color photographic material as described in (3) above, wherein the silver halide emulsion 1 is the following silver halide emulsion 2.

(Silver halide emulsion 2) 50% or more (number ratio) of tabular silver halide grains have dislocation lines in the central region and the peripheral region of the main plane, and the number of dislocation lines in the peripheral region is one. A silver halide emulsion having 30 or more grains per grain.

5) The above 3) or 4) comprising at least one compound represented by the general formula (1) and at least one magenta coupler represented by the general formula (2). A) a silver halide color photographic light-sensitive material according to

6) The composition according to the above 3), comprising at least one compound represented by the general formula (1) and at least one cyan coupler represented by the general formula (3).
Or the silver halide color photographic light-sensitive material according to 4).

Hereinafter, the present invention will be described in more detail.

In the general formula (1), the yellow coupler residue represented by Y includes a malondiamide type, a malonester monoamide type, a malondiester type, a benzoylacetanilide type, a cycloalkanoylacetamide type, a pivaloylacetanilide type, Benzoylmethane type, benzothiazolylacetamide type, benzoxazolylacetamide type, benzimidazolylacetamide type and the like can be mentioned. Representative examples are U.S. Pat. Nos. 2,298,443, 2,407,210, 2,875,057, 3,048,194, 3,265,506, and 3; , 447, 928. No. 5,021,332,
No. 5,021,330 or EP 421,22
It may be a coupler residue described in No. 1A.

In the general formula (1), as the yellow coupler residue represented by Y, a yellow coupler residue having the following structure is particularly preferable (* indicates the position where T bonds to T).

[0025]

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[0026]

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In the general formula (1), a 1,2,4-triazole skeleton optionally having a substituent represented by T and a 1,2,3-triazole skeleton optionally having a substituent are Specifically, the following general formulas (102), (103), and (10)
4) and (105).

[0028]

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The above general formulas (102), (103) and (1)
In 04) and (105), the * mark indicates the position where the bond to the yellow coupler residue represented by Y, and the ** mark indicates the position where the bond to the sulfur atom in the general formula (1).

The general formulas (102), (103) and (10)
In 4) and (105), Z represents a hydrogen atom or a substituent. Examples of the substituent represented by Z include an alkyl group (eg, a methyl group, an isopropyl group, a cyclopropyl group, etc.), an aryl group (eg, a phenyl group, a tolyl group, etc.), and a heterocyclic residue (eg, a furyl group, Thienyl group, pyridyl group, etc.), alkylthio group (eg, methylthio group, t-octylthio group, etc.), arylthio group (eg, phenylthio group, etc.), oxycarbonyl group (eg, methoxycarbonyl group, cyclohexyloxycarbonyl group, etc.) Aryloxycarbonyl groups such as carbonyl group and phenoxycarbonyl group, and 2-
A heterocyclic oxycarbonyl group such as a pyridyloxycarbonyl group) is preferable.

In the general formula (1), examples of the optionally substituted alkyl group represented by R ¹ include a methyl group, an isopropyl group, a cyclopropyl group and 2-chloroethyl. Examples of the aryl group which may have a group include a phenyl group, a tolyl group, and a p-methoxyphenyl group. As R ¹ , a hydrogen atom is particularly preferred.

In the general formula (1), examples of the alkyl group which may have a substituent represented by R ² include a methyl group, an isopropyl group, a cyclopropyl group, a t-butyl group and a 2-chloroethyl group. And examples of the aryl group which may have a substituent include a phenyl group, a tolyl group, and a p-methoxyphenyl group. R ² is preferably an alkyl group, particularly preferably an alkyl group having a total carbon number of 4 or less.

In the general formula (1), examples of the substituted phenyl group represented by R ⁰ include:

[0034]

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And the like.

R ³ is an alkyl group which may have a substituent (eg, a methyl group, an isopropyl group, a cyclopropyl group, a t-butyl group, a 2-chloroethyl group, etc.), and an aryl group which may have a substituent. Represents a group (for example, a phenyl group, a tolyl group, a p-methoxyphenyl group, etc.). R ³ is preferably an alkyl group having 8 or less carbon atoms, particularly preferably an alkyl group having 4 or less carbon atoms, and particularly preferably a branched alkyl group.

R ⁴ represents an arbitrary substituent that can be substituted on the benzene ring, and m represents an integer of 0 to 4.

The substituent represented by R ⁴ includes R ¹ and R ²
And an alkyl group which may have a substituent shown in the description of R ^3, in addition to an aryl group which may have a substituent, a Hajime Tamaki (e.g., 2-tetrahydrofuryl group, 4-imidazolyl group, An indolin-1-yl group and a 2-pyridyl group, a carbonyl group (eg, an acetyl group, an alkylcarbonyl group such as a trifluoroacetylpivaloyl group, a benzoyl group, a pentafluorobenzoyl group, and 3,5-di-t). Arylcarbonyl groups such as -butyl-4-hydroxybenzoyl group, etc.), oxycarbonyl groups (for example, alkoxycarbonyl groups such as methoxycarbonyl group, cyclohexyloxycarbonyl group, n-dodecyloxycarbonyl group, phenoxycarbonyl group, 2,4 -Di-t
-Amylphenoxycarbonyl group, aryloxycarbonyl group such as 1-naphthyloxycarbonyl group, 2-pyridyloxycarbonyl group, 1-phenylpyrazolyl-
A heterocyclic oxycarbonyl group such as a 5-oxycarbonyl group, an alkylcarbamoyl group such as a dimethylcarbamoyl group, a 4- (2,4-di-t-amylphenoxy) butylaminocarbonyl group, and a phenylcarbamoyl group; Group, an arylcarbamoyl group such as a 1-naphthylcarbamoyl group), a sulfonyl group (for example, an alkylsulfonyl group such as a methanesulfonyl group and a trifluoromethanesulfonyl group, an arylsulfonyl group such as a p-toluenesulfonyl group), and a sulfamoyl group (for example, Dimethylsulfamoyl group, 4- (2,4-di-t
-Amylphenoxy) alkylsulfamoyl group such as butylaminosulfonyl group, arylsulfamoyl group such as phenylsulfamoyl group, halogen atom (eg, chlorine atom, bromine atom, etc.), cyano group, nitro group, alkenyl Group (eg, 2-propylene group, oleyl group, etc.), hydroxy group, alkoxy group (eg, methoxy group, 2-ethoxyethoxy group, etc.), aryloxy group (eg, phenoxy group, 2,4-di-t- Amylphenoxy group, 4- (4-hydroxyphenylsulfonyl)
Phenoxy group, etc.), heterocyclic oxy group (eg, 4-pyridyloxy group, 2-hexahydropyranyloxy group, etc.), carbonyloxy group (eg, alkyl such as acetyloxy group, trifluoroacetyloxy group, pivaloyloxy group, etc.) An aryloxy group such as a carbonyloxy group, a benzoyloxy group, and a pentafluorobenzoyloxy group; a urethane group (for example, an alkylurethane group such as an N, N-dimethylurethane group; an N-phenylurethane group; an N- (p- An arylurethane group such as a cyanophenyl) urethane group, a sulfonyloxy group (for example, an alkylsulfonyloxy group such as a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, an n-dodecanesulfonyloxy group, a benzenesulfonyloxy group,
an arylsulfonyloxy group such as a p-toluenesulfonyloxy group), an amino group (for example, a dimethylamino group,
Alkylamino group such as cyclohexylamino group, n-dodecylamino group, arylamino group such as anilino group, pt-octylanilino group, etc., sulfonylamino group (eg, methanesulfonylamino group, heptafluoropropanesulfonylamino) Group, alkylsulfonylamino group such as n-hexadecylsulfonylamino group, arylsulfonylamino group such as p-toluenesulfonylamino group and pentafluorobenzenesulfonylamino), sulfamoylamino group (for example, N, N-dimethylsulfonate) Alkylsulfamoylamino group such as famoylamino group, arylsulfamoylamino group such as N-phenylsulfamoylamino group, acylamino group (for example,
Alkylcarbonylamino groups such as acetylamino group and myristoylamino group, arylcarbonylamino groups such as benzoylamino group), ureido group (for example, N, N-
Alkylureido groups such as dimethylaminoureido group, N
-Phenylureido group, arylureido group such as N- (p-cyanophenyl) ureido group), alkylthio group (eg, methylthio group, t-octylthio group, etc.), arylthio group (eg, phenylthio group, etc.). .

As the substituent represented by R ⁴ , an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, and an acylamino group are preferable, and particularly, it has 8 or less carbon atoms, and more preferably 4 or less carbon atoms. Is particularly preferred. One of the substituents represented by R ⁴ is the 6-position (o-
Position).

In the general formula (1), examples of the alkyl group in the substituted alkyl group represented by R ⁰ include methyl, ethyl, propyl, isopropyl, t-
Butyl group and the like. The substituent of the substituted alkyl group is not particularly limited, and may be any substituent. R ⁰
Preferred substituted alkyl groups represented by, for example,

[0041]

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And the like.

R ⁵ represents a substituent that can be substituted on the benzene ring, and n represents an integer of 0 to 5. R ⁶ represents a hydrogen atom or an optionally substituted alkyl group or an aryl group; R ⁷ represents a hydrogen atom or an optionally substituted alkyl group or an aryl group; X represents an oxycarbonyl group;
Represents a carbamoyl group or a carbonyl group.

W represents an aryloxy group, an arylthio group or a sulfonyl group which may have a substituent.

Examples of the substituent that can be substituted on the benzene ring represented by R ⁵ include the substituents described for R ⁴ .

Preferred substituents which can be substituted on the benzene ring represented by R ⁵ are a halogen atom, a carbonyl group, an oxycarbonyl group, a carbamoyl group, a sulfonyl group, a sulfamoyl group, a cyano group and a nitro group. Particularly preferred substituents are a halogen atom and an alkoxycarbonyl group, and the most preferred substituent is an alkoxycarbonyl group having a total carbon number of 6 or less.

Examples of the alkyl group which may have a substituent represented by R ⁶ include, for example, a methyl group, an isopropyl group,
Examples of the aryl group include a cyclopropyl group, a t-butyl group, and 2-chloroethyl. Examples of the aryl group include a phenyl group, a tolyl group, and a p-methoxyphenyl group. R ⁶ is preferably a hydrogen atom.

Examples of the alkyl group which may have a substituent represented by R ⁷ include, for example, a methyl group, an isopropyl group,
Examples of the aryl group include a cyclopropyl group, a t-butyl group, and 2-chloroethyl. Examples of the aryl group include a phenyl group, a tolyl group, and a p-methoxyphenyl group. R ⁷ is preferably a hydrogen atom or an alkyl group, and particularly preferably an alkyl group having a total carbon number of 4 or less.

The oxycarbonyl group represented by X is, for example, an alkoxycarbonyl group such as a methoxycarbonyl group, a cyclohexyloxycarbonyl group, an n-dodecyloxycarbonyl group, a phenoxycarbonyl group,
2,4-di-t-amylphenoxycarbonyl group, 1-
Examples of the carbamoyl group include an aryloxycarbonyl group such as a naphthyloxycarbonyl group, a heterocyclic oxycarbonyl group such as a 2-pyridyloxycarbonyl group, and a 1-phenylpyrazolyl-5-oxycarbonyl group. -(2,4-di-t-
Amylphenoxy) alkylcarbamoyl group such as butylaminocarbonyl group, phenylcarbamoyl group, arylcarbamoyl group such as 1-naphthylcarbamoyl group,
Examples of the carbonyl group include an acetyl group, an alkylcarbonyl group such as a trifluoroacetylpivaloyl group,
Benzoyl group, pentafluorobenzoyl group, 3,5-
And arylcarbonyl groups such as di-t-butyl-4-hydroxybenzoyl group. Preferably X is an oxycarbonyl group, particularly preferably an alkoxycarbonyl group having a total carbon number of 6 or less.

Examples of the aryloxy group which may have a substituent represented by W include, for example, phenoxy group, p-ethoxycarbonylphenoxy group, 2,4-di-t-amylphenoxy group, 4- (4 -Hydroxyphenylsulfonyl) phenoxy group and the like; arylthio groups such as phenylthio group and p-ethoxycarbonylphenylthio group; and sulfonyl groups such as alkylsulfonyl groups such as methanesulfonyl group and trifluoromethanesulfonyl group; And arylsulfonyl groups such as p-toluenesulfonyl group. Preferably W is an aryloxy group, and a substituted phenoxy group is particularly preferred.

In the compound represented by the general formula (1),
Atomic group including T other than Y

[0052]

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Is a development inhibitor residue released from Y by a coupling reaction with an oxidized color developing agent. Particularly preferred development inhibitor residues are development inhibitor residues derived from development inhibitors having the following structure.

[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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Next, typical compounds represented by the general formula (1) of the present invention are shown, but the present invention is not limited thereto.

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

[Table 3]

[0065]

[Table 4]

In the general formula (2), R ²² represents a substituted or unsubstituted aryl group, and is preferably a substituted aryl. Examples of the substituent include a halogen atom, a cyano group, an alkylsulfonyl group, and a halogen atom as described in the general formula (1).
Arylsulfonyl group, sulfamoyl group, sulfonamide group, carbamoyl group, carbonamide group, alkoxy group, acyloxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, ureido group, nitro group, alkyl group, trifluoromethyl group And the like.

Preferably, R ²² is pentachlorophenyl, 2,4,6-trichlorophenyl, 2,5-dichlorophenyl, 2,4-dichlorophenyl, 2,6
-Dichloro-4-methylphenyl group, 2,6-dichloro-4-methanesulfonylphenyl group, 2,6-dichloro-4-cyanophenyl group, 2,6-dichloro-4-morpholinosulfonylphenyl group, 2,4 -Dichloro-6-
This is the case of a methoxyphenyl group and a 2,4-dichloro-6-methylphenyl group. Particularly, a pentachlorophenyl group, a 2,6-dichloro-4-methanesulfonylphenyl group, a 2,6-dichloro-4-cyanophenyl group, a 2,6
-Dichloro-4-morpholinosulfonylphenyl is preferred.

In the general formula (2), R ²³ represents a substituent, and as described in the general formula (1), a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carbonamide group, a carbamoyl group , A sulfonamide group, a sulfamoyl group, an alkylsulfoxyl group, an arylsulfoxyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acyloxy group, a ureido group, an imide group, a carbamate group, Examples include a heterocyclic group, a cyano group, a trifluoromethyl group, an alkylthio group, a nitro group, a carboxyl group, a hydroxyl group, and a group linked to a polymer chain. At least one of the substituents among the substituents represented by R ²³ is desirably a halogen atom or an alkoxy group.

Specific examples of the compound represented by formula (2) of the present invention are shown below, but the present invention is not limited to these.

[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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In the general formula (3), examples of the alkyl group represented by R ³¹ include i-propyl, butyl and i-propyl.
-Butyl, s-butyl, t-butyl, octyl, 2-ethylhexyl, 2-hexyldecyl, tetradecyl and the like.

Examples of the cycloalkyl group represented by R ³¹ include groups such as cyclopentyl, cyclohexyl and adamantyl.

Of the substituents represented by R ³¹ , a branched alkyl group is preferred.

Examples of the group which can be substituted on the benzene ring represented by R ³² include alkyl, cycloalkyl, alkenyl, aryl, acylamino, sulfonamide, alkylthio, arylthio, halogen atom, heterocyclic ring, sulfonyl, sulfinyl, phosphonyl , Acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl , Aryloxycarbonyl, carboxy and the like, and each group. Of these, alkyl and alkoxy groups are preferred.

It is particularly preferred that R ³² is an alkyl group or an alkoxy group and n ³ is 1.

As the leaving group represented by X ³ , for example,
Examples include atoms and groups such as aryloxy, carbamoyloxy, alkoxy, acyloxy, sulfonamide, and succinimide in which a halogen atom, an oxygen atom or a nitrogen atom is directly bonded to the coupling position. Among these, an alkoxy group and an aryloxy group are preferable, and as a group that further substitutes for them, a carboxyl group, a hydroxy group, and a sulfonamide group are preferable.

Specific examples of the cyan coupler represented by the general formula (3) are shown below, but the present invention is not limited thereto.

[0084]

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[0085]

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[0086]

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[0087]

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The compounds represented by formulas (1) to (3) according to the present invention are added to the photosensitive layer, but may be added to the non-photosensitive layer. In order to introduce the compounds represented by the general formulas (1) to (3) according to the present invention into a silver halide color photographic light-sensitive material, they may be dispersed and added by various known dispersion methods described below. For example, known compounds such as dibutyl phthalate, tricresyl phosphate and the like or a mixture of low-boiling solvents such as butyl acetate and ethyl acetate and high-boiling solvents such as tricresyl phosphate, or only low-boiling solvents, the above compounds were dissolved alone or in combination. Thereafter, a method of mixing with a gelatin aqueous solution containing a surfactant, and then emulsifying and dispersing using a high-speed rotary mixer, a colloid mill or an ultrasonic dispersing machine, and directly adding the resulting mixture to a silver halide emulsion can be adopted. . or,
The above emulsified dispersion may be set, shredded, washed with water and then added to the silver halide emulsion.

In the present invention, when the magenta coupler represented by the general formula (2) is used,
147, an aromatic amine derivative described in JP-A No. 9-1,
It is desirable to use the oil-soluble organic basic compound described in No. 20122 in combination from the viewpoint of preventing stain during the bleaching treatment. When the above aromatic amine derivative or oil-soluble organic basic compound is used, it is preferably added in an amount of 1% by weight to 300% by weight based on the magenta coupler represented by the general formula (2), more preferably. 5% to 150% by weight
Add within the range. The layer to be added may be the same as or different from the layer to which the magenta coupler represented by the general formula (2) is added, but is preferably added to the same layer. The aromatic amine derivative and the oil-soluble organic basic compound are the same as the magenta coupler represented by the general formula (2),
It can be introduced into the light-sensitive material by a known dispersion method, and may be mixed and dispersed simultaneously with the magenta coupler represented by the general formula (2), or may be separately dispersed and added. It is more effective to disperse and add.

The silver halide grains contained in the silver halide emulsion of the present invention are tabular grains. Tabular grains are crystallographically classified as twins.

Twins are silver halide crystals having one or more twin planes in one grain, and the twins are classified according to the report by Klein and Moiser, Photography Photographfish
Vol. 99, p100,
Ibid., Vol. 100, p. 57.

The tabular grains in the present invention have two twin planes parallel to the main plane. The twin plane can be observed with a transmission electron microscope. The specific method is as follows. First, a silver halide photographic emulsion is coated on a support so that the contained tabular grains are substantially parallel to the main plane, thereby preparing a sample. This is cut using a diamond cutter to obtain a thin section having a thickness of about 0.1 μm. By observing this section with a transmission electron microscope, the presence of twin planes can be confirmed.

The distance between the twin planes in the tabular grains of the present invention is determined by observing the section using a transmission electron microscope as described above. The distance between the twin planes having the shortest distance among the even twin planes parallel to the main plane is determined for each particle, and the average is obtained by averaging.

In the present invention, the distance between twin planes is a factor affecting the supersaturation state during nucleation, for example, gelatin concentration, gelatin type, temperature, iodine ion concentration, pBr, pBr.
It can be controlled by appropriately selecting a combination of various factors such as H, the ion supply speed, and the stirring rotation speed. In general, the more the nucleation is performed in a supersaturated state, the narrower the distance between twin planes can be.

For details on the supersaturation factor, see, for example, JP-A-63-92924 or JP-A-1-2136.
No. 37 etc. can be referred to.

In the present invention, the average distance between twin planes is preferably 0.01 to 0.05 μm, more preferably 0.013 to 0.025 μm.

The thickness of the tabular grain of the present invention can be obtained by observing a section using the above-mentioned transmission electron microscope, similarly obtaining the thickness of each grain, and performing averaging. The thickness of the tabular grains is preferably from 0.05 to 1.5 μm, more preferably from 0.07 to 0.50 μm.

The tabular grains of the present invention comprise 50% of the total projected area.
The aspect ratio (particle diameter / grain thickness) is 5 or more, preferably 60% or more of the total projected area is 7 or more, more preferably 70% or more of the total projected area.
% Or more has an aspect ratio of 9 or more.

The grain size of the tabular grains in the present invention is represented by the equivalent circle diameter of the projected area of the silver halide grains (the diameter of a circle having the same projected area as the silver halide grains).
0.1 to 5.0 μm is preferable, and more preferably 0.5 to 5.0 μm.
〜3.0 μm.

The particle size is, for example, 1
It can be obtained by magnifying the image from 10,000 times to 70,000 times and actually measuring the particle diameter on the print or the area at the time of projection (the number of measured particles is indiscriminately 1000 or more. ).

[0102] Here, the average particle diameter r is the product ni × ri ³ of the frequency ni and ri ³ particles having a particle size ri is defined as the particle size ri when the maximum (three significant figures, the minimum Digits are rounded off to the nearest 5).

The tabular grains of the present invention comprise a monodispersed silver halide emulsion. Here, as the monodispersed silver halide emulsion, the weight of silver halide contained within a grain size range of ± 25% around the average grain size r is 6% of the total weight of silver halide grains.
It is preferably at least 0%, more preferably 70%
Above, more preferably 80% or more.

The highly monodispersed emulsion of the present invention has a distribution width defined by (standard deviation / average particle size) × 100 = coefficient of variation of particle size (%) of 25% or less. Preferably it is 16% or less. Here, the average particle diameter and the standard deviation are determined from the particle diameter ri defined above.

The average silver iodide content of the tabular grains of the present invention is as follows:
1 mol% or more, preferably 1 to 10 mol%
And more preferably 2 to 5 mol%.

The tabular grains of the present invention are emulsions mainly containing silver iodobromide as described above, but contain silver halide of another composition, for example, silver chloride, as long as the effects of the present invention are not impaired. Can be done.

The distribution state of silver iodide in the silver halide grains can be detected by various physical measurement methods, for example, as described in the Abstracts of the Annual Meeting of the Photographic Society of Japan, 1981. It can be measured by low temperature luminescence measurement, EPMA method or X-ray diffraction method.

In the present invention, the silver iodide content and the average silver iodide content of each silver halide grain are determined by an EPMA method (Electron Probe Micro Ana).
(lyzer method). According to this method, a sample in which emulsion grains are well dispersed so as not to contact each other is prepared, and element analysis of an extremely minute portion can be performed by X-ray analysis by electron beam excitation for irradiating an electron beam. By determining the characteristic X-ray intensity of silver and iodine emitted from each grain by this method, the halogen composition of each grain can be determined. At least 50
When the silver iodide content of each grain is determined by the EPMA method, the average silver iodide content is determined from the average thereof.

The tabular grains in the present invention preferably have a more uniform silver iodide content between grains. EP
When the distribution of silver iodide content between grains is measured by the MA method, the relative standard deviation is preferably 30% or less, more preferably 20% or less.

The silver iodide content on the surface of the tabular grains of the present invention is 1 mol% or more, preferably 2 to 20 mol%.
1%, and more preferably 3 to 15 mol%.

The surface of the tabular grains of the present invention is the outermost layer of the grains including the outermost surface of the silver halide grains, and refers to a depth of up to 50 ° from the outermost surface of the grains.

The halogen composition on the surface of the tabular grains of the present invention is determined by an XPS method (X-ray Photoelectron).
n Spectroscopy method: X-ray photoelectron spectroscopy)
Is determined as follows.

That is, the sample was cooled to −110 ° C. or less in an ultra-high vacuum of 1 × 10 E ⁻⁸ torr or less, and irradiated with MgKα as a probe X-ray at an X-ray source voltage of 15 kV and an X-ray source current of 40 mA. , Ag 3d5 / 2, Br 3
d, I Measure 3d3 / 2 electrons. The integrated intensity of the measured peak is used as a sensitivity factor (Sensitivit).
y Factor), and the halide composition on the silver halide surface is determined from these intensity ratios.

The tabular grains in the present invention satisfy the relation that the silver iodide content on the grain surface is higher than the average silver iodide content of the grains. Preferably, the relationship of silver iodide content on grain surface / average silver iodide content = 2.0-30 is satisfied,
More preferably, it satisfies the relationship of silver iodide content on grain surface / average silver iodide content = 3.0 to 15.

Dislocation lines of silver halide grains are described, for example, in J. Am. F. Hamilton; Photo. Sci.
Eng. , 11 (1967) 57 and T.S. Shiozaw
a; Soc. Photo. Sci. , Japan35
(1972) can be observed by a direct method using a transmission electron microscope at low temperature described in 213. That is, so as not to apply enough pressure to cause dislocations from the emulsion to the grains,
The silver halide grains taken out carefully are placed on a mesh for an electron microscope, and observation is performed by a transmission method in a cooled state of the sample so as to prevent damage (such as printout) by an electron beam. At this time, the thicker the particles, the more difficult it is for an electron beam to pass through, so that a method using a high-pressure electron microscope can observe more clearly. From the grain photograph obtained by such a method, the position and number of dislocation lines in each grain can be determined.

The tabular grains of the present invention have dislocation lines in both the central region and the peripheral region of the main plane.

The central region of the main plane of the tabular grains as used herein is defined as the radius of a circle having an area equal to the main plane of the tabular grains of 8
A region having a radius of 0% and a thickness of a tabular grain in a circular portion when the center is shared. On the other hand, the peripheral region of a tabular grain refers to a region having an area corresponding to an annular region outside the central region, existing around the tabular grain, and having a thickness of the tabular grain.

The number of dislocation lines present in one particle is measured as follows. A series of particle photographs with different inclination angles with respect to the incident electrons are taken for each particle to confirm the existence of dislocation lines. At this time, if the number of dislocation lines can be counted, the number of dislocation lines is counted. When it is not possible to count the number of dislocation lines per particle, such as when the dislocation lines exist densely or when the dislocation lines intersect with each other, it is counted that there are many dislocation lines.

The dislocation lines existing in the central region of the main plane of the tabular grains of the present invention often form a so-called dislocation network, and the number thereof may not be clearly counted.

On the other hand, dislocation lines existing in the outer peripheral region of the tabular grains of the present invention are observed as lines extending radially from the center of the grains toward the sides, but often meander.

In the tabular grains of the present invention, 30% or more of the number ratio has dislocation lines in both the central region and the peripheral region of the main plane, and the number of dislocation lines in the peripheral region is 2 per particle.
The tabular grains having 0 or more but 50% or more (number ratio) have dislocation lines in both the central region and the peripheral region of the main plane, and the number of dislocation lines in the peripheral region is 1 grain. It is preferable that the number of tabular grains is 30% or more, and 70% or more (number ratio) of tabular grains has dislocation lines in both the central region and the peripheral region of the main plane, and the number of dislocation lines in the peripheral region is 1 grain More preferably, it has 40 or more pieces.

As a method for introducing dislocation lines into silver halide grains, for example, a method in which an aqueous solution containing iodide ions such as potassium iodide and a water-soluble silver salt solution are added by a double jet, or a method including silver iodide is used. A method of adding a fine grain emulsion,
A method of adding only a solution containing iodide ions;
Known methods such as a method using an iodide ion releasing agent as described in No. 11781 can be used to form dislocations originating dislocation lines at desired positions. Among these methods, a method of adding a fine grain emulsion containing silver iodide and a method of using an iodide ion releasing agent are particularly preferable.

When an iodine ion releasing agent is used, sodium p-iodoacetamidobenzenesulfonate,
Iodoethanol, 2-iodoacetamide and the like can be preferably used.

The tabular grains of the present invention may be either grains whose latent image is mainly formed on the surface or grains mainly formed inside the grain.

The tabular grains of the present invention are produced in the presence of a dispersion medium, that is, in a solution containing the dispersion medium. Here, the aqueous solution containing a dispersion medium refers to an aqueous solution in which a protective colloid is formed in an aqueous solution by a substance (eg, a substance that can serve as a binder) that can form a hydrophilic colloid, such as gelatin.
Preferably, it is an aqueous solution containing colloidal protective gelatin.

In the practice of the present invention, when gelatin is used as the above protective colloid, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in Arthur Guice's The Macromolecular Chemistry of Gelatin (Academic Press, 1964).

Examples of hydrophilic colloids other than gelatin that can be used as a protective colloid include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate. Cellulose derivatives such as esters, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-
N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole,
There are many kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as polyvinylpyrazole.

In the case of gelatin, it is preferable to use a gelatin having a jelly strength of 200 or more in a puggy method.

In the present invention, the tabular grains may be formed and / or grown in the course of cadmium salt, zinc salt, lead salt, thallium salt, iron salt, rhodium salt, iridium salt, indium salt (including complex salt). ) Can be used to add metal ions to the inside of the particles and / or the surface of the particles to contain these metal elements.

As the means for forming tabular grains of the present invention, various methods well known in the art can be used. That is, any combination of the single jet method, the controlled double jet method, the controlled triple jet method, etc. can be used, but in order to obtain advanced monodisperse grains, it is necessary to produce silver halide grains. It is important to control the pAg in the liquid phase to be adjusted according to the growth rate of the silver halide grains.
As the pAg value, a region of 7.0 to 12 is used, and preferably a region of 7.5 to 11 can be used.

In determining the addition rate, refer to
References can be made to the techniques described in US Pat.

The step of preparing tabular grains of the present invention is roughly classified into a nucleation step, an ripening step (nucleus ripening step) and a subsequent growing step. It is also possible to separately grow a previously prepared nuclear emulsion (or seed emulsion). The growth process may include several stages, such as a first growth process and a second growth process.

The growth process of tabular grains of the present invention means all the growth processes from the nucleus (or seed) formation to the end of grain growth, and the start of growth refers to the start of the growth process.

In the production of the tabular grains of the present invention, a known silver halide solvent such as ammonia, thioether, thiourea or the like may be present, or a silver halide solvent may not be used.

In the tabular grains of the present invention, in order to form dislocation lines selectively in the central region of the main plane, it is necessary to raise the pH in the ripening step after nucleation and to ripen the tabular grains so as to increase the thickness. Is important, but if the pH is too high, the aspect ratio is too low, and it is difficult to control the aspect ratio in a subsequent growth step. Also,
It also causes unexpected fog deterioration. Therefore, the pH / temperature of the aging step is preferably 7.0 to 11.0 / 40 to 80 ° C, more preferably 8.5 to 10.0 / 50 to 70 ° C.

In the tabular grains of the present invention, in order to form dislocation lines selectively in the outer peripheral region, an iodine ion source (for example, silver iodide fine particles, It is important to increase the pAg in the grain growth after adding the iodine ion releasing agent) to the base grains. However, if the pAg is too high, the so-called Ostwald ripening proceeds simultaneously with the grain growth, and the monodispersity of the tabular grains is reduced. Will deteriorate. Therefore, the pAg at the time of forming the peripheral region of the tabular grains in the growth step is 8 to 12
Is preferable, and 9.5 to 11 are more preferable. When an iodine ion releasing agent is used as an iodine ion source, dislocation lines can be effectively formed in the outer peripheral region by increasing the amount of iodine ion releasing agent. The amount of the iodide ion releasing agent to be added is preferably 0.5 mol or more per mol of silver halide, more preferably 2 to 5 mol.

The tabular grains in the present invention may be those obtained by removing unnecessary soluble salts after the growth of the silver halide grains, or may be those containing them.

It is also possible to perform desalting at any point during silver halide growth, as in the method described in JP-A-60-138538. When the salts are removed, Research Disclosure may be used.
(hereinafter abbreviated as RD) No. 17643 No. II. More specifically, in order to remove the soluble salt from the emulsion after the formation of the precipitate or after the physical ripening, a Nudel washing method performed by gelling gelatin may be used, and inorganic salts, anionic surfactants, Anionic polymers (eg, polystyrene sulfonic acid) or gelatin derivatives (eg, acylated gelatin, carbamoylated gelatin, etc.)
A precipitation method (flocculation) using the above method may be used. As a specific example, a method described in JP-A-5-72658 can be preferably used.

The tabular grains of the present invention can be chemically sensitized by a conventional method. That is, sulfur sensitization, selenium sensitization,
A noble metal sensitization method using gold or another noble metal compound can be used alone or in combination.

The tabular grains of the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye which has no spectral sensitizing effect by itself together with the sensitizing dye or a compound which does not substantially absorb visible light and which enhances the sensitizing effect of the sensitizing dye is contained in the emulsion. May be.

An antifoggant, a stabilizer and the like can be added to the tabular grains of the present invention.

As the binder, it is advantageous to use gelatin. The emulsion layer and other hydrophilic colloid layers
It can be hardened and can contain a plasticizer, a dispersion (latex) of a water-insoluble or soluble synthetic polymer.

The additive used in such a process is R
D17643, 18716 and 308119. The following shows the location of the description.

[0143]

[Table 5]

The known photographic additives used in the silver halide emulsion layer according to the present invention are also described in the above RD. The relevant sections are described below.

[0145]

[Table 6]

Various couplers can be used in the silver halide emulsion layer, and specific examples are described in the above RD. The relevant sections are described below.

[0147]

[Table 7]

The additives to the photosensitive material according to the present invention can be added by a dispersion method described in RD308119XIV.

The light-sensitive material according to the present invention includes RD30
An auxiliary layer such as a filter layer or an intermediate layer described in 8119VII-K can be provided.

The light-sensitive material according to the present invention can be obtained by using the RD308
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in section 119VII-K can be adopted.

The light-sensitive material according to the present invention is RD1764
3 pages 28-29, RD18716 page 647 and RD
By the usual method described in XIX at 308119,
It can be developed.

The light-sensitive material of the present invention includes, for example, the type / serial number, manufacturer name, emulsion No. Various information on photographic materials such as, for example, shooting date and time,
Aperture, exposure time, lighting conditions, filters used, weather,
Various information when shooting the camera, such as the size of the shooting frame, the model of the camera, the use of anamorphic lenses, etc., such as the number of prints, selection of filters, customer's color preference, the size of the trimming frame, etc. Magnetic recording for inputting various information required at the time, for example, various information obtained at the time of printing, such as the number of prints, selection of a filter, preference of a customer's color, size of a trimming frame, and other customer information. A layer may be provided.

The magnetic recording layer is preferably coated on the opposite side of the support from the photographic component layer. The undercoat layer, the antistatic layer (conductive layer), the magnetic recording layer, It is preferred that the layers are constituted.

As the magnetic fine powder used for the magnetic recording layer, metal magnetic powder, iron oxide magnetic powder, Co-doped iron oxide magnetic powder, chromium dioxide magnetic powder, barium ferrite magnetic powder and the like can be used. . Methods for producing these magnetic powders are known, and they can be produced according to known methods.

The optical density of the magnetic recording layer is preferably small in consideration of the influence on the photographic image, and is 1.5 or less, more preferably 0.2 or less, and particularly preferably 0.1 or less. The optical density is measured by Konica Sakura Densitometer P
Using DA-65, using a filter that transmits blue light, light having a wavelength of 436 nm is vertically incident on the coating film,
According to a method of calculating light absorption by the coating film.

The amount of magnetization of the magnetic recording layer per 1 m ² of the photosensitive material is preferably 3 × 10 ⁻² emu or more. The amount of magnetization was measured by using an external magnetic field of 5000 in a coating direction of a fixed volume coating film using a sample vibration type magnetometer (VSM-3) manufactured by Toei Industry.
After saturation once with Oe, the magnetic flux density (residual magnetic flux density) when the external magnetic field is reduced to 0 is measured, and this is converted into the volume of the transparent magnetic layer contained per 1 m ² of the photosensitive material. You can ask. If the amount of magnetization per unit area of the transparent magnetic layer is smaller than 3 × 10 ⁻² emu, input / output of magnetic recording is hindered.

The thickness of the magnetic recording layer is 0.01 to 20 μm
It is preferably from 0.05 to 15 μm, more preferably from 0.1 to 10 μm.

As the binder constituting the magnetic recording layer, vinyl resins, cellulose ester resins, urethane resins, polyester resins and the like are preferably used. It is also preferable to form a binder by aqueous coating using an aqueous emulsion resin without using an organic solvent. Further, it is necessary to adjust physical properties of these binders by curing with a curing agent, heat curing, electron beam curing, and the like. In particular, curing by adding a polyisocyanate-type curing agent is preferable.

It is necessary to add an abrasive to the magnetic recording layer in order to prevent clogging of the magnetic head, and it is preferable to add nonmagnetic metal oxide particles, particularly alumina fine particles.

Examples of the support for the photosensitive material include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), cellulose triacetate film, cellulose diacetate film, polycarbonate film, polystyrene film, and polyolefin film. it can.

In particular, JP-A-1-244446 and JP-A-1-244446.
No. 291248, No. 1-298350, No. 2-890
No. 45, No. 2-93641, No. 2-181749,
When a polyester having a high water content as shown in JP-A-2-214852 and JP-A-2-291135 is used, even when the support is made thinner, the curl recovery property after development processing is excellent.

In the present invention, the supports preferably used are PET and PEN. When these are used, the thickness is preferably 50 to 100 μm, particularly preferably 60 to 90 μm.

The light-sensitive material of the present invention comprises ZnO, V ₂ O ₅ , Ti
O ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , Mg
It is preferable to have a conductive layer containing metal oxide particles such as O, BaO, MoO _3, etc. The metal oxide particles are different from those containing oxygen vacancies and different from the metal oxide used to form a donor. Those containing a small amount of atoms are generally preferred because of their high conductivity, and the latter are particularly preferred because they do not give fog to the silver halide emulsion.

As the binder for the conductive layer and the undercoat layer, the same binder as that for the magnetic recording layer can be used.

It is preferable to coat a higher fatty acid ester, a higher fatty acid amide, a polyorganosiloxane, a liquid paraffin, a wax, etc. on the magnetic recording layer as a sliding layer.

When the light-sensitive material of the present invention is used as a color light-sensitive material for roll-shaped photographing, not only can the size of the camera and the cartridge be reduced, but also resources can be saved, and the storage space for the developed negative film can be saved. , The film width is about 20 to 35 mm, preferably 20 to 35 mm.
３０30 mm. Shooting screen area is also 300-700mm
If it is in the range of about ² and preferably in the range of 400 to 600 mm ^2, the small format can be realized without deteriorating the image quality of the final photographic print, and the size of the patrone and the size of the camera can be reduced more than before. Further, the aspect ratio of the shooting screen is not limited, and the
6 size 1: 1, half size 1: 1.4,135
It can be used for various types such as (standard) size 1: 1.5, high-vision type 1: 1.8, panorama type 1: 3.

When the light-sensitive material of the present invention is used in the form of a roll, it is preferable that the light-sensitive material is housed in a cartridge. The most common cartridge is the current 135 format cartridge. Others
No. 58-67329, No. 58-195236,
JP-A-58-181035 and JP-A-58-182634
No. 4,221,479, JP-A-1-23
No. 1045, No. 2-170156, No. 2-19945
No. 1, 2-124564, 2-201441,
2-205584, 2-210346, 2-
No. 211443, No. 2-214853, No. 2-264
No. 248, No. 3-37645, No. 3-37646,
U.S. Pat. Nos. 4,846,418 and 4,848,69
Nos. 3,832,275 and the like can be used. Further, the present invention can be applied to "Small photographic roll film cartridge and film camera" in JP-A-5-210201.

[0168]

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

Example 1 A multilayer color photographic light-sensitive material sample 101 was prepared by sequentially forming layers having the following compositions from the support side on a triacetyl cellulose film support provided with an undercoat layer.

The amount of addition is expressed in grams per 1 m ² .
However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes (indicated by SD) were shown in moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV-1 0.3 CM-1 0.123 CC-1 0.044 OIL-1 0.167 Gelatin 1.33 Second Layer (Intermediate) Layer) AS-1 0.160 OIL-1 0.20 Gelatin 0.69 Third layer (low-sensitivity red-sensitive layer) Silver iodobromide a 0.20 Silver iodobromide b 0.29 SD-12 37 × 10 ^-5 SD-2 1.2 × 10 ^-4 SD-3 2.4 × 10 ^-4 SD-4 2.4 × 10 ^-6 C-1 0.20 CC-1 0.038 OIL- 2 0.28 AS-2 0.002 Gelatin 0.73 Fourth layer (medium-speed red-sensitive layer) Silver iodobromide c 0.10 EM-3 0.86 SD-1 4.5 × 10 ^{-5 SD-2 2.3 × 10 -4 SD} -3 4.5 × 10 -4 C-1 0.52 CC-1 0.06 DI-1 0.047 OI -2 0.46 AS-2 0.004 Gelatin 1.30 Fifth Layer (high sensitivity red-sensitive layer) Silver iodobromide c 0.13 EM-3 1.18 SD- 1 3.0 × 10 - ⁵ SD-2 1.5 × 10 ^-4 SD-3 3.0 × 10 ^-4 C-1 0.138 CC-1 0.036 DI-1 0.024 OIL-2 0.27 AS-20 006 Gelatin 1.28 6th layer (intermediate layer) OIL-1 0.29 AS-1 0.23 Gelatin 1.00 7th layer (low sensitivity green color sensitive layer) Silver iodobromide a 0.19 Iodine odor Silver halide b 0.062 SD-4 3.6 × 10 ^-4 SD-5 3.6 × 10 ^-4 M-1 0.14 CM-1 0.033 OIL-1 0.22 AS-2 0.002 Gelatin 0.61 Eighth layer (intermediate layer) OIL-1 0.26 AS-1 0.054 Gelatin 0.80 Ninth layer (Medium green color-sensitive layer) EM-3 0.54 iodobromide c 0.54 SD-6 1.6 × 10 -4 SD-7 1.7 × 10 -4 SD-8 1.6 × 10 -4 M-1 0.40 CM-1 0.024 CM-2 0.029 DI-2 0.024 DI-3 0.005 OIL-1 0.73 AS-2 0.003 Gelatin 1.80 10th layer (high sensitivity green color sensitivity) Layer) EM-3 1.19 Silver iodobromide c 0.22 SD-6 1.7 × 10 ^-4 SD-7 1.8 × 10 ^-4 SD-8 1.7 × 10 ^-4 M-10 0.075 CM-2 0.026 CM-1 0.022 DI-2 0.015 OIL-1 0.19 OIL-2 0.43 AS-2 0.014 Gelatin 1.23 11th layer (yellow filter layer) Yellow colloidal silver 0.05 OIL-1 0.18 AS-1 0.16 gelatin 1.00 12th layer (low sensitivity blue Color-sensitive layer) Silver iodobromide b 0.22 Silver iodobromide a 0.08 Silver iodobromide e 0.09 SD-9 6.5 × 10 ^-4 SD-10 2.5 × 10 ^-4 Y -1 0.77 DI-4 0.017 OIL-1 0.31 AS-2 0.002 Gelatin 1.29 13th layer (high-sensitivity blue-sensitive layer) Silver iodobromide e 0.41 Iodobromide Silver f 0.61 SD-9 4.4 × 10 ^-4 SD-10 1.5 × 10 ^-4 Y-1 0.23 OIL-1 0.10 AS-2 0.004 Gelatin 1.20 14th layer (First protective layer) Silver iodobromide emulsion (average particle size: 0.05 μm, silver iodide content: 2.0 mol%) 0.30 UV-1 0.055 UV-2 0.110 OIL-2 30 gelatin 1.32 15th layer (second protective layer) PM-1 0.15 PM-2 0.04 WAX-1 0.02 D-1 0.001 gelatin 0 55 displays the characteristics of the silver iodobromide below (one side length of a cube having the same volume as the average particle diameter).

Emulsion No. Average grain size (μm) Average AgI (mol%) Diameter / thickness ratio Silver iodobromide a 0.3 2.0 1.0 Silver iodobromide b 0.38 8.0 Octahedral twin silver iodobromide c 0.56 2.4 5.5 EM-3 0.70 2.4 7.2 Silver iodobromide e 0.74 3.5 6.2 Silver iodobromide f 1.0 8.0 2.0 Inventive emulsions EM-1 and EM-2 and comparative emulsion EM
The method for preparing -3 will be described below.

<< Preparation of Emulsion EM-1 of the Present Invention >> [Nucleation Step] The following reaction mother liquor (Gr-1) in a reaction vessel
The pH was adjusted to 1.96 with 1N sulfuric acid while stirring at a stirring rotation speed of 400 rpm using a mixing and stirring apparatus described in JP-A-62-160128. Thereafter, by using the double jet method, the solution (S-1) and the solution (H-1) were added at a constant flow rate for one minute to form nuclei.

(Gr-1) Alkali-treated inert gelatin (average molecular weight 100,000) 40.50 g Potassium bromide 12.40 g Finish up to 16.2 L with distilled water (S-1) 862.5 g of silver nitrate 4. Finishing to 06 L (H-1) Potassium bromide 604.5 g Finishing to 4.06 L with distilled water [Aging step] After the above nucleation step, add the (G-1) solution, and take 30 minutes to reach 60 ° C. The temperature rose. During this time, the silver potential of the emulsion in the reaction vessel (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled at 6 mV using a 2N potassium bromide solution. Subsequently, the pH was adjusted to 9.3 by adding an aqueous ammonia solution, and after further holding for 7 minutes, the pH was adjusted to 6.1 using an aqueous acetic acid solution.
The silver potential during this period was 6 m using a 2N potassium bromide solution.
V.

(G-1) Alkali-treated inert gelatin (average molecular weight 100,000) 173.9 g HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10 wt% methanol solution 5.80 ml Finished to 4.22 L with distilled water [Growth step] After the ripening step, the above (S-1) solution and the (S-1) solution were successively subjected to double jet method. (H-1) While accelerating the flow rate of the solution (the ratio of the addition flow rate at the end to the addition at the start is about 12 times)
Added in 37 minutes. After completion of the addition, the solution (G-2) was added, the stirring speed was adjusted to 550 rpm, and subsequently, while the flow rates of the solution (S-2) and the solution (H-2) were accelerated (at the time of completion) (The ratio of the addition flow rates at the start was about twice). During this time, the silver potential of the emulsion was controlled at 6 mV using a 2N potassium bromide solution. After the addition was completed, the emulsion temperature in the reaction vessel was lowered to 40 ° C. over 15 minutes. Thereafter, the solution (Z-1) and then the solution (SS) were added, the pH was adjusted to 9.3 using an aqueous potassium hydroxide solution, and iodine ions were released while aging for 4 minutes. Thereafter, the pH was adjusted to 5.0 using an aqueous acetic acid solution, and then the silver potential in the reaction vessel was adjusted to −39 mV using a 3N potassium bromide solution. 3) The solution was added for 25 minutes while accelerating the flow rate of the solution (the ratio of the addition flow rate at the end to the addition at the start was about 1.2 times).

(S-2) Silver nitrate 2.10 kg Finished to 3.53 L with distilled water (H-2) Potassium bromide 859.5 g Potassium iodide 24.45 g Finished to 2.11 L with distilled water (H-3) Potassium bromide 587.0 g Potassium iodide 8.19 g Finished to 1.42 L with distilled water (G-2) Ossein gelatin 284.9 g HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% by weight methanol solution 7.75 ml Finish up to 1.93 L with distilled water (Z-1) 83.4 g of sodium p-iodoacetamidobenzenesulfonate Make up to 1.00 L with distilled water (SS) 29.0 g of sodium sulfite Make up to 0.30 L with distilled water.

[0177] After the completion of the grain growth,
After desalting according to the method described in No. 58, gelatin was added and dispersed, and the pH was adjusted to 5.80 and pAg at 40 ° C.
Was adjusted to 8.06. EM-
Let it be 1.

From the electron micrograph of the obtained emulsion particles,
Tabular grains having an average grain size of 0.70 μm, an aspect ratio of 7.2 (60% of the total projected area), and a grain size distribution of 14.5% were confirmed.

<< Preparation of Emulsion EM-2 of the Present Invention >> This production method was the same as that of Emulsion EM-1 except that the amount of the solution (Z-1) used in the growth step was reduced to half. Invention emulsion EM-2 was prepared. From the electron micrograph of the obtained emulsion particles, tabular grains having an average particle size of 0.70 μm, an aspect ratio of 7.3 (60% of the total projected area), and a particle size distribution of 15.0% were confirmed.

The comparative emulsion EM-3 was obtained by combining (Z-1) and (SS) in the growth process of the emulsion EM-1 of the present invention.
By not adjusting the ratio of potassium bromide to potassium iodide in (H-2), the average silver iodide ratio can be further increased.
Adjustment was made so as to be the same as that of M-1 to prepare a comparative emulsion EM-3 having no dislocation line. The aspect ratio was adjusted by adjusting the silver potential during growth.

Further, silver iodobromide c, e, f (hereinafter referred to as emulsion c,
e, f) were prepared according to EM-3.

Further, silver iodobromide a and b (hereinafter also referred to as emulsions a and b) are described in JP-A-61-6643 and JP-A-61-6643.
No. 14630, No. 61-112142, No. 62-1
57024, 62-18556, 63-163
No. 451, No. 63-220238, No. 63-3112
No. 44, JP-A-3-200245 and JP-A-3-20923
No. 6, No. 5-210190, No. 5-289214,
It was prepared with reference to known methods described in JP-A-8-69064 and Japanese Patent Application No. 7-331774.

Table 8 below summarizes the analysis results of the compositions, structures, and the like of the emulsions EM-1 to EM-3.

[0184]

[Table 8]

After the above-mentioned sensitizing dyes were added to each of the above emulsions and ripened, triphenylphosphine selenide, sodium thiosulfate, chloroauric acid and potassium thiocyanate were added. Chemical sensitization was applied to optimize.

Incidentally, in addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersing aid SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, antifoggant A
F-1, AF-2, inhibitor AF-3, hardener H-1, H
-2 and the preservative Ase-1 were added.

[0187]

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[0188]

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[0189]

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[0190]

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[0191]

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[0192]

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[0193]

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[0194]

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[0195]

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Next, in the same manner as in the sample 101, the first
Two layers of DI-4, tenth layer of EM-3, M-1 and fifth
Samples 102 to 12 were prepared in the same manner as Sample 101, except that EM-3 and C-1 of the layers were replaced as shown in Tables 9 and 10.
2 was produced. Sample No. 123, 124, 125
Sample No. DI of the 10th layer of 120, 121, 122
2 was changed to 201, and DI-1 of the fifth layer was changed to 201, and it produced similarly.

The above sample No. The compound 201 of the present invention used in 102 is actually a mixture of the three regioisomers shown below.

[0198]

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When a magenta coupler represented by the general formula (2) of the present invention was used, a compound AS-3 having the following structure corresponding to 30% by weight of the coupler was dispersed and used together with the coupler.

[0200]

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The sample obtained as described above was subjected to wedge exposure with white light as a fresh sample, and subjected to the following color development treatment to measure the densities of the green and red photosensitive layers. The characteristic curve was determined.

(Evaluation of Fog / Sensitivity) From the characteristic curve obtained as described above, the minimum density (fog) and sensitivity of each sample before the running treatment were determined. The sensitivity was represented by the reciprocal of the exposure amount giving a density of fog + 0.3, and was represented by a relative value with the value of each photosensitive layer of the sample 101 being 100. The value is preferably smaller for fog and larger for sensitivity.

(Evaluation of storage stability with time) A sample obtained by storing a fresh sample in an environment of a temperature of 40 ° C. and a humidity of 80% for 8 days was used as a time-lapse sample, and the same exposure and color development processing as that of the fresh sample was performed for the time-lapse sample. Then, the characteristic curves of the green photosensitive layer and the red photosensitive layer were determined, and fog and sensitivity during storage with time were determined. The results are shown as relative values, where the value of each photosensitive layer of the fresh sample 101 is 100. It is preferable that the difference between the fresh sample and the aged sample is small.

(Evaluation of Sensitivity Fluctuation During Running Process) 35
Each sample cut to a width of mm was stored in a patrone, loaded into a camera (Konica Hexer, manufactured by Konica), photographed under appropriate exposure outdoors on a clear day, and then subjected to color development by the following processing steps. Continuous processing was performed until the cumulative replenishment amount to the tank reached 20 L. In this case, the amount of the color developing solution was 20
L. After performing this continuous process, each sample subjected to wedge exposure with white light is processed in the same manner as described above, and the characteristic curves of the green photosensitive layer and the red photosensitive layer of each sample after the running process are determined. Sensitivity variations during processing were determined. The results were shown as relative values, where the sensitivity of each sample before the running treatment was 100. The value is preferably closer to 100. The results are shown in Tables 9 and 10.

<< Reference Color Development Processing >> Processing Step Processing Time Processing Temperature Replenishment Amount * Color Development 3 min 15 sec 38 ± 0.3 ° C. 780 cc Bleaching 45 sec 38 ± 2.0 ° C. 150 cc Set 1 min 30 sec 38 ± 2.0 ° C. 830 cc Stability 60 seconds 38 ± 2.0 ° C. 830 cc Drying 1 minute 55 ± 5.0 ° C. * The replenishment amount is a value per 1 m ² of the photosensitive material.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used.

Color developer Water 800 cc Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-amino- 3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added to make 1 L, and potassium hydroxide or 20% sulfuric acid was used. And adjust the pH to 10.06.

Color developing replenisher Water 800 cc Potassium carbonate 35 g Sodium bicarbonate 3 g Potassium carbonate 5 g Sodium bromide 0.4 g Hydroxyamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxy Ethyl) aniline sulfate 6.3 g potassium hydroxide 2.0 g diethylenetriaminepentaacetic acid 3.0 g water was added to make 1 L, and the pH was adjusted to 10.18 with potassium hydroxide or 20% sulfuric acid.

Bleaching solution Water 700 cc 1,3-Diaminopropanetetraammonium iron (III) acetate 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Add water to make 1 L, and use ammonia water or glacial acetic acid. Adjust to pH 4.4.

Bleach replenisher Water 700 cc 1,3-diaminopropanetetraammonium iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g After adjusting the pH to 4.4 using aqueous ammonia or glacial acetic acid And water to make 1L.

Fixer Water 800 cc Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, add water to make 1 L.

Fixing replenisher Water 800 cc Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 using aqueous ammonia or glacial acetic acid, add water to make 1 L.

Stabilizing Solution and Stabilizing Replenisher Water 900 cc paraoctylphenyl polyoxyethylene ether (n = 10) 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 0.1 g Siloxane (L-77 manufactured by UCC) 0.1 g Aqueous ammonia 0.5 cc After adding water to make 1 L, the pH is adjusted to 8.5 using ammonia water or 50% sulfuric acid.

[0214]

[Table 9]

[0215]

[Table 10]

As is clear from the above results, the sample obtained by combining the compound represented by the general formula (1) of the present invention with the magenta coupler represented by the general formula (2) has a higher yield than the comparative sample. It can be seen that the fog is low in sensitivity, the storage stability is excellent, and the sensitivity variation during running processing is small.

The sample of the present invention in which the compound represented by the general formula (1) is combined with the cyan coupler represented by the general formula (3) has higher sensitivity and lower fog than the comparative sample, It can be seen that the sensitivity fluctuation during the running process was improved.

The sample No. As shown in FIG. 119, when the compounds (1) to (3) of the present invention were used, it was found that the compounds had higher sensitivity, storage stability with time, and less fluctuation in running processing.

Further, the sample No. As shown in Nos. 120 to 122, the silver halide emulsion of the present invention and the compound (1) of the present invention
When (3) was used, the storage stability over time was excellent, the sensitivity fluctuation during running processing was improved, and 123-1
As shown in FIG. 25, when the compound of the general formula (1) of the present invention is added to the same layer as the general formulas (2) and (3), it can be seen that the improvement is further achieved.

[0220]

According to the present invention, it is possible to provide a silver halide color photographic light-sensitive material having high sensitivity, excellent storage stability over time, and little fluctuation in sensitivity during running processing.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/035 G03C 1/035 K 7/34 7/34 7/384 7/384 F-term (reference) 2H016 BB01 BB02 BB03 BB04 BE01 BE02 BE03 BF00 BF04 BF07 BF08 BG01 BG02 BH03 BM03 BM06 2H023 BA02 BA03 BA04 BA05 CD00 CD11

Claims (6)

[Claims] 1. A silver halide color photographic light-sensitive material having a photographic constitution comprising at least one blue-sensitive layer, green-sensitive layer, red-sensitive layer and non-light-sensitive layer on a support. At least one of the photographic constituent layers contains at least one compound represented by the following general formula (1),
And at least one of the photographic constituent layers has the following general formula (2)
A silver halide color photographic material comprising at least one magenta coupler represented by the formula: Embedded image (Wherein, Y represents a yellow coupler residue capable of performing a coupling reaction with an oxidized form of a color developing agent, and T represents a 1,2, which may be substituted with a nitrogen atom at the coupling position of Y, which may have a substituent. Represents a 1,2,3-triazole skeleton which may have a substituent, S represents a sulfur atom bonded to a carbon atom of T. R ⁰ represents a substituted phenyl group or a substituted alkyl group. R ¹ represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, R ² represents an alkyl group which may have a substituent,
Represents an aryl group which may have a substituent. ) (Wherein, R ²¹ represents an arylthio group or an alkylthio group, and R ²² represents a substituted or unsubstituted aryl group.
²³ represents a substituent, n ² represents an integer of 1 to 5. n ² is 2
In the above case, R ²³ may be the same or different. ) 2. A silver halide color photographic light-sensitive material having a photographic structure comprising at least one blue light-sensitive layer, a green light-sensitive layer, a red light-sensitive layer, and a non-light-sensitive layer on a support. At least one of the photographic constituent layers contains at least one compound represented by the general formula (1), and at least one of the photographic constituent layers has a cyan coupler represented by the following general formula (3). A silver halide color photographic material comprising at least one kind. Embedded image (Wherein, R ³¹ represents an alkyl group or a cycloalkyl group;
R ³² represents a group that can be substituted on a benzene ring. n ³ is 1 to 4
Represents an integer. X ³ represents a group capable of leaving by reaction with an oxidized form of the color developing agent. ) 3. A silver halide color photographic light-sensitive material having a photographic structure comprising at least one blue light-sensitive layer, green light-sensitive layer, red light-sensitive layer, and non-light-sensitive layer on a support. Wherein at least one of the photographic constituent layers contains at least one compound represented by the general formula (1), and at least one of the photosensitive layers contains the following silver halide emulsion 1. Silver halide color photographic material. (Silver halide emulsion 1) Tabular silver halide grains having an aspect ratio of 5 or more in which the variation coefficient of the grain size of all silver halide grains is 25% or less and 50% or more of the projected area of the silver halide grains is 5% or more. And the silver iodide content on the surface of the tabular silver halide grains is larger than the average silver iodide content of the grains, and 30% or more (number ratio) of the tabular silver halide grains is the main component. A silver halide emulsion having dislocation lines in a central region and an outer peripheral region of a plane, and further having 20 or more dislocation lines per grain in the outer peripheral region. 4. The silver halide color photographic material according to claim 3, wherein the silver halide emulsion 1 is the following silver halide emulsion 2. (Silver halide emulsion 2) 50 of tabular silver halide grains
% Or more (number ratio) has dislocation lines in the central region and the peripheral region of the main plane, and the number of dislocation lines in the peripheral region is 30 or more per grain. 5. A composition comprising at least one compound represented by the general formula (1) and at least one magenta coupler represented by the general formula (2).
Or a silver halide color photographic light-sensitive material as described in 4 above. 6. The method according to claim 3, which comprises at least one compound represented by the general formula (1) and at least one cyan coupler represented by the general formula (3). The silver halide color photographic light-sensitive material described in the above.