JPS62195657A - Silver halide photographic sensitive material containing novel coupler - Google Patents

Abstract

PURPOSE:To improve a photosensitive material to have high sensitivity and to improve the graininess thereof by incorporating a specified cyan coupler into at least one silver halide emulsion layer, incorporating also a compd. liberating a group capable of changing photographic effect thereto. CONSTITUTION:A cyan coupler expressed by the formula I is incorporated in a silver halide emulsion layer. In the formula, R1 is alkyl or aryl group; R2 is H or alkyl group; the sum of C atoms in R1 and R2 is >=10; Z is a phenyl group. Also, a compd. capable of liberating a group for changing photographic effect by the interaction between different or same kind of groups is contained. The compd. is expressed by the formula II, wherein A is a component liberating (TIME)-Y after reacting with an oxidized body of a developing agent; n is 1, or 2; Y is an org. residue capable of changing photographic effect after it is eliminated. Since a cyan coupler and a compd. which liberates a group for changing photographic effect are contained in the photosensitive material, the graininess and the preservability for the lapse of time of the photosensitive material are improved.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide color photographic light-sensitive material, and particularly to a silver halide color photographic light-sensitive material with improved graininess and storage stability. be.

[Prior Art] Currently, higher and higher photosensitivity and image quality are desired for silver halide color photographic materials. Recently, the sensitivity of color negative photographic light-sensitive materials has been increased, but the image quality has deteriorated with the increase in sensitivity, and in particular, graininess cannot be said to be sufficiently good. Therefore, a color negative photographic material with high sensitivity and good graininess is desired.

A two-stroke cyan coupler is known as a technology that meets these requirements.

Various attempts have been made to convert naphthol-based cyan couplers conventionally used to form cyan dyes into 2-equivalent compounds.

For example, U.S. Pat. No. 3,227,554 describes compounds having a heterothio group or an arylthio group as reactive active site substitution components, but they can be used for special purposes as inhibitor-releasing couplers, but they can be used as image-forming couplers. However, it is not practical because the rate of pigment formation is slow.

In addition, the reactive active site is a sulfonamide group or acylamimu L.
Compounds substituted with imide groups etc. are also included in U.S. Patent No. 3,737,
No. 316, No. 3,458,315, JP-A-50-25
No. 228, No. 51-21828, etc., but the dye formation rate is still insufficient and the advantages of the 2-equivalent coupler cannot be fully utilized.

Furthermore, compounds in which the reactive active site is substituted with a heterocyclic oxy group, an aminocarbonyloxy group, an oxycarbonyloxy group, a sulfonyloxy group, a thiocarbonyloxy group, a carbonylcarbonyloxy group, an alkenylcarbonyloxy group, an alkynylcarbonyloxy group, etc. Also published in 1975
No. 0-10135, No. 51-108841, No. 51-
No. 110328, No. 51-146828, No. 52-5
No. 1939, No. 52-55529, No. 53-4552
No. 4, No. 53-47827, No. 53-39126,
Although it is described in No. 53-39745, etc., the dye formation rate is still insufficient and it has not been put to practical use.

The most excellent reactive active site substitution components of 2-equivalent couplers are alkyloxy groups and aryloxy groups, and some of them are in practical use. The representative ones are U.S. Patent No. 3,476.563, U.S. Patent No. 3,822,
No. 248, JP-A-50-117422, JP-A No. 52-18
No. 315, No. 53-52423, No. 53-1052
No. 26, No. 54-14736, No. 54-48237, No. 54-66129, No. 55-32071, No. 5
No. 5-65957, No. 56-1938, No. 56-2
No. 7147, No. 56-12643, No. 56-2714
No. 7, Japanese Patent Application No. 144352/1980, etc.

However, these two-function couplers have insufficient graininess and cannot be said to have sufficient heat resistance.

[Object of the Invention] An object of the present invention is to provide a silver halide color photographic material which is highly sensitive and has improved graininess and storage stability.

[Structure of the Invention] As a result of various studies, the object of the present invention is to unexpectedly find that at least one of the photosensitive silver halide emulsion layers on the support contains a cyan coupler represented by the following general formula [A]. When combined with an emulsion layer containing the cyan coupler and/or a silver halide emulsion layer having a different color sensitivity, a photographic effect is produced by the interaction between different or similar groups and/or compounds. It has been found that this can be achieved by including a mutable group and/or a compound that releases as a function of development.

General Formula [A] [In the formula, R1 represents an alkyl or aryl group, and R2 represents a hydrogen atom or an alkyl group. The total number of carbon atoms in R1 and R2 is one or more layers. Z represents an alkyl group or a phenyl group. 1 (Hereinafter referred to as the cyan coupler according to the present invention.) In the general formula [A], R1 is an alkyl group (for example, a methyl group,
the group represented by R1 may have a substituent, - Preferred substituents include the following groups.

That is, acylamino groups (e.g. methanamide group, ethanamide group, propaneamide group, butanamide group, hexaneamide group, octaneamide group, dodecanamide group, benzamide group, etc.), alkylsulfonamide groups (e.g. methanesulfonamide group, ethanesulfone group) Amide group, propanesulfonamide group, hexane sulfonamide group,
octanesulfonamide group, dodecanesulfonamide group, etc.), arylsulfonamide group (e.g. benzenesulfonamide group, naphthalesulfonamide group, etc.), carbamoyl group (e.g. methylcarbamoyl group, ethylcarbamoyl group, propylcarbamoyl group, dodecylcarbamoyl group) , phenylcarbamoyl group, etc.), sulfamoyl group (e.g. N-methylsulfamoyl group, N-ethylsulfamoyl group, N-butylsulfamoyl group, N-octylsulfamoyl group, N,N-dimethylsulfamoyl group) moyl group, phenylsulfamoyl group, etc.), alkylureido group (e.g. methylureido group, ethylureido group, etc.), arylureido group! (e.g. phenylureido group,
naphthylureido group, etc.), alkyl group (e.g. methyl group, ethyl group, propyl group, octyl group, dodecyl group, etc.)
, alkoxy groups (e.g. methoxy, ethoxy, propyloxy, butyloxy, octyloxy, dodecyloxy, etc.), amino groups (e.g. methylamim L)
ethylamino group, propylamino group, butylamino LL octylamino group, dodecylamino group, dimethylamino group,
diethylamine group, anilino group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.),
-ruoxycarbonyl group (for example, phenoxycarbonyl group, etc.). Particularly preferred among these groups are an acylamim L alkylsulfonamide group and an arylsulfonamide group.

Each of the above groups may have a substituent, and preferred examples of the substituent include the following.

That is, halogen atoms (eg, atoms such as fluorine, chlorine, bromine, etc.), hydroxyl groups, nitro groups, cyanoalkyl groups (eg, methyl, ethyl, propyl, 1so-propyl, butyl, is.

-butyl group, 5ec-butyl group, tert-butyl group,
Pentyl group, 1so-pentyl group, 5ec-pentyl group, tert-pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, 1so-
dodecyl group, cetyl group, etc.), cyanoalkyl group (e.g. cyanomethyl group, etc.), fluorinated alkyl group! ! (e.g. trifluoromethyl group, octafluorobutyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, etc.), alkoxy! (For example, methoxy group, ethoxy group, propyloxy group, iso-propyloxy group, butoxy group, 1SO
-butoxy group, 5ec-butoxy group, tert-butoxy group, pentyloxy group, 1so-pentyloxy group,
tert-pentyloxy group, dodecyloxy group, etc.>
, aryloxy group (e.g., phenoxy group, tolyloxy group, etc.), carboxyl group, alkyloxycarbonyl group (e.g., ethoxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, etc.), alkylacyloxy group (
(e.g., acetyloxy group, cyclohexylcarbonyloxy group, etc.), arylacyloxy group (e.g., benzoyloxy group, etc.), alkylamino group (e.g., ethylamino group, dimethylamino group, diethanolamim L dodecylamino group, hexadecylamino group, etc.), Arylamino groups (e.g., anilino group, naphthylamino group, etc.), alkylcarbamoyl groups (e.g., ethylcarbamoyl group, dodecylcarbamoyl group, etc.), arylcarbamoyl groups (e.g., phenylcarbamoyl group, etc.), acylamino M (e.g., methanamide group, dodecanamide group, etc.) group, hexadecaneamide group, benzamide group, etc.), acyl group (e.g. benzoyl group, pentafluorobenzoyl group, ethylcarbonyl group, propylcarbonyl group, etc.), alkylthio group (e.g. methylthio group, propylthio group,
octylthio group, dodecylthio group, etc.), alkylsulfonyl group (e.g. methylsulfonyl group, ethylsulfonyl group, octylsulfonyl group, decylsulfonyl group, dodecylsulfonyl group, etc.), alkylsulfamoyl group (e.g. ethylsulfamoyl group, pentylsulfonyl group, etc.), moyl group, dodecylsulfamoyl group, N-methylsulfamoyl group, N.N-dimethylsulfamoyl group, etc.), alkylsulfonamide group (e.g. methylsulfonamide group,
engineered tylsulfonamide group, dodecylsulfonamide group,
p-dodecyl phenylsulfonamide group, etc.), arylsulfonyl M (for example, phenylsulfonyl group, etc.), and the like.

R1 is preferably an alkyl group, more preferably an alkyl group substituted with a phenoxy group.

R2 is a hydrogen atom or an alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, amyl group, octyl group,
dodecyl group, etc.), and the alkyl group represented by R2 may have a substituent, and preferred substituents include the substituent for R1 described above. R2 is preferably a hydrogen atom. However, the total number of carbon atoms including the substituents of R1 and R2 is 10 or more.

2 is an alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, amyl group, octyl group, dodecyl group, etc.)
, or a phenyl group, and the alkyl group represented by 2 may have a substituent as shown below.

That is, halogen atoms (eg, atoms such as fluorine, chlorine, bromine, etc.), hydroxyl groups, nitro groups, cyanoalkyl groups (eg, methyl, ethyl, propyl, 1so-propyl, butyl, is.

-butyl group, 5ec-butyl group, tert-butyl group,
Pentyl group, 1so-pentyl group, 5ec-pentyl group, tert-pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, 1so-
dodecyl group, cetyl group, etc.), cyanoalkyl group (e.g. cyanomethyl group, etc.), fluorinated alkyl group (e.g. trifluoromethyl group, octafluorobutyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, etc.), alkoxy group ( For example, methoxy group, ethoxy group, β-ethoxy-ethoxy group, propyloxy group, 1so-protoxy group, butoxy group, 1so-butoxy group, 5ec-butoxy group, tert-butoxy group, pentyloxy group, 1so
-pentyloxy group, tert-pentyloxy group, dodecyloxy group, etc.), aryloxy group (e.g., phenoxy group, tolyloxy group, etc.), carboxyl group, alkyloxycarbonyl group (e.g., ethoxycarbonyl group,
dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, etc.), alkylacyloxy group (e.g., acetyloxy group, cyclohexylcarbonyloxy group, etc.), arylacyloxy group (e.g., benzoyloxy group, etc.), alkylamino group ( For example, ethylamino group, dimethylamino group, jetanolamino group, dodecylamim L hexadecylamino group, etc.), arylamino group (for example, anilino group, naphthylamino group, etc.), alkylcarbamoyl group (for example, ethylcarbamoyl group, carboxyethylcarbamoylmoyl group, etc.) (e.g., phenylcarbamoyl group, etc.), acylamino group (e.g., methanamide group, dodecanamide group, hexadecanamide group, penzamide group, etc.), acyl group (e.g., benzoyl group, pentafluorobenzoyl group, ethylcarbonyl group, propylcarbonyl group, etc.), alkylthio group (e.g. methylthio group, β-methylthio-ethylthio group, propylthio group, octylthio group, dodecylthio group, etc.), alkylsulfonyl group (e.g. methylsulfonyl group, ethylsulfony group, octylsulfonyl group, decylsulfonyl group, dodecylsulfonyl group, etc.), alkyl Sulfinyl groups (e.g. methylsulfinyl group, octylsulfinyl group, etc.), alkylsulfamoyl groups (e.g. ethylsulfamoyl group, pentylsulfamoyl group, dodecylsulfamoyl group, N-methylsulfamoyl group, N
．． N-dimethylsulfamoyl group, etc.), alkylsulfonamide group (e.g. methylsulfonamide group, ethylsulfonamide group, dodecylsulfonamide group, p-dodecylphenylsulfonamide group, etc.), arylsulfonyl group (e.g. phenylsulfonyl group, etc.) ) arylsulfinyl group (eg, phenylsulfinyl group, etc.).

Furthermore, alkoxy M (e.g. methoxy group, ethoxy group, protoyloxy group, butyloxy group, octyloxy group,
dodecyloxy group, etc.), nitro group, cyano group, formyl group, carboxyl group, hydroxyl group, amino group (e.g. methylamino group, ethylamino group, propylamine group, butylamino group, octylamino LL dodecylamine LL)
dimethylamino group, diethylamime L anilino group, etc.),
Acylamino group (e.g. methanamide group, ethanamide group, propaneamide group, butaneamide group, hexaneamide group, octaneamide group, dodecanamide group, penzamide group, etc.), alkylsulfonamide group (e.g. methanesulfonamide group, ethanesulfonamide group, propanesulfonamide group, hexane sulfonamide group, octane sulfonamide group, dodecane sulfonamide group, etc.),
Arylsulfonamide groups (e.g. benzenesulfonamide group, naphthalesulfonamide group, etc.), alkylureido groups (e.g. methylureido group, ethylureido group, etc.), arylureido groups (e.g. phenylureido group,
naphthylureido group, etc.), sulfamoyl group (e.g. N
-methylsulfamoyl group, N-ethylsulfamoyl group, N-butylsulfamoyl group, N-octylsulfamoyl group, N,N-dimethylsulfamoyl group, phenylsulfamoyl group, etc.), carbamoyl Groups (e.g. methylcarbamoyl group, ethylcarbamoyl group, lebamoyl group, phenylcarbamoyl group, etc.), alkoxycarbonyl M (e.g. methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.)
, or an aryloxycarbonyl group (for example, a phenoxycarbonyl group).

The phenyl group represented by 2 is as shown below! It may have a substituent.

That is, acylamino M (e.g. methanamide group, ethanamide group, propaneamide group, butanamide group, hexaneamide group, octaneamide group, dodecanamide group, benzamide group, etc.), alkylsulfonamide group (e.g. methanesulfonamide group, ethanesulfone group) Amide group, propanesulfonamide group, hexane sulfonamide group,
octanesulfonamide group, dodecanesulfonamide group, etc.), arylsulfonamide group (e.g. benzenesulfonamide group, naphthalesulfonamide group, etc.), carbamoyl group (e.g. methylcarbamoyl group, ethylcarbamoyl group, propylcarbamoyl group, dodecylcarbamoyl group) , phenylcarbamoyl group, etc.), sulfamoyl M (e.g. N-methylsulfamoyl group, N-ethylsulfamoyl group, N-butylsulfamoyl I, N-octylsulfamoyl group, N.N-dimethylsulfamoyl group) moyl group, phenylsulfamoyl group, etc.), alkylureido group (e.g. methylureido group, ethylureido group, etc.), arylureido group (e.g. phenylureido group,
naphthylureido group, etc.), alkyl group (e.g. methyl group, ethyl group, buOvyl group, octyl group, dodecyl group, etc.)
, alkoxy groups (e.g. methoxy, ethoxy, prooxy, butyloxy, octyloxy, dodecyloxy, etc.), amino groups (e.g. methylamim L)
ethylamine group, butylamino group, octylamino group, dodecylamine LL dimethylamim L diethylamine L anilino group, etc.), alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, butylamino group, octyloxycarbonyl group) , dodecyloxycarbonyl group, etc.), or aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.).

In the present invention, it is preferable that the alkyl group and phenyl group represented by 2 are substituted with each group shown below.

That is, it is preferable that the alkyl group represented by 2 is substituted with at least one alkylcarbonyl group, argylcarbamoyl group, alkylthio group, alkylsulfinyl group, alkylsulfonyl group, or alkoxy group, and further substituted with the above-mentioned groups. It is particularly preferred if each group is substituted with at least one carboxyl group.

On the other hand, it is preferable that the phenyl group represented by 2 is substituted with at least one acylamimu L alkylsulfonamide group or arylsulfonamide group,
Furthermore, it is particularly preferable that each of the above-mentioned groups is substituted with at least one carboxyl group.

A preferred embodiment of the naphthol cyan dye image-forming coupler represented by the general formula [A] of the present invention is the following general formula [A-
a ].

General formula [A-a] In the formula, R1 represents a substituted (preferably substituted with phenoxy group) or unsubstituted alkyl group having 10 or more carbon atoms, A represents substituted or unsubstituted alkylene Mtr, and X Bar 〇 〇 〇 H-1-〇〇-1-CONH-1-S-
It represents 1-8O-1-8O2-1 or -0-, and Ra is substituted, preferably with a carboxyl group. ),
Represents unsubstituted alkyl.

More preferably, in the general formula [A-b]b, R1 represents the same meaning as R1 in the general formula [A-a], and Rb represents an acylamino group, an alkylsulfonamide group, or an arylsulfonamide group, More preferably, each of these groups contains at least one carboxyl group. R' b may represent a substituent shown below or may represent the same group as Rb.

That is, halogen atoms (eg, atoms such as fluorine, chlorine, bromine, etc.), hydroxyl groups, nitro groups, cyanoalkyl groups (eg, methyl, ethyl, propyl, 1so-propyl, butyl, is.

-butyl group, 5ec-butyl group, tert-butyl group,
Pentyl group, 1so-pentyl group, 5ec-pentyl group, tert-pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, 1so-
dodecyl group, cetyl group, etc.), cyanoalkyl group (e.g. cyanmethyl group, etc.), fluorinated alkyl group (e.g. trifluoromethyl group, octafluorobutyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, etc.), alkoxy groups (e.g. methoxy, ethoxy, pro-propyloxy, iso-propyloxy, butoxy, 1so-
Butoxy group, 5ec-butoxy group, tert-butoxy group, pentyloxy group, 1so-pentyloxy group, t
ert-pentyloxy group, dodecyloxy group, etc.), aryloxy group (e.g., phenoxy group, tolyloxy group, etc.), carboxyl group, alkyloxycarbonyl group (
For example, ethoxycarbonyl group, dodecyloxycarbonyl group (e.g., phenoxycarbonyl group, etc.), alkylacyloxy group (e.g., acetyloxy group, cyclohexylcarbonyloxy group, etc.), arylacyloxy M (e.g., benzoyloxy group, etc.), alkylamine group (e.g. ethylamine group, dimethylamino group, dodecylamino group, hexadecylamino group, etc.), arylamino group (e.g., aniline naphthylamino group, etc.), alkylcarbamoyl! ! ! (For example, ethylcarbamoyl group, carboxyethylcarbamoyl group,
dodecylcarbamoyl group, etc.), arylcarbamoyl group (e.g., phenylcarbamoyl group, etc.), acylamino group (e.g., methanamide group, dodecanamide group, hexadecanamide group, penzamide group, etc.), acyl group (e.g., benzoyl group, pentafluorobenzoyl group, propyl group) carbonyl group, etc.) alkylthio group (e.g., methylthio group, propylthio group, octylthio group, dotesylthio group, etc.), alkylsulfonyl M (e.g., methylsulfonyl group, ethylsulfonyl group, octylsulfonyl group, decylsulfonyl group, dodecylsulfonyl group, etc.),
Alkylsulfamoyl group (e.g. ethylsulfamoyl group, pentylsulfamoyl group, dodecylsulfamoyl group, N-methylsulfamoyl group, N,N-dimethylsulfamoyl group, etc.), alkylsulfamoyl group! 3
(eg, methylsulfonamide group, ethylsulfonamide group, dodecylsulfonamide group, p-dodecylphenylsulfonamide group, etc.), arylsulfonyl group (eg, phenylsulfonyl group, etc.), and the like.

n represents 0 or an integer of 1 to 4, and when n is an integer of 2 to 4, R' b may be the same or different.

Specific examples of the cyan dye-forming coupler represented by the general formula [A] are listed below, but the invention is not limited thereto.

Below margin - N υ Dimension 0H H OCH2CONHC2H5 H OCHz CONHC2H40CHs 0CH2CONHCH2C0NHCH2COOH0H OCHz COOCF 3 N NNC'
J! 7 0CH2CH20CH2CH20H Processing Vermilion 1 Body or Less Margin In order to contain at least one cyan coupler according to the present invention in the emulsion layer, U.S. Patent No. 2,322.027
The method described in the issue is used. For example, one or more of the cyan couplers according to the present invention may be combined with dibutyl phthalate, dioctyl phthalate, triphenyl phosphate, tricresyl phosphate, phenoxyethanol, diethylene glycol monophenyl ether, jetoxyethyl phthalate, diethyl lauryl amide, dibutyl lauryl amide, etc. High-boiling organic solvents with a boiling point of 175°C or higher, or butyl acetate, methanol, ethanol, butanol, acetone, β-ethoxyethyl acetate, methoxytriglycol acetate, dioxane,
Dissolved in a low boiling point organic solvent such as fluorinated alcohol alone or in a mixed solvent, mixed with an aqueous gelatin solution containing a surfactant, emulsified and dispersed in a high-speed rotary mixer or colloid mill, and then added directly to the emulsion layer. Alternatively, after setting the emulsified dispersion, it may be shredded and the low-boiling organic solvent removed by washing with water, and then added to the emulsion. Further, substances having alkali solubility can also be added by the so-called Fischer dispersion method.

The cyan couplers according to the present invention may be used alone or in combination of two or more. It can also be used in combination with other types of cyan couplers, which will be described later.

The cyan coupler according to the present invention may be added to any layer constituting the light-sensitive material, but it is preferably added to at least one of the silver halide emulsion layers.

In the present invention, the amount of cyan coupler added according to the present invention is usually 1X10-' mole to 1 mole, preferably 1X10-2 mole to 8X1 mole per 11 moles of halogenide.
It can be used in a 0-' molar range.

Compounds that release groups and/or compounds as a function of development whose photographic behavior can be altered by interaction between different or similar groups and/or compounds associated with the silver halide emulsion layer. The compound according to the invention) is preferably represented by the following general formula (I).

General formula (I) A - (T IME > n - Y In the formula, A reacts with the oxidized developing agent, then (TIME >
represents a component that can release n-Y, n represents O or 1, and when n-i, TIME represents a component that can release Y after leaving A as TIME-Y;
represents organic residues that have the property of losing or producing photographic effects by reacting with each other after the m theory.

In general formula (I), A is a coupler residue or a hydroquinone residue, preferably a coupler residue. As the coupler residue, for example, for yellow couplers, U.S. Pat.
, No. 210, No. 2,875,057, No. 3.04
8.194, 3,265,506, 3,4
No. 47,928 and (Band ■) “Farbkupplereine L 1t
eraturubersieht ” Avfa M
Itteilung (Band II) ) 112~
Various types of yellow such as benzoylacetanilide type yellow couplers, piparoylacetanilide type yellow couplers, malonic acid diester type yellow couplers, malonic acid diamide type yellow couplers, or malonic acid ester monoamide type yellow couplers, which are described on page 126 (1961) etc. Couplers can be used.

Regarding the magenta coupler, U.S. Patent Nos. 2 and 3
No. 69,489, No. 2,343,703, No. 2,
No. 311.082, No. 2,600,788, No. 2
, No. 908,573, No. 3,062,653, No. 3,152,896, No. 3,519.429 and the above (Agf 7 Middelung (Band ■)) A
afa Mitteilung (Band I[)
) pyrazolone-based magenta couplers, indacylon-based magenta couplers, pyrazolobenzimidazole-based magenta couplers, pyrazolotriazole-based magenta couplers, etc., described in pages 126-156 (1961), etc.
Various magenta couplers can be used, such as cyanoacetophenone magenta couplers.

Furthermore, in the case of cyan couplers, U.S. Pat.
7.531, 2,423,730, 2,4
No. 74,293, No. 2,772,162, No. 2,
No. 895,826, No. 3,002,836, No. 3
, 034,892, 3,041.236 and the aforementioned Agfamiddelung (Pan t'II) (A
Ofa Mitteiluna (Band II)
), pages 156-175 (1961), can be used.

In addition to these couplers, West German patent publication tube 2,644.
The black dye-forming couplers described in No. 914 may also be used.

On the other hand, compounds that react with oxidized color developing agents such as cyclic carbonyl compounds but do not form coloring dyes can also be used as coupling components according to the present invention, and these coupling components are described in US Pat. 3
, No. 632,345, No. 3,928,041, No. 3,958,993, No. 3,961,959, and British Patent No. 861.138.

In the general formula (I>), TIME is used for the purpose of adjusting the coupling speed or the diffusivity of Y. For example, US Pat.
7-56837 etc., which releases a development inhibitor by an intramolecular nucleophilic substitution reaction, JP-A-56-
No. 114946, No. 57-154234, No. 57-1
No. 88035, No. 58-98728, No. 58-16
No. 0954, No. 58-162949, No. 58-20
No. 9736, No. 58-209737, No. 58-20
No. 9738, No. 58-209739, No. 58-209
No. 740, etc., which release a group with a development inhibiting effect by electron transfer along a conjugated chain; As shown in JP-A-52-90932, JP-A-53-29717, and JP-A-JP-A-60-60, the coupling component is capable of releasing the development inhibitor through a coupling reaction with the oxidized developing agent.
No. 7429, No. 60-185950, No. 60-214
No. 358, No. 60-218645, No. 60-2251
No. 56, No. 60-225844, No. 60-22903
No. 0, No. 60-230139, No. 60-2491
48, No. 60-249149, and the like.

In the general formula (I), Y is a photographically useful group, its precursor or a simple ll1lt radical, which can react intermolecularly after removal. Examples of such reactions include nucleophilic substitution reactions, nucleophilic addition reactions, coupling reactions, redox reactions, and the like.

The photographically useful group represented by Y and its precursor preferably have the following general formulas (B-I), (B-H), (
8-111>, (8IV), (8-v
, (B-Vl), (B-VI) and (B-
■).

Margin below G.

l L, -G, -N-N-G,. (B-■)G.

In the margin formula below, vl, v2F3, and v3 are N, G, and t, respectively.
C-G3 face up, V 4 Han-G 3, S *
taLtO, v5 represents O or N-G3,
V6 represents O*tny represents N-G+2, V8 represents N or C-G13, G1 represents a substituent, G2
represents a hydroxy group or a substituted or unsubstituted 7-mino group, G3 represents a hydrogen atom, an aryl group, or an aliphatic group, G4 represents an aryl group, and G5 represents a hydrogen atom or a developing agent oxidized after leaving Ll. G6 represents an alkoxy group, an arylamino group, an acylamino group, an aryl group, an aliphatic group, or a heterocyclic group, and G7 represents an aryl group, an aliphatic group, or a heterofMM. , G8 is a simple bond or Ll
represents an atomic group (having an aryl group, an aliphatic group, or a heterocyclic group) that connects a nitrogen atom with G9, and when v8 is a nitrogen atom, G9 represents an aliphatic group, an aryl group, or a heterocyclic group; is C-G13, an acyl group, a carbamoyl group, a sulfamoyl group, a nitro group, a cyan group,
Glo and G11 each represent a hydrogen atom, an aryl group, an aliphatic group, an acyl group, a carbamoyl group, a sulfonyl group, a sulfamoyl group, an alkoxycarbonyl group, or a sulfonyl group, and G12 represents an alkoxycarbonyl group, a sulfinyl group, or a sulfonyl group; represents an aliphatic group, aryl group, heterocyclic group or amino group,
Further, when v6 is N-G+2, G12 can combine with G7 to form a ring.

G13 represents a hydrogen atom, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, a carbamoyl group, a sulfamoyl group, a nitro group, a cyam L alkoxycarbonyl group, a sulfonyl group, or a sulfinyl group; Can form a ring. R1 is a hydrogen atom, a halogen atom, an alkoxycarbonylamine LL aliphatic hydrocarbon group, an N-arylureido group, an acylamino group, -
0-R2 or -8-R2 (where R2 represents an aliphatic hydrocarbon group), 2 represents an integer from 1 to 4, r represents an integer from ○ to 4, g and h
represents an integer from 1 to 3.

The simple leaving group represented by Y preferably has the following general formula (
B-IX) and (B-X).

7'-・L+N Zl (B-IX)
%, -, / L+ -V9-22 (B-X) In the formula, Zl represents a group of nonmetallic atoms that constitute a heterocycle together with a nitrogen atom, and v9 represents a group of K[atoms, sulfur atoms, selenium atoms, and hydrogen atoms]. Represents a monosubstituted nitrogen atom, a substituted nitrogen atom, a methylene group or a substituted methine group, and z2
represents an organic residue.

More preferably, the compound represented by general formula (1) is
It is represented by the following general formulas ([), (I[[), NV) and (V)].

General formula (II-1> A -(TIME) n -Z-E General formula (n-2> -Nl1 In the formula, A is the bond reacted with the oxidized developing agent, respectively (T
IME represents a component that can release Z-G or NO, n represents O or 1, and when n is 1, TIME represents a component that can release Z-E after leaving A as TIME-Z-E. In the expression, 2 represents the basic bone nucleus that exhibits a development inhibiting effect, E represents a component that reacts with NL+ after NU leaves, causes a nucleophilic substitution reaction, and leaves from Z; It is a group that generates a nuclear group, and represents a group that can generate Z-NIJ, which exhibits a development inhibiting effect, by reacting with Z-E. A in general formula (II-1> and A in general formula (II-2>) may be the same or different.

In general formula (II-1) and general formula (I[-2), the groups represented by A1 and TIME represent the same groups as described in general formula (I).

The group represented by E in the general formula (I[-1>) is preferably a halogen atom, an alkanesulfonyloxy group, an arylsulfonyloxy group, an aryloxy group, an acyloxy group, or an alkoxy group.

The development inhibitor basic nucleus represented by 7 in general formula (U-1) preferably represents a nitrogen-containing unsaturated heterocyclic ring, or a monocyclic or condensed ring heterocyclic thio group. In the nitrogen-containing unsaturated heterocyclic group, 8-(TIME)n- is bonded to a nitrogen atom, and the heterocyclic thio group is A-(TIME)n-
combines with the sulfur atom. These nitrogen-containing unsaturated heterocycles and heterocycle thio groups have one or more substituents,
Preferably, it is linked to E via one of its substituents.

In general formula (If-2), the group represented by NL+ preferably contains an oxygen atom, a nitrogen atom or a sulfur atom,
A group that is bonded to A through it, such as an alkoxy group, an aryloxy group, a benzotriazolyl group, a benzimidazolyl group, a triazolyl group, an imidazolyl group, an imidazolidinyl group, a pyrazolyl group, an alkylthio group, an arylthio group, or a heterocyclic group. Represents a thio group.

General formula (I [[) % formula % In the formula, A, n, TIME, Zl F3 and El are A, n of general formula (I) and general formula (n), respectively.

Represents something similar to TIME, Z, and E, and Zl
-E+ undergoes a nucleophilic substitution reaction between two molecules to produce Zl-Zl, -E+, which exhibits a development inhibiting effect.

General formula (IV-1) A - (TIME) n -22 General formula (IV-2) A-12-22 In the formula, A, n and TIME represent the same thing as described in general formula (1). , Z2 represents a development inhibitor, L2
-E2 represents a component that can undergo a bimolecular nucleophilic substitution reaction with z2, and L-E is attacked by the nucleophilic group generated in the separated 2. E2 is then separated from L2 to generate L2-22.

L2-22 does not substantially exhibit a development inhibiting effect.

In the general formula (IV-2), the group represented by L2 is a group that reacts with the oxidized developing agent to eliminate 11 from A, and preferably L2 contains an oxygen atom, a nitrogen atom, or a sulfur atom, and A group that connects with △, such as an alkoxy group, an aryloxy group, a benzotriazolyl group, a benzimidazolyl group, a triazolyl group, an imidazolyl group,
imidazolidinyl group, pyrazolyl group, alkylthio group,
Represents an arylthio group or a heterocyclic thio group. These leaving groups preferably have one or more substituents and are linked to E2 via one of the substituents.

General formula (V-1> A-(TIME)n -ED General formula (V-2) A-L3-E3 In the formula, A, n, TIME, L3 and E3 are General formula (1) and General formula, respectively. (II) and general formula (IV-
2> A, n, TfME, L2, and E represent the same groups as mentioned above, and ED contains a fogging agent or a development accelerator in the molecule, and after m removal from A or TIME, Represents a group that generates an anion and makes a nucleophilic attack on L3-63.

The L3-ED produced has virtually no photographic effect.

In general formula (V-1), ED is preferably thiourea,
Represents those derived from hydrazine, 3-pyrazolidone, rhodanine, thioamide, etc.

: Disaster 1z - Zheng Shiyo (1-1), General formula (i) Ma, Cho, Mesa Kazui (musical music A and Kinetsurishi Shio).

The following margins are CH, CH, CJ S(lHt(,,:Hz(JS(JzUHs).The following are representative examples of the compound represented by the general formula (n-2).

l CI! l Next, representative examples of the compound represented by the general formula (rV-1) will be shown.

cm8 CH.

C,=tHs CH2 Next, representative examples of compounds represented by general formulas (IV-2) and (V-2) are shown.

CH, CH, NHCCH2CJ O=Q S
.

Next, some examples of the compound represented by the general formula (V-1) will be shown.

O CH2 ■ Knee-NHNHCOCF3 CH.

CHl Any coupler of the present invention can be synthesized by a known method. General formula (II-2), General formula (IV-
1> and general formula (V-1) are known compounds, for example, British Patent No. 2,099,1
No. 67, No. 2,096,783, No. 2,072.3.
No. 63, No. 2,097,140, U.S. Patent No. 3,22
No. 7,554, No. 3,639,417 or No. 4.0
It can be synthesized by the synthetic route described in, for example, No. 63,950. Compounds included in general formula (It-1), general formula (I Can be synthesized.

A-+A-TIME-+A-TIME-Z-A-TIM
E-Z-E A-A-L-A-L-E The silver halide emulsion used in the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver halide, Any materials used in ordinary silver halide emulsions such as silver chloroiodobromide and silver chloride can be used, but silver bromide, silver iodobromide, and silver chloroiodobromide are particularly preferred. .

The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Alternatively, the halide ions and silver ions may be generated by sequentially and simultaneously adding the halide ions and silver ions while controlling the pH (11)Ag in the mixing pot, taking into account the critical growth rate of the silver halide crystals. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. Conversion methods may be used at any step in the formation of AgX to change the halogen composition of the particles.

Known silver halide solvents such as ammonia, thioether, thiourea, etc. can be present during the growth of silver halide grains.

During the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts ( Metal ions can be added using at least one selected from the following (including complex salts) to contain these metal elements inside the particles and/or on the surface of the particles, and also by placing them in an appropriate reducing atmosphere. By this, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disclosure (Research D 1s
Closure (hereinafter abbreviated as RD)) No. 17643, Section 2 can be carried out.

The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer.

The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (100) plane to the (111) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The size of silver halide grains is 0.05 to 30μ,
Preferably, those having a diameter of 0.1 to 20μ can be used.

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). A particle with a value of 0.20 or less when divided by the average grain size.The grain size is the diameter in the case of spherical silver halide, and the projection of the grain in the case of grains with a shape other than spherical. This indicates the diameter when the image is converted into a circular image with the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble metal corrosion compounds can be used alone or in combination.

Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dyes may be used alone or in combination of two or more. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographic Compounds known in the art as antifoggants or stabilizers can be added.

It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention contain one or two types of hardeners that bind binder (or protective colloid) molecules and increase film strength. By using the above, hardening can be achieved. A hardening agent can be added to the processing solution to harden the photosensitive material to the extent that it is not necessary to add the hardening agent.
It is also possible to add a hardening agent to the processing solution.

For example, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1,3,5 −)
-lyacryloyl-hexahydro-s-triazine, 1
．． 3-vinylsulfonyl-2-propatur, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-8-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. alone or Can be used in combination.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are A of Section X of RD 17643.
It is a compound described in .

A dispersion (latex) of a water-insoluble or releasable synthetic polymer can be contained in the photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material for the purpose of improving dimensional stability.

For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, ethylene, etc. alone or in combination, or these and acrylic acid, Polymers containing combinations of methacrylic acid, α, β-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulfoalkyl (meth)acrylates, styrene sulfonic acids, etc. as monomer components can be used.

The emulsion layer of the light-sensitive material contains a dye that forms a dye through a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p-phenylenediamine derivative, amine phenol derivative, etc.) during color development processing. Forming couplers are used. The dye-forming couplers are typically selected for each emulsion layer to form a dye that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even if these dye-forming couplers are tetraisotropic, in which four molecules of silver ions need to be reduced in order to form one molecule of dye, only two molecules of silver ions need to be reduced. Either bi-isomerism is acceptable. Dye-forming couplers include colored couplers that have a color correction effect and, by coupling with oxidized forms of developing agents, can be used as development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, and toning agents. Included are compounds that release photographically useful fragments, such as hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers.

Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. In place of the DIR coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a valent group, and the inhibitor is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction, which is released by the coupling reaction (timing DIR couplers, and timing DIR compounds). Furthermore, inhibitors that can be dispersed after release and those that are not so dispersible are used alone or in combination depending on the purpose. be able to. A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow coloring couplers that can be used include, for example, U.S. Patent No. 2,87
No. 5,057, No. 3.265,506, No. 3, 4
No. 08,194, No. 3,551,155, No. 3,
582,322%, same No. 3,725,072, same No. 3
, No. 891,445, West German Patent No. 1,547,868M,
West German Application No. 2,219,917, No. 2,261,3
No. 61, No. 2,414.006, British Patent No. 1,42
No. 5,020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 1977
-26133, 48-73147, 50-63
No. 41, No. 50-87650, No. 50-12334
No. 2, No. 50-130442, No. 51-21827
No. 51-102636, No. 52-82424, No. 52-115219, No. 58-95346, etc.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, virazolopentumiidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, and the like can be used.

Specific examples of magenta color-forming couplers that can be used include, for example, US Pat. Nos. 2,600,783 and 2,983,608!
, No. 3,062,653, No. 3,127,269
No. 3,311.416, No. 3,419,39
No. 1, No. 3,519,429, No. 3,558,3
No. 19, No. 3,582,322, No. 3,615.
No. 506, No. 3,834,908, No. 3,891
, 445, West German Patent No. 1,810,464, West German Patent Application (OLS) No. 2.408,665, West German Patent Application No. 2,417
, No. 945, No. 2,418,959, No. 2,424
, No. 467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 49-7
No. 4027, No. 49-74028, No. 49-129
No. 538, No. 50-60233, No. 50-1593
No. 36, No. 51-20826, No. 51-26541, No. 52-42121, No. 52-58922, No. 5
Examples include those described in Japanese Patent Application No. 3-55122 and Japanese Patent Application No. 110943/1983.

Phenol- or naphthol-based couplers are generally used as cyan dye-forming couplers. Specific examples of cyan coloring couplers that can be used in addition to those related to the present invention include U.S. Pat. No. 2,423,730, U.S. Pat.
No. 293, No. 2,801,171, No. 2,895
．． No. 826, No. 3,476.563, No. 3,73
No. 7,326, No. 3,758,308, No. 3,8
93,044 specification, JP-A-47-37425, JP-A-50-10135, JP-A-50-25228, JP-A-50-
No. 112038, No. 50-117422, No. 50-1
Those described in Publication No. 30441, etc., and those described in Japanese Patent Application Laid-open No. 5
The couplers described in Japanese Patent No. 8-98731 are preferred.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
compounds, image stabilizers, color antifoggants, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and usually boiling point 150
Dissolve in a high boiling point organic solvent of ℃ or higher using a low boiling point and/or water-soluble organic solvent as necessary, and add a surfactant to a hydrophilic binder such as an aqueous gelatin solution using a stirrer or homogenizer. After emulsification and dispersion using a dispersing means such as a colloid mill, a flow jet mixer, or an ultrasonic device, it may be added to the desired hydrophilic colloid layer.

A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high-boiling point solvents include organic compounds with a boiling point of 150°C or higher, such as phenol derivatives, phthalate alkyl esters, phosphate esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, and trimesic acid esters, which do not react with the oxidized form of the developing agent. A solvent is used.

Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of organic solvents having a low boiling point and substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene.

When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they can be used as an alkaline aqueous solution. They can also be incorporated into hydrophilic colloids.

Anionic surfactants, nonionic surfactants, Cationic surfactants and amphoteric surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsions of the light-sensitive material (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity or deterioration of sharpness. A color antifoggant can be used to prevent graininess from becoming noticeable.

The color antifoggant may be contained in the emulsion layer itself, or
An intermediate layer may be provided between adjacent emulsions FtI and contained in the intermediate layer.

An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. Compounds that can be preferably used are those described in RD No. 17643, Section 2 J.

Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials contain ultraviolet absorbers in order to prevent fogging due to discharge caused by charging of the photosensitive material due to FJ rubbing, etc., and to prevent deterioration of images due to ultraviolet rays. Good too.

In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material.

When dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer of a photosensitive material, they may be Is-dyed with a mordant such as a cationic polymer.

A development retardant and a bleach accelerator can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material.

Compounds that can be preferably used as a development retarder are the compounds described in Section XX B to D of No. 17643, and the development retardant is a compound described in Section XXI E of No. 17643. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes.

The emulsion layer of a photographic light-sensitive material is made of polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, urethane derivatives, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain urea derivatives, imidazole derivatives, and the like.

A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. Compounds which can preferably be used as optical brighteners are described in section V of RD 17643.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like.

In the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material, reduction of gloss of the light-sensitive material, improvement of writeability,
A matting agent can be added for the purpose of preventing photosensitive materials from sticking to each other. Any matting agent can be used, but examples include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resin, polycarbonate, and styrene. and copolymers thereof. The particle size of the matting agent is preferably 0.05μ to 10μ. The amount added is preferably 1 to 300 Il1g/f.

A lubricant can be added to the photosensitive material to reduce sliding friction.

An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for. Preferably used antistatic agents are the compounds described in RD 17643 X■.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material may be coated with coating properties, antistatic properties, slipperiness properties, emulsification dispersion,
Various surfactants can be used for the purpose of preventing adhesion and improving photographic properties (development acceleration, film hardening, sensitization, etc.).

The support used in the photosensitive material of the present invention includes α-olefin polymers (e.g. polyethylene, polypropylene,
Flexible reflective supports such as paper laminated with ethylene/butene copolymer), synthetic paper, etc., semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc. These include films made of , flexible supports made of these films with reflective layers, glass, metals, ceramics, etc.

After subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the photosensitive material can be used directly or to improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, etc. of the support surface.
It may be applied through one or more subbing layers to improve antihalation properties, S temperature properties, and/or other properties.

When coating the photosensitive material, a thickener may be used to improve coating properties. Also, for things like hardeners, which have quick reactivity and will cause gelation if added to the coating solution before coating, it is best to mix them using a static mixer or the like just before coating. preferable.

As coating methods, extrusion coating and curtain coating, which allow two or more types of layers to be applied simultaneously, are particularly useful, but packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected.

Examples of surfactants include, but are not limited to, natural surfactants such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkylamines, quaternary ammonium salts, pyridine, and others. Cationic surfactants such as heterocycles, phosphoniums or sulfoniums, carboxylic acids, sulfonic acids,
Anionic surfactants containing acidic groups such as phosphoric acid, sulfuric acid esters, and phosphoric acid esters; amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric acid or phosphoric acid esters of amino alcohols may be added.

Moreover, it is also possible to use a fluorine-based surfactant for the same purpose.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Perform color photo processing. Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleach solution and the process using a fixer. Alternatively, a bleach-fixing process can be carried out using a one-bath bleach-fixing solution, or a monobath processing process using a one-bath developing, bleach-fixing solution that allows color development, bleaching, and fixing to be carried out in one bath. You can also do this.

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development treatment step, an activator treatment step may be performed in which a color development drug or its precursor is contained in the material and the development treatment is performed with an activator solution, or an activator treatment step may be performed in which the monobath treatment is performed using an activator solution. Processing can be applied.

Among these processes, typical processes are shown below. (These treatments are carried out as a final step, one of a water washing process, a water washing process, and a stabilization process.) - Color development process - bleaching process - constant fixation process - color development process - bleach-fixing process Processes: Pre-hardening process - Color development process - Stop fixing process - Washing process - Bleaching process Constant fixation process - Washing process - Post-hardening process - Color development process - Washing process - Supplementary color development process - Stop process - Bleach process Constant fixation process/activator process - Bleach-fix process/Activator process - Bleach process Constant fixation process/Monobath process Processing temperature is usually 10 It is selected in the range of ℃~65℃,
The temperature may exceed 65°C. Preferably from 25°C
Processed at 45°C.

A color developing solution generally consists of an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol derivatives and p-phenylezine amine derivatives. These color developing agents can be used as salts of organic acids and non-la acids, such as hydrochloric acid, sulfur M salt, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate, etc. be able to.

These compounds are generally about 0.0% in color developer 12.
1 to about 30 a, more preferably a color developer of 12
at a concentration of about 1 to about 15 g. If the amount added is less than 0.1 g, sufficient color density cannot be obtained.

Examples of the above amine phenol developer include O-amine phenol, p-aminophenol, 5-amino-phenol,
Included are 2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like.

A particularly useful primary aromatic amine color developer is N-N'
-Dialkyl-p-phenylenediamine type compound, and the alkyl group and phenyl group may be substituted or unsubstituted. Among them, particularly useful examples include N-N'-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N+N'6-dimethyl-p-phenylenediamine hydrochloride, 2-amino -5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethyl Aminoaniline, 4-amino-3-methyl-N, N'-diethylaniline, 4-amino-N-(2-methoxyethyl)
-N-ethyl-3-methylaniline-p-toluenesulfonate and the like.

Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the above color developing agents may be incorporated into color photographic materials.

In this case, it is also possible to treat the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of a color developing solution, and the bleach-fixing process is carried out immediately after the alkaline solution treatment.

The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. It also contains various additives such as benzyl alcohol, alkali metal halides, such as potassium bromide or potassium chloride, development regulators such as citrazic acid, and preservatives such as hydroxyamines or sulfites. You may. Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide, etc. can be appropriately contained.

The pH of the color developing solution used in the present invention is usually 7 or more,
Preferably it is about 9-13.

In addition, the color developing solution used in the present invention may contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose, or Hexose, rogalol-1,
3-dimethyl ether etc. may be contained.

Various chelating agents can be used in combination as metal ion sequestering agents in the color developing solution used in the present invention. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminopentaacetic acid, 1-
Organic phosphonic acids such as hydroxyethylidene-1,1-diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphonic acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane 1,2. Examples include phosphocarboxylic acids such as 4-tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds.

The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed separately.

As bleaching agents, metal complex salts of organic acids are used, such as polycarboxylic acids, aminopolycarboxylic acids, oxalic acids, citric acids, etc., in which metal ions such as iron, cobalt, copper, etc. are coordinated. It will be done. Among the above-mentioned acids, the most preferred organic acids include polycarboxylic acids and aminopolycarboxylic acids. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and ethylenediamine-N-(β-oxyethyl).
-N, N', N' -Triacetic acid, propylene diamine tetraacetic acid, nitrilotriacetic acid, cyclohexane diamine tetraacetic acid, iminodiacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid , ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, and the like.

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

These bleaching agents are used at 5-450 g/ffi, more preferably 20-250 g/l.

In addition to the bleaching agents listed in m., the bleaching solution may also contain a sulfite salt as a preservative, if necessary. Alternatively, it may be a bleaching solution containing an ethylenediaminetetraacetate iron (, 2) complex salt bleaching agent and containing a large amount of a halide such as ammonium bromide. In addition to ammonium bromide, the halides include hydrochloric acid,
Hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like can also be used.

The bleaching solution used in the present invention includes JP-A No. 46-280, JP-B No. 45-8506, JP-B No. 46-556, Belgian Patent No. 770,910, JP-A No. 45-8836,
Various bleach accelerators described in JP-A-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

I)H of the bleaching solution is used at 2.0 or more, but generally it is used at 4.0 to 9.5, preferably 4.5 to 8.0.
and most preferably 5.0 to 7.0.

A fixer having a commonly used composition can be used. As fixing agents, compounds that react with silver halide to form water-soluble complex salts, such as those used in ordinary fixing processes, such as thiosulfates such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, and thiocyanic acid are used. Typical examples include thiocyanates such as potassium, sodium thiocyanate, and ammonium thiocyanate, thiourea, and thioether. These fixatives are 5
(It is used in an amount of 1/1 or more that can be dissolved, but generally it is used in an amount of 70 to 250 g/j!) A part of the fixing agent can be contained in the bleaching tank, or A portion of the bleaching agent may also be included in the fixing bath.

The bleaching solution and/or fixing solution may include boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. -1 buffer may be contained alone or in combination of two or more. In addition, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, or nitro alcohol, 514fl
Stabilizers such as salts, hardeners such as water-soluble aluminum salts, organic solvents such as methanol, dimethylsulfamide, dimethylsulfoxide, and the like can be contained as appropriate.

The pH of the fixer is used at 3.0 or higher, but generally it is 4.
．． 5 to 10, preferably 5 to 9.5, and most preferably 6 to 9.5.

Examples of the bleaching agent used in the bleach-fixing solution include gold complex salts of various acids described in the above bleaching process, and preferred compounds and concentrations in the processing solution are also the same as in the above bleaching process.

The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a solution containing sulfite as a preservative is applied. In addition, a bleach-fix solution consisting of an ethylenediaminetetraacetate iron (flI) complex salt bleach and a small amount of a halide such as ammonium bromide other than the above-mentioned silver halide fixer, or conversely, a halogen such as ammonium bromide may be used. A bleach-fix solution with a composition containing a large amount of a compound, and a special bleach-fix solution with a composition consisting of a combination of an ethylenediaminetetraacetate iron (I [[) complex salt bleaching agent and a large amount of a halide such as ammonium bromide, etc.] can also be used. In addition to ammonium bromide, the halides include hydrochloric acid, hydrobromic acid,
Lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like can also be used.

Examples of the silver halide fixing agent that can be included in the bleach-fixing solution include the fixing agents described in the above fixing process. The concentration of the fixing agent and the pH, I buffer and other additives that can be contained in the bleach-fixing solution are the same as in the above-mentioned fixing process.

The bleach-fix solution is used at a pH of 4.0 or higher, but is generally used at a pH of 5.0 to 9.5, preferably 6.0 to 8.
5, most preferably 6.5 to 8.5.

- [Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

In all the examples below, the amount added in the silver halide photographic light-sensitive material is per 112 unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver.

Example 1 Multilayer color photographic element sample 1 was prepared by sequentially forming layers having the compositions shown below on a triacetyl cellulose film support from the support side.

Sample-1 (comparison) IF: Antihalation layer (IC-1>gelatin layer containing black colloidal silver).

2nd Layer: Intermediate Layer (1,L,) Gelatin layer containing an emulsified dispersion of 2.5-di-t-octylhydroquinone.

3rd layer: Low sensitivity red-sensitive silver halide emulsion layer (RL~1) Average grain size (lower) 0.30 urn, Ao 16
Monodisperse emulsion (emulsion ■) consisting of Aa Sr r containing mol %...Silver coating j11.8g/f Sensitizing dye I...6X10-5 moles of sensitizing dye ■... per 1 mole of silver For 1 mole of silver 1. OX 10-5 mol cyan coupler (C-1)...0.06 mol per mol of silver Colored cyan coupler (CC-1)...0.003 mol per mol of silver DIR compound<D -2)... 0.002 mol per mol of silver 4th layer: High sensitivity red-sensitive silver halide emulsion layer (RH-1) Average grain size (bottom) 0.5 μn, Ag 17.0 mol % Monodisperse emulsion (emulsion ■) consisting of AgBr1 containing: 51 coatings @ 1.3 g /:
IJ sensitizing dye processing - 3 x 101 moles of sensitizing dye for 1 mole of silver ■... 1. OX i Q 'Morsian coupler (C-1>... 0.02 mol per mol of silver Colored cyan coupler (CC-1) -- 0.0015 mol DIR compound (D -2)... 0.001 mol per 1 mol of silver No. 5 M: Intermediate layer (1, L,) Same as No. 211, gelatin layer.

6th Notification: Low-sensitivity green-sensitive silver halide emulsion diagram (GL-1) Emulsion-1・-Coated silver Ik 1.5g/v2 Sensitizing dye ■・
- 2.5X 10-5 moles of sensitizing dye per mole of silver
... 1.2X 10-5 mole magenta coupler (M-1) for 1 mole of silver... 0.050 mole colored magenta coupler (CM-1) for 1 mole of silver... 0.009 mole DIR compound (D-1)... 0.0010 mole relative to 1 mole of silver DIR compound (D-3)... 0.0030 mole relative to 1 mole of silver 71st! : High-sensitivity aS silver halide emulsion (Gl-1
-1) Emulsion - ■... Coated silver ffi 1.4 /f Sensitizing dye ■... 1.5X 1075 moles per mole of silver Sensitizing dye ■...
... 1 mole of silver. Ox 1Q-5 mol Magenta coupler (M-1>... 0.020 mol per mol of silver Colored magenta coupler (CM-1)... 0.002 mol DIR compound (D -3) ... 0.0010 mol per mol of silver 8th layer: yellow filter layer (YC-1>gelatin layer containing yellow colloidal silver and emulsified dispersion of 2.5-di-1-octyl hydroquinone) .

, No. 9! i: Low-speed blue-sensitive silver halide emulsion layer (BL-
1> Average particle size 0.48μlI1. AU containing 16 mol% Ao
Monodispersed emulsion (emulsion ■) consisting of Br r...silver coating NO, 9 (1/1
'Sensitizing dye V... 1 JX 10-5 mol per mol of silver Yellow coupler (Y-1)... 0.29 mol per mol of silver 10th layer: Highly sensitive blue-sensitive emulsion layer ( B) l-1) AgSr containing average particle size 0.8μIII, 115 mol% AIJ
Monodisperse emulsion consisting of I (emulsion IV)...Silver coating @ 0.5Q
/f Sensitizing dye V --- Per mole of silver 1. Ox 10-5 mol Yellow coupler (Y-1)... 0.08 mol per mol of silver DIR compound (D-2)... 0.0015 mol per mol of silver 11th layer: 1 m FIJ (Pro -1) Silver iodobromide (,111 mol% average 0.07 Pro ) Silver coating amount 0
．． 5 (1/f Gelatin layer containing ultraviolet absorbers UV-1 and UV-2.

12th layer: Second protective layer (Pro-2) Gelatin layer containing polymethyl methacrylate particles (diameter 1.5 μm) and formalin scavenger (H8-1) In addition to the above composition, each layer also contains hardened gelatin. agent (H-1
), (H-2) and a surfactant were added.

The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye: Anhydro 5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide Sensitizing dye ■: Anhydro 9-ethyl-3,3'-di (
3-sulfopropyl)-4,5,4'.

5'-dibenzothiacarbocyanine hydroxide sensitizing dye ■: anhydride 5.5'-diphenyl-9-ethyl-
3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sensitizing dye■: Anhydro9-ethyl-3,3'-di(3-sulfopropyl>-5,6,5
'.

6'-Dibenzoxacarbocyanine hydroxide sensitizing dye V: Anhydro 3,3'-di(3-sulfopropyl)-4,5-benzo-5'-methoxythiacyanine Below margins Below margins 0 margins 1C-) Σ M-1 I I e V-1 C489 (S V-2 S-1 Sample-1 was prepared in this way, but Sample-2 or Sample-2 in which the cyan coupler in the third layer was changed or the compound of the present invention was added) Sample-12 was prepared.

(The contents of the prepared samples are shown in Table 1.) Below is the margin table 1. The amount of coupler and DIR compound added is the number of moles per 1T silver. Each of the obtained samples was placed at 40°C and a relative humidity of 80%. It was left for 3 weeks.

Each of the samples No. 001 to No. 12 thus prepared was subjected to wedge exposure using white light, and then subjected to the following development treatment.

Processing process (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water
Washing fixed at 3 minutes 15 seconds @
Washing with water for 6 minutes and 30 seconds Stabilization for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color developer 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.759 Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5 g Sodium bromide
1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2,5a Potassium hydroxide 1.0g Add water to make 12.

[Bleach solution 1 Ethylenediaminetetraacetic acid iron ammonium salt 100 il Ethylenediaminetetraacetic acid f12 Ammonium salt 10. OG ammonium bromide 150. Og glacial acetic acid
10.0 Add water to make the solution 12, and adjust the pH to -6.0 using aqueous ammonia.

[Fixer] Ammonium thiosulfate 175.0 LJ Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to adjust to 11, and use acetic acid to pH-e.

Adjust to.

[Stabilizer] Formalin (37% aqueous solution) 1.51f
i Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) Add 7.5 d of water to make 12.

RMS was measured for each of the obtained samples using white light (W). The results are shown in Table 2.

The F3RMS value ° is expressed as a value 1000 times the standard deviation of the variation in density value that occurs when the minimum density + 1.2 density is scanned by a microdensitometer with an aperture scanning area of 250 μf.

Regarding storage stability over time (heat resistance), each sample was left at 65°C and a relative humidity of 20% for 3 days.
A red exposure was applied through the wedge in the usual manner, followed by the development process described above, giving the results in Table 2.

In Table 2, the difference in fog values is the value obtained by subtracting the fog value of the untreated sample from the fog value of the sample after the high temperature treatment. The larger this value is, the worse the thermal stability is.

As is clear from the results in Margin Table 2 below, the inclusion of the compound of the present invention improves graininess and storage stability over time, and furthermore, in Samples Nos. 099 to 12, the graininess and storage stability over time are significantly improved. Improved. Further, graininess was also evaluated by printing, and similar effects were obtained by visual judgment.

Patent applicant Konishi Roku Photo Industry Co., Ltd. Procedural Amendment (May 16, 1985 Commissioner of the Patent Office Tuition fees Mr. Michibu I?s, -':;
.

1. Indication of the case 1985 patent application ptS378G No. 1 2. Name of the invention Silver halide photographic material containing a novel coupler 3. Person making the amendment 1. Relationship to the case Patent applicant address Shinjuku-ku, Tokyo Nishi-Shinjuku 1-26-2 Name (1
27) Konishi Roku Photo Industry Co., Ltd. Representative Director Keio Benko 4, Agent 102 Address 1-1 Kudan Kita 4-chome, Chiyoda-ku, Tokyo @ 1-1 Kudan-Rosaka Building 'I1 263-95246, Subject of amendment

Claims (1)

[Scope of Claims] At least one of the photosensitive silver halide emulsion layers on the support contains a cyan coupler represented by the following general formula [A], and the emulsion layer containing the cyan coupler and/or is Release of groups and/or compounds whose photographic behavior can be altered by interactions between different or similar groups and/or compounds in combination with silver halide emulsion layers having different color sensitivities as a function of development. A silver halide photographic material containing a compound. General formula [A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 represents an alkyl or aryl group, R_
2 represents a hydrogen atom or an alkyl group. The total number of carbon atoms of R_1 and R_2 is 10 or more. Z represents an alkyl group or a phenyl group. ]