JPH0577062B2 - - Google Patents

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a silver halide photographic light-sensitive material, and particularly to a silver halide photographic light-sensitive material which has excellent sharpness and improved processing variability.

[Conventional technology]

In recent years, the image quality of silver halide color photographic light-sensitive materials (hereinafter referred to as color light-sensitive materials) has improved significantly, but the sharpness is still not sufficient. In particular, in enlarged prints from small format negative color films (110 film, disk film, etc.), image roughness (granularity) and poor sharpness significantly reduce the level of print image quality. This is because the sharpness of negative film is not high enough to withstand high-magnification printing. Radiation (light) is reflected at the interface of media with different refractive indexes. In ordinary light-sensitive materials, reflection occurs at the interface between the protective layer and air, the interface between silver halide grains and the binder in the silver halide emulsion layer, the interface between the bottom layer and the support, the interface between the back surface of the support and air, etc. This is because the sharpness of the image is significantly impaired. Conventionally, various techniques for improving sharpness are known. One is light scattering prevention technology, and the other is edge effect improvement technology. As techniques for preventing light scattering, a method of adding a colored substance, a method of forming a thin film, etc. are known. The latter involves a significant reduction in the amount of silver coated, but results in a deterioration of graininess to reduce the number of color spots. There is also a reduction in the amount of gelatin, coupler, coupler solvent, etc. in the coating solution, but all of these methods have their limitations as they result in a decrease in coating properties and coloring density. In the former case, attempts have been made for a long time to add colored substances to suppress light scattering and improve sharpness, such as installing an antihalation layer, dyeing an emulsion layer, and installing a filter intermediate layer. On the other hand, as an edge effect improvement technology, so-called
There are methods using a DIR coupler and methods using an unsharp mask. Among these, the method using an unsharp mask has a practical limit because it may cause a decrease in sensitivity and deterioration of graininess. Many methods using DIR couplers are known and useful.
Special Publication No. 55-34933 as a DIR coupler, Japanese Patent Publication No. 34933
57-93344, U.S. Patent No. 3227554, U.S. Patent No. 3615506,
There are compounds described in 3617291 and 3701783. It is known that the sharpness can be greatly improved by using a so-called diffusive DIR compound which has an effect over a long distance.
No. 59-217932 and No. 59-131934. However, the present inventors found that when a diffusive DIR compound is used in a negative-working silver halide color photographic light-sensitive material, processing variability (especially with respect to developer pH and temperature)
It was found that the cyan coloring layer deteriorated significantly to the point where it became a practical problem, and the processing fluctuations in the cyan coloring layer were particularly large, and the cause of this was the presence of a diffusive DIR compound and a 2-equivalent cyan coupler in the photosensitive material. I found out that it is. The 2-equivalent naphthol-based cyan coupler used to form the cyan dye is, for example, a compound having a heterothio group or an arylthio group as a reactive active site substitution component in US Pat. No. 3,227,554, Although they can be used in special applications as emitting couplers, their slow dye formation rates make them impractical as image-forming couplers. In addition, compounds in which the reactive active site is substituted with a sulfonamide group, acylamino group, imide group, etc. are also disclosed in U.S. Pat.
No. 51-21828, etc. 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 JP-A-50-10135,
No. 51-108841, No. 51-110328, No. 51-146828
No. 52-51939, No. 52-55529, No. 53-
No. 45524, No. 53-47827, No. 53-39126, No. 53
-39745 etc. Compounds in which the reactive active site substitution component of the 2-equivalent coupler is an alkyloxy group and an aryloxy group are:
U.S. Patent No. 3,476,563, U.S. Patent No. 3,822,248, JP-A-1976-
No. 112038, No. 50-117422, No. 52-18315, No. 112038, No. 50-117422, No. 52-18315, No.
No. 53-52423, No. 53-105226, No. 54-14736,
No. 54-48237, No. 54-66129, No. 55-32071,
No. 55-65957, No. 56-1938, No. 56-27147,
It is described in No. 56-12643, etc. However, it has been found that the combined use of these conventional 2-equivalent cyan couplers and diffusive DIR deteriorates processing variability. Furthermore, the compound described in JP-A-60-144352 is an excellent 2-equivalent cyan coupler, but there is no suggestion of its use in combination with a diffusible DIR compound. [Object of the Invention] An object of the present invention is to provide a silver halide photographic material having excellent sharpness and improved processing variability. [Structure of the Invention] As a result of various studies to achieve the above object, the present inventors have found that the above object can be achieved by forming at least one
In a silver halide photographic light-sensitive material having an emulsion layer, a highly diffusible development inhibitor or a precursor of a development inhibitor is formed by the reaction between a cyan coupler represented by the general formula [ ] and an oxidized product of a color developing agent. It has been found that this can be achieved by a silver halide photographic material characterized by containing a compound that can be released (hereinafter referred to as a diffusible DIR compound). General formula []

[Specific structure of the invention]

In the general formula [], R ₁ is an alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, amyl group, octyl group, dodecyl group, etc.),
or represents an aryl group (eg, phenyl group, naphthyl group, etc.), and the group represented by R ₁ may have a substituent, and preferable 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, hexanesulfonamide group, octanesulfonamide group, dodecanesulfonamide group, etc.), arylsulfonamide group (e.g. benzenesulfonamide group, naphthalenesulfonamide 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,
-octylsulfamoyl group, N,N-dimethylsulfamoyl group, phenylsulfamoyl group, etc.), alkylureido groups (e.g. methylureido group, ethylureido group, etc.), arylureido groups (e.g. phenylureido group, naphthyl group), ureido group, etc.), alkyl group (e.g. methyl group, ethyl group, propyl group, octyl group, dodecyl group, etc.),
Alkoxy groups (e.g. methoxy, ethoxy,
propyloxy group, butyloxy group, octyloxy group, dodecyloxy group), amino group (e.g. methylamino group, ethylamino group, propylamino group, butylamino group, octylamino group, dodecylamino group, dimethylamino group, diethylamino group) group, anilino group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), or aryloxycarbonyl group (e.g., phenoxycarbonyl group, etc.) It is. Among these groups, particularly preferred are an acylamino group, an 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 (e.g. atoms such as fluorine, chlorine, bromine, etc.), hydroxyl groups, nitro groups, cyano groups, alkyl groups (e.g. methyl groups, ethyl groups,
Propyl group, iso-propyl group, butyl group, iso-
butyl group, sec-butyl group, tert-butyl group, pentyl group, iso-pentyl group, sec-pentyl group,
tert-pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group,
iso-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 groups (e.g. methoxy group, ethoxy group, propyloxy group, iso-propyloxy group, butoxy group, iso-butoxy group,
sec-butoxy group, tert-butoxy group, pentyloxy group, iso-pentyloxy group, tert-pentyloxy group, dodecyloxy group, etc.), aryloxy group (e.g. phenoxy group, tolyloxy group, etc.), carboxyl group, alkyloxycarbonyl group groups (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., benzoyl group, etc.) oxy group, etc.),
Alkylamino groups (e.g. ethylamino group, dimethylamino group, diethanolamino group, dodecylamino group, hexadecylamino group, etc.), arylamino groups (e.g. anilino group, naphthylamino group, etc.), alkylcarbamoyl groups (e.g. ethylcarbamoyl group) , carboxyethylcarbamoyl group, dodecylcarbamoyl group, etc.), arylcarbamoyl group (e.g., phenylcarbamoyl group, etc.),
Acylamino groups (e.g., methanamide group, dodecanamide group, hexadecanamide group, benzamide group, etc.), acyl groups (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, 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.),
Examples include arylsulfonyl groups (eg, phenylsulfonyl groups, etc.). R ₁ is preferably an alkyl group, more preferably an alkyl group substituted with a phenoxy group. R ₂ represents 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 R ₂
The alkyl group represented by may have a substituent,
Preferred substituents include the substituents for R ₁ described above. R ₂ is preferably a hydrogen atom.
However, the total number of carbon atoms including the substituents of R ₁ and R ₂ is 10 or more. The substituent represented by R _a will be described in detail in the general formula [a] below, but is preferably an acylamino group, an alkylsulfonamide group, or an arylsulfonamide group, and furthermore, at least one of these groups is
Particularly preferred is the case where the compound is substituted with 2 carboxyl groups. m is preferably 1 or 2. A preferred embodiment of the naphthol cyan dye image-forming coupler of the present invention represented by the general formula [] is represented by the following general formula [a]. General formula [a]

[Formula] [In the formula, R ₁ represents a substituted (preferably substituted with a phenoxy group) or unsubstituted alkyl group having 10 or more carbon atoms, and (Rb is an acylamino group, an alkylsulfonamide group, or an arylsulfone Represents an amide group, and R′b represents the substituent shown below.
It may represent the same group as Rb. That is, halogen atoms (e.g. atoms such as fluorine, chlorine, bromine, etc.), hydroxyl groups, nitro groups, cyano groups, alkyl groups (e.g. methyl groups, ethyl groups,
Propyl group, iso-propyl group, butyl group, iso-
butyl group, sec-butyl group, tert-butyl group, pentyl group, iso-pentyl group, sec-pentyl group,
tert-pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group,
iso-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 groups (e.g. methoxy group, ethoxy group, propyloxy group, iso-propyloxy group, butoxy group, iso-butoxy group,
sec-butoxy group, tert-butoxy group, pentyloxy group, iso-pentyloxy group, tert-pentyloxy group, dodecyloxy group, etc.), aryloxy group (e.g. phenoxy group, tolyloxy group, etc.), carboxyl group, alkyloxy Carbonyl groups (e.g. ethoxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl groups (e.g. phenoxycarbonyl group, etc.), alkylacyloxy groups (e.g. acetyloxy group,
cyclohexylcarbonyloxy group, etc.), arylacyloxy group (e.g. benzoyloxy group, etc.), alkylamino group (e.g. ethylamino group,
dimethylamino group, diethanolamino group, dodecylamino group, hexadecylamino group, etc.) arylamino group (e.g. anilino group, naphthylamino group, etc.), alkylcarbamoyl group (e.g. ethylcarbamoyl group, carboxyethylcarbamoyl group, dodecylcarbamoyl group, etc.) ), arylcarbamoyl group (e.g. phenylcarbamoyl group, etc.),
Acylamino groups (e.g., methanamide group, dodecanamide group, hexadecanamide group, benzamide group, etc.), acyl groups (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, benzylsulfamoyl 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.),
Examples include arylsulfonyl groups (eg, phenylsulfonyl groups, etc.). 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. At least one group among R ₁ , Rb, and R′b is
contains at least one carboxyl group,
Preferably, Rb contains at least one carboxyl group. The cyan coupler represented by the general formula [] can be synthesized by the method described in Japanese Patent Application No. 144352/1983. Specific examples of the cyan dye-forming coupler represented by the above general formula [] are illustrated below, but the invention is not limited thereto.

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[Chemical formula] The cyan coupler of the present invention is 1×10 ^-4 mol to 1 mol per mol of silver halide, preferably 1.0×
It can be used in a range of 10 ^-3 mol to 8×10 ^-1 mol. In the case of ordinary color light-sensitive materials, the cyan coupler of the present invention is contained in the red-sensitive silver halide emulsion layer, but if necessary, it is contained in other color-sensitive emulsion layers or non-light-sensitive hydrophilic colloid layers. You can let me. The cyan coupler of the present invention may be used in combination with other cyan couplers. That is, the red-sensitive silver halide emulsion layer containing the cyan coupler of the invention may contain a cyan coupler and/or a colored cyan coupler other than the cyan coupler of the invention. The content of cyan coupler and/or colored cyan coupler other than the present invention is based on the total amount of cyan coupler in the emulsion layer.
Preferably it is less than 90 mol%. Other cyan couplers that can be used in combination with the cyan coupler of the present invention include, for example, US Pat. No. 2,423,730
No. 2474293, No. 2801171, No. 2801171, No. 2474293, No. 2801171, No.
No. 2895826, No. 3476563, No. 3737326, No. 3758308, No. 3893044, JP-A-47-
No. 37425, No. 50-10135, No. 50-25228, No. 50
-112038, No. 50-117422, No. 50-130441, etc., and JP-A-58-98731.
The couplers described in the above publication are preferred. The cyan coupler of the present invention can be dispersed by a conventionally known oil protect dispersion method or latex dispersion method and incorporated into a photosensitive material. In the present invention, a diffusible DIR compound is one that is a development inhibitor or a compound capable of releasing a development inhibitor that is released by reaction with an oxidized form of a color developing agent and has a diffusivity of 0.34 or more as determined by the evaluation method described below. It is preferable that the diffusivity is 0.4 or more. In the present invention, diffusibility can be evaluated by the following method. Photosensitive material samples () and () consisting of layers having the following compositions on a (transparent) support were prepared. Sample (): A sample having a green-sensitive silver halide emulsion layer Spectrally sensitized to green-sensitivity silver iodobromide (silver iodide 6 mol%, average grain size 0.48 μm) and an exemplary coupler (M-
A gelatin coating solution containing 0.07 mole of 2) per mole of silver was applied.The amount of silver was 1.1 g/m ² and the amount of gelatin applied was
3.0 g/ ^m2 , and on top of that is a protective layer; containing silver iodobromide (silver iodide 2 mol%, average grain size 0.08 μm) that has not been chemically sensitized or spectrally sensitized. Apply gelatin coating solution with silver amount of 0.1g/m ² ,
It was applied so that the amount of gelatin applied was 0.8 g/m ² . Sample (): The protective layer of the above sample () with silver iodobromide removed. In addition to the above, each layer contains a gelatin hardening agent and a surfactant. Samples () and () were exposed to white light using a wedge and then processed in accordance with the processing method of Example 1 described below, except that the development time was 2 minutes and 40 seconds. The sensitivity of the sample () was adjusted to 60% (logarithmically expressed, −ΔlogE=
0.22) to which various development inhibitors were added and those to which no development inhibitor was added were used. The sensitivity of the sample () with no development inhibitor added is So, the sensitivity of the sample () is So′, the sensitivity of the sample () with the development inhibitor added is SI, and the sensitivity of the sample () is
When the sensitivity of is S, it is expressed as: Desensitization of sample () ΔSo = So'-S Desensitization of sample (V) ΔS = So-S Diffusivity = ΔS/ΔSo. However, all sensitivities were set as the logarithm (-logE) of the reciprocal of the exposure amount at the density point of fog density +0.3. The value obtained by this method was used as a measure of diffusivity. Table 1 illustrates the diffusibility of several types of development inhibitors.

【table】

[Table] The diffusible DIR compound of the present invention is represented by the following general formula. Diffusible DIR compound general formula (1) A(-Y)m In the formula, A represents a coupler component, m represents 1 or 2, and Y is bonded to the coupling position of the coupler component A to form an oxidized product of a color developing agent. represents a group that leaves by the reaction of , and represents a highly diffusible development inhibitor or a compound capable of releasing a development inhibitor. A only needs to have the properties of a coupler, and it is not necessarily necessary to create a dye by coupling. In the diffusible DIR compound general formula (1), Y represents the following general formulas (2A) to (5). Diffusible DIR compound general formula (2A)

【formula】 Diffusible DIR compound general formula (2B)

【formula】 Diffusible DIR compound general formula (2C)

【formula】 Diffusible DIR compound general formula (2D)

【formula】 Diffusible DIR compound general formula (2E)

【formula】 Diffusible DIR compound general formula (3)

【formula】 Diffusible DIR compound general formula (4)

【formula】 Diffusible DIR compound general formula (5)

[Formula] In the above general formulas (2A) to (2D) and (3), R ₁ is an alkyl group, an alkoxy group, an acylamino group, a halogen atom, an alkoxycarbonyl group, a thiazolylidenamino group, an aryloxycarbonyl group, an acyloxy group, carbamoyl group,
N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, nitro group, amino group, N-arylcarbamoyloxy group, sulfamoyl group, N-alkylcarbamoyloxy group, hydroxy group, alkoxycarbonylamino group, alkylthio group, arylthio group , represents an aryl group, a heterocyclic group, a cyano group, an alkylsulfonyl group or an aryloxycarbonylamino group. n
represents 1 or 2, and when n is 2, R ₁ may be the same or different, and the total number of carbon atoms contained in n R ₁ is 0 to 10. R ₂ in the above general formula (2E) is (2A) to (2D)
R ₁ has the same meaning, X represents an oxygen atom, a sulfur atom or a selenium atom, and in the general formula (4)
R ₂ represents an alkyl group, an aryl group or a heterocyclic group. In general formula (5), R ₃ is a hydrogen atom, an alkyl group,
represents an aryl group or a heterocyclic group, R ₄ is a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkanesulfonamide group, a cyano group, a heterocyclic group,
Represents an alkylthio group or an amino group. When R ₁ , R ₂ , R ₃ or R ₄ represents an alkyl group, it may be substituted or unsubstituted, linear or branched, or cyclic alkyl. Substituents include halogen atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, carbamoyl group, hydroxy group, alkanesulfonyl group, arylsulfonyl group, alkylthio group Or an arylthio group, etc. When R ₁ , R ₂ , R ₃ or R ₄ represents an aryl group, the aryl group may be substituted. As a substituent, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom,
Nitro group, amino group, sulfamoyl group, hydroxy group, carbamoyl group, aryloxycarbonylamino group, alkoxycarbonylamino group,
These include an acylamino group, a cyano group, and a ureido group. When R ₁ , R ₂ , R ₃ or R ₄ represents a heterocyclic group, it represents a 5- or 6-membered monocyclic ring or fused ring containing a nitrogen atom, oxygen atom, or sulfur atom as a hetero atom, and a pyridyl group, Quinolyl group, furyl group, benzothiazolyl group, oxazolyl group, imidazolyl group, thiazolyl group, triazolyl group,
It is selected from a benzotriazolyl group, an imide group, an oxazine group, etc., and these may be further substituted with the substituents listed for the aryl group. In general formulas (2E) and (4), the number of carbon atoms contained in R ₂ is 1 to 15. In the above general formula (5), the total number of carbon atoms contained in R ₃ and R ₄ is 1 to 15. In the above general formula (1), Y represents the following general formula (6). Diffusible DIR compound general formula (6) -TIME-INHIBIT In the formula, the TIME group is a group that binds to the coupling position of the coupler and can be cleaved by reaction with a color developing agent, and after being cleaved by the coupler, the INHIBIT group can be appropriately controlled. It is a group that can be released by
The INHIBIT group is a development inhibitor. In the general formula (6), the -TIME-INHIBIT group represents the following general formulas (7) to (13). Diffusible DIR compound general formula (7)

【formula】 Diffusible DIR compound general formula (8)

【formula】 Diffusible DIR compound general formula (9)

【formula】 Diffusible DIR compound general formula (10)

【formula】 Diffusible DIR compound general formula (11)

【formula】 Diffusible DIR compound general formula (12)

【formula】 Diffusible DIR compound general formula (13)

[Formula] In general formulas (7) to (13), R ₅ is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkoxycarbonyl group,
Represents anilino group, acylamino group, ureido group, cyano group, nitro group, sulfonamide group, sulfamoyl group, carbamoyl group, aryl group, carboxy group, sulfo group, hydroxy group, alkanesulfonyl group, and has the general formula (7), ( In 8), (9), (11) and (13),
represents 1 or 2, In general formulas (7), (11), (12) and (13), k represents an integer from 0 to 2, In general formulas (7), (10) and (11) , R ₆ represents an alkyl group, alkenyl group, aralkyl group, cycloalkyl group, or aryl group, and in general formulas (12) and (13), B is an oxygen atom or

[Formula] (R ₆ represents the same meaning as defined above), and the INHIBIT group is the general formula defined in general formulas (2A), (2B), (3), (4) and (5). and have the same meaning except for the number of carbon atoms. However, in general formulas (2A), (2B) and (3), the total number of carbons contained in each R ₁ in one molecule is 1 to 32, and in general formula (4), the number of carbons contained in each R ₁ in one molecule is 1 to 32. The number of carbon atoms is 1 to 32, and in the general formula (5), the total number of carbon atoms contained in R ₃ and R ₄ is 0 to 32.
It is 32. When R ₅ and R ₆ represent an alkyl group, it may be substituted or unsubstituted, chain-like or cyclic. Examples of the substituent include the substituents listed when R ₁ to R ₄ are alkyl groups. When R ₅ and R ₆ represent an aryl group, the aryl group may be substituted. As a substituent
The substituents listed when R ₁ to _{R 4} are aryl groups can be mentioned. Among the above-mentioned diffusible DIR compounds, those having leaving groups represented by general formulas (2A), (2B), (2E) to (5) are particularly preferred. The yellow image-forming coupler residue represented by A in general formula (1) includes pivaloylacetanilide type, benzoylacetanilide type, malondiester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type,
Coupler residues of malone ester monoamide type, benzothiazolylacetate type, benzoxazolyl acetamide type, benzoxazolyl acetate type, malon diester type, benzimidazolylacetamide type or benzimidazolylacetate type, included in U.S. Pat. No. 3,841,880 Coupler residues derived from heterocycle-substituted acetamides or heterocycle-substituted acetates or U.S. patents
Coupler residues derived from acylacetamides described in No. 3770446, British Patent No. 1459171, West German Patent (OLS) No. 2503099, JP-A-50-139738 or Research Disclosure No. 15737, or US Patent No. 4046574 Examples include the heterocyclic coupler residues described in . The magenta image-forming coupler residue represented by A is a coupler residue having a 5-oxo-2-pyrazoline nucleus, a pyrazolo-[1,5-a]benzimidazole nucleus, or a cyanoacetophenone type coupler residue. preferable. The cyan image-forming coupler residue represented by A is preferably a coupler residue having a phenol nucleus or an α-naphthol nucleus, or an indazolone or pyrazolotriazole coupler residue. Furthermore, the effect as a DIR coupler is the same even if the coupler does not substantially form a dye after coupling with the oxidized form of the developing agent and releasing the development inhibitor. This type of coupler residue represented by A includes U.S. Pat.
Examples include coupler residues described in No. 3632345, No. 3958993, and No. 3961959. Specific examples of the diffusible DIR compound of the present invention will be listed below, but the invention is not limited thereto.

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〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto. In all the examples below, the amount added in the silver halide photographic light-sensitive material is 1 m ² unless otherwise specified.
Shows winnings. In addition, silver halide and colloidal silver are shown in terms of silver. Example 1 On a triacetylcellulose film support,
Multilayer color photographic element sample 1 was prepared by sequentially forming each layer having the composition shown below from the support side. Sample-1 (comparison) First layer; antihalation layer (HC-1) Gelatin layer containing black colloidal silver. Second layer: Intermediate layer (IL) Gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone. 3rd layer; low sensitivity red-sensitive silver halide emulsion layer (RL
-1) Monodisperse emulsion (emulsion) consisting of AgBrI with an average grain size () of 0.30 μm and containing 6 mol% of AgI...Amount of silver coated: 1.8 g/m2 ^Sensitizing dye...6 x 10 ^-5 per mol of silver Molar sensitizing dye...1.0×10 ^-5 per mole of silver
Molscian coupler (C-1)...0.06 mol per 1 mol of silver Molscian coupler (C-2)...0.01 mol per 1 mol of silver Colored cyan coupler (CC-1)...0.003 mol per 1 mol of silver DIR compound (DIR-1)...0.0040 mol per mol of silver 4th layer; Highly sensitive red-sensitive silver halide emulsion layer (RH
-1) Monodispersed emulsion (emulsion) consisting of AgBrI with an average grain size () of 0.5 μm and containing 7.0 mol% of AgI...Amount of silver coated: 1.3 g/ ^m2 Sensitizing dye...3 x 10 ^-5 per mole of silver Molar sensitizing dye...1.0×10 ^-5 per mole of silver
Morcian coupler (C-2)...0.02 mol per mol of silver Colored cyan coupler (CC-1)...0.0015 mol per mol of silver DIR compound (DIR-1)...0.001 mol per mol of silver 5th layer: Intermediate layer (IL) Same as the 2nd layer, gelatin layer. 6th layer; low-sensitivity green-sensitive silver halide emulsion layer (GL
-1) Emulsion: Coated silver amount: 1.5 g/ ^m2 Sensitizing dye: 2.5 x 10 ^-5 per mole of silver
Molar sensitizing dye...1.2×10 ^-5 per mole of silver
Mol magenta coupler (M-1)...0.050 mol colored magenta coupler (CM-1) per 1 mol of silver...
0.009 mol per mol of silver DIR compound (DIR-1)...0.0040 mol per mol of silver 7th layer; Highly sensitive green-sensitive silver halide emulsion layer (GH
-1) Emulsion: Coated silver amount: 1.4 g/ ^m2 Sensitizing dye: 1.5 x 10 ^-5 per mole of silver
Molar sensitizing dye...1.0×10 ^-5 per mole of silver
Mol magenta coupler (M-1)...0.020 mol colored magenta coupler (CM-1) per 1 mol of silver...
0.002 mol per mol of silver DIR compound (DIR-1)...0.0010 mol per mol of silver 8th layer; Yellow filter layer (YC-1) Yellow colloidal silver and 2,5-di-t-octylhydroquinone A gelatin layer containing an emulsified dispersion of. 9th layer; low-speed blue-sensitive silver halide emulsion layer (BL
-1) Average particle size 0.48μm, containing 6 mol% AgI
Monodispersed emulsion (emulsion) consisting of AgBrI...silver coating amount 0.9g/ ^m2 Sensitizing dye V...1.3×10 ^-5 per mole of silver
Mol yellow coupler (Y-1)...0.29 mol per mol of silver 10th layer; High sensitivity blue-sensitive emulsion layer (BH-1) Average grain size 0.8 μm, contains 15 mol% of AgI
Monodisperse emulsion (emulsion) consisting of AgBrI...silver coating amount 0.5 g/ ^m2 Sensitizing dye V...1.0 x 10 ⁵ mol per mol of silver Yellow coupler (Y-1)...0.08 mol per mol of silver DIR compound (DIR-1)...0.0015 mol per mol of silver 11th layer; 1st protective layer (Pro-1) Silver iodobromide (AgI 1 mol% average grain size 0.07 μm)
...Silver coating amount 0.5g/m ² Gelatin layer 12 layer containing ultraviolet absorber UV-1, UV-2; 2nd protective layer (Pro-2) Polymethyl methacrylate particles (diameter
1.5 μm) and formalin scavenger (HS-1) In addition to the above composition, gelatin hardeners (H-1) and (H-2) and a surfactant were added to each layer. 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; anhydro-5,5'-diphenyl-
9-ethyl-3,3'-di-(3-sulfopropyl)oxacarbocyanine hydroxide sensitizing dye; anhydro-9-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

[ka]

[ka]

[ka]

【formula】

[ka]

[ka]

[ka]

【formula】

[ka]

【formula】

[Formula] H-2 [(CH ₂ = CHSO ₂ CH ₂ ) ₃ CCH ₂ SO ₂ CH ₂ CH ₂ ] ₂
NCH ₂ CH ₂ SO ₃ K Samples 2 to 22 were prepared by changing C-2 and D-1 of the third and fourth layers of Sample 1 as shown in Table 1. Samples 1 to 22 thus prepared were subjected to wedge exposure using white light and exposure using a square wave chart, and then subjected to the following development treatment.

【table】

[Color developer A]

4-amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)-aniline sulfate
4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate)
2.5g potassium hydroxide 1.0g Add water to make 1. [Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt
10.0g ammonium bromide 150.0g glacial acetic acid 10.0ml Add water to make 1, and adjust the pH using ammonia water.
= 6.0. [Fixer] Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to make 1, and adjust to PH=6.0 using acetic acid. [Stabilizer] Formalin (37% aqueous solution) 1.5ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5ml Add water to make 1. In addition to the above-mentioned composition, the color developing solution used was developer B, which was adjusted to pH=9.7 by adding H ₂ SO ₄ , and developer C, which was adjusted to pH=10.3 by adding NaOH. Red light (R) for each sample obtained
Sharpness (MTF) was measured using The results are shown in Table 2. Note that the sharpness improvement effect is based on the MTF of the dye image.
(Modulation Transfer Function) and 10
It is expressed as a relative value of MTF in lines/mm (specimen No. 1 is set as 100). In addition, relative values of color density at logE=0.0 were determined for samples that were developed by changing the pH of the color developer. (The color density when using developer A is 100)

【table】

[Table] From the results shown in Table 2, the present invention greatly improves the processing variability while maintaining the sharpness improvement effect, and the processing variation is equal to or lower than that when diffusive DIR is not used. The effect of the present invention is clear. Example 2 From Sample No. 1 of Example 1, the cyan coupler (C-2) in the third layer was changed to Exemplified Compound (17), and the DIR compound (DIR-1) in the sixth layer was changed to Exemplified Compound D-60. Sample No. 24 was prepared in exactly the same manner except for the change to Example 1, and was subjected to the same treatment as in Example 1 and evaluated in the same manner. As a result, the relative value of MTF was 138, the relative value of color density when developer B was used was 88, and the relative value of color density was 120 when developer C was used, demonstrating the effects of the present invention. I understand that.

Claims (1)

[Scope of Claims] 1. In a silver halide photographic light-sensitive material having at least one emulsion layer on a support, a cyan coupler represented by the general formula A silver halide photographic material characterized by containing a highly diffusible development inhibitor or a compound capable of releasing a development inhibitor precursor. General formula [] [Formula] [In the formula, R ₁ represents an alkyl or aryl group,
R ₂ represents a hydrogen atom or an alkyl group, and the total number of carbon atoms of R ₁ and R ₂ is 10 or more. Ra is a halogen atom, a hydroxyl group, a nitro group, a cyano group,
Alkyl group, aryl group, alkoxy group, aryloxy group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, alkylamino group, arylamino group,
represents an alkylcarbamoyl group, an arylcarbamoyl group, an acylamino group, an acyl group, an alkylthio group, an alkylsulfonyl group, an anylsulfonyl group, an alkylsulfamoyl group, an alkylsulfonamide group, or an arylsulfonamide group, and represents a development-inhibiting group or its precursor. Not included. m represents an integer of 1 to 5. At least one group among R ₁ , R ₂ , and Ra contains at least one carboxyl group. ]