JPS62195655A - Silver halide photographic sensitive material containing novel coupler - Google Patents

Abstract

PURPOSE:To make the sharpness of a silver halide photographic sensitive material higher and to improve the fluctuation of processability thereof by incorporating a specified cyan coupler to a silver halide emulsion layer, incorporating also a compd. capable of liberating a development inhibitor by the reaction with an oxidized body of a developing agent. CONSTITUTION:A cyan coupler expressed by the formula is incorporated into a silver halide emulsion layer, wherein R1 is alkyl or aryl; R2 is H or alkyl; the sum of C atoms in R1 and R2 is >=10; Z is a phenyl group. The cyan coupler is used in a red-sensitive emulsion. The compd. is expressed by the formula: A-(Y)m wherein A is a coupler component; m is 1 or 2; Y is a group eliminated by the reaction with a developing agent, which liberates a development inhibitor. Since a cyan coupler and a compd. liberating a development inhibitor are contained in the photosensitive material, the sharpness of the photosensitive material is improved and the fluctuation of processability is improved remarkably.

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, there has been a remarkable improvement in the image quality of silver halide color photographic materials (hereinafter referred to as color photographic materials), but their sharpness is still not satisfactory. In particular, when enlarging prints from negative-tone color films such as small film 4-matte (+10 film, disc film, etc.), image graininess and poor sharpness significantly reduce the level of print image quality. There is. 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 normal photosensitive materials, the interface between the protective layer and air,
This is because reflection occurs at the interface between the silver halide grains and the binder, the interface between the bottom layer and the support, the interface between the back surface of the support and air, etc. in the silver anodide emulsion, and the sharpness of the image is significantly impaired. be. 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 large reduction in coated silver m, but it also leads to deterioration of graininess due to the reduction in the number of color spots. There are also attempts to reduce the amount of gelatin, coupler, coupler solvent, etc. in the coating solution, but there is a limit to the reduction in coating properties and coloring density. Attempts have been made for a long time to add coloring 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 DLR (
There are methods using a 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 are known for using DrR couplers, and they are useful as Tfl couplers.
No. 34933, JP-A No. 57-93344, U.S. Patent No. 3
, No. 227,554, No. 3,615,506, No. 3,
There are compounds described in No. 617.291 and No. 3,701,783. So-called diffusive DIR, which has an effect over a particularly long distance
It is known that sharpness is greatly improved by using compounds, for example, as disclosed in JP-A-59-36249 and JP-A-59-36249.
It is described in No. 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, the processing variability (especially with respect to the pH and temperature of the developer) is greatly deteriorated.
They found that the processing variation in the cyan color-forming layer was particularly large, and that the cause of this was the presence of a diffusive DIR compound and a 2-equivalent cyan coupler in the photosensitive material. Ta. The 2 equim naphthol-based cyan couplers used to form cyan dyes are described, for example, in U.S. Pat.
．． No. 554 describes a compound having a heterothio group or an arylthio group as a reaction active site substitution component,
Although it can be used in special applications as an inhibitor-releasing coupler, its slow dye formation rate makes it impractical as an image-forming coupler. In addition, compounds in which reactive sites are substituted with sulfonamide groups, acylamino groups, imide groups, etc. are also covered by U.S. Patent No. 3,737.
, No. 316, No. 3,458,315, Japanese Unexamined Patent Publication No. 50-2
No. 5228, No. 51-21828, etc. Furthermore, 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 alkenylcarbonyloxy group, etc. The compounds are also disclosed in JP-A-50-10135, JP-A-51-108841, and JP-A-51.
No. -110328-, No. 51-146828, No. 52
-51939, 52-55529, 53-45
No. 524, 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 or an aryloxy group are disclosed in U.S. Pat.
No. 76.563, No. 3,822,248, Japanese Unexamined Patent Publication No. 1973
112038 So, No. 50-117422, No. 52-1
No. 8315, 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. 56-27
No. 147, No. 56-1.2643, etc. However, it has been found that the combined use of these conventional 2/j11 cyan couplers and the diffusive 1) T rt deteriorates the process variability. Moreover, as an excellent 2-equivalent cyan coupler, JP-A-60
-144352, but there is no suggestion of OF use with diffusible Dlr compounds. [Object of the Invention] The object of the present invention is to provide a silver halide photographic material which has excellent sharpness and has reduced processing variability. [Structure of the Invention] As a result of various studies in order to achieve the above object, the present inventors found that the above object is a silver halide photographic material having at least one emulsion layer on a support, which has the general formula [[ ]
It is characterized by containing a compound (hereinafter referred to as a diffusible DIR compound) that can release a highly diffusible development inhibitor or a precursor of a development inhibitor through the reaction between the cyan coupler represented by the formula and the oxidized form of the color phenomenon agent. It has been found that this can be achieved by using a silver halide photographic light-sensitive material. [In the formula, R represents an alkyl or aryl group, and R3 represents a hydrogen atom or an alkyl group. The total number of carbon atoms of R and R8 is 10 or more. Z represents a phenyl group. ] A combination of a diffusible DIR compound and a conventional cyan coupler and a cyan coupler of the general formula CI) according to the present invention are used, but when the diffusible DIR compound is not used, the diffusible DIR
(The cyan coupler represented by the general formula C1) is also degraded in processing variability compared to the case where neither of the cyan couplers is used, whereas the diffusible D I IN compound and the general formula [r]
It was completely unexpected that processing variability could only be improved by using both of the cyan couplers shown in the following. The present invention will be explained in more detail below. [Specific Structure of the Invention] In the general formula CI), R+ is an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group,
(naphthyl group, dodecyl group, etc.) or an aryl group (e.g. phenyl group, naphthyl group, etc.), and the group represented by R+ may have a substituent (f), and preferred substituents include:
List the groups below. I can do it. That is, acylamino groups (e.g. methanamide group, ethanamide group, propaneamide group, butanamide group, hexaneamide group, octaneamide group, dodecanamide group, penzamide group, etc.), alkylsulfonamide groups (e.g. methanesulfonamide group, ethanesulfonamide group) 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, dodenane carbamoyl 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, naphthylureido group, etc.) groups), alkyl groups (e.g. methyl group, ethyl group, propyl group, naphthyl group, dodecyl group, etc.), alkoxy groups (e.g. methoxy group, ethoxy group, propyloxy group, butyloxy group, octyloxy group, dodecyloxy group) etc.), amino groups (e.g. methylamino group, ethylamino group, propylamino group, butylamino group, octylamino group, dodecylamino group, diethylamino group, diethylamino group, anilino group, etc.), alkoxycarbonyl group (e.g. methoxycarbonyl group) ,
ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), or aryloxycarbonyl group (for example, phenoxycarbonyl group, etc.). 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 groups, 1so
-propyl group, butyl group, 1so-butyl group, 5ec-
Butyl group, tert-butyl group, heptyl group, 1so-
pentyl group, 5ec-pentyl group, tert-pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
acyl group, dodecyl group, 1sO-doacyl group, cetyl group, etc.), cyanoalkyl group (e.g. cyanomethyl group, etc.),
Fluorinated alkyl groups (e.g. trifluoromethyl group, octafluorobutyl group, etc.), aryl groups (e.g. phenyl group, octyl group, etc.), alkoxy groups (e.g. methoxy group, etkyne group, propyloxy group, 1so-propyloxy group, butoxy group, 1so-butquine 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 groups (e.g., ethoxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl groups (e.g., phenoxycarbonyl group, etc.),
Alkylacyloxy groups (e.g., acyloquine group, cyclohexylcarbonyloxy group, etc.), arylacyloxy groups (e.g., pentyloxy group, etc.), alkylamino groups (e.g., ethylamino group, dimethylamino group, jetanolamino 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, penzamide group, etc.), acyl groups (e.g., benzoyl group, pentafluorobenzoyl group, ethylcarbonyl group, propylcarbonyl group, etc.), alkylthio groups (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. ethylsulfonyl group, dodecylsulfonyl group, etc.), famoyl group, pentylsulfamoyl group, dodecylsulfamoyl group, N-methylsulfamoyl group, N,N-dimethylsulfamoyl group, etc.), alkylsulfonamide group (e.g. methylsulfonamide group, ethylsulfonamide group) group, dodecylsulfonamide group, p-
dodecyl phenylsulfonamide group, etc.), arylsulfonyl group (eg, phenylsulfonyl group, etc.), and the like. R1 is preferably an alkyl group, more preferably an alkyl group substituted with a phenoxy group. R7 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 the alkyl group represented by R3 may have a substituent. , Preferred substituents include the substituents for R1 described above. R7 is preferably a hydrogen atom. However, the total number of carbon atoms including the substituents of R and R3 is 10 or more. Z represents a phenyl group, and the phenyl group represented by Z may have a substituent as shown below. That is, acylamino groups (e.g. methanamide group, ethanamide group, propaneamide group, butanamide group, hexaneamide group, octaneamide group, dodecanamide group, penzamide group, etc.), alkylsulfonamide groups (e.g. methanesulfonamide group, ethanesulfonamide group) 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, N-
octylsulfamoyl group, N,N-dimethylsulfamoyl group, phenylsulfamoyl group, etc.), alkylureido groups (e.g. methylureido group, ethylureido group, etc.), arylureido groups (e.g. phenylureido group, naphthylureido group, etc.) groups), alkyl groups (e.g. methyl group, ethyl group, propyl group, octyl group, dodecyl group, etc.), alkoxy groups (e.g. methoxy group, ethoxy group, propyloxy group, butyloxy group, octyloxy group,
dodecyloxy group, etc.), amino group (e.g. methylamino group, ethylamino group, propylamino group, butylamino group, octylamino group, dodecylamino group, dimethylamino group, diethylamino group, anilino group, etc.), alkoxycarbonyl group ( Examples include methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), or aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.). In the present invention, it is preferable that the phenyl group represented by Z is substituted with each group shown below. It is preferable that the phenyl group represented by Z is substituted with at least one acylamino group, alkylsulfonamide group or arylsulfonamide group, and each of the above groups is further substituted with at least 61 carboxyl groups. It is particularly preferable that the A preferred embodiment of the naphthol cyan dye image-forming coupler represented by the general formula [I] of the present invention is the following general formula ([a
). [In the formula, R represents a substituted (preferably substituted with a phenoxy group) or unsubstituted alkyl group having 10 or more carbon atoms, (Rb represents an acylamino group, an alkylsulfonamide group, or an arylsulfonamide group) represents, R' b
may represent a substituent shown below or 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 groups, 1so
-propyl group, butyl group, 1so-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 groups (e.g. trifluoromethyl group, octafluorobutyl group, etc.), aryl groups (e.g. phenyl group, naphthyl group, etc.), alkoxy groups (e.g. methoxy group, etkyne group, propyloxy group, 1so-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., phenoquine group, tolyloxy group, etc.), NJMk:
/ It/K? +1/A It/-#
#:/-? t ILJ j +I, Kr
(for example, ethoxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, etc.), alkylacyloxy group (e.g., acetyloxy group, cyclohexylcarbonyloxy group, etc.), alkylacyloxy group (e.g., benzoyloxy group, etc.) ), alkylamino groups (e.g. ethylamino group, dimethylamino group, jetanolamino group, dodecylamino group, hexadecylamino group, etc.), arylamino groups (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 group (e.g. methanamide group, dodecanamide group, hexadecanamide group, penzamide group, etc.) , acyl groups (e.g. benzoyl group, pentafluorobenzoyl group, ethylcarbonyl group, propylcarbonyl group, etc.), alkylthio groups (e.g. medildio group, propylthio group, octylthio group, dodecylthio group, etc.), alkylsulfonyl groups (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) famoyl, etc.), alkylsulfonamide groups (e.g., methylsulfonamide group, ethylsulfonamide group, dodecylsulfonamide group, p-dodecyl phenylsulfonamide group, etc.), arylsulfonyl groups (e.g., phenylsulfonyl group, etc.), etc. be able to. 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. It is preferable that at least one group among R, Rb, and R'b contains at least one carboxyl group, and more preferably Rh contains at least one carboxyl group. be. The cyan coupler represented by the general formula [I] is
It can be synthesized by the method described in No. 144352. Specific examples of the cyan dye-forming coupler represented by the general formula [■] are shown below, but the invention is not limited thereto. (r) Llt H IJ (■4) nH NIIrMl+,. nl-1 n+1 N111;OL;1ItL;1ltU○011IT υC1+, ni II, ni IJUII0■ N41L: (J ni II Ullt
υshi11 = UILIJIJtl crystal OH Nawate C,, I+□ N11shishishi lhL;1huLlsu11Nsu2 The cyan coupler of the present invention has lX per mole of silver halide.
It can be used in a range of 10' mol to 1 mol, preferably 1.0X10' mol to 8XIO' 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 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 i'+'i of cyan couplers and/or colored cyan couplers other than those of the present invention is preferably less than 90 mo 1% of the total amount of cyan couplers in the emulsion layer. Other cyan couplers that can be used in combination with the cyan coupler of the present invention include, for example, U.S. Patent No. 2,423,730;
Same No. 2,474,293, Same No. 2.1101,171
No. 2゜895.826, No. 3,476.56
No. 3, No. 3,737,326, No. 3,758,3
No. 08, Specification No. 3,893,044, JP-A No. 4
No. 7-37425, No. 50-1.0135, No. 50-
No. 25228, No. 50-112038, No. 50-11
Couplers described in Japanese Patent Application No. 7422, No. 50-130441, etc., and especially those described in 1fl Publication No. 1987-987:H are preferred. The cyan coupler of the present invention can be dispersed by the conventionally known oil protect dispersion or latex dispersion method and incorporated into the sensitive material. In the present invention, a diffusible DIR compound is a development inhibitor or a compound capable of releasing a development inhibitor that is released by reaction with an oxidized product of a color developing agent, and has a diffusivity of 0.34 or more according to the evaluation method described below. It has a diffusivity of 0.
4 or more are preferred. In the present invention, diffusibility can be evaluated by the following method. Photosensitive material samples (I) and (II) consisting of a (transparent) support and layers having the following compositions were prepared. Sample (I): 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 exemplary coupler (M-2). silver 1
A gelatin coating solution containing 0.07 mol per mole was applied, the amount of silver coated was 1.1 g/I11", and the amount of gelatin applied was 3.09/
Silver iodobromide (silver iodide 2 mol %) which has not been chemically or spectral sensitized.
A gelatin coating solution containing particles having an average particle size of 0.08 μm was coated so that the amount of silver coated was 0.19/m'' and the amount of gelatin applied was 81F/m''. Sample (U) 2 The protective layer of the above sample (1) except that silver iodobromide was removed. In addition to the above, each layer contains a gelatin hardening agent and a surfactant. After exposing samples (1) and (ff) to white light using a wedge,
The processing was carried out in accordance with the processing method of Example 1 described later, except that the development time was 2 minutes and 40 seconds. The sensitivity of sample (II) was 60% (logarithmically expressed, -Δlog E = 0.22) in the developing solution.
) Various types of development inhibitors were used: one containing an agent I and one containing no development inhibitor. The sensitivity of sample (1) with no development inhibitor added is So, the sensitivity of sample (II) is So', the sensitivity of sample (1) with development inhibitor added is Sl, and the sensitivity of sample (II) is s
When n, the desensitization of the sample (IV) Δ5o=So′ −Sn The desensitization of the sample (V) Δ5=So−Sl Diffusivity=ΔS/ΔSO. However, all sensitivities were set as the logarithm (-1ogE) 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. The diffusible DIR compound of the present invention has the following general formula. Diffusible DIR compound general formula (1) 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 and released by reaction with the oxidized product of the color developing agent. 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. Diffusible Dlr (In compound general formula (1), Y represents the following general formulas (2A) to (5). Diffusible DIR compound general formula (2A) Diffusible DIR compound general formula (2B) Diffusible DIR compound general formula (2C) General formula of diffusible DIR compound (2D) General formula of diffusible DIR compound (2E) (X; O, S or Se) General formula of diffusible DIR compound (3) General formula of diffusible DIR compound (4) R7 Diffusion DIR compound general formula (5) In the above general formulas (2A) to (2D) and (3),
R3 is an alkyl group, an alkoxy group, an acylamino group, a halogen atom, an alkoxycarbonyl group, a thiazolylideneamino group, an aryloxycarbonyl group, an acyloxy group, a carbamoyl group, an 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, aryl group, heterocyclic group , represents a cyano group, an alkylsulfonyl group or an aryloxycarbonylamino group. n represents 1 or 2, and when n is 2, the RIs may be the same or different, and the total number of carbons contained in the n RIs is 0 to 1O. R7 in the above general formula (2E) is R8 in (2A) to (2D)
, X represents an oxygen atom, a sulfur atom, or a selenium atom, and in the general formula (4), R1 represents an alkyl group, an aryl group, or a heterocyclic group. In general formula (5), R3 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R4 represents a hydrogen atom, an alkyl group, an aryl group, a 7% logean atom, an acylamino group, an alkoxycarbonylamino group, or an aryloxycarbonyl group. It represents an amino group, an alkanesulfonamide group, a cyano group, a heterocyclic group, an alkylthio group, or an amino group. When R7, R3 or R4 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,
Examples include carbamoyl group, hydroxy group, alkanesulfonyl group, arylsulfonyl group, alkylthio group, and arylthio group. When R4, such as R1, R7, and R3, represents an aryl group, the aryl group may be substituted. As substituents, alkyl groups, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, halogen atoms, nitro groups, amino groups,
Examples include sulfamoyl group, hydroxy group, carbamoyl group, aryloxycarbonylamino group, alkoxycarbonylamino group, acylamino group, cyano group, and ureido group. When R=, Ra or R4 represents a heterocyclic group, it represents a fused ring or a 5- or 6-membered monocyclic ring containing a nitrogen atom, oxygen atom, or sulfur atom as a heteroatom,
Pyridyl group, quinolyl group, furyl group, benzothiazolyl group, oxacylyl group, imidazolyl group, thiazolyl group,
It is selected from a triazolyl group, 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 R7 is 1 to 15. In the above general formula (5), the total number of carbon atoms contained in R3 and R4 is 1 to 15. In the above general formula (1), Y represents the following general formula (6). Diffusible DIR Compound General Formula (6) % Formula % ([ In the formula, the TIME bracket is bonded to the coupling position of the coupler,
It is a group that can be cleaved by reaction with a color developing agent, and is a group that can release the INIII[31T group in a moderately controlled manner after being cleaved from the coupler. The INHIBIT group is a development inhibitor. In general formula (6), -TIMP and -IN old and old T groups represent the following general formulas (7) to (13). Diffusible DIR compound general formula (7) Diffusible DIR compound general formula (8) Diffusible D I Tl compound general formula (9) Diffusible DIR compound general formula (10) O Diffusible DIR compound general formula ( 11) Diffusible DIR compound general formula (12) Diffusible DIR compound general formula (13) In general formulas (7) to (13), R6 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aralkyl group, an alkoxy group. , alkoxycarbonyl group, anilino group, acylamino group, ureido group, cyano group, nitro group,
Represents a sulfonamide group, sulfamoyl group, carbamoyl group, aryl group, carboxy group, sulfo group, hydroxy group, alkanesulfonyl group, and has general formulas (7), (8), (9), (11) and (13).
), a represents 1 or 2, and in general formulas (7), (11), (12) and (13), k represents an integer from 0 to 2, and in general formulas (7), (10) and In (11), R,
represents an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, or an aryl group, and in the general formulas (12) and (13), B represents an oxygen atom. ), and the INIIIBIT group has the general formula (2A), (2B),
It has the same meaning as the general formula defined in (3), (4) and (5) except for the number of carbon atoms. However, in general formulas (2A), (2B), and (3), the total number of carbon atoms contained in R in the middle of the molecule is 1 to
32, and in the general formula (4), the number of carbon atoms contained in R3 is 1 to 32, and in the general formula (5), the total number of carbon atoms contained in R5 and R4 is 0 to 32. When R6 and R8 represent an alkyl group, it may be substituted or unsubstituted, chain-like or cyclic. Examples of the substituent include the substituents listed when R4 is an alkyl group. When R5 and R11 represent an aryl group, the aryl group may be substituted. Examples include the substituents listed for the aryl group. Among the above diffusible DIR compounds, those having a general formula % filtration leaving group are particularly preferred. A yellow color image represented by A in the general formula (1) Forming coupler residues include pivaloylacetanilide type, benzoylacetanilide type, malondiester type,
malondiamide type, dibenzoylmethane type, benzodepyrylacetamide type, malon ester monoamide type,
Benzothiazolylacetate type, benzoxacylylacetamide type°, benzoxacylylacetate type, malon diester type, benzimidazolylacetamide type, likely benzimidazolylacetate type coupler residue, included in U.S. Patent No. 3,841,880 Coupler residues derived from heterocycle-substituted acetamides or heterocycle-substituted acetates or U.S. Pat. No. 3,770,446
No. 1,459,171, West German Patent (OLS)
)2.503,099, JP-A-50-139738 or Research Disclosure No. 15737, etc., coupler residues derived from acylacetamides, or heterocycles as described in U.S. Pat. No. 4,046,574. type coupler residues, etc. The magenta image-forming coupler residue represented by A includes 5-oxo-2-pyrazoline nucleus, pyrazolo-[1,5-
a] Coupler residues having a benzimidazole core or an anoacetophenone type coupler residue are preferred. 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 indacylon 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 is described in U.S. Pat.
, No. 213, No. 4,088,491, No. 3,632,
No. 345, No. 3,958,993 or No. 3,981.
Examples include the coupler residues described in No. 959. Specific examples of the diffusible DIR compound of the present invention will be listed below, but the invention is not limited thereto. [Exemplary Compound] I13 ■)-7 is Q 11+1 D-19 D-20 C,211,,0cOc)IcOOc, ,)! ,. D-32 D-33 4~D 40 CyHs D”' C+, 1ltsO2 O3 D-54 J5 These compounds are described in U.S. Pat.
, 227.554, 3,617,291, 3,
No. 958,993, No. 4,149.886, No. 3,9
No. 33,500, Japanese Patent Publication No. 57-56837, Special Publication No. 5
1-13239, British Patent No. 2,072,363, British Patent No. 2,070°266, Research Disclosure-1
It can be easily synthesized by the method described in No. 21228, December 981, etc. The DIR compounds of the present invention are usually 1/mol silver halide.
X 10-" mol to 5 X 10-" mol, preferably 1X10-' to IX 10-' mol. In the light-sensitive material of the present invention, a DIR compound that does not have much diffusivity can be used together with the above-mentioned diffusive DIR compound. The DIR compound of the present invention may be contained in the same color-sensitive layer as the cyan coupler of the present invention or may be contained in a different color-sensitive layer, but is preferably used in the same color-sensitive layer. This is the case when the layer having the same color sensitivity contains two layers having different sensitivity.
If it consists of more than one layer, is it the dawn in the direction of F'+fNyjZ? - Thick Suner Mb on the right side - The layer structure preferably used in the present invention is, from the side closest to the support, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a blue-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer. When the structure is in the order of the silver anoride emulsion diagram (so-called sequential structure), or when the layer structure is reversed (Japanese Patent Application No. 193609/1989,
(described in No. 59-202065). In the case of a forward layer structure, the same color-sensitive layer may consist of two or more layers with different sensitivities, and in the case of a reverse layer structure, the same color-sensitive layers may consist of three or more layers with different sensitivities. It may consist of In addition, a non-photosensitive hydrophilic colloid layer may be provided between the photosensitive silver emulsion layers, and in particular, the non-photosensitive hydrophilic colloid layer may be provided between the photosensitive silver emulsion layers having different color sensitivities. It is preferable to provide Furthermore, it is preferable to provide an S ration prevention layer, a filter layer, and a protective layer. The /-lambda silver roanide emulsion used in the present invention includes conventional silver roanides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, and silver chloride. Any of those used in silver anion emulsions can be used, but
In particular, silver bromide, silver iodobromide, and silver chloroiodobromide are 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. Further, while taking into account the critical growth rate of the noroanide crystal, the noroanide ion and silver ion may be generated by sequentially and simultaneously adding the noroanide ion and silver ion while controlling p)l and pΔg in the mixing tank. 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 ΔgX to change the halogen composition of the particles. Known silver halide agents such as ammonia, thioether, thiourea, etc. can be present during the growth of silver halide grains. C [J Silver anodide grains contain cadmium salt, ;tb, lead salt, lead salt, thallium salt, iridium salt (including complex salts), rhodium salt (complex salt), These metal elements can be added inside the particles and/or on the surface of the particles by adding metal ions using at least IN selected from iron salts (including complex salts) and iron salts (including complex salts). A reduction sensitizing solution can be applied to the inside of the particles and/or to the surface of the particles by placing the particles in a positive atmosphere. 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, use a reservoir disk [J jar (Rcs-carch Di
sclosure (hereinafter abbreviated as It D) No. 17643 ■
This can be done based on the method described in Section 1. C (J silver annide grains may have a uniform silver halide composition distribution within the grain, or C (J silver annide grains may have a different silver halide composition in the interior and surface layer of the grain. The silver halide grains may be grains in which latent images are mainly formed on the surface, or grains in which the latent image is mainly formed inside the grains. They may have regular crystal shapes such as a hedron or tetradecahedron, or they may have irregular crystal shapes such as a sphere or a plate. In these particles, the (100) plane and ( 111) Any ratio can be used.Also, particles having a composite form of these crystal forms may be used, or particles of various crystal forms may be mixed.The grain size of the silver halide grains is 0. .05-30
μ, preferably 0.1 to 20 μ can be used. The silver halide emulsion 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 polydisperse emulsion) may be used. When the standard deviation is divided by NV - average grain size, the value is 0.20 or less.Here, i, 7 diameter is the diameter for spherical silver halide, and for shapes other than spherical. (1: f, in the case of a child, indicates the diameter when its projected image is converted into a circular image of the same area) may be used alone or in combination. Further, a polydisperse emulsion and a polydisperse emulsion may be used in combination. 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 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 dye may be used alone, but 2'! T
! , the above may be used in combination. 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 may be used. Particularly useful pigments include cyanine pigments, melonanine pigments,
and a complex melonanine 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. Binder (or protective colloid) for silver halide emulsions
Although it is advantageous to use gelatin, gelatin derivatives, graft polymers of gelatin and other polymers,
Hydrophilic colloids such as other proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used. Photographic emulsion layers and other hydrophilic colloid layers of light-sensitive materials using silver halide emulsions should use one or more hardening agents that crosslink binder (or protective colloid) molecules and increase film strength. It can go up to the dura mater. The hardening agent can be added in an amount capable of hardening the photosensitive material to such an extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution. For example, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-medilol compounds (dimedylorurea, methyloldimethylhydantoin, 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 the compounds described in RD 17643, section 2, A. The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer 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, styrene, etc. alone or in combination, or these and acrylic acid, A polymer containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used. The magenta and yellow dye-forming couplers used in the present invention desirably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, these dye-forming couplers are 4-isoh, which requires reduction of four molecules of silver ions in order to form one molecule of dye.
Even if it is l-character, it may be di-isojil, which only requires that two molecules of silver ions are reduced. The dye-forming coupler is a colored coupler that has a color correction effect and a development accelerator by coupling with an oxidized form of a developing agent.
Photographically useful fragments such as bleach accelerators, developers, silver halide solvents, toning agents, hardeners, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and sensitizers. Compounds that release . Colorless couplers (also referred to as competitive couplers) that undergo a coupling reaction with the oxidized product of the aromatic primary amine developer but do not form dyes can be used in combination with dye-forming couplers. 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 couplers that can be used include, for example, U.S. Patent No. 2,87
No. 5,057, No. 3,265.506, No. 3,4
08゜194, same No. 3.551.155, same No. 3,
No. 582,322, No. 3,725.072, No. 3
, 891°445, West German Patent No. 1,547,868,
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, 4g-73147, 50-63
No. 41, No. 50-87650, No. 50-123342
No. 50-130442, No. 51-21827,
No. 51-102636, No. 52-82424, No. 5
It is described in No. 2-115219, No. 58-95346, etc. As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain anruacetonitrile couplers, indacylon couplers, and the like can be used. Specific examples of magenta coloring couplers that can be used include, for example, U.S. Pat. Nos. 2,600,788 and 2,983,608
No. 3,062,653, No. 3,127.26
No. 9, No. 3.311.476, No. 3,419,3
No. 91, No. 3,519,429, No. 3゜558.
No. 319, No. 3,582,322, No. 3,615
, No. 506, No. 3,834.908, No. 3,89
1,445, West German Patent Application 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. 49-74
No. 027, No. 49-74028, No. 49-12953
No. 8, No. 50-60233, No. 50-159336, No. 51-20826, No. 51-2 [) No. 541, No. 52-42121, No. 52-58922, No. 53-
55122, Japanese Patent Application No. 55-110943, and the like. No need to adsorb onto silver halide crystal surface 1 Dye-forming puller, colored coupler, DIR coupler, D[
Among R compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc., hydrophobic compounds can be treated using various methods such as solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method, etc. This can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 150.
Add low boiling point organic solvent as necessary to high boiling point organic solvent above ℃
Or, dissolve it in combination with a water-soluble organic solvent, use a surfactant in a hydrophilic binder such as an aqueous gelatin solution, and use a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device. After emulsifying and dispersing it, it may be added to the desired hydrophilic colloid liquid. 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 phenol derivatives, phthalate alkyl esters, phosphate esters, citrate esters, benzoate esters, alkylamides, fatty acid esters, trimesate esters, etc. that do not react with the oxidized form of the developing agent. Organic solvents are 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. Dye-forming couplers, I) I rt couplers, colored couplers, D I It compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc., with acid groups such as carboxylic acids and sulfonic acids They can also be introduced into hydrophilic colloids as alkaline aqueous solutions. 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 emulsion layers of the light-sensitive material (between the same color-sensitive layers and/or between redundant color-sensitive layers), causing color turbidity or deterioration of sharpness. , prevent graininess from becoming noticeable 111. A color antifoggant can be used to do this. The color antifoggant may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer. 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 to prevent fogging caused by discharge caused by electrostatic charging of photosensitive materials and to prevent image deterioration 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 containing dyes, ultraviolet absorbers, etc. in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer. Compounds that change the developability, such as development accelerators and development retarders, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material. Compounds that can be preferably used as development accelerators are
The compound is a compound described in Section XXI B to D of No. 7643, 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 for development acceleration and 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. For photosensitive materials, a fluorescent whitening agent can be used to emphasize the whiteness of the white background and to prevent coloring of the white background. Compounds which can be preferably 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, a Harrayon-proof 1j layer, and an irradiation-proof top 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. The silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material can be used to reduce the gloss of the light-sensitive material, improve the ease of writing,
A matting agent can be added for the purpose of preventing photosensitive materials from sticking to each other. Any matting agent can be used, such as silicon dioxide, titanium dioxide, magnesium dioxide,
aluminum dioxide, barium sulfate, calcium carbonate,
Examples include polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resins, polycarbonates, and styrene polymers and copolymers thereof. The particle size of the matting agent is preferably 0.05 μm to 10 μm. 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 is It may be used in an antistatic layer on the side of the support on which the emulsion is not laminated, and it may be used in a protective colloid layer other than the emulsion layer on the emulsion layer and/or the side on which the emulsion layer is laminated with respect to the support. Preferably used antistatic agents are the compounds described in RD 17643 X[I. Improvement, emulsification and 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 paper laminated with an α-olefin polymer (e.g., polyethylene, polypropylene, ethylene/butene copolymer), etc.
Flexible reflective supports such as synthetic paper, films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, and reflective layers provided on these films. flexible support, glass, metal,
Includes pottery 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 anti-friction properties, friction properties, and/or other properties. When coating the photosensitive material, a thickener may be used to improve coating properties. In addition, for example, hardeners, which are highly reactive and may cause gelation of the coated material if added to the coating solution in advance, should be mixed using a static mixer etc. immediately before coating. is preferred. Extrusion coating and curtain coating, which allow two or more layers to be applied simultaneously, are particularly useful as coating methods, but packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected. Examples of the surfactant include, but are not limited to, natural surfactants such as Zabonin, nonionic surfactants such as alkylene oxide type, glycerin type, and glycidol type, 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. Furthermore, it is possible to use a fluorine-containing 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 washing process, and, if necessary, a stabilizing process, or alternatively a process using a bleach solution and a process using a fixing solution. In addition, the bleach-fixing process can be carried out using a 1-bath bleach-fixing solution, and the monobath process using a 1-bath developing, bleach-fixing solution can perform color development, bleaching, and fixing in one bath. Treatment steps may also be performed. In combination with these processing steps, a surface hardening process, its neutralization process, a stop-fixing process, a post-fil' film process, etc. may be performed. In these processes, instead of the color development process, an activator process may be performed in which a color developing agent or its precursor is contained in the material and the development process is performed using an activator solution, or an activator process may be performed in which the monobath process is performed using an activator solution. Processing can be applied. Among these processes, typical processes are shown below. (These treatments are carried out as the final step, which is either a water washing process, a water washing process, or a stabilization process.) Color development process - Bleach process Constant fixation process - Color development process - Bleach-fixing process Processes: Pre-hardening process - Color development process - One stop Fixing process - Washing process - Bleaching process Constant fixation process - Washing process - Post fecal film treatment process - Color development P■ process - Washing process - Supplementary color development processing process - Stopping process - Bleaching process Constant fixation process / activator process - Bleach-fixing process / activator process - Bleaching process Constant fixation process / Monobath process Processing temperature is usually 10°C Should we proceed to the range of ~65℃?
The temperature may exceed 65°C. Preferably 25
The temperature is between 45°C and 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 amine color developing agent, and includes aminophenol derivatives and p-phenylenediamine derivatives. These color developing agents can be used as salts of organic acids and inorganic acids; for example, salt-like acids, sulfates, p-toluenesulfonates, sulfites, sulfates, benzenesulfonates, etc. can be used. can. These compounds generally have a color developer IQ of about 0.
Concentration of 1 to 30 g, more preferably color developer 1i2
It is used at a concentration of about 1 to 15 g. If the amount added is less than 0.1 g, sufficient color density cannot be obtained. Examples of the aminophenol-based developer include 0-aminophenol, p-aminophenol, 5-aminophenol, and 5-aminophenol.
Included are 2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethylbenzene, and the like. Particularly useful primary aromatic amine color developers are N, N'
-Dialkyl-p-phenylenediamine type compound, and the alkyl group and phenyl group may be substituted or unsubstituted. Among them, examples of particularly useful compounds include N-N'-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride% N +N'N-dimethyl-p-phenylenediamine hydrochloride, 2-amino- 5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethy 3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroquinoethylamino Aniline, 4-amino-3-methyl-N, N
Examples include '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 color-producing agent may be incorporated into the color photographic material. In this case, it is 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. In addition, various additives such as Hensyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, development regulators such as citrazic acid, preservatives such as hydroxylamine or sulfites, etc. May contain. 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, pyrogallol-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 and diethylenetriaminopentaacetic acid,
-Hydroxyethylidene-organic phosphonic acids such as 1,1'-diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylene phosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or glyconic acid, 2-phosphonobutane Examples include phosphonocarboxylic acids such as 1,2,4-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 the bleaching agent, a metal complex salt of an organic acid is used, and for example, one in which a metal ion such as iron, cobalt, or copper is coordinated with an organic acid such as polycarboxylic acid, aminopolycarboxylic acid, oxalic acid, or citric acid is used. Among the above Yj organic 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, nclohexanoamine tetraacetic acid, iminodiacetic acid, dihyloquinoethylglycine citric acid (or tartaric acid), ethyl ether diamine tetraacetic acid, glycol ether Examples include noaminetitraacetic acid, ethylenediaminetetrapropionic acid, and phenylenediaminetetraacetic acid. These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaches have a content of 5 to 450 g/Q, more preferably 20 to 2
50g/ (Used in 2) In addition to the above-mentioned bleaching agents, a solution containing sulfite as a preservative may be used as a bleaching solution. [[) It may be a bleaching solution containing a complex salt bleaching agent and containing a large amount of a halide such as ammonium bromide.As the halide, in addition to ammonium bromide, 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 from 4.0 to 9.5, preferably from 4.5 to 8.
0, 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 diosulfate, and ammonium thiosulfate, and thionic acid; Typical examples include potassium, thionate salts such as sodium thiocyanate and ammonium diocyanate, 1,000 urea, and dioether. These fixatives are 5
It is used on bases that can be dissolved at 9/Q or higher, but is generally used at 70-2509/i2. Incidentally, a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the fixing tank. 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) H buffering agents may be contained alone or in combination of two or more. Furthermore, 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, stabilizers such as nitroalcohols and nitrates, hardening agents such as water-soluble aluminum salts, A solvent such as methanol, dimethylsulfamide, dimethylsulfoxide, etc. can be added as appropriate. The pI-I of the fixer is used at 3.0 or more, but generally it is used at 4.5 to 10, preferably 5 to 9.5.
and most preferably 6 to 9. As the bleaching agent used in the bleach-fix solution, the above bleaching treatment 2 [
Examples include the metal complex salts of the IY-acid described above.
Preferred compounds and concentrations in the treatment solution are also the same as in the above bleaching treatment step. 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 edylenoamine iron (III) tetraacetate complex salt bleach and a small amount of a halide such as ammonium bromide other than the silver halide fixer mentioned above, or conversely, a halide such as ammonium bromide may be used. A bleaching solution containing a large amount of iron ethylenediaminetetraacetate (
A special bleach-fix solution having a composition consisting of a combination of a II complex salt bleach and a large amount of a halide such as ammonium bromide can also be used. As the halide,
In addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. 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 pHtli 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 thereto. In all of the following Examples, the amounts added in the silver halide photographic light-sensitive materials are those for In+'' unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver. Example 1 On a triacetyl cellulose film support, each layer having the composition shown below was sequentially formed on the side of the support to prepare a large quantity color photographic element sample 1. Sample 1 (comparison) 1st layer: antihalation Layer (HC-1) Gelatin layer containing black colloidal silver. Second layer: Intermediate layer (1, L,) Gelatin layer containing an emulsified dispersion of 2.5-di-ocdylhydroquinone. Third layer: Low Sensitivity Red-sensitive silver halide emulsion layer (RL-1)
Monodisperse emulsion (emulsion I) consisting of AgBr1 with an average grain size (r) of 0.30 μto and 6 mol% of Agl...silver coating! 1!1.8g/m
"Sensitizing dye r... 6 x 10-5 mol sensitizing dye for 1 mol of silver...
- 1.0% per mole of silver. OX 10"-'Morsian coupler (C-1)... 0.06 moles cyan coupler (C-2)... 0.01 moles colored cyan coupler (C-2)... 0.01 moles per mole of silver cc-B... 0.003 mol per mol of silver DIR compound (DIr(-1)... 0.0040 mol per mol of silver 4th layer; High sensitivity red-sensitive silver halide emulsion layer (R11-1
) Average particle size (r) 0.5 μm, Agl 7.0 mol%
A monodisperse emulsion (emulsion ■) consisting of AgBr1 containing: Silver coating amount: 1.3 g/m2 Sensitizing dye I... 3 x 10-5 moles of sensitizing dye ■... per 1 mole of silver
- 1.0% per mole of silver. OX 11) 'Morsian coupler (C-2)... 0.02 mol per mol of silver Colored cyan coupler (CC-1)... 0.0015 mol per mol of silver DIR compound (DIrt -1 L... O, oot mole per 1 mole of silver 5th layer: Intermediate layer (1, L,) Same as the 2nd layer, gelatin layer. - 6th layer: Low-sensitivity green-sensitive silver halide emulsion F ;'t (
GL-1) Emulsion-1...Coating silver amount 1.5g/m'
Sensitizing dye H1... 2.5X 10-' mol sensitizing dye for 1 mol of silver...
... 1.2X 10-' mole magenta coupler (M-1) per 1 mole of silver... 0.050 mole colored magenta coupler (CM-1) per 1 mole of silver... DIR compound (DIR-1): 0.0040 mol per mol of silver 7th layer: High-sensitivity green-sensitive silver halide emulsion layer (Gll-1)
) Emulsion - ■... Coated silver d1.4 g/n + "sensitizing dye III... 1.5X 10-5 mol per mole of silver sensitizing dye...
... 1 mole of silver. OX 10-' mol Magenta coupler (M-1)... 0.020 mol per mol of silver Colored magenta coupler (CM I) ・0.002 mol per mol of silver DIR compound (DIR-1) ... 10 moles of Q,0O per mole of silver 8th layer; Yellow filter layer (VC-1) A gelatin layer containing an emulsified dispersion of yellow colloidal silver and 2,5-di-t-ofdelhydroquinone. 9th layer: Low-speed blue-sensitive silver halide emulsion layer (BL-1)
AgBr containing 16 mol% Ag with an average particle size of 0.48 μm
Monodisperse emulsion consisting of I (emulsion ■ Le... Trowel coating mQ, 9 g/m" sensitizing dye ■... 1.3X 10-5 mol yellow coupler (Y-1) per mol of silver... 0.29 mol per mol of silver 10th layer: Highly sensitive blue-sensitive emulsion 15 (BH-1) A monodispersed emulsion (emulsion ■) consisting of AgBr1 with an average grain size of 0.8 μm and containing 15 mol% of Agl (emulsion ■)... Silver coating ff10.5g/m2
Sensitizing dye V... 1.0 x 1 G' mol per mol of silver Yellow coupler (Y-1)... - 0.08 mol per mol of silver Dlrt compound (DIR-1)... Silver 1 0.0015 mol per mole Eleventh layer: First protective layer (Pro-1) Silver iodobromide (8 g + 1 mol% average grain size 0.07 μm)
... Silver coating amount 0.5 g/m'' Gelatin layer containing UV absorbers UV-1 and UV-2 12th layer: 2nd protective layer (Pro-2) Polymethyl methacrylate particles (diameter 1.5 μm) and formalin In addition to the above composition, gelatin hardening agent (■1-
1), (rt-2) and a surfactant were added. The compounds contained in each layer of sample 1 are as follows. Sensitizing dye I; anhydro-5,5'-fuchloro-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbonanine 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'-no(3-sulfopropyl)-5,6,5'. 6'-Dibenzoxacarbocyanine hydroquinode sensitizing dye ■; Anhydro-3,3'-di(3-sulfopropyl)-4,5-benzo-5'-methoxythiacyanine-I C-2 V-2 υ r −2 [(C1l t = Cll5OtCII t) , C
CII,5OtCIltclI-]2NCII
- C-2 of the third layer and fourth FT of CIItSOaK sample 1
, show D-1! Samples 2 to 22 were created with the following changes. Samples 1 to 22 thus prepared were subjected to wedge exposure using white light and exposure using a rectangular wave chart, and then subjected to the development treatment described in 'F'. Processing process (38℃) Color development 3 minutes 15 seconds bleaching
Wash with water for 6 minutes and 30 seconds
3 minutes 15 seconds fixed stone
Wash with water for 6 minutes and 30 seconds 3
Stabilization for 1 minute and 30 seconds. Drying for 1 minute and 30 seconds. The composition of the treatment liquid used in each treatment step is as follows. [Color developer A] Eamino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75 g Anhydrous 111 (sodium sulfate 4.25
5/Human [l xylamine 1/2 sulfate 2.0g
511 as glacial potassium carbonate 37.5g
Sodium bromide 1.3 Cinitrilotriacetic acid tristrium salt (I hydrate) 2.5 g Potassium hydroxide 1. Add Oy water to make IQ. [Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 15Q, og hydroxyl acid
Add 10.0 KQ water to adjust to IQ, and use aqueous ammonia to adjust pi (=6.0). [Fixer] Ammonium diosulfate F-175, 0g Anhydrous 1■1 Sodium sulfate 8.5g Meta 11 [Sodium sulfate 2.3g Add water to make IQ, and adjust to H=6.0 using acetic acid. [Stabilizing solution] Formalin (37% aqueous solution) i,
5mQ Conidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.
5m (j° Add water and prepare II2 and 4-. Also, in addition to the above composition, add II, So, and I) to J to H==9.7, and prepare developer B and Na
Development C, which was prepared by adding OII to pl+-10,3, was also used. The sharpness (MTI) of each of the obtained samples was measured using red light (R). The results are shown in Table 2.
duration Transfer Function
n), lO books/ma ”'7: (1) M i
' It is shown as a relative value of F (sample No., l is 100). In addition, for samples developed by changing the pH of the color developing solution, the relative color density at IogE J, 0 (-°
(The color density when using developer is 10
0) 2・, :\ ′″′Vυ Table 2 From the results in Table 2, the present invention improves the processing variability to a large rl+ while maintaining the sharpness improvement effect, and the diffusivity 1) I It can be seen that the processing variation III is equal to or lower than that when R is not used, and the effect of the present invention is clear.Example 2 From Sample No.
C-2) was changed to exemplified compound (II), and the DI of the sixth layer
Sample No. 24 was prepared in exactly the same manner except that the R compound (Dllt-1) was changed to exemplified compound D-60, and the same treatment and evaluation as in Example 1 were performed. As a result, the relative value of M '1'l'' is 138, and the developer L
Relative value of color density when using 1: 88 Relative color density when using developer C (-'' [obtained a result of 120,
It can be seen that the effects of the present invention are significant. Patent Applicant Roku Konishi Photo Industry Co., Ltd. [11 Positive-4B (Method) % Formula % 1. Indication of the case Patent Application No. 37621 filed in 1985 2. Name of the invention Containing a novel coupler - Halogenated Ginsha J″L Photosensitive Shrine 31+Ii Tadashiozurotsuro Moss Incident Patent Applicant Address: 26-2 Nishi-Shinjuku 1-chome, Shinjuku-ku, Tokyo Contact Address: Sh46sha, 1-Sakura-cho, Kuchino-shi, Tokyo 191 Japan 1°L Industrial Company (0425-83-152
1) Mochi 15'F part 4, hli positive life all orders 611,
・′), 2-Mockery/Queen・, 1 1 ′・
L-, '51+li positive subject specification 6, hli positive statement of contents, letter a (no change in content)

Claims (1)

[Scope of Claims] 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 [I] and an oxidized form of a color developing agent are reacted. 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 [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 represents an alkyl or aryl group, and 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 a phenyl group. ]