JPS6358346B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel development inhibitor-releasing compound capable of releasing a development inhibitor through a coupling reaction with an oxidation product of a color developing agent, and more particularly, the present invention relates to a novel development inhibitor-releasing compound capable of releasing a development inhibitor through a coupling reaction with an oxidation product of a color developing agent, and more particularly, the present invention relates to a novel development inhibitor-releasing compound capable of releasing a development inhibitor by a coupling reaction with an oxidation product of a color developing agent. This invention relates to a silver halide color photographic material with improved properties. BACKGROUND ART Conventionally, there is a well-known technique for improving image characteristics by incorporating into a color photographic material a compound capable of releasing a development inhibitor in accordance with the image density during color development. Representative examples of these compounds include, for example, U.S. Patent Nos. 3148062, 3227554, 3701783,
No. 3733201, etc., and these compounds generally have a compound residue introduced as a substituent that forms a compound that exhibits a development inhibiting effect when released from the active site of the coupler molecule. It is called a development inhibitor-releasing coupler (DIR coupler) because it undergoes a coupling reaction with the oxidation product of a color developing agent during color development to simultaneously form a dye and a development inhibitor. On the other hand, for example, U.S. Pat. No. 3,632,345;
Specification No. 3928041, JP-A-49-77635, JP-A No. 49-
No. 104630, No. 50-36125, No. 50-15273, No. 51
The compounds described in JP-A-6724 and JP-A-55-161237 have a compound residue introduced as a substituent into the active site, which can form a compound that exhibits a development inhibiting effect when released in the same manner as described above. This compound is called a development inhibitor-releasing substance (DIR substance) because it releases only a development inhibitor when it undergoes a coupling reaction with the oxidation product of a color developing agent during color development. As mentioned above, both the above-mentioned DIR couplers and DIR substances are characterized by releasing a development inhibitor in accordance with the density of the image during color development. In the case of a silver oxide emulsion layer, development is suppressed within the layer in accordance with the image density, improving the gradation, graininess, sharpness, etc. of the image, and this effect is called the so-called intra-image effect. I'm here. On the other hand, the development inhibitor released as described above also diffuses into the adjacent layer, and in that layer there is a mask effect that suppresses development in accordance with the density of the image in the diffusion source layer, and in other layers in the case of monochromatic exposure. It also has an effect on color reproducibility due to the suppression of development in
It's called the image effect. However, the above mentioned DIR coupler and
DIR substances cannot be said to be compounds that can satisfy all of the above effects, and there has been a strong desire for improvement. That is, for example, in both of the above-mentioned compounds, if the leaving group is a residue of a compound that forms a mercapto compound, not only the development suppressing power is too strong, but also the diffusivity is small, so that it is mainly intra-intra. - Since the image effect is large and the inter-image effect is not always sufficiently exhibited, satisfactory results have not been obtained, especially in terms of improving color reproducibility. In this case, increasing the amount of the compound added produces an inter-image effect and improves color reproducibility, but desensitization is large and satisfactory results cannot be obtained. Therefore, as a development inhibitor-releasing compound to improve the above-mentioned drawbacks, for example, JP-A-49-122335
A DIR coupler, which is a compound in which an azole compound is substituted at the active site as a leaving group, was proposed, as described in Japanese Patent No. 52-82424. However, these DIR couplers had a weak development inhibitory effect due to the released development inhibitor, and hardly any intra-image or inter-image effects were observed. Furthermore, JP-A-55-135835 describes a DIR coupler in which a mercapto compound having a hydrophilic group is substituted as a leaving group; Compared to DIR couplers that have active sites, they have weaker development suppressing power and almost no desensitization, but they have greater diffusivity. Therefore, even if the intra-image effect is not sufficient, the inter-image effect is large, and it is possible to enhance the intra-image effect by increasing the amount added. However, this DIR coupler forms not only a development inhibitor but also a dye, so it is necessary to select the dye appropriately for hue harmony, and it is difficult to strike a balance between the dye and the development suppressing power. It has disadvantages, and if added to layers of different hues, it may cause color turbidity, so it is necessary to select the layer to which it is added, and it lacks convenience in use. Therefore, a first object of the present invention is to provide a novel development inhibitor-releasing compound that has excellent intra-image effects and inter-image effects, and is particularly useful for improving color reproducibility. The second object is to provide a silver halide color photographic light-sensitive material with improved photographic properties by containing the above-mentioned novel development inhibitor-releasing compound, and the third object is to provide a silver halide color photographic material with improved photographic properties. There is no
Another object of the present invention is to provide a silver halide color photographic material containing a novel development inhibitor-releasing compound that prevents color turbidity. As a result of repeated studies on the above-mentioned problems, the present inventors have discovered that at least one compound represented by the following general formula [) or [) that undergoes a coupling reaction with the oxidation product of a color developing agent and releases a development inhibitor. It has been found that the above object can be achieved by a silver halide color photographic light-sensitive material containing in a hydrophilic colloid layer.

【formula】 or

【formula】 [In the formula, A is

【formula】

【formula】

[Formula _] [wherein, where X ₂ represents a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a triazole group, or a tetrazole group, and R ₃ represents an alkyl group or an aryl group. ], Z represents a nitrogen atom, oxygen atom, selenium atom, sulfur atom or carbon atom necessary to form a 5-membered heterocycle, X represents a divalent organic group, and R
represents OR ₁ , COOR ₁ , SO ₂ NHR ₁ or SO ₃ R ₁ (where R ₁ represents a hydrogen atom, ammonium ion or metal ion), and Y represents an oxygen atom, a sulfur atom, a selenium atom, or NR ₂ (here, R ₂ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms). m is 0 or 1, n is 1
Or 2. ] The silver halide color photographic light-sensitive material of the present invention (hereinafter abbreviated as the light-sensitive material of the present invention) will be described in more detail below. The photosensitive material of the present invention is characterized in that the hydrophilic colloid layer contains at least one development inhibitor-releasing compound (hereinafter simply referred to as DIR substance) represented by the general formula [] or [)]. . First, Z in the general formula [] represents the above-mentioned atoms necessary to form a 5-membered plural ring, and examples of the 5-membered heterocyclic group include, for example, a tetrazole group, an oxadiazole group, Examples include selenazole group, thiazole group, triazole group, imidazole group, imidazolinone group, thiazolinone group and thiadiazole. In addition, examples of the fused heterocyclic group formed by Y in the general formula [] include a benzimidazole group, a benzothiazole group, a benzoxazole group, and a benzoselenazole group, and these heterocyclic groups further include It may be substituted with an amino group, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, or the like. Furthermore, the divalent organic group represented by , ethylene group, isopropylene group, etc.), arylene groups (phenylene group, naphthylene group, toluylene group, etc.), and heterocyclic groups (furandiyl group, pyridinediyl group, thionindiyl group, etc.). Also, these interconnected groups, e.g.

【formula】

[Formula], etc., and furthermore, these are oxygen atoms, etc., and these are further connected by oxygen atoms, sulfur atoms, sulfonyl groups, carbonyl groups, imino groups, etc., such as -
_NHCOCH2- , -S- _{CH2CH2- ,} etc. are also included. Further, the preferred substituent represented by R ₁ in the general formula [] or [] is a hydrogen atom or a metal ion, and the preferred substituent represented by R ₂ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. It is. Next, the carbocycle of B in the above general formula [] includes those that form a fused ring at an appropriate position, and specifically, examples include monocyclic rings such as a cyclopentanone ring, a cyclohexanone ring, an indanone ring, and a benzindanone ring. or a fused ring, and the carbocyclic ring includes at least one substituted or unsubstituted alkyl group, aryl group, nitro group, cyano group, alkoxy group,
Aryloxy groups, acylamino groups, sulfonamide groups, sulfamoyl groups, carbamoyl groups, acyloxy groups, multi-ring groups, etc. may be substituted, and specific examples of these include alkyl groups (e.g. tert-butyl group, octyl group, etc.). group, dodecyl group, etc.), as an aryl group (e.g. phenyl group,
tolyl group, etc.), an alkoxy group (e.g. octyloxy group, dodecyloxy group, etc.), an aryloxy group (e.g. phenoxy group, p
-tert-butylphenoxy group, naphthoxy group, etc.), acylamino group (e.g. acetamide group, butylamide group, etc.), sulfonamide group (e.g. tert-butylsulfonamide group, phenylsulfonamide group, etc.), sulfamoyl group: (for example, butylsulfamoyl group, phenylsulfamoyl group, etc.), carbamoyl group (for example, dodecylcarbamoyl,
octylcarbamoyl, etc.), acyloxy groups (e.g. dodecanoyloxy, benzoyloxy, 3-pentadecylphenylacetoxy, etc.), heterocyclic groups preferably include nitrogen, oxygen, sulfur, etc. as heteroatoms. 5
or 6-membered multiple rings, fused multiple ring groups, such as benzthiazole group, succinimide group, oxadiazole group, thiadiazole group, triazine group, triazole group, diazole group, pyrimidine group, naphthothiazole group, etc. These heterocyclic groups have one or more substituents such as an alkyl group, a halogen atom, an acylamino group, an alkylamino group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a sulfamoyl group, a carbamoyl group, a nitro group, or a cyano group. You may do so. Examples of the halogen atom of X ₂ in the general formula [] include F, Cl, Br, etc., examples of the alkyl group include methyl group, ethyl group, butyl group, and examples of the aryl group include phenyl group. , 2-chlorophenyl group, 4-nitrophenyl group, etc.; examples of alkoxy groups include methoxy group, ethoxy group, butoxy group; examples of aryloxy group include phenoxy group, 4-hydroxycarbonylphenoxy group, etc. Examples of the heterocyclic group include a tetrazole group and a triazole group. The alkyl group and aryl group of R ₃ in the general formula [ ] [ ] may have a substituent. This alkyl group is
Examples include octyl group, dodecyl group, octadecyl group, biloxyethyl group, and aryl groups include phenyl group, p-chlorophenyl group, p-dodecyloxyphenyl group, and the like. Next, useful DIR substances used in the present invention include, but are not limited to, the following. 〔Concrete example〕 The above DIR substance according to the present invention can be synthesized by the following method. Synthesis Example 1 (Synthesis of Exemplified Compound D-2) 10.3 g of 2-chloro-4-octadecylsuccinimide-1-indanone and 6.0 g of diK salt of 1-(4-carboxyphenyl)-5-mercaptotetrazole were added to 100 ml. of dimethylformamide and stirred at room temperature for 2 hours while bubbling nitrogen gas. Then, pour the reaction solution into 500ml of ice water.
Filter the precipitate and wash with water. 200 of this excess
Suspend in 1 ml of ethyl acetate, add 50 ml of 2N hydrochloric acid, and stir vigorously. After removing the aqueous layer, the ethyl acetate solution was washed twice with water, dehydrated using a sieve, and the ethyl acetate was distilled off under reduced pressure. The residue was recrystallized from a mixed solvent of 40 ml of alcohol and 20 ml of methanol to obtain 7.3 g of Exemplary Compound D-2. melting point
78-81°C Synthesis Example 2 (Synthesis of Exemplary Compound D-3) 5.3 g of 2-chloro-4-octadecylsuccinimide-1-indanone and 2.5 g of di-Na salt of 1-(4-hydroxyphenyl)-5-mercaptotetrazole g is boiled under reflux for 1 hour in 100 ml of acetonitrile while bubbling nitrogen gas. After distilling off the solvent under reduced pressure, the residue was diluted with 200ml of ethyl acetate.
Add 50 ml of 2N hydrochloric acid and stir vigorously.
After removing the aqueous layer, the organic phase was washed twice with water and dehydrated using a sieve, and then ethyl acetate was distilled off under reduced pressure. The residue was chromatographed on a silica gel column using hexane and ethyl acetate as eluent. Combine the fractions containing the product, remove the solvent under reduced pressure, and collect 50 ml of the residue.
When heated and dissolved in methanol and left to cool in ice water, 2.7 g of Exemplified Compound D-3 is obtained as a white fine powder.
Obtained. DIR according to the present invention obtained by a synthesis method with a melting point of 71 to 73°C or higher
A method for incorporating a substance into a light-sensitive material is, for example, similar to the method described in U.S. Pat. It can be added and contained in the hydrophilic colloid layer. Alternatively, it can be dissolved in an alkaline aqueous solution or a hydrophilic organic solvent such as methanol, ethanol, acetone, dimethylformamide, etc., and added directly to the hydrophilic colloid layer. The above DIR substances may be used alone or in combination of two or more. Furthermore, other known DIR substances and
It can also be used with DIR couplers. The DIR substance according to the present invention can be used in combination with a colorless coupler or a colored coupler, and can be added to the silver halide emulsion layer as the same emulsion as the coupler, or as an independent emulsion in an auxiliary layer such as an intermediate layer. It can also be added. and above
When the DIR substance is added to the silver halide emulsion layer, the amount of the compound of the present invention added is in the range of 0.01 to 10 mol %, preferably about 0.05 to 5 mol %, per 1 mol of silver halide. The DIR substance according to the present invention can be used in various silver halide photographic materials, for example, it is useful for black and white, color, pseudocolor, etc., and it is also useful for general black and white, printing black and white, and X-ray. It can be applied to silver halide photographic materials for various purposes such as electron beam, high resolution black and white, general color, color X-ray, and diffusion transfer color. When applying the DIR substance according to the present invention to a silver halide color photographic light-sensitive material, the known 2 equivalent, 4 equivalent
Can be used in conjunction with equivalent couplers. As the yellow coupler used in the present invention, an open chain ketomethylene compound such as a pivalyl acetanilide type or benzoylacetanilide type yellow coupler is used. Further, as the magenta coupler, compounds such as pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, and indazolone type are used. Colorless magenta couplers are generally used as masking couplers.
A compound in which an arylazo group is substituted at the active site of a magenta coupler is used. Furthermore, colored magenta couplers of the type in which the dye is leached into the processing bath by reaction with the oxidation products of the color developing agent can also be used. Furthermore, as the cyan coupler, phenol or naphthol derivatives are generally used. Colored masking coupler
As the cyan coupler, a colorless cyan coupler having an active site substituted with an aryl azo group is generally used. Furthermore, colored cyan couplers of the type in which the dye is leached into the processing bath by reaction with the oxidation product of the color developing agent can also be used. The photographic material of the present invention may also contain a so-called competing coupler, a coupler that forms a colorless dye, in order to improve photographic properties. The coupler used in the present invention is
Preferred are the 2-equivalent couplers described on pages 68 to 80 of Specification No. 53-144727, and the 4-equivalent couplers or colored couplers described on pages 109 to 115 of the same. The emulsion layer or non-light-sensitive hydrophilic colloid layer containing the DIR substance according to the invention may contain reducing agents or antioxidants, such as sulfites (sodium sulfite, potassium sulfite, etc.), bisulfites (sodium bisulfite, potassium bisulfite, etc.). etc.), hydroxylamines (hydroxylamine, N-methylhydroxylamine, N-phenylhydroxylamine, etc.),
Sulfuric acids (sodium phenylsulfinate, etc.), hydrazines (N,N'-dimethylhydrazine, etc.), reductones (ascorbic acid, etc.), aromatic hydrocarbons having one or more hydroxyl groups (p-aminophenol, etc.) , alkylhydroquinone, gallic acid, catechol, pyrogallol, resorcinol, 2,3-dihydroxynaphthalene, etc.). Furthermore, in order to further improve the light fastness of the magenta color image formed from the magenta coupler used in the present invention, p-alkoxyphenols and phenolic compounds are added to the emulsion layer or its adjacent layer. can do. Regarding the layer structure of the photosensitive material of the present invention, the usual subtractive color method may be used. In principle, a yellow coupler is used to form a yellow dye in the blue-sensitive photosensitive layer, and a magenta dye is formed in the green-sensitive photosensitive layer. The basic layer structure consists of three layers, each containing a magenta coupler to form a cyan dye in the red-sensitive photosensitive layer, and a cyan coupler to form a cyan dye in the red-sensitive photosensitive layer. By forming the layers into double or triple layers, it is possible to improve various photographic properties of the light-sensitive material, such as color development characteristics, color reproducibility, and color pigment granularity. In addition to these basic emulsion layers, various layers such as a protective layer on the top layer, an intermediate layer, a filter layer between the layers, an undercoat layer on the bottom layer, and an anti-halation layer are used to protect and prevent color staining. It is possible to measure improvements in graininess, color reproduction, film adhesion, etc. Examples of the silver halide used in the light-sensitive material of the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. Any silver halide used is included. The above silver halide emulsion can be sensitized using a known chemical sensitizer. As the chemical sensitizer, noble metal sensitizers, sulfur sensitizers, selenium sensitizers, and reduction sensitizers can be used alone or in combination. A known binder is used as the binder for silver halide. Furthermore, the silver halide emulsion of the present invention can be spectrally sensitized using a known sensitizing dye, if necessary. The above silver halide emulsions include 1-phenyl-5-mercaptotetrazole, 3-methylbenzothiazole, 4-methylbenzothiazole, and
Various compounds such as heterocyclic compounds such as hydroxy-6-methyl-1,3,3a,7-tetraazaindene, mercapto compounds, metal salts, etc. can be added. Further, the hardening treatment of the above emulsion is carried out according to a conventional method. A surfactant may be added alone or in combination to the silver halide emulsion. These surfactants include coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, antistatic agents, adhesive resistance agents, and various active agents for improving photographic properties or controlling physical properties. agent can be used. The color developing agent used in the processing of the light-sensitive material of the present invention has a pH of 8 or more including the developing agent, preferably
It is an alkaline aqueous solution with a pH of 9 to 12. The aromatic primary amine developing agent used as the developing agent is a compound having a primary amino group on an aromatic ring and having the ability to develop exposed silver halide, or
It refers to a precursor that forms such a compound. The above-mentioned developing agent is typically p-phenylenediamine type, and the following are preferred examples. 4-amino-N,N-diethylaniline, 3-
Methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-ethyl-N-β-hydroxyethylaniline,
3-Methyl-4-amino-N-ethyl-N-β-
Methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethyl-4-amino-N,N-diethylaniline, 3-methoxy-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-
N,N-diethylaniline, 4-amino-N,N
-dimethylaniline, N-ethyl-N-β-[β
-(β-methoxyethoxy)ethoxy]ethyl-
3-methyl-4-aminoaniline, N-ethyl-
N-β-(β-methoxyethoxy)ethyl-3-
Methyl-4-aminoaniline and salts thereof, such as sulfate, hydrochloride, sulfite, p-toluenesulfonate, and the like. Moreover, various additives can be added to these color developing solutions as necessary. After imagewise exposure of the color light-sensitive material according to the present invention and color development processing, bleaching processing can be carried out by a conventional method. This process may be performed simultaneously with fixing or separately. This processing solution can also be used as a bleach-fixing bath by adding a fixing agent if necessary. Various compounds are used as bleaching agents,
Various additives can also be added, including bleach accelerators. The present invention is realized in various forms of color photosensitive materials. One method is to process a photographic light-sensitive material having a silver halide emulsion layer containing a diffusion-resistant coupler on a support with an alkaline developer containing an aromatic primary amine color developing agent to make it water-insoluble or diffusion-resistant. This is to leave the coloring dye in the emulsion layer. In another form, a photographic light-sensitive material having a silver halide emulsion layer combined with a diffusion-resistant coupler on a support is processed with an alkaline developer containing an aromatic primary amine color developing agent to form an aqueous medium. A soluble and diffusible dye is produced and transferred to an image-receiving layer consisting of another hydrophilic colloid. That is, it is a diffusion transfer color method. The light-sensitive materials of the present invention include all kinds of color light-sensitive materials such as color negative films, color positive films, color reversal films, and color papers. Next, the present invention will be specifically explained with reference to examples, but the embodiments of the present invention are not limited thereby. Example 1 The following samples 1 to 6 were prepared by multilayer coating on a transparent triacetate film base in the following order.
It was created. 1st layer: red-sensitive emulsion layer As a cyan coupler, 1-hydroxy-N-
10.6 g of [4-(2,4-di-tert-amylphenoxy)butyl]-2-naphthamide was dissolved in 11 ml of tricresyl phosphate and 30 ml of ethyl acetate,
This was mixed with 10 ml of a 10% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) and 200 ml of a 5% aqueous gelatin solution, and emulsified and dispersed in a colloid mill to obtain an emulsion []. This dispersion was then added to 1 kg of red-sensitive silver iodobromide emulsion (containing 6 mol% silver iodide), and a 2% solution of 1,2-bis-(vinylsulfonyl)ethane ( 40 ml of water and methanol (mixing ratio: 1:1) was added and coated and dried. The amount of silver coated at this time was 20 mg/dm ² . Second layer: Interlayer A gelatin interlayer containing 0.5 g/m ² of gelatin and 0.1 g/m ² of 2,5-di-tert-octylhydroquinone was applied. 3rd layer: Green-sensitive emulsion layer 1-(2,4,6-
trichlorophenyl)-3-[3-(2,4-di-
15 g of tert-amylphenoxyacetamido)benzamide]-5-pyrazolone was dissolved in 15 g of tricresyl phosphate and 45 ml of ethyl acetate, and an emulsion was prepared in the same manner as in Example 1 (1). I got (2). This emulsion was mixed into a green-sensitive silver iodobromide emulsion (6 mol%
A hardener was added in the same manner as in the first layer of Example 1, and the film was coated and dried. The amount of silver coated at this time was 20 mg/dm ² . Fourth layer: Protective layer A gelatin layer containing 0.5 g/m ² of gelatin was applied. The sample obtained in this way is designated as sample-(1),
Each of the development inhibitor-releasing compounds listed in Table 1 below was added to the oil component of the third layer of sample-(1),
The emulsion was emulsified and dispersed in the same manner as in (2). Samples (2) to (6) were prepared in the same manner as sample-(1) except that the amount of the development inhibitor-releasing compound was adjusted so that γ _G (gamma of the green-sensitive layer) was approximately the same. It was created.

【table】

【table】

【table】

Samples 1 to 6 thus obtained were wedge exposed to green light and then uniformly exposed to red light at an exposure dose such that the density of red light was 2.0, and then the following development treatment was performed. [Processing process] (38℃) Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilizing bath 1 minute 30 seconds In each processing step The composition of the treatment liquid used was as follows. [Color developer composition] 4-amino-3-methyl-N-ethyl-N-
(β-hydroxyethyl)-aniline sulfate
4.75g Anhydrous sodium sulfite 4.25g Hydroxyamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Trisodium nitrilotriacetate (monohydrate)
2.5g Potassium hydroxide 1.0g Add water to make 1, and adjust the pH to 10.0 using potassium hydroxide. [Bleach solution composition] Ethylenediaminetetraacetic acid iron ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt
10.0g Ammonium Bromide 150.0g Ice Acetic Acid 10.0ml Add water to make 1, and adjust the pH to 6.0 using aqueous ammonia. [Fixer composition] Ammonium thiosulfate (50% aqueous solution) 162ml Anhydrous sodium sulfite 12.4g Add water to make 1, and adjust to PH6.5 using acetic acid. [Stabilizing liquid composition] Formalin (37% aqueous solution) 5.0ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.)
Add 7.5ml water to make 1. The results of Samples 1 to 6 developed in this way are shown in Table 2 below. Incidentally, the interlayer effect (inter-image effect) on the red-sensitive layer was calculated as follows. The red-sensitive layer is originally exposed uniformly so that D=2.0,
The interimage effect shows the rate at which the red light density decreases as the development of the red-sensitive layer is suppressed in accordance with the density developed in the green-sensitive layer. If the red light density when the green light density is maximum is D ₁ , the intensity of the interimage can be expressed as (2.0−D ₁ /2.0×100). That is, the larger this value is, the stronger the interimage effect is and the color reproducibility is improved.

[Table] The amount added in the above table is expressed as compound mole/Ag mole x 100. Also, the sensitivity value is the sample −
The relative sensitivity value is entered when the sensitivity of 1 (control) is set to 100. From the results in Table 2, the DIR substance of the present invention has a comparative DIR
-Even if the amount added is increased compared to A, there is less sensitivity loss and less fog, which is almost the same as γ.
given the value. At this time, it can be seen that the interimage effect on the red-sensitive layer is clearly emphasized. On the other hand, when comparing DIR-C, which has a similar inhibitory group, with the DIR substance of the present invention, the compound of the present invention has a greater intra-image effect (γ reduction, anti-fogging) even in a small amount, and shows that the compound of the present invention has a greater intra-image effect (γ reduction, anti-fogging).・It can be seen that the image effect is also large. Also compare DIR-B
Even when the amount added was increased, the intra-image effect was weak, and the inter-image effect was also weak. Therefore, it is understood that the DIR material according to the present invention has extremely good intra-image and inter-image effects. Example 2 The magenta coupler used in Example 1 was applied onto a triacetate film having an antihalation layer.
15g and a DIR compound as shown in Table 3 below were emulsified and dispersed in the same manner as emulsion-(2) of Example 1, and added to a silver halide emulsion having the same composition as the third layer of Example 1,
A hardening agent was added, and the coating was dried to obtain samples 7 to 11.
The amount of silver coated at this time was 20 mg/dm ² .

[Table] Samples 7 to 11 thus obtained were wedge exposed to green light, developed in the same manner as in Example 1, and the graininess of the color image was measured by RMS using green light.
(Root ment squre) method. The RMS granularity results at a concentration of 0.7 are shown in Table 4. On the other hand, samples 7 to 11 have a spatial frequency of 3 lines/mm.
The color image was exposed to green light through a wedge varying in the range of up to 100 lines/mm, developed in the same manner as in Example 1, and the obtained color image was subjected to MTF using green light.
(Modulation Transfer Function) was calculated, the MTF values were compared at spatial frequencies of 10 lines/mm and 30 lines/mm, and the sharpness improvement effect was examined. Table 4 shows the results.

[Table] (In addition, the amount added in the above table is compound mole/Ag
It is expressed in moles x 100. ) The RMS value is 1000 times the standard deviation of the variation in concentration value that occurs when scanning with a microdensitometer with a circular scanning aperture of 25μ. The MTF value was determined by measuring the density using a slitter with a slit width of 300μ in length and 2μ in width, and expressed the resolution as a percentage of the input. According to Table 4, the DIR substances of the present invention are compared to DIR−
It can be seen that graininess is specifically improved where A and γ almost match. Moreover, compared to comparative DIR-Coupler C, DIR according to the present invention can be obtained with a small amount added.
It can be seen that the material has a large decrease in γ and is excellent in both graininess and sharpness. Example 3 Coupler used in the third layer of Example 1 as a magenta coupler on a clear triacetate base
15g of the DIR compound shown in the table below was emulsified and dispersed in the same manner as Emulsion-2 of Example 1, and
It was added to a silver halide emulsion having the same composition as the layer, coated and dried in the same manner to obtain samples 12 to 15. On the other hand, a sample obtained by dissolving exemplified compound D-7 of the present invention in methanol, directly adding it to the above green-sensitive emulsion, and coating it was designated as Sample-16. Samples 12 to 16 thus obtained were used in Example 1.
The gradation control effect and degree of color turbidity were examined by exposing and developing green light in the same manner as above.

[Table] The amount added in the above table is expressed as compound mole/Ag mole x 100. For color turbidity, the blue light density where the green density of the characteristic curve is 1.0 is entered. The larger the value, the more muddy the color. From Table 5, it can be seen that the DIR material of the present invention lowers γ with a smaller amount than the comparative DIR compound, and also has a greater reduction in fog. In addition, when examining the color turbidity of the coloring dye, the comparative DIR compound develops a yellow color during development, so
Although the B/G value is large and color turbidity occurs, the DIR material of the present invention does not form a dye during development, so no color turbidity occurs and good results are obtained. On the other hand, Sample 16 in which the DIR substance was directly added to the emulsion using methanol had the same performance as Sample 15 in which oil protection was dispersed, giving good results. Example 4 Multilayer samples 17 to 20 were prepared in the same manner as in Example 1, except that the DIR material in the third layer of Example 1 was changed to a DIR material as shown in Table 6 below. This sample was exposed in the same manner as in Example 1, and the interimage effect on the red-sensitive layer was examined. The results were as follows.

【table】

[Table] It can be seen from Table 6 that all DIR substances according to the present invention have stronger interimage effects than the control materials.

Claims (1)

[Scope of Claims] 1. A hydrophilic colloid layer containing at least one compound represented by the following general formula [] or [) that undergoes a coupling reaction with an oxidation product of a color developing agent to release a development inhibitor. A silver halide color photographic material characterized by: [Formula] or [Formula] [where A is [Formula] [Formula] [Formula] (X ₁ represents a hydrogen atom or a halogen atom, and B is 5
~ Represents a group of nonmetallic atoms required to form a 6-membered saturated or unsaturated carbocyclic ring, X ₂ represents a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a triazole group, a tetrazole group, R ₃ represents an alkyl group or an aryl group. ) Z is a nitrogen atom necessary to form a 5-membered heterocycle,
represents an oxygen atom, selenium atom, or carbon atom,
X represents a divalent organic group, R represents OR ₁ , COOR ₁ ,
SO ₂ NHR ₁ or SO ₃ R ₁ (where R ₁ is a hydrogen atom,
Represents ammonium ion or metal ion. )
, and Y represents an oxygen atom, a sulfur atom, a selenium atom, or NR ₂ (herein, R ₂ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms).
m is 0 or 1, and n is 1 or 2. ]