JPS62177557A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having an improved shelf life and development processing characteristics by incorporating a diffusive DIR compd. capable of releasing a diffusive controller or its precursor by reacting with an oxidant of a color developing agent to at least one layer until the 2nd layer among adjacent photosensitive silver halide layers. CONSTITUTION:The diffusive DIR compd. capable of releasing the diffusive controller or its precursor by reacting with the oxidant of the color developing agent is incorporated to a layer or two layers until the 2nd layer of the adjacent silver halide photosensitive layers which are adjacent to a non-photosensitive hydrophilic colloidal layer on the side of a substrate and do not have the silver halide photosensitive layer on the another side of the substrate. The non- photosensitive silver halide fine particle has preferably <=0.3mum mean particle size. If the particle size is more than the prescribed size, as a light scattering of the particle is large and a sharpness of the image reduces, the mean particle size is 0.02-0.2mum, preferably 0.01-0.1mum. Thus, the titled material having excellent image characteristics and the improved shelf life and development processing property is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material, and more specifically, a silver halide color photographic material which has excellent image quality characteristics and improved storage stability and development processing characteristics. Regarding materials.

[Prior art]

2. Description of the Related Art Conventionally, silver halide color photographic materials, particularly silver halide color photographic materials for photographing, have been required to have various properties, such as high sensitivity and excellent image sharpness. Particularly in recent years, compact cameras that are convenient to carry have become popular, and small-sized films have come into use as a result. These small-sized films have a small screen size, and in order to print an image on photographic paper on photographic paper, it must be enlarged ten times, which reduces resolution and sharpness. However, there was a problem that the image quality was impaired.

By the way, it is well known that the sharpness of an image is improved by the adjacency effect. This effect is achieved by utilizing the concentration gradient of the development inhibitor during development, and is achieved by containing in the photosensitive material a compound that reacts with the oxidized form of the developing agent to release the development inhibitor. Examples of this type of development inhibitor include, for example, as described in U.S. Pat. Nos. 3,148,062 and 3,227,554.
Compounds that form dyes and release development inhibitors by combination with oxidized forms of color developing agents, or compounds that form dyes and release development inhibitors by combination with oxidized forms of color developing agents, or as described in U.S. Pat. No. 3,632,345. There are known compounds that release development inhibitors and form compounds that do not form dyes upon coupling (hereinafter referred to as DIR).
It is called a compound. ). Particularly preferably, U.S. Pat.
48,962, JP-A-57-154234, JP-A-58-217932, etc., a method of improving sharpness using a DIR compound that releases a highly diffusible development inhibitor. be.

By the way, DIR that releases this highly diffusible development inhibitor
The compound has the disadvantage that it reduces the color density when the silver halide photographic light-sensitive material is stored for a long period of time or left in a passenger car during the summer. Furthermore,
Even if the development inhibitor is diffused and accumulated in the color developer during color development processing, or even if the inhibitor has a small accumulation effect, it may be difficult to use when a light-sensitive material containing a diffusible DIR compound is undergoing color development or immediately after development. It has been discovered that the color density decreases when the treatment is carried out, and improvements to these problems have been desired.

[Purpose of the invention]

The object of the present invention is to provide a diffusible DI that releases diffusivity inhibitors or precursors essential for obtaining excellent image quality characteristics.
The object of the present invention is to provide a silver halide photographic material containing an R compound, which has improved storage stability and development processing characteristics.

[Structure of the invention]

The above-mentioned object of the present invention is to provide a silver halide photographic material having at least one non-photosensitive hydrophilic colloid layer containing substantially non-photosensitive fine silver halide grains on a support. The hydrophilic colloid layer has a photosensitive silver halide layer adjacent to the support side, and the other side has no photosensitive silver halide layer, and the adjacent photosensitive silver halide layer A silver halide photographic light-sensitive material, characterized in that one or two of the photosensitive silver halide layers up to at least the second layer contain a diffusible DIR compound that releases an oxidized product of a color developing agent or its precursor. This is achieved by using .

In the present invention, the non-photosensitive silver halide fine grains refer to those that are substantially non-photosensitive, that is, those that are not substantially developed in a developer, and any such grains may be used. However, it is preferred that the material is not substantially developed or dissolved in the developer. Further, it is preferable to have an average particle size of 0.3 μm or less, and if the particles are larger, light scattering is large and sharpness deteriorates, so the average particle size is 0.02 to 0.2 am, preferably 0.01 am.
It is more preferable that it is 0.1 μm. Further, the particle distribution may be wide or narrow, but a narrow distribution is preferable.

Silver halide grains used as substantially non-photosensitive silver halide fine grains include silver chloride, silver bromide, silver iodide,
Any silver halide such as silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. may be used, and these silver halides may be used alone or in combination of two or more. Further, the silver halide grains preferably contain silver bromide from the viewpoint of solubility, particularly 10 mol % of silver halide grains.
Silver iodobromide containing less silver iodide is preferred. The silver halide grains may be physically ripened with rhodan ions, cyano ions, thiocyanate ions, etc., or may be etched with a silver halide solvent. These silver halide grains are produced using the neutral method, half ammonia method,
It is manufactured by various manufacturing methods such as the ammonia method, and by various manufacturing methods such as the simultaneous mixing method and the conversion method.

Silver halide in the non-photosensitive layer is 0.01 to 1.5 gAg/
Generally, it is applied at a thickness of 0.m, preferably 0.
3 to Q, used by coating at 7 gAg/rd. The non-photosensitive layer contains colloidal silica, capping agents such as polymethyl methacrylate, high boiling point solvents (e.g. tricresyl phosphate, dioctyl phthalate, etc.), lipophilic components such as ultraviolet absorbers, antioxidants, hydroquinone derivatives, and interfaces. Coating aids such as activators, hardened gelatin emulsions, etc. may be used at the same time.

Gelatin is generally used as a binder for the non-photosensitive layer, but colloidal albumin, agar, acacia, alginic acid, hydrolyzed cellulose acetate, etc. can be used in place of some or all of the gelatin.
Cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, or synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyacrylamide,
Poly-N, N-dimethylacrylamide, poly-N-vinylpyrrolidone, U.S. Pat. No. 3,847,620, No. 3
, No. 655,389, No. 3,341,332, No. 3,
615°424, 3,860,428, etc.;
Gelatin derivatives such as phenylcarbamylated gelatin, acylated gelatin, and phthalated gelatin as described in US Pat.
Grafting monomers with polymerizable ethylene groups such as acrylic acid (ester), methacrylic acid (ester), acrylonitrile, etc. to gelatin as described in , 548゜520, 2,831,767, etc. Copolymerized materials may also be used.

The layer structure of the silver halide photographic light-sensitive material of the present invention will be described below, focusing on the non-photosensitive hydrophilic colloid layer containing non-photosensitive fine halide particles. When viewed from the surface side of the photosensitive material, the non-photosensitive fine grain silver layer is located closer to the photosensitive halogenated layer. Conversely, when viewed from the support side, a non-photosensitive fine grain silver layer is present on the surface side adjacent to the farthest photosensitive silver halide layer among the photosensitive silver halide layers.

In the present invention, the silver halide emulsion in the photosensitive silver halide layer adjacent to the non-photosensitive fine grain silver layer includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, Any of those used in conventional silver halide emulsions can be used, such as silver chloroiodobromide and silver chloride. Especially silver bromide,
Silver iodobromide and silver chloroiodobromide are preferred.

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

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

During the growth of halogen (11) grains, known silver halide solvents such as ammonia, thioether, thiourea, etc. can be present.

During the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts ( (including complex salts) to add metal ions to the inside of the particles and/or
Alternatively, these metal elements can be contained on the particle surface, and reduction sensitizing nuclei can be provided inside the particle and/or on the particle surface by placing the particle in an appropriate reducing 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, Research Disc
Losure (hereinafter sometimes abbreviated as RD) can be carried out based on the method described in No. 17643, Section 3.

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

Silver halide grains may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the +1001 plane to the (1111 plane) can be used.

Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed. The size of silver halide grains is 0.05 to 30μ, preferably 0.1 to 30μ.
20μ can be used.

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

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

Silver halide emulsions can be chemically enhanced by conventional methods. Namely, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
Noble metal aggravation methods using gold or other noble metal compounds can be used alone or in combination.

Silver halide emulsions can be optically enhanced to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. Aggravating pigments may be used alone, or two or more types 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, hemin cyanine dyes, steryl dyes and hemioxanol dyes are used.

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

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographs may be taken during chemical ripening, at the end of chemical ripening, and/or after chemical ripening and before coating a silver halide emulsion. Compounds known in the art as antifoggants or stabilizers can be added.

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

Photographic emulsion layers and other hydrophilic colloid layers of light-sensitive materials using silver halide emulsions as described above contain one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. It can be used to harden the membrane. 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-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1,3,5 -1
-lyacryloyl-hexahydro-5-1-lyazine,
1.3-vinylsulfonyl-2-propatol, etc.),
Active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.), mucohalogen acids M (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or 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 A1 of RD 17643, section
l1l! It is a compound listed above.

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 together with acrylic acid. , methacrylic acid, α, β-unsaturated dicarboxylic acid,
A polymer containing a combination of hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

In the photosensitive silver halide layers adjacent to the non-photosensitive fine-grain silver layer of the present invention, at least the second photosensitive silver halide layer counting from the non-photosensitive fine-grain silver layer to the support side contains a color developing agent. contains a diffusible DIR compound that reacts with the oxidant of to release a diffusive inhibitor or precursor.

In the present invention, it is sufficient that the diffusible DIR compound is contained in one or two of the up to two photosensitive halogenated silver layers on the side of the support. In addition, other layers (layers from the 3Nth layer onward to the support, etc.) have diffusivity D.
An IR compound may or may not further be contained.

In the present invention, the diffusion beam and the IR compound are represented by 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 group capable of releasing a highly diffusible development inhibitor or a development inhibitor.

A only needs to have the properties of a coupler, and it is not necessarily necessary to create a dye by cutting.

In the present invention, the group Y in the above general formula (1) is D represented by the following formulas (2A) to (2E), (3) to (5).
IR compounds can be preferably used. More preferably, the leaving group Y has the formula (2A) (2B) (2B) (4
), particularly preferably a compound represented by the formula (2B
)(2E)(4).

General formula of Y (2A) General formula of Y (2B) General formula of Y (2C) General formula of Y (2D) General formula of Y (2E) X is O19 or Se General formula of Y (3) General formula of Y Formula (4) General formula (5) of Y In the above general formulas (2A) to (2D) and (3), R
I 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, N-alkylcarbamoyl 5, N,
N-dialkylcarbamoyl group, nitro group, amino group,
N-arylcarbamoyloxy group, sulfamoyl group, N-alkylcarbamoyloxy group, hydroxy group,
It represents an alkoxycarbonylamino group, an alkylthio group, an arylthio group, an aryl group, a heterocyclic group, a cyano group, an alkylsulfonyl group, or an aryloxycarbonylamino group. n represents 1 or 2, and when n is 2, RI may be the same or different, and the total number of carbon atoms contained in n R3s is preferably 0 to 10.

and in the general formula (4), R2 represents an alkyl group, an aryl group or a heterocyclic group.

In general formula (5), R1 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 halogen atom, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group. , alkanesulfonamide group, cyano group, heterocyclic group, alkylthio group or amino group.

When R,,R+R3 or R4 represents an alkyl group, it may be substituted or unsubstituted, linear or branched, or cyclic alkyl.The substituent may be a halogen atom, a nitro group, cyano group, aryl group,
Examples include an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a carbamoyl group, a hydroxy group, an alkanesulfonyl group, an arylsulfonyl group, an alkylthio group, and an arylthio group.

RI+ When Rz, Rs or R4 represents an aryl group, the aryl group may be substituted.

As a substituent, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, a nitro group, an amino group, a sulfamoyl group, a hydroxy group, a carbamoyl group, an aryoloxycarbonylamino group, an alkoxycarbonylamino group, an acylamino group. group, cyano group, or ureido group.

When Rt, Rz, Rs or R1 represents a heterocyclic group, it represents a 5- or 6-membered monocyclic ring or fused ring containing a nitrogen atom, oxygen atom, or sulfur atom as a 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 Rz is preferably 1 to 15.

In the above general formula (5), the total number of carbon atoms contained in R1 and R4 is preferably 1 to 15.

In the above general formula (1), Y can take the structure of the following general formula (6).

General formula (6) of Y -T IME-I NHI B 17 In the formula, the TIME group is a group that is bonded to the coupling position of the coupler and can be cleaved by reaction with a color developing agent,
It is a group that can release the I NHI BIT group in a moderately controlled manner after being cleaved from the coupler.

The INHIBIT group is a group that provides a development inhibitor or a compound capable of releasing a development inhibitor.

In general formula (6), the -TIME-INHIBIT group can be represented by the following general formulas (7) to (13).

General formula of Y (7) General formula of Y (8) General formula of Y (9) % formula %) General formula of Y (10) cut-INHIBIT General formula of Y (11) General formula of Y (12) Y General formula (13) In general formulas (7) to (13), R3 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkoxycarbonyl group, an anilino group, an acylamino group, a 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)
In the general formulas (7), (11), (12) and (13), k represents an integer from O to 2, and in the general formulas (7), (10) and ( In 11), R4 represents an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, or an aryl group, and is represented by the general formula (12) and (
13), B represents an oxygen atom, ), and the INHIBIT group represents the general formula (2A), (2B), (3)
, has the same meaning as the general formula defined in (4) and (5), but differs in the number of carbon atoms.

However, in general formulas (2A), (2B) and (3),
-The total number of carbon atoms contained in each R in the molecule is 1 to 32
In the general formula (4), the number of carbon atoms contained in Rt is 1 to 32, and in the general formula (5), R3 and R
The total number of carbon atoms contained in 4 is 0 to 32.

When R% and R6 represent an alkyl group, it may be substituted or unsubstituted, chain-like or cyclic. Examples of the substituent include the substituents listed when R1 to R4 are alkyl groups.

When Rs and R6 represent an aryl group, the aryl group may be substituted, and the substituent is R.

- The substituents listed when R4 is a 7-aryl group can be mentioned.

Among the above diffusible DIR compounds, general formula (2A), (
Particularly preferred are those having a leaving group represented by 2B), (2E) or 5).

The yellow image-forming coupler residue represented by A in general formula (1) includes pivaloylacetanilide type, benzoylacetanilide type, malondiester type,
malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, malon ester monoamide type,
Coupler residues of benzothiazolylacetate type, benzoxacylylacetamide type, benzoxacylylacetate type, malon diester type, benzimidazolylacetamide type or benzimidazolylacetate type, 7 included in U.S. Pat. No. 3,841,880 Coupler residues derived from heterocycle-substituted acetamides or heterocycle-substituted acetates or U.S. Pat. No. 3.770.4
No. 46, British Patent No. 1.459.171, West German Patent (
OL S) No. 2.503.099, Japanese Patent Publication No. 50-13
No. 9738 or Research Disclosure 157
Examples thereof include coupler residues derived from acylacetamides described in No. 37 and heterocyclic coupler residues described in US Pat. No. 4,046.574.

The magenta image-forming coupler residue represented by A includes a 5-oxo-2-pyrazoline nucleus, pyrazolo-(1,5
-a) Coupler residues having a benzimidazole core or a cyanoacetophenone 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. Patent No. 4.05.
2.213, 4,088.491, 3.6
32.345, 3.958,993 or 3
．． Examples include the coupler residues described in No. 961.959.

Next, preferred specific examples of DIR compounds that can be used in the present invention are listed. However, as a matter of course, the DIR of the present invention
The compounds are not limited to those shown below.

Below margin 0 Lolo -ω Hit Lo0
RoC+J□0OCCHCO
OCIJts D-120H HNHz 0 RoQ
＾ 0 RoD
-190I -N Shini D-23 C, zlhsOcOcHcOOc+ zHtsH H Ro Toro Ql
0 0
b0
2 D-46 CH, CH.

H Uz r NO□ NO! O3H D-54 D-55 CJs CsH++(j) trIs IlHz3 These compounds are described in U.S. Pat.
, No. 958.993, No. 2.070.266, Research Disclosure No. 21228, December 1981, and the like.

In the present invention, the diffusible DIR compound is a photosensitive silver halide layer adjacent to the non-photosensitive fine-grain silver layer of the present invention, at least up to the second layer counting from the non-photosensitive fine-grain silver layer toward the support. It is essential that it be contained in 1Jlffl or 2 layers of the silver layer. However, in the third and subsequent layers counted toward the support, any non-photosensitive hydrophilic colloid layer or photosensitive silver halide layer may contain the diffusible DIR compound of the present invention. It may or may not be included.

The diffusible DIR compounds of the present invention are preferably halogenated! ! It can be added per mole of 1X10-' mol-1 mol, more preferably from 1X10-' mol to 1×1-1 mol.

In order to incorporate the diffusible DIR compound of the present invention into a coating solution for a silver halide emulsion or other photographic constituent layer, if the diffusible DIR compound is alkali-soluble, it may be added as an alkaline solution. If it is soluble,
For example, U.S. Patent No. 2.322.027, U.S. Patent No. 2.80
No. 1,170, No. 2.801.171, No. 2,2
72.181 and No. 2.304.840, the diffusible DIR compound is dissolved in a high boiling point solvent, if necessary in combination with a low boiling point solvent, and dispersed in the form of fine particles. It is preferable to add it to a silver halide emulsion or the like. At this time, if necessary, other haloquinone derivatives, ultraviolet absorbers, anti-browning agents, etc. may be used in combination, or two or more types of diffusible DIR compounds may be used in combination. Further, in detail, the preferred method of adding the diffusible DIR compound in the present invention is as follows:
The species or two or more of the diffusible DIR compounds are mixed with organic acid amides, carbamates, esters, ketones, urea derivatives together with other couplers, hydroquinone derivatives, anti-browning agents, ultraviolet absorbers, etc. as necessary. , ethers,
Hydrocarbons, etc., especially di-n-butyl phthalate, triresyl phosphate, triphenyl phosphate, di-isooctyl azelate, di-n-butyl sebacate, tri-hexyl phosphate, N, N-di-
Ethyl-caprylamidobutyl, N,N-diethyl laurylamide, n-pentadecyl phenyl ether, di-
Octyl phthalate, n-nonylphenol, 3-pentadecyl phenylethyl ether, 2,5-no 30I
- high boiling point solvents such as amyl phenyl butyl ether, monophenyl-di-0-chlorophenyl phosphate or fluoroparaffin, and/or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol monoacetate, nitromethane, Carbon tetrachloride, chloroform, cyclohexanetetrahydrofuran, methyl alcohol,
Acetonitrile, dimethylformamide, dioxane,
Silver halide is dissolved in a low boiling point solvent such as methyl ethyl ketone, mixed with an aqueous solution containing an alkyl benzene agent and/or a hydrophilic binder such as gelatin, and emulsified and dispersed using a high-speed rotation mixer, colloid mill, or ultrasonic dispersion device. Added to emulsifier.

In addition, the diffusible DIR compound may be dispersed using a latex dispersion method. The latex dispersion method and its effects are described in JP-A-49-74538, JP-A-51-59943, JP-A-54-32552, various publications, and Research Disclosure August 1876, 11&114850,
It is described on pages 77-79.

In the photosensitive silver halide layer of the present invention, a dye is formed by a campling reaction with an oxidized form of an aromatic primary amine developer (for example, a p-phenylenediamine derivative or an aminophenol derivative) in the color development process. A dye-forming coupler that forms is used. If dye-forming couplers are typically selected for each light-sensitive emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, and a yellow dye-forming coupler is selected for the blue-sensitive emulsion layer. , a magenta dye-forming coupler is used in the green-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

It is desirable that these dye-forming couplers have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Either 4-isomerism, in which 100 silver ions need to be reduced, or 2-isomerism, in which only 2 molecules of silver ions need to be reduced, may be used. The dye-forming coupler has a color correction effect, and by coupling with the oxidized form of the developing agent, it can be used as a development accelerator, bleach accelerator, developer, halogenated W&solvent, toning agent, and hardening agent. Compounds that release photographically useful fragments such as , fogging agents, anticapri agents, chemical sensitizers, spectral enhancers, and desensitizers are included.

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

Among these, benzoylacetanilide-based and pivaloylacetanilide-based compounds are useful. Specific examples of yellow coloring couplers that can be used include, for example, U.S. Patent No. 2,87
5.057, 3.265.506, 3.4
No. 08.194, No. 3.551.155, No. 3.
No. 582.322, No. 3.725.072, No. 3
．． No. 891,445, West German Patent 1, 547, 868
No., West German Application No. 2,219,917, West German Application No. 2,261
．． No. 361, No. 2,414.006, British Patent No. 1.
425.020, JP 51-10783, JP 47-26133, JP 48-73147, JP 50-
No. 6341, No. 50-87650, No. 50-1233
No. 42, No. 50-130442, No. 51-21827
No. 51-102636, No. 52-82424,
It is described in No. 52-115219, No. 58-95346, etc.

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

Specific examples of magenta color-forming couplers that can be used include, for example, U.S. Pat.
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. 3,553.
No. 319, No. 3.582, 322, No. 3.615
．． No. 506, No. 3,834,908, No. 3,8
91.445, West German Patent No. 1,810,464, West German Patent Application (OLS) No. 2,408.665, West German Patent No. 2,41
No. 7.945, No. 2,418.959, No. 2.424
．． No. 467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 49-7
No. 4027, No. 49-74028, No. 49-1295
No. 38, No. 50-60233, No. 50-159336
No. 51-20826, No. 51-26541, No. 52-42121, No. 52-58922, No. 53-
55122, Japanese Patent Application No. 55-110943, and the like.

Phenol or naphthol couplers are commonly used as cyan dye-forming couplers. Specific examples of cyan color-forming couplers that can be used include, for example, U.S. Patent No. 2.42.
3.730, 2.474,293, 2.8
No. 01.171, No. 2.895.826, No. 3.
No. 476.563, No. 3.737.326, No. 3
．． No. 758.308, specification No. 3,893,044, JP-A-47-37425, JP-A No. 50-10135,
No. 50-25228, No. 50-112038, No. 5
Couplers described in Japanese Patent Application Publication No. 0-117422, Japanese Patent Application Publication No. 50-130441, etc., and couplers described in Japanese Patent Application Laid-open No. 58-98731 are preferred.

Among dye-forming couplers, colored couplers, image stabilizers, color antifoggants, ultraviolet absorbers, fluorescent brighteners, etc. that do not need to be adsorbed on the silver halide crystal surface, hydrophobic compounds can be used using solid dispersion methods or latex dispersion methods. Various methods can be used, such as the method, oil-in-water emulsion dispersion method, etc., and 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.
Usually, it is dissolved in a high-boiling organic solvent with a boiling point of about 150°C or higher, if necessary in combination with a low-boiling point and/or water-soluble organic solvent, and stirred with a surfactant in a hydrophilic binder such as an aqueous gelatin solution. Homogenizer, homogenizer, colloid mill,
After emulsifying and dispersing using a dispersion means such as a flow jet mixer or an ultrasonic device, a zero dispersion can be added to the desired hydrophilic colloid liquid, or a step of removing a low-boiling organic solvent at the same time as dispersion is added. It's okay.

Examples of high-boiling point solvents include phenol m11 which does not react with the oxidized form of the developing agent, phthalic acid alkyl esters, phosphoric esters, citric esters, benzoic esters, alkylamides, fatty acid esters, trimesic esters, etc. with a boiling point of 150°C or higher. Organic solvents are used.

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

When dye-forming couplers, colored couplers, image stabilizers, color antifoggants, ultraviolet absorbers, fluorescent brighteners, etc. contain acid groups such as carboxylic acid or sulfonic acid, they can be added to a woody colloid as an alkaline aqueous solution. It can also be introduced into

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 different color-sensitive layers), causing color turbidity or deterioration of sharpness. A color antifoggant can be used to prevent graininess from becoming noticeable.

The color antifoggant may be contained in the emulsion layer itself, or
An 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 photosensitive materials and intermediate layers may contain ultraviolet absorbers to prevent fogging caused by discharge caused by charging of photosensitive materials due to friction, etc., and to prevent image deterioration due to ultraviolet rays. good.

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 a dye or an ultraviolet absorber is contained 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. A compound that can be preferably used as a development accelerator is RD 17
The compound is a compound described in Section XX1 B to D of No. 643, and the development retardant is a compound described in Section XXI E of No. 17643. black and white developing agents for development acceleration and other purposes, and/or
Alternatively, its precursor may be used.

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

A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. Compounds which can preferably be used as fluorescent brighteners are described in RD 17643, item 7.

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

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

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

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

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

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

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

When coating photosensitive materials, thickeners may be used to improve coating properties.For example, thickeners, such as hardeners, have quick reactivity, so if they are added to the coating solution in advance, they will form a gel before coating. For substances that may cause oxidation, it is preferable to mix them using a static mixer or the like immediately before coating.

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

Examples of the surfactant include, but are not limited to, natural surfactants such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkylamines, quaternary ammonium salts, lysine, and others. complex ig, cationic surfactants such as phosphonium or sulfoniums, anionic surfactants containing acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, sulfuric esters, phosphoric esters, amino acids, aminosulfonic acids,
Amphoteric surfactants such as sulfuric or phosphoric esters of aminoalcohols may be added. Also, for the same purpose,
It is also possible to use fluorosurfactants.

In carrying out the present invention, the total weight of the color photosensitive material is preferably 30 to 80 A/100ak, more preferably 30 to 70111r/1OOcIi, and most preferably 40 to 60A/100ak.

The layer structure that can particularly enhance the effects of the present invention includes a colloidal silver antihalation layer, (intermediate layer), red-sensitive layer, (intermediate layer), green-sensitive layer, (intermediate layer), and colloidal silver yellow layer in order from the support. One filter layer, a blue sensitive layer, (intermediate layer), a protective layer coated, and a colloidal silver halide prevention layer, (intermediate layer), a red sensitive layer, (intermediate layer), and a green sensitive layer in order from the support. , (intermediate layer), blue-sensitive layer, (intermediate layer), red-sensitive layer, (intermediate layer), green-sensitive layer, (one layer of colloidal silver yellow filter), blue-sensitive layer, (intermediate layer), coated with protective layer layer structure,
It is complete. Note that the layers in parentheses may be omitted. The red-sensitive layer, green-sensitive layer, and blue-sensitive layer may each be divided into a low-sensitivity layer and a high-sensitivity layer. In addition, the special public service 1977-154
A layer structure in which at least one of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer is divided into three partial layers as seen in No. 95, and a high-sensitivity emulsion layer unit as seen in JP-A-51-49027. Layer structure with separate low-speed emulsion layer units, and West German Publications 2 and 6
No. 22,922, No. 2622923, No. 262292
4, No. 2,764,826, and No. 2,704,797.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Color photographic processing is performed, and color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process. Instead of the process used above, a bleach-fixing process can be carried out using a one-bath bleach-fixing solution, or a one-bath developing, bleach-fixing solution that allows color development, bleaching, and fixing to be performed in one bath. It is also possible to perform a monobath treatment process using

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed.In these processes, a color developing agent, or An activator treatment step may be performed in which the precursor is contained in the material and the development treatment is performed with an activator solution, or the activator treatment can be applied to the monobath treatment. Typical treatments during these treatments are as follows: (In these treatments, any of the water washing process, body washing process, and stabilization process is performed as the final process.)・Color development process - Bleaching Processing process Constant fixation process/Color development process - Bleach fixing process/Pre-hardening process - Color development process - Stop fixing process - Washing process - Bleach process Constant fixing process - Washing process - After Hardening process/Color development process - Water washing process - Supplementary color development process - Stop process - Bleach process Constant fixation process/Active bake process - Bleach-fix process/Activator process - Constant bleach process The treatment temperature is usually selected in the range of 10°C to 65°C,
The temperature may exceed 65°C, preferably 25°C to
Processed at 45°C.

The color developing solution is generally an alkaline aqueous solution containing a color developing agent.The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol-based and p-phenylezine-based derivatives. These color developing agents can be used as salts of organic acids and inorganic acids; for example, hydrochloric acid, sulfate, p-h luenesulfonate, sulfite, shelerate, benzenesulfonate, etc. can be used. I can do it.

These compounds are generally about 0.0% in color developer 11.
A concentration of 1 to 30 g is used, more preferably a concentration of about 1 to 15 g for color developer 1e. If the amount added is less than 0.1 g, sufficient color density cannot be obtained.

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

Particularly useful primary aromatic amine color developers include N, N-
A dialkyl-p-phenylenediamine compound,
Alkyl groups and phenyl groups may be substituted or unsubstituted. Among them, examples of particularly useful compounds include N-N-dimethyl-p-phenylenediamine hydrochloride and N-methyl-p-phenylenediamine hydrochloride N.

N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amino Aniline sulfur [1, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N, N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl- 3-
Examples include methylaniline-p-1-luenesulfonate.

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

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

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

The p value 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.

In the color developing solution used in the present invention, various chelating agents can be used in combination as metal ion sequestering agents.
-Organic phosphonic acids such as hydroxyethylidene-1,1-diphosphonic acid, 7-minobolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphonic acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonophosphonic acid, etc. Examples include phosphonocarboxylic acids such as 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 a bleaching agent, a metal complex salt of an organic acid is used, for example, an organic acid such as polycarboxylic acid, aminopolycarboxylic acid, oxalic acid, citric acid, etc., coordinated with a metal ion such as iron, cobalt, copper, etc. is used. . Among the above 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, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, Examples include ethylenediaminetetrapropionic acid and phenylenediaminetetraacetic acid.

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts, these bleaching agents have a content of 5 to 450 g/j! , more preferably 20~
Use at 250 g/l.

In addition to the above bleaching agent, the bleaching solution may contain a sulfite as a preservative, if necessary. Alternatively, it may be a bleaching solution containing an ethylenediaminetetraacetate iron(I[I) complex salt bleaching agent and containing a large amount of a halide such as ammonium bromide. In addition, 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.

The pH of the bleaching solution used is 2.0 or higher, but generally it is 4.0.
It is used between 0 and 9.5, preferably between 4.5 and 8.0, and most preferably between 5.0 and 7.0.

A fixer having a commonly used composition can be used. As a fixing agent, a compound that reacts with silver halide to form a water-soluble complex salt, such as a thiosulfate such as potassium thiosulfate, sodium thiosulfate, or ammonium thiosulfate, or potassium thiocyanate, which is used in ordinary fixing processing, may be used. Typical examples thereof include thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea, and thioether. These fixatives are 5
It is used in an amount of 70 to 250 g/l or more, but it is generally used in an amount of 70 to 250 g/l.

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.

In addition, the bleaching solution and/or fixing solution includes various PI buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. These agents may be contained alone or in combination of two or more. Furthermore, various fluorescent 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, and hardening agents such as water-soluble aluminum salts. ,methanol,
Organic solvents such as dimethylsulfamide and dimethylsulfoxide can be appropriately contained.

The pH of the fixer is used at 3.0 or higher, but generally it is 4.
．． 5 to 10, preferably 5 to 9.5, most preferably 6 to 9.

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

The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. In addition, a bleach-fixing solution consisting of an ethylenediaminetetraacetic acid iron (Ill) complex salt bleach and a small amount of a halide such as ammonium bromide other than the silver halide fixing agent mentioned above, or conversely, a halide such as ammonium bromide may be used. A bleach-fix solution containing a large amount of iron ethylenediaminetetraacetate (iron ethylenediaminetetraacetate)
m)t! A special bleach-fix solution having a composition consisting of a combination of a salt bleach and a large amount of a halide such as ammonium bromide may 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 halogenation-limited adhesive that can be included in the bleach-fix solution include the fixing agents described in the above-mentioned fixing process. The concentration of the fixing agent, the pH 1L additive 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 has a ρ■ of 4.0 or more, but is generally used in a range of 5.0 to 9.5, preferably 6.0 to 8.
5, most preferably 6.5 to 8.5.

〔Example〕

Specific examples of the present invention will be described below. However, it goes without saying that the embodiments of the present invention are not limited to these embodiments.

The following layers were coated on a cellulose triacetate film to prepare a multilayer color negative photographic material (sample ll & ll
, comparison) was created.

1st layer: Antihalation layer 2nd layer: Intermediate layer gelatin ・・・・・・・・・・・・・・・・・・
・ 1.2 g/rd 3rd layer: Low-sensitivity red-sensitive emulsion layer 4th layer: High-sensitivity red-sensitive emulsion 1 (t! Coating amount) 5th M = Intermediate layer gelatin ・・・・・・・・・・・・・・・・・・
・ 0.80g/nl 6th layer: Low sensitivity green irritant layer 1.1 g
/rd 7th layer: High sensitivity green sensitive layer 8th layer: Yellow filter layer 9th layer: Low sensitivity blue sensitive layer 10th layer: High sensitivity blue sensitive layer 11N: 1st protective layer 12th layer: 2nd protection Layer In addition to the above composition, each emulsion layer contains 4-hydroxy-6-methyl-1,3,3a, 7-titrazaindene, 1-phenyl-5-mercaptotetrazole, etc. In addition to the above composition, each layer contains Gelatin hardener (-1 and H-2, surfactant, etc.) were added.

Also, No. 8. 9. S-1 on the 10th layer, 3 on the 9th and 10th layer
-2, S-3 was added to the 11th layer.

The composition of the emulsion used is shown in the table below. In addition, the compounds indicated by abbreviations above are shown below.

UV-1 Exacerbating dye-I Exacerbating dye-■ Exacerbating dye-m C-1011 NaOzS 5O=NaE D −
201+ H OClhCONIIClhCIIgOCLHB S −
1 C, O.

C00CII□Cl1C4Hq C, II.

B5-2 Sensitizing dye■ Sensitizing dye V Multiplying dye■ C.I. 'C.J. 'CI D-4 0 ■ C.I. CHt=lCHClhCfhSO□CH=C11.

S-I S-2C11.

NiI□CONH - CIl Clh - NI
ICONII□In this example, the 11th layer is a non-photosensitive hydrophilic colloid layer, and the 10th layer and the 9th layer are photosensitive silver halide layers adjacent to the non-photosensitive hydrophilic colloid layer on the support side. . Sample 11hl is the 9th layer, 10F
lj does not contain any DIR compounds, and the sample is 1 lkL.
7 further contains no fine silver halide grains in the 11th layer,
Sample 8.15.16 contains a DIR compound in the 9th FJ but does not contain fine silver halide grains in the 11th layer.
Both are comparative samples outside the present invention.

Each sample flint-18 thus prepared was subjected to wedge exposure using white light and green light, and then subjected to the following development treatment.

Processing process (38℃) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Fixing
6 minutes 30 seconds Wash with water 3 minutes 1
Stabilization for 5 seconds Drying for 1 minute and 30 seconds The composition of treatment W1 used in each treatment step is as follows.

Color developer> 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine sulfate 2.0g anhydrous carbonate Potassium 37.5 g Sodium Bromide
1.3g nitrilotriacetic acid trisodium salt (monohydrate) 2.5g potassium hydroxide 1.0g Add water to prepare Iy.

<Bleach solution> Ethylenediaminetetraacetic acid iron ammonium salt 100. g Ethylenediaminetetraacetic acid 2 Ammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 +*1 Add water to make 11, and adjust to pn=60 using aqueous ammonia.

Fixer> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water and mix 11
and adjust to pl+ = 6.0 using acetic acid.

Stabilizer> Formalin (contains 37% water) 1.5
ml Conidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5
Add ml water to make 12.

Second, the magenta image density difference obtained with white light and green light,
That is, the density difference of green light when the white light has a green density of 1.7 is shown as a relative value when sample 5 is taken as 100.

Table 2 As shown in Table 2, samples 2-6.9-14 of the present invention were
Comparative sample 1. Compared to No. 7, color separation in monochromatic green light was clearly superior, and an improvement in color reproducibility was observed.

Further, a slight improvement in color separation was also observed with respect to comparative samples 8.15.16.

Next, samples 1 to 16 were humidity-controlled to 25° C. 153% R1+, sealed in a barrier bag, and heat-treated at 55° C. for 5 days. Thereafter, the untreated sample was exposed simultaneously to a wedge using white light, and then the above-mentioned development process was performed.

Table 3 shows the Capri density difference (blue density value) values of the thermo-treated samples.

Table 3 From Table 3, it can be seen that the sample of the present invention has very little thermocapri generation compared to the comparative sample.

Next, using the color developing solution mentioned above, sample 2.5°7.8
, 11, 13.15 were used to examine the processing running characteristics. The replenishment amount of color developer during running is 22
The rate was set at 0 m1/drrr, and the rate was increased until the mother liquor exchange rate was 90%.

Sample 15 was exposed to a wedge with white light and then developed using this running solution. Table 4 shows the minimum blue density and the sensitivity when processed with the running solution obtained by running sample 5 as 100. Relative values are shown.

Table 4 As can be seen from Table 4, the running liquids using the comparison sample as opposed to the sample of the present invention resulted in a decrease in the minimum concentration value and a decrease in sensitivity, which is a problem. On the other hand, good results were obtained with the samples of the present invention.

(Effects of the Invention) As described above, the silver halide photographic material of the present invention maintains the advantage that excellent image quality characteristics can be obtained by containing a diffusive DIR compound that releases a diffusivity inhibitor or precursor. However, the storage stability and development processing characteristics are improved, and the problems of the prior art are solved.

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one non-photosensitive hydrophilic colloid layer containing substantially non-photosensitive fine silver halide grains on a support, comprising: The colloid layer has a photosensitive silver halide layer adjacent to the support side, and has no photosensitive silver halide layer on the other side, and at least one of the adjacent photosensitive silver halide layers. 2
It is characterized by containing a diffusible DIR compound that reacts with an oxidized product of a color developing agent to release a diffusivity inhibitor or its precursor in one or two of the photosensitive silver halide layers up to the second layer. Silver halide photographic material.