JPH0629957B2 - Silver halide photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material having improved photographic characteristics, and further has excellent sensitivity, graininess and processing stability and a latent image after exposure. The present invention relates to a silver halide photographic light-sensitive material having greatly improved storability.

[Conventional technology]

In recent years, the demand for silver halide photographic light-sensitive materials (hereinafter, simply referred to as light-sensitive materials) has been extremely strict, and as photographic performances, high sensitivity, excellent graininess, sharpness, rich latitude, sufficiently high optical density, and low Fogging density is required, and in terms of processability, rapid and efficient development, fixing, washing with water, or processed physical properties are required, and these photographic performances and processability are long-lasting and storable. To be done.

In order to improve the image quality of a high-sensitivity light-sensitive material, silver halide composition, especially silver iodide in silver halide grains, is used as one of the techniques for improving image characteristics such as gradation, graininess and sharpness. It is a well-known technique to improve the image quality by including the effect of suppressing the development by the iodide ion released during development.

For example, a silver halide emulsion generally used for a black and white light-sensitive material contains 2 mol% or more of silver iodide, and the above-mentioned technique can be used for adjusting the above-mentioned image quality. The material generally has a silver iodide content of 4 mol% or more, and the above-mentioned technique can be utilized more effectively. However, increasing the content of silver iodide in this way can improve the image quality. Although it is preferable as a means for improving the sensitivity, on the other hand, it cannot be said to be a preferable means for improving the sensitivity because silver iodide works suppressively against the sulfur sensitizing reaction or the developing reaction during the chemical ripening.

The desensitization resulting from the inhibitory action that occurs during the above chemical ripening or development can be considerably recovered, for example, by adding an increased amount of a sulfur sensitizer or a gold sensitizer during the chemical ripening,
At the same time, the emulsion coating solution and the light-sensitive material are deteriorated in stability over time, and fog is likely to occur.

On the other hand, most conventional silver halide emulsions have a wide grain size distribution and a non-uniform crystal habit, and therefore, it is said that the optimum chemical sensitization is performed on any grain during chemical sensitization. Hard to say. Therefore, at present, the sensitivity that each particle originally has has not been sufficiently extracted.

Therefore, in recent years, a monodisperse emulsion (that is, a silver halide emulsion having a narrow grain size distribution and a uniform crystal habit) has been attracting attention.

On the other hand, based on the study of the growth mechanism of silver halide crystals, the next-stage precipitation was sequentially laminated on the crystal nuclei of the preceding silver halide, and the composition or progress environment of each precipitate was intentionally controlled (core / shell) emulsion. Is also well known.

A photographic emulsion composed of core / shell type silver halide grains, which are substantially monodisperse and have a higher silver iodide content in the core portion than in the shell portion, derived from the above-mentioned technique, has sensitivity, graininess, and processing properties. It is expected that it will be most suitable for producing a photosensitive material having excellent stability.

[Problems to be solved]

However, in a color light-sensitive material, a silver halide emulsion layer is generally spectrally sensitized in each of red, green and blue light sensitive regions. For example, as a sensitizing dye used when spectrally sensitizing the silver halide emulsion layer in the red light region, for example, U.S. Pat.Nos. 2,269,234, 2,270,378, 2,442,710, and 2,4
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes described in the specifications of Nos. 54,620 and 2,776,280.

When the above emulsion is spectrally sensitized red-sensitive with such a sensitizing dye, the latent image keeping property is remarkably deteriorated. On the other hand, the ureido type cyan coupler is an excellent coupler such as less dye loss in a fatigue bleaching bath, but it also has a drawback that the latent image fluctuation with time is large.

An object of the present invention is to provide a light-sensitive material having high sensitivity, excellent graininess, sharpness, low fog density, and less variation in latent image with time after exposure.

[Means for solving problems]

As a result of various studies, the present inventors have found that the problems can be solved as follows. That is, in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer contains a group of substantially monodisperse silver halide grains. The silver halide grains forming the silver halide grain group are each composed of a core portion and a shell portion made of silver iodobromide, and the average silver iodide content in the shell portion is the average silver iodide content in the core portion. Core / shell type silver halide in which the ratio of the volume of the shell portion to the total volume of the silver halide grains including the core portion and the shell portion is 15% to 80%. The silver halide emulsion layer is a silver halide photographic light-sensitive material characterized by containing a cyan coupler represented by the following general formula [I].

General formula [I] In the formula, X represents a hydrogen atom or a group capable of splitting off upon coupling with an oxidation product of an aromatic primary amine color developing agent, and R ₁ represents an optionally substituted aryl group (eg, phenyl group, naphthyl group, etc.). ) Or a heterocyclic group, R ₂
Represents a ballast group necessary for imparting diffusion resistance to the cyan coupler represented by the general formula [I] and the cyan dye formed from the cyan coupler.

R ₁ is preferably a substituted phenyl group, and as the substituent, a trifluoromethyl group, a cyano group, a halogen,
A substituted phenyl group having at least one group selected from a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted phenylsulfonyl group, a cycloalkylsulfonyl group, an alkylsulfamoyl group and an arylsulfamoyl group is particularly preferable.

R ₂ preferably represents an aliphatic group or an aromatic group, and examples thereof include an alkyl group having 4 to 30 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, a 5-membered or 6-membered heterocyclic group and the like. Preferred is a group represented by the general formula [Ia].

General formula [Ia] In the formula, J is an oxygen atom or a sulfur atom, k is an integer of 0 to 4, l is 0 or 1, and when k is 2 or more, two or more R _{4 s} may be the same or different, R ₃ is a linear or branched alkylene group having 1 to 20 carbon atoms, R ₄
Represents a monovalent group, for example, a halogen atom (preferably,
Chlorine, bromine), alkyl group (preferably linear or branched alkyl group having 1 to 20 carbon atoms (eg, methyl, tert-
Butyl, tert-pentyl, tert-octyl, dodecyl,
Pentadecyl)}, an aralkyl group (eg, benzyl, phenethyl), an aryl group (eg, phenyl), a heterocyclic group (preferably a nitrogen-containing heterocyclic group), an alkoxy group (preferably a linear or branched carbon number of 1 to 20) Alkyloxy group (eg, methoxy, ethoxy, tert-butyloxy, octyloxy, decyloxy, dodecyloxy)}, aryloxy group (eg, phenoxy), hydroxyl group, acyloxy group {preferably alkylcarbonyloxy group, arylcarbonyl An oxy group (eg acetoxy, benzoyloxy)}, a carboxy group, an alkoxycarbonyl group (preferably having a carbon number of 1
20 linear or branched alkyloxycarbonyl), aryloxycarbonyl group (preferably phenoxycarbonyl), alkylthio group (preferably having 1 to 20 carbon atoms)
Alkylthio group), an acyl group (preferably a linear or branched alkylcarbonyl having 1 to 20 carbon atoms), an acylamino group (preferably a linear or branched alkylcarbamide having 1 to 20 carbon atoms, benzenecarbamide), Sulfonamide group (preferably linear or branched alkylsulfonamide having 1 to 20 carbon atoms, benzenesulfonamide), carbamoyl group (preferably linear or branched alkylaminocarbonyl having 1 to 20 carbon atoms, phenylaminocarbonyl) , A sulfamoyl group (preferably a linear or branched alkylaminosulfonyl having 1 to 20 carbon atoms, phenylaminosulfonyl), an arylsulfonyl group (preferably phenylsulfonyl) and the like.

Among the groups represented by the general formula [Ia], a particularly preferred group is represented by the following general formula [Ib].

General formula [Ib] In the formula, R ₅ is a linear or branched alkyl group having 1 to 20 carbon atoms (eg, ethyl, iso-propyl, butyl, dodecyl), and R ₆ is a branched alkyl group having 3 to 20 carbon atoms (eg, tert-butyl). , Tert-pentyl) and R ₇ are the same as R ₄ in the general formula [Ia]. m and n each represent an integer of 1 or 2.

X represents a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidation product of a color developing agent, and examples thereof include a halogen atom (for example, each atom of chlorine, bromine, fluorine, etc.), an oxygen atom, a sulfur atom or Examples thereof include an alkoxy group having a nitrogen atom directly bonded to the coupling position, an aryloxy group, a carbamoyloxy group, a carbamoylmethoxy group, an acyloxy group, an allylthio group, a sulfonamide group, and a succinimide group. Examples include U.S. Pat.No. 3,741,563, JP-A-47-37425, and JP-B-48-36894.
No. 50, No. 50135, No. 50-117422, No. 50-130441
No. 51, No. 51-108841, No. 50-120334, No. 52-18315, No.
Examples include those described in No. 53-105226.

The ureido type cyan coupler according to the present invention can be easily synthesized by the method described in, for example, US Pat. No. 3,758,308 and JP-A-56-65134.

The preferred compounds of the present invention will be described below in specific examples.
It is not limited by this.

(1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (21) (22) (23) (24) (25) The monodisperse silver halide grain in the present invention means that when the emulsion is observed by an electron micrograph, the shape of each silver halide grain looks uniform and the grain size is uniform and is defined by the following formula. The particle size distribution is as follows. That is, when the standard deviation S of the particle size distribution is divided by the average particle size, the value is 0.20 or less.

The grain size referred to here is the diameter of spherical silver halide grains, and the diameter of the projected image converted to a circular image of the same area in the case of cubic or non-spherical grains. That is, the average particle diameter is the average value thereof, and when the individual particle diameter thereof is r _i and the number thereof is n _i , is defined by the following formula.

Here, the standard deviation S is usually used in science and is calculated by the following formula.

The above particle size can be measured by various methods generally used in the art for the above purpose. A typical method is Loveland's “particle size analysis method” A. S. T. M. Symposium on Right Microscopy, 1955, 94-122
P. Or "Theory of Photographic Processes" by Mies and James, Third Edition, Chapter 2, Macmillan, Inc. (1966). This particle size can be measured using the projected area of the particle or an approximate diameter. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The silver halide grains used in the present invention are cubic, tetradecahedral,
It may be a normal crystal such as an octahedron, may be composed of twin crystals, or may be a mixture thereof, but is preferably a normal crystal. As a method for obtaining a core / shell type normal crystal emulsion, a water-soluble silver salt solution and a water-soluble halide solution are added to a gelatin solution containing normal crystal seed particles under a double jet method under the control of pAg and pH. Can be obtained by adding. In determining the addition rate, reference can be made to JP-A-54-48521 and JP-A-58-49938.

The method for producing an emulsion consisting of twin crystals of the core / shell type is as follows.
For example, JP-A-54-118823 can be referred to.
These methods are characterized by forming a silver iodide nucleus in the initial stage and then adding a water-soluble silver salt and a water-soluble halide solution to cause a conversion reaction to form a core made of silver iodobromide.

The core / shell type twin crystal emulsion can also be produced by ripening a multi-twin crystal nuclei emulsion in the presence of a silver halide solvent into a spherical seed emulsion and growing it by a double jet method. it can.

The silver halide grain used in the present invention has a grain structure composed of two or more layers having different silver iodide contents, and the outermost surface layer (shell) of the two or more layers. (Part) is lower than the silver iodide content of the inner layer (core part). The silver iodide content of the core part may be 5 to 40 mol%, preferably 6 to 30 mol%, more preferably 7 mol%.
~ 20 mol%. The silver iodide content of the shell part is characterized by being lower than the silver iodide content of the core part, and the silver iodide content of the core part may be lower than 40 mol%. The silver iodide content of the shell portion can be taken.
The silver iodide content of the shell portion is preferably less than 5 mol%, more preferably 0.5 to 4.0 mol%.

In the present invention, the difference in content between the core portion having a high silver iodide content and the shell portion having a low content of the silver halide grains may have a sharp boundary, and the boundary is not always clear and continuous. It may change. Further, the silver iodide composition in the core portion and the shell portion may be unevenly distributed.

Further, the proportion of the shell portion of the silver halide grains used in the present invention is 15 to 80%, preferably 15 to 70%, more preferably 20 to 60%.

The distribution state of silver iodide in the above silver halide grains can be detected by various physical measurement methods, for example, at a low temperature as described in Abstracts of the Annual Meeting of the Photographic Society of Japan, 1981. It can also be investigated by measuring the luminescence at.

The distribution state of silver iodide in the silver halide grains can be confirmed by analysis of diffraction peaks obtained by powder X-ray diffractometry.

In the present invention, silver iodide or silver iodobromide can be used as the silver halide, but silver iodobromide is particularly preferable, and a trace amount of silver chloride can be used as long as the photographic performance of the emulsion is not impaired.

Further, a highly monodispersed emulsion can be obtained by allowing a hydroxytetrazaindene compound to exist during grain growth of the core / shell type monodispersed emulsion used in the present invention.

These silver halides are active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine, etc .; selenium sensitizers; reduction sensitizers, such as stannous salt, thiourea dioxide, polyamines, etc .; precious metal sensitizers. Agents such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurosulfobenzothiazole methyl chloride and the like, or sensitizers of water-soluble salts such as ruthenium, palladium, platinum, rhodium and iridium , Specifically ammonium chloroparadate, potassium chlorobratinate, sodium chloroparadate, etc. (some of these act as sensitizers or antifoggants depending on the amount), alone, Alternatively, they are used in combination as appropriate (for example, a gold sensitizer and a sulfur sensitizer are used in combination, a gold sensitizer and a sulfur sensitizer are used together. Such as the combination of the down sensitizer) that may be chemically sensitized.

Further, this silver halide can be optically sensitized to a desired wavelength range, and for example, an optical sensitizer such as a cyanine dye such as a zeromethine dye, a monomethine dye, a dimethine dye, and a trimethine dye or a merocyanine dye alone, Alternatively, they can be used in combination (for example, supersensitization) to perform optical sensitization.

The silver amount of the monodisperse silver halide grains contained in the silver halide emulsion layer constituting the light-sensitive material according to the present invention is generally 1.0 to 10.0 g / m ² , but preferably 1.5 to 6.0 g. / M
^{Is 2} .

The light-sensitive material according to the present invention includes not only the silver halide emulsion layer containing the cyan coupler of the present invention but also a silver halide emulsion layer containing a magenta coupler and a silver halide emulsion layer containing a yellow coupler. Of course, the total amount of light-sensitive silver halide in the light-sensitive material is generally 5.5 to 15.0 g.
/ M ² , preferably 5.5 to 10.0 g / m ² . In addition,
The silver halide grains contained in the silver halide emulsion layer containing the magenta and yellow couplers may or may not be monodisperse.

When the present invention is applied to a color light-sensitive material, for example, a silver halide emulsion layer containing a cyan coupler according to the present invention is generally a red-sensitive light-sensitive layer, but the light-sensitive layer is substantially It may be composed of a plurality of silver halide emulsion layers having the same color sensitivity and different sensitivities. Depending on the purpose and use, the cyan coupler-containing layer is not limited to the red-sensitive photosensitive layer.

In the present invention, the combination of the cyan coupler and the monodisperse core / shell type silver halide grains may be contained in at least one of the plurality of silver halide emulsion layers.

The photographic emulsion layer of the color light-sensitive material according to the present invention may contain a dye-forming coupler other than the present invention, that is, a compound which reacts with an oxidation product of an aromatic amine (usually primary amine) developing agent to form a dye. Good. The coupler is preferably a non-diffusing coupler having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ions.

As the yellow coupler, a known open chain ketomethylene type coupler can be used. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous. Specific examples of yellow color-forming couplers that can be used include U.S. Patents 2,875,057, 3,265,506, and 3,408,194.
No., 3,551,135, 3,582,322, 3,725,072,
3,891,445, West German patent 1,547,868, West German application publication (OLS) 2,219,917, 2,261,361, 2,414,006.
No., British Patent No. 1,425,020, Japanese Patent Publication No. 51-10783, JP-A No. 4
7-26133, 48-73147, 51-102636, 50-6341
No. 50, No. 123342, No. 50-130442, No. 51-21827, No.
50-87650, 52-82424, 52-115219, etc.

As the magenta color coupler, a pyrazolone compound, an indazolone compound, a cyanoacetyl compound or the like can be used, and a pyrazolone compound is particularly advantageous.
Specific examples of magenta color couplers that can be used are described in US Pat.
600,788, 2,983,608, 3,062,653, 3,127,2
No. 69, No. 3,311,476, No. 3,419,391, No. 3,519,429
No., No. 3,558,319, No. 3,582,322, No. 3,615,506,
No. 3,834,908, No. 3,891,445, West German patent 1,810,464
Issue, West German application publication (OLS) 2,408,665, 2,417,945
No. 2,418,959, 2,424,467, Japanese Patent Publication No. 40-6031
No. 5, JP-A-51-20826, No. 52-58922, No. 49-129538
No. 49, No. 74027, No. 50-159336, No. 52-42121, No. 4
9-74028, 50-60233, 51-26541, 53-55122
No., etc.

The cyan coupler according to the present invention may be used in combination with other couplers. For example, as the cyan coupler which can be used in combination, a phenol compound, a naphthol compound or the like can be used. A specific example is U.S. Pat.
2,434,272, 2,474,293, 2,521,908, 2,89
5,826, 3,034,892, 3,311,476, 3,458,315
No., No. 3,476,563, No. 3,583,971, No. 3,591,383,
No. 3,767,411, No. 4,004,929, West German application published (OL
S) 2,414,830, 2,454,329, JP-A-48-59838,
51-26034, 48-5055, 51-146828, 52-696
24 and 52-90932.

Two or more of the above couplers can be contained in the same layer.
The same compound may be contained in two or more different layers. These couplers generally contain 2 per mole of silver in the emulsion layer.
× 10 ^{-3 to} 5 × 10 ^-1 mol, preferably 1 × 10 ^{-2 to} 5 × 10 ^-1
Mol added.

To introduce the above coupler into the silver halide emulsion layer, a known method such as the method described in US Pat. No. 2,322,027 can be used. For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.),
Phosphate ester (diphenyl phosphate, tolphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, etc.), citric acid ester (eg, tributyl acetylcitrate), benzoic acid ester (eg, octyl benzoate), alkylamide (eg, diethyllaurylamide) ), Alkyl-substituted phenols (eg 2,4-di-t-amylphenol, 2,4-
Di-t-nonylphenol), fatty acid esters (eg dibutoxyethyl succinate, dioctyl azelate), etc., or organic solvents having a boiling point of about 30 to 150 ° C., for example, lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate. , Sec-butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., and then dispersed in a hydrophilic colloid. The above high boiling point organic solvent (H
BS) and a low boiling point organic solvent (LBS) may be mixed and used.

Further, the dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

The color light-sensitive material according to the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, a benzotriazole compound substituted with an aryl group (see US Pat. No. 3,533,
No. 794), 4-thiazolidone compounds (for example, those described in US Pat. Nos. 3,314,794 and 3,352,681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds ( For example, a butadiene compound (for example, those described in US Pat. No. 4,045,229) or a benzoxazole compound (for example, those described in US Pat. No. 3,700,455) can be used. Further, those described in US Pat. No. 3,499,762 and JP-A-54-48535 can also be used. Ultraviolet absorbing couplers (for example, α-naphthol type cyan dye forming couplers) and ultraviolet absorbing polymers may be used.
These UV absorbers may be mordanted in a specific layer.

In the color light-sensitive material to which the present invention is applied, hydrophilic colloids which are advantageously used for preparing a silver halide emulsion and hydrophilic colloids which are used in the non-photosensitive hydrophilic colloid layer include gelatin and phenylcarbamylation. Derivatives such as gelatin, acylated gelatin, phthalated gelatin, colloidal albumin, agar, gum arabic, hydrolyzed cellulose acetate, carboxymethyl cellulose, hydroxyethyl cellulose, cellulose derivatives such as methyl cellulose, acrylamide,
Imidized polyacrylamide, casein, vinyl alcohol polymers containing urethanecarboxylic acid groups or cyanoacetyl groups such as vinyl alcohol-vinyl cyanoacetate copolymer, polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, proteins or saturated acylated proteins and vinyl. A polymer obtained by polymerization with a monomer having a group is included.

The above-mentioned silver halide emulsion contains 1-phenyl-5-mercaptotetrazole, 3-sodium in order to prevent sensitivity deterioration and fogging during the production process, storage or processing of the light-sensitive material.
Various compounds such as a heterocyclic compound such as methylbenzothiazole and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, a mercapto compound, and a metal salt can be added.

Hardening treatment of the emulsion is carried out according to a conventional method. The hardener used is a conventional photographic hardener, for example, aldehyde compounds such as formaldehyde, glyoxal, and glutaraldehyde, and their derivative compounds such as acetal or sodium bisulfite adduct, methanesulfonic acid ester compounds. Compounds, epoxy compounds, aziridine compounds, active halogen compounds, maleimide compounds, active vinyl compounds, carbodiimide compounds, isoxazole compounds, N-methylol compounds, isocyanate compounds, or chrome meiban,
An inorganic hardener such as zirconium sulfate can be used.

A surfactant may be added to the above silver halide emulsion alone or as a mixture. As the surfactant, a coating aid, an emulsifier, a penetrating agent for treating liquid, an antifoaming agent, an antistatic agent, an anti-adhesive agent, a material for improving photographic properties or controlling physical properties, Natural products such as saponins, nonionic surfactants such as alkylene oxides, glycerins, glycidols, higher alkylamines, pyridine, other heterocycles, quaternary nitrogen onium salts, phosphonium or sulfonium cations, etc. Various surfactants such as surfactants, anionic surfactants containing acidic groups such as carboxylic acid, sulfonic acid, phosphoric acid, sulfuric acid ester group and phosphoric acid ester group, and amphoteric surfactants such as amino acids and aminosulfonic acids are available. Can be used.

Further, for the purpose of increasing the stability of color photographs, p-substituted phenols can be contained in the emulsion layer of the color light-sensitive material of the present invention and / or the non-light-sensitive hydrophilic colloid layer which is a layer adjacent thereto. . Particularly preferred p-substituted phenols include alkyl-substituted hydroquinones, bishydroquinones, polymer hydroquinones, p-alkoxyphenols, phenolic compounds and the like. Furthermore, alkoxy or acyloxy derivatives of 6-chromanol or 6,6'-dihydroxy-2,2'-spirochroman are likewise used.

The color light-sensitive material according to the present invention is produced by applying it on a support having good flatness and having little dimensional change during the production process or processing. As this support, a film such as cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyethylene terephthalate, polyamide, polycarbonate, polystyrene or polyethylene laminated paper,
There are polypropylene synthetic paper, baryta paper, and the like, and these supports are appropriately selected according to the intended use of each light-sensitive material.

These supports are generally subjected to a subbing process in order to enhance the adhesion with the silver halide emulsion layer. Typical subbing materials used for subbing processing include vinyl chloride or vinylidene chloride copolymers, vinyl alcohol ester copolymers, unsaturated carboxylic acid-containing copolymers, and dienes such as butadiene. Copolymer of, acetal copolymer,
Copolymers of unsaturated carboxylic acid anhydrides such as maleic anhydride, especially vinyl alcohol esters such as vinyl acetate, or copolymers with styrene or its water, alkali,
Examples thereof include ring-opened products with alcohols or amines, cellulose derivatives such as nitrocellulose and diacetylcellulose, compounds containing an epoxy group, gelatin or gelatin modified products, and polyolefin copolymers.

Furthermore, gelatin or polyols, monohydric or polyhydric phenols and halogen-substituted products thereof, cross-linking agents (hardeners), metal oxides and the like may be used in combination with these subbing materials to perform subbing processing. it can.

When the support is actually subjected to undercoating, the above-mentioned undercoat materials can be used alone or in combination. In addition, these undercoating processes can form the undercoating layer with a single layer or multiple layers, but of course, it may be used in combination with the undercoating material to further overlay. For example, a method in which a gelatin layer is multilayer-coated on a vinylidene chloride copolymer layer, or a layer composed of a vinylidene chloride copolymer, a mixture of gelatin and a vinylidene chloride copolymer, and a gelatin layer are applied in this order in combination such as undercoating. Then, any material can be used in combination depending on the purpose, and multi-layers can be used in combination.

In addition to the subbing process by the above material processing, the support surface and emulsion are treated by corona discharge, glow discharge, other electron impact flame treatment, ultraviolet irradiation, oxidation treatment, saponification treatment, roughening treatment etc. on the support surface. The layers can also be glued. These treatments can be used alone or in combination, and by further combining with the above-mentioned material processing, sufficient subbing processing can be performed.

The color light-sensitive material according to the present invention includes all kinds of color light-sensitive materials such as a color negative film, a color positive film, a color reversal film and a color paper. Generally, it means a so-called natural color light-sensitive material that feels red, green, and blue and develops its complementary colors of cyan, magenta, and yellow, but it is a two-color light-sensitive material and a false color light-sensitive material used for a special purpose. Of course, materials and the like are included.

Any known method can be used for processing the light-sensitive material of the present invention. A known treatment liquid can be used. The treatment temperature can be 10-80 ℃,
It is preferably used at 20 to 55 ° 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 compound, sometimes preferably a p-phenylenediamine based developing agent such as 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-methoxyethylaniline, 3-β-methanesulfonamidoethyl-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 sulfates, hydrochlorides,
Examples thereof include sulfite and p-toluenesulfonate.

The photographic additives used in these color developers include alkali agents (eg, alkali metal or ammonium hydroxides, carbonates, phosphates), pH adjusters or buffers (eg, acetic acid, boric acid, etc.). Weak acids and weak bases and their salts), development accelerators (eg pyridinium compounds,
Cationic compounds, potassium nitrate and sodium nitrate,
Polyethylene glycol condensates and their derivatives, nonionic compounds such as polythioethers, polymer compounds having sulfite ester, other pyridines,
Ethanolamines, organic amines, benzyl alcohol, hydrazines, etc., antifoggants (eg alkali bromide, alkali iodide and nitrobenzimidazoles, mercaptobenzimidazole, 5-methylbenzotriazole, 1-phenyl- 5-mercaptotetrazole), inhibitors for rapid processing liquids (nitrobenzoic acid, benzothiazolium derivatives, phenazine-N-oxides), stain or sludge inhibitors, layering effect accelerators, preservatives (eg sulfites) , Acid sulfite, hydroxylamine hydrochloride, formaldehyde bisulfite, alkanolamine sulfite adduct, etc.).

The photographic emulsion layer after color development is usually bleached. The bleaching treatment may be performed at the same time as the fixing treatment (bleach-fixing bath) or may be performed individually.

For example, various bleaching agents used in bleach-fixing solutions have been proposed. The metal complex salt of an organic acid has a function of oxidizing metal silver produced by development to convert it to silver halide and simultaneously developing an uncolored part of a color former, and its structure is aminopolycarboxylic acid or oxalic acid, citrate. An organic acid such as an acid is coordinated with a metal ion such as iron, cobalt, or copper. The most preferred organic acid used to form such a metal complex salt of an organic acid includes
The following can be mentioned.

Ethylenediaminetetraacetic acid Diethylenetriaminepentaacetic acid Ethylenediamine-N- (β-oxyethyl) -N,
N ', N'-triacetic acid propylenediaminetetraacetic acid nitrilotriacetic acid cyclohexanediaminetetraacetic acid iminodiacetic acid dihydroxyethylglycine ethyl etherdiaminetetraacetic acid glycol etheramine tetraacetic acid ethylenediaminetetrapropionic acid phenylenediaminetetraacetic acid ethylenediaminetetraacetic acid disodium salt ethylenediaminetetraacetic acid Tetra (trimethylammonium) salt Ethylenediaminetetraacetic acid tetrasodium salt Diethylenetriaminepentaacetic acid pentasodium salt Ethylenediamine-N- (β-oxyethyl) -N,
N ', N'-triacetic acid sodium salt Propylenediaminetetraacetic acid sodium salt As the bleaching agent contained in the bleach-fixing solution, at least one of the above-mentioned bleaching agents may be used, and of course two or more kinds may be used in combination.
The amount used varies depending on the type of bleaching agent used, but is generally 0.01 mol or more per bleach-fixing solution, and more preferably
It is 0.05 mol or more.

The bleach-fixing solution contains a metal complex salt of an organic acid (for example, an iron complex salt) as described above as a bleaching agent and a silver halide fixing agent such as thiosulfates, thiocyanates and thioureas. Is applied. Further, from a bleach-fixing solution comprising a composition containing a small amount of a halogen compound such as potassium bromide in addition to a bleaching agent and the above-mentioned silver halide fixing agent, or conversely, comprising a composition containing a large amount of a halogen compound such as potassium bromide. It is also possible to use a bleach-fixing solution containing a bleach-fixing solution, and a special bleach-fixing solution having a composition comprising a combination of a bleaching agent and a large amount of a halogen compound such as potassium bromide. As the halogen compound, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, potassium iodide, ammonium iodide and the like can be used in addition to potassium bromide.

The silver halide fixing agent contained in the bleach-fixing solution is a compound which reacts with silver halide as used in usual fixing processing to form a water-soluble complex salt, for example, potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate. Typical examples thereof include thiosulfates such as the above, thiocyanate such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, thiourea, thioether, high concentration bromide and iodide.

The amount of the fixing agent contained in the bleach-fixing solution is generally 5.0 g to 200 g, preferably 50 g to 10 g per bleach-fixing solution.
It is 0 g.

The bleach-fix solution contains boric acid, borax, sodium hydroxide,
A pH buffering agent comprising various salts such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide may be contained alone or in combination of two or more kinds. it can. Furthermore, various antifoaming agents or surfactants may be contained. In addition, preservatives such as hydroxylamine, hydrazine and bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids or a kind of stabilizers such as nitroalcohol and nitrates, methanol, dimethyl-formamide and dimethyl sulfoxide. It is possible to appropriately contain an organic solvent and the like.

The pH of the bleach-fixing solution according to the present invention is used at 5.0 or higher, but it is generally used at pH 5.5 or higher and pH 9.0 or lower, preferably pH 6.0 or higher and pH 8.5 or lower. More specifically, the most preferable pH is 7.0 to 8.5.

The processing temperature of the bleach-fixing solution is used at 80 ° C. or lower, but it is preferably 55 ° C. or lower to suppress evaporation and the like.

The processing time for the bleach-fixing process is generally 30 seconds to 10 minutes, preferably 1 to 5 minutes, although it varies depending on the processing temperature and the like.

These color developing and bleach-fixing processes do not necessarily have to be carried out continuously, and other processes such as hardening, stopping, neutralizing, washing with water and stabilizing can be carried out before and after each process.

Hereinafter, the present invention will be described specifically with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example (1) As shown in Table 1, three emulsions (referred to as P-1, 2, 3) composed of polydisperse twin crystals that have been conventionally used were prepared.

A silver nitrate solution and a potassium bromide solution were added to a solution containing 1% gelatin, potassium iodide and potassium bromide while stirring at 60 ° C. The silver iodide content was adjusted by the amount of potassium iodide, and the grain size was adjusted by changing the addition time in the range of 20 to 90 minutes.

Next, the monodisperse core / shell type silver iodobromide emulsion according to the present invention
12 kinds (M-1, 2, 3, 4, 5, 6, 22, 23, 24, 28,
29, 30).

First, the silver iodide content of 2.0 mol% by the acid method, the average grain size
Seed particles of 0.10μ and 0.30μ were prepared. Next, using this seed emulsion, referring to the method described in JP-A-54-48521 and JP-A-58-49938, pAg and pH were controlled in the presence of ammonia, and a core / shell emulsion was prepared by the double jet method. Prepared. The grain size was prepared by changing the composition of the halide solution to be added, and the composition of the core and the shell was prepared by changing the selection of seed particles and the amount of added silver. However, for the purpose of increasing the monodispersity of grains, 0.15 g per mol of silver halide
Of 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene of Comparative Monodisperse Core / Shell Type Silver Iodobromide Emulsion M-10, prepared in the same manner as above.
11 and 12 were prepared. (Table 2). Comparative monodisperse core / shell type silver iodobromide emulsion M-10, 11, 12, 1 in the same manner
9, 20, 21, 25, 27, 31, 32, 33 were prepared.

Further, three monodisperse core / shell type silver iodobromide emulsions (referred to as M-7, 8 and 9) according to the present invention were prepared. An aqueous solution containing gelatin and potassium bromide was stirred at 40 ° C, a silver nitrate solution was added to make a nuclear emulsion consisting of multiple twins, and then physically ripened in the presence of ammonia and potassium bromide to obtain a monodisperse spherical shape. A seed emulsion was obtained. Using this seed emulsion, a core / shell emulsion was prepared by a double jet method in the presence of ammonia and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene while controlling pAg and pH. The composition of the core and shell was adjusted by changing the composition of the halide solution added (Table 3).

Comparative monodisperse core / shell type silver iodobromide emulsions M-13, 14 and 15 were prepared in the same manner.

Further, the monodisperse core / shell type silver iodobromide emulsions M-16, 17, and 18 according to the present invention were prepared by a method similar to that for the emulsions M-7, 8 and 9. However, compared to pBr1.8 at the time of manufacturing M-7 to 9,
The pBr at the time of manufacturing -16 to 18 was set to 2.2.

Next, a coated sample was prepared.

Multilayer color negative photosensitive materials (Samples 1 to 30) were prepared by sequentially coating the following 1st to 13th layers on a transparent cellulose triacetate film.

1st layer: antihalation layer An aqueous gelatin solution containing black colloidal silver has a silver content of 0.3 g / m 2.
^It was applied so as to be ² .

Second layer: intermediate layer An aqueous gelatin solution was applied to give a dry film thickness of 1.0 μm.

Third layer: Red-sensitive low-sensitivity silver halide emulsion layer Two kinds of silver iodobromide emulsions as shown in Table 4 were chemically sensitized with gold and sulfur sensitizers, and further as a red-sensitive sensitizing dye, anhydrous 9-ethyl-3,3'-di- (3-sulfopropyl)
4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide, anhydrous 5,5'-dichloro-9-ethyl-3,
3'-di- (3-sulfobutyl) thiacarbocyanine hydroxide and anhydrous 2- [2-{(5-chloro-3-
Ethyl-2 (3H) -benzothiazolidene) methyl}-
1-Butenyl-5-chloro-3- (4-sulfobutyl) benzoxazolium was added followed by 4-hydroxy-6.
-Methyl-1,3,3a, 7-tetrazaindene 1.0
g, 1-phenyl-5-mercaptotetrazole 20.0 mg
Was added. The two types of emulsion thus obtained were mixed 1: 1.
To produce a red-sensitive low-sensitivity emulsion. Further, a mixture of 33 g of a cyan coupler as shown in Table 4 and an organic solvent for dispersion (HBS and LBS) per 1 mol of silver halide was dissolved by heating and dissolved in 550 ml of 7.5% gelatin aqueous solution containing 5 g of sodium triisopropylnaphthalenesulfonate. In addition, a dispersion which was emulsified and dispersed by a colloid mill was added to prepare a red-sensitive low-sensitivity coating emulsion, which was coated so that the coated silver amount was 2.0 g / m ² . (Contains 160 g of gelatin per mol of silver halide.) Fourth layer: Red-sensitive high-sensitivity silver halide emulsion layer Chemical sensitization of silver iodobromide emulsions as shown in Table 4 with gold and sulfur sensitizers. In addition, anhydrous 9-ethyl-3,3'-di- (3-sulfopropyl) 4,5,5 as a red-sensitive sensitizing dye
4 ', 5'-dibenzothiacarbocyanine hydroxide, anhydrous 5,5'-dichloro-9-ethyl-3,3'-
Di- (3-sulfobutyl) thiacarbocyanine hydroxide and anhydrous 2- [2-{(5-chloro-3-ethyl-2 (3H) -benzothiazolidene) methyl} -1-butenyl-5-chloro- After 3- (4-sulfobutyl) benzoxazolium was added, 1.0 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 10.0 mg of 1-phenyl-5-mercaptotetrazole were added. A red-sensitive high-sensitivity emulsion was prepared. Further silver halide 1
A mixture of 9 g of a cyan coupler as shown in Table 4 and an organic solvent for dispersion (HBS and LBS) per mol was dissolved by heating, and triisopropylnaphthalenesulfonic acid sodium salt 1.5 was added.
A red-sensitive high-sensitivity coating emulsion was prepared by adding the dispersion obtained by emulsifying and dispersing in 30 ml of 7.5% gelatin aqueous solution containing g and using a colloid mill, and coating so that the coated silver amount was 2.0 g / m ² . (Contains 160 g of gelatin per mol of silver halide.) Fifth layer: intermediate layer Same as second layer Sixth layer: green-sensitive low-sensitivity silver halide emulsion layer Average grain size 0.6 μ, silver iodide 4 mol% And a silver iodobromide emulsion having an average grain size of 0.3 μ and 7 mol% of silver iodide were chemically sensitized with gold and sulfur sensitizers respectively, and anhydrous green sensitizing dye of anhydrous 5 , 5'-Dichloro-9-ethyl-3,3'-di- (3-sulfobutyl) oxacarbocyanine hydroxide anhydrous 5,5'-diphenyl-9-ethyl-3,3'-di- (3-sulfobutyl ) Oxacarbocyanine hydroxide and anhydrous 9-
Ethyl-3,3'-di- (3-sulfopropyl) -5,
6,5 ', 6'-Benzoxacarbocyanine hydroxide was added, followed by 4-hydroxy-6-methyl-1,
It was prepared by the usual method by adding 1.0 g of 3,3a, 7-tetrazaindene and 20.0 mg of 1-phenyl-5-mercaptotetrazole. The two kinds of silver halide emulsions thus obtained were mixed at a ratio of 1: 1 to prepare a green-sensitive silver halide emulsion.

Further, 1 mol as a magenta coupler per mol of silver halide
-(2,4,6-Trichlorophenyl) -3- {3-
(2,4-di-t-amylphenoxy) acetamide}
100 g of -5-pyrazolone, 1- (2,4,6-trichlorophenyl) -4 as a colored magenta coupler
-(1-Naphthylazo) -3- (2-chloro-5-octadecenylsuccinimidoanilino) -5-pyrazolone
2.5 g, dodecyl gallate 0.5 g, as a DIR compound, 2- (1-phenyl-5-tetrazolylthio) -4
-Octadecyl succinimide-1-indanone 1.8g
Is added, and a mixture of 120 g of tricresyl phosphate and 240 ml of ethyl acetate is heated and dissolved, and then added to an aqueous gelatin solution containing sodium triisopropylnaphthalenesulfonate, and a dispersion that is emulsified and dispersed by a colloid mill is added. A coated emulsion was prepared and coated so that the coated silver amount was 1.5 g / m ² . (Contains 160 g of gelatin per mol of silver halide.) Seventh layer: green sensitive high-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 1.2 μ, silver iodide 7 mol%)
Are chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfobutyl) oxacarbo as a green sensitizing dye. Cyanine hydroxide, anhydrous 5,5'-diphenyl-
9-Ethyl-3,3'-di- (3-sulfobutyl) oxacarbocyanine hydroxide and anhydrous -9-ethyl-3,3'-di- (3-sulfopropyl) -5,6.
5 ', 6'-dibenzooxacarbocyanine hydroxide was added, followed by 4-hydroxy-6-methyl-1,
A green-sensitive high-sensitivity silver halide emulsion was prepared by adding 1.0 g of 3,3a, 7-tetrazaindene and 10.0 mg of 1-phenyl-5-mercaptotetrazole. Further, 1- (2,4,6) as a magenta coupler per mol of silver halide.
-Trichlorophenyl) -3- {3- (2,4-di-t
-Amylphenoxy) acetamide} -5-pyrazolone
80g, 1- (2,4,4 as colored magenta coupler
6-trichlorophenyl) -4- (1-naphthylazo)
2.5 g of -3- (2-chloro-5-octadecenylsuccinimidoanilino) -5-pyrazolone, 2,5-di-t
-Octylhydroquinone 1.5 g, as a DIR compound, 2- (1-phenyl-5-tetrazolylthio) -4
-Octadecyl succinimide-1-indanone 1.0 g
Is heated and dissolved in a mixture of 120 g of tricresyl phosphate and 240 ml of ethyl acetate, and the mixture is added to an aqueous gelatin solution containing sodium triisopropylnaphthalenesulfonate, and the dispersion is emulsified and dispersed by a colloid mill to add a green-sensitive high-sensitivity coating emulsion. Was prepared and coated so that the coated silver amount was 1.8 g / m ² . (Contains 160 g of gelatin per mol of silver halide.) 8th layer: intermediate layer Same as 2nd layer 9th layer: yellow filter layer 2 in a gelatin aqueous solution in which yellow colloidal silver is dispersed.
3-Di-t-octylhydroquinone (3 g) and di-2-ethylhexyl phthalate (1.5 g) were dissolved in ethyl acetate (10 ml), and triisopropylnaphthalenesulfonic acid sodium salt 0.3 was added.
A dispersion liquid dispersed in a gelatin aqueous solution containing g was added, and this was applied so that gelatin was 0.9 g / m ² and 2,5-di-t-octylhydroquinone was 0.10 g / m ² .

Layer 10: Blue-sensitive low-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 0.6 μ, silver iodide 6 mol%
Are chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5'-dimethoxy-3,3'- as a green sensitizing dye.
Di- (3-sulfopropyl) thiacyanine hydroxide was added, followed by 4-hydroxy-6-methyl-1,3.
3a, 7-tetrazidene 1.0 g, 1-phenyl-5-
A blue-sensitive low-sensitivity silver halide emulsion was prepared by adding 20.0 mg of mercaptotetrazole and preparing by a conventional method. Furthermore, as a yellow coupler per mol of silver halide, α-pivaloyl-α- (1-benzyl-2-phenyl-3,5-
Dioxo-1,2,4-triazolidin-4-yl)-
2'-chloro-5 '-[α- (dodecyloxycarbonyl) ethoxycarbonyl] acetanilide 120 g, α-
50 g of {3- [α- (2,4-di-t-amylphenoxy) butylamide)} benzoyl-2′-methoxyacetanilide was added, and a mixture of 120 g of dibutyl phthalate and 300 ml of ethyl acetate was dissolved by heating to give triisopropylnaphthalene. A blue-sensitive, low-sensitivity silver halide coating emulsion was prepared by adding a dispersion obtained by emulsifying and dispersing in a gelatin aqueous solution containing sodium sulfonate and using a colloid mill.
It was applied so as to be g / m ² . (Contains 160 g of gelatin per mol of silver halide) 11th layer: Blue-sensitive high-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 1.2 μ, silver iodide 7 mol%)
Are chemically sensitized with gold and sulfur sensitizers, and anhydrous 5,5-dimethoxy-3,3-di-
(3-Sulfopropyl) thiacyanine hydroxide was added, followed by 4-hydroxy-6-methyl-1,3,3.
1.0 g of a, 7-tetrazaindene and 1-phenyl-
5-Mercaptotetrazole (10.0 mg) was added and the mixture was prepared by an ordinary method to prepare a blue-sensitive high-sensitivity silver halide emulsion.
Further, as a yellow coupler per mol of silver halide, α
-Pivaloyl-α- (1-benzyl-2-phenyl-
3,5-dioxo-1,2,4-triazolidine-4-
Yl) -2'-chloro-5 '-[α- (dodecyloxycarbonyl) ethoxycarbonyl] acetanilide 80 g
A mixture of 80 g of dibutyl phthalate and 240 ml of ethyl acetate is dissolved by heating and added to an aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate, and the resulting dispersion is emulsified and dispersed by a colloid mill to add a blue-sensitive high-sensitivity silver halide. A coated emulsion was prepared and coated so that the coated silver amount was 0.9 g / m ² . (Containing 240 g of gelatin per mol of silver halide) 12th layer: intermediate layer 2 g of di-2-ethylhexyl phthalate, 2- [3-
(Cyano-3- (n-dodecylaminocarbonyl) arylindene] -1-ethylpyrrolidine 2 g and ethyl acetate 2
ml was mixed, and a dispersion liquid dispersed in an aqueous gelatin solution containing 0.6 g of sodium triisopropylnaphthalene sulfonate was added, and this was applied to give gelatin of 1.0 g / m ² .

Thirteenth layer: Protective layer An aqueous gelatin solution containing 4 g of gelatin and 0.2 g of 1,2-bisvinylsulfonylethane was applied at a rate of 1.3 g / m ² per 100 ml.

In the table, C-1 and C-2 are comparative couplers having the following structures. HBS in the table means the following high boiling point solvents.

C-1 C-2 HBS-1 dibutyl phthalate 〃 -2 diethyl lauryl amide 〃 -3 tricresyl phosphate 〃 -4 dioctyl phthalate 〃 -5,4-di-t-amylphenol LBS means ethyl acetate.

Each of the samples thus obtained was divided into two pieces, and subjected to wedge exposure by a usual method for treatment. That is, one is immediately after exposure, and the other is subjected to forced deterioration for 4 days under the condition of relative humidity of 65% and temperature of 50 ° C (corresponding to storage for about 3 months at room temperature). The latent image stability was evaluated.

Processing process (38 ℃) Processing time Color development ……………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………… also also 3 minutes and 15 seconds. ……………… 6 minutes 30 seconds Rinsing with water …………………… 3 minutes 15 seconds Stabilization bath ……………… 1 minute 30 seconds The composition of the treatment liquid used in each treatment step is as follows. It was like.

[Color developer composition] [Bleaching liquid composition] [Fixer composition] [Stabilizing liquid composition] The results of sensitometry of the red-sensitive layer at this time are shown in Table 5.

The sensitivity is indicated by the relative value of the reciprocal of the exposure amount that gives a density of fog +1.0. However, the sensitivity when developed immediately after exposure
It was 100.

As is apparent from the table, the combination samples 8-16 and 23 of the core / shell type monodisperse emulsion of the present invention and the cyan coupler of the present invention were used.
25 and 27 to 29, changes in sensitivity and γ with the passage of time after exposure are scarcely observed. However, the combination of the emulsion of the present invention and the conventional cyan coupler (Samples 2, 4, 5) and the conventional emulsion were In the combination of conventional couplers (Samples 1 and 3), the changes in both sensitivity and γ are more remarkable than in the present invention. The silver iodide content of the shell is 0 (Samples 17 to 2).
2), using silver halide grains in which the volume ratio of the shell portion is 10% and 85% (Samples 26 and 30) and not monodisperse grains (Sample 28), the sensitivity is higher than that of the present invention. The fluctuation is large.

Further, the effect of the present invention is greater in emulsions composed of normal crystals.
Furthermore, the effect of the present invention is sufficiently exerted even with a slight change in the halogen composition of the core / shell and the particle shape, and is the same as in the change of the organic solvent for dispersing the coupler.

Example (2) Using the coating sample prepared in Example (1), latent image stability was evaluated according to the following method. That is, each sample is divided into two,
Wedge exposure was performed in the same manner as in Example (1), one was subjected to forced deterioration immediately after exposure and the other was subjected to forced deterioration for 4 days under the conditions of relative humidity of 60% and temperature of 50 ° C., and then the following treatment was performed. Evaluated.

Processing step (38 ° C.) Processing time Color development 3 minutes 15 seconds Bleach fixing 3 minutes 15 seconds Water washing 3 minutes 15 seconds Stabilizing bath 1 minute 30 seconds The composition of the processing solution used in the processing step was as follows.

[Color developer composition]

[Bleaching fixer] [Stabilizing liquid composition] The results of sensitometry of the red-sensitive layer at this time are shown in Table 6.

The sensitivity is indicated by the relative value of the reciprocal of the exposure amount that gives a density of fog +1.0. However, the sensitivity when developed immediately after exposure
It was 100.

As is clear from the table, in the combination of the core / shell type monodisperse emulsion of the present invention and the cyan coupler of the present invention, almost no change in sensitivity and γ with time after exposure is observed. On the contrary, in the combination of the emulsion of the present invention and the conventional cyan coupler, and in the combination of the conventional emulsion and the conventional coupler, both the sensitivity and γ are greatly changed as compared with the present invention.

Further, the effect of the present invention is greater in emulsions composed of normal crystals.
Further, the effect of the present invention is sufficiently exerted with respect to changes in the halogen composition of the core / shell and the particle shape, although there are some differences, and the same is true for changes in the organic solvent for dispersing the coupler.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer contains a group of substantially monodisperse silver halide grains. The silver halide grains forming the silver halide grain group are each composed of a core portion and a shell portion composed of silver iodobromide, and the average silver iodide content in the shell portion is an average iodide content of the core portion. It is lower than the silver content, and the ratio of the volume of the shell portion to the total volume of the silver halide grains including the core portion and the shell portion is 15% to 80%.
Which is a core / shell type silver halide grain, and the silver halide emulsion layer further contains a cyan coupler represented by the following general formula [I]. . General formula [I] [Wherein, X represents a hydrogen atom or a group capable of splitting off upon coupling with an oxidation product of an aromatic primary amine color developing agent, and R ₁ represents an optionally substituted aryl group or heterocyclic group. , R ₂ represents a ballast group necessary for imparting diffusion resistance to the cyan coupler represented by the general formula [I] and the cyan dye formed from the cyan coupler. ]