JPS6324255A - Color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having an improved storage stability by incorporating an oxidant of an aromatic primary amine color developing agent, silver halide emulsion and an anti-fogging agent to a photosensitive layer, and using a substrate body having mirror reflective surface. CONSTITUTION:The photosensitive layer contains at least one kind of a coupler capable of forming a color developing matter by coupling reaction of the oxidant of the aromatic primary amine color developing agent, a silver halide emulsion contg. >=70mol% silver chloride and one or two or more than two kinds of the anti-fogging agents selected from the group comprising mercaptothiadiazole, mercaptotriazole, mercaptotetrazole and an aromatictriazole compd. And, the substrate body is the photographic substrate body having the surface of mirror reflection or 2nd kind diffused reflection property, and has the photosensitive layer on the surface of said body. The 2nd kind diffused reflection property has >=5% spectral reflectance (measured by a monochromatic light of 550nm). Thus, the surface of the 2nd kind diffused reflection property has further preferably >=20% spectral reflectance (measured by the monochromatic light of 550nm).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention enables quick and easy development processing without causing fog, has excellent stability over time, and improves saturation, tone reproducibility in dark areas, and sharpness. This invention relates to an excellent color photographic material.

[Conventional technology]

Conventionally, color photographic materials have been prepared by forming an antihalation layer, a red photosensitive layer, a green photosensitive layer, and a yellow photosensitive layer on a support such as a film, a film or paper containing a white pigment, e.g. baryta paper, or paper with a water-resistant resin layer on both sides. A filter layer, a blue photosensitive layer, a protective layer, etc. are appropriately provided.

In order to obtain excellent color images, improvements in the transparency of each layer, thinning, layer structure, prevention of irradiation and halation, and improvement of the spectral absorption characteristics of coloring dyes obtained from the materials used, such as color couplers, are necessary. Improvements have been made to improve transparency. In particular, in order to improve sharpness, the selection of silver halide emulsions, such as halogen composition, grain size, etc., and layer structure, which facilitate the multilayer effect of development, have been devised. Additionally, techniques have been used to use materials that release compounds that have the effect of inhibiting or accelerating development during color development.

However, it is still insufficient, especially for photography where color images are formed on reflective supports such as color photographic paper.

A silver halide emulsion is contained in microcapsules,
It is known that bright images can be produced by using a photographic material coated on an aluminum support that reflects light well and has a metallic luster (for example, Japanese Patent Publication No. 49-3378
(description in No. 3). However, if a conventional emulsion is superimposed on this aluminum support, the image will only be slightly brighter, but this is not sufficient. It is also known that not only is the reflection of light unsightly, but small scratches on the surface are noticeable and undesirable. Lithographic printing plates in which a silver halide emulsion layer is provided on an aluminum support are known (for example, British Patent No. 1227603 and Japanese Patent Application Laid-Open No. 1983-90053).
number, etc.). The Aβ support used in lithographic printing plates has been subjected to surface treatments such as graining, which has no effect at all, and methods to improve this defect by preventing halation have been proposed (for example, Japanese Patent Application Laid-Open No. 124927/1983). ). Nor is it a material that forms color images. It is also known to provide a vapor-deposited metal layer of aluminum or chromium to prevent static (eg Birt).

-130403, Special Publication No. 59-41573 and Special Publication No. 59
-10420 etc.). However, it is not related to the present invention, and there is no description that suggests any improvement in color images.

On the other hand, there is a desire to simplify and speed up the development process, and various efforts have been made. For example, various development accelerators and benzyl alcohol are widely used in color developing solutions to enhance color development. However, benzyl alcohol has low water solubility and requires a solvent such as diethylene glycol to facilitate dissolution. These compounds, including benzyl alcohol, have large BOD (biological oxygen demand) and C0D (chemical oxygen demand), which indicate environmental pollution loads.
From the standpoint of environmental protection, it is preferable not to use these compounds. Furthermore, when benzyl alcohol is used, it takes time to dissolve it even if the above-mentioned solvent is used, so it is desired to remove benzyl alcohol also for the purpose of reducing solution preparation work.

However, simply removing this will cause a significant delay in color development, which goes against the market's demand for speedy development, so it has been difficult to develop an alternative means.

[Problem that the invention seeks to solve]

SUMMARY OF THE INVENTION The present inventors therefore sought to provide a color photographic material that can be quickly and easily developed without causing fog and without using benzyl alcohol, and has excellent saturation, gradation reproducibility in dark areas, and sharpness. Various studies were conducted for this purpose.

In particular, from the viewpoint of rapid development, the standard color development time is generally 3 minutes and 30 seconds at 38°C with ordinary color photographic paper, excluding special processing, but in the present invention, the standard color development time is 2 minutes and 30 seconds or less, preferably 1 minute and 30 seconds. The aim was to shorten the time to about 45 seconds.

Furthermore, in the process of studying to achieve the above object, it was found that when a photographic support having a specular reflective surface or a type 2 diffuse reflective surface is used, spots occur over time in a developing machine. Therefore, another object of the present invention is to provide a light-sensitive material for color photography which can suppress the occurrence of such spots over time, that is, has excellent stability over time.

[Means for solving problems]

The object of the present invention is to provide a color photographic material comprising at least one photosensitive layer on a support, in which the photosensitive layer forms a coloring dye by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent. At least one type of coupler to be formed, a silver halide emulsion containing 70 mol% or more of silver chloride, and one or two anti-gabbing agents selected from the group consisting of mercaptothiadiazole, mercaptotriazole, mercaptotetrazole, and aromatic triazole compounds. and the support is a photographic support having a specular reflective or type 2 diffuse reflective surface, and a photosensitive layer is provided on the surface. achieved by the material.

The color photographic material of the present invention will be explained below.

(Photographic support) In general, the reflection characteristics of the surface of an object can be broadly classified into specular reflection and diffuse reflection. Furthermore, diffuse reflection can be divided into first type diffuse reflection and second type diffuse reflection. Specular reflection is reflection from a smooth surface and follows the normal rules of specular reflection. On the other hand, diffuse reflection refers to paper, painted surfaces,
Reflection from wood and walls causes parallel incident light to be reflected not only in the specular direction but also in all directions.

Type 2 diffuse reflectance generally refers to reflection from rough surfaces with small slope boundaries, such as ground glass or metal polished surfaces. In the present invention, type 2 diffuse reflectance refers to reflectivity in which a smooth mirror-reflecting surface has small boundaries due to small irregularities. In this case, the diffusely reflected light can be considered to be a collection of specularly reflected lights from small reflecting surfaces. This is the second
This is why the species diffuse reflectance is called "small specular reflectance."

For example, Color Science Handbook (Japan Color Society, 1932)
Chapter 18, Chapter 1 of 05th edition, published by the University of Tokyo Press)
Defined by Section.

Type 1 diffuse reflectance and type 2 diffuse reflectance can be distinguished by the difference in reflectance of the smooth surface of the material. The reflectance of the smooth surface of the material that gives the first type diffuse reflectance is the second type.
Generally lower than the reflectance of a smooth surface of a material that provides diffuse reflectance. In the present invention, type 2 diffuse reflectance refers to a case where the reflectance R is 0.5 or more. Therefore, the second
The seed diffusely reflective surface has a surface area of 0.5 or more, more preferably 0.5 or more.
It has a reflectance of 7 to 1.0. The reflectance R of a smooth surface made of the same material when irradiated with light in the vertical direction can be determined using a goniole left meter. Incidentally, type 1 diffuse reflectance refers to the reflectivity that, when a light-transmitting solid is made into a fine powder, becomes diffused light due to the total reflection of light that is mostly transmitted through the solid and its multiple reflections. .

Specular reflection and diffuse reflection can be distinguished based on the difference in spectral reflectance. Here, spectral reflectance is measured using monochromatic light of 550nffl incident at an incident angle of 7 degrees from the normal direction of the test sample, and a trap is set at a viewing angle of 10 degrees centered on the direction of specular reflection of the incident light. The specular reflection component is removed, and the other components that are diffusely reflected in a viewing angle range of 90 degrees from the normal are integrated using an integrating sphere and calculated as a percentage of the incident light. The second type diffuse reflectance in the present invention has the above spectral reflectance (measured with monochromatic light of 550 nm) of 5% or more. Therefore, the type 2 diffuse reflective surface of the present invention is 5
% or more, preferably 10% or more, more preferably 20% or more (measured with monochromatic light at 550 nm). The spectral reflectance can be determined using, for example, Hitachi Color Analyzer Model 307. In addition, in the present invention, 5 is used as a representative of the green area with high visual sensitivity.
Monochromatic light of 50 nm was used. In addition, in order to accurately measure the spectral reflectance of the second type diffuse reflective material, the measurement is performed without adding dye or pigment to the resin.

As a result, the reflectance R of the material used to form the surface against light irradiation in the vertical direction and Hitachi Color.

From the value of spectral reflectance when a trap of a goniole left meter such as an analyzer is provided, the second aspect of the present invention is determined.
A distinction can be made between specular reflection and first type diffuse reflection.

A packed layer of solid powder providing a type 2 diffusely reflective surface is
Composed of solid powder and resin.

The solid powder is preferably a metal powder. For metals, F, Benford et al.
Opt, Sac.

Amer, Vol. 32, pp. 174-184 (1942), such as silver, aluminum, gold, copper,
Chromium, nickel, platinum, and alloys thereof such as aluminum/magnesium alloy, aluminum/copper, aluminum/antimony, and sinchu are used. In addition to metal powders, inorganic powders can also be suitably used. Examples of the inorganic substance powder include pieces of natural mica and pieces of fish scales.

In the present invention, in order to make the surface of the solid powder packed layer have type 2 diffuse reflection, the average particle size of the solid powder is preferably about 0.01 to 100 μm. In particular, in the case of aluminum, 1 to 100μ, preferably 5 to 70μ
Preferably it is μ.

Moreover, in the case of silver, it is preferable that it is 0.1-100 micrometers. In the case of gold, it is preferably 0.01 to 100μ.

In addition, resins include water-soluble polymers (e.g. gelatin, etc.), aqueous latexes (e.g. styrene acrylic, acrylonitrile butadiene, acrylic, styrene acrylic, vinylidene chloride, vinegar vinyl chloride, ethylene-vinegar). organic solvent-based resins (e.g. acrylic, etc.), organic solvent-based resins (e.g. acrylic,
Examples include polyester-based, cellulose-based, polystyrene-based, polyvinyl chloride-based, polyvinyl acetate-based, etc.).

In the present invention, the above-mentioned resin and the above-mentioned solid powder are mixed, and then the mixture is coated on a substrate using a known method such as a knife coater, and if necessary, dried. A support can be obtained. still,
Preferably, the particles of the solid powder are coated with a resin in advance and mixed with the resin.

In addition, as a different method, photopolymerizable monomers or oligomers (for example, acroyl-based monomers having unsaturated double bonds,
A metaacroyl-based or acrylamide-based compound, a compound containing an allyl group, a vinyl ether group, a vinyl thioether group, etc., or an unsaturated polyester-based (molecules! 1000 to 20,000) compound) is mixed with the solid powder, and the mixture is mixed. The photographic support of the present invention can also be obtained by applying it onto a substrate and then irradiating it with an electron beam or the like to produce the pancreas. In the present invention, for example, pages 235 to 236 of the photosensitive resin data collection published by Sogo Kagaku Kenkyusho (1967) and 8, Franken
cken), Fatipek Combres (Fatip
ec Congress), Volume 11, No. 19 (1972
Compounds described in 2003) can be suitably used as the photopolymerizable monomer or oligomer.

The irregularities on the outer surface of the solid powder in the packed bed of solid powder can be determined by embedding and fixing the sample in resin, cutting an ultrathin section, and observing the cross section using an electron microscope. It can be directly measured with submicron accuracy using a cross-sectional shape measuring device that uses electron beam irradiation. The number of cylinders of unevenness can be measured as the frequency of surface roughness, and preferably the average frequency is 0.1 to
2000 pieces/mm, more preferably 1 to 1000 pieces/mm.

The solid, preferably metal, constituting the thin film layer providing the surface with type 2 diffuse reflection is F, Benfurt (F, Benfurt).
Ford) et al. J, Opt, Sac, A+ner, 32
Metals shown in Vol. 174-184 (1942), such as silver, aluminum, gold, copper, chromium, nickel, platinum, alloys thereof, such as aluminum/magnesium alloy, aluminum/copper, aluminum/antimony, Shinchu etc. are used.

Further, the surface of the solid thin film layer, preferably the metal thin film layer, which provides the second kind of diffuse reflection is obtained as follows. First, the surface of the specularly reflective metal plate is baked during rolling, or mechanically, for example, with a brush of appropriate strength, or grained by spraying fine particles of an abrasive agent such as Vumice with a jet stream. , an etching method using an electrolytic method, etc.

The metal thin film layer having reflective properties of the present invention can be laminated or formed into a film layer on a substrate to serve as a support. Second
Vacuum evaporation, sputtering, ion blating, electrodeposition, electroless plating, etc. are known methods for forming metal thin film layers on a given substrate. layers can be provided. In the case of specular reflection, it can be made into a type 2 diffuse reflection surface by the method described above.

Surface irregularities can be determined by embedding and fixing the sample in resin, cutting an ultrathin section, and observing the cross section using an electron microscope. It can be directly measured with submicron accuracy using a cross-sectional shape measuring device that uses electron beam irradiation. The number of cylinders of unevenness can be measured as the frequency of surface roughness, preferably the average frequency is 0.1 to 2000 Kel/more preferably 1
~1000 ke/bo.

The specular reflectance in the present invention is the spectral reflectance (550n
m) is less than 5%.

Accordingly, the specular reflective surface of the present invention is one that exhibits a spectral reflectance (measured with monochromatic light at 550 nm) of less than 5%.

Mention may be made of metals that provide specularly reflective surfaces. Such metals include F, Benford et al. J, Opt, Sac,
Amer.

32, pp. 174-184 (1942), such as silver, aluminum, gold, copper, chromium, platinum, alloys thereof, such as aluminum/magnesium alloy, aluminum/L-aluminum/antimony, and sinter. etc. are used.

Metal foils or sheets with specularly reflective surfaces for use in the present invention are processed by conventional metal rolling and by laminating the rolled film to a substrate. Other methods include vacuum evaporation, sputtering,
Known methods for forming thin films such as ion blating method and electrodeposition method can be used.
A layer or more than one thin film layer can be provided.

A portion of this mirror surface may be roughened to provide diffuse reflection properties. This specularly reflected light may be mixed with the first type of diffusely reflected light from fine powder such as titanium oxide or magnesium oxide.

The substrate can be provided with a layer having a specularly reflective surface and containing a high density of fine powders of metals such as aluminum, silver or nickel, or fine powders of, for example, mica or the scales of fish, such as standing fish. .

As the substrate of the support according to the present invention, those conventionally used can be used as they are without any problem. For example, plastic, film, paper, RC paper, synthetic paper, metal plate, etc. are used. Preferably, it is paper or RC-paper, and the polyethylene layer of RC-paper is laminated with aluminum foil that has been pre-textured using low-density polyethylene. 8 can also be used as a substrate.

The support according to the present invention can be provided with a silver halide emulsion layer via an undercoat layer. The undercoat layer is obtained using a thermoplastic resin such as polyethylene or polypropylene, or an ionomer resin containing an epoxy adhesive. A gelatin or seratin silver halide emulsion layer can be provided thereon, with or without corona discharge treatment.

This undercoat layer prevents the adhesion of the silver halide emulsion layer and prevents harmful photographic effects from the support on the silver halide emulsion layer, such as the formation of spots, fogging, and deterioration of storage stability. Although the undercoat layer is uniformly coated, it is preferably thin. For example, the film thickness is preferably 5 μm or less, preferably 2 μm or less.

In some cases, the present invention may include a first type of diffusely reflecting fine particles in an upper layer such as an undercoat layer, for example, 1 g/mr or less, and a first type of diffusely reflecting latex or finely dispersed particles of a high boiling point organic solvent in the upper layer. can also be included.

Further, by mixing fine powder of titanium oxide or barium sulfate in the substrate and providing minute holes in the metal thin film layer according to the present invention on the surface thereof, the first type of diffuse reflection is mixed with the second type of diffuse reflection. It is also possible to mix them.

As a result, the viewing angle can be expanded with less deterioration of sharpness.

(Photosensitive layer) According to the present invention, the color photographic material is provided with an underlayer on the support, if necessary, and a photosensitive layer (BL) containing silver halide grains and a yellow color coupler each having spectral sensitivity in the blue region. ), a photosensitive layer (GL) containing silver halide grains with spectral sensitivity in the green region and a magenta coupler.
, a photosensitive layer (RL) containing silver halide grains having spectral sensitivity in the red region and a cyan color coupler, and a protective layer (P).
L), middle layer (ML), yellow filter layer (YL)
With an appropriate layer structure, you can make a profit. Each photosensitive layer can be divided into two or three layers depending on the sensitivity and the grain size of the silver halide.

(Silver halide emulsion) The silver halide emulsion according to the present invention contains 70 mol% of silver chloride.
It is to contain the above. By using this silver halide emulsion, the speed of color development can be increased. However, if the silver chloride content is 70 mol % or more, preferably 80 mol % or more in the silver chloride emulsion, it becomes difficult to achieve high sensitivity, suppress fogging, and ensure stability over time. In particular, since a metal having a different ionization tendency than silver ions, such as aluminum or an alloy thereof, is used for the support, spots and fog tend to occur over time.

However, these problems can be overcome by combining it with an antifoggant, which will be described later.

The silver halide emulsion used in the present invention consists of silver halide containing substantially no silver iodide and containing 70 mol % or more of silver chloride. The silver chloride content is preferably 90 mol% or more, more preferably 95 mol% or more. It may be pure silver chloride.

When the silver chloride content decreases, development progresses slowly (and sufficient density cannot be obtained).

Substantially no silver iodide means that the content of silver iodide is 1 mol% or less, more preferably 0.5 mol% or less, and most preferably no silver iodide at all. . Including silver iodide slows down the development speed,
In some cases, this may increase fog, which is undesirable.

The amount of silver halide coated on the support is 0.
．． 78 g/m' or less is preferable. If the coating amount of silver halide is too large, the progress of development will be slow in this case as well, making it impossible to obtain a sufficient density.

The silver halide emulsion used in the present invention has an average grain size of 0.1 μm as expressed by the diameter of an equivalent circle in projection.
~2 μm is preferable, more preferably 0.2 μm ~1
．． It is 3 μm. Preferably, the emulsion is a monodisperse emulsion, and the grain size distribution representing the degree of monodispersion is 0 in terms of the ratio (s/7) of the statistical standard deviation (s) to the average grain size (R).
．． It is preferably 2 or less, more preferably 0.15 or less.

The silver halide grains used in the present invention may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform phase throughout the grain. Moreover, they may be mixed.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
), may have an irregular crystal shape such as a spherical shape, or may have a composite shape of these crystal shapes. Further, tabular grains may be used, and in particular, an emulsion may be used in which tabular grains having a length/thickness ratio of 5 or more, particularly 8 or more occupy 50% or more of the total projected area of the grains. An emulsion consisting of a mixture of these various crystal forms may also be used. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention is described in "Chemistry and Physics of Photography J" by Glafkides, Chim.
ie etPhysique Photography
que (published by Paul! Jonte 1, 196)], “Photographic Emulsion Chemistry” by Du Huynh, CG, F, Du
Photographic Emuls by f f in
ionChemistry (Focal Press
[Published, 1966)], Zelikman et al., "Manufacture and Coating of Photographic Emulsions J" (V, L.

Making and by Zelikman et al.
Coating Potographic Emuls
ion (Focal Press, 1964)].

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). A method of keeping pAg constant in the liquid phase in which silver halide is produced as a form of simultaneous mixing method,
That is, the so-called Chondral double jet method can be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Furthermore, emulsions prepared by the so-called conversion method, which involves a process of converting silver halide already formed before the completion of the silver halide grain formation process to silver halide with a smaller solubility product, and emulsions prepared by 1. Emulsions which have undergone similar halogen conversion after the completion of the silver halide grain formation process can also be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

After grain formation, silver halide emulsions are usually subjected to physical ripening, desalting and chemical ripening before being used for coating.

Known silver halide solvents (e.g., ammonia, rhodankali or U.S. Pat. No. 3,271,157, JP
1-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717, JP-A-54-155828, etc.) by precipitation, physical Can be used for ripening and chemical ripening.

To remove soluble silver salts from the emulsion after physical ripening,
Nudel washing 1. Follow the flocculation sedimentation method or ultraconcentration method.

The silver halide emulsion used in the present invention contains active gelatin and sulfur-containing compounds that can react with silver (for example, thiosulfate,
Sulfur sensitization method using reducing substances (e.g. stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); metal A noble metal sensitization method using a compound (for example, a total complex salt or a complex salt of a metal of group Ⅰ of the periodic table such as Pt, Ir, Pd5Rh, Fe, etc.) can be used alone or in combination.

Among the above chemical sensitizations, sulfur sensitization alone is more preferred.

In order for the color photographic light-sensitive material of the present invention to satisfy the target gradation, two or more types of monodisperse silver halide emulsions (monodisperse (preferably those having the above-mentioned fluctuation rate) can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or used in combination.

The blue-sensitive, green-sensitive and red-sensitive emulsions of the present invention are spectrally sensitized with methine dyes and others so that they have color sensitivity. The pigments used include cyanine pigments, merocyanine pigments, composite cyanine pigments, composite merocyanine pigments, poropolar cyanine pigments, hemicyanine pigments,
Included are styryl color patches, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus: namely, an indole nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus , quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbyl nucleus, and the like can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Representative examples are U.S. Patent Nos. 2,688,545, 2,977, 229, and 3
, No. 397,060, No. 3, No. 522.052, No. 3,
527,641, 3.617,293, 3.6
No. 28,964, No. 3.666.480, No. 3,67
No. 2.898, No. 3.679,428, No. 3,703
, No. 377, No. 3.769, 301, No. 3,814.
No. 609, No. 3.837,862, No. 4,026,7
No. 07, British Patent No. 1,344,281, British Patent No. 1,507
, No. 803, Special Publication No. 43-4936, No. 537123
No. 75, JP-A-52-110618, JP-A No. 52-109
No. 925.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

(Coupler) The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent color coupler substituted with a leaving group can reduce the amount of silver coated than a four-equivalent color coupler in which the coupling active position is a hydrogen atom. Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2.40
No. 7,210, No. 2.875.057 and No. 3
．． 265.506, etc. The use of two-equivalent yellow couplers is preferred for the present invention; U.S. Pat.
3.933.501 and 4,022,62
0, etc., or Japanese Patent Publication No. 58-10739, U.S. Patent No. 4,
No. 401,752, No. 4,326.024, RD1
8053 (April 1979), British Patent No. 1,425
．． 020, West German Application No. 2,219,917, West German Application No. 2.261,361, West German Application No. 2.329,587 and West German Application No. 2.433.812, etc. Yellow coupler is a typical example. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group in terms of the color of the coloring dye [in terms of appearance and color density; a typical example is U.S. Pat. No. 2,311,082. No. 2.
No. 343.703, No. 2,600,788, No. 2
．． No. 908,573, No. 062,653, No. 3,152,896, No. 3,936,015, etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or U.S. Pat. No. 4,351
．． The arylthio group described in No. 897 is preferred. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73,636 provides high color density.

As a pyrazoloazole coupler, US Patent No. 3.
369.879, preferably pyrazolo(5,1-C)[:1,2°4] triazole neck as described in U.S. Pat.
(June 1984) and Research Disclosure 24230 (19
Examples include the pyrazolopyrazoles described in June 1984). The imidazo compound described in European Patent No. 119,741 in terms of the low yellow side absorption of the coloring dye and the light fastness.
1゜2-b] Pyrazoles are preferred, as described in European Patent No. 11
Pyrazolo[1,5-b)(1,2
, 4]) Riazole is particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenolic couplers, such as the naphthol-based couplers described in U.S. Pat. No. 2.474.293, preferably U.S. Pat.
．． No. 212, No. 4.146.396, No. 4,22
Typical examples include the oxygen atom elimination type double-weight naphthol couplers described in No. 8.233 and No. 4.296.200. Specific examples of phenolic couplers include U.S. Patent Nos. 2.369.929 and 2.8.
OL No. 171, OL No. 2.772.162, OL No. 2,8
95.826, etc. Humidity and temperature robust cyan couplers are preferably used in the present invention, exemplified by U.S. Pat.
Phenolic cyan coupler having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus described in US Pat. No. 002, US Pat.
．． 308, 4.126, 396, 4.33
No. 4,011, No. 4.327.173, West German Patent Publication No. 3.329.729, and Patent Application No. 1983-4267
2,5-diacylamino substituted phenolic couplers such as those described in US Pat. No. 3,446,622.
No. 4.333,999, No. 4.451,55
These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, which are described in No. 9 and No. 4,427,767.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such dye-diffusive couplers are magenta couplers in U.S. Pat. No. 4,366,237 and British Patent No. 2,125,570; No. 234,533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451,82.
No. 0 and No. 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367.2.
It is described in No. 82.

The various couplers used in the present invention can be used in combination in the same layer of the photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or in two or more different layers using the same compound. It can also be introduced into

The coupler used in the present invention can be introduced into the light-sensitive material by an oil-in-water dispersion method. In the oil-in-water dispersion method, the boiling point is 1
After dissolving in either a high boiling point organic solvent of 75°C or higher and a low boiling point so-called auxiliary solvent alone or in a mixture of both, finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. . Examples of high boiling point organic solvents are described in U.S. Pat. No. 2,322,027 and others. Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

Specific examples of high boiling point organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate,
di-2-ethylhexyl phthalate, decyl tucrate, etc.), ethesurs of phosphoric or phosphonic acids (triphenyl phosphate, tricresyl phosphate, 2-ethyl phosphate, etc.)
ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc.), benzoic acid ester (2-ethylhexyl benzoate,
dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyl dodecanamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol) ), fatty acid carboxylic acid esters (dioctyl azelate, glycerol tributyrate, instearyl lactate, trioctyl citrate, etc.), aniline derivatives (N
, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. In addition, as an auxiliary solvent, those with a boiling point of about 30°C or higher,
Preferably, an organic solvent having a temperature of 50° C. or more and about 160° C. or less can be used, and typical examples include ethinope acetate, butyl acetate, etinope methyl ethyl ketone propionate, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of the process, effects, and latex for impregnation of the latex limb method can be found in U.S. Pat. No. 4,199,363, West German Patent Application No. It is written in the number etc.

The PA standard usage amount of color couplers ranges from 0.001 to 1 mole per mole of photosensitive silver halide, preferably from 0.01 to 0 for yellow couplers.
．． 5 mole, 0.003 to 0.00 for magenta coupler.
3 mono or cyan coupler is 0. OQ is 2 to 0.3 mol.

The light-sensitive materials produced using the present invention contain hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, and sulfonamide phenols as color-fogging inhibitors or color-mixing inhibitors. It may also contain derivatives and the like.

Known anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
Hindered phenols, mainly 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, and bisphenols;
Typical examples include gallic acid derivatives, methylene dioxybenzenes, amine phenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
As described in U.S. Pat. No. 4,268.593,
Compounds having a hindered amine and a hindered phenol structure in the same molecule give good results. In addition, in order to prevent the deterioration of magenta dye images, especially the deterioration caused by light, the substitution of spiroindanes as described in JP-A-56-159644 and hydroquinone diether or monoether as described in JP-A-55-89835 is recommended. chromans give favorable results.

In order to improve the storage stability of cyan images, especially the light fastness, it is preferable to use a benzo)IJ azole external radiation absorber in combination. This UV absorber may be emulsified with a cyan coupler.

The amount of ultraviolet absorber applied should be sufficient to impart photostability to the cyan dye image, but if too much is used, it may cause yellowing of the unexposed areas (white areas) of the color photographic light-sensitive material. Therefore, usually preferably I x 10-'
mol/m" to 2 x 104 mol/m, in particular 5 x 10-'mol/m' to 1.5 x 10-3 mol/m>.

In the conventional light-sensitive material layer structure of color paper, an ultraviolet absorber is contained in one of the layers on both sides adjacent to the cyan coupler-containing red-sensitive emulsion layer, preferably in both layers. When an ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with a color mixing inhibitor. When a UV absorber is added to the protective layer, another protective layer may be applied as the outermost layer. This protective layer can contain a matting agent of any particle size.

In the photosensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

The light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation or halation.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the invention may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener.

Water-soluble brighteners may be used, and water-insoluble brighteners may be used in the form of dispersions.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate, etc.; sugar derivatives such as sodium alginate, starch derivatives;
Various synthetic hydrophilic compounds such as single or copolymers of polyvinylalconope polyvinyl alcohol partial acetanobevoly N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazonope polyvinylpyrazole, etc. Polymeric substances can be used.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Sac, Sci, Phot,
Enzyme-treated gelatin as described in Japan, No. L, p. 6.30 (1966) may be used, and gelatin hydrolyzed or enzymatically decomposed products may also be used.

In addition to the above-mentioned additives, the photosensitive material of the present invention further contains various stabilizers, anti-staining agents, developers or their precursors,
Development accelerators or precursors thereof, lubricants, mordants, matting agents, antistatic agents, plasticizers, and other various additives useful for photographic materials may be added. Representative examples of these additives are Research Disclosure 1764
3 (December 1978) and 18716 (197
(November 9).

(Antifoggant) The present invention is characterized by using a high silver chloride composition in which the halogen composition of the silver halide in the silver halide emulsion is 70 mol% or more, preferably 80 mol% or more; The method is to add a compound (antifoggant) selected from asiazonovemercaptotetrazole and aromatic triazole compounds. These compounds can also be added to the subbing layer adjacent to the surface of the metal used in this invention. It can also be added to the color developing solution.

It not only suppresses fogging but also improves storage stability (stability over time) without reducing sensitivity, and when added in a sufficient amount, improves color turbidity and sharpness.

Surprisingly, the occurrence of spots can be prevented. In particular, it is effective in preventing the occurrence of spots or contamination on the metal, especially aluminum surface of the support.

The antifoggant of the present invention preferably has the following general formula (%) (%) General formula (1) In the formula, R represents an alkyl group, an alkenyl group, or an aryl group. X represents a hydrogen atom, an alkali metal atom, an ammonium group or a precursor.

Examples of the alkali metal atom include a sodium atom and a potassium atom, and examples of the ammonium group include a tetramethylammonium group and a trimethylbenzylammonium group. Further, the precursor refers to a group that can form X=H or an alkali metal under alkaline conditions, and represents, for example, an acetyl group, a cyanoethyl group, a methanesulfonylethyl group, and the like.

Among the above R, the alkyl group and alkenyl group include unsubstituted and substituted groups, and also include alicyclic groups.

Substituents for substituted alkyl groups include halogen atoms, nitro groups, cyan groups, hydroxyl groups, alkoxy groups, aryl groups, acylamino groups, alkoxycarbonylamino groups, ureido groups, amino groups, heterocyclic groups, acyl groups, and sulfamoyl groups. , sulfonamide group, thioureido group,
Examples include a carbamoyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, and further a carboxylic acid group, a sulfonic acid group, or salts thereof.

The above ureido group, thioureido group, sulfamoyl group, carbamoyl group, and amino group are each unsubstituted,
Including those substituted with N-alkyl and those substituted with N-aryl. Examples of the aryl group include a phenyl group and a substituted phenyl group, and examples of the substituent include an alkyl group and the substituents of the alkyl group listed above.

General formula ([) In the formula, L represents a divalent linking group, and R represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. The alkyl group, alkenyl group and X of R have the same meanings as in general formula (I).

Specific examples of the divalent linking group represented by the above can be mentioned.

n represents 0 or 1, and ROlRl and R2 each represent a hydrogen atom, an alkyl group, or an aralkyl group.

General formula (III) In the formula, R and X are as defined in general formula (I),
L has the same meaning as that in general formula (II).

R3 has the same meaning as R, and may be the same or different.

General formula (rV) Z represents an aromatic ring-forming atomic group.

Specific examples of the compound of general formula (I) are listed below, but the invention is not limited thereto.

Specific examples of the compound of general formula (IV) are listed below,
It is not limited to these.

(rV-1) (rV-2> (rV-3) (IV-4) (TV-5'') General formula (I), general formula (II), general formula (III) or general formula used in the present invention The compound represented by formula (rV) can be contained in any layer of the silver halide color photographic light-sensitive material and/or in the color developer.

Any layer in the silver halide color photographic light-sensitive material means a photosensitive and non-photosensitive hydrophilic colloid layer.

The amount of the antifoggant represented by the general formula (■), general formula (■), general formula (III), or general formula (IV) to be added is as follows: 1 x 104 to 5 x 10 per mole of silver halide
-' moles are preferred, and moreover 1 x 10-3 to I X 1
0-2 mol is preferred. In addition, when it is contained in a color developing solution, I
is preferable, and furthermore 5X10-g to 5X10-'mol/
1 is preferred.

(Development treatment) The color photographic light-sensitive material of the present invention is processed at 38°C for 2 minutes and 3 minutes.
A good image can be obtained with a color development time of 0 seconds or less.

The preferred development time is about 10 seconds to 2 minutes. The development time here is the time from when the silver halide color photographic light-sensitive material comes into contact with the color developing solution until it comes into contact with the next bath, and includes the transit time.

The first aromatic amine color developer used in the color developer of the present invention includes known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. Preferred examples are p-phenylenediamine derivatives, and representative examples are shown below, but the invention is not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-CN-ethyl-N -(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-6N-ethyl-N-(β-methanesulfonamidoethyl) -3-Methyl-4-aminoaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p~phenylenediamine D-94-amino-3-methyl-N -ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-butoxyethylaniline These p-phenylenediamine derivatives may also be salts such as sulfate, hydrochloride, sulfite, and p-)luenesulfonate. The above compound is disclosed in U.S. Patent No. 2.193
．． No. 015, No. 2.552.241, No. 2, 566,
No. 271, No. 2.592.364, No. 3.656.9
No. 50, No. 3.698.525, etc.

The amount of the aromatic-grade amine developing agent used is about 0.1 g to about 20 g, more preferably about 0.5 g to about 20 g, per 1β of the developing solution.
The concentration is approximately 10 g.

As is well known, the color developer used in the present invention may contain hydroxylamines.

Although hydroxylamines can be used in the free amine form in color developers, it is more common to use them in the form of water-soluble acid salts. Common examples of such salts are sulfates, oxalates, chlorides, phosphates, carbonates, acetates, and the like. The hydroxylamines may be substituted or unsubstituted, and the nitrogen atom of the hydroxylamines may be substituted with an alkyl group-substituted alkyl group. For example, dihydroxydiethylamine and dihydroxymethylamine are preferred.

The amount of hydroxylamine added is 0 per 11 parts of color developer.
The amount is preferably from g to 10 g, more preferably from 0 to 5 g. If the stability of the color developer is to be maintained, it is preferable that the amount added be small.

Also, as a preservative, sodium sulfite, potassium sulfite,
It can contain sulfites such as sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, carbonyl sulfite adduct sulfinate, and the like. The amount of these added is preferably Og to 20g/β, more preferably Og to 5g/j! If the stability of the color developer is maintained, the smaller the amount, the better.

Other preservatives include JP-A Nos. 52-49828, 56-47038, 56-32140, and 59-
Aromatic polyhydroxy compounds described in US Pat. No. 1,601,42 and US Pat. No. 3,746,544; US Pat. No. 3,615.
503 and British Patent No. 1.306.176; α-aminocarbonyl compounds described in JP-A-52-143020 and JP-A-53-89425; JP-A-57-44148 and JP-A-57- 53749
various metals described in JP-A No. 52-102727; hydroxamic acids described in JP-A No. 52-27638; α-α'-sialbonyl compounds described in JP-A No. 59-160141; Salicylic acids described in No. 54-3532; poly(alkyleneimines) described in No. 56-94349; gluconic acid derivatives described in No. 56-75647. Two or more of these preservatives may be used in combination, if necessary. Particularly preferred are 4,5-dihydroxy-m-benzenedisulfonic acid, poly(ethyleneimine), triethanolamine, and the like.

The color developer used in the present invention preferably has a pH of 9
to 12.0, more preferably 9 to 11.0, and the color developer may contain other compounds of known developer components.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt,
N,N dimethylglycine salt, roncine salt, norleucine salt, quanine salt, 3゜4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1゜3-propanediol salt, valine salt, Proline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates have excellent solubility and buffering ability in the high pH range of 9.0 or higher, and even when added to color developers, they have no effect on photographic performance. It is particularly preferable to use these buffers because they have the advantages of having no adverse effects (fogging, etc.) and being inexpensive.

Specific examples of these buffers include carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate,
Trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (salicylic acid) sodium), potassium 0-hydroxybenzoate, 5
Examples include sodium -sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention
It is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/β
It is preferably at least 0.1 mol/l-0, particularly 0.1 mol/l-0,
Particularly preferred is 4 mol/1.

In addition, various caloric acid agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or for improving the stability of the color developer.

The chelating agent is preferably an organic acid compound, such as the aminopolycarboxylic acids described in Japanese Patent Publications No. 48-30496 and No. 44-30232, and JP-A No. 56-9.734.
No. 7, Special Publication No. 56-39359 and West German Patent No. 2.2
Organic phosphonic acids described in No. 27.639, JP-A-52-
No. 102726, No. 53-42730, No. 54-12
No. 1127, No. 55-126241 and No. 55-65
Examples include phosphonocarboxylic acids described in JP-A-58-195845, JP-A-58'-203440, and JP-B-Sho 53-40900. , specific examples are shown below, but the invention is not limited to these.

・Nitrilotriacetic acid ・Diethyleneaminopentaacetic acid ・Ethylenediaminetetraacetic acid ・Triethylenetetraminehexaacetic acid ・N,N,N-trimethylenephosphonic acid ・ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid-・1 .3-diamino-2-propanol-tetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, Ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethane-1,1-diphosphonic acid, N,
N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid Two or more of these chelating agents may be used in combination as necessary. These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example, it is about 0.1 g to 10 g per 1β.

Any development accelerator can be added to the color developer if necessary.

As a development accelerator, Japanese Patent Publication No. 57-16088 and No. 3
No. 7-5987, No. 38-7826, No. 44-123
No. 80, No. 45-9019 and U.S. Patent No. 3.813
．． Thioether compounds described in No. 247, etc.: JP-A No. 1973
p-phenylenediamine compounds described in No. 2-49829 and No. 50-15554, JP-A-50-137
'726, JP 44-30074, JP 56
-156826 and 52-43429, etc.: U.S. Patent No. 2.610.122
p-aminophenols described in U.S. Patent Nos. 2.494.903 and 4.119.462;
．． 128.182, 4.230.796, 3.
253.919, Japanese Patent Publication No. 41-11431, U.S. Pat.
Japanese Patent Publication No. 37-16088, Japanese Patent Publication No. 42-25201, U.S. Patent No. 3.128.183, Japanese Patent Publication No. 41-1143
No. 1, No. 42-23883 and U.S. Patent No. 3.532
．． The polyalkylene oxide described in No. 501, etc., 1-phenyl-3-pyrazolidones, hydrazines, meso ion type compounds, thione type compounds, imidazoles, etc. can be added as necessary. Particularly preferred are thioether compounds and 1-phenyl-3-pyrazolidones.

In the present invention, an arbitrary antifoggant can be added to the color developer, if necessary. As antifoggants, potassium bromide,
Alkali metal halides such as sodium chloride, potassium iodide and other organic antifoggants may also be used.

Examples of the organic antifoggant include benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazone, 5-methylbenzotriazole, 5-nitropenzotriazole, and 5-chloropenzotriazole. Nitrogen-containing heterocyclic compounds such as Nope 2-thiazolylpenzimidazole Nope 2-thiazolylmethyl-benzimidazole Nope hydroxyazaindolizine and general compounds such as 2-mercaptobenzimidazole and 2-mercaptobenzothiazole Formula (■), General formula (■), General formula (III)
Alternatively, mercapto-substituted heterocyclic compounds other than general formula (rV), adenine, and mercapto-substituted aromatic compounds such as thiosalicylic acid can be used.

These antifoggants may be eluted from the color photosensitive material during processing and may accumulate in the color developer, but from the viewpoint of reducing the amount of discharge, it is preferable that the amount of these accumulated is small.

The color developer of the present invention preferably contains a fluorescent brightener. As an optical brightener, 4,4-diamino-2
, 2'-disulfostilbene type compounds are preferred. The amount added is 0 to 5 g/β, preferably 0.1 g to 2 g/i.

Further, if necessary, surfactants such as alkylphosphonic acids, arylphosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added.

The processing temperature of the color developer in the present invention is 30°C to 5°C.
The temperature is preferably 0°C, more preferably 33°C to 42°C. The replenishment amount is 30mj per 1m2 of photosensitive material! ~2000
mf is preferably 30mj2 to 1500mA+. From the viewpoint of reducing the amount of waste liquid, it is preferable that the amount of these replenishments be small.

The bleaching agent used in the bleaching solution or bleach-fixing solution used in the present invention is a ferric ion complex that is a combination of ferric ion and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or a salt thereof. It is a complex. Aminopolycarboxylic acid salts or aminopolyphosphonic acid salts are salts of aminopolycarboxylic acids or aminopolyphosphonic acids with alkali metals, ammonium, or water-soluble amines. Examples of alkali metals include sodium, potassium, lithium, etc.; examples of water-soluble amines include alkyl amines such as methylamine, diethylamine, triethylamine, and butylamine; ring amines such as cyclohexylamine; aryl amines such as aniline and m-toluidine; Heterocyclic amines such as pyridine, morpholine, and piperidine.

Typical examples of chelating agents such as these aminopolycarboxylic acids and aminopolyphosphonic acids or their salts include: ethylenediaminetetraacetic acid ethylenediaminetetraacetic acid disodium salt ethylenediaminetetraacetic acid diammonium salt ethylenediaminetetraacetic acid tetra(trimethylammonium) salt ethylenediamine Tetraacetic acid tetrapotassium salt Ethylenediaminetetraacetic acid tetrasodium salt Ethylenediaminetetraacetic acid trisodium salt Diethylenetriaminepentaacetic acid Diethylenetriaminepentaacetic acid pentasodium salt Ethylenediamine-N-(β-oxyethyl)-N,N
',N'-ethylenediamine triacetate-N-(β-oxyethyl)-N,N
',N'-Triacetic acid trisodium salt ethylenediamine-N-(β-oxyethyl)-N,N
',N'-) triammonium acetate propylene diamine tetraacetic acid propylene diamine tetraacetic acid disodium salt nitrilotriacetic acid nitrilotriacetic acid trisodium salt cyclohexanediamine tetraacetic acid cyclohexane diamine tetraacetic acid disodium salt iminodiacetic acid dihydroxyethylglycine ethyl ether diamine tetraacetic acid Glycol ether diamine tetraacetic acid ethylene diamine tetraprobionic acid phenylene diamine tetraacetic acid 1,3-diaminopropanol-N,N,N'.

N'-tetramethylenephosphonic acid ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid 1,3-propylenediamine-N,N,N'.

Examples include N'-tetramethylenephosphonic acid, but the compound is not limited to these exemplified compounds.

The ferric ion complex salt may be used in the form of a complex salt, or as a ferric ion complex salt.
Iron salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc. and chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, phosphonocarboxylic acids, etc. may be used to form a ferric ion complex salt in a solution. When used in the form of a complex salt, one type of complex salt may be used, or two or more types of complex salts may be used. On the other hand, when forming a complex salt in a solution using a ferric salt and a chelating agent, one or more types of ferric salts may be used. Furthermore, one type or two or more types of chelating agents may be used. In any case, the chelating agent may be used in excess of the amount needed to form the ferric ion complex. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 mol/l, preferably 0.05 to 0.50 mol/l.

Further, a bleach accelerator may be used in the bleaching solution or bleach-fixing solution, if necessary. Specific examples of useful bleaching accelerators include U.S. Pat. No. 57831, same 3
No. 7418, No. 53-65732, No. 53-7262
No. 3, No. 53-95630, No. 53-95631,
No. 53-104232, No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure No. Nα17129 (July 1978)
Compounds having a mercapto group or disulfide group such as those described in Japanese Patent Publication No. 1987-140129; Thiazolidine derivatives such as those described in Japanese Patent Publication No. 140129/1983;
No., JP-A-52-2'0832, JP-A No. 53-32735
Thiourea derivatives described in US Pat. No. 3,706,561;
- Iodide described in No. 16235; West German Patent No. 966, 4
No. 10, same 2. ．． Polyethylene oxides described in Japanese Patent Publication No. 748.430; polyamine compounds described in Japanese Patent Publication No. 45-8836; and other JP-A Nos. 49-42434 and 4
No. 9-59644, No. 53-94927, No. 54-3
No. 5727, No. 55-26506 and No. 58-'1
Examples include the compound described in No. 63940 and iodine and bromide ions. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and in particular, compounds described in U.S. Pat. Compounds are preferred.

In addition, the bleaching solution or bleach-fixing solution of the present invention contains bromide (
For example, a rehalogenating agent of potassium bromide, IJium bromide, ammonium bromide) or chloride (eg potassium chloride, sodium chloride, ammonium chloride) or iodide (eg ammonium iodide) can be included.

If necessary, one or more inorganic substances having pH buffering ability such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Acids, organic acids, alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The fixing agent used in the bleach-fixing solution or fixing solution of the present invention is:
Known fixatives, i.e. thiosulfates such as sodium thiosulfate, ammonium thiosulfate; sodium thiocyanate;
Thiocyanates such as ammonium thiocyanate; ethylene bisthioglycolic acid, 3,6-cythia 1,8-
These are water-soluble silver halide dissolving agents such as thioether compounds such as octanediol and thioureas, and these can be used alone or in combination of two or more. It is also possible to use a special bleach-fix solution made of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred.

The amount of fixing agent per B is preferably 0.3 to 2 mol,
More preferably, it is in the range of 0.5 to 1.0 mol.

The pH range of the bleach-fix solution or fix solution in the present invention is 3 to 3.
10 is preferable, and 4 to 9 are particularly preferable. If the pH is lower than this, the desilvering performance is improved, but the deterioration of the solution and the leucoization of the cyan dye are accelerated.

On the other hand, if the pH is higher than this, desilvering is delayed and staining is likely to occur.

In order to adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid (glacial acetic acid), bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate, etc. can be added as necessary.

Further, the bleach-fix solution may contain various other optical brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

The bleach-fix solution and fixer of the present invention contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives. , metabisulfite (e.g. potassium metabisulfite,
Sodium metabisulfite, ammonium metabisulfite,
etc.) containing sulfite ion-releasing compounds. These compounds are approximately 0.02 to 0.5 in terms of sulfite ion.
The content is preferably 0 mol/l, more preferably 0.04 to 0.40 mol/β.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

Furthermore, buffering agents, optical brighteners, chelating agents, antifungal agents, etc. may be added as necessary.

Next, the water washing step of the present invention will be explained. In the present invention, instead of the usual "water washing treatment", a simple treatment method may be used in which only a so-called "stabilization treatment" is performed without providing a substantial water washing step. As described above, the term "water washing treatment" as used in the present invention is used in the broad meaning described above.

The amount of washing water in the present invention is difficult to specify because it varies depending on the number of baths in multistage countercurrent washing and the amount of prebath components brought in for the amount of photosensitive material. It is sufficient if it is I x 10-' or less. For example, in the case of three-tank countercurrent water washing, it is preferable to use about 1000 mβ or more per m2 of photosensitive material, more preferably 5000 m1 or more. Further, in the case of water-saving treatment, it is preferable to use 100 to 1000 mβ per 1 m 2 of the photosensitive material.

The water washing temperature is 15°C to 45°C, more preferably 20°C to 3°C.
The temperature is 5°C.

In the washing process, for the purpose of preventing precipitation and stabilizing the washing water,
Various known compounds may be added. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid, bactericidal agents and anti-inflammatory agents that prevent the growth of various bacteria, algae, and molds (for example, "Journal of Antibacterial and・Antibact, Antifung, A
gents) Vol, 11, N015, p207
~223 (1983) and compounds described in Hiroshi Horiguchi's "Chemistry of Antibacterial and Antifungal", metal salts such as magnesium salts and aluminum salts, alkali metal and ammonium salts, or dry loads and unevenness. A surfactant or the like may be added as necessary to prevent this.

Or West's ``Photographic Science and Engineering Link Magazine (Photo.

SCI, Eng.), Volume 6, 344-359.
Compounds described in Page (1965) etc. may be added.

Furthermore, chelating agents, bactericides, and anti-piping agents are added to the washing water.
The present invention is particularly effective when the amount of washing water is significantly reduced by multistage countercurrent washing using two or more tanks. It is also particularly effective when carrying out a multi-stage countercurrent stabilization process (so-called stabilization process) as described in JP-A-57-8543 instead of the usual water washing process. In these cases, the bleach-fix components of the final bath should be less than or equal to 5X10-2, preferably 1X
It is sufficient if it is 10-2 or less.

Various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, adjust the membrane pH (e.g. pH 3~
8) various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) (used in combination) and aldehydes such as formalin are representative examples. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), fungicides (thiazole series, isothiazole series, halogenated phenols (sulfanilamide, benzotriazole, etc.) ), various additives such as surfactants, optical brighteners, and hardeners may be used (and two or more compounds for the same or different purposes may be used in combination).

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order to improve image storage stability.

When the amount of washing water is significantly reduced as described above, it is preferable for the purpose of reducing the amount of waste liquid to flow some or all of the overflow liquid of the washing water into the bleach-fix bath or fixing bath, which is a pre-bath.

In this treatment step, during continuous treatment, a constant finish can be obtained by using a replenisher for each treatment solution to prevent fluctuations in the liquid composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

Each treatment bath may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, nitrogen stirring, air stirring, etc., as necessary.

If the method of the present invention uses a color developer,
It can be applied to any processing step. For example, it can be applied to color photographic paper, color reversal photographic paper, direct positive color photographic paper, etc.

Example 1 Metal aluminum is roughly rolled, annealed, and then two roughly rolled aluminum sheets are stacked on top of each other between the upper and lower rolling rollers at the center. An aluminum foil with a thickness of about 10 μm was obtained by passing the aluminum foil through the middle rolling roller and then through the middle rolling roller at the bottom. Photographic RC-Paper RC using low density polyethylene as a solvent
- One side of the paper was laminated with aluminum foil.

Next, an ionomer resin (manufactured by DuPont) was applied onto the thin aluminum layer, subjected to corona discharge treatment, and then undercoated using gelatin and a hardening agent, 1-oxy-3,5-dichloro-8-sodium triazine.

This will be referred to as support I. The RC-paper whose surface was laminated with polyethylene was placed in a vacuum evaporator, and aluminum was applied to the substrate surface at a vacuum level of 10-1 torr.
A vapor-deposited film with a thickness of 0.0 cm was formed. This was coated with low-density polyethylene to provide a polyethylene resin layer having a thickness of 20 μm.

A similar undercoat layer was provided on this to prepare support (2). Further, aluminum powder having an average particle size of about 2 μm was mixed with an ionomer resin and applied onto RC-paper treated with corona discharge. The aluminum powder was approximately 5 g/m'. Thereon, an undercoat layer was provided using gelatin and a hardening agent 1-oxy-3,5-dichloro-s-to-IJ7 sodium. This was used as support (■).

Supports I, II, and ■ were used, and each layer having the composition shown in Table 6 was provided thereon. The composition of the silver halide emulsion shown in Table 6 is shown in Table 7. Sensitive material samples 1 to 5 according to the present invention and comparative samples 1 to 4 were obtained. However, the emulsion for the blue-sensitive layer contains a sensitizing dye (m
) per mole of silver halide? , 0x10"' mol, 4.0x10-4 mol of sensitizing dye (d) per 1 mol of silver halide in the emulsion for the green-sensitive layer, and sensitizing dye (V) in the emulsion for the red-sensitive layer. Spectral sensitization was carried out by adding 1.0×10 −' mol of per mol of silver halide.

The present invention will be described in detail below with reference to Examples. Silver halide emulsion (1) used in the Examples of the present invention was prepared as follows.

(1 liquid) (2 liquid) Sulfuric acid (IN) 24 cc (
3 liquids) The following silver halide solvent (1%) 3ccH3CH.

(Liquid 5) (Liquid 6) (Liquid 7) (Liquid 1) was heated to 56°C, and (Liquid 2) and (Liquid 3) were added. Thereafter, (liquid 4) and (liquid 5) were added simultaneously for 30 minutes. After another 10 minutes, (6 liquids, 7 liquids)
were added simultaneously over a period of 20 minutes. After 5 minutes of addition, the temperature was lowered and desalted. Add water and dispersed gelatin and adjust the pH to 6.
2, the average particle size is 0.45 μm1. The coefficient of variation (the value obtained by dividing the standard deviation by the average particle size: S/d) is 0.
08, a monodispersed cubic silver chlorobromide emulsion containing 70 mol % of silver bromide was obtained.

Sodium thiosulfate was added to this emulsion to perform optimal chemical sensitization.

Next, silver chloride emulsion (2) with different silver chloride contents (
3) Substitute (4) and (5) with the above 4-liquid and 6-liquid KBr
, were prepared in the same manner by changing the amount of NaCl and the addition times of liquids 4 and 5 as shown in Table 1.

Table 1 Average grain size of silver halide emulsions (1) to (5),
The coefficient of variation and halogen composition are shown in Table 2.

Table 2 Silver halide emulsion (6) used in the examples of the present invention was prepared as follows.

(9 liquids) Sulfuric acid (IN) 20 cc (10 liquids) The following silver halide solvents (1%) 3 ccH3 ~ (11 liquids) (12 liquids) (13 liquids) (14 liquids) (8 liquids) heated to 75°C Then, (9 liquids) and 10 liquids) were added. Thereafter, (Liquid 11) and (Liquid 12) were added simultaneously over a period of 9 minutes. After another 10 minutes, (5 liquids) and (1
4 liquids) were simultaneously added over a period of 45 minutes. 5 minutes after addition,
The temperature was lowered and desalted.

Add water and dispersed gelatin, adjust the pH to 6.2, average particle size 1.01 μm, coefficient of variation (standard deviation divided by average particle size: S/d) 0.08, silver bromide 70
A monodisperse cubic silver chlorobromide emulsion of mol % was obtained. Sodium thiosulfate was added to this emulsion to perform optimal chemical sensitization.

Next, silver halide emulsions (7) (8) with different silver chloride contents
), change the liquid temperature of the above 8 liquids to 62 ° C, and further change the composition of liquids 11 to 14, liquids 11, 12, 13, and 14.
Similar preparations were made by changing the addition time of the liquid as shown in Tables 3 and 4.

Average grain size of silver halide emulsions (6) to (8),
Table 5 shows the coefficient of variation and halogen composition.

Table 5 (a) Magenta coupler (b) Color image stabilizer H3 (c) Solvent “H.

(d) Sensitizing dye So, 11 ・N(Ca++5)p ('') Yellow coupler 1M H (k) Color image stabilizer (f) Solvent (m) Blue-sensitive sensitizing dye (n) Color mixing inhibitor H (Q ) Magenta coupler (J (p) Anti-fading agent 0■ (q) 1:5:3 mixture (molar ratio) of ultraviolet absorber) ('') Color mixing inhibitor 0■ (s) Solvent (iso C5LsO+TP=0 (1> Cyan coupler I (u) 1:3:3 mixture (molar ratio) of color image stabilizer (V) Red-sensitive sensitized color chart Samples 1 to 5 Comparative samples 1 to 4 were mixed with a photosensitive needle (FWH type manufactured by Fuji Film Co., Ltd.) , with a light source color temperature of 3200°), three-color separation was performed using a blue filter, a green filter, and a red filter to give gradation exposure.

Next, the strips were developed, bleach-fixed, and rinsed under the following conditions. In addition, we developed a cabinet-sized sample without exposing it to light and examined the presence or absence of spots, and the results are shown in Table 8.
Shown below.

Process Temperature Time Development Prescription C 35℃ 45 seconds bleach fixing Prescription separate note 35℃ 45 second rinse Prescription separate note
28-35℃ 1 minute 30 seconds (bleach-fix solution formulation) Ammonium thiosulfate (54vt%) 50ml Na2SO* 15g
N)+4 (Fe(III)(BDTA))
55 gEDTA ・2
Na 4 g glacial acetic acid
Add 8.61g water to make the total amount
1000mf100O, 4) (Rinse liquid formulation) Add BDTA, 2Na, 2H, 200, 4g water to make a total volume of 1000ml100O, 0) Color developer (C) Water 8
00 cc diethylene and triaminepentaacetic acid 1,
0g Sodium sulfite 0.2g
N,N-diethylhydroxylamine 4.2g Potassium bromide 0.01g Sodium chloride 1.5g Triethanolamine 8.0g Potassium carbonate
30 gN-ethyl-N-(β-
Methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 4.5g4.4'
- Diaminostilbene-based fluorescent whitening agent (Seiseikagaku@Whitex4) 2.0
g Add water to 1000 c
cKOH pH 10.25 As a result, Samples 1 to 5 of the present invention showed good color development even with extremely short development time of 45 seconds, and no spots were observed when fresh. Furthermore, even over time (45° C. x 80 RH% x 4 days), almost no spots were observed, indicating good stability.

On the other hand, Comparative Sample 1 suppressed the occurrence of spots, but had low color development and was unsuitable for short-term development. Further, in Comparative Samples 2 to 4, the number of spots was observed both when fresh and after a certain period of time had passed, indicating that fogging had occurred.

Procedural amendments Director General of the Patent Office Kunio Ogawa 1. Indication of the case 1985 Patent Application No. 168805 2. Title of the invention Color photographic light-sensitive material 3. Person making the amendment Relationship to the case Applicant name Title (520) Fuji Photographic Film Co., Ltd. 4, Agent 6, Subject of amendment Column for detailed explanation of the invention in the specification (1) Specification Cattle The following sections are corrected as follows.

(2) The same book, page 66, line 11, “...2 minutes.

Correct "this" as follows.

"...2 minutes. This short development time can be achieved by setting the development temperature (including other related processing temperatures) to approximately 50-70°C." (3) Ibid., 102jt. (The structural formula of the al magenta coupler is corrected as follows.

(4) Same book, page 115, line 6, “...showed.”
Add the following sentence after .

Claims (20)

[Claims] (1) In a color photographic material comprising at least one photosensitive layer provided on a support, the photosensitive layer contains a coupler that forms a coloring dye through a coupling reaction with an oxidized product of an aromatic primary amine color developing agent. At least one silver halide emulsion containing 70 mol% or more of silver chloride, and one or two anti-gabbing agents selected from the group consisting of mercaptothiadiazole, mercaptotriazole, mercaptotetrazole and aromatic triazole compounds. 1. A color photographic light-sensitive material, characterized in that the support is a photographic support having a specular reflective surface or a type 2 diffuse reflective surface, and a photosensitive layer is provided on the surface. (2) Mercaptotetrazole has the general formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents an alkyl group, alkenyl group, or aryl group, and 2. The color photographic material according to claim 1, which is represented by (representing a precursor). (3) Mercaptothiadiazole has the general formula (II) ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, L represents a divalent linking group, R represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group , X represents a hydrogen atom, an alkali metal atom, an ammonium group, or a precursor, and n represents 0 or 1. (4) Mercaptotriazole has the general formula (III) ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents an alkyl group, alkenyl group, or aryl group, and (represents a precursor, L represents a divalent linking group, R^3 represents an alkyl group, alkenyl group, or aryl group, and n represents 0 or 1) according to claim 1. Color photographic material. (5) The aromatic triazole compound is represented by the general formula (IV) ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, Z represents an aromatic ring-forming atomic group) Claim 1 described color photographic material. (6) Antifoggant is 1×10 per mole of silver halide
The color photographic material according to claim 1, which contains ^-^4 to 1 x 10^-^2 moles. (7) A color photographic light-sensitive material according to claim 1, wherein the photographic support is provided with a solid thin film layer having a type 2 diffuse reflective surface on the substrate. (8) The color photographic material according to claim 7, wherein the solid is a metal. (9) The color photographic material according to claim 8, wherein the metal is aluminum, silver, gold, nickel, magnesium, or an alloy thereof. (10) The color photographic material according to any one of claims 7 to 9, wherein a thermoplastic resin layer or an adhesive layer is provided between the solid thin film layer and the substrate. (11) Claims 7 to 10, wherein the type 2 diffuse reflective surface of the solid thin film layer is a mirror surface of the solid thin film layer with irregularities of about 0.1 to 2000 spots/mm. The color photographic material described in any one of paragraphs. (12) The color photographic material as claimed in claim 1, wherein a packed layer of solid powder having a surface of type 2 diffuse reflection is provided on a substrate. (13) The color photographic material according to claim 12, wherein the solid powder filling layer is composed of solid powder and resin. (14) Claim 1 in which the solid powder is a metal powder
Color photographic material according to item 2 or 13. (15) Metal powder is aluminum, silver, gold, nickel,
15. The color photographic material according to claim 14, which is a powder of magnesium or an alloy thereof. (16) The color photographic material according to claim 14 or 15, wherein the metal powder has an average particle diameter of 0.01 to 100 μm. (17) Claim 14 in which the resin is a water-resistant resin
Color photographic material described in Section 1. (18) A thermoplastic resin layer or an adhesive layer is provided between the solid powder filling layer and the base layer.
The color photographic material according to any one of Item 17. (19) The color photographic light-sensitive material according to claim 1, wherein the support having a specular reflective surface is formed by providing a metal thin film layer on the substrate. (20) The color photographic material according to claim 19, wherein the metal is aluminum, gold, silver, copper, chromium, nickel, platinum, or an alloy thereof.