JP2631140B2 - Silver halide color photographic materials - Google Patents

Description

The present invention relates to a silver halide color photographic light-sensitive material,
More specifically, the present invention relates to a silver halide color photographic light-sensitive material having excellent color reproducibility and improved storage stability under high temperature and high humidity.

(Prior Art) In recent years, color photographic materials have been required to have higher and higher image quality, and it is necessary to improve photographic characteristics such as color reproducibility and tone reproducibility, graininess and sharpness. In order to satisfy both requirements for sensitivity and image quality of a silver halide photographic material, it is necessary to improve the light absorption, quantum efficiency and developability of a silver halide emulsion.

Further, when the photographic light-sensitive material is stored under high temperature or high temperature and high humidity, it may cause performance changes such as increase in fog and decrease in sensitivity during storage, and improvement of temporal stability has been strongly desired. .

U.S. Pat. No. 3,979,213 (hereinafter referred to as Reference A) discloses that the intrinsic desensitization of an internal latent image type silver halide emulsion during color sensitization is the same as that of a silver halide emulsion having the same grain size chemically sensitized only to the surface. It is disclosed that the color sensitization can be effectively performed using a large amount of a sensitizing dye. However, the internal latent image type emulsion used here has most of the radiation sensitive portions (or latent image forming portions) inside the grains, and the ratio of surface sensitivity to total sensitivity is 10% or less. The emulsion which forms a latent image sufficiently inside the grains as described above becomes insufficiently developed even when it is developed with a developing solution of a black-and-white, color negative or color reversal photosensitive material which is practically used, and the sensitivity is substantially impaired. Will be. Moreover, when a large amount of the sensitizing dyes disclosed herein is adsorbed on silver halide grains, the development of the grains is further suppressed, which is not preferable.

Similarly, Journal of Photographic Science, Vol. 13, p. 48 (1965), Vol. 22, p. 174 (1974),
Vol. 25, p. 19 (1977), Vol. 31, p. 41 (1986), Photographic Science and Engineering, Vol. 19, p. 333 (1975), U.S. Patent Nos. 4,035,185, 3,850,637, Berichte der Bunsen, Gezershyaft Fuyah Fijicalitssie Chemie, 67, 356
The internal latent image type emulsion described in page (1963) has the most radiation-sensitive part at a depth of 0.01 μm or more, and can be easily developed with a practical processing solution. However, it is not possible to achieve optimum sensitivity and granularity.

Further, U.S. Pat. No. 3,966,476 discloses an emulsion in which a latent image is disposed in a cavity opening toward the grain surface and can be developed with a surface developer. However, an emulsion which can exhibit sensitivity equal to or higher than that of a surface latent image type emulsion of the same size by processing with a surface developer is hardly called an internal latent image type emulsion, and the internal latent image type emulsion described in Reference A is referred to. Cannot be used sufficiently. Further, since the latent image is open on the surface, the latent image is oxidized in the preservation process after the formation of the latent image until the development processing, and the sensitivity is substantially reduced.

The silver halide emulsion having a high internal sensitivity is prepared by mixing a chemically sensitized large-size grain with an unchemically sensitized fine grain emulsion and subjecting it to Ostwald ripening as described in U.S. Patent No. 3,206,313. U.S. Pat. No. 3,917,485 also describes that it is prepared by adding silver ions and halide ions to the chemically sensitized grains in alternating excess. By controlling the shell thickness using such a preparation method, the balance between surface sensitivity and internal sensitivity can be adjusted appropriately.

However, it is not clear how the depth at which the most latent images are formed is clear, and what the latent image distribution from the surface to the inside is for a practical processing solution has good sensitivity and image quality. Has not been studied as to whether or not it is preferable for the expression of

On the other hand, in the production of a silver halide color photographic light-sensitive material, dyeing the silver halide emulsion layer itself is described in U.S. Pat. No. 3,647,460, Japanese Patent Publication No. 51-1419 and British Patent 1,17.
It is well known in the art as described in 7,429 and the like. However, dyes used in photosensitive materials are (1)
It has appropriate spectral absorption for the purpose of not deteriorating color reproducibility, (2) it has no desensitizing effect or fogging effect on silver halide, and (3) it is prompt and complete in the development process. Needs to be decolorized.

(Problems to be Solved by the Invention) However, although a very wide variety of dyes have been proposed as dyes for photographic light-sensitive materials, they cannot satisfy all of the above-mentioned conditions and have drawbacks in color reproducibility. Or the silver halide emulsion has a desensitizing effect or a fogging effect on the silver halide emulsion.

Accordingly, a first object of the present invention is to provide a silver halide color photographic material having excellent color reproducibility.

A second object of the present invention is to provide a silver halide color photographic light-sensitive material which has a small increase in fog and a small decrease in sensitivity even when stored under high temperature or high temperature and high humidity.

(Means for Solving the Problems) As a result of diligent studies, the present inventors have found that the object of the present invention is to provide at least one red-sensitive silver halide emulsion layer and at least one green-sensitive halide In a photographic light-sensitive material having a silver emulsion layer and a blue-sensitive silver halide emulsion layer, at least one of the emulsion layers has a latent image distribution in a depth direction from a grain surface to an internal depth direction of the silver halide emulsion. Having at least one maximum value, the position where the maximum value exists is less than 0.01 μm from the particle surface, and the number of latent images on the particle surface is 1/5 or more of the maximum value and less than 1 time. A silver halide color photographic light-sensitive material, characterized in that the photographic light-sensitive material contains at least one compound represented by the following general formula (I). Achieved.

General formula (I) Wherein R _1, R ₂ represents an alkyl group or an aryl group, R _3,
R ₄ represents at least one carboxyl group or sulfo group, an alkyl group or an aralkyl group.

 n represents 0, 1 or 2.

Here, the latent image distribution has a depth (x μm) from the particle surface of the latent image on the horizontal axis and the number of latent images (y) on the vertical axis, and x is S: Average grain size of silver halide emulsion (μm) Ag ₁ : Amount of residual silver after performing the following processing on an unexposed emulsion-coated sample Ag ₀ : Amount of coated silver before processing, and y is 1 / This is the reciprocal of the exposure amount that gives a density of +0.2 when the following processing is performed after white exposure for 100 seconds. The processing conditions for obtaining the latent image distribution were as follows: N-methyl-p-aminophenol sulfate 2.5 g L-ascorbate 10 g Sodium metaborate 35 g Potassium bromide 1 g Add water 1 (pH 9.6) 0 to 10 g / anhydrous sodium sulfite
The treatment is performed at 25 ° C. for 5 minutes. Here, by changing the amount of anhydrous sodium sulfite from 0 to 10 g /,
The depth from the surface of the latent image in the silver halide grains developed during processing changes, and the change in the number of latent images in the depth direction can be known.

Next, the oxonol type dye represented by the general formula (I) will be described in detail.

Wherein R _1, R ₂ represents an alkyl group or an aryl group, R _3,
R ₄ represents an alkyl group or an aralkyl group having at least one carboxyl group or sulfo group, respectively.

 n represents 0.1 or 2.

The methine chain of the compound represented by the general formula (I) may have a substituent (for example, an alkyl group such as ethyl, a halogen atom such as chlorine or bromine), and the carboxyl group and the sulfo group are salts (for example, Na, K, ammonium).

In the present invention, the alkyl group and aryl group represented by R ₁ and R ₂ in the general formula (I) may be a substituent (for example, an alkoxy group such as sulfo, carboxy, hydroxy or methoxy, ethoxy, R ₁ and R 2) _{When 2} is an aryl group, alkyl such as methyl and ethyl, cyano and halogen atoms)
May be provided. The alkyl group represented by R ₁ and R ₂ is an alkyl group having 1 to 20 carbon atoms, for example, methyl,
Ethyl, isopropyl, t-butyl, phenethyl, octyl, dodecyl, octadecyl, methoxyethyl, 4-
Sulfobutyl, 2-dimethylaminoethyl and the like. The aryl group represented by R ₁ and R ₂ includes, for example, phenyl, naphthyl, 2-sulfophenyl, 4-methylphenyl and the like.

The alkyl group and aralkyl group represented by R ₃ and R ₄ are a substituent other than a carboxy group or a sulfo group (eg, hydroxy, cyano), a substituted or unsubstituted amino group (eg, dimethylamino, N-ethyl-N-2-) Sulfobutylamino,
Halogen atoms such as diethylamino, piperidino, morpholino), chlorine and bromine, alkoxy groups (eg, methoxy, ethoxy, 4-sulfobutoxy, 2-carboxyethoxy), amide groups (eg, acetamido, methanesulfonamido), carbamoyl groups (eg, It may have an unsubstituted carbamoyl, methylcarbamoyl, hydroxyethylcarbamoyl), sulfamoyl group, or alkyl group (eg, methyl, ethyl). Examples of the alkyl group represented by R ₃ and R ₄ include sulfomethyl, carboxymethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 3-sulfo-2-methylpropyl, 4-carboxybutyl, 6-sulfohexyl and the like. No. R ₃
And aralkyl groups represented by R ₄ are, for example, 2-sulfobenzyl, 2,4-disulfobenzyl, 4-methoxy-2
-(4-sulfobutyloxy) benzyl, 4-sulfophenethyl, 4- {N-methyl-N- (3-sulfopropyl) amino} -2-methylbenzyl, 4-carboxybenzyl, 4- (2-sulfoethylcarbamoyl ) Benzyl and the like.

Hereinafter, typical examples of the compound represented by formula (I) of the present invention are shown, but the present invention is not limited thereto.

The compound represented by the general formula (I) is disclosed in JP-A-49-5125.
And JP-A-49-114420.

The compound represented by the above general formula (I) of the present invention is added to an aqueous solution or a solution of an organic solvent (methanol, ethanol or the like) and added to a silver halide emulsion layer or an intermediate layer and coated. The coating amount is preferably 5 × 10 ⁻² mol to 5 × 10 ⁻⁷ mol / m ² , particularly preferably 1 × 10 ^{−3 to} 5 × 10 ⁻⁵ mol / m ² .

In the silver halide photographic emulsion used in the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used. Preferred silver halides are silver iodobromide or silver iodochlorobromide containing up to about 30 mol% silver iodide. Particularly preferred is silver iodobromide containing from about 0.5 mol% to about 15 mol% of silver iodide.

A method for preparing an internal latent image type emulsion is described in U.S. Pat.
No. 3, 3,966,476, 3,206,313, 3,917,485,
The methods described in JP-B-43-29405, JP-B-45-13259 and the like can be used. The method of sensitization, the amount of silver halide precipitated after chemical sensitization, and the conditions of precipitation must be adjusted.

Specifically, in U.S. Pat. No. 3,979,213, an internal latent image type emulsion is prepared by a method in which silver halide is precipitated again by a controlled double jet method on emulsion grains whose surface is chemically sensitized. If the amount of silver halide precipitated in the literature is precipitated on the grains, the ratio of surface sensitivity to total sensitivity will be less than one tenth. For this reason, in order to obtain the latent image distribution of the present invention, the amount of silver halide precipitated after chemical sensitization is smaller than that carried out in U.S. Pat.No. 3,979,213, less than 0.01 μm, preferably less than 0.01 μm from the grain surface. 0.003-0.0
It must be 08 μm thick.

U.S. Pat. No. 3,966,476 also describes a method of precipitating silver halide on emulsion grains after chemical sensitization by a control double jet method. However,
When the silver halide is precipitated by a method as practiced in the above literature after the chemical sensitization, the photosensitive nucleus cannot be embedded in the grain. Therefore, the emulsions carried out in the above-mentioned literature exhibit a sensitivity increase of at least 0.02 logE or more even by surface development compared with the emulsions whose original surfaces have been chemically sensitized. For this reason, in order to obtain the latent image distribution of the present invention, the amount of silver halide precipitated after chemical sensitization should be higher than that carried out in U.S. Pat. It is necessary to control the solubility of silver halide and the rate of addition of soluble silver salt and soluble halide.

The maximum value of the distribution of silver iodide in the grains may be one or plural. Further, the silver iodide content at the maximum value is preferably at least twice the average silver iodide content of the whole grains, more preferably at least four times, and most preferably silver iodide itself. The change gradient of the silver iodide composition reaching the maximum value is preferably as large as possible. In an extreme case, the silver iodide composition may have an epitaxial junction.

The crystal structure other than the portion where the maximum value of the silver iodide distribution is formed may be uniform, may have a different halogen composition, or may have a layered structure. These emulsion grains are described in UK Patent 1,027,146, US Patent 3,505,068,
No. 4,444,877 and Japanese Patent Application No. 59-248469.

Further, the grains of the present invention may be bonded to silver halides having different compositions by epitaxial bonding.
Further, for example, it may be bonded to a compound other than silver halide such as silver rhodan or lead oxide. These emulsion grains, U.S. Pat.Nos. 4,094,684, 4,142,900, 4,459,353,
UK Patent No. 2,038,792, U.S. Patent Nos. 4,349,622,
395,478, 4,433,501, 4,463,087, 3,656,9
No. 62, 3,852,067 and JP-A-59-162540.

The silver halide grains may be so-called regular grains having regular crystals such as cubes, octahedrons, and tetradecahedrons, may have irregular crystal forms such as tabular spheres, and twin crystals. It may be one having a crystal defect such as a plane or a complex form thereof, but a regular particle is preferable in controlling the latent image distribution. Also, a mixture of various crystal forms may be used.

Chemical sensitization is described in The James of the Theory of Photographic Process, 4th Edition.
Edition, published by Macmillan, 1977, (THJames, The Theory
of the Photographic Process, 4th ed, Macmillan, 197
7) It can be carried out using active gelatin as described on pages 67-76, and can also be performed in Research Disclosure, Volume 120, April 1974, 12008; Research Disclosure, 34, 1975. June 13452, U.S. Patent No. 2,642,3
No. 61, No. 3,297,446, No. 3,772,031, No. 3,857,711
Nos. 3,901,714, 4,266,018, and 3,904,41
No. 5, and pAg 5-10, pH 5-8 and a temperature of 30-80 ° C. as described in GB 1,315,755, sulfur, selenium, chillyl, gold, platinum, palladium, iridium or a plurality of these sensitizers. Can be performed using a combination of Chemical sensitization is optimally performed in the presence of a gold compound and a thiocyanate compound, and in U.S. Pat.
The reaction is carried out in the presence of a sulfur-containing compound described in JP-A-4,266,018 and JP-A-4,054,457, or a sulfur-containing compound such as hypo, thiourea-based compound and rhodanine-based compound. Chemical sensitization can also be performed in the presence of a chemical sensitization aid. The chemical sensitizing aids used include azaindene, azapyridazine,
Compounds known to suppress fog and increase sensitivity during chemical sensitization, such as azapyrimidine, are used. Examples of chemical sensitization aid modifiers are described in U.S. Pat.
No. 1,038, No. 3,411,914, No. 3,554,757, JP-A-58-1
No. 26526 and the aforementioned "Photographic Emulsion Chemistry" by Daffin, 138-
It is described on page 143. In addition to or in lieu of chemical sensitization, reduction sensitization, for example with hydrogen, as described in U.S. Pat.Nos. 3,891,446 and 3,984,249, and U.S. Pat.Nos. 2,518,698, 2,743,182 Or using a reducing agent such as stannous chloride, thiourea dioxide, polyamines and the like, or low pAg (eg, less than 5) and / or high pH (eg, greater than 8) as described in US Pat. Reduction sensitization can be achieved by the treatment. U.S. Pat.Nos. 3,917,485 and 3,9
Color sensitization can also be improved by the chemical sensitization method described in JP-A-66,476. When the surface of the silver halide emulsion grains of the present invention is chemically sensitized, the number of latent images formed is such that the number of latent images formed is 1/5 or more and less than 1 time the maximum value of the latent image distribution formed inside the grains. Is controlled.

Tabular grains having an aspect ratio of 5 or more are also preferably used in the present invention.

The grain size of silver halide may be fine grains of about 0.1 micron or less or large grains having a projected area diameter of up to about 10 microns, and may be a monodisperse emulsion having a narrow distribution or a monodisperse emulsion having a wide distribution. However, a monodispersed emulsion is preferred for improving graininess.

A typical monodispersed emulsion is one in which at least 95% by weight is within ± 40% of the average grain diameter. Emulsions having an average grain diameter of 0.05 to 3 microns and having at least 95% by weight or at least 95% (by number of grains) of silver halide grains within the range of an average grain diameter ± 20% can be used in the present invention. . Methods for preparing such emulsions are described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748. JP-A-48-860
Nos. 0, 51-39027, 51-83097, 53-137133
No. 54-48521, No. 54-99419, No. 58-37635,
Monodisperse emulsions such as those described in JP-A-58-49938 can also be preferably used in the present invention.

Particularly, monodisperse hexagonal tabular grains described in Japanese Patent Application No. 61-299155 are extremely preferred in the present invention.

The emulsion of the present invention can be sensitized by a method well known in the art. The amount of the sensitizing dye should be such that the maximum negative blue sensitivity is obtained, but this amount is similar to the amount that obtains the maximum negative blue sensitivity in the surface latent image type emulsion, and is much larger than that amount. It is not preferable to add a large amount of the dye because the development of the particles is suppressed.

The emulsion of the present invention can be used in the state without color sensitization.

The emulsion of the present invention can be used together with a usual so-called "surface latent image type emulsion" in the same emulsion layer. Further, the emulsion of the present invention and the above-mentioned ordinary emulsion can be used alone between emulsion layers having the same color sensitivity or different color sensitivity.

The silver halide other than silver halide in which the latent image distribution contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention has one maximum value inside the grains contains about 30 mol% or less of silver iodide. Silver iodobromide, silver iodochloride, or silver iodochlorobromide is preferred.

Particularly preferred is silver iodobromide containing from about 2 mol% to about 2 mol% silver iodide.

Silver halide grains in photographic emulsions are cubic, octahedral,
Those having regular crystals like tetradecahedron, spherical,
It may be a material having an irregular crystal such as a plate, a material having a crystal defect such as a twin plane, or a compound thereof.

The grain size of the silver halide may be as fine as about 0.2 microns or less, or as large as up to about 10 microns in projected area diameter.

The silver halide photographic emulsion that can be used in the present invention is described, for example, in Research Disclosure (RD) No. 17643 (1978).
December, p. 22-23, "I. Emulsion preparati
on and types) ”and No. 18716 (January 1979),
648 pages, Physics and Chemistry of Photography by Grafkid, published by Paul Montell (P. Glafkides, Chemic Phisique Photograph
ique Paul Montel, 1967), Photographic Chemistry by Daffin, published by Focal Press (GFDuffin, Photographi)
c Emulsion Chemistry (Focal Press, 1966)), Zekriman et al., "Production and Coating of Photographic Emulsions", published by Focalprene (VLZelikman et al, Making and Coating Photog).
raphic Emulsion, Focal Press, 1964).

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention.
Photographic Science and Engineerin (Gutoff, Photographic Science and Engineerin
g), 14, 248-257 (1970); U.S. Pat.
4,226, 4,414,310, 4,433,048, 4,439,520
And British Patent No. 2,112,157.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure.Also, silver halides having different compositions are joined by epitaxial bonding. And it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide.

 Also, a mixture of particles of various crystal forms may be used.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additive used in such a process is Research Disclosure No. 1
7643 and No. 18716, and the relevant portions are summarized in the table below.

Further, fogged silver halide emulsions disclosed in U.S. Pat. No. 4,082,553 and U.S. Pat. No. 4,626,498 may be used.

Known photographic additives which can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in the aforementioned Research Disclosure (RD) No. 17643, VII-CG.

As a yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, JP-B-58-10739, UK Patent No. 1,425,020
And Nos. 1,476,760 and the like.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferred, and U.S. Pat.
No. 0,619, No. 4,351,897, European Patent No. 76,636, U.S. Pat. No. 3,061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33
No.552, Research Disclosure No.24230 (1984
June), JP-A-60-43659, U.S. Patent No. 4,500,630
And No. 4,540,654 are particularly preferred.

Cyan couplers include phenolic and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200,
No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826, No. 3,772,002, No. 3,758,308,
No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,
No. 329,729, European Patent No. 121,365A, U.S. Patent No. 3,446,6
No. 22, No. 4,333,999, No. 4,451,559, No. 4,427,
No. 767, EP 161,626A, JP-A-60-55340, etc. are preferred.

Colored couplers for correcting unwanted absorption of coloring dyes are described in Research Disclosure No.17643 VII.
Section G, U.S. Pat.No. 4,163,670, JP-B-57-39413,
U.S. Pat.Nos. 4,004,929 and 4,138,258; British Patent No.
Those described in 1,146,368 are preferred.

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent (Published) No. 3,234,533.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
And British Patent No. 2,102,173.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are described in RD17643, VII-F above.
Patents, JP-A-57-151944 and JP-A-57-1542
Nos. 34, 60-184248 and U.S. Pat. No. 4,248,962 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include UK Patent Nos. 2,097,140 and 2,1
No. 31,188, JP-A Nos. 59-157638 and 59-170840 are preferred.

In addition, as couplers that can be used in the light-sensitive material of the present invention, competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472 and 4,338,393,
No. 4,310,618 and the like, multi-equivalent couplers described in
And DIR redox compound releasing couplers described in, for example, JP-A-185950, and couplers that release dyes that recolor after release as described in EP 173,302A.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

The steps and effects of the latex dispersion method, and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363 and West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Suitable supports that can be used in the present invention include, for example, those described above.
From page 28 of RD.No.17643, and from the right column of page 647 of No.18716
It is described in the left column on page 648.

The photosensitive material to which the present invention is applied is, for example, a color photographic photosensitive material such as a color negative film, a color reversal film (inner and outer types), a color paper, a color positive film, a color reversal paper, a color diffusion transfer process, and a die transfer process. Any material may be used, but it is particularly preferably applied to color reversal films and color reversal papers.

The color developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as this color developing agent, but p-
Phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N, -diethylaniline and 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 and sulfates, hydrochlorides or p-toluenesulfonates thereof. These compounds can be used in combination of two or more depending on the purpose.

Color developing solutions include pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
It generally contains a development inhibitor or an antifoggant such as a benzimidazole, a benzothiazole or a mercapto compound. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers,
Fogging agent such as sodium boron hydride, 1
An auxiliary developing agent such as phenyl-3-pyrazolidone,
It may contain a viscosity-imparting agent, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid.

When the reversal process is performed, color development is usually performed after black and white development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone and 1-phenyl-3-.
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing processing before bleach-fixing processing or bleaching processing after bleach-fixing processing can be arbitrarily performed according to the purpose.
Examples of the bleaching agent include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used. Representative bleaching agents include pheuliocyanide; dichromate; iron (II
Organic complex salts of I) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Aminocarboxylic acids such as diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. . Among these, iron aminopolycarboxylates (II) including iron (III) complex salts of ethylenediaminetetraacetate
I) Complex salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. In addition, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching and bleach-fixing solutions. The pH of the bleaching solution or bleach-fixing solution using these iron (III) aminocarboxylate complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH to speed up the processing.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their prebaths, if necessary.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether-based compounds, thioureas, and a large amount of iodide.The use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. As a preservative of the bleach-fixing solution, a sulfite, a bisulfite or a carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the application, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers, Vol. 64, pp. 248-253 (May, 1955).

In the processing of the photosensitive material of the present invention, the pH of the washing water is 4-
9, preferably 5-8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, application, etc., but generally, the temperature is 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds-5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, Japanese Unexamined Patent Application Publication No.
Known methods described in Nos. 57-8,543, 58-14,834, and 60-220,345 can all be used.

Further, after the above-mentioned water washing treatment, a stabilization treatment may be further carried out. For example, a stabilizing bath containing formalin and a surfactant used as a final bath of a color light-sensitive material for photography can be mentioned. . Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in various steps such as a desilvering step.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to.

(Examples) Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1 Fifteen kinds of silver iodobromide emulsions (iodine content: 3 mol%) as shown in Table 1 below were prepared.

The method for preparing these emulsions is described below.

Preparation of Monodisperse Emulsion Having (100) Crystal Habit While adding PBr to 4.5 in an aqueous gelatin solution kept at 70 ° C., an aqueous solution containing silver nitrate aqueous solution containing KBr and KI was added by double jet to prepare a monodisperse emulsion having (100) crystal habit. Dispersion emulsion (Ayanaga 0.6
8 μm). Next, this core emulsion was dispersed in three parts, and shells were formed under the following different conditions. The final grain size was 0.7 μm, and the AgI content was 3 mol%.

(Emulsion A) Sodium thiosulfate and potassium chloroaurate were added to the above core to perform chemical sensitization. Thereafter, the shell was precipitated under the same conditions as for the core formation.

(Emulsion B) A shell was precipitated on the core under the same conditions as in Emulsion A, and then subjected to chemical sensitization.

(Emulsion C) The core was subjected to chemical sensitization and shell precipitation in the same manner as Emulsion A, and then to chemical sensitization.

(Emulsion D) Emulsion D was prepared under the same conditions as Emulsion A except that a core smaller in size than the core used in preparing Emulsions A to C was used.

(Emulsion E) Emulsion E was prepared under the same conditions as Emulsion D, except that the shell was precipitated under the condition that the solubility of silver halide was increased by increasing the pBr to 5.0.

(Emulsion F) Emulsion F was prepared under the same conditions as Emulsion A, except that the shell was precipitated under the conditions that the pBr was lowered to 4.0 and the solubility of silver halide was lowered.

(Emulsions G and I) Emulsions having the same latent image distribution and final average grain sizes of 0.3 μm and 0.9 μm were prepared in the same manner as Emulsion A, and each was designated as Emulsion GI.

(Emulsions H, J, K) Emulsions having the same latent image distribution and final average grain sizes of 0.3 .mu.m and 0.9 .mu.m, 1.1 .mu.m were prepared in the same manner as Emulsion B. .

(111) Preparation of Monodisperse Emulsion Having Habit Equivalent to A, B, C, D in the same manner except that pBr at the time of grain formation of emulsions A, B, C, D was changed to 3.3 Were prepared as emulsions L, M, N, and O, respectively.

Sensitizing dye S-1 was added to the above emulsion and coated at a silver amount of 2 μg per square centimeter. FIG. 1 shows the results of the latent image distribution obtained for these coated samples.

The above film was passed through a blue filter (BPN-42) for 1/100 second, and a minus blue filter (SC-3).
Exposure was performed for 1/100 second through 9), and development processing (20 ° C., 4 minutes) was performed using the following processing solution.

Table 2 shows the sensitometric results thus obtained. Here, the sensitivity is represented by the relative value of the reciprocal of the exposure amount giving a density of fog + 0.1.

As a result, it is understood that the light-sensitive material containing the emulsion having the latent image distribution of the present invention is superior in sensitivity and storage stability to the emulsions having other latent image distributions.

For example, Emulsion F is similar to that of the present invention at the depth where the maximum value of the latent image distribution exists, but has a smaller number of latent images on the surface and has lower sensitivity than the present invention. Emulsion E is similar to the present invention in the maximum value of the latent image distribution and the number of latent images on the surface, but the depth at which the maximum value exists is deeper than in the present invention, and lower sensitivity can be obtained. Absent.

Treatment liquid 1-phenyl-3-pyrazolidone 0.5 g hydroquinone 10 g ethylenediaminetetraacetic acid / disodium 2 g sodium sulfite 60 g boric acid 4 g potassium carbonate 20 g sodium bromide 5 g diethylene glycol 20 g sodium hydroxide pH 10.0 Add conditioned water to Next, a multi-layered color light-sensitive material comprising the following layers was prepared on an undercoated cellulose triacetate film support.

First layer: anti-halation layer Black colloidal silver 0.25 g / m ² UV absorber U-1 0.1 g / m ² UV absorber U-2 0.1 g / m ² High boiling organic solvent Oil-1 gelatin 1.9 g / m ² Second layer: Intermediate layer-1 Cpd D 10 mg / m ² High boiling organic solvent Oil-3 40 mg / m ² Gelatin 0.4 g / m ² Third layer: Intermediate layer-2 Fine grain silver iodobromide emulsion having a fogged surface (Average particle size 0.06
μg, AgI content 1 mol%) Silver amount 0.05 g / m ² Gelatin 0.4 g / m ² Fourth layer: First red-sensitive emulsion layer Iodobromide spectrally sensitized with sensitizing dyes S-1 and S-2 Silver emulsion (average particle size 0.2μ and AgI content 5 mol%) Silver amount 0.4 g / m ² Coupler C-1 0.2 g / m ² C-2 0.05 g / m ² High boiling organic solvent Oil-1 0.1 cc / m ² Gelatin 0.8 g / m ² Fifth layer: Second red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (AgI content of an average particle diameter of 0.7 μm, 3 mol% Cubic monodispersed emulsion B) Silver amount 0.4 g / m ² Coupler C-1 0.2 g / m ² C-3 0.2 g / m ² C-2 0.05 g / m ² High boiling organic solvent Oil-1 0.1 cc / m ² Gelatin 0.8 g / m ² 6th layer: 3rd red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (AgI content of 2 μm with an average particle size of 0.9 μm) Spherical polydisperse emulsion of silver) 0.4 g / m ² coupler C-3 0.7 g / m ² gelatin 1.1 g / m ² 7th layer: intermediate layer-3 gelatin 0.6 g / m ² eighth layer: intermediate layer-4 fine grain silver iodobromide emulsion having a fogged surface, having an average grain size of 0.06 μm,
AgI content 1 mol% Silver content 0.05 g / m ² Compound Cpd A 0.2 g / m ² Gelatin 1.0 g / m ² Ninth layer: First green-sensitive emulsion layer Spectral sensitization with sensitizing dyes S-3 and S-4 Silver iodobromide emulsion (average grain size 0.2 μm, AgI content 5 mol%) Silver amount 0.5 g / m ² Gapler C-4 0.3 g / m ² Compound Cpd B 0.03 g / m ² Gelatin 0.5 g / m ² Tenth layer: Second green-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-3 and S-4 (monodisperse cube having an average particle diameter of 0.4 µm and an AgI content of 3 mol%) Silver amount 0.4 g / m ² Gapura C-4 0.3 g / m ² compound Cpd B 0.03 g / m ² gelatin 0.6 g / m ² 11th layer: iodobromide containing third increase green-sensitive emulsion layer Sensitizing dye S-3 and S-4 Silver halide emulsion (tabular emulsion having an average particle size of 0.7 μm and an aspect ratio of 3 and a content of 2 mol%) Silver amount 0.5 g / m ² Coupler C-4 0.8 g / m ² Compound Cpd B 0.08 g / m ² Gelatin 1.0 g / m ² 12th layer: Intermediate layer-5 Dye D-1 0.02 g / m ² Dye D-2 0.05 g / m ² Gelatin 0.6 g / m ² 13th layer: yellow filter layer Yellow colloidal silver 0.1 g / m ² compound Cpd A 0.01 g / m ² gelatin 1.1 g / m ² 14th layer: intermediate layer-5 gelatin 0.7 g / m ² 15th layer: 1st Blue-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-5 and S-6 (monodisperse cubic emulsion having an average grain size of 0.5 µm and an AgI content of 3 mol%) Silver content 0.6 g / m ² Coupler C- 5 0.6 g / m ² gelatin 0.8 g / m ² 16th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-7 and S-8 (average grain size: 0.6 μm, aspect ratio: 7) And a tabular emulsion having an AgI content of 2 mol%) Silver amount 0.4 g / m ² Coupler C-5 0.3 g / m ² C-6 0.3 g / m ² Gelatin 0.9 g / m ² 17th layer: third blue-sensitive emulsion Layer Silver iodobromide emulsion containing sensitizing dyes S-7 and S-8 (tabular emulsion having an average grain size of 1.0 μm and an AgI content of 2 mol% with an aspect ratio of 7) Silver amount 0.4 g / m ² Gapler C- 6 0.7 g / m ² Gelatin 1.2 g / m ² 18th layer: 1st protective layer UV absorption Adsorbents U-1 0.04g / m ² UV absorber U-3 0.03g / m ² UV absorber U-4 0.03g / m ² UV absorber U-5 0.05g / m ² UV absorber U-6 0.05 g / m ² compound Cpd C 0.8 g / m ² dye D-3 0.05g / m ² gelatin 0.7 g / m ² 19 layer: fine silver iodobromide emulsion fogged the second protective layer surface (the average particle size 0.06
mu, AgI content 1 mol%) silver 0.1 g / m ² Polymethyl methacrylate particles (average particle size 1.5μ) 0.1 g / m ² of methyl methacrylate and acrylic acid 4: a copolymer of 6 (average particle size 1.5 microns 0.1 g / m ² Cpd E 0.03 g / m ² Fluorine-containing surfactant W-13 mg / m ² W-2 5 mg / m ² Gelatin 2.1 g / m ² Each layer contains the above composition. In addition, a gelatin hardener H-1 and a surfactant were added.

 The compounds used to make the samples are shown below.

Oil 1 Dibutyl phthalate Oil 2 Tricresyl phosphate Cpd E C ₁₅ H ₃₁ COOC ₁₆ H ₃₃ Next, a sample 102 was prepared in the same manner as the sample 101, except that the (I-12) dye was replaced by an equimolar instead of the irradiation prevention dye D-1 in the twelfth layer.

Samples were also obtained except that silver halide emulsion A was used in place of silver halide emulsion B used in the fifth layer and coating was performed.
Sample 103 was produced in the same manner as 101.

Further, as shown in Table 3, samples 104 to 117 were prepared in order to compare the difference between the dye and the silver halide emulsion.

These samples 101 to 117 were prepared using a light source of 4800K,
Exposure was performed through a sensitometric wedge with red light or green light, respectively, at an exposure of 50 lux seconds. The exposed sample was subjected to the following development processing.

Processing Step Time Temperature First development 6 minutes 38 ° C Rinse 2 minutes 38 ° C Inversion 2 minutes 38 ° C. Color development 6 minutes 38 ° C Adjustment 2 minutes 38 ° C Bleaching 6 minutes 38 ° C Fixed 4 minutes 38 ℃ Water washing 4 minutes 38 ° C Stable 1 minute Room temperature Drying The composition of the treatment liquid is as follows.

First developer Water 700ml Natrilo-N, N, N-trimethylenesulfonic acid pentasodium salt 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (monohydrate) 30g 1-phenyl-4-methyl-4- Hydroxymethyl-3pyrazolidone 2g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0.1% solution) 2ml Add water 1000ml Reversal water 700ml Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3 g stannous chloride (dihydrate) 1 g p-aminophenol 0.1 g sodium hydroxide 8 g glacial acetic acid 15 ml Add water 1000 ml Color developing solution water 700 ml Nitrilo-N, N, N-trimethylene phosphonic acid pentasodium salt 3g Sodium sulfite 7g Trisodium phosphate (12-hydrate) 36g Potassium bromide 1g Potassium iodide (0.1% solution) 90ml Sodium hydroxide 3g Citrazinic acid 1. 5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 11 g 3,6-dithiaoctane-1,8-diol 1 g Add water 1000 ml Adjustment solution Water 700 ml Sodium sulfite 12g Sodium ethylenediaminetetraacetate (dihydrate) 8g Thioglycerin 0.4ml Glacial acetic acid 3ml Add water 1000ml Bleach solution Water 800ml Sodium ethylenediaminetetraacetate (dihydrate) 2g Iron (III) ammonium ethylenediaminetetraacetate (dihydrate) Water salt) 120g Potassium bromide 100g Add water 1000ml Fixer water 800ml Sodium thiosulfate 80.0g Sodium sulfite 5.0g Sodium bisulfite 5.0g Add water 1000ml Stabilized water 800ml Formalin (37% by weight) 5.0 ml Fuji Drywell (surfactant manufactured by Fuji Film Co., Ltd.) 5.0 ml Add 1000 ml of water to complete these treatments. By measuring the pointer concentration (D _M) and cyan density (D _C), it was determined each characteristic curve.

From the characteristic curve, constant density (D = 1.00 and D = 2.00)
The red and green color reproducibility was evaluated based on the difference in exposure (sensitivity) required to obtain magenta and cyan densities of
Table 4 and Table 5 show the results.

As can be seen from the results in Table 4, since the sensitivity of the red photosensitive layer to green light is reduced by about 0.1 or more in logE value according to the present invention, it is possible to significantly reduce red turbidity to green, It can be seen that the color reproducibility of is greatly improved.

As can be seen from the results in Table 5, the sensitivity of the green photosensitive layer to red light is reduced by about 0.5 or more in logE value according to the present invention, so that green turbidity to red can be significantly reduced. It can be seen that the color reproducibility of is greatly improved.

Example 2 Using the samples 101 to 177 prepared in Example 1, one of each sample was left at 75% relative humidity and 50 ° C. for 3 days.

The other is sensitometry with white light at a light exposure of 50 lux-second using a light source of 4800 ゜ K after leaving the sample for 3 days at a relative humidity of 20% and a temperature of 50 ° C. Exposure was performed through a wedge.

The exposed sample was developed in the same manner as in Example 1, and the sensitivity of the red photosensitive layer was adjusted to the maximum density ^*** (Dmax.
C) was measured. The obtained results are shown in the table as relative values.
6 is shown.

*** Decreasing the maximum density value of the red photosensitive layer indicates that fog has increased.

As can be seen from the results in Table 6, the present invention causes a small decrease in Dmax at high temperatures (50 ° C., 20% RH) and a small decrease in sensitivity even at high temperatures and high humidity (50 ° C., 70% RH). You can see that.

Example 3 On an undercoated cellulose triacetate film support, a multilayer color light-sensitive material comprising the following layers was prepared, and the second red-sensitive emulsion layer was coated with the emulsion B described in Example-1. The sample containing was 201.

First layer; anti-halation layer Black colloidal silver Silver 0.18 g / m ² Gelatin 1.40 g / m ² Second layer; Intermediate layer 2,5-di-t-pentadecylhydroquinone 0.18 g / m ² C-11 0.07 g / m ² C-13 0.02 g / m ² U-11 0.08 g / m ² U-12 0.08 g / m ² Oil-2 0.10 g / m ² Oil-1 0.02 g / m ² Gelatin 1.0 g / m ² Layer: First red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-11, 12, 13, and 18 Silver 0.50 g / m ² (iodine content 5 mol%, average particle sphere equivalent diameter 0.3 irregular multiple twinned particles μ) C-12 0.14 g / m 2 Oil-2 0.005g / m 2 C-20 0.005g / m 2 gelatin 1.20 g / m ² 4th layer: second red-sensitive emulsion layer up Silver iodobromide emulsion spectrally sensitized with dyes S-11, 12, 13 and 18 (Emulsion-B described in Example 1) Silver 1.15 g / m ² C-12 0.060 g / m ² C-13 in the third red-sensitive emulsion layer sensitizing dye ^{S-11,12,13,18; 0.008g / m 2} C-20 0.004g / m 2 Oil-2 0.005g / m 2 gelatin 1.50 g / m ² layer 5 Spectral sensitized iodobromination Silver emulsion Silver 1.50 g / m ² (irregular multiple twin grains having an iodine content of 8 mol% and an average particle sphere equivalent diameter of 0.8 μm) C-15 0.012 g / m ² C-13 0.003 g / m ² C-14 0.004 g / m ² Oil-2 0.32 g / m ² gelatin 1.63 g / m ² sixth layer; intermediate layer gelatin 1.06 g / m ² seventh layer; first green-sensitive emulsion layer Sensitizing dyes S-14, 15, 16 Silver iodobromide emulsion spectrally sensitized with (irregular multiple twin grains having an iodine content of 5 mol% and an average particle sphere equivalent diameter of 0.3 μm) silver 0.35 g / m ² C-16 0.120 g / m ² C-11 0.021 g / m ² C-17 0.030 g / m ² C-18 0.025 g / m ² Oil-2 0.20 g / m ² Gelatin 0.70 g / m ² 8th layer; 2nd green emulsion layer Sensitizing dye S- Silver iodobromide emulsion spectrally sensitized at 14, 15, and 16 (irregular multiple twin grains having an iodine content of 8 mol% and an average grain sphere equivalent diameter of 0.6 μm) Silver 0.75 g / m ² C-16 0.021 g / ^{m 2 C-18 0.004g / m} 2 C-11 0.002g / m 2 C-17 0.003g / m 2 Oil-2 0.15 g / m 2 gelatin 0.80 g / m ² ninth layer; third green-sensitive emulsion layer Sensitizing dye S-1 Silver iodobromide spectrally sensitized in 4, 15, and 16 1.80 g / m ² (irregular multiple twin grains having an iodine content of 12 mol% and an average equivalent diameter of 1.2 μm) C-16 0.011 g / m ² C-11 0.001 g / m ² Oil-1 0.69 g / m ² Gelatin 1.74 g / m ² 10th layer; yellow filter layer Yellow colloidal silver Silver 0.05 g / m ² 2,5-di-t-pentatedisyl Hydroquinone 0.03 g / m ² Gelatin 0.95 g / m ² 11th layer; 1st blue-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dye S-17 Silver 0.24 g / m ² (iodine content 7 mol %, amorphous multiple twin grains having an average particle equivalent sphere diameter 0.3μ) C-19 0.27 g / m 2 C-18 0.005g / m 2 Oil-2 0.28 g / m 2 gelatin 1.28 g / m ² 12th layer A second blue-sensitive emulsion layer: a silver iodobromide emulsion spectrally sensitized with a sensitizing dye S-17, silver: 0.45 g / m ² (irregular amorphous twin having an iodine content of 7 mol% and an average grain sphere equivalent diameter of 0.6 μm) ^{particles) C-19 0.098g / m 2} Oil-2 0.03 g / m 2 gelatin 0.46 g / m ² 13th layer; third blue-sensitive emulsion layer Iodobromide emulsion silver sensitive dye S-17 was spectrally sensitized 0.77 g / m ² (iodine content 12 mole%, the amorphous multi-twin grains having an average particle equivalent sphere diameter 0.8μ) C-19 0.036g / m ² Oil-2 0.07 g / m ² gelatin 0.69 g / m ² 14th layer; 1st protective layer Silver iodobromide (silver iodide 1 mol%, average grain size 0.07μ) Silver 0.5 g / m ² U- 11 0.11 g / m ² U-12 0.17 g / m ² Oil-2 0.90 g / m ² 15th layer; 2nd protective layer Polymethylmethacrylate particles (about 1.5 μm in diameter) 0.54 g / m ² U-13 0.15 g / m ² U-14 0.10 g / m ² F-1 0.10 g / m ² F-2 0.02 g / m ² F-3 0.02 g / m ² Gelatin 0.72 g / m ² Gelatin hardener H-1 and a surfactant were added.

 The compounds used to make the samples are shown below.

Oil-1 Dibutyl phthalate Oil-2 Tricresyl phosphate Sample 202 was prepared in the same manner as for sample 201, except that the dye (I-1) was replaced with an equimolar amount instead of the irradiation prevention dye F-1 of the 15th layer.

Sample 101 was also used except that silver halide A was used instead of silver halide emulsion B used in the fourth layer.
A sample 103 was prepared in the same manner as described above.

Further, according to Table 7, samples 204 to 214 were prepared to compare the difference between the dye and the silver halide emulsion.

These samples 201 to 214 were exposed to red light or green light, respectively, through a sensibility wedge using a light source of 4800 ° K at an exposure amount of 25 lux · sec.

The exposed sample was developed at 38 ° C. according to the following processing steps.

Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 2 minutes 10 seconds Fixed 4 minutes 20 seconds Rinse 3 minutes 15 seconds Stable 1 minute 05 seconds The processing solutions used in each process are as follows. Was.

Color developer diethylenetriaminepentaacetic acid 1.0 g 1-hydroxyethylidene-1, -1-diphosphonic acid 2.0 g sodium sulfite 4.0 g potassium carbonate 30.0 g potassium bromide 1.4 g potassium iodide 1.3 mg hydroxylamine sulfate 2.4 g 4- (N -Ethyl-N-β-hydroxyethylamino)
-2-Methylaniline sulfate 4.5 g Add water 1.0 pH 10.0 Bleaching solution Ferric ammonium ethylenediaminetetraacetate 100.0 g Disodium ethylenediaminetetraacetate 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Add water 1.0 pH 6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 175.0 ml Sodium bisulfite 4.6 g Add water 1.0 pH 6.6 Stabilizer Formalin (40%) 2.0 ml Polyoxyethylene p-Monononylphenyl ether (average degree of polymerization 10) 0.3 g 1.0 after adding water After completing these treatments, measure the cyan concentration (D _C ) and magenta concentration (D _M ) obtained on the sample. Thus, each characteristic curve was obtained.

From the characteristic curves, the color reproducibility of red and green was evaluated based on the difference in exposure amount (sensitivity) required to obtain a constant density (Dmin + 0.2) of cyan and magenta densities. Table 8 shows the results. Was.

As can be seen from the results in Table 8, it can be seen that the color reproducibility of green and red is greatly improved by the present invention.

Example 4 Samples 201 to 214 prepared in Example 3 were used. One of each sample was left at 75% relative humidity and 50 ° C. for 3 days, and the other was set at 20% relative humidity. % And a temperature of 50 ° C. for 3 days, each sample was exposed through a sensitometric wedge with white light at an exposure of 25 lux · sec using a light source of 4800 ° K.

The exposed sample was developed in the same manner as in Example 3, and the sensitivity and the fog density (Dmin) of the red photosensitive layer were measured. Table 9 shows the obtained results as relative values.

As can be seen from the results shown in Table 9, the present invention has a small increase in fog even under high temperature and high humidity, and a small decrease in sensitivity.

(Effect of the Invention) According to the present invention, a silver halide color photographic light-sensitive material having excellent color reproducibility and little change in photographic characteristics even when stored under high temperature and high humidity can be obtained, and the practical merits are great. .

Claims (1)

(57) [Claims] 1. A photographic light-sensitive material comprising at least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer on a support. The latent image distribution in the depth direction from the grain surface of the silver halide emulsion contained in at least one of the layers has at least one maximum value, and the location of the maximum value is 0.01 μm from the grain surface. And the particles are chemically sensitized so as to have a latent image number of not less than one-fifth and less than one time of the maximum value on the particle surface, and the photographic material is further represented by the following general formula (I): A silver halide color photographic light-sensitive material containing at least one of the compounds shown below. General formula (I) Wherein R _1, R ₂ represents an alkyl group or an aryl group, R _3,
R ₄ represents an alkyl group or an aralkyl group having at least one carboxyl group or sulfo group, respectively. n represents 0, 1 or 2.