JPS62136640A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve a shelf life under high-temp. conditions by sandwiching a nonphotosensitive filter layer contg. yellow colloid silver and nonphotosensitive fine-grain silver halide with nonphotosensitive layers from above and below. CONSTITUTION:This photosensitive material has respectively >=1 layers of red-sensitive silver halide emulsion layers, green-sensitive silver halide emulsion layers, and blue-sensitive silver halide emulsion layers. The silver halide color photographic sensitive provided with the blue-sensitive emulsion layers on the side further from the base than the other photosensitive layers has the nonphotosensitive filter layer contg. the yellow colloid silver and non photosensitive fine-grain silver halide between the blue-sensitive silver halide emulsion layer and the other photosensitive silver halide emulsion layer. Said photosensitive material is so constituted as to have the nonphotosensitive layer between the nonphotosensitive filter layer and the photosensitive layers to sand wich said nonphotosensitive filter layer. The stability under the severe preserva tion conditions such as high temp. and high humidity or high temp. and low humidity is remarkably improved by the above-mentioned constitution.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color having improved stability over time under high temperature and high temperature and low temperature conditions. It relates to photographic materials.

[Conventional technology]

In recent years, the screen size of photosensitive materials has become smaller due to advances in camera manufacturing technology, and as a result, the magnification of printed photosensitive materials is increasing. For this reason, there has been a demand for photosensitive materials with higher image quality (graininess and sharpness).

On the other hand, from the perspective of stabilizing the quality of photosensitive materials, there are various conditions (for example, high temperature and high humidity).

There is a need for stable photosensitive materials that exhibit little change in properties even when stored for long periods in dry conditions (low humidity).

The latter technique for stabilizing the quality of photosensitive materials during storage over time includes the use of tetrazaindene compounds, mercapto compounds, quaternary ammonium salts, polyhydroxybenzene compounds, gallic acid ester compounds, thione compounds, or inorganic salts in photosensitive materials. It is well known to add substances such as these, and these are generally referred to as "fogging inhibitors". However, in recent photosensitive materials that are highly sensitive and suitable for rapid processing at high temperatures, these fog suppressants have not yet achieved fully satisfactory properties in terms of stabilizing quality.

In the course of research on stabilizing the quality of such photosensitive materials, the present inventors found that the presence of a yellow filter layer containing colloidal silver, which is commonly used in color photosensitive materials, can reduce fogging under high temperature and high humidity. It was found that this was caused by an increase in the sensitivity and an accompanying decrease in sensitivity.

Usually, a color light-sensitive material is composed of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer. Generally, a yellow filter layer containing colloidal silver is provided to cut out unnecessary blue light.

In such light-sensitive materials, due to the adjacency with the yellow filter layer containing colloidal silver, fog may occur in unexposed light under high temperature and/or high temperature conditions, so-called "contact fog", or when a sensitizing dye is used. It has an adverse effect on green- and red-sensitive silver halides that have been spectrally sensitized.
In recent years, it has been found that this method significantly reduces the spectral sensitization rate.

As a method to solve the problem of the yellow filter layer containing colloidal silver, Japanese Patent Application Laid-open Nos. 58-95728 and 59-74557 disclose a method in which a 1-phenyl-5-mercaptotetrazole derivative is added to the yellow filter layer. Although a method for preventing contact fog by adding a nitride has been disclosed, it is insufficient in terms of the fog suppressing effect.

In addition, a method using yellow filter dye instead of yellow colloidal silver is disclosed in Japanese Patent Publications Nos. 57-51658 and 58-849.
No. 9 or European Patent Application No. 29412, however, compared to colloidal silver, it has insufficient absorption characteristics for blue light, and it is also inferior to colloidal silver in terms of coating properties and decolorization properties during the development process. However, it has many problems and has not yet been put into practical use.

On the other hand, the applicant has previously proposed an attempt to improve the stability under high temperature conditions by adding fine grain silver halide to the yellow filter layer (Japanese Patent Application No. 59-200982). issue). However, this technique alone tends to reduce stability under high temperature, low humidity conditions, and does not necessarily improve stability under all conditions.

[Purpose of the invention]

The purpose of the present invention is to solve the problems of the above-mentioned prior art,
The object of the present invention is to provide a silver halide color photographic light-sensitive material that has significantly improved stability under storage conditions, whether under high temperature and high humidity or high temperature and low humidity.

[Structure and operation of the invention]

The present invention has one or more red-sensitive silver halide emulsion layers, one or more green-sensitive silver halide emulsion layers, and one or more blue-sensitive silver halide emulsion layers on a support, and the blue-sensitive emulsion layer forms another light-sensitive layer. In a silver halide color photographic light-sensitive material provided on a side farther from the support than the blue-sensitive silver halide emulsion layer and another light-sensitive silver halide emulsion layer, yellow colloidal silver and a non-light-sensitive silver halide emulsion layer are provided. The above objective can be achieved by having a structure having a non-photosensitive filter layer containing fine grain silver halide, and having a non-photosensitive layer between the non-photosensitive filter layer and a photosensitive layer sandwiching the non-photosensitive filter layer. achieve.

According to the structure of the present invention, the non-photosensitive filter layer contains yellow colloidal silver and non-photosensitive fine grain silver halide, and has a structure in which the top and bottom of the non-photosensitive filter layer are sandwiched between the non-photosensitive layers. By adopting this structure, storage properties under both high and low temperature conditions and high and low temperature conditions are improved, and both storage characteristics are satisfied at the same time.

The silver halide color photographic light-sensitive material of the present invention can employ various layer configurations. For example, the structure may include, in order from the support side, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a non-light-sensitive filter layer sandwiched between non-light-sensitive layers, and a blue-sensitive silver halide emulsion layer. I can do it. The order of the red-sensitive and green-sensitive emulsion layers is arbitrary. Each color-sensitive silver halide emulsion layer may be one layer or 2N or more (for example, two or more layers with different sensitivities).

Further, if necessary, an appropriate intermediate layer or the like may be formed between the respective constituent layers.

The non-photosensitive filter layer of the present invention may be one layer or two or more layers. In addition, the non-photosensitive layer between the non-photosensitive filter layer and the photosensitive layer sandwiching it, that is, the non-photosensitive layer sandwiching the non-photosensitive filter layer, may be one layer each, or one or both may be two layers. It may be more than that.

The dry film thickness of the non-photosensitive layer sandwiching the non-photosensitive filter layer is:
It is preferable that it is 0.1-5 micrometers. If the film thickness is larger than this, the sharpness tends to deteriorate, and if it is smaller than this, there may be problems with coating properties during film formation, or the effect of the structure sandwiching the non-photosensitive filter layer may be insufficient. may not be fully demonstrated. More preferably, this film thickness is 0.3 to 2 μm.

Together with the filter layer and the non-photosensitive layers above and below it,
The film thickness is preferably 8 μm or less, more preferably 5 μm or less, particularly preferably 4 μm or less.

The filter layer of the present invention contains yellow colloidal silver and non-photosensitive fine grain silver halide, and the yellow colloidal silver in this case can be obtained by various methods. For example, it is made by reducing silver salts with phenols such as hydroquinone or pyrogallol, or alternatively with tannins.

Specifically, reducing agents include hydroquinone, pyrogallol, pyrocatechin, p-phenylenediamine, phenols such as 1,4-dihydronaphthalene, and 1-phenyl-3
-pyrazolidone, 1-(p-aminophenol)-3-
Examples include 5-membered ring compounds such as amino-2-pyrazolidone. Many examples of these reducing agents are described in "The Theory of the Photographic Process," 3rd edition, by C-E-Mies, T-H James, pages 278-3o6. Also, dextrin as a reducing agent,
Examples include reducing tin such as glucose, compounds such as ferrous oxalate, sodium hydrosulfite, hydroxylamine, and hydrazine, and inorganic compounds such as polyvalent ion metal salts such as titanium, vanadium, and tin.

The raw material and silver salt to be reduced are water-soluble radical salts such as silver nitrate and silver ammonium complex salts, or fine particles of silver salts such as silver chloride, silver bromide, silver iodide, silver chlorobromide, and silver halides. There are also dispersions.

The above-mentioned fine grain silver halide can also be used as a material contained in a non-photosensitive layer between the filter layer and the blue-sensitive layer.

In the present invention, the AS agent, particularly the Dp scavenger, may not be used, but is preferably contained in one or both of the non-photosensitive layers sandwiching the filter layer. When used in one layer, it is contained in a non-photosensitive layer close to the support. Preferably, it is contained in both non-photosensitive layers.

In this specification, Dp' scavenger refers to a scavenger of the oxidized product of a color developing agent, but when the Dp' scavenger is contained in the non-photosensitive layer of the present invention, this non-photosensitive layer is added to the filter layer. It is preferably directly adjacent, and more preferably also adjacent to the blue-sensitive silver halide emulsion layer.

When Dp' scavenger is included, the amount added is I x 10-6 to I x 10-' mol/rd
is preferable, and 5 X 10-' to 5 X 10-'mo
l/rd is more preferred.

Dp' scavengers that can be used include the following.

Any material that effectively scavenges the oxidized product of the color developing agent may be used, but examples include polyhydroxybenzene compounds or their precursors, and materials that do not form colored dyes after scavenging, such as commonly used photographic couplers, preferable.

Particularly preferred are alkylhydroquinone derivatives represented by the following general formula (I) and pyrogallol derivatives represented by (n).

H In the formula, R1 and R2 each represent a hydrogen atom or an alkyl group.

R3 In the formula, R3 represents an alkoxycarbonyl group, an N-substituted carbamoyl group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, a cyano group, or a halogen atom.

Among these, an alkoxycarbonyl group is more preferred.

In the general formula (I), the alkyl group represented by R1 and R1 can be a straight chain or branched alkyl group, preferably an alkyl group having 4 to 30 carbon atoms. This alkyl group can have a substituent, and examples of the substituent include an alkoxy group, an alkyloxy group, a hydroxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom, a carboxy group, a sulfo group,
cyano group, alkyl group, alkenyl group, aryol group, amino group, carbamoyl group, acyl group, alkylsulfonyl group, arylsulfonyl group, and acyloxy group,
Examples include acylamino groups.

Moreover, R1 and R2 may be the same or different from each other.

In the alkoxycarbonyl group represented by R3 in the general formula (n), for example, the number of carbon atoms in the alkyl portion is 3 to 3.
Specific examples include propoxycarbonyl group, octyloxycarbonyl group, dodecylcarbonyl group, and octadecylcarbonyl group.

Examples of the N-substituted carbamoyl group represented by R5 include N-butylcarbamoyl group, N-dodecylcarbamoyl group, N-octadecyl-N-methylcarbamoyl group, and N-phenylcarbamoyl group.

Specific examples of the acyl group represented by R3 include an acetyl group, a stearoyl group, a morpholyl group, a benzoyl group, a chloroacetyl group, a piperidinoyl group, and further examples of the alkylsulfonyl group 5C-75C-8 SC-95C-10 SC-115C-12 SC-135C-14 SC-153C-16 To introduce the Dp' scavenger into the desired layer,
Various methods may be used, such as those described in US Pat. No. 2,322,027. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl citric acid) tributyl), benzoic acid esters (e.g. octyl benzoate),
High boiling organic solvents such as alkylamides (e.g. diethyl laurylamide) or boiling points from about 30°C to 150°C
low-boiling organic solvents such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, 2
After dissolving in butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

When the Dp' scavenger has an acid group such as carboxylic acid or sulfonic acid, it is added to an alkaline aqueous solution and then introduced into the hydrophilic colloid.

In the present invention, as the silver halide in the emulsion layer, any silver halide used in ordinary silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride can be used. can be used.

The silver halide grains used may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape.

In these particles, any ratio of the (100) plane to the (111) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

In the practice of this invention, the striped silver halide emulsions used can be chemically sensitized by various methods.

That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal compound using gold or other noble metal compounds, etc. can be used alone or in combination.

For example, British Patent No. 618,061, British Patent No. 1,315.7
No. 5'5, No. 1,396.696, Special Publication No. 1973-15
No. 748, U.S. Patent No. 1.574.944, U.S. Patent No. 1,6
No. 23.499, No. 1,673.522, No. 2.27
No. 8,947, No. 2,399.083, No. 2,410
．． No. 689, No. 2.419.974, No. 2,448,
No. 060, No. 2,487,850, No. 2,518.6
No. 98, No. 2,521.926, No. 2,642.36
No. 1, No. 2.694.637, No. 2.728.668
No. 2.739.060, No. 2,743.182, No. 2.743.183, No. 2.983.609,
No. 2,983,610, No. 3,021,215, No. 3,026,203, No. 3.297.446, No. 3
．． 297.447, 3,361.564, 3,
No. 411,914, No. 3, No. 554, No. 757, No. 3
, No. 565,631, No. 3,565.633, No. 3,
59L385, 3,656,955, 3,76
L267 No. 3,772,031, No. 3,857,
No. 711, No. 3,891,446, No. 3,90171
No. 4, No. 3,904,415, No. 3.930.867
No. 3.984.249, No. 4,054,457, No. 4,067.740, Research Disclosure 1
No. 2008, No. 13452, No. 13654, T, H
, James, “The Theory of the Photographic Process”
Theory of the Photography
cProcess, ) (4th t!d, Macm
It is preferable to sensitize using a chemical aggravating agent or sensitization method described in, eg, "Illan, 1977)", pp. 67-76.

Furthermore, it is possible to optically sensitize to a desired wavelength range using a dye known as an exacerbating dye. The sensitizing dyes may be used alone or in combination of two or more. Along with aggravating dyes, dyes that do not themselves have spectral sensitizing effects,
Or a compound that does not substantially absorb visible light,
A supersensitizer that enhances the sensitizing effect of the sensitizing dye may be included in the emulsion.

Exacerbating pigments include cyanine pigment, merocyanine pigment,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment. 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, and a nucleus 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, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus,
These include naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, and quinoline nucleus. 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.

Useful sensitizing dyes used in blue-sensitive silver halide emulsion layers include, for example, West German Patent No. 929.080, US Pat. No. 2,231,658, and US Pat.
, No. 2,503.776, No. 2,519,001,
No. 2,912,329, No. 3,656,959, No. 3,672,897, No. 3,694,217, No. 4
, 025,349, 4,046,572, British Patent No. 1,242,588, Japanese Patent Publication No. 44-14030, Japanese Patent Publication No. 52-24844, and the like. In addition, useful enhancing dyes used in green-sensitive silver halide emulsions include, for example, U.S. Pat.
9.201, 2,072,908, 2,739
．． No. 149, No. 2,945°763, British Patent No. 50
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 5.979. Furthermore, useful enhancing dyes for use in red-sensitive silver halide emulsions include, for example, U.S. Pat.
No. 78, No. 2,442゜710, No. 2,454,62
Typical examples include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 9, No. 2,776.280, and the like. Furthermore, U.S. Pat. Nos. 2,213,995 and 2,493.
No. 748, No. 2,519.001, West German Patent No. 929
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in , No. 080, etc. can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone or in combination. Combinations of enhancing dyes are often used, especially for the purpose of supersensitization. Typical examples are Special Publications No. 43-4932, No. 43-4933, No. 4
No. 3-4936, No. 44-32753, No. 45-25
No. 831, No. 45-26474, No. 46-11627
No. 46-18107, No. 47-8741, No. 4
No. 7-11114, No. 47-25379, No. 47-3
No. 7443, No. 4B-28293, No. 48-384
No. 06, No. 48-38407, No. 48-38408, No. 4B-41203, No. 4B-41204,
No. 49-6207, No. 50-40662, No. 53-
No. 12375, No. 54-34535, No. 55-156
No. 9, JP-A No. 50-33220, JP-A No. 50-33828
No. 50-38526, No. 51-107127,
No. 51-115820, No. 51-135528, No. 51-151527, No. 52-23931, No. 52
-51932, 52-104916, 52-1
No. 04917, No. 52-109925, No. 52-11
No. 0618, No. 54-80118, No. 56-2572
No. 8, No. 57-1483, No. 58-10753, No. 58-91445, No. 58-153926, No. 59
-114533, 59-116645, 59-
116647, U.S. Patent No. 2.688.545, U.S. Patent No. 2,977.229, U.S. Patent No. 3,397.060, U.S. Pat.
, No. 506.443, No. 3.578゜447, No. 3,
No. 672,898, No. 3,679,428, No. 3゜7
69.301, 3,814.609, 3,83
No. 7,862.

In carrying out the present invention, the present invention may be carried out during chemical ripening, at the end of chemical ripening, and/or for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of photosensitive materials, or to maintain stable photographic performance. After completion of ripening and before coating the silver halide emulsion, compounds known in the photographic industry as antifoggants or stabilizers can be added.

As an antifoggant and a stabilizer, U.S. Patent No. 2.713
, No. 541, No. 2,743.180, No. 2.743.
Pentazaindenes described in U.S. Pat. No. 181, U.S. Pat. No. 2.716.062, U.S. Pat.
, No. 444,605, No. 2,756,147, No. 2,
No. 835.581, No. 2,852.375, Research Disclosure (Research Disclosure)
azaindenes such as tetrazaindenes described in U.S. Pat. No. 14851, triazaindenes described in U.S. Pat. Class; U.S. Patent Nos. 2.131.038 and 3,342.
596, quaternary salts such as thiazolium salts described in U.S. Pat. No. 3,954,478, pyrylium salts described in U.S. Pat. Onium salts: U.S. Patent Nos. 2.403.927, 3,266.897, 3.708.303, JP-A-55-135835
Mercaptotetrazoles, mercaptotriazoles, and mercaptodiazoles described in U.S. Pat. No. 59-71047, mercaptothiazoles described in U.S. Pat. No. 2.824,001, and U.S. Pat.
Mercaptobenzthiazoles and mercaptobenzimidazoles described in US Patent No. 2.843.
Mercaptooxadiazoles described in No. 491,
Mercapto-substituted heterocyclic compounds such as mercaptothiadiazoles described in U.S. Pat. No. 3,364.028; U.S. Pat. No. 3,236.652, Japanese Patent Publication No. 43-1
Catechols described in No. 0256, Special Publication No. 56-4
Resorcinols described in No. 4413 and Japanese Patent Publication No. 43
-4133; polyhydroxybenzenes such as gallic acid ester; tetrazoles described in West German Patent No. 1,189.380; US Patent No. 3,157;
509, the triazoles described in U.S. Pat.
Benztriazoles described in No. 704.721;
The urazoles described in U.S. Pat. No. 3,287,135, the pyrazoles described in U.S. Pat. No. 3,106,467, the indazoles described in U.S. Pat. No. 2,271,229, and the Azoles such as polymerized benztriazoles described in Japanese Patent Publication No. 59-90844, pyrimidines described in U.S. Pat. No. 3,161,515, and 3 described in U.S. Pat. -pyrazolidones, and U.S. Pat. No. 3,021,
Heterocyclic compounds such as polymerized pyrrolidones, that is, polyvinylpyrrolidones, described in No. 213;
No. 130929, No. 59-137945, No. 1404
45, British Patent No. 1.356.142, U.S. Pat. No. 3,575,699, U.S. Pat. No. 3,649.267, etc.;
Sulfinic acid and sulfonic acid derivatives described in US Pat. No. 47,393; US Pat. No. 2.566.263, US Pat.
39.405, 2.488.709, 2.72
Examples include inorganic salts described in No. 8,663.

The color photographic window optical material of the present invention usually has dye image-forming constituent units that are sensitive to each of the three primary color regions of the spectrum, and each constituent unit is a single layer emulsion that is sensitive to a certain region of the spectrum. layer or multiple emulsion layers (in this case,
It is preferable that the respective emulsion layers have different sensitivities.

A typical multicolor color photographic material comprises a cyan dye image-forming unit consisting of at least one red-sensitive silver halide emulsion layer having at least one cyan dye-forming coupler;
A magenta dye image forming unit consisting of at least one green-sensitive silver halide emulsion layer having at least one magenta dye-forming coupler, and at least one blue-sensitive silver halide emulsion layer having at least one yellow dye-forming coupler. It consists of a yellow dye image-forming structural unit coated on a support together with a non-photosensitive layer. In the practice of this invention, yellow dye-forming couplers include:
Various acylacetanilide couplers can be preferably used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow couplers that can be used include British Patent No.
．． 077゜874, JP 45-40757, JP 47-1031, JP 47-26133, JP 4B
-94432, 50-87650, 51-36
No. 31, No. 52-115219, No. 54-99433
No. 54-133329, No. 56-30127,
U.S. Patent No. 2,875.057, U.S. Patent No. 3,253.92
No. 4, No. 3,265,506, No. 3.408.194
No. 3,551.155, No. 3,551,156, No. 3,664.841, No. 3,725,072,
3,730°722, 3,891,445, 3,900,483, 3,929.484, 3
, No. 933.500, No. 3,973.968, No. 3990.896, No. 4,012.259, No. 4,0
No. 22.620, No. 4.029,508, No. 4.05
No. 7.432, No. 4,106,942, No. 4,133
．． No. 95B, No. 4,269.936, No. 4, 286
, No. 053, No. 4,304.845, No. 4,314
．． No. 023, No. 4,336.327, No. 4,356.
No. 258, No. 4,386.155, No. 4,401,7
This is described in No. 52, etc.

As the magenta dye-forming coupler, 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazoloazole couplers such as pyrazolotriazole couplers, and open-chain acylacetonitrile couplers can be preferably used. Specific examples of magenta couplers that can be advantageously used are disclosed in Japanese Patent Application Nos. 58-164882 and 58-164882;
No. 8-167326, No. 58-206321, No. 58
-214863, 5B -217339, 59
-24653, Special Publication No. 40-6031, No. 40-6
No. 035, No. 45-40757, No. 47-27411
No. 49-37854, JP-A-50-13041, JP-A No. 51-26541, JP-A No. 51-37646, JP-A No. 5
No. 1-105820, No. 52-42121, No. 53-
No. 123129, No. 53-125835, No. 53-1
No. 29035, No. 54-48540, No. 56-292
No. 36, No. 56-75648, No. 57-17950, No. 57-35858, No. 57-146251, No. 59-99437, British Patent No. 1.252,418, U.S. Patent No. 2.600, No. 788, 3.005.7
No. 12, No. 3,062, No. 653, No. 3.127.26
No. 9, No. 3,214.437, No. 3.253,924
No. 3,311,476, No. 3,419,391, No. 3,519,429, No. 3,558.319,
3.582,322, 3,615,506, 3.658.544, 3,705,896, 3
, No. 725,067, No. 3,758.309, No. 3,
No. 823.156, No. 3,834,908, No. 3,8
No. 91,445, No. 3.907.571, No. 3,92
No. 6.631, No. 3,928,044, No. 3,935
．． No. 015, No. 3,960,571, No. 4.076,
No. 533, No. 4,133.686, No. 4,237,2
No. 17, No. 4,241.168, No. 4,264.72
No. 3, No. 4,301,235, No. 4,310,623
This is what is written in the number etc.

As the cyan dye-forming coupler, naphthol couplers and phenol couplers can be preferably used. Specific examples of cyan couplers that can be advantageously used include British Patent Nos. 1.038.331 and 1,543,040; -146828, same 5
No. 3-105226, No. 54-115230, No. 56
-29235, 56-104333, 56-1
No. 26833, No. 57-133650, No. 57-15
No. 5538, No. 57-204545, No. 58-118
No. 643, No. 59-31953, No. 59-31954
No. 59-59656, No. 59-124341,
No. 59-166956, U.S. Patent No. 2.369.92
No. 9, No. 2,423.730, No. 2,434,272
No. 2.474.293, No. 2,698,794, No. 2,772.162, No. 2,801,171,
2,895.826, 3,253,924, 3,311,476, 3,458.315, 3
, 476.563, 3,591.383, 3,
737.316, 3,758,308, 3,7
．． No. 67.411, No. 3,790.384, No. 3,8
No. 80.661, No. 3,926,634, No. 4,00
No. 4,929, No. 4, 009, No. 035, No. 4,0
No. 12,258, No. 4,052,212, No. 4,12
No. 4.396, No. 4,134,766, No. 4,138
, No. 258, No. 4,146,396, No. 4,149,
No. 886, No. 4,178,183, No. 4,205,9
No. 90, No. 4,254,212, No. 4,264.72
No. 2, No. 4,288,532, No. 4,296,199
No. 4,296,200, No. 4,299.914, No. 4,333,999, No. 4,334,011,
These are described in 4,386.155, 4,401,752, 4,427,767, etc.

In addition, in order to improve photographic characteristics, so-called competing
It can also contain couplers that form colorless dyes called couplers.

In addition to the coupler, the silver halide emulsion layer may contain a so-called DIR substance that releases a development inhibitor or its precursor, such as a diffusive DIR substance or a timing DIR substance.

In addition, when carrying out the present invention, hydrophobic Various methods can be used for the compound, such as a solid dispersion method, a latex dispersion method, and an oil-in-water emulsion dispersion method, which can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. The oil-in-water type emulsification dispersion method can be applied using conventionally known methods for dispersing hydrophobic additives such as couplers. Usually, a high boiling point organic solvent with a boiling point of about 150°C or higher is mixed with a low boiling point and/or water soluble one as necessary. Emulsification and dispersion are carried out using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, and ultrasonic device using a surfactant in a hydrophilic binder such as an aqueous gelatin solution. After that, it may be added to the desired hydrophilic colloid layer.

A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

The ratio of high boiling point organic solvent to low boiling point organic solvent is i:o to 1:50. More preferably, the ratio is 1:1 to 1:20.

High boiling point oils include organic compounds with a boiling point of 150°C or higher, such as phenol derivatives, phthalate alkyl esters, phosphate esters, citric acid esters, benzoate esters, alkylamides, fatty acid esters, and trimesic acid esters, which do not react with the oxidized form of the developing agent. A solvent is used.

Examples of high-boiling organic solvents that can be used include U.S. Pat. No. 2,322,027, U.S. Pat.
, 353.262, 2, 852.383, 3,
No. 554,755, No. 3,676, No. 137, No. 3,6
76.142, 3,700.454, 3,74
8.141, 3,779,765, 3,837
．． No. 863, British Patent No. 958.441, 1,22
No. 2,753, OL S2.538,889, JP-A-47-1031, JP-A No. 49-90523, JP-A No. 50-2
No. 3823, No. 51-26037, No. 51-2792
No. 1, No. 51-27922, No. 51-26035,
No. 51-26036, No. 50-62632, No. 53
-1520, 53-1521, 53-1512
No. 7, No. 54-119921, No. 54-119922
No. 55-25057, No. 55-36869, No. 56-19049, No. 56-81836, Special Publication No. 4
No. 8-29060, etc.

Examples of low-boiling or water-soluble organic solvents that can be used in conjunction with or in place of high-boiling solvents include those described in U.S. Pat. Examples of organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, and benzene, and examples of water-soluble organic solvents include acetone. , methyl isobutyl ketone, β-ethoxyethyl acetate, methoxy glycol acetate, methanol, ethanol, acetonitrile, dioxane, dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, diethylene glycol monophenyl ether, phenoxyethanol, etc. It will be done.

Surfactants can be used as dispersion aids, such as alkylbenzene sulfonates, alkylbenzene sulfonates, alkyl sulfonates, alkyl sulfates, alkyl phosphates, sulfosuccinates, and sulfoalkyl polyoxy Anionic surfactants such as ethylene alkylphenyl ether, steroidal saponins, nonionic surfactants such as alkylene oxide derivatives and glycidol derivatives, amino acids, aminoalkylsulfonic acids, alkyl betaines, etc. It is preferred to use amphoteric surfactants such as cationic surfactants such as quaternary ammonium salts, and cationic surfactants such as quaternary ammonium salts. Specific examples of these surfactants can be found in "Surfactant Handbook" (Sangyo Tosho, 1966)
and "Emulsifier, Emulsifier Research, Technical Data Collection" (Science Panronsha, 1978).

The hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention contain ultraviolet absorbers to prevent capri due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. May contain.

As the ultraviolet absorber, benzophenone compounds (for example, JP-A-46-2784, U.S. Pat. No. 3,215,53) are used.
No. 0, No. 3,698.907), butadiene compounds (e.g., those described in U.S. Pat. No. 4,045,229), 4-thiazolidone compounds (e.g., those described in U.S. Pat. No. 3,314. No. 794, 3.352.681
benzotriazole compounds substituted with aryl groups (e.g., Japanese Patent Publication No. 36-10466, Japanese Patent Publication No. 41-1687, Japanese Patent Publication No. 42-26187, Japanese Patent Publication No. 44-2)
No. 9620, No. 48-41572, JP-A-54-95
No. 233, No. 57-142975, U.S. Patent No. 3.2
No. 53,921, No. 3,533,794, No. 3,75
No. 4.919, No. 3,794.493, No. 4,009
, No. 038, No. 4,220,711, No. 4,323.
No. 633, Research Disclosure
Arch Disclosure) No. 22519), benzoxidol compounds (e.g., those described in U.S. Pat. No. 3.700.455), cinnamate ester compounds (e.g., U.S. Pat. No. 3.705.805).
No. 3,707,375, JP-A-52-49029
) can be used.

Furthermore, U.S. Pat.
Those described in No. 48535 can also be used. Ultraviolet absorbing couplers (for example, α-naphthol cyan dye-forming couplers), ultraviolet absorbing polymers (for example, JP-A-58-111942, JP-A-178351, JP-A-181041, JP-A-59-19945, 233
．． 44 Evening Gazette (-) etc. can be used. These ultraviolet absorbers may be mordanted in specific layers.

In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material of the present invention.

As a formalin scavenger, for example,
-87028, 57-133450, 58-1
No. 50950, U.S. Patent No. 2.895.827, No. 3
, No. 652.278, No. 3,811,891, No. 4,
No. 003.748, No. 4,411,987, No. 4,4
14.309, 4,418.142, 4,46
4゜463, US Defense Patent No. 900.02f3, West German Patent No. 3,223.699, US Defense Patent No. 3.227.961
No. 3,227.962, Research Disclosure (Research Disc-1osure)
) Those described in No. 10133 etc. can be preferably used.

An antistatic agent for the purpose of preventing static electricity can be added to the photosensitive material of the present invention. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated. It may be used in layers.

Antistatic agents include British Patent No. 1,446,600 and Research Disclosure.
Disc-1osure) No. 15840, No. 1625
No. 8, No. 16630, U.S. Patent No. 2.327,828
No. 2,861.056, No. 3,206゜312, No. 3,245,833, No. 3,428.451,
3,775, 126, 3,963,498, 4.025.342, 4.025,463, 4
, No. 025.691, No. 4,025,704, etc. can be preferably used.

Examples of the support used in the photosensitive material of the present invention include baryta, polyethylene-coated paper, polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate, polyvinyl acecool, polypropylene,
For example, there are polyester films such as polyethylene terephthalate, polystyrene, etc., and these supports are appropriately selected depending on the intended use of the silver halide photographic material.

These supports are subjected to undercoating processing as necessary.

The color developing solution used for processing the light-sensitive material of the present invention contains a developing agent and has a pH of 8 or more, preferably a pH of 9 to 12.
It is an alkaline aqueous solution of This aromatic primary amine developing agent as a developing agent is a compound having a primary amine group on an aromatic ring and capable of developing exposed silver halogenide, or a compound forming such a compound. means a precursor to

The above-mentioned developing agent is typically p-phenylenediamine type, and the following are preferred examples.

4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N, N-diethylaniline, 4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methoxyethyl-4-amino-N, N-diethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3- Methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-N, N-diethylaniline, 4-
Amino-N, N-dimethylaniline, N-ethyl-N-
β-[β-(β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl-N-
β-(β-methoxyethoxy)ethyl-3-methyl-4
-aminoaniline and their salts such as sulfate, hydrochloride, sulfite, p-)luenesulfonate, etc. Moreover, various additives can be added to these color developing solutions as necessary.

The light-sensitive material of the present invention can be subjected to imagewise exposure, color development treatment, and then bleaching treatment by a conventional method.

This treatment may be done simultaneously with fixing or separately. This processing solution can also be used as a bleach-fixing bath by adding a fixing agent if necessary. Various compounds can be used as bleaching agents, and various additives including bleaching accelerators can also be added.

The present invention is realized in various forms of color photosensitive materials. One method is to process a light-sensitive material having an emulsion layer containing a diffusion-resistant coupler on a support with an alkaline developer containing an aromatic primary amine color developing agent to form an emulsion of a water-insoluble or diffusion-resistant dye. It is to leave it in the layer. the other one
In one form, a light-sensitive material having an emulsion layer containing silver halide in combination with a diffusion-resistant coupler on a support is processed with an alkaline developer containing an aromatic primary amine color developing agent to form an aqueous medium. A soluble and diffusible dye is produced and transferred to an image-receiving layer consisting of another hydrophilic colloid.

That is, it is a diffusion transfer color type.

The present invention can be applied to all kinds of color photosensitive materials such as color negative films, color positive films, color reversal films, and color papers.

〔Example〕

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

The following samples (1) to (12) were produced. In addition, sample (1
) (2) and (9) to (12) are samples of the present invention,
The others are comparative samples.

(2) Preparation of Sample (1) A multilayer color negative light-sensitive material (Sample (1)) was prepared by sequentially coating the following layers on a transparent support made of subbed cellulose triacetate film.

1st layer: Antihalation layer Black gelatin aqueous solution containing colloidal silver was added at 0.3 g/r of silver.
It was applied at a ratio of d to give a dry film thickness of 3.0 μm.

2nd layer: Intermediate layer An aqueous gelatin solution containing dispersion A shown below is applied as an oil droplet component in dispersion A at a rate of 0.32 g/rrf (dry film thickness 1.2 μm).

(Dispersion A): 2-(2,5-t-aminophenoxybutylcarbamoyl')-4-(2-methyl-4-
12 g of dibutyl phthalate and 30 g of ethyl acetate were added to 1 g of (N-ethyl-N-hydroxyethylamino)phenylimino)-1(4H)-naphthalene, dissolved by heating at 65°C, and the triisopropyl solution was heated to 50°C. 5% containing 1.6g of sodium naphthalene sulfonate
Dispersion A was prepared by adding it to 150 ec of an aqueous gelatin solution and then dispersing it using a colloid mill.

3rd layer: Red-sensitive, low-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 0.6 μm, silver iodobromide emulsion containing 4 mol% silver iodide, average grain size 0.3 μm, iodide emulsion) A silver iodide emulsion containing 4 mol% silver (mixed in a ratio of 2:1) was chemically sensitized with gold and sulfur sensitizers, and further anhydrous 9-ethyl-3,3' was added as a red-sensitive sensitizing dye. -di(3-sulfopropyl)-4,5,4'5'-dibenzothiacarbocyanine hydroxide; N water 5.5'-dichloro-9-ethyl-3,3'-di(3-sulfobutyl)thia carbocyanine hydroxide; and anhydrous 2-(2-((5-
After adding chloro-3-ethyl-2(3H)-benzothiazoliden)methyl)-1-butenyl-5-chloro-3-(4-sulfobutyl)benzoxacilium, 4-
Hydroxy-6-methyl-1,3'3a,7-chitrazaindene 1. A red-sensitive low-sensitivity emulsion was prepared by adding 20.0 µm of Og, 1-phenyl-5-methcaptotetrazole. To this emulsion, 1-hydroxy-N7Cδ-(2,4-di-t-
amylphenoxy)butyl]-2-naphthamide 60g
1-hydroxy-4-(4-
(1-Hydroxy-δ-acetamido-3,6-disulfo-2-naphthylazo)phenoxy)-N-(δ-(2
, 4-di-t-amylphenoxy)butyl2-naphthamidodisodium salt 4g, dodecyl gallate 0.
5 g of tricresyl phosphate was added as a high-boiling solvent and mixed with 1 times the weight of the coupler, and ethyl acetate was added to the mixture to dissolve it. A dispersion prepared in an aqueous gelatin solution was added. A silver iodobromide emulsion containing this dispersion was coated at a ratio of 2.0 g/n silver (dry film jV 4 μm).

4th layer: Red-sensitive high-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 1.2 μm, containing 7 mol% silver iodide)
was chemically sensitized with gold and sulfur sensitizers, and anhydrous 9-ethyl-3,3'-di(3-sulfopropyl)-4,5,4'5'-dibenzothiocarbocyanine was added as a red-sensitizing dye. hydroxide, anhydrous 5,5'-dichloro-9-ethyl-3,3'-di(3-sulfobutyl)thiacarboxyanine hydroxide; and anhydrous 2-(2-((
5-chloro-3-ethyl-2(3H)-benzothiazoliden)methyl)-1-butenyl-5-chloro-3-(4
-Sulfobutyl)benzoxacilium was added, and then 1 g of 4-hydroxy-6-methyl-1,3,3a, 7-chitrazaindene and 10 μ of 1-phenyl-5-mercaptotetrazole were added to prepare a red-sensitive emulsion. did. This emulsion contains 1-hydroxy-4-(isopropylcarbamoyl)-methoxy 5-N-dodecyl-2-naphthamide as a cyan coupler per mole of silver halide.
5g1 1-Hydroxy-4-( as a colored coupler
4-(1-Hydroxy-δ-acetamido-3,6-disulfo-2-naphthylazo)phenoxy 1-N-[δ-
(2,4-di-t-amylphenoxy)butyl-2-
Add 1.5 g of naphthamide disodium salt and 0.5 g of dodecyl gallate, and mix with tricresyl phosphate in an amount of 1 times the weight of the coupler as a high-boiling solvent.
Furthermore, ethyl acetate was added to these mixtures to dissolve and disperse in the same manner as above.・1.4 g/n of silver iodobromide emulsion containing dispersion? (dry film thickness 2 μm).

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

6th layer: green-sensitive, low-sensitivity silver halide emulsion layer containing a silver iodobromide emulsion with an average grain size of 0.6 μm and 4 mol% of silver iodide; The dispersed silver iodobromide emulsion was chemically sensitized with gold and sulfur sensitizers, respectively, and anhydrous 5,5'-dichloro-9-ethyl-3,3'-di(3-sulfobutyl) was added as a green-sensitive sensitizing dye. Oxacarbocyanine hydroxide; anhydrous 5,5'-diphenyl-9-ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide and anhydrous 9
-Ethyl-3゜3'-di(3-sulfopropyl) -
5, 6, 5'.

Add 6'-dibenzoxacarbocyanine hydroxide followed by 4-hydroxy-6-methyl-1,3,3a
, 1.0 g of 7-chitrazaindene and 1-phenyl-
It was prepared in a conventional manner by adding 20.0 ml of 5-mercaptotetrazole. The two types of silver halide emulsions thus obtained were mixed at a ratio of 1:1 to prepare a green-sensitive silver halide emulsion.

This emulsion contains 1-(2,4,6-)dichlorophenyl) - as a magenta coupler per mole of silver halide.
3-(3-(2,4-di-t-amylphenoxyacetamide)benzamide-5-pyrazolone 48 g, 1-(2,4,6-)dichlorophenyl)-3=(2-chloro-5- 12 g of octadecenylsuccinimidoanilino)-4-(4-hydroxyphenylazo)-5-pyrazolone are mixed with tricresyl phosphate in an amount of 1 times the weight of the coupler as a high-boiling solvent, and then added to the mixture. Add ethyl acetate and dissolve.
Dispersion was performed in the same manner as above. A silver iodobromide emulsion containing this dispersion was coated at a ratio of 1.7 g silver/distance (dry film thickness 3 μm).

7th layer: Green-sensitive high-sensitivity silver halide emulsion layer Silver iodobromide emulsion (average grain size 1.2 μm, containing 7 mol% silver iodide)
was chemically sensitized with gold and sulfur sensitizers, and then anhydrous 5,5'-dichloro-9-ethyl-3 was added as a green-sensitive sensitizing dye.
, 3'-di(3-sulfobutyl)oxacarbocyanine hydroxide; anhydrous 5,5'-diphenyl-9-ethyl-3,3'-di(3-sulfobutyl)oxacarbocyanine hydroxide and anhydrous-9-ethyl -3,3'
-di(3-sulfopropyl)-5,6,5',6'
-add dibenzoxacarbocyanine hydroxide;
then 4-hydroxy-6-methyl-1,3+ 3a,
7-chitrazaindene 1.0g and 1-phenyl-5
- A green-sensitive high-strength silver halide emulsion was prepared by adding 10.0 μm of mercaptotetrazole. The magenta coupler is 1-(
2,4,6,-trichlorophenyl)-3-(3-(2
, 4-di-t-aminophenoxyacetamido)benzamide] -5-pyrazolone 21 g, 1-(2°4.6-)dichlorophenyl'')-3 as colored coupler
-(2-chloro-5-octadecenylsuccinimidoanilino)-4-(4-hydroxyphenylazo)-5-
3 g of pyrazolone was mixed with 1 times the amount of tricresyl phosphate as a coupler as a high boiling point solvent, and ethyl acetate was added to the mixture to dissolve and disperse in the same manner as above. The silver iodobromide emulsion containing this dispersion was 1.2
Coated at a ratio of g/g (dry film thickness 1.8 μm)
.

8th layer: (corresponds to the non-photosensitive layer of the present invention) 2.5-di-
Dissolve 3 g of t-octylhydroquinone and 1.5 g of di-2-ethylhexyl phthalate in 10 m6 of ethyl acetate, and add 0.3 g of sodium triisopropylnaphthalenesulfonate.
A dispersion of gelatin containing 0.9 g of gelatin/I was added to the gelatin aqueous solution, and this was added to the gelatin aqueous solution containing
2.5-di-t-octylhydroquinone IX 10-
Dry membrane K 1.2 μm at the ratio of 'mo II/rd
I applied it so that it covered the skin.

9th layer: yellow filter layer (corresponds to the non-photosensitive filter layer of the present invention) 2,
3 g of 5-di-t-octylhydroquinone and 1.5 g of di-2-ethylhexyl phthalate were added to 10 m of ethyl acetate.
A dispersion prepared by dissolving the gelatin in an aqueous gelatin solution containing 0.3 g of sodium triisopropylnaphthalene sulfonate was added, 1-phenyl-5-mercaptotetrazole was added, and this was dissolved in gelatin 0.9 g/rrf, 2
．． 5-di-t-octylhydroquinone I X 10-
'mol/d11-phenyl-5-mercaptotetrazole 1.4rrg/rrr, average particle size 0.08
A non-photosensitive silver iodobromide emulsion containing 4 mol % of silver iodobromide in micrometers was coated at a rate of 0.1 g/m of silver to give a dry film thickness of 1.2 micrometers. - 10th layer: intermediate N (corresponds to the non-photosensitive layer of the present invention) 2.5
- 3 g of di-t-octylhydroquinone and 1.5 g of di-2-ethylhexyl phthalate in 10+wl of ethyl acetate.
A dispersion prepared by dissolving 0.3 g of sodium triisopropylnaphthalene sulfonate in an aqueous gelatin solution is added to the aqueous gelatin solution.
9 g/rri, dry film thickness 1 at the rate of 2.5-di-t-octylhydroquinone lXl0-'moj2/m
．． It was coated to a thickness of 2 μm.

11th layer: blue-sensitive, low-sensitivity silver halide emulsion layer A silver iodobromide emulsion (average grain size 0.6 μm, containing 6 mol% silver iodide) is chemically sensitized with gold and sulfur enhancers, and further aggravated. Anhydrous 5°5'-dimethoxy-3,5-di(3
-sulfopropyl) thiacyanine hydroxide,
Then 4-hydroxy-6-methyl-1,3,3a.

1.0 g of 7-chitrazaindene and 20 μg of 1-phenyl-5-mercaptotetrazole were added and prepared in a conventional manner to prepare a blue-sensitive, low-sensitivity silver halide emulsion. .

In addition, α as a yellow coupler per mole of silver halide
-pivaloyl-α-(1-benzyl-2-phenyl-3
,5-dioxo-1,2,4-triacylidin-4-yl)-21-chloro-5'-[α-(dodecyloxycarbonyl)ethoxycarbonyl]acetanilide 120
g, 50 g of α-(3-(α-(2,4-di-t-amylphenoxy)butyramide))benzoyl-2′-methoxyacetanilide was added, and 1 times the amount of dibutyl phthalate as the coupler was added as a high-boiling solvent. After mixing, ethyl acetate was added to dissolve and dispersed in the same manner as above.

A silver iodobromide emulsion containing this dispersion was prepared at a concentration of 0.7 g of silver/
% (dry film thickness: 4 μm).

12th layer: blue-sensitive, high-sensitivity silver halide emulsion layer A silver iodobromide emulsion (average grain size 1.2 μm, containing 7 mol% silver iodide) is chemically sensitized with gold and sulfur enhancers, and further aggravated. Anhydrous 5゜5'-dimethoxy-3,3'-di(
3-sulfopropyl) thiacyanine hydroxide followed by 4-hydroxy-6-methyl-1,3,3a.

7-chitrazaindene 1.0g and l-phenyl-5
- 10.0 mg of mercaptotetrazole was added and prepared in a conventional manner to produce a blue-sensitive, high-sensitivity silver halide emulsion. A silver iodobromide emulsion containing 130 g of the same coupler as the 10th layer as a yellow coupler per mole of silver halide was coated onto this emulsion at a rate of 0.5 g/m (dry film thickness: 3 .mu.m).

13th layer: Intermediate layer 2 g of di-2-ethylhexyl phthalate, 2 g of 2-[3-cyano-3-(n-dodecylaminocarbonyl)allylidene]-1-ethylpyrrolidine and 2 ml of ethyl acetate were mixed, and triisopropylnaphthalene was added. A dispersion prepared in an aqueous gelatin solution containing 0.6 g of sodium sulfonate was added, and this was applied at a rate of 1.0 g/n (gelatin) to give a dry film thickness of 1.0 μm.

14th layer: Protective layer As a cloak agent, an aqueous gelatin solution containing silica with an average particle size of 5 μm, a slipping agent (1), and an organic fluoro compound (2) is used as a mantle agent, 0.02 g/m of silica, and 0.04 g/m of slipping agent.
g/cd and organic fluoro compounds 5+ng/f
fl (dry film thickness 0.5 μm).

Slip agent"' CI!, -00C-n-C,,H
,.

CHOOCn-CzHz CH2OOCn-C++Hzs Organic fluoro compound (2) CHz C00CHz (Ch)b HNaO:
+S CHC00CHz (CFz)6H ■Sample (
Preparation of 2) Sample (2) was prepared in the same manner as Sample (1) except that the 8th layer and the 2.5-di-t-octylhydroquinone (SC-2) of the first ON were removed.

(2) Preparation of Sample (3) Sample (3) was prepared in the same manner as Sample (1) except that the 8th layer was removed. This sample (3) lacks one non-photosensitive layer (non-photosensitive layer formed from the support) sandwiching the filter layer and is outside the scope of the present invention.

(2) Preparation of Sample (4) Sample (4) was prepared in the same manner as Sample (3) except that the IO layer (SC-2) was removed. This sample (4)
Similarly to sample (3), this sample is outside the scope of the present invention.

(2) Preparation of Sample (5) Sample (5) was prepared in the same manner as Sample (1) except that the 10th layer was removed. This sample (5) lacks the non-photosensitive layer on the side far from the support (blue-sensitive emulsion layer side) sandwiching the filter layer, and is outside the scope of the present invention.

(2) Preparation of Sample (6) Sample (6) was prepared in the same manner as Sample (5) except that the eighth layer (SC-2) was removed. This sample (6) is
Like sample (5), it is outside the scope of the present invention.

(2) Preparation of Sample (7) Sample (7) was prepared in the same manner as Sample (1) except that the 8th and 10th layers were removed. This sample (7) lacks any non-photosensitive layers sandwiching the filter layer and is outside the scope of the present invention.

(2) Preparation of Sample (8) Sample (8) was prepared in the same manner as Sample (7) except that the non-photosensitive silver iodobromide layer of the ninth layer was removed. This sample (8)
is outside the scope of the present invention because the filter layer does not contain fine particles/silver halide.

■Preparation of sample (9) (SC-2) of the 8th and 10th layers of sample (1)
Sample (9) was prepared in the same manner except that -11) was changed.

■Preparation of sample (10) The 8th and 10th layers (SC-2) of sample (1) are
Sample (10) was prepared in the same manner except that the sample (10) was changed to -6).

■Preparation of sample (11) The 8th layer and 10th layer (SC-2) of sample (1) are
Sample (11) was prepared in the same manner except that -7) was changed.

■Preparation of sample (12) Sample (12) was prepared in the same manner as sample (1) except that the amount of (SC-2) added in the 8th and 10th layers was changed to 3 x 10-'mol/m. .

Samples (1) to (13) obtained as above were stored at 50°C and 80% relative humidity for 2 days to check their storage stability.
After conducting a forced deterioration test for 2 days at 60°C and 20% relative humidity, wedge exposure was performed according to the conventional method.
I performed the following processing.

(Processing process) (37,8°C) Processing time 1,
Color development 3 minutes 15 seconds 2, bleaching 6 minutes 30 seconds 3, washing 3 minutes 15 seconds 4, fixing 6 minutes 30 seconds 5, washing 3 minutes 15 seconds 6, stabilization 1 minute 30 seconds 7, drying The composition of the treatment liquid used in each treatment step was as follows.

(Color developer composition) (Bleach solution composition) (Fixer composition) and adjust.

(Stabilizing liquid composition) Add water, □, good.

Next, the minimum concentration Dmin of each sample (densitometer base concentration by foggable colored coupler) and sensitivity (IS
O) was measured and the results are shown in Table 1.

As is clear from Table 1, there are comparison samples that lack one (sample (3) to sample (6)) or both (sample (7)) of the non-photosensitive layers sandwiching the filter layer, and those that contain particulate halogen in the filter layer. The comparison sample (sample (8)) that does not contain silver shows a decrease in sensitivity and an increase in fog values under high temperature and high temperature conditions or under high temperature and low humidity conditions, whereas the samples of the present invention exhibit low sensitivity under high temperature and high temperature conditions and high temperature and low humidity conditions. It can be seen that the stability is excellent.

Especially samples (1) and (9) to (12) containing Dp' scavenger in the non-photosensitive layer (8th layer, 10th layer)
The effects of the present invention are evident in the following.

〔Effect of the invention〕

As mentioned above, the silver halide color photographic light-sensitive material of the present invention has significantly improved stability under harsh storage conditions such as high temperature and high humidity, high temperature and low humidity.

Claims (1)

[Scope of Claims] A support has at least one red-sensitive silver halide emulsion layer, one or more green-sensitive silver halide emulsion layers, and one or more blue-sensitive silver halide emulsion layers, and the blue-sensitive emulsion layer In a silver halide color photographic light-sensitive material provided on the side farther from the support than the photosensitive layer, yellow colloidal silver and non-colloidal silver are provided between the blue-sensitive silver halide emulsion layer and another light-sensitive silver halide emulsion layer. A halogen characterized by having a non-photosensitive filter layer containing photosensitive fine grain silver halide, and having a non-photosensitive layer between the non-photosensitive filter layer and a photosensitive layer sandwiching the non-photosensitive filter layer. Silver chemical color photographic material.