JPH0322970B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a color photographic light-sensitive material that prevents color staining, and more particularly to a silver halide color photographic light-sensitive material containing a hydroquinone derivative as a color stain preventive agent. In a multilayer color photographic material containing a color-forming coupler in a silver halide photographic emulsion and developed using a color developer such as paraphenylene diamine, the oxidized product of the color developer generated during development is It is well known that the phenomenon of so-called "color turbidity" (color mixing) occurs in which undesirable dyes are formed by migrating into the image forming layer. It is also known that during color development, undesirable "color fog" development occurs due to air oxidation of the developing agent, fog of the emulsion, and the like. In the following, this "color turbidity" and "color fog" will be collectively referred to as "color contamination." In order to prevent color staining, various methods using hydroquinone have been proposed. For example, regarding the use of monolinear alkylhydroquinone, US Pat.
Regarding the use of monobranched alkylhydroquinone, see US Pat. No. 3,700,453,
It is described in West German Patent Publication No. 2149789, Japanese Patent Application Laid-open No. 156438/1982, and Japanese Patent Publication No. 49-106329. On the other hand, regarding dilinear alkylhydroquinone, the US patent
No. 2728659, No. 2732300, British Patent No. 752146, No. 2732300, British Patent No. 752146,
1086208 issue and "Chemical Abstracts" magazine 58
Volume 6367h, etc., and U.S. Patent Nos. 3700453 and 2732300 regarding di-branched alkylhydroquinone,
British Patent No. 1086208, above-mentioned "Chemical Abstracts" magazine, Japanese Patent Application Publication No. 156438 (1972), Japanese Patent Publication No. 156438 (1972), Publication No. 156438 (1977)
It is described in No. 21249, No. 56-40818, etc. In addition, regarding the use of alkylhydroquinone as a color stain prevention agent, British Patent No. 558258
No. 557750 (corresponding U.S. Patent No. 2360290);
No. 557802, No. 731301 (corresponding U.S. Patent No. 2701197)
U.S. Patent No. 2331327, U.S. Patent No. 2403721, U.S. Patent No. 3582333,
West German Patent Publication No. 2505016 (corresponding Japanese Patent Publication No. 50-110337)
(No.), Special Publication No. 51-12250, and No. 56-40816. In recent years, there has been a strong demand for improving the quality of photographic images, especially the graininess and sharpness. Among these, in order to improve the graininess, the molar ratio of silver halide to the color image forming coupler is increased in a specific emulsion layer of the sensitive material, and the coupling of the oxidized color developer generated by silver development is achieved. It is possible to reduce the appearance of grainy roughness by reducing the chance of diffusion, and by setting the pigment so that it exists uniformly rather than in particulate form. Here, the influence of the graininess of color photosensitive materials on the human eye varies depending on the hue formed, and the effect is greatest on the green-sensitive layer, which develops a magenta color, and on the red-sensitive layer, which develops a cyan color. This is followed by the blue-sensitive layer, which develops a yellow color. For this reason, improvement of the green-sensitive layer is the most important. However, when the graininess is improved using the above method, the amount of silver used in the photosensitive material increases significantly, and when normal processing is performed, developed silver remains in the photosensitive material (desilvering failure). ). Therefore, it is necessary to divide the photosensitive layer into two or more layers that sense colors in the same area, expand the latitude by using emulsions with different sensitivities, and also focus on the density range where graininess needs to be improved among these two or more layers. By increasing the molar ratio of silver to the color image-forming coupler in the photosensitive layer and making it relatively low in other layers, latitude expansion, graininess, desilvering properties, and other photographic properties are satisfied. . However, if there is a layer with a high silver coupler ratio, an excess of oxidized color developing agent is produced relative to the coupler, and as a result, color contamination such as "color turbidity (color mixing)" is likely to occur. In order to prevent this color staining, in sensitive materials containing a sufficient amount of conventional color staining preventive agents such as the aforementioned hydroquinones, the layer containing the color staining preventive agent often becomes thick, resulting in poor sharpness. This results in a decrease in As described above, there is a dilemma that improving graininess results in a decrease in sharpness, and there has been a desire to develop a technology that can achieve both at a high level. A first object of the present invention is to provide a photographic material with improved graininess. A second object of the present invention is to provide a photographic material with improved graininess without reducing sharpness or causing color stains such as color turbidity. Other objects of the invention will become apparent from the description below. The above object of the present invention is to provide a silver halide color photographic light-sensitive material having at least two or more light-sensitive emulsion layers having substantially the same color sensitivity and an intermediate layer on a support. at least one of
This is achieved by having a molar ratio of silver halide to color image forming coupler contained in the layer of 10 or more, and further containing at least one compound represented by the following general formula () in the intermediate layer. I got it. (In the formula, R ¹ and R ² may be the same or different, and include 1-methylhexyl group, 1-ethylpentyl group, 1-propylbutyl group, 1-methylheptyl group, 1-ethylhexyl group, and 1-propyl (Represents a group selected from pentyl group.) When R ₁ and R ₂ have 8 carbon atoms, that is, 1
-Methylheptyl group, 1-ethylhexyl group, 1
The most preferred group is a group selected from -propylpentyl group. Further, it is preferable that the composition contains a mixture of two or more, particularly four or more, compounds of the general formula () as a color stain preventive agent. Below, the compound 21 of the general formula () according to the present invention
Here are some specific examples of the species. Compound 1 2,5-di(1-methylheptyl)hydroquinone 2 2,5-di(1-ethylhexyl)hydroquinone 3 2,5-di(1-propylpentyl)hydroquinone 4 2-(1-methylheptyl)-5 -(1-ethylhexyl)hydroquinone 5 2-(1-methylheptyl)-5-(1-propylpentyl)hydroquinone 6 2-(1-ethylhexyl)-5-(1-propylpentyl)hydroquinone 7 2,5-di (1-Methylhexyl)hydroquinone 8 2,5-di(1-ethylpentyl)hydroquinone 9 2,5-di(1-propylbutyl)hydroquinone 10 2-(1-methylheptyl)-5-(1-methylhexyl ) Hydroquinone 11 2-(1-ethylhexyl)-5-(1-ethylpentyl)hydroquinone 12 2-(1-propylpentyl)-5-(1-propylbutyl)hydroquinone Synthesis of compounds of general formula () according to the present invention teeth,
This can be easily carried out by the methods described in French Patent No. 1496562, West German Patent No. 2110521, etc., and methods similar thereto. The color stain preventive agent according to the present invention is an oil itself at room temperature and does not cause precipitation of crystals, so it can be dispersed in a hydrophilic colloid composition without using oil as a solvent. Also,
It can also be dispersed with dispersing oils and low-boiling organic solvents commonly known in photographic systems. The color stain preventive agent according to the present invention can be used in combination with color stain preventive agents other than the present invention. In particular, it is advantageous to use it in combination with hydroquinones. Examples of hydroquinones to be mixed include 2,5-di-t
-octylhydroquinone, 2,5-di-t-hexylhydroquinone, 2,5-di-n-octylhydroquinone, 2,5-di-secondary dodecylhydroquinone, 2-secondary octylhydroquinone, 2,6- Examples include di-secondary octylhydroquinone, 2-n-octyl-5-secondary octylhydroquinone, 2,5-di-t-pentadecylhydroquinone, and 2-methyl-5-secondary octadecylhydroquinone. The compound represented by the general formula () of the present invention is used in an intermediate layer sandwiched between each light-sensitive emulsion layer, and is used in an emulsion layer in which the molar ratio of silver halide and color image-forming coupler is 10 or more. It is preferable to use it in an adjacent intermediate layer from the viewpoint of preventing color mixture. In particular, it is preferable when used in an intermediate layer sandwiched between a green-sensitive emulsion layer and a red-sensitive emulsion layer, in view of the graininess of the green-sensitive emulsion layer and color mixing with the red-sensitive layer, which have a large effect on human eyes. . The compound represented by the general formula () of the present invention preferably has a concentration of 0.01 to 2 g/m ² , more preferably 0.05 to 2 g/m 2 .
It is used at an addition amount of 1 g/m ² . These compounds are usually mixed with hydrophilic colloids such as gelatin and used as an intermediate layer. The compounds of the invention can also be used as color antifoggants or antioxidants in red, green or blue light-sensitive emulsion layers containing silver halide. Each of the light-sensitive emulsion layers of the color photographic light-sensitive material of the present invention has at least two light-sensitive emulsion layers in which at least one light-sensitive emulsion layer has substantially the same color sensitivity.
layers (2 layers: o layer and u layer, 3 layers: o layer, m layer and u layer)
The layers, etc., are provided on the support in this order: U layer, M layer, O layer. ), the number of other photosensitive emulsion layers may be one, two, or three. In what order is the layer structure of the color photographic light-sensitive material of the present invention: a blue-sensitive emulsion layer, a green-sensitive emulsion layer,
In addition to the red-sensitive emulsion layer, there may be an intermediate layer, a protective layer, an antihalation layer, a filter layer, etc. Generally, in color reversal light-sensitive materials and color negative light-sensitive materials, light-sensitive emulsion layers are provided on a support in the order of red sensitivity, green sensitivity, and blue sensitivity. The emulsion layers may also be replaced. Furthermore, in color photographic paper and color positives for movies, a layer structure opposite to that described above is generally used. Specifically, an antihalation layer, a low red-sensitive emulsion layer, a high red-sensitive emulsion layer, an intermediate layer containing a compound of general formula (), a low red-sensitive emulsion layer, and a high red-sensitive emulsion layer are formed on a support. A color negative light-sensitive material comprising an emulsion layer, a yellow filter layer, a low-sensitivity blue-sensitivity emulsion layer, a high-sensitivity blue-sensitivity emulsion layer, and a protective layer, an antihalation layer, a low-sensitivity red-sensitivity emulsion layer, and a low-sensitivity green emulsion layer on a support. Sensitive emulsion layer, intermediate layer, highly sensitive red-sensitive emulsion layer, intermediate layer containing a compound of general formula (), highly sensitive green-sensitive emulsion layer, yellow filter layer, low-sensitive blue-sensitive emulsion layer, highly sensitive blue-sensitive emulsion layer , a color negative light-sensitive material in which protective layers are sequentially provided, a low-sensitivity red-sensitive emulsion layer, a medium-sensitivity red-sensitivity emulsion layer, a high-sensitivity red-sensitivity emulsion layer, an intermediate layer containing a compound of the general formula (), a low-sensitivity Green-sensitive emulsion layer, medium-sensitivity green-sensitivity emulsion layer, high-sensitivity green-sensitivity emulsion layer, intermediate layer, yellow filter layer, low-sensitivity blue-sensitivity emulsion layer, intermediate blue-sensitivity emulsion layer, high-sensitivity blue-sensitivity emulsion layer, second protective layer , a color reversal photosensitive material in which a first protective layer is sequentially provided. In the present invention, the emulsion layer in which the molar ratio of silver halide to the color image forming coupler is 10 or more generally corresponds to the emulsion layer that shares the low density region, and generally corresponds to the u layer in the case of a color reversal light-sensitive material. death,
In addition, in color negative photosensitive materials, this corresponds to the o layer. In at least one emulsion layer of the color photographic light-sensitive material of the present invention, the molar ratio of silver halide to dye-forming coupler is 10 or more, preferably 15 to 10.
It is 200. Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material of the present invention. Preferred silver halides are silver iodobromide or silver iodochlorobromide containing 1 to 15 mole percent silver iodide. The average grain size of the silver halide grains in the photographic emulsion (the grain size is the grain diameter in the case of spherical or approximately spherical grains, the ridge length in the case of cubic grains,
(expressed as an average based on the projected area) is not particularly limited, but is preferably 3μ or less. The particle size distribution may be narrow or wide. Silver halide grains in photographic emulsions may have regular crystal shapes such as cubes and octahedrons, or irregular crystal shapes such as spherical and plate shapes. It may be a crystalline substance or a compound of these crystalline forms.
It may also consist of a mixture of particles of various crystalline forms. The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.
Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particles. The photographic emulsion used in the present invention is P. Glafkides
Written by Chimie et Physique Photographique (Paul
Montel Publishing, 1967), GFDuffin
Photographic Emulsion Chemistry (The Focal
Press, 1966), VLZelikman et al.
Making and Coating Photographic Emulsion
(The Focal Press, 1964). In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, see for example H. Frieser ed. Die
Grudlagen der Photographischen Prozesse
mit Silberhalogeniden.
Verlagsgesellschaft, 1968) 675-734 can be used. That is, sulfur-containing compounds that can react with activated gelatin and silver (e.g., thiosulfates, thioureas,
Sulfur sensitization method using reducing substances (e.g. stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds);
Noble metal compounds (e.g. gold complexes, Pt, Ir,
A noble metal sensitization method using complex salts of metals in the periodic table group such as Pd can be used alone or in combination. Specific examples of these include U.S. Patent Nos. 1574944, 2410689, and 2278947 for sulfur sensitization methods;
U.S. Patent No. 2728668, U.S. Patent No. 3656955, etc., and U.S. Patent No. 2983609, U.S. Patent No. 2419974 for reduction sensitization method
No. 4054458, U.S. Patent No. 2399083, No. 2448060, British Patent No.
It is described in each specification such as No. 618061. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidales (particularly nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzotizoles, Mercaptobenzimidazoles, mercaptothiazoles,
Mercaptotetrazoles (especially 1-phenyl-
5-mercaptotetrazole), mercaptopyrimidines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindenes (especially 4-hydroxy substituted 1, 3, 3a, 7)
Many compounds known as antifoggants or stabilizers can be added, such as tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; and the like. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, and quaternary ammonium salts for the purpose of increasing sensitivity, increasing contrast, or accelerating development. compounds, urethane derivatives, urea derivatives,
It may also contain imidazole derivatives, 3-pyrazolidones, and the like. For example, U.S. Patent No. 2400532,
No. 2423549, No. 2716062, No. 3617280, No.
No. 3772021, No. 3808003, British Patent No. 1488991,
Those described in, etc. can be used. Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., synthetic hydrophilic polymer substances, etc. can be used. . The photographic emulsions used in this invention may be spectrally sensitized with methine dyes and others. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure, Vol. 176, 17643 (1978).
Published in December 2017), page 23, Section J. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains a color-forming coupler, that is, a color is formed by oxidative coupling with an aromatic primary amine developer (for example, a phenylene diamine derivative or an aminophenol derivative) during a color development process. It may also contain compounds that can. For example, as a magenta coupler, 5
- Pyrazolone couplers, pyrazolone benzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc., and yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides), etc.
Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ions. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). In addition to the DIR coupler, the coupling reaction product is colorless and may contain a colorless DIR coupling compound that releases a development inhibitor. A specific example of a magenta coloring coupler is a U.S. patent
No. 2600788, No. 2983608, No. 3062653, No.
No. 3127269, No. 3311476, No. 3419391, No. 3127269, No. 3311476, No. 3419391, No.
No. 3519429, No. 3558319, No. 3582322, No.
No. 3615506, No. 3834908, No. 3891445, West German Patent No. 1810464, West German Patent Application (OLS) No. 2408665,
No. 2417945, No. 2418959, No. 2424467, Special Publication No. 40-6031, No. 52-58922, No. 49-129538,
No. 49-74027, No. 50-159336, No. 52-42121
No. 49-74028, No. 50-60233, No. 51-
No. 26541, No. 53-55122, etc. Further, polymer couplers described in JP-A-58-28745 and the like can also be preferably used. A specific example of a yellow coupler is U.S. Patent No. 2875057.
issue. Same number 3265506. No. 3408194. No. 3551155,
No. 3582322. Same No. 3725072, No. 3891445. West German Patent No. 1547868, West German Application No. 2219917, same
No. 2261361, No. 2414006, British Patent No. 1425020,
Special Publication No. 51-10783, Japanese Patent Publication No. 47-26133, No. 48-
No. 73147, No. 51-102636, No. 50-6341, No. 50
−123342, No. 50-130442, No. 51-21827,
These are described in No. 50-87650, No. 52-82424, No. 52-115219, etc. Specific examples of cyan couplers are U.S. Patent No. 2369929,
Same No. 2434272, No. 2474293, No. 2521908, Same No.
No. 2895826, No. 3034892, No. 3311476, No. 3311476, No.
No. 3458315, No. 3476563, No. 3583971, No.
No. 3591383, No. 3767411, No. 4004929, West German patent application (OLS) No. 2414830, No. 2454329, Japanese Patent Application Publication No. 48-59838, No. 51-26034, No. 48-5055,
These are those described in No. 51-146828, No. 52-69624, and No. 52-90932. As a colored coupler, for example, a US patent
No. 3476560, Special Publication No. 44-2016, No. 38-22335,
No. 42-11304, No. 44-32461, JP-A No. 1973-
Those described in Specification No. 26034, Specification No. 52-42121, and West German Patent Application (OLS) No. 2418959 can be used. As a DIR coupler, for example, the US patent
No. 3227554, No. 3617291, No. 3701783, No. 3227554, No. 3617291, No. 3701783, No.
No. 3790384, No. 3632345, West German patent application (OLS)
No. 2414006, No. 2454301, No. 2454329, British Patent No. 953454, Japanese Patent Application Publication No. 1983-69624, No. 49-12335
Those described in Japanese Patent Publication No. 51-16141 can be used. In addition to the DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor during development; for example, U.S. Pat.
West German Patent Application (OLS) No. 2417914, Japanese Unexamined Patent Publication No. 1983-
Those described in No. 15271 and JP-A-53-9116 can be used. A coupler can be introduced into the silver halide emulsion layer by any known method, such as the method 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 tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkyl amides (e.g. diethyl laurylamide), aliphatic esters (e.g. dibutoxyethyl succinate, dioctyl azelate), phenols (e.g. 2,4-ditertiary amylphenol), trimesic acid esters (e.g. tributyl trimesate), or organic solvents with a boiling point of about 30°C to 150°C, For example, it is dissolved in a lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., and then dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-Open No. 51-59943 can also be used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. The color photographic material of the present invention includes Research
Hardeners, dyes, coating aids, plasticizers, slipping agents, matting agents, brighteners, and the like described in Disclosure vol. 176 (1978) RD-17643 can be used. Specific examples of color photographic materials to which the present invention can be applied include color reversal films, color negative films, color photographic papers, color positives for movies, and the like. However, it is particularly effectively used in color photographic materials. For photographic processing of the light-sensitive material of the present invention, for example, Research Disclosure Co., Ltd.
Any of the known methods and known treatment liquids as described in RD-17643, No. 176, pp. 28-30 (RD-17643) can be applied. This photographic processing may be either photographic processing that forms a silver image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing), depending on the purpose. The processing temperature is usually chosen between 18°C and 50°C, but temperatures below 18°C or above 50°C may also be used. Conventional methods for forming dye images can be applied. For example, negative-positive method (e.g. “Journal of the
Society of Motion Picture and Television
Engineers, Volume 61 (1953), pp. 667-701); developed in a developer containing a black and white developing agent to produce a negative silver image, followed by at least one uniform exposure or other suitable A color reversal method in which a dye-positive image is obtained by performing a fog treatment followed by color development; a silver dye method in which a photographic emulsion containing a dye is exposed and developed to create a silver image, and this is used as a bleaching catalyst to bleach the dye. A bleaching method or the like is used.The color developer generally consists of an alkaline aqueous solution containing a color developing agent.The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (e.g. 4-amino-N-diethyl). Aniline, 3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxy Ethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methanesulfamide ethylaniline, 4-
amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used. Other Photography by LFAMason
Processing Chemistry (Focal Prese, 1966)
pages 226-229, U.S. Patent No. 2193015, U.S. Patent No. 2592364
JP-A No. 48-64933, etc. may be used. The color developer may also contain a PH buffer, a development inhibitor or an antifoggant. In addition, if necessary, water softeners, preservatives, organic solvents, development accelerators, dye-forming couplers, competitive couplers, fogging agents, auxiliary developers, viscosity imparting agents, polycarboxylic acid chelating agents, and antioxidants are added. It may also include. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Bleach agents include iron (), cobalt (), chromium (), and copper ().
Compounds of polyvalent metals such as, peracids, quinones, nitroso compounds, etc. are used. Bleach or bleach-fix solution has US Patent 3042520
No. 3241966, Special Publication No. 1977-8506, Special Publication No. 1973
- Bleaching accelerator described in No. 8836, etc., JP-A-53-
In addition to the thiol compound described in No. 65732, various additives can also be added. Example 1 Sample A was obtained by coating an emulsion layer and an auxiliary layer in the following order on a triacetyl cellulose support provided with an undercoat layer. 1st layer; low-sensitivity red-sensitivity emulsion layer: 100 g of cyan coupler 2-(heptafluorobutyramide)-5-{2'-(2″,4″-di-t-aminophenoxy)butyramide}-phenol
Sensitizing Dye A 1 kg of red-sensitive low iodobromide emulsion containing (81% within ±40% of the average grain size of silver halide grains)
It is silver iodobromide with a size distribution in which the number of particles is present, and it is mixed with 70 g of silver and 60 g of gelatin (iodine content is 6 mol%) and coated to a dry film thickness of 2μ (silver amount 0.5 g/ ^m2 ). 2nd layer; medium-sensitivity red-sensitivity emulsion layer 100 g of cyan coupler 2-(heptafluorobutyramide)-5-{2'-(2″,4″-di-t-aminophenoxy)butyramide}-phenol
was dissolved in 100 c.c. of tricresyl phosphate and 100 c.c. of ethyl acetate, and stirred at high speed with 10 g of sodium dodecylbenzenesulfonic acid and 1 kg of 10% gelatin aqueous solution. 1 kg of red-sensitive medium silver iodobromide emulsion containing (the size distribution mentioned in the first layer emulsion is 76%, silver
70 g of gelatin (containing 60 g of gelatin, iodine content: 6 mol %) and coated to a dry film thickness of 1 μm (silver amount: 0.4 g/m ² ). 3rd layer: Highly sensitive red-sensitive emulsion layer 100 g of cyan coupler 2-(heptafluorobutyramide)-5-{2'-(2'',4''-di-t-aminophenoxy)butyramide}-phenol
was dissolved in 100 c.c. of tricresyl phosphate and 100 c.c. of ethyl acetate and stirred at high speed with 10 g of sodium dodecylbenzenesulfonic acid and 1 kg of 10% gelatin aqueous solution. 1 kg of the red-sensitive highly iodosilver bromide emulsion (the above size distribution is 78%, contains 70 g of silver, 60 g of gelatin, and the iodine content is 6 mol%) was mixed to determine the dry film thickness.
It was coated to a thickness of 1μ (silver amount 0.4g/m ² ). 4th layer; middle layer 2,5-di-t-octylhydroquinone 50g
, dibutyl phthalate 100 c.c. and ethyl acetate 100 c.c.
Sodium dodecylbenzenesulfonate dissolved in cc
1 kg of 10% gelatin aqueous solution and 1 kg of emulsion obtained by high-speed stirring were mixed with 1 kg of 10% gelatin, and applied so that the coating amount of 2,5-di-t-octylhydroquinone was 200 mg/ ^m2 . did. 5th layer; low edge sensitivity emulsion layer 1-(2,4,6-trichlorophenyl)-3- which is a magenta coupler instead of a cyan coupler
Emulsion obtained in the same manner as the emulsion of the first layer except that {3-(2,4-di-t-amylphenoxyacetamide)benzamide}-5-pyrazolone was used
250g as sensitizing dye B (B/C molar ratio...0.5)
1kg of edge-sensitive, low-iod silver bromide emulsion containing (the above size distribution is 81%, 70g silver, 60g gelatin)
(silver content: 5.2 mol%) and coated to a dry film thickness of 2.0μ (silver amount: 0.7g/
m ² , molar ratio of silver to color image-forming coupler approximately 23). 6th layer; medium edge sensitive emulsion layer 1-(2,4,6-trichlorophenyl)-3- which is a magenta coupler instead of a cyan coupler
Emulsion obtained in the same manner as the emulsion of the first layer except that {3-(2,4-di-t-amylphenoxyacetamide)benzamide}-5-pyrazolone was used
1000g as sensitizing dye B (B/C molar ratio...0.5)
1 kg of edge-sensitive medium-sensitive silver iodobromide (75% of the above size distribution, containing 70 g of silver, 60 g of gelatin, and iodine content of 5.2 mol%) was mixed and applied to a dry film thickness of 1 μm. (Coated silver amount 0.35g/
m ² , the ratio of silver to color imaging coupler, approximately 6). 7th layer: highly sensitive emulsion layer 1-(2,4,6-trichlorophenyl)-3- which is magenta coupler instead of cyan coupler
Emulsion obtained in the same manner as the emulsion of the first layer except that {3-(2,4-di-t-amylphenoxyacetamide)benzamide}-5-pyrazolone was used
1000g as sensitizing dye B (B/C molar ratio...0.5)
(75% of the above size distribution, containing 70 g of silver, 60 g of gelatin, and iodine content of 5.2 mol %) containing 1 kg of edge-sensitive highly iodo-bromide emulsion, and adjusted to a dry film thickness of 1 μm. Coated (coated silver amount 0.35g/
m ² , the ratio of silver to color imaging coupler approximately 6). 8th layer; middle layer 1 kg of the emulsion used in the 4th layer was mixed with 1 kg of 10% gelatin.
Kg and applied to a dry film thickness of 1 μm. Ninth layer; yellow filter layer An emulsion containing yellow colloidal silver was coated to a dry film thickness of 1 μm. 10th layer; Low-sensitivity blue-sensitive emulsion layer. Yellow coupler instead of cyan coupler, α-(pivaloyl)-α-(1-benzyl-5
-Ethoxy-3-hydantoinyl)-2-chloro-5-dodecyloxycarbonylacetanilide was used, but 1000 g of the emulsion obtained in the same manner as the emulsion of the first layer was mixed with blue-sensitive low-iodobromide silver. Emulsion 1
Kg (the above size distribution is 77%, contains 70 g of silver, 60 g of gelatin, and the iodine content is 5.5 mol%) and coated to a dry film thickness of 2.0 μ (coated silver amount: 0.6 g/m ² ). 11th layer; Medium blue-sensitive emulsion layer. Yellow coupler instead of cyan coupler, α-(pivaloyl)-α-(1-benzyl-5
-Ethoxy-3-hydantoinyl)-2-chloro-5-dodecyloxycarbonylacetanilide was used, but 1000 g of the emulsion obtained in the same manner as the emulsion of the first layer was mixed with blue-sensitive highly iodobromide silver. Emulsion 1
Kg (the above size distribution is 72%, contains 70 g of silver, 60 g of gelatin, and the iodine content is 5.5 mol%) and coated to a dry film thickness of 1.0 μ (coated silver amount: 0.5 g/m ² ). 12th layer; Highly blue-sensitive emulsion layer. Yellow coupler is used instead of cyan coupler, α-(pivaloyl)-α-(1-benzyl-5
-Ethoxy-3-hydantoinyl)-2-chloro-5-dodecyloxycarbonylacetanilide was used, but 1000 g of the emulsion obtained in the same manner as the emulsion of the first layer was mixed with blue-sensitive highly iodobromide silver. Emulsion 1
Kg (size distribution 72% above, containing 70 g silver, 60 g gelatin, iodine content 5.5 mol%) and coated to a dry film thickness of 1.0 μ (coated silver amount 0.5 g/m ² ). . 13th layer; 2nd protective layer UV absorber 5-chloro-2-(2-hydroxy-3,5-
Di-t-butylphenyl-2H-benzotriazole 15g 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole 30g 2-(2-hydroxy-3-sec-butyl-5-
t-Butylphenyl-2H-benzotriazole
35g Dodecyl 5-(N,N-diethylamino)-2-
Benzenesulfonyl-2,4-pentadienoate 100g Triclean diphosphate 200c.c. Ethyl acetate 200c.c. Sodium dodecylbenzenesulfonate 20g 1Kg of emulsion obtained by stirring 2Kg of 10% gelatin aqueous solution at high speed % gelatin, water and coating aids and coated to a dry film thickness of 2 μm. 14th layer; 1st protective layer Fine grain emulsion that is not chemically sensitized (grain size
A 10% aqueous gellan solution containing 0.15μ, 1 mol % silver iodobromide emulsion) was applied to give a silver coating amount of 0.3g/m ² and a dry film thickness of 1μ. The obtained multilayer coated film is designated as Sample A. Only the fourth layer (intermediate layer) of sample A was coated with the emulsion and its usage amount, and the amount of hydroquinone derivative applied was the first layer.
Samples B to N were prepared with the changes shown in the table.

【table】

【table】

[Table] Note that dibutyl phthalate is not used in the emulsion of C to N. The prepared samples A to N were exposed through a red filter and a wedge with continuously different gray densities,
The following processing was performed. Processing process Process Time Temperature 1st development 6' 38℃ (±0.3) Washing 2' Reversing 2' Color development 6' Adjusting 2' Bleaching 6' Fixing 4' Washing 4 ' Stable 1' Dry at room temperature First developing water 700ml Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (monohydrate) 30g 1-phenyl 4-methyl 4-methoxy -3
Pyrazolidone 2g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0.1% solution) 2ml Add water 1000ml Invert water 700ml Nitrilo-N-N-N-trimethylenephosphonic acid 6Na salt 3g Stannous chloride ( Dihydrate) 1g P-aminophenol 0.1g Sodium hydroxide 8g Glacial acetic acid 15ml Add water to 1000ml Color developing water 700ml Sodium tetrapolyphosphate 2g Sodium sulfite 7g Sodium triphosphate (dihydrate) 36g Potassium bromide 1g Potassium iodide (0.1% solution) 90ml Sodium hydroxide 3g Citrazic acid 1.5g 4-Amino-3-methyl-N-ethyl-β-hydroxyethylaniline sesquisulfate monohydrate 11g Ethylenediamine 3g Add water to 1000ml Adjusted water 700ml Sodium sulfite 12g Sodium ethylenediaminetetraacetate (dihydrate) 8g Thioglycerin 0.4ml Glacial acetic acid 3ml Add water 1000ml Bleach water 800ml Sodium ethylenediaminetetraacetate (dihydrate) 2.0g Iron()ammonium ethylenediaminetetraacetate (dihydrate) Salt) 120.0g Potassium bromide 100.0g Add water 1.0 Fixing water 800ml Ammonium thiosulfate 80.0g Sodium sulfite 5.0g Sodium bisulfite 5.0g Add water 1.0 Stable water 800ml Formalin (37% by weight) 5.0ml Fuji Drywell 5.0 After adding 1.0 ml of water, the R density of samples A to N after the treatment was measured, and the coloring density of the R photosensitive layer, that is, the cyan density was measured. Here, when the compound added to the intermediate layer has a high ability to prevent color mixture, the minimum cyan density decreases and the red color becomes more vivid. In addition, after exposing the prepared samples A to N through a wedge for measuring sharpness and performing the above-mentioned processing,
Measurements were made using a sharpness measuring device. 20cycle/
The value in mm is based on sample A (1.00)
show. The higher the value, the better the response to the original and the higher the sharpness.

【table】

[Table] As shown in Table 2, compared to samples (A, B, I to N) using conventional hydroquinone derivatives, 2,5-di-sec-octylhydroquinone, a compound of the present invention, Samples used (C to H)
has the effect of improving both color mixing prevention ability and sharpness to a high level in a well-balanced manner. Example 2 A third sample was prepared in which the molar ratio of silver halide to color image forming coupler was varied from 5 to 23 by changing only the amount of emulsion added to the low sensitivity emulsion layer in Sample C of Example 1. It was created as shown in the table. Also,
In Sample E of Example 1, only the amount of emulsion added in the low sensitivity emulsion layer was changed, and the molar ratio of silver halide to color image forming coupler was varied from 5 to 23. Created as shown. These samples were subjected to the same treatment as shown in Example 1 and evaluated, and the results obtained are shown in Table 3.

[Table] From the above results, the degree of color mixing hardly changes when the molar ratio of silver to color image forming coupler is 10 or less, but increases significantly when it is 10 or more. When Compound 1 of the present invention is used in the intermediate layer in order to suppress the degree of color mixing, sufficient sharpness can be obtained even when used in a large amount of 600 mg/m ² .

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material having, on a support, at least two or more light-sensitive emulsion layers having substantially the same color sensitivity and an intermediate layer, in which the emulsion layer is The molar ratio of silver halide to color image forming coupler contained in at least one layer is 10 or more, and the intermediate layer further contains at least one compound represented by the following general formula (). A silver halide color photographic light-sensitive material. (In the formula, R ¹ and R ² may be the same or different, and include 1-methylhexyl group, 1-ethylpentyl group, 1-propylbutyl group, 1-methylheptyl group, 1-ethylhexyl group, and 1-propyl Represents a group selected from pentyl groups.)