JPS6113582B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method of forming a dye image by a dye image reinforcement method. More specifically, the present invention relates to a method for forming a dye image that does not cause interlayer color turbidity during color development and has good color reproducibility. Silver halide photographic materials have been widely used since they have high photosensitivity and excellent image properties. However, silver halide photographic materials that use a large amount of silver have been seriously affected by the recent shortage of silver resources and the resulting rise in raw material costs, and the development of technology that can save the amount of silver has been serious. It is requested. As one of the techniques to meet this demand, silver-saving silver halide photographic materials have been proposed, and several techniques have already been proposed. For example, as described in Japanese Patent Publication No. 49-13576, by introducing a substituent to the active site of a color coupler, conventionally four atoms of silver were required to form one molecule of dye. In contrast, 2
A technique using a so-called two-equivalent type coupler in which atomic silver is sufficient is known. With this method, it is possible to theoretically reduce the amount of silver used to one half of that when using a conventional so-called 4-equivalent type coupler, but in reality, the amount of silver used can be reduced compared to the 4-equivalent type coupler. Since the efficiency is high, it is possible to reduce the amount by half or more. Even so, the amount of silver that can be achieved using this method is limited to about one-third of the current amount, and no further progress can be expected. Another method focuses on the image silver obtained by imagewise exposure and development of a silver halide photographic light-sensitive material, and uses this silver as a catalyst to more efficiently remove the oxidation products of the developing agent. So-called dye image reinforcement methods are known in which dye images are produced, thereby forming dye images of high density. According to this method, the developed silver can be recycled and used many times, so a dye image can be obtained extremely efficiently, and the amount of silver can be greatly reduced. Conventional techniques for reinforcing dye images in silver halide photographic materials include a method for reinforcing dye images with a peroxy compound, as described in US Pat. No. 1,268,121, for example. As described in JP-A-48-9728 and JP-A-48-9729, a dye image reinforcement method using the catalytic action of a cobalt complex is known as a typical technique. A similar method of reinforcing dye images is also described by G.S. Friedman (J.
History of Color Photography (S.Friedman)
Photography (1956), page 406, suggests the possibility of dye image enhancement using hydrogen peroxide and paraphenylenediamine. All of these methods have the effect of increasing dye image density extremely effectively, and are extremely effective means from the standpoint of saving silver resources. However, when a conventionally known silver halide color photographic light-sensitive material is processed by the dye image reinforcing method described above, it suffers from significant color turbidity and poor color reproducibility. In conventional silver halide color photographic materials processed by normal processing methods without this reinforcing treatment, developing agent oxides generated in one layer are not only contained in that layer but also in other layers. spread,
Color turbidity occurs as a result of reaction with couplers in other layers, but in the dye image reinforcement method described above, not only the developing agent oxide but also the image silver produced by development is released as a catalyst. The oxidizing agent diffuses into other layers, oxidizes the developing agent generated in the other layer, and causes a coupling reaction with the coupler in the other layer, resulting in color turbidity. For example, silver halide color photographic light-sensitive materials have been known in which color turbidity is prevented by containing a developing agent oxide scavenger in the intermediate layer of the light-sensitive material, as shown in US Pat. No. 2,360,290. When these conventional silver halide color photographic materials are applied to the dye image reinforcement method of the present invention, color turbidity cannot be prevented. Furthermore, various techniques have been proposed for preventing color turbidity during color development for silver halide color photographic materials processed by the dye image reinforcement method described above, but none of them are currently satisfactory. . The present invention has been made in view of the above points, and it is an object of the present invention to provide a method for forming a dye image by a dye image reinforcement method, which is free from color turbidity and has good color reproducibility. The above object of the present invention is to have a plurality of light-sensitive silver halide emulsion layers and at least one non-light-sensitive intermediate layer on a support, and each of the plurality of silver halide emulsion layers has a coating amount of 1.5 mg/silver. The intermediate layer is coated so that the amount of hydrophilic colloid is 10 mg/100 cm ² or ^more , and the intermediate layer is coated with a developing agent oxidizing agent scavenger of 1 to 10 mg/100 cm 2 or less.
A dye image forming method is achieved, which comprises exposing and developing a silver halide color photographic light-sensitive material containing 100 cm ² and then treating it with a color reinforcement agent in the presence of image silver and a color developing agent. Ru. The multilayer silver halide emulsion layer in the present invention is
One of the important requirements is that the amount of silver applied is 1.5 mg/100 cm ² or less. The amount of coated silver in one silver halide emulsion layer is 1.5mg/
When the amount is more than 100 cm ² , it is not possible to substantially prevent color turbidity during color development, regardless of the structure and composition conditions of the intermediate layer and other photographic constituent elements. This is because in a silver halide emulsion layer in which the amount of silver coated is greater than the above specified amount, the amount of image silver produced during development processing will inevitably increase, so the release of oxidizing agent will be large and excessive, especially in high density areas. This will diffuse not only into the emulsion layer but also into other emulsion layers and oxidize the color developing agent contained in the other emulsion layers.
This is because color turbidity occurs as a result of a coupling reaction with the coupler here. In order to solve this problem, it is conceivable to use a developing agent oxidizing agent scavenger in the intermediate layer in a larger amount than specified in the present invention, but if such a large amount is used, there will be an adverse effect on photographic performance such as desensitization. cannot be adopted. Another aspect of the present invention is that the intermediate layer in the present invention, that is, the intermediate layer interposed between the silver halide emulsion layers, is coated so that the amount of hydrophilic colloid is 10 mg/100 cm ² or more. This is an important requirement. The amount of hydrophilic colloid in the intermediate layer is 10 mg/
When the amount is less than 100 cm ² , color turbidity can be substantially prevented within the range in which the developing agent oxidizing agent capture agent contained in the intermediate layer can exert its effect without adversely affecting photographic performance. Can not do it. Another important requirement of the present invention is that a developing agent oxidizing agent trapping agent is added to the intermediate layer in a range of 10 mg/100 cm ² . As mentioned above, the amount of coated silver in the silver halide emulsion layer is 1.5 mg/100 cm ² or less, and the amount of hydrophilic colloid in the intermediate layer interposed between the emulsion layers is 10 mg/100 cm 2 or less.
mg/100cm ² or more, and the developing agent oxidizing agent scavenger used in the present invention is added to the intermediate layer within the specified content range, and the above-mentioned object of the present invention can be achieved only when the content is within the specified content range. . If the content of the oxidizing agent trapping agent is more than 10 mg/100 ^cm2 , it will adversely affect photographic performance such as desensitization, and if the content is more than 10 mg/100 cm
When it is less than 100 cm ² , the effect of preventing color turbidity cannot be exhibited regardless of the structure and composition of the emulsion layer and intermediate layer. The intermediate layer in the present invention refers to a non-photosensitive hydrophilic colloid layer interposed between silver halide emulsion layers. When a non-photosensitive hydrophilic colloid layer is provided between the lowermost silver halide emulsion layer and the support, the amount of the hydrophilic colloid is set to 10 mg/100 cm ² as in the present invention. It is preferable to do so, and it is further preferable that the hydrophilic colloid layer contains a developing agent oxidizing agent scavenger in an amount within the scope of the present invention. As a result, the developing agent oxidizing agent capture agent in the hydrophilic colloid layer captures the oxidizing agent released and diffused from the silver halide emulsion layer above the hydrophilic colloid layer, and The amount of oxidant migrating to the intermediate layer can be reduced. The developing agent oxidizing agent capture agent used in the present invention may be any agent as long as it is cross-oxidized with the oxidizing agent, and representative specific examples particularly preferred in the present invention include the following. [Exemplary compounds] (A) Hydroquinone derivatives [1] 2,5-di-t-butylhydroquinone [2] 2,5-di-t-octylhydroquinone [3] 2-octylhydroquinone [4] 2-sec-dodecyl Hydroquinone [5] 2,5-sec-dodecylhydroquinone (B) bishydroquinone derivative [6] 2,2'-methylenebis-5-n-octadecylhydroquinone [7] 2,2'-methylenebis-(5-t-butyl -4-methoxyphenol) [8] 1,1'-methylenebis-(2,5-dimethoxy-4-octadecylbenzene) [9] 2,2'-iso-butylidenebis-(5-
t-butyl-4-methoxyphenol) (C) Phenol derivative [10] 2,6-di-t-butylphenol [11] 2,5-di-t-butylphenol [10] 4-hydroxymethyl-2. 6-G-
t-Butylphenol [13] 2,6-dibutylhydroxytoluene [14] 2-t-butyl-4-methoxyphenol [15] 2,4,6-t-butylphenol (D) Bisphenol derivative [16] 2・2'-Butylidenebis-(4-methyl-6-t-butylphenol) [17] 2,2'Methylenebis-(4-methyl-
6-t-butylphenol) [18] 2,2'-methylenebis-(4-ethyl-6-t-butylphenol) [19] 4,4'-butylidenebis-(6-t-
butyl-m-cresol) [20] 4,4'-methylenebis-(6-t-butyl-m-cresol) [21] 4,4'-thiobis-(6-t-butyl-m-cresol) [22] ] 2,2'-thiobis(4-methyl-6-
t-Butylphenol) (E) Ascorbic acid derivative [23] 6-α-isoascorbyl palmitate [24] 6-l-ascorbyl laurate [25] 6-l-ascorbyl benzoate [26] Ascorbyl-2, 3. 5-Triacetate-6-palmitate (F) Chroman derivative [27] 2,2'-dimethyl-4-isopropyl-6-hydroxy-7-t-butylchroman [28] 2,2,4-trimethyl-6-hydroxy -7-t-butylchroman [29] 2,2,4-trimethyl-6-hydroxy-7-t-octylchroman The developing agent oxidizing agent capture agent used in the present invention is not limited to the above-mentioned ones. It is sufficient to use at least one type of these oxidizing agent scavengers, but two or more types may be used in combination depending on the purpose. The developing agent oxidizing agent scavenger described above is disclosed in, for example, US Pat.
Specification No. 2360290, Specification No. 2735765, Tokukosho
Publication No. 48-31256, US Patent No. 2728661,
It is described in the specification of the same No. 3432300. The developing agent oxidizing agent scavenger used in the present invention may be dissolved, for example, in a high-boiling point solvent or a low-boiling point solvent that is hardly miscible with water, and dispersed in the form of fine particles in a suitable hydrophilic colloid solution such as gelatin before being added. I can do it. High-boiling solvents that are poorly miscible with water used for such purposes are described, for example, in U.S. Pat.
Specification No. 2272191, Specification No. 2322027, Specification No.
Dibutyl phthalate, dibutyl lauroylamide, torqueresyl phosphate, etc. described in 2533514, etc. can be used, and in addition, various high-boiling point solvents used for dispersing oil-soluble couplers in gelatin can be used. can be used. Further, depending on the purpose, it may be added after being dissolved in a water-miscible solvent such as dimethylformamide, dimethylsulfoxide, or acetone. The hydrophilic colloid used in the intermediate layer in the present invention is generally gelatin, and other gelatin derivatives such as phthalated gelatin, methacrylate gelatin, colloidal albumin, cellulose derivatives, polyvinyl alcohol,
Polyvinyl compounds such as polyvinylpyrrolidone, acetyl cellulose, water-soluble ethanolamine, cellulose acetate, etc. can also be used in combination with gelatin. The silver halide used in the silver halide color photographic light-sensitive material according to the present invention is, for example, silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. These silver halide emulsions are prepared by any known method. For example, the silver halide emulsion used in the present invention may be a so-called compound emulsion, a Lippmann emulsion, a copper grain emulsion, or an emulsion that has been optically or chemically fogged in advance, and these emulsions are used in photographic materials. It is selected appropriately depending on the type and purpose. Further, the type of silver halide, content and mixing ratio of silver halide, average grain size, size distribution, etc. are similarly selected appropriately depending on the type and use of the photographic light-sensitive material. For example, in photographic materials that require relatively low sensitivity and high image quality, emulsions mainly consisting of silver chloride emulsions with fine grains and narrow size distribution are used; , an emulsion with relatively large grain size and low silver chloride content is used. Further, in direct reversal type photographic materials, an emulsion to which a capri is added in advance is used. These silver halides are activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine, etc.; selenium sensitizers; reduction sensitizers such as stannous salts, polyamines, etc.; noble metal sensitizers such as gold sensitizers. Examples of agents include potassium aurithiocyanate, potassium chloroaurate, 2-oresulfobenzothiazole methochloride, and sensitizers of water-soluble salts such as ruthenium, rhodium, and iridium, specifically ammonium chloroparadate, potassium, etc. Chloroplatinate, sodium chloroparadide, etc. (some of these act as sensitizers or fog suppressants depending on the amount); alone or in combination as appropriate (for example, gold sensitization); Chemical sensitization may be carried out by using a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.). Furthermore, this silver halide can be optically sensitized to a desired wavelength range, for example, by using an optical sensitizer such as a cyanine dye such as a zeromethine dye, a monomethine dye, a dimethine dye, a trimethine dye, or a merocyanine dye. can be optically sensitized (for example, by superchromatic sensitization). This silver halide constitutes a light-sensitive emulsion layer dispersed in a suitable hydrophilic colloid such as gelatin, and the light-sensitive emulsion layer and other non-light-sensitive constituent layers such as a protective layer, a filter layer, etc. As the hydrophilic colloid used for the constituent elements, the hydrophilic colloid for the intermediate layer described above can be used. The silver halide color photographic light-sensitive material of the present invention contains couplers for forming color images, and useful couplers include, for example, open-chain methylene yellow couplers, 5-pyrazolone magenta couplers, phenolic couplers, Examples include naphthol-based cyan couplers,
These couplers may be so-called 2-equivalent type or 4-equivalent type couplers, and in combination with these couplers, azo-type colored couplers, osazone-type compounds, and development-diffusive dye-releasing couplers can be used. It is also possible to use Further, at this time, it is desirable to use a so-called colorless coupler, which is colorless before color development, in combination with the above-mentioned masking coupler. Furthermore, in order to improve photographic characteristics, so-called computing couplers, DIR couplers, BAR (Bleach Accelerator Releasing) are used in combination with various couplers.
It can also include couplers called couplers. Open-chain ketomethylene compounds have traditionally been used as yellow couplers.
For example, pivallylacetanilide type yellow couplers are described in French Patent No. 1291110, etc., and benzoylacetanilide type yellow couplers are described in Japanese Patent Publication No. 19031/1983, US Patent No. 2875051, etc. U.S. Pat.
3408194 specification, U.S. Patent No. 3447928 for active point -o-acyl substitution, JP-A-48-29432 for active point substitution with hydantoin compound, JP-A-48-66834 for active point substitution with urazole compound ,
Patent application for substitution of active site with succinimide compound 1972-
Specification No. 119053, Japanese Patent Application No. 1987-7930 for active point substitution with a monooxoimide compound, JP-A-49-10736 for active point substitution with a pyritazone compound, British Patent No. 944490 specification for active point substitution with fluorine British Patent No. 780507 for active point chlorine or bromine substitution, British Patent No. 780507 for active point -o-sulfonyl substitution
Those described in the specification of No. 1092506 etc. can be used as effective yellow couplers. Among these yellow couplers, those that are particularly effective are described in U.S. Patent No. 3408194, Japanese Patent Application Laid-Open No. 1982-29432, Japanese Patent Application No. 79309-1982, and Japanese Patent Application Laid-Open No. 1983-1989.
Couplers described in Japanese Patent No. 66834 can be mentioned. Examples of magenta couplers used in the present invention include pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indazolone compounds. As a pyrazolone mazeta coupler, U.S. Patent No. 3127269
US Pat. No. 2,600,788, US Pat. No. 3,519,429, US Pat. No. 3,419,391, US Pat. No. 3,062,653, British Patent No.
Specification No. 1342553, West German Patent No. 2162778,
Those described in Japanese Patent Application Laid-open No. 49-29639, Japanese Patent Application No. 44-8433, etc., pyrazolotriazole maze couplers are described in West German Patent No. 1810464, Peruvian Patent No. 792525, etc. The pyrazolinobenzimidazole magenta couplers described are described in U.S. Patent No. 3061432, Japanese Patent Publication No. 46-60479, and West German Patent No.
As the indazolone magenta coupler, those described in Belgian Patent No. 769116 are used. Particularly preferable magenta couplers in the present invention include those described in Japanese Patent Application No. 44-8433 and 3-3 described in U.S. Pat. No. 3,127,269.
Examples include anilinopyrazolone magenta coupler. Furthermore, useful cyan couplers used in the present invention include, for example, the phenolic compounds described in U.S. Pat. No. 2,423,730, U.S. Pat. No. 2,801,171, U.S. Pat. , U.S. Patent No.
Active point -o-aryl substituted naphthol compounds described in Specification No. 2474293, British Patent No. 1084480, etc., JP-A-47-37425, Japanese Patent Application No. 1984-57829
specification, patent application No. 1983-69866, patent application No. 1973
Examples include phenol and naphthol compounds described in -10787, Japanese Patent Application No. 16057, Japanese Patent Application No. 49-25388, Japanese Patent Application No. 37160-1980, etc. . As the colored magenta coupler, a compound in which the active site of a colorless magenta coupler is substituted with arylazo or heteroarylazo is used, such as those described in US Pat. No. 3005712, US Pat. No. 2983608, and US Pat. No. 2801171. , British Patent No. 937621, Special Publication No. 1973-
Compounds described in Japanese Patent No. 27930 can be mentioned. Examples of colored cyan couplers include active site arylazo-substituted compounds described in US Pat. No. 3,034,892, US Pat.
Furthermore, Japanese Patent Application Publication No. 50-10135, Japanese Patent Application Publication No. 50-25228, Japanese Patent Application Publication No. 50-117422, Japanese Patent Application Publication No. 50-120334,
Masking couplers of the type described in Publication No. 50-130441 and British Patent No. 1074480, which react with the developing oxidant and cause the dye to flow out into the processing bath, can also be used. U.S. Patent No. 1 for a computing coupler
Those described in the specification of No. 2742832, for example, citradinic acid, etc. can be used, and as the Weis coupler, those described in West German Patent No. 1155676 can be used. The couplers used in the present invention can be of various types as described above, and the amount added is at least 50% in excess of the stoichiometric amount based on the effective amount of silver in the coupler-added layer. It is preferable to achieve the object of the present invention more effectively. A silver halide emulsion containing a photographic coupler etc. prepared as described above is passed through an intermediate layer consisting of a hydrophilic colloid containing a developing agent oxidizing agent scavenger etc. in the above amount, as necessary. Together with the subbing layer, filter layer, anti-curl layer, protective layer, etc., the amount of coated silver in the emulsion layer is 1.5 mg/100 cm ² or less, and the amount of hydrophilic colloid binder in the intermediate layer is 10 mg/100 cm ^{2 .} By forming the layers on the support as described above, the silver halide color photographic light-sensitive material according to the present invention is prepared. Supports that can be used at this time include paper, laminated paper (for example, a laminate of polyethylene and paper), glass,
Examples include film or sheet substrates of cellulose, acetate, cellulose nitrate, polyester, polycarbonate, polyamide, polystyrene, polyolefin and the like. These supports can be subjected to various surface treatments such as hydrophilic treatment for the purpose of improving adhesion to each constituent layer, such as saponification treatment, corona discharge treatment, subbing treatment, and setting treatment. etc. are performed. The photosensitive material basically consists of at least a support, two or more emulsion layers provided thereon, and an intermediate layer interposed between the emulsion layers, but as described above, It is generally composed of several layers or more, with appropriate layers at various positions depending on the purpose, and if necessary, the developing agent oxidizing agent trapping agent according to the present invention is contained in the intermediate layer. In addition, it may be contained in other constituent elements such as an emulsion layer. In addition, the emulsion layer itself is composed of a layer containing silver halide with relatively high sensitivity and a layer containing silver halide with relatively low sensitivity, which are sensitized to the same wavelength range or different wavelength ranges. It may be configured as follows. Furthermore, the silver halide color photographic light-sensitive material according to the present invention has various photographic properties in the emulsion layer, intermediate layer, and/or other constituent elements (for example, subbing layer, filter layer, protective layer, image-receiving layer, etc.) depending on the purpose. It can contain additives for use. Examples of such photographic additives include stabilizers (mercury compounds, triazoles, azaindenes, quaternary benzothiazolium, zinc or cadmium salts, etc.); sensitizers such as quaternary ammonium salts, polyethylene glycols, etc. Membrane property improvers such as glycerin, dihydroxyalkanes such as 1,5-pentadiol, esters of ethylene bisglycolic acid, bisethoxydiethylene glycol sacinate, amides of acrylic acids, emulsified dispersions of polymers, etc.; Hardeners such as formaldehyde, halogen-substituted fatty acids such as mucochromic acid, mucobromic acid, compounds with acid anhydride groups, dicarboxylic acid chlorides, disulfonic acid chlorides, biesters of methanesulfonic acid, aldehyde groups having 2 to 3 carbon atoms. Sodium bisulfite derivatives of dialdehydes, bisaziridine, ethyleneimines, etc.; spreading agents such as saponin, lauryl or oleyl monoethers of polyethylene glycol, sulfated and alkylated polyethylene glycol salts, etc.; coating aids; For example, sulfosuccinates; organic solvents such as coupler solvents (high-boiling organic solvents and/or low-boiling organic solvents, specifically dibutyl phthalate, tricresyl phosphate,
Acetone, methanol, ethanol, ethylene cell solve, etc. ); so-called DIR compounds that release color development inhibitors and produce substantially colorless compounds during color development, other antistatic agents, antifoaming agents,
Various agents such as ultraviolet absorbers, fluorescent whitening agents, anti-slip agents, matting agents, halation or irradiation inhibitors can be used alone or in combination. The silver halide color photographic light-sensitive material used in the present invention is preferably applied to various uses in which it is processed by a dye image reinforcing method. For example, negative photosensitive materials for general use, reversal photosensitive materials for general use, positive photosensitive materials for general use, direct positive photosensitive materials, special use (for example, printing, X-ray, high resolution, infrared, ultraviolet, etc.) halogenated Used in silver color photographic materials. The dye image reinforcing method applied to the processing of the silver halide color photographic light-sensitive material according to the present invention is a method having the step of processing with a color reinforcing agent in the presence of image silver and a color developing agent after development. Name everything. Here, the term “color reinforcing agent” refers to the above-mentioned US Pat.
It may be any of the peroxy compounds described in JP-A No. 1268121, etc., and the cobalt complexes described in JP-A-48-9728, etc., but especially the silver halide color photographic light-sensitive material according to the present invention. As the coloring reinforcing agent used in the reinforcing treatment method, hydrogen peroxide and a cobalt-6 combination complex are desirable. A dye image reinforcing method using the above cobalt complex as a coloring reinforcing agent is described in the above-mentioned U.S. Pat.
The method described in detail in the specification of No. 1268121 etc. can be adopted. That is, a photographic element in which the reinforcing processing bath contains a cobalt() complex as an active ingredient and an imagewise distribution of image silver as a catalyst is brought into contact with the above-mentioned reinforcing solution in the presence of a reducing agent or color developing agent. can be effectively employed in the silver halide color photographic light-sensitive material according to the present invention. In the above dye image reinforcing method, the cobalt() complex is most preferably a cobalt hexacoordination complex, and the reducing agent is, for example, an aromatic
Preferably, the color developing agent is a color developing agent such as a class amino compound. Further, regarding the dye image reinforcing method using the peroxy compound, for example, hydrogen peroxide solution as a coloring reinforcing agent, the above-mentioned Japanese Patent Publication No. 49-46419, Japanese Patent Application Laid-open No. 51-7929, and Japanese Patent Application Laid-open No. 16023-1989 disclose ,
The methods described in detail in JP-A No. 51-36136, Japanese Patent Application No. 127936-1980, etc. can be effectively employed as a method for processing the silver halide color photographic light-sensitive material according to the present invention. . That is, the photosensitive material after exposure is developed to form image silver, and then processed with a reinforcing processing solution containing hydrogen peroxide in the presence of a color developing agent to form an image distributed as per the image. It is possible to employ a method in which an oxidized product of a developing agent is more efficiently produced using silver as a catalyst, thereby forming a dye image with high density. Further, in the dye image reinforcing method using hydrogen peroxide as a color reinforcing agent, the silver halide color photographic light-sensitive material according to the present invention can be used to remove silver halide from unexposed areas after developing the light-sensitive material before the color reinforcing treatment. The reinforcing treatment can also be effectively carried out by a method of treating with a solution containing a deactivating compound (deactivating agent) or a removing compound (silver halide solvent). The color developing agent used in the dye image reinforcing method employed in the processing of the silver halide color photographic material according to the present invention may be added to the silver halide photographic material from the beginning, or may be added to the silver halide color photographic material from the beginning. The color developing agent may be included in the developer, or a solution containing a color developing agent may be provided separately and the color developing agent may be included in the photosensitive material by means such as dipping or spraying. Preferred color developing agents are typically p-aminophenol or p-phenylenediamine, and specific examples include p-aminophenol, diethyl-p-phenylenediamine hydrochloride, and monomethyl-p-phenylenediamine. p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-ano-5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-
N-dodecylamine)-toluene, N-ethyl-
N-β-methanesulfonamide doethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-
N-β-methanesulfonamidoethyl-4-aminoaniline, 4-N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl, N・N-diethylaniline hydrochloride, 4-amino -3-methyl-N-ethyl-N-
β-hydroxyethylaniline sulfate, 4
-amino-3-β-(methanesulfonamido)ethyl-N・N-diethylaniline, 4-amino-
N-(2-methoxyethyl)m-toluidine and the like can be mentioned. These color developing agents can be used alone or in combination of two or more, and in the present invention, black and white developing agents such as hydroquinone can be used in combination. In addition to these, alkaline agents such as sodium hydroxide, ammonium hydroxide,
It contains sodium carbonate, sodium sulfate, sodium sulfite, etc., and may further contain various additives such as alkali metal halides such as urium bromide, or development regulators such as citradinic acid. The silver halide color photographic light-sensitive material of the present invention which has been subjected to color development processing in this way is directly or briefly washed with water (rinsed), or passed through a prebath containing a color developing agent, and then reinforced with a solution containing hydrogen peroxide. be done. The concentration of the hydrogen peroxide solution used in the dye image reinforcing method varies depending on the embodiment, such as the type of photosensitive material, the type of color developing agent, and the running speed, but is generally 0.1 to 40%, preferably 0.3%.
~12% solutions can be used. The reinforcing treatment with a solution containing hydrogen peroxide in the present invention can be carried out by a conventional dipping method, spraying method, or intermittent dipping method. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the embodiments of the present invention are not limited thereby. Example 1 Samples 1 to 14 were prepared by sequentially applying the following layers onto resin-coated photographic paper. (1) Blue-sensitive silver halide emulsion layer 2-(1-benzyl-2.4 as a coupler)
-dioxyimidazolidin-3-yl)-2-
Dissolving pivalyl-2'-chloro-5'-[4-2,4-di-t-pentylphenoxy)butanamide]acetanilide in dibutyl phthalate,
After protection was dispersed in an aqueous gelatin solution, it was mixed with a blue-sensitive silver chlorobromide emulsion, coated in an amount shown in Table 1 below, and dried.
The amount of coupler applied was stoichiometrically 200% based on the effective amount of silver. (2) First intermediate layer 2,5-di-t as a developing agent oxidizing agent capture agent
- Gelatin containing octylhydroquinone was applied so that the oxidizing agent scavenger and gelatin were in the amounts shown in Table 1 below. (3) Green-sensitive silver halide emulsion layer 3-(2-chloro-5-[1-
(octadecyl)succinimide]anilino}−
1-(2,4,6-trichlorophenyl)-5-
Pyrazolone was dissolved in dibutyl phthalate, protected and dispersed in an aqueous gelatin solution, mixed with a green-sensitive silver chlorobromide emulsion, coated in an amount shown in Table 1, and dried. In addition,
The amount of coupler was applied in a stoichiometric excess of 200% based on the effective amount of silver. (4) Second intermediate layer 2,5-di-t as a developing agent oxidizing agent capture agent
- Gelatin containing octylhydroquinone was applied so that the oxidant scavenger and gelatin were in the respective amounts shown in Table 1. (5) Red-sensitive silver halide emulsion layer 2-[2-(2,4-di-t-
Pentylphenoxy)butanamide]-4,6
-Dichloro-5-methylphenol is dissolved in dibutyl phthalate, protected and dispersed in an aqueous gelatin solution, then mixed with a red-sensitive silver chlorobromide emulsion and coated so that the amount of coated silver is as shown in Table 1. and dried. The amount of coupler applied was stoichiometrically 200% based on the effective amount of silver. (6) Protective layer Gelatin was applied at a concentration of 9 mg/100 cm ² .

[Table] The obtained samples 1 to 14 were wedge-exposed to blue light, green light, and red light, respectively, and processed in the following processing steps. Processing steps (processing temperature: 30°C) Development: 1 minute and 30 seconds Reinforcement: 4 minutes Washing with water: 1 minute Bleach-fixing: 1 minute Washing with water: 1 minute Stabilization: 1 minute The composition of the processing solution used is as follows. Developer Anhydrous sodium sulfite 10 g Hydroquinone 2 g Phenidone 0.6 g Potassium carbonate 20 g N-ethyl-N-β-methanesulfonamido-ethyl-4-amino-3-methylaniline sulfate 11 g Sodium hydroxide 5 g 2 -Mercaptobenzimidazole 10 mg 5-Nitrobenzimidazole 1.5 g Water was added to bring the concentration to 1, and the pH was adjusted to 11. Reinforcing solution (bath) 35% hydrogen peroxide solution 25ml Water was added to adjust the pH to 1 and the pH was adjusted to 8. Bleach-fixer ethylenediaminetetraacetate iron ammonium
61.0g Ammonium thiosulfate 124.5g Sodium metabisulfite 2.7g 2-Ammonium ethylenediaminetetraacetate
Add 5.0g of water to make the solution 1 and adjust the pH to 6.5. After adding 20 ml of stabilized glacial acetic acid and 800 ml of water, the pH was adjusted to 3.5 with sodium acetate, and then water was added to bring the pH to 1. For each treated sample, the blue density (D _B ), green density (D _G ), and red density (D _R ) were measured using a densitometer (manufactured by Konishiroku Photo Industry Co., Ltd., model PD-60). D _G at D _B =1.0 when exposed to blue light,
D _B and D at D _G = 1.0 when exposed to green light
_R and the D _G value at D _R =1.0 when exposed to red light were as shown in Table 2 below.

[Table] As is clear from Table 2, it can be seen that the samples according to the present invention (sample numbers 5, 6, 8, and 9) have substantially no interlayer color turbidity. In contrast, samples (sample Numbers 1-4, 7, 10
~14), it can be seen that there is significant color turbidity between the layers. Example 2 Samples 1 to 14 of Example 1 were each subjected to wedge exposure in the same manner as in Example 1, and processed through the following processing steps. Processing steps (processing temperature: 30°C) Development: 3 minutes Reinforcement: 4 minutes Bleach-fixing: 1 minute and 30 seconds Washing: 1 minute Stabilization: 1 minute The composition of the processing solution used is as follows. Developer Benzyl alcohol 10 ml Anhydrous potassium sulfite 2 g Potassium bromide 0.4 g Hydroxylamine sulfate 2 g 4-Amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine-di-paratoluenesulfonate 5 g Potassium carbonate 30 g Ethylenediaminetetraacetic acid-4-sodium 5 g Water was added to bring the concentration to 1, and the pH was adjusted to 10.1. Reinforcement liquid Benzyl alcohol 15 ml Hexaammine cobalt chloride 10 g Potassium bromide 2 g Anhydrous potassium carbonate 7.5 g Anhydrous potassium sulfite 2 g Sodium ethylenediaminetetraacetate 5 g Water was added to bring the pH to 1, and the pH was adjusted to 10.1. The same bleach-fix solution and stabilizing solution as in Example 1 were used. For each treated sample, _DG in the case of blue light exposure, _DB and _DR in the case of green light exposure, and _DG in the case of red light exposure were measured in the same manner as in Example 1. As a result, samples according to the present invention (sample number 5,
6, 8 and 9), similar to the results of Example 1 above, no color turbidity was observed between the layers, and it was confirmed that they had excellent color reproducibility. On the other hand, samples not based on the present invention (sample numbers 1-4, 7, 10-14)
In both cases, interlayer color turbidity was significant, and color reproducibility was extremely poor. Example 3 In sample 5 of Example 1, 2.5-di-t-
Samples 15 to 24 were treated under the same conditions as Sample 5, except that a developing agent oxidizing agent scavenger shown in Table 3 below (indicated by the number of the exemplified compound) was added in the amount shown in the table instead of octylhydroquinone. It was created.
The sample was processed in the same way as in Example 1, and D _B and D _R at D _G =1.0 for green light exposure in the same way.
was measured. The results were as shown in Table 3.

【table】

[Table] As is clear from Table 3, it can be seen that virtually no interlayer color turbidity was observed in all the samples according to the present invention.

Claims (1)

[Scope of Claims] A support has a plurality of photosensitive silver halide emulsion layers and at least one non-photosensitive intermediate layer, each of the plurality of silver halide emulsion layers having a coated silver amount of 1.5.
mg/100cm ² or less, and the intermediate layer is coated so that the amount of hydrophilic colloid is 10 mg/100cm ² or more, and the intermediate layer contains a developer oxidizing agent capture agent. A method for forming a dye image, which comprises exposing and developing a silver halide color photographic material containing up to 10 mg/100 cm ² , and then treating the material with a color reinforcing agent in the presence of image silver and a color developing agent. 2. The method for forming a dye image according to claim 1, wherein the hydrophilic colloid is gelatin.