JPH038535B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a color image forming method that does not require washing with water and causes less staining. In recent years, in urban areas, the cost of supplying washing water for photographic processing has become high, and discharging washing wastewater also costs a huge amount of money, so there is a strong desire to conserve water. Furthermore, due to the rise in the price of petroleum, there is a problem in that it costs a lot of money to heat the washing water. However, it was impossible to remove the water washing by ordinary photosensitive material processing. This is because, if water washing is excluded, processing chemicals are included, which can cause problems such as stains due to precipitation on the surface of the sensitive material, discoloration and fading of silver images, and fading and discoloration of color images in the case of color sensitive materials. . Eliminating the fixing process (in the case of color sensitive materials, bleaching and fixing, ie, desilvering process) is advantageous because it is simple and quick, but it is disadvantageous because it increases staining. The main stains are silver stain and color stain in the case of color photosensitive materials, but in this case both increase. Conversely, in the case of black and white photosensitive materials, stains are removed by fixing, but in the case of color photosensitive materials, desilvering reduces the silver stains, but color stains remain. If both washing, fixing, or desilvering steps are omitted, it is inevitable that the stain will increase further.
If a normal photosensitive material is subjected to normal processing without an intensifying bath, staining cannot be prevented even if processing is performed using a low PH bath. It is also known that in general, with sensitive materials having a very low silver halide content, the fixing or bleach-fixing steps can be omitted. This is natural because there is less silver, so less silver stain occurs. However, in the case of color sensitive materials, color stains occur unless they are thoroughly washed with water. For example lineagraph 705
There are color photosensitive materials on the market that do not require washing, but they tend to stain over time. The first object of the present invention is to provide a color image forming method that can omit water washing, and the second object is to provide a color intensified image that causes less staining and has a high amplification rate, using a color photosensitive material with an extremely small amount of silver. Thirdly, it provides a color intensification image forming method that requires a small number of processing solutions. We have found that these stains can be effectively prevented by post-processing with a low PH bath when intensifying a photosensitive material with a low silver content, and have completed the present invention. The object of the present invention is to process a silver halide color light-sensitive material with a low silver content that has been imagewise exposed to light in the presence of a reducing agent and, if necessary, a coloring agent, using a peroxide, a halogen acid, an iodoso compound, and a cobalt () complex. After forming a reinforced color image by acting with at least one intensifying agent consisting of a compound, it is treated with a solution containing a dilute buffering agent with a pH of 2 to 7 without desilvering, and then washed with water. This was achieved using a color image forming method that is characterized by drying without drying. Here, in the present invention, "without washing" means washing the photosensitive material with water only. It is actually contrary to expectations that staining can be prevented by post-treatment with a low PH bath when intensifying treatment is performed. Conventionally, many methods are known for developing and intensifying silver halide photosensitive materials to enhance image formation.
Oxidation of a color developing agent based on paraphenylenediamine by decomposition of hydrogen peroxide on a catalyst surface in the presence of a color former, followed by formation of a dye by coupling with a color former (this development is called color intensification).
For example, see Friedman's History of
It is described on page 406 of Color Photography 2nd Ed. (1956). In addition, descriptions of various other photographic methods that utilize the decomposition of peroxide on the surface of precious metals can be found in West German Patent Application (OLS) No. 1813920;
No. 1950102, No. 1961029, No. 2044833, No.
No. 2044993, No. 2056360, No. 2056359 and No.
2120091 etc. On the other hand, descriptions of color enhancement methods using cobalt complex salts on the surface of noble metals are available, for example, in JP-A-48-9728, JP-A-48-9729, and JP-A-48-9729.
No. 48130, No. 49-84229, No. 49-84240, No. 49
-97614, 49-102340, 49-102314, etc. Further, color intensification methods using halous acids such as chlorous acid are described in JP-A-51-53826 and JP-A-52-13335. In addition, the color intensification method using iodosobenzoic acid and other iodosobenzoic acid compounds is disclosed in Japanese Patent Application Laid-Open No. 52-73731.
listed in the number. Compounds that have reinforcing effects such as peroxides, halous acids, iodoso compounds, and cobalt () complex compounds are called intensifying agents, and processing baths containing these intensifying agents are called intensifying baths. . Among these, peroxy compounds or cobalt ()
Color image reinforcement technology that utilizes the catalytic action of complexes is known as a typical technology, and hydrogen peroxide reinforcement is considered to be the most efficient, especially in terms of amplification efficiency. These methods involve imagewise exposure of a silver halide photosensitive material, development using the resulting developed silver as a catalyst, and efficient redox reaction between an intensifying agent and a color developing agent on the catalytic silver nucleus. This method is known as a method of producing an oxidized product of the main drug, forming a high-density dye image, and reinforcing the image. In other words, intensification processing is a method in which a color photosensitive material is immersed in an intensification bath after color development, or is immersed in a color developer after black and white development, and then immersed in an intensification bath. After the growth, the color developing agent is retained in the photosensitive material film, and the color developing agent and intensifier are formed on the developed silver nuclei in an intensifying bath using the color developing agent brought in from the photosensitive material. This is commonly referred to as a processing method that enhances images using redox reactions. As the buffering agent used in the present invention, known buffering agents can be used. For example, potassium phosphate-dipotassium phosphate, sodium citrate-hydrochloric acid, sodium citrate-sodium hydroxide, succinic acid-
Borax, acetic acid-sodium acetate, tartaric acid-sodium tartrate, borax-boric acid, sodium diethylbarbiturate-hydrochloric acid, glycine-sodium chloride-hydrochloric acid, lactic acid-sodium lactate, Britton-
Robinson's broad-spectrum buffer and the like can be used. The concentration of buffer agent depends on the type, but it is 1 per processing solution.
A range of ×10 ^-2 mole to /mole is preferable. In particular, since the subsequent water washing process is omitted, the concentration of the buffering agent should be as low as possible, for example, 1 x 10 ^-2 mole to 1 x 10 ^-2 to prevent salt from adhering to the photosensitive material and contaminating the image. mole range is desirable. The pH of the buffer solution is preferably 2 or more and less than 7, but from the viewpoint of the effects of the present invention, the pH is particularly preferably 2 to 5. The solution containing the dilute buffer with pH 2 to 7 of the present invention includes sulfite, bisulfite, metabisulfite, formaldehyde bisulfite adduct, thiosulfate,
It may also contain thiocyanate. When using sulfite, bisulfite, or metabisulfite in a processing solution containing a dilute buffer with a pH of 2 to 7, these have buffering capacity, so other buffers do not need to be used together. good. The amount of these additions is 1×10 ^-2 mole or 1× per treatment solution.
A range of 10 ^-1 mole is desirable. In addition, when thiosulfate, thiocyanate, and formaldehyde bisulfite adducts are used in a processing solution containing a dilute buffer with a pH of 2 to 7, the amount of these added is 1 x 10 ^-3 mole per processing solution. or 1×
A range of 10 ^-1 mole is desirable. The processing solution containing a dilute buffer with a pH of 2 to 7 according to the present invention may optionally contain an aminopolycarboxylic acid or a salt thereof such as ethylenediaminetetraacetic acid, an organic phosphonic acid such as 1-hydroxyethane-1,-diphosphonic acid, etc. or a salt thereof, a hardening agent such as formalin, and an organic solvent such as ethanol, methanol, acetonitrile, and acetone. It may also contain surfactants, antifoaming agents, and the like. The temperature of the processing solution containing a dilute buffer with a pH of 2 to 7 according to the present invention is usually selected between 18°C and 50°C, but 18°C
Lower temperatures and even temperatures above 50°C are possible. As the reducing agent used in the present invention, a color developing agent of P-phenylenediamine derivative, a U.S. patent
P-aminophenol derivative color developing agent in onium salt form as described in No. 3791827 etc., US patent
Dye developer described in No. 2983606, etc., JP-A-48-
A developing agent that reacts with a diffusible dye-releasing (DDR) redox compound described in Japanese Patent Publication No. 33826, an amidrazone compound described in Japanese Patent Publication No. 48-39165, etc., which itself oxidizes to form a dye or lakes. type reducing agents (e.g. telelazonium salts,
2,4-diaminophenol, α-nitroso-β
-naphthol leuco pigments), others, JP-A-1978
Examples include reducing agents capable of forming colored images after oxidation, which are described on pages 9 to 13 of Specification No. 6338. The reducing agent is a developing agent, and in order to form a dye, it must undergo oxidation itself and be coupled with a coloring agent, and the reducing agent itself must be oxidized to form a dye. Some are colored and become non-diffusible pigments through oxidation. In p-phenylenediamine derivative color developing agents, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-5-(N-ethyl-N
-laurylamino)toluene, 4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline sulfate, 2-methyl-4-[N-ethyl-N-
(β-hydroxyethyl)amino]aniline sulfate, N-ethyl-N- as described in U.S. Pat. No. 2,193,015
(β-methanesulfamidoethyl)-3-methyl-
4-aminoaniline sesquisulfate monohydrate, N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide sulfate, N,N-dimethyl-p described in U.S. Pat. No. 2,592,364
-Phenylenediamine hydrochloride, US Pat. No. 3,656,950
4-amino-3- as described in No. 3698525, etc.
Methyl-N-ethyl-N-methoxyethylaniline, 4-amino-3-methyl-N-ethyl-N-
Ethyl-N-β-ethoxyethylaniline and 4-amino-3-methyl-N-ethyl-N-β-
Preferred representative examples include butoxyethylaniline and salts thereof (eg, sulfate, hydrochloride, sulfite, p-toluenesulfonate, etc.). Other Photography by LFAMason
Processing Chemistry (Focal Press, 1966, 226)
Those described on pages 1 to 229 can also be used. There are types of reducing agents that form color images themselves when oxidized, and types that form complexes with metal salts. 3655382
Other examples include 2,4-diaminophenol and α-nitroso-β naphthol. These reducing agents are compounds that are oxidized by the intensifying agent in the presence of the catalytic material, but in the absence of the catalyst the oxidation reaction oxidizes only at a very slow rate, and are themselves developer-forming elements. However, the oxidant reacts with the color forming agent to form an image. General photographic materials contain 3 to 10 g/ ^m2 of silver salt, and printing materials also contain 1 to 4 g/m2 of silver salt.
In ^{the photographic material of the present invention, the amount of coated silver may be 1 g/m 2 or} less, particularly 0.5 g/m ² or less. In the case of multilayer photographic materials, the amount of coated silver is 1 g/layer per photosensitive layer.
m ² or less, especially 0.5 g/m ² or less and 1 mg/m ² or more. The color forming agent used in the present invention is a compound, ie, a coupler, that reacts with an oxidized color developing agent to form a dye. Couplers used in the present invention include the following color-forming couplers, which develop color through oxidative coupling with aromatic primary amine developers (e.g., phenylene diamine derivatives, aminophenol derivatives, etc.) during color development processing. Examples of magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloyl cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusive or polymerized couplers that have hydrophobic properties called ballast groups in their molecules.
The coupler may be either 4-equivalent or 2-equivalent to silver ion. 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). Two or more types of the above-mentioned couplers and the like can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, and the same compound can of course be added to two or more different layers. In order to introduce the coupler into the silver halide emulsion layer, known methods such as the method described in US Pat. No. 2,322,027 can be used. 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), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. di- butoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc., or organic solvents with a boiling point of about 30°C to 150°C, such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, After being dissolved in secondary 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. 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. Silver halide emulsions are usually prepared by mixing a water-soluble silver salt (eg, silver nitrate) solution and a water-soluble halide salt (eg, potassium bromide) solution in the presence of a water-soluble polymeric solvent such as gelatin. In addition to silver chloride and silver bromide, the silver halide includes mixed silver halides such as silver chlorobromide, silver iodobromide,
Silver chloroiodobromide or the like can be used. The average grain size of the silver halide grains (in the case of spherical or approximately spherical grains, the grain size is taken as the grain size, and in the case of cubic grains, the grain size is expressed as an average based on the projected area) is preferably 2μ or less, but it is particularly preferred. Noha
It is 0.4 μ or less. The particle size distribution may be narrow or wide. The shape of these silver halide grains may be cubic, octahedral, or a mixed crystal thereof. Furthermore, two or more types of silver halide photographic emulsions formed separately may be mixed. Furthermore, even if the crystal structure of silver halide grains is uniform throughout,
Also, those with a layered structure with different interior and exterior,
It may be of the so-called conversion type as described in British Patent No. 635,841 and US Pat. No. 3,622,318. Further, either a type in which a latent image is formed mainly on the surface or an internal latent image type in which a latent image is formed inside the particle may be used. These photographic emulsions are described by Mees, “The Theory of Photographic
Process” (The Theory of Photographic Processes), published by MacMillan: P.
“Chimie” by Grafkides
Photographique”
Written by P. Glafkides, which is generally recognized and is also written in books such as Paul Montel (1957).
Chimieet 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). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the methods for reacting the soluble silver salt and soluble halogen salt include one-sided mixing method, simultaneous mixing method,
Any combination thereof may be used. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
As one type of simultaneous mixing method, a method in which PAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion with a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. The soluble salts are usually removed from the emulsion after precipitation or physical ripening, and the long-known Nudel water washing method, which involves gelatinizing gelatin, may be used. Utilizing inorganic salts such as sodium sulfate, anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) A sedimentation method (flocculation) may also be used. The process of removing soluble salts may be omitted. Silver halide emulsions do not undergo chemical sensitization,
Although so-called primitive emulsions can be used, they are usually chemically sensitized. For chemical sensitization, the authors of Glafkids or Zelikman et al. or H. Frieser ed.
Photographischen Prozesse mit
Silberhalogeniden (Akademische
Verlagsgesellschaft, 1968) can be used. That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. are used alone or in combination. be able to. It may be preferable for the photographic material to further contain various additives in order to obtain desired development characteristics, image characteristics, film properties, etc. These additives include iodides in salt form and structural compounds with mercapto free radicals, such as phenylmercaptotetrazole, alkali metal iodide salts, etc. However, it is desirable to avoid using large amounts of these. . For the purpose of increasing sensitivity, increasing contrast, or accelerating development, photographic light-sensitive materials contain, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, quaternary ammonium salt compounds, urethane derivatives, and urea derivatives. , imidazole derivative,
It may also contain 3-pyrazolidones and the like. For example, US Patent No. 2400532, US Patent No. 2423549, US Patent No. 2716062,
It can be used with those described in No. 3617280, No. 3772021, No. 3808003, British Patent No. 1488991, etc. Antifoggants are generally added to the light-sensitive silver halide emulsion layer and non-light-sensitive auxiliary layer of photographic light-sensitive materials. Preferred specific examples include heterocyclic organic compounds such as tetrazole, azaindene, and triazole aminopurine. be. Other additives in photographic materials include
Hardeners, plasticizers, lubricants, surface agents, brighteners and other additives known in the photographic art may also be included. 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, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal,
Poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. In addition to lime-treated gelatin, acid-treated gelatin and enzyme-treated gelatin as described in Bull.Soc.Sci.Phot.Japan.No.1630 (1966) may also be used as the gelatin. or enzymatic decomposition products can also be used. Gelatin derivatives can be obtained by reacting gelatin with various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds. The one obtained by doing so is used. The gelatin. As the graft polymer, a gelatin grafted with a single (homo) or copolymer of a vinyl monomer such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, and styrene can be used. can. Particularly preferred are graft polymers with polymers which are compatible with gelatin to some extent, such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates and the like. Examples of these are U.S. Pat.
It is described in issues such as No. 2956884. If necessary, the photographic emulsion can be spectral sensitized by using cyanine dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or by using them in combination with styryl dye or the like. The photographic light-sensitive material used in the present invention has at least one silver halide emulsion layer on a support, and usually has a red-sensitive silver halide emulsion layer and a green-sensitive silver halide emulsion layer on the support. , has a blue-sensitive silver halide emulsion layer. Or, on a support, a red-sensitive silver halide emulsion layer containing a cyan image-forming coupler, a green-sensitive silver halide emulsion layer containing a magenta image-forming coupler, a blue-sensitive silver halide emulsion containing a yellow image-forming coupler. It has layers. The photographic light-sensitive material may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation.
Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. The photographic material may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups, 4-thiazolidone compounds, benzophenone compounds, cinnamic acid ester compounds, butadiene compounds, benzoxazole compounds, and ultraviolet absorbing polymers can be used. These ultraviolet absorbers may be fixed in the hydrophilic colloid layer. In the photographic light-sensitive material, the photographic emulsion layer and other hydrophilic colloid layers may contain brighteners such as stilbene-based, triazine-based, oxazole-based, or coumarin-based brighteners. These brighteners may be water-soluble, or water-insoluble brighteners may be used in the form of a dispersion. In photographic materials, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like. The light-sensitive material may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. The following known antifading agents can be used in the photographic material used in the present invention, and color image stabilizers can be used alone or in combination of two or more.
Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material used in the present invention contains coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast, sensitization). Various surfactants may be included for various purposes such as. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic interfaces such as alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Activator: Alkyl carboxylate, alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyl taurine, sulfosuccinic acid Contains acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphoric acid ester groups, etc., such as esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphate esters, etc. Anionic surfactants; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts Cationic surfactants such as heterocyclic quaternary ammonium salts such as , pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. The photographic light-sensitive material may contain an inorganic or organic hardening agent in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glitaraldehyde, etc.), N
- Methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.),
Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.) ) Mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.),
These can be used alone or in combination. The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, Acrylic acid, α,
β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)
Polymers containing a combination of acrylate, styrene sulfonic acid, etc. as monomer components can be used. The invention is also applicable to multilayer natural color photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as necessary. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. The present invention is also applicable to color image transfer methods, absorption transfer methods, and the like. The present invention is particularly advantageous when applied to the single-bath development method described in JP-A-58-18629, as its effects are great. In addition to containing one or more of the various intensifying agents described above, the intensifying liquid used in the present invention may also contain known intensifying liquid component compounds. For example, PH buffers, antifoggants, intensifier stabilizers, etc. can be included. In addition, development accelerators, preservatives, water softeners, organic solvents,
Dye-forming couplers, competitive couplers, fogging agents,
It may also contain an auxiliary developer, a viscosity-imparting agent, a polycarboxylic acid chelating agent, an antioxidant, an alkaline agent, a solubilizing agent, a surfactant, an antifoaming agent, and the like. Specific examples of these additives are available from the West German Publication (OLS)
No. 1813920, JP-A-48-9728, JP-A-52-13335
No. 52-73731, etc. In one of the representative processes belonging to the present invention,
After the AgX color sensitive material is exposed, it is developed in one bath and immediately processed with a dilute buffer-containing processing solution having a pH of 2 to 7, followed by drying to give a color image. It is sufficient to simply perform the above-mentioned treatment after the one-bath development intensification. The present invention is particularly effective in a process in which the above-mentioned treatment is performed after one-bath development and intensification treatment using peroxide as an intensification agent. In another process, after a latent image is grown by development, a color developing agent is retained in a photosensitive material film, and the developing agent is brought into an intensifier bath, and the image is enhanced with an intensifier. After applying power, PH2~7
It is also possible to process with a dilute buffer-containing processing solution. In another process, a developing agent may be included in the light-sensitive material, for example in the emulsion layer, and the light-sensitive material may be processed in an alkaline intensifier to form an intensified image, followed by the above processing. In another process, the coupler may be included in a developing intensifier solution and processed to form an intensified image, followed by the processing of the present application. As the so-called diffusible external coupler used by being added to the development intensifying solution, cyan couplers are disclosed, for example, in US Pat. No. 3,002,836;
Examples of the magenta coupler described in U.S. Patent No. 3,542,552, etc.
Examples of yellow couplers include those described in US Pat. No. 3,510,306 and the like. in this case,
The coupler concentration is between 0.5 and 5 g/, especially 1
It is used in the range of 25g/ to 25g/. In another process, a photosensitive layer and an image-receiving layer are superimposed, and a developer intensifier is interposed between them, so that development and intensification are performed simultaneously, and the dyes, which have become mobile due to oxidation by the intensifier, are Diffuses into the image receiving layer. Conversely, it is also possible to receive an image of a mobile dye from a portion that has not undergone oxidation. As a process after forming a color image in this way, the process of the present invention can be performed. Example 1 A low-silver color light-sensitive material was prepared by coating the following first layer (bottom layer) to sixth layer (top layer) on a paper support laminated on both sides with polyethylene in which titanium dioxide was dispersed. (mg/ ^m2 in the table below represents the amount of application.)

【table】

[Table] This sample was exposed with a sensitometer and processed as follows. Processing process Temperature Time One-bath development intensification 35℃ 1 minute Post-processing 35℃ 30 seconds One-bath development intensification solution Potassium sulfite 4g Tripotassium phosphate 40g Dipotassium phosphate 6g 1-Hydroxyethane-1,1-diphosphonic acid
2g benzotriazole 6mg 4-amino-3-methyl-N-ethyl-N-β
-(methanesulfonamide)ethylaniline 3/2 sulfate 4g Hydrogen peroxide (30%) 20ml Add water 1 (PH11.0) Post-treatment liquid No. 1 0.1N hydrochloric acid 350ml Sodium citrate dihydrate 4.4g Add water 1 (PH3.2) No.2 0.1N hydrochloric acid 110ml Sodium citrate dihydrate 4.1g Add water 1 (PH5.3) No.3 Sodium sulfite 2.5g Sodium bisulfite 3.0g Add water 1 (PH6.7) No.4 Sodium sulfite 2.5g Sodium bisulfite 3.0g Sodium thiosulfate 1.6g Add water 1 (PH6.7) No.5 Monopotassium phosphate 3.5g Dipotassium phosphate 4.1g Thio Sodium sulfate 1.0g Added water 1 (PH6.7) For comparison, the following treatment was performed. Processing process Temperature Time One-bath development intensification 35℃ 1 minute Washing (running water) 25℃ 30 seconds or 2 minutes In both cases, dry after processing, minimum temperature (Dmin)
The results of the measurements are shown in Table 1.

[Table] It can be seen that the process of the present invention, which requires a long time with water washing alone, shows a low Dmin in a very short time. Further, even after drying, there was almost no staining on the surface. Example 2 A photographic element was prepared by coating the following first and second layers on a paper support laminated on both sides with polyethylene dispersed with titanium dioxide.

[Table] Support

Claims (1)

[Claims] 1. An imagewise exposed silver halide color light-sensitive material is treated with a small amount of an intensifying agent consisting of a peroxide, a halogen acid, an iodoso compound, and a cobalt () complex compound in the presence of a reducing agent and, if necessary, a coloring agent. Tomo1
A color characterized by forming a reinforced color image by forming a reinforced color image, and then treating it with a solution containing a dilute buffering agent of pH 2 to 7 without desilvering, and then drying without washing with water. Image forming method.