EP0132806A2

EP0132806A2 - Method of processing silver halide color light-sensitive materials

Info

Publication number: EP0132806A2
Application number: EP84108626A
Authority: EP
Inventors: Takatoshi Ishikawa; Junya Nakajima
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1983-07-20
Filing date: 1984-07-20
Publication date: 1985-02-13
Also published as: EP0132806A3; JPS6023857A

Abstract

A method of processing silver halide color light-sensitive materials is disclosed, which comprises the steps of:

developing an exposed silver halide color light-sensitive material,
thereafter substantially washing the material with water for a period from about 5 to 90 seconds, and
thereafter bleach-fixing the material using a bleach-fixing solution to which is added from about 30 ml to 120 ml replenisher solution of a bleach-fix per m' of said material processed,
by which contamination of the light-sensitive materials and inferior recovery of color are prevented in spite of using a reduced amount of a bleach-fix replenisher solution.

Description

FIELD OF THE INVENTION

The present invention relates to a method of processing silver halide color light-sensitive materials using a reduced amount of a bleach-fix replenisher solution. More particularly, it relates to a method of processing silver halide color light-sensitive materials, by which contamination of color light-sensitive materials is substantially prevented and formation of a leuco form of dyes is substantially prevented.

BACKGROUND DF THE INVENTION

Generally, in order to obtain color images by carrying out development processing of an imagewise exposed silver halide color light-sensitive material, a process generally is used which comprises bleaching metallic silver formed upon a color development step with an oxidizing agent (bleaching agent) followed by fixing with a silver halide fixing agent. For the purpose of shortening photographic processing steps or processing time, or reducing of labor,..a process is also used which comprises a bleach-fixing step in which the bleaching step is combined with the fixing step. Typical bleach-fix solutions used for such a process have been described in West German Patents 866,605 and 966,410, British Patent 1,014,396, U.S. Patents 3,189,452 and 3,615,508, and Japanese Patent Application (OPI) Nos. 781/71, 13934/72, 65940/73 and 140128/75 (the term "OPI" as used herein refers to a "published unexamined Japanese patent application"), etc.
In the bleach-fix solution, a bleaching agent (oxidizing agent) and a fixing agent must be present together in a stabilized state. Since the thiosulfates used chiefly as fixing agents are reducing agents, a comparatively weak oxidizing agent such as a metal complex of an organic acid is selected as the bleaching agent. Thus, the prepared bleach-fix solution is inherently inferior in oxidation ability as compared with the bleaching solution.
Consequently, known methods of processing color light-sensitive materials with a bleach-fix solution have the disadvantage that dyes are not completely formed, because the leuco dyes formed in the color development step are not sufficiently oxidized in the bleach-fixing step and remain present as leuco dyes which are reaction intermediates. This phenomenon of inferior recovery of color is remarkable in the case of cyan dyes.
Furthermore, in recent years, in order to meet environmental requirements, in to economize and to reduce labor, there has been a tendency to reduce replenishing amounts of processing solutions. However, when the replenishing amount of the bleach-fix solution is greatly reduced, unsuitable contamination of sensitive materials (adhesion of contaminants and formation of fog) occurs, and it becomes very difficult to avoid both inferior recovery of color and contamination at the same time.
Various methods of improving the inferior recovery of color are known. For example, a method wherein bromic acid salts or persulfates are added to a bleaching solution is described in Japanese Patent Application (OPI) Nos. 17732/74 (corresponding to U. S. Patent 3,770,437) and 65939/76, this method has the disadvantage that bleaching fog is formed. A method which comprises oxidizing leuco substances with. ferricyanides to change them into dyes after processing with a bleach-fix solution is desclosed in Japanese Patent Application (OPI) Nos. 43938/73, 45238/73, and 46334/73, but this method is not suitable because it causes environmental pollution. A method wherein bromic acid salts and iodides or bromides are added to a bleach-fix solution is disclosed in U. S. Patent 3,770,437, but it is not suitable because it deteriorates the stability of the bleach-fix solution and bleaching fog is formed. A method which comprises processing with a solution containing persulfates as a pre-bath or post-bath of the bleach-fix bath is also know from Japanese Patent Application (OPI) No. 26139/73, but it is unsuitable for practical use, because of inferior recovery of color and formation of bleaching fog. Further, a method wherein various aminopolycarboxylic acid metal complexes are combined is described in Japanese Patent Publication No. 38894/79, but this is not a practical method, because stability of the bleach-fix solution is inferior and the cost is disadvantageous. Moreover, a method wherein p-phenylenediamines or pyrazolidones are added to the bleach-fixing solution is described in Japanese Patent Publication No. 23179/76 and a method wherein alkanolamines are added to the bleach-fix solution is described in Japanese Patent Application (OPI) No. 192953/82, but both methods show an inferior effect.
Several methods of preventing fog, are known, e.g., a method wherein amines are added -to the-bleach-fix solution described in Japanese Patent Publication No. 556/71 (corresponding to U.S. Patent 3,578,453); a method wherein bromides or iodides are added,described in Japanese Patent Publication No. 11854/78 (corresponding to U.S. Patent 4,040,837); and a method wherein 3-pyrazolidones or p-aminophenols are added, described in British Patents 1,132,399 and 1,133,500. These known.methods, however, are insufficient in effect.
No satisfactory method has been known of preventing contamination of sensitive materials (particularly formation of fog) caused in the bleach-fixing step and avoiding inferior recovery of color while greatly reducing the replenishing amount of bleach-fix solution required, although these problems are well-known in the art.

SUMMARY OF THE INVENTION

Accordingly, an object of'the present invention is to provide a method of processing silver halide color light-sensitive materials, by which the replenishing amount of bleach-fix solution required is greatly reduced and contamination of the-light-sensitive materials and inferior recovery of color are prevented.
This object is attained by the method of the present invention, which comprises the steps of color developing a silver halide color light-sensitive material, substantially washing the .silver halide color light-sensitive material with water for 5 to 90 seconds and thereafter bleach-fixing in a bath which is replenished by the addition of a standard replenisher solution in a reduced amount of from about 30 ml to 120 ml per m² of silver halide color light-sensitive material.

DETAILED DESCRIPTION OF THE INVENTION

Although it is known from Japanese Patent Application (OPI) No. 192953/82 to use a water wash bath between a color development step and a bleach-fixing step, there is no disclosure that by using such a washing step the replenishing amount of the bleach-fixing solution can be remarkably reduced as in the present invention, and, further, there is no disclosure regarding contamination of the light-sensitive materials or inferior recovery of color due to the remarkable reduce.
It is an entirely unexpected discovery that the above-described problems of contamination of sensitive materials and inferior recovery of color, can be solved while greatly reducing the replenishing amount of the bleach-fix solution required by providing a water wash step as in the present invention.
In the color development step in the present invention,-the processing temperature is typically-about 25°C -to 50°C and, preferably, about 30°C to 42°C. The processing time is 30 seconds to 10 minutes and, preferably, about 1 minute to 5 minutes. Further, the replenishing amount is about 50 ml to 600 ml and, preferably, about 100 ml to 500 ml per m² of the sensitive material.
The pH of the color developing solution of the present invention is about 9 to 12. The composition of the color developing solution is not limited, and can contain various compounds including any color developing agents known in the art.
As the color developing agents, aromatic primary amine developing agents are widely used and p-phenylenediamine derivatives are particularly preferred. Typical examples of such agents include the following, but the present invention is not to be construed as limited to the examples cited.

N,N-Diethyl-p-phenylenediamine,
2-Amino-5-diethylaminotoluene,
2-Amino-5-(N-ethyl-N-laurylamino)toluene,
4-[N-Ethyl-N-(β-hydroxyethyl)amino]aniline,
2-Methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline, N-Ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline,
N-(2-Amino-5-diethylaminophenylethyl)methanesulfonamide, N,N-Dimethyl-p-phenylenediamine,
4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline,
4-Amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline,
4-Amino-3-methyl-N-ethyl-N-β-butoxyethylaniline, and their salts (for example, sulfates, hydrochlorides, sulfites and p-toluenesulfonates, etc.). The above compounds have been described in U.S. Patents 2,193,015, 2,552,241, 2,566,271, 2,592,364, 3,656,950, and 3,698,525. The amount of the above-described aromatic primary amine developing agents used is in a range of about 0.1 g to about 20 g and, preferably, about 0.5 g to about 10 g, per liter of the developing solution.

The color developing solution used in the present invention may contain various kinds of organic or inorganic chelating agents. Typical inorganic chelating agents include sodium tetrapolyphosphate and sodium hexametaphosphate, and typical organic chelating agents include organic carboxylic acids, organic phosphonic acids and organic phosphonocarboxylic acids.
The organic carboxylic acids, used may include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cork acid, azelaic acid, sebacic acid, nonane dicarboxylic acid, decane dicarboxylic acid, undecane dicarboxylic acid, maleic acid, fumalic acid, phthalic acid, citraconic acid, mesaconic acid, itaconic-acid, malic acid, citric acid, and tartaric acid, etc. However, useful organic carboxylic acids are not limited to these examples.
Further, aminopolycarboxylic acids can be used, for example, iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetramine- hexaacetic acid, hydroxyethylethylenediaminetetraacetic acid, glycol ether diaminetetraacetic acid, hydroxyethyl- iminodiacetic acid, diaminopropanol tetraacetic acid, 1,2-diaminopropanetetraacetic acid and compounds described in Japanese Patent Application (OPI) Nos. 25632/77, 67747/80, and 102624/82 and Japanese Patent Publication No. 40900/78, etc.
Organic phosphonic acids include the hydroxy- alkylidene-diphosphonic acids described in U.S. Patents 3,214,454 and 3,794,591 and German Patent Application (OLS) No. 2,227,639, and compounds described in Research Disclosure, No. 18170.
Aminophosphonic acids include aminotris-(methylenephosphonic acid) and ethylenediamine-N,N,N',N'-tetramethylene- phosphonic acid. In addition, there are compounds described in Research Disclosure, No. 18170, and Japanese Patent Applications (OPI) 208554/82, 61125/79, 29883/77, and 97347/81.
Phosphonocarboxylic acids include the compounds described in Japanese Patent Application (OPI) Nos. 102726/77, 42730/78, 121127/79, 4024/80, 4025/80, 126241/80, 65955/80, and 65956/80, and Research Disclosure, No. 18170.
These chelating agents may be used in the form of an alkali metal salt or ammonium salt. Further, two or more kinds of chelating agents may be used in combination.
The amount of these chelating agents to be added is in a range of about 1 x 10 ^-4 mols to 1 x 10 1 mols and, preferably, about 1 x 10^-3 mols to 1 x 10 2 mols per liter of the color developing solution.
Of these chelating agents, preferred compounds are aminopolycarboxylic acids, organic phosphonic acids and aminophosphonic acids.
Further, in order to improve stability of the color developing solution, various preservatives can be added, such as, for example, sulfites and hydroxylamines. In addition, the compounds described in Japanese Patent Application (OPI) Nos. 27638/77, 49828/77, 102727/77, 3532/79, 94349/81, 143020/77, 89425/78, 75647/81, 41448/80, 47038/81, and 32140/81 and U.S. Patents 3,615,503, 3,746,544, and 3,823,017, and British Patent 1,306,176 may be added.
In addition to the above-described substances, the color developing solution used in the present invention may contain compounds known as developer components.
For example, as alkali agents and buffer agents, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate, potasium tertiary phosphate, potassium metaborate, and borax, etc. are used alone or in combination. Further, in order to give buffering ability, for reasons of preparation or to increase ionic strength, it is possible to use various salts such as disodium or dipotassium hydrogen phosphate, sodium or potassium dihydrogen phosphate, sodium or potassium bicarbonate, boric acid, alkali nitrates or alkali sulfates, etc.
If necessary, suitable developing accelerators can be added to the color developing solution. These include various pyridinium compounds and other cationic compounds described in U.S. Patents 2,648,604, and 3,171,247, and Japanese Patent Publication No. 9503/69; cationic dyes such as phenosafranine; neutral salts such as thallium nitrate or potassium nitrate; nonionic compounds such as polyethylene glycol or derivatives or polythioethers, etc., described in Japanese Patent Publication 9304/69 and U.S. Patents 2,531,832, 2,533,990, and 2,577,127, and 2,950,970; organic solvents described in Japanese Patent Publication No. 9509/69 and Belgium Patent 682,862; and other known accelerators such as organic amines, ethanolamine, ethylenediamine and diethanolamine, etc. It is also possible to use accelerators described in L.F.A. Mason,-Photographic Processing Chemistry p. 40-43 (Focal Press London, 1966); benzyl alcohol and phenylethyl alcohol described in U..S. Patent 2,515,147; and pyridine, ammonia, hydrazine, amines and pyrazolidinones described in Nippon Shashin Gakkaishi Vol. 14, page 74 (1952), and thioether compounds described in U. S. Patent 3,201,242. Preferred compounds are benzyl alcohol and thioether compounds.
In the present invention, if necessary, it is possible to add suitable inorganic or organic antifoggants to the color developing solution. As the inorganic antifoggants, alkali metal halides such as potassium bromide, sodium bromide or potassium iodide can be used. As the organic antifoggants, it is possible to use nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethyl-benzimidazole or hydroxyazaindolidine, mercapto-substituted heterocyclic compounds such as l-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole or 2-mercaptobenzothiazole, and mercapto-substituted aromatic compounds such as thiosalicylic acid. Particularly preferred examples are nitrogen-containing heterocyclic compounds. These antifoggants may accumulate in the color developing solution by being released from the color light-sensitive material during processing.
Further, if necessary, competing couplers, foggants and compensating developing agents known in the art can be added to the color developing solution.
. As competing couplers, citrazinic acid, J acid and H acid, etc., are known and, for example, it is possible to use compounds described in U. S. Patent 2,742,832, 3,520,690, 3,560,212, and 3,645,737 and Japanese Patent Publication Nos. 9504/69, 9506/69, and 9507/69, etc.
As foggants, alkali metal borohydride, aminoborane, and ethylenediamine, etc. can be used. In addition, compounds described in Japanese Patent Publication No. 38816/72 can be used.
As compensating developing agents, p-aminophenol, N-benzyl-p-aminophenol and l-phenyl-3-pyrazolidones, etc. can be used. For example, compounds described in Japanese Patent Publication Nos. 41475/70 and 19037/71 are available.
In the present process, the step of washing with water is carried out after the color development step. The time of water wash processing may be shorter than the conventional washing time, in a range of about 5 seconds to 90 seconds and, preferably, of about 10 seconds to 40 seconds. The term "washing time" means the time from the beginning of washing to introduction of the color light-sensitive material into the bleach-fixing bath, which includes the time during which the color light-sensitive material travels into the next bath (crossover time). The amount of water used for washing is in a range of about 50 ml to 20 ! and, preferably, about 100 ml to 5 ℓ per m ² of the color light-sensitive material. The temperature of washing is in a range of about 5°C to 60°C and, preferably, about 15°C to 40°C. The method of washing with water is not unduly limited, and may be carried out by a method which comprises providing baths and immersing the light-sensitive material in the baths, by a method which comprises spraying water by a sprayer, or by any other method known in the art.
As used herein, the term "substantially washing with water" means to treat with water or with conventional washing water, or in addition to treat with a aqueous solution prepared by adding various buffer agents, chelating agents or antifungal agents to water or washing water.
Typical examples of typical buffer agents include borates, metaborates, borax, phosphates, mono- carboxylates, dicarboxylates, polycarboxylates, oxy- carboxylates, amino acids, aminocarboxylates, primary phosphates, secondary phosphates, tertiary phosphates, sulfonates, sodium hydroxide and potassium hydroxide.
Typical examples of chelating agents include polyphosphates, pyrophosphates, metaphosphates, organic carboxylates, aminopolycarboxylates, alkylidene di- phosphonates, aminopolyphosphonates and phosphonocarboxylates, etc. as described above.
Typical examples of antifungal agents include sorbic acid, sodium dehydroacetate, propionic acid, thiabenzazole, benzoic acids, and chloramines, etc.
The bleach-fixing step in the present invention is carried out at a processing temperature of about 25°C to 50°C and, preferably, about 30°C to 42°C. The processing time is in a range of about 20 seconds to 10 minutes and, preferably, about 40 seconds to 3 minutes. Further, in the present invention, the replenishing amount is significantly less than the amount typically used of several hundred ml/m² (a range of 1/several tens to 1/several, as compared with the amount typically used), and in the present process it is in a range of about 30 ml to 120 ml and, preferably, about 40 ml to 100 ml per m² of the sensitive material.
The pH of the bleach-fix replenisher solution used in the present invention is in a range of about 5 to 8 and, preferably, about 6 to 7. The bleach-fix replenisher solution is mainly comprised of three components of a bleaching agent, a fixing agent and a preservative.
As the bleaching agents, iron (III) complexes of aminopolycarboxylic acids are used, which may include sodium salts, potassium salts, ammonium salts or watersoluble amine salts. Particularly preferred examples are ferric salts of ethylenetetradiaminetetraacetic acid, for example, sodium ethylenediaminetetraacetato iron (III) complex, potassium ethylenediaminetetraacetato iron (III) complex and ammonium ethylenediaminetetraacetato iron (III) complex. The amount of them used is in a range of about 0.1 mol/l to 0.5 mol/l and, preferably, about 0.15 mol/l to 0.40 mol/1.
As fixing agents, known thiosulfates, thiocyanates, and thioureas, etc., can be used, and thiosulfates such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate are particularly preferred. The amount used is in a range of about 0.5 mol/l to 3.0 mol/l and, preferably, about 1.0 mol/l to 2.0 mol/1.
As preservatives, sulfites, metabisulfites, ascorbic acids described in Japanese Patent Application (OPI) No. 52748/81 and carbonyl-bisulfurous acid addition products described in Japanese Patent Publication 38895/79 can be used. It is particularly preferred to use sodium sulfite, potassium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, ammonium bisulfite, sodium metabisulfite, potassium metabisulfite, and ammonium metabisulfite. The amount used is in a range of about 0.1 mol/l to about 0.4 mol/l and, preferably, about 0.15 mol/l to 0.35 mol/1.
In addition, pH buffer agents, accelerators, chelating agents, fluorescent-whitening agents, surface active agents and hardeners, etc. may be incorporated as desired.
Examples of pH buffer agents typically used include boric acid, borax, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, and sodium acetate.
Examples of bleach-fixing accelerators include bromine ion, iodine ion, thiourea compounds described in U. S. Patent 3,706,561, Japanese Patent Publication Nos. 8506/70 and 26586/74 and Japanese Patent Application (OPI) Nos. 32735/78, 36233/78, and 37016/78; thiol compounds described in Japanese Patent Application (OPI) Nos. 124424/78, 95631/78, 57831/78, 32736/78, 65732/78 and 52534/79 and U. S. Patent 3,893,858; heterocyclic compounds described in Japanese Patent Application (OPI) Nos. 59644/74, 140129/75, 28426/78, 141623/78, 104232/78, and 35727/79 and Research Disclosure No. 17129; thioether compounds described in Japanese Patent Application (OPI) Nos. 94927/78, 20832/77, 37418/78, 95630/78, 25064/80, and 26506/80; quaternary amines described in Japanese Patent Application (OPI) No. 84440/73; and thiocarbamoyl compounds described in Japanese Patent Application (OPI) No. 42349/74.
-Examples of the chelating agents include organic carboxylates, aminopolycarboxylates, alkylidenediphosphonates, aminopolyphosphonates and phosphonocarboxylates.
In the bleach-fix replenisher solution used in the present invention, about 60%-100% of cation content is present as ammonium ions and, preferably, about 70%-100% consists of ammonium ions. These ammonium ions may be added as a pair salt of aminopolycarboxylic acid iron (III) complexes, sulfites or thiosulfates or may be added as ammonium hydroxide.
In the present invention, the light-sensitive material after bleach-fix processing is carried out is advantageously again subjected to water wash processing. The second washing step is carried out at a temperature of about 5°C to 50°C and, preferably, about 15°C to 40°C for a washing time of about 50 seconds to 5 minutes. The second washing step may be carried out by any method, but a multistage counter current washing process wherein water runs as a counter current from the post-bath to the pre-bath is preferably used. The number of baths for counter current washing is typically 2 to 10 and, preferably 2 to 9. Further in order to improve washing efficiency, the washing tank may be fitted with a heater to increase the washing temperature or may be fitted with an air bubbling apparatus. The amount of water for washing varies widely according to the method of washing, but it is generally, in a range of about 500 ml to 50 ! and, preferably, about 1 ℓ to 30 ! per m² of the light-sensitive material.
Further, in the present invention, a stabilizing step described in Japanese Patent Application (OPI) Nos. 8543/82, 132146/82, 1863/83, 34448/83, and 14834/83 may be used instead of a washing step after the bleach-fix processing step.
In the present invention, the method of processing the imagewise.exposed color light-sensitive material fundamentally comprises the steps of color development, washing with water, and bleach-fixing, but the present invention is not limited to those steps, and may also advantageously include other steps, such as the following:

(1) Color development, washing with water, bleach-fixing, and washing with water
(2) Color development, washing with water, bleach-fixing washing with water, and stabilization
(3) Black-and-white development,-stopping, washing with water, fogging, color development, washing with water, bleach-fixing, washing with water, and stabilization.

In example (3), the stopping bath and the stabilizing bath can be omitted. Further, the fogging bath can be omitted by adding a foggant-to the color developing bath.
The method of processing of the present invention can be applied to processing of any conventional silver halide color photographic materials such as color negative films, color papers, color positive films or color reversal films. It is particularly preferred to apply the present method to the processing of color papers.
The photographic emulsions used in the present invention can be prepared by processes described in P. Glafkides, Chimie et Physique Photographique, (Paul Montel Co., 1967), G.F. Duffin, Photographic Emulsion Chemistry, (Focal Press, 1966), and V.L. Zelikmann et al., Making and Coating Photographic Emulsion, (Focal Press, 1964). They may be prepared by any conventional process, including the acid process, neutral process and ammonia process. Further, to react soluble silver salts with soluble halogen salts, the single jet mixing process, the double jet mixing process and a combination of them may be used.
In the photographic emulsion layers of the photographic light-sensitive materials used in the present invention, any of silver bromide, silver iodobromide, silver iodochlorobrmide, silver chlorobromide and silver chloride may be used as the silver halide component.
Formation of silver halide grains or physical ripening may be carried out in a presence of cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, or iron salts or complex salts thereof.
- The photographic emulsions used in the present may be spectrally sensitized with methine dyes and others. Examples of dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes and complex merocyanine dyes. In these dyes, any nucleus conventionally used for cyanine dyes can be utilized as a basic heterocyclic nucleus.
These sensitizing dyes may be used alone, or in combination. Combinations of such sensitizing dyes are frequently used, particularly for the purpose of supersensitization.
The emulsions may contain dyes which do not have a spectral sensitization function themselves or substances which do not substantially absorb visible rays, but which dyes and substances show supersensitization together with the sensitizing dyes.
As a binder or a protective colloid in the photographic emulsions, gelatin is preferably used, but other known hydrophilic-colloids can also-be-used.
The color light-sensitive materials of the present invention have generally at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on a base. The order of these layers applied is arbitrarily selected as occasion demands. Generally, the red-sensitive emulsion layer contains a cyan coupler, the green-sensitive emulsion layer contains a magenta coupler, and the blue-sensitive emulsion layer contains a yellow coupler, and, if necessary, other combinations can be used.
In the light-sensitive materials used in the present invention, the hydrophilic colloid layers may also contain water soluble dyes as filter dyes or for other purposes such as the preventing irradiation. Typical examples of such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Particularly preferred are oxonol dyes, hemioxonol dyes and merocyanine dyes.
In the present invention, the following known antifading agents or the color image stabilizers can be used alone or in a combination of two or more. Known antifading agents include, for example, hydroquinone derivatives described in U. S. Patents 2,360,290, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,710,801, 2,728,659, 2,732,300, 2,735,765, and 2,816,028 and British Patent 1,363,921; gallic acid derivatives described in U. S. Patents 3,069,262, 3,457,079; p-alkoxyphenols described -in U. S. Patents 2,735,765 and 3,698,909 and Japanese Patent Publication Nos. 20977/74 and 6623/77; p-oxyphenol derivatives described in U. S. Patents 3,432,300, 3,573,050, 3,574,627, and 3,764,337, and Japanese Patent Application (OPI) Nos. 35633/77, 147434/77, and 152225/77; and bisphenols described in U. S. Patent 3,700,455.
In the light-sensitive materials used in the present invention, the hydrophilic colloid layers may contain ultraviolet absorbing agents, such as benzotriazole compounds substituted by aryl groups (for example, those described in U. S. Patent 3,533,794); 4-thiazolidone compounds (for example, those described in U. S. Patents 3,314,794 and 3,352,681; benzophenone compounds (for example, those described in Japanese Patent Application (O_PI) No. 2784/71); cinnamic acid ester compounds (for example, those described in U. S. Patents 3,705,805 and 3,707,375); butadiene compounds (for example, those described in U. S. Patent 4,045,229); and benzoxazole compounds (for example those described in U. S. Patent 3,700,455); as well as compounds described in U. S. Patent 3,499,762 and Japanese Patent Application No. 48535/79. Infrared absorbing couplers (for example, a-naphthol type cyan forming couplers) and ultraviolet absorbing polymers, also be used.
These ultraviolet absorbing agents may be mordanted in any specified layer as desired.
In the light-sensitive materials used in the present_.invention, the photographic emulsion layers and other hydrophilic colloid layers may contain known stilbene type, triazine type, oxazole type or coumarine type whitening agents. They may be soluble in water, or water-insoluble whitening agents may be used. as a dispersion.
The photographic emulsion layers of the photographic light-sensitive materials used in the present invention contain couplers capable of oxidative coupling with aromatic primary amine developing agents (for example, phenylenediamine derivatives or aminophenol derivatives, etc.) in the color development processing to form color dyes. The couplers used are not limited, and may be freely selected from those known in the art.
Examples of magenta couplers include those described in U. S. Patents 2,600,788, 2,983,608, 3,062,653, 3,127,269, 3,311,476, 3,419,391, 3,519,429, 3,558,319, 3,582,322, 3,615,506, 3,834,908, 3,891,445 and 4,351,897; German Patent 1,810,464, German Patent Application (OLS) Nos. 2,408,665, 2,417,945, 2,418,959, and 2,424,467; Japanese Patent Publication No. 6031/65 and Japanese Patent Application (OPI) Nos. 20826/76, 58922/77, 129538/74, 74027/74, 159336/75, 42121/77, 74028/74, 60233/75, 26541/76, and 55122/78.
As yellow couplers, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageously used. Examples-of yellow couplers include U. S. Patents 2,875,057, 3,265,506, 3,408,194, 3,551,155, 3,582,322, 3,725,072, and 3,891,445; German Patent 1,547,868, German Patent Application (OLS) Nos. 2,219,917, 2,414,₀₀₆, and 2,261,361; British Patent 1,425,020; Japanese Patent Publication No. 10783/76, and Japanese Patent Application (OPI) Nos. 26133/72, 73147/73, 102636/76, 6341/75, 123342/75, 130442/75, 21327/76, 87650/75, 82424/77 and 115219/77, etc.
As cyan couplers, phenol compounds and naphthol compounds, can be used. Examples of such couplers are described in U. S. Patents 2,359,929, 2,434,272, 2,474,293, 2,521,908, 2,895,826, 3,034,892, 3,311,476, 3,458,315, ₃,₄₇6,563, 3,583,971, 3,591,3a3, 3,767,411, and 4,004,929; German Patent Application (OLS) Nos. 2,414,830 and 2,454,329; and Japanese Patent Application (OPI) Nos. 59838/73, 26034/76, 5055/73, 146828/76, 69624/77, 90932/77, 155533/82, and 204545/82.
As colored couplers, it is possible to use, for example, those described in U. S. Patents 3,034,892, 3,476,560, and 2,521,908; Japanese Patent Publication Nos. 2016/69, 22335/63, 11304/67, and 32461/69, Japanese Patent Application (OPI) Nos. 26034/76 and 42121/77; and German Patent Application (OLS) No. 2,418,959.
As DIR couplers, it is possible to use, for example, those described in U. S. Patents 3,227,554, 3,617,291, 3,632,345, 3,701,783, and 3,790,384; West German Patent Application (OLS) Nos. 2,414,006, 2,454,301, and 2,454,329; British Patent 953,454; Japanese Patent Application Nos. 69624/77 and 12335/74, and Japanese Patent Publication No. 16141/76.
The light-sensitive materials may also contain compounds which release a development restrainer by development, other than DIR couplers. For example, it is possible to use those described in U. S. Patents 3,297,445 and 3,379,529; German Patent Application (OLS) No. 2,417,914; and Japanese Patent Application (OPI) Nos. 15271/77 and 9116/78.
and 9116/78.
Two or more of the above-described couplers may be contained in the same layer. The same compound may be contained in two or more layers.
These couplers are added generally in an amount of about 2 x 10^-3 mol to 5 x 10^-1 mol and, preferably, about 1 x 10 ^-2mol to 5 x 10-1 mol per mol of silver in the emulsion layer.
The present invention is illustrated in greater detail by reference to the following examples, but the present invention is not to be construed as being limited thereto.

EXAMPLE 1

A processor FPRP 102 for Fuji color roll papers (produced by Fuji Photo Film Co.) was altered so as to have the following processing steps.
(Each processing time includes the time for processing in each bath and the crossover time for the next bath.)
Imagewise exposed Fuji color papers (Type 01, produced by Fuji Photo Film Co.) were continuously processed by the above-described two processors.
Each processing solution used was as follows. Color developing solution:
Bleach-fix solution:
Processing conditions were as follows.
The imagewise exposed Fuji color papers (produced by Fuji Photo Film Co.) were continuously processed in processors (A) and (B) using the above-described processing solutions under the above-described processing conditions.
The processing amount was 50 m² of rolled paper. having a width of 8.25 cm per day, and the processing was repeated for 30 days.
Further, wedge-exposed Fuji color papers were developed at the intervals indicated in Table 1, and their photographic properties were compared. Results, that is, the changes with rapse of time in optical density, of each a blue-sensitive layer (B), a green-sensitive layer (G) and a red-sensitive layer (R), obtained by processed with the processors (A) and (B), are shown in Table 1.
The samples of the 30th day from processor (A) which had exhibited low red sensitivity and soft tone as the processing amount had increased, were measured again after they were immersed in a 20% solution of EDTA Fe (III). NH₄ (pH 7.0), and they were restored to the photographic properties of the first day. Accordingly, it was concluded that formation of the leuco form of the cyan dye (inferior recovery of color) occurred in the processing by the processor (A), but it did not occur in the processing by the processor (B).
The yellow densities of the D min portions of the wedge-exposed light-sensitive materials processed in processors (A) and (B) were again measured after samples exposed on the first day and samples exposed on the 30th day had been allowed to stand at 80°C for 15 days. The samples processed in processor (B) using the method of the present invention were shown to be clearly superior to the samples processed in processor (A). Remarkably, the processing performance attained after thirty days using the method of the present invention was nearly the same as that of the first day.

EXAMPLE 2

Fuji color papers (produced by Fuji Photo Film Co.) were exposed and processed in the.same manner as in Example 1, with the difference that the processing amount was 25 m² of rolled paper having a width of 8.25 cm per day, and the processing was repeated for 60 days.
Variations of photographic properties are shown in Table 2 in the same manner as in Example 1.
Once again, with increasing amounts of light-sensitive materials processed in processor (A), red- sensitivity and soft tone decreased, and inferior recovery of color was experienced as in Example 1. However, in the processing by the processor (B), it was not experienced. The samples of the first day and the 60th day were allowed to stand at 80°C for 15 days.
Variations of yellow density of the D min portion of the exposed light-sensitive material for both processed samples were measured, and the results are shown in Table 3.
In the processing by the processor (A), yellow stains were remarkably increased in the sample processed with the processing equilibrium solution (i.e., the tank solution wherein the processing was repeated for 60 days). However, in the processing by the processor (B), the result after 15 days was greatly superior, with the processing performance of the equilibrium solution remaining nearly the same as that of the tank solution.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and the scope thereof.

Claims

1. A method of processing silver halide color light-sensitive materials, particularly color print paper which comprises the steps of:

developing an exposed silver halide color light sensitive material,

thereafter substantially washing the material with water for a period from about 5 to 90s, particularly about 10 to 40s and

thereafter bleach-fixing the material using a bleach-fixing solution to which is added from about 30 ml to 120 ml replenisher solution of a bleach-fix per m² of said material processed.

2; The method as claimed in Claim 1, whereby contamination of the color light-sensitive materials and formation of leuco dyes is substantially prevented.

3. The method as claimed in Claim 1, wherein in the developing step is used a developing solution comprising an aromatic primary amine developing agent and optionally in addition chelating agents.

4. The method as claimed in Claim 1, wherein the developing solution is replenished by adding from about 50 ml to 600 ml replenisher solution of a developer per m² of, said material process.

5. The method as claimed in Claim 1, wherein said bleach-fix replenisher solution comprises a bleaching agent, a fixing agent, and a preservative.

6. The method as claimed in Claim or 5, wherein the bleaching agent is an iron (III) complex of an aminopolycarboxylic acid selected from the group consisting of sodium salts, potassium salts, ammonium salts, and watersoluble amine salts of such complexes, said complexes being used in a range of about 0.1 mol/1 to 0.5 mol/1.

7. The method as claimed in Claim 6, wherein said aminopolycarboxylic acid salt complex is a ferric salt of ethylenetetradiaminetetraacetic acid_used_in_an amount of about 0.15 mol/1 to 0.40 mol/l.

8. The method as claimed in Claim or 5, wherein said fixing agent is selected from the group consisting of thiosulfate, thiocyanata, thiourea and thiosulfate compounds, particularly sodium thiosulfate, potassium thiosulfate or ammonium thiosulfate, used in an amount of about 0.5 mol/l to 3.0 mol/1, particularly in an amount of about 1.0 mol/l to 2.0 mol/l.

9. The method as claimed in Claim 1, wherein the bleach-fix replenisher solution is added in an amount of from about 40 ml to 100 ml per m² of the light-sensitive material process.

₁₀. The method as claimed in Claim 1, wherein after the bleach-fixing, the light-sensitive material is further washed with water in a second washing step.

11. The method as claimed in Claim 1, wherein said water comprises chelating agents and antifungal agents.