US3820997A - Method of color development processing for forming stable photographic images - Google Patents

Method of color development processing for forming stable photographic images Download PDF

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US3820997A
US3820997A US00297163A US29716372A US3820997A US 3820997 A US3820997 A US 3820997A US 00297163 A US00297163 A US 00297163A US 29716372 A US29716372 A US 29716372A US 3820997 A US3820997 A US 3820997A
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solution
processing
color
fixing
bleach
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K Shirasu
T Hatano
H Iwano
I Shimamura
M Ozawa
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3046—Processing baths not provided for elsewhere, e.g. final or intermediate washings

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  • ABSTRACT In a color development process for forming stable photographic images by color-developing and bleachfixing a silver halide color photographic material containing one or more couplers, the improvement which further comprises processing the material with an oxidizing solution containing 0.3 31' g/liter of a ferricyanide complex salt.
  • this processing is followed by processing in a solution containing a reducing compound.
  • the solutions used are also set out in detail.
  • the present invention relates to a method of color development for forming stable photographic images and, more particularly, to an improved method of color photographic processing whereby stable images capable of being stored for a long period of time can be obtained with a lowered amount of harmful materials which pollute the environment, and to the composition of the processing solution used therefor.
  • the development processing of a .color photographic material includes the step of development with a color developer, bleaching wherein the developed silver is oxidized, and fixing wherein silver salt produced by the oxidation is dissolved to be removed from the photographic material.
  • a bleach-fixing step is included wherein bleaching and fixing are conducted at the same time.
  • the bleaching solution and the bleach-fixing solution contain an oxidizing agent for oxidizing the developed silver.
  • oxidizing agents include red prussiate, potassium dichromate, ethylenediaminetetraacetic acid-iron (ill) complex salt, copper (ll) compounds, etc.
  • red prussiate is particularly strong in its silver salt-bleaching ability and, since it is easily available atlow price and can be stored for long periods, it has been widely used.
  • red prussiate has a defect, i.e., its main component, ferricyanide ion, is decomposed by photolysis to form the cyanide ion, and discharge of the processing waste liquor is harmful to the environment.
  • Coupler groups are used in photographic color materials, e.g., Z-equivalent couplers, which are so called because 1 mol of dye is formed by the reduction of 2 mols of silver halide.
  • Z-equivalent couplers which are so called because 1 mol of dye is formed by the reduction of 2 mols of silver halide.
  • To this group belong the phenol-type or naphthol-type couplers wherein the p-position with respect to an OH group i.e., the coupling position, is substituted with an atom or atoms other than H, and those of the pyrazolone-type or benzoylacetanilide-type containing an active methylene group wherein one of the hydrogen atoms attached to the active methylene carbon is substituted by another atom or atoms. Since these couplers rarely remain in the non-colored structure upon coupling, the density of the image is rarely insufficient even when the aforesaid bleach-fixing solutions are used.
  • a photographic material suitable for being processed with a bleach-fixing solution containing ethylene-diaminetetraacetic acid-iron(lll) complex salt is limited to color photographic materials prepared by selecting a color former capable of providing a practical level of color density even when processed with such an oxidizing agent, and thus the possible range of selection of the color former is narrow.
  • Another object of the invention is to provide a method of color photographic processing of high quality, which always provides a definite color density regardless of small changes in the daily processing conditions.
  • a further object of the invention is to provide a stable oxidative coloring method wherein the processing solution deteriorates little even in continuous development processing by an automatic developing machine.
  • Still a further object of the invention is to provide an excellent color photographic processing method causing no color stain on the white support of the color photograph.
  • Yet a further object of the invention is to provide a method of color development processing which provides a safe working environment avoiding using strongly oxidative processing solutions or irritating solutions.
  • the processing method of the present invention comprises forming a color image or uncolored leuco-type dye and developed silver by developing an exposed silver halide color photographic material containing a coupler or couplers with a color developer containing an aromatic primary amine developer agent, subsequently processing the material with a bleach-fixing solution containing an oxidizing agent, e.g., an iron(III) complex salt such as aminopolycarboxylic acidiron(lll) or a cobalt(III) complex salt such as polyamite-cobalt(l) or cobalt nitrate(lll) or quinone, or a mixture thereof, to thereby remove the developed silver and nonreacted silver halide from the emulsion, and further processing the material with an oxidizing solution containing 0.3 3 g/liter of a ferricyanide complex salt to thereby oxidize and color substantially all of the remaining non-colored leuco-type compound, and then preferably processing with a final solution containing one or more reducing agents.
  • the inventors have discovered that there exists a range of red prussiate concentration wherein the color density is not reduced and the problem of environmental pollution is almost removed. This range of concentration varies depending upon the coupler contained in the photographic material, but it ranges approximately from 0.3 to 3 g/liter.
  • a bleach-fixing solution containing aminopolycarboxylic acid-iron(III) complex salt is capable of bleaching and removing the developed silver with sufficient speed, but it insufficient to oxidize the noncolored leuco-type compound remaining in the emulsion film to thereby form a dye, it can be expected that the oxidation potential necessary to provide enough coloring is higher than that required to bleach the developed silver.
  • the above-described concentration is smaller by more than one order of magnitude. Therefore, the discovery of the fact that oxidation to a dye can take place at a concentration at which bleaching is impossible is one of the features of the present invention.
  • the inventors have found that the lightfastness of the color image can further be improved by immersing the photographic material in a reducing solution after processing with the red prussiate solution.
  • a reducing solution after processing with the red prussiate solution.
  • this stain formation can effectively be prevented by processing with the above-described reducing solution.
  • bleach-fixing solutions used in the present invention are well known in the art, for example, bleach fixing solutions as are disclosed in German Pat. No. 866,605, British Pat. No. 991,412, U.S. Pat. No. 3,293,036 and U.S. Pat. No. 3,582,322 are representative of the types which may be used in the present invention.
  • Specific examples of the oxidizing agents are:
  • aminopolycarboxylic acid-iron(lll) complex salts such as iron(lll) chelate compounds with ethylene sliamisemtst ea a id, fi mim-lzp s assl tetraacetic acid, propylenediaminetetraacetic acid, aminotriacetic acid, cyclohexane-l ,3- diaminotetraacetic acid, aminodiacetic acid, N- hydroxyethyl-ethylenediamine-triacetic acid, nitrilotriacetic acid, and the like.
  • cobalt(lll) complex salt such as tetraminecarbonatocobalt(lll) nitrate, quinone, and simple water-soluble iron salts such as ferric chloride.
  • silver halide-dissolving agent present together with such oxidizing agents, there can be illustrated thiosulfates, thiocyanates, thioureas, thioglycol, watersoluble organic diols containing sulfur and oxygen in the molecule (e.g., 3,6-dithia-1,8-octanediol), and the like.
  • bleachfixing solution other general additives for bleach-fixing solutions may be incorporated, such as pH-buffering salts, antiswelling salts, or sulfite or like stabilizers.
  • the silver halide dissolving agent is preferably present in an amount of from about to about 150 g/liter of solution.
  • Such bleach-fixing solutions are known not only from the specifications of German Pat. No. 866,605, British Pat. No. 1,014,396 and German Pat. No. 966,410, but also from the color development method used by the main photographic companies in Europe and described in The British Journal of Photography (1960), at pages 122, 123 and 126.
  • a second oxidizing agent may also be added such as persulfuric acid or salts thereof, in addition to the ferricyanide complex salt (e.g., potassium or sodium salt).
  • the second oxidizing agent is unable to provide sufficient color density when used independently.
  • sufficient color can be provided by the presence of persulfuric acid or the salt thereof even when the concentration of ferricyanide complex salt is at a low degree where sufficient color cannot be obtained by the independent use of the ferricyanide complex salt.
  • hypochlorous acid chlorous acid, chloric acid or the alkali metal salts thereof, hydrogen peroxide, or iodine.
  • suitable mixtures of such materials may, of course, be used.
  • an alkali halide such as potassium bromide, sodium bromide, potassium iodide or sodium iodide, and/or an ammonium halide such as ammonium bromide or ammonium iodide, is added in an amount of 0.1 100 g per liter of oxidizing solution, singly or preferably in combination with the above compounds such as the persulfate, better color images can be obtained.
  • the sodium salt, ammonium salt or like salts are preferred.
  • the amount thereof is about 1 to about 20 g per liter, with the optimum amount being about 4 to about 10 g per liter, though the value will vary depending upon the kind and the amount of the coupler in the light-sensitive material processed.
  • ferricyanide complex salt As the ferricyanide complex salt to be used in such a combination, there is used a water-soluble salt comprising ferricyanide ion and a monovalent metal cation, such as potassium ferricyanide or sodium ferricyanide.
  • concentration thereof in the solution is dependant upon the kind and the amount of the coupler in the light-sensitive material and the thickness of the film.
  • the range (of the concentration of ferricyanide complex salt) satisfying the aforesaid various factors is from about 0.3 to about 3.0 g per liter and, particularly favorably, about 0.5 to l g per liter.
  • the amount thereof added is from about 8 to about 50 g per liter and, in the case of using hypochlorous acid or a salt thereof, from about 10 to about 100 ml/liter of a concentrated aqueous solution of sodium hypochlorite or potassium hypochlorite is used and, in the case of iodine from about 0.2 to about 3 g per liter of iodine is used.
  • hydrogen peroxide When used, it is preferably used in an amount of from 10 to 100 ml/liter of oxidizing solution percent aqueous hydrogen peroxide solution).
  • lodine is preferably used together with potassium iodide.
  • oxidizing solution there may further be incorporated acids, bases or salts for the purpose of adjust ing the pH and providing a buffering property, e.g., so dium carbonate, sodium bicarbonate, borax, boric acid, sodium phosphate, potassium hydrogen phthalate, sodium acetate, acetic acid, etc.
  • acids, bases or salts for the purpose of adjust ing the pH and providing a buffering property, e.g., so dium carbonate, sodium bicarbonate, borax, boric acid, sodium phosphate, potassium hydrogen phthalate, sodium acetate, acetic acid, etc.
  • the pH of the oxidizing solution may be varied over a wide range, the pH being adjusted to a value most favorable considering the relationship with the steps before and after the bath in the processing steps. ln general, the solution is used at a pH of from about 3 to about 10, but the pH value is not overly important.
  • hardeners such as aluminum sulfate and potash alum, fluorescent brightening agent (e.g., such as described in U.S. Pat. No. 2,632,701), surface active agents such as polyoxyethylene nonylphenyl ether, antiseptic or antifungal agents such as benzoic acid or salts thereof, trichlorophenol, etc. may be incorporated therein.
  • fluorescent brightening agent e.g., such as described in U.S. Pat. No. 2,632,701
  • surface active agents such as polyoxyethylene nonylphenyl ether
  • antiseptic or antifungal agents such as benzoic acid or salts thereof, trichlorophenol, etc.
  • the final bath of the present invention contains a reducing agent in an amount just sufficient to prevent the formation of color stain in the color image by oxidation during storage for a long period of time. This solution at the same time improves the light-fastness of the ma genta color image.
  • a solution bath called a stabilizing bath
  • a stabilizing bath is provided as a final bath.
  • Some conventional final baths have the effect of improving the waterdraining property by including a surface active agent, control the pH inside the image-forming layer by including a pl-l-buffering agent, stabilize the image by adding formalin, or enhance the whiteness of the tin ished print by adding a brightening agent.
  • the conventional final bath is further provided with a reducing composition.
  • the reducing agent to be used can be found among,
  • R and R represent alkyl, hydroxyalkyl, aryl or allyl, or R and R may be connected with each other to form a 5 or 6 membered heterocyclic ring, R represents alkyl, hydroxyalkyl or allyl when R, and R do not form a heterocyclic ring, or represents hydrogen, alkyl or hydroxyalkyl when R, and R form a heterocyclic ring, and X represents 0, S or NH),
  • R -SO M (wherein R represents aryl or substituted aryl, and M represents a monovalent metal)
  • R R and R represent lower alkyl such as methyl, ethyl, etc.; hydrogen, hydroxyl; lower alkoxy such as methoxy, ethoxy, etc.; carboxyl; sulfo or halogen, provided that R R and R are not hydrogen at the same time or two or more of R R and R are not hydroxyl groups at the same time, and when one of R R and R is hydrogen, halogen, carboxyl or sulfo, the other two are not lower alkyl groups),
  • HONR R (wherein R and R represent lower alkyl such as methyl or ethyl; or lower alkoxyalkyl such as methoxy or ethoxy; this compound may be in the form of a salt such as a hydrochloride, sulfate, etc.), and
  • reducing agent used in the method of this invention there are, for example, the following compounds.
  • the above-described compounds may also be used in the form of monovalent metal salt such as a alkali metal salt, e.g., a sodium salt or potassium salt, or ammonium salt, or may form isomeric structures.
  • a alkali metal salt e.g., a sodium salt or potassium salt, or ammonium salt
  • the concentration of the reducing agent-containing solution can be varied depending upon various processing conditions, and a concentration is satisfactory which maintains the interior of the image-forming layer processed in a more reduced state than in the case of conducting washing with water. Accordingly, there is no limit on the concentration of the reducing agent in order to achieve the objects of the invention.
  • the agents are preferably used in an amount (or concentration) which is as small as possible solely for economic reasons. Considering this point alone, the amount of the reducing agent used is generally less than g per liter. For practical ease of operator measurement, usually more than about 0.1 g liter of the reducing agent I will be present.
  • surface active agents such as polyoxyethylene nonyl phenyl ether wherein the polymerization degree of the oxyethylene chain is about 6 14, polyoxyethylene methylphenyl ether alkylsulfates wherein the polymerization degree of the oxyethylene chain is about 6 l0, and sodium dodecylbenzenesulfonate can be incorporated therein.
  • known fluorescent brightening agents or bluing agents may also be incorporated therein.
  • a small amount of formaldehyde or acetaldehyde is also added.
  • Short-chain alcohols such as methanol and ethanol may also be added in order to aid dissolution.
  • the inorganic hardening salts such as potash alum, aluminum sulfate or zirconium sulfate, or ionic strength-increasing additives such as sodium sulfate are added to the final bath. Additives as are described in British Pat. No. 1,001,446 and US. Pat. No. 2,647,057 can also be used in the present invention.
  • the color photographic material is processed in the final bath, and then dried as it is or after a short-water washing.
  • the color developer used in the present invention is in accordance with those that generally used by the prior art, i.e., an aqueous alkaline solution of an aromatic primary amine color developing agent which preferably contains benzyl alcohol.
  • an aromatic primary amine color developing agent which preferably contains benzyl alcohol.
  • the color developing agent there can be used, for example, any of the known aromatic primary amine color developing agents broadly described as phenylene diamine derivatives such as N-diethyl-p-phenylenediamine sulfate, 4- amino-N-ethyl-N-beta-hydroxyethylaniline sulfate, 3- methyl-4-amino-N-ethyl-beta-methanesulfoamidoethylaniline sesquisulfate monohydrate, 3-methyl-4- amino-N-ethyl-N-beta-hydroxyethylaniline sulfate, 3- methyl-4-amino-N,N-
  • developer additives such as alkali metal sulfites, carbonates, bicarbonates, bromides, iodides, antifogging carried out, and, if necessary, processing with a reduc ing solution and/or with an image-stabilizing solution, for example, as disclosed in US. Pat. No. 3,140,177.
  • the color photographic material to which the present invention is applied shows a large effect particularly when it contains I it'iest ofibr more 4-equivalent couplers in the emulwherein R represents a substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted heterocyclic group, and R represents an alkyl, carbamyl, amino or amido group.
  • such materials there are l-psec-amylphenyl-3-n-amyl-S-pyrazolone, 2-cyanoacetyl- -(p-sec-amylbenzoylamino)-coumarone, 2- cyanoacetylcoumarone-S-(N-n-amyl-p-tamylsulfoanilide), 2-cyanoacetylcoumarone-S-sulfo-N- n-butyl-anilide, l-p-laurylphenyl-3-methyl-5 pyrazolone, l-beta-naphthyl-3-amyl-5-pyrazolone, 1-p nitrophenyl-3-n-amyl-5-pyrazolone, l-phenyl-3- acetylamino-5pyrazolone, l-phenyl-3-n-valeriamino- 5-pyrazolone, l-phenyl-3-chloroace
  • couplers form dyes via a comparatively stable leuco-type structure which is different from the 2-equivalent couplers, in many cases the couplers do not form a sufficient color in a bleach-fixing bath. However, by subjecting these couplers to the processing step of the present invention. even these couplers can form sufficient color and, in addition. the problem of discharging harmful material is markedly improved.
  • the method of the invention can be applied to the processing of any general silver halide color photo graphic materials such as color negative films, color papers, color positive films, color reversal films for slides, color reversal films for movies, color reversal films for TV, etc. Therefore, there are essentially no restrictions on the type of silver halide, type of protective colloid or the type of additives to be added to the silver halide mul on...
  • the effect of the invention is particularly large when the method of the invention is employed in developing of films for general amateurs or in the developing of movie films in large amounts, since the large scale of development in such places is particularly liable to cause envionrmental pollution due to waste liquor from the development processing.
  • EXAMPLE 1 Color papers were prepared by applying onto a baryta paper a silver bromide emulsion containing a yellow coupler emulsion dispersion, a silver chlorobromide emulsion containing a magenta coupler emulsion dispersion (silver chloride content: mol percent), a silver chlorobromide emulsion containing a cyan coupler emulsion dispersion (silver chloride content: 70 mol percent), and a gelatin layer containing an ultraviolet absorbing agent.
  • Each coupler emulsion used was prepared by dispersing each coupler in a mixture of dibutyl phthalate and tricresyl phosphate and dispersing the resulting mixture in a gelatin solution as an o/w emulsion using as the dispersing emulsifier sorbitan monolaurate, Turkey red oil and sodium dodecylbenzenesulfonate.
  • the couplers used were l-(2',4,6'- trichlorophenyl)-3-[3-(2,4-di-tamylphenoxyacetamido)benzamido]-5-pyrazolone, l- (hydroxy)-4-chloro-2-n-dodecylnaphthamide, and a-(Z-methylbenzoyl)-acet-(2-chloro5-dodecoxycarbonyl)anilide.
  • the ultraviolet absorbing agent described in Japanese Patent Publication No. 9586/70 was employed.
  • the sodium salt of 2,4-dichIoro-6- hydroxy-l,3,5-triazine was added to each emulsion.
  • composition of each layer is further described in the following Table:
  • the processing solution used had the 13 14 Layer Coupler Emulsion Coupler! Coupler/ (Solvent Coupler Gelatin Solvent Gelatin)/ (wt/7a) (weight (weight Emulsit'ying ratio) ratio) Agent Red Cyan AgBr 100% III III lOO/l Green Magenta AgBr 30% do. do. do.
  • processing ll where the bleaching step and the hardening step in processing l were changed to a bleach-fixing step and an immersion in an oxidizing bath, respectively; processing Ill where the bleaching and oxidizing bath were conducted similarly to processing ll, and further the stabilizing solution of processing I was changed to stabilizing bath lll.
  • Processing ll is also a comparative example, while processing III is an example of the invention.
  • EXAMPLE 2 Color papers as described in Example 1 were exposed as in Example 1 and were continuously developed with the use of a small color paper developing ma- V
  • R, G and B represent the reflection density values measured with the use of light passed through a red filter, a green filter, and a blue filter, respectively.
  • the whiteness of the blank portion of the color paper in processing [11 in accordance with the invention is obviously whiter than that in the conventional method (processing 1) as shown by the reflection density values.
  • each of the developed samples was set in a fading resistance testing machine provided with a xenon light source wherein it was irradiated for 50 hours at an illumination of 100,000 lux.
  • processing I the ratio of density reduction at the portion whose green filter light density before irradiation had been 1.0 reached 35 percent, whereas in processing 11, the reduction ratio was only 12 percent and in processing 111 in accordance with the invention the reduction ratio was 8%.
  • the light-fastness is excellent in processings 11 and 111 and, above all, in processing 111.
  • Processing 1 is inferior in every point other than the first, and processing 11 has the fatal defect of forming stain during storage, though some improvement is achieved over processing 1.
  • the papers were processed in thefollowing color developer for 6 minutes, then in the following stop-fixing bath for 2 minutes, washed for 2 minutes, and processed in the following bleach-fixing solution for 4 minutes.
  • Oxidizing solution (in processings V and V1) Red prussiate Potassium persulfate Each sample was then subjected to an one-day incubation test in dry air at a temperature of 80C. Processing V was seriously inferior, and only processing VI in accordance with the invention wasmexcellent in both color density and storage stability.
  • the total cyanide concentration in the discharged water was less than 1 ppm.
  • EXAM LE 3 The following experiment was conducted using a color negative photographic light-sensitive material prepared by coating on a cellulose triacetate film base a red-sensitive silver halide bromoiodide emulsion (Agl content: 7 mol percent) in which l-hydroxy-4-chloro- 2-n-dodecylnaphthamide had been emulsified as a cyan coupler, a green-sensitive silver bromoiodide emulsion in which l-(2,4', 6'-trichlorophenyl )-3-[ 3 2",4' "-di-t-amylphenoxyacetamido)benzamido]--pyrazolone had been emulsitied as a magenta coupler, and a blue-sensitive silver bromoiodide emulsion in which a-(2-methylbenzoyl)- acet-(2'-chloro-5'-dodecoxycarbonyl)-anilide had been
  • Example 1 The materials were used in amounts as shown in Example 1 and were otherwise the same except that all AgX emulsions were replaced by an AgBr 93 percent Agl 7 percent emulsion.
  • the resulting film sample was divided into two portions one being processed according to a conventional development processing method (processing VII) and the other being processed according to the method of the present invention(processing VIII).
  • ashing do Bleaching bath do. Washing do. Fixing bath do. Washing do. Drying 12 min. ⁇ i do. 4 do. 4 do. 6 do. 4 do. 8 do. 8 do.
  • Steps of processing VIII (Present invention): The steps after bleaching in processing VII were ssw siefel sus.
  • Ferric sulfate Disodium cthylenediaminetctraacetate'(2 H O) Sodium carbonate monohydrate Boric acid Sodium sulfite Aqueous solution of ammonium thiosulfate The pH was adjusted to 5.5. and
  • a color development process for forming stable photographic images which comprises colordeveloping with a developer containing a non-colored leuco dye compound and bleach-fixing in the absence of a ferricyanide complex salt, a silver halide color photographic material containing one or more couplers, the improvement comprising then processing the material with an oxidizing solution containing 0.3 3g/liter of a ferricyanide complex salt to thereby oxidize and color substantially all the non-colored leuco dye compound and then processing with a solution of a reducing compound.
  • R-SO -R (wherein R and R represent NH NHR or NR R R and R being lower alkyl), 5.
  • R, and R represent alkyl, hydroxyalkyl, aryl (wherein R R and R represent lower alkyl, H, OH, OCH;,, OC H COOH, halogen or -SO H, provided that two or more of R R and R do not represent OH at the same time, or
  • R,,, R and R do not represent H at the same time, and that, when one of R R and R represents H, COOH, halogen or -SO H, the remaining two of R R or R do not represent aly 8.
  • HONR R wherein R and R represent H, lower alkyl or lower alkoxyalkyl, or a salt thereof
  • a color development processing for forming stable photographic images which comprises (1 developing a silver halide color photographic material containing one or more couplers with a developer containing an aromatic primary amine developing agent to form color image, a non-colored leuco dye compound and developed silver, (2) processing with a bleachfixing solution in the absence of a ferricyanide complex salt to remove developed silver and residual silver salt, the improvement comprising then: (3) processing with an oxidizing processing solution containing 0.3 3 g/liter of a ferricyanide complex salt to thereby oxidize and color substantially all the noncolored leuco dye compound, and then (4) processing with a solution of a reducing compound.
  • R-SO -R (wherein R and R represent NH NHR or NR R R and R being lower alkyl),
  • R -SO M (wherein R represents aryl or substituted aryl, and M represents a monovalent metal)
  • R R and R represent lower alkyl, H, OH, OCH OC H COOl-l, halogen or -SO H, provided that two or more of R R and R do not represent OH at the same time, or that R R and R do not represent H at the same time,
  • R R and R represents H, COOH, halogen or -SO H. the remaining two of R R or R do not represent alkyl
  • bleach-fixing solution contains at least one of an iron(l ll) complex salt, a cobalt(Ill) complex salt or quinone.
  • bleach-fixing solution contains at least one of an iron(lIl) complex salt, a cobalt(lll) complex salt or quinone.
  • bleach-fixing solution contains at least one of an iron(lll) complex salt, a cobalt(Ill) complex salt or quinone.
  • bleach-fixing is with a solution comprising from about 50 to about 300 g/liter of an oxidizing agent and from about 1 to about 300 g/liter of a silver halide fixing agent.
  • bleach-fixing is with a solution comprising from about 50 to about 300 g/liter of an oxidizing agent and from about i to about 300 g/liter of a silver halide fixing agent.

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4040837A (en) * 1974-12-05 1977-08-09 Konishiroku Photo Industry Co., Ltd. Photographic bleach-fixer
US4045225A (en) * 1975-07-23 1977-08-30 Fuji Photo Film Co., Ltd. Method of forming a photographic image
US4062684A (en) * 1975-07-23 1977-12-13 Fuji Photo Film Co., Ltd. Method for forming images by a stabilized color intensifying treatment
US4113490A (en) * 1974-07-12 1978-09-12 Konishiroku Photo Industry Co., Ltd. Method for processing light-sensitive silver halide photographic materials
US4134767A (en) * 1973-10-22 1979-01-16 Konishiroku Photo Industry Co., Ltd. Silver halide photosensitive material for color photography
US4268618A (en) * 1979-07-05 1981-05-19 Fuji Photo Film Co., Ltd. Bleaching composition for photographic processing
US4277556A (en) * 1976-08-18 1981-07-07 Konishiroku Photo Industry Co., Ltd. Process for treating light-sensitive silver halide color photographic materials
US4301236A (en) * 1979-01-23 1981-11-17 Fuji Photo Film Co., Ltd. Photographic bleach solutions
US4366233A (en) * 1980-05-26 1982-12-28 Fuji Photo Film Co., Ltd. Blix process for silver halide color photographic materials
US4554242A (en) * 1984-01-12 1985-11-19 Fuji Photo Film Co., Ltd. Method for processing color photographic light-sensitive material
US4756918A (en) * 1985-10-18 1988-07-12 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic materials including a counter-current bleaching-fixation system

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* Cited by examiner, † Cited by third party
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JPS5814834A (ja) * 1981-07-21 1983-01-27 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料の安定化処理方法
JPS61118753A (ja) * 1984-11-14 1986-06-06 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
US4859574A (en) * 1988-03-15 1989-08-22 Eastman Kodak Company Process for stabilizing photographic elements using a solution comprising a water-soluble N-methylol compound and a buffering agent
JPH0760258B2 (ja) * 1988-09-28 1995-06-28 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料の処理方法
DE19549103A1 (de) * 1995-12-29 1997-07-03 Agfa Gevaert Ag Bleichbad für fotografisches Schwarz-Weiß-Material

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4134767A (en) * 1973-10-22 1979-01-16 Konishiroku Photo Industry Co., Ltd. Silver halide photosensitive material for color photography
US4113490A (en) * 1974-07-12 1978-09-12 Konishiroku Photo Industry Co., Ltd. Method for processing light-sensitive silver halide photographic materials
US4040837A (en) * 1974-12-05 1977-08-09 Konishiroku Photo Industry Co., Ltd. Photographic bleach-fixer
US4045225A (en) * 1975-07-23 1977-08-30 Fuji Photo Film Co., Ltd. Method of forming a photographic image
US4062684A (en) * 1975-07-23 1977-12-13 Fuji Photo Film Co., Ltd. Method for forming images by a stabilized color intensifying treatment
US4277556A (en) * 1976-08-18 1981-07-07 Konishiroku Photo Industry Co., Ltd. Process for treating light-sensitive silver halide color photographic materials
US4301236A (en) * 1979-01-23 1981-11-17 Fuji Photo Film Co., Ltd. Photographic bleach solutions
US4268618A (en) * 1979-07-05 1981-05-19 Fuji Photo Film Co., Ltd. Bleaching composition for photographic processing
US4366233A (en) * 1980-05-26 1982-12-28 Fuji Photo Film Co., Ltd. Blix process for silver halide color photographic materials
US4554242A (en) * 1984-01-12 1985-11-19 Fuji Photo Film Co., Ltd. Method for processing color photographic light-sensitive material
US4756918A (en) * 1985-10-18 1988-07-12 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic materials including a counter-current bleaching-fixation system

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JPS4847341A (en:Method) 1973-07-05
DE2250673A1 (de) 1973-04-19
GB1376519A (en) 1974-12-04

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