US3879202A - Color photographic process - Google Patents

Color photographic process Download PDF

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US3879202A
US3879202A US293719A US29371972A US3879202A US 3879202 A US3879202 A US 3879202A US 293719 A US293719 A US 293719A US 29371972 A US29371972 A US 29371972A US 3879202 A US3879202 A US 3879202A
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color
water
methylol
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Seiya Yamaguchi
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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
    • 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
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
    • G03C7/421—Additives other than bleaching or fixing agents

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  • ABSTRACT In a process for processing a color photographic material using a waterproof support, the stability of color images formed is remarkably improved by processing the color photographic material, after color develop ment, in a blix-stabilizing bath containing a Fe (III)- organic acid complex salt, a solvent for silver halide, and a water-soluble compound having an aldehyde group or a methylol group.
  • the present invention relates to a method for processing a color photographic material and more particularly to a color photographic process for forming stable color photographic images.
  • color photographic materials by subjecting multilayer color photographic materials; after exposure, to such processings as development, bleaching, fixing, etc.
  • these color photographic materials have, on one side of the support, three spectrally sensitized emulsion layers, i.e., a bluesensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer.
  • the color photographic materials have further, where appropriate, non-sensitive subsidiary layers such as a yellow filter layer, an antihalation layer, etc.
  • Each of the light-sensitive emulsion layers of the color photographic materials may contain a ketomethylene type coupler for forming yellow images, a pyrazolone coupler for forming magenta images, or a phenolic or naphtholic coupler for forming cyan images.
  • the exposed multilayer color photographic materials are usually subjected, after color development, to a series of processings such as bleaching, fixing, water washing, etc., and then dried. Since it requires a considerably long period of time for such a color photographic process, it has recently been desired to shorten the processing time and thus various attempts have been proposed for such a purpose. For instance, it has been proposed to shorten or simplify a conventional five-bath system composed of color development, fixing, bleaching, washing and stabilization steps by employing a blix step, that is, a step which combines the bleaching step and the fixing step.
  • a blix step that is, a step which combines the bleaching step and the fixing step.
  • the three-bath system thus proposed is composed of a color development, blix, (washing) and stabilization step, and by employing such a three-bath system the color photographic processing period may be shortened to some extent as compared with the aforesaid five-bath system.
  • a three-bath system requires a considerable processing time.
  • An object of this invention is, therefore, to provide a simplified and shortened photographic process for forming stable color photographic images.
  • the aforesaid object of this invention can be attained by processing a color photographic material having a waterproof support, after color development, in a bath which simultaneously bleaches, fixes, and stabilizes the color photographic materials.
  • the novel blixstabilizing bath used in the process of this invention contains an oxidizing agent for silver, a solvent for silver halide, and a stabilizer for color images.
  • potassium ferricyanide As an oxidizing agent for silver, potassium ferricyanide is conventionally used for bleaching in the conventional five-bath system.
  • the use of potassium ferricyanide is accompanied with disadvantages, i.e., it is difficult to form a stable system of potassium ferricyanide together with a thiosulfate which is a solvent for silver halide, and the use of potassium ferricyanide causes problems of the waste liquid leading to water pollution. Accordingly, it is not appropriate to employ such a ferricyanide in the blix-stabilizing bath of this invention. Therefore, in the process of this invention, a water-soluble ferric complex salt of an organic acid is used as the oxidizing agent for silver.
  • Such a ferric complex salt has the advantages that it is stable with a thiosulfate, is excellent in chemical and photochemical stability, has less toxicity to humans, and can be readily regenerated after use.
  • the organic acid capable of forming the watersoluble ferric complex salt of the acid used in this invention includes a compound represented by the following general formula,
  • X represents a hydrocarbon group, an oxygen atom, a sulfur atom, or
  • R R R R and R each represents a substituted or unsubstituted hydrocarbon group; and R represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
  • suitable organic acids are malonic acid, tartaric acid, ethylmalonic acid, malic acid, fumaric acid, diglycolic acid, thioglycolic acid, ethyliminodipropionic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, aminotriacetic acid, ethylenedithioglycolic acid, dithioglycolic acid, and the like.
  • Such an organic acid readily forms a stable ferric chelate compound with a tri-valent iron salt such as ferric chloride, ferric sulfate, or iron alum in an aqueous medium.
  • the aforesaid organic acid may be used together with the tri-valent iron salt in an aqueous medium or a ferric complex salt of the organic acid may be used.
  • the ferric complex salt of polyaminocarboxylic .acid for example, ethylenediaminetetraacetic acid (EDTA)
  • EDTA ethylenediaminetetraacetic acid
  • the processing bath in this invention can also contain a bleach-accelerator such as potassium bromide, potassium iodide, sodium iodide, polyalkylene oxide, 2- mercaptoimidazole, 3-mercapto-l,2,4-triazole, dithioglycol, a copper complex salt of an organic acid such as cupric complex salt of EDTA, a cobalt complex salt of an organic acid such as cobaltic complex salt of EDTA, thiourea, ethylene thiourea, a selenium compound such as sodium selenosulfate, etc.
  • a bleach-accelerator such as potassium bromide, potassium iodide, sodium iodide, polyalkylene oxide, 2- mercaptoimidazole, 3-mercapto-l,2,4-triazole, dithioglycol
  • a copper complex salt of an organic acid such as cupric complex salt of EDTA
  • a cobalt complex salt of an organic acid such as
  • the processing bath can further contain an anti-bleach-fogging agent such as a hydroxylamine salt, p-aminophenol, hydroxymorpholine, ascorbic acid, l-phenyl-3- pyrazolidone, semicarbazide, hydrazine salt, etc.
  • an anti-bleach-fogging agent such as a hydroxylamine salt, p-aminophenol, hydroxymorpholine, ascorbic acid, l-phenyl-3- pyrazolidone, semicarbazide, hydrazine salt, etc.
  • a silver halide solvent is employed as the fixing component for the blix-stabilizing bath in this invention.
  • solvents are thiosulfates such as sodium thiosulfate, ammonium thiosulfate, etc., thiocyanates such as potassium thiocyanate, etc., sulfurcontaining organic dibasic acids such as bisthioglycollic acid, etc., organic diols such as 3-thia-l,5-pentanediol, etc., and imidazolidine thion.
  • Sodium sulfite, etc. can be used in combination therewith as a fixing aid.
  • the inventor investigated the following compounds. That is to say, there are ultraviolet absorbents such as water-soluble sulfo compounds, monoazo compounds, etc.; aldehyde compounds; combinations of aldehyde compounds and ultraviolet absorbents or fluorescent brightening agents; cysteine; methylol; methylolbiuret; methylolurea; biuret derivatives as are described in French Pat. No.
  • ultraviolet absorbents such as water-soluble sulfo compounds, monoazo compounds, etc.
  • aldehyde compounds combinations of aldehyde compounds and ultraviolet absorbents or fluorescent brightening agents
  • cysteine methylol
  • methylolbiuret methylolurea
  • biuret derivatives as are described in French Pat. No.
  • R-CHO General formula (I) OCH-R '-CHO wherein R represents a direct bond, a divalent aliphatic group, or a divalent aromatic group.
  • compounds represented by general formula (II) are glyoxal, succinaldehyde, tartardialdehyde, terephthalaldehyde, glutaraldehyde, oz-methylglutaraldehyde, cyclopentane-dicarboxyaldehyde, and dialdehydes as disclosed in British Pat. No. 1,102,001 and French Pat. 1,543,694.
  • the precursors of the above compounds such as 2,5-dialkoxytetrahydrofuran, etc., described in Japanese Pat. Publication No. 27,570/'64 can also be used.
  • N-methylolurea N,N'- dimethylolurea, N-methylolmethylene bismonoethylurea, N'-methylol-N,N'-dimethylolurea, methylolhydantoin, dimethylolmelamine, monomethylol dimethylhydantoin, hydroxydimethylbiuret, trihydroxymethylbiuret, 2,2,6,6-tetramethylolcyclohexanol, methyloldicyandiamide, compounds such as 3-hydroxy- 2,2-dihydroxymethylpropionic acid, etc., described in British Pat. No. l,l [6,944, 2-nitroethanol derivatives such as 2-nitro-2-methyl-l,3-propanediol described in Japanese Pat. application No. 67,799/69, etc.
  • the novel blix-stabilizing bath used in the process of this invention contains, as fundamental components, the water-soluble ferric complex salt of the organic acid, the solvent for silver halide, and the water-soluble compound having an aldehyde group or a methylol group.
  • the discovery of such a blix-stabilizing bath is quite astonishing on considering the difficulty of using an oxidizing agent such as a water-soluble ferric complex salt of an organic acid and a reducing agent such as formaldehyde simultaneously in a mono-processing bath.
  • the inventors have succeeded in using the both components in a stable manner effectively in a processing bath by adding a silver halide solvent, such as sodium thiosulfate, to the system and adjusting the pH of the solution.
  • the bath is inferior in bleaching power and the stabilizing effect for images and the density of the color images is sometimes reduced, while if the pH thereof is too high, the bleaching power is reduced.
  • the pH of it is suitably about 5.5 to about 7.5, preferably 6.0 to 7.0. Any known pH controlling agent may be used, but usually a carbonate is employed for this purpose.
  • the amount of the water-soluble compound having an aldehyde group of a methylol group depends on the nature of the compound and is usually determined upon considering the stabilizing effect for images and the stability of the solution. For instance, when a 37% aqueous solution of formaldehyde is employed, a preferred amount of the solution is 2 to 6 ml per liter of the bath solution, while when 2% aqueous solution of dimethylurea is employed, a preferred amount thereof is 4 to 15 ml per liter of the bath solution. ln general, a suitable amount of the water-soluble compound having an aldehyde group or a methylol group is in the range of from 0.05 to 5 g per liter of the solution.
  • the amounts of the bleaching component and the fixing component are easily determined according to the characteristics desired. Generally from 40 to 60 g per liter of the bleaching component and from g to 200 g per liter of the fixing component, respectively, are employed.
  • a water-soluble fluorescent brightening agent can be incorporated in the blix-stabilizing composition of this invention to add a color image stabilizing action and brightening action.
  • a surface active agent may be incorporated in the bath composition as a draining agent or an extender.
  • Any color photographic material such as a color photographic negative film, color photographic paper, reversal color photographic film, color reversal paper, etc., can be used in the process of this invention.
  • an anti-halation layer In a color negative film and color reversal film, an anti-halation layer, a red-sensitive emulsion layer containing a cyan coupler, a green-sensitive emulsion layer containing a magenta coupler, a yellow filter layer, a blue-sensitive emulsion layer containing a yellow coupler, and a gelatin protective layer are formed on a support, in this order.
  • a blue-sensitive emulsion layer containing a yellow coupler, a greensensitive emulsion layer containing a magenta coupler, a red-sensitive emulsion layer containing a cyan coupler, and a gelatin protective layer are formed on a support, in this order.
  • a packet-type color photographic material having a single light-sensitive layer having dispersed therein a packet containing a blue-sensitive emulsion and a yellow coupler, a packet containing a greensensitive emulsion and a megenta coupler, and a packet containing a red-sensitive emulsion and a cyan coupler can be used in the process of this invention.
  • the support for the color photographic material must absorb no or substantially no water or photographic processing solution.
  • Such supports are well known in this art as waterproof or waterrepellent support.
  • Such supports are cellulose nitrate films, cellulose acetate films, polystyrene films, polycarbonate films, polyester films etc., and such films further containing a white pigment, cellulose films opacified by dispersing a fine foam therein as described in U.S. Pat. No. 2,422,008, a metallic sheet such as an aluminum sheet, baryta-coated papers having incorporated in the paper pulp polygalactomannan as described in German Pat. No. 1,262,756, supports composed of acyl cellulose fibers as described in U.S. Pat. Nos.
  • the photographic layers applied onto the support may be any of the conventionally known ones. That is to say, as the hydrophilic colloid forming each of the photographic layers, there can be used gelatin, albumin, cellulose derivatives such as cellulose hydrates, polyvinyl alcohol, etc. These photographic layers are preferably hardened by hardening agents.
  • Magenta couplers l-phenyl-3-benzamidopyrazole-5-one, 1-pnitrophenyl-3-n-amyl-5-pyrazolone, l-phenyl-3- acetylamino-S-pyrazolone, 2-cyanoacetyl-5 benzoylaminocoumarone, and 2- cyanoacetylcoumarone-S-sulfodimethylamide.
  • couplers can be incorporated into the hydrophilic colloid in any conventional manner.
  • photographic materials are, after color development, processed in the blix-stabilizing bath and then washed and dried.
  • an alkaline aqueous solution containing a primary aromatic amine developing agent is used as the color developing solution used for developing the photographic materials.
  • Any such conventional developing agent as used in present color developing processes may be used in the present invention.
  • phenylenediamine compounds and p-aminophenol compounds there are illustrated phenylenediamine compounds and p-aminophenol compounds.
  • Known additives conventionally used in this field may be added to the developing solution.
  • such additives as a sulfite, a bisulfite, a carbonate, a bromide, an iodide, an amine, benzyl alcohol, etc.
  • processing steps of this invention vary to some extent according to the nature and use of the photographic materials to be processed as shown below.
  • a color developing solution containing a color developing agent such as 2-amino-5-diethylaminotoluene hydrochloride together with benzyl alcohol, sodium metaborate, potassium bromide, etc.
  • the photographic films are immediately processed in a stopping solution containing glacial acetic acid and, after washing, processed in the blix-stabilizing bath of this invention followed by washing and drying.
  • color photographic papers In the case of processing color photographic papers, after developing the color photographic papers in a color developing solution containing a color developing agent such as p-hydroxyethylaminoaniline sulfate together with benzyl alcohol, sodium metaborate, hydroxylamine sulfate, sodium hydroxide, etc., the color photographic papers are immediately washed in a short period of time and then processed in the blix-stabilizing bath of this invention followed by washing and drying.
  • a color developing agent such as p-hydroxyethylaminoaniline sulfate together with benzyl alcohol, sodium metaborate, hydroxylamine sulfate, sodium hydroxide, etc.
  • the number of processing steps and the time required for each step in the conventional five-bath and three-bath system are compared with those in the two-bath system of this invention as shown in the following table, in which the processing temperature is 24 C in each step.
  • the number of steps in the two-bath system of this invention is less than half of those in the five-bath system and is less than the number of the steps in the three-bath system by one step. Furthermore, the processing time in the two-bath system of this invention is shortened about 40% as compared to the processing period in the five-bath system and about 25% as compared to the processing period in the three-bath system. Furthermore, in the process of this invention it is possible to finish the whole process within minutes when the processing temperature is increased to 35 38 C.
  • a stabilization bath is employed before the drying step as an independent step, but in the system of this invention a stabilization effect similar to or better than that obtained by the conventional step is obtained by the processing in the blixstabilization bath. That is to say, when the color paper processed according to the process described in Example 2 after stepwise exposure through a red filter, a green filter, and a blue filter, and a color paper processed in the same way as in Example 2 except that only formalin was, removed from the blix-stabilizing composition, were placed for 10 days in a chamber maintained at a temperature of 60 C and a humidity of 70%, the color densities, i.e., the cyan density, magenta density, and yellow density, of the color papers were measured, and compared.
  • the color densities i.e., the cyan density, magenta density, and yellow density
  • the yellow fog density of the paper processed in the bath containing formalin was 0.08, while that of the paper processed in the bath containing no formalin was 0.12. This shows that the blix-stabilizing solution of this invention prevents increased of yellow stain by heat and humidity with the passage of time.
  • An aldehyde compound is believed to stabilize unreacted couplers in emulsion layers by reaction with them and at the same time it is believed that it has the effect of preventing change of the color images due to moisture by the hardening action thereof.
  • the emulsion layers softened during the development step, washing step, etc. are hardened again by the hardening action of the compound having an aldehyde group or a methylol group in the blix-stabilizing bath and thus the emulsion layers are also prevented from being swollen in the blix-stabilizing bath and during washing. Therefore, the occurrence of mechanical damage such as scratches, reticulation, etc., to the emulsion layers during processing and washing can be effectively prevented. Furthermore, because the emulsion layers will not be melted by the action of the hardening action even if the photographic materials are processed at a high temperature, it is possible to dry the photographic material at high temperature in a shortened period of time.
  • the stabilization action for color images tends to be reduced when the washing after the blix-stabilizing process is conducted for a long period of time but there is no such difficulty since in the process of this invention color photographic materials having waterproof supports are employed.
  • EXAMPLE 1 A polyethylene-coated waterproof paper prepared as a blue-sensitive silver iodobromide emulsion layer containing ethyl-p-benzoylacetaminobenzene sulfonate, a green-sensitive silver chlorobromide emulsion layer containing 1-p-nitrophenyl-3-n-amyl-5-pyrazolone, a red-sensitive silver chlorobromide emulsion layer containing 2.4-dichloro-S-palmitylamino-l-naphthol, and a protective layer of gelatin to provide a multilayer color photographic paper. Then the color paper was, after exposure, processed at 29.5 C in the following way:
  • the processing time was shortened to about l2 minutes and the properties of the color image as well as the stability thereof to light and heat were not inferior to those in a conventional system employing individual bleaching, fixing, and stabilizing steps.
  • composition of the color developing solution used in the above processings was the same as that described in Example 1.
  • Glacial acetic acid 20 ml Anhydrous sodium sulfite l0 g Water to 1 liter pH 4.5
  • the processing period of time was shortened and a color image stable to light and heat was obtained.
  • a process for developing a color photographic material having a waterproof support wherein the material is subjected to a color development process and then simultaneously bleached, fixed and stabilized with an oxidizer, a silver halide solvent and a compound containing an aldehyde group or a methylol group, wherein the improvement consists essentially of color developing said material and then simultaneously bleaching, fixing and stabilizing said photographic material by processing the color photographic material in a blixstabilizing bath containing a water-soluble ferric complex salt of an organic acid, a solvent for silver halide,
  • said water-soluble compound having an aldehyde group or a methylol group is a compound represented by the formula RCHO wherein R represents an alkyl group, an aryl group, an ally] group, or a heterocyclic group.
  • said water-soluble compound having an aldehyde group or a methylol group is a compound represented by the formula OHC-R'CHO wherein R represents a direct bond, a divalent aliphatic group or a divalent aromatic group.
  • said water-soluble compound having an aldehyde group or a methylol group is a compound represented by the formula R"-CH OH HOOC-R X-R COOH i 3.. LOOC R II R COOH HOOC-R -N-R COOH wherein X represents a hydrocarbon group, an oxygen tetramethylolcyclohexanol,
  • R R R R and R each represents a substituted or unsubstituted hydrocarbon group; and R represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
  • organic acid is malonic acid, tartaric acid, ethylmalonic acid, malic acid, fumaric acid, diglycolic acid, thioglycolic acid, ethyliminodipropionic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, aminotriacetic acid, ethylenedithioglycolic acid, or dithioglycolic acid.
  • said solvent for silver halide is a thiosulfate, a thiocyanate, an organic sulfur-containing dibasic acid, or an organic diol.
  • said water soluble compound having a aldehyde group or a methylol group is formaldehyde, paraformaldehyde, trioxymethylene, glycolaldehyde, methylal, chloral, acetaldehyde, aldol, propiolaldehyde, acrolein, dibromoacrolein, crotonaldehyde, salicylaldehyde, gluoxylic acid, mucochloric acid, mucobromic acid, arabinose, xylose, glyceraldehyde, furfural or precursors thereof.
  • said water soluble compound having an aldehyde group or a methylol group is glyoxal, succinaldehyde, tartardialdehyde, terephthalaldehyde, glutaraldehyde, a-methylglutaraldehyde, cyclopentanedicarboxyaldehyde, or precursors thereof.
  • said water soluble compound having an aldehyde group or a methylol group is N-methylolurea, N,N'-dimethylolurea, N- methylolmethylene bis-monoethylurea, N'-methylol- N,N'-dimethylolurea, methylohydantoin, dimethylolmelamine, monomethylol dimethylhydantoin, hydroxydimethylberiet, trihydroxymethylbuiret, 2,2,6,6-
  • said blixstabilizing bath additionally contains a water-soluble fluorescent brightening agent.

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Abstract

In a process for processing a color photographic material using a waterproof support, the stability of color images formed is remarkably improved by processing the color photographic material, after color development, in a blix-stabilizing bath containing a Fe (III)- organic acid complex salt, a solvent for silver halide, and a water-soluble compound having an aldehyde group or a methylol group.

Description

United States Patent [1 1 Yamaguchi 1 Apr. 22, 1975 1 COLOR PI-IOTOGRAPI-IIC PROCESS [75] Inventor:
[22] Filed: Sept. 29, 1972 [21] Appl. No.: 293,719
Seiya Yamaguchi, Kanagawa. Japan [30] Foreign Application Priority Data Sept. 30. 1971 Japan 46-76516 [52] U.S. Cl. 96/22; 96/60 BF [51] Int. Cl. G036 7/16; G03c 5/32 [58] Field of Search 96/60, 60 BF, 22
[56] References Cited UNITED STATES PATENTS 3.335.004 8/1967 Wrisley et a1 96/22 3.582.322 6/1971 Edens et al. 96/22 3.591.380 7/1971 Ohkubo et a1. I 6/22 3.667.950 6/1972 Amano ct a]. 96/22 3.741.763 6/1973 Amano ct al. 96/22 FOREIGN PATENTS OR APPLICATIONS 2.102.713 8/1972 Germany 96/60 BF 1.190.855 5/1970 United Kingdom 96/60 BF OTHER PUBLICATIONS Mason. Processing Chemistry. 1966, pp. 210-211, 265-266.
Primary Examiner-Mary F. Kelley Attorney, Agent, or Firm-Sughrue, Rothwell. Mion, Zinn and Macpeak [57] ABSTRACT In a process for processing a color photographic material using a waterproof support, the stability of color images formed is remarkably improved by processing the color photographic material, after color develop ment, in a blix-stabilizing bath containing a Fe (III)- organic acid complex salt, a solvent for silver halide, and a water-soluble compound having an aldehyde group or a methylol group.
12 Claims, No Drawings COLOR PHOTOGRAPIIIC PROCESS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a color photographic material and more particularly to a color photographic process for forming stable color photographic images.
2. Description of the Prior Art It is well known in the color photographic field to form color photographic images by subjecting multilayer color photographic materials; after exposure, to such processings as development, bleaching, fixing, etc. Generally these color photographic materials have, on one side of the support, three spectrally sensitized emulsion layers, i.e., a bluesensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer. The color photographic materials have further, where appropriate, non-sensitive subsidiary layers such as a yellow filter layer, an antihalation layer, etc.
Each of the light-sensitive emulsion layers of the color photographic materials may contain a ketomethylene type coupler for forming yellow images, a pyrazolone coupler for forming magenta images, or a phenolic or naphtholic coupler for forming cyan images.
The exposed multilayer color photographic materials are usually subjected, after color development, to a series of processings such as bleaching, fixing, water washing, etc., and then dried. Since it requires a considerably long period of time for such a color photographic process, it has recently been desired to shorten the processing time and thus various attempts have been proposed for such a purpose. For instance, it has been proposed to shorten or simplify a conventional five-bath system composed of color development, fixing, bleaching, washing and stabilization steps by employing a blix step, that is, a step which combines the bleaching step and the fixing step. The three-bath system thus proposed is composed of a color development, blix, (washing) and stabilization step, and by employing such a three-bath system the color photographic processing period may be shortened to some extent as compared with the aforesaid five-bath system. However, even such a three-bath system requires a considerable processing time.
SUMMARY OF THE INVENTION An object of this invention is, therefore, to provide a simplified and shortened photographic process for forming stable color photographic images.
The aforesaid object of this invention can be attained by processing a color photographic material having a waterproof support, after color development, in a bath which simultaneously bleaches, fixes, and stabilizes the color photographic materials.
The novel blixstabilizing bath used in the process of this invention contains an oxidizing agent for silver, a solvent for silver halide, and a stabilizer for color images.
DETAILED EXPLANATION OF THE INVENTION As an oxidizing agent for silver, potassium ferricyanide is conventionally used for bleaching in the conventional five-bath system. However, the use of potassium ferricyanide is accompanied with disadvantages, i.e., it is difficult to form a stable system of potassium ferricyanide together with a thiosulfate which is a solvent for silver halide, and the use of potassium ferricyanide causes problems of the waste liquid leading to water pollution. Accordingly, it is not appropriate to employ such a ferricyanide in the blix-stabilizing bath of this invention. Therefore, in the process of this invention, a water-soluble ferric complex salt of an organic acid is used as the oxidizing agent for silver. Such a ferric complex salt has the advantages that it is stable with a thiosulfate, is excellent in chemical and photochemical stability, has less toxicity to humans, and can be readily regenerated after use.
The organic acid capable of forming the watersoluble ferric complex salt of the acid used in this invention includes a compound represented by the following general formula,
-COOH wherein X represents a hydrocarbon group, an oxygen atom, a sulfur atom, or
R R R R and R each represents a substituted or unsubstituted hydrocarbon group; and R represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
Specific examples of suitable organic acids are malonic acid, tartaric acid, ethylmalonic acid, malic acid, fumaric acid, diglycolic acid, thioglycolic acid, ethyliminodipropionic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, aminotriacetic acid, ethylenedithioglycolic acid, dithioglycolic acid, and the like. Such an organic acid readily forms a stable ferric chelate compound with a tri-valent iron salt such as ferric chloride, ferric sulfate, or iron alum in an aqueous medium. Accordingly, in the present invention, the aforesaid organic acid may be used together with the tri-valent iron salt in an aqueous medium or a ferric complex salt of the organic acid may be used. Among them, the ferric complex salt of polyaminocarboxylic .acid, for example, ethylenediaminetetraacetic acid (EDTA), is most generally used because such a complex salt has a high bleaching power, is stable and is easily obtained commercially.
The processing bath in this invention can also contain a bleach-accelerator such as potassium bromide, potassium iodide, sodium iodide, polyalkylene oxide, 2- mercaptoimidazole, 3-mercapto-l,2,4-triazole, dithioglycol, a copper complex salt of an organic acid such as cupric complex salt of EDTA, a cobalt complex salt of an organic acid such as cobaltic complex salt of EDTA, thiourea, ethylene thiourea, a selenium compound such as sodium selenosulfate, etc. Also, the processing bath can further contain an anti-bleach-fogging agent such as a hydroxylamine salt, p-aminophenol, hydroxymorpholine, ascorbic acid, l-phenyl-3- pyrazolidone, semicarbazide, hydrazine salt, etc.
As the fixing component for the blix-stabilizing bath in this invention, a silver halide solvent is employed. Examples of such solvents are thiosulfates such as sodium thiosulfate, ammonium thiosulfate, etc., thiocyanates such as potassium thiocyanate, etc., sulfurcontaining organic dibasic acids such as bisthioglycollic acid, etc., organic diols such as 3-thia-l,5-pentanediol, etc., and imidazolidine thion. Sodium sulfite, etc., can be used in combination therewith as a fixing aid.
in order to find the compounds capable of being used together with the above-mentioned bleaching component and fixing component and having the function of improving the stability of the color images, the inventor investigated the following compounds. That is to say, there are ultraviolet absorbents such as water-soluble sulfo compounds, monoazo compounds, etc.; aldehyde compounds; combinations of aldehyde compounds and ultraviolet absorbents or fluorescent brightening agents; cysteine; methylol; methylolbiuret; methylolurea; biuret derivatives as are described in French Pat. No. 1,290,631; thiol compounds; polyhydroxy compounds; combinations of aldehydes and polycarboxylic acids; carbohydrazide; water-soluble salts of cysteine; water-soluble salts of copper, manganese, uranyl, nickel, lead, or zinc; glucoheptonic acid; glucoheptonate; glycine; glycylglycine; N,N-dialkylglycine; and adducts of aldehyde or methylketones and alkali metal sulfites.
As a result of the overall investigation of the systems resulting when the above compounds are used together with the bleaching component and the fixing component indicated above, the stability of the solution, the function of stabilizing color images, the influence on the photographic properties and physical properties of photographic materials, and the toxicity to humans, it has been discovered that the water soluble compounds having an aldehyde group or a methylol group represented by the general formula (I), (II), or (III) shown below are effective.
R-CHO General formula (I) OCH-R '-CHO wherein R represents a direct bond, a divalent aliphatic group, or a divalent aromatic group.
Specific examples of compounds represented by general formula (II) are glyoxal, succinaldehyde, tartardialdehyde, terephthalaldehyde, glutaraldehyde, oz-methylglutaraldehyde, cyclopentane-dicarboxyaldehyde, and dialdehydes as disclosed in British Pat. No. 1,102,001 and French Pat. 1,543,694. The precursors of the above compounds such as 2,5-dialkoxytetrahydrofuran, etc., described in Japanese Pat. Publication No. 27,570/'64 can also be used.
General formula (II) General Formula (lll) R" CH OH wherein R" represents an aliphatic group, an aromatic group, or a heterocyclic group.
Specific examples of the compounds represented by general formula (III) are N-methylolurea, N,N'- dimethylolurea, N-methylolmethylene bismonoethylurea, N'-methylol-N,N'-dimethylolurea, methylolhydantoin, dimethylolmelamine, monomethylol dimethylhydantoin, hydroxydimethylbiuret, trihydroxymethylbiuret, 2,2,6,6-tetramethylolcyclohexanol, methyloldicyandiamide, compounds such as 3-hydroxy- 2,2-dihydroxymethylpropionic acid, etc., described in British Pat. No. l,l [6,944, 2-nitroethanol derivatives such as 2-nitro-2-methyl-l,3-propanediol described in Japanese Pat. application No. 67,799/69, etc.
The novel blix-stabilizing bath used in the process of this invention contains, as fundamental components, the water-soluble ferric complex salt of the organic acid, the solvent for silver halide, and the water-soluble compound having an aldehyde group or a methylol group. The discovery of such a blix-stabilizing bath is quite astonishing on considering the difficulty of using an oxidizing agent such as a water-soluble ferric complex salt of an organic acid and a reducing agent such as formaldehyde simultaneously in a mono-processing bath. However, the inventors have succeeded in using the both components in a stable manner effectively in a processing bath by adding a silver halide solvent, such as sodium thiosulfate, to the system and adjusting the pH of the solution.
If the pH of the blix-stabilizing bath used in this invention is too low, the bath is inferior in bleaching power and the stabilizing effect for images and the density of the color images is sometimes reduced, while if the pH thereof is too high, the bleaching power is reduced. The pH of it is suitably about 5.5 to about 7.5, preferably 6.0 to 7.0. Any known pH controlling agent may be used, but usually a carbonate is employed for this purpose.
The amount of the water-soluble compound having an aldehyde group of a methylol group depends on the nature of the compound and is usually determined upon considering the stabilizing effect for images and the stability of the solution. For instance, when a 37% aqueous solution of formaldehyde is employed, a preferred amount of the solution is 2 to 6 ml per liter of the bath solution, while when 2% aqueous solution of dimethylurea is employed, a preferred amount thereof is 4 to 15 ml per liter of the bath solution. ln general, a suitable amount of the water-soluble compound having an aldehyde group or a methylol group is in the range of from 0.05 to 5 g per liter of the solution.
The amounts of the bleaching component and the fixing component are easily determined according to the characteristics desired. Generally from 40 to 60 g per liter of the bleaching component and from g to 200 g per liter of the fixing component, respectively, are employed.
Furthermore, a water-soluble fluorescent brightening agent can be incorporated in the blix-stabilizing composition of this invention to add a color image stabilizing action and brightening action.
Also, a surface active agent may be incorporated in the bath composition as a draining agent or an extender.
Any color photographic material such as a color photographic negative film, color photographic paper, reversal color photographic film, color reversal paper, etc., can be used in the process of this invention.
In a color negative film and color reversal film, an anti-halation layer, a red-sensitive emulsion layer containing a cyan coupler, a green-sensitive emulsion layer containing a magenta coupler, a yellow filter layer, a blue-sensitive emulsion layer containing a yellow coupler, and a gelatin protective layer are formed on a support, in this order.
In a color photographic paper, a blue-sensitive emulsion layer containing a yellow coupler, a greensensitive emulsion layer containing a magenta coupler, a red-sensitive emulsion layer containing a cyan coupler, and a gelatin protective layer are formed on a support, in this order.
Also, a packet-type color photographic material having a single light-sensitive layer having dispersed therein a packet containing a blue-sensitive emulsion and a yellow coupler, a packet containing a greensensitive emulsion and a megenta coupler, and a packet containing a red-sensitive emulsion and a cyan coupler can be used in the process of this invention.
In the present invention, the support for the color photographic material must absorb no or substantially no water or photographic processing solution. Such supports are well known in this art as waterproof or waterrepellent support. Examples of such supports are cellulose nitrate films, cellulose acetate films, polystyrene films, polycarbonate films, polyester films etc., and such films further containing a white pigment, cellulose films opacified by dispersing a fine foam therein as described in U.S. Pat. No. 2,422,008, a metallic sheet such as an aluminum sheet, baryta-coated papers having incorporated in the paper pulp polygalactomannan as described in German Pat. No. 1,262,756, supports composed of acyl cellulose fibers as described in U.S. Pat. Nos. 3,098,786 and 3,132,944, and the socalled resin-coated papers prepared by coating both sides of a paper with a waterproof synthetic resin such as polyethylene, as described in U.S. Pat. No. 3,448,000, French Pat. No. 1,517,560, German Pat. Nos. 1,261,746 and 1,809,606, and British Pat. No. 1,183,613. Ordinary baryta-coated papers are unsuitable in the process of this invention since they require water washing for a long period of time to remove chemicals absorbed therein during photographic processings.
The photographic layers applied onto the support may be any of the conventionally known ones. That is to say, as the hydrophilic colloid forming each of the photographic layers, there can be used gelatin, albumin, cellulose derivatives such as cellulose hydrates, polyvinyl alcohol, etc. These photographic layers are preferably hardened by hardening agents. Known silver halide emulsions used in this invention. Each silver halide emulsion may contain, if desired, conventional additives such as a sensitizer, a sensitizing dye, a stabilizer, etc.
Moreover, the photographic materials used in this inw-benzoylacet-(Z-n-pentadecyloxy)-4-sulfoanilide,
N-phenyl-N'-(p-acetaminophenol)-urea, ethyl-pbenzoylacetaminobenzene sulfonate, w-benzoylacet- 2,5-dichloroanilide, N,N'-di-(acetoacetamino)-3,3'-
dimethyldiphenyl, N-amyl-pbenzoylacetaminobenzene sulfonate.
Magenta couplers: l-phenyl-3-benzamidopyrazole-5-one, 1-pnitrophenyl-3-n-amyl-5-pyrazolone, l-phenyl-3- acetylamino-S-pyrazolone, 2-cyanoacetyl-5 benzoylaminocoumarone, and 2- cyanoacetylcoumarone-S-sulfodimethylamide.
Cyan couplers:
l-stearoylamido4-( l '-hydroxy-2 '-naphthoylamido benzene-S-sulfonic acid, l-naphthol-5-sulfocyclohexylamide, 5-(n-benzyl-N-n-valerylamino l -naphthol, 2,4-dichloro-5-palmithylaminol -naphthol, 2-benzoylamino-5-methylphenol, and 2,2'-dihydroxy-5.5-
' dibromostilbene.
These couplers can be incorporated into the hydrophilic colloid in any conventional manner.
According to the process of this invention photographic materials are, after color development, processed in the blix-stabilizing bath and then washed and dried. As the color developing solution used for developing the photographic materials, an alkaline aqueous solution containing a primary aromatic amine developing agent is used. Any such conventional developing agent as used in present color developing processes may be used in the present invention. For example, there are illustrated phenylenediamine compounds and p-aminophenol compounds. Known additives conventionally used in this field may be added to the developing solution. For example, such additives as a sulfite, a bisulfite, a carbonate, a bromide, an iodide, an amine, benzyl alcohol, etc.
Of course, the processing steps of this invention vary to some extent according to the nature and use of the photographic materials to be processed as shown below. In the case of processing color negative films, after developing the color photographic films in a color developing solution containing a color developing agent such as 2-amino-5-diethylaminotoluene hydrochloride together with benzyl alcohol, sodium metaborate, potassium bromide, etc., the photographic films are immediately processed in a stopping solution containing glacial acetic acid and, after washing, processed in the blix-stabilizing bath of this invention followed by washing and drying.
In the case of processing color photographic papers, after developing the color photographic papers in a color developing solution containing a color developing agent such as p-hydroxyethylaminoaniline sulfate together with benzyl alcohol, sodium metaborate, hydroxylamine sulfate, sodium hydroxide, etc., the color photographic papers are immediately washed in a short period of time and then processed in the blix-stabilizing bath of this invention followed by washing and drying.
In the case of processing color reversal films or color reversal papers, after developing the color reversal materials in 'a black and white developing solution containing a developing agent such as metol, hydroquinone, and phenidone together with sodium carbonate, potassium thiocyanide, potassium bromide, etc., the photographic materials are immediately processed in a stopping solution containing glacial acetic acid, washed, subjected to a reversal exposure, subjected to color development in a color developing solution containing a color developing agent such as 2-amino-5- diethylaminotoluene hydrochloride together with benzyl alcohol, sodium tertiary phosphate, sodium hydroxide, ethylenediamine, potassium bromide, etc., processed in the blix-stabilizing bath of this invention, washed, and then dried.
Now, the advantages obtained by the process of this invention will be described in greater detail.
1. Reduction of the number of processing baths and shortage of processing period of time:
As an example, in the case of using color photographic papers prepared by coating waterproof papers with the above-indicated photographic emulsions, the number of processing steps and the time required for each step in the conventional five-bath and three-bath system are compared with those in the two-bath system of this invention as shown in the following table, in which the processing temperature is 24 C in each step.
Five-bath system Three-bath system Two-bath system 1. Color devel. Color devel. Color development lopment lopment 6 min. 6 min. 6 min 2. Stop-fixing 2. Blixing 2. Blix-stabili- 2 min. 6 min. zation 6 min. 3. Washing 3. Washing 3. Washing 2 min. 3 min. 2 min. 4. Bleaching 4. Stabilization 2 min. 4 min. 5. Washing 2 min. 6. Hardeningfixing 4 min. 7. Washing 3 min. 8. Stabilization 4 min. 8 steps 4 steps 3 steps 25 min. 19 min. 14 min.
As is clear from the above table, the number of steps in the two-bath system of this invention is less than half of those in the five-bath system and is less than the number of the steps in the three-bath system by one step. Furthermore, the processing time in the two-bath system of this invention is shortened about 40% as compared to the processing period in the five-bath system and about 25% as compared to the processing period in the three-bath system. Furthermore, in the process of this invention it is possible to finish the whole process within minutes when the processing temperature is increased to 35 38 C.
Such a reduction in the number of processing baths and shortening of the processing time are quite effective to compactness the time required for processing in an automatic developing machine, to reduce the processing cost, increase the processing capacity, and increase the efficiency of operation.
2. Stabilization of the color images to heat, humidity, and light:
In the conventional systems a stabilization bath is employed before the drying step as an independent step, but in the system of this invention a stabilization effect similar to or better than that obtained by the conventional step is obtained by the processing in the blixstabilization bath. That is to say, when the color paper processed according to the process described in Example 2 after stepwise exposure through a red filter, a green filter, and a blue filter, and a color paper processed in the same way as in Example 2 except that only formalin was, removed from the blix-stabilizing composition, were placed for 10 days in a chamber maintained at a temperature of 60 C and a humidity of 70%, the color densities, i.e., the cyan density, magenta density, and yellow density, of the color papers were measured, and compared. The yellow fog density of the paper processed in the bath containing formalin was 0.08, while that of the paper processed in the bath containing no formalin was 0.12. This shows that the blix-stabilizing solution of this invention prevents increased of yellow stain by heat and humidity with the passage of time.
Furthermore, when the above samples subjected to the described processings were exposed to a xenon lamp for 12 hours, the yellow density of the sample obtained by the process using the processing bath containing no formalin was reduced to 0.87, while the yellow density of the sample processed in the processing solution containing formalin was 1.00, which shows that the color image obtained with the blix-stabilizing bath was prevented from being faded by light.
An aldehyde compound is believed to stabilize unreacted couplers in emulsion layers by reaction with them and at the same time it is believed that it has the effect of preventing change of the color images due to moisture by the hardening action thereof.
3. Prevention of the damage of films during processing and speed up of drying by the hardening action:
The emulsion layers softened during the development step, washing step, etc., are hardened again by the hardening action of the compound having an aldehyde group or a methylol group in the blix-stabilizing bath and thus the emulsion layers are also prevented from being swollen in the blix-stabilizing bath and during washing. Therefore, the occurrence of mechanical damage such as scratches, reticulation, etc., to the emulsion layers during processing and washing can be effectively prevented. Furthermore, because the emulsion layers will not be melted by the action of the hardening action even if the photographic materials are processed at a high temperature, it is possible to dry the photographic material at high temperature in a shortened period of time.
4. Prevention of the generation of irritative gases:
In the conventional system of employing a stabilizing bath containing formalin, etc., directly before drying, irritative formalin vapors are formed during drying. Such a problem does not occur in the process of this invention since a washing treatment is conducted after the blix-stabilizing process.
The stabilization action for color images tends to be reduced when the washing after the blix-stabilizing process is conducted for a long period of time but there is no such difficulty since in the process of this invention color photographic materials having waterproof supports are employed.
Now, the invention will be described in greater detail by reference to the following examples. Unless otherwise stated, all parts and percents are by weight.
EXAMPLE 1 A polyethylene-coated waterproof paper prepared as a blue-sensitive silver iodobromide emulsion layer containing ethyl-p-benzoylacetaminobenzene sulfonate, a green-sensitive silver chlorobromide emulsion layer containing 1-p-nitrophenyl-3-n-amyl-5-pyrazolone, a red-sensitive silver chlorobromide emulsion layer containing 2.4-dichloro-S-palmitylamino-l-naphthol, and a protective layer of gelatin to provide a multilayer color photographic paper. Then the color paper was, after exposure, processed at 29.5 C in the following way:
Color development 6 min Washing 30 sec. Blix-stabilization 3 min Washing 2 min Color developing solution:
Sodium tertiary phosphate (lIZH- O) g Sodium metaborate 10 g Anhydrous sodium sulfite l g Hydroxylamine sulfate 2 g Potassium bromide 0.5 g o-Nitrobenyjoimidazole nitrate (0.2%) ml Benzyl alcohol 40% solution 45 ml Sodium hydroxide 1.2 g 4-Am ino-N-ethyl-N-( B-methasulfonamidoethyl)-mtoluidine sulfate 8.5 g Water to 1 liter pH 10.0
Blix-stabilizing solution:
Ferric chloride 6H O 2.9 g Z-Sodium ethylenediaminetetraacetic acid 40 g Anhydrous sodium carbonate 16 g Anhydrous sodium thiosulfate 150 g Anhydrous sodium sulfite 10 g Formalin (37% formaldehyde) 4 ml Water to l liter pH 6.7
The processing time was shortened to about l2 minutes and the properties of the color image as well as the stability thereof to light and heat were not inferior to those in a conventional system employing individual bleaching, fixing, and stabilizing steps.
EXAMPLE 2 In place of the blix-stabilizing solution used in Example l, a solution having the formula composition was used.
Ferric complex salt of EDTA Anhydrous sodium carbonate Anhydrous sodium thiosulfate l Anhydrous sodium sulfite Formalin (37'71 formaldehyde) Water to Almost the same results as obtained in Example 1 were obtained.
EXAMPLE 3 In place of the blix-stabilizing solution used in Example l, a solution having the following composition was employed.
Ferric complex salt of EDTA 50 g Anhydrous sodium carbonate 6 g Potassium bromide l2 g Thiourea 10 g Ammonium thiosulfate 100 g Tinopal GS 2 g Dimethylolurea (2% aqueous solution) 10 ml Water to 1 liter pH 6.8 (C) mide Almost the same results as in Example 1 were obtained.
EXAMPLE 4 Color development 14 min. Stop 4 min. Wash 4 min. Blix-stabilization 12 min. Wash 6 min.
The composition of the color developing solution used in the above processings was the same as that described in Example 1.
Stop solution:
Glacial acetic acid 20 ml Anhydrous sodium sulfite l0 g Water to 1 liter pH 4.5
Blix-stabilizing solution:
Ferric complex salt of EDTA 60 g Anhydrous sodium sulfite 10 g Anhydrous sodium thiosulfate 200 g Anhydrous sodium carbonate 5 g Monomethylol dimethylhydantoin l g Water to 1 liter pH 6.5
The processing period of time was shortened and a color image stable to light and heat was obtained.
While the invention has been described in detail and in terms of 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 scope thereof.
What is claimed is:
l. A process for developing a color photographic material having a waterproof support wherein the material is subjected to a color development process and then simultaneously bleached, fixed and stabilized with an oxidizer, a silver halide solvent and a compound containing an aldehyde group or a methylol group, wherein the improvement consists essentially of color developing said material and then simultaneously bleaching, fixing and stabilizing said photographic material by processing the color photographic material in a blixstabilizing bath containing a water-soluble ferric complex salt of an organic acid, a solvent for silver halide,
and 0.05 to 5.0 g. per liter of said bath of a watersoluble compound having an aldehyde group or a methylol group and being selected from the group consisting of compounds represented by the formula RCHO wherein R represents an alkyl group, an aryl group, an allyl group or a heterocyclic group, compounds represented by the formula Ol-lC-R'Cl-lO wherein R represents a direct bond, a divalent aliphatic group or a divalent aromatic group and compounds represented by the formula R"CH OH wherein R" represents an aliphatic group, an aromatic group, or a heterocyclic group, said blix-stabilizing bath having a pH within the range of about 5.5 to about 7.5.
2. The process of claim 1 wherein said water-soluble compound having an aldehyde group or a methylol group is a compound represented by the formula RCHO wherein R represents an alkyl group, an aryl group, an ally] group, or a heterocyclic group.
3. The process of claim 1 wherein said water-soluble compound having an aldehyde group or a methylol group is a compound represented by the formula OHC-R'CHO wherein R represents a direct bond, a divalent aliphatic group or a divalent aromatic group.
4. The process of claim 1 wherein said water-soluble compound having an aldehyde group or a methylol group is a compound represented by the formula R"-CH OH HOOC-R X-R COOH i 3.. LOOC R II R COOH HOOC-R -N-R COOH wherein X represents a hydrocarbon group, an oxygen tetramethylolcyclohexanol,
atom, a sulfur atom, or a group; R R R R and R each represents a substituted or unsubstituted hydrocarbon group; and R represents a hydrogen atom or a substituted or unsubstituted hydrocarbon group.
7. The process of claim 5, wherein said organic acid is malonic acid, tartaric acid, ethylmalonic acid, malic acid, fumaric acid, diglycolic acid, thioglycolic acid, ethyliminodipropionic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, aminotriacetic acid, ethylenedithioglycolic acid, or dithioglycolic acid.
8. The process of claim 1, wherein said solvent for silver halide is a thiosulfate, a thiocyanate, an organic sulfur-containing dibasic acid, or an organic diol.
9. The process of claim 2, wherein said water soluble compound having a aldehyde group or a methylol group is formaldehyde, paraformaldehyde, trioxymethylene, glycolaldehyde, methylal, chloral, acetaldehyde, aldol, propiolaldehyde, acrolein, dibromoacrolein, crotonaldehyde, salicylaldehyde, gluoxylic acid, mucochloric acid, mucobromic acid, arabinose, xylose, glyceraldehyde, furfural or precursors thereof.
10. The process of claim 3, wherein said water soluble compound having an aldehyde group or a methylol group is glyoxal, succinaldehyde, tartardialdehyde, terephthalaldehyde, glutaraldehyde, a-methylglutaraldehyde, cyclopentanedicarboxyaldehyde, or precursors thereof.
11. The process of claim 4, wherein said water soluble compound having an aldehyde group or a methylol group is N-methylolurea, N,N'-dimethylolurea, N- methylolmethylene bis-monoethylurea, N'-methylol- N,N'-dimethylolurea, methylohydantoin, dimethylolmelamine, monomethylol dimethylhydantoin, hydroxydimethylbuiret, trihydroxymethylbuiret, 2,2,6,6-
methyloldicyandiamide, 3-hydroxy-2,2-dihydroxymethylpropionic acid, 2-nitro- 2-methyll ,3-propanediol.
12. The process of claim 1, wherein said blixstabilizing bath additionally contains a water-soluble fluorescent brightening agent.

Claims (12)

1. A process for developing a color photographic material having a waterproof support wherein the material is subjected to a color development process and then simultaneously bleached, fixed and stabilized with an oxidizer, a silver halide solvent and a compound containing an aldehyde group or a methylol group, wherein the improvement consists essentially of color developing said material and then simultaneously bleaching, fixing and stabilizing said photographic material by processing the color photographic material in a blix-stabilizing bath containing a water-soluble ferric complex salt of an organic acid, a solvent for silver halide, and 0.05 to 5.0 g. per liter of said bath of a water-soluble compound having an aldehyde group or a methylol group and being selected from the group consisting of compounds represented by the formula R-CHO wherein R represents an alkyl group, an aryl group, an allyl group or a heterocyclic group, compounds represented by the formula OHC-R''-CHO wherein R'' represents a direct bond, a divalent aliphatic group or a divalent aromatic group and compounds represented by the formula R''''-CH2OH wherein R'''' represents an aliphatic group, an aromatic group, or a heterocyclic group, said blix-stabilizing bath having a pH within the range of about 5.5 to about 7.5.
1. A PROCESS FOR DEVELOPING A COLOR PHOTOGRAPHIC MATERIAL HAVING A WATERPROFF SUPPORT WHEREIN THE MATERIAL IS SUBJECTED TO A COLOR DEVELOPMENT PROCESS AND THEN SIMULTANEOUSLY BLEACHED, FIXED AND STABILIZED WITH AN OXIDIZER, A SILVER HALIDE SOLVENT AND A COMPOUND CONTAINING AN ALDEHYDE GROUP OR A METHYLOL GROUP, WHEREIN THE IMPROVEMENT CONSISTS ESSENTIALLY OF COLOR DEVELOPING SAID MATERIAL AND THEN SIMULTANEOUSLY BLEACHING, FIXING AND STABILIZING SAID PHOTOGRAPHIC MATERIAL BY PROCESSING THE COLOR PHOTOGRAPHIC MATERIAL IN A BLIX-STABILIZING BATH CONTAINING A WATER-SOLUBLE FERRIC COMPLEX SALT OF AN ORGANIC ACID, A SOLVENT FOR SILVER HALIDE, AND 0.05 TO 5.0 G. PER LITER OF SAID BATH OF A WATER-SOLUBLE COMPOUND HAVING AN ALDEHYDE GROUP OR A METHYLOL GROUP AND BEING SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS REPRESENTED BY THE FORMULA R-CHO WHEREIN R REPRESENTS AN ALKYL GROUP, AN ARYL GROUP, AN ALLYL GROUP OR A HETEROCYCLIC GROUP, COMPOUNDS REPRESENTED BY THE FORMULA OHC-R''-CHL WHEREIN R'' REPRESENTS A DIRECT BOND, A DIVALENT ALIPHATIC GROUP OR A DIVALENT AROMATIC GROUP AND COMPOUNDS REPRESENTED BY THE FORMULA R" -CH2OH WHEREIN R" REPRESENTS AN ALIPHATIC GROUP, AN AROMATIC GROUP, OR A HETEROCYCLIC GROUP, SAID BLIXSTABILIZING BATH HAVING A PH WITHIN THE RANGE OF ABOUT 5.5 TO ABOUT 7.5.
2. The process of claim 1 wherein said water-soluble compound having an aldehyde group or a methylol group is a compound represented by the formula R - CHO wherein R represents an alkyl group, an aryl group, an allyl group, or a heterocyclic group.
3. The process of claim 1 wherein said water-soluble compound having an aldehyde group or a methylol group is a compound represented by the formula OHC-R''-CHO wherein R'' represents a direct bond, a divalent aliphatic group or a divalent aromatic group.
4. The process of claim 1 wherein said water-soluble compound having an aldehyde group or a methylol group is a compound represented by the formula R''''-CH2OH wherein R'''' represents an aliphatic group, an aromatic group, or a heterocyclic group.
5. The process of claim 1 wherein the pH of said blix-stabilizing bath is in the range of from 6.0 to 7.0.
6. The process of claim 1, wherein said organic acid has the general formula HOOC-R1-X-R2-COOH or
7. The process of claim 5, wherein said organic acid is malonic acid, tartaric acid, ethylmalonic acid, malic acid, fumaric acid, diglycolic acid, thioglycolic acid, ethyliminodipropionic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, aminotriacetic acid, ethylenedithioglycolic acid, or dithioglycolic acid.
8. The process of claim 1, wherein said solvent for silver halide is a thiosulfate, a thiocyanate, an organic sulfur-containing dibasic acid, or an organic diol.
9. The process of claim 2, wherein said water soluble compound having a aldehyde group or a methylol group is formaldehyde, paraformaldehyde, trioxymethylene, glycolaldehyde, methylal, chloral, acetaldehyde, aldol, propioLaldehyde, acrolein, dibromoacrolein, crotonaldehyde, salicylaldehyde, gluoxylic acid, mucochloric acid, mucobromic acid, arabinose, xylose, glyceraldehyde, furfural or precursors thereof.
10. The process of claim 3, wherein said water soluble compound having an aldehyde group or a methylol group is glyoxal, succinaldehyde, tartardialdehyde, terephthalaldehyde, glutaraldehyde, Alpha -methylglutaraldehyde, cyclopentanedicarboxyaldehyde, or precursors thereof.
11. The process of claim 4, wherein said water soluble compound having an aldehyde group or a methylol group is N-methylolurea, N,N''-dimethylolurea, N-methylolmethylene bis-monoethylurea, N''-methylol-N,N''-dimethylolurea, methylohydantoin, dimethylolmelamine, monomethylol dimethylhydantoin, hydroxydimethylbuiret, trihydroxymethylbuiret, 2,2,6,6-tetramethylolcyclohexanol, methyloldicyandiamide, 3-hydroxy-2,2-dihydroxymethylpropionic acid, 2-nitro-2-methyl-1,3-propanediol.
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US4033771A (en) * 1973-08-16 1977-07-05 Eastman Kodak Company Stabilized bleach-fixing baths
US4040837A (en) * 1974-12-05 1977-08-09 Konishiroku Photo Industry Co., Ltd. Photographic bleach-fixer
US4075014A (en) * 1973-03-17 1978-02-21 Tetenal Photowerk Walter Grabig Color picture development process
US4125402A (en) * 1976-08-19 1978-11-14 Ciba-Geigy Ag Method of processing silver dye bleaching materials and preparations suitable for the dye and silver bleaching
US4144068A (en) * 1977-01-28 1979-03-13 Fuji Photo Film Co., Ltd. Method for color photographic processing
US4232112A (en) * 1978-02-10 1980-11-04 Konishiroku Photo Industry Co., Ltd. Process for treating silver halide color photographic photosensitive material
US4268618A (en) * 1979-07-05 1981-05-19 Fuji Photo Film Co., Ltd. Bleaching composition for photographic processing
US4293639A (en) * 1979-05-09 1981-10-06 Fuji Photo Film Co., Ltd. Bleaching compositions for photographic processing
US4469781A (en) * 1981-10-30 1984-09-04 Fuji Photo Film Co., Ltd. Processing for silver halide color photographic materials
US4855217A (en) * 1984-12-26 1989-08-08 Konishiroku Photo Industry Co., Ltd. Processing of color photographic material utilizing a stabilizing solution after fixing
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
US4921779A (en) * 1988-12-19 1990-05-01 Eastman Kodak Company Bleach-accelerating compositions containing a dye-stabilizing agent and use thereof in photographic color processing
US4960682A (en) * 1988-12-19 1990-10-02 Eastman Kodak Company Bleaching compositions containing a dye-stabilizing agent and use thereof in photographic color processing
US4975356A (en) * 1988-12-19 1990-12-04 Eastman Kodak Company Bleach-accelerating compositions containing a dye-stabilizing agent and use thereof in photographic color processing
EP0432499A1 (en) * 1989-11-16 1991-06-19 Fuji Photo Film Co., Ltd. Method for processing silver halide photographic material and composition having fixing ability
EP0434097A1 (en) * 1989-12-21 1991-06-26 Fuji Photo Film Co., Ltd. A method for processing silver halide color photographic materials
US5037725A (en) * 1989-12-11 1991-08-06 Eastman Kodak Company Process for stabilizing photographic elements
US5360700A (en) * 1989-01-13 1994-11-01 Konica Corporation Process for treating silver halide photographic light-sensitive material
US5424177A (en) * 1991-07-05 1995-06-13 Konica Corporation Stabilizer for silver halide color photographic light-sensitive materials and its concentrated composition, and processing method using said stabilizer
US5441852A (en) * 1991-12-27 1995-08-15 Konica Corporation Method of stabilizing a color silver halide image

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IT7925699A0 (en) 1978-09-14 1979-09-12 Eastman Kodak Co PHOTOGRAPHIC COMPOSITIONS OF BIANCA, AND METHODS FOR PHOTOGRAPHIC TREATMENT.
JPS5815784B2 (en) * 1979-10-08 1983-03-28 コニカ株式会社 How to store bleach-fix solution separately
JPS57185434A (en) * 1981-05-11 1982-11-15 Fuji Photo Film Co Ltd Processing method for color photography
JP2534227B2 (en) * 1986-02-07 1996-09-11 富士写真フイルム株式会社 Processing method of silver halide color photographic light-sensitive material
EP0244177B1 (en) * 1986-04-30 1994-05-04 Konica Corporation Method for processing light-sensitive silver halide color photographic material
JPH0752289B2 (en) * 1987-03-31 1995-06-05 コニカ株式会社 A safe photographic stabilizer with good image stabilization performance
JP2782565B2 (en) * 1990-12-07 1998-08-06 富士写真フイルム株式会社 Processing method for color image stabilizing processing solution, stabilizing solution, stabilizing replenisher, adjusting solution, bleaching solution and silver halide color photographic light-sensitive material
JP2904948B2 (en) * 1991-03-28 1999-06-14 コニカ株式会社 Processing method and stabilizer for silver halide color photographic light-sensitive material
JP2816612B2 (en) * 1991-05-20 1998-10-27 富士写真フイルム株式会社 Processing method of silver halide color photographic light-sensitive material
EP0529794A1 (en) * 1991-07-26 1993-03-03 Konica Corporation Formaldehyde-free stabilizing process

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US3335004A (en) * 1963-12-09 1967-08-08 Eastman Kodak Co Method for stabilization processing of color emulsions
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US3591380A (en) * 1967-07-28 1971-07-06 Fuji Photo Film Co Ltd Rapid stabilizing process for color photographic materials
US3582322A (en) * 1968-06-11 1971-06-01 Eastman Kodak Co Color photographic elements and process
US3667950A (en) * 1969-12-16 1972-06-06 Fuji Photo Film Co Ltd Bleach-fixing solution for color photography
US3741763A (en) * 1970-06-10 1973-06-26 Fuji Photo Film Co Ltd Rapid color reversal photographic developing process

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4075014A (en) * 1973-03-17 1978-02-21 Tetenal Photowerk Walter Grabig Color picture development process
US4033771A (en) * 1973-08-16 1977-07-05 Eastman Kodak Company Stabilized bleach-fixing baths
US4040837A (en) * 1974-12-05 1977-08-09 Konishiroku Photo Industry Co., Ltd. Photographic bleach-fixer
US4125402A (en) * 1976-08-19 1978-11-14 Ciba-Geigy Ag Method of processing silver dye bleaching materials and preparations suitable for the dye and silver bleaching
US4144068A (en) * 1977-01-28 1979-03-13 Fuji Photo Film Co., Ltd. Method for color photographic processing
US4232112A (en) * 1978-02-10 1980-11-04 Konishiroku Photo Industry Co., Ltd. Process for treating silver halide color photographic photosensitive material
US4293639A (en) * 1979-05-09 1981-10-06 Fuji Photo Film Co., Ltd. Bleaching compositions for photographic processing
US4268618A (en) * 1979-07-05 1981-05-19 Fuji Photo Film Co., Ltd. Bleaching composition for photographic processing
US4469781A (en) * 1981-10-30 1984-09-04 Fuji Photo Film Co., Ltd. Processing for silver halide color photographic materials
US4855217A (en) * 1984-12-26 1989-08-08 Konishiroku Photo Industry Co., Ltd. Processing of color photographic material utilizing a stabilizing solution after fixing
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
EP0359803B1 (en) * 1988-03-15 1993-12-15 Eastman Kodak Company Process for stabilizing photographic elements
US4921779A (en) * 1988-12-19 1990-05-01 Eastman Kodak Company Bleach-accelerating compositions containing a dye-stabilizing agent and use thereof in photographic color processing
US4960682A (en) * 1988-12-19 1990-10-02 Eastman Kodak Company Bleaching compositions containing a dye-stabilizing agent and use thereof in photographic color processing
US4975356A (en) * 1988-12-19 1990-12-04 Eastman Kodak Company Bleach-accelerating compositions containing a dye-stabilizing agent and use thereof in photographic color processing
US5360700A (en) * 1989-01-13 1994-11-01 Konica Corporation Process for treating silver halide photographic light-sensitive material
EP0432499A1 (en) * 1989-11-16 1991-06-19 Fuji Photo Film Co., Ltd. Method for processing silver halide photographic material and composition having fixing ability
US5120635A (en) * 1989-11-16 1992-06-09 Fuji Photo Film Co., Ltd. Method for processing silver halide photographic material and composition having fixing ability
US5037725A (en) * 1989-12-11 1991-08-06 Eastman Kodak Company Process for stabilizing photographic elements
EP0434097A1 (en) * 1989-12-21 1991-06-26 Fuji Photo Film Co., Ltd. A method for processing silver halide color photographic materials
US5534394A (en) * 1989-12-21 1996-07-09 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic materials
US5424177A (en) * 1991-07-05 1995-06-13 Konica Corporation Stabilizer for silver halide color photographic light-sensitive materials and its concentrated composition, and processing method using said stabilizer
US5441852A (en) * 1991-12-27 1995-08-15 Konica Corporation Method of stabilizing a color silver halide image

Also Published As

Publication number Publication date
CA989229A (en) 1976-05-18
FR2154699A1 (en) 1973-05-11
FR2154699B1 (en) 1978-03-03
DE2247582A1 (en) 1973-04-05
JPS4842733A (en) 1973-06-21
GB1365453A (en) 1974-09-04

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