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United States Patent (19) 11 4,040,838 Yamaguchi 45) Aug

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United States Patent (19) 11 4,040,838 Yamaguchi 45) Aug United States Patent (19) 11 4,040,838 Yamaguchi 45) Aug. 9, 1977 (54) PROCESSING COLORPHOTOGRAPHIC MATER ALS FOREIGN PATENT DOCUMENTS 1,297,905 11/1972 United Kingdom - C - - a 96/60 BF 75) Inventor: Seiya Yamaguchi, Minami-ashigara, 1,311,001 3/1973 United Kingdom .... Japan 1,131,096 10/1968 United Kingdom .............. 96/60 BF Primary Examiner-Mary F. Kelley 73 Assignee: Fuji Photo Film Co., Ltd., Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, Minami-ashigara, Japan Zinn and Macpeak 21 Appl. No.: 664,225 57 ABSTRACT In the high temperature color development processing (22 Filed: Mar. 5, 1976 of color photographic materials, the formation of retic ulation and scratches on the surfaces of the photo (30) Foreign Application Priority Data graphic films is prevented and drying can be performed Mar. 5, 1975 Japan .................................. 50-27276 in a shortened period of time at a high temperature by processing the color photographic materials in a bleach (51) Int. C.?................................................ G03C 5/32 solution or blix solution containing a metal complex of 52 U.S. C. .................................. 96/60 R; 96/60 BF an organic acid, a water soluble ammonium compound 58) Field of Search .......................... 96/60, 60 BF, 55 and a magnesium compound. The bleach solution or blix solution does not give rise to (56) References Cited environmental pollution and can be easily regenerated U.S. PATENT DOCUMENTS for reuse. 3,773,510 11/1973 Fisch ................................. 96/60 BF 3,960,565 6/1976 Fisch et al. .......................... 96/60 R 15 Claims, No Drawings 4,040,838 1 2 of shortening the processing time and economic profit PROCESSING COLOR PHOTOGRAPHIC ability. MATER ALS It is known to incorporate a hardening agent in a bleach solution or a blix solution containing a metal BACKGROUND OF THE INVENTION complex salt of an organic acid as a bleaching agent, but 1. Field of the Invention with conventional techniques the usable hardening The present invention relates to processing silver agents are quite limited since the effective pH range of halide photographic materials, more particularly, to the processing solution is in the weak acid or neutral hardening color photographic materials with a bleach region of 5.0 to 7.5, and, hence, a hardening agent solution or a blix solution. O which can only be used in an acid solution, such as 2. Description of the Prior Art potassium alum or chromium alum, cannot be used. To rapidly process color photographic materials, it is Furthermore, it is also known to add an aldehyde com generally necessary to process at a temperature higher pound such as formaldehyde or glutaraldehyde to such than 30 C, but in such a case the photographic emul a processing solution, but in such a conventional pro sion layers of photographic materials are apt to be 15 cess it is difficult to add a sufficient amount of the hard swollen and softened to cause reticulation or are apt to ening agent to the processing solution to provide to the be scratched and peel off during processing. In fact, solution a hardening function which can endure high sometimes the emulsion layers melt during drying after temperature processing since the addition of such a processing. In particular, these faults tend to become compound tends to deteriorate the stability of the solu more pronounced as the processing temperature is in 20 tion to form precipitates during storage of the solution creased, and thus are a great obstacle to practice high and has a bad influence on the photographic properties temperature rapid processing. of color photographic materials processed therein to To prevent softening of the emulsion layers of color form fog during the storage of processed photographic photographic materials in high temperature processing materials. thereof, a process has hitherto been employed wherein 25 a hardening bath is used during processing or a harden SUMMARY OF THE INVENTION ing agent such as alum or formalin is added to another Thus, one object of this invention is to provide a processing bath. The former process is, however, un process for preventing swelling and softening of the suitable for rapid processing since the number of pro emulsion layers of color photographic materials in high cessing steps increases and the time required to com 30 temperatures processing by providing a hardening func plete total processing is prolonged. On the other hand, tion to a bleach solution or a blix solution. the latter process is suitable for rapid processing since Another object of this invention is to provide a stable the number of processing steps and the processing time bleach solution or blix solution possessing a hardening are the same as those of conventional high temperature function. processes. The process of this invention belongs to the 35 According to the present invention, there is provided latter type of processes. a process of processing color photographic materials Processing steps for silver halide color photographic which comprises processing silver halide color photo materials include as necessary steps a silver removal graphic materials with a bleach solution or a blix solu step for removing silver images after color develop tion containing a metal complex salt of an organic acid, ment. The silver removal step is usually composed of a a water soluble ammonium compound and a magnesium bleach step and a fix step or a blix step which performs compound. the bleach step and the fix step in one bath. In silver As a result of various investigations to provide a suffi removal, silver formed by development is oxidized by a cient hardening function and stability to a bleach solu bleaching agent (oxidizing agent) to silver halide and tion or a blix solution containing a metal complex salt of the silver halide thus formed is converted into a water 45 organic acid as a bleaching agent, the inventors found soluble silver salt by the fixing agent. that by adding one or more water soluble ammonium As the bleaching agent, potassium ferricyanide, potas compounds and one or more magnesium compounds to sium dichromate, and a metal complex salt of an organic a bleach solution or a blix solution containing one or acid are usually used. As potassium ferricyanide and more metal complex salts of organic acids, a stable potassium dichromate have a high bleaching power, 50 bleach solution or blix solution having a hardening they are used for bleaching color photographic materi function sufficiently durable to high temperature pro als containing a large proportion of silver, such as color cessing and having no bad influence on the photo negative films and color reversal films, but the demand graphic properties of color photographic materials can for these materials has recently gradually been reducing be obtained. It should, however, be noted that the met due to the difficulty in treating water solutions contain 55 als, organic acids capable of forming complex salts ing these materials which cause water pollution. On the therewith, water soluble ammonium compounds and other hand, a metal complex salt of an organic acid can magnesium compounds useful in the present invention profitably be used in blix solutions since the complex will easily be appreciated by one skilled in the art, and salts causes less pollution problems and the treatment of there is no substantial limitation on such materials here waste solution containing such a complex salt is easy, 60 inafter disclosed. and, further, it can be present together with a fixing The bleach solution or blix solution used in the pro agent due to the comparatively weak oxidative power cess of this invention containing one or more metal thereof. Further, in the case of using the complex salt, complex salts of an organic acid as a bleaching agent the used processing solution can be easily regenerated and further containing a hardening component and a by air oxidation for repeated use. Accordingly, metal 65 stabilization component exhibits a hardening function complex salts of organic acids are widely used as excel and, at the same time, improved stability of the solution. lent bleaching agents from the viewpoint of causing less Hereinafter these various components will generally pollution problems, simplicity of processing, capability be referred to in the singular for purposes of brevity. 4,040,838 3 4. Among these water soluble ammonium compounds, DETAILED DESCRIPTION OF PREFERRED ammonium chloride, ammonium thiosulfate, ammo EMBODIMENTS nium acetate, and aqueous ammonia are particularly The magnesium compound used in this invention has useful. Ammonium thiosulfate also has functions as a the function of hardening the emulsion layers of color fixing agent and thus is preferably used in a blix solu photographic materials and the water soluble ammo tion. Aqueous ammonia is an aqueous solution of ammo nium compound has the function of maintaining the nia and the solution contains ammonia and ammonium magnesium compound in the processing solution in a hydroxide. stable manner. That is, the effect of this invention is due A proper amount of the water soluble ammonium to the co-action of these two components and thus the 10 compound is about 0.05 to about 2 mols per liter of the presence of these two components is mandatory. bleach solution or blix solution. It is known that a magnesium compound such as Magnesium compounds used in the invention are magnesium sulfate possesses the effect of hardening an water soluble magnesium compounds having a solubil emulsion layer containing gelatin as the vehicle, for ity of not less than about 0.1 g per 100 ml of water at 20 example, it is known to harden color negative films by 15 C, and magnesium compounds which are insoluble in processing in a 3% aqueous solution of magnesium water, but substantially soluble in the presence of an sulfate after color development.
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