Method for processing silver halide color photographic material

Abstract: A method for development processing a silver halide color photographic material comprising a support having thereon a magnetic recording layer, wherein the conductivity of a final processing solution of the development processing is 0.1 mS/cm or less; the calcium concentration in a final processing solution of the development processing is 5 mg/ℓ or less; or the adhered amount of a final processing solution remained on a surface of the photographic material on which the magnetic recording layer is provided after development processing is 0.3 ml/m 2 or less.

Description: The present invention relates to a method for development processing a photographic material having a magnetic recording layer and, more particularly, to a processing method in which a read error of a magnetic information from the magnetic recording layer of a photographic material after development processing is prevented. In a silver halide photographic material (hereinafter, referred to as a photographic material or a film), it has been almost impossible to input various informations of the time when photographing using a camera (e.g., the date of photographing, the weather, the enlargement ratio, the number of sheets of printing), except for only being capable of inputting the date of photographing optically. Further, inputting informations to a photographic material when printing has been completely impossible, which has been hindrance to speedup of the processing and reduction in cost. It is a very important means to input various informations into a photographic material for improving and more simplifying the manipulation of a camera in future. As such a means of inputting informations, a magnetic recording method has been variously studied because it is capable of arbitrarily inputting and outputting informations and due to its inexpensiveness. It has become feasible to input various informations to a photographic material by providing a magnetic recording layer in a photographic material which was formerly difficult, that is, the conditions when developing and printing have become possible to be inputted in a magnetic recording layer of a photographic material, e.g., the date of photographing, the weather, the conditions of lighting, the conditions at the time of photographing such as the reduction/enlargement ratio, etc., the number of sheets of reprinting, the place to be zoomed, and the messages. Further, a magnetic recording layer can be applied as a means of input and output signals when a photographic material is directly outputted to a television/video signals to form images, therefore, this is a very promising field. However, it has been found that, with respect to input and output of informations, the input and output error due to the space loss, in particular, the output error which is generated by development processing is a severe problem when handling a photographic material provided with a magnetic recording layer. Major causes of the space loss include the components coated on the side of a photographic material on which a magnetic recording layer is provided (e.g., magnetic grains and binder components), dusts adhered on the film during development processing, components of the processing solution, dirt from the hands adhered on the film, and dust in the atmosphere. A magnetic output error is generated presumably because they adhere and accumulate on the surface of a magnetic head while a film is traveling to cause the space loss between the film and the magnetic head. As a method for solving the input and output error attributable to the space loss, the techniques of inclusion of a lubricating agent in a magnetic recording layer have been proposed in JP-A-4-73743 and JP-A-4-124659 (the term "JP-A" as used herein refers to a "published unexamined Japanese patent application"). It is also disclosed in JP-A-4-73736 and JP-A-6-161033 that this problem can be resolved by the addition of grains insoluble in a developing solution into a surface layer of the support on which the magnetic recording layer is provided such that the surface has projections having an average height of from 0.1 to 3.0 µm. However, neither of these methods could provide a sufficient effect with respect to the output reduction of magnetic recording after development processing. An object of the present invention is to provide a processing method of a photographic material having a magnetic recording layer in which the magnetic output is not reduced after processing. Other objects and effects of the present invention will be apparent from the following description. The present invention relates to a method for development processing a silver halide color photographic material comprising a support having thereon a magnetic recording layer, wherein the conductivity of the final processing solution of said development processing is 0.1 mS/cm or less at 25°C. Specific embodiments of the present invention are set forth in claims 2 to 7. The silver halide color photographic material having a magnetic recording layer used in the present invention is subjected to ordinary color development processing (hereinafter referred to as only processing) followed by drying. Magnetic recording is generally carried out before processing and reading is carried out after processing in many cases, and it has been found that adhered materials accumulate on the surface of the magnetic head during reading of the information after processing to cause the space loss between the film and the magnetic head, thereby an output is reduced. As a result of analyzing this phenomenon, the present inventors have found that the components of the processing solution adhered after processing on the side of the film on which the magnetic recording layer is provided, in particular, the ionic component causes the above reduction of the output. The method of the present invention comprises reducing the conductivity of the final processing solution of the development processing to 0.1 mS/cm or less. Further, it has also been found that the curling characteristics after processing of the photographic material can be improved by the present invention. In the present invention, the term "final processing solution" means a processing solution just before the drying process, that is, a stabilizing solution or a rinsing solution, with a stabilizing solution being particularly effective. The present invention is conspicuously effective when a processing solution containing a surfactant is used as the final processing solution. A method for reducing the conductivity of the final processing solution to 0.1 mS/cm or less is described below. A processing solution such as a stabilizing solution and a rinsing solution contains various compounds for stabilizing images or other purposes. For reducing the conductivity of the final processing solution, it is effective to reduce ionic compounds in the chemicals which are added as the components of the final processing solution, and also it is effective to previously remove ionic compounds from water to which these chemicals are to be dissolved (hereinafter referred to as preparation water). Further, it is also effective that washing and stabilizing steps are carried out by a multistage countercurrent system to reduce the amount of carryover of the previous processing solution by the photographic material. As a method of removing ionic compounds from the preparation water, methods such as distillation, amphoteric ion exchange and reverse osmosis can be utilized. It is not preferred to apply these methods to a stabilizing solution or a replenisher thereof, since the performances of the stabilizing solution (e.g., stabilization of images, prevention of staining of a film, liquid extraction of a film) are deteriorated by the removal or reduction of the compounds added to the stabilizing solution. A most preferred method of the above is a method of amphoteric ion exchanging the preparation water previously. In the amphoteric ion exchange method, the preparation water is contacted with various ion exchangers such as an ion exchange resin and an ion exchange membrane with a method of using an ion exchange resin being most preferred. When using an ion exchange resin in the amphoteric ion exchange method, an H-type strongly acidic cation exchange resin and an OH-type strongly basic anion exchange resin are preferably used in admixture. It is preferred that the preparation water is passed through a column packed with the mixture of these resins. The passing rate is generally from 1 to 100 times, preferably from 5 to 50 times, of the volume of resins per hour. As the structure of a resin, a gel type, a porous type and a support carrying type can be used. Specific examples of ion exchange resins include combinations of Amberlite IR-120B and IRA-400 manufactured by Rohm & Haas and Diaion SK-1B and SA-10A or SA-20A manufactured by Mitsubishi Kasei Corp. A reverse osmosis equipment for reverse osmosis treating the preparation water is preferably a low pressure type equipment, for example, from 2 to 30 kg/cm 2 . As a reverse osmosis membrane, a cellulose acetate membrane, an ethyl cellulose-polyacrylic acid membrane, a polyacrylonitrile membrane, and a polybutylene carbonate membrane can be used. Specific examples include NTR-959HR, NTR-950UP, NTR-729HF, NTR-7250, NTR-719HF, NTR-7410, and NTR-7450 manufactured by Nitto Kagaku Kogyo Co., Ltd., UTC-70, UTC-40HR, SC-3000, SU-700, SU-410, SU-600, SU-200S, and PEC-1000 manufactured by Toray Industries Inc., BW-30, HR-30, NF-40, NF-40HF, NF-50, and NF-70 manufactured by Film Tec (Dow) Co., and Permasep B-9, B-10, B-15 and C-1 manufactured by DuPont, E.I. de Nemours. The conductivity used herein is a value at 25°C and is measured by a commercially available conductivity meter. As a conductivity meter, for example, CM-40S and CM-60S manufactured by Toa Denpa Kogyo Co., Ltd. can be used. The conductivity of the final processing solution is 0.1 mS/cm or less, preferably from 0.001 to 0.05 mS/cm, and more preferably from 0.003 to 0.03 mS/cm. The calcium concentration in the final processing solution may be reduced. When reducing the calcium concentration in the final processing solution, it is also effective to reduce the calcium concentration in the processing chemicals and/or the preparation water thereof. If the concentration of calcium ions can be reduced, any of the above methods for reducing the conductivity can be used. Other than the above methods, a cation exchange method can be used in which calcium ions are exchanged with monovalent ions such as sodium or potassium ions. Examples of ion exchangers in the cation exchange method include an ion exchange resin, an ion exchange membrane and zeolite, with an ion exchange resin being most preferred of these. A method of exchanging calcium ions with Na ions using a strongly acidic or a weakly acidic cation exchange resin as the ion exchange resin is preferred. A method of using the cation exchange resin may be the same as the case of the above described amphoteric ion exchange method. When the final processing solution has the effect of stabilizing images, the solution is called a stabilizing solution and solutions other than that are called a rinsing solution. The stabilizing solution and the rinsing solution are explained below. The stabilizing solution contains image stabilizers, for example, formaldehyde, benzaldehydes such as m-hydroxy-benzaldehyde, bisulfite addition products of formaldehyde, hexamethylenetetramine and derivatives thereof, hexahydrotriazine and derivatives thereof, dimethylolurea, N-methylol compounds such as N-methylolpyrazole, organic acids and pH buffers. The preferred amount added of these compounds is from 0.001 to 0.02 mol per liter of the stabilizing solution, and the lower the concentration of the free formaldehyde in the stabilizing solution, the less is the splashing of the formaldehyde gas, which is preferred. From these points, m-hydroxybenzaldehyde, hexamethylenetetramine, N-methylolazoles such as N-methylolpyrazole disclosed in JP-A-4-270344, and azolylmethylamines such as N,N'-bis(1,2,4-triazol-1-ylmethyl)piperazine, etc., disclosed in JP-A-4-313753 are preferred as dye image stabilizers. In particular, a combined use of azoles such as 1,2,4-triazole disclosed in JP-A-4-359249 (corresponding to EP-A-519190) with azolylmethylamine such as 1,4-bis(1,2,4-triazol-1-ylmethyl)-piperazine, and derivatives thereof is preferred because the high image stability can be obtained thereby and also which generates low vapor pressure of the formaldehyde. Further, it is preferred to include various compounds in the stabilizing solution, if necessary, for example, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, a whitening agent, a hardening agent, alkanolamine disclosed in U.S. Patent 4,786,583, and preservatives which can be generally included in fixing solutions and bleach-fixing solutions, e.g., sulfinic acid compounds as disclosed in JP-A-1-231051. These compounds each is generally added in an amount of from 0.01 to 1 g/ℓ, preferably from 0.05 to 0.5 g/ℓ. The rinsing solution and the stabilizing solution can contain various surfactants to prevent the generation of water marks during drying of the processed photographic materials. Nonionic surfactants are preferably used, and ethylene oxide addition product of alkylphenol is particularly preferred. Octyl-, nonyl-, dodecyl-, and dinonylphenol are preferred as the alkylphenol and the addition mol number of the ethylene oxide is preferably from 8 to 14. Further, it is preferred to use silicone surfactants which have the high defoaming ability. The surfactant is generally added in an amount of from 0.001 to 5 g/ℓ, preferably from 0.05 to 0.5 g/ℓ. The rinsing solution and the stabilizing solution are preferred to contain various kinds of chelating agents. Preferred examples of the chelating agents include aminopolycarboxylic acid, e.g., ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, organic phosphonic acid, e.g., 1-hydroxyethylidene-1,1-diphosphonic acid, N,N,N'-trimethylenephosphonic acid, diethylenetriamine-N,N,N',N'-tetramethylenephosphonic acid, and a hydrolysis product of a maleic anhydride polymer disclosed in EP-A-345172, and the like. The chelating agent is generally added in an amount of from 0.001 to 5 g/ℓ, preferably from 0.01 to 0.5 g/ℓ. The rinsing solution and the stabilizing solution are preferred to contain 1,2-benzisothiazolin-3-one from not only stabilization of the processing solution but also capable of obtaining the effect of preventing the reduction of the magnetic output after processing. The amount added of this compound is from 0.01 to 0.5 mg, preferably from 0.03 to 0.3 mg, per liter of the processing solution. The overflow generated by the replenishment of the above described rinsing solution and/or stabilizing solution can be reused in other steps such as a desilvering step, etc. A processing method preferably used in the present invention is explained below. The processing method may generally be effected by conducting a developing process, a desilvering process, and a finishing process, in this order. The developing process may comprise color developing, or in a reversal process, black-and-white developing followed by color developing, and optionally a stopping process. The black-and-white developing may comprise a reversing process (such as reversal exposure and a reversal bath), a washing process, and a rinsing process. The desilvering process may comprise a process, in which a material is processed with a solution having bleaching ability such as a bleaching solution and a bleach-fixing solution, and a process, in which a material is processed with a solution having a fixing ability, such as a fixing solution and a bleach-fixing solution. In the present invention, both the processes are conducted or only a bleach-fixing process is conducted. After the desilvering process, a finishing process such as washing, rinsing or stabilizing is conducted. Any combination of them may be employed, and in general, washing or rinsing is conducted and stabilizing is then conducted. The material thus processed by the above processes is then dried by a drying process. The present invention can be applied to various silver halide color photographic materials such as color papers coated with a silver chlorobromide emulsion and a silver bromide emulsion, color autopositive paper, color negative films coated with a silver iodobromide emulsion, color reversal films and color reversal papers, and in particular, color negative films are preferred. Among these, color negative films having a magnetic recording layer on the back surface of the support (opposite surface to the emulsion layer) are preferred. A photographic material having a magnetic recording layer is described below. A magnetic recording layer is a layer coated on a support with a water-soluble or organic solvent based coating solution comprising magnetic grains dispersed in a binder. Examples of the magnetic grains for use in the present invention include ferromagnetic iron oxide such as γ-Fe 2 O 3 , Co-coated γ-Fe 2 O 3 , Co-coated magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal system Ba ferrite, Sr ferrite, Pb ferrite, and Ca ferrite. Co-coated ferromagnetic iron oxide such as Co-coated γ-Fe 2 O 3 is preferred of them. The shape of the grain may be any of an acicular shape, a granular shape, a spherical shape, a cubic shape, or a plate-like shape. The specific surface area (S BET ) is preferably 20 m 2 /g or more, and particularly preferably 30 m 2 /g or more. The saturation magnetization (σ s ) of the ferromagnetic substance is preferably from 3.0 × 10 4 to 3.0 × 10 5 A/m and particularly preferably from 4.0 × 10 4 to 2.5 × 10 5 A/m. The ferromagnetic grains may be surface treated with silica and/or alumina or organic materials. Further, the surface of the magnetic grains may be treated with a silane coupling agent or a titanium coupling agent as disclosed in JP-A-6-161032. In addition, the magnetic grains the surfaces of which are covered with inorganic or organic substance as disclosed in JP-A-4-259911 and JP-A-5-81652 can also be used. The binders which can be used for the magnetic grains includes the thermoplastic resins, thermosetting resins, radiation hardening resins, reactive type resins, acid-, alkali- or bio-degradable polymers, natural polymers (e.g., cellulose derivatives, sugar derivatives), and mixtures thereof disclosed in JP-A-4-219569. The above described resins have a glass transition temperature Tg of from -40°C to 300°C, and a weight average molecular weight of from 2,000 to 1,000,000. Examples of such binders include vinyl copolymers, cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate and cellulose tripropionate, acrylic resins, and polyvinyl acetal resins. Gelatin is also preferably used. Cellulose diacetate and cellulose triacetate are particularly preferred. The binder can be hardening treated by adding an epoxy, aziridine or isocyanate crosslinking agent. Examples of the isocyanate crosslinking agents include isocyanates such as tolylenediisocyanate, 4,4'-diphenylmethanediisocyanate, hexamethylenediisocyanate and xylylenediisocyanate, reaction products of these isocyanates with polyalcohols (e.g., a reaction product of 3 mol of tolylenediisocyanate with 1 mol of trimethylolpropane), and polyisocyanate formed by condensation of these isocyanates, and they are disclosed, e.g., in JP-A-6-59357. The above magnetic substances are dispersed in a binder preferably using, as disclosed in JP-A-6-35092, a kneader, a pin type mill, and an annular type mill, and the combined use thereof is also preferred. The dispersants disclosed in JP-A-5-88283 and other known dispersants can be used. The thickness of a magnetic recording layer is from 0.1 µm to 10 µm, preferably from 0.2 µm to 5 µm, and more preferably from 0.3 µm to 3 µm. The weight ratio of the magnetic grains to the binder is preferably from 0.5/100 to 60/100, and more preferably from 1/100 to 30/100. The coating amount of the magnetic grains is from 0.005 to 3 g/m 2 , preferably from 0.01 to 2 g/m 2 , and more preferably from 0.02 to 0.5 g/m 2 . The magnetic recording layer for use in the present invention can be provided on the back surface of the photographic support entirely or in the form of stripes by coating or printing. Coating of the magnetic recording layer can be carried out by means of air doctor coating, blade coating, air knife coating, squeeze coating, impregnation coating, reverse-roll coating, transfer-roll coating, gravure coating, kiss coating, cast coating, spray coating, dip coating, bar coating, or extrusion coating, and the coating solution disclosed in JP-A-5-341436 is preferably used. A magnetic recording layer may be provided with functions of lubrication improvement, curling adjustment, antistatic property, adhesion prevention and head abrasion, or another functional layer having these functions may be provided. At least one kind or more of the grains of non-spherical inorganic grains having Mohs' hardness of 5 or more are preferably used as abrasives. The composition of the non-spherical inorganic grain is preferably oxide such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide, etc., carbide such as silicon carbide and titanium carbide, silicon carbide, etc., and diamond in the form of powder. The surface of these abrasives may be treated with a silane coupling agent or a titanium coupling agent. These grains may be added to a magnetic recording layer, or may be overcoated on a magnetic recording layer (e.g., a protective layer, a lubricating layer). The above described binders can be used at this time, the same binders as the binder of the magnetic recording layer are preferably used. Photographic materials having a magnetic recording layer are disclosed, e.g., in U.S. Patents 5,336,589, 5,250,404, 5,229,259, 5,215,874 and European Patent 466130. Photographic materials which are processed by the method of the present invention are preferably photographic materials for photographing, and the support therefor is preferably a polyester support, details of which are disclosed in Kokai-Giho, Kogi No. 94-6023 (Hatsumei-Kyokai, March 15, 1994). The polyester for use in the present invention comprises diol and aromatic dicarboxylic acid as essential components. Examples of the aromatic dicarboxylic acids include 2,6-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, and phthalic acid. Examples of the diols include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of the polyester include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, polycyclohexanedimethanol terephthalate and the like. Particularly preferred is a polyester comprising from 50 mol% to 100 mol% of 2,6-naphthalenedicarboxylic acid. Particularly preferred above all is polyethylene 2,6-naphthalate. The average molecular weight of the polyester used in the present invention is generally about 5,000 to 200,000. Tg of the polyester is generally 50°C or more, and preferably 90°C or more. The polyester support may be heat treated at 40°C or more and less than Tg, more preferably at a temperature lower than Tg by 20°C or more and less than Tg, for the purpose of being reluctant to get curling habit. The heat treatment may be carried out at constant temperature within this range or may be carried out with cooling. The heat treatment time is from 0.1 hours to 1,500 hours, preferably from 0.5 hours to 200 hours. The heat treatment of the support may be carried out in a rolled state or may be carried out in a web state while transporting. The surface of the support may be provided with unevenness (e.g., coating conductive inorganic fine grains such as SnO 2 or Sb 2 O 5 ) to improve the surface state. Further, it is desired to contrive so as to prevent transfer of a cut end shape of the rolled support at the core part by providing knurling at the side edge part and making only the side edge part a little high. The heat treatment may be carried out at any stage of after formation of the support, after the surface treatment, after coating of a backing layer (an antistatic agent, a lubricating agent, etc.), or after undercoating, but preferably conducted after coating of an antistatic agent. An ultraviolet absorbing agent may be incorporated into the polyester support. Further, light piping can be prevented by incorporating the commercially available dye or pigment for polyester such as Diaresin manufactured by Mitsubishi Kasei Corp. or Kayaset manufactured by Nippon Kayaku Co., Ltd. into the support. To ensure adhesion of the support and the constitutional layers of the photographic material for use in the present invention, the surface activation treatment is preferably carried out, such as a chemical treatment, a mechanical treatment, a corona discharge treatment, a flame treatment, an ultraviolet treatment, a high frequency treatment, a glow discharge treatment, an active plasma treatment, a laser treatment, a mixed acid treatment, and an ozone oxidation treatment, and preferred of these surface treatments are an ultraviolet irradiation treatment, a flame treatment, a corona discharge treatment, and a glow discharge treatment. An undercoat layer may be a single layer or may be two or more layers. The binder for an undercoat layer include copolymers with monomers selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid and maleic anhydride being starting materials, as well as polyethyleneimine, an epoxy resin, grafted gelatin, nitrocellulose and gelatin. Compounds which swell the support include resorcin and p-chlorophenol. A gelatin hardening agent for an undercoat layer include chromium salt (chrome alum), aldehydes (formaldehyde, glutaraldehyde), isocyanates, active halide compounds (2,4-dichloro-6-hydroxy-s-triazine), epichlorohydrin resins, and active vinyl sulfone compounds. SiO 2 , TiO 2 , inorganic fine grains or polymethyl methacrylate copolymer fine grains (0.01 to 10 µm) may be contained as a matting agent. Further, antistatic agents are preferably used in the photographic material used in the present invention. Examples of such antistatic agents include polymers containing carboxylic acid, carboxylate and sulfonate, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agents are fine grains of a crystalline metal oxide of at least one selected from ZnO, TiO 2 , SnO 2 , Al 2 O 3 , In 2 O 3 , SiO 2 , MgO, BaO, MoO 3 and V 2 O 5 having a volume resistivity of 10 7 Ω·cm or less, more preferably 10 5 Ω·cm or less and having a grain size of from 0.001 to 1.0 µm or fine grains of composite oxides of them (Sb, P, B, In, S, Si, C), and fine grains of a metal oxide in the form of sol or fine grains of composite oxides of them. The addition amount to the photographic material is preferably from 5 to 500 mg/m 2 and particularly preferably from 10 to 350 mg/m 2 . The ratio of the crystalline oxides or composite oxides thereof to the binder is preferably from 1/300 to 100/1, and more preferably from 1/100 to 100/5. It is preferred for the photographic material used in the present invention to have a lubricating property. The lubricating agent-containing layer is preferably provided on both of a light-sensitive layer side and a backing layer side. Preferred lubricating property is a dynamic friction coefficient of from 0.01 to 0.25. Measurement of the lubricating property is conducted using a stainless steel ball having a diameter of 5 mm at a transporting speed of 60 cm/min (25°C, 60% RH). In this evaluation, when the opposite material is replaced with the light-sensitive layer surface, almost the same level of value can be obtained. Examples of the lubricating agent which can be used in the present invention include polyorganosiloxane, higher fatty acid amide, higher fatty acid metal salt, esters of higher fatty acid and higher alcohol. Examples of the polyorganosiloxane which can be used in the present invention include polydimethylsiloxane, polydiethylsiloxane, polystyrylmethylsiloxane, and polymethylphenylsiloxane. The layer to be added is preferably the outermost layer of emulsion layers or a backing layer. Polydimethylsiloxane or esters having a long chain alkyl group are particularly preferred. Further, the photographic material used in the present invention preferably contains a matting agent. The matting agent may be added to either of an emulsion layer side or a backing layer side but it is particularly preferably to be added to the outermost layer of emulsion layers. The matting agent may be either soluble or insoluble in the processing solution, preferably both types are used in combination. For example, polymethyl methacrylate, copolymer of methyl methacrylate and methacrylic acid (methyl methacrylate/ methacrylic acid = 9/1 or 5/5 by mol), and polystyrene grains are preferably used. The average grain size is preferably from 0.8 to 10 µm, and grain size distribution is preferably narrow, preferably 90% or more of the entire grain number accounts for from 0.9 to 1.1 times of the average grain size. For increasing the matting property, fine grains having a grain size of 0.8 µm or less are preferably added at the same time. For example, polymethyl methacrylate (0.2 µm), copolymer of methyl methacrylate and methacrylic acid (methyl methacrylate/methacrylic acid = 9/1 by mol) (0.3 µm), polystyrene grains (0.25 µm), and colloidal silica (0.03 µm) are enumerated. The film patrone preferably used in the present invention is described below. The main material of the patrone for use in the present invention may be metal or synthetic plastics. Preferred are plastic materials such as polystyrene, polyethylene, polypropylene, polyphenyl ether, etc. Further, the patrone may contain various antistatic agents, and carbon black, metal oxide grains, nonionic, anionic, cationic and betaine based surfactants or polymers can preferably be used. Such a patrone static prevented is disclosed in JP-A-1-312537 and JP-A-1-312538. In particular, those having the resistivity of 10 12 Ω or less at 25°C, 25% RH are preferred. Usually, a plastic patrone is produced using plastics including carbon black or a pigment to impart light shielding. The size of the patrone may be 135 size of the present as it is, or for a compact size camera, it is effective that the diameter of the patrone of 25 mm of the present 135 size may be decreased to 22 mm or less. The capacity of the case of the patrone is 30 cm 3 or less and preferably 25 cm 3 or less. The weight of the plastics used for the patrone and patrone case is preferably from 5 g to 15 g. Further, the patrone may be a type of sending out the film by revolving a spool. Further, it may be the structure such that the tip of the film is encased in the body of the patrone and the tip of the film is sent to outside through the port of the patrone by revolving the axle of the spool in the feeding direction of the film. These are disclosed in U.S. Patents 4,834,306 and 5,226,613. The photographic material after development processing can be encased again in a patrone. In this case, the patrone to be used may be the same patrone as used before processing or may be different one. The processing solution and the processing method of the present invention are described further in detail below. The compounds disclosed in JP-4-121739, page 9, right upper column, line 1 to page 11, left lower column, line 4 can be used in the color developing solution used in the present invention. In particular, when carrying out rapid processing with the color developing time being reduced to 2 min 30 s or less, 2-methyl-4-(N-ethyl-N-(2-hydroxyethyl)amino)aniline, 2-methyl-4-(N-ethyl-N-(3-hydroxypropyl)amino)aniline, and 2-methyl-4-(N-ethyl-N-(4-hydroxybutyl)amino)aniline are preferably used as a color developing agent. These color developing agents are contained in a color developing solution preferably in an amount of from 0.01 to 0.08 mol/ℓ, more preferably from 0.015 to 0.06 mol/ℓ, and still more preferably from 0.02 to 0.05 mol/ℓ. In the replenisher of a color developing solution, from 1.1 to 3 times of these amounts are preferably used. In the present invention, hydroxylamine is preferably not contained in a color developing solution, and N,N-bis(2-sulfoethyl)hydroxylamine is particularly preferably used in place of hydroxylamine. N,N-bis(2-sulfoethyl)hydroxylamine is preferably added in the form of an alkali metal salt of sodium, potassium and lithium, and the addition amount is from 0.001 to 0.1 mol, preferably from 0.01 to 0.05 mol, per liter of the color developing solution. The concentration of sulfite in a color developing solution is preferably from 0.01 to 0.05 mol/ℓ, and the concentration in the replenisher is preferably from 1.3 to 3 times of these amounts. The pH of a color developing solution is preferably from 10 to 10.5, and that of the replenisher is preferably from 10.2 to 10.7. Known pH buffers such as carbonate, phosphate, sulfosalicylate, and borate are used for the adjustment of pH as well as alkali hydroxide such as potassium hydroxide, sodium hydroxide, and lithium hydroxide. Carbonate is particularly preferred as a pH buffer. The replenishment rate of a color developing solution is preferably from 80 to 1,300 ml per m 2 of the photographic material but, the less, the better, from the viewpoint of the reduction of environmental pollution, and is generally from 80 to 600 ml, preferably from 80 to 400 ml. The concentration of bromide ions in a color developing solution is generally from 0.01 to 0.06 mol/ℓ but for purposes of preventing the generation of fog and improving the discrimination while maintaining sensitivity and, further, improving graininess, it is also preferred to set the concentration from 0.015 to 0.03 mol/ℓ. When the concentration of bromide ions is defined in such a range, the concentration of bromide ions in the replenisher can be obtained from the following equation, however, when C is minus, bromide ions are preferably not contained in the replenisher. C = A-W/V C: The concentration of bromide ions in the replenisher of a color developing solution (mol/ℓ) A: The concentration of bromide ions in an objective color developing solution (mol/ℓ) W: The amount of bromide ions dissolved out from a photographic material into a color developing solution when m 2 of a photographic material is color developed (mol) V: The replenishment rate of the color developing replenisher per m 2 of the photographic material (ℓ) The bromide necessary for preparing the above described color developing solution or color developing replenisher is contained in the color developing solution used in the present invention. Accordingly, bromide may be contained in the color developing solution or may not be contained at all. Moreover, when the replenishment rate is reduced or bromide ions are set in a high concentration, as a method of increasing sensitivity, pyrazolidones such as 1-phenyl-3-pyrazolidone and 1-phenyl-2-methyl-2-hydroxymethyl-3-pyrazolidone, thioether compounds such as 3,6-dithia-1,8-octanediol, sodium thiosulfate and potassium thiosulfate are preferably used as a development accelerator. In the present invention, it is preferred to apply the compounds and the processing conditions disclosed in JP-A-4-125558, page 4, left lower column, line 16 to page 7, left lower column, line 6 to the processing solution having a bleaching ability. A bleaching agent having an oxidation reduction potential of 150 mV or more is preferred, and specific examples thereof disclosed in JP-A-5-72694 and JP-A-5-173312 are preferably used in the present invention, in particular, 1,3-diaminopropanetetraacetic acid and the ferric complex salt of the compounds in specific example 1, page 7 of JP-A-5-173312 are preferred. In addition, for improving the biodegradability of a bleaching agent, it is preferred to use the ferric complex salt of the compounds disclosed in JP-A-4-251845, JP-A-4-268552, EP-A-588289, EP-A-591934, and JP-A-6-208213 as a bleaching agent. The concentration of these bleaching agents in the processing solution having a bleaching ability is preferably from 0.05 to 0.3 mol/ℓ, and for reducing the discharge amount to the environment, the concentration from 0.1 to 0.15 mol/ℓ is preferred. When the solution having a bleaching ability is a bleaching solution, the amount of bromide is preferably from 0.2 to 1 mol/ℓ, and particularly preferably from 0.3 to 0.8 mol/ℓ. The replenisher of the solution having a bleaching ability contains fundamentally the concentration of each component calculated by the following equation. According to this, the concentration in the mother solution can be maintained constant. C R = C T × (V 1 + V 2 )/V 1 + C P C R : The concentration of the component in the replenisher C T : The concentration of the component in the mother solution (processing tank solution) C P : The concentration of the component consumed during processing V 1 : The replenishment rate of the replenisher having a bleaching ability per m 2 of the photographic material (ml) V 2 : The amount of carryover from the previous tank by a photographic material of m 2 (ml) In addition, a bleaching solution preferably contains a pH buffer, in particular, a comparatively odorless dicarboxylic acid such as succinic acid, maleic acid, malonic acid, glutaric acid, and adipic acid are preferred. It is also preferred to use the known bleaching accelerators disclosed in JP-A-53-95630, Research Disclosure (RD), No. 17129, and U.S. Patent 3,893,858. A bleaching solution is preferably replenished with a bleaching replenisher in an amount of from 50 to 1,000 ml per m 2 of the photographic material, more preferably from 80 to 500 ml and most preferably from 100 to 300 ml. Further, a bleaching solution is preferably conducted aeration. The compounds and the processing conditions disclosed in JP-A-4-125558, page 7, left lower column, line 10 to page 8, right lower column, line 19 can be applied to the processing solution having a fixing ability. In particular, for improving fixing speed and preservability, the compounds represented by formulae (I) and (II) disclosed in JP-A-6-301169 are preferably added to the processing solution having a fixing ability alone or in combination. Further, the use of the sulfinic acid disclosed in JP-A-1-224762 as well as p-toluenesulfinate is preferred for improving preservability. In the solution having a bleaching ability and the solution having a fixing ability, ammonium is preferably used as a cation for improving a desilvering ability but taking the reduction of the environmental pollution into consideration, ammonium is preferably reduced or, if possible, zero. In bleaching, bleach-fixing and fixing processes, it is particularly preferred to carry out the jet stirring disclosed in JP-A-1-309059. The replenishment rate of the replenisher in bleach-fixing process or fixing process is from 100 to 1,000 ml, preferably from 150 to 700 ml, and particularly preferably from 200 to 600 ml, per m 2 of the photographic material. It is preferred to recover silver by installing various silver recovery devices by in-line and off-line systems in bleach-fixing and fixing processes. Using an in-line system, processing can be carried out with a reduced concentration of silver in a solution, as a result, the replenishment rate can be reduced. Further, it is preferred to recover silver by an off-line system and reuse the solution after silver recovery as a replenisher. Bleach-fixing process and fixing process may comprise a plurality of processing tanks and it is preferred to adopt a multistage countercurrent system with each tank being arranged in cascade piping. From the balance with the size of a processor, in general, two-tank cascade structure is effective and the proportion of the processing time in the preceding tank and the succeeding tank is preferably from 0.5/1 to 1/0.5, particularly preferably from 0.8/1 to 1/0.8. From the viewpoint of improving preservability, it is preferred that a free chelating agent not in the form of a metal complex is contained in a bleach-fixing solution or a fixing solution, and the biodegradable chelating agent described above with respect to the bleaching solution is preferably used as such a chelating agent. In the processing of the present invention, it is particularly preferred to conduct the compensation of evaporation disclosed in Kokai-Giho, Kogi No. 94-4992 (Hatsumei-Kyokai). In particular, the method of compensation based on the informations of the temperature and humidity of the atmosphere where the processor is installed according to formula-1 on page 2 of the above literature is preferred. The water to be used for the compensation of evaporation is preferably drawn from the replenisher tank of water washing, and in this case deionized water is preferably used as the water washing replenisher. The film processor disclosed in the above Kokai Giho, page 3, right column, lines 22 to 28 is preferably used in the present invention. Preferred processing agents, automatic processors, and specific examples of the evaporation compensation method for carrying out the present invention are disclosed in the above Kokai Giho, page 5, right column, line 11 to page 7, right column to the last line. The photographic materials disclosed in JP-A-4-125558, page 14, left upper column, first line to page 18, left lower column, line 11 are preferably used in the present invention. In particular, silver iodobromide emulsions having an average silver iodide content of from 3 to 20 mol% is preferably used as a silver halide emulsion, and tabular grains having an aspect ratio of 5 or more and double structure grains the interior and exterior parts of which have different halogen compositions are preferred. Further, the interior and exterior of the grains may comprise a clear layered structure. The aspect ratio is preferably from 5 to 20 and more preferably from 6 to 12. The monodisperse emulsions disclosed in U.S. patents 3,574,628 and 3,655,394 are also preferred. The photographic material for use in the present invention preferably has a layer containing light-insensitive fine grain silver halide of the average grain size of from 0.02 to 0.2 µm. The fine grain silver halide is preferably silver bromide containing from 0.5 to 10 mol% of silver iodide. Additives which can be used in the photographic material of the present invention are disclosed in the following table. Various dye-forming couplers can be used in the photographic material used in the present invention, and the following couplers are particularly preferred. Yellow Couplers: The couplers represented by formulae (I) and (II) disclosed in EP-A-502424; the couplers represented by formulae (1) and (2) disclosed in EP-A-513496 (in particular, Y-28 on page 18); the couplers represented by formula (I) disclosed in claim 1 of EP-A-568037; the couplers represented by formula (I), column 1, lines 45 to 55 of U.S. Patent 5,066,576; the couplers represented by formula (I), column 0008 of JP-A-4-274425; the couplers disclosed in claim 1 on page 40 of EP-A-498381 (in particular, D-35 on page 18); the couplers represented by formula (Y) on page 4 of EP-A-447969 (in particular, Y-1 (page 17) and Y-54 (page 41)); and the couplers represented by formulae (II) to (IV), column 7, lines 36 to 58 of U.S. Patent 4,476,219 (in particular, II-17 and II-19 (column 17), and II-24 (column 19)). Magenta Couplers: L-57 (page 11, right lower column), L-68 (page 12, right lower column), and L-77 (page 13, right lower column) of JP-A-3-39737; [A-4]-63 (page 134), and [A-4]-73 to [A-4]-75 (page 139) of EP 456257; M-4 to M-6 (page 26) and M-7 (page 27) of EP 486965; M-45 (page 19) of EP-A-571959; (M-1) (page 6) of JP-A-5-204106; and M-22, column 0237 of JP-A-4-362631. Cyan Couplers : CX-1, -3, -4, -5, -11, -12, -14 and -15 (pages 14 to 16) of JP-A-4-204843; C-7 and -10 (page 35), -34 and -35 (page 37), and (I-1) and (I-17) (pages 42 and 43) of JP-A-4-43345; and the couplers represented by formula (Ia) or (Ib) disclosed in claim 1 of JP-A-6-67385. Polymer Couplers : P-1 and P-5 (page 11) of JP-A-2-44345. The couplers disclosed in U.S. Patent 4,366,237, British Patent 2,125,570, EP-B-96873 and German Patent 3,234,533 are preferred as couplers the colored dyes of which have an appropriate diffusibility. Examples of preferred couplers for correcting the unnecessary absorption of colored dyes include the yellow colored cyan couplers represented by formulae (CI), (CII), (CIII) and (CIV) disclosed on page 5 of EP-A-456257 (in particular, YC-86 on page 84); the yellow colored magenta couplers ExM-7 (page 202), EX-1 (page 249), and EX-7 (page 251) disclosed in EP-A-456257; the magenta colored cyan couplers CC-9 (column 8) and CC-13 (column 10) disclosed in U.S. Patent 4,833,069; the coupler (2) (column 8) of U.S. Patent 4,837,136; and the colorless masking couplers represented by formula (A) disclosed in claim 1 of WO 92/11575 (in particular, the compounds disclosed on pages 36 to 45). Known materials such as Permalloy or Sendust can be used for the magnetic head having the function of reading magnetic informations of the film after processing, in particular, Sendust is preferred. Further, for preventing the reduction of output due to the stains adhered to the magnetic head, it is preferred that before the part of the film which contacts with the magnetic head (track) passes through the magnetic head, the stains adhered to the film are removed by making the film contact with a different head or analogues. The present invention will be illustrated in more detail with reference to examples below. EXAMPLE 1 1) Support The support which was used in the present invention was prepared as follows. 100 weight parts of polyethylene-2,6-naphthalate polymer and 2 weight parts of Tinuvin P. 326 (product of Ciba Geigy), as an ultraviolet absorbing agent, were dried, then melted at 300°C, subsequently, extruded through a T-type die, and stretched 3.3 times in a lengthwise direction at 140°C and then 3.3 times in a width direction at 130°C, and further thermal fixed for 6 seconds at 250°C and a polyethylene naphthalate (PEN) film having the thickness of 90 µm was obtained. Further, appropriate amounts of blue dyes, magenta dyes and yellow dyes were added to this PEN film (I-1, I-4, I-6, I-24, I-26, I-27 and II-5 disclosed in Kokai-Giho, Kogi No. 94-6023). Further, the film was wound on to a stainless steel spool having a diameter of 20 cm and provided heat history at 110°C for 48 hours to obtain a support reluctant to get curling habit. 2) Coating of Undercoat Layer After both surfaces of the above support were subjected to corona discharge, UV discharge and glow discharge treatments, an undercoat solution having the following composition was coated on each side of the support (10 ml/m 2 , using a bar coater): 0.1 g/m 2 of gelatin, 0.01 g/m 2 of sodium α-sulfo-di-2-ethylhexylsuccinate, 0.04 g/m 2 of salicylic acid, 0.2 g/m 2 of p-chlorophenol, 0.012 g/m 2 of (CH 2 =CHSO 2 CH 2 CH 2 NHCO) 2 CH 2 , and 0.02 g/m 2 of polyamide-epichlorohydrin polycondensation product. The undercoat layer was provided on the hotter side at the time of stretching. Drying was conducted at 115°C for 6 min (the temperature of the roller and transporting device of the drying zone was 115°C). 3) Coating of Backing Layer On one side of the above support after undercoat layer coating, an antistatic layer, a magnetic recording layer and a lubricating layer having the following compositions were coated as backing layers. 3-1) Coating of Antistatic Layer 0.2 g/m 2 of a dispersion of fine grain powder of a stannic oxide-antimony oxide composite having the average grain size of 0.005 µm and specific resistance of 5 Ω·cm (the grain size of secondary agglomerate: about 0.08 µm), 0.05 g/m 2 of gelatin, 0.02 g/m 2 of (CH 2 =CHSO 2 CH 2 CH 2 NHCO) 2 CH 2 , 0.005 g/m 2 of polyoxyethylene-p-nonylphenol (polymerization degree: 10) and resorcin were coated. The electric resistance at 25°C, 10% RH was 10 8.1 . 3-2) Coating of Magnetic Recording Layer 0.06 g/m 2 of cobalt-γ-iron oxide which was coating-treated with 3-polyoxyethylene-propyloxytrimethoxysilane (polymerization degree: 15) (15 wt%) (specific surface area: 43 m 2 /g, major axis: 0.14 µm, minor axis: 0.03 µm, saturation magnetization: 89 emu/g, Fe +2 /Fe +3 is 6/94, the surface was surface-treated with 2 wt%, respectively, based on the iron oxide, of aluminum oxide and silicon oxide), 1.2 g/m 2 of diacetyl cellulose (dispersion of the iron oxide was carried out using an open kneader and a sand mill), 0.3 g/m 2 of C 2 H 5 C(CH 2 OCONH-C 6 H 13 (CH 3 )NCO) 3 as a hardening agent, with acetone, methyl ethyl ketone and cyclohexanone as solvents, were coated with a bar coater to obtain a magnetic recording layer having the film thickness of 1.2 µm. As matting agents, silica grains (0.3 µm) and an aluminum oxide abrasive (0.15 µm) coating-treated with 3-poly(polymerization degree: 15)oxyethylene-propyloxytrimethoxysilane (15 wt%) were added each in an amount of 10 mg/m 2 . Drying was conducted at 115°C for 6 minutes (the temperature of the roller and transporting device of the drying zone was 115°C). The increase of the color density of D B of the magnetic recording layer by X-light (a blue filter) was about 0.1, and saturation magnetization moment of the magnetic recording layer was 4.2 emu/g, coercive force was 7.3 × 10 4 A/m, and rectangular ratio was 65%. 3-3) Preparation of Lubricating Layer Diacetyl cellulose (25 mg/m 2 ), and a mixture of C 6 H 13 CH(OH)C 10 H 20 COOC 40 H 81 (Compound a, 6 mg/m 2 )/C 50 H 101 O(CH 2 CH 2 O) 16 H (Compound b, 9 mg/m 2 ) were coated. This mixture of Compound a/Compound b was dissolved in xylene/propylene monomethyl ether (1/1, volume ratio) by heating at 105°C, and poured into propylene monomethyl ether (10 times amount) at room temperature and dispersed, and further dispersed in acetone (average grain size: 0.01 µm), then added to the coating solution. 4) Coating of Light-Sensitive Layer Each layer having the following composition was multilayer coated on the opposite side of the above obtained backing layer and a color negative film was prepared as Sample No. 101. Composition of Light-Sensitive Layer The main components for use in each layer are classified as follows: ExC Cyan Coupler ExM Magenta Coupler ExY Yellow Coupler ExS Sensitizing Dye UV Ultraviolet Absorbing Agent HBS High Boiling Point Organic Solvent H Hardening Agent for Gelatin The numeral corresponding to each component indicates the coated weight in unit of g/m 2 , and the coated weight of silver halide is shown as the calculated weight of silver. Further, in the case of a sensitizing dye, the coated weight is indicated in unit of mol per mol of silver halide in the same layer. First Layer : Antihalation Layer Black Colloidal Silver 0.09 as silver Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 -3 Solid Dispersion Dye ExF-2 0.030 Solid Dispersion Dye ExF-3 0.040 HBS-1 0.15 HBS-2 0.02 Second Layer : Interlayer Silver Iodobromide Emulsion M 0.065 as silver ExC-2 0.04 Polyethyl Acrylate Latex 0.20 Gelatin 1.04 Third Layer : Low Sensitivity Red-Sensitive Emulsion Layer Silver Iodobromide Emulsion A 0.25 as silver Silver Iodobromide Emulsion B 0.25 as silver ExS-1 6.9 × 10 -5 ExS-2 1.8 × 10 -5 ExS-3 3.1 × 10 -4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87 Fourth Layer : Middle Sensitivity Red-Sensitive Emulsion Layer Silver Iodobromide Emulsion C 0.70 as silver ExS-1 3.5 × 10 -4 ExS-2 1.6 × 10 -5 ExS-3 5.1 × 10 -4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75 Fifth Layer : High Sensitivity Red-Sensitive Emulsion Layer Silver Iodobromide Emulsion D 1.40 as silver ExS-1 2.4 × 10 -4 ExS-2 1.0 × 10 -4 ExS-3 3.4 × 10 -4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10 Sixth Layer : Interlayer Cpd-1 0.090 Solid Dispersion Dye ExF-4 0.030 HBS-1 0.050 Polyethyl Acrylate Latex 0.15 Gelatin 1.10 Seventh Layer : Low Sensitivity Green-Sensitive Emulsion Layer Silver Iodobromide Emulsion E 0.15 as silver Silver Iodobromide Emulsion F 0.10 as silver Silver Iodobromide Emulsion G 0.10 as silver ExS-4 3.0 × 10 -5 ExS-5 2.1 × 10 -4 ExS-6 8.0 × 10 -4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73 Eighth Layer : Middle Sensitivity Green-Sensitive Emulsion Layer Silver Iodobromide Emulsion H 0.80 as silver ExS-4 3.2 × 10 -5 ExS-5 2.2 × 10 -4 ExS-6 8.4 × 10 -4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 -3 Gelatin 0.80 Ninth Layer : High Sensitivity Green-Sensitive Emulsion Layer Silver Iodobromide Emulsion I 1.25 as silver ExS-4 3.7 × 10 -5 ExS-5 8.1 × 10 -5 ExS-6 3.2 × 10 -4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl Acrylate Latex 0.15 Gelatin 1.33 Tenth Layer : Yellow Filter Layer Yellow Colloidal Silver 0.015 as silver Cpd-1 0.16 Solid Dispersion Dye ExF-5 0.060 Solid Dispersion Dye ExF-6 0.060 Oil-Soluble Dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60 Eleventh Layer : Low Sensitivity Blue-Sensitive Emulsion Layer Silver Iodobromide Emulsion J 0.09 as silver Silver Iodobromide Emulsion K 0.09 as silver ExS-7 8.6 × 10 -4 ExC-8 7.0 × 10 -3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 -3 HBS-1 0.28 Gelatin 1.20 Twelfth Layer : High Sensitivity Blue-Sensitive Emulsion Layer Silver Iodobromide Emulsion L 1.00 as silver ExS-7 4.0 × 10 -4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 -3 HBS-1 0.070 Gelatin 0.70 Thirteenth Layer : First Protective Layer UV-1 0.19 UV-2 0.075 Acid-Processed Gelatin (Ca 150 ppm) 0.70 Fourteenth Layer : Second Protective Layer Lime-Processed Gelatin (Ca 1,900 ppm) 0.048 Polymethyl Methacrylate (average grain size: 2.3 µm, 95% or more of grains account for between 2.1 to 2.5 µm) 0.05 Poly(methyl Methacrylate/Methyl Acrylate = 55/45 in mol ratio) (average grain size: 2.3 µm, 95% or more of the grains account for between 2.1 to 2.4 µm) 0.07 Polymethyl Methacrylate (average grain size: 0.2 µm, 95% or more of grains account for between 0.10 to 0.30 µm) 0.22 Polydimethylsiloxane (viscosity: 100 cp (25°C)) 0.12 Stearic Acid Cetyl Ester (dispersed to 0.1 µm with sodium dodecylbenzenesulfonate) 0.03 Colloidal Silver (average grain size: 0.05 µm) 0.01 Further, W-1 to W-3, B-4 to B-6, F-1 to F-17, iron salt, lead salt, gold salt, platinum salt, palladium salt, iridium salt and rhodium salt were appropriately included in each layer to improve storage stability, processing properties, pressure resistance, fungicidal and biocidal properties, antistatic properties and coating properties. In Table 1: (1) Emulsions J, K and L were reduction sensitized during preparation of the grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to I were gold, sulfur, and selenium sensitized, respectively, in the presence of the spectral sensitizing dyes which are described at each light-sensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. (3) Low molecular weight gelatin was used in the preparation of the tabular grains according to the examples of JP-A-1-158426. (4) In tabular grains, there were observed such dislocation lines as disclosed in JP-A-3-237450 using a high pressure electron microscope. (5) Emulsion L comprised double structure grains containing an internal high iodide core as disclosed in JP-A-60-143331. Preparation of Dispersion of Organic Solid Dispersion Dye ExF-2 shown below was dispersed according to the following method. 21.7 ml of water, 3 ml of a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethanesulfonate, and 0.5 g of a 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (polymerization degree: 10) were put in a pot mill having a capacity of 700 ml, and 5.0 g of Dye ExF-2 and 500 ml of zirconium oxide beads (diameter: 1 mm) were added thereto and the content was dispersed for 2 hours. The vibrating ball mill which was used was BO type ball mill manufactured by Chuo Koki. The content was taken out after dispersion and added to 8 g of a 12.5% aqueous solution of gelatin and the beads were removed by filtration and the gelatin dispersion of the dye was obtained. The average grain size of fine grains of the dye was 0.44 µm. Solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained in the same manner. The average grain sizes of fine grains of the dyes were 0.24 µm, 0.45 µm and 0.52 µm, respectively. ExF-5 was dispersed according to the microprecipitation dispersion method disclosed in Working Example 1 of EP-A-549489. The average grain size was 0.06 µm. HBS-1 Tricresyl Phosphate HBS-2 Di-n-butyl Phthalate HBS-4 Tri(2-ethylhexyl) Phosphate The thus prepared photographic material was cut to a size of 24 mm in width and 160 cm in length, and two perforations of 2 mm square at an interval of 5.8 mm were provided 0.7 mm inside from one side of the width direction in the length direction of the photographic material. The sample provided with this set of two perforations at intervals of 32 mm was prepared and encased in the plastic film cartridge explained in FIG. 1 to FIG. 7 in U.S. Patent 5,296,887. This sample was charged in a camera and photographed standard subjects with the optimal exposure. Subsequently, digital saturation recording of recording wavelength of 50 µm was conducted from the side of the support having the magnetic recording layer using an audio type magnetic recording head made of Permalloy with head gap of 5 µm, the number of turns of 50 at a feed rate of 100 mm/s. One hundred and two sheets of the samples thus written with magnetic informations were continuously processed using the following described automatic processor with each stabilizing or rinsing solution. Processing was carried out using a pendant type automatic processor H4-220S type manufactured by Noritsu Koki Co., Ltd. The center part of the film was hung on a hanger with the emulsion surface outside and clips were attached at both ends of the film. The hanger supported the near sides of the film edges so as not to touch the image part, and so that the processing solution did not stay at this part. A plastic pole was fixed between clips of both ends to make an interval of 10 cm to prevent the film from touching each other. Processing Step Step Processing Time Processing Temperature (°C) Replenishment Rate (ml) Color Development 3 min 15 s 38 400 Bleaching 6 min 30 s 38 130 Washing (1) 2 min 10 s 24 countercurrent system from (2) to (1) Washing (2) 2 min 10 s 24 1,200 Fixing 6 min 30 s 38 400 Washing (3) 2 min 10 s 24 countercurrent system from (4) to (3) Washing (4) 2 min 10 s 24 1,200 Stabilization 1 min 5 s 38 400 Drying 22 min 20 s 45 The composition of each processing solution is described below. Color Developing Solution Tank Solution (g) Replenisher (g) Diethylenetriaminepentaacetic Acid 3.0 3.0 Disodium Catechol-3,5-disulfonate 0.3 0.3 Sodium Sulfite 3.9 5.5 Potassium Carbonate 39.0 39.0 Disodium N,N-Bis(2-sulfonato-ethyl)hydroxylamine 8.0 10.0 Potassium Bromide 1.3 - Potassium Iodide 1.3 mg - 4-Hydroxy-6-methyl-1,3,3a,7-tetraazaindene 0.05 - 2-Methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline Sulfate 4.5 6.8 Water to make 1.0 ℓ 1.0 ℓ pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.23 Bleaching Solution Tank Solution (g) Replenisher (g) N-(2-Carboxyphenyl)iminodiacetato Ferrate Pentahydrate 25.0 35.0 1,3-Diaminopropanetetraacetic Acid 2.0 3.0 Ammonium 1,3-Diaminopropanetetraacetato Ferrate Dihydrate 25.0 35.0 Succinic Acid 60.0 85.0 Malonic Acid 7.0 10.0 Glutaric Acid 15.0 20.0 Sodium Bromide 40.0 60.0 Sodium Nitrate 30.0 50.0 Sodium Hydroxide 30.0 45.0 Diethanolamine 20.0 - Water to make 1.0 ℓ 1.0 ℓ pH (adjusted with sodium hydroxide and nitric acid) 4.2 3.8 Fixing Solution Tank Solution (g) Replenisher (g) 1,3-Diaminopropanetetraacetic Acid 6.0 7.0 Ammonium Sulfite 20.0 22.0 An Aqueous Solution of Ammonium Thiosulfate (750 g/ℓ) 270.0 ml 300.0 ml Acetic Acid (90%) 5.0 5.0 Water to make 1.0 ℓ 1.0 ℓ pH (adjusted with aqueous ammonia and acetic acid) 6.4 6.3 The replenisher was in common with the tank solution in stabilizing process and the following solution was used. When the processing solution does not have the effect of image stabilization, the rinsing solution is used (unit: gram). Stabilizing Solution A Polyoxyethylene-p-monononylphenyl Ether (average polymerization degree: 10) 0.2 1,2,4-Triazole 0.6 1,4-Bis(1,2,4-triazol-1-ylmethyl)piperazine 0.40 1,2-Benzisothiazolin-3-one 0.10 Water to make 1.0 ℓ Rinsing Solution A Polyoxyethylene-p-monononylphenyl Ether (average polymerization degree: 10) 0.2 Water to make 1.0ℓ Rinsing Solution B Water only With respect to each processing solution in stabilizing process, Sample Nos. 4, 6 and 8 were processed with tap water, Sample Nos. 1, 5 and 7 with the following described amphoteric ion exchange water, and Nos. 2 and 3 with the mixed water of amphoteric ion exchange water and tap water. Amphoteric Ion Exchange Water Tap water was passed through a mixed bed column packed with an H-type strongly acidic cation exchange resin (Amberlite IR-120B of Rohm & Haas) and an OH-type strongly basic anion exchange resin (Amberlite IR-400 of Rohm & Haas) and treated so as to reduce the calcium concentration to 3 mg/ℓ. The above photographic materials after processing were measured for the output signal level of the isolated reproduction wave using a magnetic reproducing head made of Sendust with head gap of 2.5 µm, the number of turns of 2,000. The same magnetic reproducing heads were arranged in series with the intervals of 5 cm and measurement was conducted using the rear head. From the above results, the average output level of the first photographic material was taken as 100, and the average output of the 100th based on the first output was represented by percentage and shown in Table 1 (magnetic output). Further, 101st photographic material after processing was allowed to stand for 5 hours in a room of 20°C, 50% RH with the emulsion surface down, then the length in the width direction at the center of the film was measured using calipers. In the case of the film curls, the length is less than 24 mm (curling characteristics). Criteria of evaluation: AA 24.0 mm (no curling) A 23.8 mm or more B 23.5 mm or more and less than 23.8 mm C less than 23.5 mm The results are also shown in Table 1. The adhered amount of each of the final processing solution of the backing layer side of the 102nd photographic material was measured, all were 1.0 ml/m 2 or more. The measured value was obtained by extracting 1,2-benzisothiazolin-3-one adhered on the backing layer side with distilled water and determined through a liquid chromatography. The conductivity of each final processing solution was the value at 25°C measured with a conductivity meter CM-60S manufactured by Toa Denpa Kogyo Co., Ltd. Further, the concentration of calcium in the final processing solution was measured according to the atomic absorption method. As is shown in Table 2, in the processing using comparative final processing solutions, as Nos. 4, 6 and 8, when reading of the magnetic recording informations of 100 sheets were conducted continuously, the output of the 100th film was largely reduced. On the contrary, in the processing using processing solutions used in the present invention, 70% or more of the magnetic recording informations have been secured, and the lower the conductivity, the better were the results obtained. Further, with respect to curling characteristics, excellent results were obtained when using the final processing solutions used in the present invention. After 102 sheets of the above films were processed in each processing, color negative films 160S manufactured by Fuji Photo Film Co., Ltd. which were exposed with white light so as to obtain magenta density of 1.5 were processed. The films after processing were preserved under 60°C, 60% RH conditions for three days, then magenta density was measured. Nos. 5 to 8 were all discolored to 1.3 or less but densities of Nos. 1 to 4 were all 1.45 or more and image stabilizing effect was sufficient.

Claims: A method for development processing a silver halide color photographic material comprising a support having thereon a magnetic recording layer, wherein the conductivity of the final processing solution of said development processing is 0.1 mS/cm or less at 25°C. The method of claim 1, wherein said final processing solution is a stabilizing solution. The method of claim 1, wherein said final processing solution contains surfactant. The method of claim 1, wherein the conductivity of said final processing solution is from 0.001 to 0.05 mS/cm. The method of claim 4, wherein the conductivity of said final processing solution is from 0.003 to 0.03 mS/cm. The method of claim 1, wherein a color developing solution used in said method does not contain hydroxylamine. The method of claim 1, wherein said final processing solution contains 1,2-benzisothazolin-3-one.

Inventors: FUJITA YOSHIHIRO, FUJITA, YOSHIHIRO, FUJITA, YOSHIHIRO, C/O FUJI PHOTO FILM CO., LTD.
Applicants: FUJI PHOTO FILM CO LTD, FUJI PHOTO FILM CO., LTD.
Application year: 1996
Main classification: G03C7
IPC codes: G03C11, G03C7