[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

EP0735419A2 - Method for processing silver halide color photographic material - Google Patents

Method for processing silver halide color photographic material Download PDF

Info

Publication number
EP0735419A2
EP0735419A2 EP96105087A EP96105087A EP0735419A2 EP 0735419 A2 EP0735419 A2 EP 0735419A2 EP 96105087 A EP96105087 A EP 96105087A EP 96105087 A EP96105087 A EP 96105087A EP 0735419 A2 EP0735419 A2 EP 0735419A2
Authority
EP
European Patent Office
Prior art keywords
solution
processing
photographic material
magnetic recording
processing solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP96105087A
Other languages
German (de)
French (fr)
Other versions
EP0735419A3 (en
EP0735419B1 (en
Inventor
Yoshihiro C/O Fuji Photo Film Co. Ltd. Fujita
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0735419A2 publication Critical patent/EP0735419A2/en
Publication of EP0735419A3 publication Critical patent/EP0735419A3/en
Application granted granted Critical
Publication of EP0735419B1 publication Critical patent/EP0735419B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C11/00Auxiliary processes in photography
    • G03C11/02Marking or applying text
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3046Processing baths not provided for elsewhere, e.g. final or intermediate washings

Definitions

  • 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.
  • 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.
  • 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 about from 0.1 to 3.0 ⁇ m.
  • neither of these methods could provide a sufficient effect with respect to the output reduction of magnetic recording after development processing.
  • the present invention relates to, as a first embodiment, 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 present invention also relates to, as a second embodiment, a method for development processing a silver halide color photographic material comprising a support having thereon a magnetic recording layer, wherein the calcium concentration in a final processing solution of the development processing is 5 mg/l or less.
  • the present invention further relates to, as a third embodiment, a method for development processing a silver halide color photographic material comprising a support having thereon a magnetic recording layer, wherein 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.
  • a color developing solution used in the method for development processing does not contain hydroxylamine, and it is also preferred that the final processing solution contains 1,2-benzisothiazolin-3-one.
  • the silver halide color photographic material having a magnetic recording layer of the present invention is subjected to ordinary color development processing (hereinafter referred to as only processing) then 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.
  • 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 conducting any one of reducing the conductivity of the final processing solution of the development processing to 0.1 mS/cm or less, reducing the calcium concentration in the final processing solution to 5 mg/l or less, or reducing the adhered amount of the final processing solution to 0.3 ml/m 2 or less which is remained after development processing on the surface of the silver halide color photographic material on which the magnetic recording layer is provided.
  • 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 processing solution such as a stabilizing solution and a rinsing solution contains various compounds for stabilizing images or other purposes.
  • 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.
  • 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 in the stabilizing solution.
  • 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.
  • 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.
  • 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.
  • a gel type, a porous type and a support carrying type can be used as the structure of a resin.
  • 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. but the present invention is not limited thereto.
  • a reverse osmosis equipment for reverse osmosis treating the preparation water is preferably a low pressure type equipment, for example, about from 2 to 30 kg/cm 2 .
  • 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.
  • the conductivity used herein is a value at 25°C and is measured by a commercially available conductivity meter.
  • 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 is reduced to 5 mg/l or less, preferably 3 mg/l or less.
  • the calcium concentration may be zero.
  • the calcium concentration means the total calcium concentration of the calcium compounds contained in one liter of the final processing solution and represented as the weight of calcium.
  • any of the above methods for reducing the conductivity can be used.
  • ion exchangers in the cation exchange method include an ion exchange resin, an ton exchange membrane and zeolite, with an ion exchange resin being most preferred of these.
  • a method of exchanging a calcium ion with an Na ion 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.
  • a method for reducing the adhered amount of the final processing solution to 0.3 ml/m 2 or less which is remained after development processing on the surface of the silver halide color photographic material on which the magnetic recording layer is provided (third embodiment) is described below.
  • the adhered amount of the remaining final processing solution used herein is the amount of the components of the final processing solution adhered on the film and remained after drying, and the remaining amount of the components of the final processing solution is expressed as the volume of the solution before drying.
  • the adhered amount of the remaining final processing solution can be measured by coating the surface of the film other than the surface having the magnetic recording layer after processing, extracting the components adhered on a definite area of the surface having the magnetic recording layer into distilled water at 25°C, and determining the concentration of the components in the water.
  • the compound to be determined is the main component in the final processing solution but if such a compound cannot be determined, other compounds contained in the final processing solution may be determined. However, a compound that has a behavior of specific adsorption or an unstable compound cannot be used for the determination. In such a case, for the measurement of the adhered amount of the final processing solution, a definite amount of a compound (e.g., heavy metal ion or a fluorescent compound) is previously added in the final processing solution as a marker, and the determination can be conducted by measuring the marker in the solution extracted from the film after processing.
  • a compound e.g., heavy metal ion or a fluorescent compound
  • Various known methods can be used for reducing the adhered amount of the remaining final processing solution. Specifically, a method of squeezing the solution with a rubber blade or air, a method of wiping off the solution adhered with a water absorptive cloth or polymer, and a method of vibrating the film in the air before drying can be used.
  • the contact area of a hanger with a film is preferably as small as possible and not to provide a closed space between the hanger and the film.
  • the structure in which the clips attached to the lower ends of the film keep a distance between the films is preferred.
  • the adhered amount of the final processing solution which is remained after development processing on the surface of the silver halide color photographic material on which the magnetic recording layer is provided is preferably from 0 to 0.2 ml/m 2 , particularly preferably from 0 to 0.1 ml/m 2 .
  • 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-hydroxybenzaldehyde, 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.
  • image stabilizers for example, formaldehyde, benzaldehydes such as m-hydroxybenzaldehyde, 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.
  • image stabilizers for example, formaldehyde, benzaldehydes such as m-hydroxybenzaldehyde
  • 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.
  • 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.
  • 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.
  • a solution having bleaching ability such as a bleaching solution and a bleach-fixing solution
  • a fixing ability such as a fixing solution and a bleach-fixing solution.
  • 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.
  • 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.
  • the magnetic grains for use in the present invention include ferromagnetic iron oxide such as ⁇ -Fe 2 O 3 , Co-coated ⁇ -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 ⁇ -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 ( ⁇ 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.
  • 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.
  • 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.
  • isocyanate crosslinking agents examples 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.
  • 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 tolylenediisocyan
  • the thickness of a magnetic recording layer is from 0.1 ⁇ m to 10 ⁇ m, preferably from 0.2 ⁇ m to 5 ⁇ m, and more preferably from 0.3 ⁇ m to 3 ⁇ m.
  • 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).
  • 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.
  • aromatic dicarboxylic acids include 2,6-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, and phthalic acid.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ m) may be contained as a matting agent.
  • antistatic agents are preferably used in the photographic material of the present invention.
  • 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 ⁇ cm or less, more preferably 10 5 ⁇ cm or less and having a grain size of from 0.001 to 1.0 ⁇ m 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.
  • the photographic material of the present invention prefferably has 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.
  • fine grains having a grain size of 0.8 ⁇ m or less are preferably added at the same time.
  • polymethyl methacrylate 0.2 ⁇ m
  • copolymer of methyl methacrylate and methacrylic acid 9/1 by mol
  • polystyrene grains 0.25 ⁇ m
  • colloidal silica 0.03 ⁇ m
  • 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.
  • 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.
  • 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 of the present invention.
  • 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.
  • 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.
  • 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.
  • 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.
  • replenisher of a color developing solution from 1.1 to 3 times of these amounts are preferably used.
  • 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.
  • 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 ion 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.
  • concentration of bromide ion is defined in such a range, the concentration of bromide ion in the replenisher can be obtained from the following equation, however, when C is minus, bromide ion is preferably not contained in the replenisher.
  • C A-W/V
  • bromide necessary for preparing the above described color developing solution or color developing replenisher is contained in the color developing solution of the present invention. Accordingly, bromide may be contained in the color developing solution of the present invention or may not be contained at all.
  • 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.
  • 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.
  • 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 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.
  • 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
  • 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 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.
  • the use of the sulfinic acid disclosed in JP-A-1-224762 as well as p-toluenesulfinate is preferred for improving preservability.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • silver iodobromide emulsions having an average silver iodide content of from 3 to 20 mol% is preferably used as a silver halide emulsion
  • 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.
  • 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 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 ⁇ m.
  • 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.
  • Type of Additives RD 17643 RD 18716 RD 307105 1. Chemical Sensitizers page 23 page 648, right column page 866 2. Sensitivity Increasing Agents ⁇ page 648, right column ⁇ 3. Spectral Sensitizers and Supersensitizers pages 23-24 page 648, right column to page 649, right column pages 866-868 4. Whitening Agents page 24 page 647, right column page 868 5. Light Absorbing Agents, Filter Dyes, and Ultraviolet Absorbing Agents pages 25-26 page 649, right column to page 650, left column page 873 6.
  • Couplers can be used in the photographic material of the present invention, and the following couplers are particularly preferred.
  • 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)).
  • 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).
  • the yellow colored cyan couplers represented by formulae (CI), (CII), (CIII) and (CIV) disclosed on page 5 of
  • 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.
  • the stains adhered to the film are removed by making the film contact with a different head or analogues.
  • the support which was used in the present invention was prepared as follows.
  • 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.
  • 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).
  • an antistatic layer, a magnetic recording layer and a lubricating layer having the following compositions were coated as backing layers.
  • 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 ⁇ m and specific resistance of 5 ⁇ cm (the grain size of secondary agglomerate: about 0.08 ⁇ m), 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 .
  • silica grains 0.3 ⁇ m
  • an aluminum oxide abrasive (0.15 ⁇ m) 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
  • saturation magnetization moment of the magnetic recording layer was 4.2 emu/g
  • coercive force was 7.3 ⁇ 10 4 A/m
  • rectangular ratio was 65%.
  • 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 ⁇ m), then added to the coating solution.
  • 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.
  • the main components for use in each layer are classified as follows:
  • 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.
  • Second 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
  • Fourth Layer Middle Sensitivity Red-Sensitive Emul
  • 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.
  • 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 ⁇ m.
  • ExF-3, ExF-4 and ExF-6 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 ⁇ m, 0.45 ⁇ m and 0.52 ⁇ m, 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 ⁇ m.
  • HBS-1 Tricresyl Phosphate
  • 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.
  • Step Processing Time Processing Temperature (°C) Replenishment Rate* (ml) Color Development 3 min 15 sec 38 400 Bleaching 6 min 30 sec 38 130 Washing (1) 2 min 10 sec 24 countercurrent system from (2) to (1) Washing (2) 2 min 10 sec 24 1,200 Fixing 6 min 30 sec 38 400 Washing (3) 2 min 10 sec 24 countercurrent system from (4) to (3) Washing (4) 2 min 10 sec 24 1,200 Stabilization 1 min 5 sec 38 400 Drying 22 min 20 sec 45 * Replenishment rate: per m 2 of the photographic material
  • 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.
  • the processing solution does not have the effect of image stabilization, the rinsing solution is used (unit: gram).
  • 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, Nos. 2 and 3 with the mixed water of amphoteric ion exchange water and tap water, and No. 9 with the cation exchange water shown below.
  • 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.
  • H-type strongly acidic cation exchange resin Amberlite IR-120B of Rohm & Haas
  • Amberlite IR-400 of Rohm & Haas
  • Tap water was passed through a mixed bed column packed with an Na-type strongly acidic cation exchange resin (Amberlite IR-120B of Rohm & Haas) and treated so as to reduce the calcium concentration to 1 mg/l.
  • an Na-type strongly acidic cation exchange resin Amberlite IR-120B of Rohm & Haas
  • the same magnetic reproducing heads were arranged in series with the intervals of 5 cm and measurement was conducted using the rear head.
  • 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).
  • 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).
  • 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. TABLE 2 No.
  • FP-560B manufactured by Fuji Photo Film Co., Ltd. according to the following.
  • the processor was modified such that all of the overflow from the bleaching bath was introduced to the waste solution tank not to the next bath.
  • FP-560B is loaded with the evaporation compensation means disclosed in Kokai Giho No. 94-4992, Hatsumei Kyokai.
  • Stabilization and fixation were conducted in a countercurrent system from (2) to (1), and the overflow from the washing tank was all introduced into the fixing tank (2). Further, the amount of carryover of the developing solution into the bleaching step, the amount of carryover of the bleaching solution to the fixing step, and the amount of carryover of the fixing solution to the washing step were 2.5 ml, 2.0 ml and 2.0 ml per 1.1 meter of 35 mm wide photographic material, respectively. Further, the crossover time was 6 seconds in each case, and this time is included in the processing time of the previous step.
  • Open areas of the above processor were 100 cm 2 with the color developing solution, 120 cm 2 with the bleaching solution and 100 cm 2 with other processing solutions.
  • 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 ion and magnesium ion concentrations to 3 mg/l or less, subsequently 20 mg/l of sodium isocyanurate dichloride and 150 mg/l of sodium sulfate were added thereto.
  • the pH of this washing water was in the range of from 6.5 to 7.5.
  • Each developing solution was aged in a processor for one week while controlling the temperature, then processing was carried out.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

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/m2 or less.

Description

    FIELD OF THE INVENTION
  • 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.
  • BACKGROUND OF THE INVENTION
  • 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 about 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.
  • SUMMARY OF THE INVENTION
  • 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, as a first embodiment, 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 present invention also relates to, as a second embodiment, a method for development processing a silver halide color photographic material comprising a support having thereon a magnetic recording layer, wherein the calcium concentration in a final processing solution of the development processing is 5 mg/ℓ or less.
  • The present invention further relates to, as a third embodiment, a method for development processing a silver halide color photographic material comprising a support having thereon a magnetic recording layer, wherein 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/m2 or less.
  • In the first embodiment of the present invention, it is preferred that a color developing solution used in the method for development processing does not contain hydroxylamine, and it is also preferred that the final processing solution contains 1,2-benzisothiazolin-3-one.
  • In the first embodiment of the present invention, it is further preferred that the adhered amount of the 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/m2 or less.
  • DETAILED DESCRIPTION OF THE INVENTION
  • The silver halide color photographic material having a magnetic recording layer of the present invention is subjected to ordinary color development processing (hereinafter referred to as only processing) then 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 conducting any one of reducing the conductivity of the final processing solution of the development processing to 0.1 mS/cm or less, reducing the calcium concentration in the final processing solution to 5 mg/ℓ or less, or reducing the adhered amount of the final processing solution to 0.3 ml/m2 or less which is remained after development processing on the surface of the silver halide color photographic material on which the magnetic recording layer is provided.
  • 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 (first embodiment) 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 in the stabilizing solution.
  • 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. but the present invention is not limited thereto.
  • A reverse osmosis equipment for reverse osmosis treating the preparation water is preferably a low pressure type equipment, for example, about from 2 to 30 kg/cm2. 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 Du Pont, 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.
  • In the second embodiment of the present invention, the calcium concentration in the final processing solution is reduced to 5 mg/ℓ or less, preferably 3 mg/ℓ or less. The calcium concentration may be zero.
  • The calcium concentration means the total calcium concentration of the calcium compounds contained in one liter of the final processing solution and represented as the weight of calcium.
  • When reducing the calcium concentration in the final processing solution, as in the case of reducing the conductivity described above, it is also effective to reduce the calcium concentration in the processing chemicals and/or the preparation water thereof.
  • If the concentration of a calcium ion 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 a calcium ion is exchanged with a monovalent ion such as sodium or potassium.
  • Examples of ion exchangers in the cation exchange method include an ion exchange resin, an ton exchange membrane and zeolite, with an ion exchange resin being most preferred of these.
  • A method of exchanging a calcium ion with an Na ion 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.
  • A method for reducing the adhered amount of the final processing solution to 0.3 ml/m2 or less which is remained after development processing on the surface of the silver halide color photographic material on which the magnetic recording layer is provided (third embodiment) is described below.
  • The adhered amount of the remaining final processing solution used herein is the amount of the components of the final processing solution adhered on the film and remained after drying, and the remaining amount of the components of the final processing solution is expressed as the volume of the solution before drying.
  • The adhered amount of the remaining final processing solution can be measured by coating the surface of the film other than the surface having the magnetic recording layer after processing, extracting the components adhered on a definite area of the surface having the magnetic recording layer into distilled water at 25°C, and determining the concentration of the components in the water.
  • In general, the compound to be determined is the main component in the final processing solution but if such a compound cannot be determined, other compounds contained in the final processing solution may be determined. However, a compound that has a behavior of specific adsorption or an unstable compound cannot be used for the determination. In such a case, for the measurement of the adhered amount of the final processing solution, a definite amount of a compound (e.g., heavy metal ion or a fluorescent compound) is previously added in the final processing solution as a marker, and the determination can be conducted by measuring the marker in the solution extracted from the film after processing.
  • Various known methods can be used for reducing the adhered amount of the remaining final processing solution. Specifically, a method of squeezing the solution with a rubber blade or air, a method of wiping off the solution adhered with a water absorptive cloth or polymer, and a method of vibrating the film in the air before drying can be used.
  • When processing is carried out using a hanging type automatic processor, if a processing solution is pooled at a hanger or a clip part supporting a film, the amount of the solution adhered that part increases, which causes staining of the film or the reduction of output when reading magnetic information. Therefore, the structure which does not pool a processing solution is preferred. Specifically, the contact area of a hanger with a film is preferably as small as possible and not to provide a closed space between the hanger and the film.
  • Further, when a film is turned up and processed, if the film is dried with keeping in contact each other in the vicinity of the lower ends, the amount of the solution adhered that part also increases. Accordingly, the structure in which the clips attached to the lower ends of the film keep a distance between the films is preferred.
  • The adhered amount of the final processing solution which is remained after development processing on the surface of the silver halide color photographic material on which the magnetic recording layer is provided is preferably from 0 to 0.2 ml/m2, particularly preferably from 0 to 0.1 ml/m2.
  • 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-hydroxybenzaldehyde, 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-Fe2O3, Co-coated γ-Fe2O3, 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-Fe2O3 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 (SBET) is preferably 20 m2/g or more, and particularly preferably 30 m2/g or more. The saturation magnetization (σs) of the ferromagnetic substance is preferably from 3.0 × 104 to 3.0 × 105 A/m and particularly preferably from 4.0 × 104 to 2.5 × 105 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/m2, preferably from 0.01 to 2 g/m2, and more preferably from 0.02 to 0.5 g/m2.
  • 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 SnO2 or Sb2O5) 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. SiO2, TiO2, 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 of 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, TiO2, SnO2, Al2O3, In2O3, SiO2, MgO, BaO, MoO3 and V2O5 having a volume resistivity of 107Ω·cm or less, more preferably 105Ω·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/m2 and particularly preferably from 10 to 350 mg/m2. 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 of 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 of 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 of the present invention 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 1012Ω 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 cm3 or less and preferably 25 cm3 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 of the present invention. In particular, when carrying out rapid processing with the color developing time being reduced to 2 min 30 sec 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 m2 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 ion 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 ion is defined in such a range, the concentration of bromide ion in the replenisher can be obtained from the following equation, however, when C is minus, bromide ion is preferably not contained in the replenisher. C = A-W/V
    Figure imgb0001
  • C:
    The concentration of bromide ion in the replenisher of a color developing solution (mol/ℓ)
    A:
    The concentration of bromide ion in an objective color developing solution (mol/ℓ)
    W:
    The amount of bromide ion dissolved out from a photographic material into a color developing solution when m2 of a photographic material is color developed (mol)
    V:
    The replenishment rate of the color developing replenisher per m2 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 of the present invention. Accordingly, bromide may be contained in the color developing solution of the present invention or may not be contained at all.
  • Moreover, when the replenishment rate is reduced or bromide ion is 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
    Figure imgb0002
  • CR:
    The concentration of the component in the replenisher
    CT:
    The concentration of the component in the mother solution (processing tank solution)
    CP:
    The concentration of the component consumed during processing
    V1:
    The replenishment rate of the replenisher having a bleaching ability per m2 of the photographic material (ml)
    V2:
    The amount of carryover from the previous tank by a photographic material of m2 (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 m2 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 m2 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.
    Type of Additives RD 17643 RD 18716 RD 307105
    1. Chemical Sensitizers page 23 page 648, right column page 866
    2. Sensitivity Increasing Agents page 648, right column
    3. Spectral Sensitizers and Supersensitizers pages 23-24 page 648, right column to page 649, right column pages 866-868
    4. Whitening Agents page 24 page 647, right column page 868
    5. Light Absorbing Agents, Filter Dyes, and Ultraviolet Absorbing Agents pages 25-26 page 649, right column to page 650, left column page 873
    6. Binders page 26 page 651, left column pages 873-874
    7. Plasticizers and Lubricants page 27 page 650, right column page 876
    8. Coating Aids and Surfactants pages 26-27 page 650, right column pages 875-876
    9. Antistatic Agents page 27 page 650, right column pages 876-877
    10. Matting Agents pages 878-879
  • Various dye-forming couplers can be used in the photographic material of 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, but these are not to be construed as limiting the present invention.
  • 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 cc/m2, using a bar coater): 0.1 g/m2 of gelatin, 0.01 g/m2 of sodium α-sulfo-di-2-ethylhexylsuccinate, 0.04 g/m2 of salicylic acid, 0.2 g/m2 of p-chlorophenol, 0.012 g/m2 of (CH2=CHSO2CH2CH2NHCO)2CH2, and 0.02 g/m2 of polyamideepichlorohydrin 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/m2 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/m2 of gelatin, 0.02 g/m2 of (CH2=CHSO2CH2CH2NHCO)2CH2, 0.005 g/m2 of polyoxyethylene-p-nonylphenol (polymerization degree: 10) and resorcin were coated. The electric resistance at 25°C, 10% RH was 108.1.
  • 3-2) Coating of Magnetic Recording Layer
  • 0.06 g/m2 of cobalt-γ-iron oxide which was coating-treated with 3-polyoxyethylene-propyloxytrimethoxysilane (polymerization degree: 15) (15 wt%) (specific surface area: 43 m2/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/m2 of diacetyl cellulose (dispersion of the iron oxide was carried out using an open kneader and a sand mill), 0.3 g/m2 of C2H5C(CH2OCONH-C6H13(CH3)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/m2. 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 DB 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 × 104A/m, and rectangular ratio was 65%.
  • 3-3) Preparation of Lubricating Layer
  • Diacetyl cellulose (25 mg/m2), and a mixture of C6H13CH(OH)C10H20COOC40H81 (Compound a, 6 mg/m2)/C50H101O(CH2CH2O)16H (Compound b, 9 mg/m2) 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/m2, 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. TABLE 1
    Emulsion Average AgI Content (%) Variation Coefficient of the AgI Content among Grains (%) Average Grain Size Corresponding to Sphere (µm) Variation Coefficient of the Grain Size (%) Projected Area Diameter Corresponding to Circle (µm) Diameter/Thickness Ratio
    A 1.7 10 0.46 15 0.56 5.5
    B 3.5 15 0.57 20 0.78 4.0
    C 8.9 25 0.66 25 0.87 5.8
    D 8.9 18 0.84 26 1.03 3.7
    E 1.7 10 0.46 15 0.56 5.5
    F 3.5 15 0.57 20 0.78 4.0
    G 8.8 25 0.61 23 0.77 4.4
    H 8.8 25 0.61 23 0.77 4.4
    I 8.9 18 0.84 26 1.03 3.7
    J 1.7 10 0.46 15 0.50 4.2
    K 8.8 18 0.64 23 0.85 5.2
    L 14.0 25 1.28 26 1.46 3.5
    M 1.0 0.07 15 1
  • 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.
    Figure imgb0003
    Figure imgb0004
    Figure imgb0005
    Figure imgb0006
    Figure imgb0007
    Figure imgb0008
    Figure imgb0009
    Figure imgb0010
    Figure imgb0011
    Figure imgb0012
    HBS-1 Tricresyl Phosphate
    HBS-2 Di-n-butyl Phthalate
    Figure imgb0013
    HBS-4 Tri(2-ethylhexyl) Phosphate
    Figure imgb0014
    Figure imgb0015
    Figure imgb0016
    Figure imgb0017
    Figure imgb0018
    Figure imgb0019
  • 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/sec.
  • 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 sec 38 400
    Bleaching 6 min 30 sec 38 130
    Washing (1) 2 min 10 sec 24 countercurrent system from (2) to (1)
    Washing (2) 2 min 10 sec 24 1,200
    Fixing 6 min 30 sec 38 400
    Washing (3) 2 min 10 sec 24 countercurrent system from (4) to (3)
    Washing (4) 2 min 10 sec 24 1,200
    Stabilization 1 min 5 sec 38 400
    Drying 22 min 20 sec 45
    * Replenishment rate: per m2 of the photographic material
  • 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-sulfonatoethyl)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 1.0 ℓ
  • 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, Nos. 2 and 3 with the mixed water of amphoteric ion exchange water and tap water, and No. 9 with the cation exchange water shown below.
  • 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.
  • Cation Ion Exchange Water
  • Tap water was passed through a mixed bed column packed with an Na-type strongly acidic cation exchange resin (Amberlite IR-120B of Rohm & Haas) and treated so as to reduce the calcium concentration to 1 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/m2 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. TABLE 2
    No. Processing Solution in Stabilizing Process Conductivity in Final Bath (mS/cm) Concentration of Calcium in Final Bath (mg/ℓ) Magnetic Output (%) Curling Characteristics Remarks
    1 Stabilizing Solution A 0.03 3 98 A Invention
    2 " 0.05 5 92 A Invention
    3 " 0.1 8 88 A Invention
    4 " 0.3 30 30 C Comparison
    5 Rinsing Solution A 0.01 3 97 B Invention
    6 " 0.28 30 60 C Comparison
    7 Rinsing Solution B 0.01 3 95 B Invention
    8 " 0.28 30 50 C Comparison
    9 Stabilizing Solution A 0.3 1 79 A Invention
  • 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 of the present invention, 70% or more of the magnetic recording informations have been secured, and the lower the conductivity or the lower the calcium concentration, the better was the results obtained. Further, with respect to curling characteristics, excellent results were obtained when using the final processing solutions of 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 and No. 9 were all 1.45 or more and image stabilizing effect was sufficient.
  • EXAMPLE 2
  • In processing of No. 4 of Example 1, after coming out from the final processing solution and before entering drying section, films were subjected to treatment of reducing the adhered amount of solution on the back surface by blowing dry air (Nos. 11 to 13). In processing of No. 3 of Example 1, the same procedures as in Nos. 11 to 13 were conducted (Nos. 14 to 16). Control of the adhered amount of solution was conducted by changing the blowing time of dry air.
  • Evaluation was carried out in the same manner as in Example 1. As shown in Table 3, magnetic output and curling characteristics were improved by reducing the adhered amount of the final processing solution. Particularly, extremely superior results were obtained if the conductivity of the final processing solution was 0.1 mS/cm or less. TABLE 3
    No. Adhered Amount of Final Processing Solution (ml/m2) Magnetic Output (%) Curling Characteristics Remarks
    11 0.1 93 A Invention
    12 0.2 88 A Invention
    13 0.3 74 B Invention
    4 1.0 30 C Comparison
    14 0.1 100 AA Invention
    15 0.2 99 AA Invention
    16 0.3 97 A Invention
    3 1.0 88 A Invention
  • EXAMPLE 3
  • The following processing was carried out with samples' prepared in Example 1.
  • Each processing was conducted using an automatic processor FP-560B manufactured by Fuji Photo Film Co., Ltd. according to the following. The processor was modified such that all of the overflow from the bleaching bath was introduced to the waste solution tank not to the next bath. FP-560B is loaded with the evaporation compensation means disclosed in Kokai Giho No. 94-4992, Hatsumei Kyokai.
  • The processing step and the composition of each processing solution are shown below.
  • Processing Step
  • Step Processing Time Processing Temperature (°C) Replenishment Rate* (ml) Tank Capacity (liter)
    Color Development 3 min 5 sec 37.8 400 17.2
    Bleaching 50 sec 38.0 130 5
    Fixing (1) 50 sec 38.0 5
    Fixing (2) 50 sec 38.0 200 5
    Washing 30 sec 38.0 400 3.5
    Stabilization (1) 20 sec 38.0 3
    Stabilization (2) 20 sec 38.0 380 3
    Drying 1 min 30 sec 60
    * Replenishment rate: per m2 of the photographic material
  • Stabilization and fixation were conducted in a countercurrent system from (2) to (1), and the overflow from the washing tank was all introduced into the fixing tank (2). Further, the amount of carryover of the developing solution into the bleaching step, the amount of carryover of the bleaching solution to the fixing step, and the amount of carryover of the fixing solution to the washing step were 2.5 ml, 2.0 ml and 2.0 ml per 1.1 meter of 35 mm wide photographic material, respectively. Further, the crossover time was 6 seconds in each case, and this time is included in the processing time of the previous step.
  • Open areas of the above processor were 100 cm2 with the color developing solution, 120 cm2 with the bleaching solution and 100 cm2 with other processing solutions.
  • 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
    Preservative (shown in Table 4) 0.03 mol 0.03 mol
    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 6.5
    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)
    Ammonium 1,3-Diaminopropanetetraacetato Ferrate Monohydrate 113 170
    Ammonium Bromide 70 105
    Ammonium Nitrate 14 21
    Succinic Acid 40 60
    Maleic Acid 33 50
    Water to make 1.0 ℓ 1.0 ℓ
    pH (adjusted with aqueous ammonia) 4.6 4.0
  • Fixing (1) Tank Solution
  • The mixed solution of 5/95 mixture (volume ratio) of the above bleaching tank solution and the following fixing tank solution (pH: 6.8)
  • Fixing (2) Tank Solution
  • Tank Solution (g) Replenisher (g)
    Aqueous Ammonium Thiosulfate Solution (750 g/ℓ) 240 ml 727 ml
    Imidazole 7 20
    Ammonium Methanethiosulfonate 5 15
    Ammonium Methanesulfinate 10 30
    Ethylenediaminetetraacetic Acid 13 39
    Water to make 1.0 ℓ 1.0 ℓ
    pH (adjusted with aqueous ammonia and acetic acid) 7.4 7.45
  • Washing 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 ion and magnesium ion concentrations to 3 mg/ℓ or less, subsequently 20 mg/ℓ of sodium isocyanurate dichloride and 150 mg/ℓ of sodium sulfate were added thereto. The pH of this washing water was in the range of from 6.5 to 7.5.
  • Stabilizing Solution
  • The same as No. 2 in Example 1.
  • Each developing solution was aged in a processor for one week while controlling the temperature, then processing was carried out.
  • The processing in which the preservatives shown in Table 4 were used was evaluated for magnetic output in the same manner as in Example 1. TABLE 4
    No. Preservative for Color Developing Solution Magnetic Output
    21 Disodium-N,N-bis(2-sulfonatoethyl)hydroxylamine 98
    22 Diethylhydroxylamine 94
    23 Monomethylhydroxylamine 94
    24 Hydroxylaminesulfate 90
  • As is understood from Table 4, if hydroxylamine is used in a color developing solution, magnetic output is deteriorated.
  • Further, processing was carried out in the same manner as No. 21 except for removing 1,2-benzisothiazolin-3-one from the stabilizing solution in No. 21. in Table 4 (No. 25) and evaluation of magnetic output was conducted. As a result, the magnetic output of No. 25 was 85%, from which it was found that the reduction of the output of No. 25 was large compared with No. 21.
  • While the invention has been described in detail and with reference to specific examples 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.

Claims (17)

  1. 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 said development processing is 0.1 mS/cm or less.
  2. A method as claimed in claim 1, wherein said final processing solution is a stabilizing solution.
  3. A method as claimed in claim 1, wherein said final processing solution contains surfactant.
  4. A method as claimed in claim 1, wherein the conductivity of said final processing solution is from 0.001 to 0.05 mS/cm.
  5. A method as claimed in claim 4, wherein the conductivity of said final processing solution is from 0.003 to 0.03 mS/cm.
  6. A method as claimed in claim 1, wherein a color developing solution used in said method does not contain hydroxylamine.
  7. A method as claimed in claim 1, wherein said final processing solution contains 1,2-benzisothazolin-3-one.
  8. A method as claimed in claim 1, wherein the adhered amount of said final processing solution remained on a surface of said photographic material on which said magnetic recording layer is provided after development processing is 0.3 ml/m2 or less.
  9. A method for development processing a silver halide color photographic material comprising a support having thereon a magnetic recording layer, wherein the calcium concentration in a final processing solution of said development processing is 5 mg/ℓ or less.
  10. A method as claimed in claim 9, wherein said final processing solution is a stabilizing solution.
  11. A method as claimed in claim 9, wherein said final processing solution contains surfactant.
  12. A method as claimed in claim 9, wherein the calcium content in said final processing solution is 3 mg/ℓ or less.
  13. A method for development processing a silver halide color photographic material comprising a support having thereon a magnetic recording layer, wherein the adhered amount of a final processing solution remained on a surface of said photographic material on which said magnetic recording layer is provided after development processing is 0.3 ml/m2 or less.
  14. A method as claimed in claim 13, wherein said final processing solution is a stabilizing solution.
  15. A method as claimed in claim 13, wherein said final processing solution contains surfactant.
  16. A method as claimed in claim 13, wherein the adhered amount of said final processing solution remained on a surface of said photographic material on which said magnetic recording layer is provided after development processing is from 0.2 ml/m2 or less.
  17. A method as claimed in claim 16, wherein the adhered amount of said final processing solution remained on a surface of said photographic material on which said magnetic recording layer is provided after development processing is from 0.1 ml/m2 or less.
EP19960105087 1995-03-30 1996-03-29 Method for processing silver halide color photographic material Expired - Lifetime EP0735419B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP7371995 1995-03-30
JP73719/95 1995-03-30

Publications (3)

Publication Number Publication Date
EP0735419A2 true EP0735419A2 (en) 1996-10-02
EP0735419A3 EP0735419A3 (en) 1997-01-02
EP0735419B1 EP0735419B1 (en) 1999-03-03

Family

ID=13526321

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19960105087 Expired - Lifetime EP0735419B1 (en) 1995-03-30 1996-03-29 Method for processing silver halide color photographic material

Country Status (2)

Country Link
EP (1) EP0735419B1 (en)
DE (1) DE69601585T2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0853256A2 (en) * 1997-01-10 1998-07-15 Konica Corporation Stabilizing solution for processing silver halide color photographic light-sensitive material and method for processing silver halide color photographic light-sensitive material using the same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0496346A1 (en) * 1991-01-21 1992-07-29 Fuji Photo Film Co., Ltd. Silver halide photographic material
US5238794A (en) * 1990-07-16 1993-08-24 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0611990A1 (en) * 1993-02-17 1994-08-24 Fuji Photo Film Co., Ltd. A photographic composition having fixing capacity and a method for processing using the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5238794A (en) * 1990-07-16 1993-08-24 Fuji Photo Film Co., Ltd. Silver halide color photographic material
EP0496346A1 (en) * 1991-01-21 1992-07-29 Fuji Photo Film Co., Ltd. Silver halide photographic material
EP0611990A1 (en) * 1993-02-17 1994-08-24 Fuji Photo Film Co., Ltd. A photographic composition having fixing capacity and a method for processing using the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0853256A2 (en) * 1997-01-10 1998-07-15 Konica Corporation Stabilizing solution for processing silver halide color photographic light-sensitive material and method for processing silver halide color photographic light-sensitive material using the same
EP0853256A3 (en) * 1997-01-10 1999-01-13 Konica Corporation Stabilizing solution for processing silver halide color photographic light-sensitive material and method for processing silver halide color photographic light-sensitive material using the same

Also Published As

Publication number Publication date
EP0735419A3 (en) 1997-01-02
DE69601585D1 (en) 1999-04-08
EP0735419B1 (en) 1999-03-03
DE69601585T2 (en) 1999-07-01

Similar Documents

Publication Publication Date Title
EP0735419B1 (en) Method for processing silver halide color photographic material
US5843631A (en) Silver halide photographic material
JP3354035B2 (en) Processing method of silver halide color photographic light-sensitive material
JPH08234389A (en) Liquid coloring developer for silver halide color photographic sensitive material, and processing method using it
EP0750226B1 (en) A method for processing a silver halide color photographic light-sensitive material
JPH086220A (en) Method for processing silver halide color photographic sensitive material and regenerating agent for bleaching solution used in the method
US5976775A (en) Silver halide color photographic light-sensitive material
JP3563510B2 (en) Processing of silver halide photographic materials
JPH08328225A (en) Method for processing silver halide color photographic sensitive material
EP0789275B1 (en) Method for processing silver halide color light-sensitive material
JPH09179247A (en) Method for processing silver halide photographic sensitive material
US6013426A (en) Silver halide color photographic light-sensitive material
JP3856255B2 (en) Color developer composition for silver halide color photographic light-sensitive material and development processing method
EP0750225A1 (en) Method for reducing residual sensitizing dyes after development processing
JPH0934046A (en) Silver halide color photographic sensitive material
JPH0961976A (en) Method for reducing residual sensitizing dye after development processing
JPH0934047A (en) Silver halide color photographic sensitive material
JPH09211799A (en) Silver halide photographic sensitive material
JPH08328231A (en) Processing leader tape and cleaning method using the same
JPH09203997A (en) Silver halide photographic sensitive material and its package
JPH08190182A (en) Color image forming method
JPH09230558A (en) Processing method for silver halide photographic sensitive material and development processing device therefor
JPH095958A (en) Silver halide photographic sensitive material and picture forming method
JPH09179239A (en) Silver halide photographic sensitive material and its packed body
JPH08234346A (en) Silver halide color photographic sensitive material

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): BE DE FR GB NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): BE DE FR GB NL

17P Request for examination filed

Effective date: 19970114

17Q First examination report despatched

Effective date: 19970526

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE FR GB NL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990303

Ref country code: FR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990303

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990303

REF Corresponds to:

Ref document number: 69601585

Country of ref document: DE

Date of ref document: 19990408

EN Fr: translation not filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20100322

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20100303

Year of fee payment: 15

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20110329

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111001

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69601585

Country of ref document: DE

Effective date: 20111001

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110329