EP0853256A2 - Solution stabilisante pour la traitement d'un produit photographique couleur à l'halogénure d'argent et procédé de traitement l'utilisant - Google Patents

Solution stabilisante pour la traitement d'un produit photographique couleur à l'halogénure d'argent et procédé de traitement l'utilisant Download PDF

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Publication number
EP0853256A2
EP0853256A2 EP98300119A EP98300119A EP0853256A2 EP 0853256 A2 EP0853256 A2 EP 0853256A2 EP 98300119 A EP98300119 A EP 98300119A EP 98300119 A EP98300119 A EP 98300119A EP 0853256 A2 EP0853256 A2 EP 0853256A2
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Prior art keywords
group
stabilizing
sensitive material
stabilizing solution
solution
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EP98300119A
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German (de)
English (en)
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EP0853256A3 (fr
Inventor
Atsuro Yanata
Manabu Nakahanada
Hiroaki Kobayashi
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Konica Minolta Inc
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Konica Minolta Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3046—Processing baths not provided for elsewhere, e.g. final or intermediate washings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • G03C2007/3025—Silver content
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C2200/00—Details
    • G03C2200/10—Advanced photographic system
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C2200/00—Details
    • G03C2200/33—Heterocyclic
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C2200/00—Details
    • G03C2200/40—Mercapto compound

Definitions

  • the present invention relates to a stabilizing solution for processing a silver halide color photographic light-sensitive material and a method for processing a silver halide color photographic light-sensitive material using the above-mentioned stabilizing solution.
  • the ratio of high speed light-sensitive material in the light-sensitive material to be processed is incresed, simple decrease of the amount of replenishing of stabilizing solution causes increase of amount of the sensitizing dye dissolved from the light-sensitive material accumulated in the stabilizing solution.
  • the sensitizing dye accumulated in the stabilizing solution causes re-dyeing the light-sensitive material and inhibits dissolving out the sensitizing dye from the light-sensitive material so as to remain the dye in the light-sensitive material.
  • the remained sensitizing dye causes a stain, so-called remained-color stain, which raises problems of color patches or divergence of color balance in the print.
  • components of the fixing solution arranged just before the sensitizing bath such as thiosulfate, silver ion and a halogen ion such as iodide ion, stuck on the light-sensitive material are brought and largely accumulated in the stabilizing solution.
  • These components accumulated in the stabilizing solution inhibit dissolution of sensitizing dye, give bad influence on the processing ability of the stabilizing solution by forming precipitation therein, and form the stain on the light-sensitive material.
  • such the components accumulated in the stabilizing solution cause lowering the stability of the image during a prolonged storage.
  • JP O.P.I. Japanese Patent Publication Open to Public Inspection
  • JP O.P.I. Japanese Patent Publication Open to Public Inspection
  • these publications describe nothing relating to addition of the heterocyclic compound to a stabilizing solution and improving the remained-color stain. Accordingly, the problems to be solved by the present invention cannot be sufficiently solved by such the technique described in these publications.
  • JP O.P.I. Nos. 64-15734, 1-230043 and 2-103037 describe nothing relating to the improvement of the storage ability of dye image.
  • various conditions such as the kind of sensitizing dye and the procssing conditions, in the black-and-white light-sensitive material are consideraably different from those in the color light-sensitive material. Accordingly, sufficient effcts cannot be obtained if the technique described in these publications is applied to the color light-sensitive materail, particularly under a recent processing in which the replenishing amount of processing solution is reduced.
  • the object of the invention is to provide a stabilizing solution for processing a silver halide color photographic light-sensitive material and a method for processing a silver halide color photographic light-sensitive material using the stabilizing solution, by which a decrease of the amount of waste liquids and a rapid processing can be realized without causing the remained-color stain and formation of precipitation in the stabilizing solution even when the high speed light-sensitive material is processed in a high ratio.
  • a stabilizing solution for processing a silver halide color photographic light-sensitive material which contains a composition represented by the following Formula 1; in the formula, Q 1 represents a group of atoms necessary to form a nitrogen-containing heterocyclic ring (5- or 6-member ring including one condensed with an unsaturated ring), R 1 represents a hydrogen atom, an alkali metal atom, a group or an alkyl group, Q' is a synonym with Q 1 .
  • Fig. 1 shows a position on an automatic processor, at which a solid processing composition suplying device.
  • Fig. 2 shows a constitution of an example of a solid processing composition supplying device.
  • preferably usable compounds are (1-9), (1-10), (1-13), (1-31) and (1-32), particularly preferably (1-32), from the view point of the object of the invention.
  • Dissolution of sensitizing dye remained in the light-sensitive material is accelerated by the compound of Formula 1 contained in the stabilizing solution and the formation remained-color stain can be prevented even when the amount of sensitizing dye accumulated in the stabilizing solution is increased by reducing the replenishing amount of fixing solution, or the time for the stabilizing treatment is reduced.
  • insoluble substance which is usually composed of silver ions and the decomposition product of thiosulfate, can be inhibited by adding such the compound in the stabilizing solution since the compound tend to interact with silver ions.
  • the compound of Formula 1 is contained in the stabilizing solution in am amount of 0.01 to 1.0 g/l, more preferably 0.1 to 0.5 g/l.
  • the stabilizing solution according to the invention preferably contains no formaldehyde.
  • Formaldehyde is frequently contained in a stabilizing solution for preventing the formation of color stains during prolonged storage and improving the stability of discoloration of color image by blocking the reactive portion of the unreacted coupler remained in the processed light-sensitive material.
  • formaldehyde reacts with sulfite which is brought from the fixing bath together with thiosulfate, and tends to form precipitates or to accelerate sulfidation of the stabilizing solution.
  • a 1 through A 4 are each a hydrogen atom, an alkyl group, an alkenyl group or a pyridyl group, and l is 0 or 1.
  • an inorganic acid salt such as hydrochloric acid salt, sulfate and nitrate
  • an organic acid salt such as phenol salt
  • a double salt of a complex salt with a metal salt such as a metal salt
  • an aqueous salt and an intramolecular salt are cited.
  • the adding amount of the compound represented by Formula F-11 is preferably 0.1 to 20 g per liter of the stabilizing solution.
  • Z 4 is a group of atoms necessary for forming a hydrocarbon ring or a heterocyclic ring
  • X represents an aldehyde group, a in which R 41 and R 42 are each a lower alkyl group, and n is an integer of 1 to 4.
  • Z 4 is a group of atoms necessary to form a substituted or unsubstituted carbon ring or a substituted or unsubstituted heterocyclic ring, and the carbon ring and the heterocyclic ring each may be a single ring or condensed ring.
  • Z 4 is preferably an aromatic carbon ring having a substituent or a heterocyclic ring.
  • the substituent of Z 4 is preferably selected from the following groups; an aldehyde group, a hydroxyl group, an alkyl group such as methyl group, ethyl group, methoxyethyl group, benzyl group, carboxymethyl group and sulfopropyl group, an aralkyl group, an alkoxy group such as methoxy group, ethoxy group and methoxyethoxy group, a halogen atom, a nitro group, a sulfo group, a carboxyl group, an amino group such as N,N-dimethylamino group, N-ethylamino group and N-phenylamino group, a hydroxyalkyl group, an aryl group such as phenyl group and p-methoxyphenyl group, a cyano group, an aryloxy group such as phenoxy group and p-carboxyphenyl group, an acyloxy group, an acylamin
  • the carbon ring represented by Z 4 is preferably a benzene ring
  • the heterocyclic ring represented by Z 4 is preferably a 5- or 6-member heterocyclic ring
  • the 5-member ring includes a thiophene ring, a pyrrole ring, a furan ring, a thiazole ring, an imidazole ring, a pyrazole ring, a succinimide ring, a triazole ring, and tetrazole ring
  • the 6-member ring includes a pyridine ring, a pyrimidine ring, a triazine ring and a thiazine ring.
  • a naphthalene ring As the condensed ring, a naphthalene ring, a benzofuran ring, an indole ring, a thionaphthalene ring, a benzimidazole ring, a benzotriazole ring and a quinoline ring may be cited.
  • Exemplified compounds F-12-1 to F-12-52 are shown by inserting substituents at the positions 1 to 6 in the above-mentioned formula as shown in the following tables.
  • More preferable compounds are F-12-2, F-12-3, F-12-4, F-12-6, F-12-23, F-12-24, F-12-52, and the most preferable compound is F-12-3.
  • the compounds represented by F-12 are usually available on the market.
  • the adding amount of the compound represented by F-12 is preferably 0.05 to 20 g, more preferably 0.1 to 15 g, particularly preferably 0.5 to 10 g, per liter of the stabilizing solution.
  • At least one of Z 5 and Z 6 is a group of non-metal atoms necessary to form an aromatic ring or a ring, an isomeric chemical structure of which can be an aromatic ring, together with the nitrogen atom, X 2 and X 3 , or the nitrogen atom, X 4 and X 5 in Formula F-14.
  • Z 5 is a group of non-metal atoms necessary to form an aromatic ring or a ring, an isomeric structure of which can be an aromatic ring, together with the nitrogen atom, X 2 and X 3 in Formula F-14 and Z 6 is a group of non-metal atom necessary to form a non-aromatic ring together with the nitrogen atom, X 4 and X 5 .
  • the aromatic ring or the ring the isomeric structure of which can be an aromatic ring, a 5-member ring is preferable, and a pyrazole ring, a triazole ring such as a 1,2,4-triazole ring and a 1,2,3-triazole ring and an urazole ring are more preferable.
  • a non-aromatic ring formed by Z 6 a pyrrolidine ring, a piperidine ring, a morpholine ring and a piperazine ring are preferable.
  • the stabilizing solution according to the invention has a surface tension of 15 to 60 dyne/cm, more preferably 15 to 45 dyne/cm.
  • the surface tension is a value determined by an usual method described in, for example, H. Kitahara, S. Hayano & I. Hara, "Analysis and Test Method of Surfactant” March 1, 1082, Kodansha.
  • the surface tension is a value measured by by the usual method at 20° C.
  • the stabilizing solution contains a water-soluble surfactant.
  • a surfactant a compound represented by the following Formula SI, SII or SIII, or a water-soluble organic siloxane compound.is particularly preferred.
  • R 1 is a hydrogen atom, an aliphatic group or an acyl group
  • R 2 is a hydrogen atom or an aliphatic group
  • E 1 is an ethylene oxide group
  • E 2 is a propylene oxide group
  • E 3 is an ethylene oxide
  • X is an oxygen atom or a -R 3 N- group, in which R 3 is an aliphatic group
  • a hydrogen atom or an R 4 is a hydrogena tom or an aliphatic group
  • l 1 , l 2 , m 1 , m 2 , n 1 and n 2 are each 0 or an integer of 1 to 300.
  • a 1 is a mono-valent organic group, for example, an alkyl group having 4 to 50, preferably 4 to 35, carbon atoms such as a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group or a dodecyl group, which may be substituted by a fluorine atom, or an aryl group which is substituted by an alkyl group having 3 to 35 carbon atoms or an alkenyl group having 2 to 35 carbon atoms.
  • an alkyl group having 4 to 50 preferably 4 to 35, carbon atoms
  • carbon atoms such as a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group or a dodecyl group, which may be substituted by a fluorine atom, or an aryl
  • the preferable substituent of the aryl group includes the following group: an alkyl group having 1 to 18 carbon atoms, for example, an unsubstituted alkyl group such as a methyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group, a substituted alkyl group such as a benzyl group and a phenetyl group, an alkenyl group having 2 to 20 carbon atoms, for example, an unsubstituted alkenyl group such as an oleyl group, and an allyl group, and a substituted alkenyl group such as styryl group.
  • an alkyl group having 1 to 18 carbon atoms for example, an unsubstituted alkyl group
  • aryl group a phenyl group, a biphenyl group and a naphthyl group, preferably a phenyl group, are cited.
  • the position of the aryl group at which the substituent is bonded may be any of orto-, metha- and para-position and a plurailty of the substituent may be bonded.
  • B and C are each a group, and C is a group selected from an ethylene oxide group, a propylene oxide group and a oprovided that the group represented by B and the group represented by C is different from each other, n 1 , m 1 and l 1 are each 0, 1, 2 or 3, m and n are each an integer of 0 to 100, X 1 a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, for example, a group the same as that represented by A 2 .
  • the adding amount of the water-soluble surfactant is preferably 0.1 to 40 g, more preferably 0.3 to 20 g per liter of the stabilizing solution.
  • Formula SIII is described below.
  • Formula SIII Rf-(x) m -(Y) n -A
  • Rf is a saturated or unsaturated hydrocarbon group each having a fluorine atoms
  • X is a sulfonamido group
  • a Y is an alkylene oxide group or an alkylene group
  • Rf' is a saturated or unsaturated hydrocarbon group each having a fluorine atoms
  • A is a hydrophilic group such as an -SO 3 M group, an -OSO 3 M group, a -COOM group, an -OPO 3 (M 1 ) (M 2 ) group or a -PO 3 (M 1 ) (M 2 ) group
  • M, M 1 and M 2 are each a hydrogen atom, a lithium atom, a potassium atom, a sodium atom or an ammonium group
  • m is 0 or 1
  • n is 0 or an integer of 1 to 10.
  • Rf is a saturated or unsaturated hydrocarbon group such as an alkyl group, an alkenyl group or an alkinyl group each ahving a fluorine atom, and is preferably an alkyl group having 4 to 12 carbon atoms, more preferably 6 to 9 carbon atoms, which has a fluorine atom.
  • A is preferably an -SO 3 M group, M, M 1 and M 2 are preferably a lithium atom, a potassium atom or a sodium atom, more preferably a lithium atom.
  • m is 0 or 1
  • n is 0 or an integer of 1 to 10, and preferably both of m and n are 0.
  • SIII-1, SIII-2 and SIII-3 are particularly preferred among the above examples.
  • a compound represented by the following Formula SU-I is preferable as the water-soluble organic siloxane compound.
  • R 9 is a hydrogen atom, a hydroxyl group, a lower alkyl group, an alkoxy group, an or an R 10 , R 11 and R 12 are each a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, the groups each represented by R 10 , R 11 and R 12 may be the same or different.
  • l 1 , l 2 and l 3 are each 0 or an integer of 1 to 30 and p, q 1 and q 2 are each 0 or an integer of 1 to 30.
  • X 1 and X 2 are each a -CH 2 CH 2 - group, a -CH 2 CH 2 CH 2 -group, a or a
  • the adding amount of the water-soluble organic siloxane compound having a polysiloxane group is preferable 0.01 to 20 g per liter of the stabilizing solution.
  • the water-soluble organic siloxane compound includes usual organic compounds such as ones described in, for example, JP O.P.I. Nos. 47-19333 and 49-62128, Japanese Patent Nos. 55-51172 and 51-37538, and U.S. Patent 3,545,970.
  • Components usually used in a stabilizing solution for example, a chelating agent such as ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid and 1-hydroxyethylidene-l,l-disulfonic acid, a buffering agnet such as potassium carbonate, a borate, an acetate and a phosphate, an anti-mold agent such as Diacide 702(trade name), p-chloro-m-cresole and benzo-iso-thiazoline-3-one, a fluorescent whitening agent such as a triazinylstylbene compound, an antioxidant such as a sulfite and an ascorbic acid, and a metal salt such as a zinc salt and a magnesium salt, may be optionally added in the stabilizing solution according to the invention.
  • a chelating agent such as ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid and 1-hydroxyethylidene-l,l-
  • the effect of the invention is enhanced when the processing is carried out by applying a reduced replenishing amount of the stabilizing solution, the replenishing amount is preferably not more than 1200 ml, more preferably 100 to 900 ml, further preferably 200 to 650 ml, per 1 m 2 of the light-sensitive material to be processed.
  • the number of the stabilizing tank may be one, the number of the tank may be increased by 2 to 10.
  • the number of the stabilizing tank is preferably 2 to 6 from the viewpoint of compactness of the processor.
  • the replenishing solution may be supplied to the stabilizing tank separately from several portions, it is preferred that the replenishing solution is supplied by a method so-called counter-current method.
  • the replenishing solution is supplied to the tank arranged at a lower course of the conveying direction of light-sensitive material and the overflow from the tank is introduced into the tank arranged before the tank to which the replenishing solution is supplied.
  • This method includes a case in which these tanks are connected by a pipe and the overflow is flow through the pipe.
  • a cascade-flow method is also included in this method. It is further preferred that two or more tanks are provided and the replenishing solution is supplied to the tank arranged at the last step and the overflow is successively flowed to the tank arranged at the upper course.
  • the processing solution take out from the stabilizing tank is introduced into a fixing solution in the fixing process or a bleach-fixing solution in the bleach-fixing process which are the processes positioned just before the stabilizing process.
  • a fixing solution in the fixing process or a bleach-fixing solution in the bleach-fixing process which are the processes positioned just before the stabilizing process.
  • the temperature and time of the stabilizing treatment are preferably 10 to 50° C and 10 to 80 seconds, more preferably 20° C and 70 seconds, further preferably 20 to 40° C and 15 to 70 seconds, respectively.
  • the pH value of the stabilizing solution is preferable 3 to 10. more preferably 6 to 9.
  • the treating process to which the present invention is applied includes the followings;
  • a solid processing composition in a form of powder, granule or tablet is used for replenishing the processing solution.
  • the granuled processing composition and tableted processing composition are more preferable and the tableted composition is most preferable.
  • the powder is a mass of fine crystals
  • the granule is a grain-shape matter having a diameter of 50 to 5000 ⁇ m, which is preferably prepared by granulation of the powder.
  • the tablet is a product prepared by compressing the powder or the granule to a certain form. It is preferable that the tablet is prepared by the method by which powder or granules are granuled and then the granuled matter is tableted since the processing ability of the composition can be stably maintained.
  • the average diameter of the granuled matter is preferably 100 to 2,000 ⁇ m. more preferably 200 to 1,500 ⁇ m, for tableting since unevenness of the composition, so-called segregation, is hardly occurred at the time of compressing the granuled matter. It is preferable that the sizes of the grains accounting for 50 % of the whale granules are within a deviation range of ⁇ 200 to 250 ⁇ m.
  • granuled matter may be directly used as the granuled processing composition.
  • a known compressing machine such as an oil-pressure compressing machine, a single tableting machine, a rotary tableting machine or a briquetting machine can be used for compressing the granuled matter. It is allowed that the granuled matter prepared by the above-mentioned method and a crystalline material available on the market are mixed and tableted.
  • the solid processing composition prepared by compressing may be formed in any shape, the cylindrical shape, so-called tablet, is preferred from the viewpoint of the production efficiency, handling facility and formation of powder dust in the practical use.
  • Silver halide used in the silver halide photographic light-sensitive material to be processed may be any one such as silver chloride, silver chlorobromide, silver bromide, silver iodobromide and silver iodide as far as the silver halide is spectrally sensitized by a sensitizing dye.
  • the effect of the invention is enhanced in the processing of a light-sensitive material for photographing by a camera which includes a silver halide having relatively high silver iodide content such as 5 mol-% or more, and has a coating amount of silver is 3 to 20 g/m 2 , preferably 6 to 20 g/m 2 .
  • the silver halide emulsion can be prepared according to the methods described in, for example, Research Disclosure, hereinafter referred to RD, No. 17643, p.p. 22-23, I. Emulsion preparation and types, December 1978, RD No. 18716, p. 648, P. Glafkides, Chimie et Phisique Photographique, Paul Montel, 1967, G. F. Duffin, Photographic Emulsion Chemistry, Focal Press, 1966, V. L. Zelikman et al. Making and Coating Photographic Emulsion, Focal Press, 1964. Monodisperse emulsions described in U. S. Patent Nos. 3,574,628 and 3,665,394, and British Patent No. 1,413,748 are also preferred. Although the average grain diameter is without any limitation, 0.1 to 5 ⁇ m is preferable. Two or more kinds of separately prepared emulsions may be mixed for used.
  • Various kinds of photographic additives may be used to the emulsion in the course of physical ripening or chemical ripening process.
  • Various compounds described in RD Nos. 17643, 18716 and 308119 can be used as the additives.
  • a compound described in U. S. Patent Nos. 4,411,987 and 4,435,503, which is capable of reacting with formaldehyde and fixing it, is preferably added to the light-sensitive material to prevent degradation of the photographic properties caused by formaldehyde gas.
  • Various kinds of coupler can be used, concrete examples thereof are described in RD Nos. 17643 and 308119.
  • the additives can be added by the dispersing method described in RD No. 308119, XIV.
  • the present invention is preferably used when the silver halide photographic light-sensitive material to be processed has a magnetic layer containing ferromagnetic particles.
  • the magnetic layer may be provided at any portion in the light-sensitive material, for example, the magnetic layer may be not adjoined to the support.
  • the magnetic layer may be arranged on the emulsion side or the opposite side of the support.
  • ferromagnetic particles ferromagnetic iron oxide such as ⁇ -Fe 2 O 3 (FeO x , 4/3 ⁇ x ⁇ 3/2), Cobalt-adhered ferromagnetic iron oxide such as Co-adhered ⁇ -Fe 2 O 3 (FeO x , 4/3 ⁇ x ⁇ 3/2), Co-adhered magnetite, another Cobalt-containing ferromagnetic iron oxide, Co-containing magnetite, ferromagnetic chromium dioxide, a ferromagnetic metal, a ferromagnetic alloy, another ferrite such as hexagonal Baferrite, Sr-ferrite, Pb-ferrite, Ca-ferrite, a solid solution of them or a ion substituted substance
  • the preparation method of these ferromagnetic particles has be known, and the ferromagnetic particle usable in the light-sensitive material of the invention can be also prepared by the known method.
  • the shape of the ferromagnetic particle may be any of a needle-like, rice grain-like, spherical, cubic and tabular, the needle-like particle is preferable from the viewpoint of electromagnetic conversion property.
  • the particle size in the major axis length of 0.01 to 0.8 ⁇ m and the ratio of major axis/minor axis is 2 to 100, are preferable, and the major axis length of 0.05 to 0.3 ⁇ m and the major axis/minor axis ratio of 4 to 15 are more preferable.
  • the specific surface area S BET of the ferromagnetic particles is preferably not less than 20 m 2 /g, more preferably 30 m 2 /g.
  • a larger saturation magnetization ( ⁇ s) value is preferred, and a saturate magnetization of not less that 50 emu/g is preferable and that not less than 70 emu/g is more preferable, the value is practically not more than 100 emu.
  • the square ratio ( ⁇ r/ ⁇ s) of the ferromagnetic substance is preferably not less than 40%, more preferably not less than 45%.
  • a proper coercive force (Hc) is preferred. When the coercive force is too small, recorded signals is too easily erased and when the coercive force is too large, signals are hardly written.
  • the coercive force is usually 200 to 3,000 Oe, preferably 500 to 2,000, more preferably 650 to 950 Oe.
  • Konica Color Negative Film LV400 manufactured by Konica Corporation, was imagewise exposed by a camera and processed by a color negative film processor CL-KP-50QA using processing solutions and replenishing solutions prepared by the following receipts. The processing was run for 8 weeks. In the course of the running of the processing, 60 roles of 135-24 size film were processed per day. (Processing steps) Time Temperature Replenishing amount Color developing 3min. 15 sec. 38° C 520 ml/m 2 Bleaching 45 sec. 38° C 100 ml/m 2 Fixing-1 45 sec. 38° C Fixing-2 45 sec. 38° C 510 ml/m 2 Stabilizing-1 20 sec. 38° C Stabilizing-2 20 sec. 38° C Stabilizing-3 20 sec. 38° C 860 ml/m 2 Drying 80 sec. 55° C
  • D min (R) the red density of the processed specimen
  • D' min (R) The red density of the washed specimen
  • D' min (R) was measured after drying. Degree of the remained-color stain ⁇ D min (R) was defined by the different of D min (R) and D' min (R) .
  • the degree of the remained-color stain of 0.05 or less is a level of the stain acceptable for practical use, and a value nearer to 0 is preferred.
  • a specimen of the light-sensitive material exposed through an optical wedge was processed.
  • the transparent density at 440 nm of the maximum density portion of the processed specimen was measured.
  • the specimen was stood in a lighted room for 10 days inder conditions of a temperature of 40° C, a relative humidity of 30% and a lightness of 70,000 Lux/h. After standing, the specimen was subjected to densitometry and a ratio of the difference of the density caused by the standing, a discoloration ratio of yellow color, was determined.
  • Example 2 The processing was run in the same manneras in Example 1 using the above-mentioned stabilizing solution. An unexposed specimen of the light-sensitive material was processed and the stain on the back surface of the specimen was observed and ranked as follows.
  • the condition of the stain on the back surface of the specimen is particularly excellent when the surface tension of the stabilizing solution is 60 dyne/cm or less, and the appearance of the first stabilizing tank is particularly maintained clear when the surface tension is 45 dyne/cm or less. Accordingly, such the condition is particularly preferred as the embodiment of the invention.
  • formalin is an about 37% aqueous solution of formaldehyde.
  • the stain on the back surface of the light-sensitive material and the appearance of the second stabilizing tank were observed after running of the processing. Furthermore, the red color density of the unexposed portion of the processed light-sensitive material was measured and the degree of remained color was calculated.
  • the stain on the back surface was eavaluated in the same manner as in Example 2 and the appearance in the second stabilizing thank was ranked accoeding to the followings.
  • the stain decreasing effect of the compound of the invention is enhanced and the back surface stain and the appearance in the second stabilizing tank are also improved when the stabilizing solution contains no formaldehyde which is usually used in an ordinary stabilizing solution.
  • Color negative film processor CL-KP-50QA manufactured by Konica Corporation
  • the replenishment was carried out by the use of a solid processing composition supplying device shown in Fig. 2.
  • a pillar-shaped container including tablets was set on the solid processing composition supplying device, and imagewise exposed Konica Color LV400 Film, manufactured by Konica Corporation, was processed in a rate of 60 rolls per day. The processing was run for 8 weeks.
  • Fig. 1 shows the constitution of KP-50QA (hereinafter referred to automatic processor), in which 1A is a developing tank and 1B is a bleaching tank, 1C 1 to 1C 2 were each a first and second fixing tank, and 1D 1 to 1D 3 are each first, second and third stabilizing tank, respectively, and F is a drying zone.
  • Solid processing composition supplying devices 2A, 2B, 2C and 2D, each shown by hatching, were each attached the upper portion of color developing tank 1A, bleaching tank 1B, second fixing tank 1C 2 and third stabilizing tank 1D 3 , respectively.
  • the fixing process-1 and -2 were carried out in the fixing tanks C 1 and C 2
  • the stabilizing process-1, -2 and -3 were carried out in the stabilizing tanks 1D 1 , 1D 2 , and 1D 3 , respectively.
  • FIG. 2 shows the constitution of the solid processing composition supplying device.
  • a dissolving chamber 106 in which a solid processing composition 111 is supplied, is provided at a side of each of the processing tanks.
  • the solid processing composition (a tablet in the drawing) 111 is packed in a container (cartridge) 101 and sealed by a slidable cap 102.
  • the slidable cap 102 is open and the tablet is rolled down into a pocket 105 of the rotating cylinder 104.
  • a plurarity of pocket 105 was made on the rotating cylinder 104 at staggered positions so that two or more tablets contained in the container was hardly rolled down in the same time.
  • the fixing process and the stabilizing process were each carried out by counter flow systems in the order of fixing-2 ⁇ fixing-1 and stabilizing-3 ⁇ stabilizing 2 ⁇ stabilizing-1, respectively.
  • 10 ml, 6.5 ml, 7 ml, 7 ml, 8.6 ml, 8.6 ml and 9.3 ml per hour of water was replenished to each the tank of color developing, bleaching, fixing-1, fixing-2, stabilizing-1, stabilizing-2 and stabilizng-3, respectively, while the temperature was controlled.
  • 7.5 ml, 5 ml, 6 ml, 6 ml, 5 ml, 5 ml and 5 ml per hour of water was replenished to each the tank of color developing, bleaching, fixing-1, fixing-2, stabilizing-1, stabilizing-2 and stabilizng-3 at the time of restart the processing based on the integration of the rest time.
  • the tank solutions at the start of running of the processing were prepared by using the starter and the replenisher of Processing composition CNK-4-52 for Konica Color Negative Film, manufactured by Konica Corporation.
  • the above-mentioned granules 1 to 3 were mixed, and 2 g of sodium N-myristoylalanine was added to the mixture.
  • the mixture was uniformly mixed by a mixer installed in a room conditioned at a temperature of 25° C and a relative humidity of not more than 40%.
  • the mixture was tableted by a tableting machine, modified Tough Press Collect 1527HU, manufactured by Kikusui Seisakusho Co., Ltd., in a rate of 10 g per tablet to prepare a color developer replenisher tablet for color negative film having a diameter of 30 mm and a thickness of 10 mm.
  • the granules prepared by procedures 4 to 6 were uniformly mixed for 10 minutes by a mixer installed in a room conditioned at a temperature of 25° C and a relative humidity of not more than 40%.
  • the mixture was tableted by a tableting machine, modified Tough Press Collect 1527HU in a rate of 10 g per tablet to prepare a bleaching solution replenisher tablet for color negative film having a diameter of 30 mm and a thickness of 10 mm.
  • the granules prepared by the above-mentioned procedure were tableted by a tableting machine, modified Tough Press Collect 1527HU in a rate of 10 g per tablet to prepare a stabilizing solution replenisher tablet for color negative film having a diameter of 30 mm and a thickness of 10 mm.
  • a processing was run in the same manner as in Example 1 except that 255 ml/m 2 of the light-sensitive material of the stabilizing solution was introduced to the fixing tank from the stabilizing tank nearest the fixing tank among the tree stabilizing tanks and a stabilizing solution having a concentration 2 times of that of the replenishing solution used in Example 1 is replenished to the second stabilizing tank in a rate of 255 ml/m 2 of the light-sensitive material.
  • a stabilizing solution having a concentration 2 times of that of the replenishing solution used in Example 1 is replenished to the second stabilizing tank in a rate of 255 ml/m 2 of the light-sensitive material.
  • the fixing solution in the second fixing tank was stored for 1 week at 50° C in a container having a ratio of area opened to air to volume of the solution of 10 cm 2 /l, and the storage stability of the stabilizing solution was evaluated according to the following norm.
  • the polymer was dried in a vacuum for 8 hours at 150° C, and molten and extruded from a T-die in a form of layer.
  • the extruded layer of the polymer was contacted on a cooling drum of 50° C while applying a electrostatic field to solidify to obtain a non-expanded sheet.
  • the non-expanded sheet was longitudinally expanded 3.3 times at 135° C by a roller type expanding machine.
  • uniaxis-expanded film was laterally expanded by a tenter type lateral expanding machine by 50% of the total lateral expanding ratio at 45 ° C in the first expanding zone, and further expanded in the second expanding zone so that the total expanding ration was 3.3 times.
  • the sheet was heated for 2 seconds at 100° C, and thermally fixed at 200° C for 5 seconds in the first thermal fixing zone and at 240° C for 15 seconds in the second thermal fixing zone. Then the sheets was gradually cooled to a room temperature spending 30 seconds while slacking laterally by 5 % to obtain a polyethylene naphthalate film having a thickness of 85 ⁇ m.
  • the film was wound on a core made by stainless steel and annealed at 110° C for 48 hours. Thus a support was prepared.
  • a corona discharge treatment of 12W/m 2 /min. was applied on the both sided of the support.
  • the following subbing liquid B-1 was coated so that the dried layer thickness of it was 0.2 ⁇ m, and a corona discharge treatment of 12W/m 2 /min. was applied on it.
  • the following subbing liquid B-2 was coated on this surface so that the dried layer thickness was 0.2 ⁇ m.
  • subbing liquid B-3 On the other surface of the support, which had been treated by corona discharge of 12W/m 2 /min., the following subbing liquid B-3 was coated and corona discharge of 12W/m 2 /min. was further applied. Then the following subbing liquid B-4 was coated on this surface.
  • a magnetic recording layer having the following composition was coated by a precision ⁇ m, and the magnetic particles in the coated layer were oriented along the coating direction in an orientation magnetic field before drying the coated layer for raising the output level of playback signal of the magnetic record.
  • a lubricant coating liquid or the later-mentioned wax liquid was prepared by dispersing carnauba wax in a water/methanol mixture solvent so that the solution contained 0.15 of carnauba wax.
  • the lubricant liquid was coated on the above-mentioned magnetic recording layer so that the coated amount of the wax was 15 mg/m 2 .
  • the bulk support coated with the wax was dried for 5 minutes at 100° C by passing through a thermal treatment zone, and stored in an oven for 5 days at 40° C so that the cross-linking reaction of isocyanate was sufficiently progressed.
  • a subbing layer was provided by coating the following subbing liquids B-1 and B-2 under the same condition.
  • Photographic constituting layers having the following compositions were provided to prepare Sample 101. The adding amounts are described in grams per square meter, provided that the amounts of silver halide emulsion and that of colloidal silver are described in terms of silver and the amount of sensitizing dye, referred to SD, is described in terms of moles per mole of silver.
  • the light-sensitive material prepared as above was processed by using the stabilizing solution and the replenishing solution for stabilizing solution the same as in Example 5.
  • the processing was run in the same manner as in Experiment No. 1-1 or 1-6.
  • the remained-color stain was evaluated in the same manner as in Example 1 and the magnetic record of the magnetic recording layer of the processed light-sensitive material was evaluated according to the following norms.
  • the square wave signal recorded on the processed light-sensitive material was read by a reading head at an uniform conveying speed and a point at which the output was lowered by 3 dB was defined as the head clogging point.
  • the level of head clog was evaluated according to the length in meter of the light-sensitive material for the starting point to the head cloggin point. A lower value, namely the head was clogged after passing a shorter length, means an undesirable property.
  • the test was carried out in the same manner as in the evaluation of the clogging of the magnetic head, and the samples by each of which the lowering of the playback signal level from the initial level was less than 0.5 dB, not less than 0.5 dB and less than 1 dB, and 1 dB or more were classified as A, B and C, respectively.
  • Samples of light-sensitive material were prepared in the same manner in Example 9 except that the coating amount of silver of 6.85 g/m 2 was changed as to be the amount shown in Table 13 by changing the amount of silver halide in each of the emulsion layers in the same proportion. The amount of each of the sensitizing dyes was also changed in proportion of the amount of silver.
  • the samples were each subjected to experiment the same as in example 9 for evaluating the remained-color stain in the samples. Results are shown in table 13. Experiment No.
  • the N-containing heterocyclic ring completed by Q 1 may be a 5- to 10- membered, preferably 5- or 6-membered, heterocyclic ring optionally containing one or more further heteroatoms chosen from e.g. O, N or S.
  • the heterocyclic ring may be optionally substituted.
  • the alkali metal atom represented by R 1 may be a sodium, potassium or caesium atom.
  • the alkyl group represented by R 1 may be substituted and is preferably C 1-6 , more preferably C 1-4 .
  • alkyl or alkenyl groups represented by A 1 to A 4 may be optionally substituted, and are preferably C 1-6 , more preferably C 1-4 .
  • the substituents R 60-64 are preferably those which may be included on ring Z 4 .

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  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP98300119A 1997-01-10 1998-01-08 Solution stabilisante pour la traitement d'un produit photographique couleur à l'halogénure d'argent et procédé de traitement l'utilisant Withdrawn EP0853256A3 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0961166A3 (fr) * 1998-05-01 2000-04-12 Konica Corporation Méthode de traitement d'un matériau photographique transparent à l'halogénure d'argent sensible à la lumiére et produit obtenu par cette méthode

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63306446A (ja) * 1987-06-08 1988-12-14 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
EP0474461A1 (fr) * 1990-09-05 1992-03-11 Konica Corporation Procédé de traitement de matériau photographique couleur à l'halogénure d'argent sensible à la lumière
JP2904948B2 (ja) * 1991-03-28 1999-06-14 コニカ株式会社 ハロゲン化銀カラー写真感光材料の処理方法及び安定液
JP2729545B2 (ja) * 1991-06-05 1998-03-18 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料用の処理液及びそれを用いた処理方法
DE69601585T2 (de) * 1995-03-30 1999-07-01 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Verfahren zur Verarbeitung eines farbphotographischen Silberhalogenidmaterials

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0961166A3 (fr) * 1998-05-01 2000-04-12 Konica Corporation Méthode de traitement d'un matériau photographique transparent à l'halogénure d'argent sensible à la lumiére et produit obtenu par cette méthode

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