EP0465228B1 - Méthode de traitement pour matériau photographique couleur à halogénure d'argent - Google Patents

Méthode de traitement pour matériau photographique couleur à halogénure d'argent Download PDF

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Publication number
EP0465228B1
EP0465228B1 EP19910306008 EP91306008A EP0465228B1 EP 0465228 B1 EP0465228 B1 EP 0465228B1 EP 19910306008 EP19910306008 EP 19910306008 EP 91306008 A EP91306008 A EP 91306008A EP 0465228 B1 EP0465228 B1 EP 0465228B1
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Prior art keywords
mol
ammonium
stabilizer
group
silver
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EP0465228A3 (en
EP0465228A2 (fr
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Yutaka Ueda
Shigeharu Kobosi
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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
    • G03C7/44—Regeneration; Replenishers

Definitions

  • the present invention relates to a silver halide color photographic light-sensitive material processing method, more specifically to a silver halide color photographic light-sensitive material processing method which offers improvements in the prevention of residual dye stain and crystal deposition onto the processing tanks and rollers and which permits rapid processing and reduction in the amount of replenisher.
  • a light-sensitive material For obtaining a color image by processing an imagewise-exposed silver halide color photographic light-sensitive material (hereinafter simply referred to as a light-sensitive material), it is a common practice to remove the metallic silver formed after the color developing process and subsequently process the light-sensitive material by washing, stabilization, stabilizing treatment without water washing and other processes.
  • the light-sensitive material is sent to a processing laboratory where it is processed in 24 to 48 hours from reception to finish.
  • mini-labo the in-house processing equipment
  • the methods classified under (1) above include:
  • the methods classified under (2) above include methods of stirring a processing solution, such as the method described in Japanese Patent O. P. I. Publication No. 180369/1987.
  • the methods classified under (3) above include:
  • Figure 1 is a cross-sectional view of a mode of the automatic developing machine used for the present invention.
  • Figure 2 is a plane view of the automatic developing machine.
  • the numerical symbols 1 through 16 respectively denote the following: 1...main body of the developing machine, 2...negative light-sensitive material, 3...positive light-sensitive material, 4...supply portion, 5...take-out portion, 6...developer tank, 7...bleacher tank, 8...fixer tank, 9, 10 and 11...stabilizer tank, and 13,14, 15 and 16...cascade piping.
  • a silver halide color photographic light-sensitive material processing method wherein a silver halide color photographic light-sensitive material comprising a support and a silver halide emulsion having an average silver chloride content of not less than 80 mol% coated thereon is subjected to imagewise exposure, after which it is subjected to color development and subsequent bleaching, fixation and stabilization and wherein a water-soluble surfactant is added to the stabilizer so that the surface tension of the stabilizer is 15 to 60 dyne/cm and ion exchange resin or adsorbent is brought into contact with the light-sensitive material in the stabilizing bath.
  • the water-soluble surfactant is represented by the following formula I or II.
  • a silver halide color photographic light-sensitive material comprising a support and a silver halide emulsion having an average silver iodide content of not less than 2 mol% coated thereon and another silver halide color photographic light-sensitive material comprising a support and a silver halide emulsion having an average silver chloride content of not less than 80 mol% coated thereon are subjected to mixed processing using at least one same replenisher in a processing bath other than the color developing bath and wherein a part or all of the overflow is allowed to enter in the stabilizing bath to process the former silver halide color photographic light-sensitive material therein.
  • R represents a hydrogen atom or a linear or branched alkyl group having a carbon number of 4 to 25 which may have a substituent or (R 1 and R 2 independently represent a hydrogen atom or an alkyl group having a carbon number of 1 to 20 which may have a substituent; l represents an integer of 0 to 4) or a hydrogen atom; n and m independently represent an integer of 0 to 200, but they are not 0 concurrently; A and B, whether identical or not, independently represent
  • n 1 , m 1 and l 1 independently represent 0, 1, 2 or 3, but n 1 , m 1 and l 1 are not 0 concurrently;
  • D represents a hydrogen atom or -SO 3 M or -PO 3 M group, wherein M represents a hydrogen atom, alkali metal or ammonium.
  • R 3 represents a hydrogen atom, hydroxyl group, lower alkyl group, alkoxy group or or R 4 , R 5 and R 6 , whether identical or not, independently represent a lower alkyl group, with preference given to an alkyl group having a carbon number of 1 to 3, such as a methyl, ethyl or propyl group; l 1 through l 3 independently represent an integer of 0 to 4; p, q 1 and q 2 independently represent an integer of 1 to 15.
  • the present invention thus aims at promoting the elution of weakly hydrophilic sensitizing dyes by adding a water-soluble surfactant to the stabilizing bath, in which dying is likely to occur, and at preventing the dying-back of the pigments and dyes accumulated in the stabilizer to the light-sensitive material and their crystal deposition onto the processing tank wall and rollers by removing the pigments and dyes by adding ion exchange resin or adsorbent to the stabilizing bath.
  • the ion exchange resin or adsorbent used for the present invention is commercially available under various trade names such as Diaion (produced by Mitsubishi Chemical Industries Ltd.), Amberlite (produced by Japan Organo Co., Ltd.), Duolite, Sumikaion and Sumichelate (all produced by Sumitomo Chemical Co., Ltd.) and * Uniselek * (produced by Unitika Ltd.).
  • Anion exchange resin is particularly preferred for the enhancement of the effect of the invention, and its chemical structure is exemplified as follows: Commercial products: Mitsubishi Diaion SA-10A, SA-11A, PA-308 Commercial products: Mitsubishi Diaion SA-20A, SA-21A, PA-408 wherein R represents a hydrogen atom, N(R') 2 or lower alkyl group (R' represents a hydrogen atom or lower alkyl group, but the two R' members do not represent a hydrogen atom concurrently); n represents an integer of 0 to 3.
  • Adsorbents In the present invention, the following adsorbents can also be used.
  • Adsorbents In the present invention, the following adsorbents can also be used.
  • the activated charcoal (a) may be any activated charcoal, as long as it is adsorptive.
  • the activated charcoal may be made from any of wood, sawdust, coconut shell, lignin, bovine bone, blood, lignite, brown coal, peat and coal. Morphologically two types are available, namely powdery and granular, both of which can be used for the present invention.
  • powdered activated charcoal the raw material is pulverized and then carbonated at high temperature for activation. In some cases, activation is carried out by steam sparging at high temperature or by burning carbonization after immersion in a solution such as of zinc chloride, phosphoric acid, sulfuric acid or alkali.
  • charcoal is partially oxidized by ignition under reduced pressure or by heating in air, carbon dioxide or gaseous chlorine. Activation is normally followed by washing to remove the ash and chemicals, pulverization and drying to yield powdered activated charcoal.
  • Granular activated charcoal is obtained by forming pulverized charcoal powder to a given granularity in the presence of a caking agent such as tar or pitch, drying and burning. When coconut shell or coal is used, it is pulverized and sieved, after which it is carbonized at high temperature for activation to yield granular activated charcoal.
  • any form of activated charcoal can be used, whether it is powdery or granular, but preference is given to granular activated charcoal. More preference is given to coconut shell activated charcoal and activated charcoal capable of molecular sieving.
  • the activated charcoal capable of molecular sieving is defined to have slit-like pores, whose size is desirably not less than 6 Angstrom in diameter and not more than 15 Angstrom in width.
  • Such activated charcoal capable of molecular sieving can be prepared in accordance with Japanese Patent O. P. I. Publication No. 14831/1983 of the present applicant.
  • the clay substance (b) is an inorganic substance containing silica and alumina as the essential components and, as necessary, other components, including silica gel, bentonite, activated clay, acid clay, kaolin and substances in the zeolite group such as zeolite.
  • Bentonite is a clay acid based on hydrated aluminum silicate, derived mainly from montmorillonite ore.
  • Activated clay is a clay substance derived mainly from montmorillonite or halloysite ore.
  • Acid clay is a similar clay substance.
  • Kaolin is a clay substance comprising naturally-occurring hydrated aluminum silicate.
  • Substances in the zeolite group such as zeolite are clay substances which comprise naturally-occurring or synthetic zeolite, which have uniform pore size and which act as a molecular sieve.
  • non-zeolite substances in the zeolite group include natrolite and chabazite.
  • the polyamide polymer compound (c) is a polymer having an acid amide bond, such as 6-nylon, 6,6-nylon or 6,10-nylon.
  • the polyurethane polymer compound (d) is a polymer compound having the urethane linkage -NHCOO- in the repeat unit of the principal chain.
  • the phenol resin (e) includes resins prepared from a phenolic substance such as phenol, cresol, xylenol or resorcinol and an aldehyde such as formaldehyde, acetaldehyde or furfural, and modified resins thereof, with preference given to phenol-formaldehyde resin.
  • phenolic substance such as phenol, cresol, xylenol or resorcinol
  • an aldehyde such as formaldehyde, acetaldehyde or furfural
  • modified resins thereof with preference given to phenol-formaldehyde resin.
  • Examples of commercial products include Duolite S-761 resin, produced by Sumitomo Chemical Co., Ltd.
  • the polymer compound (g) having a hydrazide group include adducts of sulfohydrazide group, carbonylhydrazide group or hydrazide group with methyl acrylate-divinylbenzene copolymer, styrene-divinylbenzene copolymer or the like.
  • the polytetrafluoroethylene-containing polymer compound (h) is a mixture of polytetrafluoroethylene and polyethylene, polypropylene or polyvinyl chloride, or pure polytetrafluoroethylene.
  • the polytetrafluoroethylene content is preferably not less than 50%.
  • Any methacrylate copolymer serves as the methacrylic acid monoester of monohydric or polyhydric alcohol as a component of the copolymer (i) of methacrylic acid monoester of monohydric or polyhydric alcohol and methacrylic acid polyester of polyhydric alcohol, with preference given to methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-hydroxy-ethyl methacrylate and 2-hydroxy-propyl methacrylate.
  • methacrylic acid polyester of polyhydric alcohol for crosslinking monomer ethylene glycol dimethacrylate is most preferable.
  • trimethylolpropane trimethacrylate and pentaerythritol tetramethacrylate are also preferred.
  • This methacrylate copolymer is preferably porous.
  • the porous methacrylate copolymer should contain 10 to 90% by weight of methacrylic acid monoester of monohydric or polyhydric alcohol.
  • the content of methacrylic acid polyester of polyhydric alcohol is preferably not more than 50%.
  • Examples of preferred commercial products include Amberlite XDA-7, 8 and 9, produced by Rohm & Haas Company.
  • These substances are preferably porous, having a large surface area.
  • the specific surface area is preferably about 1 to 3000 m 2 /g, more preferably 100 to 1000 m 2 /g.
  • the pore radius is preferably 4 to 2000 Angstrom.
  • the color developer used for the color developing process preferably incorporates an organic preservative selected from the group comprising the hydroxylamine derivatives described in Japanese Patent O. P. I. Publication Nos. 146043/1988, 146042/1988, 146041/1988, 146040/1988, 135938/1988 and 118748/1988, the hydroxamic acids, hydrazines, hydrazides, phenols, ⁇ -hydroxyketones, ⁇ -aminoketones, sugars, monoamines, diamines, quaternary ammonium salts, nitroxyl radicals, alcohols, oximes, diazide compounds and condensed cyclic amines described in Japanese Patent O. P. I.
  • R 1 and R 2 independently represent an alkyl group or hydrogen atom.
  • R 1 and R 2 do not represent a hydrogen atom concurrently.
  • R 1 and R 2 may bind together to form a ring.
  • R 1 and R 2 independently represent an alkyl group or hydrogen atom, but they do not represent a hydrogen atom concurrently.
  • the alkyl groups represented by R 1 and R 2 may be identical or not, each of which preferably has a carbon number of 1 to 3.
  • the alkyl groups for R 1 and R 2 include those having a substituent.
  • R 1 and R 2 may bind together to form a ring, such as a heterocyclic ring like a piperidine or morpholine ring.
  • the concentration of the compound represented by the formula IV in the color developer is normally 0.2 g/l to 50 g/l, preferably 0.5 g/l to 30 g/l, and still more preferably 1 g/l to 15 g/l.
  • the compound represented by the formula IV may be used in combination with conventionally used hydroxylamine and an organic preservative, it is preferable from the viewpoint of developability to avoid the use of hydroxylamine.
  • R 21 represents a hydroxylalkyl group having a carbon number of 2 to 6
  • R 22 and R 23 independently represent a hydrogen atom, alkyl group having a carbon number of 1 to 6, hydroxylalkyl group having a carbon number of 2 to 6, benzyl group or -Cn 1 H 2 n 1 -N (n 1 is an integer of 1 to 6
  • X' and Y' independently represent a hydrogen atom, an alkyl group having a carbon number of 1 to 6 or hydroxylalkyl group having a carbon number of 2 to 6).
  • the compound represented by the formula V is used preferably at 1 to 100 g, more preferably 2 to 30 g per liter of color developer.
  • the color developing agent for the color developer is preferably a p-phenylenediamine compound having a water-soluble group. At least one water-soluble group is present on the amino group or benzene nucleus of the p-phenylenediamine compound.
  • preferred water-soluble groups include - (CH 2 ) n -CH 2 OH, - (CH 2 ) m -NHSO 2 -(CH 2 ) n -CH 3 , - (CH 2 ) m -O-(CH 2 ) n -CH 3 , - (CH 2 CH 2 O) n C m H 2m+1 (m and n independently represent any integer, -COOH group and -SO 3 H group.
  • Exemplified Compound Nos. CD-1, CD-2, CD-3, CD-4, CD-6, CD-7 and CD-15 are preferred, with more preference given to Exemplified Compound No. CD-1.
  • the color developing agent is used normally in the form of a salt such as hydrochloride, sulfate or p-toluenesulfonate.
  • the amount of addition of the preferably used p-phenylenediamine compound is preferably not less than 0.5 x 10 -2 mol, more preferably 1.0 x 10 -2 to 1.0 x 10 -1 mol, ideally 1.5 x 10 -2 to 7.0 x 10 -2 mol per liter of color developer.
  • the color developer may contain the following developer components in addition to the components described above.
  • Alkalis such as sodium hydroxide, potassium hydroxide, silicate, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate and borax, whether singly or in combination, can be added, as long as their addition has a pH stabilizing effect without causing precipitation.
  • various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate and borate can be used.
  • An inorganic or organic anti-fogging agent may be added as necessary.
  • a development accelerator may also be used as necessary.
  • developing accelerators include the various pyridinium compounds described in US Patent Nos. 2,648,604 and 3,671,247 and Japanese Patent Examined Publication No. 9503/1969 and other cationic compounds, cationic pigments such as phenosafranine, neutral salts such as thallium nitrate, the polyethylene glycol and its derivatives described in US Patent Nos. 2,533,990, 2,531,832, 2,950,970 and 2,577,127 and Japanese Patent Examined Publication No. 9504/1969, nonionic compounds such as polythioethers, the phenethyl alcohol described in US Patent No. 2,304,925, and acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine and amines.
  • benzyl alcohol it is undesirable to use benzyl alcohol, and it is preferable to avoid the use of a poor organic solvent such as phenetyl alcohol.
  • a poor organic solvent such as phenetyl alcohol.
  • Its use is liable to cause tar formation during long term use of color developer, particularly during a running process using a reduced amount of replenisher, which tar formation can even cause a significant failure, namely considerable damage of the commercial value of the paper light-sensitive material to be processed by adhering thereto.
  • a poor organic solvent is weakly soluble in water, its use is troublesome, for example, a stirrer is required to prepare the color developer but also the obtained development accelerating effect is limited by the low solubility even when such a stirrer is used.
  • the color developer may contain the fluorescent brightening agent represented by the above formula Z-1.
  • the color developer may also appropriately incorporate organic solvents such as ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, ⁇ -cyclodextrin and the compounds described in Japanese Patent Examined Publication Nos. 33378/1972 and 9509/1969 for increasing the solubility of the developing agent.
  • organic solvents such as ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, ⁇ -cyclodextrin and the compounds described in Japanese Patent Examined Publication Nos. 33378/1972 and 9509/1969 for increasing the solubility of the developing agent.
  • auxiliary developing agent may be used in combination with the principal developing agent.
  • auxiliary developing agents include N-methyl-p-aminophenol sulfate (Metol), phenidone, N,N-diethyl-p-aminophenol hydrochloride and N,N,N',N'-tetramethyl-p-phenylenediamine hydrochloride.
  • the amount of their addition is preferably 0.01 to 1.0 g/l.
  • the color developer may appropriately contain chelating agents represented by the above formulas K-I through K-XV.
  • the color developer components can be prepared by sequential addition to a given amount of water with stirring.
  • the components which are less soluble in water can be added in mixture with triethanolamine or another organic solvent described above.
  • a color developer can be obtained by adding to, and stirring in, water a dense aqueous solution or solid of a plurality of components which are capable of stable presence, previously prepared in a small vessel.
  • the color developer can be used in any pH range, but the pH is preferably 9.5 to 13.0, more preferably 9.8 to 12.0 from the viewpoint of rapid processing.
  • the color developer processing temperature is normally over 30°C, preferably over 33°C, and ideally over 35 to 65°C.
  • the processing time is preferably within 90 seconds, more preferably between 3 seconds and 60 seconds, and ideally between 3 seconds and 45 seconds.
  • the amount of replenishment for the color developer is preferably 20 to 150 ml/m 2 , more preferably 30 to 120 ml/m 2 for the desired anti-staining effect, since the effect of the present invention is enhanced when the amount of replenishment is small.
  • Color development can be achieved by various methods such as the spray method using the processing solution in the form of a spray, the web method based on the contact of the light-sensitive material with a carrier impregnated with the processing solution and the developing method using a viscous processing solution, as well as the one-bath processing method.
  • Examples of the bleaching agent for the bleacher of the present invention include ferric complex salts of the organic acid represented by the following formula A-I or B-I and ferric complex salts of Exemplified Compounds A'-1 through A'-16 shown below, with preference given to ferric complex salts of the organic acid represented by the following formula A-I or B-I.
  • a 1 through A 4 whether identical or not, independently represent -CH 2 OH, -COOM or -PO 3 M 1 M 2 ;
  • M, M 1 and M 2 independently represent a hydrogen atom, atom of alkali metal such as sodium or potassium, or an ammonium group.
  • X represents a substituted or unsubstituted alkylene group having a carbon number of 3 to 6, such propylene, butylene or pentamethylene.
  • substituents include a hydrogen group and an alkyl group having a carbon number of 1 to 3.
  • the ferric complex salt of these compounds A 1 -1 through A 1 -12 may be the sodium salt, potassium salt or ammonium salt thereof.
  • a 1 -1, A 1 -3, A 1 -4, A 1 -5 and A 1 -9 are preferred, with more preference given to A 1 -1.
  • a 1 through A 4 have the same definitions as above; n represents an integer of 1 to 8.
  • B 1 and B 2 whether identical or not, independently represent a substituted or unsubstituted alkylene group having a carbon number of 2 to 5, such as an ethylene, propylene, butylene or pentamethylene group.
  • the substituent include a hydroxyl group and a lower alkyl group having a carbon number of 1 to 3, such as a methyl group, ethyl group and propyl group.
  • the ferric complex salt of these compounds B 1 -1 through B 1 -7 may be the sodium salt, potassium salt or ammonium salt thereof.
  • the ferric complex salt of the organic acid represented by the above formula A-I or B-I be sufficiently oxidative and the ammonium salt content be not more than 50 mol%, more preferably not more than 20 mol%, and ideally not more than 10 mol% from the viewpoint of prevention of environmental pollution.
  • B 1 -1, B 1 -2 and B 1 -7 are preferred, with more preference given to B 1 -1.
  • the amount of addition of the ferric complex salt of organic acid is preferably 0.1 to 2.0 mol, more preferably 0.15 to 1.5 mol per liter of bleacher.
  • Examples of preferred bleachers other than the compound represented by the above formula A-I or B-I include the ferric complex salts such as ammonium, sodium, potassium and triethanolamine salts of the following compounds, but these are not to be construed as limitative.
  • the bleacher may incorporate one or more ferric complex salts of the compounds A'-1 through A'-16 in combination with the ferric complex salt of the compound represented by the above formula A-I or B-I.
  • ferric complex salt of the compound represented by the above formula A-I or B-I account for not less than 70 mol%, more preferably not less than 90 mol%, and ideally not less than 95 mol%.
  • ammonium is desirable as the cation in the bleacher, but it is possible to use non-ammonium salt such as potassium, sodium or alkanolamine salt, since the ferric complex salt of the organic acid represented by the above formula A-I or B-I is highly oxidative as stated above, which forms a preferred mode of the embodiment of the invention.
  • the ammonium salt content is preferably not more than 50 mol%, more preferably not more than 20 mol%, and ideally not more than 10 mol% of the total cation content for the enhancement of the desired effect.
  • the iron (III) complex salt of organic acid may be used in the form of a complex salt as such or may be converted to an iron (III) ion complex salt by reaction in a solution between an iron (III) salt such as ferrous sulfate, ferrous chloride, ferrous acetate, ferrous ammonium sulfate or ferrous phosphate and aminopolycarboxylic acid or its salt.
  • an iron (III) salt such as ferrous sulfate, ferrous chloride, ferrous acetate, ferrous ammonium sulfate or ferrous phosphate
  • aminopolycarboxylic acid or its salt When using in the form of a complex salt as such, one or more complex salts may be used.
  • ferrous salt and aminopolycarboxylic acid When using a ferrous salt and aminopolycarboxylic acid to form a complex salt in a solution, one or more ferrous salts may be used. Similarly, one or more aminopolycarboxylic acids may be used. In either
  • the bleach-fixer or bleacher containing the iron (III) ion complex may incorporate an ion complex salt of a metal other than iron, such as cobalt, copper, nickel or zinc.
  • the rapid processing effect can be enhanced by incorporating in the bleacher at least one of the imidazole described in Japanese Patent Application No. 48931/1988 and its derivatives and the compounds represented by the formulas I through IX described in the same patent application.
  • bleaching accelerators may be used alone or in combination.
  • the amount of their addition is preferably about 0.01 to 100 g, more preferably 0.05 to 50 g, and ideally 0.05 to 15 g per liter of bleacher.
  • the bleaching accelerator may be added and dissolved as such, but it is common practice to add it in solution in water, alkali or organic acid, and an organic solvent such as methanol, ethanol or acetone may be appropriately used to dissolve it before its addition.
  • the temperature of the bleacher is normally 20 to 50°C, and desirably 25 to 45°C.
  • the pH of the bleacher is preferably not more than 6.0, more preferably not less than 1.0 and not more than 5.5.
  • the pH of the bleacher means the pH in the silver halide light-sensitive material processing tank solution and is clearly differentiated from the pH of the replenisher.
  • the bleacher normally incorporates a halide such as ammonium bromide, potassium bromide or sodium bromide.
  • a halide such as ammonium bromide, potassium bromide or sodium bromide.
  • Various fluorescent brightening agents, defoaming agents and surfactants may be added.
  • the amount of bleacher replenisher is normally not more than 500 ml, preferably 20 to 400 ml, and ideally 40 to 350 ml per m 2 of silver halide color photographic light-sensitive material. As the amount of replenisher decreases, the effect of the present invention is more enhanced.
  • air or oxygen sparging may be carried out in the processing bath and in the replenisher storage tank if necessary, and an appropriate oxidant such as hydrogen peroxide, hydrobromate or persulfate may be appropriately added.
  • the fixing agent used in the fixer in the fixation process following the bleaching process is at least 0.2 mol/l thiosulfate as stated above, but its use in combination with thiocyanate offers improvement in the prevention of sagging, a problem to be solved by the invention.
  • the amount of addition of thiocyanate is preferably 0.1 to 3.0 mol/l, more preferably 0.2 to 2.5 mol/l.
  • the fixer may contain one or more pH buffers selected from the group comprising various acids and salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide.
  • various acids and salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide.
  • a re-halogenating agent such as an alkali halide or ammonium halide, such as potassium bromide, sodium bromide, sodium chloride or ammonium bromide.
  • pH buffers such as borate, oxalate, acetate, carbonate and phosphate and compounds which are known as additives to the fixer such as alkylamines and polyethylene oxides.
  • the ammonium ion concentration is not more than 50 mol%, more preferably not more than 20 mol%, and ideally 0 to 10 mol% of the total cation content from the viewpoint of prevention of staining upon processing with fixer immediately after bleaching and suppression of environmental pollution by reducing the ammonium ion concentration.
  • thiocyanate at about 0.1 to 3.0 mol/l, or to keep the thiosulfate concentration at not less than 0.5 mol/l, more preferably not less than 1.0 mol/l, and ideally 1.2 to 2.5 mol/l.
  • Silver may be recovered from the fixer by a known method.
  • Examples of method which serve well for this purpose include the electrolytic method described in French Patent No. 2,299,667, the precipitation method described in Japanese Patent O. P. I. Publication No. 73037/1977 and German Patent No. 2,331,220, the ion exchange method described in Japanese Patent O. P. I. Publication No. 17114/1976 and German Patent No. 2,548,237 and the metal replacement method described in British Patent No. 1,353,805.
  • silver recovery it is particularly preferable to recover silver from the tank solution on an in-line basis using the electrolytic method or ion exchange resin method, since the rapid processing suitability improves, but silver may be recovered from the overflow waste liquid for recycled use.
  • the amount of replenishment for the fixer is preferably not more than 1200 ml, more preferably 20 to 1000 ml, and ideally 50 to 800 ml per m 2 of light-sensitive material.
  • the pH of the fixer is preferably 4 to 8.
  • a compound represented by the formula FA described in Japanese Patent Application No. 48931/1988, pp. 56 may be added to the fixer, which offers an additional effect in that sludge formation is significantly suppressed during prolonged processing of a small amount of light-sensitive material with a bleach-fixer or fixer.
  • a compound represented by the formula FA can be synthesized by the ordinary method described in US Patent Nos. 3,335,161 and 3,260,718. These compounds represented by the formula FA may be used alone or in combination.
  • the fixer may incorporate a sulfite and sulfite-releasing compound.
  • a sulfite and sulfite-releasing compound examples include potassium sulfite, sodium sulfite, ammonium sulfite, ammonium hydrogen sulfite, potassium hydrogen sulfite, sodium hydrogen sulfite, potassium metabisulfite, sodium metabisulfite and ammonium metabisulfite, as well as the compound represented by the formula B-1 or B-2 described in Japanese Patent Application No. 48931/1988, p. 60.
  • sulfites and sulfite-releasing compounds should necessarily be present in an amount of at least 0.1 mol as sulfite ion per liter of fixer, but their concentration is preferably 0.12 to 0.65 mol/l, more preferably 0.15 to 0.50 mol/l, and ideally 0.20 to 0.40 mol/l.
  • the processing times respectively for the bleacher and fixer of the present invention may be set at any level, but each processing time is preferably shorter than 4 minutes and 30 seconds, more preferably 20 seconds to 3 minutes and 20 seconds, more preferably 40 seconds to 3 minutes, and ideally 60 seconds to 2 minutes and 40 seconds.
  • forced stirring does not imply ordinary diffusive migration of solution but implies stirring by means of a stirrer.
  • This forced stirring can be achieved by the methods described in Japanese Patent Application No. 48930/1988 and Japanese Patent O. P. I. Publication No. 206343/1989.
  • bleach fogging an additional effect of the invention, is effected when the crossover time between processing solution tanks such as between the color developer tank and the bleach tank is within 10 seconds, preferably within 7 seconds. It is another preferred mode of the embodiment of the invention to reduce the amount of processing solution carried by the light-sensitive material by means of, for example, a duckbill valve, which enhances the effect of the invention.
  • sulfite it is preferable to add sulfite to the stabilizer. Any sulfite, whether organic or inorganic, can be used, as long as it releases sulfite ions, but preference is given to an inorganic salt. Examples of preferred compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite.
  • the sulfite is added preferably in amounts such that its concentration in the stabilizer is at least 1 x 10 -3 mol/l, more preferably 5 x 10 -3 mol/l to 10 -1 mol/l. Its addition is preferred, since it has an anti-staining effect. Although it may be added directly to the stabilizer, it is preferable to add it to the stabilizer replenisher.
  • Ammonium compounds are particularly desirable for addition to the stabilizer. They are supplied via ammonium salts of various inorganic compounds. Examples thereof include ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium fluoride, acidic ammonium fluoride, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammonium hydrofluoride, ammonium hydrogen sulfite, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, ammonium laurin tricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, am
  • the amount of addition of ammonium compounds is preferably 0.001 to 1.0 mol, more preferably 0.002 to 2.0 mol per liter of stabilizer.
  • the chelate stability constant is the constant which is well known in L. G. Sillen and A. E. Martell, "Stability Constants of Metal Ion Complexes", the Chemical Society, London (1964), S. Chaberek and A. E. Martell in “Organic Sequestering Agents", Wiley (1959), and other publications.
  • Examples of chelating agents having an iron ion chelate stability constant of over 8 include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents and polyhydroxy compounds.
  • the iron ion means the ferric ion (Fe 3+ ).
  • chelating agents having a ferric ion chelate stability constant of over 8 include ethylenediaminediorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethyl glycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, trans-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1
  • diethylenetriaminepentaacetic acid diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid and 1-hydroxyethylidene-1,1-diphosphonic acid are more preferable, with most preference given to 1-hydroxyethylidene-1,1-diphosphonic acid.
  • the amount of the chelating agent is preferably 0.01 to 50 g, more preferably 0.05 to 20 g per liter of stabilizer.
  • Examples of other commonly known compounds which can be added to the stabilizer include polyvinylpyrrolidone (PVPK-15, K-30, K-90), salts of organic acid such as citric acid, acetic acid, succinic acid, oxalic acid and benzoic acid, pH regulators such as phosphate, borate, hydrochloric acid and sulfuric acid, antifungal agents such as phenol derivatives, catechol derivatives, imidazole derivatives, triazole derivatives, cyabendazole derivatives, organic halides and others known as slime controlling agents in the paper-pulp industry, fluorescent brightening agents, surfactants, preservatives, and salts of metals such as Bi, Mg, Zn, Ni, Al, Sn, Ti and Zr. These compounds may be used in any combination, as long as they are necessary to maintain a desired pH level in the stabilizing bath and it does not affect the storage stability of color photographic images or cause precipitation.
  • PVPK-15, K-30, K-90 polyvinyl
  • the stabilization processing temperature is normally 15 to 70°C, preferably 20 to 55°C.
  • the processing time is preferably within 120 seconds, more preferably 3 to 90 seconds, and ideally 6 to 50 seconds for the enhancement of the effect of the present invention.
  • Washing is not necessary at all after stabilization, but rinsing, surface washing, etc. with a small amount of water for a very short time may be carried out optionally.
  • the presence of a soluble salt of iron in the stabilizing solution is preferred for the enhancement of the effect of the invention.
  • soluble salts of iron include iron salts of inorganic acid such as ferric chloride, ferrous chloride, ferric phosphate, ferric bromide, ferric nitrate and ferrous nitrate and iron salts of organic acid such as ferric ethylenediaminetetraacetate, ferric 1-hydroxyethylidene-1,1-diphosphonate, ferrous 1-hydroxyethylidene-1,1-diphosphonate, ferrous ethylenediaminetetraacetate, ferric diethylenetriaminepentaacetate, ferrous diethylenetriaminepentaacetate, ferric citrate, ferrous citrate, ethylenediaminetetramethylenephosphonate, ferrous ethylenediaminetetramethylenephosphonate, ferric nitrilotrimethylenephosphonate, ferric nitrilotriacetate and ferrous nitrilotriacetate.
  • iron salts of inorganic acid such as ferric chloride, ferrous chloride, ferric phosphat
  • iron salts of organic acid may be used in the form of a free acid or sodium salt, potassium salt, ammonium salt, lithium salt, alkylammonium salt such as triethanolammonium salt, trimethylammonium salt or tetramethylammonium salt.
  • These soluble salts of iron are used preferably at a concentration of at least 5 x 10 -3 mol/l, more preferably 8 x 10 -3 to 150 x 10 -3 mol/l, and still more preferably 12 x 10 -3 to 100 x 10 -3 mol/l in the stabilizer.
  • soluble salts of iron may be by adding them to the stabilizer replenisher, or by eluting them in the stabilizer from the light-sensitive material, or by introducing them while adhering to the light-sensitive material from the previous bath.
  • the stabilizer may be subjected to ion exchange resin treatment so that the calcium ion and magnesium ion concentration is below 5 ppm, and the antifungal agent and halogen ion releasing compound may be added to such a stabilizer.
  • the pH of the stabilizer is preferably 5.5 to 10.0.
  • the pH regulator which may be added to the stabilizer may be any one of the commonly known alkali or acid agents.
  • the amount of stabilizer replenisher is preferably 0.1 to 50 times the amount of processing solution carried from the previous bath (bleach-fixer), more preferably 0.5 to 30 times, per unit area of light-sensitive material.
  • the stabilizer tank preferably comprises 1 to 5 chambers, more preferably 1 to 3 chambers, and ideally 1 chamber from the viewpoint of silver removal efficiency and rapid processing.
  • Light-sensitive materials which are preferably used for the present invention are described below.
  • silver halide grains preferably used for the light-sensitive material include silver chloride grains and silver chlorobromide grains. It is preferable to use silver halide grains based mainly on silver chloride wherein the silver chloride content is at least 80 mol%, more preferably at least 90 mol%, still more preferably at least 95 mol%, and ideally at least 99 mol%. It is a preferred mode of the embodiment of the present invention to process a light-sensitive material incorporating a silver halide emulsion based mainly on such a silver chloride.
  • the silver halide emulsion based mainly on silver chloride may contain silver bromide and/or silver iodide in addition to silver chloride in the silver halide composition.
  • the silver bromide content is preferably not more than 20 mol%, more preferably not more than 10 mol%, and still more preferably not more than 3 mol%.
  • silver iodide When silver iodide is contained, its content is preferably not more than 1 mol%, more preferably not more than 0.5 mol%, and ideally zero.
  • Such silver halide grains based mainly on silver chloride having a silver chloride content of over 80 mol% are added to at least one silver halide emulsion layer, but it is preferable to add them to all silver halide emulsion layers.
  • the crystal configuration of the silver halide grains may be normal crystal, twin crystal or any other crystal, and any ratio of the [1.0.0] plane and the [1.1.1] plane is usable. With respect to the crystal structure of these silver halide grains, it may be uniform from the core to the outer portion and may be of the core shell type wherein the core and the outer portion are of different layer structures.
  • silver halides may be of the type wherein latent images are formed mainly on the surface.
  • tabular grains of silver halide such as those described in Japanese Patent O. P. I. Publication No. 113934/1983 and Japanese Patent Application No. 170070/1984 may be used.
  • the silver halide grains may be prepared by any of the acid method, neutral method, ammoniacal method and other methods.
  • the silver halide emulsion layer of the light-sensitive material processed in accordance with the present invention contains color couplers.
  • the color couplers form a non-diffusible dye upon reaction with the oxidation product of a color developing agent.
  • the color couplers are bound together in, or in close contact with, the light-sensitive layer preferably in a non-diffusible form.
  • the red-sensitive layer may thus contain a non-diffusible color coupler which forms a cyan color image, normally a phenol or ⁇ -naphthol coupler.
  • the green-sensitive layer may contain at least one non-diffusible color coupler which forms a magenta color image, normally a 5-pyrazolone color coupler and pyrazolotriazole.
  • the blue-sensitive layer may contain at least one non-diffusible color coupler which forms a yellow color image, normally a color coupler having an open chain ketomethylene group.
  • the color coupler may be a 6-, 4- or 2-equivalent coupler, for instance.
  • a 2-equivalent coupler is particularly preferred for the present invention.
  • magenta coupler represented by the formula M-1 described in Japanese Patent O. P. I. Publication No. 106655/1988, p. 26 (exemplified by Magenta Coupler Nos. 1 through 77 described in Japanese Patent O. P. I. Publication No. 106655/1988, pp. 29-34)
  • the cyan coupler represented by the formula C-I or C-II described in Japanese Patent O. P. I. Publication No. 106655/1988, p. 34 (exemplified by Cyan Coupler Nos. C'-1 through C'-82 and C"-1 through C"-36 described in Japanese Patent O. P. I. Publication No.
  • nitrogen-containing heterocyclic mercapto compounds examples include Compound Nos. I'-1 through I'-87 exemplified in Japanese Patent O. P. I. Publication No. 106655/1988, pp. 42-45.
  • a silver halide emulsion based mainly on silver chloride can be prepared by a conventional method such as single or double feeding of the starting materials at constant or accelerated rate. It is preferable to prepare it by double feeding while regulating the pAg (cf. Research Disclosure No. 17643, Sections I and II.
  • the emulsion based mainly on silver chloride may be chemically sensitized.
  • a sulfur-containing compound such as allylisothiocyanate, allylthiourea or thiosulfate is particularly preferred as a chemical sensitizer.
  • Reducing agents can also be used as chemical sensitizers, including the silver compounds described in Belgian Patent Nos. 493,464 and 568,687 and polyamine or aminomethylsulfinic acid derivatives such as the diethylenetriamine in accordance with Belgian Patent No. 547,323.
  • Noble metals such as gold, platinum, palladium, iridium, ruthenium and rhodium and noble metal compounds also serve as appropriate sensitizers.
  • the emulsion based mainly on silver chloride may be optically sensitized by a known method using, for example, an ordinary polymethine dye such as neutrocyanine, basic or acidic carbocyanine, rhodacyanine or hexacyanine, or a styryl dye, oxonol or related substance (cf. F. M. Hamer, "The Cyanine Dyes and Related Compounds", Ullmanns Enbzyklpadie der Technischen Chemie, 4th edition, vol. 18, p. 431 (1964); Research Disclosure No. 17643, Section IV.
  • an ordinary polymethine dye such as neutrocyanine, basic or acidic carbocyanine, rhodacyanine or hexacyanine, or a styryl dye, oxonol or related substance
  • the emulsion based mainly on silver chloride may incorporate an ordinary anti-fogging agent and stabilizer.
  • Azaindene is particularly suitable as a stabilizer, with preference given to tetra- and penta-azaindenes and more preference given to those substituted by a hydroxyl group or amino group.
  • Such compounds are described in Zeitschrift fürticianliche Photographie by Birr, 47, 2-58 (1952) and Research Disclosure No. 17643, Section IV.
  • Additives can be added to the light-sensitive material by known methods such as those described in US Patent Nos. 2,322,027, 2,533,514, 3,689,271, 3,764,336 and 3,765,897.
  • a coupler and UV absorbent can be incorporated in the form of a charged latex (cf. German Patent Publication No. 2,541,274 and European Patent Application No. 14,924). These components can also be immobilized as polymers in the light-sensitive material (cf. German Patent Publication No. 2,044,992 and US Patent Nos. 3,370,952 and 4,080,211).
  • An ordinary support can be used for the light-sensitive material, but a reflective support such as a paper support is most suitable, which can be coated with polyolefin, particularly polyethylene or polypropylene (cf. Research Disclosure No. 17643, Sections V and VI).
  • Any light-sensitive material can be used, as long as it contains a coupler therein and is processed by so-called internal development, such as a color paper, color negative film, color positive film, color reversal film for slide, color reversal film for movie, color reversal film for TV and reversal color paper, with most preference given to a color paper based mainly on silver chloride.
  • the stabilizer which contains the water-soluble surfactant of the present invention and which is brought into contact with the ion exchange resin or adsorbent of the invention is normally used to process light-sensitive materials for color paper.
  • a mixed processing system is very useful, since it permits mixed processing of two different light-sensitive materials such as a combination of a light-sensitive material for films and a light-sensitive material for paper.
  • Second through seventh coating solutions were prepared in the same manner as with the first layer coating solution.
  • Layer Composition Amount of addition (g/m 2 )
  • Layer 7 Protective layer Gelatin 1.0
  • Layer 6 Ultraviolet absorbing layer Gelatin 0.4
  • UV absorbent UV-1 0.10 UV absorbent UV-2 0.04
  • UV absorbent UV-3 0.16 Antistaining agent HQ-1 0.01 DNP 0.2
  • PVP 0.03 Anti-irradiation dye AI-2 0.02
  • Layer 5 Red-sensitive layer Gelatin 1.30 Red-sensitive silver chlorobromide emulsion EmC (as silver) 0.21 Cyan coupler C-1 0.17 Cyan coupler C-2 0.25 Dye image stabilizer ST-1 0.20
  • Layer 4 Ultraviolet absorbing layer Gelatin 0.94
  • Antistaining agent HQ-1 0.03 DNP 0.40 Layer 3 Green-sensitive
  • pAg was regulated by the method described in Japanese Patent O. P. I. Publication No. 45437/1984, and pH was regulated using an aqueous solution of sulfuric acid or sodium hydroxide.
  • solution A Sodium chloride 3.42 g Potassium bromide 0.03 g
  • the mixture was desalted with a 5% aqueous solution of Demol N, a product of Kao Atlas and a 20% aqueous solution of magnesium sulfate and then mixed with an aqueous solution of gelatin to yield a monodispersed emulsion EMP-1 comprising cubic grains having an average grain size of 0.85 ⁇ m, a coefficient of variance ( ⁇ /r) of 0.07 and a silver chloride content of 99.5 mol%.
  • the emulsion EMP-1 was chemically ripened with the following compounds at 50°C for 90 minutes to yield a blue-sensitive silver halide emulsion EmA.
  • Sodium thiosulfate 0.8 mg/mol AgX Chloroauric acid 0.5 mg/mol AgX stabilizer SB-5 6 x 10 -4 mol/mol AgX Sensitizing dye D-l 5 x 10 -4 mol/mol AgX
  • a monodispersed emulsion EMP-2 comprising cubic grains having an average grain size of 0.43 ⁇ m, a coefficient of variance ( ⁇ /r) of 0.08 and a silver chloride content of 99.5 mol% was prepared in the same manner as with EMP-1 except that the addition time for Solutions A and B and the addition time for Solutions C and D were changed.
  • the emulsion EMP-2 was chemically ripened with the following compounds at 55°C for 120 minutes to yield a green-sensitive silver halide emulsion EmB.
  • Sodium thiosulfate 1.5 mg/mol AgX Chloroauric acid 1.0 mg/mol AgX Stabilizer SB-5 6 x 10 -4 mol/mol AgX Sensitizing dye D-2 4 x 10 -4 mol/mol AgX
  • a monodispersed emulsion EMP-3 comprising cubic grains having an average grain size of 0.50 ⁇ m, a coefficient of variance ( ⁇ /r) of 0.08 and a silver chloride content of 99.5 mol% was prepared in the same manner as with EMP-1 except that the addition time for Solutions A and B and the addition time for Solutions C and D were changed.
  • the emulsion EMP-3 was chemically ripened with the following compounds at 60°C for 90 minutes to yield a red-sensitive silver halide emulsion EmC.
  • Sodium thiosulfate 1.8 mg/mol AgX
  • Chloroauric acid 2.0 mg/mol AgX
  • the color paper sample was subjected to running processing using the processing solutions thus prepared.
  • Running processing was carried out by filling an automatic developing machine with the color developer tank solution and bleach-fixer tank solution and stabilizer tank solution, and the color paper sample was processed therein while supplying the color developer replenisher, bleach-fixer replenisher and stabilizer replenisher using a fixation pump at 3-minute intervals.
  • the filter portion of the stabilizing bath was equipped with a small bag, like a tea bag, containing ion exchange resin or adsorbent.
  • the amounts of replenishment were 100 ml per m 2 of color paper for the color developer tank, 220 ml per m 2 of color paper for the bleach-fixer tank and 250 ml per m 2 of color paper for the stabilizer tank.
  • Running processing was continued at 0.05 R every day until the amount of the color developer replenisher added to the color developer tank solution reached 3 times the capacity of the color developer tank, wherein 1 R corresponds to the addition of the color developer replenisher in an amount equal to the capacity of the color developer tank.
  • the spectral reflective density at 640 nm in the unexposed portion was determined and the stain was evaluated. Also evaluated was the crystal deposition on the rollers and tank wall in the stabilizing bath.
  • the evaluation criteria are as follows:
  • Example 2 An experiment was carried out in the same manner as in Example 1 except that Exemplified Compound I-17 was added as a water-soluble surfactant to the stabilizer so that the stabilizer surface tension was 20 dyne/cm and the ion exchange resin or adsorbent to be brought into contact with the stabilizer in the stabilizing bath were changed as shown in Table 2.
  • the obtained samples were evaluated with respect to stain in the unexposed portion and crystal deposition on the rollers and tank wall in the stabilizing bath. The results are shown in Table 2.
  • Figure 4 is a cross-sectional view of a mode of the automatic developing machine for use in the method of the present invention.
  • Figure 2 is a plane view of the automatic developing machine.
  • the symbol 1 denotes the main body of the developing machine, in front of which a supply part 4 is furnished to supply an undeveloped color negative light-sensitive material 2 or color positive paper light-sensitive material 3 and in the rear of which a take-out portion 5 is furnished where the processed light-sensitive materials 2 and 3 are taken out.
  • a developer tank 6 bleacher tank 7, fixer tank 8, stabilizer tanks 9, 10 and 11 and a drying portion 12 in sequential arrangement from the supply portion side to the take-out portion side.
  • the developer tank 6, bleacher tank 7, fixer tank 8, first stabilizer tanks 9 and 10 and second stabilizer tank 11 are configured as shown in Figure 1.
  • the developer tank 6 is configured with a negative developer tank 6a and a positive developer tank 6b, each of which is filled with a dedicated developer.
  • the negative light-sensitive material 2 and positive light-sensitive material 3 are separately processed in the negative developer tank 6a and positive developer tank 6b, respectively, so that the photographic performance is maximized.
  • the processing tanks located in the rear of the developer tank 6, i.e., the bleacher tanks 7a and 7b and fixer tanks 8a and 8b are filled with a bleacher and fixer of the same composition, respectively.
  • the stabilizer tank combinations of 9a, 10a and 11a and 9b and 10b they may be filled with differently composed stabilizers, and 9a, 10a, 11a, 9b and 10b may all be filled with a stabilizer of the same composition.
  • stabilization of the light-sensitive material does not use water but uses the stabilizer, thus requiring no water.
  • no drain piping is necessary, so there is no limitation as to the site of installation.
  • negative developer and positive developer replenishers with different compositions may be used.
  • bleacher replenisher fixer replenisher and stabilizer replenisher
  • a single replenisher may be used commonly for negative and positive development.
  • a coating aid SU-4 a dispersing agent SU-3, hardeners H-1 and H-2, a stabilizer ST-1, a preservative D1-1, antifogging agents AF-1 and AF-2 and dyes AI-1 and AI-2 were added to appropriate layers.
  • the emulsions used to prepare the sample described above are as follows, all of which are monodispersed emulsions having a high inside iodide content.
  • Octahedral grains having an average AgI content of 7.5 mol% and an average grain size of 0.55 ⁇ m.
  • Octahedral grains having an average AgI content of 2.5 mol% and an average grain size of 0.36 ⁇ m.
  • Octahedral grains having an average AgI content of 8.0 mol% and an average grain size of 0.84 ⁇ m.
  • Octahedral grains having an average AgI content of 8.5 mol% and an average grain size of 1.02 ⁇ m.
  • the processing solutions thus obtained were added to the automatic developing machine illustrated in Figures 1 and 2.
  • the filter portion of the stabilizing bath was equipped with a small bag, like a tea bag, containing ion exchange resin or adsorbent, and continuous running processing was carried out at a daily processing rate of 2.0 m 2 for the color negative film and 12 m 2 for the color paper for 30 days.
  • the spectral reflective density at 640 nm in the unexposed portion was determined and the stain was evaluated. Also evaluated was crystal deposition on the rollers and tank wall in the stabilizing bath for paper using the evaluation criteria shown below. The results are given in Table 4.
  • Example 4 An experiment was carried out in the same manner as in Example 4 except that the ion exchange resin or adsorbent described in Example 2 was brought into contact with the stabilizer for paper, and the obtained sample was evaluated with respect to stain in the unexposed portion of paper and crystal deposition on the rollers and tank wall in the stabilizing bath. Good results were obtained like in Example 3.
  • Example 5 An experiment was carried out in the same manner as in Example 4 except that the water soluble surfactant to be added to the stabilizer and the amount of stabilizer replenisher for paper processing were changed as shown in Table 5, and the obtained sample was evaluated with respect to stain in the unexposed portion and crystal deposition on the rollers and tank wall in the stabilizing bath. The results are given in Table 5.
  • the present invention has provided a silver halide color photographic light-sensitive material processing method which prevents stain attributable to residual pigments and dyes in color printing paper and crystal deposition on the processing tanks and rollers and which permits rapid processing and reduction in the amount of replenisher.

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Claims (7)

  1. Procédé de traitement d'un matériau photographique photosensible couleur à base d'halogénure d'argent, comprenant un support revêtu d'une émulsion à base d'halogénure d'argent contenant des grains d'halogénure d'argent ayant une teneur moyenne en chlorure d'argent qui n'est pas inférieure à 80 % en moles de chlorure d'argent par rapport à la teneur totale en halogénure d'argent, comprenant les étapes consistant :
    à développer, décolorer, fixer et stabiliser le matériau dans un bain de stabilisation, dans lequel
    une solution de stabilisation, contenue dans le bain de stabilisation ayant une tension superficielle de 15 à 60 dynes/cm, comprend un agent tensioactif, et une résine échangeuse d'ions ou un adsorbant étant mis en contact avec la solution de stabilisation dans le bain de stabilisation, dans lequel l'agent tensioactif est représenté par la fomule I ou II,
    Figure 01530001
    dans laquelle R représente un atome d'hydrogène, une groupe alkyle linéaire ou ramifié ayant de 4 à 25 atomes de carbone, qui peut porter un susbstituant, ou
    Figure 01530002
    dans laquelle R1 et R2 représentent indépendamment un atome d'hydrogène ou un groupe alkyle ayant de 1 à 20 atomes de carbone qui peut porter un substituant, 1 représente un nombre de 0 à 4,
    n et m représentent indépendamment un nombre de 0 à 200, mais ne peuvent être simultanément 0; A et B, qui peuvent être identiques ou différents, représentent indépendamment
    Figure 01540001
    où n1, m1 et l1 représentent indépendamment 0, 1, 2 ou 3, et n1, m1 et l1 ne représentent pas simultanément 0; D représente un atome d'hydrogène ou un groupe -SO3M ou -PO3M, où M représente un atome d'hydrogène, un métal alcalin ou l'ammonium ;
    Figure 01540002
    dans laquelle R3 représente un atome d'hydrogène, un groupe hydroxyle, alkyle inférieur, alcoxy,
    Figure 01540003
    R4, R5 et R6, qui peuvent être identiques ou différents, représentent indépendamment un groupe alkyle inférieur, ayant de 1 à 3 atomes de carbone ; ll, l2 et l3 représentent indépendamment un nombre de 0 à 4 ; et p, q1 et q2 représentent indépendamment un nombre de 1 à 15.
  2. Procédé selon la revendication 1, dans lequel une solution de régénération de la solution de stabilisation est une partie ou la totalité de la solution de trop-plein provenant d'un bain ayant une solution de stabilisation utilisée pour le traitement d'un matériau photographique couleur à base d'halogénure d'argent d'un type différent, qui présente une teneur en iodure d'argent supérieure à 2 % en moles.
  3. Procédé selon l'une quelconque des revendications 1 ou 2, dans lequel la résine échangeuse d'ions est un échangeur d'anions.
  4. Procédé selon la revendication 3, dans lequel l'échangeur d'anions est représenté par la formule III
    Figure 01550001
    dans laquelle A représente un monomère ayant plus de deux radicaux éthylène qui sont capables de se copolymériser et au moins l'un des radicaux forme une ramification, B représente un groupe éthylène monomère qui est capable de se copolymériser, R13 représente un atome d'hydrogène, un groupe alkyle inférieur ou un groupe aralkyle,
    Q représente une liaison simple, un groupe alkylène, phénylène, aralkylène,
    Figure 01550002
    où L représente un groupe alkylène, arylène ou aralkylène, R est un groupe aralkyle,
    G représente
    Figure 01560001
    où R14, R15, R16, R17, R18, R19, R20 et R21, qui peuvent être identiques ou différents, représentent chacun indépendamment un atome d'hydrogène, un groupe alkyle, aryle ou aralkyle éventuellement substitué, et X est un ion négatif ;
    plus de deux groupes de Q, R14, R15, R16, ou Q, R17, R18, R19, R20 et R21. peuvent former un groupe hétérocyclique avec un atome d'azote ;
    x, y et z désignent des % en moles, x est compris entre 0 et 60, y entre 0 et 60 et z entre 30 et 100.
  5. Procédé selon la revendication 3, dans lequel l'échangeur d'anions est représenté par la formule IV,
    Figure 01560002
    dans laquelle A, B, x, y, z, R13, R14, R15, R16, X- sont tels que définis pour la formule III.
  6. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'adsorbant est du charbon actif, une substance argileuse, un composé polymère polyamide, un composé polymère polyuréthanne, une résine phénolique, un composé polymère ayant un groupe hydrazide, ou un composé polymère comprenant du polytétrafluoroéthylène; ou un copolymère d'un monoester d'acide méthacrylique et d'un alcool monohydrique ou polyhydrique et un polyester d'acide méthacrylique et d'un alcool polyhydrique.
  7. Procédé selon la revendication 6, dans lequel l'adsorbant est du charbon actif, ou un composé polymère comprenant du polytétrafluoroéthylène; ou un copolymère d'un monoester d'acide méthacrylique et d'un alcool monohydrique ou polyhydrique et un polyester d'acide méthacrylique et d'un alcool polyhydrique.
EP19910306008 1990-07-03 1991-07-02 Méthode de traitement pour matériau photographique couleur à halogénure d'argent Expired - Lifetime EP0465228B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP176656/90 1990-07-03
JP2176656A JP2942963B2 (ja) 1990-07-03 1990-07-03 ハロゲン化銀カラー写真感光材料の処理方法

Publications (3)

Publication Number Publication Date
EP0465228A2 EP0465228A2 (fr) 1992-01-08
EP0465228A3 EP0465228A3 (en) 1992-04-08
EP0465228B1 true EP0465228B1 (fr) 1998-12-16

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EP19910306008 Expired - Lifetime EP0465228B1 (fr) 1990-07-03 1991-07-02 Méthode de traitement pour matériau photographique couleur à halogénure d'argent

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EP (1) EP0465228B1 (fr)
JP (1) JP2942963B2 (fr)
DE (1) DE69130625T2 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07152135A (ja) * 1993-08-11 1995-06-16 Eastman Kodak Co ハロゲン化銀写真要素をリンスするための水溶液及びハロゲン化銀写真要素の処理方法
US5534396A (en) * 1994-11-09 1996-07-09 Eastman Kodak Company Rinse composition for photographic paper containing alkyl ether sulfate and biocide, and method of use
CA2711915C (fr) * 2008-01-18 2016-04-12 Rhodia Operations Liants latex, revetements aqueux et peintures presentant une stabilite au gel/degel et procedes d'utilisation correspondants

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1235325A (fr) * 1983-12-16 1988-04-19 Shigeharu Koboshi Ensemble de revelation et de tirage de photos
JPS60220345A (ja) * 1984-04-17 1985-11-05 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
JPS6275451A (ja) * 1985-09-27 1987-04-07 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
DE3800681A1 (de) * 1987-10-17 1989-04-27 Agfa Gevaert Ag Waschwasserfreies fotografisches verarbeitungsverfahren und fuer dieses verfahren benutztes stabilisierbad
JPH0297940A (ja) * 1988-10-04 1990-04-10 Konica Corp ハロゲン化銀写真感光材料

Also Published As

Publication number Publication date
JPH0463344A (ja) 1992-02-28
EP0465228A3 (en) 1992-04-08
DE69130625D1 (de) 1999-01-28
EP0465228A2 (fr) 1992-01-08
DE69130625T2 (de) 1999-05-27
JP2942963B2 (ja) 1999-08-30

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