EP0217643B1 - Procédé de traitement d'un matériau photographique couleur à l'halogénure d'argent sensible à la lumière - Google Patents

Procédé de traitement d'un matériau photographique couleur à l'halogénure d'argent sensible à la lumière Download PDF

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Publication number
EP0217643B1
EP0217643B1 EP86307394A EP86307394A EP0217643B1 EP 0217643 B1 EP0217643 B1 EP 0217643B1 EP 86307394 A EP86307394 A EP 86307394A EP 86307394 A EP86307394 A EP 86307394A EP 0217643 B1 EP0217643 B1 EP 0217643B1
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Prior art keywords
processing
light
silver halide
sensitive silver
photographic material
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EP86307394A
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German (de)
English (en)
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EP0217643A2 (fr
EP0217643A3 (en
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Masayuki Kurematsu
Shigeharu Koboshi
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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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
    • G03C5/39—Stabilising, i.e. fixing without washing out
    • 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
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes

Definitions

  • This invention relates to a method for processing of a light-sensitive silver halide color photographic material (hereinafter called light-sensitive material) in which a water washing processing step is omitted, more particularly to a processing method without water washing of a light-sensitive material in which stain generation at an unexposed portion by continuous processing is substantially prevented.
  • light-sensitive material a light-sensitive silver halide color photographic material
  • light-sensitive materials after imagewise exposure, are processed according to processing steps such as color developing, bleaching, fixing, stabilizing, bleach-fixing, water washing, etc.
  • processing steps such as color developing, bleaching, fixing, stabilizing, bleach-fixing, water washing, etc.
  • the increased cost for water washing due to exhaustion of water resources, and the rise in price of crude oil are becoming an increasingly serious problem.
  • Japanese Application No. 58189634 discloses a silver halide photosensitive material which contains a specific phenolic cyan coupler which possesses a substituted or condensed 4-cyanophenylureido group at the 2-position and a ballasting acylamino group at the 5-position. This material is imagewise exposed and developed with a color developing solution containing no benzyl alcohol.
  • an object of the present invention is to provide a method for processing in which contamination at the unexposed portion of a light-sensitive material generated in the case of continuous processing by use of a stabilizing solution substituting for water washing is largely prevented without a deterioration in storage stability, particularly deterioration of the light fading characteristic of the dye image.
  • a method for processing a light-sensitive silver halide color photographic material which comprises subjecting a light-sensitive silver halide color photographic material having a total dried film thickness of the light-sensitive silver halide emulsion layers and the non-light-sensitive layers on one surface of a support of 10 ⁇ m or more, to imagewise exposure, then processing the expose material with a color forming developing solution containing at most 1 ml/l of benzyl alcohol, thereafter processing the material with a processing solution having fixing ability and subsequently for water washing having a surface tension of 8 to 50 dyne/cm (mN/m) at 20°C and containing at most 0.1 g/l of aldehyde compound, followed by drying.
  • the present inventors have also found that the effect of the present invention is more marked when the light-sensitive material contains a sensitizing dye represented by the formula (I) shown below: wherein each of Z1 and Z2 independently represents a group of atoms to complete a benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, benzoimidazole nucleus, naphthoimidazole nucleus, pyridine nucleux or quinoline nucleus, each of R1 and R2 independently represents an alkyl group, an alkenyl group or an aryl group, R3 represents a hydrogen atom, a methyl group or an ethyl group and X1 ⁇ represents an anion and l represents 0 or 1.
  • a sensitizing dye represented by the formula (I) shown below: wherein each of Z1 and
  • the stabilizing solution substitution for water washing will be stored over a long time due a reduction in the rate of renewal thereof, and the stabilizing solution is considerably colored due to the coloring components of the above substances in it. Accordingly, it may be estimated that these coloring components are adsorbed onto the light-sensitive material in the stabilizing solution substituting for water washing, or washing-out from the light-sensitive material is inhibited, whereby the unex­posed portion of the light-sensitive material becomes stained.
  • Benzyl alcohol has been used for a long time in a color developing solution generally as a developing accelerator. Also, it is well known in the art that formalin which is an aldehyde compound has been used in the final stabilizing solution for the purpose of image stability in the final step of conventional color processing steps.
  • processing with a processing solution having fixing ability after color developing refers to the step of using a fixing bath or a bleach-fixing bath for the purpose of fixing the light-sensitive material after processing with a conven­tional color developing solution. That is, the present invention has solved the problem with the stabilizing solution substituting for water washing after a process­ing in a bleaching bath _ fixing bath or a bleach-fixing bath after color developing.
  • the present invention is particularly effective for the latter, namely processing in a bleach-fixing bath.
  • the color developing solution containing substantially no benzyl alcohol refers to a color developing solution containing benzyl alcohol in such an amount that the color developing solution has substantially no developing accelerating effect.
  • the color developing solution contains benzyl alcohol in an amount of 1 ml or less, especially 0.1 ml or less, per liter of the color developing solution, and more preferably it contains no benzyl alcohol.
  • processing with a stabilizing solution substituting for water washing refers to a processing for stabilizing processing in which stabilizing processing is performed without sub­stantial water washing processing, or without using flow­ing water immediately after processing with a processing solution having fixing ability. That is, while a large amount of water is required for conventional water washing using flowing or running water which is led into a processing machine, in the present invention, since the stabilizing solution substituting for water washing may be a stabilizing solution or water placed in a processing machine, its amount is extremely small.
  • the processing solution used for said stabilizing processing is called “the stabilizing solution substituting for water washing” (or stabilizing solution for short) and the processing tank is called “a stabilizing bath” or “a stabilizing tank”.
  • the effect of the present invention is great when the stabilizing solution is in 1 to 5 tanks, particularly preferably 1 to 3 tanks. That is, with the same amount of supplementing solution, the effect of the present invention becomes reduced as the number of tanks is increased, because the concentration of contaminating components in the final stabilizing tank is reduced.
  • the surface tension of the stabilizing solution substituting for water washing used in the processing of the present invention is measured according to the general measuring method as described in "Analysis and test Method of Surfactants” (written by Fumio Kitahara, Shigeo Hayano and Ichiro Hara, published by Kodansha K.K., March 1, 1982), in the present invention, the surface tension in the value measured according to the conventional general measuring method at 20°C.
  • the stabilizing solution of the present invention may contain any compound which can give a surface tension of 8 to 50 dyne/cm (mN/m) (20°C), but it is particularly preferable to use at least one compound selected from the compounds of the following formula (II), formula (III) and water-soluble organic siloxane type compounds,
  • A is a monovalent organic group, for example an alkyl group having 6 to 20, preferably 6 to 12, carbon atoms such as hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl.
  • it may be an aryl group substituted with an alkyl group having 3 to 20 carbon atoms, and the substituent is preferably an alkyl group having 3 to 12 carbon atoms such as propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl.
  • the aryl group may be, 29, phenyl, tolyl, xylyl, biphenyl or naphthyl, preferably phenyl or tolyl.
  • the position at which the alkyl group is bonded to the aryl group may be either ortho-, meta-or para-position.
  • B represents an ethylene oxide or propylene oxide mit, and m represents an integer of 4 to 50.
  • X2 represents a hydrogen atom, SO3Y or PO3Y2, and Y represents a hydrogen atom, an alkali metal (eq. Na, K or Li) or an ammonium ion.
  • each of R4, R5, R6 and R7 represents a hydrogen atom, an alkyl group or a phenyl group, and the total number of carbon atom of R4, R5, R6 and R7 is 3 to 50.
  • X3 represents an anion such as a halogen atom, a hydroxyl group, a sulfate group, a carbonate group, a nitrate group, an acetate group or a p-toluenesulfonate group.
  • the water-soluble organic siloxane type compounds used in the present invention may be water-soluble organic siloxane type compounds as described in, for example, Japanese Provisional Patent Publication No. 18333/1972, Japanese Patent Publication No. 51172/1980, Japanese Patent Publication No. 37538/1976, Japanese Provisional Patent Publication No. 62128/1974 and U.S. Patent No. 3,545,970.
  • the compounds represented by the formula (IV) shown below are more preferably used, since they can exhibit well the effects of the present invention.
  • R8 represents a hydrogen atom, a hydroxy group a lower alkyl group, an alkoxy group
  • R9, R 10 and R 11 represents a lower alkyl group (preferably an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl or propyl) and the above R9, R 10 and R 11 may be either the same or different.
  • n represents an integer of 1 to 4
  • each of p and q represents an integer of 1 to 15.
  • the compounds capable of giving a surface tension of 8 to 50 dyne/cm to the stabilizing solution those capable of giving a surface tension of 15 to 40 dyne/cm are particularly preferred.
  • the compounds represented by the above formulae (II), (III) and water-soluble organic siloxane type com­pounds may be used either individually or as a combination. Further, the amounts used are typically within the range of from 0.01 to 20 g per 1 l of the stabilizing solution to exhibit a good effect.
  • the stabilizing solution substituting for water washing contains 0.1 g/l or less of the aldehyde which may have been added at a concentration of 1.5 to 2.0 g/l for the purpose of improvement in storability of the dye image into the final stabilizing solution in the processing step accompanying water washing of the prior art.
  • a concentration of about 0.02 g/l can be regarded as substantially no aldehyde, but it is particularly preferred for there to be no aldehyde at all.
  • aldehyde As the aldehyde to be used in the stabilizing bath in the processing step of the prior art, formaldehyde has been extensively used; other examples of aldehyde include glutaraldehyde, chloral, mucochloric acid, formaldehyde sodium bisulfite and glutaraldehyde sodium bisbisulfite; they will not only deteriorate the storability of the dye image but also give troubles such as precipitation formation in the stabilizing solution substituting for water washing of the present invention.
  • the nucleus represented by Z1 and Z2 may be substituted, and examples of the substituent include halogen atoms, (e.g. chlorine) alkyl groups (e.g. methyl, ethyl) alkoxy groups (e.g. methoxy, ethoxy), alkoxycarbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl), aryl groups (e.g. phenyl) cyano group, etc.
  • halogen atoms e.g. chlorine
  • alkyl groups e.g. methyl, ethyl
  • alkoxy groups e.g. methoxy, ethoxy
  • alkoxycarbonyl groups e.g. methoxycarbonyl, ethoxycarbonyl
  • aryl groups e.g. phenyl
  • the alkyl group and the alkenyl group represented by R1 and R2 may preferably have 5 or less carbon atoms, and R1 and R2 may preferably be alkyl goups
  • the amount of the sensitizing dye reprsented by the above formula (I) added in the emulsion is suitably within the range of from 2 ⁇ 10 -6 to 1 ⁇ 10 -3 mole preferably from 5 ⁇ 10 -6 to 5 ⁇ 10 -4 mole per mole of silver halide.
  • sensitizing dyes are sensitizing dyes having spectral sensitizing ability at the wave­length region which is called green-sensitive or blue-­sensitive, and the light-­sensitive material to be used in the present invention should desirably be spectrally sensitized with the above sensitizing dye within the limit afforded by spectral sensitizing ability ; it is preferred that the sensitizing dye in the sum of green-sensitive emulsion and the blue-sensitive emulsion represents the greater part (50 mole% or more) of the sensitizing dye.
  • mildewproofing agent fungicidal
  • mildew­proofing agents are salicylic acid, sorbic acid, dehydroacetic acid, hydroxy benzoic acid type compounds, alkylphenol type compounds, thiazole type compounds, pyridine type compounds, guanidine type com­pounds, carbamate type compounds, morpholine type com­pounds, quaternary phosphonium type compounds, ammonium type compounds, urea type compounds, isoxazole type compounds, propanolamine type compounds, sulfamide derivatives and amino acid type compounds.
  • hydroxybenzoic acid type compounds include hydroxybenzoic acid and esters of hydroxybenzoic acid such as methyl ester, ethyl ester, propyl ester and butyl ester, preferably n-butyl ester, isobutyl ester and propyl ester of hydroxybenzoic acid, more preferably a mixture of the aforesaid three hydroxybenzoic acid esters.
  • the alkylphenol type compounds are compounds in which the alkyl group has, as the substituent, an alkyl group having 1 to 6 carbon atoms, preferably ortho­phenylphenol and ortho-cyclohexylphenol.
  • the thiazole type compound is preferably 1,2-benzisothiazolin-3-one, 2-­methyl-4-isothiazolin-3-one, 2-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one or (2-(4-thiazolyl)-benzimidazole.
  • pyridine compounds include 2,6-dimethylpyridine, 2,4,6-trimethylpyridine and sodium-2-pyridinethiol-1-oxide, preferably sodium-­2-pyridinethiol-1-oxide.
  • the guanidine type compounds may be specifically cyclohexidine polyhexamethylenebiguanidine hydrochloride and dodecylguanidine hydrochloride, preferably dodecylguanidine and salts thereof.
  • the carbamate type compounds may be exemplified by methyl-1-(butylcabomoyl)-2-benzimidazolecarbamate and methylimidazolecarbamate.
  • Typical examples of the morpholine type compounds are 4-(2-nitrobutyl)morpholine and 4-(3-nitrobutyl)morpholine.
  • the quaternary phosphonium type compounds include tetraalkylphosphonium salt and tetraalkoxyphosphonium salt, preferably tetraalkylphosphonium salt, more preferably tributyl ⁇ tetradecylphosphonium chloride and triphenyl ⁇ nitrophenylphosphonium chloride.
  • quaternary ammonium compounds include benzalkonium salt, benzetonium salt, tetraalkylammonium salt and alkylpyridinium salt, more specifically dodecyldimethylbenzylammonium chloride, dodecyldimethylammonium chloride and laurylpyridinium chloride.
  • Urea type compounds may be exemplified by N-(3,4-dichlorophenyl)-N ⁇ -(4-chlorophenyl) urea and N-(3-trifluoromethyl-4-clorophenyl)-N ⁇ -(4-chlorophenyl) urea.
  • a typical example of the isoxazole type compound is 3-hydroxy-5-methyl-isoxazole.
  • the propanolamine type compounds include amino n-propanols and isopropanols, specifically DL-2-benzyl­amino-1-propanol, 3-diethylamino-1-propanol, 2-dimethyl­amino-2-methyl-1-propanol, 3-amino-1-propanol, isopropanolamine, diisopropanolamine and N,N-dimethylisopropanol-amine.
  • sulfamide derivatives include fluorinated sulfamide, 4-chloro-3,5-dinitro­benzenesulfamide sulfanylamide, acetosulfamine sulfa­pyridine, sulfaguanidine, sulfathiazole, sulfadiadine, sulfameladine, sulfamethadine, sulfaisooxazole homo­sulfamine, sulfisomidine, sulfaguanidine, sulfametizole, sulfapyrazine, phthalisosulfathiazole and succinylsufathiazole.
  • amino acid type compound is N-lauryl- ⁇ -alanine.
  • the compounds preferably used in the present invention are pyridine type compounds, guanidine type compounds and quaternary ammonium type compounds.
  • the amount of the antifungal agent added in the stabilizing solution is typically from 0.002 g to 50 g, preferably from 0.005 to 10 g, per 1 l of the stabilizing solution substituting for water washing.
  • the pH of the stabilizing solution substituting for water washing hard in the present invention is preferably from 3.0 to 10.0, more preferably from 5.0 to 9.5, particularly preferably form 6.0 to 9.0.
  • the pH adjustor which can be present in the stabilizing solution substituting for water washing of the present invention there may be employed any of the alkali agents or acid agents generally known in the art.
  • the present invention can exhibit great effect when the amount of the stabilizing solution added to the stabilizing bath is small, and it is preferred that said supplementd amount should be within the range of from 1 to 50 times the amount brought in from the previous bath per unit area of the light-sensitive material to be processed; the effect of the present invention is particularly marked when said amount is within the range of from 2 to 20 times.
  • the processing temperature for the stabilizing processing is typically 15°C to 60°C, preferably 20°C to 45°C.
  • the processing time is preferably as short as possible from the standpoint ofblock processing, but is generally 20 seconds to 10 minutes, most preferably 1 minute to 3 minutes.
  • the processing time should be shorter for earlier stage tanks and longer for later stage tanks. Particularly it is desirable that processing should be successively performed in a processing time increased by 20 % to 50 % as compared with that in the tank of the preceding stage.
  • the method for feeding the stabilizing solution substituting for water washing in the stabilizing pro­cessing step according to the present invention is preferably to feed the solution to the later bath and permit it to overflow to the earlier bath.
  • the above compounds can be added according to any desired addition method. For example, they can be added into the stabilizing solution as a con­centrated solution. Alternatively the above compounds and other additives may be added to the stabilizing solu­tion substituting for water washing to be fed into the stabilizing tank and this is used as the feed solution for supplementing the stabilizing solution substituting for water washing.
  • the bleaching solution or bleach-fixing solution to be used in the present invention should preferably contain an organic acid ferric complex salt as the bleaching agent.
  • the organic acid for forming the organic acid ferric complex salt includes those set forth below.
  • organic acid ferric complex salt is not limited to these; further a combination of two or more species can be used, if desired.
  • organic acids for forming the organic acid ferric complex salt to be used in the present invention particularly preferable ones include the following:
  • the organic acid ferric complex salt to be used in the present invention may be used in the form of a free acid (hydroacid salt), an alkali metal salt such as a sodium salt, potassium salt or lithium salt, or an ammonium salt, or a water-soluble amine salt such as triethanol amine salt but is preferably a potassium salt, sodium salt or ammonium salt.
  • the bleaching agents are suitably used in amounts of 5 to 450 g/l more preferably 20 to 250 g/l.
  • a solution having a composition contain­ing a silver halide fixing agent other than the above bleaching agent and also containing a sulfite as the preservative, if desired, can be used.
  • a bleach-fixing solution such as a bleach-fix­ing solution comprising a composition in which a small amount of a halide such as ammonium bromide other than the organic acid iron (III) complex salt bleaching agent and the above silver halide fixing agent or a bleach-­fixing solution comprising a composition in which a halide such as ammonium bromide is added in large amounts or further a special bleach-fixing solution comprising a composition in which the organic acid iron (III) complex salt bleaching agent is combined with a large amount of a halide such as ammonium bromide or the like.
  • a bleach-fixing solution such as a bleach-fix­ing solution comprising a composition in which a small amount of a halide such as ammonium bromide other than the organic acid iron (III) complex salt bleaching agent and the above silver halide fixing agent
  • a bleach-­fixing solution comprising a composition in which a halide such as ammonium bromide is added in large
  • hydrochloric acid hydrobromic acid lithium bromide, sodium bromide, potassium bromide sodium iodide, potassium iodide and ammonium iodide may be used.
  • the silver halide fixing agent contained in the fixing solution or bleach-fixing solution there may be employed compounds capable of forming water-soluble complex salts by reaction with silver halide as used in conventional fixing processing, including thiosulfates such as potassium thiosulfate, sodium thiosufate and ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, thiourea and thioether.
  • thiosulfates such as potassium thiosulfate, sodium thiosufate and ammonium thiosulfate
  • thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate
  • thiourea and thioether thioether.
  • the bleach-fixing solution can contain various kinds of pH buffering agents such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide, used either alone or in combination of two or more. Further, various fluorescent brighteners, defoaming agents or surfactants may be included. Also, organic chelating agents such as hydroxylamine, hydrazine and aminopolycarboxylic acid, stabilizers such as nitroalcohol or nitrate, or organic solvents such as methanol, dimethylsufonamide and dimethyl sulfoxide may be incorporated or appropriate.
  • pH buffering agents such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide, used either alone or in combination of two or more.
  • the bleach-fixing solution is generally used at a pH of 4.0 or higher, generally from pH 5.0 to pH 9.5, desirably from pH 6.0 to pH 8.5, most preferably at pH 6.5 to pH 8.5.
  • the processing temperature is suitably 80°C or lower, and lower by 3°C or more, preferably 5°C or more than the processing solution temperature in the color developing tank, desirably 55°C or lower while suppressing evaporation etc.
  • the light-sensitive material to be used in the method of the present invention comprises silver halide emulsion layers and non-light-sensitive layers (non-­emulsion layers) coated on a support.
  • the silver halide emulsion any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide or silver chloroiodobromide may be used.
  • all couplers and additives known in the field of photography can be present.
  • yellow dye forming couplers there may be included as appropriate yellow dye forming couplers, magenta dye forming couplers cyan dye forming couplers stabilizers, sensitizing dyes, gold compounds, high boiling point organic solvents, antifog­gants, dye image fading preventives, color staining preventives fluorescent brighteners, antistatic agents, film hardeners, surfactants, plasticizers, wetting agents and UV-ray absorbers, for example.
  • the light-sensitive material to be used in the method of the present invention can be prepared by coating the respective constituent emulsion layers and non-light-sensitive layers, containing various additives for photography as mentioned above, if necessary, on a support, for example one treated with a corona discharging treatment, flame treatment or UV-ray irradiation treatment, or alternatively through an intermediary subbing layer or intermediate layer on the support.
  • the support advantageously used is, for example, baryta paper, polyethylene coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate or polyester film such as polyethylene terephthalate, polyamide film, polycarbonate film or polystyrene film.
  • the above silver halide emulsion layers and non-light-sensitive layers are generally in the form of hydrophilic colloid layers containing a hydrophilic binder.
  • a hydrophilic binder gelatin or gelatin derivatives such as acylated gelatin, guanidylated gelatin, phenylcarbamylated gelatin, phthalated gelatin, cyanoethanolated gelatin and esterified gelatin may be used.
  • the film hardening agent for hardening the hydrophilic colloid layer it is possible to use, for example, chromium salts (chrome alum, chromium acetate) aldehydes (formaldehyde, glyoxal, glutaraldehyde), N-methylol compounds (dimethylolurea, methylol-­dimethylhydantoin), dioxane derivatives (2,3-dihydroxydioxane), active vinyl compounds (1,3,5-triacryloyl-­hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol), active halide compounds (2,4-dichloro-6-hydroxy-s-triazine) and mucohalogenic acid (mucochloric acid, mucophenoxychloric acid), either alone or in combination.
  • chromium salts chrome alum, chromium acetate
  • the present invention is particularly effective in the case of the so-called oil protect type in which a dispersion of a coupler in a high boilling point organic solvent is present.
  • the effect of the present invention is great when using, as such a high boiling point organic solvent, organic acid amides, carbamates, esters, ketones and urea derivatives, particularly phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, diamyl phthalate, dinonyl phthalate and diisodecyl phthalate ; phosphoric acid esters such as tricresyl phosphate, triphenyl phosphate, (tri-(2-ethylhexyl)phosphate and trinonyl phosphate; sebacic acid esters such as dioctyl sebacate, di-(2-eth
  • the layer constitution of the light-sensitive material to be used in the present invention can be one known in color negative film, color paper and reversal color film.
  • it can be in the form of a blue-sensitive silver halide emulsion layer containing a yellow dye forming coupler, a green-­sensitive silver halide emulsion layer containing a magenta dye forming coupler and a red-sensitive silver halide emulsion layer containing a cyan dye forming coupler on one surface of a support (these respective color-sensitive layers may consist of one layer or two or more layers).
  • R1 represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, each of which may have a substituent
  • R2 represents a cyano group or an N-phenylcarbamyl group which may have a substituent
  • Y represents -CO-, -SO2-, a nitrogen atom, an oxygen atom, a sulfur atom, a carbon atom having no oxygen atom bonded with a double bond
  • Z represents a group of non-metallic atoms necessary for the completion of a 4- to 6-membered nitrogen containing heterocyclic nucleus.
  • yellow coupler represented by the above formula (V) which can be used include those as described in Japanese Provisional Patent Publications No. 85426/1978, No. 102636/1976 and No. 2613/1972.
  • yellow couplers can be synthesized according to the general synthetic methods described in West German OLS's No. 20 57 941 and No. 21 63 812, Japanese Provisional Patent Publications No. 26133/1972, No. 29432/1973, No. 65231/1975, No. 3631/1976, No. 50734/ 1976, No. 102636/1976, No. 66834/1973, No. 66835/1973, No. 94432/1973, No. 1229/1974, No. 10739/1974 and Japanese Patent Publication No. 25733/1976.
  • the effect of the present invention can be exhibited when the total dried film thickness of the light-sensitive silver halide emulsion layers on one surface of a support is 10 ⁇ m or more, and the effect of the present invention is particularly remarkable when it is 30 ⁇ m or less, particularly within the range of from 15 to 25 ⁇ m. If the total dried film thickness is less than 10 ⁇ m, the improve went in staining becomes small.
  • aromatic primary amine color forming agents are normally used and various known compounds widely used in color photographic process can be included in said developing agent.
  • These developing agents include aminophenol type and p-phenylenediamine type derivatives.
  • These compounds are used generally in the form of a salt such as hydrochloride or sulfate, since they are more stable than in the free state.
  • These compounds are used generally at a concentration of 0.1 g to 30 g per 1 l of the color developing solution, preferably at a concentration of 1 g to 1.5 g per 1 l of color developing solution.
  • aminophenol type developing agent examples include o-aminophenol, p-aminophenol, 5-amino-2-hydroxytoluene, 2-amino-3-hydroxytoluene and 2-hydroxy-3-amino-1,4-dimethylbenzene.
  • Particularly useful aromatic primary amine type color developing agents are N,N ⁇ -dialkyl-p-phenylenedi­amine type compounds of which the alkyl group and phenyl group may be substituted with any desired substituent.
  • examples of particularly useful compounds include N,N ⁇ -diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-­p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-­dodecylamino)-toluene, N-ethyl-N- ⁇ -methanesulfoneamido­ethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N- ⁇ -­hydroxyethylaminoaniline, 4-amino-3-methyl-N,N ⁇ -diethylaniline and 4-amino-N-(2-meth
  • the color developing solution contains substantially no benzyl alcohol, i.e. at a concentration of 1 ml/l or less; it is usually present concentration of 10 to 20 ml/l in a conventional color developing solution.
  • a concentration of about 05. ml/l comes within the region containing substantially no benzyl alcohol, but it is particularly preferred for there to be no benzyl alcohol at all.
  • the color developing solution in addition to the above aromatic primary amine type color developing agent, various components generally added to color developing solutions, for example, alkali agents such as sodium hydroxide, sodium carbonate and potassium carbonate, alkali metal thiocyanates, alkali metal halides, water softeners and thickeners, can be incorporated as desired.
  • alkali agents such as sodium hydroxide, sodium carbonate and potassium carbonate
  • alkali metal thiocyanates alkali metal halides
  • water softeners and thickeners water softeners and thickeners
  • the soluble silver complex salt contained in the stabilizing solution substituting for water washing and the bleach-fixing solution to be used in the processing method of the present invention may be subjected to silver recovery according to a known method.
  • a known method for example, it is possible to utilize the electrolytic method (disclosed in French Patent No. 2,299,667), the precipitation method (disclosed in Japanese Provisional Patent Publication No. 73037/1977 and West German Patent No. 23 31 220), the ion exchange method (disclosed in Japanese Provisional Patent Publication No. 17114/1976 and West German Patent No. 25 48 237) and the metal substitution method (disclosed in U.K. Patent No. 1,353,805).
  • the processing method of the present invention is advantageously applied for processing color negative film, reversal color film, color negative paper, color positive paper and reversal color paper.
  • processing steps to which the present invention can be applied particularly effectively include the following (1) and (2):
  • the polyethylene coated paper used was prepared by forming a coated layer of a composition comprising a mixture of 200 parts by weight of a polyethylene having an average molecular weight of 100,000 and a density of 0.95 and 20 parts by weight of a polyethylene having an average molecular weight of 2,000 and a density of 0.80 mixed with 6.8% by weight of an anatase type titanium oxide according to the extrusion coating method to a thickness of 0.035 mm onto the surface of a pure paper with a weight of 170 g/m2 and providing a coated layer with a thickness of 0.040 mm only of polyethylene on the back surface. After application of a pre-treatment by corona discharging on the polyethylene coated surface on the support surface, the respective layers were coated successively.
  • This is a blue-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion contain­ing 80 mole % of silver bromide; said emulsion contains 450 g of gelatin per mole of silver halide, is sensitized with 2.5 ⁇ 10 -3 mole of a sensitizing dye of the present invention (exemplary compound I-12) per mole of silver halide (isopropyl alcohol is used as the solvent), contains 200 mg/m2 of 2,5-di-t-butyl hydro­quinone dispersed by dissolving it dibutylphthalate and 2 ⁇ 10 -3 mole per mole of silver halide of Y - 5 as the yellow coupler, and is coated to a silver quantity of 500 mg/m2.
  • This is a green-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion contain­ing 85 mole % of silver bromide, and said emulsion contains 450 g of gelatin per mole of silver halide, is sensitized with 2.5 ⁇ 10 -3 mole of a sensitizing dye having the following structure: per mole of silver halide, contains 150 mg/m2 of 2,5-di-t-butylhydroquinone dispersed by dissolving it in a solvent comprising a mixture of 2:1 of dibutylphthalate and tricresyl phosphate and 1.5 ⁇ 10 -1 mole of 1-(2,4,6-tri­chlorophenyl)-3-(2-chloro-5-octadecenylsuccinimido­anilino)-5-pyrazolone per mole of silver halide as the magenta coupler, and is coated to a silver quantity of 400 mg/m2. Also, as
  • This is a red-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion contain­ing 85 mole % of silver bromide, and said emulsion contains 500 g of gelatin per mole of silver halide, is sensitized with 2.5 ⁇ 10 -3 mole of a sensitizing dye having the following structure: per mole of silver halide, contains 55 mg/m2 of 2,5-di-­t-butylhydroquinone dispersed by dissolving it in dibutyl phthalate and 3.5 ⁇ 10 -1 mole of 2,4-dichloro-3-methyl-6-[y-(2,4-diamylphenoxy)butyramido]phenol per mole of silver halide as the cyan coupler, and is coated to a silver quantity of 400 mg/m2.
  • This is a gelatin layer and is coated to a gelatin quantity of 1000 mg/m2.
  • the silver halide emulsions used for the respec­tive light-sensitive emulsion layers were prepared according to the method described in Japanese Patent Publication No. 7772/ 1971, and each of them was chemically sensitized with sodium thiosulfate pentahydrate and incorporated with 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene as the stabilizer, bis(vinylsulfonylmethyl)ether as the film hardener and saponin as the coating aid.
  • the film thickness after coating and drying as described above was measured to be 17 ⁇ m.
  • the color paper prepared according to the above method was exposed to light and then the experiments were conducted with the use of the following processing steps and processing solutions.
  • Processing solution compositions ⁇ Color developing tank solution> (made up to 1 liter with addition of water, and adjusted to pH 10.20 with potassium hydroxide or sulfuric acid).
  • ⁇ Color developing supplementing solution> (made up to 1 liter with addition of water, and adjusted to pH 10.70 with potassium hydroxide).
  • ⁇ Bleach-fixing tank solution> ⁇ Bleach-fixing supplementing solution A> (made up to the total amount of 1 liter with addition of water; this solution has a pH of 6.7 ⁇ 0.1).
  • ⁇ Bleach-fixing supplementing solution B> made up to the total amount of 1 liter with addition of water; this solution has a pH of 5.3 ⁇ 0.1).
  • ⁇ Stabilizing tank solution substituting for water washing and supplementing solution> (made up to 1 liter with addition of water, and adjusted to pH 7.0 with sulfuric acid).
  • An automatic developing machine was filled with the above color developing tank solution, bleach-fixing tank solution and the stabilizing tank with tap water and continuous processing was performed by processing color paper while supplementing the color developing supple­menting solution and the bleach-fixing supplementing solutions A and B as described above through quantitating cups at intervals of 3 minutes.
  • the amounts supplemented were, per 1 m2 of color paper, 190 ml for the color developing tank, and 50 ml each for the bleach-fixing supplementing solutions A and B for the bleach-fixing tank, and 20 l of tap water were added (run in) to the stabilizing processing bath per 1 m2.
  • the first tank to the third tank in the direction of the flow of the light-sensitive material constituted the stabilizing tank, and an multitank countercurrent system was employed in which supplementing was conducted in the final tank, the overflow from the final tank was permitted to flow into the tank in the preceding stage, and further the overflow from this stage was permitted to flow into the tank in the stage preceding thereto.
  • a light-sensitive material was prepared in entirely the same manner except for removing the sensitizing dye (exemplary compound I-12) added in the first layer; using this light-sensitive material, processing as shown in Table 1 was conducted similarly to Experiments 1 to 9.
  • the present invention is particularly effective when the light-sensitive materials contain a sensitizing dye represented by the formula (I).
  • the sixth layer was coated after coating of the first layer to prepare a light-sensitive material in which the second layer to the fifth layer were omitted.
  • light-sensitive materials were prepared by varying the amount of the first layer coated to 2-fold, 3-fold, 4-fold, 5-fold and 6-fold. These dried film thicknesses were found to be 7.1 ⁇ m, 12.8 ⁇ m, 18.4 ⁇ m, 24.2 ⁇ m, 29.9 ⁇ m and 35.7 ⁇ m, respectively.
  • the present invention is effective when the light-sensitive material has a dried film thickness of 10 ⁇ m or more, particularly effective in the range from about 10 ⁇ m to 30 ⁇ m and most effective in the range from about 15 ⁇ m to 25 ⁇ m.
  • a halation preventive layer and a gelatin layer were provided, and a red-sen­sitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver and a blue-sensitive silver halide emulsion layer were coated thereon to a total silver quantity of 70 mg/100 cm2.
  • the above emulsion layers comprise a silver iodo­bromide containing about 4.5 mole % of silver iodide and, in this case, Y - 12 was employed as the yellow coupler in the blue-sensitive silver halide emulsion layer; 1-(2,4,6-trichlorophenyl)-3- ⁇ [ ⁇ -(2,4-di-t-amylphenoxy)acet­amido]-benzamido ⁇ -3-pyrazolone and 1-(2,4,6-trichloro­phenyl)-3- ⁇ [ ⁇ -(2,4-di-t-amylphenoxy)acetamido]benzamido ⁇ -­4-(4-methoxyphenylazo)-5-pyrazolone were employed as the magenta coupler in the green-sensitive silver halide emulsion layer; 1-hydroxy-N- ⁇ -(2,4-t-amylphenoxy)butyl ⁇ -­2-naphthoamide was employed as the
  • the color negative film thus obtained was found to have a dried film thickness of 23 ⁇ m.
  • Formalin (35% aqueous solution) 7.0 ml (made up to 1 liter with addition of water).
  • An automatic developing machine was filled with the above color developing tank solution, the bleach-fix­ing tank solution, the washing water and the stabilizing tank solution, and continuous processing was performed by processing the color negative film while supplementing the above color developing supplementing solution, the bleach-fixing supplementing solution and the stabilizing supplementing solution through a quantitating cup at intervals of 3 minutes.
  • the amounts supplemented were, per 1 m2 of the color negative film, 1475 ml for the color developing tank, 926 ml for the bleach-fixing tank and 926 ml of the stabilizing supplementing solution for the stabilizing processing tank, respectively.
  • the amount of the washing water in the washing step was 30 l/m2.
  • a multi-tank countercurrent system was used, in which the first tank to the third tank in the direction of the flow of the light-sensitive material constituted the stabilizing tank, and supplementing was performed from the final tank, with the overflow from the final tank flowing into the tank in the preceding stage and further the overflow from this stage flowing into the tank in the stage preceding thereto.
  • the amount supplemented of the stabilizing solution substituting for water washing was the same as the stabilizing solution in Experiment 12.
  • Stabilizing tank solution substituting for water washing and supplementing solution (made up to 1 liter with water, and adjusted to pH 7.0 with sulfuric acid or potassium hydroxide).

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Claims (13)

1. Procédé de traitement d'un matériau photographique photosensible couleur, à base d'halogénure d'argent, comprenant les opérations consistant à soumettre à une exposition d'image le matériau photographique photosensible couleur, à base d'halogénure d'argent, ayant une épaisseur totale de film sec, des couches d'émulsion photosensible d'halogénure d'argent et des couches non photosensibles, de 10 µm ou plus, sur une surface d'un support, à traiter le matériau exposé à l'aide d'un développeur formateur de couleur contenant au plus 1 ml/litre d'alcool benzylique, ensuite à traiter le matériau à l'aide d'une solution de traitement ayant une aptitude au fixage, et ensuite, au lieu d'un lavage à l'eau, à traiter le matériau à l'aide d'une solution stabilisante ayant une tension superficielle de 8 à 50 dyn/cm (mN/m) à 20°C et contenant au plus 0,1 g/g d'un composé aldéhyde, puis à sécher.
2. Procédé de traitement d'un matériau photographique photosensible couleur, à base d'halogénure d'argent, selon la revendication 1, dans lequel ledit matériau photographique photosensible couleur, à base d'halogénure d'argent, contient un colorant sensibilisant représenté par la formule suivante :
Figure imgb0047
 où Z₁ et Z₂ représentent, chacun indépendamment, un groupe d'atomes nécessaires pour compléter un noyau benzoxazole, naphtoxazole, benzothiazole, naphtothiazole, benzosélénazole, naphtosélénazole, benzoimidazole, naphtoimidazole, pyridine ou quinoléine, R₁ et R₂ représentent chacun indépendamment un groupe alkyle, un groupe alcényle ou un groupe aryle, R₃ représente un atome d'hydrogène, un groupe méthyle ou un groupe éthyle et X₁⁻ représente un anion et ℓ représente 0 ou 1.
3. Procédé de traitement d'un matériau photographique photosensible couleur, à base d'halogénure d'argent, selon la revendication 2, dans lequel la quantité de colorant sensibilisant de formule (I) ajoutée à l'émulsion est de 2 × 10-6 à 1 × 10-3 mole par mole d'halogénure d'argent.
4. Procédé de traitement d'un matériau photographique photosensible couleur, à base d'halogénure d'argent, selon la revendication 3, dans lequel la quantité de colorant sensibilisant de formule (I) ajoutée à l'émulsion est de 5 × 10-6 à 5 × 10-4 mole par mole d'halogénure d'argent.
5. Procédé de traitement d'un matériau photgraphique photosensible couleur, à base d'halogénure d'argent, selon l'une quelconque des revendications 1 à 4, dans lequel ladite solution stabilisante est présente dans 1 à 5 cuves.
6. procédé de traitement d'un matériau photographique photosensible couleur, à base d'halogénure d'argent, selon l'une des quelconque des revendications 1 à 5, dans lequel ladite solution stabilisante présente une tension superficielle de 15 à 40 dyn/cm (mN/m).
7. Procédé de traitement d'un matériau photographique photosensible couleur, à base d'halogénure d'argent, selon l'une quelconque des revendications 1 à 6, dans lequel ladite solution stabilisante contient au moins un composé de formule (II) ou (III), ou un composé du type siloxane organique hydrosoluble:
Figure imgb0048
 où A est un groupe alkyle ayant 6 à 20 atomes de carbone ou un groupe aryle substituté par un groupe alkyle ayant 3 à 20 atomes de carbone; B représente une unité oxyde d'éthylène ou oxyde de propylène; m représente un nombre entier de 4 à 50; et X₂ représente un atome d'hydrogène, SO₃Y ou PO₃Y₂, où Y représente un atome d'hydrogène, un métal alcalin ou un ion ammonium,
Figure imgb0049
 où R₄, R₅, R₆ et R₇ représentent chacun indépendamment un atome d'hydrogène, un groupe alkyle ou un groupe phényle, et le nombre total des atomes de carbone de R₄, R₅, R₆ et R₇est de 3 à 50; X₃ représente un anion d'un atome d'halogène, un groupe hydroxyle, un groupe sulfate, un groupe carbonate, un groupe nitrate, un groupe acétate ou un groupe p-­toluènesulfonate
8. Procédé de traitement d'un matériau photographique photosensible couleur, à base d'halogénure d'argent, selon la revendication 7, dans lequel la quantité dudit composé est de 0,01 à 20 g par litre de la solution stabilisante.
9. Procédé de traitement d'un matériau photographique photosensible couleur, à base d'halogénure d'argent, selon l'une quelconque des revendications 1 à 8, dans lequel ladite solution de développement couleur ne contient pas d'alcool benzylique.
10. Procédé de traitement d'un matériau photographique photosensible couleur, à base d'halogénure d'argent, selon l'une quelconque des revendications 1 à 9, dans lequel ladite solution de développement couleur ne contient pas d'aldéhyde.
11. Procédé de traitement d'un matériau photographique photosensible couleur, à base d'halogénure d'argent, selon l'une quelconque des revendications 1 à 10, dans lequel la quantité de ladite solution stabilisante ajoutée au bain de stabilisation est de 1 à 50 fois la quantité amenée depuis un bain précédent, par unité de surface du matériau photosensible à traiter.
12. Procédé de traitement d'un matériau photographique photosensible couleur, à base d'halogénure d'argent, selon la revendication 11, dans lequel ladite quantité est de 2 à 20 fois supérieure.
13. Procédé de traitement d'un matériau photographique photosensible couleur, à base d'halogénure d'argent, selon l'une quelconque des revendications 1 à 12, dans lequel le traitement est effectué dans une série de cuves, le temps de traitement étant prolongé de 20% à 50% par rapport à celui de la précédente cuve.
EP86307394A 1985-09-27 1986-09-25 Procédé de traitement d'un matériau photographique couleur à l'halogénure d'argent sensible à la lumière Expired - Lifetime EP0217643B1 (fr)

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JPS6278556A (ja) * 1985-10-01 1987-04-10 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法及び水洗代替安定液
JPH0614180B2 (ja) * 1986-01-30 1994-02-23 富士写真フイルム株式会社 カラ−画像形成法
JP2521436B2 (ja) * 1986-05-23 1996-08-07 コニカ株式会社 ハロゲン化銀写真感光材料の処理方法
JPH07117708B2 (ja) * 1987-11-12 1995-12-18 コニカ株式会社 長期処理安定性を有する写真処理剤及び写真感光材料の処理方法
US4980272A (en) * 1988-07-15 1990-12-25 Konica Corporation Method and a solution for processing a photosensitive silver halide color photographic materials
JPH02195349A (ja) * 1989-01-24 1990-08-01 Konica Corp ハロゲン化銀カラー写真感光材料の処理方法
JPH0367257A (ja) * 1989-04-28 1991-03-22 Konica Corp ハロゲン化銀写真感光材料用安定液及び該安定液を用いたハロゲン化銀写真感光材料の処理方法
WO1991005289A1 (fr) * 1989-09-29 1991-04-18 Eastman Kodak Company Bain de lavage utilise dans le traitement photographique
US5583198A (en) * 1989-12-22 1996-12-10 Commonwealth Scientific And Industrial Research Organization Amino acids, peptides or derivatives thereof coupled to fats
JP2942963B2 (ja) * 1990-07-03 1999-08-30 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
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
EP0476434A3 (en) * 1990-09-05 1992-05-06 Konica Corporation Method for processing silver halide color photographic light sensitive materials
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
EP0529794A1 (fr) * 1991-07-26 1993-03-03 Konica Corporation Procédé de stabilisation sans formaldéhyde
EP0593734B1 (fr) * 1992-05-12 1997-12-03 Eastman Kodak Company Additifs pour solution aqueuse de stabilisation photographique
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

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JPS578543A (en) * 1980-06-18 1982-01-16 Konishiroku Photo Ind Co Ltd Processing method for color photographic sensitive silver halide material
JPS58134636A (ja) * 1982-02-05 1983-08-10 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料処理用画像安定化液
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JPS6064349A (ja) * 1983-09-20 1985-04-12 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料用最終処理液
JPH0612433B2 (ja) * 1983-12-26 1994-02-16 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
JPS60239749A (ja) * 1984-05-15 1985-11-28 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
JPS60260952A (ja) * 1984-06-08 1985-12-24 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料の処理方法及び処理液
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