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EP0243168B1 - Procédé de traitement d'un matériau photosensible à l'halogénure d'argent - Google Patents

Procédé de traitement d'un matériau photosensible à l'halogénure d'argent Download PDF

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Publication number
EP0243168B1
EP0243168B1 EP19870303532 EP87303532A EP0243168B1 EP 0243168 B1 EP0243168 B1 EP 0243168B1 EP 19870303532 EP19870303532 EP 19870303532 EP 87303532 A EP87303532 A EP 87303532A EP 0243168 B1 EP0243168 B1 EP 0243168B1
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EP
European Patent Office
Prior art keywords
group
nitrogen
silver halide
ring
color
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP19870303532
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German (de)
English (en)
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EP0243168A3 (en
EP0243168A2 (fr
Inventor
Kazuhiro Murai
Keiji Ohbayashi
Kaoru Onodera
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of EP0243168A2 publication Critical patent/EP0243168A2/fr
Publication of EP0243168A3 publication Critical patent/EP0243168A3/en
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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
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/16—Methine and polymethine dyes with an odd number of CH groups with one CH group

Definitions

  • the present invention relates to a method for processing silver halide photo-sensitive materials, in particular to a method for fast and stably processing silver halide photo-sensitive materials which is capable of preventing fog from increasing.
  • a silver halide color photo-sensitive material is provided with three kinds of silver halide color emulsion layer each selectively and spectrometrically sensitized so as to be sensitive to blue light, green light and red light, respectively, applied on a support member.
  • a color negative photo-sensitive material is generally provided with a blue light-sensitive emulsion layer, a green lightsensitive emulsion layer and a red light-sensitive layer applied in this order from the side exposed.
  • a bleachable yellow filter layer is disposed between the blue light-sensitive emulsion layer and the green light-sensitive emulsion layer to absorb blue light passing through the blue light-sensitive emulsion layer.
  • each emulsion layer is provided with other intermediate layers and a protective layer as the outermost layer for various purposes.
  • a color printing paper photo-sensitive material is generally provided with a red light-sensitive emulsion layer, a green light-sensitive emulsion layer and a blue light-sensitive emulsion layer applied in this order from the side exposed.
  • the color printing paper photo-sensitive material is provided with an intermediate layer, a protective layer and the like in addition to an ultraviolet ray-absorption layer, in the same manner as in the color negative photo-sensitive material. It has been known that these emulsion layers can be arranged in a manner other than that described.
  • a sensitive emulsion layer consisting of two layers having a sensitivity in substantially the same wave length range to light of each color is used as the emulsion layer.
  • a sensitive emulsion layer consisting of two layers having a sensitivity in substantially the same wave length range to light of each color is used as the emulsion layer.
  • silver halide photo-sensitive materials for example an aromatic primary amine color developing agent is used as color developing agent.
  • Silver halide particles exposed are developed and a reaction between an oxidized product of the color developing agent and a dye forming coupler leads to the formation of a dye image.
  • a cyan, magenta or yellow dye-forming coupler is used, respectively.
  • a silver halide color photo-sensitive material (hereinafter referred to as a color sensitive material), which can be fast and stably processed, giving a high image quality, without being expensive, has been desired.
  • a fast processable silver halide color photo-sensitive material has been desired.
  • a silver halide photo-sensitive material is sujected to a continuous process in an automatic developing machine in a developing shop but there has been a need to develop and provide the finished material to the user within the same day so as to improve the service for the user. Recently, it is being required even to provide the finished material to the user within a few hours of receipt. Thus, the rapid development of an increasingly fast processable silver halide color photo-sensitive material is desired.
  • the speed-up of the color developing process can be achieved also by processing a silver halide photo-sensitive material containing silver halide particles substantially comprising silver chloride in the presence of a bromide ion in a color developer.
  • the hydroxyl amine salt serves as a superior preservative for preventing the color developing agent from being oxidized with air, particularly in the event that it is used together with sulfite salts.
  • a color sensitive material is processed with a color developer containing benzyl alcohol at pH of about 10, its influence upon the coloring capacity is remarkably small.
  • hydroxyl amine derivatives having at least one substituent on the nitrogen atom are useful as compounds having a sufficient preservative capacity without significantly reducing the coloring capacity even in the event that the concentration of color developer is sufficiently high and benzyl alcohol is not present.
  • the dye image of a silver halide photo-sensitive material can reach the maximum density quickly but a disadvantage occurs in that the fog is apt to be generated when the dye image of the silver halide photo-sensitive material has reached the maximum density.
  • mercapto compounds are preferably used as fog inhibitors. Although mercapto compounds are effective as fog inhibitors, they exhibit an insufficient effect such that fog is apt to be generated in the event that the color developing process is speeded up in the above described manner.
  • the present invention provides a method of processing a light-sensitive silver halide color photographic material which comprises processing an image-wise exposed light-sensitive silver halide color photographic material comprising a support and, provided thereon, at least one silver halide emulsion layer containing silver halide grains which are sensitized with a sensitizing dye represented by general formula 111;
  • Z 1 and Z 2 are independently represent a group of atoms necessary to complete a heterocyclic ring which is a thiazole, a benzothiazole, a selenazole, a benzoselenazole, a naphthoselenazole, a benzimidazole, a naphthoimidazole, a pyridine or a quinoline ring, wherein said heterocyclic ring may have a substituent;
  • R 1 and R 2 are independently an optionally substituted alkyl, alkenyl or aryl group;
  • R 3 is a hydrogen atom, a methyl group
  • US-A-4252892 and Research Disclosure 16480121 page 61 disclose the antioxidant preservative properties of various hydroxylamine derivatives.
  • FR-A-1080483 and FR-A-1210904 disclose that certain nitrogen containing heterocyclic mercapto compounds have antifoggant properties.
  • US-A-3752670 discloses the use of such heterocyclic mercapto compounds to improve the photographic recordal of objects submerged in water.
  • Heterocyclic rings expressed by Z 1 and 2 2 in said general formula [I] preferably include a thiazole, a benzothiazole, a naphthothiazole ring, a selenazole, a benzoselenazo and a naphthoselenazo ring more preferably a thiazole, a bensothiazole, a selenazole, a benzoselenazole or a naphthoselenazole ring, and most preferably a benzothiazole ring.
  • These rings may be substituted by various substituents, preferably one or more halogen atoms, hydroxyl groups, cyano groups, aryl groups, alkyl groups, alkoxy groups or alkoxycarbonyl groups, more preferably halogen atoms, cyano groups, aryl groups, C, to C 6 alkyl groups or C, to C 6 alkoxy groups, and most preferably halogen atoms, cyano groups, methyl groups, ethyl groups, methoxy groups and ethoxy groups.
  • substituents preferably one or more halogen atoms, hydroxyl groups, cyano groups, aryl groups, alkyl groups, alkoxy groups or alkoxycarbonyl groups, more preferably halogen atoms, cyano groups, aryl groups, C, to C 6 alkyl groups or C, to C 6 alkoxy groups, and most preferably halogen atoms, cyano groups, methyl groups, ethyl groups, meth
  • R 1 and R 2 are alkyl groups, alkenyl groups or aryl groups.
  • alkyl groups expressed by R 1 and R 2 are preferably C 1 to C 6 alkyl groups, and most preferably an ethyl group, a propyl group or a butyl group.
  • These alkyl groups may be substituted by various kinds of substituent, preferably a carboxylic group and a sulfonic group i.e.
  • R 1 and R 2 are carboxyalkyl or sulfoalkyl.
  • salts may be formed e.g. with alkaline metal ions and an ammonium ion.
  • At least one of R 1 and R 2 is preferably an alkyl group substituted by a sulfonic group.
  • the alkenyl groups include an allyl group while the aryl groups include a phenyl group.
  • R 3 is a hydrogen atom, a methyl group or an ethyl group, preferably a hydrogen atom.
  • X is an anion, preferably a chloride ion, a bromide ion, an iodide ion or a p-toluene sulfonic acid ion.
  • l is an integer of 1.
  • l is 0 in the event that at least one of R 1 and R 2 is a group having a minus electric charge itself such as a carboxylic group and a sulfonic group.
  • Typical examples of a sensitizing dye expressed by the general formula [I] are given below.
  • the sensitizing dye expressed by said general formula [I] according to the present invention can be easily synthesized in accordance with methods disclosed in for example British patent 660,408 and USP 3,149,105.
  • the sensitizing dye expressed by said general formula [I] is preferably dissolved in an organic solvent, such as methanol and ethanol, which can be optionally blended with water.
  • the sensitizing dye may be added at any step in the process of manufacturing an emulsion, preferably in the chemical ageing step.
  • the quantity of the sensitizing dye to be added is dependant upon the nature of the sensitizing dye and the nature of the silver halide emulsion but the sensitizing dye is preferably added in an amount of 0.01 to 0.5 g per mol of silver halide.
  • hydroxyl amine derivatives used in the present invention are preferably added to the color developer solution, a system, in which the hydroxyl amine derivative is previously incorporated in the sensitive material and the hydroxyl amine derivative of the present invention is supplied in the color developer by continuously processing the sensitive material, is also possible.
  • the hydroxyl amine derivative represented by general formula [II] includes, as preferable examples, those compounds listed below:
  • the hydroxylamine derivative can be used in the form of an acid salt such as a hydrochloride, sulfate, p-toluenesulfate, oxalate, phosphate or acetate.
  • an acid salt such as a hydrochloride, sulfate, p-toluenesulfate, oxalate, phosphate or acetate.
  • Preferred hydroxylamine derivatives include N,N-dimethylhydroxylamine, N,N-diethylhydroxylamine, N,N-dipropylhydroxylamine and N,N-dibutylhydroxylamine, and water soluble acid salts thereof.
  • the hydroxyl amine derivative or acid salt thereof is typically used in an amount of 0.5 to 50 g, preferably 1 to 20 g, based on one liter of the color developer.
  • the above described hydroxylamine derivative can be used together with hydroxylamine salts as far as the effects of the present invention are not spoiled, the latter is typically added in an amount of 1 g or less, preferably 0.5 g or less, based on 1 liter of the color developer (calculated as NH 2 0H.1/2H 2 SOo).
  • the hydroxylamine derivative when the hydroxylamine derivative is incorporated in the photo-sensitive material and the color developer is supplied with it by continuously processing the photo-sensitive material, the hydroxylamine is generally used in an amount of 0.05 to 5 g, preferably 0.1 to 2 g, per 1 M 2 of the photo-sensitive material.
  • Heterocyclic rings in the nitrogen-containing heterocyclic mercapto compounds used in the present invention are preferably selected from an imidazoline ring, an imidazole ring, an imidazolone ring, a pyrazoline ring, a pyrazole ring, a pyrazolone ring, an oxazoline ring, an oxazole ring, an oxazolone ring, a thiazoline ring, a thiazole ring, a thiazolone ring, a selenazoline ring, a selenazole ring, a selenazolone ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, a tetrazole ring, a benzimidazole ring, a benztriazole ring, an indazole ring, a benzoxaxole ring, a benzthi
  • mercapto oxadiazole mercapto thiadiazole
  • mercapto triazole expressed by the following general formula [III] and mercapto tetrazole are preferably used: wherein X is a hydrogen atom, an amino group, a hydroxyl group, a hydrazino group, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a -NHCOR 31 group, a -NHSO 2 R 31 group or a -R 32 S group; Y is a hydrogen atom, an amino group, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a -CONHR 33 group, a -COR 34 group, a -NHCOR 35 group or a -NHSOzRs group; Z is a nitrogen atom, sulfur atom or oxygen atom
  • the alkyl group expressed by X and Y is preferably one containing 1 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group or a benzyl group.
  • the cycloalkyl group is preferably a cyclohexyl group or a cyclopentyl group.
  • the alkenyl group is preferably one containing 2 to 18 atoms such as an allyl group or an octenyl group.
  • the aryl group is, for example, a phenyl group or a naphthyl group.
  • the alkyl group expressed by R 31 , R 32 , R 33 , R 34 and R 35 is preferably a linear or branched alkyl group containing 1 to 18 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group and a hexyl group.
  • the cycloalkyl group is preferably a cyclopentyl group or a cyclohexyl group.
  • the alkenyl group is preferably one containing 2 to 18 carbon atoms such as an allyl group, an octenyl group and an octadecenyl group.
  • the aryl group is preferably a phenyl group or a naphthyl group.
  • the alkyl groups, cycloalkyl groups, alkenyl groups and aryl groups expressed by said X, Y, R 31 , R 32 , R 33 , R 34 and R 35 may have a substituent.
  • a substituent may be, for example, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a halogen atom, nitro group, cyano group, mercapto group, an amino group, a carboxyl group or a hydroxyl group.
  • the compounds expressed by the general formula [III] show the following isomerization.
  • the present invention includes also these isomers.
  • Said compounds have been generally known and disclosed in ,for example, Japanese Patent Unexamined Publication No. 107129/ 1976, Japanese Patent Unexamined Publication No. 102621/1973, Japanese Patent Unexamined Publication No. 59463/1980, Japanese Patent Unexamined Publication No. 124333/1984 and BP 1,204,623.
  • heterocyclic mercapto compounds of formula (IV) can also be mentioned as preferable examples.
  • the use of the above-mentioned heterocyclic mercapto compound in a photo-sensitive material comprising a photo-sensitive silver halide emulsion containing silver halide grains which consist essentially of silver chloride in combination with the sensitizing dye of formula [I] has the advantage that occurrence of fog can be restrained effectively even in the case where the possibility of contamination of the bleach-fixing solution with a color developer solution carried in from a previous step is increased and the pH value thereof tends to increase when a photo-sensitive material undergoes a bleach-fixing process immediately after a color development process.
  • nitrogen-containing heterocyclic mercapto compounds may be added to either the color developer or the sensitive material but it is preferable to add them to the sensitive material. In the event that they are added to the color developer, they are suitably added at a ratio of 10- 6 to 10-4- mol based on 1 liter of the color developer.
  • the nitrogen-containing heterocyclic mercapto compounds can be added to a sensitive silver halide emulsion layer or a non-sensitive constituent layer but it is preferable to add the nitrogen-containing heterocyclic compound to a sensitive silver halide emulsion layer.
  • nitrogen-containing heterocyclic mercapto compounds may be added and they may be added to two or more different layers.
  • These nitrogen-containing heterocyclic mercapto compounds are suitably used at a ratio of 10- 8 to 10-4- mol/m 2 , preferably 10- 7 to 10- 5 mol/m 2 .
  • nitrogen-containing heterocyclic mercapto compounds may be added in the form of alkali metal salts such as a sodium salt, a potassium salt or a lithium salt.
  • the fog-preventing effect by the combination of said sensitizing dye expressed by the general formula [I] with said nitrogen-containing heterocyclic mercapto compounds in a method of forming a dye image according to the present invention can reduce not only fog of a silver halide emulsion layer containing silver halide particles spectrally sensitized with said sensitizing dye but also that of other silver halide emulsion layers. This cannot be easily anticipated from the prior art.
  • the silver halide particles used in the present invention may be formed of, for example, silver chloride, silver bromide, silver iodide, silver chloro-bromide, silver iodo-bromide or silver chloro-iodide, preferably silver chloro-bromide, and particularly preferably silver chloro-bromide containing silver chloride at a ratio of 10 or more mol%.
  • the average particle diameter of said single dispersive silver halide particles is not especially limited but it should generally be 1.0 I lm or less, preferably 0.8 u.m or less.
  • the silver halide particles used in the present invention may have regular shapes, such as cubic shape and octahedral shape, and irregular shapes such as sharp shapes.
  • the silver halide emulsion of the sensitive silver halide emulsion layer may be doped with platinum, palladium, iridium, rhodium, ruthenium, bismuth, cadmium or copper, for example.
  • this silver halide emulsion can be chemically sensitized. Specifically, it can be sensitized by sulfur sensitizing agents, such as allylthiocarbamides, N, N-diphenyl thiourea, sodium thiosulfate and cystine, noble metal sensitizing agents, such as gold compounds, palladium compounds, platinum compounds, ruthenium compounds, rhodium compounds and iridium compounds, or combinations thereof. Also, it can be sensitized by reducing agents such as stannous chloride.
  • sulfur sensitizing agents such as allylthiocarbamides, N, N-diphenyl thiourea, sodium thiosulfate and cystine
  • noble metal sensitizing agents such as gold compounds, palladium compounds, platinum compounds, ruthenium compounds, rhodium compounds and iridium compounds, or combinations thereof.
  • reducing agents such as stannous chloride.
  • the binder used in the constituent layer of the silver halide photo-sensitive material is most generally formed of gelatine such as alkali-treated gelatine or acid-treated gelatine. Also, a part of this gelatine can be used together with, say, gelatine derivatives, such as phthalized gelatine and phenylcarbamoylgelatine, albumin, agar-agar, Arabian rubber, alginic acid, partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate, polyacrylamide, polyvinylalcohol, polyvinylpyrolidone and copolymers of these vinyl compounds.
  • gelatine derivatives such as phthalized gelatine and phenylcarbamoylgelatine, albumin, agar-agar, Arabian rubber, alginic acid, partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate, polyacrylamide, polyvinylalcohol, polyvinylpyr
  • the silver halide photo-sensitive material is subjected to the color developing process after the imagewise exposure to form the dye image.
  • Particularly useful color developing agents used in the color developer include N, N-diethyl-p-phenylene diamine hydrochloride, N-methyl-p-phenylene diamine hydrochloride, N, N-dimethyl-o-phenylene diamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N- ⁇ -methane sulfonamide ethyl-3-methyl-4-aminoanilin sulfate, N-ethyl-N-0-hydrox- ylethylaminoanilin sulfate, 4-amino-3-methyl-N, N-diethylaniline hydrochloride, N-ethyl-N-,e-hydroxylethyl-3-methyl-4-aminoani
  • color developing agents can be used singly or in the form of mixtures of two or more.
  • concentration of the color developing agents is suitably selected within the range of 0.01 to 0.05 mol based on 1 liter of the color developer.
  • the color developer can comprise various kinds of additive in addition to said color developing agent and said hydroxylamine derivative as the preservative.
  • alkali agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium meta-borate and tertiary potassium phosphate
  • pH-buffer agents such as sodium hydrogen phosphate, potassium bihydrogen phosphate, bisodium hydrogen phosphate and potassium bicarbonate
  • organic solvents such as methanol and ethylene glycol triethanol amine and can be used.
  • benzyl alcohol as the coloring capacity-improving agent is not present in the color developer according to the present invention. However, it can be present in a slight amount.
  • Benzyl alcohol may be present in the color developer in an amount of, say, 0 to 5 ml, preferably 0 to 3 ml, per liter of the color developer.
  • the color developer comprises a small amount of sulfite, such as sodium sulfite or potassium sulfite, in combination with said hydroxylamine derivative.
  • the sulfites are typically used in an amount of 0.05 to 2 g, preferably 0.1 to 0.3 g, per I liter of the color developer.
  • the color developer can comprise known development-inhibitors.
  • development-inhibitors include bromides, such as sodium bromide and potassium bromide, chlorides, such as potassium chloride and sodium chloride, and organic development-inhibitors, such as benztriazole and benzimidazole.
  • the effects of the present invention are particularly remarkable where the concentration of the color developer according to the present invention is about 0.005 mol or more.
  • the effect of the present invention that is to say the effect of inhibiting the generation of fog due to speedy processing in the event that hydroxylamine derivative is used, is remarkably increased.
  • speedy processing is meant processing in which the color development processing time is 90 seconds or less.
  • the temperature of the color developer is generally set at 20 to 50 C, preferably 30 to 40 C.
  • the bleach-fixing time is typically set at 90 seconds or less, preferably 60 seconds or less.
  • the bleach used in the bleach-fixing solution includes metal complexes of organic acids in which metallic ions, such as iron ions, cobalt ions and copper ions, are coordinated with organic acids such as polycarboxylic acids, polyaminocarboxylic acids, oxalic acid and citric acid.
  • organic acids such as polycarboxylic acids, polyaminocarboxylic acids, oxalic acid and citric acid.
  • the most preferable organic acids are polycarboxylic acids and polyaminocarboxylic acids.
  • These polycarboxylic acids may be used also in the form of an alkali metal salt, ammonium salt or water soluble amine salt, for example. Concrete examples of these include the following compounds:
  • bleaches are suitably used in an amount of 5 to 450 g/liter, preferably 20 to 250 g/liter.
  • the bleach-fixing solution may comprise sulfites as preservatives in addition to said bleaches if necessary.
  • the bleach-fixing solution may comprise an ethylene diamine tetraacetic acid iron (III) complex salt bleach and halides such as ammonium bromide.
  • Said halides include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide and ammonium iodide in addition to ammonium bromide.
  • the silver halide-fixing agents used in the bleach-fixing solution include compounds which react with silver halide to form water soluble complex salts, used in the usual fixing process, typically thiosulfates, such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, thiocyanates, such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, thiourea and thioether.
  • thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate
  • thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate
  • thiourea and thioether are typically used in an amount of 5 g/liter or more but in a quantity at which they can be dissolved, in general in an amount of 25 to 250 g/liter.
  • the bleach-fixing solution can comprise various kinds of pH-buffer agent, such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide, singly or in combination.
  • the bleach-fixing solution can comprise various kinds of fluorescent whitening agent, anti-foamant or surfactant.
  • the bleach-fixing solution can comprise bisulfite-addition products of hydroxylamine, hydrazine and aldehyde compounds, preservatives such as N, N-dialkyl-hydroxylamine, organic chelating agents such as polyaminocarboxylic acids, stabilizers such as nitroalcohol and nitrates, organic solvents such as methanol, dimethylsulfonamide and dimethylsulfoxide according to circumstance.
  • preservatives such as N, N-dialkyl-hydroxylamine
  • organic chelating agents such as polyaminocarboxylic acids
  • stabilizers such as nitroalcohol and nitrates
  • organic solvents such as methanol, dimethylsulfonamide and dimethylsulfoxide according to circumstance.
  • the bleach-fixing solution can comprise various kinds of bleach-accelerator such as disclosed in Japanese Patent Unexamined Publication No. 280/1971, Japanese Patent Examined Publication No. 8506/1970, Japanese Patent Examined Publication No. 556/1971, Belgian Patent 770,910, Japanese Patent Examined Publication No. 8836/1970, Japanese Patent Examined Publication No. 9854/1978, Japanese Patent Unexamined Publication No. 71634/1979 and Japanese Patent Unexamined Publication No. 42349/1974.
  • bleach-accelerator such as disclosed in Japanese Patent Unexamined Publication No. 280/1971, Japanese Patent Examined Publication No. 8506/1970, Japanese Patent Examined Publication No. 556/1971, Belgian Patent 770,910, Japanese Patent Examined Publication No. 8836/1970, Japanese Patent Examined Publication No. 9854/1978, Japanese Patent Unexamined Publication No. 71634/1979 and Japanese Patent Unexamined Publication No
  • the pH of the bleach-fixing solution is typically at 5.0 to 9.0, preferably 5.5 to 8.5.
  • the silver halide photo-sensitive material may be subjected to washing-substitute stabilizing treatments disclosed in e.g. Japanese Patent Unexamined Publication No. 14834/1983, Japanese Patent Unexamined Publication No. 105145/1983, Japanese Patent Unexamined Publication No. 134634/1983, Japanese Patent Unexamined Publication No. 18631/1983, Japanese Patent Application No. 2709/1983 and Japanese Patent Application No. 89288/1984.
  • the following layers were coated in turn on a titanium dioxide-containing polyethylene side of a support member obtained by laminating polyethylene on one side of a paper support member of 170 g/m 2 and laminating polyethylene containing anatase type titanium dioxide in an amount of 11% by weight on the other side of the paper support member to form silver halide color photo-sensitive materials No. 1 to 25.
  • the addition quantity is expressed as a quantity per 1 m 2 in so far as it is not specially mentioned otherwise.
  • the layer 1 - - - comprising 1.9 g of gelatin, 0.39 g of (based on silver) blue light-sensitive silver chloro- bromide emulsion (Note-1), 1.2 x 10 mol of a yellow coupler Y-1, the following photo-stabilizer STB-1 (0.3 g), 0.05 g of the following color contamination-inhibitor (HQ-1), 0.50 g of di-(2-ethylhexyl) phthalate (hereinafter referred to as DOP) and mercapto compounds as shown in Table 1 (0.08 g/m 2 ).
  • the layer 2 - - - an intermediate layer comprising 0.7 g of gelatine, 15 mg of an irradiation-inhibiting dye (AI-1) and 0.05 g of DOP, in which 10 mg of (AI-2) and 0.05 g of said color contamination-inhibitor HQ-1 are dissolved.
  • AI-1 an irradiation-inhibiting dye
  • DOP 0.05 g of DOP
  • the layer 3 - - - comprising 1.25 g of gelatine, 0.22 g of green light-sensitive silver chloro-bromide emulsion (containing silver chloride in an amount of 70% by mol), 0.30 g of DOP, in which 0.45 g of the following magenta coupler (M-1) is dissolved, and 0.02 g of HQ-1.
  • the layer 4 - - - comprising 1.2 g of gelatine, 0.08 g of HQ-11 and 0.35 g of DOP, in which 0.5 of ultraviolet absorbent (UV-1) is dissolved.
  • the layer 5 - - - comprising 1.4 g of gelatine, 0.20 g of red light-sensitive silver chloride emulsion, 0.20 g of DOP, in which 0.45 g of the following cyan coupler (C-1) is dissolved, and 0.02 g of HQ-1.
  • the layer 6 - - - comprising 1.0 g of gelatine and 0.20 g of DOP, in which 0.30 g of UV-1 is dissolved.
  • the layer 7 - - - comprising 0.5 g of gelatine.
  • Silver chloro-bromide emulsion containing silver chloride in an amount of 90% by mol was chemically ripened until the optimum sensitivity point to sodium thiosulfate and then spectrally sensitized by the use of sensitizing dyes as shown in Table 1 (at a ratio of 5 x 10- 3 mol per 1 mol of silver halide).
  • Each of said sensitive materials No. 1 to No. 25 was exposed to a white light through an optical wedge and then subjected to the following processes:
  • compositions of the color developer and the bleach-fixing solution are as follows:
  • the reflective concentration of a blue monochromatic light was measured for each of the resulting samples.
  • the sensitivity was measured from the characteristic curve [B] corresponding to the yellow dye image.
  • the gradation and fog were measured. Fog was also measured by the use of green monochromatic light.
  • the obtained results are shown in Table 1.
  • the sensitivity is expressed as a relative sensitivity with the sensitivity obtained in the event that the sensitive material 1 was processed in accordance with the process [A] as 100.
  • the gradation is expressed as an inclination of the characteristic curve having a reflective density of 0.5 to 1.5.
  • Table 2 shows the results obtained in the cases where the samples obtained by adding the mercapto compound [III]-24, which exhibited the best effect of preventing fog in EXAMPLE 1, to the layers containing the blue light-sensitive silver chloro-bromide emulsion sensitized by the comparative sensitizing dye and the sensitizing dyes [I]-3, [1]-7 and [1]-21 and the samples obtained by adding said mercapto compound [111]-19 to the layers containing the green light-sensitive emulsion were processed with the color developers [A], [B] and [C] used in EXAMPLE 1.
  • the samples obtained by adding the heterocyclic mercapto compounds partly to the layer 1 and partly to the layer 3 exhibit a great effect of preventing yellow fog and magenta fog when processed with the color developer [C].
  • Silver chlorobromide emulsion containing cubic silver chlorobromide crystals said silver chlorobromide containing silver chloride (99.5 % by mol) and having an average grain size of 0.70um, was chemically ripened by the use of sodium thiosulfate and potassium choloroaurate to an optimum sensitivity point. Thereafter, 5 x 10- 3 mol per 1 mol of silver halide of a sensitizing dye given in Table 4 and 2 x 10 -4 mol per 1 mol of silver halide of the mercapto compound given in Table 4 were added to the emulsion.
  • Silver chlorobromide emulsion containing cubic silver chlorobromide crystals said silver chlorobromide containing silver chloride (99.1 % by mol) and having an average grain size of 0.40 ⁇ m, was chemically ripened by the use of sodium thiosulfate and potassium choloroaurate to an optimum sensitivity point. Thereafter, 3 x 10- 3 mol per 1 mol of silver halide of a sensitising dye (GSD-1) given hereinbelow and 2.5 x 10 -4 mol per 1 mol of silver halide of the mercapto compound given in Table 4 were added to the emulsion.
  • GSD-1 sensitising dye
  • Silver chlorobromide emulsion containing cubic silver chlorobromide crystals said silver chlorobromide containing silver chloride at a ratio of 99.6 % by mol and having an average grain size of 0.42 ⁇ , m, was chemically ripened by the use of sodium thiosulfate and potassium choloroaurate to an optimum sensitivity point. Thereafter, 0.8 x 10- 4 mol per 1 mol of silver halide of a sensitizing dye (RSD-1) given hereinbelow and 2.5 x 10- 4 mol per 1 mol of silver halide of the mercapto compound given in Table 4 were added to the emulsion.
  • RSD-1 sensitizing dye
  • the photo-sensitive materials thus obtained were subjected to white exposure through an optical wedge and, thereafter, to the following processes:
  • the bleach-fixing solution used for process [D] and the color developer used for [F] were mixed at a ratio of 1:1 and the pH thereof was adjusted to 7.0.
  • the reflective density measurement of the respective samples were carried out and sensitivity, gradation and fog of the respective samples were obtained from the characteristic curves thereof.
  • occurrence of fog can be effectively restrained even in the process [G] and this effect was found to be particularly good when a mercapto tetrazole compound such as IV-14 or IV-20 is employed.
  • Samples 63 thru 86 were prepared respectively in the same manner as Samples 39 thru 62 in EXAMPLE 4, except that in the samples of this EXAMPLE half the amount of mercapto compound used in layer 1 of the respective samples in EXAMPLE 3 was added to layer 2.

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Claims (14)

1. Procédé de traitement d'un matériau photographique couleur photosensible à l'halogénure d'argent qui comprend le traitement d'un matériau photographique couleur photosensible à l'halogénure d'argent exposé à une image, ledit matériau comprenant un support qui comporte au moins une couche d'émulsion à l'halogénure d'argent contenant des grains d'halogénure d'argent qui sont sensibilisés avec un colorant sensibilisateur de la formule (1) :
Figure imgb0127
dans laquelle :
Z1 et Z2, qui peuvent être identiques ou différents, sont chacun un groupe qui, ensemble avec les atomes d'azote et de carbone auxquels ils sont reliés, forment un noyau hétérocyclique substitué ou non-substitué qui est un noyau thiazole, benzothiazole, sélénazole, benzosélénazole, naphtosélénazole, benzimidazole, naphtoimidazole, pyridine ou quinoline ;
R1 et R2, qui peuvent être identiques ou différents, sont chacun un groupe alkyle , alkényle ou aryle substitué ou nonsubstitué ;
R3 est hydrogène, un groupe méthyle ou un groupe éthyle :
X - est un anion ; et
1 est 1 ou 0 si au moins l'un des radicaux R1 et R2 contient un anion,
par une solution de développement couleur comprenant un agent de développement couleur d'amine primaire aromatique pendant 90 secondes tout au plus, en présence de :
au moins un dérivé hydroxylamine de la formule (II) :
Figure imgb0128
dans laquelle R21 et R22, qui peuvent être identiques ou différents, sont chacun hydrogène ou un groupe alkyle substitué ou non-substitué ayant de 1 à 4 atomes de carbone, à condition que R21, et R22 ne soient pas simultanément hydrogène, ou R21 et R22 ainsi que l'atome d'azote auquel ils sont reliés, forment un anneau contenant de l'azote, ou un sel acide hydrosoluble de ce dernier ; et
au moins un composé mercapto hétérocyclique contenant de l'azote.
2. Procédé selon la revendication 1 dans lequel Z1 et Z2, qui peuvent être identiques ou différents, sont chacun un groupe qui, ensemble avec les atomes d'azote et de carbone auxquels ils sont reliés, forment un cycle substitué ou nonsubstitué thiazole, benzothiazole, sélénazole, benzosélénazole ou naphtosélénazole.
3. Procédé selon la revendication 2 dans lequel Z1 et Z2 sont tous deux des groupes qui, ensemble avec les atomes d'azote et de carbone auxquels ils sont reliés forment un cycle benzothiazole substitué ou non-substitué.
4. Procédé selon l'une quelconque des revendications 1 à 3 dans lequel R1 et R2, qui peuvent être identiques ou différents sont chacun un groupe alkyle substitué ou nonsubstitué ayant de 1 à 6 atomes de carbone.
5. Procédé selon la revendication 4 dans lequel R1 et R2, qui peuvent être identiques ou différents sont chacun un groupe éthyle, un groupe propyle ou un groupe butyle.
6. Procédé selon l'une quelconque des revendications 1 à 4 dans lequel au moins l'un parmi R1 et R2, qui peuvent être identiques ou différents, est un groupe carboxyalkyle ou un groupe sulphoalkyle.
7. Procédé selon l'une quelconque des revendications 1 à 6 dans lequel R21 et R22, qui peuvent être identiques ou différents, sont chacun un groupe alkyle substitué ou nonsubstitué ayant de 1 à 4 atomes de carbone.
8. Procédé selon la revendication 7 dans lequel R21 et R22 sont tous deux des groupes éthyle.
9. Procédé selon la revendication 7 dans lequel le dérivé d'hydroxylamine est la N,N-diméthylhydroxyla- mine, la N,N-diéthylhydroxylamine, la N,N-dipropylhydroxylamine ou la N,Ndibutylhydroxylamine, ou un sel acide hydrosoluble de ce dérivé.
10. Procédé selon l'une quelconque des revendications 1 à 9 dans lequel le composé mercapto hétérocyclique contenant de l'azote est un mercapto oxadiazole, un mercapto thiadiazole, un mercapto triazole ou un mercapto tétrazole.
11. Procédé selon l'une quelconque des revendications 1 à 10 dans lequel le composé mercapto hétérocyclique contenant de l'azote est un composé de la formule (III) :
Figure imgb0129
dans laquelle :
X est hydrogène, un groupe amino, un groupe hydroxyle, un groupe hydrazino, un groupe alkyle, alkényle, cycloalkyle ou aryle éventuellement substitué, un groupe -NHCOR31, un groupe -NHS02R31, ou un groupe -R32S :
Y est hydrogène, un groupe amino, un groupe alkyle, un groupe alkényle, un groupe cyloalkyle, un groupe aryle, un groupe -CONHR33, un groupe -COR34-, un groupe -NHCOR35, ou un groupe -NHS02R35;
Z représente un azote, un soufre ou un oxygène;
n représente 1 quand Z est un azote, ou zéro quand Z est un oxygène ou un soufre; et
R3,, R32, R33, R34 et R35 représentent un groupement alkyle, alcényle, cycloalkyle ou aryle éventuellement substitué.
12. Procédé selon l'une quelconque des revendications 1 à 11, dans lequel le composé mercapto hétérocyclique contenant de l'azota est présent dans le matériau photographique photosensible à l'halogénure d'argent.
13. Procédé selon la revendication 12, dans lequel le composé mercapto hétérocyclique est présent dans le matériau photographique photosensible à l'halogénure d'argent à raison de 10-7 à 10-5 mol par m2.
14. Procédé selon la revendication 12 ou 13, dans lequel le dérivé hydroxylamine est présent dans la solution de développement couleur.
EP19870303532 1986-04-22 1987-04-22 Procédé de traitement d'un matériau photosensible à l'halogénure d'argent Expired EP0243168B1 (fr)

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JPH0750322B2 (ja) * 1986-06-25 1995-05-31 富士写真フイルム株式会社 ハロゲン化銀カラ−写真感光材料の処理方
JP2835611B2 (ja) * 1987-06-18 1998-12-14 富士写真フイルム株式会社 カラー画像形成法
JP2597206B2 (ja) * 1989-11-13 1997-04-02 富士写真フイルム株式会社 カルボキシアルキル置換ヒドロキシルアミン類の製造方法
JPH04170538A (ja) * 1990-11-01 1992-06-18 Chiyuugai Shashin Yakuhin Kk ハロゲン化銀写真感光材料用現像液
JP2887715B2 (ja) * 1992-06-10 1999-04-26 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料の処理方法
US6579669B1 (en) * 2001-10-30 2003-06-17 Eastman Kodak Company Method to reduce corrosivity of photographic processing effluent

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EP0243168A2 (fr) 1987-10-28
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JPS6346454A (ja) 1988-02-27
DE3773730D1 (de) 1991-11-21
JP2591616B2 (ja) 1997-03-19

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