WO1987004809A1 - Procede de formation d'images en couleur - Google Patents

Procede de formation d'images en couleur Download PDF

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Publication number
WO1987004809A1
WO1987004809A1 PCT/JP1987/000062 JP8700062W WO8704809A1 WO 1987004809 A1 WO1987004809 A1 WO 1987004809A1 JP 8700062 W JP8700062 W JP 8700062W WO 8704809 A1 WO8704809 A1 WO 8704809A1
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WIPO (PCT)
Prior art keywords
group
color
image forming
forming method
divalent
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PCT/JP1987/000062
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English (en)
Japanese (ja)
Inventor
Osamu Takahashi
Hideaki Naruse
Jun Arakawa
Jiro Yamaguchi
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Fuji Photo Film Company Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Company Limited filed Critical Fuji Photo Film Company Limited
Priority to DE19873785270 priority Critical patent/DE3785270T2/de
Publication of WO1987004809A1 publication Critical patent/WO1987004809A1/fr

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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
    • 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
    • G03C1/38—Dispersants; Agents facilitating spreading
    • G03C1/385—Dispersants; Agents facilitating spreading containing fluorine
    • 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

Definitions

  • the present invention relates to a method for forming a color image using a halogenated color light-sensitive material, and particularly to a color image forming method using a benzene and / or alcohol to reduce the processing time. It relates to a forming method.
  • a photographic power blur of five colors of yellow, magenta and cyan is contained in the photosensitive layer, and after exposure, it is processed with a color developing solution containing a color developing agent.
  • the oxidized aromatic primary amine reacts with the coupler to give a coloring dye by a coupling reaction.In this case, it is necessary to give as high a coloring density as possible within a limited development time. It is necessary.
  • benzyl alcohol when benzyl alcohol is introduced into a bleaching bath or a bleach-fixing bath, which is a post-bath, it causes the formation of the cyan pigment ⁇ ico-dye and causes a decrease in color density. In the latter case, since the washing speed of the developing solution component is slowed down, the image storability of the photosensitive material may be adversely affected. Therefore, the above reasons It is preferable to use benzyl alcohol. Conventionally, in color development, processing was usually performed in 3 to 4 minutes. However, with the recent reduction in finish delivery time and reduction in lab work, reduction in processing time has been desired.
  • a method incorporating 3-virazolines is used (for example, the method described in JP-A-60-26338, JP-A-60-1584844, JP-A-60-158446).
  • JP-A-60-26338, JP-A-60-1584844, JP-A-60-158446 has the disadvantage that the sensitivity is lowered during the life and fog is generated.
  • Surfactants used in conventional color photographic light-sensitive materials subjected to such color development processing include: sanonin; sulfosuccinic acid; anolekybenzenesnolefonic acid such as dodecylbenzenesnolefonic acid; alkylnaphthalene Sulfonic acid; Sorbitan sesquiyl oleate; Sorbitan monolaurate; Anionic and nonionic surfactants such as alkylene oxide derivatives o
  • a color developer containing substantially no benzyl alcohol can be used to process a color light-sensitive material within 2 minutes and 30 seconds. It was insufficient for the purpose of obtaining a color photograph with a high maximum color density (Dma ⁇ ) and a low minimum color density (Dinin) with little sensitivity and gradation change.
  • a first object of the present invention is to provide an image forming method which can provide a high color density in a short time even when a color developer containing substantially no benzyl alcohol is used. .
  • a second object of the present invention is to reduce the generation of capri and to speed up development.
  • An object of the present invention is to provide an image forming method.
  • a third object of the present invention is to provide a color image forming method in which changes in sensitivity and gradation are small.
  • the present invention has at least one silver halide emulsion layer on a reflective support, and the emulsion layer or a layer adjacent thereto has a fluorine-substituted fatty acid having 4 to 18 carbon atoms as a hydrophobic group in the molecule.
  • have a family group and as the parent-aqueous base - S_ ⁇ 3 M or - 0s0 3 M c ⁇ Gen Kaginka error (where M is a is hydrogen atom or a cation) containing Anion surfactant having After exposure, photographic light-sensitive material contains benzyl alcohol substantially.
  • ⁇ O is an image forming method that is characterized by developing in a color developer for 2 minutes and 30 seconds or less.
  • substantially containing benzyl alcohol means that the concentration of benzyl alcohol in the developer is 0.5 or less.
  • Preferable anionic surfactants in the present invention can be represented by the following general formula.
  • a divalent or trivalent aliphatic hydrocarbon group for example, alkylene group or alkylene group in which the titylene in the alkylene group is partially substituted with an aromatic group
  • aryl Diene groups eg, phenylene, 1,4-naphthylene, 2-hydroxy-1,4-naphthylene, etc.
  • divalent heterocyclic groups eg, divalent benzimidazoyl group, 1- Alkenylbenzmidazol-2-yl, etc.
  • ⁇ also represents a divalent or trivalent organic residue and a divalent bonding group (eg, -C0-0-,
  • G0-NR- one S0 2 NR-, where R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms.
  • Group (I j, (S ⁇ 2— N— — 0— ⁇ ) 2 R 2 —, -C00R 1- , -R 1 0-C0-R 1- , -CONH-R ⁇ , -S0 2 NR -R 1- , represents ⁇
  • R 2 represents a trivalent aliphatic hydrocarbon group.
  • n is an integer of 1-2, and m represents 0 or 1.
  • n 1 0
  • carbon-containing surfactants containing carbon fluoride used in the present invention are commercially available from Dainippon Ink Chemical Industry Co., Ltd. under the trade name of Megafac F (for example, F-109). , F-110 and F-115), and are commercially available from Imperial Chemical Industries, Ltd. under the trade name of Monflor (for example, Monflor 31).
  • the anionic surfactant containing carbon fluoride used in the present invention is added to one or both of an oil-soluble photographic additive (eg, force blur, etc.) solution and a colloid aqueous solution as far as the solubility permits. can do.
  • an oil-soluble photographic additive eg, force blur, etc.
  • a colloid aqueous solution as far as the solubility permits. can do.
  • a DIR non-coloring power blur an ultraviolet absorber, an anti-fading agent, a color mixing inhibitor, a stain inhibitor, an antioxidant, and the like can coexist in an oil droplet containing a coupler.
  • the surfactant used in the present invention is used alone. Can be used in combination with other surfactants. In some cases, it may be preferable to use it in combination with some other surfactant.
  • the fluorine-substituted anionic surfactant used in the present invention can be used in combination with a so-called fluorine-unsubstituted anionic surfactant and a non- or non-ionic surfactant.
  • nonionic surfactant it is preferable to use a nonionic surfactant described in JP-A-48-30933 and a fatty acid ester-based surfactant of a polyhydric alcohol.
  • the fatty acid ester-based surfactant of the polyhydric alcohol preferably has at least two, preferably at least three, hydroxyl groups, and more preferably has 6 to 25 carbon atoms of the fatty acid.
  • the fatty acid ester nonionic surfactant of nrubitan described in US Pat. No. 3,676,141 is advantageously used in the present invention.
  • fluorine-unsubstituted anionic surfactant include the following compounds.
  • At least one fluorine-substituted surface active agent for use in the present invention, the hydrophobic group and -S0 3 M also properly from 8 carbon atoms to 3 0 per molecule - OS0 3 M Group (where M has the same meaning as in the above [I]). It is particularly preferred to use at least one and at least one of Z or sorbitan fatty acid ester nonionic surfactants.
  • organic solvent ie, a so-called oil component
  • a solvent which is practically insoluble in water and has a boiling point of 190 TC or more at normal pressure is useful.
  • This type of organic solvent can be selected from carboxylic esters, phosphoric esters, carboxylic amides', ethers, and substituted hydrocarbons.
  • di-n-butyl phthalate ester di-iso-butynophthal ester, di-meth-oxyethyl phthal ester, di-n-butyl adipate ester, Disoctylazelenate, tri-n-butynolephthate monooleate, butynolaureate, di-n-cenomycinate, tricresyl phosphate, tri-n-butylphosphate Esters, triinooctyl phosphoric esters, N ⁇ N-methyl cuff.
  • a low-boiling solvent having a boiling point of 130 or less at room pressure
  • a solvent having a low boiling point in addition to such a solvent for dissolving the power brush is used.
  • a water-soluble high-boiling solvent for example, propylene carbonate, ethyl acetate, butyl acetate, ethyl propyl.
  • Acid esters sec-butynoleanolone, tetrahydrofuran, cyclohexanone, dimethylhonolenamim, dimethylsulfoxyside ', methylseptol sorb and the like.
  • a device that applies a large shear force to the treatment liquid or a device that applies high-intensity ultrasonic energy is suitable.
  • a colloid, a mill, a homogenizer, a capillary emulsifier, a liquid siren, an electromagnetic strain type ultrasonic generator, and an emulsifier having a woolman whistle can give good results.
  • a silver halide emulsion layer and / or a layer adjacent thereto are preferable, and a silver halide emulsion layer is particularly preferable.
  • the amount of the fluorine-substituted anionic surfactant used in the present invention depends on the type of the coupler to be used, the type of the other coexisting additive, the type and the amount of the dispersing solvent, and in some cases, the other surfactant used in combination. Although it depends on the type and amount of the agent, it is generally preferred that the dispersing substance (that is, a solution in which a coloring agent and other oil-soluble photographic additives are dissolved in a dispersing solvent) be 0.2 to 50% by weight.
  • an oil-soluble copying agent additive such as an anti-fading agent, an ultraviolet absorber, a DIR coupler, an antioxidant and the like can be contained.
  • reflective support used in the present invention means a material which enhances reflectivity to sharpen a dye image formed in a silver halide emulsion layer
  • a reflective support is made of a support coated with a hydrophobic resin containing a light-reflective material such as titanium oxide, zinc oxide, calcium carbonate, calcium sulfate, or the like, or a light-reflective material.
  • Warabi containing dispersed content includes those using an aqueous resin as a support.
  • a parasite paper ⁇ ethylene-coated nylon, ⁇ reprovylene-based synthetic paper, a transparent support with a reflective layer or with a reflective material, for example, a glass plate, a 'ten-ethylene terephthalate, ⁇ 1 ⁇ Acid cellulose, slightly acid cellulose, etc. ⁇ polyester film, ⁇ rearm, film, carbonate film, ⁇ polystyrene film etc.), these supports are used Select according to the purpose.
  • the processing time of the color development process in the present invention is as short as 2 minutes and 30 seconds or less. Preferred processing times are 30 seconds to 2 minutes.
  • the processing time is the time from when the photosensitive material comes into contact with the developing solution until it comes into contact with the next bath.
  • the color developing solution used in the developing process of the present invention is preferably an aqueous alkaline solution mainly containing an aromatic primary amine color developing solution.
  • an aromatic primary amine color developing solution p-phenylenediamine-based compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-ethylenirinine, and 3-methinolen-4-in.
  • aminophenol derivatives include 0- aminophenol, -aminophenol, 4-amino-2-methylphenol, 2-amino-3-methylphenol, Contains 2-year-old 3-amino-3,4-dimethylbenzene.
  • the processing temperature of the color developer in the present invention is preferably from 301C to 50C, more preferably from 33C to 45C.
  • antifoggants in the present invention preferred are alkali metal halides such as lithium bromide, sodium bromide and potassium iodide, and organic antifoggants.
  • alkali metal halides such as lithium bromide, sodium bromide and potassium iodide
  • organic antifoggants examples include, for example, benzotriazole, 6-nitonibenzene, zonole, 5-nitroysonda, zonole, and 5-methinobenzone azonole.
  • the color developing solution of the present invention may be a pH buffer such as an alkali metal carbonate, borate or phosphate; hydroxypropylamine, triethanolamine, West German patent application. (0 LS) No. 2,622,950, preservatives such as sulphite or bisulphite; organic solvents such as diethylene glycol; dye-forming agents; competitive couplers; Dry nucleating agents, such as nucleating agents; auxiliary developing agents, such as 1-phenyl-3-virazolidone; saccharifying agents; ethylenediaminetetraacetic acid, nitric acid triacetic acid, silicone Patent application title: Rohexanediaminetetraacetic acid, iminoniacetic acid, N-hydroxymethylethylenediamintrisulfuric acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid
  • Amino ⁇ carboxylic acid represented by the compound described in No. 58-195 5 845, 1-hydroxylidene-1,1,1'-diphosphonic acid, lysate (ResearctL Disclosure.) / 1817 (March 1979)
  • l 18170 may contain a chelating agent such as phosphonocarboxylic acid.
  • the color developing bath is divided into two or more parts as necessary, and the replenisher is added from the first or last bath to shorten the development time and reduce the amount of replenishment. May be.
  • the bleaching process may be performed simultaneously with the fixing process (bleach-fixing) or may be performed individually.
  • the bleaching agent include compounds of polyvalent metals such as iron (II), cobalt (H), chromium (VI), copper (n), peracids, quinones, and nitroso compounds. .
  • DI iron
  • copartite ethylenediaminetetraacetic acid
  • diethylenetriaminepentaacetic acid diethylenetriaminepentaacetic acid
  • ditrilotriic acid complex salts of aminocarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid or organic acids such as citric acid, tartaric acid, and linoleic acid; persulfates, manganates; and ⁇ -sophenol.
  • aminocarboxylic acids such as 1,3-diamino-2-propanoltetraacetic acid or organic acids such as citric acid, tartaric acid, and linoleic acid
  • persulfates, manganates and ⁇ -sophenol.
  • potassium ferricyanide sodium ethylenediaminetetraacetate (I) sodium and ethylenediaminetetraacetate (II) ammonium, triethylenetetramineironpentapentanate (III) ammonium, Persulfates are particularly useful.
  • Ethylenediaminetetraacetic acid (H) complex salt is useful in both an independent bleaching solution and a single bath bleach-fixing solution.
  • Various accelerators may be used in the bleaching solution or the bleach-fixing solution, if necessary.
  • JP-B No. 45-856 JP-A-49-26659, JP-A-53-32753, JP-B53-36233 As shown in JP-A-53-37010 and thiourea-based compounds, or JP-A-53-124424, JP-A-53-95631, JP-A-5-3-5 No. 7 831, No. 53-3 2 7 3 6, No. 5 3-6 5 7 32, No. 5 4-5 2 5 3 4 and U.S. Patent No.
  • JP-A-49-5964 JP-A-50-140201, JP-A-53-284426, JP-A-53-114416, Heterocyclic compounds described in JP-A-53-104432 and JP-A-54-357272, or JP-A-52-20832, JP-A-55 Thioether compounds described in JP-A-25064 and JP-A-55-26506, or quaternary amines described in JP-A-48-84440 Or compounds such as thiocarbamoyls described in JP-A-49-42349.
  • the fixing agent examples include thiocyanate sulfate, thiocyanate, thiocyanate compounds, thiamine ureas, and a large amount of iodide. It is used.
  • thiocyanate sulfate thiocyanate
  • thiocyanate compounds thiocyanate compounds
  • thiamine ureas thiamine ureas
  • a washing process is usually performed.
  • various known compounds may be added for the purpose of preventing precipitation and saving water.
  • hard water softeners such as inorganic phosphoric acid, amino-carboxylic acid, and organic phosphoric acid to prevent precipitation, fungicides and pie-proofing agents to prevent the occurrence of various bacterium algae and power plants, and magnesium
  • a hardening agent represented by a salt / aluminum salt or a surfactant for preventing drying load and unevenness can be added.
  • LE West Photographic 'Science' And 'Engineering' Phot. Sci. And Eng.
  • Vol. 9, No. 6, (1965) And the like In particular, a sword that is a sharpener or anti-binder is effective.
  • a multi-stage for example, 2 to 5 stages
  • a multi-stage countercurrent stabilizing step as described in JP-A-57-8543 may be carried out.
  • 2 to 9 countercurrent baths are required.
  • Various compounds are added to the stabilizing bath for the purpose of stabilizing an image.
  • buffers for adjusting membrane pH eg, borate, metaborate, borax, phosphate, carbonate, hydroxylation, sodium hydroxide, ammonia water, monocarbonate
  • Acids, dicarboxylic acids, polycarbonates, etc. and formalin.
  • water softeners optionally (inorganic-phosphate, amino ⁇ Li carboxylic acids, organic-phosphate, amino ⁇ Rihosuhon acid, and phosphonocarboxylic acid), killing KinHitoshi 1 j (Proxel, Lee Sochiazoron, A surfactant, a fluorescent brightener, a hardener, and the like may be added, for example, 4-thiazolylbenzimidazole, halogenide phenolbenzotriazoles and the like.
  • ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate and the like can be added as a membrane pH adjuster after the treatment.
  • the color coupler incorporated in the light-sensitive material preferably has a palladium group or is remarkable to have a diffusion resistance.
  • the two-equivalent color coupler substituted with a leaving group can reduce the amount of coated silver.
  • a coupler, a non-color coupler or a coupler that has an appropriate diffusibility DIR couplers releasing an image inhibitor or couplers releasing a development accelerator can also be used.
  • yellow couplers examples include oil-protected acylacetamide couplers. Specific examples thereof are described in U.S. Patent Nos. 2,407,210, 2,870,057, and 2,626,506. In the present invention, the use of two-equivalent yellow couplers is preferred, as described in U.S. Pat. Nos. 4,040,194, 4,447,928, and 93,501. Nos. 4,702,620 and 4,432,024, and U.S. Pat.Nos. 440,175,2, and 432,024. , RD 18053 (April 1979), UK Patent No.
  • a typical example is a nitrogen pull-out type yellow puller described in No. 4 3 8 1 No. 2.
  • the a-piparoylacetide-based coupler is excellent in the fastness of a coloring dye, particularly in light fastness, while the ⁇ -benzoylacetanilide-based coupler can obtain a high color density.
  • magenta couplers usable in the present invention include oil-protected, orzinazo-based or cyanoacetyl-based, preferably 5-birazolone- and birazolo-azo-based, such as, bisazolo-triazols. Kabbler. 5-hee.
  • couplers in which the 3-position is substituted with an arylamino group or an acylamino group are used in view of the hue and color density of the coloring dye.
  • Preferable examples thereof include U.S. Pat.Nos. 2,311,082, SSa TOS, 60Q788, 290-573, and 3 ⁇ 4062. «No. 653, No. 5152>, No. 896 and No. 1993.
  • a nitrogen atom leaving group described in US Pat. No. 4,310,619 or US Pat. No. 4,351,89 The arylthio group described in No. 7 is preferred.
  • a 5-pirazolone-based plastic having a pallas group described in European Patent No. 73636 can obtain a high color density.
  • Birazoloazole couplers include U.S. Patent No.
  • Cyan couplers usable in the present invention include oil-protected naphthol-based couplers and phenol-based couplers.
  • the naphthalene-based couplers described in U.S. Pat. No. 2,474,293. And, preferably, U.S. Pat. And Nos.> 22-233 and 4,292,000 are examples of oxygen-equivalent double-equivalent naphthol-based couplers.
  • Specific examples of phenolic couplers are described in U.S. Pat.No. 2,369,929, U.S. Pat.No. 2> 80 L171, U.S. Pat. No. Humidity and temperature-resistant cyan couplers are preferred for use in the present invention, and are exemplified by U.S. Pat.
  • Granularity can be improved by using a power blur in which the coloring dye has an appropriate diffusibility.
  • a dye-diffusing power brush examples include U.S. Pat. No. 4,362,37 and British Patent No. 12-570, and specific examples of the magenta power brush are disclosed in European Patent No. 9557. No. 0 and West German Patent Application No. 234,533 describe specific examples of yellow, magenta or cyan couplers.
  • Dye-forming couplers and the above special couplers are dimers or more May be formed.
  • a typical example of a reimaged dye forming power brush is U.S. Pat.
  • the various couplers used in the present invention can be used in combination of two or more in the same layer of the photosensitive layer in order to satisfy the characteristics required for the photosensitive material. The above can also be introduced.
  • the standard amount of color coupler used is that of photosensitive silver halide.
  • the light-sensitive material used in the present invention may be a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an asconolevic acid derivative, or a colorless antifoggant or color mixture inhibitor. It may contain a coupler, a sulfonamide, a phenol compound and the like.
  • a well-known discoloration inhibitor can be used in the light-sensitive material processed in the present invention.
  • organic discoloration inhibitors include hydroquinones, 61-hydroxychromans, 5-hydroxycoumarins, and sucrose. Mouth chromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylated xybenzenes, aminophenols, hindered doors
  • Representative examples include amines and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds.
  • metal complexes represented by (bis-salicyaldaldoximato) nickel complexes and (bis-N, N-dialkyldithiol-rubamat nickel complexes) can also be used.
  • UV absorber In order to improve the storage stability of the cyan image, particularly the light fastness, it is preferable to use a benzotriazole-based ultraviolet absorber in combination.
  • This UV absorber may be co-emulsified with a cyan coupler.
  • the amount of the UV absorber applied may be sufficient to provide photostability to the cyan dye image, but if it is used in large amounts, yellowing will occur in the unexposed areas (white areas) of the color photographic material. in is located may result ', usually favored properly 1 X 1 0 - 4 mol / ⁇ 2 ⁇ 2 X 1 0- 3 mol / m 2, in particular 5 X 1 0- 4 Monore Zm 2 ⁇ : 1. 5 X It is set in the range of 1 0 3 mole Zm 2.
  • an ultraviolet absorber is contained in one or both layers of the red-sensitive emulsion layer containing a cyan coupler, preferably in both layers. Between the green and red layers When an ultraviolet absorber is added to the intermediate layer, it may be co-emulsified with a color mixing inhibitor. When an ultraviolet absorber is added to the protective layer, another protective layer may be applied as the outermost layer. This protective layer can contain a matting agent flute of any particle size.
  • an ultraviolet absorber can be added to the hydrophilic ⁇ -side layer.
  • the light-sensitive material to be processed in the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as anti-irradiation or halation.
  • the photographic emulsion layer or other hydrophilic color or layer of the photographic material to be processed in the present invention may contain any of stilbene, triazine, thiazole or coumarin brighteners.
  • a water-soluble one may be used, and a water-insoluble brightener may be used in the form of a dispersion.
  • the light-sensitive material used in the present invention can be applied to a multilayer multicolor photographic material having at least two different spectral sensitivities on a support.
  • Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one real-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as needed.
  • Each emulsion layer in the previous period may be composed of two or more emulsion layers having different sensitivities, or a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity. .
  • the light-sensitive material used in the present invention includes a protective layer, an intermediate layer, a filter layer, an anti-halation layer, and a pack layer in addition to the silver halide emulsion layer. 3 ⁇ 4 It is preferable to appropriately provide any auxiliary layer.
  • gelatin is advantageously used, but other hydrophilic colloids can also be used. .
  • gelatin derivatives proteins such as graphitic oligomers of gelatin and other macromolecules, albumin, casein, etc .
  • Cellulose derivatives such as sulfates, sugar derivatives such as sodium alginate and starch derivatives
  • vinyl alcohol polyvinyl alcohol partial acetal
  • ⁇ -N-Bilhi Mouth or copolymers
  • lidone acrylic acid, polymethacrylic acid, polyacrylamide, polyvinylamide, polyvinyl razol, etc.
  • Many types of synthetic hydrophilic polymer substances can be used.
  • the light-sensitive material of the present invention may further contain various stabilizers, antifouling agents, developing agents or their precursors, development accelerators or their precursors, lubricants, mordants, mats Agents, antistatic agents, plasticizers, or other useful photographic materials.
  • various additives may be added. A representative example of these additives is Research 'Disclosure 1 176 4 3 (1972 January 1 February) and the same. 1 8 7 16 (January 19, 1997).
  • silver chlorobromide, silver chloride, silver chloroiodobromide, silver bromide, silver iodobromide and the like are used as ⁇ -halogenated silver, and preferably silver iodide is substantially contained.
  • Silver bromide, silver chlorobromide, and silver chloride] and more preferably silver chlorobromide having a silver bromide content of 20 to 98 mol.
  • the silver halide grains used in the present invention may have a phase different from the inside and the surface layer, may have a multi-phase structure having a bonding structure, or the whole grains may be composed of a uniform phase. They may be mixed. .
  • Average grain size of silver halide grains used in the present invention (in the case of spherical or nearly spherical grains, the grain diameter is used, and in the case of cubic grains, the ridge length is defined as the grain size, and the average is based on the projected area) Is preferably 2 or less and 0.1 or more, and particularly preferably 1 or less and 0.15 or more.
  • the grain size distribution may be either narrow or wide, but the value obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size (variation rate) is 20 or less, particularly preferably. It is preferable to use so-called monodispersed silver halide emulsions having a size of 15 or less in the present invention.
  • two or more monodisperse silver halide emulsions having different grain sizes in the emulsion layer having substantially the same color sensitivity (the monodispersity The above-mentioned fluctuation rate is preferable) is mixed in the same layer or multi-layer coated in another layer be able to.
  • two or more polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be used as a mixture or as a mixture.
  • the shape of the silver halide grains used in the present invention may be cubic, octahedral, dodecahedral, or tetradecahedral, or may have regular crystals, or may be irregular such as spherical. (Irregular) It may have a crystal form, or a compound form of these crystal forms, but preferably has a regular 3 ⁇ 4 crystal such as a cube or a tetrahedron. Further, tabular grains may be used. In particular, an emulsion in which tabular grains having a ratio of length to thickness of 5 or more, particularly 8 or more, occupy 50% or more of the total projected area of the grains may be used. An emulsion comprising a mixture of these various crystal forms may be used. These various types of emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains, but the former is preferred.
  • the photographic emulsion used in the light-sensitive material processed in the present invention is P.
  • a so-called conversion method including a process of converting silver halide haptogen that has already been formed into silver halide having a lower solubility product until the process of forming silver halide halides is completed.
  • Emulsions prepared and emulsions which have undergone the same halogen exchange after completion of the silver halide grain formation process can also be used.
  • potassium salt zinc salt, copper salt, iron salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or its salt. Salt and the like may coexist.
  • the silver halide emulsion is usually subjected to physical ripening, desalting and chemical ripening after grain formation, and then used for coating.
  • Known silver halide solvents e.g., ammonia, rodancali or U.S. Pat. No. 2,711,157, JP-A-5-123660, JP-A-5-3-8240
  • Thia ethers and thien compounds described in JP-A-53-144319, JP-A-54-107171 or JP-A-54-155828 Can be used for precipitation, physical ripening, and chemical ripening.
  • a washing method such as a Nudell washing method, a flow-setting method or an ultra-leakage method is used.
  • the silver halide emulsion used in the light-sensitive material to be processed in the present invention contains a compound containing sulfur capable of reacting with active gelatin or silver (eg, sulphate sulfate, thioureas, mercapto compounds, rhodanines).
  • Sulfur sensitization method used Reduction sensitization method using a reducing substance (for example, stannous salt, amines, hydrazine derivative, formamidine sulphinic acid, silani conjugate); metal compound (for example, gold) in addition to ⁇ can be used P t, l r, P d , Rh, or in combination with etc.
  • F e which periodic table f metals complex salts) noble metal sensitization method 3 ⁇ 4 using alone.
  • the blue-sensitive, green-sensitive and red-sensitive emulsions of the color light-sensitive material used in the present invention are spectrally sensitized by a methine dye or the like so as to have color sensitivity.
  • Dyes used include cyanine dyes, melocyanin dyes, complex cyanine dyes, complex melocyanin dyes, holo-larocyanin dyes, hemicyanin dyes, styryl dyes, and hemiokinol dyes. Included. Particularly useful dyes are those belonging to cyanine dyes, melocyanine dyes and complex melocyanine dyes.
  • any of nuclei usually used in cyanine dyes as basic heterocyclic nuclei can be applied. That is, a viroline nucleus, an oxazoline nucleus, a thiazoline nucleus, and a nucleus.
  • Melocyanine dyes or complex melo and cyanine dyes have a pyrazolin-5-one nucleus, a chi-hydantoin nucleus, and a 2-thio-xoxazolidin-2,4-di-nucleus having a ketomethylene structure.
  • Five- to six-membered heterocyclic nuclei such as nuclei, thiazolidin-2,4-dione nuclei, rhodanine nuclei, and genius parbituric acid nuclei can be applied.
  • These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos.
  • the emulsion may contain a dye which itself has no spectral sensitizing action or a substance which does not substantially absorb visible light and exhibits supersensitization.
  • the yellow coupler (Y-1) 2 4.09 was dissolved by adding ethyl acetate 3 and a solvent: 7 dibutyl tartrate 12 4.0 as a solvent, and using this solution as an emulsifying dispersant, the following comparative compound R-1
  • the solution was added to a solution of 10 (dibutyl naphthalene sulfonato sodium) in 10 2 aqueous gelatin solution containing 10 ⁇ , and emulsified and dispersed by a high-speed stirrer.
  • samples (B) to (R) were prepared as follows.
  • R 1 Kawa! Is an exemplary compound A of the present invention.
  • the exemplary compound of the present invention A- Sample identical to sample (A) except using 20 ⁇ 1.0 ⁇
  • the silver coating amount of the silver chlorobromide emulsion composed of 0.37 / m 2 Br 75 mol was 0.209 / 2
  • the cyan coating amount was 0.33 / 2
  • the silver coating amount of silver chlorobromide emulsion comprising br 7 0 mo was 0.28 1 ⁇ 4 2.
  • Comparative multilayer photographic paper (A) having the layer configuration shown in Table 2 was prepared on a paper support laminated on both sides with ethylene.
  • the coating solution was prepared as follows.
  • the emulsified dispersion and the emulsion were mixed and dissolved, and the gelatin concentration was adjusted so as to obtain the composition shown in Table 2, thereby preparing a coating solution for the first layer.
  • the coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.
  • the following dyes were used as the anti-irradiation dyes in each emulsion layer.
  • Green-sensitive emulsion layer Green-sensitive emulsion layer
  • Solvent (j) ⁇ 0.09 cc m 2 ; i fifth layer I silver chlorobromide emulsion (70 mol of silver bromide) silver: I 0.239 m 2; (red sensitive layer Zephthene 0.98 '
  • Anti-color mixing agent 0.05 "solvent (0.26 cm 2 silver chlorobromide emulsion (75 mol of silver) silver: I 0.13 1 ⁇ 4 2 gelatin i 1.80 magenta cuff. ;! 0.20 "solvent (g) 0.68 cc m 2 second layer - gelatin of 0.99 ⁇ / m 2 (color mixing preventing layer) color mixing preventing layer (0.08 i first layer 'silver chlorobromide emulsion (Nioii 80 mol) of silver 0.27 ⁇ m 2 : (blue sensitive layer) gelatin 1.86 "
  • the light-sensitive material (A) was used except that 1.2-1 of the exemplary compound A-9 of the present invention was used as an emulsifying dispersant in the glue j of R-1. Same photosensitive material
  • the gradation for sensitometry is passed through blue, green, and red filters. Exposure was given. The exposure at this time was performed so that the exposure amount was 250 GMS with an exposure time of 0.5 second.
  • the photographic properties were evaluated by changing the development time from the color development, bleach-fix, and washing steps to 1, 2, and 3 minutes.
  • the contents of the processing A and B represent the difference between the color developing solutions A and B, and the other processing contents are the same for both A and B.
  • the relative sensitivity is a relative value where the sensitivity at a color development time of 2 minutes in process A of each photosensitive layer of each photosensitive material is 100.
  • the sensitivity was expressed as a relative value of the reciprocal of the exposure required to give a density obtained by adding 0.5 to the minimum density.
  • the gradation was expressed as a density difference from the sensitivity point to a point increased by 0.5 by the logarithm of the exposure (iogE :).
  • the present invention is obtained by developing photosensitive materials (B), (G) and (D) by processing B.
  • the photosensitive materials (B) to (D) used in the present invention are comparative photosensitive materials. It can be seen that the performance of Treatment B, which is small and does not contain benzyl alcohol, is comparable to that of Treatment A.
  • the light-sensitive materials (B) to (D) of the present invention even in a high bromine content emulsion whose development progresses relatively slowly, good photographic properties can be obtained in a processing time of 2 minutes even in processing B containing benzyl alcohol. showed that. Therefore, it can be seen that the development is further shortened in the emulsion having a high chlorine content.
  • the pollution load is reduced, the preparation of the solution is reduced, and the effect of eliminating the decrease in the concentration due to the cyan dye remaining in the silicone body is eliminated. It has.
  • the use of the silver halide emulsion of the present invention provides an effect that high Dmax, low Dmin, and sensitivity and photographic properties with little gradation change can be obtained without using j? And benzyl alcohol.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Abstract

Procédé de formation d'images en couleur consistant à traiter un papier couleur exposé de manière à y former une image et contenant un agent tensioactif anionique possédant un groupe aliphatique à substitution fluore en tant que groupe hydrophobe et un groupe -SO3M ou -OSO3M (où M représente hydrogène ou un cathion) en tant que groupe hydrophyle, avec un révélateur couleur essentiellement exempt d'alcool benzylique. Par le traitement du papier couleur ci-décrit contenant l'agent tensioactif anionique à substitution fluore, il est possible d'obtenir en peu de temps des images en couleur présentant une forte densité chromatique même lorsque le papier est traité avec un révélateur couleur ne contenant essentiellement aucun stimulateur de développement polluant.
PCT/JP1987/000062 1986-01-30 1987-01-29 Procede de formation d'images en couleur WO1987004809A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE19873785270 DE3785270T2 (de) 1986-01-30 1987-01-29 Farbbildverfahren.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP1848786A JPH0614180B2 (ja) 1986-01-30 1986-01-30 カラ−画像形成法
JP61/18487 1986-01-30

Publications (1)

Publication Number Publication Date
WO1987004809A1 true WO1987004809A1 (fr) 1987-08-13

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PCT/JP1987/000062 WO1987004809A1 (fr) 1986-01-30 1987-01-29 Procede de formation d'images en couleur

Country Status (4)

Country Link
EP (1) EP0258443B1 (fr)
JP (1) JPH0614180B2 (fr)
AU (1) AU596149B2 (fr)
WO (1) WO1987004809A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0318936A2 (fr) * 1987-12-03 1989-06-07 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière pour une exposition à la lumière laser

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5004669A (en) * 1988-10-31 1991-04-02 Konica Corporation Light-sensitive silver halide photographic material

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51129229A (en) * 1975-05-02 1976-11-10 Fuji Photo Film Co Ltd Method for manufacturing photographic light sensitive materials
JPS60158446A (ja) * 1984-01-27 1985-08-19 Konishiroku Photo Ind Co Ltd 色素画像形成方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD269028A1 (de) * 1982-12-04 1989-06-14 Wolfen Filmfab Veb Verfahren zum einbringen hydrophober fotografischer zusaetze
JPS6275451A (ja) * 1985-09-27 1987-04-07 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
AU6892687A (en) * 1986-01-23 1987-08-14 Fuji Photo Film Co., Ltd. Process for forming colored image

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51129229A (en) * 1975-05-02 1976-11-10 Fuji Photo Film Co Ltd Method for manufacturing photographic light sensitive materials
JPS60158446A (ja) * 1984-01-27 1985-08-19 Konishiroku Photo Ind Co Ltd 色素画像形成方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0258443A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0318936A2 (fr) * 1987-12-03 1989-06-07 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière pour une exposition à la lumière laser
EP0318936A3 (fr) * 1987-12-03 1990-08-22 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière pour une exposition à la lumière laser

Also Published As

Publication number Publication date
AU596149B2 (en) 1990-04-26
EP0258443B1 (fr) 1993-04-07
JPS62175747A (ja) 1987-08-01
EP0258443A4 (en) 1990-11-28
JPH0614180B2 (ja) 1994-02-23
AU6936287A (en) 1987-08-25
EP0258443A1 (fr) 1988-03-09

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