EP0250723B1 - Farbphotographische Silberhalogenidmaterialien - Google Patents

Farbphotographische Silberhalogenidmaterialien Download PDF

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Publication number
EP0250723B1
EP0250723B1 EP19870104526 EP87104526A EP0250723B1 EP 0250723 B1 EP0250723 B1 EP 0250723B1 EP 19870104526 EP19870104526 EP 19870104526 EP 87104526 A EP87104526 A EP 87104526A EP 0250723 B1 EP0250723 B1 EP 0250723B1
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EP
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Prior art keywords
group
silver halide
compound
color photographic
photographic material
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EP19870104526
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English (en)
French (fr)
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EP0250723A2 (de
EP0250723A3 (en
Inventor
Keiji Fuji Photo Film Co. Ltd. Mihayashi
Nobutaka Fuji Photo Film Co. Ltd. Ohki
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP61156979A external-priority patent/JPH07107601B2/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0250723A2 publication Critical patent/EP0250723A2/de
Publication of EP0250723A3 publication Critical patent/EP0250723A3/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
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/39212—Carbocyclic
    • G03C7/39216—Carbocyclic with OH groups

Definitions

  • This invention relates to silver halide color photographic materials, and more particularly to silver halide color photographic materials resistant to formation of color stain and color fog.
  • a process of forming color images by processing a silver halide photographic material after imagewise exposure with a color developer containing an aromatic primary amino developing agent is well known.
  • the above-described developing agent is oxidized by oxygen in the air and the oxidation product of the developing agent forms colored fog by reacting with color couplers at the unexposed portions or little-exposed portions of a photographic light- sensistive material to form dyes.
  • hydroquinone compounds As one means for preventing the formation of such undesirable color fog and color stain, it has been proposed to use hydroquinone compounds.
  • hydroquinones substituted by an aliphatic acylamino group, a ureido group, a urethane group, etc. is proposed by U.S. Patent 4,198,239. These compounds certainly show a high faculty of preventing the formation of color stain to some extent and cause less coloring but the function of preventing color stain is still insufficient. Furthermore, these hydroquinones have a problem with respect to storage stability in that they sometimes deposit crystals during the production of light-sensitive materials.
  • hydroquinones substituted by an alkyl group, aralkyl group, or acylamino group each having a sulfonic acid group is proposed in U.S. Patent 2,701,197 but these compounds have disadvantages such as that the compound diffuses into other photographic layers containing no such compound from the photographic layer containing it during the production and storage of the light-sensitive material, to reduce the function thereof for preventing the formation of color stain and color fog in the photographic layer containing the compound as well as to change the photographic performance of other photographic layers during the production and storage of the light-sensitive material.
  • hydroquinones having an electron attractive group for example, hydroquinone substituted by a carbamoyl group
  • OPI Japanese Patent Application
  • Japanese Patent Publication No. 7578/80 relates to a compound wherein a hydroquinone residue and a coupler residue are contained in the same molecule. This compound forms a color image by coupling reaction upon developing process. Such a property is not admitted for preventing color stain and color fog, which are the object of the present invention.
  • a first object of this invention is to provide a color photographic light-sensitive material having low color stain and color fog.
  • a second object of this invention is to provide a color photographic light-sensitive material containing a color stain preventing agent which is resistant to formation of colored matter during storage and development of the light-sensitive material.
  • a third object of this invention is to provide a color photographic light-sensitive material excellent in color reproducibility showing stable photographic performance for a long period of time without reducing or changing the function of preventing the formation of color stain and colorfog during the production and/ or the storage of the light-sensitive material.
  • a fourth object of this invention is to provide a color photographic light-sensitive material having thinner silver halide emulsion layers and interlayers.
  • R 1 and R 2 in formula (I) described above each represents a hydrogen atom, a halogen atom (e.g., chlorine atom, bromine atom, fluorine atom, etc.), a substituted or unsubstituted alkyl group (having from 1 to 60 carbon atoms, e.g., a methyl group, a t-butyl group, a t-octyl group, a cyclohexyl group, an n-hexadecyl group, a 3-decanamidopropyl group, etc.), a substituted or unsubstituted acylamino group (having from 2 to 60 carbon atoms, e.g., an acetylamino group, an n-butanamido group, a 2-hexyidecan- amido group, a 2-(2',4'-di-t-amylphenoxy)butanamido group, a benzo
  • R 3 in formula (I) represents a hydrogen atom or an alkyl group (having 1 to 20 carbon atoms, e.g., a methyl group, an ethyl group, etc.).
  • R 4 , R 5 , R 6 , R 7 , and R S in formula (I) each represents a hydrogen atom, a halogen atom (e.g., chlorine atom, bromine atom, fluorine atom, etc.), a hydroxyl group, a cyano group, a nitro group, a substituted or unsubstituted alkyl group (having 1 to 60 carbon atoms, e.g., a cyclohexyl group, a dodecyl group, an octadecyl group, a 3-(N,N-dihexylcarbamoyl)propyl group, etc.), a substituted or unsubstituted acylamino group (having 2 to 60 carbon atoms, e.g., an octanoylamino group, a 2-hexyldecanoylamino group, a benzoylamino group, a nico
  • the compound represented by formula (I) may form a bis, tris, or tetrakis compound or a polymer.
  • R 1 and R 2 are preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group and an alkylthio group, more preferably a hydrogen atom, a halogen atom, and an alkyl group, and most preferably are a hydrogen atom.
  • R 3 is a hydrogen atom.
  • R 4 , R 5 , R 6 , R' and R" are a hydrogen atom, an alkyl group, an acylamino group, a sulfonamido group, an alkoxy group, an acyloxy group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or an alkoxysulfonyl group.
  • R 4 , R 5 , R 6 , R' and R" are a hydrogen atom, an alkyl group, an acylamino group, a sulfonamido group, an alkoxy group, an acyloxy group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or an alkoxysulfonyl group.
  • R 4 , R 5 , R 6 , R' and R" are a hydrogen atom, an alkyl group, an acylamino group,
  • the total carbon number of R 1 to R S is preferably at least 15, and more preferably at least 25.
  • R 1 to R S in formula (I) described above may have a substituent.
  • a substituent there are conventional organic groups (e.g., an acylamino group, an alkoxy group, an aryloxy group, an arylthio group, a sulfonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, etc.), halogen atoms, hydroxyl groups, etc., but it is excluded that the substituent is a sulfo or a carboxyl group or an alkali metal- substituted group thereof.
  • the compound represented by formula (I) is substantially water insoluble.
  • the compound does not have sulfo or carboxyl groups or alkali metal substituted groups thereof. If such a group is introduced in the compound of this invention, the compound of this invention becomes soluble in water and hence the compound becomes easily capable of diffusing in photographic layers, which reduces the performance of the photographic layer containing the compound as well as influences on the photographic performance of other photographic layers due to diffusion of the compound therein.
  • the compound of this invention is substantially colorless.
  • substantially colorless means that the compound does not have an absorption of more than 5,000 in molar extinction coefficient in the visible wavelength region of from 400 n.m. to 700 n.m.
  • the compound of this invention does not have in the molecule thereof a coupler residue (e.g., an acylacetanilide residue, a 5-pyrazolone residue, 1- naphthol residue, etc.), which is known to form color images by causing a coupling reaction with the oxidation product of a color developing agent, therefor the compound does not form color images by the coupling reaction during development process.
  • a coupler residue e.g., an acylacetanilide residue, a 5-pyrazolone residue, 1- naphthol residue, etc.
  • the alkali unstable precursor for the compound of this invention represented by formula (I) described above is a compound having at the hydroxyl group of the 1-position and the 4-position of the hydroquinone skeleton of the compound of formula (I) a protective group which can be cleaved under an alkaline conditions.
  • the protective group are an acyl group (e.g., an acetyl group, a chloroacetyl group, a benzoyl group, an ethoxycarbonyl group, etc.) and a ⁇ -releasable group (e.g., a 2-cyanoethyl group, a 2-methanesulfonylethyl group, a 2-toluenesulfonylethyl group, etc.).
  • an acyl group e.g., an acetyl group, a chloroacetyl group, a benzoyl group, an ethoxycarbonyl group, etc.
  • a ⁇ -releasable group e.g., a 2-cyanoethyl group, a 2-methanesulfonylethyl group, a 2-toluenesulfonylethyl group, etc.
  • the compound of this invention is preferably incorporated in at least one of light-sensitive emulsion layers (blue-sensitive layer, green-sensitive layer, and red-sensitive layer), adjacent layers thereto (e.g., an interlayer adjacent to emulsion layers having different color sensitivity, an interlayer formed between two emulsion layers having the same color sensitivity, etc.), a protective layer, an antihalation layer, etc., but it is preferred that the compound exists in the interlayer formed between emulsion layers each having a different color sensitivity.
  • light-sensitive emulsion layers blue-sensitive layer, green-sensitive layer, and red-sensitive layer
  • adjacent layers thereto e.g., an interlayer adjacent to emulsion layers having different color sensitivity, an interlayer formed between two emulsion layers having the same color sensitivity, etc.
  • a protective layer e.g., an antihalation layer, etc.
  • the content of the compound is generally from 1 x 10 -7 to 1 x 10 -2 mol/m 2 , preferably from 1 x 10 -6 to 3 x 10 -3 mol/m 2 , and more preferably from 1 x 10- 5 to 1 x 10- 3 mol/m 2 .
  • the content thereof is generally from 1 x 10 -4 to 1 mol, preferably from 3 x 10 -4 to 3 x 10 -1 mol, and more preferably from 1 x 10 -3 to 1 x 10 -1 mol per mol of silver halide contained in the emulsion layer.
  • the compounds of this invention shown by formula (I) described above can be obtained by the amidation reaction of 2,5-dihydroxyanilines and arylcarboxylic acid chlorides according to Synthesis Example 1 described below, and further can be obtained by the synthesis route wherein the amidation reaction is performed in the form of introducing a protective group such as an alkyl group, a benzyl group, etc. to the hydroxyl group of the 2,5-dihydroxyanilines and then the protective group is removed as shown in Synthesis Examples 2 and 3 described below.
  • a protective group such as an alkyl group, a benzyl group, etc.
  • Monomers used as starting materials for obtaining polymers used in the present invention may be obtained according on the method disclosed in Synthesis Example 5 shown hereinbelow or the method disclosed in Makromol. Chem., Vol. 175, pp. 3133-3146 (1974).
  • the oily product obtained was dissolved in 600 ml of ethanol and after adding thereto 70 ml of an aqueous solution of 35 g of potassium hydroxide, the mixture was refluxed for about 2 hours. After allowing the reaction mixture to cool, the mixture was gradually added dropwise to 500 ml of ice-water containing 100 ml of concentrated hydrochloric acid, and the crystals thus deposited were collected by filtration and recrystallized from acetonitrile to provide 156 g of the crystals of the desired compound.
  • reaction mixture was extracted by adding firstly ethyl acetate and then a hydrochloric acid aqueous solution and the extract thus obtained was dried by anhydrous magnesium sulfate, concentrated, and purified by column chromatography to provide 32 g of oily N-(2,5-dimethoxyphenyl)-N',N'-di(2-ethylhexyl)phthalamide.
  • the oily product thus obtained was dissolved in 200 ml of chloroform and then 20 ml of boron tribromide was gradually added dropwise to the solution with stirring at room temperature. After stirring for one hour, the mixture was poured into ice-water, extracted with ethyl acetate, and the extract was dried and concentrated.
  • the crude crystals thus obtained were purified by column chromatography and then recrystallized from a 20/1 (by volume) mixed solvent of hexane and ethyl acetate to provide 22 g of colorless crystals of N-(2,5-dihydroxyphenyl)-N',N'-di-(2-ethylhexyl)phthalamide having melting point of 118 to 119°C.
  • the product thus obtained was recrystallized from a mixed solvent of hexane and ethyl acetate to provide 24 g of the colorless crystals of 3-acrylamido-N-(2,5-dimethoxyphenyl)benzamide having melting point of 149 to 150°C.
  • the product thus obtained was added to 200 ml of dichloroethane with stirring and dissolved by heating the mixture up to 60°C. After then 20 ml of boron tribromide was gradually added dropwise to the solution. Thereafter, the mixture was further stirred for one hour at 60°C, poured into ice-water, and extracted with ethyl acetate. The extract obtained was concentrated, and purified by column chromatography using chloroform as solvent. Thus purified product was concentrated to provide 17 g of a light-yellow solid polymer.
  • the compounds of this invention shown by formula (I) or the couplers or dye-image-providing compounds with which the compounds of this invention are used, described hereinafter, can be introduced into the photographic light-sensitive materials of this invention by various known dispersion methods. Examples include a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil drop-in-water dispersion method.
  • the compound is dissolved in a high-boiling organic solvent having boiling point of at least 175°C or a low-boiling so-called auxiliary solvent or a mixture thereof and the solution of the compound is finely dispersed in an aqueous medium such as water and an aqueous gelatin solution, etc., in the existence of a surface active agent.
  • a high-boiling organic solvent such as water and an aqueous gelatin solution, etc.
  • the dispersion may be accompanied by a phase inversion or the dispersion may be used for coating after, if necessary, reducing the auxiliary solvent by distillation, noodle water washing, or ultrafiltration method.
  • the high-boiling organic solvent are phthalic acid esters (e.g., dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, didodecyl phthalate, etc.), phosphoric acid esters or phosphonic acid esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate, etc.), benzoic acid esters (e.g., 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl p-hydroxy
  • an auxiliary solvent having boiling point of about 30°C to about 160°C and specific examples of such auxiliary solvent are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, etc.
  • a latex dispersion method can be applied for dispersing the compound of this invention shown by formula (I) and specific examples of the dispersion process, the effects thereof, and the latex for impregnation are described in U.S. Patent 4,199,363, West German Patent Application (OLS) Nos. 2,541,274, 2,541,230, etc.
  • the compounds of this invention represented by formula (I) described above are preferably utilized for ordinary color photographic light-sensitive materials for coupler system and color diffusion transfer photographic light-sensitive materials using dye-providing compounds.
  • the photographic film unit may have a construction of a peel-apart type film unit or an integrated type film unit as described in Japanese Patent Publication Nos. 16,356/71, 33,697/73, Japanese Patent Application (OPI) No. 13,040/75, and British Patent No. 1,330,524, or the non-peel-apart type film unit as described in Japanese Patent Application (OPI) No. 119,345/82.
  • the compound of this invention shown by formula (I) may exist in any layer of the light-sensitive material or may be incorporated in a container for processing composition as a component of the processing composition.
  • silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, or silver chloride can be used as silver halide.
  • a preferred silver halide is silver iodobromide or silver iodochlorobromide containing at most about 30 mole% silver iodide.
  • a particularly preferred silver halide is silver iodobromide containing about 2% to about 25% silver iodide.
  • the silver halide grains in the photographic emulsions may be so-called regular grains having a regular crystal form such as cube, octahedron, tetradecahedron, etc., an irregular crystal form such as sphere, etc., or a crystal form having a crystal defect such as twinning plane. Furthermore, the silver halide grains may be a composite form thereof.
  • the silver halide grains may be fine grains having grain sizes (diameters) of not more than about 0.1 micron or large grains that the diameter of the projected area becomes about 10 microns.
  • the silver halide emulsion for use in this invention may be a mono-dispersed silver halide emulsion having a narrow grain size distribution or a poly-dispersed silver halide emulsion have a broad grain distribution.
  • the silver halide photographic emulsions for use in this invention can be prepared by known methods, such as the methods described, for example, in Research Disclosure. No. 17643 (Dec., 1978), pages 22-23, "Emulsion Preparation and Types", and No. 18716 (Nov. 1979), page 648.
  • the silver halide emulsions for use in this invention can be prepared using the methods described in P. Glafkides, Chimie et Physique Photographique Paul Montel, published by Paul Montel, 1967; G. F. Duffin, Photographic Emulsion Chemistry, published by Focal Press, 1966; V. L. Zelikman et al., Making and Coating Photographic Emulsion, published by Focal Press, 1964, etc.
  • the photographic emulsion may be prepared by an acid method, a neutralization method, an ammonia method, etc.
  • a system for reacting a soluble silver salt and a soluble halide a single jet method, a double jet method, or a combination thereof may be used.
  • a so-called back mixing method for forming silver halide grains in the existence of excessive silver ion can be used.
  • a so-called controlled double jet method wherein the pAg in the liquid phase of forming silver halide is kept at a constant value can be used. According to this method, a silver halide emulsion having a regular crystal form and almost uniform grain sizes is obtained.
  • Two or more kinds of silver halide emulsions separately prepared cn be used as a mixture thereof.
  • the silver halide emulsion containing the above-described regular silver halide grains can be obtained by controlling the pAg and pH during the formation of the silver halide grains. More practically, such a method is described in Photographic Science and Engineering, Vol. 6, 159-165 (1962); Journal of Photographic Science, Vol. 12, 242-251 (1964); U.S. Patent 3,655,394, and British Patent 1,413,748.
  • a mono-dispersed silver halide emulsion is typically a silver halide emulsion wherein the mean grain size of the silver halide grains is at least about 0.1 pm and about 95% by weight of the silver halide grains are within ⁇ 40% of the mean grain size.
  • the silver halide emulsion that the mean grain size of the silver halide grains is from about 0.25 to 2 pm and at least about 95% by weight or at least about 95% by number of the silver halide grains are in the range of ⁇ 20% of the mean grain size can be preferably used in this invention.
  • the production methods for such a silver halide emulsion are described in U.S. Patents 3,547,628, 3,655,394, and British Patent 1,413,748.
  • the mono-dispersed silver halide emulsions as described in Japanese Patent Application (OPI) Nos. 8600/73, 39,027/76, 83,097/76, 137,133/78, 48,521/79, 99,419/79, 37,635/83, 49,938/83, etc. can be preferably used in this invention.
  • tabular silver halide grains having an aspect ratio of at least about 5 can be used in this invention.
  • Tabular silver halide grains can be easily prepared by the methods described in Gutoff, Photographic Science and Engineering, Vol. 14, 248-257 (1970); U.S. Patents 4,434,226, 4,414,310, 4,433,048, 4,439,520, British Patent 2,112,157, etc.
  • U.S. Patents 4,434,226, 4,414,310, 4,433,048, 4,439,520 British Patent 2,112,157, etc.
  • there are such advantages as the increase of the color sensitizing effect by sensitizing dyes, the improvement of graininess, and the increase of sharpness as described in detail for instance, in above-described U.S. Patent 4,434,226.
  • the silver halide grains may have a different halogen composition between the inside and the outside thereof or may have a layer structure.
  • These silver halide emulsion grains are disclosed in British Patent 1,027,146, U.S. patents 3,505,068, 4,444,877 and Japanese Patent Application (OPI) No. 143331/85.
  • silver halides each having different composition may be connected each other by an epitaxial junction or a silver halide may be connected to other compound than silver halide, such as silver rhodanide, lead oxide, etc.
  • These silver halide emulsion grains are disclosed in U.S. Patents 4,094,684, 4,142,900, 4,459,353, British Patent 2,038,792, U.S. Patents 4,349,622, 4,395,478, 4,433,501, 4,463,087, 3,656,962, 3,852,067, Japanese Patent Application (OPI) No. 162,540/84, etc.
  • the silver halide emulsions for use in this invention are usually subjected to physical ripening, chemical ripening, and spectral sensitization. Additives which are used in such steps are described in Research Disclosures, RD No. 17643 (Dec. 1978) and RD No. 18716 (Nov. 1979) and they are summarized in the following table.
  • various color couplers can be used. Specific examples of these couplers are described in above-described Research Disclosure, No. 17643, VII-C to VII-G as patent references.
  • dye-forming couplers couplers giving three primary colors (i.e., yellow, magenta, and cyan) by subtraction color process by color development are typically important, and specific examples of non-diffusible couplers, four-equivalent couplers, and two-equivalent couplers are described in Patents referred in above-described Research Disclosure, No. 17643, VII-C and VII-D and further the following couplers can be also preferably used in this invention.
  • Typical yellow couplers which can be used in this invention include hydrophobic acetylacetamide series couplers having a ballast group. Specific examples of the yellow coupler are described in U.S. Patents 2,407,210, 2,875,057 and 3,265,506. In this invention, the use of two-equivalent yellow couplers is preferred. Typical examples thereof are the oxygen atom-releasing type yellow couplers described in U.S. Patents 3,408,194, 3,447,928, 3,933,501, and 4,022,620 and the nitrogen atom-releasing type yellow couplers described in Japanese Patent Publication 10,739/83, U.S. Patents 4,401,752, 4,326,024, Research Disclosure, No.
  • a-pivaloylacetanilide series couplers are excellent in fastness, in particular light fastness of the colored dye.
  • a-benzoylacetanilide series couplers show high coloring density.
  • Typical magenta couplers which can be used in this invention include hydrophobic indazolone type or cyanoacetyl series, preferably 5-pyrazolone type and pyrazoloazole series couplers each having a ballast group.
  • the 5-pyrazolone series couplers the 3-position of which is substituted by an arylamino group or an acylamino group are preferred in the view points of the hue and coloring density of the colored dye.
  • Specific examples of such couplers are described in U.S. Patents 2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653,3,152,896,3,936,015, etc.
  • the nitrogen atom releasing group described in U.S. Patent 4,310,619 and the arylthio group described in U.S. Patent 4,351,897 are particularly preferred.
  • the 5-pyrazolone type couplers having ballast group described in European Patent No. 73,636 give high coloring density.
  • the pyrazoloazole type magenta couplers there are the pyrazolobenzimidazoles described in U.S. Patent 3,369,879, preferably the pyrazolo[5,1-c][1,2,4]triazoles described in U.S.
  • Patent 3,725,067 the pyrazolotetrazoles described in Research Disclosure, RD No. 24220 (June, 1984) and Japanese Patent Application (OPI) No. 33,552/85, and the pyrazolopyrazoles described in Research Disclosure, RD No. 24230 (June, 1984) and Japanese Patent Application (OPI) No. 43,659/85.
  • the imidazo[1,2-b]pyrazoles described in U.S. Patent 4,500,630 are preferred and the pyrazoio[1,5-b][1,2,4]triazofos described in European Patent 119,860A are particularly preferred.
  • Typical cyan couplers which can be used in this invention include hydrophobic and non-diffusible naphtholic and phenolic couplers.
  • Typical examples of the cyan couplers are the naphtholic couplers described in U.S. Patent 2,474,293 and preferably the oxygen atom releasing type two-equivalent naphtholic couplers described in U.S. Patents 4,052,212, 4,146,396, 4,228,233, and 4,296,200.
  • specific examples of the phenolic couplers are described in U.S. Patents 2,369,929, 2,801,171, 2,772,162, 2,895,826, etc.
  • Cyan couplers having fastness to humidity and temperature are preferably used in this invention and specific examples of such cyan couplers are the phenolic cyan couplers having an alkyl group of at least 2 carbon atoms at the meta-position of the phenol nucleus described in U.S. Patent 3,772,002, the 2,5-diacyl- amino-substituted phenolic couplers described in U.S. Patents 2,772,162, 3,758,308, 4,126,396, 4,334,011, 4,327,173, West German Patent Application (OLS) No. 3,329,720, and European Patent No.
  • OLS West German Patent Application
  • colored couplers For correcting additional, undesirable absorption of colored dye, it is preferred to perform color masking by using colored couplers together in the case of color photographic materials for in-camera use.
  • these colored couplers are the yellow-colored magenta couplers described in U.S. Patent 4,163,670 and Japanese Patent Publication No. 39,413/82, and the magenta-colored cyan couplers described in U.S. Patents 4,004,929, 4,138,258 and British Patent 1,146,368.
  • Other colored couplers which can be used in this invention are described in above-described Research Disclosure, RD No. 17643, VII-G.
  • the graininess can be improved by using together couplers capable of forming colored dyes having proper diffusibility.
  • couplers capable of forming colored dyes having proper diffusibility.
  • specific examples of magenta couplers are described in U.S. Patent 4,366,237 and British Patent 2,125,570 and specific examples of yellow couplers, magenta couplers and cyan couplers are described in European Patent 96,570 and West German Patent Application (OLS) No. 3,234,533.
  • the dye-forming couplers and the above-described specific couplers each may form a dimer or higher polymers.
  • Typical examples of the polymerized dye-forming couplers are described in U.S. Patents 3,451,820 and 4,080,211.
  • specific examples of the polymerized magenta couplers are described in British Patent 2,102,173 and U.S. Patent 4,367,282.
  • Couplers releasing a photographically useful residue upon coupling are preferably used in this invention.
  • DIR couplers i.e., couplers releasing development inhibitor are described in the patents cited in above-described Research Disclosure, No. 17643, VII-F.
  • these couplers which can be used in this invention are the developer inactivating type couplers described in Japanese Patent Application (OPI) No. 151,944/82, the timing type couplers described in U.S. Patent 4,248,962 and Japanese Patent Application (OPI) No. 154,234/82, the reaction type couplers described in Japanese Patent Application (OPI) No. 184248/85, etc.
  • Particularly preferred examples of these couplers are the development in activating type DIR couplers described in Japanese Patent Application (OPI) Nos. 151,944/82, 217,932/83, Japanese Patent Application (OPI) Nos. 218645/85, 225156/85, 233650/85, etc., and the reaction type DIR couplers described in Japanese Patent Application (OPI) No. 184248/85, etc.
  • couplers imagewise releasing a nucleating agent or a development accelerator or a precursor thereof at development can be used. Specific examples of these couplers are described in British Patents 2,097,140 and 2,131,188. Also, couplers releasing a nucleating agent having an adsorptive action for silver halide are particularly preferred in this invention and specific examples thereof are described in Japanese Patent Application (OPI) Nos. 157,638/94 and 170,840/84.
  • OPI Japanese Patent Application
  • the color photographic light-sensitive materials of this invention can be processed by the ordinary processes as described, for example, in above-described Research Disclosure, No. 17643, pages 28 to 29 and ibid., No. 18716, page 651, left column to right column.
  • the color photographic light-sensitive materials of this invention are usually subjected to water- washing treatment or a stabilization treatment after development and blixing or fixing.
  • the water washing step is generally performed by a countercurrent washing using two or more water baths in order to save water.
  • the stabilization process the multistage countercurrent stabilization process described in Japanese Patent Application (OPI) No. 8543/82 is typical. Such a stabilization process may be used in place of the water washing step. In the case of the stabilization process, 2 to 9 countercurrent baths are required.
  • the stabilization composition contains various compounds for stabilizing images.
  • buffers e.g., borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc., or a combination thereof
  • formalin for adjusting the pH of films e.g., pH 3 to 8
  • the stabilization composition may contain other additives such as a water softener (e.g., an inorganic phosphoric acid, aminopolycarboxylic acid, an organic phosphoric acid, and aminopolyphosphoric acid, a phosphonocarboxylic acid, etc.), a germicide (e.g., benzoisothiazolinone, isothiazolone, 4-thiazolinebenzimidazole, halogenated phenol, etc.), a surface active agent, an optical whitening agent, a hardening agent, etc. Two or more kinds of these compounds may be used in combination.
  • a water softener e.g., an inorganic phosphoric acid, aminopolycarboxylic acid, an organic phosphoric acid, and aminopolyphosphoric acid, a phosphonocarboxylic acid, etc.
  • a germicide e.g., benzoisothiazolinone, isothiazolone, 4-thiazolinebenzimidazole, halogenated
  • ammonium salt such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate, etc.
  • an ammonium salt such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate, etc.
  • the dye image-providing compounds which are used in association with silver halide emulsion layers can be of a negative type or of a positive type, and can be initially mobile or immobile in the photographic element, depending on the particular embodiment, when it is processed by an alkaline processing composition.
  • Typical negative-type (negative-working) dye image-providing compounds useful for this invention include couplers forming or releasing dyes by causing reaction with the oxidized product of a color developing agent. Specific examples of these couplers are described in U.S. Patent 3,227,550 and Canadian Patent 602,607, etc.
  • As the preferred negative-working dye image-providing compounds for use in this invention there are dye-releasing redox compounds releasing a dye by reacting with a developing agent in an oxidized state or an electron transferring agent and specific examples thereof are described in U.S. Patents 3,928,312, 4,135,929, 4,055,428, 4,336,322, 4,053,312, etc.
  • immobile positive-working dye-providing compounds for use in this invention there are compounds releasing a diffusible dye without receiving no electron (that is, without being reduced) or after receiving at least one electron (that is, after being reduced) during photographic processing under an alkaline condition and specific examples thereof are described in U.S. Patents 4,199,354, 3,980,479, 4,199,355, 4,139,379, 4,139,389, 4,232,107, and Japanese Patent Application (OPI) No. 69,033/78.
  • positive-working dye image-providing compounds which are mobile from the first under an alkaline photographic processing condition are useful for the photographic elements of this invention.
  • Typical examples thereof are dye developing agents and specific examples of these compounds are described in U.S. Patents 3,482,972 and 3,880,658.
  • the dye formed from the dye image-providing compound for use in this invention may be a dye itself or a dye precursor which can be converted into dye in a photographic processing step or an addition processing step.
  • the final image dye may be or may not be in a metal complex form.
  • typical dye structures useful for this invention there are azo dyes, azomethine dyes, anthraquinone dyes, phthalocyanine dyes, either in a metal complex form or not in a metal complex form. In these dyes, cyan, magenta and yellow dyes are particularly important.
  • a dye-releasing redox compound having a dye moiety, the light absorption of which is temporarily shifted, in the light-sensitive element can be used in this invention.
  • Specific examples thereof are described in U.S. Patents 4,310,612, T-999,003, 3,336,287, 3,579,334, 3,982,946, British Patent 1,467,317, and Japanese Patent Application (OPI) No. 158,638/82.
  • any silver halide developing agents which can cross-oxidize dye-releasing redox compounds can be used.
  • a developing agent may exist in an alkaline processing composition or in a proper layer of the photographic element.
  • the developing agent which can be used for processing the photographic element are hydroquinones, aminophenols, phenylenediamines, and pyrazolidinones (e.g., pheidone, 1-phenyl-3-pyrazolidinone, dimeson (i.e., 1-phenyl-4,4-dimethyl-3-pyrazolidinone), 1-p-tolyl-4-methyl-4-oxymethyl-3-pyrazolidinone, 1-(4'- methoxyphenyl)-4-methyl-4- oxymethyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-oxymethyl-3-pyrazolidinone, etc., as described, for example, in Japanese Patent Application (OPI) No. 16,131/81.
  • the processing composition which is used for processing the photographic element according to a color diffusion transfer process contains sodium hydroxide, potassium hydroxide, sodium carbonate, sodium phosphate, etc., for adjusting the pH thereof about above 9, preferably 11.5 or above.
  • the processing composition may further contain an antioxidant such as sodium sulfite, an ascorbate, piperidinohexose reduction, etc., and further may contain a silver ion concentration controlling agent such as potassium bromide, etc.
  • the processing composition may further contain a viscosity increasing compound such as hydroxyethyl cellulose, sodium carboxymethyl cellulose, etc.
  • This invention can be applied to various kinds of color photographic light-sensitive materials.
  • color photographic light-sensitive materials there are general color photographic films, negative color photographic cine films, color reversal photographic films for slide or television, color photographic papers, color positive photographic films, color diffusion transfer direct positive light-sensitive materials, color reversal photographic papers, etc.
  • This invention can be also applied to a black and white light-sensitive material utilizing a mixture of three- color couplers described in Research Disclosure, RD No. 17123 (July, 1978).
  • a multilayer color photographic light-sensitive material (101) having layers of the following compositions on a transparent triacetyl cellulose film support was prepared.
  • compositions described above contained a gelatin hardening agent H-1 and a surface active agent in addition to the above-described components.
  • each of the samples was imagewise exposed to red light and processed as described below. After processing, the density of the sample was measured using a red filter or a green filter, and the value obtained by subtracting the magenta fog density from the magenta density in the exposure amount that the cyan density measured by the red filter gave a density of fog + 1.5 is shown in Table 1 below as color turbidity.
  • compositions of the processing liquids used for the above process were as follows.
  • condition (A) the samples were imagewise exposed to white light and subjected to photographic processing as described above.
  • the densities of these samples thus processed were measured and the yellow, magneta and cyan densities under condition (B), which was a forcible deterioratig condition, at the exposure amount that each of yellow, magenta and cyan densities under condition (A) density 1.5 are shown in Table 1 above.
  • a light-sensitive sheet A was prepared by coating the following layers in succession on a transparent polyethylene terephthalate film support.
  • light-sensitive sheets B, C, and D were prepared as comparison samples by the following manners.
  • the light-sensitive sheet was prepared by following the same procedure as the case for preparing Sheet A except that 0.49 g/m 2 (same molar amount) of 2,5-di-t-pentadecylhydroquinone described in Japanese Patent Application (OPI) No. 29637/79 was used in place of the compound of this invention as the color stain preventing agent in Layer (6) of Light-sensitive Sheet (A).
  • the light-sensitive sheet was prepared by following the same procedure as the case of preparing Sheet A except that 0.47 g/m 2 (same molar amount) of 2-sec-octadecyl-5-benzenesulfonylhydroquinone (compound (22) of U.S. Patent 4,277,553) was used in place of the color stain preventing agent in Layer (6) of Light-sensitive Sheet A.
  • the light-sensitive sheet was prepared by following the same procedure as the case of preparing Light-sensitive Sheet A except that Layer (7) and Layer (8) of Light-sensitive Sheet A were omitted.
  • a cover sheet was prepared by successively coating the following layers on a transparent polyester support.
  • a processing solution having the following composition was prepared.
  • each of the samples was integrated in a body together with a container containing the above-described processing solution and the cover sheet and the processing solution was spread between the light-sensitive sheet and the cover sheet at a thickness of 80 pm by means of pressure-applying members at 25°C or 35°C to provide transferred color images.
  • the green filter density (Dg) and the blue-filter density (Db) were obtained.
  • each layer (6) containing each color stain preventing agent was formed for preventing the release of yellow dye by the reaction with an oxidation product of a developing agent (whereby, preventing the occurrence of magenta color turbidity, i.e., the deterioration of magenta hue by the mixing of yellow with magenta) when the oxidation product of developing agent formed in Layer (5) containing the green-sensitive silver halide emulsion diffused into layer (7) containing the yellow dye-releasing redox compound, which was not associated with the silver halide emulsion layer (5) through Layer (6).
  • a developing agent whereby, preventing the occurrence of magenta color turbidity, i.e., the deterioration of magenta hue by the mixing of yellow with magenta
  • a color photographic light-sensitive material was prepared by forming the following photographic layers composed for layer 1 to layer 7 on a paper support both surfaces of which were laminated with polyethylene.
  • the polyethylene layer at the side of carrying the photographic layers contained titanium dioxide and a slight amount of ultramarine blue.
  • the numeral for each component shown below shows a coated amount (coverage) shown by the unit of g/m 2 and the numeral about silver halide emulsion shows a coated amount calculated as silver.
  • DBP include dibutyl phthalate
  • TOP indicates tri(n-octyl phosphate)
  • TNP indicates tri(n-nonyl phthalate).
  • Green-Sensitive Emulsion Layer Red-Sensitive Emulsion Layer:
  • compositions of the processing solutions used in the above steps were as follows.
  • the density of each of the samples thus processed was measured using a green filter (magenta coloring density). Then, by obtaining the difference between the magenta density in the maximum yellow coloring density and the magenta density on the lowest yellow coloring density, the magenta color mixing in the yellow colored portion was determined. The results are shown in Table 3 below.
  • the film sample was prepared by forming the following emulsion layers and auxiliary layers successively in the order shown below on a triacetyl cellulose support.
  • An emulsion was prepared by following the same procedure as the case of preparing the emulsion for Layer 1 except that 125 g of a magenta coupler, 1-(2,4,6-trichlorophenyl)-3- ⁇ 3-(2,4-di-t-amylphenoxyacet- amido)benzamido ⁇ -5-pyrazoione in place of the cyan coupler, 500 g of the emulsion thus obtained was mixed with 1 kg of a green-sensitive silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin and having an iodine content of 2.5 mol%), and the resultant mixture was coated thereon at a dry thickness of 2.0 pm.
  • a green-sensitive silver iodobromide emulsion containing 70 g of silver and 60 g of gelatin and having an iodine content of 2.5 mol%
  • a mixture of 700 g of the emulsion as used for Layer 3 and 1 kg of a 10% aqueous gelatin solution was coated thereon at a dry thickness of 0.9 pm.
  • An aqueous gelatin solution containing yellow colloid silver was coated thereon at a dry thickness of 1pm.
  • An emulsion was prepared by following the same procedure as the case of preparing the emulsion for Layer 1 except that 70 g of a yellow coupler, a-(pivaloyl)-a-(l-benzyl-5-ethoxy-3-hydantoinyl)-2-chloro-5-dodecyloxycarbonylacetanilide was used in place of the cyan coupler, 800 g of the emulsion thus obtained was mixed with 1 kg of a blue-sensitive silver iodobromide emulsion (containing 70 g of silver and 60 g of gelatin and having an iodine content of 2.5 mol%), and the resultant mixture was coated thereon at a dry thickness of 2.0 pm.
  • a blue-sensitive silver iodobromide emulsion containing 70 g of silver and 60 g of gelatin and having an iodine content of 2.5 mol%
  • a mixture of 1 kg of the emulsion as used for Layer 3 and 1 kg of a 10% aqueous gelatin solution was coated thereon at a dry thickness of 1 pm.
  • a 10% aqueous gelatin solution containing a fine grain silver iodobromide emulsion (having a mean grain size of 0.15 ⁇ m and an iodine content of 1 mol%) which was not chemically sensitized was coated thereon with a silver coverage of 0.3 g/m 2 and at a dry thickness of 1 pm.
  • compositions of the processing solutions used for the above processing steps were as follows.
  • the maximum coloring density (Dmax) and the minimum density (Dmin) were measured using red filter. Also, the maximum coloring density of the blue-sensitive emulsion layer and the green-sensitive emulsion layer of each sample were measured using a blue-filter and a green filter, respectively.

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  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (12)

1. Farbphotographisches Silberhalogenidmaterial, enthaltend wenigstens eine im wesentlichen farblose Verbindung, gewählt aus der Gruppe, bestehend aus Verbindungen der Formel I
Figure imgb0141
und alkalischen, instabilen Vorläufern davon, Bis-, Tris- und Tetrakisverbindungen, abgeleitet aus der Verbindung, und Polymeren, abgeleitet aus der Verbindung; worin R1 und R2 jeweils ein Wasserstoffatom, ein Halogenatom, eine substituierte oder unsubstituierte Alkyl-, Acylamino-, Alkoxy-, Aryloxy-, Alkylthio-, Arylthio-, Sulfonyl-, Carbamoyl- oder Sulfamoylgruppe bedeutet; oder R1 und R2 zusammen einen carbocyclischen Ring bilden; R3 ein Wasserstoffatom oder eine Alkylgruppe bedeutet; und R', R5, R6, R7 und R8 jeweils ein Wasserstoffatom, ein Halogenatom, eine Hydroxylgruppe, eine Cyanogruppe, eine Nitrogruppe oder eine substituierte oder unsubstituierte Alkyl-, Acylamino-, Sulfonamido-, Alkoxy-, Aryloxy- Alkylthio-, Arylthio-, Amino-, Acyl-, Acyloxy-, Carbamoyl-, Carbamoylamino-, Carbamoyloxy-, Sulfamoyl-, Sulfamoylamino-, Alkoxycarbonyl-, Aryloxycarbonyl-, Alkoxycarbonylamino-, Aryloxycarbonylamino-, Alkoxycarbonyloxy-, Aryloxycarbonyloxy-, heterocyclische Ring-, Alkoxysulfonyl oder Aryloxysulfonylgruppe bedeutet; oder zwei benachbarte Gruppen zusammen einen carbocyclischen Ring einen oder heterocyclischen Ring bilden; die Summe der Kohlenstoffatomzahl von R1 bis RB wenigstens 8 ist; und die Verbindung der Formel I in Wasser im wesentlichen unlöslich ist und kein Farbbild durch eine Kupplungsreaktion mit einem oxidierten Produkt eines Entwicklungsmittels bildet.
2. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin die im wesentlichen farblose Verbindung in wenigstens einer Schicht, gewählt aus einer Zwischenschicht, einer Antilichthofschicht und Schutzschichten des photographischen Materials, und in einer Menge von 1 x 107 bis 1 x 10-2 Mol/m2 vorliegt.
3. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin die im wesentlichen farblose Verbindung in einer Silberhalogenidemulsionsschicht in einer Menge von 1 x 10-4 bis 1 Mol pro Mol Silberhalogenid, enthalten in der Emulsionsschicht, vorliegt.
4. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin die Substituenten für R1 bis R8 wenigstens eine Gruppe, gewählt aus der Gruppe, bestehend aus einer Acylaminogruppe, einer Alkoxygruppe, einer Aryloxygruppe, einer Arylthiogruppe, einer Sulfonylgruppe, einer Acylgruppe, einer Carbamoylgruppe, einer Sulfamoylgruppe, Halogenatomen und eine Hydroxylgruppe, sind.
5. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin der alkalische instabile Vorläufer der Verbindung der Formel eine Verbindung ist, die an der Hydroxylgruppe in der 1-Position und der 4-Position des Hydrochinongerüsts der Verbindung der Formel I eine Schutzgruppe besitzt, die unter alkalischen Bedingungen abgespalten werden kann.
6. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin das farbphotographische Silberhalogenidmaterial ein farbphotographisches lichtempfindliches Material für ein Kupplersystem ist.
7. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin das farbphotographische Silberhalogenidmaterial ein photographisches lichtempfindliches Farbdiffusionsübertagungsmaterial unter Verwendung wenigstens einer farbstoffliefernden Verbindung ist.
8. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin die farblose Verbindung in einem Behälter für eine Behandlungszusammensetzung als Komponente der Behandlungszusammensetzung eingearbeitet ist.
9. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin R' und R2 jeweils einge Gruppe, gewählt aus der Gruppe, bestehend aus einem Wasserstoffatom, einem Halogenatom, einer Alkylgruppe, einer Alkoxygruppe und einer Alkylthiogruppe, ist.
10. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin R3 ein Wasserstoffatom ist.
11. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin R4, R5, R6, R7 und R8 jeweils eine Gruppe, gewählt aus der Gruppe, bestehend aus einem Wasserstoffatom, einer Alkylgruppe, einer Acylaminogruppe, einer Sulfonamidgruppe, einer Alkoxygruppe, einer Acyloxygruppe, einer Carbamoylgruppe, einer Sulfamoylgruppe, einer Alkoxycarbonylgruppe und einer Alkoxysulfonylgruppe, ist.
12. Farbphotographisches Silberhalogenidmaterial nach Anspruch 1, worin die Gesamtkohlenstoffzahl von R' bis RB wenigstens 15 ist.
EP19870104526 1986-07-03 1987-03-26 Farbphotographische Silberhalogenidmaterialien Expired EP0250723B1 (de)

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JP61156979A JPH07107601B2 (ja) 1985-07-26 1986-07-03 ハロゲン化銀カラー写真感光材料
JP156979/86 1986-07-03

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