US3926631A - Silver halide photographic light-sensitive material - Google Patents

Silver halide photographic light-sensitive material Download PDF

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US3926631A
US3926631A US461204A US46120474A US3926631A US 3926631 A US3926631 A US 3926631A US 461204 A US461204 A US 461204A US 46120474 A US46120474 A US 46120474A US 3926631 A US3926631 A US 3926631A
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group
light
coupler
silver halide
sensitive
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Atsuaki Arai
Yasushi Oishi
Minoru Yamada
Nobuo Furutachi
Kotaro Nakamura
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • G03C7/32—Colour coupling substances
    • G03C7/36—Couplers containing compounds with active methylene groups
    • G03C7/38—Couplers containing compounds with active methylene groups in rings
    • G03C7/384—Couplers containing compounds with active methylene groups in rings in pyrazolone rings

Definitions

  • ABSTRACT A light-sensitive silver halide: emulsion containing a S-pyrazolone coupler in which the 4-position is substituted with a carbonic acid ester group or an oxalic acid ester group.
  • FILMB DEVELOPED SILVER/COLORED DYE (MDLAR RATIO) N J4 4 in 03 ⁇ I 00 to I I FILMA 160 200 360 400 AMOUNT OF DEVELOPED SILVER (mg/m SILVER I-IALIDE PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL BACKGROUND OF THE INVENTION phy and a silver halide color photographic material containing the same.
  • a coupler of the acylacetanilide or dibenzoylmethane type is used for forming a yellow color image
  • a coupler of the pyrazolone, cyanoacetophenone or indazolone type is used for forming a magenta color image
  • a coupler of the phenol type such as a phenol and a naphthol, is used for forming a cyan color image.
  • a coupler forming a dye is added to a developer or incorporated in a light-sensitive photographic emulsion layer. Therefore, an oxidized color developing agent, which is formed when a latent image is developed, is reacted with the coupler to form a color image.
  • the color image-forming couplers of the prior art are almost all four equivalent couplers which require theoretically four mols of silver halide as an oxidizer for forming 1 mol of the dye through the coupling reaction.
  • a two equivalent coupler having an active methylene group which is substituted by a group capable of being split off through the coupling of an oxidized product of the developing agent consisting of an aromatic primary amine requires only the development of two mols of silver halide for forming 1 mol of the dye.
  • the two-equivalent coupler Since the quantity of silver halide required for forming a dye in the case of a two equivalent coupler is one half of that required in the case of an ordinary four equivalent coupler, the two-equivalent coupler has many advantages in that a thinner light-sensitive layer can be used and the layer can be processed rapidly. In addition, the photographic properties and economy can be increased through a reduction in the film thick ness.
  • a two'equivalent magenta coupler has been desired because generally a higher coupler to dye conversion ratio is obtained than the four equivalent coupler and less influence upon the fading of a color image due to remaining of the coupler is exhibited.
  • the hitherto proposed two equivalent couplers have various disadvantages in that the reactivity is not suitable, staining and fogging occur and there are many difficulties in synthesizing the couplers.
  • R and R represent conventional groups such as are used in four equivalent pyrazolone couplers, R represents a monovalent group, R represents a divalent group and n represents or l-.
  • R is a hydrogen atom or a group of l to about 50 carbon atoms, preferably 1 to 35 carbon atoms, i.e., a straight chain or branched chain alkyl group such as a methyl, ethyl, i-propyl, tert-butyl, hexyl, tert-octyl or dodecyl group; an alkenyl group such as an allyl group; a cycloalkyl group such as a cyclohexyl or norbornyl group; a substituted alkyl or cycloalkyl group containing as a substituent, a halogen atomor a nitro, cyano, aryl, alkoxy, aryloxycarboxy, alkoxycarbonyl, aryloxycarbonyl, sulfo, sulfamoyl, carbamoyl, acylamino, ureido, arylsul
  • R is' an aryl group such as a phenyl or an aor B-naphthyl group; an aryl group having one or more substituents such as alkyl, alkoxy, aryloxy, carboxy, alkoxycarbonyl, acylamino, carbamoyl, alkylcarbamoyl, dialkylcarbamoyl, arylcarbamoyl, alkylsulfonamide, arylsulfonamide, sulfamoyl, alkylsulfamoyl, cyano and nitro groups or halogen atoms.
  • substituents such as alkyl, alkoxy, aryloxy, carboxy, alkoxycarbonyl, acylamino, carbamoyl, alkylcarbamoyl, dialkylcarbamoyl, arylcarbamoyl, alkylsulfonamide, arylsulfonamide,
  • R represents a heterocyclic group such as S-membered or 6-membered heterocyclic group or condensed heterocyclic group containing, as a hetero-atom, a nitrogen, oxygen or sulfur atom, for example, pyridyl, quinolyl, furyl, benzothiazolyl, oxazolyl, imidazolyl or naphthoxazolyl group, or a substituted heterocyclic group with the substituents above described for the aryl group.
  • R represents a carbamoyl or thiocarbamoyl group.
  • R represents a group having 1 to about 50 carbon atoms, preferably 1 to 35 carbon atoms, i.e., the same alkyl, substituted alkyl, aryl, substituted aryl, heterocyclic group or substituted heterocyclic group as described for R
  • R represents an alkoxycarbonyl group such as a methoxycarbonyl or ethoxycarbonyl group; an aryloxycarbonyl group; an aralkyloxycarbonyl group; substituted oxy group such as an alkoxy group, e.g., methoxy, ethoxy, decycloxy, etc., or an aryloxy group, e.g., a phenoxy, tolyloxy, etc.; a substituted thio group such as an alkylthio group, e.g., ethylthio, propylthio, etc., or an arylthio group, e.g., phenylthio, tolylthio,
  • R represents a group having I to about 30 carbon atoms, i.e., a straight chain or branched chain alkyl group such as a methyl, ethyl, i-propyl, i-amyl, 2-ethylhexyl, dodecyl or stearyl group; an alkenyl group such as an allyl or oleyl group; a cycloalkyl group such as cyclohexyl group; an alkyl or cycloalkyl group substituted with a halogen atom or a nitro, cyano, aryl, alkoxy, aryloxy, carboxyester, sulfoester, amido, sulfonamido, ureido, carbamyl or sulfamyl group, such as a 2-chloroethyl, 2-chloropropyl, 2-chlorocyclohexyl, 2- cyanoethyl,
  • R represents an aryl group such as a phenyl or an aor B-naphthyl group or an aryl group substituted with one or more nitro, cyano, alkyl, aryl, alkoxy, aryloxy, alkox-ycarbonyl, acyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, sulfoester, amido, sulfonamido, ureido, carbamyl and sulfamyl groups or halogen atoms.
  • aryl group such as a phenyl or an aor B-naphthyl group or an aryl group substituted with one or more nitro, cyano, alkyl, aryl, alkoxy, aryloxy, alkox-ycarbonyl, acyl, arylcarbonyl, alkylsulfonyl, aryls
  • R represents a S-membered or 6-membered heterocyclic group containing, as a hetero-atom, nitrogen, oxygen and/or sulfur, such as a tetrahydrofuryl, 2-furylmethyl, tetrahydrofurfuryl or 3- or 4-pyridyl group. These rings can be substituted with substituents above described for the aryl group.
  • R represents a divalent group (e.g., having 1 to about 30 carbon atoms) obtained by eliminating two hydroxyl groups from a divalent alcohol or divalent phenol, such as an alkylene group (e.g., ethylene, propylene, hexamethylene,, octadecamethylene, 2-buty lene, l,4-cyclohexanedimethylene, etc.), an arylene group (e.g., phenylene, methylphenylene, 2,5-di-tertoctylphenylene, chlorophenylene, methoxyphenylene, phenylphenylene, naphthylene, biphenylene, isopropylidene bisphenylene, etc.) or a xylylene group (e.g., xylylene, chloroxylylene, ethoxyxylylene, etc.).
  • a divalent group e.g., having 1 to about 30 carbon atoms
  • R or R may represent a divalent group of about 30 or less carbon atoms to form a bis-pyrazolone coupler.
  • the pyrazolone compound in which the 4-position is substituted by a carbonic ester group or an oxalic ester group, used according to the present invention can provide various properties depending on the substituents on l-, 3- and 4-positions and this feature is applicable to various photographic objects.
  • the coupler associates in a hydrophilic colloid and becomes non-diffusible in the hydrophilic colloid layer of a light-sensitive material.
  • Such a coupler can be incorporated in a silver halide emulsion layer.
  • R or R contains a hydrophobic group of 8 or more carbon atoms and at least one of R.
  • the coupler is non-diffusible per se but can provide a diffusible dye by the oxidizing coupling reaction with an aromatic primary amine developing agent.
  • a diffusible dye providing coupler is suitable for diffusion transfer color photography.
  • the process of forming a dye image by the oxidizing and coupling reaction with an aromatic primary amine developing agent is classified mainly into two types according to the method of adding of coupler.
  • the so-called internal type the coupler is incorporated in an emulsion during the production of the light-sensitive material.
  • a suitable amount of the pyrazolone compound of this invention which can be incorporated with emulsion layer ranges from about 2 X l to 1 X 10" mol/m of the support.
  • the so-called external type the coupler is dissolved in a developer and provided in the emulsion layer through diffusion during development.
  • a suitable amount of the pyrazolone compound of this invention which can be used in the developer solution ranges from about 5 X l0 to 5 X mol/liter of the developer solution.
  • the coupler used in the internal type must be fixed in an emulsion layer, that is, must be diffusion-resistant. If the coupler is not diffusion-resistant, the coupler migrates in a light-sensitive material and the color is formed in the wrong color-sensitive emulsion layer, thus markedly deteriorating the color reproduction capability of the light-sensitive material.
  • ballast group In order to render a coupler diffusion-resistant, a group containing a hydrophobic radical of 8 to 32 carbon atoms is introduced into the coupler molecule. This radical is generally called a ballast group.
  • the ballast group can be combined with the coupler skeleton directly or through an imino-, ether-, carbonamidesulfonamide-, ureide-, ester-, imide-, carbamoylor sulfamoyl-bond.
  • ballast groups suitable for use in the coupler according to the invention are as follows:
  • Alkyl groups and alkenyl groups e.g.,
  • This coupler is a so-called two equivalent coupler that reacts with the oxidation product of an aromatic primary amine color developing agent to give the corresponding leucoazomethine dye and to form the pyrazoloneazomethine dye upon releasing of the carbonic monoester or oxalic monoester group.
  • 4-acyloxy-5-pyrazolone compounds have hitherto been known as a S-pyrazolone having an ester group at the 4-position of the pyrazolone.
  • the coupler used in the invention which has a carbonic ester group or oxalic ester group at the 4-position of the pyrazolone, can be clearly distinguished from the above described coupler in chemical structure, shows a much higher stability and the synthesis thereof is very easy as is set forth hereinafter.
  • the pyrazolone coupler used in the invention has the following valuable features:
  • the coupler of the invention is a two equivalent coupler which theoretically requires only two equivalents of silver halide, as an oxidizer, for forming one molecule of a colored dye.
  • the required silver halide can be reduced to about half of that in using a prior art four equivalent pyrazolone type coupler, thus not only halving the silver halide contained in a light-sensitive material and reducing the production cost of the light-sensitive material, but also reducing the light scattering due to the emulsion grains and improving the sharpness of the image.
  • the coupler of the 4-position-substituted S-pyrazolone type used in the invention can be converted into an azomethine dye in a high yield by the oxidizing and coupling reaction using an exposed silver halide as an oxidizer.
  • Some of the four equivalent couplers used in the prior art have a low conversion yield into the dye, since the leuco dye as an intermediate product produces side reactions such as azine ring formation.
  • the coupler of the 4-position-substituted S-pyrazolone type used in the invention can be converted into an azomethine dye with a high yield, since reaction procession is not through such a reactive intermediate product.
  • the color light-sensitive material of the invention it is possible to reduce the quantity of the magenta-forming coupler, to reduce the content of the silver halide and to reduce the thickness of the emulsion layer.
  • the coupler of the 4-position-substituted S-pyrazolone typeused in the invention has generally a strong coupling activity for an oxidized aromatic primary amine color developing agent and rapidly removes the oxidized product of the developing agent formed during color development, so that the development of a silver halide emulsion is accelerated.
  • the process of forming a dye is completed in a color developing bath and it is not necessary to use thereafter a bleaching bath containing a strong oxidizer such as potassium ferricyanide or potassium bichromate.
  • a bleaching and fixing bath containing a silver complex salt fonning agent and weak oxidizer such as a ferric chelate of EDTA or a bleaching bath containing a mercuric salt such as mercuric chloride is possible and, consequently, it is easy to shorten the time for all the processings of color development as well as to solve the problem of environmental pollution in processing solution discharge.
  • the 4-position-substituted S-pyrazolone coupler used in the invention is inactivated by carbonyl compounds such as aldehydes and ketones to a less extent, while the 4-position-non-substituted 5-pyrazolone coupler used in the prior art, in particular, in an emulsion layer is changed into a compound of low color forming reactivity such as a methylol or methylene-bis compound by formaldehyde in the air, which often does not provide sufficient color forming property during color development.
  • a change in the coupler markedly reduces the color reproduction of a color light-sensitive material.
  • One feature of the color light-sensitive material of the invention is that the material is hardly influenced by such chemicals.
  • the 4-position-substituted S-pyrazolone of the invention has the advantages, when used for conventional color light-sensitive materials as described in the Examples, that the stability during the passage of time is high in an emulsion film and, in particular, the color forming property is reduced to a lesser extent even after the passage of time at low temperature under high humidity, as compared with the above described known couplers.
  • the stability of the duration of a fresh film is one of the most important factors as to the assessment of the characters thereof.
  • a color developed image from the 4-position-substituted coupler of the invention has more excellent heat resistance than that from 4-position-non-substituted couplers and, even in comparison with the foregoing known coupler having a 4-position substituent on the same pyrazolone nucleus, the coupler of the invention has a higher heat resistance.
  • the coupler of the invention in which the 4-position is substituted by a carbonic ester group or an oxalic ester group, as represented by the foregoing General Formula (I) or (II), can readily be obtained by reaction of a 4-hydroxy-5-pyrazolone represented by General Formula (III),
  • the 4-hydroxy-5-pyrazolones represented by General Formula (111) can be obtained with a high yield by reducing the corresponding pyrazolone-4,5-dione compound in conventional manner (for example, a catalytic hydrogenation using a metallic catalyst such as palladium-carbon or a reduction using zincacetic acid or sodium borohydride), e.g., as described in US. Pat. No. 3,419,391.
  • the pyrazolone-4,5-dione compound can be obtained by converting the S-pyrazolone into the corresponding azomethine dye, followed by hydrolysis with sulfuric acid, as described in US. Pat. No. 3,311,476, or by converting the 5-pyrazolone into the 4-amino-5-pyrazolone, followed by oxidation of the amino group, as disclosed in US. Pat. No. 3,419,391.
  • aromatic primary amine developing agent means a compound which has a primary amino group on an aromatic ring and is capable of developing exposed silver halide, or a precursor which is capable of forming such a compound.
  • N,N-p-phenylenediamines are suitable for the practice of the invention.
  • amines are 4-amino-3-methyl-N-ethyl-N-(methoxyethyl)aniline, 4-amino-3-methyl-N-ethyl-N-(ethoxyethyl)aniline, 4-amino-3-ethoxy-N,N-diethylaniline, 4- amino-3,5-dimethyl-N,N-diethyl aniline, 4-amino-3- methyl-N-ethyl-N-( B-hydroxyethyDaniline, 4-amino-3- methyl-N,N-diethylaniline, 4-amino-3-methyl-N-ethyl- N-( ,B-methanesulfonamidoethyl )aniline, 4-amino-3 [3- methanesulfonamidoethyl)-N,N-diethylaniline, 4- amino-N-ethyl-N-( B-hydroxyethyl )
  • the photographic material of the invention is developed with a solution containing the above described aromatic primary amine developing agents, an alkali agent, and optionally, a preservative, antifoggant and a sensitizer, after exposure.
  • Suitable examples of such addenda are disclosed in C.E.K.Mees and T.I-I.James, The Theory of the Photographic Process, and vU.S. Pat. Nos. 2,592,364; 2,193,015; etc.
  • the silver halide emulsion of the invention comprises a silver halide such as silver chloride, silver bromide, silver iodide, or a mixed silver halide such as silver chlorobromide, silver iodobromide or silver chloroiodobromide, dispersed in a hydrophilic high molecule material such as gelatin.
  • the grain size can range from a uniform grain size to a grain size having a broad grain size distribution.
  • an emulsion is suitably selected having an average grain size within a range of from about 0.05 to about 3 microns.
  • the silver halide emulsion can be prepared, for example, using a mixing method such as single or double jet methods or using an ripening method such as ammonia, neutral or acidic methods. Moreover, the silver halide emulsion can be subjected to a sensitizing treatment such as sulfur sensitization, gold sensitization or reduction sensitization using conventional techniques.
  • Suitable examples of chemical sensitizers are auric compounds such as auric chloride compounds as disclosed in US. Pat. Nos. 2,399,083; 2,540,085; 2,597,856; 2,597,915; etc.; the noble metal salts of platinum, palladium, iridium, rhodium, or ruthenium as disclosed in US. Pat. Nos.
  • Suitable hydrophilic high molecular weight materials for forming the light-sensitive layer of the invention are proteins such as gelatin, high molecular weight nonelectrolytes such as polyvinyl alcohol, polyvinylpyrrolidone and polyacrylamide, acidic high molecular weight materials such as alginates and polyacrylates and high molecular weight amphoteric electrolytes such as polyacrylamide treated by the Hofmann rearrangement reaction and acrylic acid-N-vinylimidazole copolymers.
  • the hydrophilic high molecular material forming a continuous phase can contain a dispersed hydrophobic high molecular weight material, for example, a latex of polyacrylic acid butyl ester.
  • the silver halide photographic emulsion of the invention is suitably applied to a support.
  • a support hard materials such as glass, metals and ceramics, and flexible materials can be used depending on the enduse objects.
  • Typical flexible supports are cellulose nitrate films, cellulose acetate films, polyvinyl acetal films, polystyrene films, polyethylene terephthalate films, polycarbonate films and their laminates, papers coated with baryta and a-olefin polymers such as polyethylene, polypropylene and ethylene-butene polymers, and plastic films having a roughened surface as disclosed in Japanese Patent Publication No. 19068/ 1972.
  • the support can be transparent, colored by adding a dye or pigment, opaque by adding, for example, titanium white or blackened by adding, for example, carbon black.
  • Formation of a color image according to the invention can be achieved in light-sensitive materials of various forms.
  • a light-sensitive material having a silver halide emulsion layer containing a diffusion resistant coupler on a support is treated with an alkaline developer containing an aromatic primary amine color developing agent to retain a water-insoluble or diffusion resistant dye in the emulsion layer.
  • alkaline developer containing an aromatic primary amine color developing agent to retain a water-insoluble or diffusion resistant dye in the emulsion layer.
  • a light-sensitive material having a silver halide emulsion layer in combination with a diffusion resistant coupler on a support is treated with an alkaline developer containing an aromatic primary amine color developing agent to form a dye soluble in an aqueous medium and diffusible and then transferred to another receiving layer of a hydrophilic colloid.
  • This is a diffusion and transfer color system. Examples of such systems are disclosed in US. Pat. Nos. 3,342,597; 3,227,551; 3,227,550; 3,227,554; 3,644,498; 3,476,563; 3,353,672; 3,330,655; etc.
  • Couplers 16, 17 and 21 can be used for the second form described above, while the others can be used for the first form described.
  • the 5-pyrazolone coupler of the invention in which the 4-position is substituted with a carbonic ester or oxalic ester group and which has a hydrophobic radical of 8 or more carbon atoms, is dissolved in an aqueous medium or organic solvent and then dispersed in a photographic emulsion.
  • the oil-soluble and diffusion-resistant coupler used in the internal type is incorporated in a light-sensitive material by dissolving the coupler in an organic solvent and then dispersing the solution in a photographic emulsion as fine colloidal grains.
  • a coupler dispersing method suitable for the practice of the invention is illustrated in detail, for example, in US. Pat. No. 3,676,137.
  • Organic solvents capable of dissolving the coupler, hardly soluble in water, having a high boiling point (e.g., above 170C) and present with the coupler in a color light sensitive material are selected from substituted hydrocarbons, carboxylic acid amides, phosphoric acid esters and ethers, for example, di-n-butyl phthalate, di-i-octyl acetate, di-n-butyl sebacate, tricresyl phosphate, tri-n-hexyl phosphate, N,N- diethylcaprylamide, butyl-n-pentadecylphenyl ether and chlorinated paraffins.
  • auxiliary solvents for dissolving thecoupler which can be removed during the production of a light-sensitive material, are preferably used, for example, ethyl acetate, butyl acetate, cyclohexanol, tetrahydrofuran and cyclohexanone.
  • Surfactants are preferably used as an aid to disperse the oil-soluble coupler of the internal type finely in a hydrophilic high molecular material used in the photographic emulsion.
  • Illustrative of such surfactants are anionic surfactants such as sodium cetylsulfate, sodium p-dodecylbenzenesulfonate, sodium nonylnaphthalenesulfonate and sodium di(2-ethylhexyl)-a-sulfosuccinate, and nonionic surfactants such as sorbitan sesquioleic acid esters and sorbitan monolauric acid esters.
  • an emulsifying homogenizer, colloid mill and ultrasonic wave emulsifying apparatus are suitable for the dispersion of an oil-soluble coupler.
  • a diffusion resistant coupler having a ballast group and carboxylic acid group or sulfonic acid group in the same molecule is soluble in a neutral or weakly alkaline aqueous solution.
  • the coupler can be incorporated in a photographic emulsion by adding an aqueous solution containing the coupler to the photographic emulsion.
  • the coupler is believed to be diffusion resistant through the formation of micelles in the hydrophilic high molecular material.
  • the two equivalent coupler of the invention can be used together with one or more of the magenta couplers as described in U.S. Pat. Nos. 2,439,098; 2,369,489; 2,600,788; 3,558,319; 2,311,081; 3,419,391, 3,006,759; 2,725,292; 2,908,573; 3,519,429; 3,152,896; 3,062,653 and 3,311,476, British Pat. No. 956,261, Japanese Pat. Publication No. 19032/1971, Japanese Pat. Application Nos. 114445/1972 and 114446/1972, the magenta colored couplers described in U.S. Pat. Nos.
  • the light-sensitive material of the invention contain a p-substituted phenol derivative in the emulsion layer or in an adjacent layer thereof.
  • Particularly suitable p-substituted phenol derivatives can be selected from one or more of the hydroquinone derivatives described in U.S. Pat. Nos. 2,360,290; 2,418,613; 2,675,314; 2,701,197; 2,704,713;
  • the light-sensitive material of the invention can preferably contain an ultraviolet absorbent in the emulsion layer or in an adjacent layer, as described in U.S. Pat. Nos. 3,250,617 and 3,253,921.
  • the hydrophilic colloid layer in the light-sensitive material of the invention in particular, the gelatin layer can be hardened employing conventional techniques using various cross-linking agents.
  • hardeners are aldehyde group compounds such as formaldehyde, glutaraldehyde, ketone compounds such as diacetyl, cyclopentandione, etc.; reactive halogen containing compounds such as bis-(2-chloroethylurea) 2-hydroxy-4,6-dich.1oro-1 ,3,5-triazine, as disclosed in U.S. Pat. Nos. 3,288,775 and 2,732,303, British Pat. Nos.
  • active vinyl group containing compounds such as divinylsulfone, 5-acetyll ,3-diacryloylhexahydro-1 ,3,5-triazine, as disclosed in U.S. Pat. Nos. 3,635,718 and 3,232,763, British Pat. No. 994,869, etc.
  • N-methylol compounds such as N-hydroxymethylphthalimide as disclosed in U.S. Pat. Nos. 2,732,316 and 2,586,168, etc.
  • isocyanate group containing compounds such as those disclosed in U.S. Pat. Nos. 3,017,280; 2,983,611, etc.
  • organic sulfuric or carboxylic acid derivatives such as those disclosed in U.S.
  • alkali metal bisulfite aldehyde adducts can be used as a hardening agent.
  • Non-aldehyde type cross-linking agents such as those compounds having a plurality of epoxy rings as described in Japanese Pat. Publication 7133/1959, the poly-(1-aziridinyl) compounds described in Japanese Pat. Publication 8790/ 1962 and the active halogen compounds described in U.S. Pat. Nos. 3,362,827 and 3,325,287 are particularly suitable for use in the light-sensitive material of the invention.
  • EXAMPLE 1 A mixture of 23g of 1-(2,4,6-trichlorophenyl)-3-(3- (a-( 2,4-d i-tert-amylphenoxy )acetamido )benzamido 5-pyrazolonyl-(4)benzyl carbonic acid ester (Coupler 3), 20 ml of tricresyl phosphate and 40ml of ethyl acetate was heated at 60C to prepare a solution and the resulting solution was added to 250ml of an aqueous solution containing 25g of gelatin and 075g of sodium dodecylbenzenesulfonate at 60C, followed by vigorous mechanical stirring, thus obtaining an emulsified coupler dispersion.
  • the resulting coupler emulsion was mixed with 200g of a photographic emulsion containing 11.2 X 10 mol of silver chlorobromide (silver bromide 45 mol%, silver chloride 55 mol%) and 20g of gelatin and, after 10ml of a 3% acetone solution of triethylenephosphamide as a hardener was added thereto and the final pH was adjusted to 6.5, the mixture was coated onto a cellulose triacetate film base to 5 give a film thickness of 4.3 microns on dry basis (Film A). This film contained, per lm 1.55 X 10 mol of the coupler and 6.2 X 10 mol of silver chlorobromide.
  • the dyes were extracted with a mixture of dimethylformamdescribed l Sion as 32 54323; g i m i figfgj fi m ide and water in a ratio of 85:15 by volume and suba film thickness of 5 1 microns on d 3 2 g jected to quantitative measurement using an absor- 2 FY 1 lmnadoy method.
  • Relative sensitivity means the quantity of exposure necessary for giving a density of fog 0.1.
  • Stabilizing Bath two kinds of stabilizing baths, i.e., Stabilizing Bath (a) containing no formaldehyde and Stabilizing Bath (b) containing 1% of 40% formaldehyde were prepared.
  • the films were treated respectively with these baths, allowed to stand at 80C for one week and the decreasing ratio of the density was measured based on the initial density and the results are tabulated in Table 4.
  • This emulsion was mixed with 100g of a photographic emulsion containing 4.7 X 10 mol of silver chlorobromide (silver chloride mol%, silver bromide 50 mol%) and 9g of gelatin, to which 3ml of a 4% aqueous solution of 2- hydroxy-4,6-dichloro-s-triazine sodium salt as a hardener was then added, and the pH was adjusted to 6.3.
  • the resultant mixture was coated onto a baryta paper resin-coated with polyethylene to give a coating thickness of 1.6 microns on dry basis (Film C).
  • EXAMPLE 3 A mixture of 10g of l-(2,4,6-trichlorophenyl)-3-(3- (a-( 3-n-pentadecylphenox y )butylamido )benzamido 5-pyrazolonyl-(4)-ethyl carbonic acid ester (Coupler 18), 0.8g of 2,5-di-tert-octylhydroquinone, 0.8g of 6,6-dihydrox-7,7-dimethyl-4,4,4',4'-tetramethyl-bis- 2,2-spirochroman, 10ml of dioctyl butyl phosphate and 30ml of ethyl acetate was heated and dissolved on a steam bath and added to an aqueous solution contain- It is apparent from the results in Table 5 that the lightsensitive material using the coupler of the invention provides similar photographic properties to those of the prior art even though the coating amounts of the coupler and silver halide are decreased.
  • EXAMPLE 4 Onto a baryta paper resin-coated with polyethylene were coated, as a first layer, a blue-sensitive silver chlorobromide emulsion'containing a-pivaloyl-a-(2,4-dioxo-5 ,S-dimethyloxazolidinyl )-2-chlor0-5-( a-( 2,4-ditert-amylphenoxy)butylamido) acetanilide in a thickness of 3.0 microns (silver coated amount: 3.53 X mol/m coupler coated amount: 1.2 X 10 mol/m and further, as a second layer, a gelatin containing 2-t-octylhydroquinone in a thickness of 1.5 microns.
  • an emulsified dispersion of a coupler was prepared in the same manner but using 8.25g of the Coupler 19 of the invention, i.e., l-(2,4,6-trichloro)- phenyl-3-( 2-chloro-5-n-tetradecanamido) anilino )-5- pyrazolonyl-(4)-ethyl carbonic ester in place of Coupler 18 of Example 3, and using tricresyl phosphate in place of the dioctyl butyl phosphate, added to a green sensitive photographic emulsion having the same composition as in Example 3 and coated in a coating thickness of 1.7 microns as a third layer (silver coated amount: 2.08 X 10 3 mol/m coupler coated amount: 5.2 X 10 mol/m a gelatin containing 2,5-di-t-octylhydroquinone and, as an ultraviolet absorbent, 2-(5- chlorobenzotriazol-Z
  • This color print paper was exposed through a color negative and developed in a manner analogous to Example 2.
  • the resulting color print was a sharp color photographic image very excellent in color reduction and containing a magenta color image having an absorption maximum at 541 t.
  • the resulting emulsified dispersion was mixed with 100g of a photographic emulsion containing 5.6 X 10 mol of silver bromide and 10g of gelatin and 3ml of a 4% aqueous solution of 2-hydroxy-4,6-dichloro-s-triazine sodium salt as a hardener and then applied to a film of cellulose triacetate in a coating thickness of 2.5 microns.
  • the thus obtained film was exposed and then subjected to the same developing processings as those of Example 1 but using the following color developing solution and effecting the treatment in 14 minutes, thus obtaining a sharp magenta color image.
  • Coupler and Absorption Maximum of the Developed Color Image Onto a transparent support of cellulose triacetate were coated, as a first layer, a red-sensitive silver iodobromide emulsion containing l-hydroxy-2-tetradecylnaphthamide in a thickness of 5.0 microns and, as a second layer (coated silver amount: 2.12 X 10 mol/m coated coupler amount: 1.8 X 10' mol/m a gelatin containing 2,5-di-t-octylhydroquinone in a thickness of 1.0 micron.
  • Coupler 23 of the invention 2.0g of 1(2,4,6- trichlorophenyl )-3-( 2-chloro-5-tetradecyloxycarbonyl)anilino)-4-(a-naphthylazo)-5-pyrazolone, 12ml of tricresyl phosphate and 50ml of ethyl acetate were heated at 60C and dissolved.
  • the resultant solution was added to 150ml of an aqueous solution containing 15g of gelatin and 0.4g of sodium dodecylbenzenesulfonate at 60C and the mixed solution was vigorously and mechanically stirred using a homogenizer to obtain an emulsified coupler dispersion.
  • the resulting emulsion was mixed with 500g of a green-sensitive photographic emulsion containing 3 X 10 mol of silver iodobromide (silver iodide 6 mol%, silver bromide 94 mol%) and 30g of gelatin, to which ml of a 3% acetone solution of the sodium salt of 2-hydroxy-4,6- dichloro-s-triazine as a hardener was then added, and the pH was finally adjusted to 7.0.
  • a green-sensitive photographic emulsion containing 3 X 10 mol of silver iodobromide (silver iodide 6 mol%, silver bromide 94 mol%) and 30g of gelatin, to which ml of a 3% acetone solution of the sodium salt of 2-hydroxy-4,6- dichloro-s-triazine as a hardener was then added, and the pH was finally adjusted to 7.0.
  • the emulsion was coated as a third layer (coated silver amount: 1.85 X 10" mol/m coated coupler amount: 1.74 X 10 mol/m including 1.59 X 10 mol/m of Coupler 23) onto the above described coating in a coating thickness of 5.1 microns on dry basis.
  • a gelatin mixture containing yellow colloidal silver and 2,5-di-t-octylhydroquinone in a thickness of 1.5 microns a blue-sensitive silver iodobromide photographic emulsion containing a-(p-methoxybenzoyl)-a-(5,5-dimethyl-3- hydantoinyl )-2-chloro-5-( y-( 2 ,4 '-di-t-amylphenoxy)-butylamido)acetanilide as a fifth layer
  • coated silver amount: 1.0 X 10 mol/m coated coupler amount: 1 X 10 mol/m in a thickness of 5.0 microns and a protective layer of gelatin in a thickness of 1.0 micron as an uppermost layer thus obtaining a color negative light-sensitive material.
  • the resulting mixture was cooled at 5C and set, cut in square rods of about 5mm, washed with an aqueous solution containing 0.6g of magnesium sulfate per 1000ml at 5C for 5 hours, heated for redissolving at 40C, mixed with 10ml of a 3% methanol solution of triethylene phosphamide and 15ml of a 5% aqueous solution of saponin and then coated, as a sixth layer, onto the above described coating in a thickness of 7.5 microns on dry basis.
  • a gelatin layer of 1 micron was coated as an uppermost layer to thus obtain a light-sensitive material.
  • the resulting light-sensitive material was exposed stepwise for sensitometry through, as a cover, a sheet of cellulose triacetate of a thickness of 0.1mm.
  • n O or 1 R is a hydrogen atom or a group having 1 to about 50 carbon atoms selected from the group consisting of a straight chain or branched chain alkyl group; an alkenyl group; a cycloalkyl group; a substituted alkyl or substituted cycloalkyl group containing as a substituent, a halogen atom or a nitro, cyano, aryl, alkoxy, aryloxycarboxy, alkoxycarbonyl, aryloxycarbonyl, sulfo, sulfamoyl, carbamoyl, acylamino, ureido,
  • R represents a group having 1 to about 50 carbon atoms selected from the group consisting of the same alkyl, substituted alkyl, aryl, substituted aryl, heterocyclic or substituted heterocyclic groups as described for R and alkoxycarbonyl group; an aryloxycarbonyl group; an aralkyloxycarbonyl group; an alkoxy group; an aryloxy group; an alkythio group; an arylthio group; a carboxy group; an amino group; an alkylamino group; a cycloalkylamino group, an N,N-dialkylamino group; an N-alkyl-N-arylamino group; an N-arylamino group; an amido group; an N-alkylacylamino group; an N-arylacylamino group; a ureido group; an N- arylureido group; an N-alkylureido group; a thioureido group;
  • R represents a group having 1 to about 30 carbon atoms selected from the group consisting of a straight chain or branched chain alkyl group; an alkenyl group; a cycloalkyl group; an alkyl or cycloalkyl group substituted with a halogen atom or a nitro, cyano, aryl, alkoxy, carboxyester, sulfoester, amido, sulfonamido, ureido, carbamyl or sulfamyl group; an aryl group substituted with one or more halogen atoms, or nitro, cyano, alkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, acyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, sulfoester, amido, sulfonamido, ureido, carbamyl and sulfa
  • R represents a divalent group having from 1 to 30 carbon atoms selected from the group consisting of as an alkylene group and an arylene group;
  • R or R may form a divalent group of about 30 or less carbon atoms linking two 5- pyrazolone moieties of the General Formula (I) and/or ([1); I
  • a light-sensitive photographic element comprising a support having thereon at least one light-sensitive layer comprising a hydrophilic colloid silver halide emulsion having dispersed therein an uncolored dye image forming two equivalent coupler selected from the group consisting of the couplers represented by the General Formula (I) and (II) t C (CL)nC 3 substituted alkyl or substituted cycloalkyl group containing as a substituent, a halogen atom or a nitro,
  • R represents a group having 1 to about 50 carbon atoms selected from the group consisting of the same alkyl, substituted alkyl, aryl, substituted aryl, heterocyclic or substituted heterocyclic groups as described for R an alkoxycarbonyl group; an aryloxycarbonyl group; an aralkyloxycarbonyl group; an alkoxy group; an aryloxy group; an alkythio group; an arylthio group; a carboxy group; an amino group; an alkylamino group; a cycloalkylamino group, an N,N-dialkylamino group; an N-alkyl-N-arylamino group; an N-arylamino group; an amidogroup; an N-al1kylacylamino group; an N-arylacylamino group; a ureido group; an N- arylureido group; an N-alkylureido group; a thioureido group
  • R represents a group having 1 to about 30 carbon atoms selected from the group consisting of a straight chain or branched chain alkyl group; an alkenyl group; a cycloalkyl group; an alkyl or cycloalkyl group substituted with a halogen atom or a nitro, cyano, aryl, alkoxy, carboxyester, sulfoester, amido, sulfonamido, ureido, carbamyl or sulfamyl group; an aryl group substituted with one or more halogen atoms, or nitro, cyano, alkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, acyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, sulfoester, amido, sulfonamido, ureido, carbamyl and sulfa
  • R represents a divalent group having from 1 to 30 carbon atoms selected from the group consisting of as an alkylene group and an arylene group;
  • R or R may form a divalent group of about 30 or less carbon atoms linking two 5- pyrazolone moieties of the General Formula (I) and/or (II).
  • said silver halide emulsion contains additionally a 4-equivalent S-pyrazolone compound in which the 4-position is unsubstituted and/or a colored magenta coupler.
  • a process of forming a color image which comprises developing a silver halide photographic emulsion with an aromatic primary amine as a color developing agent in the presence of a coupler as defined in claim 1.
  • a process of forming a color image which comprises developing an exposed silver halide photographic emulsion with an alkaline aqueous solution containing an aromatic primary amine color developing agent in the presence of a magenta-forming coupler represented by General Formula (I) or (II) oco(co) oa (I) wherein n is O and 1 R is a hydrogen atom or a group having 1 to about 50 carbon atoms selected from the group consisting of a straight chain or branched chain alkyl group; an alkenyl group; a cycloalkyl group; a substituted alkyl or substituted cycloalkyl group containing as a substituent, a halogen atom or a nitro, cyano, aryl, alkoxy, aryloxycarboxy, alkoxycarbonyl, aryloxycarbonyl, sulfo, sulfamoyl, carbamoyl, acylamino, ureido, heterocycl
  • R represents a group having 1 to about 50 carbon atoms selected from the group consisting of the same alkyl, substituted alkyl, aryl, substituted aryl, heterocyclic or substituted heterocyclic groups as described for R an alkoxycarbonyl group; an aryloxycarbonyl group; an aralkyloxycarbonyl group; an alkoxy group; an aryloxy group; an alkylthio group; an arylthio group; a carboxy group; an amino group; an alkylamino group; a cycloalkylamino group, an N,N-dialkylamino group; an N-alkyl-N-arylamino group; an N-arylamino group; an amido group; an N-alkylacylamino group; an N-arylacylamino group; a ureido group; an N- arylureido group; an N-alkylureido group; a thioureido group
  • R represents a group having I to about 30 carbon atoms selected from the group consisting of a straight chain or branched chain alkyl group; an alkenyl group; a cycloalkyl group; an alkyl or cycloalkyl group substituted with a halogen atom or a nitro, cyano, aryl, alkoxy, carboxyester, sulfoester, amido, sulfonamido, ureido, carbamyl or sulfamyl group; an aryl group substituted with one or more halogen atoms, or nitro, cyano, alkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, acyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, sulfoester, amido, sulfonamido, ureido, carbamyl and sulfa
  • R represents a divalent group having from 1 to 30 carbon atoms selected from the group consisting of as an alkylene group and an arylene group;
  • R or R may form a divalent group of about 30 or less carbon atoms linking two 5 pyrazolone moieties of the General Formula (I) and/or (II).
  • a process of forming a color image which comprises exposing a light-sensitive material comprising a support having thereon a silver halide photographic emulsion layer containing a magenta-forming coupler represented by General Formula (I) or (II) coo-(c) me,
  • n O or 1 R is a hydrogen atom or a group having I to about 50 carbon atoms selected from the group consisting of a straight chain or branched chain alkyl group; an alkenyl group; a cycloalkyl group; a substituted alkyl or substituted cycloalkyl group containing as a substituent, a halogen atom or a nitro, cyano, aryl, alkoxy, aryloxycarboxy, alkoxycarbonyl, aryloxycarbonyl, fulfo, sulfamoyl, carbamoyl, acylamino, ureido, heterocyclic, arylsulfonyloxy or oxo group; a substituted aryl group containing at least one of an alkyl, alkoxy, aryloxy, carboxy, alkoxycarbonyl, acylamino, carbamoyl, alkylcarbamoyl
  • R represents a group having I to about 50 carbon atoms selected from the group consisting of the same alkyl, substituted alkyl, aryl, substituted aryl, heterocyclic or substituted heterocyclic groups as described for R an alkoxycarbonyl group; an aryloxycarbonyl group; an aralkyloxycarbonyl group; an alkoxy group; an aryloxy group; an alkylthio group; an arylthio group; a carboxy group; an amino group; an alkylamino group; a cycloalkylamino group; an N,N-dialkylamino group; an N-alkyl-N-arylamino group; an N-arylamino group; an amido group; an Nalkylacylamino group; an N-arylacylamino group; a ureido group; an N- arylureido group; an N-alkylureido group; a thioureido group;
  • R represents a group having 1 to about 30 carbon atoms selected from the group consisting of a straight chain or.branched chain alkyl group; an alkenyl group; a cycloalkyl group; an alkyl or cycloalkyl group substituted with a halogen atom or a nitro, cyano, aryl, alkoxy, carboxyester, sulfoester, amido, sulfonamido, ureido, carbamyl or sulfamyl group; an aryl group substituted with one or more halogen atoms, or nitro, cyano, alkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, acyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, sulfoester, amido, sulfonamido, ureido, carbamyl and sulfa
  • R represents a divalent group having from 1 to 30 carbon atoms selected from the group consisting of as an alkylene group and an arylene group;
  • R or R may form a divalent group of about 30 or less carbon atoms linking two 5- pyrazolone moieties of the General Formula (I) and/or (II); and having at least one hydrophobic radical of eight or more carbon atoms in the molecule and developing said material with an alkaline aqueous solution containing an aromatic primary amine color developing agent.
  • a process of forming a color image which comprises developing a light-sensitive material comprising 50 a support having thereon a silver halide photographic emulsion layer in combination with a magenta-forming coupler having the General Formula (I) or (II) oco(co) oR r jcouomomocowm o R2 (II) N 0 0 N/ l 1 R1 R1 wherein n is O or 1 R is a hydrogen atom or a group having 1 to about 50 carbon atoms selected from the group consisting of a straight chain or branched chain alkyl group; an alkenyl group; a cycloalkyl group; a substituted alkyl or substituted cycloalkyl group containing as a substituent, a halogen atom or a nitro, cyano, aryl, alkoxy, aryloxycarboxy, alkoxycarbonyl, aryloxycarbonyl, sulfo,
  • R represents a group having 1 to about 50 carbon atoms selected from the group consisting of the same alkyl, substituted alkyl, aryl, substituted aryl, heterocyclic or substituted heterocyclic groups as described for R an alkoxycarbonyl group; an aryloxycarbonyl group; an aralkyloxycarbonyl group; an alkoxy group; an aryloxy group; an alkythio group; an arylthio group; a carboxy group; an amino group; an alkylamino group; a cycloalkylamino group, an N,N-dialkylamino group; an
  • N-alkyl-N-arylamino group an N-arylamino group; an amido group; an N-alkylacylamino group; an
  • N-arylacylamino group a ureido group; an N- arylureido group; an N-alkylureido group; a thioureido group; an N-alkylthioureido; an N-arylthioureido group; a carbamoyl group; a sulfamoyl group; a piperidino group; a pyrrolidino group; a guanidino group; an N-alkylguanidino group; and an N-arylguanidino group;
  • R represents a group having 1 to about 30 carbon atoms selected form the group consisting of a straight chain or branched chain alkyl group; an alkenyl group; a cycloalkyl group; an alkyl or cycloalkyl group substituted with a halogen atom or a nitro, cyano, aryl, alkoxy, carboxyester, sulfoester, amido, sulfonamido, ureido, carbamyl or sulfamyl group; an aryl group substituted with one or more halogen atoms, or nitro, cyano, alkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, acyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, sulfoester, amido, sulfonamido, ureido, carbamyl and sulfa
  • R represents a divalent group having from 1 to 30 carbon atoms selected from the group consisting of as an alkylene group and an arylene group;
  • R or R may form a divalent group of about 30 or less carbon atoms linking two 5- pyrazolone moieties of the General Formula (I) and/or (II); and in which at least one of R and R contains a water-solubilizing sulfo, carboxyl or sulfonamido group and R is a hydrophobic group of either or more carbon atoms with an alkaline aqueous solution containing an aromatic primary amine color developing agent and then transferring the resultant magenta dye to a receiving layer containing a basic polymer.

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US4062683A (en) * 1975-05-30 1977-12-13 Agfa-Gevaert N.V. Photographic material containing 3-anilino-5-pyrazolylalkylcarbonate or arylcarbonate couplers
US4075022A (en) * 1975-04-03 1978-02-21 Wignsberghe Leo Augus Aqueous dispersions of photographic ingredients
US4409323A (en) * 1980-02-15 1983-10-11 Konishiroku Photo Industry Co., Ltd. Silver halide photographic material
US4789624A (en) * 1983-01-20 1988-12-06 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US6165229A (en) * 1996-03-22 2000-12-26 L'oreal Imidazoloazole-containing compositions for dyeing keratin fibers; their use in dyeing as couplers; dyeing process
US6179882B1 (en) 1996-03-22 2001-01-30 L'oreal Keratin fibre dye composition containing pyrazolopyrimidinoxo compounds, use thereof as dye couplers, and dyeing methods
US6210447B1 (en) 1996-03-22 2001-04-03 L'oreal Compositions containing pyrazolin-3,5-dione couplers for use in keratin fiber dyeing methods and kits
US6231623B1 (en) 1996-03-22 2001-05-15 L'oreal S.A. Methods of dyeing keratin fibers with compositions containing pyrazolo-azole couplers
US6238440B1 (en) 1996-03-22 2001-05-29 L'oreal S.A. Keratin fibre dye compositions containing pyrrolo-azole compounds, use thereof as couplers, and dyeing method
WO2001068043A2 (fr) 2000-03-14 2001-09-20 L'oreal Compositions pour la teinture des fibres keratiniques contenant des derives de paraphenylenediamine a groupement pyrrolidinyle
US6322775B1 (en) 1996-03-22 2001-11-27 L'oreal S.A. Cosmetic compositions containing pyrazolin-4,5-diones, novel pyrazolin-4,5-diones, preparation methods therefor and uses thereof
US6379397B2 (en) 1997-12-16 2002-04-30 L'oreal S.A. Compositions for dyeing keratinous fibers comprising pyrazoloazoles; their use in dyeing as oxidation base and dyeing process; and novel pyrazoloazoles
US6391063B1 (en) 1998-11-20 2002-05-21 L'oreal Composition for the oxidation dyeing of keratin fibers and dyeing process using this composition
US6395042B1 (en) 1998-11-20 2002-05-28 L'oréal Composition for the oxidation dyeing of keratin fibers and dyeing process using this composition
US6702863B1 (en) 1999-06-22 2004-03-09 Lion Corporation Hairdye composition
US20040064902A1 (en) * 2000-12-06 2004-04-08 Stephane Sabelle Oxidatiton dyeing composition based on 1-(4-aminophenyl) pyrrolidines substituted in position 2 and 5
US20040077852A1 (en) * 2002-07-05 2004-04-22 Stephane Sabelle Para-phenylenediamine derivatives containing a pyrrolidyl group, and use of these derivatives for coloring keratin fibers
US20040074013A1 (en) * 2000-12-06 2004-04-22 Eric Terranova Oxidation dyeing composition based on 1-(4-aminophenyl) pyrrolidines substituted in positions 3 and 4, and dyeing method using same
US20040083559A1 (en) * 2000-12-06 2004-05-06 Stephane Sabelle Dyeing composition based on 1-(4-aminophenyl)pyrrolidines substituted at least in positions 2 and 3
US20040088799A1 (en) * 2000-12-06 2004-05-13 Stephane Sabelle Oxidation dyeing composition based on 1-(4-aminophenyl) pyrrolidines substituted in position 2
US20040123401A1 (en) * 2002-09-09 2004-07-01 Stephane Sabelle Bis-para-phenylenediamine derivatives comprising a pyrrolidyl group and use of these derivatives for dyeing keratin fibres
US6890362B2 (en) 2000-03-06 2005-05-10 L'oreal, S.A. Oxidation dyeing composition for keratinous fibers and dyeing method using same
US6893470B1 (en) 1998-01-13 2005-05-17 L'oreal S.A. Keratinous fibre oxidation dyeing composition containing a laccase and dyeing method using same
US6946005B2 (en) 2002-03-27 2005-09-20 L'oreal S.A. Pyrrolidinyl-substituted para-phenylenediamine derivatives substituted with a cationic radical, and use of these derivatives for dyeing keratin fibers

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JPS59116647A (ja) 1982-12-13 1984-07-05 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料
JPS59188641A (ja) 1983-04-11 1984-10-26 Fuji Photo Film Co Ltd ハロゲン化銀写真乳剤
JPS60143331A (ja) 1983-12-29 1985-07-29 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JPS61251852A (ja) 1985-04-30 1986-11-08 Konishiroku Photo Ind Co Ltd ハロゲン化銀カラ−写真感光材料の処理方法
AU590563B2 (en) 1985-05-16 1989-11-09 Konishiroku Photo Industry Co., Ltd. Method for color-developing a silver halide color photographic light-sensitive material
AU588878B2 (en) 1985-05-31 1989-09-28 Konishiroku Photo Industry Co., Ltd. Method for forming direct positive color image
AU591540B2 (en) 1985-12-28 1989-12-07 Konishiroku Photo Industry Co., Ltd. Method of processing light-sensitive silver halide color photographic material
JPH05248065A (ja) * 1991-04-08 1993-09-24 Yasuo Onishi タイルおよびその取付方法

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Cited By (31)

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Publication number Priority date Publication date Assignee Title
US4075022A (en) * 1975-04-03 1978-02-21 Wignsberghe Leo Augus Aqueous dispersions of photographic ingredients
US4062683A (en) * 1975-05-30 1977-12-13 Agfa-Gevaert N.V. Photographic material containing 3-anilino-5-pyrazolylalkylcarbonate or arylcarbonate couplers
US4409323A (en) * 1980-02-15 1983-10-11 Konishiroku Photo Industry Co., Ltd. Silver halide photographic material
US4789624A (en) * 1983-01-20 1988-12-06 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material
US6210447B1 (en) 1996-03-22 2001-04-03 L'oreal Compositions containing pyrazolin-3,5-dione couplers for use in keratin fiber dyeing methods and kits
US6179882B1 (en) 1996-03-22 2001-01-30 L'oreal Keratin fibre dye composition containing pyrazolopyrimidinoxo compounds, use thereof as dye couplers, and dyeing methods
US6551360B2 (en) 1996-03-22 2003-04-22 Laurent Vidal Pyrazoline-3,5-dione-containing compositions for dyeing keratin fibres; their use in dyeing as couplers; dyeing process
US6231623B1 (en) 1996-03-22 2001-05-15 L'oreal S.A. Methods of dyeing keratin fibers with compositions containing pyrazolo-azole couplers
US6238440B1 (en) 1996-03-22 2001-05-29 L'oreal S.A. Keratin fibre dye compositions containing pyrrolo-azole compounds, use thereof as couplers, and dyeing method
US6322775B1 (en) 1996-03-22 2001-11-27 L'oreal S.A. Cosmetic compositions containing pyrazolin-4,5-diones, novel pyrazolin-4,5-diones, preparation methods therefor and uses thereof
US6379395B1 (en) 1996-03-22 2002-04-30 L'oreal S.A. Pyrazolopyrimidinoxo-containing compositions for dyeing keratin fibres; their use in dyeing as couplers; dyeing processes
US6165229A (en) * 1996-03-22 2000-12-26 L'oreal Imidazoloazole-containing compositions for dyeing keratin fibers; their use in dyeing as couplers; dyeing process
US6379397B2 (en) 1997-12-16 2002-04-30 L'oreal S.A. Compositions for dyeing keratinous fibers comprising pyrazoloazoles; their use in dyeing as oxidation base and dyeing process; and novel pyrazoloazoles
US6855827B2 (en) 1997-12-16 2005-02-15 L'oréal Compositions for dyeing keratinous fibers comprising pyrazoloazoles; their use in dyeing as oxidation base and dyeing process; and novel pyrazoloazoles
US6893470B1 (en) 1998-01-13 2005-05-17 L'oreal S.A. Keratinous fibre oxidation dyeing composition containing a laccase and dyeing method using same
US6395042B1 (en) 1998-11-20 2002-05-28 L'oréal Composition for the oxidation dyeing of keratin fibers and dyeing process using this composition
US6391063B1 (en) 1998-11-20 2002-05-21 L'oreal Composition for the oxidation dyeing of keratin fibers and dyeing process using this composition
US6702863B1 (en) 1999-06-22 2004-03-09 Lion Corporation Hairdye composition
US6890362B2 (en) 2000-03-06 2005-05-10 L'oreal, S.A. Oxidation dyeing composition for keratinous fibers and dyeing method using same
US20030093866A1 (en) * 2000-03-14 2003-05-22 Laurent Vidal Dyeing compositions for keratinous fibres containing paraphenylenediamine derivatives with pyrrolidinyl group
US7179301B2 (en) 2000-03-14 2007-02-20 L'oreal S.A. Dyeing compositions for keratinous fibers containing paraphenylenediamine derivatives with pyrrolidinyl group
WO2001068043A2 (fr) 2000-03-14 2001-09-20 L'oreal Compositions pour la teinture des fibres keratiniques contenant des derives de paraphenylenediamine a groupement pyrrolidinyle
US20040088799A1 (en) * 2000-12-06 2004-05-13 Stephane Sabelle Oxidation dyeing composition based on 1-(4-aminophenyl) pyrrolidines substituted in position 2
US20040083559A1 (en) * 2000-12-06 2004-05-06 Stephane Sabelle Dyeing composition based on 1-(4-aminophenyl)pyrrolidines substituted at least in positions 2 and 3
US20040074013A1 (en) * 2000-12-06 2004-04-22 Eric Terranova Oxidation dyeing composition based on 1-(4-aminophenyl) pyrrolidines substituted in positions 3 and 4, and dyeing method using same
US20040064902A1 (en) * 2000-12-06 2004-04-08 Stephane Sabelle Oxidatiton dyeing composition based on 1-(4-aminophenyl) pyrrolidines substituted in position 2 and 5
US6946005B2 (en) 2002-03-27 2005-09-20 L'oreal S.A. Pyrrolidinyl-substituted para-phenylenediamine derivatives substituted with a cationic radical, and use of these derivatives for dyeing keratin fibers
US20040077852A1 (en) * 2002-07-05 2004-04-22 Stephane Sabelle Para-phenylenediamine derivatives containing a pyrrolidyl group, and use of these derivatives for coloring keratin fibers
US7132534B2 (en) 2002-07-05 2006-11-07 L'oreal Para-phenylenediamine derivatives containing a pyrrolidyl group, and use of these derivatives for coloring keratin fibers
US20040123401A1 (en) * 2002-09-09 2004-07-01 Stephane Sabelle Bis-para-phenylenediamine derivatives comprising a pyrrolidyl group and use of these derivatives for dyeing keratin fibres
US6923835B2 (en) 2002-09-09 2005-08-02 L'oreal S.A. Bis-para-phenylenediamine derivatives comprising a pyrrolidyl group and use of these derivatives for dyeing keratin fibres

Also Published As

Publication number Publication date
FR2225774B1 (en, 2012) 1976-12-17
DE2417945C2 (de) 1984-11-15
GB1421319A (en) 1976-01-14
DE2417945A1 (de) 1974-11-21
JPS49129538A (en, 2012) 1974-12-11
JPS5529421B2 (en, 2012) 1980-08-04
FR2225774A1 (en, 2012) 1974-11-08

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