EP0433229A1 - Procédé de teinture du cuir - Google Patents

Procédé de teinture du cuir Download PDF

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Publication number
EP0433229A1
EP0433229A1 EP90810941A EP90810941A EP0433229A1 EP 0433229 A1 EP0433229 A1 EP 0433229A1 EP 90810941 A EP90810941 A EP 90810941A EP 90810941 A EP90810941 A EP 90810941A EP 0433229 A1 EP0433229 A1 EP 0433229A1
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EP
European Patent Office
Prior art keywords
dye
black
formula
sulfo
substituted
Prior art date
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Granted
Application number
EP90810941A
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German (de)
English (en)
Other versions
EP0433229B1 (fr
Inventor
Hans Dr. Altermatt
Alois Dr. Püntener
Peter Dr. Moser
Ernst Dr. Tempel
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Novartis AG
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Ciba Geigy AG
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Publication of EP0433229A1 publication Critical patent/EP0433229A1/fr
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Publication of EP0433229B1 publication Critical patent/EP0433229B1/fr
Anticipated expiration legal-status Critical
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/32—Material containing basic nitrogen containing amide groups leather skins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/32—Material containing basic nitrogen containing amide groups leather skins
    • D06P3/3206—Material containing basic nitrogen containing amide groups leather skins using acid dyes
    • D06P3/3226—Material containing basic nitrogen containing amide groups leather skins using acid dyes dis-polyazo
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/916—Natural fiber dyeing

Definitions

  • the present invention relates to a method for dyeing leather and dye mixtures suitable therefor.
  • compositions which contain an anionic dye, an inorganic pigment and a suitable binder, for example an acrylic resin; the colored composition forms e.g. after the application by spraying a film on the leather surface.
  • mixtures which consist essentially of a black anionic dye and a modified carbon black are eminently suitable for dyeing leather using the exhaust process.
  • the invention therefore relates to a process for dyeing leather by the exhaust process, characterized in that an aqueous liquor which has a dye mixture comprising a black anionic dye and a sulfonated carbon black is allowed to act on the leather.
  • Suitable black anionic dyes are all dyes customarily used in leather dyeing; Acid dyes and direct dyes such as, in particular, sulfo-containing monoazo, disazo and polyazo dyes and metal complex dyes are preferred.
  • black dyes In addition to dyes with a black shade, black dyes also mean those with a dark blue, blue-gray, gray or yellowish, reddish or greenish black shade.
  • a group of particularly suitable black anionic dyes corresponds to the formula in which one X is hydroxy and the other X is amino or hydrogen, A is an optionally substituted phenyl or naphthyl radical, B is a phenyl or naphthyl radical containing at least one amino and / or hydroxyl group and optionally further substituents, Z a rest represents
  • R and R 'independently of one another are hydrogen, sulfo, C1-C4-alkyl or C1-C4-alkoxy and n is 1 or 2.
  • the phenyl or naphthyl radical A can carry one or more identical or different substituents, for example: C1-C4-alkyl, which here and in general methyl, ethyl, n- or iso-propyl or n-, iso-, sec.- or includes tert-butyl; C1-C4 alkoxy, which generally means methoxy, ethoxy, n- or iso-propoxy or n-, iso, sec.- or tert.-butoxy; Halogen, e.g.
  • Fluorine, bromine and especially chlorine is meant; Trifluoromethyl; C1-C4 alkyl sulfonyl, especially methyl or ethyl sulfonyl; Sulfamoyl, e.g. ⁇ SO2NH2 or N-mono- or N, N-di-C1-C4-alkylaminosulfonyl; Carbamoyl, e.g. ⁇ CONH2 or N-mono- or N, N-di-C1-C4-alkylaminocarbonyl, sulfo; Nitro; Cyano; Carboxy; Phenoxy.
  • A is preferably an unsubstituted or halogen, nitro, sulfo, C1-C4-alkyl and / or C1-C4-alkoxy substituted phenyl radical.
  • the phenyl or naphthyl radical B can carry other radicals besides amino and hydroxy, e.g. an N-mono- or N, N-di-C1-C4-alkylamino, phenylamino, o-, m- or p-methylphenylamino, an unsubstituted or e.g. benzoylamino, C1-C4alkanoylamino or carboxymethylamino or methyl, chlorine or nitro substituted or one of the substituents mentioned above for A.
  • an N-mono- or N, N-di-C1-C4-alkylamino, phenylamino, o-, m- or p-methylphenylamino an unsubstituted or e.g. benzoylamino, C1-C4alkanoylamino or carboxymethylamino or methyl, chlorine or nitro substituted or one of the substituents mentioned above for A
  • B is preferably a phenyl radical which has a hydroxyl or amino group and a further substituent selected from the group consisting of hydroxyl, amino, phenylamino, o-, m- or p-methylphenylamino, C1-C4alkoxy and phenoxy.
  • B particularly preferably represents the remainder of 1,3-dihydroxybenzene, 1,3-diaminobenzene or 3-aminophenol.
  • R and R 'independently of one another are preferably hydrogen, methyl, methoxy or sulfo.
  • Preferred Z radicals are: where R ⁇ means, for example, hydrogen, methyl, methoxy or sulfo.
  • n is preferably the number 2.
  • the black anionic dyes of the formula (1) have, for example, 2-amino-5-naphthol-7-sulfonic acid (I-acid), 1-amino-8-naphthol-4,6-disulfonic acid as the naphthol coupling component (K-acid) or preferably 1-amino-8-naphthol-3,6-disulfonic acid (H-acid).
  • a group of black anionic dyes which is particularly preferred for the process according to the invention corresponds to the formula wherein A 'is a phenyl radical which is unsubstituted or substituted by halogen, nitro, sulfo, C1-C4-alkyl and / or C1-C4-alkoxy, B' is a phenyl radical which has a hydroxyl or amino group and a further substituent selected from the group hydroxyl , Amino, phenylamino, o-, m- or p-methylphenylamino, C1-C4 alkoxy and phenoxy, means Z 'is a radical of the formula wherein R ⁇ has the meaning given above, and one X ′ is hydroxy and the other X ′ is amino.
  • the dyes of the formula (1) or (1a) are known per se or can in themselves can be obtained in a known manner.
  • black anionic dyes are heavy metal-containing monoazo, disazo or polyazo dyes and azomethine dyes.
  • the anionic character of these dyes can be achieved by metal complex formation alone and / or by acidic salt-forming substituents, e.g. Carboxylic acid groups, phosphonic acid groups and especially sulfonic acid groups.
  • the 1: 1 or 1: 2 metal complex dyes are preferred.
  • the 1: 1 metal complexes preferably have one or two sulfonic acid groups and contain e.g. a copper, nickel, iron or in particular a chromium atom.
  • the 1: 2 metal complex dyes contain a heavy metal atom such as e.g. an iron, cobalt or in particular a chromium atom.
  • Two complex-forming components are connected to the central atom, at least one of which is a dye molecule, but preferably both are dye molecules.
  • the two dye molecules involved in the complex formation can be the same or different from one another.
  • the 1: 2 metal complex dyes can e.g. contain two azomethine molecules, an azo and an azomethine dye or preferably two azo dyes, which dyes can be substituted with further arylazo and / or arylazoaryleno groups.
  • Aryl means above all benzene or naphthalene residues, which can be optionally substituted, e.g. by nitro, sulfo, halogen, C1-C4-alkyl or C1-C4-alkoxy.
  • the azo or azomethine dye molecules can have water solubilizing groups such as e.g. Carbamoyl, C1-C4 alkylsulfonyl or the acid groups mentioned above. Preference is given to 1: 2 cobalt or 1: 2 chromium complexes of monoazo or disazo dyes which have sulfonic acid groups.
  • the black complex dyes particularly suitable for the process according to the invention correspond, for example, to the formula in the form of the free acid in which D and D ′ each independently represent an optionally further substituted benzene or naphthalene radical which contains a hydroxyl group in the ortho position to the azo group, K and K 'each independently represent the rest of a coupling component of the benzene or naphthalene series, which contains a hydroxyl group in the ortho position to the azo group and is optionally further substituted, and Me represents chromium or cobalt.
  • Both symmetrical and asymmetrical 1: 2 metal complexes are suitable as dyes of the formula (2).
  • Me in formula (2) is preferably chromium.
  • D and D 'independently of one another preferably represent a phenyl or naphthyl radical, optionally by sulfo, nitro, C1-C4-alkylsulfonyl, C1-C4-alkyl, halogen, sulfamoyl, N-mono- or N, N-di-C1 -C4-Alkylaminosulfonyl and / or in the phenyl part optionally substituted by C1-C4-alkyl, C1-C4-alkoxy, sulfo, nitro or halogen substituted phenylazo.
  • the residues D and D ' can be derived, for example, from the following compounds: Anthranilic acid, 4- or 5-sulfo-2-aminophenol, 4- or 5-nitro-2-aminophenol, 4-nitro-6-sulfo-2-aminophenol, 6-nitro-4-sulfo-2-aminophenol, 4-chloro-5-nitro-2-aminophenol, 4-methyl-2-aminophenol, 6-chloro-4-sulfo-2-aminophenol, 4-chloro-6-sulfo-2-aminophenol, 4-chloro or 4 -Methyl- 6-nitro-2-aminophenol, 4-chloro-2-aminophenol, 4-methylsulfonyl-2-aminophenol, 4- (2-methoxyphenylazo) -2-aminophenol, 4- (2-, 3rd - or 4-sulfophenylazo) -2-aminophenol, 4-phenylazo-2-aminophenol, 1-amino-2-hydroxy
  • D and D 'independently of one another particularly preferably represent the remainder of a 2-aminophenol, which optionally one or more times by identical or different substituents from the series nitro, sulfo, chlorine, methyl, methoxy, methylsulfonyl, sulfamoyl and optionally by sulfo, methyl , Methoxy, nitro or chlorine-substituted phenylazo is substituted, or for the remainder of a 1-amino-2-hydroxynaphthalene, which is optionally substituted by sulfo and / or nitro.
  • K and K ′ means e.g. a phenol or 1- or 2-naphthol residue, which may be e.g. by amino, hydroxy, C1-C4-alkoxy, C1-C4-alkyl, sulfamoyl, N-mono- or N, N-di-C1-C4-alkylaminosulfonyl, C1-C4-alkanoylamino, e.g.
  • Suitable coupling components which can be the basis of the radicals K and K 'are: 1-naphthol, 2-naphthol, 1,3- or 1,5-dihydroxynaphthalene, 2-hydroxy-8-acetylaminonaphthalene, 2-naphthol 3-, -4-, -5-, -6-, -7- or -8-sulfonic acid, resorcinol, 3-dimethylamino- or 3-diethylaminophenol, phenyl-azoresorcinol, o-, m- or p-chlorophenylazoresorcinol, Bis- (o-, m- or p-chlorophenylazo) resorcinol.
  • K and K 'independently of one another represent an unsubstituted or substituted by hydroxy, amino, sulfo, sulfamoyl or acetylamino 1- or 2-naphthol residue or an unsubstituted or optionally substituted by methyl, methoxy, chlorine, sulfo or nitro substituted resorcinol .
  • the complex dyes of formula (2) have e.g. 0 to 4, preferably 1 to 4 and particularly preferably 1 or 2 sulfo groups.
  • Black complex dyes which are in the form of the free acid of the formula are particularly preferred for the process according to the invention correspond in which D1 and D2 independently of one another the residue of an unsubstituted or substituted by sulfo and / or nitro 1-amino-2-hydroxynaphthalene or the residue of an unsubstituted or by nitro, sulfo, chlorine, methyl, methoxy, methylsulfonyl or optionally by sulfo, Methyl, methoxy, nitro or chlorine-substituted phenylazo are substituted 2-aminophenols and K1 and K2 independently of one another for an unsubstituted or substituted by hydroxyl, amino, sulfo or acetylamino or 1- or 2-naphthol radical or for an unsubstituted or optionally by methyl, methoxy , Chlorine, sulfo or nitro substituted phenylazo substituted res
  • Examples of preferred black complex dyes are:
  • the metal complex compounds of the formula (2) which are advantageously used in the form of their salts, in particular alkali metal salts, such as lithium, potassium and especially sodium salts or also ammonium salts, are known per se or can be obtained in a manner known per se.
  • Suitable sulfonated Russian are known, for example, from US Pat. No. 3,528,840 or from German Offenlegungsschrift No. 1 927 597 or can be prepared analogously to the processes specified there. They are Russian, the sulfo groups contain chemically and / or physically bound, so that they cannot be removed by washing with water.
  • the sulfonated carbon blacks used according to the invention advantageously have a sulfur content of, for example, 0.5 to 6% by weight and preferably 1 to 3% by weight, and an acidic pH, ie a pH below 7 and preferably between 1 and 5 , on; the pH value of the soot here means the pH value of the soot suspended in distilled water.
  • the sulfonated Russian can be obtained e.g. by using a conventional carbon black based on US Pat. No. 3,528,840 - all types of carbon black and in particular those with an average particle size of 10 to 100 nm and preferably 20 to 50 nm are suitable - together with ammonium sulfite or preferably ammonium sulfate to a temperature heated above 230 ° C, preferably to a temperature between 250 and 300 ° C, with stirring.
  • the amount of ammonium sulfite or ammonium sulfate required depends on the desired pH and sulfur content of the sulfated carbon black, but is generally 1 to 20% by weight, preferably 2-15% by weight and particularly preferably 5 to 12% by weight. %, based on the weight of the soot used.
  • a carrier gas e.g. Air or nitrogen.
  • Oleum can serve as a SO3 supplier, and nitrogen is then passed through the oleum, for example, so that SO3 is carried along by the nitrogen stream.
  • the supply of SO3 and nitrogen to the reaction vessel in which the soot is stirred at the reaction temperature is interrupted as soon as the desired amount of SO3 has been introduced.
  • the pH of the carbon black can be used to determine the amount of SO3 required.
  • soot samples are taken, the pH of which is determined and the SO 3 feed is ended when the desired pH of the soot has been reached.
  • the dye mixtures used according to the invention contain the black anionic dye and the sulfonated carbon black, for example in a weight ratio of 95: 5 to 60:40, preferably 90:10 to 70:30 and particularly preferably 80:20 to 75:25; Mixtures of various anionic dyes and / or carbon black are also possible.
  • the dye mixtures can also optionally contain a dedusting agent, for example a dust oil.
  • Dye mixtures containing a black dye of the formula (1) or (2) given above and a sulfonated carbon black with a sulfur content of 0.5 to 6% by weight are preferred for the process according to the invention.
  • a dye mixture comprising a black anionic dye of the formula (1a) or (2a) given above and a sulfonated carbon black with a sulfur content of 1 to 3% by weight in a weight ratio of 90:10 to 70:30, and especially 80:20 to 75:25.
  • the above-mentioned dye mixtures which consist essentially of a black anionic dye and a sulfonated carbon black, are new and a further object of the present invention. They can be made e.g. by mechanical mixing of the components in a suitable mixing device, e.g. in a ball or pin mill or in a kneader or mixer.
  • the process according to the invention is advantageously carried out by first pretreating the leather to be dyed, e.g. subject to retanning, neutralization and / or Walke.
  • the leather pretreated in this way is then dyed by means of a pull-out method known per se, using one of the aforementioned dye mixtures; for example, the leather is dyed in an aqueous solution with a liquor ratio of 1: 1.5 to 1:20, preferably 1: 2 to 1:10 and a temperature of e.g. 20 to 100 ° C, preferably 40 to 60 ° C.
  • a liquor ratio of 1: 1.5 to 1:20, preferably 1: 2 to 1:10
  • a temperature e.g. 20 to 100 ° C, preferably 40 to 60 ° C.
  • the dyeing time also depends on the type of leather to be dyed, but is generally e.g. 20 to 180 minutes.
  • the dye bath can optionally be added before, during or after dyeing generally customary additives, for example wetting agents, leveling agents, color deepening agents and / or greasing agents, are added.
  • wetting agents for example, to improve bath exhaustion and to continue to run for some time.
  • the dyed leather is finished in a manner known per se.
  • the dyeing process according to the invention is suitable for all types of leather, e.g. Grain and suede leather - chrome leather, retanned leather or suede from goat, sheep, beef and pork - suitable.
  • Level, deep, well covering dyeings with good general fastness properties are obtained, e.g. Water, washing, welding, dry cleaning, acid, alkali, solvent, rubbing and diffusion fastness to soft PVC;
  • the excellent lightfastness of the dyeings obtainable according to the invention deserves special mention.
  • 100 parts of intermediate-dried sheep nappa leather are pretreated in a liquor prepared from 1000 parts of water, 2 parts of a nonionic wetting agent (polyethylene glycol ether derivative) and 1 part of ammonia 24% strength at 50 ° C. for 60 minutes and then rinsed well.
  • a nonionic wetting agent polyethylene glycol ether derivative
  • the leather prepared in this way is now dyed in a fresh liquor consisting of 500 parts of water and 5 parts of one of the color mixtures mentioned in the table at 50 ° C. for 30 minutes.
  • a fatliquor mixture consisting of 2 parts of sulfited marine oil, 2 parts of a mixture of sulfitated fatty acid esters and animal fat and 4 parts of a mixture of sulfited natural oils and animal fat.
  • a cationic color deepening agent polyquaternary amine / ethylene oxide adduct
  • the dye mixtures used according to Examples 3 to 18 are obtained by simply mixing the components in a mixer.
  • chrome cowhide 100 parts are pretreated in a liquor consisting of 200 parts of water, 1 part of sodium formate and 2 parts of an anionic wetting agent (Na salts of aromatic sulfonic acids and aliphatic dicarboxylic acids) for 15 minutes at 30 ° C, then 2 parts of an anionic fatliquor (sulfited marine oil) , 2 parts of an anionic retanning agent (condensation product of aromatic sulfonic acids) and 1.5 parts of sodium hydrogen carbonate are added and the mixture is left to run for 60 minutes.
  • an anionic wetting agent Na salts of aromatic sulfonic acids and aliphatic dicarboxylic acids
  • the leather is rinsed well with warm water and then retanned in a fresh liquor consisting of 100 parts of water and 8 parts of an anionic retanning agent (condensation product of aromatic sulfone derivatives with dialkylolcarbamide) at 40 ° C. for 30 minutes. Then 5 parts of the aforementioned anionic fatliquor are added, the mixture is left to run for 60 minutes, 0.5 parts of 85% formic acid are then added and the treatment is continued for a further 15 minutes.
  • an anionic retanning agent condensation product of aromatic sulfone derivatives with dialkylolcarbamide
  • the leather retanned in this way is now dyed in a fresh liquor consisting of 100 parts of water, 0.5 part of ammonia, 1 part of a leveling agent (polyglycol ether derivative) and 2.65 parts of the dye mixture according to Example 4 at 30 ° C. for 30 minutes. Then 8 parts of the above-mentioned fatliquor and 4 parts of a hydrophobizing agent are added. After a further 60 minutes, it is acidified with 2.5 parts of 85% formic acid and the treatment is then continued for 30 minutes.
  • a leveling agent polyglycol ether derivative
  • the liquor additionally contains 0.5 parts of a cationic color deepening agent (polyquaternary amine-ethylene oxide adduct).
  • a cationic color deepening agent polyquaternary amine-ethylene oxide adduct
  • 1 part of 85% strength formic acid is added to the dyebath and after a further 15 minutes 1.5 parts of a cationic fatliquor (preparation based on chlorinated hydrocarbons and n-alkyl derivatives) are added.
  • a cationic fatliquor preparation based on chlorinated hydrocarbons and n-alkyl derivatives
  • 100 parts of shoe leather are first washed in a liquor consisting of 300 parts of water and 0.5 parts of an anionic wetting agent for 15 minutes at 35 ° C. and then in a fresh bath of 150 parts of water and 4 parts of an anionic retanning agent (Na salts of aromatic sulfonic acids and aliphatic dicarboxylic acids) existing liquor treated at 35 ° C for 30 minutes.
  • a liquor consisting of 300 parts of water and 0.5 parts of an anionic wetting agent for 15 minutes at 35 ° C. and then in a fresh bath of 150 parts of water and 4 parts of an anionic retanning agent (Na salts of aromatic sulfonic acids and aliphatic dicarboxylic acids) existing liquor treated at 35 ° C for 30 minutes.
  • an anionic retanning agent Na salts of aromatic sulfonic acids and aliphatic dicarboxylic acids
  • the mixture is acidified with 1 part of 85% formic acid and the treatment is then continued for 30 minutes. Then in a fresh bath with 2 parts of the dye mixture used above in 300 parts of water, 0.5 parts of 85% formic acid and 1 part of a deepening agent (polyquaternary amine / ethylene oxide adduct) for 50 minutes at 50 ° C, then another 0 , 5 parts of 85% formic acid were added and the mixture was allowed to continue running for 20 minutes. The leather is rinsed and finished as usual. The result is a level black coloring with good general fastness properties.
  • a deepening agent polyquaternary amine / ethylene oxide adduct

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)
EP90810941A 1989-12-11 1990-12-03 Procédé de teinture du cuir Expired - Lifetime EP0433229B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH4438/89 1989-12-11
CH443889 1989-12-11

Publications (2)

Publication Number Publication Date
EP0433229A1 true EP0433229A1 (fr) 1991-06-19
EP0433229B1 EP0433229B1 (fr) 1994-01-26

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Application Number Title Priority Date Filing Date
EP90810941A Expired - Lifetime EP0433229B1 (fr) 1989-12-11 1990-12-03 Procédé de teinture du cuir

Country Status (5)

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US (1) US5152801A (fr)
EP (1) EP0433229B1 (fr)
JP (1) JPH04241174A (fr)
DE (1) DE59004417D1 (fr)
ES (1) ES2049014T3 (fr)

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EP0558450A1 (fr) * 1992-02-28 1993-09-01 Ciba-Geigy Ag Procédé pour teindre du cuir avec des mélanges de colorants
EP0572353A1 (fr) * 1992-05-26 1993-12-01 Ciba-Geigy Ag Procédé de teinture du cuir
EP0577556A1 (fr) * 1992-06-30 1994-01-05 Ciba-Geigy Ag Procédé pour teindre du cuir par trichromie avec des mélanges de colorants
EP0648816A1 (fr) * 1993-10-15 1995-04-19 Ciba-Geigy Ag Teinture du cuir avec des mélanges de colorants
WO1997035927A1 (fr) * 1996-03-26 1997-10-02 Basf Aktiengesellschaft Compositions stables de colorants
WO1998000465A1 (fr) * 1996-07-01 1998-01-08 Basf Aktiengesellschaft Melanges de colorants contenant des colorants polyazoiques et le colorant noir au soufre 1 ci
RU2178466C2 (ru) * 1999-07-22 2002-01-20 Общество с ограниченной ответственностью "ЭКОХИМ-2000" Состав для жирования кож с окрашивающим эффектом
RU2215790C1 (ru) * 2002-12-25 2003-11-10 Московский государственный университет дизайна и технологии Способ обработки волосяного покрова меха
RU2246542C1 (ru) * 2004-02-10 2005-02-20 Федеральное государственное унитарное предприятие "Центральный научно-исследовательский институт кожевенно-обувной промышленности" Способ выработки подкладочных кож из свиного сырья

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US6821334B2 (en) * 2001-09-19 2004-11-23 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Process for producing sulfonated solid particles
EP1509929A4 (fr) 2002-05-23 2007-03-21 Columbian Chem Materiau conducteur carbone greffe sur un polymere destine a des applications de pile a combustible
US7459103B2 (en) * 2002-05-23 2008-12-02 Columbian Chemicals Company Conducting polymer-grafted carbon material for fuel cell applications
US7195834B2 (en) * 2002-05-23 2007-03-27 Columbian Chemicals Company Metallized conducting polymer-grafted carbon material and method for making
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US7390441B2 (en) * 2002-05-23 2008-06-24 Columbian Chemicals Company Sulfonated conducting polymer-grafted carbon material for fuel cell applications
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US6958308B2 (en) 2004-03-16 2005-10-25 Columbian Chemicals Company Deposition of dispersed metal particles onto substrates using supercritical fluids
US20060068987A1 (en) * 2004-09-24 2006-03-30 Srinivas Bollepalli Carbon supported catalyst having reduced water retention
RU2263713C1 (ru) * 2004-10-27 2005-11-10 Курский государственный технический университет (КГТУ) Способ получения черной красящей композиции для жирующих составов
RU2272846C1 (ru) * 2004-10-27 2006-03-27 Курский государственный технический университет (КГТУ) Способ получения совместимой с жирующим составом черной красящей композиции
CN114855469B (zh) * 2022-04-15 2023-07-04 苏州大学 一种基于液体炭黑@分散染料黑制备功能涤氨纶针织物的印花方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2162122A1 (fr) * 1971-11-30 1973-07-13 Bayer Ag
FR2360634A1 (fr) * 1976-08-03 1978-03-03 Ugine Kuhlmann Nouveaux colorants trisazoiques hydrosolubles
DE3825755A1 (de) * 1987-08-08 1989-02-16 Sandoz Ag Faerben und bedrucken von leder

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3528840A (en) * 1967-11-15 1970-09-15 Huber Corp J M Sulfonated carbon black
NL6807617A (fr) * 1968-05-30 1969-12-02
AU552418B2 (en) * 1982-07-08 1986-05-29 Toray Industries, Inc. Artificial grain leather with different colour spots
IT1211465B (it) * 1987-06-19 1989-11-03 Lorica Spa Procedimento per ottenere un pellame scamosciato sintetico simile a quello naturale
IT1224686B (it) * 1987-08-08 1990-10-18 Sandoz Ag Procedimento per la tintura o lastampa di pelli
ES2068915T3 (es) * 1989-01-02 1995-05-01 Ciba Geigy Ag Procedimiento para teñir el cuero.

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2162122A1 (fr) * 1971-11-30 1973-07-13 Bayer Ag
FR2360634A1 (fr) * 1976-08-03 1978-03-03 Ugine Kuhlmann Nouveaux colorants trisazoiques hydrosolubles
DE3825755A1 (de) * 1987-08-08 1989-02-16 Sandoz Ag Faerben und bedrucken von leder

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI,no 74-76430v Derwent Publications Ltd, London, GB, & JP-A-56025557 (YAMAMOTO KAGAKU GOSEI CO) *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0558450A1 (fr) * 1992-02-28 1993-09-01 Ciba-Geigy Ag Procédé pour teindre du cuir avec des mélanges de colorants
US5376147A (en) * 1992-02-28 1994-12-27 Ciba-Geigy Corporation Process for dyeing leather with dye mixtures
EP0572353A1 (fr) * 1992-05-26 1993-12-01 Ciba-Geigy Ag Procédé de teinture du cuir
EP0577556A1 (fr) * 1992-06-30 1994-01-05 Ciba-Geigy Ag Procédé pour teindre du cuir par trichromie avec des mélanges de colorants
EP0648816A1 (fr) * 1993-10-15 1995-04-19 Ciba-Geigy Ag Teinture du cuir avec des mélanges de colorants
WO1997035927A1 (fr) * 1996-03-26 1997-10-02 Basf Aktiengesellschaft Compositions stables de colorants
US6080209A (en) * 1996-03-26 2000-06-27 Basf Aktiengesellschaft Stable colorant compositions
WO1998000465A1 (fr) * 1996-07-01 1998-01-08 Basf Aktiengesellschaft Melanges de colorants contenant des colorants polyazoiques et le colorant noir au soufre 1 ci
US5972050A (en) * 1996-07-01 1999-10-26 Basf Aktiengesellschaft Dye mixtures containing polyazo dyes and CI Sulphur Black 1 dye
RU2178466C2 (ru) * 1999-07-22 2002-01-20 Общество с ограниченной ответственностью "ЭКОХИМ-2000" Состав для жирования кож с окрашивающим эффектом
RU2215790C1 (ru) * 2002-12-25 2003-11-10 Московский государственный университет дизайна и технологии Способ обработки волосяного покрова меха
RU2246542C1 (ru) * 2004-02-10 2005-02-20 Федеральное государственное унитарное предприятие "Центральный научно-исследовательский институт кожевенно-обувной промышленности" Способ выработки подкладочных кож из свиного сырья

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US5152801A (en) 1992-10-06
DE59004417D1 (de) 1994-03-10
EP0433229B1 (fr) 1994-01-26
ES2049014T3 (es) 1994-04-01
JPH04241174A (ja) 1992-08-28

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