EP0433229B1 - Process for dyeing leather - Google Patents
Process for dyeing leather Download PDFInfo
- Publication number
- EP0433229B1 EP0433229B1 EP90810941A EP90810941A EP0433229B1 EP 0433229 B1 EP0433229 B1 EP 0433229B1 EP 90810941 A EP90810941 A EP 90810941A EP 90810941 A EP90810941 A EP 90810941A EP 0433229 B1 EP0433229 B1 EP 0433229B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- dye
- formula
- black
- sulfo
- radical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 0 C*1C=CC(N)=C*(*)C=C1 Chemical compound C*1C=CC(N)=C*(*)C=C1 0.000 description 5
- NLRKCXQQSUWLCH-UHFFFAOYSA-N O=Nc1ccccc1 Chemical compound O=Nc1ccccc1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
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- 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 which are customarily used in leather dyeing; Acid dyes and direct dyes such as, in particular, sulfo group-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 or 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 comprises 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.
- 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, Z 'means 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 as the central atom, 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 here means above all benzene or naphthalene residues which may be 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 above acidic groups. 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 which are particularly suitable for the process according to the invention correspond, for example, to the formula in the form of the free acid wherein D and D 'independently of one another each represent an optionally further substituted benzene or naphthalene radical which contains a hydroxy 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-, 3- or 4-sulfophenylazo) -2-aminophenol, 4-phenylazo-2-aminophenol, 1-amino-2-hydroxy-naphthalene-4-sulf
- D and D 'independently of one another particularly preferably represent the remainder of a 2-aminophenol, which may be substituted 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, 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 optionally 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 may be the basis of the radicals K or 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 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 residue or for an unsubstituted or optionally by methyl, methoxy , Chlorine, sulfo or nitro substituted phenylazo substituted resor
- Examples of preferred black complex dyes are:
- 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 above all 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-A-3,528,840 or from DE-A-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 is to be understood here as 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 above of 230 ° C, preferably to a temperature between 250 and 300 ° C, heated 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.
- sulfonated carbon black based on DE-A-1 927 597 by reacting a conventional carbon black as described above in the dry state with gaseous sulfur trioxide (SO3) at elevated temperature, e.g. at 100 to 300 ° C and preferably at 150 to 200 ° C.
- SO3 gaseous sulfur trioxide
- SO3 in the soot with the help of a carrier gas, e.g. Air or nitrogen.
- a carrier gas e.g. Air or nitrogen.
- Oleum can serve as 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 subject 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 an extraction process known per se, using one of the dye mixtures mentioned above; 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 then 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 sulfited fatty acid esters and animal fat and 4 parts of a mixture of sulfited natural oils and animal fat.
- the mixture is acidified with 4 parts of 85% formic acid (pH approx. 3.2) and the treatment is then continued for 20 minutes.
- 2 parts of 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 sea 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 dialkylol carbamide) 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, then 0.5 parts of 85% formic acid are added and the treatment is continued for 15 minutes.
- an anionic retanning agent condensation product of aromatic sulfone derivatives with dialkylol carbamide
- the leather retanned in this way is then 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, the mixture 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 and after a further 15 minutes 1.5 parts of a cationic fatliquor (preparation based on chlorinated hydrocarbons and n-alkyl derivatives) are added to the dyebath.
- a final treatment time of 20 minutes rinsing and finishing as usual. The result is a level, deep black color with good general fastness properties.
- 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
Description
Die vorliegende Erfindung betrifft ein Verfahren zum Färben von Leder sowie dafür geeignete Farbstoffmischungen.The present invention relates to a method for dyeing leather and dye mixtures suitable therefor.
Es ist bereits bekannt, Leder mit Zusammensetzungen, die einen anionischen Farbstoff, ein anorganisches Pigment und einen geeigneten Binder, etwa ein Acrylharz, enthalten, zu beschichten; die farbige Zusammensetzung bildet dabei nach dem Auftrag z.B. durch Besprühen einen Film auf der Lederoberfläche.It is already known to coat leather with 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.
Es wurde nun überraschend gefunden, dass sich Mischungen, die im wesentlichen aus einem schwarzen anionischen Farbstoff und einem modifizierten Russ bestehen, hervorragend für das Färben von Leder nach dem Ausziehverfahren eignen.It has now surprisingly been found that mixtures which consist essentially of a black anionic dye and a modified carbon black are eminently suitable for dyeing leather using the exhaust process.
Gegenstand der Erfindung ist daher ein Verfahren zum Färben von Leder nach dem Ausziehverfahren, dadurch gekennzeichnet, dass man auf das Leder eine wässrige Flotte, die eine Farbstoffmischung enthaltend einen schwarzen anionischen Farbstoff und einen sulfierten Russ aufweist, einwirken lässt.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.
Als schwarze anionische Farbstoffe kommen alle üblicherweise in der Lederfärberei verwendeten Farbstoffe in Frage; bevorzugt sind hierbei Säurefarbstoffe und Direktfarbstoffe wie insbesondere sulfogruppenhaltige Monoazo-, Disazo- und Polyazofarbstoffe sowie Metallkomplexfarbstoffe.Suitable black anionic dyes are all dyes which are customarily used in leather dyeing; Acid dyes and direct dyes such as, in particular, sulfo group-containing monoazo, disazo and polyazo dyes and metal complex dyes are preferred.
Unter schwarzen Farbstoffen sind neben Farbstoffen mit einer schwarzen Nuance auch solche mit einer dunkelblauen, blaugrauen, grauen oder gelbstichig, rotstichig oder grünstichig schwarzen Nuance zu verstehen.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.
Eine Gruppe von besonders geeigneten schwarzen anionischen Farbstoffen entspricht der Formel
worin ein X Hydroxy und das andere X Amino oder Wasserstoff bedeutet, A ein gegebenenfalls substituierter Phenyl- oder Naphthylrest ist, B einen Phenyl- oder Naphthylrest enthaltend mindestens eine Amino- und/oder Hydroxygruppe sowie gegebenenfalls weitere Substituenten bedeutet,
Z einen Rest
oder
darstellt,
R und R' unabhängig voneinander Wasserstoff, Sulfo, C₁-C₄-Alkyl oder C₁-C₄-Alkoxy bedeuten und n 1 oder 2 ist.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
or
represents
R and R 'independently of one another are hydrogen, sulfo, C₁-C₄-alkyl or C₁-C₄-alkoxy and n is 1 or 2.
Der Phenyl- oder Naphthylrest A kann einen oder mehrere gleiche oder verschiedene Substituenten tragen, z.B.: C₁-C₄-Alkyl, welches hier und im weiteren generell Methyl, Ethyl, n- oder iso-Propyl oder n-, iso-, sec.- oder tert.-Butyl umfasst; C₁-C₄-Alkoxy, worunter generell Methoxy, Ethoxy, n- oder iso-Propoxy oder n-, iso, sec.- oder tert.-Butoxy zu verstehen ist; Halogen, womit z.B. Fluor, Brom und insbesondere Chlor gemeint ist; Trifluormethyl; C₁-C₄-Alkylsulfonyl, besonders Methyl-, oder Ethylsulfonyl; Sulfamoyl, z.B. -SO₂NH₂ oder N-Mono- oder N,N-Di-C₁-C₄-alkylaminosulfonyl; Carbamoyl, z.B. -CONH₂ oder N-Mono- oder N,N-Di-C₁-C₄-alkylaminocarbonyl, Sulfo; Nitro; Cyano; Carboxy; Phenoxy.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 comprises 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.
Vorzugsweise steht A für einen unsubstituierten oder durch Halogen, Nitro, Sulfo, C₁-C₄-Alkyl und/oder C₁-C₄-Alkoxy substituierten Phenylrest.A is preferably an unsubstituted or halogen, nitro, sulfo, C₁-C₄ alkyl and / or C₁-C₄ alkoxy substituted phenyl.
Der Phenyl- oder Naphthylrest B kann ausser Amino und Hydroxy noch weitere Reste tragen, z.B. einen N-Mono- oder N,N-Di-C₁-C₄-Alkylamino-, Phenylamino-, o-, m- oder p-Methylphenylamino-, einen unsubstituierten oder z.B. durch Methyl, Chlor oder Nitro substituierten Benzoylamino-, C₁-C₄-Alkanoylamino- oder Carboxymethylaminorest oder einen der zuvor für A genannten Substituenten.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.
Vorzugsweise handelt es sich bei B um einen Phenylrest, der eine Hydroxy- oder Aminogruppe und einen weiteren Substituenten ausgewählt aus der Gruppe Hydroxy, Amino, Phenylamino, o-, m- oder p-Methylphenylamino, C₁-C₄-Alkoxy und Phenoxy trägt.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 steht besonders bevorzugt für den Rest von 1,3-Dihydroxybenzol, 1,3-Diaminobenzol oder 3-Aminophenol.B particularly preferably represents the remainder of 1,3-dihydroxybenzene, 1,3-diaminobenzene or 3-aminophenol.
R und R' bedeuten unabhängig voneinander vorzugsweise Wasserstoff, Methyl, Methoxy oder Sulfo.R and R 'independently of one another are preferably hydrogen, methyl, methoxy or sulfo.
Bevorzugte Reste Z sind:
worin R'' z.B. Wasserstoff, Methyl, Methoxy oder Sulfo bedeutet.Preferred Z radicals are:
where R '' means, for example, hydrogen, methyl, methoxy or sulfo.
n steht vorzugsweise für die Zahl 2.n is preferably the number 2.
Die schwarzen anionischen Farbstoffe der Formel (1) weisen als Naphthol-Kupplungskomponente z.B. 2-Amino-5-naphthol-7-sulfonsäure (I-Säure), 1-Amino-8-naphthol-4,6-disulfonsäure (K-Säure) oder vorzugsweise 1-Amino-8-naphthol-3,6-disulfonsäure (H-Säure) auf.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).
Eine für das erfindungsgemässe Verfahren besonders bevorzugte Gruppe von schwarzen anionischen Farbstoffen entspricht der Formel
worin A' ein unsubstituierter oder durch Halogen, Nitro, Sulfo, C₁-C₄-Alkyl und/oder C₁-C₄-Alkoxy substituierter Phenylrest ist, B' einen Phenylrest, der eine Hydroxy- oder Aminogruppe und einen weiteren Substituenten ausgewählt aus der Gruppe Hydroxy, Amino, Phenylamino, o-, m- oder p-Methylphenylamino, C₁-C₄-Alkoxy und Phenoxy aufweist, bedeutet, Z' einen Rest der Formel
worin R'' die zuvor angegebene Bedeutung hat, darstellt und ein X' Hydroxy und das andere X' Amino ist.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, Z 'means a radical of the formula
wherein R "has the meaning given above, and one X 'is hydroxy and the other X' is amino.
Beispiele für besonders bevorzugte schwarze Farbstoffe der Formel (1) sind
Die Farbstoffe der Formel (1) bzw. (1a) sind an sich bekannt oder können in an sich bekannter Weise erhalten werden.The dyes of the formula (1) or (1a) are known per se or can in themselves can be obtained in a known manner.
Eine weitere Gruppe von geeigneten schwarzen anionischen Farbstoffen stellen schwermetallhaltige Monoazo-, Disazo- oder Polyazofarbstoffe sowie Azomethinfarbstoffe dar. Der anionische Charakter dieser Farbstoffe kann durch Metallkomplexbildung allein und/oder durch saure salzbildende Substituenten, wie z.B. Carbonsäuregruppen, Phosphonsäuregruppen und insbesondere Sulfonsäuregruppen, bedingt sein. Bevorzugt sind die 1:1-oder 1:2-Metallkomplexfarbstoffe. Die 1:1-Metallkomplexe weisen bevorzugt eine oder zwei Sulfonsäuregruppen auf und enthalten als Schwermetall z.B. ein Kupfer-, Nickel-, Eisen- oder insbesondere ein Chromatom.Another group of suitable 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.
Die 1:2-Metallkomplexfarbstoffe enthalten als Zentralatom ein Schwermetallatom wie z.B. ein Eisen-, Kobalt- oder insbesondere ein Chromatom. Mit dem Zentralatom sind zwei komplexbildende Komponenten verbunden, von denen mindestens eine ein Farbstoffmolekül ist, vorzugsweise jedoch beide Farbstoffmoleküle sind. Dabei können die beiden an der Komplexbildung beteiligten Farbstoffmoleküle gleich oder voneinander verschieden sein. Die 1:2-Metallkomplexfarbstoffe können z.B. zwei Azomethinmoleküle, einen Azo- und einen Azomethinfarbstoff oder bevorzugt zwei Azofarbstoffe enthalten, wobei diese Farbstoffe mit weiteren Arylazo- und/oder Arylazoarylenazogruppen substituiert sein können. Mit Aryl sind hier vor allem Benzol- oder Naphthalinreste gemeint, welche gegebenenfalls substituiert sein können, z.B. durch Nitro, Sulfo, Halogen, C₁-C₄-Alkyl oder C₁-C₄-Alkoxy. Die Azo- oder Azomethinfarbstoffmoleküle können wasserlöslichmachende Gruppen aufweisen wie z.B. Carbamoyl-, C₁-C₄-Alkylsulfonyl- oder die obengenannten sauren Gruppen. Bevorzugt sind 1:2-Kobalt- oder 1:2-Chromkomplexe von Monoazo- oder Disazofarbstoffen, die Sulfonsäuregruppen aufweisen.The 1: 2 metal complex dyes contain a heavy metal atom as the central atom, 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 here means above all benzene or naphthalene residues which may be 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 above acidic groups. Preference is given to 1: 2 cobalt or 1: 2 chromium complexes of monoazo or disazo dyes which have sulfonic acid groups.
Die für das erfindungsgemässe Verfahren besonders geeigneten schwarzen Komplexfarbstoffe entsprechen in Form der freien Säure z.B. der Formel
worin D und D' unabhängig voneinander je einen gegebenenfalls weitersubstituierten Benzol-oder Naphthalinrest, der in ortho-Stellung zur Azogruppe eine Hydroxygruppe enthält, bedeuten,
K und K' unabhängig voneinander je den Rest einer Kupplungskomponente der Benzol-oder Naphthalinreihe, der in ortho-Stellung zur Azogruppe eine Hydroxygruppe enthält und gegebenenfalls weitersubstituiert ist, darstellen und Me für Chrom oder Kobalt steht.The black complex dyes which are particularly suitable for the process according to the invention correspond, for example, to the formula in the form of the free acid
wherein D and D 'independently of one another each represent an optionally further substituted benzene or naphthalene radical which contains a hydroxy 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.
Als Farbstoffe der Formel (2) kommen sowohl symmetrische als auch asymmetrische 1:2 Metallkomplexe in Frage.Both symmetrical and asymmetrical 1: 2 metal complexes are suitable as dyes of the formula (2).
Me in Formel (2) steht vorzugsweise für Chrom.Me in formula (2) is preferably chromium.
D und D' stehen unabhängig voneinander bevorzugt für einen Phenyl- oder Naphthylrest, der gegebenenfalls durch Sulfo, Nitro, C₁-C₄-Alkylsulfonyl, C₁-C₄-Alkyl, Halogen, Sulfamoyl, N-Mono- oder N,N-Di-C₁-C₄-Alkylaminosulfonyl und/oder im Phenylteil gegebenenfalls durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Sulfo, Nitro oder Halogen substituiertes Phenylazo substituiert ist.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.
Die Reste D und D' können sich z.B. von folgenden Verbindungen ableiten: Anthranilsäure, 4- oder 5-Sulfo-2-aminophenol, 4- oder 5-Nitro-2-amino- phenol, 4-Nitro-6-sulfo-2-aminophenol, 6-Nitro-4-sulfo-2-aminophenol, 4-Chlor-5-nitro-2-aminophenol, 4-Methyl-2-aminophenol, 6-Chlor-4-sulfo-2-aminophenol, 4-Chlor-6-sulfo-2-aminophenol, 4-Chlor- oder 4-Methyl-6-nitro-2-aminophenol, 4-Chlor-2-amino-phenol, 4-Methylsulfonyl-2-amino- phenol, 4-(2-Methoxyphenylazo)-2-aminophenol, 4-(2-, 3- oder 4-Sulfo- phenylazo)-2-aminophenol, 4-Phenylazo-2-aminophenol, 1-Amino-2-hydroxy- naphthalin-4-sulfonsäure, 1-Amino-2-hydroxy-6-nitronaphthalin-4-sulfonsäure.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-, 3- or 4-sulfophenylazo) -2-aminophenol, 4-phenylazo-2-aminophenol, 1-amino-2-hydroxy-naphthalene-4-sulfonic acid, 1 -Amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid.
D und D' stehen unabhängig voneinander besonders bevorzugt für den Rest eines 2-Aminophenols, welches gegebenenfalls ein- oder mehrfach durch gleiche oder verschiedene Substituenten aus der Reihe Nitro, Sulfo, Chlor, Methyl, Methoxy, Methylsulfonyl, Sulfamoyl und gegebenenfalls durch Sulfo, Methyl, Methoxy, Nitro oder Chlor substituiertes Phenylazo substituiert ist, oder für den Rest eines 1-Amino-2-hydroxynaphthalins, welches gegebenfalls durch Sulfo und/oder Nitro substituiert ist.D and D 'independently of one another particularly preferably represent the remainder of a 2-aminophenol, which may be substituted 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, or for the remainder of a 1-amino-2-hydroxynaphthalene, which is optionally substituted by sulfo and / or nitro.
K und K' bedeutent z.B. einen Phenol- oder 1- oder 2-Naphtholrest, welcher gegebenenfalls z.B. durch Amino, Hydroxy, C₁-C₄-Alkoxy, C₁-C₄-Alkyl, Sulfamoyl, N-Mono- oder N,N-Di-C₁-C₄-Alkylaminosulfonyl, C₁-C₄-Alkanoylamino, z.B. Acetylamino, Benzolyamino, Sulfo, Halogen oder gegebenenfalls im Phenylteil durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Sulfo, Nitro oder Halogen substituiertes Phenylazo substituiert ist.K and K 'means e.g. a phenol or 1- or 2-naphthol residue which may optionally 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. Acetylamino, benzolyamino, sulfo, halogen or optionally substituted in the phenyl part by C₁-C₄-alkyl, C₁-C₄-alkoxy, sulfo, nitro or halogen-substituted phenylazo.
Beispiele für geeignete Kupplungskomponenten, die den Resten K bzw. K' zugrunde liegen können, sind: 1-Naphthol, 2-Naphthol, 1,3- oder 1,5-Dihydroxynaphthalin, 2-Hydroxy-8- acetylaminonaphthalin, 2-Naphthol-3-, -4-, -5-, -6-, -7- oder -8-sulfonsäure, Resorcin, 3-Dimethylamino- oder 3-Diethylaminophenol, Phenyl- azoresorcin, o-, m-, oder p-Chlorphenylazoresorcin, Bis-(o-, m- oder p-Chlorphenylazo)-resorcin.Examples of suitable coupling components which may be the basis of the radicals K or 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.
Vorzugsweise stehen K und K' unabhängig voneinander für einen unsubstituierten oder durch Hydroxy, Amino, Sulfo, Sulfamoyl oder Acetylamino substituierten 1- oder 2-Naphtholrest oder für einen unsubstituierten oder durch gegebenenfalls durch Methyl, Methoxy, Chlor, Sulfo oder Nitro substituiertes Phenylazo substituierten Resorcinrest.Preferably 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 .
Die Komplexfarbstoffe der Formel (2) weisen z.B. 0 bis 4, vorzugsweise 1 bis 4 und besonders bevorzugt 1 oder 2 Sulfogruppen auf.The complex dyes of formula (2) have e.g. 0 to 4, preferably 1 to 4 and particularly preferably 1 or 2 sulfo groups.
Besonders bevorzugt für das erfindungsgemässe Verfahren sind schwarze Komplexfarbstoffe, die in Form der freien Säure der Formel
entsprechen, worin D₁ und D₂ unabhängig voneinander den Rest einer unsubstituierten oder durch Sulfo und/oder Nitro substituierten 1-Amino-2-hydroxynaphthalins oder den Rest eines unsubstituierten oder durch Nitro, Sulfo, Chlor, Methyl, Methoxy, Methylsulfonyl oder gegebenenfalls durch Sulfo, Methyl, Methoxy, Nitro oder Chlor substituiertes Phenylazo substituierten 2-Aminophenols bedeuten und K₁ und K₂ unabhängig voneinander für einen unsubstituierten oder durch Hydroxy, Amino, Sulfo oder Acetylamino substituierten 1- oder 2-Naphtholrest oder für einen unsubstituierten oder durch gegebenenfalls durch Methyl, Methoxy, Chlor, Sulfo oder Nitro substituiertes Phenylazo substituierten Resorcinrest stehen, und worin der Komplexfarbstoff 1 oder 2 Sulfogruppen aufweist.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 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 residue or for an unsubstituted or optionally by methyl, methoxy , Chlorine, sulfo or nitro substituted phenylazo substituted resorcinol, and wherein the complex dye has 1 or 2 sulfo groups.
Beispiele für bevorzugte schwarze Komplexfarbstoffe sind:
Die Metallkomplexverbindungen der Formel (2), die vorteilhaft in Form ihrer Salze, insbesondere Alkali-, wie Lithium-, Kalium- und vor allem Natriumsalze oder auch Ammoniumsalze, eingesetzt werden, sind an sich bekannt oder können in an sich bekannter Weise erhalten werden.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 above all sodium salts or also ammonium salts, are known per se or can be obtained in a manner known per se.
Geeignete sulfierte Russe sind z.B. aus der US-A-3,528,840 oder aus der DE-A-1 927 597 bekannt oder können analog zu den dort angegebenen Verfahren hergestellt werden. Es handelt sich dabei um Russe, die Sulfogruppen chemisch und/oder physikalisch gebunden enthalten, so dass sie durch Waschverfahren mit Wasser nicht entfernt werden können. Die erfindungsgemäss verwendeten sulfierten Russe weisen vorteilhaft einen Schwefelgehalt von z.B. 0,5 bis 6 Gew.-% und vorzugsweise 1 bis 3 Gew.-% sowie einen sauren pH-Wert, d.h. einen pH-Wert unterhalb von 7 und vorzugsweise zwischen 1 und 5, auf; unter pH-Wert des Russes ist hierbei der pH-Wert des in destilliertem Wasser angeschlämmten Russes zu verstehen.Suitable sulfonated Russian are known for example from US-A-3,528,840 or from DE-A-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 is to be understood here as the pH value of the soot suspended in distilled water.
Die sulfierten Russe können erhalten werden, z.B. indem man in Anlehnung an die US-A-3,528,840 einen üblichen Russ - geeignet sind alle Arten von Russ und insbesondere solche mit einer mittleren Teilchengrösse von 10 bis 100 nm und vorzugsweise 20 bis 50 nm - zusammen mit Ammoniumsulfit oder vorzugsweise Ammoniumsulfat auf eine Temperatur oberhalb von 230°C, vorzugsweise auf eine Temperatur zwischen 250 und 300°C, unter Rühren erhitzt. Die dabei benötigte Ammoniumsulfit- bzw. Ammoniumsulfatmenge ist abhängig vom gewünschten pH-Wert und Schwefelgehalt des sulfierten Russes, beträgt jedoch im allgemeinen 1 bis 20 Gew.-%, vorzugsweise 2-15 Gew.-% und besonders bevorzugt 5 bis 12 Gew.-%, bezogen auf das Gewicht des eingesetzten Russes.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 above of 230 ° C, preferably to a temperature between 250 and 300 ° C, heated 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.
Es ist weiterhin möglich, geeignete sulfierte Russe in Anlehnung an die DE-A-1 927 597 durch Umsetzung eines üblichen wie zuvor charakterisierten Russes in trockenem Zustand mit gasförmigem Schwefeltrioxid (SO₃) bei erhöhter Temperatur, z.B. bei 100 bis 300°C und vorzugsweise bei 150 bis 200°C, zu erhalten.It is also possible to use suitable sulfonated carbon black based on DE-A-1 927 597 by reacting a conventional carbon black as described above in the dry state with gaseous sulfur trioxide (SO₃) at elevated temperature, e.g. at 100 to 300 ° C and preferably at 150 to 200 ° C.
Man geht z.B. so vor, dass man das SO₃ in den Russ mit Hilfe eines Trägergases, z.B. Luft oder Stickstoff, einleitet. Oleum kann als SO₃-Lieferant dienen, und Stickstoff wird dann beispielsweise so durch das Oleum geleitet, dass SO₃ durch den Stickstoffstrom mitgeführt wird. Die Zuführung von SO₃ und Stickstoff zum Reaktionsgefäss, in welchem der Russ bei der Reaktionstemperatur gerührt wird, wird unterbrochen, sobald die gewünschte SO₃-Menge eingeführt ist. Zur Bestimmung der benötigten SO₃-Menge kann der pH-Wert des Russes benutzt werden. Während der Reaktion werden dazu Russproben entnommen, deren pH-Wert bestimmt und die SO₃-Zuführung dann beendet, wenn der gewünschte pH-Wert des Russes erreicht worden ist.One goes e.g. so that the SO₃ in the soot with the help of a carrier gas, e.g. Air or nitrogen. Oleum can serve as 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. During the reaction, 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.
Die erfindungsgemäss verwendeten Farbstoffmischungen enthalten den schwarzen anionischen Farbstoff und den sulfierten Russ z.B. in einem Gewichtsverhältnis von 95:5 bis 60:40, vorzugsweise 90:10 bis 70:30 und besonders bevorzugt 80:20 bis 75:25; möglich sind auch Gemische verschiedener anionischer Farbstoffe und/oder Russe. Die Farbstoffmischungen können ausserdem gegebenenfalls ein Entstäubungsmittel, z.B. ein Stauböl, enthalten.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.
Bevorzugt für das erfindungsgemässe Verfahren sind Farbstoffmischungen enthaltend einen schwarzen Farbstoff der zuvor angegebenen Formel (1) oder (2) und einen sulfierten Russ mit einem Schwefelgehalt von 0,5 bis 6 Gew.-%.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.
In einer besonders bevorzugten Ausführungsform des erfindungsgemässen Verfahrens verwendet man eine Farbstoffmischung enthaltend einen schwarzen anionischen Farbstoff der zuvor angegebenen Formel (1a) bzw. (2a) und einen sulfierten Russ mit einem Schwefelgehalt von 1 bis 3 Gew.-% im Gewichtsverhältnis 90:10 bis 70:30, und insbesondere 80:20 bis 75:25.In a particularly preferred embodiment of the process according to the invention, use is made of 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.
Die oben genannten Farbstoffmischungen, die im wesentlichen aus einem schwarzen anionischen Farbstoff und einem sulfierten Russ bestehen, sind neu und ein weiterer Gegenstand der vorliegenden Erfindung. Sie können hergestellt werden z.B. durch mechanisches Mischen der Komponenten in einer geeigneten Mischvorrichtung, z.B. in einer Kugel- oder Stiftmühle oder in einem Kneter oder Mixer.The above-mentioned dye mixtures, which consist essentially of a black anionic dye and a sulfonated carbon black, are new and a further subject 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.
Das erfindungsgemässe Verfahren wird vorteilhaft so ausgeführt, dass man das zu färbende Leder zunächst einer Vorbehandlung, z.B. einer Nachgerbung, Neutralisation und/oder Walke unterwirft.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.
Das solchermassen vorbehandelte Leder wird dann mittels eines an sich bekannten Ausziehverfahrens unter Verwendung einer der zuvor genannten Farbstoffmischungen ausgefärbt; beispielsweise färbt man das Leder in einer wässrigen Lösung mit einem Flottenverhältnis von 1:1,5 bis 1:20, vorzugsweise 1:2 bis 1:10 und einer Temperatur von z.B. 20 bis 100°C, vorzugsweise 40 bis 60°C. Man verwendet je nach Art des zu färbenden Leders z.B. 0,25 bis 15,0 Gew.-%, vorzugsweise 1,0 bis 10,0 Gew.-%, bezogen auf das Gewicht des Leders, der jeweiligen Farbstoffmischung. Auch die Färbedauer hängt von der Art des zu färbenden Leders ab, beträgt aber im allgemeinen z.B. 20 bis 180 Minuten.The leather pretreated in this way is then dyed by means of an extraction process known per se, using one of the dye mixtures mentioned above; 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. Depending on the type of leather to be dyed, e.g. 0.25 to 15.0% by weight, preferably 1.0 to 10.0% by weight, based on the weight of the leather, of the respective dye mixture. The dyeing time also depends on the type of leather to be dyed, but is generally e.g. 20 to 180 minutes.
Dem Färbebad können gegebenenfalls vor, während oder nach der Färbung weitere allgemein übliche Zusätze, z.B. Netzmittel, Egalisiermittel, Farbvertiefungsmittel und/oder Fettungsmittel zugegeben werden. Am Ende des Färbevorgangs wird vorteilhaft z.B. mit Ameisensäure zur besseren Baderschöpfung angesäuert und noch einige Zeit weiterlaufen gelassen. Gegebenenfalls kann es angezeigt sein, das Leder mit einem weiteren Teil der jeweiligen Farbstoffmischung in einem frischen Bad nachzufärben. Die Fertigstellung des gefärbten Leders erfolgt in an sich bekannter Weise.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. At the end of the dyeing process, it is advantageous to acidify with formic acid, for example, to improve bath exhaustion and to continue to run for some time. It may be appropriate to recolour the leather with a further part of the respective dye mixture in a fresh bath. The dyed leather is finished in a manner known per se.
Das erfindungsgemässe Färbeverfahren ist für alle Ledersorten, z.B. Narben- und Rauhleder - Chromleder, nachgegerbte Leder oder Velourleder von Ziege, Schaf, Rind und Schwein - geeignet. Man erhält egale, tiefe gut deckende Färbungen mit guten Allgemein-Echtheiten, z.B. Wasser-, Wasch-, Schweiss-, Trockenreinigungs-, Säure-, Alkali-, Lösungsmittel-, Reib- und Diffusionsechtheit gegenüber Weich-PVC; besondere Erwähnung verdient die hervorragende Lichtechtheit der erfindungsgemäss erhältlichen Färbungen.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.
Die nachfolgenden Beispiele dienen der Erläuterung der Erfindung, ohne sie darauf zu beschränken. Teile bedeuten, soweit nicht anders angegeben, Gewichtsteile und Prozente Gewichtsprozente.The following examples serve to illustrate the invention without restricting it. Unless otherwise stated, parts mean parts by weight and percentages by weight.
50 Teile Russ (ASTM-Spezifikation N 330, mittlere Teilchengrosse 26-30 nm) werden zusammen mit 5 Teilen Ammoniumsulfat während 5 Stunden in einer Stahlkugelmühle gemahlen und gemischt. Das Mahlgut wird dann in einem Stahlgefäss unter schwachem Rühren auf eine Temperatur von 280-290°C erhitzt und 1 Stunde dabei belassen. Nach dem Erkalten wird der so behandelte Russ während 4 Stunden im Vakuum bei 80°C entgast. Der erhaltene sulfierte Russ weist einen Schwefelgehalt von 2,7 Gew.-% auf.50 parts of carbon black (ASTM specification N 330, average particle size 26-30 nm) are ground and mixed together with 5 parts of ammonium sulfate in a steel ball mill for 5 hours. The millbase is then heated in a steel vessel with gentle stirring to a temperature of 280-290 ° C and left for 1 hour. After cooling, the soot treated in this way is degassed in vacuo at 80 ° C. for 4 hours. The sulfonated carbon black obtained has a sulfur content of 2.7% by weight.
25 Teile Russ (ASTM-Spezifikation N 330, mittlere Teilchengrösse 26-30 nm) werden in einem Kolben unter schwachem Rühren auf 175°C erwärmt. Nun wird während 6 Stunden langsam ein Stickstoffstrom in den Kolben eingeleitet, der zuvor durch 5 Vol.-Teile Oleum 66%ig bei 50°C geblasen worden ist. Der so behandelte Russ wird anschliessend 4 Stunden im Vakuum bei 80°C entgast; er weist danach einen Schwefelgehalt von 2,9 Gew.-% auf.25 parts of carbon black (ASTM specification N 330, average particle size 26-30 nm) are heated in a flask to 175 ° C. with gentle stirring. A stream of nitrogen is then slowly introduced into the flask over a period of 6 hours, which has previously been blown through 5 parts by volume of 66% oleum at 50 ° C. The soot treated in this way is then degassed in vacuo at 80 ° C. for 4 hours; it then has a sulfur content of 2.9% by weight.
100 Teile zwischengetrocknetes Schafnappaleder werden in einer aus 1000 Teilen Wasser, 2 Teilen eines nichtionogenen Netzmittels (Polyethylenglykolether-Derivat) und 1 Teil Ammoniak 24%ig zubereiteten Flotte während 60 Minuten bei 50°C vorbehandelt und anschliessend gut gespült.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.
Das derart vorbereitete Leder wird nun in einer frischen Flotte, bestehend aus 500 Teilen Wasser und 5 Teilen einer der in der Tabelle genannten Farbmischungen, 30 Minuten bei 50°C gefärbt. Danach erfolgt ein Zusatz von 8 Teilen eines Fettungsmittelgemisches, das aus 2 Teilen sulfitiertem Seetieröl, 2 Teilen eines Gemisches aus sulfitierten Fettsäureestern und animalischen Fettstoffen sowie 4 Teilen eines Gemisches aus sulfitierten natürlichen Ölen und animalischen Fettstoffen besteht. Nach weiteren 60 Minuten wird mit 4 Teilen Ameisensäure 85%ig angesäuert (pH ca. 3,2) und hierauf die Behandlung 20 Minuten fortgesetzt. Man gibt 2 Teile eines kationischen Farbvertiefungsmittels (Polyquaternäres Amin-Ethylenoxid-Addukt) hinzu und lässt noch 20 Minuten weiterlaufen.The leather prepared in this way is then 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. This is followed by the addition of 8 parts of a fatliquor mixture consisting of 2 parts of sulfited marine oil, 2 parts of a mixture of sulfited fatty acid esters and animal fat and 4 parts of a mixture of sulfited natural oils and animal fat. After a further 60 minutes, the mixture is acidified with 4 parts of 85% formic acid (pH approx. 3.2) and the treatment is then continued for 20 minutes. 2 parts of a cationic color deepening agent (polyquaternary amine / ethylene oxide adduct) are added and the mixture is left to run for a further 20 minutes.
Anschliessend wird in einem frischen Bad noch mit 5 Teilen der oben eingesetzten Farbstoffmischung in 500 Teilen Wasser während 30 Minuten bei 50°C nachgefärbt. Dann werden dem Färbebad 3 Teile eines nichtionischen synthetischen Nachfettungsmittels (Fettsäure-Polyamid-Kondensationsprodukt) und nach weiteren 20 Minuten noch 1 Teil Ameisensäure 85%ig zugesetzt. Nach einer abschliessenden Behandlungsdauer von 20 Minuten wird gespült und wie üblich fertiggestellt. Es ergeben sich jeweils egale tiefe Schwarzfärbungen mit guten Allgemeinechtheiten.
Die gemäss den Beispielen 3 bis 18 verwendeten Farbstoffmischungen werden durch einfaches Mischen der Komponenten in einem Mixer erhalten.The dye mixtures used according to Examples 3 to 18 are obtained by simply mixing the components in a mixer.
100 Teile Chromrindleder werden in einer aus 200 Teilen Wasser, 1 Teil Natriumformiat und 2 Teilen eines anionischen Netzmittels (Na-Salze aromatischer Sulfonsäuren und aliphatischer Dicarbonsäuren) bestehenden Flotte 15 Minuten bei 30°C vorbehandelt, anschliessend 2 Teile eines anionischen Fettungsmittels (sulfitiertes Seetieröl), 2 Teile eines anionischen Nachgerbmittels (Kondensationsprodukt aus aromatischen Sulfonsäuren) und 1,5 Teile Natriumhydrogencarbonat zugegeben und 60 Minuten weiterlaufen gelassen.100 parts of chrome cowhide 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 sea 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.
Das Leder wird gut mit warmem Wasser gespült und anschliessend in einer frischen Flotte bestehend aus 100 Teilen Wasser und 8 Teilen eines anionischen Nachgerbmittels (Kondensationsprodukt aromatischer Sulfonderivate mit Dialkylolcarbamid) 30 Minuten bei 40°C nachgegerbt. Dann werden 5 Teile des zuvor genannten anionischen Fettungsmittels zugegeben, 60 Minuten weiterlaufen gelassen, inder Folge 0,5 Teile Ameisensäure 85%ig addiert und noch 15 Minuten weiterbehandelt.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 dialkylol carbamide) 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, then 0.5 parts of 85% formic acid are added and the treatment is continued for 15 minutes.
Das derart nachgegerbte Leder wird nun in einer frischen Flotte, bestehend aus 100 Teilen Wasser, 0,5 Teilen Ammoniak, 1 Teil eines Egalisiermittels (Polyglycolether-Derivat) und 2,65 Teilen der Farbstoffmischung gemäss Beispiel 4 30 Minuten bei 30°C gefärbt. Danach erfolgt ein Zusatz von 8 Teilen des zuvor genannten Fettungsmittels und 4 Teilen eines Hydrophobiermittels. Nach weiteren 60 Minuten wird mit 2,5 Teilen Ameisensäure 85%ig angesäuert und hierauf die Behandlung 30 Minuten fortgesetzt. Anschliessend wird in einem frischen Bad mit 1,35 Teilen der oben eingesetzten Farbstoffmischung in 200 Teilen Wasser während 30 Minuten nachgefärbt, wobei die Flotte zusätzlich noch 0,5 Teile eines kationischen Farbvertiefungsmittels (polyquaternäres Amin-Ethylenoxid-Addukt) enthält. Dann werden dem Färbebad 1 Teil Ameisensäure 85%ig und nach weiteren 15 Minuten 1,5 Teile eines kationischen Fettungsmittels (Zubereitung auf Basis chlorierter Kohlenwasserstoffe und n-Alkyl-Derivaten) zugesetzt. Nach einer abschliessenden Behandlungsdauer von 20 Minuten wird gespült und wie üblich fertiggestellt. Es ergibt sich eine egale tiefe Schwarzfärbung mit guten Allgemeinechtheiten.The leather retanned in this way is then 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, the mixture is acidified with 2.5 parts of 85% formic acid and the treatment is then continued for 30 minutes. Subsequently, in a fresh bath with 1.35 parts of the dye mixture used above in 200 parts of water for 30 minutes, the liquor additionally contains 0.5 parts of a cationic color deepening agent (polyquaternary amine-ethylene oxide adduct). Then 1 part of 85% strength formic acid and after a further 15 minutes 1.5 parts of a cationic fatliquor (preparation based on chlorinated hydrocarbons and n-alkyl derivatives) are added to the dyebath. After a final treatment time of 20 minutes, rinsing and finishing as usual. The result is a level, deep black color with good general fastness properties.
100 Teile Schuhleder werden zunächst in einer aus 300 Teilen Wasser und 0,5 Teilen eines anionischen Netzmittels bestehenden Flotte 15 Minuten bei 35°C gewaschen und dann in einer frischen aus 150 Teilen Wasser und 4 Teilen eines anionischen Nachgerbmittels (Na-Salze aromatischer Sulfosäuren und aliphatischer Dicarbonsäuren) bestehenden Flotte 30 Minuten bei 35°C behandelt. Anschliessend werden 4,0 Teile Mimosa, 5 Teile eines anionischen Nachgerbmittels (Oxomethan-Kondensationsprodukt aus Sulfon und Sulfonsäure cyclischer Verbindungen) und 2 Teile eines anionischen Fettungsmittels (Gemisch sulfitierter Fettsäureester und animalischer Fettstoffe) zugegeben und 30 Minuten weiterlaufen gelassen. Man gibt anschliessend 4 Teile der Farbstoffmischung gemäss Beispiel 4 hinzu und färbt 45 Minuten bei 35°C. Danach erfolgt der Zusatz von 5 Teilen des zuvor genannten Fettungsmittels, 3 Teilen eines weiteren Fettungsmittels (Zubereitung auf Basis von sulfoniertem Chlorparaffin) und 150 Teilen warmem Wassers (50°C). Nach weiteren 30 Minuten wird mit 1 Teil Ameisensäure 85%ig angesäuert und hierauf die Behandlung 30 Minuten fortgesetzt. Anschliessend wird in einem frischen Bad mit 2 Teilen der oben eingesetzten Farbstoffmischung in 300 Teilen Wasser, 0,5 Teilen Ameisensäure 85%ig und 1 Teil eines Farbvertiefungsmittels (polyquaternäres Amin/Ethylenoxid-Addukt) 15 Minuten bei 50°C nachgefärbt, dann weitere 0,5 Teile Ameisensäure 85%ig zugesetzt und noch 20 Minuten weiterlaufen gelassen. Das Leder wird gespült und wie üblich fertiggestellt. Es ergibt sich eine egale Schwarzfärbung mit guten Allgemeinechtheiten.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. Then 4.0 parts of Mimosa, 5 parts of an anionic retanning agent (oxomethane condensation product of sulfone and sulfonic acid cyclic compounds) and 2 parts of an anionic fatliquor (mixture of sulfited fatty acid esters and animal fatty substances) are added and the mixture is left to run for 30 minutes. 4 parts of the dye mixture according to Example 4 are then added, and dyeing is carried out at 35 ° C. for 45 minutes. This is followed by the addition of 5 parts of the aforementioned fatliquor, 3 parts of another fatliquor (preparation based on sulfonated chlorinated paraffin) and 150 parts of warm water (50 ° C). After a further 30 minutes, it is acidified with 1 part of 85% formic acid and the treatment is then continued for 30 minutes. Subsequently, 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 color 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.
Claims (14)
- A process for dyeing leather by the exhaust process, which comprises treating leather with an aqueous liquor which contains a dye formulation comprising a black anionic dye and a sulfonated carbon black.
- A process according to claim 1, wherein the black anionic dye is an acid dye, a direct dye or a metal complex dye.
- A process according to claim 1 or claim 2, wherein the black anionic dye is of the formula
Z is a radical
- A process according to any one of claims 1 to 3, wherein the black anionic dye is of the formula
- A process according to claim 1 or 2, wherein the black anionic dye is in the form of the free acid of the formula
- A process according to any one of claims 1, 2 or 5, wherein the anionic dye is of the formula
- A process according to any one of claims 1 to 6, wherein the sulfonated carbon black has a sulfur content of 0.5 to 6 % by weight and preferably of 1 to 3 % by weight.
- A process according to any one of claims 1 to 7, wherein the dye formulation used contains the black anionic dye and the sulfonated carbon black in the weight ratio of 95:5 to 60:40, preferably 90:10 to 70:30 and, particularly preferably, 80:20 to 75:25.
- A process according to any one of claims 1 to 8, wherein the dye formulation contains a black anionic dye of the formula (1) as indicated in claim 3, or of the formula (2) as indicated in claim 5, and a sulfonated carbon black having a sulfur content of 0.5 to 6 % by weight.
- A process according to any one of claims 1 to 9, wherein the dye formulation contains a black anionic dye of the formula (1a) as indicated in claim 4, or of the formula (2a) as indicated in claim 6, and a sulfonated carbon black having a sulfur content of 1 to 3 % by weight in the weight ratio of 90:10 to 70:30, preferably 80:20 to 75:25.
- A dye formulation comprising a black anionic dye and a sulfonated carbon black.
- A dye formulation according to claim 11 comprising a black anionic dye of the formula (1) as indicated in claim 3 or of the formula (2) as indicated in claim 5, and a sulfonated carbon black having a sulfur content of 0.5 to 6 % by weight.
- A dye formulation as claimed in claim 11 comprising a black anionic dye of the formula (1a) as indicated in claim 4 or of the formula (2a) as indicated in claim 6, and a sulfonated carbon black having a sulfur content of 1 to 3 % by weight in the weight ratio of 90:10 to 70:30, preferably 80:20 to 75:25.
- Use of a dye formulation as claimed in any one of claims 11 to 13 for dyeing leather.
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 EP0433229A1 (en) | 1991-06-19 |
| EP0433229B1 true EP0433229B1 (en) | 1994-01-26 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90810941A Expired - Lifetime EP0433229B1 (en) | 1989-12-11 | 1990-12-03 | Process for dyeing leather |
Country Status (5)
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| US (1) | US5152801A (en) |
| EP (1) | EP0433229B1 (en) |
| JP (1) | JPH04241174A (en) |
| DE (1) | DE59004417D1 (en) |
| ES (1) | ES2049014T3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10242875B4 (en) * | 2001-09-19 | 2014-02-27 | Dainichiseika Color & Chemicals Mfg. Co. Ltd. | Process for producing sulfonated solid particles |
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| DE59309441D1 (en) * | 1992-02-28 | 1999-04-22 | Ciba Geigy Ag | Process for dyeing leather with dye mixtures |
| CH685251A5 (en) * | 1992-05-26 | 1995-05-15 | Ciba Geigy Ag | A process for dyeing leather. |
| ES2098709T3 (en) * | 1992-06-30 | 1997-05-01 | Ciba Geigy Ag | PROCEDURE FOR DYING LEATHER BY TRICHROMY WITH DYEING MIXTURES. |
| JPH06340820A (en) * | 1993-05-31 | 1994-12-13 | Sumitomo Chem Co Ltd | Trisazo compound, method for dyeing textile material, paper or leather using the same, and recording liquid containing the same |
| ES2144503T3 (en) * | 1993-10-15 | 2000-06-16 | Tfl Ledertechnik Gmbh & Co Kg | LEATHER DYEING WITH DYEING MIXTURES. |
| US6203814B1 (en) * | 1994-12-08 | 2001-03-20 | Hyperion Catalysis International, Inc. | Method of making functionalized nanotubes |
| US5575845A (en) * | 1994-12-15 | 1996-11-19 | Cabot Corporation | Carbon black products for coloring mineral binders |
| US5571311A (en) * | 1994-12-15 | 1996-11-05 | Cabot Corporation | Ink jet ink formulations containing carbon black products |
| IL116379A (en) * | 1994-12-15 | 2003-12-10 | Cabot Corp | Aqueous inks and coatings containing modified carbon products |
| IL116378A (en) * | 1994-12-15 | 2003-05-29 | Cabot Corp | Non-aqueous coating or ink composition with improved optical properties containing modified carbon product and method of preparation of the composition |
| IL154538A (en) * | 1994-12-15 | 2009-12-24 | Cabot Corp | Reaction of carbon black with diazonium salts, resultant carbon black products and their uses |
| IL116376A (en) * | 1994-12-15 | 2001-03-19 | Cabot Corp | Aqueous ink jet ink compositions containing modified carbon products |
| US5559169A (en) * | 1994-12-15 | 1996-09-24 | Cabot Corporation | EPDM, HNBR and Butyl rubber compositions containing carbon black products |
| US5554739A (en) * | 1994-12-15 | 1996-09-10 | Cabot Corporation | Process for preparing carbon materials with diazonium salts and resultant carbon products |
| US6028137A (en) | 1995-05-22 | 2000-02-22 | Cabot Corporation | Elastomeric compounds incorporating silicon-treated carbon blacks |
| US6323273B1 (en) | 1995-05-22 | 2001-11-27 | Cabot Corporation | Elastomeric compounds incorporating silicon-treated carbon blacks |
| US5622557A (en) | 1995-05-22 | 1997-04-22 | Cabot Corporation | Mineral binders colored with silicon-containing carbon black |
| AU5867396A (en) | 1995-05-22 | 1996-12-11 | Cabot Corporation | Elastomeric compounds incorporating partially coated carbon blacks |
| KR20000004920A (en) * | 1996-03-26 | 2000-01-25 | 스타르크, 카르크 | Stable dye compositions |
| US5958999A (en) | 1996-04-05 | 1999-09-28 | Cabot Corporation | Ink compositions and method for generating images produced therefrom |
| US5707432A (en) | 1996-06-14 | 1998-01-13 | Cabot Corporation | Modified carbon products and inks and coatings containing modified carbon products |
| US5747562A (en) | 1996-06-14 | 1998-05-05 | Cabot Corporation | Ink and coating compositions containing silicon-treated carbon black |
| US5698016A (en) * | 1996-06-14 | 1997-12-16 | Cabot Corporation | Compositions of modified carbon products and amphiphilic ions and methods of using the same |
| DE19626318A1 (en) * | 1996-07-01 | 1998-01-08 | Basf Ag | Dye mixtures containing polyazo dyes |
| US5919855A (en) | 1997-02-11 | 1999-07-06 | Cabot Corporation | Use of modified carbon black in gas-phase polymerizations |
| US7195834B2 (en) * | 2002-05-23 | 2007-03-27 | Columbian Chemicals Company | Metallized conducting polymer-grafted carbon material and method for making |
| US7241334B2 (en) * | 2002-05-23 | 2007-07-10 | Columbian Chemicals Company | Sulfonated carbonaceous materials |
| WO2003100883A2 (en) | 2002-05-23 | 2003-12-04 | Columbian Chemicals Company | Conducting polymer-grafted carbon material for fuel cell applications |
| US7459103B2 (en) * | 2002-05-23 | 2008-12-02 | Columbian Chemicals Company | Conducting polymer-grafted carbon material for fuel cell applications |
| CA2486790A1 (en) * | 2002-05-23 | 2003-12-04 | Columbian Chemicals Company | Sulfonated conducting polymer-grafted carbon material for fuel cell applications |
| US7390441B2 (en) * | 2002-05-23 | 2008-06-24 | Columbian Chemicals Company | Sulfonated conducting polymer-grafted carbon material for fuel cell applications |
| 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 |
| CN114855469B (en) * | 2022-04-15 | 2023-07-04 | 苏州大学 | Printing method for preparing functional polyester spandex knitted fabric based on liquid carbon black @ disperse dye black |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3528840A (en) * | 1967-11-15 | 1970-09-15 | Huber Corp J M | Sulfonated carbon black |
| NL6807617A (en) * | 1968-05-30 | 1969-12-02 | ||
| BE791994A (en) * | 1971-11-30 | 1973-05-28 | Bayer Ag | POLYAZOIC DYES |
| FR2360634A1 (en) * | 1976-08-03 | 1978-03-03 | Ugine Kuhlmann | NEW WATER-SOLUBLE TRISAZOIC DYES |
| AU552418B2 (en) * | 1982-07-08 | 1986-05-29 | Toray Industries, Inc. | Artificial grain leather with different colour spots |
| IT1211465B (en) * | 1987-06-19 | 1989-11-03 | Lorica Spa | PROCEDURE FOR OBTAINING A SYNTHETIC SUEDE LEATHER SIMILAR TO THE NATURAL ONE |
| DE3825755A1 (en) * | 1987-08-08 | 1989-02-16 | Sandoz Ag | Dyeing and printing of leather |
| IT1224686B (en) * | 1987-08-08 | 1990-10-18 | Sandoz Ag | PROCESS FOR DYEING OR PRINTING OF LEATHER |
| US5007941A (en) * | 1989-01-02 | 1991-04-16 | Ciba-Geigy Corporation | Process for dyeing leather: aqueous bath containing mixture of carbon black and acid dye, direct dye or metal complex dye |
-
1990
- 1990-12-03 DE DE90810941T patent/DE59004417D1/en not_active Expired - Fee Related
- 1990-12-03 EP EP90810941A patent/EP0433229B1/en not_active Expired - Lifetime
- 1990-12-03 ES ES90810941T patent/ES2049014T3/en not_active Expired - Lifetime
- 1990-12-05 US US07/622,888 patent/US5152801A/en not_active Expired - Fee Related
- 1990-12-11 JP JP2401394A patent/JPH04241174A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10242875B4 (en) * | 2001-09-19 | 2014-02-27 | Dainichiseika Color & Chemicals Mfg. Co. Ltd. | Process for producing sulfonated solid particles |
Also Published As
| Publication number | Publication date |
|---|---|
| US5152801A (en) | 1992-10-06 |
| DE59004417D1 (en) | 1994-03-10 |
| EP0433229A1 (en) | 1991-06-19 |
| ES2049014T3 (en) | 1994-04-01 |
| JPH04241174A (en) | 1992-08-28 |
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