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
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/30—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using sulfur dyes
• • 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
  • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
  • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
• • 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
• • 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
• • 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
  • D06P3/3233—Material containing basic nitrogen containing amide groups leather skins using acid dyes dis-polyazo using dis-polyazo premetallised dyes
• • 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.
• 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 an anionic dye and a pigment is allowed to act on the leather, the dye and pigment in a weight ratio of 90: 10 to 70:30 are available.
• Anionic dyes that can be used are all dyes usually 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.
• the anionic dyes can have any color: black dyes are preferred, this term e.g. also includes dyes with a dark blue, blue-gray, gray or yellowish, reddish or greenish black shade.
• the phenyl or naphthyl radical A can carry one or more identical or different substituents, for example: C 1 -C 4 -alkyl, which here and in the following is generally methyl, ethyl, n- or isopropyl or n-, comprises iso-, sec- or tert-butyl; C 1 -C 4 alkoxy, which generally includes methoxy, ethoxy, n- or iso-propoxy or n-, iso. sec.- or tert.-butoxy is to be understood; Halogen, which means for example fluorine, bromine and especially chlorine; Trifluoromethyl: C1-C4 alkylsulfonyl.
• C 1 -C 4 -alkyl which here and in the following is generally methyl, ethyl, n- or isopropyl or n-, comprises iso-, sec- or tert-butyl
• C 1 -C 4 alkoxy which generally includes me
• methyl- or ethylsulfonyl especially methyl- or ethylsulfonyl; Sulfamoyl, for example -S02NH2 or N-mono- or N, N-di-C 1 -C 4 -alkylaminosulfonyl; Carbamoyl, for example -CONH 2 or N-mono- or N, N-di-C i -C 4 -alkylaminocarbonyl, sulfo; Nitro; Cyano; Carboxy; Phenoxy.
• A is preferably an unsubstituted or substituted by halogen, nitro, sulfo, C1-C4-alkyl and / or C 1 -C 4 alkoxy.
• the phenyl or naphthyl radical B can also carry further radicals, for example an N-mono- or N, N-di-C 1 -C 4 -alkylamino, phenylamino, o-, m- or p-methylphenylamino -, An unsubstituted or substituted by methyl, chlorine or nitro, for example, benzoylamino, C 1 -C 4 -alkanoylamino or carboxymethylamino residue or one of the substituents mentioned above for A.
• B is preferably a phenyl radical which carries a hydroxyl or amino group and a further substituent selected from the group consisting of hydroxyl, amino, phenylamino, o-, m- or p-methylphenylamino, C 1 -C 4 alkoxy 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.
• the anionic dyes of the formula (1) have as a naphthol coupling component e.g. 2-amino-5-naphthol-7-sulfonic acid (I-acid), 1-amino-8-naphthol-4,6-disulfonic acid (K-acid) or preferably 1-amino-8-naphthol-3,6-disulfonic acid (H acid).
• a naphthol coupling component e.g. 2-amino-5-naphthol-7-sulfonic acid (I-acid), 1-amino-8-naphthol-4,6-disulfonic acid (K-acid) or preferably 1-amino-8-naphthol-3,6-disulfonic acid (H acid).
• a group of 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 C 1 -C 4 -alkoxy, B' is a phenyl radical which has a hydroxyl or amino group and a further substituent selected from the group Group hydroxyl, amino, phenylamino, o-, m- or p-methylphenylamino, C 1 -C 4 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 (1 a) are known per se or can be obtained in a manner known per se.
• 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 an iron, cobalt or in particular a chromium atom as the central 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 contain, for example, two azomethine molecules, an azo and an azomethine dye, or preferably two azo dyes, where these dyes can be substituted with further arylazo and / or arylazoarylenazo groups.
• Benzene or naphthalene radicals are meant, which may optionally be substituted, for example by nitro, sulfo, halogen, C1-C4-alkyl or C 1 -C 4 -alkoxy.
• the azo or azomethine dye molecules can have water-solubilizing groups such as carbamoyl, C 1 -C 4 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 complex dyes particularly suitable for the process according to the invention correspond, for example, to the formula in the form of the free acid where D and D 'independently of one another each represent an optionally further substituted benzene or naphthalene radical which contains a hydroxyl group in the ortho position to the azo group,
• 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 which may be substituted by sulfo, nitro, C1-C4-alkylsulfonyl, C 1 -C 4 -alkyl, halogen and / or in the phenyl part optionally by C 1 -C 4 - Alkyl, C 1 -C 4 alkoxy, sulfo, nitro or halogen substituted phenylazo is substituted.
• 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-sulfo2-aminophenol, 4-chloro-6-sulfo -2-aminophenol, 4-chloro or 4-methyl-6-nitro-2-aminophenol, 4-chloro-2-aminophenol, 4-methylsulfonyl-2-amino phenol, 4- (2-methoxyphenylazo) -2-aminophenol , 4- (2-, 3- or 4-sulfophenylazo) -2-aminophenol, 4-phenylazo-2-aminophenol, 1-amino-2-hydroxynaphthalene-4
• D and D 'independently of one another particularly preferably represent the remainder of a 2-aminophenol, which may optionally be substituted one or more times by identical or different substituents from the series nitro, sulfo, chlorine, methyl, methoxy, methylsulfonyl 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 'independently of one another represent an unsubstituted or substituted by hydroxy, amino, sulfo 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.
• 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.
• the pigment used for the process according to the invention is, for example, all customary inorganic white, black and colored pigments, such as those from Kirk Othmer, Encyclopedia of Chemical Technology Vol. 17, Pages 788-838, John Wiley 1982, are known in question.
• Examples are: titanium dioxide, zinc oxide, barium sulfate, silicon dioxide [white]; Chrome oxide green (Cr 2 0 3 ) [green]; Cobalt blue (CoOAI 2 0 3 ), ultrararin blue (Na ( 6-8 ) AI 6 Si 6 0 24 S ( 2 - 4 ), iron blue (FeNH 4 Fe (CN) 6 ) [blue]; natural and artificial iron oxides, e.g. Siena -Brown, iron black (Fe 3 0 4 ); Russ [black].
• black pigments in particular carbon black, is preferred, all types of carbon black being suitable.
• the pigments have an average particle size of e.g. 0.01 to 100 ⁇ m, preferably 0.01 to 1 ⁇ m and particularly preferably 0.015 to 0.5 ⁇ m.
• the pigment is a carbon black, it preferably has an average particle size of 10 to 100 nm and particularly preferably 20 to 50 nm.
• the dye mixtures used according to the invention contain the anionic dye and the pigment in a weight ratio of 90:10 to 70:30 and particularly preferably 80:20 to 70:30: mixtures of different anionic dyes and / or pigments are also possible.
• the dye mixtures may also optionally contain a dusting agent, e.g. a dust oil.
• Mixtures of a black anionic dye and a black inorganic pigment are preferably used for the process according to the invention.
• Dye mixtures containing a black dye of the formula (1) or (2) given above and a carbon black pigment are particularly preferred.
• a dye mixture containing a black anionic dye of the formula (1 a) or (2a) given above and a carbon black pigment in a weight ratio of 90:10 to 70:30, and in particular 80:20 to 70, are used : 30.
• the above-mentioned dye mixtures which consist essentially of an anionic dye and an inorganic pigment, are new and a further subject of the present invention. They can be made e.g. by mechanically mixing 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 known pull-out process 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 and a temperature of e.g. 20 to 100 ° C. preferably 40 to 60 ° C.
• 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 be admixed with other commonly used additives, e.g. Wetting agents, leveling agents, color deepening agents and / or fatty agents are added.
• Wetting agents e.g. Acidified with formic acid to improve bath exhaustion and let it 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 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 and diffusion fastness to soft PVC;
• the outstanding lightfastness of the dyeings obtainable according to the invention and the coloration of the leather achieved deserve special mention.
• Parts mean parts by weight and percentages percentages by weight.
• 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 one Mixture of sulfited natural oils and animal fat substances.
• 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 1 to 16 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 (sodium salts of aromatic sulfonic acids and aliphatic dicarboxylic acids) at 30 ° C. for 15 minutes. then 2 parts of an anionic fatliquor (sulfited marine oil), 2 parts of an anionic retanning agent (condensation product from 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 sodium salts of aromatic sulfonic acids and aliphatic dicarboxylic acids
• the leather is rinsed well with warm water and then retanned for 30 minutes at 40 ° C. in a fresh liquor consisting of 100 parts of water and 8 parts of an anionic retanning agent (concentration product of aromatic sulfone derivatives with dialkylol carbamide). 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 subsequently added and the treatment is continued for 15 minutes.
• an anionic retanning agent concentration 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 2 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). Then 1 part of 85% strength formic acid and 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 period of

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• 1989
  • 1989-12-21 ES ES89810976T patent/ES2068915T3/es not_active Expired - Lifetime
  • 1989-12-21 US US07/454,499 patent/US5007941A/en not_active Expired - Lifetime
  • 1989-12-21 DE DE58909090T patent/DE58909090D1/de not_active Revoked
  • 1989-12-21 EP EP89810976A patent/EP0377409B1/de not_active Revoked
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  • 1989-12-28 HU HU896806A patent/HU209331B/hu not_active IP Right Cessation
  • 1989-12-28 JP JP1338886A patent/JPH02229282A/ja active Pending
  • 1989-12-28 AR AR89315850A patent/AR245514A1/es active
  • 1989-12-29 KR KR1019890020052A patent/KR0143078B1/ko not_active IP Right Cessation
• 1990
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