EP0572353A1 - Procédé de teinture du cuir - Google Patents

Procédé de teinture du cuir Download PDF

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Publication number
EP0572353A1
EP0572353A1 EP93810365A EP93810365A EP0572353A1 EP 0572353 A1 EP0572353 A1 EP 0572353A1 EP 93810365 A EP93810365 A EP 93810365A EP 93810365 A EP93810365 A EP 93810365A EP 0572353 A1 EP0572353 A1 EP 0572353A1
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EP
European Patent Office
Prior art keywords
dye
weight
methyl
formula
methoxy
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.)
Granted
Application number
EP93810365A
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German (de)
English (en)
Other versions
EP0572353B2 (fr
EP0572353B1 (fr
Inventor
Campbell Thomas Dr. Page
Ernst Dr. Tempel
Alois Dr. Püntener
Roberto Dr. Galli
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Original Assignee
Ciba Geigy AG
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Publication date
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Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of EP0572353A1 publication Critical patent/EP0572353A1/fr
Application granted granted Critical
Publication of EP0572353B1 publication Critical patent/EP0572353B1/fr
Publication of EP0572353B2 publication Critical patent/EP0572353B2/fr
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/32—Material containing basic nitrogen containing amide groups leather skins
    • 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

Definitions

  • the present invention relates to a method for dyeing leather with anionic dyes and to the leather dyed by the method.
  • the dyes are usually used in the form of solid or liquid commercial forms which contain more or less large amounts of alkali halide which has been added as a coupage to adjust a certain color strength or which is present due to the production process. As a result, the dyeing liquors also contain alkali halide.
  • the invention thus relates to a process for dyeing leather with anionic dyes, characterized in that an aqueous solution is used for dyeing, comprising a polyazo dye with at least 2 sulfo groups and less than 1.5% by weight, based on the weight of the dye , Alkali halide.
  • a preferred embodiment of the method according to the invention consists in using an aqueous solution for dyeing which contains a dye of the formula wherein A the rest of an aromatic diazo component, B the rest of a coupling component, X OH or NH2, Y NH, O or SO2NH, n 1 or 2 and m denotes 0, 1 or 2.
  • a very particularly preferred embodiment of the process according to the invention consists in using an aqueous solution for dyeing which contains a dye of the formula wherein A the rest of an aromatic diazo component, B the rest of a coupling component, X OH or NH2, n 1 or 2 and m denotes 0, 1 or 2.
  • the diazo residue A leads e.g. from a heterocyclic or carbocyclic aromatic amine, preferably from 1- or 2-naphthylamine or aminobenzene, it being possible for the aromatic amines mentioned to be further substituted by one or more identical or different radicals.
  • Suitable substituents on the phenyl or naphthyl radical A are, for example, C1-C4-alkyl, which here and in general includes methyl, ethyl, n- or iso-propyl or n-, iso-, sec- or tert-butyl; C1-C4 alkoxy, which generally means methoxy, ethoxy, n- or iso-propoxy or n-, iso-, sec- or tert-butoxy; Halogen, for example fluorine, bromine and especially chlorine; Trifluoromethyl; C1-C4 alkylsulfonyl, especially methyl or ethylsulfonyl; Sulfamoyl; N-mono- or N, N-di-C1-C4-alkylsulfamoyl; Carbamoyl; N-mono- or N, N-di-C1-C4-alkylcarbamoyl,
  • Preferred diazo components are compounds of the formula wherein R1 and R2 each independently represent hydrogen, C1-C4-alkyl, C1-C4-alkoxy, halogen, nitro, trifluoromethyl, C1-C4-alkylsulfonyl, acetylamino, hydroxyacetylamino, propionylamino, sulfamoyl, carbamoyl, cyano, carboxy or phenoxy.
  • radical R1 or R2 is C1-C4-alkylsulfonyl, it is e.g. ethylsulfonyl and especially methylsulfonyl.
  • R1 and R2 are independently hydrogen, methyl, ethyl, methoxy, ethoxy, chlorine, nitro, trifluoromethyl, methylsulfonyl, ethylsulfonyl, sulfamoyl, carbamoyl, cyano, acetylamino and phenoxy.
  • R1 and R2 independently of one another particularly preferably represent hydrogen, methyl, methoxy, nitro or chlorine.
  • Examples of preferred compounds of the formula (3) are: Aniline, 2-, 3- or 4-methylaniline, 2-, 3- or 4-methoxyaniline, 2-, 3- or 4-chloroaniline, 2-, 3- or 4-nitroaniline, 2-chloro-4-nitroaniline, 2-methyl-4-nitroaniline, 2,5-dichloroaniline, 2,5-dimethylaniline, 2,5-dimethoxyaniline or 2-methoxy-5-methylaniline.
  • X is OH and it is also preferred that the group X is not on the same ring as the NH2 group.
  • B denotes the rest of a coupling component, in particular a coupling component from the benzene or naphthalene series.
  • B is preferably a radical of the formula wherein R3 is hydroxy, amino, N-mono- or N, N-di-C1-C4-alkylamino, phenylamino or o-, m- or p-methylphenylamino and R4 and R5 independently of one another each have the meaning of R3 or for hydrogen , Benzoylamino, C1-C4-alkanoylamino, carboxymethylamino, C1-C4-alkyl, C1-C4-alkoxy, phenoxy, carboxy, halogen, nitro or sulfo.
  • R3 is N-mono- or N, N-di-C1-C4 alkylamino e.g. for methyl, ethyl, n- or iso-propyl- or n-, iso-, sec- or tert-butylamino or N, N-dimethyl-, N, N-diethyl-, N, N-di- n- or -iso-propyl- or N, N-di-n-, -iso-, -sec.- or -tert.-butylamino and preferably for N-methylamino, N-ethylamino, N, N-dimethylamino or N , N-diethylamino.
  • R3 are hydroxy, amino, N-methyl- and N-ethylamino, N, N-dimethyl- and N, N-diethylamino and phenylamino.
  • R3 particularly preferably represents hydroxy or amino.
  • R4 and / or R5 as well as in the variables below as C1-C4 alkyl, it is generally methyl, ethyl, n- or iso-propyl or n-, iso-, sec.- or tert-butyl .
  • R4 and / or R5 or the following variables stand for C1-Coxy-alkoxy, this generally includes methoxy, ethoxy, n- or iso-propoxy or n-, iso-, sec- or tert-butoxy.
  • R4 and / or R5 as halogen are generally as follows, e.g. fluorine, bromine and especially chlorine.
  • R4 and / or R5 in the meaning C1-C4-alkanoylamino are, for example, propionylamino, hydroxyacetylamino and in particular acetylamino.
  • Sulfo generally includes the free acid form (-SO3H) as well as the salt form, alkali metal salts (Li, Na, K) or ammonium salts being particularly suitable.
  • R4 and R5 independently of one another preferably represent hydrogen, sulfo, acetylamino, methyl, ethyl, methoxy, ethoxy, chlorine, carboxy, hydroxy, amino, N-methyl- or N-ethylamino, N, N-dimethyl- or N, N- Diethylamino or phenylamino and particularly preferably for hydrogen, amino, hydroxy, methyl, methoxy, phenylamino or N, N-dimethyl- or N, N-diethylamino.
  • R3 is hydroxyl, amino, N-methyl- or N-ethylamino, N, N-dimethyl- or N, N-diethylamino or phenylamino
  • R4 and R5 are each independently of the other hydrogen, Acetylamino, methyl, ethyl, methoxy, ethoxy, chlorine, carboxy, hydroxy, amino, N-methyl- or N-ethylamino, N, N-dimethyl- or N, N-diethylamino or phenylamino.
  • Suitable compounds of the formula (4) are: phenol, 4-methylphenol, 1,3-dihydroxybenzene (resorcinol), 3-aminophenol, 1,3-phenylenediamine, 3-N, N-diethylaminophenol, 3-phenylaminophenol, 2, 5-dimethylaniline, 2-methoxy-5-methylaniline, salicylic acid, 2- or 3-methylaniline, 2-methoxyaniline, 1,3-diamino-4-methylbenzene, 1,3-diamino-4-chlorobenzene and 1,3-diamino -4-methoxybenzene.
  • a particularly preferred embodiment of the present invention relates to the use of 3-aminophenol, resorcinol or 1,3-phenylenediamine as the coupling component.
  • n is preferably 2 and m is preferably 1.
  • the dyes of the formula (1) and (2) are known or can be prepared in a known manner.
  • the use of dyes of the formula (1) which are described in DE-A-41 24 437 is particularly preferred.
  • the dyes of the formula (1) or (2) prepared in the customary manner normally contain about 5 to 30% by weight of alkali metal halide, based on the weight of the dye.
  • This alkali halide is formed in the synthesis of the dye and / or added to the dye solution obtained for the deposition of the dye.
  • the solid or liquid commercial form of the dye is often adjusted to the desired color strength by adding alkali halide.
  • an aqueous solution containing a dye with less than 1.5% by weight, based on the weight of the dye, of alkali metal halide is used.
  • the dyes which are commercially available or prepared in the customary manner must therefore be largely freed from the alkali halide before they can be used in the dyeing process according to the invention. This is done in a manner known per se, for example by reverse osmosis, ultrafiltration or dialysis. Such desalination processes are known, e.g. from EP-A 0 059782. Also known are the membranes used in these processes, e.g. from EP-A 0 061 424.
  • the process conditions for this desalination are selected so that dye solutions are obtained which contain less than 1.5% by weight, based on the weight of the dye, of alkali metal halide.
  • Dye salts and salts with higher molecular weight cations and / or anions are not or only slightly removed.
  • alkali halide is to be understood as meaning lithium, sodium and potassium fluoride, chloride, bromide and iodide.
  • the dye is in the form of an aqueous solution, which, if desired, can be concentrated or evaporated to dryness, for example by spray drying.
  • a preferred embodiment of the dyeing process according to the invention is characterized in that an aqueous solution is used for dyeing, comprising a polyazo dye of the formula (2) and less than 1.0% by weight, based on the weight of the dye, of alkali metal halide.
  • the dyes are preferably used as aqueous dye preparations. These preparations preferably contain 5 to 40% by weight of dye, 65 to 95% by weight of water, 0 to 20% by weight of further additives and less than 1.5% by weight, based on the weight of the dye, of alkali halide.
  • Dye preparations used with preference contain 10 to 25% by weight of dye, 70 to 90% by weight of water, 0 to 20% by weight of further additives and less than 1.0% by weight, based on the weight of the dye, of alkali metal halide.
  • the dye preparations can e.g. contain surface-active substances, buffer substances, foam-suppressing aids, antifreezing agents and substances that inhibit fungal and / or bacterial growth.
  • the amounts in which the dyes are used in the dye baths can vary within wide limits depending on the desired depth of color. In general, amounts of dye of 0.1 to 10, preferably 0.5 to 4,% by weight, based on the weight of the leather to be colored, are advantageous.
  • the dye liquor can also contain other additives, e.g. Acids or bases for setting the desired pH value, as well as auxiliaries such as Wetting agents, greasing agents, color-deepening aids, leveling agents, and / or anti-foaming agents.
  • additives e.g. Acids or bases for setting the desired pH value
  • auxiliaries such as Wetting agents, greasing agents, color-deepening aids, leveling agents, and / or anti-foaming agents.
  • the process according to the invention has the great advantage that less dye is required to achieve a certain depth of color than when using dyeing liquors which contain large amounts of alkali metal halides, since the dyestuff capacity is greater.
  • the method according to the invention is not only suitable for a specific type of leather, but can also be applied to the various types of leather, for example chrome leather. retanned leather or suede from goat, beef or pork.
  • the dyeing is preferably carried out using the exhaust method, e.g. at a liquor ratio of 1: 1.5 to 1:20, preferably 1: 2 to 1:10, and at temperatures of 20 to 100 ° C, preferably 30 to 60 ° C.
  • the leather can be pretreated be subjected to, for example, a neutralization or Walke.
  • the dyeing time varies depending on the type of leather and the desired depth of color, but is generally between 30 and 180 minutes. After the dyeing, the leather is rinsed and finished as usual.
  • the process according to the invention gives leather dyeings in the same hues and fastnesses as when dyeing with dye liquors which are richer in alkali halide.
  • This solution is desalinated in a laboratory reverse osmosis system under the following conditions: polysulfone membrane, approx. 40 ° C, feed: 12 l / h, 25 bar, flux 1289 l / m2d (average). After 4.5 hours, 1.9 kg of a solution with a dye content of 18.0% by weight and a sodium chloride content of 0.05% by weight (0.9% by weight, based on the dye) are obtained. This desalted and concentrated solution is adjusted to a dye content of 15% after filtration through a 10 ⁇ m sieve with water.
  • the leather is dyed in a liquor of 1000 parts of water, 2 parts of 24% ammonia and 13.33 parts of the dye solution described above at 50 ° C.
  • the mixture After a dyeing time of 60 minutes, the mixture is acidified with 4 parts of 85% formic acid and then dyeing is continued for 20 minutes.
  • the dyed leather is finished after treatment in a fresh bath with 1000 parts of water, 2.5 parts of a condensation product of formaldehyde, dicyandiamide, ammonium chloride and ethylenediamine and 0.5 part of 85% strength Formic acid for 45 minutes at 50 ° C.
  • the leather obtained is dyed black. It is characterized by good fastness properties and good opacity.
  • 100 parts of chrome-tanned cowhide with a fold thickness of 1.4 mm are drummed in a fleet consisting of 200 parts of water, 1 part of sodium bicarbonate and 1 part of sodium formate for 45 minutes at 30 ° C. and then washed twice with 300 parts of water at the same temperature.
  • the leather neutralized in this way is then dyed at 50 ° C. in a liquor composed of 1000 parts of water, 2 parts of 24% ammonia and 15 parts of the dye solution described in Example 1. After 30 minutes, 3 parts of a synthetic fatliquor (mixture of alkylbenzenes, aliphatic hydrocarbons, alkanesulfonic acids and surfactants) are added to the dyeing liquor and, after a further 30 minutes, 0.5 part of 85% formic acid, diluted with 5 parts of water, is added. The treatment is then continued at 50 ° C. for 20 minutes.
  • a synthetic fatliquor mixture of alkylbenzenes, aliphatic hydrocarbons, alkanesulfonic acids and surfactants
  • the result is leather of any color black with excellent fastness properties, in particular good diffusion fastness to soft PVC.
  • the color corresponds to the color obtained in Example 1.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
EP19930810365 1992-05-26 1993-05-18 Procédé de teinture du cuir Expired - Lifetime EP0572353B2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH1687/92 1992-05-26
CH168792 1992-05-26
CH168792A CH685251A5 (de) 1992-05-26 1992-05-26 Verfahren zum Färben von Leder.

Publications (3)

Publication Number Publication Date
EP0572353A1 true EP0572353A1 (fr) 1993-12-01
EP0572353B1 EP0572353B1 (fr) 1996-06-19
EP0572353B2 EP0572353B2 (fr) 1999-06-09

Family

ID=4216257

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19930810365 Expired - Lifetime EP0572353B2 (fr) 1992-05-26 1993-05-18 Procédé de teinture du cuir

Country Status (6)

Country Link
EP (1) EP0572353B2 (fr)
JP (1) JPH0665869A (fr)
CH (1) CH685251A5 (fr)
DE (1) DE59302989D1 (fr)
ES (1) ES2089774T3 (fr)
MX (1) MX9303069A (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008012085A1 (fr) 2006-07-25 2008-01-31 Joseph Mellini Composition de réparation des surfaces en cuir, et procédé de réparation superficielle des surfaces en cuir
US8382857B2 (en) 2004-06-08 2013-02-26 Basf Se Method for the reactive coloration of leather
CN106349751A (zh) * 2015-07-16 2017-01-25 台湾永光化学工业股份有限公司 黑色染料组合物及其用途

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2360634A1 (fr) * 1976-08-03 1978-03-03 Ugine Kuhlmann Nouveaux colorants trisazoiques hydrosolubles
EP0433229A1 (fr) * 1989-12-11 1991-06-19 Ciba-Geigy Ag Procédé de teinture du cuir
DE4124437A1 (de) * 1990-07-26 1992-01-30 Ciba Geigy Ag Polyazofarbstoffe

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2360634A1 (fr) * 1976-08-03 1978-03-03 Ugine Kuhlmann Nouveaux colorants trisazoiques hydrosolubles
EP0433229A1 (fr) * 1989-12-11 1991-06-19 Ciba-Geigy Ag Procédé de teinture du cuir
DE4124437A1 (de) * 1990-07-26 1992-01-30 Ciba Geigy Ag Polyazofarbstoffe

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8382857B2 (en) 2004-06-08 2013-02-26 Basf Se Method for the reactive coloration of leather
WO2008012085A1 (fr) 2006-07-25 2008-01-31 Joseph Mellini Composition de réparation des surfaces en cuir, et procédé de réparation superficielle des surfaces en cuir
CN106349751A (zh) * 2015-07-16 2017-01-25 台湾永光化学工业股份有限公司 黑色染料组合物及其用途

Also Published As

Publication number Publication date
DE59302989D1 (de) 1996-07-25
MX9303069A (es) 1994-06-30
ES2089774T3 (es) 1996-10-01
CH685251A5 (de) 1995-05-15
JPH0665869A (ja) 1994-03-08
EP0572353B2 (fr) 1999-06-09
EP0572353B1 (fr) 1996-06-19

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