EP0591108B1 - Process for dyeing of wool containing fiber materials - Google Patents

Process for dyeing of wool containing fiber materials Download PDF

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Publication number
EP0591108B1
EP0591108B1 EP93810677A EP93810677A EP0591108B1 EP 0591108 B1 EP0591108 B1 EP 0591108B1 EP 93810677 A EP93810677 A EP 93810677A EP 93810677 A EP93810677 A EP 93810677A EP 0591108 B1 EP0591108 B1 EP 0591108B1
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EP
European Patent Office
Prior art keywords
wool
dyeing
parts
weight
dyed
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
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EP93810677A
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German (de)
French (fr)
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EP0591108A1 (en
Inventor
Martin Dr. Kuhn
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Novartis AG
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Ciba Geigy AG
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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
    • D06P3/82—Textiles which contain different kinds of fibres
    • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
    • D06P3/8214—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing ester and amide groups
    • 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
    • D06P1/64—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 using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/642—Compounds containing nitrogen
    • D06P1/645—Aliphatic, araliphatic or cycloaliphatic compounds containing amino groups
    • 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
    • D06P3/14—Wool
    • D06P3/16—Wool using acid 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
    • Y10S8/917—Wool or silk
    • 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
    • Y10S8/93—Pretreatment before dyeing

Definitions

  • the present invention relates to a new process for high-temperature dyeing wool or wool-containing fiber materials.
  • auxiliaries in order to counteract fiber damage which occurs in particular during high-temperature dyeing.
  • auxiliaries Many of the known auxiliaries contain formaldehyde or release formaldehyde when heated, which is not toxicologically harmless.
  • the present invention thus relates to a process for dyeing wool-containing fiber materials with anionic dyes, which is characterized in that these materials are prepared in the presence of a reaction product of an epihalohydrin and ammonia or an amine of the formula R - NH 2 (1), where RC 1 -C 6 alkyl, dyes as a wool protection agent.
  • R as C 1 -C 6 alkyl is, for example, n- or isopropyl, n-, iso-, sec- or tert-butyl, straight-chain or branched pentyl or hexyl or, preferably, methyl or Ethyl.
  • R preferably represents methyl or ethyl.
  • Epihalohydrins suitable for the production of the wool protection agents according to the invention are, for example, epibromohydrin or preferably epichlorohydrin.
  • the procedure is generally such that ammonia or the amine of the formula (1) is reacted with excess epihalohydrin; a molar ratio of 1-5 moles of epihalohydrin per mole of ammonia or amine of the formula (1), preferably 2.5-3 moles of epihalohydrin per mole of ammonia or amine of the formula (1) and particularly preferably 3 moles of epihalohydrin per mole of ammonia or Amine of formula (1) as practical.
  • the reaction is preferably carried out in an aqueous medium at temperatures of 100 100 ° C. and the exotherm that occurs is controlled by suitable cooling. It is preferred here to use the reactants e.g.
  • reaction times can vary within wide limits, but are generally 1 to 24 hours and preferably 2-10 hours.
  • the solution of the reaction product obtained can then be used in a conventional manner, e.g. by subjecting it to steam distillation to remove unwanted by-products.
  • the wool preservative is obtained in the form of an aqueous solution, the water content of which can be determined and, if necessary, adjusted to a certain value.
  • the general procedure is to obtain the wool-containing fiber material in the presence of e.g. 0.5 to 10% by weight, preferably 1 to 6% by weight, based on the weight of the material to be dyed, dyes wool protection agent according to the invention.
  • a preferred embodiment of the present invention relates to a method for dyeing wool-containing fiber materials with anionic dyes, which is characterized in that these materials in the presence of 0.5 to 10 wt .-%, based on the weight of the material to be dyed, from a reaction product 2.5-3.0 molar equivalents of epichlorohydrin and 1 molar equivalent of ammonia or amine of the formula R - NH 2 (1), where R is methyl or ethyl dyes as a wool protection agent.
  • a particularly preferred embodiment of the present invention relates to a process for dyeing wool-containing fiber materials with anionic dyes, which is characterized in that these materials are present in the presence of 1 to 6 % By weight, based on the weight of the material to be dyed, of a reaction product of 2.5-3.0 mol equivalents of epichlorohydrin and 1 mol equivalent of ammonia as wool preservative.
  • the wool-containing fiber material can be wool alone or a mixture of e.g. Trade wool / polyamide or wool / polyester.
  • Mixtures of wool and synthetic polyamide are preferably dyed with anionic dyes and mixtures of wool and polyester fibers are preferably dyed with disperse and anionic dyes. Suitable anionic dyes and disperse dyes are known to the person skilled in the art.
  • the fiber material can be in various stages of processing, e.g. in the form of yarns, flakes, sliver, knitwear such as knitwear or knitted fabrics, as a nonwoven fabric or preferably as a woven fabric.
  • the mixed fiber materials are preferably fiber blends of wool and polyester, which are generally present in a proportion of 20 to 50 parts by weight of wool to 80-50 parts by weight of polyester.
  • the fiber mixtures preferred for the process contain 45 parts of wool and 55 parts of polyester fibers.
  • the liquor ratio can be selected within a wide range in the process according to the invention; it is e.g. 1: 1 to 1: 100 and preferably 1:10 to 1:50.
  • the dyebath can contain other customary additives.
  • other customary additives e.g. Mineral acids, organic acids and / or their salts, which serve to adjust the pH value of the dye bath, further electrolytes, leveling agents, wetting agents and defoamers and, if dyeing wool / polyester mixtures, carriers and / or dispersant.
  • the dye bath has a pH of e.g. 4 to 6.5 and preferably from 5.2 to 5.8.
  • the process according to the invention is generally carried out at a temperature of e.g. 60 to 130 ° C carried out.
  • the dyeing is expediently carried out by the exhaust process, for example at a temperature in the range from 60 to 106 ° C., preferably from 95 to 98 ° C.
  • the dyeing time can vary depending on the requirements, however, it is preferably 60-120 minutes.
  • the dyeing of the polyester / wool mixed fiber materials is advantageously carried out in a single bath from an aqueous liquor using the exhaust process. It is preferably dyed by the so-called high-temperature process in closed, pressure-resistant apparatus at temperatures above 100 ° C., expediently between 110 and 125 ° C. and preferably at 118 to 120 ° C. and, if appropriate, under pressure.
  • the mixed fiber materials can also be processed by the usual carrier dyeing process at temperatures below 106 ° C, e.g. in the temperature range from 75 to 98 ° C in the presence of one or more carriers.
  • the dyeing of the polyester / wool mixed fiber materials can be carried out in such a way that the material to be dyed is first treated with the wool protection agent and, if appropriate, the carrier and then dyed.
  • the procedure can also be such that the material to be dyed is treated simultaneously with the wool protection agent, the dyes and, if appropriate, auxiliaries .
  • the textile mixed fiber material is preferably added to a liquor which contains the wool protection agent and, if appropriate, other customary auxiliaries and has a temperature of 40-50 ° C., and the material is treated at this temperature for 5 to 15 minutes.
  • the temperature is then increased to about 60 to 70 ° C., the dye is added, the mixture is slowly heated to the dyeing temperature and then dyeing is carried out at this temperature for about 20 to 60, preferably 30 to 45 minutes. Finally, the liquor is cooled to about 60 ° C and the colored material is worked up as usual.
  • Parts mean parts by weight, percentages by weight.
  • the water content of the reaction solution is determined and the mixture is made up by adding dist. Water to an active substance content of 50 wt .-% and receives 7526 parts of a slightly yellow, clear, practically odorless 50% solution of the wool protection agent.
  • the reaction mixture is then subjected to steam distillation in order to drive off by-products formed, in particular 1,3-dichloro-2-propanol and 1-chloro-2,3-propanediol.
  • the water content of the reaction solution is determined and the mixture is made up by adding dist. Water to an active substance content of 40 wt .-% and receives 518 parts of a slightly yellow, clear, practically odorless 40% solution of the wool protection agent.
  • 100 parts of a wool fabric with a m 2 weight of 180 g are treated in 1000 parts of an aqueous liquor containing 4 parts of ammonium sulfate, 2 parts of an aqueous preparation according to Example 1 and 0.5 part of a naphthalenesulfonic acid condensate product at 50 ° C. for 10 minutes; the pH of the liquor is previously adjusted to about 6 with acetic acid. Then 3 parts of the dye of the formula added and a further 5 min. treated. The dyeing liquor is then removed within approx. 45 min. heated to approx. 98 ° C and the tissue for 60 min. colored at this temperature. Then allow to cool to approx. 60 ° C, rinse as usual and dry the dyed fabric. You get a rub-fast, level blue color without negatively influencing the wool quality.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)

Description

Die vorliegende Erfindung betrifft ein neues Verfahren zum Hochtemperatur-Färben von Wolle oder wollhaltigen Fasermaterialien.The present invention relates to a new process for high-temperature dyeing wool or wool-containing fiber materials.

Es ist bekannt, Wolle oder wollhaltige Fasermaterialien in Gegenwart von Hilfsmitteln zu färben, um so Faserschädigungen entgegenzuwirken, welche insbesondere beim Hochtemperatur-Färben auftreten. Viele der bekannten Hilfsmittel enthalten Formaldehyd oder setzen beim Erhitzen Formaldehyd frei, was toxikologisch nicht unbedenklich ist.It is known to dye wool or wool-containing fiber materials in the presence of auxiliaries in order to counteract fiber damage which occurs in particular during high-temperature dyeing. Many of the known auxiliaries contain formaldehyde or release formaldehyde when heated, which is not toxicologically harmless.

Es wurde nun überraschend ein verbessertes Verfahren zum Hochtemperatur-Färben von wollhaltigen Fasermaterialien gefunden, welches auf der Verwendung einer neuen Klasse von Wollschutzmitteln basiert.Surprisingly, an improved process for high-temperature dyeing of wool-containing fiber materials has now been found, which is based on the use of a new class of wool protection agents.

Gegenstand der vorliegenden Erfindung ist somit ein Verfahren zum Färben von wollhaltigen Fasermaterialien mit anionischen Farbstoffen, welches dadurch gekennzeichnet ist, dass man diese Materialien in Gegenwart eines Umsetzungsprodukts aus einem Epihalogenhydrin und Ammoniak oder einem Amin der Formel

        R - NH2     (1),

worin R C1-C6-Alkyl bedeutet, als Wollschutzmittel färbt.The present invention thus relates to a process for dyeing wool-containing fiber materials with anionic dyes, which is characterized in that these materials are prepared in the presence of a reaction product of an epihalohydrin and ammonia or an amine of the formula

R - NH 2 (1),

where RC 1 -C 6 alkyl, dyes as a wool protection agent.

Bei R als C1-C6-Alkyl handelt es sich z.B. um n- oder iso-Propyl, n-, iso-, sec.- oder tert.-Butyl, geradkettiges oder verzweigtes Pentyl oder Hexyl oder, vorzugsweise, um Methyl oder Ethyl.R as C 1 -C 6 alkyl is, for example, n- or isopropyl, n-, iso-, sec- or tert-butyl, straight-chain or branched pentyl or hexyl or, preferably, methyl or Ethyl.

R steht bevorzugt für Methyl oder Ethyl.R preferably represents methyl or ethyl.

Für die Herstellung der erfindungsgemässen Wollschutzmittel geeignete Epihalogenhydrine sind z.B. Epibromhydrin oder vorzugsweise Epichlorhydrin.Epihalohydrins suitable for the production of the wool protection agents according to the invention are, for example, epibromohydrin or preferably epichlorohydrin.

Bei der Herstellung der erfindungsgemässen Wollschutzmittel geht man im allgemeinen so vor, dass man Ammoniak oder das Amin der Formel (1) mit überschüssigem Epihalogenhydrin umsetzt; hierbei erweist sich ein Molverhältnis von 1-5 Mol Epihalogenhydrin pro Mol Ammoniak oder Amin der Formel (1), vorzugsweise 2,5-3 Mol Epihalogenhydrin pro Mol Ammoniak oder Amin der Formel (1) und besonders bevorzugt 3 Mol Epihalogenhydrin pro Mol Ammoniak oder Amin der Formel (1) als praktikabel. Die Reaktion wird vorzugsweise in einem wässrigen Medium bei Temperaturen von ≤ 100°C ausgeführt und die auftretende Exothermie durch geeignete Kühlung kontrolliert. Hierbei ist es bevorzugt, die Reaktanden z.B. durch Zutropfen des Ammoniaks oder Amins der Formel (1) zur wässrigen Lösung des Epihalogenhydrins oder umgekehrt allmählich bei einer moderaten Temperatur, die z.B. 30 bis 50°C und vorzugsweise ca. 40 bis 45°C beträgt, zusammenzubringen und das Reaktionsgemisch anschliessend bei erhöhter Temperatur, z.B. bei 70 bis 100°C, ausreagieren zu lassen. Die Reaktionszeiten können innerhalb weiter Grenzen variieren, betragen jedoch im allgemeinen 1 bis 24 Stunden und vorzugsweise 2-10 Stunden. Die erhaltene Lösung des Reaktionsprodukts kann anschliessend in üblicher Weise, z.B. indem sie einer Wasserdampfdestillation unterworfen wird, von unerwünschten Nebenprodukten befreit werden. Das Wollschutzmittel fällt in Form einer wässrigen Lösung an, deren Wassergehalt bestimmt und gegebenenfalls auf einen bestimmten Wert eingestellt werden kann.In the manufacture of the wool protection agents according to the invention, the procedure is generally such that ammonia or the amine of the formula (1) is reacted with excess epihalohydrin; a molar ratio of 1-5 moles of epihalohydrin per mole of ammonia or amine of the formula (1), preferably 2.5-3 moles of epihalohydrin per mole of ammonia or amine of the formula (1) and particularly preferably 3 moles of epihalohydrin per mole of ammonia or Amine of formula (1) as practical. The reaction is preferably carried out in an aqueous medium at temperatures of 100 100 ° C. and the exotherm that occurs is controlled by suitable cooling. It is preferred here to use the reactants e.g. by dropwise adding the ammonia or amine of formula (1) to the aqueous solution of the epihalohydrin or vice versa gradually at a moderate temperature e.g. 30 to 50 ° C and preferably about 40 to 45 ° C, and then bring the reaction mixture at elevated temperature, e.g. at 70 to 100 ° C. The reaction times can vary within wide limits, but are generally 1 to 24 hours and preferably 2-10 hours. The solution of the reaction product obtained can then be used in a conventional manner, e.g. by subjecting it to steam distillation to remove unwanted by-products. The wool preservative is obtained in the form of an aqueous solution, the water content of which can be determined and, if necessary, adjusted to a certain value.

Man geht im allgemeinen so vor, dass man das wollhaltige Fasermaterial in Gegenwart von z.B. 0,5 bis 10 Gew.-%, vorzugsweise 1 bis 6 Gew.-%, bezogen auf das Gewicht des Färbeguts, an erfindungsgemässem Wollschutzmittel färbt.The general procedure is to obtain the wool-containing fiber material in the presence of e.g. 0.5 to 10% by weight, preferably 1 to 6% by weight, based on the weight of the material to be dyed, dyes wool protection agent according to the invention.

Eine bevorzugte Ausführungsform der vorliegenden Erfindung betrifft ein Verfahren zum Färben von wollhaltigen Fasermaterialien mit anionischen Farbstoffen, welches dadurch gekennzeichnet ist, dass man diese Materialien in Gegenwart von 0,5 bis 10 Gew.-%, bezogen auf das Gewicht des Färbeguts, eines Umsetzungsprodukts aus 2,5-3,0 Moläquivalenten Epichlorhydrin und 1 Moläquivalent Ammoniak oder Amin der Formel

        R - NH2     (1),

worin R Methyl oder Ethyl bedeutet, als Wollschutzmittel färbt.A preferred embodiment of the present invention relates to a method for dyeing wool-containing fiber materials with anionic dyes, which is characterized in that these materials in the presence of 0.5 to 10 wt .-%, based on the weight of the material to be dyed, from a reaction product 2.5-3.0 molar equivalents of epichlorohydrin and 1 molar equivalent of ammonia or amine of the formula

R - NH 2 (1),

where R is methyl or ethyl dyes as a wool protection agent.

Eine besonders bevorzugte Ausführungsform der vorliegenden Erfindung betrifft ein Verfahren zum Färben von wollhaltigen Fasermaterialien mit anionischen Farbstoffen, welches dadurch gekennzeichnet ist, dass man diese Materialien in Gegenwart von 1 bis 6 Gew.-%, bezogen auf das Gewicht des Färbeguts, eines Umsetzungsprodukts aus 2,5-3,0 Moläquivalenten Epichlorhydrin und 1 Moläquivalent Ammoniak als Wollschutzmittel färbt.A particularly preferred embodiment of the present invention relates to a process for dyeing wool-containing fiber materials with anionic dyes, which is characterized in that these materials are present in the presence of 1 to 6 % By weight, based on the weight of the material to be dyed, of a reaction product of 2.5-3.0 mol equivalents of epichlorohydrin and 1 mol equivalent of ammonia as wool preservative.

Bei dem wollhaltigen Fasermaterial kann es sich um Wolle allein oder um Mischungen aus z.B. Wolle/Polyamid oder Wolle/Polyester handeln. Dabei werden Gemische aus Wolle und synthetischem Polyamid vorzugsweise mit anionischen Farbstoffen und Gemische aus Wolle und Polyesterfasern vorzugsweise mit Dispersions- und anionischen Farbstoffen gefärbt. Geeignete anionische Farbstoffe und Dispersionsfarbstoffe sind dem Fachmann bekannt.The wool-containing fiber material can be wool alone or a mixture of e.g. Trade wool / polyamide or wool / polyester. Mixtures of wool and synthetic polyamide are preferably dyed with anionic dyes and mixtures of wool and polyester fibers are preferably dyed with disperse and anionic dyes. Suitable anionic dyes and disperse dyes are known to the person skilled in the art.

Das Fasermaterial kann in den verschiedensten Verarbeitungsstadien vorliegen, z.B. in Form von Garnen, Flocken, Kammzug, Maschenware, wie Strickware oder Gewirke, als Faservliesstoff oder vorzugsweise als Gewebe.The fiber material can be in various stages of processing, e.g. in the form of yarns, flakes, sliver, knitwear such as knitwear or knitted fabrics, as a nonwoven fabric or preferably as a woven fabric.

Bei den Mischfasermaterialien handelt es sich vorzugsweise um Fasermischungen aus Wolle und Polyester, die in der Regel in einem Teilverhältnis von 20 bis 50 Gewichtsteilen Wolle zu 80-50 Gewichtsteilen Polyester vorliegen. Die für das Verfahren bevorzugten Fasermischungen enthalten 45 Teile Wolle und 55 Teile Polyesterfasern.The mixed fiber materials are preferably fiber blends of wool and polyester, which are generally present in a proportion of 20 to 50 parts by weight of wool to 80-50 parts by weight of polyester. The fiber mixtures preferred for the process contain 45 parts of wool and 55 parts of polyester fibers.

Das Flottenverhältnis kann beim erfindungsgemässen Verfahren innerhalb eines weiten Bereiches gewählt werden; es beträgt z.B. 1:1 bis 1:100 und vorzugsweise 1:10 bis 1:50.The liquor ratio can be selected within a wide range in the process according to the invention; it is e.g. 1: 1 to 1: 100 and preferably 1:10 to 1:50.

Das Färbebad kann neben dem Farbstoff, Wasser und dem Wollhilfsmittel weitere übliche Zusätze enthalten. Zu erwähnen sind z.B. Mineralsäuren, organische Säuren und/oder deren Salze, die der Einstellung des pH-Werts des Färbebads dienen, weiterhin Elektrolyte, Egalisier-, Netz- und Entschäumungsmittel sowie, falls es sich um das Färben von Wolle/Polyester-Gemischen handelt, Carrier und/oder Dispergiermittel.In addition to the dye, water and the wool auxiliary, the dyebath can contain other customary additives. Worth mentioning are e.g. Mineral acids, organic acids and / or their salts, which serve to adjust the pH value of the dye bath, further electrolytes, leveling agents, wetting agents and defoamers and, if dyeing wool / polyester mixtures, carriers and / or dispersant.

Das Färbebad weist einen pH-Wert von z.B. 4 bis 6,5 und vorzugsweise von 5,2 bis 5,8 auf. Das erfindungsgemässe Verfahren wird im allgemeinen bei einer Temperatur von z.B. 60 bis 130°C durchgeführt.The dye bath has a pH of e.g. 4 to 6.5 and preferably from 5.2 to 5.8. The process according to the invention is generally carried out at a temperature of e.g. 60 to 130 ° C carried out.

Wenn das zu färbende Material Wolle allein ist, erfolgt die Färbung zweckmässig nach dem Ausziehverfahren, z.B. bei einer Temperatur im Bereich 60 bis 106°C, vorzugsweise 95 bis 98°C. Die Färbedauer kann in Abhängigkeit von den Erfordernissen variieren, beträgt jedoch vorzugsweise 60-120 Minuten.If the material to be dyed is wool alone, the dyeing is expediently carried out by the exhaust process, for example at a temperature in the range from 60 to 106 ° C., preferably from 95 to 98 ° C. The dyeing time can vary depending on the requirements, however, it is preferably 60-120 minutes.

Die Färbungen der Polyester/Wolle-Mischfasermaterialien erfolgen mit Vorteil einbadig aus wässriger Flotte nach dem Ausziehverfahren. Man färbt vorzugsweise nach dem sogenannten Hochtemperaturverfahren in geschlossenen, druckbeständigen Apparaturen bei Temperaturen von über 100°C, zweckmässig zwischen 110 und 125°C und vorzugsweise bei 118 bis 120°C und gegebenenfalls unter Druck.The dyeing of the polyester / wool mixed fiber materials is advantageously carried out in a single bath from an aqueous liquor using the exhaust process. It is preferably dyed by the so-called high-temperature process in closed, pressure-resistant apparatus at temperatures above 100 ° C., expediently between 110 and 125 ° C. and preferably at 118 to 120 ° C. and, if appropriate, under pressure.

Die Mischfasermaterialien können auch nach dem üblichen Carrier-Färbeverfahren bei Temperaturen unter 106°C, z.B. im Temperaturbereich von 75 bis 98°C in Gegenwart eines oder mehrerer Carrier gefärbt werden.The mixed fiber materials can also be processed by the usual carrier dyeing process at temperatures below 106 ° C, e.g. in the temperature range from 75 to 98 ° C in the presence of one or more carriers.

Das Färben der Polyester/Wolle-Mischfasermaterialien kann so durchgeführt werden, dass man das Färbegut zuerst mit dem Wollschutzmittel und gegebenenfalls dem Carrier behandelt und anschliessend färbt Man kann auch so vorgehen, dass man das Färbegut gleichzeitig mit dem Wollschutzmittel, den Farbstoffen und gegebenenfalls Hilfsmitteln behandelt. Vorzugsweise geht man mit dem Textilmischfasermaterial in eine Flotte ein, die das Wollschutzmittel und gegebenenfalls weitere übliche Hilfsmittel enthält und eine Temperatur von 40-50°C aufweist, und behandelt das Material 5 bis 15 Minuten bei dieser Temperatur. Danach erhöht man die Temperatur auf ca. 60 bis 70°C, gibt den Farbstoff zu, erhitzt langsam auf die Färbetemperatur und färbt dann ca. 20 bis 60, vorzugsweise 30 bis 45 Minuten, bei dieser Temperatur. Am Schluss wird die Flotte auf etwa 60°C abgekühlt und das gefärbte Material wie üblich aufgearbeitet.The dyeing of the polyester / wool mixed fiber materials can be carried out in such a way that the material to be dyed is first treated with the wool protection agent and, if appropriate, the carrier and then dyed. The procedure can also be such that the material to be dyed is treated simultaneously with the wool protection agent, the dyes and, if appropriate, auxiliaries . The textile mixed fiber material is preferably added to a liquor which contains the wool protection agent and, if appropriate, other customary auxiliaries and has a temperature of 40-50 ° C., and the material is treated at this temperature for 5 to 15 minutes. The temperature is then increased to about 60 to 70 ° C., the dye is added, the mixture is slowly heated to the dyeing temperature and then dyeing is carried out at this temperature for about 20 to 60, preferably 30 to 45 minutes. Finally, the liquor is cooled to about 60 ° C and the colored material is worked up as usual.

Mittels des erfindungsgemässen Verfahrens ist es möglich, Wolle oder insbesondere Wolle/Polyester-Fasergemische bei hoher Temperatur unter einwandfreiem Schutz des Wollanteils, d.h. unter Erhaltung der wichtigen, fasertechnologischen Eigenschaften der Wolle, wie Reissfesigkeit, Berstbeständigkeit und Dehnung, zu färben. Hervorzuheben ist weiterhin, dass der Polyesteranteil bei Mischgeweben keine Angilbung zeigt.By means of the method according to the invention it is possible to wool or in particular wool / polyester fiber mixtures at high temperature with perfect protection of the wool content, i.e. dyeing while maintaining the important fiber-technological properties of the wool, such as tear resistance, bursting resistance and elongation. It should also be emphasized that the proportion of polyester in mixed fabrics shows no yellowing.

Die folgenden Beispiele veranschaulichen die Erfindung. Teile bedeuten Gewichtsteile, Prozente Gewichtsprozente.The following examples illustrate the invention. Parts mean parts by weight, percentages by weight.

Herstellung der WollschutzmittelManufacture of wool protection products Beispiel 1:Example 1:

In einem geeigneten Glaskolben, der zuvor mit Stickstoff gespült worden ist, werden 3514 Teile entionisiertes Wasser und 1125 Teile 22,7%ige Ammoniaklösung vorgelegt und homogen gerührt. Man tropft langsam unter Rühren 4164 Teile Epichlorhydrin zu (Zutropfzeit ca. 5 Stunden); im Verlauf der Reaktion steigt die Temperatur auf ca. 35°C an und wird über die gesamte Zutropfdauer mittels Aussenkühlung bei diesem Wert gehalten. Nach Beendigung des Zutropfens wird ca. 12 Stunden lang bei Raumtemperatur nachgerührt. Anschliessend wird das Reaktionsgemisch ca. 3,5 Stunden bei ca. 85°C nachreagieren gelassen und dann einer Wasserdampfdestillation unterworfen, um entstandene Nebenprodukte, insbesondere 1,3-Dichlor-2-propanol und 1-Chlor-2,3-propandiol, auszutreiben. Man ermittelt den Wassergehalt der Reaktionslösung, stellt durch Zugabe von dest. Wasser auf einen Wirksubstanzgehalt von 50 Gew.-% ein und erhält 7526 Teile einer leicht gelben, klaren, praktisch geruchsfreien 50%igen Lösung des Wollschutzmittels.In a suitable glass flask that has previously been flushed with nitrogen, 3514 parts of deionized water and 1125 parts of 22.7% ammonia solution are introduced and stirred homogeneously. 4164 parts of epichlorohydrin are slowly added dropwise with stirring (dropping time approx. 5 hours); in the course of the reaction, the temperature rises to approximately 35 ° C. and is kept at this value over the entire dropwise period by means of external cooling. After the dropping has ended, the mixture is stirred at room temperature for about 12 hours. The reaction mixture is then left to react for about 3.5 hours at about 85 ° C. and then subjected to steam distillation in order to drive off the by-products formed, in particular 1,3-dichloro-2-propanol and 1-chloro-2,3-propanediol . The water content of the reaction solution is determined and the mixture is made up by adding dist. Water to an active substance content of 50 wt .-% and receives 7526 parts of a slightly yellow, clear, practically odorless 50% solution of the wool protection agent.

Beispiel 2:Example 2:

In einem geeigneten Glaskolben, der zuvor mit Stickstoff gespült worden ist, werden 50 Teile destilliertes Wasser und 222 Teile Epichlorhydrin (Reinheit ≥ 99,5 %) vorgelegt und auf 35°C erwärmt. Man tropft unter heftigem Rühren 60,5 Teile konz. Ammoniak (Gehalt 22,5%) in 60,2 Teilen dest. Wasser zu; im Verlauf der Reaktion steigt die Temperatur auf ca. 45°C an und wird über die gesamte Zutropfdauer mittels Aussenkühlung bei diesem Wert gehalten. Nach Beendigung des Zutropfens wird bis zum Ausklingen der Exothermie ausgerührt und anschliessend ca. 1,5 Stunden lang bei ca. 80°C nachreagieren gelassen. Anschliessend wird das Reaktionsgemisch einer Wasserdampfdestillation unterworfen, um entstandene Nebenprodukte, insbesondere 1,3-Dichlor-2-propanol und 1-Chlor-2,3-propandiol, auszutreiben. Man ermittelt den Wassergehalt der Reaktionslösung, stellt durch Zugabe von dest. Wasser auf einen Wirksubstanzgehalt von 40 Gew.-% ein und erhält 518 Teile einer leicht gelben, klaren, praktisch geruchsfreien 40%igen Lösung des Wollschutzmittels.50 parts of distilled water and 222 parts of epichlorohydrin (purity 99 99.5%) are placed in a suitable glass flask which has previously been flushed with nitrogen and heated to 35 ° C. 60.5 parts of conc. Ammonia (22.5% content) in 60.2 parts of dist. Water too; in the course of the reaction the temperature rises to approx. 45 ° C. and is kept at this value over the entire dropwise period by means of external cooling. After the dropping has ended, the mixture is stirred until the exotherm has subsided and then left to react at about 80 ° C. for about 1.5 hours. The reaction mixture is then subjected to steam distillation in order to drive off by-products formed, in particular 1,3-dichloro-2-propanol and 1-chloro-2,3-propanediol. The water content of the reaction solution is determined and the mixture is made up by adding dist. Water to an active substance content of 40 wt .-% and receives 518 parts of a slightly yellow, clear, practically odorless 40% solution of the wool protection agent.

Beispiel 3: Example 3 :

Verfährt man wie im Beispiel 1 beschrieben, verwendet jedoch anstelle von Ammoniak die äquivalente Menge Ammoniumhydrogencarbonat (NH4HCO3) und setzt dieses mit dem Epichlorhydrin bei einer Temperatur von 60-80°C um, erhält man unter CO2-Entwicklung ein Produkt von ähnlicher Qualität.If the procedure is as described in Example 1, but instead of ammonia, the equivalent amount of ammonium bicarbonate (NH 4 HCO 3 ) is used and this is reacted with the epichlorohydrin at a temperature of 60-80 ° C, a product of is obtained with CO 2 evolution of similar quality.

FärbebeispieleColoring examples Beispiel 4: Example 4 :

100 Teile eines Mischgewebes, bestehend aus 55 % Polyester und 45 % Wolle, werden in einem Zirkulationsapparat mit einer Flotte, die

  • 2,0 Teile einer wässrigen Zubereitung gemäss Beispiel 1,
  • 0,5 Teile eines sulfatierten Fettaminpolyglycolethers,
  • 1,0 Teile eines handelsüblichen Hilfsmittelgemisches (auf Basis carbonsäure- und phosphorsäure-aromatischer Verbindungen) und
  • 2,0 Teile Natriumacetat
  • in 1200 Teilen Wasser enthält und mit Essigsäure auf pH 5,5 eingestellt ist, 5 min. bei 40°C vorbehandelt Darauf wird die Flotte innerhalb von 30 Minuten auf 120°C erhitzt,
  • wobei bei 70°C 2,0 Teile der Farbstoffmischung bestehend aus
  • 1,6 Gew.-% Farbstoff der Formel
    Figure imgb0001
  • 60 Gew.-% Farbstoff der Formel
    Figure imgb0002
     (R = 50% -CH2-CH3 + 50% -C6H5)
  • 5,0 Gew.-% Farbstoff der Formel
    Figure imgb0003
  • 4,0 Teile Farbstoff der Formel
    Figure imgb0004
  • 3,3 Teile Farbstoff der Formel
    Figure imgb0005
  • 15,0 Teile Farbstoff der Formel
    Figure imgb0006
  • und 10 Teile Natriumsulfat
der Flotte zugefügt werden. Darauf färbt man 40 min. bei 120°C und kühlt anschliessend die Färbeflotte auf 60°C ab. Darauf wird die übliche Nachwäsche durchgeführt. Man erhält eine reibechte, egale, rote Ton-in-Ton Färbung ohne Einbusse der Wollqualität.100 parts of a mixed fabric, consisting of 55% polyester and 45% wool, are in a circulation apparatus with a liquor
  • 2.0 parts of an aqueous preparation according to Example 1,
  • 0.5 parts of a sulfated fatty amine polyglycol ether,
  • 1.0 parts of a commercially available auxiliary mixture (based on carboxylic and phosphoric acid aromatic compounds) and
  • 2.0 parts sodium acetate
  • contains in 1200 parts of water and is adjusted to pH 5.5 with acetic acid, 5 min. pretreated at 40 ° C. The liquor is then heated to 120 ° C within 30 minutes,
  • whereby at 70 ° C 2.0 parts of the dye mixture consisting of
  • 1.6% by weight of dye of the formula
    Figure imgb0001
  • 60% by weight of dye of the formula
    Figure imgb0002
     (R = 50% -CH 2 -CH 3 + 50% -C 6 H 5 )
  • 5.0% by weight of dye of the formula
    Figure imgb0003
  • 4.0 parts of dye of the formula
    Figure imgb0004
  • 3.3 parts of dye of the formula
    Figure imgb0005
  • 15.0 parts of dye of the formula
    Figure imgb0006
  • and 10 parts of sodium sulfate
be added to the fleet. It is stained for 40 min. at 120 ° C and then cools the dye liquor to 60 ° C. The usual post-wash is then carried out. You get a rub-fast, level, red tone-on-tone coloring without loss of wool quality.

Verwendet man anstelle der wässrigen Zubereitung gemäss Beispiel 1

  • (a) 2 Teile der Zubereitung gemäss Beispiel 2
  • (b) 2 Teile der Zubereitung gemäss Beispiel 3,
so erhält man ebenfalls Färbungen mit guten Eigenschaften und ohne negative Beeinflussung der Wollqualität.Is used instead of the aqueous preparation according to Example 1
  • (a) 2 parts of the preparation according to Example 2
  • (b) 2 parts of the preparation according to Example 3,
this also gives dyeings with good properties and without adversely affecting the quality of the wool.

Beispiel 5: Example 5 :

100 Teile eines Wollgewebes mit einem m2-Gewicht von 180 g werden in 1000 Teilen einer wässrigen Flotte enthaltend 4 Teile Ammoniumsulfat, 2 Teile einer wässrigen Zubereitung gemäss Beispiel 1 und 0,5 Teile eines Naphthalinsulfonsäure-Kondensatprodukts 10 min bei 50°C behandelt; der pH-Wert der Flotte wird zuvor mit Essigsäure auf ca. 6 eingestellt. Danach werden 3 Teile des Farbstoffs der Formel

Figure imgb0007
zugesetzt und weitere 5 min. behandelt. Anschliessend wird die Färbeflotte innerhalb von ca. 45 min. auf ca. 98°C erhitzt und das Gewebe 60 min. bei dieser Temperatur gefärbt. Danach lässt man auf ca. 60°C abkühlen, spült wie üblich und trocknet das gefärbte Gewebe. Man erhält eine reibechte, egale Blaufärbung ohne negative Beeinflussung der Wollqualität.100 parts of a wool fabric with a m 2 weight of 180 g are treated in 1000 parts of an aqueous liquor containing 4 parts of ammonium sulfate, 2 parts of an aqueous preparation according to Example 1 and 0.5 part of a naphthalenesulfonic acid condensate product at 50 ° C. for 10 minutes; the pH of the liquor is previously adjusted to about 6 with acetic acid. Then 3 parts of the dye of the formula
Figure imgb0007
 added and a further 5 min. treated. The dyeing liquor is then removed within approx. 45 min. heated to approx. 98 ° C and the tissue for 60 min. colored at this temperature. Then allow to cool to approx. 60 ° C, rinse as usual and dry the dyed fabric. You get a rub-fast, level blue color without negatively influencing the wool quality.

Verwendet man anstelle der wässrigen Zubereitung gemäss Beispiel 1

  • (a) 2 Teile der Zubereitung gemäss Beispiel 2,
  • (b) 2 Teile der Zubereitung gemäss Beispiel 3,
so erhält man ebenfalls Färbungen mit guten Eigenschaften und ohne negative Beeinflussung der Wollqualität.Is used instead of the aqueous preparation according to Example 1
  • (a) 2 parts of the preparation according to Example 2,
  • (b) 2 parts of the preparation according to Example 3,
this also gives dyeings with good properties and without adversely affecting the quality of the wool.

Beispiel 6: Example 6 :

Je 10 Teile eines Wollgewebes und 10 Teile eines gebleichten Polyestergewebes werden zusammen in 200 Teilen einer mit Essigsäure auf pH 5,5 eingestellten Flotte enthaltend 0,8 Teile der wässrigen Zubereitung gemäss Beispiel 1 und 0,4 Teile Natriumacetat 5 min. bei 40°C vorbehandelt. Darauf erhitzt man die Flotte innerhalb von 30 min. auf 120°C, behandelt das Gewebe 40 min. bei dieser Temperatur und kühlt anschliessend auf 60°C ab. Nach der so durchgeführten Blindbadbehandlung (ohne Farbstoff) zeigt das Wollgewebe keine Qualitätseinbussen z.B. bezüglich der Berstbeständigkeit; ebenso zeigt das Polyester-Begleitgewebe keine Angilbung durch den hydrolytischen Abbau der Wolle.10 parts each of a wool fabric and 10 parts of a bleached polyester fabric are combined in 200 parts of a liquor adjusted to pH 5.5 with acetic acid, containing 0.8 parts of the aqueous preparation according to Example 1 and 0.4 parts of sodium acetate for 5 minutes. pretreated at 40 ° C. Then the fleet is heated within 30 min. to 120 ° C, the fabric is treated for 40 min. at this temperature and then cools down to 60 ° C. After the blind bath treatment (without dye) carried out in this way, the wool fabric shows no loss in quality, for example with regard to bursting resistance; the polyester accompanying fabric also shows no yellowing due to the hydrolytic degradation of the wool.

Aehnlich gute Effekte bezüglich der Berstbeständigkeit der Wolle und dem Nicht-Angilben des Polyester-Gewebes werden erzielt, wenn man anstelle der wässrigen Zubereitung gemäss Beispiel 1

  • (a) 0,8 Teile der Zubereitung gemäss Beispiel 2 oder
  • (b) 0,8 Teile der Zubereitung gemäss Beispiel 3
verwendet.Similar good effects with regard to the bursting resistance of the wool and the non-yellowing of the polyester fabric are achieved if instead of the aqueous preparation according to Example 1
  • (a) 0.8 parts of the preparation according to Example 2 or
  • (b) 0.8 parts of the preparation according to Example 3
used.

Claims (8)

  1. A process for dyeing wool-containing fibre materials with anionic dyes, which comprises dyeing said materials in the presence of a wool protective agent which is a reaction product of an epihalohydrin and ammonia or an amine of formula

            R-NH2     (1),

    wherein R is C1-C6alkyl.
  2. A process according to claim 1, wherein R is methyl or ethyl.
  3. A process according to claim 1 or 2, wherein the epihalohydrin used is epichlorohydrin.
  4. A process according to any one of claims 1 to 3, wherein the wool protective agent used is obtained by reacting 2.5 to 3 molar equivalents of epihalohydrin with 1 molar equivalent of ammonia or amine of formula (1).
  5. A process according to any one of claims 1 to 4, wherein the wool-containing fibre material is dyed in the presence of 0.5 to 10 % by weight, preferably 1 to 6 % by weight, of the wool protective agent, based on the weight of the goods to be dyed.
  6. A process according to claim 1 for dyeing wool-containing fibre materials with anionic dyes, which comprises dyeing said materials in the presence of 0.5 to 10 % by weight, based on the weight of the goods to be dyed, of a wool protective agent which is a reaction product of 2.5 to 3.0 molar equivalents of epichlorohydrin and 1 molar equivalent of ammonia or amine of formula

            R-NH2     (1),

    wherein R is methyl or ethyl.
  7. A process according to claim 1 for dyeing wool-containing fibre materials with anionic dyes, which comprises dyeing said materials in the presence of 1 to 6 % by weight, based on the weight of the goods to be dyed, of a wool protective agent which is a reaction product of 2.5 to 3.0 molar equivalents of epichlorohydrin and 1 molar equivalent of ammonia.
  8. A process according to any one of claims 1 to 7 for dyeing wool/polyester blends by the exhaust process.
EP93810677A 1992-10-01 1993-09-23 Process for dyeing of wool containing fiber materials Expired - Lifetime EP0591108B1 (en)

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JP2672458B2 (en) * 1993-11-05 1997-11-05 ツヤック株式会社 Low temperature dyeing agent for protein fiber products and dyeing method using the same
US5830240A (en) * 1996-10-23 1998-11-03 Solutia Inc. Fibers and textile materials having enhanced dyeability and finish compositions used thereon
US5944852A (en) * 1996-10-23 1999-08-31 Solutia Inc. Dyeing process
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US1977252A (en) * 1933-05-12 1934-10-16 Du Pont Vat dyestuff paste
US1977250A (en) * 1933-05-12 1934-10-16 Du Pont Vat dyestuff paste
US3441609A (en) * 1964-03-24 1969-04-29 Us Agriculture Ammonia-epichlorohydrin reaction products
US3544363A (en) * 1965-11-09 1970-12-01 Cassella Farbwerke Mainkur Ag Dyed textile materials having improved wet fastness properties and method of producing same
US4054542A (en) * 1975-04-14 1977-10-18 Buckman Laboratories, Inc. Amine-epichlorohydrin polymeric compositions
GB1543572A (en) * 1975-05-09 1979-04-04 Iws Nominee Co Ltd Fibre treatment process
JPS60134080A (en) * 1983-12-16 1985-07-17 一方社油脂工業株式会社 Improvement in dyeability of fiber material, cationic fiber reactive product and its producton
US4728337A (en) * 1985-11-08 1988-03-01 Ciba-Geigy Corporation Assistant combination and use thereof as wool textile finishing agent
DE3706176A1 (en) * 1987-02-26 1988-09-08 Sandoz Ag MIX WITH SYNERGISTIC PROPERTIES
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