EP0099111B1 - Process for ht-dyeing polyester materials - Google Patents

Process for ht-dyeing polyester materials Download PDF

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Publication number
EP0099111B1
EP0099111B1 EP83106830A EP83106830A EP0099111B1 EP 0099111 B1 EP0099111 B1 EP 0099111B1 EP 83106830 A EP83106830 A EP 83106830A EP 83106830 A EP83106830 A EP 83106830A EP 0099111 B1 EP0099111 B1 EP 0099111B1
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EP
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Prior art keywords
dye
dyeing
block polymer
dyes
ethylene oxide
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German (de)
French (fr)
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EP0099111A1 (en
Inventor
Hans Dr. Mollet
Paul Dussy
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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
    • 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
    • D06P1/60—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 polyethers
    • D06P1/613—Polyethers without nitrogen
    • D06P1/6138—Polymerisation products of glycols, e.g. Carbowax, Pluronics
    • 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
    • D06P3/34—Material containing ester groups
    • D06P3/52—Polyesters
    • D06P3/54—Polyesters using dispersed dyestuffs
    • 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
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/922—Polyester fiber
    • 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
    • Y10S8/934—High temperature and pressure dyeing

Definitions

  • polyester materials were practically only colored using the carrier process.
  • the disadvantages of this process were soon recognized, such as blotchy discolouration (carrier stains), poor light and rub fastness or the unpleasant smell during dyeing.
  • blotchy discolouration carrier stains
  • poor light and rub fastness or the unpleasant smell during dyeing.
  • high-temperature dyeing HT dyeing for short, which is free from the disadvantages mentioned, was able to do so compared to carrier dyeing in general push through.
  • the HT process in which the material to be dyed and the dyeing liquor are heated to temperatures of 125 to 135 ° C., not only gives dyeings with good fastness properties, but also only requires relatively short dyeing times. With all the advantages, however, HT dyeing is also not entirely problem-free in the implementation.
  • the stability of the dye dispersion in the HT range is particularly difficult, i.e. at temperatures above 100 ° C. Many disperse dyes tend to agglomerate or recrystallize at these temperatures and fail. Agglomerates of this type are particularly noticeable when dyeing cross-wound bobbins, since the coarser dye particles are filtered off on the outer sides of the bobbins and thereby cause uneven dyeings.
  • anionic dispersant In order to increase the dispersion stability of the dyes under HT conditions, large amounts of anionic dispersant are generally added to the dyebath or dye preparations are used which contain a large amount of anionic dispersant.
  • concentration of dispersant is up to 80%, based on the dye preparation.
  • Such high dispersant concentrations not only represent a heavy burden on the wastewater, but also have an unfavorable effect on the degree of exhaustion, which in some cases means that considerable amounts of dye remain in the dye bath. In addition to a loss of valuable dye, this also means pollution of the wastewater.
  • nonionic auxiliaries namely ethylene oxide / propylene oxide block polymers with a molecular weight of at least 5,000, surprisingly ensure the dispersion stability of disperse dyes in the HT range and, moreover, are extremely effective even in low concentrations.
  • the present invention thus relates to a process for HT-dyeing polyester fiber material with dyes which are sparingly soluble in water, which is characterized in that a dyeing liquor is used which contains at least one nonionic ethylene oxide / propylene oxide block polymer with a molecular weight of at least 5,000.
  • the ethylene oxide / propylene oxide block polymers used are preferably those with a molecular weight of 5,000 to 20,000 of the following structure: where the indices a, b and c represent an integer greater than 1; the sum of a + b + c is in the range of 200 to 400 and (a + c) / b is 3 to 9.
  • a particularly favorable influence on the dispersion stability are ethylene oxide / propylene oxide block polymers with a molecular weight of 15,000 to 17,000 at a ratio of (a + c): b equal to 4 to 6.
  • the nonionic dispersant is preferably added to the dyebath in a concentration of 5 to 20% by weight, in many cases a concentration of 10% by weight, based on the dye, is sufficient.
  • the dyeing temperature of the process according to the invention is in a range from 120 ° to 140 ° C. Approx.
  • the material to be dyed is left in the dyebath at this temperature for 1 hour.
  • the dye bath is then allowed to cool, the dyed material is removed from the dyeing machine and finished using customary methods.
  • the sparingly water-soluble dyes used in the process according to the invention are above all disperse dyes which can belong to the following chemical classes: nitro dyes, amino ketone dyes, ketone imine dyes, methine dyes, nitrodiphenylamine dyes, quinoline dyes, amino naphthoquinone dyes, coumarin dyes and in particular anthraquinone dyes, and in particular anthraquinazo dyes Disazo dyes.
  • the dyes are used in finely dispersed form (primary particle size ⁇ 5 p.m), but can also have a particle size of up to 20 ⁇ m.
  • Humectants such as N, N-bis (dihydroxypropyl) butylamine and Antifreezes, for example the polyols, ethylene glycol, monopropylene glycol, diethylene glycol, glycerin, sorbitol and others or formamide; Antimicrobica; Fungicides, for example aqueous formalin solution; Antifoam and viscosity improver.
  • solid dye preparations obtained by spray drying for example, can also be used in the present dyeing process.
  • additives can be added to the dye liquor, such as inorganic salts such as e.g. Ammonium sulfate or small amounts of anionic dispersants, such as lignin sulfonates or formaldehyde condensates of naphthalene sulfonic acids.
  • the pH of the liquor is conveniently e.g. adjusted to a value between 4 and 6 by adding formic acid.
  • the polyester fiber material which can be dyed by the present process consists of aromatic polyesters, in particular of polyethylene glycol terephthalate, and can be in various processing forms, such as knitted fabrics, fabrics, yarns and fibers, as well as finished articles, such as Shirts or ties.
  • the dyeing units for dyeing polyester flakes and card sliver HT circulation apparatuses with packing cylinders are suitable. Smooth yarns can also be dyed on X-bobbins and textured yarns as a cross wrap in HT circulation machines. Fabrics and knitwear are dyed in HT reel runners or HT jet machines or HT tree dyeing machines.
  • the liquor is heated to 60 ° C. and 10 parts of a fabric made of polyethylene terephthalate are added and the mixture is further heated to 130 ° C. with good filter circulation.
  • the dyeing is continued at 130 ° C. for 1 hour, then cooled to 90 ° C. and the fabric is rinsed first with warm, then with cold water.
  • the dyeing liquor is practically completely drawn out and you get a level deep red dyeing with excellent fastness properties.
  • Fabric made of polyethylene terephthalate is dyed in an HT dyeing machine as described in Example 1.
  • 3 parts of a formulation which, in 100 g, contain 25.4 g of a dye mixture consisting of two dyes of the following constitution (particle size ⁇ 2 ⁇ m) where the radical R in one case is hydrogen and in the other case chlorine (mixing ratio 1: 3) 3 g of the block polymer mentioned in Example 1 (MW approx. 16,500; (a + c): b - 5) and 71.6 g contains water.
  • the dye bath is here practically completely drawn out at the end of the dyeing. A deep level navy blue coloration with very good fastness properties is obtained.
  • Fabric made of polyethylene terephthalate is dyed in an HT dyeing machine as described in Example 1. Instead of 2 parts of the dye formulation given there, however, 2 parts of a formulation are used which, in 100 g, contain 38.6 g of a dye of the formula (average particle size 0.2 to 0.5 pm) contains 3 g of the block polymer mentioned in Example 1 (MW approx. 16,500; (a + c): b - 5) and 58.4 g of water, but with part of the water through a humectant of the formula can be replaced.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Coloring (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Description

Polyestermaterialien wurden anfangs praktisch nur nach dem Carrierverfahren gefärbt. Man erkannte jedoch schon bald die Nachteile dieses Verfahrens, wie etwa fleckige Ausfärbungen (Carrierflecken), mangelhafte Licht- und Reibechtheiten oder auch die Geruchsbelästigung während des Färbens. Doch erst als die Maschinenindustrie geschlossene Apparaturen für das Färben von Polyesterfasern als Flocke, Kammzug, Garn oder Stückware zur Verfügung stellte, konnte sich das Hochtemperatur-Färben, kurz HT-Färben von Polyester, das frei von den genannten Nachteilen ist, gegenüber dem Carrierfärben allgemein durchsetzen.Initially, polyester materials were practically only colored using the carrier process. However, the disadvantages of this process were soon recognized, such as blotchy discolouration (carrier stains), poor light and rub fastness or the unpleasant smell during dyeing. However, it was only when the machine industry provided closed equipment for dyeing polyester fibers as flakes, sliver, yarn or piece goods that high-temperature dyeing, HT dyeing for short, which is free from the disadvantages mentioned, was able to do so compared to carrier dyeing in general push through.

Das HT-Verfahren, bei dem Färbegut und Färbeflotte unter Druck auf Temperaturen von 125 bis 135° C erhitzt werden, ergibt nicht nur Färbungen mit guten Echtheiten, sondern beansprucht zudem nur relativ kurze Färbezeiten. Bei allen Vorteilen ist jedoch auch das HT-Färben nicht völlig problemlos in der Durchführung. Schwierigkeiten bereitet vor allem die Stabilität der Farbstoffdispersion im HT-Bereich, d.h. bei Temperaturen über 100° C. So neigen viele Dispersfarbstoffe bei diesen Temperaturen zur Agglomeration oder Rekristallisation und fallen aus. Derartige Agglomerate machen sich besonders beim Färben von Kreuzspulen störend bemerkbar, da sich die gröberen Farbstoffteilchen an den Aussenseiten der Wickelkörper abfiltrieren und dadurch unegale Färbungen verursachen.The HT process, in which the material to be dyed and the dyeing liquor are heated to temperatures of 125 to 135 ° C., not only gives dyeings with good fastness properties, but also only requires relatively short dyeing times. With all the advantages, however, HT dyeing is also not entirely problem-free in the implementation. The stability of the dye dispersion in the HT range is particularly difficult, i.e. at temperatures above 100 ° C. Many disperse dyes tend to agglomerate or recrystallize at these temperatures and fail. Agglomerates of this type are particularly noticeable when dyeing cross-wound bobbins, since the coarser dye particles are filtered off on the outer sides of the bobbins and thereby cause uneven dyeings.

Um die Dispersionsstabilität der Farbstoffe unter HT-Bedingungen zu erhöhen, setzt man dem Färbebad allgemein grosse Mengen an anionischem Dispergator zu oder verwendet Farbstoffpräparate, die viel anionisches Dispergiermittel enthalten. Die Konzentration an Dispergator beträgt bis zu 80%, bezogen auf Farbstoffpräparat. Derart hohe Dispergatorkonzentrationen stellen nicht nur eine starke Belastung des Abwassers dar, sondern wirken sich auch ungünstig auf den Ausziehgrad aus, was dazu führt, dass z.T. erhebliche Mengen an Farbstoff im Färbebad zurückbleiben. Das bedeutet neben einem Verlust an wertvollem Farbstoff auch eine Belastung des Abwassers.In order to increase the dispersion stability of the dyes under HT conditions, large amounts of anionic dispersant are generally added to the dyebath or dye preparations are used which contain a large amount of anionic dispersant. The concentration of dispersant is up to 80%, based on the dye preparation. Such high dispersant concentrations not only represent a heavy burden on the wastewater, but also have an unfavorable effect on the degree of exhaustion, which in some cases means that considerable amounts of dye remain in the dye bath. In addition to a loss of valuable dye, this also means pollution of the wastewater.

So ist z.B. in Chemical Abstracts, Vol. 92 (1980), Seite 99, Nr. 24175m das Färben von Polyestermaterial bei 135°C beschrieben mit einem Farbstoffpräparat, welches auf 92 Teile Dispersfarbstoff 45 Teile eines sulfonierten Anlagerungsproduktes von Aethylenoxid an Polypropylenglykol enthält.For example, in Chemical Abstracts, Vol. 92 (1980), page 99, No. 24175m describes the dyeing of polyester material at 135 ° C. with a dye preparation which contains 45 parts of a sulfonated adduct of ethylene oxide with polypropylene glycol on 92 parts of disperse dye.

Es wurde nun gefunden, dass spezifische nichtionische Hilfsmittel, nämlich Aethylenoxid/Propylenoxid-Blockpolymere mit einem Molgewicht von wenigstens 5'000, überraschenderweise die Dispersionsstabilität von Dispersfarbstoffen im HT-Bereich gewährleisten und zudem bereits in geringen Konzentrationen äusserst wirksam sind.It has now been found that specific nonionic auxiliaries, namely ethylene oxide / propylene oxide block polymers with a molecular weight of at least 5,000, surprisingly ensure the dispersion stability of disperse dyes in the HT range and, moreover, are extremely effective even in low concentrations.

Dies war insofern durchaus nicht vorhersehbar, da in der Literatur, s. A.N. DERBISHIRE et al. JSDC 88, 389 (1972), ausdrücklich darauf hingewiesen wird, dass der Zusatz nichtionischer Hilfsmittel vom Nicht-Carrier Typ einen ungünstigen Einfluss auf die Stabilität von Farbstoffdispersionen hat.This was by no means predictable, since in the literature, see AT. DERBISHIRE et al. JSDC 88, 389 (1972), expressly points out that the addition of nonionic auxiliaries of the non-carrier type has an unfavorable influence on the stability of dye dispersions.

Die vorliegende Erfindung betrifft somit ein Verfahren zum HT-Färben von Polyesterfasermaterial mit in Wasser schwerlöslichen Farbstoffen, das dadurch gekennzeichnet ist, dass man eine Färbeflotte verwendet, die mindestens ein nichtionisches Aethylenoxid/Propylenoxid-Blockpolymer mit einen Molgewicht von wenigstens 5'000 enthält.The present invention thus relates to a process for HT-dyeing polyester fiber material with dyes which are sparingly soluble in water, which is characterized in that a dyeing liquor is used which contains at least one nonionic ethylene oxide / propylene oxide block polymer with a molecular weight of at least 5,000.

Als Aethylenoxid/Propylenoxid-Blockpolymere werden vorzugsweise solche mit einem Molekulargewicht von 5'000 bis 20'000 der folgenden Struktur verwendet,

Figure imgb0001
wobei die Indizes a, b und c eine ganze Zahl grösser als 1 bedeuten; die Summe von a+b+c im Bereich von 200 bis 400 liegt und (a + c)/b 3 bis 9 ist.The ethylene oxide / propylene oxide block polymers used are preferably those with a molecular weight of 5,000 to 20,000 of the following structure:
Figure imgb0001
 where the indices a, b and c represent an integer greater than 1; the sum of a + b + c is in the range of 200 to 400 and (a + c) / b is 3 to 9.

Einen besonders günstigen Einfluss auf die Dispersionsstabilität haben Aethylenoxid/Propylenoxid-Blockpolymere mit einem Molgewicht von 15'000 bis 17'000 bei einem Verhältnis von (a+c):b gleich 4bis 6.A particularly favorable influence on the dispersion stability are ethylene oxide / propylene oxide block polymers with a molecular weight of 15,000 to 17,000 at a ratio of (a + c): b equal to 4 to 6.

Das nichtionische Dispergiermittel wird dem Färbebad bevorzugt in einer Konzentration von 5 bis 20 Gew.% vielfach genügt eine Konzentration von 10 Gew.%, bezogen auf Farbstoff, zugesetzt.The nonionic dispersant is preferably added to the dyebath in a concentration of 5 to 20% by weight, in many cases a concentration of 10% by weight, based on the dye, is sufficient.

Die Färbetemperatur des erfindungsgemässen Verfahrens liegt in einem Bereich von 120° bis 140° C. Ca. 1 Stunde wird das Färbegut bei dieser Temperatur im Färbebad belassen. Danach lässt man das Färbebad abkühlen, entnimmt dem Färbeapparat das gefärbte Material und stellt dieses nach üblichen Methoden fertig.The dyeing temperature of the process according to the invention is in a range from 120 ° to 140 ° C. Approx. The material to be dyed is left in the dyebath at this temperature for 1 hour. The dye bath is then allowed to cool, the dyed material is removed from the dyeing machine and finished using customary methods.

Bei den im erfindungsgemässen Verfahren eingesetzten schwer wasserlöslichen Farbstoffen handelt es sich vor allem um Dispersfarbstoffe, die folgenden chemischen Klassen angehören können: Nitrofarbstoffe, Aminoketonfarbstoffe, Ketoniminfarbstoffe, Methinfarbstoffe, Nitrodiphenylaminfarbstoffe, Chinolinfarbstoffe, Aminonaphthochinonfarbstoffe, - Cumarinfarbstoffe und insbesondere Anthrachinonfarbstoffe und Azofarbstoffe, wie Monoazo- und Disazofarbstoffe. Die Farbstoffe werden in feindisperser Form verwendet (Primärteilchengrösse < 5p.m), können aber auch eine Teilchengrösse von bis zu 20 um aufweisen.The sparingly water-soluble dyes used in the process according to the invention are above all disperse dyes which can belong to the following chemical classes: nitro dyes, amino ketone dyes, ketone imine dyes, methine dyes, nitrodiphenylamine dyes, quinoline dyes, amino naphthoquinone dyes, coumarin dyes and in particular anthraquinone dyes, and in particular anthraquinazo dyes Disazo dyes. The dyes are used in finely dispersed form (primary particle size <5 p.m), but can also have a particle size of up to 20 μm.

Das Aethylenoxid/Propylenoxid-Blockpolymer wird vorteilhaft mittels entsprechend formulierter Färbepräparate, die das Blockpolymer bereits als Dispergiermittel enthalten, in das Färbebad eingebracht. Derartige Farbstoffpräparate haben z.B. die folgende Zusammensetzung:

  • 10 -40 Gew.% Farbstoff
  • 2 - 6 Gew.% Aethylenoxid / Propylenoxid-Blockpolymer
  • mind. 10 Gew.% Wasser und gegebenenfalls weitere Zusätze, wie z.B.
The ethylene oxide / propylene oxide block polymer is advantageously introduced into the dye bath by means of appropriately formulated coloring preparations which already contain the block polymer as a dispersant. Such dye preparations have, for example, the following composition:
  • 10 -40% by weight of dye
  • 2-6% by weight ethylene oxide / propylene oxide block polymer
  • at least 10% by weight of water and, if appropriate, further additives, such as, for example

Feuchthaltemittel wie etwa N,N-Bis-(dihydroxypropyl)-butylamin und
Gefrierschutzmittel, z.B. die Polyole, Aethylenglykol, Monopropylenglykol, Diäthylenglykol, Glycerin, Sorbit und andere oder Formamid; Antimicrobica; Fungicide, z.B. wässrige Formalinlösung; Antischaummittel und viskositätsverbessernde Mittel.Humectants such as N, N-bis (dihydroxypropyl) butylamine and
Antifreezes, for example the polyols, ethylene glycol, monopropylene glycol, diethylene glycol, glycerin, sorbitol and others or formamide; Antimicrobica; Fungicides, for example aqueous formalin solution; Antifoam and viscosity improver.

Anstelle wasserhaltiger Flüssigpräparate können auch, beispielsweise durch Sprühtrocknung erhaltene feste Farbstoffpräparate im vorliegenden Färbeverfahren verwendet werden.Instead of water-containing liquid preparations, solid dye preparations obtained by spray drying, for example, can also be used in the present dyeing process.

Neben Farbstoff und Blockpolymer bzw. dem Farbstoffpräparat mit den darin enthaltenen Hilfsmitteln, können der Färbeflotte noch weitere Zusätze beigegeben werden, etwa anorganische Salze, wie z.B. Ammoniumsulfat oder auch geringe Mengen an anionischen Dispergatoren, wie Ligninsulfonate oder Formaldehydkondensate von Naphthalinsulfonsäuren. Ferner wird der pH der Flotte zweckmässigerweise, z.B. durch Zugabe von Ameisensäure auf einen Wert zwischen 4 und 6 eingestellt.In addition to the dye and block polymer or the dye preparation with the auxiliaries contained therein, further additives can be added to the dye liquor, such as inorganic salts such as e.g. Ammonium sulfate or small amounts of anionic dispersants, such as lignin sulfonates or formaldehyde condensates of naphthalene sulfonic acids. Furthermore, the pH of the liquor is conveniently e.g. adjusted to a value between 4 and 6 by adding formic acid.

Das nach vorliegendem Verfahren färbbare Polyesterfasermaterial besteht aus aromatischen Polyestern, insbesondere aus Polyäthylenglykolterephthalat und kann in verschiedenen Verarbeitungsformen vorliegen, wie Gewirke, Gewebe, Garne und Fasern sowie fertigen Artikeln, wie z.B. Hemden oder Krawatten.The polyester fiber material which can be dyed by the present process consists of aromatic polyesters, in particular of polyethylene glycol terephthalate, and can be in various processing forms, such as knitted fabrics, fabrics, yarns and fibers, as well as finished articles, such as Shirts or ties.

Als Färbeaggregate kommen zum Färben von Polyester-Flocken und -Kardenband HT-Zirkulationsapparate mit Packzylinder in Frage. Glatte Garne lassen sich auf X-Spulen und texturierte Garne als Kreuzwickel ebenfalls in HT-Zirkulationsapparaten färben. Gewebe und Maschenware werden in HT-Haspelkufen oder HT-Jet-Maschinen bzw. HT-Baumfärbeapparaten gefärbt.The dyeing units for dyeing polyester flakes and card sliver HT circulation apparatuses with packing cylinders are suitable. Smooth yarns can also be dyed on X-bobbins and textured yarns as a cross wrap in HT circulation machines. Fabrics and knitwear are dyed in HT reel runners or HT jet machines or HT tree dyeing machines.

Die wichtigsten Vorteile des erfindungsgemässen Verfahrens lassen sich wie folgt zusammenfassen:

  • a) durch den Dispergator vom Typ Aethylenoxid/Propylenoxid-Blockpolymer ist die Stabilität der Farbstoffdispersion im Färbebad unter HT-Bedingungen einwandfrei gewährleistet, es tritt z.B. keine Abfiltration von Farbstoffpartikeln auf dem Fasermaterial auf;
  • b) man erzielt einen hohen Ausziehgrad, bis zur völligen Baderschöpfung;
  • c) es wird nur wenig Blockpolymer benötigt, die Abwasserbelastung ist daher äusserst gering.
The most important advantages of the method according to the invention can be summarized as follows:
  • a) the dispersant of the ethylene oxide / propylene oxide block polymer type ensures the stability of the dye dispersion in the dyebath under HT conditions, for example there is no filtration of dye particles on the fiber material;
  • b) a high degree of exhaustion is achieved until the bathroom is completely exhausted;
  • c) only a little block polymer is required, the wastewater pollution is therefore extremely low.

Die nachfolgenden Beispiele dienen der Erläuterung der Erfindung; sofern nichts anderes angegeben wird, bedeuten Teile Gewichtsteile und Prozente Gewichtsprozente.The following examples serve to illustrate the invention; unless otherwise specified, parts are parts by weight and percentages are percentages by weight.

Beispiel 1example 1

In einen Druckfärbeapparat werden 200 Teile Wasser gefüllt und darin anschliessend 2 Teile Farbstofformulierung dispergiert. 100 g dieser Farbstofformulierung enthalten 17 g des Farbstoffs der Formel

Figure imgb0002
mit einer Teilchengrösse <211m, 3 g eines Aethylenoxid/Propylenoxid-Blockpolymeren der in der Beschreibung angegebenen Formel mit einem Mol-Gewicht von ca. 16'500 und einem Verhältnis von (a+c):b etwa gleich 5 und 80 g Wasser. Der Färbeflotte werden ausserdem noch 0,4 Teile Ammoniumsulfat zugesetzt und der pH wird mittels Ameisensäure auf einen Wert von 4,5 bis 5,5 eingestellt.200 parts of water are filled into a printing dyeing apparatus and then 2 parts of dye formulation are dispersed therein. 100 g of this dye formulation contain 17 g of the dye of the formula
Figure imgb0002
 with a particle size <211 m, 3 g of an ethylene oxide / propylene oxide block polymer of the formula given in the description with a molar weight of approximately 16,500 and a ratio of (a + c): b approximately equal to 5 and 80 g of water. In addition, 0.4 parts of ammonium sulfate are added to the dye liquor and the pH is adjusted to 4.5 to 5.5 using formic acid.

Man erwärmt die Flotte auf 60° C und geht mit 10 Teilen eines Gewebes aus Polyäthylenterephthalat ein und erwärmt unter guter Filterzirkulation weiter auf 130° C. Man färbt 1 Stunde bei 130° C weiter, kühlt anschliessend auf 90° C ab und spült das Textilgut vorerst mit warmem, dann mit kaltem Wasser aus.The liquor is heated to 60 ° C. and 10 parts of a fabric made of polyethylene terephthalate are added and the mixture is further heated to 130 ° C. with good filter circulation. The dyeing is continued at 130 ° C. for 1 hour, then cooled to 90 ° C. and the fabric is rinsed first with warm, then with cold water.

Die Färbeflotte ist praktisch vollständig ausgezogen und man erhält eine egale tiefrote Färbung mit ausgezeichneten Echtheiten.The dyeing liquor is practically completely drawn out and you get a level deep red dyeing with excellent fastness properties.

Eine ebenso einwandfreie Ausfärbung, bei wiederum fast vollständiger Baderschöpfung erhält man, wenn man anstelle des angegebenen nichtionischen Blockpolymers die gleiche Menge eines Aethylenoxid/Propylenoxid-Blockpolymers verwendet, das ein Molgewicht von ca. 13'500 bei einem Verhältnis von (a + c): b etwa gleich 3 bzw. ein Molgewicht von ca. 8'500 bei einem Verhältnis von (a + c): b etwa gleich 9 aufweist.An equally perfect coloration, with almost complete bath exhaustion, is obtained if instead of the specified nonionic block polymer the same amount of an ethylene oxide / propylene oxide block polymer is used, which has a molecular weight of approx. 13,500 with a ratio of (a + c): b has approximately 3 or a molecular weight of approximately 8,500 with a ratio of (a + c): b approximately 9.

Beispiel 2Example 2

Gewebe aus Polyäthylenterephthalat wird wie im Beispiel 1 beschrieben in einem HT-Färbeapparat gefärbt. Anstelle von 2 Teilen der dort angegebenen Farbstofformulierung verwendet man jedoch 3 Teile einer Formulierung, die in 100 g 25,4 g einer Farbstoffmischung, bestehend aus zwei Farbstoffen der folgenden Konstitution (Teilchengrösse <2 µm)

Figure imgb0003
wobei der Rest R in einem Fall Wasserstoff und im anderen Fall Chlor ist (Mischungsverhältnis 1:3) 3 g des im Beispiel 1 genannten Blockpolymeren (MG ca. 16'500; (a + c): b - 5) und 71,6 g Wasser enthält.Fabric made of polyethylene terephthalate is dyed in an HT dyeing machine as described in Example 1. Instead of 2 parts of the dye formulation given there, however, 3 parts of a formulation are used which, in 100 g, contain 25.4 g of a dye mixture consisting of two dyes of the following constitution (particle size <2 µm)
Figure imgb0003
 where the radical R in one case is hydrogen and in the other case chlorine (mixing ratio 1: 3) 3 g of the block polymer mentioned in Example 1 (MW approx. 16,500; (a + c): b - 5) and 71.6 g contains water.

Das Färbebad ist auch hier am Ende der Färbung praktisch vollständig ausgezogen. Man erhält eine tiefe egale marineblaue Färbung mit sehr guten Echtheiten.The dye bath is here practically completely drawn out at the end of the dyeing. A deep level navy blue coloration with very good fastness properties is obtained.

Beispiel 3Example 3

Gewebe aus Polyäthylenterephthalat wird wie im Beispiel 1 beschrieben in einem HT-Färbeapparat gefärbt. Anstelle von 2 Teilen der dort angegebenen Farbstofformulierung verwendet man jedoch 2 Teile einer Formulierung, die in 100 g 38,6 g eines Farbstoffs der Formel

Figure imgb0004
(mittlere Teilchengrösse 0,2 bis 0,5 pm) 3 g des im Beispiel 1 genannten Blockpolymeren (MG ca. 16'500; (a + c): b - 5) und 58,4 g Wasser enthält, wobei jedoch ein Teil des Wassers durch ein Feuchthaltemittel der Formel
Figure imgb0005
ersetzt sein kann.Fabric made of polyethylene terephthalate is dyed in an HT dyeing machine as described in Example 1. Instead of 2 parts of the dye formulation given there, however, 2 parts of a formulation are used which, in 100 g, contain 38.6 g of a dye of the formula
Figure imgb0004
 (average particle size 0.2 to 0.5 pm) contains 3 g of the block polymer mentioned in Example 1 (MW approx. 16,500; (a + c): b - 5) and 58.4 g of water, but with part of the water through a humectant of the formula
Figure imgb0005
 can be replaced.

Am Ende der Färbung, nach Entnahme des Färbeguts, bleibt ein praktisch vollständig ausgezogenes Färbebad zurück. Man erhält eine tiefe egale violette Färbung, mit ebenfalls sehr guten Echtheiten.At the end of the dyeing, after removing the material to be dyed, there remains a dye bath which is practically completely drawn out. A deep, level violet color is obtained, which also has very good fastness properties.

Verwendet man in dem, in den vorausgegangenen Beispielen beschriebenen Färbeverfahren anstelle der dort angegebenen Farbstofformulierungen solche, die kein Blockpolymer, dafür jedoch 30 bis 60 g eines anionischen Dispergators (bezogen auf 100 g Formulierung) enthalten, etwa ein Ligninsulfonat oder Naphthalinsulfonsäure-Formaldehydkondensat, so erreicht man keinen vergleichbar guten Badauszug; es bleiben noch erhebliche Mengen an Farbstoff im Färbebad zurück.If, in the dyeing process described in the preceding examples, instead of the dye formulations given there, those are used which do not contain a block polymer, but instead contain 30 to 60 g of an anionic dispersant (based on 100 g of formulation), for example a lignosulfonate or naphthalenesulfonic acid / formaldehyde condensate, achieved in this way one does not have a comparably good bathroom extract; considerable amounts of dye remain in the dye bath.

Claims (5)

1. A process for the HT dyeing of polyester fibre material with dyes which are sparingly soluble in water, which process comprises the use of a dyebath which contains at least one non-ionic block polymer of ethylene oxide and propylene oxide having a molecular weight of at least 5000.
2. A process according to claim 1, which comprises the use of a block polymer of ethylene oxide and propylene oxide having a molecular weight of 5000 to 20,000 and having the formula
Figure imgb0007
wherein each of a, b and c is an integer greater than 1, the sum of a + b + c is in the range from 200 to 400, and (a + c)/b is 3 to 9.
3. A process according to claim 2, which comprises the use of a block polymer of ethylene oxide and propylene oxide having a molecular weight of 15,000 to 17,000, wherein (a + c)/b is 4 to 6.
4. A process according to claim 1, which comprises the use of a block polymer of ethylene oxide and propylene oxide in a concentration of 5 to 20 % by weight, based on the amount of dye.
5. A process according to claim 1, wherein the block polymer of ethylene oxide and propylene oxide is put into the dyebath in the form of an appropriately formulated dye formulation.
EP83106830A 1982-07-15 1983-07-12 Process for ht-dyeing polyester materials Expired EP0099111B1 (en)

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US4655786A (en) * 1983-11-15 1987-04-07 Ciba-Geigy Corporation Process for dyeing hydrophobic fibre material with disperse dye and surfactant
US4550579A (en) * 1984-04-13 1985-11-05 Frank Clifford G Apparatus for the dyeing of shaped articles
US4653295A (en) * 1984-04-13 1987-03-31 Frank Clifford G Apparatus for the dyeing of shaped articles

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US2880050A (en) * 1956-01-27 1959-03-31 Celanese Corp Butyl benzoate as a dyeing assistant
FR1537952A (en) * 1967-07-21 1968-08-30 Ugine Kuhlmann Process for obtaining plain dyes on polyamide fibers
CH546299A (en) * 1971-01-22 1974-02-28
DE2162672A1 (en) * 1971-12-17 1973-06-20 Henkel & Cie Gmbh PROCESS FOR CARRYING OUT TEXTILE TREATMENT PROCESSES IN THE TEXTILE INDUSTRY
US3784479A (en) * 1972-05-15 1974-01-08 Dow Corning Foam control composition
JPS5810432B2 (en) * 1976-12-27 1983-02-25 花王株式会社 dye preparation
CA1124457A (en) * 1977-11-10 1982-06-01 Ciba-Geigy Investments Ltd. Dyeing process
CH632631B (en) * 1977-11-23 Ciba Geigy Ag AQUATIC PREPARATIONS OF COLORS, INSOLUBLE TO PORTIONAL, AND OPTICAL BRIGHTENERS
GB2037819B (en) * 1978-11-10 1983-07-20 Yorkshire Chemicals Ltd Disperse dye compositions
FR2446350B1 (en) * 1979-01-11 1984-08-24 Ciba Geigy Ag PROCESS FOR DYEING TEXTILE CELLULOSIC MATERIALS NOT PRE-CLEANED, PREPARATION AND PRODUCTS USED THEREFOR, AND CELLULOSIC MATERIALS DYED BY THIS PROCESS
JPS5725678A (en) * 1980-07-24 1982-02-10 Furukawa Battery Co Ltd:The Sealed storage battery

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