EP0540936A1 - Process for dyeing of polyester and polyester-containing textile materials - Google Patents

Process for dyeing of polyester and polyester-containing textile materials Download PDF

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Publication number
EP0540936A1
EP0540936A1 EP92117958A EP92117958A EP0540936A1 EP 0540936 A1 EP0540936 A1 EP 0540936A1 EP 92117958 A EP92117958 A EP 92117958A EP 92117958 A EP92117958 A EP 92117958A EP 0540936 A1 EP0540936 A1 EP 0540936A1
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Prior art keywords
polyester
dyeing
process according
pentyl
dye
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EP92117958A
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German (de)
French (fr)
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EP0540936B1 (en
Inventor
Ulrich Dr. Bühler
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Hoechst Mitsubishi Kasei Co Ltd
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Hoechst Mitsubishi Kasei Co Ltd
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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
    • D06P3/8223—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups
    • D06P3/8228—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups using one kind of dye
    • 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
    • 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

Definitions

  • the present invention relates to a process for HT dyeing textile polyester or polyester-containing textile materials.
  • polyester polyester or polyester-containing textile materials are dyed with disperse dyes from an aqueous dyebath under HT conditions in a temperature range from 120 to 140 ° C at pH values from 4 to 6, since the disperse dyes are partially or completely destroyed at higher pH values .
  • the polyester fiber is normally subjected to an alkaline rinse treatment in a separate step before dyeing in order to remove auxiliaries which have been used in the weaving or spinning of the fiber.
  • These tools are e.g. Lubricants or sizing agents which, if present, would make level dyeing of the polyester fiber difficult or impossible.
  • the alkaline treatment is also carried out in order to destroy oligomers of the polyester fiber which have emerged from the interior of the fiber during the dyeing process and make the dyeing appear uneven, and to keep it in the aqueous dyeing liquor.
  • This alkaline rinsing treatment is advantageously carried out at an elevated temperature.
  • alkaline pretreatment and dyeing the goal has always been to combine both processes into a one-bath rinsing and dyeing process. To achieve this goal however, processes are being developed which give reproducible dyeings in the aqueous dye bath at pH 8 to pH 11.
  • Polyester-cellulose or polyester-polyamide blends are usually dyed with dispersing or reactive dyes from an aqueous dyebath in two dyeing steps.
  • the disperse dyes are applied to the polyester portion at pH 4 to 6, the reactive dyes to the cellulose or polyamide portion in the pH range between pH 11 and 13.
  • the goal in the past was a to develop a single-bath application process for both dye classes.
  • a search has been made for reactive dyestuffs which can already be dyed at pH values between 8 and 11, and processes were also required here which ensure that under these conditions the polyester content can be dyed reproducibly with disperse dyestuffs.
  • DOS 39 38 631 a method is described in DOS 39 38 631 in which disperse dyes in the pH range between pH 8 and 10 in the presence of at least one amino acid which is optionally substituted on nitrogen and / or an alkali metal salt of one which is optionally substituted on nitrogen Amino acid can be colored.
  • the invention thus relates to a process for HT dyeing polyester or polyester-containing textile materials at pH 8 to pH 11, characterized in that one or more monoazo dyes of the general formula I begins, in the Hal chlorine or bromine R alkyl with 3 to 7 carbon atoms and R1 and R2 independently of one another are linear alkyl having 2 to 5 carbon atoms or allyl.
  • Alkyl radicals with 3 to 7 carbon atoms, which can represent R, are, for. B. n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, pentyl-2, pentyl-3, i-pentyl, n-hexyl and heptyl-3 .
  • Linear alkyl radicals with 2 to 5 carbon atoms which can represent R1 and R2, are ethyl, n-propyl, n-butyl and n-pentyl.
  • Preferred radicals R are n-propyl and i-propyl. Particularly preferred radicals are n-butyl, i-butyl, pentyl-2, pentyl-3 and i-pentyl. A very particularly preferred radical R is n-pentyl.
  • Preferred radicals R1 and R2 are n-propyl, n-butyl and allyl.
  • a particularly preferred residue is ethyl.
  • R1 and R2 are the same.
  • R 1 and R 2 are particularly preferably ethyl.
  • the sum of the C atoms in the radicals R, R 1 and R 2 is preferably 8 or 10, particularly preferably 9.
  • Preferred dyes to be used in the process according to the invention are those with preferred or particularly preferred radicals R, R1 and R2.
  • Particularly preferred dyes to be used in the process according to the invention are those with R equal to pentyl, in particular n-pentyl and R 1 and R 2 equal to ethyl.
  • a preferred method according to the invention is also a method in which mixtures of dyes with preferred or particularly preferred radicals R, R1 and R2 are used.
  • mixtures are preferably mixtures of three, particularly preferably mixtures of two.
  • the proportion of a mixture component in a mixture of two is preferably 10 to 90% by weight. It is particularly preferably 30 to 70% by weight and very particularly preferably 40 to 60% by weight.
  • the proportion of a mixture component in a three-component mixture is preferably 5 to 80% by weight. It is particularly preferably 20 to 40% by weight.
  • Dyes of the general formula I and their mixtures are, for. T. known and described in EPA 324 409 and 324 404. Dyes not described there can, however, be prepared in a manner known per se analogously to the information given therein, by using an amine of the general formula IV diazotized and on a coupling component of the general formula V wherein Hal, R, R1 and R2 are as defined above, coupled.
  • the process according to the invention is preferably carried out at pH 9 to pH 10.
  • the process according to the invention is preferably carried out in a dyeing autoclave.
  • polyesters to be colored by the process according to the invention are in particular those based on polyethylene glycol terephthalates.
  • Textile materials containing polyester are mixtures of polyester and polyamides and in particular polyester / cellulose blended fabrics.
  • the dyes or dye mixtures are used in a fine distribution.
  • the fine distribution of the dyes is carried out in a manner known per se by slurrying the dye obtained in manufacture together with dispersants in a liquid medium, preferably in water, and subjecting the mixture to the action of shear forces, the dye particles originally present mechanically so far be crushed so that an optimal specific surface is achieved and the sedimentation of the dye is as low as possible.
  • the particle sizes of the dyes are generally between 0.5 and 5 ⁇ m, preferably around 1 ⁇ m.
  • the dispersants used in the grinding process can be nonionic or anionic.
  • Nonionic dispersants are e.g. Reaction products of alkylene oxides, e.g. Ethylene or propylene oxide with alkylatable compounds such as e.g. Fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols and carboxamides.
  • Anionic dispersants are, for example, lignin sulfonates, alkyl or alkylaryl sulfonates or alkyl aryl polyglycol ether sulfonates.
  • the dye preparations thus obtained are said to be pourable for most applications.
  • the dye and dispersant content is therefore limited in these cases.
  • the dispersions are adjusted to a dye content of up to 50% by weight and a dispersant content of up to about 25%.
  • dye contents of 15% by weight are usually not undershot.
  • the dispersions can also contain other auxiliaries, e.g. those that act as oxidizing agents, e.g. Sodium m-nitrobenzenesulfonate or fungicidal agents such as e.g. Sodium o-phenyl phenolate and sodium pentachlorophenolate.
  • auxiliaries e.g. those that act as oxidizing agents, e.g. Sodium m-nitrobenzenesulfonate or fungicidal agents such as e.g. Sodium o-phenyl phenolate and sodium pentachlorophenolate.
  • Powder settings are preferred for certain areas of application. These powders contain the dye or dye mixture, dispersants and other auxiliaries such as e.g. Wetting, oxidizing, preserving and dedusting agents.
  • a preferred method of manufacturing powdered dye formulations is to withdraw the liquid from the liquid dye dispersions described above, e.g. by vacuum drying, freeze drying, by drying on drum dryers, but preferably also by spray drying.
  • the required amounts of the dye settings which have been prepared according to the above information are diluted with the dyeing medium, preferably with water, to such an extent that a liquor ratio of 1: 5 to 1:50 results for the dyeing.
  • further dyeing aids such as dispersing, wetting and fixing aids, are generally added to the liquors.
  • the required pH of the dye liquor is adjusted before or during the dyeing by adding bases such as alkali metal hydroxides, for example aqueous sodium hydroxide solution, alkali metal hydrogen carbonates, for example sodium bicarbonate or alkali metal carbonates, for example soda.
  • bases such as alkali metal hydroxides, for example aqueous sodium hydroxide solution, alkali metal hydrogen carbonates, for example sodium bicarbonate or alkali metal carbonates, for example soda.
  • bases such as alkali metal hydroxides, for example aqueous sodium hydroxide solution, alkali metal hydrogen carbonates, for example sodium bicarbonate or alkali metal carbonates, for example soda.
  • bases such as alkali metal hydroxides, for example aqueous sodium hydroxide solution, alkali metal hydrogen carbonates, for example sodium bicarbonate or alkali metal carbonates, for example soda.
  • a preferred pH is pH 9 to 10.
  • buffer substances are preferably added, as described, for example, in JSDC, 77 (1979) p. 47 or JSDC 79 (1981), p. 115.
  • Particularly suitable buffer substances are those which have the greatest buffer effect in the pH range between 9 and 11.
  • Suitable buffer systems are, for example, acetic acid / sodium pyrophosphate, boric acid / borax, sodium dihydrogen phosphate / disodium hydrogen phosphate, phosphoric acid / succinic acid / boric acid or combinations of organic phosphorus compounds with polycarboxylic acids.
  • the amounts of buffer system used are preferably between 0.5 and 10 g / l.
  • 1.5 g of a 20% powder preparation of the dye of the formula II are in a dyeing autoclave in a dyeing liquor consisting of 2 l of water, 2 g of a dyeing aid based on formaldehyde condensation product and 5 g of a buffer substance, which is a mixture of an organic phosphorus compound and a polycarboxylic acid, for 45 minutes at 130 ° C on 100 g of a fabric dyed from polyethylene terephthalate after the pH of the Dyeing liquor was set to 9.5 with aqueous sodium hydroxide solution. The dyeing is then rinsed, reductively cleaned, and rinsed and dried. This gives a bluish red color with a clear hue. The dyeing is repeated, 4 g of sodium acetate now being added as the buffer substance and the pH of the dyeing liquor being adjusted to 4.5 with acetic acid. The resulting coloring is practically the same shade, the dye has practically not decomposed at pH 9.5.
  • Example 1 If the dye of formula II in Example 1 is replaced by 2 g of a 10% liquid preparation of the dye of formula III If the dye liquor buffers with a mixture of 3.6 ml phosphoric acid, 4 g succinic acid and 4 g boric acid and the pH of the dye liquor is set to 9, a clear blue color is also obtained, which is also practically identical in color strength and shade to the corresponding color at pH 4.5.

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  • Textile Engineering (AREA)
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Abstract

Die vorliegende Erfindung betrifft ein Verfahren zum HT-Färben von Polyester oder polyesterhaltigen Textilmaterialien bei pH 8 bis pH 11, dadurch gekennzeichnet, daß man einen oder mehrere Monoazofarbstoffe der allgemeinem Formel I <IMAGE> einsetzt, in der Hal Chlor oder Brom R Alkyl mit 3 bis 7 C-Atomen und R¹ und R² unabhängig voneinander lineares Alkyl mit 2 bis 5 C-Atomen oder Allyl bedeuten.The present invention relates to a process for HT-dyeing polyester or polyester-containing textile materials at pH 8 to pH 11, characterized in that one or more monoazo dyes of the general formula I <IMAGE> are used in which Hal is chlorine or bromine R alkyl with 3 up to 7 carbon atoms and R 1 and R 2 independently of one another mean linear alkyl with 2 to 5 carbon atoms or allyl.

Description

Die vorliegende Erfindung betrifft ein Verfahren zum HT-Färben von textilem Polyester oder polyesterhaltigen Textilmaterialien.The present invention relates to a process for HT dyeing textile polyester or polyester-containing textile materials.

In der Regel wird textiles Polyester oder polyesterhaltige Textilmaterialien mit Dispersionsfarbstoffen aus wäßrigem Färbebad bei HT-Bedingungen in einem Temperaturbereich von 120 bis 140°C bei pH-Werten von 4 bis 6 gefärbt, da bei höheren pH-Werten die Dispersionsfarbstoffe teilweise oder ganz zerstört werden. Bei höheren pH-Werten kommt es somit zu Farbstärkeverlusten und Farbtonabweichungen beim Färben und die Färbungen sind nicht reproduzierbar. Nun wird normalerweise die Polyesterfaser in einem separaten Schritt vor dem Färben einer alkalischen Spülbehandlung unterworfen, um Hilfsmittel, die beim Weben oder Spinnen der Faser eingesetzt worden sind, zu entfernen. Diese Hilfsmittel sind z.B. Ölungs- oder Schlichtemittel, die bei ihrem Vorhandensein ein egales Anfärben der Polyesterfaser erschweren oder unmöglich machen würden. Die alkalische Behandlung wird auch durchgeführt, um Oligomere der Polyesterfaser, die beim Färbevorgang aus dem Faserinneren herausgetreten sind und die Färbung unegal erscheinen lassen, zu zerstören und in der wäßrigen Färbeflotte zu halten.As a rule, textile polyester or polyester-containing textile materials are dyed with disperse dyes from an aqueous dyebath under HT conditions in a temperature range from 120 to 140 ° C at pH values from 4 to 6, since the disperse dyes are partially or completely destroyed at higher pH values . At higher pH values, there is a loss of color strength and color deviations during dyeing and the dyeings are not reproducible. Now the polyester fiber is normally subjected to an alkaline rinse treatment in a separate step before dyeing in order to remove auxiliaries which have been used in the weaving or spinning of the fiber. These tools are e.g. Lubricants or sizing agents which, if present, would make level dyeing of the polyester fiber difficult or impossible. The alkaline treatment is also carried out in order to destroy oligomers of the polyester fiber which have emerged from the interior of the fiber during the dyeing process and make the dyeing appear uneven, and to keep it in the aqueous dyeing liquor.

Diese alkalische Spülbehandlung wird zweckmäßigerweise bei erhöhter Temperatur durchgeführt. Um Zeit und Energie zu sparen und um die Anzahl der für beide Prozesse, alkalische Vorbehandlung und Färben, benötigten Apparate zu reduzieren, war es schon immer das Ziel, beide Prozesse zu einem Ein-Bad-Spül- und Färbeverfahren zu vereinigen. Zur Realisierung dieses Zieles müssen allerdings Verfahren entwickelt werden, die im wäßrigen Färbebad bei pH 8 bis pH 11 reproduzierbare Färbungen ergeben.This alkaline rinsing treatment is advantageously carried out at an elevated temperature. In order to save time and energy and to reduce the number of apparatuses required for both processes, alkaline pretreatment and dyeing, the goal has always been to combine both processes into a one-bath rinsing and dyeing process. To achieve this goal however, processes are being developed which give reproducible dyeings in the aqueous dye bath at pH 8 to pH 11.

Polyester-Zellulose- bzw. Polyester-Polyamid-Mischgewebe werden mit Dispergier- bzw. Reaktivfarbstoffen aus wäßrigem Färbebad in der Regel in zwei Färbeschritten gefärbt. Wie oben erwähnt, werden dabei die Dispersionsfarbstoffe auf dem Polyesteranteil bei pH 4 bis 6 appliziert, die Reaktivfarbstoffe auf den Zellulose- bzw. Polyamid-Anteil im pH-Bereich zwischen pH 11 und 13. Auch hier war es in der Vergangenheit das Ziel, ein einbadiges Applikationsverfahren für beide Farbstoffklassen zu entwickeln. Hierfür hat man nach Reaktivfarbstoffen gesucht, die bereits bei pH-Werten zwischen 8 und 11 gefärbt werden können, und es waren auch hier Verfahren erforderlich, die sicherstellen, daß unter diesen Bedingungen der Polyesteranteil mit Dispersionsfarbstoffen reproduzierbar gefärbt werden kann.Polyester-cellulose or polyester-polyamide blends are usually dyed with dispersing or reactive dyes from an aqueous dyebath in two dyeing steps. As mentioned above, the disperse dyes are applied to the polyester portion at pH 4 to 6, the reactive dyes to the cellulose or polyamide portion in the pH range between pH 11 and 13. Here, too, the goal in the past was a to develop a single-bath application process for both dye classes. For this purpose, a search has been made for reactive dyestuffs which can already be dyed at pH values between 8 and 11, and processes were also required here which ensure that under these conditions the polyester content can be dyed reproducibly with disperse dyestuffs.

Zur Behebung der Mängel bisheriger Verfahren wird in der DOS-39 38 631 eine Methode beschrieben, bei der Dispersionsfarbstoffe in pH-Bereich zwischen pH 8 und 10 in Gegenwart mindestens einer, gegebenenfalls am Stickstoff substituierter Aminosäure und/oder eines Alkalimetallsalzes einer gegebenenfalls am Stickstoff substituierten Aminosäure gefärbt werden.To remedy the shortcomings of previous methods, a method is described in DOS 39 38 631 in which disperse dyes in the pH range between pH 8 and 10 in the presence of at least one amino acid which is optionally substituted on nitrogen and / or an alkali metal salt of one which is optionally substituted on nitrogen Amino acid can be colored.

Auch unter Anwendung dieser Methode ist es jedoch nicht möglich, mit den derzeit auf dem Markt befindlichen Azo-Blaufarbstoffen im genannten pH-Bereich klare Blaufärbungen ohne Einbuße an Brillianz und Farbstärke, ohne Farbtonabweichung und ohne deutlich höhere Belastung des Färbereiabwassers durch hydrolysierten Farbstoff zu erzeugen.Even using this method, however, it is not possible to use the azo blue dyes currently on the market to produce clear blue colorations in the stated pH range without loss of brilliance and color strength, without color deviations and without significantly higher loading of the dyeing plant wastewater by hydrolyzed dye.

Es ist literaturbekannt, daß Azo-Blaufarbstoffe mit o-ständiger Cyanogruppe in der Diazokomponente in der Regel eine limitierte pH-Stabilität haben, die bei pH 7 endet (s. Rev. Prog.
Coloration, Vol. 17, Seite 72 ff (1987), Tabelle 3).It is known from the literature that azo blue dyes with o-cyano group in the diazo component generally have a limited pH stability which ends at pH 7 (see Rev. Prog.
Coloration, vol. 17, page 72 ff (1987), table 3).

Es wurde nun überraschenderweise gefunden, daß sich die genannten Probleme beheben lassen, wenn man Farbstoffe der allgemeinen Formel I mit den angegebenen Bedeutungen für die Substituenten am Chromophor einsetzt.It has now surprisingly been found that the problems mentioned can be remedied if dyes of the general formula I with the meanings given for the substituents on the chromophore are used.

Die Erfindung betrifft somit ein Verfahren zum HT-Färben von Polyester oder polyesterhaltigen Textilmaterialien bei pH 8 bis pH 11, dadurch gekennzeichnet, daß man einen oder mehrere Monoazofarbstoffe der allgemeinen Formel I

Figure imgb0001

einsetzt,
in der
Hal Chlor oder Brom
R Alkyl mit 3 bis 7 C-Atomen und
R¹ und R² unabhängig voneinander lineares Alkyl mit 2 bis 5 C-Atomen oder Allyl bedeuten.The invention thus relates to a process for HT dyeing polyester or polyester-containing textile materials at pH 8 to pH 11, characterized in that one or more monoazo dyes of the general formula I
Figure imgb0001
begins,
in the
Hal chlorine or bromine
R alkyl with 3 to 7 carbon atoms and
R¹ and R² independently of one another are linear alkyl having 2 to 5 carbon atoms or allyl.

Alkylreste mit 3 bis 7 C-Atomen, die für R stehen können, sind z. B. n-Propyl, i-Propyl, n-Butyl, i-Butyl, sek.Butyl, tert.-Butyl, n-Pentyl, Pentyl-2, Pentyl-3, i-Pentyl, n-Hexyl und Heptyl-3.Alkyl radicals with 3 to 7 carbon atoms, which can represent R, are, for. B. n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, pentyl-2, pentyl-3, i-pentyl, n-hexyl and heptyl-3 .

Lineare Alkylreste mit 2 bis 5 C-Atomen, die für R¹ und R² stehen können, sind Ethyl, n-Propyl, n-Butyl und n-Pentyl.Linear alkyl radicals with 2 to 5 carbon atoms, which can represent R¹ and R², are ethyl, n-propyl, n-butyl and n-pentyl.

Bevorzugte Reste R sind n-Propyl und i-Propyl. Besonders bevorzugte Reste sind n-Butyl, i-Butyl, Pentyl-2, Pentyl-3 und i-Pentyl. Ein ganz besonders bevorzugter Rest R ist n-Pentyl.Preferred radicals R are n-propyl and i-propyl. Particularly preferred radicals are n-butyl, i-butyl, pentyl-2, pentyl-3 and i-pentyl. A very particularly preferred radical R is n-pentyl.

Bevorzugte Reste R¹ und R² sind n-Propyl, n-Butyl und Allyl. Ein besonders bevorzugter Rest ist Ethyl.Preferred radicals R1 and R2 are n-propyl, n-butyl and allyl. A particularly preferred residue is ethyl.

Bevorzugt sind R¹ und R² gleich. Besonders bevorzugt bedeuten R¹ und R² Ethyl.Preferably R1 and R2 are the same. R 1 and R 2 are particularly preferably ethyl.

Bevorzugt ist die Summe der C-Atome in den Resten R, R¹ und R² 8 oder 10, besonders bevorzugt ist sie 9.The sum of the C atoms in the radicals R, R 1 and R 2 is preferably 8 or 10, particularly preferably 9.

Bevorzugt nach dem erfindungsgemäßen Verfahren einzusetzende Farbstoffe sind solche mit bevorzugten oder besonders bevorzugten Resten R, R¹ und R².Preferred dyes to be used in the process according to the invention are those with preferred or particularly preferred radicals R, R¹ and R².

Besonders bevorzugt nach dem erfindungsgemäßen Verfahren einzusetzende Farbstoffe sind solche mit R gleich Pentyl, insbesondere n-Pentyl und R¹ und R² gleich Ethyl.Particularly preferred dyes to be used in the process according to the invention are those with R equal to pentyl, in particular n-pentyl and R 1 and R 2 equal to ethyl.

Ein bevorzugtes erfindungsgemäßes Verfahren ist weiter ein Verfahren, bei dem Mischungen von Farbstoffen mit bevorzugten oder besonders bevorzugten Resten R, R¹ und R² eingesetzt werden.A preferred method according to the invention is also a method in which mixtures of dyes with preferred or particularly preferred radicals R, R¹ and R² are used.

Bevorzugt sind diese Mischungen Dreier-Mischungen, besonders bevorzugt Zweier-Mischungen.These mixtures are preferably mixtures of three, particularly preferably mixtures of two.

Der Anteil einer Mischungskomponente in einer Zweier-Mischung beträgt bevorzugt 10 bis 90 Gew%. Er ist besonders bevorzugt 30 bis 70 Gew% und ganz besonders bevorzugt 40 bis 60 Gew%.The proportion of a mixture component in a mixture of two is preferably 10 to 90% by weight. It is particularly preferably 30 to 70% by weight and very particularly preferably 40 to 60% by weight.

Der Anteil einer Mischungskomponente in einer Dreier-Mischung beträgt bevorzugt 5 bis 80 Gew%. Er ist besonders bevorzugt 20 bis 40 Gew%.The proportion of a mixture component in a three-component mixture is preferably 5 to 80% by weight. It is particularly preferably 20 to 40% by weight.

Farbstoffe der allgemeinen Formel I und ihre Mischungen sind z. T. bekannt und in der EPA 324 409 bzw. 324 404 beschrieben. Dort nicht beschriebene Farbstoffe können aber analog den dortigen Angaben in an sich bekannter Weise hergestellt werden, indem ein Amin der allgemeinen Formel IV

Figure imgb0002

diazotiert und auf eine Kupplungskomponente der allgemeinen Formel V
Figure imgb0003
wobei Hal, R, R¹ und R² wie oben angegeben definiert sind, gekuppelt wird.Dyes of the general formula I and their mixtures are, for. T. known and described in EPA 324 409 and 324 404. Dyes not described there can, however, be prepared in a manner known per se analogously to the information given therein, by using an amine of the general formula IV
Figure imgb0002
diazotized and on a coupling component of the general formula V
Figure imgb0003
wherein Hal, R, R¹ and R² are as defined above, coupled.

Bevorzugt wird das erfindungsgemäße Verfahren bei pH 9 bis pH 10 durchgeführt.The process according to the invention is preferably carried out at pH 9 to pH 10.

Das erfindungsgemäße Verfahren wird bevorzugt im Färbeautoklaven durchgeführt.The process according to the invention is preferably carried out in a dyeing autoclave.

Die nach dem erfindungsgemäßen Verfahren zu färbenden Polyester sind insbesondere solche auf Basis von Polyethylenglykolterephthalaten. Polyesterhaltige Textilmaterialien sind Mischungen aus Polyester und Polyamiden und insbesondere Polyester/Cellulose-Mischgewebe.The polyesters to be colored by the process according to the invention are in particular those based on polyethylene glycol terephthalates. Textile materials containing polyester are mixtures of polyester and polyamides and in particular polyester / cellulose blended fabrics.

Bei dem erfindungsgemäßen Verfahren werden die Farbstoffe oder Farbstoffmischungen in feiner Verteilung eingesetzt. Die Feinverteilung der Farbstoffe erfolgt in an sich bekannter Weise dadurch, daß man den in der Fabrikation anfallenden Farbstoff zusammen mit Dispergiermitteln in einem flüssigen Medium, vorzugsweise in Wasser, aufschlämmt und die Mischung der Einwirkung von Scherkräften aussetzt, wobei die ursprünglich vorhandenen Farbstoffteilchen mechanisch so weit zerkleinert werden, daß eine optimale spezifische Oberfläche erreicht wird und die Sedimentation des Farbstoffs möglichst gering ist. Die Teilchengrößen der Farbstoffe liegen im allgemeinen zwischen 0,5 und 5 µm, vorzugsweise bei etwa 1 µm.In the process according to the invention, the dyes or dye mixtures are used in a fine distribution. The fine distribution of the dyes is carried out in a manner known per se by slurrying the dye obtained in manufacture together with dispersants in a liquid medium, preferably in water, and subjecting the mixture to the action of shear forces, the dye particles originally present mechanically so far be crushed so that an optimal specific surface is achieved and the sedimentation of the dye is as low as possible. The particle sizes of the dyes are generally between 0.5 and 5 μm, preferably around 1 μm.

Die bei dem Mahlvorgang mitverwendeten Dispergiermittel können nichtionogen oder anionaktiv sein. Nichtionogene Dispergiermittel sind z.B. Umsetzungsprodukte von Alkylenoxiden, wie z.B. Ethylen- oder Propylenoxid mit alkylierbaren Verbindungen, wie z.B. Fettalkoholen, Fettaminen, Fettsäuren, Phenolen, Alkylphenolen und Carbonsäureamiden. Anionaktive Dispergiermittel sind beispielsweise Ligninsulfonate, Alkyl- oder Alkylarylsulfonate oder Alkyl-aryl-polyglykolethersulfonate.The dispersants used in the grinding process can be nonionic or anionic. Nonionic dispersants are e.g. Reaction products of alkylene oxides, e.g. Ethylene or propylene oxide with alkylatable compounds such as e.g. Fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols and carboxamides. Anionic dispersants are, for example, lignin sulfonates, alkyl or alkylaryl sulfonates or alkyl aryl polyglycol ether sulfonates.

Die so erhaltenen Farbstoffzubereitungen sollen für die meisten Anwendungsweisen gießbar sein. Der Farbstoff- und Dispergiermittelgehalt ist daher in diesen Fällen limitiert. Im allgemeinen werden die Dispersionen auf einen Farbstoffgehalt bis zu 50 Gew.% und einen Dispergiermittelgehalt bis zu etwa 25% eingestellt. Aus ökonomischen Gründen werden Farbstoffgehalte von 15 Gew.% meist nicht unterschritten.The dye preparations thus obtained are said to be pourable for most applications. The dye and dispersant content is therefore limited in these cases. In general, the dispersions are adjusted to a dye content of up to 50% by weight and a dispersant content of up to about 25%. For economic reasons, dye contents of 15% by weight are usually not undershot.

Die Dispersionen können noch weitere Hilfsmittel enthalten, z.B. solche, die als Oxidationsmittel wirken, wie z.B. Natrium-m-nitrobenzolsulfonat oder fungicide Mittel, wie z.B. Natrium-o-phenyl-phenolat und Natriumpentachlorphenolat.The dispersions can also contain other auxiliaries, e.g. those that act as oxidizing agents, e.g. Sodium m-nitrobenzenesulfonate or fungicidal agents such as e.g. Sodium o-phenyl phenolate and sodium pentachlorophenolate.

Für gewisse Anwendungsbereiche werden Pulvereinstellungen bevorzugt. Diese Pulver enthalten den Farbstoff oder das Farbstoffgemisch, Dispergiermittel und andere Hilfsmittel, wie z.B. Netz-, Oxydations-, Konservierungs- und Entstaubungsmittel.Powder settings are preferred for certain areas of application. These powders contain the dye or dye mixture, dispersants and other auxiliaries such as e.g. Wetting, oxidizing, preserving and dedusting agents.

Ein bevorzugtes Herstellungsverfahren für pulverförmige Farbstoffzubereitungen besteht darin, daß den oben beschriebenen flüssigen Farbstoffdispersionen die Flüssigkeit entzogen wird, z.B. durch Vakuumtrocknung, Gefriertrocknung, durch Trocknung auf Walzentrocknern, vorzugsweise aber auch durch Sprühtrocknung.A preferred method of manufacturing powdered dye formulations is to withdraw the liquid from the liquid dye dispersions described above, e.g. by vacuum drying, freeze drying, by drying on drum dryers, but preferably also by spray drying.

Zur Herstellung der Färbeflotten werden die erforderlichen Mengen der Farbstoffeinstellungen, die gemäß den obigen Angaben hergestellt wurden, mit dem Färbemedium, vorzugsweise mit Wasser, so weit verdünnt, daß sich für die Färbung ein Flottenverhältnis von 1:5 bis 1:50 ergibt. Zusätzlich werden den Flotten im allgemeinen weitere Färbereihilfsmittel, wie Dispergier-, Netz- und Fixierhilfsmittel zugesetzt.To produce the dyeing liquors, the required amounts of the dye settings which have been prepared according to the above information are diluted with the dyeing medium, preferably with water, to such an extent that a liquor ratio of 1: 5 to 1:50 results for the dyeing. In addition, further dyeing aids, such as dispersing, wetting and fixing aids, are generally added to the liquors.

Der erforderliche pH-Wert der Färbeflotte wird vor bzw. auch während des Färbens durch Zugabe von Basen wie Alkalihydroxiden, z.B. wäßriger Natronlauge, Alkalihydrogencarbonaten, z.B. Natriumhydrogencarbonat oder Alkalicarbonaten z.B. Soda, eingestellt. Ein bevorzugter pH-Wert ist pH 9 bis 10.The required pH of the dye liquor is adjusted before or during the dyeing by adding bases such as alkali metal hydroxides, for example aqueous sodium hydroxide solution, alkali metal hydrogen carbonates, for example sodium bicarbonate or alkali metal carbonates, for example soda. A preferred pH is pH 9 to 10.

Um pH-Schwankungen zu minimieren, werden vorzugsweise Puffersubstanzen zugesetzt, wie sie z.B. in JSDC, 77 (1979) S. 47 oder JSDC 79 (1981), S. 115 beschrieben sind. Besonders geeignete Puffersubstanzen sind solche, die im pH-Bereich zwischen 9 und 11 die größte Pufferwirkung besitzen. Geeignete Puffersysteme sind z.B. Essigsäure/ Natriumpyrophosphat, Borsäure/Borax, Natriumdihydrogenphosphat/Dinatriumhydrogenphosphat, Phosphorsäure/Bernsteinsäure/Borsäure oder Kombinationen organischer Phosphorverbindungen mit Polycarbonsäuren. Die Einsatzmengen an Puffersystem liegen vorzugsweise zwischen 0,5 und 10 g/l.In order to minimize pH fluctuations, buffer substances are preferably added, as described, for example, in JSDC, 77 (1979) p. 47 or JSDC 79 (1981), p. 115. Particularly suitable buffer substances are those which have the greatest buffer effect in the pH range between 9 and 11. Suitable buffer systems are, for example, acetic acid / sodium pyrophosphate, boric acid / borax, sodium dihydrogen phosphate / disodium hydrogen phosphate, phosphoric acid / succinic acid / boric acid or combinations of organic phosphorus compounds with polycarboxylic acids. The amounts of buffer system used are preferably between 0.5 and 10 g / l.

An den nachfolgenden Beispielen soll der Erfindungsgedanke näher erläutert werden.The idea of the invention will be explained in more detail in the examples below.

Beispiel 1example 1

1,5 g einer 20%igen Pulverpräparation des Farbstoffs der Formel II

Figure imgb0004

werden in einem Färbeautoklaven in einer Färbeflotte bestehend aus 2 l Wasser, 2 g eines Färbereihilfsmittels auf Basis Formaldehydkondensationsprodukt und 5 g einer Puffersubstanz, die eine Mischung aus einer organischen Phosphorverbindung und einer Polycarbonsäure darstellt, 45 Min. bei 130°C auf 100 g eines Gewebes aus Polyethylenterephthalat gefärbt, nachdem vorher der pH-Wert der Färbeflotte mit wäßriger Natronlauge auf 9,5 gestellt wurde. Danach wird die Färbung gespült, reduktiv gereinigt, sowie gespült und getrocknet. Man erhält so eine blaustichig rote Färbung mit klarem Farbton. Die Färbung wird wiederholt, wobei als Puffersubstanz jetzt 4 g Natriumacetat zugesetzt und der pH-Wert der Färbeflotte mit Essigsäure auf 4,5 eingestellt wird. Die resultierende Färbung ist praktisch farbtongleich, der Farbstoff hat sich bei pH 9,5 praktisch nicht zersetzt.1.5 g of a 20% powder preparation of the dye of the formula II
Figure imgb0004
are in a dyeing autoclave in a dyeing liquor consisting of 2 l of water, 2 g of a dyeing aid based on formaldehyde condensation product and 5 g of a buffer substance, which is a mixture of an organic phosphorus compound and a polycarboxylic acid, for 45 minutes at 130 ° C on 100 g of a fabric dyed from polyethylene terephthalate after the pH of the Dyeing liquor was set to 9.5 with aqueous sodium hydroxide solution. The dyeing is then rinsed, reductively cleaned, and rinsed and dried. This gives a bluish red color with a clear hue. The dyeing is repeated, 4 g of sodium acetate now being added as the buffer substance and the pH of the dyeing liquor being adjusted to 4.5 with acetic acid. The resulting coloring is practically the same shade, the dye has practically not decomposed at pH 9.5.

Beispiel 2Example 2

Ersetzt man den Farbstoff der Formel II in Beispiel 1 durch 2 g einer 10%igen Flüssigpräparation des Farbstoffs der Formel III

Figure imgb0005

puffert die Färbeflotte mit einer Mischung aus 3,6 ml Phosphorsäure, 4 g Bernsteinsäure und 4 g Borsäure und stellt den pH-Wert der Färbeflotte auf 9, so erhält man ebenfalls eine klare blaue Färbung, die ebenfalls praktisch farbstärke- und farbtongleich zur entsprechenden Färbung bei pH 4,5 ist.If the dye of formula II in Example 1 is replaced by 2 g of a 10% liquid preparation of the dye of formula III
Figure imgb0005
If the dye liquor buffers with a mixture of 3.6 ml phosphoric acid, 4 g succinic acid and 4 g boric acid and the pH of the dye liquor is set to 9, a clear blue color is also obtained, which is also practically identical in color strength and shade to the corresponding color at pH 4.5.

In der nachfolgenden Tabelle sind weitere Farbstoffe aufgeführt, die nach dem erfindungsgemäßen Verfahren eingesetzt werden können.

Figure imgb0006
Figure imgb0007
 The table below lists further dyes which can be used by the process according to the invention.
Figure imgb0006
Figure imgb0007

In der nachfolgenden Tabelle sind Farbstoffmischungen aufgeführt, die nach dem erfindungsgemäßen Verfahren eingesetzt werden können. Hal R R¹ R² Mischungsverhältnis Br nC₅H₁₁ C₂H₅ C₂H₅ 50 Cl nC₅H₁₁ C₂H₅ C₂H₅ 50 Br nC₅H₁₁ C₂H₅ C₂H₅ 70 Cl nC₅H₁₁ C₂H₅ C₂H₅ 30 Br nC₅H₁₁ C₂H₅ C₂H₅ 55 Br nC₄H₉ C₂H₅ C₂H₅ 45 Cl nC₅H₁₁ C₂H₅ C₂H₅ 80 Cl nC₅H₁₁ nC₃H₇ C₃H₇ 20 Br nC₅H₁₁ C₂H₅ C₂H₅ 60 Br nC₄H₉ nC₃H₇ nC₃H₇ 40 Cl nC₃H₇ C ₂H₅ nC₄H₉ 10 Cl nC₅H₁₁ C₂H₅ nC₃H₇ 90 Br nC₃H₇ nC₄H₉ nC₄H₉ 50 Br nC₃H₇ nC₃H₇ nC₃H₇ 50 Cl nC₅H₁₁ C₂H₅ C₂H₅ 30 Cl CH(C₂H₅)₂ C₂H₅ C₂H₅ 70 Cl nC₅H₁₁ C₂H₅ C₂H₅ 40 Cl CH(CH₃)C₃H₇ C₂H₅ C₂H₅ 60 Br nC₅H₁₁ C₂H₅ nC₃H₇ 90 Cl CH(CH₃)C₂H₅ nC₃H₇ nC₃H₇ 10 The following table lists dye mixtures which can be used by the process according to the invention. Hal R R¹ R² Mixing ratio Br nC₅H₁₁ C₂H₅ C₂H₅ 50 Cl nC₅H₁₁ C₂H₅ C₂H₅ 50 Br nC₅H₁₁ C₂H₅ C₂H₅ 70 Cl nC₅H₁₁ C₂H₅ C₂H₅ 30th Br nC₅H₁₁ C₂H₅ C₂H₅ 55 Br nC₄H₉ C₂H₅ C₂H₅ 45 Cl nC₅H₁₁ C₂H₅ C₂H₅ 80 Cl nC₅H₁₁ nC₃H₇ C₃H₇ 20th Br nC₅H₁₁ C₂H₅ C₂H₅ 60 Br nC₄H₉ nC₃H₇ nC₃H₇ 40 Cl nC₃H₇ C ₂H₅ nC₄H₉ 10th Cl nC₅H₁₁ C₂H₅ nC₃H₇ 90 Br nC₃H₇ nC₄H₉ nC₄H₉ 50 Br nC₃H₇ nC₃H₇ nC₃H₇ 50 Cl nC₅H₁₁ C₂H₅ C₂H₅ 30th Cl CH (C₂H₅) ₂ C₂H₅ C₂H₅ 70 Cl nC₅H₁₁ C₂H₅ C₂H₅ 40 Cl CH (CH₃) C₃H₇ C₂H₅ C₂H₅ 60 Br nC₅H₁₁ C₂H₅ nC₃H₇ 90 Cl CH (CH₃) C₂H₅ nC₃H₇ nC₃H₇ 10th

Claims (9)

Verfahren zum HT-Färben von Polyester oder polyesterhaltigen Textilmaterialien bei pH 8 bis pH 11, dadurch gekennzeichnet, daß man einen oder mehrere Monoazofarbstoffe der allgemeinen Formel I
Figure imgb0008
 einsetzt,
in der
Hal Chlor oder Brom
R Alkyl mit 3 bis 7 C-Atomen und
R¹ und R² unabhängig voneinander lineares Alkyl mit 2 bis 5 C-Atomen oder Allyl
bedeuten.Process for HT dyeing polyester or polyester-containing textile materials at pH 8 to pH 11, characterized in that one or more monoazo dyes of the general formula I
Figure imgb0008
 begins,
in the
Hal chlorine or bromine
R alkyl with 3 to 7 carbon atoms and
R¹ and R² independently of one another linear alkyl having 2 to 5 carbon atoms or allyl
mean. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß man einen oder mehrere Farbstoffe der Formel I einsetzt, in der R n-Butyl, i-Butyl, Pentyl-2, Pentyl-3 oder i-Pentyl bedeutet.Process according to claim 1, characterized in that one or more dyes of the formula I are used in which R is n-butyl, i-butyl, pentyl-2, pentyl-3 or i-pentyl. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß R n-Pentyl bedeutet.A method according to claim 1, characterized in that R is n-pentyl. Verfahren gemäß einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß R¹ und R² unabhängig voneinander Ethyl, n-Propyl, n-Butyl oder Allyl bedeuten.Process according to one or more of claims 1 to 3, characterized in that R¹ and R² independently of one another denote ethyl, n-propyl, n-butyl or allyl. Verfahren gemäß einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß R¹ und R² gleich sind.Process according to one or more of claims 1 to 3, characterized in that R¹ and R² are the same. Verfahren gemäß Anspruch 5, dadurch gekennzeichnet, daß R¹ und R² Ethyl bedeuten.Process according to claim 5, characterized in that R¹ and R² are ethyl. Verfahren gemäß einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Summe der C-Atome in den Resten R, R¹ und R² 8 bis 10 beträgt.Process according to one or more of claims 1 to 6, characterized in that the sum of the C atoms in the radicals R, R¹ and R² is 8 to 10. Verfahren gemäß einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man die Färbung bei pH 9 bis pH 10 durchführt.Process according to one or more of claims 1 to 7, characterized in that the dyeing is carried out at pH 9 to pH 10. Verfahren gemäß einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die Färbung in Gegenwart einer oder mehrerer Puffersubstanzen durchgeführt wird, die in dem jeweils verwendeten pH-Bereich puffern.Method according to one or more of claims 1 to 8, characterized in that the coloring is carried out in the presence of one or more buffer substances which buffer in the pH range used in each case.
EP92117958A 1991-11-07 1992-10-21 Process for dyeing of polyester and polyester-containing textile materials Expired - Lifetime EP0540936B1 (en)

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EP0643107A1 (en) * 1993-09-11 1995-03-15 Hoechst Mitsubishi Kasei Co., Ltd. Dyeing process of polyester and polyester-containing textiles

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DE4446943A1 (en) * 1994-12-28 1996-07-04 Cassella Ag Process for dyeing polyester and textile materials containing polyester
CN105102547A (en) * 2013-01-14 2015-11-25 德司达染料分销有限公司 High wet fast disperse dye mixtures

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0324404A1 (en) * 1988-01-13 1989-07-19 CASSELLA Aktiengesellschaft Mixtures of mono azo dyes
EP0324409A1 (en) * 1988-01-13 1989-07-19 CASSELLA Aktiengesellschaft Water insoluble monoazo dyes, their preparation and their use
GB2226051A (en) * 1988-11-25 1990-06-20 Mitsubishi Chem Ind Dyeing polyester fibres under alkaline conditions in presence of amino acid

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DE4104655A1 (en) * 1991-02-15 1992-08-20 Cassella Ag METHOD FOR DYING POLYESTERS AND TEXTILE MATERIALS CONTAINING POLYESTERS
DE4106323A1 (en) * 1991-02-28 1992-09-03 Cassella Ag METHOD FOR ADVERTISING POLYESTER AND POLYESTER-BASED TEXTILE MATERIALS

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
EP0324404A1 (en) * 1988-01-13 1989-07-19 CASSELLA Aktiengesellschaft Mixtures of mono azo dyes
EP0324409A1 (en) * 1988-01-13 1989-07-19 CASSELLA Aktiengesellschaft Water insoluble monoazo dyes, their preparation and their use
GB2226051A (en) * 1988-11-25 1990-06-20 Mitsubishi Chem Ind Dyeing polyester fibres under alkaline conditions in presence of amino acid

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0643107A1 (en) * 1993-09-11 1995-03-15 Hoechst Mitsubishi Kasei Co., Ltd. Dyeing process of polyester and polyester-containing textiles

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