EP0499090A1 - Process for dyeing polyester and polyester-contaning textile materials - Google Patents

Process for dyeing polyester and polyester-contaning textile materials Download PDF

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Publication number
EP0499090A1
EP0499090A1 EP92101415A EP92101415A EP0499090A1 EP 0499090 A1 EP0499090 A1 EP 0499090A1 EP 92101415 A EP92101415 A EP 92101415A EP 92101415 A EP92101415 A EP 92101415A EP 0499090 A1 EP0499090 A1 EP 0499090A1
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EP
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Prior art keywords
hydrogen
carbon atoms
chlorine
bromine
nitro
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Application number
EP92101415A
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German (de)
French (fr)
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EP0499090B1 (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
    • D06P3/34—Material containing ester groups
    • D06P3/52—Polyesters
    • 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
    • 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
    • D06P3/8233—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 using dispersed 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
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/922—Polyester fiber

Definitions

  • the present invention relates to a process for HT dyeing polyester or polyester-containing textile materials.
  • 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 o 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.
  • 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 fibers. These aids are, for example, oiling or sizing agents, which, if present, would make leveling 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 it has always been the goal to combine both processes into a one-bath rinsing and dyeing process.
  • processes must be developed which give reproducible dyeings in the aqueous dye bath at pH 8 to pH 11.
  • Polyester-cellulose or polyester-polyamide blended fabrics 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 dyes 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 dyes.
  • DOS 39 38 631 describes a method 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.
  • a preferred radical X2 in the dyes of the general formula I is hydrogen.
  • Preferred radicals X3 are nitro and alkylsulfonyl with 1 to 4 C atoms or chlorine and bromine if X1 simultaneously denotes nitro or methylsulfonyl, where, if X1 is methylsulfonyl, X3 cannot simultaneously be X3 alkylsulfonyl and vice versa .
  • Preferred radicals R are hydrogen, allyl or alkyl having 1 to 4 carbon atoms.
  • Particularly preferred dyes of the general formula Ia are those in which X1 is nitro or methylsulfonyl, X3 nitro or alkylsulfonyl having 1 to 4 carbon atoms and Y4 is hydrogen, methyl, ethyl, methoxy or ethoxy, where either X1 or X3 is nitro.
  • Very particularly preferred dyes of the general formula Ia are those in which X1 is nitro, X3 nitro, X4 is hydrogen, chlorine or bromine and Y4 is hydrogen.
  • Particularly preferred dyes of the general formula Ib are those in which X1 is chlorine, bromine, nitro or methylsulfonyl, X2 is hydrogen, X3 is nitro or alkylsulfonyl having 1 to 4 C atoms, X4 is hydrogen and R is alkyl having 1 to 4 C atoms, where, when X1 is methylsulfonyl, X3 cannot simultaneously be alkylsulfonyl with 1 to 4 carbon atoms and vice versa.
  • a very particularly preferred dye of the general formula Ib is that in which X1 is chlorine, X3 nitro and X2, X3 and R are hydrogen.
  • Particularly preferred dyes of the general formula Ic are those in which X1 chlorine, bromine, nitro or methylsulfonyl, X2 hydrogen, X3 nitro or alkylsulfonyl having 1 to 4 carbon atoms, X4 hydrogen, chlorine or bromine, Y1 hydrogen or methyl and R allyl or mean alkyl with 1 to 4 carbon atoms and in particular hydrogen, where if X 1 is methylsulfonyl, X 3 cannot simultaneously be alkyl sulfonyl with 1 to 4 carbon atoms and vice versa.
  • the dyes of general formula I are known and e.g. described in DE-22 12 755 and in DE-31 63 272.
  • the HT 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 adding the dye obtained in production together with dispersants a liquid medium, preferably in water, and the mixture is exposed to the action of shear forces, the originally present dye particles being mechanically comminuted to such an extent 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%.
  • the dye content is usually not below 15% by weight.
  • 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 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 in accordance with the above information are diluted with the dyeing medium, preferably with water, to such an extent that a liquor ratio of 1: 5 to 150 is obtained 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 determined before or during the dyeing by adding bases such as alkali metal hydroxides, e.g. aqueous sodium hydroxide solution, alkali hydrogen carbonates, e.g. Sodium bicarbonate or alkali carbonates e.g. Soda, discontinued.
  • bases such as alkali metal hydroxides, e.g. aqueous sodium hydroxide solution, alkali hydrogen carbonates, e.g. Sodium bicarbonate or alkali carbonates e.g. Soda, discontinued.
  • a preferred pH is 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. The idea of the invention will be explained in more detail in the examples below.
  • 1.5 g of a 20% liquid 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, at 130 o C for 100 g of a fabric dyed from polyethylene terephthalate after the pH of the dye liquor had previously been set to 9 with aqueous sodium hydroxide solution. The dyeing is then reductively cleaned, rinsed and dried. This gives an orange color.
  • 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 orange coloration serves as a reference in a colorimetric comparison with the pH 9 coloration.
  • the colorimetric values of the pH9 staining are: color strength: 101.6%, ⁇ H 0.02, ⁇ C - 0.33, ie both colors are practically identical in color.
  • the dye has practically not decomposed at pH 9.
  • the dye of the formula II in Example 1 is replaced by 4 g of a 10% strength liquid preparation of the dye of the formula III
  • the dye liquor is buffered 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 adjusted to 10 with aqueous sodium hydroxide solution, a dark brown color is obtained.
  • This coloration shows the following colorimetric values in comparison to a coloration carried out at pH 4.5: color strength: 101.9%, ⁇ H-0.59, ⁇ C 0.02.
  • the dye has practically not decomposed at an elevated pH.
  • the dye of the formula II in Example 1 is replaced by 3 g of a 10% liquid setting of the dye of the formula IV and dyeing at pH 9.5, the resulting yellow-brown coloration shows the following colorimetric values compared to that obtained at pH 4.5: color strength: 102%, ⁇ H - 0.16, ⁇ C 0.1 and is therefore also almost identical in color .

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  • Textile Engineering (AREA)
  • Chemical & Material Sciences (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 allgemeinen Formel I <IMAGE> einsetzt, worin X¹ bis X<4>, Y¹ bis Y<4> sowie R wie in Anspruch 1 angegeben definiert sind.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, wherein X¹ to X <4>, Y¹ bis Y <4> and R are defined as indicated in claim 1.

Description

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

In der Regel werden Polyester oder polyesterhaltige Textilmaterialien mit Dispersionsfarbstoffen aus wäßrigem Färbebad bei HT-Bedingungen in einem Temperaturbereich von 120 bis 140oC 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 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 Fasern 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 Faserinnern herausgetreten sind und die Färbung unegal erscheinen lassen, zu zerstören und in der wäßrigen Färbeflotte zu halten.As a rule, 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 o 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 fibers. These aids are, for example, oiling or sizing agents, which, if present, would make leveling 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, benötigen 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, it has always been the goal to combine both processes into a one-bath rinsing and dyeing process. To achieve this goal, however, processes must be 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, der 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 blended fabrics 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 dyes 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 dyes.

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, DOS 39 38 631 describes a method 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.

Es wurde nun überraschenderweise gefunden, daß sich bei pH-Werten zwischen 8 und 11 auch ohne die in der DOS-39 38 631 als Färbereihilfsmittel beschriebene Aminosäuren und -derivate reproduzierbare Färbungen erzielen lassen, wenn man Farbstoffe der allgemeinen Formel I einsetzt.It has now surprisingly been found that at pH values between 8 and 11, reproducible colorations can be achieved even without the amino acids and derivatives described in DOS-39 38 631 as dyeing aids if dyes of the general formula I 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

X¹
Wasserstoff, Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen,
X²
Wasserstoff, Chlor oder Brom,
X³
Wasserstoff, Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen,
X⁴
Wasserstoff, Chlor oder Brom,
Y¹
Wasserstoff oder Methyl,
Y²
Wasserstoff,
Y³
Wasserstoff,
Y⁴
Wasserstoff, Alkyl mit 1 bis 4 C-Atomen oder Alkoxy mit 1 bis 4 C-Atomen und
R
Wasserstoff, Allyl oder Alkyl mit 1 bis 6 C-Atomen, das gegebenenfalls durch Alkoxy mit 1 bis 4 C-Atomen substituiert sein kann,
bedeuten, wobei Y¹ statt Wasserstoff oder Methyl und Y² statt Wasserstoff auch zusammen mit dem sie tragenden Benzolkern einen Naphthylrest und Y² und Y³ statt Wasserstoff zusammen eine direkte Bindung bilden können.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
X¹
Hydrogen, chlorine, bromine, nitro or alkylsulfonyl with 1 to 4 carbon atoms,
X²
Hydrogen, chlorine or bromine,
X³
Hydrogen, chlorine, bromine, nitro or alkylsulfonyl with 1 to 4 carbon atoms,
X⁴
Hydrogen, chlorine or bromine,
Y¹
Hydrogen or methyl,
Y²
Hydrogen,
Y³
Hydrogen,
Y⁴
Hydrogen, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms and
R
Hydrogen, allyl or alkyl having 1 to 6 C atoms, which may optionally be substituted by alkoxy having 1 to 4 C atoms,
mean, where Y¹ instead of hydrogen or methyl and Y² instead of hydrogen together with the benzene nucleus carrying them a naphthyl radical and Y² and Y³ together instead of hydrogen can form a direct bond.

Ein bevorzugtes erfindungsgemäßes Verfahren ist dadurch gekennzeichnet, daß ein oder mehrere Monoazofarbstoffe der allgemeinen Formel Ia,

Figure imgb0002

eingesetzt werden,
in der

X¹
Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen,
X³
Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen,
X⁴
Wasserstoff, Chlor oder Brom und
Y⁴
Wasserstoff, Alkyl mit 1 bis 4 C-Atomen oder Alkoxy mit 1 bis 4 C-Atomen
bedeuten, wobei X¹ und X³ nicht gleichzeitig für Alkylsulfonyl mit 1 bis 4 C-Atomen stehen können.A preferred method according to the invention is characterized in that one or more monoazo dyes of the general formula Ia,
Figure imgb0002
be used
in the
X¹
Chlorine, bromine, nitro or alkylsulfonyl with 1 to 4 carbon atoms,
X³
Chlorine, bromine, nitro or alkylsulfonyl with 1 to 4 carbon atoms,
X⁴
Hydrogen, chlorine or bromine and
Y⁴
Hydrogen, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms
mean, where X¹ and X³ can not simultaneously represent alkylsulfonyl having 1 to 4 carbon atoms.

Ein bevorzugtes erfindungsgemäßes Verfahren ist auch ein Verfahren, bei dem ein oder mehrere Monoazofarbstoffe der allgemeinen Formel Ib

Figure imgb0003

eingesetzt werden,
in der

X¹
Wasserstoff, Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen,
X²
Wasserstoff, Chlor oder Brom,
X³
Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen,
X⁴
Wasserstoff, Chlor oder Brom und
R
Wasserstoff, Allyl oder Alkyl mit 1 bis 6 C-Atomen, das gegebenenfalls durch Alkoxy mit 1 bis 4 C-Atomen substituiert sein kann,
bedeuten, wobei X¹ und X³ nicht gleichzeitig für Alkylsulfonyl mit 1 bis 4 C-Atomen stehen können.A preferred method according to the invention is also a method in which one or more monoazo dyes of the general formula Ib
Figure imgb0003
be used
in the
X¹
Hydrogen, chlorine, bromine, nitro or alkylsulfonyl with 1 to 4 carbon atoms,
X²
Hydrogen, chlorine or bromine,
X³
Chlorine, bromine, nitro or alkylsulfonyl with 1 to 4 carbon atoms,
X⁴
Hydrogen, chlorine or bromine and
R
Hydrogen, allyl or alkyl having 1 to 6 C atoms, which may optionally be substituted by alkoxy having 1 to 4 C atoms,
mean, where X¹ and X³ can not simultaneously represent alkylsulfonyl having 1 to 4 carbon atoms.

Schließlich ist auch ein Färbeverfahren bevorzugt, bei dem ein oder mehrere Monoazofarbstoffe der allgemeinen Formel Ic

Figure imgb0004

eingesetzt werden, in der

X¹
Wasserstoff, Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen,
X²
Wasserstoff, Chlor oder Brom,
X³
Nitro, Chlor, Brom oder Alkylsulfonyl mit 1 bis 4 C-Atomen
X⁴
Wasserstoff, Chlor oder Brom,
Y¹
Wasserstoff oder Methyl und
R
Wasserstoff, Allyl oder Alkyl mit 1 bis 6 C-Atomen, das gegebenenfalls durch Alkoxy mit 1 bis 4 C-Atomen, substituiert sein kann,
bedeuten, wobei X¹ und X³ nicht gleichzeitig für Alkylsulfonyl mit 1 bis 4 C-Atomen stehen können.Finally, a dyeing process is also preferred in which one or more monoazo dyes of the general formula Ic
Figure imgb0004
be used in the
X¹
Hydrogen, chlorine, bromine, nitro or alkylsulfonyl with 1 to 4 carbon atoms,
X²
Hydrogen, chlorine or bromine,
X³
Nitro, chlorine, bromine or alkylsulfonyl with 1 to 4 carbon atoms
X⁴
Hydrogen, chlorine or bromine,
Y¹
Hydrogen or methyl and
R
Hydrogen, allyl or alkyl having 1 to 6 C atoms, which may optionally be substituted by alkoxy having 1 to 4 C atoms,
mean, where X¹ and X³ can not simultaneously represent alkylsulfonyl having 1 to 4 carbon atoms.

Ein bevorzugter Rest X² in den Farbstoffen der allgemeinen Formel I ist Wasserstoff. Bevorzugte Reste X³ sind Nitro und Alkylsulfonyl mit 1 bis 4 C-Atomen oder aber Chlor und Brom, wenn gleichzeitig X¹ Nitro oder Methylsulfonyl bedeutet, wobei, wenn X¹ Methylsulfonyl ist, nicht gleichzeitig X³ Alkylsulfonyl mit 1 bis 4 C-Atomen sein kann und umgekehrt. Bevorzugte Reste R sind Wasserstoff, Allyl oder Alkyl mit 1 bis 4 C-Atomen.A preferred radical X² in the dyes of the general formula I is hydrogen. Preferred radicals X³ are nitro and alkylsulfonyl with 1 to 4 C atoms or chlorine and bromine if X¹ simultaneously denotes nitro or methylsulfonyl, where, if X¹ is methylsulfonyl, X³ cannot simultaneously be X³ alkylsulfonyl and vice versa . Preferred radicals R are hydrogen, allyl or alkyl having 1 to 4 carbon atoms.

Besonders bevorzugte Farbstoffe der allgemeinen Formel Ia sind solche, in denen X¹ Nitro oder Methylsulfonyl, X³ Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen und Y⁴ Wasserstoff, Methyl, Ethyl, Methoxy oder Ethoxy bedeuten, wobei entweder X¹ oder X³ Nitro bedeutet. Ganz besonders bevorzugte Farbstoffe der allgemeinen Formel Ia sind solche, in den X¹ Nitro, X³ Nitro, X⁴ Wasserstoff, Chlor oder Brom und Y⁴ Wasserstoff bedeuten.Particularly preferred dyes of the general formula Ia are those in which X¹ is nitro or methylsulfonyl, X³ nitro or alkylsulfonyl having 1 to 4 carbon atoms and Y⁴ is hydrogen, methyl, ethyl, methoxy or ethoxy, where either X¹ or X³ is nitro. Very particularly preferred dyes of the general formula Ia are those in which X¹ is nitro, X³ nitro, X⁴ is hydrogen, chlorine or bromine and Y⁴ is hydrogen.

Besonders bevorzugte Farbstoffe der allgemeinen Formel Ib sind solche, in denen X¹ Chlor, Brom, Nitro oder Methylsulfonyl, X² Wasserstoff, X³ Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen, X⁴ Wasserstoff und R Alkyl mit 1 bis 4 C-Atomen bedeuten, wobei, wenn X¹ Methylsulfonyl ist, nicht gleichzeitig X³ Alkylsulfonyl mit 1 bis 4 C-Atomen sein kann und umgekehrt. Ein ganz besonders bevorzugter Farbstoff der allgemeinen Formel Ib ist der, in dem X¹ Chlor, X³ Nitro und X², X³ und R Wasserstoff bedeuten.Particularly preferred dyes of the general formula Ib are those in which X¹ is chlorine, bromine, nitro or methylsulfonyl, X² is hydrogen, X³ is nitro or alkylsulfonyl having 1 to 4 C atoms, X⁴ is hydrogen and R is alkyl having 1 to 4 C atoms, where, when X¹ is methylsulfonyl, X³ cannot simultaneously be alkylsulfonyl with 1 to 4 carbon atoms and vice versa. A very particularly preferred dye of the general formula Ib is that in which X¹ is chlorine, X³ nitro and X², X³ and R are hydrogen.

Besonders bevorzugte Farbstoffe der allgemeinen Formel Ic sind solche, in denen X¹ Chlor, Brom, Nitro oder Methylsulfonyl, X² Wasserstoff, X³ Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen, X⁴ Wasserstoff, Chlor oder Brom, Y¹ Wasserstoff oder Methyl und R Allyl oder Alkyl mit 1 bis 4 C-Atomen und insbesondere Wasserstoff bedeuten, wobei, wenn X¹ Methylsulfonyl ist, nicht gleichzeitig X³ Alkylsulfonyl mit 1 bis 4 C-Atomen sein kann und umgekehrt.Particularly preferred dyes of the general formula Ic are those in which X¹ chlorine, bromine, nitro or methylsulfonyl, X² hydrogen, X³ nitro or alkylsulfonyl having 1 to 4 carbon atoms, X⁴ hydrogen, chlorine or bromine, Y¹ hydrogen or methyl and R allyl or mean alkyl with 1 to 4 carbon atoms and in particular hydrogen, where if X 1 is methylsulfonyl, X 3 cannot simultaneously be alkyl sulfonyl with 1 to 4 carbon atoms and vice versa.

Die Farbstoffe der allgemeinen Formel I sind bekannt und z.B. in der DE-22 12 755 und in der DE-31 63 272 beschrieben.The dyes of general formula I are known and e.g. described in DE-22 12 755 and in DE-31 63 272.

Das erfindungsgemäße HT-Verfahren wird bevorzugt im Färbeautoklaven durchgeführt.The HT 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 erfindinngsgemäßen 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 liegt 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 adding the dye obtained in production together with dispersants a liquid medium, preferably in water, and the mixture is exposed to the action of shear forces, the originally present dye particles being mechanically comminuted to such an extent 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, the dye content is usually not below 15% by weight.

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 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 prepare the dyeing liquors, the required amounts of the dye settings which have been prepared in accordance with the above information are diluted with the dyeing medium, preferably with water, to such an extent that a liquor ratio of 1: 5 to 150 is obtained 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 determined before or during the dyeing by adding bases such as alkali metal hydroxides, e.g. aqueous sodium hydroxide solution, alkali hydrogen carbonates, e.g. Sodium bicarbonate or alkali carbonates e.g. Soda, discontinued. A preferred pH is 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. An den nachfolgenden Beispielen soll der Erfindungsgedanke näher erläutert werden.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. The idea of the invention will be explained in more detail in the examples below.

Beispiel 1example 1

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

Figure imgb0005

werden in einem Färbeautoklav 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 130oC auf 100 g eines Gewebes aus Polyethylenterephthalat gefärbt, nachdem vorher der pH-Wert der Färbeflotte mit wäßriger Natronlauge auf 9 gestellt wurde. Danach wird die Färbung reduktiv nachgereinigt, gespült und getrocknet. Man erhält so eine orangefarbene Färbung.1.5 g of a 20% liquid preparation of the dye of the formula II
Figure imgb0005
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, at 130 o C for 100 g of a fabric dyed from polyethylene terephthalate after the pH of the dye liquor had previously been set to 9 with aqueous sodium hydroxide solution. The dyeing is then reductively cleaned, rinsed and dried. This gives an orange color.

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 orangefarbene Färbung dient bei einem farbmetrischen Vergleich mit der pH 9-Färbung als Bezug. Die farbmetrischen Werte der pH9-Färbung sind demgegenüber: Farbstärke: 101,6 %, ΔH 0,02, ΔC - 0,33, d.h. beide Färbungensind praktisch farbtongleich. DerFarbstoff hat sich bei pH 9 praktisch nicht zersetzt.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 orange coloration serves as a reference in a colorimetric comparison with the pH 9 coloration. In contrast, the colorimetric values of the pH9 staining are: color strength: 101.6%, ΔH 0.02, ΔC - 0.33, ie both colors are practically identical in color. The dye has practically not decomposed at pH 9.

Beispiel 2Example 2

Ersetzt man den Farbstoff der Formel II im Beispiel 1 durch 4 g einer 10%igen Flüssigpräparation des Farbstoffs der Formel III

Figure imgb0006

puffert die Färbeflotte mit einer Mischung 3,6 ml Phosphorsäure, 4 g Bernsteinsäure und 4 g Borsäure und stellt den pH-Wert der Färbeflotte mit wäßriger Natronlauge auf 10, so erhält man eine dunkelbraune Färbung. Diese Färbung zeigt im Vergleich zu einer bei pH 4,5 durchgeführten Färbung die folgenden farbmetrischen Werte: Farbstärke: 101,9 %, ΔH - 0,59, ΔC 0,02. Auch hier hat sich bei erhöhtem pH-Wert der Farbstoff praktisch nicht zersetzt.If the dye of the formula II in Example 1 is replaced by 4 g of a 10% strength liquid preparation of the dye of the formula III
Figure imgb0006
If the dye liquor is buffered 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 adjusted to 10 with aqueous sodium hydroxide solution, a dark brown color is obtained. This coloration shows the following colorimetric values in comparison to a coloration carried out at pH 4.5: color strength: 101.9%, ΔH-0.59, ΔC 0.02. Here too, the dye has practically not decomposed at an elevated pH.

Beispiel 3Example 3

Ersetzt man den Farbstoff der Formel II in Beispiel 1 durch 3 g einer 10%igen Flüssigeinstellung des Farbstoffs der Formel IV

Figure imgb0007

und färbt bei pH 9,5, so zeigt die resultierende gelbbraune Färbung im Vergleich zu der bei pH 4,5 erhaltenen die folgenden farbmetrischen Werte: Farbstärke: 102 %, ΔH - 0,16, ΔC 0,1 und ist somit ebenfalls nahezu farbtongleich.The dye of the formula II in Example 1 is replaced by 3 g of a 10% liquid setting of the dye of the formula IV
Figure imgb0007
and dyeing at pH 9.5, the resulting yellow-brown coloration shows the following colorimetric values compared to that obtained at pH 4.5: color strength: 102%, ΔH - 0.16, ΔC 0.1 and is therefore also almost identical in color .

In den nachfolgenden Tabellen sind weitere Farbstoffe aufgeführt, die nach dem erfindungsgemäßen verfahren eingesetzt werden können.

Figure imgb0008
Figure imgb0009
Figure imgb0010
 The following tables list further dyes which can be used in the process according to the invention.
Figure imgb0008
Figure imgb0009
Figure imgb0010

Claims (10)

Verfahren zum HT-Färben von Polyester oder polyesterhaltigen Textilmaterialien bei pH 8 bis pH 11, dadurch gekennzeichnet, daß man einem oder mehrere Monoazofarbstoffe der allgemeinen Formel I
Figure imgb0011
 einsetzt,
in der X¹   Wasserstoff, Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen, X²   Wasserstoff, Chlor oder Brom, X³   Wasserstoff, Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen, X⁴   Wasserstoff, Chlor oder Brom, Y¹   Wasserstoff oder Methyl Y²   Wasserstoff, Y³   Wasserstoff, Y⁴   Wasserstoff, Alkyl mit 1 bis 4 C-Atomen oder Alkoxy mit 1 bis 4 C-Atomen und R   Wasserstoff, Allyl oder Alkyl mit 1 bis 6 C-Atomen das gegebenenfalls durch Alkoxy mit 1 bis 4 C-Atomen substituiert sein kann, bedeuten,
wobei Y¹ statt Wasserstoff oder Methyl und Y² statt Wasserstoff auch zusammen mit dem sie tragenden Benzolkern einen Naphthylrest und Y² und Y³ statt Wasserstoff zusammen eine direkte Bindung bilden können.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 imgb0011
 begins,
in the X¹ is hydrogen, chlorine, bromine, nitro or alkylsulfonyl having 1 to 4 carbon atoms, X² is hydrogen, chlorine or bromine, X³ is hydrogen, chlorine, bromine, nitro or alkylsulfonyl with 1 to 4 carbon atoms, X⁴ hydrogen, chlorine or bromine, Y¹ is hydrogen or methyl Y² is hydrogen, Y³ hydrogen, Y⁴ is hydrogen, alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms and R is hydrogen, allyl or alkyl having 1 to 6 carbon atoms, which may optionally be substituted by alkoxy having 1 to 4 carbon atoms, mean,
where Y¹ instead of hydrogen or methyl and Y² instead of hydrogen together with the benzene nucleus carrying them can form a naphthyl radical and Y² and Y³ together can form a direct bond instead of hydrogen. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß in der allgemeinen Formel I X² Wasserstoff, X³ Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen oder aber Chlor oder Brom, wenn gleichzeitig X¹ Nitro oder Methylsulfonyl ist, sowie R Wasserstoff, Allyl oder Alkyl mit 1 bis 4 C-Atomen, bedeuten, wobei, wenn X¹ Methylsulfonyl ist, nicht gleichzeitig X³ Alkylsulfonyl mit 1 bis 4 C-Atomen sein kann und umgekehrt.A method according to claim 1, characterized in that in the general formula I X² hydrogen, X³ nitro or alkylsulfonyl having 1 to 4 carbon atoms or chlorine or bromine, if X¹ is simultaneously nitro or methylsulfonyl, and R is hydrogen, allyl or alkyl having 1 to 4 C atoms, where, if X¹ is methylsulfonyl, X³ cannot simultaneously be X³ alkylsulfonyl and vice versa . Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß man einen oder mehrere Monoazofarbstoffe der allgemeinen Formel Ia
Figure imgb0012
 einsetzt, in der X¹   Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen, X³   Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen, X⁴   Wasserstoff, Chlor oder Brom und Y⁴   Wasserstoff, Alkyl mit 1 bis 4 C-Atomen oder Alkoxy mit 1 bis 4 C-Atomen, bedeuten, wobei X¹ und X³ nicht gleichzeitig für Alkylsulfonyl mit 1 bis 4 C-Atomen stehen können.Process according to claim 1, characterized in that one or more monoazo dyes of the general formula Ia
Figure imgb0012
 uses in the X¹ chlorine, bromine, nitro or alkylsulfonyl with 1 to 4 carbon atoms, X³ chlorine, bromine, nitro or alkylsulfonyl with 1 to 4 carbon atoms, X⁴ hydrogen, chlorine or bromine and Y⁴ is hydrogen, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms, mean, where X¹ and X³ can not simultaneously represent alkylsulfonyl having 1 to 4 carbon atoms. Verfahren gemäß Anspruch 3, dadurch gekennzeichnet, daß in der allgemeinen Formel Ia
X¹ Nitro, X³ Nitro, X⁴ Wasserstoff, Chlor oder Brom und Y⁴ Wasserstoff bedeuten.A method according to claim 3, characterized in that in the general formula Ia
X¹ is nitro, X³ is nitro, X⁴ is hydrogen, chlorine or bromine and Y⁴ is hydrogen. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß man einen oder mehrere Monoazofarbstoffe der allgemeinen Formel Ib
Figure imgb0013
 einsetzt, in der X¹   Wasserstoff, Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen, X²   Wasserstoff, Chlor oder Brom, X³   Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen, X⁴   Wasserstoff, Chlor oder Brom und R   Wasserstoff, Allyl, Alkyl mit 1 bis 6 C-Atomen, das gegebenenfalls durch Alkoxy mit 1 bis 4 C-Atomen, substituiert sein kann, bedeuten, wobei X¹ und X³ nicht gleichtzeitig für Alkylsulfonyl mit 1 bis 4 C-Atomen stehen können.Process according to Claim 1, characterized in that one or more monoazo dyes of the general formula Ib
Figure imgb0013
 uses in the X¹ is hydrogen, chlorine, bromine, nitro or alkylsulfonyl having 1 to 4 carbon atoms, X² is hydrogen, chlorine or bromine, X³ chlorine, bromine, nitro or alkylsulfonyl with 1 to 4 carbon atoms, X⁴ hydrogen, chlorine or bromine and R is hydrogen, allyl, alkyl having 1 to 6 carbon atoms, which may optionally be substituted by alkoxy having 1 to 4 carbon atoms, mean, where X¹ and X³ can not simultaneously represent alkylsulfonyl having 1 to 4 carbon atoms. Verfahren gemäß Anspruch 5, dadurch gekennzeichnet, daß in der allgemeinen Formel Ib X¹ Chlor, X³ Nitro und X², X³ und R Wasserstoff bedeuten.Process according to claim 5, characterized in that in the general formula Ib X¹ is chlorine, X³ nitro and X², X³ and R are hydrogen. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß man einen oder mehrere Monoazofarbstoffe der allgemeinen Formel Ic
Figure imgb0014
 einsetzt, in der X¹   Wasserstoff, Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen, X²   Wasserstoff, Chlor oder Brom, X³   Chlor, Brom, Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen X⁴   Wasserstoff, Chlor oder Brom Y¹   Wasserstoff oder Methyl und R   Wasserstoff, Allyl oder Alkyl mit 1 bis 6 C-Atomen, das gegebenenfalls durch Alkoxy it 1 bis 4 C-Atomen substituiert sein kann, bedeuten, wobei X¹ und X³ nicht gleichzeitig für Alkylsulfonyl mit 1 bis 4 C-Atomen stehen können.A method according to claim 1, characterized in that one or more monoazo dyes of the general formula Ic
Figure imgb0014
 uses in the X¹ is hydrogen, chlorine, bromine, nitro or alkylsulfonyl having 1 to 4 carbon atoms, X² is hydrogen, chlorine or bromine, X³ chlorine, bromine, nitro or alkylsulfonyl with 1 to 4 carbon atoms X⁴ hydrogen, chlorine or bromine Y¹ is hydrogen or methyl and R is hydrogen, allyl or alkyl having 1 to 6 carbon atoms, which may optionally be substituted by alkoxy having 1 to 4 carbon atoms, mean, where X¹ and X³ can not simultaneously represent alkylsulfonyl having 1 to 4 carbon atoms. Verfahren gemäß Anspruch 7, dadurch gekennzeichnet, daß in der allgemeinen Formel Ic X¹   Chlor, Brom, Nitro oder Methylsulfonyl, X²   Wasserstoff, X³   Nitro oder Alkylsulfonyl mit 1 bis 4 C-Atomen, X⁴   Wasserstoff, Chlor oder Brom, Y¹   Wasserstoff oder Methyl und R   Allyl oder Alkyl mit 1 bis 4 C-Atomen und insbesondere Wasserstoff bedeuten, wobei, wenn X¹ Methylsulfonyl ist, nicht gleichzeitig X³ Alkylsulfonyl mit 1 bis 4 C-Atomen sein kann oder umgekehrt.A method according to claim 7, characterized in that in the general formula Ic X¹ is chlorine, bromine, nitro or methylsulfonyl, X² is hydrogen, X³ nitro or alkylsulfonyl with 1 to 4 carbon atoms, X⁴ hydrogen, chlorine or bromine, Y¹ is hydrogen or methyl and R allyl or alkyl having 1 to 4 carbon atoms and in particular hydrogen mean, where if X¹ is methylsulfonyl, X³ cannot simultaneously be alkylsulfonyl having 1 to 4 carbon atoms or vice versa. Verfahren gemäß einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß man die Färbung bei pH 9 bis pH 10 durchführt.Process according to one or more of claims 1 to 8, characterized in that the dyeing is carried out at pH 9 to pH 10. Verfahren gemäß einem oder mehreren der Ansprüche 1 bis 9, 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 9, 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.
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DE4303359C2 (en) * 1992-05-26 2002-06-20 Inst Chemii Przemyslowej Warsc Reactive carbazole dyes and process for their preparation

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DE59201801D1 (en) 1995-05-11
ES2070533T3 (en) 1995-06-01
JPH04333677A (en) 1992-11-20
DE4104655A1 (en) 1992-08-20
EP0499090B1 (en) 1995-04-05
US5244471A (en) 1993-09-14

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