EP0151552B1 - Process for the continuous dyeing of cellulosic/polyamide blended fabrics - Google Patents

Process for the continuous dyeing of cellulosic/polyamide blended fabrics Download PDF

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Publication number
EP0151552B1
EP0151552B1 EP85810011A EP85810011A EP0151552B1 EP 0151552 B1 EP0151552 B1 EP 0151552B1 EP 85810011 A EP85810011 A EP 85810011A EP 85810011 A EP85810011 A EP 85810011A EP 0151552 B1 EP0151552 B1 EP 0151552B1
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Prior art keywords
process according
metal complex
pad
liquor
dyes
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EP85810011A
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German (de)
French (fr)
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EP0151552A1 (en
Inventor
Hellmut Felle
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Novartis AG
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Ciba Geigy AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/22—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/60—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/241—Polyamides; Polyurethanes using acid dyes
    • 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
    • D06P3/8219—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and amide groups

Definitions

  • the present invention relates to a process for the continuous dyeing of cellulose / polyamide blended fabrics, and to the padding liquor used to carry out the process.
  • Cellulose / polyamide blended fabrics are generally dyed using the two-bath method, for example the cotton portion using the pad-steam method in the first step and then the polyamide portion using the pull-out method or vice versa (W. Bernard, practice of bleaching and dyeing textiles; Springer 1966, Page 368 ff). This process proves to be time-consuming and labor-intensive, especially when dyeing large crops.
  • thermosol pad-steam process has become generally accepted for the continuous dyeing of polyester / cotton blended fabrics.
  • the textile material is impregnated with a padding liquor that already contains a combination of polyester and cotton dyes.
  • a padding liquor that already contains a combination of polyester and cotton dyes.
  • the result is a perfectly dyed cellulose fiber, but the polyamide portion is only dyed on the surface, rather soiled, i.e. the dye has not diffused into the fiber under these conditions.
  • the object of the present invention was therefore to develop a dyeing process for cellulose / polyamide blended fabrics which enables the continuous single-bath dyeing of both types of fibers in one operation.
  • thermosol pad steam dyeing process for the continuous dyeing of cellulose / polyamide blended fabrics with a padding liquor containing vat dyes and special 2: 1 metal complex dyes.
  • non-ionic surfactants In contrast to the present application, however, only a few special 2: 1 metal complex dyes (telogens) can be used.
  • GB-A-896 019 describes a process exclusively for dyeing polyamide fabrics using certain metal complex dyes. If necessary, the additional use of dispersants and / or thickeners is recommended, if appropriate in the presence of a humectant and / or acid dispenser.
  • the invention thus relates to a continuous dyeing process for cellulose / polyamide blended fabrics according to the Thermosol-Pad-Steam method, with a padding liquor containing at least one vat dye and at least one metal complex dye, and optionally further additives, characterized in that the padding liquor is a nonionic Contains surfactant or a mixture of non-ionic surfactants.
  • Preferred nonionic surfactants are ethylene oxide adducts of ethylene oxide with alkylphenols, fatty alcohols, fatty amines or fatty acids (ethoxylates); as well as polyethylene glycols.
  • the molecular weight of the ethylene oxide adducts is between 500 and 10,000 and that of the polyethylene glycols between 200 and 6000.
  • ethylene oxide adducts those mentioned under a) are preferred, namely those with a molecular weight of 800 to 1500.
  • Mixtures of the ethylene oxide adducts according to a), b), c) and d) with one another can also be used. These mixtures are obtained by mixing individual adducts or directly by ethoxylating a mixture of the compounds on which the adducts are based. Mixtures of ethylene oxide adducts within a group are of course also possible, such as those obtained by ethoxylating a mixture of fatty alcohols of different chain lengths.
  • Suitable saturated and / or unsaturated fatty alcohols for a) dodecanol, palmityl alcohol, stearyl alcohol, oleyl alcohol or tallow fatty alcohols, preferably a mixture of C 12 to C 19 fatty alcohols.
  • alkylphenols for b) are butylphenol, hexylphenol, but especially isooctylphenol, p-tert-octylphenol, nonylphenol and dodecylphenol.
  • For d) are as saturated and / or unsaturated fatty acids such.
  • polyethylene glycols preferably the low molecular weight z. B. those with a molecular weight from 300 to 500 for use.
  • the nonionic surfactant is advantageously added to the padding liquor in an amount of 2 to 50 g / l, in particular 5 to 20 g / l.
  • Suitable metal complex dyes with which the polyamide portion is colored are, for example, 1: 1 or 1: 2 metal complexes of azo or azomethine dyes or metallized phthalocyanines, such as copper or nickel phthalocyanines.
  • the 1: 1 and 1: 2 metal complexes are preferably 1: 1 nickel complexes, 1: 1 cobalt complexes, 1: 1 copper complexes, 1: 1 chromium complexes, 1: 1 iron complexes or symmetrical or asymmetrical 1: 2 cobalt complexes, 1: 2 iron complexes or 1: 2 chromium complexes, which are used as coloring ligands e.g. B.
  • carboxyl and sulfonic acid groups optionally substituted sulfonic acid amides or alkyl sulfones, halogen atoms or the nitro, acetyl or acetamido group, furthermore alkyl radicals, such as the methyl, ethyl or propyl radical.
  • the azo dyes can be mono-, bis- or polyazo dyes.
  • colorless ligands such as bidentate hydroxyquinoline derivatives, are also suitable in addition to the azo dyes.
  • Metal complex dyes are preferably used 1: 2 in the process according to the invention.
  • the block liquor can in particular also have migration inhibitors, e.g. B. Hypophosphite-acrylic acid telomeres or those based on polyacrylate, these effectively prevent edge runs and a two-sided coloring.
  • migration inhibitors e.g. B. Hypophosphite-acrylic acid telomeres or those based on polyacrylate, these effectively prevent edge runs and a two-sided coloring.
  • buffer substances for. B. ammonium sulfate, sodium hydrogen or dihydrogen phosphate, acids, for. B. acetic acid and / or light stabilizers in question.
  • the fabric first passes through a chemical bath, where the vat dye in alkaline is converted into the water-soluble leuco form using hydrosulfite. Then the fabric enters the air-free steamer, where steaming takes about 1 minute at 100 ° C (saturated steam). After leaving the steamer, the fabric goes into the wide washing machine, where the dyeing is completed by rinsing, oxidizing and soaping.
  • the dyeings obtained with the combination vat dye / metal complex dye on cellulose / polyamide blended fabric in the presence of the specific surfactants according to the present process are distinguished by excellent general fastness properties, in particular by very good light and weather fastness and very good wet fastness properties.
  • the method according to the invention is ideally suited for dyeing large quantities; Compared to the prior art mentioned at the outset, this saves time, is more cost-effective and also saves energy, while at the same time improving shade conformity. It is also surprising that the coloring of the polyamide portion is not damaged by the subsequent development of the vat dye on the cotton fiber.
  • the polyamide fiber component dyed with the metal complex dye survives the treatment with the reducing agent largely without damage; there is practically no destruction of the dye and no color shift.
  • Blended fabrics made of 50% polyamide 6.6 and 50% cotton are dyed on a continuous system using the Thermosol Padsteam process.
  • the pH of the padding liquor is adjusted to 5.5 by adding acetic acid.
  • the textile material has been impregnated with the padding liquor of the specified composition (liquor absorption 60%), intermediate drying (hotflue, temp. 110-130 ° C) and then thermal insulation in a thermo-hotflue for 1 minute at 210-220 ° C.
  • the fabric web then runs through the pad-steam system, where the vat dyes are fixed.
  • the goods first enter the chemical fleet, which contains the amounts of alkali required to reduce vat pigments.
  • B. sodium hydroxide solution and hydrosulfite Then the goods enter the air-free steamer, where steaming takes place for 1 minute at 100 ° C (saturated steam).
  • the textile material runs through the individual compartments of a wide washing machine, where the dyeing is completed by rinsing, oxidizing and soaping.
  • a uniform olive-colored textile material with excellent weather and light fastness and excellent wet fastness properties is obtained.
  • Example 1 If the procedure described in Example 1 is followed, however, a padding liquor is used which, instead of the fatty alcohol ethoxylate, contains the same amount (10 g / liter padding liquor) of one of the following nonionic surfactants, this also gives a uniform olive-colored textile material with excellent weather and Light fastness and excellent wet fastness.

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

Description

Die vorliegende Erfindung betrifft ein Verfahren zum kontinuierlichen Färben von Cellulose/Polyamid-Mischgewebe, sowie die zur Durchführung des Verfahrens verwendete Klotzflotte.The present invention relates to a process for the continuous dyeing of cellulose / polyamide blended fabrics, and to the padding liquor used to carry out the process.

Cellulose/Polyamid-Mischgewebe wird allgemein nach der Zweibadmethode gefärbt, beispielsweise im ersten Schritt der Baumwollanteil nach dem Pad-Steam-Verfahren und anschliessend der Polyamidanteil im Ausziehverfahren oder auch umgekehrt (W. Bernard, Praxis des Bleichens und Färbens von Textilien; Springer 1966, Seite 368 ff). Gerade beim Färben von grossen Metragen erweist sich dieses Verfahren als zeitraubend und arbeitsintensiv.Cellulose / polyamide blended fabrics are generally dyed using the two-bath method, for example the cotton portion using the pad-steam method in the first step and then the polyamide portion using the pull-out method or vice versa (W. Bernard, practice of bleaching and dyeing textiles; Springer 1966, Page 368 ff). This process proves to be time-consuming and labor-intensive, especially when dyeing large crops.

Andrerseits hat sich zum kontinuierlichen Färben von Polyester/-Baumwoll-Mischgewebe das leistungsfähige Thermosol-Pad-Steam-Verfahren allgemein durchgesetzt. Danach wird das Textilmaterial zu Beginn mit einer Klotzflotte imprägniert, die bereits eine Kombination von Polyester- und Baumwollfarbstoffen enthält. Versucht man jedoch Baumwoll/Polyamid-Mischgewebe nach diesem Verfahren zu färben und klotzt das Gewebe mit einer für diese Substrate geeignete Farbstoffe enthaltenden Flotte, so erhält man zwar eine einwandfrei gefärbte Cellulosefaser, der Polyamidanteil ist jedoch nur oberflächlich angefärbt, eher angeschmutzt, d.h. der Farbstoff ist unter diesen Bedingungen nicht in die Faser hineindiffundiert.On the other hand, the powerful thermosol pad-steam process has become generally accepted for the continuous dyeing of polyester / cotton blended fabrics. Then the textile material is impregnated with a padding liquor that already contains a combination of polyester and cotton dyes. However, if one tries to dye cotton / polyamide blended fabrics using this method and blocks the fabric with a liquor containing dyes suitable for these substrates, the result is a perfectly dyed cellulose fiber, but the polyamide portion is only dyed on the surface, rather soiled, i.e. the dye has not diffused into the fiber under these conditions.

Die Aufgabe vorliegender Erfindung bestand somit darin, für Cellulose/-Polyamid-Mischgewebe ein Färbeverfahren zu entwickeln, welches die kontinuierliche einbadige Färbung beider Fasertypen in einem Arbeitsgang ermöglicht.The object of the present invention was therefore to develop a dyeing process for cellulose / polyamide blended fabrics which enables the continuous single-bath dyeing of both types of fibers in one operation.

Bekannt ist aus Textile Chemist and Colorist, Band 2, Nr. 3 (1970) Seiten 60 - 62 ein Thermosol-Pad-Steam Färbeverfahren zum Kontinuefärben von Cellulose/Polyamid-Mischgewebe mit einer Klotzflotte enthaltend Küpenfarbstoffe und spezielle 2 : 1 Metallkomplexfarbstoffe. Auf eine Verwendung von nicht-ionischen Tensiden wird nicht hingewiesen. Im Unterschied zur vorliegenden Anmeldung können jedoch nur wenige spezielle 2 : 1 Metallkomplexfarbstoffe (Telogene) angewendet werden. Desweiteren beschreibt die GB-A-896 019 ein Verfahren ausschliesslich zum Färben von Polyamid-Gewebe, unter Verwendung bestimmter Metallkomplexfarbstoffe. Gegebenenfalls wird eine zusätzliche Verwendung von Dispergiermittel und/oder Verdickungsmittel gegebenenfalls in Gegenwart eines Feuchthaltemittels und/oder Säurespenders empfohlen.Known from Textile Chemist and Colorist, Volume 2, No. 3 (1970) pages 60-62 is a thermosol pad steam dyeing process for the continuous dyeing of cellulose / polyamide blended fabrics with a padding liquor containing vat dyes and special 2: 1 metal complex dyes. There is no reference to the use of non-ionic surfactants. In contrast to the present application, however, only a few special 2: 1 metal complex dyes (telogens) can be used. Furthermore, GB-A-896 019 describes a process exclusively for dyeing polyamide fabrics using certain metal complex dyes. If necessary, the additional use of dispersants and / or thickeners is recommended, if appropriate in the presence of a humectant and / or acid dispenser.

Gefunden wurde, dass sich auch der Polyamidanteil in Cellulose/Polyamid-Mischgewebe nach dem Thermosol-Pad-Steam-Verfahren einwandfrei färben lässt, wenn man der Klotzflotte ein nicht-ionisches Tensid oder Tensidgemisch zusetzt.It was found that the polyamide content in cellulose / polyamide blended fabrics can also be dyed perfectly using the thermosol pad-steam process if a non-ionic surfactant or surfactant mixture is added to the padding liquor.

Gegenstand der Erfindung ist somit ein Kontinuefärbeverfahren für Cellulose/Polyamid-Mischgewebe nach der Thermosol-Pad-Steam-Methode, mit einer Klotzflotte enthaltend mindestens einen Küpenfarbstoff und mindestens einen Metallkomplexfarbstoff, sowie gegebenenfalls weitere Zusätze, dadurch gekennzeichnet, dass die Klotzflotte ein nicht-ionisches Tensid oder ein Gemisch nicht-ionischer Tenside enthält.The invention thus relates to a continuous dyeing process for cellulose / polyamide blended fabrics according to the Thermosol-Pad-Steam method, with a padding liquor containing at least one vat dye and at least one metal complex dye, and optionally further additives, characterized in that the padding liquor is a nonionic Contains surfactant or a mixture of non-ionic surfactants.

Als nicht-ionische Tenside kommen bevorzugt Äthylenoxid-Addukte von Äthylenoxid mit Alkylphenolen, Fettalkoholen, Fettaminen oder Fettsäuren (Äthoxylate); sowie Polyäthylenglykole in Betracht. Das Molgewicht der Äthylenoxid-Addukte bewegt sich zwischen 500 bis 10 000 und das der Polyäthylenglykole zwischen 200 und 6000.Preferred nonionic surfactants are ethylene oxide adducts of ethylene oxide with alkylphenols, fatty alcohols, fatty amines or fatty acids (ethoxylates); as well as polyethylene glycols. The molecular weight of the ethylene oxide adducts is between 500 and 10,000 and that of the polyethylene glycols between 200 and 6000.

Als Äthylenoxid-Addukte sind vor allem genannt:

  • a) Umsetzungsprodukte von gesättigten und/oder ungesättigten Fettalkoholen mit 10 bis 20 C-Atomen, mit 5 bis 40 Mol Äthylenoxid je Mol Fettalkohol;
  • b) Umsetzungsprodukte von Alkylphenolen mit 4 bis 12 C-Atomen im Alkylrest mit 5 bis 40 Mol, vorzugsweise 5 bis 15 Mol, Äthylenoxid je Mol Alkylphenol;
  • c) Umsetzungsprodukte von gesättigten und/oder ungesättigten Fettaminen mit 14 bis 25 C-Atomen mit 10 bis 40 Mol Äthylenoxid je Mol Fettamin;
  • d) Umsetzungsprodukte von gesättigten und/oder ungesättigten Fettsäuren mit 14 bis 20 C-Atomen mit 5 bis 40 Mol Äthylenoxid je Mol Fettsäure.
The following are mentioned as ethylene oxide adducts:
  • a) reaction products of saturated and / or unsaturated fatty alcohols with 10 to 20 carbon atoms, with 5 to 40 moles of ethylene oxide per mole of fatty alcohol;
  • b) reaction products of alkylphenols with 4 to 12 carbon atoms in the alkyl radical with 5 to 40 moles, preferably 5 to 15 moles, of ethylene oxide per mole of alkylphenol;
  • c) reaction products of saturated and / or unsaturated fatty amines with 14 to 25 carbon atoms with 10 to 40 moles of ethylene oxide per mole of fatty amine;
  • d) reaction products of saturated and / or unsaturated fatty acids with 14 to 20 carbon atoms with 5 to 40 moles of ethylene oxide per mole of fatty acid.

Von diesen Äthylenoxid-Addukten sind die unter a) genannten bevorzugt und zwar solche mit einem Molgewicht von 800 bis 1500.Of these ethylene oxide adducts, those mentioned under a) are preferred, namely those with a molecular weight of 800 to 1500.

Auch Gemische der Äthylenoxid-Addukte nach a), b), c) und d) untereinander sind verwendbar. Diese Gemische erhält man durch Mischen einzelner Addukte oder direkt durch Äthoxylierung eines Gemisches der den Addukten zugrunde liegenden Verbindungen. Selbstverständlich kommen auch Gemische von Äthylenoxid-Addukten innerhalb einer Gruppe in Frage, wie sie beispielsweise durch Äthoxylieren einer Mischung von Fettalkoholen unterschiedlicher Kettenlänge erhalten werden.Mixtures of the ethylene oxide adducts according to a), b), c) and d) with one another can also be used. These mixtures are obtained by mixing individual adducts or directly by ethoxylating a mixture of the compounds on which the adducts are based. Mixtures of ethylene oxide adducts within a group are of course also possible, such as those obtained by ethoxylating a mixture of fatty alcohols of different chain lengths.

Als gesättigte und/oder ungesättigte Fettalkohole kommen für a) Dodecanol, Palmitylalkohol, Stearylalkohol, Oleylalkohol oder Talgfettalkohole, vorzugsweise ein Gemisch aus C12 bis C19-Fettalkoholen in Betracht.Suitable saturated and / or unsaturated fatty alcohols for a) dodecanol, palmityl alcohol, stearyl alcohol, oleyl alcohol or tallow fatty alcohols, preferably a mixture of C 12 to C 19 fatty alcohols.

Als Alkylphenole für b) sind Butylphenol, Hexylphenol, vor allem jedoch Isooctylphenol, p-tert.-Octylphenol, Nonylphenol und Dodecylphenol zu nennen.As alkylphenols for b) are butylphenol, hexylphenol, but especially isooctylphenol, p-tert-octylphenol, nonylphenol and dodecylphenol.

Als Fettamin für c) kommt z. B. neben Stearylamin, Palmitylamin und Oleylamin vor allem ein Gemisch von C18 bis C22-Fettaminen in Betracht.As a fatty amine for c) z. B. in addition to stearylamine, palmitylamine and oleylamine, especially a mixture of C 18 to C22 fatty amines into consideration.

Für d) sind als gesättigte und/oder ungesättigte Fettsäuren z. B. Palmitinsäure, vor allem Stearinsäure und Ölsäure zu nennen.For d) are as saturated and / or unsaturated fatty acids such. B. palmitic acid, especially stearic acid and oleic acid.

Von den Polyäthylenglykolen gelangen bevorzugt die niedermolekularen z. B. solche mit einem Molgewicht von 300 bis 500 zur Anwendung.Of the polyethylene glycols preferably the low molecular weight z. B. those with a molecular weight from 300 to 500 for use.

Das nicht-ionische Tensid wird der Klotzflotte vorteilhaft in einer Menge von 2 bis 50 g/I, insbesondere 5 bis 20 g/I zugesetzt.The nonionic surfactant is advantageously added to the padding liquor in an amount of 2 to 50 g / l, in particular 5 to 20 g / l.

Als Küpenfarbstoffe zur Färbung der cellulosischen Faserkomponente sind beispielhaft verküpbare polycyclische Chinone der folgenden Verbindungsklassen angeführt:

  • Perylentetracarbonsäureimide, vor allem die Phenylimide, Anthrapyrimidine, Anthrapyridone, lsothiazolanthrone, Chinazolinanthrachinone, Oxazolanthrachinone, Thiazolanthrachinone, Oxdiazolanthrachinone, Anthrachinonyltriazole, Pyrazolanthrachinone, Dipyrazolanthronyle, Pyrazinoanthrachinone, Azabenzanthrone, Indanthrone, Thioxanthronanthrachinone, Anthrachinonacridone, Dihydroacridine, Anthanthrone, Pyranthrone, Flavanthrone, Acedianthrone und insbesondere Anthrimide, Anthrimidcarbazole, Phthaloylacridine und die Anthrachinone selber, worunter nicht nur Derivate mit reinen 9,10-Dioxoanthracenringen zu verstehen sind, sondern auch solche mit Thiophanthronresten und dergl. sowie Anthrachinonverbindungen, die 9,10-Dioxoanthracenringe aufweisen. All diese Polycyclen können die für Küpfenfarbstoffe üblichen Substituenten tragen. Solche Substituenten sind beispielsweise Halogenatome, insbesondere Chlor, Fluor oder Brom, Alkyl-, Alkoxy-, Aryl-, Aryloxy-, Aralkyl-, Aralkoxy-, Carbalkoxy-, Arylamino, Alkylmercapto-, Arylmercapto-, Cyano- und Thiocyanogruppen. Mit Alkyl sind insbesondere Reste mit 1 bis 4 Kohlenstoffatomen gemeint, mit Aryl insbesondere Reste wie Phenyl-, Toluyl-, Chlorphenyl-, Methoxyphenyl- oder Naphthylreste und mit Aralkyl insbesondere der Benzylrest. Besonders wichtige Substituenten sind ausserdem die Acyl- und die Acylaminogruppe.
Examples of viable polycyclic quinones of the following classes of compounds are given as vat dyes for dyeing the cellulosic fiber component:
  • Perylentetracarbonsäureimide, especially the phenylimides, anthrapyrimidines, anthrapyridones, lsothiazolanthrone, Chinazolinanthrachinone, Oxazolanthrachinone, Thiazolanthrachinone, Oxdiazolanthrachinone, Anthrachinonyltriazole, Pyrazolanthrachinone, Dipyrazolanthronyle, Pyrazinoanthrachinone, Azabenzanthrone, indanthrones, Thioxanthronanthrachinone, anthraquinoneacridones, dihydroacridines, anthanthrones, pyranthrones, flavanthrones, Acedianthrone and especially anthrimides Anthrimidecarbazoles, phthaloylacridines and the anthraquinones themselves, which include not only derivatives with pure 9,10-dioxoanthracene rings, but also those with thiophanthrone residues and the like, and anthraquinone compounds which have 9,10-dioxoanthracene rings. All of these polycycles can carry the substituents customary for vat dyes. Such substituents are, for example, halogen atoms, in particular chlorine, fluorine or bromine, alkyl, alkoxy, aryl, aryloxy, aralkyl, aralkoxy, carbalkoxy, arylamino, alkylmercapto, arylmercapto, cyano and thiocyano groups. Alkyl means in particular residues with 1 to 4 carbon atoms, with aryl especially residues such as phenyl, toluyl, chlorophenyl, methoxyphenyl or naphthyl residues and with aralkyl especially the benzyl residue. The acyl and acylamino groups are also particularly important substituents.

Als Metallkomplexfarbstoffe, mit denen der Polyamidanteil gefärbt wird, kommen beispielsweise 1 : 1 oder 1: 2 Metallkomplexe von Azo- oder Azomethinfarbstoffen oder metallisierte Phthalocyanine, wie Kupfer- oder Nickelphthalocyanine in Betracht. Bei den 1 : 1 und 1 : 2-Metallkomplexen handelt es sich vorzugsweise um 1 : 1-Nickelkomplexe, 1 : 1-Kobaltkomplexe, 1 : 1-Kupferkomplexe, 1 : 1-Chromkomplexe, 1 : 1-Eisenkomplexe oder symmetrische bzw. asymmetrische 1 : 2-Kobaltkomplexe, 1 : 2-Eisenkomplexe oder 1 : 2-Chromkomplexe, die als farbgebende Liganden z. B. o-Carboxy-o'-hydroxy-, o-Hydroxy-o'-amino- oder o,o'-Dihydroxyazofarbstoffe des Benzol-azo-benzol-, Naphthalin-azo-naphthalin-, Benzol-azo-naphthalin-, Benzol-azo-pyrazolon-, Benzol-azo-pyridon- oder Benzol-azo-acetessigsäureamid-Typs aufweisen, wobei diese unsubstituiert oder auch substituiert sein können. Als Substituenten kommen z. B. in Betracht: Carboxyl- und Sulfonsäuregruppen, gegebenenfalls substituierte Sulfonsäureamide oder Alkylsulfone, Halogenatome oder die Nitro-, Acetyl- oder Acetamidogruppe, ferner Alkylreste, wie der Methyl-, Äthyl- oder Propylrest.Suitable metal complex dyes with which the polyamide portion is colored are, for example, 1: 1 or 1: 2 metal complexes of azo or azomethine dyes or metallized phthalocyanines, such as copper or nickel phthalocyanines. The 1: 1 and 1: 2 metal complexes are preferably 1: 1 nickel complexes, 1: 1 cobalt complexes, 1: 1 copper complexes, 1: 1 chromium complexes, 1: 1 iron complexes or symmetrical or asymmetrical 1: 2 cobalt complexes, 1: 2 iron complexes or 1: 2 chromium complexes, which are used as coloring ligands e.g. B. o-carboxy-o'-hydroxy, o-hydroxy-o'-amino or o, o'-dihydroxyazo dyes of benzene-azo-benzene, naphthalene-azo-naphthalene, benzene-azo-naphthalene, Have benzene-azo-pyrazolone, benzene-azo - pyridone or benzene-azo-acetoacetic acid amide type, which may be unsubstituted or substituted. As substituents such. B. into consideration: carboxyl and sulfonic acid groups, optionally substituted sulfonic acid amides or alkyl sulfones, halogen atoms or the nitro, acetyl or acetamido group, furthermore alkyl radicals, such as the methyl, ethyl or propyl radical.

Bei den Azofarbstoffen kann es sich um Mono-, bis- oder Polyazofarbstoffe handeln. In asymmetrischen 1 : 2-Metallkomplexfarbstoffen kommen neben den Azofarbstoffen auch farblose Liganden, wie etwa zweizähnige Hydroxychinolinderivate, in Betracht.The azo dyes can be mono-, bis- or polyazo dyes. In asymmetric 1: 2 metal complex dyes, colorless ligands, such as bidentate hydroxyquinoline derivatives, are also suitable in addition to the azo dyes.

Bevorzugt gelangen im erfindungsgemässen Verfahren 1 : 2 Metallkomplexfarbstoffe zur Anwendung.Metal complex dyes are preferably used 1: 2 in the process according to the invention.

Als weitere Zusätze kann die Klotzflotte insbesondere noch Migrationsinhibitoren, z. B. Hypophosphit-Acrylsäure-Telomere oder solche auf Polyacrylatbasis enthalten, diese verhindern wirksam Kantenabläufe und eine Zweiseitigkeit der Färbung. Ferner kommen als Zusätze Puffersubstanzen, z. B. Ammoniumsulfat, Natriumhydrogen- bzw. Dihydrogenphosphat, Säuren, z. B. Essigsäure und/oder Lichtschutzmittel in Frage.As further additives, the block liquor can in particular also have migration inhibitors, e.g. B. Hypophosphite-acrylic acid telomeres or those based on polyacrylate, these effectively prevent edge runs and a two-sided coloring. Furthermore come as additives buffer substances, for. B. ammonium sulfate, sodium hydrogen or dihydrogen phosphate, acids, for. B. acetic acid and / or light stabilizers in question.

Die Durchführung des erfindungsgemässen Färbeverfahrens gestaltet sich z. B. folgendermassen:

  • Das Cellulose/Polyamid-Mischgewebe, beispielsweise eine 1 : 1 Mischung aus Baumwolle und Polyamid, vor allem Polyamid, 6,6, wird zunächst mit der Klotzflotte imprägniert. Diese enthält je nach Tiefe des gewünschten Farbtons ca. 50 g/I an Farbstoff, ca. 10 g/1 Fettalkoholäthoxylat und zweckmässigerweise ca. 5 g/I Migrationsinhibitor. Anschliessend wird das Gewebe auf eine Flottenaufnahme von etwa 60 % abgequetscht und zwischengetrocknet. Diese Zwischentrocknung kann z. B. mit trockener Luft bei 100-130°C vorgenommen werden. Dann erfolgt die Fixierung des Metallkomplexfarbstoffs auf dem Polyamidanteil durch Thermosolieren, wobei das Gewebe während 30 bis 120 Sekunden auf Temperaturen von 190 bis 230°C trocken erhitzt wird. Dies geschieht z. B. mit Hilfe eines Spannrahmens oder in einer Thermo-Hotflue mit oder auch ohne Breitenkontrolle. Andere Möglichkeiten sind die Zylinderfixierung (ölbeheizte aneinander und übereinander gereihte Trockenzylinder) oder auch die Anwendung von Siebtrommeltrocknern.
The implementation of the dyeing process according to the invention is, for. B. as follows:
  • The cellulose / polyamide blend, for example a 1: 1 mixture of cotton and polyamide, especially polyamide, 6.6, is first impregnated with the padding liquor. Depending on the depth of the desired color, this contains about 50 g / l of dye, about 10 g / l of fatty alcohol ethoxylate and expediently about 5 g / l of migration inhibitor. The fabric is then squeezed to a liquor absorption of about 60% and dried in between. This intermediate drying can, for. B. with dry air at 100-130 ° C. Then the metal complex dye is fixed on the polyamide portion by thermosolating, the fabric being heated dry to temperatures of 190 to 230 ° C. for 30 to 120 seconds. This happens e.g. B. with the help of a tenter or in a thermal hotflue with or without width control. Other options are cylinder fixing (oil-heated drying cylinders lined up and one above the other) or the use of screen drum dryers.

Es schliesst sich die Fixierung des Küpenfarbstoffs an. Dazu durchläuft das Gewebe zunächst ein Chemikalienbad, wo der Küpenfarbstoff im Alkalischen mittels Hydrosulfit in die wasserlösliche Leukoform überführt wird. Dann tritt das Gewebe in den luftfreien Dämpfer ein, wo ca. 1 Minute bei 100°C (Sattdampf) gedämpft wird. Nach Verlassen des Dämpfers gelangt das Gewebe in die Breitwaschmaschine, wo durch Spülen, Oxidieren und Seifen die Färbung fertiggestellt wird.This is followed by the fixation of the vat dye. To do this, the fabric first passes through a chemical bath, where the vat dye in alkaline is converted into the water-soluble leuco form using hydrosulfite. Then the fabric enters the air-free steamer, where steaming takes about 1 minute at 100 ° C (saturated steam). After leaving the steamer, the fabric goes into the wide washing machine, where the dyeing is completed by rinsing, oxidizing and soaping.

Die mit der Kombination Küpenfarbstoff/Metallkomplexfarbstoff auf Cellulose/Polyamid-Mischgewebe in Gegenwart der spezifischen Tenside nach vorliegendem Verfahren erzielten Färbungen zeichnen sich durch hervorragende Allgemeinechtheiten aus, insbesondere durch eine sehr gute Licht- und Wetterechtheit und sehr gute Nassechtheiten. Darüber hinaus und vor allem ist das erfindungsgemässe Verfahren bestens geeignet, um grosse Metragen zu färben; dies stellt gegenüber dem eingangs genannten Stand der Technik einen Zeitgewinn dar, ist kostengünstiger und spart zudem Energie, bei gleichzeitig besserer Nuancenkonformität. Überraschend ist zudem, dass die Färbung des Polyamidanteils durch die nachfolgende Entwicklung des Küpenfarbstoffs auf der Baumwollfaser nicht geschädigt wird. Die mit dem Metallkomplexfarbstoff gefärbte Polyamid-Faserkomponente übersteht die Behandlung mit dem Reduktionsmittel weitgehend unbeschadet; es kommt praktisch zu keiner Zerstörung des Farbstoffs und zu keiner Farbverschiebung.The dyeings obtained with the combination vat dye / metal complex dye on cellulose / polyamide blended fabric in the presence of the specific surfactants according to the present process are distinguished by excellent general fastness properties, in particular by very good light and weather fastness and very good wet fastness properties. In addition, and above all, the method according to the invention is ideally suited for dyeing large quantities; Compared to the prior art mentioned at the outset, this saves time, is more cost-effective and also saves energy, while at the same time improving shade conformity. It is also surprising that the coloring of the polyamide portion is not damaged by the subsequent development of the vat dye on the cotton fiber. The polyamide fiber component dyed with the metal complex dye survives the treatment with the reducing agent largely without damage; there is practically no destruction of the dye and no color shift.

Die folgenden Beispiele dienen der Veranschaulichung der Erfindung. Die Mengenangaben beziehen sich bei den Farbstoffen auf die handelsübliche, d.h, coupierte Ware.The following examples serve to illustrate the invention. The quantities given for the dyes relate to the commercially available, i.e. coupéed goods.

Beispiel 1:Example 1:

Mischgewebe aus 50 % Polyamid 6.6 und 50 % Baumwolle wird auf einer Kontinueanlage nach dem Thermosol-Padsteam-Verfahren gefärbt. Die Klotzflotte enthält die folgenden Farbstoffe und Hilfsmittel, wobei sich die Mengenangaben jeweils auf 1 Liter Flotte beziehen: 5 g C.I. Vat Orange 11 C.I. 70805, 5,5 g C.I. Vat Green C.I. 69510, 23 g C.I. Vat Black 25 C.I. 69525, 3 g C.I. Acid Yellow 220 C.I. 11714, ferner 2 g Farbstoff der Formel

Figure imgb0001
und 14 g Farbstoff der Formel II
Figure imgb0002
sowie 10 g Fettalkoholäthoxylat der Formel R-O-(CH2CH2O),H mit R = Alkyl C11-18 und n im Mittel = 18; (MG-r1050), 5 g 2-Acrylamido-2-methylpropansulfonsäure-Polymerisat als Kaliumsalz (Migrationsinhibitor) und 2 g Natriumdihydrogenphosphat. Der pH der Klotzflotte wird durch Zusatz von Essigsäure auf 5,5 eingestellt. Nachdem das Textilmaterial mit der Klotzflotte der angegebenen Zusammensetzung imprägniert wurde (Flottenaufnahme 60 %) erfolgt eine Zwischentrocknung (Hotflue, Temp. 110-130° C) und anschliessend die Thermosolierung in einer Thermo-Hotflue während 1 Minute bei 210-220°C. Anschliessend durchläuft die Gewebebahn die Pad-Steam-Anlage, wo die Fixierung der Küpenfarbstoffe erfolgt. Die Ware gelangt zunächst in die Chemikalienflotte, welche die zur Reduktion der Küpenpigmente nötigen Mengen an Alkali z. B. Natronlauge und Hydrosulfit enthält. Dann tritt die Ware in den luftfreien Dämpfer ein, wo 1 Minute bei 100° C (Sattdampf) gedämpft wird. Nach Verlassen des Dämpfers durchläuft das Textilmaterial die einzelnen Abteile einer Breitwaschmaschine, wo die Färbung durch Spülen, Oxidieren und Seifen fertiggestellt wird. Man erhält ein gleichmässig olive gefärbtes Textilmaterial mit ausgezeichneter Wetter- und Lichtechtheit und hervorragenden Nassechtheiten.Blended fabrics made of 50% polyamide 6.6 and 50% cotton are dyed on a continuous system using the Thermosol Padsteam process. The padding liquor contains the following dyes and auxiliaries, the amounts given refer to 1 liter of liquor: 5 g CI Vat Orange 11 CI 70805, 5.5 g CI Vat Green CI 69510, 23 g CI Vat Black 25 CI 69525, 3 g CI Acid Yellow 220 CI 11714, further 2 g of dye of the formula
Figure imgb0001
 and 14 g of dye of the formula II
Figure imgb0002
 and 10 g of fatty alcohol ethoxylate of the formula RO- (CH 2 CH 2 O), H with R = alkyl C 11-18 and n on average = 18; (MG-r1050), 5 g of 2-acrylamido-2-methylpropanesulfonic acid polymer as potassium salt (migration inhibitor) and 2 g sodium dihydrogen phosphate. The pH of the padding liquor is adjusted to 5.5 by adding acetic acid. After the textile material has been impregnated with the padding liquor of the specified composition (liquor absorption 60%), intermediate drying (hotflue, temp. 110-130 ° C) and then thermal insulation in a thermo-hotflue for 1 minute at 210-220 ° C. The fabric web then runs through the pad-steam system, where the vat dyes are fixed. The goods first enter the chemical fleet, which contains the amounts of alkali required to reduce vat pigments. B. sodium hydroxide solution and hydrosulfite. Then the goods enter the air-free steamer, where steaming takes place for 1 minute at 100 ° C (saturated steam). After leaving the steamer, the textile material runs through the individual compartments of a wide washing machine, where the dyeing is completed by rinsing, oxidizing and soaping. A uniform olive-colored textile material with excellent weather and light fastness and excellent wet fastness properties is obtained.

Beispiele 2 bis 6:Examples 2 to 6:

Verfährt man, wie im Beispiel 1 beschrieben, verwendet jedoch eine Klotzflotte, die anstelle des Fettalkoholäthoxylats, in gleicher Menge (10 g/Liter Klotzflotte) eines der folgenden nichtionischen Tenside enthält, so erhält man ebenfalls ein gleichmässig olive gefärbtes Textilmaterial mit ausgezeichneter Wetter-und Lichtechtheit und hervorragenden Nassechtheiten.If the procedure described in Example 1 is followed, however, a padding liquor is used which, instead of the fatty alcohol ethoxylate, contains the same amount (10 g / liter padding liquor) of one of the following nonionic surfactants, this also gives a uniform olive-colored textile material with excellent weather and Light fastness and excellent wet fastness.

Beispiel nichtionisches TensidExample of nonionic surfactant

  • 2 N-Stearyl-N',N"-bis(phenylhydroxyäthyl)-diäthylentriamin umgesetzt mit 106 Mol Äthylenoxid (30 %-ige wässrige Lösung).2 N-stearyl-N ', N "-bis (phenylhydroxyethyl) -diethylenetriamine reacted with 106 moles of ethylene oxide (30% aqueous solution).
  • 3 CZO/C22-Fettamin umgesetzt mit 34,5 Mol Äthylenoxid (33 %-ige wässrige Lösung).3 CZO / C22 fatty amine reacted with 34.5 mol ethylene oxide (33% aqueous solution).
  • 4 p-tert.Octylphenol umgesetzt mit 8,2 Mol Äthylenoxid.4 p-tert.Octylphenol reacted with 8.2 mol of ethylene oxide.
  • 5 Stearylalkohol umgesetzt mit 36 Mol Äthylenoxid.5 stearyl alcohol reacted with 36 moles of ethylene oxide.
  • 6 Polyäthylenglykol MG 400.6 MG 400 polyethylene glycol.

Claims (8)

1. A thermosol pad-steam process for the continuous dyeing of cellulose/polyamide blend fabrics, using a pad liquor which contains at least one vat dye and at least one metal complex dye and optionally further auxiliaries, wherein the pad liquor contains a non-ionic surfactant or a mixture of non-ionic surfactants.
2. A process according to claim 1, wherein the non-ionic surfactant is an alkylphenol ethoxylate, a fatty alcohol ethoxylate, a fatty acid ethoxylate or a fatty amine ethoxylate, each having a molecular weight of 500 to 10 000, or a polyethylene glycol having a molecular weight of 200 to 6000.
3. A process according to claim 2, wherein the non-ionic surfactant is a fatty alcohol ethoxylate having a molecular weight of 800 to 1500.
4. A process according to claim 1, wherein the no-ionic surfactant is added to the pad liquor in an amount of 2 to 50 g/I, in particular 5 to 20 g/I.
5. A process according to claim 1, wherein the vat dyes used are from the class of the anthrimides, anthrimidecarbazoles, anthraquinones and/or phthaloylacridines, and the metal complex dyes used are 1 : 2 metal complex dyes.
6. A process according to claim 1, wherein migration inhibitors, buffer substances, acids and/or light stabilisers are used as further auxiliaries.
7. A pad liquor for carrying out the process according to claim 1, which liquor contains one or more vat dyes, one or more metal complex dyes, and optionally further auxiliaries, wherein the pad liquor contains a non-ionic surfactant or mixture of surfactants.
8. A pad liquor according to claim 7, which contains a migration inhibitor as a further auxiliary.
EP85810011A 1984-01-23 1985-01-17 Process for the continuous dyeing of cellulosic/polyamide blended fabrics Expired EP0151552B1 (en)

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CH284/84 1984-01-23

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GB896019A (en) * 1957-12-13 1962-05-09 Sandoz Ltd Improvements in or relating to the dyeing of polyamide fibers
FR1297776A (en) * 1961-05-04 1962-07-06 Sandoz Sa Mixed fabric dyeing and printing process
US3653801A (en) * 1967-08-29 1972-04-04 Du Pont Pad-acid steam nylon-cotton blend with acid and vat dyes
US3706525A (en) * 1971-03-08 1972-12-19 Du Pont Water swollen cellulose dyeing with high molecular weight disperse dye in a glycol ether solution
DE2156639B2 (en) * 1971-11-15 1978-07-20 Chemische Fabrik Tuebingen R. Beitlich, 7400 Tuebingen Process for the production of soft, elastic, non-chipping and easily washable thickener films
DE2334014A1 (en) * 1972-07-06 1974-01-24 Sandoz Ag Dyeing polyamide/cellulose blends - using anionic dye/leuco ester in acid bath
IT7823117A0 (en) * 1978-05-08 1978-05-08 Acna COLD DYEING PROCEDURE OF CELLULOSIC FIBERS WITH VAT DYES USING SUBSTANCES THAT SWELL THE FIBERS THEMSELVES.
DE2921949A1 (en) * 1979-05-30 1980-12-11 Hoechst Ag METHOD FOR EVENLY COLORING PIECE PRODUCTS FROM MIXTURES OF CELLULOSE FIBERS WITH SYNTHETIC POLYAMIDE FIBERS BY A BLOCK-DAMPING PROCESS

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