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EP0055694B1 - Process for dyeing or printing cellulosic materials and mixed cellulose/polyester fabrics - Google Patents

Process for dyeing or printing cellulosic materials and mixed cellulose/polyester fabrics Download PDF

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Publication number
EP0055694B1
EP0055694B1 EP81810513A EP81810513A EP0055694B1 EP 0055694 B1 EP0055694 B1 EP 0055694B1 EP 81810513 A EP81810513 A EP 81810513A EP 81810513 A EP81810513 A EP 81810513A EP 0055694 B1 EP0055694 B1 EP 0055694B1
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Prior art keywords
vatting
hydrogen
accelerator
group
alkyl
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EP81810513A
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German (de)
French (fr)
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EP0055694A2 (en
EP0055694A3 (en
Inventor
Zdenek Koci
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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
    • D06P1/221—Reducing systems; Reducing catalysts
    • 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
    • D06P1/30—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 sulfur dyes

Definitions

  • the invention relates to a process for dyeing or printing cellulosic materials or cellulose / polyester blended fabrics using specific organic vatting accelerators, also vat or sulfur dye preparations which contain vatting accelerators of this type, and dye baths, printing pastes and reduction baths for carrying out the process.
  • reducing agents for single-bath dyeing of cellulose-containing textile material with vat and / or sulfur dyes DE-A-2 350 961.
  • the combination consists of a reducing agent obtained by condensing ketones with sodium dithionite and basic nitrogen-containing compounds and nitrophenol. This specific combination of reducing agents enables the dyeing of cellulose textile material by the one-bath block-steaming process or by the cold residence process.
  • FR-A-2 250 848 describes a process for dyeing polyamide fiber material with sulfur dyes.
  • Polyamide materials are difficult or impossible to dye with the sulfur dyes that are commonly used.
  • esters of aromatic or aliphatic carboxylic acids for example benzoic acid or terephthalic acid esters or also acetic acid or propionic acid esters.
  • FR-A-1 393 050 a process for dyeing or printing cellulose fiber material with water-soluble sulfur dyes is known.
  • the dyes are then applied in the form of an aqueous preparation which, in addition to the dye, contains a compound having a thiocarbonyl and / or sulfhydryl function or can be converted into a thiocarbonyl derivative or thiol.
  • a compound having a thiocarbonyl and / or sulfhydryl function or can be converted into a thiocarbonyl derivative or thiol.
  • Examples include thioacetamide, thiourea, 2,4,6-trimercapto-1,3,5-triazine, mercaptobenzothiazole, dithiocarbamic acid or esters of thiocarbamic acid.
  • vatting accelerators A whole series of compounds and their use as vatting accelerators are thus described in the prior art, but only a few substances have a sufficient range of use and enable a sufficiently good and rapid distribution of the vat and sulfur dyes in the dye liquor, printing paste or corresponding preparation forms.
  • the aids are tailored to a small class of dyes or special dyeing processes.
  • the known linking accelerators e.g. are difficult to access synthetically or have other disadvantages, e.g. insufficient effectiveness with different dyeing processes (e.g. poor effectiveness in the pad-steam dyeing process compared to printing), high price and sometimes dark inherent color e.g. of many quinone compounds, as well as nuances, such as. B. when using anthraquinones.
  • the heavy metal compounds or thiourea they are less suitable from an ecological point of view and polyamines are only effective at high concentrations in the dye bath.
  • the object of the invention was therefore to find vatting accelerators which do not have the disadvantages mentioned above and to develop a dyeing or printing process for cellulose and cellulose / polyester blended fabrics according to which a rapid and as complete as possible even with fast-running continuous dyeing processes The dyes are reduced, thus ensuring a good color yield.
  • vatting accelerators or mixtures thereof are used as described below.
  • These specific vatting accelerators are known per se as antioxidants, have an excellent effectiveness, are inexpensive and do not have the disadvantages mentioned at the outset. They can either be present in a vat or sulfur dye preparation, or can be added to the dye bath or reduction bath or the printing paste.
  • R 1 , R 2 and R 3 in the meaning of a C 1 -C 12 alkyl group can be unbranched or branched. It is, for example, the methyl group, ethyl group, n-propyl group, isopropyl group, the n-, sec- or tert-butyl group, the n-, sec- or tert-amyl group, the n-, sec. or tert-hexyl group, the n-, sec- or tert-octyl group or the n-, sec- or tert-dodecyl group.
  • R 1 , R 2 and R 3 represent, for example, the methoxy, ethoxy, n- or iso-propoxy and n- or iso-butoxy group.
  • benzyl radical or Phenethyl radicals are suitable, for example: halogen, such as F, CI or Br, the OH group, C 1 -C 12 alkyl, preferably C 1 -C 4 alkyl (branched or unbranched) or C 1 -C 4 alkoxy (branched or unbranched).
  • the substituents R 1 to R 3 have the following meanings: C 1 to C 5 alkyl, -CH 2 0H, hydrogen, halogen, OH, C 1 to C 4- alkoxy, benzyl, Cyclohexyl or the group again with the condition that if one of the radicals R 1 , R 2 or R 3 is -OH or -CH 3 , at most one of the remaining two radicals is hydrogen and also with the proviso that all three radicals R 1 to R 3 are not mean hydrogen at the same time.
  • vatting accelerators of the formula (A) are used in which the radicals R 1 to R 3 are independently of one another: C 1 to C 4 alkyl, hydrogen, chlorine, hydroxy or benzyl, with the condition that R 1 , R 2 and R 3 do not simultaneously represent hydrogen and furthermore, in the event that one of the radicals R 1 to R 3 is an —OH or CH 3 group, means at most one of the remaining two radicals hydrogen.
  • the type (A) compounds mentioned are known and can be prepared by known methods.
  • a further class of compounds are the compounds of group (A) which are linked to an organic radical via a bridge member R ' 3 instead of the substituent R 3 .
  • These are compounds of the formula organic radical in which R 1 and R 2 have the meaning given above, m is a number 1 or 2 and R ' 3 is any bridging element, for example the radical of an inorganic or organic acid or the radical of an aldehyde, a styrene or an olefin, and preferably a Group in which R 4 is independently hydrogen or C 1 -C 4 alkyl.
  • R 1 , R z and R ' 3 have the meanings given above and X is an aliphatic bridge member, preferably - (CH 2 ) 2 COO-CH 2 , m is a number 1 or 2 and n is a number 1 to 4 and p is a number 1 to 3 mean.
  • This group includes the partial or full esters of compounds of type (A) with inorganic and organic acids, e.g. with phosphoric acid, corresponding mono-, di- or trisphosphites, or with isocyanuric acid.
  • inorganic and organic acids e.g. with phosphoric acid, corresponding mono-, di- or trisphosphites, or with isocyanuric acid.
  • Such connections are e.g. the tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite.
  • Group B also includes those compounds which are formed by condensation of compounds of type A with, for example, aldehydes, such as formaldehyde or crotonaldehyde, or also reaction products of compounds (A) with, for. B. styrene and its derivatives or with olefins.
  • A is the direct bond or a divalent bridge member of the formula where R 4 is independently hydrogen or C 1 -C 4 alkyl, and R s and R 6 are independently: C 1 -C 12 alkyl, C 3 -C 12 alkenyl, halogen, C 1 -C 4 - Alkoxy, optionally substituted phenyl, cyclohexyl, benzyl, phenethyl, hydrogen, S0 3 H, COOH or CONH 2 .
  • Preferred from these classes of compounds (A) and (B) are those compounds which contain a sterically hindered phenol group, in particular those in which the o-position to the OH group is occupied by a tertiary alkyl radical.
  • R 11 is a C 1 -C 4 -alkyl group or a C 1 -C 3 -alkoxy group, this can be unbranched or branched.
  • R 12 is a C 1 -C 12 alkyl group, this can be unbranched or branched; for example, the methyl, ethyl, n or iso-hexyl and n or iso-octyl group are mentioned.
  • these are dihydroxy and, on the other hand, hydroxyamino naphthalenes, where the two OH or. OH and NH 2 groups are preferably in the 1,6, 1,8, 2,5 and 2,7 positions.
  • R 16 represents an unbranched or branched C 1 -C 4 alkyl group, such as the methyl, ethyl, n or iso-propyl or n, sec. or tert-butyl group. These compounds are known and can be prepared by known methods. A preferred compound from this class is 4-hydroxy-acetophenone.
  • Z is independently a bridge member of the formula or p is a number from 2-6, R 28 and R 29 independently of one another hydrogen, C 1 -C 6 alkyl (unbranched or branched) or C 1 -C 3 alkoxy (unbranched or branched), R 23 , R 24, R 2s and R 27 independently of one another hydrogen, C 1 -C 12 alkyl (unbranched or branched), C 1 -C 12 hydroxyalkyl, optionally substituted phenyl or cyclohexyl, a- or ⁇ -naphthyl or benzyl and R 26 C 1 -C 12 -alkyl (unbranched or branched) or optionally substituted phenyl, a- or ⁇ -naphthyl; Cyclohexyl or benzyl, where R 21 and R 24 or R 25 and R 26 do not simultaneously denote hydrogen, with the condition that when Z is - (CH 2 ) p-, R 23 ,
  • R 23 , R 24 , R 25 , R 26 and R 17 OH, halogen (F, Cl, Br), NH 2 and C 1 -C 4 alkyl.
  • R 30 represents an unbranched or branched C 1 -C 12 alkyl group, such as the methyl, ethyl, n or iso-propyl, n or iso-hexyl or n or iso-octyl group.
  • the compounds mentioned under A) to I) are generally easily accessible and are notable for good distributability in the dye preparations, dye baths or reduction baths and printing pastes.
  • the compounds mentioned should be water-soluble and / or soluble in an alkaline reductive bath (ph ⁇ 12). If they do not meet these solubility requirements, it is advisable to use these compounds before their use, e.g. to be ground with an anionic dispersing agent to a grain size of ⁇ 5 ⁇ m, in particular about 11 m. In principle, this is done in such a way that the vatting accelerator or a mixture thereof with a dispersant, e.g.
  • naphthalenesulfonic acid / formaldehyde condensation product for example by joint wet grinding in a corundum disk mill, ball mill, agitator mill, sand mill or other grinding units, optionally with subsequent drying of the mixture, e.g. in an atomizing dryer.
  • the phenols and amines according to groups A), B), C) and G) are preferably used as vatting accelerators.
  • vatting accelerators are advantageously used in an amount of 0.5 to 10% by weight, based on the dye, or in an amount of 0.05 to 1 g per liter of reduction bath.
  • the term process for dyeing or printing cellulosic materials or cellulose / polyester blended fabrics in the present case is to be understood as general dyeing and printing processes with which vat and sulfur dyes are normally applied to the textile materials mentioned.
  • the dyeing process is both a pull-out and a continuous process.
  • pull-out process in the jigger, in the reel runner and in the jet dyeing machine the pad-jig process, the standfast process, the semi-pigmentation process, the block fixing process, e.g. B. the Einbadklotzdampf psychologist, the pad-roll process, the pad-roll process with intermediate drying, the wet steam process and especially the pad-steam process.
  • As printing processes e.g. called: single-phase and two-phase development processes.
  • the vatting accelerators are contained in the preparations in a concentration of 0.1 to 20% by weight, in particular 0.5 to 10% by weight, based on the dye.
  • the dye preparations usually also contain anionic dispersants or possibly nonionic fillers, preferably in amounts of 0.5 to 80% by weight. Dispersants of this type are primarily used as described in DE-A-2 816 539. Further additives are the auxiliaries generally contained in dye preparations, such as humectants, antifoams, preservatives, wetting agents, leveling agents, thickeners, etc.
  • vat and sulfur dyes are primarily indanthrones, flavanthrones, pyranthrones, violanthrones, isoviolanthrones, benzanthrones, nitrogen-substituted imides of perylene tetracarboxylic acid, acridones, anthraquinone oxazoles, anthraquinone thiazoles and compounds that are derived primarily from anthraquinone.
  • the invention also relates to the dye baths and printing pastes, and the reduction baths as such.
  • the dyebaths or printing pastes are produced in a simple manner by dissolving a vat or sulfur dye preparation which already contains the vatting accelerator in the dyebath or by incorporating them in a suitable thickener.
  • the textile material can also initially only be impregnated or printed with the dye, then optionally dried and then the dye on the fabric can be vetted in a reduction bath containing the vatting accelerator.
  • the linking accelerators are substances which belong to the compound classes already described in detail. The compounds are used individually or in a mixture, specifically per liter of reduction bath in an amount of 0.01 to 5 g, preferably 0.05 to 1 g.
  • the reduction baths contain, in addition to the vatting accelerator, a reducing agent, e.g. B. sodium dithionite, sodium formaldehyde sulfoxylate of thiourea dioxide, and alkali, especially sodium hydroxide solution or potassium hydroxide solution.
  • a reducing agent e.g. B. sodium dithionite, sodium formaldehyde sulfoxylate of thiourea dioxide, and alkali, especially sodium hydroxide solution or potassium hydroxide solution.
  • Parts mean parts by weight.
  • the cotton fabric is then steamed in the steamer at 100 ° C for 30 seconds. Then rinsed as usual, with 3 ml / l H 2 0 2 30%, oxidized for 15 minutes at 50 ° C, rinsed and for 15 minutes at cooking temperature with 2 g / i of an anionic detergent and 1 g / l soda calc. soaped. A blue coloration is obtained which is more intense in color than a comparison coloration without the addition of 30% aqueous dispersion of tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate ]-methane.
  • Washed-out cotton fabric is padded with this dye liquor and treated as in Example 4 until the dyeing is finished.

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Description

Die Erfindung betrifft ein Verfahren zum Färben oder Bedrucken von Cellulosematerialien bzw. von Cellulose/Polyester-Mischgewebe unter Verwendung spezifischer organischer Verküpungsbeschleuniger, ferner Küpen- oder Schwefelfarbstoffzubereitungen, die derartige Verküpungsbeschleuniger enthalten, sowie Färbebäder, Druckpasten und Reduktionsbäder zur Durchführung des Verfahrens.The invention relates to a process for dyeing or printing cellulosic materials or cellulose / polyester blended fabrics using specific organic vatting accelerators, also vat or sulfur dye preparations which contain vatting accelerators of this type, and dye baths, printing pastes and reduction baths for carrying out the process.

Es sind zahlreiche Verfahren bekannt, nach denen die Farbausbeute beim Färben und Bedrukken von Cellulosematerialien mit Küpen- und Schwefelfarbstoffen durch den Zusatz von Verküpungsbeschleunigern, meistens Oxidationsmitteln, verbessert wird. Eine zusammenfassende Übersicht findet sich z.B. in der DE-A-1 469 670. In der DE-A-2 252 944 wird in diesem Zusammenhang die Verwendung von chinoiden Verbindungen wie Benzochinon, Naphthochinon und Anthrachinon sowie deren Derivate beschrieben. Weiterhin ist für denselben Zweck aus den DE-C-1 239269. FR-B-1 314630 und 1 353 730 die Verwendung von anorganischen und organischen Schwermetallverbindungen bekannt und in der GB-B-1 130 908 wird die Verwendung von aliphatischen und aromatisch-aliphatischen primären Diaminen oder Polyaminen empfohlen.Numerous processes are known by which the color yield when dyeing and printing cellulose materials with vat and sulfur dyes is improved by adding vatting accelerators, mostly oxidizing agents. A summary overview can be found e.g. in DE-A-1 469 670. DE-A-2 252 944 describes the use of quinoid compounds such as benzoquinone, naphthoquinone and anthraquinone and their derivatives in this connection. Furthermore, for the same purpose from DE-C-1 239269. FR-B-1 314630 and 1 353 730 the use of inorganic and organic heavy metal compounds is known and in GB-B-1 130 908 the use of aliphatic and aromatic aliphatic primary diamines or polyamines recommended.

Bekannt ist ferner eine Reduktionsmittelkombination zum einbadigen Färben von Cellulose enthaltendem Textilmaterial mit Küpen- und/oder Schwefelfarbstoffen (DE-A-2 350 961). Die Kombination besteht aus einem Reduktionsmittel, das durch Kondensation von Ketonen mit Natriumdithionit und basischen Stickstoff enthaltenden Verbindungen erhalten wird und Nitrophenol. Diese spezifische Reduktionsmittelkombination ermöglicht das Färben von Cellulose-Textilmaterial nach dem Einbad-Klotz-Dämpf-Verfahren oder nach dem Kalt-Verweilverfahren.Also known is a combination of reducing agents for single-bath dyeing of cellulose-containing textile material with vat and / or sulfur dyes (DE-A-2 350 961). The combination consists of a reducing agent obtained by condensing ketones with sodium dithionite and basic nitrogen-containing compounds and nitrophenol. This specific combination of reducing agents enables the dyeing of cellulose textile material by the one-bath block-steaming process or by the cold residence process.

Weiter ist in der FR-A-2 250 848 ein Verfahren zum Färben von Polyamid-Fasermaterial mit Schwefelfarbstoffen beschrieben. Polyamidmaterialien lassen sich nicht oder nur schwer mit den üblicherweise verwendeten Schwefelfarbstoffen anfärben. Um dennoch auf Polyamidfasern Färbungen mit dieser Farbstoffklasse zu erhalten, wird in dieser Literaturstelle vorgeschlagen, dem Färbebad Ester aromatischer oder aliphatischer Carbonsäuren zuzusetzen, beispielsweise Benzoesäure- oder Terephthalsäureester oder auch Essigsäure- oder Propionsäureester.Furthermore, FR-A-2 250 848 describes a process for dyeing polyamide fiber material with sulfur dyes. Polyamide materials are difficult or impossible to dye with the sulfur dyes that are commonly used. In order to obtain dyeings with this class of dyes on polyamide fibers, it is proposed in this reference to add esters of aromatic or aliphatic carboxylic acids to the dyebath, for example benzoic acid or terephthalic acid esters or also acetic acid or propionic acid esters.

Schliesslich ist aus der FR-A-1 393 050 ein Verfahren zum Färben oder Bedrucken von Cellulose-Fasermaterial mit wasserlöslichen Schwefelfarbstoffen bekannt. Danach werden die Farbstoffe in Form einer wässrigen Präparation appliziert, die neben dem Farbstoff eine Verbindung mit einer Thiocarbonyl- und/oder Sulfhydrylfunktion enthält oder in ein Thiocarbonylderivat oder Thiol überführbar ist. Genannt sind beispielsweise Thioacetamid, Thioharnstoff, 2,4,6-Trimercapto-1,3,5-triazin, Mercaptobenzthiazol, Dithiocarbaminsäure oder Ester der Thiocarbaminsäure.Finally, from FR-A-1 393 050 a process for dyeing or printing cellulose fiber material with water-soluble sulfur dyes is known. The dyes are then applied in the form of an aqueous preparation which, in addition to the dye, contains a compound having a thiocarbonyl and / or sulfhydryl function or can be converted into a thiocarbonyl derivative or thiol. Examples include thioacetamide, thiourea, 2,4,6-trimercapto-1,3,5-triazine, mercaptobenzothiazole, dithiocarbamic acid or esters of thiocarbamic acid.

Im Stand der Technik sind somit eine ganze Reihe von Verbindungen und deren Verwendung als Verküpungsbeschleuniger beschrieben, jedoch nur wenige Substanzen haben eine ausreichende Anwendungsbreite und ermöglichen eine hinreichend gute und rasche Verteilung der Küpen- und Schwefelfarbstoffe in der Farbstoffflotte, Druckpaste oder entsprechenden Zubereitungsformen. Vielfach sind die Hilfsmittel auf eine kleine Klasse von Farbstoffen oder besondere Färbeverfahren abgestimmt. Hinzu kommt, dass die bekannten Verküpungsbeschleuniger z.B. präparativ schwer zugänglich sind, oder andere Nachteile aufweisen, wie z.B. eine ungenügende Wirksamkeit bei unterschiedlichen Färbeverfahren (z.B. schlechte Wirksamkeit im Pad-Steam-Färbeverfahren im Vergleich zum Druck), hoher Preis und teilweise dunkle Eigenfarbe z.B. von vielen Chinonverbindungen, sowie Nuancenänderungen, wie z. B. bei der Verwendung von Anthrachinonen. Was die Schwermetallverbindungen anbetrifft oder auch Thioharnstoff, so sind diese aus ökologischer Sicht weniger gut geeignet und Polyamine sind erst bei hohen Konzentrationen im Färbebad wirksam.A whole series of compounds and their use as vatting accelerators are thus described in the prior art, but only a few substances have a sufficient range of use and enable a sufficiently good and rapid distribution of the vat and sulfur dyes in the dye liquor, printing paste or corresponding preparation forms. In many cases, the aids are tailored to a small class of dyes or special dyeing processes. In addition, the known linking accelerators e.g. are difficult to access synthetically or have other disadvantages, e.g. insufficient effectiveness with different dyeing processes (e.g. poor effectiveness in the pad-steam dyeing process compared to printing), high price and sometimes dark inherent color e.g. of many quinone compounds, as well as nuances, such as. B. when using anthraquinones. As for the heavy metal compounds or thiourea, they are less suitable from an ecological point of view and polyamines are only effective at high concentrations in the dye bath.

Aufgabe der Erfindung war es daher, Verküpungsbeschleuniger zu finden, die die oben genannten Nachteile nicht aufweisen und ein Färbe- bzw. Druckverfahren für Cellulose und Cellulose/ Polyester-Mischgewebe zu entwickeln, gemäss dem auch bei schnell ablaufenden Kontinue-Färbeverfahren eine rasche und möglichst vollständige Reduktion der Farbstoffe erfolgt, und damit eine gute Farbausbeute gewährleistet ist.The object of the invention was therefore to find vatting accelerators which do not have the disadvantages mentioned above and to develop a dyeing or printing process for cellulose and cellulose / polyester blended fabrics according to which a rapid and as complete as possible even with fast-running continuous dyeing processes The dyes are reduced, thus ensuring a good color yield.

Die Lösung dieser Aufgabe besteht darin, dass man zur Verbesserung der Verküpbarkeit von Küpen- und Schwefelfarbstoffen beim Färben oder Bedrucken von cellulosehaltigen Textilmaterialien, vor allem Baumwolle oder Mischgewebe aus Baumwolle/Polyester, spezifische Verküpungsbeschleuniger bzw. Mischungen davon wie im folgenden beschrieben einsetzt. Diese spezifischen Verküpungsbeschleuniger sind an sich als Antioxydantien bekannt, besitzen eine ausgezeichnete Wirksamkeit, sind günstig im Preis und weisen die eingangs genannten Nachteile nicht auf. Sie können entweder in einer Küpen- oder Schwefelfarbstoffzubereitung vorhanden sein, oder dem Färbebad bzw. Reduktionsbad oder der Druckpaste zugesetzt werden.The solution to this problem is that to improve the viability of vat and sulfur dyes when dyeing or printing cellulosic textile materials, especially cotton or blended fabrics made of cotton / polyester, specific vatting accelerators or mixtures thereof are used as described below. These specific vatting accelerators are known per se as antioxidants, have an excellent effectiveness, are inexpensive and do not have the disadvantages mentioned at the outset. They can either be present in a vat or sulfur dye preparation, or can be added to the dye bath or reduction bath or the printing paste.

Gegenstand vorliegender Erfindung ist somit ein Verfahren zum Färben oder Bedrucken von Cellulosematerialien bzw. von Cellulose/Polyester-Mischgewebe mit Küpen- oder Schwefelfarbstoffen unter Verwendung von organischen Verküpungsbeschleunigern, das dadurch gekennzeichnet ist, dass als Verküpungsbeschleuniger eine oder ein Gemisch mehrerer Verbindung zur Anwendung gelangt, die mindestens eine aromatische Hydroxygruppe und/oder eine sekundäre oder tertiäre Aminogruppe, eine -CONHOH-Gruppe, oder eine ::::S = O Gruppierung aufweisen, ausgenommen Nitrophenole, und Derivate aromatischer Carbonsäuren mit weniger als 3 aromatischen Hydroxygruppen, und welche man in einer Menge von 0,1 bis 20 Gew.%, bezogen auf Farbstoff, dem Färbebad bzw. der Druckpaste, oder in einer Menge von 0,01 bis 5 g/I dem Reduktionsbad zusetzt.The present invention thus relates to a process for dyeing or printing cellulose materials or cellulose / polyester blended fabrics with vat or sulfur dyes using organic vatting accelerators, which is characterized in that one or a mixture of several compounds is used as vatting accelerator, which have at least one aromatic hydroxy group and / or a secondary or tertiary amino group, a -CONHOH group, or a :::: S = O grouping, with the exception of nitrophenols, and derivatives of aromatic carboxylic acids with less than 3 aromatic hydroxy groups, and which one in an amount of 0.1 to 20% by weight, based on the dye, the dyebath or the printing paste, or in an amount of 0.01 to 5 g / l of the reducing bath.

Bei den Verküpungsbeschleunigern handelt es sich vor allem um folgende Verbindungen:

  • A) Verbindungen der Formel
    Figure imgb0001
    worin R1, R2 und R3 unabhängig voneinander bedeuten: C1-C12 Alkyl, C3-C12 Alkenyl, -CH2OH, Wasserstoff, Halogen, OH, C1-C4-Alkoxy, gegebenenfalls substituiertes Phenyl, Benzyl oder Phenäthyl, Cyclohexyl, SO3H, COOH, CONH2 oder die Gruppe
    Figure imgb0002
    mit der Bedingung, dass R1, Rz und R3 nicht gleichzeitig Wasserstoff bedeuten und ferner wenn einer der Reste R1, R2 und R3-OH oder-CH3 ist, dann ist höchstens einer der verbleibenden zwei Reste Wasserstoff.
The linking accelerators are primarily the following connections:
  • A) Compounds of the formula
    Figure imgb0001
     wherein R 1 , R 2 and R 3 independently of one another are: C 1 -C 12 alkyl, C 3 -C 12 alkenyl, -CH 2 OH, hydrogen, halogen, OH, C 1 -C 4 alkoxy, optionally substituted phenyl, Benzyl or phenethyl, cyclohexyl, SO 3 H, COOH, CONH 2 or the group
    Figure imgb0002
     with the condition that R 1 , R z and R 3 are not simultaneously hydrogen and furthermore if one of the radicals R 1 , R 2 and R 3 is -OH or -CH 3 , then at most one of the remaining two radicals is hydrogen.

R1, R2 und R3 in der Bedeutung einer C1-C12-Alkylgruppe kann unverzweigt oder verzweigt sein. Es handelt sich beispielsweise um die Methylgruppe, Äthylgruppe, n-Propylgruppe, iso-Propylgruppe, die n-, sec.- oder tert.-Butylgruppe, die n-, sec.- oder tert.-Amylgruppe, die n-, sec.-oder tert.-Hexylgruppe, die n-, sec.- oder tert.-Octylgruppe oder die n-, sec.- oder tert.-Dodecylgruppe. Handelt es sich um eine Alkenylgruppe(C3- C12) so ist beispielsweise n-Propenyl oder die Allylgruppe genannt. Handelt es sich bei R1, R2 und R3 um Halogen so kommt vor allem F, CI oder Br in Frage. In der Bedeutung einer C1-C4 Alkoxygruppe stellen R1, R2 und R3 beispielsweise die Methoxy-, Äthoxy-, n- oder iso-Propoxy- und n-oder iso-Butoxygruppe dar. Als Substituenten im Phenylrest, Benzylrest bzw. Phenäthylrest kommen z.B. in Frage: Halogen, wie F, CI oder Br, die OH-Gruppe, C1-C12- Alkyl, vorzugsweise C1-C4-Alkyl (verzweigt oder unverzweigt) oder C1-C4-Alkoxy (verzweigt oder unverzweigt).R 1 , R 2 and R 3 in the meaning of a C 1 -C 12 alkyl group can be unbranched or branched. It is, for example, the methyl group, ethyl group, n-propyl group, isopropyl group, the n-, sec- or tert-butyl group, the n-, sec- or tert-amyl group, the n-, sec. or tert-hexyl group, the n-, sec- or tert-octyl group or the n-, sec- or tert-dodecyl group. If it is an alkenyl group (C 3 - C 12 ), n-propenyl or the allyl group is mentioned, for example. If R 1 , R 2 and R 3 are halogen, F, CI or Br are particularly suitable. In the meaning of a C 1 -C 4 alkoxy group, R 1 , R 2 and R 3 represent, for example, the methoxy, ethoxy, n- or iso-propoxy and n- or iso-butoxy group. As substituents in the phenyl radical, benzyl radical or Phenethyl radicals are suitable, for example: halogen, such as F, CI or Br, the OH group, C 1 -C 12 alkyl, preferably C 1 -C 4 alkyl (branched or unbranched) or C 1 -C 4 alkoxy (branched or unbranched).

In bevorzugt verwendeten Verbindungen der Formel (A) haben die Substituenten R1 bis R3 die folgende Bedeutung: C1 bis C5-Alkyl, -CH20H, Wasserstoff, Halogen, OH, C1 bis C4-Alkoxy, Benzyl, Cyclohexyl oder die Gruppe

Figure imgb0003
wiederum mit der Bedingung, dass wenn einer der Reste R1, R2 oder R3 -OH oder -CH3 ist, höchstens einer der verbleibenden zwei Reste Wasserstoff bedeutet und ferner mit der Massgabe, dass alle drei Reste R1 bis R3 nicht gleichzeitig Wasserstoff bedeuten.In compounds of formula (A) used with preference, the substituents R 1 to R 3 have the following meanings: C 1 to C 5 alkyl, -CH 2 0H, hydrogen, halogen, OH, C 1 to C 4- alkoxy, benzyl, Cyclohexyl or the group
Figure imgb0003
 again with the condition that if one of the radicals R 1 , R 2 or R 3 is -OH or -CH 3 , at most one of the remaining two radicals is hydrogen and also with the proviso that all three radicals R 1 to R 3 are not mean hydrogen at the same time.

Insbesondere finden im erfindungsgemässen Färbeverfahren solche Verküpungsbeschleuniger der Formel (A) Verwendung, worin die Reste R1 bis R3 unabhängig voneinander bedeuten: C1 bis C4-Alkyl, Wasserstoff, Chlor, Hydroxy oder Benzyl, mit der Bedingung, dass R1, R2 und R3 nicht gleichzeitig für Wasserstoff stehen und ferner, im Fall dass einer der Reste R1 bis R3 eine -OH oder CH3-Gruppe ist, höchstens einer der verbleibenden zwei Reste Wasserstoff bedeutet.In particular, in the dyeing process according to the invention, such vatting accelerators of the formula (A) are used in which the radicals R 1 to R 3 are independently of one another: C 1 to C 4 alkyl, hydrogen, chlorine, hydroxy or benzyl, with the condition that R 1 , R 2 and R 3 do not simultaneously represent hydrogen and furthermore, in the event that one of the radicals R 1 to R 3 is an —OH or CH 3 group, means at most one of the remaining two radicals hydrogen.

Es handelt sich beispielsweise um folgende Verbindungen:

  • 3,5-Di-tert.-butyl-brenzkatechin,
  • Hydrochinon-monobenzyläther,
  • 5-Methyl-resorcin, 4-Cyclohexyl-resorcin,
  • 2,5-Di-(tert.-amyl)-hydrochinon,
  • Tert.-butyl-hydrochinon,
  • 4-Hydroxymethyl-2,6,-di-(tert.-butyl)-phenol
  • und vor allem
  • 4-Chlor-m-kresol, 2,6-Di-tert.-butyl-p-kresol, 2,5-Di-tert.-butyl-hydrochinon
  • und insbesondere
  • 2-Benzyl-4-chlor-phenol.
These are, for example, the following connections:
  • 3,5-di-tert-butyl pyrocatechol,
  • Hydroquinone monobenzyl ether,
  • 5-methyl-resorcinol, 4-cyclohexyl-resorcinol,
  • 2,5-di (tert-amyl) hydroquinone,
  • Tert-butyl hydroquinone,
  • 4-hydroxymethyl-2,6, -di (tert-butyl) phenol
  • and especially
  • 4-chloro-m-cresol, 2,6-di-tert-butyl-p-cresol, 2,5-di-tert-butyl hydroquinone
  • and particularly
  • 2-benzyl-4-chlorophenol.

Die genannten Verbindungen des Typus (A) sind bekannt und können nach bekannten Methoden hergestellt werden.The type (A) compounds mentioned are known and can be prepared by known methods.

B) Eine weitere Verbindungsklasse sind die Verbindungen der Gruppe (A), welche über ein Brückenglied R'3 anstelle des Substituenten R3 an einen organischen Rest angeknüpft sind. Es handelt sich um Verbindungen der Formel

Figure imgb0004
organischer Rest, worin R1 und R2 die oben angegebene Bedeutung haben, m eine Zahl 1 oder 2 und R'3 ein beliebiges Brückenglied wie z.B. der Rest einer anorganische oder organischer Säure oder der Rest eines Aldehyds, eines Styrols oder eines Olefins und vorzugsweise eine
Figure imgb0005
Gruppe darstellt, worin R4 unabhängig voneinander Wasserstoff oder C1-C4- Alkyl bedeutet.B) A further class of compounds are the compounds of group (A) which are linked to an organic radical via a bridge member R ' 3 instead of the substituent R 3 . These are compounds of the formula
Figure imgb0004
 organic radical in which R 1 and R 2 have the meaning given above, m is a number 1 or 2 and R ' 3 is any bridging element, for example the radical of an inorganic or organic acid or the radical of an aldehyde, a styrene or an olefin, and preferably a
Figure imgb0005
 Group in which R 4 is independently hydrogen or C 1 -C 4 alkyl.

Von besonderer Bedeutung sind die Verbindungen der Formel

Figure imgb0006
worin R1, Rz und R'3 die oben angegebenen Bedeutungen haben und X ein aliphatisches Brükkenglied, vorzugsweise -(CH2)2 COO-CH2, m eine Zahl 1 oder 2 und n eine Zahl 1 bis 4 und p eine Zahl 1 bis 3 bedeuten.The compounds of the formula are of particular importance
Figure imgb0006
 wherein R 1 , R z and R ' 3 have the meanings given above and X is an aliphatic bridge member, preferably - (CH 2 ) 2 COO-CH 2 , m is a number 1 or 2 and n is a number 1 to 4 and p is a number 1 to 3 mean.

Zu dieser Gruppe gehören die Teil- oder Vollester von Verbindungen des Typus (A) mit anorganischen und organischen Säuren, wie z.B. mit Phosphorigsäure, entsprechende Mono-, Di- oder Trisphosphite, oder mit Isocyanursäure. Verbindungen dieser Art sind z.B. das Tris(3,5-di-tert.-butyl-4-hydroxyphenyl)-phosphit.This group includes the partial or full esters of compounds of type (A) with inorganic and organic acids, e.g. with phosphoric acid, corresponding mono-, di- or trisphosphites, or with isocyanuric acid. Such connections are e.g. the tris (3,5-di-tert-butyl-4-hydroxyphenyl) phosphite.

Ferner umfasst die Gruppe B auch noch solche Verbindungen, welche durch Kondensation von Verbindungen des Typus A mit beispielsweise Aldehyden, wie Formaldehyd oder Crotonaldehyd, entstehen, oder auch Umsetzungsprodukte der Verbindungen (A) mit z. B. Styrol und seinen Derivaten oder mit Olefinen.Group B also includes those compounds which are formed by condensation of compounds of type A with, for example, aldehydes, such as formaldehyde or crotonaldehyde, or also reaction products of compounds (A) with, for. B. styrene and its derivatives or with olefins.

Als weitere Verbindungen dieser Art sind beispielsweise genannt:

  • 2,2'-Methylen-bis(4-methyl-6-tert.-butyl-phenol),
  • 2,2'-Thio-bis(4-methyl-6-tert: butyl-phenol),
  • Thio-bis(di-sec.-amyl-phenol),und vor allem
  • 4,4'-Methylen-bis(2,6-di-tert.-butyl-phenol), und vorzugsweise
  • Tetrakis [methylen-3-(3',5'-di-tert.-butyl-
  • 4'-hydroxyphenyl)-propionat]-methan der Formel
    Figure imgb0007
Examples of further compounds of this type are:
  • 2,2'-methylene-bis (4-methyl-6-tert-butyl-phenol),
  • 2,2'-thio-bis (4-methyl-6-tert: butylphenol),
  • Thio-bis (di-sec.-amyl-phenol), and above all
  • 4,4'-methylene-bis (2,6-di-tert-butyl-phenol), and preferably
  • Tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-
  • 4'-hydroxyphenyl) propionate] methane of the formula
    Figure imgb0007

Weitere Beispiele der Verbindungen der Klasse (B) in der m = 1 ist, sind Verbindungen der Formel

Figure imgb0008
worin bedeuten:Further examples of the compounds of class (B) in which m = 1 are compounds of the formula
Figure imgb0008
 in which mean:

A die direkte Bindung oder ein zweiwertiges Brückenglied der Formel

Figure imgb0009
wobei R4 unabhängig voneinander Wasserstoff oder C1-C4-Alkyl ist, und Rs und R6 unabhängig voneinander bedeuten: C1-C12- Alkyl, C3-C12-Alkenyl, Halogen, C1-C4-Alkoxy, gegebenenfalls substituiertes Phenyl, Cyclohexyl, Benzyl, Phenäthyl, Wasserstoff, S03H, COOH oder CONH2.A is the direct bond or a divalent bridge member of the formula
Figure imgb0009
 where R 4 is independently hydrogen or C 1 -C 4 alkyl, and R s and R 6 are independently: C 1 -C 12 alkyl, C 3 -C 12 alkenyl, halogen, C 1 -C 4 - Alkoxy, optionally substituted phenyl, cyclohexyl, benzyl, phenethyl, hydrogen, S0 3 H, COOH or CONH 2 .

Bedeutet R4 eine C1-C4 Alkylgruppe, so handelt es sich beispielsweise um die Methyl-, Äthyl-, n-oder iso-Propyl- oder um die n-, sec.- oder tert.-Butylgruppe. Bedeuten R5 und/oder R6 eine C1-C12-Alkylgruppe, so handelt es sich beispielsweise um eine unverzweigte oder verzweigte Alkylgruppe, wie die Methyl-, Äthyl-, n- oder iso-Propyl-, n-, sec.- oder tert.-Butyl-, n- oder iso-hexyl-, n- oder iso-Octyl- oder um die n- oder iso-Dodecylgruppe. Bedeutet Rs und/oder R6 eine C3-C12-Alkenylgruppe, so ist beispielsweise die Allylgruppe genannt. Bedeuten R5 und/oder R6 Halogen, so handelt es sich um Fluor, Chlor oder Brom. Bedeuten Rs und/oder R6 und C,-C4-Alkoxygruppe, so handelt es sich beispielsweise um die Methoxy-, Äthoxy-, n- oder iso-Propoxy- und n-oder iso-Butoxygruppe. Handelt es sich bei R5 und/oder R6 um ein substituiertes Phenyl, so kommen als Substituenten beispielsweise in Frage: Halogen, wie Fluor, Chlor oder Brom, die OH-Gruppe, eine C1-C4 Alkoxygruppe (verzweigt oder unverzweigt) und eine C1-C12-Alkylgruppe (verzweigt oder unverzweigt). Beispielsweise sind genannt:

  • 4,4'-Methylen-bis(phenol),
  • 4,4'-Äthyliden-bis(phenol),
  • 4,4'-Thio-bis(phenol),
  • 4,4'-Thionyl-bis(phenol),
  • 4,4'-Dithio-bis(phenol),
  • 4,4'-Dihydroxystilben,
  • 4,4'-Biphenyldiol und vor allem
  • 4,4'-lsopropyliden-bis(phenol) und
  • 2,2'-Methylen-bis(4-chlor-phenol).
If R 4 is a C 1 -C 4 alkyl group, it is, for example, the methyl, ethyl, n- or iso-propyl group or the n-, sec- or tert-butyl group. If R 5 and / or R 6 are a C 1 -C 12 alkyl group, it is, for example, an unbranched or branched alkyl group, such as the methyl, ethyl, n- or isopropyl, n-, sec. - or tert-butyl, n- or iso-hexyl, n- or iso-octyl or around the n- or iso-dodecyl group. If R s and / or R 6 is a C 3 -C 12 alkenyl group, the allyl group is mentioned, for example. If R 5 and / or R 6 are halogen, it is fluorine, chlorine or bromine. If R s and / or R 6 and C, -C 4 -alkoxy group, it is, for example, the methoxy, ethoxy, n- or iso-propoxy and n- or iso-butoxy group. If R 5 and / or R 6 is a substituted phenyl, the following may be used as substituents: halogen, such as fluorine, chlorine or bromine, the OH group, a C 1 -C 4 alkoxy group (branched or unbranched) and a C 1 -C 12 alkyl group (branched or unbranched). Examples include:
  • 4,4'-methylene-bis (phenol),
  • 4,4'-ethylidene bis (phenol),
  • 4,4'-thio-bis (phenol),
  • 4,4'-thionyl-bis (phenol),
  • 4,4'-dithio-bis (phenol),
  • 4,4'-dihydroxystilbene,
  • 4,4'-biphenyldiol and above all
  • 4,4'-isopropylidene bis (phenol) and
  • 2,2'-methylene-bis (4-chlorophenol).

Bevorzugt aus diesen Verbindungsklassen (A) und (B) sind solche Verbindungen welche eine sterisch gehinderte Phenolgruppe enthalten, insbesondere solche, bei denen die o-Stellung zur OH-Gruppe durch einen tertiären Alkylrest besetzt ist.Preferred from these classes of compounds (A) and (B) are those compounds which contain a sterically hindered phenol group, in particular those in which the o-position to the OH group is occupied by a tertiary alkyl radical.

Die unter B) aufgeführten Verbindungen sind bekannt, und können nach bekannten Methoden hergestellt werden.

  • C) Verbindungen der Formel
    Figure imgb0010
    worin bedeuten:
    • R10 Wasserstoff oder einen unverzweigten oder verzweigten Acylrest (C1-C18)
    • R11 Wasserstoff, C1-C4- Alkyl, COOH, OH, C,-C3-Alkoxy, CONH2 oder SO3H und
    • R12 Wasserstoff, OH, C1-C12-Alkyl, COOH, S03H, gegebenenfalls substituiertes Phenyl, Cyclohexyl, Benzyl oder Phenäthyl.
The compounds listed under B) are known and can be prepared by known methods.
  • C) Compounds of the formula
    Figure imgb0010
     in which mean:
    • R 10 is hydrogen or an unbranched or branched acyl radical (C 1 -C 18 )
    • R 11 is hydrogen, C 1 -C 4 alkyl, COOH, OH, C, -C 3 alkoxy, CONH 2 or SO 3 H and
    • R 12 is hydrogen, OH, C 1 -C 12 alkyl, COOH, S0 3 H, optionally substituted phenyl, cyclohexyl, benzyl or phenethyl.

Bedeutet R11 eine C,-C4-Alkylgruppe oder eine C1-C3- Alkoxygruppe, so kann diese unverzweigt oder verzweigt sein.If R 11 is a C 1 -C 4 -alkyl group or a C 1 -C 3 -alkoxy group, this can be unbranched or branched.

Bedeutet R12 eine C1-C12-Alkylgruppe, so kann diese unverzweigt oder verzweigt sein; beispielsweise sind genannt die Methyl-, Äthyl-, n- oder iso-Hexyl- und n- oder iso-Octylgruppe. Als Substituenten für Phenyl kommen z. B. in Frage: Halogen, wie Fluor, Chlor oder Brom, die NH2-Gruppe und die OH-Gruppe.If R 12 is a C 1 -C 12 alkyl group, this can be unbranched or branched; for example, the methyl, ethyl, n or iso-hexyl and n or iso-octyl group are mentioned. As substituents for phenyl z. B. in question: halogen, such as fluorine, chlorine or bromine, the NH 2 group and the OH group.

Die unter C) genannten Verbindungen sind bekannt und können nach bekannten Methoden hergestellt werden. Beispielsweise sind genannt:

  • o-Aminophenol,
  • m-Aminophenol und vor allem
  • 2-Aminophenol-sulfonsäure und
  • N-Pelargonoyl-p-aminophenol.
The compounds mentioned under C) are known and can be prepared by known methods. Examples include:
  • o-aminophenol,
  • m-aminophenol and above all
  • 2-aminophenol sulfonic acid and
  • N-pelargonoyl-p-aminophenol.

D) Verbindungen der Formel

Figure imgb0011
worin bedeuten:

  • R13 die OH- oder NH2-Gruppe, und R14 und R15 unabhängig voneinander H oder SO3H.
D) Compounds of the formula
Figure imgb0011
 in which mean:
  • R 13 is the OH or NH 2 group, and R 14 and R 15 independently of one another are H or SO 3 H.

Es handelt sich hier einerseits um Dihydroxy-und andererseits um Hydroxyamino-Naphthaline, wo die beiden OH- resp. OH- und NH2-Gruppe sich vorzugsweise in 1,6, 1,8-, 2,5- und 2,7-Stellung befinden.On the one hand, these are dihydroxy and, on the other hand, hydroxyamino naphthalenes, where the two OH or. OH and NH 2 groups are preferably in the 1,6, 1,8, 2,5 and 2,7 positions.

Die Verbindungen sind bekannt und können nach bekannten Methoden hergestellt werden. Beispielsweise sind genannt:

  • 1,8-Dihydroxynaphthalin,
  • 2-Amino-7-hydroxynaphthalin,
  • 2,7-Dihydroxynaphthalin, und insbesondere
  • 1,8-Dihydroxynaphthalin-3,5-disulfonsäure.
The compounds are known and can be prepared by known methods. Examples include:
  • 1,8-dihydroxynaphthalene,
  • 2-amino-7-hydroxynaphthalene,
  • 2,7-dihydroxynaphthalene, and in particular
  • 1,8-dihydroxynaphthalene-3,5-disulfonic acid.

E) Verbindungen der Formel

Figure imgb0012
worin R16 eine unverzweigte oder verzweigte C1-C4- Alkylgruppe darstellt, wie die Methyl-, Äthyl-, n- oder iso-Propyl- oder n-, sec.- oder tert.-Butylgruppe. Diese Verbindungen sind bekannt und können nach bekannten Methoden hergestellt werden. Eine bevorzugte Verbindung aus dieser Klasse stellt das 4-Hydroxy-acetophenon dar.E) Compounds of the formula
Figure imgb0012
 wherein R 16 represents an unbranched or branched C 1 -C 4 alkyl group, such as the methyl, ethyl, n or iso-propyl or n, sec. or tert-butyl group. These compounds are known and can be prepared by known methods. A preferred compound from this class is 4-hydroxy-acetophenone.

F) Verbindungen der Formel

Figure imgb0013
worin R17 die folgende Bedeutung hat:

  • C1-C18-Alkyl (unverzweigt oder verzweigt, wie Methyl, tert.-Butyl, Dodecyl), unsubstituiertes Phenyl; Phenyl substituiert z.B. durch Halogen (F, Cl, Br); Cyclohexyl, Benzyl oder Phenäthyl. Es handelt sich um bekannte Verbindungen, deren interessantester Vertreter Benzhydroxamsäure, ist.
F) Compounds of the formula
Figure imgb0013
 where R 17 has the following meaning:
  • C 1 -C 18 alkyl (unbranched or branched, such as methyl, tert-butyl, dodecyl), unsubstituted phenyl; Phenyl substituted, for example, by halogen (F, Cl, Br); Cyclohexyl, benzyl or phenethyl. These are known compounds, the most interesting representative of which is benzhydroxamic acid.

G) Verbindungen der Formel

Figure imgb0014
worin bedeuten:G) compounds of the formula
Figure imgb0014
 in which mean:

Z unabhängig voneinander ein Brückenglied der Formel

Figure imgb0015
Figure imgb0016
oder
Figure imgb0017
p eine Zahl von 2-6, R28 und R29 unabhängig voneinander Wasserstoff, C1-C6- Alkyl (unverzweigt oder verzweigt) oder C1-C3-Alkoxy (unverzweigt oder verzweigt), R23, R24, R2s und R27 unabhängig voneinander Wasserstoff, C1-C12-Alkyl (unverzweigt oder verzweigt), C1-C12- Hydroxyalkyl, gegebenenfalls substituiertes Phenyl oder Cyclohexyl, a- oder β-Naphthyl oder Benzyl und R26 C1-C12 -Alkyl (unverzweigt oder verzweigt) oder gegebenenfalls substituiertes Phenyl, a- oder β-Naphthyl; Cyclohexyl oder Benzyl, wobei R21 und R24 bzw. R25 und R26 nicht gleichzeitig Wasserstoff bedeuten, mit der Bedingung, dass wenn Z-(CH2)p- ist, R23, R24' R25 und R27 nicht C1-C12-Hydroxyalkyl bedeuten.Z is independently a bridge member of the formula
Figure imgb0015
Figure imgb0016
 or
Figure imgb0017
 p is a number from 2-6, R 28 and R 29 independently of one another hydrogen, C 1 -C 6 alkyl (unbranched or branched) or C 1 -C 3 alkoxy (unbranched or branched), R 23 , R 24, R 2s and R 27 independently of one another hydrogen, C 1 -C 12 alkyl (unbranched or branched), C 1 -C 12 hydroxyalkyl, optionally substituted phenyl or cyclohexyl, a- or β-naphthyl or benzyl and R 26 C 1 -C 12 -alkyl (unbranched or branched) or optionally substituted phenyl, a- or β-naphthyl; Cyclohexyl or benzyl, where R 21 and R 24 or R 25 and R 26 do not simultaneously denote hydrogen, with the condition that when Z is - (CH 2 ) p-, R 23 , R 24 ' R 25 and R 27 do not C 1 -C 12 hydroxyalkyl.

Als Substituenten für Phenyl gemäss den Symbolen R23, R24, R25, R26 und R17 kommen vor allem in Frage: OH, Halogen (F, Cl, Br), NH2 und C1-C4-Alkyl.The following are particularly suitable as substituents for phenyl according to the symbols R 23 , R 24 , R 25 , R 26 and R 17 : OH, halogen (F, Cl, Br), NH 2 and C 1 -C 4 alkyl.

Die Verbindungen sind bekannt oder können nach bekannten Methoden hergestellt werden. Es handelt sich beispielsweise um folgende Verbindungen:

  • N,N'-Diphenyl-p-phenylendiamin,
  • N,N'-N,N'-Tetramethylguanidin,
  • Pentamethyldiäthylentriamin,
  • Di-o-tolyläthylendiamin und
  • N,N'-Diphenyläthylendiamin.
The compounds are known or can be prepared by known methods. These are, for example, the following connections:
  • N, N'-diphenyl-p-phenylenediamine,
  • N, N'-N, N'-tetramethylguanidine,
  • Pentamethyldiethylenetriamine,
  • Di-o-tolylethylenediamine and
  • N, N'-diphenylethylenediamine.

H) Verbindungen der Formel

Figure imgb0018
worin R30 eine unverzweigte oder verzweigte C1-C12-Alkylgruppe, wie die Methyl-, Äthyl-, n-oder iso-Propyl-, n- oder iso-Hexyl- oder n- oder iso-Octylgruppe darstellt.H) Compounds of the formula
Figure imgb0018
 wherein R 30 represents an unbranched or branched C 1 -C 12 alkyl group, such as the methyl, ethyl, n or iso-propyl, n or iso-hexyl or n or iso-octyl group.

Es handelt sich hier um die bekannten Gallussäureester, deren interessantesten Vertreter in diesem Zusammenhang

  • n-Propylgallat, und
  • n-Octylgallat sind.
These are the well-known gallic acid esters, their most interesting representatives in this context
  • n-propyl gallate, and
  • are n-octyl gallate.

I) Verbindungen der Formel

Figure imgb0019
worin R3, Wasserstoff, CHzOH oder die C,-C2-Alkylgruppe bedeutet. Als Vertreter dieser Klasse sei z. B. Propylenglykolsulfit genannt.I) compounds of the formula
Figure imgb0019
 wherein R 3 is hydrogen, CH z OH or the C, -C 2 alkyl group. As a representative of this class B. called propylene glycol sulfite.

Die unter A) bis I) genannten Verbindungen sind allgemein leicht zugänglich und zeichnen sich durch eine gute Verteilbarkeit in den Farbstoffzubereitungen, Färbebädern bzw. Reduktionsbädern und Druckpasten aus. Die genannten Verbindungen sollen wasserlöslich sein und/oder löslich in einem alkalisch reduktiven Bad (ph ≽ 12). Erfüllen sie diese Löslichkeitsanforderungen nicht, so ist es zweckmässig, diese Verbindungen vor ihrer Verwendung, z.B. mit einem anionischen Dispergiermittel auf eine Korngrösse von < 5 µm insbesondere ca. 1 11m zu mahlen. Das geschieht im Prinzip derart, dass man den Verküpungsbeschleuniger bzw. eine Mischung davon mit einem Dispergiermittel, z.B. einem Naphthalinsulfonsäure/Formaldehyd-Kondensationsprodukt vermischt, beispielsweise durch gemeinsames Nass-Vermahlen in einer Korundscheibenmühle, Kugelmühle, Rührwerksmühle, Sandmühle oder anderen Mahlaggregaten, gegebenenfalls unter anschliessender Trocknung der Mischung, z.B. in einem Zerstäubungstrockner.The compounds mentioned under A) to I) are generally easily accessible and are notable for good distributability in the dye preparations, dye baths or reduction baths and printing pastes. The compounds mentioned should be water-soluble and / or soluble in an alkaline reductive bath (ph ≽ 12). If they do not meet these solubility requirements, it is advisable to use these compounds before their use, e.g. to be ground with an anionic dispersing agent to a grain size of <5 µm, in particular about 11 m. In principle, this is done in such a way that the vatting accelerator or a mixture thereof with a dispersant, e.g. mixed with a naphthalenesulfonic acid / formaldehyde condensation product, for example by joint wet grinding in a corundum disk mill, ball mill, agitator mill, sand mill or other grinding units, optionally with subsequent drying of the mixture, e.g. in an atomizing dryer.

Bevorzugt werden als Verküpungsbeschleuniger die Phenole und Amine gemäss der Gruppen A), B), C) und G) verwendet.The phenols and amines according to groups A), B), C) and G) are preferably used as vatting accelerators.

Eingesetzt werden die Verküpungsbeschleuniger vorteilhaft in einer Menge von 0,5 bis 10 Gew.%, bezogen auf Farbstoff, bzw. in einer Menge von 0,05 bis 1 g pro Liter Reduktionsbad.The vatting accelerators are advantageously used in an amount of 0.5 to 10% by weight, based on the dye, or in an amount of 0.05 to 1 g per liter of reduction bath.

Unter dem Begriff Verfahren zum Färben oder Bedrucken von Cellulosematerialien bzw. Cellulose/Polyester-Mischgewebe sind im vorliegenden Fall allgemein übliche Färbe- und Druckverfahren zu verstehen, mit denen Küpen- und Schwefelfarbstoffe normalerweise auf den genannten Textilmaterialien appliziert werden. Beim Färbeverfahren handelt es sich sowohl um Auszieh- wie Kontinue-Verfahren. Im einzelnen sind z.B. genannt: Ausziehverfahren im Jigger, in der Haspelkufe und in der Jetfärbemaschine, das Pad-Jig-Verfahren, das Standfastverfahren, das Halbpigmentierverfahren, die Klotzfixierverfahren, z. B. das Einbadklotzdämpfverfahren, das Pad-Roll-Verfahren, das Pad-Roll-Verfahren mit Zwischentrocknung, das Nassdampfverfahren und vor allem das Pad-Steam-Verfahren. Als Druckverfahren sind z.B. genannt: einphasige und zweiphasige Entwicklungsverfahren.The term process for dyeing or printing cellulosic materials or cellulose / polyester blended fabrics in the present case is to be understood as general dyeing and printing processes with which vat and sulfur dyes are normally applied to the textile materials mentioned. The dyeing process is both a pull-out and a continuous process. In particular, e.g. called: pull-out process in the jigger, in the reel runner and in the jet dyeing machine, the pad-jig process, the standfast process, the semi-pigmentation process, the block fixing process, e.g. B. the Einbadklotzdampfverfahren, the pad-roll process, the pad-roll process with intermediate drying, the wet steam process and especially the pad-steam process. As printing processes e.g. called: single-phase and two-phase development processes.

Durch den Zusatz der genannten Verküpungsbeschleuniger wird eine Verbesserung der Farbausbeute von ca. 7% bis 10% und mehr erreicht. Man kommt daher bei gleicher Farbtiefe mit weniger Farbstoff aus, was zu erheblichen wirtschaftlichen Einsparungen führt.By adding the vatting accelerators mentioned, an improvement in the color yield of about 7% to 10% and more is achieved. It is therefore possible to use less dye with the same color depth, which leads to considerable economic savings.

Ein weiterer Gegenstand der vorliegenden Erfindung sind Küpen- und Schwefelfarbstoffpräparate, die neben dem Farbstoff und gegebenenfalls weiteren Zusätzen, einen organischen Verküpungsbeschleuniger enthalten, wobei als Verküpungsbeschleuniger eine oder mehrere der vorstehend im einzelnen beschriebenen Verbindungen zur Anwendung gelangen, also Verbindungen, die mindestens eine aromatische Hydroxygruppe und/oder eine sekundäre oder tertiäre Aminogruppe, eine -CONHOH-Gruppe, oder eine >S=O-Gruppierung aufweisen, ausgenommen Nitrophenole und Derivate aromatischer Carbonsäuren mit weniger als 3 aromatischen Hydroxygruppen. Enthalten sind die Verküpungsbeschleuniger in den Präparaten in einer Konzentration von 0,1 bis 20 Gew.%, insbesondere 0,5 bis 10 Gew.%, bezogen auf Farbstoff.The present invention furthermore relates to vat and sulfur dye preparations which, in addition to the dye and, if appropriate, further additives, contain an organic coupling accelerator, one or more of the compounds described above in detail being used as coupling accelerators, that is to say compounds which have at least one aromatic hydroxyl group and / or have a secondary or tertiary amino group, a -CONHOH group, or a> S = O group, with the exception of nitrophenols and derivatives of aromatic carboxylic acids with less than 3 aromatic hydroxy groups. The vatting accelerators are contained in the preparations in a concentration of 0.1 to 20% by weight, in particular 0.5 to 10% by weight, based on the dye.

Ausser den genannten Verküpungsbeschleunigern enthalten die Farbstoffzubereitungen üblicherweise noch anionische Dispergiermittel oder eventuell nicht-ionogene Füllmittel, vorzugsweise in Mengen von 0,5 bis 80 Gew.%. Als derartige Dispergiermittel werden vor allem solche verwendet, wie sie in der DE-A-2 816 539 beschrieben sind. Als weitere Zusätze kommen die in Farbstoffpräparaten allgemein enthaltenen Hilfsmittel in Frage, wie Feuchthaltemittel, Schaumverhütungsmittel, Konservierungsmittel, Netzmittel, Egalisiermittel, Verdickungsmittel usw.In addition to the vatting accelerators mentioned, the dye preparations usually also contain anionic dispersants or possibly nonionic fillers, preferably in amounts of 0.5 to 80% by weight. Dispersants of this type are primarily used as described in DE-A-2 816 539. Further additives are the auxiliaries generally contained in dye preparations, such as humectants, antifoams, preservatives, wetting agents, leveling agents, thickeners, etc.

Bei den Küpen- und Schwefelfarbstoffen handelt es sich in erster Linie um Indanthrone, Flavanthrone, Pyranthrone, Violanthrone, Isoviolanthrone, Benzanthrone, am Stickstoff substituierte Imide der Perylentetracarbonsäure, Acridone, Anthrachinonoxazole, Anthrachinonthiazole und Verbindungen, die sich vor allen vom Anthrachinon ableiten.The vat and sulfur dyes are primarily indanthrones, flavanthrones, pyranthrones, violanthrones, isoviolanthrones, benzanthrones, nitrogen-substituted imides of perylene tetracarboxylic acid, acridones, anthraquinone oxazoles, anthraquinone thiazoles and compounds that are derived primarily from anthraquinone.

Gegenstand der Erfindung sind ferner die Färbebäder und Druckpasten, sowie die Reduktionsbäder als solche. Hergestellt werden die Färbebäder bzw. Druckpasten in einfacher Weise dadurch, dass man eine bereits den Verküpungsbeschleuniger enthaltende Küpen- oder Schwefelfarbstoffzubereitung im Färbebad auflöst, bzw. in ein geeignetes Verdickungsmittel einarbeitet.The invention also relates to the dye baths and printing pastes, and the reduction baths as such. The dyebaths or printing pastes are produced in a simple manner by dissolving a vat or sulfur dye preparation which already contains the vatting accelerator in the dyebath or by incorporating them in a suitable thickener.

Neben der Möglichkeit, den Farbstoff zusammen mit dem Verküpungsbeschleuniger auf das Gewebe aufzubringen, kann das Textilmaterial auch zunächst nur mit dem Farbstoff imprägniert oder bedruckt, dann gegebenenfalls zwischengetrocknet und anschliessend der auf dem Gewebe befindliche Farbstoff in einem den Verküpungsbeschleuniger enthaltenden Reduktionsbad verküpt werden. Bei den Verküpungsbeschleunigern handelt es sich um Substanzen, die den bereits im einzelnen beschriebenen Verbindungsklassen angehören. Die Verbindungen werden einzeln oder im Gemisch eingesetzt und zwar pro Liter Reduktionsbad in einer Menge von 0,01 bis 5 g, vorzugsweise 0,05 bis 1 g.In addition to the possibility of applying the dye to the fabric together with the vatting accelerator, the textile material can also initially only be impregnated or printed with the dye, then optionally dried and then the dye on the fabric can be vetted in a reduction bath containing the vatting accelerator. The linking accelerators are substances which belong to the compound classes already described in detail. The compounds are used individually or in a mixture, specifically per liter of reduction bath in an amount of 0.01 to 5 g, preferably 0.05 to 1 g.

Zum Verküpen der Farbstoffe enthalten die Reduktionsbäder neben dem Verküpungsbeschleuniger ein Reduktionsmittel und zwar z. B. Natriumdithionit, Natriumformaldehydsulfoxylat der Thioharnstoffdioxyd, sowie Alkali, vor allem Natronlauge oder Kalilauge.For vatting the dyes, the reduction baths contain, in addition to the vatting accelerator, a reducing agent, e.g. B. sodium dithionite, sodium formaldehyde sulfoxylate of thiourea dioxide, and alkali, especially sodium hydroxide solution or potassium hydroxide solution.

Die nachfolgenden Beispiele veranschaulichen die Erfindung, ohne sie darauf zu limitieren. Teile bedeuten Gewichtsteile.The following examples illustrate the invention without restricting it to them. Parts mean parts by weight.

Beispiel 1example 1

Vorgereinigtes und gebleichtes Baumwollgewebe wird in einer Pad-Steam-Anlage gefärbt. Das Gewebe wird mit einer Färbeflotte, die

  • 40 Teile der flüssigen Handelsform des Farbstoffes C.I. Vat Blue 18 (Colour Index Nr. 59 815) und 960 Teile Wasser enthält, in einem Foulard geklotzt (Abquetscheffekt 70%), bei 100°C getrocknet und in einem zweiten Foulard mit einer Flotte folgender Zusammensetzung (Abquetscheffekt 80%) geklotzt:
  • 60 Teile konz. NaOH 36°Be
  • 50 Teile Natriumdithionit
  • 25 Teile Glaubersalz calc. 1,5 Teile 30%-iger wässriger Dispersion von Tetrakis-[methylen-3-(3',5'-di-tert.-butyl-4'-hydroxyphenyl)-propionat]-methan (durchschnittliche Feinheit 1 gm) 863,5 Teile Wasser.
Pre-cleaned and bleached cotton fabric is dyed in a pad steam system. The fabric is washed with a dye liquor
  • Contains 40 parts of the liquid commercial form of the dye CI Vat Blue 18 (Color Index No. 59 815) and 960 parts of water, padded in a foulard (squeezing effect 70%), dried at 100 ° C. and in a second foulard with a liquor of the following composition (Squeezing effect 80%) padded:
  • 60 parts conc. NaOH 36 ° Be
  • 50 parts of sodium dithionite
  • 25 parts Glauber's salt calc. 1.5 parts of 30% aqueous dispersion of tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane (average fineness 1 gm) 863, 5 parts water.

Danach wird das Baumwollgewebe 30 Sekunden bei 100°C im Dämpfer gedämpft. Anschliessend wird wie üblich gespült, mit 3 ml/l H202 30%-ig, 15 Minuten bei 50°C oxidiert, gespült und 15 Minuten bei Kochtemperatur mit 2 g/i eines anionaktiven Waschmittels und 1 g/I Soda calc. geseift. Man erhält eine blaue Färbung, die farbstärker ist als eine Vergleichsfärbung ohne Zusatz von 30%-iger wässriger Dispersion von Tetrakis-[methylen-3-(3',5'-di-tert.-butyl-4'-hydroxyphenyl)-propionat]-methan.The cotton fabric is then steamed in the steamer at 100 ° C for 30 seconds. Then rinsed as usual, with 3 ml / l H 2 0 2 30%, oxidized for 15 minutes at 50 ° C, rinsed and for 15 minutes at cooking temperature with 2 g / i of an anionic detergent and 1 g / l soda calc. soaped. A blue coloration is obtained which is more intense in color than a comparison coloration without the addition of 30% aqueous dispersion of tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate ]-methane.

Verwendet man anstelle der 1,5 Teile der 30%-igen wässrigen Dispersion von Tetrakis-[methylen-3-(3',5'-di-tert.-butyl-4'-hydroxyphenyl)-propionat]-methan als Verküpungsbeschleuniger folgende Produkte:

  • 0,5 Teile Benzhydroxamsäure,
  • 0,5 Teile 4,4'-lsopropyliden-bis(phenol),
  • 0,5 Teile 2-Benzyl-4-chlor-phenol,
  • 0,5 Teile 4,4'-Methylen-bis(2,6-di-tert.-butyl-phenol),
  • 0,5 Teile 2,6-Di-tert.-butyl-p-kresol,
  • 0,5 Teile Na-Salz von 2-Aminophenol-4-sulfonsäure,
  • 0,5 Teile n-Propylgallat,- so erhält man bei im übrigen gleichen Vorgehen ebenfalls farbstärkere blaue Ausfärbungen als die Vergleichsfärbung ohne Verküpungsbeschleuniger.
In place of the 1.5 parts of the 30% aqueous dispersion of tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane, the following are used as vatting accelerators Products:
  • 0.5 parts of benzhydroxamic acid,
  • 0.5 parts of 4,4'-isopropylidene bis (phenol),
  • 0.5 part of 2-benzyl-4-chlorophenol,
  • 0.5 parts of 4,4'-methylene-bis (2,6-di-tert-butylphenol),
  • 0.5 parts of 2,6-di-tert-butyl-p-cresol,
  • 0.5 parts Na salt of 2-aminophenol-4-sulfonic acid,
  • 0.5 parts of n-propyl gallate, so that with the rest of the same procedure, more intense blue colorations are obtained than the comparison coloration without vatting accelerator.

Beispiel 2Example 2

Vorgereinigtes Baumwollgewebe wird im Pad-Steam-Verfahren mit einer Färbeflotte, enthaltend

  • 50 Teile der flüssigen Handelsform des Farbstoffes C.I. Vat Yellow 2 (Colour Index Nr. 67 300) und
  • 950 Teile Wasser geklotzt und nach der Trocknung mit einer Flotte folgender Zusammensetzung geklotzt:
    • 60 Teile konz. NaOH 36°Be
    • 50 Teile Na-Dithionit
    • 25 Teile Glaubersalz calc.
    • 0,5 Teile Propylenglykolsulfit und 864,5 Teile Wasser.
Pre-cleaned cotton fabric is contained in the pad-steam process with a dyeing liquor
  • 50 parts of the liquid commercial form of the dye CI Vat Yellow 2 (Color Index No. 67 300) and
  • 950 parts of water were padded and, after drying, padded with a liquor of the following composition:
    • 60 parts conc. NaOH 36 ° Be
    • 50 parts of Na dithionite
    • 25 parts Glauber's salt calc.
    • 0.5 parts propylene glycol sulfite and 864.5 parts water.

Anschliessend wird 30 Sekunden bei 100 °C gedämpft und das Gewebe fertiggestellt wie in Beispiel 1 beschrieben. Es resultiert eine gelbe Färbung, die viel farbstärker ist als eine Vergleichsfärbung ohne Propylenglykolsulfit.It is then steamed at 100 ° C. for 30 seconds and the fabric is finished as described in Example 1. The result is a yellow color, which is much stronger in color than a comparison color without propylene glycol sulfite.

Ebenfalls farbtiefere gelbe Färbungen im Vergleich zu analogen Färbungen ohne Verküpungsbeschleunigerzusatz erhält man, wenn anstelle von 0,5 Teilen Propylenglykolsulfit 0,5 Teile der folgenden Produkte verwendet werden: 4,4'-Isopropyliden-bis(phenol), 2,2'-Methylen-bis(4-chlorphenol).Similarly deep yellow colorations in comparison to analogous colorations without addition of vatting accelerator are obtained if 0.5 part of the following products are used instead of 0.5 part propylene glycol sulfite: 4,4'-isopropylidene-bis (phenol), 2,2'-methylene -bis (4-chlorophenol).

Beispiel 3Example 3

Eine Druckpaste folgender Zusammensetzung:

  • 70 Teile der flüssigen Handelsform des Farbstoffes C.I. Vat Green 1 (Colour Index Nr. 59 825)
  • 60 Teile Verdickungsmittel
  • 120 Teile Kaliumcarbonat
  • 100 Teile hydroxymethansulfonsäures Natrium
  • 70 Teile Glycerin 2 Teile 30%-iger wässriger Dispersion von Tetrakis-[methylen-3-(3',5'-di-tert.-butyl-4'-hydroxyphenyl)-propionat]-methan und
  • 578 Teile Wasser wird mittels einer Filmdruckmaschine auf Baumwollgewebe gedruckt. Dieses wird anschliessend 8 Minuten bei 100°C im Dämpfer gedämpft und dann wie in Beispiel 1 behandelt.
A printing paste with the following composition:
  • 70 parts of the liquid commercial form of the dye CI Vat Green 1 (Color Index No. 59 825)
  • 60 parts of thickener
  • 120 parts of potassium carbonate
  • 100 parts of hydroxymethanesulfonic acid sodium
  • 70 parts of glycerin, 2 parts of 30% aqueous dispersion of tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane and
  • 578 parts of water are printed on cotton fabric using a film printing machine. This is then steamed for 8 minutes at 100 ° C in the steamer and then treated as in Example 1.

Es resultiert eine farbtiefere grüne Färbung im Vergleich zu einem Druck ohne die 2 Teile der 30%-igen wässrigen Dispersion von Tetrakis-[methylen-3-(3',5'-di-tert.-butyl-4'-hydroxyphenyl)-propionat]-methan.The result is a deep green color in comparison to a print without the 2 parts of the 30% aqueous dispersion of tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) - propionate] methane.

Eine farbtiefere Färbung wird auch erhalten; wenn anstelle der 2 Teile der 30%-igen wässrigen Dispersion von Tetrakis-[methylen-3-(3',5'-di-tert.-butyl-4'-hydroxyphenyl)-propionat]-methan eines der folgenden Produkte der Druckpaste zugesetzt wird:

  • 0,5 Teile 2-Benzyl-4-chlor-phenol,
  • 0,5 Teile 4-Chlor-m-kresol,
  • 0,5 Teile Propylenglykolsulfit, oder 4 Teile Pentamethyldiäthylentriamin.
A color-deep coloring is also obtained; if instead of the 2 parts of the 30% aqueous dispersion of tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane one of the following products is added to the printing paste:
  • 0.5 part of 2-benzyl-4-chlorophenol,
  • 0.5 parts of 4-chloro-m-cresol,
  • 0.5 part propylene glycol sulfite, or 4 parts pentamethyldiethylenetriamine.

Beispiel 4Example 4

  • 98,5 Teile des Farbstoffes Vat Black 25 (Colour Index Nr. 69 525) in flüssiger Handelsform und98.5 parts of the dye Vat Black 25 (Color Index No. 69 525) in liquid commercial form and
  • 1,5 Teile Propylenglykolsulfit werden vermischt und homogenisiert.1.5 parts of propylene glycol sulfite are mixed and homogenized.

Mit dieser Farbstoffzubereitung wird eine Färbeflotte für eine Pad-Steam-Färbung vorbereitet:

  • 50 Teile der Farbstoffzubereitung
  • 950 Teile Wasser.
This dye preparation is used to prepare a dye liquor for pad-steam dyeing:
  • 50 parts of the dye preparation
  • 950 parts of water.

Ausgewaschenes Baumwollgewebe wird mit dieser Färbeflotte geklotzt und wie in Beispiel 4 bis zur fertigen Färbung behandelt.Washed-out cotton fabric is padded with this dye liquor and treated as in Example 4 until the dyeing is finished.

Es resultiert eine olive-graue Färbung, die farbtiefer ist als eine Vergleichsfärbung ohne Zusatz von Propylenglykolsulfit.The result is an olive-gray coloration that is deeper in color than a comparison coloration without the addition of propylene glycol sulfite.

Beispiel 5Example 5

Gereinigtes Baumwollgewebe wird im Pad-Steam-Verfahren mit einer Färbeflotte, enthaltend

  • 50 Teile der flüssigen Handelsform des Farbstoffes Vat Blue 6 (Colour Index Nr. 69 825) und
  • 950 Teilen Wasser geklotzt, getrocknet und mit einer Flotte folgender Zusammensetzung geklotzt:
  • 70 Teile konz. NaOH 36°Be
  • 50 Teile Na-Dithionit 0,5 Teile 2-Benzyl-4-chlorphenol und
  • 879,5 Teile Wasser. Nach ca. 30 Sekunden Dämpfen bei 100°C wird das Gewebe gleich behandelt wie in Beispiel 1.
Cleaned cotton fabric is contained in the pad-steam process with a dyeing liquor
  • 50 parts of the liquid commercial form of the dye Vat Blue 6 (Color Index No. 69 825) and
  • 950 parts of water padded, dried and padded with a liquor of the following composition:
  • 70 parts conc. NaOH 36 ° Be
  • 50 parts Na dithionite 0.5 parts 2-benzyl-4-chlorophenol and
  • 879.5 parts water. After about 30 seconds steaming at 100 ° C, the fabric is treated in the same way as in Example 1.

Es resultiert eine blaue Färbung, die viel farbstärker ist als eine Vergleichsfärbung ohne 2-Benzyl-4-chlorphenol.The result is a blue color, which is much stronger than a comparison color without 2-benzyl-4-chlorophenol.

Ebenfalls farbtiefere blaue Färbungen im Vergleich zur Färbung ohne Beschleuniger erhält man, wenn anstelle von 0,5 Teilen 2-Benzyl-4- chlorphenol

  • 0,5 Teile 2,6-Di-tert.-butyl-p-kresol,
  • 1,5 Teile 30%-ige flüssige Dispersion von 2,5-Di- tert.-butyl-hydrochinon,
  • 0,5 Teile 2-Aminophenol-4-sulfonsäure,
  • 0,5 Teile 4,4'-lsopropyliden-bis(phenol), oder
  • 0,5 Teile 4-Hydroxyacetophenon verwendet werden.
Also deep blue colorings in comparison to the coloring without accelerator are obtained when 2-benzyl-4-chlorophenol is used instead of 0.5 part
  • 0.5 parts of 2,6-di-tert-butyl-p-cresol,
  • 1.5 parts of 30% liquid dispersion of 2,5-di-tert-butyl-hydroquinone,
  • 0.5 parts of 2-aminophenol-4-sulfonic acid,
  • 0.5 parts of 4,4'-isopropylidene bis (phenol), or
  • 0.5 parts of 4-hydroxyacetophenone can be used.

Beispiel 6Example 6

Gereinigtes Baumwollgewebe wird im Pad-Steam-Verfahren mit einer Färbeflotte, enthaltend

  • 40 Teile der flüssigen Handelsform des Farbstoffes Vat Green 3 (Colour Index Nr. 69 500) und 960 Teilen Wasser geklotzt, getrocknet und mit einer Flotte folgender Zusammensetzung geklotzt:
  • 60 Teile konz. NaOH 36°Be
  • 50 Teile Na-Dithionit
  • 1 Teil N,N',N,N'-Tetramethylguanidin und 889 Teilen Wasser.
Cleaned cotton fabric is contained in the pad-steam process with a dyeing liquor
  • 40 parts of the liquid commercial form of the dye Vat Green 3 (Color Index No. 69 500) and 960 parts of water, padded, dried and padded with a liquor of the following composition:
  • 60 parts conc. NaOH 36 ° Be
  • 50 parts of Na dithionite
  • 1 part of N, N ', N, N'-tetramethylguanidine and 889 parts of water.

Nach ca. 30 Sekunden Dämpfen bis 100 °C wird das Gewebe gleich wie in Beispiel 1 behandelt.After about 30 seconds steaming up to 100 ° C the fabric is treated in the same way as in example 1.

Es resultiert eine grüne Färbung, die farbstärker ist als eine Vergleichsfärbung ohne Zusatz von N,N'N,N'-Tetramethylguanidin.The result is a green coloration which is stronger in color than a comparison coloration without addition of N, N'N, N'-tetramethylguanidine.

Ebenfalls farbtiefere grüne Färbungen im Vergleich zur Färbung ohne Verküpungsbeschleuniger erhält man, wenn anstelle von 1,0 Teil N,N',N,N'-Tetramethylguanidin

  • 1,5 Teile 30%-iger flüssiger Dispersion von 2,5-Di-tert.-butyl-hydrochinon, oder
  • 1,0 Teil einer 50%-igen flüssigen Verküpungsbeschleunigermischung der Zusammensetzung: 20 Teile 4,4'-lsopropyliden-bis(phenol),
  • 15 Teile 2-Benzyl-4-chlorphenol
  • 15 Teile N-(Hydroxyäthyl)-äthylendiamin 5 Teile konz. NaOH 36°Be und
  • 45 Teile Butyldiglykol verwendet werden.
Also deep green colorings in comparison to the coloring without vatting accelerators are obtained if instead of 1.0 part N, N ', N, N'-tetramethylguanidine
  • 1.5 parts of 30% liquid dispersion of 2,5-di-tert-butyl-hydroquinone, or
  • 1.0 part of a 50% liquid vatting accelerator mixture of the composition: 20 parts of 4,4'-isopropylidene-bis (phenol),
  • 15 parts of 2-benzyl-4-chlorophenol
  • 15 parts of N- (hydroxyethyl) ethylenediamine 5 parts of conc. NaOH 36 ° Be and
  • 45 parts of butyl diglycol can be used.

Claims (17)

1. A process for dyeing or printing cellulose material or cellulose/polyester blends with vat dyes or sulfur dyes using a vatting accelerator, which process comprises using as vatting accelerator a compound, or a mixture of several such compounds, containing at least one aromatic hydroxyl group and/or a secondary or tertiary amino group, a -CONHOH group, or an >S = O grouping, with the exception of nitrophenols and derivatives of aromatic carboxylic acids containing less than 3 aromatic hydroxyl groups, which vatting accelerator is added to the dye bath or printing paste in an amount of 0.1 to 20% by weight, based on the dye, or to the reduction bath in an amount of 0.01 to 5 g/I.
2. A process according to claim 1, which comprises using as vatting accelerator a compound selected from any one of the following classes:
A) compounds of the formula
Figure imgb0043
wherein each of R,, Rz and R3 independently of one another is: C1-C12alkyl, C3-C12alkenyl, -CH2OH, hydrogen, halogen, OH, C1-C4alkoxy or unsubstituted or substituted phenyl, benzyl or phenethyl, or is cyclohexyl, S03H, COOH, CONHz or the group
Figure imgb0044
with the proviso that R1, R2 and R3 are not simultaneously each hydrogen, and also that, if one of the radicals R1, R2 and R3 is -OH or-CH3, at most one of the remaining two radicals is hydrogen;
B) compounds of the formula
Figure imgb0045
organic radical wherein
each of R, and R2 independently of the other is: C1-C12alkyl, C3-C12alkenyl, -CH20H, hydrogen, halogen, OH, -S03H, -COOH, -CONH2, C1-C4alkoxy or unsubstituted or substituted phenyl, benzyl or phenethyl, or is cyclohexyl, or the group
Figure imgb0046
m is a number 1 or 2, and R'3 is any bridge member;
C) compounds of the formula
Figure imgb0047
wherein
R10 is hydrogen or a straight chain or branched C1-C18acyl group, R11 is hydrogen, C,-C4alkyl, COOH, OH, C1-C3alkoxy, CONH2 or S03H, and R12 is hydrogen, OH, C1-C12alkyl, COOH, SO3H, unsubstituted or substituted phenyl, or is cyclohexyl, benzyl or phenethyl;
D) compounds of the formula
Figure imgb0048
wherein
R13 is the OH or NH2 group, and each of R14 and R,5 independently of the other is H or SO3H;
E) compounds of the formula
Figure imgb0049
wherein
R16 is a C1-C4alkyl group;
F) compounds of the formula
Figure imgb0050
wherein
R17 has the following meanings: C1-C18alkyl, unsubstituted or substituted phenyl, or cyclohexyl, benzyl or phenethyl;
G) compounds of the formula
Figure imgb0051
wherein each
Z independently of the other is a bridge member of the formula
Figure imgb0052
Figure imgb0053
or
Figure imgb0054
p is a number from 2-6, each of R28 and R29 independently of the other is hydrogen, C,-C6alkyl or C1-C3alkoxy, each of R23, R24 and R25 and R27 independently of one another is hydrogen, C1-C12alkyl, C1-C12hydroxyalkyl, unsubstituted or substituted phenyl, or benzyl, a- or β-naphthyl or cyclohexyl, and R26 is C1-C12alkyl, or unsubstituted or substituted phenyl, or is cycloalkyl, a- or β-naphthyl or benzyl, R23 and R24 or R25 and R26 not simultaneously being hydrogen, with the proviso that, if Z is -(CH2)p-, R23, R24 and R25 and R27 are not C1-C12hydroxyalkyl;
H) compounds of the formula
Figure imgb0055
wherein
R30 is a C1-C12alkyl group; and
I) compounds of the formula
Figure imgb0056
wherein
R3, is hydrogen, CH2OH or C1-C2alkyl.
3. A process according to claim 1, which comprises employing the vatting accelerator in an amount of 0.5 to 10% by weight, based on the dye, or in an amount of 0.05 to 1 g per litre of reduction bath.
4. A process according to claim 2, which comprises using as vatting accelerator a compound of class A, B, C or G.
5. A process according to claim 2, which comprises using as vatting accelerator a compound of the formula
Figure imgb0057
wherein each of
R1, R2 and R3 independently of one another is: C1-C5alkyl, -CH20H, hydrogen, halogen, OH, C1-C4alkoxy, benzyl, cyclohexyl or the group
Figure imgb0058
with the proviso that
R1, R2 and R3 are not simultaneously hydrogen, and also that, if one of the radicals R1, R2 and R3 is -OH or-CH3, at most one of the two remaining radicals is hydrogen.
6. A process according to claim 5, which comprises using as vatting accelerator a compound of the formula indicated, wherein each of R1, R2 and R3 independently of one another is: C1-C4alkyl, hydrogen, Cl, OH or benzyl, with the proviso that R1, R2 and R3 are not simultaneously hydrogen, and also that, if one of the radicals R,, R2 and R3 is -OH or-CH3, at most one of the two remaining radicals is hydrogen.
7. A process according to claim 2, which comprises using as vatting accelerator a compound of the formula
Figure imgb0059
wherein
R1 and R2 are as defined in claim 2, and X is an aliphatic bridge member, m is the number 1 or 2, n is a number 1 to 4, and p is a number 1 to 3, and R'3 is a bridge member having n valencies selected from the following groups: radicals of an inorganic or organic acid or radicals of an aldehyde, of a styrene or of an olefin.
8. A process according to claim 7, which comprises using as vatting accelerator a compound of the formula
Figure imgb0060
wherein
R1, R2 and m are as defined in claim 7, R'3 is a bridge member having n valencies selected from the following groups:
Figure imgb0061
or the
Figure imgb0062
Figure imgb0063
10. A process according to claim 2, which comprises using as vatting accelerator a compound of the formula
Figure imgb0064
wherein
A is the direct bond, or a bivalent bridge member of the formula
Figure imgb0065
each R4 independently of the other is hydrogen or C,-C4alkyl, and each of R5 and R6 independently of the other is: C1-C12alkyl, C3-C12alkenyl, halogen, C1-C4alkoxy, or unsubstituted or substituted phenyl, or is cyclohexyl, benzyl, phenethyl, S03H, COOH, CONH2 or hydrogen.
11. A process according to claim 2, which comprises using as vatting accelerator a compound of class (A) and/or class (B) which contains a sterically hindered phenol group.
12. A process according to claim 11, which comprises using as vatting accelerator a compound of class (A) or class (B) which carries a tertiary alkyl group in the o-position with respect to the OH group.
13. A vat dye or sulfur dye composition containing an organic vatting accelerator, together with the dye and, if desired, further additives, in which composition the vatting accelerator, which is used in a concentration of 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the dye, is a compound, or a mixture of several such compounds, containing at least one aromatic hydroxyl group and/or a secondary or tertiary amino group, a -CONHOH group or an >S=O grouping, with the exception of nitrophenols and derivatives of aromatic carboxylic acids containing less than 3 aromatic hydroxyl groups.
14. A dye bath or printing paste for carrying out the process according to claim 1, which bath or paste contains a vat dye or sulfur dye composition according to claim 13.
15. A reduction bath for carrying out the process according to claim 1 containing a reducing agent conventionally employed for reducing vat dyes or sulfur dyes, and containing an organic vatting accelerator and alkali metal, in which reduction bath the vatting accelerator is a compound, or a mixture of several such compounds, containing at least one aromatic hydroxyl group and/or a secondary or tertiary amino group, a-CONHOH group or an >S=O grouping, with the exception of nitrophenols and derivatives of aromatic carboxylic acids containing less than 3 aromatic hydroxyl groups, and in which bath the vatting accelerator is contained in an amount of 0.01 to 5 g per litre of reduction bath.
16. A reduction bath according to claim 15, which contains 0.05 to 1 g of vatting accelerator per litre of reduction bath.
EP81810513A 1980-12-30 1981-12-22 Process for dyeing or printing cellulosic materials and mixed cellulose/polyester fabrics Expired EP0055694B1 (en)

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CH9644/80 1980-12-30
CH964480 1980-12-30

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EP0055694A3 EP0055694A3 (en) 1983-01-19
EP0055694B1 true EP0055694B1 (en) 1986-06-04

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EP (1) EP0055694B1 (en)
JP (2) JPS57133281A (en)
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EP0055694A2 (en) 1982-07-07
JPH0423031B2 (en) 1992-04-21
JPH0376876A (en) 1991-04-02
ZA818967B (en) 1982-11-24
JPH0329827B2 (en) 1991-04-25
EP0055694A3 (en) 1983-01-19
US4519805A (en) 1985-05-28
JPS57133281A (en) 1982-08-17
US4886549A (en) 1989-12-12
DE3174788D1 (en) 1986-07-10

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