EP0310556B1 - Process for dyeing cellulosic fibres without tailing - Google Patents

Process for dyeing cellulosic fibres without tailing Download PDF

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Publication number
EP0310556B1
EP0310556B1 EP88810652A EP88810652A EP0310556B1 EP 0310556 B1 EP0310556 B1 EP 0310556B1 EP 88810652 A EP88810652 A EP 88810652A EP 88810652 A EP88810652 A EP 88810652A EP 0310556 B1 EP0310556 B1 EP 0310556B1
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Prior art keywords
formula
process according
independently
dyes
unsubstituted
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EP88810652A
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German (de)
French (fr)
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EP0310556A1 (en
Inventor
Jean-Marie Sire
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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
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/34—Material containing ester groups
    • 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
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/68—Preparing azo dyes on the material
    • 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
    • D06P1/30—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
    • 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
    • D06P1/62—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 low-molecular-weight organic compounds with sulfate, sulfonate, sulfenic or sulfinic groups
    • D06P1/628—Compounds containing nitrogen
    • 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
    • D06P1/64—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 low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/642—Compounds containing nitrogen
    • D06P1/6429—Compounds containing nitrogen bound to a six-membered aromatic carbocyclic ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/916—Natural fiber dyeing
    • Y10S8/918—Cellulose textile

Definitions

  • the present invention relates to a novel process for dyeing textile cellulosic fibers with vat dyes, sulfur dyes, leuco vat ester dyes or azo development dyes using the padding process.
  • the foulard process is a dyeing process known for cellulose fibers, which allows large amounts of textile fiber materials to be dyed and soaked by impregnating or impregnating the fiber with the dye solution in a trough with the shortest liquor ratio and usually only once passing through the foulard with a short dyeing time then fix it.
  • Tailing / reverse tailing is the difference in strength and nuance between the beginning and end of a game. When only one dye is used, the end unevenness is noticeable in differences in strength, while shades in the shade can often also occur with combination dyeings.
  • Tailing is a weakening of the color strength between the beginning and end of the batch, which is due to a decrease in the dye concentration in the trough. This depletion of the dye in the liquor is caused by drawing up the dye in the padding process caused. Differences in strength and shade based on tailing occur particularly in the case of dyes with medium to high substantivity and very particularly often when coloring light shades.
  • Reverse tailing is an increase in color strength between the beginning and end of the batch, which is due to the increase in the dye concentration in the trough. This dye accumulation in the padding liquor is caused by a preferred water adsorption in the padding process. Differences in strength and shade based on reverse tailing occur with dyes of low substantivity, especially when coloring dark shades.
  • the azine compounds of formula (1) are preferred.
  • the colorless nitrogen-containing compound of formula (1) or (2) used in the process according to the invention is water-soluble and has substantivity for cellulose fibers, i.e. it is fiber-affine.
  • the amount of the fiber-affine compound in the processes according to the invention depends in particular on the amount of dye used, a minimum amount of 0.5 g / l and generally from 0.5 to 20 g / l, preferably 3 g / l to 10 g / l has proven to be very beneficial.
  • the fiber-affine compound contains 1 to 6, expediently 1 to 4, acidic water-solubilizing groups, which are in particular carboxyl groups or especially sulfonic acid groups.
  • the fiber-affine compound can contain only carboxyl groups or only sulfo groups as well as both carboxyl and sulfo groups.
  • the fiber-affine compound preferably contains 2 to 4 sulfonic acid groups.
  • C1-C5-alkyl means alkyl radicals or alkyl constituents which contain 1 to 5 carbon atoms and can be straight-chain or branched. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl or isoamyl.
  • C1-C5 alkoxy examples are methoxy, ethoxy, isopropoxy, sec-butoxy, tert. Butoxy or tert-amyloxy.
  • aromatic or heteroaromatic radicals R1, R2 and R3 mean, for example, the phenyl, biphenylyl, naphthyl, stilbenyl, furfuryl or quinolinyl radical. Phenyl and naphthyl are preferred. In addition to Z, preferred substituents of these radicals are halogens and hydroxyl.
  • Halogen means for example fluorine, bromine or preferably chlorine.
  • the phen group hydroxy, cyano, nitro, halogen, C1-C5-alkyl, trifluoromethyl, C1-C5-alkoxy, C2-C5-alkoxycarbonyl, amino, mono- or di-C1-C5-alkylamino, phenylamino, carbamoyl, Sulfamoyl, ureido, C1-C7 acylamino, such as Acetylamino, propionylamino or benzoylamino, C1-C5 alkylsulfonyl, e.g. Contain methylsulfonyl, or sulfomethyl or sulfatoethyl.
  • the colorless nitrogen-containing compounds used in the process according to the invention are known per se or can be prepared by processes known per se. They are either in the form of the free acid or, preferably, as their salts.
  • suitable salts are the alkali, alkaline earth or ammonium salts or the salts of an organic amine. Examples include the sodium, potassium or ammonium salts or the salt of triethylamine or triethanolamine.
  • V is preferably R2-X2 ⁇ and W is especially R3-X3 ⁇ .
  • Azine compounds of the formula (1) in which X1, X2 and X3 each represent ⁇ NH- are particularly preferred.
  • aryl radical such as e.g. is a naphthyl or especially a phenyl radical.
  • V R2-X2 ⁇ and W are hydroxyl.
  • triazine compounds of the formula (5) in which X1, X2 and X3 each have ⁇ NH ⁇ , R1, R2 and R3, independently of one another, each phenyl or naphthyl, Z is the sulfonic acid group and m 2 to 4, preferably 2 or 3 mean.
  • triazine compounds of formula (6) in which V 'R2-X2 ⁇ and W' are hydroxyl.
  • colorless nitrogen-containing compounds which can be used according to the invention are and
  • Suitable cellulose fibers are natural fibers, such as mercerized or bleached cotton and linen (bleached), and regenerated fibers, such as viscose, rayon, polynosic and copper rayon. Mainly woven or knitted fabrics made of these fibers, especially cotton.
  • Fiber blends e.g. those made of polyester / cotton, the polyester portion being colored with disperse dyes, can also be used.
  • Suitable dyestuffs which can be used in the process according to the invention are the dyestuffs of the type mentioned which are customarily used for dyeing or printing cellulose textile materials.
  • the leuco vat ester dyes are e.g. from vat dyes of the indigo, anthraquinone or indanthrene series by reduction e.g. with iron powder and subsequent esterification e.g. available with chlorosulfonic acid and are referred to in the Color Index 3rd Edition, 1971, Vol. 3 as "Solubilized Vat Dyes".
  • vat dyes are, for example, higher fused and heterocyclic benzoquinones or naphthoquinones, in particular anthraquinone or indigoid dyes, especially sulfur dyes.
  • vat dyes which can be used according to the invention are listed in the Color Index 3rd Edition (1971) Vol. 3 on pages 3649 to 3837 under the names "Sulfur Dyes” and "Vat Dyes”.
  • the components for the azo development dyes are the color index 3rd edition 1971 as Azoic Coupling Components ("Naphthole”) and the chemical compounds listed as Azoic Diazo Components.
  • the amount of dyes in the process according to the invention generally depends on the desired color strength, with end unevenness especially in the case of light shades, i.e. at a concentration of 0.03 g / l to 10 g / l, preferably 0.05 to 6 g / l.
  • a particularly preferred embodiment of the process according to the invention consists in that an aqueous dye liquor is used which contains 1 to 6 g / l of dye and 3 to 10 g / l of azine compound.
  • the term g / l means grams per liter. For dyes, it refers to 100% powder trading form.
  • the dyeing liquors can contain other conventional additives in addition to the colorless compound, e.g. Alkali such as sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, trisodium phosphate, borax, aqueous ammonia, or alkali dispensers such as e.g. Sodium formate or sodium trichloroacetate, electrolytes such as e.g. Contain sodium chloride or sodium sulfate as well as urea, thiourea or glycerin. If necessary, thickeners such as e.g. Alginates, starch ether or locust bean gum may be contained therein.
  • Alkali such as sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, trisodium phosphate, borax, aqueous ammonia
  • alkali dispensers such as e.g. Sodium formate or sodium trichloroacetate, electrolytes such as e.g. Contain
  • Sodium dithionite sodium hydrosulfite
  • the linking is usually carried out in an alkaline medium.
  • alkali-resistant wetting agents e.g. Sulfonates of polycarboxylic acid esters, e.g. Dihexyl sulfosuccinate or dioctyl sulfosuccinate; Straight chain or branched chain alkylarylsulfonates with at least 6 carbon atoms, e.g. Dodecylbenzenesulfonates or preferably alkylsulfonates whose alkyl chain contains 8 to 20 carbon atoms, e.g. Add dodecyl sulfonates or pentadecyl sulfonates.
  • the sulfonates mentioned as wetting agents are generally present as alkali metal salts, in particular as sodium salts or also as ammonium salts.
  • the amounts in which the wetting agents are added to the dyeing liquor are more appropriately between 0.2 to 10 g, preferably 0.5 to 3 g, per liter of liquor.
  • the dye fixation on pure cellulose fibers is carried out by customary methods, the fixing time and fixing temperature depending on the fiber material and on the dye. Steaming times in saturated steam between 30 seconds and 5 minutes at 100 to 105 ° C. are generally sufficient to achieve a uniform and optimal dye fixation. High-temperature steaming or dry heat steaming is used to fix at 105-190 ° C for 20 seconds to 3 minutes. In particular, the dyes are fixed with steam at a temperature of 100 ° C to 120 ° C for 30 seconds to 3 minutes. If necessary, the textile material is dried before fixing.
  • fixation can also be carried out by the cold dwell process, such as 6 to 24 hours residence time at room temperature.
  • the dyed cellulose material can be washed out in a conventional manner in order to remove unfixed dye.
  • the substrate is treated, for example, at from 40 ° C. to cooking temperature in a solution which contains soap or synthetic detergent. Treatment with a fixative can then be carried out to improve wet fastness.
  • the dyeings are completed by rinsing in hot and / or cold water and, if appropriate, with subsequent washing in the presence of a commercially available detergent, followed by rinsing in water and drying.
  • the dive time is 3 seconds.
  • the fabric is steamed at 101-103 ° C for one minute and rinsed with water at 25 ° C.
  • the dyeing is then oxidized with 5 ml of hydrogen peroxide for 2 minutes at 70 ° C., then soaped and rinsed hot and cold.
  • a cotton cord fabric dyed in the same shade of red with very good fastness properties is obtained.
  • Example 1 If one proceeds as described in Example 1, but uses a liquor without the triazine compound of the formula (8), a cotton cord fabric dyed in a different shade of red is obtained, the beginning of the lot being darker in color compared to the end of the lot, because the squeezed liquor is depleted of dye and thus diluted.
  • the dyeing is treated with saturated steam at 101 ° C for 90 seconds and rinsed cold, then the dyeing is oxidized at 70 ° C for 60 seconds with 7 ml / l hydrogen peroxide, boiling soaped with 1 g / l detergent, hot and rinsed cold and dried.
  • the fabric is rinsed cold, neutralized with an aqueous solution containing 2 g / l sodium carbonate, soaped at the boil, rinsed hot and cold and finally dried.
  • a cotton fabric dyed in the same shade of blue with very good fastness properties is obtained.
  • the cotton cretonne fabric After 30 seconds of air, the cotton cretonne fabric is dried in a hot flue at 120 ° C. for 45 seconds. The color is then developed by impregnation on the pad with a squeezing effect of 80% liquor absorption with an aqueous liquor which contains 13 g / l of an Azoic Diazo Component 1 with a CI No. 37135. The dive time is 6 seconds. After passing the development pad, there is an air passage of 30 seconds. The cotton cretonne fabric is then rinsed with water at 70 ° C., soaped at the boil with 2 g / l detergent, rinsed hot and cold and dried.
  • the fabric is rinsed cold, neutralized with an aqueous solution containing 2 g / l sodium carbonate, soaped at the boil, rinsed hot and cold and finally dried.

Abstract

A process for dyeing cellulose fibres or cellulose-containing blend fibres with vat dyes, sulfur dyes, leuco vat ester dyes or azoic dyes by the pad dyeing process without incurring ending, in which an aqueous dyeing liquor is used which, aside from the dye, contains a colorless compound of the formula <IMAGE> (1) or of the formula [R1-NH-A-R2]-Zm (2) where Q is <IMAGE> or =N-, Y is hydrogen, halogen, cyano, C1-C5alkyl or C1-C5alkylsulfonyl, V and W, independently of each other, are each R2-X2-, R3-X3-, hydroxyl C1-C5alkoxy or an unsubstituted or C1-C5alkyl- or C5-C6cycloalkyl-monosubstituted or -disubstituted amino group, the alkyl radical being unsubstituted or substituted by hydroxyl, cyano, sulfo or sulfato, R1, R2 and R3, independently of one another, are each an aromatic or heteroaromatic radical, X1, X2 and X3, independently of one another, are each -O-, -S-, <IMAGE> -NH-CO-Phen-NH- or NH-CO-Phen-CO-NH-, R4 ishydrogen, C1-C5alkyl, C5-C6cycloalkyl or phenyl, Phen is an unsubstituted or substituted phenylene group, A is a direct bond, -CO- or -CONH-, Z is an acidic, water-solubilizing group and m is 1 to 6.

Description

Die vorliegende Erfindung betrifft eine neues Verfahren zum endengleichen Färben von textilen Cellulosefasern mit Küpenfarbstoffen, Schwefelfarbstoffen, Leukoküpenesterfarbstoffen oder Azoentwicklungsfarbstoffen nach dem Foulard-Verfahren.The present invention relates to a novel process for dyeing textile cellulosic fibers with vat dyes, sulfur dyes, leuco vat ester dyes or azo development dyes using the padding process.

Das Foulard-Verfahren ist ein für Cellulosefasern bekanntes Färbeverfahren, welches es erlaubt, durch Tränken bzw. Imprägnieren der Faser mit der Farbstofflösung in einem Trog bei kürzestem Flottenverhältnis und meist nur einmaliger Warenpassage auf dem Foulard bei kurzer Färbedauer grosse Metragen von textilen Fasermaterialien zu färben und anschliessend zu fixieren.The foulard process is a dyeing process known for cellulose fibers, which allows large amounts of textile fiber materials to be dyed and soaked by impregnating or impregnating the fiber with the dye solution in a trough with the shortest liquor ratio and usually only once passing through the foulard with a short dyeing time then fix it.

Ein bekannter Nachteil dieser Verfahrensweise ist die in vielen Fällen zu beobachtende Endenungleichheit der gefärbten Fasermaterialien (Partien).A known disadvantage of this procedure is the end inequality of the dyed fiber materials (lots) that can be observed in many cases.

Unter Endenungleichheit (tailing/reverse tailing) versteht man die Differenzen in der Stärke und Nuance zwischen dem Anfang und dem Ende einer Partie. Bei der Verwendung nur eines Farbstoffes macht sich die Endenungleichheit in Stärkedifferenzen bemerkbar, während bei Kombinationsfärbungen oft auch noch Verschiebungen in der Nuance auftreten können.Tailing / reverse tailing is the difference in strength and nuance between the beginning and end of a game. When only one dye is used, the end unevenness is noticeable in differences in strength, while shades in the shade can often also occur with combination dyeings.

Unter tailing versteht man eine Abschwächung der Farbstärke zwischen Anfang und Ende der Partie, die auf eine Abnahme der Farbstoffkonzentration im Trog zurückzuführen ist. Diese Farbstoffverarmung der Flotte wird durch ein Aufziehen des Farbstoffes bei dem Foulardierprozess verursacht. Auf dem tailing beruhende Stärke- und Nuancendifferenzen treten insbesondere bei Farbstoffen mit mittlerer bis hoher Substantivität und ganz besonders häufig beim Färben heller Nuancen auf.Tailing is a weakening of the color strength between the beginning and end of the batch, which is due to a decrease in the dye concentration in the trough. This depletion of the dye in the liquor is caused by drawing up the dye in the padding process caused. Differences in strength and shade based on tailing occur particularly in the case of dyes with medium to high substantivity and very particularly often when coloring light shades.

Unter reverse tailing versteht man eine Zunahme der Farbstärke zwischen Anfang und Ende der Partie, die auf der Zunahme der Farbstoffkonzentration im Trog beruht. Diese Farbstoffanreicherung in der Foulardflotte wird durch eine bevorzugte Wasseradsorption bei dem Foulardierprozess verursacht. Auf dem reverse tailing beruhende Stärke- und Nuancendifferenzen treten bei Farbstoffen niedriger Substantivität, besonders beim Färben dunkler Nuancen auf.Reverse tailing is an increase in color strength between the beginning and end of the batch, which is due to the increase in the dye concentration in the trough. This dye accumulation in the padding liquor is caused by a preferred water adsorption in the padding process. Differences in strength and shade based on reverse tailing occur with dyes of low substantivity, especially when coloring dark shades.

Die aufgrund der Untersuchungen zur Endenungleichheit (Journal of the Society of Dyers and Colourists, 71 (1955), Seiten 13 bis 20; oder SVF (Schweizerische Vereinigung von Färbereifachleuten-Fachorgan 16 (1961), Seiten 341 bis 351, ITS Veredlung 33, (1987/1), Seiten 5-6, 9, 12, 16, 19) bisher ergriffenen Massnahmen zur Verbesserung dieses nachteiligen Effekts, wie z.B. Verkürzung der Tauchzeit, spezifische Farbstoffauswahl und die der Affinität des Farbstoffes auf der jeweiligen Faser bzw. dem Färbeverfahren angepasste Farbstoffkonzentration der Foulardflotte, die kontinuierlich nachgesetzt wird, haben sich in der Praxis nicht durchsetzen können. So wirkt sich für schwere, dichtgeschlagene bzw. ungenügend hydrophile und langsam quellende Waren eine zu kurze Tauchzeit nachteilig aus; die Verwendung weniger, ausgewählter Farbstoffe bedingt geringere Möglichkeiten zur Nuanceneinstellung und beschränkt den Einsatz solcher Farbstoffe auf nur helle oder nur dunkle Nuancen; und die variierte Farbstoffkonzentration in der Nachsatzflotte ist für die Praxis oft zu kompliziert, u.a. wegen mangelnder Reproduzierbarkeit.The due to the studies on the inequality of ends (Journal of the Society of Dyers and Colorists, 71 (1955), pages 13 to 20; or SVF (Swiss Association of Dyeing Experts Specialist Organ 16 (1961), pages 341 to 351, ITS finishing 33 , ( 1987/1), pages 5-6, 9, 12, 16, 19) measures taken so far to improve this disadvantageous effect, such as shortening the dipping time, specific choice of dye and the dye's affinity for the respective fiber or the dyeing process The dye concentration of the padding fleet, which is continuously topped up, has not been able to establish itself in practice, so that too short a diving time has an adverse effect on heavy, tightly packed or insufficiently hydrophilic and slowly swelling goods; the use of fewer, selected dyes means fewer possibilities Adjustment of shades and limits the use of such dyes to only light or only dark shades; and that Varying dye concentration in the make-up liquor is often too complicated for practical reasons, among other things due to the lack of reproducibility.

So besteht seit langem ein Bedürfnis, die Endenungleichheit einer Partie zu verbessern.There has long been a need to improve the end inequality of a lot.

Ueberraschenderweise wurde nun ein neues Verfahren gefunden, das die genannten Nachteile nicht aufweist und welches erlaubt, auf einfache Art und Weise textile Cellulosefasern mit Küpenfarbstoffen, Schwefelfarbstoffen, Leukoküpenesterfarbstoffen oder Azoentwicklungsfarbstoffen insbesondere in hellen Nuancen nach dem Foulard-Verfahren endengleich zu färben.Surprisingly, a new process has now been found which does not have the disadvantages mentioned and which allows textile cellulose fibers with vat dyes, sulfur dyes, To dye leuco vat ester dyes or azo development dyes, especially in light shades, using the foulard process.

Gegenstand der vorliegenden Erfindung ist somit ein Verfahren zum endengleichen Färben von Cellulosefasern oder cellulosehaltigen Mischfasern mit Küpenfarbstoffen, Schwefelfarbstoffen, Leukoküpenesterfarbstoffen oder Azoentwicklungsfarbstoffen nach dem Foulard-Verfahren, welches dadurch gekennzeichnet ist, dass man eine wässrige Färbeflotte verwendet, welche ausser dem Farbstoff eine farblose stickstoffhaltige Verbingung der Formel

Figure imgb0001

oder der Formel
Figure imgb0002
enthält, worin
Figure imgb0003

Y
Wasserstoff, Halogen, Cyano, C₁-C₅-Alkyl oder C₁-C₅-Alkylsulfonyl,
V und W,
unabhängig voneinander, je R₂-X₂―, R₃-X₃―, Hydroxy, C₁-C₅-Alkoxy oder eine unsubstituierte oder durch einen C₁-C₅-Alkylrest oder C₅-C₆-Cycloalkylrest mono- oder disubstituierte Aminogruppe, wobei der Alkylrest unsubstituiert oder durch Hydroxy, Cyano, Sulfo (―SO₃H) oder Sulfato (―OSO₃H) substituiert ist,
R₁, R₂ und R₃,
unabhängig voneinander, je einen aromatischen oder heteroaromatischen Rest,
X₁, X₂ und X₃
unabhängig voneinander, je ―O―, ―S―,
Figure imgb0004
 ―NH-CO-Phen-NH― oder ―NH-CO-Phen-CO-NH―,
R₄
Wasserstoff, C₁-C₅-Alkyl, C₅-C₆-Cycloalkyl oder Phenyl,
Phen
eine unsubstituierte oder substituierte Phenylengruppe,
A
die direkte Bindung, ―CO― oder ―CONH―,
Z
eine saure, wasserlöslichmachende Gruppe und
m
1 bis 6 bedeuten.

The present invention thus relates to a process for dyeing cellulose fibers or cellulose-containing mixed fibers with vat dyes, sulfur dyes, leucocubes ester dyes or azo development dyes according to the fouling method, which is characterized in that an aqueous dye liquor is used which, in addition to the dye, contains a colorless nitrogen-containing compound of the formula
Figure imgb0001
or the formula
Figure imgb0002
contains what
Figure imgb0003
Y
Hydrogen, halogen, cyano, C₁-C₅-alkyl or C₁-C₅-alkylsulfonyl,
V and W,
independently of one another, each R₂-X₂―, R₃-X₃―, hydroxy, C₁-C₅-alkoxy or an unsubstituted or by a C₁-C₅-alkyl radical or C₅-C₆-cycloalkyl radical mono- or disubstituted amino group, the alkyl radical being unsubstituted or by Hydroxy, cyano, sulfo (―SO₃H) or sulfato (―OSO₃H) is substituted,
R₁, R₂ and R₃,
independently of one another, each an aromatic or heteroaromatic radical,
X₁, X₂ and X₃
independently of each other, each ―O―, ―S―,
Figure imgb0004
 ―NH-CO-Phen-NH― or ―NH-CO-Phen-CO-NH―,
R₄
Hydrogen, C₁-C₅-alkyl, C₅-C₆-cycloalkyl or phenyl,
Phen
an unsubstituted or substituted phenylene group,
A
the direct bond, ―CO― or ―CONH―,
Z
an acidic, water solubilizing group and
m
1 to 6 mean.

Die Azinverbindungen der Formel (1) sind bevorzugt.The azine compounds of formula (1) are preferred.

Die im erfindungsgemässen Verfahren verwendete farblose stickstoffhaltige Verbindung der Formel (1) oder (2) ist wasserlöslich und besitzt Substantivität für Cellulosefasern, d.h. sie ist faseraffin.The colorless nitrogen-containing compound of formula (1) or (2) used in the process according to the invention is water-soluble and has substantivity for cellulose fibers, i.e. it is fiber-affine.

Die Menge der faseraffinen Verbindung in den erfindungsgemässen Verfahren richtet sich insbesondere nach der eingesetzten Farbstoffmenge, wobei eine Mindestmenge von 0,5 g/l und in der Regel von 0,5 bis 20 g/l, vorzugsweise 3 g/l bis 10 g/l sich als sehr vorteilhaft erwiesen hat.The amount of the fiber-affine compound in the processes according to the invention depends in particular on the amount of dye used, a minimum amount of 0.5 g / l and generally from 0.5 to 20 g / l, preferably 3 g / l to 10 g / l has proven to be very beneficial.

Die faseraffine Verbindung enthält 1 bis 6, zweckmässigerweise 1 bis 4, saure wasserlöslichmachende Gruppen, die insbesondere Carboxylgruppen oder vor allem Sulfonsäuregruppen sind. Dabei kann die faseraffine Verbindung sowohl nur Carboxylgruppen oder nur Sulfogruppen wie auch beide Carboxyl- und Sulfogruppen enthalten. Vorzugsweise enthält die faseraffine Verbindung 2 bis 4 Sulfonsäuregruppen.The fiber-affine compound contains 1 to 6, expediently 1 to 4, acidic water-solubilizing groups, which are in particular carboxyl groups or especially sulfonic acid groups. The fiber-affine compound can contain only carboxyl groups or only sulfo groups as well as both carboxyl and sulfo groups. The fiber-affine compound preferably contains 2 to 4 sulfonic acid groups.

C₁-C₅-Alkyl bedeutet Alkylreste oder Alkylbestandteile, die 1 bis 5 Kohlenstoffatome enthalten und geradkettig oder verzweigt sein können. Beispiele sind Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, sek.Butyl, Isobutyl, tert.-Butyl, n-Amyl oder Isoamyl.C₁-C₅-alkyl means alkyl radicals or alkyl constituents which contain 1 to 5 carbon atoms and can be straight-chain or branched. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-amyl or isoamyl.

Beispiele für C₁-C₅-Alkoxy sind Methoxy, Ethoxy, Isopropoxy, sek.-Butoxy, tert. Butoxy oder tert.-Amyloxy.Examples of C₁-C₅ alkoxy are methoxy, ethoxy, isopropoxy, sec-butoxy, tert. Butoxy or tert-amyloxy.

Als aromatische oder heteroaromatische Reste bedeuten R₁, R₂ und R₃ beispielsweise den Phenyl-, Biphenylyl-, Naphthyl-, Stilbenyl, Furfuryl- oder Chinolinylrest. Phenyl und Naphthyl sind bevorzugt. Bevorzugte Substituenten dieser Reste sind ausser Z Halogene und Hydroxyl.As aromatic or heteroaromatic radicals R₁, R₂ and R₃ mean, for example, the phenyl, biphenylyl, naphthyl, stilbenyl, furfuryl or quinolinyl radical. Phenyl and naphthyl are preferred. In addition to Z, preferred substituents of these radicals are halogens and hydroxyl.

Halogen bedeutet beispielsweise Fluor, Brom oder vorzugsweise Chlor.Halogen means for example fluorine, bromine or preferably chlorine.

Als Substituenten kann die Phengruppe Hydroxy, Cyano, Nitro, Halogen, C₁-C₅-Alkyl, Trifluormethyl, C₁-C₅-Alkoxy, C₂-C₅-Alkoxycarbonyl, Amino, Mono- oder Di-C₁-C₅-alkylamino, Phenylamino, Carbamoyl, Sulfamoyl, Ureido, C₁-C₇-Acylamino, wie z.B. Acetylamino, Propionylamino oder Benzoylamino, C₁-C₅-Alkylsulfonyl, wie z.B. Methylsulfonyl, oder Sulfomethyl oder Sulfatoethyl enthalten.As a substituent, the phen group hydroxy, cyano, nitro, halogen, C₁-C₅-alkyl, trifluoromethyl, C₁-C₅-alkoxy, C₂-C₅-alkoxycarbonyl, amino, mono- or di-C₁-C₅-alkylamino, phenylamino, carbamoyl, Sulfamoyl, ureido, C₁-C₇ acylamino, such as Acetylamino, propionylamino or benzoylamino, C₁-C₅ alkylsulfonyl, e.g. Contain methylsulfonyl, or sulfomethyl or sulfatoethyl.

Die im erfindungsgemässen Verfahren verwendeten farblosen stickstoffhaltigen Verbindungen sind an sich bekannt oder können nach an sich bekannten Verfahren hergestellt werden. Sie liegen entweder in der Form der freien Säure oder vorzugsweise als deren Salze vor. Als Salze kommen beispielsweise die Alkali-, Erdalkali- oder Ammoniumsalze oder die Salze eines organischen Amins in Betracht. Als Beispiele seien die Natrium-, Kalium- oder Ammoniumsalze oder das Salz des Triethylamins oder Triethanolamins genannt.The colorless nitrogen-containing compounds used in the process according to the invention are known per se or can be prepared by processes known per se. They are either in the form of the free acid or, preferably, as their salts. Examples of suitable salts are the alkali, alkaline earth or ammonium salts or the salts of an organic amine. Examples include the sodium, potassium or ammonium salts or the salt of triethylamine or triethanolamine.

In den Azinverbindungen der Formel (1) bedeutet V vorzugsweise R₂-X₂― und W ist vor allem R₃-X₃―. Besonders bevorzugt werden Azinverbindungen der Formel (1), worin X₁, X₂ und X₃ jeweils ―NH-bedeuten. Ganz besonders bevorzugt sind Verbindungen der Formel (1), in der R₁, R₂ und R₃ je einen Arylrest, wie z.B. einen Naphthyl-oder besonders einen Phenylrest bedeuten. Von praktischem Interesse sind auch Azinverbindungen der Formel (1), in der V R₂-X₂― und W Hydroxyl bedeuten.In the azine compounds of formula (1) V is preferably R₂-X₂― and W is especially R₃-X₃―. Azine compounds of the formula (1) in which X₁, X₂ and X₃ each represent ―NH- are particularly preferred. Compounds of formula (1) in which R₁, R₂ and R₃ each have an aryl radical, such as e.g. is a naphthyl or especially a phenyl radical. Of practical interest are also azine compounds of formula (1) in which V R₂-X₂― and W are hydroxyl.

Aus der grossen Zahl möglicher wasserlöslicher, faseraffiner Azinverbindungen kommen beispielsweise Verbindungstypen der folgenden Formeln in Betracht:

Figure imgb0005
Figure imgb0006
 worin

Y
die angegebene Bedeutung hat, besonders Wasserstoff oder Halogen,
V′ und W′,
unabhängig voneinander, je Hydroxy, C₁-C₄-Alkoxy, oder eine unsubstituierte oder durch einen C₁-C₅-Alkylrest mono- oder disubstituierte Aminogruppe, wobei der Alkylrest unsubstituiert oder durch Hydroxy, Cyano, Sulfo oder Sulfato substituiert ist und V′ auch den Rest R₂-X₂―,
R₁, R₂ und R₃,
unabhängig voneinander, je einen aromatischen oder heteroaromatischen Rest, wie z.B. den Phenyl-, Biphenylyl-, Naphthyl-, Stilbenyl-, Furfuryl- oder Chinolinylrest bedeuten, wobei R₁, R₂ und R₃ ausser Z beliebige nicht-ionogene Substituenten enthalten können, wie z.B. Alkylgruppen mit 1 bis 5 Kohlenstoffatomen, wie Methyl, Aethyl, Propyl, Isopropyl, Butyl oder Amyl, Alkoxygruppen mit 1 bis 4 Kohlenstoffatomen, wie Methoxy, Aethoxy, Propoxy, Isopropoxy oder Butoxy, Acylaminogruppen mit 1 bis 7 Kohlenstoffatomen, wie z.B. Acetylamino, Propionylamino oder Benzoylamino, Amino, Mono- oder Dialkylamino mit 1 bis 5 Kohlenstoffatomen im Alkylrest, Phenylamino, Alkoxycarbonyl mit 1 bis 4 Kohlenstoffatomen im Alkoxyrest, Nitro, Cyano, Trifluormethyl, Halogen, wie z.B. Fluor, Chlor oder Brom, Sulfamoyl, Carbamoyl, Ureido, Hydroxy, C₁-C₄-Alkylsulfonyl, wie z.B. Methylsulfonyl, oder auch Sulfomethyl (HO₃S-CH₂―),
X₁, X₂ und X₃,
unabhängig voneinander, je ―O―, ―S―, oder ―N(R₅)― sind, wobei R₅ Wasserstoff, C₁₋₄-Alkyl oder Phenyl ist, Z eine saure, wasserlöslichmachende Gruppe, wie z.B. die Carboxyl- oder vorzugsweise Sulfonsäuregruppe ist und
m
= 2, 3, 4, 5 oder 6, vorzugsweise 2 bis 4 ist.

From the large number of possible water-soluble, fiber-affine azine compounds, for example, compound types of the following formulas come into consideration:
Figure imgb0005
Figure imgb0006
 wherein
Y
has the meaning given, especially hydrogen or halogen,
V ′ and W ′,
independently of one another, each hydroxyl, C₁-C₄-alkoxy, or an unsubstituted or mono- or disubstituted amino group by a C₁-C₅-alkyl radical, the alkyl radical being unsubstituted or substituted by hydroxy, cyano, sulfo or sulfato and V 'also the rest R₂-X₂―,
R₁, R₂ and R₃,
independently of one another, each represent an aromatic or heteroaromatic radical, such as, for example, the phenyl, biphenylyl, naphthyl, stilbenyl, furfuryl or quinolinyl radical, where R₁, R₂ and R₃ apart from Z can contain any nonionic substituents, such as alkyl groups with 1 to 5 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl or amyl, alkoxy groups with 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy or butoxy, acylamino groups with 1 to 7 carbon atoms, such as acetylamino, propionylamino or Benzoylamino, amino, mono- or dialkylamino with 1 to 5 carbon atoms in the alkyl radical, phenylamino, alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy radical, nitro, cyano, trifluoromethyl, halogen, such as fluorine, chlorine or bromine, sulfamoyl, carbamoyl, ureido, hydroxy , C₁-C₄-alkylsulfonyl, such as methylsulfonyl, or sulfomethyl (HO₃S-CH₂―),
X₁, X₂ and X₃,
independently of one another, each ―O―, ―S―, or ―N (R₅) -, where R₅ is hydrogen, C₁₋₄-alkyl or phenyl, Z is an acidic, water-solubilizing group, such as the carboxyl or preferably sulfonic acid group and
m
= 2, 3, 4, 5 or 6, preferably 2 to 4.

Im Vordergrund des Interesses stehen Triazinverbindungen der Formel (5), in der X₁, X₂ und X₃ jeweils ―NH―, R₁, R₂ und R₃, unabhängig voneinander, je Phenyl oder Naphthyl, Z die Sulfonsäuregruppe und m 2 bis 4, vorzugsweise 2 oder 3 bedeuten. Von praktischem Interesse sind auch Triazinverbindungen der Formel (6), in der V′ R₂-X₂― und W′ Hydroxyl bedeuten.In the foreground of interest are triazine compounds of the formula (5) in which X₁, X₂ and X₃ each have ―NH―, R₁, R₂ and R₃, independently of one another, each phenyl or naphthyl, Z is the sulfonic acid group and m 2 to 4, preferably 2 or 3 mean. Of practical interest are also triazine compounds of formula (6) in which V 'R₂-X₂― and W' are hydroxyl.

Besonders interessante Triazinverbindungen entsprechen z.B. den Formeln

Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
 Particularly interesting triazine compounds correspond, for example, to the formulas
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018

Weitere Beispiele für erfindungsgemäss verwendbare farblose stickstoffhaltige Verbindungen sind

Figure imgb0019
und
Figure imgb0020
 Further examples of colorless nitrogen-containing compounds which can be used according to the invention are
Figure imgb0019
 and
Figure imgb0020

Als Cellulosefasern kommen natürliche Fasern, wie mercerisierte oder gebleichte Baumwolle und Leinen (gebleicht), und regenerierte Fasern, wie Viskose, Zellwolle, Polynosic und Kupfer-Kunstseiden in Betracht. Hauptsächlich werden Gewebe oder Gewirke dieser Fasern, vor allem aus Baumwolle verwendet.Suitable cellulose fibers are natural fibers, such as mercerized or bleached cotton and linen (bleached), and regenerated fibers, such as viscose, rayon, polynosic and copper rayon. Mainly woven or knitted fabrics made of these fibers, especially cotton.

Fasermischungen, z.B. solche aus Polyester/Baumwolle, wobei der Polyesteranteil mit Dispersionsfarbstoffen gefärbt wird, können auch verwendet werden.Fiber blends, e.g. those made of polyester / cotton, the polyester portion being colored with disperse dyes, can also be used.

Als im erfindungsgemässen Verfahren verwendbare Farbstoffe kommen die üblicherweise zum Färben oder Bedrucken von Cellulose-Textilmaterialien eingesetzten Farbstoffe der genannten Art in Betracht.Suitable dyestuffs which can be used in the process according to the invention are the dyestuffs of the type mentioned which are customarily used for dyeing or printing cellulose textile materials.

Die Leukoküpenesterfarbstoffe sind z.B. aus Küpenfarbstoffen der Indigo-, Anthrachinon- oder Indanthren-Reihe durch Reduktion z.B. mit Eisenpulver und anschliessende Veresterung z.B. mit Chlorsulfonsäure erhältlich und sind im Colour Index 3rd Edition, 1971, Vol. 3 als "Solubilised Vat Dyes" bezeichnet.The leuco vat ester dyes are e.g. from vat dyes of the indigo, anthraquinone or indanthrene series by reduction e.g. with iron powder and subsequent esterification e.g. available with chlorosulfonic acid and are referred to in the Color Index 3rd Edition, 1971, Vol. 3 as "Solubilized Vat Dyes".

Bei den Küpenfarbstoffen handelt es sich z.B. um höher annellierte und heterocyclische Benzochinone oder Naphthochinone, insbesondere um anthrachinoide oder indigoide Farbstoffe, vor allem um Schwefelfarbstoffe. Beispiele von erfindungsgemäss verwendbaren Küpenfarbstoffen sind im Colour Index 3rd Edition (1971) Vol. 3 auf den Seiten 3649 bis 3837 unter der Bezeichnung "Sulphur Dyes" und "Vat Dyes" aufgeführt.The vat dyes are, for example, higher fused and heterocyclic benzoquinones or naphthoquinones, in particular anthraquinone or indigoid dyes, especially sulfur dyes. Examples of vat dyes which can be used according to the invention are listed in the Color Index 3rd Edition (1971) Vol. 3 on pages 3649 to 3837 under the names "Sulfur Dyes" and "Vat Dyes".

Als Komponenten für die Azo-Entwicklungsfarbstoffe kommen die im Colour Index 3. Auflage 1971 als Azoic Coupling Components ("Naphthole") und die als Azoic Diazo Components aufgelisteten chemischen Verbindungen in Frage.The components for the azo development dyes are the color index 3rd edition 1971 as Azoic Coupling Components ("Naphthole") and the chemical compounds listed as Azoic Diazo Components.

Die Menge der Farbstoffe im erfindungsgemässen Verfahren richtet sich in der Regel nach der gewünschten Farbstärke, wobei sich Endenungleichheit insbesondere bei hellen Nuancen, d.h. bei einer Konzentration von 0,03 g/l bis 10 g/l, vorzugsweise 0,05 bis 6 g/l, bemerkbar macht.The amount of dyes in the process according to the invention generally depends on the desired color strength, with end unevenness especially in the case of light shades, i.e. at a concentration of 0.03 g / l to 10 g / l, preferably 0.05 to 6 g / l.

Eine besonders bevorzugte Ausführungsform des erfindungsgemässen Verfahrens besteht darin, dass eine wässerige Färbeflotte verwendet wird, die 1 bis 6 g/l Farbstoff und 3 bis 10 g/l Azinverbindung enthält. Die Bezeichnung g/l bedeutet Gramm pro Liter. Für Farbstoffe bezieht sie sich auf 100% Pulverhandelsform.A particularly preferred embodiment of the process according to the invention consists in that an aqueous dye liquor is used which contains 1 to 6 g / l of dye and 3 to 10 g / l of azine compound. The term g / l means grams per liter. For dyes, it refers to 100% powder trading form.

Die Färbeflotten können je nach dem zu verwendenden Farbstoff zusätzlich zu der farblosen Verbindung weitere übliche Zusätze enthalten, z.B. Alkali wie Natriumcarbonat, Natriumbicarbonat, Natriumhydroxyd, Kaliumhydroxid, Trinatriumphosphat, Borax, wässriges Ammoniak, oder Alkalispender wie z.B. Natriumformiat oder Natriumtrichloracetat, Elektrolyte, wie z.B. Natriumchlorid oder Natriumsulfat sowie auch Harnstoff, Thioharnstoff oder Glycerin enthalten. Gegebenenfalls können auch Verdickungsmittel, wie z.B. Alginate, Stärkeether oder Johannisbrotkernmehlether darin enthalten sein.Depending on the dye to be used, the dyeing liquors can contain other conventional additives in addition to the colorless compound, e.g. Alkali such as sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, trisodium phosphate, borax, aqueous ammonia, or alkali dispensers such as e.g. Sodium formate or sodium trichloroacetate, electrolytes such as e.g. Contain sodium chloride or sodium sulfate as well as urea, thiourea or glycerin. If necessary, thickeners such as e.g. Alginates, starch ether or locust bean gum may be contained therein.

Als Reduktionsmittel zur Ueberführung der Küpenfarbstoffe in die faseraffine Form der Leukoverbindung (Verküpen) wird beispielsweise Natriumdithionit (Natriumhydrosulfit) eingesetzt. Die Verküpung erfolgt in der Regel im alkalischen Medium.Sodium dithionite (sodium hydrosulfite), for example, is used as a reducing agent for converting the vat dyes into the fiber-affine form of the leuco compound (vatting). The linking is usually carried out in an alkaline medium.

Es hat sich vielfach als vorteilhaft erwiesen, den Färbeflotten zusätzlich noch handelsübliche alkalibeständige Netzmittel, z.B. Sulfonate von Polycarbonsäureestern, wie z.B. Dihexylsulfosuccinate oder Dioctylsulfosuccinate; Alkylarylsulfonate mit geradkettiger oder verzweigter Alkylkette mit mindestens 6 Kohlenstoffatomen, wie z.B. Dodecylbenzolsulfonate oder vorzugsweise Alkylsulfonate, deren Alkylkette 8 bis 20 Kohlenstoffatome enthält, wie z.B. Dodecylsulfonate oder Pentadecylsulfonate, zuzusetzen. Die als Netzmittel genannten Sulfonate liegen in der Regel als Alkalimetallsalze, insbesondere als Natriumsalze oder auch als Ammoniumsalze vor.It has proven to be advantageous in many cases to add commercially available alkali-resistant wetting agents, e.g. Sulfonates of polycarboxylic acid esters, e.g. Dihexyl sulfosuccinate or dioctyl sulfosuccinate; Straight chain or branched chain alkylarylsulfonates with at least 6 carbon atoms, e.g. Dodecylbenzenesulfonates or preferably alkylsulfonates whose alkyl chain contains 8 to 20 carbon atoms, e.g. Add dodecyl sulfonates or pentadecyl sulfonates. The sulfonates mentioned as wetting agents are generally present as alkali metal salts, in particular as sodium salts or also as ammonium salts.

Die Einsatzmengen, in denen die Netzmittel der Färbeflotte zugesetzt werden, bewegen sich zweckmässiger zwischen 0,2 bis 10 g, vorzugsweise 0,5 bis 3 g, pro Liter Flotte.The amounts in which the wetting agents are added to the dyeing liquor are more appropriately between 0.2 to 10 g, preferably 0.5 to 3 g, per liter of liquor.

Die Farbstoff-Fixierung auf reinen Cellulosefasern erfolgt nach üblichen Verfahren, wobei Fixierzeit und Fixiertemperatur von dem Fasermaterial und von dem Farbstoff abhängen. Zur Erzielung einer gleichmässigen und optimalen Farbstoff-Fixierung genügen im allgemeinen Dämpfzeiten im Sattdampf zwischen 30 Sekunden und 5 Minuten bei 100 bis 105°C. Durch Hochtemperatur-Dämpfen bzw. Trockenhitze-Dämpfen wird während 20 Sekunden bis 3 Minuten bei 105-190°C fixiert. Insbesondere werden die Farbstoffe mit Dampf bei einer Temperatur von 100°C bis 120°C während 30 Sekunden bis 3 Minuten fixiert. Gegebenenfalls wird das Textilmaterial vor dem Fixieren getrocknet.The dye fixation on pure cellulose fibers is carried out by customary methods, the fixing time and fixing temperature depending on the fiber material and on the dye. Steaming times in saturated steam between 30 seconds and 5 minutes at 100 to 105 ° C. are generally sufficient to achieve a uniform and optimal dye fixation. High-temperature steaming or dry heat steaming is used to fix at 105-190 ° C for 20 seconds to 3 minutes. In particular, the dyes are fixed with steam at a temperature of 100 ° C to 120 ° C for 30 seconds to 3 minutes. If necessary, the textile material is dried before fixing.

Ferner kann die Fixierung auch nach dem Kaltverweilverfahren erfolgen, wie z.B. 6 bis 24 Stunden Verweilzeit bei Raumtemperatur.Furthermore, the fixation can also be carried out by the cold dwell process, such as 6 to 24 hours residence time at room temperature.

In Anschluss an den Färbeprozess kann man das gefärbte Cellulosematerial in üblicher Weise auswaschen, um nichtfixierten Farbstoff zu entfernen. Man behandelt dazu das Substrat beispielsweise bei 40°C bis Kochtemperatur in einer Lösung, die Seife oder synthetisches Waschmittel enthält. Anschliessend kann zur Verbesserung der Nassechtheiten eine Behandlung mit einem Fixiermittel erfolgen.Following the dyeing process, the dyed cellulose material can be washed out in a conventional manner in order to remove unfixed dye. For this purpose, the substrate is treated, for example, at from 40 ° C. to cooking temperature in a solution which contains soap or synthetic detergent. Treatment with a fixative can then be carried out to improve wet fastness.

Die Fertigstellung der Färbungen erfolgt durch Spülen in heissem und/oder kaltem Wasser und gegebenenfalls mit anschliessendem Waschen in Gegenwart eines handelsüblichen Waschmittels, nachfolgendem Spülen in Wasser und Trocknen.The dyeings are completed by rinsing in hot and / or cold water and, if appropriate, with subsequent washing in the presence of a commercially available detergent, followed by rinsing in water and drying.

Die nachfolgenden Beispiele dienen der Veranschaulichung der Erfindung. Darin sind die Teile Gewichtsteile und die Prozente Gewichtsprozente. Die Temperaturen sind in Celsiusgraden angegeben.The following examples serve to illustrate the invention. The parts are parts by weight and the percentages are percentages by weight. The temperatures are given in degrees Celsius.

Beispiel 1: Example 1 :

Ein gebleichtes Baumwoll-Cord-Gewebe wird auf dem Foulard mit einem Abquetscheffekt von 90% Flottenaufnahme mit einer wässrigen Flotte imprägniert, die im Liter

6 g
des Farbstoffes Leuko Sulphur Red 1 C.I. 53721
5 g
Schwefelnatrium
1 ml
Natronlauge 36° Bé
1 g
Netzmittel und
8 g
einer Triazinverbindung der Formel (8)


enthält.A bleached cotton cord fabric is impregnated on the foulard with a squeezing effect of 90% liquor absorption with an aqueous liquor, which is in liters
6 g
of the Leuko Sulfur Red 1 CI 53721 dye
5 g
Sulfur sodium
1 ml
Sodium hydroxide solution 36 ° Bé
1 g
Wetting agents and
8 g
a triazine compound of the formula (8)


contains.

Die Tauchzeit beträgt 3 Sekunden. Nach dem Foulardieren wird das Gewebe während einer Minute bei 101-103°C gedämpft und bei 25°C mit Wasser gespült. Alsdann wird die Färbung mit 5 ml Wasserstoffsuperoxid während 2 Minuten bei 70°C oxydiert, anschliessend geseift und heiss und kalt gespült.The dive time is 3 seconds. After padding, the fabric is steamed at 101-103 ° C for one minute and rinsed with water at 25 ° C. The dyeing is then oxidized with 5 ml of hydrogen peroxide for 2 minutes at 70 ° C., then soaped and rinsed hot and cold.

Man erhält ein endengleich in rotem Farbton gefärbtes Baumwoll-Cord-Gewebe mit sehr guten Echtheiten.A cotton cord fabric dyed in the same shade of red with very good fastness properties is obtained.

Vergleichsbeispiel 1: Comparative Example 1 :

Wenn man wie in Beispiel 1 angegeben vorgeht, jedoch eine Flotte ohne die Triazinverbindung der Formel (8) verwendet, erhält man ein endenungleich in rotem Farbton gefärbtes Baumwoll-Cord-Gewebe, wobei der Anfang der Partie gegenüber dem Ende der Partie dunkler gefärbt ist, da die abgequetschte Flotte an Farbstoff verarmt und somit verdünnt wird.If one proceeds as described in Example 1, but uses a liquor without the triazine compound of the formula (8), a cotton cord fabric dyed in a different shade of red is obtained, the beginning of the lot being darker in color compared to the end of the lot, because the squeezed liquor is depleted of dye and thus diluted.

Beispiel 2: Example 2 :

3 g/l des Farbstoffes der Formel

Figure imgb0021
werden bei 50°C mit einer wässrigen Zubereitung, die

25 ml/l
Natronlauge 36° Bé
20  g/l
Natriumhydrosulfit


enthält, während 15 Minuten verküpt. Nach dem Abkühlen auf 25°C werden 7 g/l der Triazinverbindung der Formel (13) zu der verküpten Zubereitung zugesetzt. Mit dieser Zubereitung wird ein gebleichtes mercerisiertes Baumwoll-Cretonne-Gewebe auf einem Foulard mit einem Abquetscheffekt von 70% Flottenaufnahme imprägniert. Die Tauchzeit beträgt 2 Sekunden.3 g / l of the dye of the formula
Figure imgb0021
 be at 50 ° C with an aqueous preparation that
25 ml / l
Sodium hydroxide solution 36 ° Bé
20 g / l
Sodium hydrosulfite


contains while fogged for 15 minutes. After cooling to 25 ° C., 7 g / l of the triazine compound of the formula (13) are added to the linked preparation. This preparation is used to impregnate a bleached, mercerized cotton cretonne fabric on a foulard with a squeezing effect of 70% liquor absorption. The dive time is 2 seconds.

Nach dem Imprägnieren wird die Färbung während 90 Sekunden bei 101°C mit Sattdampf behandelt und kalt gespült, alsdann wird die Färbung bei 70°C während 60 Sekunden mit 7 ml/l Wasserstoffperoxid oxydiert, kochend mit 1 g/l Waschmittel geseift, heiss und kalt gespült und getrocknet.After impregnation, the dyeing is treated with saturated steam at 101 ° C for 90 seconds and rinsed cold, then the dyeing is oxidized at 70 ° C for 60 seconds with 7 ml / l hydrogen peroxide, boiling soaped with 1 g / l detergent, hot and rinsed cold and dried.

Man erhält ein endengleich in rotem Farbton gefärbtes Baumwollgewebe mit sehr guten Echtheiten.A cotton fabric dyed in the same shade of red with very good fastness properties is obtained.

Beispiel 3: Example 3 :

Ein gebleichtes mercerisiertes Baumwoll-Popeline-Gewebe wird auf dem Foulard mit einem Abquetscheffekt von 75% Flottenaufnahme mit einer wässrigen Flotte imprägniert, die im Litter

Figure imgb0022
enthält. Die Tauchzeit beträgt 2,5 Sekunden. Nach dem Imprägnieren wird das Gewebe während einer Minute bei 100°C getrocknet. Danach wird das gefärbte Material mit einer wässrigen Lösung behandelt, die im Litter

20 ml
Schwefelsäure 66° Bé
 2  g
eines Dispergiermittels z.B. Mischung von Fettsäure/Eiweiss-Kondensationsprodukt mit Alkylphenolpolyglykolether und
 1  g
Thioharnstoff enthält.

A bleached mercerized cotton poplin fabric is impregnated on the foulard with a squeezing effect of 75% liquor absorption with an aqueous liquor, which is in the litter
Figure imgb0022
 contains. The dive time is 2.5 seconds. After impregnation, the fabric is dried for one minute at 100 ° C. Then the colored material is treated with an aqueous solution, which is in the litter
20 ml
Sulfuric acid 66 ° Bé
2 g
a dispersant, for example a mixture of fatty acid / protein condensation product with alkylphenol polyglycol ether and
1 g
Contains thiourea.

Nach einem Luftgang von 20 Sekunden wird das Gewebe kalt gespült, mit einer wässrigen Lösung enthaltend 2 g/l Natriumcarbonat neutralisiert, kochend geseift, heiss und kalt gespült und schliesslich getrocknet.After 20 seconds of air, the fabric is rinsed cold, neutralized with an aqueous solution containing 2 g / l sodium carbonate, soaped at the boil, rinsed hot and cold and finally dried.

Man erhält ein endengleich in blauem Farbton gefärbtes Baumwollgewebe mit sehr guten Echtheiten.A cotton fabric dyed in the same shade of blue with very good fastness properties is obtained.

Beispiel 4: Example 4 :

Ein laugiertes Baumwoll-Cretonne-Gewebe wird bei 50°C auf einem Foulard mit einem Abquetscheffekt von 80% Flottenaufnahme mit einer wässrigen Zubereitung imprägniert, die im Litter

4 g
Azoic Coupling Component 20 mit der C.I. Nr. 37530
4 ml
30% Natriumhydroxidlösung und
4 g
der Azinverbindung der Formel (12)


enthält. Die Tauchzeit beträgt 3 Sekunden.A leached cotton cretonne fabric is impregnated at 50 ° C. on a foulard with a squeezing effect of 80% liquor absorption with an aqueous preparation which is in the litter
4 g
Azoic Coupling Component 20 with CI No. 37530
4 ml
30% sodium hydroxide solution and
4 g
the azine compound of formula (12)


contains. The dive time is 3 seconds.

Nach einem Luftgang von 30 Sekunden wird das Baumwoll-Cretonne-Gewebe in einer Hotflue während 45 Sekunden bei 120°C getrocknet. Danach wird die Farbe entwickelt durch Imprägnieren auf dem Foulard mit einem Abquetscheffekt von 80% Flottenaufnahme mit einer wässrigen Flotte, die 13 g/l eines Azoic Diazo Component 1 mit einer C.I. Nr. 37135 enthält. Die Tauchzeit beträgt 6 Sekunden. Nach dem Passieren des Entwicklungsfoulards folgt ein Luftgang von 30 Sekunden. Alsdann wird das Baumwoll-Cretonne-Gewebe bei 70°C mit Wasser gespült, mit 2 g/l Waschmittel kochend geseift, heiss und kalt gespült und getrocknet.After 30 seconds of air, the cotton cretonne fabric is dried in a hot flue at 120 ° C. for 45 seconds. The color is then developed by impregnation on the pad with a squeezing effect of 80% liquor absorption with an aqueous liquor which contains 13 g / l of an Azoic Diazo Component 1 with a CI No. 37135. The dive time is 6 seconds. After passing the development pad, there is an air passage of 30 seconds. The cotton cretonne fabric is then rinsed with water at 70 ° C., soaped at the boil with 2 g / l detergent, rinsed hot and cold and dried.

Man erhält ein endengleich in rotem Farbton gefärbtes Baumwoll-Cretonne-Gewebe mit guten Echtheiten.A cotton cretonne fabric dyed in the same shade of red with good fastness properties is obtained.

Beispiel 5: Example 5 :

Ein Polyester-Baumwolle (50/50) Mischgewebe wird auf dem Foulard mit einem Abquetscheffekt von 65% Flottenaufnahme mit einer wässerigen Flotte imprägniert, die im Litter

Figure imgb0023
enthält. Die Tauchzeit beträgt 2,5 Sekunden. Nach dem Imprägnieren wird das Gewebe während 60 Sekunden bei 100°C getrocknet. Danach wird das gefärbte Gewebe mit einer wässerigen Lösung behandelt, die im Liter

20 ml
Schwefelsäure 66° Bé
 2 g
eines üblichen Dispergiermittels z.B. Mischung von Fettsäure/Eiweiss-Kondensationsprodukt mit Alkylphenolpolyglykolether und
 1 g
Thioharnstoff


enthält.A polyester-cotton (50/50) blended fabric is impregnated on the foulard with a squeezing effect of 65% liquor absorption with an aqueous liquor which is in the litter
Figure imgb0023
 contains. The dive time is 2.5 seconds. After impregnation, the fabric is dried for 60 seconds at 100 ° C. Then the dyed fabric is treated with an aqueous solution, which is in liters
20 ml
Sulfuric acid 66 ° Bé
2 g
a conventional dispersant, for example a mixture of fatty acid / protein condensation product with alkylphenol polyglycol ether and
1 g
Thiourea


contains.

Nach einem Luftgang von 20 Sekunden wird das Gewebe kalt gespült, mit einer wässerigen Lösung enthaltend 2 g/l Natriumcarbonat neutralisiert, kochend geseift, heiss und kalt gespült und schliesslich getrocknet.After an air passage of 20 seconds, the fabric is rinsed cold, neutralized with an aqueous solution containing 2 g / l sodium carbonate, soaped at the boil, rinsed hot and cold and finally dried.

Man erhält einen endengleich in rosa Farbton gefärbten Baumwollanteil mit sehr guten Echtheiten.The result is a cotton portion dyed in the same shade of pink with very good fastness properties.

Claims (12)

1. A process for dyeing cellulose fibres or cellulose-containing fibre blends with vat dyes, sulfur dyes, leuco vat ester dyes or azoic dyes by the pad dyeing process without incurring ending, which comprises using an aqueous dyeing liquor which, aside from the dye, contains a colourless compound of the formula
Figure imgb0029
 or of the formula
Figure imgb0030
 where
Q   is =C-Y or =N―,
Y   is hydrogen, halogen, cyano, C₁-C₅alkyl or C₁-C₅alkylsulfonyl,
V and W,   independently of each other, are each R₂-X₂―, R₃-X₃―, hydroxyl, C₁-C₅alkoxy or an unsubstituted or C₁-C₅alkyl- or C₅-C₆cycloalkyl- monosubstituted or -disubstituted amino group, the alkyl radical being unsubstituted or substituted by hydroxyl, cyano, sulfo or sulfato,
R₁, R₂ and R₃,   independently of one another, are each an aromatic or heteroaromatic radical,
X₁, X₂ and X₃,   independently of one another, are each ―O―, ―S―,
Figure imgb0031
 ―NH-CO-Phen-NH― or NH-CO-Phen-CO-NH―,
R₄   is hydrogen, C₁-C₅akyl, C₅-C₆cycloalkyl or phenyl,
Phen   is an unsubstituted or substituted phenylene group,
A   is a direct bond, ―CO― or ―CONH―,
Z   is an acidic, water-solubilising group and
m   is 1 to 6.

2. A process according to claim 1, wherein use is made of an azine compound of the formula (1) where Q is ―N=.
3. A process according to either of claims 1 and 2, wherein use is made of an azine compound of the formula (1) where V is R₂-X₂― and W is R₃-X₃―.
4. A process according to any one of claims 1 to 3, wherein use is made of an azine compound of the formula (1) where X₁, X₂ and X₃ are each ―NH―.
5. A process according to any one of claims 1 to 4, wherein use is made of an azine compound of the formula (1) where R₁, R₂ and R₃ are each aryl.
6. A process according to any one of claims 1 to 5, wherein use is made of an azine compound of the formula (1) where m is 2 to 4.
7. A process according to any one of claims 1 to 6, wherein use is made of an azine compound of the formula (1) where Z is a sulfonic acid group.
8. A process according to claim 1, wherein use is made of an azine compound of the following formulae:
Figure imgb0032
Figure imgb0033
 where
Y   is as defined in claim 1, in particular hydrogen or halogen,
V′ and W′,   independently of each other, are each hydroxyl, C₁-C₄alkoxy or an unsubstituted or C₁-C₅alkyl-monosubstituted or -disubstituted amino group, the alkyl radical being unsubstituted or substituted by hydroxyl, cyano, sulfo or sulfato, and V′ is also the radical R₂-X₂―,
R₁, R₂ and R₃,   independently of one another, are each an aromatic or heteroaromatic radical and, besides Z, may contain nonionic substituents,
X₁, X₂ and X₃,   independently of one another, are each ―O―, ―S― or ―N(R₅)―, R₅ being hydrogen, C₁-C₄alkyl or phenyl, Z is an acidic, water-solubilising group and
m   is 2 to 6.

9. A process according to claim 8, wherein use is made of a triazine compound of the formula (5) where X₁, X₂ and X₃ are each ―NH―, R₁, R₂ and R₃, independently of one another, are each phenyl or naphthyl, Z is a sulfonic acid group and m is 2 to 4.
10. A process according to claim 8, wherein use is made of a triazine compound of the formula (6) where V′ is R₂-X₂― and W′ is hydroxyl.
11. A process according to any one of claims 1 to 10, wherein cellulose fibres are dyed.
12. A process according to any one of claims 1 to 11, wherein cellulose fibres are dyed with sulfur dyes and the dyeing is finished with steam at a temperature of 100 to 120°C.
EP88810652A 1987-10-01 1988-09-23 Process for dyeing cellulosic fibres without tailing Expired - Lifetime EP0310556B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88810652T ATE68836T1 (en) 1987-10-01 1988-09-23 PROCESS FOR DYING CELLULOSE FIBERS TO THE SAME END.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH382387 1987-10-01
CH3823/87 1987-10-01

Publications (2)

Publication Number Publication Date
EP0310556A1 EP0310556A1 (en) 1989-04-05
EP0310556B1 true EP0310556B1 (en) 1991-10-23

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ID=4264234

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EP (1) EP0310556B1 (en)
JP (1) JPH01111078A (en)
KR (1) KR890006914A (en)
AT (1) ATE68836T1 (en)
DE (1) DE3865800D1 (en)
ES (1) ES2027036T3 (en)
ZA (1) ZA887308B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE59306916D1 (en) * 1992-08-18 1997-08-21 Ciba Geigy Ag Process for the photochemical and thermal stabilization of undyed and dyed polyester fiber materials
EP0818450B1 (en) 1996-07-08 2003-01-15 Ciba SC Holding AG Triazine derivatives as UV filter in sunscreen products
BRPI0804658B1 (en) * 2008-08-11 2012-06-26 Textile dyeing process of cellulosic fibers and their combinations with other fibers with reused dyebaths without any subsequent purification treatment.
CN117005215B (en) * 2023-08-16 2024-02-23 韶关市北纺智造科技有限公司 Vulcanized black dye solution and application thereof

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2298533A (en) * 1942-10-13 Capillary active condensation
US2928711A (en) * 1960-03-15 New colouration process
CH155747A (en) * 1931-02-10 1932-07-15 Chem Ind Basel Vat dye preparation.
US2940814A (en) * 1953-12-04 1960-06-14 Gen Aniline & Film Corp Vat dye compositions containing pyrimidines
US3400121A (en) * 1966-03-30 1968-09-03 Hoechst Ag 2, 4, 6-tri-(1-amino-substituted aromatic)-s-triazines
CH610702B (en) * 1976-06-16 Ciba Geigy Ag PROCESS FOR IMPROVING COLORS CREATED WITH ANIONIC COLORS ON CELLULOSE TEXTILE MATERIAL.
DE2930756A1 (en) * 1979-07-28 1981-02-26 Cassella Ag BLOCKING AIDS AND METHOD FOR COLORING CELLULOSE FIBERS OR MIXTURES OF CELLULOSE FIBERS TOGETHER WITH SYNTHESIS FIBERS WITH SULFUR, SULFUR COAT, COW AND REACTIVE DYES
US4313732A (en) * 1980-10-30 1982-02-02 Burlington Industries, Inc. Process for improving washfastness of indigo-dyed fabrics
EP0055694B1 (en) * 1980-12-30 1986-06-04 Ciba-Geigy Ag Process for dyeing or printing cellulosic materials and mixed cellulose/polyester fabrics
DE3247727A1 (en) * 1982-12-23 1984-06-28 Hoechst Ag, 6230 Frankfurt NUANCING PROCESS USING REACTIVE AND NON-REACTIVE DYES
ATE47168T1 (en) * 1986-04-07 1989-10-15 Ciba Geigy Ag PROCESS FOR DYING CELLULOSE FIBERS TO THE SAME END.

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KR890006914A (en) 1989-06-16
ES2027036T3 (en) 1992-05-16
JPH01111078A (en) 1989-04-27
ATE68836T1 (en) 1991-11-15
US4886518A (en) 1989-12-12
DE3865800D1 (en) 1991-11-28
EP0310556A1 (en) 1989-04-05

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