EP0610156A1 - Process for dyeing or printing cellulosic textile materials - Google Patents

Process for dyeing or printing cellulosic textile materials Download PDF

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Publication number
EP0610156A1
EP0610156A1 EP94810046A EP94810046A EP0610156A1 EP 0610156 A1 EP0610156 A1 EP 0610156A1 EP 94810046 A EP94810046 A EP 94810046A EP 94810046 A EP94810046 A EP 94810046A EP 0610156 A1 EP0610156 A1 EP 0610156A1
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EP
European Patent Office
Prior art keywords
alkaline earth
earth metal
metal salts
per liter
aqueous solution
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EP94810046A
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German (de)
French (fr)
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EP0610156B1 (en
Inventor
Wolfgang Sütterlin
Rolf Bitterli
Paul Schafflützel
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BASF Schweiz AG
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Ciba Geigy AG
Ciba Spezialitaetenchemie Holding AG
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • 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
    • D06P1/673—Inorganic compounds
    • D06P1/67333—Salts or hydroxides
    • D06P1/6735—Salts or hydroxides of alkaline or alkaline-earth metals with anions different from those provided for in D06P1/67341
    • D06P1/67358—Halides or oxyhalides
    • 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
    • D06P1/38—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 reactive dyes
    • D06P1/382—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 reactive dyes reactive group directly attached to heterocyclic group
    • 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
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • D06P3/663—Natural or regenerated cellulose using reactive dyes reactive group directly attached to heterocyclic group
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/921—Cellulose ester or ether

Definitions

  • the present invention relates to a novel process for dyeing or printing cellulose-containing fiber materials with chlorine-containing reactive dyes, in which the dyeings or prints obtained are washed with an aqueous solution to which alkaline earth metal salts have been added.
  • the present invention thus relates to a process for dyeing or printing cellulose-containing fiber materials with reactive dyes, which is characterized in that the fiber material is dyed or printed with at least one reactive dye containing a chlorotriazine residue and with an aqueous solution, to which an amount of at least 0 , 01 grams per liter of alkaline earth salts was added, washes.
  • the reactive dyes are derived in particular from the remainder of a monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, nitroaryl , Naphthoquinone, pyrenchinone or perylene tetracarbimide dye, preferably the rest of a monoazo, disazo, metal complex azo, anthraquinone or phthalocyanine dye.
  • the reactive dyes can contain, as further substituents, the substituents customary in organic dyes.
  • alkyl groups with 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl or butyl
  • alkoxy groups with 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy or butoxy
  • acylamino groups with 1 up to 8 carbon atoms especially alkanoylamino groups and alkoxycarbonylamino groups, such as acetylamino, propionylamino, methoxycarbonylamino, ethoxycarbonylamino or benzoylamino, phenylamino, NN-di- ⁇ -hydroxyethylamino, N, N-di- ⁇ -sulfatoethylamino, sulfobenzylamino, N, N, N Alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy radical, such as methoxycarbonyl or
  • the phenyl radicals mentioned can, for example, be further substituted by C1-C Alkyl-alkyl, C1-C4-alkoxy, halogen or sulfo.
  • the reactive dyes preferably contain one or more sulfonic acid groups.
  • Preferred substituents are C1-C4-alkyl, C1-C4-alkoxy, halogen, amino, hydroxy, ureido, methylsulfonyl, sulfo, phenyl, phenylamino, sulfamoyl, N-alkylsulfamoyl with 1 to 4 carbon atoms and N-phenylsulfamoyl, where the phenyl radicals mentioned can be further substituted, for example by C1-C4-alkyl, C1-C4-alkoxy, halogen or sulfo.
  • Preferred chlorotriazine residues are those of the formula in which R2 and R3 are independently hydrogen or C1-C4 alkyl and T1 is hydrogen; phenyl optionally substituted by C1-C4 alkyl, halogen or sulfo, especially by sulfo; or C1-C6-alkyl, which may optionally be interrupted by a radical -O- and may optionally be further substituted by hydroxyl.
  • Another possible substituent for the phenyl radical mentioned is 1-amino-2-sulfo-anthraquinone- (4) -yl.
  • T1 is preferably hydrogen; phenyl optionally substituted by sulfo; C1-C6 alkyl; a radical of the formula -CH2CH2OCH2CH2OH; or 1-amino-2-sulfo-anthraquinone- (4) -yl.
  • T1 is particularly preferably hydrogen; phenyl optionally substituted by sulfo; or a radical of the formula -CH2CH2OCH2CH2OH.
  • Magnesium, calcium or barium salts, in particular magnesium or calcium salts, are preferably used as alkaline earth metal salts. Mixtures of alkaline earth salts can also be used, e.g. Mixtures of magnesium and calcium salts. Common salts such as e.g. the corresponding halides, e.g. Fluorine, bromine or especially chlorine, sulfates or oxides into consideration.
  • An addition of alkaline earth metal salts of 0.01 to 1 gram per liter, in particular 0.01 to 0.2 gram per liter, preferably 0.05 to 0.2 gram per liter is particularly preferred.
  • the customary dyeing or printing processes can be used for the process according to the invention.
  • the dyeing liquors or printing pastes can contain other additives, for example wetting agents, anti-foaming agents, leveling agents or agents which influence the property of the textile material, such as e.g. Plasticizers, additives for flame retardants or dirt, water and oil repellents as well as water softening agents and natural or synthetic thickeners, e.g. Alginates and cellulose ethers.
  • the method for printing is preferred.
  • the printed fiber material is washed in a first washing process with water which does not has substantial content of alkaline earth metal salts, washed, and washed in a second washing process with an aqueous solution to which at least 0.01 grams per liter of alkaline earth metal salts were added.
  • An insignificant content of alkaline earth metal salts means a content of less than 0.01 grams per liter, in particular less than 0.005 grams per liter and preferably less than 0.001 grams per liter.
  • the printed fiber material is cold washed in a first washing process with water which has no substantial content of alkaline earth metal salts (for example at a temperature of 5 to 40 ° C.) and in a second washing process with a aqueous solution, to which at least 0.01 grams per liter of alkaline earth metal salts have been added, first washed hot (for example at a temperature of 80 to 110 ° C) and then cold (for example at a temperature of 5 to 40 ° C).
  • mixtures of two or more dyes can also be used as dyes.
  • At least one of the dyes of the formulas (6) to (8) is preferably used.
  • the dyes used in the process according to the invention are known or can be prepared by known processes.
  • cellulose-containing fiber materials are natural cellulose fibers such as cotton, linen and hemp, as well as cellulose and regenerated cellulose.
  • Cellulose-containing fiber materials which are contained in blended fabrics may also be mentioned, e.g. Mixtures of cotton with polyester fibers or polyamide fibers.
  • the dyeings and prints obtained by the process according to the invention have a high color strength and a high fiber-dye binding stability, furthermore good light fastness and very good wet fastness properties, such as fastness to washing, water, sea water, overdyeing and sweating, and good fastness to pleating , Ironing fastness and rubbing fastness.
  • a printing paste is made according to the following recipe:
  • This printing paste is used to print a cotton fabric in a conventional manner (flat film printing).
  • the printed cotton fabric is dried and steamed in saturated steam for 10 minutes at approx. 100 ° C.
  • the printed fabric is then washed cold with deionized water and then boiled, and then washed with an aqueous solution containing 0.09 g / l calcium chloride, cold, boiling and then cold again.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Coloring (AREA)

Abstract

Process for dyeing or printing cellulosic fibre materials with reactive dyes, characterised in that the fibre material is dyed or printed with at least one reactive dye containing a chlorotriazine radical and washed with an aqueous solution to which an amount of at least 0.01 gram per litre of alkaline earth metal salts has been added. The dyeings and prints obtained have good fastness properties.

Description

Die vorliegende Erfindung betrifft ein neues Verfahren zum Färben oder Bedrucken von cellulosehaltigen Fasermaterialien mit chlortriazinhaltigen Reaktivfarbstoffen, worin die erhaltenen Färbungen oder Drucke mit einer wässrigen Lösung, zu welcher Erdalkalisalze gegeben wurden, nachgewaschen werden.The present invention relates to a novel process for dyeing or printing cellulose-containing fiber materials with chlorine-containing reactive dyes, in which the dyeings or prints obtained are washed with an aqueous solution to which alkaline earth metal salts have been added.

Verfahren zum Färben oder Bedrucken von cellulosehaltigen Fasermaterialien mit Reaktivfarbstoffen sind seit langem bekannt. Die bekannten Verfahren können jedoch nicht in allen Fällen den in der Praxis an die erhaltenen Färbungen oder Drucke gestellten Anforderungen genügen, wie z.B. bezüglich der Echtheiten, wobei die Nassechtheiten hervorzuheben sind.Processes for dyeing or printing cellulosic fiber materials with reactive dyes have long been known. However, the known methods cannot in all cases meet the practical requirements for the dyeings or prints obtained, e.g. with regard to the fastnesses, the wet fastnesses being emphasized.

Es wurde nun gefunden, dass das weiter unten beschriebene Verfahren diesen Anforderungen genügt.It has now been found that the method described below meets these requirements.

Gegenstand der vorliegenden Erfindung ist somit ein Verfahren zum Färben oder Bedrucken von cellulosehaltigen Fasermaterialien mit Reaktivfarbstoffen, welches dadurch gekennzeichnet ist, dass man das Fasermaterial mit mindestens einem einen Chlortriazinrest enthaltenden Reaktivfarbstoff färbt oder bedruckt und mit einer wässrigen Lösung, zu welcher eine Menge von mindestens 0,01 Gramm pro Liter an Erdalkalisalzen zugegeben wurde, wäscht.The present invention thus relates to a process for dyeing or printing cellulose-containing fiber materials with reactive dyes, which is characterized in that the fiber material is dyed or printed with at least one reactive dye containing a chlorotriazine residue and with an aqueous solution, to which an amount of at least 0 , 01 grams per liter of alkaline earth salts was added, washes.

Die Reaktivfarbstoffe leiten sich insbesondere von dem Rest eines Monoazo-, Polyazo-, Metallkomplexazo-, Anthrachinon-, Phthalocyanin-, Formazan-, Azomethin-, Dioxazin-, Phenazin-, Stilben-, Triphenylmethan-, Xanthen-, Thioxanthon-, Nitroaryl-, Naphthochinon-, Pyrenchinon- oder Perylentetracarbimid-Farbstoffes, vorzugsweise dem Rest eines Monoazo-, Disazo-, Metallkomplexazo-, Anthrachinon- oder Phthalocyaninfarbstoffes, ab.The reactive dyes are derived in particular from the remainder of a monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazane, azomethine, dioxazine, phenazine, stilbene, triphenylmethane, xanthene, thioxanthone, nitroaryl , Naphthoquinone, pyrenchinone or perylene tetracarbimide dye, preferably the rest of a monoazo, disazo, metal complex azo, anthraquinone or phthalocyanine dye.

Die Reaktivfarbstoffe können an ihrem Grundgerüst neben der Reaktivgruppe als weitere Substituenten die bei organischen Farbstoffen üblichen Substituenten gebunden enthalten.In addition to the reactive group, the reactive dyes can contain, as further substituents, the substituents customary in organic dyes.

Als Beispiele für solche weiteren Substituenten der Reaktivfarbstoffe seien genannt: Alkylgruppen mit 1 bis 4 Kohlenstoffatomen, wie Methyl, Ethyl, Propyl, Isopropyl oder Butyl, Alkoxygruppen mit 1 bis 4 Kohlenstoffatomen, wie Methoxy, Ethoxy, Propoxy, Isopropoxy oder Butoxy, Acylaminogruppen mit 1 bis 8 Kohlenstoffatomen, insbesondere Alkanoylaminogruppen und Alkoxycarbonylaminogruppen, wie Acetylamino, Propionylamino, Methoxycarbonylamino, Ethoxycarbonylamino oder Benzoylamino, Phenylamino, N-N-Di-β-hydroxyethylamino, N,N-Di-β-sulfatoethylamino, Sulfobenzylamino, N,N-Disulfobenzylamino, Phenyl, Alkoxycarbonyl mit 1 bis 4 Kohlenstoffatomen im Alkoxyrest, wie Methoxycarbonyl oder Ethoxycarbonyl, Alkylsulfonyl mit 1 bis 4 Kohlenstoffatomen, wie Methylsulfonyl oder Ethylsulfonyl, Trifluormethyl, Nitro, Cyano, Halogen, wie Fluor, Chlor oder Brom, Carbamoyl, N-Alkylcarbamoyl mit 1 bis 4 Kohlenstoffatomen im Alkylrest, wie N-Methylcarbamoyl oder N-Ethylcarbamoyl, Sulfamoyl, N-Alkylsulfamoyl mit 1 bis 4 Kohlenstoffatomen, wie N-Methylsulfamoyl, N-Ethylsulfamoyl, N-Propylsulfamoyl, N-Isopropylsulfamoyl oder N-Butylsulfamoyl, N-(β-Hydroxyethyl)-sulfamoyl, N,N-Di-(β-hydroxyethyl)-sulfamoyl, N-Phenylsulfamoyl, Ureido, Hydroxy, Carboxy, Amino, Sulfomethyl oder Sulfo. Die genannten Phenylreste können beispielsweise durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen oder Sulfo weitersubstituiert sein. Vorzugsweise enthalten die Reaktivfarbstoffe eine oder mehrere Sulfonsäuregruppen.Examples of such further substituents of the reactive dyes are: alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl or butyl, alkoxy groups with 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy or butoxy, acylamino groups with 1 up to 8 carbon atoms, especially alkanoylamino groups and alkoxycarbonylamino groups, such as acetylamino, propionylamino, methoxycarbonylamino, ethoxycarbonylamino or benzoylamino, phenylamino, NN-di-β-hydroxyethylamino, N, N-di-β-sulfatoethylamino, sulfobenzylamino, N, N, N Alkoxycarbonyl with 1 to 4 carbon atoms in the alkoxy radical, such as methoxycarbonyl or ethoxycarbonyl, alkylsulfonyl with 1 to 4 carbon atoms, such as methylsulfonyl or ethylsulfonyl, trifluoromethyl, nitro, cyano, halogen, such as fluorine, chlorine or bromine, carbamoyl, N-alkylcarbamoyl with 1 to 4 Carbon atoms in the alkyl radical, such as N-methylcarbamoyl or N-ethylcarbamoyl, sulfamoyl, N-alkylsulfame oyl with 1 to 4 carbon atoms, such as N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl or N-butylsulfamoyl, N- (β-hydroxyethyl) sulfamoyl, N, N-di- (β-hydroxyethyl) - sulfamoyl, N-phenylsulfamoyl, ureido, hydroxy, carboxy, amino, sulfomethyl or sulfo. The phenyl radicals mentioned can, for example, be further substituted by C₁-C Alkyl-alkyl, C₁-C₄-alkoxy, halogen or sulfo. The reactive dyes preferably contain one or more sulfonic acid groups.

Bevorzugte Substituenten sind C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, Amino, Hydroxy, Ureido, Methylsulfonyl, Sulfo, Phenyl, Phenylamino, Sulfamoyl, N-Alkylsulfamoyl mit 1 bis 4 Kohlenstoffatomen und N-Phenylsulfamoyl, wobei die genannten Phenylreste beispielsweise durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen oder Sulfo weitersubstituiert sein können.Preferred substituents are C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, amino, hydroxy, ureido, methylsulfonyl, sulfo, phenyl, phenylamino, sulfamoyl, N-alkylsulfamoyl with 1 to 4 carbon atoms and N-phenylsulfamoyl, where the phenyl radicals mentioned can be further substituted, for example by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen or sulfo.

Bevorzugt leiten sich die Reaktivfarbstoffe von folgenden Farbstoffresten ab:

  • a) Farbstoffreste eines 1:1-Kupferkomplexazofarbstoffes der Formel
    Figure imgb0001
     worin A und B unabhängig voneinander ein Rest der Benzol- oder Naphthalinreihe sind und die Reste -O- beidseitig in ortho-Stellung zur Azobrücke gebunden sind. Für mögliche Substituenten der Reste A und B gelten die oben angegebenen Bedeutungen und Bevorzugungen. Vorzugsweise handelt es sich hierbei um C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, Amino, Hydroxy oder Sulfo, insbesondere um Sulfo.
  • b) Farbstoffreste eines Mono- oder Disazofarbstoffes, der Formel

            D₁-N=N-(M-N=N)u-K-   (2a)

    oder

            -D₁-N=N-(M-N=N)u-K   (2b),

    worin D₁ der Rest einer Diazokomponente der Benzol- oder Naphthalinreihe, M der Rest einer Mittelkomponente der Benzol- oder Naphthalinreihe, und K der Rest einer Kupplungskomponente der Benzol-, Naphthalin-, 6-Hydroxypyridon-(2)- oder Pyrazolon-Reihe ist und u die Zahl 0 oder 1 ist. Für mögliche Substituenten der Reste D₁, M und K gelten die oben angegebenen Bedeutungen und Bevorzugungen. Vorzugsweise handelt es sich hierbei um C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen, Amino, Hydroxy, Ureido, Methylsulfonyl, Sulfo oder Phenyl, wobei der genannte Phenylrest beispielsweise durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen oder Sulfo weitersubstituiert sein kann.
  • c) Farbstoffreste eines Anthrachinonfarbstoffes, der Formel
    Figure imgb0002
     worin G ein gegebenenfalls durch C₁-C₄-Alkyl, C₁-C₄-Alkoxy, Halogen oder Sulfo substituierter Phenylenrest ist.
  • d) Farbstoffreste eines Phthalocyaninfarbstoffes, der Formel
    Figure imgb0003
     worin Pc der Rest eines Kupferphthalocyanins ist, W Hydroxyl oder Amino, R₁ Wasserstoff oder C₁-C₄-Alkyl, E ein gegebenenfalls durch C₁-C₄-Alkyl, Halogen oder Sulfo substituierter Phenylenrest oder ein C₂-C₆-Alkylenrest, vorzugsweise ein Sulfophenylen- oder Ethylenrest, ist, m 2 bis 3 und n 1 bis 2 ist.
The reactive dyes are preferably derived from the following dye residues:
  • a) dye residues of a 1: 1 copper complex azo dye of the formula
    Figure imgb0001
     wherein A and B are independently a residue of the benzene or naphthalene series and the radicals -O- are bound on both sides in the ortho position to the azo bridge. The meanings and preferences given above apply to possible substituents of the radicals A and B. It is preferably C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, amino, hydroxy or sulfo, in particular sulfo.
  • b) dye residues of a mono- or disazo dye, the formula

    D₁-N = N- (MN = N) u -K- (2a)

    or

    -D₁-N = N- (MN = N) u -K (2b),

    wherein D₁ is the remainder of a diazo component of the benzene or naphthalene series, M is the remainder of a middle component of the benzene or naphthalene series, and K is the remainder of a coupling component of the benzene, naphthalene, 6-hydroxypyridone (2) or pyrazolone series and u is the number 0 or 1. For possible substituents of the radicals D₁, M and K, the meanings and preferences given above apply. These are preferably C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen, amino, hydroxy, ureido, methylsulfonyl, sulfo or phenyl, the phenyl radical mentioned being, for example, by C₁-C₄-alkyl, C₁-C₄-alkoxy, Halogen or sulfo can be further substituted.
  • c) dye residues of an anthraquinone dye, the formula
    Figure imgb0002
     wherein G is a phenylene radical optionally substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy, halogen or sulfo.
  • d) dye residues of a phthalocyanine dye, the formula
    Figure imgb0003
     wherein Pc is the radical of a copper phthalocyanine, W is hydroxyl or amino, R₁ is hydrogen or C₁-C₄-alkyl, E is a phenylene radical optionally substituted by C₁-C₄-alkyl, halogen or sulfo or a C₂-C₆-alkylene radical, preferably a sulfophenylene or Is ethylene, m is 2 to 3 and n is 1 to 2.

Als Chlortriazinreaktivreste kommen vorzugsweise solche der Formel

Figure imgb0004

in Betracht, worin R₂ und R₃ unabhängig voneinander Wasserstoff oder C₁-C₄-Alkyl sind und T₁ Wasserstoff; gegebenenfalls durch C₁-C₄-Alkyl, Halogen oder Sulfo, insbesondere durch Sulfo, substituiertes Phenyl; oder C₁-C₆-Alkyl, welches gegebenenfalls durch einen Rest -O- unterbrochen und gegebenenfalls durch Hydroxyl weitersubstituiert sein kann, ist. Als weiterer möglicher Substituent des genannten Phenylrestes kommt 1-Amino-2-sulfo-Anthrachinon-(4)-yl in Betracht.Preferred chlorotriazine residues are those of the formula
Figure imgb0004
in which R₂ and R₃ are independently hydrogen or C₁-C₄ alkyl and T₁ is hydrogen; phenyl optionally substituted by C₁-C₄ alkyl, halogen or sulfo, especially by sulfo; or C₁-C₆-alkyl, which may optionally be interrupted by a radical -O- and may optionally be further substituted by hydroxyl. Another possible substituent for the phenyl radical mentioned is 1-amino-2-sulfo-anthraquinone- (4) -yl.

Bevorzugt ist T₁ Wasserstoff; gegebenenfalls durch Sulfo substituiertes Phenyl;
C₁-C₆-Alkyl; ein Rest der Formel -CH₂CH₂OCH₂CH₂OH; oder
1-Amino-2-sulfo-Anthrachinon-(4)-yl. Besonders bevorzugt ist T₁ Wasserstoff;
gegebenenfalls durch Sulfo substituiertes Phenyl; oder ein Rest der Formel -CH₂CH₂OCH₂CH₂OH.T₁ is preferably hydrogen; phenyl optionally substituted by sulfo;
C₁-C₆ alkyl; a radical of the formula -CH₂CH₂OCH₂CH₂OH; or
1-amino-2-sulfo-anthraquinone- (4) -yl. T₁ is particularly preferably hydrogen;
phenyl optionally substituted by sulfo; or a radical of the formula -CH₂CH₂OCH₂CH₂OH.

Ganz besonders bevorzugt verwendet man für das erfindungsgemässe Verfahren mindestens einen der Reaktivfarbstoffe der Formeln (6) bis (23)

Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
 It is very particularly preferred to use at least one of the reactive dyes of the formulas (6) to (23) for the process according to the invention
Figure imgb0005
Figure imgb0006
Figure imgb0007
Figure imgb0008
Figure imgb0009
Figure imgb0010
Figure imgb0011
Figure imgb0012
Figure imgb0013
Figure imgb0014
Figure imgb0015
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022

Als Erdalkalisalze verwendet man vorzugsweise Magnesium-, Calcium- oder Bariumsalze, insbesondere Magnesium- oder Calciumsalze. Es können auch Mischungen von Erdalkalisalzen verwendet werden, wie z.B. Mischungen von Magnesium- und Calciumsalzen. Hierbei kommen übliche Salze, wie z.B. die entsprechenden Halogenide, wie z.B. Fluor, Brom oder insbesondere Chlor, Sulfate oder Oxide in Betracht.Magnesium, calcium or barium salts, in particular magnesium or calcium salts, are preferably used as alkaline earth metal salts. Mixtures of alkaline earth salts can also be used, e.g. Mixtures of magnesium and calcium salts. Common salts such as e.g. the corresponding halides, e.g. Fluorine, bromine or especially chlorine, sulfates or oxides into consideration.

Als obere Grenze für die Zugabe der Erdalkalisalze hat sich ein Wert von 1 Gramm pro Liter, insbesondere 0,2 Gramm pro Liter, als vorteilhaft erwiesen. Als untere Grenze für die Zugabe der Erdalkalisalze ist ein Wert von 0,05 Gramm pro Liter bevorzugt. Besonders bevorzugt ist eine Zugabe an Erdalkalisalzen von 0,01 bis 1 Gramm pro Liter, insbesondere 0,01 bis 0,2 Gramm pro Liter, vorzugsweise 0,05 bis 0,2 Gramm pro Liter.A value of 1 gram per liter, in particular 0.2 gram per liter, has proven to be advantageous as the upper limit for the addition of the alkaline earth metal salts. A value of 0.05 grams per liter is preferred as the lower limit for the addition of the alkaline earth metal salts. An addition of alkaline earth metal salts of 0.01 to 1 gram per liter, in particular 0.01 to 0.2 gram per liter, preferably 0.05 to 0.2 gram per liter is particularly preferred.

Für das erfindungsgemässe Verfahren können die üblichen Färbe- bzw. Druckverfahren verwendet werden. Die Färbeflotten oder Druckpasten können ausser Wasser und den Farbstoffen weitere Zusätze, beispielsweise Netzmittel, Antischaummittel, Egalisiermittel oder die Eigenschaft des Textilmaterials beeinflussende Mittel, wie z.B. Weichmachungsmittel, Zusätze zum Flammiestausrüsten oder schmutz-, wasser- und öl-abweisende Mittel sowie wasserenthärtende Mittel und natürliche oder synthetische Verdicker, wie z.B. Alginate und Celluloseäther, enthalten.The customary dyeing or printing processes can be used for the process according to the invention. In addition to water and the dyes, the dyeing liquors or printing pastes can contain other additives, for example wetting agents, anti-foaming agents, leveling agents or agents which influence the property of the textile material, such as e.g. Plasticizers, additives for flame retardants or dirt, water and oil repellents as well as water softening agents and natural or synthetic thickeners, e.g. Alginates and cellulose ethers.

Bevorzugt ist das Verfahren zum Bedrucken.The method for printing is preferred.

In einer besonders bevorzugten Ausführungsform des Verfahrens zum Bedrucken wird das bedruckte Fasermaterial in einem ersten Waschvorgang mit Wasser, welches keinen wesentlichen Gehalt an Erdalkalisalzen aufweist, gewaschen, und in einem zweiten Waschvorgang mit einer wässrigen Lösung, zu welcher mindesten 0,01 Gramm pro Liter Erdalkalisalze gegeben wurden, gewaschen. Für die Mengen der Erdalkalisalze gelten hierbei die oben angegebenen Bevorzugungen. Unter einem nicht wesentlichen Gehalt an Erdalkalisalzen ist ein Gehalt von weniger als 0,01 Gramm pro Liter, insbesondere von weniger als 0,005 Gramm pro Liter und vorzugsweise von weniger als 0,001 Gramm pro Liter zu verstehen.In a particularly preferred embodiment of the method for printing, the printed fiber material is washed in a first washing process with water which does not has substantial content of alkaline earth metal salts, washed, and washed in a second washing process with an aqueous solution to which at least 0.01 grams per liter of alkaline earth metal salts were added. The preferences given above apply to the amounts of the alkaline earth metal salts. An insignificant content of alkaline earth metal salts means a content of less than 0.01 grams per liter, in particular less than 0.005 grams per liter and preferably less than 0.001 grams per liter.

In einer ganz besonders bevorzugten Ausführungsform des Verfahrens zum Bedrucken wird das bedruckte Fasermaterial in einem ersten Waschvorgang mit Wasser, welches keinen wesentlichen Gehalt an Erdalkalisalzen aufweist, kalt gewaschen (z.B. bei einer Temperatur von 5 bis 40°C) und in einem zweiten Waschvorgang mit einer wässrigen Lösung, zu welcher mindesten 0,01 Gramm pro Liter Erdalkalisalze gegeben wurden, erst heiss (z.B. bei einer Temperatur von 80 bis 110°C) und dann kalt (z.B. bei einer Temperatur von 5 bis 40°C) gewaschen.In a very particularly preferred embodiment of the method for printing, the printed fiber material is cold washed in a first washing process with water which has no substantial content of alkaline earth metal salts (for example at a temperature of 5 to 40 ° C.) and in a second washing process with a aqueous solution, to which at least 0.01 grams per liter of alkaline earth metal salts have been added, first washed hot (for example at a temperature of 80 to 110 ° C) and then cold (for example at a temperature of 5 to 40 ° C).

Als Farbstoffe können neben Einzelfarbstoffen auch Mischungen von zwei oder mehreren Farbstoffen verwendet werden.In addition to individual dyes, mixtures of two or more dyes can also be used as dyes.

Bevorzugt verwendet man mindestens einen der Farbstoffe der Formeln (6) bis (8).At least one of the dyes of the formulas (6) to (8) is preferably used.

Die in dem erfindungsgemässen Verfahren verwendeten Farbstoffe sind bekannt oder können gemäss bekannten Verfahren hergestellt werden.The dyes used in the process according to the invention are known or can be prepared by known processes.

Als cellulosehaltige Fasermaterialien sind beispielsweise die natürlichen Cellulosefasern, wie Baumwolle, Leinen und Hanf, sowie Zellstoff und regenerierte Cellulose zu nennen. Weiterhin seien cellulosehaltige Fasermaterialien genannt, die in Mischgeweben enthalten sind, z.B. Gemische aus Baumwolle mit Polyesterfasern oder Polyamidfasern.Examples of cellulose-containing fiber materials are natural cellulose fibers such as cotton, linen and hemp, as well as cellulose and regenerated cellulose. Cellulose-containing fiber materials which are contained in blended fabrics may also be mentioned, e.g. Mixtures of cotton with polyester fibers or polyamide fibers.

Die gemäss dem erfindungsgemässen Verfahren erhaltenen Färbungen und Drucke besitzen eine hohe Farbstärke und eine hohe Faser-Farbstoff-Bindungsstabilität, weiterhin eine gute Lichtechtheit und sehr gute Nassechtheitseigenschaften, wie Wasch-, Wasser-, Seewasser-, Ueberfärbe- und Schweissechtheiten, sowie eine gute Plissierechtheit, Bügelechtheit und Reibechtheit.The dyeings and prints obtained by the process according to the invention have a high color strength and a high fiber-dye binding stability, furthermore good light fastness and very good wet fastness properties, such as fastness to washing, water, sea water, overdyeing and sweating, and good fastness to pleating , Ironing fastness and rubbing fastness.

Hervorzuheben sind die guten Nassechtheiten, welche durch das erfindungsgemässe Verfahren verbessert sind.The good wet fastness properties which are to be emphasized by the inventive Procedures are improved.

Die nachfolgenden Beispiele dienen zur Erläuterung der Erfindung. Die Temperaturen sind in Celsiusgraden angegeben, Teile sind Gewichtsteile, die Prozentangaben beziehen sich auf Gewichtsprozente, sofern nicht anders vermerkt. Gewichtsteile stehen zu Volumenteilen im Verhältnis von Kilogramm zu Liter.The following examples serve to explain the invention. The temperatures are given in degrees Celsius, parts are parts by weight, the percentages relate to percentages by weight, unless stated otherwise. Parts by weight relate to parts by volume in the ratio of kilograms to liters.

Beispiel 1:Example 1:

Eine Druckpaste wird nach folgender Rezeptur angesetzt:A printing paste is made according to the following recipe:

30 g des Reaktivfarbstoffes der Formel

Figure imgb0023

und 100 g Harnstoff werden gelöst in
350 g Wasser und anschliessend mit
450 g einer 5%-igen Na-Alginat-Verdickung zusammen homogenisiert.30 g of the reactive dye of the formula
Figure imgb0023
and 100 g of urea are dissolved in
350 g of water and then with
450 g of a 5% Na alginate thickener homogenized together.

Unter einem Schnellrührer werden
60 g einer wässrigen Sodalösung (25%) und
10 g o-Nitrobenzolsulfonsäure-Na-Salz eingestreut.Be under a quick stirrer
60 g of an aqueous soda solution (25%) and
Sprinkled 10 g of o-nitrobenzenesulfonic acid sodium salt.

Mit dieser Druckpaste wird in herkömmlicher Weise (Flachfilmdruck) ein Baumwollgewebe bedruckt. Das bedruckte Baumwollgewebe wird getrocknet und 10 Minuten bei ca. 100°C im Sattdampf gedämpft.This printing paste is used to print a cotton fabric in a conventional manner (flat film printing). The printed cotton fabric is dried and steamed in saturated steam for 10 minutes at approx. 100 ° C.

Anschliessend wird das bedruckte Gewebe mit deionisiertem Wasser kalt und dann kochend gewaschen, und daraufhin mit einer wässrigen Lösung, welche 0,09 g/l Calciumchlorid enthält, kalt, kochend und dann wieder kalt gewaschen.The printed fabric is then washed cold with deionized water and then boiled, and then washed with an aqueous solution containing 0.09 g / l calcium chloride, cold, boiling and then cold again.

Nach Trocknung erhält man einen marineblauen Druck mit guten Nassechtheiten.After drying, a navy blue print with good wet fastness properties is obtained.

Beispiele 2 bis 18:Examples 2 to 18:

Verfährt man wie in Beispiel 1 angegeben, verwendet jedoch anstelle des Reaktivfarbstoffes der Formel (6) einen der Reaktivfarbstoffe der Formeln (7) bis (23), so werden ebenfalls Drucke mit guten Nassechtheiten erhalten.If the procedure is as described in Example 1, but instead of the reactive dye of the formula (6), one of the reactive dyes of the formulas (7) to (23) is used, prints with good wet fastness properties are likewise obtained.

Claims (9)

Verfahren zum Färben oder Bedrucken von cellulosehaltigen Fasermaterialien mit Reaktivfarbstoffen, dadurch gekennzeichnet, dass man das Fasermaterial mit mindestens einem einen Chlortriazinrest enthaltenden Reaktivfarbstoff färbt oder bedruckt und mit einer wässrigen Lösung, zu welcher eine Menge von mindestens 0,01 Gramm pro Liter an Erdalkalisalzen zugegeben wurde, wäscht.Process for dyeing or printing cellulosic fiber materials with reactive dyes, characterized in that the fiber material is dyed or printed with at least one reactive dye containing a chlorotriazine residue and with an aqueous solution to which an amount of at least 0.01 grams per liter of alkaline earth metal salts has been added , washes. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass man mindestens einen der Reaktivfarbstoffe der Formeln (6) bis (23)
Figure imgb0024
Figure imgb0025
Figure imgb0026
Figure imgb0027
Figure imgb0028
Figure imgb0029
Figure imgb0030
Figure imgb0031
Figure imgb0032
Figure imgb0033
Figure imgb0034
Figure imgb0035
Figure imgb0036
Figure imgb0037
Figure imgb0038
Figure imgb0039
Figure imgb0040
Figure imgb0041
 verwendet.A method according to claim 1, characterized in that at least one of the reactive dyes of the formulas (6) to (23)
Figure imgb0024
Figure imgb0025
Figure imgb0026
Figure imgb0027
Figure imgb0028
Figure imgb0029
Figure imgb0030
Figure imgb0031
Figure imgb0032
Figure imgb0033
Figure imgb0034
Figure imgb0035
Figure imgb0036
Figure imgb0037
Figure imgb0038
Figure imgb0039
Figure imgb0040
Figure imgb0041
 used. Verfahren gemäss einem der Ansprüche 1 und 2, dadurch gekennzeichnet, dass man das Fasermaterial bedruckt.Method according to one of claims 1 and 2, characterized in that the fiber material is printed. Verfahren gemäss einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass man das Fasermaterial bedruckt, anschliessend in einem ersten Waschvorgang mit Wasser, welches keinen wesentlichen Gehalt an Erdalkalisalzen aufweist, wäscht, und in einem zweiten Waschvorgang mit einer wässrigen Lösung, zu welcher mindestens 0,01 Gramm pro Liter Erdalkalisalze gegeben wurden, wäscht.Method according to one of claims 1 to 3, characterized in that the fiber material is printed, then washed in a first washing process with water which has no substantial content of alkaline earth metal salts, and in a second washing process with an aqueous solution to which at least 0 , 01 grams per liter of alkaline earth metal salts were washed. Verfahren gemäss einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass man zum Waschen eine wässrige Lösung verwendet, zu welcher 0,01 bis 1 Gramm pro Liter Erdalkalisalze gegeben wurden.Method according to one of claims 1 to 4, characterized in that an aqueous solution is used for washing, to which 0.01 to 1 gram per liter of alkaline earth metal salts have been added. Verfahren gemäss einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass man zum Waschen eine wässrige Lösung verwendet, zu welcher 0,01 bis 0,2 Gramm pro Liter Erdalkalisalze gegeben wurden.Method according to one of claims 1 to 5, characterized in that an aqueous solution is used for washing, to which 0.01 to 0.2 grams per liter of alkaline earth metal salts have been added. Verfahren gemäss einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass man zum Waschen eine wässrige Lösung verwendet, zu welcher 0,05 bis 0,2 Gramm pro Liter Erdalkalisalze gegeben wurden.Method according to one of claims 1 to 6, characterized in that an aqueous solution is used for washing, to which 0.05 to 0.2 grams per liter of alkaline earth metal salts have been added. Verfahren gemäss einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass es sich bei den Erdalkalisalzen um Magnesium- oder Calciumsalze handelt.Method according to one of claims 1 to 7, characterized in that the alkaline earth metal salts are magnesium or calcium salts. Verfahren gemäss einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass man mindestens einen der Reaktivfarbstoffe der Formeln (6) bis (8) verwendet.Method according to one of claims 1 to 8, characterized in that at least one of the reactive dyes of the formulas (6) to (8) is used.
EP94810046A 1993-02-05 1994-01-27 Process for dyeing or printing cellulosic textile materials Expired - Lifetime EP0610156B1 (en)

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