EP0641402B1 - Continuous dyeing of cellulose-containing textiles - Google Patents

Abstract

PCT No. PCT/EP93/01172 Sec. 371 Date Oct. 31, 1994 Sec. 102(e) Date Oct. 31, 1994 PCT Filed May 12, 1993 PCT Pub. No. WO93/23605 PCT Pub. Date Nov. 25, 1993.Process for the continuous production of surface dyeings on cellulose fiber textile materials, characterized in that the textile materials are treated with an aqueous liquor containing at least 5 g/l of benzyl halide quaternized condensation products of precondensates of trialkanolamines and ureas, cyclic carbonates and/or epihalohydrins and/or benzyl chloride quaternized condensation products of piperazine and epichloronydrin, and 0.02 to 1 g/l of a phosphoric triester whose alcohol component has 6 to 18 carbon atoms, the textile materials thus treated are then dyed in another bath with reactive dyes in an aqueous medium and the dyes are fixed by treatment with an alkaline aqueous liquor and the dyeing finished in conventional manner. The individual cellulose fibers of the textile material are not completely penetrated by the dye but, on the contrary, exhibit ring dyeing.

Description

The invention relates to a process for the continuous production of surface dyeings on cellulose fibers, which are in the form of textile materials, by treating the textile materials with an aqueous liquor which contains cationic polyquaternary condensation products and phosphoric acid esters, and then dyeing the textile materials with reactive dyes and finishing the dyeings in the usual way.

• (a) primäre und/oder sekundäre basische Aminogruppen enthaltende wasserlösliche Verbindungen und
• (b) Propylenchlorhydringruppen enthaltende wasserlösliche Verbindungen, die daraus gebildeten Epoxide, N-Methylol- oder N-Methylolethergruppen enthaltende wasserlösliche Kondensator aufbringt,

From DE-A-3 320 629 a process for dyeing textile materials made of cellulose fibers is known, in which one first creates a firmly adhering film on the textile materials in which it is placed

• (a) water-soluble compounds containing primary and / or secondary basic amino groups and
• (b) water-soluble compounds containing propylene chlorohydrin groups, the epoxides formed therefrom, water-soluble condensers containing N-methylol or N-methylol ether groups,

the textile material then dries and dyes in the usual manner with reactive dyes or acid dyes in an aqueous medium at pH values from 6 to 12. The dyeings available in this way correspond to the properties of an indigo dyeing. This process can be used to produce denim items in all colors. As with indigo dyeing, with these denim dyeings the colored chain of the denim fabric becomes lighter after repeated washing and gets a more brilliant tone.

Quaternized condensation products are known from US Pat. No. 5,015,754, which can be obtained by reacting precondensates of trialkanolamines with carboxylic acid derivatives or epichlorohydrin and subsequent quaternization with benzyl chloride are. These condensation products are used for the aftertreatment for the fixation of dyeings and prints on textile materials containing cellulose fibers.

The object of the present invention is to provide a method for the continuous production of surface dyeings on cellulose fibers which are in the form of textile materials.

• (i) mindestens 5 g/l an mit Benzylhalogeniden quaternierten Kondensationsprodukten aus Präkondensaten von Trialkanolaminen und Harnstoffen, cyclischen Carbonaten und/oder Epihalogenhydrinen und/oder mit Benzylchlorid quaternisierte Kondensationsprodukte aus Piperazin und Epichlorhydrin und
• (ii) 0,02 bis 1 g/l eines Phosphorsäuretriesters enthält, dessen Alkoholkomponente sich von aliphatischen, Arylsubstituenten aufweisenden aliphatischen Alkoholen, Phenolen oder alkylsubstituierten Phenolen mit jeweils 6 bis 18 C-Atomen im Alkohol- oder Phenolrest ableitet,

die so behandelten textilen Materialien dann in einem anderen Bad mit Reaktivfarbstoffen in wäßrigem Medium färbt und anschließend die Farbstoffe durch Behandlung mit einer alkalischen Flotte in üblicher Weise fixiert und die Färbung fertigstellt.The object is achieved according to the invention if the textile materials are first treated with an aqueous liquor which

• (i) at least 5 g / l of condensation products quaternized with benzyl halides from precondensates of trialkanolamines and ureas, cyclic carbonates and / or epihalohydrins and / or condensation products quaternized with benzyl chloride from piperazine and epichlorohydrin and
• (ii) contains 0.02 to 1 g / l of a phosphoric acid triester, the alcohol component of which is derived from aliphatic, aryl-substituted aliphatic alcohols, phenols or alkyl-substituted phenols each having 6 to 18 carbon atoms in the alcohol or phenol radical,

the textile materials treated in this way are then dyed in a different bath with reactive dyes in an aqueous medium and the dyes are then fixed in a customary manner by treatment with an alkaline liquor and the dyeing is completed.

The cellulose fibers of the textile materials dyed in this way are not continuously dyed, but only on the surface. In such cases one also speaks of ring colorations. However, the textile material is colored no matter what. Textile materials which can be dyed by the process according to the invention are, for example, yarns, woven fabrics, knitted fabrics or nonwovens which consist of cellulose fibers or, if appropriate, contain them in a mixture with other fibers. Warp yarns made from cellulose fibers are preferably dyed by the process according to the invention.

• A) einem Präkondensat aus einem oder mehreren Trialkanolaminen der allgemeinen Formel I
  
  in der die Reste R¹ bis R³ für 1,2-Alkylengruppen mit 2 bis 4 C-Atomen stehen, und
• B) 1 bis 30 mol-% pro Mol I einer der folgenden Verbindungen II:
  • a) einer Carbonsäure oder eines Carbonsäurederivates der allgemeinen Formel IIa
    
    in der

    n

    0 oder 1

    R⁴, R⁵

    Hydroxylgruppen, ausgenommen für den Fall n = 0, oder C₁-C₈-Alkoxygruppen, die im Falle n = 0 zu einem fünf- oder sechsgliedrigen Ring verbunden sein können, oder Chlor oder Brom und

    R⁶

    eine Alkylengruppe mit 1 bis 50 C-Atomen, die durch ein oder mehrere nicht benachbarte Sauerstoffatome unterbrochen sein kann,

    bedeuten,
  • b) einem Carbonsäureamid der allgemeinen Formel IIb
    
    in der

    m, n, r

    0 oder 1

    R⁷

    Wasserstoff oder eine C₁-C₄-Alkylgruppe und

    R⁸

    Wasserstoff, eine C₁-C₂₅-Alkylgruppe, eine C₂-C₂₅-Alkenylgruppe oder einen Phenylrest, der C₁-C₄-Alkylgruppen, C₁-C₄-Alkoxygruppen sowie Fluor, Chlor oder Brom als Substituenten tragen kann,

    bedeuten,
  • c) einem Epihalogenhydrin in der allgemeinen Formel IIc
    
    in der

    X

    Chlor oder Brom

    bedeutet,
  • d) einer monofunktionellen Verbindung der allgemeinen Formel IId
    
            R⁹-Y     IId
    
    in der

    R⁹

    eine C₁-C₂₅-Alkylgruppe, eine C₂-C₂₅-Alkenylgruppe oder einen Phenylrest, der C₁-C₄-Alkylgruppen, C₁-C₄-Alkoxygruppen sowie Fluor, Chlor oder Brom als Substituenten tragen kann, und

    Y

    Isocyanat oder eine der Gruppen

    

    bedeutet. oder

  • e) einer bifunktionellen Verbindung der allgemeinen Formel IIe
    
            Z¹-R¹⁰-Z²     IIe
    
    in der

    R¹⁰

    eine Alkylengruppen mit 1 bis 50 C-Atomen, die durch ein oder mehrere nicht benachbarte Sauerstoffatome unterbrochen sein Und/oder eine oder mehrere nicht vicinal zueinander stehende Hydroxylgruppen enthalten kann, und

    Z¹, Z²

    Chlor, Brom, Isocyanat oder eine der Gruppen

    

    bedeutet,
  oder von Gemischen hiervon, und
• C) 25 bis 100 mol-% pro Mol I eines Benzylhalogenids der allgemeinen Formel III
  
  in der

  p

  für 0 bis 2 und

  R¹¹

  für eine C₁-C₄-Alkylgruppe, eine C₁-C₄-Alkoxygruppe, Fluor, Chlor oder Brom

  steht.

The textile materials are first treated with an aqueous liquor which contains at least 5 g / l of condensation products quaternized with benzyl halides from precondensates of trialkanolamines and ureas, cyclic carbonates and / or epihalohydrins. Quaternized condensation products of this type are described in detail in US-A-5 015 754. The quaternized condensation products consist of

• A) a precondensate of one or more trialkanolamines of the general formula I.
  
  in which the radicals R ¹ to R ^{3 represent} 1,2-alkylene groups having 2 to 4 carbon atoms, and
• B) 1 to 30 mol% per mole I of one of the following compounds II:
  • a) a carboxylic acid or a carboxylic acid derivative of the general formula IIa
    
    in the

    n

    0 or 1

    R ⁴ , R ⁵

    Hydroxyl groups, except for the case n = 0, or C ₁ -C ₈ alkoxy groups, which can be connected to a five- or six-membered ring in the case n = 0, or chlorine or bromine and

    R ⁶

    an alkylene group with 1 to 50 C atoms, which can be interrupted by one or more non-adjacent oxygen atoms,

    mean,
  • b) a carboxamide of the general formula IIb
    
    in the

    m, n, r

    0 or 1

    R ⁷

    Hydrogen or a C ₁ -C ₄ alkyl group and

    R ⁸

    Hydrogen, a C ₁ -C ₂₅ alkyl group, a C ₂ -C ₂₅ alkenyl group or a phenyl radical which can carry C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxy groups and fluorine, chlorine or bromine as substituents,

    mean,
  • c) an epihalohydrin in the general formula IIc
    
    in the

    X

    Chlorine or bromine

    means
  • d) a monofunctional compound of the general formula IId
    
    R ⁹ -Y IId
    
    in the

    R ⁹

    a C ₁ -C ₂₅ alkyl group, a C ₂ -C ₂₅ alkenyl group or a phenyl radical which can carry C ₁ -C ₄ alkyl groups, C ₁ -C ₄ alkoxy groups and fluorine, chlorine or bromine as substituents, and

    Y

    Isocyanate or one of the groups

    

    means. or

  • e) a bifunctional compound of the general formula IIe
    
    Z ¹ -R ¹⁰ -Z ² IIe
    
    in the

    R ¹⁰

    an alkylene group with 1 to 50 carbon atoms which can be interrupted by one or more non-adjacent oxygen atoms and / or can contain one or more non-vicinal hydroxyl groups, and

    Z ¹ , Z ²

    Chlorine, bromine, isocyanate or one of the groups

    

    means
  or mixtures thereof, and
• C) 25 to 100 mol% per mole I of a benzyl halide of the general formula III
  
  in the

  p

  for 0 to 2 and

  R ¹¹

  for a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group, fluorine, chlorine or bromine

  stands.

The precondensates used to prepare the cationic resins can be prepared by heating the trialkanolamines I, in particular triethanolamine or triisopropanolamine N [CH ₂ -CH (CH ₃ ) -OH] ₃ , in the presence of acidic catalysts, preferably phosphorous or hypophosphorous acid, at temperatures of 120 to 280 ° C, as described in EP-A 223 064, can be obtained. Deviating from the process of this EP-A, the reaction is expedient after reaching a viscosity range of 5,000 to 35,000 mPa · s, preferably from 10,000 to 25,000 mPa · s, for triethanolamine or from 100,000 to 600,000 mPa · s, preferably from 200,000 to 500,000 mPa.s. · S, for triisopropanolamine or from 100,000 to 250,000 mPa · s for a mixed condensate from preferably equimolar amounts of triethanolamine and triisopropanolamine (each measured in the undiluted state at 20 ° C.), broken off significantly below the gel point by cooling. For further crosslinking and / or for the incorporation of groups of different polarity on the chains which carry the alcohol functions and / or with quaternization on the central nitrogen atoms, the precondensates obtained are reacted with one or more compounds IIa to IIe. The amount of this Compounds is in the range from 1 to 30 mol%, preferably from 1 to 15 mol%, per mol of I.

• a) die defintionsgemäßen Carbonsäuren oder deren Derivate IIa, wobei die Reste R⁴ und R⁵ Hydroxylgruppen, C₁-C₈-Alkoxygruppen, vorzugsweise C₁-C₄-Alkoxygruppen, Chlor oder Brom bedeuten und für das Brückenglied R⁶ insbesondere die Gruppierungen
  
  in Betracht kommen, wobei q Werte von 1 bis 50, vorzugsweise 2 bis 10 und k Werte von 0 bis 24, vorzugsweise 0 bis 12, annehmen und R¹² Wasserstoff, Methyl oder Ethyl bedeutet; bevorzugt werden weiterhin unverzweigte Brükkenglieder R⁶.
  Als Beispiele für Verbindungen IIa sind zu nennen:
  • α) Kohlensäurederivate (n = 0), z.B. Kohlensäuredimethylester, Kohlensäurediethylester, Kohlensäuredipropylester, Kohlensäuredibutylester, Ethylencarbonat, 1,2-Propylencarbonat, 1,3-Propylencarbonat, 1,2-Butylencarbonat, 1,3-Butylencarbonat, 2,3-Butylencarbonat, Phosgen, Chlor- oder Bromkohlensäuremonomethylester und Chlor- oder Bromkohlensäuremonoethylester. Bevorzugt wrden cyclische Carbonate, darunter vor allem Ethylencarbonat und 1,3-Propylencarbonat;
  • β) Dicarbonsäuren (n = 1, R⁴=R⁵ = OH), z.B. Malonsäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Pimelinsäure, Korksäure, Azelainsäure und Sebacinsäure;
  • γ) Dicarbonsäurederivate (n = 1; R⁴, R⁵ = Alkoxy, Cl, Br); als Beispiele können hier die Dimethyl-, Diethyl-, Dipropyl- und Dibutylester sowie die Chloride und Bromide der unter β) aufgeführten Dicarbonsäuren dienen;
• b) die definitionsgemäßen Carbonsäureamide IIb, für die als Beispiele zu nennen sind:
  • α) Monocarbonsäureamide (n = r = O), z.B. Formamid, Acetamid, Propionsäureamid, Buttersäureamid, Benzamid sowie die N-Methyl-, N-Ethyl-, N-Propyl- und N-Butyl-Derivate dieser Amide;
  • β) Dicarbonsäureamide (m = 0, n = r = 1), z.B. Malonsäurediamid, Bernsteinsäurediamid, Glutarsäurediamid, Adipinsäurediamid, Pimelinsäurediamid, Korksäurediamid, Azelainsäurediamid, Sebacinsäurediamid sowie die N,N'-Dimethyl-, N,N'-Diethyl-, N,N'-Dipropyl- und N,N'-Dibutyl-Derivate dieser Diamide;
  • γ) Harnstoffe (n = 0, r = 1), z.B. Harnstoff, N-Methylharnstoff, N-Ethylharnstoff, N-Propylharnstoff, N-Butylharnstoff, N,N'-Dimethylharnstoff, N,N'-Diethylharnstoff, N,N'-Dipropylharnstoff, N,N'-Dibutylharnstoff, N-(2-Ethylhexyl)harnstoff, N-iso-Nonylharnstoff, N-iso-Tridecylharnstoff, N-Laurylharnstoff, N-Myristylharnstoff, N-Palmitylharnstoff, N-Stearylharnstoff, N-Oleylharnstoff, N-Linolylharnstoff, N-Linolylharnstoff, N-Linolenylharnstoff und N-Phenylharnstoff. Bevorzugt werden monosubstituierte Harnstoffe, und vor allem unsubstituierter Harnstoff;
  • δ) Bisharnstoffe (m = n = r = 1), z.B. Methylendiharnstoff, Ethylen-1,2-diharnstoff, Propylen-1,3-diharnstoff, Butylen-1,4-diharnstoff, Pentamethylen-1,5-diharnstoff, Hexamethylen-1,6-diharnstoff, Di(2-ureidoethyl)ether, Di(3-ureidopropyl)ether, Ethylenglykol-bis(2-ureidoethyl)ether, Ethylenglykol-bis(3-ureidoproyl)ether, Diethylenglykol-bis-(2-ureidoethyl)ether, Triethylenglykol-bis(2-ureidoethyl)ether und Tetraethylenglykol-bis(2-ureidoethyl)ether. Bevorzugt werden Bisharnstoffe mit einer Alkylenbrücken R⁶ mit 4 bis 10 C-Atomen und besonders bevorzugt wird Hexamethylen-1,6-diharnstoff;
• c) ein Epihalogenhydrin IIc, in der X Chlor oder Brom bedeutet. Bevorzugt wird Epichlorhydrin;
• d) die definitionsgemäßen monofunktionellen Verbindungen IId, für die als Beispiele zu nennen sind:
  • α) Isocyanate, z.B. Methylisocyanat, Ethylisocyanat, Propylisocyanat, Butylisocyanat, 2-Ethylhexylisocyanat, iso-Nonylisocyanat, iso-Tridecylisocyanat, Laurylisocyanat, Myristylisocyanat, Palmitylisocyanat, Stearylisocyanat, Oleylisocyanat, Linolylisocyanat, Linolenylisocyanat, Phenylisocyanat, o-, m- oder p-Chlorphenylisocyanat und o-, m- oder p-Tolylisocyanat;
  • β) Urethane, z.B. Carbaminsäuremethylester, Carbaminsäureethylester, Carbaminsäurepropylester, Carbaminsäurebutylester sowie die N-Methyl-, N-Ethyl-, N-Propyl- und N-Butyl-Derivate dieser Verbindungen;
  • γ) Glycidylether, z.B. Methylglycidylether, Ethylglycidylether, Propylglycidylether, Butylglycidylether, (2-Ethylhexyl)glycidylether, iso-Nonylglycidylether, iso-Decylglycidylether, iso-Tridecylglycidylether, Laurylglycidylether, Myristylglycidylether, Palmitylglycidylether, Stearylglycidylether, Oleylglycidylether, Linolylglycidylether, Linolenylglycidylether, Cyclohexylglycidylether, Glycidylether aus C₁₃-C₁₅-Oxoalkohol, C₁₂-C₁₄-Fettalkohol sowie C₁₆-C₁₈-Fettalkohol und Phenylglycidylether;
• e) die definitionsgemäßen bifunktionellen Verbindungen IIe, in der R¹⁰ eine Alkylengruppe mit 1 bis 50 C-Atomen, vorzugsweise mit 2 bis 26 C-Atomen, die durch ein oder mehrere nicht benachbarte Sauerstoffatome unterbrochen sein und/oder eine oder mehrere nicht vicinal zueinander stehende Hydroxylgruppen enthalten kann, bedeutet. Für das Brückenglied R¹⁰ kommen insbesondere die Gruppierungen
  
  in Betracht, wobei q Werte von 1 bis 50, vorzugsweise 2 bis 10 und k Werte von 0 bis 24, vorzugsweise 0 bis 12, annehmen und R¹² Wasserstoff, Methyl oder Ethyl bedeutet; bevorzugt werden weiterhin unverzweigte Brückenglieder R¹⁰.

Possible compounds IIa to IIe are:

• a) the defined carboxylic acids or their derivatives IIa, where the radicals R ⁴ and R ^{5 are} hydroxyl groups, C ₁ -C ₈ alkoxy groups, preferably C ₁ -C ₄ alkoxy groups, chlorine or bromine and for the bridge member R ⁶ in particular the groups
  
  come into consideration, wherein q values from 1 to 50, preferably 2 to 10 and k values from 0 to 24, preferably 0 to 12, and R ^{12 is} hydrogen, methyl or ethyl; unbranched bridge links R ⁶ are also preferred.
  The following are examples of compounds IIa:
  • α) carbonic acid derivatives (n = 0), for example dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, ethylene carbonate, 1,2-propylene carbonate, 1,3-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylene carbonate, Phosgene, monomethyl chloro- or bromocarbonate and monoethyl chloro- or bromocarbonate. Cyclic carbonates, in particular ethylene carbonate and 1,3-propylene carbonate, are preferred;
  • β) dicarboxylic acids (n = 1, R ⁴ = R ⁵ = OH), for example malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid;
  • γ) dicarboxylic acid derivatives (n = 1; R ⁴ , R ⁵ = alkoxy, Cl, Br); examples include the dimethyl, diethyl, dipropyl and dibutyl esters and the chlorides and bromides of the dicarboxylic acids listed under β) are used;
• b) the carboxamides IIb according to the definition, of which the following may be mentioned as examples:
  • α) Monocarboxamides (n = r = O), for example formamide, acetamide, propionic acid amide, butyric acid amide, benzamide and the N-methyl, N-ethyl, N-propyl and N-butyl derivatives of these amides;
  • β) Dicarboxamides (m = 0, n = r = 1), for example malonic acid diamide, succinic acid diamide, glutaric acid diamide, adipic acid diamide, pimelic acid diamide, corkic acid diamide, azelaic acid diamide, sebacic acid diamide and the N, N'-N'-dimethyl, diethyl , N'-dipropyl and N, N'-dibutyl derivatives of these diamides;
  • γ) ureas (n = 0, r = 1), e.g. urea, N-methylurea, N-ethylurea, N-propylurea, N-butylurea, N, N'-dimethylurea, N, N'-diethylurea, N, N ' -Dipropylurea, N, N'-dibutylurea, N- (2-ethylhexyl) urea, N-iso-nonylurea, N-iso-tridecylurea, N-laurylurea, N-myristylurea, N-palmitylurea, N-stearylurea, N- , N-linolylurea, N-linolylurea, N-linolenylurea and N-phenylurea. Monosubstituted ureas, and especially unsubstituted urea, are preferred;
  • δ) bisureas (m = n = r = 1), for example methylene diurea, ethylene 1,2-diurea, propylene 1,3-diurea, butylene 1,4-diurea, pentamethylene 1,5-diurea, hexamethylene 1,6-diurea, di (2-ureidoethyl) ether, di (3-ureidopropyl) ether, ethylene glycol bis (2-ureidoethyl) ether, ethylene glycol bis (3-ureidoproyl) ether, diethylene glycol bis (2-ureidoethyl) ) ether, triethylene glycol bis (2-ureidoethyl) ether and tetraethylene glycol bis (2-ureidoethyl) ether. Bis-ureas with an alkylene bridge R ⁶ with 4 to 10 carbon atoms and particularly preferred is hexamethylene-1,6-diurea;
• c) an epihalohydrin IIc in which X is chlorine or bromine. Epichlorohydrin is preferred;
• d) the monofunctional compounds IId according to the definition, of which the following may be mentioned as examples:
  • α) Isocyanates, for example methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, 2-ethylhexyl isocyanate, iso-nonyl isocyanate, iso-tridecyl isocyanate, lauryl isocyanate, myristyl isocyanate, palmityl isocyanate, stearyl isocyanate, oleyl isocyanate, linolyl isocyanate, linolenyl isocyanate, chlorophenyl isocyanate, phenyl isocyanate, phenyl isocyanate, phenyl isocyanate, phenyl isocyanate, phenyl isocyanate, phenyl isocyanate and o-, m- or p-tolyl isocyanate;
  • β) urethanes, for example methyl carbamate, ethyl carbamate, propyl carbamate, butyl carbamate and the N-methyl, N-ethyl, N-propyl and N-butyl derivatives of these compounds;
  • γ) glycidyl ether, eg methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, (2-ethylhexyl) glycidyl ether, iso-Nonylglycidylether, iso-decyl, iso-Tridecylglycidylether, Laurylglycidylether, Myristylglycidylether, Palmitylglycidylether, stearyl, oleyl glycidyl ether, Linolylglycidylether, Linolenylglycidylether, Cyclohexylglycidylether, glycidyl ether of C ₁₃ -C ₁₅ oxo alcohol, C ₁₂ -C ₁₄ fatty alcohol and C ₁₆ -C ₁₈ fatty alcohol and phenylglycidyl ether;
• e) the bifunctional compounds IIe according to the definition, in which R ^{10 is} an alkylene group with 1 to 50 C atoms, preferably with 2 to 26 C atoms, which are interrupted by one or more non-adjacent oxygen atoms and / or one or more not vicinally to one another may contain standing hydroxyl groups means. For the bridge member R ¹⁰ come in particular the groupings
  
  into consideration, q taking values from 1 to 50, preferably 2 to 10 and k taking values from 0 to 24, preferably 0 to 12, and R ^{12 being} hydrogen, methyl or ethyl; unbranched bridge members R ¹⁰ are also preferred.

• α) Dichloride oder Dibromide, z.B. Methylenchlorid, 1,2-Dichlorethan, 1,3-Dichlorpropan, 1,4-Dichlorbutan, 1,5-Dichlorpentan, 1,6-Dichlorhexan, Di[2-chlorethyl]ether, Di[3-chlorpropyl]ether, Ethylenglykol-bis[2-chlorethyl]ether, Ethylenglykol-bis[3-chlorpropyl]ether, Diethylenglykol-bis[2-chlorethyl]ether, Triethylenglykol-bis[2-chlorethyl]ether, 1,3-Dichlor-2-propanol, Di[3-chlor-2-hydroxypropyl]ether, Ethylenglykol-bis[3-chlor-2-hydroxypropyl]ether, Diethylenglykol-bis[-3chlor-2-hydroxypropyl]ether und Triethylenglykol-bis [3-chlor-2-hydroxypropyl]ether, Neopentylen-bis[3-chlor-2-hydroxypropyl]ether oder die entsprechenden Bromverbindungen;
• β) Diisocyanate, z.B. Ethylen-1,2-diisocyanat, Propylen-1,3-diisocyanat, Butylen-1,4-diisocyanat, pentamethylen-1,5-diisocyanat, Hexamethylen-1,6-diisocyanat, Di(2-isocyanatoethyl)ether, Di(3-isocyanatopropyl)ether, Ethylenglykol-bis(2-isocyanatoethyl)ether, Ethylenglykol-bis(3-isocyanatopropyl)ether, Diethylenglykol-bis(2-isocyanatoethyl)ether, Triethylenglykol-bis(2-isocyanatoethyl)ether und Tetraethylenglykol-bis(2-isocyanatoethyl)ether;
• γ) Bisurethane, z.B. die Dimethylester, Diethylester, Dipropylester und Dibutylester von Ethylen-1,2-dicarbaminsäure, Propylen-1,3-dicarbaminsäure, Butylen-1,4-dicarbaminsäure, Pentamethylen-1,5-dicarbaminsäure, Hexamethylen-1,6-dicarbaminsäure, Di[2-(carboxyamino)ethyl]ether, Di[3-(carboxyamino)ethyl]ether, Di[-(carboxyamino)-propyl]ether, Ethylenglykol-bis[2-(carboxyamino)ethyl]ether, Ethylenglykol-bis[3-(carboxyamino)propyl]ether, Diethylenglykol-bis[2-(carboxyamino)ethyl]ether, Triethylenglykol-[2-(carboxyamino))ethyl]ether und Tetraethylenglykol-bis[2-(carboxyamino)-ethyl]ether;
• δ) Bisglycidylether, z.B. Ethylenglykol-bisglycidylether, Propan-1,3-diol-bisglycidylether, Butan-1,4-diol-bisglycidylether, Pentan-1,5-diol-bisglycidylether, Hexan-1,6-diol-bis-glycidylether, Diethylenglykol-bis-glycidylether, Di[3-(glycidyloxy)propyl]ether, Triethylenglykol-bis-glycidylether, Ethylenglykol-bis[3-glycidyloxy)-propyl]ether, Tetraethylenglykolbis-glycidylether, Pentaethylenglykol-bis-glycidylether, Hexaethylenglykol-bis-glycidylether und Neopentylenglykol-bis-glycidylether;
• ε) γ-Alkoxy- oder γ-Aryloxypropylenhalogenhyride, z.B. [3-Chlor-2-hydroxypropyl]-methylether, [3-Chlor-2-hydroxypropyl]-ethylether, [3-Chlor-2-hydroxypropyl]-propylether, [3-Chlor-2-hydroxylpropyl]-butylether, [3-chlor-2-hydroxypropyl]-2-ethylhexylether, [3-Chlor-2-hydroxypropyl]-isononylether, [3-Chlor-2-hydroxypropyl]-isotridecylether, [3-Chlor-2-hydroxypropyl]-laurylether, [3-Chlor-2-hydroxypropyl]-myristylether, [3-Chlor-2-hydroxypropyl]-palmitylether, [3-Chlor-2-hydroxylpropyl]-stearylether, [3-Chlor-2-hydroxypropyl]-olelylether, [3-Chlor-2-hydroxypropyl]-linolylether, [3-Chlor-2-hydroxypropyl]-linolenylether und [3-Chlor-2-hydroxypropyl]-phenylether oder die entsprechenden Bromverbindungen.

The following are examples of compounds IIe:

• α ) dichlorides or dibromides, e.g. methylene chloride, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane, di [2-chloroethyl] ether, di [3 -chloropropyl] ether, ethylene glycol bis [2-chloroethyl] ether, ethylene glycol bis [3-chloropropyl] ether, diethylene glycol bis [2-chloroethyl] ether, triethylene glycol bis [2-chloroethyl] ether, 1,3-dichloro -2-propanol, di [3-chloro-2-hydroxypropyl] ether, ethylene glycol bis [3-chloro-2-hydroxypropyl] ether, diethylene glycol bis [-3chloro-2-hydroxypropyl] ether and triethylene glycol bis [3- chloro-2-hydroxypropyl] ether, neopentylene bis [3-chloro-2-hydroxypropyl] ether or the corresponding bromine compounds;
• β) diisocyanates, for example ethylene-1,2-diisocyanate, propylene-1,3-diisocyanate, butylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, hexamethylene-1,6-diisocyanate, di (2-isocyanatoethyl ) ether, di (3-isocyanatopropyl) ether, ethylene glycol bis (2-isocyanatoethyl) ether, ethylene glycol bis (3-isocyanatopropyl) ether, diethylene glycol bis (2-isocyanatoethyl) ether, triethylene glycol bis (2-isocyanatoethyl) ether and tetraethylene glycol bis (2-isocyanatoethyl) ether;
• γ) bisurethanes, for example the dimethyl esters, diethyl esters, dipropyl esters and dibutyl esters of ethylene-1,2-dicarbamic acid, propylene-1,3-dicarbamic acid, butylene-1,4-dicarbamic acid, Pentamethylene-1,5-dicarbamic acid, hexamethylene-1,6-dicarbamic acid, di [2- (carboxyamino) ethyl] ether, di [3- (carboxyamino) ethyl] ether, di [- (carboxyamino) propyl] ether, ethylene glycol -bis [2- (carboxyamino) ethyl] ether, ethylene glycol bis [3- (carboxyamino) propyl] ether, diethylene glycol bis [2- (carboxyamino) ethyl] ether, triethylene glycol [2- (carboxyamino)) ethyl] ether and tetraethylene glycol bis [2- (carboxyamino) ethyl] ether;
• δ) bisglycidyl ether, for example ethylene glycol bisglycidyl ether, propane-1,3-diol-bisglycidyl ether, butane-1,4-diol-bisglycidyl ether, pentane-1,5-diol-bisglycidyl ether, hexane-1,6-diol-bis-glycidyl ether , Diethylene glycol bis-glycidyl ether, di [3- (glycidyloxy) propyl] ether, triethylene glycol bis-glycidyl ether, ethylene glycol bis [3-glycidyloxy) propyl] ether, tetraethylene glycol bis-glycidyl ether, pentaethylene glycol bis-glycidyl ether, hexaethylene glycol glycidyl ether and neopentylene glycol bis-glycidyl ether;
• ε) γ-alkoxy or γ-aryloxypropylene halohydrides, for example [3-chloro-2-hydroxypropyl] methyl ether, [3-chloro-2-hydroxypropyl] ethyl ether, [3-chloro-2-hydroxypropyl] propyl ether, [3 -Chlor-2-hydroxylpropyl] butyl ether, [3-chloro-2-hydroxypropyl] -2-ethylhexyl ether, [3-chloro-2-hydroxypropyl] isonyl ether, [3-chloro-2-hydroxypropyl] isotridecyl ether, [3 -Chlor-2-hydroxypropyl] lauryl ether, [3-chloro-2-hydroxypropyl] myristyl ether, [3-chloro-2-hydroxypropyl] palmityl ether, [3-chloro-2-hydroxylpropyl] stearyl ether, [3-chloro -2-hydroxypropyl] olelyl ether, [3-chloro-2-hydroxypropyl] linolyl ether, [3-chloro-2-hydroxypropyl] linolenyl ether and [3-chloro-2-hydroxypropyl] phenyl ether or the corresponding bromine compounds.

The precondensate from triethanolamine is preferably reacted with a urea IIb (n = 0, r = 1), a bis urea IIb (m = n = r = 1) or a cyclic carbonate IIa (R ⁴ -R ⁵ = 0-alkylene- 0, n = 0) at temperatures from 100 to 210 ° C, preferably 140 to 200 ° C, without solvent up to a viscosity of 20,000 to 300,000 mPa · s, preferably 28,000 to 150,000 mPa · s, and with an epihalohydrin IIc without using a solvent at temperatures from 40 to 150 ° C, preferably 60 to 130 ° C, or in at least 40 vol .-% aqueous, optionally also aqueous-alcoholic solution at temperatures from 40 to 100 ° C to a viscosity of 80 wt .-% aqueous solution at 20 ° C of 12,000 to 40,000 mPa · s, preferably 15,000 to 36,000 mPa · s.

The precondensate from triisopropanolamine is preferably reacted with a urea IIb (n = 0, r = 1), a bis urea IIb (m = n = r = 1) or a cyclic carbonate IIa (R ⁴ -R ⁵ = 0-alkylene- 0, n = 0) at temperatures from 100 to 210 ° C, preferably 140 to 200 ° C, without solvent up to a viscosity of more than 500,000 mPa · s and with an epihalohydrin IIc without using a solvent at temperatures from 40 to 150 ° C, preferably 60 to 130 ° C, or in at least 40 vol .-% aqueous, optionally also aqueous alcoholic solution at temperatures from 40 to 100 ° C.

The quaternary condensation products described above as preferred are also preferably used in the first treatment bath in the dyeing process according to the invention.

Condensation products of piperazine and epichlorohydrin quaternized with benzyl chloride are also suitable. Condensation products of this type are, for example, from "The latest advances in the use of dyes" (Volume 2, page 96f) by L. Diserens, [2. Edition, published by Birkhäuser Basel 1949]. Piperazine and epichlorohydrin are condensed in a molar ratio (0.5-1): (1-0.5), preferably in a molar ratio of 1: 1. The condensation product is then quaternized by reaction with benzyl chloride. The quaternized condensation products in the form of a 50% aqueous solution have viscosities of 100 to 1000 Pa · s, preferably 200 to 500 mPa · s (measured at 20 ° C).

The concentration of the quaternized condensation products in the aqueous liquor is at least 5 g / l. Mixtures of the various condensation products can also be used. The concentration of quaternized condensation products can be up to 100 g / l or even more and is preferably in the range of 15 to 50 g / l. The quaternized condensation products are soluble in the aqueous liquor. The temperature of the aqueous liquor into which the textile materials for treatment are introduced can be varied within a wide range. Temperatures of 15 to 95 ° C are suitable. The preferred treatment temperatures are 20 to 35 ° C.

The aqueous liquor as component (ii) 0.02 to 1 g / l of a phosphoric acid triester, the alcohol component of which is derived from aliphatic, aryl-substituted aliphatic alcohols, phenols or alkyl-substituted phenols each having 6 to 18 carbon atoms in the alcohol or phenol radical. Suitable phosphoric triesters are, for example, triisobutyl phosphate, tri (2-ethylhexyl) phosphate, trihexyl phosphate, tridecyl phosphate, tridodecyl phosphate, tri-tert-butylphenyl phosphate, tridodecylphenyl phosphate and mixtures of at least 2 of the phosphates mentioned.

The surface or ring dyeing of the cellulose fibers is carried out continuously by first passing textile materials which contain or consist of cellulose fibers, for example on an indigo dyeing machine, through a bath which contains the compounds (i) and (ii) in the amounts indicated above contains. The textile materials are preferably in the form of a yarn which, after treatment with the aqueous liquor described above, is squeezed out and passed into another bath and dyed therein with reactive dyes in an aqueous medium.

All water-soluble reactive dyes are suitable for the process according to the invention. These dyes are described in detail in the Color Index, 3rd edition, published by the Soc. of Dyes and Colorists, Vol. 3, 6 to 8 and in Additions and Amendments No. 65 to 81. The most important feature of this class of dyes is the reactive group via which the chromophoric part of the dye molecule is bound to the substrate to be colored. Suitable reactive groups are, for example, vinylsulfone, beta-sulfatoethylsulfone, beta-chloroethylsulfone and beta-dialkylaminoethylsulfone groups or heterocycles substituted by 1 to 3 halogen atoms, such as triazine, pyrdazine, pyridazone, quinoxaline and pyrimidine. The reactive dyes can be one or contain several reactive groups. The chromophoric part is primarily derived from azo compounds, disazo compounds, metal complexes of azo dyes or disazo dyes, anthraquinone derivatives, formazans and phthalocyanines.

The cellulose fibers are dyed with reactive dyes by known methods, e.g. in the temperature range from 20 to 95 ° C.

The textile material coming from the dyebath is then continuously treated with an alkaline liquor to fix the reactive dyes, through which it is passed continuously. The staining is also fixed and completed in a conventional manner. To complete the dyeing, the textile material is preferably passed through an aqueous liquor which contains 0.5 to 2 g / l of a washing and / or dispersing agent. The material is then rinsed once or several times with water.

This gives colored cellulose textile materials in which the individual fibers are only colored on the surface and not on the inside. The individual cellulose fibers are therefore not colored over the entire cross-section of the fiber, but only in the outer areas. One speaks therefore of a ring coloring. With the textile materials dyed in this way, the "washdown" effects known from indigo can be achieved. With the method according to the invention, a simple method is used to dye textile materials made of cellulose fibers on dyeing systems, on which dyeing is otherwise carried out with indigo dyes, and dyeings are obtained with any reactive dyes. The textile materials dyed in this way can advantageously be used to produce denim fabrics in practically any color shade which, after the corresponding treatment, have wash-down effects.

Unless stated otherwise, the percentages in the examples are% by weight.

Examples Cationic compound I

Aqueous solution of a polyquaternary compound, which was obtained according to synthesis example 5 of US Pat. No. 5,015,754 by condensation of a triethanolamine precondensate with 5 mol% urea and subsequent quaternization with 90 mol% benzyl chloride.

Cationic compound II

Condensation product of piperazine and epichlorohydrin in a molar ratio of 1: 1 and quaternization with 1.4 mol of benzyl chloride, based on piperazine. The viscosity of the 47% aqueous solution is: 325 mPa · s.

Phosphoric acid ester I

Neutral phosphoric triester of an aliphatic alcohol with 8 carbon atoms.

example 1

A raw cotton yarn (12 Nm / l) is passed for 10 seconds through a liquor which contains 4 parts of the cationic compound I, 0.03 parts of the phosphoric acid ester I.

The cotton yarn is squeezed to about 40% liquor absorption and passed through an air passage for one minute. In the second liquor trough, through which the yarn is again immersed wet for 10 seconds, contains 3 parts of the reactive dye CI Reactive Blue 21 and 3 parts of NaCl. The liquor addition after padding was approximately 25%. A one-minute airflow followed. In the third liquor trough, the dye was fixed with an alkaline solution at 95 ° C. The fixing liquor contained 15 parts by volume of NaOH 38 ° Bé and 20 parts of Nacl. After squeezing the yarn, there was a double rinse with water (room temperature) for 10 seconds each and then padding, a soaping process with 0.1 part of a commercially available detergent at boiling temperature for 10 seconds, followed by squeezing of warp yarn. The yarn was then rinsed again and then dried.

A turquoise-colored yarn is obtained in which the cellulose fibers have a very good ring color, which is essential for the denim article with wash-down effects. The fastness properties achieved correspond to those which are usually obtained for a denim article with wash-down effects.

Example 2

A raw cotton yarn (12 Nm / l) is passed through a liquor containing 4 parts of the cationic compound I, 0.03 part of the phosphoric acid ester I and 0.05 part of a commercially available nonionic wetting agent for 10 seconds.

The cotton yarn is squeezed to about 40% liquor absorption and passed through an air passage for one minute. In the second liquor trough, through which the yarn is again immersed wet for 10 seconds, contains 3 parts of the reactive dye C.I. Reactive Blue 21 and 3 parts NaCl. The liquor addition after padding was approximately 25%. A one-minute airflow followed. In the third liquor trough, the dye was fixed with an alkaline solution at 95 ° C. The fixing liquor contained 15 parts by volume of NaOH 38 ° Bé and 20 parts of Nacl. After squeezing the yarn, there was a double rinse with water (room temperature) for 10 seconds each and then padding, a soaping process with 0.1 part of a commercially available detergent at cooking temperature for 10 seconds, followed by squeezing off the warp yarn. The yarn was then rinsed again and then dried.

A turquoise thread is obtained. The individual cellulose fibers have a very good ring color. Compared to Example 1, the depth of penetration of the dye into the textile material is greater. This is due to the wetting agent content in the 1st treatment bath.

The fastness properties obtained correspond to those which are customary for a denim article with wash-down effects.

Example 3

A raw cotton yarn (12 Nm / l) is passed through a liquor containing 4 parts of the cationic compounds II and 0.03 parts of the phosphoric acid ester I for 10 seconds.

The cotton yarn is squeezed to about 40% liquor absorption and passed through an air passage for one minute. In the second liquor trough, through which the yarn is dipped wet in wet again for 10 seconds, contains 3 parts of the reactive dye C.I. Reactive Red 24 and 3 parts NaCl. The liquor addition after fouarding was approx. 25%. A one-minute airflow followed. In the third liquor trough, the dye was fixed with an alkaline solution at 95 ° C. The fixing liquor contained 15 parts by volume of NaOH 38 ° Bé and 20 parts of NaCl. After squeezing the yarn, there was a double rinse with water (room temperature) for 10 seconds each and then padding, a soaping process with 0.1 part of a commercially available detergent at cooking temperature for 10 seconds, followed by squeezing off the warp yarn. The yarn was then rinsed again and then dried.

A red yarn is obtained. The individual cellulose fibers have a very good ring color. The fastness properties obtained correspond to those which are customary for a denim article with wash-down effects.

Claims (3)

1. A process for the continuous production of surface dyeings on cellulose fibers present in the form of textile materials, characterized in that the textile materials are initially treated with an aqueous liquor which contains

   (i) at least 5 g/l of benzyl halide-quaternized condensation products of precondensates of trialkanolamines and ureas, cyclic carbonates and/or epihalohydrins and/or benzyl chloride-quaternized condensation products of piperazine and epichlorohydrin and

   (ii) 0.02 to 1 g/l of a phosphoric triester whose alcohol component is derived from aliphatic, aryl-substituted aliphatic alcohols, phenols or alkyl-substituted phenols having in each case 6 to 18 carbon atoms in the alcohol or phenol radical,

   the textile materials thus treated are then dyed with reactive dyes in another bath in an aqueous medium, and subsequently the dyes are fixed in a conventional manner by treatment with an alkaline liquor, and the dyeing is finished.
2. A process as claimed in claim 1, characterized in that the textile materials are treated with the aqueous liquor which contains the compounds (i) and (ii) at 15 to 95°C.
3. A process as claimed in claim 1 or 2, characterized in that the aqueous liquor, as well as the compounds (I) and (II), additionally contains (iii) 0.1 to 1 g/l of a nonionic wetting agent.