EP0768423A2 - Process for dyeing, printing, coating condensations products of melamin-formaldehyde, with pigments - Google Patents

Process for dyeing, printing, coating condensations products of melamin-formaldehyde, with pigments Download PDF

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Publication number
EP0768423A2
EP0768423A2 EP96115893A EP96115893A EP0768423A2 EP 0768423 A2 EP0768423 A2 EP 0768423A2 EP 96115893 A EP96115893 A EP 96115893A EP 96115893 A EP96115893 A EP 96115893A EP 0768423 A2 EP0768423 A2 EP 0768423A2
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EP
European Patent Office
Prior art keywords
pigment
alkyl
aqueous
formaldehyde
hydroxy
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP96115893A
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German (de)
French (fr)
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EP0768423A3 (en
Inventor
Uwe Dr. Nahr
Günther Widler
Rainer Eichler
Horst Fuchs
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BASF SE
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BASF SE
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Publication of EP0768423A2 publication Critical patent/EP0768423A2/en
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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
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/82—Textiles which contain different kinds of fibres
    • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
    • 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
    • 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
    • D06P1/52—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 synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
    • D06P1/5257—(Meth)acrylic acid
    • 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
    • D06P1/52—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 synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5285—Polyurethanes; Polyurea; Polyguanides
    • 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
    • D06P1/52—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 synthetic macromolecular substances
    • D06P1/54—Substances with reactive groups together with crosslinking agents
    • 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
    • D06P3/605—Natural or regenerated cellulose dyeing with polymeric dyes; building polymeric dyes on fibre
    • D06P3/6066—Natural or regenerated cellulose dyeing with polymeric dyes; building polymeric dyes on fibre by using reactive polyfunctional compounds, e.g. crosslinkers

Definitions

  • the present application relates to a new process for dyeing, printing or coating condensation products in textile form, which can be obtained by condensing a mixture containing unsubstituted melamine, substituted melamine and hydroxyphenyl compounds, with formaldehyde or formaldehyde-providing compounds, using pigments.
  • condensation products based on melamine and formaldehyde are known from US Pat. No. 5,322,915. These condensation products can be used for the production of refractory fibers, fabrics, knitted fabrics or nonwovens, for example refractory suits.
  • the object of the present invention was to provide a method by means of which such condensation products can be colored, printed or coated in an advantageous manner by means of pigments.
  • the condensation products should be in textile form, i.e. in the form of fibers, yarns, threads, knitwear, woven goods or non-wovens.
  • component (A) consists essentially of 50 to 99 mol%, in particular 85 to 95 mol%, melamine and 1 to 50 mol%, in particular 5 to 15 mol% %, Melamine of formula I.
  • condensation products which can be obtained by reacting components (A) and (B) with formaldehyde or compounds providing formaldehyde are also preferably used, wherein the molar ratio of melamines to formaldehyde is in the range from 1: 1.8 to 1: 3.0.
  • Y is, for example, hydroxy-C 2 -C 10 -alkyl, such as 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxyisopropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl or 3-hydroxy-2,2-dimethylpropyl.
  • Y is preferably hydroxy-C 2 -C 6 -alkyl, in particular hydroxy-C 2 -C 4 -alkyl and very particularly preferably 2-hydroxyethyl or 2-hydroxyisopropyl.
  • Y is furthermore, for example, hydroxy-C 2 -C 4 -alkyl- (oxa-C 2 -C 4 -alkyl) n , such as 5-hydroxy-3-oxapentyl, 5-hydroxy-3-oxa-2,5-dimethylpentyl, 5-hydroxy-3-oxa-1,4-dimethylpentyl, 5-hydroxy-3-oxa-1,2,4,5-tetramethylpentyl or 8-hydroxy-3,6-dioxaoctyl.
  • N is preferably 1 to 4, in particular 1 or 2.
  • Y is furthermore, for example, amino-C 2 -C 12 -alkyl, such as 2-aminoethyl, 3-aminopropyl, 4-aminobutyl, 5-aminopentyl, 6-aminohexyl, 7-aminoheptyl or 8-aminooctyl.
  • Y is preferably amino-C 2 -C 8 -alkyl, particularly preferably 2-aminoethyl or 6-aminohexyl and very particularly preferably 6-aminohexyl.
  • Suitable substituted melamines of the formula I are, for example, the following compounds: 2-hydroxyethylamino-1,3,5-triazines, such as 2-hydroxyethylamino-1,3,5-triazine, 2,4-bis (2-hydroxyethylamino) -1,3,5-triazine or 2,4,6- Tris (2-hydroxyethylamino) -1,3,5-triazine, 2-hydroxyisopropylamino-1,3,5-triazines, such as 2- (2-hydroxyisopropylamino) -1,3,5-triazine, 2,4-bis ( 2-hydroxyisopropylamino) -1,3,5-triazine or 2,4,6-tris (2-hydroryisopropylamino) -1,3,5-triazine, 5-hydroxy-3-oxapentylamino-1,3,5-triazine, such as 2- (5-hydroxy-3-oxapentylamino) -1
  • Suitable compounds (B) are, for example, phenol, 4-methylphenol, 4-tert-butylphenol, 4-octylphenol, 4-nonylphenol, pyrocatechol, resorcinol, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane or 4,4'- Dihydroxydiphenyl sulfone. Phenol, resorcinol or 2,2-bis (4-hydroxyphenyl) propane are preferred.
  • Formaldehyde is generally used as an aqueous solution with a concentration of e.g. 40 to 50% by weight or in the form of compounds providing formaldehyde during the reaction with (A) and (B), for example as oligomeric or polymeric formaldehyde in solid form, such as paraformaldehyde, 1,3,5-trioxane or 1,3 , 5,7-tetroxocan.
  • Fibers can be produced in a manner known per se from the condensation products described above (e.g. EP-A-408 947).
  • the method according to the invention can also be used to advantageously dye, print or coat mixed fabrics of the condensation products specified above with cotton, wool, acetate, polyacrylonitrile or aramid fibers.
  • Particularly suitable aramids consist essentially of a polycondensation product of iso- or terephthalic acid with a meta- or para-phenylenediamine. Such products are known and e.g. commercially available under the name Nomex® or Kevlar® (DuPont).
  • Pigments which can be used in the process according to the invention are both inorganic and organic pigments.
  • Inorganic pigments which serve as colorants in the process according to the invention are, for example, titanium dioxide, zinc oxide, zinc sulfide, cadmium pigments, such as cadmium sulfide, cadmium selenide or cadmium mercury sulfide, chromate pigments, chromium oxides, iron oxides, ultramarine pigments, iron cyanoferrates or carbon blacks.
  • Organic pigments which serve as colorants in the process according to the invention are, for example, those from the class of the monoazo pigments (for example products which are derived from acetoacetic acid derivatives or from ⁇ -naphthol derivatives), lacquered monoazo dyes, such as lacquered ⁇ -oxynaphthoic acid dyes, disazo pigments, condensed disazo pigments , Azomethine metal complex pigments, benzimidazolone pigments, isoindoline derivatives, derivatives of naphthalene, naphthalene tetracarbonate or perylene tetracarboxylic acid, perinones, anthraquinone pigments, trioindigo derivatives, azomethine derivatives, quinacridone, dioxazines, pyrazoloquinophenazolone dyes, verbenzene phenol enolone, verbenzene phenol enolone, verbenzene enol dye
  • Such pigments are known per se and are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Volume A 20, pages 243 to 360 and pages 371 to 412.
  • Pigment Yellow 42 examples include the inorganic pigments Pigment Yellow 42 (CI 77 492), Pigment White 6 (CI 77 891), Pigment Red 101 (CI 77 491), Pigment Red 102, Pigment Blue 27 (CI 77 510), Pigment Blue 29 (CI 77 007) or Pigment Black 7 (CI 77 266) and the organic pigments Pigment Yellow 1 (CI 11 680), Pigment Yellow 3 (CI 11 710), Pigment Yellow 16 (CI 20 040), Pigment Yellow 17 (CI 21 705 , Pigment Yellow 42 (CI 77 492), Pigment Yellow 74 (CI 11 741), Pigment Yellow 81 (CI 21 127), Pigment Yellow 83 (CI 21 108), Pigment Yellow 106, Pigment Yellow 108 (CI 68 240), Pigment Yellow 113, Pigment Yellow 117, Pigment Yellow 126, Pigment Yellow 138 (CI 56 300), Pigment Yellow 139, Pigment Yellow 185, Pigment Orange 5 (CI 12 075), Pigment Orange 13 (CI 21 110), Pigment Orange
  • Particularly suitable binders which can be used in the process according to the invention are polyacrylates or polyurethanes or mixtures thereof.
  • suitable polyacrylates are polyacrylic acids, polymethacrylic acids, copolymers of acrylic or methacrylic acid and acrylic or methacrylic acid esters, copolymers of acrylamide and acrylic acid and copolymers of acrylamide and hydroxyalkyl acrylates. These products are known per se and are commercially available.
  • suitable polyurethanes here are those as described in DE-A-2 645 779 and US-A-4 092 286.
  • Hydrophilically modified polyisocyanates are advantageously suitable as crosslinking agents. These are in particular customary diisocyanates and / or customary higher-functionality polyisocyanates an average NCO functionality of 2.0 to 4.5. These components can be present alone or in a mixture. They are described in the earlier patent application WO-A-95/30045, to which express reference is made here.
  • thickeners e.g. high polymer synthetic thickener based on acrylate.
  • auxiliaries which are known and customary, e.g. Wetting agents, anti-migration agents, process aids such as anti-roll coating agents, defoamers or crease-resistant agents with associated catalysts are used.
  • the liquid phase in the aqueous preparations used according to the invention is generally purely aqueous.
  • Mixtures of water with water-miscible organic solvents such as alcohols, e.g. Ethanol or isopropanol, dioxane, glycols or glycol ethers can be used.
  • Mixtures of water and ethyl acetate, acetone, methyl ethyl ketone, carbonic acid esters, such as diethyl carbonate, 1,2-ethylene carbonate or 1,2-propylene carbonate, or lactones, such as ⁇ -propiolactone, ⁇ -butyrolactone or ⁇ -caprolactone, can also be used.
  • the water content or the content of mixtures of water with water-miscible organic solvents is usually about 45 to about 99% by weight.
  • the dyeing of the condensation products with an aqueous pigment dyeing liquor is expediently carried out in such a way that the condensation product in the form of fibers, yarns, twists, knitted fabrics, woven goods or nonwovens is impregnated with the aqueous pigment dyeing liquor at a temperature of from 20 to 70 ° C. and then squeezed off , dries (e.g. at 80 to 140 ° C) and thermally treated (e.g. 0.5 to 3 minutes at 140 to 200 ° C).
  • the printing of the condensation products with an aqueous printing paste is expediently carried out in such a way that the condensation product in the form of fibers, yarns, twists, knitted fabrics, woven goods or non-wovens at a temperature of 20 to 40 ° C. with the aqueous printing paste using a template or printed on an engraved roller, dries (e.g. at 80 to 160 ° C) and thermally treated (e.g. 1 to 6 minutes at 180 to 140 ° C).
  • the coating of the condensation products with an aqueous coating paste is expediently carried out in such a way that the condensation product is in the form of fibers, yarns, twists, knitted fabrics, woven goods or nonwovens at a temperature of 20 to 40 ° C. with the aqueous coating paste using a template or coated with a doctor blade, dries (eg at 80 to 180 ° C), condensed (eg 0.5 to 5 minutes at 190 to 140 ° C) and post-condensed (eg 1 to 5 days at 10 to 60 ° C).
  • the liquor intake was limited to 63% by squeezing pressure.
  • the mixture was then dried at 100 to 120 ° C and fixed at about 180 ° C for 1 to 3 min.
  • the resulting printing paste was then printed with a planographic stencil onto a fabric with a weight of approx. 300 g / m 2 , which was produced from fibers of condensation products, the production of which is described in Example 3b of US Pat. No. 5,322,915.
  • the fabric was then dried at 100 ° C. for 2 minutes and condensed with superheated steam at 150 ° C. for 5 minutes. (Instead of superheated steam, hot air at a temperature of 120 ° C can be used with equally good results.
  • a binder based on a conventional polyurethane Perapret PU, BASF Aktiengesellschaft
  • 30 g of crosslinking agent nonionically hydrophilically modified polyisocyanate, according to Example 1 of WO-A-95/30045
  • 2 g of a commercially available defoamer were added to 600 ml of water .
  • the mixture was stirred for 4 min in a high-speed stirrer at 5000 rpm.
  • 100 g of pigment and 35 g of a commercially available high-polymer synthetic thickener based on acrylate were added and the mixture was stirred at 2000 rpm for 5 minutes.
  • the resulting coating paste was then coated with an air knife over a fabric with a weight of approx. 300 g / m 2 , which was produced from fibers of condensation products, the production of which is described in Example 3b of US Pat. No. 5,322,915 (20 g / m 2 ).
  • the fabric was then dried for 2 minutes at 95 ° C., condensed for 1.5 minutes with hot air at 180 ° C. and then condensed for 2 days at 20 ° C.
  • Pigment Red 101 (C.I. 77491)
  • Pigment Red 102 Pigment Black 7
  • Pigment Black 7 (C.I. 77266).

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • Coloring (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

Verfahren zum F{rben, Bedrucken oder Beschichten von Kondensationsprodukten, die erh{ltlich sind durch Kondensation eines Gemisches, enthaltend unsubstituiertes Melamin, substituiertes Melamin und Hydroxyphenylverbindungen, mit Formaldehyd oder formaldehydliefernden Verbindungen, in Form von Fasern, Garnen, Zwirnen, Maschenware, Webware oder Non-wovens mit einer w{ssrigen Pr{paration, enthaltend Pigmente.

Description

Die vorliegende Anmeldung betrifft ein neues Verfahren zum Färben, Bedrucken oder Beschichten von Kondensationsprodukten in textiler Form, die erhältlich sind durch Kondensation eines Gemisches, enthaltend unsubstituiertes Melamin, substituiertes Melamin und Hydroxyphenylverbindungen, mit Formaldehyd oder formaldehydliefernden Verbindungen, mittels Pigmenten.The present application relates to a new process for dyeing, printing or coating condensation products in textile form, which can be obtained by condensing a mixture containing unsubstituted melamine, substituted melamine and hydroxyphenyl compounds, with formaldehyde or formaldehyde-providing compounds, using pigments.

Aus der US-A-5 322 915 sind spezielle Kondensationsprodukte auf Basis von Melamin und Formaldehyd bekannt. Diese Kondensationsprodukte können zur Herstellung von feuerfesten Fasern, Geweben, Gewirken oder Vliesen, beispielsweise feuerfeste Anzüge, verwendet werden.Special condensation products based on melamine and formaldehyde are known from US Pat. No. 5,322,915. These condensation products can be used for the production of refractory fibers, fabrics, knitted fabrics or nonwovens, for example refractory suits.

Aus der älteren Patentanmeldung EP-A-702 107 ist das Färben dieser Kondensationsprodukte mit speziellen Farbstoffen bekannt.The dyeing of these condensation products with special dyes is known from the earlier patent application EP-A-702 107.

Aufgabe der vorliegenden Erfindung war es, ein Verfahren bereitzustellen, mittels dessen solche Kondensationsprodukte mittels Pigmenten in vorteilhafter Weise gefärbt, bedruckt oder beschichtet werden können. Die Kondensationsprodukte sollten dabei in textiler Form, d.h. in Form von Fasern, Garnen, Zwirnen, Maschenware, Webware oder Non-wovens zur Anwendung gelangen.The object of the present invention was to provide a method by means of which such condensation products can be colored, printed or coated in an advantageous manner by means of pigments. The condensation products should be in textile form, i.e. in the form of fibers, yarns, threads, knitwear, woven goods or non-wovens.

Es wurde nun gefunden, daß das Färben, Bedrucken oder Beschichten von Kondensationsprodukten, die erhältlich sind durch Kondensation eines Gemisches, enthaltend als wesentliche Komponenten

  • (A) 90 bis 99,9 Mol-% eines Gemisches, bestehend im wesentlichen aus
    • (a) 30 bis 99 Mol-% Melamin und
    • (b) 1 bis 70 Mol-% eines substituierten Melamins der Formel I
      Figure imgb0001
       in der die Reste Y unabhängig voneinander jeweils Wasserstoff, Hydroxy-C2-C10-alkyl, Hydroxy-C2-C4-alkyl-(oxa-C2-C4-alkyl)n, worin n für 1 bis 5 steht, oder Amino-C2-C12-alkyl bedeuten, mit der Maßgabe, daß mindestens ein Rest Y von Wasserstoff verschieden ist, oder Mischungen von Melaminen der Formel I sowie
  • (B) 0,1 bis 10 Mol-%, bezogen auf (A) und (B), Phenol, das gegebenenfalls durch C1-C9-Alkyl oder Hydroxy substituiert ist, C1-C4-Alkane, die durch Hydroxyphenyl substituiert sind, Bis(hydroxyphenyl)sulfone oder Mischungen dieser Verbindungen,
mit
Formaldehyd oder formaldehydliefernden Verbindungen, wobei das Molverhältnis von Melaminen zu Formaldehyd im Bereich von 1:1,15 bis 1:4,5 liegt,
vorteilhaft gelingt, wenn man die Kondensationsprodukte in Form von Fasern, Garnen, Zwirnen, Maschenware, Webware oder Non-wovens mit einer wäßrigen Präparation, enthaltend eines oder mehrere Pigmente, Bindemittel und gegebenenfalls Vernetzer und Verdickungsmittel, bei einer Temperatur von 10 bis 200°C behandelt.It has now been found that the dyeing, printing or coating of condensation products which can be obtained by condensing a mixture containing as essential components
  • (A) 90 to 99.9 mol% of a mixture consisting essentially of
    • (a) 30 to 99 mole% melamine and
    • (b) 1 to 70 mol% of a substituted melamine of the formula I.
      Figure imgb0001
       in which the radicals Y independently of one another are each hydrogen, hydroxy-C 2 -C 10 -alkyl, hydroxy-C 2 -C 4 -alkyl- (oxa-C 2 -C 4 -alkyl) n , where n is 1 to 5 , or amino-C 2 -C 12 alkyl, with the proviso that at least one radical Y is different from hydrogen, or mixtures of melamines of the formula I and
  • (B) 0.1 to 10 mol%, based on (A) and (B), phenol which is optionally substituted by C 1 -C 9 -alkyl or hydroxy, C 1 -C 4 -alkanes which are substituted by hydroxyphenyl are substituted, bis (hydroxyphenyl) sulfones or mixtures of these compounds,
With
Formaldehyde or compounds providing formaldehyde, the molar ratio of melamines to formaldehyde being in the range from 1: 1.15 to 1: 4.5,
it succeeds advantageously if the condensation products in the form of fibers, yarns, twists, knitwear, woven goods or nonwovens with an aqueous preparation containing one or more pigments, binders and optionally crosslinking agents and thickeners at a temperature of 10 to 200 ° C. treated.

Wie eingangs schon erwähnt, ist die Herstellung der Kondensationsprodukte in der US-A-5 322 915 beschrieben, auf die hier ausdrücklich Bezug genommen wird.As already mentioned at the beginning, the preparation of the condensation products is described in US Pat. No. 5,322,915, to which reference is expressly made here.

Im erfindungsgemäßen Verfahren kommen vorzugsweise solche Kondensationsprodukte zur Anwendung, bei denen die Komponente (A) im wesentlichen aus 50 bis 99 Mol-%, insbesondere 85 bis 95 Mol-%, Melamin und 1 bis 50 Mol-%, insbesondere 5 bis 15 Mol-%, Melamin der Formel I besteht.In the process according to the invention, preference is given to using condensation products in which component (A) consists essentially of 50 to 99 mol%, in particular 85 to 95 mol%, melamine and 1 to 50 mol%, in particular 5 to 15 mol% %, Melamine of formula I.

Weiterhin bevorzugt kommen solche Kondensationsprodukte zur Anwendung, die erhältlich sind durch Umsetzung der Komponenten (A) und (B) mit Formaldehyd oder formaldehydliefernden Verbindungen, wobei das Molverhältnis von Melaminen zu Formaldehyd im Bereich von 1:1,8 bis 1:3,0 liegt.Those condensation products which can be obtained by reacting components (A) and (B) with formaldehyde or compounds providing formaldehyde are also preferably used, wherein the molar ratio of melamines to formaldehyde is in the range from 1: 1.8 to 1: 3.0.

Y ist z.B. Hydroxy-C2-C10-alkyl, wie 2-Hydroxyethyl, 3-Hydroxypropyl, 2-Hydroxyisopropyl, 4-Hydroxybutyl, 5-Hydroxypentyl, 6-Hydroxyhexyl oder 3-Hydroxy-2,2-dimethylpropyl. Y ist vorzugsweise Hydroxy-C2-C6-alkyl, insbesondere Hydroxy-C2-C4-alkyl und ganz besonders bevorzugt 2-Hydroxyethyl oder 2-Hydroxyisopropyl.Y is, for example, hydroxy-C 2 -C 10 -alkyl, such as 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxyisopropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl or 3-hydroxy-2,2-dimethylpropyl. Y is preferably hydroxy-C 2 -C 6 -alkyl, in particular hydroxy-C 2 -C 4 -alkyl and very particularly preferably 2-hydroxyethyl or 2-hydroxyisopropyl.

Y ist weiterhin z.B. Hydroxy-C2-C4-alkyl-(oxa-C2-C4-alkyl)n, wie 5-Hydroxy-3-oxapentyl, 5-Hydroxy-3-oxa-2,5-dimethylpentyl, 5-Hydroxy-3-oxa-1,4-dimethylpentyl, 5-Hydroxy-3-oxa-1,2,4,5-tetramethylpentyl oder 8-Hydroxy-3,6-dioxaoctyl. Dabei ist n vorzugsweise 1 bis 4, insbesondere 1 oder 2.Y is furthermore, for example, hydroxy-C 2 -C 4 -alkyl- (oxa-C 2 -C 4 -alkyl) n , such as 5-hydroxy-3-oxapentyl, 5-hydroxy-3-oxa-2,5-dimethylpentyl, 5-hydroxy-3-oxa-1,4-dimethylpentyl, 5-hydroxy-3-oxa-1,2,4,5-tetramethylpentyl or 8-hydroxy-3,6-dioxaoctyl. N is preferably 1 to 4, in particular 1 or 2.

Y ist weiterhin z.B. Amino-C2-C12-alkyl, wie 2-Aminoethyl, 3-Aminopropyl, 4-Aminobutyl, 5-Aminopentyl, 6-Aminohexyl, 7-Aminoheptyl oder 8-Aminooctyl. Y ist vorzugsweise Amino-C2-C8-alkyl, besonders bevorzugt 2-Aminoethyl oder 6-Aminohexyl und ganz besonders bevorzugt 6-Aminohexyl.Y is furthermore, for example, amino-C 2 -C 12 -alkyl, such as 2-aminoethyl, 3-aminopropyl, 4-aminobutyl, 5-aminopentyl, 6-aminohexyl, 7-aminoheptyl or 8-aminooctyl. Y is preferably amino-C 2 -C 8 -alkyl, particularly preferably 2-aminoethyl or 6-aminohexyl and very particularly preferably 6-aminohexyl.

Geeignete substituierte Melamine der Formel I sind z.B. folgende Verbindungen:
2-Hydroxyethylamino-1,3,5-triazine, wie 2-Hydroxyethylamino-1,3,5-triazin, 2,4-Bis(2-hydroxyethylamino)-1,3,5-triazin oder 2,4,6-Tris(2-hydroxyethylamino)-1,3,5-triazin, 2-Hydroxyisopropylamino-1,3,5-triazine, wie 2-(2-Hydroxyisopropylamino)-1,3,5-triazin, 2,4-Bis(2-hydroxyisopropylamino)-1,3,5-triazin oder 2,4,6-Tris(2-hydroryisopropylamino)-1,3,5-triazin, 5-Hydroxy-3-oxapentylamino-1,3,5-triazine, wie 2-(5-Hydroxy-3-oxapentylamino)-1,3,5-triazin, 2,4-Bis(5-hydroxy-3-oxapentylamino)-1,3,5-triazin oder 2,4,6-Tris(5-hydroxy-3-oxapentylamino)-1,3,5-triazin, oder 6-Aminohexylamino-1,3,5-triazine, wie 2-(6-Aminohexylamino)-1,3,5-triazin, 2,4-Bis(6-aminohexylamino)-1,3,5-triazin oder 2,4,6-Tris(6-aminohexylamino)-1,3,5-triazin oder Gemische dieser Verbindungen, beispielsweise ein Gemisch aus 10 Mol-% 2-(5-Hydroxy-3-oxapentylamino)-1,3,5-triazin, 50 Mol-% 2,4-Bis(5-hydroxy-3-oxapentylamino)-1,3,5-triazin und 40 Mol-% 2,4,6-Tris(5-hydroxy-3-oxapentylamino)-1,3,5-triazin.Suitable substituted melamines of the formula I are, for example, the following compounds:
2-hydroxyethylamino-1,3,5-triazines, such as 2-hydroxyethylamino-1,3,5-triazine, 2,4-bis (2-hydroxyethylamino) -1,3,5-triazine or 2,4,6- Tris (2-hydroxyethylamino) -1,3,5-triazine, 2-hydroxyisopropylamino-1,3,5-triazines, such as 2- (2-hydroxyisopropylamino) -1,3,5-triazine, 2,4-bis ( 2-hydroxyisopropylamino) -1,3,5-triazine or 2,4,6-tris (2-hydroryisopropylamino) -1,3,5-triazine, 5-hydroxy-3-oxapentylamino-1,3,5-triazine, such as 2- (5-hydroxy-3-oxapentylamino) -1,3,5-triazine, 2,4-bis (5-hydroxy-3-oxapentylamino) -1,3,5-triazine or 2,4,6- Tris (5-hydroxy-3-oxapentylamino) -1,3,5-triazine, or 6-aminohexylamino-1,3,5-triazines, such as 2- (6-aminohexylamino) -1,3,5-triazine, 2 , 4-bis (6-aminohexylamino) -1,3,5-triazine or 2,4,6-tris (6-aminohexylamino) -1,3,5-triazine or mixtures of these compounds, for example a mixture of 10 mol % 2- (5-hydroxy-3-oxapentylamino) -1,3,5-triazine, 50 mol% 2,4-bis (5-hydroxy-3-oxapentylamino) -1,3,5-triazine and 40 mol -% 2,4,6-tris (5-hydroxy-3-oxapentylamino) -1,3,5-triazine.

Geeignete Verbindungen (B) sind z.B. Phenol, 4-Methylphenol, 4-tert-Butylphenol, 4-Octylphenol, 4-Nonylphenol, Brenzcatechin, Resorcin, Hydrochinon, 2,2-Bis(4-hydroxyphenyl)propan oder 4,4'-Dihydroxydiphenylsulfon. Bevorzugt sind Phenol, Resorcin oder 2,2-Bis(4-hydroxyphenyl)propan.Suitable compounds (B) are, for example, phenol, 4-methylphenol, 4-tert-butylphenol, 4-octylphenol, 4-nonylphenol, pyrocatechol, resorcinol, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane or 4,4'- Dihydroxydiphenyl sulfone. Phenol, resorcinol or 2,2-bis (4-hydroxyphenyl) propane are preferred.

Formaldehyd wendet man in der Regel als wäßrige Lösung mit einer Konzentration von z.B. 40 bis 50 Gew.-% oder in Form von bei der Umsetzung mit (A) und (B) formaldehydliefernden Verbindungen an, beispielsweise als oligomeren oder polymeren Formaldehyd in fester Form, wie Paraformaldehyd, 1,3,5-Trioxan oder 1,3,5,7-Tetroxocan.Formaldehyde is generally used as an aqueous solution with a concentration of e.g. 40 to 50% by weight or in the form of compounds providing formaldehyde during the reaction with (A) and (B), for example as oligomeric or polymeric formaldehyde in solid form, such as paraformaldehyde, 1,3,5-trioxane or 1,3 , 5,7-tetroxocan.

Aus den oben näher bezeichneten Kondensationsprodukten können auf an sich bekannte Weise Fasern hergestellt werden (z.B. EP-A-408 947).Fibers can be produced in a manner known per se from the condensation products described above (e.g. EP-A-408 947).

Selbstverständlich können mittels des erfindungsgemäßen Verfahrens auch Mischgewebe der oben näher bezeichneten Kondensationsprodukte mit Baumwolle-, Wolle-, Acetat-, Polyacrylnitril- oder Aramidfasern in vorteilhafter Weise gefärbt, bedruckt oder beschichtet werden. Besonders geeignete Aramide bestehen dabei im wesentlichen aus einem Polykondensationsprodukt von Iso- oder Terephthalsäure mit einem meta- oder para-Phenylendiamin. Solche Produkte sind bekannt und z.B. unter der Bezeichnung Nomex® oder Kevlar® (Firma DuPont) handelsüblich.Of course, the method according to the invention can also be used to advantageously dye, print or coat mixed fabrics of the condensation products specified above with cotton, wool, acetate, polyacrylonitrile or aramid fibers. Particularly suitable aramids consist essentially of a polycondensation product of iso- or terephthalic acid with a meta- or para-phenylenediamine. Such products are known and e.g. commercially available under the name Nomex® or Kevlar® (DuPont).

Als Pigmente, die im erfindungsgemäßen Verfahren verwendet werden können, kommen sowohl anorganische wie auch organische Pigmente in Betracht.Pigments which can be used in the process according to the invention are both inorganic and organic pigments.

Anorganische Pigmente, die im erfindungsgemäßen Verfahren als Farbmittel dienen, sind beispielsweise Titandioxid, Zinkoxid, Zinksulfid, Cadmiumpigmente, wie Cadmiumsulfid, Cadmiumselenid oder Cadmiumguecksilbersulfid, Chromatpigmente, Chromoxide, Eisenoxide, Ultramarinpigmente, Eisencyanoferrate oder Ruße.Inorganic pigments which serve as colorants in the process according to the invention are, for example, titanium dioxide, zinc oxide, zinc sulfide, cadmium pigments, such as cadmium sulfide, cadmium selenide or cadmium mercury sulfide, chromate pigments, chromium oxides, iron oxides, ultramarine pigments, iron cyanoferrates or carbon blacks.

Organische Pigmente, die im erfindungsgemäßen Verfahren als Farbmittel dienen, sind beispielsweise solche aus der Klasse der Monoazopigmente (z.B. Produkte, die sich von Acetessigarylidderivaten oder von β-Naphtholderivaten ableiten), verlackten Monoazofarbstoffe, wie verlackte β-Oxynaphthoesäurefarbstoffe, Disazopigmente, kondensierten Disazopigmente, Azometallkomplexpigmente, Azomethinmetallkomplexpigmente, Benzimidazolonpigmente, Isoindolinderivate, Derivate der Naphthal-, Naphthalintetracarbon- oder Perylentetracarbonsäure, Perinone, Anthrachinonpigmente, Thioindigoderivate, Azomethinderivate, Chinacridone, Dioxazine, Pyrazolochinazolone, Benzopyrane, Phthalocyaninpigmente oder verlackten basischen Farbstoffe, wie verlackte Triarylmethanfarbstoffe, zu nennen.Organic pigments which serve as colorants in the process according to the invention are, for example, those from the class of the monoazo pigments (for example products which are derived from acetoacetic acid derivatives or from β-naphthol derivatives), lacquered monoazo dyes, such as lacquered β-oxynaphthoic acid dyes, disazo pigments, condensed disazo pigments , Azomethine metal complex pigments, benzimidazolone pigments, isoindoline derivatives, derivatives of naphthalene, naphthalene tetracarbonate or perylene tetracarboxylic acid, perinones, anthraquinone pigments, trioindigo derivatives, azomethine derivatives, quinacridone, dioxazines, pyrazoloquinophenazolone dyes, verbenzene phenol enolone, verbenzene phenol enolone, verbenzene enol dyes

Solche Pigmente sind an sich bekannt und beispielsweise in Ullmann's Encyclopedia of Industrial Chemistry, Band A 20, Seiten 243 bis 360, sowie Seiten 371 bis 412, beschrieben.Such pigments are known per se and are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Volume A 20, pages 243 to 360 and pages 371 to 412.

Beispielhaft seien die anorganischen Pigmente Pigment Yellow 42 (C.I. 77 492), Pigment White 6 (C.I. 77 891), Pigment Red 101 (C.I. 77 491), Pigment Red 102, Pigment Blue 27 (C.I. 77 510), Pigment Blue 29 (C.I. 77 007) oder Pigment Black 7 (C.I. 77 266) sowie die organischen Pigmente Pigment Yellow 1 (C.I. 11 680), Pigment Yellow 3 (C.I. 11 710), Pigment Yellow 16 (C.I. 20 040), Pigment Yellow 17 (C.I. 21 705, Pigment Yellow 42 (C.I. 77 492), Pigment Yellow 74 (C.I. 11 741), Pigment Yellow 81 (C.I. 21 127), Pigment Yellow 83 (C.I. 21 108), Pigment Yellow 106, Pigment Yellow 108 (C.I. 68 240), Pigment Yellow 113, Pigment Yellow 117, Pigment Yellow 126, Pigment Yellow 138 (C.I. 56 300), Pigment Yellow 139, Pigment Yellow 185, Pigment Orange 5 (C.I. 12 075), Pigment Orange 13 (C.I. 21 110), Pigment Orange 34 (C.I. 21 115), Pigment Orange 36 (C.I. 11 780), Pigment Orange 43 (C.I. 71 105), Pigment Orange 67, Pigment Red 3 (C.I. 12 120), Pigment Red 12 (C.I. 12 385), Pigment Red 48:1 (C.I. 15 865:1) Pigment Red 48:4 (15 865:4), Pigment Red 112 (C.I. 12 370), Pigment Red 122 (C.I. 73 915), Pigment Red 123 (C.I. 71 145), Pigment Red 146 (C.I. 12 485), Pigment Red 169 (C.I. 45 160:2), Pigment Red 170 (C.I. 12 475), Pigment Violett 19 (C.I. 46 500), Pigment Violet 23 (C.I. 51 319), Pigment Violet 27 (C.I. 42 555:3), Pigment Violet 33 (C.I. 60 005), Pigment Blue 1 (C.I. 42 595:2), Pigment Blue 15 (C.I. 74 160), Pigment Blue 15:1 (C.I. 74 160), Pigment Blue 15:3 (C.I. 74 160), Pigment Blue 61 (C.I. 42 765:1), Pigment Blue 152 (C.I. 74 160), Pigment Green 7 (C.I. 74 260), Pigment Green 8 (C.I. 10 008) oder Pigment Green 36 (C.I. 74 265) genannt.Examples include the inorganic pigments Pigment Yellow 42 (CI 77 492), Pigment White 6 (CI 77 891), Pigment Red 101 (CI 77 491), Pigment Red 102, Pigment Blue 27 (CI 77 510), Pigment Blue 29 (CI 77 007) or Pigment Black 7 (CI 77 266) and the organic pigments Pigment Yellow 1 (CI 11 680), Pigment Yellow 3 (CI 11 710), Pigment Yellow 16 (CI 20 040), Pigment Yellow 17 (CI 21 705 , Pigment Yellow 42 (CI 77 492), Pigment Yellow 74 (CI 11 741), Pigment Yellow 81 (CI 21 127), Pigment Yellow 83 (CI 21 108), Pigment Yellow 106, Pigment Yellow 108 (CI 68 240), Pigment Yellow 113, Pigment Yellow 117, Pigment Yellow 126, Pigment Yellow 138 (CI 56 300), Pigment Yellow 139, Pigment Yellow 185, Pigment Orange 5 (CI 12 075), Pigment Orange 13 (CI 21 110), Pigment Orange 34 (CI 21 115), Pigment Orange 36 (CI 11 780), Pigment Orange 43 (CI 71 105), Pigment Orange 67, Pigment Red 3 (CI 12 120), Pigment Red 12 (CI 12 385), Pigment Red 48: 1 (CI 1 5 865: 1) Pigment Red 48: 4 (15 865: 4), Pigment Red 112 (C.I. 12 370), Pigment Red 122 (CI 73 915), Pigment Red 123 (CI 71 145), Pigment Red 146 (CI 12 485), Pigment Red 169 (CI 45 160: 2), Pigment Red 170 (CI 12 475) , Pigment Violet 19 (CI 46 500), Pigment Violet 23 (CI 51 319), Pigment Violet 27 (CI 42 555: 3), Pigment Violet 33 (CI 60 005), Pigment Blue 1 (CI 42 595: 2), Pigment Blue 15 (CI 74 160), Pigment Blue 15: 1 (CI 74 160), Pigment Blue 15: 3 (CI 74 160), Pigment Blue 61 (CI 42 765: 1), Pigment Blue 152 (CI 74 160) , Pigment Green 7 (CI 74 260), Pigment Green 8 (CI 10 008) or Pigment Green 36 (CI 74 265).

Als Bindemittel, die im erfindungsgemäßen Verfahren zur Anwendung gelangen können, eignen sich insbesondere Polyacrylate oder Polyurethane oder Mischungen hieraus. Als Polyacrylate kommen hierbei beispielsweise Polyacrylsäuren, Polymethacrylsäuren, Copolymerisate aus Acryl- oder Methacrylsäure und Acryl- oder Methacrylsäureestern, Copolymerisate aus Acrylamid und Acrylsäure und Copolymerisate aus Acrylamid und Hydroxyalkylacrylaten in Betracht. Diese Produkte sind an sich bekannt und handelsüblich. Als Polyurethane kommen hierbei beispielsweise solche, wie sie in der DE-A-2 645 779 und der US-A-4 092 286 beschrieben sind, in Betracht.Particularly suitable binders which can be used in the process according to the invention are polyacrylates or polyurethanes or mixtures thereof. Examples of suitable polyacrylates are polyacrylic acids, polymethacrylic acids, copolymers of acrylic or methacrylic acid and acrylic or methacrylic acid esters, copolymers of acrylamide and acrylic acid and copolymers of acrylamide and hydroxyalkyl acrylates. These products are known per se and are commercially available. Examples of suitable polyurethanes here are those as described in DE-A-2 645 779 and US-A-4 092 286.

Als Vernetzer eignen sich in vorteilhafter Weise hydrophil modifizierte Polyisocyanate. Das sind insbesondere übliche Diisocyanate und/oder übliche höher funktionelle Polyisocyanate mit einer mittleren NCO-Funktionalität von 2,0 bis 4,5. Diese Komponenten können alleine oder im Gemisch vorliegen. Sie sind in der älteren Patentanmeldung WO-A-95/30045, auf die hier ausdrücklich Bezug genommen wird, beschrieben.Hydrophilically modified polyisocyanates are advantageously suitable as crosslinking agents. These are in particular customary diisocyanates and / or customary higher-functionality polyisocyanates an average NCO functionality of 2.0 to 4.5. These components can be present alone or in a mixture. They are described in the earlier patent application WO-A-95/30045, to which express reference is made here.

Als Verdickungsmittel eignen sich handelsübliche Produkte, z.B. hochpolymere synthetische Verdickungsmittel auf Acrylatbasis.Commercial products are suitable as thickeners, e.g. high polymer synthetic thickener based on acrylate.

Im erfindungsgemäßen Verfahren können weitere, an sich bekannte und übliche Hilfsmittel, z.B. Netzmittel, Antimigrationsmittel, Prozeßhilfsmittel, wie Antiwalzenbelagsmittel, Entschäumer oder Knitterfestmittel mit zugehörigen Katalysatoren, zur Anwendung gelangen.In the process according to the invention, further auxiliaries which are known and customary, e.g. Wetting agents, anti-migration agents, process aids such as anti-roll coating agents, defoamers or crease-resistant agents with associated catalysts are used.

Die flüssige Phase in den erfindungsgemäß zur Anwendung gelangenden wäßrigen Präparationen ist in der Regel rein wäßrig. Es können aber auch Mischungen von Wasser mit wassermischbaren organischen Lösungsmitteln, wie Alkoholen, z.B. Ethanol oder Isopropanol, Dioxan, Glykolen oder Glykolethern angewandt werden. Weiterhin lassen sich auch Mischungen aus Wasser und Ethylacetat, Aceton, Methylethylketon, Kohlensäureestern, wie Diethylcarbonat, 1,2-Ethylencarbonat oder 1,2-Propylencarbonat, oder Lactonen, wie β-Propiolacton, γ-Butyrolacton oder ε-Caprolacton, verwenden. Der Wassergehalt oder der Gehalt an Mischungen von Wasser mit wassermischbaren organischen Lösungsmitteln liegt üblicherweise bei ca. 45 bis ca. 99 Gew.-%.The liquid phase in the aqueous preparations used according to the invention is generally purely aqueous. Mixtures of water with water-miscible organic solvents, such as alcohols, e.g. Ethanol or isopropanol, dioxane, glycols or glycol ethers can be used. Mixtures of water and ethyl acetate, acetone, methyl ethyl ketone, carbonic acid esters, such as diethyl carbonate, 1,2-ethylene carbonate or 1,2-propylene carbonate, or lactones, such as β-propiolactone, γ-butyrolactone or ε-caprolactone, can also be used. The water content or the content of mixtures of water with water-miscible organic solvents is usually about 45 to about 99% by weight.

Im erfindungsgemäßen Färbeverfahren gelangen wäßrige Pigmentfärbeflotten als wäßrige Präparationen zur Anwendung. Diese enthalten in der Regel:

  • 0,01 bis 20 Gew.-%, vorzugsweise 0,1 bis 15 Gew.-%, Pigment,
  • 0,05 bis 25 Gew.-%, vorzugsweise 0,1 bis 20 Gew.-%, Bindemittel,
  • 0,01 bis 10 Gew.-%vorzugsweise 0,05 bis 7 Gew.-%, Vernetzer sowie
  • weitere obengenannte Hilfsmittel in den hierfür üblichen Mengen.
In the dyeing process according to the invention, aqueous pigment dye liquors are used as aqueous preparations. These usually contain:
  • 0.01 to 20% by weight, preferably 0.1 to 15% by weight, pigment,
  • 0.05 to 25% by weight, preferably 0.1 to 20% by weight, of binder,
  • 0.01 to 10 wt .-%, preferably 0.05 to 7 wt .-%, crosslinker and
  • further aids mentioned above in the usual quantities for this.

Das Färben der Kondensationsprodukte mit einer wäßrigen Pigmentfärbeflotte wird zweckmäßig so durchgeführt, daß man das Kondensationsprodukt in Form von Fasern, Garnen, Zwirnen, Maschenware, Webware oder Non-wovens bei einer Temperatur von 20 bis 70°C mit der wäßrigen Pigmentfärbeflotte imprägniert, danach abquetscht, trocknet (z.B. bei 80 bis 140°C) und thermisch nachbehandelt (z.B. 0,5 bis 3 Minuten bei 140 bis 200°C).The dyeing of the condensation products with an aqueous pigment dyeing liquor is expediently carried out in such a way that the condensation product in the form of fibers, yarns, twists, knitted fabrics, woven goods or nonwovens is impregnated with the aqueous pigment dyeing liquor at a temperature of from 20 to 70 ° C. and then squeezed off , dries (e.g. at 80 to 140 ° C) and thermally treated (e.g. 0.5 to 3 minutes at 140 to 200 ° C).

Man erhält auf diese Weise Färbungen, die gute Gebrauchsechtheiten, z.B. gute Wasch- und Reibechtheit, aufweisen.In this way, dyeings are obtained which have good fastness properties, e.g. good fastness to washing and rubbing.

Im erfindungsgemäßen Druckverfahren gelangen als wäßrige Präparationen wäßrige Druckpasten zur Anwendung. Diese enthalten in der Regel

  • 0,1 bis 10 Gew.-%, vorzugsweise 1 bis 5 Gew.-%, Pigment,
  • 5 bis 25 Gew.-%, vorzugsweise 10 bis 20 Gew.-%, Bindemittel,
  • 1 bis 10 Gew.-%, vorzugsweise 2,5 bis 5 Gew.-%, Verdickungsmittel sowie
  • weitere obengenannte Hilfsmittel in den hierfür üblichen Mengen.
In the printing process according to the invention, aqueous printing pastes are used as aqueous preparations. These usually contain
  • 0.1 to 10% by weight, preferably 1 to 5% by weight, pigment,
  • 5 to 25% by weight, preferably 10 to 20% by weight, of binder,
  • 1 to 10% by weight, preferably 2.5 to 5% by weight, of thickeners and
  • further aids mentioned above in the usual quantities for this.

Das Bedrucken der Kondensationsprodukte mit einer wäßrigen Druckpaste wird zweckmäßig so durchgeführt, daß man das Kondensationsprodukt in Form von Fasern, Garnen, Zwirnen, Maschenware, Webware oder Non-wovens bei einer Temperatur von 20 bis 40°C mit der wäßrigen Druckpaste unter Anwendung einer Schablone oder einer gravierten Walze bedruckt, trocknet (z.B. bei 80 bis 160°C) und thermisch nachbehandelt (z.B. 1 bis 6 Minuten bei 180 bis 140°C).The printing of the condensation products with an aqueous printing paste is expediently carried out in such a way that the condensation product in the form of fibers, yarns, twists, knitted fabrics, woven goods or non-wovens at a temperature of 20 to 40 ° C. with the aqueous printing paste using a template or printed on an engraved roller, dries (e.g. at 80 to 160 ° C) and thermally treated (e.g. 1 to 6 minutes at 180 to 140 ° C).

Man erhält auf diese Weise farbechte, brillante Drucke mit guter Egalität, scharfen Konturen, weichem Griff und guten Gebrauchsechtheiten.In this way you get color-fast, brilliant prints with good levelness, sharp contours, soft touch and good fastness to use.

Im erfindungsgemäßen Beschichtungsverfahren gelangen als wäßrige Präparationen wäßrige Beschichtungspasten zur Anwendung. Diese enthalten in der Regel

  • 0,1 bis 20 Gew.-%, vorzugsweise 1 bis 15 Gew.-%, Pigment,
  • 10 bis 80 Gew.-%, vorzugsweise 20 bis 40 Gew.-%, Bindemittel,
  • 2 bis 10 Gew.-%, vorzugsweise 3 bis 6 Gew.-%, Verdickungsmittel sowie
  • weitere obengenannte Hilfsmittel in den hierfür üblichen Mengen.
In the coating process according to the invention, aqueous coating pastes are used as aqueous preparations. These usually contain
  • 0.1 to 20% by weight, preferably 1 to 15% by weight, pigment,
  • 10 to 80% by weight, preferably 20 to 40% by weight, of binder,
  • 2 to 10 wt .-%, preferably 3 to 6 wt .-%, thickeners and
  • further aids mentioned above in the usual quantities for this.

Das Beschichten der Kondensationsprodukte mit einer wäßrigen Beschichtungspaste wird zweckmäßig so durchgeführt, daß man das Kondensationsprodukt in Form von Fasern, Garnen, Zwirnen, Maschenware, Webware oder Non-wovens bei einer Temperatur von 20 bis 40°C mit der wäßrigen Beschichtungspaste unter Anwendung einer Schablone oder einer Rakel beschichtet, trocknet (z.B. bei 80 bis 180°C), kondensiert (z.B. 0,5 bis 5 Minuten bei 190 bis 140°C) und nachkondensiert (z.B. 1 bis 5 Tage bei 10 bis 60°C).The coating of the condensation products with an aqueous coating paste is expediently carried out in such a way that the condensation product is in the form of fibers, yarns, twists, knitted fabrics, woven goods or nonwovens at a temperature of 20 to 40 ° C. with the aqueous coating paste using a template or coated with a doctor blade, dries (eg at 80 to 180 ° C), condensed (eg 0.5 to 5 minutes at 190 to 140 ° C) and post-condensed (eg 1 to 5 days at 10 to 60 ° C).

Man erhält auf diese Weise farbechte, brillante Beschichtungen mit guten Gebrauchsechtheiten, z.B. gute Wasch- und Reibechtheit.In this way, color-fast, brilliant coatings with good fastness properties, e.g. good fastness to washing and rubbing.

In manchen Fällen kann es von Vorteil sein, bei der Anwendung von Buntpigmenten das Färben oder Bedrucken in Gegenwart eines oder mehrerer Bisstyrylbenzole der Formel II

Figure imgb0002
vorzunehmen. Man erhielt dabei besonders brillante Färbungen oder Drucke. In der Regel wendet man 0,5 bis 10 Gew.-%, vorzugsweise 1 bis 3 Gew.-%, an Bisstyrylbenzol II, jeweils bezogen auf das Gewicht des Kondensationsprodukts, an.In some cases, it can be advantageous when using colored pigments to dye or print in the presence of one or more bisstyrylbenzenes of the formula II
Figure imgb0002
 to make. Particularly brilliant dyeings or prints were obtained. As a rule, 0.5 to 10% by weight, preferably 1 to 3% by weight, of bisstyrylbenzene II is used, in each case based on the weight of the condensation product.

Die folgenden Beispiele sollen die Erfindung näher erläutern.The following examples are intended to explain the invention in more detail.

A) FärbevorschriftA) Staining instructions

Ein Gewebe mit einem Gewicht von ca. 300 g/m2, das aus Fasern von Kondensationsprodukten erzeugt wurde, deren Herstellung in Beispiel 3b der US-A-5 322 915 beschrieben ist, wurde bei 20°C mit einer wäßrigen Pigmentflotte imprägniert, die folgende Zusammensetzung aufwies

X g/l
Pigment
15 g/l
Vernetzer (nichtionisch hydrophil modifiziertes Polyisocyanat, gemäß Beispiel 1 der WO-A-95/30045)
150 g/l
Bindemittel auf Basis eines üblichen Polyurethans (Perapret® PU, BASF Aktiengesellschaft)
2 g/l
handelsübliches Netzmittel
4 g/l
handelsübliches Antiwalzenbelagsmittel
20 g/l
handelsübliches Antimigrationsmittel
0,2 g/l
handelsüblicher Entschäumer
A fabric with a weight of approximately 300 g / m 2 , which was produced from fibers of condensation products, the production of which is described in Example 3b of US Pat. No. 5,322,915, was impregnated at 20 ° C. with an aqueous pigment liquor which had the following composition
X g / l
pigment
15 g / l
Crosslinker (nonionically hydrophilic modified polyisocyanate, according to example 1 of WO-A-95/30045)
150 g / l
Binder based on a common polyurethane (Perapret® PU, BASF Aktiengesellschaft)
2 g / l
commercial wetting agent
4 g / l
commercial anti-roll coating agent
20 g / l
commercial anti-migration agent
0.2 g / l
commercially available defoamers

Die Flottenaufnahme wurde durch Abquetschdruck auf 63 % begrenzt. Anschließend wurde bei 100 bis 120°C getrocknet und 1 bis 3 min bei ca. 180°C fixiert.The liquor intake was limited to 63% by squeezing pressure. The mixture was then dried at 100 to 120 ° C and fixed at about 180 ° C for 1 to 3 min.

B) DruckvorschriftB) Printing instructions

In 770 ml Wasser wurden 45 g eines handelsüblichen hochpolymeren synthetischen Verdickungsmittels auf Acrylatbasis, 10 g eines handelsüblichen Emulgators auf Basis eines Arylpolyglykolethers, 150 g eines handelsüblichen thermisch vernetzbaren Bindemittels auf Basis einer 40 gew.-%igen wäßrigen Dispersion eines Copolymerisats aus Butylacrylat, Styrol und N-Methylolmethacrylamid gegeben. Die Mischung wurde 4 min im Schnellrührer bei 5000 U/min gerührt. Danach gab man 30 g Pigment zu und rührte 5 Minuten bei 2000 U/min.45 g of a commercially available high-polymer synthetic thickener based on acrylate, 10 g of a commercially available emulsifier based on an aryl polyglycol ether, 150 g of a commercially available thermally crosslinkable binder based on a 40% strength by weight aqueous dispersion of a copolymer of butyl acrylate, styrene and Given N-methylol methacrylamide. The mixture was stirred for 4 min in a high-speed stirrer at 5000 rpm. 30 g of pigment were then added and the mixture was stirred at 2000 rpm for 5 minutes.

Die resultierende Druckpaste wurde anschließend mit einer Flachdruckschablone auf ein Gewebe mit einem Gewicht von ca. 300 g/m2, das aus Fasern von Kondensationsprodukten erzeugt wurde, deren Herstellung in Beispiel 3b der US-A-5 322 915 beschrieben ist, gedruckt. Danach trocknete man das Gewebe 2 min bei 100°C und kondensierte 5 min mit Heißdampf bei 150°C. (Anstelle von Heißdampf kann mit gleich gutem Erfolg auch Heißluft mit einer Temperatur von 120°C verwendet werden.The resulting printing paste was then printed with a planographic stencil onto a fabric with a weight of approx. 300 g / m 2 , which was produced from fibers of condensation products, the production of which is described in Example 3b of US Pat. No. 5,322,915. The fabric was then dried at 100 ° C. for 2 minutes and condensed with superheated steam at 150 ° C. for 5 minutes. (Instead of superheated steam, hot air at a temperature of 120 ° C can be used with equally good results.

Man erhält auf diese Weise farbechte, brillante Drucke mit guter Egalität, scharfen Konturen, weichem Griff, guter Trockenmigrationsechtheit, guter Trocken- und Naßreibechtheit sowie guter Waschechtheit.In this way, color-fast, brilliant prints with good levelness, sharp contours, soft touch, good fastness to dry migration, good fastness to dry and wet rubbing and good fastness to washing are obtained.

In den Färbe- und Druckvorschriften können anstelle der Webware z.B. auch Fasern, Garne, Zwirne, Maschenware oder Non-wovens zur Anwendung kommen.In the dyeing and printing instructions instead of the woven goods e.g. Fibers, yarns, threads, knitwear or non-wovens are also used.

Folgende Pigmente wurden angewandt.The following pigments were used.

Pigment 1Pigment 1

Mischung aus Pigment Black 7 (C.I. 77 266) und Pigment Blue 15 (C.I. 74 160)
(Färbevorschrift A: X = 100 g/l).Mixture of Pigment Black 7 (CI 77 266) and Pigment Blue 15 (CI 74 160)
(Staining instruction A: X = 100 g / l).

Pigment 2Pigment 2

Mischung aus Pigment Blue 15:3 (C.I. 74 160) und Pigment Violet 23 (C.I. 51 319)
(Färbevorschrift A: X = 50 g/l).Mixture of Pigment Blue 15: 3 (CI 74 160) and Pigment Violet 23 (CI 51 319)
(Staining instruction A: X = 50 g / l).

Pigment 3Pigment 3

Pigment Orange 43 (C.I. 71 105)
(Färbevorschrift A: X = 50 g/l)Pigment Orange 43 (CI 71 105)
(Dyeing instruction A: X = 50 g / l)

Pigment 4Pigment 4

Mischung aus Pigment Blue 15 (C.I. 74 160) und Pigment Green 7 (C.I. 74 260)
(Färbevorschrift A: X = 50 g/l).Mixture of Pigment Blue 15 (CI 74 160) and Pigment Green 7 (CI 74 260)
(Staining instruction A: X = 50 g / l).

C) BeschichtungsvorschriftC) Coating regulation

In 600 ml Wasser wurden 300 g eines Bindemittels auf Basis eines üblichen Polyurethans (Perapret PU, BASF Aktiengesellschaft), 30 g Vernetzer (nichtionisch hydrophil modifiziertes Polyisocyanat, gemäß Beispiel 1 der WO-A-95/30045) und 2 g eines handelsüblichen Entschäumers gegeben. Die Mischung wurde 4 min im Schnellrührer bei 5000 U/min gerührt. Danach gab man 100 g Pigment und 35 g eines handelsüblichen hochpolymeren synthetischen Verdickungsmittels auf Acrylatbasis zu und rührte 5 Minuten bei 2000 U/min.300 g of a binder based on a conventional polyurethane (Perapret PU, BASF Aktiengesellschaft), 30 g of crosslinking agent (nonionically hydrophilically modified polyisocyanate, according to Example 1 of WO-A-95/30045) and 2 g of a commercially available defoamer were added to 600 ml of water . The mixture was stirred for 4 min in a high-speed stirrer at 5000 rpm. Then 100 g of pigment and 35 g of a commercially available high-polymer synthetic thickener based on acrylate were added and the mixture was stirred at 2000 rpm for 5 minutes.

Mit der resultierenden Beschichtungspaste wurde anschließend mittels einer Luftrakel ein Gewebe mit einem Gewicht von ca. 300 g/m2, das aus Fasern von Kondensationsprodukten erzeugt wurde, deren Herstellung in Beispiel 3b der US-A-5 322 915 beschrieben ist, beschichtet (20 g/m2). Danach trocknete man das Gewebe 2 min bei 95°C, kondensierte 1,5 min mit Heißluft bei 180°C und kondensierte 2 Tage bei 20°C nach.The resulting coating paste was then coated with an air knife over a fabric with a weight of approx. 300 g / m 2 , which was produced from fibers of condensation products, the production of which is described in Example 3b of US Pat. No. 5,322,915 (20 g / m 2 ). The fabric was then dried for 2 minutes at 95 ° C., condensed for 1.5 minutes with hot air at 180 ° C. and then condensed for 2 days at 20 ° C.

Man erhält auf diese Weise farbechte Beschichtungen mit weichem Griff, guter Trockenmigrationschtheit, guter Trocken- und Naßreibechtheit sowie guter Waschechtheit.In this way, color-fast coatings with a soft handle, good fastness to dry migration, good fastness to dry and wet rubbing and good fastness to washing are obtained.

Folgendes Pigment wurde angewandt.The following pigment was used.

Pigment 5Pigment 5

Mischung aus Pigment Red 101 (C.I. 77491), Pigment Red 102 und Pigment Black 7 (C.I. 77266).Mixture of Pigment Red 101 (C.I. 77491), Pigment Red 102 and Pigment Black 7 (C.I. 77266).

Claims (4)

Verfahren zum Färben, Bedrucken oder Beschichten von Kondensationsprodukten, die erhältlich sind durch Kondensation eines Gemisches, enthaltend als wesentliche Komponenten (A) 90 bis 99,9 Mol-% eines Gemisches, bestehend im wesentlichen aus (a) 30 bis 99 Mol-% Melamin und (b) 1 bis 70 Mol-% eines substituierten Melamins der Formel I
Figure imgb0003
 in der die Reste Y unabhängig voneinander jeweils Wasserstoff, Hydroxy-C2-C10-alkyl, Hydroxy-C2-C4-alkyl-(oxa-C2-C4-alkyl)n, worin n für 1 bis 5 steht, oder Amino-C2-C12-alkyl bedeuten, mit der Maßgabe, daß mindestens ein Rest Y von Wasserstoff verschieden ist, oder Mischungen von Melaminen der Formel I sowie (B) 0,1 bis 10 Mol-%, bezogen auf (A) und (B), Phenol, das gegebenenfalls durch C1-C9-Alkyl oder Hydroxy substituiert ist, C1-C4-Alkane, die durch Hydroxyphenyl substituiert sind, Bis(hydroxyphenyl)sulfone oder Mischungen dieser Verbindungen, mit
Formaldehyd oder formaldehydliefernden Verbindungen, wobei das Molverhältnis von Melaminen zu Formaldehyd im Bereich von 1:1,15 bis 1:4,5 liegt,
dadurch gekennzeichnet, daß man die Kondensationsprodukte in Form von Fasern, Garnen, Zwirnen, Maschenware, Webware oder Non-wovens mit einer wäßrigen Präparation, enthaltend eines oder mehrere Pigmente, Bindemittel und gegebenenfalls Vernetzer und Verdickungsmittel, bei einer Temperatur von 10 bis 200°C behandelt.Process for dyeing, printing or coating condensation products which can be obtained by condensing a mixture containing as essential components (A) 90 to 99.9 mol% of a mixture consisting essentially of (a) 30 to 99 mole% melamine and (b) 1 to 70 mol% of a substituted melamine of the formula I.
Figure imgb0003
 in which the radicals Y independently of one another are each hydrogen, hydroxy-C 2 -C 10 -alkyl, hydroxy-C 2 -C 4 -alkyl- (oxa-C 2 -C 4 -alkyl) n , where n is 1 to 5 , or amino-C 2 -C 12 alkyl, with the proviso that at least one radical Y is different from hydrogen, or mixtures of melamines of the formula I and (B) 0.1 to 10 mol%, based on (A) and (B), phenol which is optionally substituted by C 1 -C 9 -alkyl or hydroxy, C 1 -C 4 -alkanes which are substituted by hydroxyphenyl are substituted, bis (hydroxyphenyl) sulfones or mixtures of these compounds, With
Formaldehyde or compounds providing formaldehyde, the molar ratio of melamines to formaldehyde being in the range from 1: 1.15 to 1: 4.5,
characterized in that the condensation products in the form of fibers, yarns, twists, knits, woven or non-wovens with an aqueous preparation containing one or more pigments, binders and optionally Crosslinker and thickener, treated at a temperature of 10 to 200 ° C. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als wäßrige Präparation eine wäßrige Pigmentfärbeflotte verwendet, die 0,01 bis 20 Gew.-% Pigment, 0,05 bis 25 Gew.-% Bindemittel und 0,01 bis 10 Gew.-% Vernetzer enthält.A method according to claim 1, characterized in that an aqueous pigment dye liquor is used as the aqueous preparation, which contains 0.01 to 20 wt .-% pigment, 0.05 to 25 wt .-% binder and 0.01 to 10 wt .-% Contains crosslinker. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als wäßrige Präparation eine wäßrige Druckpaste verwendet, die 0,1 bis 10 Gew.-% Pigment, 5 bis 25 Gew.-% Bindemittel und 1 bis 10 Gew.-% Verdickungsmittel enthält.Process according to Claim 1, characterized in that an aqueous printing paste which contains 0.1 to 10% by weight of pigment, 5 to 25% by weight of binder and 1 to 10% by weight of thickener is used as the aqueous preparation. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als wäßrige Präparation eine wäßrige Beschichtungspaste verwendet, die 0,1 bis 20 Gew.-% Pigment, 10 bis 80 Gew.-% Bindemittel und 2 bis 10 Gew.-% Verdickungsmittel enthält.A method according to claim 1, characterized in that an aqueous coating paste is used as the aqueous preparation, which contains 0.1 to 20 wt .-% pigment, 10 to 80 wt .-% binder and 2 to 10 wt .-% thickener.
EP96115893A 1995-10-13 1996-10-04 Process for dyeing, printing, coating condensations products of melamin-formaldehyde, with pigments Withdrawn EP0768423A3 (en)

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DE19538140A DE19538140A1 (en) 1995-10-13 1995-10-13 Process for dyeing or printing melamine-formaldehyde condensation products using pigments
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EP1130065A2 (en) * 2000-02-04 2001-09-05 Dainichiseika Color & Chemicals Mfg. Co. Ltd. Pigment compositions, production process thereof; colorants; and colored articles
US6451070B1 (en) 1998-03-06 2002-09-17 Basf Corporation Ultraviolet stability of aramid and aramid-blend fabrics by pigment dyeing or printing

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US6451070B1 (en) 1998-03-06 2002-09-17 Basf Corporation Ultraviolet stability of aramid and aramid-blend fabrics by pigment dyeing or printing
US6200355B1 (en) 1999-12-21 2001-03-13 Basf Corporation Methods for deep shade dyeing of textile articles containing melamine fibers
EP1130065A2 (en) * 2000-02-04 2001-09-05 Dainichiseika Color & Chemicals Mfg. Co. Ltd. Pigment compositions, production process thereof; colorants; and colored articles
EP1130065A3 (en) * 2000-02-04 2001-10-31 Dainichiseika Color & Chemicals Mfg. Co. Ltd. Pigment compositions, production process thereof; colorants; and colored articles

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KR970021503A (en) 1997-05-28
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JPH09158060A (en) 1997-06-17

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