EP0316784A2 - Process for coating textiles - Google Patents

Process for coating textiles Download PDF

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Publication number
EP0316784A2
EP0316784A2 EP88118789A EP88118789A EP0316784A2 EP 0316784 A2 EP0316784 A2 EP 0316784A2 EP 88118789 A EP88118789 A EP 88118789A EP 88118789 A EP88118789 A EP 88118789A EP 0316784 A2 EP0316784 A2 EP 0316784A2
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EP
European Patent Office
Prior art keywords
melamine
textiles
film
carbon atoms
coating
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EP88118789A
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German (de)
French (fr)
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EP0316784A3 (en
Inventor
Wolfram Dr. Bergold
Heinz Dr. Bille
Horst Fuchs
Toni Simenc
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BASF SE
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BASF SE
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Publication of EP0316784A2 publication Critical patent/EP0316784A2/en
Publication of EP0316784A3 publication Critical patent/EP0316784A3/en
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins

Definitions

  • the invention relates to a process for improving the resistance to washing and dry cleaning of finely coated textiles, in which water-insoluble modified condensation products of the melamine are added to the polymeric dispersions used for coating the textile materials and are fixed after drying of the coated textile material at higher temperatures, and the use of water-insoluble modified condensation products of melamine together with aqueous polymer dispersions in the fine coating of textiles.
  • fine coating is understood to mean a coating of textiles whose amount per m2 of textile area is less than that of conventional coatings, down to the application quantities that can be achieved with a foulard; for fine coating, calculated as a solid, it is between about 5 and about 35 g / m2 of textile surface. This can be achieved by applying the coating composition in paste form and applying it with a pressure roller or a doctor blade.
  • the resistance to washing and dry cleaning as well as the hydrophobizing effect of the fine coating is tested in practice indirectly via the water impermeability of the coated material.
  • the coated textile must withstand a water pressure that is generated with a water column over 1 m high.
  • the height of the water column in mm is given as a Schopper value and is the orientation value for practical use when assessing the water-repellent fine coating and its durability, for example after use.
  • a thin, closed polymer film is formed on the textile surface during the fine coating.
  • This polymer film is expediently applied in the form of an aqueous polymer dispersion which contains conventional auxiliaries, in particular emulsifiers.
  • the emulsifiers used partly adhere to the textile material and can absorb the cleaning medium during washing or cleaning, which can cause the polymer film to swell. At these points and especially at the folds of the fabric, damage to the applied film is easily possible due to mechanical stress during cleaning or washing. Such places become permeable to water and the Schopper value decreases.
  • the object of the present invention is to optimize the resistance to washing and dry cleaning of finely coated textiles and the hydrophobic properties of the polymer films applied to the textile surface.
  • the solution to the problem consists in a process for the production of washable and dry-cleaning-resistant finely coated textiles with aqueous dispersions of film-forming and reactive groups-containing polymers, characterized in that the aqueous dispersions of the film-forming polymers are water-insoluble reaction products of condensation products of melamine and formaldehyde, the methylol groups of which or partially etherified with a saturated monohydric aliphatic alcohol with 1 to 4 carbon atoms, with a fatty alcohol with 12 to 18 carbon atoms or a fatty acid with 12 to 18 carbon atoms, the textile is coated with this mixture, dries and Fixed temperatures from 150 to 200 ° C.
  • the invention also relates to the use of the above-mentioned modified condensation products of melamine in the fine coating of textiles together with aqueous dispersions of film-forming and reactive group-containing polymers.
  • the properties of the coated textile materials are decisively improved by the modified condensation products of melamine added according to the invention.
  • Crosslinking reactions of the added products with existing reactive and in particular hydrophilic groups, such as carboxyl, N-methylol or amide groups, of the coating agent used, as well as crosslinking of the condensation product with itself, are likely to play a role, so that the durability of the coating and the hydrophobizing properties of the Fabric can be significantly improved.
  • Textiles to be coated are in particular textile materials or textile goods made of natural fibers or synthetic fibers, such as cotton, polyester or polyamides, and their mixtures with one another, in particular cotton with synthetic fibers.
  • Fine coating usually means an application, based on a solid, in an amount of 5 to 30, preferably 10 to 20 g / m2 of textile fabric.
  • aqueous dispersions of film-forming polymers which contain reactive groups capable of crosslinking, such as, for example, carboxyl, N-methylol, amide, amine or OH groups.
  • polyacrylate dispersions based on an acrylic acid or methacrylic acid ester with an alcohol of 1 to 4 carbon atoms, the comonomers acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-methylolacrylamide, N-methylol methacrylamide, N-methoxymethylacrylamide, N-methoxymethyl methacrylamide and Acrylic acid, methacrylic acid, maleic acid or itaconic acid, preferably in the form of their ammonium salts.
  • the (meth) acrylic acid esters on which the polyacrylate dispersions are based are, for example, butyl acrylate, ethyl acrylate and methyl methacrylate.
  • polyurethane dispersions can also be used. Suitable, stable aqueous polyurethane dispersions can be found, for example, in US Pat. No. 3,905,929 or the overview from Angew. Chem. 82, 53-90 (1970).
  • aqueous polyurethane dispersion based on adipic acid, butanediol, neopentyl glycol, hexanediol, tolylene diisocyanate, hexamethylene diisocyanate and 3- (2-aminoethyl) aminopropionic acid sodium salt should be mentioned as examples.
  • the aqueous dispersions of the film-forming and reactive group-containing polymers are water-insoluble reaction products of condensation products of melamine and formaldehyde, the methylol groups of which are wholly or partly etherified with a saturated monohydric aliphatic alcohol with 1 to 4 carbon atoms, with a higher fatty alcohol with 12 to 18 C atoms or a higher fatty acid with 12 to 18 C atoms added.
  • the modified condensation products or derivatives of melamine used are water-insoluble. They advantageously have self-emulsifying properties in water. As a rule, these are the mixtures or reaction mixtures formed during industrial production.
  • condensation products for the modification by additional etherification or by esterification are condensation products of 1 mol of melamine and 2 to 6 mol, preferably 2.5 to 5.5 mol, of formaldehyde, with 2.2 to 6 mol of a lower alcohol, such as ethanol, propanol , Butanol or preferably methanol, have been implemented.
  • Technical hexamethoxymethylmelamine which is generally a mixture of 50 to 70% by weight of hexamethoxymethylmelamine, which contains condensation products (precondensates) with 2 and 3 and moreover with up to 6 melamine cores, is particularly preferred.
  • An exemplary mixture contains about 60% by weight of hexamethoxymethylmelamine, about 13% by weight of two- to four-nucleus and about 26% by weight of up to six-core condensation products.
  • Such mixtures are commercially available, for example in the form of aqueous mixtures.
  • stearyl alcohol and stearic acid are particularly preferred.
  • the etherification of a melamine methylolated with a lower alcohol, preferably of hexamethyloxymethylmelamine, with stearyl alcohol or the esterification with stearic acid is advantageously carried out with 0.2 to 3 mol of stearyl alcohol or stearic acid per mol of hexamethoxymelamine at temperatures from 120 to 150 ° C., preferably around 135 ° C. , in the presence of phthalic acid as a catalyst within 6 to 10 hours, if appropriate with volatile constituents being distilled off under reduced pressure.
  • the water-insoluble product obtained can advantageously be dissolved in a high-boiling aliphatic hydrocarbon free of aromatics and suitable for the textile industry to give a clear solution of 50 to 70% by weight.
  • Suitable hydrocarbons are commercially available, for example, under the name Shellsol.
  • the aqueous dispersions of the film-forming polymers are generally present as 40 to 50% by weight dispersions, based on solids.
  • the products to be used according to the invention are expediently incorporated into these dispersions in an organic solvent with stirring and advantageously together with a synthetic thickener, so that the mixture thickens to form a spreading paste.
  • the mixture to be applied to the tissue is then applied in the usual way as a spreading paste.
  • the commercially available, preferably fully synthetic, thickeners are added to the mixture in a customary amount of 1 to 2% by weight, based on the total weight.
  • Examples of synthetic thickeners are homopolymers or copolymers of ethylenically unsaturated mono- or dicarboxylic acids, in particular acrylic acid or maleic acid, optionally with comonomers, such as acrylamide, and copolymers of ethylenically unsaturated carboxylic acids with one another, in particular of acrylic and maleic acid.
  • the thickening effect occurs in aqueous solution, especially in the case of partial or complete neutralization with bases, preferably with ammonia or sodium hydroxide solution.
  • the following drying of the coating on the fabric is advantageously carried out at temperatures of 80 to 120 ° C.
  • the mixture is then fixed or cured at from 150 to 200 ° C., in particular 160 to 170 ° C., within 1 to 5, preferably 2 to 3 minutes.
  • the crosslinking or hardening can be accelerated by acidic substances as acidic catalysts, as are customary in the high refinement of cellulose, for example by zinc or magnesium chlorides, nitrates, zinc fluoroborates or in particular ammonium chloride. These can be used in the quantities customary for high-level finishing. Quantities of up to 10, preferably up to 5 parts by weight of catalyst per 100 parts by weight of melamine compound (calculated as a solid) have proven useful.
  • Synthetic thickeners can act as a catalyst due to their composition, for example by polymerized carboxyl groups, so that the above-mentioned catalysts can be largely replaced.
  • the melamine condensation product and the film-forming polymer are used in a ratio of 1: 3 to 1:10, preferably 1: 4 to 1: 8.
  • a polyamide fabric with a fabric weight of 65 g / m2 is coated with one of the coating pastes, which are composed as follows:
  • the polyamide fabric is coated with 2 strokes using an air knife and by hand, a total of 20 g of solid being applied in paste A or B / m2. It is dried at 100 ° C. and then fixed at 160 ° C. for 2 minutes.
  • Recipe B gives a soft, hydrophobic coating that has a Schopper value of over 1000 mm even after 5 washes. In contrast, with coating A, the Schopper value drops significantly after washing 5 times to about 500 mm.
  • sample B remains perfect, while sample A appears washed out.
  • a base coat is first applied to the polyamide fabric (65 g / m2), dried and then coated in a second coat as a top coat with one of the following pastes C or D, the paste C being A and D are applied to B. In each case 12 g of solid / m2 are applied.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to a process for improving the washing and drycleaning resistance of finely coated textiles, wherein water-insoluble condensation products of melamine, formaldehyde and lower alcohol which have been modified with higher fatty alcohols or fatty acids are added to the aqueous film-forming polymer dispersions with reactive groups used for coating the textile materials and, after the coated textile material has been dried, fixed at elevated temperatures, and the use of condensation products of melamine together with aqueous polymer dispersions in the fine coating of textiles.

Description

Die Erfindung betrifft ein Verfahren zur Verbesserung der Wasch- und Chemischreinigungsbeständigkeit feinbeschichteter Textilien, bei dem man den zur Beschichtung der Textilmaterialien verwendeten wäßrigen, filmbil­denden und reaktive Gruppen enthaltenden Polymerdispersionen wasser­unlösliche modifizierte Kondensationsprodukte des Melamins zusetzt und nach dem Trocknen des beschichteten Textilgutes bei höheren Temperaturen fixiert, sowie die Verwendung von wasserunlöslichen modifizierten Kondensationsprodukten des Melamins zusammen mit wäßrigen Polymer­dispersionen bei der Feinbeschichtung von Textilien.The invention relates to a process for improving the resistance to washing and dry cleaning of finely coated textiles, in which water-insoluble modified condensation products of the melamine are added to the polymeric dispersions used for coating the textile materials and are fixed after drying of the coated textile material at higher temperatures, and the use of water-insoluble modified condensation products of melamine together with aqueous polymer dispersions in the fine coating of textiles.

Unter Feinbeschichtung wird im vorliegenden Zusammenhang eine Beschichtung von Textilien verstanden, deren Menge je m² Textilfläche geringer als die gewöhnlicher Beschichtungen ist, bis herab zu den mit einem Foulard er­zielbaren Auftragsmengen; sie liegt also bei der Feinbeschichtung, ge­rechnet als Feststoff, zwischen etwa 5 und etwa 35 g/m² Textilfläche. Das kann man dadurch erzielen, daß man die Beschichtungsmasse in Pastenform anwendet und sie mit einer Druckwalze oder einer Rakel aufbringt.In the present context, fine coating is understood to mean a coating of textiles whose amount per m² of textile area is less than that of conventional coatings, down to the application quantities that can be achieved with a foulard; for fine coating, calculated as a solid, it is between about 5 and about 35 g / m² of textile surface. This can be achieved by applying the coating composition in paste form and applying it with a pressure roller or a doctor blade.

Die Wasch- und Chemischreinigungspermanenz sowie die hydrophobierende Wir­kung der Feinbeschichtung wird in der Praxis indirekt über die Wasserun­durchlässigkeit des beschichteten Materials geprüft. Das beschichtete Textilgut muß einem Wasserdruck standhalten, der mit einer über 1 m hohen Wassersäule erzeugt wird. Die Höhe der Wassersäule in mm wird als Schopper-Wert angegeben und ist für die Praxis der Orientierungswert bei der Beurteilung der wasserabweisenden Feinbeschichtung und ihrer Beständigkeit beispielsweise nach Beanspruchungen.The resistance to washing and dry cleaning as well as the hydrophobizing effect of the fine coating is tested in practice indirectly via the water impermeability of the coated material. The coated textile must withstand a water pressure that is generated with a water column over 1 m high. The height of the water column in mm is given as a Schopper value and is the orientation value for practical use when assessing the water-repellent fine coating and its durability, for example after use.

In der Regel wird bei der Feinbeschichtung auf der textilen Oberfläche ein dünner, geschlossener Polymerfilm gebildet. Dieser Polymerfilm wird zweck­mäßig in Form einer wäßrigen Polymerdispersion, die als übliche Hilfs­stoffe, insbesondere Emulgatoren enthält, aufgebracht. Die verwendeten Emulgatoren bleiben teilweise auf dem Textilmaterial mit haften und können beim Waschen oder Reinigen das Reinigungsmedium aufnehmen, wodurch der aufgebrachte Polymerfilm aufquellen kann. An diesen Stellen und vor allem an den Falten der Gewebe ist durch mechanische Beanspruchung während des Reinigens oder Waschens eine Beschädigung des aufgetragenen Films leicht möglich. Solche Stellen werden wasserdurchlässig und der Schopper-Wert vermindert sich.As a rule, a thin, closed polymer film is formed on the textile surface during the fine coating. This polymer film is expediently applied in the form of an aqueous polymer dispersion which contains conventional auxiliaries, in particular emulsifiers. The emulsifiers used partly adhere to the textile material and can absorb the cleaning medium during washing or cleaning, which can cause the polymer film to swell. At these points and especially at the folds of the fabric, damage to the applied film is easily possible due to mechanical stress during cleaning or washing. Such places become permeable to water and the Schopper value decreases.

Aufgabe der vorliegenden Erfindung ist es, die Wasch- und Chemischreini­gungsbeständigkeit feinbeschichteter Textilien sowie die hydrophoben Eigenschaften der auf der textilen Oberfläche aufgebrachten Polymerfilme zu optimieren.The object of the present invention is to optimize the resistance to washing and dry cleaning of finely coated textiles and the hydrophobic properties of the polymer films applied to the textile surface.

Die Lösung der Aufgabe besteht in einem Verfahren zur Herstellung von wasch- und chemischreinigungsbeständigen feinbeschichteten Textilien mit wäßrigen Dispersionen filmbildender und reaktive Gruppen enthaltender Polymerer, dadurch gekennzeichnet, daß man den wäßrigen Dispersionen der filmbildenden Polymeren wasserunlösliche Umsetzungsprodukte von Kondensationsprodukten aus Melamin und Formaldehyd, deren Methylolgruppen ganz oder teilweise mit einem gesättigten einwertigen aliphatischen Alkohol mit 1 bis 4 C-Atomen verethert sind, mit einem Fettalkohol mit 12 bis 18 C-Atomen oder einer Fettsäure mit 12 bis 18 C-Atomen zusetzt, das Textilgut mit dieser Mischung beschichtet, trocknet und bei Temperaturen von 150 bis 200°C fixiert.The solution to the problem consists in a process for the production of washable and dry-cleaning-resistant finely coated textiles with aqueous dispersions of film-forming and reactive groups-containing polymers, characterized in that the aqueous dispersions of the film-forming polymers are water-insoluble reaction products of condensation products of melamine and formaldehyde, the methylol groups of which or partially etherified with a saturated monohydric aliphatic alcohol with 1 to 4 carbon atoms, with a fatty alcohol with 12 to 18 carbon atoms or a fatty acid with 12 to 18 carbon atoms, the textile is coated with this mixture, dries and Fixed temperatures from 150 to 200 ° C.

Gegenstand der Erfindung ist auch die Verwendung der obengenannten modifizierten Kondensationsprodukte des Melamins bei der Feinbeschichtung von Textilien zusammen mit wäßrigen Dispersionen filmbildender und reaktive Gruppen enthaltendender Polymerer.The invention also relates to the use of the above-mentioned modified condensation products of melamine in the fine coating of textiles together with aqueous dispersions of film-forming and reactive group-containing polymers.

Durch die erfindungsgemäß zugesetzten modifizierten Kondensationsprodukte des Melamins werden die Eigenschaften der beschichteten Textilmaterialien entscheidend verbessert. Dabei dürften Vernetzungsreaktionen der zuge­setzten Produkte mit vorhandenen reaktiven und insbesondere hydrophilen Gruppen, wie Carboxyl-, N-Methylol- oder Amidgruppen, des verwendeten Beschichtungsmittels, sowie Vernetzungen des Kondensationsproduktes mit sich selbst eine Rolle spielen, wodurch die Beständigkeit der Beschichtung und die hydrophobierenden Eigenschaften des Gewebes wesentlich verbessert werden.The properties of the coated textile materials are decisively improved by the modified condensation products of melamine added according to the invention. Crosslinking reactions of the added products with existing reactive and in particular hydrophilic groups, such as carboxyl, N-methylol or amide groups, of the coating agent used, as well as crosslinking of the condensation product with itself, are likely to play a role, so that the durability of the coating and the hydrophobizing properties of the Fabric can be significantly improved.

Im einzelnen kann das erfindungsgemäße Verfahren wie folgt näher erläutert werden:The process according to the invention can be explained in more detail as follows:

Als zu beschichtende Textilien kommen insbesondere Textilmaterialien oder Textilgut aus Naturfasern oder synthetischen Fasern, wie Baumwolle, Poly­ester oder Polyamide, und ihre Mischungen untereinander, insbesondere Baumwolle mit synthetischen Fasern, in Betracht.Textiles to be coated are in particular textile materials or textile goods made of natural fibers or synthetic fibers, such as cotton, polyester or polyamides, and their mixtures with one another, in particular cotton with synthetic fibers.

Feinbeschichtung bedeutet in der Regel einen Auftrag, bezogen als Fest­stoff, in einer Menge von 5 bis 30, bevorzugt 10 bis 20 g/m² Textilgewebe.Fine coating usually means an application, based on a solid, in an amount of 5 to 30, preferably 10 to 20 g / m² of textile fabric.

Die für die Feinbeschichtung von Textilien verwendeten filmbildenden Produkte sind dem Fachmann bekannt und meist handelsüblich und können ohne weiteres der Literatur entnommen werden.The film-forming products used for the fine coating of textiles are known to the person skilled in the art and are usually commercially available and can readily be found in the literature.

Bevorzugt handelt es sich um wäßrige Dispersionen filmbildender Polymerer, die reaktive und zur Vernetzung befähigte Gruppen, wie beispielsweise Carboxyl-, N-Methylol-, Amid-, Amin- oder OH-Gruppen enthalten.These are preferably aqueous dispersions of film-forming polymers which contain reactive groups capable of crosslinking, such as, for example, carboxyl, N-methylol, amide, amine or OH groups.

Insbesondere sind zu nennen Polyacrylatdispersionen auf Basis eines Acryl­säure- oder Methacrylsäureesters mit einem Alkohol von 1 bis 4 C-Atomen, die als Comonomere Acrylnitril, Methacrylnitril, Acrylamid, Methacrylamid, N-Methylolacrylamid, N-Methylolmethacrylamid, N-Methoxymethylacrylamid, N-Methoxymethylmethacrylamid sowie Acrylsäure, Methacrylsäure, Maleinsäure oder Itakonsäure, bevorzugt in Form ihrer Ammoniumsalze, enthalten können.Particular mention should be made of polyacrylate dispersions based on an acrylic acid or methacrylic acid ester with an alcohol of 1 to 4 carbon atoms, the comonomers acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-methylolacrylamide, N-methylol methacrylamide, N-methoxymethylacrylamide, N-methoxymethyl methacrylamide and Acrylic acid, methacrylic acid, maleic acid or itaconic acid, preferably in the form of their ammonium salts.

Hervorzuhebende den Polyacrylatdispersionen zugrundeliegende (Meth)Acryl­säureester sind beispielsweise Butylacrylat, Ethylacrylat und Methylmeth­acrylat.The (meth) acrylic acid esters on which the polyacrylate dispersions are based are, for example, butyl acrylate, ethyl acrylate and methyl methacrylate.

Besonders hervorzuheben ist ein Polymerisat aus 90 bis 95 Gew.% Butyl­acrylat, 1 bis 5 Gew.% Acrylnitril, 0,5 bis 5 Gew.% N-Methylol­methacrylamid und 0,5 bis 2 Gew.% Acrylsäure.Of particular note is a polymer made from 90 to 95% by weight of butyl acrylate, 1 to 5% by weight of acrylonitrile, 0.5 to 5% by weight of N-methylol methacrylamide and 0.5 to 2% by weight of acrylic acid.

Es können auch handelsübliche Polyurethandispersionen verwendet werden. Geeignete, stabile wäßrige Polyurethandispersionen können beispielsweise der US-PS 3 905 929 oder der Übersicht aus Angew. Chem. 82, 53-90 (1970) entnommen werden.Commercially available polyurethane dispersions can also be used. Suitable, stable aqueous polyurethane dispersions can be found, for example, in US Pat. No. 3,905,929 or the overview from Angew. Chem. 82, 53-90 (1970).

Beispielhaft soll eine wäßrige Polyurethandispersion auf Basis Adipin­säure, Butandiol, Neopentylglykol, Hexandiol, Toluylendiisocyanat, Hexamethylendiisocyanat und 3-(2-Aminoethyl)-aminopropionsäure-natriumsalz genannt werden.An aqueous polyurethane dispersion based on adipic acid, butanediol, neopentyl glycol, hexanediol, tolylene diisocyanate, hexamethylene diisocyanate and 3- (2-aminoethyl) aminopropionic acid sodium salt should be mentioned as examples.

Erfindungsgemäß werden den wäßrigen Dispersionen der filmbildenden und reaktive Gruppen enthaltenden Polymeren wasserunlösliche Umsetzungs­produkte von Kondensationsprodukten aus Melamin und Formaldehyd, deren Methylolgruppen ganz oder teilweise mit einem gesättigten einwertigen aliphatischen Alkohol mit 1 bis 4 C-Atomen verethert sind, mit einem höheren Fettalkohol mit 12 bis 18 C-Atomen oder einer höheren Fettsäure mit 12 bis 18 C-Atomen zugesetzt.According to the invention, the aqueous dispersions of the film-forming and reactive group-containing polymers are water-insoluble reaction products of condensation products of melamine and formaldehyde, the methylol groups of which are wholly or partly etherified with a saturated monohydric aliphatic alcohol with 1 to 4 carbon atoms, with a higher fatty alcohol with 12 to 18 C atoms or a higher fatty acid with 12 to 18 C atoms added.

Für den Anwendungserfolg ist wesentlich, daß die verwendeten modifizierten Kondensationsprodukte bzw. Derivate des Melamins wasserunlöslich sind. Sie weisen vorteilhafterweise selbstemulgierende Eigenschaften in Wasser auf. In der Regel handelt es sich um die bei der technischen Herstellung entstehenden Gemische bzw. Reaktionsmischungen.It is essential for the success of the application that the modified condensation products or derivatives of melamine used are water-insoluble. they advantageously have self-emulsifying properties in water. As a rule, these are the mixtures or reaction mixtures formed during industrial production.

Ausgangsprodukte für die Modifizierung durch zusätzliche Veretherung oder durch Veresterung sind Kondensationsprodukte aus 1 Mol Melamin und 2 bis 6 Mol, bevorzugt 2,5 bis 5,5 Mol, Formaldehyd, die mit 2,2 bis 6 Mol eines niederen Alkohols, wie Ethanol, Propanol, Butanol oder bevorzugt Methanol, umgesetzt worden sind. Besonders bevorzugt wird technisches Hexamethoxy­methylmelamin, das in der Regel ein Gemisch aus 50 bis 70 Gew.% Hexameth­oxymethylmelamin, das von der Herstellung her Kondensationsprodukte (Präkondensate) mit 2 und 3 und darüber hinaus mit bis zu 6 Melaminkernen enthält, darstellt. Eine beispielhafte Mischung enthält ca. 60 Gew.% Hexamethoxymethylmelamin, ca. 13 Gew.% zwei- bis vierkernige und ca. 26 Gew.% bis zu sechskernige Kondensationsprodukte. Solche Mischungen sind im Handel beispielsweise in Form wäßriger Mischungen erhältlich.Starting products for the modification by additional etherification or by esterification are condensation products of 1 mol of melamine and 2 to 6 mol, preferably 2.5 to 5.5 mol, of formaldehyde, with 2.2 to 6 mol of a lower alcohol, such as ethanol, propanol , Butanol or preferably methanol, have been implemented. Technical hexamethoxymethylmelamine, which is generally a mixture of 50 to 70% by weight of hexamethoxymethylmelamine, which contains condensation products (precondensates) with 2 and 3 and moreover with up to 6 melamine cores, is particularly preferred. An exemplary mixture contains about 60% by weight of hexamethoxymethylmelamine, about 13% by weight of two- to four-nucleus and about 26% by weight of up to six-core condensation products. Such mixtures are commercially available, for example in the form of aqueous mixtures.

Von den höheren Fettalkoholen und Fettsäuren mit 12 bis 18 C-Atomen als Umsetzungskomponente der Melaminkondensationsprodukte sind Stearylalkohol und Stearinsäure besonders bevorzugt.Of the higher fatty alcohols and fatty acids with 12 to 18 carbon atoms as the reaction component of the melamine condensation products, stearyl alcohol and stearic acid are particularly preferred.

Die Veretherung eines mit einem niederen Alkohol methylolierten Melamins, bevorzugt von Hexamethyloxymethylmelamin, mit Stearylalkohol oder die Veresterung mit Stearinsäure erfolgt zweckmäßigerweise mit 0,2 bis 3 Mol Stearylalkohol oder Stearinsäure pro Mol Hexamethoxymelamin bei Temperaturen von 120 bis 150°C, bevorzugt um 135°C, in Gegenwart von Phthalsäure als Katalysator innerhalb von 6 bis 10 Stunden gegebenenfalls unter Abdestillieren flüchtiger Bestandteile unter vermindertem Druck.The etherification of a melamine methylolated with a lower alcohol, preferably of hexamethyloxymethylmelamine, with stearyl alcohol or the esterification with stearic acid is advantageously carried out with 0.2 to 3 mol of stearyl alcohol or stearic acid per mol of hexamethoxymelamine at temperatures from 120 to 150 ° C., preferably around 135 ° C. , in the presence of phthalic acid as a catalyst within 6 to 10 hours, if appropriate with volatile constituents being distilled off under reduced pressure.

Das gewonnene, in Wasser unlösliche Produkt kann vorteilhafterweise in einem aromatenfreien, für die Textilindustrie geeigneten hochsiedenden aliphatischen Kohlenwasserstoff zu einer 50 bis 70 gew.%igen klaren Lösung gelöst werden. Geeignete Kohlenwasserstoffe sind beispielsweise im Handel unter der Bezeichnung Shellsol erhältlich.The water-insoluble product obtained can advantageously be dissolved in a high-boiling aliphatic hydrocarbon free of aromatics and suitable for the textile industry to give a clear solution of 50 to 70% by weight. Suitable hydrocarbons are commercially available, for example, under the name Shellsol.

Eine solche Lösung läßt sich für die Praxis beispielsweise gut handhaben, wobei sich der Zusatz eines üblichen Emulgators von 1 bis 2 Gew.%, bezogen auf das Kondensationsprodukt, empfehlen kann.Such a solution can be handled well in practice, for example, the addition of a conventional emulsifier of 1 to 2% by weight, based on the condensation product, can be recommended.

Im übrigen liegen die wäßrigen Dispersionen der filmbildenden Polymeren in der Regel als 40 bis 50 gew.%ige Dispersionen, bezogen auf Feststoff, vor.Otherwise, the aqueous dispersions of the film-forming polymers are generally present as 40 to 50% by weight dispersions, based on solids.

In diese Dispersionen werden die erfindungsgemäß zu verwendenden Produkte zweckmäßig gelöst in einem organischen Lösungsmittel unter Rühren und vorteilhaft zusammen mit einem synthetischen Verdickungsmittel, so daß die Mischung zu einer Streichpaste verdickt, eingearbeitet.The products to be used according to the invention are expediently incorporated into these dispersions in an organic solvent with stirring and advantageously together with a synthetic thickener, so that the mixture thickens to form a spreading paste.

Die auf das Gewebe aufzutragende Mischung wird dann als Streichpaste in üblicher Weise aufgetragen. Hierzu werden den wäßrigen Dispersionen die handelsüblichen, vorzugsweise vollsynthetischen Verdicker in einer üblichen Menge von 1 bis 2 Gew.%, bezogen auf das Gesamtgewicht, der Mischung zugegeben.The mixture to be applied to the tissue is then applied in the usual way as a spreading paste. For this purpose, the commercially available, preferably fully synthetic, thickeners are added to the mixture in a customary amount of 1 to 2% by weight, based on the total weight.

Als synthetische Verdickungsmittel sind Homopolymerisate oder Copolymeri­sate von ethylenisch-ungesättigten Mono- oder Dicarbonsäuren, insbesondere von Acrylsäure oder Maleinsäure gegebenenfalls mit Comonomeren, wie Acryl­amid, sowie Copolymerisate von ethylenisch-ungesättigten Carbonsäuren untereinander, insbesondere von Acryl- und Maleinsäure, zu nennen. Die verdickende Wirkung tritt in wäßriger Lösung, insbesondere bei teilweiser oder vollständiger Neutralisation mit Basen, vorzugsweise mit Ammoniak oder Natronlauge, ein.Examples of synthetic thickeners are homopolymers or copolymers of ethylenically unsaturated mono- or dicarboxylic acids, in particular acrylic acid or maleic acid, optionally with comonomers, such as acrylamide, and copolymers of ethylenically unsaturated carboxylic acids with one another, in particular of acrylic and maleic acid. The thickening effect occurs in aqueous solution, especially in the case of partial or complete neutralization with bases, preferably with ammonia or sodium hydroxide solution.

Bevorzugt wird ein hochmolekulares Verdickungsmittel auf Basis von Acryl­säure mit Acrylamid als Comonomer, neutralisiert mit Ammoniak auf einen pH von 8, verwendet.A high molecular weight thickener based on acrylic acid with acrylamide as comonomer, neutralized with ammonia to a pH of 8, is preferably used.

Die folgende Trocknung der Beschichtung auf dem Gewebe erfolgt zweckmäßig bei Temperaturen von 80 bis 120°C. Anschließend wird bei Temperaturen von 150 bis 200°C, insbesondere 160 bis 170°C, innerhalb von 1 bis 5, bevorzugt 2 bis 3 Minuten fixiert oder ausgehärtet.The following drying of the coating on the fabric is advantageously carried out at temperatures of 80 to 120 ° C. The mixture is then fixed or cured at from 150 to 200 ° C., in particular 160 to 170 ° C., within 1 to 5, preferably 2 to 3 minutes.

Bei der Fixierung erfolgen Vernetzungen sowie eine Auskondensation des verwendeten Melaminkondensationsproduktes. Dadurch werden außerordentlich beständige Feinbeschichtungen erreicht, die sich durch besonders gute wasserabweisende Eigenschaften auszeichnen.During fixation, crosslinking and condensation of the melamine condensation product used take place. This results in extremely durable fine coatings that are characterized by particularly good water-repellent properties.

Die Vernetzung oder Aushärtung kann beschleunigt werden durch acid wirken­de Substanzen als saure Katalysatoren, wie sie bei der Hochveredlung von Cellulose üblich sind, beispielsweise durch Zink- oder Magnesiumchloride, -nitrate, Zinkfluoroborate oder insbesondere Ammoniumchlorid. Diese können in den bei der Hochveredlung üblichen Mengen eingesetzt werden. Bewährt haben sich Mengen von bis zu 10, vorzugsweise bis zu 5 Gew.-Teilen Katalysator je 100 Gew.-Teile Melaminverbindung (als Feststoff gerechnet).The crosslinking or hardening can be accelerated by acidic substances as acidic catalysts, as are customary in the high refinement of cellulose, for example by zinc or magnesium chlorides, nitrates, zinc fluoroborates or in particular ammonium chloride. These can be used in the quantities customary for high-level finishing. Quantities of up to 10, preferably up to 5 parts by weight of catalyst per 100 parts by weight of melamine compound (calculated as a solid) have proven useful.

Synthetische Verdicker können aufgrund ihrer Zusammensetzung, beispiels­weise durch einpolymerisierte Carboxylgruppen, als Katalysator wirken, so daß die obengenannten Katalysatoren dadurch weitgehend ersetzt werden können.Synthetic thickeners can act as a catalyst due to their composition, for example by polymerized carboxyl groups, so that the above-mentioned catalysts can be largely replaced.

Bei einer vorteilhaften und zweckmäßigen Ausführungsform werden das Mel­aminkondensationsprodukt und das filmbildende Polymer, jeweils bezogen als Feststoff, in einem Verhältnis von 1:3 bis 1:10, bevorzugt 1:4 bis 1:8, verwendet.In an advantageous and expedient embodiment, the melamine condensation product and the film-forming polymer, each based on a solid, are used in a ratio of 1: 3 to 1:10, preferably 1: 4 to 1: 8.

Die folgenden Beispiele erläutern die Erfindung. Dabei sind Teile Gewichtsteile.The following examples illustrate the invention. Parts are parts by weight.

Beispiel 1example 1

Ein Polyamid-Gewebe von 65 g/m² Warengewicht wird mit einer der Streich­pasten, die wie folgt zusammengesetzt sind, beschichtet:

Figure imgb0001
A polyamide fabric with a fabric weight of 65 g / m² is coated with one of the coating pastes, which are composed as follows:
Figure imgb0001

Das Polyamidgewebe wird mit 2 Strichen per Luftrakel und mit der Hand be­schichtet, wobei eine Gesamtmenge von 20 g Feststoff in Paste A oder B/m² aufgetragen wird. Es wird bei 100°C getrocknet und anschließend 2 min bei 160°C fixiert.The polyamide fabric is coated with 2 strokes using an air knife and by hand, a total of 20 g of solid being applied in paste A or B / m². It is dried at 100 ° C. and then fixed at 160 ° C. for 2 minutes.

Mit dem Rezept B erhält man eine weiche, hydrophobe Beschichtung, die auch nach 5-maligem Waschen einen Schopperwert über 1000 mm aufweist. Dagegen fällt bei der Beschichtung A der Schopperwert nach 5-maligem Waschen deutlich auf etwa 500 mm ab.Recipe B gives a soft, hydrophobic coating that has a Schopper value of over 1000 mm even after 5 washes. In contrast, with coating A, the Schopper value drops significantly after washing 5 times to about 500 mm.

Das Aussehen der Probe B bleibt einwandfrei, während die Probe A verwaschen wirkt.The appearance of sample B remains perfect, while sample A appears washed out.

Beispiel 2Example 2

Mit einer der Pasten A oder B gemäß Beispiel 1 wird auf das Polyamidgewebe (65 g/m²) zuerst ein Grundstrich aufgetragen, getrocknet und dann in einem zweiten Strich als Deckstrich mit einer der folgenden Pasten C oder D beschichtet, wobei die Paste C auf A und D auf B aufgetragen werden. Es werden jeweils 12 g Feststoff/m² aufgetragen.

Figure imgb0002
With one of the pastes A or B according to Example 1, a base coat is first applied to the polyamide fabric (65 g / m²), dried and then coated in a second coat as a top coat with one of the following pastes C or D, the paste C being A and D are applied to B. In each case 12 g of solid / m² are applied.
Figure imgb0002

Mit der erfindungsgemäßen Beschichtung wird eine außerordentlich gute Wasch- und Chemischreinigungspermanenz erreicht. Nach mehrmaligem Waschen beträgt der Schopperwert noch immer über 1000 mm, dagegen wird beim Ver­gleich die beschichtete Ware bereits nach einer Wäsche wasserdurchlässig.With the coating according to the invention, an extraordinarily good washing and dry cleaning durability is achieved. After washing several times, the Schopper value is still over 1000 mm, whereas in comparison the coated goods become water-permeable after just one wash.

Claims (4)

1. Verfahren zur Herstellung von wasch- und chemischreinigungsbeständigen feinbeschichteten Textilien, mit wäßrigen Dispersionen filmbildender und reaktive Gruppen enthaltender Polymerer, dadurch gekennzeichnet, daß man den wäßrigen Dispersionen der filmbildenden Polymeren wasserunlösliche Umsetzungsprodukte von Kondensationsprodukten aus Melamin und Formaldehyd, deren Methylolgruppen ganz oder teilweise mit einem gesättigten einwertigen aliphatischen Alkohol mit 1 bis 4 C-Atomen verethert sind, mit einem Fettalkohol mit 12 bis 18 C-Atomen oder einer Fettsäure mit 12 bis 18 C-Atomen zusetzt, das Textilgut mit dieser Mischung beschichtet, trocknet und bei Temperaturen von 150 bis 200°C fixiert.1. A process for the preparation of washable and dry-cleaning-resistant finely coated textiles, with aqueous dispersions of film-forming and reactive groups-containing polymers, characterized in that the aqueous dispersions of the film-forming polymers are water-insoluble reaction products of condensation products of melamine and formaldehyde, the methylol groups of which, in whole or in part, with a saturated monohydric aliphatic alcohol with 1 to 4 carbon atoms are etherified, with a fatty alcohol with 12 to 18 carbon atoms or a fatty acid with 12 to 18 carbon atoms, the textile is coated with this mixture, dried and at temperatures of 150 to Fixed at 200 ° C. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man das Umsetzungsprodukt von technischem Hexamethoxymethylmelamin mit einem Fettalkohol oder einer Fettsäure mit 12 bis 18 C-Atomen einsetzt.2. The method according to claim 1, characterized in that one uses the reaction product of technical hexamethoxymethylmelamine with a fatty alcohol or a fatty acid having 12 to 18 carbon atoms. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man den Umsetzungsprodukten zur Beschleunigung ihrer Fixierung saure Katalysatoren zusetzt.3. The method according to claim 1 or 2, characterized in that acidic catalysts are added to the reaction products to accelerate their fixing. 4. Verwendung von wasserunlöslichen Umsetzungsprodukten von Konden­sationsprodukten des Melamins, wie in Anspruch 1 oder 2 definiert, bei der Feinbeschichtung von Textilien zusammen mit wäßrigen Dispersionen filmbildender und reaktive Gruppen enthaltender Polymerer.4. Use of water-insoluble reaction products of condensation products of melamine, as defined in claim 1 or 2, in the fine coating of textiles together with aqueous dispersions of film-forming and reactive groups-containing polymers.
EP88118789A 1987-11-19 1988-11-11 Process for coating textiles Withdrawn EP0316784A3 (en)

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DE4107779A1 (en) * 1991-03-11 1992-09-17 Stefan Wagner Kg Artificial, esp. silk, flower treatment with acrylic] resin binder - by dipping in or brushing with opt. coloured dispersion paste for dimensional stability

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2509174A (en) * 1947-05-22 1950-05-23 Monsanto Chemicals Process of waterproofing textile fabrics
CH381194A (en) * 1958-06-06 1962-12-15 Ciba Geigy Process for finishing textile fibers
DE2002003A1 (en) * 1969-01-27 1970-07-30 Ciba Geigy Aqueous emulsions
FR2155774A1 (en) * 1971-10-04 1973-05-25 Rousselot Cie

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2509174A (en) * 1947-05-22 1950-05-23 Monsanto Chemicals Process of waterproofing textile fabrics
CH381194A (en) * 1958-06-06 1962-12-15 Ciba Geigy Process for finishing textile fibers
DE2002003A1 (en) * 1969-01-27 1970-07-30 Ciba Geigy Aqueous emulsions
FR2155774A1 (en) * 1971-10-04 1973-05-25 Rousselot Cie

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