EP0121078B1 - Textile auxiliaries - Google Patents

Textile auxiliaries Download PDF

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Publication number
EP0121078B1
EP0121078B1 EP19840101888 EP84101888A EP0121078B1 EP 0121078 B1 EP0121078 B1 EP 0121078B1 EP 19840101888 EP19840101888 EP 19840101888 EP 84101888 A EP84101888 A EP 84101888A EP 0121078 B1 EP0121078 B1 EP 0121078B1
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Prior art keywords
weight
textile
atoms
und
parts
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EP19840101888
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German (de)
French (fr)
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EP0121078A1 (en
Inventor
Wilfried Dipl.-Ing. Kortmann
Helmut Dr. Steinberger
Ulrich Dr. Koemm
Josef Dipl.-Ing. Pfeiffer
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Bayer AG
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Bayer AG
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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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • 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
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/576—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them containing fluorine
    • 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
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

  • the present invention relates to a textile finishing agent which allows textile fibers to be made dirt, oil and water repellent.
  • Dirt substances can be e.g. of the following composition and consistency: oil and oil-containing substances, liquid, aqueous colored substances, inorganic dry pigment-like substances (street dust), aqueous suspensions of the same and mixtures of the substances mentioned.
  • the principle of protective equipment is that the finishing agent gives the pole materials hydrophobic and oleophobic properties that prevent the sinking of liquid contaminants. Dry dirt does not adhere to the fibers and can e.g. can be easily removed by vacuuming from and out of the pile.
  • silsesquioxane suspensions described there are, however, relatively unstable and are not universally suitable for dirt-repellent and pole-stabilizing finishing.
  • DE-B-1 285 978 discloses a process for rendering oil and water repellant and for reducing the absorption of dry dirt from textile materials.
  • substances containing perfluoroalkyl groups are applied to the materials to be protected.
  • Organosilsesquioxanes as described, for example, in DE-B-1 594 985 or in DE-A-3 004 824 can be used as component A). These are prepared by, for example, silanes of the general formula R-Si (OR ') 3 alone or together with silanes (Si (OR') 4 in which R is substituted or unsubstituted hydrocarbon radical having 1 to 7 carbon atoms, the substituents of which are halogen atoms, amino, Mercapto and epoxy groups and up to 95% of the radicals R are methyl and R 'is an alkyl radical having 1 to 4 carbon atoms to a mixture of water, a buffer substance, a surface-active agent and optionally an organic solvent with agitation and under acid or basic conditions are added.
  • silane In order to achieve a very narrow particle size distribution and a small average pond size of approximately 200 to 500 angstroms, such as are required to achieve optimal pole-stabilizing and dirt-repellent effects, a uniform and slow addition of the amount of silane is required.
  • the exact amount of silane that can be added depends on the substituent R and whether an anionic or cationic surfactant is used.
  • the simultaneous hydrolysis of the silanes results in copolymers of the silsesquioxanes in which the units can be present in block form or in a random distribution.
  • the preferred amount of added silane of the general formula Si (OR ') 4 is 2 to 50%, based on the total amount of the silanes used, preferably 3 to 20% (% by weight).
  • the surface-active agents mentioned have the function of stabilizing the particles formed in the colloidal suspension.
  • Suitable anionic surfactants are aliphatic and / or aromatic sulfonic acids, for example decyl, dodecyl, cetyl, stearyl, myristic or oleyl sulfonic acids or their alkali metal salts. If cationic surfactants are used, it is advantageous to use halides and especially chlorides and bromides. Other surfactants, including those of a nonionic and amphoteric nature, can be used in conjunction with the above agents provided they do not interfere with the stability of the colloidal suspension due to their nature or amount.
  • the surfactants are used in an amount of about 0.01 to about 15%, based on the amount of silane used.
  • the process for the preparation of the colloidal suspensions can be carried out at temperatures between room temperature and 80 ° C .; the temperature range between 50 and 70 ° C. is particularly preferred.
  • Aqueous dispersions of a fluorocarbon resin can be used as the perfluoroalkyl group-containing compounds.
  • the chemically bound fluorine is in the form of perfluoroalkyl ligands with a chain length of 3 to 20 carbon atoms and, in addition to fluorine atoms, can contain a maximum of 1 hydrogen or chlorine atom per 2 carbon atoms.
  • the perfluoroalkyl chain can also be interrupted by oxygen atoms.
  • the perfluoroalkyl ligand is bound to a water-insoluble monomeric or polymeric organic compound. Examples of such compounds are polyacrylates containing perfluoroalkyl ligands (cf.
  • the perfluoroalkyl group-containing dispersion contains about 5 to 50% by weight of fluorocarbon resin with a fluorine content of 0.2 to 40, preferably 1.0 to 20% by weight.
  • organic solvents can also be added to the dispersion in smaller amounts in order to obtain particularly favorable behavior when applied to the fiber.
  • the finish is effective on all types of fibers, i.e. fibers made of synthetic and organic and inorganic fibers and natural fibers.
  • the treatment agent according to the invention is used in an amount of 0.5-2% by weight, based on the fiber material.
  • finishing products can be applied either before, during or after the dyeing of the textile or subsequent further finishing steps, or subsequently after processing as a cover, upholstery or floor covering textile by treatment in the liquor, padding or spraying.
  • Another method of applying the agent according to the invention to the fiber material is to use it together with a cleaning agent, especially if the textile to be treated has been soiled by use or previous processing steps. It is preferable to finish goods that have not been equipped by the manufacturer after wet cleaning by spraying the preparation onto the goods.
  • the above mixture is dried, roughly crushed, ground in a powder mill and then sieved through a sieve with a mesh size of 100 ⁇ m using a sieving machine.
  • the samples are loaded after the chair roller test, which is described in detail in DIN 54 324, with a total roller load of 60 kg and a change in the roller pressure direction after every 50 revolutions.
  • a polyester tufted fabric (loop, 100%, PES) with a pile weight of 400 g / m 2 was treated as indicated in Example 1.
  • a polyacrylic tufting fabric (loop, 100%, PAC) with a pile weight of 500 g / m 2 was treated as indicated in Example 1.
  • the concentration of the equipment used was 10 g / l in all cases.
  • a polyamide tufted fabric (velor, 100% PA) with a weight per square meter of 700 g was treated as indicated in Example 1.

Description

Die vorliegende Erfindung betrifft ein Textilausrüstungsmittel, das es erlaubt, Textilfasern schmutz-, öl- und wasserabweisend auszurüsten.The present invention relates to a textile finishing agent which allows textile fibers to be made dirt, oil and water repellent.

Von modernen Textilmaterialien, die z.B. als Möbelbezugsstoffe oder als textiler Bodenbelag Verwendung finden, erwartet der Verbraucher günstige Eigenschaften im Hinblick auf ihre mechanische Beanspruchbarkeit, also ihre statische und dynamische Belastbarkeit und eine Unempfindlichkeit gegen Wasser, Öl und/oder Schmutz.Of modern textile materials, e.g. used as upholstery fabrics or as textile flooring, the consumer expects favorable properties with regard to their mechanical strength, i.e. their static and dynamic resilience and insensitivity to water, oil and / or dirt.

Ein grosses Problem bei Textilien mit dreidimensionaler Struktur, z.B. Polmaterialien, die durch Schlingen oder aufgeschnittene Schlingen (= Velours) eine bestimmte Oberflächenstruktur besitzen und einer starken Beanspruchung währens des Gebrauches ausgesetzt sind, ist die Erhaltung der Sauberkeit über einen längeren Zeitraum.A big problem with textiles with a three-dimensional structure, e.g. Pole materials that have a certain surface structure due to loops or cut loops (= velor) and are exposed to heavy use during use are to maintain cleanliness over a longer period of time.

Dazu müssen zwangsläufig entstandene Verschmutzungen leicht und soweit entfernbar sein, dass keine nur geringe Rückstände auf dem Material verbleiben, die es optisch nicht oder nur unwesentlich beeinträchtigen.Inevitably, soiling must be easy and so far removed that no small residues remain on the material, which do not affect it visually or only insignificantly.

Schmutzsubstanzen können von z.B. folgender Zusammensetzung und Konsistenz sein: Öl und ölenthaltende Substanzen, flüssige, wässrige angefärbte Substanzen, anorganische trockene pigmentartige Substanzen (Strassenstaub), wässrige Suspensionen derselben und Mischungen der genannten Substanzen.Dirt substances can be e.g. of the following composition and consistency: oil and oil-containing substances, liquid, aqueous colored substances, inorganic dry pigment-like substances (street dust), aqueous suspensions of the same and mixtures of the substances mentioned.

Das Prinzip einer Schutzausrüstung besteht darin, dass durch das Ausrüstungsmittel den Polmaterialien hydrophobe und oleophobe Eigenschaften verliehen werden, die das Einsinken von flüssigen Verschmutzungen verhindern. Trockenschmutz haftet nicht an den Fasern und kann z.B. durch Stabsaugen von und aus der Polware leicht entfernt werden.The principle of protective equipment is that the finishing agent gives the pole materials hydrophobic and oleophobic properties that prevent the sinking of liquid contaminants. Dry dirt does not adhere to the fibers and can e.g. can be easily removed by vacuuming from and out of the pile.

Es wird bereits an andere Stelle Verfahren zur Behandlung von Fasermaterialien wie Fäden, Fasern, Gewebe und Teppich beschrieben worden (z.B. DE-B 1 594 985), um diesen Rutschsicherheit und Widerstandsfähigkeit gegen Trockenschmutz zu verleihen. Bei diesen Verfahren werden kolloidale Suspensionen von Silsequioxanen aus Einheiten der Formel RSi03,2 mit einer Teilchengrösse von 10 bis 1000 Ängström verwendet.Processes for treating fiber materials such as threads, fibers, fabrics and carpets have already been described elsewhere (for example DE-B 1 594 985) in order to give them slip resistance and resistance to dry dirt. In these processes, colloidal suspensions of silsequioxanes from units of the formula RSi0 3 , 2 with a particle size of 10 to 1000 angstroms are used.

Die dort beschriebenen Silsesquioxansuspensionen sind aber relativ unbeständig und sind nicht universell zur schmutzabweisenden und polstabilisierenden Ausrüstung geeignet.The silsesquioxane suspensions described there are, however, relatively unstable and are not universally suitable for dirt-repellent and pole-stabilizing finishing.

Aus der DE-B-1 285 978 ist ein Verfahren zum Öl-und Wasserabweisendmachen sowie zur Verminderung der Aufnahme von Trockenschmutz von Textilmaterialien bekannt. Um diese Effekte zu erreichen, werden Perfluoralkyl-gruppenhaltige Substanzen auf die zu schützenden Materialien aufgebracht.DE-B-1 285 978 discloses a process for rendering oil and water repellant and for reducing the absorption of dry dirt from textile materials. In order to achieve these effects, substances containing perfluoroalkyl groups are applied to the materials to be protected.

Die Ausrüstung mit Silsesquioxanen einerseits bzw. mit Perfluoralkyl-gruppenhaltigen Substanzen andererseits liess jedoch immer noch Wünsche offen, die bisher nicht erfüllt werden konnten. Es wurden zwar bereits Versuche unternommen, Textilien mit Silico-Fluorchemikalien auszurüsten (vgl. z.B. Textil-Praxis Int., 1972, August-Heft, Seite 503 oder DE-A-2 361 976). Dabei musste allerdings festgestellt werden, dass zwar der Hydrophob-Effekt sehr verstärkt wird, jedoch der Oleophob-Effekt der Fluorchemikalie völlig aufgehoben wird. Dies ist wohl der Grund, weshalb bis heute keine derartige Kombination eingesetzt werden konnte.Equipping with silsesquioxanes on the one hand or with substances containing perfluoroalkyl groups, on the other hand, still left something to be desired that could not previously be fulfilled. Attempts have already been made to equip textiles with silico-fluorochemicals (see e.g. Textil-Praxis Int., 1972, August issue, page 503 or DE-A-2 361 976). However, it had to be determined that the hydrophobic effect is greatly enhanced, but the oleophobic effect of the fluorochemical is completely eliminated. This is probably the reason why no such combination has been used to date.

Aus GB-A-1 155 741 sowie aus Chemical Abstract, Bd. 90, No. 2, S. 61, No. 7548 b sind ebenfalls Gemische zur Ausrüstung textiler Materialien beschrieben. Auch hierbei handelt es sich um Gemische fluorierter Verbindungen mit Polysiloxansuspensionen. Dabei werden als Polysiloxane Polydimethylsiloxane oder Polydimethylhydrogensiloxane eingesetzt. Auch bei diesen Gemischen stellt sich der obengenannte Nachteil ein.From GB-A-1 155 741 and from Chemical Abstract, Vol. 90, No. 2, p. 61, no. 7548 b mixtures are also described for finishing textile materials. These are also mixtures of fluorinated compounds with polysiloxane suspensions. Polydimethylsiloxanes or polydimethylhydrogensiloxanes are used as polysiloxanes. The above-mentioned disadvantage also arises with these mixtures.

Überraschenderweise hat sich jedoch herausgestellt, dass Kombinationen bestimmter Organosilikatverbindungen mit bestimmten Perfluor-Verbindungen sich hervorragend als Textilausrüstungsmittel eignen und somit für einen universellen Schutz der Faser eingesetzt werden können.Surprisingly, however, it has been found that combinations of certain organosilicate compounds with certain perfluoro compounds are outstandingly suitable as textile finishing agents and can therefore be used for universal protection of the fiber.

Gegenstand der vorliegenden Erfindung sind somit Textilausrüstungsmittel, die gekennzeichnet sind durch einen Gehalt an

  • A) 50 bis 80 Gew.-Teilen einer in Form eines Sols wässrigen kolloidalen Suspension von Organosilsesquioxanen aus Einheiten der Formel RSi0312 (R = gegebenenfalls mit Halogen, Amino-, Mercapto- oder Epoxygruppen substituierter Alkylrest mit bis zu 7 Kohlenstoffatomen) und/oder Cokondensaten aus Hydrolysaten von Tetraalkoxysilanen mit Organotrialkoxysilanen mit RSi03/2- bzw. SiOz- Einheiten und
  • B) 20 bis 50 Gew.-Teilen einer wässrigen Dispersion eines organischen Polymerharzes, das Perfluoralkylgruppen mit 3 bis 20 C-Atomen enthält, wobei die Perfluoralkylgruppen ausser Fluoratomen höchstens 1 Wasserstoffatom- oder Chloratom pro 2 C-Atome enthalten können und wobei die perfluoralkylkette durch Sauerstoff unterbrochen sein kann und wobei die wässrige Dispersion 5 bis 50 Gew.-% fluorgruppen-haltiges organisches Polymerharz mit einem Fluorgehalt von 0,2 bis 40 Gew.-% aufweist.
The present invention thus relates to textile finishing agents which are characterized by a content of
  • A) 50 to 80 parts by weight of a colloidal suspension of organosilsesquioxanes in the form of a sol, consisting of units of the formula RSi0 312 (R = alkyl radical optionally substituted with halogen, amino, mercapto or epoxy groups and having up to 7 carbon atoms) and / or Cocondensates from hydrolysates of tetraalkoxysilanes with organotrialkoxysilanes with RSi0 3/2 or SiO z units and
  • B) 20 to 50 parts by weight of an aqueous dispersion of an organic polymer resin which contains perfluoroalkyl groups having 3 to 20 carbon atoms, the perfluoroalkyl groups apart from fluorine atoms being able to contain at most 1 hydrogen atom or chlorine atom per 2 carbon atoms and wherein the perfluoroalkyl chain contains Oxygen can be interrupted and the aqueous dispersion has 5 to 50% by weight fluorine-containing organic polymer resin with a fluorine content of 0.2 to 40% by weight.

Als Komponente A) können Organosilsesquioxane, wie sie z.B. in der DE-B-1 594 985 oder in der DE-A-3 004 824 beschrieben sind, eingesetzt werden. Diese werden hergestellt, indem man z.B. Silane der allgemeinen Formel R-Si (OR' )3 alleine oder zusammen mit Silanen (Si(OR')4 worin R substituierter oder unsubstituierter Kohlenwasserstoffrest mit 1 bis 7 Kohlenstoffatomen, dessen Substituenten Halogenatome, Amino-, Mercapto- und Epoxygruppen sein können und bis zu 95% der Reste R Methyl sind und R' einen Alkylrest mit 1 bis 4 Kohlenstoffatomen bedeutet zu einem Gemisch aus Wasser, einer Puffersubstanz, einem oberflächenaktiven Mittel und gegebenenfalls einem organischen Lösungsmittel unter Bewegung und unter sauren oder basischen Bedingungen zugegeben werden.Organosilsesquioxanes as described, for example, in DE-B-1 594 985 or in DE-A-3 004 824 can be used as component A). These are prepared by, for example, silanes of the general formula R-Si (OR ') 3 alone or together with silanes (Si (OR') 4 in which R is substituted or unsubstituted hydrocarbon radical having 1 to 7 carbon atoms, the substituents of which are halogen atoms, amino, Mercapto and epoxy groups and up to 95% of the radicals R are methyl and R 'is an alkyl radical having 1 to 4 carbon atoms to a mixture of water, a buffer substance, a surface-active agent and optionally an organic solvent with agitation and under acid or basic conditions are added.

Zur Erzielung einer sehr engen Teilchengrössenverteilung und einer geringen durchschnittlichen Teichengrösse von etwa 200 bis 500 Ängström, wie sie zur Erzielung optimaler polstabilisierender und schmutzabweisender Effekte erforderlich sind, ist eine gleichförmige und langsame Zugabe der Silanmenge erforderlich. Die genaue Silanmenge, die zugegeben werden kann, hängt vom Substituenten R ab und davon, ob ein anionisches oder kationisches oberflächenaktives Mittel verwendet wird.In order to achieve a very narrow particle size distribution and a small average pond size of approximately 200 to 500 angstroms, such as are required to achieve optimal pole-stabilizing and dirt-repellent effects, a uniform and slow addition of the amount of silane is required. The exact amount of silane that can be added depends on the substituent R and whether an anionic or cationic surfactant is used.

Es entstehen durch die gleichzeitige Hydrolyse der Silane Mischpolymerisate der Silsesquioxane, worin die Einheiten in Blockform oder statistisch verteilt vorliegen können. Die bevorzugte Menge an zugesetztem Silan der allgemeinen Formel Si(OR')4 beträgt 2 bis 50%, bezogen auf die Gesamtmenge der eingesetzten Silane, vorzugsweise 3 bis 20% (Gew.-%).The simultaneous hydrolysis of the silanes results in copolymers of the silsesquioxanes in which the units can be present in block form or in a random distribution. The preferred amount of added silane of the general formula Si (OR ') 4 is 2 to 50%, based on the total amount of the silanes used, preferably 3 to 20% (% by weight).

Die Silsesquioxan Dispersion ist etwa wie folgt zusammengesetzt:

  • 0,001 bis 3% Oberflächenaktives Mittel
  • 0,005 bis 4% Puffersubstanz
  • 5 bis 22% Silanmischung
  • 95 bis 71 % Wasser,(%-Angaben = Gew.-%) wobei es etwa 2 bis 9 Gew.-% Silsesquioxane und ca. 0,1 bis 0,4 Gew.-% SiOz-Einheiten enthält.
The silsesquioxane dispersion is composed approximately as follows:
  • 0.001 to 3% surfactant
  • 0.005 to 4% buffer substance
  • 5 to 22% silane mixture
  • 95 to 71% water, (% data =% by weight), it containing about 2 to 9% by weight of silsesquioxane and about 0.1 to 0.4% by weight of SiO z units.

Die genannten oberflächenaktiven Mittel haben die Funktion, die gebildeten Teilchen der kolloidalen Suspension zu stabilisieren.The surface-active agents mentioned have the function of stabilizing the particles formed in the colloidal suspension.

Bevorzugt werden folgende Silane eingesetzt:

  • Methyltrimethoxysilan, Methyltriethoxysilan, Methyltriisopropoxysilan, Ethyltrimethoxysilan, Ethyltriethoxysilan, Propyltrimethoxysilan, Isobutyltrimethoxysilan, Isobutyltriethoxysilan, 2-Ethylbutyltriethoxysilan, Tetraethoxysilan, 2-Ethylbutoxytriethoxysilan.
The following silanes are preferably used:
  • Methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, 2-ethylbutyltriethoxysoxoxysilane, 2-ethylbutyltriethoxysoxysilane.

Als anionische oberflächenaktive Mittel kommen aliphatische und/oder aromatische Sulfonsäuren in Betracht, beispielsweise Decyl-, Dodecyl-, Cetyl-, Stearyl-, Myristil- oder Oleylsulfonsäuren oder deren Alkalisalze. Werden kationische oberflächenaktive Mittel verwendet, ist es vorteilhaft, Halogenide und insbesondere Chloride und Bromide zu verwenden. Andere oberflächenaktive Mittel, einschliesslich solche von nichtionogener und amphoterer Natur, können in Verbindung mit den obengenannten Mitteln verwendet werden, sofern dieselben weder aufgrund ihrer Natur noch ihrer Menge einen störenden Einfluss auf die Stabilität der kolloidalen Suspension ausüben.Suitable anionic surfactants are aliphatic and / or aromatic sulfonic acids, for example decyl, dodecyl, cetyl, stearyl, myristic or oleyl sulfonic acids or their alkali metal salts. If cationic surfactants are used, it is advantageous to use halides and especially chlorides and bromides. Other surfactants, including those of a nonionic and amphoteric nature, can be used in conjunction with the above agents provided they do not interfere with the stability of the colloidal suspension due to their nature or amount.

Die oberflächenaktiven Mittel werden in einer Menge von etwa 0,01 bis etwa 15%, bezogen auf die eingesetzte Silanmenge, eingesetzt.The surfactants are used in an amount of about 0.01 to about 15%, based on the amount of silane used.

Das Verfahren zur Herstellung der kolloidalen Suspensionen kann bei Temperaturen zwischen Raumtemperatur und 80°C durchgeführt werden; besonders bevorzugt ist der Temperaturbereich zwischen 50 und 70°C.The process for the preparation of the colloidal suspensions can be carried out at temperatures between room temperature and 80 ° C .; the temperature range between 50 and 70 ° C. is particularly preferred.

Als Perfluoralkylgruppen-haltige Verbindungen können wässrige Dispersionen eines Fluorcarbonharzes eingesetzt werden.Aqueous dispersions of a fluorocarbon resin can be used as the perfluoroalkyl group-containing compounds.

Das chemisch gebundene Fluor liegt vor in Form von Perfluoralkylliganden mit einer Kettenlänge von 3 bis 20 C-Atomen und kann ausser Fluoratomen höchstens 1 Wasserstoff- oder Chloratom auf je 2 Kohlenstoffatome enthalten. Die Perfluoralkylkette kann auch durch Sauerstoffatome unterbrochen sein. Der Perfluoralkylligand ist an eine wasserunlösliche monomere oder polymere organische Verbindung gebunden. Als Beispiel für derartige Verbindungen sind Perfluoralkylliganden enthaltende Polyacrylate (vgl. z.B. DE-B 1 595 017, DE-B 1 595 018, DE-A 2 939 549, DE-B 2 134 978, DE-B 2 660 200, DE-B 1 106 960, DE-B 1 745 089), Perfluoralkylliganden enthaltende Urethane und Polyurethane (vgl. z.B. DE-A 1 468 295, DE-B 1 794 356, DE-C 2 702 305, DE-B 1 795 261, DE-A 1 956 198), Perfluoralkylliganden enthaltende Ester aromatischer und aliphatischer Di- und Polycarbonsäuren, (vgl. z.B. DE-A 3 002 369, EP-A 19 732, DE-A 3 119 071, DE-A 2 015 332) zu nennen.The chemically bound fluorine is in the form of perfluoroalkyl ligands with a chain length of 3 to 20 carbon atoms and, in addition to fluorine atoms, can contain a maximum of 1 hydrogen or chlorine atom per 2 carbon atoms. The perfluoroalkyl chain can also be interrupted by oxygen atoms. The perfluoroalkyl ligand is bound to a water-insoluble monomeric or polymeric organic compound. Examples of such compounds are polyacrylates containing perfluoroalkyl ligands (cf. for example DE-B 1 595 017, DE-B 1 595 018, DE-A 2 939 549, DE-B 2 134 978, DE-B 2 660 200, DE- B 1 106 960, DE-B 1 745 089), urethanes and polyurethanes containing perfluoroalkyl ligands (see, for example, DE-A 1 468 295, DE-B 1 794 356, DE-C 2 702 305, DE-B 1 795 261, DE-A 1 956 198), esters of aromatic and aliphatic di- and polycarboxylic acids containing perfluoroalkyl ligands (see, for example, DE-A 3 002 369, EP-A 19 732, DE-A 3 119 071, DE-A 2 015 332) to call.

Die perfluoralkylgruppenhaltige Dispersion enthält etwa 5 bis 50 Gew.-% Fluorcarbonharz mit einem Fluorgehalt von 0,2 bis 40, bevorzugt 1,0 bis 20 Gew.-%.The perfluoroalkyl group-containing dispersion contains about 5 to 50% by weight of fluorocarbon resin with a fluorine content of 0.2 to 40, preferably 1.0 to 20% by weight.

Die wässrigen Dispersionen der Fluorcarbonharze können darüber hinaus Polymere oder Polykondensate enthalten, die die filmbildenden oder wasserabstossenden Eigenschaften des Polyfluorharzes verstärken [s.a. Sherman, Smith, Johannessen, Text. Res. J., 39 (1969) 449; Tomasino, Seastrunk, Am. Dyestuff. Reptr., 71 (1982) 221. Speziell bevorzugt werden:

  • 1. Eine 40%ige (Gew.-%) wässrige Dispersion eines Perfluorharzgemische, das zusammengesetzt ist aus 4 Teilen eines Copolymeren A und 6 Teilen eines Copolymeren B. Das Copolymere A besteht zu 70% aus Einheiten der Formel
    Figure imgb0001
    und aus 30% aus Einheiten der Formel
    Figure imgb0002
    B ist ein Methylmethacrylat-Ethylmethacrylat-Copolymeres mit einem Methylmethacrylatanteil von ca. 80%.
  • 11. Eine 30%ige wässrige Dispersion eines Perfluorharzgemisches, das zusammengesetzt ist aus 9 Teilen des in (1) beschriebenen Copolymeren A, aus 6 Teilen des in (I) beschriebenen Copolymeren B und 5 Teilen eines Perfluoralkylgruppen-enthaltenden Polyurethans C. Das Polyurethan C hat ein mittleres Molekulargewicht von 3500 und enthält die wiederkehrende Förmeleinheit
    Figure imgb0003
    Figure imgb0004
    sowie Kettenenden der Formel
    Figure imgb0005
    bzw.
    Figure imgb0006
    Figure imgb0007
  • 111. Eine 40%ige wässrige Dispersion eines Perfluorharzgemisches, das zusammengesetzt ist aus 2 Teilen eines Copolymeren D, 4 Teilen eines Polykondensats E und 4 Teilen Paraffin. Das Copolymere D besteht aus Einheiten der Formel
    Figure imgb0008
    Figure imgb0009
  • E ist durch Polykondensation eines C20-Fett- säuregemisches (2 Mol) mit Hexamethylolmelaminpentamethylether (1 Mol) und Methyldiethanolamin (1 Mol) erhältlich.
  • IV. Eine 40%ige Dispersion eines Perfluorharzgemisches, bestehend aus 6 Teilen des in Beispiel (I) beschriebenen Copolymeren A, 9 Teilen des in Beispiel (I) beschriebenen Copolymeren B und 5 Teilen eines Perfluorcarbonsäureesters F. F besteht aus monomeren Einheiten der Formel
    Figure imgb0010
    die über Polyurethanpräpolymere der Formel
    Figure imgb0011
    mit einem mittleren Molekulargewicht von 3000 verknüpft sind.
  • V. Eine ca. 10%ige Dispersion eines Perfluorharzes, bestehend aus einem Copolymeren mit Einheiten der Formel
    Figure imgb0012
    mit n = 4, 6, 8, 10, 12, 14.
The aqueous dispersions of the fluorocarbon resins can also contain polymers or polycondensates which enhance the film-forming or water-repellent properties of the polyfluororesin [see Sherman, Smith, Johannessen, Text. Res. J., 39 (1969) 449; Tomasino, Seastrunk, Am. Dyestuff. Reptr., 71 (1982) 221. The following are particularly preferred:
  • 1. A 40% (wt .-%) aqueous dispersion of a perfluoro resin mixture, which is composed of 4 parts of a copolymer A and 6 parts of a copolymer B. The copolymer A consists of 70% of units of the formula
    Figure imgb0001
     and 30% from units of the formula
    Figure imgb0002
     B is a methyl methacrylate-ethyl methacrylate copolymer with a methyl methacrylate content of approx. 80%.
  • 11. A 30% aqueous dispersion of a perfluoro resin mixture, which is composed of 9 parts of the copolymer A described in (1), 6 parts of the copolymer B described in (I) and 5 parts of a perfluoroalkyl group-containing polyurethane C. The polyurethane C has an average molecular weight of 3500 and contains the recurring formula unit
    Figure imgb0003
    Figure imgb0004
     and chain ends of the formula
    Figure imgb0005
     respectively.
    Figure imgb0006
    Figure imgb0007
  • 111. A 40% aqueous dispersion of a perfluororesin mixture composed of 2 parts of a copolymer D, 4 parts of a polycondensate E and 4 parts of paraffin. The copolymer D consists of units of the formula
    Figure imgb0008
    Figure imgb0009
  • E can be obtained by polycondensation of a C 20 fatty acid mixture (2 mol) with hexamethylolmelamine pentamethyl ether (1 mol) and methyldiethanolamine (1 mol).
  • IV. A 40% dispersion of a perfluororesin mixture consisting of 6 parts of the copolymer A described in Example (I), 9 parts of the copolymer B described in Example (I) and 5 parts of a perfluorocarboxylic acid ester F. F consists of monomeric units of the formula
    Figure imgb0010
     the about polyurethane prepolymers of the formula
    Figure imgb0011
     are linked to an average molecular weight of 3000.
  • V. An approximately 10% dispersion of a perfluoro resin, consisting of a copolymer with units of the formula
    Figure imgb0012
     with n = 4, 6, 8, 10, 12, 14.

Neben Wasser können auch noch in geringeren Mengen organische Lösungsmittel der Dispersion zugegeben werden, um ein besonders günstiges Verhalten beim Auftragen auf die Faser zu erhalten.In addition to water, organic solvents can also be added to the dispersion in smaller amounts in order to obtain particularly favorable behavior when applied to the fiber.

Die Ausrüstung ist auf jeder Art von Fasern, also auf Fasern aus Chemiefaserstoffen auf organischer und anorganischer Basis und auf Naturfaserstoffen wirksam.The finish is effective on all types of fibers, i.e. fibers made of synthetic and organic and inorganic fibers and natural fibers.

Das erfindungsgemässe Behandlungsmittel wird in einer Menge von 0,5-2 Gew.-% - bezogen auf das Fasermaterial - eingesetzt.The treatment agent according to the invention is used in an amount of 0.5-2% by weight, based on the fiber material.

Die Applikation der Ausrüstungsprodukte kann entweder vor, während oder nach der Einfärbung des Textils oder anschliessender weiterer Veredlungsschritte erfolgen oder nachträglich nach erfolgter Verarbeitung als Bezugs-, Polster- oder Bodenbelagstextil durch Behandlung in der Flotte, Klotzen oder Aufsprühen.The finishing products can be applied either before, during or after the dyeing of the textile or subsequent further finishing steps, or subsequently after processing as a cover, upholstery or floor covering textile by treatment in the liquor, padding or spraying.

Eine weitere Methode zum Aufbringen des erfindungsgemässen Mittels auf das Fasermaterial besteht darin, diese zusammen mit einem Reinigungsmittel zu verwenden, besonders dann, wenn das zu behandelnde Textil durch Gebrauch oder vorhergegangene Verarbeitungsschritte verschmutzt wurde. Vorzugsweise erfolgt die Ausrüstung bisher noch nicht vom Hersteller ausgerüsteter Ware nach ihrer Nassreinigung durch Aufsprühen der Zubereitung auf die Ware.Another method of applying the agent according to the invention to the fiber material is to use it together with a cleaning agent, especially if the textile to be treated has been soiled by use or previous processing steps. It is preferable to finish goods that have not been equipped by the manufacturer after wet cleaning by spraying the preparation onto the goods.

Die nachfolgenden Beispiele sollen die Erfindung näher erläutern, ohne sie dadurch einzuschränken (Prozent bzw. Teilangaben beziehen sich auf Gew.-% bzw. Gew.-Teile).The following examples are intended to explain the invention in greater detail without restricting it (percentages or parts given relate to% by weight or parts by weight).

Beispiel 1example 1

Eine Polyamid Tuftingware (Schlinge, 100% Polyamid) mit einem Polgewicht von 300 g/m2 wurde nach dem Färben vor dem Trocknen durch Aufsprühen mit Hilfe einer Einstoff-Sprühanlage aufgerüstet und anschliessend bei 125°C während 5 Minuten auf einem Spannrahmen getrocknet, anschliessend während 24 Stunden bei 23°C und 65% relativer Luftfeuchtigkeit klimatisiert. Als Ausrüstungsmittel wurden hierzu verwendet:

  • 1) 0,25%, bezogen auf das Polgewicht der Teppichware, einer 50% wässrigen Verdünnung (mit 1 % Ethylacetat als Zusatz) einer Perfluorharzdispersion entsprechend I.
  • 2) 0,75%, bezogen auf das Polgewicht der Teppichware, einer Verdünnung einer Methylsilsesquioxanzubereitung (gemäss DE-A 3 004 824, Beispiel 2)
  • 3) 1,00%, bezogen auf das Polgewicht der Teppichware, der erfindungsgemässen Zubereitung (0,25% entsprechend 1) und (0,75% entsprechend 2)).
A polyamide tufting fabric (loop, 100% polyamide) with a pile weight of 300 g / m 2 was upgraded after dyeing before drying by spraying with the aid of a one-component spraying system and then dried at 125 ° C. for 5 minutes on a tenter frame, then Air-conditioned for 24 hours at 23 ° C and 65% relative humidity. The following were used as equipment:
  • 1) 0.25%, based on the pile weight of the carpet, a 50% aqueous dilution (with 1% ethyl acetate as an additive) of a perfluororesin dispersion corresponding to I.
  • 2) 0.75%, based on the pile weight of the carpet, of a dilution of a methylsilsesquioxane preparation (according to DE-A 3 004 824, Example 2)
  • 3) 1.00%, based on the pile weight of the carpet, of the preparation according to the invention (0.25% corresponding to 1) and (0.75% corresponding to 2)).

Aus den so vorbehandelten Materialien wurden Muster zur Prüfung folgender Effekte entnommen :

  • a) Wasserabweisung: Einzelne Tropfen destillerten Wassers wurden auf den Teppich aufgebracht (der Durchmesser jedes Tropfens betrug etwa 5 mm) und die Eindringzeit in den Teppichpol gemessen.
  • b) Abweisung gegen Wasser/Alkohol-Gemisch: Einzelne Tropfen einer Mischung aus 20 Teilen Isopropanol und 80 Teilen destillierten Wassers wurden auf den Teppich aufgebracht (der Durchmesser jedes Tropfens betrug etwa 5 mm) und die Eindringzeit in den Teppichpol gemessen.
  • c) Ölabweisung (gemäss AATCC 118-1966). Das Prüfmuster wird auf eine horizontale, glatte Oberfläche gelegt, und mit Hilfe einer Tropfpipette ein kleiner Tropfen (Tropfendurchmesser etwa 5 mm) der Testflüssigkeiten 1 bis 8 auf verschiedene Stellen des Prüfmusters aufgetragen und gemäss Vorschrift nach jeweils 30 Sekunden bewertet. Die AATCC-Ölabweisungsstufe eines Testgewebes ist die Höchstzahl derjenigen Testflüssigkeit, die innerhalb einer Zeitspanne von 30 Sekunden das Testmaterial nicht benetzt oder darin eindringt.
  • d) Schmutzabweisung (Laboranschmutztest in Anlehnung an DIN 54 324, Stuhlrollenversuch):
Samples for testing the following effects were taken from the materials pretreated in this way:
  • a) Water repellency: Individual drops of distilled water were applied to the carpet (the diameter of each drop was about 5 mm) and the penetration time into the carpet pole was measured.
  • b) Repellency against water / alcohol mixture: Individual drops of a mixture of 20 parts of isopropanol and 80 parts of distilled water were applied to the carpet (the diameter of each drop was about 5 mm) and the penetration time into the carpet pole was measured.
  • c) Oil repellency (according to AATCC 118-1966). The test sample is placed on a horizontal, smooth surface, and with the help of a dropper, a small drop (drop diameter about 5 mm) of test liquids 1 to 8 is applied to various points on the test sample and evaluated according to the instructions after 30 seconds. The AATCC oil repellency level of a test fabric is the maximum number of test liquid that does not wet or penetrate the test material within a period of 30 seconds.
  • d) Dirt repellency (laboratory soiling test based on DIN 54 324, chair roll test):

Aus der behandelten Teppichware wurden gemäss den DIN-Vorschriften Muster entnommen und mit 10 g eines synthetischen Schmutzes folgender Zusammensetzung angeschmutzt:

Figure imgb0013
Samples were taken from the treated carpet goods in accordance with the DIN regulations and soiled with 10 g of synthetic dirt of the following composition:
Figure imgb0013

Nach einer 40stündigen Behandlung in einer Porzellan-Kugelmühle wird die obige Mischung getrocknet, grob zerkleinert, in einer Pulvermühle gemahlen und abschliessend mittels Siebmaschine durch ein Sieb mit einer Maschenweite von 100 µm gesiebt.After a 40-hour treatment in a porcelain ball mill, the above mixture is dried, roughly crushed, ground in a powder mill and then sieved through a sieve with a mesh size of 100 μm using a sieving machine.

Die Belastung der Proben erfolgt nach dem Stuhlrollenversuch, der in der DIN 54 324 ausführlich beschrieben ist, bei einer Rollenbelastung von insgesamt 60 kg und einer Änderung der Rollendruckrichtung nach jeweils 50 Umdrehungen.The samples are loaded after the chair roller test, which is described in detail in DIN 54 324, with a total roller load of 60 kg and a change in the roller pressure direction after every 50 revolutions.

Die Prüfergebnisse sind in der folgenden Tabelle wiedergegeben:

Figure imgb0014
Figure imgb0015
 The test results are shown in the following table:
Figure imgb0014
Figure imgb0015

Beispiel 2Example 2

Eine Polyester Tuftingware (Schlinge, 100%, PES) mit einem Polgewicht von 400 g/m2 wurde, wie in Beispiel 1 angegeben, behandelt.

Figure imgb0016
A polyester tufted fabric (loop, 100%, PES) with a pile weight of 400 g / m 2 was treated as indicated in Example 1.
Figure imgb0016

Beispiel 3Example 3

Eine Polyacryl Tuftingware (Schlinge, 100%, PAC) mit einem Polgewicht von 500 g/m2 wurde wie in Beispiel 1 angegeben behandelt.

Figure imgb0017
A polyacrylic tufting fabric (loop, 100%, PAC) with a pile weight of 500 g / m 2 was treated as indicated in Example 1.
Figure imgb0017

Beispiel 4Example 4

Ein Polyacryl-Markisenstoff (Quadratmetergewicht 280 g) wurde nach dem Färben und nach dem Trocknen im Foulard imprägniert. Die Flottenaufnahme betrug 80%. Anschliessend wurde während 1,5 Minuten bei 120°C auf dem Spannrahmen getrocknet und darauf folgend 48 Stunden lang bei 20-22°C und einer relativen Luftfeuchtigkeit von 65% klimatisiert. Als Ausrüstungsmittel wurden hierzu verwendet:

  • 1) Ein Textilimprägniermittel, enthaltend eine kolloidale Suspension eines Organosilsesquioxans aus Einheiten der Formel R Si03/2 (R = Methyl) und von Kieselsäure mit Si02-Einheiten, gemäss Beispiel 1 der DE-AS (3 004 824)
  • 2) Ein Textilausrüstungsmittel, wie unter II beschrieben
  • 3) Eine Mischung aus 1) und 2) im Verhältnis 75:25
  • 4) Eine Mischung aus 1) und 2) im Verhältnis 50:50
  • 5) Eine Mischung aus 1) und 2) im Verhältnis 25:75.
A polyacrylic awning fabric (weight 280 g) was impregnated after dyeing and after drying in a padder. The fleet uptake was 80%. It was then dried on the stenter at 120 ° C for 1.5 minutes and then air-conditioned for 48 hours at 20-22 ° C and a relative humidity of 65%. The following were used as equipment:
  • 1) A textile impregnating agent containing a colloidal suspension of an organosilsesquioxane composed of units of the formula R Si0 3/2 (R = methyl) and of silica with Si0 2 units, according to Example 1 of DE-AS (3 004 824)
  • 2) A textile finishing agent as described under II
  • 3) A mixture of 1) and 2) in the ratio 75:25
  • 4) A mixture of 1) and 2) in the ratio 50:50
  • 5) A mixture of 1) and 2) in the ratio 25:75.

Die Konzentration der angewendeten Ausrüstungsmittel betrug in allen Fällen 10 g/I.The concentration of the equipment used was 10 g / l in all cases.

Nach beendeter Klimatisierung wurden aus den vorbehandelten Materialien Muster zur Prüfung der in Beispiel 1 beschriebenen Effekte entnommen:

  • a) Wasserabweisung
  • b) Abweisung gegen Wasser/Alkohol-Gemisch (29% Isopropanol/80% Wasser)
  • c) Ölabweisung gemäss AATCC 118-1966.
After the air conditioning had been completed, samples were taken from the pretreated materials to test the effects described in Example 1:
  • a) Water repellency
  • b) Rejection against water / alcohol mixture (29% isopropanol / 80% water)
  • c) Oil repellency according to AATCC 118-1966.

Die Prüfergebnisse sind in der folgenden Tabelle wiedergegeben:

Figure imgb0018
The test results are shown in the following table:
Figure imgb0018

Beispiel 5Example 5

Eine Polyamid Tuftingware (Velour, 100% PA) mit einem Quadratmetergewicht von 700 g wurde, wie in Beispiel 1, angegeben, behandelt.A polyamide tufted fabric (velor, 100% PA) with a weight per square meter of 700 g was treated as indicated in Example 1.

Als Ausrüstungsmittel wurden hierzu verwendet:

  • 1. Gemäss Beispiel 1 der DE-OS 3 004 824
  • 2. Ein Textilausrüstungsmittel wie unter V beschrieben
  • 3. Eine Mischung aus 1 und 2 im Verhältnis 75:25
  • 4. Eine Mischung aus 1 und 2 im Verhältnis 50:50
The following were used as equipment:
  • 1. According to Example 1 of DE-OS 3 004 824
  • 2. A textile finishing agent as described under V.
  • 3. A mixture of 1 and 2 in a ratio of 75:25
  • 4. A mixture of 1 and 2 in a ratio of 50:50

Aus den so vorbehandelten Materialien wurden Muster zur Prüfung folgender in Beispiel 1 beschriebenen Effekte entnommen:

  • a) Wasserabweisung
  • b) Abweisung gegen Wasser/Alkohol-Gemisch (20% Isopropanol/80% Wasser)
  • c) Ölabweisung gemäss AATCC 118-1966
  • d) Schmutzabweisung (Laboranschmutztest in Anlehnung an DIN 54 324, Stuhlrollenversuch)
Samples for testing the following effects described in Example 1 were taken from the materials pretreated in this way:
  • a) Water repellency
  • b) Rejection against water / alcohol mixture (20% isopropanol / 80% water)
  • c) Oil repellency according to AATCC 118-1966
  • d) Dirt repellency (laboratory soil test based on DIN 54 324, chair roll test)

Die Prüfergebnisse sind in der folgenden Tabelle wiedergegeben:

Figure imgb0019
The test results are shown in the following table:
Figure imgb0019

Claims (3)

1. Textile finishing agent, characterised by a content of
A) 50 to 80 parts by weight of an aqueous colloidal suspension, in the form of a sol, of organosil- sesquioxanes of units of the formula RSi03/2 (R = an alkyl radical which has up to 7 carbon atoms and is optionally substituted by halogen, or amino, mercapto or epoxy groups) and/or cocondensates of hydrolysates of tetraalkoxysilanes with organotri- alkoxysilanes having RSi03/2 or Si02 units and
B) 20 to 50 parts by weight of an aqueous dispersion of an organic polymer resin which contains perfluoroalkyl groups with 3 to 20 C atoms, it being possible for the perfluoroalkyl groups to contain, in addition to fluorine atoms, at most 1 hydrogen atom or chlorine atom per 2 C atoms and for the perfluoroalkyl chain to be interrupted by oxygen, the aqueous dispersion containing 5 to 50% by weight of a fluorine-group-containing organic polymer resin with a fluorine content of 0.2 to 40% by weight.
2. Textile finishing agent according to Claim 1, characterised in that the perfluoroalkyl groups are bonded to an organic polymer which has been formed by polymerisation from acrylate, isocyanate and/or carboxylic acid ester.
3. Process for finishing textile materials, characterised in that the textile material is finished with an agent according to one of Claims 1 or 2.
EP19840101888 1983-03-03 1984-02-23 Textile auxiliaries Expired EP0121078B1 (en)

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DE3307420A1 (en) 1984-09-13
US4781844A (en) 1988-11-01
DE3461660D1 (en) 1987-01-22

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