EP0314944B1 - Finishing composition and process for the treatment of fiber materials - Google Patents

Finishing composition and process for the treatment of fiber materials Download PDF

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Publication number
EP0314944B1
EP0314944B1 EP88116823A EP88116823A EP0314944B1 EP 0314944 B1 EP0314944 B1 EP 0314944B1 EP 88116823 A EP88116823 A EP 88116823A EP 88116823 A EP88116823 A EP 88116823A EP 0314944 B1 EP0314944 B1 EP 0314944B1
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Prior art keywords
weight
process according
component
dispersion
treatment composition
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EP88116823A
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German (de)
French (fr)
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EP0314944A3 (en
EP0314944A2 (en
Inventor
Hans-Burkhardt Vogel
Franz Mosch
Erich Rössler
Michael Dr. Bernheim
Johan Emiel De Witte
Rudolf Jozef Dams
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3M Co
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Minnesota Mining and Manufacturing Co
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Priority to AT88116823T priority Critical patent/ATE95584T1/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
    • D06M15/564—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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • 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
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain

Definitions

  • the present invention describes aqueous finishing agents for the soft hydrophobic / oleophobic treatment of fiber materials based on perfluoroaliphatic compositions and extenders.
  • a method for soft hydrophobic / oleophobic treatment is also claimed.
  • Finishing agents have now been found which can be used for the simultaneous particularly smooth and soft hydrophobic / oleophobic treatment of fiber materials. These finishing agents contain perfluoroaliphatic group-containing hydrophobic / oleophobic agents, selected polyethylene emulsions and fluorine-free soft handle extender emulsions in selected proportions.
  • finishing agents of this invention namely the perfluoroaliphatic group-containing agent, the polyethylene emulsion and the fluorine-free polysiloxane softener extender are either available as a finished formulation or are added individually to the finishing bath. In this way, finishing agents are created which, surprisingly, are distinguished by overall very good effects, which also have excellent washing and dry cleaning resistance.
  • the present invention therefore describes in claims 1 to 10 aqueous finishing agents for the soft hydrophobic / oleophobic treatment of fiber materials. A method for the soft hydrophobic / oleophobic treatment of the fiber materials is then claimed in claims 11 to 13.
  • Ingredient A) is a hydrophobic / oleophobic agent containing perfluoroaliphatic groups, many of which are commercially available and which in the finished formulation have at least 5% by weight, in particular 5.5 to 15% by weight, very particularly preferably 7 to Contain 12% by weight fluorine.
  • the perfluoroaliphatic group R f can be straight-chain, branched-chain or, if the length is appropriate, also cyclic be. Combinations of these are of course also conceivable for R f .
  • the basic structure of the perfluoroaliphatic radical can contain oxygen and / or trivalent nitrogen heteroatoms in the chain, bound only to carbon atoms.
  • fluoroaliphatic agents are well known to those skilled in the art and he will have no difficulty in using the useful products.
  • the reaction of perfluoroaliphatic thioglycols with diisocyanates results in polyurethanes containing perfluoroaliphatic groups.
  • These products are typically used in aqueous dispersion for fiber treatment.
  • Such reaction products are described, for example, in US Pat. No. 4,054,592.
  • N-methylol condensation products containing perfluoroaliphatic groups are N-methylol condensation products containing perfluoroaliphatic groups. These compounds also belong to the prior art and are described in US Pat. No. 4,477,498, where the emulsification of such products is also discussed in detail.
  • the polycarbodiimides containing perfluoroaliphatic groups (R f groups) are prepared, for example, by reacting perfluoroaliphatic sulfonamide alkanols with polyisocyanates in the presence of suitable catalysts.
  • This class of compounds can also be used alone, but mostly it is used with other compounds containing R f groups, especially together with the (co) polymers. And this addresses another group of compounds that can be used in dispersion as component A).
  • fluoroaliphatic radical-containing polymers can be used, with condensation polymers such as polyesters and polyamides containing corresponding perfluoroaliphatic groups, and especially (co) polymers based on, for example, R f acrylates and R f methacrylates, different fluorine-free vinyl compounds being used as comonomers.
  • condensation polymers such as polyesters and polyamides containing corresponding perfluoroaliphatic groups
  • polymers based on, for example, R f acrylates and R f methacrylates different fluorine-free vinyl compounds
  • fluorochemical compounds can also be used as constituent A), for example guanidines containing R f groups (US Pat. No. 4,540,479), allophanates containing R f groups (US Pat. No. 4,606,737) and Biurete containing R f groups (US-A 4,668,406). These classes of component A) are mostly used in combination.
  • the active compounds of component A) generally have one or more perfluoroaliphatic radicals with preferably at least 4, in particular 6 to 14, carbon atoms.
  • Component A) is used in the finishing agents according to the invention in amounts of 25 to 65% by weight, based on the finishing agent. Since the components A) preferably contain about 7 to 12% by weight of fluorine, agents which have 30 to 55% by weight of these components are particularly suitable.
  • the emulsifiable polyethylene (polyethylene wax) contained in component B) is known and is described in detail in the prior art (DE-A-2 359 966, DE-A 2 824 716 and DE-A 1 925 993).
  • the emulsifiable polyethylene is one with functional groups, in particular COOH groups, which can be partially esterified. These functional groups are introduced by oxidation of the polyethylene.
  • functional groups in particular COOH groups, which can be partially esterified. These functional groups are introduced by oxidation of the polyethylene.
  • the emulsifiable polyethylenes contained in component B) have a density of at least 0.92 g / cm3 and an acid number at 20 ° C from at least 5 to.
  • the finishing agents according to the invention are particularly preferred of those emulsifiable polyethylenes which have a density at 20 ° C. of 0.95 to 1.05 g / cm 3, an acid number of 10 to 60 and a saponification number of 15 to 80.
  • This material is generally commercially available in the form of scales, lozenges and the like.
  • Component B that is to say the dispersion of the emulsifiable polyethylene, is used in the finishing agents in amounts of 10 to 35% by weight, based on the finishing agent and based on a 20 to 35% dispersion (based on polyethylene wax). It has been shown that higher amounts of component B) make the soft handle even more pleasant, flowing, even softer, so that amounts of 20 to 35% by weight of component B), based on the overall finishing agent, are particularly good are preferred.
  • the polyethylene wax is used in the form of emulsions. Different emulsifiers are required for this. These emulsifiers can support the soft hand effect of the finishing agents.
  • Modified hydrogen alkyl polysiloxanes in the form of aqueous dispersions are suitable as component C).
  • component C Modified hydrogen alkyl polysiloxanes in the form of aqueous dispersions.
  • compounds which are obtained by modification of hydrogen methyl polysiloxane with a long-chain alkyl radical are suitable as fluorine-free soft-grip extenders.
  • This alkyl radical should contain an average of at least 8 carbon atoms, in particular 8 to 18 carbon atoms. This condition does not preclude the presence of low-chain alkyl radicals, but it should be noted that the average carbon chain length is at least 8 carbon atoms. Compounds of this type are described in the aforementioned US-A-4,004,059.
  • those components C) which are modified to an even greater extent are particularly preferred, ie which, in addition to the above-mentioned groups, also include epoxyalkyl groups and possibly additionally aryl, in particular phenyl, groups contained in the molecule (US-A-4,625,010).
  • Such compounds then have an Si-H content of approximately 0.02 to 6, in particular 0.3 to 1.8% by weight, an epoxy number of approximately 0.01 to 0.06 and, moreover, hydrogen per g-atom of the siloxane, at least 0.2 g atom of the same is substituted by an alkyl radical (see above).
  • the constituents C) are present as an average of 25 to 40% dispersions and based on these dispersions 25 to 40% by weight, in particular 25 to 35% by weight, based on the finishing agent, of the component C) are used.
  • components C are prepared in a known manner (see the literature mentioned).
  • emulsifiers there are basically no restrictions with regard to dispersion or dispersion polymerization, i.e. Both nonionic and conventional cationic and anionic emulsifiers can be used.
  • the finished dispersions that is to say the constituents A), B) and C
  • the finishing agent according to the invention and, in addition, are frequently used in combination with other constituents
  • the emulsifiers that can be used individually are well known and do not require any special explanation.
  • the emulsifiers are used in customary amounts. In general, the amount of emulsifier is 3 to 50, preferably 8 to 40,% by weight, based on the respective solid.
  • finishing agents can be produced in a simple manner by combining components A) to C) in the stated amounts. These agents have the advantage of being a stable one-component finishing agent.
  • the fibers thus produced are used directly from fiber materials.
  • the amounts used depend on the desired effects and are usually 40 to 100, in particular 50 to 80 g / l, based on a 25 to 35% by weight finishing agent.
  • the use of the agents according to the invention is preferred due to the presence of a one-component finishing agent.
  • the equipment itself is carried out according to known methods.
  • fiber materials of all kinds can be finished as well as according to the known methods.
  • textiles are to be mentioned as fiber materials, these textiles in turn being particularly suitable, which consist of cellulose fibers or at least partially contain cellulose fibers.
  • synthetic fibers such as polyester, polyamide or polyacrylonitrile fibers and wool can also be considered as additional fibers.
  • the oil and water repellent finishing of cotton / polyester blended fabrics is particularly critical and it is precisely here that the finishing agents according to the invention show their superiority over the prior art.
  • Equipment I The following components are mixed together to produce an equipment (equipment I):
  • a commercially available dispersion emulsifier: polyethoxylated quaternary ammonium salt
  • emulsifier polyethoxylated quaternary ammonium salt
  • polymer X see DE-A 2 310 801
  • R f polycarbodiimide emulsion see example 1, DE-A 2 310 801 in a weight ratio of 2: 1.
  • polyetylene wax dispersion 50% nonylphenol ethoxylated with an average of 15 moles of ethylene oxide, based on polyethylene wax, as an emulsifier; polyethylene wax with a density at 20 ° C. of about 1, an acid number of about 13 and a saponification number of about 22).
  • an aqueous finishing liquor is prepared as follows: 60 g / l finishing agent I, 40 g / l of an approx. 60% aminoplast resin solution (contains dimethylol dihydroxyethylene urea etherified with methanol and pentamethylolmelamine in a ratio of 12: 1 and approx. 5% neutral salt), 6 g / l of a 30% zinc nitrate solution (pH approx. 1.0) and 2 g / l 60% acetic acid.
  • components A 1) to C 1) of the fleet are added separately but in equal amounts.
  • component C 1 Like fleet II, but instead of component C 1) the same amount of ⁇ , ⁇ -dihydroxy-polydimethylsiloxane (viscosity (20 ° C.) approx. 5000 mPa.s) is used in aqueous dispersion.
  • a polyester / cotton jacket Popeline 67/33 (approx. 210 g / m2) was padded with liquors I to V (liquor absorption approx. 65%), then dried at 110 ° C. for 10 minutes and condensed at 150 ° C. for 5 minutes.
  • the results of the equipment are summarized in the table below, the laundry being the usual 40 ° C. household machine wash and the chemical cleaning (CR) washing in the presence of 2 g / l of a conventional cleaning booster and 2 g / l of water (Fleet ratio 1:10).
  • the measurements were carried out after 5 days of exposure in a normal climate.
  • aqueous liquors are prepared with the finishing agents II and II a: 90 or 100 g / l of finishing agent II or IIa, 30 g / l of a 60% aqueous solution of pentamethylolmelamine trimethyl ether, 6 g / l of the catalyst solution mentioned in Example 1 and 2 g / l of 60% acetic acid ( Fleets I and II).
  • Example 1 The textile material described in Example 1 is finished with the two liquors produced and the following effects are obtained, a comparison based on the prior art (Fleet III with 80 g / l of an agent from A 2) and C2), ie without polyethylene dispersion) was also added.
  • a cotton fabric (170 g / m2) is soaked in an aqueous liquor which contains the following constituents, squeezed to a liquor absorption of about 70%, dried briefly at 105 ° C. and condensed for 5 minutes at 155 ° C.
  • Example 1 The fabric described in Example 1 is immersed in a liquor of the following composition, squeezed to a liquor absorption of 55%, dried and condensed at 160 ° C. for 3 minutes:
  • the washing and cleaning resistance is given in the same way as in the other examples.

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

Description

Die vorliegende Erfindung beschreibt wäßrige Ausrüstungsmittel zur weichen Hydrophob/Oleophob-Behandlung von Fasermaterialien auf Basis von perfluoraliphatischen Zusammensetzungen und Extendern. Außerdem wird ein Verfahren zur weichen Hydrophob/Oleophob- Behandlung beansprucht.The present invention describes aqueous finishing agents for the soft hydrophobic / oleophobic treatment of fiber materials based on perfluoroaliphatic compositions and extenders. A method for soft hydrophobic / oleophobic treatment is also claimed.

Die wasser-, öl- und schmutzabweisende Ausrüstung mit fluorchemischen Mitteln oder Zusammensetzungen ist seit langem bekannt (siehe Chwala/Anger "Handbuch der Textilhilfsmittel", 1977, Verlag Chemie, Weinheim, Seiten 470 ff). Ein wesentlicher Nachteil dieser Ausrüstungen ist ihr hoher Preis. Man hat deshalb schon bald sogenannte Extender entwickelt, um in erster Linie die Kosten dieser Ausrüstung zu senken und später um außerdem in grifflicher Hinsicht Verbesserungen zu erhalten. Zuerst wurden für diesen Zweck metallsalzhaltige Paraffinemulsionen, fettmodifizierte Kunstharze, Wachse und ähnliche Produkte eingesetzt, die jedoch allesamt bei Beurteilung der Summe der Effekte nicht überzeugen können. Die danach entwickelten Additionsprodukte von u.a. Olefinen, Vinyl-und Allylestern aliphatischer geradkettiger oder verzweigtkettiger Säuren an Wasserstoffpolysiloxane (US-A 4 004 059) brachten zwar eine Verbesserung der Wasser- und Ölabweisung, waren aber im Hinblick auf die heute geforderten Permanenzen noch nicht ganz überzeugend und konnten vor allem hinsichtlich des gewünschten Soft-hand-Effektes ebenfalls die gestellten Anforderungen nicht erfüllen.The water, oil and dirt repellent finish with fluorochemical agents or compositions has long been known (see Chwala / Anger "Handbook of Textile Aids", 1977, Verlag Chemie, Weinheim, pages 470 ff). A major disadvantage of this equipment is its high price. So so-called extenders were soon developed in order to reduce the cost of this equipment first and later and also to obtain improvements in terms of convenience. First, metal salt-containing paraffin emulsions, fat-modified synthetic resins, waxes and similar products were used for this purpose, but all of these cannot convince when evaluating the sum of the effects. The addition products of olefins, vinyl and allyl esters of aliphatic straight-chain or branched-chain acids on hydrogen polysiloxanes (US-A 4 004 059) brought about an improvement in water and oil repellency, but were not yet completely convincing in view of the permanences required today and, especially with regard to the desired soft-hand effect, were also able to achieve the same Not meet requirements.

Es wurden nun Ausrüstungsmittel gefunden, die zur gleichzeitigen besonders glatten und weichen Hydrophob/Oleophob-Behandlung von Fasermaterialien einsetzbar sind. Diese Ausrüstungsmittel enthalten perfluoraliphatische Gruppen enthaltende Hydrophob/Oleophob-Mittel, ausgewahlte Polyethylenemulsionen und fluorfreie Weichgriffextenderemulsionen in ausgewählten Mengenverhältnissen.Finishing agents have now been found which can be used for the simultaneous particularly smooth and soft hydrophobic / oleophobic treatment of fiber materials. These finishing agents contain perfluoroaliphatic group-containing hydrophobic / oleophobic agents, selected polyethylene emulsions and fluorine-free soft handle extender emulsions in selected proportions.

Die Ausrüstungsmittel dieser Erfindung, nämlich das perfluoraliphatische Gruppen enthaltende Mittel, die Polyethylenemulsion und der fluorfreie Polysiloxan-weichgriffextender stehen entweder als fertige Formulierung zur Verfügung, oder sie werden individuell dem Ausrüstungsbad zugesetzt. Auf diese Weise entstehen Ausrüstungsmittel, die sich überraschenderweise durch insgesamt gesehen sehr gute Effekte, die zudem eine hervorragende Wasch- und Chemisch-Reinigungsbeständigkeit aufweisen, auszeichnen. Die vorliegende Erfindung beschreibt demnach in den Patentansprüchen 1 bis 10 wäßrige Ausrüstungsmittel zur weichen Hydrophob/Oleophob-Behandlung von Fasermaterialien. Ein Verfahren zur weichen Hydrophob/Oleophob-Behandlung der Fasermaterialien wird dann in den Patentansprüchen 11 bis 13 beansprucht.The finishing agents of this invention, namely the perfluoroaliphatic group-containing agent, the polyethylene emulsion and the fluorine-free polysiloxane softener extender are either available as a finished formulation or are added individually to the finishing bath. In this way, finishing agents are created which, surprisingly, are distinguished by overall very good effects, which also have excellent washing and dry cleaning resistance. The present invention therefore describes in claims 1 to 10 aqueous finishing agents for the soft hydrophobic / oleophobic treatment of fiber materials. A method for the soft hydrophobic / oleophobic treatment of the fiber materials is then claimed in claims 11 to 13.

Bei dem Bestandteil A) handelt es sich um perfluoraliphatische Gruppen enthaltende Hydrophob/Oleophobmittel, von denen zahlreiche im Handel erhältlich sind und die in der fertigen Formulierung mindestens 5 Gew.%, insbesondere 5,5 bis 15 Gew.%, ganz besonders bevorzugt 7 bis 12 Gew.% Fluor enthalten. Die perfluoraliphatische Gruppe Rf kann geradkettig, verzweigtkettig oder bei entsprechender Länge auch cyclisch sein. Natürlich sind auch Kombinationen daraus für Rf denkbar. Das Grundgerüst des perfluoraliphatischen Radikals kann dabei in der Kette Sauerstoff- und/oder trivalente Stickstoff-Heteroatome, gebunden allein an Kohlenstoffatome, enthalten. Diese Typen fluoraliphatischer Mittel sind dem Fachmann hinreichend bekannt und er wird keine Schwierigkeiten haben, die brauchbaren Produkte einzusetzen.
Als Beispiele seien folgende genannt:
Durch die Umsetzung von perfluoraliphatischen Thioglykolen mit Diisocyanaten entstehen perfluoraliphatische Gruppen enthaltende Polyurethane. Diese Produkte werden für die Faserbehandlung normalerweise in wäßriger Dispersion angewandt. Derartige Umsetzungsprodukte sind z.B. in der US-A-4 054 592 beschrieben.Ingredient A) is a hydrophobic / oleophobic agent containing perfluoroaliphatic groups, many of which are commercially available and which in the finished formulation have at least 5% by weight, in particular 5.5 to 15% by weight, very particularly preferably 7 to Contain 12% by weight fluorine. The perfluoroaliphatic group R f can be straight-chain, branched-chain or, if the length is appropriate, also cyclic be. Combinations of these are of course also conceivable for R f . The basic structure of the perfluoroaliphatic radical can contain oxygen and / or trivalent nitrogen heteroatoms in the chain, bound only to carbon atoms. These types of fluoroaliphatic agents are well known to those skilled in the art and he will have no difficulty in using the useful products.
The following are examples:
The reaction of perfluoroaliphatic thioglycols with diisocyanates results in polyurethanes containing perfluoroaliphatic groups. These products are typically used in aqueous dispersion for fiber treatment. Such reaction products are described, for example, in US Pat. No. 4,054,592.

Eine andere Gruppe von Verbindungen im Bestandteil A) sind perfluoraliphatische Gruppen enthaltende N-Methylolkondensationsprodukte. Auch diese Verbindungen gehören zum Stand der Technik und sind in der US-A 4 477 498 beschrieben, wo auch auf die Emulgierung derartiger Produkte eingehend eingegangen wird.
Die perfluoraliphatischen Gruppen (Rf-Gruppen) enthaltenden Polycarbodiimide werden z.B. durch Umsetzung von perfluoraliphatischen Sulfonamidalkanolen mit Polyisocyanaten in Gegenwart geeigneter Katalysatoren hergestellt. Diese Verbindungsklasse kann auch allein verwendet werden, aber zumeist wird sie mit anderen Rf-Gruppen enthaltenden Verbindungen, vor allem zusammen mit den (Co)polymeren eingesetzt. Und damit ist eine weitere Gruppe von Verbindungen, die in Dispersion als Bestandteil A) verwendbar ist, angesprochen. Unter diesen Verbindungen können alle bekannten, fluoraliphatische Reste enthaltenden Polymeren verwendet werden, wobei auch Kondensationspolymere, wie Polyester und Polyamide, die entsprechende perfluoraliphatische Gruppen enthalten, und vor allem (Co)polymere auf Basis von z.B. Rf-Acrylaten und Rf-Methacrylaten, wobei als Comonomere unterschiedliche fluorfreie Vinylverbindungen Verwendung finden, in Frage kommen. In der DE-A- 2 310 801 (siehe auch GB-A-1.413.051/052) werden diese Verbindungen unter weiterer Literaturbenennung ausführlich besprochen und auch die Herstellung von Rf-Gruppen enthaltenden Polycarbodiimiden sowie die Mischung dieser Verbindungen untereinander wird hier ausführlich abgehandelt.Another group of compounds in component A) are N-methylol condensation products containing perfluoroaliphatic groups. These compounds also belong to the prior art and are described in US Pat. No. 4,477,498, where the emulsification of such products is also discussed in detail.
The polycarbodiimides containing perfluoroaliphatic groups (R f groups) are prepared, for example, by reacting perfluoroaliphatic sulfonamide alkanols with polyisocyanates in the presence of suitable catalysts. This class of compounds can also be used alone, but mostly it is used with other compounds containing R f groups, especially together with the (co) polymers. And this addresses another group of compounds that can be used in dispersion as component A). Among these compounds, all known fluoroaliphatic radical-containing polymers can be used, with condensation polymers such as polyesters and polyamides containing corresponding perfluoroaliphatic groups, and especially (co) polymers based on, for example, R f acrylates and R f methacrylates, different fluorine-free vinyl compounds being used as comonomers. In DE-A-2 310 801 (see also GB-A-1.413.051 / 052) these compounds are discussed in detail with further reference to the literature, and the preparation of polycarbodiimides containing R f groups and the mixture of these compounds with one another are dealt with in detail here .

Neben den obengenannten perfluoraliphatischen Gruppen enthaltenden Mitteln können noch weitere fluorchemische Verbindungen als Bestandteil A) verwendet werden, z.B. Rf-Gruppen enthaltende Guanidine (US-A 4.540.479), Rf-Gruppen enthaltende Allophanate (US-A 4.606.737) und Rf-Gruppen enthaltende Biurete (US-A 4.668.406). Diese Klassen an Bestandteil A) werden meistens in Kombination verwendet.In addition to the above-mentioned agents containing perfluoroaliphatic groups, other fluorochemical compounds can also be used as constituent A), for example guanidines containing R f groups (US Pat. No. 4,540,479), allophanates containing R f groups (US Pat. No. 4,606,737) and Biurete containing R f groups (US-A 4,668,406). These classes of component A) are mostly used in combination.

Wie aus der gesamten Literatur zu entnehmen ist, weisen die Aktivverbindungen des Bestandteils A) im allgemeinen einen oder mehrere perfluoraliphatische Reste mit vorzugsweise mindestens 4, insbesondere 6 bis 14 Kohlenstoffatomen auf. Der Bestandteil A) wird dabei in den erfindungsgemäßen Ausrüstungsmitteln in Mengen von 25 bis 65 Gew.%, bezogen auf das Ausrüstungsmittel, eingesetzt. Da die Bestandteile A) bevorzugt etwa 7 bis 12 Gew.% Fluor enthalten, sind Mittel, die von diesen Bestandteilen 30 bis 55 Gew.% aufweisen, besonders geeignet.As can be seen from the entire literature, the active compounds of component A) generally have one or more perfluoroaliphatic radicals with preferably at least 4, in particular 6 to 14, carbon atoms. Component A) is used in the finishing agents according to the invention in amounts of 25 to 65% by weight, based on the finishing agent. Since the components A) preferably contain about 7 to 12% by weight of fluorine, agents which have 30 to 55% by weight of these components are particularly suitable.

Das in dem Bestandteil B) enthaltene emulgierbare Polyethylen (Polyethylenwachs) ist bekannt und im Stand der Technik (DE-A-2 359 966, DE-A 2 824 716 und DE-A 1 925 993) ausführlich beschrieben. In aller Regel handelt es sich bei dem emulgierbaren Polyethylen um solches mit funktionellen Gruppen, insbesondere COOH-Gruppen, die teilweise verestert sein können. Diese funktionellen Gruppen werden durch Oxidation des Polyethylens eingeführt. Es ist aber auch möglich, durch Copolymerisation von Ethylen mit z.B. Acrylsäure die Funktionalität zu erhalten. Die im Bestandteil B) enthaltenen emulgierbaren Polyethylene weisen bei 20°C eine Dichte von mindestens 0,92 g/cm³ und eine Säurezahl von mindestens 5 auf. Besonders bevorzugt sind die erfindungsgemäßen Ausrüstungsmittel solcher emulgierbaren Polyethylene, die eine Dichte bei 20°C von 0,95 bis 1,05 g/cm³, eine Säurezahl von 10 bis 60 und eine Verseifungszahl von 15 bis 80 besitzen. Im Handel ist dieses Material im allgemeinen in Form von Schuppen, Pastillen und ähnliches zu haben. Der Bestandteil B), also die Dispersion des emulgierbaren Polyethylens, wird in den Ausrüstungsmitteln in Mengen von 10 bis 35 Gew. %, bezogen auf das Ausrüstungsmittel und bezogen auf eine 20 bis 35 %ige Dispersion (bezogen auf Polyethylenwachs), eingesetzt. Es hat sich dabei gezeigt, daß durch höhere Mengen an Bestandteil B) der Weichgriff noch angenehmer, noch fließender, noch weicher gestaltet werden kann, so daß Mengen von 20 bis 35 Gew.% an Bestandteil B), bezogen auf das gesamte Ausrüstungsmittel, besonders bevorzugt sind.The emulsifiable polyethylene (polyethylene wax) contained in component B) is known and is described in detail in the prior art (DE-A-2 359 966, DE-A 2 824 716 and DE-A 1 925 993). As a rule, the emulsifiable polyethylene is one with functional groups, in particular COOH groups, which can be partially esterified. These functional groups are introduced by oxidation of the polyethylene. However, it is also possible to obtain the functionality by copolymerizing ethylene with, for example, acrylic acid. The emulsifiable polyethylenes contained in component B) have a density of at least 0.92 g / cm³ and an acid number at 20 ° C from at least 5 to. The finishing agents according to the invention are particularly preferred of those emulsifiable polyethylenes which have a density at 20 ° C. of 0.95 to 1.05 g / cm 3, an acid number of 10 to 60 and a saponification number of 15 to 80. This material is generally commercially available in the form of scales, lozenges and the like. Component B), that is to say the dispersion of the emulsifiable polyethylene, is used in the finishing agents in amounts of 10 to 35% by weight, based on the finishing agent and based on a 20 to 35% dispersion (based on polyethylene wax). It has been shown that higher amounts of component B) make the soft handle even more pleasant, flowing, even softer, so that amounts of 20 to 35% by weight of component B), based on the overall finishing agent, are particularly good are preferred.

Das Polyethylenwachs wird in Form von Emulsionen eingesetzt. Dazu sind unterschiedliche Emulgatoren erforderlich. Diese Emulgatoren können den Soft-hand-effekt der Ausrüstungsmittel unterstützen.The polyethylene wax is used in the form of emulsions. Different emulsifiers are required for this. These emulsifiers can support the soft hand effect of the finishing agents.

Als Bestandteil C) sind modifizierte Wasserstoffalkylpolysiloxane in Form wäßriger Dispersionen geeignet. Vor allem aber kommen als fluorfreie Weichgriffextender Verbindungen in Frage, die durch Modifikation von Wasserstoffmethylpolysiloxan mit einem langkettigen Alkylrest erhalten werden. Dieser Alkylrest soll durchschnittlich mindestens 8 C-Atome, insbesondere 8 bis 18 C-Atome enthalten. Diese Bedingung schließt nicht aus, daß auch niederkettige Alkylreste zugegen sind, doch ist zu beachten, daß die durchschnittliche C-Kettenlänge mindestens 8 Kohlenstoffatome ausmacht. Verbindungen dieser Art werden in der bereits genannten US-A-4.004.059 beschrieben. Ganz besonders aber sind solche Bestandteile C) bevorzugt, die in noch größerem Maße modifiziert sind, d.h. die neben den obengenannten Gruppen noch Epoxyalkylgruppen und evtl. zusatzlich noch Aryl-, insbesondere Phenylgruppen im Molekül enthalten (US-A-4.625.010). Derartige Verbindungen weisen dann einen Si-H-Gehalt von etwa 0,02 bis 6, insbesondere 0,3 bis 1,8 Gew.%, eine Epoxidzahl von etwa 0,01 bis 0,06 auf und außerdem sind je g-Atom Wasserstoff des Siloxans mindestens 0,2 g-Atom desselben durch einen Alkylrest (siehe oben) substituiert.Modified hydrogen alkyl polysiloxanes in the form of aqueous dispersions are suitable as component C). Above all, however, compounds which are obtained by modification of hydrogen methyl polysiloxane with a long-chain alkyl radical are suitable as fluorine-free soft-grip extenders. This alkyl radical should contain an average of at least 8 carbon atoms, in particular 8 to 18 carbon atoms. This condition does not preclude the presence of low-chain alkyl radicals, but it should be noted that the average carbon chain length is at least 8 carbon atoms. Compounds of this type are described in the aforementioned US-A-4,004,059. However, those components C) which are modified to an even greater extent are particularly preferred, ie which, in addition to the above-mentioned groups, also include epoxyalkyl groups and possibly additionally aryl, in particular phenyl, groups contained in the molecule (US-A-4,625,010). Such compounds then have an Si-H content of approximately 0.02 to 6, in particular 0.3 to 1.8% by weight, an epoxy number of approximately 0.01 to 0.06 and, moreover, hydrogen per g-atom of the siloxane, at least 0.2 g atom of the same is substituted by an alkyl radical (see above).

Die Bestandteile C) liegen als durchschnittlich 25 bis 40%ige Dispersionen vor und bezogen auf diese Dispersionen werden von dem Bestandteil C) 25 bis 40 Gew.%, insbesondere 25 bis 35 Gew.%, bezogen auf Ausrüstungsmittel, verwendet.The constituents C) are present as an average of 25 to 40% dispersions and based on these dispersions 25 to 40% by weight, in particular 25 to 35% by weight, based on the finishing agent, of the component C) are used.

Diese Bestandteile C) werden ebenso wie die Bestandteile A) und B) in bekannter Weise hergestellt (siehe genannte Literatur). Hinsichtlich der Emulgatoren bestehen bei der Dispergierung bzw. Dispersionspolymerisation grundsätzlich keine Einschränkungen, d.h. es sind sowohl nichtionogene wie auch übliche kationische und anionische Emulgatoren verwendbar. Aufgrund der Tatsache aber, daß die fertigen Dispersionen, also die Bestandteile A), B) und C) bei der Herstellung des erfindungsgemäßen Ausrüstungsmittels gemischt werden und außerdem zusätzlich noch häufig mit anderen Bestandteilen kombiniert angewandt werden, ist es bevorzugt, zur Herstellung mehr oder weniger nichtionogene oder nur schwach kationische Emulgatoren einzusetzen, um die Gefahr von gegenseitigen Beeinflussungen möglichst gering zu halten. Die im einzelnen einsetzbaren Emulgatoren sind hinreichend bekannt und bedürfen keiner besonderen Erläuterung. Die Emulgatoren werden dabei in üblichen Mengen angewandt. Im allgemeinen beträgt die Emulgatormenge 3 bis 50, vorzugsweise 8 bis 40 Gew.%, bezogen auf den jeweiligen Feststoff.These components C), like components A) and B), are prepared in a known manner (see the literature mentioned). With regard to the emulsifiers, there are basically no restrictions with regard to dispersion or dispersion polymerization, i.e. Both nonionic and conventional cationic and anionic emulsifiers can be used. However, due to the fact that the finished dispersions, that is to say the constituents A), B) and C), are mixed in the preparation of the finishing agent according to the invention and, in addition, are frequently used in combination with other constituents, it is preferred to produce more or less use non-ionic or only weakly cationic emulsifiers to keep the risk of mutual interference as low as possible. The emulsifiers that can be used individually are well known and do not require any special explanation. The emulsifiers are used in customary amounts. In general, the amount of emulsifier is 3 to 50, preferably 8 to 40,% by weight, based on the respective solid.

Die Herstellung der Ausrüstungsmittel gelingt auf einfache Weise durch Zusammengeben der Bestandteile A) bis C) in den angegebenen Mengen. Diese Mittel haben den Vorteil, daß ein stabiles Einkomponentenausrüstungsmittel vorliegt.The finishing agents can be produced in a simple manner by combining components A) to C) in the stated amounts. These agents have the advantage of being a stable one-component finishing agent.

Für das Verfahren zur weichen Hydrophob/Oleophob-Behandlung von Fasermaterialien werden die so hergestellten Mittel direkt eingesetzt. Die verwendeten Mengen richten sich nach den angestrebten Effekten und liegen üblicherweise bei 40 bis 100, insbesondere bei 50 bis 80 g/l, bezogen auf ein 25 bis 35 gew.%-iges Ausrüstungsmittel.For the soft hydrophobic / oleophobic treatment process The fibers thus produced are used directly from fiber materials. The amounts used depend on the desired effects and are usually 40 to 100, in particular 50 to 80 g / l, based on a 25 to 35% by weight finishing agent.

Die Verwendung der erfindungsgemäßen Mittel ist, wie oben bereits ausgeführt, aufgrund des Vorliegens eines Einkomponentenausrüstungsmittels bevorzugt. Es ist aber im Rahmen des vorliegenden Verfahrens auch möglich, mit den entsprechenden Mengen der Bestandteile A), B) und C) die üblicherweise wäßrigen Ausrüstungsflotten anzusetzen und der Fachmann wird keine Mühe haben, auch dann zu den angestrebten hervorragenden Gesamteffekten zu gelangen. Die Ausrüstung selbst erfolgt nach bekannten Methoden.As already stated above, the use of the agents according to the invention is preferred due to the presence of a one-component finishing agent. However, it is also possible in the context of the present process to prepare the usually aqueous finishing liquors with the appropriate amounts of constituents A), B) and C) and the person skilled in the art will have no trouble in achieving the desired overall effects even then. The equipment itself is carried out according to known methods.

Es ist selbstverständlich, daß dem obenbeschriebenen Ausrüstungsbad auch bei dem vorliegenden Verfahren weitere, in der Textilindustrie übliche Hilfsmittel zugefügt werden können. Besonders hervorgehoben seien in diesem Zusammenhang Knitterfreimittel, da hierbei nicht nur die gewünschte Knitterfestigkeit, sondern zusätzlich auch noch eine weitere Stabilisierung der Effekte erzielt wird. Daneben sind aber auch Füllharze, Flammschutzmittel, Schiebefestmittel und ähnliche Produkte sowie gegebenenfalls die außerdem notwendigen Katalysatoren, alle in üblichen Mengen, als Zusatzprodukte zu nennen.It goes without saying that further aids customary in the textile industry can also be added to the finishing bath described above in the present process. In this context, special emphasis should be given to crease-free agents, since not only the desired crease resistance but also a further stabilization of the effects is achieved. In addition, however, fillers, flame retardants, anti-slip agents and similar products and, if necessary, the catalysts which are also necessary, all in customary amounts, are to be mentioned as additional products.

Nach dem vorliegenden Gegenstand können ebenso wie nach den bekannten Verfahren Fasermaterialien aller Art ausgerüstet werden. Als Fasermaterialien sind dabei insbesondere Textilien zu nennen, wobei wiederum diese Textilien besonders gut geeignet sind, die aus Cellulosefasern bestehen oder mindestens teilweise Cellulosefasern enthalten. Als zusätzliche Fasern neben der Cellulose kommen dabei sowohl synthetische Fasern, wie Polyester-, Polyamid- oder Polyacrylnitrilfasern, als auch Wolle in Betracht. Selbstverständlich kann aber das erfindungsgemäße Verfahren auch zur Ausrüstung von reinen Synthesefaser- und Wollfasermaterialien herangezogen werden. Besonders kritisch ist die öl- und wasserabweisende Ausrüstung von Baumwoll/Polyester-Mischgeweben und gerade hierbei zeigen die erfindungsgemäßen Ausrüstungsmittel ihre Überlegenheit gegenüber dem Stand der Technik.According to the present subject matter, fiber materials of all kinds can be finished as well as according to the known methods. In particular, textiles are to be mentioned as fiber materials, these textiles in turn being particularly suitable, which consist of cellulose fibers or at least partially contain cellulose fibers. In addition to cellulose, synthetic fibers such as polyester, polyamide or polyacrylonitrile fibers and wool can also be considered as additional fibers. Of course you can but the method according to the invention can also be used for finishing pure synthetic fiber and wool fiber materials. The oil and water repellent finishing of cotton / polyester blended fabrics is particularly critical and it is precisely here that the finishing agents according to the invention show their superiority over the prior art.

Die Vorteile des erfindungsgemäßen Gegenstandes liegen weniger in den öl- und wasserabweisenden Effekten. Aber schon bei der Beurteilung der Wasch- und Reinigungspermanenzen sind gegenüber dem Stand der Technik (US-A-4.004.059) merkliche Vorteile erkennbar.The advantages of the object according to the invention lie less in the oil and water repellent effects. But already when assessing the washing and cleaning persistence there are noticeable advantages over the prior art (US-A-4,004,059).

Vor allem aber ist bei dem Vergleich des Griffes ohne weiteres eine deutliche Überlegenheit des Anmeldungsgegenstandes festzustellen. Nach dem Stand der Technik war es aufgrund der verwendeten Extender bereits möglich, einen guten bis sehr guten Silikongriff zu erhalten. Es ließ jedoch bei dieser bekannten Ausrüstung die Oberflächenglätte und vor allem die innere Weichheit noch zu wünschen übrig. Bei dem vorliegenden Gegenstand werden auch in dieser Hinsicht alle Anforderungen erfüllt, so daß nunmehr die Erzielung von insgesamt überragenden Soft-hand-Effekten zu nennen ist. Es muß als überraschend angesehen werden, daß vor allem durch den Zusatz des ausgewählten Bestandteiles B) in den angegebenen Mengen noch eine - wenn auch geringe - Steigerung der öl- und wasserabweisenden Effekte, eine merkliche Verbesserung der Permanenzen und vor allem eine beachtliche positive Griffbeeinflussung erreichbar ist, nachdem ja der Silikongriff allein schon allgemein als besonders weich und oberflächenglatt angesehen worden ist. Weiterhin ist als Vorteil die Effektstabilität der vorliegenden Ausrüstungsmittel hervorzuheben.Above all, however, a clear superiority of the subject of the application can be ascertained when comparing the handle. According to the prior art, it was already possible to obtain a good to very good silicone handle due to the extenders used. However, the surface smoothness and above all the inner softness left something to be desired in this known equipment. In the present subject, all requirements are also met in this regard, so that the achievement of outstanding soft-hand effects can now be mentioned. It must be regarded as surprising that, above all, the addition of the selected component B) in the stated amounts can achieve a - albeit slight - increase in the oil- and water-repellent effects, a noticeable improvement in the permanence and, above all, a considerable positive influence on the grip is, after all, the silicone handle has been generally considered to be particularly soft and smooth. Another advantage is the stability of the effects of the present finishing agents.

Die vorliegende Erfindung wird in den nachfolgenden Beispielen näher beschrieben, wobei Teile gleich Gewichtsteile und Prozentangaben gleich Gewichtsprozent sind.The present invention is described in more detail in the examples below, parts being parts by weight and percentages being weight percent.

Beispiel 1example 1

Zur Herstellung eines Ausrüstungsmittels werden folgende Bestandteile zusammengerührt (Ausrüstungsmittel I):The following components are mixed together to produce an equipment (equipment I):

Bestandteil A 1)Part A 1)

55 Teile einer handelsüblichen Dispersion (Emulgator: polyethoxyliertes quaternäres Ammoniumsalz) bestehend aus Polymer X (siehe DE-A 2 310 801) und Rf-Polycarbodiimid-Emulsion (siehe Beispiel 1, DE-A 2 310 801) im Gewichtsverhältnis 2:1.55 parts of a commercially available dispersion (emulsifier: polyethoxylated quaternary ammonium salt) consisting of polymer X (see DE-A 2 310 801) and R f polycarbodiimide emulsion (see example 1, DE-A 2 310 801) in a weight ratio of 2: 1.

Bestandteil B 1)Part B 1)

20 Teile einer handelsüblichen, nichtionogenen, feinteiligen, wäßrigen 20 %-igen Polyetylenwachsdispersion (50% Nonylphenol ethoxyliert mit durchschnittlich 15 Mol Ethylenoxyd, bezogen auf Polyethylenwachs, als Emulgator; Polyethylenwachs mit einer Dichte bei 20°C von ca. 1, einer Säurezahl von etwa 13 und einer Verseifungzahl von etwa 22).20 parts of a commercially available, nonionic, finely divided, aqueous 20% polyetylene wax dispersion (50% nonylphenol ethoxylated with an average of 15 moles of ethylene oxide, based on polyethylene wax, as an emulsifier; polyethylene wax with a density at 20 ° C. of about 1, an acid number of about 13 and a saponification number of about 22).

Bestandteil C 1)Component C 1)

35 Teile einer wäßrigen, nichtionogenen (Emulgator: 3% eines mit 6 Mol Ethylenoxyd ethoxylierten C₁₀-C₁₂-Fettalkohols) 35%-igen Weichgriffextenderdispersion (H- und Epoxyfunktionelles Aryl-Methyl-C₁₂-Alkyl-Polysiloxan mit folgenden Daten: Viskosität (25°C) ca. 1350 mPa.s, Brechungsindex nD²⁵ 1,460-1,465, Si-H-Gehalt ca. 1 Gew.%, Epoxidzahl ca. 0,03, Verhältnis der 2-Phenyl-propyl- zu den C₁₂-Alkylresten ca. 1:5, keine Dimethyl-Si-Gruppen).35 parts of an aqueous, nonionic (emulsifier: 3% of a C₁₀-C₁₂ fatty alcohol ethoxylated with 6 moles of ethylene oxide) 35% soft-handle extender dispersion (H- and epoxy-functional aryl-methyl-C₁₂-alkyl polysiloxane with the following data: viscosity (25 ° C) approx. 1350 mPa.s, refractive index n D ²⁵ 1.460-1.465, Si-H content approx. 1% by weight, epoxy number approx. 0.03, ratio of the 2-phenyl-propyl to the C₁₂-alkyl residues approx 1: 5, no dimethyl-Si groups).

Flotte IFleet I

Mit diesem Ausrüstungsmittel I wird eine wäßrige Ausrüstungsflotte wie folgt angesetzt:
60 g/l Ausrüstungsmittel I,
40 g/l einer ca. 60%-igen Aminoplastharzlösung (enthält mit Methanol veretherten Dimethylol-dihydroxy-ethylenharnstoff und Pentamethylolmelamin im Verhältnis 12:1 und ca. 5% Neutralsalz),
6 g/l einer 30%-igen Zinknitratlösung (pH-Wert ca. 1,0) und 2 g/l 60%-ige Essigsäure.With this finishing agent I, an aqueous finishing liquor is prepared as follows:
60 g / l finishing agent I,
40 g / l of an approx. 60% aminoplast resin solution (contains dimethylol dihydroxyethylene urea etherified with methanol and pentamethylolmelamine in a ratio of 12: 1 and approx. 5% neutral salt),
6 g / l of a 30% zinc nitrate solution (pH approx. 1.0) and 2 g / l 60% acetic acid.

Flotte IIFleet II

Wie Flotte I, wobei anstelle des Ausrüstungsmittels I die Bestandteile A 1) bis C 1) der Flotte getrennt, aber mengengleich zugegeben werden.Like fleet I, but instead of finishing agent I, components A 1) to C 1) of the fleet are added separately but in equal amounts.

Flotte IIIFleet III

Wie Flotte II, aber mit doppelter Menge an Bestandteil B1).Like fleet II, but with double the amount of component B1).

Flotte IV (Vergleich) Fleet IV (comparison)

Wie Flotte II, aber ohne den Bestandteil B 1).Like fleet II, but without component B 1).

Flotte V (Vergleich)Fleet V (comparison)

Wie Flotte II, wobei anstelle des Bestandteils C 1) die gleiche Menge an α,ω -Dihydroxy-polydimethylsiloxan (Viskosität (20°C) ca. 5000 mPa.s) in wäßriger Dispersion verwendet wird.Like fleet II, but instead of component C 1) the same amount of α, ω -dihydroxy-polydimethylsiloxane (viscosity (20 ° C.) approx. 5000 mPa.s) is used in aqueous dispersion.

Ausrüstungequipment

Mit den Flotten I bis V wurde ein Polyester/Baumwollmantelpopeline 67/33 (ca. 210 g/m²) foulardiert (Flottenaufnahme ca. 65%), dann bei 110°C 10 Minuten getrocknet und bei 150°C 5 Minuten kondensiert.A polyester / cotton jacket Popeline 67/33 (approx. 210 g / m²) was padded with liquors I to V (liquor absorption approx. 65%), then dried at 110 ° C. for 10 minutes and condensed at 150 ° C. for 5 minutes.

Die Ergebnisse der Ausrüstungen sind in der nachfolgenden Tabelle zusammengestellt, wobei es sich bei den Wäschen um übliche 40°C-Haushaltsmaschinenwäschen und bei den chemischen Reinigungen (CR) um solche in Gegenwart von 2 g/l eines üblichen Reinigungsverstärkers und 2 g/l Wasser (Flottenverhältnis 1:10) handelt. Die Messungen wurden nach 5-tägigem Ausliegen unter Normalklima vorgenommen. Die Ölabweisung wurde dabei nach AATCC 118-1972, die Wasserabweisung nach DIN 53888 (a= Wasseraufnahme in %; b= Abperleffekt) bzw. dem Spraytest entsprechend AATCC 22-1974 durchgeführt.

Figure imgb0001
The results of the equipment are summarized in the table below, the laundry being the usual 40 ° C. household machine wash and the chemical cleaning (CR) washing in the presence of 2 g / l of a conventional cleaning booster and 2 g / l of water (Fleet ratio 1:10). The measurements were carried out after 5 days of exposure in a normal climate. The oil repellency was carried out according to AATCC 118-1972, the water repellency according to DIN 53888 (a = water absorption in%; b = water repellency) and the spray test according to AATCC 22-1974.
Figure imgb0001

Beispiel 2Example 2

Zur Herstellung der Ausrüstungsmittel II bzw. II a werden folgende Bestandteile zusammengerührt:The following constituents are stirred together to produce the equipment II or II a:

Bestandteil A 2)Part A 2)

40 Teile einer Formulierung entsprechend Beispiel 1 der PCT-Anmeldung WO 86/02115 (ca. 6 % Fluor).40 parts of a formulation according to Example 1 of PCT application WO 86/02115 (approx. 6% fluorine).

Bestandteil B 2)Part B 2)

10 bzw. 20 Teile (II bzw. II a) einer handelsüblichen, nichtionogenen, feinteiligen, wäßrigen 21%-igen Polyethylenwachsdispersion (25% Talgfettamin ethoxyliert mit 8 Mol Ethylenoxyd, bezogen auf Polyethylenwachs, als Emulgator; Polyethylenwachs mit Dichte ca. 0,96 g/cm³ bei 20°C, Säurezahl 27 und Verseifungszahl ca. 52).10 or 20 parts (II or II a) of a commercially available, nonionic, finely divided, aqueous 21% polyethylene wax dispersion (25% tallow fatty amine ethoxylated with 8 mol ethylene oxide, based on polyethylene wax, as an emulsifier; polyethylene wax with a density of approx. 0.96 g / cm³ at 20 ° C, acid number 27 and saponification number approx. 52).

Bestandteil C 2)Component C 2)

40 Teile einer 15%-igen, wäßrigen Weichgriffextenderemulsion eines Additionsproduktes von n-Hexadecen (α-Olefin mit durchschnittlich 16 C-Atomen) an Methylwasserstoffpolysiloxan (Molverhältnis 1:2) hergestellt entsprechend US-A-4.004.059 (Umsetzung in Butylacetat während insgesamt 1,5 Stunden; Inaktivator: tertiäres Hexadecylmercaptan; Emulgierung wie beschrieben).40 parts of a 15% aqueous soft handle extender emulsion of an addition product of n-hexadecene (α-olefin with an average of 16 carbon atoms) of methyl hydrogen polysiloxane (molar ratio 1: 2) prepared in accordance with US Pat. No. 4,004,059 (reaction in butyl acetate for a total of 1.5 hours; inactivator: tertiary hexadecyl mercaptan; emulsification as described).

Mit den Ausrüstungsmitteln II bzw. II a werden folgende wäßrige Flotten angesetzt:
90 bzw. 100 g/l Ausrüstungsmittel II bzw. IIa, 30 g/l einer 60%-igen wäßrigen Lösung von Pentamethylolmelamin-trimethylether, 6 g/l der im Beispiel 1 genannten Katalysatorlösung und 2 g/l 60%-ige Essigsäure (Flotten I bzw. II).The following aqueous liquors are prepared with the finishing agents II and II a:
90 or 100 g / l of finishing agent II or IIa, 30 g / l of a 60% aqueous solution of pentamethylolmelamine trimethyl ether, 6 g / l of the catalyst solution mentioned in Example 1 and 2 g / l of 60% acetic acid ( Fleets I and II).

Mit den beiden hergestellten Flotten wird das im Beispiel 1 beschriebene Textilmaterial in der dort angegebenen Weise ausgerüstet und dabei werden die nachfolgenden Effekte erhalten, wobei ein Vergleich in Anlehnung an den Stand der Technik (Flotte III mit 80 g/l eines Mittels aus A 2) und C2), also ohne Polyethylendispersion) zusätzlich aufgenommen wurde.

Figure imgb0002
The textile material described in Example 1 is finished with the two liquors produced and the following effects are obtained, a comparison based on the prior art (Fleet III with 80 g / l of an agent from A 2) and C2), ie without polyethylene dispersion) was also added.
Figure imgb0002

Beispiel 3Example 3

Ein Baumwollgewebe (170 g/m²) wird mit einer wäßrigen Flotte, die folgende Bestandteile enthält, getränkt, auf eine Flottenaufnahme von etwa 70% abgequetscht, kurz bei 105°C getrocknet und 5 Minuten bei 155°C kondensiert:
40 g/l Asahi Guard AG 310 (Dispersion auf Basis von Perfluoralkylacrylatpolymer mit ca. 9 % Fluor), 15 g/l der im Beispiel 1 beschriebenen Polyethylenwachsdispersion (Polyethylenwachs mit d(20°C)=0,93, Säure-/Verseifungszahl = 16), 20 g/l einer 25%-igen, nichtionogenen Dispersion eines Weichgriffextenders (H-funktionelles Methyl-C₁₀₋₁₂-Alkylpolysiloxan mit 11 Mol% Me-Si-H-Gruppen und 89 Mol% Me-Si-Alkyl-Gruppen, einer Viskosität bei 25°C von 930 mPa.s und nD25= 1,453), 20 g/l einer waßrigen, ca. 50%-igen Lösung von Pentamethylol-Melaminmethylether,
20 g/l einer 45%-igen wäßrigen Lösung von Dimethylol-dihydroxyethylenharnstoff,
2 g/l 60%-ige Essigsäure und
8 g/l Magnesiumchloridhexahydrat (Flotte I).A cotton fabric (170 g / m²) is soaked in an aqueous liquor which contains the following constituents, squeezed to a liquor absorption of about 70%, dried briefly at 105 ° C. and condensed for 5 minutes at 155 ° C.
40 g / l Asahi Guard AG 310 (dispersion based on perfluoroalkyl acrylate polymer with about 9% fluorine), 15 g / l of the polyethylene wax dispersion described in Example 1 (polyethylene wax with d (20 ° C.) = 0.93, acid / saponification number = 16), 20 g / l of a 25% nonionic dispersion of a soft handle extender (H-functional methyl-C₁₀₋₁₂-alkylpolysiloxane with 11 mol% Me-Si-H groups and 89 mol% Me-Si-alkyl- Groups, a viscosity at 25 ° C of 930 mPa.s and n D 25 = 1.453), 20 g / l of an aqueous, about 50% solution of pentamethylol-melamine methyl ether,
20 g / l of a 45% aqueous solution of dimethylol dihydroxyethylene urea,
2 g / l 60% acetic acid and
8 g / l magnesium chloride hexahydrate (fleet I).

Im Vergleich zum Stand der Technik wird eine Flotte ohne die Polyethylenwachsdispersion angesetzt (Flotte II).In comparison to the prior art, a liquor is prepared without the polyethylene wax dispersion (liquor II).

Es wird bei der erfindungsgemäßen Ausrüstung ein Gewebe mit einer ebenfalls sehr guten und permanenten Öl- und Wasserabweisung und einem wirklich ausgeprägten Soft-hand-Effekt erhalten. Nach dem Stand der Technik sind die Effekte und vor allem der Griff schwächer ausgeprägt. Einzelheiten können der nachfolgenden Tabelle entnommen werden:

Figure imgb0003
With the equipment according to the invention, a fabric with an equally very good and permanent oil and water repellency and a really pronounced soft-hand effect is obtained. According to the state of the art, the effects and especially the grip are less pronounced. Details can be found in the table below:
Figure imgb0003

Wird dieser Flotte I anstelle des Aminoplast/Katalysatorsystems ein übliches Schiebefestmittel auf Basis Polykieselsäure/basisches Aluminiumchlorid (Wirksubstanz ca. 16%) in Mengen von 15 g/l zugesetzt, so wird gleichzeitig die Schiebefestigkeit verbessert, wenn zum Beispiel eine Polyestermaschenware ausgerüstet wird.If, in place of the aminoplast / catalyst system, a conventional sliding firming agent based on polysilicic acid / basic aluminum chloride (active substance approx. 16%) is added to this liquor I in amounts of 15 g / l, the sliding resistance is improved at the same time if, for example, a polyester knitted fabric is equipped.

Beispiel 4Example 4

In gleicher Weise wie im Beispiel 1 beschrieben können zur Herstellung des Bestandteils C) auch folgende beiden Silikone verwendet werden:

Figure imgb0004
In the same way as described in Example 1, the following two silicones can also be used to prepare component C):
Figure imgb0004

Das Effekt-niveau entsprechender Ausrüstungen entspricht den im Beispiel 1 angegebenen Werten.The effect level of corresponding equipment corresponds to the values given in example 1.

Beispiel 5Example 5

Das in Beispiel 1 beschriebene Gewebe wird in eine Flotte folgender Zusammensetzung eingetaucht, auf eine Flottenaufnahme von 55 % abgequetscht, getrocknet und bei 160°C 3 Minuten kondensiert:The fabric described in Example 1 is immersed in a liquor of the following composition, squeezed to a liquor absorption of 55%, dried and condensed at 160 ° C. for 3 minutes:

32 g/l Rf-Acrylatcopolymer (kationische Dispersion auf Basis des Acrylats von C₆₋₁₀-Perfluoroalkyl-N-ethyl-N-β-hydroxyethyl-sulfonamid mit ungefähr 10% Fluorgehalt), 15 g/l einer 27 %igen Polyethylenwachsdispersion (Polyethylenwachs mit d= 0,98 (20°C), Säurezahl 25, Verseifungszahl 50; 50%, bezogen auf Polyethylenwachs, einer Emugatormischung aus C16/18-Fettalkohol ethoxyliert mit durchschnittlich 40 Mol Ethylenoxyd je Mol Alkohol und Emulgator nach Beispiel 1 der US-A-3.904.661 im Verhältnis 1:9) und 20 g/l des Bestandteils C 1) aus Beispiel 1 vorliegender Anmeldung mit dem modifizierten Hydrogenalkylpolysiloxan aus Beispiel 1 der US-A-4.625.010 als Weichgriffextender (Flotte I).32 g / l R f acrylate copolymer (cationic dispersion based on the acrylate of C₆₋₁₀-perfluoroalkyl-N-ethyl-N-β-hydroxyethyl-sulfonamide with approximately 10% fluorine content), 15 g / l of a 27% polyethylene wax dispersion ( Polyethylene wax with d = 0.98 (20 ° C), acid number 25, saponification number 50; 50%, based on polyethylene wax, an emugator mixture of C 16/18 fatty alcohol ethoxylated with an average of 40 moles of ethylene oxide per mole of alcohol and emulsifier according to Example 1 US-A-3,904,661 in the ratio 1: 9) and 20 g / l of component C 1) from example 1 of the present application with the modified hydrogenalkylpolysiloxane from example 1 of US-A-4,625,010 as a soft-grip extender (fleet I).

Als Vergleich nach dem Stand der Technik wird die gleiche Ausrüstung ohne die Polyethylenwachsdispersion durchgeführt (Flotte II).

Figure imgb0005
As a comparison according to the prior art, the same equipment is carried out without the polyethylene wax dispersion (Fleet II).
Figure imgb0005

Die Wasch- und Reinigungsbeständigkeit ist in gleicher Weise wie in den anderen Beispielen gegeben.The washing and cleaning resistance is given in the same way as in the other examples.

Claims (13)

  1. Process for conferring a soft water/oil-repellent finish on fiber materials, in particular on textiles, characterised in that an aqueous liquor containing a treatment composition based on perfluoroaliphatic compositions and extenders, the treatment composition having the following composition (sum 100%):
    A) 25 to 65% by weight, relative to the treatment composition, of a water/oil-repellent containing perfluoroaliphatic groups and at least 5% by weight of fluorine in dispersion,
    B) 10 to 35% by weight, relative to the treatment composition, of a 20 to 35% strength dispersion of an emulsifiable polyethylene having a density (at 20°C) of at least 0.92 g/cm³ and an acid number of at least 5 and
    C) 25 to 40% by weight, relative to the treatment composition, of a 25 to 40% strength fluorine-free dispersion of a soft-handle extender based on a modified hydrogenalkylpolysiloxane
    is applied to the material, and said material is finished in the usual manner.
  2. Process according to Claim 1, characterised in that mixtures of water/oil-repellents containing perfluoroaliphatic groups are used as component A).
  3. Process according to Claims 1 and 2, characterised in that
    - polyurethanes containing perfluoroaliphatic groups,
    - N-methylol condensation products containing perfluoroaliphatic groups,
    - polycarbodiimides containing perfluoroaliphatic groups and/or
    - polymers or copolymers containing perfluoroaliphatic groups are used in the form of a dispersion individually or in a mixture as component A).
  4. Process according to Claims 1 to 3, characterised in that the agents containing perfluoroaliphatic groups in component A) contain 5.5 to 15% by weight of fluorine, relative to the dispersion.
  5. Process according to Claims 1 to 4, characterised in that the emulsifiable polyethylene in component B) has a density of 0.95 to 1.05 g/cm³, an acid number of 10 to 60 and a saponification number of 15 to 80.
  6. Process according to Claims 1 to 5, characterised in that the emulsifier content in component B) is at least 3% by weight, in particular 8 to 40% by weight, relative to the polyethylene wax.
  7. Process according to Claims 1 to 6, characterised in that 20 to 35% by weight of component B) is contained in the treatment composition.
  8. Process according to Claims 1 to 7, characterised in that mixtures of silicone-based soft-handle extenders are used as component C).
  9. Process according to Claims 1 to 8, characterised in that
    - an H-functional C₈₋₁₈-alkylmethylpolysiloxane and/or
    - H-and epoxy-functional C₈₋₁₈-alkylmethylpolysiloxane, each of which, if desired, may contain aryl groups,
    are used in the form of a dispersion as component C).
  10. Process according to Claims 1 to 9, characterised in that 25 to 35% by weight of component C) is contained in the treatment composition.
  11. Process according to Claims 1 to 10, characterised in that an aqueous liquor containing 40 to 100, in particular 50 to 80, g/l of the about 25 to 35% strength by weight treatment composition is used.
  12. Process according to Claims 1 to 11, characterised in that additionally 10 to 45 g/l of a commercially available, 40 to 60% strength by weight amino resin are used.
  13. Process according to Claims 1 to 12, characterised in that furthermore customary textile auxiliaries are used in a known manner.
EP88116823A 1987-11-06 1988-10-11 Finishing composition and process for the treatment of fiber materials Expired - Lifetime EP0314944B1 (en)

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