EP0370326A2 - Method for the treatment of fibrous materials with modified organopolysiloxanes, and materials so treated - Google Patents

Method for the treatment of fibrous materials with modified organopolysiloxanes, and materials so treated Download PDF

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Publication number
EP0370326A2
EP0370326A2 EP19890120826 EP89120826A EP0370326A2 EP 0370326 A2 EP0370326 A2 EP 0370326A2 EP 19890120826 EP19890120826 EP 19890120826 EP 89120826 A EP89120826 A EP 89120826A EP 0370326 A2 EP0370326 A2 EP 0370326A2
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EP
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Prior art keywords
stage
organopolysiloxane copolymer
compound
materials
emulsifiers
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EP19890120826
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German (de)
French (fr)
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EP0370326A3 (en
EP0370326B1 (en
Inventor
Franz Dr. Dirschl
Jürgen Uhl
Michael Dr. Bernheim
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PFERSEE CHEMIE GMBH
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Pfersee Chemie GmbH
Chemische Fabrik Pfersee GmbH
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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
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3568—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing silicon
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/128—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with silicon polymers

Definitions

  • the present invention relates to a method for treating fibrous materials with modified organopolysiloxanes and the fibrous materials treated in this way.
  • the object of the present invention was to find a system which eliminates the disadvantages of the prior art and gives the treated textiles a particularly soft feel, good to very good water resistance with good whiteness retention, the effects also with regard to washing - and resistance to cleaning should meet increased requirements.
  • the present patent application thus relates to a method for treating fibrous materials with modified organopolysiloxanes, as described in more detail in claim 1.
  • a method for treating fibrous materials with modified organopolysiloxanes as described in more detail in claim 1.
  • claims 2 to 13 certain embodiments of this method are protected and in claim 14 the fibrous materials treated with the modified organopolysiloxanes are claimed.
  • the modified organopolysiloxane copolymers are prepared in two stages. In the first stage, organopolysiloxane copolymers are prepared from conventional cyclic siloxanes (A) and (meth) acrylate silanes, vinylsilanes and / or cyclic vinylsiloxanes (B).
  • the cyclic siloxanes (A) are known. Suitable Compounds are hexamethyltricyclosiloxane, octamethyltetracyclosiloxane, decamethylpentacyclosiloxane, dodekamethylhexacyclosiloxane and trimethyltriphenyltricyclosiloxane.
  • connections are: -Acryloyloxipropyldimethoximethylsilan, -Acryloyloxipropyltrimethoxisilane, Methacryloyloxypropyl diethoxymethylsilane, Methacryloyloxypropyltriethoxysilane, -Methacryloyloxipropyldimethoximethylsilan, -Methacryloyloxipropyltrimethoxisilan and -Methacryloyloxypropyltris (methoxiethoxi) silane.
  • cyclic vinylsiloxanes can be considered as starting components (B).
  • the tetramethyltetravinylcyclosiloxane may be mentioned as an example, but other known cyclic vinylsiloxanes can also be used according to the invention without any problems.
  • Octamethyltetracyclosiloxane and compounds of the formula (1) or. Have proven to be particularly suitable for the preparation of the first stage organopolysiloxane copolymers.
  • the compounds (A) and (B) are used to prepare the organopolysiloxane copolymers in amounts of from 85 to 99.99, in particular 90 to 99.8,% by weight to 15 to 0.01, in particular 10 to 0.2,% by weight implemented.
  • this 1st stage is known in principle from DE-OS 3 617 267.
  • this preparation is carried out in the presence of a crosslinking agent.
  • Tetraalkoxysilanes and / or also can be used as crosslinkers the compounds (B), if n 3, are used.
  • trifunctional crosslinkers such as methyltrimethoxisilane or ethyltriethoxisilane are also suitable. These compounds are used in amounts of 0.1 to 15% by weight; in particular 0.5 to 10% by weight, based on the sum of (A) and (B).
  • alkylbenzenesulfonic acids such as dodecyclobenzenesulfonic acid
  • dodecyclobenzenesulfonic acid are used in amounts of 0.05 to 10% by weight, in particular in amounts of 0.5 to 6% by weight, based on the sum of the compounds (A) and (B).
  • a mixture of alkylbenzenesulfonic acids and a dispersing aid is used as emulsifier (1).
  • Straight and / or branched chain alcohols with 8 to 20, in particular 12 to 18, carbon atoms have proven to be such assistants.
  • the amount of dispersing aid in the emulsifier (1) can outweigh this.
  • copolymerization is carried out with at least one vinyl monomer.
  • the known base monomers such as vinyl esters, e.g. Vinyl acetate, but especially methacrylic or acrylic acid esters, e.g. Methacrylic or acrylic acid esters of alcohols with 1 to 6 carbon atoms, are used.
  • the alkyl acrylates with 2 to 6 carbon atoms in the alkyl radical are particularly suitable as base monomers.
  • these monomers are used in amounts of at least 50% by weight, in particular 55-90% by weight.
  • monomers are acrylonitrile and methacrylonitrile, acrylamide, styrene, vinyl ether, methacrylic and acrylic acid esters of alcohols with 8 to 12 carbon atoms, conjugated diolefins, such as e.g. Butadiene or isoprene, vinyl chloride, vinylidene chloride, allyl methacrylate and ethylene dimethacrylate.
  • Particularly suitable vinyl monomers are alkyl acrylates with 2 to 6 carbon atoms in the alkyl radical, acrylonitrile and styrene.
  • crosslinkable vinyl monomers are incorporated into the modified organopolysiloxane copolymers.
  • Suitable vinyl monomers here are monomers which contain N-methylol groups, in particular carboxamide methylol groups.
  • Etherified N-methylol groups where alcohols having 1 to 4 carbon atoms, in particular methanol, are used for the etherification, are also suitable as reactive groups.
  • Monomers by means of which these groups are introduced into the modified product include, in particular, N-addition products of formaldehyde with methacrylamide or acrylamide, and also allyl or methallyl carbamate, the relevant monomethylol compounds preferably being copolymerized.
  • N-methylolacrylamide etherified with methanol can be used.
  • the crosslinkable monomers are copolymerized in amounts, based on the total vinyl monomer, of at least 0.5% by weight, preferably 1.0 to 10% by weight.
  • hydrophilic vinyl monomers examples include 2-acrylamido-2-methylpropane sodium sulfonate and / or sodium vinyl sulfonate, but also allyl alcohol.
  • the reaction in the second stage is carried out such that the weight ratio of organopolysiloxane copolymer to vinyl monomer is 1: 0.5 to 1: 4, in particular 1: 1 to 1: 2.5.
  • the 2nd stage reaction also takes place in the presence of emulsifiers. It is generally sufficient to continue working with the emulsifier (1). However, it is particularly advantageous to add additional emulsifiers during the second stage.
  • the known nonionic emulsifiers namely the customary ethoxylation products of higher fatty alcohols, fatty acids, fatty amines and fatty acid amides or their salts with volatile acids, can be used for this purpose.
  • nonionic compounds examples include: ethoxylated isotridecyl alcohol with an average of 10 to 50 ethylene oxide, 2,6,8-trimethylnonyloxipolyethylene glycol with 10 to 30 ethylene oxide, ethoxylated N- (stearyl) - or (N-hexadecyl) trimethylene diamine with 10 ethylene oxide .
  • emulsifier (2) emulsifiers
  • emulsifier (2) emulsifiers
  • emulsifier (2) emulsifiers
  • sulfonated or sulfated ethoxylated fatty alcohols or alkylphenols for example nonylphenol 5 to 15 ethylene oxide ether sulfate and sulfated cetyl, stearyl and / or isotridecyl alcohol ethoxylated with 10 to 15 ethylene oxide.
  • protective colloids that can be used are known to the person skilled in the art.
  • the compounds known for emulsion polymerization in particular polyvinyl alcohol, polyacrylic derivatives and particularly preferably polyvinylpyrrolidone, are used, in quantities of 0.1 to 5% by weight, based on the finished dispersion.
  • the copolymerization is carried out essentially in a known manner.
  • the procedure is such that the component prepared in process step (1), together with any additional emulsifiers and protective colloids and water, is placed in a reaction vessel and adjusted to a weakly acidic to neutral pH.
  • the monomers or the monomer mixture are placed in a feed vessel and slowly stirred into the reaction vessel.
  • the polymerization takes place with slow stirring at temperatures of about 50 to 75 ° C.
  • the reaction is started by adding the usual polymerization initiators, especially hydrogen peroxide, sodium hydroxymethanesulfinate and tertiary butyl hydroperoxide, which are used in a customary manner.
  • process steps 1 and 2 can also be carried out in immediate succession (one-pot process).
  • dispersions of the modified organopolysiloxane copolymers are obtained in the manner described.
  • These dispersions can be used directly for the treatment of fiber materials, in particular by coating, i.e. the coating pastes can generally be prepared in a simple manner, especially without catalysts and stabilizers.
  • the dispersions obtained are thus used directly in the coating, it being only necessary to use customary thickening and defoaming agents.
  • Preparations known from textile printing e.g. Starch and modified starch, gum and mucilages such as tragacanth, alginates and locust bean gum, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose and synthetic thickeners such as polyacrylic acid.
  • the desired viscosity is set using these thickeners, for which purpose generally only small amounts, namely 0.4 to 6% by weight, based on the coating composition, are required.
  • the defoaming agents used are also known. For this purpose, those based on silicones or ethoxylated compounds are preferably used.
  • the coating composition is then applied to the textile material to be treated in a known manner by doctoring (for example using rollers or, above all, air and rubber-coated doctor blades), brushing, printing and the like.
  • doctoring for example using rollers or, above all, air and rubber-coated doctor blades
  • work is generally carried out continuously, while the coating composition, for example, is spread on discontinuously in the laboratory.
  • the goods run at a speed of 5 to 25 m / minute depending on the material and are passed through a heating channel immediately after application and dried here at temperatures of 100 to 190 ° C and condensed if necessary, the average residence time being between half and Is 6 minutes.
  • the circulation is between 5 to 100 g / m2.
  • Lighter materials which are processed for leisure and rainwear or umbrella fabrics, have a circulation of 5 to 20 g / m2.
  • Medium-weight materials such as tarpaulin, canvas, tent and awning fabrics or terry articles are provided with 20 to 70 g / m2 and heavier materials, such as particularly technical fabrics, have a print run of up to 100 g / m2 (information based on solid substance) , it being expedient or even necessary to apply the desired number of runs in two or more passes, in particular in the case of larger runs, in order to achieve a uniform, coherent film, which is easily possible by the process according to the invention.
  • Most articles are only coated on one side, but the other side can also be coated in the same way.
  • the materials coated on both sides, but especially the one-sided, are impregnated.
  • This re-impregnation optimizes the effects and, in the case of the coating on one side only, also provides the other side with a particular water-repellent finish.
  • the post-impregnation is carried out in a known manner using the known finishing agents, such as metal salt-containing paraffin emulsions and silicone emulsions, and can also be carried out with an oleophobic, rot-proof and / or crease Free equipment can be combined, with the known equipment also being used.
  • the post-impregnation process engineering is generally known. As a rule, padding is carried out and then completed by drying and condensing. The additional impregnation can also be carried out before coating.
  • the coating compositions can also contain other substances suitable for textile treatment, such as, in particular, finishing agents.
  • substances suitable for textile treatment such as, in particular, finishing agents. Examples include aminoplast condensates. Soft-grip agents and flame retardants, as well as the corresponding catalysts if necessary, should also be mentioned.
  • finishing liquors can also contain other substances suitable for textile treatment, such as finishing agents.
  • finishing agents include aminoplast condensates.
  • the method according to the invention is for the coating and finishing of fibrous materials of all kinds, Particularly suitable for textile fibrous materials in the form of woven, knitted or non-woven fabrics. These can be made both from natural fibers, such as cellulose or keratin fibers, and from synthetic fibers, such as polyacrylonitrile, polyamide or polyester. Of course, textile materials that consist of mixtures of natural and synthetic fibers are also suitable. It should be emphasized that, according to the method of the invention, even slightly adjusted fabrics. how taffeta and / or slightly adjusted poplin fabrics can be treated. This is particularly important, for example, for rain protection clothing such as anoraks or the like.
  • the modified organopolysiloxane copolymers used according to the invention have the advantage that they can be easily formulated into liquors and pastes and, above all, the pastes can be processed well with only minimal stickiness and good durability (pot life approx. 1 week).
  • the compatibility with other polymers is almost unlimited due to the lack of catalysts.
  • fibrous materials in particular textiles, are obtained from the coating, which have excellent waterproof properties and at the same time have a pleasant, soft feel, without the whiteness being significantly impaired. It is particularly noteworthy that the watertightness and above all its resistance to cleaning is given to a remarkably high degree. Otherwise, the further properties of the treated remain in the method according to the invention as well as in the known methods Materials such as especially the filling effect and the improved crease resistance are preserved. It cannot be inferred from the prior art in any way that the modified organopolysiloxane copolymers used here would provide the desired synergism with regard to the level of effects and the persistence of the effects. But excellent overall effects can also be achieved in a simple manner within the scope of the usual equipment.
  • the whiteness is determined using a formula developed by GANZ (see RG Griesser, Textilveredlung 18 (1983), No. 5, pages 157 to 162).
  • the "ELREPHO 2000 spectral photometer for remission measurements” from DATACOLOR has proven itself for these investigations.
  • the water resistance is determined according to DIN 53886 and the irrigation according to DIN 53888 (duration 10 minutes).
  • the mixture obtained is then homogenized on a high-pressure homogenizing machine at 250 bar and 55 ° C. for homogenization.
  • the emulsion obtained is then placed in a 1 liter four-necked flask equipped with a contact thermometer, reflux condenser, stirrer and nitrogen inlet tube and the polymerization is completed under nitrogen at 95 ° C. for 3 hours.
  • the organopolysiloxane copolymer dispersion obtained has a dry matter content of approximately 22%.
  • the mixture in the feed vessel is pumped into the polymerization vessel over 15 minutes (stirrer speed 200 revolutions per minute), the temperature is set to 64 ° C. and the polymerization is carried out as follows:
  • a white polyamide taffeta (approx. 70 g / m2) is treated as follows:
  • a product B is prepared as follows:
  • the polyamide taffeta is coated in one coat with 8 g / m 2 (based on solid substance), finally dried, with an aqueous liquor composed of 60 g / l® Scotchgard FC 270 (3M Company) and 10 g / l of a commercially available approx. 60% extender based on fat-modified synthetic resin, impregnated again, briefly dried and condensed at approx. 150 ° C for 2-3 minutes.
  • the results of the equipment obtained are summarized in the following table after being displayed in a normal climate: product Whiteness according to WHOLE Watertightness Handle (Water column in mm) Whiteness drop Whiteness Orig. 5X40 ° C Masch. 3XChem.
  • Example 1 is repeated in the manner described, with the exception that 7.45 g of vinyl tributoxisilane are used instead of the methacryloyloxypropyltriethoxisilane given there and the same amount of lauryl alcohol is used in the 1st stage for the reaction instead of the cetyl alcohol.
  • Example 1 the following monomers are copolymerized based on the organopolysiloxane copolymer of stage 1 of Example 1 in the manner described in Example 1, stage 2: 147 g butyl acrylate, 98 g vinyl acetate, 17 g styrene and 12 g of N-methoxymethylacrylamide.
  • a polyester / cotton poplin (67:33, approx. 110 g / m2) or a pure cotton poplin (120 g / m2) is coated in one coat with the dispersion prepared in this way, which is adjusted to approx. 45% by weight dry matter (edition 10 or 12 g / m2) and, as indicated in Example 1, impregnated and finished, a good degree of whiteness, good washable and cleaning-resistant water resistance and, above all, a pleasantly soft soft hand grip are obtained.
  • stage 2 is carried out as follows, based on the organopolysiloxane copolymer of stage 1 of example 1:
  • the polymerization is carried out as described in Example 1. A stable dispersion of 30% by weight is obtained.
  • a cotton poplin (approx. 120 g / m2) is equipped with the dispersion prepared in this way as follows:
  • the fabric finished in this way has a very good, durable water repellency and a pleasantly soft, full silicone handle, without significantly affecting the degree of whiteness.
  • Example 1 the following monomers are copolymerized based on the organopolysiloxane copolymer of stage 1 of this example in the manner described there under stage 2: 182 g butyl acrylate 99.3 g of ethyl acrylate 5.1 g acrylamide 1.6 g of 2-acrylamido-2-methylpropane sodium sulfonate and 24.3 g of N-butoxymethyl methacrylamide.
  • a commercially available release paper is coated with the following composition: 200 g of product A according to the invention mentioned in Example 1, 2 g of a commercially available thickener based on polyacrylic acid (diluted 1: 1 with distilled water), 0.5 g of a commercially available defoamer (®RESPUMIT SI from Bayer) and 5 ml / l of a 10% ammonia.
  • 200 g of product A according to the invention mentioned in Example 1 2 g of a commercially available thickener based on polyacrylic acid (diluted 1: 1 with distilled water), 0.5 g of a commercially available defoamer (®RESPUMIT SI from Bayer) and 5 ml / l of a 10% ammonia.
  • the circulation is 5 g / m2 (based on dry matter).
  • the coated paper is then dried at 90 ° C. for 10 minutes and condensed at 120 ° C. for 15 minutes.
  • the paper which is provided with a soft, water-repellent and waterproof film in this way, is outstandingly suitable as release paper.

Abstract

The present invention relates to a method for the treatment of fibrous materials with modified organopolysiloxanes wherein in an aqueous medium an organopolysiloxane copolymer prepared in a first stage from customary cyclic siloxanes (A) and unsaturated silanes (B) in the presence of a crosslinker and emulsifier (1) and copolymerised in a second stage with at least one vinyl monomer in the presence of emulsifiers (2) is applied as a dispersion to the material, dried and condensed in a conventional manner. The method has the advantage that the materials, in particular textiles, treated, especially coated, therewith have very good watertight properties coupled with good to very good water repellency. At the same time, however, the materials also have a pleasant, soft handle without the whiteness thereof being significantly impaired.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Behandlung von faserigen Materialien mit modifizierten Organopolysiloxanen und die so behandelten faserigen Materialien.The present invention relates to a method for treating fibrous materials with modified organopolysiloxanes and the fibrous materials treated in this way.

Es ist bekannt, daß die Beschichtung von faserigen Mate­rialien, insbesondere Textilien, mit α,ω-Dihydroxydi­methylpolysiloxanen denselben einen weichen Griff ver­leiht. Es ist weiterhin bekannt, daß Acrylatcopolymere mit eingebauten vernetzungsfähigen Gruppen bei der Be­schichtung der faserigen Materialien eine merkliche Wasserdichtigkeit bewirken (DE-PS 2 616 797). Es wurde auch schon versucht, durch Kombination der Polysiloxane mit den vernetzungsfähigen Copolymeren beide Effekte zu kombinieren. Diese Versuche haben nur zu einem be­grenzten Erfolg geführt, da dann die Wasserdichtigkeit doch sehr zu wünschen übrig läßt und vor allem der Weiß­grad der behandelten Materialien in keiner Weise den heutigen Anforderungen entspricht.
Die Aufgabe der vorliegenden Erfindung lag nun darin, ein System zu finden, das die Nachteile des Standes der Technik beseitigt und den behandelten Textilien einen besonders weichen Griff, eine gute bis sehr gute Wasserdichtigkeit bei gutem Erhalt des Weißgrades ver­leiht, wobei die Effekte auch hinsichtlich Wasch- und Reinigungsbeständigkeit erhöhte Anforderungen erfüllen sollen.It is known that the coating of fibrous materials, in particular textiles, with α, ω-dihydroxydimethylpolysiloxanes gives them a soft feel. It is also known that acrylate copolymers with built-in crosslinkable groups bring about noticeable water resistance when coating the fibrous materials (DE-PS 2 616 797). Attempts have also been made to combine both effects by combining the polysiloxanes with the crosslinkable copolymers. These attempts have only met with limited success because of the water resistance leaves a lot to be desired and especially the whiteness of the treated materials does not meet today's requirements.
The object of the present invention was to find a system which eliminates the disadvantages of the prior art and gives the treated textiles a particularly soft feel, good to very good water resistance with good whiteness retention, the effects also with regard to washing - and resistance to cleaning should meet increased requirements.

Überraschenderweise konnte diese Aufgabe dadurch gelöst werden, daß zur Behandlung der faserigen Materialien bestimmte ausgewählte modifizierte Organopolysiloxane herangezogen werden.Surprisingly, this object was achieved in that certain selected modified organopolysiloxanes are used to treat the fibrous materials.

Die vorliegende Patentanmeldung betrifft somit ein Ver­fahren zur Behandlung von faserigen Materialien mit modifizierten Organopolysiloxanen, wie es im Patentan­spruch 1 naher beschrieben ist. In den Ansprüchen 2 bis 13 werden bestimmte Ausgestaltungen dieses Verfahrens unter Schutz gestellt und im Patentanspruch 14 werden die mit den modifizierten Organopolysiloxanen behandelten faserigen Materialien beansprucht.The present patent application thus relates to a method for treating fibrous materials with modified organopolysiloxanes, as described in more detail in claim 1. In claims 2 to 13 certain embodiments of this method are protected and in claim 14 the fibrous materials treated with the modified organopolysiloxanes are claimed.

Die Herstellung der modifizierten Organopolysiloxanco­polymere erfolgt in zwei Stufen. In der ersten Stufe werden aus üblichen cyclischen Siloxanen (A) und (Meth)­acrylatsilanen, Vinylsilanen und/oder cyclischen Vinyl­siloxanen (B) Organopolysiloxancopolymere hergestellt.The modified organopolysiloxane copolymers are prepared in two stages. In the first stage, organopolysiloxane copolymers are prepared from conventional cyclic siloxanes (A) and (meth) acrylate silanes, vinylsilanes and / or cyclic vinylsiloxanes (B).

Die cyclischen Siloxane (A) sind bekannt. Geeignete Verbindungen sind Hexamethyltricyclosiloxan, Octamethyl­tetracyclosiloxan, Dekamethylpentacyclosiloxan, Dodeka­methylhexacyclosiloxan und Trimethyltriphenyltricyclo­siloxan.The cyclic siloxanes (A) are known. Suitable Compounds are hexamethyltricyclosiloxane, octamethyltetracyclosiloxane, decamethylpentacyclosiloxane, dodekamethylhexacyclosiloxane and trimethyltriphenyltricyclosiloxane.

Unter die Verbindungen (B) fallen verschiedene Substan­zen. Als erstes seien (Meth)acrylatsilane, und zwar vor allem solche der Formel

Figure imgb0001
genannt, wobei R1 = H oder CH₃ x = 2 bis 6, R = vorzugs­weise C1-6 - alkyl - aber auch C2-3- alkyl-C1-3 - alkoxy und n = 1, 2 oder 3, insbesondere 2 oder 3 sind, wobei wiederum besonders diejenigen Verbindungen als Ausgangs­verbindungen geeignet sind, in denen R1 = Methyl, R = C1-6 - alkyl, x einen Wert von 3 oder 4 und n einen Wert von 2 oder 3 aufweist. Als Beispiele für derartige Ver­bindungen seien genannt:
-Acryloyloxipropyldimethoximethylsilan,
-Acryloyloxipropyltrimethoxisilan,
-Methacryloyloxipropyldiethoximethylsilan,
-Methacryloyloxipropyltriethoxisilan,
-Methacryloyloxipropyldimethoximethylsilan,
-Methacryloyloxipropyltrimethoxisilan und
-Methacryloyloxipropyltris(methoxiethoxi)silan.Various substances fall under the compounds (B). The first are (meth) acrylate silanes, especially those of the formula
Figure imgb0001
 called, wherein R1 = H or CH₃ x = 2 to 6, R = preferably C1-6 - alkyl - but also C2-3- alkyl-C1-3 - alkoxy and n = 1, 2 or 3, in particular 2 or 3 , where again those compounds are particularly suitable as starting compounds in which R1 = methyl, R = C1-6-alkyl, x has a value of 3 or 4 and n has a value of 2 or 3. Examples of such connections are:
-Acryloyloxipropyldimethoximethylsilan,
-Acryloyloxipropyltrimethoxisilane,
Methacryloyloxypropyl diethoxymethylsilane,
Methacryloyloxypropyltriethoxysilane,
-Methacryloyloxipropyldimethoximethylsilan,
-Methacryloyloxipropyltrimethoxisilan and
-Methacryloyloxypropyltris (methoxiethoxi) silane.

Die aufgeführten Verbindungen sind aus wirtschaftlichen Gründen bevorzugt, doch können selbstverständlich auch andere Verbindungen der Formel (1) als Ausgangskomponen­ten herangezogen werden.The compounds listed are preferred for economic reasons, but other compounds of the formula (1) can of course also be used as starting components.

Weiterhin kommen zur Umsetzung mit den cyclischen Silo­xanen (A) vor allem auch Vinylsilane in Betracht. Diese Verbindungen weisen die Formel
CH₂ = CH - Si (R)3-n(OR)n      (2)
auf, wobei R und n die gleiche Bedeutung wie oben angege­ben aufweisen, aber R zusätzlich auch Acetoxy sein kann. Als Beispiele seien Vinyltriethoxisilan, Vinyltris(2-­methoxiethoxi)silan, und Vinyldimethoximethylsilan ge­nannt.Furthermore, vinyl silanes are also particularly suitable for reaction with the cyclic siloxanes (A). These compounds have the formula
CH₂ = CH - Si (R) 3-n (OR) n (2)
, where R and n have the same meaning as given above, but R can also be acetoxy. Examples include vinyl triethoxysilane, vinyl tris (2-methoxiethoxi) silane, and vinyl dimethoximethylsilane.

Schließlich kommen als Ausgangskomponenten (B) cyclische Vinylsiloxane in Betracht. Aus wirtschaftlichen Gründen sei als Beispiel vor allem das Tetramethyltetravinyl­cyclosiloxan genannt, doch sind auch andere bekannte cyclische Vinylsiloxane erfindungsgemäß ohne weiteres einsetzbar.
Als besonders geeignet für die Herstellung der Organopo­lysiloxancopolymere der ersten Stufe haben sich Octame­thyltetracyclosiloxan und Verbindungen der Formel (1)bzw. (2), in denen R1 = CH₃, R = C1-6 - alkyl, x = 3 oder 4 und n = 2 oder 3 ist, erwiesen. Aber auch das Tetrame­thyltetravinylcyclosiloxan kann vorteilhaft als Ausgangs­komponente eingesetzt werden.Finally, cyclic vinylsiloxanes can be considered as starting components (B). For economic reasons, the tetramethyltetravinylcyclosiloxane may be mentioned as an example, but other known cyclic vinylsiloxanes can also be used according to the invention without any problems.
Octamethyltetracyclosiloxane and compounds of the formula (1) or. Have proven to be particularly suitable for the preparation of the first stage organopolysiloxane copolymers. (2), in which R1 = CH₃, R = C1-6 - alkyl, x = 3 or 4 and n = 2 or 3. But the tetramethyltetravinylcyclosiloxane can also be used advantageously as a starting component.

Die Verbindungen (A) und (B) werden zur Herstellung der Organopolysiloxancopolymeren in Mengen von 85 bis 99,99, insbesondere 90 bis 99,8 Gew.% zu 15 bis 0,01, insbe­sondere 10 bis 0,2 Gew.%, miteinander umgesetzt.The compounds (A) and (B) are used to prepare the organopolysiloxane copolymers in amounts of from 85 to 99.99, in particular 90 to 99.8,% by weight to 15 to 0.01, in particular 10 to 0.2,% by weight implemented.

Die Umsetzung dieser 1. Stufe ist aus der DE-OS 3 617 267 grundsätzlich bekannt. So wird diese Herstellung in aller Regel in Gegenwart eines Vernetzers vorgenommen. Als Vernetzer können dabei Tetraalkoxisilane und/oder auch die Verbindungen (B), sofern n = 3 ist, herangezogen werden. Aber auch trifunktionelle Vernetzer wie Methyl­trimethoxisilan oder Ethyltriethoxisilan sind geeignet. Diese Verbindungen werden dabei in Mengen von 0,1 bis 15 Gew.%; insbesondere 0,5 bis 10 Gew.%, bezogen auf die Summe von (A) und (B), herangezogen.The implementation of this 1st stage is known in principle from DE-OS 3 617 267. As a rule, this preparation is carried out in the presence of a crosslinking agent. Tetraalkoxysilanes and / or also can be used as crosslinkers the compounds (B), if n = 3, are used. However, trifunctional crosslinkers such as methyltrimethoxisilane or ethyltriethoxisilane are also suitable. These compounds are used in amounts of 0.1 to 15% by weight; in particular 0.5 to 10% by weight, based on the sum of (A) and (B).

Ein weiterer Bestandteil während des Verfahrens der 1. Stufe sind die Emulgatoren (1). Hierzu werden vor allem Alkylbenzolsulfonsäuren, wie Dodecyclbenzolsulfon­säure, in Mengen von 0,05 bis 10 Gew.%, insbesondere in Mengen von 0,5 bis 6 Gew.%, bezogen auf die Summe der Verbindungen (A) und (B), eingesetzt. Als vorteilhaft hat es sich dabei erwiesen, wenn als Emulgator (1) ein Gemisch aus Alkylbenzolsulfonsäuren und einem Dispergier­hilfsmittel verwendet wird. Als solche Hilfsmittel haben sich gerad- und/oder verzweigtkettige Alkohole mit 8 bis 20, insbesondere 12 bis 18 C-Atomen erwiesen. Dabei kann in dem Emulgator (1) die Menge des Dispergierhilfs­mittels durchaus überwiegen.Another component during the 1st stage process are the emulsifiers (1). For this purpose, especially alkylbenzenesulfonic acids, such as dodecyclobenzenesulfonic acid, are used in amounts of 0.05 to 10% by weight, in particular in amounts of 0.5 to 6% by weight, based on the sum of the compounds (A) and (B). It has proven to be advantageous if a mixture of alkylbenzenesulfonic acids and a dispersing aid is used as emulsifier (1). Straight and / or branched chain alcohols with 8 to 20, in particular 12 to 18, carbon atoms have proven to be such assistants. The amount of dispersing aid in the emulsifier (1) can outweigh this.

Die Stufe 1 wird nun folgendermaßen durchgeführt:Stage 1 is now carried out as follows:

Zuerst werden Wasser, vorteilhaft destilliertes bzw. doppelt destilliertes Wasser und der Emulgator bzw. die Emulgatormischung eingewogen und durch Rühren, gegebe­nenfalls unter Erwärmen, eine homogene Lösung hergestellt. Anschließend werden die Verbindungen (A) und (B) und der Vernetzer langsam zu der vorher hergestellten wäßrigen Lösung gegeben und unter Rühren bei leicht erhöhter Tempe­ratur eine homogene Mischung hergestellt. Die so herge­stellte Voremulsion wird mit Hilfe einer Hochdruckemul­giervorrichtung homogenisiert. Es wird eine beständige Dispersion des Organopolysiloxancopolymers erhalten (Kon­zentration etwa 10 bis 45 %ig).Water, advantageously distilled or double-distilled water and the emulsifier or the emulsifier mixture are weighed in first and a homogeneous solution is prepared by stirring, if appropriate with heating. Then the compounds (A) and (B) and the crosslinker are slowly added to the previously prepared aqueous solution and a homogeneous mixture is prepared with stirring at a slightly elevated temperature. The pre-emulsion thus produced is homogenized using a high-pressure emulsifying device. A stable dispersion of the organopolysiloxane copolymer is obtained (concentration about 10 to 45%).

In der anschließenden 2. Stufe wird mit mindestens einem Vinylmonomeren copolymerisiert. Als Vinylmonomere kommen dabei die bekannten Basismonomeren, wie Vinylester, z.B. Vinylacetat, vor allem aber Methacryl- bzw. Acrylsäure­ester, z.B. Methacryl- bzw. Acrylsäureester von Alkoholen mit 1 bis 6 C-Atomen, zum Einsatz. Die Alkylacrylate mit 2 bis 6 C-Atomen im Alkylrest sind als Basismonomere besonders geeignet. Diese Monomeren werden in 2. Stufe, bezogen auf Gesamtmonomer, in Mengen von mindestens 50 Gew.%, insbesondere 55 - 90 Gew., eingesetzt. Daneben kommen als Monomere Acryl- und Methacrylsäurenitril, Acrylamid, Styrol, Vinylether, Methacryl- bzw. Acrylsäure­ester von Alkoholen mit 8 bis 12 C-Atomen, konjugierte Diolefine, wie z.B. Butadien oder Isopren, Vinylchlorid, Vinylidenchlorid, Allylmethacrylat und Ethylendimethacry­lat in Betracht. Besonders geeignete Vinylmonomere sind dabei Alkylacrylate mit 2 bis 6 C-Atomen im Alkylrest, Acrylnitril und Styrol.In the subsequent second stage, copolymerization is carried out with at least one vinyl monomer. The known base monomers, such as vinyl esters, e.g. Vinyl acetate, but especially methacrylic or acrylic acid esters, e.g. Methacrylic or acrylic acid esters of alcohols with 1 to 6 carbon atoms, are used. The alkyl acrylates with 2 to 6 carbon atoms in the alkyl radical are particularly suitable as base monomers. In the second stage, based on the total monomer, these monomers are used in amounts of at least 50% by weight, in particular 55-90% by weight. In addition, monomers are acrylonitrile and methacrylonitrile, acrylamide, styrene, vinyl ether, methacrylic and acrylic acid esters of alcohols with 8 to 12 carbon atoms, conjugated diolefins, such as e.g. Butadiene or isoprene, vinyl chloride, vinylidene chloride, allyl methacrylate and ethylene dimethacrylate. Particularly suitable vinyl monomers are alkyl acrylates with 2 to 6 carbon atoms in the alkyl radical, acrylonitrile and styrene.

Daneben hat es sich gezeigt, daß es besonders vorteilhaft ist, wenn vernetzungsfähige Vinylmonomere in die modifi­zierten Organopolysiloxancopolymere eingebaut werden. Als solche Vinylmonomere kommen dabei Monomere in Frage, die N-Methylolgruppen, insbesondere Carbonsäureamidmethy­lolgruppen enthalten. Auch veretherte N-Methylolgruppen, wobei zur Veretherung Alkohole mit 1 bis 4 C-Atomen, insbesondere Methanol, verwendet werden, sind als reaktive Gruppen geeignet. Als Monomere, durch die diese Gruppen in das modifizierte Produkt eingeführt werden, sind insbe­sondere N-Additionsprodukte von Formaldehyd an Methacryl­amid bzw. Acrylamid, sowie Allyl- bzw. Methallylcarbamat, wobei vorzugsweise die betreffenden Monomethylolverbin­dungen einpolymerisiert werden, zu nennen. Daneben kommen z.B. mit Methanol verethertes N-Methylolacrylamid in Betracht. Die vernetzungsfähigen Monomeren werden dabei in Mengen, bezogen auf das gesamte Vinylmonomer, von mindestens 0,5 Gew.%, vorzugsweise 1,0 bis 10 Gew.% ein­polymerisiert.In addition, it has been shown that it is particularly advantageous if crosslinkable vinyl monomers are incorporated into the modified organopolysiloxane copolymers. Suitable vinyl monomers here are monomers which contain N-methylol groups, in particular carboxamide methylol groups. Etherified N-methylol groups, where alcohols having 1 to 4 carbon atoms, in particular methanol, are used for the etherification, are also suitable as reactive groups. Monomers by means of which these groups are introduced into the modified product include, in particular, N-addition products of formaldehyde with methacrylamide or acrylamide, and also allyl or methallyl carbamate, the relevant monomethylol compounds preferably being copolymerized. In addition, N-methylolacrylamide etherified with methanol can be used. The crosslinkable monomers are copolymerized in amounts, based on the total vinyl monomer, of at least 0.5% by weight, preferably 1.0 to 10% by weight.

Weiterhin sind als Vinylmonomere besonders hydrophile Vinylmonomere geeignet. Als Beispiele seien hier vor allem 2-Acrylamido-2-methylpropannatriumsulfonat und/oder Natriumvinylsulfonat, aber auch Allylalkohol, genannt.Also particularly suitable as vinyl monomers are hydrophilic vinyl monomers. Examples include 2-acrylamido-2-methylpropane sodium sulfonate and / or sodium vinyl sulfonate, but also allyl alcohol.

Die Umsetzung in der 2. Stufe wird dabei so geführt, daß das Gewichtsverhältnis von Organopolysiloxancopolymer zu Vinylmonomer 1:0,5 bis 1:4, insbesondere 1:1 bis 1:2,5 beträgt.The reaction in the second stage is carried out such that the weight ratio of organopolysiloxane copolymer to vinyl monomer is 1: 0.5 to 1: 4, in particular 1: 1 to 1: 2.5.

Auch die Reaktion der 2. Stufe findet in Gegenwart von Emulgatoren statt. Dabei reicht es im allgemeinen schon aus, wenn mit dem Emulgator (1) weitergearbeitet wird. Besonders vorteilhaft ist es aber, während der 2. Stufe zusätzlich noch weitere Emulgatoren zuzufügen. Für diesen Zweck können die bekannten nichtionogenen Emulgatoren, nämlich die üblichen Ethoxilierungsprodukte von höheren Fettalkoholen, Fettsäuren, Fettaminen und Fettsäureamiden bzw. deren Salze mit flüchtigen Säuren eingesetzt werden. Als Beispiele für besonders geeignete nichtionogene Ver­bindungen seien genannt: Ethoxilierter Isotridecylalkohol mit durchschnittlich 10 bis 50 Ethylenoxid, 2,6,8-Tri­methylnonyloxipolyethylenglykol mit 10 bis 30 Ethylenoxid, ethoxiliertes N-(Stearyl)- oder (N-Hexadecyl-)trimethylen­diamin mit 10 Ethylenoxid.The 2nd stage reaction also takes place in the presence of emulsifiers. It is generally sufficient to continue working with the emulsifier (1). However, it is particularly advantageous to add additional emulsifiers during the second stage. The known nonionic emulsifiers, namely the customary ethoxylation products of higher fatty alcohols, fatty acids, fatty amines and fatty acid amides or their salts with volatile acids, can be used for this purpose. Examples of particularly suitable nonionic compounds are: ethoxylated isotridecyl alcohol with an average of 10 to 50 ethylene oxide, 2,6,8-trimethylnonyloxipolyethylene glycol with 10 to 30 ethylene oxide, ethoxylated N- (stearyl) - or (N-hexadecyl) trimethylene diamine with 10 ethylene oxide .

Besonders bevorzugt ist es aber als Emulgator (2) eine Mischung aus den Emulgatoren (1) und ethoxilierten, an­ionaktiven Emulgatoren zum Einsatz zu bringen. Als solche Verbindungen seien sulfonierte bzw. sulfatierte ethoxilierte Fettalkohole oder Alkylphenole genannt, z.B. Nonylphenol- 5 bis 15 Ethylenoxid -ethersulfat und sulfatierter, mit 10 bis 15 Ethylenoxid ethoxilierter Cetyl-, Stearyl- und/oder Isotridecylalkohol.However, it is particularly preferred to use a mixture of the emulsifiers (1) and ethoxylated, anionic emulsifiers as the emulsifier (2). As such compounds may be mentioned sulfonated or sulfated ethoxylated fatty alcohols or alkylphenols, for example nonylphenol 5 to 15 ethylene oxide ether sulfate and sulfated cetyl, stearyl and / or isotridecyl alcohol ethoxylated with 10 to 15 ethylene oxide.

Zusatzlich zu den Emulgatoren (2) ist es angebracht, die Umsetzung in Gegenwart von Schutzkolloiden durchzu­führen. Die einsetzbaren Schutzkolloide sind dem Fachmann bekannt. Es werden die für die Emulsionspolymerisation bekannten Verbindungen, insbesondere Polyvinylalkohol, Polyacrylderivate und besonders bevorzugt Polyvinylpyrro­lidon verwendet, und zwar in Mengen von 0,1 bis 5 Gew.%, bezogen auf die fertige Dispersion.In addition to the emulsifiers (2), it is appropriate to carry out the reaction in the presence of protective colloids. The protective colloids that can be used are known to the person skilled in the art. The compounds known for emulsion polymerization, in particular polyvinyl alcohol, polyacrylic derivatives and particularly preferably polyvinylpyrrolidone, are used, in quantities of 0.1 to 5% by weight, based on the finished dispersion.

Die Copolymerisation wird im wesentlichen in bekannter Weise durchgeführt. Im allgemeinen wird so verfahren, daß in ein Reaktionsgefäß die in der Verfahrensstufe (1) hergestellte Komponente zusammen mit eventuell zusätzli­chen Emulgatoren und Schutzkolloiden und Wasser vorgelegt und auf einen schwach-sauren bis neutralen pH-Wert einge­stellt wird. In ein Zulaufgefaß werden die Monomeren bzw. das Monomerengemisch vorgelegt und langsam in das Reaktionsgefaß eingerührt. Dabei erfolgt die Polymerisa­tion unter langsamen Ruhren bei Temperaturen von etwa 50 bis 75°C. Die Reaktion wird gestartet durch Zugabe der üblichen Polymerisationsinitiatoren, vor allen Dingen Wasserstoffperoxid, hydroximethansulfinsaures Natrium und Tertiärbutylhydroperoxid, die in ublicher Weise angewandt werden. Während der Polymerisation ist durch Zugabe von z.B. Soda auf einen weitgehend konstanten pH-Wert zu achten. Am Schluß wird durch nochmalige Zugabe von Katalysator die Polymerisation zum Abschluß gebracht und dann kalt geruhrt. - Vorteilhaft können auch die Ver­fahrensstufen 1 und 2 unmittelbar aufeinanderfolgend durchgeführt werden (Eintopfverfahren).The copolymerization is carried out essentially in a known manner. In general, the procedure is such that the component prepared in process step (1), together with any additional emulsifiers and protective colloids and water, is placed in a reaction vessel and adjusted to a weakly acidic to neutral pH. The monomers or the monomer mixture are placed in a feed vessel and slowly stirred into the reaction vessel. The polymerization takes place with slow stirring at temperatures of about 50 to 75 ° C. The reaction is started by adding the usual polymerization initiators, especially hydrogen peroxide, sodium hydroxymethanesulfinate and tertiary butyl hydroperoxide, which are used in a customary manner. During the polymerization, the addition of soda, for example, ensures that the pH is largely constant. In the end, the polymerization is brought to a conclusion by adding catalyst again and then stirred cold. - Advantageously, process steps 1 and 2 can also be carried out in immediate succession (one-pot process).

In der beschriebenen Weise werden 20 bis 50%-ige, insbe­sondere 30 bis 45%-ige Dispersionen der modifizierten Organopolysiloxancopolymeren erhalten. Diese Dispersionen können unmittelbar zur Behandlung von Fasermaterialien, insbesondere durch Beschichten eingesetzt werden, d.h. die Beschichtungspasten können im allgemeinen in einfa­cher Weise, vor allem ohne Katalysatoren und Stabilisato­ren, angesetzt werden.20 to 50%, in particular 30 to 45%, dispersions of the modified organopolysiloxane copolymers are obtained in the manner described. These dispersions can be used directly for the treatment of fiber materials, in particular by coating, i.e. the coating pastes can generally be prepared in a simple manner, especially without catalysts and stabilizers.

Bei der Beschichtung werden die erhaltenen Dispersionen also direkt eingesetzt, wobei es lediglich notwendig ist, unter Umständen übliche Verdickungs- und Entschäu­mungsmittel mitzuverwenden. Als Verdickungsmittel kommen die vom Textildruck her bekannten Präparate, z.B. Stärke und abgewandelte Stärke, Pflanzengummi und Pflanzen­schleime, wie Tragant, Alginate und Johannisbrotkernmehl, Cellulosederivate wie Carboxymethylcellulose, Hydroxy­ethylcellulose und synthetische Verdickungsmittel, wie Polyacrylsäure, in Betracht. Mit diesen Verdickungsmit­teln wird die gewünschte Viskosität eingestellt, wozu im allgemeinen nur geringe Mengen, nämlich 0,4 bis 6 Gew.%, bezogen auf die Beschichtungsmasse, erforderlich sind. Die verwendeten Entschäumungsmittel sind ebenfalls bekannt. Es werden hierzu vorzugsweise solche auf Basis von Silikonen oder ethoxilierten Verbindungen herangezo­gen.The dispersions obtained are thus used directly in the coating, it being only necessary to use customary thickening and defoaming agents. Preparations known from textile printing, e.g. Starch and modified starch, gum and mucilages such as tragacanth, alginates and locust bean gum, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose and synthetic thickeners such as polyacrylic acid. The desired viscosity is set using these thickeners, for which purpose generally only small amounts, namely 0.4 to 6% by weight, based on the coating composition, are required. The defoaming agents used are also known. For this purpose, those based on silicones or ethoxylated compounds are preferably used.

Die Beschichtungsmasse wird dann in bekannter Weise durch Rakeln (z.B. mit Walzen oder vor allem Luft- und Gummituchrakel), Streichen, Drucken und ähnliches auf das zu behandelnde Textilgut aufgebracht. In der Praxis wird in der Regel kontinuierlich gearbeitet, während im Labor auch diskontinuierlich die Beschichtungsmasse, z.B. aufgestrichen, wird. Bei der kontinuierlichen Ar­ beitsweise läuft die Ware je nach Material mit einer Geschwindigkeit von 5 bis 25 m/Minute und wird unmittel­bar nach dem Auftragen durch einen Wärmekanal geleitet und hier bei Temperaturen von 100 bis 190°C getrocknet und gegebenenfalls kondensiert, wobei die Verweilzeit durchschnittlich zwischen einer halben und 6 Minuten beträgt. Die Auflage liegt zwischen 5 bis 100 g/m². Leichtere Materialien, die zur Freizeit- und Regenbeklei­dung oder Schirmstoffen verarbeitet werden, erhalten eine Auflage von 5 bis 20 g/m². Mittelschwere Materia­lien, wie Planen-, Segeltuch-, Zelt- und Markisenstoffe oder Frotteeartikel werden mit 20 bis 70 g/m² versehen und schwerere Materialien, wie besonders technische Gewebe, erhalten eine Auflage von bis zu 100 g/m² (Anga­ben bezogen auf Festsubstanz), wobei es besonders bei höheren Auflagemengen zur Erzielung eines gleichmäßigen, zusammenhängenden Films zweckmäßig, bzw. sogar notwendig ist, die gewünschte Auflagenmenge in zwei oder mehr Durchgängen zu applizieren, was nach dem erfindungsge­mäßen Verfahren problemlos möglich ist. Die meisten Artikel werden nur einseitig beschichtet, doch kann in gleicher Weise auch die andere Seite mit einer Be­schichtung versehen werden.The coating composition is then applied to the textile material to be treated in a known manner by doctoring (for example using rollers or, above all, air and rubber-coated doctor blades), brushing, printing and the like. In practice, work is generally carried out continuously, while the coating composition, for example, is spread on discontinuously in the laboratory. With the continuous ar In some cases, the goods run at a speed of 5 to 25 m / minute depending on the material and are passed through a heating channel immediately after application and dried here at temperatures of 100 to 190 ° C and condensed if necessary, the average residence time being between half and Is 6 minutes. The circulation is between 5 to 100 g / m². Lighter materials, which are processed for leisure and rainwear or umbrella fabrics, have a circulation of 5 to 20 g / m². Medium-weight materials such as tarpaulin, canvas, tent and awning fabrics or terry articles are provided with 20 to 70 g / m² and heavier materials, such as particularly technical fabrics, have a print run of up to 100 g / m² (information based on solid substance) , it being expedient or even necessary to apply the desired number of runs in two or more passes, in particular in the case of larger runs, in order to achieve a uniform, coherent film, which is easily possible by the process according to the invention. Most articles are only coated on one side, but the other side can also be coated in the same way.

Häufig werden die beidseitig, insbesondere aber die einseitig beschichteten Materialien nachimprägniert. Durch diese Nachimprägnierung wird eine Optimierung der Effekte erreicht und außerdem bei der nur einseitigen Beschichtung auch die andere Seite mit einer insbesonde­ren wasserabweisenden Ausrüstung versehen. Die Nachim­prägnierung erfolgt in bekannter Weise unter Verwendung der bekannten Ausrüstungsmittel, wie metallsalzhaltige Paraffinemulsionen und Silikonemulsionen und kann auch mit einer oleophoben, verrottungsfesten und/oder Knitter­ freiausrüstung kombiniert werden, wobei ebenfalls die bekannten Ausrüstungsmittel zum Einsatz gelangen. Die Verfahrenstechnik der Nachimprägnierung ist allgemein bekannt. In der Regel wird foulardiert und dann durch Trocknen und Kondensieren fertiggestellt. Die zusätzliche Imprägnierung kann auch vor der Beschichtung erfolgen.Frequently, the materials coated on both sides, but especially the one-sided, are impregnated. This re-impregnation optimizes the effects and, in the case of the coating on one side only, also provides the other side with a particular water-repellent finish. The post-impregnation is carried out in a known manner using the known finishing agents, such as metal salt-containing paraffin emulsions and silicone emulsions, and can also be carried out with an oleophobic, rot-proof and / or crease Free equipment can be combined, with the known equipment also being used. The post-impregnation process engineering is generally known. As a rule, padding is carried out and then completed by drying and condensing. The additional impregnation can also be carried out before coating.

Die Beschichtungsmassen können noch andere zur Textilbe­handlung geeignete Substanzen, wie insbesondere Appretur­mittel enthalten. Genannt seien beispielsweise Amino­plastkondensate. Auch Weichgriffmittel und Flammschutz­mittel, sowie nötigenfalls die entsprechenden Katalysato­ren sind zu nennen.The coating compositions can also contain other substances suitable for textile treatment, such as, in particular, finishing agents. Examples include aminoplast condensates. Soft-grip agents and flame retardants, as well as the corresponding catalysts if necessary, should also be mentioned.

Bei der Ausrüstung werden in der Regel in Abhängigkeit von der Flottenaufnahme und dem gewünschten Effekt 4 bis 200 g/l (höhere Mengen sind aus wirtschaftlichen Gründen nicht angebracht), insbesondere 5 bis 100 g/l der 100%-igen modifizierten Organopolysiloxancopolymeren in Wasser eingerührt und in üblicher Weise durch Tauchen und Abquetschen (Foulardieren), Pflatschen oder Sprühen behandelt. Danach wird getrocknet und in Abhängigkeit des behandelten Materials einige Sekunden bis Minuten bei 120 bis 190°C kondensiert.Depending on the liquor absorption and the desired effect, 4 to 200 g / l (higher amounts are not appropriate for economic reasons), in particular 5 to 100 g / l, of the 100% modified organopolysiloxane copolymers are generally stirred into the equipment in water and treated in the usual way by dipping and squeezing (padding), splashing or spraying. It is then dried and condensed for a few seconds to minutes at 120 to 190 ° C, depending on the material being treated.

Die Ausrüstungsflotten können ebenfalls noch andere zur Textilbehandlung geeignete Substanzen, wie Appretur­mittel enthalten. Genannt seien beispielsweise Amino­plastkondensate. Auch Weichgriffmittel und Flammschutz­mittel sowie nötigenfalls die entsprechenden Katalysato­ren sind zu nennen.The finishing liquors can also contain other substances suitable for textile treatment, such as finishing agents. Examples include aminoplast condensates. Soft-grip agents and flame retardants and, if necessary, the corresponding catalysts should also be mentioned.

Das erfindungsgemäße Verfahren ist zur Beschichtung und Ausrüstung von faserigen Materialien aller Art, insbesondere von textilen faserigen Materialien in Form von Geweben, Gewirken oder Vliesen geeignet. Diese können sowohl aus natürlichen Fasern, wie Cellulose- oder Kera­tinfasern, als auch aus synthetischen Fasern, wie Poly­acrylnitril, Polyamid oder Polyester hergestellt sein. Selbstverständlich kommen auch Textilmaterialien in Betracht, die aus Mischungen von natürlichen mit synthe­tischen Fasern bestehen. Hervorzuheben ist, daß nach dem erfindungsgemäßen Verfahren auch leicht eingestellte Gewebe. wie Taft und/oder leicht eingestellte Popeline­stoffe, behandelt werden können. Dies ist beispielsweise für Regenschutzbekleidung, wie Anoraks oder dergleichen, von besonderer Bedeutung.The method according to the invention is for the coating and finishing of fibrous materials of all kinds, Particularly suitable for textile fibrous materials in the form of woven, knitted or non-woven fabrics. These can be made both from natural fibers, such as cellulose or keratin fibers, and from synthetic fibers, such as polyacrylonitrile, polyamide or polyester. Of course, textile materials that consist of mixtures of natural and synthetic fibers are also suitable. It should be emphasized that, according to the method of the invention, even slightly adjusted fabrics. how taffeta and / or slightly adjusted poplin fabrics can be treated. This is particularly important, for example, for rain protection clothing such as anoraks or the like.

Die erfindungsgemäß verwendeten modifizierten Organopoly­siloxancopolymeren haben den Vorteil, daß sie in ein­facher Weise zu Flotten und Pasten formuliert und vor allem die Pasten durch nur minimale Klebrigkeit und gute Haltbarkeit (Topfzeit ca. 1 Woche) gut verarbeitet werden können. Auch die Verträglichkeit mit anderen Polymeren ist durch fehlende Katalysatoren nahezu unbe­grenzt.The modified organopolysiloxane copolymers used according to the invention have the advantage that they can be easily formulated into liquors and pastes and, above all, the pastes can be processed well with only minimal stickiness and good durability (pot life approx. 1 week). The compatibility with other polymers is almost unlimited due to the lack of catalysts.

Nach dem erfindungsgemäßen Verfahren werden durch die Beschichtung faserige Materialien, insbesondere Texti­lien, erhalten, die hervorragende wasserdichte Eigen­schaften und gleichzeitig einen angenehmen, weichen Griff aufweisen, ohne daß der Weißgrad in nennenswerter Weise beeinträchtigt wird. Dabei ist es besonders bemer­kenswert, daß die Wasserdichtigkeit und vor allem auch deren Reinigungsbeständigkeit in einem beachtenswert hohen Maße gegeben ist. Im übrigen bleiben bei dem erfin­dungsgemäßen Verfahren ebenso wie bei den bekannten Verfahren die weiteren Eigenschaften der behandelten Materialien, wie vor allem die Füllwirkung und die ver­besserte Knitterfestigkeit, erhalten. Es ist dabei aus dem Stand der Technik in keiner Weise zu entnehmen, daß gerade die hier verwendeten modifizierten Organopoly­siloxancopolymeren den angestrebten Synergismus hinsicht­lich des Effektniveaus und der Beständigkeit der Effekte liefern würden.
Aber auch im Rahmen der üblichen Ausrüstung können her­vorragende Gesamteffekte in einfacher Weise erzielt werden.In the process according to the invention, fibrous materials, in particular textiles, are obtained from the coating, which have excellent waterproof properties and at the same time have a pleasant, soft feel, without the whiteness being significantly impaired. It is particularly noteworthy that the watertightness and above all its resistance to cleaning is given to a remarkably high degree. Otherwise, the further properties of the treated remain in the method according to the invention as well as in the known methods Materials such as especially the filling effect and the improved crease resistance are preserved. It cannot be inferred from the prior art in any way that the modified organopolysiloxane copolymers used here would provide the desired synergism with regard to the level of effects and the persistence of the effects.
But excellent overall effects can also be achieved in a simple manner within the scope of the usual equipment.

Die Bestimmung des Weißgrades erfolgt nach einer von GANZ entwickelten Formel (vergleiche hierzu R.G. Gries­ser, Textilveredlung 18 (1983), Nr. 5, Seiten 157 bis 162). Für diese Untersuchungen hat sich das "ELREPHO 2000 Spektral-Fotometer für Remmissionsmessungen" von DATACOLOR bewährt.
Die Wasserdichtigkeit wird nach DIN 53886 und die Bereg­nung nach DIN 53888 (Dauer 10 Minuten) bestimmt.The whiteness is determined using a formula developed by GANZ (see RG Griesser, Textilveredlung 18 (1983), No. 5, pages 157 to 162). The "ELREPHO 2000 spectral photometer for remission measurements" from DATACOLOR has proven itself for these investigations.
The water resistance is determined according to DIN 53886 and the irrigation according to DIN 53888 (duration 10 minutes).

Die Erfindung wird nun anhand der nachfolgenden Beispiele näher erläutert, wobei Teile = Gewichtsteile und Prozen­te = Gew.% bedeuten.The invention will now be explained in more detail with reference to the following examples, parts = parts by weight and percentages =% by weight.

Beispiel 1example 1 Herstellung des modifizierten OrganopolysiloxancopolymerPreparation of the modified organopolysiloxane copolymer Verfahren der 1. Stufe:1st stage procedure:

In ein 2000 ml-Becherglas werden nacheinander 667 g doppelt destilliertes Wasser, 2,5 g Dodecylbenzolsulfonsäure und 7,5 g Cetylalkohol gegeben und unter Rühren auf 60°C erwärmt bis alle Komponenten gelöst sind. Man läßt dann zur Vervoll­ständigung noch 5 Minuten nachrühren.
Daneben werden in einem 400 ml-Becherglas 2,5 g Tetra­ethylorthosilikat, 1,95 g Methacryloyloxipropyltriethoxy­silan und 249 g Octamethyltetracyclosiloxan eingewogen und langsam in die Mischung des 2000 ml-Becherglases einge­gossen. Es wird nun noch 10 Minuten bei 60°C rühren gelas­sen.667 g of double distilled water, 2.5 g of dodecylbenzenesulfonic acid and 7.5 g of cetyl alcohol are added in succession to a 2000 ml beaker and heated to 60 ° C. with stirring until all components have dissolved. The mixture is then left to stir for 5 minutes to complete.
In addition, 2.5 g of tetraethyl orthosilicate, 1.95 g of methacryloyloxypropyltriethoxysilane and 249 g of octamethyltetracyclosiloxane are weighed into a 400 ml beaker and slowly poured into the mixture of the 2000 ml beaker. It is then left to stir at 60 ° C. for a further 10 minutes.

Die erhaltene Mischung wird danach zur Homogenisierung bei 250 bar und 55°C auf einer Hochdruckhomogenisiermaschine homogenisiert.The mixture obtained is then homogenized on a high-pressure homogenizing machine at 250 bar and 55 ° C. for homogenization.

Anschließend wird die erhaltene Emulsion in einen 1 Liter-­Vierhalskolben, versehen mit Kontaktthermometer, Rückfluß­kühler, Rührer und Stickstoffeinleitungsrohr gegeben und während 3 Stunden bei 95°C die Polymerisation unter Stick­stoff vervollständigt. Die erhaltene Organopolysiloxanco­polymerdispersion weist einen Trockensubstanzgehalt von ca. 22% auf.The emulsion obtained is then placed in a 1 liter four-necked flask equipped with a contact thermometer, reflux condenser, stirrer and nitrogen inlet tube and the polymerization is completed under nitrogen at 95 ° C. for 3 hours. The organopolysiloxane copolymer dispersion obtained has a dry matter content of approximately 22%.

Verfahren der 2. Stufe:2nd stage procedure:

In einem Polymerisationsgefäß werden 645 g der in Stufe 1 hergestellten Dispersion, 16,8 g eines ethoxilierten Nonyl­phenolnatriumsulfates mit durchschnittlich 8 Ethylenoxid-­Einheiten je Molekül, 38,3 g einer 10%-igen Lösung von Polyvinylpyrrolidon, 4,6 g doppelt destilliertes Wasser, 1,1 g 2-Acrylamido-2-methylpropan-Natriumsulfonat und 5,5 g einer 10%-igen Sodalösung im Abstand von etwa 3 Minuten eingefüllt und mit einer Geschwindigkeit von 250 Umdrehungen pro Minute eine Stunde zusammengerührt.645 g of the dispersion prepared in stage 1, 16.8 g of an ethoxylated nonylphenol sodium sulfate with an average of 8 ethylene oxide units per molecule, 38.3 g of a 10% strength solution of polyvinylpyrrolidone, 4.6 g of double-distilled water are placed in a polymerization vessel. 1.1 g of 2-acrylamido-2-methylpropane sodium sulfonate and 5.5 g of a 10% sodium carbonate solution were introduced at intervals of about 3 minutes and stirred together for one hour at a speed of 250 revolutions per minute.

Daneben werden in einem Zulaufbehälter 211,3 g Butylacrylat stabilisiert, 1,7 g ethoxilierter Isotridecylalkohol mit 40 Ethylenoxid je Mol auf 40°C erwärmt bis eine klare Lösung erhalten wird und dann 51,5 g Acrylnitril unter Kühlen auf 25°C und 16,6 g N-Butoximethylmethacrylamid zugegeben (pH-Wert ca. 5).In addition, 211.3 g of butyl acrylate are stabilized in an inlet tank, 1.7 g of ethoxylated isotridecyl alcohol with 40 ethylene oxide per mole are heated to 40 ° C. until a clear solution is obtained, and then 51.5 g of acrylonitrile are cooled to 25 ° C. and 16 ° C. 6 g of N-butoxymethyl methacrylamide were added (pH approx. 5).

Zur Polymerisation wird die in dem Zulaufgefäß befindliche Mischung während 15 Minuten in das Polymerisationsgefäß gepumpt (Rührergeschwindigkeit 200 Umdrehungen pro Minute), die Temperatur auf 64°C eingestellt und wie folgt polymeri­siert:For the polymerization, the mixture in the feed vessel is pumped into the polymerization vessel over 15 minutes (stirrer speed 200 revolutions per minute), the temperature is set to 64 ° C. and the polymerization is carried out as follows:

Zuerst werden 4 ml 30%-iges Wasserstoffperoxid zugegeben, 2 Minuten gerührt und mit dem Zusatz von 8680 Mikroliter einer 10%-igen Lösung von hydroximethansulfinsaurem Natrium begonnen (Dosiergeschwindigkeit 104 Mikroliter pro Minute) und dabei die Temperatur zwischen 63 und 67°C konstant gehalten. Nach 60 Minuten werden 0,5 ml 10%-ige Sodalösung eingefüllt und nach 135 Minuten ist die Hauptreaktion been­det. Es werden nun 0,5 ml t-Butylhydroperoxid 85%-ig,nach 150 Minuten nochmals 2 ml der 10%-igen Lösung von hydroxi­methansulfinsaurem Natrium zugegeben, ohne Heizung 15 Minu­ten weitergerührt und dann auf 25°C abgekühlt. Die erhaltene Dispersion weist einen Trockensubstanzgehalt von 42,3% und einen pH-Wert von 4 bis 5 auf.First 4 ml of 30% hydrogen peroxide are added, the mixture is stirred for 2 minutes and the addition of 8680 microliters of a 10% solution of sodium hydroxymethanesulfinate is started (metering rate 104 microliters per minute) and the temperature is kept constant between 63 and 67.degree . After 60 minutes, 0.5 ml of 10% sodium carbonate solution are poured in and after 135 minutes the main reaction has ended. 0.5 ml of 85% t-butyl hydroperoxide and then, after 150 minutes, a further 2 ml of the 10% solution of sodium hydroxymethanesulfinic acid are added, stirring is continued for 15 minutes without heating and then cooled to 25.degree. The dispersion obtained has a dry matter content of 42.3% and a pH of 4 to 5.

Zur Beschichtung wird ein weißer Polyamidtaft (ca. 70 g/m²) wie folgt behandelt:For the coating, a white polyamide taffeta (approx. 70 g / m²) is treated as follows:

1000 g der wie oben beschrieben hergestellten Dispersion des modifizierten Organopolysiloxancopolymeren werden mit 30 g eines handelsublichen Verdickers auf Basis Poly­acrylsäure (verdunnt 1:1 mit destilliertem Wasser) und 3 ml eines handelsüblichen nichtionogenen Entschäumers vermischt und unter Rühren langsam 1 ml 25%-iger Ammoniak zugetropft. Die Beschichtungsmasse wird so auf eine Viskosi­tät von 13000 mPa.s eingestellt (erfindungsgemäßes Pro­dukt A).1000 g of the dispersion of the modified organopolysiloxane copolymer prepared as described above mixed with 30 g of a commercially available thickener based on polyacrylic acid (diluted 1: 1 with distilled water) and 3 ml of a commercially available nonionic defoamer and slowly added 1 ml of 25% ammonia while stirring. The coating composition is adjusted to a viscosity of 13000 mPa.s (product A according to the invention).

Zum Vergleich gegenüber dem Stand der Technik wird ein Produkt B wie folgt bereitet:For comparison with the prior art, a product B is prepared as follows:

1000 g der im Beispiel 1 der DE-PS 2 616 797 angegebenen Copolymerisatdispersion werden mit 10 g einer Verbindung mit der Formel H₂N(CH₂)₂NH(CH₂)₃Si(OC₂H₅)₃ 20 g Dibutyl­zinndilaurat und 20 g 60%-iger Essigsäure zu einer Beschich­tungsmasse vermischt.1000 g of the copolymer dispersion specified in Example 1 of DE-PS 2 616 797 are combined with 10 g of a compound having the formula H₂N (CH₂) ₂NH (CH₂) ₃Si (OC₂H₅) ₃ 20 g of dibutyltin dilaurate and 20 g of 60% acetic acid Coating compound mixed.

Zum weiteren Vergleich nach dem Stand der Technik wird ein Produkt C wie folgt bereitet:For a further comparison according to the prior art, a product C is prepared as follows:

600 g der im Beispiel 1 der DE-PS 2 616 797 angegebenen Copolymerisationsdispersion und 400 g einer handelsüblichen ca. 60%-igen Dispersion eines α,ω -Dihydroxidimethylpoly­siloxans (Viskosität des Silikons ca. 80000 mPa.s bei 20°C) werden mit den unter Produkt B genannten Komponenten zu einer Beschichtungsmasse vermischt.600 g of the copolymerization dispersion given in Example 1 of DE-PS 2 616 797 and 400 g of a commercially available approximately 60% dispersion of an α, ω -dihydroxidimethylpolysiloxane (viscosity of the silicone approximately 80,000 mPa.s at 20 ° C.) are mixed with the components mentioned under product B are mixed to form a coating material.

Mit den so hergestellten Produkten A bis C wird der Poly­amidtaft in einem Strich mit 8 g/m² (bezogen auf Festsub­stanz) beschichtet, abschließend getrocknet, mit einer waßrigen Flotte aus 60 g/l® Scotchgard FC 270 (3M Company) und 10 g/l eines handelsüblichen ca. 60%-igen Extenders auf Basis fettmodifiziertes Kunstharz nachimprägniert, nochmals kurz getrocknet und bei ca. 150°C 2-3 Minuten kondensiert.
Die Ergebnisse der erhaltenen Ausrüstung sind - nach Auslie­gen im Normalklima - in der folgenden Tabelle zusammenge­faßt: Produkt Weißgrad nach GANZ Wasserdichtigkeit Griff (Wassersäule in mm) Weißgradabfall Weißgrad Orig. 5X40°C Masch. 3XChem. Reinigung A (entspr. d. Erfindung) + 3 24 üb.1000 210 350 Weich, angenehm fließend B (entspr. d. Stand der Technik) -20 1 üb.1000 190 235 Leicht klebrig, wenig weich C (entspr. d. Stand der Technik) -50 -29 220 120 180 Weich, papierig unbehandelt - 21 - - -

Figure imgb0002
With the products A to C thus produced, the polyamide taffeta is coated in one coat with 8 g / m 2 (based on solid substance), finally dried, with an aqueous liquor composed of 60 g / l® Scotchgard FC 270 (3M Company) and 10 g / l of a commercially available approx. 60% extender based on fat-modified synthetic resin, impregnated again, briefly dried and condensed at approx. 150 ° C for 2-3 minutes.
The results of the equipment obtained are summarized in the following table after being displayed in a normal climate: product Whiteness according to WHOLE Watertightness Handle (Water column in mm) Whiteness drop Whiteness Orig. 5X40 ° C Masch. 3XChem. cleaning A (according to the invention) + 3 24th over 1000 210 350 Soft, pleasantly flowing B (corresponding to the state of the art) -20 1 over 1000 190 235 Slightly sticky, not very soft C (corresponding to the state of the art) -50 -29 220 120 180 Soft, papery untreated - 21st - - -
Figure imgb0002

Beispiel 2Example 2

Das Beispiel 1 wird in der beschriebenen Weise wiederholt mit der Ausnahme, daß anstelle des dort angegebenen Meth­acryloyloxipropyltriethoxisilans 7,45 g Vinyltributoxisilan und anstelle des Cetylalkohols die gleiche Menge Lauryl­alkohol in der 1. Stufe zur Umsetzung verwendet werden.Example 1 is repeated in the manner described, with the exception that 7.45 g of vinyl tributoxisilane are used instead of the methacryloyloxypropyltriethoxisilane given there and the same amount of lauryl alcohol is used in the 1st stage for the reaction instead of the cetyl alcohol.

Wird mit dem so erhaltenen Produkt in gleicher Weise das gleiche Material beschichtet, so werden ähnliche Ausrü­stungsresultate erhalten.If the same material is coated in the same way with the product thus obtained, similar equipment results are obtained.

Beispiel 3Example 3

In der im Beispiel 1 angegebenen Weise werden aufbauend auf dem Organopolysiloxancopolymer der Stufe 1 des Bei­spiels 1 in der im Beispiel 1, Stufe 2 beschriebenen Weise folgende Monomeren copolymerisiert:
147 g Butylacrylat,
98 g Vinylacetat,
17 g Styrol und
12 g N-Methoximethylacrylamid.In the manner given in Example 1, the following monomers are copolymerized based on the organopolysiloxane copolymer of stage 1 of Example 1 in the manner described in Example 1, stage 2:
147 g butyl acrylate,
98 g vinyl acetate,
17 g styrene and
12 g of N-methoxymethylacrylamide.

Wird mit der so hergestellten, auf ca. 45 Gew.% Trockensub­stanz eingestellten Dispersion ein Polyester/Baumwollpope­line (67:33, ca. 110 g/m²) bzw. ein reiner Baumwollpopeline (120 g/m²) in einem Strich beschichtet (Auflage 10 bzw. 12 g/m²) und wie im Beispiel 1 angegeben, nachimprägniert und fertiggestellt, so wird ein guter Weißgrad, eine gute wasch- und reinigungsbeständige Wasserdichtigkeit und vor allem ein angenehm weicher Softhand-Griff erhalten.If a polyester / cotton poplin (67:33, approx. 110 g / m²) or a pure cotton poplin (120 g / m²) is coated in one coat with the dispersion prepared in this way, which is adjusted to approx. 45% by weight dry matter (edition 10 or 12 g / m²) and, as indicated in Example 1, impregnated and finished, a good degree of whiteness, good washable and cleaning-resistant water resistance and, above all, a pleasantly soft soft hand grip are obtained.

Beispiel 4Example 4

In der im Beispiel 1 angegebenen Weise wird aufbauend auf dem Organopolysiloxancopolymer der Stufe 1 des Beispiels 1 die Stufe 2 wie folgt durchgeführt:In the manner specified in Example 1, stage 2 is carried out as follows, based on the organopolysiloxane copolymer of stage 1 of example 1:

In dem Polymerisationsgefaß werden
645 g der in Stufe 1 hergestellten Dispersion,
11,2 g des dort genannten ethoxilierten Nonylphenolna­triumsulfats,
2,55 g der 10 %igen Losung von Polyvinylpyrrolidon,
169 g doppelt destilliertes Wasser,
0,55 g 2-Acrylamido-2-methylpropannatriumsulfonat und
5,9 g einer 10 %igen Sodalösung
im Abstand von etwa 3 Minuten eingefüllt und mit einer Geschwindigkeit von 250 Umdrehungen / Minute 1 Stunde zu­sammengerührt.Be in the polymerization vessel
645 g of the dispersion prepared in stage 1,
11.2 g of the ethoxylated nonylphenol sodium sulfate mentioned there,
2.55 g of the 10% solution of polyvinylpyrrolidone,
169 g of double distilled water,
0.55 g of 2-acrylamido-2-methylpropane sodium sulfonate and
5.9 g of a 10% soda solution
filled at intervals of about 3 minutes and stirred together at a speed of 250 revolutions / minute for 1 hour.

Daneben werden in einem Zulaufbehalter
105,4 g stabilisiertes Butylacrylat,
1,1 g des genannten ethoxilierten Isotridecylalkohols
auf 40°C erwärmt, bis eine klare Lösung erhalten wird und dann werden 25,7 g Acrylnitril unter Kühlen auf 25°C und 8,3 g N-Butoximethylmethacrylamid zugegeben (pH-Wert ca. 5,2).In addition, in an inlet container
105.4 g stabilized butyl acrylate,
1.1 g of said ethoxylated isotridecyl alcohol
heated to 40 ° C until a clear solution is obtained and then 25.7 g of acrylonitrile are added with cooling to 25 ° C and 8.3 g of N-butoximethyl methacrylamide (pH approx. 5.2).

Die Polymerisation wird wie im Beispiel 1 beschrieben durchgeführt. Es wird eine stabile Dispersion von 30 Gew.% erhalten.The polymerization is carried out as described in Example 1. A stable dispersion of 30% by weight is obtained.

Mit der so hergestellten Dispersion wird ein Baumwollpo­peline (ca. 120 g/m²) wie folgt ausgerüstet:A cotton poplin (approx. 120 g / m²) is equipped with the dispersion prepared in this way as follows:

Es wird eine Flotte aus
30 g/l einer 70 %igen wässrigen Lösung eines Cellulose­vernetzers (Mischung aus Dimethyloldihydroxiethy­lenharnstoff und mit Methanol verethertem Penta­methylolmelamin 6:1 mit ca. 4 % Neutralsalz),
9 g/l einer ca. 35 %igen, schwach sauren Zinknitratlö­sung,
2 ml/l 60 %ige Essigsäure
300 g/l der wie oben hergestellten 30 %igen Dispersion und
5 g/l Ethylenharnstoff
hergestellt, der Baumwollpopeline mit dieser Flotte foular­diert (Flottenaufnahme ca. 92 %), 10 Minuten bei 110°C getrocknet, anschließend bei 140°C kalandert und danach 5 Minuten bei 150°C nachkondensiert.It's going to be a fleet
30 g / l of a 70% aqueous solution of a cellulose crosslinker (mixture of dimethyloldihydroxyethylene urea and 6: 1 pentamethylolmelamine etherified with methanol with about 4% neutral salt),
9 g / l of an approx. 35% weakly acidic zinc nitrate solution,
2 ml / l 60% acetic acid
300 g / l of the 30% dispersion prepared as above and
5 g / l ethylene urea
prepared, padded the cotton poplin with this liquor (liquor absorption approx. 92%), dried at 110 ° C for 10 minutes, then calendered at 140 ° C and then post-condensed at 150 ° C for 5 minutes.

Das auf diese Weise ausgerüstete Gewebe weist eine sehr gute, beständige Wasserabweisung und einen angenehm wei­chen, fülligen Silikongriff auf, ohne daß der Weißgrad nennenswert in Mitleidenschaft gezogen wird.The fabric finished in this way has a very good, durable water repellency and a pleasantly soft, full silicone handle, without significantly affecting the degree of whiteness.

Beispiel 5Example 5

In der im Beispiel 1 beschriebenen Weise werden aufbauend auf dem Organopolysiloxancopolymer der Stufe 1 dieses Bei­spiels in der dort unter Stufe 2 beschriebenen Art folgende Monomeren copolymerisiert:
182 g Butylacrylat
99,3 g Ethylacrylat
5,1 g Acrylamid
1,6 g 2-Acrylamido-2-methylpropannatriumsulfonat und
24,3 g N-Butoximethylmethacrylamid.In the manner described in Example 1, the following monomers are copolymerized based on the organopolysiloxane copolymer of stage 1 of this example in the manner described there under stage 2:
182 g butyl acrylate
99.3 g of ethyl acrylate
5.1 g acrylamide
1.6 g of 2-acrylamido-2-methylpropane sodium sulfonate and
24.3 g of N-butoxymethyl methacrylamide.

Wird mit der so hergestellten, auf ca. 43,5 Gew.% Trocken­substanz eingestellten Dispersion eine Beschichtung auf dem in Beispiel 1 angegebenen Polyamidtaft vorgenommen, so werden ähnlich gute Resultate wie dort angegeben, er­zielt.If the dispersion prepared in this way, which is adjusted to approximately 43.5% by weight of dry substance, is coated on the polyamide taffeta given in Example 1, similarly good results are achieved as indicated there.

Beispiel 6Example 6

Ein handelsübliches Release-Papier wird mit folgender Zu­sammensetzung beschichtet:
200 g des in Beispiel 1 genannten erfindungsgemäßen Pro­duktes A,
2 g eines handelsublichen Verdickers auf Basis Poly­acrylsäure (verdunnt 1:1 mit destilliertem Wasser),
0,5 g eines handelsublichen Entschäumers (®RESPUMIT SI der Firma Bayer) und
5 ml/l eines 10%-igen Ammoniaks.A commercially available release paper is coated with the following composition:
200 g of product A according to the invention mentioned in Example 1,
2 g of a commercially available thickener based on polyacrylic acid (diluted 1: 1 with distilled water),
0.5 g of a commercially available defoamer (®RESPUMIT SI from Bayer) and
5 ml / l of a 10% ammonia.

Die Auflage beträgt (bezogen auf Trockensubstanz) 5 g/m². Danach wird das beschichtete Papier bei 90°C 10 Minuten getrocknet und bei 120°C 15 Minuten kondensiert. Das auf diese Weise mit einem weichen, wasserabweisenden und was­serdichten Film versehene Papier ist in hervorragender Weise als Trennpapier geeignet.The circulation is 5 g / m² (based on dry matter). The coated paper is then dried at 90 ° C. for 10 minutes and condensed at 120 ° C. for 15 minutes. The paper, which is provided with a soft, water-repellent and waterproof film in this way, is outstandingly suitable as release paper.

Claims (15)

1. Verfahren zur Behandlung von faserigen Materialien mit modifizierten Organopolysiloxanen, dadurch gekennzeichnet, daß in wäßrigem Medium ein Organopolysiloxancopolymer, hergestellt in einer 1. Stufe aus üblichen cyclischen Siloxanen (A) und (Meth)acrylatsilanen, Vinylsilanen und/oder cyclischen Vinylsiloxanen (B) in Gegenwart eines Vernetzers und Emulgators (1), in einer 2. Stufe mit mindestens einem Vinylmonomeren in Gegenwart von Emulga­toren (2) copolymerisiert und die entstandene Dispersion des modifizierten Organopolysiloxancopolymers in üblicher Weise auf das Material aufgebracht, getrocknet und konden­siert wird.1. A process for the treatment of fibrous materials with modified organopolysiloxanes, characterized in that an organopolysiloxane copolymer, prepared in a first stage from conventional cyclic siloxanes (A) and (meth) acrylatesilanes, vinylsilanes and / or cyclic vinylsiloxanes (B) in an aqueous medium. in the presence of a crosslinking agent and emulsifier (1), in a second stage copolymerized with at least one vinyl monomer in the presence of emulsifiers (2) and the resulting dispersion of the modified organopolysiloxane copolymer is applied to the material in a customary manner, dried and condensed. 2. Verfahren nach Patentanspruch (1), dadurch gekennzeichnet, daß das Organopolysiloxancopolymer durch Umsetzung von 90 bis 99,8 Gew.% Verbindung (A) mit 10 bis 0,2 Gew.% Verbindung (B) hergestellt worden ist, wobei als Verbin­dung (B) ein Tetramethylvinylcyclosiloxan und/oder eine Verbindung der Formel
Figure imgb0003
 Formel
und/oder der CH₂ = CH - Si(R)3-n(OR)n,
eingesetzt worden sind, worin R1 = H oder CH₃, x = 2-6, R = C2-3-alkyl - C1-3-alkoxy, oder C1-6-alkyl und n = 1, 2 oder 3 sind.2. The method according to claim (1), characterized in that the organopolysiloxane copolymer has been prepared by reacting 90 to 99.8% by weight of compound (A) with 10 to 0.2% by weight of compound (B), the compound being (B) a tetramethylvinylcyclosiloxane and / or a compound of the formula
Figure imgb0003
 formula
and / or the CH₂ = CH - Si (R) 3-n (OR) n ,
have been used, wherein R1 = H or CH₃, x = 2-6, R = C2-3-alkyl - C1-3-alkoxy, or C1-6-alkyl and n = 1, 2 or 3. 3. Verfahren nach Patentanspruch 2, dadurch gekennzeichnet, daß in den genannten Formeln R1 = CH₃, R = C1-6-alkyl, x = 3 oder 4 und n = 2 oder 3 bedeuten.3. The method according to claim 2, characterized in that in the formulas mentioned R1 = CH₃, R = C1-6-alkyl, x = 3 or 4 and n = 2 or 3. 4. Verfahren nach mindestens einem der Patentansprüche 1 bis 3, dadurch gekennzeichnet, daß die Herstellung des Organopolysiloxancopolymers in Gegenwart von 0,1 bis 15, insbesondere in Gegenwart von 0,5 bis 10 Gew.% Ver­netzer erfolgt ist.4. The method according to at least one of claims 1 to 3, characterized in that the preparation of the organopolysiloxane copolymer is carried out in the presence of 0.1 to 15, in particular in the presence of 0.5 to 10 wt.% Crosslinking agent. 5. Verfahren nach mindestens einem der Patentansprüche 1 bis 4, dadurch gekennzeichnet, daß die Verbindung (B) gleichzeitig als Vernetzer eingesetzt worden ist.5. The method according to at least one of claims 1 to 4, characterized in that the compound (B) has been used simultaneously as a crosslinker. 6. Verfahren nach mindestens einem der Patentansprüche 1 bis 5, dadurch gekennzeichnet, daß als Emulgator (1) eine Mischung aus einer anionischen Sulfonsäure und einem Dispergierhilfsmittel verwendet worden ist.6. The method according to at least one of claims 1 to 5, characterized in that a mixture of an anionic sulfonic acid and a dispersing aid has been used as emulsifier (1). 7. Verfahren nach mindestens einem der Patentansprüche 1 bis 6, dadurch gekennzeichnet, daß als Dispergierhilfs­mittel ein gerad- und/oder verzweigtkettiger Alkohol mit 8 bis 20°C-Atomen verwendet worden ist.7. The method according to at least one of claims 1 to 6, characterized in that a straight and / or branched chain alcohol having 8 to 20 ° C atoms has been used as the dispersing aid. 8. Verfahren nach mindestens einem der Patentansprüche 1 bis 7, dadurch gekennzeichnet, daß als Verbindung (A) Octamethyltetracyclosiloxan verwendet worden ist.8. The method according to at least one of claims 1 to 7, characterized in that octamethyltetracyclosiloxane has been used as compound (A). 9. Verfahren nach mindestens einem der Patentansprüche 1 bis 8, dadurch gekennzeichnet, daß in der 2. Stufe mindes­tens 1 Vinylmonomeres in solchen Mengen copolymerisiert worden ist, daß das Gewichtsverhältnis von Organopoly­siloxancopolymer zu Vinylmonomer 1:0,5 bis 1:4, ins­besondere 1:1 bis 1:2,5 beträgt.9. The method according to at least one of claims 1 to 8, characterized in that in the second stage at least 1 vinyl monomer has been copolymerized in such amounts that the weight ratio of organopolysiloxane copolymer to vinyl monomer 1: 0.5 to 1: 4, in particular 1 : 1 to 1: 2.5. 10. Verfahren nach mindestens einem der Patentansprüche 1 bis 9, dadurch gekennzeichnet, daß in der 2. Stufe als Vinylmonomere Alkylacrylate mit 2 bis 6 C-Atomen im Alkyl­rest als Basismonomere, weiterhin Acrylnitril, Styrol und/oder ein vernetzungsfähiges Monomeres copolymerisiert worden sind.10. The method according to at least one of claims 1 to 9, characterized in that in the second stage as vinyl monomers alkyl acrylates having 2 to 6 carbon atoms in the alkyl radical as base monomers, acrylonitrile, styrene and / or a crosslinkable monomer have been copolymerized. 11. Verfahren nach mindestens einem der Patentansprüche 1 bis 10, dadurch gekennzeichnet, daß in der 2. Stufe zu­sätzlich ein hydrophiles Vinylmonomeres, vor allem 2-­Acrylamido-2-methylpropan-Natrumsulfonat und/oder Natrium­vinylsulfonat copolymerisiert worden ist.11. The method according to at least one of claims 1 to 10, characterized in that in the second stage, a hydrophilic vinyl monomer, especially 2-acrylamido-2-methylpropane sodium sulfonate and / or sodium vinyl sulfonate has been copolymerized. 12. Verfahren nach mindestens einem der Patentansprüche 1 bis 11, dadurch gekennzeichnet, daß zur Emulgierung wäh­rend der 2. Stufe zusätzlich zum Emulgator (1) noch nicht­ionische Emulgatoren und/oder ethoxylierte, anionaktive Emulgatoren (=Emulgatoren (2)) und Schutzkolloide ver­wendet worden sind und die Copolymerisation bei einem schwachsauren bis neutralen pH-Wert durchgeführt worden ist.12. The method according to at least one of claims 1 to 11, characterized in that non-ionic emulsifiers and / or ethoxylated, anionic emulsifiers (= emulsifiers (2)) and protective colloids have been used in addition to the emulsifier (1) for emulsification during the second stage and the copolymerization has been carried out at a weakly acidic to neutral pH. 13. Verfahren nach mindestens einem der Patentansprüche 1 bis 12, dadurch gekennzeichnet, daß die Herstellung des Organopolysiloxancopolymers und die anschließende Copoly­merisation des/der Vinylmonomeren im Eintopfverfahren durchgeführt worden ist.13. The method according to at least one of claims 1 to 12, characterized in that the preparation of the organopolysiloxane copolymer and the subsequent copolymerization of the vinyl monomer (s) has been carried out in a one-pot process. 14. Verfahren nach mindestens einem der Patentansprüche 1 bis 13, dadurch gekennzeichnet, daß das modifizierte Organopolysiloxancopolymer in Mengen von mindestens 5, insbesondere 5 bis 70 g/m², bevorzugt 5 bis 20 g/m², auf die faserigen Materialien durch Beschichten in üb­licher Weise aufgebracht wird.14. The method according to at least one of claims 1 to 13, characterized in that the modified organopolysiloxane copolymer in amounts of at least 5, in particular 5 to 70 g / m², preferably 5 to 20 g / m², on the fibrous materials by coating in a conventional manner is applied. 15. Nach mindestens einem der Patentansprüche 1 bis 14 be­handelte faserige Materialien, insbesondere Textilien.15. According to at least one of claims 1 to 14 treated fibrous materials, especially textiles.
EP89120826A 1988-11-19 1989-11-10 Method for the treatment of fibrous materials with modified organopolysiloxanes, and materials so treated Expired - Lifetime EP0370326B1 (en)

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AT89120826T ATE92551T1 (en) 1988-11-19 1989-11-10 PROCESSES FOR TREATMENT OF FIBROUS MATERIALS WITH MODIFIED ORGANOPOLYSILOXANES AND THE MATERIALS SO TREATED.

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DE3839136 1988-11-19
DE3839136A DE3839136A1 (en) 1988-11-19 1988-11-19 METHOD FOR THE TREATMENT OF FIBROUS MATERIALS WITH MODIFIED ORGANOPOLYSILOXANS AND THE MATERIALS TREATED THEREFORE

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EP0370326A2 true EP0370326A2 (en) 1990-05-30
EP0370326A3 EP0370326A3 (en) 1992-04-08
EP0370326B1 EP0370326B1 (en) 1993-08-04

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JP (1) JPH02175973A (en)
AT (1) ATE92551T1 (en)
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ES (1) ES2058445T3 (en)

Cited By (2)

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EP0643090A2 (en) * 1993-09-13 1995-03-15 Pfersee Chemie GmbH Organic silicon compound-containing compositions suitable for treating fibrous materials
EP0731207A1 (en) * 1995-03-09 1996-09-11 Wacker-Chemie GmbH Binder for textile material

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DE4101884C2 (en) * 1991-01-23 2001-05-03 Sonderhoff Ernst Fa Process for the production of foam coatings or for surface bonding of materials and its use
FR2796272B1 (en) * 1999-07-15 2003-09-19 Oreal COMPOSITION WITHOUT WAX STRUCTURED IN A RIGID FORM BY A POLYMER
GB0029198D0 (en) * 2000-11-30 2001-01-17 Ciba Sc Holding Ag Liquid dispersion polymer compositions their preparation and their use
US8080257B2 (en) 2000-12-12 2011-12-20 L'oreal S.A. Cosmetic compositions containing at least one hetero polymer and at least one film-forming silicone resin and methods of using
US6716420B2 (en) 2001-10-05 2004-04-06 L′Oreal Methods of use and of making a mascara comprising at least one coloring agent and at least one heteropolymer
US20050008598A1 (en) 2003-07-11 2005-01-13 Shaoxiang Lu Cosmetic compositions comprising a structuring agent, silicone powder and swelling agent

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FR2398782A1 (en) * 1977-07-25 1979-02-23 Bausch & Lomb CONTACT LENS
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EP0643090A2 (en) * 1993-09-13 1995-03-15 Pfersee Chemie GmbH Organic silicon compound-containing compositions suitable for treating fibrous materials
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US5562761A (en) * 1993-09-13 1996-10-08 Ciba-Geigy Corporation Compositions, containing organic silicon compounds, for the treatment of fibre materials
EP0731207A1 (en) * 1995-03-09 1996-09-11 Wacker-Chemie GmbH Binder for textile material

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ATE92551T1 (en) 1993-08-15
DE3839136A1 (en) 1990-05-23
EP0370326A3 (en) 1992-04-08
ES2058445T3 (en) 1994-11-01
JPH02175973A (en) 1990-07-09
DE58905149D1 (en) 1993-09-09
EP0370326B1 (en) 1993-08-04

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