EP2004728A2

EP2004728A2 - Organosilicone copolymers

Info

Publication number: EP2004728A2
Application number: EP07729528A
Authority: EP
Inventors: Oliver Minge; Peter Ball; Andrea Kneissl
Original assignee: Wacker Chemie AG
Current assignee: Wacker Chemie AG
Priority date: 2006-06-01
Filing date: 2007-05-25
Publication date: 2008-12-24
Also published as: DE102006025668A1; KR20080112402A; WO2007138010A3; CN101460544B; CN101460544A; US20090186982A1; JP2009538945A; WO2007138010A2

Abstract

The invention relates to organosilicone copolymers (O) obtained by radically polymerizing A1) ethylenically unsaturated monomers selected among N-methylolacrylamide (NMA), N-methylolmethacrylamide, N-methylolallylcarbamate, alkyl ethers or esters of N-methylolacrylamide, N-methylolmethacrylamide, and N- methylolallylcarbamate, with A2) ethylenically unsaturated monomers selected among vinyl esters, (meth)acrylic acid esters, vinyl aromatics, olefins, 1,3-dienes, vinyl ethers, and vinyl halides, and A3) optional auxiliary monomers, and B) ethylenically monounsatured or polyunsaturated polyorganosiloxanes in an aqueous medium.

Description

organosilicone copolymers

The present invention relates to organosilicone copolymers of ethylenically unsaturated monomers and ethylenically unsaturated polyorganosiloxanes, their preparation and use.

It is known that the use of polymers in the field of paper and textile equipment is necessary in order to give the substrates mechanical properties such as tensile strength,

To give and improve elongation at break, elasticity or dry and wet abrasion resistance. Besides natural polymers, in particular starch, synthetic polymers are also used, which, due to environmental considerations and legal regulations, are ideally used in aqueous solutions

Dosage form can be used. Ideally, good adhesion to the substrate should be achieved after application of the polymer or binder to the fiber. The aqueous polymer dispersions most commonly used in the art are therefore those which are functionalized with crosslinking monomers which, when dried at high temperature, can provide covalent bonds between the polymer chains and between the polymer and the fiber. In this way, it is possible to form crosslinked structures which are resistant to the action of foreign substances.

The functional monomers most effective for this application are methylol derivatives of (meth) acrylamide, e.g. N-methylol (meth) acrylamide (N (M) MA). These monomers are characterized by an ethylenic double bond, which allows them to undergo a radical polymerization, and by a NHCH2θH group, the crosslinking by means of a

Condensation reaction with other functional groups at a high temperature generally above 100 ⁰ C, often under acidic catalysis granted. In this way, covalent bonds are formed between chains or between a polymer chain and the support.

For example, EP 1482081 A1 describes an aqueous copolymer dispersion for the treatment of non-woven fabrics based on vinyl acetate and ethylene, which contain post-crosslinking groups of the ZV-methylolacrylamide type. The disclosed binders impart high dry and wet tensile strength to the fibers.

EP 143175 B2 discloses N-methylolacrylamide-modified polymer dispersions based on vinyl ester / acrylate copolymers. Another route is disclosed in US 6913628. It describes silane-modified binders based on acrylates. The silane modification achieves postcrosslinkability, resulting in improved tensile strengths, but the permanence of the fiber connection is not given since the resulting Si-O-C bonds are hydrolysis-labile and pH-sensitive.

All of these systems mentioned are two principal

Inadequacies in common:

Thus, on the one hand an even greater dry and wet strength is desired, or a polymer, which at reduced

Active ingredient content corresponding to the prior art

Strengths guaranteed.

On the other hand, it is known that the known polymers affect the haptic properties, such as the softness of a fabric or a fiber (hand feeling) usually very unfavorable. By applying other polymers, the feel of fibers and fabrics can be improved. For example, to positively influence the softness, silicones and silicone-containing structures are generally used. Again, adhesion of the drug to the substrate is desired. Examples of these are amino-functional silicone oils ("amine oils"), which, in addition to hydrophobicity, are known to have a positive effect on the softness of textiles, because of their Lewis-basic amino groups, they also have the property of Lewis acid fibers

Such silicone amine oils and their applications are described, for example, in WO2005010076 and are state of the art, however, as is known, the permanence generated by the application of the amine oils is only temporary and insufficient and the coating can be easily removed both mechanically and chemically. A further disadvantage of aminosilicones is the fact that although a softening is desired for certain applications, hydrophobing is by no means an advantage since, for example, the water absorption capacity of the fibers is adversely affected.

The invention relates to organosilicone copolymers (O) obtainable by free-radical polymerization in an aqueous medium of

Al) ethylenically unsaturated monomers selected from N-methylolacrylamide (NMA), N-methylolmethacrylamide, N-methylolallyl carbamate, alkyl ethers or esters of N-methylolacrylamide, N-methylolmethacrylamide and N-methylolallylcarbamate, with

A2) ethylenically unsaturated monomers which are selected from vinyl esters, (meth) acrylic acid esters, vinylaromatics, olefins, 1,3-dienes, vinyl ethers and vinyl halides and A3) optionally auxiliary monomers and

B) mono or multiply ethylenically unsaturated

Polyorganosiloxanes.

The resulting organosilicone copolymers (O) give dry and wet tensile strength to treated substrates such as fibers, paper and textiles superior to those of the prior art and at the same time transfer silicone character to the polymer at the appropriate silicone content without adversely affecting the hydrophilicity of the fiber. The

Hydrophobization of the substrate can be easily adjusted.

Preferably, the free radical polymerization takes place in emulsion or miniemulsion. The resulting aqueous dispersions of Organosiliconcopolymere (O) can be used directly for the treatment of the substrates. The aqueous dispersions can also be processed by drying to redispersible polymer powders. Most preferably, the polymerization takes place in miniemulsion.

Preferred esters (Al) of acrylamidoglycolic acid (AGA) and of methylacrylamidoglycolic acid are the C 1 -C -alkyl esters.

Preferred esters (Al) of N-methylolacrylamide, N-methylol methacrylamide and N-Methylolallylcarbamats are the esters of _C] _{_-C]} _ _Q ~ alkyl carboxylic acids. Preferred ethers (Al) of the N-

Methylolacrylamide, N-Methylolmethacrylamids and N-Methylolallylcarbamats are the C] _ C] _g-alkyl ethers.

Particularly preferred ethylenically unsaturated monomers A1) are N-methylolacrylamide (NMA), N-methylolmethacrylamide and N-methylolallyl carbamate which have postcrosslinkable methylol groups. Preferred ethylenically unsaturated monomers A2) are vinyl esters of carboxylic acids having 1 to 15 carbon atoms. Particular preference is given to vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate and vinyl esters of C-C-branched monocarboxylic acids having 9 to 11 C atoms, for example VeoVa9R or VeoValOR (trade name of the company Resolution). Particularly preferred is vinyl acetate. Preferred monomers A2) from the group of acrylic acid esters or methacrylic acid esters are esters of unbranched or branched alcohols having 1 to 15 C atoms. preferred

Methacrylic acid esters or acrylates are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate and

Norbornyl acrylate. Particularly preferred are methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and norbornyl acrylate. Preferred vinylaromatics A2) are styrene, alpha-

Methylstyrene, the isomeric vinyltoluenes and Vinylxylole and divinylbenzenes. Particularly preferred is styrene. Among the vinyl halide compounds are vinyl chloride, vinylidene chloride, further tetrafluoroethylene, difluoroethylene, hexylperfluoroethylene, 3, 3, 3-trifluoropropene, perfluoropropyl vinyl ether, hexafluoropropylene, chlorotrifluoroethylene and vinyl fluoride mentioned. Particularly preferred is vinyl chloride. A preferred vinyl ether A2) is, for example, methyl vinyl ether. The preferred olefins A2) are ethene,

Propene, 1-alkylethenes and polyunsaturated alkenes, and the preferred dienes are 1,3-butadiene and isoprene. Particularly preferred are ethene and 1, 3-butadiene. Particular preference is given as monomers A2) to one or more monomers from the group of vinyl acetate, vinyl esters of C-C-branched monocarboxylic acids having 9 to 11 C atoms, vinyl chloride, ethylene, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, styrene, 1, 3-butadiene. Particularly preferred monomers A2) are mixtures of n-butyl acrylate and 2-ethylhexyl acrylate and / or methyl methacrylate; Mixtures of

Styrene and one or more monomers from the group of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate; Mixtures of vinyl acetate and one or more monomers from the group of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and optionally ethylene; Mixtures of 1,3-butadiene and styrene and / or methyl methacrylate.

Optionally, it is also possible to copolymerize 0.1 to 5% by weight, based on the total weight of the monomers Al) + A2), auxiliary monomers A3). Preferably, 0.5 to 2.5 wt .-% auxiliary monomers are used. Examples of auxiliary monomers A3) are ethylenically unsaturated mono- and dicarboxylic acids, preferably acrylic acid, methacrylic acid, fumaric acid and maleic acid; ethylenically unsaturated carboxylic acid amides and nitriles, preferably acrylamide and acrylonitrile; Mono- and diesters of fumaric acid and maleic acid such as diethyl and diisopropyl esters and maleic anhydride, ethylenically unsaturated sulfonic acids or their salts, preferably vinylsulfonic acid, 2-acrylamido-2-methyl-propanesulfonic acid.

Also suitable are epoxide-functional ethylenically unsaturated comonomers such as glycidyl methacrylate and glycidyl acrylate. Also mentioned are ethylenically unsaturated monomers with hydroxy or CO groups, for example methacrylic acid and

Acrylic acid hydroxyalkyl esters such as hydroxyethyl, hydroxypropyl or hydroxybutyl acrylate or methacrylate and compounds such as diacetoneacrylamide and acetylacetoxyethyl acrylate or methacrylate. Also mentioned are copolymerizable ethylenically unsaturated silanes, for example vinylsilanes such as vinyltrimethoxysilane or vinyltriethoxysilane or (meth) acrylsilanes, for example the silanes GENIOSIL® GF-31 (methacryloxypropyltrimethoxysilane) sold by Wacker-Chemie AG, Munich, Germany, XL-33 (methacryloxymethyltrimethoxysilane) , XL-32 (methacryloxymethyldimethylmethoxysilane), XL-34 (methacryloxymethylmethyldimethoxysilane) and XL-36 (methacryloxymethyltriethoxysilane).

Preferred mono- or polyethylenically unsaturated polyorganosiloxanes B) have the general formula [1]

(SiO ^ k CR ^ IOA ^ MCR ^ S ^^ ^ pCR SIOI ^ q [Oi / 2SiR3 ₂ -LX] _s [Oi / 2H] _t [1]

on, where

L is a bivalent optionally substituted aromatic, heteroaromatic or aliphatic radical (CR ⁴ ₂ ) b,

R ^, R ^, R ^ represents a hydrogen atom or a monovalent, optionally with -CN, -NCO, -NR ² ₂ , -COOH, -COOR ² , -PO (OR ² ) 2, -halogen, -acrylic, -epoxy, -SH, -OH or -CONR ² ₂ substituted C] _- C20 ~ ^κ ° hydrogen radical or C] _- C20 ~ hydrocarbonoxy, in which in each case one or more, not adjacent methylene units by groups

-0-, -CO-, -COO-, -OCO-, or -Oc00-, -S-, or -NR ² - and in which one or more non-adjacent methine units can be replaced by groups, -N =, -N = N-, or -P =, X is an ethylenically unsaturated radical, R 2 is hydrogen or a monovalent optionally substituted Hydrocarbon residue, b integer values of at least 1, s integer values of at least 1, t 0 or integer values, k + m + p + q mean integer values of at least 2.

Preferred polyorganosiloxanes B) are those whose C] _C _2Q - hydrocarbon radicals and C] _C ₂ o-Kohlenwasserstoffoxyreste RA,

R 3, R ^ may be aliphatically saturated or unsaturated, aromatic, straight-chain or branched. R 1, R 2, R 2 preferably have 1 to 12 atoms, in particular 1 to 6 atoms, preferably only carbon atoms, or an alkoxy oxygen atom and otherwise only carbon atoms.

Preferably, R ^ -, R ^, R ^ are straight-chain or branched C] _-C5-alkyl radicals or phenyl radicals. The radicals methyl, ethyl, phenyl and vinyl are particularly preferred.

Preferably, R 1 is a methyl radical and R 1 is hydrogen.

X is preferably an ethylenically unsaturated radical of the vinyl (-C ₂ H ₃ ), acrylic (-OCOC ₂ H ₃ ) or methacrylic type (-OCOC ₂ H ₂ CH ₃ ) _#

Preferably, b has values of at most 50, in particular at most 10. In particularly preferred embodiments, b is 2 or 3.

The polyorganosiloxane B) of the general formula [1] may be linear, cyclic, branched or crosslinked. The sum of k, m, p, q, s and t is preferably a number of 3 to 20,000, especially 8 to 1,000. Another preferred variant of a polyorganosiloxane B) of the general formula [1] is an organosilicone resin. This may consist of several units as described in the general formula [1], wherein the molar percentages of the units contained are denoted by the indices k, m, p, q, k + m must be> 0. Preference is given here to using polysiloxane resins B) in which k + m is> 50%, based on the sum of k, m, p, q. Particularly preferred are resins for which k + m> 90%.

A further preferred variant of a polyorganosiloxane B) of the general formula [1] is an organosilicone resin which consists exclusively or almost exclusively of SiC> 4/2 units; where k is greater than m + p + q. Preferably, the proportion of k, based on the sum of k, m, p, q is at least 51%, particularly preferably the proportion of k> 95% or from 55 to 65%.

A further preferred variant of a polyorganosiloxane B) of the general formula [1] is a linear polyorganosiloxane which consists exclusively or almost exclusively of SiC> 2/2 ~

Consists of units; It is true that the silicone is composed almost exclusively of difunctional units p. Preferably, the proportion of p, based on the sum of k, m, p, q is at least 95%, more preferably, the proportion of p> 95%.

The monomer selection or the selection of the weight fractions of the comonomers Al), A2), optionally A3) and B) is carried out so that in general a glass transition temperature Tg of <60 ⁰ C, preferably -50 ⁰ C to + 60 ° C results. The

Glass transition temperature Tg of the organosilicone copolymers (O) can be determined in a known manner by means of differential scanning calorimetry (DSC). The Tg can also be determined by means of the Fox Approximated approximate equation. After Fox TG, Bull. Am. Physics Soc. 1, 3, page 123 (1956): l / Tg = xl / Tgl + x2 / Tg2 + ... + xn / Tgn, where xn is the mass fraction (wt .-% / 100) of the monomer n, and Tgn is the glass transition temperature in Kelvin of the homopolymer of

Monomers n is. Tg values for homopolymers are listed in Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975).

Based on 100 parts by weight of the ethylenically unsaturated monomers A2) are preferably at least 2, in particular at least 8 parts by weight and preferably at most 100 parts by weight, in particular at most 30 parts by weight of ethylenically unsaturated monomers Al).

Based on 100 parts by weight of the ethylenically unsaturated monomers A2) are preferably at least 3, in particular at least 10 parts by weight and preferably at most 150 parts by weight, in particular at most 500 parts by weight of ethylenically unsaturated polyorganosiloxanes B).

The organosilicone copolymers (O) are preferably prepared in a heterophasic process by the known techniques of suspension, emulsion or miniemulsion polymerization (cf., for example, Peter A. Lovell, MS El-Aasser, "Emulsion Polymerization and Emulsion Polymers" 1997, John Wiley and Sons, Chichester). In a particularly preferred form, the reaction is carried out according to the method of miniemulsion polymerization. Miniemulsion polymerizations differ in some key respects, making them particularly suitable for the copolymerization of water-insoluble comonomers or macromers from other heterophase polymerizations (see eg K. Landfester, "Polyreactions in Miniemulsions", Macromol Rapid Commun. 2001, 22, 896-936 and MS El-Aasser, Ed Sudol, "Miniemulsions: Overview of Research and Applications"). 2004, JCT Research, 1, 20-31).

The reaction temperatures range from 0 ⁰ C to 100 ⁰ C, preferably 5 ° C to 80 ⁰ C, particularly preferably from 30 ⁰ C to 80 ° C. The pH of the dispersing medium is from 2 to 9, preferably from 4 to 8. In a particularly preferred embodiment, from 6.5 to 7.5. The adjustment of the pH value before the beginning of the reaction can be carried out by hydrochloric acid or sodium hydroxide solution. The polymerization can be carried out batchwise or continuously, with presentation of all or individual constituents of the reaction mixture, with partial introduction and subsequent addition of individual constituents of the reaction mixture or after the metering process without presentation. All dosages are preferably carried out in proportion to the consumption of the respective component. Particularly preferred is a polymerization in the batch mode.

The heterogeneous phase polymerization preferably proceeds in the presence of one or more dispersants. Dispersants which can be used are all commonly used emulsifiers and / or protective colloids. Suitable protective colloids are, for example, partially hydrolyzed polyvinyl alcohols, polyvinylpyrrolidones, polyvinyl acetals and starches and celluloses and their carboxymethyl, methyl, hydroxyethyl, hydroxypropyl derivatives. Suitable emulsifiers are anionic, cationic and nonionic emulsifiers, for example anionic surfactants, such as alkyl sulfates having a chain length of 8 to 18 carbon atoms, alkyl or alkylaryl ether sulfates having 8 to 18 carbon atoms in the hydrophobic radical and up to 60 ethylene or Propylene oxide units, alkyl or alkylaryl sulfonates having 8 to 18 C atoms, esters and half esters of succinic acid with monohydric alcohols or alkylphenols, or nonionic surfactants such as alkyl polyglycol ethers or alkylaryl polyglycol ethers having up to 60 ethylene oxide or propylene oxide units. Other useful emulsifiers and protective colloids can be found in McCutchen's Detergents and Emulsifiers, North American Edition, 1979. The protective colloids and / or emulsifiers are generally added in an amount of generally 1 to 20% by weight, based on the total weight of the comonomers Al ), A2), optionally A3) and B) are added during the polymerization.

The initiation of the polymerization by means of the customary, usually at least partially water-soluble initiators or redox initiator combinations. Examples of initiators are the sodium, potassium and ammonium salts of peroxodisulfuric acid, hydrogen peroxide, t-butyl peroxide, t-butyl hydroperoxide, potassium peroxodiphosphate, t-butyl peroxypivalate, cumene hydroperoxide, isopropylbenzene monohydroperoxide and azobisisobutyronitrile. The initiators mentioned are preferably used in amounts of from 0.01 to 4.0% by weight, based on the total weight of the comonomers Al), A2), if appropriate A3) and B). As redox initiator combinations used above initiators in conjunction with a reducing agent. Suitable reducing agents are sulfites and bisulfites of monovalent cations, for example sodium sulfite, the derivatives of sulfoxylic acid, such as zinc or alkali metal formaldehyde sulfoxylates, for example sodium hydroxymethanesulfinate and ascorbic acid. The amount of reducing agent is preferably 0.15 to 3% by weight of the comonomers Al), A2) used, if appropriate A3) and B). In addition, small amounts of an im

Polymerization medium soluble metal compound are introduced, the metal component of which Polymerization is redox active, for example, based on iron or vanadium. Particularly preferred initiators are peroxodisulfate salts, in particular ammonium peroxodisulfates, optionally in combination with reducing agents, in particular sodium hydroxymethanesulfinate. In the case of Reaktionsfuhrung after the

Miniemulsion polymerization can also be used predominantly oil-soluble initiators, such as cumene hydroperoxide, isopropylbenzene monohydroperoxide, dibenzoyl peroxide or azobisisobutyronitrile. Preferred initiators for miniemulsion polymerizations are potassium persulfate, ammonium persulfate, azobisisobutyronitrile and dibenzoyl peroxide. An overview of suitable initiators in addition to the representatives just described can be found in the Handbook of Free Radical Initiators, E.T. Denisov, T.G. Denisova, T.S. Pokidova, 2003, Wiley Verlag

To prepare water-redispersible polymer powders, the aqueous dispersions of the organosilicone copolymers (O) are dried in a manner known to the person skilled in the art, preferably by the spray-drying process.

Depending on the application, optionally one or more additives may be added to the organosilicone copolymers (O). Examples of these are solvents or film-forming aids; Mixtures of at least two organic solvents; Pigment wetting and dispersing agents; surface effect additives, such as those used to achieve textures such as the hammered texture or the orange peel; Anti-foaming agent; Substrate wetting agents; Surface leveling agents; Adhesion promoters; Release agents; another organic polymer which is not identical to the organic polymer according to the invention; surfactant; hydrophobic Adjuvant; a non-radically polymerizable silicone resin.

The Organosiliconcopolymere (O) are suitable in pure form or as a component of aqueous or organic formulations as coating agents, binders and coating agents for a variety of substrates, especially fabrics and fibers of any kind, such as cellulose fibers, cotton and paper fibers, as well as Kunsstofffasern comprising but not limited to polyester, polyamide or polyurethane fibers.

The organosilicone copolymers (O) having postcrosslinkable methylol unsaturated monomers Al) are suitable for coating moldings and surfaces capable of

To react chemically methylol functions, such as wood or wood composites, and paper-coated substrates and Formkorper.

The treatment of the above substrates with the

Organosilicone copolymers (O) impart improved mechanical properties to the treated substrate, especially dry and wet tensile strengths. In addition, at the same silicone content at the same time typical

Mediated silicone properties, including an adjustable hydrophobing of the substrate is effected.

All the above symbols of the above formulas each have their meanings independently of each other. In all formulas, the silicon atom is tetravalent. The following examples serve to further illustrate the invention. In the following examples, unless stated otherwise, all amounts and percentages are by weight.

Examples

Example 1 (preparation of a polymer dispersion according to the invention):

Reaction components:

27 parts of methyl methacrylate

27 parts of n-butyl acrylate

7.7 parts of monomethacrylic PDMS (M _n about 3200 g / mol) 7.5 parts of N- (hydroxymethyl) acrylamide (50% in H ₂ O)

2 parts of itaconic acid

0.15 parts of ammonium peroxodisulfate

1.5 parts sodium dodecyl sulfate

292 parts water 0.5 parts hexadecane

All starting materials were weighed in a kettle and stirred for five minutes at room temperature. Subsequently, the mixture was homogenized using a high-pressure homogenizer of the type EmulsiFlex C5 Avestin Europe GmbH, Mannheim, Germany, at a pressure of about 750 bar. The resulting miniemulsion was transferred to a stirred tank and polymerized under nitrogen atmosphere at 75 ° C within 6 hours. An aqueous polymer dispersion having a solids content of 19% is obtained.

Example 2 (preparation of a polymer dispersion according to the invention): Reaction components: 27 parts of methyl methacrylate 27 parts of n-butyl acrylate 7.7 parts of polymethacrylic silicone resin from approx. 59%

SiO _{_4/2} -, Z ₁ ₃ SiO ₂ 37% Me - & oylmethyldimethylsilyleinheiten 4% methacrylic

7.5 parts of N- (hydroxymethyl) acrylamide (50% in H ₂ O)

2 parts of itaconic acid

0.15 parts of ammonium peroxodisulfate

1.5 parts sodium dodecyl sulfate

292 parts of water

0.5 parts hexadecane

The procedure corresponds to the procedure in Example 1. Fixed content: 18%

Example 3 Production of a Polymer Dispersion According to the Invention

Reaction components: 27 parts of methyl methacrylate

27 parts of n-butyl acrylate

7.7 parts of monomethacrylic PDMS (M _n approx. 6000 g / mol)

7.5 parts of N- (hydroxymethyl) acrylamide (50% in H ₂ O)

4 parts ZV, ZV-diethylaminoethyl methacrylate 0, 15 parts of ammonium peroxodisulfate

1.5 parts sodium dodecyl sulfate

292 parts of water

0.5 parts hexadecane

The procedure corresponds to the procedure in Example 1. Fixed content: 18% Example 4 Production of a Polymer Dispersion According to the Invention

Reaction components:

27 parts of methyl methacrylate

27 parts of n-butyl acrylate

7.7 parts of monomethacrylic PDMS (M _n approx. 6000 g / mol)

7.5 parts of N- (hydroxymethyl) acrylamide (50% in H2O)

4 parts ZV, ZV-diethylaminoethyl methacrylate

2 parts of itaconic acid

0.15 parts of ammonium peroxodisulfate

1.5 parts sodium dodecyl sulfate

292 parts of water

0.5 parts hexadecane

The procedure corresponds to the procedure in Example 1. Fixed content: 19%

Example 5: (Preparation of a Polymer Dispersion According to the Invention)

Reaction components: 27 parts of methyl methacrylate 27 parts of n-butyl acrylate 23 parts of polymethacrylic silicone resin of approx. 59%

7.5 parts of N- (hydroxymethyl) acrylamide (50% in H ₂ O)

4 parts of N, N-Oiethylaminoethylmethacrylat

0.15 parts of ammonium peroxodisulfate

1.5 parts sodium dodecyl sulfate

292 parts of water

0.5 parts hexadecane The procedure corresponds to the procedure in Example 1. Fixed content: 24%

Example 6 Production of a Polymer Dispersion According to the Invention

Reaction components:

27 parts of methyl methacrylate

27 parts of n-butyl acrylate

7.7 parts α, ω-bis-methacrylic PDMS (M _n ca. 1000) 7.5 parts ZV- (hydroxymethyl) acrylamide (50% in H 2 O)

2 parts ZV, ZV-diethylaminoethyl methacrylate

2 parts of itaconic acid

0.15 parts of ammonium peroxodisulfate

1.5 parts of sodium dodecylsulfate 292 parts of water

0.5 parts hexadecane

The procedure corresponds to the procedure in Example 1 Fixed content: 19%

Example 7: (Preparation of a Polymer Dispersion According to the Invention)

Reaction components: 27 parts of methyl methacrylate 27 parts of n-butyl acrylate 7.7 parts of polymethacrylic silicone resin from approx. 59%

7.5 parts of ZV- (hydroxymethyl) acrylamide (50% in H ₂ O)

2 parts ZV, ZV-diethylaminoethyl methacrylate

6 parts of itaconic acid

0.15 parts of ammonium peroxodisulfate

1.5 parts sodium dodecyl sulfate 292 parts water 0.5 parts hexadecane

The procedure corresponds to the procedure in Example 1. Fixed content: 19%

Example 8: (Preparation of a polymer dispersion according to the invention):

Reaction components: 27 parts of methyl methacrylate

27 parts n-butyl acrylate 7.7 parts polymethacrylic silicone resin from approx. 59%

SiO _{_4/2} - 37% Me ₃ SiO ₁ Z ₂ - 4% methacrylic & oylmethyldimethylsilyleinheiten 7.5 parts of N- (hydroxymethyl) acrylamide (50% in H ₂ O)

2 parts ZV, ZV-diethylaminoethyl methacrylate

0.15 parts of ammonium peroxodisulfate

7 parts polyvinyl alcohol, degree of hydrolysis 88%,

Höppler viscosity 4 mPas 292 parts water

0.5 parts hexadecane

The procedure corresponds to the procedure in Example 1. Fixed content: 18%

application test

The polymer dispersions obtained in Examples 1 to 7 were diluted with water to an active ingredient content of 5% and applied to a nonwoven cloth by spraying with an airbrush gun (SATA® 2000 Dekor). After drying at room temperature and storage at 140 ^° C. for 5 minutes, various tests were carried out: Drop Test: The time it takes a drop to wet the fiber.

Tensile-strain measurements: Measurements were taken on a ZWICK® Type 1446 instrument at a speed of 12.7 mm / min on dry and wet fabric samples measuring 152 mm x 25 mm. Measured sizes were: F-max [N], F-max [g-force], stretch F-max [%], work tili break, TEA [J].

Claims

Claims:

1. Organosilicone copolymers (O) obtainable by free-radical polymerization in an aqueous medium of Al) ethylenically unsaturated monomers selected from N-methylolacrylamide (NMA), N-methylolmethacrylamide, N-methylolallyl carbamate, alkyl ethers or esters of N-methylolacrylamide, N-methylolmethacrylamide and N-methylolallylcarbamate, with A2) ethylenically unsaturated monomers selected from vinyl esters, (meth) acrylic esters, vinylaromatics, olefins, 1,3-dienes, vinyl ethers and vinyl halides, and A3) optional auxiliary monomers, and B) single or multiple ethylenically unsaturated polyorganosiloxanes.

2. organosilicone copolymers (O) according to claim 1, in which the ethylenically unsaturated monomers A2) are vinyl esters of carboxylic acids having 1 to 15 carbon atoms.

3. organosilicone copolymers (O) according to claim 1 or 2, wherein the auxiliary monomers A3) are selected from ethylenically unsaturated mono- and dicarboxylic acids, ethylenically unsaturated carboxylic acid amides and nitriles, mono- and diesters of fumaric acid and maleic acid, ethylenically unsaturated sulfonic acids and their salts , epoxide-functional ethylenically unsaturated comonomers, ethylenically unsaturated monomers having hydroxyl or CO groups and ethylenically unsaturated silanes.

4. Organosilicone copolymers (O) according to Claims 1 to 3, in which the ethylenically unsaturated polyorganosiloxanes B) have the general formula [1]

^(SiO ^4/2) k ^(Rl Siθ3 / ²⁾ m ^(R 2 SiO _^2/2) p ^(R ¹ 3 ^SiO l / ²⁾ q [O _{_1/2} SiR ³ 2-LX] _s [O _{_1/2} H] _t [1]

have, wherein

L is a bivalent optionally substituted aromatic, heteroaromatic or aliphatic radical

(CR ⁴ 2) tv

RA, R 3, R 4 is a hydrogen atom or a monovalent, optionally with -CN, -NCO, -NR ² ₂ , -COOH, -COOR ² , -PO (OR ² ) _{2 /,} -halogen, -acryl, -epoxy, -SH, -OH or -CONR ² ₂ substituted C] _- C ₂ o ~ hydrocarbon radical or C] _- C ₂ o ~ hydrocarbonoxy radical in which in each case one or more, non-adjacent methylene units by groups -0-, -CO-, -COO-, -OCO-, or -OCOO-, -S-, or

-NR ² - may be replaced and in which one or more non-adjacent methine units are represented by groups,

-N =, -N = N-, or -P = may be replaced, X is an ethylenically unsaturated radical,

R 1 represents hydrogen or a monovalent optionally substituted hydrocarbon radical, b integer values of at least 1, s integer values of at least 1, t 0 or integer values, k + m + p + q denote integer values of at least 2.

5. organosilicone copolymers (O) according to claim 1 to 4, in which the free radical polymerization takes place in emulsion or miniemulsion.

6. Redispersible polymer powder obtainable by drying the aqueous dispersions of the organosilicone copolymers (O) according to claims 1 to 5.

7. A process for the preparation of Organosiliconcopolymers (O), in which

Al) ethylenically unsaturated monomers selected from N-methylolacrylamide (NMA), N-methylolmethacrylamide, N-methylolallyl carbamate, alkyl ethers or esters of N-methylolacrylamide, N-methylolmethacrylamide and N-Methylolallylcarbamats, with

A2) ethylenically unsaturated monomers selected from vinyl esters, (meth) acrylic esters, vinyl aromatics, olefins, 1,3-dienes, vinyl ethers and vinyl halides, and A3) optional auxiliary monomers and

B) ethylenically unsaturated one or more times

Polyorganosiloxanes are polymerized in aqueous medium radically.

8. Use of the Organosiliconcopolymere (O) according to claim 1 to 6 as a coating agent, binder and coating agent.