Laundry-resistant textile hydrophobization

Abstract

The present invention relates to siloxane-based fluorocarbon substitutes for fabric coatings, which are associated with excellent, reactivatable hydrophobicity and high wash durability. The invention thus provides a polymer obtainable by free-radical polymerization of a starting mixture comprising (i) at least one ethylenically unsaturated silicon-containing monomer of formula (I), (ii) at least one active monomer and (iii) optionally at least one ethylenically unsaturated monomer of formula (II).

Description

TECHNICAL FIELD

[0001] The present invention relates to the field of textile hydrophobization by means of fluorine-free siloxane copolymers, their method of preparation and use, and textiles coated therewith. BACKGROUND

[0002] Durable textile hydrophobization is essential for many functional and outdoor textiles and is advertised by many outdoor brands. Important criteria here are the water repellency effect and the durability of the coating.

[0003] This "DWR" (durable water repellent) treatment is often based on per- and polyfluorinated alkyl compounds (PFAS) which are well established in the technical field. The excellent properties of the fluorocarbon coatings thus obtained are manifested, for example, in high hydrophobicity, which also withstands washing of the textile (wash durability). In addition, the reduced hydrophobicity over time can be reactivated, for example, by heat treatment of the coated (treated) textile.

[0004] However, the high durability of PFAS, in particular of their toxic transformation and degradation products, requires the use of fluorine-free alternatives.

[0005] Many alternative technologies are already commercially available and exhibit good water repellent properties. An excellent hydrophobization alternative is, for example, silicone, which has already been commercially available.

[0006] For example, from US 2022 / 0275124 A1 textile hydrophobization by copolymers based on acrylate, acid and siloxane acrylate monomers is known. Although these polymers have good suitability for hydrophobizing textiles, they do not have sufficient wash durability.

[0007] The co-authors of Progress In Organic Coatings volume 150, January 2021, 105968 describe a similar use of copolymer dispersions based on acrylate and siloxane acrylate monomers as fluorocarbon alternatives for textile coatings.

[0008] Although the silicones used hitherto in textile coatings, such as those described above, can cause excellent hydrophobization of the textile, this effect is significantly reduced under mechanical and / or chemical stress, for example after use or washing of the textile. Hitherto, it has not been possible for siloxane-based textile coatings to have a reactivation of the hydrophobic effect similar to fluorocarbons.

[0009] It is therefore desirable to provide fluorine-free siloxane-based polymers which enable excellent reactivatable hydrophobization of textiles and at the same time have high wash durability. SUMMARY

[0010] It has been surprisingly found that the use of specific active monomers as anchoring groups in copolymers enables an excellent hydrophobization of textiles. Due to the interaction of these anchoring groups with organometallic complexes added during the hydrophobization of the textiles, the treated textiles additionally have an excellent wash durability: the textile coatings of the present invention can be easily reactivated, i.e. the reduced hydrophobicity can be very easily maximized again by thermal activation. The effect of being able to thermally renew the hydrophobizing effect of silicone-based coatings is unexpected and thus particularly surprising with respect to the fluorocarbon compound alternatives available in the technical field so far.

[0011] Thus, by means of the first subject matter of the present invention, which relates to a polymer obtainable by free-radical polymerization of a starting mixture comprising:

[0012] (i) at least one monomer of the following chemical formula (I)

[0013]

[0014] wherein,

[0015] R1is H or a hydrocarbon group having 1 to 6 carbon atoms, preferably having 1 to 3 carbon atoms, more preferably having 1 to 2 carbon atoms;

[0016] R2is a hydrocarbon group unit having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 3 to 6 carbon atoms; and

[0017] R3, R4and R5are identical or different and each independently CH3, C2H5, n-propyl, i-propyl, OC2H5, O-n-propyl, O-i-propyl, O-Si(CH3)3, O-Si(C2H5)3, O-Si-(n-propyl)3or O-Si-(i-propyl)3, preferably CH3, O-Si(CH3)3, O-Si(C2H5)3or O-Si-(i-propyl)3, more preferably O-Si(CH3)3;

[0018] and

[0019] (ii) at least one active monomer selected from the group consisting of esters and amides of unsaturated carboxylic acids, wherein the carboxylic acid preferably has up to 6 carbon atoms, more preferably up to 4 carbon atoms, in particular selected from esters and amides of acrylic acid or methacrylic acid, more preferably selected from N-hydroxymethyl acrylamide (NMA), N-hydroxymethyl methacrylamide, glycidyl methacrylate and alkyl ethers or esters of N-hydroxymethyl acrylamide (NMA), N-hydroxymethyl methacrylamide and glycidyl methacrylate,

[0020] and

[0021] (iii) optionally one or more monomers of the formula (II)

[0022]

[0023] wherein,

[0024] R6 is H or a hydrocarbon group having 1 to 6 carbon atoms, preferably having 1 to 3 carbon atoms, more preferably having 1 to 2 carbon atoms;

[0025] R7 is a hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably having 1 to 10 carbon atoms.

[0026] Due to the mutual polymerization of the active monomers (ii), the polymers of the present application achieve superior hydrophobization properties compared to the prior art, which are in particular manifested in high wash durability and the possibility of thermal reactivation in case of loss of hydrophobicity.

[0027] In order to limit the number of pages of the specification of the present application, only preferred embodiments of individual features are stated in the following.

[0028] However, the expert reader shall explicitly understand this disclosure approach to mean that any combination of different preferred levels is also explicitly disclosed and explicitly intended.

[0029] In preferred embodiments, R1 is H or methyl, preferably methyl.

[0030] R2 can be an alkyl group or an alkenyl group, preferably an alkyl group, more preferably ethyl or n-propyl, in particular n-propyl. R2 can also comprise at least one heteroatom selected from the group consisting of O, P, N and S, preferably selected from O and N, more preferably selected from O. R2 can also be an alkyl group or an alkenyl group interrupted by an ether group and / or an amine group. R2 is preferably unsubstituted or substituted by a substituent selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, -OH, -SH, -NH2, =0, -F, -Cl, -Br and -I.

[0031] At least one of R3, R4 and R5 is in particular selected from O-Si(CH3)3, O-Si(C2H5)3, O-Si-(n-propyl)3 or O-Si-(i-propyl)3, preferably O-Si(CH3)3, O-Si(C2H5)3 or O-Si-(i-propyl)3, more preferably O-Si(CH3)3.

[0032] In preferred embodiments, R3, R4 and R5 are identical.

[0033] For example, the monomer of formula (I) is tris(trimethylsilyloxy)silylpropyl methacrylate or bis(trimethylsilyloxy)methyl)silylpropyl methacrylate, preferably tris(trimethylsilyloxy)silylpropyl methacrylate (CL A30).

[0034] Even though it is clear from the general formula (I) that these monomers do not comprise any repeating siloxane units in particular, it should be emphasized that the at least one monomer of formula (I) is not a polymeric structure, in particular not a polysiloxane.

[0035] The ester of the active monomer mentioned can be, for example, a C1-C 10 alkyl ether. The ether of the active monomer mentioned above can be, for example, a C1-C 10 alkyl ether. The ether of the active monomer mentioned above can be, for example, a C1-C

[0036] It is preferred that the active monomer is an ester of an unsaturated carboxylic acid, in particular of an unsaturated carboxylic acid having up to 6 carbon atoms, more preferably having up to 4 carbon atoms. More preferably, the active monomer is an ester of acrylic acid or methacrylic acid, in particular of methacrylic acid.

[0037] The active monomer is, for example, N-methylol acrylamide (NMA), N-methylol methacrylamide or glycidyl methacrylate.

[0038] In a particularly preferred embodiment, the active monomer is glycidyl methacrylate.

[0039] In a preferred embodiment, the starting mixture comprises exactly one monomer of formula (I) and / or exactly one active monomer (ii).

[0040] More preferably, the starting mixture comprises exactly one monomer of formula (I) and / or exactly one active monomer (ii) and / or exactly one monomer of formula (II).

[0041] In a preferred embodiment, R6is H or methyl, more preferably methyl.

[0042] R7may be an alkyl group or an alkenyl group, in particular an alkyl group. R7may also be linear or branched. For example, R7is a linear alkyl group having 1 to 20 carbon atoms, in particular having 1 to 10 carbon atoms.

[0043] R7may comprise at least one heteroatom selected from the group consisting of O, P, N and S, preferably selected from O and N, more preferably selected from O. R7is preferably unsubstituted or substituted with a substituent selected from the group consisting of -OH, -SH, -NH2, =0, -F, -Cl, -Br and -I.

[0044] In a preferred embodiment, R7is selected from the group consisting of methyl, ethyl, propyl, allyl, butyl, butenyl, pentyl, pentenyl, hexyl, hexenyl, heptyl, heptenyl, octyl, octenyl, nonyl, nonenyl, decyl, decenyl, undecyl, undecenyl, dodecyl, dodecenyl, tridecyl, tridecenyl, tetradecyl, tetradecenyl, pentadecyl, pentadecenyl, hexadecyl, hexadecenyl, heptadecyl, heptadecenyl, octadecyl and octadecenyl, preferably methyl, ethyl, propyl, allyl, butyl, butenyl, pentyl, pentenyl, hexyl, hexenyl, heptyl, heptenyl, octyl, octenyl, undecyl, undecenyl, octadecyl and octadecenyl, and in particular methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, undecyl and octadecyl groups.

[0045] The monomer of formula (II) is preferably an acrylate, such as methyl methacrylate, stearyl methacrylate, lauryl methacrylate or octyl methacrylate, preferably methyl methacrylate.

[0046] If the starting mixture further comprises (iv) at least one co-monomer, it is for example selected from the group consisting of styrene, (meth)acrylic acid, butyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate.

[0047] In one particular embodiment, the starting mixture comprises exactly one co-monomer (iv).

[0048] The starting mixture can further comprise at least one solvent (v), which is for example water.

[0049] The starting mixture preferably further comprises an emulsifier system (vi), which comprises for example an ionic component, a non-ionic component and a superhydrophobe.

[0050] The ionic component can be a cationic or an anionic component.

[0051] Suitable cationic components are all commonly used cationic components, such as quaternary alkyl ammonium salts.

[0052] Suitable anionic components are all those commonly used, such as alkyl sulfate salts having a chain length of 8 to 18 carbon atoms, alkyl or alkyl aryl ether sulfate salts having 8 to 18 carbon atoms in the hydrophobic group and up to 60 ethylene oxide or propylene oxide units, alkyl or alkyl aryl sulfonate salts having 8 to 18 carbon atoms, esters and monoesters of sulfosuccinic acid with monohydric alcohols or alkyl phenols, such as sodium dodecyl sulfate (SDS).

[0053] The non-ionic component is selected, for example, from the group consisting of ethoxylated isotridecanol (IT8), IT20 and IT16, preferably IT8.

[0054] Suitable superhydrophobes are, for example, selected from the group consisting of hexadecane, cetyl alcohol, pentanol and octanol, preferably hexadecane.

[0055] The emulsifier system can additionally comprise at least one protective colloid. Suitable protective colloids are, for example, partially hydrolyzed polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetal, and starch and cellulose and their carboxymethyl, methyl, hydroxyethyl, hydroxypropyl derivatives.

[0056] Further useful emulsifiers and protective colloids can be found in "McCutchen's Detergents and Emulsifiers", North American Edition, 1979.

[0057] The starting mixture can further comprise at least one reaction initiator (vii), which can be thermally initiated or redox initiated. The reaction initiator is preferably at least partially water-soluble.

[0058] Thermally initiated reaction initiators are known to decompose after thermal treatment into reactive components which initiate the polymerization reaction. Redox initiated reaction initiators are, as is known in the art, combinations of oxidizing and reducing compounds for initiating radical polymerization.

[0059] The reaction initiator is preferably a peroxide, which is preferably selected from the group consisting of sodium, potassium and ammonium salts of peroxydisulfuric acid, hydrogen peroxide, di-tert-butyl peroxide (DTBP), tert-butyl hydroperoxide (TBHP), potassium peroxydiphosphate, tert-butyl peroxy pivalate, cumene hydroperoxide, isopropylbenzene monoperoxyhydroquinone, dilauroyl peroxide, dibenzoyl peroxide, dicumyl peroxide, preferably TBHP; or an azo initiator such as azobis(isobutyronitrile) (AIBN) or 2,2'-azobis(2-methylpropionamidine) dihydrochloride (V-50), preferably V-50.

[0060] It has been found that the reaction initiator is preferably used in combination with a redox system. The redox reaction initiator combination used is the above-mentioned initiator in combination with a reducing agent. Suitable reducing agents are monovalent cationic sulfites and bisulfites, for example sodium sulfite, derivatives of sulfoxylate, such as zinc or alkali metal formaldehyde sulfoxylate, for example sodium hydroxymethanesulfinic acid and ascorbic acid, in particular sodium hydroxymethanesulfinic acid.

[0061] The redox reaction initiator combination has the advantage that the polymerization reaction can be started even at relatively low temperatures. In addition to reducing the energy consumption, the monomers can also be protected from any thermal decomposition.

[0062] In addition, small amounts of metal compounds can be introduced which are soluble in the polymerization medium and have a metal component which is redox-active under the polymerization conditions, such as those based on iron or vanadium, for example iron ammonium sulfate.

[0063] Particularly preferred initiators are peroxodisulfate salts, in particular ammonium peroxodisulfate, optionally in combination with a reducing agent, in particular sodium hydroxymethanesulfinate.

[0064] In the case of reactions by means of microemulsion polymerization techniques, it is also possible to use primarily oil-soluble initiators, such as cumene hydroperoxide, isopropylbenzene monoperoxide, dibenzoyl peroxide or azobisisobutyronitrile. Preferred reaction initiators for microemulsion polymerization are potassium persulfate, ammonium persulfate, azobisisobutyronitrile and dibenzoyl peroxide. In addition to the representatives just described, an overview of suitable initiators can be found in "Handbook of Free Radical Initiators", E. T. Denisov, T. G. Denisova, T. S. Pokidova, 2003, Wiley Verlag.

[0065] The amount of at least one monomer of formula (I) in the polymer of the present application can be 40-99.9% by weight, preferably 50-99.9% by weight, more preferably 60-99.9% by weight, based on the total weight of the at least one monomer of formula (I), the at least one reactive monomer (ii), optionally the at least one monomer of formula (II), and optionally the at least one auxiliary monomer (iv).

[0066] The amount of at least one reactive monomer (ii) in the polymer of the present application can be 0.1-15% by weight, preferably 0.5-10% by weight, more preferably 1-6% by weight, based on the total weight of the at least one monomer of formula (I), optionally the at least one monomer of formula (II), the at least one reactive monomer (ii), and optionally the at least one auxiliary monomer (iv).

[0067] The amount of at least one monomer of formula (II) in the polymer of the present application can be 1-60% by weight, preferably 3-50% by weight, more preferably 5-40% by weight, based on the total weight of the at least one monomer of formula (I), the at least one monomer of formula (II), the at least one reactive monomer (ii), and optionally the at least one auxiliary monomer (iv).

[0068] The amount of at least one solvent (v) in the polymer of the present application can be 40 to 90 % by weight, preferably 50 to 80 % by weight, based on the total amount of the starting mixture.

[0069] The amount of at least one solvent (v) in the polymer of the present application can be 40 to 90 % by weight, preferably 50 to 80 % by weight, based on the total amount of the starting mixture.

[0070] The amount of emulsifier system (vi) in the polymer of the present application can be 0.3 to 2.5 % by weight, preferably 0.5 to 2 % by weight, based on the total amount of the starting mixture.

[0071] The amount of reaction initiator (vii) in the polymer of the present application can be 0.1 to 5 % by weight, preferably 0.1 to 2 % by weight, based on the total amount of the starting mixture.

[0072] As already explained, the polymer is obtainable by free-radical polymerization of the starting mixture.

[0073] The free-radical polymerization in the context of the present application can be described as chain polymerization, in which two carbon atoms of an olefinically unsaturated C2 unit of a monomer are each covalently bound to a carbon atom of an olefinically unsaturated C2 unit of any other monomer. This converts the double bond of these C2 units into a single bond. This bond-forming reaction is initiated by a reaction initiator (INIT·) which releases free radicals. These radicals bind to the olefinically unsaturated C2 unit (C=C) to form a primary radical (INIT-C-C·), which in turn undergoes chain polymerization with a further olefinically unsaturated C2 unit. Finally, the C2 units covalently bound in this way form the main chain of the resulting copolymer.

[0074] The free-radical polymerization is carried out, in particular, in an aqueous medium. The starting mixture preferably has the usual properties for free-radical polymerization. The free-radical polymerization is preferably emulsion polymerization, in which the starting mixture is an emulsion, in particular microemulsion polymerization, in which the starting mixture is a microemulsion.

[0075] The emulsion polymerization in the context of the present application can be described as a special procedure of the above-described free-radical polymerization. In this case, water-insoluble monomers are emulsified in water by means of an emulsifier system, wherein these monomers are present within micelles formed by these emulsifiers. Using a water-soluble reaction initiator, these monomers polymerize within the micelles to produce so-called latex particles. Finally, a polymer dispersion is obtained from the emulsion used.

[0076] The difference between microemulsion polymerization and emulsion polymerization is that in addition to the monomers contained in the micelles, a superhydrophobe can be added as a stabilizer. Furthermore, the mixture is subjected to a step of thorough homogenization, for example by treatment with ultrasound, for example ultrasound fingers, and / or treatment with pressure, for example a high-pressure homogenizer. As a result, micelles which are significantly smaller and more monodisperse can be formed. Ideally, in each case only these monomers polymerize within the micelles, independently of further micelles. The result here is also a polymer dispersion in which the individual "latex particles" are significantly smaller and more monodisperse after emulsion polymerization than in a polymer dispersion. The micelles have an average diameter of, for example, 50-350 nm. The micelle size can be determined by colloid-analytical methods known to the person skilled in the art, for example dynamic light scattering (DLS).

[0077] In contrast to emulsion polymerization reactions in which the size of the polymer latex particles is essentially determined by kinetic processes and the stability of the micelles, the basis of microemulsion polymerization reactions is thus that the monomers are already completely within the micelles before the polymerization and thus no longer have to diffuse into the micelles during the polymerization. In other words, the latex particles formed can thus be considered to be polymerized copies of the monomer-filled micelles present at the start. As a result, the size of the latex particles is determined only by the dispersion process and the stability of the monomer-filled micelles.

[0078] As a result, the method has some advantages over conventional emulsion polymerization:

[0079] • It is also possible to polymerize absolutely water-insoluble monomers in the microemulsion, since the monomers do not have to be transported through a continuous, usually aqueous phase.

[0080] • The size of the latex particles generally corresponds to the size of the previously formed monomer-filled micelles and can be adjusted very precisely by the amount and type of emulsifier system used.

[0081] • Each monomer-filled micelle is homogeneous in terms of its composition. In particular for copolymerization, the monomer ratio in each micelle is thus identical and is not subject to any differences in monomer diffusion.

[0082] • The amount of emulsifier system used is lower, since the microemulsion is only kinetically stable and not thermodynamically stable.

[0083] A particular advantage of the present application is that the polymers of the present application can be used directly, i.e. without prior purification, for the treatment of textiles.

[0084] In the context of the present application, textiles mean textile substrates, i.e. substrates formed from fibers.

[0085] The polymer of the present application preferably does not comprise any acid monomers, in particular any carboxylic acid monomers, such as acrylic acid, any phosphoric acid monomers and / or any sulfuric acid monomers.

[0086] The present application further provides a hydrophobizing composition comprising:

[0087] (a) the polymer of the present application;

[0088] (b) at least one organometallic complex; and

[0089] (c) optionally at least one auxiliary.

[0090] The hydrophobizing composition is in particular a hydrophobizing dispersion.

[0091] In the context of the present application, an organometallic complex is a compound in which an organic group or organic compound is directly bonded to a metal atom.

[0092] The hydrophobizing composition can further comprise a diluent, such as water. In this case, the amount of the polymer is preferably 0.1 to 30 % by weight, more preferably 0.5 to 10 % by weight, based on the total weight of the hydrophobizing composition consisting of the polymer of the present application, the at least one organometallic complex, the optional at least one auxiliary and the diluent. The amount of the organometallic complex can be 0.01 to 2.0 % by weight, preferably 0.01 to 1.5 % by weight, more preferably 0.03 to 1.0 % by weight, based on the total weight of the hydrophobizing composition consisting of the polymer of the present application, the at least one organometallic complex, the optional at least one auxiliary and the diluent.

[0093] In a preferred embodiment, the organometallic complex is an amine salt, an alkoxide, a carboxylate or a phosphonate or a chelate of a metal selected from the group consisting of Pb, Zn, Zr, Sb, Fe, Cd, Sn, Ti, Ba, Ca, Mn, V, Al or Co, preferably from Zn, Zr, Ti and Al, more preferably from Zr and Ti, preferably an alkoxide or a carboxylate. The carboxylate is for example a naphthenate, an octoate, a hexanoate, a laurate, an acetate, a formate, a citrate or a lactate, preferably an acetate.

[0094] The organometallic complex is preferably selected from the group consisting of zinc octoate, tin octoate and zirconium octoate; aluminium alkoxides such as aluminium tris-sec-butylate, aluminium di-sec-butylate monoacetylacetone, aluminium mono-sec-butylate diacetylacetone, aluminium di-sec-butylate monoethylacetoacetate, aluminium mono-sec-butylate diethylacetoacetate, aluminium di-sec-butylate monoacetate and aluminium mono-sec-butylate diacetate; alkyl titanates; alkyl zirconates; zinc, tin, zirconium, iron and cobalt naphthenates; zinc and zirconium formates; tin, zinc and zirconium acetates; dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate and dibutyltin maleate; dioctyltin diformate, diphenyltin diformate and dioctyltin dipalmitate; alkyl titanates and zirconates of alkanolamines; titanium phosphate; titanium acetylacetonate; butyl titanate; ethyl citrate zirconate; and trialkoxy vanadates such as trimethoxy vanadate, tri-n-butoxy vanadate and trihexyloxy vanadate, preferably from butyl titanate, zirconium octoate and zirconium acetate.

[0095] The fabric substrate treated with the hydrophobizing composition of the present application has superior properties compared to the prior art, in particular due to the at least one organometallic complex. The substrate treated in this way is not only remarkable due to the outstanding wash-resistant hydrophobicity, but can also be thermally reactivated. If the hydrophobicity decreases (for example due to mechanical and / or chemical stress on the fabric substrate, such as in use and / or washing), this can be maximized again by thermal treatment of the substrate.

[0096] The thermal treatment is preferably achieved by ironing in an oven and / or by treatment in a commercially available tumble dryer.

[0097] The coated textile can here be exposed to an activation temperature in the range from 50°C to 200°C, preferably from 80°C to 180°C, more preferably from 120°C to 180°C, wherein the activation time is in particular from 1 to 30 minutes, preferably from 1 to 15 minutes.

[0098] A particular advantage of the present application is that the polymers of the present application can be used directly for treating a fabric substrate, i.e. without prior purification, can be present in the hydrophobizing composition. Surprisingly, this does not reduce the hydrophobizing effect. Since a further purification step of the polymers is superfluous, the economic viability of the hydrophobizing mixture of the present application is significantly improved.

[0099] Suitable auxiliaries are, for example, surface-active substances such as wetting agents or surfactants, dispersants, fragrances, dyes, solvents, antifoams, adhesion promoters or separating agents. The amount of auxiliaries in the hydrophobizing composition is preferably from 0.1 to 10% by weight, more preferably from 0.5 to 5% by weight, based on the total weight of the hydrophobizing composition.

[0100] The present application further provides a redispersible polymer powder obtainable by drying the polymer of the present application.

[0101] For example, such a polymer powder which is redispersible in water can be produced by drying an aqueous dispersion obtained by free-radical polymerization of a starting mixture, for example by spray drying, in a manner known to the person skilled in the art.

[0102] Drying the polymer into powder form significantly reduces the volume of the product; thus lower transport costs can be achieved. Furthermore, the polymer dried in this way is particularly storage-stable and can be converted into a dispersion, i.e. redispersed in a simple manner by mixing with a suitable solvent, for example water, prior to use.

[0103] The present application further provides a process for hydrophobizing a textile substrate, comprising the following steps in the order mentioned:

[0104] (A) providing a textile substrate;

[0105] (B) wetting the textile substrate with the hydrophobizing composition according to the present application as described above; and

[0106] (C) heat-treating the wetted textile substrate obtained after step (B).

[0107] The textile substrate here includes, for example, at least one natural fiber or at least one synthetic fiber or mixtures thereof.

[0108] Examples of such natural fibers are cotton, flax, hemp, wool, such as cotton wool, alpaca wool, angora wool, cashmere wool, mohair wool, yak wool or merino wool, silk and mixtures thereof, preferably cotton. Examples of synthetic fibers are viscose, polyester, polyethylene terephthalate, polyamide, polyethylene, polypropylene, elastane and mixtures thereof, preferably polyester and polyamide. In a particular embodiment, the textile comprises cotton and / or polyester and / or polyamide.

[0109] Particularly preferred is a textile which is a mixture of cotton and at least one synthetic fiber, for example a mixture of cotton and polyester, or a textile produced from polyester, polyamide or a mixture of polyamide and polyester.

[0110] In step (B), the textile substrate can be wetted with the hydrophobizing composition in any desired manner suitable for treating textiles, for example by impregnation, brushing, pouring, spraying, roller coating, printing, padding or foam application.

[0111] Wetting is in particular complete wetting. Complete wetting in the context of the present application means that 70 to 100 %, preferably 80 to 100 %, more preferably 90 to 100 % of the total surface area of the textile is brought into contact with the hydrophobizing dispersion.

[0112] The moistened textile substrate obtained after step (B) is preferably dried at 10 to 40°C, in particular at 20 to 30°C, for 1 to 5 h, preferably 2 to 4 h, or at 80 to 150°C, in particular at 100 to 130°C, for 1 to 15 min, preferably 1 to 5 min, prior to the heat treatment in step (C).

[0113] The heat treatment in step (C) can be carried out at 50 to 200°C, preferably at 80 to 180°C, more preferably at 100 to 180°C, for 1 to 60 min, preferably for 1 to 45 min, more preferably for 1 to 30 min.

[0114] The present application further provides a process for the preparation of the polymers of the present application. In this process, the starting mixture described in detail above comprises

[0115] (i) at least one monomer of the following formula (I)

[0116]

[0117] wherein

[0118] R1is H or a hydrocarbon group having 1 to 6 carbon atoms, preferably having 1 to 3 carbon atoms, more preferably having 1 to 2 carbon atoms;

[0119] R2is a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 3 to 6 carbon atoms; and

[0120] R3, R4and R5are identical or different and each independently CH3, C2H5, n-propyl, i-propyl, OC2H5, O-n-propyl, O-i-propyl, O-Si(CH3)3, O-Si(C2H5)3, O-Si-(n-propyl)3or O-Si-(i-propyl)3, preferably CH3, O-Si(CH3)3, O-Si(C2H5)3or O-Si-(i-propyl)3, more preferably O-Si(CH3)3;

[0121] and

[0122] (ii) at least one active monomer selected from the group consisting of esters and amides of unsaturated carboxylic acids, wherein the carboxylic acid preferably has up to 6 carbon atoms, more preferably up to 4 carbon atoms, in particular selected from esters and amides of acrylic acid or methacrylic acid, more preferably selected from N-hydroxymethyl acrylamide (NMA), N-hydroxymethyl methacrylamide, glycidyl methacrylate and alkyl ethers or esters of N-hydroxymethyl acrylamide (NMA), N-hydroxymethyl methacrylamide and glycidyl methacrylate,

[0123] and

[0124] (iii) optionally one or more monomers of the following formula (II)

[0125]

[0126] wherein

[0127] R6is H or a hydrocarbon group having 1 to 6 carbon atoms, preferably having 1 to 3 carbon atoms, more preferably having 1 to 2 carbon atoms;

[0128] R7is a hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably having 1 to 10 carbon atoms;

[0129] The starting mixture is polymerized free-radically, preferably in an aqueous medium.

[0130] As already mentioned, the process is preferably an emulsion polymerization, in particular a microemulsion polymerization.

[0131] The process comprises the following steps, in particular in the order mentioned:

[0132] (a) providing the starting mixture of the application, further comprising water (v) and an emulsifier system (vi);

[0133] (b) homogenizing the provided starting mixture, preferably by stirring, dispersing, treatment with ultrasound and / or treatment with pressure;

[0134] (gamma) adding at least one reaction initiator (vii), optionally in combination with a redox system as described above, to the homogenized reaction mixture over a period of several hours, preferably 2 to 8 hours, more preferably 4 to 6 hours, at a temperature of 0 to 100°C, preferably 5 to 80°C, more preferably 30 to 80°C;

[0135] (delta) allowing the reaction mixture obtained after (gamma) to react with the added initiator at a temperature of 30 to 60°C, preferably 40 to 55°C, for a period of several hours, preferably in the range of 2 to 8 hours, more preferably 4 to 6 hours; and

[0136] (epsilon) cooling the reaction mixture obtained after (delta) to room temperature.

[0137] The pH of the emulsifier system is, for example, 2 to 9, preferably 4 to 8; in a particularly preferred embodiment, 4 to 6. The pH can be adjusted before the start of the reaction by means of hydrochloric acid, acetic acid, sodium hydroxide solution or EDTA solution. The polymerization can be carried out batchwise or continuously by using the initial charge of all or individual components of the reaction mixture, using a partial initial charge of individual components of the reaction mixture and subsequent metering addition, or by means of a feed method without initial charge. All feeds are preferably at the rate of consumption of the respective components. Particularly preferred is the polymerization in batch operation.

[0138] The homogenization in step (β) can be carried out until a particle size of the resulting emulsion in the range of 50-500 nm, preferably 100-350 nm, is obtained, as measured by colloid analytical methods known in the art, such as dynamic light scattering (DLS) or static light scattering (LLS).

[0139] It can be particularly advantageous to purify the cooled reaction mixture obtained after (ε) or to further use it without further purification.

[0140] The present application further provides a coated textile substrate obtainable by the hydrophobizing process of the present application as detailed above.

[0141] The textile substrate treated in this way (coated textile) has excellent, wash-resistant, hydrophobic properties.

[0142] It is particularly unexpected that the textile thus treated is heat reactivatable. Heat reactivatable means that a reduced hydrophobicity of the textile (for example by mechanical and / or chemical stress, such as during use or washing of the textile) can be increased again, in particular maximized, by a heat treatment.

[0143] The heat treatment is preferably achieved by ironing in an oven and / or by treatment in a commercially available tumble dryer.

[0144] The coated textile can here be exposed to an activation temperature in the range of 50 °C to 200 °C, preferably 80 °C to 180 °C, more preferably 100 °C to 180 °C, wherein the activation time is in particular 1 to 120 min, preferably 1 to 30 min, more preferably 1 to 15 min.

[0145] All of the above-mentioned symbols in the above formulae are each defined independently of one another. In all formulae, the silicon atoms are tetravalent. DETAILED DESCRIPTION

[0146] Working Examples

[0147] The present application and the unexpected technical benefits associated therewith will be further elucidated by the following working examples.

[0148] 1. Analytical methods used

[0149] Particle size determination:

[0150] Particle size is measured by dynamic light scattering (Mie analysis method) on a Zetasizer Nano-S particle size analyser from Malvern (software version 8.01). For this purpose, the dispersions are diluted with filtered and degassed water to 0.1% by weight to a maximum of 0.5% by weight. The values reported always refer to the D(50) value. D(50) means the volume average particle size, under which 50% of all particles analysed have a volume average diameter smaller than the reported D(50) value. The measurement is carried out at 25°C with the following specific settings: refractive index of water (dispersant RI) 1.330; viscosity (cP) 0.8872; refractive index of the dispersed phase (material RI) 1.55; material absorption 0.010; measurement duration (duration used) 50 s; measurement position 0.85 mm.

[0151] Evaluation of the hydrophobicity of the treated textile:

[0152] The hydrophobicity of the treated textile can be evaluated by measuring the contact angle relative to water or by performing a "spray test".

[0153] Determination of the contact angle relative to water:

[0154] The measurement is carried out on a Krüss DSA25E contact angle measuring instrument, which is equipped with a curved sample stage with magnet clamps. The measurement is evaluated in the ADVANCE software from Krüss. After clamping of the material, the contact angle relative to water is determined repeatedly by means of an automatic double-feeding unit by applying 0.2 μl of water, and the average value is determined. The higher the measured contact angle, the more hydrophobic the treated textile is relative to water.

[0155] The test is performed by spray test according to AATCC test method No. 22-2005: this involves spraying the textile with deionised water. The result of the comparison of the sprayed fabric surface with the rating images gives an indication of approximately what percentage of the area remains unwetted. A spray test index of 100% indicates a textile which is completely unwetted. The higher the spray test index, the more hydrophobic the treated textile is relative to water.

[0156] 2. Preparation of silicone acrylate dispersions

[0157] The production of the hydrophobizing compositions of the present application (Examples 2-5) and of comparative dispersions not containing the active monomer (ii) of the present application (Example 1) is described below. As Example 6, further comparative examples not according to the present application are also detailed, in which textile hydrophobizing agents based on amine-containing silicone oils according to the state of the art are produced.

[0158] Example 1 : (comparative example; not according to the present application)

[0159] Example 1 : (Prior art) 0.02 g SDS (sodium dodecyl sulfate) and 0.48 g IT8 (ethoxylated isotridecanol) were dissolved in water at 40°C while stirring. 4.95 g of stearyl methacrylate, 19.8 g of WACKER CLA30 (3-[tris(trimethylsilyloxy)silyl]propyl methacrylate) and 0.36 g of hexadecane were added and mixed homogenously at 40°C and then dispersed on an Ultraturrax for 15 minutes. The pre-emulsion was then further emulsified with an ultrasonic probe (10 Wh) while stirring for 15 minutes until a microemulsion with a particle size of about 300 nm was obtained. Subsequently, the resulting microemulsion was free-radically polymerized. To this end, 157 μl of acetic acid (diluted; 10% by weight), 140 μl of NaOH solution (2% by weight) and 30 μl of FAS (ferric (II) ammonium sulfate, 1% by weight) were dissolved in water and 20 ml of water formed the initial feed in a 250 ml laboratory reactor. Subsequently, the pre-prepared microemulsion was added and the mixture was heated to 50°C while stirring. Upon reaching this temperature, 0.4 ml of a 10% by weight TBHP solution (tert-butyl hydroperoxide) and 0.4 ml of a 5% by weight aqueous sodium formaldehyde sulfoxylate solution were metered in over a period of four hours. The progress of the reaction was observed and monitored based on the solids content formed. To this end, 1 ml aliquots were taken from the stirred vessel and precipitated in ethanol. The solids formed were centrifuged off and dried. The reaction was polymerized in total for 5.5 hours at 50°C until the conversion was complete and then cooled to room temperature. The resulting dispersion was used as obtained.

[0160] It should be noted that Example 1 is a hydrophobized dispersion described in the prior art (Organic Coatings volume 150, January 2021, 105968).

[0161] Example 2: (Invention)

[0162] At 40°C, 0.02 g SDS and 0.48 g IT8 were dissolved in water (53 ml) while stirring. 16.8 g WACKER CLA 30, 0.63 g glycidyl methacrylate and 0.36 g hexadecane were added and mixed homogeneously at 40°C and then dispersed on an Ultraturrax for 15 minutes. The pre-emulsion was then further emulsified with an ultrasound probe (10 Wh) while stirring for 15 minutes until a microemulsion with a particle size of about 220 nm was obtainable. Subsequently, the resulting microemulsion was free-radically polymerized. To this end, 157 μl of acetic acid (diluted; 10% by weight), 140 μl NaOH solution (2% by weight), 30 μl FAS (1% by weight) were dissolved in water and in a 250 ml laboratory reactor, 20 ml water formed the initial feed. Subsequently, the previously prepared microemulsion was added, the mixture was heated to 50°C while stirring. Upon reaching this temperature, 0.4 ml of a 10% by weight TBHP solution and 0.4 ml of a 5% by weight sodium formaldehyde sulfoxylate aqueous solution were metered in over a period of four hours. The progress of the reaction was observed and monitored based on the solids content formed. To this end, 1 ml aliquots were taken from the stirred vessel and precipitated in ethanol. The solids formed were centrifuged off and dried. The reaction was polymerized at 50°C for a total of 5.5 hours until the conversion was complete and then cooled to room temperature. The resulting dispersion was used in the state as obtained.

[0163] Example 3: (of the application)

[0164] At 40°C, 0.02 g SDS and 0.48 g IT8 were dissolved in water (53 ml) while stirring. 2.17 g methyl methacrylate, 16.93 g WACKER CLA 30, 0.63 g glycidyl methacrylate and 0.36 g hexadecane were added and mixed homogeneously at 40°C and then dispersed on an Ultraturrax for 15 minutes. The pre-emulsion was then further emulsified with an ultrasonic probe (10 Wh) while stirring for 15 minutes until a microemulsion with a particle size of about 250 nm was obtainable. Subsequently, the resulting microemulsion was free-radically polymerized. To this end, 157 μl of acetic acid (diluted; 10% by weight), 140 μl NaOH solution (2% by weight), 30 μl FAS (1% by weight) were dissolved in water and in a 250 ml laboratory reactor, 20 ml water formed the initial charge. Subsequently, the previously prepared microemulsion was added and the mixture was heated to 50°C while stirring. Upon reaching this temperature, 0.4 ml of a 10% by weight TBHP solution and 0.4 ml of a 5% by weight sodium formaldehyde sulfoxylate aqueous solution were metered in over a period of four hours. The progress of the reaction was observed and monitored based on the solids content formed. To this end, 1 ml aliquots were taken from the stirred vessel and precipitated in ethanol. The solids formed were centrifuged off and dried. The reaction was polymerized at 50°C for a total of 5.5 hours until the conversion was complete and then cooled to room temperature. The resulting dispersion was used in the state as obtained.

[0165] Example 4: (of the application)

[0166] At 40°C, 0.02 g SDS and 0.48 g IT8 were dissolved in water (53 ml) while stirring. 3.10 g methyl methacrylate, 13.0 g WACKER CLA 30, 0.63 g glycidyl methacrylate and 0.36 g hexadecane were added and mixed homogeneously at 40°C and then dispersed on an Ultraturrax for 15 minutes. The pre-emulsion was then further emulsified with an ultrasonic probe (10 Wh) while stirring for 15 minutes until a microemulsion with a particle size of about 200 nm was obtained. Subsequently, the resulting microemulsion was free-radically polymerized. To this end, 157 μl of acetic acid (diluted; 10% by weight), 140 μl NaOH solution (2% by weight), 30 μl FAS (1% by weight) were dissolved in water and in a 250 ml laboratory reactor, 20 ml water formed the initial feed. Subsequently, the pre-prepared microemulsion was added, the mixture was heated to 50°C while stirring. Upon reaching this temperature, 0.4 ml of a 10% by weight TBHP solution and 0.4 ml of a 5% by weight sodium formaldehyde sulfoxylate aqueous solution were metered in over four hours. The progress of the reaction was observed and monitored based on the formed solid content. To this end, 1 ml aliquots were taken from the stirred vessel and precipitated in ethanol. The formed solids were centrifuged off and dried. The reaction was polymerized in total for 5.5 hours at 50°C until the conversion was complete and then cooled to room temperature. The resulting dispersion was used in the as-obtained state.

[0167] Example 5: (of the application)

[0168] At 40°C, 0.02 g SDS and 0.48 g IT8 were dissolved in water (53 ml) while stirring. 4.03 g methyl methacrylate, 9.24 g WACKER CLA 30, 0.63 g glycidyl methacrylate and 0.36 g hexadecane were added and mixed homogeneously at 40°C and then dispersed on an Ultraturrax for 15 minutes. The pre-emulsion was then further emulsified with an ultrasonic probe (10 Wh) while stirring for 15 minutes until a microemulsion with a particle size of about 200 nm was obtained. Subsequently, the resulting microemulsion was free-radically polymerized. To this end, 157 μl of acetic acid (diluted; 10% by weight), 140 μl of NaOH solution (2% by weight), 30 μl of FAS (1% by weight) were dissolved in water and in a 250 ml laboratory reactor, 20 ml of water formed the initial feed. Subsequently, the pre-prepared microemulsion was added, the mixture was heated to 50°C while stirring. At this temperature, 0.4 ml of a 10% by weight TBHP solution and 0.4 ml of a 5% by weight aqueous sodium formaldehyde sulfoxylate solution were metered in over a period of four hours. The progress of the reaction was observed and monitored based on the formed solid content. To this end, 1 ml aliquots were taken from the stirred vessel and precipitated in ethanol. The formed solids were centrifuged off and dried. The reaction was polymerized at 50°C for a total of 5.5 hours until the conversion was complete and then cooled to room temperature. The resulting dispersion was used as obtained.

[0169] Example 6 (not inventive):

[0170] First, 12.6 g of an organopolysiloxane having functional groups -(CH2)3NH(CH2)2NH2and a viscosity of 1000 mm2 / s and an amine value of 0.3 meq / g at 20°C, 2.2 g of a dimethylpolysiloxane having a viscosity of 5 mm / s at 25°C, 2.2 g of an MQ-methylsilicone resin and 3 g of ethylene glycol monohexyl ether were mixed at room temperature and then 6 g of diethylene glycol monobutyl ether, 0.25 g of acetic acid and 73.75 g of demineralized water were stirred in succession at room temperature. A slightly turbid emulsion was obtained. 2 / s of an organopolysiloxane having functional groups -(CH2)3NH(CH2)2NH2and a viscosity of 1000 mm2 / s and an amine value of 0.3 meq / g at 20°C, 2.2 g of a dimethylpolysiloxane having a viscosity of 5 mm / s at 25°C, 2.2 g of an MQ-methylsilicone resin and 3 g of ethylene glycol monohexyl ether were mixed at room temperature and then 6 g of diethylene glycol monobutyl ether, 0.25 g of acetic acid and 73.75 g of demineralized water were stirred in succession at room temperature. A slightly turbid emulsion was obtained.

[0171] 3. Production of the samples and determination of the hydrophobizing properties:

[0172] Production of the samples:

[0173] In the working examples, the respective dispersions or emulsions used for the modification on the textile were diluted with water to an active content of 1% by weight, in some cases with an additional 0.7% by weight of a zirconium acetate solution (16% by weight) (Examples 1 b, 2b, 3, 4, 5, 6b) and then applied to the textile sample.

[0174] In case of a padding process, the respective dispersion or emulsion for modification on the textile is diluted with water to an active content of 10% by weight, in some cases with an additional 0.7% by weight of a zirconium acetate solution (16% by weight) (Examples 1 b, 2b, 3, 4, 5, 6b), and then applied to the textile sample.

[0175] The textile samples used are pieces of unmodified fabric with the following composition, each piece having a size of 20 cm x 20 cm:

[0176] • Polyester (PES) - Cotton (CO) twill

[0177] (214 g / m2) 2 ; 65% by weight PES, 35% by weight CO)

[0178] • Polyester (128 g / m2) 2

[0179] • Polyamide / TAFT (66 g / m2) 2

[0180] The textile samples are treated (= processed) as follows:

[0181] In each case the fabric is immersed in the hydrophobizing composition ten times so that the entire piece of fabric is completely wetted. Subsequently, the material is first dried at room temperature for 2 hours and then conditioned in a climate-controlled room at 23°C and 60% humidity for at least 72 hours in order to condition it sufficiently for the spray test and the contact angle measurement to determine the hydrophobization.

[0182] Alternatively, the fabric can also be coated by padding the roll at a pressure of 3 bar. Subsequently, the material is first dried in a tenter at 130°C for 2 minutes and then conditioned in a climate-controlled room at 23°C and 60% humidity for at least 72 hours in order to condition it sufficiently for the spray test and the contact angle measurement to determine the hydrophobization.

[0183] Spray test after treatment:

[0184] For all treated textiles, the spray test is carried out after the final treatment (including the conditioning described above) (result: "after treatment").

[0185] Subsequently, the textiles are again dried overnight on a clothesline in a climate-controlled room.

[0186] Wash durability study:

[0187] ​​To check the wash durability, after the above drying, the finally treated textile was washed and spun together with about 2 kg ballast in a Miele PROFESSIONAL WS 5426 domestic washing machine in the minimum iron program at 40°C for 40 minutes. The washing surfactant used here was a 3+1 color detergent from the SpeePower Caps brand from Henkel. The textile was then dried and acclimatized in a climate-controlled room at 23°C and 60% humidity for at least 24 hours. To remove laundry wrinkles, these test samples can optionally be ironed with a Tristar iron in the "cotton / linen" setting.

[0188] The wrinkle-free washed samples were then retested for hydrophobicity by the spray test method and by contact angle measurement (results: "after washing").

[0189] Activation:

[0190] The coated fabric can be activated in various ways; thus reactivation in this way is possible even after washing.

[0191] The treatment can be carried out in a drying cabinet at 150-180°C for 5-15 minutes, in a tenter frame at 130-180°C for 1-5 minutes, in a standard domestic condenser tumble dryer at 90-120°C for 30-120 minutes, or by ironing at maximum setting.

[0192] The hydrophobicity of the samples thus activated was retested by the spray test method and contact angle measurement (results: "after washing and activation").

[0193] The "washing" and "activation" sequence was repeated and accompanied by hydrophobicity measurements, so that conclusions can be drawn about the activatability of the hydrophobicity of the textiles treated according to the application.

[0194] 4. Results

[0195] Table 1 shows the results of the spray test on polyester-cotton twill fabric samples treated with the hydrophobizing compositions of Examples 1-6. In some cases, the treatment was carried out by adding zirconium acetate to the hydrophobizing composition.

[0196] Table 1: Spray test results on polyester-cotton twill for all working examples.

[0197]

[0198]

[0199] The results of comparative examples 1a and 1b, which reflect the state of the art, clearly show that the absence of the active monomer (ii) of the present application leads to an unsatisfactory hydrophobization of the textile, even directly after the treatment without washing. Moreover, the fabric coated in this way does not have an excellent wash durability.

[0200] Surprisingly, the polymer of the present application comprising only the active monomer (ii) (and only in combination with the organometallic complex in the hydrophobization composition) leads to the desired effect, i.e. a high hydrophobicity of the final textile (see examples 2a and 2b), which is also reactivatable.

[0201] Examples 2b, 3, 4 and 5 clearly show that the interaction of the active monomer (ii) and the organometallic complex results in a coated fabric with excellent hydrophobicity. Even after mechanical and chemical stress by washing, the reduced but still sufficient hydrophobicity can be maximized again by thermal activation of the textile. This is the fact that even after the tenth washing cycle the excellent wash durability of the fabric coated with the hydrophobization composition of the present application is possible and not limited.

[0202] These properties cannot be achieved even with amine-containing silicone oils conventional in the art (see examples 6a and 6b).

[0203] Table 2 summarizes the results similarly obtained for textile samples made of pure synthetic fibers.

[0204] Table 2: Spray test results of working examples 2b and 3 on other textiles.

[0205]

[0206] For these textile samples, the excellent hydrophobicity of the textile treated according to the present application and the possibility of reactivating the hydrophobicity after stress by washing are demonstrated and in fact exceed the results of table 1. The coating has the following effect by means of the hydrophobicity of the active monomer (ii) and its wash resistance: even in some cases after ten washes the excellent water-repellent effect is completely maintained (see examples 2b and 3).

[0207] In addition to the spray test, the contact angles of the coated textile samples from table 1 were also determined (see table 3).

[0208] Table 3: Results of the contact angle measurements of all working examples on polyester-cotton twill.

[0209]

[0210] Even after washing, the fabrics coated according to the application (Examples 2-5) have a higher hydrophobicity (indicated by higher contact angles) than the comparative examples. Moreover, it is clear that the unexpected effect that the hydrophobicity reduced by washing can be increased again by thermal activation is only possible in the case of the textiles coated according to the application.

[0211] The application is further characterized by the following points:

[0212] 1. A polymer obtainable by radical polymerization of a starting mixture comprising:

[0213] (i) at least one monomer of the following chemical formula (I)

[0214]

[0215] wherein,

[0216] R1is H or a hydrocarbon radical having 1 to 6 carbon atoms, preferably having 1 to 3 carbon atoms, more preferably having 1 to 2 carbon atoms;

[0217] R2is a hydrocarbon radical having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 3 to 6 carbon atoms; and

[0218] R3, R4and R5are identical or different and each independently CH3, C2H5, n-propyl, i-propyl, OC2H5, O-n-propyl, O-i-propyl, O-Si(CH3)3, O-Si(C2H5)3, O-Si-(n-propyl)3or O-Si-(i-propyl)3, preferably CH3, O-Si(CH3)3, O-Si(C2H5)3or O-Si-(i-propyl)3, more preferably O-Si(CH3)3;

[0219] and

[0220] (ii) at least one active monomer selected from the group consisting of esters and amides of unsaturated carboxylic acids, wherein the carboxylic acid preferably has up to 6 carbon atoms, more preferably up to 4 carbon atoms, in particular selected from esters and amides of acrylic acid or methacrylic acid, more preferably selected from N-hydroxymethyl acrylamide (NMA), N-hydroxymethyl methacrylamide, glycidyl methacrylate and alkyl ethers or esters of N-hydroxymethyl acrylamide (NMA), N-hydroxymethyl methacrylamide and glycidyl methacrylate,

[0221] and

[0222] (iii) optionally one or more monomers of the following chemical formula (II)

[0223]

[0224] wherein,

[0225] R6 is H or a hydrocarbyl group having 1-6 carbon atoms, preferably having 1-3 carbon atoms, more preferably having 1-2 carbon atoms;

[0226] R7 is a hydrocarbyl group having 1-30 carbon atoms, preferably 1-20 carbon atoms, more preferably having 1-10 carbon atoms.

[0227] 2. The polymer according to point 1, wherein R1 is H or methyl, preferably methyl.

[0228] 3. The polymer according to any of the preceding points, wherein R2 is an alkyl or alkenyl unit, preferably an alkyl unit, more preferably an ethyl or n-propyl unit, in particular an n-propyl unit.

[0229] 4. The polymer according to any of the preceding points, wherein R2 comprises at least one heteroatom selected from the group consisting of O, P, N and S, preferably selected from O and N, more preferably selected from O.

[0230] 5. The polymer according to any of the preceding points, wherein R2 is an alkyl or alkenyl unit interrupted by an ether group and / or an amine group.

[0231] 6. The polymer according to any of the preceding points, wherein R2 is unsubstituted or substituted by a substituent selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, -OH, -SH, -NH2, =0, -F, -Cl, -Br and -I.

[0232] 7. The polymer according to any of the preceding points, wherein R3, R4 and R5 are identical.

[0233] 8. The polymer according to any of the preceding points, wherein the monomer of formula (I) is tris(trimethylsiloxy)silylpropyl methacrylate or (bis(trimethylsiloxy)methyl)silylpropyl methacrylate, preferably tris(trimethylsiloxy)silylpropyl methacrylate (CLA30).

[0234] 9. The polymer according to any of the preceding points, wherein the ester of the active monomer is an ester of a C1-C 10 alkyl carboxylic acid.

[0235] 10. The polymer according to any of the preceding points, wherein the ether of the active monomer is a C1-C 10 alkyl ether.

[0236] 11. The polymer according to any of the preceding points, wherein the reactive monomer is N-hydroxymethyl acrylamide (NMA), N-hydroxymethyl methacrylamide or glycidyl methacrylate, preferably glycidyl methacrylate.

[0237] 12. The polymer according to any of the preceding points, wherein R6 is H or methyl, more preferably methyl.

[0238] 13. The polymer according to point 1 or 2, wherein R7 is an alkyl or alkenyl group, in particular an alkyl group.

[0239] 14. The polymer according to any of the preceding points, wherein R7 is linear or branched.

[0240] 15. The polymer according to any of the preceding points, wherein R7 is a linear alkyl group having 1 to 20 carbon atoms, in particular having 1 to 10 carbon atoms.

[0241] 16. The polymer according to any of the preceding points, wherein R7 comprises at least one heteroatom selected from the group consisting of O, P, N and S, preferably selected from O and N, more preferably selected from O.

[0242] 17. The polymer according to any of the preceding points, wherein R7 is unsubstituted or substituted by a substituent selected from the group consisting of -OH, -SH, -NH2, =0, -F, -Cl, -Br and -I.

[0243] 18. The polymer according to any of the preceding points, wherein R7 is preferably selected from the group consisting of methyl, ethyl, propyl, allyl, butyl, butenyl, pentyl, pentenyl, hexyl, hexenyl, heptyl, heptenyl, octyl, octenyl, nonyl, nonenyl, decyl, decenyl, undecyl, undecenyl, dodecyl, dodecenyl, tridecyl, tridecenyl, tetradecyl, tetradecenyl, pentadecyl, pentadecenyl, hexadecyl, hexadecenyl, heptadecyl, heptadecenyl, octadecyl and octadecenyl, preferably methyl, ethyl, propyl, allyl, butyl, butenyl, pentyl, pentenyl, hexyl, hexenyl, heptyl, heptenyl, octyl, octenyl, undecyl, undecenyl, octadecyl and octadecenyl, in particular methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, undecyl and octadecyl.

[0244] 19. The polymer according to any of the preceding points, wherein the monomer of formula (II) is an acrylate, such as methyl methacrylate, stearyl methacrylate, lauryl methacrylate or octyl methacrylate, preferably methyl methacrylate.

[0245] 20. The polymer according to any of the preceding points, wherein the starting mixture is an emulsion, preferably a microemulsion.

[0246] 21. The polymer according to any of the preceding points, wherein the starting mixture comprises exactly one monomer of formula (I) and / or exactly one reactive monomer (ii).

[0247] 22. The polymer according to any of the preceding points, wherein the free radical polymerization is a free radical polymerization in an aqueous medium.

[0248] 23. The polymer according to any of the preceding points, wherein the starting mixture further comprises (iv) at least one co-monomer selected from the group consisting of styrene, (meth)acrylic acid, butyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate.

[0249] 24. The polymer according to any of the preceding points, wherein the starting mixture comprises exactly one co-monomer (iv).

[0250] 25. The polymer according to any of the preceding points, wherein the starting mixture further comprises (v) at least one solvent, preferably water.

[0251] 26. The polymer according to any of the preceding points, wherein the starting mixture further comprises (vi) an emulsifier system, which preferably comprises an ionic component, a non-ionic component and a superhydrophobe.

[0252] 27. The polymer according to point 26, wherein the ionic component is a cationic or anionic component, wherein the cationic component is preferably an alkyl quaternary ammonium salt, or the anionic component is preferably sodium dodecyl sulfate (SDS).

[0253] 28. The polymer according to point 26 or 27, wherein the non-ionic component is selected from the group consisting of ethoxylated isotridecanol IT8, IT20 and IT16, preferably IT8.

[0254] 29. The polymer according to any of points 26 to 28, wherein the superhydrophobe is selected from the group consisting of hexadecane, cetyl alcohol, pentanol and octanol, preferably hexadecane.

[0255] 30. The polymer according to any of the preceding points, wherein the starting mixture further comprises (vii) at least one reaction initiator, which can be thermally initiated or redox initiated.

[0256] 31. The polymer according to point 30, wherein the reaction initiator is a peroxide, preferably selected from the group consisting of sodium, potassium and ammonium salts of peroxydisulfuric acid, hydrogen peroxide, di-tert-butyl peroxide (DTBP), tert-butyl hydroperoxide (TBHP), potassium peroxydiphosphate, tert-butyl peroxy pivalate, cumene hydroperoxide, isopropylbenzene monoperoxide, dilauroyl peroxide, dibenzoyl peroxide and dicumyl peroxide, preferably TBHP; or an azo initiator such as azobis(isobutyronitrile) (AIBN) or 2,2'-azobis(2-methylpropionamidine) dihydrochloride (V-50), preferably V-50.

[0257] 32. A hydrophobizing composition comprising

[0258] (a) a polymer according to any one of the preceding points;

[0259] (b) at least one organometallic complex; and

[0260] (c) optionally at least one auxiliary.

[0261] 33. The hydrophobizing composition according to point 32, wherein the hydrophobizing composition further comprises a diluent, preferably water, and

[0262] the amount of polymer is 0.1 to 30 % by weight, preferably 0.5 to 10 % by weight, based on the total weight of the hydrophobizing composition; and / or

[0263] the amount of organometallic complex is 0.01 to 2.0 % by weight, preferably 0.01 to 1.5 % by weight, more preferably 0.03 to 1.0 % by weight, based on the total weight of the hydrophobizing composition.

[0264] 34. The hydrophobizing composition according to point 32 or 33, wherein the organometallic complex is an amine, alkoxide, carboxylate or phosphonate salt or chelate of a metal selected from the group consisting of Pb, Zn, Zr, Sb, Fe, Cd, Sn, Ti, Ba, Ca, Mn, V, Al or Co, preferably selected from Zn, Zr, Ti and Al, more preferably selected from Zr and Ti.

[0265] 35. The hydrophobizing composition according to point 34, wherein the carboxylate salt is a naphthenate, octoate, hexanoate, laurate, acetate, formate, citrate or lactate salt, preferably an acetate salt.

[0266] 36. The hydrophobizing composition according to any one of points 32 to 35, wherein the organometallic complex is selected from the group consisting of zinc octoate, tin octoate and zirconium octoate; aluminium alkoxides such as aluminium tri-sec-butoxide, aluminium di-sec-butoxide monoacetylacetone, aluminium mono-sec-butoxide diacetylacetone, aluminium di-sec-butoxide monoethylacetoacetate, aluminium mono-sec-butoxide diethylacetoacetate, aluminium di-sec-butoxide monoacetate and aluminium mono-sec-butoxide diacetate; alkyl titanates; alkyl zirconates; zinc, tin, zirconium, iron and cobalt naphthenates; zinc and zirconium formates; tin, zinc and zirconium acetates; dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate and dibutyltin maleate; dioctyltin diformate, diphenyltin diformate and dioctyltin dipalmitate; alkyl titanates and zirconates of alkanolamines; titanium phosphate; titanium acetylacetonate; butyl titanate; ethyl citrate zirconate; and trialkoxy vanadates such as trimethoxy vanadate, tri-n-butoxy vanadate and trihexyloxy vanadate, preferably butyl titanate, zirconium octoate and zirconium acetate.

[0267] 37. The hydrophobizing composition according to any one of points 32 to 36, wherein the polymer is present in the hydrophobizing composition without prior purification.

[0268] 38. The hydrophobizing composition according to any one of points 32 to 37, wherein the adjuvant is selected from the group consisting of surface-active substances such as wetting agents or surfactants, dispersants, fragrances, dyes, solvents, antifoams, adhesion promoters or separating agents; and / or

[0269] wherein the amount of adjuvant in the hydrophobizing composition is 0.1 to 10 % by weight, preferably 0.5 to 5 % by weight, based on the total weight of the hydrophobizing composition.

[0270] 39. A redispersible polymer powder obtainable by drying a polymer according to any one of points 1 to 31.

[0271] 40. A method of hydrophobizing a textile substrate, comprising the following steps in the order specified:

[0272] (A) providing a textile substrate;

[0273] (B) wetting the textile substrate with a hydrophobizing composition according to any one of points 32 to 38; and

[0274] (C) heat-treating the wetted textile substrate obtained after step (B).

[0275] 41. The method according to point 40, wherein the textile substrate comprises at least one natural fibre, at least one synthetic fibre or a mixture thereof.

[0276] 42. The method according to point 41, wherein the natural fibers are selected from the group consisting of cotton, flax, hemp, wool such as cotton wool, alpaca wool, angora wool, cashmere wool, mohair wool, yak wool or merino wool, silk and mixtures thereof, preferably cotton.

[0277] 43. The method according to point 41 or 42, wherein the synthetic fibers are selected from the group consisting of viscose, polyester, polyethylene terephthalate, polyamide, polyethylene, polypropylene, elastane, and mixtures thereof, preferably polyester and polyamide.

[0278] 44. The method according to any one of points 40 to 43, wherein the fabric substrate comprises cotton, polyester and / or polyamide.

[0279] 45. The method according to any one of points 40 to 44, wherein the fabric substrate is a mixture of cotton and at least one synthetic fiber, such as a mixture of cotton and polyester, or wherein the textile is a polyester, a polyamide or a mixture of polyamide and polyester.

[0280] 46. The method according to any one of points 40 to 45, wherein in step (B) the fabric substrate is wetted with the hydrophobizing composition in any desired manner suitable for fabric treatment, such as by dipping, brushing, pouring, spraying, roll coating, printing, padding or foam application.

[0281] 47. The method according to any one of points 40 to 46, wherein

[0282] The wetted fabric substrate obtained after step (B) is dried at 10 to 40 °C, in particular at 20 to 30 °C, for 1 to 5 h, preferably 2 to 4 h, or at 80 to 150 °C, in particular at 100 to 130 °C, for 1 to 15 min, preferably 1 to 5 min, prior to the heat treatment in step (C).

[0283] 48. The method according to any one of points 40 to 47, wherein the heat treatment in step (C) is carried out at 50 to 200 °C, preferably 80 to 180 °C, more preferably 100 to 180 °C, for 1 to 60 min, preferably 1 to 45 min, more preferably 1 to 30 min.

[0284] 49. A method for preparing a polymer according to any one of points 1 to 31, wherein the starting mixture comprises

[0285] (i) at least one monomer of the following chemical formula (I)

[0286]

[0287] wherein,

[0288] R1is H or a hydrocarbyl group having 1 to 6 carbon atoms, preferably having 1 to 3 carbon atoms, more preferably having 1 to 2 carbon atoms;

[0289] R2is a hydrocarbyl unit having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 3 to 6 carbon atoms; and

[0290] R3, R4and R5are the same or different and each independently CH3, C2H5, n-propyl, i-propyl, OC2H5, O-n-propyl, O-i-propyl, O-Si(CH3)3, O-Si(C2H5)3, O-Si-(n-propyl)3or O-Si-(i-propyl)3, preferably CH3, O-Si(CH3)3, O-Si(C2H5)3or O-Si-(i-propyl)3, more preferably O-Si(CH3)3;

[0291] and

[0292] (ii) at least one active monomer selected from the group consisting of esters and amides of unsaturated carboxylic acids, wherein the carboxylic acid preferably has up to 6 carbon atoms, more preferably up to 4 carbon atoms, especially selected from esters and amides of acrylic acid or methacrylic acid, more preferably selected from N-hydroxymethyl acrylamide (NMA), N-hydroxymethyl methacrylamide, glycidyl methacrylate and alkyl ethers or esters of N-hydroxymethyl acrylamide (NMA), N-hydroxymethyl methacrylamide and glycidyl methacrylate,

[0293] and

[0294] (iii) optionally one or more monomers of the following formula (II)

[0295]

[0296] wherein,

[0297] R6is H or a hydrocarbyl group having 1 to 6 carbon atoms, preferably having 1 to 3 carbon atoms, more preferably having 1 to 2 carbon atoms;

[0298] R7is a hydrocarbyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably having 1 to 10 carbon atoms;

[0299] radical polymerization, which is preferably carried out in an aqueous medium.

[0300] 50. The process according to point 49, wherein the process is emulsion polymerization, preferably microemulsion polymerization.

[0301] 51. The process according to point 49 or 50, wherein the process comprises the following steps in the specified order:

[0302] (α) providing a starting mixture of the application as described in any of points 1-31, which further comprises water (v) and an emulsifier system (vi);

[0303] (β) homogenizing the provided starting mixture, preferably by stirring, dispersing, treating with ultrasound and / or treating with pressure;

[0304] (γ) adding at least one reaction initiator (vii), optionally in combination with a redox system, to the homogenized reaction mixture at a temperature in the range of 0-100°C, preferably 5-80°C, more preferably 30-80°C, within a time period of several hours, preferably in the range of 2-8 hours, more preferably 4-6 hours;

[0305] (δ) allowing the reaction mixture obtained after (γ) to react with the added initiator at a temperature in the range of 30°C-60°C, preferably 40°C-55°C, for a time period of several hours, preferably in the range of 2-8 hours, more preferably 4-6 hours; and

[0306] (ε) cooling the reaction mixture obtained after (δ) to room temperature.

[0307] 51. A coated textile substrate obtainable by the method according to any of points 40 to 48.

Claims

1. A polymer obtainable by free-radical polymerization of a starting mixture, the starting mixture comprising: (i) at least one monomer of the following chemical formula (I) wherein, R1 is H or a hydrocarbon group having 1 to 6 carbon atoms; R2 is a hydrocarbon group unit having 1 to 10 carbon atoms; and R3, R4 and R5 are identical or different and each independently CH3, C2H5, n-propyl, i-propyl, OC2H5, O-n-propyl, O-i-propyl, O-Si(CH3)3, O-Si(C2H5)3, O-Si-(n-propyl)3 or O-Si-(i-propyl)3; and (ii) at least one reactive monomer selected from the group consisting of esters and amides of unsaturated carboxylic acids. R1 is H or methyl; and / or wherein R2 is an alkyl or alkenyl unit.

2. The polymer of claim 1, wherein, At least one of R3, R4 and R5 is selected from O-Si(CH3)3, O-Si(C2H5)3, O-Si-(n-propyl)3 or O-Si-(i-propyl)3.

3. The polymer of claim 1 or 2, wherein, 4. The polymer according to any one of the preceding claims, further comprising (iii) one or more monomers of the following chemical formula (II) wherein, R6 is H or a hydrocarbon group having 1 to 6 carbon atoms; R7 is a hydrocarbon group having 1 to 30 carbon atoms.

5. The polymer according to any one of the preceding claims, the starting mixture further comprising (iv) at least one auxiliary monomer selected from the group consisting of styrene, methyl (meth)acrylate, (meth)acrylic acid and butyl (meth)acrylate; and / or wherein wherein the starting mixture further comprises (v) at least one solvent; and / or wherein the starting mixture further comprises (vi) an emulsifier system; and / or wherein the starting mixture further comprises (vii) at least one reaction initiator.

6. A hydrophobizing composition comprising (a) the polymer of any one of the preceding claims; (b) at least one organometallic complex; and (c) optionally at least one auxiliary. the hydrophobizing composition further comprising a diluent, and 7. The hydrophobizing composition of claim 6, wherein, the amount of the polymer is 0.1 to 30 % by weight, based on the total weight of the hydrophobizing composition; and / or the amount of the organometallic complex is 0.01 to 2.0 % by weight, based on the total weight of the hydrophobizing composition. the organometallic complex is an amine salt, an alkoxide salt, a carboxylate salt or a phosphate salt or a chelate of a metal selected from the group consisting of Pb, Zn, Zr, Sb, Fe, Cd, Sn, Ti, Ba, Ca, Mn, V, Al or Co.

8. The hydrophobizing composition according to claim 6 or 7, wherein, the polymer is present in the hydrophobizing composition without prior purification.

9. The hydrophobizing composition according to any one of claims 6-8, wherein, 10. The hydrophobizing composition according to any one of claims 6 to 9, the auxiliary is selected from the group consisting of surface-active substances such as wetting agents or surfactants, dispersants, fragrances, dyes, solvents, antifoams, adhesion promoters or separating agents; wherein, and / or wherein the amount of the auxiliary in the hydrophobizing composition is 0.1 to 10 % by weight, based on the total weight of the hydrophobizing composition. ​ 11. A redispersible polymer powder, obtainable by drying the polymer of any one of claims 1 to 5.

12. A method of hydrophobizing a textile substrate, comprising the following steps in the specified order: (A) providing a textile substrate; (B) wetting the textile substrate with the hydrophobizing composition of any one of claims 6 to 10; and (C) heat treating the wetted textile substrate obtained after step (B).

13. The method of hydrophobizing according to claim 12, drying the wetted textile substrate obtained after step (B) for 1 to 5 hours prior to the heat treatment in step (C), and / or wherein wherein the heat treatment in step (C) is carried out at 50 to 200 °C for 1 to 60 minutes.

14. A process for the preparation of the polymer of any one of claims 1 to 5, wherein the starting mixture comprises (iv) at least one monomer of the following chemical formula (I) wherein, R1 is H or a hydrocarbon group having 1 to 6 carbon atoms; R2 is a hydrocarbon group having 1 to 10 carbon atoms; and R3, R4 and R5 are identical or different and each independently CH3, C2H5, n-propyl, i-propyl, OC2H5, O-n-propyl, O-i-propyl, O-Si(CH3)3, O-Si(C2H5)3, O-Si-(n-propyl)3 or O-Si-(i-propyl)3; and (v) at least one reactive monomer selected from the group consisting of esters and amides of unsaturated carboxylic acids, and (vi) optionally one or more monomers of the following chemical formula (II) wherein, R6 is H or a hydrocarbon group having 1 to 6 carbon atoms; R7 is a hydrocarbon group having 1 to 30 carbon atoms; radically polymerizing the starting mixture, preferably in an aqueous medium.

15. A coated textile substrate, obtainable by the method of hydrophobizing of claim 12 or 13. ​

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