Wash-resistant hydrophobic fabric

Abstract

The present invention relates to siloxane-based fluorocarbon substitutions for fabric coatings relating to excellent reactivatable hydrophobicity and high wash durability. Accordingly, the present invention provides polymers obtained by free radical polymerization of a starting mixture comprising (i) at least one ethylenically unsaturated silicon-containing monomer of chemical formula (I), (ii) at least one active monomer, and (iii) optionally at least one ethylenically unsaturated monomer of chemical formula (II).

Description

Technical Field

[0001] The present invention relates to the field of fabric hydrophobization with fluorine-free siloxane copolymers, their preparation and use, and fabrics coated therewith.

Background Art

[0002] Long-lasting fabric hydrophobization is essential for many functional and outdoor fabrics and is advertised by many outdoor brands. The important criteria here are the water repellent effect and the durability of the coating.

[0003] This "DWR" (durable water repellency) finish is often based on perfluorinated and polyfluorinated alkyl compounds (PFAS) that have been established in this technical field for a long time. The remarkable profile of the properties of the fluorocarbon coating thus obtained appears, for example, in high hydrophobicity (washing durability) that can withstand the washing of the fabric. Furthermore, the decreasing hydrophobicity over time can be reactivated, for example, by heat treatment of the coated (finished) fabric.

[0004] However, the high persistence of PFAS, especially its toxic transformation and degradation products, requires the use of fluorine-free alternatives.

[0005] Some alternative technologies are already commercially available and show good water repellency. Excellent hydrophobization alternatives are, for example, commercially available silicones.

[0006] Fabric hydrophobization with copolymers based on acrylates, acids and siloxane acrylate monomers is known, for example, from US Patent Application Publication No. 2022 / 0275124. These polymers are well suited for fabric hydrophobization but do not have sufficient washing durability.

[0007] The authors have previously described similar uses of copolymer dispersions based on acrylate and siloxane acrylate monomers as fluorocarbon substitutions for fabric coatings in Progress In Organic Coatings volume 150, January 2021, 105968.

[0008] While silicones, as described above, have been used in fabric coatings to date, they can provide excellent hydrophobicity to fabrics. However, this effect is significantly reduced under mechanical and / or chemical stress (e.g., after use or washing of the fabric). Reactivating the hydrophobic effect, similar to that of fluorocarbons, has been impossible with siloxane-based fabric coatings until now. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] U.S. Patent Application Publication No. 2022 / 0275124 [Non-patent literature]

[0010] [Non-Patent Document 1] Progress In Organic Coatings volume 150,January 2021,105968 [Overview of the project] [Problems that the invention aims to solve]

[0011] Therefore, it would be desirable to provide a fluorine-free siloxane polymer that enables the achievement of excellent reactivatable hydrophobicity of fabrics while simultaneously possessing high wash durability. [Means for solving the problem]

[0012] Surprisingly, it was found that excellent hydrophobicity of the fabric could be achieved by using specific active monomers as anchor groups within the copolymer. As a result of the interaction between the organometallic complexes added during the fabric hydrophobicity process and these anchor groups, the treated fabric further exhibited extremely excellent wash durability, and the coating of the fabric according to the present invention could be easily reactivated; that is, the decreasing hydrophobicity could be very easily maximized again by thermal activation. The effect of being able to thermally regenerate the hydrophobic effect of siloxane-based coatings was unexpected and was particularly surprising considering the fluorocarbon substitutions available in the art to date.

[0013] Therefore, surprisingly, the requirements for fluorocarbon substitutes for fabric coatings having outstanding hydrophobic properties can be met with the help of the first subject of the present invention, and the first subject of the present invention is (i) at least one monomer of the following chemical formula (I):

[0014] [ka]

[0015] (In the formula, R1 is a hydrocarbyl group having H or 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms; R2 is a hydrocarbyl unit having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 3 to 6 carbon atoms; R3, R4, and R5 are either the same or different, and each is independently CH3, C2H5, n-propyl, iso-propyl, OC2H5, On-propyl, O-iso-propyl, O-Si(CH3)3, O-Si(C2H5)3, O-Si-(n-propyl)3, or O-Si-(iso-propyl)3, preferably CH3, O-Si(CH3)3, O-Si(C2H5)3, or O-Si-(iso-propyl)3, more preferably O-Si(CH3)3. and (ii) at least one active monomer selected from the group consisting of esters of unsaturated carboxylic acids and amides of unsaturated carboxylic acids, wherein the carboxylic acid preferably has a maximum of 6 carbon atoms, more preferably a maximum of 4 carbon atoms, and is particularly selected from esters and amides of acrylic acid or methacrylic acid, more preferably N-methylolacrylamide (NMA), N-methylolmethacrylamide, glycidyl methacrylate, and alkyl ethers or esters of N-methylolacrylamide (NMA), N-methylolmethacrylamide, and glycidyl methacrylate and (iii) optionally, one or more monomers of the following chemical formula (II)

[0016]

Chemical formula

[0017] (wherein R6 is a hydrocarbyl group having H or 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms; R7 is a hydrocarbyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms) relates to a polymer obtained by free radical polymerization of a starting mixture containing

[0018] As a result of the copolymerization of the active monomer (ii), the polymer of the present invention achieves excellent hydrophobization characteristics compared to the prior art, which is particularly evident in that it is thermally reactivatable when high washing durability and hydrophobicity are lost.

Embodiments for Carrying out the Invention

[0019] To limit the number of pages in the description of the present invention, only the preferred embodiments of individual features are described below.

[0020] However, expert readers should clearly understand that this method of disclosure also means that any combination of different levels of preferences is explicitly disclosed and, along with it, explicitly desired.

[0021] In a preferred embodiment, R1 is H or methyl, preferably methyl.

[0022] R2 may be an alkyl unit or an alkenyl unit, preferably an alkyl unit, more preferably an ethyl or n-propyl unit, particularly an n-propyl unit. R2 may also contain at least one heteroatom selected from the group consisting of O, P, N, and S, preferably from O and N, more preferably from O. R2 may also be an alkyl unit or alkenyl unit interrupted by an ether group and / or an amine group. R2 is preferably unsubstituted or substituted with substituents selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, -OH, -SH, -NH2, =O, -F, -Cl, -Br, and -I.

[0023] At least one of R3, R4, and R5 is particularly selected from O-Si(CH3)3, O-Si(C2H5)3, O-Si-(n-propyl)3, or O-Si-(iso-propyl)3, preferably from O-Si(CH3)3, O-Si(C2H5)3, or O-Si-(iso-propyl)3, and more preferably from O-Si(CH3)3.

[0024] In a preferred embodiment, R3, R4, and R5 are the same.

[0025] For example, the monomer of chemical formula (I) is tris(trimethylsiloxy)silylpropyl methacrylate or (bis(trimethylsiloxy)methyl)silylpropyl methacrylate, preferably tris(trimethylsiloxy)silylpropyl methacrylate (CLA30).

[0026] While it is already clear from the general chemical formula (I) that these monomers do not contain repeating siloxane units, it should be emphasized that at least one monomer in chemical formula (I) is not a polymer structure, and is not a polysiloxane in particular.

[0027] The ester of the active monomer described above may be, for example, an ester of a C1-C10-alkylcarboxylic acid. The ether of the active monomer described above may be, for example, a C1-C10-alkyl ether.

[0028] The active monomer is preferably an ester of an unsaturated carboxylic acid, particularly an ester of an unsaturated carboxylic acid having up to six carbon atoms, more preferably up to four carbon atoms. More preferably, the active monomer is an ester of acrylic acid or methacrylic acid, particularly an ester of methacrylic acid.

[0029] The active monomers are, for example, N-methylolacrylamide (NMA), N-methylolmethacrylamide, or glycidyl methacrylate.

[0030] In a particularly preferred embodiment, the active monomer is glycidyl methacrylate.

[0031] In a preferred embodiment, the starting mixture comprises exactly one monomer of chemical formula (I) and / or exactly one active monomer (ii).

[0032] More preferably, the starting mixture comprises exactly one monomer of chemical formula (I) and / or exactly one active monomer (ii) and / or exactly one monomer of chemical formula (II).

[0033] In a preferred embodiment, R6 is H or methyl, more preferably methyl.

[0034] R7 may be an alkyl or alkenyl group, particularly an alkyl group. R7 may be linear or branched. For example, R7 is a linear alkyl group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms.

[0035] R7 may contain at least one heteroatom selected from the group consisting of O, P, N, and S, preferably from O and N, and more preferably from O. R7 is preferably unsubstituted or substituted with a substituent selected from the group consisting of -OH, -SH, -NH2, =O, -F, -Cl, -Br, and -I.

[0036] In preferred embodiments, R7 is methyl, ethyl, propyl, allyl, butyl, butenyl, pentyl, pentenyl, hexyl, hexenyl, heptyl, heptenyl, octyl, octenyl, nonyl, nonyl, decyl, decenyl, undecyl, undecenyl, dodecyl, dodecenyl, tridecyl, tridecenyl, tetradecyl, tetradecenyl, pentadecyl, pentadecenyl, hexadecyl, hexadecenyl, hepta Decenyl, octadecyl, and octadecenyl groups, preferably methyl, ethyl, propyl, allyl, butyl, butenyl, pentyl, pentenyl, hexyl, hexenyl, heptenyl, octyl, octenyl, undecyl, undecenyl, octadecyl, and octadecenyl groups, particularly selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, undecyl, and octadecyl groups.

[0037] The monomer of chemical formula (II) is preferably an acrylic acid ester, such as methyl methacrylate, stearyl methacrylate, lauryl methacrylate, or capryl methacrylate, preferably methyl methacrylate.

[0038] If the starting mixture (iv) further comprises at least one auxiliary monomer, this is selected from the group consisting of, for example, styrene, (meth)acrylic acid, butyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate.

[0039] In certain embodiments, the starting mixture contains exactly one auxiliary monomer (iv).

[0040] The starting mixture may also contain at least one solvent (v), such as water.

[0041] The starting mixture preferably further comprises, for example, an emulsifier system (vi) containing an ionic component, a nonionic component, and a superhydrophobic substance.

[0042] The ionic component may be a cationic component or anionic component.

[0043] All suitable cationic components are conventionally used, such as quaternary alkylammonium salts.

[0044] All suitable anionic components are conventionally used and include, for example, alkyl sulfates having a chain length of 8 to 18 carbon atoms, alkyl or alkylaryl ether sulfates having 8 to 18 carbon atoms and up to 60 ethylene oxide or propylene oxide units in the hydrophobic group, alkyl or alkylaryl sulfonates having 8 to 18 carbon atoms, and esters and monoesters of sulfosuccinic acid with monohydric alcohols or alkylphenols, such as sodium dodecyl sulfate (SDS).

[0045] The nonionic component is selected from the group consisting of, for example, ethoxylated isotridecyl alcohol (IT8), IT20, and IT16, preferably IT8.

[0046] A suitable superhydrophobic substance is selected from the group consisting of, for example, hexadecane, cetyl alcohol, pentanol, and octanol, preferably hexadecane.

[0047] The emulsifier system may further contain at least one protective colloid. Suitable protective colloids include, for example, partially hydrolyzed polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetal, and starch and cellulose, as well as their carboxymethyl, methyl, hydroxyethyl, and hydroxypropyl derivatives.

[0048] Further usable emulsifiers and protective colloids can be found in “McCutchen's Detergents and Emulsifiers”, North American Edition, 1979.

[0049] The starting mixture may further contain at least one reaction initiator (vii) that can be thermally initiated or redox initiated. The reaction initiator is preferably at least partially water-soluble.

[0050] It is known that thermally initiated reaction initiators decompose into reactive components that initiate polymerization reactions after heat treatment. As is known in the art, redox-initiated reaction initiators are combinations of oxidizing and reducing compounds used to initiate free radical polymerization.

[0051] The reaction initiator is preferably a peroxide preferably selected from the group consisting of sodium, potassium, and ammonium salts of peroxodisulfate, hydrogen peroxide, di-t-butyl peroxide (DTBP), t-butyl hydroperoxide (TBHP), potassium peroxodiphosphate, t-butyl peroxypivalate, cumene hydroperoxide, isopropylbenzene monohydroperoxide, 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.

[0052] It has been found that it is preferable to use the reaction initiator in combination with a redox system. The combination of redox reaction initiator used is the initiator described above in combination with a reducing agent. Suitable reducing agents are monovalent cation sulfites and bisulfites, such as sodium sulfite; derivatives of sulfoxylic acids, such as zinc or alkali metal formaldehyde sulfoxylates, such as sodium hydroxymethanesulfinate and ascorbic acid, particularly sodium hydroxymethanesulfinate.

[0053] The combination of redox initiators has the advantage of allowing polymerization reactions to begin even at relatively low temperatures. In addition to reducing energy consumption, it can also protect monomers from thermal decomposition.

[0054] Furthermore, it is possible to introduce a small amount of a metal compound having a metallic component that is soluble in the polymerization medium and redox-active under polymerization conditions, such as an iron or vanadium-based metal compound, such as ammonium iron sulfate.

[0055] Particularly preferred initiators are peroxodisulfates, especially ammonium peroxodisulfate, in combination with a reducing agent, particularly sodium hydroxymethanesulfinate, which can be optionally selected.

[0056] When reactions are carried out using miniemulsion polymerization technology, oil-soluble initiators, such as cumene hydroperoxide, isopropylbenzene monohydroperoxide, dibenzoyl peroxide, or azobisisobutyronitrile, can also be used. Preferred reaction initiators for miniemulsion polymerization are potassium persulfate, ammonium persulfate, azobisisobutyronitrile, and dibenzoyl peroxide. In addition to the representative examples described above, an overview of suitable initiators can be found in “Handbook of Free Radical Initiators”, E.T. Denisov, T.G. Denisova, T.S. Spokidova, 2003, Wiley Verlag.

[0057] In the polymer of the present invention, the amount of at least one monomer of chemical formula (I) may be 40 to 99.9% by weight, preferably 50 to 99.9% by weight, and more preferably 60 to 99.9% by weight, based on the total weight of at least one monomer of formula (I), at least one active monomer (ii), optionally at least one monomer of formula (II), and optionally at least one auxiliary monomer (iv).

[0058] In the polymer of the present invention, the amount of at least one active monomer (ii) may be 0.1 to 15% by weight, preferably 0.5 to 10% by weight, and more preferably 1 to 6% by weight, based on the total weight of at least one monomer of formula (I), optionally at least one monomer of formula (II), at least one active monomer (ii), and optionally at least one auxiliary monomer (iv).

[0059] In the polymer of the present invention, the amount of at least one monomer of chemical formula (II) may be 1 to 60% by weight, preferably 3 to 50% by weight, and more preferably 5 to 40% by weight, based on the total weight of at least one monomer of formula (I), at least one monomer of formula (II), at least one active monomer (ii), and optionally at least one auxiliary monomer (iv).

[0060] In the polymer of the present invention, the amount of at least one auxiliary monomer (iv) may be 1 to 30% by weight, preferably 5 to 25% by weight, and more preferably 10 to 20% by weight, based on the total weight of at least one monomer of formula (I), optionally at least one monomer of formula (II), at least one active monomer (ii), and at least one auxiliary monomer (iv).

[0061] In the polymer of the present invention, the amount of at least one solvent (v) may be 40 to 90% by weight, preferably 50 to 80% by weight, based on the total amount of the starting mixture.

[0062] In the polymer of the present invention, the amount of emulsifier system (vi) may be 0.3 to 2.5% by weight, preferably 0.5 to 2% by weight, based on the total amount of the starting mixture.

[0063] In the polymer of the present invention, the amount of reaction initiator (vii) may be 0.1 to 5% by weight, preferably 0.1 to 2% by weight, based on the total amount of the starting mixture.

[0064] As already explained, polymers can be obtained by free radical polymerization of the starting mixture.

[0065] Free radical polymerization in the context of this invention can be described as a chain polymerization in which two carbon atoms of an ethylenically unsaturated C2 unit of a monomer are covalently bonded to a carbon atom of an ethylenically unsaturated C2 unit of any other monomer. This converts the double bonds of these C2 units into single bonds. This bond-forming reaction is initiated by a reaction initiator that releases a free radical (INIT·). The radical bonds to an ethylenically unsaturated C2 unit (C=C) to form a primary radical (INIT-CC·), which further chain polymerizes with an ethylenically unsaturated C2 unit. Finally, the C2 units thus covalently bonded form the backbone of the resulting copolymer.

[0066] Free radical polymerization is carried out particularly in aqueous media. The starting mixture preferably has properties conventional to free radical polymerization. Free radical polymerization is preferably emulsion polymerization, and the starting mixture is an emulsion, particularly miniemulsion polymerization, and the starting mixture is a miniemulsion.

[0067] Emulsion polymerization in the context of the present invention can be described as a special procedure of the free radical polymerization described above. In this case, water-insoluble monomers are emulsified in water with the help of an emulsifier system, and the monomers reside within micelles formed by the emulsifier. Using a water-soluble reaction initiator, the monomers are polymerized within the micelles to obtain so-called latex particles. Finally, a polymer dispersion is obtained from the emulsion used.

[0068] Miniemulsion polymerization differs from emulsion polymerization in that it is further possible to add superhydrophobic substances as stabilizers to monomer-containing micelles. Furthermore, the mixture is subjected to an intensive homogenization step, for example, by sonication (e.g., ultrasonic fingers) and / or pressure treatment (e.g., high-pressure homogenizer). Thus, it is possible to form significantly smaller and more monodisperse micelles. Ideally, in each case, only monomers polymerize within the micelles, independently of further micelles. Here again, the result is a polymer dispersion, where the individual "latex particles" are significantly smaller and more monodisperse compared to the polymer dispersion after emulsion polymerization. The micelles have an average diameter, for example, 50–350 nm. The size of the micelles can be determined by colloidal analysis methods known to those skilled in the art, such as dynamic light scattering (DLS).

[0069] In contrast to emulsion polymerization, where the size of polymer latex particles is essentially determined by kinetic methods and micelle stability, the basis of miniemulsion polymerization is that the monomers are already completely contained within the micelles before polymerization and therefore no longer need to diffuse into the micelles during polymerization. In other words, the formed latex particles can be considered polymerized copies of the monomer-filled micelles that exist at the start. As a result, the size of the latex particles is determined solely by the dispersion method and the stability of the monomer-filled micelles.

[0070] As a result, this method has several advantages over conventional emulsion polymerization.

[0071] Since monomers do not need to be transported through a continuous phase, usually the aqueous phase, it is also possible to polymerize completely water-insoluble monomers in miniemulsions.

[0072] The size of the latex particles typically corresponds to the size of the monomer-filled micelles formed earlier and can be adjusted very precisely by the amount and type of emulsifier system used.

[0073] Each monomer-filled micelle is homogeneous in terms of its composition. Therefore, especially in copolymerization, the monomer ratio in each micelle is the same and is not affected by differences in monomer diffusion.

[0074] Since miniemulsions are stabilized kinetically only and not thermodynamically, less emulsifier is used.

[0075] A particular advantage of the present invention is that the polymer of the present invention can be used directly (i.e., without prior purification) for the treatment of fabrics.

[0076] In the context of this invention, "fabric" means a fabric base material, that is, a base material formed from fibers.

[0077] The polymer of the present invention preferably does not contain acid monomers, particularly carboxylic acid monomers such as acrylic acid, phosphate monomers and / or sulfuric acid monomers.

[0078] The present invention (a) Polymer of the present invention, (b) at least one organometallic complex, and (c) at least one adjuvant at the discretion of Further, the present invention provides a hydrophobic composition containing the following.

[0079] The hydrophobic composition is, in particular, a hydrophobic dispersion.

[0080] In the context of the present invention, an organometallic complex is a compound in which an organic radical or organic compound is directly bonded to a metal atom.

[0081] The hydrophobic composition may further contain a diluent, such as water. In this case, the amount of polymer is preferably 0.1 to 30% by weight, more preferably 0.5 to 10% by weight, based on the total amount of the hydrophobic composition comprising the polymer of the present invention, at least one organometallic complex, at least one optional auxiliary, and a diluent. The amount of organometallic complex may then 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 amount of the hydrophobic composition comprising the polymer of the present invention, at least one organometallic complex, at least one optional auxiliary, and a diluent.

[0082] In preferred embodiments, the organometallic complex is an amine, alkoxide, carboxylic acid, or phosphoric acid 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 from the group consisting of Zn, Zr, Ti, and Al, and more preferably from the group consisting of Zr and Ti, preferably an alkoxide or carboxylate salt. Examples of carboxylate salts are naphthenate, octanoate, hexoate, laurate, acetate, formate, citrate, or lactate, preferably acetate.

[0083] Organometallic complexes are preferably zinc octanoate, tin octanoate and zirconium octanoate; aluminum alkoxides, for example, aluminum tri-sec-butoxide, aluminum di-sec-butoxide monoacetylacetonate, aluminum mono-sec-butoxide diacetylacetonate, aluminum di-sec-butoxide monoacetoate, aluminum mono-sec-butoxide diacetoate, aluminum di-sec-butoxide monoacetate and aluminum mono-sec-butoxide diacetate; alkyl titanate; alkyl zirconate; zinc naphthenate, tin naphthenate, zirconium naphthenate The following are selected from the group consisting of: um, iron naphthenate and cobalt naphthenate; zinc formate and zirconium formate; tin acetate, zinc acetate and zirconium acetate; dibutyltin dicaprylate, dilaurate, diacetate and maleate; dioctyltin diformate, dibenzoate and diclotonate; alkanolamine titanate and zirconate; titanium phosphate; titanium acetylacetonate; butyl titanate; ethyl zirconium citrate; and trialkoxyvanadates, such as trimethoxyvanadate, tri-n-butoxyvanadate and triheptoxyvanadate, preferably butyl titanate, zirconium octanoate and zirconium acetate.

[0084] In particular, for at least one organometallic complex, fabric substrates finished with the hydrophobic composition of the present invention have superior properties compared to the prior art. It is noteworthy that the substrates thus treated not only exhibit remarkable wash-resistant hydrophobicity but can also be thermally reactivated. If 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 heat treatment of the substrate.

[0085] This heat treatment is preferably carried out in an oven by ironing and / or by treatment in a commercially available rotary dryer.

[0086] The coated fabric can be exposed to an activation temperature in the range of 50 to 200°C, preferably 80 to 180°C, more preferably 120 to 180°C, and the activation time is particularly 1 to 30 minutes, preferably 1 to 15 minutes.

[0087] A particular advantage of the present invention is that the polymer can be used directly in the treatment of fabric substrates, i.e., it can be present in the hydrophobic composition without prior purification. Surprisingly, this does not reduce the hydrophobic effect. Since no further steps of polymer purification are required, the economic viability of the hydrophobic mixture of the present invention is clearly improved.

[0088] Suitable additives include, for example, surface-active substances such as wetting agents or surfactants, dispersants, fragrances, dyes, solvents, defoamers, adhesion promoters, or separation agents. The amount of additives in the hydrophobic composition is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the total weight of the hydrophobic composition.

[0089] The present invention further provides a redispersible polymer powder obtained by drying the polymer of the present invention.

[0090] For example, such polymer powders that can be redispersed in water are preferably produced by drying an aqueous dispersion resulting from the free radical polymerization of a starting mixture, for example by a spray-drying method, as is known to those skilled in the art.

[0091] By drying the polymer into a powder form, the volume of the product is significantly reduced, making it possible to achieve lower transport costs. Furthermore, the polymer dried in this way is particularly stable in terms of storage and can be converted into a dispersion, or redispersed, in a simple manner by mixing it with a suitable solvent, such as water, before use.

[0092] The present invention is a method for hydrophobizing a fabric substrate, comprising the following steps in a specified order: (A) Step of providing a fabric base material, (B) The step of wetting the fabric substrate with the hydrophobic composition of the present invention described above, and (C) A step of heat-treating the wet fabric substrate obtained after step (B). Further methods are provided, including the following.

[0093] The fabric base material here includes, for example, at least one natural fiber or at least one synthetic fiber or a mixture thereof.

[0094] Examples of such natural fibers include cotton, linen, flax, wool, such as sheep's wool, alpaca wool, angora wool, cashmere wool, mohair wool, yak wool, or merino wool, silk, and mixtures thereof, preferably cotton. Examples of synthetic fibers include viscose, polyester, polyethylene terephthalate, polyamide, polyethylene, polypropylene, elastane, and mixtures thereof, preferably polyester and polyamide. In certain embodiments, the fabric may include cotton and / or polyester and / or polyamide.

[0095] A mixture of cotton and at least one synthetic fiber, for example, a mixture of cotton and polyester, or a fabric made from polyester, polyamide, or a mixture of polyamide and polyester is particularly preferred.

[0096] The fabric substrate can be moistened in step (B) with the hydrophobic composition by any desired method suitable for processing the fabric, such as immersion, brushing, injection, spraying, roll-on, printing, padding, or foam coating.

[0097] Wetting is, in particular, complete wetting. In the context of the present invention, complete wetting means that 70-100%, preferably 80-100%, and more preferably 90-100% of the total surface area of ​​the fabric is in contact with the hydrophobic dispersion.

[0098] The wet fabric substrate obtained after step (B) is dried before the heat treatment in step (C) at a temperature of 10 to 40°C, particularly 20 to 30°C for 1 to 5 hours, preferably 2 to 4 hours, or at a temperature of 80 to 150°C, particularly 100 to 130°C for 1 to 15 minutes, preferably 1 to 5 minutes.

[0099] The heat treatment in step (C) can be carried out at 50 to 200°C, preferably 80 to 180°C, more preferably 100 to 180°C for 1 to 60 minutes, preferably 1 to 45 minutes, more preferably 1 to 30 minutes.

[0100] The present invention further provides a method for preparing the polymer of the present invention. In this method, the starting mixture detailed above is (i) at least one monomer of the following chemical formula (I):

[0101] [ka]

[0102] (In the formula, R1 is a hydrocarbyl group having H or 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms; R2 is a hydrocarbyl unit having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 3 to 6 carbon atoms; R3, R4, and R5 are either the same or different, and each is independently CH3, C2H5, n-propyl, iso-propyl, OC2H5, On-propyl, O-iso-propyl, O-Si(CH3)3, O-Si(C2H5)3, O-Si-(n-propyl)3, or O-Si-(iso-propyl)3, preferably CH3, O-Si(CH3)3, O-Si(C2H5)3, or O-Si-(iso-propyl)3, more preferably O-Si(CH3)3. and (ii) At least one active monomer selected from the group consisting of esters of unsaturated carboxylic acids and amides of unsaturated carboxylic acids, wherein the carboxylic acid preferably has up to 6 carbon atoms, more preferably up to 4 carbon atoms, and is particularly selected from esters and amides of acrylic acid or methacrylic acid, more preferably selected from N-methylolacrylamide (NMA), N-methylolmethacrylamide, glycidyl methacrylate, and alkyl ethers or esters of N-methylolacrylamide (NMA), N-methylolmethacrylamide and glycidyl methacrylate, and (iii) Optionally, one or more monomers of the following chemical formula (II)

[0103] [ka]

[0104] (In the formula, R6 is a hydrocarbyl group having H or 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms; R7 is a hydrocarbyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Includes, Free radical polymerization occurs, and free radical polymerization preferably takes place in an aqueous medium.

[0105] As already mentioned, this method preferably involves emulsion polymerization, particularly miniemulsion polymerization.

[0106] This method, in particular, involves the following steps in the specified order: (α) A step of providing a starting mixture of the present invention further comprising water (v) and an emulsifier system (vi), (β) Homogenizing the provided starting mixture, preferably by stirring, dispersion, ultrasonic treatment and / or pressure treatment. (γ) Adding at least one reaction initiator (vii), optionally in combination with the redox system described above, to a homogenized reaction mixture at a temperature of 0 to 100°C, preferably 5 to 80°C, more preferably 30 to 80°C, for several hours, preferably 2 to 8 hours, more preferably 4 to 6 hours. The reaction mixture obtained after (δ)(γ) is reacted with the added initiator at a temperature of 30-60°C, preferably 40-55°C, for several hours, preferably 2-8 hours, more preferably 4-6 hours, and (ε)(δ) Step: Cool the reaction mixture obtained after (ε)(δ) to room temperature. Includes.

[0107] The pH of the emulsifier system is, for example, 2 to 9, preferably 4 to 8, and in a particularly preferred embodiment, 4 to 6. The pH can be adjusted with hydrochloric acid, acetic acid, sodium hydroxide solution, or EDTA solution before the start of the reaction. Polymerization can be carried out in batches or continuously by using initial charging of all or individual components of the reaction mixture, by using partial initial charging of individual components of the reaction mixture followed by metered addition, or by a feeding method without initial charging. All feeding is preferably carried out at the consumption rate of each component. Polymerization in batch operation is particularly preferred.

[0108] Homogenization in step (β) can be performed by measuring using colloidal analysis methods known in the art, such as dynamic light scattering (DLS) or static light scattering (LLS), until a particle size of the resulting emulsion in the range of 50 to 500 nm, preferably 100 to 350 nm, is obtained.

[0109] It may be particularly advantageous to purify the cooled reaction mixture obtained after (ε) or to use it further without further purification.

[0110] As detailed above, the present invention further provides a coated fabric substrate obtained by the hydrophobic treatment method of the present invention.

[0111] The fabric base material (coated fabric) finished in this way has excellent washability and hydrophobic properties.

[0112] It was particularly surprising that the fabrics finished in this way were thermally reactivatable. Thermal reactivation means that, for example, the decrease in the hydrophobicity of the fabric due to mechanical and / or chemical stress during the process of use or washing can be increased again, and especially maximized, by heat treatment.

[0113] This heat treatment is preferably carried out in an oven by ironing and / or by treatment in a commercially available rotary dryer.

[0114] The coated fabric can be exposed to an activation temperature in the range of 50 to 200°C, preferably 80 to 180°C, more preferably 100 to 180°C, and the activation time is particularly 1 to 120 minutes, preferably 1 to 30 minutes, more preferably 1 to 15 minutes.

[0115] All the symbols in the above formulas are defined independently of each other. The silicon atom is tetravalent in all formulas. [Examples]

[0116] The present invention and its remarkable related technical benefits are further illustrated by the following embodiments.

[0117] 1. <Analysis Method Used> Determination of particle size: Particle size is measured by dynamic light scattering (Mie analysis method) using a Malvern Zetasizer Nano-S particle size analyzer, software version 8.01. For this purpose, the dispersion is diluted to 0.1% to a maximum of 0.5% by weight with filtered and degassed water. The reported value always refers to the D(50) value. D(50) means the volume-average particle diameter in which 50% of all particles analyzed have a volume-average diameter smaller than the reported D(50) value. The measurement is performed at 25°C using the following specified 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 period (use period) 50 seconds; measurement position 0.85 mm.

[0118] Evaluate the hydrophobicity of the treated fabric.

[0119] The hydrophobicity of a treated fabric can be evaluated by measuring the contact angle with water or by conducting a "spray test."

[0120] <Determination of the contact angle with water>: Measurements are performed using a KrussDSA 25E contact angle analyzer equipped with a curved sample stage and a magnetic holder. Measurements are evaluated using Kruss ADVANCE software. After clamping the material, the contact angle to water is repeatedly determined by applying 0.2 μl of water using an automated dual-dosing unit, and the average is determined. The higher the measured contact angle, the more hydrophobic the treated fabric is to water.

[0121] <Test by spray test according to AATCC test method number 22-2005>: This involves spraying deionized water onto the fabric. The comparison between the sprayed fabric surface and the evaluation image in the method description shows the approximate percentage of the area that remains unwetted. A spray test index of 100% means the fabric is completely unwetted. The higher the spray test index, the more hydrophobic the treated fabric is to water.

[0122] 2. <Manufacturing of Silicone Acrylate Dispersion> The following describes the production of the hydrophobic compositions of the present invention (Examples 2-5) and a comparative dispersion (Example 1) that does not contain the active monomer (ii) of the present invention. Furthermore, as Example 6, a further comparative example not relating to the present invention is described in detail, in which a fabric hydrophobic agent based on an amine-containing silicone oil, which is conventionally used in the art, is produced.

[0123] Example 1: (Comparative example; not the present invention) Dissolve 0.02 g of SDS (sodium dodecyl sulfate) and 0.48 g of IT8 (isotridecanol ethoxylated) in water at 40°C with stirring. Add 4.95 g of stearyl methacrylate, 19.8 g of WACKER CLA 30 (3-[tris(trimethylsilyloxy)silyl]propyl methacrylate) and 0.36 g of hexadecane, and mix homogeneously at 40°C, then disperse in Ultraturrax for 15 minutes. Next, further emulsify the preemulsion with an ultrasonic finger (10 Wh) with stirring for 15 minutes until a miniemulsion with a particle size of approximately 300 nm is obtained. Subsequently, the obtained miniemulsion is subjected to free radical polymerization. For this purpose, 157 μl of acetic acid (diluted; 10 wt%), 140 μl of NaOH solution (2 wt%), and 30 μl of FAS (ammonium iron(II) sulfate), 1 wt%, are dissolved in water, and 20 ml of water is added to form the initial charge in a 250 ml experimental reactor. Subsequently, the pre-prepared miniemulsion is added, and the mixture is heated to 50°C while stirring. Once the temperature is reached, 0.4 ml of 10 wt% TBHP solution (tert-butyl hydroperoxide) and 0.4 ml of 5 wt% sodium formaldehyde sulfoxylate aqueous solution are metered and supplied over 4 hours. The progress of the reaction is observed and monitored based on the solid content formed. For this purpose, a 1 ml aliquot is taken from the stirring vessel and precipitated in ethanol. The formed solid is centrifuged and dried. The entire reaction is polymerized at 50°C for 5.5 hours until the transformation is complete, and then cooled to room temperature. The resulting dispersion is used as is.

[0124] Please note that Example 1 is a hydrophobic dispersion described in the prior art (Organic Coatings volume 150, January 2021, 105968).

[0125] Example 2: (The present invention) Dissolve 0.02 g of SDS and 0.48 g of IT8 in 53 ml of water at 40°C with stirring. Add 16.8 g of WACKER CLA 30, 0.63 g of glycidyl methacrylate, and 0.36 g of hexadecane, and mix homogeneously at 40°C, then disperse in Ultraturrax for 15 minutes. Next, further emulsify the pre-emulsion with an ultrasonic finger (10 Wh) with stirring for 15 minutes until a miniemulsion with a particle size of approximately 220 nm is obtained. Subsequently, the obtained miniemulsion is subjected to free radical polymerization. For this purpose, dissolve 157 μl of acetic acid (diluted; 10 wt%), 140 μl of NaOH solution (2 wt%), and 30 μl of FAS (1 wt%) in water, and 20 ml of water form the initial charge in a 250 ml experimental reactor. Subsequently, add the pre-prepared miniemulsion and heat the mixture to 50°C with stirring. Once the temperature is reached, 0.4 ml of 10 wt% TBHP solution and 0.4 ml of 5 wt% sodium formaldehyde sulfoxylate aqueous solution are added by weighing over 4 hours. The progress of the reaction is observed and monitored based on the solid content formed. For this purpose, a 1 ml aliquot is taken from the stirring vessel and precipitated in ethanol. The formed solid is centrifuged and dried. The entire reaction is polymerized at 50°C for 5.5 hours until the transformation is complete, and then cooled to room temperature. The resulting dispersion is used as is.

[0126] Example 3: (The present invention) Dissolve 0.02 g of SDS and 0.48 g of IT8 in 53 ml of water at 40°C with stirring. Add 2.17 g of methyl methacrylate, 16.93 g of WACKER CLA 30, 0.63 g of glycidyl methacrylate, and 0.36 g of hexadecane, and mix homogeneously at 40°C, then disperse in Ultraturrax for 15 minutes. Next, further emulsify the pre-emulsion with an ultrasonic finger (10 Wh) with stirring for 15 minutes until a miniemulsion with a particle size of approximately 250 nm is obtained. Subsequently, the obtained miniemulsion is subjected to free radical polymerization. For this purpose, dissolve 157 μl of acetic acid (diluted; 10 wt%), 140 μl of NaOH solution (2 wt%), and 30 μl of FAS (1 wt%) in water, and 20 ml of water form the initial charge in a 250 ml experimental reactor. Next, the pre-prepared miniemulsion is added, and the mixture is heated to 50°C while stirring. Once the temperature is reached, 0.4 ml of 10 wt% TBHP solution and 0.4 ml of 5 wt% sodium formaldehyde sulfoxylate aqueous solution are added by weighing over 4 hours. The progress of the reaction is observed and monitored based on the solid content formed. For this purpose, a 1 ml aliquot is taken from the stirring vessel and precipitated in ethanol. The formed solid is centrifuged and dried. The entire reaction is polymerized at 50°C for 5.5 hours until the transformation is complete, and then cooled to room temperature. The resulting dispersion is used as is.

[0127] Example 4: (The present invention) Dissolve 0.02 g of SDS and 0.48 g of IT8 in 53 ml of water at 40°C with stirring. Add 3.10 g of methyl methacrylate, 13.0 g of WACKER CLA 30, 0.63 g of glycidyl methacrylate, and 0.36 g of hexadecane, and mix homogeneously at 40°C, then disperse in Ultraturrax for 15 minutes. Next, further emulsify the pre-emulsion with an ultrasonic finger (10 Wh) with stirring for 15 minutes until a miniemulsion with a particle size of approximately 200 nm is obtained. Subsequently, the obtained miniemulsion is subjected to free radical polymerization. For this purpose, dissolve 157 μl of acetic acid (diluted; 10 wt%), 140 μl of NaOH solution (2 wt%), and 30 μl of FAS (1 wt%) in water, and 20 ml of water form the initial charge in a 250 ml experimental reactor. Next, the pre-prepared miniemulsion is added, and the mixture is heated to 50°C while stirring. Once the temperature is reached, 0.4 ml of 10 wt% TBHP solution and 0.4 ml of 5 wt% sodium formaldehyde sulfoxylate aqueous solution are added by weighing over 4 hours. The progress of the reaction is observed and monitored based on the solid content formed. For this purpose, a 1 ml aliquot is taken from the stirring vessel and precipitated in ethanol. The formed solid is centrifuged and dried. The entire reaction is polymerized at 50°C for 5.5 hours until the transformation is complete, and then cooled to room temperature. The resulting dispersion is used as is.

[0128] Example 5: (The present invention) Dissolve 0.02 g of SDS and 0.48 g of IT8 in 53 ml of water at 40°C with stirring. Add 4.03 g of methyl methacrylate, 9.24 g of WACKER CLA 30, 0.63 g of glycidyl methacrylate, and 0.36 g of hexadecane, and mix homogeneously at 40°C, then disperse in Ultraturrax for 15 minutes. Next, further emulsify the pre-emulsion with an ultrasonic finger (10 Wh) with stirring for 15 minutes until a miniemulsion with a particle size of approximately 200 nm is obtained. Subsequently, the obtained miniemulsion is subjected to free radical polymerization. For this purpose, dissolve 157 μl of acetic acid (diluted; 10 wt%), 140 μl of NaOH solution (2 wt%), and 30 μl of FAS (1 wt%) in water, and 20 ml of water form the initial charge in a 250 ml experimental reactor. Next, the pre-prepared miniemulsion is added, and the mixture is heated to 50°C while stirring. Once the temperature is reached, 0.4 ml of 10 wt% TBHP solution and 0.4 ml of 5 wt% sodium formaldehyde sulfoxylate aqueous solution are added by weighing over 4 hours. The progress of the reaction is observed and monitored based on the solid content formed. For this purpose, a 1 ml aliquot is taken from the stirring vessel and precipitated in ethanol. The formed solid is centrifuged and dried. The entire reaction is polymerized at 50°C for 5.5 hours until the transformation is complete, and then cooled to room temperature. The resulting dispersion is used as is.

[0129] Example 6 (not the present invention): It has the functional group -(CH2)3NH(CH2)2NH2 and a viscosity of 1000 mmHg at 20°C. 2 12.6 g of organopolysiloxane with an amine value of 0.3 meq / g and a viscosity of 5 mm / s at 25°C, 2.2 g of dimethylpolysiloxane, 2.2 g of MQ-methyl silicone resin, and 3 g of ethylene glycol monohexyl ether were initially charged at room temperature and mixed. Then, 6 g of diethylene glycol monobutyl ether, 0.25 g of acetic acid, and 73.75 g of desalted water were continuously stirred at room temperature. A slightly turbid emulsion was obtained.

[0130] 3. <Preparation of test specimens and determination of hydrophobicity properties>: Preparation of test specimens: In the examples, the corresponding dispersion or emulsion for modifying the fabric surface is diluted with water to an active content of 1% by weight, and optionally further diluted with 0.7% by weight zirconium acetate solution (16% by weight) (Examples 1b, 2b, 3, 4, 5, 6b), and then applied to the fabric test specimen.

[0131] For finishing with padding, the corresponding dispersion or emulsion for modifying the fabric surface is diluted with water to an active content of 10% by weight, and optionally further diluted with 0.7% by weight zirconium acetate solution (16% by weight) (e.g., 1b, 2b, 3, 4, 5, 6b), and then applied to the fabric test specimen.

[0132] The fabric test specimens used are 20cm x 20cm pieces of unmodified fabric with the following composition.

[0133] Polyester (PES) - Cotton (CO) twill (214g / m2; 65% PES by weight, 35% CO by weight) • Polyester (128g / m2) • Polyamide / TAFT (66g / m2) The fabric test specimens are processed (finished) as follows:

[0134] In each case, the fabric is immersed in the hydrophobic composition 10 times to ensure that the entire fabric is completely wet. Subsequently, the material is first dried at room temperature for 2 hours, and then conditioned for at least 72 hours in a climate-controlled room at 23°C and 60% humidity to ensure that it is sufficiently conditioned to determine hydrophobicity by spray testing and contact angle measurement.

[0135] Alternatively, the fabric can be coated by padding the roll with a pressure of 3 bar. Subsequently, the material is first dried in a stent at 130°C for 2 minutes, and then conditioned for at least 72 hours in a climate-controlled room at 23°C and 60% humidity so that it is sufficiently conditioned to determine hydrophobicity by spray testing and contact angle measurement.

[0136] Spray test after finishing: For all treated fabrics, a spray test was performed after finishing (including the conditioning described above) (Result: "Post-Finishing").

[0137] Next, let the fabric dry again overnight on a clothesline in a climate-controlled room.

[0138] Research on wash durability: To test wash durability, the finished fabric, after drying as described above, was washed in a Miele PROFESSIONAL WS 5426 household washing machine on the lowest ironing program at 40°C for 40 minutes with approximately 2 kg of ballast, followed by centrifugal spin-drying. The detergent surfactant used was one capsule of Henkel's Spee Power Caps brand 3+1 color detergent. The fabric was then dried and allowed to settle for at least 24 hours in a climate-controlled room at 23°C and 60% humidity. To remove wrinkles from the laundry, the test pieces could optionally be ironed with a Tristar iron on the "cotton / linen" setting.

[0139] Next, the wrinkle-free, washed samples were retested for hydrophobicity using the spray test method and contact angle measurement (result: "after washing").

[0140] Activation: Coated fabrics can be activated in various ways, and therefore, they can be reactivated in this manner even after washing.

[0141] The process can be carried out by drying in a drying cabinet at 150-180°C for 5-15 minutes, in a stentor at 130-180°C for 1-5 minutes, in a standard household rotary condenser dryer at 90-120°C for 30-120 minutes, or by ironing at the maximum setting.

[0142] The activated samples were then retested for hydrophobicity using the spray test method and contact angle measurement (Results: "After washing and activation").

[0143] By repeatedly performing the "washing" and "activation" steps, accompanied by hydrophobicity measurements, it is possible to conclude that the hydrophobicity of the fabric finished according to the present invention can be reactivated.

[0144] 4.〈Results〉 Table 1 shows the results of spray tests on polyester-cotton twill fabric specimens finished with the hydrophobic compositions of Examples 1-6. In some cases, zirconium acetate was added to the hydrophobic composition for finishing.

[0145] Table 1: Spray test results for all examples on polyester-cotton twill.

[0146] [Table 1]

[0147] The results of Comparative Examples 1a and 1b, which reflect prior art, clearly demonstrate that the absence of the active monomer (ii) of the present invention results in insufficient hydrophobicity of the fabric, even immediately after finishing without washing. Furthermore, fabrics coated in this manner do not possess exceptional washing durability.

[0148] Surprisingly, only the polymer of the present invention containing the active monomer (ii), and only in combination with an organometallic complex in the hydrophobic composition, yields the desired effect, namely, high hydrophobicity of the finished fabric (see Examples 2a and 2b), which is further reactivatable.

[0149] Examples 2b, 3, 4, and 5 clearly demonstrate that the interaction between the active monomer (ii) and the organometallic complex results in a coated fabric with excellent hydrophobicity. Even after mechanical and chemical stress from washing, the reduced but still sufficient hydrophobic properties can be maximized again by thermally activating the fabric. The fact that this is possible without limitation even after 10 washing cycles clearly demonstrates the exceptional washing durability of fabrics coated with the hydrophobic composition of the present invention.

[0150] Such properties could not be achieved even with amine-containing silicone oils conventionally used in the art (see Examples 6a and 6b).

[0151] Table 2 summarizes the results obtained similarly for fabric test specimens made from pure synthetic fibers.

[0152] Table 2: Spray test results for Examples 2b and 3 on other fabrics

[0153] [Table 2]

[0154] The remarkable hydrophobicity of fabrics finished according to the present invention and the ability to reactivate hydrophobicity after stress from washing were confirmed for these fabric samples, and the results from Table 1 were actually exceeded. The hydrophobicity and wash resistance of the coating with active monomer (ii) have the effect of maintaining a remarkable water-repellent effect even after 10 washes in some cases (see Examples 2b and 3).

[0155] In addition to the spray test, the contact angle was also determined for the coated fabric test pieces shown in Table 1 (see Table 3).

[0156] Table 3: Results of contact angle measurements for all examples of polyester-cotton twill.

[0157] [Table 3]

[0158] Even after washing, the fabrics coated according to the present invention (Examples 2-5) exhibit even higher hydrophilicity (indicated by a higher contact angle) than the comparative examples. Furthermore, it is revealed that only in the fabrics coated according to the present invention was it possible to increase the hydrophobicity, which had decreased due to washing, again through thermal activation.

[0159] The present invention is also characterized by the following:

[0160] 1. (i) At least one monomer of the following chemical formula (I)

[0161] [ka]

[0162] (In the formula, R1 is a hydrocarbyl group having H or 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms; R2 is a hydrocarbyl unit having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 3 to 6 carbon atoms; R3, R4, and R5 are either the same or different, and each is independently CH3, C2H5, n-propyl, iso-propyl, OC2H5, On-propyl, O-iso-propyl, O-Si(CH3)3, O-Si(C2H5)3, O-Si-(n-propyl)3, or O-Si-(iso-propyl)3, preferably CH3, O-Si(CH3)3, O-Si(C2H5)3, or O-Si-(iso-propyl)3, more preferably O-Si(CH3)3. and (ii) At least one active monomer selected from the group consisting of esters of unsaturated carboxylic acids and amides of unsaturated carboxylic acids, wherein the carboxylic acid preferably has up to 6 carbon atoms, more preferably up to 4 carbon atoms, and is particularly selected from esters and amides of acrylic acid or methacrylic acid, more preferably selected from N-methylolacrylamide (NMA), N-methylolmethacrylamide, glycidyl methacrylate, and alkyl ethers or esters of N-methylolacrylamide (NMA), N-methylolmethacrylamide and glycidyl methacrylate, and (iii) Optionally, one or more monomers of the following chemical formula (II)

[0163] [ka]

[0164] (In the formula, R6 is a hydrocarbyl group having H or 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms; R7 is a hydrocarbyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. A polymer obtained by free radical polymerization of a starting mixture containing the following:

[0165] 2. The polymer according to item 1, wherein R1 is H or methyl, preferably methyl.

[0166] 3. The polymer according to item 1 or 2, wherein R2 is an alkyl unit or an alkenyl unit, preferably an alkyl unit, more preferably an ethyl unit or an n-propyl unit, particularly an n-propyl unit.

[0167] 4. The polymer according to any one of items 1 to 3, wherein R2 comprises at least one heteroatom selected from the group consisting of O, P, N, and S, preferably from O and N, and more preferably from O.

[0168] 5. The polymer according to any one of items 1 to 4, wherein R2 is an alkyl unit or alkenyl unit interrupted by an ether group and / or an amine group.

[0169] 6. The polymer according to any one of items 1 to 5, wherein R2 is unsubstituted or substituted with a substituent selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, -OH, -SH, -NH2, =O, -F, -Cl, -Br, and -I.

[0170] 7. A polymer as described in any of items 1 to 6, wherein R3, R4, and R5 are the same.

[0171] 8. The polymer according to any one of items 1 to 7, wherein the monomer of chemical formula (I) is tris(trimethylsiloxy)silylpropyl methacrylate or (bis(trimethylsiloxy)methyl)silylpropyl methacrylate, preferably tris(trimethylsiloxy)silylpropyl methacrylate (CLA30).

[0172] 9. The ester of the active monomer is C1-C 10 - A polymer according to any one of items 1 to 8, which is an ester of an alkylcarboxylic acid.

[0173] 10. The ether of the active monomer is C1-C 10 - A polymer that is an alkyl ether, as described in any of items 1 to 9.

[0174] 11. The polymer according to any one of items 1 to 10, wherein the active monomer is N-methylolacrylamide (NMA), N-methylolmethacrylamide, or glycidyl methacrylate, preferably glycidyl methacrylate.

[0175] 12. The polymer according to any one of items 1 to 11, wherein R6 is H or methyl, more preferably methyl.

[0176] 13. The polymer according to item 1 or 2, wherein R7 is an alkyl or alkenyl group, particularly an alkyl group.

[0177] 14. The polymer according to any one of items 1 to 13, wherein R7 is linear or branched.

[0178] 15. The polymer according to any one of items 1 to 14, wherein R7 is a linear alkyl group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms.

[0179] 16. The polymer according to any one of items 1 to 15, wherein R7 comprises at least one heteroatom selected from the group consisting of O, P, N, and S, preferably from O and N, and more preferably from O.

[0180] 17. The polymer according to any one of items 1 to 16, wherein R7 is unsubstituted or substituted with a substituent selected from the group consisting of -OH, -SH, -NH2, =O, -F, -Cl, -Br, and -I.

[0181] 18. R7 is preferably methyl, ethyl, propyl, allyl, butyl, butenyl, pentyl, pentenyl, hexyl, hexenyl, heptyl, heptenyl, octyl, octenyl, nonyl, nonyl, decyl, decenyl, undecyl, undecenyl, dodecyl, dodecenyl, tridecyl, tridecenyl, tetradecyl, tetradecenyl, pentadecyl, pentadecenyl, hexadecyl, hexadecenyl, heptadecenyl, octadecyl A polymer according to any one of items 1 to 17, selected from the group consisting of syl and octadecenyl groups, preferably methyl, ethyl, propyl, allyl, butyl, butenyl, pentyl, pentenyl, hexyl, hexenyl, heptenyl, octyl, octenyl, undecyl, undecenyl, octadecyl and octadecenyl groups, particularly methyl, ethyl, propyl, pentyl, hexyl, heptyl, octyl, undecyl and octadecyl groups.

[0182] 19. The polymer according to any one of items 1 to 18, wherein the monomer of chemical formula (II) is an acrylic acid ester, such as methyl methacrylate, stearyl methacrylate, lauryl methacrylate, or capryl methacrylate, preferably methyl methacrylate.

[0183] 20. The polymer according to any one of items 1 to 19, wherein the starting mixture is an emulsion, preferably a miniemulsion.

[0184] 21. A polymer according to any one of items 1 to 20, wherein the starting mixture comprises exactly one monomer of chemical formula (I) and / or exactly one active monomer (ii).

[0185] 22. The polymer according to any one of items 1 to 21, wherein the free radical polymerization is free radical polymerization in an aqueous medium.

[0186] 23. The polymer according to any one of items 1 to 22, wherein the starting mixture further comprises at least one auxiliary monomer selected from the group consisting of (iv) styrene, (meth)acrylic acid, butyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate.

[0187] 24. The polymer according to any one of items 1 to 23, wherein the starting mixture contains exactly one auxiliary monomer (iv).

[0188] 25. The polymer according to any one of items 1 to 24, wherein the starting mixture further comprises (v) at least one solvent, preferably water.

[0189] 26. The polymer according to any one of items 1 to 25, wherein the starting mixture preferably further comprises an emulsifier system comprising an ionic component, a nonionic component, and a superhydrophobic substance (vi).

[0190] 27. The polymer according to item 26, wherein the ionic component is a cationic component or an anionic component, and the cationic component is preferably a quaternary alkylammonium salt, or the anionic component is preferably sodium dodecyl sulfate (SDS).

[0191] 28. The polymer according to item 26 or 27, wherein the nonionic component is selected from the group consisting of ethoxylated isotridecyl alcohols IT8, IT20, and IT16, preferably IT8.

[0192] 29. The polymer according to any one of items 26 to 28, wherein the superhydrophobic substance is selected from the group consisting of hexadecane, cetyl alcohol, pentanol, and octanol, preferably hexadecane.

[0193] 30. The polymer according to any one of items 1 to 29, wherein the starting mixture further comprises at least one reaction initiator that can be thermally initiated or redox initiated (vii).

[0194] 31. The polymer according to item 30, wherein the reaction initiator is a peroxide preferably selected from the group consisting of sodium, potassium, and ammonium salts of peroxodisulfate, hydrogen peroxide, di-t-butyl peroxide (DTBP), t-butyl hydroperoxide (TBHP), potassium peroxodiphosphate, t-butyl peroxypivalate, cumene hydroperoxide, isopropylbenzene monohydroperoxide, 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.

[0195] 32. (a) A polymer as described in any of items 1 to 31, (b) at least one organometallic complex, and (c) at least one adjuvant at the discretion of A hydrophobic composition containing the above.

[0196] 33. The hydrophobic composition further contains a diluent, preferably water. 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 hydrophobic composition, and / or The amount of organometallic complex is 0.01 to 2.0% by weight, preferably 0.01 to 1.5% by weight, and more preferably 0.03 to 1.0% by weight, based on the total weight of the hydrophobic composition. The hydrophobic composition described in item 32.

[0197] 34. The hydrophobic composition according to item 32 or 33, wherein the organometallic complex is an amine, alkoxide, carboxylic acid, or phosphoric acid salt or chelate, preferably an alkoxide or carboxylate salt, 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 the group consisting of Zn, Zr, Ti, and Al, and more preferably from the group consisting of Zr and Ti.

[0198] 35. The hydrophobizing composition according to item 34, wherein the carboxylate is a naphthenate, octanoate, hexoate, laurate, acetate, formate, citrate, or lactate, preferably an acetate.

[0199] 36. Organometallic complexes include zinc octanoate, tin octanoate, and zirconium octanoate; aluminum alkoxides, such as aluminum tri-sec-butoxide, aluminum di-sec-butoxide monoacetylacetonate, aluminum mono-sec-butoxide diacetylacetonate, aluminum di-sec-butoxide monoacetoate, aluminum mono-sec-butoxide diacetoate, aluminum di-sec-butoxide monoacetate, and aluminum mono-sec-butoxide diacetate; alkyl titanates; alkyl zirconates; zinc naphthenate, tin naphthenate, zirconium naphthenate, iron naphthenate, and naphthate. A hydrophobic composition according to any one of claims 32 to 35, selected from the group consisting of cobalt thenate; zinc formate and zirconium formate; tin acetate, zinc acetate and zirconium acetate; dibutyltin dicaprylate, dilaurate, diacetate and maleate; dioctyltin diformate, dibenzoate and diclotonate; alkanolamine titanate and zirconate; titanium phosphate; titanium acetylacetonate; butyl titanate; ethyl zirconium citrate; and trialkoxyvanadates, such as trimethoxyvanadate, tri-n-butoxyvanadate and triheptoxyvanadate, preferably butyl titanate, zirconium octanoate and zirconium acetate.

[0200] 37. A hydrophobic composition according to any one of items 32 to 36, wherein the polymer is present in the hydrophobic composition without prior purification.

[0201] 38. The auxiliary agent is selected from the group consisting of surface active substances, such as wetting agents or surfactants, dispersants, fragrances, dyes, solvents, defoamers, adhesion promoters, or separating agents, and / or The amount of additive in the hydrophobic composition is 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the total weight of the hydrophobic composition. A hydrophobic composition as described in any of items 32 to 37.

[0202] 39. A redispersible polymer powder obtained by drying a polymer described in any of items 1 to 31.

[0203] 40. A method for hydrophobizing a fabric substrate, comprising the following steps in a specified order: (A) Step of providing a fabric base material, (B) The step of wetting the fabric substrate with a hydrophobic composition described in any of items 32 to 38, and (C) A step of heat-treating the wet fabric substrate obtained after step (B). Methods that include...

[0204] 41. The method according to item 40, wherein the fabric base material comprises at least one natural fiber, at least one synthetic fiber, or a mixture thereof.

[0205] 42. The method according to item 41, wherein the natural fiber is selected from the group consisting of cotton, linen, flax, wool, such as sheep's wool, alpaca wool, angora wool, cashmere wool, mohair wool, yak wool or merino wool, silk and mixtures thereof, preferably cotton.

[0206] 43. The method according to item 41 or 42, wherein the synthetic fiber is selected from the group consisting of viscose, polyester, polyethylene terephthalate, polyamide, polyethylene, polypropylene, elastane and mixtures thereof, preferably polyester and polyamide.

[0207] 44. The method according to any one of items 40 to 43, wherein the fabric base material comprises cotton, polyester and / or polyamide.

[0208] 45. The method according to any one of items 40 to 44, wherein the fabric base material is a mixture of cotton and at least one synthetic fiber, for example, a mixture of cotton and polyester, or the fabric is polyester, polyamide, or a mixture of polyamide and polyester.

[0209] 46. ​​The method according to any one of items 40 to 45, wherein the fabric substrate is moistened in step (B) with a hydrophobic composition in any desired method suitable for processing the fabric, for example, by dipping, brushing, injecting, spraying, roll-on, printing, padding or foam coating.

[0210] 47. The method according to any one of items 40 to 46, wherein the wet fabric substrate obtained after step (B) is dried at 10 to 40°C, particularly 20 to 30°C, for 1 to 5 hours, preferably 2 to 4 hours, or at 80 to 150°C, particularly 100 to 130°C, for 1 to 15 minutes, preferably 1 to 5 minutes, before the heat treatment in step (C).

[0211] 48. The method according to any one of items 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 minutes, preferably 1 to 45 minutes, more preferably 1 to 30 minutes.

[0212] 49. A method for preparing a polymer described in any of items 1 to 31, wherein the starting mixture is (i) at least one monomer of the following chemical formula (I):

[0213] [ka]

[0214] (In the formula, R1 is a hydrocarbyl group having H or 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms; R2 is a hydrocarbyl unit having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 3 to 6 carbon atoms; R3, R4, and R5 are either the same or different, and each is independently CH3, C2H5, n-propyl, iso-propyl, OC2H5, On-propyl, O-iso-propyl, O-Si(CH3)3, O-Si(C2H5)3, O-Si-(n-propyl)3, or O-Si-(iso-propyl)3, preferably CH3, O-Si(CH3)3, O-Si(C2H5)3, or O-Si-(iso-propyl)3, more preferably O-Si(CH3)3. and (ii) At least one active monomer selected from the group consisting of esters of unsaturated carboxylic acids and amides of unsaturated carboxylic acids, wherein the carboxylic acid preferably has up to 6 carbon atoms, more preferably up to 4 carbon atoms, and is particularly selected from esters and amides of acrylic acid or methacrylic acid, more preferably selected from N-methylolacrylamide (NMA), N-methylolmethacrylamide, glycidyl methacrylate, and alkyl ethers or esters of N-methylolacrylamide (NMA), N-methylolmethacrylamide and glycidyl methacrylate, and (iii) Optionally, one or more monomers of the following chemical formula (II)

[0215] [ka]

[0216] (In the formula, R6 is a hydrocarbyl group having H or 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms; R7 is a hydrocarbyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. Includes, A method of free radical polymerization, where free radical polymerization preferably occurs in an aqueous medium.

[0217] 50. The method according to item 49, wherein the method is emulsion polymerization, preferably miniemulsion polymerization.

[0218] 51. The method follows the steps in the specified order: (α) water (v) and emulsifier system (vi), a step of providing a starting mixture of the present invention according to any one of items 1 to 31, (β) Homogenizing the provided starting mixture, preferably by stirring, dispersion, ultrasonic treatment and / or pressure treatment. (γ) Adding at least one reaction initiator (vii), optionally in combination with a redox system, to a homogenized reaction mixture at a temperature of 0 to 100°C, preferably 5 to 80°C, more preferably 30 to 80°C, for several hours, preferably 2 to 8 hours, more preferably 4 to 6 hours. The reaction mixture obtained after (δ)(γ) is reacted with the added initiator at a temperature of 30-60°C, preferably 40-55°C, for several hours, preferably 2-8 hours, more preferably 4-6 hours, and (ε)(δ) Step: Cool the reaction mixture obtained after (ε)(δ) to room temperature. The method described in item 49 or 50, including the method described in item 49 or 50.

[0219] 51. A coated fabric substrate obtained by any of the methods described in items 40 to 48.

Claims

1. (i) at least one monomer of the following chemical formula (I) 【Chemistry 1】 (In the formula, R1 is H or a hydrocarbyl group having 1 to 6 carbon atoms; R2 is a hydrocarbyl unit having 1 to 10 carbon atoms; R3, R4, and R5 are the same or different and each independently is CH ３ , C ２ H ５ , n-propyl, iso-propyl, OC ２ H ５ , O-n-propyl, O-iso-propyl, O-Si(CH ３ ) ３ , O-Si(C ２ H ５ ) ３ , O-Si-(n-propyl) ３ or O-Si-(iso-propyl) ３ ). and (ii) At least one active monomer selected from the group consisting of esters and amides of unsaturated carboxylic acids. A polymer obtained by free radical polymerization of a starting mixture containing the following:

2. The polymer according to claim 1, wherein R1 is H or methyl, and / or R2 is an alkyl unit or an alkenyl unit.

3. At least one of R3, R4, and R5 is O-Si (CH ３ ) ３ O-Si (C ２ H ５ ) ３ O-Si-(n-propyl) ３ Or O-Si-(iso-propyl) ３ A polymer selected from, according to claim 1 or 2.

4. (iii) One or more monomers of the following chemical formula (II) 【Chemistry 2】 (In the formula, R6 is a hydrocarbyl group having H or 1 to 6 carbon atoms; R7 is a hydrocarbyl group having 1 to 30 carbon atoms. The polymer according to any one of claims 1 to 3, further comprising:

5. The starting mixture further comprises at least one auxiliary monomer selected from the group consisting of (iv) styrene, methyl (meth)acrylate, (meth)acrylic acid and butyl (meth)acrylate, and / or The starting mixture further comprises (v) at least one solvent and / or The starting mixture further comprises (vi) an emulsifier system and / or The starting mixture further comprises (vii) at least one reaction initiator. The polymer according to any one of claims 1 to 4.

6. (a) The polymer according to any one of claims 1 to 5, (b) at least one organometallic complex, and (c) at least one adjuvant, at the discretion of the party A hydrophobic composition containing the above.

7. The hydrophobic composition further comprises a diluent, The amount of the polymer is 0.1 to 30% by weight, and / or based on the total weight of the hydrophobic composition. The amount of the organometallic complex is 0.01 to 2.0% by weight, based on the total weight of the hydrophobic composition. The hydrophobic composition according to claim 6.

8. The hydrophobic composition according to claim 6 or 7, wherein the organometallic complex is an amine, alkoxide, carboxylic acid, or phosphoric acid 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.

9. The hydrophobic composition according to any one of claims 6 to 8, wherein the polymer is present in the hydrophobic composition without prior purification.

10. The aforementioned auxiliary agent is selected from the group consisting of surface active substances, such as wetting agents or surfactants, dispersants, fragrances, dyes, solvents, defoamers, adhesion promoters, or separating agents, and / or The amount of the auxiliary agent in the hydrophobic composition is 0.1 to 10% by weight, based on the total weight of the hydrophobic composition. A hydrophobic composition according to any one of claims 6 to 9.

11. A redispersible polymer powder obtained by drying the polymer according to any one of claims 1 to 5.

12. A method for hydrophobicizing a fabric substrate, comprising the following steps in a specified order: (A) The step of providing the fabric base material, (B) The step of wetting the fabric substrate with the hydrophobic composition according to any one of claims 6 to 10, and (C) A step of heat-treating the wet fabric substrate obtained after step (B). Methods that include...

13. The wet fabric substrate obtained after step (B) is dried for 1 to 5 hours before the heat treatment in step (C), and / or The heat treatment in step (C) is carried out at 50 to 200°C for 1 to 60 minutes. The method for hydrophobizing according to claim 12.

14. A method for preparing the polymer according to any one of claims 1 to 5, wherein the starting mixture is (iv) at least one monomer of the following chemical formula (I) 【Transformation 3】 (In the formula, R1 is H or a hydrocarbyl group having 1 to 6 carbon atoms; R2 is a hydrocarbyl unit having 1 to 10 carbon atoms; R3, R4, and R5 are either the same or different, and each is independently CH ３ , C ２ H ５ n-propyl, iso-propyl, OC ２ H ５ O-n-propyl, O-iso-propyl, O-Si(CH ３ ) ３ O-Si (C ２ H ５ ) ３ O-Si-(n-propyl) ３ Or O-Si-(iso-propyl) ３ (It is) and (v) At least one active monomer selected from the group consisting of esters of unsaturated carboxylic acids and amides of unsaturated carboxylic acids, and (vi) Optionally, one or more monomers of the following chemical formula (II) 【Chemistry 4】 (In the formula, R6 is a hydrocarbyl group having H or 1 to 6 carbon atoms; R7 is a hydrocarbyl group having 1 to 30 carbon atoms. Includes, A method comprising the free radical polymerization of the starting mixture, wherein the free radical polymerization preferably occurs in an aqueous medium.

15. A coated fabric substrate obtained by the hydrophobicization method described in claim 12 or 13.

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