Polysiloxane Water Repellents for Textiles

Abstract

An aqueous emulsion comprising a discontinuous oil phase comprising: a) a polyorganohydrogensiloxane; b) an amino-modified polyorganosiloxane comprising at least one amino group located in a terminal position; and c) a blocked isocyanate.

Description

[Technical field]

[0001] (CROSS REFERENCE TO RELATED APPLICATIONS) CROSS-REFERENCE TO RELATED APPLICATIONS: This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 63 / 210517, filed June 15, 2021. U.S. Provisional Patent Application No. 63 / 210517 is incorporated herein by reference.

[0002] FIELD OF THEINVENTION The present invention relates to polysiloxane-based compositions useful for treating textiles. The compositions and associated treatment methods of the present invention are useful for treating fabrics used in clothing to improve their water repellency. [Background technology]

[0003] Textiles, such as fabrics used in clothing, are commonly treated to improve water repellency. Fluoropolymers have historically been used for such treatments, but environmental and health concerns have limited their use. A known alternative approach utilizes polysiloxane-based coating compositions. Applicable compositions include one or more types of polysiloxanes, including resins (e.g., MQ resins), polydiorganosiloxanes (e.g., polydimethylsiloxanes), polyorganoalkenylsiloxanes (e.g., polyorganosiloxanes containing one or more alkenyl groups), and amino-modified polyorganosiloxanes. As an example, U.S. Patent No. 8,329,255 describes a composition that includes an alkoxy-substituted polyorganosiloxane (which may also include amino functional groups) with a blocked isocyanate crosslinker. U.S. Patent Application Publication No. 2019 / 0375897 describes a composition that includes a silicone resin, an amino-modified polysiloxane, and a blocked isocyanate. US Pat. Nos. 9,777,105 and 1,004,0891 describe the use of amino-modified or alkoxy polyorganosiloxanes in conjunction with blocked isocyanates and catalysts.

[0004] Another known class of compositions includes polyorganohydrogensiloxanes, i.e., polyorganosiloxanes that contain one or more -SiH groups.For example, US Patent No. 3,247,281 describes a composition that includes a polyorganohydrogensiloxane with at least 5% by weight of SiH groups, together with a catalytic amount of water-soluble aminosilane.US Patent No. 5,409,620 describes a hydrosilylation-based system that includes polyorganohydrogensiloxanes, unsaturated acetates, organosilicon such as polyorganoalkenylsiloxanes, and metal catalysts.As is known in the art, amino-containing components poison platinum catalysts, and therefore amino-modified polysiloxanes are excluded from such hydrosilylation-based systems.

[0005] Although not related to water repellency, polyorganosiloxanes are also known to be used in the treatment of textiles to improve other properties such as softness, lubricity, durability, fiber shrinkage, etc. For example, U.S. Pat. No. 4,177,176 describes a composition for preventing fiber shrinkage, comprising an amino-modified, hydroxyl or alkoxy-terminated polyorganosiloxane and a polyorganohydrogensiloxane. Japanese Patent Application Publication No. 2002 / 146680 describes a composition for improving the washability and softness of cellulose fiber fabrics while eliminating the "sliminess" associated with the use of silicone resins. The described composition comprises an amino-modified polyorganosiloxane and a polyorganohydrogensiloxane, together with a urethane prepolymer and a blocked isocyanate. The described amino-modified polyorganosiloxane comprises amino groups pendant to the polysiloxane.

[0006] Another class of compositions includes polyorganoalkenylsiloxanes and polyorganohydrogensiloxanes with platinum catalysts that undergo hydrosilylation reactions to form crosslinked reaction products when applied to a substrate. These hydrosilylation-based systems have been described to prepare release and water-repellent coatings for paper and PET films (see, for example, U.S. Patent Application Publication No. 2005 / 0053793) and to improve adhesion between fabrics and airbags (see, for example, U.S. Patent Application No. 7,534,499 and WO 2019 / 001901).

[0007] The industry continues to seek improved water repellent compositions and related textile treatments. Summary of the Invention

[0008] The inventors of the present invention have discovered an unexpected improvement in water repellency with the use of treatment compositions based on polyorganohydrogensiloxanes, aminosilicones and blocked isocyanates. More specifically, the inventors have discovered that the use of terminal aminosilicones in such compositions provides much better water repellency compared to the use of the corresponding pendant variants. The present invention includes such compositions, together with their preparation and their use in treating textiles, and the resulting textiles. Many embodiments have been described.

[0009] In one aspect, the invention includes an aqueous emulsion comprising an aqueous continuous phase and a discontinuous oil phase, the discontinuous oil phase comprising the following components: a) 50-95 wt. % polyorganohydrogensiloxane, b) 0.1-45 wt. % amino-modified polyorganosiloxane comprising at least one amino group located in a terminal position, and c) 5-30 wt. % blocked isocyanate. In another aspect, the invention includes the aforementioned emulsion, the discontinuous oil phase comprising at least one of i) 0.5-1.5 H wt. % and ii) 0.004-0.2 N wt. %. In yet another aspect of the invention, the aforementioned emulsion further comprises component d): 0.1-10 wt. % polyorganosiloxane comprising at least one silanol group. [Brief description of the drawings]

[0010] [Figure 1] FIG. 2 is a plot of Bundesmann water absorption after one wash cycle as a function of amine concentration (N wt %) of the amino-terminated silicones used in example coating emulsions 1-6 provided in Table 2a. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] As used herein, the term "textile" refers to a flexible material consisting of a network of natural or synthetic fibers. Representative fibers include cotton, flax, hemp, silk, wool, rayon, cellulose, linen, nylon, polypropylene, polyether-polyurea copolymers (e.g., "spandex"), and polyester. "Textile" specifically includes nonwoven and woven fabrics produced by weaving, knitting, spreading, felting, sewing, crocheting, or bonding such fibers. In selected embodiments of the present invention, the fabric of interest is one used in the manufacture of clothing (e.g., garments) where flexibility, water resistance, and durability after repeated cleaning (washing, dry cleaning, etc.) are desired.

[0012] The compositions of the present invention are preferably provided as emulsions comprising a continuous aqueous phase. The water used to prepare the emulsions may be from any source and may optionally be purified, for example, by filtration, distillation, reverse osmosis, etc. As described in more detail, the emulsions further comprise a surfactant. The surfactant (alternatively called an "emulsifier") serves to emulsify the discontinuous polysiloxane (oil) phase within the aqueous continuous phase. The discontinuous oil phase of the emulsion preferably comprises 1-10% by weight and more preferably 2-5% by weight of the total weight of the emulsion (i.e., including water, surfactant along with any other additives, solvents, etc.). As described below, the emulsions of the present invention may be prepared prior to use by combining previously prepared emulsions of different polysiloxane compositions.

[0013] The discontinuous oil phase of the emulsion comprises a) a polyorganohydrogensiloxane ("SiH polymer"), b) an amino-modified polyorganosiloxane ("terminal amino silicone") that contains at least one "amino" group located at a terminal position of the polyorganosiloxane, and c) a blocked isocyanate. The discontinuous oil phase may optionally comprise d) a polyorganosiloxane that contains at least one silanol group (-SiOH). In selected classes of embodiments, the emulsions of the present invention comprise the following weight percentages of each of the aforementioned components (where components a+b+c+d=100%): a) 50 to 95 wt. %, preferably 60 to 95 wt. %, and more preferably 60 to 90 wt. % polyorganohydrogensiloxane; b) 0.1 to 45% by weight, preferably 1 to 20% by weight, of terminal amino silicone; c) 5 to 30% by weight, preferably 10 to 25% by weight, of a blocked isocyanate, and optionally d) 0.1 to 10% by weight, preferably 0.5 to 5% by weight, of a polyorganosiloxane containing at least one silanol group. In a subclass of embodiment, the emulsion of the invention comprises: i) 0.5 to 1.5 wt % H (as -SiH) as measured by FTIR, and ii) further comprising at least one of, and preferably both of, 0.004 to 0.2 N weight % and more preferably 0.005 to 0.15 (as "amino"), as measured by acid-base titration.

[0014] a) Polyorganohydrogensiloxanes ("SiH polymers") The class of applicable polyorganohydrogensiloxanes designated as component a) is not particularly limited and includes a wide range of conventional commercially available materials. Such materials include cyclic, linear and branched polyorganohydrogensiloxanes, with linear polymers being preferred. Applicable polymers preferably have a weight average molecular weight (Mw) of 500-6000 AMU (Daltons) and more preferably 1000-4500 AMU (Daltons). Applicable polymers may have a viscosity of 5-50 cSt, more preferably 10-35 cSt, measured at 25° C. according to ASTM D2196-05. Different polyorganohydrogensiloxanes, e.g., those having different chemical structures, molecular weights and / or viscosities, may be used in combination. The polyorganohydrogensiloxanes of the present invention comprise at least one, preferably at least two, and more preferably at least three -SiH groups, which may be located at terminal (end) and / or intermediate (pendant) positions on the polysiloxane backbone. In a preferred embodiment, the -SiH groups are located primarily at pendant positions, i.e. 29 More than 90% by weight, more preferably more than 95% by weight, and even more preferably more than 99% by weight of all -SiH groups are located at pendant positions along the polysiloxane chain as measured by Si NMR. Representative polyorganohydrogensiloxanes include those having the general formula: R3SiO(RRSiO) m( RHSiO) n SiR3 (wherein m+n=10-100, preferably 10-60, n is preferably at least 3, m is preferably at least 7, n / (n+m) is preferably greater than 0.375, and "R" may be the same or different and is selected from substituted or unsubstituted monovalent hydrocarbon groups having 1-18 carbon atoms, and more preferably 1-8 carbon atoms. Representative hydrocarbon groups include a) alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, and heptyl, b) aryl groups such as phenyl, tolyl, xylyl, and naphthyl, and c) aralkyl groups such as benzyl and phenethyl, with methyl and phenyl groups being preferred, and methyl being most preferred. Commercially available polyorganohydrogensiloxanes that can be used include XIAMETER™ MEM-0075, DOWSIL™ MH 1107 FLUID, XIAMETER™ OFX-5084, SYL-OFF™ 7672, and SYL-OFF™ 7678 (all available from The Dow Chemical Company).

[0015] b) Amino-modified polyorganosiloxanes ("amino-terminated silicones") The class of applicable amino-modified polyorganosiloxanes designated as component b) is not particularly limited and includes a wide range of conventional commercially available materials, so long as at least one amino group is located at the terminal (chain end) position of the polyorganosiloxane.As demonstrated in the following examples, polyorganosiloxane species containing amino groups located at the terminal positions of the polyorganosiloxane chains have shown much better performance than those with amino groups located only at pendant (middle) positions when used in combination with components a) and c).Although the amino silicones of the present invention may contain amino groups located at both terminal and pendant positions, in a preferred class of embodiments, the amino groups are primarily located at terminal positions, i.e. 29More than 90% by weight, more preferably more than 95% by weight, and even more preferably more than 99% by weight of the amino groups are located in terminal positions as measured by Si NMR. Such polymers include linear and branched structures, with linear polymers being preferred. Applicable polymers preferably have a weight average molecular weight (Mw) of 200 to 10,000 AMU (Daltons) and more preferably 400 to 8000 AMU (Daltons). Applicable polymers preferably have a viscosity of 2 to 200 cSt, more preferably 5 to 150 cSt, measured at 25°C according to ASTM D2196-05. Different amino-modified polyorganosiloxanes, e.g., those having different chemical structures, molecular weights and / or viscosities, may be used in combination. Representative amino-modified polyorganosiloxanes include those having the general formula: XR2SiO(RRSiO) q SiR2X (wherein q is 2 to 200, preferably 25 to 100, R is as defined above, and X is an amino group containing one or more (preferably 1 to 3) primary or secondary amine groups containing 1 to 6 carbon atoms). Representative amino groups include those represented by the general formula: -R'NR''R'' (wherein R' is a divalent hydrocarbon group (e.g., an alkylene group) having 2 to 6 carbon atoms, and R'' is the same or different and is selected from monovalent hydrocarbon groups (e.g., alkyl groups) having 1 to 6 carbon atoms, which may be unsubstituted or substituted with H (hydrogen) or one or more hydrocarbon groups (so that the total carbon atoms in such substituted monovalent hydrocarbon groups is 1 to 6), primary amine groups, and secondary amine groups containing monovalent hydrocarbon groups (e.g., alkyl groups) having 1 to 6 carbon atoms. Representative examples include -(CH2)3NH2, -(CH2)3NHCH2CH2NH2, -(CH2)4NHCH2CH2NH2, -CH2CH(CH3)CH2NHCH2CH2NH2, -(CH2)3NHCH2CH2NHCH2CH2NH2, and The most preferred structures include -(CH2)3NH2 and and -CHCHR'''CHNHR''', where R''' is H or an alkyl group of 1 to 6 carbon atoms. Applicable species are further described in U.S. Pat. No. 9,777,105. Applicable commercially available amino-modified polyorganosiloxanes include DMS-A15, DMS-A21 and DMS-A31 available from Gelest.

[0016] c) Blocked isocyanate The class of applicable blocked isocyanates designated as component c) is not particularly limited and includes a wide range of conventional commercially available materials. As used herein, the term "blocked isocyanate" refers to the reaction product of an isocyanate and a blocking agent, the blocking agent being removable from the isocyanate under thermal conditions, i.e., those typically used during textile processing. Conventional blocking agents include aryl alcohols, alkanone oximes, aryl thiols, organic active hydrogen compounds, sodium bisulfite, and hydroxylamines. Preferred blocking agents include alkanone oximes (ketoximes) that can be deblocked at relatively low temperatures, such as those used during typical textile processing processes. For the purposes of the present invention, "aromatic" blocked polyisocyanates are preferred. In this context, the term "aromatic" refers to isocyanate compounds having at least one aromatic group, such as materials based on toluene diisocyanate, diphenylmethane 4,4' diisocyanate, diphenylmethane 2,4' diisocyanate, polymethylene-polyphenylisocyanate, 4,4' methylene bisphenol isocyanate, and derivatives thereof. Isocyanate A (CNO) Suitable for the Preparation of Blocked Isocyanates zwhere A is an aromatic compound and z is 1, 2, 3 or 4. These include aromatic isocyanates or derivatives such as toluene diisocyanate, polymethylene polyphenyl isocyanate, and 4,4' methylene bisphenol isocyanate, which are commercially available for this purpose. Typical commercial products include aromatic isocyanates based on polymethylene polyphenylene esters of isocyanic acid such as DESMODUR CB-75, an adduct of toluene diisocyanate and trimethylolpropane (1,1,1-trihydroxymethylpropane); (available from Covestro), MONDUR MR-100 (available from Covestro), and aromatic isocyanates based on polymethylene polyphenyl isocyanate with 4,4' methylene bisphenol isocyanate (available from Dow Chemical Co.). Pre-made blocked aromatic isocyanates are also commercially available, such as HYDROPHOBOL DL, PHOBOL XAN Extender (available from Huntsman), DM-6400, MEIKANATE FM-1, MEIKANATE ST, MEIKANATE PRO, MEIKANATE TP-10, MEIKANATE WEB, MEIKANATE ST (available from Meisei Chemical Industry Co., Ltd.). Further background information regarding such isocyanates is provided in U.S. Patent Application Publication No. 2019 / 0375897, U.S. Patent No. 839255, and U.S. Patent No. 6,451,717.

[0017] d) Polyorganosiloxanes containing at least one silanol group (-SiOH). The class of applicable polyorganosiloxanes containing at least one silanol group designated as component d) is not particularly limited and includes a wide range of conventional commercially available materials. Such materials include cyclic, linear and branched structures, with linear polymers being preferred. The applicable polymers preferably have a weight average molecular weight (Mw) of 200 to 5500 AMU (Daltons). The applicable polymers may have a viscosity of 30 to 100 cSt, measured at 25° C. according to ASTM D2196-05. Different polyorganosiloxanes, e.g., having different chemical structures, molecular weights and / or viscosities, may be used in combination. The polyorganosiloxanes of the present invention contain at least one, preferably at least two and more preferably at least three silanol (—SiOH) groups, which may be located at terminal (end) and / or intermediate (pendant) positions on the polysiloxane backbone. In a preferred embodiment, the —SiOH groups are primarily located at pendant positions, i.e., 29 More than 90 wt. %, more preferably more than 95 wt. %, and even more preferably more than 99 wt. % of all -SiOH groups are located at pendant positions along the polysiloxane chain as measured by Si NMR. The polyorganosiloxanes of the present invention preferably have a silanol content of 1 to 10 wt. %, as measured by FTIR. Representative polyorganosiloxanes include those having the general formula: Y2RSiO(YRSiO) t SiRY2 (wherein t is a number between 2 and 50; Y may be the same or different and is selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 18 carbon atoms and more preferably 1 to 8 carbon atoms and hydroxyl groups (i.e., a sufficient number of hydroxyl groups to satisfy the above criteria); and R may be the same or different and is selected from substituted or unsubstituted monovalent hydrocarbon groups having 1 to 18 carbon atoms and more preferably 1 to 8 carbon atoms. Representative hydrocarbon groups include a) alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, and heptyl; b) aryl groups such as phenyl, tolyl, xylyl, and naphthyl; and c) aralkyl groups such as benzyl and phenethyl, with methyl and phenyl groups being preferred and methyl being most preferred. Applicable commercial products include DOWSIL™ Q1-3563 Fluid and XIAMETER™ PMX-0930 Silanol Fluid (all available from The Dow Chemical Company).

[0018] Surfactants (emulsifiers) The class of surfactants applicable for use in preparing the emulsions of the present invention is not particularly limited and includes a wide range of conventional commercially available materials. The surfactants can be anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants or mixtures thereof, with cationic surfactants and nonionic surfactants being preferred.

[0019] Examples of applicable anionic surfactants include, but are not limited to, alkali metal, amine or ammonium salts of higher fatty acids, alkylarylsulfonates such as sodium dodecylbenzenesulfonate, long chain aliphatic alcohol sulfates, olefin sulfates and sulfonates, sulfated monoglycerides, sulfated esters, sulfonated ethoxylated alcohols, sulfosuccinates, alkanesulfonates, phosphate esters, alkyl isethionates, alkyl taurates, alkyl sarcosinates, and mixtures thereof. Further examples of applicable anionic surfactants include carboxylates (sodium 2-(2-hydroxyalkyloxy)acetates), amino acid derivatives (N-acyl glutamates, N-acyl glycinates or acyl sarcosinates), alkyl sulfates, alkyl ether sulfates and their oxyethylenated derivatives, sulfonates, isethionates and N-acyl isethionates, taurates and N-acyl N-methyl taurates, sulfosuccinates, alkyl sulfoacetates, phosphates and alkyl phosphates, polypeptides, anionic derivatives of alkyl polyglycosides (acyl-D-galactosiduronates) and fatty acid soaps, and mixtures thereof. Commercially available examples of applicable anionic surfactants include STEPANOL® WA-100, CALIMULSE® SLS, POLYSTEP® A-16, POLYSTEP® B-11, POLYSTEP® B-19, TRITON® QS-15, TRITON® XN-45S, and DOWFAX® 2A1.

[0020] Examples of applicable cationic surfactants include, but are not limited to, alkylamine salts, quaternary ammonium salts, sulfonium salts and phosphonium salts.Applicable commercial examples of cationic surfactants include ARQUAD® 16-29, ARQUAD® 18-50, ARLASILK EFA. ATLAS G-265, SYNPROLAM 35X15, VARISOFT® PATC, and VARISOFT® BT-85.

[0021] Examples of applicable amphoteric surfactants include, but are not limited to, imidazoline compounds, alkylamino acid salts, betaines, and mixtures thereof.

[0022] Examples of applicable non-ionic surfactants include, but are not limited to, condensation products of ethylene oxide with long chain aliphatic alcohols such as C12-C16 alcohols or fatty acids, condensation products of ethylene oxide with amines or amides, condensation products of ethylene with propylene oxide, esters of glycerol, sucrose, sorbitol, fatty acid alkylolamides, sucrose esters, fluorosurfactants, fatty amine oxides, and mixtures thereof. Further examples of nonionic surfactants include polyoxy-ethylene aliphatic alcohols, such as polyoxyethylene (23) lauryl ether, polyoxyethylene (4) lauryl ether, ethoxylated alcohols, such as ethoxylated trimethylnonanol, C12-C14 secondary alcohol ethoxylates, ethoxylated C10 Guerbet alcohols, ethoxylated iso-C13 alcohols; poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) triblock copolymers (also called poloxamers); tetrafunctional poly(oxy)ethylene derived from the sequential addition of propylene oxide and ethylene oxide to ethylenediamine. Polyoxyethylene)-poly(oxypropylene) block copolymers (also called poloxamines), silicone polyethers, polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxy-ethylene lauryl ether, polyoxyethylene sorbitan monooleate, polyoxyethylene alkyl esters, polyoxy-ethylene sorbitan alkyl esters, polyethylene glycol, polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanol, and polyoxyalkylene glycol modified polysiloxane surfactants, and combinations thereof.Further examples of applicable nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, linear primary alcohol alkoxylates, linear secondary alcohol alkoxylates, alkylphenol alkoxylates, olefin alkoxylates, branched alkoxylates, polyoxyethylene sorbitan monooleate, polyoxy-ethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycols, polypropylene glycols, diethylene glycols, ethoxylated trimethylnonanol, polyoxyalkylene substituted silicones (lake or ABn type), silicone alkanolamides, silicone esters, silicone glycosides and mixtures thereof. Further examples of applicable nonionic surfactants include dimethicone copolyols, fatty acid esters of polyols, such as sorbitol or glyceryl mono-, di-, tri-, or sesquioleate or stearate, glyceryl or polyethylene glycol laurate, fatty acid esters of polyethylene glycol (polyethylene glycol monostearate or monolaurate), polyoxyethylenated fatty acid esters of sorbitol (stearate or oleate); polyoxyethylenated alkyl (lauryl, cetyl, stearyl, or octyl) ethers.Examples of applicable commercially available non-ionic surfactants include TERGITOL™ 15-S-3, TERGITOL™ 15-S-5, TERGITOL™ 15-S-7, TERGITOL™ 15-S-9, TERGITOL™ 15-S-12, TERGITOL™ 15-S-15, TERGITOL™ 15-S-15, TERGITOL™ 15-S-20, BRIJ™ L23, BRIJ™ L24, BRIJ™ L25, BRIJ™ L26, BRIJ™ L27, BRIJ™ L28, BRIJ™ L29, BRIJ™ L30, BRIJ™ L31, BRIJ™ L32, BRIJ™ L33, BRIJ™ L34, BRIJ™ L35, BRIJ™ L36, BRIJ™ L37, BRIJ™ L38, BRIJ™ L39 ... ) LUTENSOL(R) L4, LUTENSOL(R) TO3, LUTENSOL(R) TO5, LUTENSOL(R) TO7, LUTENSOL(R) TO10, LUTENSOL(R) TO12, LUTENSOL(R) TO15, LUTENSOL(R) TO20, LUTENSOL(R) XP30, LUTENSOL(R) XP100 and LUTENSOL(R) XP140.

[0023] Further examples of applicable amphoteric and zwitterionic surfactants include betaines, N-alkylamidobetaines and their derivatives, proteins and their derivatives, glycine derivatives, sultaines, alkyl polyaminocarboxylates and alkyl amphoacetates, and mixtures thereof.

[0024] Additional water soluble ingredients may be added to the aqueous phase, including thickeners and preservatives.

[0025] In selected embodiments, the emulsions of the present invention are substantially free of one or more of the following components, including all possible combinations of the following components: i) fluoropolymers, ii) organic materials containing ethylenically unsaturated groups (e.g., unsaturated acetate, allyl ester, vinyl ester, iii) polyorganosiloxanes containing ethylenically unsaturated groups (e.g. vinyl); iv) a platinum-containing catalyst; v) resin materials (e.g., polysiloxane resins and polyurethane resins); vi) All-metal catalyst.

[0026] In this context, the term "substantially free" means less than 1 wt.-%, preferably less than 0.5 wt.-%, more preferably less than 0.1 wt.-%, and even more preferably less than 0.01 wt.-%, based on the total weight of the discontinuous oil phase.

[0027] The emulsion of the present invention can be prepared by combining the aforementioned components a), b), c) and, optionally, d) in water with one or more surfactants while mixing. Mixing can be performed using any known technique. Representative mixing devices include homogenizers, sonolators, rotor-stator turbines, colloid mills, microfluidizers, sonicators, blades, helices, and combinations thereof. Representative methods are described in U.S. Pat. No. 6,013,682, U.S. Pat. No. 8,877,293, and U.S. Patent Application Publication No. 2015 / 0010711. In a preferred embodiment, component a) and optional component d) are combined with a surfactant in water and mixed to form a first emulsion, component b) is combined with a surfactant in water and mixed to form a second emulsion, and component c) is combined with a surfactant in water and mixed to form a third emulsion. A homogenizer or sonic probe may be used to achieve the desired particle size. The first, second and third emulsions may be stored and then combined prior to use. Alternatively, components c) and / or d) may be included in the first emulsion (containing component a), the second emulsion (containing component b), or the third emulsion.

[0028] The particles of the discontinuous oil phase preferably have an average volume particle size "Dv(0.5)" of 100-5000 nm and more preferably 100-2000 nm as measured via laser diffraction according to ISO 13320 (2009) using a Malvern 3000. As used herein, the term "particles" refers to oil phase droplets.

[0029] Applicable methods of treating textiles with the subject emulsions are not particularly limited and include applying the emulsion to the textile by dipping, padding (e.g., by roll padder), curtain coating, brush coating, roll coating, and spraying methods such as air atomized spray, air assisted spray, airless spray, high volume low pressure spray, and air assisted airless spray. The resulting coating is then dried (cured) at elevated temperatures of 80-180°C for 1-3 minutes. Examples of drying steps include air drying at room temperature, hot air drying, and infrared heating. A typical coating coverage is about 1000 g / m2. 2 ) range from 0.5 to 15 grams dry weight per unit.

[0030] Many embodiments of the invention have been described, and in some instances, certain embodiments, options, ranges, components, or other features have been characterized as "preferred." The designation of such "preferred" features should in no way be construed as essential or critical aspects of the invention. Expressed ranges include the specifically specified endpoints. As used herein, the terms "molecular weight" and "Mw" refer to weight average molecular weight as measured by gel permeation chromatography (GPC). EXAMPLES

[0031] All preparations and tests were carried out at room temperature (RT) at standard pressure (1 atmosphere or 760 mm Hg) unless otherwise indicated. The following materials were used in the preparation and testing of the aqueous emulsions:

[0032] [Table 1]

[0033] The sample emulsions were prepared according to the following method. Emulsion of terminal amino 1 and terminal amino 4: Aminosilicone emulsions were prepared by combining each aminosilicone (4.00 g), BRIJ L23 (0.07 g), BRIJ L4 (0.04 g), and water (35.88 g) in a dental cup and mixed for 1 minute at 3500 rpm on a Flak-Tek Speed ​​Mixer (Model 150.1 FZV). A sonic probe (Fisherbrand Model 705) was then used at 50% power for 30 seconds to reduce the emulsion particle size.

[0034] Emulsion of terminal amino acid 2: An amino silicone emulsion was prepared by combining Terminal Amino 2 (20.00 g), BRIJ L23 (1.12 g), BRIJ L4 (0.7 g), acetic acid (10 wt % in water, 0.5 g) and water (27.68 g) in a dental cup and mixed for 30 seconds at 3500 rpm on a Flak-Tek Speed ​​Mixer (Model 150.1 FZV). Water (27.68 g) was added to the mixture, which was passed twice through a single stage homogenizer (APV Systems SPX 2000) at 15000 psi. After homogenization, acetic acid (10 wt %, 2.65 g) was added to 135.95 g of the emulsion.

[0035] Emulsion of pendant amino 1, 2 and 3 and terminal amino 3: The aminosilicone emulsions were prepared by combining the respective aminosilicone (4.00 g), BRIJ L23 (0.07 g), BRIJ L4 (0.05 g), and water (35.88 g) in a dental cup and then homogenizing using a sonic probe (Fisherbrand Model 705) at 50% power for 1 minute.

[0036] Organohydrogensiloxane-containing emulsions: XIAMETER™ OFX-5084 (60.51 g), BRIJ L23 (1.12 g), BRIJ L4 (0.61 g), and water (4.5 g) were added to the mixture and combined on a Flak-Tek speed mixer (Model 150.1 FZV) at 3500 rpm for 30 seconds. The emulsion was then diluted with water (33.26 g) and passed twice through a single-stage homogenizer (APV Systems SPX 2000) at 15000 psi. An emulsion containing DOWSIL™ MH 1107 FLUID (60.51 g) was prepared using the same procedure.

[0037] 1107 / PDMS blend emulsion: A solution of 50cSt 200 Fluid and DOWSIL™ MH 1107 FLUID was prepared by mixing the ingredients in a 1:1 ratio until homogenous and clear. To this solution (27.99g) was added ARQUAD 16-29 (2.16g) and water (4.04g) in a plastic cup and mixed on a Flak-Tek Speed ​​Mixer (Model 150.1 FZV) at 3500 rpm for 30 seconds. The emulsion was diluted with water (10.93g) and mixed with the Speed ​​Mixer at 3500 rpm for 30 seconds.

[0038] Coating emulsions were prepared by mixing the aforementioned emulsions with any additional ingredients as shown in Tables 2a, 2b, 2c and 2d (all amounts in grams). The resulting coating emulsions were then applied to standard polyester (PES Style Number 4774 075) fabrics from Burlington by padding, followed by curing at 160°C for 3 minutes in a Mathis oven (LTF 81782). All coated fabric samples were conditioned at room temperature for at least 24 hours before testing. The coated fabric samples were then allowed to equilibrate at room temperature / humidity for approximately 12 hours. Water repellency was then evaluated using ISO 9865 "Textiles-Determination of water repellency of fabrics by the Bundesmann rain-shower test" (where the sample was clamped in a sample holder and exposed to a water shower for 10 minutes). Three parameters can be measured from the test: water penetration through the fabric, fabric water absorption, and appearance (5=best, 1=worst / complete saturation of the fabric surface with water). Water absorption is calculated by (final fabric weight-initial fabric weight) / initial fabric weight. Durability was measured by performing the Bundesmann test after multiple wash / dry cycles using a standard domestic washer and dryer using TIDE® Free detergent. The wash cycle was set at 90°C, followed by a cold water rinse. The dry cycle was set at high heat with auto-sensing shutoff.

[0039] [Table 2]

[0040] [Table 3]

[0041] [Table 4]

[0042]

Table 5

Claims

1. 1. An aqueous emulsion comprising an aqueous continuous phase and a discontinuous oil phase, the discontinuous oil phase comprising the following components: a) 50 to 95 weight percent of a polyorganohydrogensiloxane; b) 0.1 to 45% by weight of an amino-modified polyorganosiloxane containing at least one amino group located in a terminal position; c) 5 to 30% by weight of a blocked isocyanate.

2. The discontinuous oil phase comprises i) 0.5 to 1.5 wt. % H; ii) 0.004 to 0.2 N weight percent.

3. 3. The emulsion of claim 1 or 2, wherein the discontinuous oil phase further comprises component d): 0.1 to 10% by weight of a polyorganosiloxane containing at least one silanol group.

4. 3. The emulsion of claim 1, wherein component a) has a weight average molecular weight (Mw) of 500 to 6000 AMU and component b) has a weight average molecular weight (Mw) of 200 to 10,000 AMU.

5. Component b) is a compound represented by the following formula: i) (CH ２ ) ３ N.H. ２ and ii) CH ２ CHR'''CH ２ 3. The emulsion of claim 1 or 2, represented by at least one of the following formulas: NHR''', where R''' is either H or an alkyl group of 1 to 6 carbon atoms.

6. The discontinuous oil phase comprises the following components: a) 60 to 90% by weight of a polyorganohydrogensiloxane; b) 1 to 20% by weight of an amino-modified polyorganosiloxane containing at least one amino group located in a terminal position; c) 10 to 25% by weight of a blocked isocyanate.

7. 3. The emulsion of claim 1 or 2, further characterized in that it is substantially free of organic materials containing ethylenically unsaturated groups.

8. 3. The emulsion of claim 1 or 2, further characterized as being substantially free of platinum-containing catalysts.

9. 3. The emulsion of claim 1 or 2, further characterized as being substantially free of resinous materials.

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