Aqueous emulsions comprising interpenetrating networks of silicone resins and organic polymers

Abstract

The present invention provides an aqueous emulsion comprising an aqueous continuous phase and a discontinuous oil phase. The discontinuous oil phase comprises particles having an interpenetrating network (IPN). The particles comprise: i) an MQ resin, ii) a polyorganosiloxane, and iii) an organic polymer.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS: This application claims the benefit under 35 USC §119(e) of U.S. Provisional Patent Application Serial No. 63 / 149,422, filed on February 15, 2021. U.S. Provisional Patent Application Serial No. 63 / 149,422 is hereby incorporated by reference. Technical field:

[0002] The present invention relates to aqueous emulsions comprising a discontinuous oil phase having particles of an interpenetrating network of silicone resins and organic polymers. These emulsions are particularly suitable for treating textiles to improve water repellency.

[0003] Preface :

[0004] Textiles, such as fabrics used for clothing, are often treated to impart water repellency. Although fluoropolymers have historically been used in such treatments, their use has decreased due to environmental and health concerns. Recent efforts have focused on the use of organosilicon (polyorganosiloxane) compositions. A commercial example is DOWSIL® from The Dow Chemical Company. TM IE-8749 brand emulsion. This product can be combined with a blocked isocyanate crosslinker and a diol penetrant to prepare a formulated finishing bath that is applied to textiles and cured at an elevated temperature, such as 160°C, for several minutes.

[0005] US2019 / 0375897 describes another silicone-based waterproofing agent comprising an amino-modified silicone, a silicone resin, and a polyfunctional isocyanate compound.

[0006] A combination of an aqueous silicone emulsion and an organic binder is also described. For example, US2019 / 0382581 describes an aqueous emulsion comprising silicone resin particles with a siloxane carrier and an organic binder. Although it relates to use in films and coatings, the reference also mentions leather and textile applications. Similarly, US2020 / 0332148 describes an aqueous emulsion for treating textiles, comprising amino-modified silicone, silicone resin, and polyorganosiloxane (e.g., polydimethylpolysiloxane, decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, etc.). The reference also describes the inclusion of poly(meth)acrylates. In these two publications, inorganic polymers (silicone resins and polyorganosiloxanes) and organic polymers are present as different particles in the emulsion. These types of emulsions cannot provide the desired combination of durability and softness. The industry is still seeking improved waterproof compositions and related textile treatments. Summary of the invention:

[0007] The inventors of the present invention have discovered that aqueous emulsions using a discontinuous oil phase comprising particles having an interpenetrating network of inorganic polymers (silicone resins and polyorganosiloxanes) and organic polymers provide superior performance compared to emulsions comprising these components as distinct particles.

[0008] In one aspect, the present invention includes an aqueous emulsion comprising an aqueous continuous phase and a discontinuous oil phase, wherein the discontinuous oil phase comprises particles having an interpenetrating network (IPN) comprising: i) an MQ resin, ii) a polyorganosiloxane, and iii) an organic polymer. In another aspect of the present invention, the subject emulsion is substantially free of fluoropolymers and / or cyclic siloxanes, such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6). In another aspect, the present invention includes a method for preparing the subject emulsion. In another aspect, the present invention includes a method for treating textiles. In another aspect, the present invention includes a textile treated with the subject emulsion. Many embodiments are described herein. Specific implementation method:

[0009] As used herein, the term "textile" refers to a flexible material composed 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 made by weaving, knitting, spreading, felting, stitching, crocheting, or bonding such fibers. In selected embodiments of the present invention, the fabric of interest is a fabric for making clothing (e.g., garments) where softness, water resistance, and durability after repeated cleaning (washing, dry cleaning, etc.) are desired.

[0010] As previously mentioned, theme emulsions comprise an aqueous continuous aqueous phase. Water can be from any source, and optionally, for example, purified by filtration, distillation, reverse osmosis technology, etc. As will be more fully described, emulsions also comprise surfactants. Surfactants can alternatively be referred to as emulsifiers, and are typically used for the discontinuous (oil) phase in the aqueous phase of emulsified emulsions.

[0011] The discontinuous oil phase of the emulsion comprises: i) an MQ resin, ii) a polyorganosiloxane, and iii) an organic polymer. The polymer of the discontinuous oil phase comprises an interpenetrating polymer network. As used herein, the term "interpenetrating polymer network" (IPN) refers to a polymeric material comprising two or more networks (polymers) that are at least partially interwoven (e.g., physically entangled) on a molecular scale but not covalently bonded to one another. The lack of covalent bonds distinguishes IPNs from block copolymers and graft copolymers. The presence of physical entanglements between the networks inhibits creep and flow; however, the lack of covalent bonds allows some migration (i.e., separation) of one network from another. The IPNs of the present invention may also be referred to as Class I mixtures or blends. As will be described in more detail, the IPNs of the present invention are prepared by imbibing organic monomers into an inorganic polymer phase (MQ resin and polyorganosiloxane), followed by in situ polymerization of the organic monomers to form the organic polymer at least partially interwoven within the inorganic polymer. More specifically, the discontinuous oil phase is prepared by emulsifying the MQ resin and polyorganosiloxane together with the organic monomers. These components are generally miscible with each other (i.e., forming an optically clear mixture when observed with the naked eye), but upon polymerization, the nascent organic polymer ("organic phase") becomes immiscible with the MQ resin and polyorganosiloxane ("silicone phase" or "inorganic phase"). While not wishing to be bound by theory, it is believed that when used to treat textiles, the silicone phase provides water repellency, while the organic phase provides reinforcement of the resulting textile coating and reduces the amount of silicone phase that migrates from the textile during washing and drying. With respect to the silicone phase, the MQ resin is believed to provide good water repellency. The polyorganosiloxane is believed to provide a softening effect when used in specific ratios with the MQ resin. Importantly, the MQ resin is not covalently bonded to the organic polymer. This allows the MQ resin to migrate and provide improved water repellency.

[0012] i) MQ resin (trimethylsiloxysilicate resin):

[0013] The subject discontinuous oil phase particles preferably comprise at least 10 wt % (e.g., 10 wt % to 50 wt %) MQ resin. MQ resins useful in the present invention include commercially available resins of the well-known class. However, it is important that, in order to prepare the subject IPN, the MQ resin must be substantially free of free radical polymerizable functional groups (e.g., vinyl, (meth) acrylic acid) which, if present, would form covalent bonds with the monomers used to prepare the organic polymer. In this context, the term "substantially free" means less than 1 wt %, more preferably less than 0.5 wt %, and even more preferably 0.0 wt %, based on the total weight of the MQ resin. Nevertheless, MQ may contain functional groups as long as the functional groups do not substantially form covalent bonds with the organic monomers under the conditions used during free radical polymerization. Specific examples of acceptable functional groups include alkoxy, amino, blocked isocyanate, methanol, epoxy, hydrocarbon, and hydroxyl groups. The quantitative ratio of the M siloxy units to the Q siloxy units of the subject MQ resin is preferably greater than 0.7:1, as determined by 29 Si NMR measurement. The weight average molecular weight (Mw) of the subject MQ resin is preferably 8000 to 50,000 AMU (Daltons). Representative commercial examples of such resins include: DOWSIL TM MQ-1600 resin, DOWSIL TM MQ-1601 resin, DOWSIL TM 2-7066 resin, DOWSIL TM MQ-7466 resin and DOWSIL TM MQ-7366 resins, all of which are commercially available from The Dow Chemical Company. Combinations of the subject MQ resins may be used together.

[0014] As background, silicone resins can generally be represented by:

[0015] (R 1 R 2 R 3 SiO 1 / 2 ) w (R 4 R 5 SiO 2 / 2 ) x (R 6 SiO 3 / 2 ) y (SiO 4 / 2 ) z ,

[0016] where R 1 -R 6Independently selected from hydrogen, hydroxyl or any organic group, such as substituted or unsubstituted hydrocarbon groups, alkoxy groups, amino groups, acetoxy groups and aminooxy groups, and w, x, y and z are independently ≥0 to ≤1, provided that y and z are not 0 at the same time and w+x+y+z=1. Subscript w represents M siloxy units, subscript x represents D siloxy units, subscript y represents T siloxy units, and subscript z represents Q siloxy units. The amount of each siloxy unit present in the resin is expressed as the mole fraction (by subscripts w, x, y and z) of the total number of moles of all M, D, T and Q siloxy units present in the silicone resin. The above formula is not intended to represent the structural order of the various siloxy units, but rather to provide convenient symbols to describe the relative amount of each type of siloxy unit in the resin, such as the mole fractions described above via subscripts w, x, y and z. The mole fractions of the various siloxy units in the silicone resin can be expressed by 29 Si NMR techniques are readily determined. When M and Q siloxy units predominate, the resulting organosiloxane is conventionally referred to as an "MQ resin."

[0017] In certain embodiments, the subject resin consists essentially of MQ units. With respect to the M and Q units in the resin, by "consisting essentially of" is meant w+z≥0.7, alternatively w+z≥0.85, alternatively w+z≥0.9, alternatively w+z≥0.95, alternatively w+z≥0.96, alternatively w+z≥0.97, alternatively w+z≥0.98, alternatively w+z≥0.99, alternatively w+z=1. Because w+x+y+z=1, when w+z<1, the balance can be attributed to the presence of at least some mole fraction of D and / or T siloxy units. Thus, the MQ resin can include at least some D and / or T siloxy units based on the above subscripts and mole fractions. In other embodiments, the MQ resin consists of M and Q siloxy units.

[0018] By R 1 -R 3 The hydrocarbyl groups represented by R, if any, may independently be substituted or unsubstituted and may be aliphatic, aromatic, cyclic, alicyclic, etc. 1 -R 3 The hydrocarbon group represented by may contain one or more heteroatoms replacing carbon atoms, for example, N, S or O may replace the carbon atoms represented by R 1 -R 3The term "substituted" as used with respect to a hydrocarbyl group, unless otherwise specified, means that one or more hydrogen atoms in the hydrocarbyl group have been replaced with another atom or substituent. Examples of unsubstituted aliphatic hydrocarbyl groups include, but are not limited to, alkyl groups such as methyl, ethyl, propyl, pentyl, octyl, decyl, dodecyl, undecyl, and octadecyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; aryl groups such as phenyl, tolyl, xylyl, and benzyl; and aralkyl groups such as 2-phenylethyl. Preferred unsubstituted aliphatic hydrocarbyl groups include methyl groups.

[0019] Suitable silicone resins can be prepared, for example, by hydrolysis of certain silane materials in solvent or in situ. A particularly preferred method involves the hydrolysis and condensation of a precursor of tetravalent siloxy units (e.g., tetraorthosilicate, tetraethyl orthosilicate, polyethyl silicate, or sodium silicate) and a precursor of monovalent trialkylsiloxy units (e.g., trimethylchlorosilane, trimethylethoxysilane, hexamethyldisiloxane, or hexamethyldisilazane) in the presence of a solvent such as xylene. The resulting MQ resin can be further trimethylsilylated to react out residual Si—OH groups, or heated in the presence of a base to induce self-condensation of the resin by eliminating Si—OH groups.

[0020] ii) Polyorganosiloxane :

[0021] The subject discontinuous oil phase particles preferably contain at least 25% by weight (e.g., 25% to 80% by weight) of polyorganosiloxane. The polyorganosiloxane used in the present invention is not particularly limited and includes linear and branched species preferably having a weight average molecular weight (Mw) of 500 to 100,000 AMU (Daltons), more preferably 1000 to 10,000, and even more preferably 1000 to 5000. In selected embodiments, the subject polyorganosiloxane is substantially free of volatile cyclic siloxanes, including D4, D5, and D6. In this context, the term "substantially free" means less than 1% by weight, more preferably less than 0.5% by weight, and even more preferably 0.0% by weight, based on the total weight of the polyorganosiloxane. In addition, in other selected embodiments, the subject polyorganosiloxane is substantially free of Q siloxy units. In this context, the term "substantially free" means less than 1% by weight, more preferably less than 0.5% by weight, and even more preferably 0.0% by weight, based on the total weight of the polyorganosiloxane. Representative subclasses of suitable polyorganosiloxanes include polyalkylsiloxanes, polyarylsiloxanes, and polyalkylarylsiloxanes. Suitable commercial examples include DOWSIL TM200 fluid (trimethylsilyl-terminated polydimethylsiloxane), available from The Dow Chemical Company in various viscosities. The preferred viscosity range is 5 mPa·s to 100,000 mPa·s (cSt), and more preferably 10 mPa·s to 70,000 mPa·s. Unless otherwise specified, the term "viscosity" refers to the dynamic viscosity at 25°C using a rotational viscometer (Brookfield DVII) according to ASTM D2196-05. Combinations of different polyorganosiloxanes can be used together.

[0022] The weight ratio of i) MQ resin to ii) polyorganosiloxane is preferably 1:0.5 to 1:5. This range provides a preferred balance of water repellency and softness.

[0023] Suitable polyorganosiloxanes can be represented by the following:

[0024] R 7 a SiO (4-a) / 2

[0025] Each R 7 Independently selected from the above 1 -R 6 The group defined herein, and "a" is preferably a number between 1.8 and 2.5 and more preferably between 1.95 and 2.05. Unlike the limitations of the above-mentioned MQ resins, polyorganosiloxanes may contain functional groups covalently bonded to the monomers used to prepare the organic polymer. That is, R 7 Functional groups may also be independently selected from groups including ethylenically unsaturated groups, such as vinyl, (meth)acrylic, and acrylic.

[0026] iii) Organic polymers :

[0027] The subject discontinuous oil phase particles preferably comprise from 1% to 50% by weight of an organic polymer having a glass transition (Tg) temperature of 0°C to 150°C. As used herein, the term "organic polymer" refers to the reaction product of ethylenically unsaturated organic monomers polymerized via a free radical mechanism. The ethylenically unsaturated organic monomers are preferably selected from one or more of the following: acrylates, vinyl esters, vinyl aromatic compounds, olefins, 1,3-dienes, and vinyl halides, with one or more of acrylates and vinyl aromatic compounds being particularly preferred. In selected embodiments, the subject organic polymer does not contain siloxy functional groups.

[0028] As used herein, the term "acrylate" or "acrylate monomer" refers to monomers based on acrylic acid and its salts, esters, and conjugate bases. Representative "acrylate monomers" include: methacrylates, substituted acrylates, and substituted methacrylates. Specific examples include acrylates and methacrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, decyl acrylate, lauryl acrylate, isodecyl methacrylate, lauryl methacrylate, and butyl methacrylate; and substituted acrylates and methacrylates such as hydroxyethyl acrylate, perfluorooctyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and hydroxyethyl methacrylate. Representative "acrylic acids" include acrylic acid, methacrylic acid, ethacrylic acid, and their corresponding salts.

[0029] Representative "vinyl halides" include vinyl chloride, vinylidene chloride, and chloroprene. Other examples of suitable monomers include: maleic anhydride, "vinyl esters" such as vinyl acetate and vinyl butyrate; vinyl pyrrolidone; conjugated dienes such as butadiene and isoprene; "vinyl aromatics" such as styrene and divinylbenzene; vinyl monomers such as ethylene; acrylonitrile and methacrylonitrile; acrylamide, methacrylamide, and N-methylolacrylamide; and monocarboxylic acid vinyl esters having up to 10 carbon atoms.

[0030] The subject monomers may include materials having multiple ethylenically unsaturated groups (i.e., containing at least two polymerizable carbon-carbon double bonds) that undergo free radical polymerization under appropriate reaction conditions. Suitable examples include allyl methacrylate, diallyl phthalate, 1,4-butanediol dimethacrylate, 1,2-ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, and divinylbenzene.

[0031] The total weight percentage is important for providing excellent textile treatment. For example, including more than 50% by weight of organic polymer in the particles of the discontinuous oil phase results in a brittle textile coating. Therefore, the total weight percentage of the subject organic polymer (including the MQ resin and the polyorganosiloxane) in the oil phase particles is preferably 1% to 50% by weight, more preferably 5% to 45% by weight, and even more preferably 10% to 40% by weight.

[0032] The subject organic polymer preferably has a glass transition (Tg) temperature of 0°C to 150°C, more preferably 1°C to 50°C, and even more preferably 10°C to 40°C. The use of polymers having Tg values below 0°C reduces the water repellency provided by the resulting emulsion. The Tg of the subject organic polymer can be determined based on a theoretical polymer having a weight average molecular weight (Mw) of 50,000, which is calculated using the Fox formula (TG Fox, Bull. Am. Physics Soc., Vol. 1, No. 3, p. 123 (1956)). For example, to calculate the Tg of a copolymer of a monomer mixture of monomers M1 and M2, 1 / Tg = w(M1) / Tg(M1) + w(M2) / Tg(M2), where w(M1) is the weight fraction of monomer M1 in the copolymer, w(M2) is the weight fraction of monomer M2 in the copolymer, Tg(M1) is the published glass transition temperature ("Fox Tg") of a high molecular weight homopolymer (>50k weight average MW) of M1, and Tg(M2) is the published glass transition temperature of a high molecular weight homopolymer of M2. Tg values for homopolymers are listed in Polymer Handbook, 4th edition, J. Wiley & Sons, New York (2003).

[0033] Various additives may be included in the subject emulsions, including during the preparation of the initial discontinuous oil phase, during the in situ polymerization of the organic material, and / or after. Examples of such additives include surfactants, initiators, penetrants, melamine, waxes, polyurethane dispersions, and the like. One such optional additive includes blocked isocyanates.

[0034] iv) Blocked isocyanate :

[0035] As mentioned above, the subject emulsion may also include one or more blocked isocyanates. As used herein, the term "blocked isocyanate" refers to the reaction product of an isocyanate and a blocking agent, wherein the blocking agent can be removed from the isocyanate under thermal conditions (i.e., those conditions commonly used when processing textiles). Conventional blocking agents include aryl alcohols, alkanoic acid oximes, aryl mercaptans, organic active hydrogen compounds, sodium bisulfite and hydroxylamine. Preferred blocking agents include alkanoic acid oximes (ketoximes), which can be deblocked at relatively low temperatures, such as the temperature used in typical textile processing processes. For purposes of the present invention, "aromatic" blocked polyisocyanates are preferred. In this context, the term "aromatic" means an isocyanate compound with at least one aromatic group, such as based on toluene diisocyanate, diphenylmethane 4,4' diisocyanate, diphenylmethane 2,4' diisocyanate, polymethylene-polyphenylisocyanate, 4,4' methylene bisphenol isocyanate and the materials of their derivatives. Suitable isocyanates A (CNO) for preparing blocked isocyanates zare those in which A is an aromatic compound and z is 1, 2, 3 or 4. These include isocyanates or derivatives such as toluene diisocyanate, polymethylene polyphenyl isocyanate and 4,4' methylene bisphenol isocyanate, and include those aromatic isocyanates commercially available for this purpose. Typical commercial products include the following: adducts such as DESMODUR CB-75 (available from Covestro), an adduct of toluene diisocyanate and trimethylolpropane (1,1,1 trimethylolpropane); aromatic isocyanates based on polymethylene polyphenylene esters of isocyanic acid, such as MONDUR MR-100 (available from Covestro), and aromatic isocyanates based on polymethylene polyphenylene isocyanate containing 4,4' methylene bisphenol isocyanate (available from The Dow Chemical Co.). Also commercially available are ready-made blocked aromatic isocyanates such as HYDROPHOBOL DL, PHOBOL XAN (available from Huntsman), DM-6400, MEIKANATE FM-1, MEIKANATE ST, MEIKANATE PRO, MEIKANATE TP-10, MEIKANATE WEB, MEIKANATE ST (available from Meisei Chemical Works, Ltd.). More background information on such isocyanates is provided in US2019 / 0375897, US839255, and US6451717.

[0036] The particles of the discontinuous oil phase preferably have an average volume particle size "D(v0.5)" of 10 nm to 5000 nm, more preferably 50 nm to 3000 nm, as measured by laser diffraction using a Malvern 3000 and according to ISO 13320 (2009). As used herein, the term "particles" refers to oil phase droplets.

[0037] In selected embodiments, the subject emulsions are substantially free of fluoropolymers and / or cyclic siloxanes, such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6). In this context, the term "substantially free" means less than 1 wt%, more preferably less than 0.5 wt%, and even more preferably 0.0 wt%, based on the total weight of the discontinuous oil phase.

[0038] The discontinuous oil phase of the subject emulsions preferably comprises 5 wt% to 80 wt%, more preferably 10 wt% to 60 wt%, based on the total weight of the emulsion.

[0039] Although related to cosmetic applications, US Pat. No. 98,008,413 describes an emulsion prepared in a manner similar to the present invention. However, the Tg and total weight of the organic polymer are unsuitable for textile treatment. For example, the organic polymer is present in an amount greater than 50% by weight (e.g., >66% by weight) of the mixed organosilicon-organic particles, resulting in a coating that is too brittle to be effectively used on textiles. Similarly, US Pat. No. 7,767,747 describes a method for preparing a mixed emulsion containing both a polysiloxane and an organic polymer, but without the use of an organosilicon resin. While none of these patents describe the treatment of the subject emulsions or textiles, the general methods they describe are instructive.

[0040] With specific reference to the present invention, a method for preparing the subject emulsion comprises the following steps: (1) obtaining or preparing an aqueous emulsion comprising a discontinuous oil phase comprising particles, the particles comprising: i) an MQ resin, the MQ resin being substantially free of free radical polymerizable functional groups; ii) a polyorganosiloxane; and iii) an ethylenically unsaturated organic monomer selected from one or more of the following: acrylates, vinyl esters, vinyl aromatic compounds, olefins, 1,3-dienes, and vinyl halides; and (2) polymerizing the ethylenically unsaturated organic monomer in situ to form an interpenetrating network within the particles. With respect to step (1), the order of addition of each component is not particularly limited, and the additional use and mixing of surfactants may be used to facilitate emulsion formation and particle size control. With respect to step (2), the use of an initiator and elevated temperatures (e.g., 70 to 95° C.) may be used to facilitate free radical polymerization of the organic monomers.

[0041] Any known technique in the field of emulsions can be used for mixing. Typically, a simple stirring technique is used to combine the oil phase with an aqueous phase containing any surfactant to form an emulsion. Representative mixing devices include homogenizers, sonographers, rotor-stator turbines, colloid mills, microfluidizers, sonicators, blades, spirals, and combinations thereof. Representative methods are described in US6013682, US8877293, and US2015 / 0010711.

[0042] The example of applicable surfactant includes cation, anion and / or nonionic surfactant, preferably cationic surfactant. As used herein, the term "cationic surfactant" means a surfactant with a positively charged functional group, for example a quaternary ammonium compound with a positively charged surface active portion. This definition includes amphoteric surfactants with positive and negative charge groups, but does not include nonionic and anionic surfactants. Cationic surfactants that can be used for the present invention can be quaternary ammonium hydroxides, such as octyl trimethyl ammonium hydroxide, dodecyl trimethyl ammonium hydroxide, hexadecyl trimethyl ammonium hydroxide, octyl dimethyl benzyl ammonium hydroxide, decyl dimethyl benzyl ammonium hydroxide, didodecyl dimethyl ammonium hydroxide, dioctadecyl dimethyl ammonium hydroxide, tallow trimethyl ammonium hydroxide and coconut oil trimethyl ammonium hydroxide and the corresponding salts of these substances, fatty amines and fatty acid amides and derivatives thereof, alkaline pyridine compounds, quaternary ammonium bases of benzimidazolin and polypropyl alcohol-polyethanolamine, but are not limited to the cationic surfactant list. Alternatively, the cationic surfactant is cetyl trimethyl ammonium chloride. These surfactants can be used individually or in combination. The surfactant is dissolved in water and the resulting aqueous solution is used as a component in the aqueous continuous phase. During the formation of the oil-in-water emulsion, the concentration of the cationic surfactant is preferably 0.5% to 4.0% by weight of the total oil phase. Auxiliary surfactants, particularly nonionic surfactants, can be added during the formation of the oil-in-water emulsion. Suitable nonionic surfactants are: polyoxyalkylene alkyl ethers such as polyethylene glycol long chain (12 to 14 carbon) alkyl ethers, polyoxyalkylene sorbitan ethers, polyoxyalkylene alkoxylate esters, polyoxyalkylene alkylphenol ethers, ethylene glycol propylene glycol copolymers, polyvinyl alcohol and alkyl polysaccharides. Additional water-soluble ingredients, including thickeners and preservatives, can be added to the aqueous phase.

[0043] Examples of suitable water-soluble free radical initiators include t-butyl peroctoate and t-butylperoxy-2-ethylhexanoate. Thermal or redox initiation processes can be used in the preparation of organic polymers. Examples of conventional thermal free radical initiators that can be used include hydrogen peroxide, sodium peroxide, potassium peroxide, t-butyl hydroperoxide, cumene hydroperoxide, ammonium and / or alkali metal persulfates, sodium perborate, perphosphoric acid and its salts; potassium permanganate; and ammonium or alkali metal salts of peroxodisulfate. These initiators are typically used at levels of 0.1% to 5.0% by weight, based on the total weight of the organic monomers. The redox initiator that can be used is generally an oxidant plus a reducing agent that is combined to effectively generate free radicals, including the same free radical initiators listed above as oxidants; and suitable reducing agents such as sodium formaldehyde sulfoxylate, ascorbic acid, isoascorbic acid, alkali metal salts and ammonium salts of sulfur-containing acids such as sodium sulfite, bisulfite, thiosulfate, bisulfite, sulfide, hydrosulfide or dithionite, formamidinesulfinic acid, hydroxymethanesulfonic acid, acetone bisulfite; amines such as ethanolamine, glycolic acid, glyoxylic acid hydrate, lactic acid, glyceric acid, malic acid, tartaric acid, and salts of the aforementioned acids that can be used. The initiator or initiator system can be added continuously in one or more additions, linearly added or not added, or as a combination thereof over the reaction period. Several azo-type organic free radical initiators that can be used in the monomer swelling process, such as azobisisobutyronitrile and azobispropionitrile.

[0044] Suitable methods for treating textiles with the subject emulsion are not particularly limited and include applying the emulsion to the textile by dipping, padding (e.g., via a roller mill), curtain coating, brushing, roller coating, and spraying methods such as air atomized spraying, air-assisted spraying, airless spraying, high volume low pressure spraying, and air-assisted airless spraying. The resulting coating is then dried (cured) at an elevated temperature of 80° C. to 180° C. Examples of drying steps include air drying at room temperature, hot air drying, and infrared heating. Typical coating coverages are 0.5-15 grams dry weight per square meter (g / m 2 ).

[0045] Many embodiments of the present invention have been described, and in some cases, certain embodiments, options, ranges, ingredients, 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 present invention. Expressed ranges specifically include the specified endpoints. As used herein, the terms "molecular weight" and "Mw" refer to the weight average molecular weight as measured by gel permeation chromatography (GPC).

[0046] Example :

[0047] Unless otherwise stated, all preparations and tests were performed at room temperature (RT) and standard pressure (1 atm or 760 mm Hg). The following materials were used to prepare and test the aqueous emulsions:

[0048] Table 1: Description of materials used in the examples

[0049]

[0050]

[0051] The sample emulsions were prepared according to the following method :

[0052] Emulsion 1: MQ-1600 / PDMS / styrene-acrylic acid mixed colloid

[0053] Emulsion preparation: Mix MQ-1600 (13.3 g), 50 cSt 200 fluid (26.6 g), butyl acrylate (5.00 g), styrene (11.17 g), AAEM (1.12 g) in a wide-mouth bottle. Add water (10.64 g), ARQUAD 16-29 (1.40 g), TERGITOL TM 15-S-20 (80% active material, 1.39 g) was added and mixed again to form a coarse emulsion. Water (140.59 g) was added and the mixture was emulsified using a sonicator (Fisher 705) at 75% power for 1.5 minutes. Dilution water (148.74 g) was added.

[0054] Free Radical Polymerization Process: The emulsion was added to a glass reactor equipped with a stirrer shaft, nitrogen flow, and a thermocouple-controlled heating mantle. The emulsion was heated to 70.0°C. In a separate glass vial, LUPEROX 26 (0.68 g), TERGITOL TM 15-S-20 (80% active, 0.09 g) and water (0.7 g) were mixed together to prepare an initiator emulsion. This emulsion was added to a glass reactor along with a water rinse (4.7 g). After 30 minutes, the temperature was raised to 85.0°C. After 60 minutes, the temperature was raised to 92.0°C and held for 60 minutes before cooling the reactor.

[0055] Emulsion 2: MQ-1600 / PDMS emulsion (without organic polymer)

[0056] A mixture of 20 cSt 200 fluid (12.71 g) and MQ-1600 (6.34 g) was mixed in a high-speed dental mixer at 3500 rpm. ARQUAD 16-29 (1.88 g) was added and mixed again. Water was added in the following increments with high-speed mixing between additions: 5.25 g, 5.66 g, 2.21 g, 4.04 g, 2.00 g, and 2.21 g.

[0057] Emulsion 3: Styrene-acrylic emulsion polymer (no MQ, no PDMS)

[0058] Emulsion preparation: Mix butyl acrylate (9.99g), styrene (22.37g), AAEM (2.16g). Add water (16.92g), ARQUAD 16-29 (1.04), TERGITOL TM 15-S-20 (80% active material, 1.05 g) was added and mixed to form a coarse emulsion. Water (100.00 g) was added and mixed using a sonic probe at 50% power for 1.5 minutes. Dilution water (140.21 g) was added. The free radical polymerization process was the same as for Emulsion 1.

[0059] Emulsion 4: MQ-1600 / PDMS / vinyl-PDMS / styrene-acrylic acid mixed colloid Mix MQ-1600 (11.24g), 20cSt 200 fluid (11.24g), SFD-128 (M Vi D 766 M Vi , 11.24g), butyl acrylate (4.22g), styrene (9.42g), AAEM (0.91g), until homogeneous. Add water (84.71g), ARQUAD 16-29 (1.13), TERGITOL TM 15-S-20 (80% active material, 1.16 g) was added and mixed to form a coarse emulsion. Water (33.15 g) was added and mixed using a sonic probe at 50% power for 1.5 minutes and 100% power for 1 minute. Homogenization was performed using a Microfluidics homogenizer at 10,000 psi. Dilution water (100.0 g) was added. The free radical polymerization procedure was the same as for Emulsion 1.

[0060] Emulsion 5: MQ-1600 / PDMS / styrene-acrylic acid mixed colloid with 4:1 PDMS:MQ

[0061] Mix MQ-1600 (8.05g), 20cSt 200 fluid (32.2g), butyl acrylate (5.00g), styrene (11.17g), AAEM (1.12g) until homogeneous. Add water (99.11g), ARQUAD 16-29 (1.35g), TERGITOL TM 15-S-20 (80% active material, 1.35 g) was added and mixed using a sonicator at 75% power for 1.5 minutes. Dilution water (134.42 g) was added. The free radical polymerization process was the same as for Emulsion 1.

[0062] Emulsion 6: MQ 2-7066 silicone / PDMS / styrene-acrylic acid mixed colloid

[0063] DOWSIL TM2-7066 silicone (17.2 g of a 78 wt% resin solution in xylene) was mixed with 20 cSt 200 fluid (26.8 g) and the solvent was removed at 70°C under reduced pressure (about 5 torr) for 2 hours. Butyl acrylate (5.00 g), styrene (11.17 g), AAEM (1.08 g) were added and mixed until homogeneous. Water (150.6 g), ARQUAD 16-29 (1.35 g), TERGITOL TM 15-S-20 (80% active material, 1.35 g) was added and mixed using a sonicator at 75% power for 1.5 minutes. Dilution water (82.93 g) was added. The free radical polymerization process was the same as for Emulsion 1.

[0064] Emulsion 7: MQ-1600 / PDMS / styrene-acrylic mixed colloid with 1000 cSt PDMS

[0065] Mix MQ-1600 (13.40 g), 1000 cSt 200 fluid (26.83 g), butyl acrylate (5.00 g), styrene (11.17 g), AAEM (1.08 g) until homogeneous. Add water (101.75 g), ARQUAD 16-29 (1.35 g), TERGITOL TM 15-S-20 (80% active material, 1.35 g) was added and mixed using a sonicator at 75% power for 1.5 minutes. Dilution water (131.8 g) was added. The free radical polymerization process was the same as for Emulsion 1.

[0066] Emulsion 8: MQ-1600 / PDMS / acrylic acid mixed colloid (styrene-free)

[0067] Mix MQ-1600 (13.40 g), 20 cSt 200 fluid (26.83 g), butyl acrylate (6.69 g), methyl methacrylate (9.47 g) and AAEM (1.08 g) until homogeneous. Add water (150.6 g), ARQUAD 16-29 (1.35 g), TERGITOL TM 15-S-20 (80% active material, 1.35 g) was added and mixed using a sonicator at 75% power for 1.5 minutes. Dilution water (82.94 g) was added. The free radical polymerization process was the same as for Emulsion 1.

[0068] Emulsion 9: MQ-1600 / PDMS / styrene-acrylic acid mixed colloid with 10% styrene-acrylic acid

[0069] Mix MQ-1600 (17.25 g), 20 cSt 200 fluid (34.50 g), butyl acrylate (1.67 g), styrene (3.72 g) and AAEM (0.36 g) in a glass jar. Add water (103.03 g), ARQUAD 16-29 (1.35 g), TERGITOL TM15-S-20 (80% active material, 1.35 g) was added and mixed using a sonicator at 75% power for 2.0 minutes. Dilution water (130.5 g) was added. The free radical polymerization process was the same as for Emulsion 1.

[0070] Emulsion 10: MQ-1600 / PDMS / acrylic acid mixed colloid (styrene-free)

[0071] Mix MQ-1600 (13.40 g), 20 cSt 200 fluid (26.83 g), MDM-ALMA (7.06 g), IBOMA (9.11 g), AAEM (1.08 g) until homogeneous. Add water (101.08 g), ARQUAD 16-29 (1.35 g), TERGITOL TM 15-S-20 (80% active material, 1.35 g) was added and mixed using a sonicator at 75% power for 1.5 minutes. Dilution water (132.45 g) was added. The free radical polymerization process was the same as for Emulsion 1.

[0072] Emulsion 11: MQ-1600 / PDMS / styrene-acrylic acid mixed colloid (without AAEM)

[0073] Mix MQ-1600 (13.40 g), 20 cSt 200 fluid (26.83 g), butyl acrylate (5.66 g) and styrene (11.58 g) in a glass jar. Add water (150.6 g), ARQUAD 16-29 (1.35 g), TERGITOL TM 15-S-20 (80% active material, 1.35 g) was added and mixed using a sonicator at 100% power for 1.5 minutes. Dilution water (82.94 g) was added. The free radical polymerization process was the same as for Emulsion 1.

[0074] Emulsion 12: MQ-1600 / PDMS / styrene-acrylic acid mixed colloid with 50% styrene-acrylic acid

[0075] The same emulsion and free radical polymerization procedures as emulsion 11 were followed, except that the emulsion composition contained MQ-1600 (9.58 g), 20 cSt PDMS (19.16 g), butyl acrylate (8.33 g), styrene (18.61 g), AAEM (1.80 g).

[0076] Emulsion 13: MQ-1600 / PDMS / styrene-acrylic acid mixed colloid with Tg = 15°C

[0077] The same emulsification and free radical polymerization procedures as for Emulsion 11 were followed, except that the emulsion composition contained MQ-1600 (13.40 g), 20 cSt 200 fluid (26.83 g), butyl acrylate (6.69 g), styrene (9.47 g), and AAEM (1.08 g), and the sonic probe was operated at 75% power for 1.5 minutes.

[0078] Emulsion 14: MQ-1600 / PDMS / styrene-acrylic acid mixed colloid with Tg = -15°C

[0079] The same emulsification and free radical polymerization procedures as for Emulsion 11 were followed, except the emulsion composition contained MQ-1600 (13.40 g), 20 cSt 200 fluid (26.83 g), butyl acrylate (10.40 g), styrene (5.78 g), and AAEM (1.08 g).

[0080] Emulsion 15: MQ resin 2 / PDMS / styrene-acrylic acid mixed colloid

[0081] MQ resin 2 (17.48 g of a 76.6 wt% resin solution in xylene) was mixed with 20 cSt 200 fluid (26.8 g) and the solvent was removed at 70°C under reduced pressure (about 5 torr) for 2 hours. Butyl acrylate (5.00 g), styrene (11.17 g), AAEM (1.08 g) were added and mixed manually. Water (200.66 g), ARQUAD 16-29 (1.35 g), TERGITOL TM 15-S-20 (80% active material, 1.35 g) was added and mixed using a sonicator at 75% power for 1.5 minutes. Dilution water (32.93 g) was added. The free radical polymerization process was the same as for Emulsion 1.

[0082] Emulsion 16: PDMS / styrene-acrylic acid mixed colloid (without MQ resin)

[0083] Mix vinyl terminated PDMS (SFD-128, 40.43 g), butyl acrylate (5.00 g), styrene (11.17 g) and AAEM (1.08 g) until homogeneous. Add water (0.41 g), ARQUAD 16-29 (1.35 g), TERGITOL TM 15-S-20 (80% active substance, 1.39 g) was added and mixed on a high-speed dental mixer at 3500 rpm for 30 seconds to form a water-in-oil emulsion. Water (39.29 g) was then added and mixed again at 3500 rpm for 30 seconds. The emulsion was diluted with water (206 g). The free radical polymerization procedure was the same as for Emulsion 1.

[0084] Table 2: Summary of selected emulsion ingredients :

[0085]

[0086] Coating emulsions (IE1-IE17, CE1-CE6) were prepared using the above emulsions (Emulsions 1-16) and various fabric samples (nylon and PES) were coated and tested according to the following methods.

[0087] The coating emulsions (IE1-IE17, CE1-CE6) were applied to the fabric samples via padding on a Mathis 2-roll padder (HVF-350) with the roll pressure set at 60 psi and the rate at 2.0 m / min. The moisture pickup for the nylon and polyester fabrics was 53% and 79%, respectively. The moisture pickup is defined as the percentage increase in weight of the fabric after passing through the treatment solution and padder but before drying. For example, if the fabric initially weighs 100 grams and after passing through the treatment solution / padder, the fabric weighs 150 grams, then the moisture pickup is 50%. Immediately after padding, the fabric was cured in a Mathis LTE oven at 160°C for 3 minutes. The coated fabric samples were then allowed to equilibrate at room temperature / humidity for approximately 12 hours before being washed using a standard household washing machine and dryer. The coated fabric samples were washed with free detergent. The wash cycle was set to 90°C followed by a cold rinse. The dry cycle was set to high temperature with the auto-sensing function turned off.

[0088] Water repellency was measured using ISO 9865:1991 "Textiles - Determination of water repellency offabrics by the Bundesmann rain-shower test". In summary, a fabric sample was placed in a Bundesmann apparatus where simulated rainfall impinged on the fabric surface for a period of 10 minutes, after which the visual appearance of the fabric was qualitatively rated (5 = best, 1 = worst / fabric surface completely saturated with water).

[0089] Softness was measured on a subjective 1-5 scale, with 1 being the hairiest / roughest and 5 being the softest / smoothest.

[0090] Seam tape adhesion was determined using ASTM method D413-98 using TAF-900 seam tape. The tape was applied to the fabric using a ChemInstruments HL-100 hot roll laminator set at 245°F. Each fabric sample was laid on a silicone rubber mat and covered with a 7 / 8-inch wide and 10-inch long strip of tape. A polyester film sheet was laid on top of the fabric / tape and fed into the laminator at a rate of 3.8 inches / minute and a roller pressure of 40 psi. After cooling to room temperature, adhesion was measured using a TMI LabMaster 8091 Release and Adhesion Tester; the tape was peeled off using 180-degree geometry at a rate of 12 inches / minute. Unless otherwise specified, tape adhesion measurements were performed in triplicate.

[0091] Table 3: Test results

[0092]

[0093] Table 4: Test results

[0094]

[0095] Table 4: Test results

[0096]

[0097] As shown in the test results above, the subject emulsions, represented by IE1-IE17, exhibit improved water repellency compared to comparative emulsions CE1-CE6. This superior performance is particularly evident through visual repellency after 10 wash cycles. Specifically, CE1 demonstrates the effect of the organic polymer; CE2 demonstrates the effect of the subject IPN structure relative to different particles with inorganic or organic polymers; CE3 demonstrates the impact of using an organic polymer with too low a Tg; CE4-5 demonstrate the effect of using an MQ resin with too low a Mw; and finally, CE6 demonstrates the effect of the MQ resin.

Claims

1. An aqueous emulsion comprising an aqueous continuous phase and a discontinuous oil phase, wherein the discontinuous oil phase comprises particles having an interpenetrating network, wherein the particles comprise: i) at least 10% by weight of an MQ resin, wherein The ratio of the number of M siloxy units to the number of Q siloxy units is greater than 0.7:1; the free radical polymerizable functional groups are less than 1 weight percent based on the total weight of the MQ resin; ii) at least 25% by weight of a polyorganosiloxane; and iii) 1 to 50 wt% of an organic polymer which is the reaction product of ethylenically unsaturated organic monomers polymerized via a free radical mechanism and has a glass transition temperature of 0°C to 150°C; The MQ resin has a weight average molecular weight of 8,000 to 50,000 Daltons.

2. The emulsion of claim 1, wherein the ethylenically unsaturated organic monomer is selected from one or more of the group consisting of acrylates, vinyl esters, vinyl aromatic compounds, olefins, and vinyl halides.

3. The emulsion of claim 1, wherein the ethylenically unsaturated organic monomers comprise acrylates and vinyl aromatic compounds. The emulsion according to claim 1 , wherein the weight ratio of the MQ resin to the polyorganosiloxane is 1:0.5 to 1:

5. The emulsion according to claim 1 , wherein the polyorganosiloxane has a weight average molecular weight of 500 to 100,000.

6. The emulsion according to claim 1, further characterized in that The cyclic silicone is present in an amount less than 1 wt % based on the total weight of the discontinuous oil phase.

7. A method for preparing an aqueous emulsion comprising an aqueous continuous phase and a discontinuous oil phase, the method comprising the steps of: (1) obtaining or preparing an aqueous emulsion comprising a discontinuous oil phase comprising particles, the particles comprising: i) at least 10 weight percent of an MQ resin, wherein the ratio of the number of M siloxy units to the number of Q siloxy units is greater than 0.7:1; and less than 1 weight percent of free radically polymerizable functional groups based on the total weight of the MQ resin; ii) at least 25 weight percent of a polyorganosiloxane; and iii) an ethylenically unsaturated organic monomer selected from one or more of the group consisting of acrylates, vinyl esters, vinyl aromatic compounds, olefins, and vinyl halides, wherein the MQ resin has a weight average molecular weight of from 8000 to 50,000 Daltons; (2) polymerizing the ethylenically unsaturated organic monomer to form an interpenetrating network within the particle, such that the particle comprises from 1 wt% to 50 wt% of an organic polymer that is a reaction product of the ethylenically unsaturated organic monomer polymerized via a free radical mechanism.

8. The method according to claim 7, wherein step (2) comprises the steps of adding an initiator to the emulsion and heating the emulsion.

9. A textile product coated according to the method of claim 7.

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