WO2022055884A1

WO2022055884A1 - Silicone polyether polymer treatments

Info

Publication number: WO2022055884A1
Application number: PCT/US2021/049287
Authority: WO
Inventors: John Christopher Sworen; Gerald Oronde Brown; Charles K. KARANJA; Amy Lizabeth WARREN
Original assignee: The Chemours Company Fc, Llc
Priority date: 2020-09-09
Filing date: 2021-09-07
Publication date: 2022-03-17

Abstract

Described is a treated substrate, wherein the treatment composition has: a) about 20-99.5% by weight of a silicone polyether polymer; b) about 0.5-4% by weight of at least one anionic surfactant, cationic surfactant, nonionic surfactant, zwitterionic surfactant, or mixtures thereof; and optional additional components; where the silicone polyether polymer has about 40-100% by weight of formula (I) or formula (II) and about 0-60% by weight of ethylenically unsaturated comonomers; a and b are integers of 1 to 40 where a+b is an integer of at least 2; c and d are integers of 0 to 20; e is an integer of 1 to 40; X is a linear or branched C₁-C₄ alkylene group; R¹ is a C₁-C₄ alkyl group; and R² is -C(R¹)=CH₂ or polymer backbone unit –[C(R¹)-CH₂]- bonded at C(R¹). Treatments exhibit improved balance of water repellency and oily stain release performance.

Description

TITLE OF INVENTION

SILICONE POLYETHER POLYMER TREATMENTS FIELD OF THE INVENTION

[0001] Silicone polyether polymer compositions are employed as coating or finishing agents to provide surface effects to various substrates.

BACKGROUND OF THE INVENTION

[0002] Various compositions are known to be useful as treating agents to provide surface effects to substrates. Surface effects include repellency to moisture, soil and stain resistance, and other effects which are particularly useful for hard or fibrous substrates such as fibers, fabrics, textiles, carpets, paper, leather, stone and tile, glass, metal, and other such substrates. Many such treating agents are partially fluorinated polymers or copolymers.

[0003] Fluorinated polymer compositions are used in the preparation of a wide variety of surface treatment materials to provide surface effects to substrates. Many such compositions are fluorinated surfactants which contain predominantly eight or more carbons in the perfluoroalkyl chain to provide the desired properties. Honda, et al., in Macromolecules, 2005, 38, 5699-5705 teach that for perfluoroalkyl chains of greater than 8 carbons, orientation of the perfluoroalkyl groups, designated Rf groups, is maintained in a parallel configuration while for such chains having 6 or less carbons, reorientation occurs. This reorientation is recited to decrease surface properties such as contact angle. Thus, compounds containing shorter perfluoroalkyl chains or having no fluorine content have traditionally exhibited lower performance.

BRIEF SUMMARY OF THE INVENTION

[0004] The need exists for compositions that provide surface effects to various substrates, where performance of water repellency is balanced with oily stain release properties. The present invention meets these needs.

[0005] The present invention relates to a treated substrate comprising a substrate and a treatment composition applied thereon, wherein the treatment composition comprises: a) about 20-99.5% by weight of a silicone polyether polymer; b) about 0.5-4% by weight of at least one surfactant selected from anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants, and mixtures thereof; and c) about CI- 79.5% by weight of one or more additional components; all based on the total dry weight of the treatment composition; wherein the substrate is carpet, concrete, brick, tile, granite, limestone, marble, grout, mortar, statuary, monument, wood, composite, terrazzo, gypsum, wall panel, metal, glass plates or glass articles, inorganic particles, polymer films or polymer articles; the silicone polyether polymer has about 40-100% by weight of repeat units from formula (I) or formula (II) and about 0-60% by weight of repeat units from ethylenically unsaturated comonomers, all based on the total weight% of the polymer;

a and b are independently integers of 1 to 40 where a+b is an integer of at least 2; c and d are independently integers of 0 to 20; e is an integer of 1 to 40; X is a linear or branched C1-C4 alkylene group; R¹ is a C1-C4 alkyl group; and R² is -C(R¹)=CH2 or polymer backbone unit - [C(R¹)-CH2]- bonded at C(R¹); provided that if c+d is 0, then the silicone polyether polymer has repeat units from at least one ethylenically unsaturated comonomer having at least one pendant alkoxylate group. [0006] The present invention further comprises a process of providing a surface effect to a substrate comprising contacting a treatment composition with a substrate, where the treatment composition comprises: a) about 20-99.5% by weight of a silicone polyether polymer; b) about 0.5- 4% by weight of at least one surfactant selected from anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants, and mixtures thereof, and c) about 0-79.5% by weight of one or more additional components; all based on the total dry weight of the treatment composition; wherein the substrate is carpet, concrete, brick, tile, granite, limestone, marble, grout, mortar, statuary, monument, wood, composite, terrazzo, gypsum, wall panel, metal, glass plate or glass article, inorganic particle, polymer film or polymer article; the silicone polyether polymer has about 40-100% by weight of repeat units from formula (I) or formula (II) as shown above and about 0-60% by weight of repeat units from ethylenically unsaturated comonomers, all based on the total weight% of the polymer; a and b are independently integers of 1 to 40 where a+b is an integer of at least 2; c and d are independently integers of 0 to 20; e is an integer of 1 to 40; X is a linear or branched C1-C4 alkylene group; R¹ is a C1-C4 alkyl group; and R² is -C(R¹)=CH2 or polymer backbone unit -[C(R¹)-CH2]- bonded at C(R¹); provided that if c+d is 0, then the silicone polyether polymer has repeat units from at least one ethylenically unsaturated comonomer having at least one pendant alkoxylate group.

DETAILED DESCRIPTION OF THE INVENTION

[0007] Features of the embodiments of the present invention as described in the Detailed Description of the Invention can be combined in any manner.

[0008] The present invention provides treated substrates having improved water repellency, oil or stain repellency, cleanability, water and/or oil contact angle, and/or other surface effects. The treatment compositions provide a balance of hydrophobic properties and oleophobic properties without the use of fluorine. The coatings formed are durable, by which is meant that the coatings are lasting films that are not readily removed by water or cleaning agents. In one aspect, the coatings are not soluble or dispersable in water or cleaning agents once they are dry, and in another aspect, the coatings withstand multiple cleanings without loss of performance.

[0009] In one aspect, the present invention relates to a treated substrate comprising a substrate and a treatment composition applied thereon, wherein the treatment composition comprises: a) about 20-99.5% by weight of a silicone polyether polymer; b) about 0.5-4% by weight of at least one surfactant selected from anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants, and mixtures thereof; and c) about 0-79.5% by weight of one or more additional components; all based on the total dry weight of the treatment composition; wherein the substrate is carpet, concrete, brick, tile, granite, limestone, marble, grout, mortar, statuary, monument, wood, composite, terrazzo, gypsum, wall panel, metal, glass plates or glass articles, inorganic particles, polymer films or polymer articles; the silicone polyether polymer has about 40-100% by weight of repeat units from formula (I) or formula (II) and about 0-60% by weight of repeat units from ethylenically unsaturated comonomers, all based on the total weight% of the polymer;

a and b are independently integers of 1 to 40 where a+b is an integer of at least 2; c and d are independently integers of 0 to 20; e is an integer of 1 to 40; X is a linear or branched C1-C4 alkylene group; R¹ is a C1-C4 alkyl group; and R² is -C(R¹)=CH2 or polymer backbone unit - [C(R¹)-CH2]- bonded at C(R¹); provided that if c+d is 0, then the silicone polyether polymer has repeat units from at least one ethylenically unsaturated comonomer having at least one pendant alkoxylate group. [0010] The term “copolymer” is intended to mean a polymeric compound having at least two different monomeric units. The term includes terpolymers and polymers having more than three different monomeric units. The -(OCH2CH2)- of formula (I) or (II) represents oxyethylene groups (EO) and -(OCH2CH(CH3))- represents oxypropylene groups (PO). These compounds can contain only EO groups, only PO groups, or mixtures thereof in random or block configuration. These compounds can also be present as a tri-block copolymer designated PEG- PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol), for example. In one embodiment, c+d is 1 to 30; in another embodiment, c+d is 1 to 15; and in a third embodiment, c+d is 1 to 12. In one aspect, when c+d is 0, the ethylenically unsaturated comonomer has 1-20 pendant alkoxylate groups; in another aspect, when c+d is 0, the ethylenically unsaturated comonomer has 2-20 pendant alkoxylate groups; an in a third aspect, when c+d is 0, the ethylenically unsaturated comonomer has 3-20 pendant alkoxylate groups.

[0011] The silicone polyether segment of the polymer may be part of a pendant endgroup of a (meth)acrylic repeat unit, such as in formula (I), or it may be a divalent linear segment between two (meth)acrylic repeat units, such as in formula (II). Polymers with repeat units of formula (I) are formed from free radical polymerization of silicone polyether (meth)acrylate compounds with or without comonomers, while repeat units of formula (II) are formed from free radical polymerization of silicone polyether di(meth)acrylate compounds with or without comonomers. The monomers to form the repeat units are found, for example, under the tradename Silmer® ACR or Silmer® MACR. The compounds have significant hydrophilic content by the incorporation of the silicone polyether monomeric unit. Such polymers may optionally include additional repeat units, such as alkyl siloxane units having alkyl groups of C-i-Ce. In formula (I), a and b may independently be integers of 1 to 40; in another aspect, a and b may independently be integers of 2 to 40, and in a third aspect, a and b may independently be integers of 3 to 40. In one aspect, b is at least 1 ; in another aspect, b is at least 2, and in a third aspect, b is at least 3. In one aspect, a+b is at least 2; in another aspect, a+b is at least 4, and in a third aspect, a+b is at least 6. In formula (II), e is an integer of 1 to 40; in another aspect, e is an integer of 2 to 40; and in a third aspect, e is an integer of 3 to 40.

[0012] The polymers of formula (II) are formed by silicone diacrylate monomers of formula (III):

where R¹, c, d, X, and e are defined as above. In formula (II), R² may either be a polymerizable unit -C(R¹)=CH2 or a polymer backbone unit -[C(R¹)-CH2]- bonded at C(R¹). The polymer backbone unit -[C(R¹)- CH2]- bonded at C(R¹) results from a polymerizable unit -C(R¹)=CH2 reacting with another polymerizable unit -C(R¹)=CH2 of a silicone diacrylate monomer.

[0013] For either formula (I) or (II), if c+d is 0, then the silicone polyether polymer has repeat units from at least one ethylenically unsaturated comonomer having at least one pendant alkoxylate group. This comonomer may be any ethylenically unsaturated compound having one or more pendant alkoxylate groups such as, but not limited to, (meth)acrylate compounds, (meth)acrylamide compounds, or vinyl compounds. For example, the ethylenically unsaturated compounds may have 1 -40 pendant alkoxylate groups; in another aspect, the ethylenically unsaturated compound has 1-20 pendant alkoxylate groups; and in another aspect, the ethylenically unsaturated compound has 1-10 pendant alkoxylate groups. Alkoxylate groups may be, for example, ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof.

[0014] The silicone polyether polymer may be a homopolymer, having 100% repeat units from formula (I) or formula (II). In another aspect, the silicone polyether polymer may be a copolymer having repeat units from formula (I) or formula (II) and repeat units from one or more comonomers. When a comonomer is used, the silicone polyether polymer may be in the form of a random copolymer, block copolymer, or other configuration of copolymer. The comonomer may be any suitable ethylenically unsaturated comonomer. For example, the comonomer may be selected from alkoxylated (meth)acrylates, hydroxyalkyl (meth)acrylates, glycidyl (meth)acrylates, cyclic hydrocarbon (meth)acrylates, linear or branched alkyl (meth)acrylates, vinylidene halide, vinyl halide, vinyl acetate, diacetone (meth)acrylamide, alkoxylated (meth)acrylamides, hydroxyalkyl (meth)acrylamides, glycidyl (meth)acrylamides, cyclic hydrocarbon (meth)acrylamides, linear or branched alkyl (meth)acrylamides, or mixtures thereof. When c+d is 0, the ethylenically unsaturated monomer having at least one pendant group may be selected from alkoxylated (meth)acrylates, hydroxyalkyl (meth)acrylates, alkoxylated (meth)acrylamides, hydroalkyl (meth)acrylamides, or mixtures thereof.

[0015] The silicone polyether polymer has about 40-100% by weight repeat units from formula (I) or formula (II) and 0-60% repeat units from ethylenically unsaturated comonomers; in another aspect, the silicone polyether polymer has about 50-100% by weight repeat units from formula (I) or formula (II) and 0-50% by weight repeat units from ethylenically unsaturated comonomers; in another aspect, the silicone polyether polymer has about 60-100% by weight repeat units from formula (I) or formula (II) and 0-40% by weight repeat units from ethylenically unsaturated comonomers; in another aspect, the silicone polyether polymer has about 70-100% by weight repeat units from formula (I) or formula (II) and 0-30% by weight repeat units from ethylenically unsaturated comonomers; in another aspect, the silicone polyether polymer has about 80-100% by weight repeat units from formula (I) or formula (II) and 0-20% by weight from ethylenically unsaturated comonomers; and in another aspect, the silicone polyether polymer has about 90-100% by weight repeat units from formula (I) or formula (II) and 0-10% by weight from ethylenically unsaturated comonomers; all based on the total weight % of the silicone polyether polymer.

[0016] In another aspect, comonomers are positively present. In one aspect, the silicone polyether polymer has about 40-99% by weight repeat units from formula (I) or formula (II) and 1-60% repeat units from ethylenically unsaturated comonomers; in another aspect, the silicone polyether polymer has about 50-99% by weight repeat units from formula (I) or formula (II) and 1-50% by weight repeat units from ethylenically unsaturated comonomers; in another aspect, the silicone polyether polymer has about 60-95% by weight repeat units from formula (I) or formula (II) and 5-40% by weight repeat units from ethylenically unsaturated comonomers; in another aspect, the silicone polyether polymer has about 70-95% by weight repeat units from formula (I) or formula (II) and 5-30% by weight repeat units from ethylenically unsaturated comonomers; in another aspect, the silicone polyether polymer has about 70-90% by weight repeat units from formula (I) or formula (II) and 10-30% by weight from ethylenically unsaturated comonomers; and in another aspect, the silicone polyether polymer has about 80-90% by weight repeat units from formula (I) or formula (II) and 10-20% by weight from ethylenically unsaturated comonomers; all based on the total weight % of the silicone polyether polymer.

[0017] In one embodiment, the silicone polyether polymer may have repeat units from more than two comonomers. For example, the silicone polyether polymer may have repeat units from formula (I) or formula (II), as well as repeat units from copolymerizing at least one hydrophilic monomer selected from alkoxylated (meth)acrylates, alkoxylated (meth)acrylamides, hydroxyalkyl (meth)acrylates, hydroxyalkyl (meth)acrylamides, glycidyl (meth)acrylates, or mixtures thereof; and at least one additional monomer selected from cyclic hydrocarbon (meth)acrylates, linear or branched alkyl (meth)acrylates, vinylidene halide, vinyl halide, vinyl acetate, diacetone (meth)acrylamide, glycidyl (meth)acrylamides, cyclic hydrocarbon (meth)acrylamides, linear or branched alkyl (meth)acrylamides, or mixtures thereof. In one aspect, the silicone polyether polymer has about 40-89% by weight repeat units from formula (I) or formula (II), about 1-20% by weight repeat units from hydrophilic monomers, and about 10-40% by weight repeat units from additional monomers cited above; in another aspect, the silicone polyether polymer has about 50-85% by weight repeat units from formula (I) or formula (II), about 5-20% by weight repeat units from hydrophilic monomers, and about 10-30% by weight repeat units from additional monomers cited above; and in a third aspect, the silicone polyether polymer has about 60-75% by weight repeat units from formula (I) or formula (II), about 10-15% by weight repeat units from hydrophilic monomers, and about 15-25% by weight repeat units from additional monomers cited above; all based on the total weight of the ethylenically unsaturated comonomers. In one embodiment, the non-fluorinated compound is soluble or dispersible in water at 1 % by weight at room temperature.

[0018] In one aspect, the silicone polyether polymer has a molecular weight M_n of at least 5,000 Da; in another aspect, the molecular weight M_n is at least 10,000 Da; and in another aspect, the molecular weight M_n is at least 20,000 Da. Molecular weight M_n and M_w can be measured by a size exclusion chromatographer using a calibration standard. For example, polymer solutions are diluted, allowed to sit at ambient temperature for 4 days, and passed through 0.2 pm syringe filter. The polymer solution is injected into a mobile phase through an AGILENT 1100 system equipped with a G1362A refractive index detector and pumped at 1 .0 mL/min for 40 min through two PSS SUPREMA columns (10,000 A, 10 pm; 1 ,000 A, 5 pm, both 8 x 300 mm) held at 30 °C.

[0019] The at least one surfactant may be any surfactant selected from anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants, and mixtures thereof. Blends of surfactants, especially blends of nonionic surfactants with ionic surfactants, may also be used. In one aspect, the treatment composition comprises a mixture of surfactants selected from an anionic surfactant mixed with nonionic surfactant, an anionic surfactant mixed with zwitterionic surfactant, a cationic surfactant mixed with nonionic surfactant, a cationic surfactant mixed with a zwitterionic surfactant.

[0020] Cationic surfactants include those used in treatment or coating applications, including but not limited to salts of protonated amines; quarternary ammonium salts; or alkyl amine oxides. Protonated amines are formed by mixing an amine compound with an acid such as hydrochloric acid or acetic acid. Amine compound examples include alkyl dimethyl amines, dialkyl methyl amines, alkyl ethoxylated amines, alkyl diamines, and their respective ethoxylates, including those compounds sold under the brand Armeen®. Quarternary amine salts are typically produced by the alkylation of amines, including those listed above.

Alkylating agents include but are not limited to methyl chloride, dimethyl sulfate, diethyl sulfate, and benzyl chloride. Specific examples include alkyl trimethyl ammonium salts; dialkyl dimethyl ammonium salts, specifically dialkyl dimethyl ammonium chloride; alkyl methyl ethoxylated ammonium; alkyl dimethyl benzyl ammonium; dialkyl methyl benzyl ammonium; alkyl, alkylamidomethyl, and carboalkoxy pyridinium (with and without ring substitution); alkyl quinolinium; alkyl isoquinolinium; N, N-alkyl methyl pyrollidinium ; amidoimidazolinium; amido ammonium; and quaternary ammonium salts of alkyl diamines and their ethoxylates. Some of these compounds are sold under the brand Arquad®. Alkyl amine oxides include compounds such as alkyl dimethyl amine oxide, dialkyl methyl amine oxide, and alkyl diamine oxide.

[0021] Thus, the cationic surfactant is typically selected from a protonated alkyl dimethyl amine salt, protonated dialkyl methyl amine salt, protonated alkyl ethoxylated amine salt, protonated alkyl diamine salt, protonated alkyl ethoxylated diamine salt, alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl methyl ethoxylated ammonium salt, alkyl dimethyl benzyl ammonium salt, dialkyl methyl benzyl ammonium salt, alkyl pyridinium salt, alkylamidomethyl pyridinium salt, carboalkoxy pyridinium salt, alkyl quinolinium salt, alkyl isoquinolinium salt, N, N-alkyl methyl pyrollidinium salt, amidoimidazolium salt, amido ammonium salt; quaternary ammonium salt of alkyl diamine; ethoxylate of quaternary ammonium salt of alkyl diamine; alkyl dimethyl amine oxide; dialkyl methylamine oxide; and alkyl diamine oxide.

[0022] Suitable anionic surfactants which are used herein include alkyl carboxylic acids and their salts, alkyl hydrogen sulfates and their salts, alkyl sulfonic acids and their salts, alkyl ethoxy sulfates and their salts, alpha olefin sulfonates, alkylamidoalkylene sulfonates, and the like. In one aspect, the alkyl groups of the surfactants have 8-18 carbon atoms; in another aspect, the alkyl groups of the surfactants have 10-14 carbon atoms. Examples include an alkyl sulfate sodium salt such as sodium lauryl sulfate, i.e. , where the alkyl group averages about 12 carbons.

[0023] Nonionic surfactants include those used in treatment applications, including but not limited to alkoxylate condensate compounds. Examples include alkoxylate condensates with fatty acid alkanol amides such as amides of fatty acids and diethanol amine; with alkyl phenols such as isooctylphenol; with a fatty acid such as a stearate; with a linear fatty alcohol; with a branched fatty alcohol; and with poly(oxypropylene) block-copolymers. Zwitterionic surfactants include but are not limited to lecithin, amino acid compounds, betaine compounds, imidazoline compounds, or phospholipids.

[0024] In one aspect, the treatment composition comprises about 20- 99.5% by weight of the silicone polyether polymer; in a second aspect, about 40-99.5% by weight of the silicone polyether polymer; and in a third aspect, about 50-99.5% by weight of the silicone polyether polymer, all based on the total dry weight of the treatment composition. In one aspect, the treatment composition comprises about 0.5-4% by weight of at least one surfactant as defined above; in another aspect, about 0.5-3.5% by weight of the surfactant; and in a third aspect, about 0.5-3% by weight of the surfactant, all based on the total dry weight of the treatment composition. The coating composition may also contain a liquid carrier that is not present once the coating is dry or solid, such as water or organic solvent. In one aspect, the liquid carrier is water. Additional components present in the coating composition that make up the balance of the total dry weight of the treatment composition may include but are not limited to surface effect agents; pigments such as dyes or TiC ; surfactants; curing agents; pH adjustors; or wetting agents. The term “total dry weight of the coating” is used to mean the sum of the coating components that would remain once the aqueous, solvent, or other liquid components evaporated. In other words, it is the sum of the non-aqueous, non-solvent, and nonvolatile components of the coating.

[0025] The coating composition may further comprise a hydrophobic surface effect agent, which may be fluorinated or non-fluorinated. For example, the coating composition may further comprise a fatty acid ester of cyclic or acyclic polyols, fatty esters of polycarboxylic acids, hydrophobic non-fluorinated (meth)acrylic polymers, partially fluorinated urethanes, hydrophobic non-fluorinated urethanes, partially fluorinated (meth)acrylic polymers or copolymers, partially fluorinated (meth)acrylamide polymers or copolymers, fluorinated phosphates, fluorinated ethoxylates, fluorinated or non-fluorinated organosilanes, silicones, waxes, including parafins, and mixtures thereof. In one embodiment, the treatment composition is non-fluorinated. In another aspect, a fluorinated hydrophobic surface effect agent is used to supplement the silicone polyether polymer. In one aspect, the amount of silicone polyether polymer is greater than the amount of hydrophobic surface effect agent.

[0026] In one embodiment, the treatment composition comprises a) about 20-95% by weight of a silicone polyether polymer, b) about 0.5-4% by weight of at least one surfactant, and c) about 1 -79.5% by weight of a hydrophobic surface effect agent, all based on the total dry weight of the treatment composition. In another embodiment, the treatment composition comprises a) about 20-86% by weight of a silicone polyether polymer, b) about 0.5-4% by weight of at least one surfactant, and c) about 10-79.5% by weight of a hydrophobic surface effect agent, all based on the total dry weight of the treatment composition; and in a third embodiment, the treatment composition comprises a) about 39.5-86% by weight of a silicone polyether polymer, b) about 0.5-4% by weight of at least one surfactant, and c) about 10-60% by weight of a hydrophobic surface effect agent, all based on the total dry weight of the treatment composition. Hydrophobic surface effect agents provide surface effects such as moisture control, strength, anti-slip, anti-static, anti-snag, anti-pill, stain repellency, stain release, soil repellency, soil release, water repellency, oil repellency, odor control, antimicrobial, sun protection, anti-blocking, cleanability, dust resistance, leveling, corrosion resistance, acid resistance, anti-fog, or anti-ice, and similar effects. Some stain release and soil release agents are hydrophilic and include compounds such as polymethyl acrylates or hydrophilic urethanes.

[0027] Superior properties, along with desirable properties of low yellowing and good durability, are imparted to articles by the combination of the silicone polether polymers with hydrophobic surface effect agents before application to the articles. These combined blends are applied to the articles in the form of a dispersion in water or other solvent either before, after or during the application of other treatment chemicals. In one aspect, the treatment composition is in the form of an aqueous emulsion of the silicone polyether polymer.

[0028] Suitable fatty acid esters of cyclic or acyclic polyols include reaction products of fatty acids with cyclic or acyclic sugar alcohols, or pentaerythritols including dipentaerythritol, which may also contain internal alkoxide units. Fatty esters of polycarobyxlic acids include reaction products of long-chain alkanols with polycarboxylic acids. Examples of polyols and polycarboxylic acids include but are not limited to glucose, 1 ,4- anhydro-D-glucitol, 2,5-anhydro-D-mannitol, 2,5-anhydro-L-iditol, isosorbide, sorbitan, glyceraldehyde, erythrose, arabinose, ribose, arabinose, allose, altrose, mannose, xylose, lyxose, gulose, glactose, talose, fructose, ribulose, mannoheptulose, sedohelptulose, threose, erythritol, threitol, glucopyranose, mannopyranose, talopyranose, allopyranose, altropyranose, idopyranose, gulopyranose, glucitol, mannitol, erythritol, sorbitol, arabitol, xylitol, ribitol, galactitol, fucitol, iditol, inositol, pentaerythritol, dipentaerythritol, volemitol, gluconic acid, glyceric acid, xylonic acid, galactaric acid, ascorbic acid, citric acid, gluconic acid lactone, glyceric acid lactone, xylonic acid lactone, glucosamine, galactosamine, or mixtures thereof. Suitable fatty acids include, but are not limited to, caprylic acid, capric acid, lauric acid, mysteric acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, palmitoleic acid, lineolic acid, oleic acid, erucic acid, alkoxylated versions of these acids, and mixtures thereof. In one embodiment, the fatty acid esters or fatty esters contain linear or branched alkyl groups having 11 to 29 carbons, and in another embodiment, the contain linear or branched alkyl groups having 17 to 21 carbons. Particular examples include monosubstituted, di-substituted, or tri-substituted sorbitans, such as SPAN, sorbitan stearates, or sorbitan behenins; mono-, di-, and tri-substituted sorbitans derived from palmitoleic acid, lineolic acid, arachidonic acid, and erucic acid; polysorbates such as polysorbate tristearate and polysorbate monostearate; citrates that are mono-substituted, di-substituted, or tri- substituted with alkyl groups; pentaerythriol esters that are monosubstituted, di-substituted, or tri-substituted with alkyl groups.

[0029] Other useful hydrophobic surface effect agents include fluorinated polymers that provide repellency properties to the surface of treated substrates. These include fluorochemical compounds or polymers containing one or more fluoroaliphatic groups (designated here as Rf groups) which are fluorinated, stable, inert, and non-polar, preferably saturated, monovalent, and both oleophobic and hydrophobic. The Rf groups contain at least 3 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably about 4 to about 6 carbon atoms. The Rf groups may contain straight or branched chain or cyclic fluorinated alkylene groups or combinations thereof. The terminal portion of the Rf groups is preferably a perfluorinated aliphatic group of the formula C_nF2n+i wherein n is from about 3 to about 20. Examples of fluorinated polymer treating agents are CAPSTONE and ZONYL available from The Chemours Company, Wilmington, DE; ASAHI GARD from Asahi Glass Company, Ltd., Tokyo, Japan; UNIDYNE from Daikin America, Inc., Orangeburg, NY; SCOTCHGARD from 3M Company, St. Paul, MN; and NANO TEX from Nanotex, Emeryville, CA. [0030] Examples of such fluorinated polymers include Rf-containing polyurethanes and poly(meth)acrylates. Especially preferred are copolymers of fluorochemical (meth)acrylate monomers with a co- polymerizable monovinyl compound or a conjugated diene. The co- polymerizable monovinyl compounds include alkyl (meth)acrylates, vinyl esters of aliphatic acids, styrene and alkyl styrene, vinyl halides, vinylidene halides, alkyl esters, vinyl alkyl ketones, and acrylamides. The conjugated dienes are preferably 1 ,3-butadienes. Representative compounds within the preceding classes include the methyl, propyl, butyl, 2-hydroxypropyl, 2-hydroxyethyl, isoamyl, 2-ethylhexyl, octyl, decyl, lauryl, cetyl, and octadecyl acrylates and methacrylates; vinyl acetate, vinyl propionate, vinyl caprylate, vinyl laurate, vinyl stearate, styrene, alpha methyl styrene, p-methylstyene, vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride, vinylidene chloride, allyl heptanoate, allyl acetate, allyl caprylate, allyl caproate, vinyl methyl ketone, vinyl ethyl ketone, 1 ,3-butadiene, 2- chloro-1 ,3-butadiene, 2, 3-dichloro-1 ,3-butadiene, isoprene, N- methylolacrylamide, N-methylolmethacrylamide, glycidyl acrylate, glycidyl methacrylate, amine-terminated (meth)acrylates, and polyoxy(meth)acrylates.

[0031] Hydrophobic non-fluorinated acrylic polymers include copolymers of monovinyl compounds, including alkyl (meth)acrylates, vinyl esters of aliphatic acids, styrene and alkyl styrene, vinyl halides, vinylidene halides, alkyl esters, vinyl alkyl ketones, and acrylamides. The conjugated dienes are preferably 1 ,3-butadienes. Representative compounds within the preceding classes include the methyl, propyl, butyl, 2-hydroxypropyl, 2-hydroxyethyl, isoamyl, 2-ethylhexyl, octyl, decyl, lauryl, cetyl, and octadecyl acrylates and methacrylates; vinyl acetate, vinyl propionate, vinyl caprylate, vinyl laurate, vinyl stearate, styrene, alpha methyl styrene, p-methylstyene, vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride, vinylidene chloride, allyl heptanoate, allyl acetate, allyl caprylate, allyl caproate, vinyl methyl ketone, vinyl ethyl ketone, 1 ,3-butadiene, 2- chloro-1 ,3-butadiene, 2, 3-dichloro-1 ,3-butadiene, isoprene, N- methylolacrylamide, N-methylolmethacrylamide, glycidyl acrylate, glycidyl methacrylate, amine-terminated (meth)acrylates, and polyoxy(meth)acrylates.

[0032] Hydrophobic non-fluorinated urethanes include, for example, urethanes synthesized by reacting an isocyanate compound with the hydrophobic compounds described above as an alcohol reagent. These compounds are described in US 10,138,392 and US 10,246,608. Hydrophobic non-fluorinated nonionic acrylic polymers include, for example, polymers made by polymerizing or copolymerizing an acrylic ester of the hydrophobic compounds described above. Such compounds are described in US 9,915,025.

[0033] The silicone polyether polymer is generally formed by reacting the silicone polyether monomer along with optional comonomers and surfactant in water. The monomers and surfactant are emulsified using a blender, homogenizer, or other sheer mechanism. The contents are then heated and reacted in the absence of oxygen using a peroxide or other free radical initiator. In one aspect, the reaction silicone polyether polymer is formed in an aqueous reaction medium; in another aspect, the reaction medium contains less than 5% by weight of an organic solvent; in another aspect, the reaction medium contains less than 1% by weight of an organic solvent; and in another aspect, the reaction medium contains no organic solvent; all based on the total weight of the reaction contents. In another aspect, the silicone polyether polymer, surfactant, and optional surface effect agents may be effectively mixed to form the treatment composition by thoroughly stirring it in at room or ambient temperature. More elaborate mixing can be employed such as using a mechanical shaker or providing heat or other methods.

[0034] The coating composition of the present invention optionally further comprises additional components such as additional treating agents or finishes to achieve additional surface effects, or additives commonly used with such agents or finishes. One or more such treating agents or finishes can be combined with the blended composition and applied to the article. Other additives commonly used with such treating agents or finishes may also be present such as surfactants, pH adjusters, cross linkers, wetting agents, and other additives known by those skilled in the art. Further, other extender compositions are optionally included to obtain a combination of benefits.

[0035] In one aspect, the invention relates to a process of providing a surface effect to a substrate comprising contacting a treatment composition with a fibrous substrate, wherein the treatment composition comprises a) about 20-99.5% by weight of a silicone polyether polymer, and b) about 0.5-4% by weight of at least one surfactant selected from at least one cationic surfactant or a mixture of at least one cationic and at least one nonionic surfactant all based on the total dry weight of the treatment composition; wherein the silicone polyether polymer has about 6 to about 100% by weight of repeat units from formula (I) or formula (II) as shown above and about 0% to about 94% by weight of repeat units from ethylenically unsaturated comonomers, all based on the total weight of the polymer; wherein a and b are independently integers of 1 to 40 where a+b is an integer of at least 2; c and d are independently integers of 0 to 20; e is an integer of 1 to 40; X is a linear or branched C1-C4 alkylene group; R¹ is a C1-C4 alkyl group; and R² is -C(R¹)=CH2 or polymer backbone unit - [C(R¹)-CH2]- bonded at C(R¹); provided that if c+d is 0, then the silicone polyether polymer has repeat units from at least one ethylenically unsaturated comonomer having at least one pendant alkoxylate group. This embodiment may be combined with one or more of the previously described embodiments.

[0036] The substrate may be any surface selected from carpet, concrete, brick, tile, granite, limestone, marble, grout, mortar, statuary, monument, wood, composite, terrazzo, gypsum, wall panel, metal, glass plates or glass articles, inorganic particles, polymer films or polymer articles. The treatment composition is applied to the surface of the substrate or article to provide increased balance of water and oil repellency. The contacting step may occur by applying the treatment composition in the form of a solid, an aqueous solution, aqueous dispersion, organic solvent solution or dispersion, or cosolvent solution or dispersion. The contacting step may occur by any conventional method, including but not limited to exhaustion, foam, flex-nip, nip, pad, kiss-roll, beck, skein, winch, liquid injection, overflow flood, brush, spraying, rolling, dip-squeeze, brushing, sprinkling, dripping, immersing, powder coating, tumbling, or screen printing.

[0037] In one aspect, the substrate is a porous hard surface, such as unglazed concrete, grout, stone, granite, limestone, brick, tile, marble, grout, terrazzo, gypsum board, wall or ceiling panel, mortar, statuary, monument, wood, or composite material. In this case, the treatment composition may penetrate the pores of the substrate as well as cover the top surface of the substrate. In another aspect, the substrate is a non- porous hard surface, such as metal, glass plates, glass articles, or inorganic particles. In another aspect, the substrate is a polymer film or polymer article. The metal, glass, or polymeric surfaces may be in the form of a flexible or inflexible film, solid plate, or finished article, such as a three-dimensional article. Such three-dimensional articles may be formed by any method, including but not limited to extrusion molding, blow molding, pouring the molten material into a mold, or mechanically bending a film or plate into a three-dimensional shape. When the substrate is an inorganic particle, it may be any inorganic particle including but not limited to inorganic oxide particles, such as titanium dioxide, silica, glass beads, alumina, or clay particles.

[0038] In one aspect, the substrate is a carpet. In this case, the treatment composition may be applied to the finished carpet surface during manufacture or in a home or industrial environment. The treatment may form a barrier at the pile surface to provide a balance of oil and water repellency. The carpet may be any material, for example, it may be made of natural fibers, nylon, acrylics, aromatic polyamides, polyesters, polyacrylonitrile, or polyacrylonitrile copolymers. Specific representative examples of carpet compositions include but are not limited to natural fibers, such as cotton, wool, silk, jute, sisal, and other cellulosics; nylon including nylon 6, nylon 6,6 and aromatic polyamides; polyesters including poly(ethyleneterephthalate) or poly(trimethyleneterephthalate) such as Triexta; polyacrylonitrile or polyacrylonitrile copolymers. The contacting step may occur by applying the hydrophobic compound as a solid, or by liquid carrier. When applied by liquid carrier, the hydrophobic compound may be in the form of an aqueous solution, aqueous dispersion, organic solvent solution or dispersion, or cosolvent solution or dispersion.

[0039] The treatment compositions of the present invention optionally further comprise a blocked isocyanate to promote durability, added after copolymerization (i.e., as a blended isocyanate). An example of a suitable blocked isocyanate is PHOBOL XAN available from Huntsman Corp, Salt Lake City, UT. Other commercially available blocked isocyanates are also suitable for use herein. The desirability of adding a blocked isocyanate depends on the particular application for the copolymer. For most of the presently envisioned applications, it does not need to be present to achieve satisfactory cross-linking between chains or bonding to fibers. When added as a blended isocyanate, amounts up to about 20% by weight of the total composition are added.

[0040] In one aspect, the method further comprises the step of heating the partially or completely coated article. For example, the treatment composition may be applied, and the treated article may be heated to melt, flow, dry, or otherwise fix the hydrophobic agent onto the article surface. In another aspect, the method further comprises the step of subjecting the coating composition to UV radiation. The final coating on the article surface will be a solidified, lasting, permanent coating. In another aspect, the method further comprises the step of solidifying the coating by drying, cooling, or allowing to cool. The liquid carrier may be dried by heating or air drying to allow for evaporation of the liquid carrier, thus leaving a permanent solid coating.

EXAMPLES

[0041] All solvents and reagents, unless otherwise indicated, were purchased from Sigma-Aldrich, St. Louis, MO, and used directly as supplied. [0042] Vazo™ 56 is a free radical initiators; Zelan™ R3 is a durable water repellent agent; all available from The Chemours Company, Wilmington, DE.

[0043] Armeen® DM-18D is a dimethyl stearamine cationic surfactant commercially available from Nouryon, Chicago, IL.

[0044] PHOBOL® XAN is a repellency extender having a solids content of 28% available from Huntsman Corp, Salt Lake City, UT.

[0045] Silmer® MACR D212-CG is a multifunctional methacrylate silicone polyether; Silmer® MACR D208 is a multifunctional methacrylate silicone polyether; all commercially available from Siltech, Toronto, Canada.

[0046] The following test methods and materials were used in the examples herein.

Test Method - Water Contact Angle

[0047] Water contact angle measurements are used to test for the migration of additive to the surface of the compression molded sheet samples. Testing is performed by a Rame-Hart Standard Automated Goniometer Model 200 employing DROPimage standard software and equipped with an automated dispensing system, 250 pl syringe, and illuminated specimen stage assembly is used. The goniometer camera is connected through an interface to a computer, allowing the droplet to be visualized on a computer screen. The horizontal axis line and the cross line can both be independently adjusted on the computer screen using the software.

[0048] Prior to contact angle measurement, the sample is placed on the sample stage and the vertical vernier is adjusted to align the horizontal line (axis) of the eye piece coincident to the horizontal plane of the sample. The horizontal position of the stage relative to the eye piece is positioned so as to view one side of the test fluid droplet interface region at the sample interface.

[0049] To determine the contact angle of the test fluid on the sample, one drop (5 pL) of test fluid is dispensed onto the sample using a 30 pL pipette tip and an automated dispensing system to displace a calibrated amount of the test fluid. Deionized water is used for water contact angle measurements. Horizontal and cross lines are adjusted via the software in case of the Model 200 after leveling the sample via stage adjustment, and the computer calculates the contact angle based upon modeling the drop appearance. The initial contact angle is the angle determined immediately after dispensing the test fluid to the sample surface. Initial contact angles above 30 degrees are indicators of effective oil repellency.

Comparative Example A

[0050] A glass slide having no treatment was tested for water contact angle according to the Test Method above.

Examples 1-2

[0051] In a vessel, Silmer® MACR D208 (10.99% by weight), 7EO MA (1.21 % by weight), hydroxyethyl methacrylate (1.10% by weight), IBOMA (3.05% by weight), Armeen® DM18D (0.57% by weight), glacial acetic acid (0.46% by weight) and deionized water (81.73% by weight) were weighed. The contents were blended for 2 minutes on setting 3 in a blender. The mixture was added to a reactor, sparged with nitrogen, and heated to 55 °C. Under a nitrogen blanket, initiator (Vazo™ 56, 0.04% by weight of total mixture in 0.86% by weight water) was added. The composition was mixed at 70 °C for 4 hours. The resulting polymer emulsions were applied onto glass and tested according to the Test Method above. In Example 2, 0.4 g of PHOBOL® XAN was added to 10 g of the polymer emulsion before applying onto glass.

Example 3

[0052] In a vessel, Silmer® MACR D212-CG (13.08% by weight), hydroxyethyl methacrylate (3.27% by weight), Armeen® DM18D (0.57% by weight), glacial acetic acid (0.46% by weight) and deionized water (81 .73% by weight) were weighed. The contents were blended for 2 minutes on setting 3 in a blender. The mixture was added to a reactor, sparged with nitrogen, and heated to 55 °C. Under a nitrogen blanket, initiator (Vazo™ 56, 0.03% by weight of total mixture in 0.86% by weight water) was added. The composition was mixed at 70 °C for 4 hours. The resulting polymer emulsion was applied onto glass and tested according to the Test Method above. Examples 4-7

[0053] The components were blended according to the table below. The % by weight of each component was based on the solids content of that component. The blended product was then diluted to 20% solids. In Examples 5 and 7, 0.4 g of PHOBOL® XAN was added to 10 g of the component blend before applying onto glass.

Table 1. Composition of Examples 4-7

Table 2. Water Contact Angle on Glass

Claims

What is claimed is:

1 . A treated substrate comprising a substrate and a treatment composition applied thereon, wherein the treatment composition comprises: a) about 20-99.5% by weight of a silicone polyether polymer; b) about 0.5-4% by weight of at least one surfactant selected from anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants, and mixtures thereof; and c) about 0-79.5% by weight of one or more additional components; all based on the total dry weight of the treatment composition; wherein the substrate is carpet, concrete, brick, tile, granite, limestone, marble, grout, mortar, statuary, monument, wood, composite, terrazzo, gypsum, wall panel, metal, glass plates or glass articles, inorganic particles, polymer films or polymer articles; the silicone polyether polymer has about 40-100% by weight of repeat units from formula (I) or formula (II) and about 0-60% by weight of repeat units from ethylenically unsaturated comonomers, all based on the total weight% of the polymer;

a and b are independently integers of 1 to 40 where a+b is an integer of at least 2; c and d are independently integers of 0 to 20; e is an integer of 1 to 40;

X is a linear or branched C1-C4 alkylene group;

R¹ is a C1-C4 alkyl group; and

R² is -C(R¹)=CH2 or polymer backbone unit -[C(R¹)-CH2]- bonded at C(R¹); provided that if c+d is 0, then the silicone polyether polymer has repeat units from at least one ethylenically unsaturated comonomer having at least one pendant alkoxylate group.

2. The treated substrate of claim 1 , where the silicone polyether polymer has about 100% repeat units from formula (I) or formula (II).

3. The treated substrate of claim 1 , where the silicone polyether polymer has about 40-99% repeat units from formula (I) or formula (II) and about 1-60% repeat units from copolymerizing monomers selected from alkoxylated (meth)acrylates, alkoxylated (meth)acrylamides, hydroxyalkyl (meth)acrylates, hydroxyalkyl (meth)acrylamides, glycidyl (meth)acrylates, cyclic hydrocarbon (meth)acrylates, linear or branched alkyl (meth)acrylates, vinylidene halide, vinyl halide, vinyl acetate, diacetone (meth)acrylamide, glycidyl (meth)acrylamides, cyclic hydrocarbon (meth)acrylamides, linear or branched alkyl (meth)acrylamides, or mixtures thereof.

4. The treated substrate of claim 3, where the silicone polyether polymer has repeat units from copolymerizing: at least one monomer selected from alkoxylated (meth)acrylates, alkoxylated (meth)acrylamides, hydroxyalkyl (meth)acrylates, hydroxyalkyl (meth)acrylamides, glycidyl (meth)acrylates, or mixtures thereof; and at least one additional monomer selected from cyclic hydrocarbon (meth)acrylates, linear or branched alkyl (meth)acrylates, vinylidene halide, vinyl halide, vinyl acetate, diacetone (meth)acrylamide, glycidyl (meth)acrylamides, cyclic hydrocarbon (meth)acrylamides, linear or branched alkyl (meth)acrylamides, or mixtures thereof.

5. The treated substrate of claim 1 , wherein the treatment composition comprises a) about 20-95% by weight of a silicone polyether polymer, b) about 0.5-4% by weight of at least one surfactant, and c) about 1-79.5% by weight of a hydrophobic surface effect agent, all based on the total dry weight of the treatment composition.

6. The treated substrate of claim 5, where the hydrophobic surface effect agent is selected from the group consisting of fatty acid ester of cyclic or acyclic polyols, fatty esters of polycarboxylic acids, hydrophobic non-fluorinated (meth)acrylic polymers, partially fluorinated urethanes, hydrophobic non-fluorinated urethanes, partially fluorinated (meth)acrylic polymers or copolymers, partially fluorinated (meth)acrylamide polymers or copolymers, fluorinated phosphates, fluorinated ethoxylates, fluorinated or non-fluorinated organosilanes, silicones, waxes, including parafins, and mixtures thereof.

7. The treated substrate of claim 1 , where the treatment composition is non-fluorinated.

8. The treated substrate of claim 1 , where the treatment composition comprises a mixture of surfactants selected from an anionic surfactant mixed with nonionic surfactant, an anionic surfactant mixed with zwitterionic surfactant, a cationic surfactant mixed with nonionic surfactant, a cationic surfactant mixed with a zwitterionic surfactant.

9. A process of providing a surface effect to a substrate comprising contacting a treatment composition with a substrate, where the treatment composition comprises: a) about 20-99.5% by weight of a silicone polyether polymer; b) about 0.5-4% by weight of at least one surfactant selected from anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants, and mixtures thereof; and c) about 0-79.5% by weight of one or more additional components; all based on the total dry weight of the treatment composition; wherein the substrate is carpet, concrete, brick, tile, granite, limestone, marble, grout, mortar, statuary, monument, wood, composite, terrazzo, gypsum, wall panel, metal, glass plate or glass article, inorganic particle, polymer film or polymer article; the silicone polyether polymer has about 40-100% by weight of repeat units from formula (I) or formula (II) and about 0-60% by weight of repeat units from ethylenically unsaturated comonomers, all based on the total weight% of the polymer;

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X is a linear or branched C1-C4 alkylene group;

R¹ is a C1-C4 alkyl group; and

10. The process of claim 9, where the silicone polyether polymer has about 100% repeat units from formula (I) or formula (II).

27

11 . The process of claim 9, where the silicone polyether polymer has repeat units from copolymerizing: at least one monomer selected from alkoxylated (meth)acrylates, alkoxylated (meth)acrylamides, hydroxyalkyl (meth)acrylates, hydroxyalkyl (meth)acrylamides, glycidyl (meth)acrylates, or mixtures thereof; and at least one additional monomer selected from cyclic hydrocarbon (meth)acrylates, linear or branched alkyl (meth)acrylates, vinylidene halide, vinyl halide, vinyl acetate, diacetone (meth)acrylamide, glycidyl (meth)acrylamides, cyclic hydrocarbon (meth)acrylamides, linear or branched alkyl (meth)acrylamides, or mixtures thereof.

12. The process of claim 9, wherein the treatment composition comprises a) about 20-95% by weight of a silicone polyether polymer, b) about 0.5-4% by weight of at least one surfactant, and c) about 1-79.5% by weight of a hydrophobic surface effect agent, all based on the total dry weight of the treatment composition.

13. The process of claim 12, where the hydrophobic surface effect agent is selected from the group consisting of fatty acid esters of cyclic or acyclic polyols, fatty esters of polycarboxylic acids, hydrophobic non-fluorinated (meth)acrylic polymers, partially fluorinated urethanes, hydrophobic non-fluorinated urethanes, partially fluorinated (meth)acrylic polymers or copolymers, partially fluorinated (meth)acrylamide polymers or copolymers, fluorinated phosphates, fluorinated ethoxylates, fluorinated or non-fluorinated organosilanes, silicones, waxes, including parafins, and mixtures thereof.

14. The process of claim 9, where the silicone polyether polymer has about 40-99% repeat units from formula (I) or formula (II) and about 1- 60% repeat units from copolymerizing monomers selected from alkoxylated (meth)acrylates, alkoxylated (meth)acrylamides, hydroxyalkyl (meth)acrylates, hydroxyalkyl (meth)acrylamides, glycidyl (meth)acrylates,

28 cyclic hydrocarbon (meth)acrylates, linear or branched alkyl (meth)acrylates, vinylidene halide, vinyl halide, vinyl acetate, diacetone (meth)acrylamide, glycidyl (meth)acrylamides, cyclic hydrocarbon (meth)acrylamides, linear or branched alkyl (meth)acrylamides, or mixtures thereof.

15. The process of claim 9, where the treatment composition is an aqueous emulsion of the silicone polyether polymer.

16. The process of claim 9, where the contacting step occurs by exhaustion, foam, flex-nip, nip, pad, kiss-roll, beck, skein, winch, liquid injection, overflow flood, brush, spraying, rolling, dip-squeeze, brushing, sprinkling, dripping, immersing, powder coating, tumbling, or screen printing.

18. The process of claim 9, where the surface effect is no iron, easy to iron, shrinkage control, wrinkle free, permanent press, moisture control, softness, strength, anti-slip, anti-static, anti-snag, anti-pill, stain release, soil repellency, soil release, water repellency, odor control, antimicrobial, sun protection, or cleanability.

19. The process of claim 9, where the treatment composition comprises a mixture of surfactants selected from an anionic surfactant mixed with nonionic surfactant, an anionic surfactant mixed with zwitterionic surfactant, a cationic surfactant mixed with nonionic surfactant, a cationic surfactant mixed with a zwitterionic surfactant.

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