Silicone Polyether Polymer Treatments for Textile Substrates

Abstract

A textile substrate treatment composition is provided, comprising: a) 20 to 99.5 wt. % of a silicone polyether polymer; and b) 0.5 to 4 wt. % of a cationic surfactant or a mixture of a cationic surfactant and a nonionic surfactant, wherein the silicone polyether polymer has 6 to 100 wt. % of repeat units derived from formula (I) or (II) and 0 to 94 wt. % of an ethylenically unsaturated comonomer; [Formula 1] TIFF2023541036000022.tif123145In the formula, a and b are integers of 1 to 40, 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 to C4 alkylene group, and R 1 is a C1-C4 alkyl group, and R 2 is C(R 1 )=CH2 or C(R 1 ) linked polymer backbone units -[C(R 1 )-CH2]-. The treatment exhibits an improved balance of water repellency and oily stain removal performance.

Description

[Technical Field]

[0001] Silicone polyether polymer compositions are used as coatings or finishes to impart surface effects to fibrous substrates. [Background technology]

[0002] Various compositions are known to be useful as treatments for providing water repellency and, optionally, stain release properties to fabric substrates. Many such treatments are fluorinated or non-fluorinated polymers and copolymers. The non-fluorinated compounds are primarily polyacrylate- or urethane-based 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 containing primarily 8 or more carbons in the perfluoroalkyl chain to provide desired properties. Honda, et al., in Macromolecules, 2005, 38, 5699-5705, state that perfluoroalkyl chains of more than 8 carbons have R f It teaches that the orientation of perfluoroalkyl groups, called groups, is maintained in a parallel configuration, while reorientation occurs in chains with six or fewer carbons. This reorientation is said to reduce surface properties such as contact angle. Therefore, compounds with short perfluoroalkyl chains or no fluorine content have previously shown poor performance. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Honda,et al.Macromolecules,2005,38,5699-5705 Summary of the Invention [Means for solving the problem]

[0005] There is a need for compositions that provide surface benefits to fibrous substrates that balance water repellency performance with oily soil release properties. The present invention meets these needs.

[0006] The present invention relates to a treated substrate comprising a fibrous substrate and a treatment composition applied onto the fibrous substrate, the treatment composition comprising: a) about 20 to 99.5 wt. % of a silicone polyether polymer; and b) about 0.5 to 4 wt. % of at least one surfactant selected from at least one cationic surfactant or a mixture of at least one cationic surfactant and at least one nonionic surfactant, all based on the total dry weight of the treatment composition; the silicone polyether polymer having from about 6 to about 100 wt. % of repeat units derived from Formula (I) or Formula (II) and from about 0% to about 94 wt. % of repeat units derived from an ethylenically unsaturated comonomer, all based on the total weight of the polymer;

[0007] [ka] In the formula, a and b are independently integers of 1 to 40, 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 to C4 alkylene group, and R 1 is a C1-C4 alkyl group, and R 2 is C(R 1 )=CH2 or C(R 1 ) linked polymer backbone units -[C(R 1 )—CH2]—, with the proviso that when c+d is 0, the silicone polyether polymer has repeat units derived from at least one ethylenically unsaturated comonomer having at least one pendant alkoxylate group.

[0008] The present invention further includes a process for providing a surface benefit to a fibrous substrate, comprising contacting the substrate with a treatment composition, the treatment composition comprising: a) about 20 to 99.5 wt. % of a silicone polyether polymer; and b) about 0.5 to 4 wt. % of at least one surfactant selected from at least one cationic surfactant or a mixture of at least one cationic surfactant and at least one nonionic surfactant, all based on the total dry weight of the treatment composition, the silicone polyether polymer having from about 6 to about 100 wt. % of repeating units derived from Formula (I) or Formula (II) as set forth above, and from about 0% to about 94 wt. % of repeating units derived from an ethylenically unsaturated comonomer, all based on the total weight of the polymer, wherein a and b are independently integers from 1 to 40, a + b is an integer of at least 2, c and d are independently integers from 0 to 20, e is an integer from 1 to 40, X is a linear or branched C1 to C4 alkylene group, and R 1 is a C1-C4 alkyl group, and R 2 is -C(R 1 )=CH2 or C(R 1 ) linked polymer backbone units -[C(R 1 )—CH2]—, with the proviso that when c+d is 0, the silicone polyether polymer has repeat units derived from at least one ethylenically unsaturated comonomer having at least one pendant alkoxylate group. DETAILED DESCRIPTION OF THE INVENTION

[0009] The features of the embodiments of the invention described in the Detailed Description may be combined in any way.

[0010] The present invention provides treated textile substrates with improved water, oil or stain repellency, cleanability, and / or other surface benefits. The treatment composition provides a balance of hydrophobic and oleophobic properties without the use of fluorine. The coating formed is durable, i.e., the coating is a persistent film that is not easily removed by water or cleaning agents. In one aspect, the coating is insoluble or indispersible in water or cleaning agents once dry, and in another aspect, the coating remains durable even after multiple washes without loss of performance.

[0011] In one aspect, the invention relates to a treated substrate comprising a fibrous substrate and a treatment composition applied onto the fibrous substrate, the treatment composition comprising: a) about 20 to 99.5 wt. % of a silicone polyether polymer; and b) about 0.5 to 4 wt. % of at least one surfactant selected from at least one cationic surfactant or a mixture of at least one cationic surfactant and at least one nonionic surfactant, all based on the total dry weight of the treatment composition; wherein the silicone polyether polymer has from about 6 to about 100 wt. % of repeat units derived from Formula (I) or Formula (II) and from about 0% to about 94 wt. % of repeat units derived from an ethylenically unsaturated comonomer, all based on the total weight of the polymer;

[0012] [ka] In the formula, a and b are independently integers of 1 to 40, 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 to C4 alkylene group, and R 1 is a C1-C4 alkyl group, and R 2 is C(R 1 )=CH2 or C(R 1 ) linked polymer backbone units -[C(R 1)—CH2]—, with the proviso that when c+d is 0, the silicone polyether polymer has repeat units derived from at least one ethylenically unsaturated comonomer having at least one pendant alkoxylate group.

[0013] The term "copolymer" is intended to mean a polymeric compound having at least two different monomer units. The term includes terpolymers and polymers having four or more different monomer units. In formula (I) or (II), -(OCHCH)- represents an oxyethylene group (EO), and -(OCHCH(CH))- represents an oxypropylene group (PO). These compounds can contain only EO groups, only PO groups, or mixtures thereof in a random or block configuration. These compounds can also exist as triblock copolymers, designated, for example, as PEG-PPG-PEG (polyethylene glycol-polypropylene glycol-polyethylene glycol). 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 embodiment, when c+d is 0, the ethylenically unsaturated comonomer has 1 to 20 pendant alkoxylate groups; in another embodiment, when c+d is 0, the ethylenically unsaturated comonomer has 2 to 20 pendant alkoxylate groups; and in a third embodiment, when c+d is 0, the ethylenically unsaturated comonomer has 3 to 20 pendant alkoxylate groups.

[0014] The silicone polyether segment of the polymer may be part of a pendant end group of a (meth)acrylic repeating unit, such as formula (I), or may be a divalent linear segment between two (meth)acrylic repeating units, such as formula (II). Polymers having repeating units of formula (I) are formed from free radical polymerization of silicone polyether (meth)acrylate compounds, with or without comonomers, while repeating units of formula (II) are formed from free radical polymerization of silicone polyether di(meth)acrylate compounds, with or without comonomers. Monomers forming the repeating units are found, for example, under the trade names Silmer® ACR or Silmer® MACR. The compounds have significant hydrophilic content due to the incorporation of silicone polyether monomer units. Such polymers may optionally contain additional repeating units, such as alkylsiloxane units having C1-C6 alkyl groups. In formula (I), a and b may independently be integers from 1 to 40; in another embodiment, a and b may independently be integers from 2 to 40; and in a third embodiment, a and b may independently be integers from 3 to 40. In one embodiment, b is at least 1; in another embodiment, b is at least 2; and in a third embodiment, b is at least 3. In one embodiment, a+b is at least 2; in another embodiment, a+b is at least 4; and in a third embodiment, a+b is at least 6. In formula (II), e is an integer from 1 to 40; in another embodiment, e is an integer from 2 to 40; and in a third embodiment, e is an integer from 3 to 40.

[0015] The polymer of formula (II) is formed by a silicone diacrylate monomer of formula (III):

[0016] [ka] In the formula, R 1 , c, d, X, and e are defined as above. 2 is the polymerizable unit -C(R 1 )=CH2 or C(R 1) linked polymer backbone units -[C(R 1 )-CH2]-. C(R 1 ) linked polymer backbone units -[C(R 1 )-CH2]- is another polymerizable unit of the silicone diacrylate monomer, -C(R 1 )=CH2 reacting with the polymerizable unit -C(R 1 )=CH2.

[0017] For either Formula (I) or (II), when c + d is 0, the silicone polyether polymer has repeat units derived from at least one ethylenically unsaturated comonomer having at least one pendant alkoxylate group. The comonomer can be any ethylenically unsaturated compound having one or more pendant alkoxylate groups, including, but not limited to, a (meth)acrylate compound, a (meth)acrylamide compound, or a vinyl compound. For example, the ethylenically unsaturated compound can have 1 to 40 pendant alkoxylate groups; in another embodiment, the ethylenically unsaturated compound has 1 to 20 pendant alkoxylate groups; and in another embodiment, the ethylenically unsaturated compound has 1 to 10 pendant alkoxylate groups. The alkoxylate group can be, for example, ethylene oxide, propylene oxide, butylene oxide, or a mixture thereof.

[0018] The silicone polyether polymer may be a homopolymer having 100% repeat units derived from Formula (I) or Formula (II). In another embodiment, the silicone polyether polymer may be a copolymer having repeat units derived from Formula (I) or Formula (II) and repeat units derived from one or more comonomers. When a comonomer is used, the silicone polyether polymer may be in the form of a random copolymer, a block copolymer, or other copolymer configuration. 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 halides, vinyl halides, 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 an alkoxylated (meth)acrylate, a hydroxyalkyl (meth)acrylate, an alkoxylated (meth)acrylamide, a hydroalkyl (meth)acrylamide, or a mixture thereof.

[0019] The silicone polyether polymer has about 6 to 100 weight percent repeat units derived from Formula (I) or Formula (II) and 0 to 94 weight percent repeat units derived from an ethylenically unsaturated comonomer; in another embodiment, the silicone polyether polymer has about 10 to 100 weight percent repeat units derived from Formula (I) or Formula (II) and 0 to 90 weight percent repeat units derived from an ethylenically unsaturated comonomer; in another embodiment, the silicone polyether polymer has about 20 to 100 weight percent repeat units derived from Formula (I) or Formula (II) and 0 to 80 weight percent repeat units derived from an ethylenically unsaturated comonomer; in another embodiment, the silicone polyether polymer has about 10 to 100 weight percent repeat units derived from Formula (I) or Formula (II) and 0 to 90 weight percent repeat units derived from an ethylenically unsaturated comonomer; In one embodiment, the silicone polyether polymer has about 30-100% by weight of repeating units derived from Formula (I) or Formula (II) and 0-70% by weight of repeating units derived from an ethylenically unsaturated comonomer; in another embodiment, the silicone polyether polymer has about 40-100% by weight of repeating units derived from Formula (I) or Formula (II) and 0-60% by weight of repeating units derived from an ethylenically unsaturated comonomer; and in another embodiment, the silicone polyether polymer has about 60-100% by weight of repeating units derived from Formula (I) or Formula (II) and 0-40% by weight of repeating units derived from an ethylenically unsaturated comonomer, all based on the total weight percent of the silicone polyether polymer.

[0020] In another embodiment, the comonomer is distinctly present. In one embodiment, the silicone polyether polymer has about 6 to 99 wt. % repeat units derived from Formula (I) or Formula (II) and 1 to 94 wt. % repeat units derived from an ethylenically unsaturated comonomer, in another embodiment, the silicone polyether polymer has about 10 to 99 wt. % repeat units derived from Formula (I) or Formula (II) and 1 to 90 wt. % repeat units derived from an ethylenically unsaturated comonomer, in another embodiment, the silicone polyether polymer has about 20 to 99 wt. % repeat units derived from Formula (I) or Formula (II) and 1 to 80 ...80 wt. % repeat units derived from an ethylenically unsaturated comonomer, in another embodiment, the silicone polyether polymer has about 10 to 99 wt. % repeat units derived from Formula (I) or Formula (II) and 1 to 80 wt. % repeat units derived from an ethylenically unsaturated comonomer, in another embodiment, the silicone polyether polymer has about 10 to 99 wt. % repeat units derived from Formula (I) or Formula (II) and 1 to 80 w The terpolymer has about 30-99 wt. % repeat units derived from Formula (I) or Formula (II) and 1-70 wt. % repeat units derived from the ethylenically unsaturated comonomer; in another embodiment, the silicone polyether polymer has about 40-99 wt. % repeat units derived from Formula (I) or Formula (II) and 1-60 wt. % repeat units derived from the ethylenically unsaturated comonomer; and in another embodiment, the silicone polyether polymer has about 60-99 wt. % repeat units derived from Formula (I) or Formula (II) and 1-40 wt. % repeat units derived from the ethylenically unsaturated comonomer, all based on the total wt. % of the silicone polyether polymer.

[0021] In one embodiment, the silicone polyether polymer may have repeating units derived from more than two comonomers. For example, the silicone polyether polymer may have repeating units derived from Formula (I) or Formula (II) and 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 halides, vinyl halides, vinyl acetate, diacetone (meth)acrylamide, glycidyl (meth)acrylamide, cyclic hydrocarbon (meth)acrylamides, linear or branched alkyl (meth)acrylamides, or mixtures thereof. In one embodiment, the silicone polyether polymer has about 40-89 wt. % repeat units derived from Formula (I) or Formula (II), about 1-20 wt. % repeat units derived from hydrophilic monomers, and about 10-40 wt. % repeat units derived from the additional monomers described above; in another embodiment, the silicone polyether polymer has about 50-85 wt. % repeat units derived from Formula (I) or Formula (II), about 5-20 wt. % repeat units derived from hydrophilic monomers, and about 10-30 wt. % repeat units derived from the additional monomers described above; and in a third embodiment, the silicone polyether polymer has about 60-75 wt. % repeat units derived from Formula (I) or Formula (II), about 10-15 wt. % repeat units derived from hydrophilic monomers, and about 15-25 wt. % repeat units derived from the additional monomers described above, all based on the total weight of the ethylenically unsaturated comonomers. In one embodiment, the silicone polyether polymer is soluble or dispersible in 1% by weight water at room temperature.

[0022] In one embodiment, the silicone polyether polymer has a molecular weight M of at least 5,000 Da. n and in another embodiment, the molecular weight M nis at least 10,000 Da, and in another embodiment, the molecular weight M n The molecular weight M is at least 20,000 Da. n and M w The RI can be measured by size exclusion chromatography using calibration standards. For example, the polymer solution was diluted, allowed to stand at ambient temperature for 4 days, and passed through a 0.2 μm syringe filter. The polymer solution was injected into the mobile phase through an Agilent 1100 system equipped with a G1362A refractive index detector and pumped at 1.0 mL / min for 40 minutes through two PSS SUPREMA columns (10,000 A, 10 μm; 1,000 A, 5 μm, both 8 × 300 mm) held at 30 °C.

[0023] The at least one surfactant may be any cationic surfactant or any mixture of at least one cationic surfactant and at least one nonionic surfactant. Because anionic surfactants are not beneficial in these treatment compositions, in one embodiment, the treatment composition contains less than 0.01% anionic surfactants. Cationic surfactants include those used in textile applications, including, but not limited to, salts of protonated amines; quaternary ammonium salts; or alkylamine oxides. Protonated amines are formed by mixing an amine compound with an acid such as hydrochloric acid or acetic acid. Examples of amine compounds include alkyldimethylamines, dialkylmethylamines, alkylethoxylated amines, alkyldiamines, and their respective ethoxylates, including compounds sold under the Armeen® brand name. Quaternary amine salts are typically produced by 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 alkyltrimethylammonium salts; dialkyldimethylammonium salts, specifically dialkyldimethylammonium chloride; alkylmethylethoxylated ammonium; alkyldimethylbenzylammonium; dialkylmethylbenzylammonium; alkyl, alkylamidomethyl, and carboalkoxypyridinium (with and without ring substitution); alkylquinolinium; alkylisoquinolinium; N,N-alkylmethylpyrrolidinium; amideimidazolinium; amideammonium; and quaternary ammonium salts of alkyldiamines and their ethoxylates. Some of these compounds are sold under the trade name Arquad®. Alkylamine oxides include compounds such as alkyldimethylamine oxide, dialkylmethylamine oxide, and alkyldiamine oxide.

[0024] Thus, cationic surfactants in either category are typically selected from protonated alkyldimethylamine salts, protonated dialkylmethylamine salts, protonated alkylethoxylated amine salts, protonated alkyldiamine salts, protonated alkylethoxylated diamine salts, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylmethylethoxylated ammonium salts, alkyldimethylbenzylammonium salts, dialkylmethylbenzylammonium salts, alkylpyridinium salts, alkylamidomethylpyridinium salts, carboalkoxypyridinium salts, alkylquinolinium salts, alkylisoquinolinium salts, N,N-alkylmethylpyrrolidinium salts, amidoimidazolium salts, amidoammonium salts; quaternary ammonium salts of alkyldiamines; ethoxylates of quaternary ammonium salts of alkyldiamines; alkyldimethylamine oxides; dialkylmethylamine oxides; and alkyldiamine oxides.

[0025] Nonionic surfactants include those used in textile applications, including, but not limited to, alkoxylate condensate compounds. Examples include alkoxylate condensates of fatty acid alkanolamides, such as amides of fatty acids and diethanolamine; alkoxylate condensates of alkylphenols, such as isooctylphenol; alkoxylate condensates of fatty acids, such as stearates; alkoxylate condensates of linear fatty alcohols; alkoxylate condensates of branched fatty alcohols; and alkoxylate condensates of poly(oxypropylene) block copolymers.

[0026] In one embodiment, the treatment composition comprises about 20-99.5 wt. % silicone polyether polymer; in a second embodiment, about 40-99.5 wt. % silicone polyether polymer; and in a third embodiment, about 50-99.5 wt. % silicone polyether polymer, all based on the total dry weight of the treatment composition. In one embodiment, the treatment composition comprises about 0.5-4 wt. % of at least one surfactant as defined above; in another embodiment, about 0.5-3.5 wt. % surfactant; and in a third embodiment, about 0.5-3 wt. % surfactant, all based on the total dry weight of the treatment composition. The coating composition may also contain a liquid carrier, such as water or an organic solvent, that is not present once the coating is dry or solid. In one embodiment, the liquid carrier is water. Additional components present in the coating composition that make up the remainder of the total dry weight of the treatment composition may include, but are not limited to, surface effect agents, dyes or pigments such as TiO, surfactants, hardeners, pH adjusters, or wetting agents. The term "total dry weight of a coating" is used to refer to the total amount of coating components remaining after the aqueous, solvent, or other liquid components have evaporated; that is, the total amount of non-aqueous, non-solvent, non-volatile components of the coating.

[0027] 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 a cyclic or acyclic polyol, a fatty ester of a polycarboxylic acid, a hydrophobic non-fluorinated (meth)acrylic polymer, a partially fluorinated urethane, a hydrophobic non-fluorinated urethane, a partially fluorinated (meth)acrylic polymer or copolymer, a partially fluorinated (meth)acrylamide polymer or copolymer, a fluorinated phosphate, a fluorinated ethoxylate, a fluorinated or non-fluorinated organosilane, a silicone, a wax including paraffin, and mixtures thereof. In one embodiment, the treatment composition is not 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 the hydrophobic surface effect agent.

[0028] In one embodiment, the treatment composition comprises: a) about 20-95 wt. % silicone polyether polymer; b) about 0.5-4 wt. % at least one surfactant; and c) about 1-79.5 wt. % 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 wt. % silicone polyether polymer; b) about 0.5-4 wt. % at least one surfactant; and c) about 10-79.5 wt. % hydrophobic surface effect agent, all based on the total dry weight of the treatment composition. In a third embodiment, the treatment composition comprises: a) about 39.5-86 wt. % silicone polyether polymer; b) about 0.5-4 wt. % at least one surfactant; and c) about 10-60 wt. % hydrophobic surface effect agent, all based on the total dry weight of the treatment composition. Hydrophobic surface effect agents provide surface benefits 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, antibacterial, sun protection, anti-stick, cleanability, dust resistance, dye leveling, corrosion resistance, acid resistance, anti-fog, or anti-icing, and similar effects. Some stain release and soil release agents are hydrophilic and include compounds such as polymethyl acrylate and hydrophilic urethanes.

[0029] Suitable fatty acid esters of cyclic or acyclic polyols include the reaction products of fatty acids with cyclic or acyclic alcohols, or pentaerythritol, including dipentaerythritol, and may further contain internal alkoxide units. Fatty acid esters of polycarotyloxy acids include the reaction products of polycarboxylic acids with long-chain alkanols. Examples of polyols and polycarboxylic acids include 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, galactose, talose, fructose, ribulose, mannoheptulose, sedoheptulose, threose, erythritol, threitol, glucopyranose, mannopyranose, talopyranose, allose, glyceraldehyde, erythritol ... Suitable fatty acids include, but are not limited to, pyranose, 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, linoleic acid, oleic acid, erucic acid, alkoxylated versions of these acids, and mixtures thereof. In one embodiment, the fatty acid ester or fatty acid esters comprise straight or branched chain alkyl groups having 11 to 29 carbons, and in another embodiment, straight or branched chain alkyl groups having 17 to 21 carbons.Specific examples include mono-, di-, or tri-substituted sorbitans such as SPAN, sorbitan stearate, or sorbitan behenin; mono-, di-, and tri-substituted sorbitans derived from palmitoleic acid, linoleic acid, arachidonic acid, and erucic acid; polysorbates such as polysorbate tristearate and polysorbate monostearate; citrates mono-, di-, or tri-substituted with alkyl groups; and pentaerythriol esters mono-, di-, or tri-substituted with alkyl groups.

[0030] Prior to application to an article, the combination of silicone polyether polymers with hydrophobic surface effect agents imparts superior properties to the article in addition to the desirable properties of low yellowing and good durability. These combined blends are applied to the article in the form of a dispersion in water or other solvent either before, after, or during the application of other treatment chemicals.

[0031] Other useful hydrophobic surface effect agents include fluorinated polymers that provide water-repellent properties to the surface of a treated substrate, which contain one or more fluorinated, stable, inert, and non-polar, preferably saturated, monovalent, fluoroaliphatic groups (referred to herein as R f Fluorochemical compounds or polymers containing a fluorocarbon group (hereinafter referred to as an R group) are included. f The group contains 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. f The group may contain straight chain, branched chain, or cyclic fluorinated alkylene groups or combinations thereof. f The terminal portion of the group has the formula C n F 2n+1Preferably, the perfluorinated aliphatic group is of the formula: where n is from about 3 to about 20. Examples of fluorinated polymer treating agents include CAPSTONE and ZONYL available from Chemours Company (Wilmington, Del.), ASAHI GARD available from Asahi Glass Company, Ltd. (Tokyo, Japan), UNIDYNE available from Daikin America, Inc. (Orangeburg, N.Y.), SCOTCHGARD available from 3M Company, St. Paul, Minn., and NANO TEX available from Nanotex, Emeryville, Calif.

[0032] Examples of such fluorinated polymers include R fPolyurethanes and poly(meth)acrylates containing fluorochemical (meth)acrylate monomers are particularly preferred. Copolymers of fluorochemical (meth)acrylate monomers with copolymerizable monovinyl compounds or conjugated dienes are particularly preferred. Copolymerizable monovinyl compounds include alkyl (meth)acrylates, fatty acid vinyl esters, styrene and alkylstyrenes, vinyl halides, vinylidene halides, alkyl esters, vinyl alkyl ketones, and acrylamides. The conjugated diene is preferably 1,3-butadiene. Representative compounds in the above categories include 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-methylstyrene, p-methylstyrene, vinyl fluoride, vinyl chloride, vinyl bromide, vinylyl fluoride, and vinyl fluoride. Examples of suitable olefin copolymers include olefin copolymers such as olefin copolymers, vinyl ...

[0033] Hydrophobic non-fluorinated acrylic polymers include alkyl (meth)acrylates, fatty acid vinyl esters, styrene and alkylstyrene, vinyl halides, vinylidene halides, alkyl esters, vinyl alkyl ketones, and acrylamides. The conjugated diene is preferably 1,3-butadiene. Representative compounds in the above categories include 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-methylstyrene, p-methylstyrene, vinyl fluoride, vinyl chloride, vinyl bromide, vinyl fluoride, and vinyl methacrylate. Examples of suitable olefin copolymers include olefin copolymers such as olefin copolymers, vinyl ...

[0034] Examples of hydrophobic non-fluorinated urethanes include urethanes prepared by reacting an isocyanate compound with the aforementioned hydrophobic compounds as an alcohol reagent. These compounds are described in U.S. Patents 10,138,392 and 10,246,608. Examples of hydrophobic non-fluorinated nonionic acrylic polymers include those prepared by polymerizing or copolymerizing acrylic esters of the aforementioned hydrophobic compounds. Such compounds are described in U.S. Patent No. 9,915,025.

[0035] Silicone polyether polymers are generally formed by reacting silicone polyether monomers with optional comonomers and surfactants in water. The monomers and surfactants are emulsified using a blender, homogenizer, or other shearing mechanism. The contents are then heated and reacted in the absence of oxygen using a peroxide or other free radical initiator. In one embodiment, the reacted silicone polyether polymer is formed in an aqueous reaction medium; in another embodiment, the reaction medium contains less than 5% by weight of an organic solvent; in another embodiment, the reaction medium contains less than 1% by weight of an organic solvent; and in another embodiment, the reaction medium contains no organic solvent, all based on the total weight of the reaction contents. In another embodiment, the silicone polyether polymer, surfactant, and optional surface effect agent can be effectively mixed by sufficient stirring at room or ambient temperature to form a treatment composition. More precise mixing can be achieved using a mechanical shaker, the application of heat, or other methods.

[0036] The blend compositions of the present invention optionally further comprise additional components, such as additional treatments or finishes to achieve additional surface benefits, or additives commonly used with such treatments or finishes. One or more such treatments or finishes may be combined with the blend composition and applied to an article. Other additives commonly used with such treatments or finishes may also be present, such as surfactants, pH adjusters, crosslinkers, wetting agents, and other additives known to those skilled in the art. Additionally, other extender compositions are optionally included to achieve a combination of benefits.

[0037] In one aspect, the present invention relates to a process for providing a surface benefit to a fibrous substrate, comprising contacting the substrate with a treatment composition comprising: a) about 20 to 99.5 wt. % of a silicone polyether polymer; and b) about 0.5 to 4 wt. % of at least one surfactant selected from at least one cationic surfactant or a mixture of at least one cationic surfactant and at least one nonionic surfactant, all based on the total dry weight of the treatment composition, the silicone polyether polymer having from about 6 to about 100 wt. % of repeat units derived from Formula (I) or Formula (II) as set forth above, and from about 0% to about 94 wt. % of repeat units derived from an ethylenically unsaturated comonomer, all based on the total weight of the polymer; a and b are independently integers from 1 to 40, a + b is an integer of at least 2, c and d are independently integers from 0 to 20, e is an integer from 1 to 40, X is a linear or branched C1-C4 alkylene group, R 1 is a C1-C4 alkyl group, and R 2 is -C(R 1 )=CH2 or C(R 1 ) linked polymer backbone units -[C(R 1 )—CH2]—, with the proviso that when c+d is 0, the silicone polyether polymer has repeat units derived from at least one ethylenically unsaturated comonomer having at least one pendant alkoxylate group. This embodiment can be combined with one or more of the previous embodiments.

[0038] The contacting step may be carried out by applying the treatment composition in the form of an aqueous solution, aqueous dispersion, organic solvent solution or dispersion, or co-solvent 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 jet, overflow flood, brushing, spraying, rolling, dip squeeze, painting, dripping, dipping, powder coating, tumbling, or screen printing. Fibrous substrates include, but are not limited to, fibers, fabrics including woven or blended fabrics, paper, nonwoven fabrics, leather, or combinations thereof. "Fabric" refers to natural or synthetic fabrics, or blends thereof, composed of fibers such as cotton, rayon, silk, wool, polyester, polypropylene, polyolefin, nylon, and aramid. "Blended fabric" refers to fabrics made of two or more types of fibers. Typically, these blends are a combination of at least one natural fiber and at least one synthetic fiber, but may also be blends of two or more natural fibers or two or more synthetic fibers.

[0039] The treatment composition of the present invention, applied to a fibrous substrate, optionally further comprises a blocked isocyanate (i.e., as a blended isocyanate) added after copolymerization to enhance durability. 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 specific application of the copolymer. For most applications contemplated by the present invention, the presence of a blocked isocyanate is not necessary to achieve sufficient interchain crosslinking or bonding to the fiber. When added as a blended isocyanate, amounts up to about 20% by weight are added. When treating synthetic textiles, a wetting agent such as ALKANOL 6112, available from EI du Pont de Nemours and Company, Wilmington, DE, can be used. As a further example, when treating cotton or cotton-blend fabrics, wrinkle-resistant resins such as PERMAFRESH EFC available from Emerald Carolina, LLC (Cahrlotte, NC) can be used. When treating nonwoven fabrics, wax extenders such as FREEPEL 1225WR available from Omnova Solutions (Chester, SC) can be used. Antistatic agents such as ZELEC KC available from Stepan (Northfield, IL) or wetting agents such as Hexanol are also suitable.

[0040] The dispersion is typically applied to a fibrous substrate by spraying, dipping, padding, or other known methods. After removing excess liquid, for example, by squeeze rolls, the treated fibrous substrate is dried and then cured, for example, by heating to about 100°C to about 190°C for at least 30 seconds, typically about 60 to about 240 seconds. Such curing enhances oil, water, and soil repellency, as well as the durability of repellency. While these curing conditions are typical, some commercially available equipment may operate outside of these ranges due to its unique design features.

[0041] In one embodiment, the contacting step occurs inside a washing machine. This step can be carried out by any suitable method. For example, the use of water, such as in the washing or rinsing step of the washing machine, facilitates dispersion of the coating composition. The temperature of the water in the washing or rinsing step can be low, room, or high. Methods of contacting the additive with the substrate include, but are not limited to, introducing the coating composition by pouring it into the washing machine tub, by pouring the coating composition into the detergent or treatment reservoir of the washing machine, by adding a dissolvable pouch containing the coating composition, or by adding a controlled coating composition that is introduced into an aqueous liquid and can be contacted with the fibrous substrate in a tub, bucket, or sink, such as when washing textiles by hand. In one aspect, the coating composition is part of a detergent composition, and the non-fluorinated compound forms a finish coating on the finished, dried textile.

[0042] In one embodiment, the coating composition is placed in the washing machine tub or poured into the detergent or treatment dispenser, and the washing machine is programmed to run a wash or rinse cycle. In one embodiment, once the tub is partially filled with water, the laundry treatment or laundry additive composition is poured into the water, and the tub is then filled with water. Optionally, detergent is then added, and the textile substrate is placed in the tub, allowing the washing machine to run a complete rough or rinse cycle.

[0043] In one aspect, the method further comprises heating the partially or completely coated article. For example, a treatment composition can be applied, and the treated article can be heated to melt, flow, dry, or otherwise fix the hydrophobic agent to the surface of the article. In another aspect, the method further comprises exposing the coating composition to ultraviolet light. The final coating on the article is a hardened, durable, permanent coating. In another aspect, the method further comprises hardening the coating by drying, cooling, or allowing to cool. The liquid carrier can be dried by heating or air drying to evaporate the liquid carrier, thus leaving a permanent, solid coating. [Example]

[0044] All solvents and reagents were purchased from Sigma-Aldrich (St. Louis, MO) and used directly as supplied unless otherwise indicated.

[0045] Vazo™ 56 and Vazo™ 68 are free radical initiators, and Zelan™ R3 is a durable water repellent, all available from The Chemours Company (Wilmington, Del.).

[0046] Armeen® DM-18D is a dimethylstearamine cationic surfactant, Arquad® 16-50 is a C16 trimethylammonium chloride cationic surfactant with 50% solids by weight, and Arquad® 15-29 is a C16 trimethylammonium chloride cationic surfactant with 27-30% solids by weight, all commercially available from Nouryon (Chicago, IL).

[0047] PHOBOL® XAN is a water repellency extender, ULTRATEX® SI is a fabric softening additive, TURPEX® ACN is a fabric softening additive, INVADINE® PBN is a wetting agent, and KNITTEX® 7636 is a crosslinking agent, all available from Huntsman Corp (Salt Lake City, UT).

[0048] C13-methacrylate is a linear C13 alkyl methacrylate and IBOMA is isobornyl methacrylate, both available from Evonik (Essen, Germany).

[0049] Blemmer® GLM is glycerol monomethacrylate, Blemmer® PLE-200 is lauroxy polyethylene glycol methacrylate, Blemmer® AME-400 is methoxy polyethylene glycol acrylate, Blemmer® ADE-400A is polyalkylene glycol diacrylate, Blemmer® PE-90 is hydroxy-terminated polyethylene glycol methacrylate, and Blemmer® VMA-70 is behenyl methacrylate, all available from NOF (Tokyo, Japan).

[0050] CD9075 is an alkoxylated lauryl acrylate available from Sartomer (Exton, PA).

[0051] Tergitol® TMN-10 is a nonionic surfactant available from Dow Chemicals (Midland, MI).

[0052] Chemidex™ S is a cationic surfactant available from Lubrizol (Wickliffe, OH).

[0053] Silmer® ACR D208 is a multifunctional acrylate silicone polyether having a molecular weight of 3000, Silmer® ACR Di-1010 is a difunctional acrylate silicone polyether, Silmer® ACR Di-1508 is a linear silicone polyether diacrylate having a molecular weight of 1500, Silmer® ACR Di-2010-D is a difunctional acrylate silicone polyether, Silmer® MACR Di-1010 is a difunctional methacrylate silicone polyether, Silmer® MACR Di-1017 is a difunctional methacrylate silicone polyether, Silmer® MACR Di-1508 is a difunctional methacrylate silicone polyether, 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).

[0054] The following test methods and materials were used in the examples herein.

[0055] Test Method Test Method 1 - Fabric Treatment The fabric treated in this test was 100% khaki cotton twill, available from SDL Atlas Textile Testing Solutions (Rock Hill, South Carolina 29732). Aqueous dispersions of various emulsion polymers were used to treat the fabric using a conventional pad-bath (dipping) process. The prepared concentrated dispersions were diluted with deionized water to obtain a pad bath with 60 g / L of product in the bath. The fabric was padded in the bath, and excess liquid was removed with a squeeze roller. The wet pick-up was approximately 95% based on the cotton substrate. "Wet pick-up" refers to the weight of the emulsion polymer bath solution applied to the fabric, based on the dry weight of the fabric. The emulsions were cured at approximately 165°C for 3 minutes and allowed to "set" for at least 15 hours after treatment and curing.

[0056] Test Method 2 - Spray Test The dynamic water repellency of the treated substrates was measured according to American Association of Textile Chemists and Colorists (AATCC) TM-22. Samples were visually scored with reference to published standards, with a rating of 100 indicating no water penetration or surface adhesion. A rating of 90 indicates some random adhesion or wetting with no penetration, with lower values ​​representing progressively increased wetting and penetration. The dynamic water repellency test is a demanding, realistic test of water repellency.

[0057] Test Method 3 - Stain Removal This test measures the ability of textiles to remove oily stains. The treated fabric was placed on a flat surface. Using an eyedropper, five drops of MAZOLA Corn Oil or mineral oil (0.2 mL) were placed on the fabric to form one drop of oil. A weight (5 lb, 2.27 kg) was placed on the drop of oil along with a piece of glassine paper to separate it. The weight was left in place for 60 seconds. After 60 seconds, the weight and glassine paper were removed. An initial evaluation was made. The fabric was rated for residual staining from 1 to 5, with 1 being the most residual stain remaining and 5 being no visible stain remaining. The fabric samples were then washed for 12 minutes on the "high" setting in a fully automatic washing machine with AATCC 1993 Standard Reference Detergent WOB12 or granular detergent (100 g). The fabrics were then dried on "High" for 45-50 minutes. The fabrics were again rated for residual staining from 1 to 5 as described above. In the following examples, the corn oil stain removal rating is referred to as "Corn Oil" and the mineral oil stain removal rating is referred to as "Mineral Oil." The term "HW" indicates home wash cycles, and "10HW" indicates that 10 home wash cycles were performed before the final rating was recorded.

[0058] Comparative example A The cotton fabric was tested according to the test method described above without the treatment composition.

[0059] Examples 1 to 7 Silicone monomer (16.35 wt%), Armeen® DM18D (0.57 wt%), glacial acetic acid (0.46 wt%), and deionized water (81.73 wt%) were weighed into a container. The contents were blended in a blender at setting 3 for 2 minutes. The mixture was added to a reactor, sparged with nitrogen, and heated to 55°C. Under a nitrogen blanket, initiator (Vazo™ 56, 0.03 wt% of the total mixture in 0.86 wt% water) was added. The composition was mixed at 70°C for 4 hours. The resulting polymer emulsion was applied to textiles and tested according to the test methods described above. For Example 4, the composition was applied to the substrate from a pad bath at 100 g / L.

[0060] Examples 8 to 11 Example 1 was repeated except that Phobol® XAN was added to the pad bath at 5 g / L.

[0061] [Table 1]

[0062] Comparative example B Silmer® ACR Di-1508 (16.52 wt%) and deionized water (85.58 wt%) were weighed into a container. The contents were blended in a blender at setting 3 for 2 minutes. The mixture was added to a reactor, sparged with nitrogen, and heated to 55°C. Under a nitrogen blanket, initiator (Vazo™ 56, 0.04 wt% of the total mixture in 0.87 wt% water) was added. The composition was mixed at 70°C for 4 hours. The resulting polymer gelled and could not be tested for performance.

[0063] Comparative example C Silmer® ACR Di-1508 (13.14 wt%), 7EO MA (3.29 wt%), Armeen® DM18D (0.28 wt%), glacial acetic acid (0.23 wt%), and deionized water (82.15 wt%) were weighed into a container. The contents were blended in a blender at setting 3 for 2 minutes. The mixture was added to a reactor, sparged with nitrogen, and heated to 55°C. Under a nitrogen blanket, initiator (Vazo™ 56, 0.04 wt% of the total mixture in 0.86 wt% water) was added. The composition was mixed at 70°C for 4 hours. The resulting polymer emulsion was applied to textiles and tested according to the test methods described above.

[0064] Examples 12-13 Comparative Example C was repeated using the amounts listed in Table 2. Example 12 used Chemidex® S instead of Armeen® DM18D. The resulting polymer emulsion was applied to textile and tested according to the test methods described above.

[0065] [Table 2]

[0066] Examples 14-15 Examples 12-13 were repeated except that Phobol® XAN was added to the pad bath at 5 g / L.

[0067] [Table 3]

[0068] Example 16 Silmer® ACR Di-2010-D (13.08 wt%), 7EO MA (3.27 wt%), Armeen® DM18D (0.57 wt%), glacial acetic acid (0.46 wt%), and deionized water (81.73 wt%) were weighed into a container. The contents were blended in a blender at setting 3 for 2 minutes. The mixture was added to a reactor, sparged with nitrogen, and heated to 55°C. Under a nitrogen blanket, initiator (Vazo™ 56, 0.03 wt% of the total mixture in 0.86 wt% water) was added. The composition was mixed at 70°C for 4 hours. The resulting polymer emulsion was applied to textiles and tested according to the test methods described above.

[0069] Examples 17 to 22 Example 16 was repeated except that the additives were included in the pad bath in the amounts shown below.

[0070] [Table 4]

[0071] Examples 23 to 25 Example 16 was repeated using the silicone monomers listed.

[0072] Example 26 Example 16 was repeated using Silmer® ACR Di-1508 instead of Silmer® ACR Di-2010-D and hydroxyethyl methacrylate (HEMA) instead of 7EO MA. The resulting polymer emulsion was applied to textile and tested according to the test methods described above.

[0073] [Table 5]

[0074] Comparative example D Example 26 was repeated using 16.35 wt% HEMA and no Silmer® ACR Di-1508. The resulting polymer gelled and could not be tested for performance.

[0075] Examples 27 to 35 Silmer® ACR Di-1508 (4.09 wt%), 7EO MA (4.09 wt%), additional monomer (8.17 wt%), Armeen® DM18D (0.57 wt%), glacial acetic acid (0.46 wt%), and deionized water (81.73 wt%) were weighed into a container. The contents were blended in a blender at setting 3 for 2 minutes. The mixture was added to a reactor, sparged with nitrogen, and heated to 55°C. Under a nitrogen blanket, initiator (Vazo™ 56, 0.03 wt% of the total mixture in 0.86 wt% water) was added. The composition was mixed at 70°C for 4 hours. The resulting polymer emulsion was applied to textiles and tested according to the test methods described above.

[0076] Examples 36 to 38 Example 27 was repeated except that PHOBOL® XAN was added to the pad bath at 5 g / L.

[0077] [Table 6]

[0078] Examples 39 to 69 and Comparative Examples E to H Example 27 was repeated using the following monomers: DI water (81.71 wt%) and Vazo™ 56 (0.05 wt%) were varied from the procedure above. The resulting polymer emulsion was applied to textile and tested according to the test methods described above. Example 69 and Comparative Example H used 0.03 wt% Vazo™ 56.

[0079] [Table 7]

[0080] Examples 70 to 73 Example 27 was repeated using methyl methacrylate as an additional monomer and using the silicone monomers listed below.

[0081] Examples 74-75 Example 27 was repeated using methyl methacrylate as an additional monomer and Blemmer® ADE-400A instead of 7EO MA. In Example 75, PHOBOL® XAN was added to the pad bath at 5 g / L.

[0082] [Table 8]

[0083] Examples 76-77 Silmer® ACR Di-1508 (4.09 wt%), methyl methacrylate (12.26 wt%), Armeen® DM18D (0.57 wt%), glacial acetic acid (0.46 wt%), and deionized water (81.73 wt%) were weighed into a container. The contents were blended in a blender at setting 3 for 2 minutes. The mixture was added to a reactor, sparged with nitrogen, and heated to 55°C. Under a nitrogen blanket, initiator (Vazo™ 56, 0.03 wt% of the total mixture in 0.86 wt% water) was added. The composition was mixed at 70°C for 4 hours. The resulting polymer emulsion was applied to textiles and tested according to the test methods described above. For Example 77, PHOBOL® XAN was added to the pad bath at 5 g / L.

[0084] Example 78 Example 76 was repeated using Silmer® ACR Di-1010 instead of Silmer® ACR Di-1508.

[0085] [Table 9]

[0086] Examples 79 to 82 Example 27 was repeated using ethylhexyl methacrylate as an additional monomer and substituting the following monomers for 7EO MA: The resulting polymer emulsion was applied to textile and tested according to the test methods described above.

[0087] Examples 83-84 Example 79 was repeated using 4.09 wt % ethylhexyl methacrylate and 8.17 wt % of the following monomers:

[0088] [Table 10]

[0089] Examples 85-86 Example 16 was repeated using Silmer® ACR Di-1508 instead of Silmer® ACR Di-2010-D and Blemmer® PLE-200 instead of 7EO MA. In Example 86, PHOBOL® XAN was added to the pad bath at 5 g / L.

[0090] Example 87 Example 16 was repeated using Silmer® ACR Di-1010 instead of Silmer® ACR Di-2010-D and Blemmer® AME-400 instead of 7EO MA. PHOBOL® XAN was added to the pad bath at 5 g / L.

[0091] Examples 88-89 Example 16 was repeated using CD9075 instead of 7EO MA. In Example 89, PHOBOL® XAN was added to the pad bath at 5 g / L.

[0092] Example 90 Example 27 was repeated using Blemmer® VMA-70 as an additional monomer and using Silmer® ACR Di-2010 instead of Silmer® ACR Di-1010-D.

[0093] Example 91 Silmer® ACR Di-2010-D (7.84 wt%), dodecyl mercaptan (0.01 wt%), ethylene glycol dimethacrylate (1.96 wt%), Armeen® DM18D (0.57 wt%), glacial acetic acid (0.46 wt%), and deionized water (81.65 wt%) were weighed into a container. The contents were blended in a blender at setting 3 for 2 minutes. The mixture was added to a reactor, sparged with nitrogen, and heated to 55°C. Under a nitrogen blanket, initiator (Vazo™ 56, 0.03 wt% of the total mixture in 0.86 wt% water) was added. The composition was mixed at 70°C for 2.5 hours. At this point, a mixture of ethylhexyl methacrylate (3.27 wt%), IBOMA (2.94 wt%), and 7EO MA (0.33 wt%) was added to the reactor over 10 minutes. Additional Vazo™ 56 (0.003 wt % of the total mixture in 0.09 wt % water) was added. The composition was mixed for 4 hours at 70° C. The resulting polymer emulsion was applied to textiles and tested according to the test methods described above.

[0094] Example 92 Example 91 was repeated using ethylhexyl methacrylate (6.53 wt %) and omitting IBOMA and 7EO MA in the second step.

[0095] [Table 11]

[0096] Examples 93 to 95 Example 27 was repeated using Silmer® MACR Di-1508 instead of Silmer® ACR Di-1508 and using the monomers in the table below.

[0097] [Table 12]

[0098] Examples 96-97 Silmer® MACR D208 (10.99 wt%), 7EO MA (1.21 wt%), hydroxyethyl methacrylate (1.10 wt%), IBOMA (3.05 wt%), Armeen® DM18D (0.57 wt%), glacial acetic acid (0.46 wt%), and deionized water (81.73 wt%) were weighed into a container. The contents were blended in a blender at setting 3 for 2 minutes. The mixture was added to a reactor, sparged with nitrogen, and heated to 55°C. Under a nitrogen blanket, initiator (Vazo™ 56, 0.04 wt% of the total mixture in 0.86 wt% water) was added. The composition was mixed at 70°C for 4 hours. The resulting polymer emulsion was applied to textiles and tested according to the test methods described above. In Example 97, PHOBOL® XAN was added to the pad bath at 5 g / L.

[0099] Example 98 Silmer® MACR D208 (11.44 wt%), 7EO MA (3.27 wt%), vinylidene chloride (1.63 wt%), Armeen® DM18D (0.57 wt%), glacial acetic acid (0.46 wt%), and deionized water (81.72 wt%) were weighed into a container. The contents were blended in a blender at setting 3 for 2 minutes. The mixture was added to a reactor, sparged with nitrogen, and heated to 55°C. Under a nitrogen blanket, initiator (Vazo™ 56, 0.05 wt% of the total mixture in 0.86 wt% water) was added. The composition was mixed at 70°C for 4 hours. The resulting polymer emulsion was applied to textiles and tested according to the test methods described above.

[0100] Example 99 Silmer® MACR D208 (12.07 wt%), HEMA (2.73 wt%), vinylidene chloride (0.82 wt%), Tergitol® TMN-10 (0.43 wt%), Armeen® DM18D (0.57 wt%), glacial acetic acid (0.46 wt%), and deionized water (82.01 wt%) were weighed into a container. The contents were blended in a blender at setting 3 for 2 minutes. The mixture was added to a reactor, sparged with nitrogen, and heated to 55°C. Under a nitrogen blanket, initiator (Vazo™ 56, 0.05 wt% of the total mixture in 0.87 wt% water) was added. The composition was mixed at 70°C for 4 hours. The resulting polymer emulsion was applied to textiles and tested according to the test methods described above.

[0101] Example 100 Silmer® ACR Di-1508 (10.99 wt%), HEMA (1.10 wt%), 7EO MA (1.21 wt%), ethylhexyl methacrylate (3.05 wt%), Armeen® DM18D (0.57 wt%), glacial acetic acid (0.46 wt%), and deionized water (81.73 wt%) were weighed into a container. The contents were blended in a blender at setting 3 for 2 minutes. The mixture was added to a reactor, sparged with nitrogen, and heated to 55°C. Under a nitrogen blanket, initiator (Vazo™ 56, 0.04 wt% of the total mixture in 0.86 wt% water) was added. The composition was mixed at 70°C for 4 hours. The resulting polymer emulsion was applied to textiles and tested according to the test methods described above.

[0102] Example 101 Silmer® ACR Di-1508 (10.77 wt%), HEMA (1.08 wt%), 7EO MA (1.19 wt%), ethylhexyl methacrylate (2.99 wt%), Arquad® 16-50 (3.00 wt%), and deionized water (80.09 wt%) were weighed into a container. The contents were blended in a blender at setting 3 for 2 minutes. The mixture was added to a reactor, sparged with nitrogen, and heated to 55°C. Under a nitrogen blanket, initiator (Vazo™ 56, 0.03 wt% of the total mixture in 0.85 wt% water) was added. The composition was mixed at 70°C for 4 hours. The resulting polymer emulsion was applied to textiles and tested according to the test methods described above.

[0103] Example 102 Example 16 was repeated using Silmer® MACR D212-CG instead of Silmer® ACR Di-2010-D and hydroxyethyl methacrylate (HEMA) instead of 7EO MA. The resulting polymer emulsion was applied to textile and tested according to the test methods described above.

[0104] Example 103 Example 102 was repeated using Arquad® 16-29 instead of Armeen DM18D, and only 0.04 wt.% Vazo® 56 was used. The resulting polymer emulsion was applied to textile and tested according to the test methods described above.

[0105] Example 104 Example 16 was repeated using Silmer® ACR D208 instead of Silmer® ACR Di-2010-D and hydroxyethyl methacrylate (HEMA) instead of 7EO MA. The resulting polymer emulsion was applied to textile and tested according to the test methods described above.

[0106] Example 105 Example 104 was repeated using Arquad® 16-29 instead of Armeen DM18D. The resulting polymer emulsion was applied to a textile and tested according to the test methods described above.

[0107] [Table 13]

[0108] Examples 106 to 121 The products of the different examples were blended according to the table below. The weight % of each component was based on the solids content of that component. The blended products were then diluted to 20% solids. PHOBOL® XAN was added to the pad bath at 5 g / L, except for Examples 112-114 and 119-121.

[0109] [Table 14]

[0110] [Table 15]

Claims

1. 1. A treated substrate comprising a fibrous substrate and a treatment composition applied onto the fibrous substrate, the treatment composition comprising, based on a total dry weight of the treatment composition: a) 20 to 99.5 wt. % of a silicone polyether polymer; b) 0.5 to 4 wt. % of at least one surfactant selected from at least one cationic surfactant or a mixture of at least one cationic surfactant and at least one nonionic surfactant; Including, the silicone polyether polymer having from 6 to 100 wt. % repeat units derived from Formula (I) or Formula (II) and from 0 wt. % to 94 wt. % repeat units derived from an ethylenically unsaturated comonomer, all based on the total weight of the silicone polyether polymer; 【Chemistry 1】 [In the formula, a and b are independently integers from 1 to 40, and a+b is an integer of at least 2; c and d are independently integers from 0 to 20; e is an integer from 1 to 40, X is a linear or branched C 1 ~C 4 is an alkylene group, R 1 is C 1 ~C 4 is an alkyl group, R 2 is -C(R 1 ) = CH 2 or C(R 1 ) linked polymer backbone units -[C(R 1 )-CH 2 ]- with the proviso that when c+d is 0, the silicone polyether polymer has repeat units derived from at least one ethylenically unsaturated comonomer having at least one pendant alkoxylate group; Treated substrate.

2. 10. The treated substrate of claim 1, wherein the silicone polyether polymer has from 10 to 100% by weight of repeat units derived from Formula (I) or Formula (II) and from 0 to 90% by weight of repeat units derived from an ethylenically unsaturated comonomer.

3. 10. The treated substrate of claim 1, wherein the silicone polyether polymer has 40 to 100 weight percent repeat units derived from Formula (I) or Formula (II) and 0 to 60 weight percent repeat units derived from an ethylenically unsaturated comonomer.

4. 10. The treated substrate of claim 1, wherein the silicone polyether polymer has 100% by weight of repeat units derived from formula (I) or formula (II).

5. 4. The treated substrate of any one of claims 1 to 3, wherein the ethylenically unsaturated comonomer is 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 halides, vinyl halides, vinyl acetate, diacetone (meth)acrylamide, glycidyl (meth)acrylamide, cyclic hydrocarbon (meth)acrylamides, linear or branched alkyl (meth)acrylamides, or mixtures thereof.

6. the silicone polyether polymer at least one monomer selected from alkoxylated (meth)acrylates, alkoxylated (meth)acrylamides, hydroxyalkyl (meth)acrylates, hydroxyalkyl (meth)acrylamides, glycidyl (meth)acrylates, or mixtures thereof; at least one additional monomer selected from cyclic hydrocarbon (meth)acrylates, linear or branched alkyl (meth)acrylates, vinylidene halides, vinyl halides, vinyl acetate, diacetone (meth)acrylamide, glycidyl (meth)acrylamide, cyclic hydrocarbon (meth)acrylamides, linear or branched alkyl (meth)acrylamides, or mixtures thereof; 6. The treated substrate of claim 5, having repeat units derived from the copolymerization of:

7. 7. The treated substrate of any one of claims 1 to 6, wherein the treatment composition further comprises a hydrophobic surface effect agent 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 paraffins, and mixtures thereof.

8. The treated substrate of claim 1, wherein the treatment composition is fluorine-free.

9. 9. The treated substrate of any one of claims 1 to 8, wherein the treatment composition comprises: a) 20 to 95 wt. % of a silicone polyether polymer; b) 0.5 to 4 wt. % of at least one surfactant; and c) 1 to 79.5 wt. % of a hydrophobic surface effect agent, the hydrophobic surface effect agent being 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 paraffins, and mixtures thereof, all based on the total dry weight of the treatment composition.

10. 1. A process for providing a surface effect to a substrate, the process comprising contacting a treatment composition with a fibrous substrate, the treatment composition comprising: a) 20 to 99.5 wt. % of a silicone polyether polymer; b) 0.5 to 4 wt. % of at least one surfactant selected from at least one cationic surfactant or a mixture of at least one cationic surfactant and at least one nonionic surfactant; Including, the silicone polyether polymer having from 6 to 100 wt. % repeat units derived from Formula (I) or Formula (II) and from 0 to 94 wt. % repeat units derived from an ethylenically unsaturated comonomer, all based on the total weight of the silicone polyether polymer; 【Chemistry 2】 [In the formula, a and b are independently integers from 1 to 40, and a+b is an integer of at least 2; c and d are independently integers from 0 to 20; e is an integer from 1 to 40, X is a linear or branched C 1 ~C 4 is an alkylene group, R 1 is C 1 ~C 4 is an alkyl group, R 2 is -C(R 1 ) = CH 2 or C(R 1 ) linked polymer backbone units -[C(R 1 )-CH 2 ]- with the proviso that when c+d is 0, the silicone polyether polymer has repeat units derived from at least one ethylenically unsaturated comonomer having at least one pendant alkoxylate group; process.

11. 11. The process of claim 10, wherein the silicone polyether polymer has from 10 to 100 weight percent repeat units derived from Formula (I) or Formula (II) and from 0 to 90 weight percent repeat units derived from an ethylenically unsaturated comonomer.

12. 11. The process of claim 10, wherein the silicone polyether polymer has 40 to 100 weight percent repeat units derived from Formula (I) or Formula (II) and 0 to 60 weight percent repeat units derived from an ethylenically unsaturated comonomer.

13. 11. The process of claim 10, wherein the silicone polyether polymer has 100% by weight of repeat units derived from formula (I) or formula (II).

14. 14. The process of any one of claims 10 to 13, wherein the ethylenically unsaturated comonomer is 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 halides, vinyl halides, vinyl acetate, diacetone (meth)acrylamide, glycidyl (meth)acrylamide, cyclic hydrocarbon (meth)acrylamides, linear or branched alkyl (meth)acrylamides, or mixtures thereof.

15. the silicone polyether polymer at least one monomer selected from alkoxylated (meth)acrylates, alkoxylated (meth)acrylamides, hydroxyalkyl (meth)acrylates, hydroxyalkyl (meth)acrylamides, glycidyl (meth)acrylates, or mixtures thereof; at least one additional monomer selected from cyclic hydrocarbon (meth)acrylates, linear or branched alkyl (meth)acrylates, vinylidene halides, vinyl halides, vinyl acetate, diacetone (meth)acrylamide, glycidyl (meth)acrylamide, cyclic hydrocarbon (meth)acrylamides, linear or branched alkyl (meth)acrylamides, or mixtures thereof; 15. The process of claim 14, having repeat units derived from the copolymerization of

16. 16. The process of any one of claims 10 to 15, wherein the treatment composition further comprises a fatty acid ester of a cyclic or acyclic polyol, a fatty ester of a polycarboxylic acid, a hydrophobic non-fluorinated (meth)acrylic polymer, a partially fluorinated urethane, a hydrophobic non-fluorinated urethane, a partially fluorinated (meth)acrylic polymer or copolymer, a partially fluorinated (meth)acrylamide polymer or copolymer, a fluorinated phosphate, a fluorinated ethoxylate, a fluorinated or non-fluorinated organosilane, a silicone, a wax including paraffin, and mixtures thereof.

17. The process of claim 10, wherein the treatment composition is fluorine-free.

18. 18. The process of any one of claims 10 to 17, wherein the contacting step occurs by exhaustion, foam, flex nip, nip, pad, kiss roll, beck, skein, winch, liquid jet, overflow flood, brushing, spraying, rolling, dip squeeze, painting, dripping, immersion, powder coating, tumbling, or screen printing.

19. The process of any one of claims 10 to 17, wherein the contacting step occurs in a washing machine.

20. 20. The process of any one of claims 10 to 19, wherein the treatment composition comprises: a) 20 to 95 wt. % of a silicone polyether polymer; b) 0.5 to 4 wt. % of at least one surfactant; and c) 1 to 79.5 wt. % of a hydrophobic surface effect agent, the hydrophobic surface effect agent being 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 paraffins, and mixtures thereof, all based on the total dry weight of the treatment composition.

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