Silicone polyether polymer treatment for fiber substrates

Abstract

A fiber substrate treatment composition having a) from 20 wt% to 99.5 wt% of a silicone polyether polymer and b) from 0.5 wt% to 4 wt% of a cationic surfactant or a mixture of a cationic surfactant and a nonionic surfactant; wherein the silicone polyether polymer has from 6 wt% to 100 wt% of Formula (I) or Formula (II) and from 0 wt% to 94 wt% of repeat units from an ethylenically unsaturated comonomer; (Formula (I) (II)) wherein a and b are integers from 1 to 40, wherein a+b is an integer of at least 2; c and d are 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 a polymer backbone unit -[C(R 1 )-CH2] bonded at C(R 1 ). The treatment exhibits an improved balance of water repellency and oil stain removal performance.

Description

Technical Field

[0001] Organosilicon polyether polymer compositions are used as coatings or finishing agents to provide surface effects to fibrous substrates. Background Technology

[0002] Various compositions are known to be used as treatment agents to provide water repellency and, optionally, stain removal to textile substrates. Many of these treatment agents are fluorinated polymers and copolymers, or non-fluorinated polymers and copolymers. Non-fluorinated compounds are primarily polyacrylate or urethane copolymers.

[0003] Fluorinated polymer compositions are used to prepare a variety of surface treatment materials to provide surface effects to substrates. Many of these compositions are fluorinated surfactants that primarily contain eight or more carbons in the perfluoroalkyl chain to provide the desired properties. Honda et al., in Macromolecules, 2005, Vol. 38, 5699-5705, teach that for perfluoroalkyl chains with more than eight carbons, the orientation of the perfluoroalkyl groups named after the Rf group remains parallel, while for such chains with six or fewer carbons, reorientation occurs. This reorientation is said to reduce surface properties such as contact angle. Therefore, compounds containing shorter perfluoroalkyl chains or no fluorine content generally exhibit lower performance. Summary of the Invention

[0004] There is a need for compositions that provide a surface effect to a fibrous substrate, wherein water-repellent properties are balanced with oil-removing properties. This invention fulfills these needs.

[0005] The present invention relates to a treated substrate comprising a fibrous substrate and a treatment composition applied to the fibrous substrate, wherein the treatment composition comprises: a) about 20% to 99.5% by weight of a silicone polyether polymer, and b) about 0.5% to 4% by weight 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 about 6% to about 100% by weight of repeating units from formula (I) or formula (II) and about 0% to about 94% by weight of repeating units from olefinic unsaturated comonomers, all based on the total weight of the polymer;

[0006]

[0007] Where a and b are independent integers from 1 to 40, and a+b is an integer of at least 2; c and d are independent integers from 0 to 20; e is an integer from 1 to 40; X is a straight-chain or branched C1-C4 alkylene group; R1 It is a C1-C4 alkyl group; and R 2 -C(R) 1 )=CH2 or C(R) 1 The polymer backbone unit bonded at ) - [C(R 1 [-CH2]-; the prerequisite is that if c+d is 0, then the organosilicon polyether polymer has repeating units from at least one olefinic unsaturated comonomer having at least one alkoxylated side group.

[0008] The present invention also includes a method for providing a surface effect to a substrate, the method comprising contacting a treatment composition with a fibrous substrate, wherein the treatment composition comprises a) about 20% to 99.5% by weight of a silicone polyether polymer, and b) about 0.5% to 4% by weight 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 about 6% to about 100% by weight of repeating units from formula (I) or formula (II) as shown above and about 0% to about 94% by weight of repeating units from an olefinically unsaturated comonomer, all based on the total weight of the polymer; wherein a and b are independently integers from 1 to 40, wherein a+b is at least 2; c and d are independently integers from 0 to 20; e is an integer from 1 to 40; X is a straight-chain or branched C1-C4 alkylene group; R 1 It is a C1-C4 alkyl group; and R 2 -C(R) 1 )=CH2 or C(R) 1 The polymer backbone unit bonded at ) - [C(R 1 [-CH2]-; the prerequisite is that if c+d is 0, then the organosilicon polyether polymer has repeating units from at least one olefinic unsaturated comonomer having at least one alkoxylated side group. Detailed Implementation

[0009] The features of the embodiments of the present invention described in the specific embodiments of the present invention can be combined in any way.

[0010] This invention provides treated fiber substrates with improved water repellency, oil repellency or stain repellency, cleanability, and / or other surface effects. The treatment composition provides a balance of hydrophobic and oleophobic properties without the use of fluorine. The resulting coating is durable, meaning that it is a long-lasting film that is not easily removed by water or detergents. In one aspect, once the coating dries, it is insoluble or dispersible in water or detergents, and in another aspect, the coating can withstand multiple cleanings without loss of performance.

[0011] In one aspect, the present invention relates to a treated substrate comprising a fibrous substrate and a treatment composition applied to the fibrous substrate, wherein the treatment composition comprises: a) about 20% to 99.5% by weight of a silicone polyether polymer, and b) about 0.5% to 4% by weight 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 about 6% to about 100% by weight of repeating units from formula (I) or formula (II) and about 0% to about 94% by weight of repeating units from olefinic unsaturated comonomers, all based on the total weight of the polymer;

[0012]

[0013] Where a and b are independent integers from 1 to 40, and a+b is an integer of at least 2; c and d are independent integers from 0 to 20; e is an integer from 1 to 40; X is a straight-chain or branched C1-C4 alkylene group; R 1 It is a C1-C4 alkyl group; and R 2 -C(R) 1 )=CH2 or C(R) 1 The polymer backbone unit bonded at ) - [C(R 1 [-CH2]-; the prerequisite is that if c+d is 0, then the organosilicon polyether polymer has repeating units from at least one olefinic unsaturated comonomer having at least one alkoxylated side group.

[0014] The term "copolymer" is intended to refer to a polymeric compound having at least two different monomer units. This term includes terpolymers and polymers having more than three different monomer units. -(OCH2CH2)- in formula (I) or (II) represents oxyethylene (EO), and -(OCH2CH(CH3))- represents oxypropylene (PO). These compounds may contain only EO groups, only PO groups, or mixtures thereof in random or block configurations. For example, these compounds may also exist as a triblock copolymer named 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 aspect, when c+d is 0, the olefinic unsaturated comonomer has 1 to 20 alkoxylated side groups; in another aspect, when c+d is 0, the olefinic unsaturated comonomer has 2 to 20 alkoxylated side groups; and in a third aspect, when c+d is 0, the olefinic unsaturated comonomer has 3 to 20 alkoxylated side groups.

[0015] The silicone polyether segment of the polymer can be part of the side chain end group of the (meth)acrylic acid repeating unit, as in formula (I), or it can be a divalent linear segment between two (meth)acrylic acid repeating units, as in formula (II). Polymers having repeating units of formula (I) are formed by free radical polymerization of silicone polyether (meth)acrylate compounds with or without comonomers, while repeating units of formula (II) are formed by free radical polymerization of silicone polyether di(meth)acrylate compounds with or without comonomers. The monomers used to form the repeating units are, for example, trade names... ACR or MACR is present. The compound exhibits a significant hydrophilic content by incorporating organosilicon 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 can be independently integers from 1 to 40; in another aspect, a and b can be independently integers from 2 to 40; and in a third aspect, a and b can be independently integers from 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 from 1 to 40; in another aspect, e is an integer from 2 to 40; and in a third aspect, e is an integer from 3 to 40.

[0016] The polymer of formula (II) is formed from the organosilicon diacrylate monomer of formula (III):

[0017]

[0018] Where R 1 c, d, X, and e are as defined above. In equation (II), R 2 It can be an aggregateable unit -C(R) 1 )=CH2 or C(R) 1 The polymer backbone unit bonded at ) - [C(R 1 )-CH2]-. In C(R 1 The polymer backbone unit bonded at ) - [C(R 1 [-CH2]- is derived from the polymerizable unit -C(R) 1 )=CH2 and another polymerizable unit of organosilicon diacrylate monomer -C(R 1 The reaction of CH2.

[0019] For formula (I) or formula (II), if c+d is 0, the organosilicon polyether polymer has repeating units from at least one olefinically unsaturated comonomer having at least one alkoxylated side group. The comonomer can be any olefinically unsaturated compound having one or more alkoxylated side groups, such as, but not limited to, (meth)acrylate compounds, (meth)acrylamide compounds, or vinyl compounds. For example, the olefinically unsaturated compound may have 1 to 40 alkoxylated side groups; in another aspect, the olefinically unsaturated compound has 1 to 20 alkoxylated side groups; and in yet another aspect, the olefinically unsaturated compound has 1 to 10 alkoxylated side groups. The alkoxylated group can be, for example, ethylene oxide, propylene oxide, butane oxide, or mixtures thereof.

[0020] The silicone polyether polymer can be a homopolymer having 100% repeating units from formula (I) or formula (II). Alternatively, the silicone polyether polymer can be a copolymer having repeating units from formula (I) or formula (II) and repeating units from one or more comonomers. When a comonomer is used, the silicone polyether polymer can be a random copolymer, a block copolymer, or other configuration of the copolymer. The comonomer can be any suitable olefinically unsaturated comonomer. For example, the comonomer can 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)acrylamide, hydroxyalkyl (meth)acrylamide, glycidyl (meth)acrylamide, cyclic hydrocarbon (meth)acrylamide, linear or branched alkyl (meth)acrylamide, or mixtures thereof. When c+d is 0, the alkene-bonded unsaturated monomer having at least one side group may be selected from alkoxylated (meth)acrylates, hydroxyalkyl (meth)acrylates, alkoxylated (meth)acrylamides, hydroxyalkyl (meth)acrylamides, or mixtures thereof.

[0021] The silicone polyether polymer has about 6% to 100% by weight of repeating units from formula (I) or formula (II) and 0% to 94% by weight of repeating units from olefinic unsaturated comonomers; in another aspect, the silicone polyether polymer has about 10% to 100% by weight of repeating units from formula (I) or formula (II) and 0% to 90% by weight of repeating units from olefinic unsaturated comonomers; in yet another aspect, the silicone polyether polymer has about 20% to 100% by weight of repeating units from formula (I) or formula (II) and 0% to 80% by weight of repeating units from olefinic unsaturated comonomers; in yet another aspect, the silicone polyether polymer... The polymer has about 30% to 100% by weight of repeating units from formula (I) or formula (II) and 0% to 70% by weight of repeating units from olefinic unsaturated comonomers; on the other hand, the silicone polyether polymer has about 40% to 100% by weight of repeating units from formula (I) or formula (II) and 0% to 60% by weight of repeating units from olefinic unsaturated comonomers; and on the other hand, the silicone polyether polymer has about 60% to 100% by weight of repeating units from formula (I) or formula (II) and 0% to 40% by weight of repeating units from olefinic unsaturated comonomers; all based on the total weight of the silicone polyether polymer.

[0022] On the other hand, comonomers are advantageously present. In one aspect, the silicone polyether polymer has about 6% to 99% by weight of repeating units from formula (I) or formula (II) and 1% to 94% by weight of repeating units from olefinically unsaturated comonomers; in another aspect, the silicone polyether polymer has about 10% to 99% by weight of repeating units from formula (I) or formula (II) and 1% to 90% by weight of repeating units from olefinically unsaturated comonomers; in another aspect, the silicone polyether polymer has about 20% to 99% by weight of repeating units from formula (I) or formula (II) and 1% to 80% by weight of repeating units from olefinically unsaturated comonomers; in another aspect, the silicone polyether polymer has about 20% to 99% by weight of repeating units from formula (I) or formula (II) and 1% to 80% by weight of repeating units from olefinically unsaturated comonomers; in another aspect, the silicone polyether polymer has about 20% to 99% by weight of repeating units from formula (I) or formula (II) and 1% to 80% by weight of repeating units from olefinically unsaturated comonomers; in another aspect, the silicone polyether polymer has about 1 ... The ether polymer has about 30% to 99% by weight of repeating units from formula (I) or formula (II) and 1% to 70% by weight of repeating units from olefinic unsaturated comonomers; on the other hand, the silicone polyether polymer has about 40% to 99% by weight of repeating units from formula (I) or formula (II) and 1% to 60% by weight of repeating units from olefinic unsaturated comonomers; and on another hand, the silicone polyether polymer has about 60% to 99% by weight of repeating units from formula (I) or formula (II) and 1% to 40% by weight of repeating units from olefinic unsaturated comonomers; all based on the total weight of the silicone polyether polymer.

[0023] 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 repeating units derived from comonomerizing 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 aspect, the silicone polyether polymer has about 40% to 89% by weight of repeating units from formula (I) or formula (II), about 1% to 20% by weight of repeating units from hydrophilic monomers, and about 10% to 40% by weight of repeating units from the aforementioned additional monomers; in another aspect, the silicone polyether polymer has about 50% to 85% by weight of repeating units from formula (I) or formula (II), about 5% to 20% by weight of repeating units from hydrophilic monomers, and about 10% to 30% by weight of repeating units from the aforementioned additional monomers; and in a third aspect, the silicone polyether polymer has about 60% to 75% by weight of repeating units from formula (I) or formula (II), about 10% to 15% by weight of repeating units from hydrophilic monomers, and about 15% to 25% by weight of repeating units from the aforementioned additional monomers; all based on the total weight of the olefinic unsaturated comonomers. In one embodiment, the organosilicon polyether polymer is dissolved or dispersed in water at 1% by weight at room temperature.

[0024] In one respect, the organosilicon polyether polymer has a molecular weight M of at least 5,000 Da. n On the other hand, molecular weight M n It is at least 10,000 Da; and on the other hand, the molecular weight M n It must be at least 20,000 Da. Molecular weight M n and M wIt can be determined by size exclusion chromatography using a calibration standard. For example, the polymer solution is diluted, allowed to stand at ambient temperature for 4 days, and passed through a 0.2 μm injection filter. The polymer solution is injected into the mobile phase using 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 μm; 1,000 A, 5 μm, both 8 x 300 mm) maintained at 30 °C.

[0025] At least one surfactant can 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 aspect, the treatment composition has less than 0.01% anionic surfactant. 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 alkyl dimethylamines, dialkyl methylamines, alkyl ethoxylated amines, alkyl diamines, and their respective ethoxylated derivatives, including those marketed under trademarks. The compounds sold are typically produced by alkylation of amines (including those listed above). Alkylating agents include, but are not limited to, chloromethane, dimethyl sulfate, diethyl sulfate, and benzyl chloride. Specific examples include alkyltrimethylammonium salts; dialkyldimethylammonium salts, particularly dialkyldimethylammonium chloride; alkylmethylethoxyammonium; alkyldimethylbenzylammonium; dialkylmethylbenzylammonium; alkyl, alkylamide methyl, and alkoxycarbonylpyridinium (with and without ring substitution); alkylquinolineon; alkylisoquinolineon; N,N-alkylmethylpyrrolidineon; amide imidazolineon; amide ammonium; and quaternary ammonium salts of alkyl diamines and their ethoxylates. Some of these compounds are marketed under trademarks. For sale. Alkylamine oxides include compounds such as alkyl dimethylamine oxides, dialkyl methylamine oxides, and alkyl diamine oxides.

[0026] Therefore, any kind of cationic surfactant is typically selected from protonated alkyl dimethylamine salts, protonated dialkyl methylamine salts, protonated alkyl ethoxylated amine salts, protonated alkyl diamine salts, protonated alkyl ethoxylated diamine salts, alkyl trimethylammonium salts, dialkyl dimethylammonium salts, alkyl methyl ethoxylated ammonium salts, alkyl dimethyl benzylammonium salts, dialkyl methyl benzylammonium salts, alkyl pyridinium salts, alkyl amide methyl pyridinium salts, alkoxycarbonyl pyridinium salts, alkyl quinolineium salts, alkyl isoquinolineium salts, N,N-alkyl methyl pyrrolidineium salts, amide imidazolineium salts, amide ammonium salts; quaternary ammonium salts of alkyl diamines; ethoxylated derivatives of quaternary ammonium salts of alkyl diamines; alkyl dimethylamine oxides; dialkyl methylamine oxides; and alkyl diamine oxides.

[0027] Nonionic surfactants include those used in textile applications, including but not limited to alkoxylated condensate compounds. Examples include alkoxylated condensates with: fatty acid alkyl alcohol amides such as fatty acid amides and diethanolamine; alkylphenols such as isooctylphenol; fatty acids such as stearates; linear fatty alcohols; branched fatty alcohols; and poly(oxypropylene) block copolymers.

[0028] In one aspect, the treatment composition comprises about 20% to 99.5% by weight of a silicone polyether polymer; in a second aspect, about 40% to 99.5% by weight of a silicone polyether polymer; and in a third aspect, about 50% to 99.5% by weight of a silicone polyether polymer, all based on the total dry weight of the treatment composition. In one aspect, the treatment composition comprises about 0.5% to 4% by weight of at least one surfactant as defined above; in another aspect, about 0.5% to 3.5% by weight of a surfactant; and in a third aspect, about 0.5% to 3% by weight of a 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, which is not present once the coating is dry or solid. In one aspect, the liquid carrier is water. Additional components present in the coating composition constituting 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 TiO2; surfactants; curing agents; pH adjusters; or wetting agents. The term "total dry weight of the coating" refers to the sum of the coating components that would remain once the aqueous solvent or other liquid components evaporate. In other words, it is the sum of the non-aqueous, non-solvent, and non-volatile components of the coating.

[0029] 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 fatty acid esters of cyclic or acyclic polyols, fatty acid esters of polycarboxylic acids, hydrophobic non-fluorinated (meth)acrylic polymers, partially fluorinated polyurethanes, hydrophobic non-fluorinated polyurethanes, partially fluorinated (meth)acrylic polymers or copolymers, partially fluorinated (meth)acrylamide polymers or copolymers, fluorinated phosphate esters, fluorinated ethoxylates, fluorinated or non-fluorinated organosilanes, organosilicones, waxes including paraffin, 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 organosilicon polyether polymer. In one aspect, the amount of the organosilicon polyether polymer is greater than the amount of the hydrophobic surface effect agent.

[0030] In one embodiment, the treatment composition comprises a) about 20% to 95% by weight of a silicone polyether polymer, b) about 0.5% to 4% by weight of at least one surfactant, and c) about 1% to 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% to 86% by weight of a silicone polyether polymer, b) about 0.5% to 4% by weight of at least one surfactant, and c) about 10% to 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% to 86% by weight of a silicone polyether polymer, b) about 0.5% to 4% by weight of at least one surfactant, and c) about 1% to 79.5% by weight of a hydrophobic surface effect agent, all based on the total dry weight of the treatment composition. Surfactants, and c) about 10% to 60% by weight of hydrophobic surface effect agents, all based on the total dry weight of the treated composition; the hydrophobic surface effect agents provide surface effects such as moisture control, strength, antislip properties, antistatic properties, antisnagging properties, anti-pilling properties, stain repellency, detergency, scale repellency, water repellency, oil repellency, odor control, antimicrobial properties, sun protection, anti-blocking properties, cleanability, dust resistance, leveling properties, corrosion resistance, acid resistance, antifogging, or anti-icing properties, and similar effects. Some detergents and scale removers are hydrophilic and include compounds such as polymethyl methacrylate or hydrophilic polyurethanes.

[0031] Suitable fatty acid esters of cyclic or acyclic polyols include reaction products of fatty acids with cyclic or acyclic sugar alcohols, or pentaerythritol (including dipentaerythritol), which may also contain internal alkoxide units. Fatty esters of polycarboxylic 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-dehydro-D-glucanol, 2,5-dehydro-D-mannitol, 2,5-dehydro-L-idultitol, isosorbide, dehydrosorbitol, glyceraldehyde, erythrose, arabinose, ribose, arabinose, allose, arbutin, mannose, xylose, leucose, gulose, galactose, tarose, fructose, ribulose, mannoheptanose, sedoheptulose, threose, erythritol, threitol, pyranose, and pyranose. Mannose, pyrantrolose, pyranoylose, pyranoylose, pyranoyl-Idoleose, pyranogulose, glucol, mannitol, erythritol, sorbitol, arabinitol, xylitol, ribitol, galactitol, fucitol, idoleitol, inositol, pentaerythritol, dipentaerythritol, heptaheptanol, gluconic acid, glyceric acid, xylanic acid, galactobionic acid, ascorbic acid, citric acid, gluconolactone, glycerolactone, xylanolactone, glucosamine, galactosamine, or mixtures thereof. Suitable fatty acids include, but are not limited to, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, ceramide, palmitoleic acid, linoleic acid, oleic acid, erucic acid, alkoxylated forms of these acids, and mixtures thereof. In one embodiment, the fatty acid or fatty ester contains a straight-chain or branched alkyl group having 11 to 29 carbons, and in another embodiment, it contains a straight-chain or branched alkyl group having 17 to 21 carbons. Specific examples include monosubstituted, disubstituted, or trisubstituted sorbitols, such as SPAN, sorbitol stearate, or sorbitol behenate; monosubstituted, disubstituted, and trisubstituted sorbitols derived from palmitoleic acid, linoleic acid, arachidonic acid, and erucic acid; polysorbates, such as polysorbate tristearate and polysorbate monostearate; citrates monosubstituted, disubstituted, or trisubstituted with alkyl groups; and pentaerythritol esters monosubstituted, disubstituted, or trisubstituted with alkyl groups.

[0032] By combining silicone polyether polymers with hydrophobic surface effect agents prior to application to the article, the article is endowed with excellent properties, along with the desired characteristics of low yellowing and good durability. These blends are applied to the article in the form of a dispersion in water or other solvents before, after, or during the application of other treatment chemicals.

[0033] Other useful hydrophobic surface effectors include fluorinated polymers, which provide repulsion to the surface of the treated substrate. These include fluorinated compounds or polymers containing one or more fluorinated aliphatic groups (referred to herein as R...). f(The group) is fluorinated, stable, inert, and nonpolar, preferably saturated, monovalent, and both oleophobic and hydrophobic. R 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. R f The group may contain straight-chain, branched, or cyclic fluorinated alkylene groups or combinations thereof. f The terminal portion of the group is preferably of formula C n F 2n+1 The perfluorinated aliphatic group, wherein n is from about 3 to about 20. Examples of fluorinated polymer treatment agents are CAPSTONE and ZONYL 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).

[0034] Examples of such fluorinated polymers include those containing R f Polyurethanes and poly(meth)acrylates. Particularly preferred are copolymers of fluorinated chemical (meth)acrylate monomers with copolymerizable monovinyl compounds or conjugated dienes. Copolymerizable monovinyl compounds include alkyl (meth)acrylates, vinyl esters of aliphatic acids, styrene and alkylstyrene, vinyl halides, vinylidene halides, alkyl esters, vinyl alkyl ketones, and acrylamides. The conjugated diene is preferably 1,3-butadiene. Representative compounds within the aforementioned categories include: methyl, propyl, butyl, 2-hydroxypropyl, 2-hydroxyethyl, isopentyl, 2-ethylhexyl, octyl, decyl, lauryl, hexadecyl and octadecyl acrylates and methacrylates; vinyl acetate, vinyl propionate, vinyl octanoate, vinyl laurate, vinyl stearate, styrene, α-methylstyrene, p-methylstyrene, vinyl fluoride, vinyl chloride, vinyl bromo, vinylidene fluoride, vinylidene chloride, allyl heptanoate, allyl acetate, allyl octanoate, allyl hexanoate, vinyl methyl ketone, vinyl ethyl ketone, 1,3-butadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, isoprene, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, glycidyl acrylate, glycidyl methacrylate, amine-terminated (meth)acrylates and polyoxy(meth)acrylates.

[0035] Hydrophobic, non-fluorinated acrylic polymers include vinyl compounds, including alkyl methacrylates, vinyl esters of aliphatic acids, styrene and alkylstyrene, vinyl halides, vinylidene halides, alkyl esters, vinyl alkyl ketones, and copolymers of acrylamide. The conjugated diene is preferably 1,3-butadiene. Representative compounds within the aforementioned categories include: methyl, propyl, butyl, 2-hydroxypropyl, 2-hydroxyethyl, isopentyl, 2-ethylhexyl, octyl, decyl, lauryl, hexadecyl and octadecyl acrylates and methacrylates; vinyl acetate, vinyl propionate, vinyl octanoate, vinyl laurate, vinyl stearate, styrene, α-methylstyrene, p-methylstyrene, vinyl fluoride, vinyl chloride, vinyl bromo, vinylidene fluoride, vinylidene chloride, allyl heptanoate, allyl acetate, allyl octanoate, allyl hexanoate, vinyl methyl ketone, vinyl ethyl ketone, 1,3-butadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, isoprene, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, glycidyl acrylate, glycidyl methacrylate, amine-terminated (meth)acrylates and polyoxy(meth)acrylates.

[0036] Hydrophobic nonfluorinated polyurethanes include, for example, polyurethanes synthesized by reacting an isocyanate compound with the aforementioned hydrophobic compound as an alcohol reagent. These compounds are described in US 10,138,392 and US 10,246,608. Hydrophobic nonfluorinated nonionic acrylic polymers include, for example, polymers prepared by polymerizing or copolymerizing acrylates of the aforementioned hydrophobic compounds. Such compounds are described in US 9,915,025.

[0037] Silicone polyether polymers are typically 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 using a peroxide or other free radical initiator in the absence of oxygen. In one aspect, the reactive silicone polyether polymer is formed in an aqueous reaction medium; in another, the reaction medium contains less than 5% by weight of an organic solvent; in yet another, the reaction medium contains less than 1% by weight of an organic solvent; and in yet another, the reaction medium contains no organic solvent; all based on the total weight of the reaction contents. Alternatively, the silicone polyether polymer, surfactant, and optional surface-effect agent can be effectively mixed to form a treatment composition by thoroughly stirring at room temperature or ambient temperature. More complex mixing methods may be employed, such as using a mechanical shaker or providing heating or other methods.

[0038] The coating compositions of the present invention optionally further comprise additional components, such as additional treatment agents or finishing agents for achieving additional surface effects, or additives commonly used with such agents or finishing agents. One or more such treatment agents or finishing agents may be combined with the blend composition and applied to the article. Other additives commonly used with such treatment agents or finishing agents may also be present, such as surfactants, pH adjusters, crosslinking agents, wetting agents, and other additives known to those skilled in the art. Additionally, additional extender compositions may optionally be included to achieve a combination of beneficial effects.

[0039] In one aspect, the present invention relates to a method for providing a surface effect to a substrate, the method comprising contacting a treatment composition with a fibrous substrate, wherein the treatment composition comprises a) about 20% to 99.5% by weight of a silicone polyether polymer, and b) about 0.5% to 4% by weight 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 about 6% to about 100% by weight of repeating units from formula (I) or formula (II) as shown above and about 0% to about 94% by weight of repeating units from an olefinically unsaturated comonomer, all based on the total weight of the polymer; wherein a and b are independently integers from 1 to 40, wherein a+b is at least 2; c and d are independently integers from 0 to 20; e is an integer from 1 to 40; X is a straight-chain or branched C1-C4 alkylene group; R 1 It is a C1-C4 alkyl group; and R 2 -C(R) 1 )=CH2 or C(R) 1 The polymer backbone unit bonded at ) - [C(R 1 [-CH2]-; the prerequisite is that if c+d is 0, then the organosilicon polyether polymer has repeating units from at least one olefinic unsaturated comonomer having at least one alkoxylated side group. This embodiment can be combined with one or more of the foregoing embodiments.

[0040] The contact step can be carried out by applying the treatment composition in the form of an aqueous solution, an aqueous dispersion, an organic solvent solution or dispersion, or a co-solvent solution or dispersion. The contact step can be carried out by any conventional method, including but not limited to dyeing, foaming, flex-nip, nip, padding, wet rollers, rolling, twisting, winch, liquid injection, overflow, brushing, spraying, rolling, dip-extrusion, coating, dripping, impregnation, powder coating, calendering, or screen printing. The fibrous substrate includes, but is not limited to, fibers, textiles (including fabrics or fabric blends), paper, nonwovens, 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, polyolefins, nylon, and aramids. "Fabric blend" means a fabric made of two or more types of fibers. These blends are typically a combination of at least one natural fiber and at least one synthetic fiber, but they can also be blends of two or more natural fibers or blends of two or more synthetic fibers.

[0041] The treatment compositions of the present invention applied to a fiber substrate optionally further comprise a terminated isocyanate to promote durability, which is added after copolymerization (i.e., as a blended isocyanate). An example of a suitable terminated isocyanate is PHOBOL XAN, available from Huntsman Corp (Salt Lake City, UT). Other commercially available terminated isocyanates are also suitable herein. The need for the addition of a terminated isocyanate depends on the specific application of the copolymer. For most currently envisioned applications, its presence is not required to achieve satisfactory crosslinking between chains or bonding with the fiber. When added as a blended isocyanate, the amount added is at most about 20% by weight. When treating synthetic fabrics, wetting agents such as ALKANOL 6112, available from EI du Pont de Nemours and Company (Wilmington, DE), can be used. As another example, when treating cotton or cotton blends, anti-wrinkle resins such as PERMAFRESH EFC, available from Emerald Carolina, LLC, Cahrlotte, NC, South Carolina, can be used. When treating nonwoven fabrics, wax extenders such as FREEPEL 1225WR, available from Omnova Solutions Chester, SC, Chester, South Carolina, can be used. Antistatic agents (such as ZELEC KC, available from Stepan, Northfield, IL, Northfield, IL) or wetting agents (such as hexanol) are also suitable.

[0042] The dispersion is typically applied to a fibrous substrate by spraying, impregnation, padding, or other well-known methods. After excess liquid is removed, for example by squeezing rollers, the treated fibrous substrate is dried and then cured by heating to, for example, about 100°C to about 190°C for at least 30 seconds, typically about 60 seconds to about 240 seconds. Such curing enhances oil repellency, water repellency, and scale repellency, as well as the durability of these resistances. While these curing conditions are typical, some commercial equipment may operate outside these ranges due to their specific design features.

[0043] In one embodiment, the contact step is performed inside the washing machine. This step can be carried out by any suitable method. For example, water is used to facilitate the distribution of the coating composition, such as through a wash cycle or rinse cycle of the washing machine. The water temperature used in the wash cycle or rinse cycle can be any temperature, including cold, room temperature, warm, or hot. Methods of contacting the additive with the substrate include, but are not limited to, introducing the coating composition by pouring it into the washing tub of the washing machine, pouring the coating composition into the detergent or treatment agent reservoir of the washing machine, adding a soluble sachet containing the coating composition, or adding a controlled coating composition that can be introduced into an aqueous liquid and contact the fiber substrate to a basin, tub, or sink, such as when hand-washing fabrics. In one aspect, the coating composition is part of a detergent composition, and a non-fluorinated compound forms a finishing coating on the finished dry fabric.

[0044] In one embodiment, the coating composition is poured into the washing tub of a washing machine, or into a detergent or treatment agent reservoir, and the washing machine is programmed to run a wash cycle or a rinse cycle. In another embodiment, the washing tub is partially filled with water, the laundry treatment composition or laundry additive composition is poured into the water, and the water is allowed to fill the washing tub. Detergent is then optionally added to the washing tub to add the fiber base, and the washing machine is allowed to run a complete wash or rinse cycle.

[0045] In one aspect, the method further includes the step of heating the partially or completely coated article. For example, a treatment composition may be applied, and the treated article may be heated to melt, flow, dry, or otherwise fix the hydrophobic agent to the surface of the article. In another aspect, the method further includes the step of exposing the coating composition to ultraviolet radiation. The final coating on the surface of the article will be a cured, persistent, permanent coating. In yet another aspect, the method further includes the step of curing the coating by drying, cooling, or subjecting it to cooling. The liquid carrier may be dried by heating or air drying to allow the liquid carrier to evaporate, thereby leaving a permanent solid coating.

[0046] Example

[0047] Unless otherwise specified, all solvents and reagents were purchased from Sigma-Aldrich, St. Louis, MO, and used directly as supplied.

[0048] Vazo TM 56 and Vazo TM 68 is a free radical initiator; Zelan TM R3 is a durable water repellent; all were purchased from Chemours Company, Wilmington, DE.

[0049] DM-18D is a dimethyl stearylamine cationic surfactant; 16-50 is a C16 trimethylammonium chloride cationic surfactant with a solid content of 50% by weight; and 15-29 are C16 trimethylammonium chloride cationic surfactants with a solid content of 27% to 30% by weight, commercially available from Nouryon, Chicago, IL.

[0050] XAN is a repulsive expander; SI is a fabric softening additive; ACN is a fabric softening additive; PBN is a wetting agent; 7636 is a crosslinking agent; all were purchased from Huntsman Corp., Salt Lake City, UT.

[0051] C13-methacrylate is a straight-chain C13 alkyl methacrylate, and IBOMA is isobornyl methacrylate, both purchased from Evonik (Essen, Germany) in Duits.

[0052] GLM is glyceryl monomethacrylate; PLE-200 is lauryl methacrylate polyethylene glycol ester; AME-400 is methoxylated polyethylene glycol acrylate; ADE-400A is polyalkylene glycol diacrylate; PE-90 is hydroxyl-terminated polyethylene glycol methacrylate; VMA-70 is behenyl methacrylate; purchased from NOF Corporation, Tokyo, Japan.

[0053] CD9075 is alkoxylated lauryl acrylate purchased from Sartomer, Exton, PA, Pennsylvania.

[0054] TMN-10 is a nonionic surfactant purchased from Dow Chemicals, Midland, MI.

[0055] Chemidex TMS is a cationic surfactant purchased from Lubrizol, Wickliffe, OH, Ohio, USA.

[0056] ACR D208 is a multifunctional acrylate silicone polyether with a molecular weight of 3000. ACRDi-1010 is a bifunctional acrylate silicone polyether; ACR Di-1508 is a linear organosilicon polyether diacrylate with a molecular weight of 1500; ACR Di-2010-D is a difunctional acrylate silicone polyether; MACR Di-1010 is a bifunctional methacrylate silicone polyether. MACR Di-1017 is a bifunctional methacrylate silicone polyether. MACR Di-1508 is a bifunctional methacrylate silicone polyether. MACR D212-CG is a multifunctional methacrylate silicone polyether; MACR D208 is a multifunctional methacrylate silicone polyether; all were commercially available from Siltech Inc. (Siltech, Toronto, Canada).

[0057] The following test methods and materials are used in the embodiments described herein.

[0058] Test methods

[0059] Test Method 1 - Fabric Treatment

[0060] The fabrics treated in this study were 100% khaki cotton twill, available from SDL Atlas Textile Testing Solutions, Rock Hill, South Carolina 29732, USA. The fabrics were treated with aqueous dispersions of various emulsion polymers using a conventional pad-bath (immersion) method. The prepared concentrated dispersions were diluted with deionized water to achieve a pad-bath with 60 g / L of product in the bath. The fabric was immersed in the bath solution, and excess liquid was removed using a wringer. The moisture absorption on the cotton substrate was approximately 95%. "Moisture absorption" is the weight of the emulsion polymer bath solution applied to the fabric based on the dry weight of the fabric. The fabric was cured at approximately 165°C for 3 minutes and then allowed to "rest" for at least 15 hours after treatment and curing.

[0061] Test Method 2 - Spray Test

[0062] Dynamic water repellency of treated substrates is determined according to the American Association of Colorists and Chemists (AATCC) TM-22 standard. Samples are visually scored using a grade of 100, indicating no water penetration or surface adhesion, referencing the published standard. A grade of 90 indicates slight, random adhesion or no wetting; lower values ​​indicate progressively increasing wetting and penetration. The dynamic water repellency test is a rigorous and realistic test of water repellency.

[0063] Test Method 3 - Stain Removal

[0064] This test measures a fabric's ability to remove oil stains. The treated textile is placed on a flat surface. Using a dropper, 5 drops of MAZOLA corn oil or mineral oil (0.2 mL) are placed on the fabric to form 1 drop of oil. A weight (5 Ib, 2.27 kg) is placed on top of the oil drop using a sheet of cellophane to separate the oil drop. The weight is left in place for 60 seconds. After 60 seconds, the weight and cellophane are removed. An initial grade is observed. The textile is rated from 1 to 5 for residual stains, where 1 indicates the largest remaining residual stain and 5 indicates no visible residual stain. The textile sample is then washed for up to 12 minutes using an automatic washing machine with AATCC 1993 standard reference detergent WOB12 or granular detergent (100 g). The textile is then dried for up to 45–50 minutes. The residual stains of the fabric are again evaluated from 1 to 5 as described above. In the following examples, the detergency grade of corn oil is specified by the term "corn oil," and the detergency grade of mineral oil is specified by the term "mineral oil." The term "HW" stands for Home Wash Cycle, and "10HW" means 10 home wash cycles before the final rating is recorded.

[0065] Comparative Example A

[0066] The cotton fabric was tested according to the above test method without any treatment composition.

[0067] Examples 1 to 7

[0068] Weigh the organosilicon monomer (16.35% by weight) in the container. DM18D (0.57 wt%), glacial acetic acid (0.46 wt%), and deionized water (81.73 wt%). The contents were mixed in a mixer at setting 3 for 2 minutes. The mixture was added to a reactor, purged with nitrogen, and heated to 55°C. Under nitrogen protection, the initiator (Vazo) was added. TM56, 0.03 wt% of the total mixture in 0.86 wt% water). The composition was mixed at 70°C for 4 hours. The resulting polymer emulsion was applied to a fabric and tested according to the test methods described above. In Example 4, the composition was applied to a substrate at 100 g / L from a padding bath.

[0069] Examples 8 to 11

[0070] Repeat Example 1, except that... XAN was added to the padding bath at a concentration of 5 g / L.

[0071] Table 1: Performance of Examples 1 to 11 and Comparative Example A

[0072]

[0073]

[0074] Comparative Example B

[0075] Weigh in the container. ACR Di-1508 (16.52 wt%) and deionized water (85.58 wt%) were mixed in a mixer at setting 3 for 2 minutes. The mixture was added to a reactor, purged with nitrogen, and heated to 55°C. Under nitrogen protection, the initiator (Vazo) was added. TM 56,004 wt% of the total mixture in 0.87 wt% water). The composition was mixed at 70°C for 4 hours. The resulting polymer gelled and its properties could not be tested.

[0076] Comparative Example C

[0077] Weigh in the container. ACR Di-1508 (13.14 wt%), 7EO MA (3.29 wt%) DM18D (0.28 wt%), glacial acetic acid (0.23 wt%), and deionized water (82.15 wt%). The contents were mixed in a mixer at setting 3 for 2 minutes. The mixture was added to a reactor, purged with nitrogen, and heated to 55°C. Under nitrogen protection, the initiator (Vazo) was added. TM 56,004 wt% of the total mixture in 0.86 wt% water). The composition was mixed at 70°C for 4 hours. The resulting polymer emulsion was applied to a fabric and tested according to the test method described above.

[0078] Examples 12 to 13

[0079] Comparative Example C was repeated using the quantities listed in Table 2. Example 12 used... S replaces DM18D. The resulting polymer emulsion was applied to the fabric and tested according to the test method described above.

[0080] Table 2: Components of Examples 12 to 13

[0081]

[0082] Examples 14 to 15

[0083] Repeat Examples 12 and 13, except that... XAN was added to the padding bath at a concentration of 5 g / L.

[0084] Table 3: Performance of Examples 12 to 15 and Comparative Example C

[0085]

[0086] Example 16

[0087] Weigh in the container. ACR Di-2010-D (13.08 wt%), 7EO MA (3.27 wt%) DM18D (0.57 wt%), glacial acetic acid (0.46 wt%), and deionized water (81.73 wt%). The contents were mixed in a mixer at setting 3 for 2 minutes. The mixture was added to a reactor, purged with nitrogen, and heated to 55°C. Under nitrogen protection, the initiator (Vazo) was added. TM 56,0.03% by weight of the total mixture in 0.86% by weight of water). The composition was mixed at 70°C for 4 hours. The resulting polymer emulsion was applied to a fabric and tested according to the test method described above.

[0088] Examples 17 to 22

[0089] Example 16 was repeated, except that the following amounts of additives were added to the padding bath.

[0090] Table 4: Performance of Examples 16 to 22

[0091]

[0092] Examples 23 to 25

[0093] Repeat Example 16 using the listed organosilicon monomers.

[0094] Example 26

[0095] Repeat Example 16, using ACR Di-1508 replacement ACR Di-2010-D was used, with hydroxyethyl methacrylate (HEMA) instead of 7EO MA. The resulting polymer emulsion was applied to the fabric and tested according to the above test method.

[0096] Table 5: Performance of Examples 23 to 26

[0097]

[0098] Comparative Example D

[0099] Repeat Example 26, using 16.35% by weight of HEMA and without using ACR Di-1508. The resulting polymer gelled and its properties could not be tested.

[0100] Examples 27 to 35

[0101] Weigh in the container. ACR Di-1508 (4.09 wt%), 7EO MA (4.09 wt%), additional monomers (8.17 wt%) DM18D (0.57 wt%), glacial acetic acid (0.46 wt%), and deionized water (81.73 wt%). The contents were mixed in a mixer at setting 3 for 2 minutes. The mixture was added to a reactor, purged with nitrogen, and heated to 55°C. Under nitrogen protection, the initiator (Vazo) was added. TM 56,0.03% by weight of the total mixture in 0.86% by weight of water). The composition was mixed at 70°C for 4 hours. The resulting polymer emulsion was applied to a fabric and tested according to the test method described above.

[0102] Examples 36 to 38

[0103] Repeat Example 27, except that... XAN was added to the padding bath at a concentration of 5 g / L.

[0104] Table 6: Performance of Examples 27 to 38

[0105]

[0106] Examples 39 to 69 and Comparative Examples E to H

[0107] Example 27 was repeated using the following monomers: DI water (81.71 wt%) and Vazo. TMThe amount of 56 (0.05 wt%) was varied according to the above procedure. The resulting polymer emulsion was applied to the fabric and tested according to the above test method. For Example 69 and Comparative Example H, 0.03 wt% Vazo was used. TM 56.

[0108] Table 7: Components and properties of Examples 39 to 69 and Comparative Examples E to H

[0109]

[0110]

[0111] Examples 70 to 73

[0112] Repeat Example 27, using methyl methacrylate as an additional monomer and using the organosilicon monomers listed below.

[0113] Examples 74 to 75

[0114] Repeat Example 27, using methyl methacrylate as an additional monomer and using ADE-400A replaces 7EO MA. In Example 75, XAN was added to the padding bath at a concentration of 5 g / L.

[0115] Table 8: Performance of Examples 70 to 75

[0116]

[0117] Examples 76 to 77

[0118] Weigh in the container. ACR Di-1508 (4.09 wt%), methyl methacrylate (12.26 wt%) DM18D (0.57 wt%), glacial acetic acid (0.46 wt%), and deionized water (81.73 wt%). The contents were mixed in a mixer at setting 3 for 2 minutes. The mixture was added to a reactor, purged with nitrogen, and heated to 55°C. Under nitrogen protection, the initiator (Vazo) was added. TM 56, 0.03 wt% of the total mixture in 0.86 wt% water). The composition was mixed at 70°C for 4 hours. The resulting polymer emulsion was applied to a fabric and tested according to the test method described above. In Example 77, XAN was added to the padding bath at a concentration of 5 g / L.

[0119] Example 78

[0120] Repeat Example 76, using ACR Di-1010 replacement ACR Di-1508.

[0121] Table 9: Performance of Examples 76 to 78

[0122] Example Spraying level Corn oil grades Mineral oil grade initial initial initial 76 85 2 2.5 77 85 2.5 2.5 78 75 3 3

[0123] Examples 79 to 82

[0124] Example 27 was repeated, using ethylhexyl methacrylate as an additional monomer and replacing 7EO MA with the following monomer. The resulting polymer emulsion was applied to the fabric and tested according to the test methods described above.

[0125] Examples 83 to 84

[0126] Example 79 was repeated, using 4.09% by weight of ethylhexyl methacrylate and 8.17% by weight of the following monomers.

[0127] Table 10: Performance of Examples 79 to 84

[0128]

[0129] Examples 85 to 86

[0130] Repeat Example 16, using ACR Di-1508 replacement ACR Di-2010-D, and using PLE-200 replaces 7EO MA. In Example 86, XAN was added to the padding bath at a concentration of 5 g / L.

[0131] Example 87

[0132] Repeat Example 16, using ACR Di-1010 replacement ACR Di-2010-D, and using The AME-400 replaces the 7EO MA. XAN was added to the padding bath at a concentration of 5 g / L.

[0133] Examples 88 to 89

[0134] Repeat Example 16, using CD9075 instead of 7EO MA. In Example 89, XAN was added to the padding bath at a concentration of 5 g / L.

[0135] Example 90

[0136] Repeat Example 27, using VMA-70 is used as an additional monomer and is employed ACRDi-1010 replacement ACR Di-2010-D.

[0137] Example 91

[0138] Weigh in the container. ACR Di-2010-D (7.84 wt%), dodecyl mercaptan (0.01 wt%), ethylene glycol dimethacrylate (1.96 wt%) DM18D (0.57 wt%), glacial acetic acid (0.46 wt%), and deionized water (81.65 wt%). The contents were mixed in a mixer at setting 3 for 2 minutes. The mixture was added to a reactor, purged with nitrogen, and heated to 55°C. Under nitrogen protection, the initiator (Vazo) was added. TM 56,0.03 wt% of the total mixture in 0.86 wt% water). The composition was mixed at 70°C for 2.5 hours. At this time, a mixture of ethylhexyl methacrylate (3.27 wt%), IBOMA (2.94 wt%), and 7EOMA (0.33 wt%) was added to the reactor over 10 minutes. Additional Vazo was added. TM 56 (0.003 wt% total mixture in 0.09 wt% water). The composition was mixed at 70°C for 4 hours. The resulting polymer emulsion was applied to a fabric and tested according to the above test method.

[0139] Example 92

[0140] Example 91 was repeated, with ethylhexyl methacrylate (6.53 wt%) used in the second stage and IBOMA and 7EOMA omitted.

[0141] Table 11: Performance of Examples 85 to 92

[0142] Example Spraying level Corn oil grades Mineral oil grade initial initial initial 85 60 3.5 3 86 60 3.5 3.5 87 75 2.5 2.5 88 60 3.5 3 89 60 3 3 90 55 3.5 3.5 91 70 2 2 92 75 2 2

[0143] Examples 93 to 95

[0144] Repeat Example 27, using MACR Di-1508 replacement ACR Di-1508 uses the monomers listed in the table below.

[0145] Table 12: Performance of Examples 93 to 95

[0146]

[0147] Examples 96 to 97

[0148] Weigh in the container. MACR D208 (10.99 wt%), 7EO MA (1.21 wt%), hydroxyethyl methacrylate (1.10 wt%), IBOMA (3.05 wt%) DM18D (0.57 wt%), glacial acetic acid (0.46 wt%), and deionized water (81.73 wt%). The contents were mixed in a mixer at setting 3 for 2 minutes. The mixture was added to a reactor, purged with nitrogen, and heated to 55°C. Under nitrogen protection, the initiator (Vazo) was added. TM 56, 0.04 wt% of the total mixture in 0.86 wt% water). The composition was mixed at 70°C for 4 hours. The resulting polymer emulsion was applied to a fabric and tested according to the test method described above. In Example 97, XAN was added to the padding bath at a concentration of 5 g / L.

[0149] Example 98

[0150] Weigh in the container. MACR D208 (11.44 wt%), 7EO MA (3.27 wt%), vinylidene chloride (1.63 wt%) DM18D (0.57 wt%), glacial acetic acid (0.46 wt%), and deionized water (81.72 wt%). The contents were mixed in a mixer at setting 3 for 2 minutes. The mixture was added to a reactor, purged with nitrogen, and heated to 55°C. Under nitrogen protection, the initiator (Vazo) was added. TM 56,0.05% by weight of the total mixture in 0.86% by weight of water). The composition was mixed at 70°C for 4 hours. The resulting polymer emulsion was applied to a fabric and tested according to the test method described above.

[0151] Example 99

[0152] Weigh in the container. MACR D208 (12.07 wt%), HEMA (2.73 wt%), vinylidene chloride (0.82 wt%) TMN-10 (0.43% by weight), DM18D (0.57 wt%), glacial acetic acid (0.46 wt%), and deionized water (82.01 wt%). The contents were mixed in a mixer at setting 3 for 2 minutes. The mixture was added to a reactor, purged with nitrogen, and heated to 55°C. Under nitrogen protection, the initiator (Vazo) was added. TM 56, 0.05 wt% of the total mixture in 0.87 wt% water). The composition was mixed at 70°C for 4 hours. The resulting polymer emulsion was applied to a fabric and tested according to the above test method.

[0153] Example 100

[0154] Weigh in the container. ACR Di-1508 (10.99 wt%), HEMA (1.10 wt%), 7EOMA (1.21 wt%), ethylhexyl methacrylate (3.05 wt%) DM18D (0.57 wt%), glacial acetic acid (0.46 wt%), and deionized water (81.73 wt%). The contents were mixed in a mixer at setting 3 for 2 minutes. The mixture was added to a reactor, purged with nitrogen, and heated to 55°C. Under nitrogen protection, the initiator (Vazo) was added. TM 56,004 wt% of the total mixture in 0.86 wt% water). The composition was mixed at 70°C for 4 hours. The resulting polymer emulsion was applied to a fabric and tested according to the test method described above.

[0155] Example 101

[0156] Weigh in the container. ACR Di-1508 (10.77 wt%), HEMA (1.08 wt%), 7EO MA (1.19 wt%), ethylhexyl methacrylate (2.99 wt%) 16-50 (3.00 wt%) and deionized water (80.09 wt%). The contents were blended in a mixer at setting 3 for 2 minutes. The mixture was added to a reactor, purged with nitrogen, and heated to 55°C. Under nitrogen protection, the initiator (Vazo) was added. TM 56, 0.03 wt% of the total mixture in 0.85 wt% water). The composition was mixed at 70°C for 4 hours. The resulting polymer emulsion was applied to a fabric and tested according to the above test method.

[0157] Example 102

[0158] Repeat Example 16, using MACR D212-CG Replacement ACR Di-2010-D was used, with hydroxyethyl methacrylate (HEMA) instead of 7EO MA. The resulting polymer emulsion was applied to the fabric and tested according to the above test method.

[0159] Example 103

[0160] Repeat Example 102, which uses 16-29 replaces Armeen DM18D. Furthermore, only 0.04% by weight is used. 56. Apply the obtained polymer emulsion to the fabric and test it according to the test method described above.

[0161] Example 104

[0162] Repeat Example 16, using ACR D208 replacement ACR Di-2010-D was used, with hydroxyethyl methacrylate (HEMA) instead of 7EO MA. The resulting polymer emulsion was applied to the fabric and tested according to the above test method.

[0163] Example 105

[0164] Repeat Example 104, which uses Replace Armeen DM18D with 16-29. Apply the resulting polymer emulsion to the fabric and test according to the above test method.

[0165] Table 13: Performance of Examples 96 to 105

[0166]

[0167] Examples 106 to 121

[0168] The products of different embodiments were blended according to the table below. The weight % of each component is based on its solids content. The blended products were then diluted to 20% solids. Except for Examples 112 to 114 and Examples 119 to 121, the following were... XAN was added to the padding bath at a concentration of 5 g / L.

[0169] Table 14: Compositions of Examples 106 to 121

[0170]

[0171]

[0172] Table 15: Performance of Examples 106 to 121

[0173]

Claims

1. A treated substrate comprising a fibrous substrate and a treatment composition applied to the fibrous substrate, wherein the treatment composition comprises: a) 20% to 99.5% by weight of organosilicon polyether polymers, and b) 0.5% to 4% by weight of at least one surfactant, said at least one surfactant being 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 said treated composition; The organosilicon polyether polymer wherein the organosilicon polyether polymer comprises 6% to 100% by weight of repeating units from formula (I) or formula (II) and 0% to 94% by weight of repeating units from olefinic unsaturated comonomers, all based on the total weight of the polymer. (I) (II) in a and b are independent integers from 1 to 40, where a+b is an integer of at least 2; c and d are independent integers from 0 to 20; e is an integer from 1 to 40; X is a straight-chain or branched C1-C4 alkylene group; R 1 It is a C1-C4 alkyl group; and R 2 -C(R) 1 )=CH2 or C(R) 1 The polymer backbone unit bonded at ) - [C(R 1 )-CH2]-; The prerequisite is that if c+d is 0, then the organosilicon polyether polymer has repeating units from at least one olefinic unsaturated comonomer having at least one alkoxylated side group.

2. The treated substrate according to claim 1, wherein the polymer has 10% to 100% by weight of repeating units from formula (I) or formula (II) and 0% to 90% by weight of repeating units from olefinic unsaturated comonomers.

3. The treated substrate according to claim 1, wherein the polymer has 40% to 100% by weight of repeating units from formula (I) or formula (II) and 0% to 60% by weight of repeating units from olefinic unsaturated comonomers.

4. The treated substrate according to claim 1, wherein the polymer has 100% by weight of repeating units from formula (I) or formula (II).

5. The treated substrate according to claim 1, wherein the olefinic 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 treated substrate according to claim 5, wherein the silicone polyether polymer has repeating units copolymerized from: At least one monomer selected from the group consisting of 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 the following: cyclic hydrocarbon (meth)acrylates, straight-chain or branched alkyl (meth)acrylates, vinylidene halides, vinyl halides, vinyl acetate, diacetone (meth)acrylamide, glycidyl (meth)acrylamide, cyclic hydrocarbon (meth)acrylamide, straight-chain or branched alkyl (meth)acrylamide, or mixtures thereof.

7. The treated substrate according to any one of claims 1 to 6, wherein the treated composition further comprises a hydrophobic surface effect agent selected from the group consisting of: fatty acid esters of cyclic or acyclic polyols, fatty acid esters of polycarboxylic acids, hydrophobic non-fluorinated (meth)acrylic polymers, partially fluorinated polyurethanes, hydrophobic non-fluorinated polyurethanes, partially fluorinated (meth)acrylic polymers or copolymers, partially fluorinated (meth)acrylamide polymers or copolymers, fluorinated phosphate esters, fluorinated ethoxylates, fluorinated or non-fluorinated organosilanes, organosilicones, waxes including paraffin, and mixtures thereof.

8. The treated substrate according to any one of claims 1 to 6, wherein the treatment composition is non-fluorinated.

9. The treated substrate according to claim 7, wherein the treated composition comprises a) 20% to 95% by weight of an organosilicon polyether polymer, b) 0.5% to 4% by weight of at least one surfactant, and c) 1% to 79.5% by weight of a hydrophobic surface effect agent, all based on the total dry weight of the treated composition.

10. A method of providing a surface effect to a substrate, the method comprising contacting a treatment composition with a fibrous substrate, wherein the treatment composition comprises: a) 20% to 99.5% by weight of organosilicon polyether polymers, and b) 0.5% to 4% by weight of at least one surfactant, said at least one surfactant being 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 said treated composition; The organosilicon polyether polymer wherein the organosilicon polyether polymer comprises 6% to 100% by weight of repeating units from formula (I) or formula (II) and 0% to 94% by weight of repeating units from olefinic unsaturated comonomers, all based on the total weight of the polymer. (I) (II) in a and b are independent integers from 1 to 40, where a+b is an integer of at least 2; c and d are independent integers from 0 to 20; e is an integer from 1 to 40; X is a straight-chain or branched C1-C4 alkylene group; R 1 It is a C1-C4 alkyl group; and R 2 -C(R) 1 )=CH2 or C(R) 1 The polymer backbone unit bonded at ) - [C(R 1 )-CH2]-; The prerequisite is that if c+d is 0, then the organosilicon polyether polymer has repeating units from at least one olefinic unsaturated comonomer having at least one alkoxylated side group.

11. The method according to claim 10, wherein the polymer has 10% to 100% by weight of repeating units from formula (I) or formula (II) and 0% to 90% by weight of repeating units from olefinic unsaturated comonomers.

12. The method of claim 10, wherein the polymer has 40% to 100% by weight of repeating units from formula (I) or formula (II) and 0% to 60% by weight of repeating units from olefinic unsaturated comonomers.

13. The method of claim 10, wherein the polymer has 100% by weight of repeating units from formula (I) or formula (II).

14. The method according to claim 10, wherein the olefinic 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 method of claim 14, wherein the organosilicon polyether polymer has repeating units copolymerized from: At least one monomer selected from the group consisting of 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 the following: cyclic hydrocarbon (meth)acrylates, straight-chain or branched alkyl (meth)acrylates, vinylidene halides, vinyl halides, vinyl acetate, diacetone (meth)acrylamide, glycidyl (meth)acrylamide, cyclic hydrocarbon (meth)acrylamide, straight-chain or branched alkyl (meth)acrylamide, or mixtures thereof.

16. The method according to any one of claims 10 to 15, wherein the treatment composition further comprises fatty acid esters of cyclic or acyclic polyols, fatty acid esters of polycarboxylic acids, hydrophobic nonfluorinated (meth)acrylic polymers, partially fluorinated polyurethanes, hydrophobic nonfluorinated polyurethanes, partially fluorinated (meth)acrylic polymers or copolymers, partially fluorinated (meth)acrylamide polymers or copolymers, fluorinated phosphate esters, fluorinated ethoxylates, fluorinated or nonfluorinated organosilanes, organosilicones, waxes including paraffin, and mixtures thereof.

17. The method according to any one of claims 10 to 15, wherein the treatment composition is non-fluorinated.

18. The method according to any one of claims 10 to 15, wherein the contact step is performed by padding or spraying.

19. The method according to any one of claims 10 to 15, wherein the contact step is performed by dyeing, rolling, twisting, winch, tumbling, or coating.

20. The method according to any one of claims 10 to 15, wherein the contacting step is performed by interlocking, wetting rollers, or dip-extrusion.

21. The method according to any one of claims 10 to 15, wherein the contacting step is performed by brushing, dripping, impregnation, or rolling.

22. The method according to any one of claims 10 to 15, wherein the contact step is performed by liquid injection or overflow.

23. The method according to any one of claims 10 to 15, wherein the contact step is performed by foaming, powder coating or screen printing.

24. The method according to any one of claims 10 to 15, wherein the contact step is performed inside the washing machine.

25. The method according to any one of claims 10 to 15, wherein the treatment composition comprises a) 20% to 95% by weight of an organosilicon polyether polymer, b) 0.5% to 4% by weight of at least one surfactant, and c) 1% to 79.5% by weight of a hydrophobic surface effect agent, all based on the total dry weight of the treatment composition.

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