EP3356594A1

EP3356594A1 - Carpet with hydrophobic surface finish

Info

Publication number: EP3356594A1
Application number: EP16781628.9A
Authority: EP
Inventors: Gerald Oronde Brown; John Christopher Sworen; Edward Patick CAREY
Original assignee: Chemours Co FC LLC
Current assignee: Chemours Co FC LLC
Priority date: 2015-10-02
Filing date: 2016-09-30
Publication date: 2018-08-08
Also published as: AU2016330913A1; US20180320309A1; WO2017059156A1

Abstract

The present invention relates to a treated carpet comprising a partial or complete coating on a carpet surface, wherein the coating comprises 5 to 100% by weight of a hydrophobic compound, based on the total weight of the coating, selected from a cyclic or acyclic alcohol which is substituted with at least two hydrophobic groups.

Description

TITLE OF INVENTION

CARPET WITH HYDROPHOBIC SURFACE FINISH FIELD OF THE INVENTION

Hydrophobic substituted alcohols are employed in surface finish coatings to provide surface effects to carpet articles.

BACKGROUND OF THE INVENTION

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

Fluorinated polymer compositions having utility as fibrous substrate treating agents generally contain pendant perfluoroalkyi groups of three or more carbon atoms, which provide oil- and water-repellency when the compositions are applied to fibrous substrate surfaces. The perfluoroalkyi groups are generally attached by various connecting groups to

polymerizable groups not containing fluorine. The resulting monomer is then generally copolymerized with other monomers which confer additional favorable properties to the substrates. Various specialized monomers may be incorporated to impart improved cross-linking, latex stability and substantivity. Since each ingredient may impart some potentially undesirable properties in addition to its desirable ones, the specific combination is directed to the desired use. These polymers are generally marketed as aqueous emulsions for easy application to the fibrous substrates.

Various attempts have been made to increase the oil- and water- repellency imparted to the substrate and its durability while reducing the amount of fluorinated polymer required, i.e., boost the efficiency or performance of the treating agent. One method is to incorporate blocked isocyanates or melamine resins. However, only limited amounts can be used because these ingredients tend to adversely affect the handle (the feel) of the fibrous substrate. Another approach employs use of various extender polymers. These are typically hydrocarbon polymers in aqueous emulsions, which are blended with the fluorinated polymer emulsion before application to the substrate.

US Patent 7,820,745 discloses aqueous water- and oil-repellent compositions containing a fluorinated copolymer in aqueous medium and a sorbitan ester used in small amounts to act as a surfactant. The reference does not, however, show the surface effect benefits of using hydrophobic sorbitan esters or other hydrophobic ester alcohol

compounds on carpet substrates.

BRIEF SUMMARY OF THE INVENTION

There is a need for surface effect compositions which provide hydrophobicity performance to carpet with improved fluorine efficiency. The present invention provides such a composition.

The present invention comprises a treated carpet comprising a partial or complete coating on a carpet surface, wherein the carpet is made of natural fibers, nylon, acrylics, aromatic polyamides, polyesters, polyacrylonitrile, or polyacrylonitrile copolymers, wherein the coating comprises 5 to 100% by weight of a hydrophobic compound, based on the total solids weight of the coating, selected from a cyclic or acyclic alcohol which is substituted with at least two -R¹, -C(O)R¹ , -

(CH2CH2O)n(CH(CH3)CH₂O)mR², -(CH2CH2O)n(CH(CH3)CH₂O)mC(O)R¹ , or mixtures thereof; where the cyclic or acyclic alcohol is selected from a pentaerythritol, a saccharide, reduced sugar, aminosaccharide, citric acid, aldonic acid, or aldonic acid lactone; wherein each n is independently 0 to 20; each m is independently 0 to 20; m+n is greater than 0; each R¹ is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond; and each R² is independently -H, a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond.

The present invention further comprises a method of imparting a surface effect to a carpet comprising contacting a carpet surface with a coating to form a partially or completely treated carpet, wherein the carpet is made of natural fibers, nylon, acrylics, aromatic polyamides, polyesters, polyacrylonitrile, or polyacrylonitrile copolymers, wherein the coating comprises 5 to 100% by weight of a hydrophobic compound, based on the total solids weight of the coating, selected from a cyclic or acyclic alcohol which is substituted with at least two -R¹, -C(0)R¹ , - (CH2CH20)n(CH(CH3)CH₂0)mR², -(CH2CH20)n(CH(CH3)CH₂0)mC(0)R¹ , or mixtures thereof; where the cyclic or acyclic alcohol is selected from a pentaerythritol, saccharide, reduced sugar, aminosaccharide, citric acid, aldonic acid, or aldonic acid lactone; wherein each n is independently 0 to 20; each m is independently 0 to 20; m+n is greater than 0; each R¹ is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond; each R² is

independently -H, a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond.

DETAILED DESCRIPTION OF THE INVENTION

Trademarks are indicated herein by capitalization.

The present invention provides treated carpet articles having improved water repellency, oil or stain repellency, and/or other surface effects. The treated articles provide enhanced performance compared to traditional non-fluorinated commercially available treatment agents. The coating materials of the present invention can be derived from bio-sourced materials. The coatings formed are durable, by which is meant that the coatings are lasting films that are not readily removed by water or cleaning agents. In one aspect, the coatings are not soluble or dispersable in water or cleaning agents once they are dry, and in another aspect, the coatings withstand multiple cleanings without loss of performance.

The present invention comprises a treated carpet comprising a partial or complete coating on a carpet surface, wherein the carpet is made of natural fibers, nylon, acrylics, aromatic polyamides, polyesters, polyacrylonitrile, or polyacrylonitrile copolymers, wherein the coating comprises 5 to 100% by weight of a hydrophobic compound, based on the total solids weight of the coating, selected from a cyclic or acyclic alcohol which is substituted with at least two -R¹, -C(O)R¹ , - (CH2CH2O)n(CH(CH3)CH₂O)mR², -(CH2CH2O)n(CH(CH3)CH₂O)mC(O)R¹ , or mixtures thereof; where the cyclic or acyclic alcohol is selected from a pentaerythritol, a saccharide, reduced sugar, aminosaccharide, citric acid, aldonic acid, or aldonic acid lactone; wherein each n is independently 0 to 20; each m is independently 0 to 20; m+n is greater than 0; each R¹ is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond; and each R² is independently -H, a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond. These hydrophobic compounds can contain only EO groups, only PO groups, or mixtures thereof. These compounds can also be present as a tri-block copolymer designated PEG-PPG-PEG (polyethylene glycol-polypropylene glycol- polyethylene glycol), for example. In one embodiment, n+m is 1 to 20; in another embodiment, n and m are independently 0 to 15 and n+m is 1 to 15; and in a third embodiment, n and m are independently 0 to 12 and n+m is 1 to 12.

The hydrophobic compound may be a multi-ester alcohol having at least two hydrophobic substitutions, which originates from a polyol or polycarboxylic acid compound. Examples of suitable polyols include but are not limited to cyclic or acyclic sugar alcohols, or pentaerythritols including dipentaerythritol. Suitable polycarboxylic acid compounds include citric acid. The cyclic or acyclic sugar alcohol is selected from a saccharide, reduced sugar, aminosaccharide, aldonic acid, aldonic acid lactone. Mixtures of these compounds may also be used. The

hydrophobic compounds are substituted with at least two -R¹ ; -C(0)R¹; -(CH2CH20)n(CH(CH3)CH₂0)mR²; -(CH2CH20)n(CH(CH3)CH₂0)mC(0)R¹; or mixtures thereof. Such a substitution lends hydrophobic character to the monomer, and to the polymer molecules. In one embodiment, the hydrophobic compound is substituted with at least three -R¹ ; -C(0)R¹ ; - (CH2CH20)n(CH(CH3)CH₂0)mR²; -(CH2CH20)n(CH(CH3)CH₂0)mC(0)R¹ ; or mixtures thereof.

These substituted compounds can be made by the reaction of a sugar alcohol with at least one fatty acid or alkoxylated fatty acid, such as by esterification of a fatty acid; or by esterification of a polycarboxylic acid with a long-chain alcohol. Examples of such sugar alcohols include but are not limited to aldoses and ketoses such as those compounds derived from tetroses, pentoses, hexoses, and heptoses. Specific examples include glucose, 1 ,4-anhydro-D-glucitol, 2,5-anhydro-D-mannitol, 2,5- anhydro-L-iditol, isosorbide, sorbitan, glyceraldehyde, erythrose, threitol, glucopyranose, mannopyranose, talopyranose, allopyranose,

altropyranose, idopyranose, gulopyranose, glucitol, mannitol, erythritol, sorbitol, arabitol, xylitol, ribitol, galactitol, fucitol, iditol, inositol,

pentaerythritol, dipentaerythritol, volemitol, gluconic acid, glyceric acid, xylonic acid, galactaric acid, ascorbic acid, citric acid, gluconic acid lactone, glyceric acid lactone, xylonic acid lactone, glucosamine, galactosamine, or mixtures thereof.

Suitable fatty acids include, but are not limited to, caprylic acid, capric acid, lauric acid, mysteric acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, palmitoleic acid, lineolic acid, oleic acid, erucic acid, alkoxylated versions of these acids, and mixtures thereof.

In one embodiment, R¹ is a linear or branched alkyl group having 1 1 to 29 carbons, and in another embodiment, R¹ is a linear or branched alkyl group having 17 to 21 carbons. In one embodiment, R² is a linear or branched alkyl group having 12 to 30 carbons, in another embodiment, R² is a linear or branched alkyl group having 18 to 30 carbons, and in another embodiment, R² is a linear or branched alkyl group having 18 to 22 carbons. In one embodiment, the fatty acid or long-chain alcohol substitution of the cyclic or acyclic sugar alcohols has a melting point of at least -59 °C. In another embodiment, it has a melting point of at least 0 °C, and in a third embodiment, it has a melting point of at least 40 °C.

In one embodiment, the hydrophobic compound is selected from Formulas (la), (lb), or (lc):

wherein each R is independently -H; -R¹ ; -C(0)R¹;

-(CH2CH20)n(CH(CH3)CH₂0)mR²; or

-(CH2CH20)n(CH(CH3)CH₂0)mC(0)R¹ ; each n is independently 0 to 20; each m is independently 0 to 20; m+n is greater than 0; r is 1 to 3; a is 0 or 1 ; p is independently 0 to 2; provided that a is 0 when r is 3; each R¹ is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond; each R² is

independently -H, or a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond; provided when Formula (la) is chosen, then at least one R is -H and at least one R is a - R¹ ; -C(0)R¹; -(CH₂CH20)n(CH(CH3)CH₂0)mR²;

or -(CH₂CH₂0)n(CH(CH₃)CH₂0)mC(0)R¹; each R⁴ is independently -H, a linear or branched alkyl group having 6 to 30 carbons optionally

comprising at least 1 unsaturated bond, or combinations thereof;

-(CH2CH20)n(CH(CH3)CH₂0)mR²; or

-(CH2CH20)n(CH(CH3)CH₂0)mC(0)R¹ ; provided when Formula (lb) is chosen, then at least one R or R⁴ is -H; and at least two of R or R⁴ are a linear or branched alkyl group optionally comprising at least 1 unsaturated bond, or combinations thereof; -(CH₂CH20)n(CH(CH3)CH₂0)mR²;

or -(CH₂CH₂0)n(CH(CH₃)CH₂0)mC(0)R¹ ; and each R¹⁹ is -H, -C(0)R¹ , or

-CH₂C[CH₂OR]3, provided when Formula (lc) is chosen, then at least one R¹⁹ or R is -H; and at least two of R¹⁹ or R are -C(0)R¹ ,

-(CH₂CH₂0)n(CH(CH₃)CH₂0)mR²; or

-(CH₂CH₂0)n(CH(CH₃)CH₂0)mC(0)R¹.

Where the hydrophobic compound is Formula (la), any suitable substituted reduced sugar alcohol may be employed, including esters of 1 ,4-sorbitan, esters of 2,5-sorbitan, and esters of 3,6-sorbitan. In one embodiment, the hydrophobic compound is selected from Formula (a) to be Formula '):

wherein R is further limited to -H; -R¹ ; or -C(0)R¹ and at least two R groups are -C(0)R¹ or R¹. Compounds used to form residues of Formula (la'), having at least one of R is -H and at least one R is selected from - C(0)R¹, are commonly known as alkyl sorbitans. These sorbitans can be di-substituted or tri-substituted with -C(0)R¹. It is known that commercially available sorbitans, such as SPAN, contain a mixture of the various sorbitans ranging from where each R is H (un-substituted), and sorbitans where each R is -C(0)R¹ (fully substituted); wherein R¹ is a linear or branched alkyl group having 5 to 29 carbons; and mixtures of various substitutions thereof. The commercially available sorbitans may also include amounts of sorbitol, isosorbide, or other intermediates or byproducts.

In one embodiment, at least two R groups are -C(0)R¹ , and R¹ is a linear branched alkyl group having 5 to 29 carbons. In another embodiment, R¹ is a linear or branched alkyl group having 7 to 21 carbons, and in a third embodiment, R¹ is a linear or branched alkyl group having 1 1 to 21 carbons. Preferred compounds used to form these residues include mono-, di- and tri-substituted sorbitans derived from caprylic acid, capric acid, lauric acid, mysteric acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, and mixtures thereof. Particularly preferred compounds include di- and tri-substituted sorbitan stearates or sorbitan behenins.

Optionally, R¹ is a linear or branched alkyl group having 5 to 29 carbons comprising at least 1 unsaturated bond. Examples of

compounds of Formula (la) wherein at least two R groups are selected from -C(O)R¹ ; and R¹ contains least 1 unsaturated bond, include, but are not limited to, sorbitan trioleate (i.e., wherein R¹ is -C7Hi₄CH=CHC8Hi7). Other examples but are not limited to include di- and tri-substituted sorbitans derived from palmitoleic acid, lineolic acid, arachidonic acid, and erucic acid.

In one embodiment, a compound of Formula (la) is employed, wherein at least two R groups are independently

-(CH2CH2O)n(CH(CH3)CH₂O)mR² or

-(CH2CH2O)n(CH(CH3)CH₂O)mC(O)R¹. Compounds of Formula (la), wherein at least two R groups are -(CH₂CH2O)n(CH(CH3)CH₂O)mR² or -(CH₂CH₂O)n(CH(CH₃)CH₂O)mC(O)R¹ , wherein each m is

independently 0 to 20, each n is independently 0 to 20, and n+m is greater than 0 are known as polysorbates and are commercially available under the tradename TWEEN. These polysorbates can be di- substituted or tri-substituted with alkyl groups R¹ or R². It is known that commercially available polysorbates contain a mixture of the various polysorbates ranging from where each R² is H (unsubsituted), and polysorbates where each R¹ is a linear or branched alkyl group having 5 to 29 carbons (fully substituted); and mixtures of various substitutions thereof. Examples of compounds of Formula (la) include polysorbates such as polysorbate tristearate and polysorbate monostearate.

Examples of compounds of Formula (la) wherein m+n is greater than 0, and wherein R¹ comprises at least 1 unsaturated bond, but not limited to, polysorbate trioleate (wherein R¹ is and are sold commercially under the name Polysorbate 80. Reagents may include mixtures of compounds having various values for R, R¹, and R², and may also include mixtures of compounds where R¹ comprises at least one unsaturated bond with compounds where R¹ is fully saturated.

Compounds of Formula (lb) are known as alkyl citrates. These citrates can be present as a di-substituted or tri-substituted with alkyl groups. It is known that commercially available citrates contain a mixture of the various citrates as well as citric acids from where R and each R⁴ is -H, ranging to citrates where each R⁴ is a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond; and mixtures of various substitutions thereof. Mixtures of citrates having various values for R¹ , R², and R⁴ may be used, and may also include mixtures of compounds where R¹ comprises at least one unsaturated bond with compounds where R¹ is fully saturated. Alkyl citrates are also commercially available wherein m+n is greater than 0, R⁴ is -(CH2CH20)n(CH(CH3)CH₂0)mR²; or

-(CH₂CH20)n(CH(CH3)CH₂0)mC(0)R¹ and are present in the various substitutions from wherein R and each R² is H to wherein each R¹ and/or R² is a linear or branched alkyl group having 5 to 30 carbons optionally comprising at least 1 unsaturated bond. Examples of compounds of Formula (lb) include, but are not limited to, trialkyl citrates.

Compounds of Formula (lc) are known as pentaerythriol esters. These pentaerythriol esters can be present as a di-substituted or tri- substituted with alkyl groups. Preferred compounds used to form X of Formula (lc) are dipentaerythriol esters, where R¹⁹ is -CH2C[CH20R]3. It is known that commercially available pentaerythriol esters contain a mixture of the various pentaerythriol esters where R¹⁹ and each R is -H, ranging to pentaerythriol esters where each R is -C(0)R¹, and R¹ is a linear or branched alkyl group having 5 to 29 carbons optionally

comprising at least 1 unsaturated bond; and mixtures of various

substitutions thereof. The pentaerythriol esters also may contain compounds with mixtures of different chain lengths for R, or mixtures of compounds where R¹ comprises at least one unsaturated bond with compounds where R¹ is fully saturated.

Compounds of Formulas (la), (lb), and (lc) can all be bio-based derived. By "bio-based derived", it is meant that at least 10% of the material can be produced from non-crude oil sources, such as plants, other vegetation, and tallow. In one embodiment, the hydrophobic compound is from about 10% to 100% bio-based derived. In one embodiment, hydrophobic compound is from about 35% to 100% bio- based derived. In another embodiment, hydrophobic compound is from about 50% to 100% bio-based derived. In one embodiment, hydrophobic compound is from about 75% to 100% bio-based derived. In one embodiment, hydrophobic compound is 100% bio-based derived. The average OH value of the hydrophobic compounds can range from just greater than 0 to about 230. In one embodiment, the average OH value is from about 10 to about 175, and in another embodiment, the average OH value is from about 25 to about 140.

The coating on the carpet surface comprises 5 to 100% by weight of the hydrophobic compound, based on the total solids weight of the coating. In a second aspect, the coating on the carpet surface comprises 20 to 100% by weight of the hydrophobic compound; and in a third aspect, 50 to 100% by weight of the hydrophobic compound based on the total solids weight of the coating. The term "solids weight of the coating", is used to mean the sum of the coating components that would remain once the aqueous, solvent, or other liquid components evaporated. In other words, it is the sum of the non-aqueous, non-solvent, and non-volatile components of the coating. The coating may further comprise aqueous or organic solvents, polymer resins, coating bases that contain polymer resins, pigments, functional additives, surfactants, and hydrophobic surface effect agents.

In one embodiment, the hydrophobic compound is combined with a hydrophobic surface effect agent to extend or improve the performance of the surface effect agent. In this case, the hydrophobic surface effect agents may be used from about 5:95 to about 95:5 in one aspect; from about 10:90 to 90: 10 in a second aspect; and from about 20:80 to 80: 10 in a third aspect, based on the total solids weight of the coating.

Hydrophobic surface effect agents provide surface effects such as no iron, easy to iron, shrinkage control, wrinkle free, permanent press, moisture control, softness, strength, anti-slip, anti-static, anti-snag, anti-pill, stain repellency, stain release, soil repellency, soil release, water repellency, oil repellency, odor control, antimicrobial, sun protection, and similar effects. Such materials can be in the form of hydrophobic non-fluorinated cationic acrylic polymers, hydrophobic non-fluorinated anionic acrylic polymers, hydrophobic non-fluorinated nonionic acrylic polymers, partially fluorinated urethanes, hydrophobic non-fluorinated urethanes, cationic partially fluorinated acrylic polymers or copolymers, nonionic partially fluorinated acrylic polymers or copolymers, partially fluorinated acrylamide polymers or copolymers, fluorinated phosphates, fluorinated or non-fluorinated organosilanes, silicones, waxes, including parafins, and mixtures thereof. Some stain release and soil release agents are hydrophilic and include compounds such as polymethyl acrylates. These compounds may also be combined with the hydrophobic compounds, in the ratios stated above, as surface effect agents.

Superior properties, along with desirable properties of low yellowing and good durability, are imparted to articles by the combination of the hydrophobic compounds to hydrophobic surface effect agents before application to the articles. These combined blends are applied to the articles in the form of a dispersion in water or other solvent either before, after or during the application of other treatment chemicals.

Of particular interest are fluorinated polymers useful as hydrophobic surface effect agents to provide repellency properties to the surface of treated substrates. These include fluorochemical compounds or polymers containing one or more fluoroaliphatic groups (designated here as Rf groups) which are fluorinated, stable, inert, and non-polar, preferably saturated, monovalent, and both oleophobic and hydrophobic. The Rf groups contain at least 3 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably about 4 to about 6 carbon atoms. The Rf groups may contain straight or branched chain or cyclic fluorinated alkylene groups or combinations thereof. The terminal portion of the Rf groups is preferably a perfluorinated aliphatic group of the formula CnF2n+i wherein n is from about 3 to about 20.

Examples of fluorinated polymer treating agents are CAPSTONE and ZONYL available from The Chemours Company, Wilmington, DE; ASAHI GARD from Asahi Glass Company, Ltd., Tokyo, Japan; UNIDYNE from Daikin America, Inc., Orangeburg, NY; SCOTCHGARD from 3M

Company, St. Paul, MN; and NANO TEX from Nanotex, Emeryville, CA.

Examples of such fluorinated polymers include Rf-containing polyurethanes and poly(meth)acrylates. Especially preferred are copolymers of fluorochemical (meth)acrylate monomers with a co- polymerizable monovinyl compound or a conjugated diene. The co- polymerizable monovinyl compounds include alkyl (meth)acrylates, vinyl esters of aliphatic acids, styrene and alkyl styrene, vinyl halides, vinylidene halides, alkyl esters, vinyl alkyl ketones, and acrylamides. The conjugated dienes are preferably 1 ,3-butadienes. Representative compounds within the preceding classes include the methyl, propyl, butyl, 2-hydroxypropyl, 2-hydroxyethyl, isoamyl, 2-ethylhexyl, octyl, decyl, lauryl, cetyl, and octadecyl acrylates and methacrylates; vinyl acetate, vinyl propionate, vinyl caprylate, vinyl laurate, vinyl stearate, styrene, alpha methyl styrene, p-methylstyene, vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride, vinylidene chloride, allyl heptanoate, allyl acetate, allyl caprylate, allyl caproate, vinyl methyl ketone, vinyl ethyl ketone, 1 ,3-butadiene, 2- chloro-1 ,3-butadiene, 2,3-dichloro-1 ,3-butadiene, isoprene, N- methylolacrylamide, N-methylolmethacrylamide, glycidyl acrylate, glycidyl methacrylate, amine-terminated (meth)acrylates, and

polyoxy(meth)acrylates.

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

polyoxy(meth)acrylates.

Hydrophobic non-fluorinated urethanes include, for example, urethanes synthesized by reacting an isocyanate compound with the hydrophobic compounds described above as an alcohol reagent. These compounds are described in US2014/0295724 and US2016/0090508. Hydrophobic non-fluorinated nonionic acrylic polymers include, for example, polymers made by polymerizing or copolymerizing an acrylic ester of the hydrophobic compounds described above. Such compounds are described in US2016/0090686.

The coatings of the present invention applied to the carpet surface optionally further comprise a blocked isocyanate to promote durability, added after copolymerization (i.e., as a blended isocyanate). An example of a suitable blocked isocyanate is PHOBOL XAN available from

Huntsman Corp, Salt Lake City, UT. Other commercially available blocked isocyanates are also suitable for use herein. The desirability of adding a blocked isocyanate depends on the particular application for the copolymer. For most of the presently envisioned applications, it does not need to be present to achieve satisfactory cross-linking between chains or bonding to fibers. When added as a blended isocyanate, amounts up to about 20% by weight are added.

The coating composition of the present invention optionally further comprises additional components such as additional treating agents or finishes to achieve additional surface effects, or additives commonly used with such agents or finishes. Such additional components comprise compounds or compositions that provide surface effects such as no iron, easy to iron, shrinkage control, wrinkle free, permanent press, moisture control, softness, strength, anti-slip, anti-static, anti-snag, anti-pill, stain repellency, stain release, soil repellency, soil release, water repellency, oil repellency, odor control, antimicrobial, sun protection, and similar effects. One or more such treating agents or finishes can be combined with the blended composition and applied to the fibrous substrate. Other additives commonly used with such treating agents or finishes may also be present such as surfactants, pH adjusters, cross linkers, wetting agents, and other additives known by those skilled in the art. Further, other extender compositions are optionally included to obtain a combination of benefits.

In one embodiment, the present invention is method of imparting a surface effect to a carpet comprising contacting a carpet surface with a coating to form a partially or completely treated carpet, wherein the carpet is made of natural fibers, nylon, acrylics, aromatic polyamides, polyesters, polyacrylonitrile, or polyacrylonitrile copolymers, wherein the coating comprises 5 to 100% by weight of a hydrophobic compound, based on the total solids weight of the coating, selected from a cyclic or acyclic alcohol which is substituted with at least two -R¹ , -C(O)R¹ , - (CH2CH2O)n(CH(CH3)CH₂O)mR², -(CH2CH2O)n(CH(CH3)CH₂O)mC(O)R¹ , or mixtures thereof; where the cyclic or acyclic alcohol is selected from a pentaerythritol, saccharide, reduced sugar, aminosaccharide, citric acid, aldonic acid, or aldonic acid lactone; wherein each n is independently 0 to 20; each m is independently 0 to 20; m+n is greater than 0; each R¹ is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond; each R² is

independently -H, a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond. Specific representative examples of carpet compositions include but are not limited to natural fibers, such as cotton, wool, silk, jute, sisal, and other cellulosics; nylon including nylon 6, nylon 6,6 and aromatic polyamides; polyesters including poly(ethyleneterephthalate) or poly(trimethyleneterephthalate) such as Triexta; polyacrylonitrile or polyacrylonitrile copolymers. The contacting step may occur by applying the hydrophobic compound as a solid, or by liquid carrier. When applied by liquid carrier, the hydrophobic compound may be in the form of an aqueous solution, aqueous dispersion, organic solvent solution or dispersion, or cosolvent solution or dispersion. The contacting step may occur by any conventional method, including but not limited to spraying, rolling, padding, brushing, sprinkling, dipping, dripping, tumbling, screen printing, or other mechanical means known in the technology to treat fibrous substrates.

In one aspect, the method further comprises the step of heating the partially or completely coated carpet. For example, the hydrophobic agent may be applied alone or in liquid carrier, and the treated carpet may be heated to melt, flow, dry, or otherwise fix the hydrophobic agent onto the carpet surface. The final coating on the carpet surface will be a solidified, lasting, permanent coating. In another aspect, the method further comprises the step of solidifying the coating by drying, cooling, or allowing to cool. In one embodiment, the solid hydrophobic compound is sprinkled onto the carpet surface, and the treated carpet is heated to fix the hydrophobic compound onto the surface. The liquid carrier, if used, may be dried by heating or air drying to allow for evaporation of the liquid carrier, thus leaving a permanent solid coating.

Specifically, the treated carpets of the present invention are useful for providing articles with enhanced surface properties, especially durability of oil- water- and soil-repellency, while reducing or eliminating the amount of fluorinated compounds employed. The repellency property is effective with a variety of other surface effects. TEST METHODS

All solvents and reagents, unless otherwise indicated, were purchased from Sigma-Aldrich, St. Louis, MO, and used directly as supplied. Sorbitan tristearate was obtained from Croda, East Yorkshire, England and DuPont Nutrition & Health, Copenhagen, Denmark.

WITCOLATE WAQE is available from Akzo Nobel, Chicago, IL.

The following tests were employed in evaluating the examples herein.

Test Method 1 - Accelerated Soiling Test

A drum mill (on rollers) was used to tumble synthetic soil onto the carpet. Synthetic soil was prepared as described in AATCC Test Method 123-2000, Section 8. Synthetic soil, 3 g, and 1 liter of clean nylon resin beads (3/16 inch (0.32 - 0.48 cm) diameter ZYTEL 101 nylon resin beads, commercially available from E. I. du Pont de Nemours and Company, Wilmington, De., were placed into a clean, empty canister. The canister lid was closed and sealed and the canister rotated on rollers for 5 minutes. The soil-coated beads were removed from the canister.

Total carpet sample size was 8 χ 24 inch (20.3 χ 60.9 cm). One test item and one control item were tested simultaneously. The carpet pile of all samples was laid in the same direction. Strong adhesive tape was placed on the backside of the carpet pieces to hold them together. The carpet samples were placed in the clean, empty drum mill with the tufts facing toward the center of the drum. The carpet was held in place in the drum mill with rigid wires. Soil-coated resin beads, 250 ml, and 250 ml of 5/16 in. diameter ball bearings (0.79 cm.), prepared as described above, were placed into the drum mill. The drum mill lid was closed and sealed. The drum was run on the rollers for 2½ minutes at about 105 rpm. The rollers were stopped and the direction of the drum mill reversed. The drum was run on the rollers for an additional 2½ minutes at about 105 rpm. The carpet samples were removed and vacuumed uniformly with 5 passes in each direction to remove excess dirt. The Delta (Δ) E color difference for the soiled carpet was measured for the test and control items versus the unsoiled carpet for each item. Color measurement of each carpet was conducted on the carpet following the accelerated soiling test. For each test sample and control sample the color of the carpet was measured, the sample was soiled, and the color of the soiled carpet was measured. The Δ E was the difference between the color of the soiled and unsoiled samples. Color difference was measured on each item, using a Minolta Chroma Meter CR 410 (Minolta Corporation, Ramsey, NJ). Color readings were taken at three different areas on the carpet sample, and the average ΔΕ was recorded. The control carpet for each test item was of the same color and

construction as the test item.

Δ Δ E was calculated by subtracting the Δ E of the control

(untreated) carpet from the Δ E of the test item. A larger negative value for Δ Δ E indicated that the test carpet had better performance and less soiling than the control. A larger positive value for Δ Δ E indicated that the test carpet had poorer performance and soiled more than the control.

Note that, although different untreated samples may yield slightly different L ratings, the test samples are compared to the untreated control sample that is tested simultaneously with the test sample.

Test Method 2 - Oil Repellency

Oil repellency was measured according to AATCC Test Method

1 18. Higher values indicate increased oil repellency.

The treated samples were tested for oil repellency by a modification of AATCC standard Test Method No. 1 18, conducted as follows. A substrate treated with an aqueous dispersion of polymer as previously described, is conditioned for a minimum of 2 hours at 23C and 20% relative humidity and 65C and 10% relative humidity. A series of organic liquids, identified below in Table 1 , are then applied dropwise to the samples. Beginning with the lowest numbered test liquid (Repellency Rating No. 1 ), one drop (approximately 5 mm in diameter or 0.05 ml_ volume) is placed on each of three locations at least 5 mm apart. The drops are observed for 30 seconds. If, at the end of this period, two of the three drops are still spherical in shape with no wicking around the drops, three drops of the next highest numbered liquid are placed on adjacent sites and similarly observed for 30 seconds. The procedure is continued until one of the test liquids results in two of the three drops failing to remain spherical to hemispherical, or wetting or wicking occurs.

The oil repellency rating is the highest numbered test liquid for which two of the three drops remained spherical to hemispherical, with no wicking for 30 seconds. In general, treated samples with a rating of 5 or more are considered good to excellent; samples having a rating of one or greater can be used in certain applications.

Table 1 . Oil Repellency Test Liquids

Note: NUJOL is a trademark of Plough, Inc., for a mineral oil having a Saybolt viscosity of 360/390 at 38C and a specific gravity of 0.880/0.900 at 15C.

Test Method 3 - Water Repellency

The water repellency of a treated substrate was measured according to AATCC standard Test Method No. 193 and the DuPont Technical Laboratory Method as outlined in the TEFLON Global

Specifications and Quality Control Tests information packet. The test determines the resistance of a treated substrate to wetting by aqueous liquids. Drops of water-alcohol mixtures of varying surface tensions are placed on the substrate and the extent of surface wetting is determined visually. Place a test carpet sample on a flat, non-absorbent surface. Beginning with the lowest numbered test liquid, carefully place one drop in several locations on the surface of the carpet sample. If no penetration or wetting of the carpet at the liquid-carpet interface and no wicking around the drop occurs, place drops of the next higher-numbered test liquid at an adjacent site on the carpet sample. Repeat this procedure until one of the higher number test liquids shows obvious wetting or wicking of the carpet under or around the drop within 10 seconds. The water repellency rating for a carpet sample is the numerical value of the highest-numbered test liquid which will not wet the carpet within 10 seconds. Higher ratings indicate greater repellency. The composition of water repellency test liquids is shown in Table 2.

Table 2. Water Repellency Test Liquids

EXAMPLES

Example 1

Sorbitan tristearate, as a dry powder, is spread evenly over a commercial level loop nylon-6,6 carpet with stain resist to uniformly cover the carpet surface. Excess powder is removed by shaking the carpet until only a fine powder coating remained. The treated carpet is heated to 250 °F (121 °C) until the surface temperature reaches 250 °F, cooled to room temperature, allowed to equilibrate at room temperature for 24-48 hours, and the carpet sample is tested according to Test Methods 1 -3.

Comparative Example A

An untreated sample of commercial level loop nylon-6,6 carpet with stain resist is tested according to Test Methods 1 -3.

Example 2

Into a 4-neck round bottom flask equipped with an overhead stirrer, thermocouple and condenser is added sorbitan tristearate (60.1 g) and 4- methyl-2-pentanone (MIBK, 150 g). After the solution is heated to 55 °C, an aqueous dispersion is prepared by adding warm water (383 g), WITCOLATE WAQE (1 1.4 g) and dipropylene glycol (14.8 g) at 65 °C. The mixture is immersion blended (2 min), homogenized at 6000 psi, and the resulting dispersion is distilled under reduced pressure to remove the solvent and yield a non-flammable urethane dispersion at 12.91 % solids after cooling and filtering. The sample is applied as an aqueous composition by spray application to a level loop nylon-6,6 carpet with stain resist at 25 % wet pick-up (wpu) and dried to a carpet face temperature of 250 °F (121 °C). The treated carpet is tested according to Test Methods 1 -3.

Table 3. Performance on Level Loop Nylon Carpet Samples

Results indicate that the carpet treated by sorbitan tristearate compounds yields high water repellency performance when compared with an untreated sample. Further, Example 1 indicates that dry applications promote soil resistance in addition to water repellency.

Example 3

Example 1 was repeated, except a commercial SORONA carpet was used.

Table 4. Performance on SORONA Carpet

Results indicate that the carpet treated by sorbitan tristearate compounds yields water repellency performance and high soil resistance performance when compared with an untreated sample.

Claims

What is claimed is: 1 . A treated carpet comprising a partial or complete coating on a carpet surface,

wherein the carpet is made of natural fiber, nylon, acrylic, aromatic polyamide, polyester, polyacrylonitrile, or polyacrylonitrile copolymer,

wherein the coating comprises 5 to 100% by weight of a

hydrophobic compound, based on the total solids weight of the coating, selected from a cyclic or acyclic alcohol which is substituted with at least two -R¹ , -C(0)R¹ , -(CH2CH20)n(CH(CH3)CH₂0)mR², - (CH2CH20)n(CH(CH3)CH₂0)mC(0)R¹ , or mixtures thereof;

where the cyclic or acyclic alcohol is selected from a pentaerythritol, a saccharide, reduced sugar, aminosaccharide, citric acid, aldonic acid, or aldonic acid lactone; wherein

each n is independently 0 to 20;

each m is independently 0 to 20;

m+n is greater than 0;

each R¹ is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond; and

each R² is independently -H, a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond.

2. The treated carpet of claim 1 , where the hydrophobic compound is selected from Formulas (la), (lb), or (lc):

wherein each R is independently -H; -R¹ ; -C(0)R¹ ;

-(CH2CH20)n(CH(CH3)CH₂0)mR²; or

-(CH2CH20)n(CH(CH3)CH₂0)mC(0)R¹ ;

each n is independently 0 to 20;

each m is independently 0 to 20;

m+n is greater than 0;

r is 1 to 3;

a is 0 or 1 ;

p is independently 0 to 2;

provided that a is 0 when r is 3;

each R¹ is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond;

each R² is independently -H, or a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond; provided when Formula (la) is chosen, then at least one R is -H and at least two R groups are a -R¹ ; - C(0)R¹ ; -(CH2CH20)n(CH(CH3)CH₂0)mR²;

or -(CH2CH20)n(CH(CH3)CH₂0)mC(0)R¹ ; each R⁴ is independently -H, a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond, or combinations thereof; -(CH2CH20)n(CH(CH₃)CH20)_mR²;

or -(CH2CH20)n(CH(CH3)CH₂0)mC(0)R¹ ;

provided when Formula (lb) is chosen, then at least one R or R⁴ is - H; and at least two of R or R⁴ are a linear or branched alkyl group optionally comprising at least 1 unsaturated bond, or combinations thereof; -(CH2CH20)n(CH(CH3)CH₂0)mR²;

or -(CH2CH20)n(CH(CH3)CH₂0)mC(0)R¹ ; and

each R¹⁹ is -H, -C(0)R¹ , or -CH₂C[CH₂OR]3,

provided when Formula (lc) is chosen, then at least one R¹⁹ or R is -H; and at least two of R¹⁹ or R are -C(0)R¹ ,

-(CH2CH20)n(CH(CH3)CH₂0)mR²; or

-(CH2CH20)n(CH(CH3)CH₂0)mC(0)R¹.

3. The treated carpet of claim 2, where the hydrophobic compound is selected from Formula (la) to be Formula (la'):

wherein R is further limited to independently -H; -R¹ ; or -C(0)R¹.

4. The treated carpet of claim 2, where the hydrophobic pound is selected from Formula (la) to be Formula (la'):

wherein R is further limited to independently -H;

-(CH2CH20)n(CH(CH3)CH₂0)mR²; or

-(CH2CH20)n(CH(CH3)CH₂0)mC(0)R¹.

5. The treated carpet of claim 2, where the hydrophobic compound is selected from Formula (lb).

6. The treated carpet of claim 1 , where the coating further comprises a hydrophobic surface effect agent.

7. The treated carpet of claim 6, wherein the surface effect is shrinkage control, moisture control, softness, strength, anti-slip, anti-static, anti-snag, anti-pill, stain repellency, stain release, soil repellency, soil release, water repellency, oil repellency, odor control, antimicrobial, sun protection, or acid resistance.

8. The treated carpet of claim 6 wherein the hydrophobic surface effect agent is selected from the group consisting of non- fluorinated or fluorinated cationic acrylic polymers, non-fluorinated or fluorinated anionic acrylic polymers, non-fluorinated or fluorinated nonionic acrylic polymers, partially fluorinated urethanes, hydrophobic non- fluorinated urethanes, silicones, and waxes.

9. The treated carpet of claim 1 , where the coating comprises

20 to 100% by weight of the hydrophobic compound, based on the total solids weight of the coating.

10. The treated carpet of claim 1 , where the coating comprises 50 to 100% of the hydrophobic compound, based on the total solids weight of the coating.

1 1 . The treated carpet of claim 10, where the coating comprises

100% of the hydrophobic compound, based on the total weight of the coating.

12. A method of imparting a surface effect to a carpet comprising contacting a carpet surface with a coating to form a partially or completely treated carpet,

wherein the coating comprises 5 to 100% by weight of a

where the cyclic or acyclic alcohol is selected from a pentaerythritol, saccharide, reduced sugar, aminosaccharide, citric acid, aldonic acid, or aldonic acid lactone; wherein

each n is independently 0 to 20;

each m is independently 0 to 20;

m+n is greater than 0;

13. The method of claim 12, where the hydrophobic compound is selected from Formulas (la), (lb), or (lc):

wherein each R is independently -H; -R¹ ; -C(0)R¹ ;

-(CH2CH20)n(CH(CH3)CH₂0)mR²; or

-(CH2CH20)n(CH(CH3)CH₂0)mC(0)R¹ ;

each n is independently 0 to 20;

each m is independently 0 to 20;

m+n is greater than 0;

r is 1 to 3;

a is 0 or 1 ;

p is independently 0 to 2;

provided that a is 0 when r is 3;

each R¹ is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond; each R² is independently -H, or a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond; provided when Formula (la) is chosen, then at least one R is -H and at least two R groups are a -R¹ ; -C(0)R¹;

-(CH2CH20)n(CH(CH3)CH₂0)mR²;

or -(CH2CH20)n(CH(CH3)CH₂0)mC(0)R¹;

each R⁴ is independently -H, a linear or branched alkyl group having 6 to 30 carbons optionally comprising at least 1 unsaturated bond, or combinations thereof; -(CH₂CH20)n(CH(CH3)CH₂0)mR²;

or -(CH₂CH₂0)n(CH(CH₃)CH₂0)mC(0)R¹;

provided when Formula (lb) is chosen, then at least one R or R⁴ is - H; and at least two of R or R⁴ are a linear or branched alkyl group optionally comprising at least 1 unsaturated bond, or combinations thereof; -(CH₂CH₂0)_n(CH(CH₃)CH₂0)mR²;

or -(CH₂CH₂0)n(CH(CH₃)CH₂0)mC(0)R¹; and

each R¹⁹ is -H, -C(0)R¹, or -CH₂C[CH₂OR]₃,

-(CH₂CH₂0)n(CH(CH₃)CH₂0)mR²; or

-(CH₂CH₂0)n(CH(CH₃)CH₂0)mC(0)R¹.

14. The method of claim 12, further comprising the step of heating the partially or completely treated carpet.

15. The method of claim 12, further comprising the step of solidifying the coating by drying, cooling, or allowing to cool.

16. The method of claim 12, where the contacting step occurs by spraying, rolling, padding, brushing, sprinkling, dipping, dripping, tumbling, or screen printing.