HYDROPHOBIC COMPOUND EXTENDERS IN SURFACE EFFECT COATINGS

The present invention relates to a coated article comprising a partial or complete coating on the surface of an article, wherein the coating comprises 21 to 79% by weight of a hydrophobic compound, and 21 to 79% by weight of a surface effect agent, both based on the total solids weight of the coating, where the hydrophobic compound is selected from a hydrophobic cyclic or acyclic alcohol.

Skip to: Description  ·  Claims  · Patent History  ·  Patent History
Description
FIELD OF THE INVENTION

Hydrophobic substituted ester alcohols are employed as extenders for surface effect agents in coatings to provide enhanced surface effects to various 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 perfluoroalkyl groups of three or more carbon atoms, which provide oil- and water-repellency when the compositions are applied to fibrous substrate surfaces. The perfluoroalkyl 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.

U.S. Pat. No. 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.

BRIEF SUMMARY OF THE INVENTION

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

The present invention comprises a coated article comprising a partial or complete coating on the surface of an article, wherein the coating comprises 21 to 79% by weight of a hydrophobic compound, and 21 to 79% by weight of at least one surface effect agent, both 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; each R2 is independently —H, a linear or branched alkyl group having 6 to 30 carbons.

The present invention further comprises a method of imparting a surface effect to an article comprising contacting a the surface of the article with a coating to form a partially or completely coated article, wherein the coating comprises 21-79% by weight of a hydrophobic compound, and 21-79% by weight of at least one surface effect agent, both 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; each R2 is independently —H, a linear or branched alkyl group having 6 to 30 carbons.

DETAILED DESCRIPTION OF THE INVENTION

Trademarks are indicated herein by capitalization.

The present invention provides coated articles having improved water repellency, oil or stain repellency, and/or other hydrophobic surface effects. The treated articles provide enhanced performance and durability 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. For example, the coating retains some water repellency, oil repellency, or water spray performance after 30 home washes as described in the examples below.

The present invention comprises a coated article comprising a partial or complete coating on the surface of an article, wherein the coating comprises 5 to 95% by weight of a hydrophobic compound, and 5 to 95% by weight of at least one surface effect agent, both based on the total solids weight of the coating, selected from a cyclic or acyclic sugar alcohol which is substituted with at least one —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 sugar alcohol is selected from a saccharide, reduced sugar, aminosaccharide, 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. The —(CH2CH2O)— represents oxyethylene groups (EO) and —(CH(CH3)CH2O)— represents oxypropylene groups (PO). These 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+m is 1 to 15; and in a third embodiment, n+m is 1 to 12.

In one aspect, the present invention comprises a coated article comprising a partial or complete coating on the surface of an article, wherein the coating comprises 21 to 79% by weight of a hydrophobic compound, and 21 to 79% by weight of at least one surface effect agent, both 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; each R2 is independently —H, a linear or branched alkyl group having 6 to 30 carbons. In one aspect, the coating comprises 25 to 75% by weight of a hydrophobic compound, and 25 to 75% by weight of at least one surface effect agent, both based on the total solids weight of the coating; and in another aspect, the coating comprises 30 to 70% by weight of a hydrophobic compound, and 30 to 70% by weight of at least one surface effect agent, both based on the total solids weight of the coating.

The hydrophobic compound may be a polyester 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, or aldonic acid lactone. Mixtures of these compounds may also be used. The hydrophobic compounds are 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. 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(O)R1; —(CH2CH2O)n(CH(CH3)CH2O)mR2; —(CH2CH2O)n(CH(CH3)CH2O)mC(O)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, sorbitan, glyceraldehyde, erythrose, arabinose, ribose, arabinose, allose, altrose, mannose, xylose, lyxose, gulose, glactose, talose, fructose, ribulose, mannoheptulose, sedohelptulose, threose, erythritol, threitol, glucopyranose, mannopyranose, talopyranose, allopyranose, altropyranose, idopyranose, gulopyranose, glucitol, mannitol, erythritol, sorbitol, arabitol, xylitol, ribitol, galactitol, fucitol, iditol, inositol, pentaerythritol, dipentaerythritol, volemitol, gluconic acid, glyceric acid, xylonic acid, galactaric acid, ascorbic acid, citric acid, gluconic acid lactone, glyceric acid lactone, xylonic acid lactone, glucosamine, galactosamine, or mixtures thereof.

Suitable fatty acids include, but are not limited to, caprylic acid, capric acid, lauric acid, mysteric acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, alkoxylated versions of these acids, and mixtures thereof. In one embodiment, R1 is a linear or branched alkyl group having 11 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 substitution of the cyclic or acyclic sugar alcohols has a melting point of at least −59° C. In another embodiment, the fatty acid substitution of the cyclic or acyclic sugar alcohols has a melting point of at least 0° C., and in a third embodiment, the fatty acid substitution of the cyclic or acyclic sugar alcohols has a melting point of at least 40° C.

In one embodiment, the hydrophobic compound is selected from Formulas (Ia), (Ib), or (Ic):

wherein each R is independently —H; —R1; —C(O)R1; —(CH2CH2O)n(CH(CH3)CH2O)mR2; or —(CH2CH2O)n(CH(CH3)CH2O)mC(O)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; each R2 is independently —H, or a linear or branched alkyl group having 6 to 30 carbons; provided when Formula (Ia) is chosen, then at least one R is —H and at least two R groups are a —R1; —C(O)R1; —(CH2CH2O)n(CH(CH3)CH2O)mR2; or —(CH2CH2O)n(CH(CH3)CH2O)mC(O)R1; each R4 is independently —H, a linear or branched alkyl group having 6 to 30 carbons, or combinations thereof; —(CH2CH2O)n(CH(CH3)CH2O)mR2; or —(CH2CH2O)n(CH(CH3)CH2O)mC(O)R1; provided when Formula (Ib) is chosen, then at least one R or R4 is —H; and at least two of R or R4 is a linear or branched alkyl group; —(CH2CH2O)n(CH(CH3)CH2O)mR2; or —(CH2CH2O)n(CH(CH3)CH2O)mC(O)R1; and each R19 is —H, —C(O)R1, or —CH2C[CH2OR]3, provided when Formula (Ic) is chosen, then at least one R19 or R is —H; and at least two of R19 or R is —C(O)R1, —(CH2CH2O)n(CH(CH3)CH2O)mR2; or —(CH2CH2O)n(CH(CH3)CH2O)mC(O)R1. In one aspect, R, R1, R4, and R19 are saturated linear or branched alkyl groups.

Where the hydrophobic compound is Formula (Ia), 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 (Ia′):

wherein R is further limited to —H; —R1; or —C(O)R1 and at least two R groups are —C(O)R1 or R1. Compounds used to form residues of Formula (Ia′), having at least one of R is —H and at least one R is selected from —C(O)R1, are commonly known as alkyl sorbitans. These sorbitans can be di-substituted or tri-substituted with —C(O)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(O)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(O)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 11 to 21 carbons. Preferred compounds used to form these residues include 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.

In one embodiment, a compound of Formula (Ia) 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 (Ia), 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 (unsubstituted), 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 (Ia) include polysorbates such as polysorbate tristearate and polysorbate monostearate. Examples of compounds of Formula (Ia) 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 C7H14CH═CHC8H17) 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 (Ib) 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; 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 —(CH2CH2O)n(CH(CH3)CH2O)mR2; or —(CH2CH2O)n(CH(CH3)CH2O)mC(O)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. Examples of compounds of Formula (Ib) include, but are not limited to, trialkyl citrates.

Compounds of Formula (Ic) 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 (Ic) are dipentaerythriol esters, where R19 is —CH2C[CH2OR]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(O)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 (Ia), (Ib), and (Ic) 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 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, pigments, functional additives, and surfactants.

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 ethoxylates, 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 or hydrophilic urethanes. These compounds may also be used as surface effect agents and combined with the hydrophobic compounds, from about 21:79 to 79:21 in one aspect; from about 25:75 to 75:25 in a second aspect; and from about 30:70 to 70:30 in a third aspect, based on the total solids weight of the coating.

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+1 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, Del.; ASAHI GARD from Asahi Glass Company, Ltd., Tokyo, Japan; UNIDYNE from Daikin America, Inc., Orangeburg, N.Y.; SCOTCHGARD from 3M Company, St. Paul, Minn.; and NANO TEX from Nanotex, Emeryville, Calif.

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 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 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 fibrous substrates 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, Utah. 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.

For example, when synthetic fabrics are treated, a wetting agent can be used, such as ALKANOL 6112 available The Chemours Company, Wilmington, Del. As a further example, when cotton or cotton-blended fabrics are treated, a wrinkle-resistant resin can be used such as PERMAFRESH EFC available from Emerald Carolina, LLC, Charlotte, N.C. As a further example, when nonwoven fabrics are treated, a wax extender can be employed such as FREEPEL 1225WR, available from Omnova Solutions Chester, S.C. An antistat such as ZELEC KC, available from Stepan, Northfield, Ill., or a wetting agent, such as hexanol, also are suitable. The dispersions are generally applied to fibrous substrates by spraying, dipping, padding, or other well-known methods. After excess liquid has been removed, for example by squeeze rolls, the treated fibrous substrate is dried and then cured by heating, for example, to from about 100° C. to about 190° C., for at least 30 seconds, typically from about 60 to about 240 seconds. Such curing enhances oil-, water- and soil repellency and durability of the repellency. While these curing conditions are typical, some commercial apparatus may operate outside these ranges because of its specific design features.

In one embodiment, the present invention is a method of imparting a surface effect to an article comprising contacting a the surface of the article with a coating to form a partially or completely coated article, wherein the coating comprises 5 to 95% by weight of a hydrophobic compound, and 5 to 95% by weight of at least one surface effect agent, both based on the total solids weight of the coating, selected from a cyclic or acyclic sugar alcohol which is substituted with at least one —R1, —C(O)R′, —(CH2CH2O)n(CH(CH3)CH2O)mR2, —(CH2CH2O)n(CH(CH3)CH2O)mC(O)R1, or mixtures thereof; where the cyclic or acyclic sugar alcohol is selected from a saccharide, reduced sugar, aminosaccharide, 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.

In another embodiment, the present invention is method of imparting a surface effect to an article comprising contacting a the surface of the article with a coating to form a partially or completely coated article, wherein the coating comprises 21-79% by weight of a hydrophobic compound, and 21-79% by weight of at least one surface effect agent, both 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; each R2 is independently —H, a linear or branched alkyl group having 6 to 30 carbons.

The articles may include but are not limited to a fiber, textile, fabric, fabric blend, paper, nonwoven, leather, proppant particle, inorganic oxide particle, unglazed concrete, brick, tile, granite, limestone, marble, grout, mortar, statuary, monument, wood, composite material, terrazzo, glass, thermoplastic sheet, thermoformed or molded article, foam sheet or article, metal, seed, painted fabric or canvas, or a combination thereof. The contacting step may occur by applying the hydrophobic compound 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, dip-squeeze, painting, dripping, powder coating, mixing the article in a liquid carrier of the hydrophobic compound, tumbling, or screen printing.

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

In one aspect, the contacting step occurs inside a laundry machine. Specific methods that may be used are described in US2016/0090560. For example, water is used to help disperse the coating composition, such as by a wash cycle or rinse cycle of the laundry machine. The water temperature used in the wash cycle or rinse cycle may 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 laundry treatment composition by pouring the treatment composition into the basin of the laundry machine, pouring the treatment composition into a detergent or treating agent reservoir of the laundry machine, adding a dissolvable pouch containing the additive composition, or adding a controlled-release reusable container containing the additive composition. Any of the above methods may also be employed using a laundry additive composition comprising two laundry treatment compositions. Alternatively, the laundry additive composition or laundry treatment composition may be introduced into an aqueous liquor and contacted with a fibrous substrate into a tub, bucket or sink, such as when washing fabrics by hand.

In one embodiment, the laundry treatment composition or laundry additive composition is poured into the wash basin, or into a detergent or treating agent reservoir, of the laundry machine and the machine is programmed to run a wash cycle or rinse cycle. In one embodiment, the wash basin 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 wash basin. Detergent is then optionally added, the fibrous substrate is added to the wash basin, and the laundry machine is allowed to run a full wash or rinse cycle.

The method may further comprise a step of curing the hydrophobic compound with heat. Any suitable heating method may be used, such as machine drying in a dryer, ironing, steaming, blow drying, drying under a heat lamp, or drying near a radiative source of heat. In one embodiment, the cure step occurs at a temperature of about 30° C. to about 100° C. In another embodiment, the cure step occurs at a temperature of about 35° C. to about 80° C., and in another embodiment the temperature is about 40° C. to about 60° C., for a time of at least 30 minutes, preferably at least 35 minutes, and more preferably at least 40 minutes. Any drying method can be practiced, including air drying, tumbling dry, or heating the substrate to dryness. Such drying cycles are commonly found on clothes drying machines, including a tumble dry cycle, a tumble dry with heat cycle, or a heated non-tumble cycle. In one embodiment, the treated substrate is tumbled dry with heat. Such curing enhances oil-, water- and soil repellency and durability of the repellency. While these curing conditions are typical, some commercial apparatus may operate outside these ranges because of its specific design features.

In one embodiment, the articles are fibrous substrates, including fibers, textiles, paper, nonwovens, leather, fabrics, fabric blends or a combination thereof. By “fabrics” is meant natural or synthetic fabrics, or blends thereof, composed of fibers such as cotton, rayon, silk, wool, polyester, polypropylene, polyolefins, nylon, and aramids such as “NOMEX” and “KEVLAR.” By “fabric blends” is meant fabric made of two or more types of fibers. Typically these blends are a combination of at least one natural fiber and at least one synthetic fiber, but also can be a blend of two or more natural fibers or of two or more synthetic fibers.

In one aspect, the article is a solid proppant particle or inorganic oxide particle. The solid proppant or particle may be coated by any suitable method known to one skilled in the art. One suitable method includes mixing the hydrophobic compound overnight with water at a pH of 5. The solid proppant is then contacted with the liquid hydrophobic compound dispersion and mixed by roll-mill for 5 minutes. The surface-treated proppant is then separated from the excess liquid and dried in an oven at 100° C. to provide a solid surface-treated proppant. Proppant materials to be surface-treated include but are not limited to sand, thermoplastic particles, alumina particles, glass bubble or glass bead particles, and clay particles. Preferably, the proppant material is sand. The surface-treated proppants of the present invention have a mesh size of at least 100 (up to and including 149 micrometers).

Specifically, the treated articles of the present invention are useful to provide 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, sorbitan trilaurate, and 50:50 sorbitan tribehenate:sorbitan tristearate blend are available from DuPont Nutrition & Health, Copenhagen, Denmark. Decaglycerol decaoleate is available from Lonza, Allendale, N.J. Sorbitan trioleate is available from Oleon, Ghent, Belgium.

ARMEEN DM-18D was obtained from Akzo-Nobel, Bridgewater, N.J. PHOBOL XAN was obtained from Huntsman Corp, Salt Lake City, Utah.

STEPOSOL SB-W was obtained from Stepan, Northfield, Ill. VMA-70 is available from NOF Corporation.

CHEMIDEX S is a stearaminopropyl dimethylamine surfactant available from Lubrizol, Wickliffe, Ohio.

ETHAL LA-4 is an ethoxylated emulsifier available from Ethox Chemicals, Greenville, S.C.

CAPSTONE 6,2-FMA and ZELAN R3 are available from The Chemours Company, Wilmington, Del.

PLURONIC L-35 is available from BASF, Florham Park, N.J.

The following tests were employed in evaluating the examples herein.

Test Method 1—Fabric Treatment

The fabrics treated in this study were 100% by weight polyester fabric available from L. Michael OY, Finland or 100% by weight nylon fabric available from Huntsman Corp, Salt Lake City, Utah. The fabric was treated with the aqueous dispersions of hydrophobic compounds and surface effect polymers using a conventional pad bath (dipping) process. The prepared concentrated dispersions were diluted with deionized water to achieve a pad bath having 60 g/L of the final emulsion in the bath. For the treatment of the cotton fabric, a wetting agent, INVADINE PBN and a catalyzed cross-linking agent, KNITTEX 7636 (all available from Huntsman, Salt Lake City, Utah) were also included in the bath at 5 g/L and 30 g/L respectively. The fabric was padded in the bath, and the excess liquid was removed by squeeze rollers. The wet pickup was around 95% on the cotton substrate. The “wet pick up” is the weight of the bath solution of the emulsion polymer and additives applied to the fabric, based on the dry weight of the fabric. The fabric was cured at approximately 165° C. for 3 minutes and allowed to “rest” after treatment and cure for at least 2 hours.

For the treatment of the polyester fabric, a wetting agent, INVADINE® PBN (available from Huntsman, Charlotte, N.C., USA) and 60% acetic acid were also included in the bath at 5 g/L and 1 g/L respectively. The fabric was padded in the bath, and the excess liquid removed by squeeze rollers. The wet pickup was around 55% on the polyester substrate. The “wet pick up” is the weight of the bath solution of the emulsion polymer and additives applied to the fabric, based on the dry weight of the fabric. The fabric was cured at approximately 160° C. for 2 minutes and allowed to “rest” after treatment and cure for about 15 to about 18 hours.

Test Method 2—Water Drop Rating

The water repellency of a treated textile substrate was measured according to AATCC standard Test Method No. 193 and the method outlined in the Teflon® Global Specifications and Quality Control Tests booklet. The higher the water drop rating, the better the resistance the finished substrate has to staining by water-based substances.

Test Method 3—Water Spray Repellency

Water repellency was further tested by utilizing the spray test method which is a measure of dynamic water repellency. The treated fabric samples were tested for water repellency according to AATCC standard Test Method No. 22 and the method outlined in the Teflon® Global Specifications and Quality Control Tests booklet. A rating of 90 denotes slight random sticking or wetting without penetration; lower values indicate progressively greater wetting and penetration.

Test Method 4—Oil Rating

The treated fabric samples were tested for oil repellency by a modification of AATCC standard Test Method No. 118, and the method outlined in the Teflon® Global Specifications and Quality Control Tests booklet. The higher the oil drop rating, the better the resistance the finished substrate has to staining by oil-based substances.

Test Method 5—Bundesmann Absorbency (ABS)

The treated fabric samples were tested for dynamic water absorbency following ISO 9865 standard Test Method.

Test Method 6—Wash Durability

The fabric samples were laundered according to International Standard specified domestic washing procedure for textile testing. Fabric samples were loaded into a horizontal drum, front-loading type (Type A, WASCATOR FOM 71MP-Lab) of automatic washing machine with a ballast load to give a total dry load of 4 lb. A commercial detergent was added (AATCC 1993 standard Reference Detergent WOB) and the washer program 6N was used to simulate 20 home washes (20 HW) or 30 home washes (30 HW). After washing was complete, the entire load was placed into a KENMORE automatic dryer and dried on high for 45-50 min.

EXAMPLES Examples 1-10

Partially fluorinated polymer repellents are synthesized via emulsion polymerization, in the presence of hydrophobic compounds at 20 weight % of the total monomer weight. The hydrophobic compounds are listed in Table 1. Water (260 g), ARMEEN DM 18D (5.09 g), acetic acid (3.18 g), TERGITOL TMN-10 (2.55 g), dipropylene glycol (24.17 g), STEPOSOL SB-W (Steposol, 1.91 g), stearic acid (0.013), and the hydrophobic compound (26.69 g) are weighed into a beaker and stirred at 60° C. until all the components are dissolved. This mixture is transferred to a plastic bottle, and CAPSTONE 62-MA (The Chemours Company, 85.57 g), 7-EO methacrylate (1.57 g), VMA-70 (43.45 g), hydroxyethyl methacrylate (1.62 g), and dodecyl mercaptan (0.83 g) are weighed into the bottle. The mixture is premixed with a Janke & Kunkel IKA-WERK Ultra Turrax homogenizer/immersion blender for 1 minute immediately before homogenizing for 8 passes at 4350 psi (or until absorbance value was <0.25 A.U.). The homogenized material is charged into a 500 mL jacketed reactor with a temperature controller, overhead stirrer, and condenser with nitrogen line. The reaction mixture is sparged with nitrogen for 20 minutes. When the temperature of the mixture is below 30° C., VAZO 56 (0.40 g) is added and the reaction mixture is heated from 28° C. to 55° C. over 30 minutes. The reaction is held at 55° C. for 8 hours. The product is filtered through a 25 mm filter and solids are measured. Products are padded on polyester at 45 g/L of the fluorinated acrylic with 5 g/L INVADINE PBN, 1 g/L 60% acetic acid, and, in some cases, PHOBOL XAN. Samples are tested according to Test Methods 1-6.

Comparative Examples A and B

The procedure for Examples 1-10 is repeated according to Table 1, without the addition of the hydrophobic compound.

TABLE 1 Composition of Examples 1-10 and Comparative Examples A and B Example Hydrophobic compound g/L PHOBOL XAN A N/A 0 B N/A 10 1 Sorbitan tristearate 0 2 Sorbitan tristearate 10 3 50:50 blend of sorbitan 0 tribehenate and sorbitan tristearate 4 50:50 blend of sorbitan 10 tribehenate and sorbitan tristearate 5 Sorbitan trilaurate 0 6 Sorbitan trilaurate 10 7 Decaglycerol decaoleate 0 8 Decaglycerol decaoleate 10 9 Sorbitan trioleate 0 10  Sorbitan trioleate 10

TABLE 2 Performance of Examples 1-10 and Comparative Examples A and B on 100% Polyester Fabric Water Drop Oil Rating Spray Rating 20HW 20HW 20HW ABS Ex. Initial (60° C.) Initial (60° C.) Initial (60° C.) % A 9 7 5 3 100 80 10.8 B 9 9 6 5 100 95 15.9 1 10 6 5.5 2 100 75 12.9 2 10 7 5.5 4 100 90 4.1 3 9 6 5 2 100 90 8.2 4 9 7 5 4 100 95 3.3 5 10 6 5.5 2 100 70 7.0 6 10 8 5.5 4 100 80 3.4 7 10 6 5 1 100 70 15.6 8 10 6 5 2.5 100 80 17.1 9 9 6 5 1 100 70 19.6 10  10 7 5 2.5 100 80 15.5

The results indicate that the hydrophobic compounds maintain or extend the static water repellency and durable dynamic water repellency performance of partially fluorinated copolymer dispersions, while exhibiting fluorine efficiency.

Example 11

Into a 4-neck round bottom flask equipped with an overhead stirrer, thermocouple and condenser is added sorbitan tristearate (111 g) and 4-methyl-2-pentanone (MIBK, 274 g). The solution is heated to 80° C. An aqueous dispersion is then prepared by adding warm water (512 g), CHEMIDEX S (2.4 g), ETHAL LA-4 (3.2 g) and acetic acid (1.6 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 dispersion at 13.15% solids after cooling and filtering. The resulting dispersion is blended with the fluorinated acrylic of Comparative Example A in a ratio of 18.31% by weight hydrophobic compound: 81.69% by weight of fluorinated acrylic polymer, applied to the fabric at 45 g/L of the fluorinated acrylic with 5 g/L of INVADINE PBN and 1 g/L of 60% acetic acid, and tested according to the test methods above.

Example 12

Example 11 is repeated, adding 10 g/L of PHOBOL XAN to the pad bath.

TABLE 3 Performance of Examples 11-12 Water Drop Oil Rating Spray Rating 20HW 20HW 20HW ABS Ex. Initial (60° C.) Initial (60° C.) Initial (60° C.) % 100% Polyester 11 8 8 5 4 100 100 11.8 12 9 9 5 5 100 100 10.5 Nylon 11 9 9 5 5 100 100 22.7 12 9 9 5 5 100 100 20.2

Examples 13-30 and Comparative Examples C-E

ARMEEN DM18D (24.7 g), DI water (2066 g), 2-ethylhexyl methacrylate (1076 g), 7-EO methacrylate (154 g), N-methylolacrylamide (48%, 31 g), dodecyl mercaptans (1.5 g), 2% NaCl solution (58 g), glacial acetic acid (17 g), and hexylene glycol (308 g) were mixed and later blended in a large commercial blender for 2 minutes. An additional 200 g of DI water was added. The resulting mixture was transferred into a reactor, stirred at 75° C., and sparged with nitrogen for 30 minutes. VAZO 56 (2.5 g) was added with 61 g of DI water, and the mixture was stirred for 4 hours to yield a non-fluorinated acrylic dispersion product (NFAD) at 33.55% solids.

Example 11 is repeated, except the hydrophobic compound dispersion is blended with ZELAN R3 and NFAD and applied to the fabric at 60 g/L of solids content or 40 g/L in the amounts described in Table 4.

TABLE 4 Composition of Examples 13-30 and Comparative Examples C-E Hydrophobic compound Example dispersion ZELAN R3 NFAD 13 0.33 0.33 0.33 14 0.20 0.40 0.40 15 0.80 0.20 — 16 0.40 0.40 0.20 17 0.40 0.60 — 18 0.20 0.80 — 19 0.17 0.17 0.67 20 0.80 — 0.20 21 0.40 0.20 0.40 22 0.17 0.67 0.17 23 0.67 0.17 0.17 C — 0.20 0.80 D 1.00 — — 24 0.40 — 0.60 25 0.20 — 0.80 E — 0.80 0.20 26 0.20 0.60 0.20 27 0.20 0.20 0.60 28 0.60 0.20 0.20 29 0.60 0.40 — 30 0.60 — 0.40

TABLE 5 Performance of Examples 13-30 and Comparative Examples C-E Applied at 60 g/L Spray Rating ABS % 30HW 30HW Example Initial (60° C.) Initial (60° C.) 13 100 100 37.5 11.6 14 100 100 27.7 16.6 15 100 100 64.4 22.5 16 100 100 33.8 7.5 17 100 100 36.2 6.1 18 100 100 20.5 5.3 19 100 90 35.1 25.1 20 100 100 53.6 26.5 21 100 100 47.2 18.9 22 100 100 29.3 5 23 100 100 32.2 5.3 C 80 70 49.7 16.97 D 70 70 41 36.6 24 80 70 59.9 31.95 25 80 70 42.7 21 E 100 100 15.8 4.9 26 100 100 28.9 5.1 27 100 100 40 24.97 28 100 100 43.6 6.5 29 100 100 53.3 12.6 30 100 100 55.1 15.8

TABLE 6 Performance of Examples 13-30 and Comparative Examples C-E Applied at 40 g/L Spray Rating ABS % 30HW 30HW Example Initial (60° C.) Initial (60° C.) 13 100 100 34.5 12.3 14 100 100 39.1 12 15 100 100 53.4 23.2 16 100 100 32.1 7.4 17 100 100 39.9 5.5 18 100 100 31.1 3.5 19 100 90 42.9 23.8 20 100 100 49.7 24.8 21 100 100 43.2 15.96 22 100 100 34.9 5 23 100 100 50.5 5.3 C 70 100 60.3 27.1 D 80 100 48.6 23.7 24 80 80 47.4 31.6 25 100 100 22.7 3.7 E 100 100 35.1 4.7 26 100 100 40.1 20.1 27 100 100 46.9 9.2 28 100 100 42.8 25.8 29 100 100 50.7 22.5 30 100 100 34.5 12.3

Comparative Examples F-G

Samples are padded with CAPSTONE TC-A, 5 g/L INVADINE PBN, 1 g/L 60% acetic acid, and 10 g/L of PHOBOL XAN according to Table 7. Samples are tested according to Test Methods 1-6.

Comparative Examples H-I

Water (333 g), ARMEEN DM 18D (8.43 g), acetic acid (5.27 g), TERGITOL TMN-10 (4.22 g), dipropylene glycol (40.04 g), STEPOSOL SB-W (Stepan, 3.16 g), SILTECH TC11-58B (15.61 g) and stearic acid (0.022) are weighed into a beaker and stirred at 60° C. until all the components are dissolved. This mixture is transferred to a plastic bottle, and CAPSTONE 62-MA (178.11 g), 7-EO methacrylate (2.59 g), stearyl methacrylate (29.19), VMA-70 (6.36 g), hydroxyethyl methacrylate (2.68 g), 2-ethylhexyl methacrylate (0.23 g) and dodecyl mercaptan (1.37 g) are weighed into the bottle. The mixture is premixed with a Janke & Kunkel IKA-WERK Ultra Turrax homogenizer/immersion blender for 1 minute immediately before homogenizing for 8 passes at 4350 psi (or until absorbance value was <0.25 A.U.). The homogenized material is charged into a 500 mL jacketed reactor with a temperature controller, overhead stirrer, and condenser with nitrogen line. The reaction mixture is sparged with nitrogen for 20 minutes. When the temperature of the mixture is below 30° C., VAZO 56 (0.66 g) is added and the reaction mixture is heated from 28° C. to 55° C. over 30 minutes. The reaction is held at 55° C. for 8 hours. The product is filtered through a 25 mm filter and solids are measured and adjusted to 32% to form Product H. Products are padded with the resulting product, 5 g/L INVADINE PBN, 1 g/L 60% acetic acid and 10 g/L PHOBOL XAN according to Table 7. Samples are tested according to Test Methods 1-6.

Examples 31-62

Into a 4-neck round bottom flask equipped with an overhead stirrer, thermocouple, and condenser was added 2-ethylhexyl methacrylate (48 g), dodecyl mercaptan (0.07 g) and sorbitan tristearate (63.2 g). The solution was heated to 55° C. An aqueous dispersion was then prepared by adding warm water (290 g), ARMEEN DM 18D (1.35 g), glacial acetic acid (1.8 g), 2% sodium chloride solution (2.9 g), dipropylene glycol (18 g), EHAL LA-4 (0.2 g), PLURONIC L-35 (0.65 g), white mineral oil (2.25 g), and 7-EO methacrylate (13.4 g) at 55° C. The mixture was stirred, homogenized at 6000 psi, and the resulting dispersion was returned to the round bottom flask. The dispersion was sparged with nitrogen for 30 minutes while heating to 70° C. While heating, 48 wt % N-(hydroxymethyl) acrylamide solution in water (0.5 g) was added and allowed to stir for 30 minutes. VAZO 56 (0.12 g) was added to the reactor and the reactor was held at 70° C. for 4 hours. Additional PLURONIC L-35 (1.55 g) was added, the product was cooled and filtered, and the solids were adjusted to 20% solids to form a hydrophobic compound dispersion. Products are padded with the resulting product, 5 g/L INVADINE PBN, 1 g/L 60% acetic acid and 10 g/L PHOBOL XAN according to Table 7. Samples are tested according to Test Methods 1-6.

TABLE 7 Composition of Examples 31-62 and Comparative Examples F-M Additive Composition Ratio PHOBOL Hydrophobic XAN Additive CAPSTONE Product compound Example Loading Loading TC-A H dispersion F — 45 g/L 100 — — G 10 g/L 45 g/L 100 — — H — 45 g/L — 100   — I 10 g/L 45 g/L — 100   — 31 — 45 g/L 30 — 70 32 10 g/L 45 g/L 30 — 70 33 — 45 g/L — 27.4 72.6 34 10 g/L 45 g/L — 27.4 72.6 35 — 60 g/L 22.6 — 77.4 36 10 g/L 60 g/L 22.6 — 77.4 37 — 60 g/L — 20.5 79.5 38 10 g/L 60 g/L — 20.5 79.5 39 — 90 g/L 15 — 85 40 10 g/L 90 g/L 15 — 85 41 — 90 g/L — 13.7 86.3 42 10 g/L 90 g/L — 13.7 86.3 43 — 45 g/L 22.6 — 77.4 44 10 g/L 45 g/L 22.6 — 77.4 45 — 45 g/L — 20.5 79.5 46 10 g/L 45 g/L — 20.5 79.5 47 — 45 g/L 15 — 85 48 10 g/L 45 g/L 15 — 85 49 — 45 g/L — 13.7 86.3 50 10 g/L 45 g/L — 13.7 86.3 51 — 45 g/L 45 — 55 52 10 g/L 45 g/L 45 — 55 53 — 45 g/L — 41   59 54 10 g/L 45 g/L — 41   59 55 — 45 g/L 37.6 — 62.4 56 10 g/L 45 g/L 37.6 — 62.4 57 — 45 g/L — 34.2 65.8 58 10 g/L 45 g/L — 34.2 65.8 59 — 45 g/L 7.5 — 92.5 60 10 g/L 45 g/L 7.5 — 92.5 61 — 45 g/L — 10   90 62 10 g/L 45 g/L — 10   90

TABLE 8 Performance of Examples 31-50 and Comparative Examples F-I on a Cotton Substrate Water Drop Rating Oil Drop Rating Spray Rating 20 HW 20 HW 20 HW ABS % Ex. Initial (40° C.) Initial (40° C.) Initial (40° C.) Initial F 11 9 6 4 100 90 24.7 G 11 10 6 5 100 100 11.7 H 11 8 6 2 100 90 22.7 I 11 10 6 5 100 100 17.7 31 11 10 6 6 100 100 17.5 32 11 10 6 6 100 100 10.5 33 11 10 6 6 100 100 18.6 34 11 10 6 6 100 100 13.2 35 11 9 6 5 100 90 18.8 36 11 10 6 6 100 100 11.8 37 11 9 6 5 100 90 16.4 38 11 10 6 6 100 100 13.2 39 11 9 6 5 100 90 21.5 40 11 10 6 6 100 100 13.8 41 10 9 6 5 100 90 18.3 42 10 9 6 5 100 100 13.6 43 11 9 6 5 100 90 19.0 44 11 10 6 6 100 100 14.7 45 11 9 6 5 100 90 17.0 46 11 10 6 6 100 100 12.3 47 9 9 6 5 100 90 18.4 48 9 9 6 6 100 100 18.7 49 9 9 6 5 100 90 18.0 50 9 9 6 6 100 100 16.4

TABLE 9 Performance of Examples 31-34, 43-62, and Comparative Examples F-I on a Polyester Substrate Water Drop Rating Oil Drop Rating Spray Rating 20 HW 20 HW 20 HW ABS % Ex. Initial (40° C.) Initial (40° C.) Initial (40° C.) Initial F 9 7 5 4 100 100 1.9 G 9 8 5 4 100 100 1.7 H 9 8 5 4 100 100 3.1 I 9 8 9 4 100 100 2.0 51 9 8 5 4.5 100 100 3.9 52 9 8 5 4.5 100 100 0.6 53 9 8 5 4.5 100 100 2.2 54 9 8 5 4.5 100 100 0.7 55 9 8 5 4.5 100 100 3.4 56 9 8 5 4.5 100 100 1.7 57 9 8 5 4.5 100 100 2.4 58 9 8 5 4.5 100 100 0.5 31 9 8 5 4.5 100 100 4.5 32 9 8 5 4.5 100 100 1.9 33 9 8 5 4.5 100 100 5.4 34 9 8 5 4.5 100 100 0.9 43 9 8 5 4 100 100 6.0 44 9 8 5 4.5 100 100 3.4 45 9 8 5 4 100 100 7.0 46 9 8 5 4.5 100 100 1.0 47 9 7 5 4 100 100 6.5 48 9 8 5 4.5 100 100 4.4 49 8 7 5 4 100 100 7.0 50 8 7 5 4.5 100 100 6.0 59 9 7 3 2 100 100 8.6 60 9 8 3 3 100 100 6.8 61 6 6 3 2 100 100 14.7 62 6 6 3 3 100 100 10.1

TABLE 10 Performance of Examples 31-34, 43-62, and Comparative Examples F-I on a Nylon Substrate Water Drop Rating Oil Drop Rating Spray Rating 20 HW 20 HW 20 HW ABS % Ex. Initial (40° C.) Initial (40° C.) Initial (40° C.) Initial F 11 10 6 6 100 100 14.8 G 11 10 6 6 100 100 2.7 H 11 10 6 5 100 100 13.2 I 11 10 6 5 100 100 3.1 51 11 11 6 6 100 100 15.4 52 11 11 6 6 100 100 3.3 53 11 11 6 6 100 100 9.0 54 11 11 6 6 100 100 1.5 55 11 11 6 6 100 100 16.1 56 11 11 6 6 100 100 3.2 57 11 11 6 6 100 100 11.3 58 11 11 6 6 100 100 2.2 31 11 10 6 6 100 100 18.9 32 11 11 6 6 100 100 5.2 33 11 11 6 6 100 100 19.5 34 11 11 6 6 100 100 2.7 43 11 10 6 6 100 100 17.4 44 11 11 6 6 100 100 4.0 45 11 11 6 6 100 100 19.4 46 11 11 6 6 100 100 4.6 47 11 10 6 6 100 100 18.8 48 11 11 6 6 100 100 10.8 49 11 11 6 6 100 100 22.1 50 11 11 6 6 100 100 13.2 59 10 9 5 5 100 90 22.7 60 10 10 5 5 100 100 17.4 61 7 7 4 4 100 100 36.4 62 7 7 4 4 100 100 25.2

Examples 63-66

Partially fluorinated polymer repellents are synthesized via emulsion polymerization, in the presence of sorbitan tristearate at 0-50 weight % of the total monomer and hydrophobic compound weight. The ratios of active hydrophobic compound to fluorinated acrylic are listed in Table 11.

Water (340 g), ARMEEN DM 18D (0.45 g), acetic acid (0.28 g), ETHAL LA-4 (1.10 g), dipropylene glycol (17.25 g), STEPOSOL SB-W (Steposol, 1.71 g), stearic acid (0.01), and sorbitan tristearate are weighed into a beaker and stirred at 60° C. until all the components are dissolved. This mixture is transferred to a plastic bottle, and CAPSTONE 62-MA (The Chemours Company, 48.19 g), 7-EO methacrylate (8.20 g), SMA (7.90 g), VMA-70 (1.72 g), hydroxyethyl methacrylate (0.73 g), 2-ethylhexyl methacrylate (22.48 g), and dodecyl mercaptan (0.41 g) are weighed into the bottle. The mixture is premixed with a Janke & Kunkel IKA-WERK Ultra Turrax homogenizer/immersion blender for 1 minute before homogenizing 4350 psi (absorbance value was <0.25 A.U.). The homogenized material is charged into a 500 mL jacketed reactor with a temperature controller, overhead stirrer, and condenser with nitrogen line. The reaction mixture is heated to 70° C. while sparging with nitrogen for 20 minutes. Ethylene glycol dimethacrylate (0.06 g) and N-Methylolacrylamide (48 wt. % in water, 1.36 g) are added to the reaction mixture and stirred. VAZO 56 (0.24 g) is added and the reaction mixture is heated to 78° C. and held for 8 hours. The product is filtered through a 25 mm filter and solids are measured. Products are padded on polyester at equal loading as 50 g/L of a 6% fluorine fluorinated acrylic with 5 g/L INVADINE PBN, 1 g/L 60% acetic acid, and, in some cases, 10 g/L PHOBOL XAN. Samples are tested according to Test Methods 1-6.

Comparative Examples J-K

The procedure for Example 63 is repeated according to Table 11, without the addition of the hydrophobic compound.

TABLE 11 Composition of Examples 63-66 and Comparative Examples J-K Weight Ratio of Hydrophobic Example Compound:Fluoropolymer g/L PHOBOL XAN A  0:100 0 B  0:100 10 63 30:70 0 64 30:70 10 65 50:50 0 66 50:50 10

TABLE 12 Performance of Examples 63-66 and Comparative Examples J-K on 100% Polyester Fabric Water Drop Oil Rating Spray Rating 20HW 20HW 20HW ABS Ex. Initial (60° C.) Initial (60° C.) Initial (60° C.) % A 9 6 4.5 2 100 80 4.5 B 9 8 4.5 3.5 100 85 4.1 63 9 7 5 2 100 85 1.8 64 9 8 5 4.5 100 100 1.9 65 9 6 3 1 100 70 3.6 66 9 8 3.5 3 100 100 3.1

Claims

1. A coated article comprising a partial or complete coating on the surface of an article,

wherein the coating comprises 21 to 79% by weight of a hydrophobic compound, and 21 to 79% by weight of at least one surface effect agent, both 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)R′, —(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; and
each R2 is independently —H, a linear or branched alkyl group having 6 to 30 carbons.

2. The coated article of claim 1, where the hydrophobic compound is selected from Formulas (Ia), (Ib), or (Ic):

wherein each R is independently —H; —R1; —C(O)R1; —(CH2CH2O)n(CH(CH3)CH2O)mR2; or —(CH2CH2O)n(CH(CH3)CH2O)mC(O)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;
each R2 is independently —H, or a linear or branched alkyl group having 6 to 30 carbons;
provided when Formula (Ia) is chosen, then at least one R is —H and at least two R are a —R1; —C(O)R1; —(CH2CH2O)n(CH(CH3)CH2O)mR2; or —(CH2CH2O)n(CH(CH3)CH2O)mC(O)R1;
each R4 is independently —H, a linear or branched alkyl group having 6 to 30 carbons, or combinations thereof; —(CH2CH2O)n(CH(CH3)CH2O)mR2; or —(CH2CH2O)n(CH(CH3)CH2O)mC(O)R1;
provided when Formula (Ib) 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, or combinations thereof; —(CH2CH2O)n(CH(CH3)CH2O)mR2; or —(CH2CH2O)n(CH(CH3)CH2O)mC(O)R1; and
each R19 is —H, —C(O)R1, or —CH2C[CH2OR]3, provided when Formula (Ic) is chosen, then at least one R19 or R is —H; and at least two of R19 or R are —C(O)R1, —(CH2CH2O)n(CH(CH3)CH2O)mR2; or —(CH2CH2O)n(CH(CH3)CH2O)mC(O)R1.

3. The coated article of claim 2, where the hydrophobic compound is selected from Formula (Ia) to be Formula (Ia′):

wherein R is further limited to independently —H; —R1; or —C(O)R1.

4. The coated article of claim 2, where the hydrophobic compound is selected from Formula (Ia) to be Formula (Ia′):

wherein R is further limited to independently —H; —(CH2CH2O)n(CH(CH3)CH2O)mR2; or —(CH2CH2O)n(CH(CH3)CH2O)mC(O)R1.

5. The coated article of claim 2, where the hydrophobic compound is selected from Formula (Ib).

6. The coated article of claim 1, wherein the surface effect is no iron, easy to iron, shrinkage control, wrinkle free, permanent press, moisture control, softness, strength, anti-slip, anti-static, anti-snag, anti-pill, stain repellency, stain release, soil repellency, soil release, water repellency, oil repellency, odor control, antimicrobial, sun protection, anti-blocking, cleanability, dust resistance, leveling, corrosion resistance, acid resistance, anti-fog, anti-ice, or tanning.

7. The coated article of claim 1 wherein the surface effect agent is a hydrophobic polymer 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, non-fluorinated urethanes, silicones, waxes, and mixtures thereof.

8. The coated article of claim 1, where the coating comprises 25 to 75% by weight of a hydrophobic compound, and 25 to 75% by weight of a surface effect agent, both based on the total solids weight of the coating.

9. The coated article of claim 1, where the coating comprises 30 to 70% by weight of a hydrophobic compound, and 30 to 70% by weight of a surface effect agent, both based on the total solids weight of the coating.

10. The coated article of claim 1 wherein the article is a fiber, textile, fabric, fabric blend, paper, nonwoven, leather, proppant particle, inorganic oxide particle, unglazed concrete, brick, tile, granite, limestone, marble, grout, mortar, statuary, monument, glass, thermoplastic sheet, thermoformed or molded article, foam sheet or article, metal, seed, painted fabric or canvas, or a combination thereof.

11. A method of imparting a surface effect to an article comprising contacting a the surface of the article with a coating to form a partially or completely coated article,

wherein the coating comprises 21-79% by weight of a hydrophobic compound, and 21-79% by weight of at least one surface effect agent, both 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; and
each R2 is independently —H, a linear or branched alkyl group having 6 to 30 carbons.

12. The method of claim 11, where the hydrophobic compound is selected from Formulas (Ia), (Ib), or (Ic):

wherein each R is independently —H; —R1; —C(O)R1; —(CH2CH2O)n(CH(CH3)CH2O)mR2; or —(CH2CH2O)n(CH(CH3)CH2O)mC(O)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;
each R2 is independently —H, or a linear or branched alkyl group having 6 to 30 carbons;
provided when Formula (Ia) is chosen, then at least one R is —H and at least two R groups are a —R1; —C(O)R1; —(CH2CH2O)n(CH(CH3)CH2O)mR2; or —(CH2CH2O)n(CH(CH3)CH2O)mC(O)R1;
each R4 is independently —H, a linear or branched alkyl group having 6 to 30 carbons, or combinations thereof; —(CH2CH2O)n(CH(CH3)CH2O)mR2; or —(CH2CH2O)n(CH(CH3)CH2O)mC(O)R1;
provided when Formula (Ib) is chosen, then at least one R or R4 is —H; and at least two of R or R4 is a linear or branched alkyl group, or combinations thereof; —(CH2CH2O)n(CH(CH3)CH2O)mR2; or —(CH2CH2O)n(CH(CH3)CH2O)mC(O)R1; and
each R19 is —H, —C(O)R1, or —CH2C[CH2OR]3, provided when Formula (Ic) is chosen, then at least one of R19 or R is —H; and at least two of R19 or R are —C(O)R1, —(CH2CH2O)n(CH(CH3)CH2O)mR2; or —(CH2CH2O)n(CH(CH3)CH2O)mC(O)R1.

13. The method of claim 11, further comprising the step of heating the partially or completely coated article.

14. The method of claim 11, further comprising the step of solidifying the coating by drying, cooling, or allowing to cool.

15. The method of claim 11, where the step of contacting is by spraying, rolling, dip-squeeze, painting, sprinkling, dripping, powder coating, mixing the article in a liquid carrier of the hydrophobic compound, tumbling, or screen printing.

16. The method of claim 11, where the contacting step occurs inside a laundry machine.

Patent History
Publication number: 20180282571
Type: Application
Filed: Sep 30, 2016
Publication Date: Oct 4, 2018
Inventors: GERALD ORONDE BROWN (Swedesboro, NJ), JOHN CHRISTOPHER SWOREN (Lincoln University, PA), CHARLES KARANJA (NEWARK, DE), TESS CROSETTO (PHILADELPHIA, PA)
Application Number: 15/764,898
Classifications
International Classification: C09D 133/16 (20060101); C09D 7/63 (20060101); D06M 15/277 (20060101);