WO2016176388A1

WO2016176388A1 - Crosslinkable fluorinated inorganic oxide particle for architectural coatings

Info

Publication number: WO2016176388A1
Application number: PCT/US2016/029663
Authority: WO
Inventors: Anilkumar Raghavanpillai; Hau-Nan LEE; Jelena LASIO; Brad M. Rosen; Stephanie A. BERNARD; James J. Hughes; Vincent FRANCO; John Russell Crompton Jr.
Original assignee: The Chemours Company Tt, Llc
Priority date: 2015-04-30
Filing date: 2016-04-28
Publication date: 2016-11-03

Abstract

The present invention comprises a crosslinkable surface modified inorganic oxide particle, having both fluorinated and ethylenically unsaturated pendant groups grafted thereon. Such particles are useful as coatings additives such that, when the coating is applied to a substrate, the additive compound is allowed to first migrate to the surface and subsequently crosslink to form a durable oil-, dirt-, and water-repellent surface.

Description

TITLE OF INVENTION

CROSSLINKABLE FLUORINATED INORGANIC OXIDE PARTICLE FOR

ARCHITECTURAL COATINGS FIELD OF THE INVENTION

This invention relates to an ethylenically crosslinkable fluorinated inorganic oxide particle compound and its use as an additive in

architectural coating compositions such as water-based latex paints, to provide durable surface effects.

BACKGROUND OF THE INVENTION

The coating compositions of interest in the present invention include alkyd coating compositions, urethane coating compositions, water- dispersible coating compositions, and unsaturated polyester coating compositions, typically a paint, clear coating, or stain. All of the above- listed coating compositions after drying or curing often show low

hexadecane contact angles, are readily wetted by oil, and are susceptible to soiling. The coating compositions are described in Outlines of Paint Technology (Halstead Press, New York, NY, Third edition, 1990) and Surface Coatings Vol. I, Raw Materials and Their Usage (Chapman and Hall, New York, NY, Second Edition, 1984).

Inorganic particles hydrophobized with fluorosilanes have been used to impart hydrophobic as well as oleophobic properties as

exemplified by U.S. Patent Application, US2006/0222815, filed by Oles et al. which teaches making such hydrophobized particles by the covalent bonding (i.e. grafting) of fluorosilanes upon the surface of inorganic particles (e.g. silica). The fluorosilanes employed by Oles et al. consist of a silicon atom having four bonds, three of which are direct bonds to hydrolysable groups which can react with the surface of an inorganic particle thereby covalently bonding the fluorosilane to particle. The remaining bond is a direct bond from the silicon atom to a perfluoroalkyl group. Such particles are not crosslinkable to form durable surface effects in coatings.

BRIEF SUMMARY OF THE INVENTION

Water-based latex coating bases, such as those employed as paint coatings, have a tendency to have low oil repellency and poor cleanability ratings. To impart better cleanability to interior and exterior paint surfaces, small molecule additives, including fluorosurfactants, have been used. Due to their small molecular size, however, the additives do not provide long-term performance and durability in exterior paint, which is subjected to more extreme environmental conditions. The additives can wash away from the coating surface within a few days.

The present invention addresses the issues described above by introducing crosslinkable fluorinated inorganic oxide particles into a coating composition. Due to the crosslinkable nature of the fluoroadditive, the compositions of the present invention provide performance as well as durability to the water-based latex coatings. Additionally, the low surface energy of the fluorinated groups allows the particles to migrate to the coating surface before crosslinking to form a durable additive at the coating surface. The particles of the invention impart unexpectedly desirable surface effects such as: increased water and oil contact angles, enhanced dirt pickup resistance, and enhanced cleanability to the coating films.

The present invention comprises surface modified inorganic oxide particles comprising an oxide of X wherein X is independently selected from the group consisting of Si, Ti, Zn, Zr, Mn, Al, and combinations thereof; at least one of said particles having a surface covalently bonded to

a. at least one fluorosilane group represented by Formula (I)

(L¹)g(L²)hSi— A¹— Q¹x-Rfi (I); and b. at least one ethylenically unsaturated group represented by

Formula (II)

wherein each L¹ represents an oxygen covalently bonded to an X; and each L² is independently selected from the group consisting of H, a C1-C2 alkyl, OCH3, OCH2CH3, and OH; g and h are integers such that: g > 1 , h > 0, and g+h =3; A¹ is (CH₂)_k— N(R⁹-R_fi )-R⁹, (CH₂)k— NH-C(O)-NH, (CH₂)k— NH-C(S)-NH, (CH₂)k— NH-C(O)O, (CH₂)_k— NH-C(O)S, (CH₂)_k— NH-C(O)- NH-SO₂, (CH₂)k— NH-C(S)-NH-SO₂, (CH₂)_k— NH-C(O)-N[C(O)H], (CH₂)k— NH-C(O)-CH[CH(COOH)(R¹⁰)]-S, (CH₂)_k— NH-C(O)-CH(R¹⁰)[CH(COOH)]- S, 0-C(0)-NH, S-C(0)-NH, 0-C(S)-NH, or S-C(S)-NH; R⁹ is a C2-C12 hydrocarbylene interrupted by at least one of -C(0)-0- or -O-C(O)-; R¹⁰ is hydrogen, phenyl, or a monovalent Ci-Cs alkyl optionally terminated by -CeHs; x is 0 or 1 ; Q¹ is (CH₂)k, (CH₂CF2)m(CH₂)n,

(CH2)oS02N(CH₃)(CH2)p, 0(CF2)2(CH₂)r, or OCHFCF2OE; m is 1 to 4; k, n, o, p, and r are each independently 1 to 20; E is a C2 to C20 linear or branched alkyl group optionally interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a C6 to C10 aryl group; Rn is chosen from a straight or branched-chain perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted by one or more -0-, -CH₂-, -CFH-, or combinations thereof; Q² is (CH₂)k, (CH₂)kOC(0), or (CH₂)kC(0)0; R⁸ is H or a straight or branched alkyl chain of 2 to 30 carbons having 0 to 15 olefinic units, or mixtures thereof; and R⁷ is a Ci to C4 alkyl.

The present invention further comprises a method of forming a coated substrate with durable dirt pickup resistance comprising contacting a coating base with surface modified inorganic oxide particles to form a coating, contacting a substrate with the coating to form a coating film, allowing the surface modified inorganic oxide particles to migrate to the coating film surface, and crosslinking the ethylenically unsaturated groups of surface modified inorganic oxide particles of the coating film with each other, wherein the surface modified inorganic oxide particles comprise an oxide of X, where X is independently selected from the group consisting of Si, Ti, Zn, Zr, Mn, Al, and combinations thereof; the coating base is selected from a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating; and at least one of said particles has a surface covalently bonded to

a. at least one fluorosilane group represented by Formula (I)

Formula (II)

wherein each L¹ represents an oxygen covalently bonded to an X; and each L² is independently selected from the group consisting of H, a C1-C2 alkyl, OCH3, OCH2CH3, and OH; g and h are integers such that: g > 1 , h > 0, and g+h =3; A¹ is (CH₂)k— N(R⁹-R_fi)-R⁹, (CH₂)k— NH-C(O)-NH, (CH₂)k— NH-C(S)-NH, (CH₂)k— NH-C(O)O, (CH₂)_k— NH-C(O)S, (CH₂)_k— NH-C(O)- NH-SO₂, (CH₂)k— NH-C(S)-NH-SO₂, (CH₂)_k— NH-C(O)-N[C(O)H], (CH₂)k— NH-C(O)-CH[CH(COOH)(R¹⁰)]-S, (CH₂)_k— NH-C(O)-CH(R¹⁰)[CH(COOH)]- S, O-C(O)-NH, S-C(O)-NH, O-C(S)-NH, or S-C(S)-NH; R⁹ is a C₂-Ci₂ hydrocarbylene interrupted by at least one of -C(O)-O- or -O-C(O)-; R¹⁰ is hydrogen, phenyl, or a monovalent Ci-Cs alkyl optionally terminated by -CeHs; x is 0 or 1 ; Q¹ is (CH₂)_k, (CH₂CF₂)_m(CH₂)_n,

(CH₂)oSO₂N(CH₃)(CH₂)p, O(CF₂)₂(CH₂)_r, or OCHFCF₂OE; m is 1 to 4; k, n, o, p, and r are each independently 1 to 20; E is a C₂ to C₂o linear or branched alkyl group optionally interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a C6 to C10 aryl group; Rn is chosen from a straight or branched-chain perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted by one or more -O-, -CH₂-, -CFH-, or combinations thereof; Q² is (CH₂)_k, (CH₂)_kOC(O), or (CH₂)_kC(O)O; R⁸ is H or a straight or branched alkyl chain of 2 to 30 carbons having 0 to 15 olefinic units, or mixtures thereof; and R⁷ is a Ci to C4 alkyl.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 depicts a Transmission Electron Microscope (TEM) image of particles from Example 1 .

FIG. 2 depicts a TEM image of particles from Example 2.

FIG. 3 depicts a TEM image of particles from Example 3.

DETAILED DESCRIPTION OF THE INVENTION

Herein trademarks are shown in upper case.

The terms "(meth)acrylic" or "(meth)acrylate" indicate, respectively, methacrylic and/or acrylic, and methacrylate and/or acrylate; and the term (meth)acrylamide indicates methacrylamide and/or acrylamide.

By the term "alkyd coating" as used hereinafter is meant a conventional liquid coating based on alkyd resins, typically a paint, clear coating, or stain. The alkyd resins are complex branched and cross-linked polyesters containing unsaturated aliphatic acid residues.

By the term "urethane coating" as used hereinafter is meant a conventional liquid coating based on Type I urethane resins, typically a paint, clear coating, or stain. Urethane coatings typically contain the reaction product of a polyisocyanate, usually toluene diisocyanate, and a polyhydric alcohol ester of drying oil acids. Urethane coatings are classified by ASTM D16 into five categories. Type I urethane coatings contain a minimum of 10% by weight of a pre-reacted autoxidizable binder, characterized by the absence of significant amounts of free isocyanate grous. These are also known as uralkyds, urethane-modified alkyds, oil-modified urethanes, urethane oils, or urethane alkyds. Type I urethane coatings are the largest volume category of polyurethane coatings and include paints, clear coatings, or stains. The cured coating for a Type I urethane coating is formed by air oxidation and polymerization of the unsaturated drying oil residue in the binder.

By the term "unsaturated polyester coating" as used hereinafter is meant a conventional liquid coating based on unsaturated polyester resins, dissolved in monomers and containing initiators and catalysts as needed, typically as a paint, clear coating, stain, or gel coat formulation.

By the term "water-dispersed coatings" as used herein is meant surface coatings intended for the decoration or protection of a substrate, comprising essentially an emulsion, latex, or suspension of a film-forming material dispersed in an aqueous phase, and optionally containing surfactants, protective colloids and thickeners, pigments and extender pigments, preservatives, fungicides, freeze-thaw stabilizers, antifoam agents, agents to control pH, coalescing aids, and other ingredients.

Water-dispersed coatings are exemplified by, but not limited to, pigmented coatings such as latex paints, unpigmented coatings such as wood sealers, stains, and finishes, coatings for masonry and cement, and water- based asphalt emulsions. For latex paints the film forming material is a latex polymer of acrylate acrylic, styrene acrylic, vinyl-acrylic, vinyl, or a mixture thereof. Such water-dispersed coating compositions are described by C. R. Martens in "Emulsion and Water-Soluble Paints and Coatings" (Reinhold Publishing Corporation, New York, NY, 1965).

By the term "coating base" as used herein is meant a liquid formulation of a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating, which is later applied to a substrate for the purpose of creating a lasting film on said surface. The coating base includes those solvents, pigments, fillers, and functional additives found in a conventional liquid coating. For example, the coating base formulation may include a polymer resin and pigment dispersed in water, where the polymer resin is an acrylic polymer latex, vinyl-acrylic polymer, vinyl polymer, Type I urethane polymer, alkyd polymer, epoxy polymer, or unsaturated polyester polymer, or mixtures thereof.

a. at least one fluorosilane group represented by Formula (I)

Formula (II)

(II); wherein each L¹ represents an oxygen covalently bonded to an X; and each L² is independently selected from the group consisting of H, a C1-C2 alkyl, OCH3, OCH2CH3, and OH; g and h are integers such that: g > 1 , h > 0, and g+h =3; A¹ is (CH₂)k— N(R⁹-R_fi)-R⁹, (CH₂)k— NH-C(O)-NH, (CH₂)k— NH-C(S)-NH, (CH₂)k— NH-C(O)O, (CH₂)_k— NH-C(O)S, (CH₂)_k— NH-C(O)- NH-SO₂, (CH₂)k— NH-C(S)-NH-SO₂, (CH₂)_k— NH-C(O)-N[C(O)H], (CH₂)k— NH-C(O)-CH[CH(COOH)(R¹⁰)]-S, (CH₂)_k— NH-C(O)-CH(R¹⁰)[CH(COOH)]- S, O-C(O)-NH, S-C(O)-NH, O-C(S)-NH, or S-C(S)-NH; R⁹ is a C₂-Ci₂ hydrocarbylene interrupted by at least one of -C(O)-O- or -O-C(O)-; R¹⁰ is hydrogen, phenyl, or a monovalent Ci-Cs alkyl optionally terminated by -CeHs; x is 0 or 1 ; Q¹ is (CH₂)_k, (CH₂CF₂)_m(CH₂)_n,

(CH₂)oSO₂N(CH₃)(CH₂)p, O(CF₂)₂(CH₂)_r, or OCHFCF₂OE; m is 1 to 4; k, n, o, p, and r are each independently 1 to 20; E is a C₂ to C₂o linear or branched alkyl group optionally interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a C6 to C10 aryl group; Rn is chosen from a straight or branched-chain perfluoroalkyi group of 2 to 20 carbon atoms, optionally interrupted by one or more -O-, -CH₂-, -CFH-, or combinations thereof; Q² is (CH₂)_k, (CH₂)_kOC(O), or (CH₂)_kC(O)O; R⁸ is H or a straight or branched alkyl chain of 2 to 30 carbons having 0 to 15 olefinic units, or mixtures thereof; and R⁷ is a Ci to C4 alkyl.

The crosslinkable surface modified inorganic oxide particles of the present invention can be made by covalently grafting fluorosilanes and olefinic silanes to an inorganic oxide surface in order to impart to them both hydrophobic and crosslinkable properties. The silanes used in the present invention have a divalent organic linking group which connects the silicon atom to either a fluorine rich group, such as a perfluoroalkyi group, or an olefinic group. Silanes useful for the invention have at least one hydrolysable group which reacts with the surface of an inorganic particle thereby creating a covalent bond between the silane and the inorganic particle. Fluorosilanes that are useful in the present invention are also known as fluoroalkyl silanes which are further described in U.S. Patent 8,058,463. These include isocyanate-derived urea or thiourea

fluorosilanes, where A¹ is (ΟΗ₂)^ NH-C(O)-NH or (ΟΗ₂)^ NH-C(S)-NH; isocyanate-derived carbamate fluorosilanes, where A¹ is (CH2)k— NH- C(0)0 or 0-C(0)-NH; isocyanate-derived thiolcarbamate fluorosilanes, where A¹ is (CH₂)k— NH-C(0)S, 0-C(S)-NH, S-C(S)-NH, or S-C(0)-NH; isocyanate-derived N-sulfone urea fluorosilanes, where A¹ is (CH2)k— NH- C(0)-NH-S0₂ or (CH₂)k— NH-C(S)-NH-S0₂; isocyanate-derived N-formyl ureas, where A¹ is (CH2)k— NH-C(0)-N[C(0)H]; thioether succinamic acid fluorosilanes, where A¹ is (CH₂)k— NH-C(O)-CH[CH(COOH)(R¹⁰)]-S or (CH₂)k— NH-C(O)-CH(R¹⁰)[CH(COOH)]-S; and teriary amine fluorosilanes, where A¹ is (CH₂)k— N(R⁹-Rn)-R⁹. In one embodiment, x is 0 and Rn is a straight-chain perfluoroalkyl of 2 to 6 carbon atoms.

In one embodiment, the urea or thiourea fluorosilane is one wherein Q¹ is chosen from the group consisting of a C₂-Ci₂ hydrocarbylene interrupted by at least one divalent moiety chosen from the group consisting of -S- -S(O)-, -S(0)₂- and -0-C(0)-NH -. In another embodiment, a carbamate fluorosilane is one wherein Q¹ is chosen from the group consisting of a C₂-Ci₂ hydrocarbylene interrupted by at least one divalent moiety chosen from the group consisting of -S-, -S(O)-, -S(0)₂- and -0-C(0)-NH -. In a third embodiment, a thiolcarbamate fluorosilane is one wherein Q¹ is chosen from the group consisting of a C₂-Ci₂ hydrocarbylene interrupted by at least one divalent moiety chosen from the group consisting of -S- -S(O)-, -S(0)₂- and -0-C(0)-NH -.

Olefinic silanes may be any silane compounds containing at least one ethylenically unsaturated group that will covalently graft to an inorganic oxide surface. Specific olefinic silanes include, but are not limited to, allyl monoalkoxydialkylsilanes, allyl dialkoxyalkylsilanes, allyltrialkoxysilanes, monoalkoxydialkylvinylsilanes,

dialkoxyalkylvinylsilanes, trialkoxyvinylsilanes, (meth)acryloxyalkyl dialkoxysilanes, (meth)acryloxyalkyl monoalkoxysilanes, or

(meth)acryloxyalkyl trialkoxysilanes. These include (meth)acryloxyethyl trimethoxysilane, acryloxypropyl trimethoxysilane, (meth)acryloxybutyl trimethoxysilane, (meth)acryloxy-pentyl trimethoxysilane,

(meth)acryloxyhexyl trimethoxysilane, (meth)acryloxyheptyl

trimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane,

tnethoxyvinylsilane, and similar compounds made with other alkylene and alkoxy groups. In one embodiment, Q² is (CH2)k where k is 1 to 12; in another embodiment, k is 1 to 8; and in a third embodiment, k is 1 to 6.

Inorganic oxide particles useful to the invention include any inorganic oxide particles that have reactive groups on the surface thereof wherein such groups are capable of reacting with the hydrolysable groups of the silanes (or precursors thereof) of the invention thereby creating a covalent bond between the inorganic particle and the silane (or precursor thereof). Particularly useful inorganic particles are oxides, such as oxides of silicon, titanium, zinc, zirconium, manganese, and aluminum.

The surface modified inorganic oxide particles may have particle sizes of 10 nm to 15 microns, inclusive. In another embodiment, the particle size falls within 12 nm to 13 microns, and in a third embodiment, the particle size falls within 12 nm to 10 microns. The surface modified inorganic oxide particles contain grafted fluorinated groups, such that they exhibit a % Fluorine of 0.5% to 45%, based on the weight of the particles. In one embodiment, the particles have a % Fluorine of about 1 % to about 15%, and in a third embodiment, the particles have a % Fluorine of about 1 % to about 10%.

The particle surface is modified with the fluorinated groups and olefinic groups. In one embodiment, the surface modified inorganic oxide particles contain fluorosilane groups of Formula (I) in the amount of 1 to 99%, and having ethylenically unsaturated groups of Formula (II) in the amount of 1 to 99%, based on the sum total weight of groups of Formula (I) and groups of Formula (II). In another embodiment, the surface modified inorganic oxide particles contain fluorosilane groups of Formula (I) in the amount of 1 to 75%, and having ethylenically unsaturated groups of Formula (II) in the amount of 25 to 99%, based on the sum total weight of groups of Formula (I) and groups of Formula (II). In a third

embodiment, the surface modified inorganic oxide particles contain fluorosilane groups of Formula (I) in the amount of 25 to 99%, and having ethylenically unsaturated groups of Formula (II) in the amount of 1 to 75%, based on the sum total weight of groups of Formula (I) and groups of Formula (II). The crosslinkable surface modified inorganic oxide particles of the present invention can be made by dispersing inorganic particles in a non- polar solvent (e.g. toluene) and adding to this dispersion the desired fluorosilane. The dispersion is then heated to an elevated temperature (e.g. 80-100 °C) for about 8-10 hours. The dispersion is then allowed to cool to ambient temperature (about 20 °C). The dispersion is then placed in a centrifuge, the solvent is decanted, and the resulting inorganic particles are washed with fresh solvent. Washing is preferably done at least twice. The washed inorganic particles are then dried in an oven at elevated temperature (about 100-1 10 °C). The resulting dried inorganic particles are the final product of the invention. However, the resulting dried inorganic particles can be re-dispersed in a non-polar solvent (e.g. toluene) and additional fluorosilane can be added to this dispersion by repeating the entire procedure described in this paragraph.

The procedure for making the surface modified inorganic oxide particles in the preceding paragraph is preferable and is known as the "convergent" approach. Alternatively, some of the hydrophobized inorganic particles of the present invention can also be made via a

"divergent" approach wherein "functionalized inorganic particles" are made by reacting untreated inorganic particles with a first precursor wherein the first precursor comprises a silicon atom bonded to at least one terminal hydrolysable group which reacts with the surface of the inorganic particle thereby creating a covalent bond between the first precursor and the inorganic particle. The first precursor further comprises a terminal reactive group (e.g. an amine or an isocyante derived from an amine or an isothiocyanate derived an amine) thereby creating functionalized inorganic particles having "anchors" which comprise the terminal reactive group. These functionalized inorganic particles are then reacted with a second precursor wherein the second precursor comprises a corresponding reactive group (e.g. a terminal amine, an isocyante, an isothiocyanate, vinyl, sulfonyl chloride, or sulfonamide) capable of reacting with the terminal reactive group of the "anchors." The second precursor is also known herein by the term "capping agent." An example of a useful first precursor and second precursor combination is wherein the first precursor comprises a terminal amine group and the second precursor comprises a terminal isocyante, isothiocyanate, vinyl, sulfonyl chloride, or sulfonamide.

The invention further relates to a coating composition comprising a coating base and the surface modified inorganic oxide particles defined above, where the coating base is selected from a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating. The coating composition comprises the coating base in an amount of from about 95 to 99.98% and the surface modified inorganic oxide particles in an amount of from about 0.02 to 5% by weight, based on the total weight of the coating base and the surface modified inorganic oxide particles. In one embodiment, the coating composition comprises the coating base in an amount of from about 97 to 99.98% and the surface modified inorganic oxide particles in an amount of from about 0.02 to 3% by weight, based on the total weight of the coating base and the surface modified inorganic oxide particles.

The surface modified inorganic oxide partifcles composition produced as described above may be used directly in a coating

composition, or added solvent (the "application solvent") may be added to achieve a desirable solids content. The application solvent is typically a solvent selected from the group consisting of alcohols and ketones. The fluoropolymer composition is useful as a coating additive, wherein the fluoropolymer composition can be added to a coating base, which is applied to a substrate. When the coating is applied to a substrate, the additive compound is allowed to first migrate to the surface and

subsequently crosslink to form a durable oil-, dirt-, and water-repellent surface.

Thus, the present invention provides a method of forming a coated substrate with durable dirt pickup resistance comprising contacting a coating base with surface modified inorganic oxide particles to form a coating, contacting a substrate with the coating to form a coating film, allowing the surface modified inorganic oxide particles to migrate to the coating film surface, and crosslinking the ethylenically unsaturated groups of surface modified inorganic oxide particles of the coating film with each other, wherein the surface modified inorganic oxide particles comprise an oxide of X, where X is independently selected from the group consisting of Si, Ti, Zn, Zr, Mn, Al, and combinations thereof; the coating base is selected from a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating; and at least one of said particles has a surface covalently bonded to

a. at least one fluorosilane group represented by Formula (I)

Formula (II)

wherein each L¹ represents an oxygen covalently bonded to an X; and each L² is independently selected from the group consisting of H, a C1-C2 alkyl, OCH3, OCH2CH3, and OH; g and h are integers such that: g > 1 , h > 0, and g+h =3; A¹ is (CH₂)_k— N(R⁹-R_fi )-R⁹, (CH₂)k— NH-C(O)-NH, (CH₂)k— NH-C(S)-NH, (CH₂)k— NH-C(O)O, (CH₂)_k— NH-C(O)S, (CH₂)_k— NH-C(O)- NH-SO₂, (CH₂)k— NH-C(S)-NH-SO₂, (CH₂)_k— NH-C(O)-N[C(O)H], (CH₂)k— NH-C(O)-CH[CH(COOH)(R¹⁰)]-S, (CH₂)_k— NH-C(O)-CH(R¹⁰)[CH(COOH)]- S, O-C(O)-NH, S-C(O)-NH, O-C(S)-NH, or S-C(S)-NH; R⁹ is a C₂-Ci₂ hydrocarbylene interrupted by at least one of -C(O)-O- or -O-C(O)-; R¹⁰ is hydrogen, phenyl, or a monovalent Ci-Cs alkyl optionally terminated by -CeHs; x is 0 or 1 ; Q is (CH₂)_k, (CH₂CF₂)_m(CH₂)_n,

As noted above, the coating base is a liquid formulation of a water- dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating, which is later applied to a substrate for the purpose of creating a lasting film on said surface. The coating base includes those solvents, pigments, fillers, and functional additives found in a conventional liquid coating. Typically, the coating base may include a resin compound from 10 to 60% by weight, from 0.1 to 80% by weight of functional additives including pigments, fillers, and other additives, and the balance of the coating base

composition is water or solvent. For an architectural coating, the resin compound is in an amount of about 30 to 60% by weight, functional additives including pigments, extenders, fillers, and other additives are in an amount of 0.1 to 60% by weight, with the balance being water or solvent.

In one embodiment, the coating composition further comprises an additional fluoroadditive, such as a fluorinated polymer additive or fluorinated crosshnkable polymer compound. Such crosshnkable polymers include but are not limited to (meth)acrylic copolymers having

crosshnkable olefin groups or urethane polymers having crosshnkable olefin groups. In this case, the composition comprises the coating base in an amount of from about 90 to 99.96%, the surface modified inorganic oxide particles in an amount of from about 0.02 to 5% by weight, and the crosshnkable compound in an amount of from about 0.02 to 5% by weight, based on the total weight of the coating base, the surface modified inorganic oxide particles, and the crosshnkable compound. In another embodiment, the coating composition comprises the coating base in an amount of from about 96 to 99.9%, the surface modified inorganic oxide particles in an amount of from about 0.05 to 2%, and the crosshnkable compound in an amount of from about 0.05 to 2% by weight, based on the total weight of the coating base, the surface modified inorganic oxide particles, and the crosshnkable polymer.

In one specific embodiment, the coating composition further comprises a fluorocopolymer comprising repeat Unit A and at least one of repeat Units B, C, D, or E, in any order:

Unit A Unit B Unit e Unit D Unit E wherein R^ is a straight or branched-chain perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted by one or more ether oxygens -0- , -CH₂-, -CFH-, or combinations thereof; A² is 0, S, or N(R'), wherein R' is H or an alkyl of from 1 to about 4 carbon atoms; Q³ is a straight chain, branched chain or cyclic structure of alkylene, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, or combinations of such linking groups; v is 0 or 1 ; R¹ is H or Chh; R² is independently selected from H or an alkyl of 1 to about 4 carbon atoms; Z is a hydrophilic group selected from a hydroxyl- terminated straight or branched alkyl of 1 to 10 carbons; hydroxyl-, hydroxyalkyl-, thiol-, or amine-terminated straight or branched alkoxylate having 2 to 20 alkoxylate repeat units; thiol-terminated straight or branched alkyl of 1 to 10 carbons; or an amine-containing straight or branched alkyl of 1 to 10 carbons; M is H, HN(R⁵)3, Na, Li, Cs, K, or mixtures thereof; R⁵ is H or an alkyl or hydroxyalkyl of 1 to 12 carbon atoms; R³ is a straight or branched alkyl chain of 2 to 30 carbons having 1 to 15 olefinic units, or mixtures thereof;_Y is selected from -CH2O-, - C(0)0-, -OC(O)-, -R⁶OC(0)-, or -C(0)OR⁶0-;_R⁶ is a straight or branched alkylene of 1 to 10 carbons; R⁴ is a straight chain, branched chain, or cyclic structure alkyl group of 1 to 30 carbons; Unit A is present in an amount of about 10 to 60 mol %; Unit B is present in an amount of about 0 to 90 mol %; Unit C is present in an amount of about 0 to 90 mol %; Unit D is present in an amount of about 0 to 90 mol%; and Unit E is present in an amount of about 0 to 90 mol%; wherein the sum of monomer repeat units is equal to 100%. For example, the fluorocopolymer may comprise at least one of Units A and C, or at least one of Units A, B, and C. In one aspect, the fluorocopolymer comprises at least one of Units A and D in order to form a crosslinkable compound.

The (meth)acrylate copolymers comprise two or more repeating units derived from monomers from each of five groups. Monomers forming Unit A are fluorinated monomers such as perfluoroalkylalkyl

(meth)acrylates, monomers forming Unit B are hydrophilic monomers such as hydroxyalkyi (meth)acrylates or alkoxylated (meth)acrylates, monomers forming Unit C are acidic monomers such as (meth)acrylic acid which are optionally neutralized to form a salt, monomers forming Unit D are olefin- group-containing monomers such as fatty acid (meth), and monomers forming Unit E are hydrophobic monomers such as alkyl (meth)acrylates. The repeating units can occur in any random sequence in the proportions described above.

In one embodiment, Unit A is present in an amount from about 10 to about 60 mol%; in another embodiment, Unit A is present in an amount from about 25 to about 55 mol %; and in a third embodiment, Unit A is present in an amount from about 30 to about 50 mol %. In one

embodiment, Unit D is present in an amount from about 0.1 to about 90 mol%; in another embodiment, Unit D is present in an amount from about 2 to 40 mol%; and in a third embodiment, Unit D is present in an amount from about 2 to about 15 mol%. In one embodiment, Unit C is present in an amount of about 0.1 to 90 mol %; in another embodiment, Unit C is present in an amount from about 1 to about 60 mol %; and in a third embodiment Unit C is present in an amount from about 20 mol % to about 60 mol%. In one embodiment, Unit B is present in an amount of about 0.1 mol to 90 mol%; in another embodiment, Unit B is present in an amount of from about 0.1 to about 60 mol %; and in a third embodiment, Unit B is present in an amount of from about 10 to about 30 mol %. In another embodiment, Unit E is present in an amount of about 0.1 mol to 90 mol%; in another embodiment, Unit E is present in an amount of from about 0.1 to about 60 mol %; and in a third embodiment, Unit E is present in an amount of from about 10 to about 30 mol %. In another embodiment, at least three of Units A, B, C, D, or E are present; in a further embodiment, four of Units A, B, C, D, or E are present; and in yet a further embodiment, all five of Units A, B, C, D, and E are present.

The fluorocopolymer compound must have a molecular weight high enough to provide cleanability and durability but low enough to allow the polymer molecules to migrate through the coating medium. In one embodiment, the number average molecular weight M_n is about 1500 to about 50,000 Daltons; in a second embodiment, the number average molecular weight M_n is about 5000 to about 40,000 Daltons; and in a third embodiment, the number average molecular weight M_n is about 8000 to about 35,000 Daltons. In one embodiment, the weight average molecular weight M_w is about 5000 to about 50,000 Daltons; in a second

embodiment, the weight average molecular weight M_w is about 8000 to about 30,000 Daltons; and in a third embodiment, the weight average molecular weight M_w is about 10,000 to about 20,000 Daltons. The polydispersity index (PDI) may be about 1 .0 to about 3.0; in another embodiment, about 1 .1 to about 2.0, and in a third embodiment, about 1 .2 to about 1 .9. In another embodiment, the fluorocopolymer is a

hyperbranched polymer that results from the copolymerization with a monomer with at least two ethylenic unsaturated groups. In this case, the Mw can be up to 300,000, and PDI may be up to 6.0.

Fluorinated (meth)acrylate monomers useful for forming Unit A are synthesized from the corresponding alcohols. These fluorinated

(meth)acrylate compounds are prepared by either esterification of the corresponding alcohol with (meth)acrylic acid or by transesterification with methyl (meth)acrylate. Such preparations are well-known in the art.

Preferably, in Unit A is a straight or branched-chain

perfluoroalkyl group predominately containing from 2 to 6 carbon atoms, optionally interrupted by one or more -CH₂- or -CFH- groups. More particularly, in Formula (III) is a straight chain perfluoroalkyl group of 2 to 6 carbon atoms, and in another embodiment, 4 to about 6 carbon atoms. One preferred embodiment of the monomer forming Unit A is a perfluoroalkylethyl (meth)acrylate having the formula:

F(CF₂CF₂)_sC₂H₄OC(O)-C(R)=CH₂ wherein s is 1 to about 3 or a mixture thereof, and preferably

predominately 2 to about 3 or a mixture thereof, and R is H or methyl.

Examples of suitable linking groups Q³ in Unit A include straight chain, branched chain or cyclic structures of alkylene, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, and combinations of such linking groups such as

sulfonamidoalkylene. Preferably, Q³ is a straight chain alkylene of 1 to about 15 carbon atoms or -CONR'(CnH2n)-, the (C_nH_2n) group is linear or branched, and preferably is linear. In this case, n is 1 to 14. In one embodiment, Q³ is a straight or branched alkylene of 1 to 4 carbon atoms, and in a second embodiment, Q³ is a straight or branched alkylene of 2 to 4 carbon atoms. Within moiety A² and Q³, the alkyl in R' is linear or branched. Mixtures of fluorinated monomers may also be used.

Suitable fluorinated alcohols capable of forming the fluorinated (meth)acrylate monomers include but are not limited to

C4F₉S02NH(CH2)₃OH, C6Fi₃S0₂NH(CH2)30H, C₈Fi₇S02NH(CH2)30H, C4F₉S02NH(CH2)₂OH, C6Fi₃S0₂NH(CH2)20H, C₈Fi₇S02NH(CH2)20H, C4F₉S02N(CH3)(CH2)20H, C6Fi3S0₂N(CH₃)(CH2)20H,

C8Fi7S02N(CH₃)(CH2)20H, C4F₉CH2CF2S02NH(CH2)30H,

C₃F₇OCF2CF2S02NH(CH2)30H, C4F₉CH2CH2CF2CF₂S02NH(CH2)30H, C4F₉OCFHCH2CH₂S02NH(CH2)30H, C4F₉S02CH2CH₂NH(CH2)30H, C6Fi3S02CH2CH₂NH(CH2)30H, C₈Fi₇S02CH2CH2NH(CH2)30H,

C4F₉CH2CH2S02NHCH2CH₂OH, C6F13CH2CH2SO2NHCH2CH2OH, C8F17CH2CH2SO2NHCH2CH2OH, C4F₉CH₂CH2S02N(CH₃)CH2CH20H, C6Fi3CH2CH2S02N(CH3)CH2CH₂OH,

C8Fi7CH2CH2S02N(CH3)CH2CH₂OH, C₄F₉(CH₂)20H, C6Fi₃(CH₂)20H, C₈Fi7(CH2)20H, C₄F₉OH, CeFisOH, CsFiyOH, C4F₉CH2CH2CH₂OH, C6F13CH2CH2CH2OH, C₄F₉CH₂OH, C6F13CH2OH,

C4F₉CH2CF2CH2CH₂OH, C6F13CH2CF2CH2CH2OH,

C4F₉CH2CF2CH2CF2CH2CH₂OH, C6F13CH2CF2CH2CF2CH2CH2OH, C3F7OCF2CF2CH2CH2OH, C2F5OCF2CF2CH2CH2OH,

CF3OCF2CF2CH2CH2OH, C₃F₇(OCF2CF2)2CH2CH20H,

C2F5(OCF2CF2)2CH2CH₂OH, CF₃(OCF2CF2)2CH2CH₂OH, C3F7OCHFCF2OCH2CH2OH, C2F5OCHFCF2OCH2CH2OH,

CF3OCHFCF2OCH2CH2CH2OH, C3F7OCHFCF2OCH2CH2CH2OH, C2F5OCHFCF2OCH2CH2CH2OH, CF3OCHFCF2OCH2CH2OH,

C4F9CH2CH2SCH2CH2OH, C6F13CH2CH2SCH2CH2OH, C4F9SCH2CH2OH, C6F13SCH2CH2OH, C4F9CH2CH2CF2CF2CH2CH2OH,

C3F₇OCF(CF3)C(0)NHCH2CH20H,

C3F₇OCF(CF3)C(0)N(CH3)CH2CH20H, C4F₉NHC(0)NHCH2CH20H, C6Fi3NHC(0)NHCH2CH₂OH, HCF2(CF2)4CH₂OH, HCF2(CF2)6CH₂OH, HCF2(CF2)8CH20H, similar variations thereof, and mixtures thereof.

Examples of monomers used for form Unit B include

(meth)acrylates containing a hydrophilic pendant group selected from hydroxyl-terminated straight or branched alkyl of 1 to 10 carbons;

hydroxyl-, hydroxyalkyl-, thiol-, or amine-terminated straight or branched alkoxylate having 2 to 20 alkoxylate repeat units; thiol-terminated straight or branched alkyl of 1 to 10 carbons; or an amine-containing straight or branched alkyl of 1 to 10 carbons. Suitable examples include, but are not limited to, one or more hydroxyalkyl (meth)acrylates, alkyloxy

(meth)acrylates, or poly(alkylene glycol) (meth)acrylates. Suitable hydroxyalkyl (meth)acrylates have alkyl chain lengths of 2 to 4 carbon atoms, and include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, and 3-hydroxypropyl methacrylate. In one embodiment, R² is H or alkyl radical of 1 to 2 carbon atoms. Where Unit B is formed from one or more alkoxylated (meth)acrylates or poly(alkylene glycol) (meth)acrylates, suitable monomers may contain between 1 and 40 oxyalkylene units per molecule. In another embodiment, monomers contain from 2 to 20 oxyalkylene units per molecule, and in a third embodiment, from 4 to 12 oxyalkylene units per molecule. Such monomers include but are not limited to ethyltriethyleneglycol

(meth)acrylate, ethoxylated (meth)acrylates, poly(ethylene glycol)

(meth)acrylates, poly(ethylene glycol) methyl ether (meth)acrylates, propoxylated (meth)acrylates, poly(propylene glycol) (meth)acrylates, or poly(propylene glycol) methyl ether (meth)acrylates. Thiol-terminated or amine-terminated monomers of similar types can also be used, and are synthesized according to conventional methods. In one embodiment, Z in Unit B is -0-, and r in Unit B is 2 or 3. R³ and R⁴ are preferably alkyls of 1 , 2, or 3 carbon atoms. Examples of preferred monomers for forming Unit B are diethylaminoethyl acrylate, and/or dimethylaminoethyl methacrylate.

In one embodiment, the monomers used to form Unit C are acrylic acid or methacrylic acid; and M is H, HN(R⁵)3, Na, Li, Cs, K, or mixtures thereof. In one embodiment, M is NH₄ or Na, or a mixture thereof. Repeat units of Unit C can be formed by neutralizing the copolymer with a base, including but not limited to alkali metal hydroxides, alkali metal carbonates, ammonia, alkyl amines, or alkanolamines.

In one embodiment, the monomers used to form Unit D are at least one vinylic or (meth)acrylic monomer having a straight or branched alkyl chain of 2 to 30 carbons and having 1 to 15 olefinic units. In one embodiment, the alkyl chain contains 2 to 22 carbons, and in a third embodiment, the alkyl chain contains 3 to 18 carbons. The alkyl chains may contain 1 to 15 olefinic units but in another embodiment may contain 1 to 6 olefinic units, and in a third embodiment may contain 1 to 3 olefinic units. Such monomers may be formed from the reaction of hydroxyl- terminal (meth)acrylates or allylic compounds with fatty acids. Fatty acids may include but are not limited to oleic acid, linoleic acid, ricinoleic acid, erucic acid, palmitoleic acid, vaccenic acid, eicosenoic acid, eladic acid, eurucicic acid, nervonic acid, pinolenic acid, arachidonic acid,

eicosapentaenoic acid, docosahexanoic acid, eicosadienoic acid, docosatetranoic acid, and mixtures thereof. Specific examples of monomers used to form Unit D include but are not limited to oleic

(meth)acrylate, linoleic (meth)acrylate, palmitic methyl ester, soybean oil methyl ester, sunflower oil methyl ester, oleic ethyl (meth)acrylate, ricinoleic (meth)acrylate, erucic (meth)acrylate, palmitoleic (meth)acrylate, vaccenic (meth)acrylate, eicosenoic (meth)acrylate, eladic (meth)acrylate, eurucicic (meth)acrylate, nervonic (meth)acrylate, pinolenic

(meth)acrylate, arachidonic (meth)acrylate, eicosapentaenoic

(meth)acrylate, docosahexanoic (meth)acrylate, eicosadienoic (meth)acrylate, docosatetranoic (meth)acrylate, and versions of the same having different chain lengths.

Unit E may be formed from (meth)acrylic monomers having pendant straight chain, branched chain, or cyclic structure alkyl groups of 1 to 30 carbons. In one embodiment, the alkyl groups contain 1 to 22 carbons, and in a third embodiment, the alkyl groups contain 6 to 22 carbons. Specific examples of such monomers include but are not limited to stearyl (meth)acrylate, tridecyl (meth)acrylate, lauryl (meth)acrylate, 2- ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, palmitic (meth)acrylate, caprylic (meth)acrylate, captric (meth)acrylate, mysteric (meth)acrylate, arachidic (meth)acrylate, behenic (meth)acrylate, lignoceric (meth)acrylate, or cetyl (meth)acrylate.

The fluorocopolymer may or may not further comprise additional repeat units outside of the units, resulting from the use of additional monomers. Suitable monomers are ethylenically-unsaturated monomers, including but not limited to, amine monomers such as diethylaminoethyl acrylate and/or dimethylaminoethyl methacrylate, glycidyl (meth)acrylates, aminoalkyl methacrylate hydrochloride, acrylamide, alkyl acrylamides, or n-methylol (meth)acrylamide. When no additional repeat units outside of the units are used, then the sum Units A + B + C + D + E is equal to 100%. When additional repeat units are present, then the sum Units A + B + C + D + E + any additional monomer repeat units is equal to 100%.

The fluorocopolymers in the present invention are prepared by polymerization of the fluorinated and non-fluorinated monomers. The polymerization process comprises contacting the fluorinated and non- fluorinated (meth)acrylate monomers as defined hereinabove in an organic solvent in the presence of a free radical initiator, chain transfer agent, and optionally other monomers in an inert atmosphere. For example, the monomers can be mixed in a suitable reaction vessel equipped with an agitation device. A heating source and a cooling source are provided as necessary. In a typical process, the fluorinated and non-fluorinated monomers are combined in the reaction vessel with the solvent and chain transfer agent to provide a reaction mixture, and the reaction mixture is heated to an appropriate temperature, e.g. 80 °C. Alternatively, the monomers may be fed one at a time, or in a mixture, to an existing solution in a reaction vessel at a selected feed rate. In this embodiment, the existing solution in the reaction vessel may contain the solvent; the solvent and chain transfer agent; or the solvent, chain transfer agent, and one or more monomers. In another embodiment, the chain transfer agent may be fed alone, or in a mixture with one or more monomers, to an existing solution in a reaction vessel at a selected feed rate. In this embodiment, the existing solution in the reaction vessel may contain the solvent; the solvent and one or more monomers; or the solvent, one or more monomers, and the initiator. In each embodiment, the initiator may be included in the existing solution or may be fed into the reactor at a later time.

Suitable free radical initiators include organic peroxides and azo compounds. Examples of particularly useful organic peroxides are benzoyl peroxide, f-butyl peroxide, acetyl peroxide, and lauryl peroxide. Examples of particularly useful azo compounds include 2,2'-azobis(2- amidinopropane dihydrochloride, 2,2'-azobis(isobutyramidine)

dihydrochloride, and azodiisobutylronitnle. Azo initiators are commercially available from E. I. du Pont de Nemours and Company, Wilmington, DE, under the name of "VAZO".

Suitable redox initiators include potassium or ammonium

peroxydisulfate; combinations of peroxides such as hydrogen peroxide with Fe²⁺, Cr²⁺, V²⁺, Ti³⁺, Co²⁺, Cu⁺; combinations of HSOs^", SOs^2", S2O3²-, or S2O5^2" with Ag⁺, Cu²⁺, Fe³⁺' CIO^3", or H2O2; combinations of organic alcohols with Ce⁴⁺, V⁵⁺, Cr⁶⁺, or Mn³⁺; and combinations of

peroxydiphosphate compounds with Ag⁺, V⁵⁺, or Co²⁺. Such systems may be used when low temperature or rapid activation is desirable.

The fluorocopolymer compounds may further comprise residue from a chain transfer agent, also known as a polymerization regulator. The term "residue" is herein defined as the portion of the chain transfer agent structure that is covalently bonded to the polymer molecule. The total polymer reaction mixture may also include some polymer molecules that do not contain the chain transfer agent residue. The chain transfer agent can be used in amounts to limit or control the molecular weight of the fluoropolymer, typically in amounts of about 1 to 25 mol%, preferably about 2 to 20 mol%, more preferably about 3 to 15 mol%, and most preferably 5 to 10 mol%, based on the total amount of chain transfer agent and monomers employed. In one embodiment, hydrophilic chain transfer agents with the formula (III):

(III) (D-G-S)tH₂-t,

are used, wherein t is 1 or 2; G is a linear or branched alkylene of 1 to about 4 carbon atoms, optionally substituted with one or more hydrophilic functional groups selected from hydroxyl, carboxyl, or amine; and D is a hydrophilic functional group selected from hydroxyl, carboxyl, thiol, or amine. Where t=2, the chain transfer agents are disulfide compounds of the formula D-G-S-S-G-D. Suitable chain transfer agents include but are not limited to dodecanethiol, thioglycerol, mercaptoethanol, thioglycolic acid, dithioerythritol, 2-mercaptopropionic acid, and 3-mercaptopropionic acid, or mixtures thereof.

Suitable solvents are alkanes, alcohols and ketones having boiling points of less than 130°C. Suitable organic solvents useful in the preparation of the fluoropolymer include methyl isobutyl ketone, butyl acetate, tetrahydrofuran, acetone, isopropanol, ethyl acetate, methylene chloride, chloroform, carbon tetrachloride, cyclohexane, hexane, dioxane, hexafluoroisopropanol, and mixtures of two or more thereof.

Cyclohexane, isopropanol, methyl isobutyl ketone, or mixtures thereof are preferred. Blends of isopropanol and methyl isobutyl ketone are particularly preferred, since both solvents form azeotropes with water boiling below 100°C, facilitating their removal from the final aqueous dispersion. Blends of organic solvents with other types of co-solvents, including water, may also be used. Preferred are isopropanol /methyl isobutyl ketone blends containing between about 20% and about 80% of methyl isobutyl ketone.

The fluorocopolymer as described above used in the method of the present invention is preferably in the form of an aqueous dispersion. After the polymerization is complete, as can be monitored by ¹ H NMR, the acidic polymer solution can be neutralized using a basic water solution to form an aqueous dipserion. The amount of base necessary is calculated by assuming complete salt formation of all acid functionalities. Optionally 0 - 5% mole percent excess of base is added to ensure conversion of all acid to salt. The final pH of the emulsion is between about 6 and about 9, and preferably is between 6 and 8. The bases suitable for the

neutralization are alkali metal hydroxides, alkali metal carbonates, ammonia, alkyl amines, or alkanolamines. Ammonia solution is preferred. Following neutralization, the organic solvents may be removed by distillation to form a completely aqueous system.

The coating compositions may further comprise additional components to provide surface effects to the resulting coating. These additional components may include additional fluorinated additives to provide additional cleanability, dirt pickup resistance, or blocking properties to the coating. Cure additives may also be included. For example, the composition may further comprise a non-polymeric ethylenically unsaturated crosslinkable compound to provide additional crosslinking sites. In one embodiment, this non-polymeric crosslinkable compound is a fatty acid compound in an amount of about 0.001 to 1 % by weight, based on the total weight of the coating composition. Any fatty acid, including those listed above for use in forming the monomer of Unit D, may be employed. In one embodiment, the fatty acid is the same fatty acid used to form the monomer of Unit D.

The coating compositions may also include a pigment. Such a pigment may be part of the coating base formulation, or may be added subsequently. Any pigment can be used with the present invention. The term "pigment" as used herein means opacifying and non-opacifying ingredients which are particulate and substantially non-volatile in use. Pigment as used herein includes ingredients labeled as pigments, but also ingredients typically labeled in the coating trade as inerts, extenders, fillers, and similar substances.

Representative pigments that can be used with the present invention include, but are not limited to, rutile and anatase T1O2, clays such as kaolin clay, asbestos, calcium carbonate, zinc oxide, chromium oxide, barium sulfate, iron oxide, tin oxide, calcium sulfate, talc, mica, silicas, dolomite, zinc sulfide, antimony oxide, zirconium dioxide, silicon dioxide, cadmium sulfide, cadmium selenide, lead chromate, zinc chromate, nickel titanate, diatomaceous earth, glass fibers, glass powders, glass spheres, MONASTAL Blue G (C. I. Pigment Blue 15), molybdate Orange (C. I. Pigment Red 104), Toluidine Red YW (C. I. Pigment 3)- process aggregated crystals, Phthalo Blue (C. I. Pigment Blue 15)- cellulose acetate dispersion, Toluidine Red (C. I. Pigment Red 3),

Watchung Red BW (C.I. Pigment Red 48), Toluidine Yellow GW (C. I.

Pigment Yellow 1 ), MONASTRAL Blue BW (C. I. Pigment Blue 15),

MONASTRAL Green BW (C. I. Pigment Green 7), Pigment Scarlet (C. I. Pigment Red 60), Auric Brown (C. I. Pigment Brown 6), MONASTRAL Green G (C.I. Pigment Green 7), MONASTRAL Maroon B, MONASTRAL Orange, and Phthalo Green GW 951.

Titanium dioxide (T1O2) is the preferred pigment to use with the present invention. Titanium dioxide pigment, useful in the present invention, can be in the rutile or anatase crystalline form. It is commonly made by either a chloride process or a sulfate process. In the chloride process, TiCU is oxidized to T1O2 particles. In the sulfate process, sulfuric acid and ore containing titanium are dissolved, and the resulting solution goes through a series of steps to yield T1O2. Both the sulfate and chloride processes are described in greater detail in "The Pigment Handbook", Vol. 1 , 2nd Ed. , John Wiley & Sons, NY (1988), the teachings of which are incorporated herein by reference.

When used as an additive to a coating base, the surface modified inorganic oxide particles, crosslinkable polymer compound, and additives, are effectively introduced to the coating base by thoroughly contacting, e.g., by mixing the additives with the coating base at ambient temperature. More elaborate contacting or mixing methods can be employed such as using a mechanical shaker or providing heat. Such methods are generally not necessary and generally do not substantially improve the final coating composition.

When used as an additive to a coating base, the crosslinkable polymer is generally added at about 0.02 weight % to about 5 weight % on a dry weight basis of the fluoropolymer to the weight of the wet paint. In one embodiment, from about 0.02 weight % to about 0.5 weight % is used, and in a third embodiment, from about 0.05 weight % to about 0.25 weight % of the crosslinkable polymer compound is added to the paint.

The coating compositions of the present invention are useful for providing a protective and/or decorative coating to a wide variety of substrates. Such substrates include primarily construction materials and hard surfaces. The substrate is preferably selected from the group consisting of wood, metal, wallboard, masonry, concrete, fiberboard, and paper. Other materials may also be used as the substrate.

The coatings of the present invention may be used to treat a substrate by contacting the substrate with a coating composition

comprising a coating base and a polymer composition of Formula (I) and drying or curing the coating composition on the substrate. Any method of contacting a coating composition with a substrate can be used. Such methods are well known to a person skilled in the art, such as by brush, spray, roller, doctor blade, wipe, dip, foam, liquid injection, immersion or casting. Following application of the coating to a substrate, the polymer compound is polymerized using any conventional means, including allowing the additive to crosslink in air by oxidative curing. Radiation curing, including UV curing, may also be employed. Cure initiators and additives may be combined with the coating compositions to improve cure efficiency.

The compositions of the present invention provide performance as well as durability to coatings. They impart unexpectedly desirable surface effects such as: increased water and oil contact angles, enhanced dirt pickup resistance, and enhanced cleanability to the coating films. For these reasons, the compounds of the present invention are particularly suitable for use as additives to exterior coating and paints.

MATERIALS AND TEST METHODS

All solvents, monomers and reagents, unless otherwise indicated, were purchased from Sigma-Aldrich or VWR and used directly as supplied. Molecular weight analysis was performed using a Size

Exclusion Chromatography (SEC) system [Alliance 2695™, Waters Corporation (Milford, MA)] equipped with with a differential refractive index detector, multi-angle light scattering photometer and a differential capillary viscometer ViscoStar™.

Test Methods

Dosing of Fluorinated Silica and/or Polymer Additives in Paint and Test Panel Application

Aqueous dispersions of fluorinated silica were added to select commercially available exterior latex paints at various percents by weight, calculated by weight of the fluorinated silica solids; the paints were free of fluoroadditives. Where fluoroacrylic copolymers were also used, they were added at 350 ppm fluorine levels to selected commercially available interior and exterior latex paints that were, prior to dosing, free of fluoroadditives. The samples were mixed using an overhead Cowles Blade stirrer at 600 rpm for 10 minutes. The mixture was then transferred to a glass bottle, sealed and placed on a roll mill overnight to allow uniform mixing of the fluoropolymer. The samples were then drawn down uniformly on a black Leneta Mylar® card (5.5" x 10") or Aluminium Q-panel (4" x 12") via a BYK-Gardner drawdown apparatus using 5 ml_ bird- applicator. The paint films were then allowed to dry at room temperature for 7 days.

Test Method 1 . Evaluation of Oil Repellencv via Contact Angle (CA) Measurement

Oil contact angle measurements were used to test for the migration of fluoroadditive to the surface of the paint film. Oil contact angle testing was performed by goniometer on 1 inch strips of Leneta panel coated with dried paint film.

A Rame-Hart Standard Automated Goniometer Model 200 employing DROP image standard software and equipped with an automated dispensing system, 250 μΙ syringe, and illuminated specimen stage assembly was used. The goniometer camera was connected through an interface to a computer, allowing the droplet to be visualized on a computer screen. The horizontal axis line and the cross line could both be independently adjusted on the computer screen using the software.

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

To determine the contact angle of the test fluid on the sample, approximately one drop of test fluid was dispensed onto the sample using a 30 μΙ_ pipette tip and an automated dispensing system to displace a calibrated amount of the test fluid. For oil contact angle measurements, hexadecane was suitably employed. Horizontal and cross lines were adjusted via the software in case of the Model 200 after leveling the sample via stage adjustment, and the computer calculated the contact angle based upon modeling the drop appearance. The initial contact angle is the angle determined immediately after dispensing the test fluid to the sample surface. Initial contact angles above 30 degrees are indicators of effective oil repellency.

Test Method 2. Dirt Pick-up Resistance (DPR) Test for Exterior Paints

DPR testing was used to evaluate the ability of the painted panels to prevent dirt accummulation. An artificial dry dirt comprised of silica gel (38.7%), aluminum oxide powder (38.7%), black iron oxide powder (19.35%) and lamp black powder (3.22%) was used for this test. The dust components were mixed and placed on a roller for 48 hours for thorough mixing and stored in a decicator.

Exterior paint samples were drawn down to Aluminium Q-panels cut to a size of 1 .5" x 2", and four replicates of these samples were taped onto a 4" x 6" metal panel. The initial whiteness (L^* initial) of each Q-panel was measured using a Hunter Lab colorimeter. The 4" x 6" metal panel was then inserted into a 45 degree angle slot cut in a wooden block. The dust applicator containing metal mesh dispensed the dust on the panels until the panels were completely covered with dust. The excess dust was then removed by lightly tapping the mounted panels 5 times on the wooden block inside the shallow tray. The 4" x 6" panel which held the dusted panels was then clamped onto a Vortex-Genie 2 for 60 seconds to remove any remaining dust. The panel was then removed and tapped 10 times to dislodge any remaining dust. The whiteness (L^* dusted) of each 1 .5" x 2" sample was re-measured using the same colorimeter, and the difference in whiteness before and after dusting was recorded. The values were averaged. DPR is expressed in terms of AL^* where AL^* = (L^* initial - L^* dusted). A lower AL^* value indicates better dirt pick-up resistance.

Test Method 3. Weathering (WOM) for DPR and Oil Contact Angle

Durability

Accelerated weathering of coated Q-panels was performed in an ATLAS Ci5000 Xenon Lamp Weather-o-Meter. The Xenon lamp was equipped with Type S Boro Inner and Outer Filters. Weathering cycles were performed according to D6695, cycle 2. During the weathering period, the panels were subjected to repeated 2-hour programs, which included 18 minutes of light and water spray followed by 102 minutes of light only. During the entire program, panels were held at 63 °C and during the UV only segment relative humidity was held at 50%.

For a 24-hour WOM program, freshly coated aluminum Q-panels were allowed to air dry for 7-days. The initial whiteness (L^* initial) of each Q-panel was measured using a Hunter Lab colorimeter. One set of panels was subjected to DPR testing (as per Test Method 2) as well as oil contact angle testing (as per Test Method 1 ). A duplicate set of panels was placed in the weather-o-meter and allowed to proceed through 12 continuous 2- hour cycles according to the description above. After completion of the weathering cycles, the panels were dried, evaluated according to Test Methods 1 and 2, and re-subjected to DPR.

Examples

A three necked round bottom flask fitted with a nitrogen inlet, addition funnel and septum was charged with (9Z)-octadecanoic acid (4.2 g, g, 14.86 mmol) and diethyl ether (14.0 g). 1 -[3-(dimethylamino)propyl]- 3-ethylcarbodiimide hydrochloride (EDCI) (3.42 g, 17.83 mmol) and 4- (dimethylamino)pyridine (1 .82 g, 14.86 mmol) were added to the flask and the mixture stirred for 10 minutes in an ice water bath. A solution of hydroxyethylethacrylate (2.13 g, 16.3 mmol) in diethyl ether (4 g) was then added via the addition funnel. After the addition was complete the mixture was stirred at room temperature for 12 hours. The reaction mixture was then poured into a saturated solution of ammonium chloride (20 g). The layers were separated and the aqueous layer was extracted with diethyl ether (15 g). The combined organics were washed with water and dried over anhydrous MgS04. Evaporation of the solvent followed by drying under vacuum provided the product as a pale yellow oil (5.766 g, 14.8 mmol). 1 H NMR (CDCI3): δ 0.87 (t, 5.7 Hz, 3H), 1 .24-1.36 (m, 20H), 1 .62 (m, 2H), 1 .94 (m, 3H), 2.0 (dt, J = 5.7, 2.0 Hz, 4H), 2.3 (t, J = 7.0 Hz, 2H), 4.3 (m, 4H), 5.34 (m, 2H), 5.6 (dt, J = 5.7, 1 .6 Hz, 1 H), 6.1 (m, 1 H).

Preparation of Monomer B: Linoleic methacr late

By following the above procedure described for the preparation of Monomer A, from (9Z, 12Z)-9, 12-octadecanoic acid (2.40, 8.87 mmol) and hydroxyethylmethacrylate (1 .45 g, 10.8) mmol) provided the product as a pale yellow oil (3.36 g, 8.57 mmol). The product was contaminated with traces of hydroxyethylmethacrylate-". 1 H NMR (CDCI3): δ 0.88 (t, 5.7 Hz, 3H), 1 .23-1 .36 (m, 16H), 1 .62 (m, 2H), 1.94 (m, 3H), 2.0 (dt, J = 5.7, 1 .8 Hz, 4H), 2.33 (t, J = 7.0 Hz, 2H), 4.3 (m, 4H), 5.34 (m, 4H), 5.6 (dt, J = 5.7, 1 .6 Hz, 1 H), 6.1 (m, 1 H).

Preparation of Polymer 1

A 250 ml_ three-necked round bottom flask was equipped with a reflux condenser, a nitrogen sparge line, a TEFLON-coated magnetic stir bar, and a dip-tube for measurement of the internal temperature via a thermocouple was charged with MIBK (1 1 ml_) and IPA (25 ml_). The solution was subjected to sub-surface sparging with nitrogen using a needle for 1 hour at room temperature.

In a separate 100 ml flask, equipped with a rubber septa and nitrogen inlet, was charged with 1 H, 1 H,2H,2H-perfluorooctyl methacrylate (14.58 g, 33.8 mmol), hydroxyethyl methacrylate (1 .46 g, 1 1 .22 mmol), Monomer A (1 .0 g, 2.53 mmol) and methacrylic acid, (3.16 g, 36.74 mmol). The solution was subjected to sub-surface sparging with N2 using a needle for 1 hour at room temperature. The monomer solution was diluted to a total volume of 20 ml_ using MIBK/IPA from the first flask. A solution of VAZO 67 (0.395 g, 2.05 mmol) was prepared using sparged MIBK/IPA (19 ml_) from the first reaction flask. VAZO 67 solution and monomer solution were loaded into two separate 20 ml syringes equipped with a 22 gauge needle.

1 -Thioglycerol (0.988 g, 9.13 mmol) was added to the first reaction flask containing the remaining sparged MIBK/IPA solvent. The reactor was heated to 80 °C (internal temperature). When the reaction

temperature reached 80 °C, the monomers and initiator were charged via syringe pump over 6 hours. The reaction was allowed to stir for an additional 16 hours at 80 °C. Monomer consumption was monitored via NMR using mesitylene as an internal standard (97% conversion). The polymer sample was also analyzed by GPC for number average molecular weight, M_n = 5.49 kDa and PDI = 1 .8.

The polymer solution in MIBK/IPA was heated back to 70 °C. A neutralization solution consisting of NH₄OH (2.85 g, 47.0 mmol) in H2O (58.3 ml_) was prepared and heated to 45 °C. The ammonia solution was added dropwise to the polymer solution via addition funnel over 20 minutes to achieve a cloudy solution. The solution was stirred at 70 °C for an additional 1 hour, and the MIBK/IPA was removed under vacuum to produce 102.5 g of a hazy yellow dispersion of polymer in water with a pH 8.0. The dispersion was determined to be 22.9 weight % solids.

Preparation of Polymer 2

By following a similar procedure as described in the preparation of Polymer 1 , semi-batch polymerization was performed using 1 H, 1 H,2H,2H- perfluorooctyl methacrylate (14.58 g, 33.8 mmol), hydroxyethyl

methacrylate (1.46 g, 1 1 .22 mmol), Monomer B (0.55 g, 1 .41 mmol)), methacrylic acid (3.16 g, 36.74 mmol), VAZO 67 (0.395 g, 2.05 mmol) and 1 -thioglycerol (0.988 g, 9.13 mmol) chain transfer agent, yielding a polymer solution with >97 % monomer conversion (¹ H NMR). The polymer sample was analyzed by GPC for number average molecular weight, Mn = 5.1 kDa and PDI = 2.0.

Neutralization of the polymer using NH₄OH (2.85 g, 47.0 mmol) in H2O (58.3 g), followed by removal of the organic solvents under vacuum, provided a hazy yellow dispersion (27.7 wt.% solids, pH 8.0) in water. Preparation of Polymer 3

By following a similar procedure as described in the preparation of

Polymer 1 , semi-batch polymerization was performed using 1 H, 1 H,2H,2H- perfluorooctyl methacrylate (14.58 g, 33.8 mmol)), hydroxyethyl methacrylate (1 .46 g, 1 1 .22 mmol), Monomer A (6.25 g, 9.66 mmol) and methacrylic acid, (3.16 g, 36.74 mmol), VAZO 67 (0.395 g, 2.05 mmol), and 1 -thioglycerol (0.988 g, 9.13 mmol) chain transfer agent to provide a polymer solution with >98 % monomer conversion (¹ H NMR). The polymer sample was analyzed by GPC for number average molecular weight, M_n = 4.5 kDa and PDI = 1.8.

Neutralization of the polymer using NH₄OH (2.85 g, 47.0 mmol), in H2O (58.3 g) followed by removal of the organic solvents under vacuum provided a hazy yellow dispersion (1 17.5 g, 22.0 wt.% solids, pH 8.5) in water.

Preparation of Polymer 4 By following a similar procedure as described in the preparation of Polymer 1 , semi-batch polymerization was performed using 1 H, 1 H,2H,2H- perfluorooctyl methacrylate (14.58 g, 33.8 mmol), Monomer A (6.7 g, 15.45 mmol) and methacrylic acid, (3.16 g, 36.74 mmol), VAZO 67 (0.395 g, 2.05 mmol) and 1 -thioglycerol (0.988 g, 9.13 mmol) chain transfer agent, yielding a polymer solution with >97 % monomer conversion (¹ H NMR). The polymer sample was analyzed by GPC for number average molecular weight, M_n = 1 1 .0 kDa and PDI = 2.8.

Neutralization of the polymer using NH₄OH (2.85 g, 47.0 mmol) in H2O (58.3 g), followed by removal of the organic solvents under vacuum, provided a hazy yellow dispersion (23 wt.% solids, pH 8.0) in water.

Preparation of Polymer 5

By following a similar procedure as described in the Preparation of Polymer 1 , semi-batch polymerization was performed using 1 H, 1 H,2 - ,2H- perfluorooctyl methacrylate (14.58 g, 33.8 mmol), hydroxyethyl

methacrylate (3.29 g, 25.31 mmol), methacrylic acid (2.18 g, 25.31 mmol) VAZO 67 (0.395 g, 2.05 mmol), and 1 -thioglycerol (0.988 g, 9.13 mmol) in MIBK, providing the polymer solution with 99 % monomer conversion (¹ H NMR). The polymer sample was analyzed by GPC (M_n = 6.6 kDa and PDI = 2.2). The solids concentration from the organic phase was calculated to be 59.6 wt. %. A portion of the solution of polymer in MIBK (1 .0 g, 59.6 wt% solid) was further diluted with MIBK (0.3 g) and charged with allyl glycidylether (0.135 g, 1 .19 mmol) and pyridine (0.005 g) under nitrogen atmosphere. The mixture stirred at room temperature for 12 hours under nitrogen to obtain the post modified polymer.

Preparation of Polymer 6

DESMODUR N3300 (6.68 g) was added to a round-bottomed flask with magnetic stir bar kept under N2 atmosphere. Methyl isobutyl ketone (MIBK) (10.9 g), 1 H, 1 H,2H,2H-perfluorooctanol (4.16 g, 1 1 .44 mmol), glycolic acid (0.74 g, 9.7 mmol), poly(ethyleneglycol)monomethacrylate (MW 526, 3.1 g, 5.89 mmol), trimethylolpropane diallylether (1 .40 g, 5.89 mmol) and IRGACURE 2959 (0.39g, 1.73 mmol) were added. The reaction mixture was heated to 60 °C and charged with catalytic dibutyltin dilaurate (0.02 g) in MIBK (0.7 g). The reaction mixture was then heated to 90 °C for 12 hours. The reaction mixture turned to a thick yellow liquid. The mixture was then cooled to 50 °C. A neutralizing solution of NH₄OH (0.59 g, 9.7 mmol Nhta) in H2O (38 ml_) was then added. A white slurry formed at pH ~10 and the contents then stirred with heating at 50 °C for for 30 minutes. A sample was taken for weight percent solids analysis and was determined to be 14.6 % by weight. A calculated amount of this dispersion (350 ppm of F) was added to samples of exterior test paint and the drawdown panels evaluated as per the test methods described.

Example 1

An aqueous solution containing 267.0 g of water and 0.28 g of L-

Lysine was first prepared. After raising the temperature to 90 °C, a mixture containing 10.0 g tetraethyl orthosilicate, 5.0 g of 1 H, 1 H,2 - ,2H- pefluorooctyltriethoxysilane, 5.0 g of allyltrimethoxysilane, and 17.69 g of ethanol was added. The formation of the particle was achieved by stirring the solution at 90 °C for 2 days followed by allowing the solution to cure at 100 °C for one additional 1 to complete the sol-gel reaction. Finally, the particle dispersion was filtered and rinsed with water to remove ethanol, and then re-dispersed into water. The structure of the resulting particles was analyzed using transmission electron microscopy and is shown in Figure 1. The resulting fluorinated silica was added to exterior test paint at various loading levels as described in Table 1 and evaluated by the test methods above.

Example 2

An aqueous solution containing 534.0 g of water and 0.56 g of L- Lysine was first prepared. After raising the temperature to 90 °C, a mixture which contained 20.0 g tetraethyl orthosilicate, 5.0 g of

1 H, 1 H,2H,2H-pefluorooctyltriethoxysilane, 10.0 g of allyltrimethoxysilane, and 35.38 g of ethanol was added. The formation of the particle was achieved by stirring the solution at 90 °C for 2 days followed by allowing the solution to cure at 100 °C for one additional day to complete the sol- gel reaction. Finally, the particle dispersion was filtered and rinsed with water to remove ethanol, and then re-dispersed into water. The structure of the resulting particles was analyzed using transmission electron microscopy and is shown in Figure 2. The resulting fluorinated silica was added to exterior test paint at various loading levels as described in Table 1 and evaluated by the test methods above.

Example 3

An aqueous solution containing 534.0 g of water and 0.56 g of L- Lysine was first prepared. After raising the temperature to 90 °C, a mixture containing 20.0 g tetraethyl orthosilicate, 2.5 g of 1 H, 1 H,2 - ,2H- pefluorooctyltriethoxysilane, 10.0 g of allyltnmethoxysilane, and 35.38 g of ethanol was added. The formation of the particle was achieved by stirring the solution at 90 °C for 2 days followed by allowing the solution to cure at 100 °C for one additional day to complete the sol-gel reaction. Finally, the particle dispersion was filtered and rinsed with water to remove ethanol, and then re-dispersed into water. The structure of the resulting particles was analyzed using transmission electron microscopy and is shown in Figure 3. The resulting fluorinated silica was added to exterior test paint at various loading levels as described in Table 1 and evaluated by the test methods above.

Examples 4-8

The resulting fluorinated silicas from Examples 1 to 3 were added to exterior test paint at various loading levels as described in Table 1 and evaluated by the test methods above.

Comparative Example A

Samples of exterior test paint, without additive, were applied to drawdown panels and evaluated as per the test methods described.

Comparative Example B

By following a similar procedure as described in the preparation of

Polymer 1 , semi-batch polymerization was performed using 1 H, 1 H,2H,2H- perfluorooctyl methacrylate (14.58 g, 33.8 mmol), hydroxyethyl

methacrylate (2.51 g, 19.3 mmol), methacrylic acid (2.67 g, 31 .0 mmol), VAZO 67 (0.395 g, 2.05 mmol), and 1 -thioglycerol (0.840 g, 7.76 mmol) chain transfer agent, yielding a polymer solution with >95 % monomer conversion (¹H NMR). The polymer sample was analyzed by GPC for number average molecular weight, M_n = 5.7 kDa and PDI = 1 .95

Neutralization of the polymer using NH₄OH (2.39 g, 39.4 mmol) in H2O (58.3 g), followed by removal of the organic solvents under vacuum, provided a hazy yellow dispersion (90.5 g, 21 .7 wt.% solids, pH 9) in water. A calculated amount of this polymer dispersion (350 ppm of Fluorine) was added to samples of exterior test paint and the drawdown panels evaluated as per the test methods described.

Table 1. Performance of Fluorinated Silica from Examples 1 to 3

Examples 9 to 14

Several samples were prepared by mixing the fluorinated silica described in Example 1 (2% by weight of paint composition) with Polymers 1 to 6 (350 ppm of Fluorine in paint composition), and then adding the blend to the exterior test paint. The drawdown panels were then evaluated using the test methods described above, and the results are summarized in Table 2.

Comparative Examples C-D

Samples of exterior test paint, incorporating 350 ppm by Fluorine of

Polymers 1 or 2, respectively, were applied to drawdown panels and evaluated as per the test methods described.

Table 2. Performance of Fluorinated Silica of Example 1 with

Polymers 1 to 6

Examples 15 to 16

Several samples were prepared by mixing the fluorinated silica described in Example 2 (1 % by weight of paint composition) with Polymers 1 to 2 (350 ppm of Fluorine in paint composition), and then adding the blend to the exterior test paint. The drawdown panels were then evaluated using the test methods described above, and the results are summarized in Table 3.

Table 3. Performance of Fluorinated Silica of Example 2 with

Polymers 1 to 2

Examples 17 to 18

Several samples were prepared by mixing the fluorinated silica described in Example 3 (1 % by weight of paint composition) with Polymers 1 to 2 (350 ppm of Fluorine in paint composition), and then adding the blend to the exterior test paint. The drawdown panels were then evaluated using the test methods described above, and the results are summarized in Table 4.

Table 4. Performance of Fluorinated Silica of Example 3 with

Polymers 1 to 2

Example 19

Several samples were prepared by mixing the fluorinated silica described in Example 1 (2% by weight of paint composition) with the polymer from Comparative Example B (350 ppm of Fluorine in paint composition), and then adding the blend to the exterior test paint. The drawdown panels were then evaluated using the test methods described above, and the results are summarized in Table 5.

Table 5. Performance of Fluorinated Silica of Example 2 with

Polymers 1 to 2

Claims

CLAIMS What is claimed is:

1 . Surface modified inorganic oxide particles comprising an oxide of X wherein X is independently selected from the group consisting of Si, Ti, Zn, Zr, Mn, Al, and combinations thereof; at least one of said particles having a surface covalently bonded to

a. at least one fluorosilane group represented by Formula (I)

(L¹)g(L²)hSi— A¹— Q¹x-Rfi (I); and b. at least one ethylenically unsaturated group represented by Formula (II)

wherein

each L¹ represents an oxygen covalently bonded to an X; and each L² is independently selected from the group consisting of H, a C1-C2 alkyl, OCHs, OCH2CH3, and OH; g and h are integers such that: g > 1 , h > 0, and g+h =3;

A¹ is (CH₂)k— N(R⁹-Rfi )-R⁹, (CH₂)k— NH-C(O)-NH, (CH₂)_k— NH- C(S)-NH, (CH₂)k— NH-C(O)O, (CH₂)_k— NH-C(O)S, (CH₂)_k— NH-C(O)-NH- SO₂, (CH₂)k— NH-C(S)-NH-SO₂, (CH₂)_k— NH-C(O)-N[C(O)H], (CH₂)k— NH- C(O)-CH[CH(COOH)(R¹⁰)]-S, (CH₂)_k— NH-C(O)-CH(R¹⁰)[CH(COOH)]-S, O-C(O)-NH, S-C(O)-NH, O-C(S)-NH, or S-C(S)-NH;

R⁹ is a C₂-Ci₂ hydrocarbylene interrupted by at least one of

-C(O)-O- or -O-C(O)-;

R¹⁰ is hydrogen, phenyl, or a monovalent Ci-Cs alkyl optionally terminated by -C6H5;

x is 0 or 1 ;

Q¹ is (CH₂)_k, (CH₂CF₂)m(CH₂)n, (CH₂)oSO N(CH₃)(CH₂)_P,

O(CF₂)₂(CH₂)_r, or OCHFCF₂OE;

m is 1 to 4;

k, n, o, p, and r are each independently 1 to 20;

E is a C₂ to C₂o linear or branched alkyl group optionally interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a C6 to C10 aryl group; Rn is chosen from a straight or branched-chain perfluoroalkyi group of 2 to 20 carbon atoms, optionally interrupted by one or more ether oxygens -0-, -CH₂- -CFH-, or combinations thereof;

Q² is (CH₂)k, (CH₂)kOC(0), or (CH₂)kC(0)0;

R⁸ is H or a straight or branched alkyl chain of 2 to 30 carbons having 0 to 15 olefinic units, or mixtures thereof; and

R⁷ is a Ci to C4 alkyl.

2. The surface modified inorganic oxide particles of claim 1 , having a particle size of 10 nm to 15 microns.

3. The surface modified inorganic oxide particles of claim 1 , having a particle size of 12 nm to 13 microns.

4. The surface modified inorganic oxide particles of claim 1 , having a % Fluorine of 0.5 to 45%, based on the weight of the particles.

5. The surface modified inorganic oxide particles of claim 1 , where x is 0 and Rn is an uninterrupted straight perfluoroalkyi groups of 2 to 6 carbon atoms.

6. The surface modified inorganic oxide particles of claim 1 , where Q²

7. A coating composition comprising a coating base and the surface modified inorganic oxide particles of claim 1 , where the coating base is selected from a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating.

8. The coating composition of claim 7, further comprising a

crosslinkable compound selected from a urethane polymer having a crosslinkable ethylenically unsaturated group or a (meth)acrylic copolymer having an ethylenically unsaturated group.

9. The coating composition of claim 7, further comprising a

fluorocopolymer comprising repeat Unit A and at least one of repeat Units B, C, D, or E, in any order:

Unit A Unit B Unit C Unit D Unit E wherein

R,2 is a straight or branched-chain perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted by one or more ether oxygens -0- , -CH₂-, -CFH-, or combinations thereof;

A² is 0, S, or N(R'), wherein R' is H or an alkyl of from 1 to about 4 carbon atoms;

Q³ is a straight chain, branched chain or cyclic structure of alkylene, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, or combinations of such linking groups;

v is 0 or 1 ;

R¹ is H or CHs;

R² is independently selected from H or an alkyl of 1 to about 4 carbon atoms;

Z is a hydrophilic group selected from a hydroxyl-terminated straight or branched alkyl of 1 to 10 carbons; hydroxyl- hydroxyalkyl-, thiol-, or amine-terminated straight or branched alkoxylate having 2 to 20 alkoxylate repeat units; thiol-term inated straight or branched alkyl of 1 to 10 carbons; or an amine-containing straight or branched alkyl of 1 to 10 carbons;

M is H, HN(R⁵)3, Na, Li, Cs, K, or mixtures thereof;

R⁵ is H or an alkyl or hydroxyalkyl of 1 to 12 carbon atoms; R³ is a straight or branched alkyl chain of 2 to 30 carbons having 1 to 15 olefinic units, or mixtures thereof;

Y is selected from -CH2O-, -C(0)0-, -OC(O)-, -R⁶OC(0)-, or -C(0)OR⁶0-;

R⁶ is a straight or branched alkylene of 1 to 10 carbons;

R⁴ is a straight chain, branched chain, or cyclic structure alkyl group of 1 to 30 carbons;

Unit A is present in an amount of about 10 to 60 mol %;

Unit B is present in an amount of about 0 to 90 mol %;

Unit C is present in an amount of about 0 to 90 mol %;

Unit D is present in an amount of about 0 to 90 mol%; and

Unit E is present in an amount of about 0 to 90 mol%;

wherein the sum of monomer repeat units is equal to 100%.

10. The coating composition of claim 9, where the fluorocopolymer is a crosslinkable compound comprising at least one of repeat Units A and D.

1 1 . The coating composition of claim 7, where the composition comprises the coating base in an amount of from about 95 to 99.98% and the surface modified inorganic oxide particles in an amount of from about 0.02 to 5% by weight, based on the total weight of the coating base and the surface modified inorganic oxide particles.

12. The coating composition of claim 7, where the surface modified inorganic oxide particles have a particle size of 25 nm to 10 microns.

13. The coating composition of claim 7, where the surface modified inorganic oxide particles have a % Fluorine of 0.5 to 45%, based on the weight of the particles.

14. The coating composition of claim 8 or 10, where the composition comprises the coating base in an amount of from about 90 to 99.96%, the surface modified inorganic oxide particles in an amount of from about 0.02 to 5% by weight, and the crosslinkable compound in an amount of from about 0.02 to 5% by weight, based on the total weight of the coating base, the surface modified inorganic oxide particles, and the crosslinkable compound.

15. The coating composition of claim 7, where the coating base comprises an additive selected from ΤΊΟ2, clays, asbestos, calcium carbonate, zinc oxide, chromium oxide, barium sulfate, iron oxide, tin oxide, calcium sulfate, talc, mica, silicas, dolomite, zinc sulfide, antimony oxide, zirconium dioxide, silicon dioxide, cadmium sulfide, cadmium selenide, lead chromate, zinc chromate, nickel titanate, diatomaceous earth, glass fibers, glass powders, glass spheres, blue pigments, red pigments, yellow pigments, orange pigments, process aggregated crystals, brown pigments, or green pigments.

16. The coating composition of claim 7, where the coating base is a water-dispersed coating selected from an aqueous acrylic latex paint.

17. A method of forming a coated substrate with durable dirt pickup resistance comprising contacting a coating base with surface modified inorganic oxide particles to form a coating, contacting a substrate with the coating to form a coating film, allowing the surface modified inorganic oxide particles to migrate to the coating film surface, and crosslinking the ethylenically unsaturated groups of surface modified inorganic oxide particles of the coating film with each other,

wherein

the surface modified inorganic oxide particles comprise an oxide of X, where X is independently selected from the group consisting of Si, Ti, Zn, Zr, Mn, Al, and combinations thereof;

the coating base is selected from a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating; and

at least one of said particles has a surface covalently bonded to a. at least one fluorosilane group represented by Formula (I)

(L )g(L²)hSi— A¹— Q x-Rfi (I); and b. at least one ethylenically unsaturated group represented by Formula (II)

wherein

each L¹ represents an oxygen covalently bonded to an X; and each

L² is independently selected from the group consisting of H, a C1-C2 alkyl, OCH3, OCH2CH3, and OH; g and h are integers such that: g > 1 , h > 0, and g+h =3;

A¹ is (CH₂)k— N(R⁹-Rfi)-R⁹, (CH₂)k— NH-C(O)-NH, (CH₂)_k— NH- C(S)-NH, (CH₂)k— NH-C(O)O, (CH₂)_k— NH-C(O)S, (CH₂)_k— NH-C(O)-NH- SO₂, (CH₂)k— NH-C(S)-NH-SO₂, (CH₂)_k— NH-C(O)-N[C(O)H], (CH₂)k— NH- C(O)-CH[CH(COOH)(R¹⁰)]-S, (CH₂)_k— NH-C(O)-CH(R¹⁰)[CH(COOH)]-S, O-C(O)-NH, S-C(O)-NH, O-C(S)-NH, or S-C(S)-NH;

R⁹ is a C₂-Ci₂ hydrocarbylene interrupted by at least one of

-C(O)-O- or -O-C(O)-;

x is 0 or 1 ;

Q¹ is (CH₂)_k, (CH₂CF₂)m(CH₂)n, (CH₂)oSO N(CH₃)(CH₂)_P,

O(CF₂)₂(CH₂)_r, or OCHFCF₂OE;

m is 1 to 4;

k, n, o, p, and r are each independently 1 to 20;

E is a C₂ to C₂o linear or branched alkyl group optionally interrupted by oxygen, sulfur, or nitrogen atoms; a cyclic alkyl group, or a C6 to C10 aryl group;

Rn is chosen from a straight or branched-chain perfluoroalkyi group of 2 to 20 carbon atoms, optionally interrupted by one or more ether oxygens -O-, -CH₂- -CFH-, or combinations thereof;

Q² is (CH₂)_k, (CH₂)kOC(O), or (CH₂)_kC(O)O;

R⁷ is a Ci to C4 alkyl.