FLUORINATED COMPLEX COMPOUND ADDITIVES FOR ARCHITECTURAL COATINGS FIELD OF THE INVENTION

This invention relates to a composition comprising a coating base and a fluorinated complex compound for use 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).

Fluorinated polymer compositions are used in the preparation of a wide variety of surface treatment materials to provide surface effects to substrates. Many such compositions are fluorinated acrylate polymers or copolymers which contain predominantly eight or more carbons in the perfluoroalkyi chain to provide the desired properties. Honda, et al., in Macromolecules, 2005, 38, 5699-5705 teach that for perfluoroalkyi chains of greater than 8 carbons, orientation of the perfluoroalkyi groups, designated Rf groups, is maintained in a parallel configuration while for such chains having 6 or less carbons, reorientation occurs. This reorientation is recited to decrease surface properties such as contact angle. Thus, polymers containing shorter perfluoroalkyi chains have traditionally not been commercially successful. 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 fluorinated phosphate complex compounds derived from amine-functional monomers or polymers. Because the complex

compounds are polymerized either before or after application of the coating, the compositions of the present invention provide performance as well as durability to the water-based latex 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.

The present invention relates to a composition comprising (a) a coating base selected from a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating; and (b) at least one complex compound represented by formula (I):

where X is selected from a compound of formula (II), a non-fluorinated polymer comprising the repeat unit of formula (III), or (b) is a mixture of compounds of formula (I) where X is NH ₄ and a compound of formula (II) or said non-fluorinated polymer:

wherein Rf 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; x is 1 to 2; A is a straight chain, branched chain or cyclic structure of alkylene, alkoxy, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, or combinations of such linking groups; Q is O, CH2, or S; R ² is independently selected from H or an alkyl of 1 to about 4 carbon atoms; r is independently 2 to 4; Z is 0 or -NR'-, wherein R' is H or an alkyl of from 1 to about 4 carbon atoms; and R ³ and R ⁴ are each independently an alkyl of 1 to 4 carbon atoms, hydroxyethyl, benzyl, or R ³ and R ⁴ together with the nitrogen atom form a morpholine, pyrrolidine, pyridine, or piperidine ring; wherein the composition comprises (a) the coating base in an amount of from about 95 to 99.98% and (b) the polymer compound in an amount of from about 0.02 to 5% by weight, based on the total weight of (a) and (b).

The present invention further comprises a process of forming a coating with improved cleanability and dirt pickup resistance comprising a. contacting (a) a coating base comprising a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating; with (b) at least one complex compound to form a coating composition;

b. applying the coating composition to a substrate to form a coating; and

c. allowing the complex compound to migrate to the coating surface; wherein the composition comprises (a) the coating base in an amount of from about 95 to 99.98% and (b) the polymer compound in an amount of from about 0.02 to 5% by weight, based on the total weight of (a) and (b); the complex compound is represented by formula (I) X is selected from a compound of formula (II), a non-fluorinated polymer comprising the repeat unit of formula (III), or (b) is a mixture of compounds of formula (I) where X is NH ₄ and a compound of formula (II) or said non-fluorinated polymer; wherein Rf 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; x is 1 to 2; A is a straight chain, branched chain or cyclic structure of alkylene, alkoxy, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, or combinations of such linking groups; Q is O or S; R2 is independently selected from H or an alkyl of 1 to about 4 carbon atoms; r is independently 2 to 4; Z is O or -NR'-, wherein R' is H or an alkyl of from 1 to about 4 carbon atoms; and R ³ and R ⁴ are each independently an alkyl of 1 to 4 carbon atoms, hydroxyethyl, benzyl, or R ³ and R ⁴ together with the nitrogen atom form a morpholine, pyrrolidine, pyridine, or piperidine ring.

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.

The present invention relates to a composition comprising (a) a coating base selected from a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating; and (b) at least one complex compound represented by formula (I):

where X is selected from a compound of formula (II), a non-fluorinated polymer comprising the repeat unit of formula (III), or (b) is a mixture of compounds of formula (I) where X is NH ₄ and a compound of formula (II) or non-fluorinated polymer:

wherein Rf 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; x is 1 to 2; A is a straight chain, branched chain or cyclic structure of alkylene, alkoxy, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, or combinations of such linking groups; Q is 0, CH2, or S; R ² is independently selected from H or an alkyl of 1 to about 4 carbon atoms; r is independently 2 to 4; Z is 0 or -NR'-, wherein R' is H or an alkyl of from 1 to about 4 carbon atoms; and R ³ and R ⁴ are each independently an alkyl of 1 to 4 carbon atoms, hydroxyethyl, benzyl, or R ³ and R ⁴ together with the nitrogen atom form a morpholine, pyrrolidine, pyridine, or piperidine ring; wherein the composition comprises (a) the coating base in an amount of from about 95 to 99.98% and (b) the polymer compound in an amount of from about 0.02 to 5% by weight, based on the total weight of (a) and (b).

The complex compound of formula (I) may be made by any suitable method, for example by reacting a fluorinated alcohol with P2O5 or POC to form a fluorinated phosphate compound or compound mixture, and subsequently reacting the fluorinated phosphate compound(s) with an amine compound of formula (II) or amine-containing non-fluorinated polymer comprising the repeat unit of formula (III). A mixture of compounds of formula (I) may be present, where x is 1 , 2, and 3. In addition, other phosphate compounds, such as phosphoric acid amine salts, may be present in the mixture. The first step, formation of the phosphate compound mixture, may be formed by heating the alcohol to an elevated temperature, such as 80 °C, slowly adding P2O5 to the fluorinated alcohol, and allowing the mixture to heat at an elevated temperature, for example 100 °C, for 4-8 hours, or until the reaction conversion plateaus. The fluorinated phosphate compound mixture may then be cooled to around 50 °C and combined with the amine compound X in organic solvent or, if no further monomer polymerization is to be carried out immediately, in water. The complex compound where M is an amine compound of formula (II) may be further polymerized by conventional radical polymerization methods, for example, with the use of a polymer VAZO initiator. Where M is a polymer comprising the repeat unit of formula (III), the polymer may be reacted with the fluorinated phosphate compound mixture in solvent or as an aqueous dispersion, and the reaction product of formula (I) may be added directly to the coating base. In another embodiment, any organic solvents are removed from the complex compound, such as by vacuum distillation, before addition to the coating base. In one embodiment, R _f in formula (I) is a straight or branched-chain perfluoroalkyl group predominately containing from 2 to 6 carbon atoms, optionally interrupted by one or more ether oxygens -0-, -CH ₂ - or -CFH- groups. Such interrupted Rf groups include but are not limited to

C3F7OCF2CF2, C3F7OCF2CF2OCF2CF2, C5F11 OCF2CF2, C4F9CH2CF2, C6F13CH2CF2, C3F7CFH, C5F11CFH, and similar variations. In another aspect, R _f in formula (I) is a straight chain perfluoroalkyl group of 2 to 6 carbon atoms, and in another embodiment, 4 to about 6 carbon atoms.

Examples of suitable linking groups A in formula (I) include straight chain, branched chain or cyclic structures of alkylene, arylene, alkoxy, aralkylene, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, and combinations of such linking groups such as sulfonamidoalkylene. In one embodiment, A is a straight chain alkylene of 1 to about 15 carbon atoms or -CONR'(C _r H2r)-, the (C _r H _2r ) group is linear or branched, and preferably is linear. In this case, r is 1 to 14. Within moiety A, the alkyl in R' is linear or branched. In one embodiment, A is a straight or branched alkylene of 1 to 4 carbon atoms, and in a second embodiment, A is a straight or branched alkylene of 2 to 4 carbon atoms. Mixtures of fluorinated alcohols may also be used to form the complex compound. Suitable fluorinated alcohols capable of forming the complex compounds of formula (I) include but are not limited to

C4F ₉ S02NH(CH2) ₃ OH, C6Fi ₃ S0 ₂ NH(CH2)30H, C ₈ Fi ₇ S02NH(CH2)30H, C4F ₉ S02NH(CH2) ₂ OH, C6Fi ₃ S0 ₂ NH(CH2)20H, C ₈ Fi ₇ S02NH(CH2)20H, C4F ₉ S02N(CH3)(CH2)20H, C6Fi3S0 ₂ N(CH ₃ )(CH2)20H,

C8Fi7S02N(CH ₃ )(CH2)20H, C4F ₉ CH2CF2S02NH(CH2)30H,

C ₃ F ₇ OCF2CF2S02NH(CH2)30H, C4F ₉ CH2CH2CF2CF ₂ S02NH(CH2)30H, C4F ₉ OCFHCH2CH ₂ S02NH(CH2)30H, C4F ₉ S02CH2CH ₂ NH(CH2)30H, C6Fi3S02CH2CH ₂ NH(CH2)30H, C ₈ Fi ₇ S02CH2CH2NH(CH2)30H,

C4F ₉ CH2CH2S02NHCH2CH ₂ OH, C6F13CH2CH2SO2NHCH2CH2OH, C8F17CH2CH2SO2NHCH2CH2OH, C4F ₉ CH ₂ CH2S02N(CH ₃ )CH2CH20H, C6Fi3CH2CH2S02N(CH3)CH2CH ₂ OH,

C8Fi7CH2CH2S02N(CH3)CH2CH ₂ OH, C ₄ F ₉ (CH ₂ )20H, C6Fi ₃ (CH ₂ )20H, C ₈ Fi7(CH2)20H, C ₄ F ₉ OH, CeFisOH, C ₈ Fi ₇ OH, C4F ₉ CH2CH2CH ₂ OH, C6F13CH2CH2CH2OH, C4F9CH2OH, C6F13CH2OH,

C4F9CH2CF2CH2CH2OH, C6F13CH2CF2CH2CH2OH,

C4F9CH2CF2CH2CF2CH2CH2OH, C6F13CH2CF2CH2CF2CH2CH2OH, C3F7OCF2CF2CH2CH2OH, C2F5OCF2CF2CH2CH2OH,

CF3OCF2CF2CH2CH2OH, C3F7(OCF2CF2)2CH2CH ₂ OH,

C2F5(OCF2CF2)2CH2CH ₂ OH, CF3(OCF2CF2)2CH2CH ₂ OH,

C3F7OCHFCF2OCH2CH2OH, C2F5OCHFCF2OCH2CH2OH,

CF3OCHFCF2OCH2CH2CH2OH, C3F7OCHFCF2OCH2CH2CH2OH, C2F5OCHFCF2OCH2CH2CH2OH, CF3OCHFCF2OCH2CH2OH,

C4F9CH2CH2SCH2CH2OH, C6F13CH2CH2SCH2CH2OH, C4F9SCH2CH2OH, C6F13SCH2CH20H, C4F9CH2CH2CF2CF2CH2CH20H,

C3F70CF(CF3)C(0)NHCH2CH ₂ OH,

C3F70CF(CF3)C(0)N(CH3)CH2CH ₂ OH, C4F ₉ NHC(0)NHCH2CH20H, C6Fi3NHC(0)NHCH2CH ₂ OH, HCF2(CF2)4CH ₂ OH, HCF2(CF2)6CH ₂ OH, HCF2(CF2)8CH20H, and similar variations thereof.

The compound of formula (II) is an amine compound containing an ethylenically unsaturated group that may be polymerized after migrating to a coating surface. The non-fluorinated polymer comprising the repeat unit of formula (III) is a homopolymer or copolymer containing a pending amine repeat unit. In one aspect, Z in formula (II) or (III) is -0-, and r is 2 or 3. In one aspect, R ³ and R ⁴ are linear or branched alkyls of 1 , 2, or 3 carbon atoms. Examples of suitable monomers for formula (II) or for forming the polymer with formula (III) include but are not limited to diethylaminoethyl acrylate and/or dimethylaminoethyl methacrylate.

The non-fluorinated polymer 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 crosslinkable polymer 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.

The non-fluorinated polymer comprising the repeat unit of formula (III) may be a non-fluorinated homopolymer of formula (III). In another embodiment, X is a non-fluorinated copolymer comprising the repeat unit of formula (III) and one or more additional repeat units. Such repeat units may include but are not limited to those of formula (IV) or those of formula

where R ² is as defined above; Y is selected from -CH2O-, -C(0)0-, - OC(O)-, -R ⁵ OC(0)-, -C(0)0(CH2CH20)m(CH ₂ CH(CH3)0)n-, or - C(0)OR ⁵ 0-; R ⁵ is a straight or branched alkylene of 1 to 10 carbons; m and n are independently integers of 0 to 20, provided that m+n>0; and R ⁶ is a straight or branched alkyl chain of 1 to 30 carbons, optionally having at least one olefinic unit, or mixtures thereof; and where V is selected from H, Na, Li, Cs, K, HN(R ² )3, a hydroxy-term inated straight or branched alkyl of 1 to 10 carbons, or a hydroxy-term inated straight or branched alkoxylate having 2 to 20 alkoxylate repeat units, or mixtures thereof. In one embodiment, X comprises the repeat unit of formula (III) and the repeat unit of formula (IV); in another embodiment, X comprises the repeat unit of formula (III) and the repeat unit of formula (V); and in a third embodiment, X comprises all three repeat units (III), (IV), and (V). More than one different type of each repeat unit may also be present. For example, X may contain repeat unit (III), repeat unit (IV) where R ⁶ is a straight alkyl chain of 1 to 30 carbons having 0 olefinic units, and repeat unit (IV) where R ⁶ is an alkyl chain of 1 to 30 carbon atoms having 1 to 15 olefinic units. More than one repeat unit (V) may also be present, where V is different. The repeating units can occur in any random or block sequence in the proportions described above.

Where X is a copolymer, in one embodiment, formula (III) is present in X an amount from about 1 to 100 mol%; in another embodiment, formula (III) is present in an amount from about 25 to about 100 mol %; and in a third embodiment, formula (III) is present in an amount from about 35 to about 75 mol %. In one embodiment, repeat unit (IV) is present in an amount from about 0 to about 50 mol%; in another embodiment, repeat unit (IV) is present in an amount from about 0 to 35 mol%; and in a third embodiment, repeat unit (IV) is present in an amount from about 0 to about 30 mol%. In one embodiment, repeat unit (V) is present in an amount from at least 0 to 50 mol %; in another embodiment, repeat unit (V) is present in an amount from about 0 to about 40 mol %; and in a third embodiment, repeat unit (V) is present in an amount from about 0 mol % to about 30 mol%. All percentages are based on the total number of repeat units present; for example, when only repeat units (III) and (IV) are present, the mol% sum of (III) and (IV) totals 100%, and when only repeat units (III) and (V) are present, the mol% sum of (III) and (V) total 100%.

Repeat units of formula (IV) provide a hydrophobic functionality, optionally having a crosslinkable olefin group. In one embodiment, R ⁶ has at least one olefinic unit, and the monomers used to form formula (IV) 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. Where Y is -C(0)0(CH ₂ CH20)m(CH2CH(CH ₃ )0)n- or -C(0)OR ⁵ 0- the monomer is the reaction product of an alkoxylated (meth)acrylic or vinylic alcohol with fatty acids. Fatty acids may include but are not limited to lauric acid, palmitic acid, stearic acid, caprylic acid, capric acid, lauric acid, mysteric acid, arachidic acid, behenic acid, lignoceric acid, erucic acid, 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 repeat units of formula (IV) 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.

In another embodiment, repeat units of formula (IV) may be formed from (meth)acrylic monomers having pendant straight or branched 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.

Repeat units (V) are formed from hydrophilic monomer compounds, such as hydroxy-terminal or acidic (meth)acrylates, or mixtures thereof. Where V is a hydroxy-terminal straight or branched alkyl, suitable examples include, but are not limited to, one or more hydroxyalkyl

(meth)acrylates having alkyl chain lengths of 2 to 4 carbon atoms, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, and 3-hydroxypropyl methacrylate. In one embodiment, R ² is H or alkyl radical of 1 to 2 carbon atoms. Where repeat unit (V) 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.

In another embodiment, the monomers used to form repeat unit (V) are acrylic acid or methacrylic acid; and V is H, Na, Li, Cs, K, HN(R ² )3, or mixtures thereof. In one embodiment, V is NH ₄ or Na, or a mixture thereof. Repeat units of formula (V) 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.

The polymer compound may or may not further comprise additional repeat units outside of formulas (III), (IV), and (V), resulting from the use of additional monomers. Suitable monomers are ethylenically-unsaturated monomers, including but not limited to, glycidyl (meth)acrylates,

aminoalkyl methacrylate hydrochloride, acrylamide, alkyl acrylamides, or n-methylol (meth)acrylamide. When additional repeat units are present other than those of formulas (III), (IV), and (V), then the mol% sum of (III) + (IV) + (V) + other repeat units is equal to 100%.

The polymerization process comprises contacting the monomers as defined hereinabove in an organic solvent in the presence of a free radical initiator, hydrophilic 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 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. The final pH of the emulsion is between about 6 and about 9, and preferably is between 6 and 8.

Temperatures in the range of 20-90 °C may be suitable where organic peroxides or azo compounds are used, depending, for example, on the choice of organic solvent and the choice of free radical initiator. Temperatures of 0-50 °C are suitable where oxidation-reduction (redox) initiators are used. The free radical initiator is typically added after the reaction mixture has reached the appropriate reaction or activation temperature.

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 Fe ²⁺ , Cr ²⁺ , V ²⁺ , Ti ³⁺ , Co ²⁺ , Cu ⁺ ; combinations of HSOs ^" , SOs ^2" , S2O3 ² -, or S2O5 ^2" with Ag ⁺ , Cu ²⁺ , Fe ³⁺ ' CIO ^3" , or H2O2; combinations of organic alcohols with Ce ⁴⁺ , V ⁵⁺ , Cr ⁶⁺ , or Mn ³⁺ ; and combinations of

peroxydiphosphate compounds with Ag ⁺ , V ⁵⁺ , or Co ²⁺ . Such systems may be used when low temperature or rapid activation is desirable.

The polymer compound optionally further comprises a residue of a chain transfer agent, 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. Chain transfer agents may include hydrophobic chain transfer agents, including dodecyl mercaptans, or may an include a hydrophilic chain transfer agent. In one embodiment, the chain transfer agent has the formula (VI)

wherein g is 1 or 2; D 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 G is a hydrophilic functional group selected from hydroxyl, carboxyl, thiol, or amine. Where g=2, the chain transfer agents are disulfide compounds of the formula G-D-S-S-D-G. 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 complex compound 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 polymer compounds are useful as coatings additives, wherein the polymer compound 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.

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. In one embodiment, the coating base comprises a polymer which having pendant hydroxyl or carboxylic acid groups. 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.

The coating compositions may further comprise additional components to provide surface effects to the resulting coating. For example, the composition may further comprise a non-polymeric ethylenically unsaturated crosslinkable compound to provide additional crosslinking sites for the crosslinkable polymer compound. In one embodiment, this non-polymeric crosslinkable compound is (c) a fatty acid compound in an amount of about 0.001 to 1 % by weight, based on the total weight sum of coating base (a) + complex compound (b) + fatty acid (c). Any fatty acid, including those listed above for use in forming repeat unit of formula (IV), may be employed. In another embodiment, the composition further comprises an inorganic oxide particle, or the coating base further comprises an inorganic oxide particle. In another

embodiment, the coating compositions further comprise a polymerization initiator, such as a photoinitiator. Such compounds aid in further crosslinking the complex compounds, where X is a compound of formula (II) or where X contains repeat unit (IV) having at least one olefinic group, once the complex compound has migrated to the coating surface.

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 polymer

compound is effectively introduced to the coating base by thoroughly contacting, e.g., by mixing the complex compound composition with the coating base. The contacting of complex compound and coating base can be performed, for example and conveniently, 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. The complex compound of the invention is generally added at about 0.02 weight % to about 5 weight % on a dry weight basis of the polymer compound 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 complex compound is added to the paint.

In another embodiment, the invention comprises a process of forming a coating with improved cleanability and dirt pickup resistance comprising: a. contacting (a) a coating base comprising a water-dispersed coating, an epoxy polymer coating, an alkyd coating, a Type I urethane coating, or an unsaturated polyester coating; with (b) at least one complex compound to form a coating composition; b. applying the coating composition to a substrate to form a coating; and c. allowing the complex compound to migrate to the coating surface; wherein the composition comprises (a) the coating base in an amount of from about 95 to 99.98% and (b) the polymer compound in an amount of from about 0.02 to 5% by weight, based on the total weight of (a) and (b); the complex compound is represented by formula (I) X is selected from a compound of formula (II), a non-fluorinated polymer comprising the repeat unit of formula (III), or (b) is a mixture of compounds of formula (I) where X is NH ₄ and a compound of formula (II) or said non-fluorinated polymer; wherein Rf 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; x is 1 to 2; A is a straight chain, branched chain or cyclic structure of alkylene, alkoxy, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamido, carbonamido, carbonyloxy, urethanylene, ureylene, or combinations of such linking groups; Q is O, CH2, or S; R2 is

independently selected from H or an alkyl of 1 to about 4 carbon atoms; r is independently 2 to 4; Z is O or -NR'-, wherein R' is H or an alkyl of from 1 to about 4 carbon atoms; and R ³ and R ⁴ are each independently an alkyl of 1 to 4 carbon atoms, hydroxyethyl, benzyl, or R ³ and R ⁴ together with the nitrogen atom form a morpholine, pyrrolidine, pyridine, or piperidine ring. In one aspect, R ⁶ has at least one olefinic unit, and the process further comprises a step (d) of polymerizing the olefinic unit after the complex compound has migrated to the coating surface. In another aspect, X is a compound of formula (II), and the process further comprises a step (d) of polymerizing the complex compound after the complex compound has migrated to the coating surface. In this case, the ethyelenically unsaturated group of formula (II) is polymerized. In either case, the polymerization may occur between complex compound molecules, between the complex compound molecule and an ethylenically unsaturated group of a resin compound or other component of the coating base, or between the complex compound molecule and an added non- polymeric crosslinkable compound (c).

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 compound 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 complex compound, having a formula (II) or pendant olefin group in repeat unit (IV), may be further 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 compositions of the present invention are particularly useful in exterior coatings and paints.

MATERIALS AND TEST METHODS

All solvents and reagents, unless otherwise indicated, were purchased from Sigma-Aldrich and used directly as supplied.

1 H, 1 H,2H,2H-perfluorooctanol, CAPSTONE FS-61 , and CAPSTONE FS- 66 were obtained from DuPont Chemicals & Fluoroproducts, Wilmington DE. CAPSTONE FS-61 is an ammonium salt of a partially fluorinated alcohol/P2O5 reaction product, and CAPSTONE FS-66 is a partially fluorinated alcohol/P2Os reaction product.

Test Methods

Dosing of Polymer Additives in Paint and Test Panel Application

Aquesous dispersions of fluoroacrylic copolymers of the present invention 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 sample was 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 Repellency via Contact Angle

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 DROPimage 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 h 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 ΔΙ_ ^* where ΔΙ_ ^* = (L ^* initial - L ^* dusted). A lower AL ^* value indictes better dirt pick-up resistance.

Test Method 3. Leneta Oil Stain Cleanability for Interior Paints

A modified version of ASTMD3450 was used to determine the oil stain cleanability of painted panels. The test material dosed in interior flat paint was applied to a black Leneta card as decribed in the application method. The dried samples were cut into a 4" x 3" size for testing. A thin, evenly laid layer of Leneta staining medium (5 wt.% dispersion of Leneta carbon black in Vaseline®) was placed on half of the film, and left for 1 hour. The excess stain was gently scrapped off and wiped with a clean paper towel until no visible stain could be wiped off. The panel was then moved to an Gardco abrasion tester covered with 8 layers of cheese cloth at the washing block. The cheesecloth was moisturized with 10 mL of 1 % mild detergent solution in water and performed washability via moving the washing block over the stained panel. After 5 cycles, the panel was rinsed with deionized water and left to dry for 12 hours. The whiteness of the unwashed stained paint and washed stained paint were measured using a Hunter lab colorimeter to obtain L values. Cleanability was calculated as per the equation: Cleanability = (Lwashed paint - Lunwashed stained paint) X

10/(Lunstained paint - Lunwashed stained paint). Similarly a cleanability rating for a control sample that is devoid of fluorinated additive was acessed simultaneously. The difference between the cleanability rating of the sample to the control were determined and represented as a cleanability score AC. The higher the AC the better the performance, suggesting that relatively lower amounts of stain remains on the treated sample compared to control. A negative AC indicates that the sample is worse than the control.

Test Method 4. 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 and water 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

Example 1

A round-bottom flask with magnetic stir bar, temperature probe, and

N2 atmosphere was charged with 1 /-/, 1 /-/,2/-/,2/-/-perfluorooctan-1 -ol (10 g, 27.46 mmol). The liquid was heated to 75 °C, and P2O5 (1 .56 g, 10.98 mmol) was added. The reaction was heated to 100 °C with stirring for 8 hours. After cooling, isopropanol (IPA, 46.24 g) and 2-(N,N- dimethylamino)propyl acrylate (3.99 g, 25.4 mmol) were added to the product, and the mixture was heated to 50 °C for 4 hours.

A portion of the phosphate/am ine complex solution (20 wt% solids, 6 g, 1 .2 g phosphate/amine complex) was added with methyl isobutyl ketone (MIBK, 2 g) to a round-bottom flask with magnetic stir bar, reflux condenser, temperature probe, and N2 atmosphere. The solution was sparged with N2 for 1 hour. The reaction mixture was heated to 60 °C, and then a solution of VAZO 67 (0.1 g, 0.5 mmol) in IPA (1 g) was added. The reaction was further heated to 80 °C with stirring for 16 hours. Monomer conversion was calculated to be > 99% by NMR. An aliquot of the polymer solution (5.64 g) was added to a round-bottom flask and heated to 60 °C and then water (10 g) was added, and the reaction stirred with heating for 1 hour. The volatiles were removed from the reaction under reduced pressure to obtain a cloudy dispersion (9.2% solids). The polymer was analyzed by GPC for molecular weight (M _n = 33.1 kDa and PDI = 1 .42). A calculated amount (350 ppm F) of this additive was used side by side with examples for testing on both exterior and interior paints as per the test methods described.

Comparative Example A

A calculated amount of CAPSTONE FS-61 (350 ppm F) was used side by side with examples for testing on both exterior and interior paints as per the test methods described.

Comparative Example B

Interior and exterior paints with no additive were tested according to the test methods described.

Table 1. Performance of Example 1 in Exterior Paint

^* A lower number indicates better performance.

^** A higher number indicates better performance.

The polymeric amine-phosphate complex of Example 1 showed excellent initial oil contact angle and dirt pickup resistance compared to Comaparative Examples A and B. There was a 42% and 28% retention of oil contact angle in exterior paint. The polymeric amine-phosphate complex also showed slightly better DPR performance compared to Comparative Example A. In essence, the polymeric amine-phosphate complex appears to be more durable and provide better performance. Example 2

By following a procedure described in Example 1 , Μ , Μ ,2Η,2Η- perfluorooctan-1 -ol (10 g, 27.46 mmol) and P2O5 (1 .56 g, 10.98 mmol) were reacted to give fluorinated phosphates which were complexed with 3- (N, N-dimethylamino)propyl acrylate (3.99 g, 25.4 mmol) and then subsequently polymerized using VAZO 67 (0.05 g, 0.25 mmol). The polymeric phosphate complex was dispersed in water to obtain a cloudy dispersion (13.8 wt% solids). The polymer was analyzed by GPC for molecular weight (M _n = 51 .6 kDa and PDI = 1 .23). A calculated amount (350 ppm F) of this additive was used side by side with examples for testing on both exterior and interior paints as per the test methods described.

Table 2. Performance of Example 2 in Exterior Paint

* A lower number indicates better performance.

** A higher number indicates better performance.

Example 2, having a higher molecular weight than Example 1 , showed excellent oil contact angle ratings.

Table 3. Cleanability of Examples 1 and 2 in Interior Paint

* A higher number indicates better performance.

** A higher number indicates better performance.

The polymeric amine-phosphates showed excellent cleanability compared with Comparative Example A. They also showed good blooming as indicated by good oil contact angle.

Example 3 A 250 ml_ four-necked flask was equipped with a reflux condenser and a nitrogen purge line, a mechanical stirrer, a thermocouple for measurement of the internal temperature, and a rubber septa pierced with two 18-gauge needles, connected to two 30-ml syringes and syringe pumps respectively, for addition of monomer solution and VAZO solution. The reaction flask was charged with isopropanol (14.53 g), N,N- diethylaminomethacrylate (4.33 g, 23.41 mmol), 3-mercaptopropionic acid (0.41 g, 3.88 mmol), thioglycolic acid (0.42 g, 4.56 mmol), and sodium chloride (0.03 g, 0.51 mmol). The solution was stirred to a clear light yellow solution and heated to 80 °C. To this solution was added 22% of a solution of VAZO 68 (0.81 g, 2.90 mmol) and isopropanol (1 1 .62g) via syringe in one portion. The resulting reaction mixture was stirred and heated to 80 °C for 30 minutes, and then a solution of isopropanol (2.90 g) and N,N-diethylaminomethacrylate (17.30 g, 93.51 mmol) was added at a rate of 4.89 ml/hr, simultaneously with the remaining portion of VAZO solution at a rate of 2.60 ml/hr, both via syringe for 4.5 hours. Heating and stirring were maintained at 80 °C for 18 hours. The reaction mixture was cooled to room temperature. To a portion of the reaction mixture (7.43 g) was added CAPSTONE FS-66 (3.26 g) and isopropanol (14.6 g), briefly heated in water bath and stirred for 1 hour. The solution was stirred to a clear amber solution. A portion of the dispersion was lyophilized for further analysis and was calculated to be 24.2 wt% solids. A calculated amount (350 ppm Fluorine) of this polymer was used as additive for testing on both exterior and interior paints as per the test methods described.

Example 4

A 250 ml_ four-necked flask was equipped with a reflux condenser and a nitrogen purge line, a mechanical stirrer, a thermocouple for measurement of the internal temperature, and a rubber septa pierced with two 18-gauge needles, connected to two 30-ml syringes and syringe pumps respectively, for addition of monomers and VAZO solution. The reaction flask was charged with isopropanol (14.60 g), N,N- diethylaminomethacrylate (2.50 g, 13.51 mmol), methacrylic acid (0.23 g, 2.67 mmol), hydroxyethylmethacrylate (1 .40 g, 10.76 mmol), oleyl methacrylate (0.21 g, 0.62 mmol), 3-mercaptopropionic acid (0.41 g, 3.88 mmol), thioglycolic acid (0.41 g, 4.47 mmol), and sodium chloride (0.03 g, 0.51 mmol). The solution was stirred to a clear light yellow solution and heated to 80 °C (internal temperature). To this solution was added 22% of a solution of VAZO 68 (0.94 g, 3.35 mmol) and isopropanol (1 1 .71 g) via syringe in one portion. The resulting reaction mixture was stirred and heated to 80 °C (internal temperature) for 30 minutes, and then to the reaction mixture a solution of isopropanol (2.94 g), N,N- Diethylaminomethacrylate (9.98 g, 53.95 mmol), methacrylic acid (0.93 g, 10.81 mmol), hydroxyethylmethacrylate (5.62 g, 43.18 mmol) and oleyl methacrylate (0.84 g, 2.50 mmol) was added at a rate of 4.89 ml/hr, simultaneously with the remaining portion of VAZO solution at a rate of 2.60 ml/hr, both via syringe for 4.5 hours. Heating and stirring were maintained at 80 °C for 18 hours. The reaction mixture was cooled to room temperature. To a portion of the reaction mixture (1 1 .40 g) was added FS- 66 (2.88 g) and isopropanol (16.0 g), briefly heated in water bath and stirred for 1 hour. The solution was stirred to a clear amber solution. A portion of the dispersion was lyophilized for further analysis and was calculated to be 25.1 wt% solids. A calculated amount (350 ppm Fluorine) of this polymer was used as additive for testing on both exterior and interior paints as per the test methods described.