WO2016176264A1 - Additifs d'un complexe d'amine fluoré pour revêtements architecturaux - Google Patents

Additifs d'un complexe d'amine fluoré pour revêtements architecturaux Download PDF

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WO2016176264A1
WO2016176264A1 PCT/US2016/029457 US2016029457W WO2016176264A1 WO 2016176264 A1 WO2016176264 A1 WO 2016176264A1 US 2016029457 W US2016029457 W US 2016029457W WO 2016176264 A1 WO2016176264 A1 WO 2016176264A1
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unit
coating
straight
carbons
branched
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PCT/US2016/029457
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Brad M. Rosen
Anilkumar Raghavanpillai
Michael H. OBER
Hau-Nan LEE
John Russell Crompton, Jr.
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The Chemours Company Tt, Llc
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Publication of WO2016176264A1 publication Critical patent/WO2016176264A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions

Definitions

  • This invention relates to a fluorinated amine complex compound and its use as an additive in architectural coating compositions such as water-based latex paints, to provide durable surface effects.
  • 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 amine complexes have been used in applications such as textile finishes.
  • the textile finish additives in U.S. Patent 4,841 ,090 are complexes of simple acids, like glycolic acid, with two amino cations.
  • Water-based latex coating bases such as those employed as paint coatings, have a tendency to have low oil repellency and poor cleanability ratings.
  • 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 amine complexes that migrate to the coating surface to form a durable additive at the coating surface.
  • the fluorinated amine complexes 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 relates to a composition
  • 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
  • R " is selected from an acid of Formula (I la) or a polymeric acid, the polymeric acid comprising repeat Unit B and optionally comprising one or more of repeat Units A, C, D, or E, in any order:
  • Rf is a straight or branched-chain perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted by one or more ether oxygens -O- , -CH 2 -, -CFH-, or combinations thereof;
  • A is a straight or branched alkylene of from 1 to 12 carbon atoms;
  • Q is a straight or branched alkylene of 1 to 10 carbon atoms, an alkoxy, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamide, carbonamide, carbonyloxy, urethanylene, ureylene linking group, or combinations of such linking groups;
  • v is 0
  • Z is a hydrophilic group selected from a hydroxyl-term inated 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; a phosphate- or phosphonate-terminated alkylene of 1 to 10 carbons; a silane-terminated alkylne of 1 to 10 carbons; or an amine-containing straight or branched alkyl of 1 to 10 carbons; M is H, HN(R 5 )3, Na, Li, Cs, K, or mixtures thereof; Rs 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
  • the present invention further relates to a method of imparting cleanability and dirt pickup resistance to a coating composition
  • a coating composition comprising (i) contacting a coating base with a fluorinated amine complex of Formula (I); and (ii) allowing the fluorinated amine complex to migrate to the surface; wherein R " is selected from an acid of Formula (lla) or a polymeric acid, the polymeric acid comprising repeat Unit B and optionally
  • the 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;
  • the coating composition comprises coating base (a) in an amount of from about 95 to 99.98% and fluorinated amine complex (b) in an amount of from about 0.02 to 5% by weight, based on the total weight of (a) and (b);
  • Rf is a straight or branched-chain
  • A is a straight or branched alkylene of from 1 to 12 carbon atoms;
  • Q is a straight or branched alkylene of 1 to 10 carbon atoms, an alkoxy, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamide, carbonamide, carbonyloxy, urethanylene, ureylene linking group, or combinations of such linking groups;
  • v is 0 or 1 ;
  • R 1 and R 2 are each independently H or an alkyl of 1 to 4 carbon atoms;
  • R 8 is independently selected from H or an alkyl of 1 to 4 carbon atoms;
  • Z is a hydrophilic group selected from a hydroxyl- terminated straight or branched alkyl of 1 to 10 carbons; hydroxy
  • (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.
  • 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.
  • 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.
  • 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.
  • 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.
  • surfactants protective colloids and thickeners
  • pigments and extender pigments preservatives
  • fungicides fungicides
  • freeze-thaw stabilizers 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.
  • 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.
  • 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).
  • coating base 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.
  • 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
  • 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
  • R ⁇ is selected from an acid of Formula (lla) or a polymeric acid, the polymeric acid comprising repeat Unit B and optionally comprising one or more of repeat Units A, C, D, or E, in any order:
  • Rf is a straight or branched-chain perfluoroalkyl group of 2 to 20 carbon atoms, optionally interrupted by one or more ether oxygens -0- , -CH 2 -, -CFH-, or combinations thereof;
  • A is a straight or branched alkylene of from 1 to 10 carbon atoms;
  • Q is a straight or branched alkylene of 1 to 12 carbon atoms, an alkoxy, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamide, carbonamide, carbonyloxy, urethanylene, ureylene linking group, or combinations of such linking groups;
  • v is 0 or
  • Z is a hydrophilic group selected from a hydroxyl-term inated straight or branched alkyl of 1 to 10 carbons; hydroxyl-, hydroxyalkyl- thiol-, or amine- term inated straight or branched alkoxylate having 2 to 20 alkoxylate repeat units; thiol-term inated straight or branched alkyl of 1 to 10 carbons; a phosphate- or phosphonate-term inated alkylene of 1 to 10 carbons; a silane-term inated alkylne of 1 to 10 carbons; or an amine-containing straight or branched alkyl of 1 to 10 carbons; M is H, HN(R 5 )3, Na, Li, Cs, K, or mixtures thereof; Rs 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
  • R 6 is a straight or branched alkylene of 1 to 10 carbons
  • R 4 is a straight chain, branched chain, or cyclic structure alkyl group of 1 to 30 carbons
  • R 7 is a linear or branched Cs to C22 alkyl, optionally having 1 to 5 olefin groups
  • Unit A is present in an amount of 0 to 50 mol%
  • Unit B is present in an amount of 1 to 100 mol %
  • Unit C is present in an amount of 0 to 50 mol %
  • Unit D is present in an amount of 0 to 50 mol %
  • Unit E is present in an amount of 0 to 50 mol %; wherein the sum of all monomer repeat units is equal to 100%.
  • the fluorinated amine complex of Formula (I) can be formed using a fluorinated amine, which is made by conventional methods. For example, the process of U.S. Patent 4,486,391 or U.S. Patent 8,729, 138 may be used. Any fluorinated amine may be used, including but not limited to C4F 9 S02NH(CH2)3N(CH 3 )2, C6Fi 3 S02NH(CH2)3N(CH 3 )2,
  • Rf is a straight or branched perfluoroalkyl of 2 to 10 carbon atoms, and in another embodiment, Rf is a straight or branched perfluoroalkyl of 2 to 6 carbon atoms. In one embodiment, Rf is a straight chain perfluoroalkyl. In one aspect, A is a straight alkylene group of 1 to 4 carbon atoms. In one aspect, v is 0 or v is 1 and Q is a sulfonamide. In one aspect, R 1 and R 2 are independently chosen from alkyls of 1 to 2 carbons.
  • the anion of the fluorinated amine complex is formed from a carboxylic acid-containing compound.
  • R " is a compound of
  • the carboxylic acid-containing compound is a long-chain hydrophobic acid, such as a fatty acid.
  • these compounds 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, oleic (meth)acrylate, linoleic (meth)acrylate, palmitic methyl ester, soybean oil
  • the fatty acid contains at least one olefinic group.
  • Such an olefinic group could provide a crosslinking site for the coating fluorinated amine complex once the complex migrates to the coating surface.
  • R 7 is a C12 to C18 alkyl.
  • R " is a polymeric acid
  • the carboxylic acid-containing compound is a polymer having pendant carboxylic acid groups in Unit B.
  • Such a polymer may be made by conventional methods by
  • the (meth)acrylate copolymers of the polymeric acid may comprise two or more repeating units derived from monomers from each of five groups.
  • Monomers forming Unit A are hydrophilic monomers such as hydroxyalkyi (meth)acrylates or alkoxylated (meth)acrylates
  • monomers forming Units B and C are acidic monomers such as (meth)acrylic acid
  • monomers forming Unit D are olefin-group-containing monomers such as fatty acid (meth)acrylate
  • monomers forming Unit E are hydrophobic monomers such as alkyl (meth)acrylates.
  • the repeating units can occur in any random, block, or other sequence in the proportions described above.
  • the polymeric acid compound contains repeat units from at least Unit B.
  • Unit B is present in an amount of about 1 to 100 mol%; in another embodiment, Unit B is present in an amount of about 25 to 100 mol%; and in a third embodiment, Unit B is present in an amount of about 25 to 75 mol %.
  • Unit D is present in an amount of about 0.1 to 50 mol%; in another embodiment, Unit D is present in an amount of about 0.1 to 25 mol%; and in a third embodiment, Unit D is present in an amount of about 0.1 to 10 mol%. In one embodiment, Unit B is present in an amount of about 1 to 100 mol%; in another embodiment, Unit B is present in an amount of about 25 to 100 mol%; and in a third embodiment, Unit B is present in an amount of about 25 to 75 mol %. In one embodiment, Unit D is present in an amount of about 0.1 to 50 mol%; in another embodiment, Unit D is present in an amount of about 0.1 to 25 mol%; and in a third embodiment, Unit
  • Unit C is present in an amount of about 0.1 to 50 mol %; in another embodiment, Unit C is present in an amount of about 0.1 to 25 mol %; and in a third embodiment, Unit C is present in an amount of about 0.1 to 10 mol%.
  • Unit A is present in an amount of about 0.1 to 50 mol %; in another embodiment, Unit A is present in an amount of about 0.1 to 40 mol %; and in a third embodiment Unit A is present in an amount of about 0.1 to 30 mol %.
  • Unit E is present in an amount of about 0.1 to 50 mol %; in another
  • Unit E is present in an amount of about 0.1 to 40 mol %; and in a third embodiment Unit E is present in an amount of about 0.1 to 30 mol %.
  • at least two repeat units are present; in a further embodiment, at least three repeat units are present; in another embodiment, at least 4 repeat units are present; and in yet a further embodiment, all five of Units A, B, C, D, and E are present.
  • the polymeric acid 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.
  • 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.
  • the weight average molecular weight M w is about 5000 to about 50,000 Daltons; in a second
  • 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.
  • the polymeric acid is a
  • the Mw can be up to 300,000, and PDI may be up to 6.0.
  • Examples of monomers used to form Unit A 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 am ine-term inated 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.
  • R 2 is H or alkyl radical of 1 to 2 carbon atoms.
  • 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 am ine-term inated monomers of similar types can also be used, and are synthesized according to conventional methods.
  • Z is a phosphate- or phosphonate- terminated alkylene of 1 to 10 carbons
  • the monomers used to form Unit A include but are not limited to ethylene glycol (meth)acrylate phosphate, diethyl allyl phosphate, and the compounds listed below. Variations of the compounds below, including using different alkyl or alkylene units, or interchanging OH and alkoxy, are also included.
  • the monomers used to form Unit A include but are not limited to trialkoxysilyl alkyl (meth)acrylates such as trimethoxysilyl ethyl(meth)acrylate, trimethoxysilyl propyl(meth)acrylate, triethoxysilyl ethyl(meth)acrylate, or triethoxysilyl propyl(meth)acrylate; allyl trialkoxysilanes such as
  • allyltriethoxysilane allyltrimethoxysilane, or allyltripropoxysilane
  • vinyl trialkoxysilanes such as triethoxyvinylsilane or tripropoxyvinylsilane.
  • the hydrophilic functional groups of Unit A could provide a crosslinking site for the coating fluorinated amine complex once the complex migrates to the coating surface.
  • the phosphate or phosphonate groups may ionically bond to amines or cationic species already present in the coating base. They may also bind with pendant amine compounds in the polymeric acid.
  • Pendant silane groups may covalently bond to inorganic oxide particles or pigments present in the coating base.
  • the monomers used to form Units B and C are acrylic acid or methacrylic acid; and M is H, Na, Li, Cs, K, HN(R 5 )3, or mixtures thereof. In one embodiment, M is NH 4 or Na, or a mixture thereof.
  • Repeat 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.
  • 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.
  • 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,
  • Unit D eicosapentaenoic acid, docosahexanoic acid, eicosadienoic acid, docosatetranoic acid, and mixtures thereof.
  • monomers used to form Unit D include but are not limited to oleic
  • the at least one olefinic group could provide a crosslinking site for the coating fluorinated amine complex once the complex migrates to the coating surface.
  • the olefinic groups of Unit D covalently bond with olefinic groups in the polymeric acid molecules after migration to the coating surface.
  • 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.
  • the alkyl groups contain 1 to 22 carbons, and in a third embodiment, the alkyl groups contain 6 to 22 carbons.
  • 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 polymeric acid compound may or may not further comprise additional repeat units outside of Units A, B, C, D, and E, 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
  • the fluorinated amine complexes of the invention may be made by any process known to one skilled in the art. In one process, the
  • the fluorinated amine complex is useful as a coatings additive, wherein the fluorinated amine complex 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, optionally, subsequently crosslink to form a durable oil- dirt- and water-repellent surface.
  • 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 polymeric acid compound is different in composition to the polymer of the coating base resin.
  • the coating base includes those solvents, pigments, fillers, and functional additives found in a conventional liquid coating.
  • the coating base may include a resin polymer 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.
  • 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.
  • the composition may further comprise a crosslinking compound, such as a non-polymeric ethylenically unsaturated crosslinkable compound or a hydroxyl-reactive crosslinking compound, to provide crosslinking sites for the acidic compound.
  • 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 (a) + (b) + (c). Any fatty acid, including those listed above for use in forming the monomer of Unit D, may be employed.
  • the coating compositions may also include a pigment.
  • 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.
  • 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.
  • MONASTRAL Green BW C. I. Pigment Green 7
  • Pigment Scarlet C. I. Pigment Red 60
  • Auric Brown C. I. Pigment Brown 6
  • MONASTRAL Green BW C. I. Pigment Green 7
  • Pigment Scarlet C. I. Pigment Red 60
  • Auric Brown C. I. Pigment Brown 6
  • Green G (C.I. Pigment Green 7), MONASTRAL Maroon B, MONASTRAL Orange, and Phthalo Green GW 951.
  • Titanium dioxide 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.
  • the fluorinated amine complex compound When used as an additive to a coating base, the fluorinated amine complex compound is effectively introduced to the coating base by thoroughly contacting, e.g., by mixing the fluoropolymer composition with the coating base.
  • the contacting of fluoropolymer 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 composition of the invention When used as an additive to a coating base, the composition of the invention 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 present invention provides a method of imparting cleanability and dirt pickup resistance to a coating composition
  • a method of imparting cleanability and dirt pickup resistance to a coating composition comprising (i) contacting a coating base with a fluorinated amine complex of Formula (I); and (ii) allowing the fluorinated amine complex to migrate to the surface; wherein R " is selected from an acid of Formula (I la) or a polymeric acid, the polymeric acid comprising repeat Unit B and optionally comprising one or more of repeat Units A, C, D, or E, in any order;
  • 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;
  • the coating composition comprises coating base (a) in an amount of from about 95 to 99.98% and fluorinated amine complex (b) in an amount of from about 0.02 to 5% by weight, based on the total weight of (a) and (b);
  • Rf is a straight or branched-chain
  • A is a straight or branched alkylene of from 1 to 10 carbon atoms
  • Q is a straight or branched alkylene of 1 to 10 carbon atoms, an alkoxy, arylene, aralkylene, sulfonyl, sulfoxy, sulfonamide, carbonamide, carbonyloxy, urethanylene, or ureylene linking group, or combinations of such linking groups
  • v is 0 or 1
  • R 1 and R 2 are each independently an alkyl of 1 to 3 carbon atoms
  • R 8 is independently selected from H or an alkyl of 1 to 4 carbon atoms
  • Z is a hydrophilic group selected from a hydroxyl-term inated straight or branched alkyl of 1 to 10 carbons; hydroxyl-, hydroxyalkyl- thiol-, or
  • R " is an acid of Formula (lla) and R 7 comprises at least one olefinic group
  • the process further comprises the step (iii) of subsequently polymerizing the olefinic groups of Formula (lla).
  • the process further comprises the step (iii) of subsequently ionically or covalently bonding the functional groups of Unit A, Unit D or both Units A and D to another polymeric acid molecule or to a compound in the coating base. Step (iii) in either case occurs after the complex has been added to the coating and allowed to migrate to the surface.
  • a crosslinking compound is added to the composition, and the compound of Formula (lla) or polymeric acid further polymerizes with said crosslinking compound.
  • the coating compositions of the present invention are useful for providing a protective and/or decorative coating to a wide variety of substrates.
  • 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.
  • 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.
  • 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.
  • 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.
  • CAPSTONE 1 157 is a compound obtained from DuPont Chemicals & Fluoroproducts, Wilmington DE. DESMODUR N100 isocyanate available from Bayer Company, Pittsburgh, PA. CAPSTONE 1 157 is a compound obtained from DuPont Chemicals & Fluoroproducts, Wilmington DE. DESMODUR N100 isocyanate available from Bayer Company, Pittsburgh, PA. CAPSTONE 1 157 is a compound obtained from DuPont Chemicals & Fluoroproducts, Wilmington DE. DESMODUR N100 isocyanate available from Bayer Company, Pittsburgh, PA. CAPSTONE 1 157 is a compound obtained from DuPont Chemicals & Fluoroproducts, Wilmington DE. DESMODUR N100 isocyanate available from Bayer Company, Pittsburgh, PA. CAPSTONE 1 157 is a compound obtained from DuPont Chemicals & Fluoroproducts, Wilmington DE. DESMODUR N100 isocyanate available from Bayer Company, Pittsburgh, PA. CAPSTONE 1 157 is
  • perfluoroalkyl betaine surfactant and CAPSTONE FS-81 is a partially fluorinated polymer surfactant, both available from DuPont Chemicals & Fluoroproducts, Wilmington DE.
  • C6Fi3CH 2 CH2SO2NHCH2CH2CH 2 N(CH3)2 was prepared by reacting 1 /-/, 1 /-/,2/-/,2/-/-perfluorooctyl sulfonyl chloride and
  • 1 /-/, 1 /-/,2/-/,2/-/-perfluorooctyl sulfonyl chloride was prepared by adding chlorine and acetic acid to ⁇ , ⁇ ,2 ⁇ ,2 ⁇ - perfluorooctyl thiocyanate.
  • 1 H, 1 /-/,2/-/,2/-/-perfluorooctyl thiocyanate was prepared by reacting 1 /-/, 1 /-/,2/-/,2/-/-perfluorooctyl iodide with potassium thiocyanate.
  • SEC Chromatography
  • Aqueous 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.
  • 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 ⁇ 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.
  • the sample 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.
  • test fluid approximately one drop of test fluid was dispensed onto the sample using a 30 ⁇ _ pipette tip and an automated dispensing system to displace a calibrated amount of the test fluid.
  • 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.
  • 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.
  • 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 CMC is defined as the concentration of surfactants above which micelles are spontaneously formed, at which increased
  • concentrations of surfactant essentially no longer reduce the surface tension.
  • the surface tension was measured as a function of surfactant concentration. Surface tension was then plotted vs. log concentration. The resulting curve had a nearly horizontal portion at concentrations higher than the CMC and had a negative steep slope at concentrations less than the CMC. The CMC was calculated as that concentration of the curve where the flat portion and the extrapolated steep slope intersected. The Surface Tension beyond CMC was the value in the flat portion of the curve. The CMC should be as low as possible to provide the lowest cost for effective performance.
  • Example 1 Fluorinated sulfonamide complex with polvmethacrylic acid
  • a 250 ml_ three-necked flask was equipped with a reflux condenser, a nitrogen purge line, a TEFLON-coated magnetic stir bar, and a dip-tube for measurement of the internal temperature via a thermocouple.
  • the reaction flask was charged with methyl isobutyl ketone (MIBK, 9 g), isopropyl alcohol (IPA, 30.0 g) and fluorinated sulfonamide amine (9.68 g, 18.9 mmol).
  • MIBK methyl isobutyl ketone
  • IPA isopropyl alcohol
  • fluorinated sulfonamide amine 9.68 g, 18.9 mmol
  • the amber solution was subjected to sub-surface sparging with N2 using a needle for 1 hour at room temperature.
  • the reactor was heated to 80 °C (internal temperature).
  • a solution of VAZO 67 (0.15 g, 0.77 mmol) in IPA (2 g) was added in one portion via syringe. Cloudiness of the polymer solution increased as the polymerization progressed. Heating was maintained at 80 °C for 18 hours. Upon cooling, the polymer had precipitated from the reaction mixture.
  • a small portion as removed and analyzed by NMR for reaction completion (>98%) and by GPC for molecular weight (M n 46 kDa, PDI 1.9).
  • reaction mixture was heated to 70 °C.
  • a solution consisting of NH 4 OH (1 .4 g, 23.1 mmol, 28% NH 3 ) in H2O (25 mL) was heated to 50 °C and added to the polymer solution dropwise via addition funnel over 10 minutes. Solvent was removed under vacuum. Upon removal of the solvent the polymer remained undispersed. A portion of the dispersion was lyophilized for further analysis and was calculated to be 9.05 wt% solids. A calculated amount (350 ppm Fluorine) of this polymer was used as an additive for testing on both exterior and interior paints as per the test methods described.
  • Example 2 Fluorinated sulfonamide amine complex with polvmethacrylic acid/tert-butyl methacrylate
  • a 250 mL three-necked flask was equipped with a reflux condenser, a nitrogen purge line, a TEFLON-coated magnetic stir bar, and a dip-tube for measurement of the internal temperature via a thermocouple.
  • the reaction flask was charged with MIBK (9 g) and fluorinated sulfonamide amine (8.66 g, 16.9 mmol).
  • the solution was stirred to a clear amber solution.
  • methacrylic acid (5.58 g, 64.9 mmol) and IPA (18 g) with stirring to complex the acid and amine. With stirring was added tert-butyl methacrylate (2.74 g, 19.25 mmol).
  • the orange solution was subjected to sub-surface sparging with N2 using a needle for 1 hour at room temperature.
  • the reactor was heated to 80 °C (internal temperature).
  • a solution of VAZO 67 (0.297 g, 2 wt%) in IPA (2 g) was added in one portion via syringe. Heating was maintained at 80 °C for 16 hours.
  • the reaction mixture was heated to 70 °C.
  • Solvent was removed under vacuum. Upon removal of the solvent the polymer becomes a clear orange gel. A portion of the dispersion was lyophilized for further analysis and was calculated to be 17.6 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 7 Fluorinated sulfonamide amine complex with crosslinkable acrylic polymer
  • 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).

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention comprend une composition comprenant une base de revêtement sélectionnée parmi un mélange polymère acrylique, un mélange de polymère époxy, un mélange de polymère de vinyle, et un mélange de polymère de polyuréthane sous la forme d'une peinture d'intérieur pour bâtiments, d'une peinture d'extérieur pour bâtiments, d'une coloration ou d'un revêtement transparent ; et un complexe d'amine fluoré. Ces composés sont utiles en tant qu'additifs pour revêtements de sorte que, lorsque le revêtement est appliqué sur un substrat, le composé additif puisse migrer vers la surface pour former une surface résistant à l'huile, à la saleté et à l'eau.
PCT/US2016/029457 2015-04-30 2016-04-27 Additifs d'un complexe d'amine fluoré pour revêtements architecturaux WO2016176264A1 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2019005460A1 (fr) * 2017-06-26 2019-01-03 The Chemours Company Fc, Llc Additifs à composé de type ester fluoré pour revêtements architecturaux

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US4486391A (en) 1981-08-25 1984-12-04 Dainippon Ink And Chemicals, Inc. Separation and recovery of ionic substances by fluorine-containing compound
US4841090A (en) 1982-06-11 1989-06-20 Minnesota Mining And Manufacturing Company Treatment of fibrous substrates, such as carpet, with fluorochemical
US20040091725A1 (en) * 2002-11-08 2004-05-13 Far Eastern Textile Ltd. Hydrolytic condensation coating composition, hard coat film and method of preparing the same
WO2007103505A1 (fr) * 2006-03-08 2007-09-13 E. I. Du Pont De Nemours And Company Revetements contenant un produit chimique fluore et des additifs lecithine
FR2995606A1 (fr) * 2012-09-14 2014-03-21 Ass Pour Les Transferts De Technologies Du Mans Utilisation de resine epoxy fluoree pour la preparation de moules anti-adherents
US8729138B2 (en) 2010-03-25 2014-05-20 E I Du Pont De Nemours And Company Mixture of polyfluoroalkylsulfonamido alkyl amines
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US4486391A (en) 1981-08-25 1984-12-04 Dainippon Ink And Chemicals, Inc. Separation and recovery of ionic substances by fluorine-containing compound
US4841090A (en) 1982-06-11 1989-06-20 Minnesota Mining And Manufacturing Company Treatment of fibrous substrates, such as carpet, with fluorochemical
US20040091725A1 (en) * 2002-11-08 2004-05-13 Far Eastern Textile Ltd. Hydrolytic condensation coating composition, hard coat film and method of preparing the same
WO2007103505A1 (fr) * 2006-03-08 2007-09-13 E. I. Du Pont De Nemours And Company Revetements contenant un produit chimique fluore et des additifs lecithine
US8729138B2 (en) 2010-03-25 2014-05-20 E I Du Pont De Nemours And Company Mixture of polyfluoroalkylsulfonamido alkyl amines
FR2995606A1 (fr) * 2012-09-14 2014-03-21 Ass Pour Les Transferts De Technologies Du Mans Utilisation de resine epoxy fluoree pour la preparation de moules anti-adherents
WO2014178873A1 (fr) * 2013-05-02 2014-11-06 Empire Technology Development Llc Composition de surface peinte hydrophile

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"Surface Coatings", vol. I,, 1984, CHAPMAN AND HALL, article "Raw Materials and Their Usage"
"The Pigment Handbook", vol. 1, 1988, JOHN WILEY & SONS
C. R. MARTENS: "Emulsion and Water-Soluble Paints and Coatings", 1965, REINHOLD PUBLISHING CORPORATION

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019005460A1 (fr) * 2017-06-26 2019-01-03 The Chemours Company Fc, Llc Additifs à composé de type ester fluoré pour revêtements architecturaux
CN110799604A (zh) * 2017-06-26 2020-02-14 科慕埃弗西有限公司 用于建筑涂料的氟化酯化合物添加剂
CN110799604B (zh) * 2017-06-26 2021-12-03 科慕埃弗西有限公司 用于建筑涂料的氟化酯化合物添加剂
US11518894B2 (en) 2017-06-26 2022-12-06 The Chemours Company Fc, Llc Fluorinated ester compound additives for architectural coatings

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