Block resistant alkyd coating compositions containing non-fluorinated additive

Abstract

Water-based coating compositions include an aqueous alkyd emulsion, with or without acrylic modification or urethanation, and a non-fluorinated, non-polymeric additive that includes (i) an acid group that has been at least partially neutralized with a base, wherein the acid group includes at least one sulfur or phosphorus atom and (ii) a linear or branched, substituted or unsubstituted alkyl group. The coating compositions provide improved blocking resistance and in some aspects support the absence of a fluorinated anti-blocking compound.

Description

Inventors: Paul Masters Rich Tomko Revathi TomkoSW File: WO23082BLOCK RESISTANT ALKYD COATING COMPOSITIONS CONTAINING NON-FLUORINATED ADDITIVEFIELD

[0001] This disclosure relates to water-based alkyd coating compositions providing blocking resistance via inclusion of a non-fluorinated, non-polymeric additive. In some aspects, the coating composition provides adequate blocking resistance without the inclusion of fluorinated compounds.BACKGROUND

[0002] Architectural coating compositions commonly include a polymeric binder such as a latex polymer, a polyurethane dispersion, or an alkyd emulsion. Following application, coalescence, and cure / drying, the polymeric binder forms a film which adheres to the surface. The characteristics of an applied, cured coating are often driven by the polymeric binder present in the coating composition. These characteristics include gloss, scrub resistance, adhesion, washability, water resistance, and blush resistance, among others.

[0003] Some polymeric binders such as hydrophobic polyurethane emulsions, urcthanc-modificd alkyd emulsions, alkyd emulsions, and acrylic-modified alkyd emulsions, provide desirable end-use characteristics such as potential high biobased content, high gloss, and improved water resistance and blush resistance among other properties, but can be inherently soft and tacky, and may require metal driers to oxidatively cure. The tackiness of these coatings also can result in blocking, an undesirable characteristic wherein an applied, partially- or wholly-cured coating will, upon application of pressure, stick to itself. Resistance to blocking (block resistance) is particularly important for coating compositions used in architectural trim applications such as window trim.

[0004] Although metal driers can be added to speed oxidative curing and thus improve block resistance, it can remain a challenge with some alkyd -based polymeric binders. Conventional solutions for improving block resistance in coating compositions may include adding or utilizing a polymeric binder having a high glass transition temperature (Tg), utilizing a wax additive, or formulating for higher pigment-volume concentration (PVC). These solutions, however, may not provide adequate block resistance in all applications, and can be of limited use in fonnulating high gloss coatings, which require a low PVC. Existing solutions may also adversely impact other coating properties such as film quality and low temperature application.

[0005] Another approach to improve block resistance has been to include a fluorosurfactant or another fluorinated carbon compound, or a polysiloxane, as an anti-blocking agent. These solutions, however, can result in a coating that is difficult to recoat. In addition, while neither regulatory bodies nor the scientific community have shown toxicity or environmental persistence of conventional fluorosurfactants or fluorinated carbon-containing compounds that are commonly used in architectural coatings for this purpose to date, consumers often do not distinguish between conventional fluorosurfactants or fluorinated carbon-containing compounds that are commonly used in architectural coatings, which have not been shown to be environmentally persistent, on the one hand, and compounds like perfluorooctanoic acid (PFOA), which has historically been used in products like nonstick cookware and the manufacture of such products, and which has been shown to be environmentally persistent, on the other.

[0006] From the foregoing, it will be appreciated that what is needed are coating compositions that include a nominally tacky alkyd, acrylic -modified alkyd, or urethane-modified alkyd emulsion binder with excellent block resistance.SUMMARY OF THE INVENTION

[0007] Disclosed is a water-based coating composition comprising an aqueous alkyd emulsion such as a urethane-modified alkyd polymer, an acrylic-modified alkyd polymer, or a long-oil or medium -oil alkyd; and a non-fluorinated, non-polymeric additive that includes (i) an acid group that has been at least partially neutralized with a base, wherein the acid group includes at least one sulfur or phosphorus atom and (ii) a linear or branched, substituted or unsubstituted alkyl group. In some aspects, the additive may be neutralized with an amine such as triethanolamine, or a Group I or Group II base, such as a potassium compound. In some aspects, the non-fluorinated, non-polymeric additive is present in the coating composition in an amount of at least about 0.05 wt. %, at least about 0.10 wt. % or at least about 0.15 wt. % based on the total polymer solids in the coating composition. In some aspects, tire non-fluorinated, non- polymeric additive is present in the coating composition in an amount of no more than about 1.5 wt. %. no more than about 1 .0 wt. %, no more than about 0.75 wt. %, no more than about 0.5 wt. %, or no more than about 0.25 wt. % based on the total polymer solids in the coating composition.

[0008] As described further herein, the foregoing aspects may be combined with one or more optional aspects, alone or in combination with other aspects.

[0009] The foregoing summary of the invention is not intended to describe each and every aspect of the present disclosure and present inventions. Further aspects of the present disclosure are described herein.DETAILED DESCRIPTION

[0010] It has surprisingly been discovered that the block resistance of coating compositions that include certain relatively soft, tacky alkyd-based binder polymers, such as alkyd emulsions, polyurethane modified-alkyd emulsions and acrylic-modified alkyd emulsions, can be improved by inclusion of a non-fluorinated, non-polymeric additive. The non-fluorinated, non-polymeric additive of the present disclosure includes (i) an acid group that has been at least partially neutralized with a base, wherein the acid group includes at least one sulfur or phosphorus atom and (ii) a linear or branched, substituted or unsubstituted alkyl group. Surprisingly, block resistance of usually tacky coating compositions that include alkyd emulsions described herein can be improved to have acceptable block resistance (defined as 24-hour Block Resistance of 3 or greater following a 1-day, 3 -day, and 7-day cure measured according to the test described herein) by including the non-fluorinated, non-polymeric additive of the present disclosure, without inclusion of conventional fluorosurfactant or polysiloxane anti-blocking additives. Aqueous Alkyd Emulsion

[0011] Alkyd polymer emulsions of the present disclosure are an aqueous emulsion of an alkyd polymer, with or without additional urethane or (meth)acrylic modification or urethane modification.

[0012] Alkyd polymer emulsions of the present disclosure are prepared by condensation of a polyhydric alcohol with a polycarboxylic acid or anhydride in the presence of a fatty acid. The polyhydric alcohol may be a linear or branched alkylene glycol (ethylene glycol, polyethylene glycol, propylene glycol and polypropylene glycol, neopentyl glycol etc.), a hydroxy compound having three or more hydroxyl groups such as poly alky lolalkanes (e.g. trimethylolpropane, pentaerythritol) or a polyhydroxyalkanes (e.g. glycerol, trimethylol ethane (TME), erythritol, sorbitol, mannitol, and the like), or blends thereof. Suitable polycarboxylic acids include adipic acid, azelaic acid, citric acid, cyclohexane dicarboxylic acid, dodecane dioic acid, fumaric acid, glutaric acid, isophthalic acid, itaconic acid, maleic acid, nadic acid, phthalic acid, pyromellitic acid, sebacic acid, succinic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, trimellitic acid, etc. Suitable anhydrides include adipic anhydride, azelaic anhydride, phthalic anhydride, isophthalic anhydride, maleic anhydride, itaconic anhydride, nadic anhydride, pyromellitic dianhydride, succinic anhydride, sebacic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, 1,2, 4, 5 -cyclohexanetetracarboxylic dianhydride, etc. Chain growth can be controlled by end-capping through inclusion of a mono-carboxylic acid such as benzoic acid, crotonic acid, sorbic acid, cinnamic acid, etc.

[0013] Tire fatty acid component of the alkyd polymer is provided by inclusion in the reaction mixture of a saturated or unsaturated fatty acid having at least 10 carbons. In some aspects, the fatty acid has 14 to 16 carbons. Useful fatty acids include non-drying, semi-drying, and drying fatty acids. The fatty acids may be derived from natural or synthetic materials, and may be saturated or partially unsaturated. Suitable fatty acids include: stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, pinolenic acid, soya fatty acid, linseed fatty acid, tall oil fatty, acid, dehydrated castor oil fatty acid, castor oil fatty7acid, or 12- hydroxystcaric acid. Fatty acid functionality may also be introduced through a fatty oil, which is a triglyercide including three fatty acids joined by a glycerol group. Suitable fatty oils include those derivedfrom oils such as calendula oil, castor oil, coconut oil, com oil, cottonseed oil, herring oil, linseed oil, mustard seed oil, olive oil, palm oil, peanut oil, rapeseed oil, safflower oil, sesame oil, soyabean oil, sunflower oil, tall oil, tallow oil, tung oil, veronia oil, coconut oil, oiticaca oil, perilla oil, poppyseed oil etc. Tire fatty acid or fatty oil may be partially unsaturated, and typically is at least partially unsaturated. In some aspects, the alkyd polymer is derived from more than one fatty acid or more than only fatty oil.

[0014] An exemplary alkyd polymer is produced by reaction of pentaerythritol and phthalic anhydride monomers in the presence of soyabean fatty acid. Water produced in the condensation reaction is removed in situ by use of an organic azeotrope, with or without solvent, and vacuum distillation, to continue reaction until little to no acid functionality (e.g., <10 g / mol KOH) remains in the resulting alkyd polymer.

[0015] (Meth)acrylic-modified alkyd polymer emulsions of the present disclosure can be prepared first by preparation of an alkyd polymer as described above, followed by copolymerization with one or more acrylic monomers to yield an acrylic-modified alkyd emulsion. Any suitable acrylic monomer may be used to incorporate acrylic functional groups. Useful acrylic monomers include any compounds having acrylic structure, such as (meth)acrylates, alkyl(meth)acrylates, (meth)acrylic acids, acrylamide, acrylonitrile, etc. and aromatic derivatives thereof. Exemplary acrylic monomers include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate. 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate. 2-ethylhexyl methacrylate, hydroxyethyl acry late, hydroxyethyl methacry late, hydroxybutyl acrylate, hydroxybutyl methacrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, 2-(acetoacetoxy)ethyl methacry late (AAEM), diacetone acrylamide (DAAM), acry lamide, methacrylamide, itaconic acid and esters thereof, and methylol (meth)acrylamide. Suitable polyfunctional acrylates include, for example, di-, tri- and tetra-functional acrylates such as dipropylene glycol diacrylate (DPGDA). propoxylated glyceryl triacrylate (GPTA), pcntacrythritol tetraacrylate, dipentaerythritol tetraacrylate, mixtures thereof, and the like.

[0016] An acrylic -modified alkyd polymer emulsion also can include structural units derived from an aromatic monomer. Exemplary aromatic monomers include any one or more of styrene, t-butyl styrene, chlorostyrene, methyl styrene, propyl styrene, vinyl napthalene, vinyl toluene, divinyl benzene, etc. Tire polymer further can include structural units derived from a suitable phosphate-containing comonomer. Examples of phosphate-containing comonomers include bis(2 -methacryloxyethyl) phosphate, monoacryloxyethyl phosphate, and monolauryl(methacryloyloxy) phosphate. Polymerization with one or more of the foregoing monomers is contemplated.

[0017] If necessary , the particle size of an aqueous emulsion of the alkyd polymer may be reduced by high speed homogenization, including, for example, use of a microfluidizer, sonicator, homogenizator,colloid mill or another device. Particle size of the alkyd polymer is typically about 40 nm to about 700 nm. Optionally, the alkyd can be modified by dilution with free radical polymerizable monomers, emulsified in water, and then polymerized by inclusion of free radical initiators.

[0018] An initiator is added either prior or following dispersion of the alkyd in water. Suitable initiators for acrylic modification of the alkyd before dispersion into water are oil-soluble initiators such as organic peroxides: T-butyl peroctoate. t-buyl perbenzoate, di-t-butyl peroxide, or oil soluble azo initiators such as 2, 2, -azobis(2 -methylbutane nitrile) (VAZO67), are suitable. If initiators are added after dispersion into water, then water soluble initiators such as sodium persulfate, ammonium persulfate, or 4,4’-azobis(4- cyanopentanoic acid) may be used.

[0019] Tire alkyd polymer of the alkyd emulsion can be urethanated or urethane-modified before or after dispersion of tire polymer in water. Introduced by reacting an isocyanate with free hydroxyl groups that are present in the alkyd polymer, any suitable multi-isocyanate such as a polyisocyanate may be used to impart urethane modification. Exemplary isocyanates that can be used to make a urethane modified alkyd polymer include diisocy anatcs such as cyclohexyl diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5- naphthalene diisocyanate, toluene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate. 1,4- tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (trade name: Desmodur-H®), 1,10- decamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 3.3'-dimethyl-4.4'- diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexylene diisocyanate, 4,4'-methylene bis(isocyanato cyclehexane), p-phenylene diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, bis para-isocyanate cyclohexylmethane,4.4-biphenylene diisocyanate, 4,4-methylene diphenyl isocyanate, isophorone diisocyanate (IPDI) (tradename Desmodur® I) 1,5 -naphthalene diisocyanate, benzene 1.3 -bis (1 -isocyanate- 1 -methylethyl)1.5 -tetrahydronaphthalene diisocyanate. diphenylmethane-4,4'-diisocyanate (tradename Mondur XP744®, and the isocyanurate trimer of hexamethylene diisocyanate. If a branched polyurethane is desired, a triisocyanate may be used, such as the aromatic triisocyanate adduct of trimethylol propane and tolylene diisocyanate sold under the brand name Mondur CB-75, and aliphatic triisocyanate product of the hydrolytic trimerization of 1,6-hexamethylene diisocyanate, sold under the brand name Desmodur N®.

[0020] Suitable dispersants for the reaction mixture are hydrophilic materials that react with isocyanates and allow the urethane to be dispersed in water, which include (a) ionic salt groups, such as carboxylate, sulfonate, or ammonium groups, e.g., sulfonated carboxylic acid like 5-(sodiosulfo)isophthalic acid (SSIPA), carboxylate polyols such as dimethylolpropionic acid (DMPA), dimethylol butanic acid (DMBA), etc.; (b) cationic salt groups, such as ternary or quaternary ammonium groups or ternarysulfonium groups, such as hyroxyalkyl quaternary ammonium salt, and cationic salt groups, such as ternary amines that can quatemized to water-dispersable quaternary ammonium salts such as dihydroxyalkyl ammonium salts. Non-ionic hydrophilic materials can also be used to disperse the urethane in water, including materials with polyether chains. Exemplary materials with polyether chains include polyethylene glycols and polyethylene glycol copolymers, including Perstorp YMER polyethylene glycol diol from Perstorp AB. A mixture of ionic and non-ionic groups can also be used to disperse the urethane in water.

[0021] A catalyst may be used to control the reaction and polymerization. If needed, suitable catalysts include dibutyl tin dilaurate (DBTDL), bismuth octanoate, or a tertiary amine such as 1,4- diazabicyclo[2.2.2]octane (DABCO) or triethylamine (TEA).

[0022] Following emulsification, the alkyd may be further stabilized by adjusting the pH, and surfactants may be added. If needed, solvent may be stripped by vacuum evaporation. The emsulion may be adjusted to a desired NVM. In some aspects, the alkyd emulsion has an NVM of at least 35%, preferably at least 45%, preferably at least 55%. Tire alkyd emulsions may incorporated into a coating composition by methods known in the art.

[0023] Alkyd polymers of the present disclosure in some aspects have at least one extrapolated glass transition onset temperature of at least -50°C; in some aspects at least -30°C, and in some aspects at least - 10°C. In some aspects, the alkyd polymer has at least one extrapolated glass transition onset temperature of at most 30°C, preferably at most 20°C, preferably at most 10°C.

[0024] Alkyd polymer emulsions of the present disclosure are aqueous dispersions or emulsions of an alkyd polymer. As used herein, the term “aqueous” means that the alkyd polymer is in a liquid carrier comprising at least 40% water. Preferably, tire liquid carrier comprises at least 50%, at least 70%, at least 90%, at least 95%, or at least 98%, or at least 99% water.

[0025] Alkyd polymer emulsions of the present disclosure preferably have a VOC of no more than 500 g / L, or no more than 250 g / L, or no more than 150 g / L, or no more than 100 g / L, or no more than 50 g / L, or no more than 25 g / L.

[0026] In certain embodiments, the alkyd polymers of the present invention may be derived from one or more bio-based monomers. “Bio-based,” as used with respect to monomers herein, refers to monomers that are preferably obtained from bio-renewable olefinically unsaturated monomers. Such bio-renewable olefinically unsaturated monomers have a carbon-14 (C-I4) that is significantly higher than olefinically unsaturated monomers derived from fossil fuels. This is because C-14 has a relatively short half-life on the scale of the age of fossil-fuel-based materials. Tirus, “bio-renewable” monomers as used herein mean monomers for which the level of C-14 isotope is comparable to the mean level of C-14 in atmospheric CO2, as measured by ASTM D6866 or having at least about 1.5 dpm / gC (disintegrations per minute pergram carbon), at least 2.5 dpm / gC, or at least 3.0 dpm / gC of C-14, as measured through liquid scintillation counting.

[0027] Exemplary bio-based monomers include esters of itaconic acid, bio-derived (mcth)acrylic acid, and alkyl (meth)acrylic acid; as well as fatty acids derived from natural oils such as tung oil, linseed oil, etc. Bio-based monomers may be introduced through diisocyanates like bio-based IPDI and bio-based pentamethylene diisocyanate. In some embodiments, bio-based monomers make up at least 20 wt %, at least 30 wt %, or at least 40 wt % of the alkyd emulsion by weight of all monomers polymerized to form the alkyd emulsion.

[0028] Alkyd polymers of the present disclosure can be characterized according to the polymer oil length. Oil length is tire weight fraction of the fatty oil or fatty acid in the alkyd polymer, and is defined by the equation:Wt. of Oil or Faty Acid Oil legnth = -Weight of Alkyd SolidsThe alkyd polymer type is defined by the oil length.Alkyd Polymer Type _ Oil Length _Long Oil > about 60Medium Oil About 50 - about 60Short Oil < about 50

[0029] A long-oil alkyd polymer thus has an oil length of above about 60; a medium oil alkyd polymer has an oil length from about 50 to about 60, and a short oil alkyd polymer has an oil length of less than about 50.

[0030] Alkyd emulsions of the present disclosure may be one of multiple binders used in a coating composition. Coating compositions in which the alkyd emulsions of the present disclosure are incorporated may also include other binders commonly used in architectural coatings, such as a (meth)acrylic latex, styrene-acrylic latex, a urethane-modified acrylic latex, a vinyl acetate latex, a polyurethane dispersion, or combinations thereof, as described in U.S. Published Patent Application No. 2024 / 0400843-Al.Water-based Carrier

[0031] Coating compositions of the present disclosure are water-based. That is. they include a carrier that is at least 50% water, and preferably may be at least 70 wt.%, at least 90 wt.%, or at least 95 wt.% of at least 99 wt.% water. Optionally, the carrier liquid may further include a solvent selected from aliphatic, cycloaliphatic and aromatic hydrocarbons such as white spirit, cyclohexane, toluene, xylene and naptha solvent, esters such as methoxypropyl acetate, n-butyl acetate and 2-ethoxyethyl acetate;octamethyltrisiloxane, or other solvents used in solvent borne systems and mixtures thereof. Carrier liquids may also include recycled liquid from manufacturing of paints, adhesives, sealants, stains, caulks, and mineral and pigment slurries. Compositions of the present disclosure may include one or more carrier liquids. In some approaches, the carrier liquid or liquids are selected so as to provide an aqueous composition that is low VOC, very low VOC, extremely low VOC, or zero VOC.

[0032] In some embodiments, carrier liquids may constitute 5-60% by volume of a coating composition. Additives

[0033] Coating compositions in which the alkyd emulsions of the present disclosure are incorporated also generally comprise numerous other additives and components as are conventional or as otherwise may be found suitable in a coating composition. Exemplary additives include any one or more of neutralizing agents, pigments, antifoaming agents, fillers, extenders, dyes, colorants, dispersants, surfactants, adhesion promoters, wetting agents, rheology modifiers, leveling agents, deflocculants, antiblocking agents, antimicrobial agents such as mildewcides, fungicides, algaecides, bactericides, or other preservatives, humectants, thixotropic agents, drying agents, and anti-settling agents. When used, such additives may be present in any amounts suitable fortheir intended purposes. It is contemplated that some additives will play multiple roles in a coating composition. Other optional additives for use in the aqueous coating compositions herein are described in Koleske et al., Paint and Coatings Industry, April, 2003, pages 12-86.

[0034] If needed, any suitable rheology modifier may be incorporated into a coating composition. Exemplary polyurethane rheology modifiers include nonionic, solvent-free, hydrophobically modified ethylene oxide urethane (EIEUR) rheology modifiers such as ACRYSOL™ RM-2020 NPR (sold by the Dow Chemical Company) and nonionic urethane rheology modifiers such as ACRYSOL™ RM-12W and ACRYSOL™ RM-8W (sold by the Dow Chemical Company).

[0035] The coating composition may include any suitable surfactant or emulsifier. In some embodiments, a phosphate surfactant or nonionic surfactant can be included in the alkyd emulsion of the coating composition. Exemplary phosphate surfactants include phosphate esters such as methyl phosphate, 2-ethylhexyl phosphate, decyl alcohol ethoxylated phosphate esters, lauryl alcohol ethoxylated phosphate esters, n-octyl phosphate, nonylphenol ethoxylated phosphate esters, octyl phenol ethoxylated phosphate esters, styrenated phenol ethoxylated phosphate esters, tridecyl alcohol ethoxylated phosphate esters, etc. An exemplary phosphate ester surfactant is DEXTROL™ OC-50 (sold by Ashland). Other useful surfactants comprise TRITON™ CF-10 (sold by the Dow Chemical Company), E-SPERSE® RX 201, E-SPERSE® RX 202, and E-SPERSE® RX 203 (sold by Ethox Chemicals). Examples of suitable nonionic emulsifiers include tcrt-octylphcnoxycthylpoly(39)-cthoxycthanol, dodecyloxypoly(10)ethoxyethanol, nonylphenoxy ethyl -poly (40)ethoxyethanol, polyethylene glycol 2000monooleate, ethoxylated castor oil, fluorinated alkyl esters and alkoxylates, polyoxyethylene (20) sorbitan monolaurate, sucrose monococoate, di(2-butyl) phenoxypoly(20)ethoxyethanol, hydroxyethylcellulosepolybutyl acry late graft copolymer, dimethyl silicone polyalkylene oxide graft copolymer, poly(ethylene oxide)poly(butyl acrylate) block copolymer, block copolymers of propylene oxide and ethylene oxide, 2,4,7,9-tetramethyl-5-decyne-4,7-diol ethoxylated with ethylene oxide, N- polyoxyethylene(20)lauramide, N-lauryl-N-polyoxyethylene(3)amine and poly(10)ethylene glycol dodecyl thioether. Examples of suitable anionic emulsifiers include sodium lauryl sulfate, sodium dodecylbenzenesulfonate, potassium stearate, sodium dioctyl sulfosuccinate, sodium dodecyldiphenyloxide disulfonate, nonylphenoxyethylpoly(l)ethoxyethyl sulfate ammonium salt, sodium styrene sulfonate, sodium dodecyl allyl sulfosuccinate, linseed oil fatty acid, sodium, potassium, or ammonium salts of phosphate esters of ethoxylated nonylphenol or tridecyl alcohol, sodium octoxynol-3- sulfonate, sodium cocoyl sarcocinate, sodium 1 -alkoxy-2 -hydroxypropyl sulfonate, sodium alpha-olefin (C14-C16)sulfonate, sulfates of hydroxyalkanols, tetrasodium N-(l,2-dicarboxy ethyl)-N- octadecylsulfosuccinamate, disodium N-octadecylsulfosuccinamate, disodium alkylamido poly-ethoxy sulfosuccinate, disodium ethoxylated nonylphenol half ester of sulfosuccinic acid and the sodium salt of tert-octylphenoxy ethoxypoly (39)ethoxy ethyl sulfate .

[0036] In some aspects, the nonionic surfactant may be present in an amount of at least 0.25 wt. %. at least 1 wt. %.. or at least 2 wt.% based on the total weight of components of the coating composition.

[0037] Any suitable dispersant, such as any one or more of anionic dispersants, cationic dispersants, amphoteric dispersants, or nonionic dispersants may be used in the coating composition. Exemplary dispersants include 2 -amino-2 -methyl- 1 -propanol (e.g., sold as AMP™ by Angus Chemical Company), DISPERBYK®-190 (sold by Byk of Altana Group), pyrophosphates such as tetrapotassium pyrophosphate and tetrasodium pyrophosphate, tripolyphosphates such as potassium tripolyphosphate and sodium tripolyphosphate, NUOSPERSE® FA 196 (sold by Elementis Specialties), etc. Any suitable wetting agents such as any one or more of anionic wetting agents, cationic wetting agents, amphoteric wetting agents, or nonionic wetting agents may be used.

[0038] Tire coating composition may include any suitable humectant or other component suitable to improve the open time of the composition. Exemplary open time extenders include glycols such as ethylene glycol and propylene glycol. When used, the open time extenders can be used in any suitable amounts. For example, ethylene and propylene glycol may be used in amounts of at least 5 g / L. and preferably are used in amounts ranging from 40 to less than 50 g / L. Generally, the glycols may be used in amounts sufficient to improve the open time of the composition but such that the composition has a volatile organic compounds (VOC) content of less than 50 g / L as determined by ASTM D6886. The ASTM test is believed to operate within a margin of error of about ±6 g / L; in practice, a composition thatyields a result of less than about 56 g / L under this test will be deemed to be a composition that has a VOC content of less than 50 g / L. In some embodiments, the coating composition is essentially free of VOCs except for the ethylene or propylene glycol or other open time extenders.

[0039] Tire coating composition may, if desired, include one or more fillers or extenders. Exemplary fillers and extenders include, for example, sodium-potassium alumina silicates such as MINEX® 4 and MINEX® 10 (sold by Unimin Corporation), clay, glass beads, calcium carbonate, talc, silicas, feldspar, mica, barytes, ceramic microspheres, calcium metasilicates, organic fillers, and the like. When used, such fillers may be employed in any desired amount. Suitable fillers or extenders ingredients are preferably present in an aggregate amount of less than 15 wt. %, based on the total weight of the aqueous coating composition.

[0040] Useful antimicrobial additives may include isothiazolinones such as benzisothiazolinone (BIT), a mixture of methylisothiazolinone (MIT) and chloro-methylisothiazolinone (CMIT). and quaternary ammonium compounds. Inorganic biocidal additive containing metal ions may also be of use. These include ionic compounds of silver, zinc, and copper, such as zinc pyrithione or copper glass nanoparticles.

[0041] Tire coating composition also may include other ingredients to modify the properties of the coating during storage, handling, and application. Waxes, flatting agents, mar and abrasion additives, and other similar performance enhancing additives may be employed as needed in amounts effective to upgrade the performance of the cured coating and the aqueous coating composition. Some suitable wax emulsions to improve coating physical performance include those sold under the trade names MICHEMTM Emulsions 32535, 21030, 61335, 80939M and 7173MOD from Michelman, Inc.Cincinnati, Ohio and CHEMCORTM 20N35, 43A40, 950C25 and 10N30 from ChemCor of Chester, New York. Desirable performance characteristics of the coating include adhesion, chemical resistance, abrasion resistance, hardness, gloss, reflectivity, appearance, or combinations of these characteristics, and other similar characteristics. For example, the composition may include abrasion resistance promoting adjuvants such as silica or aluminum oxide (e.g., sol gel processed aluminum oxide).

[0042] Any suitable drying agent may be included in a coating composition. Exemplary drying agents include metal -based drying agents that are calcium, potassium, lithium, zinc, zirconium, aluminum, bismuth, cobalt, or neodymium based. Particularly suitable are the iron-complex catalyst BORCHI® Oxy-Coat 1101, zirconium-based catalyst 12% Hydro Cem (both sold by OMG Borchers GmbH), cobaltbased catalyst 5% Cobalt Hydro Cure® II. a 10% solution of Calcium Cem -All®, all from Borchers Americas, Inc.

[0043] One or more types of pigment may be included in a coating composition via any suitable technique, such as by adding raw pigment or a pigment vehicle during manufacture of the composition or by instilling a pigment at the point of sale. Exemplary pigments include azo pigments, anazurite,aluminum silicate, aluminum potassium silicate, aluminum paste, anthraquinone pigments, antimony oxide, barium metaborate, barium sulfate, cadmium sulfide, cadmium selenide, calcium carbonate, calcium metaborate, calcium metasilicate, carbon black, chromium oxides, clay, copper oxides, copper oxychloride, dioxazine pigments, feldspar, hansa yellows azo pigments (some of which are listed above), benzimidazolones, iron oxides such as yellow and red iron oxides, isoindoline pigments, kaolinite, lithopone, magnesium silicates, metallic flakes, mica, napthol pigments such as napthol reds, nitroso pigments, nepheline syenite, perinone pigments, perylene pigments, polycyclic pigments, pyrropyrrol pigments, pthalocyanines such as copper pthalocyanine blue and copper pthalocyanine green, quinacridones such as quinacridone violets, quinophthalone pigments, silicates, sulfides, talc, titanium dioxide, ultramarine, zinc chromate, zinc oxide, and zinc phosphate. In addition, pearlescents, optical brighteners, ultraviolet stabilizers, and the like may be added to a coating composition. Titanium dioxide is a preferred pigment / whitening agent.Non-fluorinated. Non-polymeric Additive

[0044] Coating compositions of the present disclosure include a non-fluorinated, non-polymeric additive. The non-fluorinated, non-polymeric additive preferably is a salt, derived from an at least partially neutralized acid group. In preferred embodiments, the additive includes both (i) an acid group that has been at least partially or fully neutralized with a base, wherein the acid group includes at least one sulfur or phosphorus atom and (ii) a linear or branched, substituted or unsubstituted alkyl group. In certain embodiments, the alkyl group of the non-fluorinated, non-polymeric additive is fully saturated. In certain embodiments, the non-fluorinated, non-polymeric additive is folly saturated.

[0045] Examples of suitable bases for use in at least partially, or fully, neutralizing acid group(s) of the additive include a Group I or a Group II base such as sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, or magnesium hydroxide. In some aspects, the base is a sodium compound or potassium compound. The base may include ammonia or an amine, preferably an organoamine such as diethanolamine, trimethyl amine, dimethylethanol amine, methyldiethanol amine, triethanol amine, ethyl methyl ethanol amine, dimethyl ethyl amine, dimethyl propyl amine, dimethyl 3 -hydroxy- 1 -propyl amine, dimethylbenzyl amine, dimethyl 2 -hydroxy-1 -propyl amine, diethyl methyl amine, dimethyl I -hydroxyl- propyl amine, triethyl amine, tributyl amine, or N-methyl morpholine, or a mixture thereof. In some embodiments, it may be advantageous to use a basic compound for neutralization that is a fugitive base, more preferably a fugitive nitrogen base (e.g.. ammonia and primary, secondary, and / or tertiary amines).

[0046] In certain embodiments, the non-fluorinated, non-polymeric additive is selected from the salt of one or more alkyl phosphates, alkyl phosphonates, alkyl phosphate esters, alkyl sulfates, alkyl sulfonates, alkyl sulfate esters, or a combination thereof

[0047] In certain embodiments, the non-fluorinated, non-polymeric additive (prior to neutralization with base) comprises an alkyl phosphate ester, wherein the alkyl phosphate ester has the structure:wherein Rx represents a linear or branched alkyl group, Ry represents a linear or branched alkyl group, x represents the number of carbon atoms in the branched or linear alkyl group of Rx, y represents the number of carbon atoms in the branched or linear alkyl group of Ry, and a single coating composition may contain non-fluorinated, non -polymeric additives having different Rx and Ry values. In some embodiments, x ranges from 4 to 15 (i.e., 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 carbon atoms) and y is 0 (in which case Ry is a hydrogen atom) or ranges from 4 to 15 (i.e., 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 carbon atoms), and x and y range independently. In some aspects, x ranges from 6 to 14, and in some aspects, x ranges from 8 to 10. In some embodiments, neither Rx nor Ry includes any oxygen atoms in its longest carbon chain (e g., neither Rx nor Ry is alkoxylated). In some embodiments, Rx and Ry include only carbon and hydrogen in their longest carbon chains.

[0048] In some aspects, the non-fluorinated, non-polymeric additive has a number average molecular weight of no more than about 800, preferably no more than about 500, or even more preferably, no more than about 375.

[0049] In some aspects, the non-fluorinated, non-polymeric additive has a number average molecular weight of no more than about 800, or no more than about 500, or no more than about 375.

[0050] In some aspects, the non-fluorinated, non-polymeric additive has a number average molecular weight of at least about 100, at least about 150, at least about 175, or at least about 200.

[0051] In some aspects, the non-fluorinated, non-polymeric additive is produced by the reaction of a linear or branched alkyl alcohol and phosphating agent, followed by neutralization, as disclosed in Published PCT Application WO 2022 / 150168. By way of example, suitable phosphating agents include combinations of phosphorus pentoxide with hypophosphorous acid, polyphosphoric acid, or similar compounds.

[0052] In exemplary embodiments, the non-fluorinated, non-polymcric additive may be an additive from the Stepan STEPCOTE™ multi-functional wetting agent line of products (available from the StepanCompany, Northfield, IL). In exemplary embodiments, the non-fluorinated, non -polymeric additive is selected from STEPCOTE™ W-846, STEPCOTE™ W-849, STEPCOTE™ W-888, STEPCOTE™ W- 839, STEPCOTE™ W-843, STEPCOTE™ W-877, STEPCOTE™ W- 119, or the B-681 product also from Stepan.

[0053] In some aspects, the non-fluorinated, non-polymeric additive is present in an amount of at least about 0.05 wt. %, at least about 0.10 wt. % or at least about 0.15 wt. % based on tire total polymer solids in the coating composition. In some aspects, the non-fluorinated, non-polymeric additive is present in the coating composition in an amount of no more than about 3.0 wt. %, no more than about 2.0 wt. %, no more than about 2.5 wt. %, or no more than about 1.0 wt. %, or no more than 0.5 wt. %, based on the total polymer solids in the coating composition.Other Coating Composition Characteristics

[0054] In some aspects, coating compositions or coating and colorant systems of the present disclosure contain no intentionally added fluorine -containing compounds such as fluorosurfactants. Thus, in contrast to conventional solutions to improve blocking resistance, coating compositions or coating and colorant systems of the present disclosure in some aspects contain less than 0.01 wt.% fluorosurfactant as a percentage of tire total coating composition weight. In some aspects, coating compositions or coating and colorant systems of the present disclosure contain less than 1000 parts per billion (ppb), less than 100 ppb. less than 25 ppb, or less than 1 ppb of fluorine-containing compounds. In some aspects, the coating composition or coating and colorant systems of the present disclosure contain less than 1000 parts per billion (ppb), less than 100 ppb, less than 25 ppb, or less than 1 ppb of compounds containing perfluorinated moieties.

[0055] In some aspects, coating compositions of the present disclosure are free of an intentionally added polysiloxane. In some aspects, coating compositions or coating and colorant systems of the present disclosure contain less than 1000 parts per billion (ppb). less than 100 ppb, less than 25 ppb, or less than 1 ppb of a polysiloxane. In some aspects, the coating composition or coating and colorant systems of the present disclosure contain less than 1000 parts per billion (ppb), less than 100 ppb, less than 25 ppb, or less than 1 ppb of compounds containing siloxane moieties.

[0056] In some aspects, the non-fluorinated, non-polymeric additive of the present disclosure is a postadd in coating compositions. That is, the additive is added to the coating composition after polymerization of the polymeric binder. In other aspects, however, the additive is added to the alkyd dispersion which is subsequently a component of the coating composition. If added as a component of the alkyd dispersion, the non-fluorinated, non-polymeric additive may be added to the alkyd before or after dispersion of the alkyd in water. The additive also may be added to the water or base used to disperse the alkyd.

[0057] In some desirable embodiments, coating compositions of the present disclosure include no more than 500 g / L VOC, no more than 250 g / L VOC, no more than 150 g / L VOC, no more than 100 g / L VOC, no more than 50 g / L VOC, or no more than 25 g / L VOC.

[0058] Coating compositions of the present disclosure may be used to coat substrates, for instance, as a topcoat, primer coat, or a combination primer coat and topcoat. The aqueous coating compositions of the present disclosure may be suitable to coat, directly or indirectly, architectural materials such as brief, concrete, stucco, wood, gypsum board, or the like, as well as non-architectural materials such as metals or allows in automobiles or other machines, or other polymeric materials.Inclusion Through Colorant

[0059] Tire non-fluorinated, non-polymeric additive disclosed herein may also be added to a base paint through a colorant system. The colorant system may be used to impart color to, or tint, a tintable base paint or stain formulation that includes an aqueous alkyd emulsion binder as disclosed herein.

[0060] Colorant compositions are typically distributed and used in an array of 8 to 12 colors, each colorant composition having a different pigment composition to impart a different color. At the point of sale, one or more colorant compositions from the array are added volumetrically to a tintable base coating composition to achieve a desired coloration, or tint, of the paint formulation.

[0061] Thus, as disclosed herein, the coating and colorant system comprises an in-store tintable liquid base paint formulation that includes an aqueous alkyd emulsion as disclosed herein, with 0 to 25 wt. % of one of more colorant compositions which are added to a base paint to achieve a desired color.

[0062] In some aspects, the colorant compositions include the non-fluorinated, non-polymeric additive wherein the additive is present in the colorant compositions such that when metered into the liquid base coating composition, the resulting coating composition includes a desired concentration of the non- fluorinated, non-polymeric additive.Inclusion Through Non-Colored Fluid

[0063] In some aspects, the non-fluorinated, non-polymeric additive may be added to the base coating composition by metering a non-colored fluid that includes a carrier fluid and the non-fluorinated, non- polymeric additive, such that the non-colored fluid is metered or volumetrically added to the base coating composition, the non-fluorinated, non-polymeric additive is present in the coating composition in a desired amount.

[0064] In some aspects, the carrier of the non-colored fluid is water and the non-colored fluid further includes a humectant, a thickener, surfactant, dispersant, and a preservative.

[0065] In some aspects, the colorant compositions include less than 5 wt. % VOC based on the total components of the colorant composition.

[0066] In some aspects, coating compositions include the non-polymeric, non-fluorinated additive in an effective amount to achieve an increase of at least 1 rating point, and preferably at least 2 rating points at 1-hour, 6-hour, and / or 24-hour block resistance following curing for 1 days, 3 days, and / or 7 day cure at 77°F and 50% relative humidity according to the Block Resistance Test as described herein as compared to the same coating composition without the non-polymeric. non-fluorinated additive.DEFINITIONS

[0067] The term "‘block resistance,” as used herein, refers to the ability of the surface of a coating, when applied against the same coating applied to a substrate, to resist sticking to itself following prolonged contact under pressure. Block resistance is particularly useful in assessing the possibility of doors or windows to stick closed after painting. The Block Resistance Test, as defined and used herein, is ASTM D4946-89, with the following changes: an applicator blade having 3 mil clearance is used for coating on a Leneta chart. The coated substrates are allowed to cure for 1 day, 2 days, 3 days, or 7 days at 77°F (25°C) and 50% relative humidity, the cure time noted in experimental results. Following the noted cure time, 1 inch squares of the coated substrate are placed in a blocking apparatus compressed under 1 kg weight, coated face against coated face, for 1, 6, or 24 hours as noted in results. Tire time of compression is usually identified as “1-hour,” “6-hour” or “24-hour” block resistance. Block resistance is evaluated following drawdown according to the following scale:Rating Description Performance5 No tack Excellent4 Slight tack Good3 Tacky; no seal Poor2 5 to 25% seal Fail1 26-50% seal Fail0 50-100% seal FailBlock Resistance is considered to be adequate when 24-hour block resistance is measured as greater than 3 at each of 1-day, 3-day, and 7-day cure at 77°F (25°C) and 50% relative humidity.

[0068] The term ‘‘scrub resistance,” as used herein, refers to the ability of the surface of a coating film or paint film to resist being worn away or to maintain its original appearance when rubbed with or against an abrasive surface, typically during cleaning. To measure scrub resistance, a standard test method, ASTM D2486-96 (Standard Test Method for Scrub Resistance of Wall Paints) can be used, with the cure time following drawdown reported.

[0069] The term “NVM” means non volatile material and is an assessment of the percent volatile content of coatings. NVM is also referred to as percent solids. NVM may be evaluated according to ASTMD2369-20, titled “Standard Test Method for Volatile Content of Coatings.” An aluminum foil dish is weighted (Wl), and approximately 0.5 g of a weighed coating is placed in an aluminum foil dish, and the weight of the coating is determined (S). Tire coating and dish are heated for 60 minutes at 110°C, after which the dish is placed in a dessicator to cool and is weighed (W2). The NVM is calculated according to the equation: NVM = (W2-W1) / S. NVM is expressed as a percent.

[0070] Glass transition temperature, or Tg, refers to the temperature at which an amorphous material transitions from a hard and relatively brittle glassy state into a viscous or rubbery state as the temperature is increased and is measured by Differential Scanning Calorimetry (DSC). To measure Tg, a sample of the subject alkyd emulsion or coating composition is first obtained by drawdown using a 10 mil Bird bar on a glass plate. The drawdown is dried at room temperature, then dried in a vacuum oven for 2 hours. 1 10 mg sample from the drawdown is placed in a sample pan. The sample is then subjected to DSC according to a usual heat-cool-heat program according to ASTM D3418-82. titled “Standard Test Method for Transition Temperatures of Polymers by Thermal Analysis.” The Tf, extrapolated glass transition onset temperature, Tg, glass transition temperature, Te, extrapolated glass transition end temperature, and Tm, midpoint temperature, in °C, are obtained from the DSC test results.

[0071] The term "volatile organic compound" ("VOC"), as defined by the Environmental Protection Agency (EP A) in 40 C.F.R. 1. 100(s). refers to any compound of carbon, excluding carbon monoxide, carbon dioxide, carbonic acid, metallic carbides or carbonates, and ammonium carbonate, which participates in atmospheric photochemical reactions. Typically, volatile organic compounds have a vapor pressure equal to or greater than 0.1 mm Hg. As used herein, "volatile organic compound content" ("VOC content") in a coating composition, colorant composition, aqueous emulsion, or other composition is as measured by ASTM method D6886-18, and means the weight of VOC per volume of the composition solids, and is reported, for example, as grams VOC per liter (g / L). With respect to an aqueous emulsion described herein, VOC may also be reported as grams VOC per 100 grams of polymer solids (with reference to grams of the polymer in the emulsion). EPA Method 24 may be used to determine VOC in the alternative. If unstated or otherwise unclear from context with respect to a particular VOC measure, in the present application, ASTM method D6886-18 is the method used.

[0072] The phrase “low VOC” when used with respect to a liquid coating composition means that the liquid coating composition contains less than about 250 grams volatile organic compounds per liter composition, excluding water and exempt compounds. The term “ven' low VOC” means a liquid coating composition that contains less than 150 grams volatile organic compounds per liter of composition, excluding water and exempt compounds. The term “extremely low VOC” means a liquid coating composition that contains less than 50 grams volatile organic compounds per liter of composition,excluding water and exempt compounds. The term “no VOC” means a liquid coating composition that contains less than 5 grams VOCs per liter of composition.

[0073] Unless otherwise indicated, a reference to a “(meth)acrylic” compound (where “meth” is bracketed) is meant to include both acrylic and methacrylic compounds. Similarly, unless otherwise indicated, a reference to a “(meth)acrylate” (where meth is bracketed) is meant to include both acrylate and methacrylate compounds.

[0074] The term “polycarboxylic acid” includes both polycarboxylic acids and anhydride or esterified variants thereof.

[0075] Tire term “post-add” means that the identified additive is added to a coating composition or water-based composition such as an emulsion after polymerization of the polymeric binder.

[0076] The term “essentially free of’ a compound means the identified compound is not present in a bill of materials of the composition. Tire composition may include trace amounts of the compounds, above or below a detectable limit that become present in the composition through addition of other materials.

[0077] The term “effective amount” means an amount of the non-fhiorinated. non-polymenc additive sufficient to provide improved blocking resistance of a cured water-based coa ting composition when compared to the same coating composition without the non-fluorinated, non-polymcric additive.

[0078] Unless otherwise indicated, the term “polymer” includes both homopolymers and copolymers (i.e.. polymers derived from polymerization of two or more different monomers). Similarly, unless otherwise indicated, the use of a term designating a polymer class such as, for example, “polyester” is intended to include both homopolymers and copolymers (e g., copolyester polymers).

[0079] For the purposes of this specification and appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the tenn “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that can van' depending upon the desired properties sought to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Moreover, the term “about” as used in this specification and the claims includes the identified amount or quantity, taking in to account variation from measurement error, usual raw material variation, and experimental error.

[0080] As used in this specification and the appended claims, the singular forms “a,” “an,” and “the,” include plural referents unless expressly and unequivocally limited to one referent. Thus, for example, reference to “an additive” includes two or more different additives. As used herein, the tenn “include”and its grammatical variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that can be substituted or added to the listed items

[0081] Tire recitation of numeral ranges by endpoints includes all numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.). Furthermore, disclosure of a range intended to be a specific disclosure of all subranges included within the broader range (e.g., 1 to 5 discloses 1 to 4. 1.5 to 4.5, 1 to 2, etc.).

[0082] The terms “preferred” and “preferably” refer to embodiments of the present invention that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from tire scope of the present invention.

[0083] The terms “unsaturated” or “unsaturation” when used in the context of a compound refers to a compound that includes at least one non-aromatic double bond, typically a carbon-carbon double bond.

[0084] The term “comprises” and variations thereof do not have a limiting meaning where these terms appear in the description and claim

[0085] It is to be understood that each component, compound, substituent or parameter disclosed herein is to be interpreted as being disclosed for use alone or in combination with one or more of each and every other component, compound, substituent or parameter disclosed herein.

[0086] It is further understood that each range disclosed herein is to be interpreted as a disclosure of each specific value within the disclosed range that has the same number of significant digits. Thus, for example, a range from 1 to 4 is to be interpreted as an express disclosure of the values 1, 2, 3 and 4 as well as any range of such values.

[0087] It is further understood that each lower limit of each range disclosed herein is to be interpreted as disclosed in combination with each upper limit of each range and each specific value within each range disclosed herein for the same component, compounds, substituent or parameter. Thus, this disclosure to be interpreted as a disclosure of all ranges derived by combining each lower limit of each range with each upper limit of each range or with each specific value within each range, or by combining each upper limit of each range with each specific value within each range. That is, it is also further understood that any range between the endpoint values within the broad range is also discussed herein. Thus, a range from 1 to 4 also means a range from 1 to 3. 1 to 2, 2 to 4. 2 to 3, and so forth.

[0088] Furthermore, specific amounts / values of a component, compound, substituent or parameter disclosed in the description or an example is to be interpreted as a disclosure of either a lower or an upper limit of a range and thus can be combined with any other lower or upper limit of a range or specificamount / value for the same component, compound, substituent or parameter disclosed elsewhere in the application to form a range for that component, compound, substituent or parameter.EXAMPLESEXAMPLE 1: URETHANE MODIFIED ALKYD COATINGS

[0089] An evaluation was conducted of paints that included a non-fluorinated, non-polymeric phosphate ester additive with a urethane-modified alkyd emulsion binder.

[0090] The non-flourinated, non-polymeric phosphate ester additives each had a non-substituted, linear alkyl chain. The non-polymeric phosphate ester additive was STEPCOTE™ B-681 from Stepan Corp., an approximately 40% solution of, on belief, the amine salt of the reaction product of a C6 or C8 alcohol with phosphorous pentoxide in water.

[0091] Tire urethane modified alkyd emulsion was produced by first synthesizing a polyol composed of soyabean fatty acid, benzoic acid, pentaerthritol. and phthalic anhydride. Tire water produced as a product of the reaction was removed by utilizing a xylenes azeotrope until the acid number less than 10 mg KOH / g was achieved. After reaction, the xylenes were was removed by distillation under vacuum to provide a fatty acid modified polyester polyol. The polyol was allowed to cool to ambient temperature after which it was dissolved in methyl ethyl ketone (MEK). Tire resulting fatty acid modified polyol was then polymerized by mixing it with dimethylol propionic acid, Desmodur I, 3-isocyanatomethyl-3,5,5- trimethylcyclohexyl isocyanate (a cycloaliphatic diisocyanate. IPDI), triethyl amine and dibutyl tin dilaurate catalyst in dry MEK. The mixture was heated to 60°C and allowed to react until the isocyanate content is near undetectable by infrared spectroscopy. Tire resulting urethane-modified alkyd resin was cooled to 50°C and dispersed in demineralized water. Sodium lauryl sulfate as shown in Table 1, if any, is then mixed under low shear and the remaining MEK was removed by distillation. Additional water was added to yield a dispersion with NVM about 40%.

[0092] Coating compositions including the polyurethane dispersion and a phosphate ester additive as shown in Table 1 were mixed. The phosphate ester additives shown in Table 1 were added either in low- shear mixing to the alkyd polymer emulsion following polymerization or were added during paint mixing, in both instances using low shear mixing. The paint formulation used was Sherwin-Williams Water-based Pro Industrial Alkyd Urethane, Semi-gloss sheen, Extra White base, formula B53W02151.

[0093] Tire paint of sample 1 -Control A was Sherwin-Williams Water-based Pro Industrial Alkyd Urethane, Semi-gloss sheen. Extra White base, formula B53W02151. Tire paint of 1-Control A is known to include a urethane-modified alkyd emulsion binder that provides excellent block resistance. Sample 1- Control B is formula B53W02151 substituting the urethane-modified alkyd emulsion binder produced by the reaction above, with 1 .0 wt.% sodium lauryl sulfate and no polyether phosphate additive. 1-EXP A is formula B53W02151 substituting the urethane-modified alkyd emulsion binder produced by the reaction above, with 1.0 wt.% sodium laury l sulfate and 0.2 wt. % Stcpcotc™ B-681, based on the weight of polymer solids. Sample 1-EXP B is formula B53 W02151, substituting the urethane-modified alkydemulsion binder produced by the reaction above, with no sodium lauryl sulfate and 0.5 wt.% Stepcote™ B-681, based on the weight of polymer solids.

[0094] 24-hour block resistance was evaluated as the average of two duplicate measurements. Scrub resistance was evaluated following 7-day cure at room temperature.Table 1. Block Resistance of Urethane-modified Alkyd CoatingsAmount sodium Amount 24-hour Block lauryl sulfate STEPCOTE™ B- Resistance(wt.% based on 681 (wt.% based following 1 day / 2 ScrubExample polymer solids) on polymer solids) day / 7 day cure Resistance1-Control A 0.0 0.0 4 / 5 / 5 4581-Control B 1.0 0.0 1 / 1 / 2.5 2681- EXP A 1.0 0.2 5 / 5 / 5 <4001-EXP B 0.0 0.5 2 / 2.5 / 5 426

[0095] The data shows that paint compositions including the amine-neutralized polyether phosphate additive of the present disclosure provided equivalent blocking performance and only slightly worse scrub resistance compared to paint compositions known to have excellent block resistance. (1-Control A). Paint compositions that included the polyether phosphate additive showed significantly greater block resistance than a paint composition that did not include either a polyether phosphate additive (1 -Control B) or included a polymer known to have excellent block resistance. (1-Control A).

[0096] The effect of additional non-ionic surfactant was also evaluated. The block resistance of samples 1-Control A and 1-Control B as described above were evaluated against sample 1-EXP C. Experimental Sample 1-EXP C is Sherwin-Williams Water-based Pro Industrial Alkyd Urethane, Semi -gloss sheen, Extra White base, formula B53W02151 substituting the urethane-modified alkyd emulsion binder produced by the reaction above, with no sodium lauryl sulfate surfactant added, 0.5% non-ionic surfactant (Abex-2535 from Solvay S.A.) and 1.0 wt.% Stepcote™ W-877, based on the weight of polymer solids. Stepcote™ W-877 is believed to be an approximately 40% by weight solution of a non-polymeric, nonfluorinated alkyl on belief, the potassium salt of the reaction product of 1 -octanol with phosphorous pentoxide, or potassium octyl phosphate, in water

[0097] 24-hour block resistance was evaluated following a 1 day, 2 day, or 7 day cure according to tire test described herein.Table 2: Block Resistance of Urethane-modified Alkyd CoatingsAmount STEPCOTE™ W- 24-hour Block Resistance 877 additive (wt.%, based following on polymer solids) 1 day / 2 day / 7 day cure1 -Control A 0.0 5 / 4.5 / 5 1 -Control B 0.0 0 / 1 / 11-EXP C 1.0 5 / 5 / 5

[0098] The data shows that sample 1-EXP C, which contained 1.0 wt.% STEPCOTE W-877 phosphate ester additive based on polymer solids, provided identical block resistance compared to a sample that included a conventional polysiloxane anti -blocking additive 1 -Control A. 1-EXP C also provided vastly superior anti-blocking resistance compared to the same composition that included no anti-blocking additive 1 -Control B.EXAMPLE 2: ACRYLIC MODIFIED LONG OIL ALKYD COATINGS

[0099] Block resistance resulting from inclusion of STEPCOTE™ W-877 in acrylic modified long-oil alkyd polymer coatings was evaluated.[000100] Polymer 2-EXP is a low VOC acrylic modified, long-oil alkyd emulsion prepared according to the procedure for Example V of U.S. Patent 5,371,112, substituting a mixture of butyl acetate and methyl propyl ketone as solvent, and replacing 5% of solvent with soybean oil. Following polymerization, remaining solvent was removed by distillation and the polymer was dispersed in water to yield a dispersion of about 40% NVM. Following polymerization, STEPCOTE™ W-877 in an amount of 1.0 wt.% based on polymer solids was added with or without one or more additional metal driers. Block resistance was assessed following 1 day, 3 day, and 7 days of room temperature cure according to the method described herein.Table 3. Acrylic Modified Long-oil Alkyd CoatingsMetal Block ResistanceW-877 Drier1(wt.% based (g / 50 g 1 Day 3 Day 7 Day on polymer polymer (l-hour / 6- (l-hour / 6- (l-hour / 6-Coating Polymer solids) solids) hour / 24-hour) hour / 24-hour) hour / 24-hour)2-EXP-A 2-EXP 0.0 0 2 / 0 / 0 2 / 2 / 0 2 / 2 / 22-EXP-B 2-EXP 1.0 0 3 / 2 / 1 3 / 2 / 2 3 / 2 / 22-EXP-C 2-EXP 0.0 0.25 2 / 2 / 0 3 / 3 / 1 3 / 3 / 22-EXP-D 2-EXP 1.0 0.25 3 / 3 / 2 3 / 2 / 1 3 / 3 / 2[000101] The data shows that inclusion of a phosphate-ester based anti-blocking additive (samples 2-EXP-B and 2-EXP -D) improves the 1 day block resistance compared to identical samples that do not include the blocking additive. The data also shows that inclusion of the phosphate ester anti-blocking1Added metal drier is 5% Cobalt Hydro-Cure® II, from Borchers.additive without a metal drier package achieves nearly identical block resistance compared to the same polymer with the metal drier but without any phosphate ester anti-blocking agent.EXAMPLE 3: MEDIUM OIL ALKYD COATINGS[000102] Polymer 3-EXP is a proprietary medium oil alkyd of The Sherwin-Williams Company prepared from soyabean oil, pcntacrythntol. and phthalic anhydride. This penta-phthalic medium oil alkyd was cooked to acid value 10, and had 98% NVM. Hie alkyd was emulsified in water using the procedure provided by Oxetino USA, LLC, Pasadena. Texas. More specifically, anionic and non-ionic surfactants 9900 and 9800 of Oxetino USA were used at about 8% of alkyd solids, with dimethylethanolamine neutralization to emulsify the alkyd into water, yielding an emulsion with NVM 54.5%, pH 7.24, particle size 264 nm.[000103] Table 4 shows block resistance of the emulsified medium oil alkyd with 0.25 g / 50 g polymer solids a 5% solution of Cobalt Hydro Cure® II, 0.87 g / 50 g polymer solids of a 10% solution of Calcium Cem-All®. and 0.87 g / 50 g polymer solids of a 12% solution of Zironcium Hydro-cem®, all from Borchers Americas, Inc. Coating 3-EXP-A contains no phosphate ester surfactant. Coating 3-EXP-B contains STEPCOTE™ W-877 in an amount of 1.0 wt.% based on polymer solids. Block resistance of the clear coating was evaluated according to the test described herein.Table 4: Medium Oil Alkyd Emulsion Coating With Drier PackageW-877 Blocking (wt.% 7 Day Cure based on 1 Day Cure 3 Day Cure (l-hour / 6- polymer (l-hour / 6- (l-hour / 6- hour / 24- Coating Polymer solids) hour / 24-hour) hour / 24-hour) hour)3-EXP-A 3-EXP 0.0 2 / 1 / 1 3 / 3 / 2 3 / 3 / 33-EXP-B 3-EXP 1.0 3 / 3 / 1 3 / 3 / 3 4 / 4 / 3[000104] Tire data shows significant improvement in block resistance following a 1-day cure, equivalent block resistance following a 3-day cure, and improvement in block resistance following a 7- day cure compared to a coating composition comprising the same polymer without the non-fluorinated phosphate ester surfactant.[000105] The same polymer was prepared in a coating composition including the same metal driers as used in the test of Table 4. Loadings of the W-877 non-polymeric, non-fluorinated additive were varied. The coatings included 54.5% solids of polymer 3-EXP. Block resistance was evaluated according to the test described herein. Table 5 shows the results.Table 5: Medium Oil Alkyd Emulsion Coating with Drier PackageW-877 Block Resistance (wt.% 7 Day Cure based on 1 Day Cure 3 Day Cure (l-hour / 6- polymer (l-hour / 6- (l-hour / 6- hour / 24- Coating Polymer solids) hour / 24-hour)2hour / 24-hour) hour)3-EXP-C 3 -EXP 0.0 3 / 2 / 1 2.5 / 1 / 1 3 / 3 / 13-EXP-D 3-EXP 0.25 3 / 2 / 1 3 / 1 / 1 3 / 3 / 1.53-EXP-E 3-EXP 0.50 3 / 2 / 1 3 / 1.5 / 1 3Z3Z2.53-EXP-F 3-EXP 1.00 2.5 / 2.5 / 1 3 / 1.5 / 1 31312.53-EXP-G 3-EXP 2.00 2.512.512 3.5 / 2 / 1 4.5 / 3 / 33-EXP-H 3-EXP 3.00 2 / 3 / 2.5 4 / 3 / 3 4 / 4 / 43-EXP-I 3-EXP 4.00 3*13*13* 4.5Z4Z3 4 / 4 / 43 -EXP- J 3-EXP 5.00 3*13*13* 4 / 4 / 4 4Z4.5Z43-EXP-K 3-EXP 10.00 3*13*13* 31312 4Z3.5Z3[000106] The data shown in Table 5 indicates that coating composition including W-877 improved block resistance compared to coating compositions having no W-877, up to a concentration of less than 4.00 wt. % W-877. As W-877 includes the active non-fluorinated anti-blocking additive at a concentration of about 40% in water, the data indicates the additive is present up to 2.00 wt.% based on polymer solids.[000107] What has been described above includes examples of the present specification. It is, of course, not possible to describe every conceivable combination of components or methodologies for purposes of describing the present specification, but one of ordinary skill in the art may recognize that many further combinations and permutations of the present specification are possible. Each of the systems, components, and / or methodologies described above may be combined or added together in any permutation. Accordingly, the present specification is intended to embrace all such alterations, modifications and variations that fall within the spirit and scope of the appended claims. Furthennore. to the extent that the term "includes” is used in either the detailed description or the claims, such term is intended to be inclusive in a manner similar to the term "comprising” as “comprising” is interpreted when employed as a transitional word in a claim.[000108] Illustrative embodiments have been described, hereinabove. It will be apparent to those skilled in the art that the above compositions and methods may incorporate changes and modifications2Asterisk (*) indicates that the sample separated easily without ripping the panel because the coating had not properly coalesced.without departing from the general scope of this disclosure. The general scope of the disclosure is intended to encompass all such modifications and alterations.LIST OF EXEMPLARY EMBODIMENTS[000109] Embodiment 1: A water-based coating composition comprising: an aqueous alkyd emulsion; and a non-fluorinated, non-polymeric additive that includes (i) an acid group that has been at least partially neutralized with a base, wherein the acid group includes at least one sulfur or phosphorus atom and (ii) a linear or branched, substituted or unsubstituted alkyl group.[000110] Embodiment 2: The water-based coating composition of Embodiment 1, wherein the alkyd emulsion includes a urethane -modified alkyd polymer.[000111] Embodiment 3: Hie water-based coating composition of Embodiment 1, wherein the alkyd emulsion includes an (meth)acrylic-modified alkyd polymer.[000112] Embodiment 4: The water-based coating composition of Embodiment 1, wherein the alkyd emulsion includes a long-oil alkyd polymer.[000113] Embodiment 5: The water-based coating composition of Embodiment 1, wherein the alkyd emulsion includes a medium -oil alkyd polymer.[000114] Embodiment 6: The water-based coating composition of any one of Embodiments 1 through 5. wherein an alkyd polymer of the aqueous alkyd emulsion is derived from at least one fatty acid having at least ten carbons or a fatty oil that includes a fatty acid having at least ten carbons.[000115] Embodiment 7 : The water-based coating composition of Embodiment 6, wherein at least one fatty acid has 14 to 16 carbons or at least one fatty oil includes a fatty acid having 14 to 16 carbons.[000116] Embodiment 8: Tire water-based coating composition of any one of Embodiments 6 or 7, wherein the alkyd polymer is derived from more than one fatty acid.[000117] Embodiment 9: The water-based coating composition of any preceding Embodiment, wherein an alkyd polymer has at least one extrapolated glass transition onset temperature of at least - 50°C, or at least -30°C. or at least -10°C.[000118] Embodiment 10: Tire water-based coating composition of any preceding Embodiment, wherein an alkyd polymer of the alkyd emulsion has at least one extrapolated glass transition onset temperature of at most 30°C, preferably at most 20°C, preferably at most 10°C.[000119] Embodiment 11 : The water-based coating composition of any preceding Embodiment, wherein the alkyd emulsion has an NVM of at least 35%, preferably at least 45%, and preferably at least 55%.[000120] Embodiment 12: Tire water-based coating composition of any preceding Embodiment, wherein the non-fluorinated, non-polymeric additive is selected from the salt of one or more alkylphosphates, alkyl phosphonates, alkyl phosphate esters, alkyl sulfates, alkyl sulfonates, alkyl sulfate esters, or a combination thereof.[000121] Embodiment 13: The water-based coating composition of any preceding Embodiment, wherein the alkyl group of tire non-fluorinated, non-polymeric additive is fully saturated.[000122] Embodiment 14: The water-based coating composition of any preceding Embodiment, wherein the alkyl group of the non-fluorinated, non-polymeric additive is not folly saturated.[000123] Embodiment 15: The water-based coating composition of any preceding Embodiment, wherein the non-fluorinated, non-polymeric additive comprises an alkyl phosphate ester, wherein the alkyl phosphate ester has the structure:Owherein Rx represents a linear or branched alkyl group, Ry represents a linear or branched alkyl group, x represents the number of carbon atoms in the branched or linear alkyl group of Rx, y represents the number of carbon atoms in the branched or linear alkyl group of Ry. and a single coating composition may contain non-fluorinated, non-polymeric additives having different Rx and Ry values.[000124] Embodiment 16: The coating composition of Embodiment 15, wherein x ranges from 4 to 15 (i.e., 4, 5, 6, 7, 8, 9, 10 ... , or 15 carbon atoms) and wherein is 0 (in which case Ry is a hydrogen atom) or ranges from 4 to 15 (i.e., 4, 5, 6, 7, 8, 9, 10 ..., or 15 carbon atoms).[000125] Embodiment 17: The coating composition of Embodiment 16, wherein x ranges from 6 to 14, preferably 8 to 10.[000126] Embodiment 18: The coating composition of any one of Embodiments 15 to 17, wherein neither Rx nor Ry includes any oxygen atoms in its longest carbon chain (e.g., neither Rx nor Ry is alkoxylated).[000127] Embodiment 19: The coating composition of any one of Embodiments 15 to 18, whereinRx and Ry each include only carbon and hydrogen atoms.[000128] Embodiment 20: The water-based coating composition of any preceding Embodiment, wherein the non-fluorinated non-polymeric additive has a number average molecular weight of no more than about 800, no more than about 500, or no more than about 375.[000129] Embodiment 21 : The water-based coating composition of any preceding Embodiment, wherein the non-fluorinated non-polymeric additive has a number average molecular weight of at least about 100, at least about 150, at least about 175, or at least about 200.[000130] Embodiment 22: The water-based coating composition of any preceding Embodiment, wherein the non-fluorinated, non-polymenc additive is produced by reaction of a linear or branched alkyl alcohol and a phosphating agent.[000131] Embodiment 23: The water-based coating composition of any preceding claim, wherein the base is an amine, preferably an organoamine.[000132] Embodiment 24: The water-based coating composition of Embodiment 23, wherein the base is diethanolamine.[000133] Embodiment 25: The water-based coating composition of Embodiment 24, wherein the base is triethylamine.[000134] Embodiment 26: The water-based coating composition of any preceding Embodiment, wherein the base is a Group I or Group II base.[000135] Embodiment 27: The water-based coating composition of Embodiment 27, wherein the base is a sodium compound or a potassium compound.[000136] Embodiment 28: The water-based coating composition of any preceding Embodiment, wherein the non-fluorinated. non-polymeric additive is present in the coating composition in an amount of at least about 0.05 wt. %, at least about 0.10 wt. % or at least about 0.15 wt. % based on the total polymer solids in the coating composition.[000137] Embodiment 29: The water-based coating composition of any preceding Embodiment , wherein the non-fluorinated, non-polymeric additive is present in the coating composition in an amount of no more than about 1.5 wt. %, no more than about 1.0 wt. %, no more than about 0.75 wt. %, no more than about 0.5 wt. %, or no more than about 0.25 wt. % based on the total polymer solids in the coating composition.[000138] Embodiment 30: The water-based coating composition of any preceding Embodiment, wherein the coating composition is free of an intentionally-added polysiloxane.[000139] Embodiment 31 : The water-based coating composition of any preceding Embodiment, wherein the coating composition contain less than 1000 parts per billion (ppb), less than 100 ppb, less than 25 ppb. or less than 1 ppb of polysiloxane-containing compounds.T1[000140] Embodiment 32: The coating composition of any preceding Embodiment, wherein the coating composition contains less than 1000 parts per billion (ppb), less than 100 ppb, less than 25 ppb, or less than 1 ppb of compounds containing siloxane moieties.[000141] Embodiment 33: Tire water-based coating composition of any preceding Embodiment, wherein the coating composition or coating and colorant system contains no intentionally added fluorine- containing compounds.[000142] Embodiment 34: The water-based coating composition of any preceding Embodiment, wherein the coating composition contains no intentionally added fluorine -containing compounds.[000143] Embodiment 35: The coating composition of any preceding Embodiment, wherein the coating composition or coating and colorant system contain less than 0.01 \\t % fluorosurfactants as a percentage of the total coating composition weight or coating and colorant system weight, if any.[000144] Embodiment 36: The coating composition of any preceding Embodiment, wherein the coating composition or coating and colorant system each contain less than 1000 parts per billion (ppb), less than 100 ppb, less than 25 ppb, or less than 1 ppb of fluorine -containing compounds.[000145] Embodiment 37: The coating composition of any preceding Embodiment, wherein the coating composition contains less than 1000 parts per billion (ppb), less than 100 ppb, less than 25 ppb, or less than 1 ppb of compounds containing perfluorinated moieties.[000146] Embodiment 38: The coating composition or coating of any preceding Embodiment, wherein the coating composition or coating and colorant system each contain less than 1000 parts per billion (ppb), less than 100 ppb, less than 25 ppb, or less than 1 ppb elemental fluorine as it occurs in all chemical species in the coating composition or coating and colorant system, if any is present.[000147] Embodiment 39: The water-based coating composition of any preceding Embodiment, wherein the non-polymeric additive is a post-add.[000148] Embodiment 40: The water-based coating composition of any preceding Embodiment, wherein the non-polymeric additive is added to the alkyd emulsion prior to dispersion of the alkyd in water.[000149] Embodiment 41 : Tire water-based coating composition of any preceding Embodiment, wherein the non-polymeric additive is added to the alkyd emulsion after dispersion of the alkyd in water.[000150] Embodiment 42: The water-based coating composition of any preceding Embodiment, wherein the non-polymeric additive is added to the alkyd emulsion as part of the water used to disperse the alkyd.[000151] Embodiment 43: The water-based coating composition of any preceding Embodiment, wherein the coating composition includes at least 0.25 wt. % non-ionic surfactant, preferably at least 1%non-ionic surfactant, preferably at least 2 wt.% non-ionic surfactant based on the total weight of components of the coating composition.[000152] Embodiment 44: The w ater-based coating composition of any preceding Embodiment, wherein the coating composition has no more than 500 g / L VOC, no more than 250 g / L VOC, no more than 150 g / L VOC, no more than 100, no more than 50 g / L VOC, or no more than 25 g / L VOC.[000153] Embodiment 45: The water-based coating composition of any preceding Embodiment, wherein an alkyd polymer of the alkyd emulsion is derived from at least 20 wt.% bio-based monomers, at least 30 wt.% bio-based monomers, or at least 40 wt. % bio-based monomers based on the weight of all monomers polymers to form the alkyd polymers.[000154] Embodiment 46: Hie water-based coating composition of any preceding Embodiment, wherein the coating composition has no more than 500 g / L VOC, no more than 250 g / L VOC, no more than 150 g / L VOC, no more than 100. no more than 50 g / L VOC, or no more than 25 g / L VOC.[000155] Embodiment 47: The water-based coating composition of any preceding Embodiment, wherein the coating composition further includes at least one of a neutralizing agent, pigment, antifoaming agent, filler, dye, dispersant, surfactant, extender, adhesion promoter, wetting agent, rheology modifier, leveling agent, deflocculant, anti-blocking agent, antimicrobial agent, humectant, preservative, thickener, thixotropic agent, drying agent, anti-settling agent, rust inhibitor, and flattening agent, thickener, filler, or a coalescent.[000156] Embodiment 48: A tinted coating composition comprising: an in-store tintable liquid base coating composition that includes an aqueous alkyd emulsion; and one or more colorant compositions added to the coating composition, the colorant compositions each including at least a surfactant or a dispersant, and a one or more pigments, and optionally, a non-colored fluid, wherein one or more of the colorant compositions or the non-colored fluid includes a non-fluorinated. non-polymeric additive having (i) an acid group that has been neutralized with a base, wherein the acid group includes at least one sulfur or phosphorus atom and (ii) a linear or branched, substituted or unsubstituted alkyl group.[000157] Embodiment 49: The tinted coating composition of Embodiment 48, wherein each of the one or more colorant compositions have less than 5 wt. % VOC based on the total components of the colorant composition.[000158] Embodiment 50: The tinted coating composition of Embodiment 49, wherein one or more of the colorant compositions includes the non-fluorinated. non-polymeric additive.[000159] Embodiment 51 : The tinted coating composition of claim 50, wherein the non-colored fluid includes the non-fluorinated, non-polymeric additive.[000160] Embodiment 52: The tinted coating composition of claim 51, wherein a carrier fluid of the non-colored fluid is water and wherein the non-colored fluid further comprises a humectant, a thickener, an additional surfactant, a dispersant, and a preservative.[000161] Embodiment 53: Tire tinted coating composition of any one of claims 48 to 52, wherein the non-fluorinated, non-polymeric additive is selected from the salt of one or more alkyl phosphates, alkyl phosphonates, alkyl phosphate esters, alkyl sulfates, alkyl sulfonates, alkyl sulfate esters, or a combination thereof.[000162] Embodiment 54: The tinted coating composition of Embodiment 53, wherein the alkyl group of the non-fluorinated, non-polymeric additive is fully saturated.[000163] Embodiment 55: Tire tinted coating composition of any one of Embodiments 48 to 54, wherein the non-fluorinated. non-polymeric additive comprises an alkyl phosphate ester, wherein the alkyl phosphate ester has the structure:Owherein Rx represents a linear or branched alkyl group, Ry represents a linear or branched alkyl group, x represents the number of carbon atoms in the branched or linear alkyl group of Rx, y represents the number of carbon atoms in the branched or linear alkyl group of Ry, and a single coating composition may contain non-fluorinated, non-polymeric additives having different Rx and Ry values.[000164] Embodiment 56: Hie tinted coating composition of Embodiment 55, wherein x ranges from 4 to 15 (i.e., 4, 5. 6, 7, 8, 9, 10 ... , or 15 carbon atoms) and wherein y is 0 (in which case Ry is a hydrogen atom) or ranges from 4 to 15 (i.e.. 4, 5, 6, 7. 8, 9, 10 .... or 15 carbon atoms).[000165] Embodiment 57: The tinted coating composition of Embodiment 56, wherein x ranges from 6 to 14, preferably 8 to 10.[000166] Embodiment 58: The tinted coating composition of any one of Embodiments 56 or 57, wherein neither Rx nor Ry includes any oxygen atoms in its longest carbon chain (e.g., neither Rx nor Ry is alkoxylated).[000167] Embodiment 59: The tinted coating composition of any one of Embodiments 55 through58, wherein Rx and Ry each include only carbon and hydrogen atoms.[000168] Embodiment 60: The tinted coating composition of any one of Embodiments 48 through59, wherein the non-fluorinated non-polymeric additive has a number average molecular weight of no more than about 800, no more than about 500, no more than about 375.[000169] Embodiment 61: The tinted coating composition of any one of Embodiments 48 through60, wherein the non-fluorinated non-polymeric additive has a number average molecular weight of at least about 100, at least about 150, at least about 175, or at least about 200.[000170] Embodiment 62: The tinted coating composition of any one of Embodiments 48 through61, wherein the non-fluorinated. non-polymeric additive is produced by reaction of a linear or branched alkyl alcohol and a phosphating agent.[000171] Embodiment 63: The tinted coating composition of any one of Embodiments 48 to 62, wherein the base is an amine, preferably an organoamine.[000172] Embodiment 64: Hie tinted coating composition of Embodiment 63, wherein the base is diethanolamine.[000173] Embodiment 65: The tinted coating composition of any one of Embodiments 48 to 62, wherein the base is a Group I or Group II base.[000174] Embodiment 66: The tinted coating composition of Embodiment 64, wherein the base is a sodium compound or a potassium compound.[000175] Embodiment 67: Hie water-based coating composition or tinted coating composition of any preceding Embodiment, wherein the coating composition demonstrates a 24-hour blocking of at least 3, following each of 3 days and 7 days cure, when measured according to the Blocking Resistance test described herein.[000176] Embodiment 68: The water-based coating composition or tinted coating composition of claim 67, wherein the coating composition demonstrates a 24-hour blocking of at least 4, following each of 3 days and 7 days cure, when measured according to the Blocking Resistance test described herein; and wherein the binder of the coating composition is a medium oil alkyd or a urethane modified alkyd.[000177] Embodiment 69: The water-based coating composition or tinted coating composition of any preceding claim, wherein the coating composition demonstrates the same or increased 24-hour blocking following each of 3 days and 7 days cure, when measured according to tire Blocking Resistance test described herein as compared to the same coating composition without the non-flourinated, non- polymeric additive.[000178] Embodiment 70: A method of making a water-based coating composition comprising: mixing a non-fluorinated, non-polymeric additive that includes (i) an acid group that has been at leastpartially neutralized with a base, wherein the acid group includes at least one sulfur or phosphorus atom and (ii) a linear or branched, substituted or unsubstituted alkyl group and an alkyd polymer prior to or after dispersion of the alkyd polymer in water; and one or more coating additives.[000179] Embodiment 71: Tire method of Embodiment 70, wherein the alkyd polymer includes a urethane -modified alkyd polymer.[000180] Embodiment 72: The method of Embodiment 72, wherein the alkyd polymer includes an (meth)acrylic-modified alkyd polymer.[000181] Embodiment 73: The method of Embodiment 70, wherein the alkyd polymer includes a long-oil alkyd polymer.[000182] Embodiment 74: Tire method of Embodiment 70, wherein the alkyd polymer includes a medium-oil alkyd polymer.[000183] Embodiment 75: The method of Embodiment 70. wherein an alkyd polymer is derived from at least one fatty acid having at least ten carbons or at least one fatty oil having a fatty acid of at least ten carbons.[000184] Embodiment 76: The method of Embodiment 75, wherein the at least one fatty acid has 14 to 16 carbons or the at least one fatty oil has at least one fatty acid having 14 to 16 carbons.[000185] Embodiment 77: The method of any one of Embodiments 75 or 76, wherein tire alkyd polymer is derived from more than one fatty acid or fatty oil.[000186] Embodiment 78: The method of any one of Embodiments 70 to 77, wherein an alkyd polymer has at least one extrapolated glass transition onset temperature of at least -50°C, or at least -30°C. or at least -10°C.[000187] Embodiment 79: The method of any one of Embodiments 70 to 78, wherein an alkyd polymer of the alkyd emulsion has at least one extrapolated glass transition onset temperature of at most 30°C, preferably at most 20°C, preferably at most 10°C.[000188] Embodiment 80: The method of any one of Embodiments 70 to 79 further comprising: adjusting the NVM of the alkyd polymer in water to at least 35% NVM, preferably 45%, preferably 55%. [000189] Embodiment 81: Tire method of any one of claims 70 to 80, wherein the alkyl group of the non-fluorinated, non-polymeric additive is fully saturated.[000190] Embodiment 82: The method of any one of claims 70 to 81, wherein the non-fluorinated, non-polymeric additive comprises an alkyl phosphate ester, wherein the alkyl phosphate ester has the structure:wherein Rx represents a linear or branched alkyl group, Ry represents a linear or branched alkyl group, x represents the number of carbon atoms in the branched or linear alkyl group of Rx, y represents the number of carbon atoms in the branched or linear alkyl group of Ry, and a single coating composition may contain non-fluorinated, non-polymeric additives having different Rx and Ry values.[000191] Embodiment 83: The method of Embodiment 82, wherein x ranges from 4 to 15 (i.e., 4.5, 6. 7, 8, 9, 10 .. . , or 15 carbon atoms) and wherein y is 0 (in which case Ry is a hydrogen atom) or ranges from 4 to 15 (i.e., 4, 5, 6, 7, 8, 9, 10 ... , or 15 carbon atoms).[000192] Embodiment 84: The method of Embodiment 83, wherein x ranges from 6 to 14, preferably 8 to 10.[000193] Embodiment 85: The method of any one of Embodiments 83 or 84, wherein neither Rx nor Ry includes any oxygen atoms in its longest carbon chain (e.g., neither Rx nor Ry is alkoxylated).[000194] Embodiment 86: The method of any one of Embodiments 82 to 85, wherein Rx and Ry each include only carbon and hydrogen atoms.[000195] Embodiment 87: The method of any one of claims 82 to 86. wherein the non-fluorinated non-polymeric additive has a number average molecular weight of no more than about 800, no more than about 500, no more than about 375.[000196] Embodiment 88: Hie method of any one of claims 82 to 87, wherein the non-fluorinated non-polymeric additive has a number average molecular weight of at least about 100, at least about 150, at least about 175. or at least about 200.[000197] Embodiment 89: The method of any one of claims 82 to 88, wherein the non-fluorinated, non-polymeric additive is produced by reaction of a linear or branched alkyl alcohol and a phosphating agent.

Claims

CLAIMSWHAT IS CLAIMED IS:

1. A water-based coating composition comprising: an aqueous alkyd emulsion; and a non-fluorinated. non-polymeric additive that includes (i) an acid group that has been at least partially neutralized with a base, wherein the acid group includes at least one sulfur or phosphorus atom and (ii) a linear or branched, substituted or unsubstituted alkyl group.

2. Tire water-based coating composition of any preceding claim, wherein the non-fluorinated, non-polymeric additive is selected from the salt of one or more alkyl phosphates, alkyl phosphonates. alkyl phosphate esters, alkyl sulfates, alkyl sulfonates, alkyl sulfate esters, or a combination thereof.

3. The water-based coating composition of any preceding claim, wherein the aqueous alkyd emulsion includes a polyurethane-modified alkyd polymer, an acrylic- modified alkyd polymer, a medium -oil alkyd polymer, or a long-oil alkyd polymer.

4. The water-based coating composition of any preceding claim, wherein the alkyl group of tire non-fluorinated, non-polymeric additive is fully saturated.

5. The water-based coating composition of any preceding claim. wherein the alkyl group of the non-fluorinated, non-polymeric additive is not fully saturated.

6. The water-based coating composition of any preceding claim, wherein the non-fluorinated, non-polymeric additive comprises an alkyl phosphate ester, wherein the alkyl phosphate ester has the structure:Owherein Rx represents a linear or branched alkyl group, Ry represents a linear or branched alkyl group, x represents the number of carbon atoms in the branched or linear alkyl group of Rx. y represents the number of carbon atoms in the branched or linear alkyl group of Ry, and a single coating composition may contain non-fluorinated, non-polymeric additives having different Rx and Ry values.

7. The coating composition of claim 6, wherein x ranges from 4 to 15 (i.e., 4, 5, 6, 7, 8, 9, 10 or 1 carbon atoms) and wherein y is 0 (in which case Ry is a hydrogen atom) or ranges from 4 to 15 (i.e., 4, 5, 6, 7, 8, 9, 10 .... or 15 carbon atoms).

8. Tire coating composition of claim 7, wherein x ranges from 6 to 14, preferably 8 to 10.

9. The coating composition of any of claims 6-8, wherein neither Rx nor Ry includes any oxygen atoms in its longest carbon chain (e.g., neither Rx nor Ry is alkoxylated).

10. Tire coating composition of any of claims 6-9, wherein Rx and Ry each include only carbon and hydrogen atoms.

11. The water-based coating composition of any preceding claim, wherein the non-fluorinated non-polymeric additive has a number average molecular weight of no more than about 800, no more than about 500, or no more than about 375.

12. Tire water-based coating composition of any preceding claim, wherein the non-fluorinated non-polymeric additive has a number average molecular weight of at least about 100. at least about 150, at least about 175, or at least about 200.

13. The water-based coating composition of any preceding claim, wherein the non-fluorinated, non-polymeric additive is produced by reaction of a linear or branched alkyl alcohol and a phosphating agent.

14. Tire water-based coating composition of any preceding claim, wherein the base is an amine, preferably an organoamine.

15. The water-based coating composition of claim 14, wherein the base is diethanolamine.

16. The water-based coating composition of claim 15, wherein the base is triethylamine.

17. The water-based coating composition of any preceding claim, wherein the base is a Group I or Group II base.

18. The water-based coating composition of claim 17. wherein the base is a sodium compound or a potassium compound.

19. The water-based coating composition of any preceding claim, wherein the non-fluorinated, non-polymeric additive is present in the coating composition in an amount of at least about 0.05 wt. %. at least about 0.10 wt. % or at least about 0. 15 wt. % based on the total polymer solids in the coating composition.

20. The water-based coating composition of any preceding claim,wherein the non-fluorinated, non-polymcric additive is present in the coating composition in an amount of no more than about 1.5 wt. %, no more than about 1.0 wt. %, no more than about 0.75 wt. %, no more than about 0.5 wt. %, or no more than about 0.25 wt. % based on the total polymer solids in the coating composition.

21. The water-based coating composition of any preceding claim, wherein the coating composition is free of an intentionally-added polysiloxane.

22. The water-based coating composition of any preceding claim, wherein the coating composition contain less than 1000 parts per billion (ppb), less than 100 ppb, less than 25 ppb, or less than 1 ppb of poly siloxane -containing compounds.

23. Tire coating composition of any preceding claim, wherein the coating composition contains less than 1000 parts per billion (ppb), less than 100 ppb. less than 25 ppb. or less than 1 ppb of compounds containing siloxane moieties.

24. The water-based coating composition of any preceding claim, wherein the coating composition or coating and colorant system contains no intentionally added fluorine-containing compounds.

25. The water-based coating composition of any preceding claim, wherein the coating composition contains no intentionally added fluorine-containing compounds.

26. The coating composition of any preceding claim, wherein the coating composition or coating and colorant system contain less than 0.01 wt % fluorosurfactants as a percentage of the total coating composition w eight or coating and colorant system weight, if any.

27. The coating composition of any preceding claim, wherein the coating composition or coating and colorant system each contain less than 1000 parts per billion (ppb), less than 100 ppb. less than 25 ppb, or less than 1 ppb of fluorine-containing compounds.

28. The coating composition of any preceding claim, wherein the coating composition contains less than 1000 parts per billion (ppb), less than 100 ppb. less than 25 ppb, or less than 1 ppb of compounds containing perfluorinated moieties.

29. The coating composition or coating of any preceding claim. wherein the coating composition or coating and colorant system each contain less than 1000 parts per billion (ppb), less than 100 ppb, less than 25 ppb, or less than 1 ppb elemental fluorine as it occurs in all chemical species in the coating composition or coating and colorant system, if any is present.

30. The water-based coating composition of any preceding claim,wherein the non-polymeric additive is a post-add.

31. The water-based coating composition of any preceding claim, wherein the alkyd emulsion includes a urethane -modified alkyd polymer.

32. Tire water-based coating composition of any preceding claim, wherein the alkyd emulsion includes an (meth)acrylic-modified alkyd polymer.

33. The water-based coating composition of any preceding claim, wherein the alkyd emulsion includes a long-oil alkyd polymer.

34. The water-based coating composition of any preceding claim, wherein the alkyd emulsion includes a medium -oil alkyd polymer.

35. Tire water-based coating composition of any one of claims 31 through 35, wherein an alkyd polymer of the aqueous alkyd emulsion is derived from at least one fatty acid having at least ten carbons or a fatty oil that includes a fatty acid having at least ten carbons.

36. The water-based coating composition of claim 35, wherein at least one fatty acid has 14 to 16 carbons or at least one fatty oil includes a fatty acid having 14 to 16 carbons.

37. The water-based coating composition of claim 31 to 36, wherein the alkyd polymer is derived from more than one fatty acid or fatty oil.

38. The water-based coating composition of any preceding claim. wherein an alkyd polymer has at least one extrapolated glass transition onset temperature of at least -50°C, or at least -30°C. or at least -10°C.

39. Tire water-based coating composition of any preceding claim, wherein an alkyd polymer of the alkyd emulsion has at least one extrapolated glass transition onset temperature of at most 30°C, preferably at most 20°C, preferably at most 10°C.

40. The water-based coating composition of any preceding claim. wherein the alkyd emulsion has an NVM of at least 35%, preferably at least 45%, and preferably at least 55%.

41. Tire water-based coating composition of any preceding claim, wherein the non-polymeric additive is added to the alkyd emulsion prior to dispersion of the alkyd in water.

42. The water-based coating composition of any preceding claim. wherein the non-polymeric additive is added to the alkyd emulsion after dispersion of the alkyd in water.

43. Tire water-based coating composition of any preceding claim,wherein the non-polymeric additive is added to the alkyd emulsion as part of the water used to disperse the alkyd.

44. Tire water-based coating composition of any preceding claim, wherein the coating composition includes at least 0.25 wt. % non-ionic surfactant, preferably at least 1% non-ionic surfactant, preferably at least 2 wt.% non-ionic surfactant based on the total weight of components of the coating composition.

45. The water-based coating composition of any preceding claim, wherein the coating composition has no more than 500 g / L VOC, no more than 250 g / L VOC, no more than 150 g / L VOC, no more than 100, no more than 50 g / L VOC, or no more than 25 g / L VOC.

46. The water-based coating composition of any preceding claim, wherein an alkyd polymer of the alkyd emulsion is derived from at least 20 wt.% bio-based monomers, at least 30 wt.% bio-based monomers, or at least 40 wt. % bio-based monomers based on the weight of all monomers polymers to form the alkyd polymers.

47. Tire water-based coating composition of any preceding claim, wherein the coating composition has no more than 500 g / L VOC, no more than 250 g / L VOC, no more than 150 g / L VOC, no more than 100, no more than 50 g / L VOC, or no more than 25 g / L VOC.

48. The water-based coating composition of any preceding claim, wherein the coating composition further includes at least one of a neutralizing agent, pigment, antifoaming agent, fdler, dye, dispersant, surfactant, extender, adhesion promoter, wetting agent, rheology modifier, leveling agent, deflocculant, anti-blocking agent, antimicrobial agent, humectant, preservative, thickener, thixotropic agent, drying agent, anti-settling agent, rust inhibitor, and flattening agent, thickener, filler, or a coalescent.

49. A tinted coating composition comprising: an in-store tintable liquid coating composition that includes an aqueous alkyd emulsion; and one or more colorant compositions added to the coating composition, the colorant compositions each including at least a surfactant or a dispersant, and a one or more pigments, and optionally, a non-colored fluid, wherein one or more of the colorant compositions or the non-colored fluid includes a nonfluorinated, non-polymeric additive having (i) an acid group that has been neutralized with a base, wherein the acid group includes at least one sulfur or phosphorus atom and (ii) a linear or branched, substituted or unsubstituted alkyl group.

50. The tinted coating composition of claim 49, wherein each of the one or more colorant compositions have less than 5 wt. % VOC based on the total components of the colorant composition.

51. Tire tinted coating composition of claim 50, wherein one or more of the colorant compositions includes the non-fluorinated, non-polymeric additive.

52. The tinted coating composition of claim 51. wherein the non-colored fluid includes the nonfluorinated, non-polymeric additive.

53. The tinted coating composition of claim 52, wherein a carrier fluid of the non-colored fluid is water and wherein the non-colored fluid further comprises a humectant, a thickener, an additional surfactant, a dispersant, and a preservative.

54. The tinted coating composition of any one of claims 49 to 53, wherein the non-fluorinated, non- polymeric additive is selected from the salt of one or more alkyl phosphates, alkyl phosphonates, alkyl phosphate esters, alkyl sulfates, alkyl sulfonates, alkyl sulfate esters, or a combination thereof.

55. Tire tinted coating composition of claim 54, wherein the alkyl group of the non-fluorinated, non-polymeric additive is fully saturated.

56. The tinted coating composition of any one of claims 49-55, wherein the non-fluorinated, non-polymeric additive comprises an alkyl phosphate ester, wherein the alkyl phosphate ester has the structure:OO IH wherein Rx represents a linear or branched alkyl group, Ry represents a linear or branched alkyl group, x represents the number of carbon atoms in the branched or linear alkyl group of Rx, y represents the number of carbon atoms in the branched or linear alkyl group of Ry, and a single coating composition may contain non-fluorinated. non-polymeric additives having different Rx and Ry values.

57. The tinted coating composition of claim 56, wherein x ranges from 4 to 15 (i.e., 4, 5, 6, 7, 8, 9, 10 . . . , or 15 carbon atoms) and wherein y is 0 (in which case Ry is a hydrogen atom) or ranges from 4 to 15 (i.e., 4, 5, 6, 7, 8, 9, 10 ... , or 15 carbon atoms).

58. Tire tinted coating composition of claim 57, wherein x ranges from 6 to 14, preferably 8 to 10.

59. The tinted coating composition of any of claims 56-58, wherein neither Rx nor Ry includes any oxygen atoms in its longest carbon chain (e.g., neither Rx nor Ry is alkoxylated).

60. The tinted coating composition of any of claims 56-59, wherein Rx and Ry each include only carbon and hydrogen atoms.

61. The tinted coating composition of any of claims 49-60, wherein the non-fluorinated non-polymeric additive has a number average molecular weight of no more than about 800, no more than about 500, no more than about 375.

62. The tinted coating composition of any of claims 49-61, wherein the non-fluorinated non-polymeric additive has a number average molecular weight of at least about 100, at least about 150, at least about 175, or at least about 200.

63. The tinted coating composition of any of claims 49-61, wherein the non-fluorinated, non-polymeric additive is produced by reaction of a linear or branched alkyl alcohol and a phosphating agent.

64. The tinted coating composition of any of claims 49 to 63, wherein the base is an amine, preferably an organoamine.

65. Tire tinted coating composition of any of claims 64, wherein the base is diethanolamine.

66. The tinted coating composition of any of claims 49 to 63, wherein the base is a Group I or Group II base.

67. The tinted coating composition of claim 66, wherein the base is a sodium compound or a potassium compound.

68. Tire water-based coating composition or tinted coating composition of any preceding claim, wherein the coating composition demonstrates a 24-hour blocking of at least 3, following each of 3 days and 7 days cure, when measured according to the Blocking Resistance test described herein.

69. The water-based coating composition or tinted coating composition of claim 68, w herein the coating composition demonstrates a 24-hour blocking of at least 4, following each of 3 days and 7 days cure, when measured according to the Blocking Resistance test describedherein; and wherein the binder of the coating composition is a medium oil alkyd or a urethane modified alkyd.

70. Tire water-based coating composition or tinted coating composition of any preceding claim, wherein the coating composition demonstrates the same or increased 24-hour blocking following each of 3 days and 7 days cure, when measured according to the Blocking Resistance test described herein as compared to the same coating composition without the non-flourinated, non- polymeric additive.

71. A method of making a water-based coating composition comprising: mixing a non-fhiorinated, non-polymeric additive that includes (i) an acid group that has been at least partially neutralized with a base, wherein the acid group includes at least one sulfur or phosphorus atom and (ii) a linear or branched, substituted or unsubstituted alkyl group and an alkyd polymer prior to or after dispersion of the alkyd polymer in water; and one or more coating additives72. The method of claim 71, wherein the alkyd polymer includes a urethane -modified alkyd polymer.

73. The method of claim 71, wherein the alkyd polymer includes an (meth)acrylic-modified alkyd polymer.

74. The method of claim 71, wherein the alkyd polymer includes a long-oil alkyd polymer.

75. The method of claim 71, wherein the alkyd polymer includes a medium -oil alkyd polymer.

76. The method of claim 71, wherein an alkyd polymer is derived from at least one fatty acid having at least ten carbons or at least one fatty oil having a fatty acid of at least ten carbons.

77. The method of claim 71, wherein the at least one fatty acid has 14 to 16 carbons.

78. Tire method of any one of claims 76 or 77, wherein the alkyd polymer is derived from more than one fatty acid or fatty oil.

79. The method of any one of claims 71 to 78, wherein an alkyd polymer has at least one extrapolated glass transition onset temperature of at least -50°C, or at least -30°C. or at least -10°C.

80. The method of any one of claims 71 to 79, wherein an alkyd polymer of the alkyd emulsion has at least one extrapolated glass transition onset temperature of at most 30°C, preferably at most 20°C, preferably at most 10°C.

81. The method of any one of claims 71 to 80 further comprising: adjusting the NVM of the alkyd polymer in water to at least 35% NVM, preferably 45%, preferably 55%.

82. Tire method of any one of claims 71 to 81, wherein the alkyl group of tire non-fluorinated, non-polymeric additive is fully saturated.

83. The method of any one of claims 71 to 82, wherein the non-fluorinated, non-polymeric additive comprises an alkyl phosphate ester, wherein the alkyl phosphate ester has the structure:OO IH wherein Rx represents a linear or branched alkyl group, Ry represents a linear or branched alkyl group, x represents the number of carbon atoms in the branched or linear alkyl group of Rx, y represents the number of carbon atoms in the branched or linear alkyl group of Ry, and a single coating composition may contain non-fluorinated, non-polymeric additives having different Rx and Ry values.

84. The method of claim 83, wherein x ranges from 4 to 15 (i.e., 4, 5, 6, 7, 8, 9, 10 .. . , or 15 carbon atoms) and wherein y is 0 (in which case Ry is a hydrogen atom) or ranges from 4 to 15 (i.e., 4, 5, 6, 7, 8, 9, 10 ... , or 15 carbon atoms).

85. Tire method of claim 84, wherein x ranges from 6 to 14, preferably 8 to 10.

86. Tire method of any one of claims 84 or 85, wherein neither Rx nor Ry includes any oxygen atoms in its longest carbon chain (e.g., neither Rx nor Ry is alkoxylated).

87. Tire method of any one of claims 83 to 86, wherein Rx and Ry each include only carbon and hydrogen atoms.

88. The method of any one of claims 83 to 87, wherein the non-fluorinated non-polymeric additive has a number average molecular weight of no more than about 800, no more than about 500, no more than about 375.

89. The method of any one of claims 83 to 88, wherein the non-fluorinated non-polymeric additive has a number average molecular weight of at least about 100, at least about 150, at least about 175, or at least about 200.

90. Tire method of any one of claims 83 to 89, wherein the non-fluorinated, non-polymeric additive is produced by reaction of a linear or branched alkyl alcohol and a phosphating agent.

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