Aqueous coating composition comprising a solvent system for low temperature

Abstract

Disclosed is an aqueous coating composition comprising a monohydric alcohol and a diol or polyol and a compound having a urea functionality. The aqueous coating composition has a VOC of less than 250 g / L, can be applied to a variety of substrates at temperatures below the freezing point (32 DEG F) in high quality, stored below the freezing point for more than 2 weeks without bulk freezing, and applied at temperatures below the freezing point by a variety of common application techniques (brushes, rollers, sprayers). Additives may be added either alone or together as a low temperature additive package to the coating composition during manufacture of the coating composition.

Description

[0001] References to earlier filed applications

[0002] Priority is claimed to U.S. Provisional Patent Application No. 63 / 337,789, filed on May 3, 2022, the entire contents of which are incorporated by reference. Background Art

[0003] Water-based coating compositions balance many competing factors related to coating application, drying time, and final appearance. For example, aqueous coating compositions are expected to provide relatively good flow to facilitate coating application and a smooth surface finish, while also providing good sag resistance and thick film build to reduce the number of runs and required coating applications. Such features are particularly important at low temperatures, as conventional waterborne systems become unstable as temperatures approach and fall below freezing.

[0004] Conventional aqueous coating compositions for architectural applications, such as latex-based paints and stains, can be applied under a wide range of conditions. In the past, because the properties of water-based coatings are adversely affected as they approach the freezing point of water, the conditions under which aqueous coatings can be applied have been limited to just above the freezing point (e.g., about 35°F).

[0005] The use of water-based paints at low temperatures is limited by freezing of the wet (in-can) coating composition when exposed to low temperatures for extended periods of time, and changes in the rheological properties of the coating composition at low temperatures (which may manifest as defects in workability, wet edges, and flow and leveling in the wet state). Applying the coating composition by spraying rather than brushing or rolling may present additional challenges, such as spray gun spatter, spray tip clogging, atomization, and coverage problems. In addition, at low temperatures, the applied coating composition may not form an acceptable film, but instead appear to have one or more cosmetic defects, such as a cracked appearance, an excessively gritty appearance, an "orange peel" appearance when the coating is cracked, or a "frosted" appearance when the coating freezes before drying.

[0006] Conventional solutions for providing coatings that can be applied below the freezing point of water include the inclusion of solvent systems to regulate the rate of water evaporation at low temperatures. Many industries use solvent blends containing ethylene glycol to change the boiling / freezing point of liquids. However, such approaches offer limited performance benefits in the context of coatings because the volatility of the solvent blend must be carefully balanced to allow coating coalescence to occur within an appropriate duration.

[0007] Conventional inclusion of solvent blends may be disadvantageous for other reasons. Solvent blends may have an adverse effect on volatile organic compound (VOC) content. In addition, the amount of VOC that may be present in the exterior coating is subject to restrictions by EPA, state and local regulations. Such regulations limit the amount of VOC that may be present to 250g / liter or 100g / liter or 50g / liter. In addition, some VOCs are carcinogenic and require additional personal protective equipment when used. Inclusion of solvent systems may also be incompatible with the spraying of coatings, because coating compositions with higher VOC content may become too viscous at low temperatures, and may partially evaporate after spraying but before the coating is fully adhered to the substrate.

[0008] Existing commercially available low temperature aqueous exterior architectural coatings have inadequate performance. The only known product of this type has a VOC of at least 150 g / L and therefore cannot be distributed or used in all regions of the United States. Furthermore, although the product is advertised as suitable for application at temperatures below freezing, the product manufacturer instructs it to be stored at approximately room temperature (60°F).

[0009]

[0006] Therefore, there is a need for a low VOC aqueous paint composition that can be applied to a variety of substrates by a variety of applicators at temperatures below the freezing point of water without visible defects while maintaining the durability of existing coating compositions. Summary of the invention

[0010] According to one aspect, a low-temperature aqueous coating composition is disclosed, the coating composition comprising: an aqueous carrier liquid; a polymer binder; and a diol or polyol having a first conventional vapor pressure of less than 0.2 mm Hg; and a monool having a second conventional vapor pressure, and a compound having urea functionality; wherein the first conventional vapor pressure is less than the second conventional vapor pressure; wherein the aqueous coating composition has a VOC of less than 250 g / L.

[0011] In another aspect, an additive package for adding to a coating composition to impart low temperature stability and applicability is disclosed, the additive comprising: a diol or polyol having a first normal vapor pressure of less than 0.2 mm Hg; and a monool having a second normal vapor pressure, and a compound having urea functionality, wherein the first normal vapor pressure is less than the second normal vapor pressure. A method of preparing a low temperature coating composition is also disclosed, the method comprising adding the additive package to a polymer binder.

[0012] According to yet another aspect, a method of preparing a low-temperature aqueous coating composition is disclosed, the method comprising adding to the coating composition a diol or polyol having a first conventional vapor pressure of less than 0.2 mm Hg, a monool having a second conventional vapor pressure, and a compound having urea functionality, wherein the first conventional vapor pressure is less than the second conventional vapor pressure.

[0013] The aqueous coating compositions of the present invention have a VOC of less than 250 g / L and are capable of being applied to a variety of substrates at temperatures below freezing (32° F.) with high quality, stored below freezing for more than 2 weeks without bulk freezing, and applied by a variety of commonly used application techniques (brush, roller, sprayer) at temperatures below freezing.

[0014] The above summary of the invention of the present invention is not intended to describe each and every embodiment or feature of the present invention. The following description more specifically illustrates exemplary embodiments. In several places throughout the application, guidance is provided by lists of examples, which can be used in various combinations. In each case, the cited lists are used only as representative groups and should not be interpreted as exclusive enumerations.

[0015] The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 is an image of the appearance of frosting on the applied film.

[0017] Figure 2A Figure 2B , Figures 2C and 2D show microscopic examination images at 100x of a 5 mil coating (wet) of the coating on an aluminum panel after curing the coating in a 25°F freezer. Figure 2A is a coating composition of the present invention. Figure 2B Polar described in Example 1 below Figure 2C is a conventional all-acrylic exterior masonry paint. Figure 2D is a conventional all-acrylic exterior paint.

[0018] definition

[0019] "Latex" polymer means a dispersion or emulsion of polymer particles formed in the presence of water and one or more dispersants or emulsifiers (e.g., surfactants, alkali-soluble polymers, or mixtures thereof), which need to be present to form the dispersion or emulsion. After the polymer is formed, the dispersant or emulsifier is typically separated from the polymer. In some examples, the reactive dispersant or emulsifier may become part of the polymer particles when formed.

[0020] The recitation of numerical ranges using endpoints includes all numbers subsumed within that range (eg, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

[0021] "A", "an", "the", "at least one", and "one or more" are used interchangeably. Thus, for example, an aqueous coating composition comprising "an" additive means that the aqueous coating composition comprises "one or more" additives.

[0022] The terms "comprises" and variations thereof do not have a limiting meaning when they appear in the description and claims.

[0023] The term "on" when used in the context of a coating applied on or to a surface or substrate includes coatings applied directly to the surface or substrate, as well as coatings applied indirectly to the surface or substrate, such as when there is an interstitial layer (such as a primer or treatment) between the substrate and the coating.

[0024] When used with respect to a liquid coating composition, the phrase "low VOC" means that the liquid coating composition contains less than about 250 grams of volatile organic compounds per liter of composition, excluding water and exempt compounds. The term "very low VOC" means that the liquid coating composition contains less than 150 grams of volatile organic compounds per liter of composition, excluding water and exempt compounds. The term "extremely low VOC" means that the liquid coating composition contains less than 50 grams of volatile organic compounds per liter of composition, excluding water and exempt compounds.

[0025] The term "(meth)acrylic acid" includes either or both of acrylic acid and methacrylic acid, and the term "(meth)acrylate" includes either or both of acrylate and methacrylate.

[0026] The term "topcoat" or "final topcoat" refers to an aqueous coating composition that, when dried or otherwise hardened, provides a decorative or protective outermost finish layer on a substrate, such as a polymeric film attached to a building exterior (e.g., a roof). By way of further illustration, such final topcoats include paints, stains, or sealants that are capable of withstanding extended outdoor exposure (e.g., exposure to a year's worth of vertical south-facing Florida sunlight) without adverse visual degradation, but do not include primers that would not withstand extended outdoor exposure if the topcoat were not applied.

[0027] When the terms "free of," "does not contain," "does not include," "does not include any," and similar phrases are used herein, such phrases are not intended to exclude the presence of trace amounts of related structures or compounds that may be present but not intentionally used, for example due to the presence of environmental contaminants.

[0028] Test Method

[0029] Volatile organic compounds (VOCs) are defined by the regulations of the United States Environmental Protection Agency as any carbon compound other than carbon monoxide, carbon dioxide, carbonic acid, metal carbides or carbonates, and ammonium carbonate that participates in atmospheric photochemical reactions, except for exempt compounds as specified in Part 51.100 of Title 40 of the United States Code of Federal Regulations. The amount of VOC present in the composition can be measured by gas chromatography by ASTM D6886-18 entitled "Standard Test Method for Determination of the Weight Percent of Individual Volatile Organic Compounds in Waterborne Air-Dry Coatings by Gas Chromatography". The amount of VOC is reported in grams per liter of the composition minus the exempt compounds (g / L).

[0030] The "conventional vapor pressure" of a compound is the vapor pressure of that compound at 20°C, expressed in mm Hg. Vapor pressures are available in various chemistry and chemical engineering texts, including Perry's Chemical Engineering Handbook, by Don W. Green and Robert H. Perry; and the CRC Handbook of Chemistry and Physics.

[0031] Viscosity measurements are measured by the method in ASTM D562-10 entitled "Standard Test Method for Consistency of Paints Measuring Krebs Unit (KU) Viscosity Using a Stormer-Type Viscometer", which is modified to allow viscosity measurements when the sample is cooled and equilibrated to a specified temperature.

[0032] The bulk freeze stability of a composition can be determined by a bulk freeze test in which a one gallon container or can of the composition is sealed with a lid and cooled to 25°F and held for 14 days. The lid is opened and the bulk composition is evaluated for freezing. Compositions that remain in a liquid flowable form are considered to have passed the test. Compositions that are completely or partially frozen are considered to have failed the test. DETAILED DESCRIPTION

[0033] The present disclosure describes a low temperature aqueous coating composition comprising: an aqueous carrier fluid; a polymer binder; and a low temperature additive package comprising a diol or polyol having a first conventional vapor pressure of less than 0.2 mm Hg, a monool having a second conventional vapor pressure, and a compound having urea functionality, wherein the first conventional vapor pressure is less than the second conventional vapor pressure. The monool, diol or polyol and the compound having urea functionality may be mixed first and then added to the carrier of the coating composition, or may be added to the carrier individually or in combination. The coating composition has a VOC of less than 250 g / L.

[0034] The combination of a diol or polyol, a monool and a compound having urea functionality results in a coating composition having more consistent viscosity, application characteristics and applied appearance, as well as suitable flow and rheology behavior for spraying at low temperatures. The low temperature additive package of the present invention is compatible with a wide variety of polymer binders and exhibits exceptionally low VOC content when present in a low temperature aqueous coating composition.

[0035] Without being bound by theory, it is believed that the components of the low temperature additive package of the present invention provide a diol or polyol that lowers the freezing point of the coating composition but results in relatively low coalescence of the applied coating; a monool that provides a sufficiently high vapor pressure to allow the applied film to coalesce prior to freezing; and a urea compound that is believed to slow the freezing of the aqueous coating by interfering with the hydrogen bonding that occurs in the water of the aqueous carrier. It is also believed that the solvent combination of the present invention slows the evaporation rate of the water of the aqueous coating composition, thereby preventing "frosting", i.e., the patterned appearance of ice crystals that occur during coalescence of a coating composition applied at a lower application temperature. As Figure 1 As shown, this patterned "frosted" appearance on the applied film is irreversible and persists even after the applied coating composition coalesces and dries.

[0036] Thus, it has been unexpectedly discovered that the inclusion of the mono-, di- or polyol and the urea compound in a coating composition allows for consistent, high quality application of the coating composition at low temperatures with very low VOC content.

[0037] Compared to commercially available existing coating compositions that can be applied at temperatures below the freezing point, embodiments of the present invention are low VOC and can be stored for weeks at temperatures below the freezing point (32°F), which allows the composition to be transported during the winter without bulk freezing. The VOC content of the coating composition of the present invention is preferably less than about 250 g / L, less than 150 g / L, less than 100 g / L, or most preferably less than 50 g / L. More specifically, the coating composition of the present invention is suitable for storage for more than one month at a temperature below 35°F, preferably below 30°F, below 27°F, below 25°F, or below 23°F. In addition, embodiments of the present invention can be stored at low temperatures and applied by any common application techniques (including brushing, spraying with air or airless sprayers, or roller coating). This is in contrast to existing formulations, which freeze or clog when sprayed below the freezing point.

[0038] The coating compositions of the present invention preferably provide consistent, high quality applications at temperatures below 35°F, preferably below 30°F, below 27°F, below 25°F, or below 23°F.

[0039] The monohydric alcohol of the present invention is preferably a straight or branched C1 to C4 alcohol, and preferably has a conventional vapor pressure of at least 0.4 mm Hg. Preferably, the monohydric alcohol is 1-butanol or ethanol. The monohydric alcohol of the present invention is present in the coating composition in an amount of 1.0 weight percent to 2.5 weight percent based on the total weight of the aqueous coating composition, or preferably in an amount of 1.25 weight percent to 2.25 weight percent, or even more preferably in an amount of about 1.5 weight percent to about 2.0 weight percent based on the total weight of the aqueous coating composition. The composition of the present invention may include one or more monohydric alcohols.

[0040] The diol or polyol of the present invention has a conventional vapor pressure less than 0.2 mm Hg, and is preferably a C1 to C6 diol. Preferred diols are ethylene glycol, propylene glycol, L-glutamic acid and / or DL-serine. The polyol of the present invention can be a triol, such as glycerol or ordinary sugar, preferably selected from the group ordinary sugar consisting of the following items: mannitol, sorbitol, glucose, sucrose, fructose or a combination thereof. Based on the gross weight of the aqueous coating composition, the diol or polyol of the present invention is present in the coating composition in an amount of 1.0 wt % to 2.5 wt %, or preferably based on the gross weight of the aqueous coating composition, is present in the coating composition in an amount of 1.25 wt % to 2.25 wt % or even more preferably in an amount of about 1.5 wt % to about 2.0 wt %. The composition of the present invention may comprise one or more diols or polyols.

[0041] The compounds of the present invention having urea functionality have the following structure:

[0042]

[0043] Wherein R1, R2, R3 and R4 are the same or different and contain linear or branched alkyl, aryl, linear or branched alcohol, or H group. The compound with urea functionality is preferably urea, 2-hydroxyethylurea, bis(hydroxymethyl)urea or a combination thereof. In some methods, the compound with urea functionality of the present invention is present in the coating composition in an amount of at least 1.75 wt % based on the total weight of the coating composition.

[0044] Compared to other aqueous coating compositions, the aqueous coating compositions of the present invention exhibit better fluidity and rheological properties at relatively low temperatures (e.g., about 23°F, about 25°F, about 27°F, about 30°F, or about 35°F). This rheological property, together with the absence of ice crystals from early freezing, facilitates spray atomization, reduces spray gun noise, and facilitates brush transfer and release compared to other aqueous coating compositions. Therefore, the coating compositions of the present invention have high low temperature application capabilities in various application techniques (e.g., spraying, brushing, roller coating).

[0045] Compared to coatings having less consistent loss tangent after shearing, specifically, compared to aqueous coating compositions that exhibit a lower loss tangent (tan δ) after shearing than before shearing, the aqueous coating compositions described herein that include the low temperature additive package can exhibit better flow and leveling, reduced brush lines, etc. Thus, the coatings formed from the aqueous coating compositions that include the solvent system described herein include improved appearance characteristics.

[0046] The monohydric alcohol, diol or polyol and the compound having urea functionality can be added to the coating composition separately during or after the manufacture of the coating composition, or can be added to the coating composition together as an additive package. The components of the low temperature additive system of the present invention can be added to conventional coating compositions separately, or can be pre-mixed into a low temperature additive system for addition to conventional coating compositions to improve the low temperature effect of the coating composition.

[0047] The aqueous coating composition of the present invention also comprises a polymer binder and a carrier. In some examples, the aqueous coating composition may comprise 20 to 45 weight percent of a binder, more preferably 25 to 40 weight percent of a binder, and even more preferably 30 to 35 weight percent of a binder, based on the total weight of the aqueous coating composition.

[0048] The polymer binder may be any suitable polymer binder. The polymer binder may include, for example, polymer binders used in paint formulations, clear coating formulations, stain formulations, sealant formulations, etc., and may be used in water-based formulations or solvent-free formulations. In some examples, the polymer binder may be present in a carrier liquid, and may be dispersed in the carrier liquid (e.g., dispersed in an emulsion stabilized in a colloid manner or using a surfactant), present as a solute in the carrier liquid (e.g., present in a solution polymer), etc.

[0049] In some examples, the polymer binder can be an aqueous polyurethane, latex, (meth) acrylate, acetate (e.g., ethylene-vinyl acetate), etc. The polymer binder can be synthetic, or can be a naturally occurring polymer, biopolymer, or bio-based polymer, such as a cross-linked or non-cross-linked polymer based on a polysaccharide, polypeptide, lipid, nucleic acid. Some exemplary polymer binders include poly (ethylene-vinyl acetate) "PEVA", vinyl ester homopolymers or copolymers, silane or fluorine-containing latex emulsions, etc. For example, the polymer binder may include a latex-based paint formulation, and may include a polymer binder containing a latex copolymer that is a surfactant or colloidally stable in a latex emulsion.

[0050] The latex copolymer may comprise (meth) acrylic latex, vinyl acrylic latex or styrene acrylic latex. The latex copolymer may be formed from reactants including methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, 2-(acetoacetoxy)ethyl methacrylate (AAEM), diacetone acrylamide (DAAM), acrylamide, methacrylamide, hydroxymethyl (meth) acrylamide, styrene, α-methylstyrene, vinyl toluene, vinyl acetate, vinyl propionate, allyl methacrylate and mixtures thereof. Some preferred monomers include styrene, methyl methacrylate, methacrylic acid, acetoacetoxyethyl methacrylate, butyl acrylate, butyl methacrylate and the like.

[0051] In some examples, the reactants that form the latex copolymer also include an ethylenically unsaturated polar component. For example, the ethylenically unsaturated polar component may include an ethylenically unsaturated monomer having at least one alcohol group, an ethylenically unsaturated ionic monomer, an at least partially neutralized ethylenically unsaturated ionic monomer, etc. The at least partially neutralized ethylenically unsaturated ionic monomer may be in the form of a salt of the ethylenically unsaturated ionic monomer, and the salt form may be formed before, during, or after the ethylenically unsaturated ionic monomer reacts with other monomers in the reactants to form the latex copolymer.

[0052] In some examples, the ethylenically unsaturated polar monomer may include an acid or anhydride functional ethylenically unsaturated monomer or an at least partially neutralized acid or anhydride functional ethylenically unsaturated monomer. For example, the ethylenically unsaturated polar monomer may include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methylmaleic acid, itaconic acid, 2-methylitaconic acid, anhydride variants thereof, at least partially neutralized variants thereof, or combinations thereof.

[0053] The carrier of the aqueous coating composition of the present invention is any kind of water, including purified water, tap water or distilled water, and may include recycled water.

[0054] The aqueous coating compositions of the present invention may also contain one or more additives including coalescing agents, surfactants, pigments, fillers, extenders, biocides and UV stabilizers in amounts and concentrations known to those skilled in the art.

[0055] The aqueous coating composition may contain one or more optional coalescing agents to facilitate film formation. Coalescing agents suitable for use in aqueous coating compositions will be known to those of ordinary skill in the art, or can be determined using standard methods. Exemplary coalescing agents include glycol ethers, such as those sold under the trade name EASTMAN TM EP, EASTMAN TM DM, EASTMAN TM DE, EASTMAN TM DP, EASTMAN TM DB and EASTMAN TM PMs are those sold by Eastman Chemical Company (Kingsport, Tennessee), and ester alcohols such as those sold under the trade name TEXANOL TMThe ester alcohols are those sold by Eastman Chemical Company. The optional coalescing agent may be a low VOC coalescing agent, such as described in U.S. Pat. No. 6,762,230 B2. The aqueous coating composition may include at least about 0.5 wt. %, or at least about 1 wt. %, and / or at least about 2 wt. % of the low VOC coalescing agent, based on the total non-volatile weight of the latex copolymer. The aqueous coating composition may also include less than about 10 wt. %, or less than about 6 wt. %, or less than about 4 wt. % of the low VOC coalescing agent, based on the total non-volatile weight of the latex copolymer.

[0056] In some examples, the latex copolymers disclosed above can be formed and / or stabilized with one or more emulsifiers (e.g., surfactants) used alone or together. Examples of suitable nonionic emulsifiers include tert-octylphenoxyethyl poly (39)-ethoxyethanol, dodecyloxy poly (10) ethoxyethanol, nonylphenoxyethyl-poly (40) ethoxyethanol, polyethylene glycol 2000 monooleate, ethoxylated castor oil, fluorinated alkyl esters and alkoxylates, polyoxyethylene (20) sorbitan monolaurate, sucrose monococoate, di (2-butyl) phenoxy poly (20) ethoxyethanol, Hydroxyethylcellulose polybutyl acrylate graft copolymer, dimethyl silicone polyoxyalkylene graft copolymer, poly(ethylene oxide) poly(butyl acrylate) block copolymer, block copolymer 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 sulfide. Examples of suitable anionic emulsifiers include sodium lauryl sulfate, sodium dodecylbenzene sulfonate, potassium stearate, sodium dioctyl sulfosuccinate, sodium dodecyl diphenyl ether disulfonate, nonylphenoxyethyl poly (1) ethoxyethyl ammonium sulfate, sodium styrene sulfonate, sodium dodecyl allyl sulfosuccinate, linseed oil fatty acids, sodium, potassium or ammonium salts of phosphate esters of ethoxylated nonylphenol or tridecyl alcohol, sodium octylphenol polyether-3-sulfonate, sodium cocoyl sarcosinate, sodium 1-alkoxy-2-hydroxypropyl sulfonate, α-olefin (C 14 -C 16 ) sulfonate, hydroxyalkanol sulfate, tetrasodium N-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate, disodium N-octadecyl sulfosuccinate, disodium alkylamidopolyethoxysulfosuccinate, disodium ethoxylated nonylphenol half ester of sulfosuccinic acid, and sodium salt of tert-octylphenoxyethoxypoly (39) ethoxyethyl sulfate.

[0057] The aqueous coating composition of the present invention may include a rheological package comprising one or more thickeners or rheological modifiers to obtain a coating composition having suitable low, medium and high shear flow characteristics. Suitable rheological packages are described in U.S. published patent application 2020 / 0291249. Thickeners may include hydroxyethyl cellulose (HEC), xanthan gum, alginates, guar gum and other cellulose derivatives. Other rheological agents include aqueous clays; hydrophobically modified alkali swellable emulsions (HASE); or associative thickeners, such as hydrophobically enhanced urethanes (HEUR), polyether polyols (PEPO) or hydrophobically modified ethoxylated aminoplast thickeners (HEAT).

[0058] Waterborne clays include, for example, magnesium aluminum phyllosilicates such as attapulgite ((Mg,Al)2Si4O 10 (OH)·4(H2O)), hectorite (Na 0.3 (Mg,Li)3Si4O 10 (OH)2), organically modified hectorite, synthetic hectorite, etc. Examples of trade names 400 was purchased from Active Minerals International, LLC, Sparks, Maryland; and 40 and 50 was purchased from BASF SE, Ludwigshafen, Germany.

[0059] Exemplary HASE rheological agents include those sold under the trade name ACRYSOL TM TT-935 was purchased from Dow Chemical Company (Midland, Michigan); TR-116 is available from Arkema Inc., King, Prussia, Pennsylvania; TM 3800 was purchased from Arkema Inc. (King of Prussia, Pennsylvania); TM PP 102 was purchased from Arkema Inc. (King of Prussia, Pennsylvania); 1 Available from Elementis Specialties, Inc., East Windsor, New Jersey; sold under the trade name ACRYSOL TM ASE-60 is available from Dow Chemical Company (Midland, Michigan);TM TT-615 is available from Dow Chemical Company (Midland, Michigan); TM DR-300 was purchased from Dow Chemical Company (Midland, Michigan); TR-117 is available from Arkema Inc., King, Prussia, Pennsylvania; and ACRYSOL TM RM-5 was purchased from Dow Chemical Company (Midland, Michigan).

[0060] Exemplary associative thickeners include those sold under the trade name ACRYSOL TM RM-2020NPR was purchased from Dow Chemical Company (Midland, Michigan); TM SCT-275 is available from Dow Chemical Company (Midland, Michigan); TM RM-825 is available from Dow Chemical Company (Midland, Michigan); TM RM-8W was purchased from Dow Chemical Company (Midland, Michigan); TM RM-12W was purchased from Dow Chemical Company (Midland, Michigan); 350 was purchased from Elementis Specialties, Inc. (East Windsor, New Jersey); TM NHS-310 was purchased from Ashland, Inc. (Covington, Kentucky); TM NHS-350 was purchased from Ashland, Inc. (Covington, Kentucky); L100 was purchased from Byk GmbH, Wesel, Germany; H3300 VF was purchased from Byk GmbH, Wesel, Germany; and H370 was purchased from Byk GmbH, Wesel, Germany.

[0061] The aqueous coating composition may include a surfactant (e.g., a surfactant) as part of a rheological package, as part of an aqueous coating composition, or both. The surfactant may change the dispersion of the rheological package in the aqueous coating composition, change the interaction of the coating composition with the substrate or with a previously applied coating, or both. The surfactant affects the quality of the aqueous coating composition, including how to handle the aqueous coating composition, how to spread it on the surface of the substrate, and how to bond it to the substrate. The surfactant may change the ability of the aqueous coating composition to wet the substrate and may also be referred to as a wetting agent. The surfactant may also provide leveling, defoaming or flow control properties, etc. If the aqueous coating composition includes a surfactant, the surfactant is preferably present in an amount of less than 5% by weight based on the total weight of the aqueous coating composition. Surfactants suitable for use in coating compositions will be known to those of ordinary skill in the art, or may be determined using standard methods. Some suitable surfactants include those listed below: TM KK-95H, STRODEX TM PLF100, STRODEX TM PK0VOC、STRODEX TM LFK70、STRODEX TM SEK50D and DEXTROL TM OC50 is available from Dexter Chemical L.LC (Bronx, New York); TM 100. HYDROPALAT TM 140. HYDROPALAT TM 44. HYDROPALAT TM 5040 and HYDROPALAT TM 3204 was purchased from Cognis Corporation (Cincinnati, Ohio); TM A. DISPERS TM 660C, DISPERS TM 715W and DISPERS TM 750W was purchased from Degussa Corporation (Parsippany, New Jersey); BYK TM 156. BYK TM 2001 and ANTI-TERRA TM207 was purchased from BykChemie (Wallingford, Connecticut); TM A40, DISPEX TM N40, DISPEX TM R50, DISPEX TM G40、DISPEX TM GA40、EFKA TM 1500、EFKA TM 1501、EFKA TM 1502、EFKA TM 1503、EFKA TM 3034、EFKA TM 3522、EFKA TM 3580、EFKA TM 3772、EFKA TM 4500、EFKA TM 4510、EFKA TM 4520、EFKA TM 4530、EFKA TM 4540、EFKA TM 4550、EFKA TM 4560、EFKA TM 4570、EFKA TM 6220、EFKA TM 6225、EFKA TM 6230 and EFKA TM 6525 was purchased from Ciba Specialty Chemicals (Tarrytown, New York); TM CT-111, SURFYNOL TM CT-121, SURFYNOL TM CT-131, SURFYNOL TM CT-211, SURFYNOL TM CT231、SURFYNOL TM CT-136, SURFYNOL TM CT-151, SURFYNOL TM CT-171、SURFYNOL TM CT-234, CARBOWET TM DC-01, SURFYNOL TM 104. SURFYNOL TM PSA-336、SURFYNOL TM420、SURFYNOL TM 440、ENVIROGEM TM AD-01 and ENVIROGEM AE01 were purchased from Air Products & Chemicals, Inc. (Allentown, Pennsylvania); TM 1124、TAMOL 850、TAMOL 681、TAMOL TM 731 and TAMOL TM SG-1 was purchased from Rohm and Haas Co. (Philadelphia, Pennsylvania); TM CO-210、IGEPAL TM CO-430、IGEPAL TM CO-630、IGEPAL TM CO-730 and IGEPAL TM CO-890 was purchased from Rhodia Inc. (Cranbury, New Jersey); TM and T-MULZ TM Products are available from Harcros Chemicals Inc. (Kansas City, Kansas); polydimethylsiloxane surfactants (such as those sold under the trade name SILWET TM L-760 and SILWET TM L-7622 was purchased from OSI Specialties (South Charleston, West Virginia) or under the trade name BYK TM 306 available from Byk-Chemie) and fluorinated surfactants (such as those sold under the trade name FLUORAD TM FC-430 is commercially available from 3MCo. (St. Paul, Minnesota). Preferably, the surfactant does not contain alkylphenol ethoxylates (APEO). Preferably, the coating composition does not contain alkylphenol ethoxylates (APEO).

[0062] In some examples, the surfactant can be a defoamer. The aqueous coating composition can include a single surfactant or multiple surfactants, such as a first surfactant and a second defoamer. Some suitable defoamers include those sold under the trade name BYK TM 018. BYK TM 019. BYK TM 020, BYK TM 022. BYKTM 025. BYK TM 032. BYK TM 033. BYK TM 034. BYK TM 038. BYK TM 040, BYK TM 051. BYK TM 060, BYK TM 070, BYK TM 077 and BYK TM 500 sold by Byk Chemie; under the trade name SURFYNOL TM DF-695、SURFYNOL TM DF-75、SURFYNOL TM DF-62、SURFYNOL TM DF-40 and SURFYNOL TM DF-110D is sold by Air Products & Chemicals, Inc. under the trade name DEEFO TM 3010A、DEEFO TM 2020E / 50、DEEFO TM 215.DEEFO TM 806-102 and AGITAN TM 31BP is sold by Munzing Chemie GmbH (Heilbronn, Germany); EFKA 2526, EFKA 2527 and EFKA 2550 are sold by Ciba Specialty Chemicals; and FOAMAX TM 8050、FOAMAX TM 1488, FOAMAX TM 7447、FOAMAX TM 800、FOAMAX TM 1495 and FOAMAX 810 are sold by Degussa Corp.; under the trade name FOAMASTER TM 714. FOAMASTER TM A410, FOAMASTER TM 111. FOAMASTER TM 333. FOAMASTER TM 306. FOAMASTER TM SA-3, FOAMASTER TM AP, DEHYDRAN TM 1620, DEHYDRANTM 1923 and DEHYDRAN TM 671 is sold by Cognis Corp. Suitable defoamers include mineral oil or silicones.

[0063] The aqueous coating composition can also include one or more pigments, which provide both decorative and protective features for the paint. Pigments are solid particles used to provide various qualities for the paint, including but not limited to color, opacity and durability. Pigments and other solids can increase the volume of the paint and can affect the gloss or flatness of the paint. Some suitable pigments include titanium dioxide white, carbon black, lamp black, black iron oxide, red iron oxide, yellow iron oxide, brown iron oxide (a blend of red and yellow oxides and black), phthalocyanine green, phthalocyanine blue, organic red (such as naphthol red, quinacridone red and toluidine red), quinacridone magenta, quinacridone violet, DNA orange or organic yellow (such as Hansa yellow). Pigments can be added alone or as a part of a colorant or dye. The aqueous coating composition can also include a gloss control additive or an optical brightener, such as UVITEX TM OBs are those commercially available from Ciba-Geigy.

[0064] In some examples, the aqueous coating composition may include optional fillers or inert ingredients. The fillers or inert ingredients extend the aqueous coating composition, reduce the cost of the aqueous coating composition, change the appearance of the aqueous coating composition, or provide desired features for the aqueous coating composition before and after curing. Fillers and inert ingredients suitable for use in aqueous coating compositions will be known to those of ordinary skill in the art, or standard methods can be used to measure. Some suitable fillers or inert ingredients include, for example, clay, glass beads, calcium carbonate, talc, silica, feldspar, mica, barite, ceramic microspheres, calcium metasilicate, organic fillers, etc.

[0065] In certain applications, it may also be desirable to include a biocide in the aqueous coating composition that provides wet and / or dry film preservation. Suitable wet biocides are known in the art and include isothiazolinones such as 2-methyl-4-isothiazolin-3-one (MIT), 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), benzisothiazolinone (BIT), butylbenzisothiazolinone (BBIT), and dichlorooctylisothiazolinone (DCOIT), methyl-benzimidazol-2-yl carbamate, 3-iodo-2-propynyl-butyl carbamate (IPBC), propiconazole, zinc pyrithione, and zinc oxide. Some suitable biocides or fungicides include those sold under the trade name ROZONE TM 2000、BUSAN TM1292 and BUSAN 1440 are sold by Buckman Laboratories (Memphis, Tennessee); TM 663 and POLYPHASE TM 678 sold by Troy Chemical Corp. (Florham Park, New Jersey); and KATHON TM The LX is sold by Rohm and Haas Co.

[0066] The aqueous coating composition may also contain other ingredients that modify the properties of the aqueous coating composition when the aqueous coating composition is stored, handled or applied, and at other or subsequent stages. Waxes, matting agents, wear additives and other similar performance enhancing additives may be used as needed in amounts effective to improve the properties of the cured coating and aqueous coating composition. Some suitable wax emulsions for improving the physical properties of the coating include those sold under the trade name MICHEM TM Emulsions 32535, 21030, 61335, 80939M and 7173MOD are sold by Michelman, Inc. (Cincinnati, Ohio), and under the trade name CHEMCOR TM 20N35, 43A40, 950C25 and 10N30 are those sold by ChemCor (Chester, New York). Desirable performance characteristics of the coating include adhesion, chemical resistance, wear resistance, hardness, gloss, reflectivity, appearance, or a combination of these characteristics, and other similar characteristics. For example, the composition may include a wear-resistant promoting adjuvant such as silica or alumina (e.g., sol-gel treated alumina).

[0067] Other optional additives for use in the aqueous coating compositions herein are described in Kissuke et al., Paint and Coatings Industry, April 2003, pp. 12-86. Some performance enhancing additives that may be optionally used include coalescing solvents, dispersants, amines, preservatives, biocides, mildewcides, fungicides, glycols, other colorants or dyes, heat stabilizers, leveling agents, anti-cratering agents, cure indicators, plasticizers, fillers, precipitation inhibitors, UV absorbers, UV stabilizers, optical brighteners or other additives to modify the properties of the aqueous coating composition.

[0068] The aqueous coating composition can be used to coat a substrate, for example, as a primer, a topcoat, or a combination of a primer and a topcoat. For example, the aqueous coating composition can be used for building materials, including bricks, concrete, plaster, wood, gypsum board, etc. For another example, the aqueous coating composition can be used to coat other materials, such as metals or alloys used in automobiles or other machines, polymeric materials, etc.

[0069] The present disclosure will now be illustrated with reference to the following non-limiting examples.

[0070] Example

[0071] The present invention is illustrated by the following examples, which are provided for illustrative purposes and are not intended to limit the scope of the invention.

[0072] Example 1

[0073] One embodiment of the present invention was prepared by mixing the following components according to standard latex paint mixing techniques. This embodiment comprises the following components. The weight percentages listed are based on the total weight of the composition.

[0074] Table 1: Components of Example 1

[0075]

[0076] Example 2

[0077] One embodiment of the present invention was prepared by mixing the following components according to standard latex paint mixing techniques. This embodiment comprises the following components. The weight percentages listed are based on the total weight of the composition.

[0078] Table 2: Composition of Example 2

[0079] Example 3: Rheological properties

[0080] The Stormer (Krebs Units) viscosity of the composition of Example 1 was measured at room temperature (25°C) and cold temperature (25°F) and compared to two commercially available exterior acrylic latex paints.

[0081] Stormer (Krebs Unit) viscosity can be measured by the method in ASTM D562-10 entitled "Standard Test Method for Consistency of Paints Measuring Krebs Unit (KU) Viscosity Using a Stormer-Type Viscometer". The measurement is made when the temperature of the sample is 25 ± 0.2 ° C and when the temperature of the sample is first cooled to 25 ± 2 ° F (-3.9 ° C).

[0082] Table 2 shows the Krebs unit viscosities of the following compositions at room temperature (about 70°F): (1) Polar Paint commercially available from O'Leary Paint an exterior 100% acrylic latex coating composition advertised as suitable for application at temperatures as low as 20°F; and (2) commercially available from The Sherwin-Williams Company Exterior 100% acrylic latex; and (3) the composition of Example 1.

[0083] Table 3: Stormer viscosity (Krebs units)

[0084]

[0085] The data show that at room temperature, the examples of the present disclosure have relatively similar viscosities to conventional exterior acrylic latex coating compositions at room temperature. At 25°F, the examples of the present disclosure show comparable viscosities to Polar The compositions have similar rheological properties, whereas the conventional external acrylic latex viscosity is too high to be measured because it freezes prior to measurement.

[0086] Example 4: VOC content

[0087] Determine the Polar And the VOC content of the compositions of Examples 1 and 2 above. VOC was determined by ASTM D6886-14, using an Agilent GC 7890A gas chromatograph and a 7693 series autosampler / injector for duplicate analysis. The reported data is the average of the two tests, including VOC peaks > 50 ppm. The results are shown in Table 3 below:

[0088] Table 4: VOC content

[0089]

[0090] Example 5: Low temperature storage stability

[0091] The composition of Example 1 was prepared with extender particles replacing a relatively reduced amount of urea to evaluate the effect of including urea on freeze stability. The composition was cooled to 25°F and the time for the composition to reach bulk freeze was measured.

[0092] Table 5: Time to reach freezing

[0093] Mode Time to freeze Example 1 (2.0% urea) More than 6 weeks Example 1 with 1.5% urea Less than 24 hours Example 1 with 1.0% urea Less than 24 hours

[0094] Example 5: Heat Aging Stability

[0095] The composition of Example 1 was stored in a temperature controlled environmental chamber at room temperature and at 120° F. Samples were taken after two, five, and eight weeks of storage and a battery of tests were performed to evaluate whether the composition properties were maintained.

[0096]

[0097] Example 6: Surface Quality of Coating Composition Applied to Substrate

[0098] The composition of Example 1 and the composition of Example 2 and a conventional 100% acrylic exterior latex cooled to 25°F, applied to aluminum panels at 25°F by 5 mil drawdown (wet), and allowed to cure in a 25°F freezer. The cured coatings were then examined on a Keyence optical microscope using reflected illumination at 200x magnification. Images are shown in Figures 2A, Figure 2B , as shown in Figure 2C and Figure 2D.

[0099] The conventional all-acrylic latex coating compositions shown in FIGS. 2C and 2D exhibit frosting (the appearance of ice crystals on the coated film), whereas the coatings of the present disclosure ( FIGS. 2A and 2D ) do not. ( Figure 2B ) showed no frosting or otherwise showed cracking of the coating.

[0100] Example 7: Spraying in Low Temperature Field Test

[0101] Comparison of low temperature application of Polar described in Example 1 and Example 3 Choose Polar As a comparison, this is because it is advertised as being able to be applied at temperatures below the freezing point. The tested compositions were cooled and the temperature was allowed to equilibrate at about 40°F. The compositions were applied outdoors at an air temperature of about 25°F. The compositions were applied to T-111 exterior grade plywood and cementitious laminate using (a) a Graco GX-19 airless sprayer with a .5 17 tip, (b) by brush, and (c) by roller.

[0102] Using each of the three application techniques, apply Polar The compositions of Example 3 were successfully applied to the T-111 substrate. When The compositions of Example 3 and Polar all showed a "net-like" appearance, where the coverage was uneven. Overall, the compositions of Example 3 and Polar Performance was relatively the same in terms of application ability.

[0103] Example 8: Spraying at low temperature

[0104] In a separate app, Polar The samples were then removed and sprayed onto the cementitious base using a Graco GX-19 airless sprayer with a .5 17 tip. The painted substrate was immediately placed in a 25°F temperature controlled cabinet to dry for 1 day.

[0105] Found that at 25°F, it was impossible to spray Polar due to clogging and splattering of the sprayer. However, CGM-026 was able to be sprayed without clogging, splattering, or other signs of application defects.

[0106] Example 9: Outdoor exposure test

[0107] The Polar The compositions of and Example 3 were applied in duplicate to the following substrates by brushing and allowed to cure for one day.

[0108] (1) Cement-based Primer Concrete and masonry primer / sealer, purchased from The Sherwin-Williams Company;

[0109] (2) T-111 exterior grade plywood primed with an exterior oil-based wood primer, available from The Sherwin-Williams Company;

[0110] (3) Unpretreated or unprimed VTW vinyl siding (applied with two coats of Polar or the composition of Example 3);

[0111] (4) cedar rough siding primed with an exterior oil-based wood primer, purchased from The Sherwin-Williams Company;

[0112] After application and curing, the coated substrate was exposed to the weather elements beginning in mid-winter at a Midwestern location in the United States with cold, snowy winters and hot summers. Exposure to the elements in a Midwestern state with cold, snowy winters and hot summers began in February.

[0113] The samples were graded every three months for general appearance, frosting, cracking, flaking, mold or algae growth, blistering, staining, and 60°C gloss. The composition of Example 3 showed similar The coated substrate has the same or better characteristics.

Claims

1. A low-temperature aqueous coating composition, comprising: an aqueous carrier fluid; polymer binders; a diol or polyol having a first conventional vapor pressure of less than 0.2 mm Hg; and a monohydric alcohol having a second conventional vapor pressure; as well as Compounds having urea functionality; wherein the first conventional vapor pressure is less than the second conventional vapor pressure; and wherein the aqueous coating composition has a VOC of less than 250 g / L.

2. An additive package suitable for addition to an aqueous coating composition, the additive package suitable for addition to an aqueous coating composition comprising: a diol or polyol having a first conventional vapor pressure of less than 0.2 mm Hg; and a monohydric alcohol having a second conventional vapor pressure; and Compounds having urea functionality; Wherein the first conventional vapor pressure is less than the second conventional vapor pressure.

3. A method for preparing a low-temperature aqueous coating composition, the method for preparing a low-temperature aqueous coating composition comprising: adding a diol or polyol having a first conventional vapor pressure of less than 0.2 mm Hg to the polymer binder; as well as adding a monohydric alcohol having a second conventional vapor pressure to the polymer binder; as well as adding a compound having urea functionality to the polymer binder; Wherein the first conventional vapor pressure is less than the second conventional vapor pressure.

4. A method for preparing a low-temperature aqueous coating composition, the method for preparing a low-temperature aqueous coating composition comprising: The additive package according to claim 2 is added to the polymeric binder.

5. A coating composition, package or method according to any one of claims 1 to 4, wherein said second conventional vapor pressure is at least 0.4 mm Hg.

6. A coating composition, package or method according to any one of claims 1 to 5, wherein the difference between the second conventional vapor pressure and the first conventional vapor pressure is at least 0.25 mm Hg.

7. A coating composition, package or method according to any one of claims 1 to 6, The monohydric alcohol is a straight-chain or branched C1 to C4 alcohol.

8. A coating composition, package or method according to any one of claims 1 to 7, The monohydric alcohol is ethanol.

9. A coating composition, package or method according to any one of claims 1 to 8, The monohydric alcohol is 1-butanol.

10. A coating composition, package or method according to any one of claims 1 to 9, wherein the composition comprises the diol.

11. A coating composition, package or method according to any one of claims 1 to 10, The diol is a C1 to C6 diol.

12. A coating composition, package or method according to any one of claims 1 to 11, The diol is ethylene glycol.

13. A coating composition, package or method according to any one of claims 1 to 11, The diol is propylene glycol.

14. A coating composition, package or method according to any one of claims 1 to 13, Wherein the composition or additive package comprises a polyol, the polyol is ordinary sugar.

15. A coating composition, package or method according to any one of claims 1 to 14, Wherein the common sugar is selected from the group consisting of mannitol or sorbitol or glucose or a combination thereof.

16. The coating composition, package or method of any one of claims 1 to 15, wherein the compound having urea functionality comprises urea in an amount of at least 1.75 wt. % based on the total weight of the aqueous coating composition.

17. The coating composition, package or method of any one of claims 1 to 16, wherein the diol or polyol is selected from the group consisting of ethylene glycol, propylene glycol, pentaerythritol, sucrose, fructose and mixtures thereof.

18. The coating composition, package or method of any one of claims 1 to 17, wherein the diol or polyol is present in an amount of at least about 1.0 wt. %, preferably at least about 1.25 wt. %, or preferably at least about 1.5 wt. %, based on the total weight of the aqueous coating composition.

19. The coating composition, package or method of any one of claims 1 to 18, wherein the monohydric alcohol is present in an amount of up to about 2.5 wt %, preferably up to about 2.25 wt % or preferably up to 2.0 wt %, based on the total weight of the aqueous coating composition.

20. The coating composition, package or method of any one of claims 1 to 19, wherein the monohydric alcohol is present in an amount of at least 1.0 wt%, preferably at least 1.25 wt% or preferably at least 1.5 wt%, based on the total weight of the aqueous coating composition.

21. A coating composition, package or method according to any one of claims 1 to 20, The coating composition has a VOC of less than 150 g / L.

22. A coating composition, package or method according to any one of claims 1 to 21, The coating composition has a VOC of less than 100 g / L.

23. A coating composition, package or method according to any one of claims 1 to 22, The coating composition has a VOC of less than 50 g / L.

24. The coating composition according to any one of claims 1 to 23, The coating composition does not contain alkylphenol polyoxyethylene ether.

25. The coating composition according to any one of claims 1 to 24, The coating composition may further comprise a pigment, a colorant, a dispersant, a fungicide, a UV stabilizer, a wetting agent, a surfactant, a filler or a coalescing agent, or a combination thereof.

26. The coating composition according to any one of claims 1 to 25, wherein the composition comprises a pigment.

27. The coating composition according to any one of claims 1 to 26, A defoamer and the surfactant are present therein.

28. The coating composition according to claim 27, The defoaming agent comprises mineral oil.

29. The coating composition according to claim 27, The defoaming agent comprises silicone.

30. The coating composition according to claim 25, The surfactant comprises a phosphate ester.

31. The coating composition according to any one of claims 1 to 30, The surfactant does not include an alkylphenol polyoxyethylene ether structural unit.

32. The coating composition according to any one of claims 1 to 31, The polymer binder includes at least one of (meth)acrylic latex, vinyl acrylic latex or styrene acrylic latex.

33. The coating composition according to claim 32, The at least one of the (meth)acrylic latex, the vinyl acrylic latex or the styrene acrylic latex is formed of seed particles.

34. A coating composition according to any one of claims 1 to 31, The polymer binder comprises polyurethane.

35. The coating composition of any one of claims 1 to 34, wherein the aqueous coating exhibits no bulk freezing when stored in a freezer at a temperature between 21 degrees Fahrenheit and 26 degrees Fahrenheit for 24 hours.

36. An article, comprising: substrate; and a coating on said substrate; The coating comprises at least one layer formed from the low-temperature aqueous coating composition according to any preceding claim.

37. A method for preparing a coated substrate, the method for preparing a coated substrate comprising: A coating is applied to a substrate, wherein the coating is formed from the low temperature aqueous coating composition according to any one of claims 1 to 35.

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