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WO2025147405A1 - Polyalkylèneglycols fonctionnalisés par acétoacétoxy et utilisations correspondantes - Google Patents

Polyalkylèneglycols fonctionnalisés par acétoacétoxy et utilisations correspondantes Download PDF

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Publication number
WO2025147405A1
WO2025147405A1 PCT/US2024/061333 US2024061333W WO2025147405A1 WO 2025147405 A1 WO2025147405 A1 WO 2025147405A1 US 2024061333 W US2024061333 W US 2024061333W WO 2025147405 A1 WO2025147405 A1 WO 2025147405A1
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WIPO (PCT)
Prior art keywords
coating composition
composition
crosslinking agent
base coating
water
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PCT/US2024/061333
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English (en)
Inventor
Jacob S. Donlon
Gamini S. Samaranayake
Terry D. JORDAN
Maddi M. BHAT KASHI
Xiaodong Shi
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Swimc LLC
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Swimc LLC
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Publication of WO2025147405A1 publication Critical patent/WO2025147405A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/716—Esters of keto-carboxylic acids or aldehydo-carboxylic acids
    • C07C69/72—Acetoacetic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides

Definitions

  • the present disclosure relates to a crosslinking agent formed from a polyalkylene glycol functionalized with at least one acetoacetoxy (AcAc) group, and its use in colorant compositions, paint or stain compositions, or coating compositions.
  • a crosslinking agent formed from a polyalkylene glycol functionalized with at least one acetoacetoxy (AcAc) group, and its use in colorant compositions, paint or stain compositions, or coating compositions.
  • Latex paints and coatings are often used to protect a surface from corrosion, oxidation or other types of deterioration and to provide decorative effects.
  • Water-borne, or latex paints and coatings typically include a film-forming latex binder, water, pigment and other additives.
  • Latex paints and coatings are popular consumer paints, as they are easy to apply, are usually easy to clean up, nonflammable, generally lack a disagreeable odor and can be used on both interior and exterior surfaces.
  • Latex paints and coatings can be tinted during manufacturing or at the point of sale using a colorant, which is a suspension of one or more pigments in a carrier, together with one or more additives to stably disperse the pigment in the paint or coating.
  • PEG in water-borne colorants, PEG can provide humectant and anti-freeze properties.
  • Water-borne colorants are typically added at the point-of-sale via a tinter machine.
  • a tinter adds one or more colorants from an array of usually 8 to 12 colorants, each colorant having a distinct combination of pigments. Between uses of the tinter, it is possible that remaining amounts of colorant in the machine may dry. Commonly occurring at the tip of the tinter, this phenomena is known as “tip dry,” and can result in clogging of the tinter or, if the resulting dried colorant releases, undesirable addition of agglomerated pigment into a base paint or coating.
  • (meth)acrylic acid includes either or both of acrylic acid and methacrylic acid
  • (meth)acrylate includes either or both of an acrylate and a methacrylate.
  • free of is used herein, such phrases are not intended to preclude the presence of trace amounts of the pertinent structure or compound which may be present but were not intentionally used, e.g., due to the presence of environmental contaminants.
  • compositions that comprises ‘a’ component can be interpreted to mean that the composition includes ‘one or more’ of that class of component.
  • the term 'or' is generally employed in its usual sense including “and/or unless the content clearly dictates otherwise.
  • the term “and/or” means one or all of the listed elements or a combination of any two or more of the listed elements.
  • the present invention relates to a crosslinking agent for use in a colorant composition, paint composition, stain composition, or coating composition
  • a crosslinking agent for use in a colorant composition, paint composition, stain composition, or coating composition
  • a polyalkylene glycol including at least one acetoacetoxy group wherein the polyalkylene glycol is composed of alkyloxy groups obtained from interpolymerized ethylene oxide groups, interpolymerized propylene oxide groups, or combinations thereof.
  • the polyalkylene glycol is endcapped on at least one end by one or more acetoacetoxy groups.
  • the polyalkylene glycol is endcapped on both ends by acetoacetoxy groups.
  • the crosslinking agent of the present disclosure can be prepared by any desired method.
  • One method for preparing the crosslinking agent comprises transesterifying an acetoacetoxy ester with the polyalkylene glycol. This provides an end-capped, reactive polyalkylene glycol, which can be mono- or di -functional, depending on the synthesis conditions and ratios of reactants used.
  • the acetoacetoxy ester used can be any ester, including, but not limited to, methyl-acetoacetate, ethyl -acetoacetate, propyl-acetoacetate, butyl-acetoacetate (n-butyl, s-butyl, or t-butyl esters), etc.
  • the resulting acetoacetoxy functional polyalkylene glycol has reactive functionality. Without being bound by theory, it is believed that the acetoacetoxy groups can react by UV- catalyzed oxidative crosslinking with unsaturated fatty acids and Michael addition reactions with aldehydes to crosslinking acetoacetate groups into the polymer matrix during coalescence of a base paint or stain. In addition, acetoacetoxy-containing molecules readily react with amines and hydrazides to create crosslinked matrices. Such cross-linking into the polymer matrix of an applied coating avoids migration of the polyalkylene glycol to the surface of a dried coating film. The resultant coating film displays an improvement in durability and integrity in terms of increased film hardness, decreased block and tack, decreased dirt pick up in exterior applications, and a decrease in surfactant leaching, compared to coating films comprising traditional polyalkylene glycols.
  • the resulting crosslinking agent can be used as (i) a reactive humectant in colorants, particularly water-borne colorants; (ii) a reactive coalescent in paints and coatings, particularly water-borne paints and coatings; and (iii) a reactive float in paints and coatings, particularly water-borne paints and coatings; and (iv) as a non-lapping additive in wood stains.
  • Colorants containing the crosslinking agent are particularly suitable for use as colorants for point-of-sale tinting of architectural water-borne and solvent-borne paints and stains.
  • the paints and stains containing the crosslinking agent as a coalescent, float, or nonlapping additive are particularly useful as architectural water-borne paints and stains.
  • the crosslinking agent has a mole ratio of acetoacetoxy groups to alkyloxy groups of from 1 :4 to 1 : 10, preferably 1 :4 to 1 :8, more preferably 1 :5 to 1 :7.
  • the polyalkylene glycol is a polyethylene glycol and has a Mw of 400-1000. In other preferred embodiments of the present disclosure crosslinking agent, the polyalkylene glycol is a polypropylene glycol and has a Mw of 500-2000.
  • the crosslinking agent of the present disclosure is preferably configured to be added to a colorant composition or a coating composition, or added directly or indirectly to a surface of a base coating composition, for example as an anti-skinning agent in a container of the base coating composition, for example as part of an anti-skinning layer in a container of the base coating composition.
  • the crosslinking additive can be configured to be added to a water-based stain composition as an anti-lapping additive.
  • the crosslinking agent of the present disclosure can be used in a variety of uses in the paint and coatings industry, including, but not limited to, as a reactive humectant in a colorant composition, as a reactive float in an anti-skinning layer in a container containing a base coating composition, and as a reactive coalescent in a paint or coating.
  • the present disclosure relates to a colorant composition
  • a colorant composition comprising an aqueous carrier, one or more pigments or dyes and the crosslinking agent of the present disclosure in an amount of 5 wt.% to 20 wt.% of the total components of the colorant composition.
  • the crosslinking agent may be present in an amount of at least 10 or at least 15 wt.% and/or less than 17 wt.% or less than 12 wt.% of the total components of the colorant composition.
  • Colorant compositions of the present disclosure do not form a film when applied to a substrate and cured and thus, if any polymeric binder is present in the colorant composition, the binder is present in less than a film-forming amount.
  • the amount of binder necessary to form a film varies by colorant, in some aspects, the colorant compositions will have less than 10 wt.%, less than 5 wt.%, less than 2 wt.%, less than 1 wt.%, or less than 0.5 wt.% of a binder contained therein.
  • the colorant composition may include no intentionally added polymeric binder.
  • the polymeric binder may be any polymeric binder used in an architectural paint or stain as disclosed herein.
  • the system can accordingly be used with just the water-only colorants when it is desired to tint a water-borne paint or stain, and can be used with such colorants together with an appropriate amount of the synergist when it is desired to tint a solvent-borne paint or stain.
  • the ingredients e.g., surfactants, siccatives, optional dispersing agents and optional cosolvents
  • the ingredients e.g., surfactants, siccatives, optional dispersing agents and optional cosolvents
  • the pigment or dye used can be any conventional pigment or dye used in the paint or coating industry.
  • the pigment is a member selected from the group consisting of titanium dioxide white, carbon black, lampblack, black iron oxide, red iron oxide, transparent red oxide, yellow iron oxide, transparent yellow oxide, brown iron oxide (a blend of red and yellow oxide with black), umber, phthalocyanine green, phthalocyanine blue, organic reds (including, but not limited to, naphthol red, quinacridone red and toluidine red), DPP red, quinacridone magenta, quinacridone violet, carbazole violet, DNA orange, DPP orange, organic yellows (such as monoazo yellow), bismuth vanadate yellow, and combinations thereof.
  • the colorant composition may include further additives such as one or more preservatives, humectants, biocides, fillers, defoamers, pH control agents, thickeners, anti-settling agents, and mixtures or combinations thereof, as disclosed in U.S. Published Patent Application US 2017/0174924 Al, which is incorporated by reference.
  • the colorant composition is configured such that it has less than 50 g/L VOC, preferably less than 30 g/L VOC, more preferably less than 10 g/L VOC, still more preferably less than 5 g/L VOC, and most preferably essentially zero VOC.
  • the present disclosure relates to a system for reducing skinning of a base coating composition in a container, the base coating composition including at least a film-forming polymeric binder, an aqueous carrier, a pigment, and one or more coating additives; and disposed on a top surface of the base coating composition in the container, an anti-skinning layer comprising the present disclosure crosslinking agent.
  • Water-based coating compositions such as paints are often distributed in cans, pails, vats, or other closed containers.
  • water may evaporate and condense on the sides or top of the container due to a temperature differential between the container, the coating composition therein, and headspace within the container.
  • This temperature differential can result in skinning— the generation of a polymeric skin on the surface of the wet-state coating composition.
  • a skin may grow to as much as 1/2 cm in depth or more, and may splash or stick to the lid or sides of the distribution container and thereafter become mixed with the fluid coating composition.
  • Skinning is undesirable for multiple reasons.
  • agglomeration from skins can cause spray application equipment to clog or may appear as non-uniform bumps on a surface coated with the coating composition.
  • spray application equipment Typically appearing as either dried coating composition or globules in the coating composition, skins also may be perceived adversely by customers expecting a fully uniform coating composition upon opening the container.
  • a float layer on top of a coating composition, such as water, a polyalkylene glycol such as ethylene glycol, propylene glycol, diethylene glycol or combinations thereof, polyethylene glycol, or glycerin, or a mix of the foregoing with water and surfactant.
  • a water-only float layer may be adequate in some circumstances, a water-only float is insufficient to prevent in-container skinning for all coating compositions.
  • a float that includes a polyalkylene glycol can be useful towards reducing skinning that occurs during product distribution.
  • polyalkylene glycols tend to resist evaporation of the base coating composition into the container headspace and thereby thwart the evaporation/condensation cycle believed to contribute to skinning during distribution and storage.
  • the float prior to use/application by an end-user, the float is mixed with the base coating composition, and as a result, any polyalkylene glycols used as a float can impact the coalescence of the coating composition when applied or otherwise make the coating softer and less resistant to wear.
  • crosslinking agent of the present disclosure may provide the same or improved resistance to skinning during distribution and storage.
  • crosslinking agent of the present disclosure when utilized as a float component, upon mixture into the base coating composition, crosslinking of the polyalkylene glycol with the polymeric binder can provide improved coalescence, anti-blocking, and other properties in the cured coating.
  • the anti-skinning layer of the present invention includes a alkylene glycol, such as a ethylene glycol, propylene glycol, or glycerin, with or without water, and also the crosslinking agent of the present disclosure.
  • the crosslinking agent of the present disclosure may be at least 0.1, 0.5, 1, 2, 5, 10, 25, 50, or more wt.% of the anti-skinning layer.
  • the anti-skinning layer is preferably present in an amount of from at least 1 mL/gallon container, more preferably at least 10 mL/gallon container, still more preferably at least 20 mL/gallon container, and most preferably at least 40 mL/gallon container, to at most 500 mL/gallon container, more preferably at most 70 mL/gallon container, most preferably at most 50 mL/gallon container.
  • the anti-skinning layer may be composed of at least 10 wt.%, at least 20 wt.%, at least 30 wt.%, at least 50 wt.% or at least 75 wt.% of the crosslinking agent of the present disclosure.
  • Other components of the anti-skinning layer may include water, an alkylene glycol such as ethylene glycol or propylene glycol, diethylene glycol, a polyethylene glycol, glyercin, or combinations thereof.
  • the crosslinking agent of the present disclosure is useful in association with a base coating composition.
  • the crosslinking agent may be used in a colorant composition as disclosed herein to tint a base coating composition.
  • the crosslinking agent may be used as an anti-skinning layer as part of an anti-skinning system for a base coating composition.
  • the crosslinking agent may be used as an additive in a base coating composition.
  • the crosslinking agent as disclosed herein may optionally be added as an additive to the base coating composition.
  • the crosslinking agent may be present in an amount of at least 0.1, 0.5, 1.0, 1.5, or 2 wt.% based on the total components of the base coating composition and/or at most 5, 4, 3, 2, or 1 wt.% based on the total components of the base coating composition.
  • crosslinking agent of the present disclosure provides for improved low temperature coalescence, reduced anti -blocking, and durability of coatings resulting from coating compositions that include the crosslinking agent of the present disclosure.
  • the film-forming polymeric binder may include any suitable polymer.
  • the polymeric binder Prior to addition to a coating composition, may have the form of a latex, may be dispersed in the carrier liquid (e.g., in an emulsion stabilized colloidally or using a surfactant), or present as a solute in the carrier liquid (e.g., in a solution polymer).
  • the polymeric binder may be a water-borne polyurethane dispersion, or a (meth)acrylate, acetate (e.g., ethyl ene-vinyl acetate), styrene-acrylic, or vinyl acrylic latex.
  • a latex polymer 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, methylol (meth)acrylamide, styrene, a-methyl styrene, vinyl toluene, vinyl acetate, vinyl propionate, allyl meth
  • the reactants that form the polymeric binder also include an ethylenically unsaturated polar component.
  • the ethylenically unsaturated polar component may include an ethylenically unsaturated monomer including at least one alcohol group, an ethylenically unsaturated ionic monomer, an at least partially neutralized ethylenically unsaturated ionic monomer, or the like.
  • the at least partially neutralized ethylenically unsaturated ionic monomer may be a salt form of the ethylenically unsaturated ionic monomer, and the salt form may be formed prior to, during, or after reaction of the ethylenically unsaturated ionic monomer with the other monomers in the reactants to form the latex copolymer.
  • 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.
  • the ethylenically unsaturated polar monomer may include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, 2-methyl maleic acid, itaconic acid, 2-methyl itaconic acid, anhydride variants thereof, at least partially neutralized variants thereof, or combinations thereof.
  • the polymeric binder may be comprised of a polyurethane dispersion, or a urethane-modified acrylic polymer dispersion.
  • the carrier is aqueous. That is, more than 50% of the carrier is aqueous such that the base coating composition is a water-borne coating composition.
  • the base coating compositions of the present disclosure may also optionally include one or more opacifying pigments.
  • One or more pigments may be incorporated separately as a particle, in a slurry, or as a particle-polymer complex.
  • the pigment is titanium dioxide, which may comprise anatase titanium dioxide, rutile titanium dioxide, Brookite titanium dioxide, or mixtures thereof with or without other pigments.
  • the rutile titanium dioxide is surface treated with an inorganic oxide, such as silica (SiO2), alumina, zirconia, or combinations thereof.
  • iron oxide may be used as a pigment.
  • the opacifying pigments such as titanium dioxide
  • exemplary commercially available titanium dioxide particles and those provided in slurry or dry forms e.g., KRONOSTM 1071, 2020, 2044, 2090, 2101, 2102, 2131, 2160, 2210, 2310, 4102, 4310 and 4311 from Kronos, Inc., TIONATM 595 and.596i from Millennium Specialty Chemicals Inc. TIPURETM TS- 6200, R-706, R-741, R-746, R-900, R-902+, R 931 and R-960 from E.
  • the base coating compositions disclosed herein may include about 10 to about 30 weight percent of pigment, about 15 to about 20 weight percent, or about 18 to about 25 weight percent of pigment based on the toal amount of components in the coating composition.
  • the waterborne coating compositions herein may include a pigment present in an amount of about 3 to about 60 PVC, preferably about 10 to about 50 PVC, and more preferably, about 20 to about 45 PVC. The amount of pigment may vary depending on the application.
  • the PVC of architectural exterior coatings may be about 10 to about 50
  • the PVC of masonary coatings may be about 10 to about 40
  • the PVC of a water-based metal coating may be about 10 to about 40
  • the PVC of stains may be about 10 to about 40
  • extra while formulations may contains more PVC, such as about 20 to about 45.
  • the base coating composition may include one or more additives such as coalescents, rheology modifiers, surface active-agent, fillers, extenders, biocides, and UV stabilizers, in amounts and concentrations known to those skilled in the art.
  • additives such as coalescents, rheology modifiers, surface active-agent, fillers, extenders, biocides, and UV stabilizers, in amounts and concentrations known to those skilled in the art.
  • all additives and the latex binder of the coating composition are selected such that the coating composition will have less than 150 g/L VOC, preferably less than 100 g/L VOC, and even more preferably less than 50 g/L VOC.
  • One or more optional coalescents can optionally be used to facilitate film formation.
  • Coalescents suitable for use in the aqueous coating compositions will be known to persons having ordinary skill in the art or can be determined using standard methods.
  • Exemplary coalescents include glycol ethers such those sold under the trade names as EastmanTM EP, EastmanTM DM, EastmanTM DE, EastmanTM DP, EastmanTM DB and EastmanTM PM from Eastman Chemical Company, Kingsport, Tennessee, and ester alcohols such as those sold under the trade names TexanolTM ester alcohol from Eastman Chemical Company.
  • the optional coalescent may be a low VOC coalescent such as is described in U.S. Pat. No. 6,762,230 B2.
  • the base coating composition may include one or more surfactants or emulsifiers.
  • suitable nonionic emulsifiers include tert-octylphenoxy ethylpoly (39)- ethoxyethanol, dodecyloxypoly(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) phenoxypoly(20)ethoxy ethanol, hydroxyethylcellulosepolybutyl acrylate graft copolymer, dimethyl silicone polyalkylene oxide graft copolymer, polyethylene oxide)poly(butyl acrylate) block copolymer, block copolymers of propylene oxide and ethylene oxide, 2,4,7
  • anionic emulsifiers include sodium lauryl sulfate, sodium dodecylbenzenesulfonate, potassium stearate, sodium dioctyl sulfosuccinate, sodium dodecyldiphenyloxide disulfonate, nonylphenoxyethylpoly(l)ethoxy ethyl 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 l-alkoxy-2-hydroxypropyl sulfonate, sodium alpha-olefin (C14-C16)sulfonate
  • Suitable rheology modifiers 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 rheology agents include waterborne clay; a hydrophobically modified alkali-swellable emulsion (HASE); or an associative thickener such as a hydrophobically enhanced urethane (HEUR), a polyether polyol (PEPO), or a hydrophobically modified ethoxylated aminoplast thickener (HEAT).
  • HASE hydrophobically modified alkali-swellable emulsion
  • HEAT hydrophobically enhanced urethane
  • PEPO polyether polyol
  • HEAT hydrophobically modified ethoxylated aminoplast thickener
  • rheology modifiers include waterborne clays include, for example, a magnesium aluminum phyllosilicate such as attapulgite ((Mg,Al)2Si40io(OH) 4(H2O)), hectorite (Nao.3(Mg,Li)3Si40io(OH)2), an organically modified hectorite, a synthetic hectorite, or the like. Examples are available under the trade designations MIN-U-GEL® 400 from Active Minerals International, LLC, Sparks, Maryland; and ATTAGEL® 40 and ATTAGEL® 50 from BASF SE, Ludwigshafen, Germany.
  • a magnesium aluminum phyllosilicate such as attapulgite ((Mg,Al)2Si40io(OH) 4(H2O)
  • hectorite Nao.3(Mg,Li)3Si40io(OH)2
  • organically modified hectorite a synthetic hectorite, or
  • Example HASE rheology modifiers include those available under the trade designations Aery solTM TT-935 from Dow Chemical Company, Midland, Michigan; POLYPHOBE® TR-116 from Arkema Inc., King of Prussia, Pennsylvania; RheotechTM 3800 from Arkema Inc., King of Prussia, Pennsylvania; PolyphobeTM PP 102 from Arkema Inc., King of Prussia, Pennsylvania; Rheolate® 1 from Elementis Specialties, Inc., East Windsor, New Jersey; ACRYSOLTM ASE-60 from Dow Chemical Company, Midland, Michigan; ACRYSOLTM TT-615, from Dow Chemical Company, Midland, Michigan; AcrysolTM DR- 300, from Dow Chemical Company, Midland, Michigan; PolyphobeTM TR-117 from Arkema Inc., King of Prussia, Pennsylvania; and AcrysolTM RM-5 from Dow Chemical Company, Midland, Michigan.
  • the rheology modifier may be an associative thickener.
  • Example associative thickeners include those available under the trade designations AcrysolTM RM-2020 NPR from Dow Chemical Company, Midland, Michigan; AcrysolTM SCT-275 from Dow Chemical Company, Midland, Michigan; AcrysolTM RM-825 from Dow Chemical Company, Midland, Michigan; AcrysolTM RM-8W from Dow Chemical Company, Midland, Michigan; AcrysolTM RM-12W from Dow Chemical Company, Midland, Michigan; RHEOLATE® 350 from Elementis Specialties, Inc., East Windsor, New Jersey; AcrysolTM NHS-310 from Ashland, Inc., Covington, Kentucky; AquaflowTM NHS-350 from Ashland, Inc., Covington, Kentucky; Optiflo® L100 from Byk GmbH, Wesel, Germany; Optiflo® H3300 VF from Byk GmbH, Wesel, Germany; and Optiflo® H370 from Byk GmbH, Wesel, Germany.
  • a surface-active agent may also be present as part of the base coating composition.
  • the surface-active agent may modify affect dispersion of the rheology agent in the aqueous coating composition, modify the interaction of the coating composition with the substrate or with a prior applied coating, or both.
  • the surface-active agent affects qualities of the aqueous coating composition including how the aqueous coating composition is handled, how it spreads across the surface of the substrate, and how it bonds to the substrate.
  • the surface-active agent can modify the ability of the aqueous coating composition to wet a substrate and also may be referred to as a wetting agent.
  • Surface-active agents may also provide leveling, defoaming, or flow control properties, and the like.
  • the surface-active agent may be a defoamer.
  • the aqueous coating composition may include a single surface-active agent, or multiple surface-active agents, e.g., a first surface-active agent and a second defoamer.
  • the aqueous coating composition may include an optional filler or inert ingredient.
  • Fillers or inert ingredients extend, lower the cost of, alter the appearance of, or provide desirable characteristics to the aqueous coating composition before and after curing.
  • Fillers and inert ingredients suitable for use in the aqueous coating composition will be known to persons having ordinary skill in the art or can be determined using standard methods.
  • Some suitable fillers or inert ingredients include, for example, clay, glass beads, calcium carbonate, talc, silicas, feldspar, mica, barytes, ceramic microspheres, calcium metasilicates, organic fillers, and the like.
  • UV stabilizers may include encapsulated hydroxyphenyl -tri azine compositions and other compounds known to persons having ordinary skill in the art, for example, TinuvinTM 477DW, commercially available from BASF Corporation.
  • Desirable performance characteristics of the coating include chemical resistance, abrasion resistance, hardness, gloss, reflectivity, appearance, or combinations of these characteristics, and other similar characteristics.
  • the composition may include abrasion resistance promoting adjuvants such as silica or aluminum oxide (e.g., sol gel processed aluminum oxide).
  • the base coating composition before or after tinting with a colorant composition, may be used to coat substrates, e.g., as a primer coat, a topcoat, or a combination primer coat and topcoat.
  • the tinted coating composition may be used to coat architectural materials, including brick, concrete, stucco, wood, gypsum board, drywall, Hardieboard, and the like.
  • the tinted coating composition may be used to coat other materials, such as metals or alloys used in automobiles or other machines, polymeric materials, or the like.
  • the tinted coating composition may be applied by any suitable method, including roller, brush, or air spray.
  • the tinted coating composition may be cured by allowing the coating composition to dry under ambient condi ctions, or by application of heat, UV, or chemical crosslinking.
  • the base coating composition of these tinted coated compositions have a VOC level of 250 g/L or less, 150 g/L of less, 100 g/L or less, 50 g/L or less, 25 g/L or less, 10 g/L or less, 5 g/L or less, or in certain embodiments essentially zero VOC.
  • the base coating composition is essentially free of an alkyl phenol ethoxylate.
  • the base coating composition can contain benzophenone, or can be essentially free of benzophenone, depending on the desired end use.
  • the present disclosure further relates to a coated substrate which has been coated using a base coating composition that includes the crosslinking agent disclosed herein; or the system for reducing skinning described above, after the based coating composition and antiskinning layer have been thoroughly and uniformly mixed; or a tinted coating composition of the present disclosure consisting of a base coating composition tinted with a colorant composition comprising the crosslinking agent disclosed herein, as described above.
  • Such a coated substrate of embodiments of the present disclosure comprises a substrate, having applied to at least a surface thereof either (i) a coating formed from the system for reducing skinning after it has been uniformly mixed, or (ii) a coating formed from the tinted coating composition, or (iii) a base coating composition that includes the crosslinking agent as disclosed herein. Once the coating has been applied to the surface of the substrate, the applied coating is cured to yield a cured coating.
  • the curing can be performed by any conventional method for curing of such coating compositions, and is preferably performed for 12 hours, more preferably for 18 hours, most preferably for 24 hours at room temperature.
  • the cured coating comprises a crosslinked matrix of chemical bonds formed via the acetoacetoxy groups present in the composition.
  • the chemical bonds can be (i) via the acetoacetoxy groups present in the crosslinking agent itself, (ii) via both the acetoacetoxy groups present in the crosslinking agent and acetoacetoxy groups polymerized in the polymeric latex binder, or (iii) via both the acetoacetoxy groups present in the crosslinking agent and structural units derived from interpolymerization of acetoacetoxy ethyl methacarylate monomer, or (iv) via bonds between the acetoacetoxy groups present in the crosslinking agent and structure amine units otherwise present in the coating composition.
  • the reactive crosslinking agent of the present disclosure also can be included in a wood stain as a non-lapping additive.
  • Wood stains are often employed as coatings on wood floors in housing, offices, and other architectural applications. Bare wood is stained with a wood stain to alter the color prior to application of a clearcoat. Lapping is a visual defect that occurs when applying stain to large sections of a wood substrate in sections. It results in a darker color in areas where one stained section overlaps with another. Lapping often results from pigment particles interacting strongly with water-based polymers or from one section of stained substrate partially drying or before application of a successive, partially overlapping section. Lifting is a phenomena that occurs can when a clear topcoat is applied on an underlying wood stain that is not completely dry, or when the woodstain or topcoat is water/solvent sensitive. Lapping and lifting properties often vary inversely, making it difficult to formulate compositions that address both needs.
  • US 2022/0282108 Al discloses a woodstain composition in which a polyethylene glycol having a molecular weight between 600 and 1000 Da +- 10% can be used with a water-based hydrophobic polymer to improve the lapping resistance of the woodstain.
  • a polyethylene glycol having a molecular weight between 600 and 1000 Da +- 10% can be used with a water-based hydrophobic polymer to improve the lapping resistance of the woodstain.
  • inclusion of the reactive, crosslinking polyalkylene glycol of the present disclosure in such a woodstain may improve the lapping and lifting resistance of woodstains.
  • the crosslinkable polyalkylene glycol may slow drying, thus, preventing lapping.
  • crosslinking between the crosslinkable polyalkylene glycol and other polymeric components may resist lifting through bonds formed with the polymeric matrix or other amine-containing components of the stain.
  • stains including the crosslinking agent of the present disclosure may exhibit improved durability, abrasion resistance, and other mechanical properties.
  • woodstain that comprises the crosslinking agent of the present disclosure.
  • Representative formulation ranges are as follows:
  • Woodstain Component Concentration range (wt. %)
  • Polymeric binders useful in the woodstain include acrylic latexes, vinyl acrylic latexes, styrene acrylic latexes, polyurethane dispersions, and mixtures thereof as further disclosed herein.
  • Thickeners include rheology modifiers disclosed herein.
  • the amine component of the woodstain is useful to activate the rheology modifier and includes dimethylethanolamine , monoethylethanolamine , trimethylethanolamine , morpholine , and / or ammonia.
  • Suitable biocides include those disclosed herein association with base coating compositions, and colorant compositions include those disclosed herein.
  • LTC Low Temperature Coalescence
  • a coating composition usually a paint
  • LTC may be evaluated by first cooling a Penopac panel, 1 available from Leneta Company, Inc. of Mahwah, NJ, a 4 mil drawdown bar, and 50 g of paint in a refrigerator at 40°F (4.5°C) for at least 4 hours.
  • the paint is drawn down on the Penopac panel using the 4 mil drawdown bar and the coated panel is immediately returned to the refrigerator, after which the coated panel is allowed to cure in the 40°F (4.5°C) refrigerator for 48 hours.
  • Sealed and unsealed areas of the coated panel are then separately examined under a microscope for cracking and assessed according to the following scale:
  • Block Resistance is the degree to which a cured coating resists sticking to itself after application. Block Resistance may be evaluated according to ASTM D4946-89 (2017). Face-to-face specimins of sealed paper test charts coated with 6 mils of coating applied by drawdown blade are cured for 24 hours, 3-days, or 7-days (c8uring time noted in the test results) in a room conditioned between 65 °F -85°F (18-29.5°C) at 40- 60% Rh. The cured coatings are placed face-to-face with a No. 8 stopper on top and a 1000 g
  • a Penopac chart includes sealed and unsealed areas. Sealed areas have a clear, impervious topcoat which prevents coating penetration. Unsealed areas have a semi-porous clay paper coating. weight on top of the stopper, resulting in a pressure of 127 g/cm 3 on the specimens. After 30 minutes, the stoppers and weights are removed and the samples allowed to condition in the conditioned room for 30 minutes, after which the specimins are peeled and graded according to the ratings below:
  • Surfactant leaching is a phenomena wherein the surface of an applied latex paint is stained by leaching of water-soluble materials, such as surfactants, when contacted by water after application.
  • Surfactant leaching may be measured by ASTM D7190-10 (Reapproved 2023).
  • ASTM D7190-10 Reapproved 2023.
  • a paint is applied to a wet film thickness of 5 to 10 mils and is allowed to dry for 4 hours at ambient conditions.
  • the painted panel is divided into four parts, and a row of four droplets of water are applied to the top of a panel and allowed to rest for 10 minutes. Thereafter the water droplets are removed by lifting the panel and allowing the droplets to run off the panel. Water droplets are applied and allowed to stand, and removed according to the same process after 1 and 4 days.
  • Each panel is visibly assessed and rated as follows immediately and after an overnight (O/N) dry:
  • Whether a composition includes a film-forming amount of binder can be assessed by drying a thin film of the composition on a substrate, then washing the dried composition with an aqueous solvent such as water. A composition that includes less than a film-forming amount of binder will wash away with the solvent.
  • a further crosslinking agent was prepared using the same reaction, by reacting PEG 600 with t-butyl acetoacetate in toluene solvent to prepare a di-AcAc PEG 600.
  • FIG. 1 shows the 13 C NMR spectrum of the resulting di-AcAc PEG 600 product taken in ⁇ /-chloroform (CDCh) as the NMR sample solvent.
  • the abbreviations used in Figure 1 represent the following compounds exisitng in the sample:
  • R PEG600 with un-reacted OH groups.
  • CDCL3 ⁇ /-chloroform
  • Example 2 Colorant Compositions Including Ac Ac-Functional PEG
  • Colorants of the present disclosure were prepared and tested for viscosity, block resistance and surfactant leaching.
  • Each of a yellow oxide, black, and magenta pigment were prepared having the following general formulations:
  • Table 1 Formulations for Yellow Oxide, Black, and Magenta Colorant Compositions
  • Viscosities of the colorants including AcAc-modified humectants of the present disclosure were comparable to those using an unmodified PEG 400 as humectant.
  • Example 3 Architectural Paints Tinted with Colorants Containing AcAc-Functionalized Humectants of Present Disclosure
  • Block resistance of architectural base paints tinted with colorants containing the AcAc-functionalized PEG humectants of the present disclosure were prepared. The samples were then tested for blocking resistance in architectural paints in accordance with ASTM D4946-89 (2017).
  • Colorant samples were prepared according to the formulations shown in Table 1 above and humectants added in an amount of 15.09 grams to the yellow oxide formulations; 6.11 g to the black formulations, and 10.93 g to the magenta formulations.
  • Table 7 Blocking Resistance Results for Tinted HGTV Home by Sherwin-Williams, Everlast Semi-Gloss Exterior Latex Tinted with Colorants of Present Disclosure
  • colorants including AcAc-modified PEGs of the present disclosure provided comparable or improved block resistance and surfactant leaching resistance compared to control. In no instances were AcAc-modified PEGs of the present disclosure incompatible with colorant compositions or provided undesirable effects on viscosity, block resistance, or surfactant leaching.
  • crosslinking agent of the present disclosure as a float in a system for reducing skinning in a container of paint or coating was tested.
  • Samples 1 and 2 were negative and positive controls, respectively. Sample 1 included no coalescent. Sample 2 included conventional PEG 400 as a coalescent. The remaining experimental samples, 3-6, utilized Ac Ac-modified PEG embodiments of the present disclosure.
  • Attagel 50 attapulgite clay thickener from BASF.
  • the use of the crosslinking agent of embodiments of the present disclosure as either a humectant in the colorant or as a coalescent agent in the paint provide improved block resistance rating compared to not using the present disclosure crosslinking agent. Even if only used in one of the colorant composition or base paint, the resulting block resistance rating is significantly improved compared to the use of PEG400 as a humectant in colorant or a coalescent in base paint, or to not being present in either component. Further, when used in both the colorant and the paint, the resulting product has consistently good block resistance.
  • Embodiment 1 A crosslinking agent for use in a water-borne colorant composition, paint composition, or coating composition comprising: a polyalkylene glycol including at least one acetoacetoxy group, wherein the glycol has an Mw of 400 to 3000, and wherein the polyalkylene glycol is composed of interpolymerized ethylene oxide groups, interpolymerized propylene oxide groups, or combinations thereof.

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  • Engineering & Computer Science (AREA)
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Abstract

L'invention concerne un agent de réticulation destiné à être utilisé dans une composition colorante, une composition de peinture ou une composition de revêtement, l'agent de réticulation contenant un polyalkylèneglycol comprenant au moins un groupe acétoacétoxy, le glycol présentant un poids moléculaire Mw situé dans la plage allant de 400 à 3 000, conjointement avec des compositions de colorant, des compositions de revêtement de base, des compositions de revêtement teintées, des systèmes destinés à réduire la formation de peaux dans une composition de revêtement de base, des compositions de coloration et des substrats revêtus à l'aide de l'agent de réticulation.
PCT/US2024/061333 2024-01-05 2024-12-20 Polyalkylèneglycols fonctionnalisés par acétoacétoxy et utilisations correspondantes Pending WO2025147405A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5021537A (en) * 1990-04-27 1991-06-04 Shell Oil Company Polyacetoacetate-containing epoxy resin compositions
US5426148A (en) * 1992-12-18 1995-06-20 Tremco, Inc. Fast-curling, high strength, two-part sealants using acetoacetate-amine cure chemistry
US20180079851A1 (en) * 2004-12-17 2018-03-22 Valspar Sourcing, Inc. Aqueous coating compositions containing acetoacetyl-functional polymers, coatings, and methods
US20220185762A1 (en) * 2019-04-03 2022-06-16 Lonza Solutions Ag Method for Preparation of Acetoacetylated Polyols
WO2022200415A1 (fr) * 2021-03-24 2022-09-29 Croda International Plc Revêtements, adhésifs et élastomères utilisant un polyol coiffé aux extrémités d'acétoacétate dérivé de polyesters thermoplastiques

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5021537A (en) * 1990-04-27 1991-06-04 Shell Oil Company Polyacetoacetate-containing epoxy resin compositions
US5426148A (en) * 1992-12-18 1995-06-20 Tremco, Inc. Fast-curling, high strength, two-part sealants using acetoacetate-amine cure chemistry
US20180079851A1 (en) * 2004-12-17 2018-03-22 Valspar Sourcing, Inc. Aqueous coating compositions containing acetoacetyl-functional polymers, coatings, and methods
US20220185762A1 (en) * 2019-04-03 2022-06-16 Lonza Solutions Ag Method for Preparation of Acetoacetylated Polyols
WO2022200415A1 (fr) * 2021-03-24 2022-09-29 Croda International Plc Revêtements, adhésifs et élastomères utilisant un polyol coiffé aux extrémités d'acétoacétate dérivé de polyesters thermoplastiques

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