WO2023038642A1 - Teinture à bois et apprêts de pénétration comprenant des dispersions aqueuses à faible teneur en cov - Google Patents

Teinture à bois et apprêts de pénétration comprenant des dispersions aqueuses à faible teneur en cov Download PDF

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WO2023038642A1
WO2023038642A1 PCT/US2021/050072 US2021050072W WO2023038642A1 WO 2023038642 A1 WO2023038642 A1 WO 2023038642A1 US 2021050072 W US2021050072 W US 2021050072W WO 2023038642 A1 WO2023038642 A1 WO 2023038642A1
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ethylenically unsaturated
formulation according
formulation
water
polymer
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PCT/US2021/050072
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English (en)
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Matthias Junk
Thomas Fichtner
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Celanese International Corporation
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Priority to PCT/US2021/050072 priority Critical patent/WO2023038642A1/fr
Publication of WO2023038642A1 publication Critical patent/WO2023038642A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D15/00—Woodstains
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/002—Priming paints
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond

Definitions

  • the present invention relates generally to wood stain and penetration primer formulations containing aqueous dispersions having low volatile organic component levels.
  • the aqueous dispersion comprises a polymer formed by polymerization of at least one ethylenically unsaturated strong acid monomer and at least one ethylenically unsaturated weak acid monomer.
  • the formulation also includes at least one water-soluble alkali metal silicate, at least one water-soluble alkali metal or alkaline earth metal alkyl siliconate, or a mixture thereof.
  • VOCs volatile organic compounds
  • Formulations with reduced VOC content tend to be more susceptible to bacteria, algae, yeasts, fungi and other biological agents that thrive in aqueous environments.
  • Such biological agents can grow in paint cans and containers, often imparting an unpleasant odor and rendering the formulations unusable for their intended purpose.
  • Biological agents also can cause viscosity loss, discoloration, gassing, frothing, sedimentation and pH changes in the formulations.
  • certain biological agents, such as algae and molds may grow on dried paint films covering walls or other substrates resulting in potential health issues.
  • Biocides particularly isothiazolinones, are therefore frequently added to low VOC aqueous formulations to control the growth of biological agents. Some of these biocides may remain on the dried paint film to control algae and molds.
  • isothiazolinone-based biocides are known to cause allergic contact dermatitis.
  • One such method involves maintaining the paint at high pH values, e.g., sufficiently high to inhibit microbial growth, by incorporating an inorganic alkaline buffer, such as water glass.
  • U.S. Pub. No. 2021/0002506 describes a biocide- and ammonia-free aqueous polymer dispersion obtained by radically initiated multi-stage emulsion polymerization and comprising particles comprising at least a first polymer phase formed from a monomer composition I and a second polymer phase from a different monomer composition II.
  • the first polymer phase has a glass transition temperature below 20°C
  • the second polymer phase has a glass transition temperature above 20°C, both as determined by differential scanning calorimetry according to ISO 16805.
  • the polymer dispersion further comprises at least one water-soluble alkali metal silicate, at least one water-soluble alkali metal or alkaline earth metal alkyl siliconate, or a mixture thereof and has a pH of 10.0 or higher.
  • U.S. Patent No. 7,789,959 describes coating compositions comprising at least one strongly basic agent to set a pH of at least 10, at least one selected vinyl ester copolymer, if desired, pigment and/or filler, and, if desired, further additives customary per se.
  • the coating compositions can be stored without use of additional preservatives and can be used to coat substrates of all kinds.
  • U.S. Patent No. 7,285,590 describes aqueous dispersions having a minimum film formation temperature no greater than about 50°C, that include a multi-stage emulsion polymer made by a process that includes a first polymerization stage, in which a first monomer mixture having a calculated glass transition temperature of at least about 50°C is polymerized via free radical emulsion polymerization to obtain a first-stage emulsion polymer, and a second polymerization stage, in which a second monomer mixture, having a calculated glass transition temperature from about -30°C to about 10°C, is polymerized via free radical emulsion polymerization, in the presence of the first-stage emulsion polymer.
  • U.S. Patent No. 6,756,459 describes a binder composition for aqueous coatings that exhibits high gloss and superior corrosion resistance when applied to metal substrates comprising an aqueous emulsion copolymer, the copolymer including as polymerized units, at least one ethylenically unsaturated monomer and an ethylenically unsaturated strong acid monomer, such as phosphorus containing monomers, particularly phosphoethylmethacrylate; or salts thereof Also provided is a method for achieving high gloss and superior corrosion resistance of metal substrates by coating a substrate with an aqueous coating composition comprising the binders of the present invention and drying, or allowing to dry, the aqueous composition.
  • EP Patent No. 1297079 discloses a preservative-free dispersion paint consisting of 4- 15 percent by weight polymer dispersion that is calculated as solid fraction, 10-55 percent by weight pigment and/or extender and a maximum of 2 percent by weight water glass as additive and fractions of water to complete 100 percent by weight. Said dispersion paint has the known and reliable processing properties of dispersion paints although no preservative is used.
  • DE 102014013455 discloses an improved, non-preservation dispersion-based emulsion paint based on siliconates for indoor and outdoor use with improved properties.
  • the paint contains a) 2-30% polymer dispersion calculated as solids content b) 10-60% pigment and / or filler, c) 0.5-5% siliconate as an additive and d) 100% added amounts of water.
  • the disclosure relates to a penetration primer or wood stain formulation.
  • the formulation comprises: a) an aqueous polymer dispersion comprising a polymer produced by free-radically initiated emulsion polymerization of an ethylenically unsaturated strong acid monomer with a pKa less than 4 (in water at 20°C) and an ethylenically unsaturated weak acid monomer with a pKa of 4 or greater (in water at 20°C); and b) at least one water-soluble alkali metal silicate, at least one water-soluble alkali metal or alkaline earth metal alkyl siliconate, or a mixture thereof.
  • the formulation may be free of biocides.
  • the formulation may have a pH from 10 to 12, preferably from 10.5 to 11.5.
  • the weight-average particle size of the aqueous polymer dispersion may be less than 100 nm, preferably less than 80 nm, or more preferably less than 60 nm, as measured by capillary hydrodynamic fractionation.
  • the at least one ethylenically unsaturated strong acid monomer may be present in an amount from 0.5 to 5 wt. %, preferably from 0.7 to 4.5 wt. %, more preferably from 0.8 to 4.0 wt. %, most preferably from 1.0 to 3.5 wt. %, based on the weight of all monomers used in producing the polymer.
  • the at least one ethylenically unsaturated strong acid monomer comprises a sulfonic acid or a salt thereof. In some aspects, the at least one ethylenically unsaturated strong acid monomer comprises vinyl sulfonic acid or 2-acrylamido-2- methylpropanesulfonic acid or an alkali metal or ammonium salt thereof. In some aspects, the at least one unsaturated strong acid monomer comprises 2-acrylamido-2-methylpropanesulfonic acid or an alkali metal or ammonium salt thereof.
  • the ethylenically unsaturated weak acid monomer may be present in an amount from 1 to 10 wt. %, preferably from 1.5 to 8 wt.
  • the at least one ethylenically unsaturated weak acid monomer is selected from the group consisting of an ethylenically unsaturated Cs-Cs monocarboxylic acid, an ethylenically unsaturated C4-Cs dicarboxylic acid, an ethylenically unsaturated C4-Cs dicarboxylic acid anhydride, and combinations thereof.
  • the at least one ethylenically unsaturated weak acid monomer comprises methacrylic acid, acrylic acid, or combinations thereof.
  • the ethylenically unsaturated weak acid monomer comprises at least two ethylenically unsaturated weak acid monomers.
  • the polymer may additionally be formed from at least one hard block-building monomer having a glass transition temperature of the corresponding homopolymer of greater than 25°C and at least one soft block-building monomer having a glass transition temperature of the corresponding homopolymer of less than 25°C.
  • the hard block-building monomer may comprise styrene or a combination of methyl methacrylate and styrene.
  • the soft block-building monomer may comprise 2-ethylhexyl acrylate.
  • the monomer mixture used to form the polymer does not comprise methacrylamide and/or acrylamide.
  • the glass transition temperature of the polymer may be 15°C or lower, preferably from -15°C to 10°C, more preferably from -10 to 5°C, as determined by differential scanning calorimetry according to ISO 16805 (2005).
  • the formulation may have a minimum film forming temperature of less than 5°C, preferably less than 1°C.
  • the aqueous polymer dispersion may have a Total Volatile Organic Compound (TVOC) content less than 1800 ppm, preferably less than 1500 ppm, more preferably less than 1000 ppm, as determined by gas chromatography according to ISO 11890-2 (2020).
  • the formulation may be free of organic solvent, plasticizer, and/or coalescent agent.
  • aqueous dispersions as well as primer and wood stain formulations incorporating the aqueous dispersions.
  • the aqueous dispersion comprises a polymer produced by free-radically initiated emulsion polymerization of an ethylenically unsaturated strong acid monomer with a pKa of less than 4 (as measured in water at 20°C) and an ethylenically unsaturated weak acid monomer with a pKa of 4 or greater (as measured in water at 20°C).
  • formulations for penetration primers or wood stains wherein the formulation comprises the aqueous dispersion in combination with a buffer, i.e., at least one water-soluble alkali metal silicate, at least one water-soluble alkali metal or alkaline earth metal alkyl siliconate, or a mixture thereof.
  • a buffer i.e., at least one water-soluble alkali metal silicate, at least one water-soluble alkali metal or alkaline earth metal alkyl siliconate, or a mixture thereof.
  • the pH of a penetration primer and/or wood stain formulation may be adjusted to be at a level where biocides are not needed.
  • One problem with such formulations is that the polymer in the aqueous dispersion may not be compatible with the buffer. This is particularly challenging for very finely dispersed polymer dispersions with a high internal surface area, as required for penetration primers and wood stains.
  • formulations containing (i) an aqueous dispersion of a polymer formed from a weak acid monomer and a strong acid monomer, and (ii) a water-soluble alkali metal silicate, a water-soluble alkali metal siliconate, an alkaline earth metal alkyl siliconate, or combinations thereof, were advantageously both stable and low in VOC content.
  • the formulation may also be biocide-free but still capable of preventing growth of bacteria, algae, yeasts, fungi and other biological agents that thrive in an aqueous environment Definitions and Descriptions
  • invention As used herein, the terms “invention,” “the invention,” “this invention” and “the present invention” are intended to refer broadly to all of the subject matter of this patent application and the claims below. Statements containing these terms should be understood not to limit the subject matter described herein or to limit the meaning or scope of the patent claims below.
  • biocide-free when used in relation to a formulation, means a formulation which contains less than 10 ppm by weight, preferably less than 5 ppm and most preferably no detectable amount, of a chemical preservative, such as the compounds listed as Product-Type 6 biocides in EU Biocidal Products Regulation (528/2012).
  • a chemical preservative such as the compounds listed as Product-Type 6 biocides in EU Biocidal Products Regulation (528/2012).
  • the present formulation may not be subject to labeling with the safety phase EUH 208, which is otherwise required for coating compositions using biocides.
  • the amount of a 3: 1 mixture of 5-chloro-2-methyl-4-isothiazolin-3-one (CIT) and 2-methyl-4-isothiazolin-3-one (MIT) needs to be less than 1.5 ppm to avoid EUH 208 labeling.
  • CIT 5-chloro-2-methyl-4-isothiazolin-3-one
  • MIT 2-methyl-4-isothiazolin-3-one
  • biocide does not include organic and inorganic bases, such as sodium or potassium hydroxide, used to raise the pH of the coating composition to at least 10.
  • Volatile Organic Content is defined according to the Directive 2004/42/CE of the European Parliament and The Council of The European Union and measured according to ISO 11890-2 (2020).
  • Semi Volatile Organic Content is defined according to Commission Decision 2014/312ZEU and measured according to ISO 11890-2 (2020).
  • the formulations described herein include an aqueous polymer dispersion system that contains polymer particles in disperse distribution as the disperse phase in an aqueous medium.
  • the aqueous polymer dispersions can be prepared as monomer mixtures in an aqueous medium and then polymerized, for example through an emulsion polymerization, to produce the aqueous polymer dispersion.
  • the emulsion polymerization process is a free radically initiated polymerization.
  • the monomer mixture of the aqueous dispersion, prior to polymerization, contains at least two monomers capable of polymerization.
  • a first monomer may comprise at least one ethylenically unsaturated strong acid monomer with a pKa less than 4 (in water at 20°C), referred to herein as a strong acid monomer.
  • a second monomer may comprise at least one ethylenically unsaturated weak acid monomer with a pKa of 4 or greater (in water at 20°C), referred to herein as a weak acid monomer.
  • Exemplary strong acid monomers include a sulfonic acid or a salt thereof, such as vinyl sulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid or the alkali metal or ammonium salts thereof.
  • the strong acid monomer comprises 2-acrylamido-2- methylpropanesulfonic acid or the alkali metal or ammonium salts thereof.
  • the strong acid monomer may be present in an amount from 0.5 to 5 wt. %, e.g., from 0.7 to 4.5 wt. %, from 0.8 to 4.0 wt. %, from 1.0 to 3.5 wt. %, from 1.2 to 3.0 wt. %, or from 1.4 to 2.5 wt. %, based on the weight of all monomers used in producing the polymer.
  • Exemplary weak acid monomers include ethylenically unsaturated Cs-Cs monocarboxylic acids, ethylenically unsaturated C4-Cs dicarboxylic acids, ethylenically unsaturated C4-C8 dicarboxylic acid anhydrides, and combinations thereof.
  • Exemplary ethylenically unsaturated Cs-Cs monocarboxylic acids include acrylic acid, methacrylic acid and crotonic acid.
  • Exemplary ethylenically unsaturated C4-Cs dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, and citraconic acid.
  • the weak acid monomer comprises methacrylic acid, acrylic acid, or combinations thereof.
  • the weak acid monomer comprises at least two weak acid monomers.
  • the weak acid monomer may be present in an amount from 1 to 10 wt. %, e.g., from 1.5 to 8 wt. %, from 2 to 7 wt. %, from 2.5 to 6 wt. %, or from 3 to 5 wt. %, based on the weight of all monomers used in producing the polymer.
  • the sum of strong and weak acid monomers is from 3 to 10 wt. %, such as from 4 to 8 wt. %, e.g. from 5 to 7 wt. %, based on the weight of all monomers used in producing the polymer.
  • the monomer mixture of the aqueous dispersion, prior to polymerization does not comprise methacrylamide or acrylamide.
  • the polymer in the aqueous dispersion is additionally formed from at least one hard block-building monomer having a glass transition temperature of the corresponding homopolymer of greater than 25°C and at least one soft block-building monomer having a glass transition temperature of the corresponding homopolymer less than 25°C.
  • the hard block-building monomer may be selected from vinyl esters of Ci to C2 carboxylic acids, methacrylic acid esters, vinyl aromatics, vinyl halogenides, and mixtures thereof.
  • the at least one hard block-building monomer is selected from styrene, vinyltoluene, acrylonitrile, methacrylonitrile, methyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, and mixtures thereof.
  • the hard block-building monomer comprises styrene.
  • the hard block-building monomer comprises styrene and methyl methacrylate.
  • the soft block-building monomer may be selected from acrylic and methacrylic acid esters, olefins, vinyl esters of C3 to Cis carboxylic acids and mixtures thereof.
  • the at least one soft block-building monomer is selected from ethyl acrylate, n- butyl acrylate, n-octyl acrylate, 2-octyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-propylheptyl acrylate, lauryl acrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl acrylate and mixtures thereof.
  • the soft block-building monomer comprises 2-ethylhexyl acrylate.
  • the monomer mixture of the aqueous dispersion, prior to polymerization may include additional functional monomers.
  • additional functional monomers may include ethylenically unsaturated silane co-monomers such as vinyl trialkoxy silanes or y- (meth)acryloxypropyltrialkoxysilanes, ethylenically unsaturated glycidyl co-monomers such as glycidyl methacrylate, ethylenically unsaturated ureido co-monomers such as ureido methacrylate, ethylenically unsaturated carbonyl-functional monomers such as diacetone acrylamide or acetoacetoxy ethyl methacrylate, and monomers with at least two non-conjugated ethylenically unsaturated groups.
  • silane co-monomers such as vinyl trialkoxy silanes or y- (meth)acryloxypropyltrialkoxysilanes
  • the weight-average particle size (dw) of the aqueous polymer dispersion is less than 100 nm, e.g., less than 80 nm, or less than 60 nm, as measured by capillary hydrodynamic fractionation. Finely dispersed polymer dispersions are particularly advantageous for penetration primers and wood stains, as they are able to deeply penetrate into the substrate.
  • the polymer dispersions may be prepared under conditions to produce a polymer with a uniform glass transition temperature.
  • the glass transition temperature of the polymer comprised in aqueous polymer dispersion is 15°C or lower, e.g., from -15°C to 10°C, or from -10 to 5°C, as determined by differential scanning calorimetry according to ISO 16805.
  • the glass transition temperature may be selected so as to have a low enough value that a coalescent agent is not needed.
  • Coalescent agents are known to be the main contributors to VOCs in coating applications and are therefore preferably excluded from the formulations and aqueous dispersions described herein.
  • the Brookfield viscosity of the aqueous polymer dispersion may be less than 500 mPa s, e.g., less than 200 mPa s, or less than 100 mPa s, as measured at 20°C, 20 rpm, spindle 2.
  • the coagulum content of the unfiltered aqueous polymer dispersion may be less than 0.05%, e.g., less than 0.02%, less than 0.01%, or less than 0.005% as determined by filtration over a filter with 180 pm mesh size.
  • the aqueous polymer dispersion disclosed herein may be prepared by a customary processes of emulsion polymerization, where the monomers may be emulsified in the aqueous phase in the presence of emulsifiers, initiators, and optionally protective colloids, and are advantageously polymerized at temperatures from 60°C to 95°C.
  • emulsifiers such as emulsifiers, initiators, and optionally protective colloids
  • emulsion-feed processes allows a small amount of the monomers to be pre-polymerized and then the remainder of the monomers is metered in the form of an aqueous emulsion.
  • the process may involve polymerization in one, two, and more stages with different monomer combinations. Preferably, a single stage polymerization is performed, producing a homogeneous polymer dispersion with one defined glass transition temperature.
  • the initiators may include, without limiting the scope of the embodiments of the disclosed invention, one or more free radical initiators.
  • Suitable free radical initiators include hydrogen peroxide, benzoyl peroxide, cyclohexanone peroxide, isopropyl cumyl hydroperoxide, persulfates of potassium, persulfates of sodium and persulfates of ammonium, peroxides of saturated monobasic aliphatic carboxylic acids having an even number of carbon atoms and a Cs- C12 chain length, tert-butyl hydroperoxide, di-tert-butyl peroxide, diisopropyl percarbonate, azoisobutyronitrile, acetylcyclohexanesulfonyl peroxide, tert-butyl perbenzoate, tert-butyl peroctanoate, bis(3,5,5-trimethyl)hexanoyl peroxide, tert-butyl
  • the above-mentioned compounds can also be used within redox systems, using transition metal salts, such as iron(II) salts, or other reducing agents.
  • Transition metal salts such as iron(II) salts, or other reducing agents.
  • the polymer dispersions preferably comprise no more than 5 wt. %, such as from 1 to 4 wt. % of ionic emulsifiers, and no more than 5 wt. %, e.g., no more than 3 wt. %, such as no more than 2.5 wt. %, of nonionic emulsifiers, based on the total weight of all monomers used in forming the polymer in the aqueous dispersion.
  • nonionic emulsifiers examples include alkyl polyglycol ethers, e.g., ethoxylation products of fatty alcohols such as lauryl, oleyl, or stearyl alcohol, or mixtures of the same, e.g., coconut fatty alcohol, or ethoxylation products of oxo-process alcohols; and ethoxylation products of polypropylene oxide.
  • fatty alcohols such as lauryl, oleyl, or stearyl alcohol, or mixtures of the same, e.g., coconut fatty alcohol, or ethoxylation products of oxo-process alcohols; and ethoxylation products of polypropylene oxide.
  • copolymerizable nonionic surfactants can be employed.
  • Particularly suitable are ethylene oxide ethers with a degree of ethoxylation from 20 to 40 of Cio to Cis alkyl alcohols.
  • no alkylphenol ethoxylates are used.
  • Suitable ionogenic emulsifiers are anionic emulsifiers, e.g., the alkali metal or ammonium salts of alkyl-, aryl- or alkylaryl sulfonates or -phosphonates, or of alkyl, aryl, or alkylaryl sulfates, or of alkyl, aryl, or alkylaryl phosphates, or compounds with other anionic end groups, and it is also possible here for there to be oligo- or polyethylene oxide units between the hydrocarbon radical and the anionic group.
  • anionic emulsifiers e.g., the alkali metal or ammonium salts of alkyl-, aryl- or alkylaryl sulfonates or -phosphonates, or of alkyl, aryl, or alkylaryl sulfates, or of alkyl, aryl, or alkylaryl phosphates, or compounds with other anionic end groups, and it
  • Typical examples are sodium lauryl sulfate, sodium undecyl glycol ether sulfate, sodium lauryl diglycol sulfate, sodium tetradecyl triglycol sulfate, sodium dodecylbenzenesulfonate.
  • copolymerizable anionic surfactants may be used.
  • Sodium lauryl sulfate is particularly preferred.
  • no alkylphenol ethoxylates including derivatives thereof are employed.
  • the polymer dispersions and compositions containing such dispersions described herein can be substantially free of protective colloids as stabilizing agents.
  • protective colloids include carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), and polyvinyl alcohol (PVOH).
  • CMC carboxymethyl cellulose
  • HEC hydroxyethyl cellulose
  • PVOH polyvinyl alcohol
  • Such polymer dispersions are considered to be “substantially free” of protective colloids when protective colloids comprise no more than 0.5 wt. %, e.g., no more than 0.2 wt. % or no more than 0.1 wt. %, based on the total amount of monomers used in forming the polymer in aqueous dispersion.
  • a further, preferably chemical after-treatment, especially with redox catalysts, for example combinations of the above-mentioned oxidizing agents and reducing agents, may follow to reduce the level of residual unreacted monomer on the product.
  • residual monomer can be removed in known manner, for example by physical demonomerization, i.e. distillative removal, especially by means of steam distillation, or by stripping with an inert gas.
  • the total residual monomer content of the polymer dispersion may be less than 500 ppm, e.g. less than 300 ppm, preferably less than 200 ppm, or less than 100 ppm as determined by gas chromatography according to ISO 11890-2 (2020).
  • the combination of weak acid monomer and strong acid monomer allows for the formation of a polymer dispersion, which is compatible with high pH buffers such as alkali metal silicates and alkali metal or alkaline earth metal alkyl siliconates and that has a Total Volatile Organic Compound (TVOC) content of less than 1800 ppm, e.g., less than 1500 ppm, less than 1250 ppm or less than 1000 ppm, as determined by gas chromatography according to ISO 11890-2 (2020), without the need for timeconsuming and costly physical demonomerization processes.
  • high pH buffers such as alkali metal silicates and alkali metal or alkaline earth metal alkyl siliconates
  • TVOC Total Volatile Organic Compound
  • the aqueous polymer dispersions produced by the process described herein generally have a solids content of from 25 to 50% by weight, preferably from 30 to 40% by weight, and a pH between 2.5 and 9.0, preferably between 3.0 and 8.0, more preferably between 4.5 and 7.0.
  • the pH value of the dispersion may be raised by addition of an organic or inorganic base, such as an amine or an alkali metal hydroxide, such as sodium or potassium hydroxide. In some embodiments, it is preferred to effect neutralization with a nitrogen-free base.
  • aqueous polymer dispersions described herein are usually free of ammonia. They may also be free of biocides.
  • biocides may be added that can be decomposed during subsequent preparation of the coating composition to yield a preservative-free coating.
  • DBNPA 2,2-dibromo-3- nitrilopropionamide
  • CIT 5-chloro-2-methyl- 3(2H)-isothiazolone
  • CIT can be decomposed either through increase of the pH, preferably to at least 11, or by addition of, e.g., cysteine to the coating composition.
  • the polymer dispersions may comprise up to 50 ppm CIT and up to 1000 ppm DBNPA.
  • the dispersions comprise a mixture of 5 to 14.9 ppm CIT and 50 to 500 ppm DBNPA. More information on a biocide treatment and removal process that allows aqueous polymer dispersions to be protected from microbial attack during storage, while allowing the end product, such as a coating composition, remain substantially preservative-free can be found in US Patent Application Serial No. 62/741137 filed October 4, 2018, the entire contents of which are incorporated herein by reference.
  • the aqueous polymer dispersion may be combined with a high pH buffer, e.g., at least one water-soluble alkali metal silicate, at least one water-soluble alkali metal or alkaline earth metal alkyl siliconate, or a mixture thereof, to form a penetration primer and/or wood stain formulation.
  • a high pH buffer e.g., at least one water-soluble alkali metal silicate, at least one water-soluble alkali metal or alkaline earth metal alkyl siliconate, or a mixture thereof.
  • the buffer is included to stabilize the pH of the formulation above a value of 10.0, preferably in the desired range.
  • Water-soluble alkali metal silicates also known as water glass or liquid glass, are described by the chemical formula M20*n SiCh, where M can be lithium, sodium or potassium, and where n can range between 1-4.
  • M can be lithium, sodium or potassium
  • n can range between 1-4.
  • alkali metal silicates with n>3.2 are used.
  • the alkali metal silicate is potassium silicate.
  • aqueous solutions of alkali metal silicates may be used, particularly those with a solid content not exceeding 40 wt. %.
  • water-soluble alkali metal or alkaline earth metal alkyl siliconates such as sodium, potassium or calcium methyl siliconate
  • An exemplary siliconate is potassium methyl siliconate. Due to the ease of handling and mixing, aqueous solutions of siliconates may be used.
  • preparations comprising alkali metal silicates and/or alkali metal or alkaline earth metal alkyl siliconates, such as Lopon® PHB, marketed by ICL, may be used.
  • the buffer comprises potassium silicate.
  • the formulation may comprise, based on the total weight of the formulation, from 0.1 to 4 wt. %, e.g., from 0.3 to 3 wt. %, from 0.5 to 2.5 wt. %, or from 0.7 to 2 wt. % of at the least one water-soluble alkali metal silicate, the at least one water-soluble alkali metal or alkaline earth metal alkyl siliconate, or a mixture thereof. If a water-soluble alkali metal silicate is used, preferred ranges are, based on the total weight of the formulation, 0.5 to 3 wt. %, e.g., 0.75 to 2.5 wt. %, such as 1 to 2 wt. %.
  • a water-soluble alkali metal or alkaline earth metal alkyl siliconate is used, preferred ranges are, based on the total weight of the formulation, 0.3 to 2 wt. %, e.g. 0.5 to 1.5 wt. %, such as 0.75 to 1 wt. %.
  • the at least one water-soluble alkali metal silicate, at least one water-soluble alkali metal or alkaline earth metal alkyl siliconate, or a mixture thereof, is preferably added to the polymer dispersion after polymerization. In some aspects, it may be post-added below 50° C.
  • the formulation may have a pH from 10 to 12, e.g., from 10.5 to 11.5, preferably from 11.0 to 11.5. The pH may be adjusted by the amount of buffer included, as described above. The pH value of the formulations may further be adjusted by addition of an organic or inorganic base. The formulation may be biocide-free.
  • the polymer dispersion comprises the biocide 5- chloro-2-methyl-3(2H)-isothiazolone (CIT)
  • CIT biocide 5- chloro-2-methyl-3(2H)-isothiazolone
  • cysteine or other suitable additives such as N-acetyl cysteine, mercaptoethanol, mercaptopropionic acid, methyl mercaptopropionate, glutathione, thioglycolate, sodium thiosulfate, sodium bisulfite, pyrithione, mercaptopyridine, dithiothreitol, mercaptoethanesulfonate, and/or sodium formaldehyde sulfoxylate to the coating composition, with cysteine being preferably used.
  • Polymer dispersions comprising 2,2-dibromo- 3 -nitrilopropionamide (DBNPA) do not require addition of any decomposition agents, since DBNPA readily decomposes at pH values
  • Main contributors to VOC are coalescent agents which reduce the MFFT, such as butyl glycol, butyl di glycol, butyl di glycol acetate, l-methoxy-2-propanol, 3 -methoxy- 1 -butanol, texanol, ethyl diglycol, dipropylene glycol monomethyl ether, and dipropylene glycol n-butyl ether, and plasticizers, which increase the elasticity of the coating, such as 2,2,4-trimethyl-l,3- pentanediol diisobutyrate (TXIB), hexylene glycol, triethylene glycol-bis-2-ethylhexanoate (3G8), Loxanol® PL 3060, and BenzoflexTM.
  • coalescent agents which reduce the MFFT, such as butyl glycol, butyl di glycol, butyl di glycol acetate, l-methoxy-2-propano
  • VOC sources may include co-solvents, including glycols, which help with wet edge application, open time, and freeze-thaw resistance, emulsion components and most additives at low levels.
  • co-solvents including glycols, which help with wet edge application, open time, and freeze-thaw resistance, emulsion components and most additives at low levels.
  • glycols which help with wet edge application, open time, and freeze-thaw resistance
  • emulsion components emulsion components and most additives at low levels.
  • amino methyl propanol is a volatile compound used to adjust pH.
  • the formulation may also be free of organic solvent, plasticizer, and/or coalescent agents, i.e., does not contain a detectable amount of any or all of these components.
  • the polymer dispersion may have a minimum film forming temperature (MFFT) of less than 5°C, e.g., less than 1°C.
  • MFFT film forming temperature
  • the aqueous polymer dispersions described herein are stable fluid systems which can be used to produce formulations suitable for use as penetration primers and wood stains.
  • the solid content of these formulations may range from 1 to 30%, e.g., from 5 to 25 %, or from 10 to 20%.
  • the formulation may also comprise other components, including wetting agent, defoamer, hydrophobic agent, wood protection additive, pigments, thickener, dispersing agent/stabilizer, and combinations thereof. These components may each generally be present, if at all, in an amount from 0 to 5 wt. %, based on the total weight of the formulation.
  • the formulations may further comprise stabilizers, that prevent premature silicification of the silicate of siliconate buffers.
  • stabilizers are organic compounds comprising the functionalities of primary, secondary or tertiary amines or quarternary ammonium salts.
  • Preferred pigment volume concentrations (pvc) of the formulations are below 30%, such as below 20%, preferably below 10%.
  • the penetration primer and/or wood stain formulations described herein may be applied to a variety of substrates, including hard and soft wood, gypsum, cement, fiberboard, melamine, drywall, old paint and render surfaces, and other building materials.
  • a 3 liter reactor equipped with a reflux condenser and an anchor stirrer was filled with 630 g of deionized (DI) water and 93.3 g of an aqueous sodium dodecyl sulfate solution with an active content of 15 wt. %. While stirring, the reactor content was heated to 80°C and 8.0% of the monomer feed was added, as obtained by mixing the ingredients in Table 1 under stirring. A solution of 0.7 g sodium persulfate in 14 g of DI water was added and the reactor contents were held at 80°C for 15 min. Subsequently, the remaining amount of the monomer feed was added to the reactor with a constant dosage rate over 180 min.
  • DI deionized
  • tert-butyl hydroperoxi de (TBHP, 70 wt. % in water) in 10.5 g DI water were added to the reactor.
  • 0.5 g of Briiggolit® FF6 M (supplied by L. Briiggemann GmbH & Co. KG) in 10.5 g DI water were added within 15 min.
  • the redox post-treatment was repeated.
  • the reactor contents were then cooled to 30°C.
  • the pH of the resulting polymer dispersion was then adjusted to about 6.0 with caustic soda (active content: 5 wt. %).
  • Example 1 The process of Example 1 was repeated with varying monomer feed compositions, as described in Table 1.
  • Example 1 The process of Example 1 was repeated with a varying monomer feed composition, as described in Table 1.
  • T g Glass transition temperature as measured by differential scanning calorimetry (DSC) according to ISO 16805 (2005)
  • Comparative dispersion Cl (not comprising a strong acid monomer) coagulated during the mixing process, indicating inadequate silicate stability.
  • Inventive dispersions 4 (comprising one weak acid monomer) and 6 (comprising a mixture of n-butyl acrylate and 2- ethylhexyl acrylate) solidified 7 days after being admixed with potassium silicate, indicating a slight silicate incompatibility. All other dispersions, besides being prone to slight speck formation 1 day after admixture of potassium silicate, did not show any silicate incompatibility under the harsh test conditions.
  • biocide-containing penetration primers were prepared by mixing the ingredients in Table 4 (pos. 1-3 and 5) at room temperature under stirring (Ex. 9-16).
  • Biocide- free penetration primers were obtained through addition of potassium methyl siliconate (pos. 6) and consecutive adjustment of the pH of the primers to 11.0-11.5 through addition of 10 wt. % caustic soda (Ex. 17-24).
  • the biocides added to the polymer dispersion readily decomposed (cp. WO 2020072206 Al) while the primers were protected against microbial attack through their high pH values.
  • a second class of biocide-free primers was obtained by mixing pos. 1, 4, 5, and 7 (Ex. 25-32). In this case, high pH values above 11 were affected through addition of potassium silicate (pos. 7).
  • each primer formulation into different substrates was tested. Spruce was selected as a representative of soft wood. Red cedar was used as a representative of hard wood. 0.3 mL of primer was dripped onto the surface of each test substrate. After a waiting time of one hour, the penetration was assessed visually with a score from 1 to 6, 1 representing the best and 6 representing the worst rating.
  • a beaker was filled with quartz sand (W10 from Quarzwerke Frechen, Germany) which was then compacted by repeated, gentle tapping of the beaker on the bench.
  • a defined hollow with a diameter of approximately 30 mm was created by pressing a spherical plastic stamp into the quartz surface. 2 mL of the primer were added dropwise into this hollow. After a drying time of 1 day, the solidified quartz sand body was taken out of the beaker, carefully freed from any loose sand with a brush, and weighed. The higher the weight, the better the solidification capability of the primer.
  • the performance of the biocide-free primers was on the same level or even better than the performance of the conventional biocide-containing primers.
  • the solidification capability of biocide-free primers based on inventive dispersions was excellent.
  • the pH stability of all biocide-free primers based on inventive dispersions was on a very good level. After 28 days storage at 50°C, the drop in pH was at most 0.07. C24 based on Comparative Dispersion 8 exhibited the worst pH stability with a drop of 0.18 within the same timeframe.
  • Biocide-containing wood stains were prepared by mixing the ingredients in Table 8 at room temperature under stirring (Ex. 33-40).
  • Biocide-free wood stains were obtained through addition of potassium methyl siliconate (pos. 8) and consecutive adjustment of the pH to 11.0-11.5 through addition of 10 wt. % caustic soda (Ex. 41-48).
  • a second class of biocide-free primers was obtained through addition of potassium silicate (pos. 9) and consecutive adjustment of the pH through addition of caustic soda (Ex. 49-56).
  • Wood stains protect and enhance the aesthetical appearance of the substrate.
  • a desired feature of transparent wood stains is the accentuation of the wood grain.
  • the wood stains shall protect the substrate from environmental influences. When subjected to water for an extended period of time, the wood may be prone to discoloration, either due to water whitening or due to water penetrating into the substrate.
  • Water whitening is an optical phenomenon which is caused by the hydration of hydrophilic parts of the polymeric binder when a coated substrate is immersed in or wetted with water. Hydration changes the refractive index of these parts and leads to light scattering at the interfaces of hydrated and nonhydrated domains. Penetration of water into the substrate, on the other hand, causes wood to darken. To test the magnitude of discoloration upon water exposure, the wood stain was applied twice onto spruce with a brush.
  • Embodiment 1 A penetration primer or wood stain formulation, comprising: a) an aqueous polymer dispersion comprising a polymer produced by free-radically initiated emulsion polymerization of an ethylenically unsaturated strong acid monomer with a pKa less than 4 (in water at 20°C) and an ethylenically unsaturated weak acid monomer with a pKa of 4 or greater (in water at 20°C); and b) at least one water-soluble alkali metal silicate, at least one water- soluble alkali metal or alkaline earth metal alkyl siliconate, or a mixture thereof.
  • Embodiment 2 The formulation according to Embodiment 1, wherein the formulation is free of biocides.
  • Embodiment 3 The formulation according to Embodiment 1 or 2, wherein the formulation has a pH from 10 to 12, preferably from 10.5 to 11.5.
  • Embodiment 4 The formulation according to any of the preceding Embodiments, wherein the weight-average particle size of the aqueous polymer dispersion is less than 100 nm, preferably less than 80 nm, or more preferably less than 60 nm, as measured by capillary hydrodynamic fractionation.
  • Embodiment 5 The formulation according to any of the preceding Embodiments, wherein the at least one ethylenically unsaturated strong acid monomer is present in an amount from 0.5 to 5 wt. %, preferably from 0.7 to 4.5 wt. %, more preferably from 0.8 to 4.0 wt. %, most preferably from 1.0 to 3.5 wt. %, based on the weight of all monomers used in producing the polymer.
  • Embodiment 6 The formulation according to any of the preceding Embodiments, wherein the at least one ethylenically unsaturated strong acid monomer comprises a sulfonic acid or a salt thereof.
  • Embodiment 7 The formulation according to any of the preceding Embodiments, wherein the at least one ethylenically unsaturated strong acid monomer comprises vinyl sulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid or an alkali metal or ammonium salt thereof.
  • Embodiment 8 The formulation according to any of the preceding Embodiments, wherein the at least one unsaturated strong acid monomer comprises 2-acrylamido-2- methylpropanesulfonic acid or an alkali metal or ammonium salt thereof.
  • Embodiment 9 The formulation according to any of the preceding Embodiments, wherein the ethylenically unsaturated weak acid monomer is present in an amount from 1 to 10 wt. %, preferably from 1.5 to 8 wt. %, more preferably from 2 to 7 wt. %, most preferably from 2.5 to 6 wt. %, based on the weight of all monomers used in producing the polymer.
  • Embodiment 10 The formulation according to any of the preceding Embodiments, wherein the at least one ethylenically unsaturated weak acid monomer is selected from the group consisting of an ethylenically unsaturated Cs-Cs monocarboxylic acid, an ethylenically unsaturated C4-Cs dicarboxylic acid, an ethylenically unsaturated C4-Cs dicarboxylic acid anhydride, and combinations thereof.
  • the at least one ethylenically unsaturated weak acid monomer is selected from the group consisting of an ethylenically unsaturated Cs-Cs monocarboxylic acid, an ethylenically unsaturated C4-Cs dicarboxylic acid, an ethylenically unsaturated C4-Cs dicarboxylic acid anhydride, and combinations thereof.
  • Embodiment 11 The formulation according to any of the preceding Embodiments, wherein the at least one ethylenically unsaturated weak acid monomer comprises methacrylic acid, acrylic acid, or combinations thereof.
  • Embodiment 12 The formulation according to any of the preceding Embodiments, wherein the ethylenically unsaturated weak acid monomer comprises at least two ethylenically unsaturated weak acid monomers.
  • Embodiment 13 The formulation according to any of the preceding Embodiments, wherein the polymer is additionally formed from at least one hard block-building monomer having a glass transition temperature of the corresponding homopolymer of greater than 25°C and at least one soft block-building monomer having a glass transition temperature of the corresponding homopolymer of less than 25°C.
  • Embodiment 14 The formulation according to Embodiment 13, wherein the hard block-building monomer comprises styrene.
  • Embodiment 15 The formulation according to Embodiment 13, wherein the hard block-building monomer comprises methyl methacrylate and styrene.
  • Embodiment 16 The formulation according to any of claims 13-15, wherein the soft block-building monomer comprises 2-ethylhexyl acrylate.
  • Embodiment 17 The formulation according to any of the preceding claims, wherein the monomer mixture used to form the polymer does not comprise methacrylamide and/or acrylamide.
  • Embodiment 18 The formulation according to any of the preceding Embodiments, wherein the glass transition temperature of the polymer is 15°C or lower, preferably from -15°C to 10°C, more preferably from -10 to 5°C, as determined by differential scanning calorimetry according to ISO 16805 (2005).
  • Embodiment 19 The formulation according to any of the preceding Embodiments, wherein the formulation has a minimum film forming temperature of less than 5°C, preferably less than 1°C.
  • Embodiment 20 The formulation according to any of the preceding Embodiments, where the aqueous polymer dispersion has a Total Volatile Organic Compound (TVOC) content less than 1800 ppm, preferably less than 1500 ppm, more preferably less than 1000 ppm, as determined by gas chromatography according to ISO 11890-2 (2020).
  • TVOC Total Volatile Organic Compound
  • Embodiment 21 The formulation according to any of the preceding Embodiments, wherein the formulation is free of organic solvent, plasticizer, and/or coalescent agent.

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

Abstract

L'invention concerne des formulations d'apprêt de pénétration ou de teinture à bois stables. La formulation peut comprendre a) une dispersion aqueuse de polymère comprenant un polymère produit par polymérisation en émulsion initiée par voie radicalaire d'au moins un monomère acide fort éthyléniquement insaturé ayant un pKa inférieur à 4 (dans de l'eau à 20 °C) et d'au moins un monomère acide faible éthyléniquement insaturé ayant un pKa égal ou supérieur à 4 (dans de l'eau à 20 °C) ; et b) au moins un silicate de métal alcalin soluble dans l'eau, au moins un siliconate d'alkyle de métal alcalin ou de métal alcalino-terreux soluble dans l'eau, ou un mélange de ceux-ci.
PCT/US2021/050072 2021-09-13 2021-09-13 Teinture à bois et apprêts de pénétration comprenant des dispersions aqueuses à faible teneur en cov WO2023038642A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1297079A1 (fr) 2000-06-21 2003-04-02 DEUTSCHE AMPHIBOLIN-WERKE VON ROBERT MURJAHN GmbH + Co. KG Peinture de dispersion exempte de conservateur
US6756459B2 (en) 2000-09-28 2004-06-29 Rohm And Haas Company Binder compositions for direct-to-metal coatings
US7285590B2 (en) 2003-11-13 2007-10-23 Hexion Specialty Chemicals, Inc. Aqueous dispersions containing multi-stage emulsion polymers
US7789959B2 (en) 2004-05-12 2010-09-07 Celanese Emulsions Gmbh Coating agents that are devoid of preservatives, method for their production and use thereof
DE102014013455A1 (de) 2014-09-17 2016-03-31 Diessner GmbH & Co KG Lack- und Farbenfabrik Topf-Konservierungsmittelfreie Dispersionsfarbe auf Siliconatbasis
WO2019108175A1 (fr) * 2017-11-29 2019-06-06 Celanese International Corporation Dispersions polymères exemptes de biocides et d'ammoniac
WO2020180616A1 (fr) * 2019-03-06 2020-09-10 Celanese International Corporation Utilisation de dispersions aqueuses de copolymère dans des compositions de revêtement aqueux sans conservateur
US20210269653A1 (en) * 2018-06-28 2021-09-02 Basf Se Aqueous dispersions and emulsion paints comprising ethylhexyl acrylate-butyl acrylate-styrene copolymers

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1297079A1 (fr) 2000-06-21 2003-04-02 DEUTSCHE AMPHIBOLIN-WERKE VON ROBERT MURJAHN GmbH + Co. KG Peinture de dispersion exempte de conservateur
US6756459B2 (en) 2000-09-28 2004-06-29 Rohm And Haas Company Binder compositions for direct-to-metal coatings
US7285590B2 (en) 2003-11-13 2007-10-23 Hexion Specialty Chemicals, Inc. Aqueous dispersions containing multi-stage emulsion polymers
US7789959B2 (en) 2004-05-12 2010-09-07 Celanese Emulsions Gmbh Coating agents that are devoid of preservatives, method for their production and use thereof
DE102014013455A1 (de) 2014-09-17 2016-03-31 Diessner GmbH & Co KG Lack- und Farbenfabrik Topf-Konservierungsmittelfreie Dispersionsfarbe auf Siliconatbasis
WO2019108175A1 (fr) * 2017-11-29 2019-06-06 Celanese International Corporation Dispersions polymères exemptes de biocides et d'ammoniac
US20210002506A1 (en) 2017-11-29 2021-01-07 Celanese International Corporation Biocide- and ammonia-free polymer dispersions
US20210269653A1 (en) * 2018-06-28 2021-09-02 Basf Se Aqueous dispersions and emulsion paints comprising ethylhexyl acrylate-butyl acrylate-styrene copolymers
WO2020180616A1 (fr) * 2019-03-06 2020-09-10 Celanese International Corporation Utilisation de dispersions aqueuses de copolymère dans des compositions de revêtement aqueux sans conservateur

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