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WO2024234438A1 - Latex aqueux et composition aqueuse de revêtement à cpv élevée formulée à partir de celui-ci - Google Patents

Latex aqueux et composition aqueuse de revêtement à cpv élevée formulée à partir de celui-ci Download PDF

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Publication number
WO2024234438A1
WO2024234438A1 PCT/CN2023/101534 CN2023101534W WO2024234438A1 WO 2024234438 A1 WO2024234438 A1 WO 2024234438A1 CN 2023101534 W CN2023101534 W CN 2023101534W WO 2024234438 A1 WO2024234438 A1 WO 2024234438A1
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Prior art keywords
ethylenically unsaturated
aqueous
aqueous latex
acid
coating composition
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PCT/CN2023/101534
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English (en)
Inventor
Xiaorui CHEN
Yu Zhang
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Guangdong Huarun Paints Co Ltd
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Guangdong Huarun Paints Co Ltd
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Publication of WO2024234438A1 publication Critical patent/WO2024234438A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present application relates to an aqueous latex and an aqueous coating composition formulated therefrom, and more specifically, to an aqueous latex suitable for formulating an aqueous coating composition with high PVC and excellent freeze-thaw stability.
  • aqueous coating compositions with high pigment volume concentration are increasingly used in various fields, especially in the field of construction, encompassing a wide range of aqueous coating composition from exterior to interior paints.
  • PVC pigment volume concentration
  • the storage stability (especially freeze-thaw stability) of an aqueous coating composition is a very important parameter in determining the application range of the aqueous coating composition.
  • the winter temperature is far below 0°C and can even be as low as -40°C.
  • the aqueous coating composition will gel and is difficult to be recovered from the aggregation or agglomeration state where the gel occurred, thereby not meeting actual application requirements. Therefore, it is particularly important to obtain an aqueous coating composition with excellent freeze-thaw stability.
  • the present application in one aspect provides an aqueous latex comprising polymer particles formed by emulsion polymerization of a monomer mixture comprising an ethylenically unsaturated monomer capable of providing steric hindrance, wherein the ethylenically unsaturated monomer capable of providing steric hindrance has a moiety containing 16 to 38 ethylene oxide (-CH2CH2O-) repeating units and an aliphatic hydrophobic end containing at least 16 carbon atoms.
  • the ethylenically unsaturated monomer capable of providing steric hindrance has a moiety containing 18 to 36, preferably 20 to 30 ethylene oxide (-CH2CH2O-) repeating units and an aliphatic hydrophobic end containing 16 to 20 carbon atoms.
  • the present application in another aspect provides an aqueous coating composition comprising the above aqueous latex.
  • the aqueous coating composition has a Pigment Volume Concentration (PVC) of at least 50%.
  • the aqueous coating composition has a Pigment Volume Concentration (PVC) in the range of 55%to 70%.
  • aqueous coating compositions formulated therefrom even those having a high pigment volume concentration (PVC) , have excellent freeze-thaw stability and are substantially free of volatile organic compounds.
  • PVC pigment volume concentration
  • the aqueous coating compositions formed therefrom can provide coatings with significantly improved scrub resistance, which was not expected prior to the present application.
  • compositions that comprises “an” additive can be interpreted to mean that the composition includes “one or more” additives.
  • compositions are described as having, including, or comprising specific components or fractions, or where processes are described as having, including, or comprising specific process steps
  • compositions or processes as disclosed herein may further comprise other components or fractions or steps, whether or not, specifically mentioned in the present application, as along as such components or steps do not affect the basic and novel characteristics of the present application, but it is also contemplated that the compositions or processes may consist essentially of, or consist of, the recited components or steps.
  • ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
  • ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited.
  • within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.
  • ethylenically unsaturated monomer capable of providing steric hindrance refers to a functional monomer having a specific structure, which provides a steric hindrance through the interaction of an aliphatic hydrophobic end and an ethylene oxygen hydrophilic chain attached thereto with the polymer backbone formed from the polymerization of a monomer mixture containing the monomer.
  • the ethylenically unsaturated monomer of the present application capable of providing steric hindrance have a hydrophilic chain with a specific number of ethylene oxygen (EO) and a hydrophobic end with a specific number of carbon atoms, wherein the hydrophilic chain is sandwiched between the polymer backbone formed therefrom and the hydrophobic chain.
  • EO ethylene oxygen
  • the hydrophobic chain of the ethylenically unsaturated monomer would readily attach to the polymer backbone formed from the polymerization of a monomer mixture containing the monomer based on the principle of similar compatibility, leaving the hydrophilic chain exposed, thus forming a hindrance ring.
  • post-crosslinkable ethylenically unsaturated monomer refers to an ethylenically unsaturated monomer that is capable of participating in emulsion polymerization reaction and from which an aqueous latex can be further crosslinked with other components of a composition containing the aqueous latex by other reactive functional groups, such as active hydrogen, before or after film formation.
  • post-crosslinkable ethylenically unsaturated monomer include, but are not limited to, ethylenically unsaturated monomer having an acetoacetoxy functional group, such as alkyl acetoacetate (meth) acrylate.
  • the phrase “substantially free " of a post-crosslinkable ethylenically unsaturated monomer means that said post-crosslinkable ethylenically unsaturated monomer is not intentionally added to a monomer mixture used to form an aqueous latex.
  • the phrase "substantially free" of a post-crosslinkable ethylenically unsaturated monomer mean that a monomer mixture comprises less than 0.5 %by weight, more preferably less than 0.2 %by weight, more preferably less than 0.1 %by weight of said post-crosslinkable ethylenically unsaturated monomer based on the total weight of the monomer mixture.
  • volatile organic compounds as used herein means any organic compound having a soften point lower than room temperature and a boiling point in the range of 50 to 260°C at a standard pressure of 101.3 kPa.
  • VOCs volatile organic compounds
  • pigment volume concentration refers to the ratio of the volume of the particulate solids (i.e. non-binder solids) to the total volume of polymeric particles (binder solids) and particulate solids present in the coating composition. PVC reflects the volume relationship between the particulate solids and the polymeric particles in the coating film. Where the binder and non-binder solids include multiple components, ideal mixing is assumed and all volumes are additive. Briefly, according to the present application, pigment volume concentration (PVC) can be expressed by the following equation:
  • the volume of a substance can be determined as the ratio of its mass to its density.
  • the volume of particulate solids may be the sum of volumes of individual particulate solids wherein the volume of each particulate solid is determined as the ratio of mass to density of such particulate solid.
  • the volume of polymeric particles may be determined as the ratio of the mass of non-volatile solids of the aqueous latex to the density of the polymeric particles, under the assumption that the density of polymeric particles is 1 g/cm 3 .
  • aqueous latex comprising polymer particles formed by emulsion polymerization of a monomer mixture.
  • aqueous latex refers to a dispersion of polymer particles dispersed in an aqueous medium in the presence of necessary emulsifiers and/or dispersing stabilizers.
  • Aqueous dispersion of such polymers may be made, for example, by an emulsion polymerization process.
  • Suitable emulsion polymerization processes are known to those of ordinary skill in the art and typically comprise the steps of dispersing polymerizable monomers into an emulsion in water in the presence of suitable emulsifiers and/or dispersing stabilizers and with the aid of agitation, and initiating the polymerization of the monomers, for example by the addition of suitable initiators.
  • an aqueous emulsion of polymeric particles can be a dispersion of polymeric particles dispersed in an aqueous medium in the presence of the necessary emulsifier and/or dispersion stabilizer.
  • suitable monomer or monomer mixture can be selected as desired.
  • the monomer mixture for forming an aqueous latex comprises an ethylenically unsaturated monomer capable of providing steric hindrance, wherein the ethylenically unsaturated monomer capable of providing steric hindrance has a moiety containing 16 to 38 ethylene oxide (-CH2CH2O-) repeating units and an aliphatic hydrophobic end containing at least 16 carbon atoms.
  • the ethylenically unsaturated monomer capable of providing steric hindrance refers to a functional monomer having a specific structure, which provides a steric hindrance through the interaction of an aliphatic hydrophobic end and an ethylene oxygen hydrophilic chain attached thereto with the polymer backbone formed from polymerization of a monomer mixture containing the monomer.
  • the ethylenically unsaturated monomer capable of providing steric hindrance has a moiety containing 18 to 36, preferably 20 to 30 ethylene oxide (-CH2CH2O-) repeating units and an aliphatic hydrophobic end containing 16 to 20 carbon atoms.
  • an ethylenically unsaturated monomer comprises a hydrophilic chain containing a smaller number of ethylene oxygen (EO)
  • the hydrophilic chain is too short to be coiled into a ring when its hydrophobic chain is attached to the polymer backbone formed therefrom, and thus ethylenically unsaturated monomer cannot provide proper steric hindrance
  • an ethylenically unsaturated monomer comprises a hydrophilic chain containing a greater number of ethylene oxygen (EO)
  • EO ethylene oxygen
  • the selection of the number of ethylene oxygen (EOs) in the hydrophilic chain and the number of carbon atoms in the hydrophobic chain are important elements to ensure that the ethylenically unsaturated monomer can provide steric hindrance.
  • the ethylenically unsaturated monomer having a hydrophilic chain with the above-mentioned number of ethylene oxygen repeating units and a hydrophobic end with the above-mentioned number of carbon atoms are appropriate.
  • said ethylenically unsaturated monomer capable of providing steric hindrance has the following structure:
  • R represents an aliphatic hydrophobic end containing at least 16 carbon atoms, preferably represents an aliphatic hydrophobic end containing 16-20 carbon atoms
  • n represents an integer from 16 to 38, preferably represents an integer from 18 to 36, more preferably represents an integer from 20 to 30.
  • the amount of the above-described ethylenically unsaturated monomer capable of providing steric hindrance may be in the range of 0.6 to 1.5 %by weight, preferably in the range of 0.6 to 1.3 %by weight, relative to the total weight of the monomer mixture used to prepare the aqueous latex. It was surprisingly found by the inventors of the present application that the application of a lower amount of the above-mentioned ethylenically unsaturated monomer capable of providing steric hindrance enables the aqueous latex formed therefrom to have excellent freeze-thaw stability, which was hardly foreseen prior to the present application.
  • the amount of the above-mentioned ethylenically unsaturated monomer capable of providing steric hindrance can be in the range of 0.8 to 1.2 %by weight relative to the total amount of the monomer mixture used to prepare the aqueous latex.
  • the monomer mixture used to prepare the aqueous latex may comprise ethylenically unsaturated monomer having carboxylic acid functional group.
  • the presence of such olefinically unsaturated monomer having carboxylic acid functional groups additionally provides a stable aqueous latex.
  • the above ethylenically unsaturated monomer include acrylic acid, methacrylic acid, ⁇ -acryloxypropionic acid, ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, ⁇ -phenylacrylic acid, cinnamic acid, chlorocinnamic acid, itaconic aicd, maleic acid, and combinations thereof.
  • acrylic acid, methacrylic acid or its combination is used as an example of the above ethylenically unsaturated monomer having carboxylic acid functional groups.
  • the amount of the above-mentioned ethylenically unsaturated monomer having carboxylic acid functional group may be in the range of 0 to 10%by weight, preferably in the range of 0.1 to 5%by weight, more preferably in the range of 0.5 to 2%by weight with respect to the weight of the monomer mixture used for preparing the aqueous latex.
  • a suitable amount of the ethylenically unsaturated monomer having carboxylic acid functional group is advantageous for obtaining a stable aqueous latex.
  • the amount of the aforementioned ethylenically unsaturated monomer having carboxylic acid functional group is preferably in the range of 0.8 to 1.5%by weight with respect to the weight of the monomer mixture used in the preparation of the aqueous latex.
  • the monomer mixture used to prepare the aqueous latex may comprise other ethylenically unsaturated monomers.
  • other ethylenically unsaturated monomers include any radically polymerizable ethylenically unsaturated compound other than above mentioned ethylenically unsaturated monomer capable of providing steric hindrance, and ethylenically unsaturated monomer having carboxyl functional group.
  • examples of other ethylenically unsaturated monomers include styrenes (such as styrene, alpha-methyl styrene, vinyl toluene, vinyl naphthalene) , halogenated olefins (such as vinyl chloride, vinylidene chloride, vinyl fluoride, tetrafluoroethylene, hexafluoropropylene) , allyl ethers (such as allyl anisole) , vinyl acetate, vinyl versatate (such as commercially available vinyl versatate VeoVa 10) , (meth) acrylamide, acrylonitriles (such as acrylonitrile, methacrylonitrile) , allyl urea, C 1 -C 16 alkyl (meth) acrylate, hydroxyl C 1 -C 16 alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate and its combination.
  • styrenes, alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates, (meth) acrylamide, vinyl acetate, (meth) acrylonitrile, allyl urea or combinations thereof are selected as other ethylenically unsaturated monomers. More preferably, styrenes, C1-16 alkyl (meth) acrylates, hydroxy C1-16 alkyl (meth) acrylates, or combinations thereof are used.
  • C1-16 alkyl (meth) acrylates include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, or mixtures thereof.
  • other ethylenically unsaturated monomers include styrene, methyl (meth) acrylate, butyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate or combinations thereof.
  • the amount of other ethylenically unsaturated monomers mentioned above can be adjusted according to actual demands (such as Tg, mechanical strength, and the like) .
  • the proportion of other ethylenically unsaturated compounds in the monomer mixture used for preparing the aqueous latex is generally high.
  • the monomer mixture comprises 90 to 98.9%by weight, preferably 92 to 98%by weight, more preferably 92 to 96%by weight of the above-mentioned other ethylenically unsaturated monomers relative to the weight of the monomers mixture used to form the aqueous latex.
  • the monomer mixture used to form the aqueous latex is free of a post-crosslinkable ethylenically unsaturated monomer.
  • a post-crosslinkable ethylenically unsaturated monomer is usually added to the monomer mixture used for an aqueous latex so that the resulting aqueous latex can be crosslinked with other components of the coating composition formulated therefrom prior to and after film formation, thereby improving the scrub resistance of the resulting coating.
  • the aqueous latex according to the present application is free of a post-crosslinkable ethylenically unsaturated monomer and that the coatings formed by the aqueous coating compositions formulated therefrom still have a significantly improved scrub resistance, which was unexpected.
  • the aqueous latex according to the present application is prepared by (1) mixing a monomer mixture, a chain transfer agent, and part of an emulsifier with deionized water to obtain a pre-emulsion, and mixing part of a thermal initiator with deionized water to obtain a thermal initiator solution; (2) at a temperature in the range of 70-90°C, adding the pre-emulsion and the thermal initiator solution simultaneously dropwise to a mixture of the remaining emulsifier, remaining thermal initiator and deionized water, thereby obtaining a first reaction solution; (2) at a temperature in the range of 50-60°C, to the first reaction solution adding a redox initiation system formed of a second initiator, a reducing agent and optionally a metal catalyst, to further polymerize the remaining monomer mixture to obtain a second reaction solution; and (4) neutralizing the second reaction solution, and filtering, thereby obtaining said aqueous latex.
  • examples of useful emulsifiers include any well-known anionic surfactants, nonionic surfactants, or combinations thereof.
  • suitable surfactants for emulsion polymerization are disclosed in McCutcheon's Detergents and Emulsifers (MC Publishing Co., Glen Rock, N.J. ) .
  • Other types of stabilizing agents can also be used, such as protective colloids.
  • a combination of an anionic surfactant and a nonionic surfactant is used.
  • Anionic surfactants include aliphatic carboxylates, aliphatic sulfonates, aliphatic sulfates, and aliphatic phosphates.
  • alkali metals such as Na, K or Li
  • alkaline earth metal salts such as Ca or Ba
  • aliphatic sulphonates preferably alkali dodecylsulphonates, more preferably sodium dodecylsulphate (SDSs)
  • SDSs sodium dodecylsulphate
  • Nonionic surfactants include alkyl phenol polyoxyethylene ethers, fatty alcohol polyoxyethylene ethers.
  • alkylphenol polyoxyethylene ethers are used.
  • octylphenol polyoxyethylene ether (OP-10) is used.
  • the emulsifier is present in an amount of 0.1-0.5%by weight relative to the total feed.
  • thermal initiator can be used to initiate the polymerization reaction.
  • thermal initiators include persulfates such as ammonium persulfate or alkali persulfate (including potassium, sodium or lithium) ; peroxides such as cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dioctyl peroxide, tert-butyl pervalerate, tert-butyl perisononate, tert-butyl peroctoate, tert-butyl perneodecanoate, peroxyl di (2-ethylhexyl) dicarbonate, bis (isotridecyl) peroxydicarbonate; azo compounds such as azobis (isobutyronitrile) and azobis (4-cyanovaleric acid) .
  • a water-soluble thermal initiator persulfate for example ammonium persulfate, potassium persulfate, and sodium persulfate is used.
  • the thermal initiator is present in an amount of 0.1-0.5%by weight relative to the total feed.
  • a chain transfer agent is added.
  • the chain transfer agent is one or more selected from isopropanol, halogenated compounds, linear or branched C4-C22 alkyl mercaptan, mercaptoalkanoic acid, and alkyl mercaptoalkanoate, preferably linear or branched C4-C22 alkyl mercaptan, more preferably n-dodecyl mercaptan and tert-dodecyl mercaptan.
  • the chain transfer is present in an amount of 0.1-1%by weight relative to the total feed.
  • Methods to add the chain transfer agent (s) include one or more additions, which are continuous, linear, non-linear, over most or all of the entire reaction period.
  • a redox initiation system is used for the further polymerization of the remaining monomer mixture, said redox initiation system comprising a second initiator, a reducing agent and optionally a metal catalyst.
  • the second initiator examples include, but not limited to one or more of peroxides, for example, hydrogen peroxide, sodium peroxide, potassium peroxide, t-butyl hydroperoxide, t-amyl hydroperoxide, cumene hydroperoxide; persulfates, for example ammonium, potassium and sodium persulfates; perborates; and perphosphorate salts, preferably peroxides, more preferably hydrogen peroxide, t-butyl hydroperoxide, t-amyl hydroperoxide, and cumene hydroperoxide.
  • the second initiator is present in an amount of 0.01-0.5%by weight relative to the total feed.
  • Example of the reducing agent include, but not limited to one or more of sodium formaldehyde hyposulfite, sodium sulfite, sodium bisulfite, sodium thiosulfate, sodium sulfide, sodium hydrosulfide, sodium bisulfite, formamidine sulfite, hydroxymethanesulfonic acid, acetone bisulfite, ethanolamine, ethanoic acid, hydrated glycolic acid, ascorbic acid, isoascorbic acid, lactic acid, malic acid, 2-hydroxy-2-sulfoacetic acid, tartaric acid, and salts of said acids; preferably one or more of sodium bisulfite, ascorbic acid, and isoascorbic acid.
  • the reducing agent is present in an amount of 0.01-0.5%by weight relative to the total feed.
  • the metal catalyst is one or more selected from iron, copper, manganese, silver, platinum, vanadium, nickel, chromium, palladium and cobalt catalysts, preferably iron catalysts.
  • the metal catalyst is present in an amount of 0.001-1%by weight relative to the total feed.
  • reaction conditions such as reaction temperature and stirring speed can be determined empirically by those skilled in the art.
  • the reaction temperature is maintained below 100°C, more preferably 30-95°C, most preferably 50-90°C throughout the reaction process.
  • the polymerization reaction is preferably carried out at a pH of 4-8.
  • the aqueous latex obtained by the above method has a solid content of 45-55%.
  • polymer particles of the aqueous latex thus obtained have a particle size in the range of 100 nm to 400 nm.
  • the size of said polymer particles can be measured by a Z-average particle size known in the art, which refers to size of the dispersed phase as determined by dynamic light scattering, for example using a Marvlen Zetasizer 3000HS microscopic particle size analyzer.
  • said polymer particles have a particle size of 100-300 nm, preferably 120-280 nm, more preferably 120-250 nm.
  • aqueous coating compositions formulated using such aqueous latexes prepared from a monomer mixture comprising an ethylenically unsaturated monomer capable of providing steric hindrance can achieve excellent freeze-thaw stability and low or zero VOC emission even at a high pigment volume concentration (PVC) , which was difficult to achieve prior to the present application. Therefore, another aspect of the present application provides an aqueous coating composition comprising the above-mentioned aqueous latex according to the present application.
  • the amount of said aqueous latex can vary over a wide range, the total amount of which can be in the range of about 10%to about 30%by weight relative to the total weight of said coating composition, for example in the range of about 10-14.99%by weight, or in the range of 15-24.99%by weight, or in the range of 25-35%by weight.
  • the aqueous coating compositions of the present application may further comprise one or more pigment/filler.
  • pigment/filler refers to any volume extender suitable for the coating, which may be in organic or inorganic form such as particles. There is no particular restriction on the shape of the particles, which may have any suitable shape.
  • the average particle size of the pigment/filler can vary over a wide range, for example from about 10 nm to about 50 ⁇ m.
  • Some pigment/filler impart one or more desired properties to the composition and/or the coating formed from the composition in addition to acting as a volume extender for the coating. For example, some pigment/filler may impart a desired color to the composition and to the coating obtained from the composition.
  • the pigment/filler may also be referred to as a "pigment” .
  • Some pigments/fillers can improve chemical and/or physical properties, in particular mechanical properties of the coating obtained from the composition. In this case, such fillers are also referred to as "reinforcing fillers” .
  • Suitable exemplary pigments/fillers include, for example, diatomaceous earth, kaolin, titanium oxide, calcium carbonate, talc, barium sulfate, magnesium aluminum silicate, silicon oxide and any combination thereof.
  • the filler may include diatomaceous earth, rutile titanium dioxide, calcined kaolin, calcium carbonate, talc, or combinations thereof.
  • BLR688 purchased from Baililian, China may be used; as an example of calcined kaolin, BR80 purchased from Shanxi Jinyang Kaolin Co may be used; as an example of talc, S-1250 purchased from Yuanlei, Foshan, China can be used; as an example of calcium carbonate, GF168 purchased from Guangfu Building Materials, China can be used; and as an example of diatomaceous earth, C499 purchased from Celite, USA can be used.
  • the total amount of pigment/filler can vary in a wide range, for example from about 30 wt%to about 70 wt%, preferably from about 45 wt%to about 70 wt%, more preferably from 50 wt%to 60 wt%, relative to the total weight of said coating composition.
  • the aqueous coating composition may optionally further comprise additional additives commonly used in aqueous coating compositions that do not adversely affect the coating composition or the cured coating obtained therefrom.
  • additional additives include, for example, those agents that will improve processing or manufacturing properties of the composition, enhance aesthetics of the composition, or improve specific functional properties or characteristics of the coating composition or the cured composition therefrom, such as adhesion to the substrate.
  • additives examples include carriers, emulsifiers, pigments, anti-migration agents, antimicrobial agents, chain expanders, lubricants, wetting agents, biocides, plasticizers, defoamers, colorants, waxes, antioxidants, anti-corrosion agents, flow control agents, thixotropic agents, dispersants, adhesion promoters, UV stabilizers, thickeners, defoamers, pH adjusters, silane coupling agents, high boiling point film forming aids, or combinations thereof.
  • the content of each optional ingredient is sufficient to serve its intended purpose, but preferably such content does not adversely affect the coating composition or the cured coating obtained therefrom.
  • said aqueous coating composition may further comprise as additional additives thickeners, wetting agents, dispersants, defoamers, pH adjusters, silane coupling agents, film forming aids having a boiling point above 270°C, fungicides, anti-mold agents, or any combination thereof.
  • a high PVC aqueous coating composition obtained by using the above-mentioned aqueous emulsions according to the present application as film-forming resins and incorporating into them a considerable amount (even up to 70%by weight) of pigment/filler still have an excellent freeze-thaw stability while still keeping substantially VOC-free, which was hardly expected prior to the present application.
  • the aqueous coating composition according to the present application are able to withstand three cycles of freeze-thaw testing, said freeze-thaw testing being determined according to GB/T9756-2018.
  • the aqueous coating composition of the present application can even have an excellent scrub resistance at a low ratio of film-forming resin: filler. It is well known that high filler loadings in coating compositions will reduce the scrub resistance of the resulting coating, because the high filler loadings enable the coating formed therefrom to have a rough, even porous surface. However, it was found by the inventors of the present application that the aqueous coating composition formed by adopting the above-mentioned aqueous latex according to the present application as a film-forming resin may form a paint film having an excellent scrub resistance even at high PVC.
  • the inventors speculate that the excellent scrub resistance of the present application may be attributed to the fact that the ethylenically unsaturated monomer capable of providing steric hindrance has an aliphatic hydrophobic end having a particular number of carbon atoms.
  • the aqueous coating composition comprises relative to total weight of the aqueous coating composition, i) 10-30%by weight of the aqueous latex according to the present application; ii) 30-70%by weight of pigment and/or filler; iii) 28-35%by weight deionized water; and iv) 0-10%by weight of additional additives including one or more of thickeners, dispersants, defoamers, wetting agents, coalescents, mildew inhibitors or preservatives.
  • the preparation of the aqueous coating compositions of the present application can be achieved by any suitable mixing method known to those of ordinary skill in the art.
  • the aqueous coating composition can be made by adding the aqueous latex, filler and additional additives if present to a container and then mixing the resulting mixture until homogeneous.
  • the aqueous coating composition can be made by mixing some of additional additives with a filler and then adding the aqueous latex and the remaining additional additives to form a homogeneous mixture.
  • additional water can be added during the preparation of the aqueous coating composition.
  • aqueous coating compositions of the present application can be coated by conventional methods known to those of ordinary skill in the art.
  • the aqueous coating composition can be applied by spray gun, roller or applicator brush.
  • a coating can be formed by the aqueous coating composition of the present application, which also falls within the scope of protection of the present application.
  • the aqueous coating composition according to the present application is free of VOC by gas chromatography (GC) according to GB 18582-2008.
  • GC gas chromatography
  • the aqueous coating composition according to the present application has a Pigment Volume Concentration (PVC) of at least 50%, preferably in the range of 50%to 70%.
  • PVC Pigment Volume Concentration
  • the aqueous coating composition according to the present application when the aqueous coating composition according to the present application is dried at 25°C for 7 days with a wet film thickness of 200 microns to form a coating, the resulting coating is capable of resisting wipes of 350 or more as measured according to GB/T9756-2018.
  • VOC content is determined by standard gas chromatography method according to GB 18582-2008.
  • Freeze-thaw stability is determined according to the standard test method of GB/T9756-2018.
  • the aqueous coating composition according to the present application was dried at 25°C for 7 days with a wet film thickness of 200 microns to form a coating, and the scrub resistance of the resulting coating was measured according to GB/T9756-2018.
  • a pre-emulsification kettle deionized water, emulsifier, sodium hydroxide, individual monomers and a chain transfer agent were taken to obtain a monomer pre-emulsion.
  • an initiator kettle part of an initiator was put into water to obtain an initiator solution.
  • part of the emulsifier, initiator and deionized water were put into a reaction kettle, and the temperature was raised to 70-90°C.
  • the monomer pre-emulsion and initiator solution were simultaneously put into the reaction kettle at a certain time and temperature at a uniform rate, and an emulsion containing acrylic polymers were obtained by emulsion polymerization.
  • tert-butyl hydroperoxide and reducing agent were added, and the redox initiator system was used to further polymerize the residual monomers, and the pH was adjusted by adding sodium hydroxide as needed, and the aqueous latex was obtained after filtration.
  • the four aqueous latexes prepared above were used as a film-forming resin, to which 60%by weight of pigment/filler relative to the total amount of the aqueous coating compositions and an additional additive were added, thereby formulating white coating compositions 1-4 with a PVC of about 62%.
  • the VOC content of the resulting coating compositions 1-4 were tested to be undetectable.
  • freeze-thaw stability (containing three cycles) of the four coating compositions prepared above and the scrub resistance of the coatings formed from them were tested according to GB/T9756-2018, and the results were summarized in Table 2 below.
  • the new aqueous latex synthesized using an ethylenically unsaturated monomer has a moiety containing a particular number of ethylene oxide (-CH2CH2O-) repeating units and an aliphatic hydrophobic end containing a particular number of carbon atoms enable the formulated aqueous coating compositions with high pigment volume concentration (PVC) with excellent freeze-thaw stability, and the coating formed from such coating composition also have significantly improved scrub resistance.
  • PVC pigment volume concentration
  • aqueous latexes each synthesized using control monomers with more or less ethylene oxygen (EO) repeating monomers cannot achieve the above technical effects.
  • EO ethylene oxygen
  • the invention disclosed illustratively herein may be implemented in the absence of any elements not expressly disclosed herein.
  • present application is described with reference to a large number of embodiments and examples, a person of ordinary skill in the art will be able to recognize that other embodiments can be devised in light of the disclosure of the present application, which does not depart from the scope and spirit of protection of the present application.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente demande concerne un latex aqueux et une composition aqueuse de revêtement à CPV élevée formulée à partir de celui-ci. Le latex aqueux comprend des particules de polymère formées par polymérisation en émulsion d'un mélange de monomères comprenant un monomère éthyléniquement insaturé capable de fournir un encombrement stérique, le monomère éthyléniquement insaturé capable de fournir un encombrement stérique ayant une fraction contenant de 16 à 38 unités récurrentes d'oxyde d'éthylène (-CH2CH2O-) et une extrémité hydrophobe aliphatique contenant au moins 16 atomes de carbone. Les latex aqueux susmentionnés peuvent être formulés avec succès pour former des compositions aqueuses de revêtement ayant une concentration pigmentaire volumique (CPV) élevée et présentant une excellente stabilité au gel-dégel.
PCT/CN2023/101534 2022-06-20 2023-06-20 Latex aqueux et composition aqueuse de revêtement à cpv élevée formulée à partir de celui-ci Ceased WO2024234438A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210695594.7 2022-06-20
CN202210695594.7A CN117304415A (zh) 2022-06-20 2022-06-20 水性胶乳以及由其配制形成的具有高pvc的水性涂料组合物

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WO2024234438A1 true WO2024234438A1 (fr) 2024-11-21

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202017005943U1 (de) * 2017-11-16 2018-01-10 Basf Se (Meth)acrylcopolymerdispersionen und ihre Verwendung als HASE-Verdicker
CN113527695A (zh) * 2021-07-23 2021-10-22 中山市钧纬新材料科技有限公司 一种超支化聚合物水性分散剂的制备方法及应用

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE202017005943U1 (de) * 2017-11-16 2018-01-10 Basf Se (Meth)acrylcopolymerdispersionen und ihre Verwendung als HASE-Verdicker
CN113527695A (zh) * 2021-07-23 2021-10-22 中山市钧纬新材料科技有限公司 一种超支化聚合物水性分散剂的制备方法及应用

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