WO2022151949A1 - 一种水性聚氨酯丙烯酸酯乳液及其应用 - Google Patents

一种水性聚氨酯丙烯酸酯乳液及其应用 Download PDF

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Publication number
WO2022151949A1
WO2022151949A1 PCT/CN2021/141098 CN2021141098W WO2022151949A1 WO 2022151949 A1 WO2022151949 A1 WO 2022151949A1 CN 2021141098 W CN2021141098 W CN 2021141098W WO 2022151949 A1 WO2022151949 A1 WO 2022151949A1
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WIPO (PCT)
Prior art keywords
water
urethane acrylate
acrylate emulsion
emulsion according
oligomer
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PCT/CN2021/141098
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English (en)
French (fr)
Inventor
吕波
王玉平
余立刚
彭富亮
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浙江佑谦特种材料有限公司
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Priority to US18/272,120 priority Critical patent/US11965055B2/en
Publication of WO2022151949A1 publication Critical patent/WO2022151949A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
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    • C—CHEMISTRY; METALLURGY
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    • C08F2/00—Processes of polymerisation
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    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
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    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • 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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/105—Esters of polyhydric alcohols or polyhydric phenols of pentaalcohols
    • 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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/6715—Unsaturated monofunctional alcohols or amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
    • C09D5/022—Emulsions, e.g. oil in water
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • the invention relates to the technical field of coatings, in particular to a water-based polyurethane acrylate emulsion and a water-based matte paint prepared therefrom.
  • the water-based polyurethane acrylate emulsion is a water-based resin obtained by dispersing with water instead of a solvent.
  • This emulsion is environmentally friendly because water is used instead of the solvent.
  • the preparation of matte paint with water-based polyurethane acrylate emulsion can reduce environmental pressure.
  • this matte paint can combine the excellent abrasion resistance, adhesion and flexibility of polyurethane with the weather resistance and protection of acrylic. lightness.
  • the water-based matte powder paint prepared by using conventional water-based urethane acrylates has rough appearance and poor matte powder fineness, which limits its application.
  • the purpose of the present invention is to improve the deficiencies of the prior art.
  • the present invention proposes a water-based polyurethane acrylate emulsion.
  • the raw materials used in the emulsion are high molecular components and thus have good compatibility.
  • the matte paint prepared from the emulsion has sufficient hardness, good abrasion resistance, and fineness of the matte powder paint.
  • an aqueous urethane acrylate emulsion is characterized in that, in parts by weight, it comprises the following raw material components: urethane acrylate prepolymer, and urethane acrylate oligomer.
  • the water-based polyurethane acrylate emulsion according to the second aspect of the present invention is characterized in that the polyurethane acrylate prepolymer comprises the following raw material components: oligomer diol, polyisocyanate, and a second UV-curable monomer body.
  • Both the urethane acrylate prepolymer and the urethane acrylate oligomer have a certain chain length and molecular structure. Good mechanical strength, good wear resistance.
  • the water-based urethane acrylate emulsion adopts urethane acrylate prepolymer with low organic solvent content, which provides hydrophilicity and environmental protection.
  • the water-based polyurethane acrylate emulsion according to the third aspect of the present invention is characterized in that, in parts by weight, the polyurethane acrylate prepolymer includes the following raw material components:
  • the second UV-curable monomer is 40-60.
  • the water-based polyurethane acrylate emulsion according to the fourth aspect of the present invention is characterized in that it further comprises the following raw material components: a first UV-curable monomer, and water.
  • the first UV-curable monomer can provide more functionality, ensure the crosslinking degree of the waterborne polyurethane acrylate emulsion curing, and further improve the abrasion resistance.
  • both the first UV-curable monomer and the second UV-curable monomer are acrylates.
  • Unsaturated acrylate compounds include: trimethylolpropane acrylate, pentaerythritol tri or tetraacrylate (PETA), dipentaerythritol penta or hexaacrylate (DPHA) and their modified compounds, hydroxyethyl acrylate (HEA), acrylic acid At least one of hydroxypropyl acrylate (HPA), hydroxybutyl acrylate (HBA), hydroxyethyl methacrylate (HEMA), and hydroxypropyl methacrylate (HMPA).
  • PETA pentaerythritol tri or tetraacrylate
  • DPHA dipentaerythritol penta or hexaacrylate
  • HPA hydroxyethyl acrylate
  • HPA hydroxyethyl acrylate
  • HBA hydroxybutyl acrylate
  • HEMA hydroxyethyl methacrylate
  • HMPA hydroxypropyl methacrylate
  • the acrylate is pentaerythritol triacrylate or pentaerythritol tetraacrylate (PETA), dipentaerythritol pentaacrylate (DPHA) and its modified compounds, dipentaerythritol hexaacrylate, and hydroxyethyl acrylate (HEA). one or more.
  • PETA pentaerythritol triacrylate or pentaerythritol tetraacrylate
  • DPHA dipentaerythritol pentaacrylate
  • HSA hydroxyethyl acrylate
  • the raw material components of the urethane acrylate oligomer include diisocyanate and acrylate.
  • the aqueous polyurethane acrylate emulsion according to the fifth aspect of the present invention is characterized in that,
  • the number-average molecular weight of the urethane acrylate prepolymer is 2000-5000, and the functionality is 6-10;
  • the number-average molecular weight of the urethane acrylate oligomer is 1000-2000, and the functionality is 3-10;
  • the functionality of the first UV-curable monomer is 3-6.
  • the functionality refers to the number of functional groups participating in the UV curing reaction, that is, unsaturated double bonds, which affect the curing and cross-linking degree of the paint; the greater the functionality, the higher the curing cross-linking degree, which is beneficial to improve the cured paint film. Abrasion resistance, but coatings with excessive functionality are not suitable for thick coatings, and their thick coatings are prone to cracking. Therefore, selecting polymers and monomers with appropriate functionality and controlling the ratio of each component will help Improve the performance of water-based polyurethane acrylate emulsion.
  • the water-based polyurethane acrylate emulsion according to the sixth aspect of the present invention is characterized in that, in parts by weight, it comprises the following raw material components:
  • the water-based polyurethane acrylate emulsion according to the seventh aspect of the present invention is characterized in that, in parts by weight, it comprises the following raw material components:
  • the water-based polyurethane acrylate emulsion according to the eighth aspect of the present invention is characterized in that the molar ratio of the polyurethane acrylate oligomer to the first UV-curable monomer is 0.03 to 1.05: 1.
  • the water-based urethane acrylate emulsion according to the ninth aspect of the present invention is characterized in that the molar ratio of the urethane acrylate oligomer to the first UV-curable monomer is 0.30-0.75:1.
  • the oligomer diol is selected from one of polyoxypropylene diol, polyoxyethylene diol, polyadipate diol, polytetrahydrofuran ether alcohol, polycarbonate diol and polyester diol. one or more; and
  • the polyisocyanate is selected from diisocyanates, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI), diphenylmethane diisocyanate ( MDI), one or more of toluene diisocyanate (TDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI) trimer.
  • diisocyanates isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI), diphenylmethane diisocyanate ( MDI), one or more of toluene diisocyanate (TDI), 4,4'-dicyclohexylmethane diisocyanate (HMDI) trimer.
  • IPDI is
  • the nonionic oligomer diol includes polyethylene oxide diol and its derivatives, and the molecular weight is 200-2000 g/mol; more preferably, polyethylene oxide diol with a molecular weight of 1000 g/mol.
  • the polyisocyanate is selected from diisocyanate, more preferably one or both of isophorone diisocyanate (IPDI) and 4,4'-dicyclohexylmethane diisocyanate (HMDI).
  • IPDI isophorone diisocyanate
  • HMDI 4,4'-dicyclohexylmethane diisocyanate
  • a preparation method of an aqueous polyurethane acrylate emulsion is characterized in that, comprises the following steps:
  • the non-ionic polyurethane and the second UV-curable monomer are mixed and reacted to obtain a polyurethane acrylate prepolymer;
  • the urethane acrylate prepolymer, the urethane acrylate oligomer and the first ultraviolet curing monomer are mixed and dispersed in water to obtain an aqueous urethane acrylate emulsion.
  • a polymerization inhibitor is added during the reaction of the nonionic polyurethane and the acrylate. Inhibitors prevent synthetic urethane acrylates from gelling.
  • the polymerization inhibitor is one or more of p-methoxyphenol, p-hydroxyanisole, p-tert-butylcatechol, and tert-butyl-p-benzoquinone.
  • a water-based matte paint is characterized by comprising the water-based polyurethane acrylate emulsion according to any one of claims 1 to 11.
  • the water-based polyurethane acrylate emulsion of the present invention is a water-based UV-curable non-ionic polyurethane acrylate emulsion, which reduces the usage amount of the organic solvent and obtains the water-based polyurethane acrylate emulsion with low VOCs content. It endows the emulsion with excellent matte powder encapsulation performance, and the obtained matte powder paint has good fineness; the emulsion improves the high wear resistance of the emulsion from the perspectives of resin synthesis and emulsification components, and solves the problem of poor emulsion compatibility. The problem.
  • Step 1 dehydrate the non-ionic oligomer diol in a vacuum at a temperature of 70 to 140 ° C for 30 to 180 minutes, and test the moisture of the oligomer diol to ensure that its moisture is ⁇ 0.2wt%; 40 ⁇ 70 °C, add polyisocyanate and catalyst, heat up to the material temperature of 60 ⁇ 85 °C, keep the temperature for 60 ⁇ 180min to reach the specified amount of NCO, to obtain non-ionic polyurethane;
  • Step 2 Cool down to a material temperature of 40-70°C, add unsaturated acrylate, a polymerization inhibitor and a catalyst to the nonionic polyurethane obtained in step 1, heat up to a material temperature of 60-85°C, and keep the temperature for 60-240min , to obtain a nonionic urethane acrylate prepolymer.
  • a water-based polyurethane acrylate emulsion the preparation method of which is as follows:
  • Step 1 Mix the water-based UV-curable urethane acrylate prepolymer, the UV-curable oligomer, the UV-curable diluent monomer, etc., and stir and disperse at 200-1000 r/min until the mixture is uniform to obtain a mixture;
  • Step 2 under the condition of stirring and dispersing at 600-2500 r/min, adding deionized water of a specified quality for emulsification to obtain a highly wear-resistant water-based polyurethane acrylate emulsion.
  • the urethane acrylate prepolymer, urethane acrylate oligomer, and trimethylolpropane triacrylate were stirred and dispersed at 1000 r/min for 30 min to be uniformly mixed; the rotational speed was set to 1500 r/min min, adding water for stirring and emulsification to obtain an aqueous polyurethane acrylate emulsion.
  • the physical and chemical properties of the obtained aqueous polyurethane acrylate emulsion were tested, and the results are shown in Table 3.
  • the obtained water-based high-gloss coating was sprayed on a transparent PC board with a film thickness of 10-15 ⁇ m, baked at 60° C. for 10 min, and cured into a film with 800 mj/cm 2 of photo-curing machine energy.
  • the RCA (abrasion resistance) of the paint film was tested, and the results are shown in Table 4.
  • the obtained water-based matte paint was sprayed on a black ABS or black PC+ABS board with a film thickness of 15-20 ⁇ m, baked at 60° C. for 10 min, and cured with a light curing machine energy of 800 mj/cm 2 . Observe and test the adhesion, matte fineness, blooming condition and hardness of the paint film. The results are shown in Table 4.
  • the catalyst selected in the present invention is organic bismuth.
  • waterborne polyurethane dispersion 7230 (Allnex Resin Co., Ltd., USA) and water-based polyurethane dispersion RA7011 (Mitsui Resin Co., Ltd., Japan) replaced the water-based polyurethane acrylate emulsion in Examples 1 to 3 to prepare water-based high-gloss paint and water-based matte paint, and sprayed them Curing was carried out on the same substrate, and the performance test was carried out, and the results are shown in Table 4.
  • Example 1 Example 2
  • Example 3 Polyoxyethylene glycol, molecular weight 1000g/mol 20 16 16 Polycarbonate diol, molecular weight 1000g/mol 20 16 16 isophorone diisocyanate 13 11 11 Pentaerythritol triacrylate 0 16 0 Dipentaerythritol pentaacrylate 47 41 57 organic bismuth 0.1 0.1 0.1 p-hydroxyanisole 0.05 0.05 0.05 0.05 0.05 0.05 0.05
  • Example 1 Example 2
  • Example 3 urethane acrylate prepolymer 26
  • 26 26
  • Polyurethane acrylate oligomer 6 12
  • Pentaerythritol triacrylate 18 12 4 water 50 50 50
  • Emulsion appearance Visual inspection
  • Viscosity GB Bruce Instrument 16# rotor@200rpm
  • test methods used are:
  • Pendulum hardness Pendulum hardness tester

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Abstract

一种水性聚氨酯丙烯酸酯乳液，包括以下原料组分：聚氨酯丙烯酸酯预聚体，以及聚氨酯丙烯酸酯低聚物；经紫外线固化后，水性聚氨酯丙烯酸酯乳液具有较好的机械强度，耐磨性能好，所制成的哑光涂料固化后细腻度好。

Description

一种水性聚氨酯丙烯酸酯乳液及其应用 技术领域
本发明涉及涂料技术领域，特别涉及水性聚氨酯丙烯酸酯乳液及其制成的水性哑光漆。
背景技术
在涂料中，哑光漆是相对于高光漆而言，光泽度相对降低的漆，通常哑光漆60度角的光泽度在20以下。哑光漆具有外观柔和、质感性强等特点，在3C电子领域、化妆品等高端领域受到重视并得到广泛应用，其中，高耐磨哑光漆更是受到市场的青睐。此外，随着近年来环保力度的加大，加快了高耐磨水性哑光漆的发展。
水性聚氨酯丙烯酸酯乳液是用水代替溶剂进行分散得到的水性树脂。因为用水代替了溶剂，这种乳液的环保性好。用水性聚氨酯丙烯酸酯乳液制备哑光漆，可以减轻环保压力，此外，这种哑光漆可以兼具聚氨酯优异的耐磨性、粘接性和柔韧性，同时又拥有丙烯酸酯的耐候性和保光性。但是，使用常规水性聚氨酯丙烯酸酯制得的水性哑粉漆，其表观粗糙，哑粉细腻度不佳，限制了其应用。
另一方面，为了提高哑光漆膜的耐磨性，有些现有技术(例如中国专利申请公开CN108531042A和CN107446484A等)提出，在制备哑光漆的过程中向其中引入二氧化硅无机物成分。然而，作为无机物的二氧化硅与高分子组分之间有相容性隐患，限制了该类耐磨哑粉漆在更多项目中的应用。
因此，现有的水性哑光漆技术，无论是从哑光细腻度、还是在耐磨性上，都尚不能满足漆膜产品的外观要求和实用性(例如耐磨)的要求，存在很大的待改进空间。
发明内容
本发明的目的是改进现有技术的不足之处，为了实现这个技术目的，本发明提出了一种水性聚氨酯丙烯酸酯乳液，该乳液所用原料均为高分子 组分因而相容性好，用该乳液制备的哑光漆具备足够的硬度，耐磨性好，同时哑粉漆的细腻度好。
根据本发明的一个方面，一种水性聚氨酯丙烯酸酯乳液，其特征在于，按重量份计，包括以下原料组分：聚氨酯丙烯酸酯预聚体，以及，聚氨酯丙烯酸酯低聚物。
根据本发明的第二方面的水性聚氨酯丙烯酸酯乳液，其特征在于，所述聚氨酯丙烯酸酯预聚体包括以下原料组分：低聚物二元醇，多异氰酸酯，以及，第二紫外光固化单体。
上述各组分之间能够产生协同作用或增效作用，聚氨酯丙烯酸酯预聚体和聚氨酯丙烯酸酯低聚物均具有一定的链长和分子结构，经紫外线固化后的水性聚氨酯丙烯酸酯乳液具有较好的机械强度，耐磨性能好。
此外，水性聚氨酯丙烯酸酯乳液采用有机溶剂含量少的聚氨酯丙烯酸酯预聚体，提供亲水性且绿色环保。
根据本发明的第三方面的水性聚氨酯丙烯酸酯乳液，其特征在于，按重量份计，所述聚氨酯丙烯酸酯预聚体包括以下原料组分：
低聚物二元醇            30～60
多异氰酸酯              5～20
第二紫外光固化单体      40～60。
上述原料合成的聚氨酯丙烯酸酯预聚体未经自乳化或分散于互不相溶的液体中，与聚氨酯丙烯酸酯低聚物和第一紫外光固化单体的相溶性好。
根据本发明的第四方面的水性聚氨酯丙烯酸酯乳液，其特征在于，还包括以下原料组分：第一紫外光固化单体，以及，水。
第一紫外光固化单体能够提供较多的官能度，保证水性聚氨酯丙烯酸酯乳液固化的交联度，进一步提升耐磨性。
可选的，所述第一紫外光固化单体和所述第二紫外光固化单体均为丙烯酸酯。
不饱和丙烯酸酯化合物包括：三羟甲基丙烷丙烯酸酯、季戊四醇三或四丙烯酸酯(PETA)、双季戊四醇五或六丙烯酸酯(DPHA)及其改性化合物，丙烯酸羟乙酯(HEA)、丙烯酸羟丙酯(HPA)、丙烯酸羟丁酯(HBA)、甲基丙烯酸羟乙酯(HEMA)、甲基丙烯酸羟丙酯(HMPA)中的至少一种。
优选的，所述丙烯酸酯为季戊四醇三丙烯酸酯或季戊四醇四丙烯酸酯 (PETA)、双季戊四醇五丙烯酸酯(DPHA)及其改性化合物、双季戊四醇六丙烯酸酯、丙烯酸羟乙酯(HEA)中的一种或多种。
可选的，所述聚氨酯丙烯酸酯低聚物的原料组分包括二异氰酸酯和丙烯酸酯。
根据本发明的第五方面的水性聚氨酯丙烯酸酯乳液，其特征在于，
所述聚氨酯丙烯酸酯预聚体的数均分子量为2000～5000，官能度为6～10；
所述聚氨酯丙烯酸酯低聚物的数均分子量为1000～2000，官能度为3～10；
所述第一紫外光固化单体的官能度为3～6。
所述官能度指参与紫外光固化反应的官能团数目，即不饱和双键，其影响涂漆的固化交联度；官能度越大，固化交联度越高，有利于提升固化后漆膜的耐磨性，但官能度过大的涂料不适用于厚涂，其厚涂的漆膜容易开裂，因此，选择具有适宜官能度的聚合物与单体且控制各组分的比例，有助于提高水性聚氨酯丙烯酸酯乳液的使用性能。
根据本发明的第六方面的水性聚氨酯丙烯酸酯乳液，其特征在于，按重量份计，包括以下原料组分：
Figure PCTCN2021141098-appb-000001
根据本发明的第七方面的水性聚氨酯丙烯酸酯乳液，其特征在于，按重量份计，包括以下原料组分：
Figure PCTCN2021141098-appb-000002
为了兼顾耐磨性能与细腻度，根据本发明第八方面的水性聚氨酯丙烯酸酯乳液，其特征在于，所述聚氨酯丙烯酸酯低聚物与第一紫外光固化单体的摩尔比为0.03～1.05:1。
根据本发明的第九方面的水性聚氨酯丙烯酸酯乳液，其特征在于，所 述聚氨酯丙烯酸酯低聚物与第一紫外光固化单体的摩尔比为0.30～0.75:1。
根据本发明的第十方面的水性聚氨酯丙烯酸酯乳液，其特征在于，
所述低聚物二元醇选自聚氧化丙烯二醇、聚氧化乙烯二醇、聚己二酸二元醇、聚四氢呋喃醚醇、聚碳酸脂二元醇、聚酯二元醇中的一种或多种；以及
所述多异氰酸酯选自二异氰酸酯，异佛尔酮二异氰酸酯(IPDI)、六亚甲基二异氰酸酯(HDI)、4,4'-二环己基甲烷二异氰酸酯(HMDI)、二苯甲烷二异氰酸酯(MDI)、甲苯二异氰酸酯(TDI)、4,4'-二环己基甲烷二异氰酸酯(HMDI)三聚体中的一种或多种。
作为优选，非离子低聚物二元醇中包含聚氧化乙烯二醇及其衍生物，分子量为200-2000g/mol；更为优选分子量为1000g/mol的聚氧化乙烯二醇。
作为优选，多异氰酸酯选用二异氰酸酯，更优选异佛尔酮二异氰酸酯(IPDI)、4,4'-二环己基甲烷二异氰酸酯(HMDI)中的一种或两种。
根据本发明的第十一方面，一种水性聚氨酯丙烯酸酯乳液的制备方法，其特征在于，包括以下步骤：
将低聚物二元醇和多异氰酸酯混合反应，制得非离子型聚氨酯；
所述非离子型聚氨酯和第二紫外光固化单体混合反应，得到聚氨酯丙烯酸酯预聚体；
将所述聚氨酯丙烯酸酯预聚体、聚氨酯丙烯酸酯低聚物与第一紫外光固化单体混合后分散在水中，得到水性聚氨酯丙烯酸酯乳液。
可选的，在所述非离子型聚氨酯和丙烯酸酯反应过程中加入阻聚剂。阻聚剂可以防止合成的聚氨酯丙烯酸酯胶化。
可选的，所述的阻聚剂为对甲氧基苯酚、对羟基苯甲醚、对叔丁基邻苯二酚、特丁基对苯醌中的一种或多种。
根据本发明的第十二方面，一种水性哑光漆，其特征在于，包括权利要求1～11任一项所述的水性聚氨酯丙烯酸酯乳液。
与现有技术相比，本申请至少具有以下技术效果之一：
与现有技术相比，本发明的水性聚氨酯丙烯酸酯乳液，该乳液为水性紫外光固化非离子聚氨酯丙烯酸酯乳液，减少了有机溶剂的使用量，制得低VOCs含量的水性聚氨酯丙烯酸酯乳液，赋予了乳液优异的哑粉包裹性能，制得的哑粉漆哑粉细腻度佳；该乳液同时从树脂合成、乳化组分两个 角度提升了乳液的高耐磨特性，解决了乳液相容性差的问题。
一种非离子聚氨酯丙烯酸酯预聚体的制备方法：
步骤1：将非离子低聚物二元醇在70～140℃温度下真空脱水30～180min，并测试低聚物二元醇的水分，保证其水分≤0.2wt％；降温至料温温度为40～70℃，加入多异氰酸酯和催化剂，升温至料温为60～85℃，保温60～180min至达到指定量的NCO，得到非离子聚氨酯；
步骤2：降温至料温为40～70℃，向步骤1中得到的非离子聚氨酯中加入不饱和丙烯酸酯、阻聚剂和催化剂，升温至料温为60～85℃，保温60～240min后，得到非离子聚氨酯丙烯酸酯预聚体。
一种水性聚氨酯丙烯酸酯乳液，该乳液的制备方法如下：
步骤1：将水性紫外光固化聚氨酯丙烯酸酯预聚体、紫外光固化低聚物、紫外光固化稀释单体等混合，在200～1000r/min下搅拌分散至混合均匀，得到混合物；
步骤2：在600～2500r/min搅拌分散的条件下，加入指定质量的去离子水进行乳化，得到高耐磨水性聚氨酯丙烯酸酯乳液。
具体实施方式
下面结合具体实施方式对本申请所述的技术方案做进一步的说明，但本申请不仅限于此。
实施例1～3
1、水性聚氨酯丙烯酸酯乳液的制备
(1)聚氨酯丙烯酸酯预聚体的制备
按重量份计，原料组分配比如表1所示，将聚氧乙烯二醇和聚碳酸酯二醇加入到带有机械搅拌、温度计及真空装置的玻璃反应釜中，在100℃料温、0.09Mpa真空条件下脱水60min，并测试低聚物二元醇的水分，保证其水分≤0.2wt％；降温至料温温度为50℃，加入异佛尔酮二异氰酸酯和有机铋，升温至料温为80℃，保温120min至指定残余-NCO为7.5wt％；降温至料温为50℃，继续加入不饱和丙烯酸酯、有机铋和对羟基苯甲醚，升温至料温为80℃，保温120min至残余-NCO为0.1wt％，制得聚氨酯丙烯酸酯预聚体。
(2)水性聚氨酯丙烯酸酯乳液的制备
按表2中的原料组分配比，将聚氨酯丙烯酸酯预聚体、聚氨酯丙烯酸酯低聚物、三羟甲基丙烷三丙烯酸酯在1000r/min下搅拌分散30min至混合均匀；设置转速为1500r/min，加入水进行搅拌乳化，得到水性聚氨酯丙烯酸酯乳液。测试得到的水性聚氨酯丙烯酸酯乳液的理化性质，结果见表3。
2、水性哑光漆的制备
按重量份计，将44份水性聚氨酯丙烯酸酯乳液置于PE杯中，开启分散机，转速调整为1500r/min，边分散边往乳液中加入8份水开稀，然后依次加入1份光引发剂1173、0.1份润湿剂BYK346、0.1份流平剂BYK162和2份丙二醇甲醚，最后在1500r/min条件下继续搅拌分散15min后，400目滤布过滤得到水性高光涂料。
将得到的水性高光涂料喷涂在透明PC板上，膜厚10-15μm，60℃烘烤10min，800mj/cm 2光固机能量进行固化成膜。测试漆膜的RCA(耐磨)，结果如表4所示。
在上述水性高光涂料中加入2.2份哑粉(东曹1011)，在1500r/min条件下继续搅拌分散15min后，200目滤布过滤得到水性哑光涂料。
将得到的水性哑光涂料喷涂在黑色ABS或黑色PC+ABS板上，膜厚15-20μm，60℃烘烤10min，800mj/cm 2光固机能量，进行固化。观察并测试漆膜的附着力、哑粉细腻度、发花状况和硬度，结果如表4所示。
本发明选用的催化剂为有机铋。
对比例1～2
分别采用水性聚氨酯分散体
Figure PCTCN2021141098-appb-000003
7230(美国湛新树脂有限公司)和水性聚氨酯分散体RA7011(日本三井树脂有限公司)替代实施例1～3中的水性聚氨酯丙烯酸酯乳液，制备水性高光涂料和水性哑光漆，并将其喷涂在相同基材上进行固化，进行性能测试，结果见表4。
表1、本发明实施例的聚氨酯丙烯酸酯预聚体的原料组分
组分 实施例1 实施例2 实施例3
聚氧化乙烯二醇，分子量1000g/mol 20 16 16
聚碳酸酯二元醇，分子量1000g/mol 20 16 16
异佛尔酮二异氰酸酯 13 11 11
季戊四醇三丙烯酸酯 0 16 0
双季戊四醇五丙烯酸酯 47 41 57
有机铋 0.1 0.1 0.1
对羟基苯甲醚 0.05 0.05 0.05
表2、本发明的水性聚氨酯丙烯酸酯乳液的原料组分
组分 实施例1 实施例2 实施例3
聚氨酯丙烯酸酯预聚体 26 26 26
聚氨酯丙烯酸酯低聚物 6 12 20
季戊四醇三丙烯酸酯 18 12 4
水 50 50 50
表3、本发明水性聚氨酯丙烯酸酯乳液的理化性能
理化性能 测试结果
外观 乳白泛蓝光
固含 45～50％
粘度(cP@25℃) 50～500
pH值 5～8
粒径(nm) 80～200
所用测试方法为：
乳液外观：目测
固含：国标
粘度：国标布鲁斯仪器16#转子@200rpm
pH值：国标pH计
粒径：DLS散射
表4、本发明实施例及对比例的水性哑光漆的性能测试结果
测试项目 实施例1 实施例2 实施例3 对比例1 对比例2
附着力 5B 5B 5B 5B 5B
哑光细腻度 优 优 优 一般 一般
漆膜发花状况 无 无 无 轻微 轻微
三菱铅笔硬度 H 2H 3H 2H H
摆杆硬度(次) 235 241 249 229 215
RCA次数(次) 101 159 230 89 75
所用测试方法为：
附着力：百格法
哑粉细腻度、漆膜发花状况：目视
三菱铅笔硬度：国标
摆杆硬度：摆杆硬度计
RCA：纸带摩擦测试仪(对于测试RCA的试样制备，在水性哑光漆的制备中，按重量份计，将44份水性聚氨酯丙烯酸酯乳液和一定量水性丙烯酸树脂置于PE杯中，后续操作与前文所述相同。加入水性丙烯酸树脂是为了减少RCA的测试次数，如果不加水性丙烯酸树脂，单独测乳液的RCA次数太高)。
通过表4可以看出，与采用市售水性聚氨酯分散体制成的对比例1-2相比，本发明实施例1-3的水性聚氨酯丙烯酸酯乳液在制成哑光漆膜后，哑光细腻度好，不发花，硬度高。
上述对实施例的描述是为了便于该技术领域的普通技术人员能理解和使用发明，本申请所属领域的技术人员还可以对上述实施方式进行适当的变更和修改。因此，本申请并不局限于上面揭示和描述的具体实施方式，对本发明的一些修改和变更也应当落入本申请的权利要求的保护范围内。

Claims (12)

  1. 一种水性聚氨酯丙烯酸酯乳液，其特征在于，包括以下原料组分：聚氨酯丙烯酸酯预聚体，以及，聚氨酯丙烯酸酯低聚物。
  2. 根据权利要求1所述的水性聚氨酯丙烯酸酯乳液，其特征在于，所述聚氨酯丙烯酸酯预聚体包括以下原料组分：低聚物二元醇，多异氰酸酯，以及，第二紫外光固化单体。
  3. 根据权利要求2所述的水性聚氨酯丙烯酸酯乳液，其特征在于，按重量份计，所述聚氨酯丙烯酸酯预聚体包括以下原料组分：
    低聚物二元醇               30～60
    多异氰酸酯                 5～20
    第二紫外光固化单体         40～60。
  4. 根据权利要求2所述的水性聚氨酯丙烯酸酯乳液，其特征在于，还包括以下原料组分：第一紫外光固化单体，以及，水。
  5. 根据权利要求4所述的水性聚氨酯丙烯酸酯乳液，其特征在于，
    所述聚氨酯丙烯酸酯预聚体的数均分子量为2000～5000，官能度为6～10；
    所述聚氨酯丙烯酸酯低聚物的数均分子量为1000～2000，官能度为3～10；
    所述第一紫外光固化单体的官能度为3～6。
  6. 根据权利要求4所述的水性聚氨酯丙烯酸酯乳液，其特征在于，按重量份计，包括以下原料组分：
    Figure PCTCN2021141098-appb-100001
    Figure PCTCN2021141098-appb-100002
  7. 根据权利要求4所述的水性聚氨酯丙烯酸酯乳液，其特征在于，按重量份计，包括以下原料组分：
    Figure PCTCN2021141098-appb-100003
  8. 根据权利要求4所述的水性聚氨酯丙烯酸酯乳液，其特征在于，所述聚氨酯丙烯酸酯低聚物与第一紫外光固化单体的摩尔比为0.03～1.05:1。
  9. 根据权利要求8所述的水性聚氨酯丙烯酸酯乳液，其特征在于，所述聚氨酯丙烯酸酯低聚物与第一紫外光固化单体的摩尔比为0.30～0.75:1。
  10. 根据权利要求2所述的水性聚氨酯丙烯酸酯乳液，其特征在于，
    所述低聚物二元醇选自聚氧化丙烯二醇及其衍生物、聚氧化乙烯二醇及其衍生物、聚己二酸二元醇、聚四氢呋喃醚醇、聚碳酸脂二元醇、聚酯二元醇中的一种或多种；以及
    所述多异氰酸酯选自二异氰酸酯，异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、二苯甲烷二异氰酸酯、甲苯二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯三聚体中的一种或多种。
  11. 权利要求1～10任一项所述的水性聚氨酯丙烯酸酯乳液的制备方法，其特征在于，包括以下步骤：
    将低聚物二元醇和多异氰酸酯混合反应，制得非离子型聚氨酯；
    所述非离子型聚氨酯和第二紫外光固化单体混合反应，得到具有亲水特征的聚氨酯丙烯酸酯预聚体；
    将所述聚氨酯丙烯酸酯预聚体、聚氨酯丙烯酸酯低聚物与第一紫外光固化单体混合后分散在水中，得到水性聚氨酯丙烯酸酯乳液。
  12. 一种水性哑光漆，其特征在于，包括权利要求1～11任一项所述的水性聚氨酯丙烯酸酯乳液。
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