WO2022165697A1 - Water dispersion for metallic coating material and aqueous metallic coating material - Google Patents

Water dispersion for metallic coating material and aqueous metallic coating material Download PDF

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Publication number
WO2022165697A1
WO2022165697A1 PCT/CN2021/075220 CN2021075220W WO2022165697A1 WO 2022165697 A1 WO2022165697 A1 WO 2022165697A1 CN 2021075220 W CN2021075220 W CN 2021075220W WO 2022165697 A1 WO2022165697 A1 WO 2022165697A1
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WIPO (PCT)
Prior art keywords
mass
coating material
parts
metallic coating
water dispersion
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PCT/CN2021/075220
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French (fr)
Inventor
Soichiro Omizu
Akine MIKAMI
Huashan XIE
Kundi LIANG
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DIC Corp
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DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to JP2023504048A priority Critical patent/JP7338807B2/en
Priority to CN202180090124.1A priority patent/CN116670237A/en
Priority to PCT/CN2021/075220 priority patent/WO2022165697A1/en
Publication of WO2022165697A1 publication Critical patent/WO2022165697A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • 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
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (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
    • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/29—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for multicolour effects
    • 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
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives

Definitions

  • the present invention relates to a water dispersion for a metallic coating material and an aqueous metallic coating material.
  • Metallic coating films formed by coating a coating material are generally used for improving the quality and design of cars.
  • the mainstream metallic coating material is a solvent-based coating material having excellent drying properties, but from consideration of the environment, an aqueous metallic coating material is demanded.
  • the aqueous metallic coating material causes a problem with the orientation of metallic pigments due to the low-rate water drying and thus has the problem of failing to obtain necessary high brightness.
  • a photoluminescent coating material composition containing an acrylic resin, a curing agent, a photoluminescent pigment, and a solvent at a specific ratio is proposed (for example, refer to PTL 1) .
  • the photoluminescent coating material composition has the problem of unsatisfactory lifting resistance.
  • an aqueous material for ametallic coating material having excellent coating film appearance and lifting resistance is required.
  • An object to be solved by the present invention is to provide a water dispersion for a metallic coating material, which can produce a cured coating film having excellent coating film appearance and lifting resistance, and also provide an aqueous metallic coating material containing the water dispersion.
  • a water dispersion for a metallic coating material which contains a specific acrylic polymer produced by itaconic acid as an essential raw material and dispersed in an aqueous medium, can produce a cured coating film having excellent appearance and lifting resistance, leading to the achievement of the present invention.
  • the present invention relates to a water dispersion for a metallic coating material, which contains an acrylic polymer (A) produced by itaconic acid as an essential raw material and dispersed in an aqueous medium (B) , the acid value of the acrylic polymer (A) being 40 to 100mgKOH/g and the average particle diameter of particles formed by the acrylic polymer (A) being 35 nm or less.
  • a water dispersion for a metallic coating material of the present invention can produce a coating film having excellent appearance and lifting resistance and thus can be preferably used for various industrial aqueous coating materials for a vehicle, a building exterior, a bridge, an industrial machinery, a gas tank, a construction machinery, a ship, a plastic, and the like.
  • a water dispersion for a metallic coating material of the present invention is a water dispersion for a metallic coating material, which contains an acrylic polymer (A) produced by itaconic acid as an essential raw material and dispersed in an aqueous medium (B) , the acid value of the acrylic polymer (A) being 40 to 100 mgKOH/g and the average particle diameter of particles formed by the acrylic polymer (A) being 35 nm or less.
  • the acrylic polymer (A) composed of itaconic acid as an essential raw material can be produced by copolymerizing itaconic acid with another unsaturated monomer.
  • Examples of the other unsaturated monomer include styrene and/or styrene derivatives such as styrene, tert-butylstyrene, ⁇ -methylstyrene, vinyltoluene, and the like; alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like; hydroxyl group-containing acrylic monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and the like; g
  • the term " (meth) acrylic acid” represents one or both of methacrylic acid and acrylic acid
  • the term “ (meth) acrylate” represents one or both of methacrylate and acrylate
  • the term “ (meth) acrylamide” represents one or both of methacrylamide and acrylamide.
  • the itaconic acid in unsaturated monomer raw materials of the acrylic polymer (A) is preferably 4%to 12%by mass and more preferably 7%to 12%by mass.
  • a cured coating film having excellent appearance and lifting resistance can be produced by using itaconic acid as an essential raw material of the acrylic polymer (A) , but because the lifting resistance is more improved, the unsaturated monomer raw material preferably contains styrene, and the styrene in the unsaturated monomer raw material is preferably 20%to 50%by mass.
  • a cured coating film having excellent appearance and lifting resistance can be produced by using itaconic acid as an essential raw material of the acrylic polymer (A) , but because the lifting resistance is more improved, the unsaturated monomer raw material preferably contains alkyl (meth) acrylate, and the alkyl (meth) acrylate in the unsaturated monomer raw material is preferably 20%to 70%by mass.
  • a hydroxyl group-containing acrylic monomer is preferably used.
  • the hydroxy group-containing acrylic monomer in the unsaturated monomer raw material of the acrylic polymer (A) is preferably 2%to 10%by mass and more preferably 4%to 8%by mass.
  • the acid value of the acrylic polymer (A) is 40 to 100 mgKOH/g, but is preferably 60 to 100 mgKOH/g because the appearance and lifting resistance of the resultant coating film are more improved.
  • the hydroxyl value of the acrylic polymer (A) is preferably 10 to 50 mgKOH/g and more preferably 20 to 40 mgKOH/g because the appearance and lifting resistance of the resultant coating film are more improved.
  • the weight-average molecular weight of the acrylic polymer (A) is preferably 5,000 to 100,000 and more preferably 10,000 to 50,000 because the coating film appearance and lifting resistance are more improved.
  • the average molecular weight of the present invention is a value in terms of polystyrene based on gel permeation chromatography (abbreviated as "GPC” hereinafter) measurement.
  • Various methods can be used as a method for producing the acrylic polymer (A) , and, for example, a method of polymerizing unsaturated monomer raw materials using a polymerization initiator in an organic solvent can be used.
  • organic solvent examples include aromatic hydrocarbon compounds such as toluene, xylene, and the like; alicyclic hydrocarbon compounds such as cyclohexane, methyl cyclohexane, ethyl cyclohexane, and the like; ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like; ester compounds such as ethyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, and the like; alcohol compounds such as n-butanol, isopropyl alcohol, cyclohexanol, and the like; glycol compounds such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, and the like; aliphatic hydrocarbon compounds such as heptane, hexan
  • polymerization initiator examples include organic peroxides: ketone peroxide compounds such as cyclohexanone peroxide, 3, 3, 5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, and the like; peroxyketal compounds such as 1, 1-bis (tert-butylperoxy) -3, 3, 5-trimethylcyclohexane, 1, 1-bis (tert-butylperoxy) cyclohexane, n-butyl-4, 4-bis (tert-butylperoxy) valerate, 2, 2-bis (4, 4-di-tert-butylperoxycyclohexyl) propane, 2, 2-bis (4, 4-di-tert-amylperoxycyclohexyl) propane, 2, 2-bis (4, 4-di-tert-hexylperoxycyclohexyl) propane, 2, 2-bis (4, 4-di-tert-octylperoxycyclohexyl) propane, 2, 2-bis
  • aqueous medium (B) examples include water, a hydrophilic organic solvent, and a mixture thereof.
  • the hydrophilic organic solvent is preferably a water-miscible organic solvent miscible with water without separating from water and particularly preferably an organic solvent having a water solubility (gram number of an organic solvent dissolved in 100 g of water) of 3 g or more at 25°C.
  • examples of the water-miscible organic solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, 1, 3-butylene glycol-3-monomethyl ether (general name: 3-methoxybutanol) , 3-methyl-3-methoxybutanol (product name: Solfit manufactured by Kuraray Co., Ltd.
  • glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycolmonopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycolmonomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycolmonomethyl ether,
  • the water dispersion for a metallic coating material of the present invention contains the acrylic polymer (A) dispersed in the aqueous medium (B) , and a method for dispersing the acrylic polymer (A) in the aqueous medium (B) is, for example, a phase-transfer emulsification method.
  • the phase-transfer emulsification method is, for example, a method of partially or entirely neutralizing the acid groups in the acrylic polymer (A) by adding a basic compound to the acrylic polymer (A) and then dispersing by adding water.
  • Examples of the basic compound include organic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, N, N-dimethyl ethanolamine, monoalkanolamine such as 2-aminoethanol or the like, diethanolamine, diisopropanolamine, dibutanolamine, and the like; inorganic basic compounds such as ammonia, sodium hydroxide, potassium hydroxide, and the like; quaternary ammonium hydroxides such as tetramethyl ammonium hydroxide, tetra-n-butyl ammonium hydroxide, trimethylbenzyl ammonium hydroxide, and the like; and the like.
  • organic amine and ammonia (ammonia water) are preferably used.
  • These basic compounds can be used alone or in combination of two or more.
  • the amount of the basic compound used is preferably such an amount that the neutralization rate of acid groups possessed by the acrylic polymer (A) is within a range of 50%to 100%. With the neutralization rate set high, the average particle diameter of particles formed by the acrylic polymer (A) can be controlled to be small.
  • the average particle diameter of particles formed by the acrylic polymer (A) in the water dispersion for a metallic coating material of the present invention is 35 nm or less, but is preferably 30 nm or less because the coating film appearance and lifting resistance are more improved.
  • the average particle diameter is a value measured by a method for determining a particle size distribution based on the measurement principle for detecting the dynamically scattered light of particles.
  • the water dispersion for a metallic coating material of the present invention can be mixed with a curding agent during mixing of a coating material.
  • a curding agent examples include a polyisocyanate compound, an amino resin, an epoxy compound, an oxazoline compound, a carbodiimide compound, and the like. Because the appearance of the resultant coating film is more improved, a polyisocyanate compound is preferred.
  • These curing agents can be used alone or in combination of two or more.
  • polyisocyanate compound examples include aromatic diisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, m-xylylene diisocyanate, m-phenylene bis (dimethylmethylene) diisocyanate, and the like; aliphatic or alicyclic diisocyanate compounds such as hexamethylene diisocyanate, lysine diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, 2-methyl-1, 3-diisocyanatohexane, 2-methyl-1, 5-diisocyanatocyclohexane, 4, 4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, and the like.
  • aromatic diisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, m-xylylene diisocyanate, m-pheny
  • polyisocyanate compound examples include an isocyanate group-containing prepolymer produced by addition reaction of the diisocyanate compound described above with a polyhydric alcohol; an isocyanurate ring-containing compound produced by cyclotrimerization of the diisocyanate compound; a polyisocyanate compound having a urea bond or burette bond, produced by reacting the diisocyanate compound with water; a homopolymer of an isocyanate group-containing acrylic monomer such as 2-isocyanatoethyl (meth) acrylate, 3-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate, (meth) acryloyl isocyanate, or the like; an isocyanate group-containing copolymer produced by copolymerizing the isocyanate group-containing acrylic monomer with another acrylic monomer, or a monomer such as a vinyl ester compound, a vinyl ether compound, an aromatic vinyl monomer, a fluoride,
  • the polyisocyanate compound is preferably a water dispersible polyisocyanate produced by modifying the polyisocyanate compound in view of excellent stability and curability and a high degree of freedom of usable life when mixed with the water dispersion for a metallic coating material of the present invention.
  • the polyisocyanate compounds can be used alone or in combination of two or more.
  • the amount of the polyisocyanate compound mixed is such an amount that the equivalent ratio (isocyanate group/hydroxyl group) of isocyanate group in the polyisocyanate compound to hydroxyl group in the acrylic polymer (A) is preferably within a range of 0.5 to 2.0 and more preferably within a range of 0.8 to 1.5.
  • the urethanization reaction can also be performed in the presence of a urethanization catalyst for promoting the progress of the reaction.
  • a urethanization catalyst include amine compounds such as triethylamine and the like; organic tin compounds such as dibutyltin dioctoate, dibutyltin dilaurate, dioctyltin dilaurate, octyltin trilaurate, dioctyltin dineodecanate, dibutyltin diacetate, dioctyltin diacetate, tin dioctylate, and the like; organic metal compounds such as zinc octylate (zinc 2-ethylhexanoate) and the like.
  • An aqueous metallic coating material of the present invention contains a water dispersion for a metallic coating material and a metallic pigment.
  • the metallic pigment include scale-like aluminum, vapor deposited aluminum, aluminum oxide, mica, titanium oxide-coated mica, iron oxide-coated mica, micaceous iron oxide, and the like.
  • the content of the metallic pigment in the solid content of the aqueous metallic coating material is preferably 1%to 30%by mass and more preferably 5%to 25%by mass.
  • the aqueous metallic coating material of the present invention can use, as compounds other than the above, additives such as a defoaming agent, a viscosity modifier, a light stabilizer, a weather stabilizer, a thermal stabilizer, an ultraviolet absorber, an antioxidant, a leveling agent, a pigment dispersant, a thickener, and the like. Also, a pigment other than the metallic pigment can be used.
  • Examples of a method for coating the aqueous metallic coating material of the present invention include methods such as a spray, an applicator, a bar coater, a gravure coater, a roll coater, a comma coater, a knife coater, an air knife coater, a curtain coater, a kiss coater, a shower coater, a wheeler coater, a spin coater, dipping, screen printing, and the like.
  • a method for forming a coating film after coating is, for example, a method of drying within a range of room temperature to 120°C.
  • the present invention is described in further detail below by giving examples.
  • the acid value and hydroxyl value of an acrylic polymer were measured according to JIS test method K 0070-1992.
  • the average particle diameter was measured by using Nanotrac UPA-EX150 manufactured by Nikkiso Co., Ltd. Also, the average molecular weight was measured under the following GPC measurement conditions.
  • Measurement apparatus high-speed GPC apparatus ( "HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured byTosohCorporation were connected in series and used.
  • TKgel G2000 (7.8 mm I.D. ⁇ 30 cm) ⁇ 1
  • RI differential refractometer
  • Injection amount 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 4 mg/mL)
  • Standard sample A calibration curve was formed by using the following monodisperse polystyrene.
  • a monomer mixture solution was prepared by mixing 180 parts by mass of styrene (hereinafter “St” ) , 150 parts by mass of butyl acrylate (hereinafter “BA” ) , 100 parts by mass of n-butyl methacrylate (hereinafter “n-BMA” ) , 30 parts by mass of hydroxyethyl acrylate (hereinafter “HEA” ) , and 75 parts by mass of propylene glycol methyl ether (hereinafter “PGM” ) . Also, an initiator solution was prepared by mixing 17.5 parts by mass of Perbutyl O (hereinafter “P-O” ) and 17.5 parts by mass of PGM.
  • St styrene
  • BA butyl acrylate
  • n-BMA n-butyl methacrylate
  • HOA hydroxyethyl acrylate
  • PGM propylene glycol methyl ether
  • an initiator solution was prepared by mixing 17.5 parts by
  • a monomer mixture solution was prepared by mixing 180 parts by mass of St, 163 parts by mass of BA, 70 parts by mass of n-BMA, 30 parts by mass of HEA, and 75 parts by mass of PGM.
  • an initiator solution was prepared by mixing 17.5 parts by mass of P-O and 17.5 parts by mass of PGM.
  • 19 parts by mass of ITA and 150 parts by mass of PGM were charged, and then the inside of the reactor was heated to 100°C under stirring while nitrogen gas was fed. After heating, 33%by mass of the monomer mixture solution and 33%by mass of the initiator solution were added dropwise into the reactor over 80 minutes.
  • a monomer mixture solution was prepared by mixing 180 parts by mass of St, 150 parts by mass of BA, 100 parts by mass of n-BMA, 30 parts by mass of HEA, 6 parts by mass of methacrylic acid (hereinafter "MAA" ) , and 75 parts by mass of PGM. Also, an initiator solution was prepared by mixing 17.5 parts by mass of P-O and 17.5 parts by mass of PGM. In a 2-liter reactor provided with a stirrer, a thermometer, and a condenser, 12 parts by mass of ITA and 150 parts by mass of PGM were charged, and then the inside of the reactor was heated to 100°C under stirring while nitrogen gas was fed.
  • a monomer mixture solution was prepared by mixing 180 parts by mass of St, 145 parts by mass of BA, 101 parts by mass of n-BMA, 30 parts by mass of HEA, 45 parts by mass of acrylic acid (hereinafter "AA" ) , and 75 parts by mass of PGM.
  • an initiator solution was prepared by mixing 17.5 parts by mass of P-O and 17.5 parts by mass of PGM.
  • a 2-liter reactor provided with a stirrer, a thermometer, and a condenser, 150 parts by mass of PGM was charged, and then the inside of the reactor was heated to 100°C under stirring while nitrogen gas was fed. After heating, the monomer mixture solution and the initiator solution were added dropwise into the reactor over 4 hours.
  • a monomer mixture solution was prepared by mixing 180 parts by mass of St, 150 parts by mass of BA, 100 parts by mass of n-BMA, 30 parts by mass of HEA, and 75 parts by mass of PGM.
  • a 2-liter reactor provided with a stirrer, a thermometer, and a condenser, 40 parts by mass of ITA and 150 parts by mass of PGM were charged, and then the inside of the reactor was heated to 100°C under stirring while nitrogen gas was fed. After heating, a mixture of the monomer mixture solution, 17.5 marts by mass of P-O, and 17.5 parts by mass of PGM was added dropwise into the reactor over 4 hours.
  • a monomer mixture solution was prepared by mixing 180 parts by mass of St, 140 parts by mass of BA, 130 parts by mass of n-BMA, 30 parts by mass of HEA, and 75 parts by mass of PGM.
  • a 2-liter reactor provided with a stirrer, a thermometer, and a condenser, 21 parts by mass of ITA and 150 parts by mass of PGM were charged, and then the inside of the reactor was heated to 100°C under stirring while nitrogen gas was fed. After heating, a mixture of the monomer mixture solution, 17.5 marts by mass of P-O, and 17.5 parts by mass of PGM was added dropwise into the reactor over 4 hours.
  • the aqueous metallic coating material prepared as described above was coated on a plastic material ABS plate by a spray so that the thickness was 15 ⁇ m, set for 5 minutes, and then dried at 80°C for 30 minutes by using a hot-air dryer, forming a 1-coat coating film teat plate having a dry coating film formed thereon.
  • a dilute thinner was prepared by mixing 50 parts by mass of xylene, 30 parts by mass of butyl acetate, 10 parts by mass of propylene glycol monomethyl ether acetate, and 10 parts by mass of ethyl-3-ethoxypropionate. Then, 23 parts by mass of the dilute thinner was mixed with 30 parts by mass of acrylic resin ( "Acrydic A-859-B” manufactured by DIC Corporation) , 13 parts by mass of an isocyanate curing agent ( "Desmodur N-3300" manufactured by Covestro Ltd. ) , and a surface additive ( "BYK-331” manufactured by BYK Chemie Co., Ltd. ) to prepare a clear coating material for 2 coats.
  • acrylic resin "Acrydic A-859-B” manufactured by DIC Corporation
  • 13 parts by mass of an isocyanate curing agent “Desmodur N-3300” manufactured by Covestro Ltd. )
  • a surface additive "BYK-331” manufactured by BYK
  • the aqueous metallic coating material prepared as described above was coated on a plastic material ABS plate by a spray so that the thickness was 15 ⁇ m, and was set for 5 minutes. Then, the clear coating material for 2 coats was coated so that the thickness was 30 ⁇ m, set for 5 minutes, and dried at 80°C for 30 minutes by using a hot-air dryer, forming a 2-coat coating film teat plate having a dry coating film formed thereon.
  • the coating film appearance was evaluated by visually observing the coating film surface of the 1-coat coating film test plate formed as described above according to the following criteria.
  • the lifting resistance was evaluated by visually observing and comparing the surfaces of the 1-coat coating film test plate and 2-coate coating film test plate formed as described above according to the following criteria.
  • Table 1 shows the compositions and evaluation results of the water dispersions for a metallic coating material (1) to (3) and (R1) to (R3) producing as described above.
  • the coating films obtained from the water dispersions for a metallic coating material of Examples 1 to 3 were confirmed to be excellent in coating film appearance and lifting resistance.
  • Comparative Example 1 is an example not using itaconic acid as the essential raw material, and the lifting resistance was confirmed to be unsatisfactory.
  • Comparative Example 2 is an example using an average particle diameter larger than the upper limit of the present invention, and the coating film appearance was confirmed to be unsatisfactory.
  • Comparative Example 3 is an example using the acrylic polymer having an acid value lower than the lower limit of the present invention and an average particle diameter larger than the upper limit of the present invention, and the coating film appearance was confirmed to be unsatisfactory.

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Abstract

The present invention provides a water dispersion for a metallic coating material, including an acrylic polymer (A) composed of itaconic acid as an essential raw material and dispersed in an aqueous medium (B). The acid value of the acrylic polymer (A) is 40 to 100 mgKOH/g, and the average particle diameter of particles formed by the acrylic polymer (A) is 35 nm or less. A cured coating film obtained from the water dispersion for a metallic coating material has excellent lifting resistance and is thus preferably used for a metallic coating material.

Description

WATER DISPERSION FOR METALLIC COATING MATERIAL AND AQUEOUS METALLIC COATING MATERIAL [Technical Field]
The present invention relates to a water dispersion for a metallic coating material and an aqueous metallic coating material.
[Background Art]
Metallic coating films formed by coating a coating material are generally used for improving the quality and design of cars. The mainstream metallic coating material is a solvent-based coating material having excellent drying properties, but from consideration of the environment, an aqueous metallic coating material is demanded. However, the aqueous metallic coating material causes a problem with the orientation of metallic pigments due to the low-rate water drying and thus has the problem of failing to obtain necessary high brightness.
Under these conditions, a photoluminescent coating material composition containing an acrylic resin, a curing agent, a photoluminescent pigment, and a solvent at a specific ratio is proposed (for example, refer to PTL 1) . However, the photoluminescent coating material composition has the problem of unsatisfactory lifting resistance.
Thus, an aqueous material for ametallic coating material having excellent coating film appearance and lifting resistance is required.
[Citation List]
[Patent Literature]
[PTL 1]
Japanese Unexamined Patent Application Publication No. 2006-169416
[Summary of Invention]
[Technical Problem]
An object to be solved by the present invention is to provide a water dispersion for a metallic coating material, which can produce a cured coating film having excellent coating film appearance and lifting resistance, and also provide an aqueous metallic coating material containing the water dispersion.
[Solution to Problem]
As a result of repeated earnest studies for solving the problem, the inventors found that a water dispersion for a metallic coating material, which contains a specific acrylic polymer produced by itaconic acid as an essential raw material and dispersed in an aqueous medium, can produce a cured coating film having excellent appearance and lifting resistance, leading to the achievement of the present invention.
That is, the present invention relates to a water dispersion for a metallic coating material, which contains an acrylic polymer (A) produced by itaconic acid as an essential raw material and dispersed in an aqueous medium (B) , the acid value of the acrylic polymer (A) being 40 to 100mgKOH/g and the average particle diameter of particles formed by the acrylic polymer (A) being 35 nm or less.
[Advantageous Effects of Invention]
A water dispersion for a metallic coating material of the present invention can produce a coating film having excellent appearance and lifting resistance and thus can be preferably used for various industrial aqueous coating materials for a vehicle, a building exterior, a bridge, an industrial machinery, a gas tank, a construction machinery, a ship, a plastic, and the like.
[Description of Embodiments]
A water dispersion for a metallic coating material of the present invention is a water dispersion for a metallic coating material, which contains an acrylic polymer (A) produced by itaconic acid as an essential raw material and dispersed in an aqueous medium (B) , the acid value of the acrylic polymer (A) being 40 to 100 mgKOH/g and the average particle diameter of particles formed by the acrylic polymer (A) being 35 nm or less.
The acrylic polymer (A) composed of itaconic acid as an essential raw material can be produced by copolymerizing itaconic acid with another unsaturated monomer.
Examples of the other unsaturated monomer include styrene and/or styrene derivatives such as styrene, tert-butylstyrene, α-methylstyrene, vinyltoluene, and the like; alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like; hydroxyl group-containing acrylic monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and the like; glycidyl group-containing acrylic monomers such as glycidyl (meth) acrylate and the like; saturated aliphatic carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, and the like; nitrogen atom-containing acrylic monomers such as (meth) acrylamide, N-methylolacrylamide, N-methoxybutylacrylamide, and the like; ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, and the like; ethylenically unsaturated dicarboxylic acids other than itaconic acid, such as maleic acid, fumaric acid, and the like; acid anhydrides of maleic acid, itaconic acid, and the like; monoesters of these acid  anhydrides; and the like. These monomers can be used alone or in combination of two or more.
In the present invention, the term " (meth) acrylic acid" represents one or both of methacrylic acid and acrylic acid, the term " (meth) acrylate" represents one or both of methacrylate and acrylate, and the term " (meth) acrylamide" represents one or both of methacrylamide and acrylamide.
Because coating film appearance and lifting resistance are more improved, the itaconic acid in unsaturated monomer raw materials of the acrylic polymer (A) is preferably 4%to 12%by mass and more preferably 7%to 12%by mass.
A cured coating film having excellent appearance and lifting resistance can be produced by using itaconic acid as an essential raw material of the acrylic polymer (A) , but because the lifting resistance is more improved, the unsaturated monomer raw material preferably contains styrene, and the styrene in the unsaturated monomer raw material is preferably 20%to 50%by mass.
A cured coating film having excellent appearance and lifting resistance can be produced by using itaconic acid as an essential raw material of the acrylic polymer (A) , but because the lifting resistance is more improved, the unsaturated monomer raw material preferably contains alkyl (meth) acrylate, and the alkyl (meth) acrylate in the unsaturated monomer raw material is preferably 20%to 70%by mass.
When the acrylic polymer (A) is cured by reaction with a curing component such as isocyanate or the like, a hydroxyl group-containing acrylic monomer is preferably used.
Because the lifting resistance is more improved, the hydroxy group-containing acrylic monomer in the unsaturated monomer raw  material of the acrylic polymer (A) is preferably 2%to 10%by mass and more preferably 4%to 8%by mass.
The acid value of the acrylic polymer (A) is 40 to 100 mgKOH/g, but is preferably 60 to 100 mgKOH/g because the appearance and lifting resistance of the resultant coating film are more improved.
The hydroxyl value of the acrylic polymer (A) is preferably 10 to 50 mgKOH/g and more preferably 20 to 40 mgKOH/g because the appearance and lifting resistance of the resultant coating film are more improved.
The weight-average molecular weight of the acrylic polymer (A) is preferably 5,000 to 100,000 and more preferably 10,000 to 50,000 because the coating film appearance and lifting resistance are more improved.
The average molecular weight of the present invention is a value in terms of polystyrene based on gel permeation chromatography (abbreviated as "GPC" hereinafter) measurement.
Various methods can be used as a method for producing the acrylic polymer (A) , and, for example, a method of polymerizing unsaturated monomer raw materials using a polymerization initiator in an organic solvent can be used.
Examples of the organic solvent include aromatic hydrocarbon compounds such as toluene, xylene, and the like; alicyclic hydrocarbon compounds such as cyclohexane, methyl cyclohexane, ethyl cyclohexane, and the like; ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like; ester compounds such as ethyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, and the like; alcohol compounds such as n-butanol, isopropyl alcohol, cyclohexanol, and the like;  glycol compounds such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol dimethyl ether, and the like; aliphatic hydrocarbon compounds such as heptane, hexane, octane, mineral turpentine, and the like; and the like. Among these, a water-miscible organic solvent is preferably used because it can be used directly as the aqueous medium (B) . These organic solvents can be used alone or in combination of two or more.
Examples of the polymerization initiator include organic peroxides: ketone peroxide compounds such as cyclohexanone peroxide, 3, 3, 5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, and the like; peroxyketal compounds such as 1, 1-bis (tert-butylperoxy) -3, 3, 5-trimethylcyclohexane, 1, 1-bis (tert-butylperoxy) cyclohexane, n-butyl-4, 4-bis (tert-butylperoxy) valerate, 2, 2-bis (4, 4-di-tert-butylperoxycyclohexyl) propane, 2, 2-bis (4, 4-di-tert-amylperoxycyclohexyl) propane, 2, 2-bis (4, 4-di-tert-hexylperoxycyclohexyl) propane, 2, 2-bis (4, 4-di-tert-octylperoxycyclohexyl) propane, 2, 2-bis (4, 4-di-cumylperoxycyclohexyl) propane, and the like; hydroperoxide compounds such as cumene hydroperoxide, 2, 5-dimethylhexane-2, 5-dihydroperoxidee and the like; dialkyl peroxide compounds such as 1, 3-bis (tert-butylperoxy-m-isopropyl) benzene, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, diisopropylbenzene peroxide, tert-butylcumyl peroxide, di-tert-butylperoxide, and the like; diacylperoxide compounds such as decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2, 4-dichlorobenzolyl peroxide, and the like; and peroxycarbonate compounds such as bis (tert-butylcyclohexyl) peroxydicarbonate and the like; peroxyester compounds such as tert-butylperoxy-2-ethyl hexanoate, tert-amylperoxy-2-ethyl hexanoate, tert-butyl peroxybenzoate, 2, 5-dimethyl-2, 5-di (benzoylperoxy) hexane, and the like; and  azo compounds such as 2, 2'-azobisisobutyronitrile, 2, 2'-azobis (2-methyl) butyronitrile, 1, 1'-azobis (cyclohexane-1-carbonitrile) , and the like. These polymerization initiators can be used alone or in combination of two or more.
Examples of the aqueous medium (B) include water, a hydrophilic organic solvent, and a mixture thereof. The hydrophilic organic solvent is preferably a water-miscible organic solvent miscible with water without separating from water and particularly preferably an organic solvent having a water solubility (gram number of an organic solvent dissolved in 100 g of water) of 3 g or more at 25℃. Examples of the water-miscible organic solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, 1, 3-butylene glycol-3-monomethyl ether (general name: 3-methoxybutanol) , 3-methyl-3-methoxybutanol (product name: Solfit manufactured by Kuraray Co., Ltd. ) , and the like; ketone solvents such as acetone, methyl ethyl ketone, and the like; glycol ether solvents such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycolmonopropyl ether, ethylene glycol monoisopropyl ether, monobutyl ether, diethylene glycolmonomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycolmonomethyl ether, dipropylene glycol dimethyl ether, and the like; and the like. These aqueous media (B) can be used alone or in combination of two or more.
The water dispersion for a metallic coating material of the present invention contains the acrylic polymer (A) dispersed  in the aqueous medium (B) , and a method for dispersing the acrylic polymer (A) in the aqueous medium (B) is, for example, a phase-transfer emulsification method.
The phase-transfer emulsification method is, for example, a method of partially or entirely neutralizing the acid groups in the acrylic polymer (A) by adding a basic compound to the acrylic polymer (A) and then dispersing by adding water.
Examples of the basic compound include organic amines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, butylamine, dibutylamine, tributylamine, N, N-dimethyl ethanolamine, monoalkanolamine such as 2-aminoethanol or the like, diethanolamine, diisopropanolamine, dibutanolamine, and the like; inorganic basic compounds such as ammonia, sodium hydroxide, potassium hydroxide, and the like; quaternary ammonium hydroxides such as tetramethyl ammonium hydroxide, tetra-n-butyl ammonium hydroxide, trimethylbenzyl ammonium hydroxide, and the like; and the like. Among these, an organic amine and ammonia (ammonia water) are preferably used. These basic compounds can be used alone or in combination of two or more.
In addition, because dispersibility and storage stability of the water dispersion are more improved, the amount of the basic compound used is preferably such an amount that the neutralization rate of acid groups possessed by the acrylic polymer (A) is within a range of 50%to 100%. With the neutralization rate set high, the average particle diameter of particles formed by the acrylic polymer (A) can be controlled to be small.
The average particle diameter of particles formed by the acrylic polymer (A) in the water dispersion for a metallic coating material of the present invention is 35 nm or less, but is preferably 30 nm or less because the coating film appearance  and lifting resistance are more improved. In the present invention, the average particle diameter is a value measured by a method for determining a particle size distribution based on the measurement principle for detecting the dynamically scattered light of particles.
The water dispersion for a metallic coating material of the present invention can be mixed with a curding agent during mixing of a coating material. Examples of the curing agent include a polyisocyanate compound, an amino resin, an epoxy compound, an oxazoline compound, a carbodiimide compound, and the like. Because the appearance of the resultant coating film is more improved, a polyisocyanate compound is preferred. These curing agents can be used alone or in combination of two or more.
Examples of the polyisocyanate compound include aromatic diisocyanate compounds such as tolylene diisocyanate, diphenylmethane diisocyanate, m-xylylene diisocyanate, m-phenylene bis (dimethylmethylene) diisocyanate, and the like; aliphatic or alicyclic diisocyanate compounds such as hexamethylene diisocyanate, lysine diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, 2-methyl-1, 3-diisocyanatohexane, 2-methyl-1, 5-diisocyanatocyclohexane, 4, 4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, and the like.
Other usable examples of the polyisocyanate compound include an isocyanate group-containing prepolymer produced by addition reaction of the diisocyanate compound described above with a polyhydric alcohol; an isocyanurate ring-containing compound produced by cyclotrimerization of the diisocyanate compound; a polyisocyanate compound having a urea bond or burette bond, produced by reacting the diisocyanate compound with water; a homopolymer of an isocyanate group-containing acrylic monomer  such as 2-isocyanatoethyl (meth) acrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, (meth) acryloyl isocyanate, or the like; an isocyanate group-containing copolymer produced by copolymerizing the isocyanate group-containing acrylic monomer with another acrylic monomer, or a monomer such as a vinyl ester compound, a vinyl ether compound, an aromatic vinyl monomer, a fluoroolefin, or the like.
The polyisocyanate compound is preferably a water dispersible polyisocyanate produced by modifying the polyisocyanate compound in view of excellent stability and curability and a high degree of freedom of usable life when mixed with the water dispersion for a metallic coating material of the present invention.
The polyisocyanate compounds can be used alone or in combination of two or more.
Because a coating film having high strength can be produced, the amount of the polyisocyanate compound mixed is such an amount that the equivalent ratio (isocyanate group/hydroxyl group) of isocyanate group in the polyisocyanate compound to hydroxyl group in the acrylic polymer (A) is preferably within a range of 0.5 to 2.0 and more preferably within a range of 0.8 to 1.5.
The urethanization reaction can also be performed in the presence of a urethanization catalyst for promoting the progress of the reaction. Examples of the urethanization catalyst include amine compounds such as triethylamine and the like; organic tin compounds such as dibutyltin dioctoate, dibutyltin dilaurate, dioctyltin dilaurate, octyltin trilaurate, dioctyltin dineodecanate, dibutyltin diacetate, dioctyltin diacetate, tin dioctylate, and the like; organic metal compounds such as zinc octylate (zinc 2-ethylhexanoate)  and the like.
An aqueous metallic coating material of the present invention contains a water dispersion for a metallic coating material and a metallic pigment. Examples of the metallic pigment include scale-like aluminum, vapor deposited aluminum, aluminum oxide, mica, titanium oxide-coated mica, iron oxide-coated mica, micaceous iron oxide, and the like.
Because the coating film appearance is more improved, the content of the metallic pigment in the solid content of the aqueous metallic coating material is preferably 1%to 30%by mass and more preferably 5%to 25%by mass.
The aqueous metallic coating material of the present invention can use, as compounds other than the above, additives such as a defoaming agent, a viscosity modifier, a light stabilizer, a weather stabilizer, a thermal stabilizer, an ultraviolet absorber, an antioxidant, a leveling agent, a pigment dispersant, a thickener, and the like. Also, a pigment other than the metallic pigment can be used.
Examples of a method for coating the aqueous metallic coating material of the present invention include methods such as a spray, an applicator, a bar coater, a gravure coater, a roll coater, a comma coater, a knife coater, an air knife coater, a curtain coater, a kiss coater, a shower coater, a wheeler coater, a spin coater, dipping, screen printing, and the like. In addition, a method for forming a coating film after coating is, for example, a method of drying within a range of room temperature to 120℃.
[EXAMPLES]
The present invention is described in further detail below by giving examples. The acid value and hydroxyl value of an acrylic polymer were measured according to JIS test method K  0070-1992. The average particle diameter was measured by using Nanotrac UPA-EX150 manufactured by Nikkiso Co., Ltd. Also, the average molecular weight was measured under the following GPC measurement conditions.
[GPC measurement conditions]
Measurement apparatus: high-speed GPC apparatus ( "HLC-8220GPC" manufactured by Tosoh Corporation) Column: The following columns manufactured byTosohCorporation were connected in series and used.
"TSKgel G5000" (7.8 mm I.D. × 30 cm) × 1
"TSKgel G4000" (7.8 mm I.D. × 30 cm) × 1
"TSKgel G3000" (7.8 mm I.D. × 30 cm) × 1
"TSKgel G2000" (7.8 mm I.D. × 30 cm) × 1
Detector: RI (differential refractometer)
Column temperature: 40℃
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 4 mg/mL)
Standard sample: A calibration curve was formed by using the following monodisperse polystyrene.
(Monodisperse polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation
[EXAMPLE 1: production of water dispersion for metallic coating material (1) ]
A monomer mixture solution was prepared by mixing 180 parts by mass of styrene (hereinafter "St" ) , 150 parts by mass of butyl acrylate (hereinafter "BA" ) , 100 parts by mass of n-butyl methacrylate (hereinafter "n-BMA" ) , 30 parts by mass of hydroxyethyl acrylate (hereinafter "HEA" ) , and 75 parts by mass of propylene glycol methyl ether (hereinafter "PGM" ) . Also, an initiator solution was prepared by mixing 17.5 parts by mass of Perbutyl O (hereinafter "P-O" ) and 17.5 parts by mass of PGM. In a 2-liter reactor provided with a stirrer, a thermometer, and a condenser, 13 parts by mass of itaconic acid (hereinafter "ITA" ) and 150 parts by mass of PGM were charged, and then the inside of the reactor was heated to 100℃ under stirring while nitrogen gas was fed. After heating, 33%by mass of the monomer mixture solution and 33%by mass of the initiator solution were added dropwise into the reactor over 80 minutes. Then, 13 parts by mass of ITA was charged in the reactor, and then 33%by mass of the monomer mixture solution and 33%by mass of the initiator  solution were added dropwise into the reactor over 80 minutes. Next, 13 parts by mass of ITA was added to the reactor, and then the remaining monomer mixture solution and initiator solution were added dropwise into the reactor over 80 minutes. During addition and reaction, stirring was continued while the temperature in the reactor was maintained at 100℃, and after the completion of dropwise addition, stirring was continued for 30 minutes, followed by cooling to 70℃. After cooling, 44 parts by mass of 2-dimethylaminoethanol (hereinafter "DMAE" ) was added to the reactor under stirring, and 750 parts by mass of ion exchange water was added dropwise over 1 hour. After the completion of dropwise addition, stirring was continued for 30 minutes, producing a water dispersion for a metallic coating material (1) .
[EXAMPLE 2: production of water dispersion for metallic coating material (2) ]
A monomer mixture solution was prepared by mixing 180 parts by mass of St, 163 parts by mass of BA, 70 parts by mass of n-BMA, 30 parts by mass of HEA, and 75 parts by mass of PGM. Also, an initiator solution was prepared by mixing 17.5 parts by mass of P-O and 17.5 parts by mass of PGM. In a 2-liter reactor provided with a stirrer, a thermometer, and a condenser, 19 parts by mass of ITA and 150 parts by mass of PGM were charged, and then the inside of the reactor was heated to 100℃ under stirring while nitrogen gas was fed. After heating, 33%by mass of the monomer mixture solution and 33%by mass of the initiator solution were added dropwise into the reactor over 80 minutes. Then, 19 parts by mass of ITA was charged in the reactor, and then 33%by mass of the monomer mixture solution and 33%by mass of the initiator solution were added dropwise into the reactor over 80 minutes. Next, 20 parts by mass of ITA was added to the reactor, and then the remaining monomer mixture solution and initiator solution were added dropwise into the reactor over 80 minutes. During addition and reaction, stirring was continued while the temperature in the reactor was maintained  at 100℃, and after the completion of dropwise addition, stirring was continued for 30 minutes, followed by cooling to 70℃. After cooling, 63 parts by mass of DMAE was added to the reactor under stirring, and 750 parts by mass of ion exchange water was added dropwise over 1 hour. After the completion of dropwise addition, stirring was continued for 30 minutes, producing a water dispersion for a metallic coating material (2) .
[EXAMPLE 3: production of water dispersion for metallic coating material (3) ]
A monomer mixture solution was prepared by mixing 180 parts by mass of St, 150 parts by mass of BA, 100 parts by mass of n-BMA, 30 parts by mass of HEA, 6 parts by mass of methacrylic acid (hereinafter "MAA" ) , and 75 parts by mass of PGM. Also, an initiator solution was prepared by mixing 17.5 parts by mass of P-O and 17.5 parts by mass of PGM. In a 2-liter reactor provided with a stirrer, a thermometer, and a condenser, 12 parts by mass of ITA and 150 parts by mass of PGM were charged, and then the inside of the reactor was heated to 100℃ under stirring while nitrogen gas was fed. After heating, 33%by mass of the monomer mixture solution and 33%by mass of the initiator solution were added dropwise into the reactor over 80 minutes. Then, 12 parts by mass of ITA was charged in the reactor, and then 33%by mass of the monomer mixture solution and 33%by mass of the initiator solution were added dropwise into the reactor over 80 minutes. Next, 12 parts by mass of ITA was added to the reactor, and then the remaining monomer mixture solution and initiator solution were added dropwise into the reactor over 80 minutes. During addition and reaction, stirring was continued while the temperature in the reactor was maintained at 100℃, and after the completion of dropwise addition, stirring was continued for 30 minutes, followed by cooling to 70℃. After cooling, 44 parts by mass of DMAE was added to the reactor under stirring, and 750 parts by mass of ion exchange water was added dropwise over 1 hour. After the completion of  addition, stirring was continued for 30 minutes, producing a water dispersion for a metallic coating material (3) .
[COMPARATIVE EXAMPLE 1: production of water dispersion for metallic coating material (R1) ]
A monomer mixture solution was prepared by mixing 180 parts by mass of St, 145 parts by mass of BA, 101 parts by mass of n-BMA, 30 parts by mass of HEA, 45 parts by mass of acrylic acid (hereinafter "AA" ) , and 75 parts by mass of PGM. Also, an initiator solution was prepared by mixing 17.5 parts by mass of P-O and 17.5 parts by mass of PGM. In a 2-liter reactor provided with a stirrer, a thermometer, and a condenser, 150 parts by mass of PGM was charged, and then the inside of the reactor was heated to 100℃ under stirring while nitrogen gas was fed. After heating, the monomer mixture solution and the initiator solution were added dropwise into the reactor over 4 hours. During addition and reaction, stirring was continued while the temperature in the reactor was maintained at 100℃, and after the completion of dropwise addition, stirring was continued for 30 minutes, followed by cooling to 70℃. After cooling, 44 parts by mass of DMAE was added to the reactor under stirring, and 750 parts by mass of ion exchange water was added dropwise over 1 hour. After the completion of dropwise addition, stirring was continued for 30 minutes, producing a water dispersion for a metallic coating material (R1) .
[COMPARATIVE EXAMPLE 2: production of water dispersion for metallic coating material (R2) ]
A monomer mixture solution was prepared by mixing 180 parts by mass of St, 150 parts by mass of BA, 100 parts by mass of n-BMA, 30 parts by mass of HEA, and 75 parts by mass of PGM. In a 2-liter reactor provided with a stirrer, a thermometer, and a condenser, 40 parts by mass of ITA and 150 parts by mass of PGM were charged, and then the inside of the reactor was heated to 100℃ under stirring while nitrogen gas was fed. After heating, a mixture of the monomer mixture solution, 17.5 marts by mass of P-O,  and 17.5 parts by mass of PGM was added dropwise into the reactor over 4 hours. During addition and reaction, stirring was continued while the temperature in the reactor was maintained at 100℃, and after the completion of dropwise addition, stirring was continued for 30 minutes, followed by cooling to 70℃. After cooling, 33 parts by mass of DMAE was added to the reactor under stirring, and 750 parts by mass of ion exchange water was added dropwise over 1 hour. After the completion of dropwise addition, stirring was continued for 30 minutes, producing a water dispersion for a metallic coating material (R2) .
[COMPARATIVE EXAMPLE 3: production of water dispersion for metallic coating material (R3) ]
A monomer mixture solution was prepared by mixing 180 parts by mass of St, 140 parts by mass of BA, 130 parts by mass of n-BMA, 30 parts by mass of HEA, and 75 parts by mass of PGM. In a 2-liter reactor provided with a stirrer, a thermometer, and a condenser, 21 parts by mass of ITA and 150 parts by mass of PGM were charged, and then the inside of the reactor was heated to 100℃ under stirring while nitrogen gas was fed. After heating, a mixture of the monomer mixture solution, 17.5 marts by mass of P-O, and 17.5 parts by mass of PGM was added dropwise into the reactor over 4 hours. During addition and reaction, stirring was continued while the temperature in the reactor was maintained at 100℃, and after the completion of dropwise addition, stirring was continued for 30 minutes, followed by cooling to 70℃. After cooling, 22 parts by mass of DMAE was added to the reactor under stirring, and 750 parts by mass of ion exchange water was added dropwise over 1 hour. After the completion of dropwise addition, stirring was continued for 30 minutes, producing a water dispersion for a metallic coating material (R3) .
[Preparation of aqueous metallic coating material]
Mixed were 20 parts by mass of butyl cellosolve and 20 parts  by mass of 50 mass%aluminum paste ( "Alpaste WXM-5660" manufactured by Toyo Aluminum K.K.: scale-like aluminum pigment) , producing 40 parts by mass of a butyl cellosolve mixture solution of aluminum paste.
Next, in a state where 100 parts by mass of the water dispersion for a metallic coating material produced as described above was stirred by Disper, 9 parts by mass of diethylene glycol dibutyl ether was added, and 1 part by mass of a surface additive ( "BYK-346" manufactured by BYK Chemie Co., Ltd. ) , and 2 parts by mass of a surface additive ( "Surfynol 104BC" manufactured by Evonik Co., Ltd. ) were further added. Then, 31.5 parts by mass of the butyl cellosolve mixture solution of aluminum paste and 27 parts by mass of a thickener ( "Rheovis AS-1130" manufactured by BASFC., Ltd. ) was previously diluted with water to a concentration of 3%by mass) were added and stirred for 15 minutes, producing a main agent of an aqueous metallic coating material.
Next, 100 parts by mass of the main agent of an aqueous metallic coating material was mixed with 4 parts by mass of an isocyanate curing agent ( "Burnock DNW-5500" manufactured by DIC Corporation) and adjusted to a viscosity of 40 seconds (ford cup #4/20℃) with deionized water, producing an aqueous metallic coating material. The equivalent ratio (isocyanate group/hydroxyl group) was 1.
[Formation of 1-coat coating film test plate]
The aqueous metallic coating material prepared as described above was coated on a plastic material ABS plate by a spray so that the thickness was 15 μm, set for 5 minutes, and then dried at 80℃ for 30 minutes by using a hot-air dryer, forming a 1-coat coating film teat plate having a dry coating film formed thereon.
[Preparation of clear coating material for 2 coats]
A dilute thinner was prepared by mixing 50 parts by mass of xylene, 30 parts by mass of butyl acetate, 10 parts by mass of propylene glycol monomethyl ether acetate, and 10 parts by mass of ethyl-3-ethoxypropionate. Then, 23 parts by mass of the dilute thinner was mixed with 30 parts by mass of acrylic resin ( "Acrydic A-859-B" manufactured by DIC Corporation) , 13 parts by mass of an isocyanate curing agent ( "Desmodur N-3300" manufactured by Covestro Ltd. ) , and a surface additive ( "BYK-331" manufactured by BYK Chemie Co., Ltd. ) to prepare a clear coating material for 2 coats.
[Formation of 2-coat coating film test plate]
The aqueous metallic coating material prepared as described above was coated on a plastic material ABS plate by a spray so that the thickness was 15 μm, and was set for 5 minutes. Then, the clear coating material for 2 coats was coated so that the thickness was 30 μm, set for 5 minutes, and dried at 80℃ for 30 minutes by using a hot-air dryer, forming a 2-coat coating film teat plate having a dry coating film formed thereon.
[Evaluation of coating film appearance]
The coating film appearance was evaluated by visually observing the coating film surface of the 1-coat coating film test plate formed as described above according to the following criteria.
○: Good feeling of brightness with no metallic unevenness
△: Slightly decreased feeling of brightness with a little metallic unevenness
×:No feeling of brightness with remarkable metallic unevenness
[Evaluation of lifting resistance]
The lifting resistance was evaluated by visually observing and comparing the surfaces of the 1-coat coating film test plate and 2-coate coating film test plate formed as described above according to the following criteria.
○: Good lifting resistance with no differences in color and appearance between the coating films
△:Slightly poor lifting resistance with differences in color and appearance between the coating films
×:Poor lifting resistance with remarkable differences in color and appearance between the coating films
Table 1 shows the compositions and evaluation results of the water dispersions for a metallic coating material (1) to (3) and (R1) to (R3) producing as described above.
[Table 1]
Figure PCTCN2021075220-appb-000001
The coating films obtained from the water dispersions for a metallic coating material of Examples 1 to 3 were confirmed to be excellent in coating film appearance and lifting resistance.
Comparative Example 1 is an example not using itaconic acid as the essential raw material, and the lifting resistance was  confirmed to be unsatisfactory.
Comparative Example 2 is an example using an average particle diameter larger than the upper limit of the present invention, and the coating film appearance was confirmed to be unsatisfactory.
Comparative Example 3 is an example using the acrylic polymer having an acid value lower than the lower limit of the present invention and an average particle diameter larger than the upper limit of the present invention, and the coating film appearance was confirmed to be unsatisfactory.

Claims (4)

  1. A water dispersion for ametallic coating material, comprising:
    an acrylic polymer (A) composed of itaconic acid as an essential raw material and dispersed in an aqueous medium (B) ,
    wherein the acid value of the acrylic polymer (A) is 40 to 100 mgKOH/g, and the average particle diameter of particles formed by the acrylic polymer (A) is 35 nm or less.
  2. The water dispersion for a metallic coating material according to Claim 1, wherein itaconic acid in the unsaturated monomer raw material of the acrylic polymer (A) is 4%to 12%by mass.
  3. The water dispersion for a metallic coating material according to Claim 1 or 2, wherein the acrylic polymer (A) has a hydroxyl group.
  4. An aqueous metallic coating material comprising:
    the water dispersion for a metallic coating material according to any one of Claims 1 to 3; and
    a metallic pigment.
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