WO2007013684A2 - Composition de revetement transparente aqueuse et procede de formation de film de finition multicouche - Google Patents

Composition de revetement transparente aqueuse et procede de formation de film de finition multicouche Download PDF

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Publication number
WO2007013684A2
WO2007013684A2 PCT/JP2006/315435 JP2006315435W WO2007013684A2 WO 2007013684 A2 WO2007013684 A2 WO 2007013684A2 JP 2006315435 W JP2006315435 W JP 2006315435W WO 2007013684 A2 WO2007013684 A2 WO 2007013684A2
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Prior art keywords
coating composition
group
acid
clear coating
aqueous
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PCT/JP2006/315435
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English (en)
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WO2007013684A3 (fr
Inventor
Seiji Wada
Yuta Baba
Koki Chiga
Takashi Noguchi
Takato Adachi
Hiroyuki Onoyama
Hideo Sugai
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Kansai Paint Co., Ltd.
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Application filed by Kansai Paint Co., Ltd. filed Critical Kansai Paint Co., Ltd.
Priority to JP2008503304A priority Critical patent/JP2009503122A/ja
Publication of WO2007013684A2 publication Critical patent/WO2007013684A2/fr
Publication of WO2007013684A3 publication Critical patent/WO2007013684A3/fr

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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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • 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
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
    • C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
    • C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • 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
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
    • 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

Definitions

  • the present invention relates to an aqueous clear coating composition and a method for forming a multilayer topcoat film using the aqueous clear coating composition.
  • the outer panels, etc. of automobile bodies are usually coated with coating films comprising an undercoat, an intermediate coat and a topcoat.
  • the undercoat is formed by applying an aqueous coating composition such as a cationic electrodeposition coating composition, etc.
  • an aqueous coating composition such as a cationic electrodeposition coating composition, etc.
  • a multilayer topcoat film can be formed, for example, by a two-coat one-bake method comprising applying a colored base coating composition to a substrate, further applying a clear coating composition without heat-curing the base coating layer, and then curing the two coating layers simultaneously.
  • aqueous coating compositions are used as such top coating compositions, aqueous compositions, in particular, aqueous clear coating compositions for forming the uppermost layer, are required to provide good coating appearance such as smoothness with no ' abnormalities such as foaming on the coated surface, so as to improve the appearance of automobile bodies, etc.
  • U.S. Patent No. 5,075,370 discloses a two-component coating composition comprising a polyol component containing hydroxy and carboxylate groups, and a polyisocyanate component which is present in emulsified form in the polyol component.
  • this two-component coating composition is such that compared to conventional organic solvent-based coating compositions, abnormalities such as foaming on the coated surface tend to occur and coating appearance such as smoothness are unsatisfactory.
  • An object of the present invention is to provide an aqueous clear coating composition capable of providing good coating appearance such as smoothness with no abnormalities such as foaming on the coated surface, the composition being suitable for- use as a top coating composition in methods of application such as two-coat one-bake methods for coating an automotive vehicle body, etc.
  • Another object of the present invention is to provide a method for forming a multilayer topcoat film using the aqueous clear coating composition.
  • the present inventors carried out extensive resea'rch on aqueous clear coating compositions, focusing attention on the influence of viscosity of the aqueous coating composition on the occurrence of abnormalities such as foaming on the coated surface.
  • the inventors found that when using an aqueous coating composition comprising an aqueous dispersion of a specific hydroxy group- and acid group-containing particulate resin and a crosslinking agent and having a viscosity within a specific range, the above ' objects can be achieved.
  • the present invention has been accomplished based on this finding.
  • the present invention provides the following aqueous clear coating compositions and method for forming a multilayer topcoat ' film.
  • An aqueous clear coating composition comprising:
  • composition having a viscosity such that the lowest viscosity value of the composition as measured over the temperature range of 30 0 C to 15O 0 C at a frequency of 0.1 Hz at a solids content of at least 90 mass % is 30 Pa-s or less.
  • aqueous clear coating composition according to item 1 wherein the melt viscosity of the hydroxy group- and acid group- containing particulate resin in dispersion (A) as measured at a solids content of at least 96 mass % at a shear rate of 564 s ⁇ at 14O 0 C is 1 to 12 Pa-s:
  • the aqueous clear coating composition according to item 1 wherein the hydroxy group- and acid group-containing particulate resin in dispersion (A) has a weight average molecular weight of 3,000 to 30,000.
  • aqueous clear coating composition according to item 1 wherein the hydroxy group- and acid group-containing particulate resin in dispersion (A) has a glass transition temperature within the range of from -30 0 C to +40°C.
  • crosslinking agent (B) is at least one crosslinking agent selected from the group consisting of polyisocyanate compounds, blocked polyisocyanate compounds and melamine resins. 6. The aqueous clear coating composition according to item 5 wherein crosslinking agent (B) is at least one polyisocyanate compound and/or at least one blocked polyisocyanate compound.
  • aqueous clear coating composition according to item 5 wherein crosslinking agent (B) is at least one melamine resin.
  • crosslinking agent (B) is at least one melamine resin.
  • the proportions of hydroxy group- and acid group- containing particulate resin in dispersion (A) and melamine resin, based on the total weight of these two resins are 50 to 90 wt.% of the former and 50 to 10 wt.% of the latter.
  • the aqueous clear coating composition according to item 1 having a solids content of 35 to 65 mass %.
  • a method for forming a multilayer topcoat film comprising forming on a substrate one or two color base coat layers and one or two clear coat layers, the uppermost clear coat layer being formed by using the aqueous clear coating composition of item 1.
  • aqueous clear coating composition and the method of forming a multilayer topcoat film of the invention are described below in detail.
  • the aqueous clear coating composition comprises an aqueous dispersion (A) of a specific hydroxy group- and acid group-containing particulate resin, and a crosslinking agent (B) , and has a viscosity such that the lowest viscosity value of the coating composition as measured over the temperature range of 30°C to 150°C at a frequency of 0.1 Hz at a solids' content of at least 90 mass % is 30 Pa-s or less.
  • Aqueous hydroxy group- and acid group-containing particulate resin dispersion (A) Aqueous hydroxy group- and acid group-containing particulate resin dispersion (A)
  • the aqueous dispersion (A) is prepared by dispersing in water a hydroxy group- and acid group-containing resin with a hydroxy value of about 30 to about 200 mg KOH/g and an acid value of about 5 to about 50 mg KOH/g to form an aqueous dispersion of a particulate resin with a mean particle size of about 50 to about 300 nm.
  • the hydroxy group- and acid group-containing resin preferably has a weight average molecular weight of about 3,000 to about 30,000, and/or a glass transition temperature of about -30 to about +40°C.
  • the hydroxy group- and acid group-containing resin dispersed in water may be any resin that has a hydroxy value of about 30 to about 200 mg KOH/g and an acid value of about 5 to about 50 mg KOH/g.
  • the hydroxy group mainly acts as a functional group for the reaction of the resin in dispersion (A) with crosslinking agent (B) .
  • the acid group mainly imparts water dispersibility to the resin and also acts as an internal catalyst for the crosslinking reaction of the resin in dispersion (A) with crosslinking agent (B) .
  • resins of hydroxy group- and acid group- containing resins include acrylic resins, polyester resins, polyether resins, polycarbonate resins, polyurethane resins and the like.
  • acid groups include carboxy, sulfonate, phosphate and like groups.
  • hydroxy group- and acid group-containing acrylic resins, hydroxy group- ' and carboxy group-containing polyester resins, hydroxy group- and carboxy group-containing polyurethane resins and the like are preferable.
  • Hydroxy group- and acid group-containing acrylic resins can be produced by copolymerizing at least one hydroxy group- containing vinyl monomer (M-I) , at least one acid group- containing vinyl -monomer (M-2) and at least one other copolymerizable vinyl monomer (M-3) according to usual methods.
  • the hydroxy group-containing vinyl monomer (M-I) Is a compound containing one hydroxy group and one polymerizable unsaturated bond per molecule.
  • monomers include monoesterified products of (meth) acrylic acid with a dihydric alcohol having 2 to 10 carbon atoms, such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl
  • Such monomers (M-I) can be used singly or in combination of two or more.
  • the amount of monomer (M-I) may be any amount such that the resulting hydroxy group- and acid group- containing acrylic resin has a hydroxy value of about 30 to about 200 mg KOH/g.
  • (meth) acrylate means acrylate and/or methacrylate .
  • (Meth) acrylic acid means acrylic acid and/or methacrylic acid.
  • (Meth) aeryloyl means acryloyl and/or methacryloyl.
  • the acid group-containing vinyl monomer (M-2) is a compound having one acid group and one polymerizable unsaturated bond per molecule.
  • monomers include carboxy group-containing unsaturated monomers such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, and maleic anhydride; sulfonic acid group-containing unsaturated monomers such as vinylsulfonic acid and sulfoethyl (meth) acrylate; acid phosphate unsaturated monomers such as 2- (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate, 2- (meth) acryloyloxy-3-chloropropyl acid phosphate and 2- methacrolyloxyethylphenyl phosphate; and the like.
  • Such monomers (M-2) can be used singly or in combination of two or more.
  • the amount of monomer (M-2) may be any amount such that the resulting hydroxy group- and acid group- containing acrylic resin has an acid value of about 5 to about 50 mg KOH/g.
  • the other copolymerizable vinyl monomer (M-3) is a compound other than the above hydroxy group-containing vinyl monomer (M-I) and acid group-containing vinyl monomer (M-2) and has one polymerizable unsaturated bond per molecule.
  • Specific examples of monomer (M-3) ' are listed in (I)- (6) below.
  • Monoesterified products of acrylic or methacrylic acid and a monohydric alcohol having 1 to 20 carbon atoms for example, methyl (meth) aerylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate and the like.
  • Aromatic vinyl monomers for example, styrene, ⁇ - methylstyrene, vinyltoluene and the like.
  • Glycidyl group-containing vinyl monomers compounds having one glycidyl group and one polymerizable unsaturated bond per molecule, such as glycidyl acrylate, glycidyl methacrylate, and the like.
  • Polymerizable unsaturated bond-containing amide compounds for example, acrylamide, methacrylamide, dimethylacrylamide, N,N- dimethylpropylacrylamide, N-butoxymethylacrylamide, N- methylolacrylamide, N-methylolmethacrylamide, diacetoneacrylamide and the like.
  • vinyl versatates for example, vinyl 1 acetate, vinyl propionate, vinyl chloride, vinyl versatates and the like.
  • vinyl versatates include commercially available products such as "VEOVA9” and “VEOVAlO” (trade names, products of Japan Epoxy Resin Co., Ltd.) and the like. '
  • Polymerizable unsaturated bond-containing nitrile compounds for example, acrylonitrile, methacrylonitrile and the like.
  • Such other vinyl monomers (M-3) can be used singly or in combination of two or more. !
  • a preferable polymerization method for producing the hydroxy group- and acid group-containing acrylic resin is solution polymerization of a monomer mixture in the presence of a solvent.
  • Such solution polymerization may be single-stage or multistage polymerization.
  • Single-stage polymerization is a method comprising adding a monomer mixture and a polymerization initiator dropwise ' together to allow a polymerization reaction to proceed.
  • Multistage polymerization is a method comprising adding monomers to a reaction vessel in stages to allow a multistage polymerization to proceed.
  • a hydroxy group-' and acid group-containing acrylic resin obtained by multistage polymerization i.e., two or more stage polymerization is preferably used. More specifically, for example, a hydroxy group- and acid group-containing acrylic resin obtained by a two-stage polymerization method comprising dropwise addition and polymerization of a monomer mixture not containing or substantially not containing any acid group- containing monomers, and dropwise addition and polymerization of a monomer mixture containing an acid group-containing monomer, has good dispersion stability and thus can be advantageously used.
  • the hydroxy group- and acid group-containing acrylic resin has a hydroxy value of about 30 to about 200 mg KOH/g, and preferably about 50 to about 180 mg KOH/g.
  • the hydroxy value is less than 30 mg KOH/g, the composition may have poor curability.
  • the hydroxy value exceeds 200 mg KOH/g, the coating film may have insufficient water resistance.
  • the hydroxy groups of the hydroxy group- and acid group-containing acrylic resin may be primary or secondary.
  • Primary hydroxy groups are preferable for excellent curability of the composition.
  • the presence of both the primary and secondary hydroxy groups is advantageous in terms of improving antifdarning properties of the coating film.
  • 2-Hydroxyisopropyl (meth) acrylate, etc. can be mentioned as examples of the hydroxy group-containing vinyl monomer (M-I) that provides secondary hydroxy groups.
  • the hydroxy group- and acid group-containing acrylic resin has an acid value of about 5 to about 50 mg KOH/g, and preferably about 10 to about 40 mg KOH/g.
  • the acid value is less than 5 mg KOH/g, the resulting aqueous dispersion may have poor dispersion stability.
  • the acid value exceeds 50 mg KOH/g, the obtained coating film may have insufficient water resistance.
  • the hydroxy group- and acid group-containing acrylic resin preferably has a weight average molecular weight of about 3,000 to about 30,000, and more preferably about 5,000 to about 20,000-.
  • the weight average molecular weight of the resins was determined by GPC (gel permeation chromatography) relative to polystyrene standards.
  • GPC gel permeation chromatography
  • measurements were made using a GPC apparatus "HLC8120GPC" (trade name, product of Tosoh Corporation) together with four columns “TSKgel G-4000 HXL”, “TSKgel G-3000 HXL”, “TSKgel G-2500 HXL” and "TSKgel G-2000 HXL” (trade names, products of Tosoh Corporation) under the following conditions: mobile phase: tetrahydrofuran; measurement temperature: 40 0 C; flow rate: 1 cc/min.; and detector: RI.
  • the hydroxy group- and acid group-containing acrylic resin preferably has a glass transition temperature of within the range of from about -30 0 C to about +40 0 C, and more preferably about -20 0 C to about +20 0 C.
  • the glass transition temperature was determined at a temperature increase rate of 10°C/min. by DSC (differential scanning calorimetry) according to JIS K7121 (method of measuring the transition temperature of plastics) .
  • DSC differential scanning calorimetry
  • JIS K7121 method of measuring the transition temperature of plastics
  • the hydroxy group- and carboxy group-containing polyester resin can be prepared, for example, by esterification of a polybasic acid with a polyhydric alcohol according to the usual method.
  • the polybasic acid is a compound having at least two carboxy groups per molecule, and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, itaconic acid, trimellitic acid, pyromellitic acid-,- and like polybasic acids; and anhydrides thereof.
  • the polyhydric alcohol is a compound having at least two hydroxy groups per' molecule, and examples thereof include ethylene glycol, propylene glycol, 1,3- propanediol, 1, 4-butanediol, 1,5-pentanediol, 1, 6-hexanediol, 2,2-diethyl-l,3-propanediol, neopentylglycol, 1, 9-nonanediol, 1, 4-cyclohexanediol, hydroxypivalic acid neopentyl glycol ester, 2-butyl-2-ethyl-l,3-propanediol, 3-methyl-l,5-pentanediol, 2,2,4- trimethylpentanediol, hydrogenated bisphenol A, and like diols; trimethylolpropane, trimethylolethane, glycerin, pentaerythritol and like at least trihydric
  • a monoepoxy compound such as propylene oxide, butylene oxide or like ⁇ -olefin epoxide, "Cardura ElO"
  • the introduction of carboxy groups into the polyester resin can be made, for example, by addition of an acid anhydride to a hydroxy group-containing polyester for half-esterifica'-tion.
  • Examples of usable acid anhydrides include trimellitic anhydride and the like.
  • the hydroxy group- and carboxy group-containing polyester resin has a hydroxy value of about 30 to about 200 mg KOH/g, and preferably about 50 to about 180 mg KOH/g. When the hydroxy value is less than 30 mg KOH/g, the resulting composition may have poor curability. When the hydroxy value exceeds 200 mg '
  • the obtained coating film may have insufficient water resistance.
  • the hydroxy group- and carboxy group-containing polyester resin has an acid value of about 5 to about 50 mg KOH/g, and preferably about 10 to about 40 mg KOH/g. When the acid value is less than 5 mg KOH/g, the resulting aqueous dispersion may have poor dispersion stability. When the acid value exceeds 50 mg KOH/g, the obtained coating film may have insufficient water resistance.
  • the hydroxy group- and carboxy group-containing polyester resin preferably has a weight average molecular weight of about 3,000 to about 30,000, and more preferably about 5,000 to about 20,000.
  • the hydroxy group- and carboxy group- containing polyester resin preferably has a glass transition temperature within the range of from about -3O 0 C to about +4O 0 C, and more preferably about -2O 0 C to about +20 0 C.
  • Hydroxy group- and carboxy group-containing polyurethane resins include resins known to be usable for aqueous coating compositions, such as resins having carboxy groups introduced into the molecule that are obtained by reacting a polyol mixture comprising a carboxyl group-containing polyol with a diisocyanate .
  • the polyol mixture preferably comprises a carboxy group-containing polyol and a polyol containing no carboxy groups.
  • polyols containing no carboxy groups l include low molecular weight polyols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol and like dihydric alcohols; trimethylolpropane, glycerol, pentaerythritol and like trihydric alcohols; and higher molecular weight polyols such as polyether polyols, polyester polyols, acrylic polyols, epoxy polyols and the like.
  • polyether polyols examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like.
  • polyester polyols include polycondensates of a dihydric alcohol such as dipropylene glycol, 1,4-butanediol, 1,6- hexanediol, neopentyl glycol or the like with a dibasic acid such as adipic acid, azelaic acid, sebacic acid or the like; ' polyols obtained by ring-opening polymerization of a lactone such as polycaprolactone; polycarbonate diols; etc.
  • carboxy group-containing polyols examples include
  • 2,2-dimethylolpropionic acid 2,2-dimethlolbutanoic acid and the like.
  • 2,2-dimethylolpropionic acid is particularly preferable.
  • a small quantity of solvent such as N-methylpyrrolidone can be used to accelerate the reaction.
  • polyisocyanates to be reacted with such polyols include aliphatic diisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, lysine diisocyanate and the like; biuret adducts and isocyanurate ring adducts of such aliphatic diisocyanates; alicyclic diisocyanates such as isophorone diisocyanate, 4,4'- methylenebis (cyclohexylisocyanate) , methylcyclohexane-2, 4- diisocyanate, methylcyclohexane-2, 6-diisocyanate, 1,3- di (isocyanatomethyl)cyclohexane, 1,4- di (isocyanatomethyl)cyclohexane, 1, 4-cyclohexane diisocyanate, 1, 3-cyclopentane diisocyanate, 1,
  • the hydroxy group- and carboxy group-containing polyurethane resin has a hydroxy value of about 30 to about 200 mg KOH/g, and preferably about 50 to about 180 mg KOH/g.
  • the hydroxy value is less than 30 mg KOH/g, the resulting composition may have poor curability.
  • the hydroxy value exceeds 200 mg KOH/g, the obtained coating film may have insufficient water resistance.
  • the hydroxy group- and carboxy group-containing polyurethane resin has an acid value of about 5 to about 50 mg KOH/g, and preferably about 10 to about 40 mg KOH/g.
  • the acid value is less than 5 mg KOH/g, the resulting aqueous dispersion may have poor dispersion stability.
  • the acid value exceeds 50 mg KOH/g, the obtained coating film may have insufficient water resistance.
  • the hydroxy group- and carboxy group-containing polyurethane resin preferably has a weight average molecular weight of about 3,000 to about 30,000, and more preferably about 5,000 to about 20,000.
  • the hydroxy group- and carboxy group- containing polyurethane resin preferably has a glass transition temperature of about -30 to about +4O 0 C, and more preferably about -20 to about +20 0 C.
  • the aqueous hydroxy group-containing and acid group- containing particulate resin dispersion (A) is obtained by dispersing a hydroxy group- and acid group-containing resin in water in such a manner that the particulate resin has a mean particle size of about 50 to about 300 nm.
  • the dispersion of the hydroxy group- and acid group-containing resin in water can be made, for example, in the following manner.
  • a hydroxy group- and acid group-containing resin is usually obtained in the form of an organic solvent solution by various synthetic reactions and the solvent is distilled off under reduced pressure to a solids content of about 95 mass %.
  • the temperature during the reduced pressure distillation is set to an optimal temperature according to the kind of solvent used in the preparation of the resin.
  • the organic solvent is preferably distilled off as much as possible. After the organic solvent is distilled off under reduced pressure, for example, a neutralizing agent is added at about 90 0 C to neutralize the resin solution and then a specific amount of deionized water is added dropwise with stirring at about 80 0 C, thus giving an aqueous hydroxy group- containing and acid group-containing particulate resin dispersion (A) .
  • a neutralizing agent is added at about 90 0 C to neutralize the resin solution and then a specific amount of deionized water is added dropwise with stirring at about 80 0 C, thus giving an aqueous hydroxy group- containing and acid group-containing particulate resin dispersion (A) .
  • preferable neutralizing agents include ammonia, ethylamine, isopropylamine, cyclohexylamine, dipropylamine, dibutylamine, triethylamine, tributylamine, ethylenediamine, morpholine, pyridine, isopropanolamine, methylisopropanolamine, dimethylethanolamine, aminomethylpropanol, diisopropanolamine, diethanolamine, triethanolamine, diethylethanolamine and like amine compounds.
  • the amount of neutralizing agent can be suitably selected.
  • the amount of neutralizing agent is preferably about 0.4 to about 0.9 equivalents, and particularly preferably about 0.5 to about 0.8 equivalents, per acid group of the hydroxy group- and acid 1 group- containing resin.
  • emulsifiers may be used to improve dispersibility.
  • the particulate resin in the aqueous dispersion (A) has a mean particle size of about 50 to about 300 nm, preferably about 100 to about 250 nm, and more preferably about 100 to about 200 nm.
  • the mean particle size of the dispersed resin particles is less than 50 nm, the aqueous dispersion (A) may have high viscosity and poor antifoaming properties, etc.
  • the mean particle size exceeds 300 nm, the coated surface may have insufficient smoothness.
  • the mean particle size of the particulate resin is a value obtained by measurement at 2O 0 C using a submicron particle size distribution analyzer after the resin dispersion is diluted with deionized water according to the usual method.
  • submicron particle size distribution analyzers include "COULTER N4" (trade name, product of Beckman Coulter, Inc. ) .
  • the melt viscosity of the hydroxy group- and acid group-containing particulate resin in dispersion (A) as measured at a solids content of at least 96 mass % at a shear rate of 564 s "1 at 140 0 C is preferably in the range of about 1 Pa*s to about 12 Pa-s, more preferably about 1 Pa-s to about- 8 Pa* s, and further preferably about 1 Pa* s to about 6 Pa • s . ⁇ ⁇
  • melt viscosities as measured at 120°C and 16O 0 C under the same conditions as in the measurement at 140 0 C are preferably within the following ranges, respectively.
  • the melt viscosity as measured at 120 0 C is preferably about 6 Pa* s to about 72 Pa* s, more preferably about 6 Pa*s to about 48 Pa* s, and further preferably about 6 Pa*s to about 36 Pa* s.
  • the melt viscosity as measured at 16O 0 C is preferably about 0.2 Pa* s to about 2.4 ! Pa* s, more preferably about 0.2 Pa*s to about 1.6 Pa* s, and further preferably about 0.2 Pa*s to about 1.2 Pa* s.
  • the melt viscosity of the hydroxy group- and acid group-containing particulate resin at a solids content of at least 96 mass % means that the hydroxy group- and acid group- containing particulate resin has a melt viscosity within the above-mentioned range when measured at any concentration not lower than 96 mass %, on a solids basis.
  • the melt viscosity of the hydroxy group- and acid group-containing particulate resin at a solids- content of at least 96 mass % was determined by applying the dispersion (A) to a glass plate using a 4-mil applicator, drying at 110 0 C for 3 hours to a solids content of at least 96 mass % and then measuring the viscosity at 14O 0 C at a shear rate of 564 s ⁇ using a cone-and-plate viscosity meter.
  • the aqueous dispersion (A) is not particularly limited as long as the dispersion is obtained by dispersing the hydroxy group- and acid group-containing resin in water. Such dispersions can be used singly or in combination of two or more. Dispersions obtained by dispersing a hydroxy group- and acid group-containing acrylic resin or a hydroxy group- and carboxy group-containing polyester resin in water are preferably used as aqueous dispersions (A) . -
  • the aqueous dispersion (A) preferably has a solids content of about 35 to about 55 mass %.
  • the solids content was calculated by placing about 2.0 g of the aqueous dispersion in an aluminum foil cup with a diameter of about 5 cm, heating at HO 0 C for 1 hour and measuring the amount of residue (g) .
  • the aqueous dispersion (A) preferably has a Brookfield viscosity of about 400 to about 1,000 Pa* s, and more preferably about 500 to about 900 Pa- s. In the Production Examples, etc. described later, the viscosity was measured at 20 0 C at 60 rpm using a Brookfield viscometer.
  • the aqueous dispersion (A) preferably has a pH of about 6.0 to about 8.5, and more preferably about 6.5 to about 8.0.
  • the pH was measured using a pH meter. Examples of pH meters include "F-22" (trade name, product of Horiba Ltd. ) .
  • Crosslinking agent (B)
  • the crosslinking agent (B) of the aqueous clear coating composition of the invention is not limited as long as it is capable of crosslinking with the hydroxy groups of the hydroxy group- and acid group-containing resin in the aqueous dispersion (A) .
  • Examples of usable crosslinking agents include polyisocyanate compounds, blocked polyisocyanate compounds, melamine resins and the like. Among these, polyisocyanate compounds and blocked polyisocyanate compounds are preferable.
  • Polyisocyante compounds have at least two free isocyanate groups per molecule.
  • Examples of polyisocyanate compounds include those known for use in the production of polyurethanes, such as aliphatic polyisocyanates, alicyclic polyisocyanates, aliphatic-aromatic polyisocyanates, aromatic polyisocyantates, and derivatives thereof.
  • aliphatic polyisocyanates examples include trimethylene diisocyanate,. tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, ' 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3- butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- trimethylhexamethylene diisocyanate, 2,2, 4-trimethylhexamethylene diisocyanate, 2, 6-diisocyanatomethylcaproate and like aliphatic diisocyanates; lysine ester triisocyanates, 1, 4, 8-triisocyanato octane, 1, 6, 11-triisocyanato undecane, 1, 8-diisocyanato-4- isocyanato methyloctane, 1,3, 6-triisocyanato hexane, 2,5,7- trimethyl-1, 8-diiso
  • alicyclic polyisocyanates examples include 1,3- cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3- cyclohexane diisocyanate, 3-isocyanatomethyl-3, 5,5- trimethylcyclohexyl isocyanate (common name: isophorone diisocyanate) , 4, 4' -methylenebis (cyclohexylisocyanate) , methyl- 2, 4-cyclohexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, 1,4- bis (isocyanatomethyl) cyclohexane, norbornane diisocyanate and like alicyclic diisocyanates; 1,3,5- triisocyanato cyclohexane, 1, 3, 5-trimethylisocyanato cyclohexane, 2- (3-iso
  • aliphatic-aromatic polyisocyanates examples include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, ⁇ , ⁇ ' - diisocyanato-1, 4-diethylbenzene, 1, 3-bis (1-isocyanato-l- methylethyl)benzene (common name: tetramethylxylylene diisocyanate), 1, 4-bis (1-isocyanato-l-methylethyl) benzene ('common name: tetramethylxylylene diisocyanate) and like aliphatic- aromatic diisocyanates; and 1,3,5-triisocyanate methylbenzene and like aliphatic-aromatic triisocyanates; and the like.
  • aromatic polyisocyanates include m-phenylene diisocyanate, p-phenylene diisocyanate, 4, 4' -diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2, 4' -diphenylmethane diisocyanate, 4, 4' -diphenylmethane diisocyante, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4, 4' -toluidine diisocyanate, 4, 4' -diphenylether diisocyanate and like aromatic diisocyanates; triphenylmethane-4, 4' ,4' ' -triisocyanate, 1,3,5- triisocyanato benzene, 2, 4, 6-triisocyanato toluene and like aromatic triisocyanates; 4,4' -diphenylmethane-2, 2' ,b,b r - tetraiso
  • polyisocyanate derivatives include dimers, trimers, biurets, allophonates, carbodiimides, urethodiones, urethoimines, isocyanurates, oxadiazinediones and like-modified derivatives of such polyisocyanate compounds.
  • Such polyisocyanates can be used singly or in combination of two or more.
  • aliphatic diisocyanates, alicyclic diisocyanates and derivatives thereof are preferably used in view of excellent weatherability, etc. of the obtained cured coating film.
  • Blocked polyisocyanate compounds are obtained by blocking isocyanate groups of such polyisocyanate compounds with a blocking agent.
  • a blocking agent is used to block the free isocyanate groups.
  • the blocked isocyante groups are heated, for example, at 100 0 C or more, preferably 130 0 C or more, the blocking agent is dissociated from the isocyanate groups and the recovered isocyanate groups can then easily react with hydroxy groups.
  • blocking agents include phenol, cresol, xylenol, nitrophenol, ethylphenol, hydroxydiphenyl, butylphenol, isopropylphenol, -nonylphenol, octylphenol, methyl hydroxybenzoate and like phenols; ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, ⁇ -propiolactam and like lactams; methanol, ethanol, propyl ' alcohol, butyl alcohol, amyl alcohol, lauryl alcohol and like aliphatic alcohols; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, methoxymethanol and like ethers; benzyl alcohol; glyc ⁇ lic acid; methyl glycolate, ethylphenol,
  • solvents may be used in reacting such a polyisocyanate compound with a blocking agent to form a blocked polyisocyanate compound.
  • solvents preferably used include solvents ⁇ that are not reactive to isocyanate groups .
  • solvents include acetone, methyl ethyl ketone and like ketones; ethyl acetate and like esters; N-methyl ( pyrrolidone (NMP) ; etc.
  • Preferable compounds used as crosslinking agents in the aqueous clear coating composition of the invention to improve water dispersiblity and reduce the amount of VOCs are hydrophilic polyisocyanate compounds and hydrophilic blocked polyisocyanate compounds obtained by modifying polyisocyanate compounds and blocked polyisocyanate compounds as mentioned above to hydrophilic forms.
  • Hydrophilic polyisocyanate compounds can be obtained, for example, by reacting polyisocyanate compounds and hydrophilic polyether alcohols such as polyethylene glycol monomethyl ether.
  • Hydrophilic polyisocyanate compounds can also be obtained, for example, by reacting the isocyanate groups of a polyisocyanate compound and active hydrogen group (s) of an active-hydrogen-group-containing compound having anionic group (s)
  • Active-hydrogen-group-containing compounds having anionic group (s) have anionic group (s) such as carboxy, sulfonyl, phosphate, sulfobetaine and like betaine structure-containing group (s) and contain active hydrogen group (s) capable of reacting with isocyanate groups, such as hydroxy, amino and like groups.
  • Examples of such active-hydrogen-group-containing compounds having anionic group (s) include compounds having one anionic group and two or more active hydrogen groups . More specifically, examples of active-hydrogen-group-containing compounds having carboxy group (s) include dihydroxycarboxylic acids such as 2,2-dimethylolacetic acid, 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, dimethylheptanoic acid, dimethylolnonanoic acid, 2,2- dimethylolbutyric acid, 2,2-dimethylolvaleric acid and the like; and diaminocarboxylic acids such as l-carboxy-1,5- pentylenediamine, dihydroxybenzoic acid, 3, 5-diaminobenzoic acid, lysine, arginine and the like; half-esterified products of polyoxypropyene triol with maleic anhydride or phthalic anhydride; etc.
  • active-hydrogen-group-containing compounds having sulfonyl group (s) include N,N-bis (2-hydroxyethyl) -2- aminoethanesulfonic acid, l,3-phenylenediamine-4, 6-disulfonic acid, diaminobutanesulfonic acid, 3, 6-diamino-2-toluenesulfonic acid, 2, 4-diamino-5-toluenesulfonic acid and the like.
  • active-hydrogen-group-containing compounds having phosphate group (s) include ⁇ 2,3-dihydroxypropylphenyl phosphate .
  • active-hydrogen-group-containing compounds having betaine structure-containing group (s) include sulfobetaine group-containing compounds obtained by reacting a tertiary amine such as N-methyldiethanolamine with 1,3-propanedisulfonic acid.
  • Examples of active-hydrogen-group-containing compounds having anionic group (s) further include alkyleneoxide-modified products obtained by addition of an alkyleneoxide such as ethyleneoxide, propylenoxide or the like, to anionic group- containing compounds.
  • Such active-hydrogen-group-containing compounds having anionic group (s) may be used singly or in combination of two or more. Active-hydrogen-group-containing compounds having sulfonyl group (s) and active-hydrogen-group-containing compounds having phosphate group (s) are particularly preferable.
  • Polyisocyanate compounds for modification into hydrophilic forms may be polyisocyante compounds mentioned above.
  • Preferable examples thereof include hexamethylene diisocyanate (HMDI) and derivatives thereof, isophorone diisocyanate (IPDI) and derivatives thereof.
  • HMDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • Hydrophilic blocked isocyanate compounds can be synthesized by, for example, blocking isocyante groups of such ⁇ hydrophilically modified isocyanate compounds with a blocking agent.
  • Examples of usable blocking agents are as mentioned in the description of blocked polyisocyanate compounds.
  • the blocking reaction can be carried out in the same manner as mentioned in the description of blocked polyisocyanate compounds.
  • organic tin compounds can be used as curing catalysts .
  • melamine resins include dimethylolmelamine ' , trimethylolmelamine, tetramethylolmelamine, pentamethylolmelamine, hexamethylolmelamine and like methylolmelamines; alkyl-etherified products of methylolmelamines witfi an alcohol; alkyletherified methylolmelamine condensates; etc.
  • usable alcohols include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, 2-ethylhexyl alcohol and the like.
  • preferable melamine resins include melamine resins having an average of at least three methyl-etherfied methylol groups per triazine nucleus; hydrophilic imino group- containing alkyl-etherified melamine resins with a weight average molecular weight of about 500 to about 1,000; etc.
  • Examples of usable melamine resins include commercially available products, which are available, for example, under the ' tradenames "Cymel 303", “Cymel 323", “Cymel 325"', “Cymel 327”, “Cymel 350”, “Cymel 370", “Cymel 380", “Cymel 385" and “Cymel 254" (products of Japan Cytec Industries, Inc.); “Resimene 735", “Resimene 740", “Resimene 741", “Resimene 745", “Resimene 746” and “Resimene 747” (products of Monsanto Chemical Co., Ltd.), “SUMIMAL M55”, “SUMIMAL M30W” and “SUMIMAL M50W” (products of Sumitomo Chemical Co., Ltd.); “U-VAN 20SE” (product of Mitsui Chemicals, Inc.); etc.
  • Such melamine resins can be used singly or in combination of two or more.
  • curing catalysts can be used.
  • curing catalysts include para-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid and like sulfonic acids; amine neutralization salts of such sulfonic acids; and amine neutralization salts of phosphate compounds; etc.
  • At least one crosslinking agent selected from the group consisting of polyisocyanate compounds, blocked polyisocyanate compounds, and melamine resins, is preferably used as crosslinking agent (B) .
  • the equivalent ratio (NCO/OH) of isocyanate ' groups of said polyisocyanate compound and/or blocked polyisocyanate compound to hydroxy groups of the hydroxy group- and acid group-containing particulate resin in dispersion (A) be within the range of about 0.5 to about 2.0, and more preferably about 0.8 to about 1.5.
  • the weight proportions of hydroxy group- and acid group- containing particulate resin in dispersion (A) and melamine resin based on the total weight of these two resins, be 50 to 90 wt.% of particulate resin and 50 to 10 wt.% of melamine resin, and more preferably 60 to 80 wt.% of particulate resin and 40 to 20 wt.% of melamine resin.
  • the aqueous clear coating composition of the invention may contain UV absorbers.
  • UV absorbers include benzotriazole UV absorbers / triazine UV absorbers and the like.
  • benzotriazole UV absorbers examples include 2-(2'- hydroxy-5' -methylphenyl) benzotriazole, 2- [2' -hydroxy-3' , 5' -di (1, 1-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2' -hydroxy-3' , 5' - di-tert-butylphenyl) benzotriazole, 2- (2' -hydroxy-3' -tert-butyl- 5' -methylphenyl) benzotriazole, 2- (2' -hydroxy-3' , 5' -di-tert- amylphenyl)benzotriazole, 2- (2' -hydroxy-3' , 5' -di-tert- butylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3' , 5' -di- isoamylphenyl) benzotriazole, 2- (2' -hydroxy-5' -tert
  • triazine UV absorbers examples include 2- (4,6-' diphenyl-1, 3, 5-triazin-2-yl) -5 (hexyloxy) -phenol (e.g. , "TINUVIN 1577FF", trade name, product of Ciba Specialty Chemicals) , a mixture of 2- [4- [6 (2-hydroxy-3-dodecyloxypropyl) oxy] -2- hydroxyphenyl]-4, 6-bis (2,4-dimethylphenyl)-l,3, 5-triazine and 2- [4- [6 (2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6- bis (2, 4-dimethylphenyl) -1,3, 5-triazine (e.g., "TINUVIN 400", trade name, product of Ciba Specialty Chemicals), 2,4-bis(2,4- dimethylphenyl) -6- (2-hydroxy-4-iso-octyloxypheny
  • UV absorbers can be used singly or in combination of two or more.
  • the amount of UV absorber is preferably about 0.1 to about 10 parts by weight, more preferably about 0.5 to about 5 parts by weight, and further preferably about 0.8 to about 3 parts by weight, per 100 parts by weight of the total amount of aqueous hydroxy group- and acid group-containing particulate resin dispersion (A) and crosslinking agent (B) , on a solids basis.
  • the aqueous clear coating composition of the invention may contain light stabilizers.
  • light stabilizers include hindered amine derivatives. Specific examples thereof include bis (2,2' , 6, 6'-tetramethyl-4-piperidinyl) sebacate, 4-benzoyloxy-2,2' ,6, 6' -tetramethylpiperidine and the like.
  • Such light stabilizers can be used singly or in combination of two or more.
  • the amount of light stabilizer is preferably about 0.1 to about 10 parts by weight, more preferably about 0.5 to about 5 parts by .
  • a method comprising dissolving such additives in a solvent such as toluene, followed by dispersion in water using an emulsifier; a method comprising dissolving such additives in the hydroxy group- and acid group-containing resin solution finally obtained in the resin synthesis and dispersing the additives and the resin in water at the same time; a method comprising adding such additives to a monomer mixture used as the starting material for the synthesis of a hydroxy group- and acid group-containing resin, followed by polymerizing the monomer mixture and dispersing the additives together with the resin in water.
  • the aqueous clear coating composition of the invention may contain curing catalysts, rheology control agents, surface conditioners, coloring pigments, metallic pigments, light interference pigments, extender pigments and like additives, if required.
  • the amount of coloring pigments, metallic pigments, light interference pigments, extender pigments, etc. may be within the range that transparency of the coating film is not impaired.
  • crosslinking agent (B) when a polyisocyanate compound and/or a hydrophilic polyiso ' cyante compound, which are capable of easily crosslinking with hydroxy groups at room temperature, are used as crosslinking agent (B) in the aqueous clear coating composition, it is preferable that the aqueous hydroxy group- and acid group- containing particulate resin dispersion (A) and crosslinnking agent (B) are separate as a two package composition and mixed just before application. _ In this ' case, it is usually preferable that the UV absorbers, light stabilizers and other additives be incorporated as components of aqueous dispersion (A) . Mixing can be performed by using known mixing devices such as agitators, homogenizers and the like.
  • the aqueous clear coating composition of the invention is mainly characterized in having a viscosity such that the lowest viscosity value of the composition as measured over the temperature range of 30 0 C -to 150°C at a frequency of 0.1 Hz at a solids content of at least 90 mass % is 30 Pa-s or less.
  • the lowest viscosity value is preferably 20 Pa « s or less, and more preferably 15 Pa-s or less.
  • the lowest viscosity value means that when the viscosity of the composition is measured over the temperature range of 30 0 C to 150°C at a frequency of 0.1 Hz at any solids content not lower than 90 mass %, the lowest viscosity value falls within the above-mentioned range.
  • the lowest viscosity value of the composition as measured over the temperature range of 30 0 C to 150 0 C refers to the lowest complex viscosity during the melting and flowing of the composition by heating after application of the composition to a substrate.
  • the temperature during the melting and flowing of the agueous clear coating composition by heating is usually in the range of 3O 0 C to 150 0 C.
  • the lowest viscosity was determined using a viscoelasticity meter. In the Examples, etc. described later, the viscosity was measured. using a viscoelasticity meter "Rheostress RS-150" (trade name, product of HAAKE) .
  • the aqueous clear coating composition whose viscosity as measured at 20 0 C using Ford Cup No. 4 had been adjusted to 15 to 60 seconds was applied by air spraying to the surface of a tin plate (300 x 450 x 0.3 mm) degreased with isopropanol to a film thickness of 35 ⁇ m (when dried) and heated at 6O 0 C for about 10 minutes.
  • the uncured coating film formed on the tin plate was scraped off and collected into a sample bottle, which was sealed immediately by closing the cap.
  • the solids content of the coating composition during ⁇ the viscosity measurement was calculated by placing about 2.0 g of the sample in an aluminum foil cup with- a diameter of 5 cm, heating at 110 0 C for 1 hour and then measuring the amount of residue (g) .
  • the aqueous clear coating composition when heated after application has an increased solids content and thus has low thermal flowability, so that problems such as poor surface smoothness, foaming, etc. of the obtained coating film result.
  • measurements were made at a solids content of at least 90 mass % because aqueous clear coating compositions when heated to flow after application usually have a high solids content of at least 90 mass %.
  • the viscosity mainly depends on the properties of the hydroxy group- and acid group-containing particulate resin in dispersion (A) .
  • the lowest viscosity value can be adjusted to 30 Pa-s or less by, for example, using a hydroxy group- and acid group-containing particulate resin in dispersion (A) whose melt viscosity as measured at a solids content of at least 96 mass % at a shear rate of 564 s "1 at 140 0 C is about 1 to about 12 Pa-s.
  • the aqueous hydroxy group- and acid group-containing particulate resin having such a melt viscosity preferably has a weight average molecular weight of about 3,000 to about 30,000 and/or a glass transition temperature within the range of about -30 0 C to about +40 0 C.
  • the aqueous clear coating composition of the invention can be prepared by mixing the aqueous hydroxy group- and acid group-containing particulate resin dispersion (A) and crosslinking agent (B) , optionally together with additives such as UV absorbers, light stabilizers and other additives, according to known methods.
  • the composition of the invention is a two package composition, it is preferable to mix the components just before use.
  • the composition may be diluted with deionized water, if necessary, and the viscosity is preferably adjusted to about 20 to about 60 seconds as measured at 20 0 C using Ford Cup No.. 4, and more preferably be about 30 to 50 seconds.
  • the solids content is preferably about 35 to about 65 mass %, and preferably about 40 to about 60 mass %.
  • VOCs refers to volatile organic substances classified as “highly volatile organic compounds” or “volatile organic compounds” by the World Health Organization (WHO) .
  • WHO World Health Organization
  • aqueous clear coating composition of the invention can be advantageously used in various application methods described below. Substrates
  • substrates to be coated include automobiles, motorcycles and like vehicle bodies and parts thereof.
  • substrates include those that constitute such vehicle bodies and the like, such as cold rolled steel sheets and plates, galvanized steel sheets and plates, zinc alloy-plated steel sheets and plates, stainless steel sheets and plates, tinned steel sheets and plates and like steel sheets and plates, aluminum sheets and plates, aluminum alloy sheets and plates and like metal substrates; plastic substrates; and the like.
  • Such vehicle bodies, metal substrates and the like onto which an undercoat of a cationic electrodeposition coating composition, etc. and/or an intermediate coat have been formed are also usable as substrates.
  • the method of applying the coating composition of the invention is not particularly limited.
  • air spray coating, airless spray coating, rotary atomization coating, curtain coating and like application methods can be used to form a wet coating film.
  • an electrostatic charge may be applied, if necessary.
  • the coating composition is preferably applied to a film thickness of about 10 to about 80 urn (when cured) , and more preferably about 20 to about 60 urn (when cured) .
  • Heating can be performed by known heating means.
  • drying furnaces such as hot air furnaces, electric furnaces, infrared heating furnaces and the like can be used.
  • the heating temperature " is usually within the range of from about 80 0 C to about 18O 0 C, and preferably about 100 0 C to about 160 0 C.
  • the heating time is usually about 10 to about 40 minutes .
  • preheating at about 50 0 C to about 8O 0 C for about 3 to about 10 minutes may be carried out to promote vaporization of volatile components such as water.
  • the coating composition of the invention can form a coating film with excellent properties- in terms of coating appearance such as surface smoothness, water resistance, antifoaming properties, etc. Therefore, the composition of the invention is advantageously used as a clear coating composition for forming a top clear coat in a method of forming a multilayer topcoat ' film on a substrate.
  • the multilayer topcoat formation method of the invention is a method for forming on a substrate one or two colored base coat layers and one or two clear coat layers, the uppermost clear coat layer being formed by using the coating composition of the invention.
  • Especially preferable substrates to which the multilayer topcoat formation method of the invention can be applied are automobile bodies and parts thereof.
  • multilayer topcoat formation method of the invention include the following methods (a) to (c) wherein the clear coating composition of the invention is used to form the top clear coat.
  • Method -'(a) a two-coat method for forming a multilayer topcoat film, wherein a colored base coat and a top clear coat are formed in that order on a substrate. . • i
  • Method (b) a three-coat method for forming a multilayer topcoat film, wherein a colored base coat, a clear coat and a top clear coat are formed in that order on a substrate.
  • Method (c) a three-coat method for forming a multilayer topcoat film, wherein a first colored base coat, a second colored base coat and a top clear coat are formed in that order on a substrate.
  • a topcoat film in methods (a) , (b) and (c) are described below in detail.
  • method (a) a known colored coating composition can be used as the coating composition for forming a colored base coat.
  • a coating composition for..automobile bodies or the like is preferably used as the colored base coating composition.
  • the colored base coating composition is an organic solvent-based or aqueous coating composition comprising a base resin, a crosslinking agent, and a pigment such as a coloring pigment, a metallic pigment, a light interference pigment, an extender pigment or the like.
  • a aqueous coating composition is preferably used as the colored base coating composition.
  • base resins include acrylic resins, vinyl resins, polyester resins, alkyd resins, urethane resins and the like. Such resins can be used singly or as a mixture.
  • Such base resins have crosslinkable functional groups such as hydroxy, epoxy, carboxy, alkoxysilyl and like groups.
  • crosslinking agents include alkyl-etherified melamine resins, urea resins, guanamine resins, polyisocyanate compounds, blocked polyisocyanate compounds, epoxy compounds, carboxy-containing compounds and the like. Such crosslinking agents can be used singly or as a mixture.
  • the proportions of base resin and crosslinking agent are preferably 50% to 90% by weight of base resin and 50% to- 10% by weight of crosslinking agent, based on the total amount of these components.
  • the colored base coating ⁇ composition and the clear coating composition can be applied by application methods such as airless spray coating, air spray coating, rotary atomization coating, etc. In such application ' methods, an electrostatic charge may be applied, if necessary.
  • the colored base coating composition is. applied to a substrate to a film thickness of about 10 to about 50 ⁇ m (when cured) .
  • the applied base coating composition is either cured by heating at about 100 0 C to about 180 0 C, preferably at about 120 0 C to about 160 0 C, for about 10 to about 40 minutes, or is not cured, with the coated substrate being left to stand at room temperature for several minutes or being preheated at about 40 0 C to about 100 0 C for about 1 to about 20 minutes.
  • the clear coating composition of the invention is applied to a film thickness of about 10 to about 70 ⁇ m (when cured) to form a top clear coat and then heated to form a cured multilayer coating film.
  • the heating is performed at about 100 0 C to about 180 0 C, preferably at about 120 0 C to about 160 0 C, for about 10 to about 40 minutes.
  • the method comprising applying a base coating composition, applying a clear coating composition without heat-curing the base coating layer, and then curing the resulting two coating layers simultaneously is referred to as a two-coat one-bake method.
  • the method of applying and heat-curing a base coating composition and then applying and curing a clear coating composition is referred to as a two-coat two-bake method.
  • examples of usable colored base coating compositions are the same as described in method (a) .
  • the first clear coating composition for forming a clear coat may be any coating composition for forming a clear coat.
  • examples of usable coating compositions include those obtained -by completely or almost completely removing pigments from such known colored base coating compositions as mentioned above.
  • the coating composition of the invention is used as the second clear coating composition for forming a top clear coat.
  • both the clear and top clear coats may be formed from the clear coating composition of the invention.
  • a colored base coating composition is applied to the substrate and either cured by heating, or not cured, with the coated substrate being left to stand at room temperature for several minutes or being preheated.
  • a first clear coating composition is applied to the colored base coat surface to a film thickness of about 10 to about 50 ⁇ m (when cured) , and is either cured by heating at about 100 0 C to about 18O 0 C, preferably at about 12O 0 C to about 160 0 C, for about 10 to about 40 minutes, or is not cured, with the coated substrate being left to stand at room temperature for several minutes or being preheated.
  • the coating composition of the invention is applied as a second clear coating composition to a film thickness of about 10 to about 50 ⁇ m (when cured) and then heated to form a cured multilayer coating film.
  • the heating conditions are as in method (a) .
  • the method of applying a base coating composition, applying a first clear coating composition without heat-curing the base coating layer, applying a second clear coating composition without curing the first clear coating layer, and then curing the resulting three coating layers simultaneously is referred to as a three-coat one-bake method.
  • the method of applying a base coating composition, applying a first clear coating composition without heat-curing the base coating layer, curing the resulting two coating layers simultaneously and then applying and curing a second clear coating composition is referred to as a three-coat two-bake method.
  • the method of applying and heat-curing a base coating composition, applying and curing a first clear coating composition, and applying and curing a second clear coating composition is referred to as a three-coat three-bake method.
  • examples of colored base coating ' compositions usable as the first colored base coating composition in method (c) are the same as described in method (a) .
  • a first colored base coating composition is applied to the substrate and either cured by heating, or not cured, with the coated substrate being left to stand at room temperature for several minutes or being preheated.
  • the second colored base coating composition is then applied to the first colored base coat surface to a film thickness of about 10 to about 50 ⁇ m (when cured) and is either cured by heating at about 100 0 C to about 180°C, preferably at about 12O 0 C to about 160 0 C, for about 10 to about 40 minutes, or is not cured, with the coated substrate being left to stand at room temperature for several minutes or being preheated.
  • the coating composition of the invention is applied as a top clear coating composition to a film thickness of about 10 to about 50 um (when cured) and heated to form a cured multilayer coating film.
  • the heating conditions are as in method (a) .
  • the method of applying a first base coating composition, applying a second base coating composition without heat-curing the first base coating layer, applying a clear coating composition without curing the second base coating layer, and then curing the resulting three coating layers simultaneously is referred to as a three-coat one-bake method.
  • the method of applying and heat-curing a first base coating composition, applying a second base coating composition, applying a clear coating composition without curing the second base coating layer and then curing the resulting two coating layers simultaneously is referred to as a three-coat two-bake method.
  • the method of applying and heat-curing a first base coating composition, applying and curing a second base coating composition, and applying and curing a clear coating composition is referred to as a three-coat three-bake method.
  • aqueous clear coating composition and the method of forming a multilayer topcoat film using the composition of the invention can achieve the following remarkable effects.
  • the coating composition of the invention can form on a substrate a coating film with excellent properties in terms of appearance such as surface smoothness, with no abnormalities such as foaming on the coated surface. Therefore, the coating composition of the invention is suitable for use as an aqueous clear coating composition for forming a top clear coat in methods of forming a multilayer topcoat film such as two-coat one-bake methods for coating automobile bodies, etc.
  • the composition of the invention is capable of forming a coating film with excellent appearance, antifoaming properties, etc. presumably because the applied • coating composition has improved thermal flowability and thus has good releasability of volatile component bubbles, which cause foaming during the coating film curing process, and bubble traces formed on the coating film disappear due to excellent thermal flow.
  • the obtained coating film has improved surface smoothness presumably because the hydroxy group- and acid group-containing particulate resin in dispersion (A) of the coating composition of the invention has a mean particle size of 50 to 300 nm, which optimizes the viscosity of the composition and particle size of the particulate resin.
  • the coating composition of the invention is an aqueous coating composition, the amount of VOCs discharged during the process of application to automobile bodies, etc. can be easily reduced.
  • the aqueous dispersion (A-I) had a solids content of 47%, a viscosity of 570 mPa-s (as measured at 20 0 C at 60 rpm using a Brookfield viscometer) and a pH of 7.08, and the dispersed resin particles had a mean particle size of 140 nm.
  • the solids content was determined by applying the dispersion (A-I) to a glass plate using a 4-mil applicator, drying at 110 0 C for 3 hours, scraping off the resulting uncured coating film, placing about 2.0 g of the uncured coating film in an aluminum foil - cup with a diameter of about 5 cm, heating at 110 0 C for 1 hour and measuring the amount of residue (g) .
  • This hydroxy group- and carboxy group-containing > particulate acrylic resin had a hydroxy value of 150 mg KOH/g, and an acid value of 27 mg KOH/g, a weight average molecular weight of 15,000, and a glass transition temperature (Tg) of O 0 C.
  • Production Examples 2 to 6 Aqueous dispersions (A-2) to (A-6) of hydroxy group- and carboxy group-containing particulate acrylic resins were prepared in a manner similar to Production Example 1 using the components and proportions shown in Table 1.
  • Table 1 also shows properties of the carboxy group- containing particulate acrylic resins and aqueous dispersions.
  • N-methylpyrrolidone 10 parts of methyl ethyl ketone, 21.84 parts of neopentylglycol adipate (molecular weight: 1,000, hydroxy value: 116 mg KOH/g), 3.82 parts of neopentylglycol and 4.91 parts of 2,2-dimethylolbutanoic acid were placed into a four-necked flask equipped with a heater, a stirrer, a thermometer, a reflux condenser and a water separator and heated to 7O 0 C to dissolve the mixture.
  • aqueous dispersion (A-7) of a hydroxy group- and carboxy group-containing particulate polyurethane resin.
  • the aqueous dispersion (A-7) had a solids content of
  • the solids content was determined by applying the dispersion (A-7) to a glass plate using a 4-mil applicator, drying at 110 0 C for 3 hours, scraping off the resulting uncured coating film, placing about 2.0 g of the uncured coating film in an aluminum foil cup with a diameter of about 5 cm, heating at
  • This hydroxy group- and carboxy group-containing particulate polyurethane resin had a hydroxy value of 150 mg KOH/g, an acid value of 20 mg KOH/g, a weight average molecular weight of 6,000 and a glass transition temperature (Tg) of 10 0 C.
  • Tg glass transition temperature
  • Aqueous clear coating compositions 1 to 14 were obtained by mixing with stirring aqueous dispersions of hydroxy group- and acid group-containing particulate resins (A-I) to (A-7) obtained in Production Examples 1 to 7 and crosslinking agents (B-I) to (B-5) in the proportions shown in Table 2 using a agitator.
  • the proportions of the components in the coating compositions are expressed as mass ratios of the components on a solids basis.
  • Crosslinking agents (B-I) to (B-5) in Table 2 refer to the following products.
  • (B-I) "XP-2570” (trade name, product of Sumika Bayer ⁇ rethane Co. , Ltd. , a water-dispersible polyisocyanate compound)
  • (B-2) “N-3100” (trade name, product of Sumika Bayer Urethane Co., Ltd., a hydrophilic group-containing polyisocyanate compound) ,
  • (B-3) "XP-2410” (trade name, product of Sumika Bayer ⁇ rethane Co., Ltd., a low-viscosity polyisocyanate compound)
  • (B-4) "LS2253” (trade name, product of Sumika Bayer Urethane Co., Ltd., an amine-blocked polyisocyanate compound)
  • the aqueous clear coating compositions 1 to 14 obtained in Examples 1 to 12 and Comparative Examples 1 to 2 were adjusted to a viscosity of 45 seconds as measured at 20 0 C using Ford Cup No. 4.
  • the solids content (%) , the amount of VOCs (g/1) and the lowest viscosity value of each of the viscosity-adjusted aqueous clear coating compositions were determined.
  • Solids content About 2 g of the viscosity-adjusted aqueous clear , coating composition was placed into an aluminum foil cup ⁇ with a diameter of about 5 cm, dried at 110 0 C for 1 hour and then the weight was measured to, calculate the solids content (%) of the composition. ⁇
  • VOC amount The VOC amount of the viscosity-adjusted aqueous clear coating composition was calculated from the solids content, specific gravity and moisture content of the composition according to equation (1) shown below. The specific gravity was measured by the specific gravity cup method according to JIS K-
  • VOC amount (g/1) ([100 - (S+W) ] X p) / [100 - (W x p) ] (1)
  • S represents the solids content (%) of the coating composition
  • W the moisture content (%) of the coating composition
  • p the specific gravity (g/1) of the coating composition.
  • the lowest viscosity value The viscosity-adjusted aqueous clear coating composition was applied by air spraying to a tin plate (300 x 450 x 0.3 mm) having been degreased with isopropanol, to a film thickness of 35 ⁇ m (when dried) and heated at 60 0 C for about 10 minutes.
  • the uncured coating film formed on the tin plate was scraped off, collected into a sample bottle and sealed therein as a sample by closing the cap.
  • Solids content (%) at the time of viscosity measurement About 2.0 g of the sample was placed in an aluminum foil cup with a diameter of about 5 cm and heated at 110 0 C for 1 hour to measure the amount of residue (g) . The amount of residue after the heating for 1 hour was divided by the original weight of the sample to calculate the solids content (%) of the coating ⁇ composition after applied and heated at 6O 0 C for about 10 minutes. Table 2 shows the proportions of the components, solids content, VOC amount, lowest viscosity value, and solids content at the time of viscosity measurement of each aqueous clear coating composition.
  • thermosetting epoxy resin cationic electrodeposition coating composition (trade name "Elecron GT-10", product of Kansai Paint Co., Ltd.) was applied by electrodeposition to a zinc phosphate-treated cold rolled steel plate treated using "Palbond #3020" (trade name, product of Nihon Parkerizing Co., Ltd.) to a film thickness of about 20 ⁇ m (when cured) and heat-cured at 170 0 C for 30 minutes.
  • a polyester resin/melamine resin intermediate coating composition for automobiles (trade name "Amilac TP-65-2", product of Kansai Paint Co., Ltd.) was applied to the . electrodeposition coat surface by air spraying to a film thickness of about 35 ⁇ m (when cured) and heat-cured at 140 0 C for 30 minutes.
  • the steel plate having the electrodeposition coat and the intermediate coat formed thereon was used as a substrate.
  • An acrylic resin/melamine resin base coating composition for automobiles (trade name "Aqueous metallic base coat WBC 710T #1E7", product of Kansai Paint Co., Ltd.) was applied to the substrate by air spraying to a film thickness of about 15 um (when cured) , allowed to stand at room temperature for 5 minutes and pre-heated at 80 0 C for 10 minutes.
  • Each of the above aqueous clear coating compositions 1 to 14 with a viscosity as adjusted in (1) was applied on the uncured base coating layer by air spraying to a film thickness of about 35 ⁇ m (when cured) .
  • test plates comprising a substrate and a multilayer topcoat film consisting of a base coat and a clear coat formed on the substrate were prepared by a two-coat one-bake method.
  • test plates were tested for coating i performance in terms of appearance, Tukon hardness and water resistance.
  • the coating film thickness ( ⁇ m) at which foaming occurred during the application was also examined.
  • the test methods are as follows: Appearance: The test plate was observed by the naked eye to evaluate the surface smoothness a " nd gloss according to the following criteria:
  • Tukon hardness After the test plate was left in a thermostatic room at 20°C for 24 hours, Tukon hardness of the coating film was measured ' using a Tukon Microhardness Tester (trade name, product of American Chain & Cable Company) .
  • Tukon hardness also called "Knoop Hardness Number (KHN)" is a value expressing the hardness of a coating film determined by- pressing a square pyramidal diamond indenter with a specific load in the surface of a test material and measuring the size of the diamond-shaped indentation in the surface. The greater is the Tukon hardness value, the higher is the hardness.
  • the test plate was left in a thermostatic - room at 20 0 C for 24 hours, immersed at 80 0 C in warm water for 5 hours and then gradually cooled from 80 0 C to room temperature while kept immersed. The test plate was removed from the water and the surface state of the test plate was evaluated according to the following criteria: A: Good gloss; B: Poor gloss;
  • Coating film thickness at which foaming occurred Test plates were prepared in the same manner as the above except that each aqueous coating composition was applied to form a coating film • with gradient thicknesses of from 20 um to 60 ⁇ m. The test plate was observed for air bubble traces on the coated surface due to foaming, and the minimum coating film thickness of the port ⁇ ons at which air bubble traces were observed was defined as the coating film thickness ( ⁇ m) at which foaming occurred. The greater is the value, the higher is the antifoaming property.
  • Table 3 shows the above performance test results .
  • ">60" indicates that the coating film thickness at which foaming occurred exceeds 60 ⁇ ' ⁇ m.

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Abstract

La présente invention a trait à une composition de revêtement transparente aqueuse comportant (A) une dispersion aqueuse d'une résine particulaire contenant un groupe hydroxy et un groupe acide ayant une valeur d'hydroxy de 30 à 200 mg KOH/g, une valeur d'acide de 5 à 50 mg KOH/g et une taille moyenne de particules de 50 à 300 nm, et (B) un agent de réticulation ayant une viscosité telle que la valeur de viscosité la plus faible de la composition telle que mesurée dans une plage de température de 30 °C à 150 °C à une fréquence de 0,1 Hz à une teneur en solides d'au moins 90 % en poids est égale ou inférieure à 30 Pas. L'invention a également trait à un procédé pour la formation d'un film de finition multicouche mettant en oeuvre la composition de revêtement transparente aqueuse.
PCT/JP2006/315435 2005-07-29 2006-07-28 Composition de revetement transparente aqueuse et procede de formation de film de finition multicouche WO2007013684A2 (fr)

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Cited By (5)

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JP2010526194A (ja) * 2007-05-04 2010-07-29 ビーエーエスエフ コーティングス アクチェンゲゼルシャフト ウレタンベースの水性二層被覆システム、それらの使用、および該システムで被覆した基材
WO2014025748A1 (fr) * 2012-08-10 2014-02-13 Axalta Coating Systems IP Co. LLC Compositions de revêtement à deux composants à base hydrique
JP2015155544A (ja) * 2009-06-24 2015-08-27 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ 被覆剤、及び当該被覆剤から製造され、エリクセン深さ試験における良好な結果と、良好な耐ストーンチップ性とを同時に有する、引掻強度が高い被覆物
WO2022076276A3 (fr) * 2020-10-05 2022-05-19 Ppg Industries Ohio, Inc. Procédés d'application à haute efficacité de transfert de compositions de revêtement à durcissement à basse température et substrats revêtus ainsi formés
CN114854254A (zh) * 2022-06-15 2022-08-05 福建合润包装涂料有限公司 一种用于食品三片罐的水性罩光涂料及其制备方法

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WO2010122965A1 (fr) * 2009-04-21 2010-10-28 関西ペイント株式会社 Composition de matière de revêtement et procédé de formation d'un film de revêtement
JP2011140561A (ja) * 2010-01-07 2011-07-21 Nippon Fine Coatings Inc 鋼板プレコート用水性塗料組成物およびこれを用いた塗膜
JP5350430B2 (ja) * 2011-04-19 2013-11-27 本田技研工業株式会社 水性中塗り塗料組成物
JP5991822B2 (ja) * 2012-02-10 2016-09-14 Ｂａｓｆジャパン株式会社 １液型クリヤー塗料組成物及びそれを用いた複層塗膜形成方法
JP5826079B2 (ja) * 2012-03-16 2015-12-02 日本ペイント・オートモーティブコーティングス株式会社 漆黒複層塗膜及びその形成方法
JP2015108049A (ja) * 2013-12-04 2015-06-11 関西ペイント株式会社 ちぢみ模様塗膜を形成可能な塗料組成物
JP7198615B2 (ja) * 2018-07-10 2023-01-04 ダイセル・オルネクス株式会社 硬化性樹脂組成物及びその硬化物
WO2020013067A1 (fr) * 2018-07-10 2020-01-16 ダイセル・オルネクス株式会社 Composition de résine durcissable et produit durci obtenu à partir de celle-ci
JP7383461B2 (ja) * 2019-01-08 2023-11-20 関西ペイント株式会社 複層塗膜形成方法

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JP2010526194A (ja) * 2007-05-04 2010-07-29 ビーエーエスエフ コーティングス アクチェンゲゼルシャフト ウレタンベースの水性二層被覆システム、それらの使用、および該システムで被覆した基材
JP2015155544A (ja) * 2009-06-24 2015-08-27 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ 被覆剤、及び当該被覆剤から製造され、エリクセン深さ試験における良好な結果と、良好な耐ストーンチップ性とを同時に有する、引掻強度が高い被覆物
WO2014025748A1 (fr) * 2012-08-10 2014-02-13 Axalta Coating Systems IP Co. LLC Compositions de revêtement à deux composants à base hydrique
CN104540867A (zh) * 2012-08-10 2015-04-22 涂料外国Ip有限公司 水基双组分涂料组合物
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WO2022076276A3 (fr) * 2020-10-05 2022-05-19 Ppg Industries Ohio, Inc. Procédés d'application à haute efficacité de transfert de compositions de revêtement à durcissement à basse température et substrats revêtus ainsi formés
CN114854254A (zh) * 2022-06-15 2022-08-05 福建合润包装涂料有限公司 一种用于食品三片罐的水性罩光涂料及其制备方法

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