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WO2011099639A1 - Composition de revêtement aqueuse colorée - Google Patents

Composition de revêtement aqueuse colorée Download PDF

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Publication number
WO2011099639A1
WO2011099639A1 PCT/JP2011/053308 JP2011053308W WO2011099639A1 WO 2011099639 A1 WO2011099639 A1 WO 2011099639A1 JP 2011053308 W JP2011053308 W JP 2011053308W WO 2011099639 A1 WO2011099639 A1 WO 2011099639A1
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WO
WIPO (PCT)
Prior art keywords
core
acrylic emulsion
parts
shell
acrylate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2011/053308
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English (en)
Japanese (ja)
Inventor
剛男 柳口
裕介 藤田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kansai Paint Co Ltd
Original Assignee
Kansai Paint Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kansai Paint Co Ltd filed Critical Kansai Paint Co Ltd
Priority to JP2011553922A priority Critical patent/JPWO2011099639A1/ja
Publication of WO2011099639A1 publication Critical patent/WO2011099639A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C09D7/20—Diluents or solvents
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G18/28—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
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • the present invention relates to an aqueous colored coating composition, and particularly to an aqueous colored coating composition useful as a top coating.
  • a carbodiimide compound As a curing agent, it is well known to use a carbodiimide compound as a curing agent.
  • the water-based resin contains a carboxyl group as a water-dispersing group
  • a carbodiimide group that can react with the carboxyl group is used as a crosslinking reactive group in the curing process of the coating film, thereby cross-linking while eliminating the hydrophilic carboxyl group. Since it can take in into reaction, the water resistance of the cured coating film formed improves.
  • Patent Document 1 proposes a thermosetting aqueous coating composition containing a specific hydrophilized modified polycarbodiimide compound and a carboxyl group-containing aqueous resin composition
  • Patent Document 2 proposes a three-chain hydrophilic carbodiimide compound that can be cured at a relatively low temperature and provides a coating film with excellent water resistance, and an aqueous coating composition comprising the same.
  • Patent Documents 1 and 2 it is described that these water-based coating compositions can achieve both curability and storage stability, and that the resulting coating film has good water resistance. Under relatively low temperature conditions such as drying and forced drying, a cured coating film having sufficient performance may not be obtained while satisfying the coating workability and finish performance.
  • Patent Document 3 the present applicant has proposed an aqueous paint composition comprising a base coat paint containing an aqueous acrylic resin and an aqueous urethane resin, and a diluent containing a thickener.
  • an object of the present invention is to provide a water-based colored coating composition that can form a colored coating film that achieves both water resistance and intermediate sharpening properties, and that has good coating workability and finish. .
  • an aqueous coloring paint composition containing a base paint (I) and a diluent (II), wherein the base paint (I) is a core-shell acrylic.
  • the shell portion contains, as monomer units, methyl (meth) acrylate and / or ethyl (meth) acrylate (a 1 ), and the ratio of methyl (meth) acrylate and / or ethyl (meth) acrylate (a 1 ) 40% by mass or more of the total monomer units of the core-shell acrylic emulsion (A), and the core-shell acrylic emma
  • the core portion and / or shell portion of Luchon (B) contains, as a monomer unit, a linear or branched hydrocarbon group-containing polymerizable unsaturated monomer (b 1 ) having 6 or more carbon atoms, and a hydrocarbon group The content of the
  • An aqueous coloring coating composition comprising a base coating (I) and a diluent (II),
  • the base paint (I) contains a core-shell acrylic emulsion (A), a core-shell acrylic emulsion (B), a urethane resin emulsion (C), an acrylic pigment dispersion resin (D), and a colored pigment (E).
  • the core part and / or the shell part of the core-shell type acrylic emulsion (A) contains methyl (meth) acrylate and / or ethyl (meth) acrylate (a 1 ) as monomer units, and methyl (meth) acrylate and / or ethyl.
  • the proportion of (meth) acrylate (a 1 ) is 40% by mass or more of the total monomer units of the core-shell type acrylic emulsion (A),
  • the core part and / or shell part of the core-shell type acrylic emulsion (B) contains, as a monomer unit, a linear or branched hydrocarbon group-containing polymerizable unsaturated monomer (b 1 ) having 6 or more carbon atoms,
  • the proportion of the hydrocarbon group-containing polymerizable unsaturated monomer (b 1 ) is 20 to 80% by mass of the total monomer units of the core-shell type acrylic emulsion (B), and methyl (meth) acrylate and / or ethyl (meth)
  • the proportion of acrylate (a 1 ) is less than 40% by mass of the total monomer units of the core-shell acrylic emulsion (B)
  • Diluent (II) comprises a carbodiimide compound and water, An aqueous coloring paint composition
  • the carboxyl group-containing polymerizable unsaturated monomer (a 2 ) is used as a monomer unit, and the solid content acid value of the core-shell type acrylic emulsion (A) is in the range of 5 to 40 mgKOH / g.
  • the carboxyl group-containing polymerizable unsaturated monomer (b 2 ) is used as a monomer unit, and the solid content acid value of the core-shell type acrylic emulsion (B) is in the range of 1 to 40 mgKOH / g.
  • the aqueous coloring coating composition according to the aspect 1 or 2 further comprising such an amount.
  • the core-shell type acrylic emulsion (A) is 5 to 70% by mass in solid content
  • the core-shell type acrylic emulsion (B) is 20 to 85% by mass in solid content
  • the aqueous colored coating composition according to any one of aspects 1 to 4 further comprising:
  • the aqueous colored coating composition according to any one of aspects 1 to 5, wherein the diluent (II) contains a carbodiimide compound in a range of 0.1 to 20% by mass.
  • the aqueous coloring coating composition contains the diluent (II) in a range of 5 to 100 parts by mass with respect to 100 parts by mass of the solid content of the base coating (I). The aqueous coloring coating composition as described.
  • the water-based colored coating composition of the present invention can form a colored coating film that achieves both water resistance and moderate sharpness even under conditions of room temperature drying or forced drying.
  • water-based coloring coating composition of this invention, and the diluent containing a carbodiimide compound each have favorable storage stability, and can be easily mixed. Therefore, the water-based colored coating composition of the present invention is obtained by mixing both immediately before coating, has good workability in coating, and further, a colored coating film formed from the water-based colored coating composition of the present invention and The multilayer coating film formed by coating clear on the colored coating film has a good metallic feeling, jet blackness and the like, and is excellent in finish.
  • the base paint (I) used in the present invention contains a core-shell type acrylic emulsion (A), a core-shell type acrylic emulsion (B), a urethane resin emulsion, an acrylic pigment dispersion resin (D), and a colored pigment (E). .
  • A core-shell type acrylic emulsion
  • B core-shell type acrylic emulsion
  • D acrylic pigment dispersion resin
  • E colored pigment
  • the core portion and / or shell portion of the core-shell type acrylic emulsion (A) contains methyl (meth) acrylate and / or ethyl (meth) acrylate (a 1 ) as a monomer unit.
  • the proportion of methyl (meth) acrylate and / or ethyl (meth) acrylate (a 1 ) as a monomer unit is about 40 mass of the total monomer units of the core-shell acrylic emulsion (A). And more preferably in the range of about 60 to about 90 mass%.
  • the base paint (I) and the water-based colored paint of the present invention This is not preferable because the viscosity of the composition is lowered, the coating workability varies depending on the coating conditions, and the finish of the colored coating film formed, such as metallic feel and jetness, varies.
  • methyl (meth) acrylate and / or ethyl (meth) acrylate (a 1 ) as monomer units are included as monomer units in the core part as long as the ratio is within the above range. It may be included as a monomer unit of the shell part, or may be included as a monomer unit of both the core part and the shell part.
  • polymerizable unsaturated monomer examples include those conventionally known without limitation, such as n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl (meth) acrylate, lauryl (meth) )
  • Straight chain or branched hydrocarbon group-containing polymerizable unsaturated monomers such as acrylate, stearyl (meth) acrylate, “isostearyl acrylate” (manufactured by Osaka Organic Chemical Co., Ltd.); cyclohexyl (meth) acrylate
  • Group-containing polymerizable unsaturated monomer allyl (meth) acrylate, dipropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2-propyl Polyvinyl compounds such as phenyl (meth) acrylate and 1,1,1-trishydroxymethylethanedi (meth) acrylate; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, ⁇ - (meta ) Alkoxysilyl group-containing polymerizable unsaturated monomers such as acryloyloxypropyltrimethoxysilane, ⁇ - (meth) acryloyloxypropyltriethoxysilane; perfluorobutylethyl (meth) acrylate, perfluorooctylethy
  • Perfluoroalkyl (meth) acrylate polymerizable unsaturated monomer having a fluorinated alkyl group such as fluoroolefin; glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, 3,4-epoxy Epoxy group-containing polymerizable unsaturated monomers such as cyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, 3,4-epoxycyclohexylpropyl (meth) acrylate, and allyl glycidyl ether; maleimide groups, etc.
  • Polymerizable unsaturated monomer having a photopolymerizable functional group 1,2,2,6,6-pentamethylpiperidyl (meth) acrylate, 2,2,2,6,6-tetramethylpiperidinyl (meth) acrylate Etc .
  • vinyl compounds such as N-vinylpyrrolidone, ethylene, butadiene, chloroprene, vinyl propionate, vinyl acetate; (meth) acrylonitrile, (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, Glicisi Nitrogen-containing polymerizable unsaturated monomers such as adducts of ru (meth) acrylate and amines; (meth) acrylates having polyoxyalkylene chains whose molecular ends are alkoxy groups; 2-acrylamido-2-methylpropanesulfonic acid Polymerizable unsaturated monomers having a
  • the ratio of the core part to the shell part is preferably about 10/90 from the viewpoint of the finish of the colored coating film formed using the aqueous colored coating composition of the present invention. Is in the range of about 90/10, and more preferably in the range of about 20/80 to about 80/20.
  • the core-shell type acrylic emulsion (A) is, for example, a polymerizable unsaturated monomer mixture constituting a shell in an aqueous dispersion obtained by polymerizing a polymerizable unsaturated monomer mixture constituting a core in the presence of an emulsifier. Is obtained by polymerization.
  • the average particle size of the core-shell type acrylic emulsion (A) is preferably in the range of about 0.01 to about 1.0 ⁇ m, and more preferably about 0.05 to about 0.5 ⁇ m.
  • the average particle diameter is a value measured by diluting a sample with deionized water with “Nanomizer N-4” (trade name, manufactured by Coulter, Inc., particle size distribution measuring apparatus) to 20 ° C.
  • “Nanomizer N-4” trade name, manufactured by Coulter, Inc., particle size distribution measuring apparatus
  • the core-shell type acrylic emulsion (A) contains a carboxyl group-containing polymerizable unsaturated monomer (a 2 ) as a monomer unit because it has the effect of making the viscosity of the aqueous colored coating composition moderate and improving the finish. It is preferable to do.
  • the carboxyl group-containing polymerizable unsaturated monomer (a 2 ) can be appropriately selected from the compounds listed above.
  • the amount of the carboxyl group-containing polymerizable unsaturated monomer (a 2 ) is preferably from about 5 to about 40 mgKOH / g, and more preferably from about 10 to about 30 mgKOH / g, as the solid content acid value of the core-shell acrylic emulsion (A). The amount is within the range. The said range is preferable from a viewpoint of the water resistance and finishing property of the colored coating film formed from the water-based colored coating composition of this invention, and a viewpoint of coating workability.
  • solid content means a solid content from which volatile components such as water and organic solvent in the sample are removed, and is measured by drying about 2 g of the sample at 105 ° C. for 3 hours. be able to.
  • the carboxyl group-containing polymerizable unsaturated monomer (a 2 ) may be contained as a monomer unit of the core part, may be contained as a monomer unit of the shell part, or Although it may be contained as a monomer unit of both the core part and the shell part, it is preferably contained as a monomer unit of the shell part. This is because the storage stability of the core-shell type acrylic emulsion (A) and the finish of the colored coating film formed by the aqueous colored coating composition of the present invention are excellent.
  • the core-shell acrylic emulsion (A), from the viewpoint of storage stability of the base paint (I), as a monomer unit preferably contains a hydroxyl group-containing polymerizable unsaturated monomer (a 3).
  • the hydroxyl group-containing polymerizable unsaturated monomer (a 3 ) can be appropriately selected from the compounds listed above.
  • the amount of the hydroxyl group-containing polymerizable unsaturated monomer (a 3 ) is preferably from about 1 to about 100 mgKOH / g, and more preferably from about 10 to about 50 mgKOH / g, as the solid hydroxyl value of the core-shell acrylic emulsion (A). The amount is within the range. The said range is preferable from the point of the water resistance and finishing property of the colored coating film formed from the water-based colored coating composition of this invention.
  • the hydroxyl group-containing polymerizable unsaturated monomer (a 3 ) may be included as a monomer unit of the core portion, a monomer unit of the shell portion, or a core in the core-shell type acrylic emulsion (A). It may be included as both monomer units and shell units.
  • the core-shell type acrylic emulsion (A) contains a polyvinyl compound (a 4 ) as a monomer unit from the viewpoint of the coating workability of the water-based colored coating composition of the present invention and the finish of the colored coating film to be formed. It is preferable to do.
  • the other vinyl compound (a 4 ) can be appropriately selected from the compounds listed above.
  • the ratio of the polyvinyl compound (a 4 ) is preferably about 0.1 to about 3.0% by mass, and more preferably about 0.1%, based on the total amount of monomer units of the core-shell type acrylic emulsion (A). It is in the range of about 2.0% by mass.
  • the polyvinyl compound (a 4 ) may be contained as a monomer unit of the core part, may be contained as a monomer unit of the shell part, or the core part and the shell part. These may be contained as both monomer units, but are preferably contained as monomer units in the core portion. This is because the storage stability and production stability of the core-shell type acrylic emulsion (A) and the finish of the colored coating film formed by the aqueous colored coating composition of the present invention are excellent.
  • the core-shell acrylic emulsion (A) preferably has a glass transition temperature in the range of about 0 to about 60 ° C., and more preferably about 10 to about 50 ° C.
  • T1, T2... Tn are homopolymer glass of each monomer. Transition temperature (absolute temperature).
  • the glass transition temperature of the homopolymer of each monomer is a value according to Polymer Hand Book (4th Edition), and the glass transition temperature of the monomer not described in the above literature is a homopolymer of the monomer having a weight average molecular weight of 5 A value obtained by synthesizing to about 10,000 and measuring the glass transition temperature by differential scanning thermal analysis is used.
  • polymerization initiator that can be used for the polymerization of the core-shell type acrylic emulsion (A)
  • conventionally known polymerization initiators can be used without limitation, and examples thereof include benzoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide.
  • Organic peroxides such as cumene hydroperoxide, tert-butyl peroxide, tert-butyl peroxylaurate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxyacetate, diisopropylbenzene hydroperoxide; azobisiso Butyronitrile, azobis (2,4-dimethylvaleronitrile), azobis (2-methylpropiononitrile), azobis (2-methylbutyronitrile), 4,4′-azobis (4 Cyanobutanoic acid), dimethylazobis (2-methylpropionate), azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], azobis ⁇ 2-methyl-N- [2- (1-hydroxy Butyl)]-propionamide ⁇ , persulfates such as potassium persulfate, ammonium persulfate, sodium persulfate, and the like, and combinations thereof.
  • persulfates
  • an anionic emulsifier and a nonionic emulsifier are suitable as an emulsifier that can be used for the polymerization of the core-shell type acrylic emulsion (A).
  • an anionic emulsifier and a nonionic emulsifier are suitable.
  • the anionic emulsifier include alkyl sulfonic acid, alkyl benzene sulfonic acid, and alkyl phosphoric acid. Examples include sodium salts and ammonium salts such as acids.
  • nonionic emulsifier examples include polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene phenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene nonylphenyl ether, Oxyethylene octyl phenyl ether, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate, sorbitan monolaurate, sorbitan monostearate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan A monolaurate etc. are mentioned.
  • a polyoxyalkylene group-containing anionic emulsifier having an anionic group and a polyoxyalkylene group such as a polyoxyethylene group or a polyoxypropylene group in one molecule a polyoxyalkylene group-containing anionic emulsifier having an anionic group and a polyoxyalkylene group such as a polyoxyethylene group or a polyoxypropylene group in one molecule;
  • a reactive anionic emulsifier having an anionic group and a polymerizable unsaturated group in the molecule can be used.
  • the carboxyl group is neutralized with a neutralizing agent.
  • the neutralizing agent is not particularly limited. For example, ammonia, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, monoethanolamine, diethanolamine, butylamine, ethylenediamine, methylethanolamine, dimethylethanolamine, dimethylpropanolamine.
  • An amine compound such as
  • the core part and / or the shell part of the core-shell type acrylic emulsion (B) is a linear or branched hydrocarbon group-containing polymerizable unsaturated monomer (b) having about 6 or more carbon atoms as a monomer unit. 1 ).
  • the proportion of the hydrocarbon group-containing polymerizable unsaturated monomer (b 1 ) as the monomer unit is about 20 to about 80% by mass of the total monomer units of the core-shell type acrylic emulsion (B). And preferably about 30 to about 60% by weight. If the proportion of the hydrocarbon group-containing polymerizable unsaturated monomer (b 1 ) as the monomer unit is less than about 20% by mass, the formed coating film has insufficient water resistance, while if it exceeds about 80% by mass, the base paint Since the storage stability of (I) is insufficient, it is not preferable.
  • hydrocarbon group-containing polymerizable unsaturated monomer (b 1 ) examples include, for example, n-hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, tridecyl ( Examples thereof include (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, “isostearyl acrylate” (manufactured by Osaka Organic Chemical Co., Ltd.), and combinations thereof.
  • the hydrocarbon group-containing polymerizable unsaturated monomer (b 1 ) may be contained as a monomer unit of the core part as long as the ratio is within the above range. It may be included as a monomer unit, or may be included as a monomer unit of both the core part and the shell part.
  • the proportion of methyl (meth) acrylate and / or ethyl (meth) acrylate (a 1 ) as a monomer unit is about 40 mass of the total monomer units of the core-shell acrylic emulsion (B). %.
  • the core-shell type acrylic emulsion (B) is, for example, in an aqueous dispersion obtained by polymerizing a polymerizable unsaturated monomer mixture constituting the core in the presence of an emulsifier, as in the case of the core-shell type acrylic emulsion (A).
  • the polymer is obtained by adding a polymerizable unsaturated monomer mixture constituting the shell and polymerizing.
  • the average particle size of the core-shell type acrylic emulsion (B) is preferably about 0.01 to about 1.0 ⁇ m, and more preferably about 0.05 to about 0.5 ⁇ m, like the core-shell type acrylic emulsion (A). Is in range.
  • the finish of the colored coating film formed from the aqueous colored coating composition of the present invention can be further improved.
  • the ratio of the core part to the shell part is preferably in the range of about 10/90 to about 90/10, and more preferably about 20/80 to about 80/20. Is within the range.
  • the above range is preferable from the viewpoint of setting the viscosity of the water-based colored coating composition of the present invention to a viscosity suitable for coating, the viewpoint of suppressing the viscosity reduction during storage, and the finish of the colored coating film.
  • Polymerization that can be used for the polymerization of monomer units other than the hydrocarbon group-containing polymerizable unsaturated monomer (b 1 ) in the core portion and the shell portion of the core-shell type acrylic emulsion (B), that is, the core-shell type acrylic emulsion (B).
  • unsaturated monomer include those listed in the section of the core-shell type acrylic emulsion (A).
  • polymerization initiator and the emulsifier used for the polymerization of the core-shell type acrylic emulsion (A) include those listed in the section of the core-shell type acrylic emulsion (A).
  • the core-shell type acrylic emulsion (B) is a carboxyl group-containing polymerizable unsaturated monomer (b 2) as a monomer unit from the viewpoint of water-resistant adhesion of a colored coating film formed from the aqueous colored coating composition of the present invention. ) Is preferably contained.
  • the carboxyl group-containing polymerizable unsaturated monomer (b 2 ) include the same ones as the carboxyl group-containing polymerizable unsaturated monomer (a 2 ) described in the section of the core-shell acrylic emulsion (A).
  • the amount of the carboxyl group-containing polymerizable unsaturated monomer (b 2 ) is preferably from about 1 to about 40 mg KOH / g, and more preferably from about 5 to about 30 mg KOH / g, as the solid content acid value of the core-shell acrylic emulsion (B).
  • the amount is within the range.
  • the said range is preferable from a viewpoint of the water resistance of the colored coating film formed from the water-based colored coating composition of this invention, and the finishing property of a colored coating film.
  • the carboxyl group-containing polymerizable unsaturated monomer (b 2 ) may be contained as a monomer unit of the core part, may be contained as a monomer unit of the shell part, or Although it may be contained as a monomer unit of both the core part and the shell part, it is preferably contained as a monomer unit of the shell part. This is because the storage stability of the core-shell type acrylic emulsion (B), the finish of the colored coating film formed by the aqueous colored coating composition of the present invention, and the water adhesion resistance are excellent.
  • the core-shell type acrylic emulsion (B) desirably contains a hydroxyl group-containing polymerizable unsaturated monomer (b 3 ) as a monomer unit from the viewpoint of storage stability of the base coating material (I).
  • the hydroxyl group-containing polymerizable unsaturated monomer (b 3 ) include the same hydroxyl group-containing polymerizable unsaturated monomer (a 3 ).
  • the amount of the hydroxyl group-containing polymerizable unsaturated monomer (b 3 ) is preferably from about 1 to about 100 mgKOH / g, and more preferably from about 10 to about 50 mgKOH / g, as the solid content hydroxyl value of the core-shell acrylic emulsion (B). The amount is within the range. The said range is suitable from the point of the water resistance and finishing property of the colored coating film formed from the water-based coloring coating composition of this invention.
  • the hydroxyl group-containing polymerizable unsaturated monomer (b 3 ) may be included as a monomer unit of the core portion, a monomer unit of the shell portion, or a core in the core-shell type acrylic emulsion (B). It may be included as both monomer units and shell units.
  • the polyvinyl compound (b 4 ) include the same compounds as the other vinyl compounds (a 4 ).
  • the proportion of the polyvinyl compound (b 4 ) is preferably about 0.1 to about 3% by mass, and more preferably about 0.1 to about 3% by mass, based on the total amount of all monomer units of the core-shell type acrylic emulsion (B). It is in the range of about 2% by weight.
  • the polyvinyl compound (b 4 ) may be contained as a monomer unit of the core part, may be contained as a monomer unit of the shell part, or the core part and the shell part. These may be contained as both monomer units, but are preferably contained as monomer units in the core portion. This is because the storage stability and production stability of the core-shell type acrylic emulsion (B), and the sharpening property of the colored coating film formed by the aqueous colored coating composition of the present invention are excellent.
  • the carboxyl group is neutralized with a neutralizing agent.
  • a neutralizing agent There is no restriction
  • the compound listed by the term of a core-shell type acrylic emulsion (A) can be mentioned.
  • the core-shell acrylic emulsion (B) preferably has a glass transition temperature in the range of about ⁇ 60 to about 0 ° C., and more preferably about ⁇ 50 to about ⁇ 10 ° C. Since the water-based colored coating composition of the present invention contains the core-shell type acrylic emulsion (B) and the urethane resin emulsion (C) described later, it is possible to achieve both the hardness and water resistance of the formed colored coating film. It is considered.
  • urethane resin emulsion (C) As the urethane resin emulsion (C), those usually used as urethane resin emulsions in this technical field can be used without particular limitation.
  • the urethane resin emulsion (C) preferably has an average particle size in the range of about 0.01 to about 1.0 ⁇ m, and more preferably about 0.01 to about 0.5 ⁇ m.
  • the urethane resin emulsion (C) is obtained, for example, by dispersing a urethane prepolymer produced by reacting a polyisocyanate, a polyol and a carboxyl group-containing diol in water in the presence of a desired chain extender.
  • polyisocyanate examples include aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, and lysine diisocyanate; burette type adducts, isocyanurate ring adducts of these diisocyanate compounds; isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4- (or 2,6-) diisocyanate, 1,3- (or 1,4-) di (isocyanatomethyl) cyclohexane, 1,4- Cycloaliphatic diisocyanate, 1,3-cyclopentane diisocyanate, 1,2-cyclohexane diisocyanate and other alicyclic diisocyanate compounds; these diisocyanates Burette type adducts, isocyanurate ring adducts;
  • polyol examples include polyether polyols such as polyethylene glycol, polypropylene glycol, polyethylene-propylene (block or random) glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, polyoctamethylene ether glycol; dicarboxylic acid (adipine) Acid, succinic acid, sebacic acid, glutaric acid, maleic acid, fumaric acid, phthalic acid, etc.) and glycol (ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1 , 5-pentanediol, neopentyl glycol, bishydroxymethylcyclohexane, etc.), for example, polyols produced by polycondensation such as polyethylene adipate, poly Polyester polyols such as tylene adipate, polyhexamethylene adipate, polyneopentyl adipate,
  • polycarbonate polyol examples include those obtained by reacting a carbonate and polyol, and those obtained by reacting phosgene with bisphenol A and the like.
  • Examples of the carbonate ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like.
  • examples of the polyol capable of reacting with the carbonate ester include ethylene glycol, diethylene glycol, Triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1 10-decanediol, 1,11-undecanedi
  • carboxyl group-containing diol examples include dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutyric acid, and the like. From the viewpoint of the hardness and water resistance of the colored coating film formed from the aqueous colored coating composition of the present invention. Dimethylolpropionic acid is preferred.
  • Diamines such as diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine; hydroxyethylhydrazine, hydroxyethyldiethylenetriamine, 2-[(2-aminoethyl) Amino] ethanol, the compound having an amino group and a hydroxyl group such as 3-amino-propanedio
  • the urethane resin emulsion (C) contains a carboxyl group or the like, it can be neutralized with a neutralizing agent.
  • a neutralizing agent There is no restriction
  • acrylic pigment-dispersed resin (D) examples include an acrylic resin obtained by polymerizing a polymerizable unsaturated monomer with a polymerization initiator in the presence of a hydrophilic organic solvent.
  • the acrylic pigment-dispersed resin (D) is preferably a resin that can be dissolved or dispersed in water, specifically, preferably about 10 to about 100 mg KOH / g, and more preferably about 20 to It has a hydroxyl value of about 70 mg KOH / g and an acid value of preferably about 10 to about 80 mg KOH / g, and more preferably about 20 to about 60 mg KOH / g.
  • hydrophilic organic solvent used for polymerization examples include alcohol organic solvents such as methanol, ethanol, isopropanol, n-butanol and isobutanol; ether organic solvents such as dioxane and tetrahydrofuran; ethylene glycol monomethyl ether and ethylene glycol.
  • Ethylene glycol ether organic solvents such as monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono tert-butyl ether; diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol mono n-propyl ether Diethylene glycol ether organic solvents such as diethylene glycol monoisopropyl ether, diethylene glycol mono n-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono tert-butyl ether; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol Propylene glycol ether organic solvents such as monoisopropyl ether;
  • Examples of the polymerization initiator include compounds listed in the section of the core-shell type acrylic emulsion (A).
  • acrylic pigment dispersion resin (D) has a carboxyl group, it is preferable to neutralize the said carboxyl group with a neutralizing agent.
  • the neutralizing agent is not particularly limited as long as it can neutralize a carboxyl group, and examples thereof include compounds listed in the section of the core-shell type acrylic emulsion (A).
  • the acrylic pigment dispersion resin (D) preferably has a weight average molecular weight in the range of about 1000 to about 100,000, and more preferably about 8,000 to about 70,000.
  • the number average molecular weight and the weight average molecular weight mean values obtained by converting the molecular weight measured with a gel permeation chromatograph (“HLC8120GPC” manufactured by Tosoh Corporation) based on the molecular weight of polystyrene. .
  • HSC8120GPC gel permeation chromatograph
  • TSKgel G-4000H ⁇ L “TSKgel G-3000H ⁇ L”
  • TSKgel G-2500H ⁇ L” “TSKgel G-2000H ⁇ L” (both manufactured by Tosoh Corporation)
  • the measurement is performed under the conditions of mobile phase: tetrahydrofuran, measurement temperature: 40 ° C., flow rate: 1 cc / min, detector: RI.
  • the water-based colored coating composition of the present invention is based on the total solid content of the core-shell type acrylic emulsion (A), the core-shell type acrylic emulsion (B), the urethane resin emulsion (C), and the acrylic pigment dispersion resin (D).
  • the core-shell type acrylic emulsion (A) is preferably about 5 to about 70% by mass, and more preferably about 7 to about 61% by mass in terms of solid content.
  • the core-shell type acrylic emulsion (B) is preferably about 20 to about 85% by mass, and more preferably about 25 to about 79% by mass in terms of solid content.
  • the urethane resin emulsion (C) is preferably about 5 to about 70% by mass, and more preferably about 7 to about 61% by mass, and the acrylic pigment dispersion resin (D) is preferably about solids. Is about 5 to about 70% by weight, and more preferably about 7 to about 61% by weight. The above range is preferable from the viewpoints of the storage stability of the base coating material (I), the finish of the colored coating film formed using the colored coating composition of the present invention, the water resistance, the sharpening property, and the like.
  • the water-based colored paint composition of the present invention can exhibit its effect to the maximum when it is an enamel paint containing the color pigment (E), and the color pigment (E) is included in the base paint (I). Is done.
  • the color pigment (E) those usually used in the paint field are not particularly limited, and various color pigments can be used according to the purpose.
  • the color pigment (E) include metallic pigments such as aluminum powder, bronze powder, copper powder, tin powder, lead powder, zinc powder, iron phosphide; pearl-like metal-coated mica powder, mica-like iron oxide, etc.
  • Pearl pigments white pigments such as titanium oxide; black pigments such as carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black; yellow iron oxide, titanium yellow, monoazo yellow, condensed azo yellow, azomethine Yellow pigments such as yellow, bismuth vanadate, benzimidazolone, isoindolinone, isoindoline, quinophthalone, benzidine yellow, permanent yellow; orange pigments such as permanent orange; red iron oxide, naphthol AS azo red, ansanthrone, anthrac Nonyl red, perylenema Red pigments such as cobalt, quinacridone-based red pigments, diketopyrrolopyrrole, watching red and permanent red; purple pigment
  • the color pigment (E) is mixed with the base paint (I) in a state of being dispersed by the acrylic pigment dispersion resin (D), and the amount of the color pigment (E) varies depending on the type of the pigment and the like. However, in general, it is preferably about 0.1 to about 300 parts by weight, and more preferably about 1 to about 150 parts by weight with respect to 100 parts by weight of the solid content of the resin component contained in the base paint (I). Within the range of the part.
  • the base paint (I) may be an extender pigment, a thickener, an organic solvent, an ultraviolet absorber, a light stabilizer, a surface conditioner, polymer fine particles, a dispersion aid, a basic neutralizer, a preservative, if desired.
  • Other components usually used in water-based paints such as an antifoaming agent and a curing catalyst can be included.
  • the diluent (II) gives the base coating (I) a wide range of workability by diluting the base coating (I), generally just before coating, and also provides the colored coating of the present invention. It is a component which can improve the water resistance of the colored coating film formed with a composition.
  • Diluent (II) contains a carbodiimide compound and water.
  • the carbodiimide compound preferably has two or more carbodiimide groups in the molecule and has water solubility or water dispersibility.
  • the carbodiimide compound preferably has a carbodiimide equivalent in the range of about 100 to about 800, and more preferably about 200 to about 600.
  • the carbodiimide compound can be produced, or a commercially available product can be used as it is, and specific examples of commercially available products include, for example, “Carbodilite V-02”, “Carbodilite V-04”, “Carbodilite V-06” “Carbodilite E-01”, “Carbodilite E-04” (trade name, manufactured by Nisshinbo Co., Ltd.) and the like can be mentioned. These may be used alone or in a mixture of two or more.
  • Diluent (II) is preferably a carbodiimide compound, preferably about 0.1 to about 20% by mass, more preferably about 1 from the viewpoint of the finish of a colored coating film formed from the aqueous colored coating composition of the present invention. It is contained in a range of ⁇ 10% by mass.
  • Diluent (II) is for paints usually contained in water-based paints such as organic solvents, UV absorbers, light stabilizers, basic neutralizers, preservatives, antifoaming agents, surface conditioners, curing catalysts, etc., if desired. Other components such as additives can be further included.
  • the water-based colored coating composition of the present invention can be a two-pack type coating composed of a base coating (I) and a diluent (II).
  • the aqueous coloring paint composition of the present invention can be easily prepared by mixing the base paint (I) and the diluent (II) immediately before painting.
  • the ratio of the base coating (I) and the diluent (II) can be appropriately adjusted depending on the coating environment and the like.
  • the diluent (II) is used in the base coating (I).
  • the solid content is preferably about 5 to about 100 parts by mass, and more preferably about 10 to about 60 parts by mass with respect to 100 parts by mass of the solid content. The said range is preferable from a viewpoint of the finish of the colored coating film formed from the water-based coloring coating composition of this invention, water resistance, and coating workability
  • the equivalent ratio of the carbodiimide group contained in the diluent (II) to the carboxyl group contained in the base paint (I) is preferably about 0.1 to about 1.5, and more preferably about 0.1 to Within the range of about 1.0 equivalent.
  • the said range is preferable from a water-resistant viewpoint of the colored coating film formed from the water-based coloring coating composition of invention.
  • Examples of the object to be coated with the aqueous colored coating composition of the present invention include iron, aluminum, brass, copper plate, stainless steel plate, tin plate, galvanized steel plate, alloyed zinc (Zn-Al, Zn-Ni, Zn-Fe, etc.) Metals such as plated steel sheets; Surface-treated metals obtained by subjecting these metal surfaces to chemical conversion treatment such as zinc phosphate treatment and chromate treatment; Surfaces of materials to be coated such as plastic, wood, concrete, mortar, etc. Examples of the material surface to be coated include a primer or the like undercoating, intermediate coating, overcoating, or clear coating.
  • the drying method of the water-based colored coating composition of the present invention is not particularly limited, and normal temperature drying, forced drying, and heat drying can be used. The effect is high under dry conditions.
  • a top clear coating may be applied thereon to form a clear coating film.
  • the colored coating formed from the aqueous colored coating composition of the present invention may be cured and dried, or the top clear coating is applied over the uncured colored coating, Both coatings can also be dried.
  • top clear coating conventionally known ones can be used without particular limitation, for example, acrylic resins containing a crosslinkable functional group such as a hydroxyl group, fluororesins, etc., main ingredients such as block polyisocyanates, polyisocyanates, melamine resins, etc.
  • Two-part curable paints using a curing agent lacquer paints mainly composed of cellulose acetate butyrate-modified acrylic resin, and the like.
  • a coating containing a polyisocyanate curing agent is obtained by transferring a part of the polyisocyanate curing agent from a top clear coating to a colored coating formed from an aqueous colored coating composition, and the hydroxyl group in the colored coating. And the adhesion between the colored coating film and the top clear coating film, water adhesion resistance, and the like can be improved.
  • a monomer emulsion comprising 20 parts of the following monomer mixture (2), 0.5 part of “Newcol 562SF”, 13 parts of deionized water, and 3 parts of a 0.7% ammonium persulfate aqueous solution was added to the reaction vessel over 2 hours. It was dripped in.
  • the remaining monomer emulsion was added dropwise to the reaction vessel with a metering pump over 3 hours, and aged for 1 hour after completion of the addition.
  • a monomer emulsion comprising 30 parts of the following monomer mixture (6), 0.5 part of “Newcol 562SF”, 13 parts of deionized water, and 3 parts of a 0.7% ammonium persulfate aqueous solution was added to the reaction vessel over 2 hours. It was dripped in.
  • the remaining monomer emulsion was added dropwise to the reaction vessel with a metering pump over 3 hours, and aged for 1 hour after completion of the addition.
  • 43 parts of 0.5% aqueous dimethylethanolamine solution was added to the reaction vessel, cooled to 30 ° C., filtered through a 100 mesh nylon cloth, and an acid value of 9.8 mg KOH / g, hydroxyl value of 21 mg KOH / g, A single-layer acrylic emulsion having a glass transition temperature of ⁇ 42 ° C., an average particle size of 120 nm, and a non-volatile content of 35.2% was obtained.
  • the amount of free isocyanate groups in the urethane prepolymer was 2.1%.
  • 3.1 parts of triethylamine was added to the urethane prepolymer for neutralization, and then 250 parts of distilled water was added to the urethane prepolymer and emulsified while stirring at high speed using a homomixer.
  • the urethane resin emulsion (C-1) was obtained by collect
  • NF biisomer S20W trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., methoxypolyethylene glycol methacrylate (compound containing a 45-mer of oxyethylene groups in the molecule and having a methoxy group at the end), Active ingredient 50%, molecular weight 2080.
  • the product was neutralized with dimethylethanolamine in an equivalent amount, 450 parts of propylene glycol mono n-propyl ether was added, and the pH was adjusted to 7.5 with dimethylethanolamine, and the pigment dispersion was a yellow liquid.
  • a solution (solid content 55%) of resin (D-2) was obtained.
  • the weight average molecular weight of the pigment dispersion resin (D-2) was 45,000, the acid value was 47 mgKOH / g, and the hydroxyl value was 51 mgKOH / g.
  • Phosphate group-containing resin solution A solvent consisting of 27.5 parts of methoxypropanol and 27.5 parts of isobutanol is placed in a 4 liter flask equipped with a stirrer, a temperature controller and a refrigerator.
  • Phosphoric acid group-containing polymerizable monomer 57.5 parts of monobutyl phosphoric acid and 41.1 parts of isobutanol are placed in a 4 liter flask, and 42.5 parts of glycidyl methacrylate are added dropwise over 2 hours under aeration. Then, the mixture was aged with stirring for 1 hour. Subsequently, 5.9 parts of isopropanol was added to obtain a phosphoric acid group-containing polymerizable monomer solution having a solid content of 50%.
  • Examples 2 to 8 and Comparative Examples 2 to 4 An aqueous colored coating composition was produced in the same manner as in Example 1 except that the resin and pigment were as shown in Table 1 or Table 3.
  • the resin amount of Table 1 and Table 3 means solid content
  • the quantity of an aluminum pigment means the mass of the aluminum pigment with respect to PHR, ie, 100 mass parts of resin solid content contained in a base coating material.
  • Example 1 Example 1 except that the diluent was changed to a diluent containing 5% "Baihijole VPLS2319" (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd., light yellow transparent liquid water-dispersible polyisocyanate) and 95 parts of water. In the same manner, an aqueous colored coating composition was produced.
  • a diluent containing 5% "Baihijole VPLS2319” trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd., light yellow transparent liquid water-dispersible polyisocyanate
  • Example 10 to 16 and Comparative Example 5 A black-based aqueous colored coating composition was produced in the same manner as in Example 9 except that the resin and pigment were as shown in Table 2 or Table 3. In Tables 2 and 3, the amount of the carbon black pigment means PHR as in the case of the aluminum pigment.
  • a diluent is added to a metallic paint base agent or a black paint base agent, and after mixing for 1 minute by hand stirring, the state of the paint is evaluated based on the following criteria.
  • a base plate is prepared by polishing the surface of the clear coating film of the coated plate, which has been formed in order for undercoat, intermediate coating and topcoat clear for automobile body, with # 800 water-resistant paper and then degreasing.
  • the aqueous colored coating composition produced in Examples 1 to 16 and Comparative Examples 1 to 5 is applied to the base plate in four stages under conditions of 25 ° C. and relative humidity of 40%. Between each stage, hot air of 50 ° C was blown to each test plate at 10 m / sec with a hot air generator, and the surface was dried to the touch dry state. Finally, the base coat with a dry film thickness of 15 ⁇ m Get.
  • Letane PG Multiclear HX (Q) (trade name, manufactured by Kansai Paint Co., Ltd., clear paint containing hydroxyl group-containing acrylic resin) is added to “Letane PG Multiclear Standard Curing Agent” (trade name, Kansai Paint Co., Ltd.).
  • a top clear coating material prepared by mixing 50 parts of hexamethylene diisocyanate isocyanurate type polyisocyanate curing agent) immediately before coating is air spray-coated on the base coat so as to have a dry film thickness of 40 ⁇ m, and then a dryer.
  • a test coating plate is obtained by forcibly drying for 20 minutes so that the temperature of the base plate is kept at 60 ° C. Based on the following evaluation criteria, the coating surface of the test coating plate obtained in this way is visually evaluated, aluminum orientation for the metallic coating test plate, and jetness for the black coating test plate. evaluate.
  • Many metallic unevenness is recognized ⁇ : Very much metallic unevenness is recognized
  • the base coat formed in the evaluation of the finish is left in a laboratory at about 20 ° C. for 2 hours, and then the surface of the base coat is reciprocated 5 times while applying a load of 50 g / cm 2 using a P800 abrasive paper. Grind. Based on the following criteria, how the scratches enter the surface of the base coat and the state of adhesion of the coating film to the abrasive paper are evaluated. A: No deep scratches are observed on the surface of the base coat, and no coating film is adhered to the abrasive paper. O: Slight scratches are observed on the surface of the base coat, and many coating films are adhered to the abrasive paper. Deep scratches are observed on the surface of the base coat, and many coating films are adhered to the abrasive paper. ⁇ : Many deep scratches are observed on the surface of the base coat, and many coating films are adhered to the abrasive paper.

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Abstract

La présente invention concerne une composition de revêtement aqueuse colorée permettant la formation d'un film de revêtement coloré qui peut présenter à la fois une résistance à l'eau et des propriétés de rebroyage, et qui présente une bonne aptitude à l'enduction et qui donne une bonne finition. La composition de revêtement aqueuse colorée peut être utilisée pour le revêtement de carrosseries de véhicules et possède la constitution suivante. La composition de revêtement aqueuse colorée comprend un matériau de revêtement de base (I) et un diluant (II), et est caractérisée en ce que l'agent de revêtement de base (I) comprend une émulsion acrylique de type noyau/enveloppe (A), une émulsion acrylique de type noyau/enveloppe (B), une émulsion de résine uréthane (C), une résine acrylique dans laquelle sont dispersés des pigments (D) et un pigment colorant (E) et le diluant (II) comprend un composé carbodiimide et de l'eau.
PCT/JP2011/053308 2010-02-10 2011-02-09 Composition de revêtement aqueuse colorée Ceased WO2011099639A1 (fr)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013176266A1 (fr) * 2012-05-24 2013-11-28 関西ペイント株式会社 Composition de matériau de revêtement à base d'eau, procédé de formation de film de revêtement multicouche, et article possédant un film de revêtement multicouche
JP2014125604A (ja) * 2012-12-27 2014-07-07 Kansai Paint Co Ltd 多成分系の水性塗料組成物
KR101417343B1 (ko) 2012-09-19 2014-07-10 현대자동차주식회사 고휘도의 수성 메탈릭 도료 조성물
WO2015107933A1 (fr) * 2014-01-15 2015-07-23 Dic株式会社 Agent de traitement de surface aqueux et produit l'utilisant
JP2020002244A (ja) * 2018-06-27 2020-01-09 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 水性塗料組成物および水性塗料組成物の製造方法
JP2020511582A (ja) * 2017-03-23 2020-04-16 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 ポリマーを含む水性着色顔料ペースト、およびそれから製造されるベースコート
JP2020111717A (ja) * 2019-01-08 2020-07-27 株式会社ウェルグリーン ２液常温硬化型樹脂組成物及び硬化型樹脂の製造法
WO2020153023A1 (fr) * 2019-01-21 2020-07-30 Dic株式会社 Composition de résine aqueuse, film et tissu étanche perméable à l'humidité
CN115894823A (zh) * 2022-06-14 2023-04-04 衡水新光新材料科技有限公司 一种可研磨乳液、水性工业漆及其制备方法
WO2025074864A1 (fr) * 2023-10-03 2025-04-10 Dic株式会社 Dispersion aqueuse, matériau de revêtement aqueux et produit moulé en plastique ayant un film de revêtement dudit matériau de revêtement aqueux

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CN104334658A (zh) * 2012-05-24 2015-02-04 关西涂料株式会社 水性涂料组合物、多层涂膜形成方法以及具有多层涂膜的物品
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KR101417343B1 (ko) 2012-09-19 2014-07-10 현대자동차주식회사 고휘도의 수성 메탈릭 도료 조성물
JP2014125604A (ja) * 2012-12-27 2014-07-07 Kansai Paint Co Ltd 多成分系の水性塗料組成物
WO2015107933A1 (fr) * 2014-01-15 2015-07-23 Dic株式会社 Agent de traitement de surface aqueux et produit l'utilisant
JPWO2015107933A1 (ja) * 2014-01-15 2017-03-23 Dic株式会社 水性表面処理剤及びそれを用いた物品
JP2020511582A (ja) * 2017-03-23 2020-04-16 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 ポリマーを含む水性着色顔料ペースト、およびそれから製造されるベースコート
JP7143318B2 (ja) 2017-03-23 2022-09-28 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 ポリマーを含む水性着色顔料ペースト、およびそれから製造されるベースコート
JP2020002244A (ja) * 2018-06-27 2020-01-09 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 水性塗料組成物および水性塗料組成物の製造方法
JP2020111717A (ja) * 2019-01-08 2020-07-27 株式会社ウェルグリーン ２液常温硬化型樹脂組成物及び硬化型樹脂の製造法
WO2020153023A1 (fr) * 2019-01-21 2020-07-30 Dic株式会社 Composition de résine aqueuse, film et tissu étanche perméable à l'humidité
CN115894823A (zh) * 2022-06-14 2023-04-04 衡水新光新材料科技有限公司 一种可研磨乳液、水性工业漆及其制备方法
WO2025074864A1 (fr) * 2023-10-03 2025-04-10 Dic株式会社 Dispersion aqueuse, matériau de revêtement aqueux et produit moulé en plastique ayant un film de revêtement dudit matériau de revêtement aqueux
JPWO2025074864A1 (fr) * 2023-10-03 2025-04-10

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