JP5410790B2 - Metallic paint composition - Google Patents
Metallic paint composition Download PDFInfo
- Publication number
- JP5410790B2 JP5410790B2 JP2009059314A JP2009059314A JP5410790B2 JP 5410790 B2 JP5410790 B2 JP 5410790B2 JP 2009059314 A JP2009059314 A JP 2009059314A JP 2009059314 A JP2009059314 A JP 2009059314A JP 5410790 B2 JP5410790 B2 JP 5410790B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- meth
- urethane resin
- unsaturated group
- viscosity
- 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.)
- Active
Links
- 239000000203 mixture Substances 0.000 title claims description 7
- 239000003973 paint Substances 0.000 title description 8
- 150000001875 compounds Chemical class 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 19
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 17
- 239000008199 coating composition Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- -1 acrylate compound Chemical class 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 238000000576 coating method Methods 0.000 description 22
- 239000011248 coating agent Substances 0.000 description 21
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000049 pigment Substances 0.000 description 4
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 3
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 206010040844 Skin exfoliation Diseases 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- GNQKHBSIBXSFFD-UHFFFAOYSA-N 1,3-diisocyanatocyclohexane Chemical compound O=C=NC1CCCC(N=C=O)C1 GNQKHBSIBXSFFD-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- CAYJDIDYXCENIR-UHFFFAOYSA-N 2-[5-(oxiran-2-ylmethoxy)pentoxymethyl]oxirane Chemical compound C1OC1COCCCCCOCC1CO1 CAYJDIDYXCENIR-UHFFFAOYSA-N 0.000 description 1
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 1
- BCKFVXHJSVKKBD-UHFFFAOYSA-N 2-[8-(oxiran-2-ylmethoxy)octoxymethyl]oxirane Chemical compound C1OC1COCCCCCCCCOCC1CO1 BCKFVXHJSVKKBD-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- NJRHMGPRPPEGQL-UHFFFAOYSA-N 2-hydroxybutyl prop-2-enoate Chemical compound CCC(O)COC(=O)C=C NJRHMGPRPPEGQL-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 1
- JRCGLALFKDKSAN-UHFFFAOYSA-N 3-hydroxybutyl prop-2-enoate Chemical compound CC(O)CCOC(=O)C=C JRCGLALFKDKSAN-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- KKQNEOAHDGRPDJ-UHFFFAOYSA-N CO.CO.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1 Chemical compound CO.CO.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1.C1CCCCCCCCCCC1 KKQNEOAHDGRPDJ-UHFFFAOYSA-N 0.000 description 1
- HDICIMRANLAWOM-UHFFFAOYSA-N CO.CO.C1CCc2ccccc2C1 Chemical compound CO.CO.C1CCc2ccccc2C1 HDICIMRANLAWOM-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 206010049155 Visual brightness Diseases 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- KVCNVTICIMHGNP-UHFFFAOYSA-N butane-1,4-diol;propane-1,3-diol Chemical compound OCCCO.OCCCCO KVCNVTICIMHGNP-UHFFFAOYSA-N 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 239000006223 plastic coating Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
Description
本発明は、光輝材を良好に配向させることができ、従って光輝感に優れた塗膜を形成することが可能なメタリック塗料組成物に関する。 The present invention relates to a metallic coating composition that can satisfactorily orient a glittering material and thus can form a coating film with excellent glitter feeling.
メタリック塗料において、自動車、一般工業などの被塗物が鋼板である場合には焼付塗料であるアクリルメラミン樹脂が、パソコンや携帯電話などのように被塗物がプラスチック板である場合には常温乾燥性のラッカー樹脂やイソシアネート硬化型ウレタン樹脂が、それぞれ広く使用されている。 In metallic paints, acrylic melamine resin, which is a baked paint, is used when automobiles, general industries, etc. are coated with steel sheets, and room temperature drying is performed when the coated objects are plastic boards, such as personal computers and mobile phones. Lacquer resins and isocyanate curable urethane resins are widely used.
しかし、プラスチック用塗料において使用されているイソシアネート硬化型ウレタン樹脂は、樹脂の硬化までにポットライフという反応時間（最終的な硬化までに数時間もの時間）を必要とする。また、このものは一般に塗膜硬度が低い（柔らかい）ため、擦り傷防止などの見地から、高硬度塗膜を形成し得るものの出現が要望されている。一方焼付塗料は高温度の適用を必要とするために、プラスチック用途には適さない。 However, the isocyanate curable urethane resin used in plastic coatings requires a pot life reaction time (several hours before final curing) until the resin is cured. In addition, since the coating film hardness is generally low (soft), the appearance of a material capable of forming a high-hardness coating film is desired from the viewpoint of preventing scratches. On the other hand, baking paints are not suitable for plastic applications because they require high temperature application.
種々の塗料用樹脂のうち、紫外線硬化型樹脂は紫外線の照射により短時間（数十秒）で硬化し、その間に被塗物の温度はプラスチックでも耐え得る程度にしか上昇しないので、プラスチック用途に広く使用されている。特に多官能のアクリレートオリゴマーを含んだ紫外線硬化型樹脂の場合には、高硬度の塗膜を形成できることが知られている。 Among various coating resins, UV curable resins are cured in a short time (several tens of seconds) by UV irradiation, and during that time the temperature of the object to be coated rises only to the extent that even plastics can withstand it. Widely used. In particular, in the case of an ultraviolet curable resin containing a polyfunctional acrylate oligomer, it is known that a coating film having high hardness can be formed.
しかし、このような低分子量のアクリレートオリゴマーから構成されている通常の紫外線硬化型樹脂は、これらをメタリック塗料に使用した場合にはスプレー塗布後の光輝材の動きを抑制する為に必要な溶剤の揮発に伴う十分な粘度上昇や乾燥性が期待できず、従って光輝材の配向が良好で光輝感に優れたメタリック塗膜を得ることは困難であった。 However, ordinary UV curable resins composed of such low-molecular weight acrylate oligomers, when they are used in metallic paints, have a solvent necessary for suppressing the movement of the glittering material after spray coating. It is difficult to obtain a metallic coating film that cannot be expected to have a sufficient viscosity increase or drying property due to volatilization, and therefore has a good orientation of the glittering material and excellent glitter.
従って、本発明の目的は、光輝材を良好に配向させることができ、その結果として光輝感に優れた塗膜を形成することが可能なメタリック塗料組成物を提供することである。 Accordingly, an object of the present invention is to provide a metallic coating composition that can orient the glittering material well and, as a result, can form a coating film with excellent glitter feeling.
本発明者等は、下記する特定の不飽和基含有ウレタン樹脂化合物（ａ）、有機溶剤および光輝材から成るメタリック塗料組成物をスプレー塗装によって被塗物に塗着すると、有機溶剤の揮発に伴って、適度に粘度が上昇し、これにより光輝材の動きを止められ、次いで乾燥に伴う塗膜の収縮によって光輝材が押さえつけられ、その結果として光輝材の良好な配向性が実現され、光輝感に優れたメタリック塗膜が形成されることを見出した。 When the present inventors apply a metallic paint composition comprising the following specific unsaturated group-containing urethane resin compound (a), an organic solvent and a bright material to an article by spray coating, the organic solvent volatilizes. Thus, the viscosity rises moderately, thereby stopping the movement of the glitter material, and then the glitter material is pressed down by the shrinkage of the coating film upon drying, and as a result, good orientation of the glitter material is realized and the glitter feeling is achieved. It was found that an excellent metallic coating film was formed.
本発明における上記の不飽和基含有ウレタン樹脂化合物（ａ）は、２以上の活性水素を有する分子量３００以下の化合物（Ａ）と脂環式または芳香族のポリイソシアネート化合物（Ｂ）と活性水素を有する（メタ）アクリレート化合物（Ｃ）との反応生成物であり、分子内にウレタン結合および（メタ）アクリロイル基を持ち、３０００以上、好ましくは３０００〜３００００の重量平均分子量、および２以上、好ましくは２〜１０の不飽和基を有し、粘度が２００万ｍＰａ・ｓ以上、好ましくは常温でワックス状であることによって特徴づけられるものである。 The unsaturated group-containing urethane resin compound (a) in the present invention comprises a compound (A) having a molecular weight of 300 or less having two or more active hydrogens, an alicyclic or aromatic polyisocyanate compound (B) and active hydrogens. a has the reaction products of (meth) acrylate compound (C), having a urethane bond and a (meth) acryloyl groups in the molecule, 3000 or more, preferably a weight-average molecular weight of 3,000 to 30,000, and 2 or more, preferably It is characterized by having 2 to 10 unsaturated groups and a viscosity of 2 million mPa · s or more, preferably waxy at room temperature.
不飽和基含有ウレタン樹脂化合物（ａ）は、上記化合物（Ａ）と化合物（Ｂ）と化合物
（Ｃ）との反応生成物であって前記した条件を満たすものである限り、その構造について格別に限定されるものではないが、より多官能でより高粘度であるものが好ましい。不飽和基含有ウレタン樹脂化合物（ａ）の好ましい例は、化合物（Ａ）としてのシクロヘキシルジメタノールと化合物（Ｂ）としてのイソホロンジイソシアネートと化合物（Ｃ）としてのジペンタエリスリトールペンタアクリレートとを反応させることによって得られるポリマー、すなわち、
化合物（Ｃ）−化合物（Ｂ）−（化合物（Ａ）−化合物（Ｂ））ｘ−化合物（Ｃ）
なる一般構造を有するものである（ｘは繰り返し単位の数である。）。このような構造を有する不飽和基含有ウレタン樹脂化合物（ａ）は有機溶液の形態で合成される。
As long as the unsaturated group-containing urethane resin compound (a) is a reaction product of the compound (A), the compound (B), and the compound (C) and satisfies the above-described conditions, the structure thereof is exceptional. Although not limited, what is more multifunctional and higher viscosity is preferable. A preferred example of the unsaturated group-containing urethane resin compound (a) is to react cyclohexyldimethanol as the compound (A), isophorone diisocyanate as the compound (B), and dipentaerythritol pentaacrylate as the compound (C). A polymer obtained by
Compound (C) -Compound (B)-(Compound (A) -Compound (B)) x-Compound (C)
(X is the number of repeating units). The unsaturated group-containing urethane resin compound (a) having such a structure is synthesized in the form of an organic solution.
化合物（Ａ）は水酸基を２個以上持つ、分子量が３００以下の化合物であればよい。例えば、シクロヘキシルジメタノール、トリシクロデカンジメタノール、デカヒドロナフタレンジメタノール、テトラリンジメタノール、ノルボルネンジメタノール、ペンタシクロドデカンジメタノールなどの多価脂環式アルコール類；エチレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、１，７−ヘプタンジオール、１，８−オクタンジオール、１，９−ノナンジオール、１，１０−デカンジオール、３−メチル−１．５−ペンタンジオール、ネオペンチルグリコール、２−メチル−１．８−オクタンジオールなどの多価脂肪族アルコール類などが挙げられる。 The compound (A) may be a compound having two or more hydroxyl groups and a molecular weight of 300 or less. For example, polyalicyclic alcohols such as cyclohexyldimethanol, tricyclodecane dimethanol, decahydronaphthalene diethanol, tetralin dimethanol, norbornene dimethanol, pentacyclododecane dimethanol; ethylene glycol, 1,3-propanediol 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, Examples thereof include polyhydric aliphatic alcohols such as 3-methyl-1.5-pentanediol, neopentyl glycol and 2-methyl-1.8-octanediol.
化合物（Ｂ）は脂環または芳香族構造がポリイソシアネート中に含まれている化合物であれば良い。例えば、トリレンジイソシアネート、４，４−ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、キシレンジイソシアネート、４，４−メチレンビス（シクロヘキシルイソシアネート）メチルシクロヘキサン−２，４（又は２，６）−ジイソシアネート、１，３−（イソシアネートメチル）シクロヘキサン、イソホロンジイソシアネート、１，５−ナフタレンジイソシアネート、ポリメチレンポリフェニレンジイソシアネート、トリフェニルメタントリイソシアネート、ナフタレンジイソシアネート、１，３−シクロヘキシレンジイソシアネート、トリレンジイソシアネート重合体、ジフェニルメタンジイソシアネート重合体などを挙げることができる。 The compound (B) may be a compound in which an alicyclic or aromatic structure is contained in the polyisocyanate. For example, tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, xylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate) methylcyclohexane-2,4 (or 2,6) -diisocyanate, 1,3- (isocyanate) Methyl) cyclohexane, isophorone diisocyanate, 1,5-naphthalene diisocyanate, polymethylene polyphenylene diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, 1,3-cyclohexylene diisocyanate, tolylene diisocyanate polymer, diphenylmethane diisocyanate polymer, etc. Can do.
化合物（Ｃ）は分子中に（メタ）アクリレート基と活性水素とを持つ化合物であれば良い。例えば、２−ヒドロキシエチルアクリレート、２−ヒドロキシプロピルアクリレート、２−ヒドロキシブチルアクリレート、３−ヒドロキシブチルアクリレート、ポリエチレングリコールモノアクリレート、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレート、２−ヒドロキシ−１−アクリロキシ−３−メタクリレートなどのヒドロキシアクリレート；プロピレングリコールジグリシジルエーテルの（メタ）アクリル酸付加物；１，６−ヘキサンジオールジグリシジルエーテルの（メタ）アクリル酸付加物；１，４−ブタンジオールジグリシジルエーテルの（メタ）アクリル酸付加物；１，５−ペンタンジオールジグリシジルエーテルの（メタ）アクリル酸付加物；１，７−ヘプタンジオールジグリシジルエーテルの（メタ）アクリル酸付加物；１，８−オクタンジオールジグリシジルエーテルの（メタ）アクリル酸付加物などが挙げられる。 The compound (C) may be a compound having a (meth) acrylate group and active hydrogen in the molecule. For example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, polyethylene glycol monoacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, 2-hydroxy-1-acryloxy- Hydroxyacrylates such as 3-methacrylate; (meth) acrylic acid adducts of propylene glycol diglycidyl ether; (meth) acrylic acid adducts of 1,6-hexanediol diglycidyl ether; 1,4-butanediol diglycidyl ether (Meth) acrylic acid adduct; (meth) acrylic acid adduct of 1,5-pentanediol diglycidyl ether; 1,7-heptanediol diglycidyl (Meth) acrylic acid adduct of ether; 1,8-octane diol diglycidyl ether (meth) acrylic acid adduct.
また、その他にもネオペンチルグリコールジグリシジルエーテルの（メタ）アクリル酸付加物、ビスフェノールＡジグリシジルエーテルの（メタ）アクリル酸付加物、水添ビスフェノールＡジグリシジルエーテルの（メタ）アクリル酸付加物などが挙げられる。 In addition, (meth) acrylic acid adduct of neopentyl glycol diglycidyl ether, (meth) acrylic acid adduct of bisphenol A diglycidyl ether, (meth) acrylic acid adduct of hydrogenated bisphenol A diglycidyl ether, etc. Is mentioned.
本発明のメタリック塗料組成物は、上記のような不飽和基含有ウレタン樹脂化合物（ａ）に有機溶剤および光輝材を配合したものである。 The metallic paint composition of the present invention is obtained by blending an organic solvent and a glittering material with the unsaturated group-containing urethane resin compound (a) as described above.
有機溶剤は、不飽和基含有ウレタン樹脂化合物（ａ）を溶解することができ、且つスプレーが可能なものである限り、その種類に制限はなく、例えば、メチルエチルケトン、酢酸ブチル、酢酸エチル、メチルイソブチルケトン、トルエン、エチルグリコールアセテート、ブチルアセテートなどを好適に使用することができる。有機溶剤の使用量は、塗料組成物をスプレー可能粘度とするのに必要な量、またはそれよりも少ない量とされる。後者の場合には、スプレー塗装に先立って有機溶剤を添加することにより、組成物の粘度をスプレー可能粘度に調整することが必要である。光輝材は、塗膜に金属のような光輝感を与える顔料である限り、その種類に制限はないが、一般的にはアルミニウムやその他の金属顔料、パール顔料などが好適に使用される。 The organic solvent is not limited as long as it can dissolve the unsaturated group-containing urethane resin compound (a) and can be sprayed. For example, methyl ethyl ketone, butyl acetate, ethyl acetate, methyl isobutyl Ketone, toluene, ethyl glycol acetate, butyl acetate and the like can be preferably used. The amount of the organic solvent used is an amount necessary to make the coating composition sprayable viscosity, or an amount smaller than that. In the latter case, it is necessary to adjust the viscosity of the composition to a sprayable viscosity by adding an organic solvent prior to spray coating. The glitter material is not particularly limited as long as it is a pigment that gives the coating film a glittery feeling like metal, but in general, aluminum, other metal pigments, pearl pigments, and the like are preferably used.
光輝材の使用量は不飽和基含有ウレタン樹脂化合物（ａ）の１００重量部（固形分）に対して、５〜３５重量部が好ましい。 The use amount of the glittering material is preferably 5 to 35 parts by weight with respect to 100 parts by weight (solid content) of the unsaturated group-containing urethane resin compound (a).
本発明のメタリック塗料組成物には、必要に応じて沈降防止剤やレベリング剤などのような慣用の添加剤の適量を配合することができる。 In the metallic coating composition of the present invention, an appropriate amount of a conventional additive such as an anti-settling agent or a leveling agent can be blended as necessary.
本発明のメタリック塗料組成物は、通常、スプレー塗装によって被塗物に適用される。その際、組成物の粘度が高い場合には、有機溶剤を添加することにより、その粘度をスプレー可能粘度、例えばフォードカップ＃４にて１０〜１８秒（２０℃）の粘度に調整する必要がある。スプレー塗装により５〜３０μｍ、好ましくは１０〜２０μｍの厚さの塗膜を塗着させたのち、紫外線照射することにより、光輝材の配向が良好で光輝感に優れたメタリック塗膜を得ることができる。 The metallic coating composition of the present invention is usually applied to an object by spray coating. At that time, when the viscosity of the composition is high, it is necessary to adjust the viscosity to a sprayable viscosity, for example, a viscosity of 10 to 18 seconds (20 ° C.) in Ford Cup # 4 by adding an organic solvent. is there. After applying a coating film having a thickness of 5 to 30 μm, preferably 10 to 20 μm by spray coating, irradiation with ultraviolet rays can obtain a metallic coating film having excellent orientation of the glittering material and excellent glitter. it can.
次に、本発明の実施の形態について、具体的に説明する。以下において、部および％は、いずれも重量基準である。 Next, embodiments of the present invention will be specifically described. In the following, both parts and% are based on weight.
実施例 １
不飽和基含有ウレタン樹脂化合物（ａ）とメチルエチルケトンとを
６０％対４０％の割合で含んで成る溶液 １００部
ＡＬＰＡＳＴＥ ５６２０ＮＳ １６部
（東洋アルミニウム工業株式会社製のアルミニウム顔料ペースト；固形分７０％）
ＩＲＧＡＣＵＲＥ １８４（Ｃｉｂａ社製の光開始剤） ４部
ＮＳ−５５００（楠本化成（株）製の沈降防止剤） １０部
Example 1
A solution comprising an unsaturated group-containing urethane resin compound (a) and methyl ethyl ketone in a ratio of 60% to 40% 100 parts ALPASSE 5620NS 16 parts (aluminum pigment paste manufactured by Toyo Aluminum Industry Co., Ltd .; solid content 70%)
IRGACURE 184 (Ciba photoinitiator) 4 parts NS-5500 (Enomoto Kasei Co., Ltd. anti-settling agent) 10 parts
上記の成分を酢酸ブチル中に分散させて、フォードカップ＃４にて１２秒（２０℃）の粘度に調整することにより、本発明のメタリック塗料組成物を調製した。 The metallic paint composition of the present invention was prepared by dispersing the above components in butyl acetate and adjusting the viscosity to 12 seconds (20 ° C.) with Ford Cup # 4.
上記の不飽和基含有ウレタン樹脂化合物（ａ）は、化合物（Ａ）としてのシクロヘキシルジメタノールと化合物（Ｂ）としてのイソホロンジイソシアネートと化合物（Ｃ）としてのジペンタエリスリトールペンタアクリレートとを反応させることによって得られる前記一般構造式のポリマーであって、９２００の重量平均分子量および１０の不飽和基を有しており、粘度が２００万ｍＰａ・ｓ以上であり、常温でワックス状である。 The unsaturated group-containing urethane resin compound (a) is obtained by reacting cyclohexyldimethanol as the compound (A), isophorone diisocyanate as the compound (B), and dipentaerythritol pentaacrylate as the compound (C). The obtained polymer having the above general structural formula has a weight average molecular weight of 9200 and 10 unsaturated groups, has a viscosity of 2 million mPa · s or more, and is waxy at room temperature.
実施例 ２
不飽和基含有ウレタン樹脂化合物（ａ）とメチルエチルケトンと
を５０％対５０％の割合で含んで成る溶液 １２０部
ＡＬＰＡＳＴＥ ５６２０ＮＳ（前出） １６部
ＩＲＧＡＣＵＲＥ １８４（前出） ４部
ＮＳ−５５００（前出） １０部
Example 2
A solution comprising an unsaturated group-containing urethane resin compound (a) and methyl ethyl ketone in a ratio of 50% to 50% 120 parts ALPASSE 5620NS (supra) 16 parts IRGACURE 184 (supra) 4 parts NS-5500 (supra) ) 10 copies
上記の成分を酢酸ブチル中に分散させて、フォードカップ＃４で１２秒（２０℃）の粘度に調整することにより、本発明のメタリック塗料組成物を調製した。 The metallic coating composition of the present invention was prepared by dispersing the above components in butyl acetate and adjusting the viscosity to 12 seconds (20 ° C.) with Ford Cup # 4.
上記の不飽和基含有ウレタン樹脂化合物（ａ）は、化合物（Ａ）としてのシクロヘキシルジメタノールと化合物（Ｂ）としてのイソホロンジイソシアネートと化合物（Ｃ）としての２−ヒドロキシエチルアクリレートとを反応させることによって得られる前記一般式のポリマーであって、３９００の重量平均分子量および２の不飽和基を有しており、粘度が２００万ｍＰａ・ｓ以上であり、常温でワックス状である。 The unsaturated group-containing urethane resin compound (a) is obtained by reacting cyclohexyldimethanol as the compound (A), isophorone diisocyanate as the compound (B), and 2-hydroxyethyl acrylate as the compound (C). The obtained polymer of the above general formula has a weight average molecular weight of 3900 and an unsaturated group of 2, has a viscosity of 2 million mPa · s or more, and is waxy at room temperature.
比較例
この比較例は、低分子量のウレタンオリゴマーから成る従来技術を例示するものである。
比較樹脂−１ ６０部
ＡＬＰＡＳＴＥ ５６２０ＮＳ（前出） １６部
ＩＲＧＡＣＵＲＥ １８４（前出） ４部
ＮＳ−５５００（前出） １０部
Comparative Example This comparative example illustrates the prior art consisting of low molecular weight urethane oligomers.
Comparative resin-1 60 parts ALPATHE 5620NS (supra) 16 parts IRGACURE 184 (supra) 4 parts NS-5500 (supra) 10 parts
上記の成分を酢酸ブチル中に分散させて、フォードカップ＃４で１４秒（２０℃）の粘度に調整することにより、従来技術のメタリック塗料組成物を調製した。 A prior art metallic coating composition was prepared by dispersing the above ingredients in butyl acetate and adjusting the viscosity to 14 seconds (20 ° C.) with Ford Cup # 4.
上記の比較樹脂−１は化合物（Ａ）としてのシクロヘキシルジメタノールと化合物（Ｂ）としてのイソホロンジイソシアネートと化合物（Ｃ）としてのペンタエリスリトールトリアクリレートとを反応させることによって得られる前記構造式（ただしｘの値が小さい）のポリマーであって、１５００の重量平均分子量および６の不飽和基を有しており、粘度が３５０００ｍＰａ・ｓであり、常温で液状である。 Said comparative resin-1 is the said structural formula (however, x obtained by reacting the cyclohexyldimethanol as a compound (A), the isophorone diisocyanate as a compound (B), and the pentaerythritol triacrylate as a compound (C). The polymer has a weight average molecular weight of 1500 and 6 unsaturated groups, has a viscosity of 35000 mPa · s, and is liquid at ordinary temperature.
試験例
実施例１、実施例２および比較例のメタリック塗料組成物を、それぞれポリカーボネート板にエアースプレーで塗布し、６０℃で１０分間乾燥したのち、光源として１２０Ｗ／ｃｍのメタルハライドランプを用いて、１４００ｍＪ／ｃｍ２の積算光量で紫外線照射することにより、厚さ１２μｍのメタリック塗膜を作製した。それぞれの塗膜についてフロップ・インデックス（Ｆｌｏｐ ｉｎｄｅｘ）および目視による光輝感、密着性並びに鉛筆硬度を測定し、結果を表１に示した。
Test Examples The coating compositions of Example 1, Example 2 and Comparative Example were each applied to a polycarbonate plate by air spray, dried at 60 ° C. for 10 minutes, and then a 120 W / cm metal halide lamp was used as the light source. A metallic coating film having a thickness of 12 μm was prepared by irradiating with ultraviolet light at an integrated light quantity of 1400 mJ / cm 2 . Each coating film was measured for flop index, visual brightness, adhesion, and pencil hardness. The results are shown in Table 1.
フロップ・インデックスは、Ｘ−Ｒｉｔｅ社製のフロップ・インデックス測定器（Ｘ−Ｒｉｔｅ ＭＡ−６８ＩＩ）を用いて測定した。光輝材の種類により幾分異なるが、一般的にはフロップ・インデックスが２０以上であれば、金属のような優れた光輝感があると評価できる。 The flop index was measured using a flop index measuring device (X-Rite MA-68II) manufactured by X-Rite. Although it varies somewhat depending on the type of glitter material, it can generally be evaluated that if the flop index is 20 or more, there is an excellent glitter feeling like a metal.
目視による光輝感の評価において、○は光輝感に優れていたこと（光輝材の配向ムラが殆んど認められないこと）を、×は光輝感に乏しかったこと（光輝材の配向ムラが多く認められること）を、それぞれ意味する。塗膜の密着性はカッタ−で素地に達するようにカットし、１×１ｍｍの大きさのゴバン目塗膜を１００個作り、その表面に粘着セロハンテ−プを貼着し、それを急激に剥離したのちの塗面を観察することによって測定した。○はゴバン目塗膜の剥離が全く認められなかったことを、×はゴバン目塗膜の剥離が１０個以上認められたことを、それぞれ意味する。 In the visual evaluation of the glitter feeling, ○ indicates that the glitter feeling is excellent (almost no uneven alignment of the glitter material is observed), and x indicates that the glitter feeling is poor (the glitter material has a lot of uneven alignment). Means that it is permitted). The adhesiveness of the coating is cut with a cutter to reach the substrate, 100 100x 1mm size gobanged coatings are made, adhesive cellophane tape is attached to the surface, and it is peeled off rapidly After that, it was measured by observing the coated surface. The symbol “◯” means that no peeling of the Gobang eye coating was observed, and the symbol “X” means that 10 or more peelings of the Gobang eye coating were recognized.
塗膜の鉛筆硬度は、ブリキ板に上記の塗装条件で塗膜を作製し、紫外線照射後に測定し
た。
The pencil hardness of the coating film was measured after the coating film was prepared on a tin plate under the above coating conditions and irradiated with ultraviolet rays.
上記の試験結果から明らかなように、不飽和基含有ウレタン樹脂化合物（ａ）、有機溶剤および光輝材から成る本発明のメタリック塗料組成物を使用することによって、光輝材の配向が良好で光輝感に優れたメタリック塗膜を得ることができる。 As is apparent from the above test results, the use of the metallic coating composition of the present invention comprising the unsaturated group-containing urethane resin compound (a), an organic solvent and a glittering material ensures that the glittering material has good orientation and glittering feeling. An excellent metallic coating film can be obtained.
Claims (1)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009059314A JP5410790B2 (en) | 2009-03-12 | 2009-03-12 | Metallic paint composition |
| KR1020100021182A KR101731110B1 (en) | 2009-03-12 | 2010-03-10 | Metallic coating composition |
| CN201010151420.1A CN101838499B (en) | 2009-03-12 | 2010-03-12 | Metallic coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009059314A JP5410790B2 (en) | 2009-03-12 | 2009-03-12 | Metallic paint composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2010209276A JP2010209276A (en) | 2010-09-24 |
| JP5410790B2 true JP5410790B2 (en) | 2014-02-05 |
Family
ID=42742182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009059314A Active JP5410790B2 (en) | 2009-03-12 | 2009-03-12 | Metallic paint composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5410790B2 (en) |
| KR (1) | KR101731110B1 (en) |
| CN (1) | CN101838499B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5548317B2 (en) * | 2011-12-08 | 2014-07-16 | ディーエイチ・マテリアル株式会社 | Molding materials and molded products |
| JP7121952B2 (en) * | 2020-02-04 | 2022-08-19 | 株式会社パジコ | Light energy ray-curable clay composition, method for producing light energy ray-curable clay composition, and method for producing modeled object |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0678499B2 (en) * | 1986-04-26 | 1994-10-05 | 大日本インキ化学工業株式会社 | Painting method |
| JPH037713A (en) * | 1989-03-30 | 1991-01-14 | Toyobo Co Ltd | Radiation-curing resin composition, resin composition for paint and precoat metal |
| JPH02263872A (en) * | 1989-04-03 | 1990-10-26 | Dainippon Toryo Co Ltd | Ultraviolet-curable coating |
| JP3247267B2 (en) * | 1995-02-02 | 2002-01-15 | トヨタ自動車株式会社 | Matte coating formation method |
| CN1436822A (en) * | 2002-02-08 | 2003-08-20 | 湖南亚大新材料科技股份有限公司 | Ultraviolet light cured aluminium powder paint |
| EP1488923A1 (en) * | 2002-03-01 | 2004-12-22 | C. I. Kasei Company, Limited | Decorative sheet and process for producing the same |
| CN1486960A (en) * | 2002-08-07 | 2004-04-07 | 珠海东诚化工有限公司 | Ultraviolet light cured ceramic paint |
| JP2004090294A (en) * | 2002-08-29 | 2004-03-25 | C I Kasei Co Ltd | Decorative sheet |
| JP2006056973A (en) * | 2004-08-19 | 2006-03-02 | Kansai Paint Co Ltd | Method for producing aqueous resin dispersion |
| KR100758294B1 (en) * | 2005-10-18 | 2007-09-13 | 대영고분자 주식회사 | A low-bake base and top coating paint composition and method therefor |
| JP4953637B2 (en) * | 2006-01-18 | 2012-06-13 | 株式会社システム・トート | Decorative article and method of manufacturing the same |
-
2009
- 2009-03-12 JP JP2009059314A patent/JP5410790B2/en active Active
-
2010
- 2010-03-10 KR KR1020100021182A patent/KR101731110B1/en active IP Right Grant
- 2010-03-12 CN CN201010151420.1A patent/CN101838499B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN101838499A (en) | 2010-09-22 |
| JP2010209276A (en) | 2010-09-24 |
| CN101838499B (en) | 2015-02-25 |
| KR20100103386A (en) | 2010-09-27 |
| KR101731110B1 (en) | 2017-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2003174B1 (en) | Hard coating composition for metal base | |
| JP5068513B2 (en) | Unsaturated group-containing urethane resin and active energy ray-curable resin composition containing the same | |
| JPWO2009001818A1 (en) | Coating composition for metal thin film and glitter composite coating film formed therefrom | |
| WO2015033624A1 (en) | Coating composition and coated article | |
| JP6778254B2 (en) | Polyurethane (meth) acrylate oligomer and curable composition containing the oligomer | |
| JP5215897B2 (en) | Coating method | |
| CN107298932A (en) | Coating composition and coating film-forming methods | |
| TW201610014A (en) | Active-energy-curing resin composition, coating material, coating film, and laminate film | |
| CN111417690A (en) | Low VOC aqueous UV-curable single layer coating composition, method of coating and substrates coated therewith | |
| JP2012072327A (en) | Radical polymerizable group-containing urethane prepolymer, urethane (meth)acrylate, photocurable resin composition, hard coat film, and molded product | |
| JP5410790B2 (en) | Metallic paint composition | |
| JP2021017513A (en) | Active energy ray-curable coating agent composition, cured product, and laminate | |
| WO2020067459A1 (en) | Coating material composition, method for forming coating film, and coated article | |
| JP2012057031A (en) | Active energy ray-curable resin composition and coating agent | |
| JP6504528B2 (en) | Active energy ray curable composition and coating film | |
| JP6075614B2 (en) | COATING COMPOSITION AND METHOD FOR PRODUCING LAMINATE | |
| JP2016113610A (en) | Soft feel coating composition for one time coating | |
| JP2012001578A (en) | Curable resin composition and laminate | |
| JP6845586B2 (en) | Active energy ray-curable coating agent | |
| JP5497303B2 (en) | Anti-curl coating agent | |
| KR101947240B1 (en) | Coating composition | |
| JP7369558B2 (en) | Laminated film for decorating 3D molded products | |
| KR101365053B1 (en) | Two―component type thermosetting coating composition | |
| EP2125923A1 (en) | Thermal curable powder coating composition | |
| JP2012246465A (en) | Active energy ray-curable resin composition, and coating agent for first coating containing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120210 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130704 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130723 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130919 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20131015 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20131107 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5410790 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |