JP2009074047A - Aqueous resin composition, aqueous coating composition and coating method for plastic molded article - Google Patents
Aqueous resin composition, aqueous coating composition and coating method for plastic molded article Download PDFInfo
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- JP2009074047A JP2009074047A JP2008157906A JP2008157906A JP2009074047A JP 2009074047 A JP2009074047 A JP 2009074047A JP 2008157906 A JP2008157906 A JP 2008157906A JP 2008157906 A JP2008157906 A JP 2008157906A JP 2009074047 A JP2009074047 A JP 2009074047A
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- Prior art keywords
- meth
- acrylate
- aqueous
- coating
- aqueous resin
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- 238000000576 coating method Methods 0.000 title claims abstract description 54
- 239000011342 resin composition Substances 0.000 title claims abstract description 34
- 239000008199 coating composition Substances 0.000 title claims abstract description 17
- 229920003023 plastic Polymers 0.000 title claims abstract description 17
- 239000004033 plastic Substances 0.000 title claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 47
- 239000000178 monomer Substances 0.000 claims abstract description 46
- 229920000098 polyolefin Polymers 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000007720 emulsion polymerization reaction Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 150000002429 hydrazines Chemical class 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 17
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 46
- 239000000758 substrate Substances 0.000 abstract description 10
- 239000004210 ether based solvent Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 81
- -1 polypropylene Polymers 0.000 description 41
- 239000000203 mixture Substances 0.000 description 19
- 239000003973 paint Substances 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 229920000178 Acrylic resin Polymers 0.000 description 10
- 239000004925 Acrylic resin Substances 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 239000000049 pigment Substances 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- BSXGCUHREZFSRY-UHFFFAOYSA-N 3-[[1-amino-2-[[1-amino-1-(2-carboxyethylimino)-2-methylpropan-2-yl]diazenyl]-2-methylpropylidene]amino]propanoic acid;tetrahydrate Chemical compound O.O.O.O.OC(=O)CCNC(=N)C(C)(C)N=NC(C)(C)C(=N)NCCC(O)=O BSXGCUHREZFSRY-UHFFFAOYSA-N 0.000 description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229960002887 deanol Drugs 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 239000012972 dimethylethanolamine Substances 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- ZKECVHXIVHRIIA-UHFFFAOYSA-N n-(2,2,6,6-tetramethylpiperidin-1-yl)prop-2-enamide Chemical compound CC1(C)CCCC(C)(C)N1NC(=O)C=C ZKECVHXIVHRIIA-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000518 rheometry Methods 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 3
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 2
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 2
- OYLCUJRJCUXQBQ-UHFFFAOYSA-N 1-hepten-3-one Chemical compound CCCCC(=O)C=C OYLCUJRJCUXQBQ-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- IBDVWXAVKPRHCU-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(=O)C(C)=C IBDVWXAVKPRHCU-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- NARVIWMVBMUEOG-UHFFFAOYSA-N 2-Hydroxy-propylene Natural products CC(O)=C NARVIWMVBMUEOG-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- JMADMUIDBVATJT-UHFFFAOYSA-N 2-methylprop-2-enamide;propan-2-one Chemical compound CC(C)=O.CC(C)=O.CC(=C)C(N)=O JMADMUIDBVATJT-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
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- 239000004606 Fillers/Extenders Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
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- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 description 2
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- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 2
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- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
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- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
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- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
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- 150000003623 transition metal compounds Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
本発明は、プラスチック基材への付着性に優れ、さらに耐水性、耐汚染性に優れた水性樹脂組成物、水性塗料組成物及びプラスチック成形品の塗装方法に関する。 The present invention relates to a water-based resin composition, a water-based coating composition, and a method for coating a plastic molded article, which are excellent in adhesion to a plastic substrate and further excellent in water resistance and stain resistance.
自動車のインストルメントパネル、センターコンソール、ダッシュボード、ドアトリムなどの内装部品には、プラスチック素材としてポリプロピレン、ポリカーボネート、ＡＢＳなどの各種素材が用いられており、近年、コストやリサイクル性の観点から特に難付着性のポリプロピレン素材が増えつつある。そのため、ポリプロピレン素材上での付着性や耐汚染性（耐油性）等を１コート仕上げで成立させることが急務となっている。そこで特許文献１では、塩素化ポリオレフィン樹脂エマルションと純アクリル樹脂エマルションとを特定の割合で配合してなる樹脂エマルションを必須成分とする水性塗料組成物が提案されている。 Interior parts such as automotive instrument panels, center consoles, dashboards, and door trims are made of various materials such as polypropylene, polycarbonate, and ABS as plastic materials. In recent years, they are particularly difficult to adhere to in terms of cost and recyclability. Sexual polypropylene material is increasing. Therefore, there is an urgent need to establish adhesion on a polypropylene material, contamination resistance (oil resistance), etc. by one coat finish. Therefore, Patent Document 1 proposes an aqueous coating composition containing, as an essential component, a resin emulsion obtained by blending a chlorinated polyolefin resin emulsion and a pure acrylic resin emulsion at a specific ratio.
しかしながら上記特許文献１に開示の組成物のように塩素化ポリオレフィン樹脂エマルションとアクリル樹脂エマルションを単にブレンドしただけではポリプロピレン素材に対する付着性や耐水性、耐汚染性（耐油性）が有機溶剤系の塗料組成物に比べて劣るという不都合があった。 However, just by blending a chlorinated polyolefin resin emulsion and an acrylic resin emulsion as in the composition disclosed in Patent Document 1 above, an organic solvent-based paint has adhesion, water resistance, and stain resistance (oil resistance) to a polypropylene material. There was an inconvenience that it was inferior to the composition.
そこで塩素化ポリオレフィン樹脂エマルションを変性することによって諸性能を向上させる試みが種々提案されている。例えば特許文献２では、高塩素化度の塩素化ポリオレフィンの有機溶剤溶液を界面活性剤で水中乳化させた後、該エマルション中でビニル系単量体を重合反応させて水性樹脂組成物を得ている。また特許文献３では、不飽和カルボン酸で変性した塩素化ポリオレフィンに界面活性剤、中和剤及び水を添加し水性化した後、水中で、塩素化ポリオレフィンに対し過剰の重合可能なビニル系単量体を乳化重合させることで水性樹脂組成物を得ている。これらの水性樹脂組成物によれば、付着性や耐油性などに優れた塗膜を形成できると記載されている。 Accordingly, various attempts have been proposed to improve various performances by modifying the chlorinated polyolefin resin emulsion. For example, in Patent Document 2, an organic solvent solution of a chlorinated polyolefin having a high chlorination degree is emulsified in water with a surfactant, and then a vinyl monomer is polymerized in the emulsion to obtain an aqueous resin composition. Yes. In Patent Document 3, a surfactant, a neutralizing agent and water are added to a chlorinated polyolefin modified with an unsaturated carboxylic acid to make it water-based, and then an excess of a vinyl-based monomer capable of being polymerized excessively with respect to the chlorinated polyolefin in water. An aqueous resin composition is obtained by emulsion polymerization of the monomer. According to these aqueous resin compositions, it is described that a coating film excellent in adhesion and oil resistance can be formed.
しかしながら上記特許文献２や特許文献３に開示の水性樹脂組成物では、塩素化ポリオレフィンの水性化に界面活性剤を使用するため、塗膜中に界面活性剤が残存して耐水性を低下させるという問題があった。 However, in the aqueous resin compositions disclosed in Patent Document 2 and Patent Document 3 described above, a surfactant is used to make the chlorinated polyolefin aqueous, so that the surfactant remains in the coating film and water resistance is reduced. There was a problem.
本発明の目的は、上記の問題点を解消し、プラスチック基材への付着性に優れ、さらに耐水性、耐汚染性に優れた塗膜を形成できる水性樹脂組成物、水性塗料組成物及びプラスチック成形品の塗装方法を提供することにある。 The object of the present invention is to solve the above-mentioned problems and to form a water-based resin composition, a water-based coating composition and a plastic that can form a coating film excellent in adhesion to a plastic substrate, and further excellent in water resistance and stain resistance. It is in providing the coating method of a molded article.
本発明は、酸変性ポリオレフィン（ａ）、エーテル系溶剤及び塩基性物質によって得られる水性樹脂分散体（Ａ）の存在下で、重合性不飽和単量体（Ｂ）を用いて乳化重合させることにより得られることを特徴とする水性樹脂組成物、これを含有する水性塗料組成物、及びこれを用いたプラスチック成形品の塗装方法に関する。 In the present invention, emulsion polymerization is performed using a polymerizable unsaturated monomer (B) in the presence of an aqueous resin dispersion (A) obtained from an acid-modified polyolefin (a), an ether solvent and a basic substance. It is related with the aqueous resin composition characterized by being obtained by this, the aqueous coating composition containing this, and the coating method of a plastic molded article using the same.
本発明によれば、塩素化ポリオレフィン等の水性化時に界面活性剤を使用せずとも安定に水性化でき、さらに乳化重合時にはカルボニル基含有重合性不飽和単量体や水酸基含有重合性不飽和単量体などの親水性の重合性不飽和単量体を安定して重合可能であり、そのように得られる水性樹脂組成物は、プラスチック基材への付着性に優れ、さらに耐水性、耐汚染性に優れた塗膜を形成することができる。 According to the present invention, when a chlorinated polyolefin or the like is made water-based, it can be stably made water-free without using a surfactant, and at the time of emulsion polymerization, a carbonyl group-containing polymerizable unsaturated monomer or a hydroxyl group-containing polymerizable unsaturated monomer can be used. A hydrophilic polymerizable unsaturated monomer such as a monomer can be stably polymerized, and the aqueous resin composition thus obtained has excellent adhesion to a plastic substrate, and is further resistant to water and contamination. A coating film excellent in properties can be formed.
本発明で使用する酸変性ポリオレフィン（ａ）は、通常、エチレン、プロピレン、ブチレン、ヘキセンなどの炭素数が２〜１０のオレフィン類から選ばれた１種又は２種以上を重合せしめてなるポリオレフィンを、さらに（メタ）アクリル酸、マレイン酸、フマル酸、イタコン酸などの不飽和カルボン酸又はそれらの酸無水物を用いて、既知の方法に従ってグラフト共重合させて変性したものであり、特にマレイン酸又はその酸無水物によって変性されたものが好適である。該不飽和カルボン酸又はその酸無水物によるグラフト共重合量は、ポリオレフィンの固形分質量に対して１〜２０質量％、好ましくは２〜１０質量％の範囲内が適当である。 The acid-modified polyolefin (a) used in the present invention is usually a polyolefin obtained by polymerizing one or more selected from olefins having 2 to 10 carbon atoms such as ethylene, propylene, butylene and hexene. Further, it is modified by graft copolymerization according to a known method using unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid or their acid anhydrides, particularly maleic acid Or the thing modified | denatured with the acid anhydride is suitable. The amount of graft copolymerization with the unsaturated carboxylic acid or acid anhydride thereof is suitably in the range of 1 to 20% by mass, preferably 2 to 10% by mass, based on the mass of the solid content of the polyolefin.
酸変性ポリオレフィン（ａ）に使用されるポリオレフィンとしては、特に得られるポリオレフィンの分子量分布が狭く、ランダム共重合性等にも優れる等の点から、その重合触媒としてシングルサイト触媒を用いて製造されたものが好適である。シングルサイト触媒は、活性点が同種（シングルサイト）のものであり、該シングルサイト触媒の中でも特にメタロセン系触媒が好ましく、該メタロセン系触媒は、通常、共役五員環配位子を少なくとも１個有する周期律表４〜６族及び８族の遷移金属化合物や３族の希土類遷移金属化合物であるメタロセン（ビス（シクロペンタジエニル）金属錯体及びその誘導体）と、これを活性化できるアルミノキサン等の助触媒、さらにトリメチルアルミニウム等の有機アルミニウム化合物を組合せて得られるものである。該ポリオレフィンの製造方法には、従来公知の方法が採用でき、例えばプロピレンやエチレン等と水素を反応容器に供給しながら連続的にアルキルアルミニウムとメタロセン系触媒を添加しながら製造する方法が挙げられる。 The polyolefin used for the acid-modified polyolefin (a) was produced using a single-site catalyst as the polymerization catalyst, particularly from the viewpoint that the obtained polyolefin has a narrow molecular weight distribution and excellent random copolymerizability. Those are preferred. The single-site catalyst has the same active site (single site), and among the single-site catalysts, a metallocene catalyst is particularly preferable, and the metallocene catalyst usually has at least one conjugated five-membered ring ligand. Metallocene (bis (cyclopentadienyl) metal complex and its derivatives) which are transition metal compounds of Group 4 to 6 and Group 8 and Group 3 rare earth transition metal compounds and aluminoxane which can activate this, etc. It is obtained by combining a promoter and an organoaluminum compound such as trimethylaluminum. As the method for producing the polyolefin, a conventionally known method can be adopted, and for example, a method in which propylene, ethylene or the like and hydrogen are supplied to the reaction vessel and the alkylaluminum and the metallocene catalyst are continuously added can be mentioned.
酸変性ポリオレフィン（ａ）は、必要に応じて、さらに塩素化されていても良い。ポリオレフィンの塩素化は、例えば、ポリオレフィン又はその変性物の有機溶剤溶液又は分散液に塩素ガスを吹き込むことによって行うことができ、反応温度は５０〜１２０℃とすることができる。ポリオレフィンの塩素化物（固形分）中の塩素含有率は、ポリオレフィンの塩素化物に望まれる物性などに応じて変えることができるが、形成塗膜の付着性などの点から、一般には、ポリオレフィンの塩素化物の重量を基準にして３５質量％以下、特に１０〜３０質量％、さらに特に１２〜２５質量％の範囲内とすることが望ましい。 The acid-modified polyolefin (a) may be further chlorinated as necessary. The chlorination of polyolefin can be performed, for example, by blowing chlorine gas into an organic solvent solution or dispersion of polyolefin or a modified product thereof, and the reaction temperature can be 50 to 120 ° C. The chlorine content in the chlorinated polyolefin (solid content) can be changed according to the physical properties desired for the chlorinated polyolefin. Desirably, the amount is 35% by mass or less, particularly 10 to 30% by mass, and more particularly 12 to 25% by mass based on the weight of the compound.
上記酸変性ポリオレフィン（ａ）に使用されるポリオレフィンは、特にプロピレンを重合成分として含有するものであることが好適であり、該酸変性ポリオレフィン（ａ）におけるプロピレンの質量分率は、０．５〜０．９９、好ましくは０．７〜０．９５であることが他成分との相溶性や形成塗膜の付着性の点から好適である。 The polyolefin used in the acid-modified polyolefin (a) is particularly preferably one containing propylene as a polymerization component, and the mass fraction of propylene in the acid-modified polyolefin (a) is from 0.5 to 0.99, preferably 0.7 to 0.95, is suitable from the viewpoint of compatibility with other components and adhesion of the formed coating film.
本発明では上記酸変性ポリオレフィン（ａ）を、エーテル系溶剤及び塩基性物質によって水性媒体中に分散させ、必要に応じて溶剤を減圧蒸留して水性樹脂分散体（Ａ）とする。かかるエーテル系溶剤としては、例えばテトラヒドロフラン、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、ジエチルエーテル、ジイソプロピルエーテル、ジエチレングリコールモノエチルエーテル等が挙げられ、これらのうち特にテトラヒドロフランが沸点及び溶解性の点から好適である。 In the present invention, the acid-modified polyolefin (a) is dispersed in an aqueous medium with an ether solvent and a basic substance, and the solvent is distilled under reduced pressure as necessary to obtain an aqueous resin dispersion (A). Examples of such ether solvents include tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, diethyl ether, diisopropyl ether, diethylene glycol monoethyl ether, and the like. Among these, tetrahydrofuran has a boiling point and It is preferable from the viewpoint of solubility.
上記エーテル系溶剤には必要に応じてアルコール系溶剤を併用しても良い。アルコール系溶剤としては炭素数１〜７の脂肪族系アルコール、芳香族系アルコール、脂環式アルコールを用いることができ、特に炭素数３〜５のアルコールが望ましい。アルコール系溶剤を併用する場合には、両者の合計質量中にアルコール系溶剤が４０質量％以下、好ましくは５〜３０質量％の範囲が適当である。またかかるアルコール系溶剤の代わりに水酸基含有重合性不飽和単量体を用いることもできる。水酸基含有重合性不飽和単量体としては、例えば、２−ヒドロキシエチル（メタ）アクリレ−ト、２−ヒドロキシプロピル（メタ）アクリレ−ト、３−ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレートなどの（メタ）アクリル酸のＣ２〜Ｃ８ヒドロキシアルキル（メタ）アクリレート、アリルアルコ−ル、上記Ｃ２〜Ｃ８ヒドロキシアルキル（メタ）アクリレートのε−カプロラクトン変性体などの水酸基を有する（メタ）アクリレート；分子末端が水酸基であるポリオキシエチレン鎖を有する（メタ）アクリレート等が挙げられ、これらは単独でもしくは２種以上組み合わせて使用することができる。 If necessary, an alcohol solvent may be used in combination with the ether solvent. As the alcohol solvent, aliphatic alcohols having 1 to 7 carbon atoms, aromatic alcohols, and alicyclic alcohols can be used, and alcohols having 3 to 5 carbon atoms are particularly desirable. When an alcohol solvent is used in combination, the alcohol solvent is 40% by mass or less, preferably 5 to 30% by mass in the total mass of both. Further, a hydroxyl group-containing polymerizable unsaturated monomer can be used in place of the alcohol solvent. Examples of the hydroxyl group-containing polymerizable unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth). (meth) C 2 -C 8 hydroxyalkyl (meth) acrylate acrylic acid such as acrylates, allyl alcohol - le, having a hydroxyl group such as ε- caprolactone modified products of the above C 2 -C 8 hydroxyalkyl (meth) acrylate (meth ) Acrylate; (meth) acrylate having a polyoxyethylene chain whose molecular end is a hydroxyl group, and the like can be used, and these can be used alone or in combination of two or more.
上記エーテル系溶剤、或いはエーテル系溶剤及びアルコール系溶剤の使用量は、酸変性ポリオレフィン（ａ）１００質量部に対して５０〜４００質量部、好ましくは８０〜３００質量部が適当である。 The amount of the ether solvent or the ether solvent and the alcohol solvent is 50 to 400 parts by weight, preferably 80 to 300 parts by weight, per 100 parts by weight of the acid-modified polyolefin (a).
上記塩基性物質としては、例えばトリエチルアミン、トリブチルアミン、ジメチルエタノールアミン、トリエタノールアミンなどの３級アミン；ジエチルアミン、ジブチルアミン、ジエタノールアミン、モルホリンなどの２級アミン；プロピルアミン、エタノールアミンなどの１級アミン；アンモニア等が挙げられる。塩基性物質の使用量は上記酸変性ポリオレフィン（ａ）中のカルボキシル基に対して０．８〜４．０モル当量の範囲内であることが望ましい。 Examples of the basic substance include tertiary amines such as triethylamine, tributylamine, dimethylethanolamine and triethanolamine; secondary amines such as diethylamine, dibutylamine, diethanolamine and morpholine; primary amines such as propylamine and ethanolamine. Ammonia and the like. The basic substance is preferably used in an amount of 0.8 to 4.0 molar equivalents relative to the carboxyl group in the acid-modified polyolefin (a).
本発明では形成塗膜の耐水性の点から、上記酸変性ポリオレフィン（ａ）の水性化の際に界面活性剤を使用しないことが望ましい。 In the present invention, from the viewpoint of the water resistance of the formed coating film, it is desirable not to use a surfactant when making the acid-modified polyolefin (a) aqueous.
本発明の水性樹脂組成物は、上記の通り得られる水性樹脂分散体（Ａ）の存在下で、重合性不飽和単量体（Ｂ）を用いて乳化重合させることにより得られる。 The aqueous resin composition of the present invention can be obtained by emulsion polymerization using the polymerizable unsaturated monomer (B) in the presence of the aqueous resin dispersion (A) obtained as described above.
上記重合性不飽和単量体（Ｂ）としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、ｉ−プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、オクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ノニル（メタ）アクリレート、トリデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル(メタ)アクリレート、シクロヘキシル（メタ）アクリレ−ト、メチルシクロヘキシル（メタ）アクリレ−ト、ｔ−ブチルシクロヘキシル（メタ）アクリレ−ト、シクロドデシル（メタ）アクリレ−ト等のアルキル又はシクロアルキル（メタ）アクリレート；イソボルニル（メタ）アクリレート等のイソボルニル基を有する重合性不飽和単量体；アダマンチル（メタ）アクリレート等のアダマンチル基を有する重合性不飽和単量体；スチレン、α−メチルスチレン、ビニルトルエンなどのビニル芳香族化合物；ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２−メトキシエトキシ）シラン、γ−（メタ）アクリロイルオキシプロピルトリメトキシシラン、γ−（メタ）アクリロイルオキシプロピルトリエトキシシランなどのアルコキシシリル基を有する重合性不飽和単量体；パーフルオロブチルエチル（メタ）アクリレート、パーフルオロオクチルエチル（メタ）アクリレート等のパーフルオロアルキル（メタ）アクリレート；フルオロオレフィン等のフッ素化アルキル基を有する重合性不飽和単量体；マレイミド基等の光重合性官能基を有する重合性不飽和単量体；Ｎ−ビニルピロリドン、エチレン、ブタジエン、クロロプレン、プロピオン酸ビニル、酢酸ビニル等のビニル化合物；（メタ）アクリル酸、マレイン酸、クロトン酸、β−カルボキシエチルアクリレート等のカルボキシル基を有する重合性不飽和単量体；（メタ）アクリロニトリル、（メタ）アクリルアミド、ジメチルアミノプロピル（メタ）アクリルアミド、ジメチルアミノエチル（メタ）アクリレート、グリシジル（メタ）アクリレートとアミン類との付加物等の含窒素重合性不飽和単量体；２−ヒドロキシエチル（メタ）アクリレ−ト、２−ヒドロキシプロピル（メタ）アクリレ−ト、３−ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレートなどの（メタ）アクリル酸のＣ２〜Ｃ８ヒドロキシアルキル（メタ）アクリレート、アリルアルコ−ル、上記Ｃ２〜Ｃ８ヒドロキシアルキル（メタ）アクリレートのε−カプロラクトン変性体などの水酸基を有する（メタ）アクリレート；分子末端が水酸基であるポリオキシエチレン鎖を有する（メタ）アクリレート等の水酸基を有する重合性不飽和単量体；グリシジル（メタ）アクリレートなどのエポキシ基を有する重合性不飽和単量体；分子末端がアルコキシ基であるポリオキシエチレン鎖を有する（メタ）アクリレート；２−アクリルアミド−２−メチルプロパンスルホン酸、アリルスルホン酸、スチレンスルホン酸ナトリウム塩、スルホエチルメタクリレート及びそのナトリウム塩やアンモニウム塩等のスルホン酸基を有する重合性不飽和単量体；２−ヒドロキシ−４−（３−メタクリロイルオキシ−２−ヒドロキシプロポキシ）ベンゾフェノン、２−ヒドロキシ−４−（３−アクリロイルオキシ−２−ヒドロキシプロポキシ）ベンゾフェノン、２，２’−ジヒドロキシ−４−（３−メタクリロイルオキシ−２−ヒドロキシプロポキシ）ベンゾフェノン、２，２’−ジヒドロキシ−４−（３−アクリロイルオキシ−２−ヒドロキシプロポキシ）ベンゾフェノンなどのヒドロキシベンゾフェノン類とグリシジル（メタ）アクリレートとの付加反応生成物、或いは２−（２’−ヒドロキシ−５’−メタクリロイルオキシエチルフェニル）−２Ｈ−ベンゾトリアゾール等の紫外線吸収性官能基を有する重合性不飽和単量体；４−（メタ）アクリロイルオキシ−１，２，２，６，６−ペンタメチルピペリジン、４−（メタ）アクリロイルオキシ−２，２，６，６−テトラメチルピペリジン、４−シアノ−４−（メタ）アクリロイルアミノ−２，２，６，６−テトラメチルピペリジン、１−（メタ）アクリロイル−４−（メタ）アクリロイルアミノ−２，２，６，６−テトラメチルピペリジン、１−（メタ）アクリロイル−４−シアノ−４−（メタ）アクリロイルアミノ−２，２，６，６−テトラメチルピペリジン、４−クロトノイルオキシ−２，２，６，６−テトラメチルピペリジン、４−クロトノイルアミノ−２，２，６，６−テトラメチルピペリジン、１−クロトノイル−４−クロトノイルオキシ−２，２，６，６−テトラメチルピペリジン等の紫外線安定性重合性不飽和単量体；アクロレイン、ダイアセトンアクリルアミド、ダイアセトンメタクリルアミド、アセトアセトキシエチルメタクリレート、ホルミルスチロール、４〜７個の炭素原子を有するビニルアルキルケトン（例えば、ビニルメチルケトン、ビニルエチルケトン、ビニルブチルケトン）等のカルボニル基を有する重合性不飽和単量体；アリル（メタ）アクリレ−ト、エチレングリコ−ルジ（メタ）アクリレ−ト、トリエチレングリコ−ルジ（メタ）アクリレ−ト、テトラエチレングリコ−ルジ（メタ）アクリレ−ト、１，３−ブチレングリコ−ルジ（メタ）アクリレ−ト、トリメチロ−ルプロパントリ（メタ）アクリレ−ト、１，４−ブタンジオ−ルジ（メタ）アクリレ−ト、ネオペンチルグリコ−ルジ（メタ）アクリレ−ト、１，６−ヘキサンジオ−ルジ（メタ）アクリレ−ト、ペンタエリスリト−ルジ（メタ）アクリレ−ト、ペンタエリスリト−ルテトラ（メタ）アクリレ−ト、グリセロ−ルジ（メタ）アクリレ−ト、１，１，１−トリスヒドロキシメチルエタンジ（メタ）アクリレ−ト、１，１，１−トリスヒドロキシメチルエタントリ（メタ）アクリレ−ト、１，１，１−トリスヒドロキシメチルプロパントリ（メタ）アクリレ−ト、トリアリルイソシアヌレ−ト、ジアリルテレフタレ−ト、ジビニルベンゼン等の１分子中に少なくとも２個の重合性不飽和基を有する多ビニル化合物等が挙げられ、これらは得られる水性樹脂分散体に望まれる性能などに応じて単独でもしくは２種以上組み合わせて使用することができる。 Examples of the polymerizable unsaturated monomer (B) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and n-butyl (meth). Acrylate, i-butyl (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) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, cyclodode An alkyl or cycloalkyl (meth) acrylate such as ru (meth) acrylate; a polymerizable unsaturated monomer having an isobornyl group such as isobornyl (meth) acrylate; a polymerizable having an adamantyl group such as adamantyl (meth) acrylate Unsaturated monomers; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyl toluene; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltri Polymerizable unsaturated monomers having alkoxysilyl groups such as methoxysilane and γ- (meth) acryloyloxypropyltriethoxysilane; perfluorinated compounds such as perfluorobutylethyl (meth) acrylate and perfluorooctylethyl (meth) acrylate A polymerizable unsaturated monomer having a fluorinated alkyl group such as a fluoroolefin; a polymerizable unsaturated monomer having a photopolymerizable functional group such as a maleimide group; N-vinylpyrrolidone, ethylene, Vinyl compounds such as butadiene, chloroprene, vinyl propionate and vinyl acetate; polymerizable unsaturated monomers having a carboxyl group such as (meth) acrylic acid, maleic acid, crotonic acid and β-carboxyethyl acrylate; (meth) acrylonitrile , (Meth) acrylamide, dimethylaminopropyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, nitrogen-containing polymerizable unsaturated monomers such as adducts of glycidyl (meth) acrylate and amines; 2-hydroxyethyl (Meth) acrylate, 2-hydroxypropylene (Meth) acrylate - DOO, 3-hydroxypropyl (meth) acrylate, C 2 -C 8 hydroxyalkyl (meth) acrylate (meth) acrylic acid such as hydroxybutyl (meth) acrylate, allyl alcohol - le, the C 2 ~ ( 8 ) polymerizable unsaturated units having a hydroxyl group such as a (meth) acrylate having a hydroxyl group such as a ε-caprolactone modified form of C 8 hydroxyalkyl (meth) acrylate; a polyoxyethylene chain having a molecular terminal hydroxyl group. Polymeric unsaturated monomer having an epoxy group such as glycidyl (meth) acrylate; (meth) acrylate having a polyoxyethylene chain having an alkoxy group at the molecular end; 2-acrylamido-2-methylpropanesulfonic acid , Allyl sulfonic acid, styrene sulfonic acid Polymerizable unsaturated monomer having a sulfonic acid group such as thorium salt, sulfoethyl methacrylate and sodium salt or ammonium salt thereof; 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2-hydroxy -4- (3-acryloyloxy-2-hydroxypropoxy) benzophenone, 2,2'-dihydroxy-4- (3-methacryloyloxy-2-hydroxypropoxy) benzophenone, 2,2'-dihydroxy-4- (3- Addition reaction product of hydroxybenzophenones such as acryloyloxy-2-hydroxypropoxy) benzophenone and glycidyl (meth) acrylate, or 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole Polymerizable unsaturated monomer having an ultraviolet-absorbing functional group: 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyloxy-2,2, 6,6-tetramethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2 , 6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2, 6,6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2 UV-stable polymerizable unsaturated monomers such as 6,6-tetramethylpiperidine; acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrol, vinylalkyl having 4 to 7 carbon atoms Polymerizable unsaturated monomers having a carbonyl group such as ketones (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone); allyl (meth) acrylate, ethylene glycol di (meth) acrylate, tri Ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1, 4-butanediol (meth) acrylate, ne Pentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, Glycerol di (meth) acrylate, 1,1,1-trishydroxymethylethanedi (meth) acrylate, 1,1,1-trishydroxymethylethanetri (meth) acrylate, 1,1, 1-trishydroxymethylpropane tri (meth) acrylate, triallyl isocyanurate, diallyl terephthalate, polyvinyl compound having at least two polymerizable unsaturated groups in one molecule, etc. These may be used alone or in combination of two or more depending on the performance desired for the resulting aqueous resin dispersion. Can.
本明細書において、「（メタ）アクリル」は「アクリル又はメタクリル」を、「（メタ）アクリレート」は「アクリレート又はメタクリレート」を意味する。 In the present specification, “(meth) acryl” means “acryl or methacryl”, and “(meth) acrylate” means “acrylate or methacrylate”.
これらのうち、本発明では、上記重合性不飽和単量体（Ｂ）がその成分の少なくとも一部として水酸基含有重合性不飽和単量体を含有することが、得られる水性樹脂組成物を水酸基と反応し得る硬化剤、例えばイソシアネート系やメラミン系等の硬化剤と共に用いる場合の該硬化剤との架橋性、得られる塗膜の耐候性、耐水性の点から好適である。 Among these, in the present invention, the polymerizable unsaturated monomer (B) contains a hydroxyl group-containing polymerizable unsaturated monomer as at least a part of its components. It is preferable from the viewpoint of crosslinkability with the curing agent when used together with a curing agent capable of reacting with, for example, an isocyanate-based or melamine-based curing agent, the weather resistance of the resulting coating film, and water resistance.
水酸基含有重合性不飽和単量体としては、１分子中に１個の水酸基と１個の重合性不飽和基を有する化合物が包含され、具体的には例えば、２−ヒドロキシエチル（メタ）アクリレ−ト、２−ヒドロキシプロピル（メタ）アクリレ−ト、３−ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレートなどの（メタ）アクリル酸のＣ２〜Ｃ８ヒドロキシアルキル（メタ）アクリレート、アリルアルコ−ル、上記Ｃ２〜Ｃ８ヒドロキシアルキル（メタ）アクリレートのε−カプロラクトン変性体などの水酸基を有する（メタ）アクリレート；分子末端が水酸基であるポリオキシエチレン鎖を有する（メタ）アクリレート等が挙げられ、これらは単独でもしくは２種以上組み合わせて使用することができる。かかる水酸基含有重合性不飽和単量体は、一般に、単量体（Ｂ）の合計質量を基準にして、１〜３０質量％、好ましくは３〜２０質量％の範囲内で使用するのが適している。 Examples of the hydroxyl group-containing polymerizable unsaturated monomer include compounds having one hydroxyl group and one polymerizable unsaturated group in one molecule, and specifically, for example, 2-hydroxyethyl (meth) acrylate. - DOO, 2-hydroxypropyl (meth) acrylate - DOO, 3-hydroxypropyl (meth) acrylate, C 2 -C 8 hydroxyalkyl (meth) acrylate (meth) acrylic acid such as hydroxybutyl (meth) acrylate, allyl alcohol -(Meth) acrylate having a hydroxyl group, such as a modified ε-caprolactone of the above-mentioned C 2 -C 8 hydroxyalkyl (meth) acrylate; (meth) acrylate having a polyoxyethylene chain whose molecular end is a hydroxyl group, etc. These can be used alone or in combination of two or more. Such a hydroxyl group-containing polymerizable unsaturated monomer is generally suitable for use in the range of 1 to 30% by mass, preferably 3 to 20% by mass, based on the total mass of the monomer (B). ing.
また本発明では、上記重合性不飽和単量体（Ｂ）が、その成分の少なくとも一部としてカルボニル基含有重合性不飽和単量体を含有することが、得られる水性樹脂組成物をヒドラジン誘導体と共に用いる場合の該ヒドラジン誘導体との架橋性、得られる塗膜の耐候性、耐水性の点から好適である。 In the present invention, the polymerizable unsaturated monomer (B) contains a carbonyl group-containing polymerizable unsaturated monomer as at least a part of its components. When used together with the hydrazine derivative, it is suitable from the viewpoint of the weather resistance and water resistance of the resulting coating film.
カルボニル基含有重合性不飽和単量体としては、１分子中に１個のカルボニル基と１個の重合性不飽和結合を有する化合物が包含され、具体的には例えば、アクロレイン、ダイアセトンアクリルアミド、ダイアセトンメタクリルアミド、アセトアセトキシエチルメタクリレート、ホルミルスチロール、４〜７個の炭素原子を有するビニルアルキルケトン（例えば、ビニルメチルケトン、ビニルエチルケトン、ビニルブチルケトン）等が挙げられ、これらは単独で又は２種以上組み合わせて使用することができる。中でも、特にダイアセトン（メタ）アクリルアミドが好適である。かかるカルボニル基含有重合性不飽和単量体は、一般に、単量体（Ｂ）の合計質量を基準にして、１〜３０質量％、好ましくは３〜２０質量％の範囲内で使用するのが適している。 The carbonyl group-containing polymerizable unsaturated monomer includes a compound having one carbonyl group and one polymerizable unsaturated bond in one molecule, and specifically includes, for example, acrolein, diacetone acrylamide, Examples include diacetone methacrylamide, acetoacetoxyethyl methacrylate, formylstyrene, vinyl alkyl ketones having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone) and the like. Two or more types can be used in combination. Of these, diacetone (meth) acrylamide is particularly preferred. Such a carbonyl group-containing polymerizable unsaturated monomer is generally used in the range of 1 to 30% by mass, preferably 3 to 20% by mass, based on the total mass of the monomer (B). Is suitable.
さらに本発明では、上記重合性不飽和単量体（Ｂ）が、その成分の少なくとも一部として１分子中に少なくとも２個の重合性不飽和基を有する多ビニル化合物を含有することが、形成塗膜の耐水性、耐溶剤性等の点から好適である。 Furthermore, in the present invention, the polymerizable unsaturated monomer (B) contains a polyvinyl compound having at least two polymerizable unsaturated groups in one molecule as at least a part of the component. It is suitable from the viewpoints of water resistance and solvent resistance of the coating film.
多ビニル化合物としては、例えばアリル（メタ）アクリレ−ト、エチレングリコ−ルジ（メタ）アクリレ−ト、トリエチレングリコ−ルジ（メタ）アクリレ−ト、テトラエチレングリコ−ルジ（メタ）アクリレ−ト、１，３−ブチレングリコ−ルジ（メタ）アクリレ−ト、トリメチロ−ルプロパントリ（メタ）アクリレ−ト、１，４−ブタンジオ−ルジ（メタ）アクリレ−ト、ネオペンチルグリコ−ルジ（メタ）アクリレ−ト、１，６−ヘキサンジオ−ルジ（メタ）アクリレ−ト、ペンタエリスリト−ルジ（メタ）アクリレ−ト、ペンタエリスリト−ルテトラ（メタ）アクリレ−ト、グリセロ−ルジ（メタ）アクリレ−ト、１，１，１−トリスヒドロキシメチルエタンジ（メタ）アクリレ−ト、１，１，１−トリスヒドロキシメチルエタントリ（メタ）アクリレ−ト、１，１，１−トリスヒドロキシメチルプロパントリ（メタ）アクリレ−ト、トリアリルイソシアヌレ−ト、ジアリルテレフタレ−ト、ジビニルベンゼン等が挙げられ、これらは単独で又は２種以上組み合わせて使用することができる。かかる多ビニル化合物は、一般に、単量体（Ｂ）の合計質量を基準にして、０．１〜１５質量％、好ましくは０．５〜１０質量％の範囲内で使用するのが適している。 Examples of the polyvinyl compound include allyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerol di (meth) acrylate, 1 , 1,1-Trishydroxymethylethane di (meth) acrylate, 1,1,1-trishydroxymethylethane (Meth) acrylate, 1,1,1-trishydroxymethylpropane tri (meth) acrylate, triallyl isocyanurate, diallyl terephthalate, divinylbenzene, etc. Two or more types can be used in combination. Such polyvinyl compounds are generally suitable for use in the range of 0.1 to 15% by mass, preferably 0.5 to 10% by mass, based on the total mass of the monomer (B). .
上記乳化重合においては、必要に応じて公知のアニオン性界面活性剤、ノニオン性界面活性剤、反応性乳化剤などを適宜使用することができ、該乳化剤の１種または２種以上の存在下で重合開始剤を使用して乳化重合させることができる。特に反応性乳化剤を用いると乳化粒子の安定性及び形成塗膜の耐水性等の点から好適である。重合開始剤には、例えばアゾイソバレロニトリル、４、４’−アゾビス−４−シアノ吉草酸のようなアゾ系開始剤、過硫酸アンモニウム、過硫酸カリウム、ｔ−ブチルハイドロパーオキシド等の過酸化物等の既知のものを用いることができる。また該重合開始剤には、必要に応じて、糖、ナトリウムホルムアルデヒドスルホキシレート、鉄錯体等の還元剤を併用し、レドックス重合系としてもよい。また、乳化重合反応温度は３０〜９５℃程度が好ましい。 In the above emulsion polymerization, known anionic surfactants, nonionic surfactants, reactive emulsifiers and the like can be appropriately used as necessary, and polymerization is performed in the presence of one or more of the emulsifiers. Emulsion polymerization can be performed using an initiator. In particular, use of a reactive emulsifier is preferable from the viewpoints of stability of the emulsified particles and water resistance of the formed coating film. Examples of the polymerization initiator include azo initiators such as azoisovaleronitrile, 4,4′-azobis-4-cyanovaleric acid, peroxides such as ammonium persulfate, potassium persulfate, and t-butyl hydroperoxide. Etc. can be used. In addition, the polymerization initiator may be combined with a reducing agent such as sugar, sodium formaldehyde sulfoxylate, iron complex, or the like as necessary to form a redox polymerization system. The emulsion polymerization reaction temperature is preferably about 30 to 95 ° C.
また上記乳化重合においては、前記酸変性ポリオレフィン（ａ）と上記重合性不飽和単量体（Ｂ）の使用比が固形分質量比で５／９５〜９５／５、好ましくは２０／８０〜８０／２０の範囲内となるようにすることが、両成分の相溶性や形成塗膜の付着性等の点から好適である。 In the emulsion polymerization, the use ratio of the acid-modified polyolefin (a) to the polymerizable unsaturated monomer (B) is 5/95 to 95/5, preferably 20/80 to 80 in terms of solid content mass ratio. / 20 is preferable from the viewpoint of compatibility of both components, adhesion of the formed coating film, and the like.
上記により得られる本発明の水性樹脂組成物は、固形分濃度が１５〜４５質量％の範囲にあることが適当である。 It is appropriate that the aqueous resin composition of the present invention obtained as described above has a solid concentration in the range of 15 to 45% by mass.
本発明の塗料組成物は、上記により得られる水性樹脂組成物を含有するものであり、さらに必要に応じて、ヒドラジン誘導体を含有することができる。該ヒドラジン誘導体としては、具体的には例えば、シュウ酸ジヒドラジド、マロン酸ジヒドラジド、グルタル酸ジヒドラジド、こはく酸ジヒドラジド、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド等の２〜１８個の炭素原子を有する飽和ジカルボン酸ジヒドラジド；マレイン酸ジヒドラジド、フマル酸ジヒドラジド、イタコン酸ジヒドラジドなどのモノオレフィン性不飽和ジカルボン酸ジヒドラジド；フタル酸ジヒドラジド、テレフタル酸ジヒドラジドまたはイソフタル酸ジヒドラジド；ピロメリット酸のジヒドラジド、トリヒドラジドまたはテトラヒドラジド；ニトリロトリヒドラジド、クエン酸トリヒドラジド、１，２，４−ベンゼントリヒドラジド、エチレンジアミンテトラ酢酸テトラヒドラジド、１，４，５，８−ナフトエ酸テトラヒドラジド；カルボン酸低級アルキルエステル基を有する低重合体をヒドラジンまたはヒドラジン水化物（ヒドラジンヒドラード）と反応させることにより得られるポリヒドラジド；炭酸ジヒドラジド等のヒドラジド基含有化合物；ビスセミカルバジド；ヘキサメチレンジイソシアネートやイソホロンジイソシアネート等のジイソシアネート又はそれから誘導されるポリイソシアネート化合物にＮ，Ｎ−ジメチルヒドラジン等のＮ，Ｎ−置換ヒドラジンや上記例示のヒドラジドを過剰に反応させて得られる多官能セミカルバジド、該ポリイソシアネート化合物とポリエーテルとポリオール類やポリエチレングリコールモノアルキルエーテル類等の親水性基を含む活性水素化合物との反応物中のイソシアネート基に上記例示のジヒドラジドを過剰に反応させて得られる水系多官能セミカルバジド；該多官能セミカルバジドと水系多官能セミカルバジドとの混合物等のセミカルバジド基を有する化合物；ビスアセチルジヒドラゾン等のヒドラゾン基を有する化合物等が挙げられる。 The coating composition of this invention contains the aqueous resin composition obtained by the above, and can further contain a hydrazine derivative as needed. Specific examples of the hydrazine derivatives include saturated dicarboxylic acid dihydrazides having 2 to 18 carbon atoms such as oxalic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide and the like. Monoolefinic unsaturated dicarboxylic acid dihydrazide such as maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide; phthalic acid dihydrazide, terephthalic acid dihydrazide or isophthalic acid dihydrazide; pyromellitic acid dihydrazide, trihydrazide or tetrahydrazide; nitrilotrihydride Citric acid trihydrazide, 1,2,4-benzenetrihydrazide, ethylenediaminetetraacetic acid tetrahydrazide, 1,4,5,8-naphthoic acid Polyhydrazide obtained by reacting a low polymer having a carboxylic acid lower alkyl ester group with hydrazine or a hydrazine hydrate (hydrazine hydride); a hydrazide group-containing compound such as carbonic dihydrazide; bissemicarbazide; hexamethylene diisocyanate Polyfunctional semicarbazide obtained by excessively reacting N, N-substituted hydrazine such as N, N-dimethylhydrazine or the above-described hydrazide with a diisocyanate such as chlorobenzene or isophorone diisocyanate or a polyisocyanate compound derived therefrom, and the polyisocyanate compound Dihydrazide as exemplified above for the isocyanate group in the reaction product of an active hydrogen compound containing a hydrophilic group such as a polyether and a polyol or a polyethylene glycol monoalkyl ether Excessively reacted with the resulting aqueous polyfunctional semicarbazide; compound having a semicarbazide group, such as a mixture of polyfunctional semicarbazide and aqueous polyfunctional semicarbazide; compound having a hydrazone group such as bis-acetyl-di hydrazone and the like.
水性塗料組成物が上記ヒドラジン誘導体を含有することにより、それから形成される塗膜は空気中の有害物質、例えばホルムアルデヒドを吸着するので、これらの有害物質の除去のために内装用途において有用であり、また上記水性樹脂組成物がカルボニル基を有する場合には、補助架橋のための架橋剤として作用することができる。 Since the water-based coating composition contains the hydrazine derivative, the coating film formed therefrom adsorbs harmful substances in the air, such as formaldehyde, and thus is useful in interior applications for the removal of these harmful substances. Further, when the aqueous resin composition has a carbonyl group, it can act as a crosslinking agent for auxiliary crosslinking.
上記ヒドラジン誘導体の配合量は、上記水性樹脂組成物の樹脂固形分に対して、一般に、０．０１〜１０質量％、特に０．０５〜８質量％の範囲内が望ましい。 In general, the amount of the hydrazine derivative is preferably in the range of 0.01 to 10% by mass, particularly 0.05 to 8% by mass, based on the resin solid content of the aqueous resin composition.
本発明の塗料組成物は、また、上記水性樹脂組成物が水酸基などの架橋性官能基を有する場合には、該官能基と反応し得る架橋性官能基を有する硬化剤、例えばイソシアネート系硬化剤やメラミン系硬化剤などを含有することができる。 When the aqueous resin composition has a crosslinkable functional group such as a hydroxyl group, the coating composition of the present invention also has a curing agent having a crosslinkable functional group capable of reacting with the functional group, such as an isocyanate curing agent. And a melamine-based curing agent.
本発明の塗料組成物には、さらに必要に応じて上記以外の水溶性もしくは水分散性の樹脂を配合することができ、該水溶性もしくは水分散性の樹脂としては、例えばウレタン樹脂、アクリル樹脂、ポリエステル樹脂、これらの樹脂のグラフト体、アクリル変性もしくはポリエステル変性エポキシ樹脂、さらにはブロックイソシアネート基含有ポリエステル樹脂等の自己架橋型樹脂などが挙げられ、特にウレタンディスパージョン、水溶性もしくは水分散性アクリル樹脂や水溶性もしくは水分散性ポリエステル樹脂が好適である。 If necessary, the coating composition of the present invention may further contain a water-soluble or water-dispersible resin other than those described above. Examples of the water-soluble or water-dispersible resin include urethane resins and acrylic resins. , Polyester resins, grafts of these resins, acrylic-modified or polyester-modified epoxy resins, and self-crosslinking resins such as blocked isocyanate group-containing polyester resins, especially urethane dispersions, water-soluble or water-dispersible acrylics, etc. Resins and water-soluble or water-dispersible polyester resins are preferred.
本発明の塗料組成物には、さらに必要に応じて酸化チタン、ベンガラ、アルミペースト、アゾ系、フタロシアニン系などの着色顔料；タルク、シリカ、炭酸カルシウム、硫酸バリウム、亜鉛華（酸化亜鉛）などの体質顔料を含有させることができ、これらはそれぞれ単独で又は２種以上組合せて用いることができる。またプライマー用途の場合には導電性顔料を含有させることができる。また例えば、硬化触媒、レオロジーコントロール剤、樹脂微粒子、消泡剤、表面調整剤、紫外線吸収剤、酸化防止剤、防腐剤、防カビ剤、可塑剤、有機溶剤などの塗料用添加剤等を適宜含有させることができる。 The coating composition of the present invention may further include, if necessary, color pigments such as titanium oxide, bengara, aluminum paste, azo series, and phthalocyanine series; talc, silica, calcium carbonate, barium sulfate, zinc white (zinc oxide), etc. Extender pigments can be contained, and these can be used alone or in combination of two or more. Moreover, in the case of a primer use, a conductive pigment can be contained. In addition, for example, a curing catalyst, a rheology control agent, resin fine particles, an antifoaming agent, a surface conditioner, an ultraviolet absorber, an antioxidant, an antiseptic, an antifungal agent, a plasticizer, an additive for paints such as an organic solvent, etc. It can be included.
上記により得られる本発明の水性塗料組成物はプラスチック成形品に塗装することができる。 The aqueous coating composition of the present invention obtained as described above can be applied to plastic molded articles.
プラスチック成形品としては、例えば、バンパー、スポイラー、グリル、フェンダーなどの自動車外板部；ダッシュボード、インストメンタルパネル、ハンドルなどの自動車内装部；家庭電化製品の外板部などに使用されているプラスチック成形品などが挙げられ、その材質としては、例えば、エチレン、プロピレン、ブチレン、ヘキセンなどの炭素数２〜１０のオレフィン類の１種もしくは２種以上を（共）重合せしめてなるポリオレフィンが特に好適であるが、それ以外に、ポリカーボネート、ＡＢＳ樹脂、ウレタン樹脂、ポリアミドなどにも本発明組成物を適用することができる。 Plastic molded products include, for example, automobile exterior parts such as bumpers, spoilers, grills, and fenders; automobile interior parts such as dashboards, instrumental panels, and handles; plastics used in exterior parts of home appliances, etc. Examples of the material include polyolefins obtained by (co) polymerizing one or more of olefins having 2 to 10 carbon atoms such as ethylene, propylene, butylene and hexene. However, the composition of the present invention can also be applied to polycarbonate, ABS resin, urethane resin, polyamide and the like.
これらのプラスチック成形品には、本発明組成物の塗装に先立ち、それ自体既知の方法で、脱脂処理、水洗処理などを適宜行なっておくことができる。 Prior to the application of the composition of the present invention, these plastic molded articles can be appropriately subjected to a degreasing treatment, a water washing treatment and the like by a method known per se.
本発明組成物の塗装は、被塗物に対し、通常、プライマー用途においては乾燥膜厚で１〜５０μｍ、好ましくは５〜４５μｍの範囲内となるように、また１コート仕上げ用途においては乾燥膜厚で５〜５０μｍ、好ましくは１０〜４０μｍの範囲内となるように、エアスプレー、エアレススプレー、浸漬塗装、刷毛などを用いて行なうことができる。該組成物の塗装後、得られる塗膜面を、必要に応じて室温で１〜６０分間セッティングし又は４０〜８０℃程度の温度で１〜６０分間予備加熱することができ、あるいは約６０〜約１４０℃、好ましくは約６０〜約１２０℃の温度で２０〜４０分間程度加熱して硬化させることができる。 The coating of the composition of the present invention is usually applied to the object to be coated so that the dry film thickness is 1 to 50 μm, preferably 5 to 45 μm in the primer application, and in the one-coat finishing application. Air spray, airless spray, dip coating, brush, etc. can be used so that the thickness is in the range of 5 to 50 μm, preferably 10 to 40 μm. After coating of the composition, the resulting coating surface can be set at room temperature for 1 to 60 minutes as necessary, or preheated at a temperature of about 40 to 80 ° C. for 1 to 60 minutes, or about 60 to It can be cured by heating at a temperature of about 140 ° C., preferably about 60 to about 120 ° C. for about 20 to 40 minutes.
本発明の塗装方法は、上記により得られる水性塗料組成物をプラスチック成形品に塗装して１コート仕上げとすることができ、また上記により得られる水性塗料組成物をプライマーとしてプラスチック成形品に塗装し、ついでその塗面に、上塗り塗料を塗装することもできる。上塗り塗料としては、着色塗料を単独で用いて塗装しても良いし、該着色塗料をベース塗料として用いて、ベース塗料及びクリヤー塗料を順次塗装することもできる。 In the coating method of the present invention, the water-based coating composition obtained as described above can be applied to a plastic molded article to make one coat finish. Then, a top coat can be applied to the coated surface. As the top coating, a colored coating may be used alone, or a base coating and a clear coating may be sequentially applied using the colored coating as a base coating.
上記着色ベース塗料は、通常、有機溶剤及び／又は水を主たる溶媒とし、着色顔料、光輝顔料、染料などの着色成分、基体樹脂、架橋剤などの樹脂成分を主に含有するものである。 The colored base paint usually contains an organic solvent and / or water as a main solvent, and mainly contains colored components such as colored pigments, bright pigments and dyes, and resin components such as a base resin and a crosslinking agent.
上記着色ベース塗料に使用される基体樹脂としては、例えば、水酸基、エポキシ基、カルボキシル基、シラノール基のような架橋性官能基を有するアクリル樹脂、ポリエステル樹脂、アルキド樹脂等を挙げることができる。また架橋剤としては、これらの官能基と反応しうるメラミン樹脂、尿素樹脂等のアミノ樹脂や（ブロック）ポリイソシアネート、ポリエポキシド、ポリカルボン酸等を挙げることができる。 Examples of the base resin used in the colored base paint include acrylic resins having a crosslinkable functional group such as a hydroxyl group, an epoxy group, a carboxyl group, and a silanol group, a polyester resin, and an alkyd resin. Examples of the crosslinking agent include amino resins such as melamine resin and urea resin that can react with these functional groups, (block) polyisocyanate, polyepoxide, and polycarboxylic acid.
上記着色ベース塗料には、さらに必要に応じて、体質顔料、硬化触媒、紫外線吸収剤、塗面調整剤、レオロジーコントロール剤、酸化防止剤、消泡剤、ワックス、防腐剤などの塗料用添加剤等を適宜含有させることができる。 In addition to the above-mentioned colored base paint, additives for paints such as extender pigments, curing catalysts, UV absorbers, coating surface conditioners, rheology control agents, antioxidants, antifoaming agents, waxes, preservatives, etc. Etc. can be contained appropriately.
上記着色ベース塗料を、通常、乾燥膜厚で５〜５０μｍ、好ましくは１０〜２０μｍの範囲内となるように静電塗装し、得られた塗膜面を、必要に応じて室温で１〜６０分間セッティングしたり、約４０〜８０℃程度で１〜６０分間予備加熱することができ、あるいは約６０〜１４０℃、好ましくは約８０〜１２０℃程度の温度で２０〜４０分間加熱して硬化させることができる。 The colored base paint is usually electrostatically coated so that the dry film thickness is in the range of 5 to 50 μm, preferably 10 to 20 μm, and the obtained coating surface is 1 to 60 at room temperature as necessary. It can be set for about 4 minutes, preheated at about 40-80 ° C for 1-60 minutes, or heated at about 60-140 ° C, preferably about 80-120 ° C for 20-40 minutes for curing. be able to.
本発明方法に使用されるクリヤー塗料は、基体樹脂、架橋剤などの樹脂成分、及び有機溶剤や水などを主に含有し、さらに必要に応じて紫外線吸収剤、光安定剤、硬化触媒、塗面調整剤、レオロジーコントロール剤、酸化防止剤、消泡剤、ワックスなどの塗料用添加剤を配合してなる有機溶剤系或いは水系の熱硬化性塗料であり、このクリヤー塗料の塗膜を透して下層塗膜を視認できる程度の透明性を有するものである。 The clear coating used in the method of the present invention mainly contains a base resin, a resin component such as a crosslinking agent, an organic solvent, water, and the like, and further, if necessary, an ultraviolet absorber, a light stabilizer, a curing catalyst, a coating. It is an organic solvent-based or water-based thermosetting coating that contains paint additives such as surface conditioners, rheology control agents, antioxidants, antifoaming agents and waxes. Therefore, it has transparency to the extent that the lower layer coating film can be visually recognized.
上記基体樹脂としては、例えば水酸基、カルボキシル基、シラノール基、エポキシ基などの少なくとも１種の架橋性官能基を含有するアクリル樹脂、ポリエステル樹脂、アルキド樹脂、フッ素樹脂、ウレタン樹脂、シリコン含有樹脂などが挙げられ、特に水酸基含有アクリル樹脂が好適である。架橋剤としては、これらの官能基と反応しうるメラミン樹脂、尿素樹脂、（ブロック）ポリイソシアネート化合物、エポキシ化合物、カルボキシル基含有化合物、酸無水物、アルコキシシラン基含有化合物などが挙げられ、特にポリイソシアネート化合物が好適である。 Examples of the base resin include acrylic resins, polyester resins, alkyd resins, fluororesins, urethane resins, and silicon-containing resins containing at least one crosslinkable functional group such as a hydroxyl group, a carboxyl group, a silanol group, and an epoxy group. A hydroxyl group-containing acrylic resin is particularly suitable. Examples of the cross-linking agent include melamine resins, urea resins, (block) polyisocyanate compounds, epoxy compounds, carboxyl group-containing compounds, acid anhydrides, alkoxysilane group-containing compounds that can react with these functional groups. Isocyanate compounds are preferred.
上記クリヤー塗料の塗装は、乾燥膜厚で１０〜５０μｍ、好ましくは１５〜４０μｍの範囲内となるように静電塗装し、得られた塗膜面を、必要に応じて室温で１〜６０分間セッティングしたり、約４０〜８０℃程度で１〜６０分間予備加熱した後、約６０〜１４０℃、好ましくは約７０〜１２０℃程度の温度で２０〜４０分間加熱して硬化させることにより行うことができる。 The clear coating is applied electrostatically so that the dry film thickness is within a range of 10 to 50 μm, preferably 15 to 40 μm, and the obtained coating surface is applied at room temperature for 1 to 60 minutes as necessary. Setting or preheating at about 40 to 80 ° C. for 1 to 60 minutes, and then heating and curing at about 60 to 140 ° C., preferably about 70 to 120 ° C. for 20 to 40 minutes. Can do.
以下、実施例を挙げて本発明をさらに詳細に説明する。尚、「部」及び「％」は、別記しない限り「質量部」及び「質量％」を示す。 Hereinafter, the present invention will be described in more detail with reference to examples. “Part” and “%” indicate “part by mass” and “% by mass” unless otherwise specified.
水性樹脂組成物の製造
実施例１
温度計、攪拌装置、還流冷却管を備えた４つ口フラスコを窒素置換させ、その中に「スーパークロンＳ−８５１ＬＳ」（日本製紙株式会社製、商品名、無水マレイン酸変性塩素化ポリオレフィン）１００ｇ、テトラヒドロフラン１９０ｇを加え、６５℃にて十分に融解させた。次いでその中に１−ブタノール４０ｇ、ジメチルエタノールアミン３ｇを加えて１５分間攪拌し、さらに脱イオン水３００ｇを加えて分散させた。次いで６５℃で溶剤分を減圧留去することで、酸変性塩素化ポリオレフィンの水性分散体（Ａ−１）を得た。この分散体の固形分濃度は３０％で、ｐＨは８．１であった。
Example 1 Production of Aqueous Resin Composition
A four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser was replaced with nitrogen, and "Supercron S-851LS" (manufactured by Nippon Paper Industries Co., Ltd., trade name, maleic anhydride-modified chlorinated polyolefin) 100 g Then, 190 g of tetrahydrofuran was added and sufficiently melted at 65 ° C. Next, 40 g of 1-butanol and 3 g of dimethylethanolamine were added and stirred for 15 minutes, and 300 g of deionized water was further added and dispersed. Subsequently, the aqueous solution (A-1) of acid-modified chlorinated polyolefin was obtained by depressurizingly distilling a solvent part at 65 degreeC. This dispersion had a solids concentration of 30% and a pH of 8.1.
次いで上記水性分散体（Ａ−１）１３３.３ｇに、ディスパーでの攪拌下に、脱イオン水１３１.９ｇを加えて希釈し、下記表１の配合の重合性単量体混合物（Ｂ−１）６０ｇおよび「アデカリアソープＳＲ−１０２５」（株式会社アデカ製、商品名、反応性乳化剤）４ｇを加えた。これを温度計、攪拌装置、還流冷却管を備えた４つ口フラスコに移し、６５℃に加熱した後に「ＶＡ−０５７」（和光純薬工業社製、重合開始剤）０.４２ｇを脱イオン水８.４ｇで希釈したものを加え、１.５時間反応を行って、水性樹脂組成物（Ｉ−１）を得た。この水性樹脂組成物の固形分濃度は３０％で、ｐＨは８.０であった。 Next, 131.3 g of the above-mentioned aqueous dispersion (A-1) was diluted by adding 131.9 g of deionized water under stirring with a disper, and the polymerizable monomer mixture (B-1) having the composition shown in Table 1 below was diluted. ) 60 g and 4 g of “ADEKA rear soap SR-1025” (manufactured by Adeka, trade name, reactive emulsifier) were added. This was transferred to a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, heated to 65 ° C., and 0.42 g of “VA-057” (manufactured by Wako Pure Chemical Industries, Ltd., polymerization initiator) was deionized. A solution diluted with 8.4 g of water was added and reacted for 1.5 hours to obtain an aqueous resin composition (I-1). This aqueous resin composition had a solid content of 30% and a pH of 8.0.
実施例２〜６
実施例１において、重合性単量体混合物の配合組成を表１に記載のとおりに変更する以外は上記実施例１と同様にして、水性樹脂組成物（Ｉ−２）〜（Ｉ−６）を得た。
Examples 2-6
In Example 1, the aqueous resin compositions (I-2) to (I-6) were the same as Example 1 except that the composition of the polymerizable monomer mixture was changed as shown in Table 1. Got.
比較例１
温度計、攪拌装置、還流冷却管を備えた４つ口フラスコを窒素置換させ、その中に「スーパークロンＳ−８５１ＬＳ」（日本製紙株式会社製、商品名、無水マレイン酸変性塩素化ポリオレフィン）１００ｇ、シクロヘキサン１００ｇを加え、６５℃にて十分に融解させた。次いでその中に「エマノーン１１１２」（花王ケミカル社製、ポリエチレングリコールモノラウレート）２０ｇ、「ニューコール２７１Ａ」（日本乳化剤社製、アルキルジフェニルエーテルジスルホン酸ナトリウム塩）２ｇを加えて１５分間攪拌し、さらに脱イオン水３００ｇを加えて分散させた。次いで６５℃で溶剤分を減圧留去することで、酸変性塩素化ポリオレフィンの水性分散体（Ａ−２）を得た。この分散体の固形分濃度は２５％で、ｐＨは８．１であった。
Comparative Example 1
A four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser was replaced with nitrogen, and "Supercron S-851LS" (manufactured by Nippon Paper Industries Co., Ltd., trade name, maleic anhydride-modified chlorinated polyolefin) 100 g 100 g of cyclohexane was added and sufficiently melted at 65 ° C. Next, 20 g of “Emanon 1112” (manufactured by Kao Chemical Co., polyethylene glycol monolaurate) and 2 g of “New Coal 271A” (manufactured by Nippon Emulsifier Co., Ltd., sodium alkyldiphenyl ether disulfonate) are added and stirred for 15 minutes. 300 g of deionized water was added and dispersed. Subsequently, the aqueous solution (A-2) of acid-modified chlorinated polyolefin was obtained by depressurizingly distilling a solvent part at 65 degreeC. This dispersion had a solids concentration of 25% and a pH of 8.1.
次いで上記水性分散体（Ａ−２）１６０．０ｇに、ディスパーでの攪拌下に、脱イオン水１０５．２ｇを加えて希釈し、前記表１の重合性単量体混合物（Ｂ−１）６０ｇを加えた。これを温度計、攪拌装置、還流冷却管を備えた４つ口フラスコに移し、６５℃に加熱した後に「ＶＡ−０５７」０.４２ｇを脱イオン水８.４ｇで希釈したものを加え、１.５時間反応を行って、水性樹脂組成物（Ｉ−７）を得た。この水性樹脂組成物の固形分濃度は３０％で、ｐＨは７.２であった。 Next, 105.2 g of deionized water was added to 160.0 g of the above aqueous dispersion (A-2) with stirring with a disper to dilute, and 60 g of the polymerizable monomer mixture (B-1) shown in Table 1 above. Was added. This was transferred to a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, heated to 65 ° C., and 0.42 g of “VA-057” diluted with 8.4 g of deionized water was added. Reaction was performed for .5 hours to obtain an aqueous resin composition (I-7). This aqueous resin composition had a solid content of 30% and a pH of 7.2.
実施例７
温度計、攪拌装置、還流冷却管を備えた４つ口フラスコを窒素置換させ、その中に「スーパークロンＳ−８５１ＬＳ」を１００ｇ、テトラヒドロフラン１９０ｇを加え、６５℃にて十分に融解させた。次いでその中にジブチルアミン２．６ｇ、ジメチルエタノールアミン３ｇを加えて１５分間攪拌し、さらに脱イオン水３００ｇを加えて分散させた。次いで６５℃で溶媒を減圧留去することで、酸変性塩素化ポリオレフィンの水性分散体（Ａ−３）を得た。この分散体の固形分濃度は３０％で、ｐＨは８．２であった。
Example 7
A four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser was purged with nitrogen, and 100 g of “Superclone S-851LS” and 190 g of tetrahydrofuran were added therein and sufficiently melted at 65 ° C. Next, 2.6 g of dibutylamine and 3 g of dimethylethanolamine were added and stirred for 15 minutes, and then 300 g of deionized water was added and dispersed. Subsequently, the solvent was distilled off under reduced pressure at 65 ° C. to obtain an aqueous dispersion (A-3) of acid-modified chlorinated polyolefin. This dispersion had a solids concentration of 30% and a pH of 8.2.
次いで上記水性分散体（Ａ−３）１３３．３ｇに、ディスパーでの攪拌下に、脱イオン水１３１．９ｇを加えて希釈し、前記表１の重合性単量体混合物（Ｂ−１）６０ｇおよび「アデカリアソープＳＲ−１０２５」４ｇを加えた。これを温度計、攪拌装置、還流冷却管を備えた４つ口フラスコに移し、６５℃に加熱した後に「ＶＡ−０５７」０.４２ｇを脱イオン水８.４ｇで希釈したものを加え、１.５時間反応を行って、水性樹脂組成物（Ｉ−８）を得た。この水性樹脂組成物の固形分濃度は３０％で、ｐＨは７.２であった。 Next, 131.3 g of the above aqueous dispersion (A-3) was diluted by adding 131.9 g of deionized water under stirring with a disper, and 60 g of the polymerizable monomer mixture (B-1) shown in Table 1 above. And 4 g of “ADEKA rear soap SR-1025” was added. This was transferred to a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, heated to 65 ° C., and 0.42 g of “VA-057” diluted with 8.4 g of deionized water was added. Reaction was performed for .5 hours to obtain an aqueous resin composition (I-8). This aqueous resin composition had a solid content of 30% and a pH of 7.2.
実施例８
温度計、攪拌装置、還流冷却管を備えた４つ口フラスコを窒素置換させ、その中に「スーパークロンＳ−８５１ＬＳ」を１００ｇ、テトラヒドロフラン１９０ｇを加え、６５℃にて十分に融解させた。次いでその中に２−ヒドロキシエチルアクリレート２.３ｇ、ジメチルエタノールアミン３ｇを加えて１５分攪拌し、さらに脱イオン水３００ｇを加えて分散させた。次いで６５℃で溶媒を減圧留去することで、酸変性塩素化ポリオレフィンの水性分散体（Ａ−４）を得た。この分散体の固形分濃度は３０％で、ｐＨは８．０であった。
Example 8
A four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser was purged with nitrogen, and 100 g of “Superclone S-851LS” and 190 g of tetrahydrofuran were added therein and sufficiently melted at 65 ° C. Next, 2.3 g of 2-hydroxyethyl acrylate and 3 g of dimethylethanolamine were added and stirred for 15 minutes, and 300 g of deionized water was further added and dispersed. Subsequently, the solvent was distilled off under reduced pressure at 65 ° C. to obtain an aqueous dispersion (A-4) of acid-modified chlorinated polyolefin. This dispersion had a solids concentration of 30% and a pH of 8.0.
次いで上記水性分散体（Ａ−４）１３３.３ｇに、ディスパーでの攪拌下に、脱イオン水１３１.９ｇを加えて希釈し、ｔ−ブチルメタクリレート４６ｇ、シクロヘキシルメタクリレート１１ｇ、１，６−ヘキサンジオールジアクリレート３ｇ、及び「アデカリアソープＳＲ−１０２５」４ｇを加えた。これを温度計、攪拌装置、還流冷却管を備えた４つ口フラスコに移し、６５℃に加熱した後に「ＶＡ−０５７」０.４２ｇを脱イオン水８.４ｇで希釈したものを加え、１.５時間反応を行って、水性樹脂組成物（Ｉ−９）を得た。この水性樹脂組成物の固形分濃度は３０％で、ｐＨは７．３であった。 Next, 131.3 g of the above aqueous dispersion (A-4) was diluted by adding 131.9 g of deionized water under stirring with a disper, and 46 g of t-butyl methacrylate, 11 g of cyclohexyl methacrylate, 1,6-hexanediol. 3 g of diacrylate and 4 g of “ADEKA rear soap SR-1025” were added. This was transferred to a four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, heated to 65 ° C., and 0.42 g of “VA-057” diluted with 8.4 g of deionized water was added. Reaction was performed for .5 hours to obtain an aqueous resin composition (I-9). This aqueous resin composition had a solid content of 30% and a pH of 7.3.
水性塗料の調製
実施例９
上記水性樹脂組成物（Ｉ−１）を固形分質量で６０部、「ユーコートＵＸ３１０」（三洋化成工業社製、ウレタンディスパージョン）を固形分質量で２０部、アクリル樹脂溶液（注１）を固形分質量で２０部、「ＭＩＣＲＯ ＡＣＥ Ｋ−１」（日本タルク社製、微粉タルク）５０部、「ＪＲ−８０６」（テイカ社製、チタン白）５０部、「ＭＡ１００」（三菱化学社製、カーボンブラック）２部を、常法に従って配合し、固形分３５％となるように脱イオン水で希釈して水性塗料（１）を得た。
Preparation of water-based paint Example 9
60 parts by weight of the above-mentioned aqueous resin composition (I-1) in solid mass, 20 parts by weight of “Yukot UX310” (manufactured by Sanyo Chemical Industries, Ltd., urethane dispersion), and solid acrylic resin solution (Note 1) 20 parts by weight, 50 parts “MICRO ACE K-1” (manufactured by Nippon Talc Co., Ltd., fine talc), 50 parts “JR-806” (manufactured by Teica, titanium white), “MA100” (manufactured by Mitsubishi Chemical Corporation, 2 parts of carbon black) were blended according to a conventional method, and diluted with deionized water to a solid content of 35% to obtain an aqueous paint (1).
実施例１０〜２０及び比較例２〜６
実施例９において、配合組成を表２に示す通りとする以外は実施例９と同様に行って各水性塗料（２）〜（１７）を得た。
Examples 10-20 and Comparative Examples 2-6
In Example 9, it carried out similarly to Example 9 except having set it as a compounding composition as shown in Table 2, and obtained each aqueous coating material (2)-(17).
表２の配合は固形分表示であり、表中の（注１）〜（注２）は下記の通りである。
（注１）アクリル樹脂溶液：撹拌機、温度計、還流冷却管を備えた通常のアクリル樹脂反応槽に、エチレングリコールモノブチルエーテル３５部を仕込み、加熱撹拌して１１０℃に保持した。この中に、スチレン１０部、メチルメタクリレート４０部、ｎ−ブチルメタクリレート２５部、２−ヒドロキシエチルメタクリレート１０部、メタクリル酸３部、Ｎ，Ｎ−ジメチルアミノエチルメタクリレート５部（固形分量、脱イオン水１０部に溶解して配合）、「ＮＦバイソマーＰＥＭ６Ｅ」（第一工業製薬（株）製、商品名、ポリエチレングリコールモノメタクリレート、分子量約３５０）１０部、アゾビスイソブチロニトリル４部及びイソブチルアルコール２０部からなる混合物を３時間かけて滴下した。滴下終了後、１１０℃で３０分間熟成し、次にエチレングリコールモノブチルエーテル１５部及びアゾビスイソブチロニトリル０．５部からなる追加触媒混合液を１時間かけて滴下した。ついで１１０℃で１時間熟成したのち冷却し、固形分５５％のアクリル樹脂溶液を得た。
（注２）「バルカンＸＣ−７２」、キャボットスペシャルティケミカルズインク株式会社製、導電性カーボンブラック顔料
The composition of Table 2 is a solid content display, and (Note 1) to (Note 2) in the table are as follows.
(Note 1) Acrylic resin solution: An ordinary acrylic resin reaction vessel equipped with a stirrer, a thermometer and a reflux condenser was charged with 35 parts of ethylene glycol monobutyl ether, heated and stirred, and maintained at 110 ° C. In this, 10 parts of styrene, 40 parts of methyl methacrylate, 25 parts of n-butyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 3 parts of methacrylic acid, 5 parts of N, N-dimethylaminoethyl methacrylate (solid content, deionized water) 10 parts dissolved in 10 parts), “NF biisomer PEM6E” (Daiichi Kogyo Seiyaku Co., Ltd., trade name, polyethylene glycol monomethacrylate, molecular weight about 350), 10 parts azobisisobutyronitrile and isobutyl alcohol A mixture of 20 parts was added dropwise over 3 hours. After completion of the dropwise addition, the mixture was aged at 110 ° C. for 30 minutes, and then an additional catalyst mixture composed of 15 parts of ethylene glycol monobutyl ether and 0.5 part of azobisisobutyronitrile was added dropwise over 1 hour. Subsequently, the mixture was aged at 110 ° C. for 1 hour and then cooled to obtain an acrylic resin solution having a solid content of 55%.
(Note 2) “Vulcan XC-72”, manufactured by Cabot Specialty Chemicals Inc., conductive carbon black pigment
試験塗装物の作成１
実施例２１〜２６及び比較例７〜９
ポリプロピレン（脱脂処理済）板に、上記の操作により調製した水性塗料を表３に示すように選択し、これを乾燥膜厚で約２０μｍになるようにスプレー塗装し、８０℃で２０分間加熱乾燥させて各試験塗装物を作成した。
上記により得られた各試験塗装物を下記性能試験に供した。その結果を表３に示す。
Preparation of test paint 1
Examples 21-26 and Comparative Examples 7-9
The water-based paint prepared by the above operation is selected as shown in Table 3 on a polypropylene (degreased) plate, spray-coated to a dry film thickness of about 20 μm, and heat-dried at 80 ° C. for 20 minutes. Each test coating was made.
Each test coating obtained as described above was subjected to the following performance test. The results are shown in Table 3.
性能試験方法
初期付着性：塗膜面に素地に達するようにカッターで切り込み線を入れ、大きさ２ｍｍ×２ｍｍのマス目を１００個作り、その表面に粘着セロハン（登録商標）テープを貼着し、２０℃においてそれを急激に剥離した後のマス目の残存塗膜数を調べた。○は１００個（剥離なし）、△は９９〜５１個、×は５０個以下。
Performance test method Initial adhesion: Cut lines with a cutter to reach the substrate surface, make 100 squares with a size of 2mm x 2mm, and stick adhesive cellophane (registered trademark) tape on the surface. The number of residual coatings in the squares after peeling it off rapidly at 20 ° C. was examined. ○ is 100 pieces (no peeling), Δ is 99 to 51 pieces, and x is 50 pieces or less.
耐湿性：各試験塗装物を、５０℃で９８％ＲＨ下に１０日間静置してから、乾燥後の塗装面を目視で評価した。○はブリスター発生なし、△はブリスターの発生はないがツヤがひけている状態、×はブリスター発生ありを示す。 Moisture resistance: Each test coating was allowed to stand at 98 ° C. under 98% RH for 10 days, and then the coated surface after drying was visually evaluated. ○ indicates no blistering, Δ indicates no blistering, but gloss is present, and × indicates blistering.
耐溶剤性：各試験塗装物の塗膜面を、キシレンを湿らせたガーゼを１０枚重ねて、荷重約９．８Ｎを加えて１０往復こすった後、塗膜面を目視にて確認した。素地露出が認められない場合は○、塗膜が削れて素地露出の場合は△、塗膜が溶けて素地露出の場合は×で示す。 Solvent resistance: Ten gauze moistened with xylene were piled on the coating film surface of each test coating, applied a load of about 9.8 N, and rubbed 10 times, and then the coating film surface was visually confirmed. When the substrate exposure is not recognized, it is indicated by ○, when the coating is shaved and the substrate is exposed, Δ is indicated, and when the coating is melted and the substrate is exposed, × is indicated.
試験塗装物の作成２
実施例２７〜３２及び比較例１０〜１１
自動車用バンパーに成形加工したポリプロピレン（脱脂処理済）に、上記の操作により調製した水性塗料をプライマーとして表４に示すように選択し、これを乾燥膜厚で約１０μｍになるようにスプレー塗装し、８０℃で３分間プレヒート後、その上に着色ベースコート塗料として「ソフレックス＃４２０」（関西ペイント社製、溶剤型着色ベースコート塗料）を乾燥膜厚で約１５μｍとなるように静電塗装し、８０℃で３分間プレヒート後、クリヤー塗料として「ソフレックス＃４５０クリヤー」（関西ペイント社製、アクリルウレタン系溶剤型クリヤー塗料）を乾燥膜厚で約３０μｍとなるように静電塗装して、８０℃で３０分間加熱乾燥させて各試験塗装物を作成した。
上記により得られた各試験塗装物を下記性能試験に供した。その結果を表４に示す。
Preparation of test paint 2
Examples 27-32 and Comparative Examples 10-11
For polypropylene (degreased) molded into a bumper for automobiles, the water-based paint prepared by the above operation is selected as shown in Table 4 and spray-coated so that the dry film thickness is about 10 μm. , After preheating at 80 ° C. for 3 minutes, “SOFLEX # 420” (solvent type colored base coat paint manufactured by Kansai Paint Co., Ltd.) as a colored base coat paint is electrostatically applied on the film so that the dry film thickness is about 15 μm. After preheating at 80 ° C. for 3 minutes, as a clear paint, “Soflex # 450 clear” (manufactured by Kansai Paint Co., Ltd., acrylic urethane solvent-type clear paint) is electrostatically applied so that the dry film thickness is about 30 μm. Each test coating was prepared by heating and drying at 30 ° C. for 30 minutes.
Each test coating obtained as described above was subjected to the following performance test. The results are shown in Table 4.
性能試験方法
初期付着性：塗膜面に素地に達するようにカッターで切り込み線を入れ、大きさ２ｍｍ×２ｍｍのマス目を１００個作り、その表面に粘着セロハン（登録商標）テープを貼着し、２０℃においてそれを急激に剥離した後のマス目の残存塗膜数を調べた。○は１００個（剥離なし）、△は９９〜５１個、×は５０個以下。
Performance test method Initial adhesion: Cut lines with a cutter to reach the substrate surface, make 100 squares with a size of 2mm x 2mm, and stick adhesive cellophane (registered trademark) tape on the surface. The number of residual coatings in the squares after peeling it off rapidly at 20 ° C. was examined. ○ is 100 pieces (no peeling), Δ is 99 to 51 pieces, and x is 50 pieces or less.
耐水性：各試験塗装物の塗装したバンパーの一部を切り取り、４０℃の温水に１０日間浸漬し、引き上げて乾燥してから、上記の初期付着性試験と同様にして付着性試験を行ない、残存塗膜数を調べた。また乾燥後の塗装面を目視で評価した。○はブリスター発生なし、△はブリスターの発生はないがツヤがひけている状態、×はブリスター発生ありを示す。 Water resistance: A part of the bumper coated with each test coating was cut out, immersed in warm water at 40 ° C. for 10 days, pulled up and dried, and then the adhesion test was performed in the same manner as the above initial adhesion test. The number of remaining coating films was examined. Further, the painted surface after drying was visually evaluated. ○ indicates no blistering, Δ indicates no blistering, but gloss is present, and × indicates blistering.
本発明によれば、基材への付着性に優れる塗料が得られ、またこれによって耐水性、耐汚染性に優れた塗膜が得られるので、本発明は産業上有用である。 According to the present invention, a paint having excellent adhesion to a substrate can be obtained, and a coating film having excellent water resistance and stain resistance can be obtained. Therefore, the present invention is industrially useful.
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