JP2004351650A - Resin molded object - Google Patents
Resin molded object Download PDFInfo
- Publication number
- JP2004351650A JP2004351650A JP2003149238A JP2003149238A JP2004351650A JP 2004351650 A JP2004351650 A JP 2004351650A JP 2003149238 A JP2003149238 A JP 2003149238A JP 2003149238 A JP2003149238 A JP 2003149238A JP 2004351650 A JP2004351650 A JP 2004351650A
- Authority
- JP
- Japan
- Prior art keywords
- coating film
- group
- resin molded
- component
- moles
- 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.)
- Pending
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- 239000011347 resin Substances 0.000 title claims abstract description 47
- 229920005989 resin Polymers 0.000 title claims abstract description 47
- 238000000576 coating method Methods 0.000 claims abstract description 130
- 239000011248 coating agent Substances 0.000 claims abstract description 127
- 239000000203 mixture Substances 0.000 claims abstract description 51
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 27
- 239000010703 silicon Substances 0.000 claims abstract description 27
- 229920003023 plastic Polymers 0.000 claims abstract description 23
- 239000004033 plastic Substances 0.000 claims abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 239000000758 substrate Substances 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 239000008119 colloidal silica Substances 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000002252 acyl group Chemical group 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 4
- 238000005299 abrasion Methods 0.000 abstract description 26
- 239000000463 material Substances 0.000 abstract description 8
- 239000000413 hydrolysate Substances 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 14
- -1 polyethylene terephthalate Polymers 0.000 description 12
- 239000011941 photocatalyst Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000001723 curing Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000013007 heat curing Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 230000002087 whitening effect Effects 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000003618 dip coating Methods 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 230000005923 long-lasting effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229920006353 Acrylite® Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 238000007754 air knife coating Methods 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000007611 bar coating method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000007761 roller coating Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- NBMRBPRZMHCUOR-UHFFFAOYSA-N (3-chlorophenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=CC(Cl)=C1 NBMRBPRZMHCUOR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- RBEMUBNJBBFCGP-UHFFFAOYSA-N 2-methylpropyl(tripropoxy)silane Chemical compound CCCO[Si](CC(C)C)(OCCC)OCCC RBEMUBNJBBFCGP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- OCDDDGXATNYKNE-UHFFFAOYSA-N [diacetyloxy(2-methylpropyl)silyl] acetate Chemical compound CC(C)C[Si](OC(C)=O)(OC(C)=O)OC(C)=O OCDDDGXATNYKNE-UHFFFAOYSA-N 0.000 description 1
- LSDYFQXXPCPBQV-UHFFFAOYSA-N [diacetyloxy(butyl)silyl] acetate Chemical compound CCCC[Si](OC(C)=O)(OC(C)=O)OC(C)=O LSDYFQXXPCPBQV-UHFFFAOYSA-N 0.000 description 1
- KXJLGCBCRCSXQF-UHFFFAOYSA-N [diacetyloxy(ethyl)silyl] acetate Chemical compound CC(=O)O[Si](CC)(OC(C)=O)OC(C)=O KXJLGCBCRCSXQF-UHFFFAOYSA-N 0.000 description 1
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 1
- OJBYIHGSXQWCMB-UHFFFAOYSA-N [diacetyloxy(pentyl)silyl] acetate Chemical compound CCCCC[Si](OC(C)=O)(OC(C)=O)OC(C)=O OJBYIHGSXQWCMB-UHFFFAOYSA-N 0.000 description 1
- VLFKGWCMFMCFRM-UHFFFAOYSA-N [diacetyloxy(phenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C1=CC=CC=C1 VLFKGWCMFMCFRM-UHFFFAOYSA-N 0.000 description 1
- IXUUFMQHBRPODL-UHFFFAOYSA-N [diacetyloxy(propan-2-yl)silyl] acetate Chemical compound CC(=O)O[Si](C(C)C)(OC(C)=O)OC(C)=O IXUUFMQHBRPODL-UHFFFAOYSA-N 0.000 description 1
- DKGZKEKMWBGTIB-UHFFFAOYSA-N [diacetyloxy(propyl)silyl] acetate Chemical compound CCC[Si](OC(C)=O)(OC(C)=O)OC(C)=O DKGZKEKMWBGTIB-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- 150000001491 aromatic compounds Chemical class 0.000 description 1
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 description 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
- GNRBSDIBKIHSJH-UHFFFAOYSA-N butyl(tripropoxy)silane Chemical compound CCCC[Si](OCCC)(OCCC)OCCC GNRBSDIBKIHSJH-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
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- 239000005011 phenolic resin Substances 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
- DEKZKCDJQLBBRA-UHFFFAOYSA-N tributoxy(butyl)silane Chemical compound CCCCO[Si](CCCC)(OCCCC)OCCCC DEKZKCDJQLBBRA-UHFFFAOYSA-N 0.000 description 1
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- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- QKERXNDNRCHDLW-UHFFFAOYSA-N tributoxy(pentyl)silane Chemical compound CCCCC[Si](OCCCC)(OCCCC)OCCCC QKERXNDNRCHDLW-UHFFFAOYSA-N 0.000 description 1
- INUOIYMEJLOQFN-UHFFFAOYSA-N tributoxy(phenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C1=CC=CC=C1 INUOIYMEJLOQFN-UHFFFAOYSA-N 0.000 description 1
- LEZQEMOONYYJBM-UHFFFAOYSA-N tributoxy(propan-2-yl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C(C)C LEZQEMOONYYJBM-UHFFFAOYSA-N 0.000 description 1
- WAAWAIHPWOJHJJ-UHFFFAOYSA-N tributoxy(propyl)silane Chemical compound CCCCO[Si](CCC)(OCCCC)OCCCC WAAWAIHPWOJHJJ-UHFFFAOYSA-N 0.000 description 1
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、プラスチック基材上に下塗り層（第一塗膜）を介して光触媒性酸化チタンを含む層（第二塗膜）を有する樹脂成形体に関する。
【０００２】
【従来の技術】
環境汚染に伴い、建築外装材料、屋外建造物の汚れが問題となっている。この汚れを防止するために、光触媒の強い酸化力と親水性を利用して、光触媒を含む塗料をコーティングし、硬化した建築外装材料、屋外建造物が提案されている。
【０００３】
しかしながら、アクリル樹脂（例えば、ポリメチルメタクリレートや、主成分であるメチルメタクリレートとアクリレート等の他の単量体との共重合体）、ポリカーボネート、ポリエチレンテレフタレート等のプラスチックを基材とする樹脂成形体の場合、このプラスチック基材上に光触媒を含む塗膜を直接形成すると、基材と光触媒を含む塗膜との親和性が良好とは言えず、密着性に劣る場合があった。また、光触媒の酸化作用によって、時間とともにプラスチック基材が白化したり、クッラックが発生したり、さらには光触媒層が剥離する等、耐候性に問題がある場合があった。
【０００４】
上記問題を解決するために、プラスチック基材上に、まず下塗り層を施し、その上に光触媒を含む塗膜を形成する方法が提案されている。例えば、加水分解性オルガノシランを原料とするシリカ系高分子を下塗り層とする方法が挙げられる（特許文献１、２参照）。
【０００５】
しかし、特許文献１に示された材料構成でプラスチック基材と下塗り層との優れた密着性を実現するためには、実質的に、プラスチック基材と下塗り層の間にさらにプライマー層を形成する必要があり、製造コストが高くなるという問題があった。
【０００６】
また、特許文献２に示された材料構成では、下塗り層の厚さが薄い場合、成形体の耐磨耗性が低くなることがあった。それを補うためにプラスチック基材上に２μｍ以上の厚い下塗り層を形成させると、塗膜密着性が低下する場合があった。
【０００７】
【特許文献１】
特開平１１−９１０３０号公報
【特許文献２】
特開２０００−２０２３６３号公報
【０００８】
【発明が解決しようとする課題】
本発明は、従来技術の各課題を解決するためになされたものである。本発明の目的は、耐候性、耐磨耗性、塗膜密着性にすぐれ、光触媒の効果が長期にわたり持続する樹脂成形体を提供することである。
【０００９】
【課題を解決するための手段】
本発明者らは、上述した各課題を解決するために鋭意検討した結果、プラスチック基材上にオルガノアルコキシシラン類（Ａ）の加水分解物と、フェニルアルコキシシラン類（Ｂ）の加水分解物とを含むシリコン系組成物からなる塗膜（第一塗膜）を形成させ、さらにその上に光触媒性酸化チタンを含む塗膜（第二塗膜）を形成することで、耐候性、耐磨耗性、塗膜密着性に優れ、光触媒の効果が長期にわたり持続する樹脂成形体が得られることを見出し本発明に至った。
【００１０】
すなわち、本発明は、
プラスチック基材と、
該プラスチック基材上の少なくとも一部に形成された、下記シリコン系組成物からなる第一塗膜と、
該第一塗膜上の少なくとも一部に形成された、光触媒性酸化チタンを含む第二塗膜と、
を有する樹脂成形体である。
シリコン系組成物：
（ａ）式（１）で表されるオルガノアルコキシシラン類（Ａ）の加水分解物と、
（ｂ）式（２）で表されるフェニルアルコキシシラン類（Ｂ）の加水分解物と
を含むシリコン系組成物。
【００１１】
Ｒ１Ｓｉ（ＯＲ２）３ ・・（１）
（式中、Ｒ１は炭素数１〜１０のフェニル基を持たない有機基、Ｒ２は炭素数１〜５のアルキル基または炭素数１〜４のアシル基を示す。）
ＰｈＳｉ（ＯＲ３）３ ・・（２）
（式中、Ｐｈは置換基を有してもよいフェニル基、Ｒ３は炭素数１〜５のアルキル基または炭素数１〜４のアシル基を示す。）
【００１２】
【発明の実施の形態】
以下、本発明の好適な実施形態について説明する。
【００１３】
本発明の樹脂成形体に利用できるプラスチック基材としては、特に限定されるものではないが、例えば、アクリル樹脂（ポリメチルメタクリレートや、主成分であるメチルメタクリレートとアクリレート等の他の単量体との共重合体など；なお、ここで主成分とは、その樹脂を構成する単量体単位の５０質量％以上であることを意味する）、ポリカーボネート樹脂、ポリ塩化ビニル樹脂、ウレタン樹脂、フェノール樹脂、エポキシ樹脂、ポリエステル樹脂、ポリエチレン樹脂、ポリプロピレン樹脂等のプラスチック成型品、プラスチックフィルムや繊維などをあげることが出来る。密着性の点でアクリル樹脂、特に分子量が高すぎないアクリル樹脂を用いる時に好適に実施される。
【００１４】
＜第一塗膜＞
本発明において、第一塗膜とは、プラスチック基材上の少なくとも一部に形成される塗膜であって、（ａ）式（１）で表されるオルガノアルコキシシラン類（Ａ）の加水分解物と、（ｂ）式（２）で表されるフェニルアルコキシシラン類（Ｂ）の加水分解物と、を含むシリコン系組成物からなる塗膜である。
【００１５】
Ｒ１Ｓｉ（ＯＲ２）３ ・・（１）
（式中、Ｒ１は炭素数１〜１０のフェニル基を持たない有機基、Ｒ２は炭素数１〜５のアルキル基または炭素数１〜４のアシル基を示す。）
ＰｈＳｉ（ＯＲ３）３ ・・（２）
（式中、Ｐｈは置換基を有してもよいフェニル基、Ｒ３は炭素数１〜５のアルキル基または炭素数１〜４のアシル基を示す。）
式（１）において、Ｒ１は炭素数１〜１０のフェニル基を持たない有機基であり、その具体例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、ｎ−デシル基等のアルキル基や、アリル基、３−（２−アミノエチルアミノ）プロピル基、３−アミノプロピル基、ビニル基、３−グリシドキシプロピル基、３−メタクリロキシプロピル基、３−メルカプトプロピル基、３−クロロプロピル基、３−クロロブチル基、３，４−エポキシシクロヘキシルエチル基、３，３，３−トリフロロブチル基等が挙げられる。
【００１６】
式（１）において、Ｒ２は炭素数１〜５のアルキル基または炭素数１〜４のアシル基である。Ｒ２は、３つ全て同一である必要はなく、異なっていても良い。その具体例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、アセチル基等が挙げられる。
【００１７】
式（１）で表されるオルガノアルコキシシラン類（Ａ）の具体例としては、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリプロポキシシラン、メチルトリブトキシシラン、メチルトリアセトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリプロポキシシラン、エチルトリブトキシシラン、エチルトリアセトキシシラン、ｎ−プロピルトリメトキシシラン、ｎ−プロピルトリエトキシシラン、ｎ−プロピルトリプロポキシシラン、ｎ−プロピルトリブトキシシラン、ｎ−プロピルトリアセトキシシラン、イソプロピルトリメトキシシラン、イソプロピルトリエトキシシラン、イソプロピルトリプロポキシシラン、イソプロピルトリブトキシシラン、イソプロピルトリアセトキシシラン、ｎ−ブチルトリメトキシシラン、ｎ−ブチルトリエトキシシラン、ｎ−ブチルトリプロポキシシラン、ｎ−ブチルトリブトキシシラン、ｎ−ブチルトリアセトキシシラン、イソブチルトリメトキシシラン、イソブチルトリエトキシシラン、イソブチルトリプロポキシシラン、イソブチルトリブトキシシラン、イソブチルトリアセトキシシラン、ペンチルトリメトキシシラン、ペンチルトリエトキシシラン、ペンチルトリプロポキシシラン、ペンチルトリブトキシシラン、ペンチルトリアセトキシシラン、ｎ−ヘキシルトリメトキシシラン、ｎ−ヘキシルトリエトキシシラン、ｎ−オクチルトリメトキシシラン、ｎ−オクチルトリエトキシシラン、ｎ−デシルトリメトキシシラン、ｎ−デシルトリエトキシシラン、等が挙げられる。中でも、加水分解、縮合の反応速度、および得られる塗膜の硬度、強度、耐摩耗性の点から、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシランが好ましい。中でも特にメチルトリメトキシシランが好ましい。
【００１８】
（ａ）成分は、式（１）で表されるオルガノアルコキシシラン類（Ａ）のアルコキシ基またはアシルオキシ基の一部または全部が水酸基に置換されたものである。また、（ａ）成分の分子間で、置換された水酸基同士が一部縮合していても良い。
【００１９】
（ａ）成分の製造方法としては、例えば式（１）で表されるオルガノアルコキシシラン類（Ａ）に水（オルガノアルコキシシラン類（Ａ）１モルに対して例えば１〜１０モル）、および塩酸や酢酸などを加え、溶液を酸性（例えばｐＨ２〜５）とし撹拌することにより製造することが出来る。オルガノアルコキシシラン類（Ａ）は単独で用いても良いし、あるいは２種以上を組み合わせても良い。
【００２０】
本発明の（ｂ）成分は、式（２）で表されるフェニルアルコキシシラン類（Ｂ）の加水分解物である。この（ｂ）成分は、シリコン系組成物に配合することにより、第一塗膜とプラスチック基材、かつ第一塗膜と第二塗膜との密着性を向上させる成分である。
【００２１】
式（２）においてＰｈは置換基を有していても良いフェニル基を示す。置換基としては、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｔｅｒｔ−ブチル基、ハロゲン基等が挙げられる。Ｒ３は炭素数１〜５のアルキル基または炭素数１〜４のアシル基である。なおＲ３は３つ全て同一である必要はなく、異なっていても良い。その具体例としては、先に挙げたＲ２と同様のものが挙げられる。
【００２２】
式（２）で表されるフェニルアルコキシシラン類（Ｂ）の具体例としては、フェニルトリメトキシシラン、フェニルトリエトキシシラン、フェニルトリプロポキシシラン、フェニルトリブトキシシラン、フェニルトリアセトキシシラン、ｐ−メチルフェニルトリメトキシシラン、ｍ−クロロフェニルトリメトキシシラン等が挙げられる。中でも、加水分解の速度の速い点から、フェニルトリメトキシシラン、フェニルトリエトキシシランが好ましい。
【００２３】
（ｂ）成分は、式（２）で表されるフェニルアルコキシシラン類（Ｂ）のアルコキシ基またはアシルオキシ基の一部または全部が水酸基に置換されたものである。また、（ｂ）成分の分子間で、置換された水酸基どうしが一部縮合していてもよい。
【００２４】
（ｂ）成分の製造方法としては、例えば式（２）で表されるフェニルアルコキシシラン類（Ｂ）に、水（フェニルアルコキシシラン類（Ｂ）１モルに対して、例えば１〜１０モル）、および塩酸や酢酸などを加え、溶液を酸性（例えばｐＨ２〜５）とし、攪拌することによって製造することができる。フェニルアルコキシシラン類（Ｂ）は、単独で用いても良いし、あるいは２種類以上を組み合わせて用いてもよい。
【００２５】
第一塗膜を形成するためのシリコン系組成物中の（ａ）成分、（ｂ）成分の量比は所望の塗膜物性に応じて適宜決定すれば良い。例えば（ａ）成分、（ｂ）成分の比に関しては、仕込みのモル数で（Ａ）成分と（Ｂ）成分の合計１００モルとしたとき（Ｂ）成分のモル数が１〜５５モルの範囲とすることが好ましい。１モル以上だとプラスチック基材との密着性が向上する。一方、５５モル以下だと、得られる樹脂成形体の耐摩耗性、耐候性が向上する。より好ましい範囲は、３〜４０モルである。
【００２６】
なお、上述した仕込みモル数において、（Ａ）成分、（Ｂ）成分のモル数は、以下の式で示されるものである。
（Ａ）成分のモル数＝（オルガノアルコキシシラン類（Ａ）の仕込み質量）／（オルガノアルコキシシラン類（Ａ）の分子量）
（Ｂ）成分のモル数＝（フェニルアルコキシシラン類（Ｂ）の仕込み質量）／（フェニルアルコキシシラン類（Ｂ）の分子量）
本発明のシリコン系組成物には、樹脂成形体の耐磨耗性をさらに向上させるために、（ｃ）コロイド状シリカを含有させることが好ましい。シリカ微粒子が水に均一に分散したシリカゾル、または、親水性溶剤に均一に分散したオルガノシリカゾルを用いることが好ましい。分散液中のシリカ微粒子含有率（固形分濃度）は、１０〜５０質量％が好ましく、２０〜４０質量％がより好ましい。
【００２７】
コロイド状シリカ（ｃ）の粒子径は、本発明の樹脂成形体としたときの透明性の点から１００ｎｍ以下が好ましい。また、本発明の樹脂成形体としたときの耐クラック性の点から、５ｎｍ以上が好ましい。
【００２８】
コロイド状シリカの溶剤は、シリカ系組成物中で（ａ）成分、（ｂ）成分、（ｃ）成分を凝集、沈殿させることなく均一に分散させ、かつ加水分解、縮合等の反応を進行させるという点から、水、メタノール、エタノール、イソブタノール、イソプロパノール、エチレングリコール等の親水性溶剤であることが好ましい。
【００２９】
コロイド状シリカの具体例としては、水分散コロイド状シリカ、メタノール分散コロイド状シリカ、エタノール分散コロイド状シリカ、イソプロパノール分散コロイド状シリカ、エチレングリコール分散コロイド状シリカ、イソブタノール分散コロイド状シリカ等が挙げられる。中でも、（ａ）成分、（ｂ）成分、（ｃ）成分と混合した際の安定性の点から、イソプロパノール分散コロイド状シリカが好ましい。市販品としては、日産化学工業（株）製 商品名：スノーテックスＩＰＡ−ＳＴ、触媒化成工業（株）製 商品名：ＯＳＣＡＬ１４３２などが挙げられる。
【００３０】
また、コロイド状シリカにコロイド状のアルミナやコロイド状の酸化チタンを混合して用いることもできる。
【００３１】
（ｃ）成分の配合量は、仕込みのモル数で（Ａ）成分と（Ｂ）成分の合計１００モルに対し、（ｃ）成分が２５〜２５０モルの範囲であることが好ましい。２５モル以上だと表面硬度および耐磨耗性がさらに向上する。一方、２５０モル以下だと、クラックの無い塗膜が得られる。さらに好ましい範囲は、５０〜２００モルである。
【００３２】
なお、上述した（ｃ）成分のモル数は以下の式で表されるものである。
（ｃ）成分のモル数＝（溶媒分散コロイド状シリカの仕込みシリカ分（固形分）質量）／（シリカ分子量；６０．１（ＳｉＯ２として））
本発明の第一塗膜を形成させるシリコン系組成物は、（ａ）成分、（ｂ）成分、および（ｃ）成分を均一に混合させ、固形分濃度を調整し、固形分の分散安定性、保存安定性を向上させるために有機溶媒を含有することが好ましい。有機溶媒としては、アルコール類、ケトン類、エーテル類、セロソルブ類、エステル類、芳香族化合物類などを挙げることができる。具体的には、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、ｓｅｃ−ブタノール、ｔｅｒｔ−ブタノール、イソブタノール、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコールモノメチルエーテル、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジイソブチルケトン、テトラヒドロフラン、ジオキサン、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、トルエン、キシレン、酢酸エチル、酢酸ブチル、γ−ブチロラクトン、ジアセトンアルコール、１−アセトキシ−２−エトキシエタンなどを挙げることができる。これらは１種あるいは２種以上を混合して使用することもできる。
【００３３】
第一塗膜形成用のシリコン系組成物中の有機溶媒の割合は、（Ａ）成分および（Ｂ）成分の、また場合によっては、（Ａ）成分および（Ｂ）成分および（ｃ）成分の合計１００質量部に対して４０〜１００００質量部であることが好ましい。４０質量部以上とすることは、各成分の分散安定性および保存安定性の点、ならびに液の粘度が高くなり過ぎるのを防止して良好な塗膜を得る点で意義が有る。また、１００００質量部以下とすることは、固形分が低くなりすぎて塗膜が薄くなり、十分な密着性、耐候性、耐磨耗性が得られなくなるのを避ける点で意義が有る。
【００３４】
また、シリコン系組成物には、必要に応じて表面平滑剤、界面活性剤、紫外線吸収剤、貯蔵安定剤、硬化剤、レベリング剤などの各種添加剤を適宜添加して使用することが出来る。
【００３５】
第一塗膜に適したシリコン系組成物を調製する方法の好適な一例を説明する。まず、式（１）で表されるオルガノアルコキシシラン類（Ａ）と、式（２）で表されるフェニルアルコキシシラン類（Ｂ）をよく混合する。場合によっては、コロイド状シリカ（ｃ）を加えよく混合する。この混合液を攪拌しながら、適量の水を入れ加水分解する。その際、加水分解を促進するために塩酸、酢酸などによりｐＨを酸性（例えば２〜５）に調整する。３〜５時間程度攪拌を続けた後、ＮＭＲ法により充分に加水分解されていることを確認した後、アンモニウム、水酸化ナトリウム、酢酸ナトリウム水溶液などを添加し、ｐＨを中性付近（例えば６〜７）に調整し、約２０時間程度攪拌を続け縮合を行なう。その後、有機溶媒、必要に応じ硬化剤、レベリング剤などを添加し、均一に混合して、シリコン系組成物を得ることができる。
【００３６】
この方法において、式（１）で表されるオルガノアルコキシシラン類（Ａ）、式（２）で表されるフェニルアルコキシシラン類（Ｂ）を、別々に適量の水で加水分解した後、混合してもよい。場合によっては、その後コロイド状シリカ（ｃ）を混合してもよい。
【００３７】
このようなシリコン系組成物を用いて、第一塗膜を形成する方法としては、プラスチック基材上の少なくとも一部にシリコン系組成物を塗布し、加熱硬化させる方法が挙げられる。
【００３８】
プラスチック基材上の少なくとも一部にシリコン系組成物を塗布する方法としては、刷毛塗り法、流延法、ローラーコート法、バーコート法、噴霧コート法、エアーナイフコート法、ディップコート法、スピンコート法等を挙げることが出来るが特に限定されない。
【００３９】
シリコン系組成物の塗布量としては、得られる第一塗膜の膜厚が１〜２０μｍとなるように塗布するのがよい。第一塗膜の膜厚を１μｍ以上とすることにより、耐磨耗性を向上させ、光触媒性酸化チタンを含む層（第二塗膜）による基材の劣化を長期間抑えることが出来る。また、膜厚を２０μｍ以下とすることで硬化時のクラック発生を抑制することが出来る。好ましくは２μｍ〜１０μｍである。
【００４０】
プラスチック基材上の少なくとも一部に塗布したシリコン系材料を室温で乾燥させた後、乾燥機や赤外線照射等により加熱硬化させることで第一塗膜が得られる。
【００４１】
加熱硬化温度は、７０〜１３０℃が好ましい。７０℃以上で硬化することで保護被膜の耐擦傷性を向上することができる。１３０℃以下とすることで第一塗膜のクラック発生を抑制することができる。より好ましい硬化温度は、８０〜１２０℃である。
【００４２】
＜第二塗膜＞
本発明の第二塗膜は、光触媒性酸化チタンを含有する第二塗膜形成用組成物を第一塗膜上の少なくとも一部に塗布し、加熱硬化を行なうことにより得られる。この第二塗膜形成用組成物は、光触媒性酸化チタンを含有する組成物であれば特に限定はなく、水系・有機溶媒系を問わず用いることが出来る。例えば、アルキルアルコキシシラン類の加水分解物、その縮合物のいずれか一方、または両方を主成分とする組成物に光触媒性酸化チタンを含有させた組成物などがあげられる。光触媒性酸化チタンとしては、特に限定されないが、アナタース型酸化チタン、あるいはブルッカイト型酸化チタンのいずれか一方または両方であることが、その光触媒作用が優れており好ましい。第二塗膜形成用組成物中の光触媒性酸化チタンの含有率は、特に制限がなく必要量含まれていればよいが、０．０５質量％〜１０質量％であるのが好ましい。
【００４３】
このような光触媒性酸化チタンを含有する第二塗膜形成用組成物として、一般に市販されているものを用いることもできる。例えば、石原産業（株）製 商品名：ＳＴ−Ｋ２１１、昭和電工（株）製 商品名：ＮＴＢ−１３、ＮＴＢ−１００、ＮＴＢ−３０、テイカ（株）製 商品名：ＴＫＣ−３０２、ＴＫＣ−３０３、ＴＫＣ−３０４、三井鉱山（株）製 商品名：ミラクルチタンＭ等があげられる。尚、第二塗膜形成用組成物は、これらに限定されるものではない。
【００４４】
このような第二塗膜形成用組成物を用いて、第二塗膜を形成する方法としては、第一塗膜上の少なくとも一部に第二塗膜形成用組成物を塗布し、加熱硬化させる方法が挙げられる。
【００４５】
第一塗膜上の少なくとも一部に第二塗膜形成用組成物を塗布する方法としては、刷毛塗り法、流延法、ローラーコート法、バーコート法、噴霧コート法、エアーナイフコート法、ディップコート法、スピンコート法等を挙げることが出来るが特に限定されない。第二塗膜形成用組成物の塗布量としては、得られる第二塗膜の膜厚が０．０１〜５μｍとなるように塗布するのがよい。第二塗膜の膜厚を０．０１μｍ以上とすることにより、樹脂成形体の汚れ防止機能、親水性を向上させる。また、膜厚を５μｍ以下とすることで、硬化時のクラック発生を抑制や耐擦傷性を向上することが出来る。好ましくは０．０２〜１μｍである。
【００４６】
第二塗膜は、第一塗膜上の少なくとも一部に塗布した第二塗膜形成用組成物を室温で乾燥させた後、乾燥機や赤外線照射等により加熱硬化させることで得られる。加熱硬化温度は、第二塗膜形成用組成物の組成から判断して、適宜適切な温度を選択すればよい。ただし、このとき第一塗膜も加熱されるため、劣化を抑えるために、第一塗膜の硬化温度＋６０℃以下とすることが好ましい。
【００４７】
【実施例】
以下に実施例を挙げ、本発明をさらに具体的に説明する。なお実施例中の樹脂成形体の物性は、下記の方法による測定結果を示したものである。
【００４８】
１） 外観
目視にて樹脂成形体の透明性、クラック、塗膜白化、第一塗膜あるいは第二塗膜の剥離の有無を観察し、透明でクラック、白化、剥離がないものを良好（○）とした。不透明な部分のあったもの、クラック、白化、剥離があったものを不良（×）とした。
【００４９】
２） 塗膜密着性
樹脂成形体の第一塗膜および第二塗膜へ、カミソリの刃で１ｍｍ間隔に縦横１１本ずつの切り目を入れて１００個の碁盤目をつくり、それらの上にセロハンテープをよく密着させた後、４５゜手前方向に急激に剥した時、第一塗膜および第二塗膜が剥離せずに残存したマス目の数により以下の基準で評価した。
○…剥離したマス目が無い（密着性良好）。
△…剥離したマス目が１／１００以上５／１００以下（密着性中程度）。
×…剥離したマス目が６／１００以上（密着性不良）。
【００５０】
３） 親水性（光触媒性）
樹脂成形体の親水性を水との接触角で評価した。協和界面化学（株）製ＣＡ−１５０型接触角計で測定を行なった。
○・・・樹脂成形体の水との接触角が１５度以下であった。
△・・・樹脂成形体の水との接触角が１５度より大きく２０度より小さかった。
×・・・樹脂成形体の水との接触角が２０度以上であった。
【００５１】
４） 耐磨耗性
樹脂成形体の表面を、＃０００のスチールウールにて、１ｋｇ／ｃｍ２の圧力を加え１０往復擦り、１×３ｃｍの範囲に発生した傷の程度を観察し、以下の基準で評価した。
Ａ…キズがつかない。光沢面あり。
Ｂ…１本以上〜９本以下のキズがつく。光沢面あり。
Ｃ…１０本以上〜９９本以下のキズがつく。光沢面あり。
Ｄ…１００本以上のキズがつく。光沢面あり。
Ｅ…光沢面がなくなる。
【００５２】
５） 耐候性
ＪＩＳ Ｋ５４００ サンシャインウエザーメーター加速曝露試験（ブラックパネル温度６３℃、湿度５０％ＲＨ、「１２分雨あり→４８分雨なし」を１サイクルとした。）を実施した。１０００時間曝露（耐候性試験）後の外観（透明性、クラック、白化、塗膜の剥離）、塗膜密着性、親水性、耐磨耗性について評価した。評価は１）、２）、３）、４）と同様の方法によった。
【００５３】
＜実施例１＞
［シリコン系組成物の調製］
（Ａ）成分としてメチルトリメトキシシラン３６．７ｇ（０．２７０ｍｏｌ）、（Ｂ）成分としてフェニルトリメトキシシラン５．９４ｇ（０．０３０ｍｏｌ）、を混合し均一溶液とした。この溶液を撹拌しつつ、水２０ｇを徐々に加えた。さらにｐＨが３．５になるように０．１Ｎの塩酸溶液を滴下し加水分解を行った。水を加えるにつれて溶液が発熱したので、水浴で冷却しつつ、液温を約１０℃に維持しながら４時間攪拌を続けた。次いで、ｐＨが６．６となるように１５．２質量％の酢酸ナトリウム水溶液を加えた。湯浴で液温を３５℃に維持しながら、さらに２０時間攪拌した。さらにγ−ブチロラクトン１２．０ｇおよびブチルセロソルブ１４．０ｇを加え攪拌し均一溶液とした。さらに、日本ユニカー（株）製シリコーン系界面活性剤Ｌ−７００１（商品名）を０．０１ｇ添加し、約１時間室温で攪拌し、第一塗膜形成用のシリコン系組成物を得た。
【００５４】
［塗膜形成］
メチルメタクリレート単位を主成分とするアクリル樹脂板（三菱レイヨン（株）製、商品名：アクリライトＥＸ、縦×横×厚＝１５０×１００×３ｍｍ）上に、加熱硬化後の第一塗膜の膜厚が４μｍとなるように引き上げ速度を調整し、ディップコート法により第一塗膜形成用のシリコン系組成物を塗工した。室温で約３０分間乾燥させた後、乾燥器により８０℃で２時間加熱硬化し、第一塗膜を形成した。次いで、第一塗膜を形成したアクリル板上に、加熱硬化後の第二塗膜の膜厚が０．１μｍとなるように引き上げ速度を調整し、ディップコートにより第二塗膜形成用組成物（石原産業（株）製、アナタース型酸化チタン含有コーティング材、商品名：ＳＴ−Ｋ２１１、固形分濃度：０．２質量％）を塗工した。室温で約２０分間乾燥した後、乾燥器により９０℃で３０分間加熱硬化することで第二塗膜を形成し、樹脂成形体を得た。
【００５５】
次に得られた樹脂成形体の物性評価を行なった。この樹脂成形体の初期物性は、外観は透明で、クラック、白化、塗膜の剥離もなく良好（○）であり、塗膜密着性も良好（○）であり、水との接触角は１３度と親水性は良好（○）であった。また耐磨耗性はＣランクと良好であった。耐候性試験後の樹脂成形体の物性については、外観は透明で、クラック、白化、塗膜の剥離もなく良好（○）であった。また、塗膜密着性も良好（○）であり、水との接触角は５度と良好な親水性（○）を示した。また、耐摩耗性はＣランクと良好であった。結果を表１に示した。
【００５６】
＜実施例２〜５＞
（Ａ）成分、（Ｂ）成分の量を、表１に示すように変更したこと以外は、実施例１と同じ操作で第一塗膜と第二塗膜を有する樹脂成形体を得、評価した。いずれの樹脂成形体においても、初期・耐候性試験後の外観、塗膜密着性、親水性、耐摩耗性とも良好（外観：○、塗膜密着性：△以上、親水性：○、耐摩耗性：Ｄランク以上）であった。結果を表１に示した。
【００５７】
＜実施例６＞
［シリコン系組成物の調製］
（Ａ）成分としてメチルトリメトキシシラン１２．２ｇ（０．０９０ｍｏｌ）、（Ｂ）成分としてフェニルトリメトキシシラン１．９８ｇ（０．０１０ｍｏｌ）、（ｃ）成分としてイソプロピルアルコール分散コロイド状シリカ（粒子径１０〜２０ｎｍ、固形分３０質量％、日産化学工業（株）製、商品名：スノーテックスＩＰＡ−ＳＴ）４０．１ｇ（０．２００ｍｏｌ）を混合し均一溶液とした。
【００５８】
この溶液を撹拌しつつ、さらに水２０ｇを徐々に加えて加水分解を行った。水を加えるにつれて溶液が発熱したので、水浴で冷却しつつ、液温を約１０℃に維持しながら４時間攪拌を続けた。次いで、ｐＨが６．６となるように１５．２質量％の酢酸ナトリウム水溶液を加えた。湯浴で液温を３５℃に維持しながら、さらに２０時間攪拌した。有機溶媒としてγ−ブチロラクトン１２．０ｇおよびブチルセロソルブ１４．０ｇを加え攪拌し均一溶液とした。さらに、日本ユニカー（株）製シリコーン系界面活性剤Ｌ−７００１（商品名）を０．０１ｇ添加し、約１時間室温で攪拌し、第一塗膜形成用のシリコン系組成物を得た。
【００５９】
［塗膜の形成］
メチルメタクリレート単位を主成分とするアクリル樹脂板（三菱レイヨン（株）製、商品名：アクリライトＥＸ、縦×横×厚＝１５０×１００×３ｍｍ）上に、加熱硬化後の第一塗膜の膜厚が４μｍとなるように引き上げ速度を調整し、ディップコート法により第一塗膜形成用のシリコン系組成物を塗工した。室温で約３０分間乾燥させた後、乾燥器により８０℃で２時間加熱硬化し、第一塗膜を形成した。次いで、第一塗膜を形成したアクリル板上に、加熱硬化後の第二塗膜の膜厚が０．１μｍとなるように引き上げ速度を調整し、ディップコートにより第二塗膜形成用組成物（石原産業（株）製、アナタース型酸化チタン含有コーティング材、商品名：ＳＴ−Ｋ２１１、固形分濃度：０．２質量％）塗工した。室温で約２０分間乾燥した後、乾燥器により９０℃で３０分間加熱硬化することで第二塗膜を形成し、樹脂成形体を得た。
【００６０】
次に得られた樹脂成形体の物性評価を行なった。この樹脂成形体の初期物性は、外観は透明で、クラック、白化、塗膜の剥離もなく良好（○）であり、塗膜密着性も良好（○）であり、水との接触角は１３度と親水性は良好（○）であった。また耐磨耗性はＢランクと優れていた。耐候性試験後の樹脂成形体の物性については、外観は透明で、クラック、塗膜の剥離もなく良好（○）であった。また、塗膜密着性も良好（○）であり、水との接触角は５度と良好な親水性（○）を示した。また、耐摩耗性はＢランクと優れていた。結果を表１に示した。
【００６１】
＜実施例７〜１２＞
（Ａ）成分、（Ｂ）成分、（ｃ）成分および溶媒の種類、量を、表１に示すように変更したこと以外は、実施例６と同じ操作で第一塗膜と第二塗膜を有する樹脂成形体を得、評価した。いずれの樹脂成形体においても、初期・耐候性試験後の外観、塗膜密着性、親水性、耐摩耗性とも良好（外観：○、塗膜密着性：○、親水性：○、耐摩耗性：Ｂランク）であった。結果を表１に示した。
【００６２】
＜比較例１〜４＞
（Ｂ）成分を用いず、（Ａ）成分および（ｃ）成分の種類、量を、表２に示すように変更したこと以外は、実施例１（比較例１〜３の場合）、あるいは実施例６（比較例４の場合）と同じ操作で第一塗膜と第二塗膜を有する樹脂成形体を得、評価した。結果を表２に示した。いずれの場合も良好な塗膜密着性は得られなかった（塗膜密着性：×）。
【００６３】
＜比較例５＞
（Ａ）成分を用いず、（Ｂ）成分の量を、表２に示すように変更したこと以外は、実施例１と同じ操作で第一塗膜と第二塗膜を有する樹脂成形体を得、評価した。結果を表２に示した。塗膜密着性は良好であったが、良好な耐磨耗性は得られなかった（耐摩耗性：Ｅランク）。
【００６４】
＜比較例６＞
（Ａ）成分を用いず、（Ｂ）成分および（ｃ）成分の量を、表２に示すように変更したこと以外は、実施例６と同じ操作で第一塗膜と第二塗膜を有する樹脂成形体を得、評価した。結果を表２に示した。塗膜密着性は良好であったが、良好な耐磨耗性は得られなかった（耐摩耗性：Ｅランク）。
【００６５】
【表１】
【表２】
【発明の効果】
以上説明したように、本発明によれば、耐候性、耐磨耗性、塗膜密着性にすぐれ、光触媒の効果が長期にわたり持続する樹脂成形体とすることが出来る。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a resin molded article having a layer (second coating film) containing photocatalytic titanium oxide on a plastic substrate via an undercoat layer (first coating film).
[0002]
[Prior art]
With environmental pollution, dirt on building exterior materials and outdoor buildings has become a problem. In order to prevent such contamination, there has been proposed a building exterior material and an outdoor building which are coated with a coating containing a photocatalyst by utilizing the strong oxidizing power and hydrophilicity of the photocatalyst and are hardened.
[0003]
However, resin moldings based on plastics such as acrylic resin (for example, polymethyl methacrylate or a copolymer of methyl methacrylate as a main component and other monomers such as acrylate), polycarbonate, polyethylene terephthalate, etc. In this case, if a photocatalyst-containing coating film is directly formed on the plastic substrate, the affinity between the substrate and the photocatalyst-containing coating film cannot be said to be good, and the adhesion may be poor. In addition, the oxidizing action of the photocatalyst sometimes causes a problem in weather resistance, such as whitening of the plastic substrate over time, cracking, and peeling of the photocatalyst layer.
[0004]
In order to solve the above problem, a method has been proposed in which an undercoat layer is first formed on a plastic substrate, and a coating film containing a photocatalyst is formed thereon. For example, there is a method in which a silica-based polymer using a hydrolyzable organosilane as a raw material is used as an undercoat layer (see Patent Documents 1 and 2).
[0005]
However, in order to achieve excellent adhesion between the plastic substrate and the undercoat layer with the material configuration shown in Patent Document 1, a primer layer is substantially further formed between the plastic substrate and the undercoat layer. However, there is a problem that the manufacturing cost increases.
[0006]
Further, in the material configuration shown in Patent Literature 2, when the thickness of the undercoat layer is small, the abrasion resistance of the molded body may be reduced. If a thick undercoat layer of 2 μm or more is formed on a plastic substrate to compensate for this, the adhesion of the coating film may be reduced.
[0007]
[Patent Document 1]
JP-A-11-91030
[Patent Document 2]
JP 2000-202363 A
[0008]
[Problems to be solved by the invention]
The present invention has been made to solve each problem of the related art. An object of the present invention is to provide a resin molded article having excellent weather resistance, abrasion resistance, and coating film adhesion, and having a long-lasting effect of a photocatalyst.
[0009]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to solve the above-described problems, and as a result, a hydrolyzate of an organoalkoxysilane (A) and a hydrolyzate of a phenylalkoxysilane (B) were formed on a plastic substrate. Forming a coating film (first coating film) composed of a silicon-based composition containing, and further forming a coating film (second coating film) containing photocatalytic titanium oxide thereon, to provide weather resistance and abrasion resistance It has been found that a resin molded article having excellent properties and adhesion to a coating film and having a long-lasting effect of the photocatalyst can be obtained.
[0010]
That is, the present invention
A plastic substrate,
A first coating formed of the following silicon-based composition, formed on at least a part of the plastic substrate,
A second coating film containing photocatalytic titanium oxide formed on at least a part of the first coating film,
It is a resin molding having:
Silicon based composition:
(A) a hydrolyzate of an organoalkoxysilane (A) represented by the formula (1),
(B) a hydrolyzate of a phenylalkoxysilane (B) represented by the formula (2):
A silicon-based composition comprising:
[0011]
R 1 Si (OR 2 ) 3 ・ ・ (1)
(Where R 1 Is an organic group having no phenyl group having 1 to 10 carbon atoms, R 2 Represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms. )
PhSi (OR 3 ) 3 ・ ・ (2)
(Wherein Ph is a phenyl group which may have a substituent, R 3 Represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms. )
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, a preferred embodiment of the present invention will be described.
[0013]
The plastic substrate that can be used for the resin molded article of the present invention is not particularly limited. For example, an acrylic resin (polymethyl methacrylate, or another monomer such as methyl methacrylate and acrylate, which are main components, may be used). Wherein the main component means 50% by mass or more of the monomer units constituting the resin), polycarbonate resin, polyvinyl chloride resin, urethane resin, phenol resin And plastic molded products such as epoxy resin, polyester resin, polyethylene resin and polypropylene resin, plastic films and fibers. It is preferably carried out when using an acrylic resin, particularly an acrylic resin whose molecular weight is not too high in terms of adhesion.
[0014]
<First coating>
In the present invention, the first coating film is a coating film formed on at least a part of a plastic substrate, and (a) hydrolysis of an organoalkoxysilane (A) represented by the formula (1). And (b) a hydrolyzate of a phenylalkoxysilane (B) represented by the formula (2).
[0015]
R 1 Si (OR 2 ) 3 ・ ・ (1)
(Where R 1 Is an organic group having no phenyl group having 1 to 10 carbon atoms, R 2 Represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms. )
PhSi (OR 3 ) 3 ・ ・ (2)
(Wherein Ph is a phenyl group which may have a substituent, R 3 Represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms. )
In the formula (1), R 1 Is an organic group having no phenyl group having 1 to 10 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, alkyl groups such as n-pentyl group and n-decyl group, allyl group, 3- (2-aminoethylamino) propyl group, 3-aminopropyl group, vinyl group, 3-glycidoxypropyl group, and 3-methacrylic group; Roxypropyl group, 3-mercaptopropyl group, 3-chloropropyl group, 3-chlorobutyl group, 3,4-epoxycyclohexylethyl group, 3,3,3-trifluorobutyl group and the like.
[0016]
In the formula (1), R 2 Is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms. R 2 Need not be the same for all three, but may be different. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, and an acetyl group.
[0017]
Specific examples of the organoalkoxysilanes (A) represented by the formula (1) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, methyltriacetoxysilane, and ethyltrimethoxysilane. , Ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, ethyltriacetoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltripropoxysilane, n-propyltributoxysilane, n -Propyltriacetoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltripropoxysilane, isopropyltributoxysilane, isopropyltriacetoxysilane, n Butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltripropoxysilane, n-butyltributoxysilane, n-butyltriacetoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, isobutyltripropoxysilane, isobutyltributyl Butoxysilane, isobutyltriacetoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, pentyltripropoxysilane, pentyltributoxysilane, pentyltriacetoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyl Trimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, and the like. Among them, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane are preferred from the viewpoints of the reaction rates of hydrolysis and condensation, and the hardness, strength, and abrasion resistance of the obtained coating film. Among them, methyltrimethoxysilane is particularly preferred.
[0018]
The component (a) is obtained by substituting a part or all of the alkoxy group or the acyloxy group of the organoalkoxysilanes (A) represented by the formula (1) with a hydroxyl group. Further, the substituted hydroxyl groups may be partially condensed between the molecules of the component (a).
[0019]
As a method for producing the component (a), for example, an organoalkoxysilane (A) represented by the formula (1) is added to water (for example, 1 to 10 mol per 1 mol of the organoalkoxysilane (A)), and hydrochloric acid. It can be produced by adding acid or acetic acid to make the solution acidic (for example, pH 2 to 5) and stirring. The organoalkoxysilanes (A) may be used alone or in combination of two or more.
[0020]
The component (b) of the present invention is a hydrolyzate of a phenylalkoxysilane (B) represented by the formula (2). This component (b) is a component that improves the adhesion between the first coating film and the plastic substrate and between the first coating film and the second coating film by being blended with the silicon-based composition.
[0021]
In the formula (2), Ph represents a phenyl group which may have a substituent. Examples of the substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a halogen group, and the like. R 3 Is an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms. Note that R 3 Need not be the same for all three, but may be different. As a specific example, the above-mentioned R 2 And the same.
[0022]
Specific examples of the phenylalkoxysilanes (B) represented by the formula (2) include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltributoxysilane, phenyltriacetoxysilane, p-methylphenyl Trimethoxysilane, m-chlorophenyltrimethoxysilane, and the like. Among them, phenyltrimethoxysilane and phenyltriethoxysilane are preferred from the viewpoint of high hydrolysis rate.
[0023]
The component (b) is obtained by substituting a part or all of an alkoxy group or an acyloxy group of the phenylalkoxysilanes (B) represented by the formula (2) with a hydroxyl group. The substituted hydroxyl groups may be partially condensed between the molecules of the component (b).
[0024]
As a method for producing the component (b), for example, phenylalkoxysilanes (B) represented by the formula (2) may be added to water (for example, 1 to 10 mol per 1 mol of the phenylalkoxysilanes (B)); The solution can be produced by adding hydrochloric acid, acetic acid, or the like, making the solution acidic (for example, pH 2 to 5), and stirring. The phenylalkoxysilanes (B) may be used alone or in combination of two or more.
[0025]
The ratio of the components (a) and (b) in the silicon-based composition for forming the first coating film may be appropriately determined according to the desired coating film properties. For example, regarding the ratio of the components (a) and (b), when the total number of moles of the components (A) and (B) is 100 moles in terms of the number of moles charged, the mole number of the component (B) is in the range of 1 to 55 moles. It is preferable that If it is at least 1 mol, the adhesion to the plastic substrate will be improved. On the other hand, when the amount is 55 mol or less, the abrasion resistance and weather resistance of the obtained resin molded article are improved. A more preferred range is from 3 to 40 moles.
[0026]
In the above-mentioned charged moles, the moles of the components (A) and (B) are represented by the following equations.
(A) Number of moles of component = (mass charged of organoalkoxysilanes (A)) / (molecular weight of organoalkoxysilanes (A))
Number of moles of component (B) = (mass charged of phenylalkoxysilanes (B)) / (molecular weight of phenylalkoxysilanes (B))
The silicon-based composition of the present invention preferably contains (c) colloidal silica in order to further improve the abrasion resistance of the resin molded article. It is preferable to use a silica sol in which silica fine particles are uniformly dispersed in water, or an organosilica sol in which a silica fine particle is uniformly dispersed in a hydrophilic solvent. The content (solid content concentration) of the silica fine particles in the dispersion is preferably from 10 to 50% by mass, and more preferably from 20 to 40% by mass.
[0027]
The particle size of the colloidal silica (c) is preferably 100 nm or less from the viewpoint of transparency when the resin molded article of the present invention is obtained. In addition, from the viewpoint of crack resistance when forming the resin molded article of the present invention, it is preferably 5 nm or more.
[0028]
The solvent of the colloidal silica disperses the components (a), (b) and (c) uniformly in the silica-based composition without agglomeration and precipitation, and promotes reactions such as hydrolysis and condensation. From this point, it is preferable that the solvent is a hydrophilic solvent such as water, methanol, ethanol, isobutanol, isopropanol, and ethylene glycol.
[0029]
Specific examples of the colloidal silica include aqueous dispersion colloidal silica, methanol dispersion colloidal silica, ethanol dispersion colloidal silica, isopropanol dispersion colloidal silica, ethylene glycol dispersion colloidal silica, isobutanol dispersion colloidal silica, and the like. . Among them, isopropanol-dispersed colloidal silica is preferred from the viewpoint of stability when mixed with the components (a), (b) and (c). Examples of commercially available products include Snowtex IPA-ST (trade name, manufactured by Nissan Chemical Industry Co., Ltd.) and OSCAL1432 (trade name, manufactured by Catalysis Chemical Industry Co., Ltd.).
[0030]
Further, a mixture of colloidal silica and colloidal alumina or colloidal titanium oxide can also be used.
[0031]
It is preferable that the compounding amount of the component (c) is 25 to 250 moles per 100 moles of the total of the component (A) and the component (B) in terms of the number of moles charged. If it is 25 mol or more, the surface hardness and abrasion resistance are further improved. On the other hand, when the amount is 250 mol or less, a coating film without cracks is obtained. A more preferred range is 50 to 200 moles.
[0032]
The number of moles of the component (c) is represented by the following equation.
Number of moles of component (c) = (mass of charged silica (solid content) of solvent-dispersed colloidal silica) / (silica molecular weight: 60.1 (SiO 2 As))
The silicon-based composition for forming the first coating film of the present invention is obtained by uniformly mixing the components (a), (b), and (c), adjusting the solid concentration, and dispersing the solid. It is preferable to contain an organic solvent in order to improve storage stability. Examples of the organic solvent include alcohols, ketones, ethers, cellosolves, esters, and aromatic compounds. Specifically, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl Ketone, diisobutyl ketone, tetrahydrofuran, dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, toluene, xylene, ethyl acetate, butyl acetate, γ-butyrolactone, diacetone alcohol, 1-acetoxy-2-ethoxyethane and the like can be mentioned. These can be used alone or in combination of two or more.
[0033]
The proportion of the organic solvent in the silicon-based composition for forming the first coating film is determined by the proportion of the components (A) and (B), and in some cases, the proportion of the components (A) and (B) and the component (c). It is preferably 40 to 10000 parts by mass with respect to 100 parts by mass in total. The amount of 40 parts by mass or more is significant in terms of dispersion stability and storage stability of each component, and in obtaining a good coating film by preventing the viscosity of the liquid from becoming too high. Further, the use of 10,000 parts by mass or less is significant in avoiding that the solid content becomes too low, the coating film becomes thin, and sufficient adhesion, weather resistance, and abrasion resistance cannot be obtained.
[0034]
In addition, various additives such as a surface smoothing agent, a surfactant, an ultraviolet absorber, a storage stabilizer, a curing agent, and a leveling agent can be appropriately added to the silicon-based composition as needed.
[0035]
A preferred example of a method for preparing a silicon-based composition suitable for the first coating film will be described. First, the organoalkoxysilanes (A) represented by the formula (1) and the phenylalkoxysilanes (B) represented by the formula (2) are mixed well. In some cases, colloidal silica (c) is added and mixed well. While stirring this mixture, an appropriate amount of water is added and hydrolyzed. At that time, the pH is adjusted to acidic (for example, 2 to 5) with hydrochloric acid, acetic acid or the like in order to promote hydrolysis. After stirring is continued for about 3 to 5 hours, it is confirmed that the hydrolysis has been sufficiently performed by the NMR method, and then ammonium, sodium hydroxide, an aqueous solution of sodium acetate and the like are added, and the pH is adjusted to around neutral (for example, 6 to 5). Adjust to 7) and continue stirring for about 20 hours to conduct condensation. Thereafter, an organic solvent and, if necessary, a curing agent and a leveling agent are added and uniformly mixed to obtain a silicon-based composition.
[0036]
In this method, an organoalkoxysilane (A) represented by the formula (1) and a phenylalkoxysilane (B) represented by the formula (2) are separately hydrolyzed with an appropriate amount of water, and then mixed. You may. In some cases, colloidal silica (c) may be mixed thereafter.
[0037]
As a method of forming the first coating film using such a silicon-based composition, a method of applying the silicon-based composition to at least a part of a plastic substrate and curing by heating.
[0038]
As a method of applying the silicon-based composition to at least a part of the plastic substrate, a brush coating method, a casting method, a roller coating method, a bar coating method, a spray coating method, an air knife coating method, a dip coating method, a spin coating method, A coating method or the like can be used, but is not particularly limited.
[0039]
The silicon-based composition is preferably applied such that the thickness of the obtained first coating film is 1 to 20 μm. By setting the thickness of the first coating film to 1 μm or more, abrasion resistance can be improved, and deterioration of the substrate due to the layer (second coating film) containing photocatalytic titanium oxide can be suppressed for a long time. By setting the film thickness to 20 μm or less, it is possible to suppress the occurrence of cracks during curing. Preferably it is 2 μm to 10 μm.
[0040]
After the silicon-based material applied to at least a part of the plastic substrate is dried at room temperature, it is cured by heating with a dryer, infrared irradiation, or the like to obtain the first coating film.
[0041]
The heat curing temperature is preferably from 70 to 130C. By curing at 70 ° C. or higher, the abrasion resistance of the protective coating can be improved. By setting the temperature to 130 ° C. or lower, the occurrence of cracks in the first coating film can be suppressed. A more preferred curing temperature is 80 to 120 ° C.
[0042]
<Second coating>
The second coating film of the present invention is obtained by applying a composition for forming a second coating film containing photocatalytic titanium oxide to at least a part of the first coating film, and performing heat curing. The composition for forming the second coating film is not particularly limited as long as it is a composition containing photocatalytic titanium oxide, and can be used irrespective of an aqueous or organic solvent system. For example, a composition containing a photocatalytic titanium oxide in a composition containing one or both of a hydrolyzate of an alkylalkoxysilane and a condensate thereof as a main component is exemplified. The photocatalytic titanium oxide is not particularly limited, but is preferably one or both of anatase-type titanium oxide and brookite-type titanium oxide because of its excellent photocatalytic action. The content of the photocatalytic titanium oxide in the second coating film forming composition is not particularly limited and may be a necessary amount, but is preferably 0.05% by mass to 10% by mass.
[0043]
As the composition for forming a second coating film containing such photocatalytic titanium oxide, a commercially available composition can also be used. For example, trade name: ST-K211 manufactured by Ishihara Sangyo Co., Ltd., trade name: NTB-13, NTB-100, NTB-30, manufactured by Showa Denko KK, trade name: TKC-302, TKC- 303, TKC-304, manufactured by Mitsui Mining Co., Ltd. Trade name: Miracle Titanium M and the like. The composition for forming the second coating film is not limited to these.
[0044]
As a method of forming a second coating film using such a second coating film forming composition, a second coating film forming composition is applied to at least a part of the first coating film, and then heat-cured. There is a method to make it.
[0045]
As a method of applying the second coating film forming composition to at least a part of the first coating film, a brush coating method, a casting method, a roller coating method, a bar coating method, a spray coating method, an air knife coating method, Dip coating, spin coating, and the like can be given, but are not particularly limited. The coating amount of the second coating film forming composition is preferably applied such that the thickness of the obtained second coating film is 0.01 to 5 μm. By setting the film thickness of the second coating film to 0.01 μm or more, the stain prevention function and the hydrophilicity of the resin molded article are improved. By setting the film thickness to 5 μm or less, it is possible to suppress the occurrence of cracks during curing and to improve the scratch resistance. Preferably it is 0.02 to 1 μm.
[0046]
The second coating film is obtained by drying the composition for forming a second coating film applied to at least a part of the first coating film at room temperature, and then heating and curing the composition using a dryer or infrared irradiation. The heat-curing temperature may be appropriately selected in consideration of the composition of the second coating film forming composition. However, since the first coating film is also heated at this time, the curing temperature of the first coating film is preferably set to + 60 ° C. or lower in order to suppress deterioration.
[0047]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. In addition, the physical properties of the resin molded body in the examples show measurement results by the following methods.
[0048]
1) Appearance
The resin molded body was visually observed for transparency, cracks, whitening of the coating film, and the presence or absence of peeling of the first coating film or the second coating film. . Those having opaque portions, cracks, whitening, and peeling were evaluated as defective (x).
[0049]
2) Coating adhesion
The first coating film and the second coating film of the resin molded body were cut at 11 mm intervals at 1 mm intervals with a razor blade to form 100 grids, and a cellophane tape was closely adhered to them. Thereafter, when the film was abruptly peeled 45 ° forward, the following criteria were evaluated based on the number of squares remaining without peeling of the first coating film and the second coating film.
…: No squares peeled off (good adhesion).
Δ: The peeled squares are 1/100 or more and 5/100 or less (medium adhesiveness).
X: The peeled squares were 6/100 or more (poor adhesion).
[0050]
3) hydrophilic (photocatalytic)
The hydrophilicity of the resin molded product was evaluated by the contact angle with water. The measurement was performed using a CA-150 contact angle meter manufactured by Kyowa Interface Chemical Co., Ltd.
・ ・ ・: The contact angle of the resin molded body with water was 15 degrees or less.
Δ: The contact angle of the resin molded body with water was larger than 15 degrees and smaller than 20 degrees.
X: The contact angle of the resin molded body with water was 20 degrees or more.
[0051]
4) Abrasion resistance
The surface of the resin molded product was coated with # 000 steel wool at 1 kg / cm 2 Was applied and rubbed back and forth for 10 times, and the degree of scratches generated in a range of 1 × 3 cm was observed and evaluated according to the following criteria.
A: No scratches. There is glossy surface.
B: 1 to 9 scratches. There is glossy surface.
C: Scratch of 10 or more to 99 or less. There is glossy surface.
D: 100 or more scratches. There is glossy surface.
E: The glossy surface disappears.
[0052]
5) Weather resistance
A JIS K5400 sunshine weather meter accelerated exposure test (black panel temperature 63 ° C., humidity 50% RH, one cycle of “12 minutes rain → 48 minutes no rain”) was performed. The appearance (transparency, crack, whitening, and peeling of the coating film) after 1000 hours of exposure (weather resistance test), coating film adhesion, hydrophilicity, and abrasion resistance were evaluated. The evaluation was performed in the same manner as in 1), 2), 3) and 4).
[0053]
<Example 1>
[Preparation of silicon-based composition]
A homogeneous solution was prepared by mixing 36.7 g (0.270 mol) of methyltrimethoxysilane as the component (A) and 5.94 g (0.030 mol) of phenyltrimethoxysilane as the component (B). While stirring the solution, 20 g of water was gradually added. Further, a 0.1N hydrochloric acid solution was added dropwise so that the pH became 3.5, and hydrolysis was performed. Since the solution generated heat as water was added, stirring was continued for 4 hours while maintaining the liquid temperature at about 10 ° C. while cooling in a water bath. Next, a 15.2% by mass aqueous sodium acetate solution was added so that the pH became 6.6. The solution was further stirred for 20 hours while maintaining the liquid temperature at 35 ° C. in a water bath. Further, 12.0 g of γ-butyrolactone and 14.0 g of butyl cellosolve were added and stirred to obtain a uniform solution. Further, 0.01 g of a silicone-based surfactant L-7001 (trade name) manufactured by Nippon Unicar Co., Ltd. was added and stirred at room temperature for about 1 hour to obtain a silicon-based composition for forming a first coating film.
[0054]
[Formation of coating film]
Of the first coating film after heat curing on an acrylic resin plate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acrylite EX, length × width × thickness = 150 × 100 × 3 mm) having a methyl methacrylate unit as a main component The lifting speed was adjusted so that the film thickness became 4 μm, and a silicon-based composition for forming a first coating film was applied by a dip coating method. After drying at room temperature for about 30 minutes, the mixture was cured by heating at 80 ° C. for 2 hours using a dryer to form a first coating film. Next, on the acrylic plate on which the first coating film is formed, the lifting speed is adjusted so that the thickness of the second coating film after heat curing is 0.1 μm, and the second coating film forming composition is formed by dip coating. (Anatase type titanium oxide-containing coating material, trade name: ST-K211; solid content concentration: 0.2% by mass, manufactured by Ishihara Sangyo Co., Ltd.) was applied. After drying at room temperature for about 20 minutes, the resin was cured by heating at 90 ° C. for 30 minutes using a dryer to form a second coating film, thereby obtaining a resin molded body.
[0055]
Next, physical properties of the obtained resin molded body were evaluated. The initial physical properties of this resin molded product were good in appearance (transparent) without cracks, whitening, and peeling of the coating film (good), good adhesion to the coating film (good), and a contact angle with water of 13 was obtained. The degree and the hydrophilicity were good (）). The abrasion resistance was as good as C rank. Regarding the physical properties of the resin molded article after the weather resistance test, the appearance was transparent and good (○) without cracks, whitening, and peeling of the coating film. In addition, the coating film adhesion was good (、), and the contact angle with water was 5 °, showing good hydrophilicity (○). The abrasion resistance was as good as rank C. The results are shown in Table 1.
[0056]
<Examples 2 to 5>
A resin molded article having a first coating film and a second coating film was obtained by the same operation as in Example 1 except that the amounts of the components (A) and (B) were changed as shown in Table 1, and evaluated. did. In any of the resin molded products, the appearance, coating film adhesion, hydrophilicity, and abrasion resistance after the initial and weather resistance tests are good (appearance: ○, coating film adhesion: Δ or more, hydrophilicity: ○, abrasion resistance) (D rank or higher). The results are shown in Table 1.
[0057]
<Example 6>
[Preparation of silicon-based composition]
12.2 g (0.090 mol) of methyltrimethoxysilane as the component (A), 1.98 g (0.010 mol) of phenyltrimethoxysilane as the component (B), and isopropyl alcohol-dispersed colloidal silica as the component (c) (particle diameter 10 to 20 nm, a solid content of 30% by mass, 40.1 g (0.200 mol) of Nissan Chemical Industries, Ltd., trade name: Snowtex IPA-ST, were mixed to form a uniform solution.
[0058]
While stirring this solution, 20 g of water was gradually added to carry out hydrolysis. Since the solution generated heat as water was added, stirring was continued for 4 hours while maintaining the liquid temperature at about 10 ° C. while cooling in a water bath. Next, a 15.2% by mass aqueous sodium acetate solution was added so that the pH became 6.6. The solution was further stirred for 20 hours while maintaining the liquid temperature at 35 ° C. in a water bath. 12.0 g of γ-butyrolactone and 14.0 g of butyl cellosolve were added as organic solvents and stirred to form a homogeneous solution. Further, 0.01 g of a silicone-based surfactant L-7001 (trade name) manufactured by Nippon Unicar Co., Ltd. was added and stirred at room temperature for about 1 hour to obtain a silicon-based composition for forming a first coating film.
[0059]
[Formation of coating film]
Of the first coating film after heat curing on an acrylic resin plate (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Acrylite EX, length × width × thickness = 150 × 100 × 3 mm) having methyl methacrylate unit as a main component The lifting speed was adjusted so that the film thickness became 4 μm, and a silicon-based composition for forming a first coating film was applied by a dip coating method. After drying at room temperature for about 30 minutes, the mixture was cured by heating at 80 ° C. for 2 hours using a dryer to form a first coating film. Next, on the acrylic plate on which the first coating film is formed, the lifting speed is adjusted so that the thickness of the second coating film after heat curing is 0.1 μm, and the second coating film forming composition is formed by dip coating. (Ishihara Sangyo Co., Ltd., anatase-type titanium oxide-containing coating material, trade name: ST-K211; solid content concentration: 0.2% by mass). After drying at room temperature for about 20 minutes, the resin was heat-cured at 90 ° C. for 30 minutes using a dryer to form a second coating film, thereby obtaining a resin molded body.
[0060]
Next, physical properties of the obtained resin molded body were evaluated. The initial physical properties of this resin molded product were good in appearance (transparent) without cracks, whitening, and peeling of the coating film (good), good adhesion to the coating film (good), and a contact angle with water of 13 was obtained. The degree and the hydrophilicity were good (）). Further, the abrasion resistance was excellent as rank B. Regarding the physical properties of the resin molded article after the weather resistance test, the appearance was transparent and good (ラ ッ ク) without cracks or peeling of the coating film. In addition, the coating film adhesion was good (、), and the contact angle with water was 5 °, showing good hydrophilicity (○). Further, the abrasion resistance was as excellent as B rank. The results are shown in Table 1.
[0061]
<Examples 7 to 12>
Except that the types and amounts of the components (A), (B), (c) and the solvent were changed as shown in Table 1, the first coating film and the second coating film were operated in the same manner as in Example 6. Was obtained and evaluated. In any of the resin molded products, the appearance, coating film adhesion, hydrophilicity, and abrasion resistance after the initial and weather resistance tests are good (appearance: ○, coating film adhesion: ○, hydrophilicity: ○, abrasion resistance) : B rank). The results are shown in Table 1.
[0062]
<Comparative Examples 1-4>
Example 1 (in the case of Comparative Examples 1 to 3) or Example 1 except that the component (B) was not used, and the types and amounts of the component (A) and the component (c) were changed as shown in Table 2. A resin molded article having a first coating film and a second coating film was obtained and evaluated by the same operation as in Example 6 (in the case of Comparative Example 4). The results are shown in Table 2. In each case, good coating adhesion was not obtained (coating adhesion: X).
[0063]
<Comparative Example 5>
A resin molded article having a first coating film and a second coating film was prepared in the same manner as in Example 1, except that the component (A) was not used and the amount of the component (B) was changed as shown in Table 2. Obtained and evaluated. The results are shown in Table 2. Although the coating film adhesion was good, good abrasion resistance was not obtained (abrasion resistance: rank E).
[0064]
<Comparative Example 6>
Except that the component (A) was not used and the amounts of the component (B) and the component (c) were changed as shown in Table 2, the first coating film and the second coating film were formed in the same manner as in Example 6. The obtained resin molded body was obtained and evaluated. The results are shown in Table 2. Although the coating film adhesion was good, good abrasion resistance was not obtained (abrasion resistance: rank E).
[0065]
[Table 1]
[Table 2]
【The invention's effect】
As described above, according to the present invention, it is possible to obtain a resin molded article having excellent weather resistance, abrasion resistance, and coating film adhesion, and having a long-lasting effect of the photocatalyst.
Claims (5)
該プラスチック基材上の少なくとも一部に形成された、下記シリコン系組成物からなる第一塗膜と、
該第一塗膜上の少なくとも一部に形成された、光触媒性酸化チタンを含む第二塗膜と、
を有する樹脂成形体。
シリコン系組成物：
（ａ）式（１）で表されるオルガノアルコキシシラン類（Ａ）の加水分解物と、
（ｂ）式（２）で表されるフェニルアルコキシシラン類（Ｂ）の加水分解物と
を含むシリコン系組成物。
Ｒ１Ｓｉ（ＯＲ２）３ ・・（１）
（式中、Ｒ１は炭素数１〜１０のフェニル基を持たない有機基、Ｒ２は炭素数１〜５のアルキル基または炭素数１〜４のアシル基を示す。）
ＰｈＳｉ（ＯＲ３）３ ・・（２）
（式中、Ｐｈは置換基を有してもよいフェニル基、Ｒ３は炭素数１〜５のアルキル基または炭素数１〜４のアシル基を示す。）A plastic substrate,
A first coating formed of the following silicon-based composition, formed on at least a part of the plastic substrate,
A second coating film containing photocatalytic titanium oxide formed on at least a part of the first coating film,
A resin molded article having:
Silicon based composition:
(A) a hydrolyzate of an organoalkoxysilane (A) represented by the formula (1),
(B) a silicon-based composition containing a phenylalkoxysilane (B) hydrolyzate represented by the formula (2).
R 1 Si (OR 2 ) 3 (1)
(In the formula, R 1 represents an organic group having no phenyl group having 1 to 10 carbon atoms, and R 2 represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms.)
PhSi (OR 3 ) 3・ ・ (2)
(In the formula, Ph represents a phenyl group which may have a substituent, and R 3 represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003149238A JP2004351650A (en) | 2003-05-27 | 2003-05-27 | Resin molded object |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003149238A JP2004351650A (en) | 2003-05-27 | 2003-05-27 | Resin molded object |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2004351650A true JP2004351650A (en) | 2004-12-16 |
Family
ID=34045406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003149238A Pending JP2004351650A (en) | 2003-05-27 | 2003-05-27 | Resin molded object |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2004351650A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007168137A (en) * | 2005-12-19 | 2007-07-05 | Kubota Matsushitadenko Exterior Works Ltd | Coated object |
| JP2008142636A (en) * | 2006-12-11 | 2008-06-26 | National Institute Of Advanced Industrial & Technology | Method of applying photocatalyst on polyolefin based resin molding |
-
2003
- 2003-05-27 JP JP2003149238A patent/JP2004351650A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007168137A (en) * | 2005-12-19 | 2007-07-05 | Kubota Matsushitadenko Exterior Works Ltd | Coated object |
| JP2008142636A (en) * | 2006-12-11 | 2008-06-26 | National Institute Of Advanced Industrial & Technology | Method of applying photocatalyst on polyolefin based resin molding |
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