JPH03168227A - Coated polycarbonate-based resin molded article - Google Patents
Coated polycarbonate-based resin molded articleInfo
- Publication number
- JPH03168227A JPH03168227A JP1308646A JP30864689A JPH03168227A JP H03168227 A JPH03168227 A JP H03168227A JP 1308646 A JP1308646 A JP 1308646A JP 30864689 A JP30864689 A JP 30864689A JP H03168227 A JPH03168227 A JP H03168227A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- group
- coated
- weight
- layer
- 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
Links
- 229920000515 polycarbonate Polymers 0.000 title abstract description 43
- 239000004417 polycarbonate Substances 0.000 title abstract description 43
- 229920005989 resin Polymers 0.000 title abstract description 7
- 239000011347 resin Substances 0.000 title abstract description 7
- 239000010410 layer Substances 0.000 claims abstract description 55
- 238000000576 coating method Methods 0.000 claims abstract description 52
- 239000011248 coating agent Substances 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 35
- -1 alkyl methacrylate Chemical compound 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000008119 colloidal silica Substances 0.000 claims abstract description 22
- 229920001577 copolymer Polymers 0.000 claims abstract description 17
- 125000000524 functional group Chemical group 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000006096 absorbing agent Substances 0.000 claims abstract description 10
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 239000011247 coating layer Substances 0.000 claims abstract description 7
- 125000005395 methacrylic acid group Chemical group 0.000 claims abstract description 6
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims description 21
- 238000005299 abrasion Methods 0.000 claims description 19
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 17
- 229920005668 polycarbonate resin Polymers 0.000 claims description 16
- 239000004431 polycarbonate resin Substances 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- 125000003700 epoxy group Chemical group 0.000 claims description 11
- 150000003377 silicon compounds Chemical class 0.000 claims description 10
- 239000008199 coating composition Substances 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 5
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 4
- 125000005370 alkoxysilyl group Chemical group 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004593 Epoxy Substances 0.000 abstract 1
- 239000005002 finish coating Substances 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 25
- 238000007602 hot air drying Methods 0.000 description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000005856 abnormality Effects 0.000 description 7
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 239000001632 sodium acetate Substances 0.000 description 4
- 235000017281 sodium acetate Nutrition 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920001651 Cyanoacrylate Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 2
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- KNDSIIWXDUZDJI-UHFFFAOYSA-N methoxy-tris[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound C1OC1COCC[Si](CCOCC1OC1)(OC)CCOCC1CO1 KNDSIIWXDUZDJI-UHFFFAOYSA-N 0.000 description 2
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000007761 roller coating Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- ADVORQMAWLEPOI-XHTSQIMGSA-N (e)-4-hydroxypent-3-en-2-one;oxotitanium Chemical compound [Ti]=O.C\C(O)=C/C(C)=O.C\C(O)=C/C(C)=O ADVORQMAWLEPOI-XHTSQIMGSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- WNEODWDFDXWOLU-QHCPKHFHSA-N 3-[3-(hydroxymethyl)-4-[1-methyl-5-[[5-[(2s)-2-methyl-4-(oxetan-3-yl)piperazin-1-yl]pyridin-2-yl]amino]-6-oxopyridin-3-yl]pyridin-2-yl]-7,7-dimethyl-1,2,6,8-tetrahydrocyclopenta[3,4]pyrrolo[3,5-b]pyrazin-4-one Chemical compound C([C@@H](N(CC1)C=2C=NC(NC=3C(N(C)C=C(C=3)C=3C(=C(N4C(C5=CC=6CC(C)(C)CC=6N5CC4)=O)N=CC=3)CO)=O)=CC=2)C)N1C1COC1 WNEODWDFDXWOLU-QHCPKHFHSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 101000856234 Clostridium acetobutylicum (strain ATCC 824 / DSM 792 / JCM 1419 / LMG 5710 / VKM B-1787) Butyrate-acetoacetate CoA-transferase subunit A Proteins 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- RSPISYXLHRIGJD-UHFFFAOYSA-N OOOO Chemical compound OOOO RSPISYXLHRIGJD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005083 alkoxyalkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- SYFOAKAXGNMQAX-UHFFFAOYSA-N bis(prop-2-enyl) carbonate;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.C=CCOC(=O)OCC=C SYFOAKAXGNMQAX-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- GNTHOKPJBLJTJY-UHFFFAOYSA-N dimethoxy(oxiran-2-ylmethoxymethyl)silane Chemical compound CO[SiH](OC)COCC1CO1 GNTHOKPJBLJTJY-UHFFFAOYSA-N 0.000 description 1
- OSDDERYBYVDGCN-UHFFFAOYSA-N dimethoxy-(oxiran-2-ylmethoxymethyl)-phenylsilane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)COCC1CO1 OSDDERYBYVDGCN-UHFFFAOYSA-N 0.000 description 1
- OLGFJVSABRBVFE-UHFFFAOYSA-N dimethoxy-bis(oxiran-2-ylmethoxymethyl)silane Chemical compound C1OC1COC[Si](OC)(OC)COCC1CO1 OLGFJVSABRBVFE-UHFFFAOYSA-N 0.000 description 1
- KYZBSTMQNIESBN-UHFFFAOYSA-N dimethoxy-bis[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound C1OC1COCC[Si](OC)(OC)CCOCC1CO1 KYZBSTMQNIESBN-UHFFFAOYSA-N 0.000 description 1
- CAEPKDWOZATEMI-UHFFFAOYSA-N dimethoxy-methyl-(oxiran-2-ylmethoxymethyl)silane Chemical compound CO[Si](C)(OC)COCC1CO1 CAEPKDWOZATEMI-UHFFFAOYSA-N 0.000 description 1
- PWPGWRIGYKWLEV-UHFFFAOYSA-N dimethoxy-methyl-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CO[Si](C)(OC)CCOCC1CO1 PWPGWRIGYKWLEV-UHFFFAOYSA-N 0.000 description 1
- YSRDUADNUDFRQJ-UHFFFAOYSA-N dimethoxy-methyl-[4-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CO[Si](C)(OC)CCCCOCC1CO1 YSRDUADNUDFRQJ-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- OGANKJGJBLMLGD-UHFFFAOYSA-N ethenyl-dimethoxy-(oxiran-2-ylmethoxymethyl)silane Chemical compound CO[Si](C=C)(OC)COCC1CO1 OGANKJGJBLMLGD-UHFFFAOYSA-N 0.000 description 1
- DRUOQOFQRYFQGB-UHFFFAOYSA-N ethoxy(dimethyl)silicon Chemical compound CCO[Si](C)C DRUOQOFQRYFQGB-UHFFFAOYSA-N 0.000 description 1
- KUGSJJNCCNSRMM-UHFFFAOYSA-N ethoxyboronic acid Chemical compound CCOB(O)O KUGSJJNCCNSRMM-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- BFMUNUUIHLWYSN-UHFFFAOYSA-N ethyl-dimethoxy-(oxiran-2-ylmethoxymethyl)silane Chemical compound CC[Si](OC)(OC)COCC1CO1 BFMUNUUIHLWYSN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- MDLRQEHNDJOFQN-UHFFFAOYSA-N methoxy(dimethyl)silicon Chemical compound CO[Si](C)C MDLRQEHNDJOFQN-UHFFFAOYSA-N 0.000 description 1
- MLSKXPOBNQFGHW-UHFFFAOYSA-N methoxy(dioxido)borane Chemical compound COB([O-])[O-] MLSKXPOBNQFGHW-UHFFFAOYSA-N 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- LQKLWNAGFLCROC-UHFFFAOYSA-N methoxy-dimethyl-(oxiran-2-ylmethoxymethyl)silane Chemical compound CO[Si](C)(C)COCC1CO1 LQKLWNAGFLCROC-UHFFFAOYSA-N 0.000 description 1
- UZVGEBIWBCCMAY-UHFFFAOYSA-N methoxy-dimethyl-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CO[Si](C)(C)CCOCC1CO1 UZVGEBIWBCCMAY-UHFFFAOYSA-N 0.000 description 1
- PXHGLKUGRYOERP-UHFFFAOYSA-N methoxy-dimethyl-[4-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CO[Si](C)(C)CCCCOCC1CO1 PXHGLKUGRYOERP-UHFFFAOYSA-N 0.000 description 1
- ZNEANRFOVQWASK-UHFFFAOYSA-N methoxy-tris(oxiran-2-ylmethoxymethyl)silane Chemical compound C1OC1COC[Si](COCC1OC1)(OC)COCC1CO1 ZNEANRFOVQWASK-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- FMJSMJQBSVNSBF-UHFFFAOYSA-N octocrylene Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC(CC)CCCC)C1=CC=CC=C1 FMJSMJQBSVNSBF-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 1
- 239000006100 radiation absorber Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- UNKMHLWJZHLPPM-UHFFFAOYSA-N triethoxy(oxiran-2-ylmethoxymethyl)silane Chemical compound CCO[Si](OCC)(OCC)COCC1CO1 UNKMHLWJZHLPPM-UHFFFAOYSA-N 0.000 description 1
- QMBSEKLOGVDBLD-UHFFFAOYSA-N triethoxy-[2-(oxiran-2-yl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCC1CO1 QMBSEKLOGVDBLD-UHFFFAOYSA-N 0.000 description 1
- HGCVEHIYVPDFMS-UHFFFAOYSA-N trimethoxy(7-oxabicyclo[4.1.0]heptan-4-ylmethyl)silane Chemical compound C1C(C[Si](OC)(OC)OC)CCC2OC21 HGCVEHIYVPDFMS-UHFFFAOYSA-N 0.000 description 1
- LFBULLRGNLZJAF-UHFFFAOYSA-N trimethoxy(oxiran-2-ylmethoxymethyl)silane Chemical compound CO[Si](OC)(OC)COCC1CO1 LFBULLRGNLZJAF-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- NVHGPBWXDPPIDQ-UHFFFAOYSA-N trimethoxy-[2-(oxiran-2-yl)ethyl]silane Chemical compound CO[Si](OC)(OC)CCC1CO1 NVHGPBWXDPPIDQ-UHFFFAOYSA-N 0.000 description 1
- ZNXDCSVNCSSUNB-UHFFFAOYSA-N trimethoxy-[2-(oxiran-2-ylmethoxy)ethyl]silane Chemical compound CO[Si](OC)(OC)CCOCC1CO1 ZNXDCSVNCSSUNB-UHFFFAOYSA-N 0.000 description 1
- INFBTIHDWYFQPG-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-yl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCC1CO1 INFBTIHDWYFQPG-UHFFFAOYSA-N 0.000 description 1
- ZQPNGHDNBNMPON-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CO[Si](OC)(OC)CCC(C)OCC1CO1 ZQPNGHDNBNMPON-UHFFFAOYSA-N 0.000 description 1
- WRVOWUWTWZSVSX-UHFFFAOYSA-N trimethoxy-[3-methyl-4-(oxiran-2-yl)butyl]silane Chemical compound C(C1CO1)C(CC[Si](OC)(OC)OC)C WRVOWUWTWZSVSX-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、耐摩耗性及び嗣候性が優れた被覆ボリカーボ
ネート系樹脂成形物品、特にボリカーポ外線吸収剤を含
む下塗り塗料を被覆硬化し、その上に付着性が良好な中
塗り被膜を形成し、その上に上塗り被膜を形成した３層
皮瞑構造からなる耐履耗性及び耐候性が優れた被覆ポリ
カーボネート系樹脂成形物品に関するものである．
（従来の技術）
一般にポリカーボネート系樹脂は、耐衡箪性、透明性に
優れているため透明プラスチック材料として広く使用さ
れているが、耐摩耗性、耐溶剤性に乏しく表面に偏がつ
き易く、又有機溶剤に侵され易く、更に耐光性が不十分
であって黄変し易いという欠点がある．
これらの欠点を改良する方法として、ポリカーボネート
系樹脂基材上に下塗り塗談及び上塗り塗膜の２層を形成
し、しかもその少なくともｌ層に紫外線吸収剤、紫外線
安定剤あるいは酸化防止削等を含む熱、紫外線または電
子線硬化性樹脂で被覆する方法が種々提案されている．
例えば特間昭５８−１９６２３７には、ポリカーボネー
ト表面にボリアルキルアクリレート叉は、ポリアルキル
メタクリレートボリマーと紫外線吸収剤を含有する下塗
り塗料を塗布乾燥後アルキルトリアルコキシシランの部
分加水分解縮合物を主成分とする上塗り塗料を塗布硬化
させる表面処理法が間示されている．
特表昭５５−５００８５８、特表昭５９−２４７２８に
は、ポリカーボネート成形品の表面に官能基含有アクリ
ルボリマーと紫外線吸収剤を含有する下塗り塗料を塗布
、乾燥後コロイド状シリカを充填したオルガノポリシロ
キサンを主成分とする上塗り塗料を塗布硬化させた物品
あるいは処理法が開示されている．また特公昭６０−５
３７０１には、熱硬化アクリル道合体と紫外線吸収性化
合物を含有する接着促進性ブライマー層及びこのブライ
マー層上にコロイドシＪ力充填熱硬化オルガノボリシＯ
キサンからなるトップコートを施したポリカーボネート
物品が間示されている．
更に特間昭５９−７８２４０にアルコキシシリル基を有
するアクリルまｋは／およびビニル単量体とこれらの重
量体と共遁合可能な他の単量体との共重合体、及び硬化
触媒を含む熱硬化性組成物を被覆硬化して下塗り層とな
しコロイダルシリカ含有オルガノでボリシロキサンを含
む朝成物を被覆硬化して上塗り層とした耐摩耗性が改善
された被覆ポリカーボネート系樹脂成形物品が提案され
ている．（発明が解決しようとする課８）
しかしながら上述の官能基を含まない下塗り塗膜あるい
は官能基含有熱可塑アクリルボリマーと紫外線吸収剤を
含む下塗り塗膜では、オルガノポリシロキサンを含む上
塗り塗膜の付着耐久性が不充分であり、被覆物品として
の耐候性は充分とは言えない．まｋ熱硬化アクリル重合
体と紫外線吸収性化合物を含有する下塗り塗料について
は、いわゆるポットライフと呼ばれる塗料としての寿命
が短く、またこの下塗り塗膜とコロイドシリカ充填オル
ガノポリシロキサンを含む上塗りＰＡ膜との付着耐久性
も充分満足できるものではない．更にこれらの２層塗膜
系には、ポリカーボネート系基板の光劣化を抑制する目
的で下塗り層に比較的多量の低分子量成分である一般的
な紫外線吸収剤が含まれている．従って下塗り塗膜が形
成された基板上に、通常行なわれている浸漬法では上塗
り塗料を塗布する際に、下塗り塗膜層から紫外線吸収剤
が上塗り塗料中に溶出する．またこの溶出した紫外線吸
収剤の一部は、硬化した上塗り塗膜中に含まれることに
なり、その結果、上塗り塗料及び上塗り塗膜の性能低下
に至る．
（課題を解決するための手段）
本発明は、上述の様な従来の課題を解決することを目的
とするものである．すなわち本発明は、（ａ）アルキル
メタクリレートの重合体、および（ｂ）紫外線吸収剤
を含む組成物を被覆硬化して下塗り層となし、（イ）官
能基を有するアクリルおよび／またはメタクリル単量体
と、
（口〉アルキルアクリレートおよび／まｋはアルキルメ
タクリレート
との共重合体を含み、かつ紫外線吸収剤を含まない組成
物を被覆硬化して中塗り層となし、コロイダルシリカ含
有オルガノポリシロキサンを含む組成物を被覆硬化して
上塗り層となした耐摩耗性及び耐候性が改善された被覆
ポリカーボネート系樹脂成形物品である．
すなわち本発明の特徴は、紫外線吸収剤を含まない中塗
り層を設けた３層皮膜構造とすることによって特に耐久
性が向上した被覆水リカーボネート系樹脂成形物品が得
られることである．本発明において、下塗り用組成物に
用いられるアルキルメタクリレートの重合体とは、メチ
ルメタクリレート、エチルメタクリレート、プロビルメ
タクリレート、プチルメタクリレート等の単一重合体お
よびこれらの共重合体である．このアルキルメタクリレ
ートボリマーの重量平均分子量は、好ましくは１〜５０
万、より好ましくは５〜２０万てある．１万より小さい
とポリカーボネート系樹脂基材への付着耐久性が低下し
、５０万より大きいと塗膜の外観が損なわれ好ましくな
い．本発明の下塗り用組成物に用いられる紫外線吸収剤
としては、２−ヒドロキシ−４−メトキシベンゾフヱノ
ン、２−ヒドロキシ−４−オクトキシベンゾフェノン、
２．４−ジヒドロキシベンゾフェノン、２，２′−ジヒ
ドロキシ−４−メトキシベンゾフェノンなどのペンゾフ
ェノン類；２−（２′−ヒドロキシ−５′−メチルフェ
ニル）ペンゾトリアゾール、２− （２’−ヒドロキシ
−５′−ｔ−プチルフエニル）ペンゾトリアゾール、２
一（２′−ヒドロキシ−６′オクチルフエニル）ベンゾ
トリアゾール、２−（２″−ヒドロキシージーｔ−プチ
ルフェニル〉−６−クロロベンゾトリアゾールなどのペ
ンゾトリアゾール類；エチルー２−シアノー３，３−ジ
フエニルアクリレート、２−エチルへキシル−２−シア
ノー３，３−ジフェニルアクリレート、などのシアノア
クリレート類が挙げられ、なかでもペンゾフエノン類あ
るいはシアノアクリレート類が好ましい．
紫外線吸収剤の添加量は、好ましくは下塗り組成物中の
アルキルメタクリレートポリマ−１００重量部に対して
１〜２００重量部、より好ましくはｌＯ〜ｌ００！置部
である．１１１ｉｌ部未満では、ボリカーボネート系樹
Ｎ基板の光劣化を充分抑制できず、その結果として被覆
物品の耐候性が不充分となりやすい．また２００重量部
を越えると下塗り塗膜の膜強度が弱くなり、結果として
下塗り塗膜層の凝集破壊による付着性不良となりやすく
なる．
下塗り用塗料とするためには上記の２成分に更に溶媒が
加えられる。溶媒としては、メタノール、エタノール、
イソブロバノール、ブタノール、ジアセトンアルコール
などのアルコール類；エチル工一テル、エチレングリコ
ールジメチルエーテル、テトラヒド口フラン、ジオキサ
ン等のエーテル類；メチルセロソルブ、エチルセロソル
ブ、イソブロビルセロソルブ、ブチルセロソルブなどの
セロソルブ類；酢酸エチル、酢酸ブチル、エチレングリ
コールジアセテート、エチルセロソルブアセテートなと
のエステル類：アセトン、メチルエチルケトン、メチル
イソブチルケトンなどのケトン類：ベンゼン、トルエン
、キシレン等の芳香族炭化水素類を挙げることができ、
これらを混合して用いてもよい．
上記の成分からなる下塗り組成物をポリカーボネート樹
脂成形物品の表面に塗布し、得られる塗膜を該樹脂成形
物品の熱変形温度より低い温度で煩き付けることにより
下塗り塗膜が得られる．塗布方法は通常行なわれている
浸漬法、噴霧法、ローラコート法、フローコート法など
であり、焼付けは７０〜１３０℃で２０分〜５時間行な
う．得られる焼付け後の下塗り塗膜の好ましい厚みは０
．１〜６μｍであり、所望の厚みが得られるように塗布
方法、条件に応じて上述した溶媒により下塗り組成物の
固形分が調整されるが、下塗り組成物の固形分はおおむ
ね１〜２０重量％である。Detailed Description of the Invention (Industrial Application Field) The present invention provides a coated polycarbonate resin molded article with excellent abrasion resistance and staining properties, particularly a polycarbonate-based resin molded article that is coated and cured with an undercoat containing a polycarpo external radiation absorber, This article relates to a coated polycarbonate resin molded article with excellent abrasion resistance and weather resistance, which has a three-layer skinned structure, on which an intermediate coat with good adhesion is formed, and a top coat is formed on top of that. ．． (Prior Art) Generally, polycarbonate resins are widely used as transparent plastic materials due to their excellent stability and transparency, but they lack abrasion resistance and solvent resistance and tend to have uneven surfaces. It also has the drawbacks of being easily attacked by organic solvents, and having insufficient light resistance and being prone to yellowing. As a method to improve these drawbacks, two layers, an undercoat and a topcoat, are formed on a polycarbonate resin base material, and at least the first layer contains an ultraviolet absorber, an ultraviolet stabilizer, or an anti-oxidant. Various methods have been proposed for coating with heat, ultraviolet rays, or electron beam curable resins. For example, in Tokuma 196237, an undercoat containing polyalkyl acrylate or polyalkyl methacrylate polymer and an ultraviolet absorber was applied to the surface of polycarbonate, and after drying, the main component was a partially hydrolyzed condensate of alkyltrialkoxysilane. A surface treatment method has been proposed in which a top coat is applied and cured. Japanese Patent Publication No. 55-500858 and Japanese Patent Publication No. 59-24728 disclose an organopolymer film in which an undercoat containing a functional group-containing acrylic polymer and an ultraviolet absorber is applied to the surface of a polycarbonate molded product, and after drying, it is filled with colloidal silica. Disclosed are articles and processing methods in which a top coat containing siloxane as a main component is applied and cured. Also, special public service 1986-5
3701 includes an adhesion-promoting brimer layer containing a thermosetting acrylic compound and an ultraviolet absorbing compound, and a colloidal resin filling thermosetting organoborisil O on this brimer layer.
A polycarbonate article with a top coat of xane is shown. Furthermore, the acrylic resin having an alkoxysilyl group in Tokuma 1982-78240 contains a copolymer of a vinyl monomer and another monomer that can be co-integrated with these weight bodies, and a curing catalyst. A thermosetting composition is coated and cured to form an undercoat layer.A preformed composition containing polysiloxane is coated and cured with a colloidal silica-containing organo to form a topcoat layer.A coated polycarbonate resin molded article with improved abrasion resistance is proposed. It has been done. (Problem 8 to be solved by the invention) However, in the above-mentioned undercoat film containing no functional group or undercoat film containing a functional group-containing thermoplastic acrylic polymer and an ultraviolet absorber, the top coat film containing organopolysiloxane is Adhesion durability is insufficient, and weather resistance as a coated article cannot be said to be sufficient. Undercoat paints containing thermosetting acrylic polymers and ultraviolet absorbing compounds have a short life as a paint, so-called pot life, and the difference between this undercoat film and the topcoat PA film containing colloidal silica-filled organopolysiloxane. The durability of adhesion is also not completely satisfactory. Furthermore, these two-layer coating systems contain a relatively large amount of a common ultraviolet absorber, which is a low molecular weight component, in the undercoat layer for the purpose of suppressing photodeterioration of the polycarbonate substrate. Therefore, when a topcoat is applied to a substrate on which an undercoat has been formed using the commonly used dipping method, the ultraviolet absorber is eluted from the undercoat into the topcoat. In addition, a portion of this eluted ultraviolet absorber will be included in the cured topcoat film, resulting in a decline in the performance of the topcoat paint and topcoat film. (Means for Solving the Problems) The present invention aims to solve the conventional problems as described above. That is, the present invention provides an undercoat layer by coating and curing a composition containing (a) an alkyl methacrylate polymer and (b) an ultraviolet absorber, and (a) an acrylic and/or methacrylic monomer having a functional group. (A) Alkyl acrylate and/or a composition containing a copolymer with alkyl methacrylate and containing no ultraviolet absorber is coated and cured to form an intermediate coating layer, and contains an organopolysiloxane containing colloidal silica. This is a coated polycarbonate resin molded article with improved abrasion resistance and weather resistance, in which the composition is coated and cured to form an overcoat layer.In other words, the feature of the present invention is that an intermediate coat layer that does not contain an ultraviolet absorber is provided. By forming a three-layer film structure, a coated water recarbonate-based resin molded article with particularly improved durability can be obtained.In the present invention, the alkyl methacrylate polymer used in the undercoating composition is methyl methacrylate. , ethyl methacrylate, proyl methacrylate, butyl methacrylate, and copolymers thereof.The weight average molecular weight of this alkyl methacrylate polymer is preferably 1 to 50.
10,000, more preferably 50,000 to 200,000. If it is less than 10,000, the durability of adhesion to the polycarbonate resin base material decreases, and if it is more than 500,000, the appearance of the coating film will be impaired, which is undesirable. The ultraviolet absorbers used in the undercoating composition of the present invention include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone,
2. Penzophenones such as 4-dihydroxybenzophenone and 2,2'-dihydroxy-4-methoxybenzophenone;2-(2'-hydroxy-5'-methylphenyl)penzotriazole,2-(2'-hydroxy-5'-t-butylphenyl)penzotriazole, 2
Penzotriazoles such as 1(2'-hydroxy-6'octylphenyl)benzotriazole, 2-(2''-hydroxy-di-t-butylphenyl)-6-chlorobenzotriazole; ethyl-2-cyano3,3- Examples include cyanoacrylates such as diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, and among them, penzophenones or cyanoacrylates are preferred. The amount of the ultraviolet absorber added is preferably 1 to 200 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the alkyl methacrylate polymer in the undercoat composition, and less than 111 parts will sufficiently suppress photodeterioration of the polycarbonate-based tree N substrate. If the amount exceeds 200 parts by weight, the film strength of the undercoat film will be weakened, resulting in poor adhesion due to cohesive failure of the undercoat film layer. ．To make an undercoat paint, a solvent is added to the above two components.Solvents include methanol, ethanol,
Alcohols such as isobrobanol, butanol, and diacetone alcohol; Ethers such as ethyl alcohol, ethylene glycol dimethyl ether, tetrahydrofuran, and dioxane; Cellosolves such as methyl cellosolve, ethyl cellosolve, isobrovir cellosolve, and butyl cellosolve; ethyl acetate , esters such as butyl acetate, ethylene glycol diacetate, and ethyl cellosolve acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic hydrocarbons such as benzene, toluene, and xylene;
You may use a mixture of these. An undercoat film can be obtained by applying an undercoat composition comprising the above-mentioned components to the surface of a polycarbonate resin molded article and applying the resulting coating film at a temperature lower than the heat deformation temperature of the resin molded article. The coating method is the commonly used dipping method, spraying method, roller coating method, flow coating method, etc., and baking is performed at 70 to 130°C for 20 minutes to 5 hours. The preferred thickness of the resulting undercoat film after baking is 0.
．． The solid content of the undercoat composition is adjusted with the above-mentioned solvent depending on the coating method and conditions to obtain the desired thickness, but the solid content of the undercoat composition is approximately 1 to 20% by weight. It is.
本発明において、中塗りとして用いる官能基を有するア
クリルおよび／またはメタクリル（以下（メタ）アクリ
ルと記す）単量体と、アルキルアクリレートおよび／ま
たはアルキルメタクリレート（以下アルキル（メタ〉ア
クリレートと記す）との共重合体について記す．官能基
を有する（メタ〉アクリル単量体の官能基として、水酸
基、エポキシ基、アルコキシシリル基、カルボキシル基
、アミノ基、メルカブト基およびスルホン酸基が挙げら
れ、これらの基を有する（メタ）アクリル単量体の官能
基として具体的には、ヒドロキシエチル（メタ）アクリ
レート、ヒドロキシプ口ビル（メタ）アクリレート、グ
リシジルメタクリレート、グリシジルエチル（メタ）ア
クリレート、グリシジルブロビル（メタ）アクリレート
、グリシドキシエチル（メタ）アクリレート、グリシド
キシプ口ビル（メタ）アクリレート、γ一（メタ）アク
Ｊロキシブ口ビルトリメトキシシラン、γ−（メタ）ア
クリロキシブロビルトリエトキシシラン、γ一（メタ〉
アクリロキシブ口ビルメチルジメトキシシラン、γ一（
メタ）アクリロキシブ口ビルメチルジエトキシシラン、
γ一（メタ）アクリロキシブ口ビルジメチルメトキシシ
ラン、γ一（メタ）アクリロキシブ口ビルジメチルエト
キシシラン、カルボキシエチル（メタ）アクリレート、
カルボキシブチル（メタ〉アクリレート、アミンエチル
（メタ）アクリレート、アミノブロビル（メタ〉アクリ
レート、メルカブトヘキシル（メタ）アクリレート、ス
ルホキシイソブ口ビル（メタ）アクリレート等が挙げら
れる．これらの中でより好ましい単量体は、水酸基、エ
ポキシ基及びアルコキシシリル基から選ばれる官能基を
すくなくとも１種有する化合物である．共重合体の他の
成分であるアルキル（メタ）アクリレートとしては、メ
チル（メタ）アクリレート、エチル（メタ〉アクリレー
ト、プロビル（メタ〉アクリレート、ブチル（メタ）ア
クリレート、２−エチルヘキシル（メタ）アクリレート
等を挙げることができる．前記官能基を有する（メタ）
アクリル単量体とアルキル（メタ）アクリレートとの共
重合体中には、官能基を有する（メタ〉アクリル単量体
が、１〜７０重量％、好ましくは２〜４０重量％、更に
好ましくは２〜３０１ｉ量％含まれる．含有量が１重量
％より少ないと下塗り塗膜並びにコロイダルシリカ含有
オルガノポリシロキサンを含む上塗り塗膜との付着性が
低下し、７０重量％より多い場合には３層塗膜系にクラ
ックが発生し易くなる．この中塗り層に用いる共重合体
のｉｔ平均分子量は好ましくは１〜５０万、より好まし
くは５〜３０万である．１万より小さいと下塗りおよび
上塗り層に対する付着性が低下し、５０万より大きいと
塗膜の外観が損なわれ好ましくない．中塗り用塗料とす
るためには上記の共通合体に溶媒が加えられる。この溶
媒としては、前記の下塗り用塗料に用いた溶媒を同様に
用いることが出来る．上述した成分からなる中塗り組成
物を下塗り塗膜で被覆されたポリカーボネート系樹脂成
形物品に下塗り塗料の場合と同様の方法で塗布し、７０
〜１３０℃でｌＯ分〜２時間焼付けを行なう．中塗り組
成物の固形分はおおむね１〜２０重量％で、硬化塗膜の
好ましい厚みはＯ．！〜５μｍである．本発明において
は、この中塗り塗料に紫外線吸収剤が実質的に含まれて
いないことが特徴であり、従来の２層系塗膜で認められ
る紫外線吸収剤含有下塗り塗膜からの上塗り塗料あるい
は硬化上塗り塗膜中への紫外線吸収剤の溶出あるいは混
入による性能低下が抑制される．本発明において中塗り
用組成物中の紫外線吸収剤の含有量が上記共重合体１０
０重量部に対して０．１％重量部以下であれば紫外線吸
収剤は含まれていないと定義する。また本発明者らの実
験によるとコロイダルシリカ含有オルガノポリシロキサ
ンを含む剛直な上塗り塗膜層に接する下層のガラス転移
点は、できるだけ高い方が被覆物品として耐久性の向上
が認められた．紫外線吸収剤は可塑剤的機能も有し、こ
れを上塗り塗膜層に接する下層の塗料に添加すればその
硬化塗膜のガラス転移点を低下させるので好ましくない
．本発明においては、下塗り及び後述の上塗りの両塗膜
層に対する付着性が良好でしかも紫外線吸収剤を含まな
い中塗り層を設けた３層皮膜構造とすることによって、
被覆物品としての耐久性が向上する．
本発明において、上塗り用として用いるコロイダルシリ
カ含有オルガノポリシロキサンを含む組成物としては、
好ましくは固形成分で表わしてコロイダルシリカを３〜
７０重量％含む才ルガノボリシロキサンであり、下記（
Ａ）および（Ｂ）から成る群より選ばれる少なくとも！
種、 （Ｃ）および（Ｄ）、
Ｒｂ２
番
（Ａ）一般式（１）Ｒ．’−Ｓ＋− （ＯＲ３） ａ−
ａ−ｂ （１）（式中Ｒ１はエポキシ基を有する有機基
、Ｒ２は水素、または炭素数１〜６の炭化水素基、Ｒ３
は炭素数１〜５の炭化水素基、アルコキシアルキル基ま
たは炭素数１〜４のアシル基、ａは１〜３、ｂはθ〜２
であってａ＋ｂ≦３である．）で示されるエポキシ基を
有する珪素化合物から選ばれる１種もしくは２種以上の
加水分解物．
（Ｂ）一般式（２） Ｒｃ’− Ｓ ＋− （ Ｏ
Ｒ’） ａ−。（２）（式中Ｒ４は炭素数１〜４の炭化
水素基、Ｒ％は炭素数１〜５の炭化水素基、アルコキシ
アルキル基または炭素数１〜４のアシル基、Ｃは０〜３
である．〉で示される有機珪素化合物の加水分解物．（
Ｃ）コロイダルシリカ
および
（Ｄ）硬化触媒
を含む胡成物が好適に使用される．更に好ましくは、
（Ａ）一般式（１）で示されるエポキシ基を有する珪素
化合物から選ばれるＩＮもしくは２種以上の加水分解物
１００ｆｔｌ１部（但し、固形分で計算し、
Ｒ，２
１
Ｒ ．’ − Ｓ ＋ − ０ ＋ａ−ｍ−ｂｗ２とし
て計算する．）（Ｂ）一般式（２）で示される有機珪素
化合物の加水分解物５６〜５５０重量部（但し、固形分
で計算し、
Ｒ−’−Ｓｒ−０（ａ−。）／２として計算する。）（
Ｃ）コロイダルシリカ４〜３３４重量部く但し、固形分
で計算し、ＳｉＯ２として計算する．）ただし（Ｂ）と
（Ｃ）の合計は５６７！量部を越えず、好ましくは６０
〜５６７ｉｉｊｌ部である、および
（Ｄ）硬化触媒
を含む組成物である．
本発明で使用される一般式（１）で示される成分（Ａ）
のエポキシ基を有する珪素化合物としては、下記のよう
な物が挙げられる．グリシドキシ基を１ヶ有する珪素化
合物の具体例としては、グリシドキシメチルトリメトキ
シシラン、グリシドキシメチルトリエトキシシラン、β
−グリシドキシエチルトリメトキシシラン、γ−グリシ
ドキシブ口ビルトリメトキシシラン、γ−グリシドキシ
ブロビルトリ（メトキシエトキシ）シラン、γーグリシ
ドキシブロビルトリアセトキシシラン、δーグリシドキ
シブチルトリメトキシシラン、グリシドキシメチルジメ
トキシシラン、グリシドキシメチル（メチル〉ジメトキ
シシラン、グリシドキシメチル（エチル）ジメトキシシ
ラン、グリシドキシメチル（フエニル）ジメトキシシラ
ン、グリシドキシメチル（ビニル）ジメトキシシラン、
グリシドキシメチル（ジメチル）メトキシシラン、β−
グリシドキシエチル（メチル〉ジメトキシシラン、β−
グリシドキシエチル（ジメチル）メトキシシラン、γ−
グリシドキシプ口ビル（メチル〉ジメトキシシラン、γ
−グリシドキシブ口ビル（ジメチル〉メトキシシラン、
δ−グリシドキシプチル（メチル）ジメトキシシラン、
δ−グリシドキシブチル（ジメチル）メトキシシランを
挙げることができ、
グリシドキシ基を２ヶまたは３ヶ有する珪素化合物の具
体例としては、ビス（グリシドキシメチル）ジメトキシ
シラン、ビス（グリシドキシメチル）ジエトキシシラン
、ビス（グリシドキシエチル〉ジメトキシシラン
ビス（グリシドキシブ口ビル〉ジメトキシシラン、トリ
ス（グリシドキシメチル）メトキシシラン、トリス（グ
リシドキシエチル）メトキシシラン、トリス（グリシド
キシブ口ビル〉メトキシシランを挙げることができ、グ
リシジル基を有する珪素化合物の具体例としては、グリ
シジルメチルトリメトキシシラン、グリシジルメチルト
リエトキシシラン、β−グリシジルエチルトリメトキシ
シラン、γ−グリシジルブ口ビルトリメトキシシラン、
γ−グリシジルブロビルトリ（メトキシェトキシ）シラ
ン、γ−グリシジルプロビルトリアセトキシシランを挙
げることができ、
脂環式エポキシ基を有する珪素化合物の具体例としては
、３．４−エポキシシクロヘキシルメチルトリメトキシ
シラン、３，４−エポキシシク口ヘキシルメチルトリエ
トキシシラン、３，４−エポキシシク口ヘキシルエチル
トリメトキシシラン、３，４−エポキシシクａヘキシル
ブ口ビルトリメトキシシラン、３．４−エポキシシク口
へキシルプチルトリメトキシシラン、等を挙げることが
できる．
本発明で使用される成分（Ｂ）である前記一般式（２）
で示される有機珪素化合物としては、下記のようなもの
が挙げられる．すなわち、トリメチルメトキシシラン、
ジメチルジメトキシシラン、メチルトリメトキシシラン
、テトラエトキシシラン、フエニルトリメトキシシラン
、フェニルメチルジメトキシシラン等がある．成分（Ｃ
）のコロイダルシリカとは、分散媒、たとえば水または
アルコール系分散媒に無水珪酸の好ましくは１〜１００
ミリミクロンの粒径の超微粒子を、分散せしめたコロイ
ド溶液であり、周知の方法で製造され市販されているも
のである．
これら（Ｂ）成分および（Ｃ）成分を（Ａ）成分と併用
することにより、塗膜の耐候性が向上し、かつ嗣候性テ
スト後の外観及び硬度が良好となる。In the present invention, acrylic and/or methacrylic (hereinafter referred to as (meth)acrylic) monomers having a functional group used as an intermediate coating, and alkyl acrylate and/or alkyl methacrylate (hereinafter referred to as alkyl (meth)acrylate) are combined. Regarding copolymers, the functional groups of (meth)acrylic monomers include hydroxyl groups, epoxy groups, alkoxysilyl groups, carboxyl groups, amino groups, mercabuto groups, and sulfonic acid groups. Specifically, as the functional group of the (meth)acrylic monomer having Acrylate, glycidoxyethyl (meth)acrylate, glycidoxyethyl (meth)acrylate, γ-(meth)acryloxybyltrimethoxysilane, γ-(meth)acryloxybrobyltriethoxysilane, γ-(meth)acryloxybrobyltriethoxysilane, 〉
Acryloxibylmethyldimethoxysilane, γ-(
meth)acryloxib-methyldiethoxysilane,
γ-(meth)acryloxib-based dimethylmethoxysilane, γ-(meth)acryloxib-based dimethylethoxysilane, carboxyethyl(meth)acrylate,
Examples include carboxybutyl (meth)acrylate, amine ethyl (meth)acrylate, aminobrobyl (meth)acrylate, mercabutohexyl (meth)acrylate, sulfoxyisobutyl (meth)acrylate, etc. Among these, more preferred monomers are: It is a compound that has at least one functional group selected from hydroxyl group, epoxy group, and alkoxysilyl group.As the alkyl (meth)acrylate that is another component of the copolymer, methyl (meth)acrylate, ethyl (meth)acrylate , proyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.(meth)acrylate having the above-mentioned functional group.
The copolymer of acrylic monomer and alkyl (meth)acrylate contains 1 to 70% by weight, preferably 2 to 40% by weight, more preferably 2 to 40% by weight of the (meth)acrylic monomer having a functional group. If the content is less than 1% by weight, the adhesion with the undercoat film and the topcoat film containing colloidal silica-containing organopolysiloxane will decrease, and if it is more than 70% by weight, three-layer coating will be required. Cracks are likely to occur in the film system.The IT average molecular weight of the copolymer used for this intermediate coating layer is preferably 1 to 500,000, more preferably 5 to 300,000.If it is less than 10,000, it is difficult to use for the undercoat and topcoat layers. If it exceeds 500,000 yen, the appearance of the paint film will be impaired, which is undesirable.A solvent is added to the above-mentioned common compound to form an intermediate coating. The solvent used in the paint can be used in the same way.The intermediate coating composition consisting of the above-mentioned components is applied to the polycarbonate resin molded article coated with the undercoat film in the same manner as for the undercoat paint, and
Bake at ~130°C for ~2 hours. The solid content of the intermediate coating composition is approximately 1 to 20% by weight, and the preferred thickness of the cured coating is O. ! ~5μm. The present invention is characterized in that the intermediate coating does not contain substantially any UV absorber, and the top coat or cured from the UV absorber-containing undercoat, which is recognized in conventional two-layer coatings. Performance deterioration due to elution or incorporation of UV absorbers into the top coat is suppressed. In the present invention, the content of the ultraviolet absorber in the intermediate coating composition is 10% of the above copolymer.
If it is 0.1% weight part or less relative to 0 weight part, it is defined that no ultraviolet absorber is contained. Furthermore, according to experiments conducted by the present inventors, it was found that the durability of the coated article was improved when the glass transition temperature of the lower layer in contact with the rigid topcoat layer containing colloidal silica-containing organopolysiloxane was as high as possible. Ultraviolet absorbers also have a plasticizer function, and if they are added to the lower coating that is in contact with the topcoat layer, it is undesirable because it lowers the glass transition point of the cured coating. In the present invention, by adopting a three-layer film structure including an intermediate coat layer that has good adhesion to both the undercoat layer and the top coat layer described below and does not contain a UV absorber,
Durability as a coated article is improved. In the present invention, the composition containing colloidal silica-containing organopolysiloxane used as a top coat includes:
Preferably, the amount of colloidal silica expressed as a solid component is 3 to 3.
It is a luganoborisiloxane containing 70% by weight, and the following (
At least one selected from the group consisting of A) and (B)!
Species, (C) and (D), Rb2 No. (A) General formula (1) R. '-S+- (OR3) a-
a-b (1) (in the formula, R1 is an organic group having an epoxy group, R2 is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, R3
is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group or an acyl group having 1 to 4 carbon atoms, a is 1 to 3, and b is θ to 2.
and a+b≦3. ) One or more hydrolysates selected from the silicon compounds having epoxy groups. (B) General formula (2) Rc'- S +- ( O
R') a-. (2) (In the formula, R4 is a hydrocarbon group having 1 to 4 carbon atoms, R% is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group, or an acyl group having 1 to 4 carbon atoms, and C is 0 to 3
It is. A hydrolyzate of an organosilicon compound represented by (
C) A colloidal silica and (D) a curing catalyst containing a curing catalyst are preferably used. More preferably,
(A) 1 part of 100 ftl of IN or a hydrolyzate of two or more selected from silicon compounds having an epoxy group represented by the general formula (1) (calculated on solid content, R, 2 1 R .' - S + - 0 + a-m-bw2.) (B) 56 to 550 parts by weight of a hydrolyzate of an organosilicon compound represented by general formula (2) (calculated as solid content, R-'-Sr- Calculate as 0(a-.)/2.)(
C) 4 to 334 parts by weight of colloidal silica, calculated based on solid content and calculated as SiO2. ) However, the total of (B) and (C) is 567! Not exceeding 60 parts, preferably 60 parts
~567iijl parts, and (D) a curing catalyst. Component (A) represented by general formula (1) used in the present invention
Examples of silicon compounds having an epoxy group include the following. Specific examples of silicon compounds having one glycidoxy group include glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, β
-glycidoxyethyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybrobytri(methoxyethoxy)silane, γ-glycidoxybrobytriacetoxysilane, δ-glycidoxybutyltrimethoxysilane Methoxysilane, glycidoxymethyl dimethoxysilane, glycidoxymethyl (methyl) dimethoxysilane, glycidoxymethyl (ethyl) dimethoxysilane, glycidoxymethyl (phenyl) dimethoxysilane, glycidoxymethyl (vinyl) dimethoxysilane,
Glycidoxymethyl(dimethyl)methoxysilane, β-
Glycidoxyethyl (methyl) dimethoxysilane, β-
Glycidoxyethyl(dimethyl)methoxysilane, γ-
Glycidoxypubiru(methyl>dimethoxysilane, γ
- Glycidoxibuvir (dimethyl>methoxysilane,
δ-glycidoxybutyl(methyl)dimethoxysilane,
Specific examples of silicon compounds having two or three glycidoxy groups include δ-glycidoxybutyl(dimethyl)methoxysilane, bis(glycidoxymethyl)dimethoxysilane, bis(glycidoxymethyl) ) Diethoxysilane, Bis(glycidoxyethyl) dimethoxysilane, Bis(glycidoxybuil) dimethoxysilane, Tris(glycidoxymethyl)methoxysilane, Tris(glycidoxyethyl)methoxysilane, Tris(glycidoxyethyl)methoxysilane Examples of silicon compounds having a glycidyl group include glycidylmethyltrimethoxysilane, glycidylmethyltriethoxysilane, β-glycidylethyltrimethoxysilane, γ-glycidyl butyltrimethoxysilane,
Examples of silicon compounds having an alicyclic epoxy group include γ-glycidylbrobyltri(methoxyshethoxy)silane and γ-glycidylprobyltriacetoxysilane. Specific examples of silicon compounds having alicyclic epoxy groups include 3,4-epoxycyclohexylmethyltri Methoxysilane, 3,4-Epoxyhexylmethyltriethoxysilane, 3,4-Epoxyhexylethyltrimethoxysilane, 3,4-Epoxyhexyltrimethoxysilane, 3,4-Epoxyhexylbutyltrimethoxysilane Methoxysilane, etc. can be mentioned. The above general formula (2) which is the component (B) used in the present invention
Examples of organosilicon compounds represented by are as follows. That is, trimethylmethoxysilane,
Examples include dimethyldimethoxysilane, methyltrimethoxysilane, tetraethoxysilane, phenyltrimethoxysilane, and phenylmethyldimethoxysilane. Component (C
) Colloidal silica means a dispersion medium such as water or an alcoholic dispersion medium containing preferably 1 to 100% of silicic anhydride.
This is a colloidal solution in which ultrafine particles with millimicron diameter are dispersed, and it is produced by a well-known method and is commercially available. By using these components (B) and (C) in combination with component (A), the weather resistance of the coating film is improved, and the appearance and hardness after the weathering test are improved.
本発明に於いて成分（Ａ）として用いられる前記一般式
（１）で示されるエポキシ基を有する珪素化合物から遭
ばれる１種もしくは２種以上の加水分解物および成分（
Ｂ）として用いられる前記一般式（２）で示される有機
珪素化合物から選ばれるＩｌ！もしくは２ｆ！以上の加
水分解物とは、該珪素化合物中のアルコキシ基、アルコ
キシアルコキシ基またはアシ口キシ基の一部または全部
が水酸基に置換されたもの及び置換されｋ水酸基同士が
一部自然に縮合したものを含んでいる．これらの加水分
解物は、公知のように例えば水とアルコールのごとき混
合溶媒中、酸の存在下で加水分解することによって得ら
れる．
本発明における上塗り層用のコーティング組成物中の成
分（Ｄ）の硬化触媒としては、次のような触媒を用いる
ことができる．すなわち過塩素酸アンモニウム、過塩素
酸マグネシウム、硝酸アンモニウム、塩化アンモニウム
、硫酸アンモニウム、チオシアン酸アンモニウム、過塩
素酸、塩酸、硝酸、リン酸、硫酸、スルホン酸、パラト
ルエンスルホン酸、３弗化ホウ素及びその電子供与体と
の錯体． ＳｎＣｌ． ＺｎＣ ｈ， ＦｅＣ１
３，ＡＩＣ１３１ ＳｂＣＩｓ，ＴｉＣＩ＊などのル
イス酸及びその錯体．酢酸ナトリウム、ナフテン酸亜鉛
、ナフテン酸コバルト、オクチル酸亜鉛、オクチル酸ス
ズ等の有機酸金属酸塩．ホウ弗化亜鉛、ホウ弗化スズ等
のホウ弗化金属塩類．ホウ酸エチル、ホウ酸メチル等の
ホウ酸有機エステル類．水酸化ナトリウム、水酸化カリ
ウム党のアルカリ類．テトラブトキシチタン、テトライ
ソブロポキシチタン等のチタネートエステル＊． ク
ロムアセチルアセトネート、チタニルアセチルアセトネ
ート、アルミニウムアセチルアセトネート、コバルトア
セチルアセトネート、ニッケルアセチルアセトネート等
の金属アセチルアセトネート類等が挙げられる。In the present invention, one or more hydrolysates and components (
Il! selected from the organosilicon compounds represented by the above general formula (2) used as B)! Or 2f! The above-mentioned hydrolysates are those in which a part or all of the alkoxy, alkoxyalkoxy, or acytoxy groups in the silicon compound are substituted with hydroxyl groups, and those in which some of the substituted hydroxyl groups are naturally condensed with each other. Contains. These hydrolysates can be obtained, for example, by hydrolysis in a mixed solvent such as water and alcohol in the presence of an acid, as is known. As the curing catalyst for component (D) in the coating composition for the top coat layer in the present invention, the following catalysts can be used. Namely ammonium perchlorate, magnesium perchlorate, ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium thiocyanate, perchloric acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, sulfonic acid, para-toluenesulfonic acid, boron trifluoride and its electrons. Complex with donor. SnCl. ZnC h, FeC1
3, AIC131 Lewis acids such as SbCIs and TiCI* and their complexes. Organic acid metal salts such as sodium acetate, zinc naphthenate, cobalt naphthenate, zinc octylate, and tin octylate. Borofluoride metal salts such as zinc borofluoride and tin borofluoride. Boric acid organic esters such as ethyl borate and methyl borate. Alkali such as sodium hydroxide and potassium hydroxide. Titanate esters such as tetrabutoxytitanium and tetraisopropoxytitanium*. Examples include metal acetylacetonates such as chromium acetylacetonate, titanyl acetylacetonate, aluminum acetylacetonate, cobalt acetylacetonate, and nickel acetylacetonate.
これらの硬化触媒の中で塗膜の硬度、透明性等が良好で
、しかも塗料のポットライフが長い硬化触媒として過塩
素酸アンモニウムおよび酢酸ナトリウムが特に適してい
る。これら硬化触媒の添加量は、上塗り用コーティング
組成物の固形分に対して０．０５〜１０重量部％、より
好ましくは０．１〜５＠量部％である。Among these curing catalysts, ammonium perchlorate and sodium acetate are particularly suitable as curing catalysts that provide good coating film hardness, transparency, etc., and have a long paint pot life. The amount of these curing catalysts added is 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on the solid content of the top coating composition.
上塗り用組成物に含ませてよい溶剤としては、アルコー
ル頚、ケトン類、エステル類、エーテル類、セロソルブ
類、ハロゲン化物、カルボン酸類、芳香族化合物等を挙
げることができ、これらの内の１種または２種以上の混
合溶媒として用いることができる．特にメタノール、エ
タノール、プロパノール、イソブロパノール、ブタノー
ル等の低級アルコール：メチルセロソルプ、エチルセロ
ソルブ、プチルセロソルブ等のセロソルブ類：ギ酸、酢
酸、ブロビオン酸等の低級アルキルカルボン酸類： ト
ルエン、キシレン等の芳香族化合物：酢酸エチル、酢酸
プチル等のエステル類；およびアセトン、メチルエチル
ケトン、メチルイソブチルケトンなどのケトン類等を単
独もしくは混合溶剤として用いることが好ましい．
更に必要に応じて平滑な塗膜を得るために弗素系界面活
性剤、アルキレンオキシドとジメチルシロキサンとのブ
ロック共重合体などのフローコントロール剤を添加する
ことができる．これらフローコントロール剤の添加量は
、少量で充分であり上塗り組成物全体に対し０．０１〜
６！量部％、より好ましくは０．０３〜３重量部％であ
る．上塗り塗料のコーティングは、通常行なわれている
漫潰法、ローラコーティング法またはフローコート法等
のコーティング方法によって前述の下塗り塗料および中
塗り塗料をあらかじめ塗布、焼付けされたポリカーボネ
ート系基材にコーティング後７０℃以上で基材の熱変形
（例えば１３０℃）以下の温度で２０分〜５時間焼付け
、硬化させることにより耐摩耗性、付着性、耐熱水性及
び耐候性が良好な塗膜が得られる．
この上塗り塗膜の好ましい厚みは、１〜３０μｍ５
より好ましくは３〜１５μｍである．１μｒｎ以下であ
ると耐摩耗性が充分でなく、また３０μｍ以上になると
クラックが発生し易くなる．本発明が適用できるポリカ
ーボネート系樹脂としては、ビスフェノール型ポリカー
ボネートの他ジエチレングリコールビスアリルカーボネ
ート等が挙げられる。これらは種々の成形品として、例
えば眼鏡レンズ、スキーゴーグル、ドアー、自動車用窓
、間仕切り等として使用される．以下実施例により本発
明を更に詳しく説明するが、本発明はこれらの実施例に
よって限定されるものではない．なお実施例中の部、％
はそれぞれ重量部、重量部％を示す．
また塗膜の性能評価は次の方法にて行なった．すなわち
耐摩耗性： ＃ＯＯＯＯスチールウールで摩擦し傷の付
き難さを調べ次のように判定した。Examples of solvents that may be included in the top coating composition include alcohols, ketones, esters, ethers, cellosolves, halides, carboxylic acids, aromatic compounds, etc. Alternatively, it can be used as a mixed solvent of two or more. In particular, lower alcohols such as methanol, ethanol, propanol, isopropanol, and butanol; Cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; Lower alkyl carboxylic acids such as formic acid, acetic acid, and brobionic acid; Aromatic compounds such as toluene and xylene. : Esters such as ethyl acetate and butyl acetate; and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone are preferably used alone or as a mixed solvent. Furthermore, if necessary, a flow control agent such as a fluorine-based surfactant or a block copolymer of alkylene oxide and dimethylsiloxane may be added to obtain a smooth coating film. A small amount of these flow control agents is sufficient, and the amount of the flow control agent added is 0.01 to 0.01 to the entire top coat composition.
6! % by weight, more preferably 0.03 to 3 parts by weight. Coating with the top coat is done by applying the above-mentioned undercoat and intermediate coat in advance by a commonly used coating method such as the rolling method, roller coating method, or flow coating method, and then coating the baked polycarbonate base material for 70 minutes. By baking and curing for 20 minutes to 5 hours at a temperature above 10°C and below thermal deformation of the base material (for example 130°C), a coating film with good abrasion resistance, adhesion, hot water resistance and weather resistance can be obtained. The preferred thickness of this top coat is 1 to 30 μm5
More preferably, it is 3 to 15 μm. If it is less than 1 μrn, the wear resistance will not be sufficient, and if it is more than 30 μrn, cracks will easily occur. Examples of polycarbonate resins to which the present invention can be applied include diethylene glycol bisallyl carbonate in addition to bisphenol polycarbonate. These are used as various molded products, such as eyeglass lenses, ski goggles, doors, automobile windows, and partitions. The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. In addition, parts and % in examples
indicate parts by weight and % by weight, respectively. The performance of the coating film was evaluated using the following method. That is, abrasion resistance: #OOOO The resistance to scratching by rubbing with steel wool was examined and judged as follows.
八二強く摩擦しても傷がつかない．
Ｂ：強く摩擦すると少し傷がつく
Ｃ：弱いＲＷＩでも傷がつく
付着性：いわゆるクロスカットテーブテストで塗膜表面
にナイフで１ｍ．ｍ間隔で縦横に各１１本の平行線をい
れて１００個のマス目をクロスカットし、そのうえにセ
ロフ？ン粘着チーブを付着させた後、テープを剥離して
ｌＯＯ個のマス目の中で剥離しないマス目の個数をもっ
て表示した．
促進耐候性テスト：デューバネルウエザメーター（スガ
試験機製、以下ＤＰＷＬと記す）にて耐候性を評価した
。82 Even if you rub it hard, it won't get scratched. B: Slight scratches occur when rubbed strongly C: Adhesion that causes scratches even with weak RWI: A 1 m. Cross-cut 100 squares by inserting 11 parallel lines vertically and horizontally at m intervals, and on top of that, Serov? After attaching the adhesive tape, the tape was peeled off and the number of squares that did not peel off among 100 squares was displayed. Accelerated weather resistance test: Weather resistance was evaluated using a Dew Banel Weather Meter (manufactured by Suga Test Instruments, hereinafter referred to as DPWL).
なお紫外＆！照射は、３．５ｍｗ／ｃｍ２７０℃−８時
間．結露は、５５℃−４時間のサイクルで実施した．
（実施例）
各塗料の調製を下記の如く実施した。In addition, ultraviolet &! Irradiation was performed at 3.5 mw/cm at 270°C for 8 hours. Condensation was carried out using a cycle of 55°C for 4 hours. (Example) Each paint was prepared as follows.
（１）下塗り塗料（Ａ−１〜Ａ−４）の！１１１１．（
Ａ−１）：ジアセトンアルコールとエチルセロソルプの
ｌ／１（重量比）混合溶媒にポリメチルメタクリレート
（以下ＰＭＭＡと記す．アルドリッチ社製、重量平均分
子量が約１０万〉を、その固形分が約１０％となるよう
に溶解した．次にペンゾフエノン！！！紫外線吸収剤で
あるバイオソーブー１００（共同薬品社ｍｌ）を、ＰＭ
ＭＡに対し約５０％となるように添加し、下塗り塗料Ａ
−１を調製した．
（Ａ−２）バイオソープ−１００に替え、サイアソープ
ＩＪＶ−２４ （アメリカンサイアナミッド？Ｊ：製）
をＰＭＭＡに対し約３０％となるように添加した以外は
Ａ−１と同様に：ｌ１ｕした．（Ａ−３）バイオソーブ
ー１００に習え、シアノアクリレート系のユビナールＮ
−５３９ （ＧＡＦ社ｌ！）をＰＭＭＡに対し約２０％
となるように添加した以外はＡ−１と同様に調製した。(1) Undercoat paint (A-1 to A-4)! 1111. (
A-1): Polymethyl methacrylate (hereinafter referred to as PMMA, manufactured by Aldrich Co., Ltd., weight average molecular weight is about 100,000) is added to a mixed solvent of diacetone alcohol and ethyl cellosolp at a l/1 (weight ratio), and its solid content is about 10 Next, Penzophenone!!!Biosorb 100 (Kyodo Yakuhin Co., Ltd. ml), which is an ultraviolet absorber, was dissolved in PM
It is added to approximately 50% of MA, and base coat A
-1 was prepared. (A-2) Replace Biosoap-100 with Cyasorp IJV-24 (manufactured by American Cyanamid?J:)
The same procedure as A-1 was carried out except that PMMA was added at a concentration of about 30%. (A-3) Learn from Biosorbu 100, Cyanoacrylate Uvinal N
-539 (GAF company l!) about 20% to PMMA
It was prepared in the same manner as A-1 except that it was added so as to become.
（Ａ−４）ポリエチルメタクリレート（アルドリッチ社
製、重量平均分子量が約３０万）を用いた以外はＡ−２
と同様に！ｌｉｆ製した．（２）中塗り塗料（Ｂ−１−
Ｂ−３）の調製．（Ｂ−１）メチルメタクリレート２５
０部、２ーヒドロキシエチルメタクリレート１１０部、
エチルセロソルブ１４５０部及び開始剤を少々添加し、
窒素雰囲気下、攪拌しながら８０℃で約２０時問、その
後９０℃で約４時間重合した．室温に冷却後エチルセロ
ソルブ１０００部を添加し、固形分約１３％の２元共重
合体を得た．この共重合体の重量平均分子量は、約３０
万で、ガラス転移点は約１２０℃であった．
このようにして得られた共重合体溶液８０部にジアセト
ンアルコール９７部、エチルセロソルブ７０部を添加し
中塗り塗料Ｂ−１とした．（Ｂ−２）プチルセロソルブ
３００部を窒素雰囲ス下で１００℃に保ちつつメチルメ
タクリレート１６０部、グリシジルメタクリレート４０
部、ペンゾイルバーオキサイド２．０部の混合物を３時
間かかって加えさらに３時間同温度に保った．その後プ
チルセロソルブ１１５５部、エチレングリコールジセテ
ート３６０部を加え中塗り塗料Ｂ一２とした．
（Ｂ−３）エチルセロソルブ９００部を窒素雰囲気下で
８５℃に保ちつつメチルメタクリレート４８０部、γ−
グリシドキシブ口ビルトリメトキシシラン１２０部、ペ
ンゾイルバーオキサイド３．Ｏ部の混合物を３時間かか
つて加えその後１０５℃に昇温し４時間保ち重量平均分
子量が約１１万の共重合体を得た．このようにして得ら
れた共重合体溶液８０部にジアセトンアルコール１６０
部、エチルセａソルプ１５０部を添加し、中塗り塗料Ｂ
−３とした．
（３）上塗り塗料（Ｃ− １−Ｃ−３）の調製．（Ｃ−
１）γ−グリシドキシブ口ビルトリメトキシシラン６０
部、メチルトリメトキシシランｌ７３部、コロイダルシ
リカ（日産化学工業（株）製、スノーテックスーＣ１
固形分２０％）７１部および０．１規定酢酸水溶ｆｉ１
９０部を混合し、８０〜８５℃で２時間還流して加水
分解を行なった。(A-4) A-2 except that polyethyl methacrylate (manufactured by Aldrich, weight average molecular weight approximately 300,000) was used.
alike! Manufactured by lif. (2) Intermediate paint (B-1-
Preparation of B-3). (B-1) Methyl methacrylate 25
0 parts, 110 parts of 2-hydroxyethyl methacrylate,
Add 1450 parts of ethyl cellosolve and some initiator,
Polymerization was carried out at 80°C for about 20 hours under a nitrogen atmosphere with stirring, and then at 90°C for about 4 hours. After cooling to room temperature, 1000 parts of ethyl cellosolve was added to obtain a binary copolymer with a solid content of about 13%. The weight average molecular weight of this copolymer is approximately 30
The glass transition temperature was approximately 120°C. 97 parts of diacetone alcohol and 70 parts of ethyl cellosolve were added to 80 parts of the copolymer solution thus obtained to prepare an intermediate coating B-1. (B-2) 160 parts of methyl methacrylate and 40 parts of glycidyl methacrylate while maintaining 300 parts of butyl cellosolve at 100°C under nitrogen atmosphere.
A mixture of 2.0 parts of penzoyl peroxide and 2.0 parts of penzoyl peroxide was added over a period of 3 hours, and the temperature was maintained for an additional 3 hours. Thereafter, 1155 parts of putyl cellosolve and 360 parts of ethylene glycol disetate were added to prepare intermediate coating B-12. (B-3) 480 parts of methyl methacrylate and γ-
120 parts of glycidoxib-biltrimethoxysilane, 3. penzoyl peroxide. A mixture of part O was added once for 3 hours, and then the temperature was raised to 105°C and kept for 4 hours to obtain a copolymer with a weight average molecular weight of about 110,000. Add 160 parts of diacetone alcohol to 80 parts of the copolymer solution thus obtained.
150 parts of Ethylcea Solp was added, and intermediate coating B was applied.
-3. (3) Preparation of top coat paint (C-1-C-3). (C-
1) γ-glycidoxibyltrimethoxysilane 60
73 parts of methyltrimethoxysilane, colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtech Sue C1)
solid content 20%) 71 parts and 0.1N acetic acid aqueous solution fi1
90 parts were mixed and refluxed at 80-85°C for 2 hours to perform hydrolysis.
得られた溶液の固形分組成（計算値）は、（Ｊ１２−Ｃ
ｌ−Ｃｌｌ２−０−ＣｉＨｅ−Ｓｉ−０＋．ｓ とシ
テ計算された０
γ−グリシドキシブ口ビルトリメトキシシラン加水分解
物８．６％、ＣＩＩ３ＳｉＯ＋．ｓとして計算されたメ
チルトリメトキシシラン加水分解物ｌ７，３％及びＳ１
０２として計算されたコロイダルシリカ２．９％を含ん
でいる．
このようにして得られた３元共加水分解物溶液４５０部
にエチルセロソルブ４２部、酢酸ナトリウム１．０部、
フローコントロール剤少々を添加し上塗り塗料Ｃ−１と
した。The solid content composition (calculated value) of the obtained solution was (J12-C
l-Cll2-0-CiHe-Si-0+. s and calculated 0 γ-glycidoxibu-trimethoxysilane hydrolyzate 8.6%, CII3SiO+. Methyltrimethoxysilane hydrolyzate l7.3% and S1 calculated as s
Contains 2.9% colloidal silica calculated as 02. To 450 parts of the ternary cohydrolyzate solution thus obtained, 42 parts of ethyl cellosolve, 1.0 part of sodium acetate,
A small amount of flow control agent was added to obtain top coat C-1.
（Ｃ−２） γ−グリシドキシブ口ビルトリメトキシ
シラン８０部、メチルトリメトキシシラン１４４部、コ
ロイダルシリカ（日産化学工業（株）製、スノーテック
スーＣ，固形分２０％）７１部および０．１規定塩酸水
溶液１７０部を混合し、８０〜８５℃で２時間還流して
加水分解を行なった．得られた溶液の固形分絹成（計算
値）は、ＣＴｏ−ＣＨ−（Ｊ１２−０−Ｃ３１１ｓ−Ｓ
ｉ−０＋．ｓ として計算された０
γ−グリシドキシブロビルトリメトキシシラン加水分解
物１２．２％、ＣｌｈＳｉＯ＋．ｓとして計算されたメ
チルトリメトキシシラン加水分解物１６．３％及びＳｈ
ｏ２として計算されたコロイダルシリカ３．１％を含ん
でいる．
このようにして得られた３元共加水分解物７ｄ ｉｌ！
４１０部にエチルセロソルブ７３部、過塩素酸アンモニ
ウム１．３部、フローコントロール剤少々を添加し上塗
り塗料Ｃ−２とした．
（Ｃ−３）メチルトリメトキシシラン１１０部と氷酢酸
２．０部の混合液にコロイダルシリカ（日産化学工業（
株）製、スノーテックスーＣ、固形分２０％）１８０部
を添加後、４時間攪拌し加水分解を行なった．得られた
溶液の固形分組成（計算１＋ｆｆ）は、ＣｌｈＳｉＯ＋
．ｓとして計算されたメチルトリメトキシシラン加水分
解物１８．５％及びＳ１０２として計算されたコロイダ
ルシリカ１２．３％を含んでいる。(C-2) 80 parts of γ-glycidoxibyltrimethoxysilane, 144 parts of methyltrimethoxysilane, 71 parts of colloidal silica (manufactured by Nissan Chemical Industries, Ltd., Snowtech Sue C, solid content 20%) and 0.1 parts. 170 parts of normal hydrochloric acid aqueous solution was mixed and refluxed at 80 to 85°C for 2 hours to perform hydrolysis. The solid content (calculated value) of the obtained solution was CTo-CH-(J12-0-C311s-S
i-0+. s 0 γ-glycidoxybrobyltrimethoxysilane hydrolyzate 12.2%, ClhSiO+. Methyltrimethoxysilane hydrolyzate 16.3% calculated as s and Sh
Contains 3.1% colloidal silica calculated as o2. The ternary cohydrolyzate thus obtained was 7 d il!
To 410 parts, 73 parts of ethyl cellosolve, 1.3 parts of ammonium perchlorate, and a small amount of flow control agent were added to prepare top coat C-2. (C-3) Colloidal silica (Nissan Chemical Co., Ltd.) is added to a mixed solution of 110 parts of methyltrimethoxysilane and 2.0 parts of glacial acetic acid.
After adding 180 parts of Snowtech Soo C (solid content 20%) manufactured by Co., Ltd., the mixture was stirred for 4 hours to perform hydrolysis. The solid content composition (calculation 1+ff) of the obtained solution is ClhSiO+
．． Contains 18.5% methyltrimethoxysilane hydrolyzate calculated as s and 12.3% colloidal silica calculated as S102.
このようにして得られた２元共加水分解物溶液３００部
にイソブロビルアルコール１５０部添加し室温で約４日
熟成した後、酢酸ナトリウム０．５部を加えて上塗り塗
料Ｃ−３とした。150 parts of isobrobyl alcohol was added to 300 parts of the binary cohydrolyzate solution obtained in this way, and after aging at room temperature for about 4 days, 0.5 part of sodium acetate was added to obtain top coat C-3.
実施例ｌ
あらかじめ洗浄したポリカーボネート基材に下塗り塗料
Ａ−１を塗布し、熱風乾燥炉で１２０℃、３０分間加熱
乾燥しｋ．この下塗り塗膜厚みは、約２μｍでふった．
次にこの様にして得られた下塗り層で被覆されたポリカ
ーボネートに中塗り塗料Ｂ−１を塗布し，熱風乾燥炉で
１２０℃、２０分間加熱屹燥した．この中塗り塗膜厚み
は約１μｍであった．最後に下塗り及び中塗りの２層塗
膜で被覆されたポリカーボネートに上塗り塗料Ｃ一１を
１ｉ布し、熱風乾燥炉で１２０℃、１時問加熱乾燥し、
硬化させた．この上塗り塗膜厚みは、約３μｍであった
．この様にして得られた３Ｎ被覆ポリカーボネート被覆
物品は、透明で耐摩耗性はＡ、付着性は１００／１００
と良好であった．さらにＤＰＷＬテスト５００時間後の
外観に異常は認められず、耐摩耗性、付着性とも良好で
あった．実施例２
あらかじめ洗浄したポリカーボネート基材に下塗り塗料
Ａ−２を塗布し、熱風乾燥炉で１２０℃、３０分間加熱
乾燥した．この下塗り塗膜厚みは、約２．５μｍであっ
た。次にこの様にして得られた下塗り層で被覆されたポ
リカーボネートに中塗り塗科Ｂ−１を塗布し、熱風乾燥
炉で１２０℃、２０分間加熱乾燥した．この中塗り塗膜
厚みは約１μｍであった．Ｉ＆後に下塗り及び中塗りの
２層塗膜で被覆されたポリカーボネートに上塗り塗料Ｃ
一２を塗布し、熱風乾燥炉で１２０℃、１時間加熱乾燥
し、硬化させた．この上塗り塗膜厚みは、約３７ｚｍで
あった．この様にして得られた３層被覆ポリカーボネー
ト被覆物品は、透明で耐摩耗性はＡ、付着性は１００／
１００と良好であった．ざらにＤＰＷＬテスト５５０時
間後の外観に異常は認められず、嗣摩耗性、付着性とも
良好であった．
実施例３
あらかじめ洗浄したポリカーボネート基材に下塗り塗Ｆ
４Ａ−３を塗布し、熱風乾燥炉で１２０℃、３０分間加
熱乾燥した．この下塗り塗膜厚みは、約１。５μｍであ
った．次にこの様にして得られた下塗り層で被覆された
ポリカーボネートに中塗り塗料Ｂ−２を塗布し、熱風乾
燥炉で１２０℃、３０分間加熱乾燥した．この中塗り塗
膜厚みは約２μｍであった．最後に下塗り及び中塗りの
２Ｎ塗膜で被覆されたポリカーボネートに上塗り塗料Ｃ
一１を塗布し、熱風乾燥炉で１２０℃、１時間加熱乾燥
し、硬化させた．この上塗り塗膜厚みは、約３，５μｍ
であった．この様にして得られた３層被覆ポリカーボネ
ート被覆物品は、透明で耐摩耗性はＡ、付着性は１００
／１００と良好であった．ざらにＤＰＷＬテス｝４８０
時間後の外観に異常は認められず、耐摩耗性、付着性と
も良好であった．
実施例４
あらかじめ洗浄したポリカーボネート基材に下塗り塗料
Ａ−４を塗布し、熱風乾燥炉で１２０℃、２０分問加熱
乾燥した．この下塗り塗膜厚みは、約２μｍであった．
次にこの様にして得られた下塗り層で被覆されたポリカ
ーボネートに中塗り塗料Ｂ−１を塗布し、熱風乾燥炉で
１２０℃、！５分間加熱乾燥した．この中塗りｔｊｉ膜
厚みは約１μｍであった．最後に下塗り及び中塗りの２
層塗膜で被覆されたボリカーボネートに上塗り塗料Ｃ−
１を塗布し、熱風乾燥炉で１２０℃、１時間加熱乾燥し
、硬化させた．この上塗り塗膜厚みは、約３．５μｍで
あった．この様にして得られた３Ｆ’被覆ポリカーボネ
ート被覆物品は、透明で耐摩耗性はＡ、付着性は１００
／１００と良好であった．さらにＤＰＷＬテスト４６０
時間後の外観に異常は認められず、耐摩耗性、付着性と
も良好であった。Example 1 Undercoat paint A-1 was applied to a polycarbonate substrate that had been washed in advance, and dried by heating at 120°C for 30 minutes in a hot air drying oven.k. The thickness of this undercoat film was approximately 2 μm.
Next, intermediate coating B-1 was applied to the polycarbonate coated with the undercoat layer thus obtained, and the mixture was heated and dried in a hot air drying oven at 120°C for 20 minutes. The thickness of this intermediate coating film was approximately 1 μm. Finally, 1 i coat of top coat C-1 was applied to the polycarbonate coated with the two-layer coating film of undercoat and intermediate coat, and dried by heating at 120°C for 1 hour in a hot air drying oven.
Hardened. The thickness of this topcoat film was approximately 3 μm. The 3N-coated polycarbonate coated article thus obtained is transparent, has an abrasion resistance of A, and has an adhesion of 100/100.
It was good. Furthermore, no abnormality was observed in the appearance after 500 hours of DPWL test, and both wear resistance and adhesion were good. Example 2 Undercoat paint A-2 was applied to a polycarbonate base material that had been washed in advance, and was dried by heating at 120° C. for 30 minutes in a hot air drying oven. The thickness of this undercoat film was approximately 2.5 μm. Next, intermediate coat B-1 was applied to the polycarbonate coated with the undercoat layer thus obtained, and the mixture was heated and dried in a hot air drying oven at 120°C for 20 minutes. The thickness of this intermediate coating film was approximately 1 μm. Topcoat C on polycarbonate coated with two layers of undercoat and intermediate coat
No. 1-2 was applied and dried by heating at 120°C for 1 hour in a hot air drying oven to cure. The thickness of this topcoat film was approximately 37 zm. The thus obtained three-layer polycarbonate coated article is transparent, has an abrasion resistance of A, and an adhesion of 100/
It was good at 100. Roughly speaking, no abnormality was observed in the appearance after 550 hours of the DPWL test, and both the wear resistance and adhesion were good. Example 3 Undercoat F on pre-cleaned polycarbonate substrate
4A-3 was applied and dried by heating at 120°C for 30 minutes in a hot air drying oven. The thickness of this undercoat film was approximately 1.5 μm. Next, intermediate coating B-2 was applied to the polycarbonate coated with the undercoat layer thus obtained, and the mixture was heated and dried in a hot air drying oven at 120°C for 30 minutes. The thickness of this intermediate coating film was approximately 2 μm. Finally, top coat C is applied to the polycarbonate coated with the 2N undercoat and intermediate coat.
No. 11 was applied and dried by heating at 120°C for 1 hour in a hot air drying oven to cure. The thickness of this top coat is approximately 3.5 μm.
Met. The thus obtained three-layer polycarbonate coated article is transparent, has an abrasion resistance of A, and an adhesion of 100.
/100, which was good. Zara DPWL Test}480
No abnormalities were observed in the appearance after a period of time, and both wear resistance and adhesion were good. Example 4 Undercoating paint A-4 was applied to a polycarbonate base material that had been washed in advance, and the paint was dried by heating at 120°C for 20 minutes in a hot air drying oven. The thickness of this undercoat film was approximately 2 μm.
Next, intermediate coating B-1 was applied to the polycarbonate coated with the undercoat layer obtained in this manner, and the mixture was dried at 120°C in a hot air drying oven! It was heated and dried for 5 minutes. The thickness of this intermediate coating TJI film was approximately 1 μm. Finally, undercoat and intermediate coat 2
Polycarbonate coated with layer coating film is coated with top coat C-
1 was applied and dried by heating at 120°C for 1 hour in a hot air drying oven to cure. The thickness of this topcoat film was approximately 3.5 μm. The 3F'-coated polycarbonate coated article thus obtained is transparent, has an abrasion resistance of A, and an adhesion of 100.
/100, which was good. Further DPWL test 460
No abnormality was observed in the appearance after a period of time, and both abrasion resistance and adhesion were good.
実施例５
あらかじめ洗浄したポリカーボネート基材に下塗り塗料
Ａ−１を塗布し、熱風乾燥炉で１２０℃、３０分間加熱
乾燥した．この下塗り塗膜厚みは、約２μｍであった．
次にこの様にして得られた下塗り層で被覆されたボリカ
ーボネートに中塗り塗料Ｂ−３を塗布し、熱風乾燥炉で
１２０℃、１６分間加熱乾燥しｋ．この中塗り塗膜厚み
は約０．７μｍであった．最後に下塗り及び中塗りの２
層塗膜で被覆されｋボリカーボネートに上塗り塗料Ｃ一
２を塗布し、熱風乾燥炉で１２０℃、１時間加熱乾燥し
、硬化させた．この上塗り塗膜厚みは、約３μｍであっ
た．この様にして得られｋ３層被覆ポリカーボネート被
覆物品は、透明で耐摩耗性はＡ、付着性は１００／１０
０と良好であった．ざらにＤＰＷＬテス｝５００時間後
の外観に異常は認められず、耐摩耗性、付着性とも良好
であった．
実施例６
あらかじめ洗浄したポリカーボネート基材に下塗り塗料
Ａ−２を塗布し、熱風乾燥炉で１２０℃、３０分問加熱
乾燥した．この下塗り塗膜厚みは、約２μｍであった．
次にこの様にして得られた下塗り層で被覆されたポリカ
ーボネートに中塗り塗科Ｂ−３を塗布し、熱風乾燥炉で
１２０℃、１５分間加熱乾燥した．この中塗り塗膜厚み
は約１．５μｍであった．最後に下塗り及び中塗りの２
層塗膜で被覆されたポリカーボネートに上塗り塗料Ｃ一
３を塗布し、妨風乾燥炉で１２０℃、１時間加熱乾燥し
、硬化させた．この上塗り塗膜厚みは、約３μｍであっ
た．この様にして得られた３層被覆ポリカーボネート被
覆物品は、透明で耐摩耗性はＡ，付着性は１ ００／１
００と良好であった．さらにＤＰＷＬテスト５００時
間後の外観に異常は認められず、耐摩耗性、付着性とも
良好であった．
比較例１
中塗り層を設けなかった以外は実施例ｌと同様に作製し
た２層被覆ポリカーボネート成形物品は透明で外銭に異
常は認められなかったが、初期付着性が不充分であった
．
比較例２
（１）下塗り塗料の調製：紫外線吸収剤を添加しない以
外は、下塗り塗料Ａ−１と同様に！ＰＩ％！した．
（２）中塗り塗料の！１１１１１：中塗り塗科Ｂ−１に
前記紫外線吸収剤であるバイオソーブー１００を共重合
対固形分に対し５０％添加し中塗り塗料とした．尚この
中塗り塗料硬化物のガラス転移点は、約２０℃であった
．
あらかじめ洗浄しｋボリカーボネート基材に上記下塗り
塗料塗布し、熱風乾燥炉で１２０℃、３０分間加熱乾燥
した．この下塗り７ｉ膜厚みは、約２μｍであった．次
にこの様にして得られた下塗り層で被覆されたポリカー
ボネートに上記中塗り塗料を塗布し、熱風乾燥炉で１２
０℃、１５分間加熱乾燥した．この中塗り塗膜厚みは約
２μｍであった．最後に下塗り及び中塗りの２層塗膜で
被覆されたポリカーボネートに上塗り塗林Ｃ−１を漫潰
塗布し、熱風乾燥炉で１２０℃、１時間加熱乾燥し、硬
化させた．この上塗り塗膜厚みは、約３μｍであった．
この様にして得られた３層被覆ポリカーボネート被覆物
品は、透明で耐摩耗性はＡ、付着性は１００／１００と
良好であったがＤＰＷＬテスト３００時間後クラックの
発生が認められ、また耐摩耗性もＣであった．
更に上塗り塗料塗布時に、上塗り塗料中への中塗り塗膜
から紫外線吸収剤の溶出が戎察された．比較例３
あらかじめ洗浄したポリカーボネート基材に下塗り塗料
Ａ−３を塗布し、熱風乾燥炉で１２０℃、３０分間加熱
乾燥しｋ．この下塗り塗膜厚みは、約２μｍであった。Example 5 Undercoat paint A-1 was applied to a polycarbonate base material that had been washed in advance, and was dried by heating at 120° C. for 30 minutes in a hot air drying oven. The thickness of this undercoat film was approximately 2 μm.
Next, intermediate coating B-3 was applied to the polycarbonate coated with the undercoat layer obtained in this manner, and the mixture was dried by heating at 120°C for 16 minutes in a hot air drying oven.k. The thickness of this intermediate coating film was approximately 0.7 μm. Finally, undercoat and intermediate coat 2
Topcoat C-2 was applied to the K polycarbonate coated with the layer coating film, and dried by heating at 120° C. for 1 hour in a hot air drying oven to cure. The thickness of this topcoat film was approximately 3 μm. The thus obtained K3 layer coated polycarbonate coated article is transparent, has an abrasion resistance of A, and has an adhesion of 100/10.
The score was 0, which was good. Rough DPWL test} No abnormality was observed in the appearance after 500 hours, and both abrasion resistance and adhesion were good. Example 6 Undercoat paint A-2 was applied to a polycarbonate base material that had been washed in advance, and the paint was dried by heating at 120° C. for 30 minutes in a hot air drying oven. The thickness of this undercoat film was approximately 2 μm.
Next, intermediate coat B-3 was applied to the polycarbonate coated with the undercoat layer thus obtained, and the polycarbonate was dried by heating at 120° C. for 15 minutes in a hot air drying oven. The thickness of this intermediate coating film was approximately 1.5 μm. Finally, undercoat and intermediate coat 2
Topcoat C-13 was applied to the polycarbonate coated with the layer coating film, and dried by heating at 120° C. for 1 hour in a blast drying oven to cure. The thickness of this topcoat film was approximately 3 μm. The thus obtained three-layer coated polycarbonate coated article is transparent, has an abrasion resistance of A, and an adhesion of 100/1.
00, which was good. Furthermore, no abnormality was observed in the appearance after 500 hours of DPWL test, and both wear resistance and adhesion were good. Comparative Example 1 A two-layer coated polycarbonate molded article prepared in the same manner as in Example 1 except that an intermediate coating layer was not provided was transparent and no abnormality was observed on the outer surface, but the initial adhesion was insufficient. Comparative Example 2 (1) Preparation of undercoat paint: Same as undercoat paint A-1 except that no ultraviolet absorber was added! PI%! did. (2) Intermediate paint! 11111: The UV absorber Biosorb 100 was added to intermediate coating B-1 in an amount of 50% based on the solid content of the copolymer to prepare an intermediate coating. The glass transition point of this cured intermediate coating was approximately 20°C. The above undercoat paint was applied to the K-polycarbonate substrate which had been washed in advance, and then heated and dried in a hot air drying oven at 120°C for 30 minutes. The thickness of this undercoat 7i film was approximately 2 μm. Next, the above intermediate coating paint was applied to the polycarbonate coated with the undercoat layer obtained in this way, and the mixture was dried in a hot air drying oven for 12 hours.
It was dried by heating at 0°C for 15 minutes. The thickness of this intermediate coating film was approximately 2 μm. Finally, topcoat Coorin C-1 was coated on the polycarbonate coated with the two-layer coating film of undercoat and intermediate coat, and was heated and dried in a hot air drying oven at 120°C for 1 hour to cure. The thickness of this topcoat film was approximately 3 μm.
The three-layer polycarbonate coated article obtained in this way was transparent, had abrasion resistance of A, and had good adhesion of 100/100, but cracks were observed after 300 hours of the DPWL test, and the abrasion resistance was 100/100. The gender was also C. Furthermore, during the application of the top coat, it was observed that UV absorbers were leached from the intermediate coat into the top coat. Comparative Example 3 Undercoat paint A-3 was applied to a polycarbonate substrate that had been washed in advance, and dried by heating at 120° C. for 30 minutes in a hot air drying oven. The thickness of this undercoat film was approximately 2 μm.
次にこの様にして得られた下塗り層で被覆されたポリカ
ーボネートに中塗り層を施さずに上塗り塗料Ｃ−３を塗
布し、熱風乾燥炉で１２０℃、１時間加熱乾燥し、硬化
させた．この上塗り塗膜厚みは、約３μｍであった。こ
の様にして得られた２層被覆ポリカーボネート被覆物品
は、透明で耐摩耗性はＡ、付着性は１００／１００と良
好であったが、ＤＰＷＬテスト２８０時間後にブリスタ
ー及び一部に膜剥がれが認められた．Next, topcoat C-3 was applied to the polycarbonate coated with the undercoat layer obtained in this manner without applying an intermediate coat layer, and the coating was dried by heating at 120° C. for 1 hour in a hot air drying oven to cure. The thickness of this topcoat film was about 3 μm. The thus obtained two-layer polycarbonate coated article was transparent, had abrasion resistance of A, and had good adhesion of 100/100, but blisters and some film peeling were observed after 280 hours of the DPWL test. It was done.
Claims (6)
能基を有するアクリルおよび／またはメタクリル単量体
と、 （ロ）アルキルアクリレートおよび／またはアルキルメ
タクリレート との共重合体を含み、かつ紫外線吸収剤を含まな￥い￥
組成物を被覆硬化して中塗り層となし、コロイダルシリ
カ含有オルガノポリシロキサンを含む組成物を被覆硬化
して上塗り層となした耐摩耗性及び耐候性が改善された
被覆ポリカーボネート系樹脂成形物品。(1) A composition containing (a) an alkyl methacrylate polymer and (b) an ultraviolet absorber is coated and cured to form an undercoat layer, (a) an acrylic and/or methacrylic monomer having a functional group, (b) Contains a copolymer with alkyl acrylate and/or alkyl methacrylate and does not contain a UV absorber
A coated polycarbonate resin molded article having improved abrasion resistance and weather resistance, comprising an intermediate coating layer formed by coating and curing a composition, and a top coating layer formed by coating and curing a composition containing an organopolysiloxane containing colloidal silica.
官能基が、水酸基、エポキシ基、およびアルコキシシリ
ル基から選ばれるすくなくとも１種である特許請求の範
囲第１項記載の被覆ポリカーボネート系樹脂成形物品。(2) The coated polycarbonate resin molded article according to claim 1, wherein the functional group of the acrylic and/or methacrylic monomer is at least one selected from hydroxyl group, epoxy group, and alkoxysilyl group.
び／またはメタクリル単量体を１〜７０重量％含有する
特許請求の範囲第１項記載の被覆ポリカーボネート系樹
脂成形物品。(3) The coated polycarbonate resin molded article according to claim 1, wherein the copolymer contains 1 to 70% by weight of the acrylic and/or methacrylic monomer having the functional group.
の重合体１００重量部に対して紫外線吸収剤１〜２００
重量部を含む特許請求の範囲第１項記載の被覆ポリカー
ボネート系樹脂成形物品。(4) The undercoating composition contains 1 to 200 parts of an ultraviolet absorber per 100 parts by weight of the alkyl methacrylate polymer.
The coated polycarbonate resin molded article according to claim 1, which contains parts by weight.
ンを含む上塗り用組成物が、下記（Ａ）および（Ｂ）か
ら成る群から選ばれる少なくとも１種、（Ｃ）ならびに
（Ｄ）、を含む組成物である特許請求の範囲第１項記載
の被覆ポリカーボネート系樹脂成形物品。 （Ａ）一般式（１）▲数式、化学式、表等があります▼
（１） （式中Ｒ＾１はエポキシ基を有する有機基、Ｒ＾２は水
素、炭素数１〜６の炭化水素基、Ｒ＾３は炭素数１〜５
の炭化水素基、アルコキシアルキル基または炭素数１〜
４のアシル基、ａは１〜３、ｂは０〜２であってａ＋ｂ
≦３である。）で示されるエポキシ基を有する珪素化合
物から選ばれる１種もしくは２種以上の加水分解物。 （Ｂ）一般式（２）Ｒ＿Ｃ＾４−Ｓｉ−（ＯＲ＾５）＿
４＿−＿Ｃ（２）（式中Ｒ＾４は炭素数１〜４の炭化水
素基、Ｒ＾５は炭素数１〜５の炭化水素基、アルコキシ
アルキル基または炭素数１〜４のアシル基、Ｃは０〜３
である。）で示される有機珪素化合物の加水分解物。 （Ｃ）コロイダルシリカ および （Ｄ）硬化触媒(5) The top coating composition containing the colloidal silica-containing organopolysiloxane is a composition containing at least one member selected from the group consisting of the following (A) and (B), (C) and (D). A coated polycarbonate resin molded article according to claim 1. (A) General formula (1) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼
(1) (In the formula, R^1 is an organic group having an epoxy group, R^2 is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and R^3 is an organic group having 1 to 5 carbon atoms.
hydrocarbon group, alkoxyalkyl group or carbon number 1 to
4 acyl group, a is 1 to 3, b is 0 to 2, and a+b
≦3. ) One or more hydrolysates selected from silicon compounds having an epoxy group represented by: (B) General formula (2) R_C^4-Si-(OR^5)_
4_-_C(2) (in the formula, R^4 is a hydrocarbon group having 1 to 4 carbon atoms, R^5 is a hydrocarbon group having 1 to 5 carbon atoms, an alkoxyalkyl group or an acyl group having 1 to 4 carbon atoms, C is 0-3
It is. ) A hydrolyzate of an organosilicon compound. (C) Colloidal silica and (D) curing catalyst
００重量部（但し、固形分で計算し、▲数式、化学式、
表等があります▼として計算する。）、 上記（Ｂ）加水分解物５６〜５５０重量部（但し、固形
分で計算し Ｒ＿Ｃ＾４−Ｓｉ−Ｏ＿（＿４＿−＿Ｃ＿）＿／＿２と
して計算する。）上記（Ｃ）コロイダルシリカ４〜３３
４重量部（但し、固形分で計算し、ＳｉＯ＿２として計
算する。 ）ただし（Ｂ）と（Ｃ）の合計は５６７重量部を越えず
、好ましくは６０〜５６７重量部である、および 上記（Ｄ）硬化触媒を、上塗り用コーティング組成物の
固形分に対して０．０５〜１０重量部％、を含む組成物
である特許請求の範囲第５項記載の被覆ポリカーボネー
ト系樹脂成形物品。(6) The above-mentioned top coating composition is the above-mentioned (A) hydrolyzate 1
00 parts by weight (calculated based on solid content, ▲ mathematical formula, chemical formula,
There are tables etc. Calculate as ▼. ), 56 to 550 parts by weight of the (B) hydrolyzate (calculated based on solid content as R_C^4-Si-O_(_4_-_C_)_/_2), the above (C) colloidal silica 4 to 33
4 parts by weight (calculated based on solid content and calculated as SiO_2) However, the total of (B) and (C) does not exceed 567 parts by weight, preferably 60 to 567 parts by weight, and the above (D 6. The coated polycarbonate resin molded article according to claim 5, which is a composition containing a curing catalyst in an amount of 0.05 to 10 parts by weight based on the solid content of the top coating composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1308646A JPH03168227A (en) | 1989-11-28 | 1989-11-28 | Coated polycarbonate-based resin molded article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1308646A JPH03168227A (en) | 1989-11-28 | 1989-11-28 | Coated polycarbonate-based resin molded article |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03168227A true JPH03168227A (en) | 1991-07-22 |
Family
ID=17983572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1308646A Pending JPH03168227A (en) | 1989-11-28 | 1989-11-28 | Coated polycarbonate-based resin molded article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03168227A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0428540A (en) * | 1990-05-25 | 1992-01-31 | Nissan Motor Co Ltd | Topcoating film |
| JP2003039621A (en) * | 2001-07-31 | 2003-02-13 | Dainippon Plastics Co Ltd | Polycarbonate resin plate excellent in antifouling property |
| WO2003016389A1 (en) * | 2001-08-20 | 2003-02-27 | General Electric Company | Flame retardant polycarbonate compositions with improved weathering performance containing cyanoacrylic esters |
| WO2012046784A1 (en) * | 2010-10-05 | 2012-04-12 | 旭硝子株式会社 | Resin substrate having hard coat film attached thereto, and process for production thereof |
| EP2517878A4 (en) * | 2009-12-25 | 2013-07-31 | Asahi Glass Co Ltd | Resin substrate with hard coat and process for production thereof |
-
1989
- 1989-11-28 JP JP1308646A patent/JPH03168227A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0428540A (en) * | 1990-05-25 | 1992-01-31 | Nissan Motor Co Ltd | Topcoating film |
| JP2003039621A (en) * | 2001-07-31 | 2003-02-13 | Dainippon Plastics Co Ltd | Polycarbonate resin plate excellent in antifouling property |
| WO2003016389A1 (en) * | 2001-08-20 | 2003-02-27 | General Electric Company | Flame retardant polycarbonate compositions with improved weathering performance containing cyanoacrylic esters |
| US6753367B2 (en) | 2001-08-20 | 2004-06-22 | General Electric Company | Flame retardant polycarbonate compositions with improved weathering performance containing cyanoacrylic esters |
| KR100880314B1 (en) | 2001-08-20 | 2009-01-28 | 사빅 이노베이티브 플라스틱스 아이피 비.브이. | Flame retardant polycarbonate compositions with improved weathering performance containing cyanoacrylic esters |
| EP2517878A4 (en) * | 2009-12-25 | 2013-07-31 | Asahi Glass Co Ltd | Resin substrate with hard coat and process for production thereof |
| US8609230B2 (en) | 2009-12-25 | 2013-12-17 | Asahi Glass Company, Limited | Resin substrate provided with hard coating film and its production process |
| WO2012046784A1 (en) * | 2010-10-05 | 2012-04-12 | 旭硝子株式会社 | Resin substrate having hard coat film attached thereto, and process for production thereof |
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