JP2004025726A - Polycarbonate resin laminate excellent in actual exposure weartherability - Google Patents
Polycarbonate resin laminate excellent in actual exposure weartherability Download PDFInfo
- Publication number
- JP2004025726A JP2004025726A JP2002187969A JP2002187969A JP2004025726A JP 2004025726 A JP2004025726 A JP 2004025726A JP 2002187969 A JP2002187969 A JP 2002187969A JP 2002187969 A JP2002187969 A JP 2002187969A JP 2004025726 A JP2004025726 A JP 2004025726A
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- Japan
- Prior art keywords
- layer
- concentration
- hydroxy
- polycarbonate resin
- compound
- 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.)
- Granted
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- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 37
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 45
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 27
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000008119 colloidal silica Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- 238000002835 absorbance Methods 0.000 claims abstract description 15
- 125000005375 organosiloxane group Chemical group 0.000 claims abstract description 13
- 230000003287 optical effect Effects 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 abstract description 18
- 238000000576 coating method Methods 0.000 abstract description 18
- 229920003023 plastic Polymers 0.000 abstract description 12
- 238000005299 abrasion Methods 0.000 abstract description 7
- 239000004033 plastic Substances 0.000 abstract description 5
- 238000010030 laminating Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 77
- -1 alkyl methacrylate Chemical compound 0.000 description 26
- 239000005056 polyisocyanate Substances 0.000 description 26
- 229920001228 polyisocyanate Polymers 0.000 description 26
- 238000000034 method Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 18
- 239000000178 monomer Substances 0.000 description 16
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 14
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 14
- TUKWPCXMNZAXLO-UHFFFAOYSA-N ethyl 2-nonylsulfanyl-4-oxo-1h-pyrimidine-6-carboxylate Chemical compound CCCCCCCCCSC1=NC(=O)C=C(C(=O)OCC)N1 TUKWPCXMNZAXLO-UHFFFAOYSA-N 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- 229920000515 polycarbonate Polymers 0.000 description 11
- 239000004417 polycarbonate Substances 0.000 description 11
- 239000002243 precursor Substances 0.000 description 11
- 239000002253 acid Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 229920001187 thermosetting polymer Polymers 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000003618 dip coating Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 239000008199 coating composition Substances 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 235000011054 acetic acid Nutrition 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-UHFFFAOYSA-N 0.000 description 3
- VCYCUECVHJJFIQ-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 VCYCUECVHJJFIQ-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 3
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 102100026735 Coagulation factor VIII Human genes 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000012696 Interfacial polycondensation Methods 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 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
- 230000007423 decrease Effects 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000001226 reprecipitation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-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
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-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
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- YEYCMBWKTZNPDH-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) benzoate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1=CC=CC=C1 YEYCMBWKTZNPDH-UHFFFAOYSA-N 0.000 description 1
- ZSRKUPSCNJJDFH-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) octanoate Chemical compound CCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 ZSRKUPSCNJJDFH-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- VNFXPOAMRORRJJ-UHFFFAOYSA-N (4-octylphenyl) 2-hydroxybenzoate Chemical compound C1=CC(CCCCCCCC)=CC=C1OC(=O)C1=CC=CC=C1O VNFXPOAMRORRJJ-UHFFFAOYSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
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- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
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- IAJNXBNRYMEYAZ-UHFFFAOYSA-N ethyl 2-cyano-3,3-diphenylprop-2-enoate Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC)C1=CC=CC=C1 IAJNXBNRYMEYAZ-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 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 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000002650 laminated plastic Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 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
- GMMWKYSAFBYKHU-UHFFFAOYSA-N octylsulfanylbenzene Chemical compound CCCCCCCCSC1=CC=CC=C1 GMMWKYSAFBYKHU-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- KYZSYWQFNQBTLU-UHFFFAOYSA-N phenyl bis(2,2,6,6-tetramethylpiperidin-4-yl) phosphite Chemical compound C1C(C)(C)NC(C)(C)CC1OP(OC=1C=CC=CC=1)OC1CC(C)(C)NC(C)(C)C1 KYZSYWQFNQBTLU-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BCQMBFHBDZVHKU-UHFFFAOYSA-N terbumeton Chemical compound CCNC1=NC(NC(C)(C)C)=NC(OC)=N1 BCQMBFHBDZVHKU-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
【0001】
【発明の属する技術分野】
本発明は表面を保護されたポリカーボネート樹脂積層体に関する。さらに詳しくはポリカーボネート樹脂に特定性能を持った紫外線吸収基を有する化合物を添加及び/又は共重合により導入されたアクリル樹脂層とオルガノシロキサン樹脂の硬化物層とを順次積層することにより、実曝による耐候性に対しての耐久性が著しく改善された、ポリカーボネート樹脂積層体に関する。
【0002】
【従来の技術】
プラスチック材料は、耐衝撃性、軽量性、加工性等の特長を生かして、多方面の用途で使用されている。特に、透明プラスチックであるアクリル樹脂、ポリカーボネート樹脂、スチレン系樹脂等はガラスの代替として幅広く利用されている。しかし、これらの樹脂は耐候性が十分ではなく、長期の屋外の使用において分解・劣化するため物性、外観が損われることが知られている。近年、その軽量性、安全性を活かして窓ガラス、殊に自動車の窓ガラスに有機ガラスとして透明プラスチックシートを適用しようとする動きがある。このような用途に透明プラスチックシートを適用する場合、ガラス並の高度な耐候性が要求される。また、前面ガラスではワイパー作動時のすり傷発生を防止する必要があり、サイドウィンドーではウィンドー昇降時のすり傷発生を防止する必要がある。このような用途では高いレベルの耐摩耗性が要求される。
【0003】
これらの欠点を改良する目的で、従来からプラスチック表面に熱硬化型アクリル樹脂層を設け、さらにその上にシロキサン系の硬化被膜を被覆することにより耐候性、耐久性、耐摩耗性を改良する数多くの提案がなされてきている。
【0004】
例えば、特公平3−65383号公報にはアルコキシシリル基を有するアクリル及び/又はビニル単量体と共重合可能な他の単量体との共重合体、硬化触媒及び架橋剤を含む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ポリシロキサンを含む組成物を上塗り塗料とするコーティング組成物が提案されており、この組成物でポリカーボネート樹脂成形品を被覆することによって、耐摩耗性の優れた被覆ポリカーボネート樹脂成形品が得られている。しかし、添加した紫外線吸収剤量に対して、促進試験では十分な耐候性が得られているが、実曝では予想より下回る耐候性しか得られない事、膜厚によって耐候性にバラツキがあること等の問題があり、実曝にあった紫外線吸収剤種及び濃度の選定、適正な膜厚の設計による、実曝での良好な耐候性を持ったポリカーボネート積層体が求められている。
【0005】
【発明が解決しようとする課題】
本発明の目的は高い実曝耐候性を付与しうる硬化被膜で表面を保護された、耐摩耗性にも優れた性能を有するプラスチック成形体を提供することにある。
【0006】
本発明者らは、この目的を達成するために鋭意研究を重ねた結果、ポリカーボネートの最大劣化波長が290nmであるため、290nm付近に吸収能の強い紫外線吸収剤を好んで使用されているのに対して、実曝の太陽光スペクトルが300nm以下はオゾン層によりほとんどカットされる事に注目し、300nmの吸収能をある範囲以上持った紫外線吸収基を有する化合物を添加及び/又は共重合により導入されたアクリル樹脂層を特定の膜厚で積層し、オルガノシロキサン樹脂の硬化物層を順次積層することにより、実曝による耐候性に対しての耐久性が著しく改善された透明ポリカーボネート樹脂積層体が得られることを見出し、本発明に到達した。
【0007】
【課題を解決するための手段】
すなわち、本発明によれば、透明ポリカーボネート樹脂板の少なくとも一面に、アクリル樹脂層(第一層)とコロイダルシリカ含有オルガノシロキサン樹脂を含む組成物硬化層(第二層)の2層が順次積層された積層体であって、該積層体の第一層が下記式(1)〜(3)を満足し、かつ濃度10mg/Lのクロロホルム溶液、光路長1.0cmで測定した、波長300nmにおける吸光度が0.25以上である紫外線吸収能を有する化合物を含有することを特徴とする実曝耐候性に優れたポリカーボネート樹脂積層体が提供される。
2≦d≦8・・・(1)
0.1≦c≦0.5・・・(2)
0.6≦d×c≦3・・・(3)
(但し、ここでdはμmで表された第一層膜厚であり、cは該層中のg/cm3で表された紫外線吸収能を有する化合物に由来する単位の濃度である)
【0008】
本発明で用いられる第一層のアクリル樹脂層に関して、本発明でいう「第一層中に紫外線吸収能を有する化合物を含有する」とは、「第一層中に紫外線吸収基を有する化合物を添加する及び/又は第一層中のアクリル樹脂中に紫外線吸収基を有する化合物を共重合して導入すること」を意味する。
【0009】
本発明で用いられる第一層のアクリル樹脂は、ポリカーボネート基板及び第二層のコロイダルシリカ含有オルガノシロキサン樹脂を含む硬化被膜と良好な密着性を示すものであれば特に限定しない。例えばアルキルメタクリレートモノマーとヒドロキシ基を有するアクリレートモノマーを共重合して得られるヒドロキシ基を有するアクリル樹脂に架橋剤としてポリイソシアネート化合物やトリアルコキシシラン加水分解物を溶剤に混合し、加熱硬化させたものや、アルキルメタクリレートモノマーとヒドロキシ基を有するアクリレートモノマーおよび紫外線吸収残基を有するアクリレートモノマーを共重合して得られるヒドロキシ基を有するアクリル樹脂に架橋剤としてポリイソシアネート化合物やトリアルコキシシラン加水分解物を溶剤に混合し、加熱硬化させたもの等が挙げられる。中でも硬化させたものが好ましい。更に(A)下記式(1)
【0010】
【化1】
【0011】
(但し、式中R1は炭素数1〜4のアルキル基である。)
で示される繰り返し単位を50モル%以上含むアクリル樹脂、
(B)ポリイソシアネート化合物および/またはポリイソシアネート化合物前駆体からの硬化アクリル樹脂が塗液安定性等の特性が優れ好ましい。このアクリル樹脂の具体的例は50モル%以上のアルキルメタクリレートモノマーと50モル%以下のビニル系モノマーを重合して得られるポリマーがあげられる。アルキルメタクリレートモノマーとしては、メチルメタクリレート、エチルメタクリレート、プロピルメタクリレートおよびブチルメタクリレートが挙げられ、これらは単独または2種以上を混合して使用できる。なかでもメチルメタクリレートおよびエチルメタクリレートが好ましい。また、他のビニル系モノマーとしてはアルキルメタクリレートモノマーと共重合可能なものであり、殊に接着性あるいは耐候性等の耐久性の面で、アクリル酸、メタクリル酸またはそれらの誘導体が好ましく使用される。具体的にはアクリル酸、メタクリル酸、アクリル酸アミド、メタクリル酸アミド、メチルアクリレート、エチルアクリレート、プロピルアクリレート、ブチルアクリレート、2−エチルヘキシルメタクリレート、ドデシルメタクリレート、2−ヒドロキシエチルアクリレート、2−ヒドロキシエチルメタクリレート、2−ヒドロキシプロピルメタクリレート、N,N−ジエチルアミノエチルメタクリレート、グリシジルメタクリレート、3−メタクリロキシプロピルトリメトキシシラン、3−メタクリロキシプロピルトリエトキシシラン、3−メタクリロキシプロピルメチルジメトキシシラン、2−(2′−ヒドロキシ−5−メタクリロキシエチルフェニル)−2H−ベンゾトリアゾール、2−(2′−ヒドロキシ−5−アクリロキシエチルフェニル)−2H−ベンゾトリアゾール等が挙げられ、これらは単独または2種以上を混合して使用できる。また、アクリル樹脂の2種以上を混合した混合物であってもよい。
【0012】
また、かかるアクリル樹脂は、熱硬化型であることが好ましく、0.01モル%〜50モル%の架橋性の反応基を持つビニル系モノマーを含有することが望ましい。かかる架橋性の反応基を持つビニル系モノマーとしてはアクリル酸、メタクリル酸、2−ヒドロキシエチルアクリレート、2−ヒドロキシエチルメタクリレート、2−ヒドロキシプロピルメタクリレート、ビニルトリメトキシシラン、3−メタクリロキシプロピルトリメトキシシラン、3−メタクリロキシプロピルトリエトキシシラン、3−メタクリロキシプロピルメチルジメトキシシラン等が挙げられる。
【0013】
なかでも、架橋性の反応基をもつビニル系モノマーとして2−ヒドロキシエチルアクリレート、2−ヒドロキシエチルメタクリレート、2−ヒドロキシプロピルメタクリレート等の水酸基をもつアクリルモノマーを利用し、架橋剤としてポリイソシアネート化合物もしくはその誘導体を生成するポリイソシアネート化合物前駆体を利用した熱硬化型ウレタンアクリル樹脂を好ましく使用することができる。
【0014】
上記アクリル樹脂の分子量は、重量平均分子量で20,000以上が好ましく、50,000以上がより好ましく、また、重量平均分子量で1千万以下のものが好ましく使用される。かかる分子量範囲の上記アクリル樹脂は、第一層としての密着性や強度などの性能が十分に発揮され好ましい。
【0015】
本発明に用いる上記塗膜樹脂(第一層)を形成する方法としては、アクリル樹脂等の塗膜樹脂成分および後述する光安定剤や紫外線吸収剤等の添加成分を、基材である透明プラスチックと反応したり該透明プラスチックを溶解したりしない揮発性の溶媒に溶解して、このコーティング組成物を透明プラスチック基材表面に塗布し、次いで該溶媒を加熱等により除去することにより行われる。必要であれば溶媒の除去後にさらに40〜140℃に加熱して架橋性基を架橋させることも好ましく行われる。
【0016】
かかる溶媒としてはアセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類、テトラヒドロフラン、1,4−ジオキサン、1,2−ジメトキシエタン等のエーテル類、酢酸エチル、酢酸エトキシエチル等のエステル類、メタノール、エタノール、1−プロパノール、2−プロパノール、1−ブタノール、2−ブタノール、2−メチル−1−プロパノール、2−エトキシエタノール、4−メチル−2−ペンタノール、2−ブトキシエタノール等のアルコール類、n−ヘキサン、n−ヘプタン、イソオクタン、ベンゼン、トルエン、キシレン、ガソリン、軽油、灯油等の炭化水素類、アセトニトリル、ニトロメタン、水等が挙げられ、これらは単独で使用してもよいし2種以上を混合して使用してもよい。かかるコーティング組成物中の塗膜樹脂からなる固形分の濃度は1〜50重量%が好ましく、3〜30重量%がより好ましい。
【0017】
前記の硬化アクリル樹脂用のポリイソシアネート化合物としては、例えばトリレンジイソシアネート、4,4−ジフェニルメタンジイソシアネート、1,5−ナフタレンジイソシアネート、トリフェニルメタントリイソシアネート、トリジンジイソシアネート、キシレンジイソシアネート、リジンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、ダイマー酸ジイソシアネート、ヘキサメチレンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネート、またはこれらのポリイソシアネート化合物と多価アルコール、低分子量ポリエステル樹脂との付加物、あるいは上記したポリイソシアネート化合物同士の環化重合体、さらにはイソシアネート・ビュレット体等が挙げられ、なかでもヘキサメチレンジイソシアネート、イソホロンジイソシアネート等の脂肪族および脂環族のポリイソシアネート化合物や脂肪族および/または脂環族ポリイソシアネート化合物と多価アルコール、低分子量ポリエステル樹脂との付加物、脂肪族ポリイソシアネート化合物同志の環化重合体などが特に耐候性が優れ好ましい。
【0018】
前記の硬化アクリル樹脂用のポリイソシアネート化合物前駆体としては、上記ポリイソシアネート化合物のイソシアネート基にアセトオキシム、メチルエチルケトオキシム等のオキシム類マロン酸ジメチル、マロン酸ジエチル、アセト酢酸メチル、アセト酢酸エチル、アセチルアセトン等の活性メチレン化合物、メタノール、エタノール、2−プロパノール、n−ブタノール、sec−ブタノール、2−エチル−1−ヘキサノール等のアルコール類、フェノール、クレゾール、エチルフェノール等のフェノール類に代表されるブロック化剤を付加させ、熱分解によりポリイソシアネート化合物を生成するブロックイソシアネート化合物が挙げられる。このブロックイソシアネートは熱硬化反応時に初めてイソシアネート基が生成するので塗料組成物の貯蔵安定性に優れ、またイソシアネート基が副反応に消費されることが少なく、特に好ましく使用される。上記ポリイソシアネート化合物およびポリイソシアネート化合物前駆体は単独もしくは2種類以上を混合して使用できる。
【0019】
またポリイソシアネート化合物および/またはポリイソシアネート化合物前駆体の初期および/または生成するイソシアネート基の含有率は好ましく5.0〜60重量%、より好ましくは6.0〜55重量%、最も好ましくは6.0〜50重量%である。イソシアネート基含有率が5.0重量%未満であるとアクリル樹脂に対するポリイソシアネート化合物および/またはポリイソシアネート化合物前駆体の配合量が多くなり、塗膜樹脂中の前記式(1)で表される繰返し単位の割合が低下するため、プラスチック基材との密着性が乏しくなる。また60重量%より多くなると塗膜層の可撓性が低下し、第二層を熱硬化する際に塗膜層にクラックが生じたり、環境の変化に対する耐久性を損うため好ましくない。
【0020】
本発明でいう初期イソシアネート基とは、例えば上記で例示したポリイソシアネート化合物の如く分子末端にフリーに存在しているイソシアネート基であり、また生成するイソシアネート基とは、例えばブロック化剤でイソシアネート基がブロックされているブロックイソシアネート化合物の如くブロックが熱分解し、その時生成されるポリイソシアネート化合物のイソシアネート基である。
【0021】
前記ヒドロキシ基を有するアクリル樹脂と前記ポリイソシアネート化合物もしくはその誘導体またはポリイソシアネート化合物前駆体との混合量比は(A)のアクリル樹脂のヒドロキシ基1当量に対して、(B)の初期および生成するイソシアネート基の総量が好ましくは0.6〜2.0当量、より好ましくは0.7〜1.75当量、最も好ましくは0.8〜1.5当量である。このような組成に調製することで、かかるアクリル樹脂からなる層は透明プラスチック基材および第二層のオルガノシロキサン樹脂熱硬化層との良好な密着性を保つことができ、また、高水準の架橋密度を持つので紫外線や水、酸素による架橋密度の低下を引き起こしにくく、長期にわたる密着性、環境変化および高温環境下での耐久性を維持でき耐候性に優れる。
【0022】
上記アクリル樹脂中に添加及び/又は第共重合により導入される紫外線吸収基を有する化合物は、濃度10mg/Lのクロロホルム溶液、光路長1.0cmで測定した、波長300nmにおける吸光度が0.25以上であれば特に限定されるものではない。具体的には、2,4−ジヒドロキシベンゾフェノン、2−ヒドロキシー4−オクトキシベンゾフェノン、2−ヒドロキシー4−メトキシベンゾフェノン等のベンゾフェノン類、2−(5′−メチル−2′−ヒドロキシフェニル)ベンゾトリアゾール、2−(2H−ベンゾトリアゾール−2−イル)4−6−ビス(1−メチルー1フェニルエチル)フェノール、2−(3′−t−ブチル−5′−メチル−2′−ヒドロキシフェニル)ベンゾトリアゾール、2−(3′,5′−ジ−t−ブチル−2′−ヒドロキシフェニル)−5−クロロベンゾトリアゾール等のベンゾトリアゾール類、エチル−2−シアノ−3,3−ジフェニルアクリレート、2−エチルヘキシル−2−シアノ−3,3−ジフェニルアクリレート等のシアノアクリレート類、フェニルサリシレート、p−オクチルフェニルサリシレート等のサリシレート類、ジエチル−p−メトキシベンジリデンマロネート、ビス(2−エチルヘキシル)ベンジリデンマロネート等のベンジリデンマロネート類が挙げられる。これらの剤は単独もしくは2種以上を併用してもよく、アクリル樹脂との相溶性や、溶剤との溶解性が(2)式の範囲で使用可能なものを選択することができる。
【0023】
また、アクリル樹脂と共重合可能な紫外線吸収基を有するアクリレートまたはメタクリレートモノマーで濃度10mg/Lのクロロホルム溶液、光路長1.0cmで測定した、波長300nmにおける吸光度が0.25以上であるものとしては、具体的には2−(2′−ヒドロキシ−5′−アクリロキシエチルフェニル)ベンゾトリアゾール、2−(2′−ヒドロキシ−5′−アクリロキシエトキシフェニル)ベンゾトリアゾール、2−(2′−ヒドロキシ−5′−アクリロキシプロピルフェニル)ベンゾトリアゾール、2−(2′−ヒドロキシ−5′−アクリロキシプロポキシフェニル)ベンゾトリアゾール、2−(2′−ヒドロキシ−5′−アクリロキシエチルフェニル)−5−クロロベンゾトリアゾール、2−(2′−ヒドロキシ−3′−アクリロキシエチル−5′−t−ブチルフェニル)ベンゾトリアゾール、2−(2′−ヒドロキシ−3′−アクリロキシエチル−5′−t−ブチルフェニル)−5−クロロベンゾトリアゾール、2−ヒドロキシ−4−(アクリロキシエトキシ)ベンゾフェノン、2−ヒドロキシ−4−(アクリロキシプロポキシ)ベンゾフェノン、2,2′−ジヒドロキシ−4−(アクリロキシエトキシ)ベンゾフェノン、2−ヒドロキシ−4−(アクリロイルオキシエチル)ベンゾフェノン、2−(2′−ヒドロキシ−5′−メタクリロキシエチルフェニル)ベンゾトリアゾール、2−(2′−ヒドロキシ−5′−メタクリロキシエトキシフェニル)ベンゾトリアゾール、2−(2′−ヒドロキシ−5′−メタクリロキシプロピルフェニル)ベンゾトリアゾール、2−(2′−ヒドロキシ−5′−メタクリロキシプロポキシフェニル)ベンゾトリアゾール、2−(2′−ヒドロキシ−5′−メタクリロキシエチルフェニル)−5−クロロベンゾトリアゾール、2−(2′−ヒドロキシ−3′−メタクリロキシエチル−5′−t−ブチルフェニル)ベンゾトリアゾール、2−(2′−ヒドロキシ−3′−メタクリロキシエチル−5′−t−ブチルフェニル)−5−クロロベンゾトリアゾール、2−ヒドロキシ−4−(メタクリロキシエトキシ)ベンゾフェノン、2−ヒドロキシ−4−(メタクリロキシプロポキシ)ベンゾフェノン、2,2′−ジヒドロキシ−4−(メタクリロキシエトキシ)ベンゾフェノン、2−ヒドロキシ−4−(メタクリロイルオキシエチル)ベンゾフェノン等が挙げられる。
【0024】
上記の紫外線吸収基を有する化合物が、第一層中に添加及び/又は第一層中のアクリル樹脂中に共重合により導入された加熱硬化した第一層の膜厚d(μm)は、2≦d≦8、好ましくは3≦d≦5で、膜厚が2μm未満であると第二層膜にクラックが発生したり密着性を低下させるため耐候性が乏しくなる。膜厚が8μmより厚くなると熱硬化時の架橋反応が十分進行せず、高湿度下で白化したり密着性の低下を起こしたりする、耐久性に乏しい塗膜層になる。また、上記の紫外線吸収能を有する化合物の第一層中の濃度c(g/cm3)は、0.1≦c≦0.5、好ましくは0.2≦c≦0.4で、濃度が0.1g/cm3未満であると、紫外線の透過率が高くなり基材の黄変が生じたり密着性を低下させるため耐候性が乏しくなり、0.5g/cm3を超えると、ポリカーボネート基材若しくは第二層との密着性が著しく低下し、実曝時に塗膜の自然剥離を起こしやすくなる。良好な実曝耐候性を得るには、上記d×cが、0.6≦d×c≦3、好ましくは0.8≦d×c≦2で、d×cが0.6以下であると紫外線の透過率が高くなり基材の黄変が生じたり密着性を低下させるため耐候性が乏しくなり、3を超えると、ポリカーボネート基材若しくは第二層との密着性が著しく低下し、実曝時に塗膜の自然剥離を起こしやすくなる。
【0025】
第一層に用いるアクリル樹脂層には必要に応じ硬化触媒、光安定剤、シランカップリング剤を添加することができる。
【0026】
光安定剤としては、例えばビス(2,2,6,6−テトラメチル−4−ピペリジル)カーボネート、ビス(2,2,6,6−テトラメチル−4−ピペリジル)サクシネート、ビス(2,2,6,6−テトラメチル−4−ピペリジル)セバケート、4−ベンゾイルオキシ−2,2,6,6−テトラメチルピペリジン、4−オクタノイルオキシ−2,2,6,6−テトラメチルピペリジン、ビス(2,2,6,6−テトラメチル−4−ピペリジル)ジフェニルメタン−p,p′−ジカーバメート、ビス(2,2,6,6−テトラメチル−4−ピペリジル)ベンゼン−1,3−ジスルホネート、ビス(2,2,6,6−テトラメチル−4−ピペリジル)フェニルホスファイト等のヒンダードアミン類、ニッケルビス(オクチルフェニルサルファイド、ニッケルコンプレクス−3,5−ジ−t−ブチル−4−ヒドロキシベンジルリン酸モノエチラート、ニッケルジブチルジチオカーバメート等のニッケル錯体が挙げられる。これらの剤は単独もしくは2種以上を併用してもよく、実曝耐候性に良好な効果を付与できる場合がある。
【0027】
シランカップリング剤としては、γ−(2−アミノエチル)アミノプロピルトリメトキシシラン、γ−(2−アミノエチル)アミノプロピルメチルジメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、N−β−(N−ビニルベンジルアミノエチル)−γ−アミノプロピルトリメトキシシラン・塩酸塩、γ−グリシドキシプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、ビニルトリアセトキシシラン、γ−アニリノプロピルトリメトキシシラン、ビニルトリメトキシシラン、オクタデシルジメチル〔3−(トリメトキシシリル)プロピル〕アンモニウムクロライド、γ−ウレイドプロピルトリエトキシシラン等が挙げられ、また上記シランカップリング剤の部分加水分解縮合物も使用できる。かかる剤を添加することにより、ポリカーボネート基材と第一層および第一層と第二層の密着力が長期にわたり持続される。これらの剤は単独もしくは2種以上を併用しても良い。
【0028】
本発明で用いられる第二層のコロイダルシリカ含有オルガノシロキサン樹脂を含む組成物は、第一層のアクリル樹脂の硬化被膜と良好な密着性を示すものであれば特に限定しない。例えばコロイダルシリカ、トリアルコキシシランの加水分解縮合物からなるオルガノシロキサン樹脂が好ましく、特にコロイダルシリカ、トリアルコキシシランの加水分解縮合物およびテトラアルコキシシランの加水分解縮合物からなるオルガノシロキサン樹脂が好ましい。
【0029】
かかるコロイダルシリカ(以下、a成分と称することがある)は、直径5〜200nm、好ましくは5〜40nmのシリカ微粒子が水または有機溶媒中にコロイド状に分散されたものである。該コロイダルシリカは、水分散型および有機溶媒分散型のどちらでも使用できるが、水分散型のものを用いるのが好ましい。水分散型のコロイダルシリカの場合、シリカ微粒子の表面に多数の水酸基が存在し、これがトリアルコキシシラン加水分解縮合物と強固に結合するため、より耐摩耗性に優れたプラスチック積層体が得られるものと考えられる。
【0030】
また、水分散型コロイダルシリカはさらに酸性水溶液分散型と塩基性水溶液分散型に分かれる。該水分散型コロイダルシリカは酸性水溶液分散型と塩基性水溶液分散型のどちらでも使用できるが硬化触媒選択の多様性、メチルトリアルコキシシランの適切な加水分解、縮合状態の実現の観点から酸性水溶液分散型コロイダルシリカが好ましく使用される。
【0031】
かかるコロイダルシリカとして、具体的には、酸性水溶液中で分散させた商品として日産化学工業(株)のスノーテックスO、触媒化成工業(株)のカタロイドSN、塩基性水溶液中で分散させた商品として日産化学工業(株)のスノーテックス30、スノーテックス40、触媒化成工業(株)のカタロイドS30、カタロイドS40、有機溶剤に分散させた商品として日産化学工業(株)のMA−ST、IPA−ST、NBA−ST、IBA−ST、EG−ST、XBA−ST、NPC−ST、DMAC−ST、触媒化成工業(株)のOSCAL1132、OSCAL1232、OSCAL1332、OSCAL1432、OSCAL1532、OSCAL1632、OSCAL1732等が挙げられる。
【0032】
アルコキシシランの加水分解縮合物(以下、b成分と称することがある)は、例えばテトラメトキシシラン、テトラエトキシシラン、テトラ−n−プロポキシシシラン、テトライソプロポキシシラン、テトラ−n−ブトキシシラン、テトライソブトキシシラン、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、イソブチルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、β−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、N−β(アミノエチル)−γ−アミノプロピルトリメトキシシラン、N−β(アミノエチル)−γ−アミノプロピルトリエトキシシラン、ジメチルジメトキシシラン、ビニルメチルジメトキシシラン、3−メタクリロキシプロピルメチルジメトキシシラン、3−グリシドキシプロピルメチルジメトキシシラン、3−アミノプロピルメチルジエトキシシラン等が挙げられ、なかでもアルキルトリアルコキシシランが好ましく、特にメチルトリメトキシシランおよびメチルトリエトキシシランが好ましい。これらは単独もしくは混合して使用できる。
【0033】
該オルガノシロキサン樹脂組成物は例えば以下のプロセスを経て調製される。ただし、本発明は以下のプロセスに限定されるものではない。
【0034】
コロイダルシリカ分散液中でアルコキシシランを酸性条件下加水分解縮合反応させる。
【0035】
ここで、アルコキシシランの加水分解反応に必要な水は水分散型のコロイダルシリカ分散液を使用した場合はこの分散液から供給され、必要であればさらに水を加えてもよい。アルコキシシラン1当量に対して通常1〜10当量、好ましくは1.5〜7当量、さらに好ましくは3〜5当量の水が用いられる。
【0036】
前述のようにトリアルコキシシランの加水分解縮合反応は、酸性条件下で行う必要がある。かかる条件で加水分解を行なうために一般的には加水分解剤として酸が使用される。かかる酸は、予めアルコキシシランまたはコロイダルシリカ分散液に添加するか、両者を混合後に添加してもよい。また、該添加は1回或いは2回以上に分けることもできる。また酸性水溶液分散型コロイダルシリカを用いる場合、コロイダルシリカ中の酸が反応液を酸性条件下に保つので酸の使用は必ずしも必要ない。かかる酸としては塩酸、硫酸、硝酸、リン酸、亜硝酸、過塩素酸、スルファミン酸等の無機酸、ギ酸、酢酸、プロピオン酸、酪酸、シュウ酸、コハク酸、マレイン酸、乳酸、パラトルエンスルホン酸等の有機酸が挙げられ、pHのコントロールの容易さの観点からギ酸、酢酸、プロピオン酸、酪酸、シュウ酸、コハク酸、マレイン酸等の有機カルボン酸が好ましく、酢酸が特に好ましい。
【0037】
かかる酸として無機酸を使用する場合は通常0.0001〜2mol/l、好ましくは0.001〜0.1mol/lの濃度で使用し、有機酸を使用する場合はメチルトリアルコキシシラン100重量部に対して0.1〜50重量部、好ましくは1〜30重量部の範囲で使用される。
【0038】
アルコキシシランの加水分解、縮合反応の条件は使用するアルコキシシランの種類、系中に共存するコロイダルシリカの種類、量によって変化するので一概には云えないが、通常、系の温度が20〜40℃、反応時間が1時間〜数日間である。アルコキシシランの加水分解反応は発熱反応だが、系の温度は最高でも60℃を超えないことが望ましい。このような条件で十分に加水分解反応を進行させた上で、コート剤の安定化のため40〜80℃で1時間〜数日間縮合反応を進行させることも好ましく行われる。
【0039】
本発明において、オルガノシロキサン樹脂固形分であるa、b成分の各成分の混合割合はオルガノシロキサン樹脂組成物の安定性、得られる硬化膜の透明性、耐摩耗性、耐擦傷性、密着性及びクラック発生の有無等の点から決められ、a成分、b成分の合計100重量%としたとき、この2成分の好ましい混合割合はa成分が10〜60重量%、b成分がR2 mR3 nSiO(4−m−n)/2(但し、R2、R3はそれぞれ炭素数1〜4のアルキル基、ビニル基、またはメタクリロキシ基、アミノ基、グリシドキシ基、3,4−エポキシシクロヘキシル基からなる群から選ばれる1以上の基で置換された炭素数1〜3のアルキル基であり、m、nはそれぞれ0、1、2のいずれかの整数であり、m+nは0、1、2のいずれかの整数である)に換算して40〜90重量%、好ましくはa成分が10〜40重量%、b成分がR2 mR3 nSiO(4−m−n)/2に換算して60〜90重量%である。
【0040】
第二層の厚みは、通常2〜10μm、好ましくは3〜8μmである。コート層の厚みがかかる範囲であると、熱硬化時に発生する応力のためにコート層にクラックが発生したり、コート層と基材との密着性が低下したりすることがなく、本発明の目的とする十分な耐摩耗性を有するコート層が得られることとなる。
【0041】
上記第一層および第二層のポリカーボネート基材への塗布はバーコート法、ディップコート法、フローコート法、スプレーコート法、スピンコート法、ローラーコート法等の方法を、塗装される基材の形状に応じて適宜選択することができる。
【0042】
本発明で使用されるポリカーボネート樹脂は、二価フェノールとカーボネート前駆体とを界面重縮合法または溶融法等で反応させて得られるポリカーボネート樹脂である。二価フェノールの代表的な例としては、2,2−ビス(4−ヒドロキシフェニル)プロパン(通称ビスフェノールA)、2,2−ビス(3−メチル−4−ヒドロキシフェニル)プロパン、2,2−ビス(3,5−ジメチル−4−ヒドロキシフェニル)プロパン、1,1−ビス(4−ヒドロキシフェニル)エタン、1,1−ビス(4−ヒドロキシフェニル)シクロヘキサン、2,2−ビス(4−ヒドロキシフェニル)ブタン、2,2−ビス(4−ヒドロキシフェニル)−3−メチルブタン、9,9−ビス{(4−ヒドロキシ−3−メチル)フェニル}フルオレン、2,2−ビス(4−ヒドロキシフェニル)−3,3−ジメチルブタン、2,2−ビス(4−ヒドロキシフェニル)−4−メチルペンタン、1,1−ビス(4−ヒドロキシフェニル)−3,3,5−トリメチルシクロヘキサンおよびα,α’−ビス(4−ヒドロキシフェニル)−m−ジイソプロピルベンゼン、ビス(4−ヒドロキシフェニル)サルファイド、ビス(4−ヒドロキシフェニル)スルホン等を挙げられ、なかでもビスフェノールAが好ましい。これらの二価フェノールは単独または2種以上を混合して使用できる。
【0043】
ポリカーボネート前駆体としてはカルボニルハライド、カーボネートエステルまたはハロホルメート等が使用され、具体的にはホスゲン、ジフェニルカーボネートまたは二価フェノールのジハロホルメート等が挙げられる。
【0044】
上記二価フェノールとカーボネート前駆体を界面重縮合法または溶融法によって反応させてポリカーボネート樹脂を製造するに当っては、必要に応じて触媒、末端停止剤、二価フェノールの酸化防止剤等を使用してもよい。またポリカーボネート樹脂は三官能以上の多官能性芳香族化合物を共重合した分岐ポリカーボネート樹脂であっても、芳香族または脂肪族の二官能性カルボン酸を共重合したポリエステルカーボネート樹脂であってもよく、また、得られたポリカーボネート樹脂の2種以上を混合した混合物であってもよい。
【0045】
ホスゲンを使用する界面重縮合法は、酸結合剤及び有機溶媒の存在下で反応させる。酸結合剤としては例えば水酸化ナトリウムや水酸化カリウム等のアルカリ金属水酸化物又はピリジン等のアミン化合物が用いられ、溶媒としては例えば塩化メチレン、クロロベンゼン等のハロゲン化炭化水素が用いられる。また反応促進のために例えば第三級アミン又は第四級アンモニウム塩等の触媒を用いることもできる。反応温度は通常0〜40℃であり、反応時間は数分〜5時間である。また、ジフェニルカーボネートを用いる溶融法は、不活性ガス雰囲気下所定割合の二価フェノール成分とジフェニルカーボネートとを加熱しながら攪拌して、生成するアルコール又はフェノール類を留出させる方法により行われる。反応温度は生成するアルコール又はフェノール類の沸点等により異なるが、通常120〜300℃の範囲である。反応はその初期から減圧にして生成するアルコール又はフェノール類を留出させながら完結させる。また、反応を促進するために通常のエステル交換反応用触媒を使用することもできる。
【0046】
ポリカーボネート樹脂の分子量は、粘度平均分子量(M)で10,000〜50,000が好ましく、15,000〜35,000がより好ましい。かかる粘度平均分子量を有するポリカーボネート樹脂は、十分な強度が得られ、また、成形時の溶融流動性も良好であり好ましい。本発明でいう粘度平均分子量は塩化メチレン100mlにポリカーボネート樹脂0.7gを20℃で溶解した溶液から求めた比粘度(ηsp)を次式に挿入して求めたものである。
ηsp/c=[η]+0.45×[η]2c(但し[η]は極限粘度)
[η]=1.23×10−4M0.83
c=0.7
【0047】
かかるポリカーボネート樹脂を製造する際に、必要に応じて亜燐酸エステル、燐酸エステル、ホスホン酸エステル等の安定剤、テトラブロムビスフェノールA、テトラブロムビスフェノールAの低分子量ポリカーボネート、デカブロモジフェノール等の難燃剤、着色剤、滑剤等を添加することができる。
【0048】
【実施例】
以下、実施例により本発明を詳述するが本発明はもとよりこれに限定されるものではない。なお、実施例中各種物性の測定、評価は以下の方法によって行った。また、実施例中の部および%は重量部および重量%を意味する。
【0049】
(1)紫外線吸収能を有する化合物の濃度測定
各実施例及び比較例を実施する時、記載した紫外線吸収能を有する化合物の濃度(c0:単位g/cm3)が分かっている第一層用組成物を帝人化成(株)製透明ポリカーボネート樹脂板(PC−1151:紫外線吸収剤無添加)5.0mmにディップコート法で各実施例及び比較例で記載した厚さに塗布し、20分間室温で放置後の380nmの吸光度(I1)を測定した(硬化前測定)。次に130℃で1時間熱硬化させた後、硬化前測定個所と同じ所の380nmの吸光度(I2)を再び測定した。これらの値を用いて下記式(イ)に従って塗膜中の紫外線吸収能を有する化合物の濃度(c)を計算した。
c=c0×(I2/I1) …(イ)
尚、I1及びI2の測定値は別にPC−1151単独の380nmの吸光度を測定して補償した。
(2)外観評価:目視にて試験片の1面のコート層外観(異物の有無)、ひび割れ(クラック)の有無を確認した。
(3)密着性:両面コート層の1面にカッターナイフで1mm間隔の100個の碁盤目を作りニチバン製粘着テープ(商品名“セロテープ”)を圧着し、垂直に強く引き剥がして基材上に残った碁盤目の数で評価した(JIS K5400に準拠)。
(4)耐摩耗性:JIS K6735に準じて、両面コート層の1面をCalibrase社製CS−10Fの摩耗輪を用い、荷重500gで1000回転テーバー摩耗試験を行い、テーバー摩耗試験後のヘーズとテーバー摩耗試験前のヘーズとの差△Hを測定して評価した。但し、磨耗輪のリフェースは研磨紙AA−400に代えて研磨紙S−11を用いて25回転で行った。
(ヘーズ=Td/Tt×100、Td:散乱光線透過率、Tt:全光線透過率)(5)促進試験:紫外線照射面を変更することなくスガ試験機製(株)スーパーキセノンウェザーメーターSX−75を用いて、UV照射強度180W/m2、ブラックパネル温度63℃、120分中18分降雨条件下で1500時間暴露し、試験片を取り出して紫外線照射面の外観、黄色度(△YI)を評価した。
(6)実曝試験:試験片を松山南面45°に設置し、5年間の曝露面を変更することなく実曝後、試験片を取り出して曝露面の外観、黄変度(△YI)を評価した。
【0050】
(アクリル樹脂(I)〜(IV)の合成)
[参考例1]
エチルセロソルブ400部、メタアクリル酸エチル190部及びγ−メタクリロキシプロピルトリメトキシシラン10部の混合物を窒素雰囲気下75℃に保ちつつ、ベンゾイルパーオキサイド1.0部をエチルセロソルブ200部に溶解した溶液を2時間かけて加え、更に6時間同温度に保持しアクリル樹脂(I)を得た。
【0051】
[参考例2]
還流冷却器及び撹拌装置を備え、窒素置換したフラスコ中にメチルメタクリレート(以下MMAと略称する)80.1部、2−ヒドロキシエチルメタクリレート(以下HEMAと略称する)13部、アゾビスイソブチロニトリル(以下AIBNと略称する)0.14部及び1,2−ジメトキシエタン200部を添加混合し、溶解させた。次いで、窒素気流中70℃で6時間攪拌下に反応させた。得られた反応液をn−ヘキサンに添加して再沈精製し、アクリル樹脂(II)80部を得た。
【0052】
[参考例3]
還流冷却器及び撹拌装置を備え、窒素置換したフラスコ中にエチルメタクリレート(以下EMAと略称する)91.3部、HEMA19.5部、2−(2′−ヒドロキシ−5′−メタクリロキシエチルフェニル)ベンゾトリアゾール(以下MEBTと略称する。濃度10mg/Lのクロロホルム溶液、光路長1.0cmで測定した、波長300nmにおける吸光度が0.43)16.2部、AIBN0.25部及びメチルイソブチルケトン100部および2−ブタノール50部を添加混合し、溶解させた。次いで、窒素気流中70℃で6時間攪拌下に反応させた。得られた反応液をn−ヘキサンに添加して再沈精製し、アクリル樹脂(III)100部を得た。
【0053】
[参考例4]
還流冷却器及び撹拌装置を備え、窒素置換したフラスコ中にEMA91.3部、HEMA19.5部、UVA−ST1(BASF製高分子紫外線吸収剤。濃度10mg/Lのクロロホルム溶液、光路長1.0cmで測定した、波長300nmにおける吸光度が0.21)15部、AIBN0.25部及びメチルイソブチルケトン100部および2−ブタノール50部を添加混合し、溶解させた。次いで、窒素気流中70℃で6時間攪拌下に反応させた。得られた反応液をn−ヘキサンに添加して再沈精製し、アクリル樹脂(IV)100部を得た。
【0054】
(第二層用組成物の調製)
[参考例5]
水分散型コロイダルシリカ分散液(日産化学工業(株)製 スノーテックス30 固形分濃度30重量%)100部に蒸留水2部、酢酸20部を加えて攪拌し、この分散液に氷水浴で冷却下メチルトリメトキシシラン130部を加えた。この混合液を25℃で1時間攪拌して得られた反応液に、硬化触媒として酢酸ナトリウム2部を氷水冷却下で混合し、イソプロパノール200部で希釈して得たコーティング用組成物(T−1)を得た。
【0055】
[実施例1]
アクリル樹脂(I)にエチルセロソルブ1486部、2,4−ジヒドロキシベンゾフェノン(濃度10mg/Lのクロロホルム溶液、光路長1.0cmで測定した、波長300nmにおける吸光度が0.33)30部、硬化触媒としてアルミニウムアセチルアセトネート2部及び架橋剤として1,6−ヘキサンジオール2.4部を加えて第一層用塗料とした。この塗料を紫外線吸収剤無添加の5mm厚の帝人化成(株)製透明ポリカーボネート樹脂板PC−1151(以下、PC−1151と略称する)にディップ方式でコーティングし、25℃で20分間静置後、130℃で1時間加熱硬化した。このとき第一層は、膜厚3.0μm、膜中に残っている2,4−ジヒドロキシベンゾフェノン濃度が0.30g/cm3であった。更に、第二層組成物(T−1)をディップコート方式でコーティングし、25℃で20分間静置後、120℃で1時間熱硬化させた。第二層の膜厚は5.0μmだった。得られたポリカーボネート樹脂成形体の評価結果を表1に示した。
【0056】
[実施例2]
前記アクリル樹脂(II)8.9部および2−(2′−ヒドロキシー5′−t−オクチルフェニル)ベンゾトリアゾール(濃度10mg/Lのクロロホルム溶液、光路長1.0cmで測定した、波長300nmにおける吸光度が0.45)4.0部をメチルエチルケトン20部、メチルイソブチルケトン30部および2−プロパノール30部からなる混合溶媒に溶解し、さらにこの溶液に前記アクリル樹脂(II)のヒドロキシ基1当量に対してイソシアネート基が1.5当量となるようにヘキサメチレンジイソシアネート1.1部を添加して25℃で5分間攪拌し第一層用塗料とした。この塗料を5mm厚のPC−1151にディップ方式でコーティングし、25℃で20分間静置後、130℃で1時間加熱硬化した。このとき第一層は、膜厚3.2μm、膜中に残っている2−(2′−ヒドロキシ−5′−t−オクチルフェニル)ベンゾトリアゾール濃度が0.20g/cm3であった。更に、第二層組成物(T−1)をディップコート方式でコーティングし、25℃で20分間静置後、120℃で1時間熱硬化させた。第二層の膜厚は5.1μmだった。得られたポリカーボネート樹脂成形体の評価結果を表1に示した。
【0057】
[実施例3]
実施例2の添加紫外線吸収基を有する化合物を、2−(2′−ヒドロキシ−5′−t−オクチルフェニル)ベンゾトリアゾール6.7部とした以外は、実施例2と同様の組成で第一層用塗料とした。この塗料を5mm厚のPC−1151にディップ方式でコーティングし、25℃で20分間静置後、130℃で1時間加熱硬化した。このとき第一層は、膜厚7.2μm、膜中に残っている2−(2′−ヒドロキシ−5′−t−オクチルフェニル)ベンゾトリアゾール濃度が0.40g/cm3であった。更に、第二層組成物(T−1)をディップコート方式でコーティングし、25℃で20分間静置後、120℃で1時間熱硬化させた。第二層の膜厚は5.1μmだった。得られたポリカーボネート樹脂成形体の評価結果を表1に示した。
【0058】
[実施例4]
実施例2の添加紫外線吸収基を有する化合物を、2−(2′−ヒドロキシ−5′−t−オクチルフェニル)ベンゾトリアゾール3.0部と2−(2H−ベンゾトリアゾール−2−イル)4−6−ビス(1−メチル−1−フェニルエチル)フェノール(濃度10mg/Lのクロロホルム溶液、光路長1.0cmで測定した、波長300nmにおける吸光度が0.38)1.6部の併用とした以外は、実施例2と同様の組成で第一層用塗料とした。この塗料を5mm厚のPC−1151にディップ方式でコーティングし、25℃で20分間静置後、130℃で1時間加熱硬化した。このとき第一層は、膜厚2.3μm、膜中に残っている2−(2′−ヒドロキシ−5′−t−オクチルフェニル)ベンゾトリアゾール濃度が0.13g/cm3、2−(2H−ベンゾトリアゾール−2−イル)4−6−ビス(1−メチル−1フェニルエチル)フェノール濃度が0.16g/cm3であった。更に、第二層組成物(T−1)をディップコート方式でコーティングし、25℃で20分間静置後、120℃で1時間熱硬化させた。第二層の膜厚は4.9μmだった。得られたポリカーボネート樹脂成形体の評価結果を表1に示した。
【0059】
[実施例5]
前記アクリル樹脂(III)10.0部メチルイソブチルケトン50部および2−ブタノール30部からなる混合溶媒に溶解し、さらにこの溶液に前記アクリル樹脂(III)のヒドロキシ基1当量に対してイソシアネート基が1.0当量となるようにVESTANAT B1358/100(デグサジャパン製アダクト型ポリイソシアネート化合物前駆体) 4.04部を添加し、さらにモノブチルチントリス(2−エチルヘキサノエート)0.001部を添加して25℃で30分間攪拌し第一層用塗料をとした。この塗料を5mm厚のPC−1151にディップ方式でコーティングし、25℃で20分間静置後、130℃で1時間加熱硬化した。このとき第一層は、膜厚6.0μm、膜中に残っている2−(2′−ヒドロキシ−5′−メタクリロキシエチルフェニル)ベンゾトリアゾールに相当する濃度が0.11g/cm3であった。更に、第二層組成物(T−1)をディップコート方式でコーティングし、25℃で20分間静置後、120℃で1時間熱硬化させた。第二層の膜厚は4.9μmだった。得られたポリカーボネート樹脂成形体の評価結果を表1に示した。
【0060】
[実施例6]
実施例5の添加紫外線吸収基を有する化合物、2−(2′−ヒドロキシ−5′−t−オクチルフェニル)ベンゾトリアゾール3.0部を添加した以外は、実施例5と同様の組成で第一層用塗料とした。この塗料を5mm厚のPC−1151にディップ方式でコーティングし、25℃で20分間静置後、130℃で1時間加熱硬化した。このとき第一層は、膜厚3.5μm、膜中に残っている2−(2′−ヒドロキシ−5′−メタクリロキシエチルフェニル)ベンゾトリアゾールに相当する濃度が0.11g/cm3、2−(2′−ヒドロキシ−5′−t−オクチルフェニル)ベンゾトリアゾール濃度が0.13g/cm3であった。更に、第二層組成物(T−1)をディップコート方式でコーティングし、25℃で20分間静置後、120℃で1時間熱硬化させた。第二層の膜厚は4.2μmだった。得られたポリカーボネート樹脂成形体の評価結果を表1に示した。
【0061】
[比較例1]
実施例1の第一層の膜厚を1.5μmとした以外は、実施例1と同様に試験片を作成した。得られたポリカーボネート樹脂成形体の評価結果を表1に示した。
【0062】
[比較例2]
実施例2の添加紫外線吸収基を有する化合物、2−(2′−ヒドロキシ−5′−t−オクチルフェニル)ベンゾトリアゾール(濃度10mg/Lのクロロホルム溶液、光路長1.0cmで測定した、波長300nmにおける吸光度が0.45)3.0部添加し、膜中に残っている2−(2′−ヒドロキシ−5′−t−オクチルフェニル)ベンゾトリアゾール濃度が0.15g/cm3であった以外は実施例2と同様に試験片を作成した。得られたポリカーボネート樹脂成形体の評価結果を表1に示した。
【0063】
[比較例3]
実施例3の添加紫外線吸収基を有する化合物、2−(2′−ヒドロキシ−5′−t−オクチルフェニル)ベンゾトリアゾール(濃度10mg/Lのクロロホルム溶液、光路長1.0cmで測定した、波長300nmにおける吸光度が0.45)7.5部添加し、膜中に残っている2−(2′−ヒドロキシ−5′−t−オクチルフェニル)ベンゾトリアゾール濃度が0.45g/cm3であった以外は実施例3と同様に試験片を作成した。得られたポリカーボネート樹脂成形体の評価結果を表1に示した。
【0064】
[比較例4]
実施例2の第一層の膜厚を9.0μmとした以外は実施例2と同様に試験片を作成した。得られたポリカーボネート樹脂成形体の評価結果を表1に示した。
【0065】
[比較例5]
実施例2の添加紫外線吸収基を有する化合物、2−(2′−ヒドロキシ−5′−t−オクチルフェニル)ベンゾトリアゾールの変わりに2,4−ジ−ベンチルフェニル−3,5−ジ−t−ブチル−4−ヒドロキシベンゾエート(濃度10mg/Lのクロロホルム溶液、光路長1.0cmで測定した、波長300nmにおける吸光度が0.003)4部添加し、膜中に残っている2,4−ジ−ベンチルフェニル−3,5−ジ−t−ブチル−4−ヒドロキシベンゾエート濃度が0.30g/cm3であった以外は実施例2と同様に試験片を作成した。得られたポリカーボネート樹脂成形体の評価結果を表1に示した。
【0066】
[比較例6]
実施例5のアクリル樹脂(III)の代わりにアクリル樹脂(IV)を使用した以外は、実施例5と同様に同様に試験片を作成した。得られたポリカーボネート樹脂成形体の評価結果を表1に示した。
【0067】
【表1】
【0068】
【発明の効果】
本発明のポリカーボネート積層体は、外観、密着性、耐摩耗性が良好で、高いレベルの実曝耐候性を有し、殊に両面を保護されたポリカーボネート積層体は自動車用窓ガラスやサンルーフに好適に使用され、その奏する工業的効果は格別である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polycarbonate resin laminate having a surface protected. More specifically, by adding a compound having an ultraviolet absorbing group having specific performance to a polycarbonate resin and / or laminating an acrylic resin layer introduced by copolymerization and a cured product layer of an organosiloxane resin in order, The present invention relates to a polycarbonate resin laminate having significantly improved durability against weather resistance.
[0002]
[Prior art]
Plastic materials are used in a variety of applications, taking advantage of their impact resistance, light weight, and workability. In particular, transparent plastics such as acrylic resin, polycarbonate resin, and styrene resin are widely used as an alternative to glass. However, these resins are not sufficient in weather resistance and are known to be deteriorated in physical properties and appearance because they are decomposed and deteriorated in long-term outdoor use. In recent years, there has been a movement to apply a transparent plastic sheet as an organic glass to a window glass, particularly an automobile window glass, taking advantage of its light weight and safety. When applying a transparent plastic sheet to such a use, the high weather resistance like a glass is requested | required. Further, it is necessary to prevent the occurrence of scratches when the wiper is operated on the front glass, and it is necessary to prevent the occurrence of scratches when the window is raised and lowered on the side window. In such applications, a high level of wear resistance is required.
[0003]
In order to remedy these defects, a number of improvements have been made to improve weather resistance, durability, and abrasion resistance by providing a thermosetting acrylic resin layer on the plastic surface and then covering it with a siloxane-based cured film. Proposals have been made.
[0004]
For example, Japanese Patent Publication No. 3-65383 discloses a composition containing a copolymer of an acrylic and / or vinyl monomer having an alkoxysilyl group and another monomer that can be copolymerized, a curing catalyst, and a crosslinking agent. A coating composition has been proposed in which a coating composition is formed by coating and curing to form an undercoat layer, and a composition containing colloidal silica-containing organopolysiloxane is used as an overcoat. By coating a polycarbonate resin molded article with this composition, wear resistance is proposed. An excellent coated polycarbonate resin molded product is obtained. However, with respect to the amount of added UV absorber, sufficient weather resistance is obtained in the accelerated test, but actual weather exposure can provide less weather resistance than expected, and the weather resistance varies depending on the film thickness. Thus, there is a demand for a polycarbonate laminate having good weather resistance in actual exposure by selecting an ultraviolet absorber type and concentration suitable for actual exposure and designing an appropriate film thickness.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a plastic molded article having a performance excellent in wear resistance, the surface of which is protected by a cured film capable of imparting high actual weather resistance.
[0006]
As a result of intensive studies to achieve this object, the present inventors have determined that the maximum deterioration wavelength of polycarbonate is 290 nm. On the other hand, it is noticed that the solar spectrum of actual exposure is almost cut by the ozone layer when it is 300 nm or less, and a compound having an ultraviolet absorbing group having an absorption ability of 300 nm or more is added and / or introduced by copolymerization. A transparent polycarbonate resin laminate in which the durability against weathering due to actual exposure is remarkably improved by laminating the prepared acrylic resin layer with a specific film thickness and sequentially laminating the cured layer of organosiloxane resin. As a result, the present invention was reached.
[0007]
[Means for Solving the Problems]
That is, according to the present invention, two layers of an acrylic resin layer (first layer) and a cured composition layer (second layer) containing a colloidal silica-containing organosiloxane resin are sequentially laminated on at least one surface of a transparent polycarbonate resin plate. The first layer of the laminate satisfied the following formulas (1) to (3), and the absorbance at a wavelength of 300 nm was measured with a chloroform solution having a concentration of 10 mg / L and an optical path length of 1.0 cm. A polycarbonate resin laminate excellent in actual weathering resistance is provided, which contains a compound having an ultraviolet absorbing ability of which is 0.25 or more.
2 ≦ d ≦ 8 (1)
0.1 ≦ c ≦ 0.5 (2)
0.6 ≦ d × c ≦ 3 (3)
(Where d is the thickness of the first layer expressed in μm, and c is g / cm in the layer)3The concentration of the unit derived from the compound having the ability to absorb ultraviolet rays represented by
[0008]
Regarding the acrylic resin layer of the first layer used in the present invention, “containing a compound having ultraviolet absorbing ability in the first layer” in the present invention means “compound having an ultraviolet absorbing group in the first layer”. It means adding and / or introducing a compound having an ultraviolet absorbing group into the acrylic resin in the first layer by copolymerization.
[0009]
The acrylic resin of the 1st layer used by this invention will not be specifically limited if the cured film containing the colloidal silica containing organosiloxane resin of a polycarbonate substrate and a 2nd layer shows favorable adhesiveness. For example, an acrylic resin having a hydroxy group obtained by copolymerizing an alkyl methacrylate monomer and an acrylate monomer having a hydroxy group, mixed with a polyisocyanate compound or trialkoxysilane hydrolyzate as a crosslinking agent in a solvent, and heat cured. , An acrylic resin having a hydroxy group obtained by copolymerizing an acrylate monomer having a hydroxy group and an acrylate monomer having a hydroxy group with a polyisocyanate compound or trialkoxysilane hydrolyzate as a crosslinking agent What mixed and heat-cured is mentioned. Of these, those cured are preferred. Furthermore (A) the following formula (1)
[0010]
[Chemical 1]
[0011]
(However, R in the formula1Is an alkyl group having 1 to 4 carbon atoms. )
An acrylic resin containing 50 mol% or more of a repeating unit represented by
(B) A cured acrylic resin from a polyisocyanate compound and / or a polyisocyanate compound precursor is preferable because of excellent properties such as coating solution stability. A specific example of this acrylic resin is a polymer obtained by polymerizing 50 mol% or more of an alkyl methacrylate monomer and 50 mol% or less of a vinyl monomer. Examples of the alkyl methacrylate monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate, and these can be used alone or in admixture of two or more. Of these, methyl methacrylate and ethyl methacrylate are preferred. Further, as other vinyl monomers, those which can be copolymerized with alkyl methacrylate monomers are used, and acrylic acid, methacrylic acid or derivatives thereof are preferably used particularly in terms of durability such as adhesion or weather resistance. . Specifically, acrylic acid, methacrylic acid, acrylic acid amide, methacrylic acid amide, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, N, N-diethylaminoethyl methacrylate, glycidyl methacrylate, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2- (2'- Hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole, 2- (2'-hydroxy-5-acryloxyethyl) Eniru) -2H- benzotriazole, etc. These can be used alone or in combination. Moreover, the mixture which mixed 2 or more types of acrylic resin may be sufficient.
[0012]
The acrylic resin is preferably a thermosetting type, and desirably contains a vinyl monomer having a crosslinkable reactive group of 0.01 mol% to 50 mol%. Examples of vinyl monomers having such a crosslinkable reactive group include acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, vinyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane. , 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane and the like.
[0013]
Among them, acrylic monomers having a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, etc. are used as vinyl monomers having a crosslinkable reactive group, and polyisocyanate compounds or their compounds are used as crosslinking agents. A thermosetting urethane acrylic resin using a polyisocyanate compound precursor that generates a derivative can be preferably used.
[0014]
The molecular weight of the acrylic resin is preferably 20,000 or more in terms of weight average molecular weight, more preferably 50,000 or more, and those having a weight average molecular weight of 10 million or less are preferably used. The acrylic resin having such a molecular weight range is preferable because performance such as adhesion and strength as the first layer is sufficiently exhibited.
[0015]
As a method of forming the coating film resin (first layer) used in the present invention, a coating film resin component such as an acrylic resin and additional components such as a light stabilizer and an ultraviolet absorber described later are used as a transparent plastic as a base material. The coating composition is applied to the surface of a transparent plastic substrate after being dissolved in a volatile solvent that does not react with or dissolve the transparent plastic, and then the solvent is removed by heating or the like. If necessary, it is also preferable to further crosslink the crosslinkable group by heating to 40 to 140 ° C. after removing the solvent.
[0016]
Examples of the solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethers such as tetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane, esters such as ethyl acetate and ethoxyethyl acetate, methanol, Alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-ethoxyethanol, 4-methyl-2-pentanol, 2-butoxyethanol, n -Hexanes, n-heptane, isooctane, benzene, toluene, xylene, gasoline, light oil, kerosene and other hydrocarbons, acetonitrile, nitromethane, water and the like. These may be used alone or in combination of two or more. You may mix and use. The concentration of the solid content of the coating film resin in the coating composition is preferably 1 to 50% by weight, more preferably 3 to 30% by weight.
[0017]
Examples of the polyisocyanate compound for the cured acrylic resin include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, tolidine diisocyanate, xylene diisocyanate, lysine diisocyanate, trimethylhexamethylene. Diisocyanate, dimer acid diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, or an adduct of these polyisocyanate compound and polyhydric alcohol, low molecular weight polyester resin, or a cyclized polymer of the above polyisocyanate compounds, In addition, isocyanates and burettes are listed. Of aliphatic and alicyclic polyisocyanate compounds such as methylene diisocyanate and isophorone diisocyanate, adducts of aliphatic and / or alicyclic polyisocyanate compounds with polyhydric alcohols and low molecular weight polyester resins, and aliphatic polyisocyanate compounds A cyclized polymer or the like is particularly preferable because of excellent weather resistance.
[0018]
Examples of the polyisocyanate compound precursor for the cured acrylic resin include oximes such as acetooxime and methylethylketoxime on the isocyanate group of the polyisocyanate compound, dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc. Active methylene compounds, alcohols such as methanol, ethanol, 2-propanol, n-butanol, sec-butanol and 2-ethyl-1-hexanol, and blocking agents represented by phenols such as phenol, cresol and ethylphenol And a blocked isocyanate compound that forms a polyisocyanate compound by thermal decomposition. This blocked isocyanate is particularly preferably used because an isocyanate group is generated only at the time of the thermosetting reaction, so that the storage stability of the coating composition is excellent, and the isocyanate group is hardly consumed in the side reaction. The said polyisocyanate compound and polyisocyanate compound precursor can be used individually or in mixture of 2 or more types.
[0019]
The initial isocyanate group content and / or isocyanate group content of the polyisocyanate compound and / or polyisocyanate compound precursor is preferably 5.0 to 60% by weight, more preferably 6.0 to 55% by weight, and most preferably 6. 0 to 50% by weight. When the isocyanate group content is less than 5.0% by weight, the blending amount of the polyisocyanate compound and / or the polyisocyanate compound precursor with respect to the acrylic resin increases, and the repetition represented by the formula (1) in the coating film resin Since the unit ratio decreases, the adhesion with the plastic substrate becomes poor. On the other hand, if it exceeds 60% by weight, the flexibility of the coating layer decreases, and the coating layer is cracked when the second layer is thermoset, and the durability against changes in the environment is impaired.
[0020]
The initial isocyanate group referred to in the present invention is an isocyanate group that exists freely at the molecular end, such as the polyisocyanate compounds exemplified above, and the isocyanate group that is formed is, for example, a blocking agent with an isocyanate group. Like a blocked isocyanate compound, the block is thermally decomposed and is an isocyanate group of the polyisocyanate compound produced at that time.
[0021]
The mixing amount ratio of the acrylic resin having a hydroxy group and the polyisocyanate compound or a derivative thereof or a polyisocyanate compound precursor is the initial stage of (B) and formed with respect to 1 equivalent of the hydroxy group of the acrylic resin of (A). The total amount of isocyanate groups is preferably 0.6 to 2.0 equivalents, more preferably 0.7 to 1.75 equivalents, and most preferably 0.8 to 1.5 equivalents. By preparing such a composition, the layer made of such an acrylic resin can maintain good adhesion with the transparent plastic substrate and the second-layer organosiloxane resin thermosetting layer, and has a high level of crosslinking. Due to its density, it is difficult to cause a decrease in crosslink density due to ultraviolet rays, water, and oxygen, and it can maintain long-term adhesion, environmental changes and durability under high temperature environments, and has excellent weather resistance.
[0022]
The compound having an ultraviolet absorbing group added and / or introduced by the first copolymerization in the acrylic resin has an absorbance at a wavelength of 300 nm of 0.25 or more, measured with a chloroform solution having a concentration of 10 mg / L and an optical path length of 1.0 cm. If it is, it will not specifically limit. Specifically, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, benzophenones such as 2-hydroxy-4-methoxybenzophenone, 2- (5′-methyl-2′-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1-phenylethyl) phenol, 2- (3′-tert-butyl-5′-methyl-2′-hydroxyphenyl) benzotriazole Benzotriazoles such as 2- (3 ′, 5′-di-t-butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl Cyanoacrylates such as 2-cyano-3,3-diphenylacrylate, Rusarishireto, salicylates such as p- octylphenyl salicylate, diethyl -p- methoxy benzylidene malonate, bis (2-ethylhexyl) benzylidene malonate such as benzylidene malonate and the like. These agents may be used alone or in combination of two or more, and those having compatibility with the acrylic resin and solubility with the solvent within the range of the formula (2) can be selected.
[0023]
In addition, an acrylate or methacrylate monomer having an ultraviolet absorbing group copolymerizable with an acrylic resin and having an absorbance at a wavelength of 300 nm of 0.25 or more measured with a chloroform solution having a concentration of 10 mg / L and an optical path length of 1.0 cm. Specifically, 2- (2'-hydroxy-5'-acryloxyethylphenyl) benzotriazole, 2- (2'-hydroxy-5'-acryloxyethoxyphenyl) benzotriazole, 2- (2'-hydroxy -5'-acryloxypropylphenyl) benzotriazole, 2- (2'-hydroxy-5'-acryloxypropoxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-acryloxyethylphenyl) -5 Chlorobenzotriazole, 2- (2'-hydroxy-3) -Acryloxyethyl-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-acryloxyethyl-5'-t-butylphenyl) -5-chlorobenzotriazole, 2-hydroxy- 4- (acryloxyethoxy) benzophenone, 2-hydroxy-4- (acryloxypropoxy) benzophenone, 2,2'-dihydroxy-4- (acryloxyethoxy) benzophenone, 2-hydroxy-4- (acryloyloxyethyl) benzophenone 2- (2'-hydroxy-5'-methacryloxyethylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methacryloxyethoxyphenyl) benzotriazole, 2- (2'-hydroxy-5'- Methacryloxypropylphenyl) benzotri Sol, 2- (2'-hydroxy-5'-methacryloxypropoxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -5-chlorobenzotriazole, 2- (2'- Hydroxy-3'-methacryloxyethyl-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-methacryloxyethyl-5'-t-butylphenyl) -5-chlorobenzotriazole, 2-hydroxy-4- (methacryloxyethoxy) benzophenone, 2-hydroxy-4- (methacryloxypropoxy) benzophenone, 2,2'-dihydroxy-4- (methacryloxyethoxy) benzophenone, 2-hydroxy-4- (methacryloyl) Oxyethyl) benzophenone, etc. .
[0024]
The film thickness d (μm) of the heat-cured first layer in which the compound having an ultraviolet absorbing group is added to the first layer and / or introduced into the acrylic resin in the first layer by copolymerization is 2 If ≦ d ≦ 8, preferably 3 ≦ d ≦ 5, and the film thickness is less than 2 μm, cracks occur in the second layer film or the adhesion is reduced, resulting in poor weather resistance. When the film thickness is thicker than 8 μm, the crosslinking reaction at the time of thermosetting does not proceed sufficiently, resulting in a coating layer with poor durability that whitens or deteriorates adhesion under high humidity. In addition, the concentration c (g / cm in the first layer of the compound having the ultraviolet absorbing ability described above.3) Is 0.1 ≦ c ≦ 0.5, preferably 0.2 ≦ c ≦ 0.4, and the concentration is 0.1 g / cm.3If it is less than 1, the transmittance of ultraviolet rays will be high, the yellowing of the substrate will occur or the adhesion will be reduced, so the weather resistance will be poor, 0.5 g / cm3If it exceeds 1, the adhesion with the polycarbonate substrate or the second layer is remarkably lowered, and the coating film is likely to be spontaneously peeled off during actual exposure. In order to obtain good actual weathering resistance, the above d × c is 0.6 ≦ d × c ≦ 3, preferably 0.8 ≦ d × c ≦ 2, and d × c is 0.6 or less. And the ultraviolet ray transmittance increases, causing yellowing of the base material and lowering the adhesion, resulting in poor weather resistance. When the ratio exceeds 3, the adhesion with the polycarbonate base material or the second layer is significantly reduced. It becomes easy to cause spontaneous peeling of the coating film upon exposure.
[0025]
If necessary, a curing catalyst, a light stabilizer, and a silane coupling agent can be added to the acrylic resin layer used in the first layer.
[0026]
Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2,2 , 6,6-tetramethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-octanoyloxy-2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) diphenylmethane-p, p'-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3-di Hindered amines such as sulfonate, bis (2,2,6,6-tetramethyl-4-piperidyl) phenyl phosphite, nickel bis (octylphenyl sulfide) And nickel complexes such as nickel complex-3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyldithiocarbamate, etc. These agents may be used alone or in combination of two or more. A good effect may be imparted to weatherability.
[0027]
Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N -Vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltriacetoxysilane, γ-anilinopropyltrimethoxysilane, Examples include vinyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-ureidopropyltriethoxysilane and the like, and partial hydrolysis condensates of the above silane coupling agents can also be used. By adding such an agent, the adhesion between the polycarbonate base material and the first layer and between the first layer and the second layer is maintained for a long time. These agents may be used alone or in combination of two or more.
[0028]
The composition containing the colloidal silica-containing organosiloxane resin of the second layer used in the present invention is not particularly limited as long as it exhibits good adhesion with the cured film of the acrylic resin of the first layer. For example, an organosiloxane resin made of a hydrolyzed condensate of colloidal silica and trialkoxysilane is preferred, and an organosiloxane resin made of a hydrolyzed condensate of colloidal silica, trialkoxysilane and a hydrolyzed condensate of tetraalkoxysilane is particularly preferred.
[0029]
Such colloidal silica (hereinafter sometimes referred to as “a component”) is a colloidal dispersion of silica fine particles having a diameter of 5 to 200 nm, preferably 5 to 40 nm, in water or an organic solvent. The colloidal silica can be used in either a water dispersion type or an organic solvent dispersion type, but a water dispersion type is preferably used. In the case of water-dispersed colloidal silica, there are many hydroxyl groups on the surface of the silica fine particles, which are strongly bonded to the trialkoxysilane hydrolyzed condensate, so that a plastic laminate with superior wear resistance can be obtained. it is conceivable that.
[0030]
The water-dispersed colloidal silica is further divided into an acidic aqueous dispersion type and a basic aqueous dispersion type. The water-dispersed colloidal silica can be used in either an acidic aqueous dispersion type or a basic aqueous dispersion type. However, in view of the diversity of curing catalyst selection, appropriate hydrolysis of methyltrialkoxysilane, and the realization of a condensed state, Type colloidal silica is preferably used.
[0031]
As such colloidal silica, specifically, as a product dispersed in an acidic aqueous solution, as a product dispersed in a basic aqueous solution, Snowtex O of Nissan Chemical Industry Co., Ltd., Cataloid SN of Catalytic Chemical Industry Co., Ltd. Nissan Chemical Industries, Ltd. Snowtex 30, Snowtex 40, Catalytic Chemical Industry Co., Ltd. Cataloid S30, Cataloid S40, Nissan Chemical Industries, Ltd. MA-ST, IPA-ST , NBA-ST, IBA-ST, EG-ST, XBA-ST, NPC-ST, DMAC-ST, OSCAL1132, OSCAL1232, OSCAL1332, OSCAL1432, OSCAL1532, OSCAL1632, OSCAL1732, etc.
[0032]
The hydrolysis condensate of alkoxysilane (hereinafter sometimes referred to as component b) is, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetra Isobutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4- Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltri Toxisilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, dimethyldimethoxysilane, vinylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-aminopropyl Examples thereof include methyldiethoxysilane, among which alkyltrialkoxysilane is preferable, and methyltrimethoxysilane and methyltriethoxysilane are particularly preferable. These can be used alone or in combination.
[0033]
The organosiloxane resin composition is prepared, for example, through the following process. However, the present invention is not limited to the following processes.
[0034]
In the colloidal silica dispersion, the alkoxysilane is subjected to a hydrolytic condensation reaction under acidic conditions.
[0035]
Here, water required for the hydrolysis reaction of alkoxysilane is supplied from this dispersion when a water-dispersed colloidal silica dispersion is used, and water may be added if necessary. Usually, 1 to 10 equivalents, preferably 1.5 to 7 equivalents, more preferably 3 to 5 equivalents of water are used per 1 equivalent of alkoxysilane.
[0036]
As described above, the hydrolysis-condensation reaction of trialkoxysilane must be performed under acidic conditions. In order to perform hydrolysis under such conditions, an acid is generally used as a hydrolyzing agent. Such an acid may be added in advance to the alkoxysilane or colloidal silica dispersion, or both may be added after mixing. Moreover, this addition can also be divided into 1 time or 2 times or more. When acidic aqueous dispersion type colloidal silica is used, it is not always necessary to use an acid because the acid in the colloidal silica keeps the reaction solution under acidic conditions. Such acids include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, nitrous acid, perchloric acid, sulfamic acid, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, maleic acid, lactic acid, paratoluene sulfone. Examples thereof include organic acids such as acids, and organic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, and maleic acid are preferable, and acetic acid is particularly preferable from the viewpoint of easy control of pH.
[0037]
When an inorganic acid is used as such an acid, it is usually used at a concentration of 0.0001 to 2 mol / l, preferably 0.001 to 0.1 mol / l. When an organic acid is used, 100 parts by weight of methyltrialkoxysilane The amount is 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight.
[0038]
The conditions for the hydrolysis and condensation reaction of the alkoxysilane cannot be unconditionally changed depending on the type of alkoxysilane used, the type and amount of colloidal silica coexisting in the system, but the system temperature is usually 20 to 40 ° C. The reaction time is 1 hour to several days. Although the hydrolysis reaction of alkoxysilane is an exothermic reaction, it is desirable that the temperature of the system does not exceed 60 ° C. at the maximum. It is also preferable to allow the hydrolysis reaction to proceed sufficiently under such conditions and to allow the condensation reaction to proceed at 40 to 80 ° C. for 1 hour to several days in order to stabilize the coating agent.
[0039]
In the present invention, the mixing ratio of each of the components a and b, which are solid components of the organosiloxane resin, is the stability of the organosiloxane resin composition, the transparency of the resulting cured film, the wear resistance, the scratch resistance, the adhesion and When the total of the component a and component b is 100% by weight, the preferred mixing ratio of these two components is 10 to 60% by weight for component a and R for component b.2 mR3 nSiO(4-mn) / 2(However, R2, R3Are each substituted with one or more groups selected from the group consisting of alkyl groups having 1 to 4 carbon atoms, vinyl groups, or methacryloxy groups, amino groups, glycidoxy groups, and 3,4-epoxycyclohexyl groups. M and n are each an integer of 0, 1 or 2, and m + n is an integer of 0, 1 or 2), preferably 40 to 90% by weight, A component is 10-40% by weight, b component is R2 mR3 nSiO(4-mn) / 2It is 60 to 90% by weight in terms of.
[0040]
The thickness of the second layer is usually 2 to 10 μm, preferably 3 to 8 μm. When the thickness of the coat layer is within such a range, cracks are not generated in the coat layer due to the stress generated at the time of thermosetting, and the adhesion between the coat layer and the substrate is not lowered. A desired coating layer having sufficient wear resistance can be obtained.
[0041]
The first layer and the second layer are applied to the polycarbonate substrate by a method such as a bar coating method, a dip coating method, a flow coating method, a spray coating method, a spin coating method, or a roller coating method. It can select suitably according to a shape.
[0042]
The polycarbonate resin used in the present invention is a polycarbonate resin obtained by reacting a dihydric phenol and a carbonate precursor by an interfacial polycondensation method or a melting method. Representative examples of the dihydric phenol include 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as bisphenol A), 2,2-bis (3-methyl-4-hydroxyphenyl) propane, Bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy) Phenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) 3,3,5-trimethylcyclohexane and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, and the like. But bisphenol A is preferred. These dihydric phenols can be used alone or in admixture of two or more.
[0043]
As the polycarbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.
[0044]
When producing polycarbonate resin by reacting the above dihydric phenol and carbonate precursor by interfacial polycondensation method or melting method, use catalyst, terminal terminator, dihydric phenol antioxidant, etc. as necessary May be. The polycarbonate resin may be a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or may be a polyester carbonate resin copolymerized with an aromatic or aliphatic difunctional carboxylic acid, Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.
[0045]
In the interfacial polycondensation method using phosgene, the reaction is carried out in the presence of an acid binder and an organic solvent. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as pyridine, and examples of the solvent include halogenated hydrocarbons such as methylene chloride and chlorobenzene. In order to accelerate the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. The reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours. The melting method using diphenyl carbonate is carried out by a method in which a predetermined proportion of a dihydric phenol component and diphenyl carbonate are stirred with heating in an inert gas atmosphere to distill the alcohol or phenols produced. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced by reducing the pressure from the beginning. Moreover, in order to accelerate | stimulate reaction, the catalyst for normal transesterification can also be used.
[0046]
The molecular weight of the polycarbonate resin is preferably 10,000 to 50,000, more preferably 15,000 to 35,000 in terms of viscosity average molecular weight (M). A polycarbonate resin having such a viscosity average molecular weight is preferable because sufficient strength is obtained and the melt fluidity during molding is good. The viscosity average molecular weight referred to in the present invention is obtained by inserting the specific viscosity (ηsp) obtained from a solution of 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20 ° C. into the following equation.
ηsp / c = [η] + 0.45 × [η]2c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10-4M0.83
c = 0.7
[0047]
When producing such a polycarbonate resin, if necessary, stabilizers such as phosphites, phosphates, and phosphonates, low molecular weight polycarbonates of tetrabromobisphenol A, tetrabromobisphenol A, and flame retardants such as decabromodiphenol Coloring agents, lubricants and the like can be added.
[0048]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to this from the first. In the examples, various physical properties were measured and evaluated by the following methods. Moreover, the part and% in an Example mean a weight part and weight%.
[0049]
(1) Concentration measurement of a compound having ultraviolet absorbing ability
When carrying out each example and comparative example, the concentration (c0: Unit g / cm3The composition for the first layer, which is known), was described in each example and comparative example by the dip coating method on a transparent polycarbonate resin plate (PC-1151: No UV absorber added) manufactured by Teijin Chemicals Ltd. 5.0 mm. Absorbance at 380 nm (I1) Was measured (measurement before curing). Next, after thermosetting at 130 ° C. for 1 hour, the absorbance at 380 nm (I2) Was measured again. Using these values, the concentration (c) of the compound having an ultraviolet absorbing ability in the coating film was calculated according to the following formula (A).
c = c0× (I2/ I1) …(I)
I1And I2The measured value was compensated by measuring the absorbance of PC-1151 alone at 380 nm.
(2) Appearance evaluation: The appearance of one coat layer of the test piece (presence of foreign matter) and the presence or absence of cracks (cracks) were visually confirmed.
(3) Adhesion: One side of the double-sided coating layer is made of 100 grids with a cutter knife at intervals of 1 mm, and Nichiban adhesive tape (trade name “Cellotape”) is pressure-bonded and peeled off strongly vertically on the substrate. It was evaluated by the number of grids remaining (according to JIS K5400).
(4) Abrasion resistance: According to JIS K6735, one side of the double-sided coating layer was subjected to a 1000-turn Taber abrasion test at a load of 500 g using a CS-10F abrasion wheel manufactured by Calibrase. The difference ΔH from the haze before the Taber abrasion test was measured and evaluated. However, the re-facing of the wear ring was performed at 25 rotations using the polishing paper S-11 instead of the polishing paper AA-400.
(Haze = Td / Tt × 100, Td: scattered light transmittance, Tt: total light transmittance) (5) Accelerated test: Super Xenon Weather Meter SX-75 manufactured by Suga Test Instruments Co., Ltd. without changing the ultraviolet irradiation surface UV irradiation intensity 180W / m2Then, the panel was exposed to a black panel temperature of 63 ° C. for 18 hours under 120 minutes of rain, and the test piece was taken out to evaluate the appearance and yellowness (ΔYI) of the ultraviolet irradiation surface.
(6) Actual exposure test: Place the test piece on the south side of Matsuyama 45 °, and after the actual exposure without changing the exposed surface for 5 years, take out the test piece and determine the appearance and yellowing degree (△ YI) of the exposed surface. evaluated.
[0050]
(Synthesis of acrylic resins (I) to (IV))
[Reference Example 1]
A solution in which 1.0 part of benzoyl peroxide is dissolved in 200 parts of ethyl cellosolve while maintaining a mixture of 400 parts of ethyl cellosolve, 190 parts of ethyl methacrylate and 10 parts of γ-methacryloxypropyltrimethoxysilane at 75 ° C. in a nitrogen atmosphere. Was added over 2 hours, and the temperature was further maintained for 6 hours to obtain an acrylic resin (I).
[0051]
[Reference Example 2]
A flask equipped with a reflux condenser and a stirrer and purged with nitrogen, 80.1 parts of methyl methacrylate (hereinafter abbreviated as MMA), 13 parts of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), azobisisobutyronitrile 0.14 parts (hereinafter abbreviated as AIBN) and 200 parts of 1,2-dimethoxyethane were added, mixed and dissolved. Subsequently, it was made to react under stirring at 70 degreeC in nitrogen stream for 6 hours. The obtained reaction solution was added to n-hexane and purified by reprecipitation to obtain 80 parts of acrylic resin (II).
[0052]
[Reference Example 3]
A flask equipped with a reflux condenser and a stirrer, and 91.3 parts of ethyl methacrylate (hereinafter abbreviated as EMA), 19.5 parts of HEMA, 2- (2'-hydroxy-5'-methacryloxyethylphenyl) in a flask purged with nitrogen 16.2 parts of benzotriazole (hereinafter abbreviated as MEBT; chloroform solution with a concentration of 10 mg / L, optical path length of 1.03, absorbance at 300 nm wavelength of 0.43), 16.25 parts of AIBN and 100 parts of methyl isobutyl ketone And 50 parts of 2-butanol were added, mixed and dissolved. Subsequently, it was made to react under stirring at 70 degreeC in nitrogen stream for 6 hours. The obtained reaction solution was added to n-hexane and purified by reprecipitation to obtain 100 parts of acrylic resin (III).
[0053]
[Reference Example 4]
In a flask equipped with a reflux condenser and a stirrer and purged with nitrogen, EMA 91.3 parts, HEMA 19.5 parts, UVA-ST1 (high molecular weight UV absorber made by BASF. Chloroform solution with a concentration of 10 mg / L, optical path length 1.0 cm The absorbance at a wavelength of 300 nm was 0.21), 15 parts of AIBN, 0.25 parts, 100 parts of methyl isobutyl ketone and 50 parts of 2-butanol were mixed and dissolved. Subsequently, it was made to react under stirring at 70 degreeC in nitrogen stream for 6 hours. The obtained reaction liquid was added to n-hexane and purified by reprecipitation to obtain 100 parts of acrylic resin (IV).
[0054]
(Preparation of composition for second layer)
[Reference Example 5]
2 parts of distilled water and 20 parts of acetic acid are added to 100 parts of water-dispersed colloidal silica dispersion (Snowtex 30, solid concentration 30% by weight, manufactured by Nissan Chemical Industries, Ltd.) and stirred, and the dispersion is cooled in an ice-water bath. 130 parts of lower methyltrimethoxysilane was added. The reaction mixture obtained by stirring this mixture at 25 ° C. for 1 hour was mixed with 2 parts of sodium acetate as a curing catalyst under cooling with ice water and diluted with 200 parts of isopropanol to obtain a coating composition (T- 1) was obtained.
[0055]
[Example 1]
As acrylic resin (I), 1486 parts of ethyl cellosolve, 30 parts of 2,4-dihydroxybenzophenone (chloroform solution with a concentration of 10 mg / L, optical path length of 1.0 cm, absorbance at a wavelength of 300 nm of 0.33), curing catalyst 2 parts of aluminum acetylacetonate and 2.4 parts of 1,6-hexanediol as a crosslinking agent were added to obtain a coating material for the first layer. This paint was coated on a transparent polycarbonate resin plate PC-1151 (hereinafter abbreviated as PC-1151) made by Teijin Chemicals Co., Ltd. with a thickness of 5 mm with no UV absorber added, and allowed to stand at 25 ° C. for 20 minutes. And cured at 130 ° C. for 1 hour. At this time, the first layer has a thickness of 3.0 μm and the concentration of 2,4-dihydroxybenzophenone remaining in the film is 0.30 g / cm.3Met. Furthermore, the second layer composition (T-1) was coated by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 1 hour. The film thickness of the second layer was 5.0 μm. The evaluation results of the obtained polycarbonate resin molded product are shown in Table 1.
[0056]
[Example 2]
8.9 parts of the acrylic resin (II) and 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole (chloroform solution at a concentration of 10 mg / L, measured at an optical path length of 1.0 cm, absorbance at a wavelength of 300 nm 0.45) 4.0 parts is dissolved in a mixed solvent consisting of 20 parts of methyl ethyl ketone, 30 parts of methyl isobutyl ketone and 30 parts of 2-propanol, and this solution is further added to 1 equivalent of the hydroxy group of the acrylic resin (II). Then, 1.1 parts of hexamethylene diisocyanate was added so that the isocyanate group became 1.5 equivalents, and the mixture was stirred at 25 ° C. for 5 minutes to obtain a coating material for the first layer. This paint was coated on PC-1151 having a thickness of 5 mm by a dip method, allowed to stand at 25 ° C. for 20 minutes, and then cured by heating at 130 ° C. for 1 hour. At this time, the first layer had a thickness of 3.2 μm and the concentration of 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole remaining in the film was 0.20 g / cm.3Met. Furthermore, the second layer composition (T-1) was coated by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 1 hour. The film thickness of the second layer was 5.1 μm. The evaluation results of the obtained polycarbonate resin molded product are shown in Table 1.
[0057]
[Example 3]
The first composition was the same as that of Example 2 except that the compound having an ultraviolet absorbing group added in Example 2 was 6.7 parts of 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole. A layer coating was obtained. This paint was coated on PC-1151 having a thickness of 5 mm by a dip method, allowed to stand at 25 ° C. for 20 minutes, and then cured by heating at 130 ° C. for 1 hour. At this time, the first layer had a film thickness of 7.2 μm and the concentration of 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole remaining in the film was 0.40 g / cm.3Met. Furthermore, the second layer composition (T-1) was coated by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 1 hour. The film thickness of the second layer was 5.1 μm. The evaluation results of the obtained polycarbonate resin molded product are shown in Table 1.
[0058]
[Example 4]
The compound having an ultraviolet absorbing group added in Example 2 was converted into 3.0 parts of 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole and 2- (2H-benzotriazol-2-yl) 4- Except for the combined use of 1.6 parts of 6-bis (1-methyl-1-phenylethyl) phenol (chloroform solution with a concentration of 10 mg / L, optical path length measured at 1.0 cm, absorbance at 300 nm wavelength of 0.38) Was a coating for the first layer having the same composition as in Example 2. This paint was coated on PC-1151 having a thickness of 5 mm by a dip method, allowed to stand at 25 ° C. for 20 minutes, and then cured by heating at 130 ° C. for 1 hour. At this time, the first layer had a film thickness of 2.3 μm and the concentration of 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole remaining in the film was 0.13 g / cm.3, 2- (2H-benzotriazol-2-yl) 4-6-bis (1-methyl-1-phenylethyl) phenol concentration is 0.16 g / cm3Met. Furthermore, the second layer composition (T-1) was coated by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 1 hour. The film thickness of the second layer was 4.9 μm. The evaluation results of the obtained polycarbonate resin molded product are shown in Table 1.
[0059]
[Example 5]
The acrylic resin (III) is dissolved in 10.0 parts of methyl isobutyl ketone and 30 parts of 2-butanol in a mixed solvent, and an isocyanate group is added to this solution with respect to 1 equivalent of the hydroxy group of the acrylic resin (III). 4.04 parts of VESTANAT B1358 / 100 (Degussa Japan adduct-type polyisocyanate compound precursor) was added to 1.0 equivalent, and 0.001 part of monobutyltin tris (2-ethylhexanoate) was further added. The mixture was added and stirred at 25 ° C. for 30 minutes to obtain a first layer coating material. This paint was coated on PC-1151 having a thickness of 5 mm by a dip method, allowed to stand at 25 ° C. for 20 minutes, and then cured by heating at 130 ° C. for 1 hour. At this time, the first layer had a film thickness of 6.0 μm and a concentration corresponding to 2- (2′-hydroxy-5′-methacryloxyethylphenyl) benzotriazole remaining in the film was 0.11 g / cm.3Met. Furthermore, the second layer composition (T-1) was coated by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 1 hour. The film thickness of the second layer was 4.9 μm. The evaluation results of the obtained polycarbonate resin molded product are shown in Table 1.
[0060]
[Example 6]
The same composition as in Example 5 except that 3.0 parts of 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, a compound having an ultraviolet absorbing group added in Example 5, was added. A layer coating was obtained. This paint was coated on PC-1151 having a thickness of 5 mm by a dip method, allowed to stand at 25 ° C. for 20 minutes, and then cured by heating at 130 ° C. for 1 hour. At this time, the first layer had a thickness of 3.5 μm, and the concentration corresponding to 2- (2′-hydroxy-5′-methacryloxyethylphenyl) benzotriazole remaining in the film was 0.11 g / cm.3, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole concentration is 0.13 g / cm3Met. Furthermore, the second layer composition (T-1) was coated by a dip coating method, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 1 hour. The film thickness of the second layer was 4.2 μm. The evaluation results of the obtained polycarbonate resin molded product are shown in Table 1.
[0061]
[Comparative Example 1]
A test piece was prepared in the same manner as in Example 1 except that the film thickness of the first layer in Example 1 was 1.5 μm. The evaluation results of the obtained polycarbonate resin molded product are shown in Table 1.
[0062]
[Comparative Example 2]
Compound having added ultraviolet absorbing group of Example 2, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole (chloroform solution having a concentration of 10 mg / L, measured at an optical path length of 1.0 cm, wavelength of 300 nm The concentration of 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole remaining in the film was 0.15 g / cm.3A test piece was prepared in the same manner as in Example 2 except that. The evaluation results of the obtained polycarbonate resin molded product are shown in Table 1.
[0063]
[Comparative Example 3]
Compound having an ultraviolet absorbing group added in Example 3, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole (chloroform solution having a concentration of 10 mg / L, measured at an optical path length of 1.0 cm, wavelength of 300 nm The concentration of 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole remaining in the film was 0.45 g / cm.3A test piece was prepared in the same manner as in Example 3 except that. The evaluation results of the obtained polycarbonate resin molded product are shown in Table 1.
[0064]
[Comparative Example 4]
A test piece was prepared in the same manner as in Example 2 except that the film thickness of the first layer in Example 2 was 9.0 μm. The evaluation results of the obtained polycarbonate resin molded product are shown in Table 1.
[0065]
[Comparative Example 5]
2,4-di-benzylphenyl-3,5-di-t instead of 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, a compound having an ultraviolet absorbing group added in Example 2 4 parts of 4-butyl-4-hydroxybenzoate (chloroform solution with a concentration of 10 mg / L, measured at an optical path length of 1.0 cm and an absorbance at a wavelength of 300 nm of 0.003) are added, and 2,4-diphenyl remaining in the film -Benzylphenyl-3,5-di-t-butyl-4-hydroxybenzoate concentration of 0.30 g / cm3A test piece was prepared in the same manner as in Example 2 except that. The evaluation results of the obtained polycarbonate resin molded product are shown in Table 1.
[0066]
[Comparative Example 6]
A test piece was prepared in the same manner as in Example 5 except that acrylic resin (IV) was used instead of acrylic resin (III) in Example 5. The evaluation results of the obtained polycarbonate resin molded product are shown in Table 1.
[0067]
[Table 1]
[0068]
【The invention's effect】
The polycarbonate laminate of the present invention has good appearance, adhesion, and abrasion resistance, and has a high level of actual weathering resistance. Particularly, the polycarbonate laminate with both sides protected is suitable for automobile window glass and sunroof. The industrial effects that it produces are exceptional.
Claims (1)
2≦d≦8・・・(1)
0.1≦c≦0.5・・・(2)
0.6≦d×c≦3・・・(3)
(但し、ここでdはμmで表された第一層膜厚であり、cは該層中のg/cm3で表された紫外線吸収能を有する化合物に由来する単位の濃度である)A laminate in which two layers of an acrylic resin layer (first layer) and a composition cured layer (second layer) containing a colloidal silica-containing organosiloxane resin are sequentially laminated on at least one surface of a transparent polycarbonate resin plate, Ultraviolet rays in which the first layer of the laminate satisfies the following formulas (1) to (3) and has an absorbance at a wavelength of 300 nm of 0.25 or more measured with a chloroform solution having a concentration of 10 mg / L and an optical path length of 1.0 cm. A polycarbonate resin laminate excellent in actual weathering resistance, comprising a compound having an absorptive ability.
2 ≦ d ≦ 8 (1)
0.1 ≦ c ≦ 0.5 (2)
0.6 ≦ d × c ≦ 3 (3)
(However, where d is the first layer thickness, expressed in [mu] m, c is the concentration of units derived from a compound having an ultraviolet absorbing ability, expressed in g / cm 3 in the layer)
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002187969A JP4065728B2 (en) | 2002-06-27 | 2002-06-27 | Polycarbonate resin laminate with excellent weather resistance |
KR1020047002490A KR100984993B1 (en) | 2002-06-21 | 2003-06-20 | Acrylic resin composition, organosiloxane resin composition and laminates made by using them |
AU2003244100A AU2003244100A1 (en) | 2002-06-21 | 2003-06-20 | Acrylic resin composition, organosiloxane resin composition and laminates made by using them |
EP03760926.0A EP1516722B1 (en) | 2002-06-21 | 2003-06-20 | Acrylic resin composition, organosiloxane resin composition and laminates made by using them |
CNB038011859A CN100519178C (en) | 2002-06-21 | 2003-06-20 | Acrylic resin composition, organosiloxane resin composition and laminate comprising the same |
PCT/JP2003/007883 WO2004000551A1 (en) | 2002-06-21 | 2003-06-20 | Acrylic resin composition, organosiloxane resin composition and laminates made by using them |
US10/487,218 US7070859B2 (en) | 2002-06-21 | 2003-06-20 | Acrylic resin composition organosiloxane resin composition and laminate comprising the same |
CA 2460387 CA2460387C (en) | 2002-06-21 | 2003-06-20 | Acrylic resin composition, organosiloxane resin composition and laminate comprising the same |
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CN100436560C (en) * | 2004-11-19 | 2008-11-26 | 比亚迪股份有限公司 | Ultraviolet light curing coating and production thereof |
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