JP4697386B2 - Polycarbonate resin laminate and method for producing the same - Google Patents
Polycarbonate resin laminate and method for producing the same Download PDFInfo
- Publication number
- JP4697386B2 JP4697386B2 JP2004122791A JP2004122791A JP4697386B2 JP 4697386 B2 JP4697386 B2 JP 4697386B2 JP 2004122791 A JP2004122791 A JP 2004122791A JP 2004122791 A JP2004122791 A JP 2004122791A JP 4697386 B2 JP4697386 B2 JP 4697386B2
- Authority
- JP
- Japan
- Prior art keywords
- polycarbonate resin
- weight
- coating composition
- film
- parts
- 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.)
- Expired - Lifetime
Links
- 239000004431 polycarbonate resin Substances 0.000 title claims description 46
- 229920005668 polycarbonate resin Polymers 0.000 title claims description 46
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000008199 coating composition Substances 0.000 claims description 40
- 229920005989 resin Polymers 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 26
- 238000005452 bending Methods 0.000 claims description 18
- -1 Propylene oxide-modified neopentyl glycol diacrylate Chemical class 0.000 claims description 17
- 229920003002 synthetic resin Polymers 0.000 claims description 10
- 239000000057 synthetic resin Substances 0.000 claims description 10
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- 239000003085 diluting agent Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 230000001588 bifunctional effect Effects 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 23
- 229920005862 polyol Polymers 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 13
- 150000003077 polyols Chemical class 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000000758 substrate Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 229920000570 polyether Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229920005906 polyester polyol Polymers 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- 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 2
- WXHVQMGINBSVAY-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 WXHVQMGINBSVAY-UHFFFAOYSA-N 0.000 description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229960000969 phenyl salicylate Drugs 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- POLSVAXEEHDBMJ-UHFFFAOYSA-N (2-hydroxy-4-octadecoxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 POLSVAXEEHDBMJ-UHFFFAOYSA-N 0.000 description 1
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- ARVUDIQYNJVQIW-UHFFFAOYSA-N (4-dodecoxy-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 ARVUDIQYNJVQIW-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- ASVSBPGJUQTHBG-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-dodecoxyphenol Chemical compound CCCCCCCCCCCCOc1ccc(c(O)c1)-c1nc(nc(n1)-c1ccccc1)-c1ccccc1 ASVSBPGJUQTHBG-UHFFFAOYSA-N 0.000 description 1
- LEVFXWNQQSSNAC-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexoxyphenol Chemical compound OC1=CC(OCCCCCC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 LEVFXWNQQSSNAC-UHFFFAOYSA-N 0.000 description 1
- UUINYPIVWRZHAG-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-methoxyphenol Chemical compound OC1=CC(OC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 UUINYPIVWRZHAG-UHFFFAOYSA-N 0.000 description 1
- BBBLHSHFZWKLPP-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-phenylmethoxyphenol Chemical compound Oc1cc(OCc2ccccc2)ccc1-c1nc(nc(n1)-c1ccccc1)-c1ccccc1 BBBLHSHFZWKLPP-UHFFFAOYSA-N 0.000 description 1
- DSBLSFKNWFKZON-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propoxyphenol Chemical compound CCCOc1ccc(c(O)c1)-c1nc(nc(n1)-c1ccccc1)-c1ccccc1 DSBLSFKNWFKZON-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- FROCQMFXPIROOK-UHFFFAOYSA-N 4-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]benzene-1,3-diol Chemical compound CC1=CC(C)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(O)=CC=2)O)=N1 FROCQMFXPIROOK-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- GCPDCGCMGILXLN-UHFFFAOYSA-N 5-butoxy-2-(4,6-diphenyl-1,3,5-triazin-2-yl)phenol Chemical compound OC1=CC(OCCCC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 GCPDCGCMGILXLN-UHFFFAOYSA-N 0.000 description 1
- PGDIJTMOHORACQ-UHFFFAOYSA-N 9-prop-2-enoyloxynonyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCOC(=O)C=C PGDIJTMOHORACQ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 239000004420 Iupilon Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 229940024874 benzophenone Drugs 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- SODJJEXAWOSSON-UHFFFAOYSA-N bis(2-hydroxy-4-methoxyphenyl)methanone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1O SODJJEXAWOSSON-UHFFFAOYSA-N 0.000 description 1
- YFNONBGXNFCTMM-UHFFFAOYSA-N butoxybenzene Chemical group CCCCOC1=CC=CC=C1 YFNONBGXNFCTMM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- TZAMQIAPGYOUKF-UHFFFAOYSA-N diethoxyphosphoryl(phenyl)methanone Chemical compound CCOP(=O)(OCC)C(=O)C1=CC=CC=C1 TZAMQIAPGYOUKF-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 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
- 239000012466 permeate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
Description
本発明は、ポリカーボネート樹脂シートに透明性、耐擦傷性、耐候性、耐薬品性及び耐折曲げ性に優れ、反りの小さい紫外線硬化型樹脂被覆用組成物を塗布後、硬化させて、硬化皮膜を形成させてなるポリカーボネート樹脂積層体及びその製造方法に関するものである。 The present invention is a cured film obtained by applying a UV curable resin coating composition having excellent transparency, scratch resistance, weather resistance, chemical resistance and bending resistance to a polycarbonate resin sheet, and having a small warpage, followed by curing. It is related with the polycarbonate resin laminated body formed by forming and its manufacturing method.
ポリカーボネート樹脂成形品は、軽さや加工のしやすさなどの種々の特性からガラスに代わる材料として、建物の採光材や車両の窓用、計器カバー等に用いられている。しかしながら、ガラスと比較して耐擦傷性、耐薬品性、及び耐候性等の表面特性に劣る。そこで、ポリカーボネート基材の表面を改質する方法として、例えば、（ｉ）溶剤のような非反応性で揮発性の成分をほとんど含まない紫外線硬化コーティング組成物を熱可塑性樹脂基材の表面に塗布し、（ii）未硬化のコーティング組成物と基材表面とを９０〜１５０°Ｆから選択された温度に加熱して、未硬化のコーティング組成物の一部を熱可塑性樹脂基材の表面下のある領域中に浸透させて表面下に熱可塑性樹脂基材とコーティング組成物の両方を含むコーティング組成物浸透領域を形成させ、（iii）こうして塗布したコーティング組成物を、コーティング組成物と浸透領域中に紫外線を当てることによって紫外線で硬化させることからなる。コーティング組成物の紫外線硬化の際に熱可塑性樹脂基材の表面下の浸透領域は基材と硬化したコーティングとの間の噛み合い結合を提供することが記載されている（特許文献１）。しかしながら、この方法ではコーティング組成物が熱可塑性樹脂基材に浸透しすぎるため、ポリカーボネート樹脂が本来有する耐衝撃性や耐折曲げ性が損なわれ、さらには反りが大きくなる。 Polycarbonate resin molded products are used for building lighting materials, vehicle windows, instrument covers, and the like as materials to replace glass due to various characteristics such as lightness and ease of processing. However, it is inferior in surface properties such as scratch resistance, chemical resistance, and weather resistance as compared with glass. Therefore, as a method for modifying the surface of the polycarbonate substrate, for example, (i) an ultraviolet curable coating composition containing almost no volatile components such as a solvent is applied to the surface of the thermoplastic resin substrate. And (ii) heating the uncured coating composition and the substrate surface to a temperature selected from 90 to 150 ° F., so that a portion of the uncured coating composition is below the surface of the thermoplastic resin substrate. A coating composition penetration region comprising both the thermoplastic resin substrate and the coating composition under the surface, and (iii) the coating composition thus applied is applied to the coating composition and the penetration region. It consists of curing with ultraviolet light by applying ultraviolet light inside. It is described that the penetration area below the surface of a thermoplastic resin substrate provides an intermeshing bond between the substrate and the cured coating during UV curing of the coating composition (Patent Document 1). However, in this method, since the coating composition penetrates too much into the thermoplastic resin substrate, the impact resistance and the bending resistance inherent in the polycarbonate resin are impaired, and the warpage increases.
耐候性、耐擦傷性、及び密着力に優れ、かつ表面欠陥の少ないポリカーボネート樹脂成形品として、（Ａ）１，４−ブタンジオールジ（メタ）アクリレート及び１，６−ヘキサンジオールジ（メタ）アクリレートの少なくとも一種を必須成分とする、分子中に２個以上のアクリロイルオキシ基またはメタクリロイルオキシ基を有する架橋重合性化合物（ａ−１）と、該化合物（ａ−１）と共重合可能な他の化合物（ａ−２）とからなる光重合性組成物、（Ｂ）３６５〜４００ｎｍ増感波長のピークを有する特定の光重合開始剤（ｂ−１）を含む光重合開始剤、および（Ｃ）紫外線吸収剤を主成分として含有してなる紫外線硬化型樹脂被覆用組成物で被覆したポリカーボネート樹脂成形品の製法が知られていた（特許文献２）。しかしながら、この文献に開示されている紫外線硬化型樹脂被覆用組成物では、ポリカーボネート樹脂シートの製造時に同時に硬化皮膜で被覆されたポリカーボネート樹脂積層体を製造するには、該紫外線硬化型樹脂被覆用組成物では、高温で粘度が低下するため、均一な硬化皮膜を得ることが困難であるばかりか、該紫外線硬化型樹脂被覆用組成物がポリカーボネート樹脂シートに浸透しすぎるため、ポリカーボネート樹脂が本来有する耐衝撃性や耐折曲げ性が損なわれ、反りが大きくなるという問題があり、さらに、該紫外線硬化型樹脂被覆用組成物を使用するためには、ポリカーボネートシートを室温近くまで冷却する必要があり、ポリカーボネート樹脂シートを製造する押出機から、該紫外線硬化型樹脂被覆用組成物を塗布するまでの距離が十数メートルも必要であった。 (A) 1,4-butanediol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate as polycarbonate resin molded products having excellent weather resistance, scratch resistance and adhesion, and few surface defects A cross-linkable polymerizable compound (a-1) having two or more acryloyloxy groups or methacryloyloxy groups in the molecule and at least one of the above as an essential component, and other compounds copolymerizable with the compound (a-1) A photopolymerizable composition comprising the compound (a-2), (B) a photopolymerization initiator containing a specific photopolymerization initiator (b-1) having a peak of 365 to 400 nm sensitization wavelength, and (C) There has been known a method for producing a polycarbonate resin molded article coated with an ultraviolet curable resin coating composition containing an ultraviolet absorbent as a main component (Patent Document 2). However, in the ultraviolet curable resin coating composition disclosed in this document, in order to produce a polycarbonate resin laminate coated with a cured film at the same time as the production of the polycarbonate resin sheet, the ultraviolet curable resin coating composition is used. In the product, since the viscosity decreases at high temperature, it is difficult to obtain a uniform cured film, and the ultraviolet curable resin coating composition penetrates too much into the polycarbonate resin sheet. There is a problem that impact resistance and bending resistance are impaired and warping increases, and in addition, in order to use the composition for coating an ultraviolet curable resin, it is necessary to cool the polycarbonate sheet to near room temperature, From the extruder for producing the polycarbonate resin sheet to the application of the UV-curable resin coating composition The distance is several tens of meters was also necessary.
ポリカーボネート樹脂シートに被覆用組成物を塗布し、硬化皮膜を形成することにより耐擦傷性を改良した公知のポリカーボネート樹脂積層体の場合、被覆用組成物がポリカーボネート樹脂シートに浸透しすぎるため、硬化皮膜に発生したクラックが樹脂シートに伝播して、該積層体の耐衝撃性や耐折曲げ性が著しく損なわれるという問題があった。例えば、耐擦傷性の改良された厚さ０．５ｍｍのポリカーボネート樹脂積層体からなる試験片を上１８０°、下１８０°の折曲げ試験を行うと、２回以下の折曲げで破断するような耐折曲げ性の劣る積層体であった。 In the case of a known polycarbonate resin laminate in which the coating composition is applied to the polycarbonate resin sheet and the cured film is formed to improve the scratch resistance, the coating composition is excessively permeated into the polycarbonate resin sheet. There was a problem that the cracks generated in the film propagated to the resin sheet, and the impact resistance and bending resistance of the laminate were significantly impaired. For example, when a test piece made of a polycarbonate resin laminate having a thickness of 0.5 mm with improved scratch resistance is subjected to a bending test of 180 ° above and 180 ° below, the test piece breaks when bent twice or less. The laminate was inferior in bending resistance.
本発明は、上記諸問題を解決し、透明性、耐擦傷性、耐候性、耐薬品性のみならず耐折曲げ性に優れ、反りが小さく、高温のポリカーボネート樹脂シートに塗布が可能な紫外線硬化型樹脂組成物を開発し、さらに、ポリカーボネート樹脂シートの製造時に、樹脂シート上に硬化皮膜を形成したポリカーボネート樹脂積層体及び該積層体の製造方法を提供することである。 The present invention solves the above-mentioned problems and is not only transparent, scratch resistant, weather resistant, chemical resistant but also has excellent bending resistance, small warpage, and UV curing that can be applied to a high-temperature polycarbonate resin sheet. A mold resin composition is developed, and a polycarbonate resin laminate in which a cured film is formed on the resin sheet at the time of production of the polycarbonate resin sheet and a method for producing the laminate are provided.
本発明者らは、上記課題を解決するために鋭意検討した結果、表面温度７０〜９０℃であるポリカーボネート樹脂シート上に紫外線硬化型樹脂被覆用組成物を塗布しても、ポリカーボネート樹脂への過度の浸透が起こらない紫外線硬化型樹脂被覆用組成物を見出し、さらに、該被覆用組成物からなる硬化皮膜で被覆されたポリカーボネート樹脂積層体は、透明性、耐擦傷性、耐候性及び耐薬品性のみならず、耐折曲げ性にも著しく優れ、反りも小さいことを見出し、本発明を完成させた。すなわち、本発明の要旨は、プロピレンオキサイド変性ネオペンチルグリコールジアクリレート（Ａ）２０〜７０重量％と、重量平均分子量４００以上の２〜４官能のアクリレートオリゴマ−（Ｂ）８０〜３０重量％からなる光重合性組成物（Ｃ）１００重量部に対し、光重合開始剤（Ｄ）を１〜１０重量部配合してなる紫外線硬化型樹脂被覆用組成物（Ｅ）を、ポリカーボネート樹脂シート（Ｆ）の少なくとも一方の面に塗布後、硬化させ、硬化皮膜を形成させてなる耐折曲げ性に優れたポリカーボネート樹脂積層体（Ｇ）及びその製造方法である。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that even if the composition for coating an ultraviolet curable resin is applied on a polycarbonate resin sheet having a surface temperature of 70 to 90 ° C., excessive application to the polycarbonate resin is not possible. A UV-curable resin coating composition that does not permeate water is found, and a polycarbonate resin laminate coated with a cured film made of the coating composition has transparency, scratch resistance, weather resistance, and chemical resistance. In addition, the inventors have found that the bending resistance is remarkably excellent and the warpage is small, and the present invention has been completed. That is, the gist of the present invention consists of 20 to 70% by weight of propylene oxide-modified neopentyl glycol diacrylate (A) and 80 to 30% by weight of a bi- and tetrafunctional acrylate oligomer (B) having a weight average molecular weight of 400 or more. An ultraviolet curable resin coating composition (E) obtained by blending 1 to 10 parts by weight of a photopolymerization initiator (D) with respect to 100 parts by weight of the photopolymerizable composition (C), a polycarbonate resin sheet (F) It is the polycarbonate resin laminated body (G) excellent in the bending resistance formed by making it harden | cure after application | coating to at least one surface of this, and forming a cured film, and its manufacturing method.
本発明の光重合性組成物（Ｃ）の成分の１つは、プロピレンオキサイド変性ネオペンチルグリコールジアクリレート（Ａ）である。 One of the components of the photopolymerizable composition (C) of the present invention is propylene oxide-modified neopentyl glycol diacrylate (A).
本発明の光重合性組成物（Ｃ）の成分のもう１つであるアクリレートオリゴマー（Ｂ）は、ポリヒドロキシ含有化合物をアクリル酸および／またはメタアクリル酸と反応させることによって製造される。本発明に使用しうる「ポリオール」とも称されるポリヒドロキシ含有化合物は、３個以上のヒドロキシ基を有する化合物である。一般に、本発明に使用することができるポリオールは、３個〜６個のヒドロキシ基、好ましくは３個〜４個のヒドロキシ基、および２個〜３６個の炭素原子を有する化合物である。これらのポリオールは、分岐鎖または直鎖脂肪族ポリオール、脂環式ポリオール、芳香族ポリオール、ポリエーテルポリオール、およびポリエステルポリオールである。脂肪族ポリオールとしては、トリオール、例えば、グリセリン、トリメチロールプロパン、およびトリメチロールエタン；テトラオール、例えば、ペンタエリトリトールおよびジ−トリメチロールプロパン；およびヘキサオール、例えば、ジペンタエリトリトールを挙げることができる。さらに、脂肪族および脂環式ポリオールを、種々の量のエチレンオキシドおよび／またはプロピレンオキシドと反応させて、エトキシル化および／またはプロポキシル化ポリオールを得ることができる。エトキシル化および／またはプロポキシル化ポポリオールの例としては、エトキシル化トリメチロールプロパン、プロポキシル化トリメチロールプロパン、エトキシル化グリセリン、プロポキシル化グリセリン、エトキシル化ペンタエリトリトール、およびプロポキシル化ペンタエリトリトールを挙げることができる。本発明に使用できるポリエーテルポリオールは、芳香族ポリエーテルおよび脂肪族ポリエーテルの両方である。ポリエーテルポリオールの脂肪族基は、直鎖、分岐鎖、または環状であってよい。ポリエーテルポリオールの例としては、トリ−グリコール、例えば、トリエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコール、ならびに混合ポリエーテル、例えば、ポリ（プロピレン−エチレン）グリコールを挙げることができる。ポリエステルポリオールは、エステル結合を有するポリオールである。例えば、過剰のポリオールを二塩基酸無水物と反応させて、約１個〜約６個のエステル結合および反応性ヒドロキシ基を有する低分子量化合物を得る。前記ポリオール単独および混合物のいずれかを使用して、ポリエステルポリオールを製造することができる。ポリエステルポリオールを製造するために使用することができる二塩基酸無水物の例としては、テトラヒドロフタル酸無水物のような脂環式二塩基酸無水物を使用して、ポリエステルポリオールを製造することもできる。最後に、ポリエーテルおよびポリエステルポリオールを、種々の量のエチレンオキシドおよび／またはプロピレンオキシドと反応させて、エトキシル化および／またはプロポキシル化ポリオールを得ることができる。 The acrylate oligomer (B) which is another component of the photopolymerizable composition (C) of the present invention is produced by reacting a polyhydroxy-containing compound with acrylic acid and / or methacrylic acid. The polyhydroxy-containing compound, also called “polyol”, that can be used in the present invention is a compound having three or more hydroxy groups. In general, the polyols that can be used in the present invention are compounds having 3 to 6 hydroxy groups, preferably 3 to 4 hydroxy groups, and 2 to 36 carbon atoms. These polyols are branched or straight chain aliphatic polyols, alicyclic polyols, aromatic polyols, polyether polyols, and polyester polyols. Aliphatic polyols can include triols such as glycerin, trimethylolpropane, and trimethylolethane; tetraols such as pentaerythritol and di-trimethylolpropane; and hexaols such as dipentaerythritol. In addition, aliphatic and cycloaliphatic polyols can be reacted with various amounts of ethylene oxide and / or propylene oxide to give ethoxylated and / or propoxylated polyols. Examples of ethoxylated and / or propoxylated popolyols include ethoxylated trimethylolpropane, propoxylated trimethylolpropane, ethoxylated glycerin, propoxylated glycerin, ethoxylated pentaerythritol, and propoxylated pentaerythritol. be able to. The polyether polyols that can be used in the present invention are both aromatic and aliphatic polyethers. The aliphatic group of the polyether polyol may be linear, branched or cyclic. Examples of polyether polyols include tri-glycols such as triethylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, and mixed polyethers such as poly (propylene-ethylene) glycol. The polyester polyol is a polyol having an ester bond. For example, an excess of polyol is reacted with a dibasic acid anhydride to obtain a low molecular weight compound having from about 1 to about 6 ester linkages and reactive hydroxy groups. Polyester polyols can be produced using either the polyol alone or a mixture. Examples of dibasic acid anhydrides that can be used to produce polyester polyols include the production of polyester polyols using alicyclic dibasic acid anhydrides such as tetrahydrophthalic anhydride. it can. Finally, polyether and polyester polyols can be reacted with various amounts of ethylene oxide and / or propylene oxide to give ethoxylated and / or propoxylated polyols.
本発明の方法において、ポリヒドロキシ含有化合物を、単一で、または他のポリヒドロキシ含有化合物および／またはモノヒドロキシ含有化合物と組み合わせて、使用することができる。さらに、アクリル酸およびメタクリル酸を、単一で、または相互に組み合わせて、使用することができる。当然のことであるが、ヒドロキシ含有反応物の混合物が本発明の方法に使用される場合には、混合エステル生成物が得られる。アクリル酸およびメタクリル酸の混合物が使用される場合も同様であり、生成物は混合エステル生成物となる。 In the method of the present invention, the polyhydroxy-containing compound can be used alone or in combination with other polyhydroxy-containing compounds and / or monohydroxy-containing compounds. Furthermore, acrylic acid and methacrylic acid can be used alone or in combination with each other. Of course, when a mixture of hydroxy-containing reactants is used in the process of the present invention, a mixed ester product is obtained. The same is true when a mixture of acrylic and methacrylic acid is used, and the product is a mixed ester product.
本発明で好ましく使用されるアクリレートオリゴマー（Ｂ）は、テトラヒドロ無水フタル酸及びトリメチロールプロパンと、アクリル酸とを常法によりエステル化反応させることにより得られ、かつ重量平均分子量が４００〜２５００で２〜４官能のアクリレートオリゴマーである。この範囲以外のアクリレートオリゴマーを用いた場合、光重合性組成物からの紫外線硬化型樹脂被覆用組成物の可撓性や耐折曲げ性が低下するので好ましくない。 The acrylate oligomer (B) preferably used in the present invention is obtained by subjecting tetrahydrophthalic anhydride and trimethylolpropane and acrylic acid to an esterification reaction by a conventional method, and has a weight average molecular weight of 400 to 2500. It is a tetrafunctional acrylate oligomer. When an acrylate oligomer other than this range is used, the flexibility and bending resistance of the UV-curable resin coating composition from the photopolymerizable composition are not preferred.
本発明に関わる光重合性組成物（Ｃ）には、反応性希釈剤（Ｈ）をアクリレートオリゴマ−の取扱い上から配合するのが好ましい。反応性希釈剤（Ｈ）としては、ジプロピレングリコールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、トリプロピレングリコールトリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリトリトールトリ（メタ）アクリレート、ペンタエリトリトールテトラ（メタ）アクリレート等が挙げられ、好ましくは、トリプロピレングリコールトリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレートである。 In the photopolymerizable composition (C) according to the present invention, a reactive diluent (H) is preferably blended from the handling of the acrylate oligomer. Examples of the reactive diluent (H) include dipropylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol tri ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like, preferably tripropylene glycol tri (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, dipropylene glycol di (meth) acrylate.
反応性希釈剤（Ｈ）の配合量は、アクリレートオリゴマ−（Ｂ）１００重量部に対して、１５〜７０重量部である。反応性希釈剤（Ｈ）の配合量が１５重量部未満では、紫外線硬化型樹脂被覆用組成物（Ｅ）の粘度が高すぎ、７０重量部を越えると硬化皮膜の反りが悪くなったり耐折曲げ性が低下する。
反応性希釈剤を光重合性組成物（Ｃ）に配合する場合は、アクリレートオリゴマー（Ｂ）の一部として取り扱う。
The compounding quantity of a reactive diluent (H) is 15-70 weight part with respect to 100 weight part of acrylate oligomer (B). When the amount of the reactive diluent (H) is less than 15 parts by weight, the viscosity of the UV-curable resin coating composition (E) is too high, and when it exceeds 70 parts by weight, the cured film is less warped or folded. Flexibility decreases.
When mix | blending a reactive diluent with a photopolymerizable composition (C), it handles as a part of acrylate oligomer (B).
本発明に使用される光重合開始剤（Ｄ）としては、一般に知られているものが使用できる。具体的には、ベンゾイン、ベンゾフェノン、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、２，２−ジメトキシ−２−フェニルアセトフェノン、１−ヒドロキシシクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、アゾビスイソブチロニトリル、ベンゾイルパーオキシド等が挙げられる。 As the photopolymerization initiator (D) used in the present invention, those generally known can be used. Specifically, benzoin, benzophenone, benzoin ethyl ether, benzoin isopropyl ether, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, azobisisobutyronitrile, benzoyl peroxide and the like.
また、下記一般式（１）で表されるアシロフォスフィンオキサイド系化合物を光重合開始剤（Ｄ）として併用することは好ましい態様である。 Moreover, it is a preferable aspect to use together the acylophosphine oxide type compound represented by following General formula (1) as a photoinitiator (D).
特に好ましい具体例としては、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド、ベンゾイルジエトキシフォスフィンオキサイド等が挙げられる。
Particularly preferred specific examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine oxide, and the like.
本発明に係わる光重合性組成物（Ｃ）は、前記（Ａ）２０〜７０重量％と、重量平均分子量４００以上の２〜４官能のアクリレートオリゴマー（Ｂ）８０〜３０重量％との混合物である。光重合性組成物（Ｃ）中で（Ａ）成分が２０重量％未満では、光重合性組成物（Ｃ）の粘度が高くなりすぎ塗膜の密着性が低下する。また、光重合性組成物（Ｃ）中で（Ａ）成分が７０重量％を越えると光重合性組成物（Ｃ）の粘度が低くなり過ぎて光学歪みが発生し易くなるので好ましくない。また、光重合開始剤（Ｄ）の使用量は、光重合性組成物（Ｃ）１００重量部に対し、１〜１０重量部、好ましくは３〜６重量部である。１０重量部よりも多いと硬化被膜が着色し、１重量部より少ないと十分な硬化被膜が得られない。 The photopolymerizable composition (C) according to the present invention is a mixture of (A) 20 to 70% by weight and 80 to 30% by weight of a bi- and tetrafunctional acrylate oligomer (B) having a weight average molecular weight of 400 or more. is there. When the component (A) is less than 20% by weight in the photopolymerizable composition (C), the viscosity of the photopolymerizable composition (C) becomes too high and the adhesion of the coating film is lowered. Further, if the component (A) exceeds 70% by weight in the photopolymerizable composition (C), the viscosity of the photopolymerizable composition (C) becomes too low and optical distortion tends to occur, which is not preferable. Moreover, the usage-amount of a photoinitiator (D) is 1-10 weight part with respect to 100 weight part of photopolymerizable compositions (C), Preferably it is 3-6 weight part. When the amount is more than 10 parts by weight, the cured film is colored. When the amount is less than 1 part by weight, a sufficient cured film cannot be obtained.
光重合性組成物（Ｃ）に光重合開始剤（Ｄ）を配合してなる紫外線硬化型樹脂被覆用組成物（Ｅ）には、さらに紫外線吸収剤（Ｉ）を配合することが好ましい。紫外線吸収剤（Ｉ）としては、ベンゾフェノン系、ベンゾトリアゾール系、サリチル酸フェニル系、トリアジン系等が挙げられる。 It is preferable to further mix an ultraviolet absorber (I) in the ultraviolet curable resin coating composition (E) formed by blending the photopolymerization initiator (D) with the photopolymerizable composition (C). Examples of the ultraviolet absorber (I) include benzophenone, benzotriazole, phenyl salicylate, and triazine.
ベンゾフェノン系紫外線吸収剤としては、２，４−ジヒドロキシ−ベンゾフェノン、２−ヒドロキシ−４−メトキシ−ベンゾフェノン、２−ヒドロキシ−４−ｎ−オクトキシ−ベンゾフェノン、２−ヒドロキシ−４−ドデシロキシ−ベンゾフェノン、２−ヒドロキシ−４−オクタデシロキシ−ベンゾフェノン、２，２’−ジヒドロキシ−４−メトキシ−ベンゾフェノン、２，２’−ジヒドロキシ−４，４’−ジメトキシ−ベンゾフェノン、２，２’，４，４’−テトラヒドロキシ−ベンゾフェノン等が挙げられる。 Examples of the benzophenone ultraviolet absorber include 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2- Hydroxy-4-octadecyloxy-benzophenone, 2,2′-dihydroxy-4-methoxy-benzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-benzophenone, 2,2 ′, 4,4′-tetra And hydroxy-benzophenone.
ベンゾトリアゾール系紫外線吸収剤としては、２−（２’−ヒドロキシ−５−メチルフェニル）ベンゾトリアゾール、２−（ヒドロキシ−５−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾール等が挙げられる。 Examples of the benzotriazole ultraviolet absorber include 2- (2'-hydroxy-5-methylphenyl) benzotriazole, 2- (hydroxy-5-tert-butylphenyl) benzotriazole and the like.
サリチル酸フェニル系紫外線吸収剤としては、フェニルサルチレート、２−４−ジターシャリーブチルフェニル−３，５−ジターシャリーブチル−４−ヒドロキシベンゾエート等が挙げられる。ヒンダードアミン系紫外線吸収剤としては、ビス（２，２，６，６−テトラメチルピペリジン−４−イル）セバケート等が挙げられる。 Examples of the phenyl salicylate ultraviolet absorber include phenylsulcylate, 2-4-ditertiarybutylphenyl-3,5-ditertiarybutyl-4-hydroxybenzoate, and the like. Examples of hindered amine ultraviolet absorbers include bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate.
トリアジン系紫外線吸収剤としては、２，４−ジフェニル−６−（２−ヒドロキシ−４−メトキシフェニル）−１，３，５−トリアジン、２，４−ジフェニル−６−（２−ヒドロキシ−４−エトキシフェニル）−１，３，５−トリアジン、２，４−ジフェニル−（２−ヒドロキシ−４−プロポキシフェニル）−１，３，５−トリアジン、２，４−ジフェニル−（２−ヒドロキシ−４−ブトキシフェニル）−１，３，５−トリアジン、２，４−ジフェニル−６−（２−ヒドロキシ−４−ブトキシフェニル）−１，３，５−トリアジン、２，４−ジフェニル−６−（２−ヒドロキシ−４−ヘキシルオキシフェニル）−１，３，５−トリアジン、２，４−ジフェニル−６−（２−ヒドロキシ−４−オクチルオキシフェニル）−１，３，５−トリアジン、２，４−ジフェニル−６−（２−ヒドロキシ−４−ド
デシルオキシフェニル）−１，３，５−トリアジン、２，４−ジフェニル−６−（２−ヒドロキシ−４−ベンジルオキシフェニル）−１，３，５−トリアジン、２−（２，４−ジヒドロキシフェニル）−４，６−ビス（２，４−ジメチルフェニル）−１，３，５−トリアジン等が挙げられる。
Examples of triazine ultraviolet absorbers include 2,4-diphenyl-6- (2-hydroxy-4-methoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-). Ethoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-propoxyphenyl) -1,3,5-triazine, 2,4-diphenyl- (2-hydroxy-4-) Butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-butoxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2- Hydroxy-4-hexyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazi 2,4-diphenyl-6- (2-hydroxy-4-dodecyloxyphenyl) -1,3,5-triazine, 2,4-diphenyl-6- (2-hydroxy-4-benzyloxyphenyl) -1 , 3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like.
紫外線吸収剤としては、上記以外に紫外線の保有するエネルギーを、分子内で振動エネルギーに変換し、その振動エネルギーを、熱エネルギー等として放出する機能を有する化合物が含まれる。さらに、酸化防止剤あるいは着色剤等との併用で効果を発現するもの、あるいはクエンチャーと呼ばれる、光エネルギー変換剤的に作用する光安定剤等も併用することができる。 In addition to the above, the ultraviolet absorber includes a compound having a function of converting the energy held by ultraviolet rays into vibrational energy in the molecule and releasing the vibrational energy as thermal energy or the like. Furthermore, those that exhibit an effect when used in combination with an antioxidant, a colorant, or the like, or a light stabilizer that acts as a light energy conversion agent, called a quencher, can be used in combination.
紫外線硬化型樹脂被覆用組成物（Ｅ）中の紫外線吸収剤（Ｉ）の配合量は、光重合性組成物（Ｃ）１００重量部に対し、２〜１５重量部、好ましくは３〜１０重量部である。１５重量部よりも多いと密着性が悪くなり、２重量部より少ないとポリカーボネート樹脂に対する耐候性改良効果が小さい。 The compounding quantity of the ultraviolet absorber (I) in the ultraviolet curable resin coating composition (E) is 2 to 15 parts by weight, preferably 3 to 10 parts by weight with respect to 100 parts by weight of the photopolymerizable composition (C). Part. When the amount is more than 15 parts by weight, the adhesion is deteriorated, and when it is less than 2 parts by weight, the weather resistance improving effect on the polycarbonate resin is small.
本発明の紫外線硬化型樹脂被覆用組成物（Ｅ）の粘度は、ＪＩＳ Ｋ６３６４の回転式粘度計にて測定した場合、作業性及び得られた樹脂積層体の表面平滑性の点から、７０〜９０℃における粘度が、好ましくは１２〜１２０ｍＰａ・ｓ、より好ましくは１５〜９０ｍＰａ・ｓ、最も好ましくは２０〜７０ｍＰａ・ｓである。粘度が１２ｍＰａ・ｓ未満の場合、硬化皮膜の膜厚が均一にならず、光学歪みが生じ、１２０ｍＰａ・ｓを越えるとポリカーボネート樹脂に対する硬化皮膜の密着性が低下する。 When the viscosity of the ultraviolet curable resin coating composition (E) of the present invention is measured with a rotational viscometer of JIS K6364, from the viewpoint of workability and surface smoothness of the obtained resin laminate, 70 to The viscosity at 90 ° C. is preferably 12 to 120 mPa · s, more preferably 15 to 90 mPa · s, and most preferably 20 to 70 mPa · s. When the viscosity is less than 12 mPa · s, the film thickness of the cured film is not uniform and optical distortion occurs, and when it exceeds 120 mPa · s, the adhesion of the cured film to the polycarbonate resin is lowered.
また、粘度調整のために有機溶媒を用いることもでき、この他に必要に応じてシリカ、酸化チタン、酸化アルミニウム等の無機微粒子、架橋重合体また橋共重合体よりなる有機微粒子、酸化防止剤、安定剤、消泡剤、レベリング剤、顔料、帯電防止剤、防曇剤、艶消剤、艶出剤など適宜添加してもよい。 In addition, an organic solvent can be used to adjust the viscosity. In addition to these, inorganic fine particles such as silica, titanium oxide, and aluminum oxide, organic fine particles made of a crosslinked polymer or a bridge copolymer, an antioxidant, if necessary. Stabilizers, antifoaming agents, leveling agents, pigments, antistatic agents, antifogging agents, matting agents, and polishes may be added as appropriate.
本発明で使用されるポリカーボネート樹脂としては、２，２−ビス（４−ヒドロキシフェニル）アルカンや２，２−ビス（４−ヒドロキシ−３，５−ジハロゲノフェニル）アルカンで代表されるビスフェノール化合物から周知の方法で製造された重合体が用いられ、その重合体骨格に脂肪酸ジオールに由来する構造単位が含まれるエステル結合を持つ構造単位が含まれても良い。好ましくは、２，２−ビス（４−ヒドロキシフェニル）プロパンから誘導されるポリカーボネート樹脂である。分子量についても特に制限はないが、成形性や機械的強度の観点から粘度平均分子量で１７，０００〜４０，０００、より好ましくは２０，０００〜３０，０００のものである。そして、このポリカーボネート樹脂を使用して、シートを押出法によって、製造する際に、本発明は実施される。ポリカーボネート樹脂シートの厚さは０．１〜２０ｍｍ、好ましくは０．２〜１０ｍｍ、さらに好ましくは０．３〜５ｍｍである。 Examples of the polycarbonate resin used in the present invention include 2,2-bis (4-hydroxyphenyl) alkane and bisphenol compounds represented by 2,2-bis (4-hydroxy-3,5-dihalogenophenyl) alkane. A polymer produced by a known method is used, and a structural unit having an ester bond including a structural unit derived from a fatty acid diol may be included in the polymer skeleton. A polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane is preferred. Although there is no restriction | limiting in particular about molecular weight, From a viewpoint of a moldability or mechanical strength, a viscosity average molecular weight is 17,000-40,000, More preferably, it is a thing of 20,000-30,000. And this invention is implemented when manufacturing a sheet | seat by an extrusion method using this polycarbonate resin. The thickness of the polycarbonate resin sheet is 0.1 to 20 mm, preferably 0.2 to 10 mm, and more preferably 0.3 to 5 mm.
本発明において、上記紫外線硬化型樹脂被覆用組成物（Ｅ）を被覆したポリカーボネート樹脂積層体（Ｇ）を得るには、スプレー、浸漬、カーテンフロー、ロールコーティング等公知の方法を用いて塗布した後、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ、ガリウムランプ、メタルハライドランプ等の紫外線を照射することによって速やかに硬化させることもできるが、次のような方法が好ましい。すなわち、本発明の紫外線硬化型樹脂被覆用組成物（Ｅ）を７０〜９０℃の表面温度のポリカーボネート樹脂シート（Ｆ）と合成樹脂フィルム（Ｊ）との間に挟み込み、圧着後、該紫外線硬化型樹脂被覆用組成物（Ｅ）に紫外線を照射し、硬化後、合成樹脂フィルム（Ｊ）を硬化皮膜から剥離させる方法である。 In the present invention, in order to obtain the polycarbonate resin laminate (G) coated with the ultraviolet curable resin coating composition (E), it is applied using a known method such as spraying, dipping, curtain flow, roll coating, or the like. It is possible to cure quickly by irradiating with ultraviolet rays such as low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, gallium lamp, metal halide lamp, etc., but the following method is preferred. That is, the ultraviolet curable resin coating composition (E) of the present invention is sandwiched between a polycarbonate resin sheet (F) having a surface temperature of 70 to 90 ° C. and a synthetic resin film (J). In this method, the composition resin coating composition (E) is irradiated with ultraviolet rays and cured, and then the synthetic resin film (J) is peeled off from the cured film.
このようにして被覆される硬化塗膜の厚みは１〜１５μｍ、好ましくは２〜１０μｍである。硬化皮膜の厚さが１μｍ未満では十分な耐候性や耐擦傷性を得るのが難しく、１５μｍを越えると密着性やコストの点から好ましくない。 The thickness of the cured coating film thus coated is 1 to 15 μm, preferably 2 to 10 μm. When the thickness of the cured film is less than 1 μm, it is difficult to obtain sufficient weather resistance and scratch resistance, and when it exceeds 15 μm, it is not preferable from the viewpoint of adhesion and cost.
紫外線硬化型樹脂被覆用組成物（Ｅ）をポリカーボネート樹脂シート（Ｆ）と合成樹脂フィルム（Ｊ）との間に挟み込む際に使用される合成樹脂フィルム（Ｊ）は、紫外線硬化型樹脂被覆用組成物（Ｅ）と親和性のないことが必須条件であり、合成樹脂フィルム（Ｊ）の表面が被膜の表面を形成するため、表面の微細な平滑性が要求される場合などには、特にフィルムの選択には注意を要する。一般的にはポリエチレンテレフタレート（ＰＥＴ）フィルム等を用いることができる。合成樹脂フィルムの厚さは、１０〜２００μｍが好ましく、１０μｍ未満では合成樹脂フィルムにしわがよりやすく、２００μｍを越えると硬化皮膜の厚み調整が困難になる。 The synthetic resin film (J) used when the ultraviolet curable resin coating composition (E) is sandwiched between the polycarbonate resin sheet (F) and the synthetic resin film (J) is an ultraviolet curable resin coating composition. It is an essential condition that it has no affinity with the product (E), and since the surface of the synthetic resin film (J) forms the surface of the coating, the film is particularly necessary when fine smoothness of the surface is required. Care must be taken in selecting this. In general, a polyethylene terephthalate (PET) film or the like can be used. The thickness of the synthetic resin film is preferably 10 to 200 μm, and if it is less than 10 μm, the synthetic resin film is more likely to be wrinkled, and if it exceeds 200 μm, it is difficult to adjust the thickness of the cured film.
合成樹脂フィルム（Ｊ）とポリカーボネート樹脂シート（Ｆ）の間に被覆用組成物をはさみ込み圧着させる方法としては、プレスロール、しごき棒、ハケ、ヘラなどを用いて被膜の膜厚が均一になるように圧着できれば、いかなる方法を用いてもよい。 As a method of sandwiching the coating composition between the synthetic resin film (J) and the polycarbonate resin sheet (F) and press-bonding, the film thickness of the coating becomes uniform using a press roll, a squeezing bar, a brush, a spatula, etc. Any method may be used as long as it can be crimped.
本発明で使用される紫外線硬化型樹脂被覆用組成物は、ポリカーボネート樹脂シートへの過度の浸透が起こらないので、該被覆用組成物からなる硬化皮膜で被覆されたポリカーボネート樹脂積層体は、透明性、耐擦傷性、耐候性、耐薬品性のみならず耐折曲げ性にも著しく優れ、反りも小さいので、曲げ加工の施される用途や長時間曲げ歪みの加わる用途、高度の寸法精度の要求される用途に好適に使用できる。 Since the ultraviolet curable resin coating composition used in the present invention does not excessively penetrate the polycarbonate resin sheet, the polycarbonate resin laminate coated with the cured film made of the coating composition is transparent. , Not only scratch resistance, weather resistance, chemical resistance, but also excellent bending resistance and low warpage, so bending applications, applications where bending strain is applied for a long time, and high dimensional accuracy requirements It can be suitably used for the intended use.
次に実施例によって、本発明をさらに具体的に説明するが、本発明はこれらによって限定されるものではない。なお、実施例中の「部」は重量基準を表す。 EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. In addition, "part" in an Example represents a weight reference | standard.
実施例および比較例に用いた紫外線硬化型樹脂被覆用組成物の原材料と略号は次の通りである。
Ａ；Ｒ−２４０２：４官能ポリエステルアクリレートオリゴマー、重量平均分子量６００のテトラヒドロ無水フタル酸・トリメチロールプロパン・アクリル酸の重縮合物で、反応希釈剤としてトリメチロールプロパントリアクリレートを３０重量％含有（第一工業製薬（株）製）。
Ｂ：１，９−ノナンジオールジアクリレート（大阪有機化学工業（株）製）
Ｃ；ＮＡ−３０５：プロピレンオキサイド変性ネオペンチルグリコールジアクリレート（三洋化成（株）製）
Ｄ；ＴＡＳ：コハク酸／トリメチロールエタン／アクリル酸のモル比１／２／４の縮合物で、重量平均分子量が５３８であり、２０℃での粘度３０００〜５０００ｍＰａ・ｓ。
Ｅ；Ｕ６ＨＡ：６官能ウレタンアクリレートオリゴマーで、重量平均分子量が１２００（新中村化学工業（株）製）。
Ｆ；ＴＰＯ：２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド（ビ−・エ−・エス・エフ ジャパン（株）製）
Ｇ；Ｉｒｇａｃｕｒｅ１８４：１−ヒドロキシシクロヘキシルフェニルケトン（チバ・スペシャリティケミカルズ（株）製）
Ｈ：紫外線吸収剤：チヌビン−ＰＳ（２−（ヒドロキシ−５−ｔｅｒｔ−ブチルフェニル）ベンゾトリアゾール チバ・スペシャリティケミカルス（株）製）
The raw materials and abbreviations of the ultraviolet curable resin coating compositions used in Examples and Comparative Examples are as follows.
A: R-2402: tetrafunctional polyester acrylate oligomer, polycondensate of tetrahydrophthalic anhydride / trimethylolpropane / acrylic acid having a weight average molecular weight of 600, containing 30% by weight of trimethylolpropane triacrylate as a reaction diluent Ichi Kogyo Seiyaku Co., Ltd.).
B: 1,9-nonanediol diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
C; NA-305: Propylene oxide-modified neopentyl glycol diacrylate (manufactured by Sanyo Chemical Co., Ltd.)
D: TAS: succinic acid / trimethylolethane / acrylic acid condensate having a molar ratio of 1/2/4, a weight average molecular weight of 538, and a viscosity of 3000 to 5000 mPa · s at 20 ° C.
E: U6HA: a hexafunctional urethane acrylate oligomer having a weight average molecular weight of 1200 (manufactured by Shin-Nakamura Chemical Co., Ltd.).
F; TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BFS Japan Co., Ltd.)
G; Irgacure 184: 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals)
H: Ultraviolet absorber: Tinuvin-PS (2- (hydroxy-5-tert-butylphenyl) benzotriazole Ciba Specialty Chemicals Co., Ltd.)
実施例および比較例中の各種物性の測定及び評価は以下の方法で行った。
１）耐候性試験：ＪＩＳ Ｋ５４００に準拠し、カーボンアーク式サンシャインウエザオメーターにて促進試験を行って、１０００時間処理前後の黄変度と処理後の密着性を調べ、黄変度７以下で密着性良好なものを合格とした。
２）耐擦傷性試験：ＡＳＴＭ Ｄ１０４４に準拠し、テーバー摩耗試験機にて摩耗輪ＣＳ−１０Ｆを装着し、荷重５００ｇ下で１００回転後の曇価を測定した。テーバー摩耗性（％）は（試験後の曇価）−（試験前の曇価）で示した。
３）硬化塗膜の密着性試験：ＪＩＳ Ｋ５４００に準拠し、サンプルをカミソリの刃で１ｍｍ間隔に縦横１１本ずつ切れ目を入れて１００個の碁盤目をつくり、市販セロハンテープを良く密着させた後、９０゜手前方向に急激に剥がした時、塗膜が剥離せずに残存した升目数（Ｘ）をＸ／１００で表示した。
４）反り試験：厚さ０．５ｍｍで、３１０×３９０ｍｍ試験片を定盤の上に置き、反りを測定した。
５）耐折曲げ試験：厚さ０．５ｍｍで、幅１０ｍｍの試験片を一方の側に１８０°、反対側に１８０°の折曲げ試験を行い、破断する折曲げ回数を求めた。なお、破断する折曲げ回数は試験片厚さに依存するので、試験片厚さは（０．５±０．０５）ｍｍとした。
Measurement and evaluation of various physical properties in Examples and Comparative Examples were performed by the following methods.
1) Weather resistance test: In accordance with JIS K5400, an acceleration test was conducted using a carbon arc sunshine weatherometer, and the yellowing degree before and after the 1000 hour treatment and the adhesion after the treatment were examined. Those with good adhesion were considered acceptable.
2) Scratch resistance test: In accordance with ASTM D1044, a wear wheel CS-10F was mounted with a Taber abrasion tester, and the haze value after 100 rotations under a load of 500 g was measured. Taber abrasion (%) is indicated by (cloudiness after test) − (cloudiness before test).
3) Adhesion test of the cured coating film: After slicing the sample into 11 grids at intervals of 1 mm at intervals of 1 mm with a razor blade in accordance with JIS K5400, and making a 100 cell grid well, the commercially available cellophane tape was adhered well The number of squares (X) remaining without peeling of the coating film when it was peeled off in the 90 ° front direction was expressed as X / 100.
4) Warpage test: A 310 × 390 mm test piece having a thickness of 0.5 mm was placed on a surface plate, and the warpage was measured.
5) Bending resistance test: A test piece having a thickness of 0.5 mm and a width of 10 mm was subjected to a bending test of 180 ° on one side and 180 ° on the opposite side, and the number of bendings to be broken was obtained. In addition, since the frequency | count of bending to fracture | rupture depends on test piece thickness, the test piece thickness was set to (0.5 ± 0.05) mm.
実施例１〜２、及び比較例１〜２
スクリュー径６５ｍｍ、シリンダー設定温度２９０℃、Ｔダイ設定温度２６０℃の押出機に、三菱エンジニアリングプラスチックス（株）製、ポリカーボネート（商品名：ユーピロンＥ−２０００）を供給し、０．５ｍｍ厚シートを押出し、３本ロールの最終端部から４ｍのところで、表面温度８０℃のポリカーボネートシートと１００μｍ厚のＰＥＴフィルムの間に、表１に示した配合比率にて混合した紫外線硬化型樹脂被覆用組成物を硬化後の塗膜が３〜５μｍになるように挟み込み、圧着後、出力密度８０Ｗ／ｃｍの高圧水銀灯を用い、光源下１２ｃｍの位置でコンベアスピード３．０ｍ／分の条件で紫外線を照射して硬化し、硬化後ＰＥＴフィルムを剥離し、ポリカーボネート樹脂積層体を得た。製造された積層体の評価結果を表１に示した。
Examples 1-2 and Comparative Examples 1-2
Mitsubishi Engineering Plastics Co., Ltd. polycarbonate (trade name: Iupilon E-2000) is supplied to an extruder with a screw diameter of 65 mm, a cylinder set temperature of 290 ° C, and a T die set temperature of 260 ° C. Extruded, UV curable resin coating composition mixed at a blending ratio shown in Table 1 between a polycarbonate sheet having a surface temperature of 80 ° C. and a PET film having a thickness of 100 μm at 4 m from the final end of the three rolls. Is cured so that the coated film becomes 3 to 5 μm, and after pressure bonding, a high-pressure mercury lamp with an output density of 80 W / cm is used and irradiated with ultraviolet rays at a conveyor speed of 3.0 m / min at a position of 12 cm under the light source. After curing, the PET film was peeled off to obtain a polycarbonate resin laminate. The evaluation results of the manufactured laminate are shown in Table 1.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004122791A JP4697386B2 (en) | 2004-04-19 | 2004-04-19 | Polycarbonate resin laminate and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004122791A JP4697386B2 (en) | 2004-04-19 | 2004-04-19 | Polycarbonate resin laminate and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005306928A JP2005306928A (en) | 2005-11-04 |
| JP4697386B2 true JP4697386B2 (en) | 2011-06-08 |
Family
ID=35436068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004122791A Expired - Lifetime JP4697386B2 (en) | 2004-04-19 | 2004-04-19 | Polycarbonate resin laminate and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4697386B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5040274B2 (en) * | 2006-11-28 | 2012-10-03 | 凸版印刷株式会社 | Method for producing composition for forming hard coat layer |
| JP5418321B2 (en) * | 2010-03-12 | 2014-02-19 | 株式会社豊田自動織機 | Vehicle member and manufacturing method thereof |
| JP6417936B2 (en) * | 2014-12-26 | 2018-11-07 | 三菱ケミカル株式会社 | Laminate and display cover |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005215640A (en) * | 2004-02-02 | 2005-08-11 | Mitsubishi Gas Chem Co Inc | Photochromic lens and its manufacturing method |
-
2004
- 2004-04-19 JP JP2004122791A patent/JP4697386B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005215640A (en) * | 2004-02-02 | 2005-08-11 | Mitsubishi Gas Chem Co Inc | Photochromic lens and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005306928A (en) | 2005-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4929624B2 (en) | Curable composition, cured product thereof and laminate | |
| JP2020111715A (en) | Cured product | |
| JP6836732B2 (en) | Resin composition, cured product and laminate | |
| JP5731817B2 (en) | Water-absorbent resin composition and laminate using the same | |
| JP2008546872A (en) | Abrasion resistant coating | |
| JP5092907B2 (en) | Active energy ray curable resin composition, active energy ray curable hard coating agent, cured film using these, and article having cured film | |
| KR102190726B1 (en) | Uv-curing acrylic resin compositions for thermoformable hardcoat applications | |
| JP6642737B2 (en) | Aqueous resin composition, laminate using the same, optical film and image display device | |
| JP2018203887A (en) | Active energy ray curable composition for forming cured coated film on cyclic olefin-based resin substrate, and manufacturing method of hard coat film | |
| JP6865645B2 (en) | Photocurable resin composition and sheet | |
| JP4697386B2 (en) | Polycarbonate resin laminate and method for producing the same | |
| US20230312904A1 (en) | Photocurable resin composition, cured film, and molded article with cured film | |
| JP2009096813A (en) | Curable composition and cured material obtained therefrom | |
| JP4161182B2 (en) | A method for producing a polycarbonate resin laminate having a cured coating. | |
| JP2015038173A (en) | Photocurable resin composition, laminate sheet, laminate molded article, and method for manufacturing laminate molded article | |
| JP2020042199A (en) | Antireflection hard coat film for molding | |
| JP4299513B2 (en) | Coating composition and article | |
| JP4429199B2 (en) | Multi-layer coating film forming method and paint used therefor | |
| JP6859874B2 (en) | Active energy ray-curable resin composition and laminate | |
| JP2022055398A (en) | Antireflection hard coat film for after cure type molding | |
| JP4449551B2 (en) | Method for producing polycarbonate resin laminate | |
| JP2023040446A (en) | Photocurable resin composition, hard coat film and plastic molding including the same | |
| JP7385784B1 (en) | Photocurable resin composition, hard coat film for molding, and molded products using the same | |
| JP6217135B2 (en) | Anti-fingerprint film for in-mold molding | |
| WO2021070632A1 (en) | Curved member production method and hard-coated polycarbonate resin layered body for heat bending |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070417 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090710 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100721 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100910 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20101102 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101214 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110202 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110215 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 4697386 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |