CN107636075B - Polycarbonate resin composition and optical molded article - Google Patents
Polycarbonate resin composition and optical molded article Download PDFInfo
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- CN107636075B CN107636075B CN201680031781.8A CN201680031781A CN107636075B CN 107636075 B CN107636075 B CN 107636075B CN 201680031781 A CN201680031781 A CN 201680031781A CN 107636075 B CN107636075 B CN 107636075B
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- polycarbonate resin
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- resin composition
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- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 197
- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 195
- 239000000203 mixture Substances 0.000 title claims abstract description 113
- 230000003287 optical effect Effects 0.000 title claims description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 113
- 125000003118 aryl group Chemical group 0.000 claims abstract description 85
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 72
- 239000011574 phosphorus Substances 0.000 claims abstract description 72
- -1 phosphorus compound Chemical class 0.000 claims abstract description 72
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 57
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 57
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229920005862 polyol Polymers 0.000 claims abstract description 41
- 150000003077 polyols Chemical class 0.000 claims abstract description 41
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005259 measurement Methods 0.000 claims abstract description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims description 74
- 125000004432 carbon atom Chemical group C* 0.000 claims description 54
- 238000012360 testing method Methods 0.000 claims description 37
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 25
- 229920000570 polyether Polymers 0.000 claims description 25
- 238000000691 measurement method Methods 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 238000001746 injection moulding Methods 0.000 claims description 14
- 239000012778 molding material Substances 0.000 claims description 14
- 239000004417 polycarbonate Substances 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 12
- 229920000515 polycarbonate Polymers 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- 150000002430 hydrocarbons Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 150000002009 diols Chemical class 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- WBWXVCMXGYSMQA-UHFFFAOYSA-N 3,9-bis[2,4-bis(2-phenylpropan-2-yl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C=1C=C(OP2OCC3(CO2)COP(OC=2C(=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C(C)(C)C=2C=CC=CC=2)OC3)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 WBWXVCMXGYSMQA-UHFFFAOYSA-N 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 5
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 4
- 125000001118 alkylidene group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 238000010998 test method Methods 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 230000000007 visual effect Effects 0.000 claims 6
- 238000001035 drying Methods 0.000 claims 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims 1
- 238000002411 thermogravimetry Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 40
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 25
- 239000000243 solution Substances 0.000 description 20
- 230000007062 hydrolysis Effects 0.000 description 18
- 238000006460 hydrolysis reaction Methods 0.000 description 18
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 11
- 239000003963 antioxidant agent Substances 0.000 description 10
- 230000006866 deterioration Effects 0.000 description 10
- 230000003078 antioxidant effect Effects 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 125000002723 alicyclic group Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229920001451 polypropylene glycol Polymers 0.000 description 7
- 238000004383 yellowing Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical group OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 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 4
- 125000005702 oxyalkylene group Chemical group 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- ZUTALPWLMYPAHE-UHFFFAOYSA-N 2-(dichlorophosphanyloxymethyl)-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COP(Cl)Cl ZUTALPWLMYPAHE-UHFFFAOYSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 238000012696 Interfacial polycondensation Methods 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000004427 Tarflon Substances 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 125000006353 oxyethylene group Chemical group 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- KEKQWCLOVHSOCU-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-pentacosafluorododecyl 4-hydroxybenzoate Chemical compound OC1=CC=C(C(=O)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C=C1 KEKQWCLOVHSOCU-UHFFFAOYSA-N 0.000 description 1
- 229940083957 1,2-butanediol Drugs 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- RARQGXBOCXOJPM-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F RARQGXBOCXOJPM-UHFFFAOYSA-N 0.000 description 1
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- IJBWMYBRNPIXJT-UHFFFAOYSA-N 2,3-bis(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC(O)=C(C(C)(C)C=2C=CC=CC=2)C=1C(C)(C)C1=CC=CC=C1 IJBWMYBRNPIXJT-UHFFFAOYSA-N 0.000 description 1
- HJZJMARGPNJHHG-UHFFFAOYSA-N 2,6-dimethyl-4-propylphenol Chemical compound CCCC1=CC(C)=C(O)C(C)=C1 HJZJMARGPNJHHG-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- HHKAGFTWEFVXET-UHFFFAOYSA-N 2-heptyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound CCCCCCCC(CO)(CO)CO HHKAGFTWEFVXET-UHFFFAOYSA-N 0.000 description 1
- IYBOGQYZTIIPNI-UHFFFAOYSA-N 2-methylhexano-6-lactone Chemical compound CC1CCCCOC1=O IYBOGQYZTIIPNI-UHFFFAOYSA-N 0.000 description 1
- SDQROPCSKIYYAV-UHFFFAOYSA-N 2-methyloctane-1,8-diol Chemical compound OCC(C)CCCCCCO SDQROPCSKIYYAV-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- RQCACQIALULDSK-UHFFFAOYSA-N 4-(4-hydroxyphenyl)sulfinylphenol Chemical compound C1=CC(O)=CC=C1S(=O)C1=CC=C(O)C=C1 RQCACQIALULDSK-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical class O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-UHFFFAOYSA-N 0.000 description 1
- QDYKAUYCQUNKIZ-UHFFFAOYSA-N 4-[2,3,4,5-tetrafluoro-6-(1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexyl)phenyl]phenol Chemical compound C1=CC(O)=CC=C1C1=C(F)C(F)=C(F)C(F)=C1C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QDYKAUYCQUNKIZ-UHFFFAOYSA-N 0.000 description 1
- TVLIVAKHIGPKLY-UHFFFAOYSA-N 4-[2,3,4,5-tetrafluoro-6-(1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-nonadecafluorononyl)phenyl]phenol Chemical compound C1=CC(O)=CC=C1C1=C(F)C(F)=C(F)C(F)=C1C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F TVLIVAKHIGPKLY-UHFFFAOYSA-N 0.000 description 1
- KJMVGAOYRRKQPY-UHFFFAOYSA-N 4-[2,4,6-tri(propan-2-yl)phenyl]phenol Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=C(O)C=C1 KJMVGAOYRRKQPY-UHFFFAOYSA-N 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- 125000003143 4-hydroxybenzyl group Chemical group [H]C([*])([H])C1=C([H])C([H])=C(O[H])C([H])=C1[H] 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
- CHXLFXLPKLZALY-UHFFFAOYSA-N 4-methyloxepan-2-one Chemical compound CC1CCCOC(=O)C1 CHXLFXLPKLZALY-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- VNXMFQWTDCWMDQ-UHFFFAOYSA-N 5-methyloxepan-2-one Chemical compound CC1CCOC(=O)CC1 VNXMFQWTDCWMDQ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- FPVVYTCTZKCSOJ-UHFFFAOYSA-N Ethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCCCCCCCC FPVVYTCTZKCSOJ-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- VEZXCJBBBCKRPI-UHFFFAOYSA-N beta-propiolactone Chemical class O=C1CCO1 VEZXCJBBBCKRPI-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- NWRJMFCZZOMPSU-UHFFFAOYSA-N bis(1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexyl) 5-hydroxybenzene-1,3-dicarboxylate Chemical compound OC1=CC(C(=O)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)=CC(C(=O)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)=C1 NWRJMFCZZOMPSU-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229940100608 glycol distearate Drugs 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 238000013003 hot bending Methods 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- KHLCTMQBMINUNT-UHFFFAOYSA-N octadecane-1,12-diol Chemical compound CCCCCCC(O)CCCCCCCCCCCO KHLCTMQBMINUNT-UHFFFAOYSA-N 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- DQGSJTVMODPFBK-UHFFFAOYSA-N oxacyclotridecan-2-one Chemical compound O=C1CCCCCCCCCCCO1 DQGSJTVMODPFBK-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 1
- BPHQIXJDBIHMLT-UHFFFAOYSA-N perfluorodecane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BPHQIXJDBIHMLT-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 150000008301 phosphite esters Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21S—NON-PORTABLE LIGHTING DEVICES; SYSTEMS THEREOF; VEHICLE LIGHTING DEVICES SPECIALLY ADAPTED FOR VEHICLE EXTERIORS
- F21S43/00—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights
- F21S43/20—Signalling devices specially adapted for vehicle exteriors, e.g. brake lamps, direction indicator lights or reversing lights characterised by refractors, transparent cover plates, light guides or filters
- F21S43/26—Refractors, transparent cover plates, light guides or filters not provided in groups F21S43/235 - F21S43/255
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/02—Optical fibres with cladding with or without a coating
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Liquid Crystal (AREA)
Abstract
A polycarbonate resin composition comprising an aromatic polycarbonate resin (A), a phosphorus compound (B) having an aromatic group, and a polycaprolactone polyol (C), wherein the phosphorus-containing compound (B) is contained in an amount of 0.005 to 1 part by mass and the polycaprolactone polyol (C) is contained in an amount of 0.005 to 5 parts by mass based on 100 parts by mass of the aromatic polycarbonate resin (A), the amount of the compound having a phenol structure which is decomposed after 1,500 hours when the phosphorus-based compound (B) is left to stand at 40 ℃ and a humidity of 90% is 5% by mass or less based on the phosphorus-based compound (B), the phosphorus-based compound (B) is a compound having a temperature of 340 ℃ or higher at which 2% of the weight is reduced from the weight before measurement when the weight is measured mechanically by differential thermal-thermogravimetric analysis (TG-DTA) under a nitrogen atmosphere.
Description
Technical Field
The present invention relates to a polycarbonate resin composition and an optical molded article.
Background
Aromatic polycarbonates are excellent in transparency, mechanical properties, thermal properties, electrical properties, weather resistance and the like, and aromatic polycarbonates are used for optical molded articles such as light guide members (light guide portions of daytime running Lights, light guide plates for liquid crystals and the like), lenses, optical fibers and the like, taking advantage of these characteristics. However, light transmittance, which is one of indexes indicating transparency thereof, is lower than that of polymethyl methacrylate (PMMA) or the like, and when used in a light guide member, luminance tends to decrease. Therefore, a method for improving the luminance and light transmittance of a light guide member made of an aromatic polycarbonate has been developed.
Patent document 1 discloses an aromatic polycarbonate resin composition for a light guide plate, which is obtained by adding a polyoxyalkylene glycol mainly composed of polyethylene glycol or polypropylene glycol or a fatty acid ester thereof to an aromatic polycarbonate resin for the purpose of providing a polycarbonate resin composition for a light guide plate which is free from cloudiness and a decrease in transmittance and has good transmittance and color tone.
However, in the method of patent document 1, since polyoxyalkylene glycol has low heat resistance, if molding is performed at a temperature exceeding 320 ℃ or the molding cycle is long, yellowing increases, brightness and light transmittance are greatly reduced, and there is a possibility that optical performance of the light guide product is adversely affected. Further, when molding is performed at a temperature exceeding 340 ℃, silver streaks may be generated on the surface of the molded article due to the decomposition gas of the polyoxyalkylene glycol, and the molded article may not function as a light-guiding product. Therefore, the temperature increase is limited to improve the fluidity, and the molding of a light guide plate having a thin wall and a large area cannot be performed, and the application of the polycarbonate resin composition is limited to a molding material for a partially small light guide plate molded at a low temperature of about 280 ℃.
Patent document 2 discloses an aromatic polycarbonate resin composition prepared by blending polyoxytetramethylene polyethylene glycol into an aromatic polycarbonate resin, in order to improve the heat resistance which is a disadvantage of the method of patent document 1 and to provide an aromatic polycarbonate resin composition which can withstand molding at high temperatures. According to the method of patent document 2, molding can be performed without yellowing in a temperature range of 280 ℃ to 340 ℃.
On the other hand, patent document 3 discloses an aromatic polycarbonate resin composition containing a specific diphosphite ester compound and an alicyclic epoxy compound in an aromatic polycarbonate resin, in order to provide a resin composition which can provide a molded article having excellent heat stability in high-temperature molding, excellent light transmittance and luminance, and which does not cause discoloration or internal cracking after a wet heat resistance test. According to the method of patent document 3, molding can be performed at a temperature exceeding 340 ℃ without yellowing.
Further, depending on the application of the light-guiding member, the light-guiding member is sometimes required to be less yellowed even when used for a long period of time under high-temperature and high-humidity conditions.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 4069364
Patent document 2: international publication No. 2011/083635
Patent document 3: international publication No. 2013/088796
Disclosure of Invention
Problems to be solved by the invention
The problem to be solved by the present invention is to provide a polycarbonate resin composition which does not cause a decrease in optical characteristics due to deterioration during molding even when molding is performed in a wide temperature range.
Further, the present invention provides a polycarbonate resin composition which can provide a light guide member that is less likely to be yellowed or deteriorated in light guide performance even when used for a long period of time under severe environmental conditions such as automotive use.
Means for solving the problems
The present inventors have made intensive studies and as a result, have found that a polycarbonate resin composition which is not deteriorated in optical properties due to deterioration during molding even when molded in a wide temperature range can be obtained by blending an aromatic polycarbonate resin with specific amounts of a specific phosphorus compound and a polycaprolactone polyol which are excellent in heat resistance and hydrolysis resistance. Further, they have found that an optical lens molded from the polycarbonate resin composition of the present invention maintains high optical properties as compared with a polycarbonate resin composition containing no polycaprolactone polyol even under a severe environmental test of 1,000 hours in an oven at 120 ℃.
That is, the present invention relates to the following polycarbonate resin composition, a method for producing an optical molded article, and an optical molded article.
<1> a polycarbonate resin composition comprising an aromatic polycarbonate resin (A), a phosphorus-based compound (B) having an aromatic group, and a polycaprolactone polyol (C),
the phosphorus-containing compound (B) is contained in an amount of 0.005 to 1 part by mass and the polycaprolactone polyol (C) is contained in an amount of 0.005 to 5 parts by mass based on 100 parts by mass of the aromatic polycarbonate resin (A),
the amount of the compound having a phenol structure generated by decomposition after 1,500 hours when the phosphorus-based compound (B) is left to stand at 40 ℃ and a humidity of 90% is 5% by mass or less based on the phosphorus-based compound (B),
the phosphorus-based compound (B) is a compound having a temperature of 340 ℃ or higher at which 2% of the weight is reduced from the weight before measurement when the weight is measured mechanically by differential thermal-thermogravimetric analysis (TG-DTA) under a nitrogen atmosphere.
<2> the polycarbonate resin composition according to <1>, which further comprises 5 parts by mass or less of a polyether compound (D) represented by the following formula (1) per 100 parts by mass of the aromatic polycarbonate resin (A).
RD3O-(RD1O)m(RD2O)n-RD4(1)
(in the formula, RD1And RD2Represents an alkylene group having 1 or more carbon atoms, RD1And RD2May be the same or different. m + n is 5 or more and less than 300. R when m is 2 or moreD1R may be the same or different, and when n is 2 or more, R isD2May be the same or different. RD3And RD4Represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, an alkanoyl group having 1 to 30 carbon atoms, an alkenoyl group having 2 to 30 carbon atoms, or a glycidyl group, RD3And RD4May be the same or different。)
<3> the polycarbonate resin composition according to <1> or <2>, wherein the aromatic polycarbonate resin (A) is a polycarbonate having a main chain having a repeating unit represented by the following general formula (I).
[ solution 1]
(in the formula, RA1And RA2Represents an alkyl or alkoxy group having 1 to 6 carbon atoms, RA1And RA2May be the same or different. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO2-, -O-or-CO-, a and b each independently represent an integer of 0 or more and 4 or less. R when a is 2 or moreA1R may be the same or different, and when b is 2 or moreA2May be the same or different. )
<4> the polycarbonate resin composition according to any one of <1> to <3>, wherein the phosphorus compound (B) is a phosphorus compound having a phosphite ester structure.
<5> the polycarbonate resin composition according to any one of <1> to <4>, wherein the phosphorus compound (B) is a pentaerythritol diphosphite compound represented by the following general formula (II).
[ solution 2]
(in the formula, Y1～Y4The carbon atoms may be the same or different and represent a hydrocarbon group having 6 to 15 carbon atoms. )
<6>As described above<5>The polycarbonate resin composition, wherein Y in the above formula (II)1～Y4Each independently of the others being unsubstituted or substituted cumyl, notSubstituted or substituted phenyl, unsubstituted or substituted naphthyl, or unsubstituted or substituted biphenyl.
<7> the polycarbonate resin composition according to any one of <1> to <6>, wherein the phosphorus compound (B) is a pentaerythritol diphosphite compound represented by the following general formula (II-1).
[ solution 3]
(in the formula, RB1～RB8Represents an alkyl group or an alkenyl group, and may be the same or different. RB1And RB2、RB3And RB4、RB5And RB6、RB7And RB8May be bonded to each other to form a ring. RB9～RB12Represents a hydrogen atom or an alkyl group, and may be the same or different. m1 to m4 are integers of 0 to 5 inclusive, and may be the same or different. Z1～Z4Represents a single bond or a carbon atom, and may be the same or different. At Z1～Z4When represents a single bond, RB1～RB8Are excluded from the general formula (II-1). )
<8> the polycarbonate resin composition according to any one of <1> to <7>, wherein the phosphorus compound (B) is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
<9> the polycarbonate resin composition according to any one of <1> to <8>, wherein the polycaprolactone polyol (C) is at least one selected from the group consisting of polycaprolactone diol, polycaprolactone triol and polycaprolactone tetraol having a molecular weight of 500 or more and 5,000 or less.
<10>As described above<2>～<9>The polycarbonate resin composition of any one of, wherein the polyether compound (D) is R in the formula (1)D1And RD2Is alkylene with 2-5 carbon atoms, RD3And RD4A polyether compound which is a hydrogen atom.
<11> the polycarbonate resin composition according to any one of <1> to <10> above, wherein the aromatic polycarbonate resin (A) has a viscosity average molecular weight (Mv) of 9,000 to 50,000.
<12> A method for producing an optical molded article, wherein the polycarbonate resin composition according to any one of <1> to <11> is molded.
<13> an optical molded article obtained by the production method of <12> above.
<14> an optical molded article comprising the polycarbonate resin composition according to any one of <1> to <11 >.
<15> the optical molded article according to <13> or <14>, wherein the optical molded article is a light guide member.
<16> the optical molded article according to any one of <13> to <15>, wherein the optical molded article is a light guide member for a vehicle.
<17> a light guide member for a vehicle used for a daytime running lamp, comprising the molded article of <16> above.
<18> a daytime running light comprising the optical molded article of <16> above.
Effects of the invention
According to the present invention, there can be provided a polycarbonate resin composition, a method for producing an optical molded article, and an optical molded article, in which the deterioration of optical characteristics due to the deterioration during molding does not occur even when molding is performed in a wide temperature range, and the deterioration of yellowing is small even when used under severe environmental conditions for a long period of time.
Detailed Description
The present invention will be explained below. In the present invention, a combination of preferred embodiments is a more preferred embodiment.
Depending on the application of the light guide member, there are cases where thinning is required, and the polycarbonate resin composition may be molded at a temperature exceeding 340 ℃, particularly at a temperature exceeding 360 ℃. From the above-mentioned point of view, the method of International publication No. 2011/083635 is insufficient, and further improvement is required.
On the other hand, a Daytime lamp called a Daytime Running light (or Daytime Running Lamps) (abbreviated as DRL) attached to the outer periphery of a head lamp or a tail lamp of an automobile is a light guide ring having a thick-walled lens structure. Such a DRL having a thick wall structure is often molded at a low temperature of about 280 ℃. The reason is that: since the DRL has a thick-walled structure, if a sufficient cooling time is not taken, the product surface is narrowed or shrunk to be deformed, and therefore, a long molding cycle is required. If the molding cycle is long and the molding temperature is high, the molten resin remaining in the molding machine burns, and therefore, the molding temperature must be reduced as much as possible without causing stagnation combustion. In order to suppress this combustion, there are many cases in which combustion is prevented while nitrogen molding is performed, in which molding is performed while replacing air in the molding machine with nitrogen gas. As described above, polycarbonate resins used for light guide applications are required to have a property of being capable of molding without yellowing even in molding requiring a wide temperature range and a long residence time.
In addition, as in DRL, in the use of optical polycarbonate resin, in the strict environmental test, such as a heat resistance oven test at 120 degrees C for 1000 hours or more. As shown in japanese patent No. 4069364, the polyether polyols disclosed in international publication nos. 2011/083635 and 2013/088796 have a significant effect of improving optical properties, but have the disadvantage of low long-term heat resistance and significantly reduced optical properties in a severe environmental test such as an oven test at 120 ℃. This is a problem of heat resistance of polyether polyol itself, and therefore, heat resistance cannot be improved by other additives. Therefore, a polycarbonate resin composition which can be used for an optical lens for an automobile is strongly desired to have improved brightness and improved blue color tone depending only on the optical properties of the polycarbonate itself.
The present inventors have provided a polycarbonate resin composition which can meet the performance and expectations of the above-mentioned applications.
The polycarbonate resin composition of the present invention is a polycarbonate resin composition comprising an aromatic polycarbonate resin (A), a phosphorus compound (B) having an aryl group, and a polycaprolactone polyol (C), wherein the phosphorus compound (B) is contained in an amount of 0.005 to 1 part by mass and the polycaprolactone polyol (C) is contained in an amount of 0.005 to 5 parts by mass, relative to 100 parts by mass of the aromatic polycarbonate resin (A), the amount of a compound having a phenol structure decomposed after 1 to 500 hours when the phosphorus compound (B) is left to stand at 40 ℃ and 90% humidity is 5% by mass or less relative to the phosphorus compound (B), and the phosphorus compound (B) is a compound in which the weight before measurement is reduced by 2% in a nitrogen atmosphere using a differential thermal thermogravimetry (TG-DTA) machine to measure the weight and the temperature of 2% or more by weight before the measurement is 340 ℃ or more A compound (I) is provided.
[ component (A): aromatic polycarbonate resin
The aromatic polycarbonate resin (a) contained in the polycarbonate resin composition of the present invention is not particularly limited, and an aromatic polycarbonate resin produced by a known method can be used.
For example, as the aromatic polycarbonate resin (a), an aromatic polycarbonate resin produced by reacting a dihydric phenol and a carbonate precursor by a solution method (interfacial polycondensation method) or a melt method (transesterification method), that is, an aromatic polycarbonate resin produced by an interfacial polycondensation method in which a dihydric phenol and phosgene are reacted in the presence of a terminal capping agent, or an aromatic polycarbonate resin produced by reacting a dihydric phenol and diphenyl carbonate or the like in the presence of a terminal capping agent by a transesterification method or the like can be used.
The dihydric phenol includes various dihydric phenols, and particularly includes: 2, 2-bis (4-hydroxyphenyl) propane [ bisphenol A ], bis (4-hydroxyphenyl) methane, 1-bis (4-hydroxyphenyl) ethane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 4' -dihydroxybiphenyl, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide and bis (4-hydroxyphenyl) ketone, and the like. In addition, hydroquinone, resorcinol, catechol, and the like can be cited. These may be used alone or in combination of two or more, but among them, bis (hydroxyphenyl) alkanes are preferable, and bisphenol a is particularly preferable.
The carbonate precursor is carbonyl halide, carbonyl ester, haloformate or the like, specifically phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, diethyl carbonate or the like.
In the present invention, component (a) may have a branched structure, and examples of the branching agent include 1, 1, 1-tris (4-hydroxyphenyl) ethane, α', α ″ -tris (4-hydroxyphenyl) -1, 3, 5-triisopropylbenzene, phloroglucinol, trimellitic acid, and 1, 3-bis (o-cresol).
As the blocking agent, a monocarboxylic acid and its derivative, and a monohydric phenol can be used. Examples thereof include: p-tert-butylphenol, p-phenylphenol, p-cumylphenol, p-perfluorononylphenol, p- (perfluorononylphenyl) phenol, p- (perfluorohexylphenyl) phenol, p-perfluorotert-butylphenol, 1- (p-hydroxybenzyl) perfluorodecane, p- [2- (1H, 1H-perfluorotriacontyl (tridodecyl) oxy) -1, 1, 1, 3, 3, 3-hexafluoropropyl ] phenol, 3, 5-bis (perfluorohexyloxycarbonyl) phenol, perfluorododecyl p-hydroxybenzoate, p- (1H, 1H-perfluorooctyloxy) phenol, 2H, 9H-perfluorononanoic acid, 1, 1, 3, 3, 3-hexafluoro-2-propanol, and the like.
The aromatic polycarbonate resin (a) is preferably a polycarbonate having a repeating unit represented by the following general formula (I) in the main chain.
[ solution 4]
(in the formula, RA1And RA2Each independently represents an alkyl or alkoxy group having 1 to 6 carbon atoms, RA1And RA2May be the same or different. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, or a C-groupA cycloalkylene group of 5 to 15 inclusive, a cycloalkylidene group of 5 to 15 inclusive, -S-, -SO-, -SO-2-, -O-or-CO-, a and b each independently represent an integer of 0 or more and 4 or less. R when a is 2 or moreA1R may be the same or different, and when b is 2 or moreA2May be the same or different. )
As RA1And RA2The alkyl group represented by (a) may be exemplified by: methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups ("various" means including straight-chain and all branched-chain groups, the same shall apply hereinafter), various pentyl groups, and various hexyl groups. As RA1And RA2Examples of the alkoxy group include those wherein the alkyl moiety is the above-mentioned alkyl group.
RA1And RA2Each is preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
Examples of the alkylene group represented by X include: a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, etc., preferably an alkylene group having 1 to 5 carbon atoms. Examples of the alkylidene group represented by X include ethylidene group and isopropylidene group. Examples of the cycloalkylene group represented by X include: cyclopentanediyl, cyclohexanediyl, cyclooctanediyl, and the like, and a cycloalkylene group having 5 to 10 carbon atoms is preferable. Examples of the cycloalkylidene group represented by X include: cyclohexylidene, 3, 5, 5-trimethylcyclohexylidene, 2-adamantylidene, and the like, preferably cycloalkylidene having 5 or more and 10 or less carbon atoms, and more preferably cycloalkylidene having 5 or more and 8 or less carbon atoms.
a and b each independently represent an integer of 0 or more and 4 or less, preferably 0 or more and 2 or less, and more preferably 0 or 1.
In the present invention, the aromatic polycarbonate resin (a) preferably contains a polycarbonate resin having a bisphenol a structure from the viewpoint of transparency, mechanical properties, thermal properties, and the like of the obtained molded article. Specific examples of the polycarbonate resin having a bisphenol a structure include polycarbonate resins in which X is isopropylidene in the general formula (I). The content of the polycarbonate resin having a bisphenol a structure in the aromatic polycarbonate resin (a) is preferably 50% by mass or more and 100% by mass or less, more preferably 75% by mass or more and 100% by mass or less, and still more preferably 85% by mass or more and 100% by mass or less.
In the present invention, the viscosity-average molecular weight (Mv) of the component (a) is preferably 9,000 or more and 50,000 or less, more preferably 10,000 or more and 30,000 or less, and further preferably 11,000 or more and 25,000 or less, from the viewpoint of fluidity. In particular, when the polycarbonate resin composition of the present invention is used as a thin-walled optical molded article such as a light guide plate, the Mv of the aromatic polycarbonate resin (a) is preferably 9,000 to 17,000.
In the present invention, the viscosity average molecular weight (Mv) is calculated as follows: the intrinsic viscosity [ eta ] was determined by measuring the viscosity of a methylene chloride solution (concentration unit: g/L) at 20 ℃ with an Ubbelohde viscometer, and was calculated by the following equation.
[η]＝1.23×10-5Mv0.83
[ component (B): phosphorus-based Compound having aryl group ]
The amount of the compound having a phenolic structure generated by decomposition after 1,500 hours when the phosphorus-based compound (B) having an aryl group contained in the polycarbonate resin composition of the present invention is left to stand at 40 ℃ and 90% humidity is 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less, relative to the phosphorus-based compound (B). That is, the phosphorus-based compound (B) having an aryl group used in the present invention is a phosphorus-based compound having excellent hydrolysis resistance and a small amount of a compound having a phenol structure. The amount of the compound having a phenol structure can be quantified by gas chromatography, specifically, measured by the method described in examples.
When the weight of the phosphorus-containing compound (B) contained in the polycarbonate resin composition of the present invention is measured using a differential thermal thermogravimetric (TG-DTA) machine under a nitrogen atmosphere, the temperature at which 2% of the weight is reduced from the weight before the measurement is 340 ℃ or higher. In this specification, the temperature at which the weight is reduced by 2% is also referred to as "98% holding temperature".
Here, the temperature at which the weight reduction of 2% is performed is preferably 345 ℃ or more, and more preferably 350 ℃ or more.
The conventional phosphite-based antioxidants having a pentaerythritol diphosphite structure exhibit a good antioxidant effect at ordinary processing temperatures of polycarbonate resins, but undergo thermal decomposition at high temperatures exceeding 340 ℃ to rapidly lose the antioxidant effect. Further, since the thermal decomposition itself generates a substance causing yellowing, insufficient heat resistance is a problem. In addition, many phosphite-based antioxidants are easily hydrolyzed, and in a wet heat resistance test of a light guide plate, the antioxidants in the light guide plate are easily hydrolyzed, and thus the light guide plate is easily discolored or clouded due to the influence of decomposed products thereof. International publication No. 2013/088796 discloses that a specific diphosphite-based antioxidant represented by bis (2, 4-dicumylphenyl) pentaerythritol diphosphite is effective as an antioxidant capable of satisfying the required characteristics of heat resistance and hydrolysis resistance.
However, in the method of international publication No. 2013/088796, an alicyclic epoxy compound is required from the viewpoint of moist heat resistance. In addition, in this method, although the thermal stability under high-temperature molding is excellent, sufficient performance cannot be exhibited in the molding temperature range of less than 300 ℃.
The present inventors have found that a polycarbonate resin composition which is molded at a wide temperature range and in which optical properties are not deteriorated due to deterioration during molding can be obtained by using a specific phosphorus compound (B) in combination with a polycaprolactone polyol (C).
The phosphorus-based compound (B) having an aryl group used in the present invention is preferably a phosphorus-based compound having a phosphite structure, and more preferably a pentaerythritol diphosphite compound represented by the following general formula (II).
[ solution 5]
(in the formula, Y1～Y4The carbon atoms may be the same or different and represent a hydrocarbon group having 6 to 15 carbon atoms. )
Y1～Y4Preferably each independently is unsubstituted or substituted cumyl, unsubstituted or substituted phenyl, unsubstituted or substituted naphthyl, or unsubstituted or substituted biphenyl.
The phosphorus-containing compound (B) used in the present invention is preferably a pentaerythritol diphosphite compound represented by the following general formula (II-1).
[ solution 6]
(in the formula, RB1～RB8Represents an alkyl group or an alkenyl group, and may be the same or different. RB1And RB2、RB3And RB4、RB5And RB6、RB7And RB8May be bonded to each other to form a ring. RB9～RB12Represents a hydrogen atom or an alkyl group, and may be the same or different. m1 to m4 are integers of 0 to 5 inclusive, and may be the same or different. Z1～Z4Represents a single bond or a carbon atom, and may be the same or different. At Z1～Z4When represents a single bond, RB1～RB8Are excluded from the general formula (II-1). )
RB1～RB8The carbon number is preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less, and most preferably 1. RB9～RB12Preferably a hydrogen atom. m1 to m4 are preferably 0 to 3 inclusive, more preferably 0 to 1 inclusive, and most preferably 0. Z1～Z4Preferably a carbon atom.
The pentaerythritol diphosphite compound represented by the above general formula (II) or (II-1) can be obtained as follows: the phosphorus trichloride compound is obtained by adding a chlorine-based solvent to pentaerythritol to obtain pentaerythritol dichlorophosphite, and then heating and mixing the pentaerythritol dichlorophosphite in the presence of an aromatic solvent and an organic nitrogen-containing base compound (see, for example, jp 2004-a 018406).
Among the pentaerythritol diphosphite compounds represented by the above general formula (II) or (II-1), bis (2, 4-dicumylphenyl) pentaerythritol diphosphite represented by the following general formula (II-2) is particularly suitable because it can impart good heat resistance and hydrolysis resistance to a polycarbonate resin composition and can be easily obtained. This compound is commercially available, and for example, "Doverphos (registered trademark) S-9228 PC" manufactured by Dover Chemical company can be used.
[ solution 7]
The heat resistance of a general pentaerythritol diphosphite compound is as follows: the 98% holding temperature measured under a nitrogen atmosphere using a differential thermal-thermogravimetric (TG-DTA) machine was 240 ℃ or more and 280 ℃ or less. In contrast, the 98% holding temperature of bis (2, 4-dicumylphenyl) pentaerythritol diphosphite described above was 340 ℃ or higher. Because of such heat resistance, even when molded at a high temperature exceeding 340 ℃, the performance thereof is not impaired. Instead, the oxidation resistance tends to be activated when the molding is performed at a high temperature.
Hydrolysis of a polycarbonate resin molded product is mainly caused by free phenol and phosphoric acid generated by hydrolysis of a phosphorus antioxidant contained therein. Therefore, if a phosphorus antioxidant which is easily hydrolyzed is used, the polycarbonate molded body itself is hydrolyzed to lower the molecular weight and turn white.
When the phosphorus-based compound (B) having an aryl group used in the present invention is left to stand at 40 ℃ and a humidity of 90%, the amount of free phenol and phosphoric acid generated by hydrolysis after 1,500 hours is 1/100 or less, compared with the amount of free phenol and phosphoric acid generated by hydrolysis of a general compound having a pentaerythritol diphosphite structure. Since the molded article is excellent in hydrolysis resistance, even when the molded article is stored for a long period of time, the molded article is not likely to be hydrolyzed. Therefore, a molded article using a polycarbonate resin composition containing the phosphorus-based compound (B) can be stably used for a long period of time without degrading optical characteristics.
From the viewpoint of obtaining a polycarbonate resin composition in which deterioration of optical properties due to deterioration during molding does not occur even when molding is performed in a wide temperature range, the content of the phosphorus compound (B) having an aryl group in the aromatic polycarbonate resin of the present invention is 0.005 parts by mass or more and 1 part by mass or less, preferably 0.01 parts by mass or more and 0.8 parts by mass or less, more preferably 0.03 parts by mass or more and 0.5 parts by mass or less, and further preferably 0.03 parts by mass or more and 0.3 parts by mass or less with respect to 100 parts by mass of the aromatic polycarbonate resin (a).
[ component (C): polycaprolactone polyol
The polycaprolactone polyol is obtained by ring-opening polymerization of a lactone monomer using, for example, a polyol as an initiator.
Specific examples of the polyol include: ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 2-methyl-1, 3-propanediol, 1, 4-butanediol, neopentyl glycol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 2, 4-trimethyl-1, 3-pentanediol, 2-ethyl-1, 3-hexanediol, 2-methyl-1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 12-octadecanediol, glycerol, trimethylolpropane, trimethyloloctane, pentaerythritol, and the like.
Examples of the lactone monomer include: caprolactone esters such as-caprolactone, α -methyl-caprolactone, β -methyl-caprolactone, γ -methyl-caprolactone, β -dimethyl-caprolactone, 3, 5-trimethyl-caprolactone and the like; polypentylides such as valerolactone and beta-methyl-8-valerolactone; propiolactone esters; butyrolactone esters; a heptalactone; dodecanolactone, and the like. Derivatives of the lactone monomers are also possible.
The polycaprolactone polyol (C) may be the one described in Japanese patent application laid-open No. 11-228905 paragraph [0016 ]. As the polycaprolactone polyol, for example, a polycaprolactone polyol can be used
[ solution 8]
(wherein m + n is an integer of 4 to 35 inclusive, and R is C2H4、C2H4OC2H4Or C (CH)3)2(CH2)2) Such bifunctional polycaprolactone diols,
[ solution 9]
(wherein l + m + n is an integer of 3 to 30 inclusive, and R is CH2CHCH2、CH3C(CH2)3Or CH3CH2C(CH2)3)
Such trifunctional polycaprolactone triols and tetrafunctional polycaprolactone tetrols, and the like. The polycaprolactone polyol (C) is preferably at least one selected from the group consisting of the above-mentioned polycaprolactone diol, polycaprolactone triol and polycaprolactone tetraol. The molecular weight (number average molecular weight) is in the range of 500 or more and 5,000 or less, preferably 850 or more and 4,000 or less, and more preferably 1,000 or more and 3,000 or less. When the molecular weight is less than 500, the heat resistance is low and the resin composition cannot be used in high-temperature molding. When the molecular weight exceeds 5,000, solid-state occurs and the resin is not easily dissolved and difficult to handle. When the molecular weight is about 10,000, the resin can be pelletized as a thermoplastic resin, but is not easily dispersed in polycarbonate, and the compatibility with the antioxidant (B) is poor, resulting in poor color tone.
Specific examples of the polycaprolactone polyol (C) include commercially available products such as: the trade names "PLACCEL 205", "PLACCEL 208", "PLACCEL 210 CP", "PLACCEL 212", "PLACCEL 220 CPB" (polycaprolactone diol), "PLACCEL 305", "PLACCEL 308", "PLACCEL 312", "PLACCEL 320" (polycaprolactone triol), "PLACCEL 410" (polycaprolactone tetraol), and the like, manufactured by Daicel corporation. As the polycaprolactone polyol, polycaprolactone diol is preferable.
The content of the polycaprolactone polyol (C) in the aromatic polycarbonate resin of the present invention is 0.005 part by mass or more and 5 parts by mass or less, preferably 0.01 part by mass or more and 5 parts by mass or less, more preferably 0.02 part by mass or more and 3 parts by mass or less, further preferably 0.03 part by mass or more and 2 parts by mass or less, further more preferably 0.1 part by mass or more and 2 parts by mass or less, and most preferably 0.3 part by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of the aromatic polycarbonate resin (a).
[ component (D): polyether Compound having a polyoxyalkylene Structure ]
The polycarbonate resin composition of the present invention preferably contains a polyether compound (D) having a polyoxyalkylene structure. The polyether compound (D) is a compound represented by the following formula (1).
RD3O-(RD1O)m(RD2O)n-RD4(1)
(in the formula, RD1And RD2Represents an alkylene group having 1 or more carbon atoms, RD1And RD2May be the same or different. m + n is 5 or more and less than 300. R when m is 2 or moreD1R may be the same or different, and when n is 2 or more, R isD2May be the same or different. RD3And RD4Represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, an alkanoyl group having 1 to 30 carbon atoms, an alkenoyl group having 2 to 30 carbon atoms, or a glycidyl group, RD3And RD4May be the same or different. )
RD1And RD2The carbon number is preferably 1 or more and 8 or less, more preferably 1 or more and 6 or less, and most preferably 1 or more and 5 or less. Examples thereof include: methylene, ethylene, trimethylene, propylene, tetramethylene, hexamethylene, and the like.
(RD1O)mThe polyoxyalkylene group represented is not limited to a polyoxyalkylene group having a single oxyalkylene unit as a repeating unit such as a polyoxyethylene group or a polyoxypropylene group, and may be a polyoxyalkylene group having plural oxyalkylene units having different carbon numbers such as an oxyethylene unit and an oxypropylene unit as repeating unitsThe polyoxyalkylene group of (1).
(RD2O)mThe polyoxyalkylene group represented is not limited to a polyoxyalkylene group having a single oxyalkylene unit as a repeating unit such as a polyoxyethylene group or a polyoxypropylene group, and may be a polyoxyalkylene group having plural oxyalkylene units having different carbon numbers such as an oxyethylene unit and an oxypropylene unit as repeating units.
As RD3And RD4The hydrocarbon group having 1 to 30 carbon atoms includes: an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms.
The alkyl group and the alkenyl group may be linear, branched or cyclic, and examples thereof include: methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, various hexyl groups, various octyl groups, cyclopentyl groups, cyclohexyl groups, allyl groups, propenyl groups, various butenyl groups, various hexenyl groups, various octenyl groups, cyclopentenyl groups, cyclohexenyl groups, and the like. Examples of aryl groups include: phenyl, tolyl, xylyl, and the like. Examples of the aralkyl group include: benzyl, phenethyl, methylbenzyl, and the like.
As RD3And RD4The alkanoyl group having 1 to 30 carbon atoms may be linear or branched, and examples thereof include: formyl, acetyl, n-propionyl, isopropionyl, n-butyryl, t-butyryl, n-hexanoyl, n-octanoyl, n-decanoyl, n-dodecanoyl, benzoyl and the like. Among these, alkanoyl groups having 1 to 20 carbon atoms are preferred from the viewpoint of compatibility, thermal stability and ease of production.
As RD3And RD4The alkenoyl group having 2 to 30 carbon atoms may be linear or branched, and examples thereof include: vinyl acyl, n-acryloyl, iso-acryloyl, n-butenoyl, t-butenoyl, n-hexenoyl, n-octenoyl, n-decenoyl, n-dodecenoyl and the like. Of these, fromFrom the viewpoint of low molecular weight, compatibility, solubility, and ease of production, an alkenoyl group having 2 or more and 10 or less carbon atoms is preferable, and an alkenoyl group having 2 or more and 6 or less carbon atoms is more preferable.
In addition, R in the above general formula (1) is particularly preferableD1And RD2Is alkylene with 2-5 carbon atoms, RD3And RD4A polyether compound (D) having a polyoxyalkylene structure which is a hydrogen atom.
Specific examples of the polyether compound (D) having a polyoxyalkylene structure represented by the above general formula (1) include: polyethylene glycol, polypropylene glycol, polybutylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol, polyoxyethylene monomethyl ether, polyoxyethylene dimethyl ether, polyoxyethylene-bisphenol a ether, polyoxypropylene-bisphenol a ether, polyoxyethylene-polyoxypropylene-bisphenol a ether, polyethylene glycol-allyl ether, polyethylene glycol-diallyl ether, polypropylene glycol-allyl ether, polypropylene glycol-diallyl ether, polyethylene glycol-polypropylene glycol-allyl ether, polyethylene glycol dimethacrylate, polypropylene glycol distearate, and the like.
These are commercially available, and for example, "Uniox (registered trademark)", "UNIOL (registered trademark)", "Unilub (registered trademark)", "Unisafe (registered trademark)", "POLYCERIN (registered trademark)", "epil (registered trademark)", and the like manufactured by nippon oil co.
Among these, "Unilub DE" series of random copolymerization type of polyoxyethylene glycol and polyoxypropylene glycol having a molecular weight (average molecular weight) of 1,000 to 5,000, "POLYCERIN DC" series of random copolymerization type of polyoxyethylene glycol and polyoxytetramethylene glycol, and "POLYCERIN DCB" series of random copolymerization type of polyoxypropylene glycol and polyoxytetramethylene glycol are particularly preferable.
The polyether compound (D) is superior in processing stability when compared with polycaprolactone polyol, but is inferior in long-term heat resistance such as oven heat resistance. Therefore, for optical products requiring long-term heat resistance, it is preferable to suppress the amount of the polyether compound (D) to be added. The content of the polyether compound (D) having a polyoxyalkylene structure in the aromatic polycarbonate resin of the present invention is 0 part by mass or more and 5 parts by mass or less, preferably 0 part by mass or more and 4 parts by mass or less, and more preferably 0 part by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the aromatic polycarbonate resin (a). In order to suppress an increase in the YI value, it is preferably 0.05 parts by mass or more and 5 parts by mass or less, and more preferably 0.1 parts by mass or more and 3 parts by mass or less.
For example, in the case of a product requiring long-term heat resistance at high temperatures such as DRL, the polyether (D) is not added.
[ additives ]
In the polycarbonate resin composition of the present invention, optional additives such as polyorganosiloxane may be added as appropriate in addition to the above-mentioned components (a) to (D) within the range not to impair the effects of the present invention.
[ polyorganosiloxane ]
The polyorganosiloxane is preferably a compound having at least one functional group selected from functional groups such as an alkoxy group, an aryloxy group, a polyoxyalkylene group, a carboxyl group, a silanol group, an amino group, a mercapto group, an epoxy group, and a vinyl group.
The amount of the polyorganosiloxane to be added is preferably 0.01 to 0.15 parts by mass, more preferably 0.02 to 0.15 parts by mass, and still more preferably 0.05 to 0.1 parts by mass, based on 100 parts by mass of the aromatic polycarbonate resin (a). When the amount is within the above range, the releasability can be improved in cooperation with other components, and the occurrence of silver streaks and mold deposit can be greatly reduced even under molding conditions at a high temperature exceeding 340 ℃, particularly continuous molding conditions.
The kinematic viscosity of the polyorganosiloxane at 25 ℃ is preferably 10mm from the viewpoint of the effect of slipperiness as a mold release property2More than s, preferably 200mm from the viewpoint of dispersibility in the polycarbonate resin2The ratio of the water to the water is less than s. From the above viewpoint, the viscosity of the polyorganosiloxane is more preferably 20mm2150mm of more than s2Less than s, intoOne step is preferably 40mm2120mm of more than s2(ii) a range of,/s or less.
In order not to decrease the transparency when added to polycarbonate, the refractive index difference between polyorganosiloxane and polycarbonate is preferably as small as possible. Since the refractive index of the polycarbonate is 1.58, the refractive index of the polyorganosiloxane is preferably 1.45 or more, more preferably 1.50 or more, and still more preferably 1.52 or more.
[ aliphatic Cyclic epoxy Compound ]
In order to further improve hydrolysis resistance, an aliphatic cyclic epoxy compound may be blended in the aromatic polycarbonate resin composition of the present invention. The alicyclic epoxy compound is a cyclic aliphatic compound having an alicyclic epoxy group, i.e., an epoxy group obtained by adding an atomic oxygen to a vinyl bond in an aliphatic ring, and specifically, those represented by the following formulae (1) to (10) shown in jp-a-11-158364 are preferably used.
[ solution 10]
(wherein R is H or CH)3)
[ solution 11]
(wherein R is H or CH)3)
[ solution 12]
(wherein a + b is 1 or 2)
[ solution 13]
(wherein a + b + c + d is 1 or more and 3 or less.)
[ solution 14]
(wherein a + b + c is n (integer), and R is a hydrocarbon group)
[ solution 15]
(in the formula, n is an integer)
[ solution 16]
(wherein R is a hydrocarbon group)
[ solution 17]
(wherein n is an integer and R is a hydrocarbon group)
Among the alicyclic epoxy compounds, compounds represented by formula (1), formula (7) or formula (10) are preferably used from the viewpoint of excellent compatibility with the aromatic polycarbonate resin and no deterioration in transparency. For example, the compound represented by the formula (1) can be obtained in the form of 3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexanecarboxylate ("Celloxide 2021P" (registered trademark), manufactured by Daicel K.K.). The compound represented by formula (10) can be obtained as a1, 2-epoxy-4- (2-epoxyethyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol ("EHPE 3150" (registered trademark), manufactured by Daicel co).
Further, as the mixture of "Celloxide 2021P" and "EHPE 3150", it is also possible to use "EHPE 3150 CE" (registered trademark) commercially available from Daicel co.
By blending the alicyclic epoxy compound in the aromatic polycarbonate resin composition of the present invention, as described above, the hydrolysis resistance is further improved and the transparency can be further improved. The amount of the alicyclic epoxy compound is usually about 0.001 part by mass or more and 0.5 part by mass or less, preferably 0.005 part by mass or more and 0.2 part by mass or less, and more preferably 0.01 part by mass or more and 0.1 part by mass or less, relative to 100 parts by mass of the aromatic polycarbonate resin (a).
[ aromatic polycarbonate resin composition and optical molded article ]
The method for producing the polycarbonate resin composition of the present invention is not particularly limited.
For example, the components (A) to (C) are mixed with the component (D) and other additives as required, and melt-kneaded. The melt-kneading can be carried out by a commonly used method, for example, by mixing with a ribbon mixer, a henschel mixer, a banbury mixer, or a tumbler, and then melting and kneading with a single-screw extruder, a twin-screw extruder, a co-kneader, or a multi-screw extruder. The polycaprolactone polyol (C) and the polyether (D) are usually mixed by dropping them into a mixer while appropriately heating them to reduce the viscosity, or by dropping them directly into the hopper mouth of a mixer. The heating temperature during melt kneading is appropriately selected within a range of about 220 ℃ to 300 ℃.
The polycarbonate resin composition of the present invention can be produced by using the above-mentioned melt kneaded product or the obtained resin pellet as a raw material, and applying a known molding method such as a hollow molding method, an injection compression molding method, an extrusion molding method, a vacuum molding method, a blow molding method, a press molding method, a pressure-air molding method, a foam molding method, a hot-bending molding method, a compression molding method, a calender molding method, a rotational molding method, or the like.
The polycarbonate resin composition of the present invention is improved in heat resistance insufficiency and can withstand molding at a high temperature exceeding 340 ℃, and is therefore suitable for a molding method requiring high fluidity for a molding material, such as injection molding. Further, the method is also suitable for molding with a long molding cycle such as thick wall lens molding such as DRL, and nitrogen molding in which nitrogen is introduced into a molding machine. On the other hand, in the extrusion molding method, by molding at a low temperature of about 220 ℃ to 280 ℃, products such as a sheet or a film having high optical characteristics, high transparency, no yellowing, and the like can be obtained.
The YI value of the polycarbonate resin composition of the present invention measured by the following measurement methods (1) and (2) is preferably 1.2 or less, and the difference between the YI values measured by the following measurement methods (1) and (2) is preferably 0.1 or less.
More preferably, the YI value of the polycarbonate resin composition of the present invention measured by the following measurement methods (1) and (2) is 1.15 or less, and the difference between the YI values measured by the following measurement methods (1) and (2) is 0.08 or less.
The YI value of the polycarbonate resin composition of the present invention measured by the following measurement method (1) is preferably 1.25 or less, and the YI value measured by the following measurement method (2) is preferably 1.10 or less.
Measurement method (1)
The polycarbonate resin molding material was pelletized and then dried. Then, a molded article of 50mm × 80mm × 5mm in thickness was molded by injection molding under conditions of a cylinder temperature of 360 ℃, a mold temperature of 80 ℃, and a cycle time of 50 seconds. The YI value of the molded article was measured with a spectrophotometer under the conditions of a C light source and a 2-degree field of view.
Measurement method (2)
The polycarbonate resin molding material was pelletized and then dried. Then, a molded article of 50mm × 80mm × 5mm in thickness was molded by injection molding under conditions of a cylinder temperature of 280 ℃, a mold temperature of 80 ℃, and a cycle time of 50 seconds. The YI value of the molded article was measured with a spectrophotometer under the conditions of a C light source and a 2-degree field of view.
In addition, in the polycarbonate resin composition of the present invention, when the following wet heat resistance test is performed, the difference Δ YI between YI values of molded articles before and after the test is preferably 0.2(0.20) or less.
[ method of testing moisture and Heat resistance ]
After the polycarbonate resin molding material was pelletized and dried, a molded article of 40mm × 80mm × 3mm in thickness was molded under conditions of a cylinder temperature of 350 ℃, a mold temperature of 80 ℃, and a cycle time of 30 seconds. The molded article was placed in a constant temperature and humidity chamber set at a temperature of 85 ℃ and a relative humidity of 95% for 500 hours.
In addition, in the polycarbonate resin composition of the present invention, when the following heat resistance test is performed, the difference Δ YI between YI values of the molded article before and after the test is preferably 0.5(0.50) or less.
[ Heat resistance test method ]
After the polycarbonate resin molding material was pelletized and dried, a molded article of 40mm × 80mm × 3mm in thickness was molded under conditions of a cylinder temperature of 350 ℃, a mold temperature of 80 ℃, and a cycle time of 30 seconds. The molded article was placed in a gear oven heat resistance tester at a temperature of 120 ℃ for 1,000 hours.
A preferred embodiment of the polycarbonate resin composition of the present invention is a polycarbonate resin composition comprising only the aromatic polycarbonate resin (a), the phosphorus-based compound (B), and the polycaprolactone polyol (C). Another preferred embodiment of the polycarbonate resin composition of the present invention is a polycarbonate resin composition comprising only the aromatic polycarbonate resin (a), the phosphorus-based compound (B), the polycaprolactone polyol (C) and the polyether compound (D).
The polycarbonate resin composition of the present invention is a resin composition which is excellent in light transmittance and brightness and can withstand molding at high temperatures with a long molding cycle, and therefore is particularly suitable for injection molding. On the other hand, since the low-temperature moldability is also high, molded articles having excellent light transmittance can be obtained even by molding other than injection molding, and are useful as optical molded articles, particularly as light guide members.
The polycarbonate resin composition of the present invention can be stably molded in a wide temperature range as described above, and preferably, an optical molded article can be obtained by molding at a temperature of 280 ℃ to 360 ℃.
In addition, since the molded product is excellent in moisture resistance and heat resistance, it can be used in applications requiring moisture resistance and heat resistance.
The optical molded article includes a light guide member for a vehicle, and can be used as a light guide member for a vehicle used in a DRL in particular. The thickness of the DRL molded product is more preferably 5mm or more.
The light guide plate is not particularly limited, and may be a flat plate having a thickness of several mm to several hundred μm, or a curved plate or a prism transfer plate having a lens effect. The molding method is also not particularly limited, and the shape and the molding method may be appropriately selected depending on the purpose and the application.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
[ measurement of viscosity average molecular weight (Mv) ]
The intrinsic viscosity [ eta ] was determined by measuring the viscosity of a methylene chloride solution (concentration unit: g/L) at 20 ℃ with an Ubbelohde viscometer, and then calculated from the following equation.
[η]＝1.23×10-5Mv0.83
[ differential thermal-thermogravimetric assay (TG-DTA) of phosphorus-based Compound ]
10 to 15mg of a phosphorus compound was taken, and the change in weight at the time of heating to 550 ℃ was measured and recorded for each temperature under a nitrogen atmosphere at a heating rate of 20 ℃/min using a differential thermal-thermogravimetric analyzer "TG/DTA 7200 type" manufactured by SII corporation. The initial weight was set to 100%, and the temperature at which the weight was reduced by 2% was observed and set to the 98% holding temperature.
[ hydrolysis resistance test of phosphorus-based Compound ]
The phosphorus-containing compound was allowed to stand at 40 ℃ and 90% humidity for 1,500 hours. Then, the mass of the compound having a phenol structure produced by the decomposition was quantified by using a gas chromatograph apparatus "GC-2014" manufactured by shimadzu corporation, and the ratio to the phosphorus-based compound was measured.
The components used in the examples and comparative examples are as follows.
< aromatic polycarbonate resin (A) >
(A1) The method comprises the following steps "TARFLON FN 1500" (bisphenol A polycarbonate resin, manufactured by shinko Co., Ltd., viscosity average molecular weight (Mv) ═ 14,500)
(A2) The method comprises the following steps "TARFLON FN 1200" (bisphenol A polycarbonate resin, manufactured by Shikuchen corporation, having a viscosity-average molecular weight (Mv) ═ 11,500)
< phosphorus Compound (B) >
(B1) The method comprises the following steps "Doverphos S-9228 PC" (bis (2, 4-dicumylphenyl) pentaerythritol diphosphite manufactured by Dover Chemical Co., Ltd., 0.15 mass% of dicumylphenol was produced after the hydrolysis resistance test described above)
(B2) The method comprises the following steps "ADEKA STAB PEP-36" (bis (2, 6-di-tert-butyl-4-methylphenol, manufactured by ADEKA Co., Ltd.) pentaerythritol diphosphite, which produced 45 mass% of 2, 6-di-tert-butyl-4-methylphenol after the hydrolysis resistance test)
The results of the differential thermal-thermogravimetric measurement (TG-DTA) and hydrolysis resistance test described above for each phosphorus-based compound are summarized in table 3 below.
< polycaprolactone polyol (C) >
(C1) The method comprises the following steps "PLACCEL 210 CP" (polycaprolactone diol molecular weight 1000 manufactured by Daicel, Ltd.)
(C2) The method comprises the following steps "PLACCEL 220 CPB" (polycaprolactone diol molecular weight 2000, manufactured by Daicel, Ltd.)
(C3) The method comprises the following steps "PLACCEL H1P" (manufactured by Daicel, Inc. high molecular weight polycaprolactone (thermoplastic resin) molecular weight 10000)
< polyether Compound (D) >
(D1) The method comprises the following steps "Unilub 50 DE-25" (manufactured by Nippon oil Co., Ltd., polyethylene glycol-polypropylene glycol molecular weight 1750)
< other additives >
"Celloxide 2021P" (3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexanecarboxylate, manufactured by Daicel, Ltd.)
"KR-511" (polyorganosiloxane compound produced by shin-Etsu chemical Co., Ltd.)
Examples 1 to 10 and comparative examples 1 to 9
In each example, a polycarbonate resin composition was prepared by blending the respective components in the amount ratios shown in tables 1 and 2. The polycarbonate resin composition was melt-kneaded using a vented single-screw extruder (VS-40 manufactured by Takara plastics mechanical Co., Ltd.) having a screw diameter of 40mm at a cylinder temperature of 250 ℃ and cut into pellets. The obtained pellets were dried at 110 ℃ for 5 hours, and then molded into a 50mm × 80mm × 5mm thick flat plate test piece using an injection molding machine ("ES 1000" manufactured by Nichijindo corporation) at 280 ℃ and 360 ℃ cylinder temperature setting for 50 seconds with a cycle time.
The wet heat resistance test was performed as follows. The dried pellets were molded into a flat plate test piece of 40mm X80 mm X3 mm in thickness by using an injection molding machine ("EC 40N" manufactured by Toshiba mechanical Co., Ltd.) under conditions of a cylinder temperature of 350 ℃ and a cycle time of 30 seconds. The plate test piece was placed in a constant temperature and humidity chamber of model "LH 33-12P" manufactured by Nagano Science, Inc., set at a temperature of 85 ℃ and a relative humidity of 95% for 500 hours.
Further, the dried pellets were molded into a flat plate test piece of 40mm X80 mm X3 mm in thickness by using an injection molding machine ("EC 40N" manufactured by Toshiba mechanical Co., Ltd.) under conditions of a cylinder temperature of 350 ℃, a mold temperature of 80 ℃ and a cycle time of 30 seconds. The flat plate test piece was placed in a gear oven "GPS-222" manufactured by TABAI corporation whose temperature was adjusted to 120 ℃ for 1,000 hours.
The YI value of the test piece obtained above was measured using a spectrophotometer ("U-4100" manufactured by Hitachi Kagaku K.K.) under a C light source and a 2-degree field of view. The results are shown in tables 1 and 2. The standard of acceptability of a test piece having a thickness of 5mm is that the YI value (280 ℃ C. molding) of a test piece molded at 280 ℃ is 1.10 or less and that of a test piece molded at 360 ℃ is 1.25 or less (in the table, the YI value is expressed as "plate YI"). Further, Δ YI represents the difference in hue between the 280 ℃ molding and the 360 ℃ molding.
YI after the wet heat resistance test (500 hours) using the constant temperature and humidity test chamber is not particularly specified, but Δ YI before and after the test is required to be 0.2(0.20) or less. YI after the heat resistance test (1,000 hours) using the gear oven heat resistance tester is not particularly specified, and Δ YI before and after the test is preferably 0.5(0.50) or less.
[ Table 3]
In comparative examples 1 and 6 which did not contain the specific phosphorus-based compound (B) and polycaprolactone polyol (C), the hue was good at low-temperature molding, but was poor at high-temperature molding, and the hue difference (. DELTA.YI) between low-temperature molding and high-temperature molding was large. In comparative example 2 containing the specific phosphorus-based compound (B) without polycaprolactone polyol (C), the color tone was still acceptable in the case of high-temperature molding, but the color tone was insufficient in the case of low-temperature molding. In comparative examples 3, 4, 7 and 8, a specific phosphorus antioxidant was not used as an antioxidant, and although polycaprolactone polyol was contained, the hue at high temperature molding was poor. In comparative examples 5 and 9, although polycaprolactone having a high molecular weight was contained, the color tone was further poor at the time of high-temperature molding (at the time of molding at 360 ℃). In addition to comparative example 2, the decrease in color tone after the wet heat resistance test was large, and the possibility of hydrolysis was high.
On the other hand, in examples 1 to 10 containing the phosphorus-based compound (B) having an aryl group in an amount of 5 mass% or less of the compound having a phenol structure produced after the decomposition temperature was high and the hydrolysis resistance test, and the polycaprolactone polyol (C), the difference in color at the time of high and low temperature molding was small. In examples 5 and 6 in which the polyether compound (D) was further used in combination, the color tone at the time of low-temperature molding (at the time of molding at 280 ℃) was improved. High hydrolysis resistance is also shown in the wet heat resistance test.
Industrial applicability
The polycarbonate resin composition of the present invention is excellent in heat stability under high-temperature molding, and can give a molded article which is not deteriorated in optical properties due to deterioration during molding even when molded over a wide temperature range, and is excellent in moist heat resistance and long-term heat resistance. This is suitable for optical products, for example, light guide plates, specifically, large-screen and thin light guide plates such as smart phones and tablet PCs, and also for thick-walled lenses such as DRLs for automobiles.
Claims (50)
1. A polycarbonate resin composition comprising an aromatic polycarbonate resin (A), a phosphorus-based compound (B) having an aromatic group, and a polycaprolactone polyol (C),
the phosphorus-containing compound (B) is contained in an amount of 0.005 to 1 part by mass and the polycaprolactone polyol (C) is contained in an amount of 0.005 to 5 parts by mass based on 100 parts by mass of the aromatic polycarbonate resin (A),
wherein the amount of the compound having a phenol structure generated by decomposition after 1,500 hours when the phosphorus-based compound (B) is left to stand at 40 ℃ and a humidity of 90% is 5% by mass or less based on the phosphorus-based compound (B),
wherein the phosphorus-containing compound (B) is a compound having a temperature of 340 ℃ or higher at which 2% of the weight is reduced from the weight before measurement when the weight is measured using a TG-DTA machine which is a differential thermal-thermogravimetric analyzer in a nitrogen atmosphere,
the number average molecular weight of the polycaprolactone polyol (C) is more than 500 and less than 5000.
2. The polycarbonate resin composition according to claim 1, wherein the phosphorus-based compound (B) is contained in an amount of 0.01 to 0.8 parts by mass based on 100 parts by mass of the aromatic polycarbonate resin (A).
3. The polycarbonate resin composition according to claim 1 or 2, wherein the phosphorus-based compound (B) is contained in an amount of 0.03 to 0.5 parts by mass based on 100 parts by mass of the aromatic polycarbonate resin (A).
4. The polycarbonate resin composition according to claim 1 or 2, wherein the phosphorus-based compound (B) is contained in an amount of 0.03 to 0.3 parts by mass based on 100 parts by mass of the aromatic polycarbonate resin (A).
5. The polycarbonate resin composition according to claim 1 or 2, wherein the amount of the compound having a phenol structure generated by decomposition after 1500 hours when the phosphorus-based compound (B) is left to stand at 40 ℃ and a humidity of 90% is 3% by mass or less based on the phosphorus-based compound (B).
6. The polycarbonate resin composition according to claim 1 or 2, wherein the amount of the compound having a phenol structure generated by decomposition after 1500 hours when the phosphorus-based compound (B) is left to stand at 40 ℃ and a humidity of 90% is 1% by mass or less based on the phosphorus-based compound (B).
7. The polycarbonate resin composition according to claim 1 or 2, wherein the amount of the compound having a phenol structure generated by decomposition after 1500 hours when the phosphorus-based compound (B) is left to stand at 40 ℃ and a humidity of 90% is 0.5% by mass or less based on the phosphorus-based compound (B).
8. The polycarbonate resin composition according to claim 1 or 2, wherein the phosphorus-based compound (B) is a compound having a temperature of 345 ℃ or higher at which 2% of the weight of the phosphorus-based compound (B) is reduced from the weight before measurement when the weight is measured using a differential thermal thermogravimetric analyzer, TG-DTA machine under a nitrogen atmosphere.
9. The polycarbonate resin composition according to claim 1 or 2, wherein the phosphorus-based compound (B) is a compound having a temperature of 350 ℃ or higher at which 2% of the weight of the phosphorus-based compound (B) is reduced from the weight before measurement when the weight is measured using a TG-DTA machine which is a differential thermal thermogravimetric machine under a nitrogen atmosphere.
10. The polycarbonate resin composition according to claim 1 or 2, wherein the polycaprolactone polyol (C) is contained in an amount of 0.01 to 5 parts by mass based on 100 parts by mass of the aromatic polycarbonate resin (A).
11. The polycarbonate resin composition according to claim 1 or 2, wherein the polycaprolactone polyol (C) is contained in an amount of 0.02 parts by mass or more and 3 parts by mass or less based on 100 parts by mass of the aromatic polycarbonate resin (A).
12. The polycarbonate resin composition according to claim 1 or 2, wherein the polycaprolactone polyol (C) is contained in an amount of 0.03 parts by mass or more and 2 parts by mass or less based on 100 parts by mass of the aromatic polycarbonate resin (A).
13. The polycarbonate resin composition according to claim 1 or 2, wherein the polycaprolactone polyol (C) is contained in an amount of 0.1 to 2 parts by mass based on 100 parts by mass of the aromatic polycarbonate resin (A).
14. The polycarbonate resin composition according to claim 1 or 2, wherein the polycaprolactone polyol (C) is contained in an amount of 0.3 to 1.5 parts by mass based on 100 parts by mass of the aromatic polycarbonate resin (A).
15. The polycarbonate resin composition according to claim 1, further comprising 5 parts by mass or less of a polyether compound (D) represented by the following formula (1) per 100 parts by mass of the aromatic polycarbonate resin (A),
RD3O-(RD1O)m(RD2O)n-RD4(1)
in the formula, RD1And RD2Represents an alkylene group having 1 or more carbon atoms, RD1And RD2The same or different; m + n is 5 or more and less than 300; r when m is 2 or moreD1R is the same or different, when n is 2 or moreD2The same or different; rD3And RD4Represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, an alkanoyl group having 1 to 30 carbon atoms, an alkenoyl group having 2 to 30 carbon atoms, or a glycidyl group, RD3And RD4The same or different.
16. The polycarbonate resin composition of claim 15, wherein R in the formula (1)D1And RD2Has 1 to 8 carbon atoms.
17. The polycarbonate resin composition of claim 15 or 16, wherein R in the formula (1)D1And RD2Has 1 to 6 carbon atoms.
18. The polycarbonate resin composition of claim 15 or 16, wherein R in the formula (1)D1And RD2Has 1 to 5 carbon atoms.
19. The polycarbonate resin composition according to claim 15 or 16, wherein the polyether compound (D) represented by the formula (1) is contained in an amount of 0 to 4 parts by mass based on 100 parts by mass of the aromatic polycarbonate resin (A).
20. The polycarbonate resin composition according to claim 15 or 16, wherein the polyether compound (D) represented by the formula (1) is contained in an amount of 0 part by mass or more and 3 parts by mass or less based on 100 parts by mass of the aromatic polycarbonate resin (A).
21. The polycarbonate resin composition according to claim 15 or 16, wherein the polyether compound (D) represented by the formula (1) is contained in an amount of 0.05 parts by mass or more and 5 parts by mass or less based on 100 parts by mass of the aromatic polycarbonate resin (A).
22. The polycarbonate resin composition according to claim 15 or 16, wherein the polyether compound (D) represented by the formula (1) is contained in an amount of 0.1 to 3 parts by mass based on 100 parts by mass of the aromatic polycarbonate resin (A).
23. The polycarbonate resin composition according to claim 1 or 2, wherein the aromatic polycarbonate resin (A) is a polycarbonate having a repeating unit represented by the following general formula (I) in the main chain,
in the formula, RA1And RA2Represents an alkyl or alkoxy group having 1 to 6 carbon atoms, RA1And RA2The same or different; x represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO2-, -O-or-CO-, a and b each independently represent an integer of 0 or more and 4 or less; r when a is 2 or moreA1R is the same or different, when b is 2 or moreA2The same or different.
24. The polycarbonate resin composition according to claim 1 or 2, wherein the phosphorus-based compound (B) is a phosphorus-based compound having a phosphite structure.
25. The polycarbonate resin composition according to claim 1 or 2, wherein the phosphorus-based compound (B) is a pentaerythritol diphosphite compound represented by the following general formula (II),
in the formula, Y1～Y4The carbon atoms are equal to or different from each other and represent hydrocarbon groups having 6 to 15 carbon atoms.
26. The polycarbonate resin composition of claim 25, wherein Y in the formula (II)1～Y4Each independently is unsubstituted or substituted cumyl, unsubstituted or substituted phenyl, unsubstituted or substituted naphthyl, or unsubstituted or substituted biphenyl.
27. The polycarbonate resin composition according to claim 1 or 2, wherein the phosphorus-based compound (B) is a pentaerythritol diphosphite compound represented by the following general formula (II-1),
in the formula, RB1～RB8Represents alkyl or alkenyl, identical or different; rB1And RB2、RB3And RB4、RB5And RB6、RB7And RB8May be bonded to each other to form a ring; rB9～RB12Represents a hydrogen atom or an alkyl group, the same or different; m1 to m4 are integers of 0 to 5 inclusive, and may be the same or different; z1～Z4Represents a single bond or a carbon atom, identical or different; at Z1～Z4When represents a single bond, RB1～RB8Are excluded from the general formula (II-1).
28. The polycarbonate resin composition according to claim 1 or 2, wherein the phosphorus-based compound (B) is bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.
29. The polycarbonate resin composition of claim 1 or 2, wherein the polycaprolactone polyol (C) is at least one selected from the group consisting of polycaprolactone diol, polycaprolactone triol, and polycaprolactone tetraol.
30. The polycarbonate resin composition of claim 15 or 16, wherein the polyether compound (D) is R in formula (1)D1And RD2Is alkylene group with 2-5 carbon atoms, RD3And RD4A polyether compound which is a hydrogen atom.
31. The polycarbonate resin composition according to claim 1 or 2, further comprising 0.01 to 0.15 parts by mass of a polyorganosiloxane per 100 parts by mass of the aromatic polycarbonate resin (A).
32. The polycarbonate resin composition according to claim 1 or 2, further comprising 0.02 to 0.15 parts by mass of a polyorganosiloxane per 100 parts by mass of the aromatic polycarbonate resin (A).
33. The polycarbonate resin composition according to claim 1 or 2, further comprising 0.05 to 0.1 parts by mass of a polyorganosiloxane per 100 parts by mass of the aromatic polycarbonate resin (A).
34. The polycarbonate resin composition of claim 31, wherein said polyorganosiloxane has at least one functional group selected from the group consisting of alkoxy, aryloxy, polyoxyalkylene, carboxyl, silanol, amino, mercapto, epoxy, and vinyl.
35. The polycarbonate resin composition according to claim 1 or 2, further comprising 0.001 to 0.5 parts by mass of an aliphatic cyclic epoxy compound per 100 parts by mass of the aromatic polycarbonate resin (A).
36. The polycarbonate resin composition according to claim 1 or 2, further comprising 0.005 to 0.2 parts by mass of an aliphatic cyclic epoxy compound per 100 parts by mass of the aromatic polycarbonate resin (A).
37. The polycarbonate resin composition according to claim 1 or 2, further comprising 0.01 to 0.1 parts by mass of an aliphatic cyclic epoxy compound per 100 parts by mass of the aromatic polycarbonate resin (A).
38. The polycarbonate resin composition according to claim 1 or 2, wherein the aromatic polycarbonate resin (A) has a viscosity average molecular weight Mv of 9000 or more and 50000 or less.
39. The polycarbonate resin composition according to claim 1 or 2, wherein the aromatic polycarbonate resin (A) has a viscosity average molecular weight Mv of 10000 to 30000 inclusive.
40. The polycarbonate resin composition according to claim 1 or 2, wherein the aromatic polycarbonate resin (A) has a viscosity average molecular weight Mv of 11000 or more and 25000 or less.
41. The polycarbonate resin composition according to claim 1 or 2, wherein the aromatic polycarbonate resin (A) has a viscosity average molecular weight Mv of 9000 or more and 17000 or less.
42. The polycarbonate resin composition according to claim 1 or 2, wherein the YI value measured by the following measurement methods (1) and (2) is 1.2 or less and the difference between the YI values measured by the following measurement methods (1) and (2) is 0.1 or less,
measurement method (1): granulating a polycarbonate resin molding material, drying the obtained product, molding the obtained product by an injection molding method under conditions of a cylinder temperature of 360 ℃, a mold temperature of 80 ℃ and a cycle time of 50 seconds to obtain a molded product of 50mm × 80mm × 5mm in thickness, and measuring a YI value of the molded product by a spectrophotometer under conditions of a C light source and a 2-degree visual field;
measurement method (2): a polycarbonate resin molding material was pelletized and dried, and then a molded article of 50mm X80 mm X5 mm thickness was molded by injection molding under conditions of a cylinder temperature of 280 ℃, a mold temperature of 80 ℃ and a cycle time of 50 seconds, and the YI value of the molded article was measured with a spectrophotometer under a C light source and a 2-degree visual field.
43. The polycarbonate resin composition according to claim 1 or 2, wherein the YI value measured by the following measurement methods (1) and (2) is 1.15 or less, the difference between the YI values measured by the following measurement methods (1) and (2) is 0.08 or less,
measurement method (1): granulating a polycarbonate resin molding material, drying the obtained product, molding the obtained product by an injection molding method under conditions of a cylinder temperature of 360 ℃, a mold temperature of 80 ℃ and a cycle time of 50 seconds to obtain a molded product of 50mm × 80mm × 5mm in thickness, and measuring a YI value of the molded product by a spectrophotometer under conditions of a C light source and a 2-degree visual field;
measurement method (2): a polycarbonate resin molding material was pelletized and dried, and then a molded article of 50mm X80 mm X5 mm thickness was molded by injection molding under conditions of a cylinder temperature of 280 ℃, a mold temperature of 80 ℃ and a cycle time of 50 seconds, and the YI value of the molded article was measured with a spectrophotometer under a C light source and a 2-degree visual field.
44. The polycarbonate resin composition according to claim 1 or 2, which has a YI value of 1.25 or less as measured by the following measurement method (1) and a YI value of 1.10 or less as measured by the following measurement method (2),
measurement method (1): granulating a polycarbonate resin molding material, drying the obtained product, molding the obtained product by an injection molding method under conditions of a cylinder temperature of 360 ℃, a mold temperature of 80 ℃ and a cycle time of 50 seconds to obtain a molded product of 50mm × 80mm × 5mm in thickness, and measuring a YI value of the molded product by a spectrophotometer under conditions of a C light source and a 2-degree visual field;
measurement method (2): a polycarbonate resin molding material was pelletized and dried, and then a molded article of 50mm X80 mm X5 mm thickness was molded by injection molding under conditions of a cylinder temperature of 280 ℃, a mold temperature of 80 ℃ and a cycle time of 50 seconds, and the YI value of the molded article was measured with a spectrophotometer under a C light source and a 2-degree visual field.
45. The polycarbonate resin composition according to claim 1 or 2, wherein when the following wet heat resistance test is performed, the difference Δ YI between YI values of molded articles before and after the test is 0.20 or less,
wet heat resistance test method: after the polycarbonate resin molding material was pelletized and dried, a molded article of 40mm × 80mm × 3mm in thickness was molded under conditions of a cylinder temperature of 350 ℃, a mold temperature of 80 ℃ and a cycle time of 30 seconds, and the molded article was placed in a constant temperature and humidity chamber set at a temperature of 85 ℃ and a relative humidity of 95% for 500 hours.
46. The polycarbonate resin composition according to claim 1 or 2, wherein when the following heat resistance test is performed, the difference Δ YI between YI values of molded articles before and after the test is 0.50 or less,
heat resistance test method: after the polycarbonate resin molding material was pelletized and dried, a molded article of 40mm × 80mm × 3mm in thickness was molded under conditions of a cylinder temperature of 350 ℃, a mold temperature of 80 ℃ and a cycle time of 30 seconds, and the molded article was placed in a gear oven heat resistance tester at a temperature of 120 ℃ for 1000 hours.
47. An optical molded article comprising the polycarbonate resin composition according to any one of claims 1 to 46.
48. The optical molded article according to claim 47, which is a light-guiding member.
49. The optical molded article according to claim 47 or 48, which is a light guide member for a vehicle.
50. A daytime running lamp comprising the optical molding of claim 49.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| PCT/JP2016/066973 WO2016199783A1 (en) | 2015-06-08 | 2016-06-07 | Polycarbonate resin composition and optical moulded article |
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| JP2018119071A (en) * | 2017-01-26 | 2018-08-02 | 住化ポリカーボネート株式会社 | Light guide for vehicle lamp |
| WO2018173616A1 (en) * | 2017-03-23 | 2018-09-27 | 三菱エンジニアリングプラスチックス株式会社 | Method for producing aromatic polycarbonate resin molded article |
| JP6416423B1 (en) | 2017-06-05 | 2018-10-31 | 三菱エンジニアリングプラスチックス株式会社 | Polycarbonate resin composition for optical parts and optical parts |
| JP6480068B1 (en) * | 2018-01-26 | 2019-03-06 | 住化ポリカーボネート株式会社 | Aromatic polycarbonate resin composition and optical molded article |
| CN111630108B (en) * | 2018-01-26 | 2022-12-27 | 住化Pc有限公司 | Aromatic polycarbonate resin composition and optical molded article |
| CN115605542A (en) * | 2020-05-12 | 2023-01-13 | 帝人株式会社（Jp） | Polycarbonate resin composition and molded article thereof |
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| Publication number | Publication date |
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| CN107636075A (en) | 2018-01-26 |
| TWI725032B (en) | 2021-04-21 |
| WO2016199783A1 (en) | 2016-12-15 |
| JP6702615B2 (en) | 2020-06-03 |
| TW201708383A (en) | 2017-03-01 |
| JPWO2016199783A1 (en) | 2018-03-29 |
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