JP5910298B2 - 芳香族ポリカーボネート樹脂組成物及びその成形品 - Google Patents
芳香族ポリカーボネート樹脂組成物及びその成形品 Download PDFInfo
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- JP5910298B2 JP5910298B2 JP2012112500A JP2012112500A JP5910298B2 JP 5910298 B2 JP5910298 B2 JP 5910298B2 JP 2012112500 A JP2012112500 A JP 2012112500A JP 2012112500 A JP2012112500 A JP 2012112500A JP 5910298 B2 JP5910298 B2 JP 5910298B2
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- polycarbonate resin
- aromatic polycarbonate
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- 125000003118 aryl group Chemical group 0.000 title claims description 191
- 229920005668 polycarbonate resin Polymers 0.000 title claims description 163
- 239000004431 polycarbonate resin Substances 0.000 title claims description 163
- 239000000203 mixture Substances 0.000 title claims description 99
- -1 polyfluoroethylene Polymers 0.000 claims description 122
- 229920000954 Polyglycolide Polymers 0.000 claims description 83
- 239000004633 polyglycolic acid Substances 0.000 claims description 83
- 229920001577 copolymer Polymers 0.000 claims description 74
- 150000001875 compounds Chemical class 0.000 claims description 64
- 239000003063 flame retardant Substances 0.000 claims description 60
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 57
- 229920000642 polymer Polymers 0.000 claims description 55
- 229910052698 phosphorus Inorganic materials 0.000 claims description 41
- 239000011574 phosphorus Substances 0.000 claims description 41
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 40
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 150000003839 salts Chemical class 0.000 claims description 30
- 239000004593 Epoxy Substances 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 229920000515 polycarbonate Polymers 0.000 claims description 25
- 239000004417 polycarbonate Substances 0.000 claims description 25
- 229920002554 vinyl polymer Polymers 0.000 claims description 24
- 238000000465 moulding Methods 0.000 claims description 23
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 20
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 18
- 229920001296 polysiloxane Polymers 0.000 claims description 16
- 229920001519 homopolymer Polymers 0.000 claims description 7
- 239000002253 acid Substances 0.000 description 45
- 229920001971 elastomer Polymers 0.000 description 43
- 229920005989 resin Polymers 0.000 description 43
- 239000011347 resin Substances 0.000 description 43
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 42
- 239000000178 monomer Substances 0.000 description 42
- 238000000034 method Methods 0.000 description 38
- 239000005060 rubber Substances 0.000 description 38
- 229910019142 PO4 Inorganic materials 0.000 description 37
- 239000010452 phosphate Substances 0.000 description 37
- 230000000694 effects Effects 0.000 description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 31
- 239000000126 substance Substances 0.000 description 23
- 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 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 19
- 238000002156 mixing Methods 0.000 description 19
- 125000004122 cyclic group Chemical group 0.000 description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 description 16
- 125000000217 alkyl group Chemical group 0.000 description 15
- 229920000578 graft copolymer Polymers 0.000 description 15
- 239000000049 pigment Substances 0.000 description 15
- 239000000975 dye Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 239000003963 antioxidant agent Substances 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 10
- 230000007423 decrease Effects 0.000 description 10
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 10
- 238000004898 kneading Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 230000003078 antioxidant effect Effects 0.000 description 9
- 239000012760 heat stabilizer Substances 0.000 description 9
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 8
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 8
- 229920002725 thermoplastic elastomer Polymers 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- 229920006361 Polyflon Polymers 0.000 description 7
- 239000006096 absorbing agent Substances 0.000 description 7
- 229920001893 acrylonitrile styrene Polymers 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 239000011256 inorganic filler Substances 0.000 description 7
- 229910003475 inorganic filler Inorganic materials 0.000 description 7
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 7
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 7
- 239000011342 resin composition Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 229920000800 acrylic rubber Polymers 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 239000002216 antistatic agent Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 229920000058 polyacrylate Polymers 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000005907 alkyl ester group Chemical group 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229920003244 diene elastomer Polymers 0.000 description 4
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
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- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000004310 lactic acid Substances 0.000 description 4
- 235000014655 lactic acid Nutrition 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
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- 125000005372 silanol group Chemical group 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
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- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 150000008360 acrylonitriles Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000001177 diphosphate Substances 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 3
- 235000011180 diphosphates Nutrition 0.000 description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
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- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 229940059574 pentaerithrityl Drugs 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 3
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 3
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
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- 239000004626 polylactic acid Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
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- 229920005990 polystyrene resin Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 235000014692 zinc oxide Nutrition 0.000 description 3
- VVUWYXJTOLSMFV-UHFFFAOYSA-N (2-hydroxy-4-octylphenyl)-phenylmethanone Chemical compound OC1=CC(CCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 VVUWYXJTOLSMFV-UHFFFAOYSA-N 0.000 description 2
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- 229910052759 nickel Inorganic materials 0.000 description 1
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- GHKGUEZUGFJUEJ-UHFFFAOYSA-M potassium;4-methylbenzenesulfonate Chemical compound [K+].CC1=CC=C(S([O-])(=O)=O)C=C1 GHKGUEZUGFJUEJ-UHFFFAOYSA-M 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
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- 150000003254 radicals Chemical class 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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- QBJDFZSOZNDVDE-UHFFFAOYSA-M sodium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QBJDFZSOZNDVDE-UHFFFAOYSA-M 0.000 description 1
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- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- XKFPGUWSSPXXMF-UHFFFAOYSA-N tributyl(methyl)phosphanium Chemical compound CCCC[P+](C)(CCCC)CCCC XKFPGUWSSPXXMF-UHFFFAOYSA-N 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- BWPNIANVWARHPR-UHFFFAOYSA-N tridecyl dihydrogen phosphite Chemical compound CCCCCCCCCCCCCOP(O)O BWPNIANVWARHPR-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- ILLOBGFGKYTZRO-UHFFFAOYSA-N tris(2-ethylhexyl) phosphite Chemical compound CCCCC(CC)COP(OCC(CC)CCCC)OCC(CC)CCCC ILLOBGFGKYTZRO-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- SAAMKFBWYWFBNY-UHFFFAOYSA-N tris(4-tert-butylphenyl) phosphite Chemical compound C1=CC(C(C)(C)C)=CC=C1OP(OC=1C=CC(=CC=1)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1 SAAMKFBWYWFBNY-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- PEXOFOFLXOCMDX-UHFFFAOYSA-N tritridecyl phosphite Chemical compound CCCCCCCCCCCCCOP(OCCCCCCCCCCCCC)OCCCCCCCCCCCCC PEXOFOFLXOCMDX-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
特許文献6の芳香族ポリカーボネート樹脂組成物であれば、芳香族ポリカーボネート樹脂にポリグリコール酸を所定の割合で配合することにより、芳香族ポリカーボネート樹脂の耐熱性を損なうことなく、耐薬品性と表面硬度を改善することができ、耐薬品性、耐熱性に優れる上に、表面硬度が高く、剛性に優れた成形品を与える芳香族ポリカーボネート樹脂組成物を実現することができる。
(Ea)相溶化剤:(Ea−1)エポキシ基変性重合体と(Ea−2)ビニル系重合体との共重合体
(Eb)相溶化剤:(Eb−1)ポリカーボネート系化合物と(Eb−2)エポキシ基変性重合体との共重合体
本発明の芳香族ポリカーボネート樹脂組成物は、少なくとも、(A)芳香族ポリカーボネート樹脂と、(B)ポリグリコール酸と、(C)リン系難燃剤と、(D)ポリフルオロエチレンを特定の割合で含有してなる。また、本発明の芳香族ポリカーボネート樹脂組成物は、必要に応じて更にその他の成分を含有していてもよい。
また、このような芳香族ポリカーボネート樹脂組成物に更に(C)リン系難燃剤と(D)ポリフルオロエチレンを所定の割合で配合することにより、(C)リン系難燃剤と(D)ポリフルオロエチレンとの併用による優れた相乗効果で著しく高い難燃性を得ることができると共に、(C)リン系難燃剤が(B)ポリグリコール酸の分解を抑制する効果ならびに相溶化剤として機能して、流れ値(Q値)の上昇を抑制して成形品外観を改善することができる。
本発明で使用される(A)芳香族ポリカーボネート樹脂(以下「(A)成分」と称す場合がある。)は、芳香族ジヒドロキシ化合物又はこれと少量のポリヒドロキシ化合物を、ホスゲン又は炭酸ジエステルと反応させることによって得られる、分岐していてもよい熱可塑性重合体又は共重合体である。芳香族ポリカーボネート樹脂の製造方法は、特に限定されるものではなく、従来公知のホスゲン法(界面重合法)や溶融法(エステル交換法)により製造したものを使用することができる。また、溶融法を用いた場合には、末端基のOH基量を調整した芳香族ポリカーボネート樹脂を使用することができる。
本発明の芳香族ポリカーボネート樹脂組成物は、耐薬品性、表面硬度(剛性)の改善のために、(B)下記式(I)で表される繰り返し単位を有するポリグリコール酸(以下「(B)成分」と称す場合がある。)を含有することを特徴とする。ここで、「繰り返し単位」とは、モノマーを重合又は共重合させてポリグリコール酸を製造する際に用いられる原料モノマーに由来する構造部分をさす。
本発明の芳香族ポリカーボネート樹脂組成物は、(B)ポリグリコール酸を、(A)芳香族ポリカーボネート樹脂と(B)ポリグリコール酸との合計100質量部中に、10〜50質量部、好ましくは15〜45質量部、より好ましくは20〜40質量部を含み、(A)芳香族ポリカーボネート樹脂を50〜90質量部、好ましくは55〜85質量部、より好ましくは60〜80質量部含む。芳香族ポリカーボネート樹脂組成物中の(B)ポリグリコール酸の含有量が上記下限より少なく、(A)芳香族ポリカーボネート樹脂の含有量が上記上限よりも多いと、(B)ポリグリコール酸を配合したことによる、耐薬品性、表面硬度、剛性の向上効果を十分に得ることができず、(B)ポリグリコール酸の含有量が上記上限より多く、(A)芳香族ポリカーボネート樹脂の含有量が上記下限よりも少ないと、耐熱性、成形品表面外観が低下する傾向にある。
本発明の芳香族ポリカーボネート樹脂組成物は、難燃性の改善のために(C)リン系難燃剤を含有する。
(C)リン系難燃剤は、1種を単独で用いてもよく、2種以上を混合して用いてもよい。
(C)リン系難燃剤としては、中でも難燃化効果が高く、流動性向上効果があり、金型腐食が生じにくいことから、リン酸エステル系難燃剤が好ましい。
特に、このリン酸エステル系難燃剤としては、下記の一般式(II)で表されるリン酸エステル系化合物が好ましい。
tが0の場合、一般式(II)で表される化合物はリン酸エステルであり、tが0より大きい場合は縮合リン酸エステル(混合物を含む)である。本発明には、特に縮合リン酸エステルが好適に用いられる。
ホスファゼン系難燃剤は、分子中に−P=N−結合を有する有機化合物であり、ホスファゼン系難燃剤としては、好ましくは下記一般式(IIIa)で表される環状ホスファゼン化合物、下記一般式(IIIb)で表される鎖状ホスファゼン化合物、下記一般式(IIIa)及び下記一般式(IIIb)からなる群より選択される少なくとも一種のホスファゼン化合物が架橋基によって架橋されてなる架橋ホスファゼン化合物が挙げられる。架橋ホスファゼン化合物としては、下記一般式(IIIc)で表される架橋基によって架橋されてなるものが難燃性の点から好ましい。
本発明の芳香族ポリカーボネート樹脂組成物中の(C)リン系難燃剤の含有量は、(A)芳香族ポリカーボネート樹脂と(B)ポリグリコール酸の合計100質量部に対して2〜25質量部、好ましくは5〜20質量部、特に好ましくは10〜15質量部である。(C)リン系難燃剤の含有量が上記下限よりも少ないと、(C)リン系難燃剤を配合したことによる難燃性の改善効果を十分に得ることができず、上記上限よりも多いと、耐熱性や耐衝撃性が低下するおそれがある。
本発明の芳香族ポリカーボネート樹脂組成物は、燃焼時の滴下防止を目的として、滴下防止剤として(D)ポリフルオロエチレンを含有する。
本発明の芳香族ポリカーボネート樹脂組成物は、必要に応じて以下の(Ea)相溶化剤及び/又は(Eb)相溶化剤(以下、これらを「(E)相溶化剤」又は「(E)成分」と称す場合がある。)を含有していてもよく、(E)相溶化剤を配合することにより、(B)ポリグリコール酸の分解をより一層確実に防止して、流れ値(Q値)の上昇を抑制し、成形品外観を改善すると共に、更には耐衝撃性を改善することもできる。
(Ea)相溶化剤:(Ea−1)エポキシ基変性重合体と(Ea−2)ビニル系重合体との共重合体
(Eb)相溶化剤:(Eb−1)ポリカーボネート系化合物と(Eb−2)エポキシ基変性重合体との共重合体
本発明で用いる(Ea)相溶化剤(以下、「(Ea)成分」と称す場合がある。)は、(Ea−1)エポキシ変性重合体(以下、「(Ea−1)成分」と称す場合がある。)とこの(Ea−1)成分と共重合可能な(Ea−2)ビニル系重合体(以下、「(Ea−2)成分」と称す場合がある。)を共重合してなる共重合体である。
本発明で用いる(Eb)相溶化剤(以下、「(Eb)成分」と称す場合がある。)は、(Eb−1)ポリカーボネート系化合物と(Eb−2)エポキシ基変性重合体との共重合体である。この(Eb)相溶化剤の共重合体は、ポリカーボネート構造を含む主鎖に、グラフト鎖として(Eb−2)エポキシ基変性重合体によりエポキシ変性されたスチレン系重合体が導入されたものが好ましい。
上記の(メタ)アクリル酸の低級アルキルエステルとしては、例えば、アクリル酸メチル、アクリル酸エチル、メタクリル酸メチル、メタクリル酸エチル等が挙げられる。
ブタジエン−(メタ)アクリル酸の低級アルキルエステル共重合体又はブタジエン−スチレン−(メタ)アクリル酸の低級アルキルエステル共重合体における(メタ)アクリル酸の低級アルキルエステルの割合は、ゴム重量の30質量%以下であることが好ましい。
これらのスチレン系重合体は、1種を単独で用いてもよく、2種以上を混合して用いてもよい。
本発明の芳香族ポリカーボネート樹脂組成物が(E)相溶化剤を含有する場合、本発明の芳香族ポリカーボネート樹脂組成物中の(E)相溶化剤の含有量は、(A)芳香族ポリカーボネート樹脂(A)と(B)ポリグリコール酸との合計100質量部に対して、0.1〜15質量部、特に1〜12質量部、とりわけ3〜10質量部であることが好ましい。芳香族ポリカーボネート樹脂組成物中の(E)相溶化剤の含有量が上記下限より少ないと、(E)相溶化剤を配合したことによる成形品外観及び耐衝撃性の改善効果を十分に得ることができず、上記上限より多いと表面硬度が低下する傾向にある。
本発明の芳香族ポリカーボネート樹脂組成物は、必要に応じて(F)有機スルホン酸金属塩を含有していてもよく、(C)リン系難燃剤と共に(F)有機スルホン酸金属塩を併用することにより、難燃性をより一層高めることができる。
(F)有機スルホン酸金属塩は、1種を単独で用いてもよく、2種以上を混合して用いてもよい。
本発明の芳香族ポリカーボネート樹脂組成物は必要に応じて(G)シリコーン系難燃剤を含有していてもよく、(C)リン系難燃剤と共に(G)シリコーン系難燃剤を併用することにより、難燃性をより一層高めることができる。なお、本発明の芳香族ポリカーボネート樹脂組成物は、前記(F)有機スルホン酸金属塩と共に(G)シリコーン系難燃剤を含有していてもよい。
SY430、東レダウコーニング社製217FLAKE、SH−6018等が挙げられる。
本発明の芳香族ポリカーボネート樹脂組成物は、上記(A)芳香族ポリカーボネート樹脂及び(B)ポリグリコール酸と、(C)リン系難燃剤、(D)ポリフルオロエチレン、(E)相溶化剤、(F)有機スルホン酸金属塩、(G)シリコーン系難燃剤以外に、必要に応じてその他の成分を含有していてもよい。本発明の芳香族ポリカーボネート樹脂組成物が含有し得るその他の成分としては、例えば以下のようなものが挙げられる。
本発明の芳香族ポリカーボネート樹脂組成物は(H)リン系熱安定剤を含有することができる。(H)リン系熱安定剤は一般的に、樹脂成分を溶融混練する際、高温下での滞留安定性や樹脂成形品使用時の耐熱安定性向上に有効である。
本発明の芳香族ポリカーボネート樹脂組成物は、所望によって酸化防止剤を含有することが好ましい。酸化防止剤を含有することで、色相劣化や、熱滞留時の機械物性の低下が抑制できる。
本発明の芳香族ポリカーボネート樹脂組成物は、本発明の効果を損なわない範囲で、更に種々の添加剤を含有していても良い。このような添加剤としては、離型剤、紫外線吸収剤、無機フィラー、染顔料、帯電防止剤、加水分解抑制剤、衝撃強度改良剤、(A)芳香族ポリカーボネート樹脂、(B)リン系難燃剤及び(E)成分以外の他の樹脂などが挙げられる。
本発明の芳香族ポリカーボネート樹脂組成物は、離型剤を含有していてもよく、離型剤としては、脂肪族アルコールと脂肪族カルボン酸とのフルエステル化物が好適に用いられる。
本発明の芳香族ポリカーボネート樹脂組成物は、所望によって紫外線吸収剤を含有することが好ましい。紫外線吸収剤を含有することで、本発明の芳香族ポリカーボネート樹脂組成物の耐候性を向上させることができる。
なお、紫外線吸収剤は、1種が含有されていてもよく、2種以上が任意の組み合わせ及び比率で含有されていても良い。
本発明の芳香族ポリカーボネート樹脂組成物は、剛性や強度を向上させる目的で無機フィラーを含有させることができる。無機フィラーの具体例としては、ガラス繊維(チョップドストランド)、ガラス短繊維(ミルドファイバー)、ガラスフレーク、ガラスビーズなどのガラス系フィラー、炭素繊維、炭素短繊維、カーボンナノチューブ、黒鉛などの炭素系フィラー、チタン酸カリウム、ホウ酸アルミニウムなどのウィスカー、タルク、マイカ、ウォラストナイト、カオリナイト、ゾノトライト、セピオライト、アタバルジャイト、モンモリロナイト、ベントナイト、スメクタイトなどの珪酸塩化合物、シリカ、アルミナ、炭酸カルシウム等が挙げられる。これらは、単独でも2種以上の混合して使用してもよい。上記の中で、特にガラス繊維(チョップドストランド)、ガラス短繊維(ミルドファイバー)、ガラスフレーク、タルク、マイカ、ウォラストナイト、カオリナイトが好ましい。
本発明の芳香族ポリカーボネート樹脂組成物は、所望によって染顔料を含有していてもよい。染顔料を含有することで、本発明の芳香族ポリカーボネート樹脂組成物の隠蔽性、耐候性を向上できるほか、本発明の芳香族ポリカーボネート樹脂組成物を成形して得られる成形品のデザイン性を向上させることができる。
また、染顔料は、押出時のハンドリング性改良、樹脂組成物中への分散性改良の目的のために、(A)芳香族ポリカーボネート樹脂又は(B)ポリグリコール酸とマスターバッチ化されたものも用いてもよい。
本発明の芳香族ポリカーボネート樹脂組成物は、所望によって帯電防止剤を含有していてもよい。帯電防止剤は特に限定されないが、好ましくは下記一般式(IV)で表されるスルホン酸ホスホニウム塩である。
これらは、1種を単独で用いてもよく、2種以上を併用してもよい。
本発明の芳香族ポリカーボネート樹脂組成物は、(B)ポリグリコール酸の加水分解抑制剤として、カルボジイミド化合物を含有していてもよい。
本発明の芳香族ポリカーボネート樹脂組成物は、更に、必要に応じて、衝撃強度改良剤として熱可塑性エラストマーを含有していてもよく、熱可塑性エラストマーを配合することにより、成形品の耐衝撃性をより一層高めると共に、樹脂成分の混合むらに起因する成形品表面の色むらやパール調光沢の発現などの外観不良を防止して、外観に優れた成形品を得ることが可能となる。
本発明の芳香族ポリカーボネート樹脂組成物は、本発明の目的を損なわない限りにおいて、樹脂成分として、芳香族ポリカーボネート樹脂(A)、ポリグリコール酸(B)及び(E)相溶化剤以外の他の樹脂成分を含有していてもよい。配合し得る他の樹脂成分としては、例えば、ポリスチレン樹脂、ハイインパクトポリスチレン樹脂、水添ポリスチレン樹脂、ポリアクリルスチレン樹脂、ABS樹脂、AS樹脂、AES樹脂、ASA樹脂、SMA樹脂、ポリアルキルメタクリレート樹脂、ポリメタクリルメタクリレート樹脂、ポリフェニルエーテル樹脂、(A)成分以外のポリカーボネート樹脂、非晶性ポリアルキレンテレフタレート樹脂、(B)成分以外のポリエステル樹脂、非晶性ポリアミド樹脂、ポリ−4−メチルペンテン−1、環状ポリオレフィン樹脂、非晶性ポリアリレート樹脂、ポリエーテルサルフォンなどが挙げられ、好ましくは、ポリスチレン樹脂、ABS樹脂、AS樹脂、AES樹脂、ASA樹脂、ポリフェニレンエーテル樹脂、ポリメタクリルメタクリレート樹脂、(B)成分以外のポリエステル樹脂などが挙げられる。
本発明の芳香族ポリカーボネート樹脂組成物は、所望の諸物性を著しく損なわない限り、必要に応じて、上述したもの以外にその他の成分を含有していてもよい。その他の成分としては、例えば、防曇剤、アンチブロッキング剤、流動性改良剤、摺動性改質剤、可塑剤、分散剤、抗菌剤などの各種樹脂添加剤などが挙げられる。これらの樹脂添加剤は1種が含有されていてもよく、2種以上が任意の組み合わせ及び比率で含有されていても良い。
本発明の芳香族ポリカーボネート樹脂組成物の製造方法に制限はなく、公知の芳香族ポリカーボネート樹脂組成物の製造方法を広く採用することができる。
また、例えば、分散し難い成分を混合する際には、その分散し難い成分を予め水や有機溶剤等の溶媒に溶解又は分散させ、その溶液又は分散液と混練するようにすることで、分散性を高めることもできる。
本発明の芳香族ポリカーボネート樹脂組成物は、通常、任意の形状に成形して芳香族ポリカーボネート樹脂成形品として用いる。この成形品の形状、模様、色彩、寸法などに制限はなく、その成形品の用途に応じて任意に設定すればよい。
JIS K−7201−2(ISO 4589−2)の規格に基づく方法で実施した。酸素指数は大きい程難燃性に優れる。
JIS K5400に準じ、試験片に5回の引掻き試験を行って鉛筆硬度の評価を行った。
耐熱性の指標としてISO75−1に準拠した荷重たわみ温度(荷重1.8MPa)の測定を行った。
試験片の表面外観を目視にて観察し、以下の基準で評価した。
○:パール光沢がなく、外観に優れる。
△:パール光沢が目立つことなく、外観上問題がない。
×:パール光沢がやや目立ち、外観が劣る。
<(A)芳香族ポリカーボネート樹脂>
界面重合法で製造されたビスフェノールA型芳香族ポリカーボネート(三菱エンジニアリングプラスチックス(株)製「ユーピロン(登録商標)S−3000FN」、粘度平均分子量25000)
ポリグリコール酸((株)クレハ社製「Kuredux(登録商標)100R60」、280℃、剪断速度103sec−1で測定された溶融粘度2×102Pa・sec)
C−1:縮合リン酸エステル レゾルシノールビスジキシレニルホスフェート(大八化学工業(株)製「PX−200」)
C−2:フェノキシホスファゼン((株)伏見製薬所 製「ラビトルFP110」)
<(F)有機スルホン酸金属塩>
パーフルオロブタンスルホン酸カリウム(DIC(株)製「メガファックF−114」)
<(G)シリコーン系難燃剤>
ポリジフェニルシロキサン(信越化学工業(株)製「KF−56」)
フィブリル形成能を有するPTFE ダイキン工業社製「ポリフロンF−201L」
エチレン−メタクリル酸グリシジル共重合体(日油(株)製「モディパーA4300」、メタクリル酸グリシジル含有量15質量%)(EGMA)とアクリル酸ブチル−メタクリル酸メチル共重合体(P(BA/MMA))のグラフト共重合体(EGMA/P(BA/MMA)比=70/30(質量比))
H−1:ビス(2,6−ジ−tert−ブチル−4−メチルフェニル)ペンタエリスルトールホスファイト((株)ADEKA社製「アデカスタブPEP36」)
H−2:モノ−及びジステアリルアシッドホスフェート((株)ADEKA社製「アデカスタブAX−71」)
<樹脂組成物の調製>
上記の各成分を、表1及び表2に示す質量比で配合し、タンブラーにて20分混合した後、1ベントを備えた日本製鋼所社製(TEX30HSST)に供給し、スクリュー回転数200rpm、吐出量20kg/時間、バレル温度270℃の条件で混練し、ストランド状に押出した溶融樹脂を水槽にて急冷し、ペレタイザーを用いてペレット化して、芳香族ポリカーボネート樹脂組成物のペレットを得た。
上述の製造方法で得られたペレットを100℃で5時間乾燥させた後、射出成形機(住友重機械工業社製「SG75Mk−II」)にて、シリンダー温度270℃、金型温度60℃、成形サイクル50秒の条件で射出成形を行い、ISO多目的試験片(4mm厚)を作製した。得られた試験片を前記の酸素指数測定、耐熱性評価、表面硬度評価、成形品外観評価に用いた。
本発明の実施例1,4〜11,13〜16の組成物は、難燃性、表面硬度、耐熱性、成形品外観の何れにもバランスよく優れている。(E)相溶化剤を配合していない実施例1でも成形品外観に優れることから、(C)リン系難燃剤は(A)芳香族ポリカーボネート樹脂と(B)ポリグリコール酸の相溶化剤としても効果があることがわかる。
比較例1は(B)ポリグリコール酸が含有されていないため表面硬度が劣る。
比較例2は、(C)リン系難燃剤および(E)相溶化剤の添加がないため成形品外観が劣り、酸素指数も低い。なお、比較例1と比較例2の対比より、(A)芳香族ポリカーボネート樹脂に(B)ポリグリコール酸を配合すると、表面硬度は上がるが、難燃性が低下することが分かる。
比較例3は(E)相溶化剤の添加により成形品外観が向上するが十分ではなく、酸素指数が大きく低下する。この比較例3と比較例2との対比より、(E)相溶化剤の配合で難燃性が更に低下することが分かる。
比較例4は(D)PTFEが添加されていないため難燃性の改良が不充分であり、(D)PTFE以外の配合割合がこの比較例4に近い実施例9と比べて大きく劣る。
比較例5は(C)リン系難燃剤が過剰に添加されているため耐熱性が大きく劣る。
Claims (4)
- さらに、下記の(Ea)相溶化剤及び/又は(Eb)相溶化剤を、(A)芳香族ポリカーボネート樹脂と(B)ポリグリコール酸の合計100質量部に対して、0.1〜15質量部含有することを特徴とする請求項1に記載の芳香族ポリカーボネート樹脂組成物。
(Ea)相溶化剤:(Ea−1)エポキシ基変性重合体と(Ea−2)ビニル系重合体との共重合体
(Eb)相溶化剤:(Eb−1)ポリカーボネート系化合物と(Eb−2)エポキシ基変性重合体との共重合体 - さらに、(A)芳香族ポリカーボネート樹脂と(B)ポリグリコール酸の合計100質量部に対して、0.01〜0.5質量部の(F)有機スルホン酸金属塩、及び/又は0.1〜3質量部の(G)シリコーン系難燃剤を含有することを特徴とする請求項1または2に記載の芳香族ポリカーボネート樹脂組成物。
- 請求項1ないし3のいずれか1項に記載の芳香族ポリカーボネート樹脂組成物を成形してなることを特徴とする芳香族ポリカーボネート樹脂成形品。
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