JP2021134266A - ポリカーボネート樹脂組成物 - Google Patents
ポリカーボネート樹脂組成物 Download PDFInfo
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- JP2021134266A JP2021134266A JP2020030547A JP2020030547A JP2021134266A JP 2021134266 A JP2021134266 A JP 2021134266A JP 2020030547 A JP2020030547 A JP 2020030547A JP 2020030547 A JP2020030547 A JP 2020030547A JP 2021134266 A JP2021134266 A JP 2021134266A
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- carbon atoms
- weight
- polycarbonate resin
- bis
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- Granted
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- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 119
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 119
- 239000000203 mixture Substances 0.000 title claims abstract description 94
- -1 polybutylene terephthalate Polymers 0.000 claims abstract description 177
- 125000003118 aryl group Chemical group 0.000 claims abstract description 77
- 229920005989 resin Polymers 0.000 claims abstract description 39
- 239000011347 resin Substances 0.000 claims abstract description 39
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 25
- 229920001707 polybutylene terephthalate Polymers 0.000 claims abstract description 20
- 239000000470 constituent Substances 0.000 claims abstract description 16
- 238000004891 communication Methods 0.000 claims abstract description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 137
- 239000003365 glass fiber Substances 0.000 claims description 106
- 150000001875 compounds Chemical class 0.000 claims description 39
- 125000000217 alkyl group Chemical group 0.000 claims description 35
- 239000000835 fiber Substances 0.000 claims description 34
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 22
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 21
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 10
- 125000004104 aryloxy group Chemical group 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 125000003172 aldehyde group Chemical group 0.000 claims description 7
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 125000002102 aryl alkyloxo group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000003107 substituted aryl group Chemical group 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000005017 substituted alkenyl group Chemical group 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 125000005338 substituted cycloalkoxy group Chemical group 0.000 claims description 4
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 3
- 125000002270 phosphoric acid ester group Chemical group 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 22
- 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 abstract description 22
- 229930185605 Bisphenol Natural products 0.000 abstract description 7
- 229920000515 polycarbonate Polymers 0.000 abstract description 3
- 239000004417 polycarbonate Substances 0.000 abstract description 3
- 239000011152 fibreglass Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 54
- 229910052751 metal Inorganic materials 0.000 description 35
- 239000002184 metal Substances 0.000 description 35
- 150000003839 salts Chemical class 0.000 description 32
- 239000003063 flame retardant Substances 0.000 description 29
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 29
- 239000004810 polytetrafluoroethylene Substances 0.000 description 29
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 24
- 239000011521 glass Substances 0.000 description 24
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 24
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 229920001296 polysiloxane Polymers 0.000 description 20
- 239000002253 acid Substances 0.000 description 19
- 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 description 18
- 239000007850 fluorescent dye Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000003513 alkali Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 17
- 229910019142 PO4 Inorganic materials 0.000 description 16
- 238000000465 moulding Methods 0.000 description 16
- 239000010452 phosphate Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 16
- 239000001294 propane Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 239000000178 monomer Substances 0.000 description 14
- 150000002989 phenols Chemical class 0.000 description 14
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 13
- 239000000654 additive Substances 0.000 description 13
- 239000000975 dye Substances 0.000 description 13
- 239000011342 resin composition Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000007983 Tris buffer Substances 0.000 description 11
- 229910052783 alkali metal Inorganic materials 0.000 description 11
- 150000001412 amines Chemical class 0.000 description 11
- 239000000155 melt Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 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 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000004611 light stabiliser Substances 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 8
- 150000001340 alkali metals Chemical class 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 230000001771 impaired effect Effects 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 7
- 235000006708 antioxidants Nutrition 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 229920000620 organic polymer Polymers 0.000 description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 229910018068 Li 2 O Inorganic materials 0.000 description 5
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical group 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 5
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 4
- 229910052792 caesium Inorganic materials 0.000 description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 4
- 150000004650 carbonic acid diesters Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052701 rubidium Inorganic materials 0.000 description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical group CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 3
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 3
- 0 CCC(*)[S-](C)(*)*c(cc1*)ccc1O Chemical compound CCC(*)[S-](C)(*)*c(cc1*)ccc1O 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 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 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 229960000956 coumarin Drugs 0.000 description 3
- 235000001671 coumarin Nutrition 0.000 description 3
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000006060 molten glass Substances 0.000 description 3
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 3
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 3
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 3
- 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
- KLDXJTOLSGUMSJ-KVTDHHQDSA-N (3r,3ar,6r,6ar)-2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan-3,6-diol Chemical compound O[C@@H]1CO[C@@H]2[C@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-KVTDHHQDSA-N 0.000 description 2
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- QZHDEAJFRJCDMF-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QZHDEAJFRJCDMF-UHFFFAOYSA-M 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 2
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
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- HGJYOHAIVZXUML-UHFFFAOYSA-M potassium;3-(benzenesulfonyl)benzenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C1=CC=CC(S(=O)(=O)C=2C=CC=CC=2)=C1 HGJYOHAIVZXUML-UHFFFAOYSA-M 0.000 description 1
- GLGXXYFYZWQGEL-UHFFFAOYSA-M potassium;trifluoromethanesulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)F GLGXXYFYZWQGEL-UHFFFAOYSA-M 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
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- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
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- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
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- YXTFRJVQOWZDPP-UHFFFAOYSA-M sodium;3,5-dicarboxybenzenesulfonate Chemical compound [Na+].OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 YXTFRJVQOWZDPP-UHFFFAOYSA-M 0.000 description 1
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- IFYFNVDTVZKNBZ-UHFFFAOYSA-N tetradecyl 2-hydroxybenzoate Chemical compound CCCCCCCCCCCCCCOC(=O)C1=CC=CC=C1O IFYFNVDTVZKNBZ-UHFFFAOYSA-N 0.000 description 1
- WUPCFMITFBVJMS-UHFFFAOYSA-N tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)CC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 WUPCFMITFBVJMS-UHFFFAOYSA-N 0.000 description 1
- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 description 1
- ACOVYJCRYLWRLR-UHFFFAOYSA-N tetramethoxygermane Chemical compound CO[Ge](OC)(OC)OC ACOVYJCRYLWRLR-UHFFFAOYSA-N 0.000 description 1
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- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- SUXIKHBBPQWLHO-UHFFFAOYSA-N trihydroxy-(8-methylnonyl)-(8-methyl-1-phenylnonyl)-lambda5-phosphane Chemical compound CC(C)CCCCCCCP(O)(O)(O)C(CCCCCCC(C)C)C1=CC=CC=C1 SUXIKHBBPQWLHO-UHFFFAOYSA-N 0.000 description 1
- OOZKMYBQDPXENQ-UHFFFAOYSA-N tris(2,3-diethylphenyl) phosphite Chemical compound CCC1=CC=CC(OP(OC=2C(=C(CC)C=CC=2)CC)OC=2C(=C(CC)C=CC=2)CC)=C1CC OOZKMYBQDPXENQ-UHFFFAOYSA-N 0.000 description 1
- JBXUHJUOOSISGB-UHFFFAOYSA-N tris(2,3-dimethylphenyl) phosphite Chemical compound CC1=CC=CC(OP(OC=2C(=C(C)C=CC=2)C)OC=2C(=C(C)C=CC=2)C)=C1C JBXUHJUOOSISGB-UHFFFAOYSA-N 0.000 description 1
- RMXMITCPGRBNAS-UHFFFAOYSA-N tris(2,4,6-tribromophenyl) phosphate Chemical compound BrC1=CC(Br)=CC(Br)=C1OP(=O)(OC=1C(=CC(Br)=CC=1Br)Br)OC1=C(Br)C=C(Br)C=C1Br RMXMITCPGRBNAS-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
- VRWLYUVQNRXNNS-UHFFFAOYSA-N tris(4-bromophenyl) phosphate Chemical compound C1=CC(Br)=CC=C1OP(=O)(OC=1C=CC(Br)=CC=1)OC1=CC=C(Br)C=C1 VRWLYUVQNRXNNS-UHFFFAOYSA-N 0.000 description 1
- QFGXDXGDZKTYFD-UHFFFAOYSA-N tris[2,3-di(propan-2-yl)phenyl] phosphite Chemical compound CC(C)C1=CC=CC(OP(OC=2C(=C(C(C)C)C=CC=2)C(C)C)OC=2C(=C(C(C)C)C=CC=2)C(C)C)=C1C(C)C QFGXDXGDZKTYFD-UHFFFAOYSA-N 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
本発明において使用される芳香族ポリカーボネート樹脂は、二価フェノールとカーボネート前駆体とを反応させて得られるものである。反応方法の一例として界面重合法、溶融エステル交換法、カーボネートプレポリマーの固相エステル交換法および環状カーボネート化合物の開環重合法などを挙げることができる。
[t0は塩化メチレンの落下秒数、tは試料溶液の落下秒数]
ηSP/c=[η]+0.45×[η]2c(但し[η]は極限粘度)
[η]=1.23×10−4M0.83
c=0.7
本発明のA成分に含有される変性ポリカーボネート樹脂は、樹脂中の全Cl(塩素)量が好ましくは0〜200ppm、より好ましくは0〜150ppmである。変性ポリカーボネート樹脂中の全Cl量が200ppmを越えると、色相および熱安定性が悪くなる場合があるので好ましくない。
本発明で好適に使用されるガラス繊維としては、Eガラス組成(ガラス繊維の全量に対し52.0〜56.0重量%のSiO2、12.0〜16.0重量%のAl2O3、合計で20.0〜25.0重量%のMgOおよびCaOおよび5.0〜10.0重量%のB2O3とを含む組成)を備えるガラス繊維(Eガラス繊維)、NEガラス組成(ガラス繊維全量に対し52.0〜57.0重量%のSiO2、13.0〜17.0重量%のAl2O3、15.0〜21.5重量%のB2O3、2.0〜6.0重量%のMgO、2.0〜6.0重量%のCaO、1.0〜4.0重量%のTiO2および1.5重量%未満のF2とを含み、かつ、Li2O、Na2OおよびK2Oの合計量が0.6重量%未満である組成)を備えるガラス繊維(NEガラス繊維)の他、Sガラス、Dガラス等に代表されるガラス繊維が適用されるが、特にNEガラス繊維が電波透過性に優れるため好ましい。
0重量%が好ましく、1.5〜2.5重量%がより好ましく、1.6〜2.3重量%がさらに好ましく、1.7〜2.1重量%が特に好ましく、1.8〜2.0重量%が最も好ましい。ガラス繊維全量に対するTiO2の含有量が1.0重量%未満であると、誘電正接を下げ、粘性を低下させ、初期溶融時における溶融分離を抑制し、炉表面で発生するスカムを減少させる効果が小さくなる場合がある。一方、TiO2の含有量が4.0重量%を超えると、分相を生じ易く、化学的耐久性が悪くなる場合がある。
本発明で好適に使用されるポリブチレンテレフタレート樹脂としては、ポリエステルを形成するジカルボン酸成分とジオール成分の内、ジカルボン酸成分の70モル%以上が芳香族ジカルボン酸である芳香族ポリエステル樹脂が好ましく、より好ましくは90モル%以上、最も好ましくは99モル%以上が芳香族ジカルボン酸である芳香族ポリエステル樹脂である。このジカルボン酸の例として、テレフタル酸、イソフタル酸、アジピン酸、2−クロロテレフタル酸、2,5−ジクロロテレフタル酸、2−メチルテレフタル酸、4,4−スチルベンジカルボン酸、4,4−ビフェニルジカルボン酸、オルトフタル酸、2,6−ナフタレンジカルボン酸、2,7−ナフタレンジカルボン酸、ビス安息香酸、ビス(p−カルボキシフェニル)メタン、アントラセンジカルボン酸、4,4−ジフェニルエーテルジカルボン酸、4,4−ジフェノキシエタンジカルボン酸、5−Naスルホイソフタル酸、エチレン−ビス−p−安息香酸等があげられる。これらのジカルボン酸は単独でまたは2種以上混合して使用することができる。本発明の芳香族ポリエステル樹脂には、上記の芳香族ジカルボン酸以外に、30モル%未満の脂肪族ジカルボン酸成分を共重合することができる。その具体例として、アジピン酸、セバシン酸、アゼライン酸、ドデカン二酸、1,3−シクロヘキサンジカルボン酸、1,4−シクロヘキサンジカルボン酸等があげられる。本発明のジオール成分としては、例えばエチレングリコール、ジエチレングリコール、1,2−プロピレングリコール、1,3−プロパンジオール、2,2−ジメチル−1,3−プロパンジオール、トランス−またはシス−2,2,4,4−テトラメチル−1,3−シクロブタンジオール、1,4−ブタンジオール、ネオペンチルグリコール、1,5−ペンタンジオール、1,6−ヘキサンジオール、1,4−シクロヘキサンジメタノール、1,3−シクロヘキサンジメタノール、デカメチレングリコール、シクロヘキサンジオール、p−キシレンジオール、ビスフェノールA、テトラブロモビスフェノールA、テトラブロモビスフェノールA−ビス(2−ヒドロキシエチルエーテル)などを挙げることができる。これらは単独でも、2種以上を混合して使用することができる。尚、ジオール成分中の二価フェノールは30モル%以下であることが好ましい。
本発明に使用されるリン系化合物としては、ホスファイト化合物、ホスホナイト化合物、およびホスフェート化合物のいずれも使用可能であるが、特に数平均分子量50〜300のホスフェート化合物使用時に外観が特に優れるため好ましい。
ホスホナイト化合物としては下記一般式(11)で表わされるホスホナイト化合物、および下記一般式(12)で表わされるホスホナイト化合物を挙げることができる。
式(13)中、好ましくはR36およびR37は炭素原子数1〜12のアルキル基であり、より好ましくは炭素原子数1〜8のアルキル基である。式(13)で表される化合物としては具体的に、トリス(ジメチルフェニル)ホスファイト、トリス(ジエチルフェニル)ホスファイト、トリス(ジ−iso−プロピルフェニル)ホスファイト、トリス(ジ−n−ブチルフェニル)ホスファイト、トリス(2,4−ジ−tert−ブチルフェニル)ホスファイト、トリス(2,6−ジ−tert−ブチルフェニル)ホスファイト、トリス(2,6−ジ−tert−ブチルフェニル)ホスファイトなどが挙げられ、特にトリス(2,6−ジ−tert−ブチルフェニル)ホスファイトが好ましい。
本発明のポリカーボネート樹脂組成物には、難燃剤を配合することができる。かかる化合物の配合は難燃性の向上をもたらすが、それ以外にも各化合物の性質に基づき、例えば帯電防止性、流動性、剛性、および熱安定性の向上などがもたらされる。かかる難燃剤としては、(i)有機金属塩系難燃剤(例えば有機スルホン酸アルカリ(土類)金属塩、有機ホウ酸金属塩系難燃剤、および有機錫酸金属塩系難燃剤など)、(ii)有機リン系難燃剤(例えば、有機基含有のモノホスフェート化合物、ホスフェートオリゴマー化合物、ホスホネートオリゴマー化合物、ホスホニトリルオリゴマー化合物、およびホスホン酸アミド化合物など)、(iii)シリコーン化合物からなるシリコーン系難燃剤、(iv)フィブリル化PTFEが挙げられ、その中でも有機金属塩系難燃剤、有機リン系難燃剤が好ましい。これらは一種または二種複合して使用しても良い。
有機金属塩化合物は炭素原子数1〜50、好ましくは1〜40の有機酸のアルカリ(土類)金属塩、好ましくは有機スルホン酸アルカリ(土類)金属塩であることが好ましい。この有機スルホン酸アルカリ(土類)金属塩には、炭素原子数1〜10、好ましくは2〜8のパーフルオロアルキルスルホン酸とアルカリ金属またはアルカリ土類金属との金属塩の如きフッ素置換アルキルスルホン酸の金属塩、並びに炭素原子数7〜50、好ましくは7〜40の芳香族スルホン酸とアルカリ金属またはアルカリ土類金属との金属塩が含まれる。金属塩を構成するアルカリ金属としてはリチウム、ナトリウム、カリウム、ルビジウムおよびセシウムが挙げられ、アルカリ土類金属としては、ベリリウム、マグネシウム、カルシウム、ストロンチウムおよびバリウムが挙げられる。より好適にはアルカリ金属である。かかるアルカリ金属の中でも、透明性の要求がより高い場合にはイオン半径のより大きいルビジウムおよびセシウムが好適である一方、これらは汎用的でなくまた精製もし難いことから、結果的にコストの点で不利となる場合がある。一方、リチウムおよびナトリウムなどのより小さいイオン半径の金属は逆に難燃性の点で不利な場合がある。これらを勘案してスルホン酸アルカリ金属塩中のアルカリ金属を使い分けることができるが、いずれの点においても特性のバランスに優れたスルホン酸カリウム塩が最も好適である。かかるカリウム塩と他のアルカリ金属からなるスルホン酸アルカリ金属塩とを併用することもできる。
有機リン系難燃剤としては、アリールホスフェート化合物、ホスファゼン化合物が好適に用いられる。これらの有機リン系難燃剤は可塑化効果があるため、成形加工性を高められる点で有利である。アリールホスフェート化合物は、従来難燃剤として公知の各種ホスフェート化合物が使用できるが、より好適には特に下記一般式(15)で表される1種または2種以上のホスフェート化合物を挙げることができる。
上記式(16)、(17)中、X1、X2、X3、X4で表されるハロゲン原子を含まない有機基としては、例えば、アルコキシ基、フェニル基、アミノ基、アリル基などが挙げられる。中でも上記式(16)で表される環状ホスファゼン化合物が好ましく、更に、上記式(17)中のX1、X2がフェノキシ基である環状フェノキシホスファゼンが特に好ましい。
シリコーン系難燃剤として使用されるシリコーン化合物は、燃焼時の化学反応によって難燃性を向上させるものである。該化合物としては従来芳香族ポリカーボート樹脂の難燃剤として提案された各種の化合物を使用することができる。シリコーン化合物はその燃焼時にそれ自体が結合してまたは樹脂に由来する成分と結合してストラクチャーを形成することにより、または該ストラクチャー形成時の還元反応により、特にポリカーボネート樹脂を用いた場合に高い難燃効果を付与するものと考えられている。
フィブリル化PTFEは、フィブリル化PTFE単独であっても、混合形態のフィブリル化PTFEすなわちフィブリル化PTFE粒子と有機系重合体からなるポリテトラフルオロエチレン系混合体であってもよい。フィブリル化PTFEは極めて高い分子量を有し、せん断力などの外的作用によりPTFE同士を結合して繊維状になる傾向を示すものである。その数平均分子量は、150万〜数千万の範囲である。かかる下限はより好ましくは300万である。かかる数平均分子量は、例えば特開平6−145520号公報に開示されているとおり、380℃でのポリテトラフルオロエチレンの溶融粘度に基づき算出される。即ち、フィブリル化PTFEは、かかる公報に記載された方法で測定される380℃における溶融粘度が107〜1013poiseの範囲であり、好ましくは108〜1012poiseの範囲である。かかるPTFEは、固体形状の他、水性分散液形態のものも使用可能である。またかかるフィブリル化PTFEは樹脂中での分散性を向上させ、さらに良好な難燃性および機械的特性を得るために他の樹脂との混合形態のPTFE混合物を使用することも可能である。
本発明に使用されるフェノール系安定剤としては、一般的にヒンダードフェノール、セミヒンダードフェノール、レスヒンダードフェノール化合物が挙げられるが、ポリプロピレン系樹脂に対して熱安定処方を施すという観点で特にヒンダードフェノール化合物がより好適に用いられる。かかるヒンダードフェノール化合物としては、具体例としては、例えばビタミンE、n−オクタデシル−β−(4’−ヒドロキシ−3’,5’−ジ−tert−ブチルフェル)プロピオネート、2−tert−ブチル−6−(3’−tert−ブチル−5’−メチル−2’−ヒドロキシベンジル)−4−メチルフェニルアクリレート、2,6−ジ−tert−ブチル−4−(N,N−ジメチルアミノメチル)フェノール、3,5−ジ−tert−ブチル−4−ヒドロキシベンジルホスホネートジエチルエステル、2,2’−メチレンビス(4−メチル−6−tert−ブチルフェノール)、2,2’−メチレンビス(4−エチル−6−tert−ブチルフェノール)、4,4’−メチレンビス(2,6−ジ−tert−ブチルフェノール)、2,2’−メチレンビス(4−メチル−6−シクロヘキシルフェノール)、2,2’−ジメチレン−ビス(6−α−メチル−ベンジル−p−クレゾール)2,2’−エチリデン−ビス(4,6−ジ−tert−ブチルフェノール)、2,2’−ブチリデン−ビス(4−メチル−6−tert−ブチルフェノール)、4,4’−ブチリデンビス(3−メチル−6−tert−ブチルフェノール)、トリエチレングリコール−N−ビス−3−(3−tert−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオネート、1,6−へキサンジオールビス[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート、ビス[2−tert−ブチル−4−メチル6−(3−tert−ブチル−5−メチル−2−ヒドロキシベンジル)フェニル]テレフタレート、3,9−ビス{2−[3−(3−tert−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオニルオキシ]−1,1,−ジメチルエチル}−2,4,8,10−テトラオキサスピロ[5,5]ウンデカン、4,4’−チオビス(6−tert−ブチル−m−クレゾール)、4,4’−チオビス(3−メチル−6−tert−ブチルフェノール)、2,2’−チオビス(4−メチル−6−tert−ブチルフェノール)、ビス(3,5−ジ−tert−ブチル−4−ヒドロキシベンジル)スルフィド、4,4’−ジ−チオビス(2,6−ジ−tert−ブチルフェノール)、4,4’−トリ−チオビス(2,6−ジ−tert−ブチルフェノール)、2,4−ビス(n−オクチルチオ)−6−(4−ヒドロキシ−3’,5’−ジ−tert−ブチルアニリノ)−1,3,5−トリアジン、N,N’−ヘキサメチレンビス−(3,5−ジ−tert−ブチル−4−ヒドロキシヒドロシンナミド)、N,N’−ビス[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオニル]ヒドラジン、1,1,3−トリス(2−メチル−4−ヒドロキシ−5−tert−ブチルフェニル)ブタン、1,3,5−トリメチル−2,4,6−トリス(3,5−ジ−tert−ブチル−4−ヒドロキシベンジル)ベンゼン、トリス(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)イソシアヌレート、トリス(3,5−ジ−tert−ブチル−4−ヒドロキシベンジル)イソシアヌレート、1,3,5−トリス(4−tert−ブチル−3−ヒドロキシ−2,6−ジメチルベンジル)イソシアヌレート、1,3,5−トリス2[3(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオニルオキシ]エチルイソシアヌレート、テトラキス[メチレン−3−(3’,5’−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート]メタンなどを挙げることができ、好ましく使用できる。
本発明のポリカーボネート樹脂組成物には、酸化防止剤としてイオウ含有酸化防止剤を使用することもできる。特に樹脂組成物が回転成形や圧縮成形に使用される場合には好適である。かかるイオウ含有酸化防止剤の具体例としては、ジラウリル−3,3’−チオジプロピオン酸エステル、ジトリデシル−3,3’−チオジプロピオン酸エステル、ジミリスチル−3,3’−チオジプロピオン酸エステル、ジステアリル−3,3’−チオジプロピオン酸エステル、ラウリルステアリル−3,3’−チオジプロピオン酸エステル、ペンタエリスリトールテトラ(β−ラウリルチオプロピオネート)エステル、ビス[2−メチル−4−(3−ラウリルチオプロピオニルオキシ)−5−tert−ブチルフェニル]スルフィド、オクタデシルジスルフィド、メルカプトベンズイミダゾール、2−メルカプト−6−メチルベンズイミダゾール、1,1’−チオビス(2−ナフトール)などを挙げることができる。より好ましくは、ペンタエリスリトールテトラ(β−ラウリルチオプロピオネート)エステルを挙げることができる。
本発明のポリカーボネート樹脂組成物は紫外線吸収剤を含有することができる。ベンゾフェノン系では、例えば、2,4−ジヒドロキシベンゾフェノン、2−ヒドロキシ−4−メトキシベンゾフェノン、2−ヒドロキシ−4−オクトキシベンゾフェノン、2−ヒドロキシ−4−ベンジロキシベンゾフェノン、2−ヒドロキシ−4−メトキシ−5−スルホキシベンゾフェノン、2−ヒドロキシ−4−メトキシ−5−スルホキシトリハイドライドレイトベンゾフェノン、2,2’−ジヒドロキシ−4−メトキシベンゾフェノン、2,2’,4,4’−テトラヒドロキシベンゾフェノン、2,2’−ジヒドロキシ−4,4’−ジメトキシベンゾフェノン、2,2’−ジヒドロキシ−4,4’−ジメトキシ−5−ソジウムスルホキシベンゾフェノン、ビス(5−ベンゾイル−4−ヒドロキシ−2−メトキシフェニル)メタン、2−ヒドロキシ−4−n−ドデシルオキシベンソフェノン、および2−ヒドロキシ−4−メトキシ−2’−カルボキシベンゾフェノンなどが例示される。
本発明のポリカーボネート樹脂組成物はヒンダードアミン系光安定剤を含有することができる。ヒンダードアミン系光安定剤は一般にHALS(Hindered Amine Light Stabilizer)と呼ばれ、2,2,6,6−テトラメチルピペリジン骨格を構造中に有する化合物であり、例えば、4−アセトキシ−2,2,6,6−テトラメチルピペリジン、4−ステアロイルオキシ−2,2,6,6−テトラメチルピペリジン、4−アクリロイルオキシ−2,2,6,6−テトラメチルピペリジン、4−(フェニルアセトキシ)−2,2,6,6−テトラメチルピペリジン、4−ベンゾイルオキシ−2,2,6,6−テトラメチルピペリジン、4−メトキシ−2,2,6,6−テトラメチルピペリジン、4−ステアリルオキシ−2,2,6,6−テトラメチルピペリジン、4−シクロヘキシルオキシ−2,2,6,6−テトラメチルピペリジン、4−ベンジルオキシ−2,2,6,6−テトラメチルピペリジン、4−フェノキシ−2,2,6,6−テトラメチルピペリジン、4−(エチルカルバモイルオキシ)−2,2,6,6−テトラメチルピペリジン、4−(シクロヘキシルカルバモイルオキシ)−2,2,6,6−テトラメチルピペリジン、4−(フェニルカルバモイルオキシ)−2,2,6,6−テトラメチルピペリジン、ビス(2,2,6,6−テトラメチル−4−ピペリジル)カーボネート、ビス(2,2,6,6−テトラメチル−4−ピペリジル)オキサレート、ビス(2,2,6,6−テトラメチル−4−ピペリジル)マロネート、ビス(2,2,6,6−テトラメチル−4−ピペリジル)セバケート、ビス(2,2,6,6−テトラメチル−4−ピペリジル)アジペート、ビス(2,2,6,6−テトラメチル−4−ピペリジル)テレフタレート、ビス(1,2,2,6,6−ペンタメチル−4−ピペリジル)カーボネート、ビス(1,2,2,6,6−ペンタメチル−4−ピペリジル)オキサレート、ビス(1,2,2,6,6−ペンタメチル−4−ピペリジル)マロネート、ビス(1,2,2,6,6−ペンタメチル−4−ピペリジル)セバケート、ビス(1,2,2,6,6−ペンタメチル−4−ピペリジル)アジペート、ビス(1,2,2,6,6−ペンタメチル−4−ピペリジル)テレフタレート、N,N’−ビス−2,2,6,6−テトラメチル−4−ピペリジニル−1,3−ベンゼンジカルボキシアミド、1,2−ビス(2,2,6,6−テトラメチル−4−ピペリジルオキシ)エタン、α,α’−ビス(2,2,6,6−テトラメチル−4−ピペリジルオキシ)−p−キシレン、ビス(2,2,6,6−テトラメチル−4−ピペリジルトリレン−2,4−ジカルバメート、ビス(2,2,6,6−テトラメチル−4−ピペリジル)−ヘキサメチレン−1,6−ジカルバメート、トリス(2,2,6,6−テトラメチル−4−ピペリジル)−ベンゼン−1,3,5−トリカルボキシレート、N,N’,N’’,N’’’−テトラキス−(4,6−ビス−(ブチル−(N−メチル−2,2,6,6−テトラメチルピペリジン−4−イル)アミノ)−トリアジン−2−イル)−4,7−ジアザデカン−1,10−ジアミン、ジブチルアミン・1,3,5−トリアジン・N,N’−ビス(2,2,6,6−テトラメチル−4−ピペリジル)−1,6−ヘキサメチレンジアミンとN−(2,2,6,6−テトラメチル−4−ピペリジル)ブチルアミンの重縮合物、ポリ[{6−(1,1,3,3−テトラメチルブチル)アミノ−1,3,5−トリアジン−2,4−ジイル}{(2,2,6,6−テトラメチル−4−ピペリジル)イミノ}ヘキサメチレン{(2,2,6,6−テトラメチル−4−ピペリジル)イミノ}]、テトラキス(2,2,6,6−テトラメチル−4−ピペリジル)−1,2,3,4−ブタンテトラカルボキシラート、テトラキス(1,2,2,6,6−ペンタメチル−4−ピペリジル)−1,2,3,4−ブタンテトラカルボキシラート、トリス(2,2,6,6−テトラメチル−4−ピペリジル)−ベンゼン−1,3,4−トリカルボキシレート、1−[2−{3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオニルオキシ}ブチル]−4−[3−(3,5−ジ−t−ブチル−4−ヒドロキシフェニル)プロピオニルオキシ]2,2,6,6−テトラメチルピペリジン、及び1,2,3,4−ブタンテトラカルボン酸と1,2,2,6,6−ペンタメチル−4−ピペリジノールとβ,β,β’,β’−テトラメチル−3,9−[2,4,8,10−テトラオキサスピロ(5,5)ウンデカン]ジエタノールとの縮合物などが挙げられる。
本発明のポリカーボネート樹脂組成物には更に各種の染顔料を含有し多様な意匠性を発現する成形品を提供できる。蛍光増白剤やそれ以外の発光をする蛍光染料を配合することにより、発光色を生かした更に良好な意匠効果を付与することができる。また極微量の染顔料による着色、かつ鮮やかな発色性を有するポリカーボネート樹脂組成物もまた提供可能である。
本発明のポリカーボネート樹脂組成物には、他の樹脂を本発明の効果を発揮する範囲において、少割合使用することもできる。
本発明のポリカーボネート樹脂組成物には、他の充填材を本発明の効果を発揮する範囲において、少割合使用することもできる。
本発明のポリカーボネート樹脂組成物には、成形品に種々の機能の付与や特性改善のために、それ自体知られた添加物を少割合配合することができる。これら添加物は本発明の目的を損なわない限り、通常の配合量である。かかる添加剤としては、摺動剤(例えばPTFE粒子)、蛍光染料、無機系蛍光体(例えばアルミン酸塩を母結晶とする蛍光体)、帯電防止剤、結晶核剤、無機および有機の抗菌剤、光触媒系防汚剤(例えば微粒子酸化チタン、微粒子酸化亜鉛)、ラジカル発生剤、赤外線吸収剤(熱線吸収剤)、メカノクロミック剤、およびフォトクロミック剤などが挙げられる。
本発明の樹脂組成物を製造する方法に特に制限はなく、周知の方法を用いることができる。 例えばA成分、B成分、C成分および任意に他の添加剤を、V型ブレンダー、ヘンシェルミキサー、メカノケミカル装置、押出混合機などの予備混合手段を用いて充分に混合した後、必要に応じて押出造粒器やブリケッティングマシーンなどによりかかる予備混合物の造粒を行い、その後ベント式二軸押出機に代表される溶融混練機で溶融混練し、その後ペレタイザーによりペレット化する方法が挙げられる。
1.芳香族ポリカーボネート樹脂の評価
(i)粘度平均分子量(Mv)
次式にて算出される比粘度(ηSP)を20℃で塩化メチレン100mlに芳香族ポリカーボネート樹脂を溶解した溶液からオストワルド粘度計を用いて求め、
比粘度(ηSP)=(t−t0)/t0
[t0は塩化メチレンの落下秒数、tは試料溶液の落下秒数]
求められた比粘度(ηSP)から次の数式により粘度平均分子量Mvを算出した。
ηSP/c=[η]+0.45×[η]2 c (但し[η]は極限粘度)
[η]=1.23×10−4 Mv0.83
c=0.7
(i)引張特性(引張破壊強度)
ISO527に準拠して試験速度50mm/minで測定した。試験片は下記の方法で得られたダンベル型試験片を用い、平行部形状は、長さ80mm×幅10mm×厚み4mmであった。
(ii)剛性(曲げ弾性率)
下記の方法で得られた長さ80mm×幅10mm×厚み4mmの試験片を用いてISO178に準拠して試験速度2mm/minで測定した。
(iii)衝撃特性(シャルピー衝撃値)(ノッチ有)
下記の方法で得られた長さ80mm×幅10mm×厚み4mmの試験片を用いてISO179(測定条件23℃)に準拠して測定した。
(iv)電磁波透過性
下記の方法で得られた長さ150mm×幅150mm×厚み3mmの試験片を用いて、28GHzの電波透過性を測定した。電磁波透過性測定装置として、デジタルマイクロメーター(シンワ製)とネットワークアナライザー E8361A(キーサイト製)を用いた。
(v)表面外観
下記の方法で得られた成形用材料の表面外観を観察し、ガラス繊維とポリカーボネートの密着性が不十分だったことにより発生する直径3mm以上の繊維状物質の塊および気泡が表面に確認されなかったものを○(良好)、繊維状物質の塊は確認されなかったものの気泡が確認されたものを△(やや良好)、繊維状物質の塊が確認されたものを×(不良)とした。
(vi)熱安定性
下記の方法で得られたポリカーボネート樹脂組成物をシリンダ温度330℃に設定した射出成形機に投入し10分間滞留させた際に射出ノズル先端から自然落下した樹脂量を測定した。
芳香族ポリカーボネート樹脂、ポリブチレンテレフタレート樹脂、ガラス繊維および各種添加剤を表2および表3記載の各配合量でブレンダーにて混合した後、ベント式二軸押出機を用いて溶融混練してペレットを得た。使用する各種添加剤は、それぞれ配合量の10〜100倍の濃度を目安に予め芳香族ポリカーボネート樹脂との予備混合物を作成した後、ブレンダーによる全体の混合を行った。押出は径30mmφのベント式二軸押出機((株)日本製鋼所TEX30α−38.5BW−3V)を使用し、スクリュー回転数230rpm、吐出量25kg/h、ベントの真空度3kPaで、押出温度は第一供給口から第二供給口まで300℃、第二供給口からダイス部分まで310℃として溶融混練しペレットを得た。なお、強化充填材は上記押出機のサイドフィーダーを使用し第二供給口から供給し、残りのポリカーボネート樹脂および添加剤は第一供給口から押出機に供給した。ここでいう第一供給口とはダイスから最も離れた供給口であり、第二供給口とは押出機のダイスと第一供給口の間に位置する供給口である。得られたペレットを120℃で5時間、熱風循環式乾燥機にて乾燥した後に、射出成形機(住友重機械工業(株)製 SG−150U)によりシリンダー温度300℃、金型温度80℃の成形条件で、評価用の試験片を成形した。各評価結果を表2および表3に示した。
A−1:下記条件で調製した芳香族ポリカーボネート樹脂
温度計、撹拌機および還流冷却器の付いた反応器に、48%水酸化ナトリウム水溶液3844部およびイオン交換水22,380部を仕込み、これに2,2−ビス(4−ヒドロキシ−3−メチルフェニル)プロパン(Bis−C、本州化学製)3,984部、およびハイドロサルファイト7.53部(和光純薬製)を溶解した後、塩化メチレン13,210部を加え、撹拌下、15〜25℃でホスゲン2,000部を約60分かけて吹き込んだ。ホスゲンの吹き込み終了後、48%水酸化ナトリウム水溶液640部およびp−tert−ブチルフェノール93.2部を加え、撹拌を再開、乳化後トリエチルアミン3.24部を加え、さらに28〜33℃で1時間撹拌して反応を終了した。反応終了後生成物を塩化メチレンで希釈して水洗した後、塩酸酸性にして水洗し、さらに水相の導電率がイオン交換水とほぼ同じになるまで水洗を繰り返し、芳香族ポリカーボネート樹脂の塩化メチレン溶液を得た。次いで、この溶液を目開き0.3μmのフィルターに通過させ、さらに軸受け部に異物取り出し口を有する隔離室付きニーダー中の温水に滴下、塩化メチレンを留去しながら芳香族ポリカーボネート樹脂をフレーク化し、引続き該含液フレークを粉砕・乾燥して得られた芳香族ポリカーボネート樹脂粉末を得た。
A−2:下記条件で調製した芳香族ポリカーボネート樹脂
使用するモノマーを、2,2−ビス(4−ヒドロキシ−3−メチルフェニル)プロパン(Bis−C、本州化学工業製)1,992部(7.8モル)、2,2−ビス(4−ヒドロキシフェニル)プロパン(Bis−A、新日鐵化学製)1,773部(7.8モル)に変更した以外は、A−1と同様の方法で芳香族ポリカーボネート樹脂粉末を得た。
A−3:下記条件で調製した芳香族ポリカーボネート樹脂
使用するモノマーを、2,2−ビス(4−ヒドロキシ−3−メチルフェニル)プロパン766部(3.0モル)、2,2−ビス(4−ヒドロキシフェニル)プロパン2,728部(12.0モル)に変更した以外は、A−1と同様の方法で芳香族ポリカーボネート樹脂粉末を得た。
A−4:下記条件で調製した芳香族ポリカーボネート樹脂
使用するモノマーを、2,2−ビス(4−ヒドロキシ−3−メチルフェニル)プロパン511部(2.0モル)、2,2−ビス(4−ヒドロキシフェニル)プロパン3,182部(14.0モル)に変更した以外は、A−1と同様の方法で芳香族ポリカーボネート樹脂粉末を得た。
A−5:芳香族ポリカーボネート樹脂(ビスフェノールAとホスゲンから常法によって作られた粘度平均分子量15,500のポリカーボネート樹脂粉末、帝人(株)製 パンライトCM−1000(製品名))
A−6:芳香族ポリカーボネート樹脂(ビスフェノールAとホスゲンから常法によって作られた粘度平均分子量19,700のポリカーボネート樹脂粉末、帝人(株)製 パンライトL−1225WX(製品名))
(B成分)
表1の記載の成分からなるガラス繊維B−1〜B−4を使用した。組成1はNEガラス組成に相当し、組成2はEガラス組成に相当する。
B−2:組成1からなる非円形断面ガラス繊維(繊維径15μm、カット長3mm、長径28μm、短径7μm)
B−3:組成2からなる円形断面ガラス繊維(繊維径11μm、カット長3mm、長径/短径比=1.0)
B−4:組成2からなる非円形断面ガラス繊維(繊維径15μm、カット長3mm、長径28μm、短径7μm)
なお、断面形状が非円形のガラス繊維における繊維径は、断面積を真円に換算したときの繊維径(換算繊維径)を意味する。
C−1:ポリブチレンテレフタレート(ポリプラスチックス(株)製:ジュラネックス 500FP EF202X、IV値:0.85、末端カルボキシル基:55eq/ton)
C−2:ポリブチレンテレフタレート(ポリプラスチックス(株)製:ジュラネックス 500FP EF202R、IV値:0.875、末端カルボキシル基:10eq/ton)
(D成分)
D−1:トリメチルホスフェート(大八化学工業(株)製 TMP)
D−2:トリス(2,4−ジ−tert−ブチルフェニル)ホスファイト(アデカ製2112)
(その他の成分)
UV:ベンゾトリアゾール系紫外線吸収剤(チバ・スペシャリティケミカルズ社製:Tinuvin234)
L:低分子量ポリエチレン(三井化学(株)製ハイワックスHW405MP(商品名))
CB:カーボンブラック(越谷化成工業(株)製 RB−90003S)
Claims (7)
- (A)芳香族ポリカーボネート樹脂(A成分)100重量部に対し、(B)ガラス繊維(B成分)1〜105重量部および(C)ポリブチレンテレフタレート樹脂(C成分)0.01〜3.5重量部を含有するポリカーボネート樹脂組成物であって、A成分が、下記式(1)で表されるカーボネート構成単位を全カーボネート構成単位中20〜100モル%含む芳香族ポリカーボネート樹脂(A−1成分)を20〜100重量%含む芳香族ポリカーボネート樹脂であることを特徴とするアンテナ内蔵通信機器用ポリカーボネート樹脂組成物。
- B成分が、30〜5000μmの数平均繊維長を有する(B−1)断面形状の短径に対する長径の比(長径/短径)が2.0〜10.0の範囲にあり、断面積を真円に換算したときの繊維径が3.0〜35.0μmの範囲にある非円形断面ガラス繊維(B−1成分)および(B−2)平均繊維径が7.0〜13.0μmの範囲にある円形断面ガラス繊維(B−2成分)からなる群より選ばれる1種以上のガラス繊維であることを特徴とする請求項1記載のポリカーボネート樹脂組成物。
- B成分が、52.0〜57.0重量%のSiO2、13.0〜17.0重量のAl2O3、15.0〜21.5重量%のB2O3、2.0〜6.0重量%のMgO、2.0〜6.0重量%のCaO、1.0〜4.0重量%のTiO2および1.5重量%未満のF2とを含み、かつ、Li2O、Na2OおよびK2Oの合計量が0.6重量%未満であるガラス繊維であることを特徴とする請求項1または2に記載のポリカーボネート樹脂組成物。
- A−1成分以外の芳香族ポリカーボネート樹脂の粘度平均分子量が10,000〜16,000であることを特徴とする請求項1〜3のいずれかに記載のポリカーボネート樹脂組成物。
- C成分が末端カルボキシル基量が40eq/g以上であるポリブチレンテレフタレート樹脂であることを特徴とする請求項1〜4のいずれかに記載のポリカーボネート樹脂組成物。
- A成分100重量部に対し、(D)リン系化合物(D成分)0.01〜1重量部を含有することを特徴とする請求項1〜5のいずれかに記載のポリカーボネート樹脂組成物。
- D成分が、数平均分子量が50〜300であるリン酸エステル系化合物であることを特徴とする請求項6に記載のポリカーボネート樹脂組成物。
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