JP2013023532A - 芳香族ポリカーボネート樹脂組成物及びこれを成形してなる樹脂成形体 - Google Patents
芳香族ポリカーボネート樹脂組成物及びこれを成形してなる樹脂成形体 Download PDFInfo
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- JP2013023532A JP2013023532A JP2011158101A JP2011158101A JP2013023532A JP 2013023532 A JP2013023532 A JP 2013023532A JP 2011158101 A JP2011158101 A JP 2011158101A JP 2011158101 A JP2011158101 A JP 2011158101A JP 2013023532 A JP2013023532 A JP 2013023532A
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- component
- acid
- polycarbonate resin
- aromatic polycarbonate
- aromatic
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 126
- 229920005668 polycarbonate resin Polymers 0.000 title claims abstract description 74
- 239000004431 polycarbonate resin Substances 0.000 title claims abstract description 74
- 239000000203 mixture Substances 0.000 title claims abstract description 60
- 238000000465 moulding Methods 0.000 title claims abstract description 28
- 229920005989 resin Polymers 0.000 title claims abstract description 26
- 239000011347 resin Substances 0.000 title claims abstract description 26
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 137
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 73
- 239000010439 graphite Substances 0.000 claims abstract description 71
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims abstract description 51
- 239000002245 particle Substances 0.000 claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 229920000728 polyester Polymers 0.000 claims abstract description 30
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 25
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 90
- 125000004432 carbon atom Chemical group C* 0.000 claims description 49
- 150000002148 esters Chemical class 0.000 claims description 34
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 28
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 28
- 229920000570 polyether Polymers 0.000 claims description 28
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 27
- 229910021645 metal ion Inorganic materials 0.000 claims description 12
- 150000004010 onium ions Chemical class 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 238000010943 off-gassing Methods 0.000 abstract description 12
- 229920001693 poly(ether-ester) Polymers 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 90
- 238000000034 method Methods 0.000 description 57
- 239000002253 acid Substances 0.000 description 56
- 229910052751 metal Inorganic materials 0.000 description 44
- 239000002184 metal Substances 0.000 description 44
- 229910019142 PO4 Inorganic materials 0.000 description 38
- 235000021317 phosphate Nutrition 0.000 description 38
- 239000010452 phosphate Substances 0.000 description 36
- 150000003839 salts Chemical class 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 24
- 239000000047 product Substances 0.000 description 24
- 229910052700 potassium Inorganic materials 0.000 description 23
- 239000011591 potassium Substances 0.000 description 23
- 229910052783 alkali metal Inorganic materials 0.000 description 22
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 20
- 229920001577 copolymer Polymers 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 20
- 229910052708 sodium Inorganic materials 0.000 description 20
- 239000011734 sodium Substances 0.000 description 20
- 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 18
- 239000003063 flame retardant Substances 0.000 description 18
- 239000003381 stabilizer Substances 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 14
- 239000003513 alkali Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 238000005809 transesterification reaction Methods 0.000 description 13
- 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 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 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 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 150000001340 alkali metals Chemical class 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 239000011342 resin composition Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 11
- 229920000515 polycarbonate Polymers 0.000 description 11
- 239000004417 polycarbonate Substances 0.000 description 11
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 11
- RAADBCJYJHQQBI-UHFFFAOYSA-N 2-sulfoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(S(O)(=O)=O)=C1 RAADBCJYJHQQBI-UHFFFAOYSA-N 0.000 description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 10
- 229910052731 fluorine Inorganic materials 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 9
- 239000003963 antioxidant agent Substances 0.000 description 9
- 235000006708 antioxidants Nutrition 0.000 description 9
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 9
- 238000001746 injection moulding Methods 0.000 description 9
- 239000000155 melt Substances 0.000 description 9
- 239000008188 pellet Substances 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229920005992 thermoplastic resin Polymers 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 125000002524 organometallic group Chemical group 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000001976 improved effect Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000004381 surface treatment Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 6
- 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 5
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 230000001588 bifunctional effect Effects 0.000 description 5
- 229910052792 caesium Inorganic materials 0.000 description 5
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 5
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- KTRAEKUHPXFQHU-UHFFFAOYSA-N 1-sulfonaphthalene-2,6-dicarboxylic acid Chemical compound OS(=O)(=O)C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 KTRAEKUHPXFQHU-UHFFFAOYSA-N 0.000 description 4
- ZOHVMXYKQPCRLG-UHFFFAOYSA-N 1-sulfonaphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C(S(O)(=O)=O)C2=CC(C(=O)O)=CC=C21 ZOHVMXYKQPCRLG-UHFFFAOYSA-N 0.000 description 4
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 238000012696 Interfacial polycondensation Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 4
- 150000008041 alkali metal carbonates Chemical class 0.000 description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 150000004650 carbonic acid diesters Chemical class 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 239000002685 polymerization catalyst Substances 0.000 description 4
- 238000002360 preparation method Methods 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
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 description 3
- 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 3
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 3
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 3
- UMPGNGRIGSEMTC-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexyl]phenol Chemical compound C1C(C)CC(C)(C)CC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UMPGNGRIGSEMTC-UHFFFAOYSA-N 0.000 description 3
- NUDSREQIJYWLRA-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=CC=2)=C1 NUDSREQIJYWLRA-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 3
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 238000012695 Interfacial polymerization Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- 230000002411 adverse Effects 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000001939 inductive effect Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
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- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- FEDFHMISXKDOJI-UHFFFAOYSA-M lithium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F FEDFHMISXKDOJI-UHFFFAOYSA-M 0.000 description 1
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- 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
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- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- 229950011008 tetrachloroethylene Drugs 0.000 description 1
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- 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
- QLORRTLBSJTMSN-UHFFFAOYSA-N tris(2,6-dimethylphenyl) phosphate Chemical compound CC1=CC=CC(C)=C1OP(=O)(OC=1C(=CC=CC=1C)C)OC1=C(C)C=CC=C1C QLORRTLBSJTMSN-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
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
【解決手段】(A)芳香族ポリカーボネート樹脂(A成分)65〜85重量部と、(B)平均粒径が5〜60μmである黒鉛(B成分)15〜35重量部との合計100重量部に対し、(C)スルホン酸塩基を有するポリエステル(C−1成分)およびスルホン酸塩基を有するポリエーテルエステル(C−2成分)からなる群より選択される少なくとも1種の化合物(C成分)0.1〜5重量部並びに(D)ポリテトラフルオロエチレン粒子(D成分)1〜10重量部を含有する芳香族ポリカーボネート樹脂組成物。
【選択図】なし
Description
本発明の好適な態様の1つは、(6)ストレージAV機器部品であることを特徴とする上記構成(5)に記載の樹脂成形体である。
本発明の好適な態様の1つは、(7)ハードディスクドライブ(HDD)やデジタル多用途ディスク(DVD)ドライブの空気整流板であることを特徴とする上記構成(6)に記載の樹脂成形体である。
(A成分:芳香族ポリカーボネート樹脂)
本発明でA成分として使用される芳香族ポリカーボネート樹脂は、2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。
また、上記製造方法の妨げにならない範囲で、上記2価フェノール、ヒドロキシアリール末端ポリジオルガノシロキサン以外の他のコモノマーを共重合体の全重量に対して10重量%以下の範囲で併用することもできる。
クロロホルメート化合物の生成反応におけるpH範囲は、公知の界面反応条件が利用でき、pHは通常10以上に調製される。
かかる重縮合反応においては、末端停止剤或いは分子量調節剤が通常使用される。末端停止剤としては一価のフェノール性水酸基を有する化合物が挙げられ、通常のフェノール、p−tert−ブチルフェノール、p−クミルフェノール、トリブロモフェノールなどの他に、長鎖アルキルフェノール、脂肪族カルボン酸クロライド、脂肪族カルボン酸、ヒドロキシ安息香酸アルキルエステル、ヒドロキシフェニルアルキル酸エステル、アルキルエーテルフェノールなどが例示される。その使用量は用いる全ての2価フェノール系化合物100モルに対して、好ましくは100〜0.5モル、より好ましくは50〜2モルの範囲であり、二種以上の化合物を併用することも当然に可能である。
かかる重合反応の反応時間は、透明性を向上させるためには比較的長くする必要がある。好ましくは30分以上、更に好ましくは50分以上であり、製造効率の点からその上限は好ましくは2時間以下、より好ましくは1.5時間以下である。
有機溶媒としては例えば塩化メチレン、クロロベンゼンなどのハロゲン化炭化水素が用いられる。
反応温度は通常0〜40℃、反応時間は数分〜5時間、反応中のpHは通常10以上に保つのが好ましい。
前記以外の反応形式の詳細についても、各種の文献および特許公報などで良く知られている。
粘度平均分子量が10,000未満の芳香族ポリカーボネート樹脂では、良好な機械的特性が得られない。一方、粘度平均分子量が50,000を超える芳香族ポリカーボネート樹脂から得られる樹脂組成物は、射出成形時の流動性に劣る点で汎用性に劣る。
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Mを算出する。
ηSP/c=[η]+0.45×[η]2c(但し[η]は極限粘度)
[η]=1.23×10−4M0.83
c=0.7
本発明でB成分として使用される黒鉛としては、鉱物名で石墨とされる天然黒鉛、または各種の人造黒鉛のいずれも利用することができる。天然黒鉛としては、土状黒鉛、鱗状黒鉛(塊状黒鉛とも称されるVein Graphite)および鱗片状黒鉛(Flake Graphite)のいずれを利用することもできる。また人造黒鉛は、無定形炭素を熱処理し不規則な配列の微小黒鉛結晶の配向を人工的に行わせたものであり、一般炭素材料に使用される人造黒鉛の他、キッシュ黒鉛、分解黒鉛、および熱分解黒鉛などを含む。一般炭素材料に使用される人造黒鉛は、通常石油コークスや石炭系ピッチコークスを主原料として黒鉛化処理により製造される。
本発明の芳香族ポリカーボネート樹脂組成物は、スルホン酸塩基を有するポリエステルおよびスルホン酸塩基を有するポリエーテルエステルからなる群より選択される少なくとも1重の化合物を使用することにより優れた特性を発揮し、両者を併用することがさらに好ましい。ここでポリエーテルエステルとは、3量体以上のポリ(アルキレンオキサイド)グリコール成分をその繰り返し単位に有するポリマーをいい、ポリエステルとは、3量体以上のポリ(アルキレンオキサイド)グリコール成分を含有しないポリエステルである。尚、ポリエステル中にはジエチレングリコール成分を含むことができる。該C成分はスルホン酸塩基が置換された単量体を重合反応させることによりポリマー化合物とすること、またはスルホン酸塩基で置換されていないポリマーをスルホン酸塩基で変性することにより製造することもできる。
上記式〔1〕中のArは、炭素数6〜20の3価の芳香族基であり、具体的には3価のベンゼン環、ナフタレン環が挙げられ、これらの環がアルキル基、フェニル基、ハロゲン、およびアルコキシ基などの置換基を有していてもよい。
上記式〔1〕中のArは、炭素数6〜20の3価の芳香族基であり、具体的には3価のベンゼン環、ナフタレン環が挙げられ、これらの環がアルキル基、フェニル基、ハロゲン、およびアルコキシ基などの置換基を有していてもよい。
本発明のD成分として使用されるポリテトラフルオロエチレン粒子は、成形品に摺動性を付与することにより黒鉛の脱落を抑制するために配合する。なお、ポリテトラフルオロエチレン粒子を配合することにより、黒鉛の脱落が抑制されるのは、成形品表面と接触する物質との摩擦により剪断力を受けたポリテトラフルオロエチレン粒子が繊維化して互いに絡み合うようになり、その結果黒鉛と成形品表面との結着性が高まるためと考えられる。
(i)リン系安定剤
本発明の芳香族ポリカーボネート樹脂組成物には、本発明の目的が損なわれない量のリン系安定剤を使用することができる。かかるリン系安定剤は製造時または成形加工時の芳香族ポリカーボネート樹脂の熱安定性を大きく向上させる。その結果、機械的特性、導電性、難燃性および成形安定性を向上させる。かかるリン系安定剤としては、亜リン酸、リン酸、亜ホスホン酸、ホスホン酸およびこれらのエステル、並びに第3級ホスフィンなどが例示される。これらの中でも特に、亜リン酸、リン酸、亜ホスホン酸、およびホスホン酸、トリオルガノホスフェート化合物、およびアシッドホスフェート化合物が好ましい。尚、アシッドホスフェート化合物における有機基は、一置換、二置換、およびこれらの混合物のいずれも含む。該化合物に対応する下記の例示化合物においても同様にいずれをも含むものとする。
リン系安定剤の含有量は、100重量部のA成分を基準として好ましくは0.0001〜2重量部、より好ましくは0.01〜1重量部、更に好ましくは0.05〜0.5重量部である。またリン系安定剤は、その100重量%中50重量%以上がトリアルキルホスフェートおよび/またはアシッドホスフェート化合物であることが好ましく、特にその100重量%中50重量%以上がトリアルキルホスフェートであることが好ましい。
本発明の芳香族ポリカーボネート樹脂組成物は、更にヒンダードフェノール系安定剤を含有することにより、例えば成形加工時の色相悪化や長期間の使用における色相の悪化などの効果が更に発揮される。ヒンダードフェノール系安定剤としては、例えば、α−トコフェロール、ブチルヒドロキシトルエン、シナピルアルコール、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)、2,2−チオジエチレンビス−[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]、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、およびテトラキス[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]メタンなどが例示される。これらはいずれも入手容易である。上記ヒンダードフェノール系安定剤は、単独でまたは2種以上を組合せて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離型剤を含有することができる。離型剤としては、例えば、飽和脂肪酸エステル、不飽和脂肪酸エステル、ポリオレフィン系ワックス(ポリエチレンワックス、1−アルケン重合体など。酸変性などの官能基含有化合物で変性されているものも使用できる)、シリコーン化合物、フッ素化合物(ポリフルオロアルキルエーテルに代表されるフッ素オイルなど)、パラフィンワックス、蜜蝋などが例示される。かかる離型剤の配合量は100重量部のA成分を基準として好ましくは0.005〜2重量部、より好ましくは0.01〜0.8重量部である。
本発明の芳香族ポリカーボネート樹脂組成物は、良好な耐光性を要求される場合があり、かかる場合に紫外線吸収剤の配合が効果的である。
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。
本発明の芳香族ポリカーボネート樹脂組成物には、本発明の目的が損なわれない量の難燃剤を使用することができる。難燃剤としては、(1)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、ホウ酸金属塩系難燃剤、および錫酸金属塩系難燃剤など)、並びに(2)有機リン系難燃剤(例えば、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)等が挙げられる。
有機金属塩系難燃剤は、耐熱性がほぼ維持されると共に少なからず帯電防止性を付与できる点で有利である。本発明において最も有利に使用される有機金属塩系難燃剤は、含フッ素有機金属塩化合物である。本発明の含フッ素有機金属塩化合物とは、フッ素置換された炭化水素基を有する有機酸からなるアニオン成分と金属イオンからなるカチオン成分からなる金属塩化合物をいう。より好適な具体例としては、フッ素置換有機スルホン酸の金属塩、フッ素置換有機硫酸エステルの金属塩、およびフッ素置換有機リン酸エステルの金属塩が例示される。含フッ素有機金属塩化合物は1種もしくは2種以上を混合して使用することができる。その中でも好ましいのはフッ素置換有機スルホン酸の金属塩であり、とくに好ましいのはパーフルオロアルキル基を有するスルホン酸の金属塩である。ここでパーフルオロアルキル基の炭素数は、1〜18の範囲が好ましく、1〜10の範囲がより好ましく、更に好ましくは1〜8の範囲である。
本発明の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が好適である。かかるホスフェート化合物は概して色相に優れ、光高反射性に悪影響を与えることが少ないためである。またホスフェート化合物は可塑化効果があるため本発明の樹脂組成物の成形加工性を高められる点で有利である。かかる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[7]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。
有機リン系難燃剤の配合量は、A成分とB成分との合計100重量部を基準として好ましくは1〜20重量部であり、より好ましくは2〜15重量部、更に好ましくは5〜10重量部である。
本発明の芳香族ポリカーボネート樹脂組成物には、本発明の効果を発揮する範囲において、強化フィラーとして各種充填材を配合することができる。例えば、炭酸カルシウム、ガラス繊維、ガラスビーズ、ガラスバルーン、ガラスミルドファイバー、ガラスフレーク、フラーレン、金属フレーク、金属繊維、金属コートガラス繊維、金属コート炭素繊維、金属コートガラスフレーク、シリカ、金属酸化物粒子、金属酸化物繊維、金属酸化物バルーン、並びに各種ウイスカー(チタン酸カリウムウイスカー、ホウ酸アルミニウムウイスカー、および塩基性硫酸マグネシウムなど)などが例示される。これらの強化フィラーは1種もしくは2種以上を併用して含むものであってもよい。
かかる添加剤としては、摺動剤(例えばD成分以外のPTFE粒子)、着色剤(例えばカーボンブラック、酸化チタンなどの顔料、染料)、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)、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)、およびフォトクロミック剤などが挙げられる。
本発明の芳香族ポリカーボネート樹脂組成物を製造するには、任意の方法が採用される。例えばA〜D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。
本発明の芳香族ポリカーボネート樹脂組成物からなる成形品は、通常そのペレットを射出成形して得ることができる。かかる射出成形においては、通常の成形方法だけでなく、射出圧縮成形、射出プレス成形、ガスアシスト射出成形、発泡成形(超臨界流体を注入する方法を含む)、インサート成形、インモールドコーティング成形、断熱金型成形、急速加熱冷却金型成形、二色成形、サンドイッチ成形、および超高速射出成形などを挙げることができる。また成形はコールドランナー方式およびホットランナー方式のいずれも選択することができる。
さらに本発明の成形品には、各種の表面処理を行うことが可能である。表面処理としては、ハードコート、撥水・撥油コート、親水性コート、帯電防止コート、紫外線吸収コート、赤外線吸収コート、並びにメタライジング(蒸着など)などの各種の表面処理を行うことができる。表面処理方法としては、液剤のコーティングの他、蒸着法、溶射法、およびメッキ法が挙げられる。蒸着法としては物理蒸着法および化学蒸着法のいずれも使用できる。物理蒸着法としては真空蒸着法、スパッタリング、およびイオンプレーティングが例示される。化学蒸着(CVD)法としては、熱CVD法、プラズマCVD法、および光CVD法などが例示される。
したがって本発明の芳香族ポリカーボネート樹脂組成物は、OA機器分野、電気電子機器分野などの各種工業用途に極めて有用であり、その奏する工業的効果は極めて大である。
1.ポリエーテルエステル(C−2成分)の作成
150.8部の2,6−ナフタレンジカルボン酸ジメチルエステル(C2−1成分)、24.9部の5−ナトリウムスルホイソフタル酸ジメチル(C2−2成分)、47.9部のエチレングリコール(C2−3−1成分)、74.6部の1,6−ヘキサンジオール(C2−3−2成分)、89.8部のポリエチレングリコール(数平均分子量2,000;C2−4成分)、および0.14部のテトラブチルチタネートを精留塔および攪拌装置を備えた反応器に入れ、容器内を窒素置換した後、攪拌しながら常圧下200℃まで昇温した。反応により生成するメタノールを留去しながら6時間で200℃から230℃まで徐々に昇温していき、反応を完結させた。その後、反応物を攪拌装置を備えた真空留出系を有する反応器に移送し、温度230℃にて攪拌しながら、60分後に6.7×102Pa、100分後に1.3×102Pa、120分後には0.67×102Paと系内を徐々に減圧にしていき、反応留出物を留去しながら重合反応せしめることにより、ポリエーテルエステル共重合体を得た。得られたポリエーテルエステル共重合体の還元粘度は1.35であった(フェノール/テトラクロロエタン(重量比40/60)の混合溶媒中において、濃度1.2(g/dl)、30℃にて測定した値である。)。また、得られたポリエーテルエステル共重合体は、C2−1成分とC2−2成分との割合が85:15(モル比)であり、C2−3−1成分とC2−3−2成分との割合が19:81(モル比)であり、C2−4成分の含有量は26重量%であった。
下記の方法により、組成物ペレットの製造を行った。
表1および表2に記載の各成分を、表1および表2に示す割合にてドライブレンドした後、ベント式二軸押出機(株)日本製鋼所製:TEX−30XSST(完全かみ合い、同方向回転、2条ネジスクリュー)を使用した。押出条件は吐出量15kg/h、スクリュー回転数150rpm、ベントの真空度3kPaであり、また押出温度は280℃にて溶融混練し、押出し、ストランドカットすることで、各組成物のペレットを得た。
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。乾燥後のペレットを用いてシリンダー内径40mmφの射出成形機(ファナック(株)製 FAS−T150D)を使用し、幅50mm×長さ90mm×厚み2mmの角板成形品を、シリンダー温度300℃、金型温度100℃にて成形した。この成形品を用いて、下記の導電性、溶融熱安定性およびアウトガス性を測定した。それらの測定結果を表1および表2に示す。
実施例中における各値は下記の方法で求めた。
(1)導電性(表面抵抗率)
上記の方法で得た成形品をそれぞれの抵抗値に合った抵抗率計を使用して測定した。すなわち、107〜1015Ω/sqの場合は、三菱化学株式会社製 ハイレスターUP MCP−HT400(印加電圧100V、UR-SSプローブ(JISK6911準拠))、107Ω/sq未満の場合には、三菱化学株式会社製 ロレスターGP MCP-T600(印加電圧90V、ESPプローブ(JISK7194準拠))を使用した。具体的な測定方法としては、成形品から試験片(縦×横×厚み=45mm×50mm×2mmt)を切削し、温度23℃、湿度50%RHの条件下において前記の抵抗率計を使用して試験片面内の中央部の表面抵抗率を測定し10個の試験片から得られた値の平均値を成形品の表面抵抗率とした。表面抵抗率は1.0×1011未満であることが必要である。
ISO 178(測定条件23℃)に準拠して測定した。なお、試験片は、射出成形機(ファナック(株)製 FAS−T150D)によりシリンダー温度300℃、金型温度100℃で成形した。曲げ弾性率は4000MPa以上が必要である。
A成分として使用される芳香族ポリカーボネート樹脂の粘度平均分子量を、本文記載の方法により測定した。一方、上記の方法において成形サイクル600秒とする条件で射出成形により成形品を成形した。その成形品を粉砕し、粘度平均分子量を同様に測定した。かかるA成分として使用される芳香族ポリカーボネート樹脂の分子量を100%とした時の上記成形品の分子量を百分率であらわし、分子量保持率とした。かかる分子量保持率が高いほど溶融熱安定性が良好といえる。上記分子量保持率が90%より大きいものを◎、80〜90%であるものを○、80%未満であるものを×として評価した。
上記の方法で得た成形品から0.1gを削り取り、熱重量解析装置(TA Instruments社製TGA2950型Thermogravimetric Analyzer)により、窒素ガス雰囲気中、昇温速度20℃/minで室温(23℃)から320℃まで昇温後、320℃にて30分間加熱し、試験前後の重量減少量(%)をアウトガス量として算出した。上記アウトガス量が0.1%未満であるものを◎、0.1〜0.2%であるものを○、0.2%より大きいものを×として評価した。
上記の方法で得た組成物ペレットを射出成形機(三菱重工業(株)製:80MSP−5)を使用して、シリンダー温度300℃、金型温度100℃にて、測定用の試験片(直径×高さ=10mm×20mmのピン状成形片)を成形し、往復動摩擦磨耗試験機((株)オリンテック製:AFT−15M)を使用し、23℃、50%RHの条件下において0.5kgの一定荷重の下で台紙の上で往復摩擦させ台紙に付着した黒鉛の脱落跡を評価した。台紙に黒鉛の脱落跡がほとんど見られない場合を◎、若干の黒鉛の脱落跡が認められる場合を○、黒鉛の脱落跡がはっきり確認できる場合を×として評価した。
なお、実施例及び比較例で使用した原材料は、下記の通りである。
(A成分:芳香族ポリカーボネート)
A:粘度平均分子量22,400の直鎖状ポリカーボネート樹脂パウダー[帝人化成(株)製:パンライトL−1225WP]
(B成分:黒鉛)
B−1:黒鉛(平均粒径25μm、長軸方向長さ/厚さ68、固定炭素量99.6%、揮発分0.2%、灰分0.2%)[日本黒鉛工業(株)製:UP−20]
B−2:黒鉛(平均粒径33μm、長軸方向長さ/厚さ33、固定炭素量99.6%、揮発分0.2%、灰分0.2%)[日本黒鉛工業(株)製:SP−10]
B−3:黒鉛(平均粒径8μm、長軸方向長さ/厚さ16、固定炭素量98.9%、揮発分0.4%、灰分0.7%)[西村黒鉛(株)製:PS−99]
B−4:黒鉛(平均粒径57μm、長軸方向長さ/厚さ17、固定炭素量98.5%、揮発分0.6%、灰分1.0%)[西村黒鉛(株)製:10099M]
(B成分以外)
B−5:黒鉛(平均粒径4μm、長軸方向長さ/厚さ11、固定炭素量99.6%、揮発分0.4%、灰分0.0%)[日本黒鉛工業(株)製:UP−5NH]
B−6:黒鉛(平均粒径62μm、長軸方向長さ/厚さ9、固定炭素量99.6%、揮発分0.4%、灰分0.0%)[オリエンタル産業(株)製:AT−No.5S]
B−7:炭素繊維(直径7.5μm、カット長6mm)[東邦レーヨン(株)製:ベスファイト HTA−C6−U]
(C成分:ポリエーテルエステル化合物、ポリエステル化合物)
C−1:スルホン酸ナトリウム変性ポリエステル(5−ナトリウムスルホイソフタル酸単位を繰り返し単位として含有するポリエチレンテレフタレート/イソフタレート共重合、還元粘度0.54dl/g、スルホン酸ナトリウム塩基は約5.9×10−4モル/g)[東洋紡績(株)製:バイロン280]
C−2:上記方法で作成したポリエーテルエステル共重合体(還元粘度1.35dl/g、スルホン酸ナトリウム塩基は約1.5×10−4モル/g)
(C成分以外)
C−3:ポリエチレンテレフタレート樹脂[帝人化成(株)製:TR−4550BH]
(D成分:ポリテトラフルオロエチレン粒子)
D−1:ポリテトラフルオロエチレン粒子[ダイキン工業(株)製:ルブロン L−5)
Claims (7)
- (A)芳香族ポリカーボネート樹脂(A成分)65〜85重量部と、(B)平均粒径が5〜60μmである黒鉛(B成分)15〜35重量部との合計100重量部に対し、(C)スルホン酸塩基を有するポリエステル(C−1成分)およびスルホン酸塩基を有するポリエーテルエステル(C−2成分)からなる群より選択される少なくとも1種の化合物(C成分)0.1〜5重量部並びに(D)ポリテトラフルオロエチレン粒子(D成分)1〜10重量部を含有する芳香族ポリカーボネート樹脂組成物。
- B成分が、粒子状に分散され、該粒子の厚さが0.1〜10μmであり、かつ長軸方向長さ/厚さが30以上である黒鉛であることを特徴とする請求項1記載の芳香族ポリカーボネート樹脂組成物。
- C−2成分が、(C2−1)スルホン酸塩基を持たない芳香族ジカルボン酸成分から誘導される繰り返し単位、(C2−2)下記一般式〔1〕で表されるスルホン酸塩基で置換された芳香族ジカルボン酸成分から誘導される繰り返し単位、(C2−3)炭素数2〜10のグリコール成分から誘導される繰り返し単位、および(C2−4)数平均分子量200〜50,000のポリ(アルキレンオキシド)グリコール成分から誘導される繰返し単位からなるポリエーテルエステルである請求項1〜3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。
- 請求項1〜4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樹脂成形体。
- ストレージAV機器部品であることを特徴とする請求項5に記載の樹脂成形体。
- ハードディスクドライブ(HDD)やデジタル多用途ディスク(DVD)ドライブの空気整流板であることを特徴とする請求項6に記載の樹脂成形体。
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JP2015017166A (ja) * | 2013-07-10 | 2015-01-29 | 三菱エンジニアリングプラスチックス株式会社 | 摺動性ポリカーボネート樹脂組成物及び成形品 |
JP2015048409A (ja) * | 2013-09-02 | 2015-03-16 | 三菱エンジニアリングプラスチックス株式会社 | 摺動性ポリカーボネート樹脂組成物及び成形品 |
JP2017155250A (ja) * | 2017-06-19 | 2017-09-07 | 三菱エンジニアリングプラスチックス株式会社 | 摺動性ポリカーボネート樹脂組成物及び成形品 |
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JP2015017166A (ja) * | 2013-07-10 | 2015-01-29 | 三菱エンジニアリングプラスチックス株式会社 | 摺動性ポリカーボネート樹脂組成物及び成形品 |
JP2015048409A (ja) * | 2013-09-02 | 2015-03-16 | 三菱エンジニアリングプラスチックス株式会社 | 摺動性ポリカーボネート樹脂組成物及び成形品 |
JP2017155250A (ja) * | 2017-06-19 | 2017-09-07 | 三菱エンジニアリングプラスチックス株式会社 | 摺動性ポリカーボネート樹脂組成物及び成形品 |
JP6411588B6 (ja) | 2017-06-19 | 2022-10-07 | 三菱エンジニアリングプラスチックス株式会社 | 摺動性ポリカーボネート樹脂組成物及び成形品 |
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