JP5891015B2 - High thermal conductivity thermoplastic resin composition - Google Patents
High thermal conductivity thermoplastic resin composition Download PDFInfo
- Publication number
- JP5891015B2 JP5891015B2 JP2011257589A JP2011257589A JP5891015B2 JP 5891015 B2 JP5891015 B2 JP 5891015B2 JP 2011257589 A JP2011257589 A JP 2011257589A JP 2011257589 A JP2011257589 A JP 2011257589A JP 5891015 B2 JP5891015 B2 JP 5891015B2
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- Prior art keywords
- thermal conductivity
- resin
- acid
- resin composition
- bis
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims description 48
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 32
- 229920005989 resin Polymers 0.000 claims description 50
- 239000011347 resin Substances 0.000 claims description 50
- 238000001125 extrusion Methods 0.000 claims description 37
- 229910010272 inorganic material Inorganic materials 0.000 claims description 29
- 150000002484 inorganic compounds Chemical class 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 24
- 238000000465 moulding Methods 0.000 claims description 22
- 229920006230 thermoplastic polyester resin Polymers 0.000 claims description 20
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 150000008065 acid anhydrides Chemical class 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 229920000515 polycarbonate Polymers 0.000 claims description 9
- 239000004417 polycarbonate Substances 0.000 claims description 9
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 claims description 5
- 229920001225 polyester resin Polymers 0.000 claims description 4
- 229920001169 thermoplastic Polymers 0.000 claims description 3
- 239000004416 thermosoftening plastic Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000010101 extrusion blow moulding Methods 0.000 claims description 2
- -1 polyethylene terephthalate Polymers 0.000 description 40
- 229920005668 polycarbonate resin Polymers 0.000 description 26
- 239000004431 polycarbonate resin Substances 0.000 description 26
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- 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 13
- 238000000034 method Methods 0.000 description 13
- 229920000139 polyethylene terephthalate Polymers 0.000 description 13
- 239000005020 polyethylene terephthalate Substances 0.000 description 13
- 238000010292 electrical insulation Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000004898 kneading Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 238000000071 blow moulding Methods 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 6
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- 229910000859 α-Fe Inorganic materials 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-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
- 239000007983 Tris buffer Substances 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
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- 239000003365 glass fiber Substances 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
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 235000012438 extruded product Nutrition 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- IWDCLRJOBJJRNH-UHFFFAOYSA-N para-hydroxytoluene Natural products CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 2
- YQUVCSBJEUQKSH-UHFFFAOYSA-N 3,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 2
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 101000837805 Homo sapiens Testis-expressed protein 44 Proteins 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 2
- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 102100028514 Testis-expressed protein 44 Human genes 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 150000001722 carbon compounds Chemical class 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000004650 carbonic acid diesters Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000012567 medical material Substances 0.000 description 2
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 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 2
- 229930014626 natural product Natural products 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OKJFKPFBSPZTAH-UHFFFAOYSA-N (2,4-dihydroxyphenyl)-(4-hydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O OKJFKPFBSPZTAH-UHFFFAOYSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- 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 1
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Description
本発明は、高熱伝導性と、良好な押出成形性やブロー成形性とを併せ持ち、かつ衝撃強度などの良好な実用物性をも兼ね備えた、高熱伝導性熱可塑性樹脂組成物に関する。 The present invention relates to a high thermal conductivity thermoplastic resin composition that has both high thermal conductivity and good extrusion moldability and blow moldability, and also has good practical physical properties such as impact strength.
樹脂組成物をLED照明部材、パソコンやディスプレーの筐体、電子デバイス材料、自動車の内外装、など種々の用途に使用する際、プラスチックは金属材料など無機物と比較して熱伝導性が低いため、発生する熱を逃がしづらいことが問題になる。このような課題を解決するため、高熱伝導性無機物を大量に樹脂中に配合することで、高熱伝導性樹脂組成物を得ようとする試みが広くなされている。これらのなかでも、ポリカーボネート系樹脂と熱可塑性ポリエステル系樹脂とのアロイをベースにした高熱伝導性樹脂組成物は、耐衝撃性、耐熱性、成形加工性、耐薬品性を併せ持った特性から、種々の提案されている。 When the resin composition is used for various applications such as LED lighting members, housings of personal computers and displays, electronic device materials, automobile interior and exterior, plastics have lower thermal conductivity than inorganic materials such as metal materials, It is a problem that it is difficult to release the generated heat. In order to solve such problems, attempts have been widely made to obtain a high thermal conductive resin composition by blending a large amount of a high thermal conductive inorganic substance into the resin. Among these, high thermal conductive resin compositions based on an alloy of polycarbonate resin and thermoplastic polyester resin are various in terms of properties having impact resistance, heat resistance, molding processability, and chemical resistance. Has been proposed.
例えば特許文献1では、ポリエチレンテレフタレート樹脂(主としてポリカーボネート樹脂とポリエチレンテレフタレート樹脂等とのアロイ)に、炭素繊維等の無機物を配合してなる熱伝導性樹脂組成物が報告されている。また特許文献2では、ポリエチレンテレフタレート樹脂(主としてポリカーボネート樹脂とポリエチレンテレフタレート樹脂等とのアロイ)に、熱伝導性かつ電気絶縁性の無機物を配合してなる、射出成形性良好な熱伝導性樹脂組成物が報告されている。 For example, Patent Document 1 reports a thermally conductive resin composition obtained by blending an inorganic substance such as carbon fiber with a polyethylene terephthalate resin (mainly an alloy of a polycarbonate resin and a polyethylene terephthalate resin or the like). Further, in Patent Document 2, a heat-conductive resin composition having good injection moldability, comprising a polyethylene terephthalate resin (mainly an alloy of polycarbonate resin and polyethylene terephthalate resin, etc.) and a heat-conductive and electrically insulating inorganic substance. Has been reported.
一方で、ブロー成形や押出成形に適するようポリエチレンテレフタレート樹脂(主としてポリカーボネート樹脂とポリエチレンテレフタレート樹脂等とのアロイ)を変性する方法についても種々の研究例があり、例えば特許文献3では、ポリエチレンテレフタレート樹脂(主としてポリカーボネート樹脂とポリエチレンテレフタレート樹脂等とのアロイ)に、分子内にエポキシ基を3個以上有するオレフィン系樹脂及びフッ素系樹脂を添加することで、ブロー成形性が改善されることが示されている。また特許文献4では、ポリエチレンテレフタレート樹脂(主としてポリカーボネート樹脂とポリエチレンテレフタレート樹脂等とのアロイ)に、エポキシ基を2個以上有する化合物を添加することで、同様の効果を得ている。さらに特許文献5では、ポリカーボネート樹脂とポリエチレンテレフタレート樹脂等とのアロイに、分子内にカルボキシル基又はそのエステル形成性誘導体基を3個以上有する化合物及びその酸無水物よりなる群から選ばれる少なくとも1種の化合物を添加することで、同様の効果を得ている。特許文献6では、ポリカーボネート樹脂と、分岐成分を共重合したポリエステルからなる組成物が、ブロー成形に適していることが示されている。 On the other hand, there are various research examples on a method of modifying polyethylene terephthalate resin (mainly alloy of polycarbonate resin and polyethylene terephthalate resin) so as to be suitable for blow molding and extrusion molding. For example, in Patent Document 3, polyethylene terephthalate resin ( It has been shown that blow moldability is improved by adding an olefin resin and a fluorine resin having 3 or more epoxy groups in the molecule to an alloy mainly of a polycarbonate resin and a polyethylene terephthalate resin. . In Patent Document 4, the same effect is obtained by adding a compound having two or more epoxy groups to a polyethylene terephthalate resin (mainly an alloy of a polycarbonate resin and a polyethylene terephthalate resin or the like). Further, in Patent Document 5, at least one selected from the group consisting of a compound having three or more carboxyl groups or ester-forming derivative groups thereof in the molecule and an acid anhydride thereof in an alloy of a polycarbonate resin and a polyethylene terephthalate resin or the like. The same effect is obtained by adding this compound. Patent Document 6 shows that a composition comprising a polycarbonate resin and a polyester copolymerized with a branched component is suitable for blow molding.
特許文献2に示されるような手法を用いることで、射出成形性に優れた高熱伝導性樹脂組成物が得られるようにはなっているが、一方で当該樹脂組成物を押出成形やブロー成形など、射出成形と異なる成形加工方法で成形加工しようとすると、ポリカーボネート系樹脂や熱可塑性ポリエステル系樹脂がいずれも溶融張力が低い樹脂であることに起因し、良好な成形加工が困難であるという課題を有している。
一方で、特許文献3〜6に示されるような手法をそのまま特許文献2の技術に適用するのも容易ではなかった。
By using a technique as shown in Patent Document 2, a high thermal conductive resin composition excellent in injection moldability can be obtained. On the other hand, the resin composition is extruded or blow-molded. When trying to mold by a molding method different from injection molding, the problem is that good molding processing is difficult due to the fact that both polycarbonate resins and thermoplastic polyester resins are low melt tension resins. Have.
On the other hand, it is not easy to apply the technique as shown in Patent Documents 3 to 6 to the technique of Patent Document 2 as it is.
本発明者は、熱可塑性ポリエステル系樹脂/電気絶縁性を示す高熱伝導性無機化合物(特にポリカーボネート系樹脂/熱可塑性ポリエステル系樹脂/電気絶縁性を示す高熱伝導性無機化合物)よりなる樹脂組成物の押出成形性やブロー成形性を改良するため鋭意検討を実施した結果、特定の化合物を添加することで容易にその効果が得られることを見出し本発明にいたった。 The inventor of the present invention is a resin composition comprising a thermoplastic polyester resin / a highly thermally conductive inorganic compound exhibiting electrical insulation (particularly polycarbonate resin / thermoplastic polyester resin / a highly thermally conductive inorganic compound exhibiting electrical insulation). As a result of intensive studies to improve the extrusion moldability and blow moldability, it was found that the effect can be easily obtained by adding a specific compound, and the present invention has been achieved.
すなわち本発明は、熱可塑性ポリエステル系樹脂(B)、単体での熱伝導率が5W/m・K以上を示す高熱伝導性無機化合物(C)、分子内にカルボキシル基又はそのエステル形成性誘導体基を3個以上有する化合物及びその酸無水物よりなる群から選ばれる少なくとも1種の有機化合物(D)、よりなることを特徴とする、高熱伝導性熱可塑性樹脂組成物(請求項1)であり、
ポリカーボネート系樹脂(A)、熱可塑性ポリエステル系樹脂(B)、単体での熱伝導率が5W/m・K以上を示す高熱伝導性無機化合物(C)、分子内にカルボキシル基又はそのエステル形成性誘導体基を3個以上有する化合物及びその酸無水物よりなる群から選ばれる少なくとも1種の有機化合物(D)、よりなることを特徴とする、高熱伝導性熱可塑性樹脂組成物(請求項2)であり、
分子内にカルボキシル基又はそのエステル形成性誘導体基を3個以上有する化合物及びその酸無水物よりなる群から選ばれる少なくとも1種の有機化合物(D)が、芳香族多価カルボン酸及びその誘導体よりなる群から選ばれる少なくとも1種であることを特徴とする、請求項1記載の高熱伝導性熱可塑性樹脂組成物(請求項3)であり、
分子内にカルボキシル基又はそのエステル形成性誘導体基を3個以上有する化合物及びその酸無水物よりなる群から選ばれる少なくとも1種の有機化合物(D)が、酸無水物基を分子内に2個以上有する芳香族多価カルボン酸無水物であることを特徴とする、請求項1又は2記載の高熱伝導性熱可塑性樹脂組成物(請求項4)である。
また本発明は、押出成形またはブロー成形により、上記請求項1に記載の高熱伝導性熱可塑性樹脂組成物を成形することを特徴とする、成形体の製造方法(請求項5)である。
That is, the present invention relates to a thermoplastic polyester resin (B), a high thermal conductivity inorganic compound (C) having a single thermal conductivity of 5 W / m · K or more, a carboxyl group in the molecule or an ester-forming derivative group thereof. It is a highly heat conductive thermoplastic resin composition (Claim 1), characterized by comprising at least one organic compound (D) selected from the group consisting of a compound having 3 or more and acid anhydride thereof ,
Polycarbonate-based resin (A), thermoplastic polyester-based resin (B), highly thermally conductive inorganic compound (C) having a thermal conductivity of 5 W / m · K or more as a simple substance, carboxyl group in the molecule or ester formation thereof A highly heat-conductive thermoplastic resin composition comprising at least one organic compound (D) selected from the group consisting of a compound having three or more derivative groups and an acid anhydride thereof (Claim 2). And
At least one organic compound (D) selected from the group consisting of a compound having three or more carboxyl groups or ester-forming derivative groups thereof in the molecule and an acid anhydride thereof is an aromatic polycarboxylic acid and derivatives thereof. It is at least one selected from the group consisting of the high thermal conductivity thermoplastic resin composition (claim 3) according to claim 1,
At least one organic compound (D) selected from the group consisting of a compound having three or more carboxyl groups or ester-forming derivative groups thereof in the molecule and an acid anhydride thereof has two acid anhydride groups in the molecule. 3. The highly heat-conductive thermoplastic resin composition according to claim 1 or 2, which is an aromatic polycarboxylic acid anhydride having the above (claim 4).
Moreover, this invention is a manufacturing method (Claim 5) of shape | molding the highly heat conductive thermoplastic resin composition of the said Claim 1 by extrusion molding or blow molding.
本発明の方法を用いることにより、高熱伝導性、高耐熱性、電気絶縁性、を兼ね備え、なおかつ押出成形性やブロー成形性良好な高熱伝導性樹脂組成物を得ることができる。
このようにして得られた複合材料は、樹脂フィルム、樹脂成形品、樹脂発泡体、塗料やコーティング剤、などさまざまな形態で、電子材料、磁性材料、触媒材料、構造体材料、光学材料、医療材料、自動車材料、建築材料、等の各種の用途に幅広く用いることが可能である。本発明で得られた高分子材料は、現在広く用いられているブロー成形機や押出成形機等の一般的なプラスチック用成形機が使用可能であるため、複雑な形状を有する製品への成形も容易である。特に成形加工性、耐衝撃性、耐薬品性、熱伝導性、などの重要な諸特性のバランスに優れていることから、発熱源を内部に有する照明、ディスプレー、コンピューターなどの筐体用樹脂として、非常に有用である。
By using the method of the present invention, it is possible to obtain a high thermal conductive resin composition having high thermal conductivity, high heat resistance, and electrical insulation, and having good extrusion moldability and blow moldability.
The composite materials obtained in this way are in various forms such as resin films, resin molded products, resin foams, paints and coating agents, electronic materials, magnetic materials, catalyst materials, structural materials, optical materials, medical materials, etc. It can be widely used for various applications such as materials, automobile materials, and building materials. The polymer material obtained in the present invention can be used for general plastic molding machines such as blow molding machines and extrusion molding machines which are widely used at present, and can be molded into products having complicated shapes. Easy. In particular, it has an excellent balance of important properties such as moldability, impact resistance, chemical resistance, and thermal conductivity, so it can be used as a resin for housings such as lighting, displays, and computers that have a heat source inside. Is very useful.
本発明の熱可塑性樹脂組成物は、熱可塑性ポリエステル系樹脂(B)、高熱伝導性無機化合物(C)、分子内にカルボキシル基又はそのエステル形成性誘導体基を3個以上有する化合物及びその酸無水物よりなる群から選ばれる少なくとも1種の有機化合物(D)、の三成分を必須とするものであり、必要に応じポリカーボネート系樹脂(A)、を併用するものである。 The thermoplastic resin composition of the present invention comprises a thermoplastic polyester resin (B), a highly thermally conductive inorganic compound (C), a compound having three or more carboxyl groups or ester-forming derivative groups in the molecule, and acid anhydrides thereof. Three components of at least one organic compound (D) selected from the group consisting of products are essential, and a polycarbonate resin (A) is used in combination as necessary.
本発明の熱可塑性樹脂組成物に配合される熱可塑性ポリエステル系樹脂(B)は、2価以上のカルボン酸化合物と、2価以上のアルコール及び/又はフェノール化合物とを公知の方法で重縮合することにより得られる熱可塑性ポリエステルである。具体的には、例えば、ポリエチレンテレフタレート、ポリプロピレンテレフタレート、ポリブチレンテレフタレート、ポリヘキサメチレンテレフタレート、ポリシクロヘキサンジメチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート等が挙げられるが、これらに限定されるものではない。 The thermoplastic polyester resin (B) blended in the thermoplastic resin composition of the present invention polycondenses a divalent or higher carboxylic acid compound and a divalent or higher alcohol and / or phenol compound by a known method. It is a thermoplastic polyester obtained by this. Specific examples include, but are not limited to, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate. .
2価以上のカルボン酸化合物としては特に限定されず、例えば、炭素数8〜22の2価以上の芳香族カルボン酸、これらのエステル形成性誘導体等が挙げられる。具体的には、例えば、テレフタル酸、イソフタル酸等のフタル酸;ナフタレンジカルボン酸、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′−ジフェニルジカルボン酸、1,2−ビス(フェノキシ)エタン−4,4′−ジカルボン酸、ジフェニルスルホンジカルボン酸、トリメシン酸、トリメリット酸、ピロメリット酸等のカルボン酸、これらのエステル形成能を有する誘導体等が挙げられる。これらは単独で用いてもよく、2種以上を併用してもよい。なかでも、取り扱い易さ、反応の容易さ、得られる樹脂組成物の物性等の観点から、テレフタル酸、イソフタル酸又はナフタレンジカルボン酸が好ましい。 It does not specifically limit as a carboxylic acid compound more than bivalence, For example, C8-C22 bivalent or more aromatic carboxylic acid, these ester-forming derivatives, etc. are mentioned. Specifically, for example, phthalic acid such as terephthalic acid and isophthalic acid; naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4-4′-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ) Carboxylic acids such as ethane-4,4'-dicarboxylic acid, diphenylsulfone dicarboxylic acid, trimesic acid, trimellitic acid and pyromellitic acid, derivatives having these ester forming ability, and the like. These may be used alone or in combination of two or more. Of these, terephthalic acid, isophthalic acid, or naphthalenedicarboxylic acid is preferred from the viewpoints of ease of handling, ease of reaction, and physical properties of the resulting resin composition.
2価以上のアルコール及び/又はフェノール化合物としては特に限定されず、例えば、炭素数2〜15の脂肪族化合物、炭素数6〜20の脂環式化合物、炭素数6〜40の芳香族化合物であって分子内に2個以上の水酸基を有する化合物、これらのエステル形成性誘導体等が挙げられる。具体的には、例えば、エチレングリコール、プロピレングリコール、ブタンジオール、ヘキサンジオール、デカンジオール、ネオペンチルグリコール、シクロヘキサンジメタノール、シクロヘキサンジオール、2,2′−ビス(4−ヒドロキシフェニル)プロパン、2,2′−ビス(4−ヒドロキシシクロヘキシル)プロパン、ハイドロキノン、グリセリン、ペンタエリスリトール、これらのエステル形成能を有する誘導体等が挙げられる。これらは単独で用いてもよく、2種以上を併用してもよい。なかでも、取り扱い易さ、反応の容易さ、得られる樹脂組成物の物性等の観点から、エチレングリコール、ブタンジオール又はシクロヘキサンジメタノールが好ましい。 The divalent or higher alcohol and / or phenol compound is not particularly limited, and examples thereof include aliphatic compounds having 2 to 15 carbon atoms, alicyclic compounds having 6 to 20 carbon atoms, and aromatic compounds having 6 to 40 carbon atoms. And compounds having two or more hydroxyl groups in the molecule and ester-forming derivatives thereof. Specifically, for example, ethylene glycol, propylene glycol, butanediol, hexanediol, decanediol, neopentyl glycol, cyclohexanedimethanol, cyclohexanediol, 2,2'-bis (4-hydroxyphenyl) propane, 2,2 Examples include '-bis (4-hydroxycyclohexyl) propane, hydroquinone, glycerin, pentaerythritol, and derivatives having these ester forming ability. These may be used alone or in combination of two or more. Of these, ethylene glycol, butanediol, or cyclohexanedimethanol is preferred from the viewpoints of ease of handling, ease of reaction, and physical properties of the resulting resin composition.
熱可塑性ポリエステル系樹脂(B)は、上述のカルボン酸化合物並びにアルコール及び/又はフェノール化合物に加えて、所望の特性を損なわない範囲で、公知の共重合可能な化合物を共重合して得られたものであってもよい。このような共重合可能な化合物としては特に限定されず、例えば、炭素数4〜12の2価以上の脂肪族カルボン酸、炭素数8〜15の2価以上の脂環式カルボン酸、これらのエステル形成性誘導体等が挙げられる。具体的には、例えば、アジピン酸、セバシン酸、アゼライン酸、ドデカンジカルボン酸、マレイン酸、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のジカルボン酸又はそのエステル形成能を有する誘導体等が挙げられる。その他にも、p−ヒドロキシ安息香酸等のオキシ酸又はそのエステル形成性誘導体、ε−カプロラクトン等の環状エステル等も挙げられる。 The thermoplastic polyester resin (B) was obtained by copolymerizing a known copolymerizable compound in addition to the above-described carboxylic acid compound and alcohol and / or phenol compound within a range that does not impair the desired properties. It may be a thing. Such a copolymerizable compound is not particularly limited, and examples thereof include a divalent or higher aliphatic carboxylic acid having 4 to 12 carbon atoms, a divalent or higher alicyclic carboxylic acid having 8 to 15 carbon atoms, and the like. Examples thereof include ester-forming derivatives. Specifically, for example, dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, maleic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid or derivatives having ester forming ability thereof Etc. Other examples include oxyacids such as p-hydroxybenzoic acid or ester-forming derivatives thereof, and cyclic esters such as ε-caprolactone.
また熱可塑性ポリエステル系樹脂(B)は、ポリアルキレングリコール単位を高分子鎖中に一部共重合させることにより得られた熱可塑性ポリエステル系樹脂であってもよい。このようなポリアルキレングリコールとしては特に限定されず、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリ(エチレンオキサイド・プロピレンオキサイド)ブロック及び/又はランダム共重合体、ビスフェノールA共重合ポリエチレンオキシド付加重合体、同プロピレンオキシド付加重合体、同テトラヒドロフラン付加重合体、ポリテトラメチレングリコール等が挙げられる。 The thermoplastic polyester resin (B) may be a thermoplastic polyester resin obtained by partially copolymerizing a polyalkylene glycol unit in a polymer chain. Such polyalkylene glycol is not particularly limited. For example, polyethylene glycol, polypropylene glycol, poly (ethylene oxide / propylene oxide) block and / or random copolymer, bisphenol A copolymer polyethylene oxide addition polymer, propylene Examples thereof include oxide addition polymers, tetrahydrofuran addition polymers, and polytetramethylene glycol.
熱可塑性ポリエステル系樹脂(B)における上述のような共重合成分の使用量としては、通常、20重量%以下であり、好ましくは15重量%以下、より好ましくは10重量%以下である。 The amount of the copolymer component as described above in the thermoplastic polyester resin (B) is usually 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less.
熱可塑性ポリエステル系樹脂(B)は、得られる樹脂組成物の物性バランス(例えば成形加工性)に優れることから、アルキレンテレフタレート単位を80重量%以上含有するポリアルキレンテレフタレートであることが好ましい。より好ましくは同単位を85重量%以上、更に好ましくは90重量%以上含有するポリアルキレンテレフタレートである。 The thermoplastic polyester resin (B) is preferably a polyalkylene terephthalate containing 80% by weight or more of an alkylene terephthalate unit because of excellent physical property balance (for example, molding processability) of the resulting resin composition. More preferred is a polyalkylene terephthalate containing the same unit in an amount of 85% by weight or more, and still more preferably 90% by weight or more.
熱可塑性ポリエステル系樹脂(B)は、フェノール/テトラクロロエタン=1/1(重量比)混合溶媒中、25℃で測定したときの対数粘度(IV)が0.30〜2.00dl/g以上であることが好ましい。対数粘度が0.30未満では、成形品の難燃性や機械的強度が不充分である場合が多く、2.00dl/gを超えると成形流動性が低下する傾向がある。より好ましくは0.40〜1.80dl/gであり、更に好ましくは0.50〜1.60dl/gである。 The thermoplastic polyester resin (B) has a logarithmic viscosity (IV) of 0.30 to 2.00 dl / g or more when measured at 25 ° C. in a mixed solvent of phenol / tetrachloroethane = 1/1 (weight ratio). Preferably there is. If the logarithmic viscosity is less than 0.30, the flame retardancy and mechanical strength of the molded product are often insufficient, and if it exceeds 2.00 dl / g, the molding fluidity tends to decrease. More preferably, it is 0.40-1.80 dl / g, More preferably, it is 0.50-1.60 dl / g.
本発明の熱可塑性樹脂組成物において、熱可塑性ポリエステル系樹脂(B)は1種類のみを単独で用いてもよいし、2種以上を組み合わせて使用してもよい。2種以上を組み合わせて使用する場合には、その組み合わせは特に限定されない。例えば、共重合成分やモル比が異なるもの、分子量が異なるもの等を任意に組み合わせることができる。 In the thermoplastic resin composition of the present invention, the thermoplastic polyester resin (B) may be used alone or in combination of two or more. When two or more types are used in combination, the combination is not particularly limited. For example, those having different copolymerization components and molar ratios, those having different molecular weights, and the like can be arbitrarily combined.
本発明の熱可塑性樹脂組成物に配合するポリカーボネート系樹脂(A)は、例えば2価以上のフェノール化合物と、ホスゲン又は炭酸ジエステルとを公知の方法で重合させて得られるポリカーボネートである。 The polycarbonate resin (A) to be blended in the thermoplastic resin composition of the present invention is a polycarbonate obtained by polymerizing, for example, a divalent or higher valent phenol compound and phosgene or a carbonic acid diester by a known method.
2価のフェノール化合物としては特に限定されず、例えば、2,2−ビス(4−ヒドロキシフェニル)プロパン〔通称:ビスフェノールA〕、ビス(4−ヒドロキシフェニル)メタン、ビス(4−ヒドロキシフェニル)フェニルメタン、ビス(4−ヒドロキシフェニル)ナフチルメタン、ビス(4−ヒドロキシフェニル)−(4−イソプロピルフェニル)メタン、ビス(3,5−ジメチル−4−ヒドロキシフェニル)メタン、1,1−ビス(4−ヒドロキシフェニル)エタン、1−ナフチル−1,1−ビス(4−ヒドロキシフェニル)エタン、1−フェニル−1,1−ビス(4−ヒドロキシフェニル)エタン、1,2−ビス(4−ヒドロキシフェニル)エタン、2−メチル−1,1−ビス(4−ヒドロキシフェニル)プロパン、2,2−ビス(3,5−ジメチル−4−ヒドロキシフェニル)プロパン、1−エチル−1,1−ビス(4−ヒドロキシフェニル)プロパン、2,2−ビス(3−メチル−4−ヒドロキシフェニル)プロパン、1,1−ビス(4−ヒドロキシフェニル)ブタン、2,2−ビス(4−ヒドロキシフェニル)ブタン、1,4−ビス(4−ヒドロキシフェニル)ブタン、2,2−ビス(4−ヒドロキシフェニル)ペンタン、4−メチル−2,2−ビス(4−ヒドロキシフェニル)ペンタン、2,2−ビス(4−ヒドロキシフェニル)ヘキサン、4,4−ビス(4−ヒドロキシフェニル)ヘプタン、2,2−ビス(4−ヒドロキシフェニル)ノナン、1,10−ビス(4−ヒドロキシフェニル)デカン、1,1−ビス(4−ヒドロキシフェニル)−3,3,5−トリメチルシクロヘキサン等のジヒドロキシジアリールアルカン類;1,1−ビス(4−ヒドロキシフェニル)シクロヘキサン、1,1−ビス(4−ヒドロキシフェニル)シクロデカン等のジヒドロキシジアリールシクロアルカン類;ビス(4−ヒドロキシフェニル)スルホン、ビス(3,5−ジメチル−4−ヒドロキシフェニル)スルホン等のジヒドロキシジアリールスルホン類;ビス(4−ヒドロキシフェニル)エーテル、ビス(3,5−ジメチル−4−ヒドロキシフェニル)エーテル等のジヒドロキシジアリールエーテル類;4,4′−ジヒドロキシベンゾフェノン、3,3′,5,5′−テトラメチル−4,4′−ジヒドロキシベンゾフェノン等のジヒドロキシジアリールケトン類;ビス(4−ヒドロキシフェニル)スルフィド、ビス(3−メチル−4−ヒドロキシフェニル)スルフィド、ビス(3,5−ジメチル−4−ヒドロキシフェニル)スルフィド等のジヒドロキシジアリールスルフィド類;ビス(4−ヒドロキシフェニル)スルホキシド等のジヒドロキシジアリールスルホキシド類;4,4′−ジヒロキシジフェニル等のジヒドロキシジフェニル類;9,9−ビス(4−ヒドロキシフェニル)フルオレン等のジヒドロキシアリールフルオレン類;ヒドロキノン、レゾルシノール、メチルヒドロキノン等のジヒドロキシベンゼン類;1,5−ジヒドロキシナフタレン、2,6−ジヒドロキシナフタレン等のジヒドロキシナフタレン類;等を挙げることができる。これらは単独で用いてもよく、2種以上を併用してもよい。 The divalent phenol compound is not particularly limited. For example, 2,2-bis (4-hydroxyphenyl) propane [common name: bisphenol A], bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenyl Methane, bis (4-hydroxyphenyl) naphthylmethane, bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 1,1-bis (4 -Hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ) Ethane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis 3,5-dimethyl-4-hydroxyphenyl) propane, 1-ethyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1 -Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane, 1,4-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 4 -Methyl-2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) hexane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4- Hydroxyphenyl) nonane, 1,10-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) -3,3,5-tri Dihydroxydiarylalkanes such as tilcyclohexane; dihydroxydiarylcycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl) cyclodecane; bis (4-hydroxyphenyl) sulfone Dihydroxydiaryl sulfones such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfone; dihydroxydiaryl ethers such as bis (4-hydroxyphenyl) ether and bis (3,5-dimethyl-4-hydroxyphenyl) ether Dihydroxydiaryl ketones such as 4,4′-dihydroxybenzophenone and 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybenzophenone; bis (4-hydroxyphenyl) sulfide, bis (3 -Dihydroxydiaryl sulfides such as methyl-4-hydroxyphenyl) sulfide and bis (3,5-dimethyl-4-hydroxyphenyl) sulfide; Dihydroxydiaryl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide; Dihydroxydiphenyls such as dihydroxydiphenyl; dihydroxyarylfluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene; dihydroxybenzenes such as hydroquinone, resorcinol and methylhydroquinone; 1,5-dihydroxynaphthalene, 2, Dihydroxynaphthalene such as 6-dihydroxynaphthalene; and the like. These may be used alone or in combination of two or more.
なかでも、ビスフェノールAが好適である。炭酸ジエステルとしては特に限定されず、例えば、ジフェニルカーボネート等のジアリールカーボネート;ジメチルカーボネート,ジエチルカーボネート等のジアルキルカーボネート;等を挙げることができる。これらは単独で用いてもよく、2種以上を併用してもよい。 Of these, bisphenol A is preferred. The carbonic acid diester is not particularly limited, and examples thereof include diaryl carbonates such as diphenyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; These may be used alone or in combination of two or more.
ポリカーボネート系樹脂(A)は、直鎖状のポリカーボネートに限定されず、分岐状のポリカーボネートであってもよい。この分岐状ポリカーボネートを得るために用いられる分岐剤としては特に限定されず、例えば、フロログルシン、メリト酸、トリメリト酸、トリメリト酸クロリド、無水トリメリト酸、没食子酸、没食子酸n−プロピル、プロトカテク酸、ピロメリト酸、ピロメリト酸二無水物、α−レゾルシン酸、β−レゾルシン酸、レゾルシンアルデヒド、1,3−ビス(o−クレゾール)、ベンゾフェノンテトラカルボン酸、2,4,4′−トリヒドロ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、2,4,4′−トリヒドロキシフェニルエーテル、2,2′,4,4′−テトラヒドロキシフェニルエーテル、2,4,4′−トリヒドロキシジフェニル−2−プロパン、2,2′−ビス(2,4−ジヒドロキシフェニル)プロパン、2,2′,4,4′−テトラヒドロキシジフェニルメタン、2,4,4′−トリヒドロキシジフェニルメタン、1−〔α−メチル−α−(4′−ジヒドロキシフェニル)エチル〕−3−〔α′,α′−ビス(4″−ヒドロキシフェニル)エチル〕ベンゼン、1−〔α−メチル−α−(4′−ジヒドロキシフェニル)エチル〕−4−〔α′,α′−ビス(4″−ヒドロキシフェニル)エチル〕ベンゼン、α,α′,α″−トリス(4−ヒドロキシフェニル)−1,3,5−トリイソプロピルベンゼン、2,6−ビス(2−ヒドロキシ−5′−メチルベンジル)−4−メチルフェノール、4,6−ジメチル−2,4,6−トリス(4′−ヒドロキシフェニル)−2−ヘプテン、4,6−ジメチル−2,4,6−トリス(4′−ヒドロキシフェニル)−ヘプタン、1,3,5−トリス(4′−ヒドロキシフェニル)ベンゼン、1,1,1−トリス(4−ヒドロキシフェニル)エタン、2,2−ビス〔4,4−ビス(4′−ヒドロキシフェニル)シクロヘキシル〕プロパン、2,6−ビス(2′−ヒドロキシ−5′−イソプロピルベンジル)−4−イソプロピルフェノール、ビス〔2−ヒドロキシ−3−(2′−ヒドロキシ−5′−メチルベンジル)−5−メチルフェニル〕メタン、ビス〔2−ヒドロキシ−3−(2′−ヒドロキシ−5′−イソプロピルベンジル)−5−メチルフェニル〕メタン、テトラキス(4−ヒドロキシフェニル)メタン、トリス(4−ヒドロキシフェニル)フェニルメタン、2′,4′,7−トリヒドロキシフラバン、2,4,4−トリメチル−2′,4′,7−トリヒドロキシフラバン、1,3−ビス(2′,4′−ジヒドロキシフェニルイソプロピル)ベンゼン、トリス(4′−ヒドロキシフェニル)−アミル−s−トリアジン等が挙げられる。 The polycarbonate resin (A) is not limited to a linear polycarbonate, and may be a branched polycarbonate. The branching agent used to obtain this branched polycarbonate is not particularly limited. For example, phloroglucin, mellitic acid, trimellitic acid, trimellitic acid chloride, trimellitic anhydride, gallic acid, n-propyl gallate, protocatechuic acid, pyromellitic acid Acid, pyromellitic dianhydride, α-resorcinic acid, β-resorcinic acid, resorcinaldehyde, 1,3-bis (o-cresol), benzophenone tetracarboxylic acid, 2,4,4′-trihydroxybenzophenone, 2, 2 ', 4,4'-tetrahydroxybenzophenone, 2,4,4'-trihydroxyphenyl ether, 2,2', 4,4'-tetrahydroxyphenyl ether, 2,4,4'-trihydroxydiphenyl- 2-propane, 2,2'-bis (2,4-dihydroxyphenyl) Propane, 2,2 ', 4,4'-tetrahydroxydiphenylmethane, 2,4,4'-trihydroxydiphenylmethane, 1- [α-methyl-α- (4'-dihydroxyphenyl) ethyl] -3- [α ', Α'-bis (4 "-hydroxyphenyl) ethyl] benzene, 1- [α-methyl-α- (4'-dihydroxyphenyl) ethyl] -4- [α', α'-bis (4"- Hydroxyphenyl) ethyl] benzene, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 2,6-bis (2-hydroxy-5′-methylbenzyl)- 4-methylphenol, 4,6-dimethyl-2,4,6-tris (4'-hydroxyphenyl) -2-heptene, 4,6-dimethyl-2,4,6-tris (4'-hydroxypheny L) -heptane, 1,3,5-tris (4'-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 2,2-bis [4,4-bis (4 ' -Hydroxyphenyl) cyclohexyl] propane, 2,6-bis (2'-hydroxy-5'-isopropylbenzyl) -4-isopropylphenol, bis [2-hydroxy-3- (2'-hydroxy-5'-methylbenzyl) ) -5-methylphenyl] methane, bis [2-hydroxy-3- (2'-hydroxy-5'-isopropylbenzyl) -5-methylphenyl] methane, tetrakis (4-hydroxyphenyl) methane, tris (4- Hydroxyphenyl) phenylmethane, 2 ', 4', 7-trihydroxyflavan, 2,4,4-trimethyl-2 ', 4', 7 Trihydroxyflavan, 1,3-bis (2 ', 4'-dihydroxyphenyl) benzene, tris (4'-hydroxyphenyl) - amyl -s- triazine.
場合によっては、ポリカーボネート系樹脂(A)は、ポリカーボネート部とポリオルガノシロキサン部とからなるポリカーボネート−ポリオルガノシロキサン共重合体であってもよい。この際、ポリオルガノシロキサン部の重合度は5以上であることが好ましい。 In some cases, the polycarbonate-based resin (A) may be a polycarbonate-polyorganosiloxane copolymer composed of a polycarbonate portion and a polyorganosiloxane portion. At this time, the degree of polymerization of the polyorganosiloxane portion is preferably 5 or more.
更にポリカーボネート系樹脂(A)は、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、デカンジカルボン酸等の直鎖状脂肪族二価カルボン酸を共重合させることにより得られるポリカーボネート系共重合体であってもよい。 Further, the polycarbonate resin (A) is obtained by copolymerizing a linear aliphatic dicarboxylic acid such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and decanedicarboxylic acid. It may be a coalescence.
ポリカーボネート系樹脂(A)を重合する際に用いる末端停止剤としては、公知のものを各種使用することができる。具体的には、フェノール、p−クレゾール、p−t−ブチルフェノール、p−t−オクチルフェノール、p−クミルフェノール、ノニルフェノール等の一価フェノール等が挙げられる。 As a terminal stopper used when polymerizing the polycarbonate resin (A), various known ones can be used. Specific examples include monohydric phenols such as phenol, p-cresol, pt-butylphenol, pt-octylphenol, p-cumylphenol, and nonylphenol.
難燃性を必要とする場合には、ポリカーボネート系樹脂(A)は、リン化合物とのポリカーボネート系共重合体であってもよいし、リン系化合物で末端封止したポリカーボネート系樹脂であってもよい。また、耐候性を高めるためには、ベンゾトリアゾール基を有する二価フェノールとのポリカーボネート系共重合体であってもよい。 When flame retardancy is required, the polycarbonate resin (A) may be a polycarbonate copolymer with a phosphorus compound, or may be a polycarbonate resin end-capped with a phosphorus compound. Good. Moreover, in order to improve a weather resistance, the polycarbonate-type copolymer with the bihydric phenol which has a benzotriazole group may be sufficient.
本発明の熱可塑性樹脂組成物に配合されるポリカーボネート系樹脂(A)の粘度平均分子量は、10000〜60000であることが好ましい。10000未満の場合、得られる樹脂組成物の強度や耐熱性等が不充分である場合が多い。一方60000を超えると、成形加工性が不充分である場合が多い。より好ましくは15000〜45000であり、更に好ましくは18000〜35000である。 The viscosity average molecular weight of the polycarbonate resin (A) blended in the thermoplastic resin composition of the present invention is preferably 10,000 to 60,000. When it is less than 10,000, the strength, heat resistance, etc. of the resulting resin composition are often insufficient. On the other hand, if it exceeds 60000, the moldability is often insufficient. More preferably, it is 15000-45000, More preferably, it is 18000-35000.
本発明の熱可塑性樹脂組成物において、ポリカーボネート系樹脂(A)は1種類のみを単独で用いてもよいし、2種以上を組み合わせて使用してもよい。2種以上を組み合わせて使用する場合には、その組み合わせは特に限定されない。例えば、モノマー単位が異なるもの、共重合モル比が異なるもの、分子量が異なるもの等を任意に組み合わせることができる。 In the thermoplastic resin composition of the present invention, the polycarbonate resin (A) may be used alone or in combination of two or more. When two or more types are used in combination, the combination is not particularly limited. For example, different monomer units, different copolymer molar ratios, different molecular weights, and the like can be arbitrarily combined.
本発明の熱可塑性樹脂組成物においては、熱可塑性ポリエステル系樹脂(B)単体で、あるいはポリカーボネート系樹脂(A)と熱可塑性ポリエステル系樹脂(B)との併用で、その効果を発揮するものである。ポリカーボネート系樹脂(A)と熱可塑性ポリエステル系樹脂(B)とを併用する場合に、その比率[(A)/(B)]は、体積比で、0/100〜85/15の範囲が好ましいが、さらに好ましくは15/85〜85/15の範囲である。15/85未満の場合でも、高熱伝導率を有しながら、押出成形性やブロー成形性にも優れた熱可塑性樹脂組成物をえることができるが、15/85以上とすることでさらに寸法安定性や耐衝撃性等を改善する効果がある。一方85/15を超えると、得られる成形品の熱安定性や耐溶剤性等が低下する傾向がある。 In the thermoplastic resin composition of the present invention, the thermoplastic polyester resin (B) alone or a combination of the polycarbonate resin (A) and the thermoplastic polyester resin (B) exerts its effect. is there. When the polycarbonate resin (A) and the thermoplastic polyester resin (B) are used in combination, the ratio [(A) / (B)] is preferably in the range of 0/100 to 85/15 in volume ratio. Is more preferably in the range of 15/85 to 85/15. Even in the case of less than 15/85, it is possible to obtain a thermoplastic resin composition excellent in extrusion moldability and blow moldability while having high thermal conductivity. It has the effect of improving the properties and impact resistance. On the other hand, when it exceeds 85/15, the thermal stability and solvent resistance of the obtained molded product tend to be lowered.
単体での熱伝導率が5W/m・K以上を示す高熱伝導性無機化合物(C)としては、公知の高熱伝導性無機化合物を広く使用できる。高熱伝導性無機化合物(C)単体での熱伝導率が5W/m・K未満では、組成物の熱伝導率を向上させる効果に劣るため好ましくない。(C)単体での熱伝導率は、好ましくは12W/m・K以上、さらに好ましくは15W/m・K以上、最も好ましくは20W/m・K以上、特に好ましくは30W/m・K以上のものが用いられる。高熱伝導性無機化合物(C)単体での熱伝導率の上限は特に制限されず、高ければ高いほど好ましいが、一般的には3000W/m・K以下、さらには2500W/m・K以下、のものが好ましく用いられる。 As the high thermal conductivity inorganic compound (C) having a single thermal conductivity of 5 W / m · K or more, known high thermal conductivity inorganic compounds can be widely used. If the thermal conductivity of the high thermal conductivity inorganic compound (C) alone is less than 5 W / m · K, the effect of improving the thermal conductivity of the composition is inferior. (C) The thermal conductivity of the single substance is preferably 12 W / m · K or more, more preferably 15 W / m · K or more, most preferably 20 W / m · K or more, particularly preferably 30 W / m · K or more. Things are used. The upper limit of the thermal conductivity of the high thermal conductivity inorganic compound (C) alone is not particularly limited and is preferably as high as possible, but is generally 3000 W / m · K or less, more preferably 2500 W / m · K or less. Those are preferably used.
成形体として特に電気絶縁性が要求されない用途に用いる場合には、導電性の高熱伝導性無機化合物としては金属系化合物や導電性炭素化合物等を用いることができる。導電性炭素化合物としては、熱伝導性に優れることから、グラファイト、炭素繊維をあげることができる。金属系化合物としては、導電性金属粉、導電性金属繊維、フェライト類、金属酸化物、等の高熱伝導性無機化合物を好ましく用いることができる。導電性金属粉としては各種金属を微粒子化した導電性金属粉、導電性金属繊維としては各種金属を繊維状に加工した導電性金属繊維、フェライト類としては軟磁性フェライト等の各種フェライト類、金属酸化物としては酸化亜鉛、等の金属酸化物、等の高熱伝導性無機化合物があげられる。 In the case where the molded body is used in applications where electrical insulation is not particularly required, a metal-based compound, a conductive carbon compound, or the like can be used as the conductive highly thermally conductive inorganic compound. Examples of the conductive carbon compound include graphite and carbon fiber because of excellent thermal conductivity. As the metal compound, highly heat conductive inorganic compounds such as conductive metal powders, conductive metal fibers, ferrites, and metal oxides can be preferably used. As conductive metal powder, conductive metal powder obtained by atomizing various metals, as conductive metal fiber, conductive metal fiber obtained by processing various metals into fibers, as ferrite, various ferrites such as soft magnetic ferrite, metal Examples of the oxide include highly thermally conductive inorganic compounds such as metal oxides such as zinc oxide.
中でも、グラファイト、導電性金属粉、軟磁性フェライト、炭素繊維、導電性金属繊維、酸化亜鉛、からなる群より選ばれる1種以上の導電性の高熱伝導性無機化合物が好ましい。 Among these, one or more conductive high thermal conductive inorganic compounds selected from the group consisting of graphite, conductive metal powder, soft magnetic ferrite, carbon fiber, conductive metal fiber, and zinc oxide are preferable.
成形体として電気絶縁性が要求される用途に用いる場合には、高熱伝導性無機化合物としては電気絶縁性を示す化合物が好ましく用いられる。電気絶縁性とは具体的には、電気抵抗率1Ω・cm以上のものを示すこととするが、好ましくは10Ω・cm以上、より好ましくは105Ω・cm以上、さらに好ましくは1010Ω・cm以上、最も好ましくは1013Ω・cm以上のものを用いるのが好ましい。電気抵抗率の上限には特に制限は無いが、一般的には1018Ω・cm以下である。本発明の高熱伝導性熱可塑性樹脂組成物から得られる成形体の電気絶縁性も上記範囲にあることが好ましい。 When the molded body is used for applications requiring electrical insulation, a compound exhibiting electrical insulation is preferably used as the highly thermally conductive inorganic compound. Specifically, the electrical insulating property indicates an electrical resistivity of 1 Ω · cm or more, preferably 10 Ω · cm or more, more preferably 10 5 Ω · cm or more, and further preferably 10 10 Ω · cm or more. It is preferable to use a material having a size of cm or more, most preferably 10 13 Ω · cm or more. There is no particular restriction on the upper limit of the electrical resistivity, generally less 10 18 Ω · cm. It is preferable that the electrical insulation of the molded product obtained from the high thermal conductivity thermoplastic resin composition of the present invention is also in the above range.
高熱伝導性無機化合物のうち、電気絶縁性を示す電気絶縁性高熱伝導性無機化合物としては金属酸化物、金属窒化物、金属炭化物、金属炭酸塩、絶縁性炭素材料、金属水酸化物、を例示することができる。金属酸化物としては酸化アルミニウム、酸化マグネシウム、酸化ケイ素、酸化ベリリウム、酸化銅、亜酸化銅をあげることができる。金属窒化物としては窒化ホウ素、窒化アルミニウム、窒化ケイ素をあげることができる。 Among the high thermal conductive inorganic compounds, examples of the electrically insulating high thermal conductive inorganic compounds exhibiting electrical insulation include metal oxides, metal nitrides, metal carbides, metal carbonates, insulating carbon materials, and metal hydroxides. can do. Examples of the metal oxide include aluminum oxide, magnesium oxide, silicon oxide, beryllium oxide, copper oxide, and cuprous oxide. Examples of the metal nitride include boron nitride, aluminum nitride, and silicon nitride.
金属炭化物としては炭化ケイ素を、金属炭酸塩としては炭酸マグネシウムを、絶縁性炭素材料としてはダイヤモンドを、金属水酸化物としては水酸化アルミニウム、水酸化マグネシウムをあげることができる。 Examples of the metal carbide include silicon carbide, examples of the metal carbonate include magnesium carbonate, examples of the insulating carbon material include diamond, and examples of the metal hydroxide include aluminum hydroxide and magnesium hydroxide.
中でも、窒化ホウ素、窒化アルミニウム、窒化ケイ素、酸化アルミニウム、酸化マグネシウム、炭酸マグネシウム、水酸化アルミニウム、水酸化マグネシウム、酸化ベリリウム、ダイヤモンド、からなる群より選ばれる1種以上の電気絶縁性高熱伝導性無機化合物が好ましい。これらは単独あるいは複数種類を組み合わせて用いることができる。 Among them, one or more electrically insulating high heat conductive inorganic substances selected from the group consisting of boron nitride, aluminum nitride, silicon nitride, aluminum oxide, magnesium oxide, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, beryllium oxide, and diamond Compounds are preferred. These can be used alone or in combination.
高熱伝導性無機化合物の形状については、種々の形状のものを適応可能である。例えば粒子状、微粒子状、ナノ粒子、凝集粒子状、チューブ状、ナノチューブ状、ワイヤ状、ロッド状、針状、板状、不定形、ラグビーボール状、六面体状、大粒子と微小粒子とが複合化した複合粒子状、液体、等種々の形状を例示することができる。またこれら高熱伝導性無機化合物は天然物であってもよいし、合成されたものであってもよい。天然物の場合、産地等には特に限定はなく、適宜選択することができる。これら高熱伝導性無機化合物は、1種類のみを単独で用いてもよいし、形状、平均粒子径、種類、表面処理剤等が異なる2種以上を併用してもよい。 Various shapes can be applied to the shape of the high thermal conductive inorganic compound. For example, particles, fine particles, nanoparticles, aggregated particles, tubes, nanotubes, wires, rods, needles, plates, irregular shapes, rugby balls, hexahedrons, large particles and fine particles are combined Various shapes such as a composite particle shape, a liquid, etc. can be exemplified. These high thermal conductivity inorganic compounds may be natural products or synthesized ones. In the case of a natural product, there are no particular limitations on the production area and the like, which can be selected as appropriate. These high thermal conductive inorganic compounds may be used alone or in combination of two or more different shapes, average particle diameters, types, surface treatment agents, and the like.
これら高熱伝導性無機化合物は、樹脂と無機化合物との界面の接着性を高めたり、作業性を容易にしたりするため、表面処理剤で表面処理がなされたものであってもよい。表面処理剤としては特に限定されず、例えばシランカップリング剤、チタネートカップリング剤、等従来公知のものを使用することができる。中でもエポキシシラン等のエポキシ基含有シランカップリング剤、及び、アミノシラン等のアミノ基含有シランカップリング剤、ポリオキシエチレンシラン、等が樹脂の物性を低下させることが少ないため好ましい。無機化合物の表面処理方法としては特に限定されず、通常の処理方法を利用できる。 These highly heat-conductive inorganic compounds may be those that have been surface-treated with a surface treatment agent in order to enhance the adhesion at the interface between the resin and the inorganic compound or to facilitate workability. It does not specifically limit as a surface treating agent, For example, conventionally well-known things, such as a silane coupling agent and a titanate coupling agent, can be used. Among them, an epoxy group-containing silane coupling agent such as epoxy silane, an amino group-containing silane coupling agent such as aminosilane, polyoxyethylene silane, and the like are preferable because they hardly reduce the physical properties of the resin. The surface treatment method of the inorganic compound is not particularly limited, and a normal treatment method can be used.
本発明に用いられる、(D)分子内にカルボキシル基又はそのエステル形成性誘導体基を3個以上有する化合物及び/又はその酸無水物化合物は、樹脂組成物の溶融張力が著しく向上し、良好な押出成形性やブロー成形性を得るために用いられる。 The compound (D) having 3 or more carboxyl groups or ester-forming derivative groups thereof in the molecule and / or acid anhydride compound thereof used in the present invention has a significantly improved melt tension of the resin composition and is excellent. Used to obtain extrusion moldability and blow moldability.
上記化合物としては、炭素数9〜30の3価以上の芳香族多価カルボン酸、炭素数5〜20の3価以上の脂肪族多価カルボン酸、炭素数9〜30の3価以上の脂環式多価カルボン酸、などの多価カルボン酸類及びこれらのエステル形成性誘導体、及び/又はその酸無水物が挙げられる。これらの化合物は、分子内にカルボキシル基以外に、水酸基を有するものであってもよい。添加する化合物が、カルボキシル基の数が2個以下のカルボン酸である場合には、得られた組成物の押出成形性やブロー成形性の改善効果が得られない場合がある。 Examples of the compound include trivalent or higher aromatic polyvalent carboxylic acids having 9 to 30 carbon atoms, trivalent or higher aliphatic polyvalent carboxylic acids having 5 to 20 carbon atoms, and trivalent or higher fats having 9 to 30 carbon atoms. Examples thereof include polyvalent carboxylic acids such as cyclic polyvalent carboxylic acids and ester-forming derivatives thereof, and / or acid anhydrides thereof. These compounds may have a hydroxyl group in addition to a carboxyl group in the molecule. When the compound to be added is a carboxylic acid having 2 or less carboxyl groups, there are cases where the effect of improving the extrusion moldability and blow moldability of the obtained composition cannot be obtained.
これらの具体例としては、トリメシン酸、トリメリット酸、トリメリット酸無水物、塩化トリメリット酸無水物、ヘミメリット酸無水物、ピロメリット酸、ピロメリット酸一無水物、ピロメリット酸二無水物、ナフタレンテトラカルボン酸、ナフタレンテトラカルボン酸二無水物、3,3′,4,4′−ベンゾフェノンテトラカルボン酸、3,3′,4,4′−ベンゾフェノンテトラカルボン酸二無水物、ビス(3,4−ジカルボキシフェニル)メタン二無水物、ビス(3,4−ジカルボキシフェニル)エタン二無水物、1,2,3−プロパントリカルボン酸、1,2,3−プロペントリカルボン酸、1,2,4−ブタントリカルボン酸、1,2,3,4−ブタンテトラカルボン酸、無水クエン酸、1,2,4,5−シクロヘキサンテトラカルボン酸、1,2,4,5−シクロヘキサンテトラカルボン酸二無水物等が挙げられ、これらは単独又は2種以上組み合わせて用いられる。 Specific examples of these include trimesic acid, trimellitic acid, trimellitic anhydride, chlorotrimellitic anhydride, hemimellitic anhydride, pyromellitic acid, pyromellitic monoanhydride, pyromellitic dianhydride , Naphthalenetetracarboxylic acid, naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, bis (3 , 4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3-propanetricarboxylic acid, 1,2,3-propenetricarboxylic acid, 1,2 , 4-butanetricarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, anhydrous citric acid, 1,2,4,5-cyclohexanetetracarbonate Bon acid, 1,2,4,5-cyclohexane tetracarboxylic acid dianhydride and the like, which may be used alone or in combination of two or more.
中でも、分子内にカルボキシル基又はそのエステル形成性誘導体基を3個以上有する芳香族多価カルボン酸又はその誘導体、及び/又はその酸無水物が、取り扱いが容易であるうえ、得られた組成物の押出成形性やブロー成形性がより向上するため好ましい。さらに、酸無水物基を分子内に2個以上有する芳香族カルボン酸無水物であることが、(A)ポリカーボネート系樹脂や(B)芳香族ポリエステル系樹脂の分解を防ぐことができるため特に好ましい。これらの化合物の例としては、ピロメリット酸二無水物、ナフタレンテトラカルボン酸二無水物、3,3′,4,4′−ベンゾフェノンテトラカルボン酸二無水物、等が挙げられる。 Among them, an aromatic polyvalent carboxylic acid having 3 or more carboxyl groups or ester-forming derivative groups in the molecule or a derivative thereof, and / or an acid anhydride thereof is easy to handle, and the resulting composition This is preferable because the extrusion moldability and blow moldability are improved. Furthermore, an aromatic carboxylic acid anhydride having two or more acid anhydride groups in the molecule is particularly preferable because (A) polycarbonate resin and (B) aromatic polyester resin can be prevented from being decomposed. . Examples of these compounds include pyromellitic dianhydride, naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, and the like.
(D)成分の添加量は、前記(B)(C)の合計100重量部、または前記(A)(B)(C)の合計100重量部に対し、0.01〜15重量部、好ましくは0.05〜10重量部、さらに好ましくは0.08〜7重量部、最も好ましくは0.1〜4重量部である。添加量が0.01重量部未満では成形性、耐衝撃性、耐溶剤性、等の改良効果が小さく、15重量部を超えると成形加工が困難となる傾向がある。
本発明の樹脂組成物には、前記の高熱伝導性無機化合物以外にも、その目的に応じて公知の無機充填剤を広く使用できる。
Component (D) is added in an amount of 0.01 to 15 parts by weight, preferably 100 parts by weight of (B) and (C) or 100 parts by weight of (A), (B) and (C). Is 0.05 to 10 parts by weight, more preferably 0.08 to 7 parts by weight, and most preferably 0.1 to 4 parts by weight. If the addition amount is less than 0.01 parts by weight, the effect of improving moldability, impact resistance, solvent resistance, etc. is small, and if it exceeds 15 parts by weight, the molding process tends to be difficult.
In the resin composition of the present invention, known inorganic fillers can be widely used depending on the purpose in addition to the above-described highly thermally conductive inorganic compound.
高熱伝導性無機化合物以外の無機充填剤としては、例えばケイソウ土粉;塩基性ケイ酸マグネシウム;焼成クレイ;微粉末シリカ;石英粉末;結晶シリカ;カオリン;タルク;三酸化アンチモン;微粉末マイカ;二硫化モリブデン;ロックウール;セラミック繊維;アスベストなどの無機質繊維;およびガラス繊維、ガラスパウダー、ガラスクロス、溶融シリカ等ガラス製充填剤が挙げられる。 Examples of inorganic fillers other than the high thermal conductivity inorganic compound include diatomaceous earth powder; basic magnesium silicate; calcined clay; fine powder silica; quartz powder; crystalline silica; kaolin; talc; antimony trioxide; Examples thereof include molybdenum sulfide; rock wool; ceramic fiber; inorganic fiber such as asbestos; and glass fillers such as glass fiber, glass powder, glass cloth, and fused silica.
これら充填剤を用いることで、例えば熱伝導性、機械強度、または耐摩耗性など樹脂組成物を応用する上で好ましい特性を向上させることが可能となる。さらに必要に応じて紙、パルプ、木料;ポリアミド繊維、アラミド繊維、ボロン繊維などの合成繊維;ポリオレフィン粉末等の樹脂粉末;などの有機充填剤を併用して配合することができる。 By using these fillers, for example, it is possible to improve favorable characteristics in applying a resin composition such as thermal conductivity, mechanical strength, or abrasion resistance. Further, if necessary, organic fillers such as paper, pulp, wood, synthetic fibers such as polyamide fiber, aramid fiber, and boron fiber; resin powder such as polyolefin powder; can be used in combination.
本発明の高熱伝導性熱可塑性樹脂組成物に含まれる、非繊維状無機充填剤(例えば六方晶窒化ホウ素粉末)と無機質繊維(例えばガラス繊維)の体積比は、通常100/0〜20/80であるが、好ましくは100/0〜35/65、より好ましくは90/10〜50/50である。 The volume ratio of the non-fibrous inorganic filler (for example, hexagonal boron nitride powder) and the inorganic fiber (for example, glass fiber) contained in the high thermal conductivity thermoplastic resin composition of the present invention is usually 100/0 to 20/80. However, it is preferably 100/0 to 35/65, more preferably 90/10 to 50/50.
本発明の樹脂組成物には、本発明の効果の発揮を失わない範囲で、エポキシ樹脂、ポリオレフィン樹脂、スチレン系樹脂、液晶ポリマー、ビスマレイミド樹脂、ポリイミド樹脂、ポリエーテル樹脂、フェノール樹脂、シリコーン樹脂、ポリアミド樹脂、ポリエステル樹脂、フッ素樹脂、アクリル樹脂、メラミン樹脂、ユリア樹脂、ウレタン樹脂等いかなる公知の樹脂も含有させて構わない。好ましい樹脂の具体例として、液晶ポリマー、ナイロン6、ナイロン6,6、MBS樹脂、MB樹脂、ABS樹脂、AAS樹脂、AES樹脂、オレフィン系弾性樹脂、等が挙げられる。これら樹脂を併用する場合その使用量は、通常樹脂組成物に含まれる熱可塑性樹脂(A)100重量部に対し、0〜10000重量部の範囲が例示でき好ましい。 The resin composition of the present invention includes an epoxy resin, a polyolefin resin, a styrene resin, a liquid crystal polymer, a bismaleimide resin, a polyimide resin, a polyether resin, a phenol resin, and a silicone resin as long as the effects of the present invention are not lost. Any known resin such as polyamide resin, polyester resin, fluorine resin, acrylic resin, melamine resin, urea resin, urethane resin may be contained. Specific examples of preferred resins include liquid crystal polymer, nylon 6, nylon 6,6, MBS resin, MB resin, ABS resin, AAS resin, AES resin, olefin elastic resin, and the like. When these resins are used in combination, the amount used is preferably from 0 to 10,000 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A) usually contained in the resin composition.
本発明の樹脂材料には、上記樹脂や充填剤以外の添加剤として、さらに目的に応じて他のいかなる成分、例えば、補強剤、増粘剤、離型剤、カップリング剤、難燃剤、耐炎剤、顔料、着色剤、その他の助剤等を本発明の効果を失わない範囲で、添加することができる。これらの添加剤の使用量は、熱可塑性樹脂100重量部に対し、合計で0〜200重量部の範囲であることが好ましい。 In the resin material of the present invention, as an additive other than the above resin and filler, any other components depending on the purpose, for example, reinforcing agent, thickener, release agent, coupling agent, flame retardant, flame resistance Agents, pigments, colorants, other auxiliaries and the like can be added as long as the effects of the present invention are not lost. The amount of these additives used is preferably in the range of 0 to 200 parts by weight in total with respect to 100 parts by weight of the thermoplastic resin.
本発明の組成物の製造方法としては特に限定されるものではない。例えば、上述した成分や添加剤等を乾燥させた後、単軸、2軸等の押出機のような溶融混練機にて溶融混練することにより製造することができる。また、配合成分が液体である場合は、液体供給ポンプ等を用いて溶融混練機に途中添加して製造することもできる。 The method for producing the composition of the present invention is not particularly limited. For example, it can be produced by drying the above-described components, additives and the like and then melt-kneading them in a melt-kneader such as a single-screw or twin-screw extruder. Moreover, when a compounding component is a liquid, it can also manufacture by adding to a melt-kneader on the way using a liquid supply pump etc.
本発明の組成物は、その優れた熱伝導性と成形品外観とから、高熱伝導性押出成形品や高熱伝導性プロー成形品として好適に使用可能であり、成形加工方法としては押出成形やブロー成形が適している。 The composition of the present invention can be suitably used as a highly heat-conductive extruded product or a highly heat-conductive pro-molded product because of its excellent heat conductivity and appearance of the molded product. Molding is suitable.
使用形態としては、樹脂フィルム、樹脂成形品、樹脂発泡体、塗料やコーティング剤、等さまざまな形態を例示することができる。成形加工法としては例えば、射出成形、押出成形、真空成形、プレス成形、カレンダー成形、ブロー成形、等が利用できる。 Examples of usage forms include various forms such as a resin film, a resin molded product, a resin foam, a paint and a coating agent. As the molding method, for example, injection molding, extrusion molding, vacuum molding, press molding, calendar molding, blow molding, or the like can be used.
本発明で得られた高熱伝導性熱可塑性樹脂組成物は押出成形性に優れるため、現在広く用いられている押出成形機が使用可能であり、異型形状を有する長尺製品、シートやフィルム形状への連続成形、などであっても成形が容易である。またブロー成形性にも優れるため、現在広く用いられているブロー成形機が使用可能であり、中空の三次元形状を有する製品などであっても成形が容易である。 Since the highly heat-conductive thermoplastic resin composition obtained in the present invention is excellent in extrusion moldability, currently widely used extrusion molding machines can be used, and can be used for long products having irregular shapes, sheets and film shapes. Even if it is continuous molding, etc., molding is easy. Moreover, since it is excellent in blow moldability, a blow molding machine widely used at present can be used, and even a product having a hollow three-dimensional shape can be easily molded.
本発明において、製品として用いられる成形体を押出成形により得る際の、シリンダー温度は、通常、240〜320℃で、好ましくは255〜295℃である。この際のダイス温度は、通常、40〜300℃で、好ましくは80〜290℃である。 In the present invention, the cylinder temperature when a molded body used as a product is obtained by extrusion molding is usually 240 to 320 ° C, preferably 255 to 295 ° C. The die temperature in this case is 40-300 degreeC normally, Preferably it is 80-290 degreeC.
また本発明において、製品として用いられる成形体をブロー成形により得る際の、パリソン温度は、通常、240〜320℃で、好ましくは255〜295℃である。この際の金型温度は、通常、40〜180℃で、好ましくは60〜150℃である。 Moreover, in this invention, the parison temperature at the time of obtaining the molded object used as a product by blow molding is 240-320 degreeC normally, Preferably it is 255-295 degreeC. The mold temperature at this time is usually 40 to 180 ° C, preferably 60 to 150 ° C.
本発明の熱可塑性樹脂組成物は、電子材料、磁性材料、触媒材料、構造体材料、光学材料、医療材料、自動車材料、建築材料、等の各種の用途に幅広く用いることが可能である。特に優れた成形品外観、高熱伝導性、という優れた特性を併せ持つことから、放熱・伝熱用の樹脂材料として、非常に有用である。 The thermoplastic resin composition of the present invention can be widely used for various applications such as electronic materials, magnetic materials, catalyst materials, structural materials, optical materials, medical materials, automobile materials, and building materials. In particular, since it has excellent properties such as excellent appearance of molded products and high thermal conductivity, it is very useful as a resin material for heat dissipation and heat transfer.
本発明の熱可塑性樹脂組成物は、LED照明などの照明部材、家電、OA機器部品、AV機器部品、自動車内外装部品、等の射出成形品等に好適に使用することができる。特に多くの熱を発する家電製品やOA機器において、外装材料として好適に用いることができる。さらには発熱源を内部に有するがファン等による強制冷却が困難な電子機器において、内部で発生する熱を外部へ放熱するために、これらの機器の外装材として好適に用いられる。 The thermoplastic resin composition of the present invention can be suitably used for injection molded products such as lighting members such as LED lighting, home appliances, OA equipment parts, AV equipment parts, automobile interior and exterior parts, and the like. In particular, it can be suitably used as an exterior material in home appliances and office automation equipment that generate a lot of heat. Furthermore, in an electronic device having a heat source inside but difficult to be forcibly cooled by a fan or the like, it is suitably used as an exterior material for these devices in order to dissipate the heat generated inside to the outside.
これらの中でも好ましい装置として、ノートパソコンなどの携帯型コンピューター、PDA、携帯電話、携帯ゲーム機、携帯型音楽プレーヤー、携帯型TV/ビデオ機器、携帯型ビデオカメラ、等の小型あるいは携帯型電子機器類の筐体、ハウジング、外装材用樹脂として非常に有用である。また自動車や電車等におけるバッテリー周辺用樹脂、家電機器の携帯バッテリー用樹脂、ブレーカー等の配電部品用樹脂、モーター等の封止用材料、としても非常に有用に用いることができる。 Among these, small or portable electronic devices such as portable computers such as notebook computers, PDAs, cellular phones, portable game machines, portable music players, portable TV / video devices, portable video cameras, etc. are preferable among these. It is very useful as a resin for housings, housings, and exterior materials. It can also be used very effectively as a resin for battery peripherals in automobiles, trains, etc., a resin for portable batteries in home appliances, a resin for power distribution parts such as breakers, and a sealing material for motors.
本発明の押出成形用高熱伝導性熱可塑性樹脂組成物は従来良く知られている組成物に比べて、高熱伝導性無機物の配合量を減らすことができるため成形加工性が良好であり、上記の用途における基板などの部品あるいは筐体用として有用な特性を有するものである。 The high heat conductive thermoplastic resin composition for extrusion molding of the present invention has a good molding processability because the amount of the high heat conductive inorganic substance can be reduced as compared with a conventionally well-known composition. It has characteristics useful as a component such as a substrate in an application or a housing.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
[評価方法]
[熱伝導率] : 得られた押出成形品やブロー成形品から30mm角×3.0mm厚みの板柱状試験片を2個切り出し、京都電子工業製ホットディスク法熱伝導率測定装置で4φのセンサーにて熱伝導率を測定した。
[Evaluation method]
[Thermal conductivity]: Two plate columnar test pieces of 30 mm square x 3.0 mm thickness were cut out from the obtained extrusion molded product or blow molded product, and a 4φ sensor was used with a hot disk method thermal conductivity measuring device manufactured by Kyoto Electronics Industry Co., Ltd. The thermal conductivity was measured at
[成形品外観] : 得られた押出成形品表面における凹凸やフィラー浮きなどの外観不良を目視にて観察し、以下の基準で評価した。◎:外観非常に良好、○:外観良好、△:一部外観不良が見られるがほぼ良好、×:外観不良。 [Appearance of molded product]: Appearance defects such as irregularities and filler floating on the surface of the obtained extruded product were visually observed and evaluated according to the following criteria. A: Appearance is very good, B: Appearance is good, B: Appearance is partially good but almost good, B: Appearance is poor.
(実施例1)
熱可塑性ポリエステル系樹脂(B)として三菱化学(株)製のポリエチレンテレフタレート樹脂であるPBK−2(B−1)を用いた。(B−1)100重量部に対して、(D)化合物として、ピロメリット酸二無水物(以下D−1と略す。)を0.5重量部、並びに、安定剤としてアデカスタブAO−60及びアデカスタブAO−412S(いずれも(株)ADEKA製商品名)各0.2重量部をスーパーフローターにて混合した(原料1)。
Example 1
PBK-2 (B-1), which is a polyethylene terephthalate resin manufactured by Mitsubishi Chemical Corporation, was used as the thermoplastic polyester resin (B). (B-1) With respect to 100 parts by weight, 0.5 parts by weight of pyromellitic dianhydride (hereinafter abbreviated as D-1) as the compound (D), and ADK STAB AO-60 as a stabilizer and Adeka Stub AO-412S (both trade names manufactured by ADEKA Corporation) 0.2 parts by weight were mixed in a super floater (raw material 1).
別途高熱伝導性無機化合物(C)として六方晶窒化ホウ素粉末(電気化学工業(株)製SGP、単体での熱伝導率が60W/m・K、体積平均粒子径21.0μm、電気絶縁性)(C−1)と、その他充填剤としてガラス繊維(日本電気硝子(株)製T−187H/PL)(GF−1)とを用い、両者を体積比で(C−1)/(GF−1)=35/15となるよう混合した(原料2)。 Separately, hexagonal boron nitride powder (SGP manufactured by Denki Kagaku Kogyo Co., Ltd., thermal conductivity of 60 W / m · K, volume average particle diameter 21.0 μm, electrical insulation) as highly heat conductive inorganic compound (C) (C-1) and glass fibers (T-187H / PL manufactured by Nippon Electric Glass Co., Ltd.) (GF-1) as other fillers, both of which are (C-1) / (GF- 1) It mixed so that it might become = 35/15 (raw material 2).
原料1を、日本製鋼所製TEX44同方向噛み合い型二軸押出機のスクリュー根本付近に設けられた第一供給口であるホッパーより投入した。第二供給口の手前位置に、スクリューに角度90℃のニーディングディスクを挿入し、ニーディングディスク部が終了した位置に、大気圧に開放されたベント口を設けた。ベント口のすぐ隣にサイドフィーダーを設置し、サイドフィーダーにて第二供給口より原料2を強制圧入した。両供給口からの供給量を制御することにより、原料1と原料2とが体積比率で45/55となるよう混合した。 The raw material 1 was supplied from a hopper which is a first supply port provided in the vicinity of a screw base of a TEX44 co-meshing twin screw extruder manufactured by Nippon Steel Works. A kneading disc having an angle of 90 ° C. was inserted into the screw at a position before the second supply port, and a vent port opened to atmospheric pressure was provided at a position where the kneading disc portion was completed. A side feeder was installed right next to the vent port, and the raw material 2 was forcibly pressed from the second supply port with the side feeder. By controlling the supply amount from both supply ports, the raw material 1 and the raw material 2 were mixed so as to have a volume ratio of 45/55.
第二供給口とスクリュー先端との中間部に、減圧ポンプに接続された減圧ベント口を設けた。スクリュー回転数150rpm、時間あたり吐出量を50kg/hrに設定した。設定温度は第一供給口近傍が100℃で、順次設定温度を上昇させ、ニーディングディスク部手前を270℃に設定した。ニーディングディスク部から大気圧開放ベント口までを270℃に、大気圧開放ベント口から第二供給口までを275℃に、第二供給口からスクリュー先端部までを270℃に設定した。本条件にて成形用高熱伝導性熱可塑性樹脂組成物を得た。 A decompression vent port connected to a decompression pump was provided at an intermediate portion between the second supply port and the screw tip. The screw rotation speed was set to 150 rpm and the discharge amount per hour was set to 50 kg / hr. The set temperature was 100 ° C. in the vicinity of the first supply port, and the set temperature was sequentially increased, and the front of the kneading disk was set to 270 ° C. The temperature from the kneading disk part to the atmospheric pressure release vent port was set to 270 ° C., the pressure from the atmospheric pressure release vent port to the second supply port was set to 275 ° C., and the distance from the second supply port to the screw tip was set to 270 ° C. Under these conditions, a high heat conductive thermoplastic resin composition for molding was obtained.
得られた組成物を130℃で4時間乾燥後、大阪精機工作製40mm単軸押出機10VSE−40−28Vを用いて押出成形を実施した。成形条件は、シリンダー温度270℃、ダイス温度255℃に設定し、ダイスより出てきた樹脂をダイスから5cm離した場所に設置したサイジングダイス(設定温度120℃)を通した後に引取りを行い押出加工を実施したところ、押出成形性は概ね良好であった。ダイス出口及びサイジングダイスの出入り口形状を図1に示す。 The obtained composition was dried at 130 ° C. for 4 hours, and then subjected to extrusion molding using a 40 mm single-screw extruder 10VSE-40-28V manufactured by Osaka Seiki. Molding conditions were set at a cylinder temperature of 270 ° C and a die temperature of 255 ° C, and after passing through a sizing die (set temperature of 120 ° C) placed 5 cm away from the die, it was taken out and extruded When the processing was carried out, the extrusion moldability was generally good. The shape of the entrance / exit of the die outlet and the sizing die is shown in FIG.
得られた成形品の熱伝導率を評価した結果、押出成形品外観:○、熱伝導率:3.2W/mK、であった。
得られた組成物をプラコー株式会社製のDA−50型ブロー成形機で60mm×60mm×100mm、平均肉厚2.5mmの四角柱状中空成形体をブロー成形した。成形条件は、パリソン温度約270℃、射出速度(指数)150、スクリュー回転数60rpm、ブロー圧0.59MPa(窒素)、冷却時間100秒、金型温度120℃に設定したところ、ブロー成形性は概ね良好であった。成形品を評価した結果、ブロー成形品外観:○、熱伝導率:3.2W/mK、であった。
As a result of evaluating the thermal conductivity of the obtained molded product, the appearance of the extruded molded product was ◯, and the thermal conductivity was 3.2 W / mK.
The obtained composition was blow molded into a square columnar hollow molded body of 60 mm × 60 mm × 100 mm and an average thickness of 2.5 mm with a DA-50 type blow molding machine manufactured by Plako Corporation. The molding conditions were set to a parison temperature of about 270 ° C., an injection speed (index) of 150, a screw rotation speed of 60 rpm, a blow pressure of 0.59 MPa (nitrogen), a cooling time of 100 seconds, and a mold temperature of 120 ° C. It was generally good. As a result of evaluating the molded product, the appearance of the blow molded product was ◯, and the thermal conductivity was 3.2 W / mK.
(実施例2)
ポリカーボネート系樹脂(A)として、出光興産(株)製ビスフェノールA型ポリカーボネート樹脂である、タフロンA−2200(A−1)を、熱可塑性ポリエステル系樹脂(B)として三菱化学(株)製のポリエチレンテレフタレート樹脂であるPBK−2(B−1)を用い、両者を体積比で(A−1)/(B−1)=30/20となるよう混合した。両者の合計100重量部に対して、(D)化合物として、ピロメリット酸二無水物(以下D−1と略す。)を0.5重量部、並びに、安定剤としてアデカスタブAO−60及びアデカスタブHP−10(いずれも(株)ADEKA製商品名)各0.2重量部をスーパーフローターにて混合した(原料1)。
(Example 2)
As polycarbonate resin (A), Teflon A-2200 (A-1), which is a bisphenol A type polycarbonate resin manufactured by Idemitsu Kosan Co., Ltd., and polyethylene manufactured by Mitsubishi Chemical Co., Ltd. as thermoplastic polyester resin (B). PBK-2 (B-1) which is a terephthalate resin was used, and both were mixed so that the volume ratio was (A-1) / (B-1) = 30/20. 0.5 parts by weight of pyromellitic dianhydride (hereinafter abbreviated as D-1) as the compound (D) and 100 parts by weight of Adeka Stub AO-60 and Adeka Stub HP as stabilizers with respect to 100 parts by weight of both. -10 (all trade names made by ADEKA Corporation) 0.2 parts by weight were mixed in a super floater (raw material 1).
別途高熱伝導性無機化合物(C)として六方晶窒化ホウ素粉末(電気化学工業(株)製SGP、単体での熱伝導率が60W/m・K、体積平均粒子径21.0μm、電気絶縁性)(C−1)と、その他充填剤としてガラス繊維(日本電気硝子(株)製T−187H/PL)(GF−1)とを用い、両者を体積比で(C−1)/(GF−1)=30/20となるよう混合した(原料2)。 Separately, hexagonal boron nitride powder (SGP manufactured by Denki Kagaku Kogyo Co., Ltd., thermal conductivity of 60 W / m · K, volume average particle diameter 21.0 μm, electrical insulation) as highly heat conductive inorganic compound (C) (C-1) and glass fibers (T-187H / PL manufactured by Nippon Electric Glass Co., Ltd.) (GF-1) as other fillers, both of which are (C-1) / (GF- 1) It mixed so that it might become = 30/20 (raw material 2).
原料1を、日本製鋼所製TEX44同方向噛み合い型二軸押出機のスクリュー根本付近に設けられた第一供給口であるホッパーより投入した。第二供給口の手前位置に、スクリューに角度90℃のニーディングディスクを挿入し、ニーディングディスク部が終了した位置に、大気圧に開放されたベント口を設けた。ベント口のすぐ隣にサイドフィーダーを設置し、サイドフィーダーにて第二供給口より原料2を強制圧入した。両供給口からの供給量を制御することにより、原料1と原料2とが体積比率で1/1となるよう混合した。 The raw material 1 was supplied from a hopper which is a first supply port provided in the vicinity of a screw base of a TEX44 co-meshing twin screw extruder manufactured by Nippon Steel Works. A kneading disc having an angle of 90 ° C. was inserted into the screw at a position before the second supply port, and a vent port opened to atmospheric pressure was provided at a position where the kneading disc portion was completed. A side feeder was installed right next to the vent port, and the raw material 2 was forcibly pressed from the second supply port with the side feeder. By controlling the supply amounts from both supply ports, the raw material 1 and the raw material 2 were mixed so that the volume ratio was 1/1.
第二供給口とスクリュー先端との中間部に、減圧ポンプに接続された減圧ベント口を設けた。スクリュー回転数150rpm、時間あたり吐出量を50kg/hrに設定した。設定温度は第一供給口近傍が100℃で、順次設定温度を上昇させ、ニーディングディスク部手前を270℃に設定した。ニーディングディスク部から大気圧開放ベント口までを270℃に、大気圧開放ベント口から第二供給口までを275℃に、第二供給口からスクリュー先端部までを270℃に設定した。本条件にて成形用高熱伝導性熱可塑性樹脂組成物を得た。 A decompression vent port connected to a decompression pump was provided at an intermediate portion between the second supply port and the screw tip. The screw rotation speed was set to 150 rpm and the discharge amount per hour was set to 50 kg / hr. The set temperature was 100 ° C. in the vicinity of the first supply port, and the set temperature was sequentially increased, and the front of the kneading disk was set to 270 ° C. The temperature from the kneading disk part to the atmospheric pressure release vent port was set to 270 ° C., the pressure from the atmospheric pressure release vent port to the second supply port was set to 275 ° C., and the distance from the second supply port to the screw tip was set to 270 ° C. Under these conditions, a high heat conductive thermoplastic resin composition for molding was obtained.
得られた組成物を130℃で4時間乾燥後、大阪精機工作製40mm単軸押出機10VSE−40−28Vを用いて押出成形を実施した。成形条件は、シリンダー温度260℃、ダイス温度245℃に設定し、ダイスより出てきた樹脂をダイスから5cm離した場所に設置したサイジングダイス(設定温度90℃)を通した後に引取りを行い押出加工を実施したところ、押出成形性は良好であった。ダイス出口及びサイジングダイスの出入り口形状を図1に示す。 The obtained composition was dried at 130 ° C. for 4 hours, and then subjected to extrusion molding using a 40 mm single-screw extruder 10VSE-40-28V manufactured by Osaka Seiki. Molding conditions were set at a cylinder temperature of 260 ° C and a die temperature of 245 ° C, and after passing through a sizing die (set temperature of 90 ° C) placed 5 cm away from the die, it was taken out and extruded When the processing was carried out, the extrusion moldability was good. The shape of the entrance / exit of the die outlet and the sizing die is shown in FIG.
得られた成形品の熱伝導率を評価した結果、押出成形品外観:◎、熱伝導率:1.5W/mK、であった。
得られた組成物をプラコー株式会社製のDA−50型ブロー成形機で60mm×60mm×100mm、平均肉厚2.5mmの四角柱状中空成形体をブロー成形した。成形条件は、パリソン温度約260℃、射出速度(指数)150、スクリュー回転数60rpm、ブロー圧0.59MPa(窒素)、冷却時間100秒、金型温度90℃に設定したところ、ブロー成形性は良好であった。成形品を評価した結果、ブロー成形品外観:◎、熱伝導率:1.5W/mK、であった。
As a result of evaluating the thermal conductivity of the obtained molded product, the appearance of the extruded product was ◎, and the thermal conductivity was 1.5 W / mK.
The obtained composition was blow molded into a square columnar hollow molded body of 60 mm × 60 mm × 100 mm and an average thickness of 2.5 mm with a DA-50 type blow molding machine manufactured by Plako Corporation. Molding conditions were set at a parison temperature of about 260 ° C., an injection speed (index) of 150, a screw rotation speed of 60 rpm, a blow pressure of 0.59 MPa (nitrogen), a cooling time of 100 seconds, and a mold temperature of 90 ° C. It was good. As a result of evaluating the molded product, the appearance of the blow molded product was ◎, and the thermal conductivity was 1.5 W / mK.
(実施例3)
(D−1)の代わりに、(D−2)ナフタレンテトラカルボン酸二無水物を用いた以外は実施例2と同様に評価を行った。結果、押出成形性:良好、押出成形品外観:◎、熱伝導率:1.4W/mK、ブロー成形性:良好、ブロー成形品外観:◎、熱伝導率:1.4W/mK、であった。
(Example 3)
Evaluation was performed in the same manner as in Example 2 except that (D-2) naphthalenetetracarboxylic dianhydride was used instead of (D-1). Results, extrusion moldability: good, extrusion molded product appearance: :, thermal conductivity: 1.4 W / mK, blow moldability: good, blow molded product appearance: 、, thermal conductivity: 1.4 W / mK. It was.
(実施例4)
(A−1)の代わりに、(A−2):ポリカーボネート樹脂(出光興産(株)製ビスフェノールA型ポリカーボネート樹脂である、タフロンA−2500)を用いた以外は実施例2と同様に評価を行った。結果、押出成形性:良好、押出成形品外観:◎、熱伝導率:1.5W/mK、ブロー成形性:良好、ブロー成形品外観:◎、熱伝導率:1.5W/mK、であった。
Example 4
Evaluation was performed in the same manner as in Example 2 except that (A-2): polycarbonate resin (Taflon A-2500, which is a bisphenol A type polycarbonate resin manufactured by Idemitsu Kosan Co., Ltd.) was used instead of (A-1). went. Results, extrusion moldability: good, extrusion molded product appearance: :, thermal conductivity: 1.5 W / mK, blow moldability: good, blow molded product appearance: 、, thermal conductivity: 1.5 W / mK. It was.
(実施例5)
(B−1)の代わりに、(B−2):対数粘度0.85(25℃、dl/g、フェノール/テトラクロロエタン=1/1(重量比))のポリブチレンテレフタレート樹脂を用いた以外は実施例2と同様に評価を行った。結果、押出成形性:良好、押出成形品外観:◎、熱伝導率:1.6W/mK、ブロー成形性:良好、ブロー成形品外観:◎、熱伝導率:1.6W/mK、であった。
(Example 5)
Instead of (B-2), (B-2): other than using polybutylene terephthalate resin having a logarithmic viscosity of 0.85 (25 ° C., dl / g, phenol / tetrachloroethane = 1/1 (weight ratio)) Were evaluated in the same manner as in Example 2. Results, extrusion moldability: good, extrusion molded product appearance: :, thermal conductivity: 1.6 W / mK, blow moldability: good, blow molded product appearance: 、, thermal conductivity: 1.6 W / mK. It was.
(実施例6)
(C−1)の代わりに、(C−2):丸み状アルミナ粉末(昭和電工(株)製AS−40、単体での熱伝導率36W/m・K、体積平均粒子径20μm、電気絶縁性)を用いた以外は実施例2と同様に評価を行った。結果、押出成形性:良好、押出成形品外観:◎、熱伝導率:1.1W/mK、ブロー成形性:良好、ブロー成形品外観:◎、熱伝導率:1.1W/mK、であった。
(Example 6)
Instead of (C-1), (C-2): rounded alumina powder (AS-40 manufactured by Showa Denko KK, single body thermal conductivity 36 W / m · K, volume average particle diameter 20 μm, electrical insulation Evaluation was carried out in the same manner as in Example 2 except that the property was used. Result, extrusion moldability: good, extrusion molded product appearance: :, thermal conductivity: 1.1 W / mK, blow moldability: good, blow molded product appearance: 、, thermal conductivity: 1.1 W / mK. It was.
(実施例7)
(C−1)の代わりに、(C−3):窒化ホウ素粉末(モメンティブパフォーマンスマテリアルズ製PT−110、単体での熱伝導率80W/m・K、体積平均粒子径36μm、電気絶縁性)を用いた以外は実施例2と同様に評価を行った。結果、押出成形性:良好、押出成形品外観:◎、熱伝導率:1.8W/mK、ブロー成形性:良好、ブロー成形品外観:◎、熱伝導率:1.8W/mK、であった。
(Example 7)
Instead of (C-1), (C-3): Boron nitride powder (PT-110 manufactured by Momentive Performance Materials, thermal conductivity of 80 W / m · K alone, volume average particle diameter of 36 μm, electrical insulation) Evaluation was performed in the same manner as in Example 2 except that was used. Result, extrusion moldability: good, extrusion molded product appearance: :, thermal conductivity: 1.8 W / mK, blow moldability: good, blow molded product appearance: 、, thermal conductivity: 1.8 W / mK. It was.
(比較例1)
(D−1)を添加しなかった以外は実施例2と同様に評価を行った。結果、押出成形性:不良、押出成形品外観:×、熱伝導率:1.5W/mK、ブロー成形性:不良、ブロー成形品外観:×、熱伝導率:1.5W/mK、であった。
以上から本発明の熱可塑性樹脂組成物は、諸物性と熱伝導率とのバランスに優れた高熱伝導性熱可塑性樹脂組成物が得られ、かつ押出成形性やブロー成形性に優れることが分かる。
(Comparative Example 1)
Evaluation was performed in the same manner as in Example 2 except that (D-1) was not added. Result, extrusion moldability: poor, extrusion molded product appearance: x, thermal conductivity: 1.5 W / mK, blow moldability: poor, blow molded product appearance: x, thermal conductivity: 1.5 W / mK. It was.
From the above, it can be seen that the thermoplastic resin composition of the present invention provides a high thermal conductivity thermoplastic resin composition excellent in the balance between various physical properties and thermal conductivity, and is excellent in extrusion moldability and blow moldability.
(比較例2)
(C−1)を添加しなかった以外は実施例2と同様に評価を行った。結果、押出成形性:良好、押出成形品外観:◎、熱伝導率:0.2W/mK、ブロー成形性:良好、ブロー成形品外観:◎○、熱伝導率:0.2W/mK、となり、熱伝導率は汎用の樹脂とほぼ同等であった。
(Comparative Example 2)
Evaluation was performed in the same manner as in Example 2 except that (C-1) was not added. Result, extrusion moldability: good, extrusion molded product appearance: :, thermal conductivity: 0.2 W / mK, blow moldability: good, blow molded product appearance: :, thermal conductivity: 0.2 W / mK The thermal conductivity was almost the same as that of general-purpose resins.
以上から本発明の熱可塑性樹脂組成物は、諸物性と熱伝導率とのバランスに優れた高熱伝導性熱可塑性樹脂組成物が得られ、かつ押出成形性やブロー成形性に優れることが分かる。 From the above, it can be seen that the thermoplastic resin composition of the present invention provides a high thermal conductivity thermoplastic resin composition excellent in the balance between various physical properties and thermal conductivity, and is excellent in extrusion moldability and blow moldability.
Claims (3)
上記(D)がナフタレンテトラカルボン酸二無水物であり、
上記(D)の添加量は、上記(B)と上記(C)との合計100重量部に対し0.05〜10重量部であることを特徴とする、高熱伝導性熱可塑性樹脂組成物。 Thermoplastic polyester resin (B), high thermal conductivity inorganic compound (C) having a thermal conductivity of 5 W / m · K or more alone, and having three or more carboxyl groups or ester-forming derivative groups in the molecule compounds and Ri name of at least one organic compound (D) selected from the group consisting of acid anhydride thereof,
(D) is naphthalenetetracarboxylic dianhydride,
The amount of the (D) added is 0.05 to 10 parts by weight with respect to 100 parts by weight as a total of the above (B) and the above (C) , A high thermal conductive thermoplastic resin composition.
上記(D)がナフタレンテトラカルボン酸二無水物であり、
上記(D)の添加量は、上記(A)と、上記(B)と、上記(C)との合計100重量部に対し0.05〜10重量部であることを特徴とする、高熱伝導性熱可塑性樹脂組成物。 Polycarbonate-based resin (A), thermoplastic polyester-based resin (B), highly thermally conductive inorganic compound (C) having a thermal conductivity of 5 W / m · K or more as a simple substance, carboxyl group in the molecule or ester formation thereof Ri Na from the compound having a derivative group 3 or more and at least one organic compound selected from the group consisting of an acid anhydride thereof (D),
(D) is naphthalenetetracarboxylic dianhydride,
The addition amount of (D) is 0.05 to 10 parts by weight with respect to 100 parts by weight in total of (A), (B), and (C). Thermoplastic resin composition.
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US20080277619A1 (en) * | 2005-12-09 | 2008-11-13 | Kazuaki Matsumoto | Thermoplastic Resin Composition with High Thermal Conductivity |
DE502007002446D1 (en) * | 2006-10-12 | 2010-02-04 | Basf Se | HEAT-RESISTANT POLYESTER MOLDING |
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