JP2007277299A - Copolymer composition - Google Patents
Copolymer composition Download PDFInfo
- Publication number
- JP2007277299A JP2007277299A JP2006102110A JP2006102110A JP2007277299A JP 2007277299 A JP2007277299 A JP 2007277299A JP 2006102110 A JP2006102110 A JP 2006102110A JP 2006102110 A JP2006102110 A JP 2006102110A JP 2007277299 A JP2007277299 A JP 2007277299A
- Authority
- JP
- Japan
- Prior art keywords
- component
- mass
- copolymer
- group
- vinyl aromatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 165
- 239000000203 mixture Substances 0.000 title claims abstract description 69
- -1 vinyl aromatic compound Chemical class 0.000 claims abstract description 94
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 87
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229920000642 polymer Polymers 0.000 claims abstract description 50
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 27
- 150000001993 dienes Chemical class 0.000 claims abstract description 26
- 239000011787 zinc oxide Substances 0.000 claims abstract description 23
- 125000000524 functional group Chemical group 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 19
- 239000000194 fatty acid Substances 0.000 claims abstract description 19
- 229930195729 fatty acid Natural products 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 18
- 238000000465 moulding Methods 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 150000002430 hydrocarbons Chemical group 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 125000003277 amino group Chemical group 0.000 claims description 17
- 125000003700 epoxy group Chemical group 0.000 claims description 17
- 125000005372 silanol group Chemical group 0.000 claims description 17
- 239000007822 coupling agent Substances 0.000 claims description 10
- 239000010690 paraffinic oil Substances 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000011231 conductive filler Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000003607 modifier Substances 0.000 claims description 7
- 239000011342 resin composition Substances 0.000 claims description 7
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 229920006026 co-polymeric resin Polymers 0.000 claims description 5
- 150000002900 organolithium compounds Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000002685 polymerization catalyst Substances 0.000 claims description 4
- 229920005604 random copolymer Polymers 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 35
- 238000000034 method Methods 0.000 description 26
- 238000006116 polymerization reaction Methods 0.000 description 23
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 18
- 230000017525 heat dissipation Effects 0.000 description 17
- 238000002425 crystallisation Methods 0.000 description 15
- 230000008025 crystallization Effects 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- 239000004793 Polystyrene Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 150000001339 alkali metal compounds Chemical class 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 229910052582 BN Inorganic materials 0.000 description 5
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 150000004767 nitrides Chemical class 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N pentadecanoic acid Chemical compound CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- 239000004945 silicone rubber Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- RCJMVGJKROQDCB-UHFFFAOYSA-N 2-methylpenta-1,3-diene Chemical compound CC=CC(C)=C RCJMVGJKROQDCB-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 2
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 2
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methylcycloheptane Chemical compound CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- QCEOZLISXJGWSW-UHFFFAOYSA-K 1,2,3,4,5-pentamethylcyclopentane;trichlorotitanium Chemical compound [Cl-].[Cl-].[Cl-].CC1=C(C)C(C)([Ti+3])C(C)=C1C QCEOZLISXJGWSW-UHFFFAOYSA-K 0.000 description 1
- HIACAHMKXQESOV-UHFFFAOYSA-N 1,2-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=CC=C1C(C)=C HIACAHMKXQESOV-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- NYCCIHSMVNRABA-UHFFFAOYSA-N 1,3-diethylimidazolidin-2-one Chemical compound CCN1CCN(CC)C1=O NYCCIHSMVNRABA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- UYMQPNRUQXPLCY-UHFFFAOYSA-N 1-(2-piperidin-1-ylethyl)piperidine Chemical compound C1CCCCN1CCN1CCCCC1 UYMQPNRUQXPLCY-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- DFNXHHNFURNWAF-UHFFFAOYSA-N 1-n,4-n-dioctylbenzene-1,4-diamine Chemical compound CCCCCCCCNC1=CC=C(NCCCCCCCC)C=C1 DFNXHHNFURNWAF-UHFFFAOYSA-N 0.000 description 1
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- BBLDTXFLAHKYFJ-UHFFFAOYSA-N 2,2,5,5-tetramethyloxolane Chemical compound CC1(C)CCC(C)(C)O1 BBLDTXFLAHKYFJ-UHFFFAOYSA-N 0.000 description 1
- OXMIDRBAFOEOQT-UHFFFAOYSA-N 2,5-dimethyloxolane Chemical compound CC1CCC(C)O1 OXMIDRBAFOEOQT-UHFFFAOYSA-N 0.000 description 1
- VKABKQBHBBROCU-UHFFFAOYSA-N 2-(2,2,3-trimethylpiperazin-1-yl)ethanamine Chemical compound CC1NCCN(CCN)C1(C)C VKABKQBHBBROCU-UHFFFAOYSA-N 0.000 description 1
- OHDSHGBRKMRPHC-UHFFFAOYSA-N 2-(4-ethenylphenyl)-n,n-dimethylethanamine Chemical compound CN(C)CCC1=CC=C(C=C)C=C1 OHDSHGBRKMRPHC-UHFFFAOYSA-N 0.000 description 1
- FXWRUNXMOLCZEE-UHFFFAOYSA-N 2-(4-ethenylphenyl)ethanamine Chemical compound NCCC1=CC=C(C=C)C=C1 FXWRUNXMOLCZEE-UHFFFAOYSA-N 0.000 description 1
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- CMVRXZWIGKJZKG-UHFFFAOYSA-N methyl-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]-diphenoxysilane Chemical compound C1CC2OC2CC1CC[Si](C)(OC=1C=CC=CC=1)OC1=CC=CC=C1 CMVRXZWIGKJZKG-UHFFFAOYSA-N 0.000 description 1
- VLKBRFNUOVSNJA-UHFFFAOYSA-N methyl-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]-dipropoxysilane Chemical compound C1C(CC[Si](C)(OCCC)OCCC)CCC2OC21 VLKBRFNUOVSNJA-UHFFFAOYSA-N 0.000 description 1
- ICCDZMWNLNRHGP-UHFFFAOYSA-N methyl-[3-(oxiran-2-ylmethoxy)propyl]-bis(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](C)(OC(C)=C)CCCOCC1CO1 ICCDZMWNLNRHGP-UHFFFAOYSA-N 0.000 description 1
- CUIXFHFVVWQXSW-UHFFFAOYSA-N methyl-[3-(oxiran-2-ylmethoxy)propyl]-diphenoxysilane Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(C)CCCOCC1CO1 CUIXFHFVVWQXSW-UHFFFAOYSA-N 0.000 description 1
- VOARQMXRPHXHID-UHFFFAOYSA-N methyl-[3-(oxiran-2-ylmethoxy)propyl]-dipropoxysilane Chemical compound CCCO[Si](C)(OCCC)CCCOCC1CO1 VOARQMXRPHXHID-UHFFFAOYSA-N 0.000 description 1
- UEQFSKQXQPIFDJ-UHFFFAOYSA-N methyl-bis[3-(oxiran-2-ylmethoxy)propyl]-phenoxysilane Chemical compound C1OC1COCCC[Si](OC=1C=CC=CC=1)(C)CCCOCC1CO1 UEQFSKQXQPIFDJ-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- DIHKMUNUGQVFES-UHFFFAOYSA-N n,n,n',n'-tetraethylethane-1,2-diamine Chemical compound CCN(CC)CCN(CC)CC DIHKMUNUGQVFES-UHFFFAOYSA-N 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 150000002901 organomagnesium compounds Chemical class 0.000 description 1
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 1
- 239000012285 osmium tetroxide Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- ODOPKAJVFRHHGM-UHFFFAOYSA-N phenyltin Chemical group [Sn]C1=CC=CC=C1 ODOPKAJVFRHHGM-UHFFFAOYSA-N 0.000 description 1
- 125000002270 phosphoric acid ester group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000002130 sulfonic acid ester group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- PEISWSSYWSVWHA-UHFFFAOYSA-K tert-butyl(trichloro)stannane Chemical compound CC(C)(C)[Sn](Cl)(Cl)Cl PEISWSSYWSVWHA-UHFFFAOYSA-K 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- AWIJRPNMLHPLNC-UHFFFAOYSA-N thiocarboxylic acid group Chemical group C(=S)O AWIJRPNMLHPLNC-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M thiocyanate group Chemical group [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 125000005068 thioepoxy group Chemical group S(O*)* 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical class Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- OAVPBWLGJVKEGZ-UHFFFAOYSA-N tributoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCCCC)(OCCCC)OCCCC)CCC2OC21 OAVPBWLGJVKEGZ-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFRLQYJXUZRYDN-UHFFFAOYSA-K trichloro(methyl)stannane Chemical compound C[Sn](Cl)(Cl)Cl YFRLQYJXUZRYDN-UHFFFAOYSA-K 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZQMPLYWXYJXIGG-UHFFFAOYSA-N triethyl-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethoxy]silane Chemical compound C1C(CCO[Si](CC)(CC)CC)CCC2OC21 ZQMPLYWXYJXIGG-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- LQZHZFUSFHLGHE-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)propyl]silane Chemical compound C1C(C(C)C[Si](OC)(OC)OC)CCC2OC21 LQZHZFUSFHLGHE-UHFFFAOYSA-N 0.000 description 1
- ZQPNGHDNBNMPON-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)butyl]silane Chemical compound CO[Si](OC)(OC)CCC(C)OCC1CO1 ZQPNGHDNBNMPON-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
本発明は、電子機器等の部品からの発熱を放熱させるために、優れた熱伝導性、柔軟性を備え、更にカレンダー成形加工時のシート破れや、厚みムラがなく、カレンダー成形加工性に優れた共重合体組成物及びそれを用いた放熱性に優れた樹脂シートに関するものである。 The present invention has excellent thermal conductivity and flexibility in order to dissipate heat generated from parts such as electronic devices, and further has excellent sheet forming workability without sheet breakage or thickness unevenness during the calendar forming process. The present invention relates to a copolymer composition and a resin sheet excellent in heat dissipation using the copolymer composition.
従来からデジタル家電の普及に伴い、電気部品・電子機器の高速化や高機能化の要求が高まってきている。しかしながら、これら電子部品や電子機器において、電子制御を行うＬＳＩやＣＰＵ等の電子素子は、コンピュータの集積度の増大及び動作の高速化により消費電力が増大し、それ故発熱量の増大により電子素子の不具合が生じる等問題を抱えており、放熱対策は不可欠なものとなっている。一般の電子機器における放熱は、ヒートシンクなどが取り付けられ、さらにヒートシンクを冷却ファン等により強制的に空冷することも行われている。ノート型パーソナルコンピュータを始めとする小型機器や、高密度実装される電子部品においては、冷却ファンなど設置する空間が小さいなど制約があり、シリコーングリースを塗布することにより放熱対策が行われていた。また電子部品に対する高性能化の要求に対応するため放熱シートを使用するケースが増加してきている。放熱シートはヒートシンクなどの冷却部品を発熱体に取り付ける際、両者間の接触を密にして熱を有効に冷却部品へ伝達させる目的で使用されている。 Conventionally, with the spread of digital home appliances, there is an increasing demand for higher speed and higher functionality of electrical components and electronic devices. However, in these electronic components and electronic devices, electronic elements such as LSIs and CPUs that perform electronic control have increased power consumption due to an increase in the degree of integration of computers and an increase in operation speed. Therefore, heat dissipation measures are indispensable. For heat dissipation in general electronic equipment, a heat sink or the like is attached, and the heat sink is forcibly cooled by a cooling fan or the like. Small devices such as notebook personal computers and electronic parts mounted with high density have limitations such as a small installation space such as a cooling fan, and measures against heat radiation have been taken by applying silicone grease. In addition, in order to meet the demand for higher performance of electronic components, the number of cases using heat dissipation sheets is increasing. The heat-dissipating sheet is used for the purpose of effectively transferring heat to the cooling component by attaching a close contact between the two when the cooling component such as a heat sink is attached to the heating element.
近年、各用途において、熱を拡散させるとした放熱性に優れた樹脂シートが求められている。これまで放熱シートはシリコーンゴムやシリコーンゲルシートをベースとした材料に比較的熱伝導性の高い充填材を充填させたものが使用されている。
しかしながら、シリコーン系グリスは高粘度の液状であるため、発熱部品に塗布する場合、塗布量の制御が難しく、また場合によっては発熱部品以外への付着、汚染の懸念がある。また、シリコーン樹脂は樹脂中に低分子シロキサンが含まれていることから、発熱体に取り付けて使用する場合、低分子シロキサンガスが発生し、該ガスが電極接点などへ付着して二酸化珪素が生成することが原因となって、接点不良を発生する可能性がある。
さらに、シリコーンゴムシートはシリコーン樹脂そのものが高価である他、加硫工程が必要であるため、シート製造の時に生じる余分なシートや、一度流通した使用したシートをリサイクルのため回収したとしても再度溶融成形加工して使用することは困難であることから、リサイクルが可能な熱可塑性の放熱シートが望まれている。
In recent years, in each application, a resin sheet excellent in heat dissipation property that diffuses heat has been demanded. So far, heat dissipation sheets have been used in which a material based on silicone rubber or silicone gel sheet is filled with a filler having relatively high thermal conductivity.
However, since silicone grease is a highly viscous liquid, it is difficult to control the amount applied when it is applied to a heat-generating component, and in some cases, there is a risk of adhesion to other heat-generating components or contamination. Silicone resin contains low-molecular siloxane in the resin, so when used attached to a heating element, low-molecular siloxane gas is generated and the gas adheres to electrode contacts, etc., generating silicon dioxide. This may cause contact failure.
Furthermore, because the silicone rubber sheet itself is expensive and requires a vulcanization process, it can be melted again even if an extra sheet generated during sheet production or a used sheet once distributed is collected for recycling. Since it is difficult to use after being molded, a thermoplastic heat radiation sheet that can be recycled is desired.
しかしながら、熱可塑性樹脂ベースで大量の熱伝導性充填材を配合すると、シート加工性が不十分で、満足のいくシートが出来ないのが現状である。
例えば、共役ジエンとビニル芳香族化合物からなる共重合体に水素添加してなる水添共重合体に酸化亜鉛および脂肪酸を充填した樹脂組成物が提案されている。これは材料の機械的強度の向上を目的としたものであり、酸化亜鉛の充填量が５０重量％以下であり、放熱性に関して何ら記述はない(例えば、特許文献１参照)。
また、熱可塑性樹脂に高濃度の充填材を含有させた組成物に、脂肪酸を添加する組成物が開示されている。これは、充填材の吸水性改良と押出機生産性改良を目的としたものであり、放熱性に関しては何ら記述は無い(例えば、特許文献２参照)。
さらにまた、スチレン系エラストマーに高濃度の熱伝導性充填剤を充填した樹脂組成物が開示されている。これはスチレン系エラストマーにオイルを添加することにより組成物の柔軟化を目的としたものであるが、添加剤による熱伝導性の改良や、成形性改良については、何ら記述は無い(例えば、特許文献３および４参照)。
For example, a resin composition has been proposed in which a hydrogenated copolymer obtained by hydrogenating a copolymer comprising a conjugated diene and a vinyl aromatic compound is filled with zinc oxide and a fatty acid. This is intended to improve the mechanical strength of the material, and the filling amount of zinc oxide is 50% by weight or less, and there is no description regarding heat dissipation (see, for example, Patent Document 1).
Moreover, the composition which adds a fatty acid to the composition which made the thermoplastic resin contain the high concentration filler is disclosed. This is for the purpose of improving the water absorption of the filler and improving the productivity of the extruder, and there is no description regarding heat dissipation (see, for example, Patent Document 2).
Furthermore, a resin composition in which a high-concentration heat conductive filler is filled in a styrene elastomer is disclosed. This is intended to soften the composition by adding oil to the styrenic elastomer, but there is no description of improvements in thermal conductivity and moldability by additives (for example, patents). References 3 and 4).
本発明は、上記の如き熱伝導性材料の抱える問題を解決するためになされたものであって、熱伝導性、柔軟性、カレンダ成形加工性に優れた共重合体組成物及びそれを用いた放熱性に優れた樹脂シートを提供することを課題とする。 The present invention has been made in order to solve the problems of the heat conductive material as described above, and uses a copolymer composition excellent in heat conductivity, flexibility, and calendar molding processability, and the same. It is an object to provide a resin sheet excellent in heat dissipation.
本発明は、共役ジエンとビニル芳香族化合物からなる共重合体に水素を添加してなる水添共重合体と、酸化亜鉛と、脂肪酸からなる組成物において、特定のビニル芳香族化合物含有量を有し、しかもビニル芳香族化合物重合体ブロックの含有量が特定の範囲にある水添共重合体または変性水添共重合体と、特殊形状すなわち、核部と、この核部から４軸方向に伸びた針状結晶である酸化亜鉛と、脂肪酸とにより、上記課題が効果的に解決されることを見出し、本発明を完成するに至った。 The present invention relates to a composition comprising a hydrogenated copolymer obtained by adding hydrogen to a copolymer comprising a conjugated diene and a vinyl aromatic compound, zinc oxide, and a fatty acid, and has a specific vinyl aromatic compound content. A hydrogenated copolymer or a modified hydrogenated copolymer having a vinyl aromatic compound polymer block content in a specific range, a special shape, that is, a core portion, and a four-axis direction from the core portion. It has been found that the above problem can be effectively solved by zinc oxide, which is an elongated needle crystal, and a fatty acid, and the present invention has been completed.
即ち、本発明は、
１． 共役ジエンとビニル芳香族化合物からなる共重合体に水素を添加してなる下記（ａ）〜（ｄ）を満たす水添共重合体（１）および／または共役ジエンとビニル芳香族化合物からなる共重合体に水素を添加してなり、かつ官能基を少なくとも１個結合する下記（ａ）〜（ｄ）を満たす変性水添共重合体（２）からなるスチレン系軟質樹脂５〜３５質量％および核部とこの核部から異なる４軸方向に伸びた針状結晶であることを特徴とする酸化亜鉛（３）６５〜９５質量％、かつ成分（１）〜（３）の合計量１００質量部に対して、炭素数８以上の脂肪酸（４）０．０１〜５．０質量部を含むことを特徴とする共重合体組成物、
（ａ）該成分（１）および／または（２）中の、ビニル芳香族化合物の含有量が５０質量％を越え、９０質量％以下、
（ｂ）該成分（１）および／または（２）中の、ビニル芳香族化合物重合体ブロックの量が４０質量％以下、
（ｃ）該成分（１）および／または（２）の水添共重合体の重量平均分子量が５万〜１００万、
（ｄ）該成分（１）および／または（２）中の、共役ジエン化合物に基づく二重結合の１０％以上が水添されている。
That is, the present invention
1. Hydrogenated copolymer (1) satisfying the following (a) to (d) by adding hydrogen to a copolymer comprising a conjugated diene and a vinyl aromatic compound and / or a copolymer comprising a conjugated diene and a vinyl aromatic compound. 5 to 35% by mass of a styrenic soft resin comprising a modified hydrogenated copolymer (2) formed by adding hydrogen to a polymer and satisfying the following (a) to (d) that binds at least one functional group: Zinc oxide (3) 65 to 95% by mass, and a total amount of components (1) to (3) of 100 parts by mass, characterized in that the core is a needle-like crystal extending in different four-axis directions from the core A copolymer composition characterized by containing 0.01 to 5.0 parts by mass of a fatty acid (4) having 8 or more carbon atoms,
(A) The content of the vinyl aromatic compound in the component (1) and / or (2) exceeds 50% by mass and is 90% by mass or less,
(B) The amount of the vinyl aromatic compound polymer block in the component (1) and / or (2) is 40% by mass or less,
(C) The weight average molecular weight of the hydrogenated copolymer of the component (1) and / or (2) is 50,000 to 1,000,000,
(D) 10% or more of the double bond based on the conjugated diene compound in the component (1) and / or (2) is hydrogenated.
２． 成分（１）および／または成分（２）からなるスチレン系軟質樹脂５〜３５質量％および成分（３）６５〜９５質量％、かつ成分（１）〜(３)の合計量１００質量部に対して、炭素数８以上の脂肪酸（４） ０．０１〜５．０質量部およびアクリル系樹脂（５）０．０１〜５．０質量部を含むことを特徴とする上記１に記載の共重合体組成物、
３． 成分（１）および／または成分（２）からなるスチレン系軟質樹脂が、さらにパラフィン系オイル（６）を含み、その配合割合が、成分（１）および／または成分（２）２６〜９９質量％および成分（６）１〜７４質量％であることを特徴とする上記１または２に記載の共重合体樹脂組成物、
４． 成分（１）および／または成分（２）からなるスチレン系軟質樹脂が、さらにパラフィン系オイル（６）と成分（３）以外の１０〜４００Ｗ／ｍ・Ｋの熱伝導性充填材（７）を含み、その配合割合が、成分（１）および／または成分（２）２４〜８５質量％、成分（６）１〜６６質量％および成分（３）以外の１０〜４００Ｗ／ｍ・Ｋの熱伝導性充填材（７）１０〜５０質量％であることを特徴とする上記１〜３のいずれか１項に記載の共重合体樹脂組成物、
2. 5 to 35% by mass of styrenic soft resin comprising component (1) and / or component (2), 65 to 95% by mass of component (3), and 100 parts by mass of the total amount of components (1) to (3) The co-polymer according to 1 above, comprising 0.01 to 5.0 parts by mass of a fatty acid (4) having 8 or more carbon atoms and 0.01 to 5.0 parts by mass of an acrylic resin (5) Coalescence composition,
3. The styrenic soft resin comprising the component (1) and / or the component (2) further contains a paraffinic oil (6), and the blending ratio thereof is 26 to 99% by mass of the component (1) and / or the component (2). And the copolymer resin composition as described in 1 or 2 above, wherein the component (6) is 1 to 74% by mass,
4). The styrenic soft resin comprising the component (1) and / or the component (2) further comprises a heat conductive filler (7) of 10 to 400 W / m · K other than the paraffinic oil (6) and the component (3). Including, component (1) and / or component (2) 24 to 85 mass%, component (6) 1 to 66 mass% and component (3) other than 10 to 400 W / m · K heat conduction Copolymer resin composition of any one of said 1-3 characterized by being 10-50 mass% of conductive filler (7),
５． 成分（２）が、水酸基、エポキシ基、アミノ基、シラノール基、アルコキシシラン基から選ばれる官能基を少なくとも１個有する原子団が少なくとも１個結合していることを特徴とする上記１〜４のいずれか１項に記載の共重合体組成物、
６． 成分（１）および／または成分（２）中の、ビニル芳香族化合物重合体ブロックの量が、１０質量％未満である上記１〜５のいずれか１項に記載の共重合体組成物、
７． 成分（１）および／または成分（２）中の、ビニル芳香族化合物重合体ブロックの量が、１０〜４０質量％である上記１〜５のいずれか１項に記載の共重合体組成物、
８． 成分（１）および／または成分（２）が、下記一般式から選ばれる少なくとも一つの構造を有する共重合体の水素添加物である上記１〜７のいずれかの１項に記載の共重合体組成物、
（イ）Ｂ
（ロ）Ｂ−Ａ
（ハ）Ｂ−Ａ−Ｂ
（ニ）（Ｂ−Ａ）ｍ−Ｘ
（ホ）（Ｂ−Ａ）ｎ−Ｘ−Ａｐ
（ここで、Ｂは共役ジエンとビニル芳香族化合物とのランダム共重合体ブロックであり、Ａはビニル芳香族化合物重合体ブロックである。ｍは２以上の整数であり、ｎ及びｐはそれぞれ１以上の整数である。Ｘはカップリング剤残基を示す。）
９． 成分（２）が、下記から選ばれる官能基を少なくとも１個有する原子団が少なくとも１個結合していることを特徴とする上記１〜８のいずれか１項に記載の共重合体組成物、
5). Component (2) is characterized in that at least one atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group is bonded. The copolymer composition according to any one of the above,
6). The copolymer composition according to any one of 1 to 5 above, wherein the amount of the vinyl aromatic compound polymer block in the component (1) and / or the component (2) is less than 10% by mass,
7). The copolymer composition according to any one of 1 to 5 above, wherein the amount of the vinyl aromatic compound polymer block in the component (1) and / or the component (2) is 10 to 40% by mass,
8). 8. The copolymer according to any one of 1 to 7 above, wherein component (1) and / or component (2) is a hydrogenated product of a copolymer having at least one structure selected from the following general formula Composition,
(I) B
(B) B-A
(C) B-A-B
(D) (BA) m -X
(E) (BA) n- X-A p
(Here, B is a random copolymer block of a conjugated diene and a vinyl aromatic compound, A is a vinyl aromatic compound polymer block, m is an integer of 2 or more, and n and p are each 1) (It is an integer above. X represents a coupling agent residue.)
9. The copolymer composition according to any one of 1 to 8 above, wherein the component (2) is bonded to at least one atomic group having at least one functional group selected from the following:
（上式で、Ｒ１〜Ｒ４は、水素又は炭素数１〜２４の炭化水素基、あるいは水酸基、エポキシ基、アミノ基、シラノール基、アルコキシシラン基から選ばれる官能基を有する炭素数１〜２４の炭化水素基。Ｒ５は炭素数１〜４８の炭化水素鎖、あるいは水酸基、エポキシ基、アミノ基、シラノール基、アルコキシシラン基から選ばれる官能基を有する炭素数１〜４８の炭化水素鎖。なおＲ１〜Ｒ４の炭化水素基及びＲ５の炭化水素鎖中には、水酸基、エポキシ基、シラノール基、アルコキシシラン基以外の結合様式で、酸素、窒素、シリコン等の元素が結合しも良い。Ｒ６は水素又は炭素数１〜８のアルキル基。）
１０． 成分（２）が、有機リチウム化合物を重合触媒として得た共役ジエンとビニル芳香族化合物からなる共重合体のリビング末端に、官能基を含有する変性剤を付加反応させてなる変性共重合体に水素添加してなることを特徴とする上記１〜９のいずれか１項に記載の共重合体組成物、
１１． 上記１〜１０のいずれか１項に記載の共重合体組成物をシート状に成形されてなる樹脂シート、
を提供するものである。
(In the above formula, R 1 to R 4 are hydrogen or a hydrocarbon group having 1 to 24 carbon atoms, or a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group. A hydrocarbon group having 24. R 5 is a hydrocarbon chain having 1 to 48 carbon atoms, or a hydrocarbon chain having 1 to 48 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group. In the hydrocarbon groups of R 1 to R 4 and the hydrocarbon chain of R 5 , elements such as oxygen, nitrogen, and silicon are bonded in a bonding mode other than a hydroxyl group, an epoxy group, a silanol group, and an alkoxysilane group. R 6 is hydrogen or an alkyl group having 1 to 8 carbon atoms.)
10. Component (2) is a modified copolymer obtained by adding a functional group-containing modifier to the living terminal of a copolymer composed of a conjugated diene and a vinyl aromatic compound obtained using an organolithium compound as a polymerization catalyst. The copolymer composition according to any one of the above 1 to 9, which is obtained by hydrogenation,
11. A resin sheet formed by molding the copolymer composition according to any one of 1 to 10 above into a sheet shape,
Is to provide.
本発明によって、熱伝導性、柔軟性、カレンダー成形時のシート破れや、厚みムラが少ない成形加工性に優れた共重合体組成物およびそれを用いた放熱性に優れた樹脂シートの提供が可能となった。 According to the present invention, it is possible to provide a copolymer composition having excellent heat-conductivity, flexibility, sheet breakage at the time of calendar molding, and excellent molding processability with little thickness unevenness, and a resin sheet having excellent heat dissipation using the same. It became.
本発明の成分（１）の水添共重合体又は成分（２）の変性水添共重合体（以下、水添共重合体等と呼ぶこともある。）は、共役ジエンとビニル芳香族化合物からなる共重合体に、水素を添加してなる水添共重合体等である。
本発明において、水添共重合体等におけるビニル芳香族化合物の含有量は５０質量％を越え９０質量％以下、好ましくは５０質量％を越え８８質量％以下、さらに好ましくは５０質量％を越え８６質量％以下である。ビニル芳香族化合物の含有量が本発明で規定する範囲のものを使用することは、柔軟性に富み、耐摩耗性、耐傷付き性、強度などに優れた本発明の共重合体組成物を得るために必要である。なお、本発明の水添共重合体等において、水素添加されたビニル芳香族化合物が含まれている場合があるが、この水素添加されたビニル芳香族化合物も同じく水添共重合体等中のビニル芳香族化合物含有量に含まれるものとする。本発明においては、水添共重合体等におけるビニル芳香族化合物の含有量は、水素添加前の共重合体中のビニル芳香族化合物含有量で把握しても良い。
The hydrogenated copolymer of component (1) or the modified hydrogenated copolymer of component (2) (hereinafter sometimes referred to as hydrogenated copolymer) is a conjugated diene and a vinyl aromatic compound. A hydrogenated copolymer obtained by adding hydrogen to a copolymer comprising
In the present invention, the content of the vinyl aromatic compound in the hydrogenated copolymer or the like is more than 50% by mass and 90% by mass or less, preferably more than 50% by mass and 88% by mass or less, more preferably more than 50% by mass and 86% by mass. It is below mass%. Use of a vinyl aromatic compound having a content specified by the present invention provides a copolymer composition of the present invention that is highly flexible and excellent in wear resistance, scratch resistance, strength, and the like. Is necessary for. The hydrogenated copolymer of the present invention may contain a hydrogenated vinyl aromatic compound. This hydrogenated vinyl aromatic compound is also contained in the hydrogenated copolymer. It shall be included in the vinyl aromatic compound content. In the present invention, the content of the vinyl aromatic compound in the hydrogenated copolymer or the like may be grasped by the content of the vinyl aromatic compound in the copolymer before hydrogenation.
本発明で使用する水添共重合体等において、ビニル芳香族化合物重合体ブロックの含有量は４０質量％以下、好ましくは３〜４０質量％、さらに好ましくは５〜３５質量％である。本発明において、柔軟性の良好な組成物を得たい場合、ビニル芳香族化合物重合体ブロックの含有量は１０質量％未満、好ましくは８質量％未満、さらに好ましくは５質量％未満であることが奨励される。また、本発明の共重合体組成物を得る上で、水添共重合体等として耐ブロッキング性に優れたものが好ましい場合、ビニル芳香族化合物重合体ブロックは１０〜４０質量％、好ましくは１３〜３７質量％、さらに好ましくは１５〜３５質量％であることが奨励される。 In the hydrogenated copolymer and the like used in the present invention, the content of the vinyl aromatic compound polymer block is 40% by mass or less, preferably 3 to 40% by mass, and more preferably 5 to 35% by mass. In the present invention, when it is desired to obtain a composition having good flexibility, the content of the vinyl aromatic compound polymer block is less than 10% by mass, preferably less than 8% by mass, more preferably less than 5% by mass. Encouraged. Moreover, when obtaining what is excellent in blocking resistance as a hydrogenated copolymer etc. when obtaining the copolymer composition of this invention, a vinyl aromatic compound polymer block is 10-40 mass%, Preferably it is 13 It is encouraged to be -37% by weight, more preferably 15-35% by weight.
ビニル芳香族化合物重合体ブロックの含有量の測定は、例えば四酸化オスミウムを触媒として水素添加前の共重合体をターシャルブチルハイドロパーオキサイドにより酸化分解する方法（Ｉ．Ｍ．ＫＯＬＴＨＯＦＦ，ｅｔａｌ．，Ｊ．Ｐｏｌｙｍ．Ｓｃｉ．１，４２９（１９４６）に記載の方法）により得たビニル芳香族炭化水素重合体ブロック成分の重量（但し平均重合度が約３０以下のビニル芳香族炭化水素重合体成分は除かれている）を用いて、次の式から求めることができる。
ビニル芳香族炭化水素のブロック重量（質量％）
＝｛（水素添加前の共重合体中のビニル芳香族炭化水素重合体ブロック重量／水素添加前の共重合体の重量）｝×１００
なお、本発明において水添共重合体等におけるビニル芳香族化合物のブロック率（ブロック率とは、該共重合体中の全ビニル芳香族化合物量に対するビニル芳香族化合物重合体ブロックの含有量の割合をいう）は、５０質量％未満、好ましくは２０質量％以下、さらに好ましくは１８質量％以下であることがより柔軟性の良好な組成物を得る上で奨励される。
The vinyl aromatic compound polymer block content is measured by, for example, a method in which osmium tetroxide is used as a catalyst to oxidatively decompose a copolymer before hydrogenation with tertiary butyl hydroperoxide (IM KOLTHOFF, et al., J. Polym.Sci. 1,429 (1946)) weight of vinyl aromatic hydrocarbon polymer block component (however, the vinyl aromatic hydrocarbon polymer component having an average degree of polymerization of about 30 or less is Can be obtained from the following equation.
Vinyl aromatic hydrocarbon block weight (% by mass)
= {(Vinyl aromatic hydrocarbon polymer block weight in copolymer before hydrogenation / weight of copolymer before hydrogenation)} × 100
In the present invention, the block ratio of the vinyl aromatic compound in the hydrogenated copolymer or the like (the block ratio is the ratio of the content of the vinyl aromatic compound polymer block to the total vinyl aromatic compound amount in the copolymer). Is less than 50% by weight, preferably 20% by weight or less, and more preferably 18% by weight or less, in order to obtain a more flexible composition.
本発明で使用する水添共重合体等の重量平均分子量は５〜１００万、好ましくは１０〜８０万、さらに好ましくは１３〜５０万である。ビニル芳香族化合物重合体ブロックの含有量が１０〜４０質量％の水添共重合体等を使用する場合、その重量平均分子量は１０万を越え、５０万未満、好ましくは１３万〜４０万、さらに好ましくは１５万から３０万であることが奨励される。重量平均分子量が５万未満の場合は機械的強度に劣り、また１００万を越える場合は成形加工性に劣るため好ましくない。
本発明において、水添共重合体等の分子量分布（Ｍｗ／Ｍｎ）（重量平均分子量（Ｍｗ）の数平均分子量（Ｍｎ）に対する比）は、成形加工性の点で、１．０１〜８．０が好ましく、より好ましくは１．１〜６．０、さらに好ましくは１．１〜５．０であることが奨励される。ゲルパーミュエーションクロマトグラフィー（ＧＰＣ）で測定した分子量分布の形状は特に制限はなく、山（ピーク）が二ヶ所以上存在するポリモーダルの分子量分布を持つものでもよいが、山が一つであるモノモーダルの分子量分布を持つ水添共重合体等が好ましい。
The weight average molecular weight of the hydrogenated copolymer or the like used in the present invention is 5 to 1,000,000, preferably 100 to 800,000, and more preferably 13 to 500,000. When using a hydrogenated copolymer having a vinyl aromatic compound polymer block content of 10 to 40% by mass, its weight average molecular weight is more than 100,000 and less than 500,000, preferably 130,000 to 400,000. More preferably, 150,000 to 300,000 is encouraged. When the weight average molecular weight is less than 50,000, the mechanical strength is inferior, and when it exceeds 1,000,000, the molding processability is inferior.
In the present invention, the molecular weight distribution (Mw / Mn) (ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn)) of the hydrogenated copolymer or the like is 1.01 to 8. 0 is preferred, more preferably 1.1 to 6.0, and even more preferably 1.1 to 5.0. The shape of the molecular weight distribution measured by gel permeation chromatography (GPC) is not particularly limited, and may have a polymodal molecular weight distribution having two or more peaks (peaks), but there is only one peak. Hydrogenated copolymers having a monomodal molecular weight distribution are preferred.
本発明で使用する水添共重合体等は、共役ジエンとビニル芳香族化合物からなる共重合体の水素添加物であり、共重合体中の共役ジエン化合物に基づく不飽和二重結合のトータル水素添加率は、１０％以上、好ましくは２０％以上、さらに好ましくは３０％以上である。特に耐候性に優れた組成物を得る場合は、水素添加率が７５％以上、好ましくは８５％以上、さらに好ましくは９０％以上であることが奨励される。また、加硫物特性の良好な加硫組成物を得る場合には、水素添加率は９８％以下、好ましくは９５％以下、さらに好ましくは９０％以下であることが奨励される。
さらに、本発明で使用する水添共重合体等において、特に熱安定性に優れた組成物を得る場合は、ビニル結合の水素添加率が８５％以上、好ましくは９０％以上、さらに好ましくは９５％以上であることが奨励される。
The hydrogenated copolymer used in the present invention is a hydrogenated product of a copolymer comprising a conjugated diene and a vinyl aromatic compound, and is a total hydrogen of unsaturated double bonds based on the conjugated diene compound in the copolymer. The addition rate is 10% or more, preferably 20% or more, more preferably 30% or more. In particular, when obtaining a composition excellent in weather resistance, it is recommended that the hydrogenation rate is 75% or more, preferably 85% or more, more preferably 90% or more. When obtaining a vulcanized composition having good vulcanizate properties, it is recommended that the hydrogenation rate be 98% or less, preferably 95% or less, and more preferably 90% or less.
Furthermore, in the hydrogenated copolymer used in the present invention, when obtaining a composition having particularly excellent thermal stability, the hydrogenation rate of vinyl bonds is 85% or more, preferably 90% or more, more preferably 95. % Is encouraged.
ここで、ビニル結合の水素添加率とは、水素添加前の共重合体中に組み込まれている共役ジエン中のビニル結合の内、水素添加されたビニル結合の割合をいう。
なお、共重合体中のビニル芳香族炭化水素に基づく芳香族二重結合の水添率については特に制限はないが、水添率を５０％以下、好ましくは３０％以下、さらに好ましくは２０％以下にすることが好ましい。
本発明で使用する水添共重合体等は、示差走査熱量測定法（ＤＳＣ法）において、−５０〜１００℃の温度範囲において結晶化ピークが実質的に存在しない水素添加物が好ましい。ここで、−５０〜１００℃の温度範囲において結晶化ピークが実質的に存在しないとは、この温度範囲において結晶化に起因するピークが現れない、もしくは結晶化に起因するピークが認められる場合においても、その結晶化における結晶化ピーク熱量が３Ｊ／ｇ未満、好ましくは２Ｊ／ｇ未満、さらに好ましくは１Ｊ／ｇ未満であり、特に好ましくは結晶化ピーク熱量が無いものである。
Here, the hydrogenation rate of vinyl bonds refers to the proportion of vinyl bonds that have been hydrogenated among the vinyl bonds in the conjugated diene incorporated in the copolymer before hydrogenation.
The hydrogenation rate of the aromatic double bond based on the vinyl aromatic hydrocarbon in the copolymer is not particularly limited, but the hydrogenation rate is 50% or less, preferably 30% or less, more preferably 20%. The following is preferable.
The hydrogenated copolymer or the like used in the present invention is preferably a hydrogenated product having substantially no crystallization peak in the temperature range of −50 to 100 ° C. in the differential scanning calorimetry (DSC method). Here, substantially no crystallization peak exists in the temperature range of −50 to 100 ° C. when no peak due to crystallization appears in this temperature range or when a peak due to crystallization is observed. The crystallization peak calorific value in the crystallization is less than 3 J / g, preferably less than 2 J / g, more preferably less than 1 J / g, and particularly preferably no crystallization peak calorie.
本発明において、水添共重合体等の構造は特に制限はなく、いかなる構造のものでも使用できるが、特に奨励されるものは、下記イ〜ホの一般式から選ばれる少なくとも一つの構造を有する共重合体の水素添加物である。本発明で使用する水添共重合体等は、下記イ〜ホの一般式で表される構造を有する共重合体の水素添加物からなる任意の混合物でもよい。また、水添共重合体等にビニル芳香族化合物重合体が混合されても良い。
（イ）Ｂ
（ロ）Ｂ−Ａ
（ハ）Ｂ−Ａ−Ｂ
（ニ）（Ｂ−Ａ）ｍ−Ｘ
（ホ）（Ｂ−Ａ）ｎ−Ｘ−Ａｐ
（ここで、Ｂは共役ジエンとビニル芳香族化合物とのランダム共重合体ブロックであり、Ａはビニル芳香族化合物重合体ブロックである。ｍは２以上の整数であり、ｎ及びｐはそれぞれ１以上の整数である。Ｘはカップリング剤残基を示す。）
一般式において、ランダム共重合体ブロックＢ中のビニル芳香族炭化水素は均一に分布していても、またはテーパー状に分布していてもよい。また該共重合体ブロックＢには、ビニル芳香族炭化水素が均一に分布している部分及び／又はテーパー状に分布している部分がそれぞれ複数個共存していてもよい。また、ｍは２以上、好ましくは２〜１０の整数であり、ｎ及びｐはそれぞれ１以上、好ましくは１〜１０の整数である。
In the present invention, the structure of the hydrogenated copolymer or the like is not particularly limited, and any structure can be used. However, what is particularly encouraged has at least one structure selected from the following general formulas (i) to (e). It is a hydrogenated product of a copolymer. The hydrogenated copolymer or the like used in the present invention may be an arbitrary mixture comprising a hydrogenated copolymer having a structure represented by the following general formulas (i) to (e). Further, a vinyl aromatic compound polymer may be mixed with a hydrogenated copolymer or the like.
(I) B
(B) B-A
(C) B-A-B
(D) (BA) m -X
(E) (BA) n- X-A p
(Here, B is a random copolymer block of a conjugated diene and a vinyl aromatic compound, A is a vinyl aromatic compound polymer block, m is an integer of 2 or more, and n and p are each 1) (It is an integer above. X represents a coupling agent residue.)
In the general formula, the vinyl aromatic hydrocarbons in the random copolymer block B may be distributed uniformly or in a tapered shape. In the copolymer block B, a plurality of portions where vinyl aromatic hydrocarbons are uniformly distributed and / or a portion where they are distributed in a tapered shape may coexist. M is 2 or more, preferably an integer of 2 to 10, and n and p are each 1 or more, preferably an integer of 1 to 10.
また、本発明において、水素添加前の共重合体鎖中におけるビニル結合含量の最大値と最小値との差が１０％未満、好ましくは８％以下、さらに好ましくは６％以下であることが奨励される。共重合体鎖中のビニル結合は、均一に分布していてもテーパー状に分布していても良い。ここで、ビニル結合含量の最大値と最小値との差とは、重合条件、すなわちビニル量調整剤の種類、量及び重合温度で決定されるビニル量の最大値と最小値である。
共役ジエン重合体鎖中のビニル結合含量の最大値と最小値との差は、例えば共役ジエンの重合時又は共役ジエンとビニル芳香族化合物の共重合時の重合温度によって制御することができる。第３級アミン化合物またはエーテル化合物のようなビニル量調整剤の種類と量が一定の場合、重合中のポリマー鎖に組み込まれるビニル結合含量は、重合温度によって決まる。従って、等温で重合した重合体はビニル結合が均一に分布した重合体となる。これに対し、昇温で重合した重合体は、初期（低温で重合）が高ビニル結合含量、後半（高温で重合）が低ビニル結合含量といった具合にビニル結合含量に差のある重合体となる。かかる構造を有する共重合体に、水素を添加することにより特異構造の水添共重合体等が得られる。
In the present invention, it is recommended that the difference between the maximum value and the minimum value of the vinyl bond content in the copolymer chain before hydrogenation is less than 10%, preferably 8% or less, more preferably 6% or less. Is done. The vinyl bonds in the copolymer chain may be distributed uniformly or in a tapered shape. Here, the difference between the maximum value and the minimum value of the vinyl bond content is the maximum value and the minimum value of the vinyl amount determined by the polymerization conditions, that is, the type and amount of the vinyl amount adjusting agent and the polymerization temperature.
The difference between the maximum value and the minimum value of the vinyl bond content in the conjugated diene polymer chain can be controlled by, for example, the polymerization temperature during the polymerization of the conjugated diene or the copolymerization of the conjugated diene and the vinyl aromatic compound. When the type and amount of a vinyl amount modifier such as a tertiary amine compound or an ether compound is constant, the vinyl bond content incorporated into the polymer chain during polymerization is determined by the polymerization temperature. Therefore, a polymer polymerized isothermally becomes a polymer in which vinyl bonds are uniformly distributed. In contrast, polymers polymerized at elevated temperatures become polymers with different vinyl bond contents, such as high vinyl bond content in the initial (polymerization at low temperature) and low vinyl bond content in the latter half (polymerization at high temperature). . A hydrogenated copolymer having a specific structure can be obtained by adding hydrogen to the copolymer having such a structure.
本発明において、ビニル芳香族化合物の含有量は、紫外分光光度計、赤外分光光度計や核磁気共鳴装置（ＮＭＲ）等を用いて知ることができる。また、ビニル芳香族化合物重合体ブロックの量は、前述したＫＯＬＴＨＯＦＦの方法等で知ることができる。水素添加前の共重合体中の共役ジエンに基づくビニル結合含量は、赤外分光光度計（例えば、ハンプトン法）や核磁気共鳴装置（ＮＭＲ）等を用いて知ることができる。また、水添共重合体等の水添率は、赤外分光光度計や核磁気共鳴装置（ＮＭＲ）等を用いて知ることができる。
また、本発明において、水添共重合体等の分子量は、ゲルパーミュエーションクロマトグラフィー（ＧＰＣ）による測定を行い、クロマトグラムのピークの分子量を、市販の標準ポリスチレンの測定から求めた検量線（標準ポリスチレンのピーク分子量を使用して作成）を使用して求めた重量平均分子量である。水添共重合体等の分子量分布は、同様にＧＰＣによる測定から求めることができる。
In the present invention, the content of the vinyl aromatic compound can be known using an ultraviolet spectrophotometer, an infrared spectrophotometer, a nuclear magnetic resonance apparatus (NMR), or the like. The amount of the vinyl aromatic compound polymer block can be known by the KOLTHOFF method described above. The vinyl bond content based on the conjugated diene in the copolymer before hydrogenation can be known using an infrared spectrophotometer (for example, the Hampton method), a nuclear magnetic resonance apparatus (NMR), or the like. Moreover, the hydrogenation rate of a hydrogenated copolymer etc. can be known using an infrared spectrophotometer, a nuclear magnetic resonance apparatus (NMR), etc.
In the present invention, the molecular weight of the hydrogenated copolymer or the like is measured by gel permeation chromatography (GPC), and the molecular weight of the peak of the chromatogram is obtained from a calibration curve obtained from the measurement of commercially available standard polystyrene ( The weight average molecular weight determined using the peak molecular weight of standard polystyrene). Similarly, the molecular weight distribution of a hydrogenated copolymer or the like can be determined from measurement by GPC.
本発明において共役ジエンは１対の共役二重結合を有するジオレフィンであり、例えば、１，３−ブタジエン、２−メチル−１，３−ブタジエン（イソプレン）、２，３−ジメチル−１，３−ブタジエン、１，３−ペンタジエン、２−メチル−１，３−ペンタジエン、１，３−ヘキサジエンなどであるが、特に一般的なものとしては、１，３−ブタジエン、イソプレンが挙げられる。これらは一種のみならず二種以上を使用してもよい。
また、ビニル芳香族化合物としては、例えばスチレン、α−メチルスチレン、ｐ−メチルスチレン、ジビニルベンゼン、１，１−ジフェニルエチレン、Ｎ、Ｎ−ジメチル−ｐ−アミノエチルスチレン、Ｎ、Ｎ−ジエチル−ｐ−アミノエチルスチレン等があげられ、これらは一種のみならず二種以上を使用してもよい。
In the present invention, the conjugated diene is a diolefin having a pair of conjugated double bonds, such as 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3. -Butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene and the like, and particularly common ones include 1,3-butadiene and isoprene. These may be used alone or in combination of two or more.
Examples of the vinyl aromatic compound include styrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl- Examples thereof include p-aminoethylstyrene, and these may be used alone or in combination of two or more.
本発明において、水素添加前の共重合体において共役ジエン部分のミクロ構造（シス、トランス、ビニルの比率）は、後述する極性化合物等の使用により任意に変えることができ、特に制限はない。一般的に共役ジエンとして１，３−ブタジエンを使用した場合には、１，２−ビニル結合は５〜８０％、好ましくは１０〜６０％、共役ジエンとしてイソプレンを使用した場合又は１，３−ブタジエンとイソプレンを併用した場合には、１，２−ビニル結合と３，４−ビニル結合の合計量は一般に３〜７５％、好ましくは５〜６０％であることが推奨される。なお、本発明においては、１，２−ビニル結合と３，４−ビニル結合の合計量（但し、共役ジエンとして１，３−ブタジエンを使用した場合には、１，２−ビニル結合量）を以後ビニル結合含量と呼ぶ。 In the present invention, the microstructure of the conjugated diene portion (ratio of cis, trans, vinyl) in the copolymer before hydrogenation can be arbitrarily changed by using a polar compound or the like described later, and is not particularly limited. Generally, when 1,3-butadiene is used as the conjugated diene, the 1,2-vinyl bond is 5 to 80%, preferably 10 to 60%. When isoprene is used as the conjugated diene, When butadiene and isoprene are used in combination, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is generally recommended to be 3 to 75%, preferably 5 to 60%. In the present invention, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (however, when 1,3-butadiene is used as the conjugated diene, the amount of 1,2-vinyl bonds) is Hereinafter referred to as vinyl bond content.
本発明において、水素添加前の共重合体は、例えば、炭化水素溶媒中で有機アルカリ金属化合物等の開始剤を用いてアニオンリビング重合により得られる。炭化水素溶媒としては、例えばｎ−ブタン、イソブタン、ｎ−ペンタン、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタンの如き脂肪族炭化水素類、シクロヘキサン、シクロヘプタン、メチルシクロヘプタンの如き脂環式炭化水素類、また、ベンゼン、トルエン、キシレン、エチルベンゼンの如き芳香族炭化水素類である。
また、開始剤としては、一般的に共役ジエン化合物及びビニル芳香族化合物に対しアニオン重合活性があることが知られている脂肪族炭化水素アルカリ金属化合物、芳香族炭化水素アルカリ金属化合物、有機アミノアルカリ金属化合物等が含まれ、アルカリ金属としてはリチウム、ナトリウム、カリウム等である。好適な有機アルカリ金属化合物としては、炭素数１から２０の脂肪族および芳香族炭化水素リチウム化合物であり、１分子中に１個のリチウムを含む化合物、１分子中に複数のリチウムを含むジリチウム化合物、トリリチウム化合物、テトラリチウム化合物が含まれる。
In the present invention, the copolymer before hydrogenation is obtained, for example, by anion living polymerization using an initiator such as an organic alkali metal compound in a hydrocarbon solvent. Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as n-butane, isobutane, n-pentane, n-hexane, n-heptane and n-octane, and alicyclic carbonization such as cyclohexane, cycloheptane and methylcycloheptane. Hydrogen, and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene.
Further, as the initiator, an aliphatic hydrocarbon alkali metal compound, an aromatic hydrocarbon alkali metal compound, an organic amino alkali, which are generally known to have anionic polymerization activity with respect to a conjugated diene compound and a vinyl aromatic compound. Examples of the alkali metal include lithium, sodium, and potassium. Suitable organic alkali metal compounds are aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms, a compound containing one lithium in one molecule, and a dilithium compound containing a plurality of lithiums in one molecule , Trilithium compounds, and tetralithium compounds.
具体的にはｎ−プロピルリチウム、ｎ−ブチルリチウム、ｓｅｃ−ブチルリチウム、ｔｅｒｔ−ブチルリチウム、ｎ−ペンチルリチウム、ｎ−ヘキシルリチウム、ベンジルリチウム、フェニルリチウム、トリルリチウム、ジイソプロペニルベンゼンとｓｅｃ−ブチルリチウムの反応生成物、さらにジビニルベンゼンとｓｅｃ−ブチルリチウムと少量の１，３−ブタジエンの反応生成物等があげられる。さらに、米国特許５，７０８，０９２号明細書に開示されている１−（ｔ−ブトキシ）プロピルリチウムおよびその溶解性改善のために１〜数分子のイソプレンモノマーを挿入したリチウム化合物、英国特許２，２４１，２３９号明細書に開示されている１−（ｔ−ブチルジメチルシロキシ）ヘキシルリチウム等のシロキシ基含有アルキルリチウム、米国特許５，５２７，７５３号明細書に開示されているアミノ基含有アルキルリチウム、ジイソプロピルアミドリチウムおよびヘキサメチルジシラジドリチウム等のアミノリチウム類も使用することができる。 Specifically, n-propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, benzyllithium, phenyllithium, tolyllithium, diisopropenylbenzene and sec- A reaction product of butyllithium, a reaction product of divinylbenzene, sec-butyllithium, and a small amount of 1,3-butadiene can be used. Further, 1- (t-butoxy) propyllithium disclosed in US Pat. No. 5,708,092 and a lithium compound in which 1 to several molecules of isoprene monomer are inserted to improve its solubility, British Patent 2 Siloxy group-containing alkyllithium such as 1- (t-butyldimethylsiloxy) hexyllithium disclosed in US Pat. No. 5,241,239, amino group-containing alkyl disclosed in US Pat. No. 5,527,753 Aminolithiums such as lithium, diisopropylamidolithium and hexamethyldisilazide lithium can also be used.
本発明において有機アルカリ金属化合物を重合開始剤として共役ジエン化合物とビニル芳香族化合物を共重合する際に、重合体に組み込まれる共役ジエン化合物に起因するビニル結合（１，２または３，４結合）の含有量の調整や共役ジエン化合物とビニル芳香族化合物とのランダム共重合性を調整するために、調整剤として第３級アミン化合物またはエーテル化合物を添加することができる。第３級アミン化合物としては一般式Ｒ１Ｒ２Ｒ３Ｎ（ただしＲ１、Ｒ２、Ｒ３は炭素数１から２０の炭化水素基または第３級アミノ基を有する炭化水素基である。）の化合物である。
例えば、トリメチルアミン、トリエチルアミン、トリブチルアミン、Ｎ，Ｎ−ジメチルアニリン、Ｎ−エチルピペリジン、Ｎ−メチルピロリジン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラエチルエチレンジアミン、１，２−ジピペリジノエタン、トリメチルアミノエチルピペラジン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”−ペンタメチルエチレントリアミン、Ｎ，Ｎ’−ジオクチル−ｐ−フェニレンジアミン等である。
In the present invention, when an organic alkali metal compound is used as a polymerization initiator and a conjugated diene compound and a vinyl aromatic compound are copolymerized, a vinyl bond (1, 2 or 3, 4 bond) resulting from the conjugated diene compound incorporated into the polymer A tertiary amine compound or an ether compound can be added as an adjusting agent in order to adjust the content of and to adjust the random copolymerizability between the conjugated diene compound and the vinyl aromatic compound. The tertiary amine compound is a compound of the general formula R1R2R3N (wherein R1, R2, and R3 are hydrocarbon groups having 1 to 20 carbon atoms or a tertiary amino group).
For example, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N-ethylpiperidine, N-methylpyrrolidine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′— Tetraethylethylenediamine, 1,2-dipiperidinoethane, trimethylaminoethylpiperazine, N, N, N ′, N ″, N ″ -pentamethylethylenetriamine, N, N′-dioctyl-p-phenylenediamine and the like. .
またエーテル化合物としては、直鎖状エーテル化合物および環状エーテル化合物から選ばれ、直鎖状エーテル化合物としてはジメチルエーテル、ジエチルエーテル、ジフェニルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジブチルエーテル等のエチレングリコールのジアルキルエーテル化合物類、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル等のジエチレングリコールのジアルキルエーテル化合物類が挙げられる。
また、環状エーテル化合物としてはテトラヒドロフラン、ジオキサン、２，５−ジメチルオキソラン、２，２，５，５−テトラメチルオキソラン、２，２−ビス（２−オキソラニル）プロパン、フルフリルアルコールのアルキルエーテル等が挙げられる。
The ether compound is selected from linear ether compounds and cyclic ether compounds, and the linear ether compound is an ethylene glycol such as dimethyl ether, diethyl ether, diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether or the like. And dialkyl ether compounds of diethylene glycol such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether.
Cyclic ether compounds include tetrahydrofuran, dioxane, 2,5-dimethyloxolane, 2,2,5,5-tetramethyloxolane, 2,2-bis (2-oxolanyl) propane, and alkyl ethers of furfuryl alcohol. Etc.
本発明において有機アルカリ金属化合物を重合開始剤として共役ジエン化合物とビニル芳香族化合物を共重合する方法は、バッチ重合であっても連続重合であっても、或いはそれらの組み合わせであってもよい。特に分子量分布を好ましい適正範囲に調整する上で連続重合方法が推奨される。重合温度は、一般に０℃乃至１８０℃、好ましくは３０℃乃至１５０℃である。重合に要する時間は条件によって異なるが、通常は４８時間以内であり、特に好適には０．１乃至１０時間である。また、重合系の雰囲気は窒素ガスなどの不活性ガス雰囲気にすることが好ましい。重合圧力は、上記重合温度範囲でモノマー及び溶媒を液相に維持するに充分な圧力の範囲で行えばよく、特に限定されるものではない。更に、重合系内は触媒及びリビングポリマーを不活性化させるような不純物、例えば水、酸素、炭酸ガスなどが混入しないように留意する必要がある。 In the present invention, the method of copolymerizing a conjugated diene compound and a vinyl aromatic compound using an organic alkali metal compound as a polymerization initiator may be batch polymerization, continuous polymerization, or a combination thereof. In particular, a continuous polymerization method is recommended for adjusting the molecular weight distribution to a preferable appropriate range. The polymerization temperature is generally 0 ° C. to 180 ° C., preferably 30 ° C. to 150 ° C. The time required for the polymerization varies depending on the conditions, but is usually within 48 hours, particularly preferably 0.1 to 10 hours. The polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited as long as the polymerization pressure is in a range sufficient to maintain the monomer and solvent in a liquid phase within the above polymerization temperature range. Furthermore, care must be taken so that impurities that inactivate the catalyst and living polymer, such as water, oxygen, and carbon dioxide, do not enter the polymerization system.
本発明において、前記重合終了時に２官能以上のカップリング剤を必要量添加してカップリング反応を行うことができる。２官能カップリング剤としては公知のものいずれでも良く、特に限定されない。例えば、ジメチルジクロロシラン、ジメチルジブロモシラン等のジハロゲン化合物、安息香酸メチル、安息香酸エチル、安息香酸フェニル、フタル酸エステル類等の酸エステル類等が挙げられる。
また、３官能以上の多官能カップリング剤としては公知のものいずれでも良く、特に限定されない。例えば、３価以上のポリアルコール類、エポキシ化大豆油、ジグリシジルビスフェノールＡ等の多価エポキシ化合物、一般式Ｒ4-nＳｉＸｎ（ただし、Ｒは炭素数１から２０の炭化水素基、Ｘはハロゲン、ｎは３または４）で示されるハロゲン化珪素化合物、例えばメチルシリルトリクロリド、ｔ−ブチルシリルトリクロリド、四塩化珪素およびこれらの臭素化物等、一般式Ｒ4-nＳｉＸｎ（ただし、Ｒは炭素数１から２０の炭化水素基、Ｘはハロゲン、ｎは３または４）で示されるハロゲン化錫化合物、例えばメチル錫トリクロリド、ｔ−ブチル錫トリクロリド、四塩化錫等の多価ハロゲン化合物が挙げられる。炭酸ジメチルや炭酸ジエチル等も使用できる。
In the present invention, a coupling reaction can be performed by adding a necessary amount of a bifunctional or higher functional coupling agent at the end of the polymerization. Any known bifunctional coupling agent may be used and is not particularly limited. Examples thereof include dihalogen compounds such as dimethyldichlorosilane and dimethyldibromosilane, and acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, and phthalates.
Further, any known trifunctional or higher polyfunctional coupling agent may be used without any particular limitation. For example, polyalcohols having 3 or more valences, polyepoxy compounds such as epoxidized soybean oil, diglycidyl bisphenol A, general formula R 4-n SiX n (where R is a hydrocarbon group having 1 to 20 carbon atoms, X halogen, n represents a halogenated silicon compound represented by 3 or 4), such as methyl silyl trichloride, t- butyl silyl trichloride, silicon tetrachloride and the like of these bromides formula R 4-n SiX n (provided that , R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, n is a halogenated compound represented by 3 or 4), for example, a polyvalent halogen such as methyltin trichloride, t-butyltin trichloride, tin tetrachloride Compounds. Dimethyl carbonate or diethyl carbonate can also be used.
本発明において、共重合体として重合体の少なくとも１つの重合体鎖に極性基含有原子団が結合した変性共重合体を使用することができる。極性基含有原子団としては、例えば水酸基、カルボキシル基、カルボニル基、チオカルボニル基、酸ハロゲン化物基、酸無水物基、カルボン酸基、チオカルボン酸基、アルデヒド基、チオアルデヒド基、カルボン酸エステル基、アミド基、スルホン酸基、スルホン酸エステル基、リン酸基、リン酸エステル基、アミノ基、イミノ基、ニトリル基、ピリジル基、キノリン基、エポキシ基、チオエポキシ基、スルフィド基、イソシアネート基、イソチオシアネート基、ハロゲン化ケイ素基、シラノール基、アルコキシケイ素基、ハロゲン化スズ基、アルコキシスズ基、フェニルスズ基等から選ばれる極性基を少なくとも１種含有する原子団が挙げられる。 In the present invention, a modified copolymer in which a polar group-containing atomic group is bonded to at least one polymer chain of the polymer can be used as the copolymer. Examples of the polar group-containing atomic group include a hydroxyl group, a carboxyl group, a carbonyl group, a thiocarbonyl group, an acid halide group, an acid anhydride group, a carboxylic acid group, a thiocarboxylic acid group, an aldehyde group, a thioaldehyde group, and a carboxylic acid ester group. Amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid group, phosphoric acid ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfide group, isocyanate group, iso Examples thereof include an atomic group containing at least one polar group selected from a thiocyanate group, a silicon halide group, a silanol group, an alkoxysilicon group, a tin halide group, an alkoxytin group, a phenyltin group and the like.
変性共重合体は、共重合体の重合終了時にこれらの極性基含有原子団を有する化合物を反応させることにより得られる。極性基含有原子団を有する化合物としては、具体的には、特公平４−３９４９５号公報に記載された変性処理剤を使用できる。本発明で成分（３）として用いる好ましい変性水添共重合体は、水酸基、エポキシ基、アミノ基、シラノール基、アルコキシシラン基から選ばれる官能基を少なくとも１個有する原子団が、少なくとも1個結合している変性水添共重合体である。かかる変性水添共重合体は、有機リチウム化合物を重合触媒として上述のような方法で得た共重合体のリビング末端に、官能基含有の変性剤を付加反応させることにより、共重合体に水酸基、エポキシ基、アミノ基、シラノール基、アルコキシシラン基から選ばれる官能基を少なくとも１個有する原子団が少なくとも１個結合している変性物（以後、変性共重合体と呼ぶ。）に水素を添加することにより得ることができる。 The modified copolymer is obtained by reacting a compound having these polar group-containing atomic groups at the end of polymerization of the copolymer. As the compound having a polar group-containing atomic group, specifically, a modification treatment agent described in Japanese Patent Publication No. 4-39495 can be used. A preferred modified hydrogenated copolymer used as component (3) in the present invention is a bond of at least one atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group. The modified hydrogenated copolymer. Such a modified hydrogenated copolymer is obtained by adding a functional group-containing modifier to the living end of a copolymer obtained by the above-described method using an organolithium compound as a polymerization catalyst, thereby adding a hydroxyl group to the copolymer. Hydrogen is added to a modified product (hereinafter referred to as a modified copolymer) in which at least one atomic group having at least one functional group selected from an epoxy group, an amino group, a silanol group, and an alkoxysilane group is bonded. Can be obtained.
変性共重合体を得る他の方法として、変性前の共重合体に有機リチウム化合物等の有機アルカリ金属化合物を反応（メタレーション反応）させ、有機アルカリ金属が付加した共重合体に官能基含有の変性剤を付加反応させる方法が挙げられる。なお、変性剤の種類により、変性剤を反応させた段階で一般に水酸基やアミノ基等は有機金属塩となっていることもあるが、その場合には水やアルコール等活性水素を有する化合物で処理することにより、水酸基やアミノ基等にすることができる。
本発明において、水酸基、エポキシ基、アミノ基、シラノール基、アルコキシシラン基から選ばれる官能基を少なくとも１個有する原子団として好ましい原子団は、下記一般式で示されるものから選ばれる原子団が挙げられる。
As another method for obtaining a modified copolymer, an organic alkali metal compound such as an organolithium compound is reacted (metalation reaction) with the copolymer before the modification, and the functional group-containing copolymer is added to the copolymer added with the organic alkali metal. Examples include a method in which a modifying agent is subjected to an addition reaction. Depending on the type of modifier, the hydroxyl group and amino group may generally be an organometallic salt at the stage of reaction of the modifier, but in that case, treatment with a compound having active hydrogen such as water or alcohol. By doing so, a hydroxyl group, an amino group, or the like can be obtained.
In the present invention, an atomic group preferable as an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group includes an atomic group selected from those represented by the following general formula: It is done.
（上式で、Ｒ1〜Ｒ4は、水素又は炭素数１〜２４の炭化水素基、あるいは水酸基、エポキシ基、アミノ基、シラノール基、アルコキシシラン基から選ばれる官能基を有する炭素数１〜２４の炭化水素基。Ｒ5は炭素数１〜４８の炭化水素鎖、あるいは水酸基、エポキシ基、アミノ基、シラノール基、アルコキシシラン基から選ばれる官能基を有する炭素数１〜４８の炭化水素鎖。なおＲ1〜Ｒ4の炭化水素基、及びＲ5の炭化水素鎖中には、水酸基、エポキシ基、シラノール基、アルコキシシラン基以外の結合様式で、酸素、窒素、シリコン等の元素が結合していても良い。Ｒ6は水素又は炭素数１〜８のアルキル基。）
本発明において、水酸基、エポキシ基、アミノ基、シラノール基、アルコキシシラン基から選ばれる官能基を少なくとも１個有する原子団が少なくとも１個結合している変性水添共重合体を得るために使用される変性剤としては、下記のものが挙げられる。
(In the above formula, R 1 to R 4 are hydrogen or a hydrocarbon group having 1 to 24 carbon atoms, or a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group. A hydrocarbon group having 24. R 5 is a hydrocarbon chain having 1 to 48 carbon atoms, or a hydrocarbon chain having 1 to 48 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group. In the hydrocarbon groups of R 1 to R 4 and the hydrocarbon chain of R 5 , elements such as oxygen, nitrogen, and silicon are bonded in a bonding mode other than a hydroxyl group, an epoxy group, a silanol group, and an alkoxysilane group. R6 is hydrogen or an alkyl group having 1 to 8 carbon atoms.)
In the present invention, it is used to obtain a modified hydrogenated copolymer in which at least one atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group is bonded. Examples of the modifying agent include the following.
例えば、テトラグリシジルメタキシレンジアミン、テトラグリシジル−１，３−ビスアミノメチルシクロヘキサン、テトラグリシジル−ｐ−フェニレンジアミン、テトラグリシジルジアミノジフェニルメタン、ジグリシジルアニリン、ジグリシジルオルソトルイジン、γ−グリシドキシエチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシブチルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルトリプロポキシシラン、γ−グリシドキシプロピルトリブトキシシラン、γ−グリシドキシプロピルトリフェノキシシラン、γ−グリシドキシプロピルメチルジメトキシシランが挙げられる。 For example, tetraglycidylmetaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane, diglycidylaniline, diglycidylorthotoluidine, γ-glycidoxyethyltrimethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxy Examples include silane, γ-glycidoxypropyltriphenoxysilane, and γ-glycidoxypropylmethyldimethoxysilane.
また、γ−グリシドキシプロピルエチルジメトキシシラン、γ−グリシドキシプロピルエチルジエトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルメチルジプロポキシシラン、γ−グリシドキシプロピルメチルジブトキシシラン、γ−グリシドキシプロピルメチルジフェノキシシラン、γ−グリシドキシプロピルジメチルメトキシシラン、γ−グリシドキシプロピルジエチルエトキシシラン、γ−グリシドキシプロピルジメチルエトキシシラン、γ−グリシドキシプロピルジメチルフェノキシシラン、γ−グリシドキシプロピルジエチルメトキシシラン、γ−グリシドキシプロピルメチルジイソプロペンオキシシランが挙げられる。 Γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxy Propylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldiethylethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycyl Sidoxypropyldimethylphenoxysilane, γ-glycidoxypropyldiethylmethoxysilane, and γ-glycidoxypropylmethyldiisopropeneoxysilane are exemplified.
また、ビス（γ−グリシドキシプロピル）ジメトキシシラン、ビス（γ−グリシドキシプロピル）ジエトキシシラン、ビス（γ−グリシドキシプロピル）ジプロポキシシラン、ビス（γ−グリシドキシプロピル）ジブトキシシラン、ビス（γ−グリシドキシプロピル）ジフェノキシシラン、ビス（γ−グリシドキシプロピル）メチルメトキシシラン、ビス（γ−グリシドキシプロピル）メチルエトキシシラン、ビス（γ−グリシドキシプロピル）メチルプロポキシシラン、ビス（γ−グリシドキシプロピル）メチルブトキシシラン、ビス（γ−グリシドキシプロピル）メチルフェノキシシランが挙げられる。
また、トリス（γ−グリシドキシプロピル）メトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン、γ−メタクリロキシメチルトリメトキシシラン、γ−メタクリロキシエチルトリエトキシシラン、ビス（γ−メタクリロキシプロピル）ジメトキシシラン、トリス（γ−メタクリロキシプロピル）メトキシシランが挙げられる。
Also, bis (γ-glycidoxypropyl) dimethoxysilane, bis (γ-glycidoxypropyl) diethoxysilane, bis (γ-glycidoxypropyl) dipropoxysilane, bis (γ-glycidoxypropyl) di Butoxysilane, bis (γ-glycidoxypropyl) diphenoxysilane, bis (γ-glycidoxypropyl) methylmethoxysilane, bis (γ-glycidoxypropyl) methylethoxysilane, bis (γ-glycidoxypropyl) ) Methylpropoxysilane, bis (γ-glycidoxypropyl) methylbutoxysilane, and bis (γ-glycidoxypropyl) methylphenoxysilane.
Further, tris (γ-glycidoxypropyl) methoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-methacryloxyethyltriethoxysilane, Examples include bis (γ-methacryloxypropyl) dimethoxysilane and tris (γ-methacryloxypropyl) methoxysilane.
また、β−（３，４−エポキシシクロヘキシル）エチル−トリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−トリエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−トリプロポキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−トリブトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−トリフェノキシシラン、β−（３，４−エポキシシクロヘキシル）プロピル−トリメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−メチルジメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−エチルジメトキシシランが挙げられる。 Β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-triethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tripropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tributoxysilane, β- (3,4-epoxycyclohexyl) ethyl-triphenoxysilane, β- (3,4-epoxycyclohexyl) propyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-ethyldimethoxysilane.
また、β−（３，４−エポキシシクロヘキシル）エチル−エチルジエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−メチルジエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−メチルジプロポキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−メチルジブトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−メチルジフェノキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−ジメチルメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−ジエチルエトキシシランが挙げられる。 Β- (3,4-epoxycyclohexyl) ethyl-ethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldi Propoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldibutoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethyl Examples include methoxysilane, β- (3,4-epoxycyclohexyl) ethyl-diethylethoxysilane.
さらにまた、β−（３，４−エポキシシクロヘキシル）エチル−ジメチルエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−ジメチルプロポキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−ジメチルブトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−ジメチルフェノキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−ジエチルメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチル−メチルジイソプロペンオキシシラン、１，３−ジメチル−２−イミダゾリジノン、１，３−ジエチル−２−イミダゾリジノン、Ｎ，Ｎ’−ジメチルプロピレンウレア、Ｎ−メチルピロリドン等が挙げられる。 Furthermore, β- (3,4-epoxycyclohexyl) ethyl-dimethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylpropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylbutoxysilane , Β- (3,4-epoxycyclohexyl) ethyl-dimethylphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-diethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiisopropeneoxy Examples include silane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N, N′-dimethylpropylene urea, N-methylpyrrolidone, and the like.
有機リチウム化合物を重合触媒として上述のような方法で得た共重合体のリビング末端に上記の変性剤を反応させることにより、水酸基、エポキシ基、アミノ基、シラノール基、アルコキシシラン基から選ばれる官能基を少なくとも１個有する原子団が結合している変性剤の残基が結合している変性共重合体が得られる。
本発明において、成分（１）の水添共重合体又は成分（２）の変性水添共重合体は、上記で得られた水素添加前の共重合体又は変性共重合体を水素添加することにより得られる。水添触媒としては、特に制限されず、従来から公知である（１）Ｎｉ、Ｐｔ、Ｐｄ、Ｒｕ等の金属をカーボン、シリカ、アルミナ、ケイソウ土等に担持させた担持型不均一系水添触媒、（２）Ｎｉ、Ｃｏ、Ｆｅ、Ｃｒ等の有機酸塩又はアセチルアセトン塩などの遷移金属塩と有機アルミニウム等の還元剤とを用いる、いわゆるチーグラー型水添触媒、（３）Ｔｉ、Ｒｕ、Ｒｈ、Ｚｒ等の有機金属化合物等のいわゆる有機金属錯体等の均一系水添触媒が用いられる。
A functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group by reacting the above modifier with the living end of the copolymer obtained by the above-described method using an organolithium compound as a polymerization catalyst. A modified copolymer in which the residue of the modifying agent to which the atomic group having at least one group is bonded is bonded.
In the present invention, the hydrogenated copolymer of component (1) or the modified hydrogenated copolymer of component (2) is obtained by hydrogenating the copolymer obtained before or obtained before hydrogenation. Is obtained. The hydrogenation catalyst is not particularly limited and is conventionally known (1) A supported heterogeneous hydrogenation in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, or the like. A catalyst, (2) a so-called Ziegler-type hydrogenation catalyst using an organic acid salt such as Ni, Co, Fe, Cr or a transition metal salt such as acetylacetone salt and a reducing agent such as organic aluminum, (3) Ti, Ru, A homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Rh or Zr is used.
具体的な水添触媒としては、特公昭４２−８７０４号公報、特公昭４３−６６３６号公報、特公昭６３−４８４１号公報、特公平１−３７９７０号公報、特公平１−５３８５１号公報、特公平２−９０４１号公報に記載された水添触媒を使用することができる。好ましい水添触媒としてはチタノセン化合物および／または還元性有機金属化合物との混合物があげられる。チタノセン化合物としては、特開平８−１０９２１９号公報に記載された化合物が使用できるが、具体例としては、ビスシクロペンタジエニルチタンジクロライド、モノペンタメチルシクロペンタジエニルチタントリクロライド等の（置換）シクロペンタジエニル骨格、インデニル骨格あるいはフルオレニル骨格を有する配位子を少なくとも１つ以上もつ化合物があげられる。また、還元性有機金属化合物としては、有機リチウム等の有機アルカリ金属化合物、有機マグネシウム化合物、有機アルミニウム化合物、有機ホウ素化合物あるいは有機亜鉛化合物等があげられる。
水添反応は一般的に０〜２００℃、より好ましくは３０〜１５０℃の温度範囲で実施される。水添反応に使用される水素の圧力は０．１〜１５ＭＰａ、好ましくは０．２〜１０ＭＰａ、更に好ましくは０．３〜５ＭＰａが推奨される。また、水添反応時間は通常３分〜１０時間、好ましくは１０分〜５時間である。水添反応は、バッチプロセス、連続プロセス、或いはそれらの組み合わせのいずれでも用いることができる。
Specific examples of the hydrogenation catalyst include Japanese Patent Publication No. 42-8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-337970, Japanese Patent Publication No. 1-53851, The hydrogenation catalyst described in Japanese Utility Model Publication No. 2-9041 can be used. A preferred hydrogenation catalyst is a mixture with a titanocene compound and / or a reducing organometallic compound. As the titanocene compound, compounds described in JP-A-8-109219 can be used. Specific examples thereof include (substitution) such as biscyclopentadienyl titanium dichloride and monopentamethylcyclopentadienyl titanium trichloride. Examples thereof include compounds having at least one ligand having a cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton. Examples of the reducing organometallic compound include organic alkali metal compounds such as organolithium, organomagnesium compounds, organoaluminum compounds, organoboron compounds, and organozinc compounds.
The hydrogenation reaction is generally carried out in a temperature range of 0 to 200 ° C, more preferably 30 to 150 ° C. The pressure of hydrogen used for the hydrogenation reaction is 0.1 to 15 MPa, preferably 0.2 to 10 MPa, more preferably 0.3 to 5 MPa. The hydrogenation reaction time is usually 3 minutes to 10 hours, preferably 10 minutes to 5 hours. The hydrogenation reaction can be any of a batch process, a continuous process, or a combination thereof.
本発明における成分（２）の変性水添共重合体の場合、一部変性されていない水添共重合体が変性水添共重合体に混在しても良い。成分（２）の変性水添共重合体に混在する未変性の水添共重合体の割合は、７０質量％以下、好ましくは６０質量％以下、より好ましくは５０質量％以下であることが推奨される。上記のようにして得られた水添共重合体又は変性水添共重合体の溶液は、必要に応じて触媒残査を除去し、水添共重合体又は変性水添共重合体を溶液から分離することができる。溶媒の分離の方法としては、例えば水添後の溶液にアセトンまたはアルコール等の重合体に対する貧溶媒となる極性溶媒を加えて重合体を沈澱させて回収する方法、水添共重合体又は変性水添共重合体の溶液を撹拌下熱湯中に投入し、スチームストリッピングにより溶媒を除去して回収する方法、または直接重合体溶液を加熱して溶媒を留去する方法等を挙げることができる。
なお、本発明で使用する水添共重合体又は変性水添共重合体には、各種フェノール系安定剤、リン系安定剤、イオウ系安定剤、アミン系安定剤等の安定剤を添加することができる。
In the case of the modified hydrogenated copolymer of component (2) in the present invention, a partially unmodified hydrogenated copolymer may be mixed in the modified hydrogenated copolymer. It is recommended that the proportion of the unmodified hydrogenated copolymer mixed in the modified hydrogenated copolymer of component (2) is 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less. Is done. The solution of the hydrogenated copolymer or modified hydrogenated copolymer obtained as described above removes the catalyst residue, if necessary, and removes the hydrogenated copolymer or modified hydrogenated copolymer from the solution. Can be separated. Solvent separation methods include, for example, a method in which a polar solvent that is a poor solvent for a polymer such as acetone or alcohol is added to the solution after hydrogenation to precipitate and recover the polymer, a hydrogenated copolymer or modified water Examples thereof include a method in which the additive copolymer solution is poured into hot water with stirring and the solvent is removed by steam stripping, or a method in which the solvent is distilled off by directly heating the polymer solution.
In addition, stabilizers such as various phenol stabilizers, phosphorus stabilizers, sulfur stabilizers and amine stabilizers should be added to the hydrogenated copolymer or modified hydrogenated copolymer used in the present invention. Can do.
本発明で用いる、核部とこの核部から異なる４軸方向に伸びた針状結晶である酸化亜鉛（３）とは、核部を有し、この核部からテトラポット状に異なる４軸方向に伸びた針状結晶であり、例えば、松下アムテック株式会社製「商品名：パナテトラ」等が挙げられる。
上記酸化亜鉛において、針状結晶部の核部の径が０．７〜１４μｍ、前記針状結晶部の基部から先端までの長さが３〜２００μｍであることが好ましい。さらに好ましくは上記針状結晶部の基部の径が１〜１４μｍであり、前記針状結晶部の基部から先端までの長さが１０〜２００μｍである。
The core and zinc oxide (3), which is a needle-like crystal extending in different four-axis directions from the core, used in the present invention have a core, and the four-axis directions differ from the core in a tetrapot shape. For example, “trade name: Panatetra” manufactured by Matsushita Amtech Co., Ltd. and the like can be mentioned.
In the zinc oxide, it is preferable that the diameter of the core part of the needle crystal part is 0.7 to 14 μm, and the length from the base part to the tip of the needle crystal part is 3 to 200 μm. More preferably, the diameter of the base of the acicular crystal part is 1 to 14 μm, and the length from the base to the tip of the acicular crystal part is 10 to 200 μm.
また上記酸化亜鉛において、１つの針状結晶の先端と、核部と他の針状結晶の先端とのなす角度が、１０９．５度であることが好ましい。
該酸化亜鉛はカップリング剤で表面処理された酸化亜鉛も本発明に含むことができ、ここで用いるカップリング剤はシランカップリング剤、チタネート系カップリング剤、アルミニウム系カップリング剤が好適に用いられる。
本発明の共重合体組成物中に針状の酸化亜鉛が存在することがあるが、これはテトラポット状構造の酸化亜鉛の複数方向に伸びた針状結晶部が折損したものであり、本発明の主要な特性を何ら損なうものではない。
In the zinc oxide, the angle formed by the tip of one needle crystal and the core and the tip of another needle crystal is preferably 109.5 degrees.
The zinc oxide can also include zinc oxide surface-treated with a coupling agent in the present invention, and the coupling agent used here is preferably a silane coupling agent, a titanate coupling agent, or an aluminum coupling agent. It is done.
In the copolymer composition of the present invention, acicular zinc oxide may be present, but this is caused by breakage of acicular crystal parts extending in a plurality of directions of zinc oxide having a tetrapot structure. It does not detract from the main characteristics of the invention.
本発明で用いる炭素数８以上の脂肪酸（４）とは、飽和あるいは不飽和の脂肪酸であってもよく、好ましくは炭素数３４までの脂肪酸が良い。さらに好ましくは炭素数１４〜２２のもである。よりさらに好ましくは、飽和脂肪酸である。具体的には、ラウリン酸、トリデシル酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、ヘプタデシル酸、ステアリン酸、ノナデカン酸、オレイン酸、カプリン酸、ベヘニン酸、リノール酸等の脂肪酸を挙げることができ、これらの中でもステアリン酸、オレイン酸、ラウリン酸が好適に用いられる。 The fatty acid (4) having 8 or more carbon atoms used in the present invention may be a saturated or unsaturated fatty acid, preferably a fatty acid having up to 34 carbon atoms. More preferably, it has 14 to 22 carbon atoms. Even more preferably, it is a saturated fatty acid. Specific examples include fatty acids such as lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, oleic acid, capric acid, behenic acid, linoleic acid, and the like. Of these, stearic acid, oleic acid, and lauric acid are preferably used.
本発明で用いるアクリル系樹脂とは、具体的には（メタ）アクリル酸アルキルエステルからなる群より選ばれる少なくとも１種の化合物の重合体又は共重合体である。（メタ）アクリル酸アルキルエステルとしては、例えば、メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、ｎ−プロピルアクリレート、ｎ−ブチルアクリレート、２−エチルヘキシルアクリレート、ヘキシルメタクリレート、２−エチルヘキシルメタクリレート、ドデシルメタクリレートが挙げられ、これら化合物を単独で、または２種上組み合わせて重合させて得られる共重合体であれば使用することができ、例えば、日本ゼオン株式会社製「商品名：ハイブレン」等が挙げられる。また、アクリル酸アルキルエステルを重合して得られるアクリル系ゴム粒子に（メタ）アクリル酸アルキルエステルを主成分として得られるグラフト共重合体も使用することができ、例えば、三菱レイヨン社製「商品名：メタブレン」等が挙げられる。 The acrylic resin used in the present invention is specifically a polymer or copolymer of at least one compound selected from the group consisting of (meth) acrylic acid alkyl esters. Examples of the (meth) acrylic acid alkyl ester include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, and dodecyl methacrylate. Any copolymer can be used as long as it is a copolymer obtained by polymerizing these compounds alone or in combination of two or more thereof, and examples thereof include “trade name: Hybrene” manufactured by Nippon Zeon Co., Ltd. In addition, a graft copolymer obtained using (meth) acrylic acid alkyl ester as a main component can also be used for acrylic rubber particles obtained by polymerizing alkyl acrylate, such as “trade name” manufactured by Mitsubishi Rayon Co., Ltd. : Methabrene "and the like.
本発明で用いるパラフィン系オイル（６）とは、石油留分又は残油を水素添加し、精製したもの又は分解により得られる潤滑油基油のことである。
本発明のパラフィン系オイルは４０℃における動粘度が１００ｍｍ２／ｓｅｃ以上のもの、好ましくは１００〜１００００ｍｍ２／ｓｅｃ、さらに好ましくは２００〜５０００ｍｍ２／ｓｅｃである。
このようなパラフィン系オイルとして、例えば、日本油脂株式会社製のＮＡソルベント、出光興産株式会社製のＰＷ−９０、ＰＷ−３８０、出光石油化学株式会社製のＩＰ−ソルベント２８３５、三光化学工業株式会社製のネオチオゾール等が挙げられる。
The paraffinic oil (6) used in the present invention is a lubricating base oil obtained by hydrogenating a petroleum fraction or residual oil and purifying it or by decomposition.
The paraffinic oil of the present invention has a kinematic viscosity at 40 ° C. of 100 mm 2 / sec or more, preferably 100 to 10,000 mm 2 / sec, more preferably 200 to 5000 mm 2 / sec.
As such paraffinic oil, for example, NA Solvent manufactured by Nippon Oil & Fats Co., Ltd., PW-90 and PW-380 manufactured by Idemitsu Kosan Co., Ltd., IP-Solvent 2835 manufactured by Idemitsu Petrochemical Co., Ltd., Sanko Chemical Co., Ltd. Examples thereof include neothiozole and the like.
本発明で用いる、１０〜４００Ｗ／ｍ・Ｋの熱伝導性充填剤（７）とは、核部とこの核部から異なる４軸方向に伸びた針状結晶である酸化亜鉛（３）以外の、熱伝導率が１０〜４００Ｗ／ｍ・Ｋの範囲にある充填材であり、例えば金属粉、金属窒化物、金属炭化物、金属酸化物、黒鉛化炭化水素、天然黒鉛、球状黒鉛粒子が挙げられる。金属粉としては、金、銀、銅、アルミニウム等が挙げられる。
金属窒化物としては、窒化ホウ素、窒化ケイ素、窒化アルミニウム等が挙げられる。金属炭化物としては炭化珪素等が挙げられる。また金属酸化物は、酸化亜鉛、酸化アルミニウム、酸化マグネシウム、酸化ケイ素等が挙げられる。
The heat-conductive filler (7) of 10 to 400 W / m · K used in the present invention is other than zinc oxide (3) which is a core and needle-like crystals extending in different four-axis directions from the core. , A filler having a thermal conductivity in the range of 10 to 400 W / m · K, such as metal powder, metal nitride, metal carbide, metal oxide, graphitized hydrocarbon, natural graphite, and spherical graphite particles. . Examples of the metal powder include gold, silver, copper, and aluminum.
Examples of the metal nitride include boron nitride, silicon nitride, and aluminum nitride. Examples of the metal carbide include silicon carbide. Examples of the metal oxide include zinc oxide, aluminum oxide, magnesium oxide, and silicon oxide.
また、これら熱伝導性充填剤の形状は繊維状及び／または非繊維状（板状、鱗片状、粒状、不定形状、球状）であってもよい。
この中でも、本発明の共重合体組成物に添加する際の作業性および熱伝導率改良効果から、好ましくは金属酸化物、金属窒化物であり、より好ましくは金属窒化物であり、さらに好ましくは窒化ホウ素である。
熱伝導性充填材の熱伝導率が１０Ｗ／ｍ・Ｋに満たないと、本発明の共重合体組成物に添加した際、十分な熱伝導率改良効果が得られず、好ましくない。
Moreover, the shape of these heat conductive fillers may be fibrous and / or non-fibrous (plate-like, scale-like, granular, irregular shape, spherical).
Among these, from the workability and the effect of improving the thermal conductivity when added to the copolymer composition of the present invention, preferably a metal oxide or a metal nitride, more preferably a metal nitride, still more preferably Boron nitride.
If the thermal conductivity of the thermally conductive filler is less than 10 W / m · K, when it is added to the copolymer composition of the present invention, a sufficient effect of improving the thermal conductivity cannot be obtained, which is not preferable.
（配合割合の記述）
本発明の請求項１に記載の共重合体組成物において、水添共重合体（１）及び／または変性水添共重合体（２）からなるスチレン系軟質樹脂、核部とこの核部から異なる４軸方向に伸びた針状結晶である酸化亜鉛（３）および炭素数８以上の脂肪酸（４）との配合割合は、成分（１）及び／または成分（２）からなるスチレン系軟質樹脂の合計量の含有量は５〜３５質量％および核部とこの核部から異なる４軸方向に伸びた針状結晶である酸化亜鉛（３）６５〜９５質量％、かつ成分（１）〜(３)の合計量１００質量部に対して、炭素数８以上の脂肪酸（４）０．０１〜５．０質量部である。
(Description of blending ratio)
In the copolymer composition according to claim 1 of the present invention, a styrenic soft resin comprising a hydrogenated copolymer (1) and / or a modified hydrogenated copolymer (2), a core part and the core part. The blending ratio of zinc oxide (3), which is needle crystals extending in different four-axis directions, and fatty acid (4) having 8 or more carbon atoms is a styrene-based soft resin comprising component (1) and / or component (2). The content of the total amount of is 5 to 35% by mass, and zinc oxide (3) 65 to 95% by mass, which is a needle-like crystal extending in the four-axis directions different from the core and the core, and the components (1) to ( It is 0.01-5.0 mass parts of fatty acids (4) having 8 or more carbon atoms with respect to 100 mass parts of the total amount of 3).
成分（１）〜（３）の全体量に対して、成分（１）及び／または成分（２）の合計量の含有量は５〜３５質量％であることが、組成物の熱伝導性、柔軟性、カレンダ成形加工性に優れ好ましい。
成分（３）の含有量が６５質量％未満だと、組成物の熱伝導性が不十分であり好ましくなく、９５質量％を超えると組成物の柔軟性、カレンダー成形加工性が不十分であり好ましくない。
また、成分（３）の成分（１）及び／または成分（２）の合計量に対する比率は、成分（１）及び／または成分（２）の合計量１００質量部に対して、成分（３）は２００〜９００質量部であることが熱伝導性、柔軟性、カレンダ成形加工性に優れ好ましい。より好ましくは３００〜８００質量部であり、とりわけ好ましくは３６０〜７５０質量部である。
The thermal conductivity of the composition is such that the total content of component (1) and / or component (2) is 5 to 35% by mass relative to the total amount of components (1) to (3). It is excellent in flexibility and calendar molding processability.
If the content of the component (3) is less than 65% by mass, the composition is insufficient in thermal conductivity, and if it exceeds 95% by mass, the composition has insufficient flexibility and calender molding processability. It is not preferable.
The ratio of the component (3) to the total amount of the component (1) and / or the component (2) is the component (3) with respect to 100 parts by mass of the total amount of the component (1) and / or the component (2). Is preferably 200 to 900 parts by mass because of its excellent thermal conductivity, flexibility, and calendar molding processability. More preferably, it is 300-800 mass parts, Especially preferably, it is 360-750 mass parts.
好ましい範囲は、成分（１）及び／または成分（２）の合計量６〜２５質量％、成分（３）７５〜９４質量％、さらに好ましい範囲は、成分（１）及び／または成分（２）の合計量７〜２２質量％、（２）７８〜９３質量％である。
成分（１）〜（３）の合計量１００質量部に対する炭素数８以上の脂肪酸（４）の含有量は０．０１質量部未満だと、組成物の柔軟性および熱伝導性改良効果および組成物のカレンダー成形加工性が不十分であり、５質量部を超えると組成物の放熱性が不十分となる場合があり好ましくない。
成分（４）の好ましい範囲は、成分（１）〜（３）の合計量１００質量部に対して、成分（４）の含有量は０．０５〜２．０質量部、さらに好ましい範囲は、０．０８〜０．４質量部である。
The preferred range is 6 to 25% by mass of component (1) and / or component (2), 75 to 94% by mass of component (3), and the more preferred range is component (1) and / or component (2). The total amount is 7 to 22% by mass and (2) 78 to 93% by mass.
When the content of the fatty acid (4) having 8 or more carbon atoms with respect to 100 parts by mass of the total amount of the components (1) to (3) is less than 0.01 parts by mass, the flexibility and thermal conductivity improving effect and composition of the composition The calender molding processability of the product is insufficient, and if it exceeds 5 parts by mass, the heat dissipation of the composition may be insufficient, which is not preferable.
The preferable range of the component (4) is 0.05 to 2.0 parts by mass of the content of the component (4) with respect to 100 parts by mass of the total amount of the components (1) to (3). 0.08 to 0.4 parts by mass.
（配合割合の記述 組成物２）
本発明の請求項２に記載の共重合体組成物において、成分（１）及び／または成分（２）からなるスチレン系軟質樹脂、成分（３）、成分（４）および成分（５）の配合割合は、成分（１）及び／または成分（２）からなるスチレン系軟質樹脂５〜３５質量％および成分（３）６５〜９５質量％、かつ成分（１）〜(３)の合計量１００質量部に対して、成分（４）０．０１〜５．０質量部、および成分（５）０．０１〜５．０質量部である。
成分（１）〜（３）の合計量１００質量部に対する成分（５）の含有量は０．０１〜５．０質量部であることが、組成物の熱伝導性、柔軟性、カレンダ成形加工性に優れ好ましい。
成分（５）の好ましい範囲は、成分（１）〜（３）の合計量１００質量部に対して、成分（５）の含有量は０．０５〜２．０質量部、さらに好ましい範囲は、０．０８〜０．４質量部である。
(Description of blending ratio Composition 2)
In the copolymer composition according to claim 2 of the present invention, blending of styrenic soft resin comprising component (1) and / or component (2), component (3), component (4) and component (5) The proportion is 5 to 35% by mass of the styrenic soft resin composed of component (1) and / or component (2), 65 to 95% by mass of component (3), and 100% by mass of components (1) to (3). It is 0.01-5.0 mass parts of component (4) and 0.01-5.0 mass parts of component (5) with respect to parts.
The content of the component (5) with respect to 100 parts by mass of the total amount of the components (1) to (3) is 0.01 to 5.0 parts by mass, and the thermal conductivity, flexibility, and calendar molding processing of the composition. Excellent in properties and preferable.
The preferable range of the component (5) is 0.05 to 2.0 parts by mass of the content of the component (5) with respect to 100 parts by mass of the total amount of the components (1) to (3). 0.08 to 0.4 parts by mass.
（配合割合の記述 組成物３）
本発明の請求項３に記載の共重合体組成物において、成分（１）及び／または成分（２）およびパラフィン系オイル（６）を含んだスチレン系軟質樹脂、成分（３）、成分（４）および成分（５）の配合割合は、成分（１）及び／または成分（２）およびパラフィン系オイル（６）を含めてなるスチレン系軟質樹脂５〜３５質量％および（３）６５〜９５質量％、かつ成分（１）、成分（２）、成分（６）、成分(３)の合計量１００質量部に対して、成分（４）０．０１〜５．０質量部および成分（５）０．０１〜５．０質量部である。
スチレン系軟質樹脂中における成分（１）および／または成分（２）の合計量と、成分（６）の割合は、成分（１）および／または成分（２）の合計量 ２６〜９９質量％、成分（６）１〜７４質量％であることが熱伝導性、柔軟性、カレンダ成形加工性の点から好ましい。より好ましくは、成分（１）および／または成分（２）の合計量 ３４〜９５質量％、成分（６）５〜６６質量％であり、とりわけ好ましくは、成分（１）および／または成分（２）の合計量 ４２〜９０質量％、成分（６）１０〜５８質量％である。
(Description of blending ratio Composition 3)
In the copolymer composition according to claim 3 of the present invention, a styrenic soft resin containing component (1) and / or component (2) and paraffinic oil (6), component (3), component (4) ) And component (5) are blended in proportions of 5 to 35% by mass of styrene-based soft resin including component (1) and / or component (2) and paraffinic oil (6), and (3) 65 to 95 mass. % And component (4) 0.01 to 5.0 parts by mass and component (5) with respect to 100 parts by mass of the total amount of component (1), component (2), component (6) and component (3) 0.01 to 5.0 parts by mass.
The total amount of component (1) and / or component (2) in the styrenic soft resin and the ratio of component (6) are the total amount of component (1) and / or component (2) 26 to 99% by mass, It is preferable that it is 1-74 mass% of a component (6) from the point of thermal conductivity, a softness | flexibility, and a calendar molding processability. More preferably, the total amount of the component (1) and / or the component (2) is 34 to 95% by mass and the component (6) is 5 to 66% by mass, and particularly preferably the component (1) and / or the component (2). ) 42-90 mass% and component (6) 10-58 mass%.
（配合割合の記述 組成物４）
本発明の請求項４に記載の共重合体組成物において、成分（１）及び／または成分（２）、成分（６）および成分（７）を含んだスチレン系軟質樹脂と、成分（３）、成分（４）、成分（５）の配合割合は、成分（１）及び／または成分（２）、成分（６）および成分（７）を含めてなるスチレン系軟質樹脂の合計量の含有量５〜３５質量％および核部とこの核部から異なる４軸方向に伸びた針状結晶である酸化亜鉛（３）６５〜９５質量％、かつ成分（１）、成分（２）、成分(６)、成分（７）、成分(３)の合計量１００質量部に対して、成分（４）０．０１〜５．０質量部および成分（５）０．０１〜５．０質量部である。
(Description of blending ratio Composition 4)
In the copolymer composition according to claim 4 of the present invention, a styrenic soft resin containing component (1) and / or component (2), component (6) and component (7), and component (3) , Component (4), Component (5) is mixed in a total amount of styrenic soft resin including Component (1) and / or Component (2), Component (6) and Component (7) 5 to 35% by mass and zinc oxide (3) 65 to 95% by mass, which is a needle-like crystal extending in the four axis directions different from the core part and the core part, and component (1), component (2), component (6 ), Component (7), and component (3) in a total amount of 100 parts by mass, component (4) 0.01 to 5.0 parts by mass and component (5) 0.01 to 5.0 parts by mass. .
スチレン系軟質樹脂中における成分（１）および／または成分（２）の合計量と、成分（６）と成分（７）の割合は、成分（１）および／または成分（２）２４〜８５質量％、成分（６）１〜６６質量％および成分（７）１０〜５０質量％であることが熱伝導性、柔軟性、カレンダ成形加工性の点から好ましい。より好ましくは、成分（１）および／または成分（２）２９〜８０質量％、成分（６）５〜５６質量％および成分（７）１５〜４５質量％であり、とりわけ好ましくは、成分（１）および／または成分（２）の合計量 ３４〜７２質量％、成分（６）８〜４６質量％、成分（７）２０〜４０質量％である。
本発明の共重合体組成物は、本発明の目的を損なわない範囲内で必要に応じて、難燃剤、難燃助剤、酸化防止剤、紫外線吸収剤の他の添加剤として、例えば、熱安定剤、耐電防止剤、光安定剤、老化防止剤、着色剤等の添加物を配合することができる。これらの添加物は混練時に添加しても、水添共重合体又は変性水添共重合体の製造時に予め該共重合体の中に含ませておいても良い。
The total amount of component (1) and / or component (2) in the styrenic soft resin and the ratio of component (6) and component (7) are 24 to 85 masses of component (1) and / or component (2). %, Component (6) 1 to 66 mass%, and component (7) 10 to 50 mass% are preferable from the viewpoint of thermal conductivity, flexibility, and calender molding processability. More preferably, they are component (1) and / or component (2) 29-80 mass%, component (6) 5-56 mass%, and component (7) 15-45 mass%, and particularly preferably component (1) ) And / or the total amount of component (2) is 34 to 72% by mass, component (6) is 8 to 46% by mass, and component (7) is 20 to 40% by mass.
The copolymer composition of the present invention may contain, as necessary, other additives such as a flame retardant, a flame retardant aid, an antioxidant, and an ultraviolet absorber as long as the object of the present invention is not impaired. Additives such as stabilizers, antistatic agents, light stabilizers, anti-aging agents, and coloring agents can be blended. These additives may be added at the time of kneading, or may be preliminarily included in the copolymer at the time of producing the hydrogenated copolymer or the modified hydrogenated copolymer.
これらの添加物の添加量は、本発明の共重合体組成物の合計量１００質量部に対して、合計で１００質量部を越えない範囲である。
本発明の共重合体組成物は、上記各成分を得る方法として、ブラベンダー、ニーダー、バンバリーミキサー、二軸あるいは一軸押出機など従来の公知技術によって容易に製造でき、得られた共重合体組成物は、一般的な射出成形、インジェクションプレス成形、またはガスインジェクション成形など公知の成型方法にて成形を行うことが可能である。
また該共重合体組成物をシート状として得る時の成形方法としては、上記の方法で混練した後、押出シート成形、カレンダー成形、ロール成形、プレス成形等により成形することができる。本発明における放熱性に優れた樹脂シートの厚みは、通常０．００５〜３ｍｍであり、好ましくは０．０１〜１ｍｍである。また、該樹脂シートは表面の平滑であることが好ましく、ＪＩＳ・Ｋ−７１０５に準拠して測定した樹脂シートの表面における６０度表面グロスの値が１０以上であることが好ましい。
The addition amount of these additives is in a range not exceeding 100 parts by mass in total with respect to 100 parts by mass of the total amount of the copolymer composition of the present invention.
The copolymer composition of the present invention can be easily produced by a conventional known technique such as Brabender, kneader, Banbury mixer, twin-screw or single-screw extruder as a method for obtaining each of the above components, and the obtained copolymer composition The product can be molded by a known molding method such as general injection molding, injection press molding, or gas injection molding.
As a molding method for obtaining the copolymer composition as a sheet, it can be molded by extrusion sheet molding, calender molding, roll molding, press molding or the like after kneading by the above method. The thickness of the resin sheet excellent in heat dissipation in the present invention is usually 0.005 to 3 mm, preferably 0.01 to 1 mm. The resin sheet preferably has a smooth surface, and the 60 degree surface gloss value on the surface of the resin sheet measured in accordance with JIS K-7105 is preferably 10 or more.
本発明の樹脂シートは、熱伝導性、柔軟性、カレンダ成形時の破れや厚みムラが無いといった成形加工性に優れており、パソコン、家庭用ゲーム機等のコンピュータ類の放熱部品、ＤＶＤプレーヤー、ＤＶＤレコーダー用の放熱部品、ＨＤＤレコーダー用放熱部品、家庭用テレビ、プラズマディスプレイ、液晶テレビ等のディスプレイ電源ユニット等の放熱部品、携帯電話、各種コンピュータ類、各種ＡＶ機器、ＯＡ機器等に用いられる放熱部品、カーステレオ、カーナビゲーションシステム、インバーター、照明、エアコンの自動車電装部材に用いられる放熱部品等など高熱伝導性が必要とされる用途に好適に使われる。
以下、実施例に基づき、本発明を説明する。
The resin sheet of the present invention is excellent in molding processability such as thermal conductivity, flexibility, and no tearing or uneven thickness during calendar molding, and heat dissipation parts for computers such as personal computers and home game machines, DVD players, Heat radiation parts for DVD recorders, heat radiation parts for HDD recorders, heat radiation parts such as display power supply units for home TVs, plasma displays, liquid crystal televisions, mobile phones, various computers, various AV equipment, OA equipment, etc. It is suitably used for applications that require high thermal conductivity, such as parts, car stereos, car navigation systems, inverters, lighting, and heat dissipating parts used in automotive electrical components of air conditioners.
Hereinafter, the present invention will be described based on examples.
以下に本発明を実施例により具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。
水添共重合体及び変性水添共重合体は以下に示す手順で共重合体を得た。
なお、重合体の特性や物性の測定は次のようにして行った。
１．共重合体の特性
１）スチレン含有量：紫外分光光度計（（株）島津製作所製、ＵＶ−２４５０）を用いて測定した。
２）ポリスチレンブロック含量：水添前の重合体を用い、I．M．Kolthoff，etal．，Ｊ．Polym．Sc i．１，４２９（１９４６）に記載の方法で測定した。
３）ビニル結合量及び水添率：核磁気共鳴装置（ＢＲＵＫＥＲ社製、ＤＰＸ−４００）を用いて測定した。
４）分子量及び分子量分布：ＧＰＣ〔装置は、ウォーターズ製〕で測定し、溶媒にはテトラヒドロフランを用い、測定条件は、温度３５℃で行った。分子量は、クロマトグラムのピークの分子量を、市販の標準ポリスチレンの測定から求めた検量線（標準ポリスチレンのピーク分子量を使用して作成）を使用して求めた重量平均分子量である。尚、クロマトグラム中にピークが複数有る場合の分子量は、各ピークの分子量と各ピークの組成比（クロマトグラムのそれぞれのピークの面積比より求める）から求めた平均分子量をいう。また，分子量分布は，得られた重量平均分子量と数平均分子量の比である。
５）結晶化ピーク及び結晶化ピーク熱量：ＤＳＣ［マックサイエンス社製、ＤＳＣ３２００Ｓ］で測定した。室温から３０℃／分の昇温速度で１５０℃まで昇温させ、その後１０℃／分の降温速度で−１００℃まで降温して結晶化カーブを測定して結晶化ピークの有無を確認した。また、結晶化ピークがある場合、そのピークが出る温度を結晶化ピーク温度とし、結晶化ピーク熱量を測定した。
６）変性率：シリカ系ゲルを充填剤としたＧＰＣカラムに、変性した成分が吸着する特性を応用し、試料及び低分子量内部標準ポリスチレンを含む試料溶液に関して、上記４のポリスチレン系ゲル（昭和電工製：Ｓｈｏｄｅｘ）のＧＰＣと、シリカ系カラムＧＰＣ（デュポン社製Ｚｏｒｂａｘ）の両クロマトグラムを測定し、それらの差分よりシリカカラムへの吸着量を測定し変性率を求めた。
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited only to these examples.
A hydrogenated copolymer and a modified hydrogenated copolymer were obtained by the following procedure.
In addition, the characteristics and physical properties of the polymer were measured as follows.
1. Characteristics of copolymer 1) Styrene content: measured using an ultraviolet spectrophotometer (manufactured by Shimadzu Corporation, UV-2450).
2) Polystyrene block content: The polymer before hydrogenation was used. M. Kolthoff, etal. , J .; Polym. Sc i. 1, 429 (1946).
3) Amount of vinyl bonds and hydrogenation rate: Measured using a nuclear magnetic resonance apparatus (manufactured by BRUKER, DPX-400).
4) Molecular weight and molecular weight distribution: Measured by GPC [device is manufactured by Waters], tetrahydrofuran was used as a solvent, and measurement conditions were performed at a temperature of 35 ° C. The molecular weight is a weight average molecular weight obtained by using a calibration curve (created using the peak molecular weight of standard polystyrene) obtained by measuring the molecular weight of the peak of the chromatogram from measurement of commercially available standard polystyrene. The molecular weight when there are a plurality of peaks in the chromatogram refers to the average molecular weight determined from the molecular weight of each peak and the composition ratio of each peak (determined from the area ratio of each peak in the chromatogram). The molecular weight distribution is a ratio of the obtained weight average molecular weight and number average molecular weight.
5) Crystallization peak and crystallization peak calorie: Measured by DSC [manufactured by Mac Science, DSC3200S]. The temperature was raised from room temperature to 150 ° C. at a rate of temperature rise of 30 ° C./min, and then the temperature was lowered to −100 ° C. at a rate of temperature drop of 10 ° C./min, and the crystallization curve was measured to confirm the presence or absence of a crystallization peak. Further, when there was a crystallization peak, the temperature at which the peak appeared was defined as the crystallization peak temperature, and the crystallization peak calorie was measured.
6) Modification rate: Applying the property that the modified component is adsorbed to a GPC column with a silica gel as a filler, the above-mentioned polystyrene gel (Showa Denko) Both chromatograms of GPC (manufactured by Shodex) and silica-based column GPC (Zorbax manufactured by DuPont) were measured, and the amount of adsorption to the silica column was measured from the difference between them to determine the modification rate.
＜水添共重合体及び変性水添共重合体の調製＞
水添共重合体等の調製水添共重合体等は以下の方法で調製した。なお、下記の実施例において、水添反応に用いた水添触媒は、下記の方法で調製した。
窒素置換した反応容器に乾燥、精製したシクロヘキサン２リットルを仕込み、ビス（η５−シクロペンタジエニル）チタニウムジー（ｐ−トリル）４０ミリモルと分子量が約１，０００の１，２−ポリブタジエン（１，２−ビニル結合約８５％）１５０グラムを溶解した後、ｎ−ブチルリチウム６０ミリモルを含む、シクロヘキサン溶液を溶解して室温で５分反応させ、直ちにｎ−ブタノール４０ミリモルを添加撹拌して室温で保存した。
<Preparation of hydrogenated copolymer and modified hydrogenated copolymer>
Preparation of hydrogenated copolymer and the like Hydrogenated copolymer and the like were prepared by the following method. In the following examples, the hydrogenation catalyst used for the hydrogenation reaction was prepared by the following method.
A reaction vessel purged with nitrogen was charged with 2 liters of dried and purified cyclohexane, 40 mmol of bis (η5-cyclopentadienyl) titanium di (p-tolyl) and 1,2-polybutadiene having a molecular weight of about 1,000 (1, After dissolving 150 g of 2-vinyl bond (about 85%), a cyclohexane solution containing 60 mmol of n-butyllithium was dissolved and reacted at room temperature for 5 minutes. Immediately after adding 40 mmol of n-butanol, the mixture was stirred at room temperature. saved.
＜ポリマー１の調製＞
ポリマー１（水添共重合体）の調整は、内容積が１０Ｌの撹拌装置及びジャケット付き槽型反応器を用いて、共重合を以下の方法で行った。
シクロヘキサン１０質量部を反応器に仕込んで温度７０℃に調整した後、ｎ−ブチルリチウムを全モノマー（反応器に投入したブタジエンモノマー及びスチレンモノマーの総量）の重量に対して０．０７６質量％、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン（以下ＴＭＥＤＡ）をｎ−ブチルリチウム１モルに対して０．４モル添加し、その後モノマーとしてスチレン８質量部を含有するシクロヘキサン溶液（モノマー濃度２２質量％）を約３分間かけて添加し、反応器内温を７０℃に調整しながら３０分間反応させた。
<Preparation of polymer 1>
The polymer 1 (hydrogenated copolymer) was prepared by copolymerization by the following method using a stirring apparatus having an internal volume of 10 L and a tank reactor with a jacket.
After charging 10 parts by mass of cyclohexane into the reactor and adjusting the temperature to 70 ° C., n-butyllithium is 0.076% by mass with respect to the weight of all monomers (total amount of butadiene monomer and styrene monomer charged into the reactor), 0.4 mol of N, N, N ′, N′-tetramethylethylenediamine (hereinafter TMEDA) is added to 1 mol of n-butyllithium, and then a cyclohexane solution containing 8 parts by mass of styrene as a monomer (monomer concentration 22 Mass%) was added over about 3 minutes, and the reaction was carried out for 30 minutes while adjusting the internal temperature of the reactor to 70 ° C.
次にブタジエン４８質量部とスチレン３６質量部とを含有するシクロヘキサン溶液（モノマー濃度２２質量％）を６０分かけて一定速度で連続的に反応器に供給し、その後、３０分間反応させた。この間、反応器内温は約７０℃になるように調整した。尚、供給終了直後にサンプリングしたポリマー溶液を解析したところ、ブタジエンの重合転化率；９０％、スチレンの重合転化率；１００％、ポリマー中のスチレン含量は４７．８質量％であった（ブロックＢのスチレン含量は４２．９質量％となる）。
その後、更にモノマーとしてスチレン８質量部を含有するシクロヘキサン溶液（モノマー濃度２２質量％）を約３分間かけて添加し、反応器内温を約７０℃に調整しながら３０分間反応させ、共重合体を得た。得られた共重合体のスチレン含量は５２質量％であり、スチレン重合体ブロックの含有量は１６質量％、ブタジエン部のビニル結合量は２１質量％、重量平均分子量は１６．５万、分子量分布は１．２であった。
Next, a cyclohexane solution (monomer concentration of 22% by mass) containing 48 parts by mass of butadiene and 36 parts by mass of styrene was continuously supplied to the reactor at a constant rate over 60 minutes, and then reacted for 30 minutes. During this time, the reactor internal temperature was adjusted to about 70 ° C. When the polymer solution sampled immediately after the supply was analyzed, the polymerization conversion of butadiene: 90%, the polymerization conversion of styrene: 100%, and the styrene content in the polymer was 47.8% by mass (Block B Styrene content is 42.9% by mass).
Thereafter, a cyclohexane solution containing 8 parts by mass of styrene as a monomer (monomer concentration: 22% by mass) is added over about 3 minutes, and the reaction is carried out for 30 minutes while adjusting the reactor internal temperature to about 70 ° C. Got. The resulting copolymer has a styrene content of 52% by mass, a styrene polymer block content of 16% by mass, a vinyl bond content of the butadiene part of 21% by mass, a weight average molecular weight of 16,000, and a molecular weight distribution. Was 1.2.
次に、得られた共重合体に、上記水添触媒を共重合体の重量に対してチタンとして１００重量ｐｐｍ添加し、水素圧０．７ＭＰａ、温度６５℃で水添反応を行った。反応終了後にメタノールを添加し、次に安定剤としてオクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネートを重合体の重量に対して０．３質量％添加し、水添共重合体（以下ポリマー１と称する）を得た。ポリマー１の水添率は９９％であった。また動的粘弾性測定の結果、ｔａｎδのピーク温度は−１５℃に存在した。また、ＤＳＣ測定の結果、結晶化ピークは無かった。 Next, 100 weight ppm of the hydrogenation catalyst as titanium with respect to the weight of the copolymer was added to the obtained copolymer, and a hydrogenation reaction was performed at a hydrogen pressure of 0.7 MPa and a temperature of 65 ° C. After completion of the reaction, methanol is added, and then octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer is added in an amount of 0.3% by weight based on the weight of the polymer. A hydrogenated copolymer (hereinafter referred to as polymer 1) was obtained. The hydrogenation rate of polymer 1 was 99%. As a result of dynamic viscoelasticity measurement, the peak temperature of tan δ was -15 ° C. As a result of DSC measurement, there was no crystallization peak.
＜酸化亜鉛＞
酸化亜鉛は、表面処理を行っていない、核部と核部から異なる４軸方向に伸びた針状結晶である酸化亜鉛（松下アムテック株式会社製、商品名：パナテトラ、ＷＺ−０５０１、針状結晶部の基部の径が０．７ｓ〜１４μｍ、針状結晶部の基部から先端までの長さが３〜２００μｍ）を用いた。
＜脂肪酸＞
脂肪酸は、旭電化工業株式会社製「商品名：アデカ脂肪酸 ＳＡ―２００」（ステアリン酸）を用いた。
＜アクリル系樹脂＞
アクリル系樹脂は、日本ゼオン株式会社製「商品名：ハイブレン B４０３」を用いた。
＜パラフィン系オイル＞
パラフィン系オイルは、出光興産株式会社製、商品名：ダイアナプロセスオイルＰＷ３８０（４０℃における動粘度が３８２ｍｍ２／ｓｅｃ）を用いた。
＜窒化ホウ素＞
窒化ホウ素は、電気化学工業株式会社製、商品名：デンカボロンナイトライド ＨＧＰを用いた。
<Zinc oxide>
Zinc oxide is a zinc oxide (made by Matsushita Amtech Co., Ltd., trade names: Panatetra, WZ-0501, acicular crystals) that is not surface-treated and extends from the nucleus to the four different axes from the nucleus. The diameter of the base of the part is 0.7 s to 14 μm, and the length from the base to the tip of the acicular crystal part is 3 to 200 μm.
<Fatty acid>
As the fatty acid, “trade name: Adeka Fatty Acid SA-200” (stearic acid) manufactured by Asahi Denka Kogyo Co., Ltd. was used.
<Acrylic resin>
As the acrylic resin, “trade name: Hybrene B403” manufactured by Zeon Corporation was used.
<Paraffin oil>
As the paraffinic oil, Idemitsu Kosan Co., Ltd., trade name: Diana Process Oil PW380 (dynamic viscosity at 40 ° C. is 382 mm 2 / sec) was used.
<Boron nitride>
Boron nitride was manufactured by Denki Kagaku Kogyo Co., Ltd. and trade name: DENKABORON NITRIDE HGP.
（実施例１〜４及び比較例１〜３）
上記で得られたポリマー１、酸化亜鉛、脂肪酸、アクリル系樹脂、パラフィンオイル、窒化ホウ素の各成分を表１に示す配合組成にてカレンダーシート成形を実施した。
カレンダー成形は下記の工程で行った。まず、配合組成物を、容量７５リットル、温度１５０℃、ブレード回転数２０ｒｐｍに設定した加圧ニーダ−にて５分間溶融混練を行い共重合体組成物を得た。該組成物をシリンダ温度１２０℃、押出機先端にダイスを取り付けた異方向二軸押出機にて、幅２００ｍｍ、厚さ１０ｍｍのシートを得た。該シートをロール径１０００ｍｍ、幅１６００ｍｍ、温度１４０℃、ロールギャップ間隔０．５ｍｍに調整したカレンダロール成形機にてシート成形し、幅１０００ｍｍのシートを得た。得られたシートの熱伝導率、硬度、シート成形時の破れの有無、厚みムラの程度を確認した。結果を表１に記す。
なお、評価は次の項目に従って行った。
(Examples 1-4 and Comparative Examples 1-3)
Calendar sheet molding was carried out with the blending composition shown in Table 1 for each component of polymer 1, zinc oxide, fatty acid, acrylic resin, paraffin oil, and boron nitride obtained above.
Calendar molding was performed in the following steps. First, the blended composition was melt-kneaded for 5 minutes in a pressure kneader set to a volume of 75 liters, a temperature of 150 ° C., and a blade rotation speed of 20 rpm to obtain a copolymer composition. A sheet having a width of 200 mm and a thickness of 10 mm was obtained from the composition using a different-direction twin-screw extruder having a cylinder temperature of 120 ° C. and a die attached to the tip of the extruder. The sheet was formed into a sheet with a calendar roll forming machine adjusted to have a roll diameter of 1000 mm, a width of 1600 mm, a temperature of 140 ° C., and a roll gap interval of 0.5 mm to obtain a sheet having a width of 1000 mm. The obtained sheet was confirmed for thermal conductivity, hardness, presence / absence of tearing during sheet molding, and thickness unevenness. The results are shown in Table 1.
The evaluation was performed according to the following items.
＜硬度＞
上記で得たシートの硬度を、Ａタイプ硬度計を用い、ＪＩＳ Ｋ６３０１に準じた方法で硬度を測定した。結果を表１に記す。
＜熱伝導率＞
上記で得た厚さ０．５ｍｍのシートを用いて、京都電子工業株式会社製 うす膜測定用ソフト（ＳＯＦＴ−ＱＴＭ５Ｗ）を備えた迅速熱伝導率測定機ＱＴＭ−５００（細線加熱法）を用いて熱伝導率を測定した。測定は、熱伝導率が既知であるレファレインスプレート（発泡ポリエチレン、シリコーンゴム、石英ガラス、ムライト、ジルコニア）を用いてボックス式プローブ（ＰＤ−１１）で熱伝導率を求める方法（特公平５−１２３６１号公報記載）で樹脂シートの熱伝導率を求めた。その結果を表１に示す。
<Hardness>
The hardness of the sheet obtained above was measured by a method according to JIS K6301 using an A type hardness meter. The results are shown in Table 1.
<Thermal conductivity>
Using the 0.5 mm thick sheet obtained above, a rapid thermal conductivity measuring device QTM-500 (thin wire heating method) equipped with a thin film measurement software (SOFT-QTM5W) manufactured by Kyoto Electronics Industry Co., Ltd. was used. The thermal conductivity was measured. The measurement is a method of obtaining the thermal conductivity with a box type probe (PD-11) using a reference plate (foamed polyethylene, silicone rubber, quartz glass, mullite, zirconia) whose thermal conductivity is known (Japanese Patent Publication No. 5). No. 12361), the thermal conductivity of the resin sheet was obtained. The results are shown in Table 1.
＜カレンダロール成形シートの破れの多少＞
上記で得られたカレンダロール成形シート、幅１０００ｍｍ 長さ３ｍを採取し、シートが繋がっていない箇所、及び穴の空いた個所の個数を目視で確認した。該箇所が２個未満を◎、２〜５箇所を○、５〜１０箇所を△、１０箇所以上を×として評価した。結果を表１に記す。
＜カレンダロール成形シートの厚みムラ＞
上記で得られたカレンダロール成形シート、幅１０００ｍｍのカレンダロール成形シートを２箇所、シート流れ方向に垂直に切断し、得られた切断面の端部及び中央部の厚みを測定した。６箇所の測定により得られた厚みの夫々から、調整したロール間隔０．５ｍｍを差し引いた差をもとめ、その平均値を算出した。結果を表１に記す。
<Slight tearing of calender roll molding sheet>
The calender roll molded sheet obtained above, a width of 1000 mm and a length of 3 m were collected, and the number of locations where the sheets were not connected and the locations where holes were formed was visually confirmed. The number of the points was evaluated as 箇 所, less than 2 ◎, 2 to 5 箇 所, 5 to 10 △, 10 or more ×. The results are shown in Table 1.
<Unevenness of calendar roll molded sheet>
The calender roll molded sheet obtained above and a calender roll molded sheet having a width of 1000 mm were cut at two locations perpendicular to the sheet flow direction, and the thicknesses of the end and center of the obtained cut surface were measured. The difference obtained by subtracting the adjusted roll interval of 0.5 mm was determined from each of the thicknesses obtained by the measurement at six locations, and the average value was calculated. The results are shown in Table 1.
本発明における共重合体組成物及びこれを用いて成形して得られる放熱性樹脂シートは、熱伝導性、柔軟性、カレンダ成形加工性に優れており、パソコン、家庭用ゲーム機等のコンピュータ類の放熱部品、ＤＶＤプレーヤー、ＤＶＤレコーダー用の放熱部品、ＨＤＤレコーダー用放熱部品、家庭用テレビ、プラズマディスプレイ、液晶テレビ等のディスプレイ電源ユニット等の放熱部品、携帯電話、各種コンピュータ類、各種ＡＶ機器、ＯＡ機器等に用いられる放熱部品、カーステレオ、カーナビゲーショシステム、インバーター、照明、エアコンの自動車電装部材に用いられる放熱部品等など高熱伝導性が必要とされる用途に好適に使われる。 The copolymer composition in the present invention and the heat-dissipating resin sheet obtained by molding the copolymer composition are excellent in thermal conductivity, flexibility, and calendar molding processability, and are computers such as personal computers and home-use game machines. Heat dissipation parts, heat dissipation parts for DVD players, DVD recorders, heat dissipation parts for HDD recorders, heat dissipation parts such as display power supply units for home TVs, plasma displays, liquid crystal TVs, mobile phones, various computers, various AV equipment, It is suitably used for applications that require high thermal conductivity, such as heat radiating parts used in OA equipment, car stereos, car navigation systems, inverters, lighting, and heat radiating parts used in automotive electrical components of air conditioners.
Claims (11)
（ａ）該成分（１）および／または（２）中の、ビニル芳香族化合物の含有量が５０質量％を越え、９０質量％以下、
（ｂ）該成分（１）および／または（２）中の、ビニル芳香族化合物重合体ブロックの量が４０質量％以下、
（ｃ）該成分（１）および／または（２）の水添共重合体の重量平均分子量が５万〜１００万、
（ｄ）該成分（１）および／または（２）中の、共役ジエン化合物に基づく二重結合の１０％以上が水添されている。 Hydrogenated copolymer (1) satisfying the following (a) to (d) by adding hydrogen to a copolymer comprising a conjugated diene and a vinyl aromatic compound and / or a copolymer comprising a conjugated diene and a vinyl aromatic compound. 5 to 35% by mass of a styrenic soft resin comprising a modified hydrogenated copolymer (2) formed by adding hydrogen to a polymer and satisfying the following (a) to (d) that binds at least one functional group: Zinc oxide (3) 65 to 95% by mass, and a total amount of the above components (1) to (3) of 100% by mass, characterized in that the core is a needle-like crystal extending in different four-axis directions from the core A copolymer composition comprising 0.01 to 5.0 parts by mass of a fatty acid (4) having 8 or more carbon atoms relative to parts.
(A) The content of the vinyl aromatic compound in the component (1) and / or (2) exceeds 50% by mass and is 90% by mass or less,
(B) The amount of the vinyl aromatic compound polymer block in the component (1) and / or (2) is 40% by mass or less,
(C) The weight average molecular weight of the hydrogenated copolymer of the component (1) and / or (2) is 50,000 to 1,000,000,
(D) 10% or more of the double bond based on the conjugated diene compound in the component (1) and / or (2) is hydrogenated.
（イ）Ｂ
（ロ）Ｂ−Ａ
（ハ）Ｂ−Ａ−Ｂ
（ニ）（Ｂ−Ａ）ｍ−Ｘ
（ホ）（Ｂ−Ａ）ｎ−Ｘ−Ａｐ
（ここで、Ｂは共役ジエンとビニル芳香族化合物とのランダム共重合体ブロックであり、Ａはビニル芳香族化合物重合体ブロックである。ｍは２以上の整数であり、ｎ及びｐはそれぞれ１以上の整数である。Ｘはカップリング剤残基を示す。） The copolymer (1) according to any one of claims 1 to 7, wherein the component (1) and / or the component (2) is a hydrogenated product of a copolymer having at least one structure selected from the following general formula: Combined composition.
(I) B
(B) B-A
(C) B-A-B
(D) (BA) m -X
(E) (BA) n- X-A p
(Here, B is a random copolymer block of a conjugated diene and a vinyl aromatic compound, A is a vinyl aromatic compound polymer block, m is an integer of 2 or more, and n and p are each 1) (It is an integer above. X represents a coupling agent residue.)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010007804A1 (en) * | 2008-07-17 | 2010-01-21 | ニホンハンダ株式会社 | Heat conductive oil composition, heat dissipating agent, and electronic device |
| JP2010280791A (en) * | 2009-06-03 | 2010-12-16 | Asahi Kasei E-Materials Corp | Heat-conductive molding, heat-conductive sheet, and method for producing heat-conductive sheet |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010007804A1 (en) * | 2008-07-17 | 2010-01-21 | ニホンハンダ株式会社 | Heat conductive oil composition, heat dissipating agent, and electronic device |
| JP2010280791A (en) * | 2009-06-03 | 2010-12-16 | Asahi Kasei E-Materials Corp | Heat-conductive molding, heat-conductive sheet, and method for producing heat-conductive sheet |
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