JP5481098B2 - Post-curing resin composition and electrical insulating material using the same - Google Patents
Post-curing resin composition and electrical insulating material using the same Download PDFInfo
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- JP5481098B2 JP5481098B2 JP2009133641A JP2009133641A JP5481098B2 JP 5481098 B2 JP5481098 B2 JP 5481098B2 JP 2009133641 A JP2009133641 A JP 2009133641A JP 2009133641 A JP2009133641 A JP 2009133641A JP 5481098 B2 JP5481098 B2 JP 5481098B2
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- carbon atoms
- olefin
- substituted
- ethylene
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- 239000011342 resin composition Substances 0.000 title claims description 68
- 238000011417 postcuring Methods 0.000 title claims description 59
- 239000011810 insulating material Substances 0.000 title description 12
- -1 vinyl compound Chemical class 0.000 claims description 75
- 229920001577 copolymer Polymers 0.000 claims description 68
- 125000004432 carbon atom Chemical group C* 0.000 claims description 53
- 150000004291 polyenes Chemical class 0.000 claims description 40
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical class C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 37
- 229920002554 vinyl polymer Polymers 0.000 claims description 36
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- 150000001336 alkenes Chemical class 0.000 claims description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 20
- 238000003860 storage Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 150000003623 transition metal compounds Chemical class 0.000 claims description 17
- 150000002430 hydrocarbons Chemical group 0.000 claims description 14
- 238000005259 measurement Methods 0.000 claims description 14
- 238000012718 coordination polymerization Methods 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 11
- 239000002685 polymerization catalyst Substances 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Chemical group 0.000 claims description 7
- 238000001228 spectrum Methods 0.000 claims description 7
- 239000011593 sulfur Chemical group 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000004711 α-olefin Substances 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000003426 co-catalyst Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 4
- 239000011574 phosphorus Chemical group 0.000 claims description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 4
- 229910052719 titanium Chemical group 0.000 claims description 4
- 239000010936 titanium Chemical group 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 claims description 3
- 239000007870 radical polymerization initiator Substances 0.000 claims description 3
- 229910052710 silicon Chemical group 0.000 claims description 3
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 239000010703 silicon Chemical group 0.000 claims description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims 1
- 238000001723 curing Methods 0.000 description 30
- 239000000047 product Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 239000011256 inorganic filler Substances 0.000 description 9
- 229910003475 inorganic filler Inorganic materials 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 7
- 238000011049 filling Methods 0.000 description 7
- 239000003566 sealing material Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- 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 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
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- 239000012766 organic filler Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 150000001639 boron compounds Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
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- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical group C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
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- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- QPFMBZIOSGYJDE-ZDOIIHCHSA-N 1,1,2,2-tetrachloroethane Chemical class Cl[13CH](Cl)[13CH](Cl)Cl QPFMBZIOSGYJDE-ZDOIIHCHSA-N 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
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- 230000005587 bubbling Effects 0.000 description 1
- KZUKCLOWAMFDDB-UHFFFAOYSA-L butylcyclopentane;dichlorozirconium Chemical compound Cl[Zr]Cl.CCCC[C]1[CH][CH][CH][CH]1.CCCC[C]1[CH][CH][CH][CH]1 KZUKCLOWAMFDDB-UHFFFAOYSA-L 0.000 description 1
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- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical group C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical compound C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000021003 saturated fats Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
本発明は、後硬化性樹脂組成物及びそれを用いた電気絶縁材料、特に高周波用電気絶縁材料に関する。 The present invention relates to a post-curing resin composition and an electric insulating material using the same, and particularly to an electric insulating material for high frequency.
ポリエチレン等のポリオレフィンやポリスチレン等の芳香族ビニル化合物重合体は、分子構造中に極性基を持たないため、優れた低誘電率、低誘電損失を示す材料として知られている。しかし、これらは耐熱性を結晶融点、又はガラス転移温度に依存するため電気絶縁体としての耐熱性に課題があり、さらに熱可塑性樹脂であるために製膜プロセス上の課題がある（特許文献１）。
パ−フルオロエチレン等のフッ素系樹脂は優れた低誘電率、低誘電損失と耐熱性に優れた特徴を有するが成形加工性、膜成形性が困難でありデバイス適性が低い。
一方、エポキシ樹脂、不飽和ポリエステル樹脂、ポリイミド樹脂、フェノ−ル樹脂等の後硬化樹脂を用いた基板、絶縁材料はその耐熱性、易取り扱い性から広く用いられてきているが、誘電率、誘電損失が比較的高く、高周波用の絶縁材料としては改善が望まれている（特許文献２）。
オレフィン系及びスチレン系の重合体セグメントからなるグラフト、又はブロック共重合体からなる電気絶縁材料が提案されている（特許文献３）。本材料はオレフィンやスチレン系の炭化水素系重合体の本質的な低誘電率、低誘電損失性に着目している。その製造方法は、市販のポリエチレン、ポリプロピレンにスチレンモノマ−、ジビニルベンゼンモノマ−とラジカル重合開始剤の存在下、一般的なグラフト重合を行うもので、このような手法ではグラフト効率が上がらず、ポリマ−の均一性が十分でないという課題がある。さらに、得られたポリマ−はゲルを含んでおり、加工性、充填性が悪いという課題があった。本材料は、熱可塑性樹脂で耐熱性が十分でなく、４−メチル−１−ペンテン系等の耐熱性樹脂を加える必要がある。本材料は、所定の場所に塗布あるいは充填した後硬化させる成形方法には適用できない。
特許文献４には、複数の芳香族ビニル基を有する炭化水素化合物を架橋成分として含む架橋構造体からなる絶縁層が記載されている。本架橋成分の重量平均分子量は１０００以下であることが好ましいとされており、明細書記載の例及び実施例はいずれも重量平均分子量は１０００以下である。別途、高分子量樹脂を配合し、本架橋成分と共架橋することで絶縁層を得ている。
一方、近年太陽電池（太陽光発電）は、地球環境保全の観点から注目されている。太陽電池は、高温高加湿や風雨に曝される室外などの環境下で長期にわたって使用されると、電池内部に湿気ないし水が透過する場合がある。ところで、太陽電池の封止材として用いられる架橋ＥＶＡは、透明性と軟質性に優れ、かつ長年使用され実績を有する材料ではある（特許文献５）が、透湿性が比較的高く、体積抵抗が比較的低いため、長期にわたる信頼性確保の観点からは問題点もあり、さらに信頼性を確保するためには十分な厚さが必要である等課題がある。また、酢酸の遊離による配線腐食、太陽電池セルの劣化への影響も懸念される。
そこで、非ＥＶＡ系の封止材が検討されている。例えば、特許文献６では、アイオノマ−を用い、特許文献７ではポリプロピレン系の軟質樹脂を用いてこの問題を解決使用としている。しかし、一般にはアイオノマ−樹脂は成形加工性やＥＶＡと比較すると軟質性が劣る等の課題を有している。ポリプロピレンを原料として含むオレフィン系の軟質樹脂は耐光性に課題を有していると考えられる。
Polyolefins such as polyethylene and aromatic vinyl compound polymers such as polystyrene do not have polar groups in their molecular structures, and are known as materials exhibiting excellent low dielectric constant and low dielectric loss. However, since these depend on the crystal melting point or the glass transition temperature, there is a problem in heat resistance as an electric insulator, and further, there is a problem in a film forming process because it is a thermoplastic resin (Patent Document 1). ).
Fluoro-based resins such as perfluoroethylene have excellent low dielectric constant, low dielectric loss, and excellent heat resistance, but are difficult to mold and form, and have low device suitability.
On the other hand, substrates and insulating materials using post-curing resins such as epoxy resins, unsaturated polyester resins, polyimide resins, phenol resins, etc. have been widely used due to their heat resistance and ease of handling. Loss is relatively high, and improvement is desired as a high-frequency insulating material (Patent Document 2).
An electrically insulating material composed of a graft or block copolymer composed of olefin-based and styrene-based polymer segments has been proposed (Patent Document 3). This material focuses on the intrinsic low dielectric constant and low dielectric loss of olefin and styrene hydrocarbon polymers. The production method is such that general graft polymerization is carried out in the presence of a styrene monomer, divinylbenzene monomer and a radical polymerization initiator on commercially available polyethylene or polypropylene. In such a technique, the graft efficiency is not increased and the polymer is not increased. There is a problem that the uniformity of − is not sufficient. Further, the obtained polymer contains a gel, and there is a problem that workability and filling property are poor. This material is a thermoplastic resin and does not have sufficient heat resistance, and it is necessary to add a heat-resistant resin such as 4-methyl-1-pentene. This material cannot be applied to a molding method in which a predetermined place is applied or filled and then cured.
Patent Document 4 describes an insulating layer made of a crosslinked structure containing a hydrocarbon compound having a plurality of aromatic vinyl groups as a crosslinking component. It is said that the weight average molecular weight of the crosslinking component is preferably 1000 or less, and in the examples and examples described in the specification, the weight average molecular weight is 1000 or less. Separately, a high molecular weight resin is blended and co-crosslinked with the present crosslinking component to obtain an insulating layer.
On the other hand, in recent years, solar cells (solar power generation) have attracted attention from the viewpoint of global environmental conservation. When a solar cell is used over a long period of time in an environment such as an outdoor room exposed to high temperature and high humidity or wind and rain, moisture or water may permeate inside the cell. By the way, crosslinked EVA used as a sealing material for solar cells is a material that has excellent transparency and flexibility and has been used for many years (Patent Document 5), but has relatively high moisture permeability and volume resistance. Since it is relatively low, there is a problem from the viewpoint of ensuring reliability over a long period of time, and there is a problem that a sufficient thickness is necessary to ensure reliability. In addition, there is a concern about wiring corrosion due to liberation of acetic acid and the effect on the deterioration of solar cells.
Therefore, non-EVA-based sealing materials have been studied. For example, Patent Document 6 uses an ionomer, and Patent Document 7 uses a polypropylene-based soft resin to solve this problem. However, in general, ionomer resins have problems such as molding processability and inferior flexibility as compared with EVA. Olefin-based soft resins containing polypropylene as a raw material are considered to have a problem in light resistance.
本発明は、製膜性等の成形加工性に優れ、低誘電率、低誘電損失で、軟質性、力学強度、耐熱性、温度特性、耐衝撃性、耐水性に優れる硬化体を得るための後硬化性樹脂組成物及び、その硬化体を用いた高周波用電気絶縁材料を提供することである。また、軟質性、充填性、水蒸気非透過性、電気絶縁性に優れる太陽電池封止材に用いることもできる。 The present invention is excellent in molding processability such as film forming property, low dielectric constant, low dielectric loss, and to obtain a cured product excellent in softness, mechanical strength, heat resistance, temperature characteristics, impact resistance, and water resistance. It is to provide a post-curing resin composition and a high-frequency electrical insulating material using the cured product. Moreover, it can also be used for the solar cell sealing material which is excellent in softness | flexibility, a filling property, water vapor | steam impermeability, and electrical insulation.
即ち、本発明は、以下の（以下の（１）〜（４）の条件を満たすことを特徴とするエチレン−オレフィン−ポリエン共重合体１０〜９０質量部、及び（５）の条件を満たす非極性ビニル化合物９０〜１０質量部及び硬化剤を含有することを特徴とする後硬化性樹脂組成物である。
（１）オレフィンが、炭素数３以上２０以下のαオレフィン、炭素数５以上２０以下の環状オレフィン、炭素数８以上２０以下の芳香族ビニル化合物から選ばれる一種以上である。
（２）ポリエンが、分子内にビニル基及び／又はビニレン基を複数有する炭素数５以上２０以下のポリエンから選ばれる一種以上である。
（３）エチレン−オレフィン−ポリエン共重合体の数平均分子量が１０００以上５万以下、重量平均分子量／数平均分子量が１．５以上５以下であり、かつ、ポリエン単位含有量が、数平均分子量あたり１個以上７個未満であることを満足し、オレフィン単位含有量が５モル％以上７０モル％以下であり、残部がエチレン単位である。
（４）エチレン、オレフィン及びポリエンを共重合するときに使用する触媒が、下記の一般式（１）又は（２）で表される遷移金属化合物と助触媒から構成されるシングルサイト配位重合触媒である。
式中、Ａ、Ｂは同一でも異なっていてもよく、非置換もしくは置換ベンゾインデニル基、非置換もしくは置換インデニル基、非置換もしくは置換シクロペンタジエニル基、又は非置換もしくは置換フルオレニル基から選ばれる基であり、少なくともＡ，Ｂのうち１個は非置換もしくは置換ベンゾインデニル基、非置換もしくは置換インデニル基から選ばれる基である。ここで置換ベンゾインデニル基、置換インデニル基、置換シクロペンタジエニル基、又は置換フルオレニル基とは、置換可能な水素の１個以上が炭素数１〜２０のアルキル基、炭素数６〜１０のアリール基、炭素数７〜２０のアルキルアリール基、ハロゲン原子、ＯＳｉＲ３基、ＳｉＲ３基、又はＰＲ２基（Ｒはいずれも炭素数１〜１０の炭化水素基を表す）で置換されたベンゾインデニル基、インデニル基、シクロペンタジエニル基、又はフルオレニル基である。
ＹはＡ、Ｂと結合を有し、他に置換基として水素もしくは炭素数１〜１５の炭化水素基（１〜３個の窒素、酸素、硫黄、燐、珪素原子を含んでもよい）を有するメチレン基、硼素基である。置換基は互いに異なっていても同一でもよい。また、Ｙは環状構造を有していてもよい。
Ｘは、水素、水酸基、ハロゲン、炭素数１〜２０の炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜４の炭化水素置換基を有するシリル基、又は炭素数１〜２０の炭化水素置換基を有するアミド基である。２個のＸは結合を有しても良い。
Ｍはジルコニウム、ハフニウム、又はチタンである。
式中、Ｃｐは非置換もしくは置換シクロペンタフェナンスリル基、非置換もしくは置換ベンゾインデニル基、非置換もしくは置換シクロペンタジエニル基、非置換もしくは置換インデニル基、又は非置換もしくは置換フルオレニル基から選ばれる基である。Ｙ’は、Ｃｐ、Ｚと結合を有し、他に水素もしくは炭素数１〜１５の炭化水素基を有するメチレン基、シリレン基、エチレン基、ゲルミレン基、硼素残基である。置換基は互いに異なっていても同一でもよい。また、Ｙ’は環状構造を有していてもよい。Ｚは窒素、酸素、又はイオウを含み、窒素、酸素、又はイオウでＭ’に配位する配位子でＹ’と結合を有し、他に水素、炭素数１〜１５の置換基を有する基である。
Ｍ’はジルコニウム、ハフニウム、又はチタンである。
Ｘ’は、水素、ハロゲン、炭素数１−１５のアルキル基、炭素数６−１０のアリール基、炭素数８−１２のアルキルアリール基、炭素数１−４の炭化水素置換基を有するシリル基、炭素数１−１０のアルコキシ基、又は炭素数１−６のアルキル置換基を有するジアルキルアミド基である。
ｎは、１、又は２の整数である。
（５）実質的に炭素数５以上２０以下の環状オレフィン及び／又は炭素数８以上２０以下の芳香族ビニル化合物から選ばれる一種以上からなり、かつポリエン含量が１質量部未満であることを特徴とする非極性ビニル化合物。
That is, the present invention provides the following (10 to 90 parts by mass of an ethylene-olefin-polyene copolymer characterized by satisfying the following conditions (1) to (4)) and a non-condition satisfying the condition (5): A post-curing resin composition comprising 90 to 10 parts by mass of a polar vinyl compound and a curing agent.
(1) The olefin is one or more selected from an α-olefin having 3 to 20 carbon atoms, a cyclic olefin having 5 to 20 carbon atoms, and an aromatic vinyl compound having 8 to 20 carbon atoms.
(2) The polyene is one or more selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and / or vinylene groups in the molecule.
(3) The number average molecular weight of the ethylene-olefin-polyene copolymer is from 1,000 to 50,000, the weight average molecular weight / number average molecular weight is from 1.5 to 5, and the polyene unit content is the number average molecular weight. The content of olefin units is 5 mol% or more and 70 mol% or less, and the balance is ethylene units.
(4) A single site coordination polymerization catalyst in which the catalyst used when copolymerizing ethylene, olefin and polyene is composed of a transition metal compound represented by the following general formula (1) or (2) and a co-catalyst It is.
In the formula, A and B may be the same or different and are selected from an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted indenyl group, an unsubstituted or substituted cyclopentadienyl group, or an unsubstituted or substituted fluorenyl group. At least one of A and B is a group selected from an unsubstituted or substituted benzoindenyl group and an unsubstituted or substituted indenyl group. Here, the substituted benzoindenyl group, the substituted indenyl group, the substituted cyclopentadienyl group, or the substituted fluorenyl group is an alkyl group having 1 to 20 carbon atoms, one or more hydrogen atoms that can be substituted, and having 6 to 10 carbon atoms. Benzoin substituted with an aryl group, an alkylaryl group having 7 to 20 carbon atoms, a halogen atom, an OSiR 3 group, an SiR 3 group, or a PR 2 group (wherein R represents a hydrocarbon group having 1 to 10 carbon atoms) A denenyl group, an indenyl group, a cyclopentadienyl group, or a fluorenyl group;
Y has a bond with A and B, and additionally has hydrogen or a hydrocarbon group having 1 to 15 carbon atoms (may contain 1 to 3 nitrogen, oxygen, sulfur, phosphorus, or silicon atoms) as a substituent. A methylene group and a boron group. The substituents may be different or the same. Y may have a cyclic structure.
X is hydrogen, a hydroxyl group, a halogen, a C1-C20 hydrocarbon group, a C1-C20 alkoxy group, a silyl group having a C1-C4 hydrocarbon substituent, or a C1-C20 It is an amide group having a hydrocarbon substituent. Two Xs may have a bond.
M is zirconium, hafnium, or titanium.
In the formula, Cp represents an unsubstituted or substituted cyclopentaphenanthryl group, an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, or an unsubstituted or substituted fluorenyl group. The group to be selected. Y ′ is a methylene group, a silylene group, an ethylene group, a germylene group, or a boron residue having a bond with Cp and Z, and further having hydrogen or a hydrocarbon group having 1 to 15 carbon atoms. The substituents may be different or the same. Y ′ may have a cyclic structure. Z contains nitrogen, oxygen or sulfur, is a ligand coordinated to M ′ with nitrogen, oxygen or sulfur, has a bond with Y ′, and additionally has hydrogen and a substituent having 1 to 15 carbon atoms. It is a group.
M ′ is zirconium, hafnium, or titanium.
X ′ is hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 8 to 12 carbon atoms, or a silyl group having a hydrocarbon substituent having 1 to 4 carbon atoms. , A dialkylamide group having an alkoxy group having 1 to 10 carbon atoms or an alkyl substituent having 1 to 6 carbon atoms.
n is an integer of 1 or 2.
(5) It consists essentially of one or more selected from cyclic olefins having 5 to 20 carbon atoms and / or aromatic vinyl compounds having 8 to 20 carbon atoms, and has a polyene content of less than 1 part by mass. A nonpolar vinyl compound.
本発明の後硬化性樹脂組成物は成形性に優れ、得られる硬化体は低誘電率、低誘電損失で体積抵抗が高く、かつ軟質性、力学強度、耐熱性、耐衝撃性、耐水性に優れ、弾性率の温度依存性が少なく、電気絶縁材料、特に高周波用の電気絶縁材料として好適に使用できる。
The post-curing resin composition of the present invention is excellent in moldability, and the obtained cured product has low dielectric constant, low dielectric loss, high volume resistance, and softness, mechanical strength, heat resistance, impact resistance, and water resistance. It is excellent and has a low temperature dependence of elastic modulus, and can be suitably used as an electrical insulation material, particularly an electrical insulation material for high frequencies.
以下にさらに詳細に説明する。
＜エチレン−オレフィン−ポリエン共重合体＞
本エチレン−オレフィン−ポリエン共重合体は、エチレン、オレフィンとポリエンを共重合して得られる。用いられるオレフィンとしては、炭素数３以上２０以下のαオレフィン、炭素数５以上２０以下の環状オレフィン、又は炭素数８以上２０以下の芳香族ビニル化合物から選ばれる一種以上である。
炭素数３以上２０以下のαオレフィンとしては、例えばプロピレン、１−ブテン、１−ヘキセン、１−オクテン、１−デカン、１−ドデカン、４−メチル−１−ペンテン、３，５，５−トリメチル−１−ヘキセンが例示できる。
炭素数５以上２０以下の環状オレフィンとしては、ノルボルネン、シクロペンテンが例示できる。
炭素数８以上２０以下の芳香族ビニル化合物としては、スチレン、パラメチルスチレン、パライソブチルスチレン、各種ビニルナフタレン、各種ビニルアントラセンが例示できる。
This will be described in more detail below.
<Ethylene-olefin-polyene copolymer>
The present ethylene-olefin-polyene copolymer is obtained by copolymerizing ethylene, olefin and polyene. The olefin used is at least one selected from an α-olefin having 3 to 20 carbon atoms, a cyclic olefin having 5 to 20 carbon atoms, or an aromatic vinyl compound having 8 to 20 carbon atoms.
Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-hexene, 1-octene, 1-decane, 1-dodecane, 4-methyl-1-pentene, 3,5,5-trimethyl. An example is -1-hexene.
Examples of the cyclic olefin having 5 to 20 carbon atoms include norbornene and cyclopentene.
Examples of the aromatic vinyl compound having 8 to 20 carbon atoms include styrene, paramethyl styrene, paraisobutyl styrene, various vinyl naphthalene, and various vinyl anthracene.
用いられるポリエンとしては、その分子内にビニル基及び／又はビニレン基を複数有する炭素数８以上２０以下のポリエンであり、オルト、メタ、パラの各種ジビニルベンゼン又はこれらの混合物、ジビニルナフタレン、ジビニルアントラセン、ｐ−２−プロペニルスチレン、ｐ−３−ブテニルスチレンなどの芳香族ビニル構造を有する化合物、シクロペンタジエン、ジシクロペンタジエン、エチリデンノルボルネン、各種ビニルシクロヘキセン等の環状構造を有する化合物である。この中で好ましくは、オルト、メタ、パラの各種ジビニルベンゼン、又はこれらの混合物が用いられ、最も好ましくはメタ及びパラジビニルベンゼンの混合物が用いられる。本明細書ではこれらジビニルベンゼンをジビニルベンゼン類と記す。
ポリエンとしてジビニルベンゼン類を用いた場合、硬化処理を行う際に硬化効率が高く、硬化が容易であるため好ましい。
以上のオレフィン、ポリエンには、他に極性基、例えば酸素原子、窒素原子等を含むαオレフィン、環状オレフィン、芳香族ビニル化合物やポリエンを含んでいてもよいがこれらモノマ−の総質量は、本後硬化性樹脂組成物の総質量の５質量％未満、好ましくは１質量％未満である必要がある。これを超えると本後硬化性樹脂組成物を硬化して得られる硬化体の誘電特性（誘電率／誘電損失）を悪化させてしまう。
The polyene used is a polyene having a carbon number of 8 or more and 20 or less having a plurality of vinyl groups and / or vinylene groups in the molecule, and various kinds of ortho, meta, and para divinylbenzenes or mixtures thereof, divinylnaphthalene, divinylanthracene. , Compounds having an aromatic vinyl structure such as p-2-propenylstyrene and p-3-butenylstyrene, and compounds having a cyclic structure such as cyclopentadiene, dicyclopentadiene, ethylidene norbornene, and various vinylcyclohexenes. Of these, ortho, meta and para divinylbenzene, or a mixture thereof is preferably used, and a mixture of meta and paradivinylbenzene is most preferably used. In the present specification, these divinylbenzenes are referred to as divinylbenzenes.
When divinylbenzenes are used as the polyene, it is preferable because curing efficiency is high and curing is easy when performing the curing treatment.
The above olefins and polyenes may contain other polar groups such as α-olefins, cyclic olefins, aromatic vinyl compounds and polyenes containing oxygen atoms, nitrogen atoms, etc., but the total mass of these monomers is It is necessary to be less than 5% by mass of the total mass of the post-curing resin composition, and preferably less than 1% by mass. If it exceeds this, the dielectric properties (dielectric constant / dielectric loss) of the cured product obtained by curing the post-curing resin composition will be deteriorated.
本エチレン−オレフィン−ポリエン共重合体の組成は、オレフィン単位含有量が５モル％以上７０モル％以下、好ましくは、１０モル％以上５０モル％以下である。複数のオレフィンを用いている場合には本オレフィン単位含有量はその合計を示す。 The composition of the present ethylene-olefin-polyene copolymer has an olefin unit content of 5 mol% to 70 mol%, preferably 10 mol% to 50 mol%. When a plurality of olefins are used, the present olefin unit content indicates the total.
オレフィン単位含有量が５モル％未満では、エチレン結晶性が発現し、最終的に得られる硬化体の耐衝撃性、しなやかさが失われてしまう場合がある。オレフィン単位含有量が７０モル％より高いと得られる硬化体の低温特性が悪化したり、耐衝撃性、しなやかさが失われてしまう場合がある。 When the olefin unit content is less than 5 mol%, ethylene crystallinity is exhibited, and the impact resistance and flexibility of the finally obtained cured product may be lost. When the olefin unit content is higher than 70 mol%, the low temperature characteristics of the resulting cured product may be deteriorated, and the impact resistance and flexibility may be lost.
本エチレン−オレフィン−ポリエン共重合体の軟質性と低温特性を考慮すると、結晶化度は一定値以下であり、かつガラス転移温度が室温以下であることが望ましい。より正確には、ＤＳＣ測定により３０℃〜３００℃に観測される結晶融解ピ−クの結晶融解熱が２５Ｊ／ｇ−ポリマ−以下であることが望ましい。またＤＳＣ測定（接線法）によるガラス転移温度は１０℃以下、好ましくは５℃以下、−１２０℃以上が望ましい。これら条件を満たすオレフィン単位含有量の範囲はオレフィンの種類により異なるが、当業者らは文献、公開特許、ハンドブック等からデ−タを入手し、本含有量の範囲を特定することが可能である。具体的に例示すると、オレフィンとしてスチレンが採用される場合には、スチレン単位含有量は１０モル％以上、３５モル％以下である。オレフィンとしてプロピレンが採用される場合、プロピレン単位含有量は１５モル％以上８５モル％以下である。
複数のオレフィンを用いる場合には、モノマ−分率を元に加成性に従い計算で予測するか、数点組成を代えて試作を行い、適当な含有量の範囲について判断することが出来る。
Considering the softness and low temperature characteristics of the present ethylene-olefin-polyene copolymer, it is desirable that the crystallinity is not more than a certain value and the glass transition temperature is not more than room temperature. More precisely, it is desirable that the crystal melting heat of the crystal melting peak observed at 30 ° C. to 300 ° C. by DSC measurement is 25 J / g-polymer or less. The glass transition temperature by DSC measurement (tangential method) is 10 ° C. or lower, preferably 5 ° C. or lower, and −120 ° C. or higher. The range of olefin unit content that satisfies these conditions varies depending on the type of olefin, but those skilled in the art can obtain data from literature, published patents, handbooks, etc., and specify the range of this content. . Specifically, when styrene is employed as the olefin, the styrene unit content is 10 mol% or more and 35 mol% or less. When propylene is employed as the olefin, the propylene unit content is 15 mol% or more and 85 mol% or less.
In the case of using a plurality of olefins, prediction can be made by calculation according to the additivity based on the monomer fraction, or a trial production can be performed by changing the composition of several points, and an appropriate content range can be determined.
本エチレン−オレフィン−ポリエン共重合体の数平均分子量は１０００以上５万以下、好ましくは５０００以上３万以下、重量平均分子量／数平均分子量は１．５以上５以下であり、かつ、ポリエン単位含有量が、数平均分子量あたり１個以上７個未満、好ましくは１．２以上５個未満であることを満足し、オレフィン単位含有量が５モル％以上７０モル％以下であり、残部がエチレン単位である。ポリエン含量がより少ないと、最終的に得られる硬化体の耐熱性が不足する場合があり、またポリエン含量がより高いと最終的に得られる硬化体の軟質性が不足する場合がある。 The ethylene-olefin-polyene copolymer has a number average molecular weight of 1,000 to 50,000, preferably 5,000 to 30,000, a weight average molecular weight / number average molecular weight of 1.5 to 5, and contains a polyene unit. The amount is from 1 to less than 7 per number average molecular weight, preferably from 1.2 to less than 5, the olefin unit content is from 5 mol% to 70 mol%, and the balance is ethylene units It is. When the polyene content is lower, the heat resistance of the finally obtained cured body may be insufficient, and when the polyene content is higher, the final obtained cured body may be insufficient in softness.
本エチレン−オレフィン−ポリエン共重合体として好適なのは、エチレン−プロピレン−ジビニルベンゼン共重合体、エチレン−１−ブテン−ジビニルベンゼン共重合体、エチレン−１−ヘキセン−ジビニルベンゼン共重合体、エチレン−１−オクテン−ジビニルベンゼン共重合体、エチレン−スチレン−ジビニルベンゼン共重合体、エチレン−パラメチルスチレン−ジビニルベンゼン共重合体、エチレン−ノルボルネン−ジビニルベンゼン共重合体、エチレン−プロピレン−ジシクロペンタジエン共重合体、エチレン−１−ブテン−ジシクロペンタジエン共重合体、エチレン−１−ヘキセン−ジシクロペンタジエン共重合体、エチレン−１−オクテン−プロピレン−ジシクロペンタジエン共重合体、エチレン−スチレン−ジシクロペンタジエン共重合体、エチレン−ノルボルネン−ジシクロペンタジエン共重合体である。 Suitable as the ethylene-olefin-polyene copolymer are ethylene-propylene-divinylbenzene copolymer, ethylene-1-butene-divinylbenzene copolymer, ethylene-1-hexene-divinylbenzene copolymer, ethylene-1 -Octene-divinylbenzene copolymer, ethylene-styrene-divinylbenzene copolymer, ethylene-paramethylstyrene-divinylbenzene copolymer, ethylene-norbornene-divinylbenzene copolymer, ethylene-propylene-dicyclopentadiene copolymer Polymer, ethylene-1-butene-dicyclopentadiene copolymer, ethylene-1-hexene-dicyclopentadiene copolymer, ethylene-1-octene-propylene-dicyclopentadiene copolymer, ethylene-styrene-dicyclopentadiene Emissions copolymer, ethylene - norbornene - dicyclopentadiene copolymer.
さらに、本エチレン−オレフィン−ポリエン共重合体及び非極性ビニル化合物としてスチレンを含む後硬化性樹脂組成物の硬化体を得る場合、上記低温特性及び、エチレン−オレフィン−ポリエン共重合体とスチレンの親和性を考慮すると、本エチレン−オレフィン−ポリエン共重合体としては、エチレン−スチレン−αオレフィン−ジビニルベンゼン共重合体が好ましい。ここでいうαオレフィンは上記規定と同じである。このような例としては、エチレン−スチレン−プロピレン−ジビニルベンゼン共重合体、エチレン−スチレン−１−ブテン−ジビニルベンゼン共重合体、エチレン−スチレン−１−ヘキセン−ジビニルベンゼン共重合体、エチレン−スチレン−１−オクテン−ジビニルベンゼン共重合体、エチレン−スチレン−プロピレン−ジシクロペンタジエン共重合体、エチレン−スチレン−１−ブテン−ジシクロペンタジエン共重合体、エチレン−スチレン−１−ヘキセン−ジシクロペンタジエン共重合体、エチレン−スチレン−１−オクテン−ジシクロペンタジエン共重合体が挙げられる。 Further, when obtaining a cured product of a post-curing resin composition containing styrene as the ethylene-olefin-polyene copolymer and the nonpolar vinyl compound, the low temperature characteristics and the affinity between the ethylene-olefin-polyene copolymer and styrene are obtained. In view of the properties, the ethylene-olefin-polyene copolymer is preferably an ethylene-styrene-α-olefin-divinylbenzene copolymer. The α-olefin here is the same as defined above. Examples thereof include ethylene-styrene-propylene-divinylbenzene copolymer, ethylene-styrene-1-butene-divinylbenzene copolymer, ethylene-styrene-1-hexene-divinylbenzene copolymer, ethylene-styrene. -1-octene-divinylbenzene copolymer, ethylene-styrene-propylene-dicyclopentadiene copolymer, ethylene-styrene-1-butene-dicyclopentadiene copolymer, ethylene-styrene-1-hexene-dicyclopentadiene Examples of the copolymer include an ethylene-styrene-1-octene-dicyclopentadiene copolymer.
＜シングルサイト配位重合触媒＞
本エチレン−オレフィン−ポリエン共重合体を合成するには、エチレン、オレフィン、ポリエンの各モノマ−を上記一般式（１）、又は（２）で表される遷移金属化合物と助触媒から構成されるシングルサイト配位重合触媒を用いることで、コモノマ−、特にポリエンの組成が均一であり本後硬化性樹脂組成物として好適なエチレン−オレフィン−ポリエン共重合体を得ることが出来る。さらに上記一般式（１）、又は（２）で表される遷移金属化合物と助触媒から構成されるシングルサイト配位重合触媒を用いることで、ポリエンを高い効率で共重合できるため本発明には好適である。
<Single site coordination polymerization catalyst>
In order to synthesize the ethylene-olefin-polyene copolymer, each monomer of ethylene, olefin, and polyene is composed of a transition metal compound represented by the above general formula (1) or (2) and a promoter. By using a single-site coordination polymerization catalyst, an ethylene-olefin-polyene copolymer having a uniform comonomer, particularly polyene, and suitable as the post-curing resin composition can be obtained. Furthermore, since a polyene can be copolymerized with high efficiency by using a single site coordination polymerization catalyst composed of a transition metal compound represented by the above general formula (1) or (2) and a cocatalyst, the present invention includes Is preferred.
従来の固体状チタン化合物を用いたチ−グラ−ナッタ触媒の場合、活性サイトの性能の不均一さに起因して、特にポリエン含有量の不均一性が発現し、また自己架橋の発生によるゲル分が出来やすく、不均一なエチレン−オレフィン−ポリエン共重合体が出来やすい。この様な共重合体を非極性ビニル化合物や硬化剤と混合し硬化体を得た場合、力学物性や耐熱性が低下するだけでなく、表面の平滑性や硬化性にも問題が生じる場合がある。さらに、上記一般式（１）、又は（２）で表される遷移金属化合物と助触媒から構成されるシングルサイト配位重合触媒以外のシングルサイト配位重合触媒、例えば２個の置換基を有しても良いシクロペンタジエニル基が架橋されていないジルコノセン触媒、ビス（ブチルシクロペンタジエニル）ジルコニウムジクロライドなどを用いた場合、又は架橋基Ｙが置換シリレン構造の触媒、例えば、ジメチルシリレンビス（１-インデニル）ジルコニウムジクロリドや１，２−エタンジイルビス（１-インデニル）ジルコニウムジクロリドを用いた場合、スチレンやポリエン（特にジビニルベンゼン）の共重合において、発明を満たすような高いスチレン含有量、ポリエン含有量を与えることが困難であったり、得られたポリマ−のポリエンが自己架橋し、共重合体の段階でゲル化、成形加工性、表面性の不良をもたらしてしまう。もちろん、本発明の条件を満たさない触媒を用い、重合温度、モノマ−組成比等極端に厳しい条件を採用した場合、本発明の条件を満たすエチレン−オレフィン−ポリエン共重合体を得ることは不可能ではない場合もあるが、その場合、活性、生産性は著しく低下し、工業的価値は失われてしまうと考えられる。 In the case of a conventional Ziegler-Natta catalyst using a solid titanium compound, the polyene content is not uniform due to the non-uniformity of the active site performance, and the gel is due to the occurrence of self-crosslinking. It is easy to form a heterogeneous ethylene-olefin-polyene copolymer. When such a copolymer is mixed with a non-polar vinyl compound or a curing agent to obtain a cured product, not only the mechanical properties and heat resistance deteriorate, but also the surface smoothness and curability may cause problems. is there. Further, a single site coordination polymerization catalyst other than the single site coordination polymerization catalyst composed of the transition metal compound represented by the above general formula (1) or (2) and a cocatalyst, for example, having two substituents. Or a zirconocene catalyst in which the cyclopentadienyl group is not cross-linked, bis (butylcyclopentadienyl) zirconium dichloride, or the like, or a catalyst in which the bridging group Y is a substituted silylene structure, such as dimethylsilylene bis ( When 1-indenyl) zirconium dichloride or 1,2-ethanediylbis (1-indenyl) zirconium dichloride is used, a high styrene content and polyene content satisfying the invention in the copolymerization of styrene and polyene (particularly divinylbenzene) Is difficult to give, or the polyene of the obtained polymer is self And bridges, gelation at the stage of the copolymer, moldability, thereby resulting in surface defective. Of course, when a catalyst that does not satisfy the conditions of the present invention is used and extremely severe conditions such as polymerization temperature and monomer composition ratio are adopted, it is impossible to obtain an ethylene-olefin-polyene copolymer that satisfies the conditions of the present invention. However, in that case, the activity and productivity are remarkably lowered and the industrial value is considered to be lost.
本発明において、さらに好ましくは、上記一般式（１）表される遷移金属化合物のうち、式中のＡ、Ｂは同一でも異なっていてもよく、共に非置換もしくは置換ベンゾインデニル基、非置換もしくは置換インデニル基から選ばれる基であり、かつＹはＡ、Ｂと結合を有し、他に置換基として水素もしくは炭素数１〜１５の炭化水素基（１〜３個の窒素、酸素、硫黄、燐、珪素原子を含んでもよい）を有するメチレン基である。置換基は互いに異なっていても同一でもよいし環状構造を有しても良い。本条件を満たす遷移金属化合物と助触媒から構成されるシングルサイト配位重合触媒を用いることで、ポリエンとして各種ジビニルベンゼン、又はこれらの混合物、４−プロペニルスチレン、４−ブテニルスチレンなどの芳香族ビニル構造を有するポリエンを採用した場合、特異的に高い共重合効率を示すことができ、かつ活性も高いので本発明には最も好適である。また、本条件を満たす遷移金属化合物と助触媒から構成されるシングルサイト配位重合触媒を用いることで、特にポリエンとしてジビニルベンゼン類を用いた場合、自己架橋が少ない（ゲル分が少ない）エチレン−オレフィン−ポリエン共重合体を極めて高い活性で得ることが出来る。すなわち、ジビニルベンゼンのひとつのビニル基が共重合された後にもう一方のビニル基が重合されずに保持できるという特異的な機能を示すため、後硬化体を得るためのエチレン−オレフィン−ポリエン共重合体としてはきわめて有用である。ゲル分の定量は、ASTM-D-2765-84に記載された方法により行うことが出来る。すなわち、精密に秤量されたポリマ−をＳＵＳ製網袋（１００メッシュ）に入れ、沸騰キシレン中１２ｈ処理し、網袋残留分質量をゲル分として、ゲル分質量％を求めるものである。本発明により得られるエチレン−オレフィン−ポリエン共重合体に含まれるゲル分質量％は、５質量％以下、好ましくは１質量％以下、最も好ましくは０．１質量％以下である。 In the present invention, more preferably, among the transition metal compounds represented by the general formula (1), A and B in the formula may be the same or different, and both are unsubstituted or substituted benzoindenyl groups and unsubstituted. Alternatively, it is a group selected from substituted indenyl groups, and Y has a bond with A and B, and as a substituent, hydrogen or a hydrocarbon group having 1 to 15 carbon atoms (1 to 3 nitrogen, oxygen, sulfur , Phosphorus and silicon atoms may be included). The substituents may be different from each other or the same, or may have a cyclic structure. By using a single-site coordination polymerization catalyst composed of a transition metal compound and a co-catalyst satisfying this condition, various divinylbenzenes as polyenes, or mixtures thereof, aromatics such as 4-propenylstyrene and 4-butenylstyrene When a polyene having a vinyl structure is employed, it is most suitable for the present invention because it can exhibit a particularly high copolymerization efficiency and has high activity. In addition, by using a single-site coordination polymerization catalyst composed of a transition metal compound and a co-catalyst satisfying the above conditions, especially when divinylbenzenes are used as a polyene, there is little self-crosslinking (low gel content) An olefin-polyene copolymer can be obtained with extremely high activity. In other words, the ethylene-olefin-polyene copolymer used to obtain a post-cured product has a specific function that one vinyl group of divinylbenzene can be copolymerized and the other vinyl group can be retained without being polymerized. It is extremely useful as a coalescence. The quantification of the gel content can be performed by the method described in ASTM-D-2765-84. That is, a precisely weighed polymer is put into a SUS net bag (100 mesh), treated in boiling xylene for 12 h, and the net mass of the net bag is determined as a gel content to determine the mass% of the gel content. The gel content mass% contained in the ethylene-olefin-polyene copolymer obtained by the present invention is 5 mass% or less, preferably 1 mass% or less, and most preferably 0.1 mass% or less.
本発明のシングルサイト配位重合触媒において、助触媒としては従来遷移金属化合物と組み合わせて用いられている公知の助触媒を使用することができる。そのような助触媒として、メチルアルミノキサン（又はメチルアルモキサン又はＭＡＯと記す）等のアルモキサン、又は硼素化合物が好適に用いられる。必要に応じて、これらアルモキサンや硼素化合物と共に、トリイソブチルアルミニウムやトリエチルアルミニウム等のアルキルアルミニウムを用いてもよい。かかる助触媒の例としては、ＥＰ−０８７２４９２Ａ２号公報、特開平１１−１３０８０８号公報、特開平９−３０９９２５号公報、ＷＯ００／２０４２６号公報、ＥＰ０９８５６８９Ａ２号公報、特開平６−１８４１７９号公報に記載されている助触媒やアルキルアルミニウム化合物が挙げられる。 In the single site coordination polymerization catalyst of the present invention, a known cocatalyst conventionally used in combination with a transition metal compound can be used as the cocatalyst. As such a cocatalyst, an alumoxane such as methylaluminoxane (or methylalumoxane or MAO) or a boron compound is preferably used. If necessary, alkylaluminum such as triisobutylaluminum and triethylaluminum may be used together with these alumoxanes and boron compounds. Examples of such cocatalysts are described in EP-087492A2, JP-A-11-130808, JP-A-9-309925, WO00 / 20426, EP0985689A2, and JP-A-6-184179. Cocatalysts and alkylaluminum compounds.
アルモキサン等の助触媒は、遷移金属化合物の金属に対し、アルミニウム原子／遷移金属原子比で０．１〜１０００００、好ましくは１０〜１００００の比で用いられる。０．１より小さいと有効に遷移金属化合物を活性化出来ず、１０００００を超えると経済的に不利となる。助触媒として硼素化合物を用いる場合には、硼素原子／遷移金属原子比で０．０１〜１００の比で用いられるが、好ましくは０．１〜１０、特に好ましくは１で用いられる。０．０１より小さいと有効に遷移金属化合物を活性化出来ず、１００を超えると経済的に不利となる。遷移金属化合物と助触媒は、重合設備外で混合、調製しても、重合時に設備内で混合してもよい。 A co-catalyst such as alumoxane is used in an aluminum atom / transition metal atom ratio of 0.1 to 100,000, preferably 10 to 10,000, relative to the metal of the transition metal compound. If it is less than 0.1, the transition metal compound cannot be activated effectively, and if it exceeds 100,000, it is economically disadvantageous. When a boron compound is used as the cocatalyst, it is used at a boron atom / transition metal atom ratio of 0.01 to 100, preferably 0.1 to 10, particularly preferably 1. If it is less than 0.01, the transition metal compound cannot be activated effectively, and if it exceeds 100, it is economically disadvantageous. The transition metal compound and the cocatalyst may be mixed and prepared outside the polymerization facility, or may be mixed in the facility during polymerization.
＜エチレン−オレフィン−ポリエン共重合体の製造＞
本発明のエチレン−オレフィン−ポリエン共重合体は、エチレン、オレフィン、ポリエンの各原料モノマ−と上記遷移金属化合物及び助触媒からなるシングルサイト配位重合触媒を接触させる。その順序、方法については公知の任意の方法が用いられる。例えば、ＷＯ００／３７５１７号公報にはエチレン−オレフィン−ポリエン共重合体の好適な製造方法が記載されている。
<Production of ethylene-olefin-polyene copolymer>
In the ethylene-olefin-polyene copolymer of the present invention, a single-site coordination polymerization catalyst comprising the respective ethylene, olefin, and polyene raw material monomers and the above transition metal compound and a cocatalyst is brought into contact. Any known method is used for the order and method. For example, WO 00/37517 discloses a suitable method for producing an ethylene-olefin-polyene copolymer.
製造方法としては溶媒を用いずに液状モノマー中で重合させる方法、あるいはペンタン、ヘキサン、ヘプタン、シクロヘキサン、ベンゼン、トルエン、エチルベンゼン、キシレン、クロロ置換ベンゼン、クロロ置換トルエン、塩化メチレン、クロロホルム等の飽和脂肪族、又は芳香族炭化水素、又はハロゲン化炭化水素の単独、又は混合溶媒を用いる方法がある。好ましくは混合アルカン系溶媒、シクロヘキサン、トルエン、エチルベンゼン等を用いる。重合形態は溶液重合、スラリ−重合いずれでもよい。また、必要に応じ、バッチ重合、連続重合、予備重合、多段式重合等の公知の方法を用いることが出来る。
単数や連結された複数のタンク式重合缶やリニアやル−プの単数、連結された複数のパイプ重合設備を用いることも可能である。パイプ状の重合缶には、動的、あるいは静的な混合機や除熱を兼ねた静的混合機等の公知の各種混合機、除熱用の細管を備えた冷却器等の公知の各種冷却器を有してもよい。また、バッチタイプの予備重合缶を有していてもよい。さらには気相重合等の方法を用いることができる。
As a production method, polymerization is performed in a liquid monomer without using a solvent, or saturated fat such as pentane, hexane, heptane, cyclohexane, benzene, toluene, ethylbenzene, xylene, chloro-substituted benzene, chloro-substituted toluene, methylene chloride, chloroform, etc. Group, aromatic hydrocarbons, or halogenated hydrocarbons, or a method using a mixed solvent. Preferably, a mixed alkane solvent, cyclohexane, toluene, ethylbenzene or the like is used. The polymerization form may be either solution polymerization or slurry polymerization. Moreover, well-known methods, such as batch polymerization, continuous polymerization, prepolymerization, and multistage polymerization, can be used as needed.
It is also possible to use a single tank or a plurality of connected tank polymerization cans or a single linear or loop polymerization apparatus or a plurality of connected pipe polymerization equipment. Pipe-shaped polymerization cans include various known mixers such as dynamic or static mixers and static mixers that also remove heat, and various known mixers such as coolers equipped with heat removal thin tubes. You may have a cooler. Moreover, you may have a batch type prepolymerization can. Furthermore, methods such as gas phase polymerization can be used.
重合温度は、−７８℃〜２００℃が適当である。−７８℃より低い重合温度は工業的に不利であり、２００℃を超えると遷移金属化合物の分解が起こるので適当ではない。さらに工業的に好ましくは、０℃〜１６０℃、特に好ましくは３０℃〜１６０℃である。
重合時の圧力は、０．１気圧〜１００気圧が適当であり、好ましくは１〜３０気圧、特に工業的に特に好ましくは、１〜１０気圧である。
The polymerization temperature is suitably -78 ° C to 200 ° C. A polymerization temperature lower than −78 ° C. is industrially disadvantageous, and if it exceeds 200 ° C., the transition metal compound is decomposed, which is not suitable. Furthermore, industrially preferable, it is 0 degreeC-160 degreeC, Most preferably, it is 30 degreeC-160 degreeC.
The pressure at the time of polymerization is suitably from 0.1 to 100 atm, preferably from 1 to 30 atm, particularly industrially particularly preferably from 1 to 10 atm.
＜後硬化性樹脂組成物＞
本発明においては、一定の範囲の組成を有する上記エチレン−オレフィン−ポリエン共重合体と非極性ビニル化合物を混合し、硬化剤を添加し後硬化性樹脂組成物を得る。ここにいて、エチレン−オレフィン−ポリエン−共重合体５重量部以上９５質量部以下、好ましくは、５０質量部以上９５質量部以下、非極性ビニル化合物５質量部以上９５質量部以下、好ましくは、５質量部以上５０質量部以下、合計１００質量部の範囲で本発明に用いられる。エチレン−オレフィン−ポリエン共重合体が５質量部未満では得られる硬化体が脆くなりすぎてしまう場合がある。
本発明においては、上記範囲でエチレン−オレフィン−ポリエン共重合体と非極性ビニル化合物の質量比を変更することで、本後硬化性樹脂組成物の粘度、流動性を、その目的、成形方法にあわせて調整することが出来る。例えは、高周波絶縁材として充填あるいは塗布後に硬化させる必要がある場合には、非極性ビニル化合物の量を増加させることで流動性を向上させることが出来る。また、あらかじめシートに成形し、半導体素子、基板と積層した後に加熱溶融させ充填密着させた後に硬化させる（いわゆるＢステージ法）場合、取り扱い容易なシ−ト形状とするためには非極性ビニル化合物の量を減じ、エチレン−オレフィン−ポリエン共重合体の組成、分子量を調整し、さらに適当な無機充填材、滑材を必要に応じて添加することで達成することが可能である。また、複数の硬化剤及び／または硬化条件を採用することで、本後硬化性樹脂組成物の粘度、流動性、性状を制御することができる。すなわち、第一段階の硬化（部分硬化）により、本後硬化性樹脂組成物を取扱容易な柔軟シート状に成形し、これを電子デバイス、基板に積層し圧着させた後に第二段階の硬化（完全硬化）を行い、最終形状とすることも可能である。
さらに、本発明においては、種類の異なる複数のエチレン−オレフィン−ポリエン共重合体からなる混合物を用いても良い。流動性や軟質性の異なるエチレン−オレフィン−ポリエン共重合体からなる混合物を用いることで、最終的に得られる硬化体の物性をより広い範囲で調節することが可能となる。
本発明の後硬化性樹脂組成物に対し、必要に応じて適切な溶媒を添加してもよい。溶媒は、後硬化性樹脂組成物の粘度、流動性を調節するために用いる。溶媒としては、揮発性のものが好ましく、例えばシクロヘキサン、トルエン、エチルベンゼン、アセトン等が用いられる。またその配合量は、本発明の後硬化性樹脂組成物に対し一般に１質量部〜１００質量部、好ましくは１質量部〜３０質量部の範囲であり、硬化中、硬化後の除去の点からは少ない方が好ましい。
<Post-curing resin composition>
In the present invention, the ethylene-olefin-polyene copolymer having a composition in a certain range and a nonpolar vinyl compound are mixed, and a curing agent is added to obtain a post-curing resin composition. Here, the ethylene-olefin-polyene-copolymer is 5 parts by weight or more and 95 parts by weight or less, preferably 50 parts by weight or more and 95 parts by weight or less, and the nonpolar vinyl compound is 5 parts by weight or more and 95 parts by weight or less, preferably It is used for this invention in 5 to 50 mass parts, the range of a total of 100 mass parts. If the ethylene-olefin-polyene copolymer is less than 5 parts by mass, the resulting cured product may become too brittle.
In the present invention, by changing the mass ratio of the ethylene-olefin-polyene copolymer and the nonpolar vinyl compound within the above range, the viscosity and fluidity of the post-curing resin composition can be changed to its purpose and molding method. It can be adjusted together. For example, when it is necessary to cure after filling or coating as a high-frequency insulating material, the fluidity can be improved by increasing the amount of the nonpolar vinyl compound. In addition, when it is molded into a sheet in advance, laminated with a semiconductor element and a substrate, heated and melted, filled and adhered, and then cured (a so-called B-stage method), a nonpolar vinyl compound is used to make the sheet shape easy to handle. This can be achieved by adjusting the composition and molecular weight of the ethylene-olefin-polyene copolymer, and adding an appropriate inorganic filler and lubricant as required. Moreover, the viscosity, fluidity | liquidity, and property of this post-curing resin composition are controllable by employ | adopting a several hardening | curing agent and / or hardening conditions. That is, by the first stage curing (partial curing), the post-curing resin composition is formed into a flexible sheet shape that is easy to handle, and the second stage curing ( It is also possible to perform complete curing) to obtain a final shape.
Furthermore, in this invention, you may use the mixture which consists of several ethylene-olefin-polyene copolymer from which a kind differs. By using a mixture of ethylene-olefin-polyene copolymers having different fluidity and softness, it is possible to adjust the physical properties of the finally obtained cured product in a wider range.
You may add a suitable solvent with respect to the post-curing resin composition of this invention as needed. The solvent is used for adjusting the viscosity and fluidity of the post-curing resin composition. As a solvent, a volatile thing is preferable, for example, cyclohexane, toluene, ethylbenzene, acetone etc. are used. Moreover, the compounding quantity is generally 1 mass part-100 mass parts with respect to the post-curing resin composition of this invention, Preferably it is the range of 1 mass part-30 mass parts, and from the point of the removal after hardening during hardening. Is preferably less.
＜非極性ビニル化合物＞
本発明に用いられる非極性ビニル化合物は、実質的に炭素数５以上２０以下の環状オレフィン及び／又は炭素数８以上２０以下の芳香族ビニル化合物から選ばれる一種以上からなり、かつポリエン含量が１質量部未満であることを特徴とする。
好ましくは、本非極性ビニル化合物は、実質的に炭素数５以上２０以下の環状オレフィン及び／又は炭素数８以上２０以下の芳香族ビニル化合物から選ばれる一種以上を９０質量部以上含有し、かつポリエン含量が１質量部未満であることを特徴とする。さらに好ましくは、本発明に用いられる非極性ビニル化合物は、炭素数５以上２０以下の環状オレフィン及び／又は炭素数８以上２０以下の芳香族ビニル化合物から選ばれる一種以上からなり、ポリエンを含まない。
非極性ビニル化合物として用いられる環状オレフィン及び／又は芳香族ビニル化合物は上記エチレン−オレフィン−ポリエン共重合体の環状オレフィン及び／又は芳香族ビニル化合物と同じ意味である。
<Non-polar vinyl compound>
The nonpolar vinyl compound used in the present invention is substantially composed of one or more selected from cyclic olefins having 5 to 20 carbon atoms and / or aromatic vinyl compounds having 8 to 20 carbon atoms, and has a polyene content of 1. It is less than part by mass.
Preferably, the nonpolar vinyl compound contains 90 parts by mass or more of at least one selected from cyclic olefins having 5 to 20 carbon atoms and / or aromatic vinyl compounds having 8 to 20 carbon atoms, and The polyene content is less than 1 part by mass. More preferably, the nonpolar vinyl compound used in the present invention comprises at least one selected from cyclic olefins having 5 to 20 carbon atoms and / or aromatic vinyl compounds having 8 to 20 carbon atoms, and does not contain polyene. .
The cyclic olefin and / or aromatic vinyl compound used as the nonpolar vinyl compound has the same meaning as the cyclic olefin and / or aromatic vinyl compound of the ethylene-olefin-polyene copolymer.
驚くべき事に、本発明の樹脂組成物の硬化体は、用いられる非極性ビニル化合物中のポリエン含量が１質量部未満であっても十分に硬化することが可能で、実用上十分な耐熱性（２００℃で２×１０５Ｐａ以上）を有することが出来る。ここで用いるポリエンが１質量部以上含まれる場合、得られる硬化体の引っ張り破断伸びが３０％未満となってしまい、剛直、あるいは脆くなってしまう場合がある。得られる硬化体の引っ張り破断伸びが３０％以上、好ましくは１５０％以上であるためには、エチレン−オレフィン−ポリエン共重合体が５０質量部以上９５質量部以下、好ましくは７０質量部以上で、非極性ビニル化合物が５質量部以上５０質量部以下、好ましくは３０質量部以下で、非極性ビニル化合物中のポリエン含量が１質量部未満、さらに含まれないことが最も好ましい。エチレン−オレフィン−ポリエン共重合体が９５質量部以上では耐熱性が低下し、５０質量部以下では引張り破断伸びが低下する場合がある。
また、本発明の樹脂組成物の硬化体は引っ張り弾性率で７０ＭＰａ以下、好ましくは３０ＭＰａ以下、もっとも好ましくは１０ＭＰａの軟質性を示すことが可能となる。
さらに、用いられる非極性ビニル化合物中のポリエン含量が１質量部未満である条件を満たすことにより、弾性率の温度変化を著しく小さくさせることが可能となる。具体的には粘弾性スペクトル測定により得られる５０℃における貯蔵弾性率の２００℃における貯蔵弾性率に対する比（＝５０℃のＥ‘/２００℃のＥ’）が、５倍以下、好ましくは３倍以下である。
得られる硬化体の引っ張り弾性率で７０ＭＰａ以下、好ましくは３０ＭＰａ以下、もっとも好ましくは１５ＭＰａ、引っ張り破断伸びが３０％以上、好ましくは１５０％以上であること、及び５０℃における貯蔵弾性率の２００℃における貯蔵弾性率に対する比が、５倍以下、好ましくは３倍以下であることをすべて満たすことは、耐熱、軟質、低誘電特性を有する新規率絶縁材料として有用である。例えば電子デバイスの封止、表面コート用途を想定した場合、耐熱性、軟質性、弾性率の温度変化が小さいことは、デバイス、基板、配線等の熱膨張により生ずる応力の緩和のために重要であると考えられる。
Surprisingly, the cured product of the resin composition of the present invention can be sufficiently cured even if the polyene content in the nonpolar vinyl compound used is less than 1 part by mass, and has practically sufficient heat resistance. (2 × 10 5 Pa or more at 200 ° C.). When the polyene used here is contained in an amount of 1 part by mass or more, the tensile elongation at break of the resulting cured product is less than 30%, which may be rigid or brittle. In order that the tensile elongation at break of the obtained cured product is 30% or more, preferably 150% or more, the ethylene-olefin-polyene copolymer is 50 parts by mass or more and 95 parts by mass or less, preferably 70 parts by mass or more, Most preferably, the nonpolar vinyl compound is 5 parts by mass or more and 50 parts by mass or less, preferably 30 parts by mass or less, and the polyene content in the nonpolar vinyl compound is less than 1 part by mass and is not further contained. If the ethylene-olefin-polyene copolymer is 95 parts by mass or more, the heat resistance may be reduced, and if it is 50 parts by mass or less, the tensile elongation at break may be reduced.
Further, the cured product of the resin composition of the present invention can exhibit a softness of a tensile elastic modulus of 70 MPa or less, preferably 30 MPa or less, and most preferably 10 MPa.
Furthermore, by satisfying the condition that the polyene content in the nonpolar vinyl compound used is less than 1 part by mass, the temperature change of the elastic modulus can be remarkably reduced. Specifically, the ratio of the storage elastic modulus at 50 ° C. to the storage elastic modulus at 200 ° C. obtained by measuring the viscoelastic spectrum (= E ′ of 50 ° C./E ′ of 200 ° C.) is 5 times or less, preferably 3 times It is as follows.
The resulting cured body has a tensile modulus of 70 MPa or less, preferably 30 MPa or less, most preferably 15 MPa, a tensile elongation at break of 30% or more, preferably 150% or more, and a storage modulus at 50 ° C. at 200 ° C. Satisfying all the ratios of the storage modulus to 5 times or less, preferably 3 times or less, is useful as a novel dielectric material having heat resistance, softness, and low dielectric properties. For example, when encapsulating electronic devices and surface coating applications, heat resistance, softness, and low temperature change in elastic modulus are important for relieving stress caused by thermal expansion of devices, substrates, wiring, etc. It is believed that there is.
本発明の後硬化性樹脂組成物には、他に酸素原子や窒素原子、珪素原子、硫黄原子、燐原子等を含む極性基を有する重合性モノマ−を含んでいてもよいが、これらモノマ−の総質量は本後硬化性樹脂組成物の総質量の１０質量％未満、好ましくは５質量％未満、特に好ましくは１質量％未満である必要がある。これら極性基を有する重合性モノマ−は、各種電子材料、基板、デバイスとの接着性向上に効果がある。しかし、上記以上含まれると本後硬化性樹脂組成物をから得られる硬化体の誘電特性（誘電率／誘電損失）を悪化させてしまう。
また本発明の後硬化性樹脂組成物には、力学物性改良のため共役ジエン系の重合体を本後硬化性樹脂組成物の総質量の５質量％未満含むことができる。５質量％以上では、成形加工性が低下してしまう。共役ジエン系の重合体としては、ポリブタジエン、ブロックまたはランダムのスチレン−ブタジエン共重合体、ポリイソプレン、ブロックまたはランダムのスチレン−イソプレン共重合体が例示できる。これら共役ジエン系の重合体の重量平均分子量１万以上である。
The post-curing resin composition of the present invention may contain a polymerizable monomer having a polar group containing an oxygen atom, a nitrogen atom, a silicon atom, a sulfur atom, a phosphorus atom or the like. The total mass of is required to be less than 10% by mass, preferably less than 5% by mass, particularly preferably less than 1% by mass of the total mass of the post-curing resin composition. These polymerizable monomers having a polar group are effective in improving adhesion to various electronic materials, substrates and devices. However, if it is contained above, the dielectric properties (dielectric constant / dielectric loss) of the cured product obtained from the post-curing resin composition will be deteriorated.
Further, the post-curing resin composition of the present invention may contain a conjugated diene polymer in an amount of less than 5% by mass of the total mass of the post-curing resin composition for improving mechanical properties. If it is 5% by mass or more, the moldability is lowered. Examples of the conjugated diene polymer include polybutadiene, block or random styrene-butadiene copolymer, polyisoprene, block or random styrene-isoprene copolymer. These conjugated diene polymers have a weight average molecular weight of 10,000 or more.
＜硬化剤＞
本発明には、従来ポリエン、芳香族ビニル化合物又は環状オレフィンの重合、又は硬化に使用できる公知のラジカル重合開始剤、又は硬化剤を用いることが出来、過酸化物系（パ−オキサイド）、アゾ系重合開始剤等用途、条件に応じて自由に選択することが出来る。
<Curing agent>
In the present invention, known radical polymerization initiators or curing agents that can be used for polymerization or curing of polyenes, aromatic vinyl compounds or cyclic olefins can be used. It can be freely selected according to the use and conditions such as a system polymerization initiator.
そのような例は、日本油脂カタログ有機過酸化物organic peroxides第10版がhttp://www.nof.co.jp/business/chemical/pdf/product01/Catalog_all.pdfからダウンロ−ド可能である。和光純薬社カタログ等にも記載されている。本発明に用いられる硬化剤はこれらの会社より入手することが出来る。また公知の光、紫外線、放射線、あるいは電子線に感応する硬化剤を用いることも出来る。放射線あるいは電子線そのものによる硬化も可能である。 As an example, the Japanese peroxide catalog organic peroxides 10th edition can be downloaded from http://www.nof.co.jp/business/chemical/pdf/product01/Catalog_all.pdf. It is also described in the Wako Pure Chemical Industries catalog. The curing agent used in the present invention can be obtained from these companies. In addition, a known curing agent sensitive to light, ultraviolet rays, radiation, or an electron beam can be used. Curing with radiation or electron beam itself is also possible.
硬化剤の使用量に特に制限はないが、一般的には後硬化性樹脂組成物１００質量部に対し、０．０１〜１０質量部用いる。過酸化物系（パ−オキサイド）、アゾ系重合開始剤等の硬化剤を用いる場合には、その半減期を考慮し、適切な温度、時間で硬化処理を行う。この場合の条件は、硬化剤に合わせて任意であるが、一般的には５０℃から１８０℃程度の温度範囲が適当である。 Although there is no restriction | limiting in particular in the usage-amount of a hardening | curing agent, Generally 0.01-10 mass parts is used with respect to 100 mass parts of post-curing resin compositions. When using a curing agent such as a peroxide (peroxide) or an azo polymerization initiator, the curing treatment is performed at an appropriate temperature and time in consideration of its half-life. The conditions in this case are arbitrary according to the curing agent, but generally a temperature range of about 50 ° C. to 180 ° C. is appropriate.
本発明の後硬化性樹脂組成物は、主に比較的低分子量のエチレン−オレフィン−ポリエン共重合体と液状のモノマ−である非極性ビニル化合物から構成されるため、低粘性液体から高粘性液体の性状を示し、液状のモノマ−である非極性ビニル化合物の粘度以上の粘度範囲で調整可能であり、好ましくは、約１０万ｃＰ以下、更に好ましくは３万ｃＰ以下である。そのため、適当な方法で塗布、充填、滴下し、熱や光により硬化させて目的の硬化体を得ることが出来る。このような液体から半固体状の性状は、各種トランスファー成形（圧入成形）や、基板や半導体デバイス材料の上、又は間に塗布、ラミネ−ション、又はスピンコ−トした後に硬化して絶縁皮膜や絶縁層を形成する上で非常に都合がよい。 The post-curing resin composition of the present invention is mainly composed of a relatively low molecular weight ethylene-olefin-polyene copolymer and a non-polar vinyl compound which is a liquid monomer. And can be adjusted in the viscosity range above the viscosity of the non-polar vinyl compound which is a liquid monomer, preferably about 100,000 cP or less, more preferably 30,000 cP or less. Therefore, the target cured product can be obtained by applying, filling, dropping by an appropriate method, and curing by heat or light. Such liquid to semi-solid properties can be cured by various transfer moldings (press-fit molding), coating, lamination, or spin coating on or between substrates and semiconductor device materials, This is very convenient for forming the insulating layer.
本発明の後硬化性樹脂組成物は、エチレン−オレフィン−ポリエン共重合体、非極性ビニル化合物及び硬化剤を混合・溶解して得られるが、混合・溶解の方法、順序は任意の公知の方法が採用できる。また、必要に応じてシリカ、アルミナ、沈降性バリウム（ＢａＳＯ4 ）粉等の無機充填材を添加したのちに後硬化性樹脂組成物を硬化することも出来る。これら無機充填材は、熱伝導性のコントロール、膨張係数コントロール、ガスバリア性の付与、密着性の向上、低価格化を目的として添加される。その添加量は、一般には後硬化性樹脂組成物１００質量部に対して１〜５００質量部の範囲で用いることができる。
特に、低誘電率、低誘電損失性及び放熱性に優れた後硬化性樹脂組成物を目的とする場合、無機充填材としてはボロンナイトライド（ＢＮ）が好ましい。さらには低誘電性（低誘電率、低誘電損失正接）を改善、向上させるために中空のフィラ−や空隙の多い形状のフィラ−を添加しても良い。これらは本発明の後硬化性樹脂組成物１００質量部に対して一般に１〜５００質量部の範囲で用いることができる。
また、無機充填材の替わりに、高分子量または超高分子量ポリエチレン等の有機フィラ−を用いることも可能である。これら高分子量または超高分子量ポリエチレン等の有機フィラ−は、充填性、接着性、分散性向上を目的としてその表面が変性されていても良い。これら有機充填材も、本発明の後硬化性樹脂組成物１００質量部に対して１〜５００質量部の範囲で用いることができ、好ましくは、１〜３００質量部の範囲で用いる。
一方、本発明の樹脂組成物に１ＧＨｚにおける誘電率が３．０〜１００００、好ましくは５〜１００００の高誘電率絶縁体フィラ−を混合し分散することによって誘電正接（誘電損失）の増大を抑制しつつ、誘電率が３．１〜２０の高誘電率絶縁層を有する絶縁硬化体を作成することができる。絶縁硬化体からなるフィルムの誘電率を高くすることによって回路の小型化，コンデンサの高容量化が可能となり高周波用電気部品の小型化等に寄与できる。高誘電率，低誘電正接絶縁層はキャパシタ，共振回路用インダクタ，フィルター，アンテナ等の用途に適する。本発明に用いる高誘電率絶縁体フィラ−としては、無機充填材または絶縁処理施した金属粒子が挙げられる。具体的な例は、チタン酸バリウム、チタン酸ストロンチウム等公知の高誘電率無機充填材であり、他の例は例えば特開２００４−０８７６３９号公報に具体的に記載されている。
本発明の後硬化性樹脂組成物には難燃剤を配合することができる。好ましい難燃剤は、低誘電損失（低誘電正接）性を保持する観点からは、赤リン、トリフェニルフォスフィン、リン酸トリフェニルまたはこれらの縮合体等の公知の有機リン系や公知の臭素系難燃剤である。さらに難燃助剤として三酸化アンチモン，四酸化アンチモン，五酸化アンチモン，アンチモン酸ソーダ等のアンチモン系化合物またはメラミン、トリアリル−１，３，５−トリアジン−２，３，４−（１Ｈ，３Ｈ，５Ｈ）−トリオン、２，４，６−トリアリロキシ１，３，５−トリアジン等の含窒素化合物を添加しても良い。これら難燃剤、難燃助剤の合計は、樹脂組成物１００質量部に対して通常は１〜１００質量部の範囲である。また、ポリフェニレンエーテル（PPE）系の低誘電率かつ難燃性に優れる樹脂を組成物１００質量部に対し、１〜１００質量部配合してもよい。
The post-curing resin composition of the present invention can be obtained by mixing and dissolving an ethylene-olefin-polyene copolymer, a nonpolar vinyl compound and a curing agent, and the mixing and dissolving method can be any known method. Can be adopted. In addition, the post-curing resin composition can be cured after adding an inorganic filler such as silica, alumina, precipitated barium (BaSO 4 ) powder or the like, if necessary. These inorganic fillers are added for the purpose of controlling thermal conductivity, controlling expansion coefficient, imparting gas barrier properties, improving adhesion, and reducing cost. The addition amount can generally be used in the range of 1 to 500 parts by mass with respect to 100 parts by mass of the post-curing resin composition.
In particular, when aiming at a post-curing resin composition excellent in low dielectric constant, low dielectric loss and heat dissipation, boron nitride (BN) is preferable as the inorganic filler. Furthermore, in order to improve and improve low dielectric properties (low dielectric constant, low dielectric loss tangent), a hollow filler or a filler having a large number of voids may be added. These can be generally used in the range of 1 to 500 parts by mass with respect to 100 parts by mass of the post-curing resin composition of the present invention.
Moreover, it is also possible to use organic fillers, such as high molecular weight or ultra high molecular weight polyethylene, instead of an inorganic filler. The surface of these organic fillers such as high molecular weight or ultrahigh molecular weight polyethylene may be modified for the purpose of improving filling properties, adhesiveness, and dispersibility. These organic fillers can also be used in the range of 1 to 500 parts by weight, preferably in the range of 1 to 300 parts by weight, with respect to 100 parts by weight of the post-curing resin composition of the present invention.
On the other hand, increase in dielectric loss tangent (dielectric loss) is suppressed by mixing and dispersing a high dielectric constant insulator filler having a dielectric constant at 1 GHz of 3.0 to 10,000, preferably 5 to 10,000, in the resin composition of the present invention. However, an insulating hardened body having a high dielectric constant insulating layer having a dielectric constant of 3.1 to 20 can be produced. By increasing the dielectric constant of a film made of an insulating hardened body, it is possible to reduce the size of the circuit and increase the capacity of the capacitor, thereby contributing to the downsizing of high-frequency electrical components. The high dielectric constant and low dielectric loss tangent insulating layer is suitable for applications such as capacitors, resonant circuit inductors, filters, and antennas. Examples of the high dielectric constant insulator filler used in the present invention include inorganic fillers or insulated metal particles. Specific examples are known high dielectric constant inorganic fillers such as barium titanate and strontium titanate, and other examples are specifically described in, for example, Japanese Patent Application Laid-Open No. 2004/087639.
A flame retardant can be blended in the post-curing resin composition of the present invention. From the viewpoint of maintaining low dielectric loss (low dielectric loss tangent), the preferred flame retardant is a known organic phosphorus type or a known bromine type such as red phosphorus, triphenylphosphine, triphenyl phosphate or a condensate thereof. It is a flame retardant. Further, antimony compounds such as antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate or melamine, triallyl-1,3,5-triazine-2,3,4- (1H, 3H, Nitrogen-containing compounds such as 5H) -trione and 2,4,6-trialyloxy 1,3,5-triazine may be added. The total of these flame retardants and flame retardant aids is usually in the range of 1 to 100 parts by mass with respect to 100 parts by mass of the resin composition. Moreover, you may mix | blend 1-100 mass parts of polyphenylene ether (PPE) type | system | group resin with low dielectric constant and excellent flame retardance with respect to 100 mass parts of compositions.
＜後硬化性樹脂組成物から得られた硬化体＞
本発明の後硬化性樹脂組成物から得られた硬化体の誘電率は３以下２以上、好ましくは２．７以下２．０以上、誘電損失は０．００７以下０．０００５以上、好ましくは０．００６以下０．００１以上である。また、得られた硬化体の体積抵抗率は、１×１０１５Ω・ｃｍ以上である。これらの値は、高周波回路の絶縁材料として好ましい値である。本発明の後硬化性樹脂組成物に用いられるエチレン−オレフィン−ポリエン共重合体は軟質で柔軟性に富むために、これと共に非極性ビニル化合物との組成物から得られる硬化体は、非常に軟質で耐衝撃性が高いという特徴を有することが出来る。例えば、引張破断ひずみは一般的には３０％以上１５００％以下、好ましくは１５０％以上１０００％以下の値を示す。また引張弾性率は、一般的には０．１ＭＰａ以上７０ＭＰａ以下、好ましくは０．１ＭＰａ以上７０ＭＰａ以下の値を示すことが出来る。引張破断応力は、一般的には１ＭＰａ以上５０ＭＰａ、好ましくは１ＭＰａ以上３０ＭＰａ以下の値を示すことが出来る。
<Hardened body obtained from post-curing resin composition>
The dielectric constant of the cured product obtained from the post-curing resin composition of the present invention is 3 or less, 2 or more, preferably 2.7 or less, 2.0 or more, and the dielectric loss is 0.007 or less, 0.0005 or more, preferably 0. 0.006 or less and 0.001 or more. Moreover, the volume resistivity of the obtained cured body is 1 × 10 15 Ω · cm or more. These values are preferable values as an insulating material for a high-frequency circuit. Since the ethylene-olefin-polyene copolymer used in the post-curing resin composition of the present invention is soft and flexible, the cured product obtained from the composition together with the nonpolar vinyl compound is very soft. It can be characterized by high impact resistance. For example, the tensile strain at break is generally from 30% to 1500%, preferably from 150% to 1000%. Further, the tensile elastic modulus can generally exhibit a value of 0.1 MPa to 70 MPa, preferably 0.1 MPa to 70 MPa. The tensile rupture stress can generally exhibit a value of 1 MPa to 50 MPa, preferably 1 MPa to 30 MPa.
本発明の後硬化性樹脂組成物から得られた硬化体は良好な耐熱性を示す。粘弾性スペクトルから得られる２００℃における貯蔵弾性率も１×１０5Ｐａ以上である。さらに本発明の後硬化性樹脂組成物から得られた硬化体は２７０℃でも貯蔵弾性率も１×１０5Ｐａ以上を示すことが可能であり、高温においても軟質であるが十分な力学的強度を保持している。
＜後硬化性樹脂組成物から得られた硬化体の用途＞
本発明の後硬化性樹脂組成物を用いて得られた硬化体の用途としては、高周波動作の障害となる配線間静電容量を低減するための、半導体用または配線用の低誘電率、低誘電損失充填絶縁材、被覆絶縁材、シ−ト状絶縁材、ポッティング材、表面コート材である。本発明の後硬化性樹脂組成物及び必要に応じ上記各種無機充填材（フィラ−）、難燃剤等を配合し、必要ならば適切な溶媒を添加し、半導体装置の種類、形状に応じて塗布、充填、乾燥、及び／または加熱により硬化させて用いることが出来る。
さらに高周波集積回路のインターポーザーとして、後硬化性樹脂組成物のエチレン−オレフィン−ポリエン共重合体／非極性ビニル化合物の質量比を選択することで軟質フィルム状に調整し、基板と積層し熱溶融後完全架橋硬化させることも可能である（いわゆるＢステージ法）。
また、流動性を有する後硬化性樹脂組成物とフィラ−（無機充填材あるいは有機充填材）からなる高周波集積回路アンダーフィル材としても有用である。アンダ−フィル材とは実装時の基板とチップを電気的に接続する際にこれらを密着させ強度を確保する材料である。本用途では低粘度で浸透性が高く、その補強効果によりヒ−トサイクルによる応力を緩和することができることが重要である。
本発明の後硬化性樹脂組成物を用いて得られた硬化体を絶縁層に使用した多層配線基板は誘電損失が少ない高周波特性の優れた配線基板となり得る。この場合、低誘電損失性以外にハンダに耐えうる耐熱性と、ヒートサイクルあるいは熱膨張差による応力に耐えうる耐衝撃性や軟質性がメリットとなる。例えば、ガラスクロス，不織布，フィルム材，セラミック基板，ガラス基板，エポキシ等の汎用樹脂板，汎用積層板等のコア材と本硬化体からなる絶縁層付導体箔をラミネート，プレスすることで作製することが可能である。またコア材に後硬化性樹脂組成物を含むスラリ−、または溶液を塗布し乾燥、硬化させ絶縁層を形成しても良い。絶縁層の厚さは一般的に１〜３００ミクロンである。この様な多層配線基板は、多層化、集積化して用いることも可能である。
本発明の後硬化性樹脂組成物は、太陽電池（太陽光発電装置）の封止材として用いることができる。本発明の後硬化性樹脂組成物は、上記のように液状〜軟質の性状を示すため、太陽電池セルへ注入または圧入し、その後硬化させることで封止することができる。また、半硬化状態のフィルムとすることで、太陽電池セルを挟み込み硬化させ封止することもできる。硬化温度、時間は、用いる硬化剤の種類、量により任意に変更できる。また、光硬化剤を選ぶことで、光硬化も可能となる。本後硬化性樹脂組成物からなる、または含む封止材は、その水蒸気透過率や吸水率の低さ、高体積抵抗率が封止材としての特徴である。
The cured product obtained from the post-curable resin composition of the present invention exhibits good heat resistance. The storage elastic modulus at 200 ° C. obtained from the viscoelastic spectrum is also 1 × 10 5 Pa or more. Furthermore, the cured product obtained from the post-curing resin composition of the present invention can exhibit a storage elastic modulus of 1 × 10 5 Pa or higher even at 270 ° C., and is soft at a high temperature but has sufficient mechanical strength. Holding.
<Use of cured body obtained from post-curing resin composition>
The cured product obtained by using the post-curing resin composition of the present invention has a low dielectric constant and a low dielectric constant for semiconductors or wirings for reducing the inter-wiring capacitance that hinders high-frequency operation. Dielectric loss filling insulating material, covering insulating material, sheet-like insulating material, potting material, surface coating material. The post-curing resin composition of the present invention and the above-mentioned various inorganic fillers (fillers), flame retardants, etc., if necessary, are added, and if necessary, an appropriate solvent is added, and applied according to the type and shape of the semiconductor device It can be used by being cured by filling, drying and / or heating.
Furthermore, as an interposer for high-frequency integrated circuits, the mass ratio of ethylene-olefin-polyene copolymer / non-polar vinyl compound in the post-curing resin composition is selected to adjust to a soft film shape, laminated with the substrate, and heat melted It is also possible to carry out post-crosslinking curing (so-called B-stage method).
It is also useful as a high frequency integrated circuit underfill material comprising a post-curing resin composition having fluidity and a filler (inorganic filler or organic filler). The underfill material is a material that secures strength by closely contacting a substrate and a chip at the time of mounting. In this application, it is important that stress due to heat cycle can be relieved by its reinforcing effect due to its low viscosity and high permeability.
A multilayer wiring board using a cured product obtained by using the post-curing resin composition of the present invention as an insulating layer can be a wiring board with low dielectric loss and excellent high frequency characteristics. In this case, in addition to low dielectric loss, heat resistance that can withstand solder and impact resistance and softness that can withstand stress due to heat cycle or thermal expansion difference are advantageous. For example, it is produced by laminating and pressing a core foil such as glass cloth, nonwoven fabric, film material, ceramic substrate, glass substrate, epoxy, and other general-purpose resin plates, general-purpose laminates, etc., and a hardened body. It is possible. Alternatively, a slurry containing a post-curing resin composition or a solution may be applied to the core material, followed by drying and curing to form an insulating layer. The thickness of the insulating layer is generally 1 to 300 microns. Such a multilayer wiring board can be used in a multilayered or integrated manner.
The post-curing resin composition of the present invention can be used as a sealing material for solar cells (solar power generation devices). Since the post-curing resin composition of the present invention exhibits liquid to soft properties as described above, it can be sealed by being injected or press-fitted into a solar battery cell and then cured. Moreover, by using a semi-cured film, the solar battery cell can be sandwiched and cured to be sealed. The curing temperature and time can be arbitrarily changed depending on the type and amount of the curing agent used. Moreover, photocuring is also possible by selecting a photocuring agent. The sealing material comprising or including the present post-curable resin composition is characterized by its low water vapor transmission rate, low water absorption rate, and high volume resistivity as the sealing material.
以下、実施例により、本発明を説明するが、本発明は、以下の実施例に限定して解釈されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is limited to a following example and is not interpreted.
合成例、比較合成例で得られた共重合体の分析は以下の手段によって実施した。 The analysis of the copolymer obtained by the synthesis example and the comparative synthesis example was implemented by the following means.
共重合体中のスチレン、オクテン、ジビニルベンゼン、ジシクロペンタジエンの単位含有量の決定は、１Ｈ−ＮＭＲで行い、機器は日本電子社製α−５００を用いた。重１，１，２，２−テトラクロロエタンに溶解し、測定は、８０〜１３０℃で行った。 The unit content of styrene, octene, divinylbenzene and dicyclopentadiene in the copolymer was determined by 1 H-NMR, and α-500 manufactured by JEOL Ltd. was used. It dissolved in deuterated 1,1,2,2-tetrachloroethane, and the measurement was performed at 80 to 130 ° C.
分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）を用いて標準ポリスチレン換算の重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）を求めた。測定は以下の条件で行った。
カラム：ＴＳＫ−ＧＥＬ ＭｕｌｔｉｐｏｒｅＨＸＬ-Ｍ φ７．８×３００ｍｍ（東ソ−社製）を２本直列に繋いで用いた。
カラム温度：４０℃
溶媒：ＴＨＦ
送液流量：１．０ｍｌ／ｍｉｎ．
As for the molecular weight, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene were determined using GPC (gel permeation chromatography). The measurement was performed under the following conditions.
Column: TSK-GEL MultiporeHXL-M φ7.8 × 300 mm (manufactured by Tosoh Corporation) was connected in series.
Column temperature: 40 ° C
Solvent: THF
Liquid feed flow rate: 1.0 ml / min.
ＤＳＣ測定は、セイコーインスツルメンツ社製EXSTAR６０００を用い、窒素気流下で行った。すなわち樹脂組成物１０ｍｇを用い、昇温速度２０℃／分で−１００℃から３００℃までＤＳＣ測定を行い、融点、結晶融解熱及びガラス転移点を求めた。ガラス転移温度は、接線法で求めた。 DSC measurement was performed under a nitrogen stream using an EXSTAR6000 manufactured by Seiko Instruments Inc. That is, using 10 mg of the resin composition, DSC measurement was performed from −100 ° C. to 300 ° C. at a temperature rising rate of 20 ° C./min, and the melting point, heat of crystal melting, and glass transition point were determined. The glass transition temperature was determined by the tangent method.
＜引張試験＞
ＪＩＳ Ｋ−６２５１に準拠し、フィルムシートを２号１／２号型テストピース形状にカットし、オリエンテック社製テンシロンＵＣＴ−１Ｔ型を用い、２３℃、引張速度５００ｍｍ／ｍｉｎにて測定した。
<Tensile test>
Based on JIS K-6251, the film sheet was cut into a No. 2 1/2 type test piece shape, and measured using a Tensilon UCT-1T type manufactured by Orientec Corp. at 23 ° C. and a tensile speed of 500 mm / min.
＜貯蔵粘弾率の測定＞
動的粘弾性測定装置（レオメトリックス社ＲＳＡ−III）を使用し、周波数１Ｈｚ、温度領域−６０℃〜＋３００℃の範囲で測定した。厚み約０．１から０．２ｍｍのフィルムから測定用サンプル（３ｍｍ×４０ｍｍ）を切り出した。
<Measurement of storage viscosities>
Using a dynamic viscoelasticity measuring apparatus (Rheometrics RSA-III), the frequency was 1 Hz and the temperature range was −60 ° C. to + 300 ° C. A measurement sample (3 mm × 40 mm) was cut out from a film having a thickness of about 0.1 to 0.2 mm.
＜折り曲げ試験＞
得られたフィルムに定規をあて、手で１８０°折り曲げた際に、割れやひびが発生しなかったサンプルは○とし、割れやひびが発生したサンプルは×とした。
<Bending test>
When the obtained film was applied with a ruler and bent by 180 ° by hand, a sample in which no cracks or cracks occurred was marked with “◯”, and a sample in which cracks or cracks occurred was marked with “X”.
＜吸水率＞
ＪＩＳ Ｃ ６４８１に準拠
○０．０５質量％未満、△０．０５以上０．１質量％未満、×０．１質量％以上
<Water absorption rate>
Conforms to JIS C 6481 ○ Less than 0.05% by mass, Δ0.05 or more and less than 0.1% by mass, × 0.1% by mass or more
＜ヘーズ＞
透明度はＪＩＳ Ｋ−７１０５プラスチックの光学的特性試験方法に準じて日本電色工業社製濁度計ＮＤＨ２０００を用いてヘーズを測定した。
<Haze>
Transparency measured haze using turbidimeter NDH2000 by Nippon Denshoku Industries Co., Ltd. according to the optical characteristic test method of JIS K-7105 plastic.
＜誘電率及び誘電損失＞
ＲＦ−ＩＶ法に準拠し、測定装置：アジレントテクノロジ−株式会社製ＲＦインピ−ダンス／マテリアルアナライザ ＨＰ４２９１Ａにより、測定周波数１ＭＨｚ〜１ＧＨｚの範囲で測定を実施した。
＜体積抵抗率＞
０．５ｍｍ厚さフィルムを用い、ＪＩＳＫ６９１１に従い室温で測定した。
<Dielectric constant and dielectric loss>
In accordance with the RF-IV method, measurement was carried out in the measurement frequency range of 1 MHz to 1 GHz with a measuring device: RF impedance / material analyzer HP 4291A manufactured by Agilent Technologies.
<Volume resistivity>
Measurement was performed at room temperature according to JISK6911 using a 0.5 mm thick film.
＜ジビニルベンゼン＞
以下の実施例で用いたジビニルベンゼンは、新日鐵化学社製「ＤＶＢ-810」（ジビニルベンゼンとしての純度８１％、メタ体、パラ体混合物のメタ体：パラ体質量比は７０：３０）である。
<Divinylbenzene>
The divinylbenzene used in the following examples is “DVB-810” manufactured by Nippon Steel Chemical Co., Ltd. (purity 81% as divinylbenzene, meta isomer of meta isomer, para isomer mixture: para isomer mass ratio is 70:30) It is.
＜触媒（遷移金属化合物）＞
以下の実施例では、触媒（遷移金属化合物）として、ｒａｃ（ラセミ体）−ジメチルメチレンビス（４，５−ベンゾ−１−インデニル）ジルコニウムジクロライドを用いた。
<Catalyst (transition metal compound)>
In the following examples, rac (racemic) -dimethylmethylenebis (4,5-benzo-1-indenyl) zirconium dichloride was used as a catalyst (transition metal compound).
合成例１
＜エチレン−ヘキセン−スチレン−ジビニルベンゼン共重合体の合成＞
触媒としてｒａｃ−ジメチルメチレンビス（４，５ベンゾ−１−インデニル）ジルコニウムジクロライドを用い、以下のように実施した。
容量１０Ｌ、攪拌機及び加熱冷却用ジャケット付のオートクレーブを用いて重合を行った。 トルエン２９００ｍｌ、スチレン４００ｍｌ、１−ヘキセン３００ｍｌおよび新日鉄化学社製のジビニルベンゼン（メタ、パラ混合品、ジビニルベンゼンとして１１５．３ｍｍｏｌ）を仕込み、乾燥窒素ガスを約７０Ｌバブリングして、内温６０℃にて加熱攪拌しオ−トクレ−ブ内及び重合液の水分をパージした。次いで、トリイソブチルアルミニウム８．４ｍｍｏｌ、メチルアルモキサン（ファイン・ケム社製、ＭＭＡＯ−３Ａトルエン溶液）をＡｌ基準で１６．８ｍｍｏｌ(表１中ではＭＡＯと記載)加え、ただちにエチレンを導入し、内温１０５℃、圧力０．４ＭＰａで安定した後に、オートクレーブ上に設置した触媒タンクから、ｒａｃ−ジメチルメチレンビス（４，５ベンゾ−１−インデニル）ジルコニウムジクロライドを１８．８μｍｏｌ、トリイソブチルアルミニウム約１ｍｍｏｌを溶かしたトルエン溶液約３０ｍｌをオートクレーブ中に加えた。内温を１０５℃、圧力を０．４ＭＰａに維持しながら０．５時間重合を実施した。得られた重合液に、１−イソプロパノールを投入し、その後、大量のメタノールを投入してポリマーを回収した。このポリマーを、５０℃で２昼夜真空乾燥し約４８０ｇのポリマーを得た。
Synthesis example 1
<Synthesis of ethylene-hexene-styrene-divinylbenzene copolymer>
Using rac-dimethylmethylenebis (4,5benzo-1-indenyl) zirconium dichloride as a catalyst, the following procedure was performed.
Polymerization was carried out using an autoclave with a capacity of 10 L, a stirrer and a heating / cooling jacket. Charge 2900 ml of toluene, 400 ml of styrene, 300 ml of 1-hexene and divinylbenzene (meta, para-mixed product, 115.3 mmol as divinylbenzene) manufactured by Nippon Steel Chemical Co., Ltd., and bubbling about 70 L of dry nitrogen gas to an internal temperature of 60 ° C. The mixture was heated and stirred to purge the moisture in the autoclave and the polymerization solution. Next, 8.4 mmol of triisobutylaluminum and methylalumoxane (manufactured by Fine Chem Co., Ltd., MMAO-3A toluene solution) were added in an amount of 16.8 mmol (referred to as MAO in Table 1), and ethylene was immediately introduced. After stabilization at a temperature of 105 ° C. and a pressure of 0.4 MPa, 18.8 μmol of rac-dimethylmethylenebis (4,5benzo-1-indenyl) zirconium dichloride and about 1 mmol of triisobutylaluminum were added from a catalyst tank installed on the autoclave. About 30 ml of dissolved toluene solution was added into the autoclave. Polymerization was carried out for 0.5 hours while maintaining the internal temperature at 105 ° C. and the pressure at 0.4 MPa. To the obtained polymerization solution, 1-isopropanol was added, and then a large amount of methanol was added to recover the polymer. This polymer was vacuum-dried at 50 ° C. for 2 days to obtain about 480 g of polymer.
合成例２
合成例１と同様の手順で、但し表１記載の条件で重合を行った。
Synthesis example 2
Polymerization was carried out in the same procedure as in Synthesis Example 1, but under the conditions described in Table 1.
合成例３〜７
合成例１と同様の手順で、但し、用いる触媒をｒａｃ−ジメチルメチレンビス（１−インデニル）ジルコニウムジクロライドに変更し、容量２Ｌの攪拌機および加熱冷却用ジャケット付きのオートクレーブ用い、表１記載の条件で重合を行った。
Synthesis Examples 3-7
The procedure was the same as in Synthesis Example 1, except that the catalyst used was changed to rac-dimethylmethylenebis (1-indenyl) zirconium dichloride and the autoclave with a 2 L capacity stirrer and a heating / cooling jacket was used under the conditions described in Table 1. Polymerization was performed.
合成例８
合成例１と同様の手順で、但し、容量２Ｌの攪拌機および加熱冷却用ジャケット付きのオートクレーブを用い、表１記載の条件で重合を行った。
Synthesis example 8
Polymerization was carried out in the same procedure as in Synthesis Example 1 except that a 2 L capacity stirrer and an autoclave with a heating / cooling jacket were used under the conditions shown in Table 1.
実施例１
合成例１で得られたエチレン−ヘキセン−スチレン−ジビニルベンゼン共重合体５．２ｇとスチレン２ｇの樹脂組成物を約４０度に加熱して攪拌し溶解した。さらに、パーブチルＯを樹脂組成物１００質量部に対して１質量部加えて溶解し、本発明の後硬化性樹脂組成物を得た。配合条件を表３に示す。得られた後硬化性樹脂組成物をガラス板上に設置したペットシート上のフルオロカーボン樹脂製型枠（枠部分長さ７ｃｍ、幅７ｃｍ、厚さ０．１ｍｍ）に流し込み、さらにペットシート、ガラス板で挟んで、８０℃の乾燥機中で１２時間加熱処理した。終了後、硝子板及び型枠を外し、しなやかな透明フィルムとして本発明の後硬化性樹脂組成物のフィルム状硬化体を得た。得られたフィルムを２号ダンベル１／２号型テストピース形状にカットし、力学物性を測定した結果を表４に示す。折り曲げ試験、粘弾性スペクトル測定により得られた５０℃、２００℃の貯蔵弾性率、及び吸水率（ＪＩＳＣ ６４８１に準拠）を評価した結果についても表４に示す。
Example 1
A resin composition of 5.2 g of the ethylene-hexene-styrene-divinylbenzene copolymer obtained in Synthesis Example 1 and 2 g of styrene was heated to about 40 degrees and stirred to dissolve. Furthermore, 1 part by mass of perbutyl O was added to 100 parts by mass of the resin composition and dissolved to obtain a post-curing resin composition of the present invention. Table 3 shows the blending conditions. The obtained post-curing resin composition is poured into a fluorocarbon resin mold on a pet sheet placed on a glass plate (frame portion length 7 cm, width 7 cm, thickness 0.1 mm), and further the pet sheet and glass plate And heat-treated in a dryer at 80 ° C. for 12 hours. After completion, the glass plate and the formwork were removed, and a film-like cured product of the post-curing resin composition of the present invention was obtained as a supple transparent film. Table 4 shows the results obtained by cutting the obtained film into No. 2 dumbbell No. 1/2 test piece shape and measuring the mechanical properties. Table 4 also shows the results of evaluating the storage elastic modulus at 50 ° C. and 200 ° C., and the water absorption rate (based on JISC 6481) obtained by bending test and viscoelastic spectrum measurement.
実施例２〜６
実施例１と同様の手順で、表３の配合で後硬化性樹脂組成物を調製し、同様の手順で加熱処理を行い、本発明の後硬化性樹脂組成物のフィルム状硬化体を得た。
Examples 2-6
In the same procedure as in Example 1, a post-curing resin composition was prepared with the formulation shown in Table 3, and heat treatment was performed in the same procedure to obtain a film-like cured product of the post-curing resin composition of the present invention. .
実施例１〜６で得られたフィルムを用い、誘電率、誘電損失、体積抵抗率を測定した結果を表５に示す。
Table 5 shows the results of measurement of dielectric constant, dielectric loss, and volume resistivity using the films obtained in Examples 1 to 6.
また、実施例５で得られたフィルムの粘弾性スペクトル（温度と貯蔵弾性率の関係）を図１に示す。実施例１〜６で得られた樹脂組成物の硬化体は、引っ張り弾性率が１０ＭＰａ以下の軟質性を示した。さらに引っ張り伸び１５０％以上で、５０℃における貯蔵弾性率の２００℃における貯蔵弾性率の比（＝５０℃のＥ‘/２００℃のＥ’）が５倍以下であった。また、いずれの実施例も折り曲げ試験、吸水率ともに良好な結果であった。さらに、２００℃での貯蔵弾性率が２×１０５Ｐａ以上であり耐熱性を保持していた。
比較例１〜１４は、非極性ビニル化合物計１００質量部に対し９質量部以上のジビニルベンゼンを用いているが、すべて引張り弾性率が７０ＭＰａ以上であり、破断点伸びは１５０％以下であった。比較例４及び７では５０℃における貯蔵弾性率の２００℃における貯蔵弾性率の比（＝５０℃のＥ‘/２００℃のＥ’）が５倍以下であったが、引っ張り試験における破断点伸びが３０％未満であり低く、室内折り曲げ試験において折れていることからも、本発明の範囲からは外れる。
実施例１〜６で得られた硬化体フィルムの吸水率はいずれも０．０５質量％未満であり（表４）、体積抵抗率は１×１０１５Ω・ｃｍ以上であった（表５）。一方、市販の太陽電池封止用ＥＶＡ（架橋後）フィルムの吸水率は、０．２質量％であり、体積抵抗率は３．６×１０１４Ω・ｃｍであった。
Moreover, the viscoelastic spectrum (relationship between temperature and storage elastic modulus) of the film obtained in Example 5 is shown in FIG. The hardened | cured material of the resin composition obtained in Examples 1-6 showed the softness | flexibility whose tensile elasticity modulus is 10 Mpa or less. Furthermore, when the tensile elongation was 150% or more, the ratio of the storage elastic modulus at 200 ° C. to the storage elastic modulus at 50 ° C. (= E ′ of 50 ° C./E ′ of 200 ° C.) was 5 times or less. Moreover, all the examples were good results in both the bending test and the water absorption rate. Furthermore, the storage elastic modulus at 200 ° C. was 2 × 10 5 Pa or more, and the heat resistance was maintained.
Comparative Examples 1 to 14 use 9 parts by mass or more of divinylbenzene with respect to 100 parts by mass of the nonpolar vinyl compound, but all have a tensile modulus of 70 MPa or more and an elongation at break of 150% or less. . In Comparative Examples 4 and 7, the ratio of the storage elastic modulus at 200 ° C. to the storage elastic modulus at 50 ° C. (= E ′ of 50 ° C./E ′ of 200 ° C.) was 5 times or less, but the elongation at break in the tensile test was Is less than 30% and is broken in the indoor bending test, and thus is out of the scope of the present invention.
The water absorptivity of the cured films obtained in Examples 1 to 6 were all less than 0.05% by mass (Table 4), and the volume resistivity was 1 × 10 15 Ω · cm or more (Table 5). . On the other hand, the water absorption rate of the commercially available EVA film for sealing solar cells (after crosslinking) was 0.2 mass%, and the volume resistivity was 3.6 × 10 14 Ω · cm.
以上の結果より、本発明の後硬化性樹脂組成物を硬化した成形体は優れた軟質性、力学強度、耐熱性、耐衝撃性、耐水性と同時に優れた低誘電率及び低誘電損失を示す。本後硬化性樹脂組成物は流動性を有するので、フィルム状や各種形状に成形し硬化することで、様々な形状に成形することが容易であり、特に高周波用の電気絶縁材料として好適に用いることが出来る。また、本発明の後硬化性樹脂組成物を硬化した成形体は、太陽電池封止材としての優れた低吸水性、高い体積抵抗率を示す。
From the above results, the molded product obtained by curing the post-curing resin composition of the present invention exhibits excellent softness, mechanical strength, heat resistance, impact resistance, water resistance and excellent low dielectric constant and low dielectric loss. . Since this post-curing resin composition has fluidity, it can be easily formed into various shapes by forming into a film or various shapes and curing, and is particularly suitably used as an electrical insulating material for high frequencies. I can do it. Moreover, the molded object which hardened | cured the post-curing resin composition of this invention shows the outstanding low water absorption and high volume resistivity as a solar cell sealing material.
Claims (6)
（１）オレフィンが、炭素数３以上２０以下のαオレフィン、炭素数５以上２０以下の環状オレフィン、炭素数８以上２０以下の芳香族ビニル化合物から選ばれる一種以上である。
（２）ポリエンが、分子内にビニル基及び／又はビニレン基を複数有する炭素数５以上２０以下のポリエンから選ばれる一種以上である。
（３）エチレン−オレフィン−ポリエン共重合体の数平均分子量が５０００以上３万以下、重量平均分子量／数平均分子量が１．５以上５以下であり、かつ、ポリエン単位含有量が、数平均分子量あたり１個以上７個未満であることを満足し、オレフィン単位含有量が５モル％以上７０モル％以下であり、残部がエチレン単位である。
（４）エチレン、オレフィン及びポリエンを共重合するときに使用する触媒が、下記の一般式（１）又は（２）で表される遷移金属化合物と助触媒から構成されるシングルサイト配位重合触媒である。
式中、Ａ、Ｂは同一でも異なっていてもよく、非置換もしくは置換ベンゾインデニル基、非置換もしくは置換インデニル基、非置換もしくは置換シクロペンタジエニル基、又は非置換もしくは置換フルオレニル基から選ばれる基であり、少なくともＡ，Ｂのうち１個は非置換もしくは置換ベンゾインデニル基、非置換もしくは置換インデニル基から選ばれる基である。ここで置換ベンゾインデニル基、置換インデニル基、置換シクロペンタジエニル基、又は置換フルオレニル基とは、置換可能な水素の１個以上が炭素数１〜２０のアルキル基、炭素数６〜１０のアリール基、炭素数７〜２０のアルキルアリール基、ハロゲン原子、ＯＳｉＲ３基、ＳｉＲ３基、又はＰＲ２基（Ｒはいずれも炭素数１〜１０の炭化水素基を表す）で置換されたベンゾインデニル基、インデニル基、シクロペンタジエニル基、又はフルオレニル基である。
ＹはＡ、Ｂと結合を有し、他に置換基として水素もしくは炭素数１〜１５の炭化水素基（１〜３個の窒素、酸素、硫黄、燐、珪素原子を含んでもよい）を有するメチレン基、硼素基である。置換基は互いに異なっていても同一でもよい。また、Ｙは環状構造を有していてもよい。
Ｘは、水素、水酸基、ハロゲン、炭素数１〜２０の炭化水素基、炭素数１〜２０のアルコキシ基、炭素数１〜４の炭化水素置換基を有するシリル基、又は炭素数１〜２０の炭化水素置換基を有するアミド基である。２個のＸは結合を有しても良い。
Ｍはジルコニウム、ハフニウム、又はチタンである。
式中、Ｃｐは非置換もしくは置換シクロペンタフェナンスリル基、非置換もしくは置換ベンゾインデニル基、非置換もしくは置換シクロペンタジエニル基、非置換もしくは置換インデニル基、又は非置換もしくは置換フルオレニル基から選ばれる基である。Ｙ’は、Ｃｐ、Ｚと結合を有し、他に水素もしくは炭素数１〜１５の炭化水素基を有するメチレン基、シリレン基、エチレン基、ゲルミレン基、硼素残基である。置換基は互いに異なっていても同一でもよい。また、Ｙ’は環状構造を有していてもよい。Ｚは窒素、酸素、又はイオウを含み、窒素、酸素、又はイオウでＭ’に配位する配位子でＹ’と結合を有し、他に水素、炭素数１〜１５の置換基を有する基である。
Ｍ’はジルコニウム、ハフニウム、又はチタンである。
Ｘ’は、水素、ハロゲン、炭素数１−１５のアルキル基、炭素数６−１０のアリール基、炭素数８−１２のアルキルアリール基、炭素数１−４の炭化水素置換基を有するシリル基、炭素数１−１０のアルコキシ基、又は炭素数１−６のアルキル置換基を有するジアルキルアミド基である。
ｎは、１、又は２の整数である。
（５）炭素数５以上２０以下の環状オレフィン及び／又は炭素数８以上２０以下の芳香族ビニル化合物から選ばれる一種以上からなり、かつポリエン含量が１質量部未満であることを特徴とする非極性ビニル化合物。 51-72 parts by mass of an ethylene-olefin-polyene copolymer characterized by satisfying the following conditions (1) to (4), and 49-28 parts by mass of a nonpolar vinyl compound satisfying the condition of (5) Storage elasticity at 200 ° C. obtained by curing a post-curing resin composition characterized by containing a curing agent, having a tensile modulus of 70 MPa or less, a tensile elongation at break of 30% or more, and a viscoelastic spectrum measurement The ratio of the storage elastic modulus at 50 ° C. to the storage elastic modulus at 200 ° C. obtained by measuring viscoelasticity spectrum is 2 × 10 5 Pa or more (= E ′ of 50 ° C./E ′ of 200 ° C.) is 5 times. A cured product that is:
(1) The olefin is one or more selected from an α-olefin having 3 to 20 carbon atoms, a cyclic olefin having 5 to 20 carbon atoms, and an aromatic vinyl compound having 8 to 20 carbon atoms.
(2) The polyene is one or more selected from polyenes having 5 to 20 carbon atoms and having a plurality of vinyl groups and / or vinylene groups in the molecule.
(3) The number average molecular weight of the ethylene-olefin-polyene copolymer is from 5,000 to 30,000, the weight average molecular weight / number average molecular weight is from 1.5 to 5, and the polyene unit content is the number average molecular weight. The content of olefin units is 5 mol% or more and 70 mol% or less, and the balance is ethylene units.
(4) A single site coordination polymerization catalyst in which the catalyst used when copolymerizing ethylene, olefin and polyene is composed of a transition metal compound represented by the following general formula (1) or (2) and a co-catalyst It is.
In the formula, A and B may be the same or different and are selected from an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted indenyl group, an unsubstituted or substituted cyclopentadienyl group, or an unsubstituted or substituted fluorenyl group. At least one of A and B is a group selected from an unsubstituted or substituted benzoindenyl group and an unsubstituted or substituted indenyl group. Here, the substituted benzoindenyl group, the substituted indenyl group, the substituted cyclopentadienyl group, or the substituted fluorenyl group is an alkyl group having 1 to 20 carbon atoms, one or more hydrogen atoms that can be substituted, and having 6 to 10 carbon atoms. Benzoindenyl group substituted with an aryl group, an alkylaryl group having 7 to 20 carbon atoms, a halogen atom, an OSiR3 group, an SiR3 group, or a PR2 group (wherein R represents a hydrocarbon group having 1 to 10 carbon atoms) , An indenyl group, a cyclopentadienyl group, or a fluorenyl group.
Y has a bond with A and B, and additionally has hydrogen or a hydrocarbon group having 1 to 15 carbon atoms (may contain 1 to 3 nitrogen, oxygen, sulfur, phosphorus, or silicon atoms) as a substituent. A methylene group and a boron group. The substituents may be different or the same. Y may have a cyclic structure.
X is hydrogen, a hydroxyl group, a halogen, a C1-C20 hydrocarbon group, a C1-C20 alkoxy group, a silyl group having a C1-C4 hydrocarbon substituent, or a C1-C20 It is an amide group having a hydrocarbon substituent. Two Xs may have a bond.
M is zirconium, hafnium, or titanium.
In the formula, Cp represents an unsubstituted or substituted cyclopentaphenanthryl group, an unsubstituted or substituted benzoindenyl group, an unsubstituted or substituted cyclopentadienyl group, an unsubstituted or substituted indenyl group, or an unsubstituted or substituted fluorenyl group. The group to be selected. Y ′ is a methylene group, a silylene group, an ethylene group, a germylene group, or a boron residue having a bond with Cp and Z, and further having hydrogen or a hydrocarbon group having 1 to 15 carbon atoms. The substituents may be different or the same. Y ′ may have a cyclic structure. Z contains nitrogen, oxygen or sulfur, is a ligand coordinated to M ′ with nitrogen, oxygen or sulfur, has a bond with Y ′, and additionally has hydrogen and a substituent having 1 to 15 carbon atoms. It is a group.
M ′ is zirconium, hafnium, or titanium.
X ′ is hydrogen, halogen, an alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkylaryl group having 8 to 12 carbon atoms, or a silyl group having a hydrocarbon substituent having 1 to 4 carbon atoms. , A dialkylamide group having an alkoxy group having 1 to 10 carbon atoms or an alkyl substituent having 1 to 6 carbon atoms.
n is an integer of 1 or 2.
(5) It is composed of one or more selected from cyclic olefins having 5 to 20 carbon atoms and / or aromatic vinyl compounds having 8 to 20 carbon atoms, and the polyene content is less than 1 part by mass. Polar vinyl compound.
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