JP4255073B2 - Resin composition and high frequency circuit laminate using the same - Google Patents
Resin composition and high frequency circuit laminate using the same Download PDFInfo
- Publication number
- JP4255073B2 JP4255073B2 JP2004071870A JP2004071870A JP4255073B2 JP 4255073 B2 JP4255073 B2 JP 4255073B2 JP 2004071870 A JP2004071870 A JP 2004071870A JP 2004071870 A JP2004071870 A JP 2004071870A JP 4255073 B2 JP4255073 B2 JP 4255073B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- resin composition
- pentene
- methyl
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000011342 resin composition Substances 0.000 title claims description 36
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 50
- 229920000642 polymer Polymers 0.000 claims description 41
- 229920013639 polyalphaolefin Polymers 0.000 claims description 11
- 239000011256 inorganic filler Substances 0.000 claims description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 description 37
- 239000000178 monomer Substances 0.000 description 36
- 238000000034 method Methods 0.000 description 35
- -1 polyethylene Polymers 0.000 description 32
- 238000006116 polymerization reaction Methods 0.000 description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 19
- 239000005977 Ethylene Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- 239000004711 α-olefin Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 239000004020 conductor Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 229920005601 base polymer Polymers 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- 238000003825 pressing Methods 0.000 description 8
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 7
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 7
- 229920013716 polyethylene resin Polymers 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 6
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000010030 laminating Methods 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 5
- 238000005476 soldering Methods 0.000 description 5
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 5
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920000306 polymethylpentene Polymers 0.000 description 3
- 239000011116 polymethylpentene Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229940106006 1-eicosene Drugs 0.000 description 2
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 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
- UJNVTDGCOKFBKM-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)hexane Chemical compound CCCCCC(OOC(C)(C)C)OOC(C)(C)C UJNVTDGCOKFBKM-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- GWQOYRSARAWVTC-UHFFFAOYSA-N 1,4-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=C(C(C)(C)OOC(C)(C)C)C=C1 GWQOYRSARAWVTC-UHFFFAOYSA-N 0.000 description 1
- YZFOQJOYMTZTRH-UHFFFAOYSA-N 1-(2-methylbutyl)cyclohexene Chemical compound CCC(C)CC1=CCCCC1 YZFOQJOYMTZTRH-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 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 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- JOVGLRSLWFSVNB-UHFFFAOYSA-N 3,4-dimethylcyclopentene Chemical compound CC1CC=CC1C JOVGLRSLWFSVNB-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- UZPWKTCMUADILM-UHFFFAOYSA-N 3-methylcyclohexene Chemical compound CC1CCCC=C1 UZPWKTCMUADILM-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 101100484967 Solanum tuberosum PVS1 gene Proteins 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- RZJRJXONCZWCBN-UHFFFAOYSA-N alpha-octadecene Natural products CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- HANKSFAYJLDDKP-UHFFFAOYSA-N dihydrodicyclopentadiene Chemical compound C12CC=CC2C2CCC1C2 HANKSFAYJLDDKP-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011980 kaminsky catalyst Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Description
本発明は、低誘電率・低誘電正接、耐熱性に優れた樹脂組成物及び該樹脂組成物を用いた絶縁層を有する高周波回路用積層板に関する。 The present invention relates to a resin composition excellent in low dielectric constant / low dielectric loss tangent and heat resistance, and a laminate for a high frequency circuit having an insulating layer using the resin composition.
近年、情報・通信機器分野では、伝送情報の高容量化、高スピード処理のための高周波化が進んでいる。これまでＧＨｚを超えるような高周波信号は、レーダーや衛星通信など限られた用途で用いられてきたが、最近では携帯電話や無線ＬＡＮなどきわめて身近に用いられるようになってきた。また、コンピュータや通信機器の高速化・高機能化にともない、これらの機器間の情報伝送に用いられる信号も飛躍的に高周波化している。従来、プリント配線基板用材料としては、主にエポキシ樹脂やフェノール樹脂が用いられてきた。しかしこれらの樹脂は、高周波領域における誘電特性が悪く、伝送ロスが大きいなどの理由で高周波回路に用いることができない。 In recent years, in the information / communication equipment field, transmission information has a high capacity and high frequency for high-speed processing. Until now, high-frequency signals exceeding GHz have been used for limited applications such as radar and satellite communications, but recently, they have become very close to mobile phones and wireless LANs. In addition, with the increase in speed and functionality of computers and communication devices, signals used for information transmission between these devices have also dramatically increased in frequency. Conventionally, epoxy resin and phenol resin have been mainly used as printed wiring board materials. However, these resins cannot be used for high-frequency circuits because of their poor dielectric characteristics in the high-frequency region and large transmission loss.
またセラミック・アルミナなどの無機系基板材料は一般に誘電正接が低いが、取扱い性、入手性、コストなどの観点から、有機系材料への置き換えが進みつつある。このような現状から、ＧＨｚ領域で使用可能な電気特性（高周波伝送特性、低誘電特性）に優れる基板材料の開発が強く要望され、ポリフェニレンエーテル樹脂やビスマレイミドトリアジン樹脂などが開発・実用化されてきた。（非特許文献１および特許文献１参照）。しかし信号の高周波化は数ＧＨｚを超えてさらに数十ＧＨｚへと進み、これらの新規材料ですら対応できない領域に達しようとしている。 Further, although inorganic substrate materials such as ceramic and alumina generally have a low dielectric loss tangent, replacement with organic materials is progressing from the viewpoints of handleability, availability and cost. Under such circumstances, there is a strong demand for the development of substrate materials that have excellent electrical characteristics (high-frequency transmission characteristics, low dielectric characteristics) that can be used in the GHz range, and polyphenylene ether resins and bismaleimide triazine resins have been developed and put to practical use. It was. (See Non-Patent Document 1 and Patent Document 1). However, the frequency of signals has increased from several GHz to several tens of GHz, and even these new materials are reaching an area that cannot be handled.
一方、ポリエチレン、ポリプロピレン等のポリオレフィンは、誘電率・誘電正接の面で非常に優れるが、単独では耐熱性に劣るため、ハンダ付け作業など２００℃を超える温度がかかる電気回路製造工程に耐えることができない。これを改善するため、環状オレフィンを共重合させ、優れた誘電特性を保持したまま耐熱性を向上させた材料が開発された（特許文献２参照）。しかし、最近でははんだの鉛フリー化によるはんだ付け温度の上昇などで、２６０℃以上の高い耐熱温度が望まれるようになってきている。 On the other hand, polyolefins such as polyethylene and polypropylene are very excellent in terms of dielectric constant and dielectric loss tangent, but they are inferior in heat resistance, so that they can withstand electric circuit manufacturing processes that require temperatures exceeding 200 ° C. such as soldering operations. Can not. In order to improve this, a material has been developed in which cyclic olefins are copolymerized and heat resistance is improved while maintaining excellent dielectric properties (see Patent Document 2). However, recently, a high heat-resistant temperature of 260 ° C. or higher has been desired due to an increase in soldering temperature due to lead-free soldering.
また、金属との接着性に劣るフッ素系材料やオレフィン系材料では、金属の表面粗度を大きくしアンカー効果（くいこみ）によって接着性を保持させるのが一般的である。しかし、高周波電流には金属導体の表皮部分のみを流れようとする表皮効果という性質があるため、表面粗度が大きいと抵抗が大きくなり信号伝播の劣化原因となってしまう。信号の高周波化に伴い、金属導体も表面が平滑なものが用いられるようになってきたため、これらの材料は高い誘電特性を持ちながらも、高周波材料としては使用することができなかった。接着性を改良する方法として、不飽和カルボン酸またはその誘導体でグラフト変性されたポリ４−メチル−１−ペンテンからなる樹脂を強化繊維に含浸させた強化プラスチック層を用いる方法が開示されている（特許文献３参照）。しかし、この技術においても、導体と接している樹脂層表面は、融点２３５℃程度のポリ４−メチル−１−ペンテンであり、依然として鉛フリーはんだでのはんだづけに対応できる耐熱性を有していなかった。 Moreover, in the fluorine-type material and olefin-type material which are inferior to adhesiveness with a metal, it is common to make the surface roughness of a metal large and to maintain adhesiveness by an anchor effect (squeezing). However, since the high-frequency current has the property of a skin effect that tries to flow only through the skin portion of the metal conductor, if the surface roughness is large, the resistance increases and causes deterioration of signal propagation. As the frequency of signals increases, metal conductors with smooth surfaces have come to be used. Therefore, these materials cannot be used as high frequency materials while having high dielectric properties. As a method for improving adhesiveness, a method using a reinforced plastic layer in which a reinforced fiber is impregnated with a resin composed of poly-4-methyl-1-pentene graft-modified with an unsaturated carboxylic acid or a derivative thereof is disclosed ( (See Patent Document 3). However, even in this technique, the surface of the resin layer in contact with the conductor is poly-4-methyl-1-pentene having a melting point of about 235 ° C. and still does not have heat resistance that can be used for soldering with lead-free solder. It was.
こうした状況の中、より高周波での利用が可能な基板の開発が待ち望まれているのである。
本発明が解決しようとする課題は、高周波信号の伝送に対応する積層板を提供することのできる新規な樹脂組成物を提供することである。より詳細には、低誘電率、低誘電正接、耐熱性、そして導体との接着性を併せ持つ樹脂組成物、及び該樹脂組成物を用いた高周波回路用積層板を提供することである。 The problem to be solved by the present invention is to provide a novel resin composition capable of providing a laminated plate corresponding to transmission of a high-frequency signal. More specifically, it is to provide a resin composition having a low dielectric constant, a low dielectric loss tangent, heat resistance, and adhesion to a conductor, and a laminate for a high-frequency circuit using the resin composition.
本研究者らは前記課題を解決するべく鋭意検討した結果、４−メチル−１−ペンテン系重合体、変性ポリα−オレフィン系重合体、および無機フィラーを特定の割合でブレンドして得られる樹脂組成物を用いた積層板が、低誘電率、低誘電正接、耐熱性、さらに導体との接着性に優れていることを見出し、本発明を完成した。 As a result of intensive studies to solve the above problems, the present researchers have obtained a resin obtained by blending 4-methyl-1-pentene polymer , modified poly α-olefin polymer, and inorganic filler at a specific ratio. The present inventors have found that a laminate using the composition is excellent in low dielectric constant, low dielectric loss tangent, heat resistance, and adhesiveness with a conductor, and completed the present invention.
すなわち、本発明は、
（Ｉ）４−メチル−１−ペンテン系重合体３〜７２重量部、
That is, the present invention
(I) 4-72 parts by weight of 4-methyl-1-pentene polymer,
（II）不飽和カルボン酸および／またはその誘導体によりグラフト変性された部分を、０．０１〜１０重量％有する変性ポリα−オレフィン系重合体０．５〜５０重量部
（III）無機フィラー２５〜９０重量部
からなる、但し（Ｉ）、（II）、（III）成分の合計が１００重量部であることを特徴とする樹脂組成物であり、該樹脂組成物を用いた絶縁層を有する高周波回路用積層板である。
(II) 0.5 to 50 parts by weight of a modified poly α-olefin polymer having 0.01 to 10% by weight of a portion graft-modified with an unsaturated carboxylic acid and / or derivative thereof (III) Inorganic filler 25 to 25 A resin composition comprising 90 parts by weight, wherein the total of components (I), (II), and (III) is 100 parts by weight, and has a high frequency having an insulating layer using the resin composition It is a laminated board for circuits.
本発明により、高周波特性の指標である誘電率・誘電正接に優れ、高耐熱性および導体との高接着性という特徴を併せ持った、高周波回路用積層板の提供が可能となった。 According to the present invention, it has become possible to provide a laminate for a high-frequency circuit that is excellent in dielectric constant and dielectric loss tangent, which are indicators of high-frequency characteristics, and has the characteristics of high heat resistance and high adhesion to a conductor.
以下、本発明を詳細に説明する。
本発明は、（Ｉ）４−メチル−１−ペンテン系重合体、および／または少なくとも前記一般式（１）で示されるモノマー成分を含み重合体中において該モノマー成分が前記一般式（２）で示される構造をとる環状オレフィン系共重合体より選ばれる重合体と、不飽和カルボン酸および／またはその誘導体によりグラフト変性された変性ポリα−オレフィン系重合体および／またはその組成物、そして無機フィラーを特定の比率でブレンドすることを特徴とする樹脂組成物およびそれを用いた高周波回路用積層板である。
Hereinafter, the present invention will be described in detail.
The present invention includes (I) a 4-methyl-1-pentene polymer and / or at least a monomer component represented by the general formula (1), wherein the monomer component is represented by the general formula (2). Polymers selected from cyclic olefin copolymers having the structure shown, modified poly α-olefin polymers and / or compositions graft-modified with unsaturated carboxylic acids and / or derivatives thereof, and inorganic fillers Are blended at a specific ratio, and a laminate for a high-frequency circuit using the resin composition.
本発明で（Ｉ）の成分として用いられる４−メチル−１−ペンテン系重合体としては、４−メチル−１−ペンテンの単独重合体であるか、もしくは４−メチル−１−ペンテンと他のα−オレフィン、例えばエチレン、プロピレン、１−ブテン、１−ヘキセン、１−オクテン、１−デセン、１−テトラデセン、１−オクタデセン等の炭素数２〜２０のα−オレフィンや鎖状ジエンとの共重合体が好ましい。かかる共重合体としては、４−メチル−１−ペンテンを８０重量％以上の量で含む４−メチル−１−ペンテンを主体とした共重合体が好ましい。好ましい共重合成分は、例えば１−デセン、１−ドデカン、１−テトラデカン、１−ヘキサデカン、１−オクタデカンあるいは１−エイコセンである。４−メチル−１−ペンテン系重合体の共重合成分の含有量が２０重量％以下の場合の方が、４−メチル−１−ペンテン系重合体の融点が低下することなく、また耐熱性が低下することがないため好ましい。 The 4-methyl-1-pentene polymer used as the component (I) in the present invention is a homopolymer of 4-methyl-1-pentene, or 4-methyl-1-pentene and other polymers. Co-generation with α-olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene, etc. Polymers are preferred. As such a copolymer, a copolymer mainly composed of 4-methyl-1-pentene containing 4-methyl-1-pentene in an amount of 80% by weight or more is preferable. Preferred copolymerization components are, for example, 1-decene, 1-dodecane, 1-tetradecane, 1-hexadecane, 1-octadecane or 1-eicosene. When the content of the copolymer component of the 4-methyl-1-pentene polymer is 20% by weight or less, the melting point of the 4-methyl-1-pentene polymer does not decrease, and the heat resistance is improved. Since it does not fall, it is preferable.
このような４−メチル−１−ペンテン系重合体のメルトフローレート（ＭＦＲ）は、ＡＳＴＭＤ １２３８に準じ、荷重：５.０ｋｇ、温度：２６０℃の条件で測定した値が１〜４００ｇ／１０分の範囲内にあることが望ましく、１０〜３００ｇ／１０分の範囲内にあるのがより好ましい。この範囲にあると（II）、（III）成分との混合性が低下することなく均一な樹脂組成物を得ることが可能であり、また樹脂組成物の強度的特性が低下することなく好ましい。 The melt flow rate (MFR) of such 4-methyl-1-pentene polymer is 1 to 400 g / 10 min as measured according to ASTM D 1238 under the conditions of load: 5.0 kg and temperature: 260 ° C. Is preferably in the range of 10 to 300 g / 10 min. Within this range, it is possible to obtain a uniform resin composition without lowering the mixing properties with the components (II) and (III), and it is preferable without lowering the strength properties of the resin composition.
本発明で（Ｉ）の成分として用いられる４−メチル−１−ペンテン系重合体は、公知の方法で製造することができる。重合触媒や重合方法にも特に制約はなく、例えば触媒としては、チーグラー型触媒（担持または非担持ハロゲン含有チタン化合物とアルミニウム化合物の組み合わせに基づくもの）、フィリップス型触媒（担持酸化クロムに基づくもの）、カミンスキー型触媒（担持または非担持メタロセン型化合物と有機アルミニウム化合物、特にアルモキサンとの組みあわせに基づくもの）等が挙げられる。重合方法としては、これらの触媒存在下でのスラリー重合法、気相流動床重合法、溶液重合法、あるいは圧力が２００ｋｇ／ｃｍ２以上、重合温度が１００℃以上での高圧バルク重合法等の公知の重合方法が挙げられる。 The 4-methyl-1-pentene polymer used as the component (I) in the present invention can be produced by a known method. There are no particular restrictions on the polymerization catalyst and polymerization method. Examples of the catalyst include Ziegler type catalysts (based on a combination of a supported or unsupported halogen-containing titanium compound and an aluminum compound), Philips type catalysts (based on supported chromium oxide). And a Kaminsky catalyst (based on a combination of a supported or unsupported metallocene compound and an organoaluminum compound, particularly an alumoxane). Examples of the polymerization method include slurry polymerization method in the presence of these catalysts, gas phase fluidized bed polymerization method, solution polymerization method, or high pressure bulk polymerization method in which the pressure is 200 kg / cm 2 or more and the polymerization temperature is 100 ° C. or more. Known polymerization methods may be mentioned.
本発明で（Ｉ）の成分として用いられる環状オレフィン系共重合体は、前述した一般式（１）で表されるモノマー成分を含むものであって、重合体中においては該モノマー成分が主として一般式（２）で示される構造をとっているものである。かかる重合体として好ましい態様は、一般式（１）のモノマー成分とともにα―オレフィンおよび／または一般式（１）以外の環状オレフィンとからなる共重合体が例示でき、好適なものとして一般式（１）で表されるモノマー及びエチレンを含むものを挙げることができる。 The cyclic olefin copolymer used as the component (I) in the present invention includes the monomer component represented by the general formula (1) described above, and the monomer component is mainly common in the polymer. It has a structure represented by the formula (2). As a preferred embodiment of such a polymer, there can be exemplified a copolymer comprising an α-olefin and / or a cyclic olefin other than the general formula (1) together with the monomer component of the general formula (1). ) And a monomer containing ethylene.
（Ｉ）成分中、一般式（１）のモノマー成分は少なくとも２モル％以上含むべきであるが、エチレンを共存させる場合には、エチレン／一般式（１）のモノマー成分のモル比が５／９５〜９５／５、とくに４０／６０〜９０／１０の範囲が好ましく、さらにエチレン以外のα―オレフィンや鎖状ジエンあるいは一般式（１）以外の環状オレフィンや環状ジエンたとえばサリチリデンノルボルネン、ジシクロペンタジエンなどを共存させる場合にはこれらのモノマー合計量／一般式（１）のモノマー成分のモル比が５／９５〜９５／５、とくに３０／７０〜９０／１０の範囲が好ましい。また一般式（１）のモノマー成分は単品のみならず、一般式（１）で表される複数の成分が混合していてもよい。 In the component (I), the monomer component of the general formula (1) should be contained in an amount of at least 2 mol%, but when ethylene is allowed to coexist, the molar ratio of ethylene / monomer component of the general formula (1) is 5 / The range of 95 to 95/5, particularly 40/60 to 90/10 is preferable. Furthermore, α-olefins other than ethylene, chain dienes, cyclic olefins other than general formula (1) and cyclic dienes such as salicylidene norbornene, diene When cyclopentadiene or the like is allowed to coexist, the molar ratio of the total amount of these monomers / the monomer component of the general formula (1) is preferably 5/95 to 95/5, particularly preferably 30/70 to 90/10. Moreover, the monomer component of General formula (1) may mix not only the single item but the several component represented by General formula (1).
一般式（１）で示されるモノマー成分式中、Ｒ１〜Ｒ１２は水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基などのアルキル基、または、フッ素、塩素、臭素、ヨウ素などのハロゲン原子であり、それぞれ同一または異なっていてもよく、さらにＲ９またはＲ１０とＲ１１またはＲ１２とは互いに環を形成してもよい。 In the monomer component formula represented by the general formula (1), R1 to R12 are hydrogen groups, methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, t-butyl groups, and other alkyl groups. Or halogen atoms such as fluorine, chlorine, bromine and iodine, which may be the same or different from each other, and R9 or R10 and R11 or R12 may form a ring with each other.
一般式（１）で示されるモノマー成分の具体例を示すと以下のものを挙げることができるが、ここで示される例は極めて限定されたものであって、一般式（１）で示されるものであればいかなるものも本発明のモノマー成分になりうる。 Specific examples of the monomer component represented by the general formula (1) can include the following, but the examples shown here are extremely limited and are represented by the general formula (1). Any of them can be the monomer component of the present invention.
これらの中では一般式（１）においてｎ＝１のもの、すなわち一般式（３） Among these, in general formula (1), n = 1, that is, general formula (3)
（式中、Ｒ１〜Ｒ１２は前記と同じ意味を示す。）
で示されるモノマー成分が、モノマーの入手しやすさあるいはモノマー合成のしやすさの面で好ましく、例えば、１，４，５，８−ジメタノ−１，２，３，４，４ａ，５，８，８ａ−オクタヒドロナフタレンや、２，３−ジメチル−１，４，５，８−ジメタノ−１，２，３，４，４ａ，５，８，８ａ−オクタヒドロナフタレンなどが好ましい。
(Wherein R1 to R12 have the same meaning as described above.)
Is preferable in terms of the availability of monomers or the ease of monomer synthesis. For example, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8 , 8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and the like are preferable.
上述のモノマー成分は、特開昭５７−１５４１３３号等にも記載のようにシクロペンタジエン類と相応するオレフィン類とをディールス・アルダー反応で縮合させることにより容易に製造することが可能である。例えば、上述の一般式（３）のモノマー成分を合成するには、下記式のようにノルボルネンに対してシクロペンタジエンを縮合することにより得ることができる。 The monomer component described above can be easily produced by condensing cyclopentadiene and the corresponding olefin by Diels-Alder reaction as described in JP-A-57-154133. For example, in order to synthesize the monomer component of the above general formula (3), it can be obtained by condensing cyclopentadiene with norbornene as in the following formula.
（式中、Ｒ１〜Ｒ１２は前記と同じ意味を示す。）
式（４）以外の一般式（１）で示されるモノマー成分も、基本的には出発物質の違いだけであり、同じ縮合反応の応用で製造することができる。
(Wherein R1 to R12 have the same meaning as described above.)
The monomer component represented by the general formula (1) other than the formula (4) is basically only a difference in the starting material, and can be produced by applying the same condensation reaction.
前記一般式（１）のモノマー成分と共重合されうるα−オレフィンとしては、炭素原子数２〜２０、好ましくは炭素原子数２〜１０のα−オレフィンが好ましく、例えばエチレン、プロピレン、１−ブテン、３−メチル−１−ブテン、１−ペンテン、３−メチル−１−ペンテン、４−メチル−１−ペンテン、１−ヘキセン、１−オクテン、１−デセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１−イコセンなどが挙げられる。これらの中では特にエチレンが共重合性の面から好ましく、他のα−オレフィン（炭素原子数３以上）あるいは後述する環状オレフィンや環状ジエンを一般式（１）のモノマー成分と共重合させる場合にも、エチレンが存在したほうが共重合性は良好である。 The α-olefin that can be copolymerized with the monomer component of the general formula (1) is preferably an α-olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, such as ethylene, propylene, 1-butene. 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1 -Hexadecene, 1-icocene, etc. are mentioned. Among these, ethylene is particularly preferable from the viewpoint of copolymerizability, and other α-olefins (3 or more carbon atoms) or cyclic olefins and cyclic dienes described later are copolymerized with the monomer component of the general formula (1). However, the copolymerization is better in the presence of ethylene.
前記一般式（１）のモノマー成分と共重合されうる別の成分である一般式（１）以外の環状オレフィン及び環状ジエンとしては、たとえばシクロペンテン、シクロヘキセン、３，４−ジメチルシクロペンテン、３−メチルシクロヘキセン、２−（２−メチルブチル）−１−シクロヘキセン、スチレン、α−メチルスチレン、３ａ，５，６，７ａ−テトラヒドロ−４，７−メタノ−１Ｈ−インデン、ジシクロペンタジエン、エチリデンノルボルネン、ビニルノルボルネンなどを例示できる。さらに以上述べてきたモノマー成分のほかに、ほかの共重合可能なモノマー成分を本発明の目的を損なわない範囲内で、重合体中に少量含んでいてもよい。 Examples of the cyclic olefin and cyclic diene other than the general formula (1) which are other components that can be copolymerized with the monomer component of the general formula (1) include, for example, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, and 3-methylcyclohexene. 2- (2-methylbutyl) -1-cyclohexene, styrene, α-methylstyrene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, dicyclopentadiene, ethylidene norbornene, vinyl norbornene, etc. Can be illustrated. Further, in addition to the monomer components described above, other copolymerizable monomer components may be contained in the polymer in a small amount within the range not impairing the object of the present invention.
本発明で（Ｉ）の成分として用いられる環状オレフィン系共重合体は、いかなる方法で製造されたものであっても構わないが、好ましい製造方法の一例として、上記一般式（１）で表される不飽和単量体とα−オレフィンおよび／又は環状オレフィンなどを、チーグラー触媒とくにバナジウム系のチーグラー触媒をはじめとする周知の触媒を使用して重合することにより製造することができる。 The cyclic olefin copolymer used as the component (I) in the present invention may be produced by any method, but as an example of a preferred production method, it is represented by the general formula (1). Can be produced by polymerizing an unsaturated monomer and an α-olefin and / or a cyclic olefin using a known catalyst such as a Ziegler catalyst, particularly a vanadium Ziegler catalyst.
本発明で（Ｉ）の成分として用いられる環状オレフィン共重合体のより好ましい態様は、上記一般式（１）のモノマー成分と少なくともエチレンを含み、必要に応じて他のオレフィンや環状オレフィンを含むものである。この場合、エチレン／式（１）のモノマー成分とのモル比は、５／９５〜９５／５、とくには４０／６０〜９０／１０の範囲にあるのが好ましく、さらにエチレン以外の他のモノマー成分すなわち炭素原子数３以上のα−オレフィンや環状オレフィンなどが存在する場合には、これらのモノマー成分の合計量／式（１）のモノマー成分（モル比）が５／９５〜９５／５、とくには３０／７０〜９０／１０の範囲にあるのが好ましい。 A more preferable embodiment of the cyclic olefin copolymer used as the component (I) in the present invention contains the monomer component of the general formula (1) and at least ethylene, and if necessary, other olefins and cyclic olefins. . In this case, the molar ratio of ethylene / monomer component of formula (1) is preferably in the range of 5/95 to 95/5, particularly 40/60 to 90/10, and other monomers other than ethylene. In the case where a component, that is, an α-olefin having 3 or more carbon atoms or a cyclic olefin is present, the total amount of these monomer components / the monomer component (molar ratio) of the formula (1) is 5/95 to 95/5, In particular, it is preferably in the range of 30/70 to 90/10.
本発明で（II）の成分として用いられる変性ポリα−オレフィン系重合体は、不飽和カルボン酸および／またはその誘導体によりグラフト変性された部分を０．０１から１０重量％有する変性ポリα−オレフィン系重合体である。その際のベースポリマーとしては、特に限定されるものではないが、通常炭素数２〜２０のα−オレフィンの単独重合体、もしくはそれらのα−オレフィンの共重合体が用いられ、例えば、ポリエチレン、ポリプロピレン、ポリブテン、ポリペンテン−１、ポリ（４−メチル−１−ペンテン）等のホモポリマー、エチレン・プロピレン共重合体、エチレン・ブテン共重合体、プロピレン・ブテン共重合体、ブテン・ペンテン−１共重合体、４−メチル−１−ペンテンと炭素数２〜２０の他のα−オレフィンとの共重合体、エチレン・プロピレン・ジエン共重合体、エチレン・プロピレン・ブテン共重合体、エチレン・プロピレン・ペンテン共重合体等の共重合体を用いることが出来る。これらの内では、ポリプロピレン、ポリエチレン、エチレンと他のα−オレフィンとの共重合体、ポリ（４−メチル−１−ペンテン）、４−メチル−１−ペンテンと他のα−オレフィンとの共重合体が経済性、接着性、成形性の点から好適である。該ベースポリマーがエチレンと他のα−オレフィンとの共重合体の場合、好ましい共重合成分としては、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、４−メチル−１−ペンテンであり、エチレン単位を主体とした共重合体が好ましい。該ベースポリマーが４−メチル−１−ペンテンと他のα−オレフィンとの共重合体の場合、好ましい共重合成分としては、１−デセン、１−ドデセン、１−テトラデセン、１−ヘキサデセン、１−オクタデセン、１−エイコセンであり、４−メチル−１−ペンテン単位を主体とした共重合体が好ましい。該ベースポリマーとして、本発明の（Ｉ）成分に用いられる４−メチル−１−ペンテン系重合体と同じ性状のものを用いてもよい。 The modified poly α-olefin polymer used as the component (II) in the present invention is a modified poly α-olefin having a portion graft-modified with an unsaturated carboxylic acid and / or a derivative thereof in an amount of 0.01 to 10% by weight. Based polymer. The base polymer in that case is not particularly limited, but usually a homopolymer of an α-olefin having 2 to 20 carbon atoms or a copolymer of those α-olefins is used, for example, polyethylene, Homopolymers such as polypropylene, polybutene, polypentene-1, poly (4-methyl-1-pentene), ethylene / propylene copolymer, ethylene / butene copolymer, propylene / butene copolymer, butene / pentene-1 Polymer, copolymer of 4-methyl-1-pentene and other α-olefin having 2 to 20 carbon atoms, ethylene / propylene / diene copolymer, ethylene / propylene / butene copolymer, ethylene / propylene / A copolymer such as a pentene copolymer can be used. Among these, polypropylene, polyethylene, copolymers of ethylene and other α-olefins, poly (4-methyl-1-pentene), copolymer weight of 4-methyl-1-pentene and other α-olefins The coalescence is preferable from the viewpoints of economy, adhesiveness, and moldability. When the base polymer is a copolymer of ethylene and another α-olefin, preferred copolymer components are propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, Copolymers mainly composed of ethylene units are preferred. When the base polymer is a copolymer of 4-methyl-1-pentene and other α-olefin, preferred copolymer components include 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- A copolymer mainly composed of octadecene and 1-eicosene and mainly composed of 4-methyl-1-pentene unit is preferable. As the base polymer, those having the same properties as the 4-methyl-1-pentene polymer used for the component (I) of the present invention may be used.
このベースポリマーにグラフトする不飽和カルボン酸又はその誘導体としては、例えば、マレイン酸、フマール酸、テトラヒドロフタル酸、イタコン酸、シトラコン酸、クロトン酸、イソクロトン酸、ナジック酸（登録商標）、アクリル酸、メタクリル酸等の不飽和カルボン酸、またはその誘導体、例えば上記不飽和カルボン酸の酸無水物、イミド、アミド、エステル等を挙げることが出来る。該誘導体として、具体的には、マレイミド、無水マレイン酸、無水シトラコン酸、マレイン酸モノメチル、グリシジルマレート等を例示できる。これらの中では、不飽和カルボン酸またはその酸無水物が好適であり、特に、マレイン酸、ナジック酸（登録商標）、それらの酸無水物がとりわけ好適である。 Examples of the unsaturated carboxylic acid or derivative thereof grafted to the base polymer include maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid (registered trademark), acrylic acid, Examples thereof include unsaturated carboxylic acids such as methacrylic acid or derivatives thereof, for example, acid anhydrides, imides, amides and esters of the above unsaturated carboxylic acids. Specific examples of the derivative include maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, glycidyl malate, and the like. Among these, unsaturated carboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid (registered trademark), and acid anhydrides thereof are particularly preferable.
この様な不飽和カルボン酸またはその誘導体から選ばれるグラフトモノマーを前記ベースポリマーにグラフト共重合して変性物を製造するには、従来公知の方法を用いることができる。例えば、ベースポリマーとして４−メチル−１−ペンテン系重合体を用いる場合、該４−メチル−１−ペンテン系重合体を溶融させグラフトモノマーを添加してグラフト共重合させる溶融変性法、あるいは溶媒に溶解させグラフトモノマーを添加してグラフト共重合させる溶液変性法等を用いることができる。 In order to produce a modified product by graft copolymerization of a graft monomer selected from such unsaturated carboxylic acids or derivatives thereof onto the base polymer, a conventionally known method can be used. For example, when a 4-methyl-1-pentene polymer is used as the base polymer, a melt modification method in which the 4-methyl-1-pentene polymer is melted and a graft monomer is added to perform graft copolymerization, or a solvent is used. A solution modification method in which a graft monomer is dissolved and graft copolymerized can be used.
ベースポリマーに前記変性用モノマーを効率よくグラフトさせてグラフト変性ポリα−オレフィンを得るには、ラジカル開始剤の存在下に反応を行うことが好ましく、この場合グラフト化反応は通常６０〜３５０℃の温度で行われる。ラジカル開始剤の使用割合は、ベースポリマー１００重量部に対して通常０．００１〜２重量部の範囲である。ラジカル開始剤としては、ジクミルパーオキサイド、ジ−ｔｅｒｔ−ブチルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチルパーオキシ）ヘキシン−３，２，５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチルパーオキシ）ヘキサン、１，４−ビス（ｔｅｒｔ−ブチルパーオキシイソプロピル）ベンゼン等の有機パーオキサイドが好ましい。 In order to obtain a graft-modified poly α-olefin by efficiently grafting the modifying monomer onto the base polymer, it is preferable to carry out the reaction in the presence of a radical initiator. In this case, the grafting reaction is usually carried out at 60 to 350 ° C. Done at temperature. The use ratio of the radical initiator is usually in the range of 0.001 to 2 parts by weight with respect to 100 parts by weight of the base polymer. Examples of the radical initiator include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5. -Organic peroxides such as di (tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.
本発明で（II）の成分として用いられる変性ポリα−オレフィン系重合体は、その変性量が、グラフトモノマー重量として０．０１〜１０重量％、特に１〜５重量％の範囲で変性されることが好ましく、グラフト変性量が前記範囲の下限量より少ない場合、本発明の効果の一つでもある導体との接着性が低下するため好ましくない。逆に、グラフト量を上記上限量より高くしようとすると、グラフティング反応と共に、熱、或いはパーオキサイド等のラジカル開始剤の作用により、該ベースポリマーの主鎖形成骨格、例えば、４−メチル−１−ペンテン骨格等の切断、開裂反応が不可避的に生じ、グラフト変性４−メチル−１−ペンテン系重合体等のグラフト変性ポリα−オレフィンの分子量が極端に小さくなり、それを配合した樹脂組成物の強度的特性が低下するために好ましくない。 The modified poly α-olefin polymer used as the component (II) in the present invention is modified in the range of 0.01 to 10% by weight, particularly 1 to 5% by weight as the graft monomer weight. It is preferable that the amount of graft modification is less than the lower limit of the above range because the adhesion with a conductor, which is one of the effects of the present invention, is lowered. On the other hand, when the graft amount is to be made higher than the above upper limit amount, the main chain forming skeleton of the base polymer, for example, 4-methyl-1 is produced by the action of heat or a radical initiator such as peroxide together with the grafting reaction. -Cutting and cleavage reaction of pentene skeleton inevitably occurs, and the molecular weight of graft-modified poly α-olefin such as graft-modified 4-methyl-1-pentene polymer becomes extremely small, and a resin composition containing the same This is not preferable because the strength characteristics of the resin deteriorate.
本発明で（II）の成分として用いられる変性ポリα−オレフィン系重合体は、通常、その平均分子量の指標である還元粘度、即ちデカリン溶媒中、１３５℃での還元粘度が０．５〜１０ｄｌ／ｇ、特に、０．６〜５ｄｌ／ｇであることが好ましい。 The modified poly α-olefin polymer used as the component (II) in the present invention usually has a reduced viscosity which is an index of its average molecular weight, that is, a reduced viscosity at 135 ° C. of 0.5 to 10 dl in a decalin solvent. / G, particularly 0.6 to 5 dl / g.
本発明の（II）の成分は、（II）の成分全体に対するグラフトモノマー重量が０．０１重量％を切らない範囲で、変性ポリα−オレフィン系重合体に、炭素数２〜２０のα−オレフィンの単独重合体、それらα−オレフィンの共重合体、炭化水素系ゴム等を混合して組成物とすることができる。混合することのできる重合体としては、ポリエチレン、ポリプロピレン、エチレン・ブタジエンゴム、ポリブテン、ポリペンテン−１、エチレン・プロピレン共重合体、エチレン・ブテン共重合体、プロピレン・ブテン共重合体、ブテン・ペンテン−１共重合体、エチレン・プロピレン・ジエン共重合体、エチレン・プロピレン・ブテン共重合体、エチレン・プロピレン・ペンテン共重合体、ポリイソブチレン、ポリブタジエンゴム、スチレン・ブタジエンゴム、ブチルゴム、ポリイソプレンゴム等を挙げることができる。 The component (II) of the present invention is added to the modified poly α-olefin polymer in a range of not more than 0.01% by weight of the graft monomer based on the total component (II). Olefin homopolymers, copolymers of these α-olefins, hydrocarbon rubbers and the like can be mixed to form a composition. Polymers that can be mixed include polyethylene, polypropylene, ethylene / butadiene rubber, polybutene, polypentene-1, ethylene / propylene copolymer, ethylene / butene copolymer, propylene / butene copolymer, butene / pentene- 1 copolymer, ethylene / propylene / diene copolymer, ethylene / propylene / butene copolymer, ethylene / propylene / pentene copolymer, polyisobutylene, polybutadiene rubber, styrene / butadiene rubber, butyl rubber, polyisoprene rubber, etc. Can be mentioned.
本発明で（III）の成分として用いられる無機フィラーとしては、例として炭酸カルシウム、珪酸アルミニウム（クレー）、珪酸マグネシウム（タルク）、珪酸（シリカ）、硫酸アルミニウム、硫酸バリウム、水酸化アルミニウム、アルミナ、酸化アンチモン、チタン酸バリウム、硫酸カルシウム、シリコーンカーバイト、酸化チタン、石英、酸化ジルコニウム、窒化ボロン等などが挙げられる。これらの中ではシリカが好ましく用いられる。また、これらの無機フィラーを焼成処理したもの、シランカップリング剤などで表面処理したものを使用することができる。 Examples of the inorganic filler used as the component (III) in the present invention include calcium carbonate, aluminum silicate (clay), magnesium silicate (talc), silicic acid (silica), aluminum sulfate, barium sulfate, aluminum hydroxide, alumina, Examples include antimony oxide, barium titanate, calcium sulfate, silicone carbide, titanium oxide, quartz, zirconium oxide, boron nitride, and the like. Of these, silica is preferably used. In addition, those obtained by firing these inorganic fillers or those surface-treated with a silane coupling agent can be used.
無機フィラーの平均粒径は高周波回路用積層板として用いた場合、悪影響を与えなければ特に限定されるわけではなく、０．１〜５０μｍが好ましく、より好ましくは０．５〜４０μｍ、さらに好ましくは１．０〜３０μｍである。無機フィラーの平均粒径が上記範囲内の方が、（Ｉ）、（II）成分との混合性が良好であり、また本発明の効果の一つでもある耐熱性が充分得られる。無機フィラーの形状としては、球状フィラーと破砕状、フレーク状、棒状、板状、鱗片状等の非球状フィラーのいずれでも使用することができるが、樹脂への充填性の点で球状の方が好ましい。 The average particle size of the inorganic filler is not particularly limited as long as it is not adversely affected when used as a laminate for a high frequency circuit, preferably 0.1 to 50 μm, more preferably 0.5 to 40 μm, and still more preferably. 1.0 to 30 μm. When the average particle size of the inorganic filler is within the above range, the mixing property with the components (I) and (II) is good and the heat resistance which is one of the effects of the present invention is sufficiently obtained. As the shape of the inorganic filler, any of spherical fillers and non-spherical fillers such as crushed, flakes, rods, plates, scales, etc. can be used. preferable.
本発明の樹脂組成物において、（Ｉ）、（II）、（III）の成分の配合量は、（Ｉ）、（II）、（III）成分の合計量１００重量部とした場合、（Ｉ）が３〜７２重量部、（II）が０．５〜５０重量部、（III）が２５〜９０重量部である。好ましくは（Ｉ）が６〜６２重量部、（II）が１．０〜４４重量部、（III）が３５〜８０重量部、更に好ましくは、（Ｉ）が１０〜５３重量部、（II）が１．５〜３７重量部、（III）が４５〜７０重量部である。この範囲において、それぞれの成分の配合量を調節することにより、低誘電率、低誘電正接で、耐熱性および導体との接着性に優れた性質の樹脂組成物とすることができる。（Ｉ）の組成が下限を下回れば誘電特性が満足できなくなり（誘電率、誘電正接が高くなり）好ましくない。また、上限を上回れば耐熱性が満足できなくなり好ましくない。（II）の組成が下限を下回れば導体との接着性が満足できなくなり好ましくない。また、上限を上回れば耐熱性が満足できなくなり好ましくない。（III）の組成が下限を下回れば耐熱性が満足できなくなり好ましくない。また、上限を上回れば成形加工性が満足できなくなり好ましくない。 In the resin composition of the present invention, when the blending amounts of the components (I), (II) and (III) are 100 parts by weight of the total amount of the components (I), (II) and (III), (I ) Is 3 to 72 parts by weight, (II) is 0.5 to 50 parts by weight, and (III) is 25 to 90 parts by weight. Preferably (I) is 6 to 62 parts by weight, (II) is 1.0 to 44 parts by weight, (III) is 35 to 80 parts by weight, and more preferably (I) is 10 to 53 parts by weight, (II ) Is 1.5 to 37 parts by weight, and (III) is 45 to 70 parts by weight. By adjusting the blending amount of each component within this range, a resin composition having a low dielectric constant, a low dielectric loss tangent, excellent heat resistance and adhesiveness to a conductor can be obtained. If the composition of (I) is below the lower limit, the dielectric properties cannot be satisfied (dielectric constant and dielectric loss tangent increase), which is not preferable. Further, if the upper limit is exceeded, the heat resistance cannot be satisfied, which is not preferable. If the composition of (II) is below the lower limit, the adhesion with the conductor cannot be satisfied, which is not preferable. Further, if the upper limit is exceeded, the heat resistance cannot be satisfied, which is not preferable. If the composition of (III) is below the lower limit, the heat resistance cannot be satisfied, which is not preferable. On the other hand, if the upper limit is exceeded, molding processability cannot be satisfied, which is not preferable.
本発明において用いられる樹脂組成物を調製する方法は、通常、樹脂組成物の各成分を、ロールミル、バンバリーミキサー、押出機などを使って溶融混錬する方法が一般的であるが、成分を均一に分散する方法であれば特に限定されない。すなわち、最終的に得られる樹脂組成物において、各成分の配合量が前記の範囲内であって、さらに実用上問題のない混合状態であれば、樹脂組成物を形成する各成分の配合方法や、工程はいかなるものであってもよい。たとえば、樹脂組成物の各成分を所望の配合比となるようにドライブレンドした後、樹脂の融点以上に設定した二軸押出機に導入して溶融混練して各成分を均一に分散させ、ついで冷却・ペレット化することで目的の樹脂組成物を得る方法を挙げることができる。 The method of preparing the resin composition used in the present invention is generally a method of melt kneading each component of the resin composition using a roll mill, a Banbury mixer, an extruder, etc. If it is the method of disperse | distributing to, it will not specifically limit. That is, in the finally obtained resin composition, if the blending amount of each component is within the above range and is in a mixed state with no practical problem, the blending method of each component forming the resin composition or Any process may be used. For example, after dry blending each component of the resin composition so as to have a desired blending ratio, it is introduced into a twin screw extruder set to a temperature equal to or higher than the melting point of the resin and melt kneaded to uniformly disperse each component. The method of obtaining the target resin composition by cooling and pelletizing can be mentioned.
本発明の樹脂組成物には、所望に応じて難燃剤、熱安定剤、酸化安定剤、耐候安定剤、帯電防止剤、滑剤、可塑剤等の各種添加剤を、本発明の効果を損なわない範囲で配合することができる。 In the resin composition of the present invention, various additives such as a flame retardant, a heat stabilizer, an oxidation stabilizer, a weathering stabilizer, an antistatic agent, a lubricant, and a plasticizer are added to the resin composition of the present invention as desired. It can mix | blend in the range.
本発明の樹脂組成物をシートまたはフィルム形状に成形する方法としては、押し出し成形、射出成形、プレス、キャスティングなどの各種公知の方法が適用可能である。 As a method for molding the resin composition of the present invention into a sheet or film shape, various known methods such as extrusion molding, injection molding, pressing, and casting can be applied.
また、本発明の樹脂組成物を用いて本発明の高周波回路用積層板を形成する方法に特に制限はない。例えば、樹脂組成物からシートを形成するか、または樹脂組成物のシートをガラスクロス等の基材を中心に張り合わせてコア材を形成するなどし、導体層となる金属箔を張り合わせて得ることができる。必要に応じてそれらシートやコア材などを金属箔とともに多重に積層して得ても良い。また、他の公知のコア材、フィルム、プリプレグ、金属箔などとともに常法にしたがって積層一体化して得ても良い。例えば、より具体的には、この樹脂組成物のシート１枚または複数枚を用い、さらに電解銅箔などの金属箔を重ねた構成とし、成形圧力１〜１５ＭＰａ／ｃｍ２で一定時間過熱圧締することにより、金属箔との接着性に優れ、かつ耐熱性、誘電特性の優れた高周波回路用積層板を製造することができる。この加熱圧締の温度は、金属箔とシートの組み合わせなどによるが、シートの熱融着性を利用できるので、積層圧締温度はシートのガラス転移温度以上で、１３０〜３００℃くらいの範囲にするのが好ましい。また圧締はシート同士、シートと金属箔などの接合および積層板の厚み調整のために行うので、圧締条件は必要に応じて選択することができる。 Moreover, there is no restriction | limiting in particular in the method of forming the laminated board for high frequency circuits of this invention using the resin composition of this invention. For example, it can be obtained by forming a sheet from a resin composition, or by laminating a sheet of the resin composition around a base material such as a glass cloth to form a core material, and laminating a metal foil as a conductor layer it can. If necessary, these sheets and core materials may be obtained by laminating multiple layers together with metal foil. Further, it may be obtained by laminating and integrating with other known core materials, films, prepregs, metal foils and the like according to a conventional method. For example, more specifically, one or a plurality of sheets of the resin composition are used, and a metal foil such as an electrolytic copper foil is further stacked, and overheating pressing is performed at a molding pressure of 1 to 15 MPa / cm 2 for a certain time. By doing so, it is possible to produce a laminate for a high-frequency circuit that is excellent in adhesion to a metal foil, and has excellent heat resistance and dielectric properties. The heating and pressing temperature depends on the combination of the metal foil and the sheet. However, since the heat fusion property of the sheet can be used, the lamination pressing temperature is higher than the glass transition temperature of the sheet and is in the range of about 130 to 300 ° C. It is preferable to do this. In addition, the pressing is performed for joining the sheets, joining the sheet and the metal foil, and adjusting the thickness of the laminated plate. Therefore, the pressing conditions can be selected as necessary.
導体金属としては、特に限定はなく、例えば銅、アルミニウム、ニッケル、金、銀、ステンレス等の金属を用いることができる。導体層の形成方法としては、該金属類を箔等にして熱融着させる方法以外にも、接着剤を用いて張り合わせる方法、もしくはスパッタ、蒸着、めっき等の方法で積層して形成する方法で作成することができる。本発明の高周波回路用積層板を形成する際の樹脂組成物層と導体層の接着に用いることのできる接着剤としては、特に限定されずエポキシ、ポリイミド等の公知の耐熱性接着剤を使用することができるが、絶縁層の誘電特性に影響を及ぼさない為に、本発明の樹脂組成物の層厚／接着剤の層厚の比が２以上となることが好ましく、３以上になるように形成するのがより好ましい。回路の形成は種々の公知のリソグラフィー法、例えばエッチング法などで行うことができる。積層板の態様としては、片面板、両面板のいずれでも良く、積層数にも制限はないが、２層〜３０層程度に積層するのが好ましい。 There is no limitation in particular as a conductor metal, For example, metals, such as copper, aluminum, nickel, gold | metal | money, silver, stainless steel, can be used. As a method for forming the conductor layer, in addition to the method of heat-sealing the metals into a foil or the like, a method of laminating using an adhesive or a method of forming by laminating by a method such as sputtering, vapor deposition or plating Can be created. The adhesive that can be used for bonding the resin composition layer and the conductor layer when forming the laminate for a high-frequency circuit of the present invention is not particularly limited, and a known heat-resistant adhesive such as epoxy or polyimide is used. However, in order not to affect the dielectric properties of the insulating layer, the ratio of the layer thickness of the resin composition of the present invention / the layer thickness of the adhesive is preferably 2 or more, and is preferably 3 or more. More preferably, it is formed. The circuit can be formed by various known lithography methods such as an etching method. As a mode of a laminated board, any of a single-sided board and a double-sided board may be sufficient, and although there is no restriction | limiting in the number of lamination | stacking, it is preferable to laminate | stack to about 2-30 layers.
以下、本発明を実施例によりさらに詳細に説明するが、本発明はこれにより何等制限されるものではない。実施例中の各評価方法を以下に示す。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited at all by this. Each evaluation method in the examples is shown below.
誘電率および誘電正接：空洞共振器法により、２５℃で１２ＧＨｚにおける誘電率および誘電正接を測定した。
銅引き剥がし強度：ＪＩＳ Ｃ６４８１の方法に準拠して測定した。
ガラス転移温度（Ｔｇ）：ＤＳＣ（示差走査型熱量計、島津製作所株式会社製・ＤＳＣ−６０）により、２５℃から４００℃まで昇温速度１０℃／分で測定した。
５％重量減少温度（Ｔｄ５％）：ＴＧＡ（熱重量測定装置、島津製作所株式会社製・ＴＧＡ−５０）により空気中にて、２５℃から８００℃まで昇温速度１０℃／分で測定した。
ＭＦＲ：ＡＳＴＭ Ｄ１２３８に準拠して荷重：５Ｋｇ、温度：２６０℃の条件で測定した。
還元粘度（ηinh）：サンプルの樹脂を所定の濃度で１３５℃のデカリンに溶解し、ウベローデ型粘度計により測定した。なお、コントロールユニットとして、ラウダ製ＰＶＳ１を使用した。
Dielectric constant and dielectric loss tangent: The dielectric constant and dielectric loss tangent at 12 GHz were measured at 25 ° C. by the cavity resonator method.
Copper peel strength: Measured according to the method of JIS C6481.
Glass transition temperature (Tg): Measured by DSC (Differential Scanning Calorimeter, Shimadzu Corporation DSC-60) from 25 ° C. to 400 ° C. at a heating rate of 10 ° C./min.
5% weight loss temperature (Td 5%): Measured from 25 ° C. to 800 ° C. at a rate of temperature increase of 10 ° C./min in air using TGA (Thermogravimetric apparatus, Shimadzu Corporation TGA-50).
MFR: Measured according to ASTM D1238 under conditions of load: 5 kg and temperature: 260 ° C.
Reduced viscosity (ηinh): The sample resin was dissolved in decalin at 135 ° C. at a predetermined concentration, and measured with an Ubbelohde viscometer. Note that Lauda PVS1 was used as the control unit.
元素分析：ＣＨＮ元素分析装置（ＰＥ２４００−ＩＩ型）にて定量した。
ＩＲスペクトル：測定するポリマーをＫＢｒ錠剤法にて試料化し、フーリエ変換型赤外分光光度計（デジラボジャパン製・ＦＴＳ６０００）を用いて、分解能４ｃｍ−１、積算回数１２８回でスペクトル測定を行った。
リフロー耐熱性：ＪＩＳ Ｃ６４８１の方法に準じて、一部銅箔除去面のある銅張積層板試験片を作成し、これを１０５℃、７５分間の前処理の後、沸騰水中に１時間浸して調湿した。赤外線及び熱風併用型リフロー半田装置（日本アントム工業（株）製ＳＯＬＳＹＳ−２００１Ｒ）を用いて、昇温６０秒→１７５℃保持９０秒→昇温５０秒→２６０℃保持３０秒→冷却の温度プロファイルでリフロー工程を行い、試験片外観形状の変化の有無を評価した。
Elemental analysis: quantified with CHN elemental analyzer (PE2400-II type).
IR spectrum: The polymer to be measured was sampled by the KBr tablet method, and spectrum measurement was performed using a Fourier transform infrared spectrophotometer (manufactured by Digilab Japan, FTS6000) at a resolution of 4 cm −1 and 128 times of integration. .
Reflow heat resistance: According to the method of JIS C6481, a copper clad laminate test piece with a part of the copper foil removed is prepared, and after pretreatment at 105 ° C. for 75 minutes, it is immersed in boiling water for 1 hour. Humidified. Using an infrared ray and hot air combined reflow soldering device (SOLSYS-2001R manufactured by Nippon Antom Industry Co., Ltd.), temperature rise 60 seconds → 175 ° C. hold 90 seconds → heat rise 50 seconds → 260 ° C. hold 30 seconds → cooling temperature profile The reflow process was performed, and the presence or absence of a change in the test piece appearance was evaluated.
尚、本実施例において、４−メチル−１−ペンテン共重合体は三井化学（株）社製のＴＰＸ〔登録商標〕（ＲＴ１８、ＭＦＲ＝１７０ｇ／１０分）を用いた。無機フィラーは、龍森（株）社製のシリカ（商品名：ＹＸＫ−３５Ｒ、平均粒径２６μｍ）を用いた。また、その他の原材料は、下記合成例のとおりに合成して用いた。 In this example, TPX [registered trademark] (RT18, MFR = 170 g / 10 min) manufactured by Mitsui Chemicals, Inc. was used as the 4-methyl-1-pentene copolymer. Silica (trade name: YXK-35R, average particle size 26 μm) manufactured by Tatsumori Co., Ltd. was used as the inorganic filler. Other raw materials were synthesized and used as in the following synthesis examples.
合成例１（環状オレフィン共重合体の合成−１）
攪拌翼を備えた２Ｌ重合器を用いて、連続的にエチレンと１，４，５，８−ジメタノ−１，２，３，４，４ａ，５，８，８ａ−オクタヒドロナフタレン（以下ＤＭＯＮと省略）の共重合反応を行った。すなわち、重合器上部からＤＭＯＮシクロヘキサン溶液を、重合器内でのＤＭＯＮ濃度が６０ｇ／ｌとなるように毎時０．４ｌ、触媒としてＶＯ（ＯＣ２Ｈ５）Ｃｌ２のシクロヘキサン溶液を重合器内でのバナジウム濃度が０．７mmol／ｌとなるように毎時０．７ｌ、エチルアルミニウムセスキクロリド（Ａｌ（Ｃ２Ｈ５）１５Ｃｌ１５）のシクロヘキサン溶液を重合器内でのアルミニウム濃度が５．６mol／ｌとなるように毎時０．４ｌおよびシクロヘキサンを毎時０．５ｌの速度でそれぞれ重合器内に連続的に供給し、一方、重合器下部から重合器内の重合液が常に１ｌになるように連続的に抜き出した。また重合器上部からエチレンを毎時８０ｌ、窒素を毎時８０ｌ、水素を毎時０．２ｌの速度で供給した。共重合反応は、重合器上部に取り付けられたジャケットに冷媒を循環させることにより１０℃で行った。上記条件で共重合反応を行うと、エチレン・DMONランダム共重合体を含む重合反応混合物が得られた。重合器下部から抜き出した重合液に、シクロヘキサン／イソプロピルアルコール（１／１）混合液を添加して重合反応を停止させた。その後、水１ｌに対し濃塩酸５ｍｌを添加した水溶液と重合溶液とを１対１の割合でホモミキサーを用い強攪拌下で接触させ、触媒残渣を水層へ移行させた。上記混合液を静置し、水層を除去後さらに蒸留水で２回水洗を行い、重合液を精製分離した。
Synthesis Example 1 (Synthesis of cyclic olefin copolymer-1)
Using a 2 L polymerization vessel equipped with a stirring blade, ethylene and 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene (hereinafter referred to as DMON) (Omitted) was carried out. That is, a DMON cyclohexane solution from the upper part of the polymerization vessel was added in an amount of 0.4 l per hour so that the DMON concentration in the polymerization vessel was 60 g / l, and a cyclohexane solution of VO (OC 2 H 5 ) Cl 2 as a catalyst in the polymerization vessel. The cyclohexane solution of ethylaluminum sesquichloride (Al (C 2 H 5 ) 15 Cl 15 ) was adjusted to 0.7 mol / l so that the vanadium concentration in the polymer was 5.6 mol / l. to 0.4 l / h and cyclohexane continuously at a rate of 0.5 l / h, respectively, while continuously feeding the polymerization liquid in the polymerizer from the bottom of the polymerizer to 1 l. Extracted. Further, ethylene was supplied from the top of the polymerization vessel at a rate of 80 l / h, nitrogen at 80 l / h, and hydrogen at a rate of 0.2 l / h. The copolymerization reaction was carried out at 10 ° C. by circulating a refrigerant through a jacket attached to the upper part of the polymerization vessel. When the copolymerization reaction was carried out under the above conditions, a polymerization reaction mixture containing an ethylene / DMON random copolymer was obtained. A cyclohexane / isopropyl alcohol (1/1) mixed solution was added to the polymerization solution extracted from the lower part of the polymerization vessel to stop the polymerization reaction. Thereafter, the aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 l of water and the polymerization solution were brought into contact with each other at a ratio of 1: 1 with vigorous stirring using a homomixer, and the catalyst residue was transferred to the aqueous layer. The mixture was allowed to stand, and after removing the aqueous layer, the mixture was further washed twice with distilled water to purify and separate the polymerization solution.
得られた重合液を３倍量のアセトンと強攪拌下で接触させ、固体部を濾過により採取し、アセトンで十分洗浄した。以上の方法により、環状オレフィン共重合体のポリマー粉を得た（以下ＣＯＣと省略）。このポリマーを１３５℃のデカリン中で測定した還元粘度は０．８５ｄｌ／ｇであった。13Ｃ−ＮＭＲ分析による共重合体のエチレン組成は６１モル％、ガラス転移温度：１４５℃。 The obtained polymerization solution was brought into contact with 3 times the amount of acetone under strong stirring, and the solid portion was collected by filtration and sufficiently washed with acetone. By the above method, a polymer powder of a cyclic olefin copolymer was obtained (hereinafter abbreviated as COC). The reduced viscosity of this polymer measured in decalin at 135 ° C. was 0.85 dl / g. The ethylene composition of the copolymer as determined by 13 C-NMR analysis was 61 mol%, and the glass transition temperature was 145 ° C.
合成例２（無水マレイン酸グラフト変性４−メチル−１−ペンテン共重合体の合成）
４−メチル−１−ペンテン共重合体（ＲＴ１８）１００重量部を使用し、トルエン溶媒中、ジクミルパーオキサイド触媒の存在下、１４５℃で無水マレイン酸５重量部をグラフト反応させた。得られた反応物に大量のアセトンを加え、グラフト変性ポリマーを析出させ、これを濾別し、アセトンで十分洗浄して無水マレイン酸グラフト変性４−メチル−１−ペンテン系重合体を得た（以下Ｍ−ＰＭＰと省略）。この重合体の、１３５℃、デカリン中に於ける還元粘度は０．９２ｄｌ／ｇであった。
Synthesis Example 2 (Synthesis of maleic anhydride graft-modified 4-methyl-1-pentene copolymer)
Using 100 parts by weight of 4-methyl-1-pentene copolymer (RT18), 5 parts by weight of maleic anhydride was grafted in a toluene solvent at 145 ° C. in the presence of a dicumyl peroxide catalyst. A large amount of acetone was added to the resulting reaction product to precipitate a graft-modified polymer, which was separated by filtration and sufficiently washed with acetone to obtain a maleic anhydride graft-modified 4-methyl-1-pentene polymer ( Hereinafter abbreviated as M-PMP). The reduced viscosity of this polymer in decalin at 135 ° C. was 0.92 dl / g.
合成例３（無水マレイン酸グラフト変性ポリエチレン重合体組成物の合成）
密度＝０．９２１ｇ／ｃｍ3、ＡＳＴＭ Ｄ１２３８によるＭＦＲ（１９０℃：２１６０ｇ）＝２．０ｇ／１０分、１−ブテン含有量が４モル％のポリエチレン樹脂（以下ＰＥ−１と省略）１００重量部に、無水マレイン酸０．８重量部と過酸化物［パーヘキシン２５Ｂ、日本油脂（株）製、登録商標］０．０７重量部とを混合し、得られた混合物を２３０℃に設定した１軸押出機で溶融グラフト変性することによって変性ポリエチレン樹脂を得た。この変性ポリエチレン樹脂の１３５℃デカリン溶液中で測定した還元粘度は１．８６ｄｌ／ｇであった。この変性ポリエチレン樹脂２０重量部に未変性のポリエチレン樹脂（ＰＥ−１）６５重量部とエチレンプロピレンゴム（密度＝０．８６５ｇ／ｃｍ3、ＡＳＴＭ Ｄ１２３８によるＭＦＲ〔１９０℃：２１６０ｇ〕＝０．５ｇ／１０分、エチレン含有量が８０モル％）を１５重量部、フェノール系安定剤であるイルガノックス１０１０（チバガイギー社製、登録商標）０．１重量部、燐系安定剤であるイルガフォス１６８（チバガイギー社製、登録商標）０．１重量部とをヘンシェルミキサーにて均一に混合し、この混合物を２３０℃に設定した１軸押出機で溶融混合して無水マレイン酸グラフト変性ポリエチレン重合体組成物（以下Ｍ−ＰＥと省略）を得た。
Synthesis Example 3 (Synthesis of maleic anhydride graft-modified polyethylene polymer composition)
Density = 0.921 g / cm 3 , MFR (190 ° C .: 2160 g) according to ASTM D1238 = 2.0 g / 10 min, 1-butene content 4 mol% polyethylene resin (hereinafter abbreviated as PE-1) 100 parts by weight A mixture of 0.8 parts by weight of maleic anhydride and 0.07 parts by weight of a peroxide [Perhexine 25B, registered trademark of NOF Corporation], and the resulting mixture was set to 230 ° C. A modified polyethylene resin was obtained by melt graft modification with an extruder. The reduced viscosity of the modified polyethylene resin measured in a 135 ° C. decalin solution was 1.86 dl / g. 20 parts by weight of this modified polyethylene resin, 65 parts by weight of unmodified polyethylene resin (PE-1) and ethylene propylene rubber (density = 0.865 g / cm 3 , MFR according to ASTM D1238 [190 ° C .: 2160 g] = 0.5 g / 10 minutes, ethylene content 80 mol%) 15 parts by weight, phenolic stabilizer Irganox 1010 (Ciba Geigy, registered trademark) 0.1 parts by weight, phosphorus stabilizer Irgaphos 168 (Ciba Geigy) And 0.1 parts by weight of manufactured and registered trademark are uniformly mixed with a Henschel mixer, and this mixture is melt-mixed with a single screw extruder set at 230 ° C. to obtain a maleic anhydride graft-modified polyethylene polymer composition (hereinafter referred to as “polyethylene polymer composition”). Abbreviated M-PE).
実施例１
４−メチル−１−ペンテン共重合体４８重量部、合成例２で得られた無水マレイン酸グラフト変性４−メチル−１−ペンテン共重合体２重量部、シリカ５０重量部を、ヘンシェルミキサーにて３分間混合した後、二軸押出機を用いて３００℃で溶融混練し、ペレット化した。上記ペレットを用い、３００℃、１０MPa/cm２の圧力で７分間プレスし、厚さ約０．５ｍｍのシートを得た。このシートの誘電率および誘電正接の測定結果を表１に示す。ついで、このシートの両面に厚さ３５μｍの電解銅箔（三井金属（株）社製ＳＱ−ＶＬＰ）を重ね、３００℃、１０MPa/cm２の圧力で３０分間プレスすることにより熱融着し、両面銅張りシートを得た。この両面銅張りシートの銅引き剥がし強度、リフロー耐熱性の評価結果を表１に示す。
Example 1
In a Henschel mixer, 48 parts by weight of 4-methyl-1-pentene copolymer, 2 parts by weight of maleic anhydride graft-modified 4-methyl-1-pentene copolymer obtained in Synthesis Example 2 and 50 parts by weight of silica were mixed. After mixing for 3 minutes, it was melt-kneaded at 300 ° C. using a twin-screw extruder and pelletized. Using the above pellets, pressing was performed at 300 ° C. and a pressure of 10 MPa / cm 2 for 7 minutes to obtain a sheet having a thickness of about 0.5 mm. Table 1 shows the measurement results of dielectric constant and dielectric loss tangent of this sheet. Next, an electrolytic copper foil (SQ-VLP manufactured by Mitsui Kinzoku Co., Ltd.) having a thickness of 35 μm is stacked on both sides of the sheet, and heat-sealed by pressing at 300 ° C. and a pressure of 10 MPa / cm 2 for 30 minutes. A double-sided copper-clad sheet was obtained. Table 1 shows the evaluation results of the copper peeling strength and reflow heat resistance of this double-sided copper-clad sheet.
実施例２
実施例１と同様の操作において、配合量を４−メチル−１−ペンテン共重合体９重量部、合成例２で得られた無水マレイン酸グラフト変性４−メチル−１−ペンテン共重合体１重量部、シリカ９０重量部として、樹脂組成物のペレット化を得た。これを用い、実施例１と同様にして、シートおよび両面銅張りシートを作成し、誘電率、誘電正接、銅引き剥がし強度、リフロー耐熱性の評価を行った。評価結果を表１に示す。
Example 2
In the same operation as in Example 1, the compounding amount was 9 parts by weight of 4-methyl-1-pentene copolymer, and 1 weight of maleic anhydride graft-modified 4-methyl-1-pentene copolymer obtained in Synthesis Example 2. Parts of the resin composition were obtained as 90 parts by weight of silica. Using this, a sheet and a double-sided copper-clad sheet were prepared in the same manner as in Example 1, and dielectric constant, dielectric loss tangent, copper peel strength, and reflow heat resistance were evaluated. The evaluation results are shown in Table 1.
比較例１〜２
実施例１と同様の操作において、配合量を表１に示すとおりに変更して樹脂組成物のペレット化を得た。これを用い、実施例１と同様にして、シートおよび両面銅張りシートを作成し、誘電率、誘電正接、銅引き剥がし強度、リフロー耐熱性の評価を行った。評価結果を表１に示す。
Comparative Examples 1-2
In the same operation as in Example 1, the compounding amount was changed as shown in Table 1 to obtain pelletization of the resin composition. Using this, a sheet and a double-sided copper-clad sheet were prepared in the same manner as in Example 1, and dielectric constant, dielectric loss tangent, copper peel strength, and reflow heat resistance were evaluated. The evaluation results are shown in Table 1.
実施例３〜４
合成例１で得られた環状オレフィン共重合体、合成例３で得られた無水マレイン酸グラフト変性ポリエチレン重合体、およびシリカを表１に示す配合量で用いて、実施例１と同様の操作で樹脂組成物のペレットを得た。これを用い、実施例１と同様にして、シートおよび両面銅張りシートの作成を行い、誘電率、誘電正接、銅引き剥がし強度、リフロー耐熱性の評価を行った。評価結果を表１に示す。
Examples 3-4
Using the cyclic olefin copolymer obtained in Synthesis Example 1, the maleic anhydride graft-modified polyethylene polymer obtained in Synthesis Example 3, and silica in the amounts shown in Table 1, the same operation as in Example 1 was performed. A pellet of the resin composition was obtained. Using this, a sheet and a double-sided copper-clad sheet were prepared in the same manner as in Example 1, and the dielectric constant, dielectric loss tangent, copper peel strength, and reflow heat resistance were evaluated. The evaluation results are shown in Table 1.
比較例３〜４
実施例３と同様の操作において、配合量を表１に示すとおりに変更して樹脂組成物のペレットを得た。これを用い、実施例１と同様にして、シートおよび両面銅張りシートを作成し、誘電率、誘電正接、銅引き剥がし強度、リフロー耐熱性の評価を行った。評価結果を表１に示す。
Comparative Examples 3-4
In the same operation as in Example 3, the blending amount was changed as shown in Table 1 to obtain pellets of the resin composition. Using this, a sheet and a double-sided copper-clad sheet were prepared in the same manner as in Example 1, and dielectric constant, dielectric loss tangent, copper peel strength, and reflow heat resistance were evaluated. The evaluation results are shown in Table 1.
本発明の樹脂組成物は、高周波特性の指標である誘電率・誘電正接に優れ、高耐熱性および導体との高接着性という特徴を併せ持つため、特に高周波信号伝送に対応する積層板として極めて有用である。 The resin composition of the present invention is excellent in dielectric constant and dielectric loss tangent, which are indicators of high-frequency characteristics, and also has the characteristics of high heat resistance and high adhesion to conductors, so it is extremely useful especially as a laminate for high-frequency signal transmission. It is.
Claims (2)
（II）不飽和カルボン酸および／またはその誘導体によりグラフト変性された部分を、０．０１〜１０重量％有する変性ポリα−オレフィン系重合体０．５〜５０重量部
（III）無機フィラー２５〜９０重量部
からなる、但し（Ｉ）、（II）、（III）成分の合計が１００重量部であることを特徴とする樹脂組成物。 (I) 4-72 parts by weight of 4-methyl-1-pentene polymer,
(II) 0.5 to 50 parts by weight of a modified poly α-olefin polymer having 0.01 to 10% by weight of a portion graft-modified with an unsaturated carboxylic acid and / or derivative thereof (III) Inorganic filler 25 to 25 A resin composition comprising 90 parts by weight, wherein the total of components (I), (II) and (III) is 100 parts by weight.
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