JP2023032942A - Liquid crystalline resin composition - Google Patents
Liquid crystalline resin composition Download PDFInfo
- Publication number
- JP2023032942A JP2023032942A JP2021139326A JP2021139326A JP2023032942A JP 2023032942 A JP2023032942 A JP 2023032942A JP 2021139326 A JP2021139326 A JP 2021139326A JP 2021139326 A JP2021139326 A JP 2021139326A JP 2023032942 A JP2023032942 A JP 2023032942A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystalline
- crystalline resin
- cyclic olefin
- resin composition
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000007788 liquid Substances 0.000 title claims abstract description 111
- 229920006038 crystalline resin Polymers 0.000 title claims abstract description 105
- 239000011342 resin composition Substances 0.000 title claims abstract description 66
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 48
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 46
- 239000000945 filler Substances 0.000 claims abstract description 38
- 125000003118 aryl group Chemical group 0.000 claims abstract description 17
- 238000002844 melting Methods 0.000 claims abstract description 14
- 230000008018 melting Effects 0.000 claims abstract description 14
- 229920000728 polyester Polymers 0.000 claims abstract description 12
- 239000011521 glass Substances 0.000 claims abstract description 10
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims abstract description 10
- 230000009477 glass transition Effects 0.000 claims abstract description 9
- -1 cyclic olefin Chemical class 0.000 claims description 51
- 239000000178 monomer Substances 0.000 claims description 34
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- 239000011256 inorganic filler Substances 0.000 claims description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 6
- 239000004711 α-olefin Substances 0.000 claims description 6
- 239000000470 constituent Substances 0.000 abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 21
- 239000012765 fibrous filler Substances 0.000 description 19
- 239000000835 fiber Substances 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 18
- 150000001336 alkenes Chemical class 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 14
- 239000000155 melt Substances 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000005977 Ethylene Substances 0.000 description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 125000002950 monocyclic group Chemical group 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 230000005484 gravity Effects 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 7
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000002685 polymerization catalyst Substances 0.000 description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 6
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 5
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- 238000007142 ring opening reaction Methods 0.000 description 5
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- 239000010445 mica Substances 0.000 description 4
- 229910052618 mica group Inorganic materials 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- QHORRKSZGBYGPH-UHFFFAOYSA-L benzylidene(dichloro)ruthenium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1 QHORRKSZGBYGPH-UHFFFAOYSA-L 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- VWMKUZYJGUVNJX-UHFFFAOYSA-L C(C1=CC=CC=C1)=[Ru](Cl)Cl.C1(=C(C(=CC(=C1)C)C)N1C(N(CC1)C1=C(C=C(C=C1C)C)C)=C1C(CCCC1)P(C1CCCCC1)C1CCCCC1)C Chemical compound C(C1=CC=CC=C1)=[Ru](Cl)Cl.C1(=C(C(=CC(=C1)C)C)N1C(N(CC1)C1=C(C=C(C=C1C)C)C)=C1C(CCCC1)P(C1CCCCC1)C1CCCCC1)C VWMKUZYJGUVNJX-UHFFFAOYSA-L 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 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
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- LQDSIZNFFVRKJA-XORISBCWSA-N (1z,3z)-1-methylcycloocta-1,3-diene Chemical compound C\C1=C\C=C/CCCC1 LQDSIZNFFVRKJA-XORISBCWSA-N 0.000 description 1
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- QPFMBZIOSGYJDE-QDNHWIQGSA-N 1,1,2,2-tetrachlorethane-d2 Chemical compound [2H]C(Cl)(Cl)C([2H])(Cl)Cl QPFMBZIOSGYJDE-QDNHWIQGSA-N 0.000 description 1
- LSMWOQFDLBIYPM-UHFFFAOYSA-N 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-2h-imidazol-1-ium-2-ide Chemical group CC1=CC(C)=CC(C)=C1N1[C-]=[N+](C=2C(=CC(C)=CC=2C)C)CC1 LSMWOQFDLBIYPM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- QMFJIJFIHIDENY-UHFFFAOYSA-N 1-Methyl-1,3-cyclohexadiene Chemical compound CC1=CC=CCC1 QMFJIJFIHIDENY-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- ATQUFXWBVZUTKO-UHFFFAOYSA-N 1-methylcyclopentene Chemical compound CC1=CCCC1 ATQUFXWBVZUTKO-UHFFFAOYSA-N 0.000 description 1
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 1
- OLGHJTHQWQKJQQ-UHFFFAOYSA-N 3-ethylhex-1-ene Chemical compound CCCC(CC)C=C OLGHJTHQWQKJQQ-UHFFFAOYSA-N 0.000 description 1
- YPVPQMCSLFDIKA-UHFFFAOYSA-N 3-ethylpent-1-ene Chemical compound CCC(CC)C=C YPVPQMCSLFDIKA-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
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- SUJVAMIXNUAJEY-UHFFFAOYSA-N 4,4-dimethylhex-1-ene Chemical compound CCC(C)(C)CC=C SUJVAMIXNUAJEY-UHFFFAOYSA-N 0.000 description 1
- KLCNJIQZXOQYTE-UHFFFAOYSA-N 4,4-dimethylpent-1-ene Chemical compound CC(C)(C)CC=C KLCNJIQZXOQYTE-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- OPMUAJRVOWSBTP-UHFFFAOYSA-N 4-ethyl-1-hexene Chemical compound CCC(CC)CC=C OPMUAJRVOWSBTP-UHFFFAOYSA-N 0.000 description 1
- SUWJESCICIOQHO-UHFFFAOYSA-N 4-methylhex-1-ene Chemical compound CCC(C)CC=C SUWJESCICIOQHO-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
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
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- 229910001369 Brass Inorganic materials 0.000 description 1
- KQKSBIZXVRSFIT-UHFFFAOYSA-L C1=CC2=CC=CC=C2C1[Ti](Cl)(Cl)(=CC)C1C2=CC=CC=C2C=C1 Chemical compound C1=CC2=CC=CC=C2C1[Ti](Cl)(Cl)(=CC)C1C2=CC=CC=C2C=C1 KQKSBIZXVRSFIT-UHFFFAOYSA-L 0.000 description 1
- LOXPHMRBPPCZDT-UHFFFAOYSA-L C1=CC2=CC=CC=C2C1[Zr](Cl)(Cl)(=CC)C1C2=CC=CC=C2C=C1 Chemical compound C1=CC2=CC=CC=C2C1[Zr](Cl)(Cl)(=CC)C1C2=CC=CC=C2C=C1 LOXPHMRBPPCZDT-UHFFFAOYSA-L 0.000 description 1
- YXKIUCUZHJZDFB-UHFFFAOYSA-L CC(C)C1=CC(C=C1)[Zr](Cl)(Cl)(C1C=CC2=CC=CC=C12)=C(C)C Chemical compound CC(C)C1=CC(C=C1)[Zr](Cl)(Cl)(C1C=CC2=CC=CC=C12)=C(C)C YXKIUCUZHJZDFB-UHFFFAOYSA-L 0.000 description 1
- 235000019739 Dicalciumphosphate Nutrition 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- ZUAMLZICQQHVRX-UHFFFAOYSA-L [Cl-].[Cl-].C(C)(C)=[Ti+2](C1C=C(C=C1)C(C)C)C1C=CC2=CC=CC=C12 Chemical compound [Cl-].[Cl-].C(C)(C)=[Ti+2](C1C=C(C=C1)C(C)C)C1C=CC2=CC=CC=C12 ZUAMLZICQQHVRX-UHFFFAOYSA-L 0.000 description 1
- WSIRJIPTAAEPAQ-UHFFFAOYSA-L [Cl-].[Cl-].C1CC2CC=CC=C2C1[Ti+2](=C(C)C)C1C2=CC=CCC2CC1 Chemical compound [Cl-].[Cl-].C1CC2CC=CC=C2C1[Ti+2](=C(C)C)C1C2=CC=CCC2CC1 WSIRJIPTAAEPAQ-UHFFFAOYSA-L 0.000 description 1
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- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
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- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
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- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 description 1
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- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
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- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- PCILLCXFKWDRMK-UHFFFAOYSA-N naphthalene-1,4-diol Chemical compound C1=CC=C2C(O)=CC=C(O)C2=C1 PCILLCXFKWDRMK-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
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- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
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- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、液晶性樹脂組成物に関する。 The present invention relates to a liquid crystalline resin composition.
液晶性ポリエステル樹脂に代表される液晶性樹脂は、優れた機械的強度、耐熱性、耐薬品性、電気的性質等をバランス良く有し、優れた寸法安定性も有するため高機能エンジニアリングプラスチックとして広く利用されている。一方、近年、携帯電話;無線LAN;GPS、VICS(登録商標)、ETC等のITS技術等の情報通信分野において著しい技術発達がなされている。これに応じて、マイクロ波、ミリ波等の高周波領域において適用できる高性能な高周波対応電子部品のニーズが強くなっている。このような電子部品を構成する材料は、個々の電子部品の設計に応じて、適切な誘電特性を有することが求められている。 Liquid crystalline resins, represented by liquid crystalline polyester resins, have well-balanced mechanical strength, heat resistance, chemical resistance, electrical properties, etc., and are widely used as high-performance engineering plastics due to their excellent dimensional stability. It's being used. On the other hand, in recent years, remarkable technological development has been made in the field of information communication such as mobile phones; wireless LAN; ITS technology such as GPS, VICS (registered trademark), ETC and the like. Accordingly, there is a growing need for high-performance high-frequency electronic components that can be applied in high-frequency regions such as microwaves and millimeter waves. Materials constituting such electronic parts are required to have appropriate dielectric properties according to the design of each electronic part.
例えば、特許文献1には、融点320℃以上の全芳香族液晶ポリエステル90~45重量%、アスペクト比が2以下の無機球状中空体10~40重量%、アスペクト比が4以上の無機充填剤0~15重量%を配合した組成物を射出成形して得られる、比誘電率が3.0以下、誘電正接が0.04以下の全芳香族液晶ポリエステル樹脂組成物成形体が、耐ハンダリフロー等の耐熱性を有し、誘電特性に優れ、マイクロ波、ミリ波等の高周波帯域で用いられる情報通信機器の送受信部品の固定あるいは保持部材に用いられる成形体が開示されている。 For example, in Patent Document 1, 90 to 45% by weight of wholly aromatic liquid crystal polyester having a melting point of 320° C. or higher, 10 to 40% by weight of inorganic spherical hollow bodies having an aspect ratio of 2 or less, and 0 inorganic filler having an aspect ratio of 4 or more. A wholly aromatic liquid crystal polyester resin composition molded article having a relative dielectric constant of 3.0 or less and a dielectric loss tangent of 0.04 or less obtained by injection molding a composition containing 15% by weight or less has solder reflow resistance, etc. , has excellent dielectric properties, and is used as a fixing or holding member for transmitting/receiving components of information communication equipment used in high-frequency bands such as microwaves and millimeter waves.
しかし、本発明者らの検討によれば、無機球状中空体等の中空フィラーを含有する従来の液晶性樹脂組成物は、溶融粘度が著しく高く、流動性が不良であり、又は、誘電特性若しくは耐熱性に改善の余地があることが判明した。 However, according to the studies of the present inventors, conventional liquid crystalline resin compositions containing hollow fillers such as inorganic spherical hollow bodies have remarkably high melt viscosities, poor fluidity, or poor dielectric properties or It was found that there is room for improvement in heat resistance.
本発明は、上記課題を解決するためになされたものであり、その目的は、誘電特性及び耐熱性に優れ、流動性の良好な液晶性樹脂組成物を提供することにある。 The present invention has been made to solve the above problems, and an object thereof is to provide a liquid crystalline resin composition which is excellent in dielectric properties and heat resistance and has good fluidity.
本発明者らは、上記課題を解決するために鋭意研究を重ねた。その結果、融点が300℃以上である液晶性樹脂と、ガラス転移温度が100℃以上である環状オレフィン系樹脂とを所定の含有量で含有する液晶性樹脂組成物は、誘電特性及び耐熱性に優れ、流動性の良好であることを見出し、本発明を完成するに至った。より具体的には本発明は以下のものを提供する。 The present inventors have made intensive studies to solve the above problems. As a result, a liquid crystalline resin composition containing predetermined contents of a liquid crystalline resin having a melting point of 300° C. or higher and a cyclic olefin resin having a glass transition temperature of 100° C. or higher has excellent dielectric properties and heat resistance. The present inventors have found that it is excellent and has good fluidity, and have completed the present invention. More specifically, the present invention provides the following.
(1) (A)液晶性樹脂、(B)環状オレフィン系樹脂、及び(C)中空フィラーを含有し、(A)液晶性樹脂の融点は、300℃以上であり、(B)環状オレフィン系樹脂のガラス転移温度は、100℃以上であり、(A)液晶性樹脂と(B)環状オレフィン系樹脂との合計100容量部に対して、(A)液晶性樹脂の含有量は、55~85容量部、(B)環状オレフィン系樹脂の含有量は、15~45容量部、(C)中空フィラーの含有量は、20~75容量部である液晶性樹脂組成物。 (1) containing (A) a liquid crystalline resin, (B) a cyclic olefin-based resin, and (C) a hollow filler, (A) the liquid crystalline resin has a melting point of 300° C. or higher, The glass transition temperature of the resin is 100° C. or higher, and the content of (A) the liquid crystalline resin is 55 to 100 parts by volume in total of (A) the liquid crystalline resin and (B) the cyclic olefin resin. 85 parts by volume, (B) a cyclic olefin resin content of 15 to 45 parts by volume, and (C) a hollow filler content of 20 to 75 parts by volume.
(2) (A)液晶性樹脂は、芳香族ヒドロキシカルボン酸及びその誘導体からなる群より選ばれる少なくとも1種に由来する構成単位を構成成分として有する芳香族ポリエステル又は芳香族ポリエステルアミドである(1)に記載の液晶性樹脂組成物。 (2) (A) The liquid crystalline resin is an aromatic polyester or an aromatic polyester amide having as a structural component a structural unit derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof (1 ).
(3) (C)中空フィラーは、ガラスバルーンである(1)又は(2)に記載の液晶性樹脂組成物。 (3) The liquid crystalline resin composition according to (1) or (2), wherein (C) the hollow filler is a glass balloon.
(4) (B)環状オレフィン系樹脂は、環状オレフィンモノマーとα-オレフィンとの付加型重合体である(1)から(3)のいずれかに記載の液晶性樹脂組成物。 (4) The liquid crystalline resin composition according to any one of (1) to (3), wherein the cyclic olefin resin (B) is an addition type polymer of a cyclic olefin monomer and an α-olefin.
(5) 更に、無機充填剤を含有する(1)から(4)のいずれかに記載の液晶性樹脂組成物。 (5) The liquid crystalline resin composition according to any one of (1) to (4), further containing an inorganic filler.
本発明によれば、誘電特性及び耐熱性に優れ、流動性の良好な液晶性樹脂組成物を提供することができる。 According to the present invention, it is possible to provide a liquid crystalline resin composition which is excellent in dielectric properties and heat resistance and has good fluidity.
以下、本発明の実施形態について説明する。なお、本発明は以下の実施形態に限定されない。また、液晶性樹脂組成物中の成分の含有量を表す容量部の値は、当該成分の質量部の値と当該成分の真比重とから算出される値である。本明細書において、容量部及び真比重としては、室温(20~30℃)における値を採用する。 Embodiments of the present invention will be described below. In addition, this invention is not limited to the following embodiment. Further, the value of parts by volume representing the content of a component in the liquid crystalline resin composition is a value calculated from the value of parts by mass of the component and the true specific gravity of the component. In this specification, the values at room temperature (20 to 30° C.) are adopted as the capacity part and the true specific gravity.
<液晶性樹脂組成物>
本発明に係る液晶性樹脂組成物は、(A)液晶性樹脂、(B)環状オレフィン系樹脂、及び(C)中空フィラーを含有し、(A)液晶性樹脂の融点は、300℃以上であり、(B)環状オレフィン系樹脂のガラス転移温度は、100℃以上である。
<Liquid Crystalline Resin Composition>
The liquid crystalline resin composition according to the present invention contains (A) a liquid crystalline resin, (B) a cyclic olefin resin, and (C) a hollow filler, and the melting point of the (A) liquid crystalline resin is 300° C. or higher. and (B) the cyclic olefin resin has a glass transition temperature of 100° C. or higher.
[(A)液晶性樹脂]
本発明で使用する(A)液晶性樹脂とは、光学異方性溶融相を形成し得る性質を有する溶融加工性ポリマーを指す。異方性溶融相の性質は、直交偏光子を利用した慣用の偏光検査法により確認することが出来る。より具体的には、異方性溶融相の確認は、Leitz偏光顕微鏡を使用し、Leitzホットステージに載せた溶融試料を窒素雰囲気下で40倍の倍率で観察することにより実施できる。本発明に適用できる液晶性ポリマーは直交偏光子の間で検査したときに、たとえ溶融静止状態であっても偏光は通常透過し、光学的に異方性を示す。
[(A) liquid crystalline resin]
The (A) liquid crystalline resin used in the present invention refers to a melt-processable polymer having a property capable of forming an optically anisotropic melt phase. The anisotropic melt phase properties can be confirmed by conventional polarimetry using crossed polarizers. More specifically, confirmation of the anisotropic molten phase can be carried out by using a Leitz polarizing microscope and observing the molten sample placed on a Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times. A liquid crystalline polymer applicable to the present invention normally transmits polarized light and exhibits optical anisotropy when inspected between crossed polarizers even in a molten state.
(A)液晶性樹脂の融点は、300℃以上であり、好ましくは300~360℃であり、より好ましくは315~345℃である。(A)液晶性樹脂の融点が300℃以上であると、耐熱性に優れた液晶性樹脂組成物を得やすい。(A)液晶性樹脂の融点が360℃以下であると、流動性の良好な液晶性樹脂組成物を得やすい。 (A) The melting point of the liquid crystalline resin is 300°C or higher, preferably 300 to 360°C, more preferably 315 to 345°C. (A) When the melting point of the liquid crystalline resin is 300° C. or higher, it is easy to obtain a liquid crystalline resin composition having excellent heat resistance. (A) When the melting point of the liquid crystalline resin is 360° C. or less, it is easy to obtain a liquid crystalline resin composition with good fluidity.
上記のような(A)液晶性樹脂の種類としては特に限定されず、芳香族ポリエステル及び/又は芳香族ポリエステルアミドであることが好ましい。また、芳香族ポリエステル及び/又は芳香族ポリエステルアミドを同一分子鎖中に部分的に含むポリエステルもその範囲にある。(A)液晶性樹脂としては、60℃でペンタフルオロフェノールに濃度0.1質量%で溶解したときに、好ましくは少なくとも約2.0dl/g、更に好ましくは2.0~10.0dl/gの対数粘度(I.V.)を有するものが好ましく使用される。 The type of the liquid crystalline resin (A) as described above is not particularly limited, and aromatic polyesters and/or aromatic polyesteramides are preferable. Polyesters that partially contain aromatic polyesters and/or aromatic polyesteramides in the same molecular chain are also within the scope. (A) The liquid crystalline resin is preferably at least about 2.0 dl/g, more preferably 2.0 to 10.0 dl/g when dissolved in pentafluorophenol at 60° C. at a concentration of 0.1% by mass. of logarithmic viscosity (I.V.) is preferably used.
本発明に適用できる(A)液晶性樹脂としての芳香族ポリエステル又は芳香族ポリエステルアミドは、特に好ましくは、芳香族ヒドロキシカルボン酸、芳香族ヒドロキシアミン、芳香族ジアミン、及びそれらの誘導体からなる群より選ばれる少なくとも1種に由来する構成単位を構成成分として有する芳香族ポリエステル又は芳香族ポリエステルアミドである。 The aromatic polyester or aromatic polyester amide (A) as the liquid crystalline resin applicable to the present invention is particularly preferably selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic hydroxylamines, aromatic diamines, and derivatives thereof. It is an aromatic polyester or an aromatic polyester amide having structural units derived from at least one selected as a constituent.
より具体的には、
(1)主として芳香族ヒドロキシカルボン酸及びその誘導体からなる群より選ばれる少なくとも1種に由来する構成単位からなるポリエステル;
(2)主として(a)芳香族ヒドロキシカルボン酸及びその誘導体からなる群より選ばれる少なくとも1種に由来する構成単位と、(b)芳香族ジカルボン酸、脂環族ジカルボン酸、及びそれらの誘導体からなる群より選ばれる少なくとも1種に由来する構成単位と、からなるポリエステル;
(3)主として(a)芳香族ヒドロキシカルボン酸及びその誘導体からなる群より選ばれる少なくとも1種に由来する構成単位と、(b)芳香族ジカルボン酸、脂環族ジカルボン酸、及びそれらの誘導体からなる群より選ばれる少なくとも1種に由来する構成単位と、(c)芳香族ジオール、脂環族ジオール、脂肪族ジオール、及びそれらの誘導体からなる群より選ばれる少なくとも1種に由来する構成単位と、からなるポリエステル;
(4)主として(a)芳香族ヒドロキシカルボン酸及びその誘導体からなる群より選ばれる少なくとも1種に由来する構成単位と、(b)芳香族ヒドロキシアミン、芳香族ジアミン、及びそれらの誘導体からなる群より選ばれる少なくとも1種に由来する構成単位と、(c)芳香族ジカルボン酸、脂環族ジカルボン酸、及びそれらの誘導体からなる群より選ばれる少なくとも1種に由来する構成単位と、からなるポリエステルアミド;
(5)主として(a)芳香族ヒドロキシカルボン酸及びその誘導体からなる群より選ばれる少なくとも1種に由来する構成単位と、(b)芳香族ヒドロキシアミン、芳香族ジアミン、及びそれらの誘導体からなる群より選ばれる少なくとも1種に由来する構成単位と、(c)芳香族ジカルボン酸、脂環族ジカルボン酸、及びそれらの誘導体からなる群より選ばれる少なくとも1種に由来する構成単位と、(d)芳香族ジオール、脂環族ジオール、脂肪族ジオール、及びそれらの誘導体からなる群より選ばれる少なくとも1種に由来する構成単位と、からなるポリエステルアミド等が挙げられる。更に上記の構成成分に必要に応じ分子量調整剤を併用してもよい。
More specifically,
(1) Polyester mainly composed of structural units derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof;
(2) Mainly (a) structural units derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof, and (b) aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof A polyester consisting of a structural unit derived from at least one selected from the group consisting of;
(3) Mainly (a) structural units derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof, and (b) aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof and (c) a structural unit derived from at least one selected from the group consisting of aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof. a polyester consisting of;
(4) A group consisting mainly of (a) structural units derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof, and (b) aromatic hydroxyamines, aromatic diamines, and derivatives thereof and (c) a structural unit derived from at least one selected from the group consisting of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof. Amide;
(5) A group consisting mainly of (a) structural units derived from at least one selected from the group consisting of aromatic hydroxycarboxylic acids and derivatives thereof, and (b) aromatic hydroxyamines, aromatic diamines, and derivatives thereof (c) a structural unit derived from at least one selected from the group consisting of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof; and (d) and a structural unit derived from at least one selected from the group consisting of aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof. Furthermore, a molecular weight modifier may be used in combination with the above constituents, if necessary.
本発明に適用できる(A)液晶性樹脂を構成する具体的化合物の好ましい例としては、p-ヒドロキシ安息香酸、6-ヒドロキシ-2-ナフトエ酸等の芳香族ヒドロキシカルボン酸;2,6-ジヒドロキシナフタレン、1,4-ジヒドロキシナフタレン、4,4’-ジヒドロキシビフェニル、ハイドロキノン、レゾルシン、下記一般式(I)で表される化合物、及び下記一般式(II)で表される化合物等の芳香族ジオール;1,4-フェニレンジカルボン酸、1,3-フェニレンジカルボン酸、4,4’-ジフェニルジカルボン酸、2,6-ナフタレンジカルボン酸、及び下記一般式(III)で表される化合物等の芳香族ジカルボン酸;p-アミノフェノール、p-フェニレンジアミン、N-アセチル-p-アミノフェノール等の芳香族アミン類が挙げられる。
本発明に用いられる(A)液晶性樹脂の調製は、上記のモノマー化合物(又はモノマーの混合物)から直接重合法やエステル交換法を用いて公知の方法で行うことができ、通常は溶融重合法、溶液重合法、スラリー重合法、固相重合法等、又はこれらの2種以上の組み合わせが用いられ、溶融重合法、又は溶融重合法と固相重合法との組み合わせが好ましく用いられる。エステル形成能を有する上記化合物類はそのままの形で重合に用いてもよく、また、重合の前段階で前駆体から該エステル形成能を有する誘導体に変性されたものでもよい。これらの重合に際しては種々の触媒の使用が可能であり、代表的なものとしては、酢酸カリウム、酢酸マグネシウム、酢酸第一錫、テトラブチルチタネート、酢酸鉛、酢酸ナトリウム、三酸化アンチモン、トリス(2,4-ペンタンジオナト)コバルト(III)等の金属塩系触媒、N-メチルイミダゾール、4-ジメチルアミノピリジン等の有機化合物系触媒が挙げられる。触媒の使用量は一般にはモノマーの全質量に対して約0.001~1質量%、特に約0.01~0.2質量%が好ましい。これらの重合方法により製造されたポリマーは更に必要があれば、減圧又は不活性ガス中で加熱する固相重合法により分子量の増加を図ることができる。 The liquid crystalline resin (A) used in the present invention can be prepared by a known method using a direct polymerization method or a transesterification method from the above monomer compound (or a mixture of monomers), and usually a melt polymerization method. , a solution polymerization method, a slurry polymerization method, a solid phase polymerization method, or a combination of two or more thereof is used, and a melt polymerization method or a combination of a melt polymerization method and a solid phase polymerization method is preferably used. The above-mentioned compounds having ester-forming ability may be used for polymerization as they are, or may be modified from precursors to derivatives having said ester-forming ability in the pre-polymerization stage. Various catalysts can be used in these polymerizations, and representative ones include potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, tris ,4-pentanedionato)cobalt (III), and organic compound catalysts such as N-methylimidazole and 4-dimethylaminopyridine. The amount of catalyst used is generally about 0.001 to 1% by weight, preferably about 0.01 to 0.2% by weight, based on the total weight of the monomers. Polymers produced by these polymerization methods can be further increased in molecular weight by solid phase polymerization in which heating is performed under reduced pressure or in an inert gas, if necessary.
上記のような方法で得られた(A)液晶性樹脂の溶融粘度は特に限定されない。一般には成形温度での溶融粘度が剪断速度1000sec-1で3Pa・s以上500Pa・s以下のものが使用可能である。しかし、それ自体あまり高粘度のものは流動性が非常に悪化するため好ましくない。なお、上記(A)液晶性樹脂は2種以上の液晶性樹脂の混合物であってもよい。 The melt viscosity of (A) the liquid crystalline resin obtained by the above method is not particularly limited. In general, those having a melt viscosity at a molding temperature of 3 Pa·s or more and 500 Pa·s or less at a shear rate of 1000 sec −1 can be used. However, if the viscosity is too high per se, the fluidity will be greatly deteriorated, which is not preferable. The liquid crystalline resin (A) may be a mixture of two or more liquid crystalline resins.
(A)成分の含有量は、(A)液晶性樹脂と(B)環状オレフィン系樹脂との合計100容量部に対して、55~85容量部であり、好ましくは58~82容量部であり、より好ましくは60~80容量部である。(A)成分の含有量が55容量部以上であると、耐熱性に優れた液晶性樹脂組成物を得やすい。(A)成分の含有量が85容量部以下であると、誘電特性に優れた液晶性樹脂組成物を得やすい。 The content of component (A) is 55 to 85 parts by volume, preferably 58 to 82 parts by volume, with respect to a total of 100 parts by volume of the liquid crystalline resin (A) and the cyclic olefin resin (B). , more preferably 60 to 80 parts by volume. When the content of component (A) is 55 parts by volume or more, it is easy to obtain a liquid crystalline resin composition having excellent heat resistance. When the content of component (A) is 85 parts by volume or less, it is easy to obtain a liquid crystalline resin composition having excellent dielectric properties.
[(B)環状オレフィン系樹脂]
本発明における(B)環状オレフィン系樹脂の形態としては、特に限定されず、以下が挙げられる。
(1)環構造を有する単量体と、オレフィンとの付加型重合体
(2)環構造を有する単量体と、単環構造を有する単量体との開環型重合体
[(B) Cyclic olefin resin]
The form of the (B) cyclic olefin-based resin in the present invention is not particularly limited and includes the following.
(1) Addition type polymer of a monomer having a ring structure and an olefin (2) Ring-opening type polymer of a monomer having a ring structure and a monomer having a monocyclic structure
本発明の液晶性樹脂組成物に配合される(B)環状オレフィン系樹脂の種類は、1種であってもよく、2種以上であってもよい。 The type of the (B) cyclic olefin-based resin blended in the liquid crystalline resin composition of the present invention may be one type, or two or more types.
(B)環状オレフィン系樹脂が付加型重合体及び開環型重合体のいずれの態様であっても、柔軟性等の観点から、(B)環状オレフィン系樹脂を構成する単量体は、得られる(B)環状オレフィン系樹脂にエチレンユニットが含まれるように選択されることが好ましい。なお、エチレンユニットとは、エチレンに由来する構成単位をいう。
以下、(B)環状オレフィン系樹脂を構成する単量体の例を説明する。
Regardless of whether the cyclic olefin resin (B) is an addition polymer or a ring-opening polymer, the monomers constituting the cyclic olefin resin (B) should be It is preferable that the (B) cyclic olefin-based resin to be obtained contains an ethylene unit. In addition, an ethylene unit means a structural unit derived from ethylene.
Examples of the monomers constituting the (B) cyclic olefin resin are described below.
(環構造を有する単量体)
(B)環状オレフィン系樹脂を構成する環構造を有する単量体としては、例えば、環状オレフィンモノマーが挙げられる。環状オレフィンモノマーとしては、例えば、ノルボルネン、及び下記一般式(IV)で示される複環環状単量体が挙げられる。
(Monomer having a ring structure)
Examples of (B) the monomer having a ring structure that constitutes the cyclic olefin resin include cyclic olefin monomers. Cyclic olefin monomers include, for example, norbornene and multicyclic cyclic monomers represented by the following general formula (IV).
式(I)中、R1~R12は、それぞれ同一でも異なっていてもよく、水素原子、ハロゲン原子、及び、炭化水素基からなる群より選ばれるものである。炭化水素基は飽和炭化水素基でも、不飽和炭化水素基でもよい。
不飽和炭化水素基としては、ビニル基が挙げられる。ビニル基を含む環構造を有する単量体として、5-ビニル-2-ノルボルネン等が挙げられる。
In formula (I), R 1 to R 12 may be the same or different and are selected from the group consisting of hydrogen atoms, halogen atoms and hydrocarbon groups. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
A vinyl group is mentioned as an unsaturated hydrocarbon group. Examples of monomers having a ring structure containing a vinyl group include 5-vinyl-2-norbornene.
R9とR10、R11とR12は、一体化して2価の炭化水素基を形成してもよい。
R9又はR10と、R11又はR12とは、互いに環を形成していてもよい。
nは、0又は正の整数を示し、nが2以上の場合には、R5~R8は、それぞれの繰り返し単位の中で、それぞれ同一でも異なっていてもよい。ただし、n=0の場合、R1~R4及びR9~R12の少なくとも1個は、水素原子ではない。
R 9 and R 10 , R 11 and R 12 may combine to form a divalent hydrocarbon group.
R 9 or R 10 and R 11 or R 12 may form a ring together.
n represents 0 or a positive integer, and when n is 2 or more, R 5 to R 8 may be the same or different in each repeating unit. However, when n=0, at least one of R 1 to R 4 and R 9 to R 12 is not a hydrogen atom.
R9とR10、又はR11とR12とが一体化して2価の炭化水素基を形成する場合の具体例としては、例えば、エチリデン基、プロピリデン基、イソプロピリデン基等のアルキリデン基等を挙げることができる。 Specific examples of the case where R 9 and R 10 or R 11 and R 12 are combined to form a divalent hydrocarbon group include alkylidene groups such as ethylidene group, propylidene group and isopropylidene group. can be mentioned.
R9又はR10と、R11又はR12とが、互いに環を形成する場合には、形成される環は単環でも多環であってもよく、架橋を有する多環であってもよく、二重結合を有する環であってもよく、またこれらの環の組み合わせからなる環であってもよい。また、これらの環はメチル基等の置換基を有していてもよい。 When R 9 or R 10 and R 11 or R 12 form a ring together, the ring formed may be monocyclic or polycyclic, or may be a polycyclic ring having a bridge. , a ring having a double bond, or a ring consisting of a combination of these rings. Moreover, these rings may have a substituent such as a methyl group.
環構造を有する単量体は、側鎖を有するものであってもよく、側鎖を有さないものであってもよい。 A monomer having a ring structure may or may not have a side chain.
環構造を有する単量体の具体例としては、ノルボルネン、テトラシクロドデセンが挙げられる。
オレフィンとの反応における触媒(メタロセン触媒等)に対する反応性が高いという観点から、環構造を有する単量体としては、ノルボルネンが特に好ましい。
Specific examples of monomers having ring structures include norbornene and tetracyclododecene.
Norbornene is particularly preferable as the monomer having a ring structure from the viewpoint of high reactivity with respect to catalysts (metallocene catalysts, etc.) in the reaction with olefins.
(B)環状オレフィン系樹脂において、環構造を有する単量体に由来する構成単位の含有量は特に限定されない。該構成単位の含有量の下限値は、(B)環状オレフィン系樹脂に耐熱性を付与するという観点から、(B)環状オレフィン系樹脂に含まれる全構成単位に対し、好ましくは0mol%超、より好ましくは5mol以上である。該構成単位の含有量の上限値は、架橋性を付与しやすいという観点から、(B)環状オレフィン系樹脂に含まれる全構成単位に対し、好ましくは55mol%以下、より好ましくは50mol%以下、更により好ましくは40mol%以下である。 (B) In the cyclic olefin-based resin, the content of structural units derived from monomers having a ring structure is not particularly limited. From the viewpoint of imparting heat resistance to the (B) cyclic olefin-based resin, the lower limit of the content of the structural unit is preferably more than 0 mol% with respect to all the structural units contained in the (B) cyclic olefin-based resin. More preferably, it is 5 mol or more. The upper limit of the content of the structural unit is preferably 55 mol% or less, more preferably 50 mol% or less, based on the total structural units contained in the cyclic olefin resin (B), from the viewpoint of easily imparting crosslinkability. Even more preferably, it is 40 mol % or less.
(B)環状オレフィン系樹脂を構成する環構造を有する単量体は、1種単独でもよく、2種以上を組み合わせてもよい。 (B) The monomer having a ring structure that constitutes the cyclic olefin resin may be used singly or in combination of two or more.
(オレフィン)
(B)環状オレフィン系樹脂を構成するオレフィンとしては、特に限定されず、例えば、α-オレフィンが挙げられる。α-オレフィンとしては、炭素数2以上10以下のα-オレフィンが好ましい。
(olefin)
(B) The olefin constituting the cyclic olefin resin is not particularly limited, and examples thereof include α-olefins. As the α-olefin, an α-olefin having 2 to 10 carbon atoms is preferable.
α-オレフィンの具体例としては、エチレン、プロピレン、1-ブテン、1-ペンテン、1-へキセン、3-メチル-1-ブテン、3-メチル-1-ペンテン、3-エチル-1-ペンテン、4-メチル-1-ペンテン、4-メチル-1-へキセン、4,4-ジメチル-1-ヘキセン、4,4-ジメチル-1-ペンテン、4-エチル-1-へキセン、3-エチル-1-ヘキセン、1-ヘプテン、1-オクテン、1-ノネン、1-デセン、1-ドデセン、1-テトラデセン、1-ヘキサデセン、1-オクタデセン、1-エイコセン等が挙げられる。上記のうち、エチレンが特に好ましい。 Specific examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl- 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. Of the above, ethylene is particularly preferred.
(B)環状オレフィン系樹脂において、オレフィンの含有量は特に限定されない。該オレフィンの含有量の下限値は、得られる架橋物に柔軟性を付与しやすいという観点から、(B)環状オレフィン系樹脂に含まれる全構成単位に対し、好ましくは45mol%以上、より好ましくは50mol%以上、更により好ましくは60mol%以上である。該オレフィンの含有量の上限値は、適度な弾性率を有する架橋物を得られやすいという観点から、(B)環状オレフィン系樹脂に含まれる全構成単位に対し、好ましくは100mol%未満、より好ましくは95mol%以下である。 (B) Cyclic olefin resin WHEREIN: Content of an olefin is not specifically limited. The lower limit of the content of the olefin is preferably 45 mol% or more, more preferably 45 mol% or more, based on the total structural units contained in the cyclic olefin resin (B), from the viewpoint of easily imparting flexibility to the resulting crosslinked product. It is 50 mol % or more, still more preferably 60 mol % or more. The upper limit of the content of the olefin is preferably less than 100 mol %, more preferably less than 100 mol %, based on the total structural units contained in the cyclic olefin resin (B), from the viewpoint that it is easy to obtain a crosslinked product having an appropriate elastic modulus. is 95 mol % or less.
(B)環状オレフィン系樹脂を構成するオレフィンは、1種単独でもよく、2種以上を組み合わせてもよい。 (B) The olefins constituting the cyclic olefin-based resin may be used singly or in combination of two or more.
(単環構造を有する単量体)
単環構造を有する単量体としては、環状構造を1つのみ有するオレフィンであれば特に限定されない。オレフィンとしては、炭素数3以上10以下のオレフィンが好ましい。
(Monomer having a monocyclic structure)
The monomer having a monocyclic structure is not particularly limited as long as it is an olefin having only one cyclic structure. As the olefin, an olefin having 3 or more and 10 or less carbon atoms is preferable.
単環構造を有する単量体の具体例としては、環状モノオレフィン(シクロプロペン、シクロブテン、シクロペンテン、メチルシクロペンテン、シクロヘキセン、メチルシクロヘキセン、シクロヘプテン、シクロオクテン等)、環状ジオレフィン(シクロヘキサジエン、メチルシクロヘキサジエン、シクロオクタジエン、メチルシクロオクタジエン等)が挙げられる。上記のうち、シクロペンテンが特に好ましい。 Specific examples of monomers having a monocyclic structure include cyclic monoolefins (cyclopropene, cyclobutene, cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cycloheptene, cyclooctene, etc.), cyclic diolefins (cyclohexadiene, methylcyclohexadiene , cyclooctadiene, methylcyclooctadiene, etc.). Of the above, cyclopentene is particularly preferred.
(B)環状オレフィン系樹脂において、単環構造を有する単量体の含有量は特に限定されない。該単環構造を有する単量体の含有量の下限値は、得られる架橋物に柔軟性を付与しやすいという観点から、(B)環状オレフィン系樹脂に含まれる全構成単位に対し、好ましくは40mol%以上である。該単環構造を有する単量体の含有量の上限値は、適度な弾性率を有する架橋物を得られやすいという観点から、(B)環状オレフィン系樹脂に含まれる全構成単位に対し、好ましくは100mol%未満である。(B)環状オレフィン系樹脂を構成する単環構造を有する単量体は、1種単独でもよく、2種以上を組み合わせてもよい。 (B) Cyclic olefin resin WHEREIN: Content of the monomer which has a monocyclic structure is not specifically limited. The lower limit of the content of the monomer having a monocyclic structure is preferably 40 mol % or more. The upper limit of the content of the monomer having a monocyclic structure is preferable for all structural units contained in the cyclic olefin-based resin (B), from the viewpoint that it is easy to obtain a crosslinked product having an appropriate elastic modulus. is less than 100 mol %. (B) The monomer having a monocyclic structure that constitutes the cyclic olefin resin may be used singly or in combination of two or more.
(付加型反応)
(B)環状オレフィン系樹脂が、環構造を有する単量体と、オレフィンとの付加型重合体である場合、上記の環構造を有する単量体と、オレフィンとを用いて、付加型重合体の製造方法として知られる任意の手法を採用して(B)環状オレフィン系樹脂を製造することができる。
(addition type reaction)
(B) When the cyclic olefin-based resin is an addition type polymer of a monomer having a ring structure and an olefin, the monomer having a ring structure and an olefin are used to form an addition type polymer. (B) the cyclic olefin-based resin can be produced by adopting any method known as the production method of.
付加重合触媒としては、メタロセン系触媒を特に好適に用いることができる。メタロセン触媒の具体的な例としては、(t-ブチルアミド)ジメチル-9-フルオレニルシランチタンジメチル、ラセミ-エチリデン-ビス(インデニル)ジルコニウムジクロライド、ラセミ-ジメチルシリル-ビス(2-メチル-ベンゾインデニル)ジルコニウムジクロライド、ラセミ-イソプロピリデン-ビス(テトラヒドロインデニル)ジルコニウムジクロライド、イソプロピリデン(1-インデニル)(3-イソプロピル-シクロペンタジエニル)ジルコニウムジクロライド、(t-ブチルアミド)ジメチル-9-フルオレニルシランジルコニウムジメチル、(t-ブチルアミド)ジメチル-9-フルオレニルシランジルコニウムジクロリド、(t-ブチルアミド)ジメチル-9-(3,6-ジメチルフルオレニル)シランジルコニウムジメチル、(t-ブチルアミド)ジメチル-9-[3,6-ジ(i-プロピル)フルオレニル]シランジルコニウムジメチル、(t-ブチルアミド)ジメチル-9-[3,6-ジ(t-ブチル)フルオレニル]シランジルコニウムジメチル、(t-ブチルアミド)ジメチル-9-[2,7-ジ(t-ブチル)フルオレニル]シランジルコニウムジメチル、(t-ブチルアミド)ジメチル-9-(2,3,6,7-テトラメチルフルオレニル)シランジルコニウムジメチル、ラセミ-エチリデン-ビス(インデニル)チタンジクロライド、ラセミ-ジメチルシリル-ビス(2-メチル-ベンゾインデニル)チタンジクロライド、ラセミ-イソプロピリデン-ビス(テトラヒドロインデニル)チタンジクロライド、イソプロピリデン(1-インデニル)(3-イソプロピル-シクロペンタジエニル)チタンジクロライド、(t-ブチルアミド)ジメチル-9-フルオレニルシランチタンジクロリド、(t-ブチルアミド)ジメチル-9-(3,6-ジメチルフルオレニル)シランチタンジメチル、(t-ブチルアミド)ジメチル-9-[3,6-ジ(i-プロピル)フルオレニル]シランチタンジメチル、(t-ブチルアミド)ジメチル-9-[3,6-ジ(t-ブチル)フルオレニル]シランチタンジメチル、(t-ブチルアミド)ジメチル-9-[2,7-ジ(t-ブチル)フルオレニル]シランチタンジメチル、(t-ブチルアミド)ジメチル-9-(2,3,6,7-テトラメチルフルオレニル)シランチタンジメチルが挙げられるが、これらに限定されるものではない。付加重合触媒は、1種単独で又は2種以上組み合わせて使用することができる。 As the addition polymerization catalyst, a metallocene catalyst can be particularly preferably used. Specific examples of metallocene catalysts include (t-butylamido)dimethyl-9-fluorenylsilanetitanium dimethyl, racemic-ethylidene-bis(indenyl)zirconium dichloride, racemic-dimethylsilyl-bis(2-methyl-benzoinde nyl)zirconium dichloride, racemic-isopropylidene-bis(tetrahydroindenyl)zirconium dichloride, isopropylidene(1-indenyl)(3-isopropyl-cyclopentadienyl)zirconium dichloride, (t-butylamido)dimethyl-9-fluore Nilsilanezirconium dimethyl, (t-butylamido)dimethyl-9-fluorenylsilanezirconium dichloride, (t-butylamido)dimethyl-9-(3,6-dimethylfluorenyl)silanezirconium dimethyl, (t-butylamido)dimethyl -9-[3,6-di(i-propyl)fluorenyl]silanezirconium dimethyl, (t-butylamido)dimethyl-9-[3,6-di(t-butyl)fluorenyl]silanezirconium dimethyl, (t-butylamide ) dimethyl-9-[2,7-di(t-butyl)fluorenyl]silanezirconium dimethyl, (t-butylamido)dimethyl-9-(2,3,6,7-tetramethylfluorenyl)silanezirconium dimethyl, racemic-ethylidene-bis(indenyl)titanium dichloride, racemic-dimethylsilyl-bis(2-methyl-benzoindenyl)titanium dichloride, racemic-isopropylidene-bis(tetrahydroindenyl)titanium dichloride, isopropylidene(1-indenyl) (3-isopropyl-cyclopentadienyl)titanium dichloride, (t-butylamido)dimethyl-9-fluorenylsilanetitanium dichloride, (t-butylamido)dimethyl-9-(3,6-dimethylfluorenyl)silanetitanium dimethyl, (t-butylamido)dimethyl-9-[3,6-di(i-propyl)fluorenyl]silanetitanium dimethyl, (t-butylamido)dimethyl-9-[3,6-di(t-butyl)fluorenyl] Silantitanium dimethyl, (t-butylamido)dimethyl-9-[2,7-di(t-butyl)fluorenyl]silanetitanium dimethyl, (t-butylamido)dimethyl-9-(2,3,6,7-tetramethyl fluorenyl)silanetitanium dimethyl, but are not limited to these. An addition polymerization catalyst can be used individually by 1 type or in combination of 2 or more types.
(B)環状オレフィン系樹脂は、上記重合触媒とともに、助触媒を使用するとより容易に得られやすい。助触媒は、1種単独で又は2種以上組み合わせて使用することができる。助触媒としては、アルキルアルミノキサン、アルキルアルミニウム等が挙げられる。 (B) The cyclic olefin resin can be obtained more easily by using a co-catalyst together with the polymerization catalyst. A promoter can be used individually by 1 type or in combination of 2 or more types. Examples of co-catalysts include alkylaluminoxanes and alkylaluminums.
(開環型反応)
(B)環状オレフィン系樹脂が、環構造を有する単量体と、単環構造を有する単量体との開環型重合体である場合、上記の環構造を有する単量体と、単環構造を有する単量体と、連鎖移動剤とを用いて、開環重合触媒の存在下で開環重合させたのち必要に応じて水素化することで得られる。
(ring-opening reaction)
(B) When the cyclic olefin resin is a ring-opening polymer of a monomer having a ring structure and a monomer having a monocyclic structure, the monomer having a ring structure and the monocyclic It can be obtained by carrying out ring-opening polymerization using a monomer having a structure and a chain transfer agent in the presence of a ring-opening polymerization catalyst, followed by hydrogenation if necessary.
連鎖移動剤としては、分子量を制御でき、末端に炭素原子間の二重結合を1つ持つものであれば特に制約されないが、例えば上述のα-オレフィン(1-ヘキセン等)が挙げられる。 The chain transfer agent is not particularly limited as long as it can control the molecular weight and has one double bond between carbon atoms at the terminal.
開環重合触媒としては、単環の環状オレフィンと、ノルボルネン化合物とを、開環共重合できるものであればよく、ルテニウムカルベン錯体が好ましい。ルテニウムカルベン錯体の具体例としては、ビス(トリシクロヘキシルホスフィン)ベンジリデンルテニウムジクロリド、ビス(トリフェニルホスフィン)-3,3-ジフェニルプロペニリデンルテニウムジクロリド、ビス(トリシクロヘキシルホスフィン)t-ブチルビニリデンルテニウムジクロリド、ジクロロ-(3-フェニル-1H-インデン-1-イリデン)ビス(トリシクロヘキシルホスフィン)ルテニウム、ビス(1,3-ジイソプロピルイミダゾリン-2-イリデン)ベンジリデンルテニウムジクロリド、ビス(1,3-ジシクロヘキシルイミダゾリン-2-イリデン)ベンジリデンルテニウムジクロリド、(1,3-ジメシチルイミダゾリン-2-イリデン)(トリシクロヘキシルホスフィン)ベンジリデンルテニウムジクロリド、(1,3-ジメシチルイミダゾリジン-2-イリデン)(トリシクロヘキシルホスフィン)ベンジリデンルテニウムジクロリド、ビス(トリシクロヘキシルホスフィン)エトキシメチリデンルテニウムジクロリド、(1,3-ジメシチルイミダゾリジン-2-イリデン)(トリシクロヘキシルホスフィン)エトキシメチリデンルテニウムジクロリドが挙げられる。開環重合触媒は、1種単独で又は2種以上組み合わせて使用することができる。 As the ring-opening polymerization catalyst, any catalyst capable of ring-opening copolymerization of a monocyclic cyclic olefin and a norbornene compound can be used, and a ruthenium carbene complex is preferable. Specific examples of ruthenium carbene complexes include bis(tricyclohexylphosphine)benzylideneruthenium dichloride, bis(triphenylphosphine)-3,3-diphenylpropenylideneruthenium dichloride, bis(tricyclohexylphosphine)t-butylvinylideneruthenium dichloride, Dichloro-(3-phenyl-1H-inden-1-ylidene)bis(tricyclohexylphosphine)ruthenium, bis(1,3-diisopropylimidazolin-2-ylidene)benzylidene ruthenium dichloride, bis(1,3-dicyclohexylimidazoline-2) -ylidene) benzylidene ruthenium dichloride, (1,3-dimesitylimidazolin-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, (1,3-dimesitylimidazolidin-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, bis(tricyclohexylphosphine)ethoxymethylideneruthenium dichloride, (1,3-dimesitylimidazolidin-2-ylidene)(tricyclohexylphosphine)ethoxymethylideneruthenium dichloride. A ring-opening polymerization catalyst can be used individually by 1 type or in combination of 2 or more types.
本発明においては、開環重合を行った後、必要に応じて開環重合工程における反応系に水素化触媒及び水素を添加して、開環重合体中の炭素原子間の二重結合を水素化してもよい。水素化触媒は、オレフィン類や芳香族化合物の水素化反応に一般的に使用されるものであればよい。水素化触媒の具体例としては、以下が挙げられる。
(1)遷移金属を担体(カーボン、アルミナ、シリカ、ケイソウ土等)に担持させた担持型金属触媒
(2)有機遷移金属化合物(チタン、コバルト、ニッケル等)と、有機金属化合物(リチウム、マグネシウム、アルミニウム、スズ等)からなる均一系触媒
(3)金属錯体触媒(ロジウム、ルテニウム等)
In the present invention, after carrying out the ring-opening polymerization, if necessary, a hydrogenation catalyst and hydrogen are added to the reaction system in the ring-opening polymerization step to replace the double bonds between the carbon atoms in the ring-opening polymer with hydrogen. may be changed. The hydrogenation catalyst may be one generally used for hydrogenation reactions of olefins and aromatic compounds. Specific examples of hydrogenation catalysts include the following.
(1) A supported metal catalyst in which a transition metal is supported on a carrier (carbon, alumina, silica, diatomaceous earth, etc.) (2) An organic transition metal compound (titanium, cobalt, nickel, etc.) and an organic metal compound (lithium, magnesium) , aluminum, tin, etc.) (3) metal complex catalysts (rhodium, ruthenium, etc.)
((B)環状オレフィン系樹脂のガラス転移温度)
(B)環状オレフィン系樹脂のガラス転移温度(以下、「Tg」ともいう。)は、100℃以上である。(B)環状オレフィン系樹脂のTgが100℃以上であると、良好な流動性を維持しつつ、耐熱性に優れた液晶性樹脂組成物を得やすい。(B)環状オレフィン系樹脂のTgの下限は、好ましくは120℃以上、より好ましくは140℃以上である。(B)環状オレフィン系樹脂のTgの上限は、特に限定されず、200℃以下でよく、170℃以下でもよい。
(Glass transition temperature of (B) cyclic olefin resin)
(B) The glass transition temperature (hereinafter also referred to as “Tg”) of the cyclic olefin resin is 100° C. or higher. (B) When the Tg of the cyclic olefin-based resin is 100° C. or higher, it is easy to obtain a liquid crystalline resin composition excellent in heat resistance while maintaining good fluidity. (B) The lower limit of Tg of the cyclic olefin resin is preferably 120°C or higher, more preferably 140°C or higher. (B) The upper limit of the Tg of the cyclic olefin resin is not particularly limited, and may be 200°C or lower, or 170°C or lower.
本発明において、Tgは、DSC法(JIS K 7121記載の方法)によって昇温速度20℃/分の条件で測定した値を採用する。 In the present invention, Tg adopts a value measured by the DSC method (method described in JIS K 7121) at a temperature increase rate of 20°C/min.
(B)成分の含有量は、(A)液晶性樹脂と(B)環状オレフィン系樹脂との合計100容量部に対して、15~45容量部であり、好ましくは18~42容量部であり、より好ましくは20~40容量部である。(B)成分の含有量が15容量部以上であると、誘電特性に優れた液晶性樹脂組成物を得やすい。(A)成分の含有量が45容量部以下であると、耐熱性に優れた液晶性樹脂組成物を得やすい。 The content of component (B) is 15 to 45 parts by volume, preferably 18 to 42 parts by volume, per 100 parts by volume in total of (A) the liquid crystalline resin and (B) the cyclic olefin resin. , more preferably 20 to 40 parts by volume. When the content of component (B) is 15 parts by volume or more, it is easy to obtain a liquid crystalline resin composition having excellent dielectric properties. (A) It is easy to obtain the liquid crystalline resin composition excellent in heat resistance as content of a component is 45 volume parts or less.
[(C)中空フィラー]
(C)中空フィラーは、一般にバルーンと呼ばれているものであり、中空球体の材料としては、例えば、アルミナ、シリカ、ガラス等の無機材料;尿素樹脂、フェノール樹脂、等の有機材料;が挙げられる。中でも、耐熱性や強度の観点からガラスが好ましい。即ち、中空フィラーとしては、ガラスバルーンが好適に用いられる。(C)成分は、単独で用いても、2種以上を併用してもよい。
[(C) Hollow filler]
(C) Hollow fillers are generally called balloons, and examples of hollow sphere materials include inorganic materials such as alumina, silica, and glass; organic materials such as urea resins and phenol resins; be done. Among them, glass is preferable from the viewpoint of heat resistance and strength. That is, glass balloons are preferably used as the hollow filler. (C) component may be used independently or may use 2 or more types together.
(C)中空フィラーのアスペクト比は、溶融粘度上昇及び流動性悪化の抑制並びに成形性等の観点から、好ましくは1.15以上であり、より好ましくは1.20以上2.00以下であり、更により好ましくは1.22以上1.50以下であり、一層更により好ましくは1.25以上1.30未満である。本明細書において、アスペクト比としては、動的画像解析法/粒子状態分析計を用いて、粒子投影面において最も長い部分の長さである最大長Lと、粒子投影面において最大長Lに対し垂直な方向で最も長い部分の長さである最大垂直長Sとを3000個の粒子について測定し、その測定を数回繰り返して、各粒子について計算された比L/Sの平均の値を採用する。 (C) The aspect ratio of the hollow filler is preferably 1.15 or more, more preferably 1.20 or more and 2.00 or less, from the viewpoint of suppression of increase in melt viscosity and deterioration of fluidity, moldability, etc. Still more preferably 1.22 or more and 1.50 or less, and still more preferably 1.25 or more and less than 1.30. In this specification, the aspect ratio is defined as the maximum length L, which is the length of the longest portion on the particle projection surface, and the maximum length L on the particle projection surface using a dynamic image analysis method/particle state analyzer. Measure the maximum vertical length S, which is the length of the longest part in the vertical direction, for 3000 particles, repeat the measurement several times, and adopt the average value of the ratio L / S calculated for each particle do.
(C)成分のメディアン径は、成形性の観点から、5μm以上であることが好ましく、より好ましくは10μm以上であり、(C)成分の破壊抑制や成形性の観点から、好ましくは200μm以下、より好ましくは100μm以下、更により好ましくは50μm以下である。なお、本明細書において、メディアン径とは、レーザー回折/散乱式粒度分布測定法で測定した体積基準の中央値をいう。 The median diameter of component (C) is preferably 5 μm or more, more preferably 10 μm or more, from the viewpoint of moldability, and preferably 200 μm or less from the viewpoint of suppression of breakage of component (C) and moldability. It is more preferably 100 μm or less, still more preferably 50 μm or less. In this specification, the median diameter refers to the volume-based median value measured by a laser diffraction/scattering particle size distribution measurement method.
(C)成分の含有量は、(A)液晶性樹脂と(B)環状オレフィン系樹脂との合計100容量部に対して、20~75容量部であり、好ましくは25~73容量部であり、より好ましくは30~70容量部である。(C)成分の含有量が20容量部以上であると、誘電特性に優れた液晶性樹脂組成物を得やすい。(C)成分の含有量が75容量部以下であると、流動性の良好な液晶性樹脂組成物を得やすい。 The content of component (C) is 20 to 75 parts by volume, preferably 25 to 73 parts by volume, with respect to a total of 100 parts by volume of liquid crystalline resin (A) and cyclic olefin resin (B). , more preferably 30 to 70 parts by volume. When the content of component (C) is 20 parts by volume or more, it is easy to obtain a liquid crystalline resin composition having excellent dielectric properties. When the content of component (C) is 75 parts by volume or less, it is easy to obtain a liquid crystalline resin composition with good fluidity.
[(D)(C)中空フィラーを除く無機充填剤]
本発明に係る液晶性樹脂組成物は、任意に(D)(C)中空フィラーを除く無機充填剤を含有してもよい。該液晶性樹脂組成物が(D)成分を含有すると、該液晶性樹脂組成物の成形体は曲げ弾性率等の機械的強度が向上しやすい。(D)成分は、単独で用いても、2種以上を併用してもよい。(D)成分としては、例えば、板状充填剤、繊維状充填剤、粒状充填剤等が挙げられる。
[(D) (C) Inorganic fillers other than hollow fillers]
The liquid crystalline resin composition according to the present invention may optionally contain inorganic fillers other than (D) and (C) hollow fillers. When the liquid crystalline resin composition contains the component (D), the molded article of the liquid crystalline resin composition tends to have improved mechanical strength such as bending elastic modulus. Component (D) may be used alone or in combination of two or more. Component (D) includes, for example, plate-like fillers, fibrous fillers, granular fillers, and the like.
(板状充填剤)
本発明に係る液晶性樹脂組成物が板状充填剤を含有すると、該液晶性樹脂組成物からなる成形体は、曲げ弾性率等の機械的強度が向上しやすく、反りが抑制されやすい。板状充填剤は、単独で用いても、2種以上を併用してもよい。
(plate-like filler)
When the liquid crystalline resin composition according to the present invention contains a plate-like filler, the molded article made of the liquid crystalline resin composition is likely to have improved mechanical strength such as bending elastic modulus, and is likely to be prevented from warping. Plate-like fillers may be used alone or in combination of two or more.
板状充填剤は、メディアン径が15~50μmであることが好ましい。上記メディアン径が15μm以上であると、必要な機械的強度が確保されやすく、成形体の反り抑制効果が高くなりやすい。上記メディアン径が50μm以下であると、組成物の溶融時の流動性が向上しやすい。好ましい上記メディアン径は20~30μmである。 The plate-like filler preferably has a median diameter of 15 to 50 μm. When the median diameter is 15 μm or more, the necessary mechanical strength is likely to be secured, and the effect of suppressing warpage of the molded body is likely to be enhanced. When the median diameter is 50 μm or less, the fluidity of the composition during melting is likely to be improved. The preferred median diameter is 20-30 μm.
板状充填剤としては、特に限定されず、例えば、マイカ、タルク、ガラスフレーク、黒鉛、各種の金属箔(例えば、アルミ箔、鉄箔、銅箔)等が挙げられる。本発明においては板状充填剤として、マイカを使用することが好ましい。 The plate-like filler is not particularly limited, and examples thereof include mica, talc, glass flakes, graphite, various metal foils (eg, aluminum foil, iron foil, copper foil), and the like. In the present invention, mica is preferably used as the plate-like filler.
(繊維状充填剤)
本発明に係る液晶性樹脂組成物が繊維状充填剤を含有すると、該液晶性樹脂組成物からなる成形体は、曲げ弾性率等の機械的強度が向上しやすい。繊維状充填剤は、1種単独で又は2種以上組み合わせて使用することができる。
(Fibrous filler)
When the liquid crystalline resin composition according to the present invention contains a fibrous filler, the molded article made of the liquid crystalline resin composition tends to have improved mechanical strength such as flexural modulus. A fibrous filler can be used individually by 1 type or in combination of 2 or more types.
繊維状充填剤の平均繊維長は、特に限定されず、例えば、250μm以上でよく、好ましくは350~600μmであり、より好ましくは450~500μmである。上記平均繊維長が250μm以上であると、本発明の液晶性樹脂組成物からなる成形体は、機械的強度及び耐熱性が向上しやすい。上記平均繊維長が600μm以下であると、液晶性樹脂組成物の流動性が十分となりやすい。なお、本明細書において、繊維状充填剤の平均繊維長としては、繊維状充填剤の実体顕微鏡画像10枚をCCDカメラからPCに取り込み、画像測定機によって画像処理手法により、実体顕微鏡画像1枚ごとに100本の繊維状充填剤、即ち、合計1000本の繊維状充填剤について繊維長を測定した値の平均を採用する。液晶性樹脂組成物中の繊維状充填剤の平均繊維長は、液晶性樹脂組成物を600℃で2時間の加熱により灰化して残存した繊維状充填剤について、上記方法を適用することで測定される。 The average fiber length of the fibrous filler is not particularly limited, and may be, for example, 250 μm or more, preferably 350 to 600 μm, more preferably 450 to 500 μm. When the average fiber length is 250 μm or more, the molded article made of the liquid crystalline resin composition of the present invention tends to have improved mechanical strength and heat resistance. When the average fiber length is 600 µm or less, the fluidity of the liquid crystalline resin composition tends to be sufficient. In this specification, the average fiber length of the fibrous filler is obtained by capturing 10 stereomicroscopic images of the fibrous filler from a CCD camera into a PC, and performing an image processing method using an image measuring machine to obtain 1 stereomicroscopic image. The average of the fiber length measurements of 100 fibrous fillers, ie a total of 1000 fibrous fillers, is adopted. The average fiber length of the fibrous filler in the liquid crystalline resin composition is measured by applying the above method to the remaining fibrous filler after incineration by heating the liquid crystalline resin composition at 600° C. for 2 hours. be done.
繊維状充填剤の平均繊維径としては、特に限定されず、例えば、20μm以下でよく、5~15μmでもよい。なお、本明細書において、繊維状充填剤の平均繊維径としては、繊維状充填剤を走査型電子顕微鏡で観察し、30本の繊維状充填剤について繊維径を測定した値の平均を採用する。液晶性樹脂組成物中の繊維状充填剤の平均繊維径は、液晶性樹脂組成物を600℃で2時間の加熱により灰化して残存した繊維状充填剤について、上記方法を適用することで測定される。 The average fiber diameter of the fibrous filler is not particularly limited, and may be, for example, 20 μm or less, or 5 to 15 μm. In the present specification, the average fiber diameter of the fibrous filler is the average of the values obtained by observing the fibrous filler with a scanning electron microscope and measuring the fiber diameters of 30 fibrous fillers. . The average fiber diameter of the fibrous filler in the liquid crystalline resin composition is measured by applying the above method to the remaining fibrous filler after incineration by heating the liquid crystalline resin composition at 600° C. for 2 hours. be done.
以上の形状を満足する繊維状充填剤であれば、何れの繊維も用いることができるが、繊維状充填剤としては、例えば、ガラス繊維、ミルドファイバー、カーボン繊維、アスベスト繊維、シリカ繊維、シリカ・アルミナ繊維、ジルコニア繊維、窒化硼素繊維、窒化硅素繊維、硼素繊維、チタン酸カリウム繊維、更にステンレス、アルミニウム、チタン、銅、真鍮等の金属の繊維状物等の無機質繊維状物質が挙げられる。本発明においては、機械的強度の観点から、繊維状充填剤として、ガラス繊維を使用することが好ましい。 Any fiber can be used as long as it is a fibrous filler that satisfies the above shape. Inorganic fibrous materials such as alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, potassium titanate fibers, and fibrous materials of metals such as stainless steel, aluminum, titanium, copper and brass can be used. In the present invention, it is preferable to use glass fiber as the fibrous filler from the viewpoint of mechanical strength.
(粒状充填剤)
本発明に係る液晶性樹脂組成物が粒状充填剤を含有すると、該液晶性樹脂組成物からなる成形体は、曲げ弾性率等の機械的強度が向上しやすく、表面白化が抑制されやすい。粒状充填剤は、1種単独で又は2種以上組み合わせて使用することができる。
(granular filler)
When the liquid crystalline resin composition according to the present invention contains a granular filler, the molded article made of the liquid crystalline resin composition tends to have improved mechanical strength such as bending elastic modulus, and tends to suppress surface whitening. A granular filler can be used individually by 1 type or in combination of 2 or more types.
粒状充填剤のメディアン径は、好ましくは0.3~5.0μmである。上記メディアン径が0.3μm以上であると、成形体の耐衝撃性が維持されやすい。上記メディアン径が5.0μm以下であると、成形体の表面白化抑制効果が高くなりやすい。上記メディアン径は、より好ましくは0.5~5.0μmであり、更により好ましくは0.5~4.0μmである。液晶性樹脂組成物中の粒状充填剤のメディアン径は、液晶性樹脂組成物を600℃で2時間の加熱により灰化して残存した粒状充填剤について測定した値である。 The median diameter of the particulate filler is preferably 0.3-5.0 μm. When the median diameter is 0.3 μm or more, the impact resistance of the molded article is likely to be maintained. When the median diameter is 5.0 μm or less, the effect of suppressing surface whitening of the molded article tends to be enhanced. The median diameter is more preferably 0.5 to 5.0 μm, still more preferably 0.5 to 4.0 μm. The median diameter of the particulate filler in the liquid crystalline resin composition is a value measured for the particulate filler remaining after incineration by heating the liquid crystalline resin composition at 600° C. for 2 hours.
粒状充填剤としては、例えば、シリカ、石英粉末、ガラスビーズ、ガラス粉、硅酸カリウムアルミニウム、珪藻土、酸化鉄、酸化チタン、酸化亜鉛、アルミナ等の金属酸化物;炭酸カルシウム、炭酸マグネシウム等の金属炭酸塩;硫酸カルシウム、硫酸バリウム等の金属硫酸塩;ピロリン酸カルシウム、無水リン酸二カルシウム等のリン酸塩;炭化硅素;窒化硅素;窒化硼素等が挙げられる。本発明においては、成形体の表面白化抑制及び成形体の低発塵性の観点から、粒状充填剤として、シリカ及び硫酸バリウムからなる群より選択される1種以上を使用することが好ましく、シリカを使用することがより好ましい。 Granular fillers include, for example, silica, quartz powder, glass beads, glass powder, potassium aluminum silicate, diatomaceous earth, iron oxide, titanium oxide, zinc oxide, metal oxides such as alumina; metals such as calcium carbonate and magnesium carbonate; carbonates; metal sulfates such as calcium sulfate and barium sulfate; phosphates such as calcium pyrophosphate and anhydrous dicalcium phosphate; silicon carbide; silicon nitride; In the present invention, from the viewpoint of suppression of surface whitening of the molded article and low dust generation of the molded article, it is preferable to use at least one selected from the group consisting of silica and barium sulfate as the granular filler. is more preferred.
(D)成分の含有量は、(A)液晶性樹脂と(B)環状オレフィン系樹脂との合計100容量部に対して、好ましくは2~15容量部であり、より好ましくは5~12容量部であり、更により好ましくは7~10容量部である。(D)成分の含有量が上記範囲内であると、液晶性樹脂組成物の流動性が十分に確保されつつ、液晶性樹脂組成物からなる成形体の機械的強度が向上しやすい。 The content of component (D) is preferably 2 to 15 parts by volume, more preferably 5 to 12 parts by volume, with respect to a total of 100 parts by volume of liquid crystalline resin (A) and cyclic olefin resin (B). parts, and even more preferably 7 to 10 parts by volume. When the content of the component (D) is within the above range, the fluidity of the liquid crystalline resin composition is sufficiently ensured, and the mechanical strength of the molded article made of the liquid crystalline resin composition tends to be improved.
[その他の成分]
本発明に係る液晶性樹脂組成物には、本発明の効果を害さない範囲で、その他の重合体、その他の充填剤、一般に合成樹脂に添加される公知の物質、即ち、酸化防止剤や紫外線吸収剤等の安定剤、帯電防止剤、難燃剤、染料や顔料等の着色剤、潤滑剤、離型剤、結晶化促進剤、結晶核剤等も要求性能に応じ適宜添加することができる。
[Other ingredients]
The liquid crystalline resin composition according to the present invention contains other polymers, other fillers, and known substances generally added to synthetic resins, such as antioxidants and ultraviolet rays, as long as they do not impair the effects of the present invention. Stabilizers such as absorbents, antistatic agents, flame retardants, coloring agents such as dyes and pigments, lubricants, mold release agents, crystallization accelerators, crystal nucleating agents, etc. can be added as appropriate according to the required performance.
その他の重合体とは、(A)液晶性樹脂及び(B)環状オレフィン系樹脂以外の重合体をいい、例えば、エポキシ基含有共重合体が挙げられる。その他の充填剤とは、(C)中空フィラー及び(D)無機充填剤以外の充填剤をいい、例えば、(C)中空フィラーを除く有機充填剤;カーボンブラックが挙げられる。 Other polymers refer to polymers other than (A) the liquid crystalline resin and (B) the cyclic olefin resin, and examples thereof include epoxy group-containing copolymers. Other fillers refer to fillers other than (C) hollow fillers and (D) inorganic fillers, and include, for example, (C) organic fillers other than hollow fillers; carbon black.
[液晶性樹脂組成物の調製]
本発明に係る液晶性樹脂組成物の調製は特に限定されない。例えば、(A)成分、(B)成分、(C)成分、任意に(D)成分、及び任意にその他の成分を配合して、これらを1軸又は2軸押出機を用いて溶融混練処理することで、液晶性樹脂組成物の調製が行われる。
[Preparation of liquid crystalline resin composition]
Preparation of the liquid crystalline resin composition according to the present invention is not particularly limited. For example, (A) component, (B) component, (C) component, optionally (D) component, and optionally other components are blended, and these are melt-kneaded using a single-screw or twin-screw extruder. By doing so, the liquid crystalline resin composition is prepared.
[液晶性樹脂組成物]
上記のようにして得られた本発明に係る液晶性樹脂組成物は、溶融時の流動性の観点、成形加工性の観点から、溶融粘度が80Pa・sec以下であることが好ましく、75Pa・sec以下であることがより好ましく、73Pa・sec以下であることが更により好ましい。本明細書において、溶融粘度としては、液晶性樹脂の融点よりも10~20℃高いシリンダー温度、剪断速度1000sec-1の条件で、ISO 11443に準拠した測定方法で得られた値を採用する。
[Liquid Crystalline Resin Composition]
The liquid crystalline resin composition according to the present invention obtained as described above preferably has a melt viscosity of 80 Pa·sec or less, more preferably 75 Pa·sec, from the viewpoint of fluidity when melted and moldability. It is more preferably 73 Pa·sec or less, and even more preferably 73 Pa·sec or less. As used herein, the melt viscosity is a value obtained by a measurement method according to ISO 11443 under the conditions of a cylinder temperature 10 to 20° C. higher than the melting point of the liquid crystalline resin and a shear rate of 1000 sec −1 .
本発明に係る液晶性樹脂組成物は、比誘電率が好ましくは2.75以下、より好ましくは2.73以下、更により好ましくは2.7以下である。本発明に係る液晶性樹脂組成物は、誘電正接が好ましくは0.005以下、より好ましくは0.004以下、更により好ましくは0.003以下である。 The liquid crystalline resin composition according to the present invention preferably has a dielectric constant of 2.75 or less, more preferably 2.73 or less, and even more preferably 2.7 or less. The liquid crystalline resin composition according to the present invention preferably has a dielectric loss tangent of 0.005 or less, more preferably 0.004 or less, and even more preferably 0.003 or less.
以下に実施例を挙げて、本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。 EXAMPLES The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples.
<液晶性樹脂>
・液晶性ポリエステルアミド樹脂(LCP1)
重合容器に下記の原料を仕込んだ後、反応系の温度を140℃に上げ、140℃で1時間反応させた。その後、更に340℃まで4.5時間かけて昇温し、そこから15分かけて10Torr(即ち1330Pa)まで減圧して、酢酸、過剰の無水酢酸、及びその他の低沸分を留出させながら溶融重合を行った。撹拌トルクが所定の値に達した後、窒素を導入して減圧状態から常圧を経て加圧状態にして、重合容器の下部からポリマーを排出し、ストランドをペレタイズしてペレットを得た。得られたペレットについて、窒素気流下、300℃で2時間の熱処理を行って、目的のポリマーを得た。得られたポリマーの融点は336℃、350℃における溶融粘度は19.0Pa・s、真比重は1.4であった。なお、上記ポリマーの溶融粘度は、後述する溶融粘度の測定方法と同様にして測定した。
4-ヒドロキシ安息香酸(HBA);1380g(60モル%)
2-ヒドロキシ-6-ナフトエ酸(HNA);157g(5モル%)
1,4-フェニレンジカルボン酸(TA);484g(17.5モル%)
4,4’-ジヒドロキシビフェニル(BP);388g(12.5モル%)
N-アセチル-p-アミノフェノール(APAP);126g(5モル%)
金属触媒(酢酸カリウム触媒);110mg
アシル化剤(無水酢酸);1659g
<Liquid crystal resin>
・Liquid crystal polyester amide resin (LCP1)
After charging the following raw materials into the polymerization vessel, the temperature of the reaction system was raised to 140° C., and the reaction was carried out at 140° C. for 1 hour. After that, the temperature is further raised to 340°C over 4.5 hours, and the pressure is reduced to 10 Torr (that is, 1330 Pa) over 15 minutes to distill off acetic acid, excess acetic anhydride, and other low-boiling components. Melt polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to increase the pressure from reduced pressure to normal pressure to pressurized state, the polymer was discharged from the bottom of the polymerization vessel, and the strand was pelletized to obtain pellets. The obtained pellets were heat-treated at 300° C. for 2 hours in a nitrogen stream to obtain the desired polymer. The obtained polymer had a melting point of 336° C., a melt viscosity at 350° C. of 19.0 Pa·s, and a true specific gravity of 1.4. The melt viscosity of the polymer was measured in the same manner as the melt viscosity measurement method described below.
4-hydroxybenzoic acid (HBA); 1380 g (60 mol%)
2-hydroxy-6-naphthoic acid (HNA); 157 g (5 mol%)
1,4-phenylene dicarboxylic acid (TA); 484 g (17.5 mol%)
4,4'-dihydroxybiphenyl (BP); 388 g (12.5 mol%)
N-acetyl-p-aminophenol (APAP); 126 g (5 mol%)
Metal catalyst (potassium acetate catalyst); 110 mg
Acylating agent (acetic anhydride); 1659g
・液晶性ポリエステル樹脂(LCP2)
重合容器に下記の原料を仕込んだ後、反応系の温度を140℃に上げ、140℃で1時間反応させた。その後、更に330℃まで3.5時間かけて昇温し、そこから15分かけて10Torr(即ち1330Pa)まで減圧して、酢酸、過剰の無水酢酸、及びその他の低沸分を留出させながら溶融重合を行った。撹拌トルクが所定の値に達した後、窒素を導入して減圧状態から常圧を経て加圧状態にして、重合容器の下部からポリマーを排出し、ストランドをペレタイズして、ペレットとして目的のポリマーを得た。得られたポリマーの融点は323℃、340℃における溶融粘度は30Pa・s、真比重は1.4であった。なお、上記ポリマーの溶融粘度は、後述する溶融粘度の測定方法と同様にして測定した。
4-ヒドロキシ安息香酸(HBA);2524g(79.3モル%)
6-ヒドロキシ-2-ナフトエ酸(HNA);867g(20モル%)
1,4-フェニレンジカルボン酸(TA);27g(0.7モル%)
金属触媒(酢酸カリウム触媒);150mg
アシル化剤(無水酢酸);2336g
・Liquid crystalline polyester resin (LCP2)
After charging the following raw materials into the polymerization vessel, the temperature of the reaction system was raised to 140° C., and the reaction was carried out at 140° C. for 1 hour. After that, the temperature is further raised to 330° C. over 3.5 hours, and the pressure is reduced to 10 Torr (that is, 1330 Pa) over 15 minutes to distill off acetic acid, excess acetic anhydride, and other low-boiling components. Melt polymerization was performed. After the stirring torque reaches a predetermined value, nitrogen is introduced to increase the pressure from reduced pressure to normal pressure to pressurized state, the polymer is discharged from the bottom of the polymerization vessel, and the strand is pelletized to obtain the target polymer as pellets. got The obtained polymer had a melting point of 323° C., a melt viscosity at 340° C. of 30 Pa·s, and a true specific gravity of 1.4. The melt viscosity of the polymer was measured in the same manner as the melt viscosity measurement method described below.
4-hydroxybenzoic acid (HBA); 2524 g (79.3 mol%)
6-hydroxy-2-naphthoic acid (HNA); 867 g (20 mol%)
1,4-phenylene dicarboxylic acid (TA); 27 g (0.7 mol%)
Metal catalyst (potassium acetate catalyst); 150 mg
Acylating agent (acetic anhydride); 2336 g
<環状オレフィン系樹脂(COC)>
加熱装置、攪拌機、窒素挿入装置を備えた5リットルのオートクレーブ中に、トルエン(4リットル)、及び濃度を2.2mol/lに調整したPMAO(東ソー・ファインケム株式会社製)のトルエン溶液(75ml)を投入した。次いで、ノルボルネン(1650g)を注入し、容器を窒素で置換して減圧後、エチレンボンベよりエチレンを圧入し、10atmのゲージ圧で満たした。その後、70℃に加熱し、5分間攪拌した。グローブボックス内にて1μmol/mlに調整したイソプオピリデン(9-フルオレニル)-(1-(3-メチル)シクロペンタジエニル)ジルコニウムジクロライドのトルエン溶液(5ml)をオートクレーブ内に加え、15分放置して反応を進めた。反応後、内容物を排出し、これに500mlの蒸留水、濾過剤を加えた後、加圧濾過した。アセトン10リットル中に濾液を注入し、攪拌、濾過後に、同量のアセトンで洗浄した後、乾燥させ、約60gの白色粉末として、付加型重合体である目的の環状オレフィン系樹脂を得た。得られた環状オレフィン系樹脂のガラス転移温度は155℃、エチレンユニットの比率は40mol%、真比重は1.02であった。なお、上記環状オレフィン系樹脂のTg及びエチレンユニットの比率は、後述の通りに測定した。
<Cyclic olefin resin (COC)>
Toluene (4 liters) and a toluene solution (75 ml) of PMAO (manufactured by Tosoh Finechem Co., Ltd.) adjusted to a concentration of 2.2 mol/l were placed in a 5-liter autoclave equipped with a heating device, stirrer, and nitrogen insertion device. was put in. Next, norbornene (1650 g) was injected, the container was purged with nitrogen and the pressure was reduced, and then ethylene was injected from an ethylene bomb to fill the container with a gauge pressure of 10 atm. After that, it was heated to 70° C. and stirred for 5 minutes. A toluene solution (5 ml) of isopropylidene(9-fluorenyl)-(1-(3-methyl)cyclopentadienyl)zirconium dichloride adjusted to 1 μmol/ml in a glove box was added to the autoclave and allowed to stand for 15 minutes. proceeded with the reaction. After the reaction, the contents were discharged, 500 ml of distilled water and a filtering agent were added, and pressure filtration was performed. The filtrate was poured into 10 liters of acetone, stirred, filtered, washed with the same amount of acetone, and dried to obtain the desired cyclic olefin resin as an addition polymer as about 60 g of white powder. The obtained cyclic olefin resin had a glass transition temperature of 155° C., a ratio of ethylene units of 40 mol %, and a true specific gravity of 1.02. The Tg and ethylene unit ratio of the cyclic olefin resin were measured as described below.
なお、上記環状オレフィン系樹脂は主鎖に炭素原子間の不飽和結合を含まない(つまり、主鎖に炭素原子間の飽和結合のみを含む)。また、上記環状オレフィン系樹脂は側鎖にも炭素原子間の不飽和結合を含まない(つまり、側鎖に炭素原子間の飽和結合のみを含む)。 The cyclic olefin resin does not contain unsaturated bonds between carbon atoms in the main chain (that is, contains only saturated bonds between carbon atoms in the main chain). In addition, the side chains of the cyclic olefin resin do not contain unsaturated bonds between carbon atoms (that is, the side chains contain only saturated bonds between carbon atoms).
(ガラス転移温度(Tg))
JIS K 7121に準拠して、DSC法に基づく下記の条件で、環状オレフィン系樹脂のTg(単位:℃)を測定した。
DSC装置:示差走査熱量計「DSC-7000X」(株式会社日立ハイテクサイエンス製)
測定雰囲気:窒素
昇温条件:20℃/分
(Glass transition temperature (Tg))
Based on JIS K 7121, the Tg (unit: °C) of the cyclic olefin resin was measured under the following conditions based on the DSC method.
DSC device: Differential scanning calorimeter "DSC-7000X" (manufactured by Hitachi High-Tech Science Co., Ltd.)
Measurement atmosphere: Nitrogen Heating conditions: 20°C/min
(エチレンユニットの比率の測定)
13C-NMRを用いた方法で、環状オレフィン系樹脂中のエチレンユニットの比率(単位:mol%)を測定した。なお、用いた装置及び測定条件は以下の通りである。
(Measurement of ethylene unit ratio)
A ratio (unit: mol %) of ethylene units in the cyclic olefin resin was measured by a method using 13 C-NMR. The apparatus and measurement conditions used are as follows.
[13C-NMRの測定条件]
NMR装置:「BrukerAVANCE600」(Bruker社製)
測定溶媒:1,1,2,2-テトラクロロエタン-d2
測定核種:13C
測定温度:381K
サンプル濃度:80mg/mL
サンプルチューブ径:10mm
積算回数:18000回
パルス繰り返し時間:3秒
[ 13 C-NMR measurement conditions]
NMR device: "Bruker AVANCE600" (manufactured by Bruker)
Measurement solvent: 1,1,2,2-tetrachloroethane- d2
Measurement nuclide: 13 C
Measurement temperature: 381K
Sample concentration: 80 mg/mL
Sample tube diameter: 10mm
Accumulation times: 18000 times Pulse repetition time: 3 seconds
[エチレンユニットの比率の算出方法]
ノルボルネン由来(C1~C7)のシグナル積分値、及びエチレン由来(E)のシグナル積分値から、下記計算式によりノルボルネンの比率Nb(mol%)を算出し、100からその値を引くことで、エチレンユニットの比率を算出した。なお、C1~C7、及びEの位置は、下記式(V)に示す通りである。
[Method for calculating ratio of ethylene unit]
From the signal integral value derived from norbornene (C1 to C7) and the signal integral value derived from ethylene (E), the ratio Nb (mol%) of norbornene is calculated by the following formula, and by subtracting that value from 100, ethylene The unit ratio was calculated. The positions of C1 to C7 and E are as shown in formula (V) below.
<樹脂以外の材料>
・ガラスバルーン:Y12000((株)セイシン企業製、アスペクト比(平均)1.264、メディアン径35μm、真比重0.6)
・ガラス繊維:ECS03T-786H(日本電気硝子(株)製、チョプドストランド、繊維径10μm、長さ3mm、真比重2.6)
・マイカ:AB-25S((株)ヤマグチマイカ製、マイカ、メディアン径25.0μm、真比重2.8)
<Materials other than resin>
・ Glass balloon: Y12000 (manufactured by Seishin Enterprise Co., Ltd., aspect ratio (average) 1.264, median diameter 35 μm, true specific gravity 0.6)
・ Glass fiber: ECS03T-786H (manufactured by Nippon Electric Glass Co., Ltd., chopped strand, fiber diameter 10 μm, length 3 mm, true specific gravity 2.6)
・ Mica: AB-25S (manufactured by Yamaguchi Mica Co., Ltd., mica, median diameter 25.0 μm, true specific gravity 2.8)
<液晶性樹脂組成物の製造>
上記成分を、表1又は表2に示す割合で二軸押出機((株)日本製鋼所製TEX30α型)を用いて、下記のシリンダー温度で溶融混練し、液晶性樹脂組成物ペレットを得た。
〔製造条件〕
シリンダー温度:
350℃:液晶性ポリエステルアミド樹脂(LCP1)を含有する液晶性樹脂組成物の場合
340℃:液晶性ポリエステル樹脂(LCP2)を含有する液晶性樹脂組成物の場合
<Production of liquid crystalline resin composition>
The above components were melt-kneaded at the following cylinder temperature using a twin-screw extruder (TEX30α type manufactured by Japan Steel Works, Ltd.) at the ratios shown in Table 1 or Table 2 to obtain liquid crystalline resin composition pellets. .
[Manufacturing conditions]
Cylinder temperature:
350° C.: For a liquid crystalline resin composition containing a liquid crystalline polyester amide resin (LCP1) 340° C.: For a liquid crystalline resin composition containing a liquid crystalline polyester resin (LCP2)
<溶融粘度>
(株)東洋精機製作所製キャピログラフ1B型を使用し、液晶性樹脂の融点よりも10~20℃高い温度で、内径1mm、長さ20mmのオリフィスを用いて、剪断速度1000/秒で、ISO11443に準拠して、液晶性樹脂組成物の溶融粘度を測定した。なお、具体的な測定温度は、液晶性ポリエステルアミド樹脂(LCP1)を含有する液晶性樹脂組成物については350℃、液晶性ポリエステル樹脂(LCP2)を含有する液晶性樹脂組成物については340℃であった。結果を表1及び表2に示す。
<Melt viscosity>
Using Capilograph Model 1B manufactured by Toyo Seiki Seisakusho Co., Ltd., at a temperature 10 to 20 ° C higher than the melting point of the liquid crystalline resin, using an orifice with an inner diameter of 1 mm and a length of 20 mm, at a shear rate of 1000 / sec, ISO 11443 The melt viscosity of the liquid crystalline resin composition was measured according to the above. The specific measurement temperature is 350° C. for the liquid crystalline resin composition containing the liquid crystalline polyester amide resin (LCP1) and 340° C. for the liquid crystalline resin composition containing the liquid crystalline polyester resin (LCP2). there were. The results are shown in Tables 1 and 2.
<曲げ試験>
下記成形条件で、液晶性樹脂組成物を射出成形して0.8mm厚の成形体を得、ASTM D790に準拠し、曲げ強度、曲げ弾性率、及び曲げ歪を測定した。
[成形条件]
成形機:住友重機械工業(株)、SE100DU
シリンダー温度:
350℃(実施例1~6及び8並びに比較例1~7)
340℃(実施例7)
金型温度:90℃
射出速度:33mm/sec
<Bending test>
The liquid crystalline resin composition was injection molded under the following molding conditions to obtain a 0.8 mm-thick molded body, and the flexural strength, flexural modulus, and flexural strain were measured according to ASTM D790.
[Molding condition]
Molding machine: Sumitomo Heavy Industries, Ltd., SE100DU
Cylinder temperature:
350° C. (Examples 1-6 and 8 and Comparative Examples 1-7)
340°C (Example 7)
Mold temperature: 90°C
Injection speed: 33mm/sec
<誘電特性>
実施例及び比較例のペレットを、成形機(住友重機械工業(株)製 「SE-100DU」)を用いて、以下の成形条件で成形し、80mm×80mm×1mmの平板状試験片を作製した。図1に示す通り、平板状試験片の中央から流動直角方向に80mm×1mm×1mmの試験片を切り出し、これを誘電特性評価用試験片とした。この試験片について、(株)関東電子応用開発製の以下の構成の空洞共振器摂動法複素誘電率評価装置を用いて、1GHzでの比誘電率及び誘電正接を測定した。
スカラーネットワークアナライザー:アジレントテクノロジー8757D
周波数シンセサイザー:アジレントテクノロジー 83650LスイープCWジェネレータ
固定減衰器:アジレントテクノロジー85025Dディテクター
空洞共振器:関東電子応用開発CP431
測定プログラム:関東電子応用開発CPMA-S2/V2
〔成形条件〕
シリンダー温度:
350℃(実施例1~6及び8並びに比較例1~7)
340℃(実施例7)
金型温度:80℃
射出速度:33mm/sec
保圧:60MPa
<Dielectric properties>
The pellets of Examples and Comparative Examples are molded under the following molding conditions using a molding machine ("SE-100DU" manufactured by Sumitomo Heavy Industries, Ltd.) to prepare flat test pieces of 80 mm × 80 mm × 1 mm. bottom. As shown in FIG. 1, a test piece of 80 mm×1 mm×1 mm was cut from the center of the flat test piece in the direction perpendicular to the flow, and this was used as a test piece for evaluating dielectric properties. For this test piece, the relative permittivity and dielectric loss tangent at 1 GHz were measured using a cavity resonator perturbation method complex permittivity evaluation device manufactured by Kanto Denshi Applied Development Co., Ltd. having the following configuration.
Scalar network analyzer: Agilent Technologies 8757D
Frequency synthesizer: Agilent Technologies 83650L sweep CW generator Fixed attenuator: Agilent Technologies 85025D detector Cavity resonator: Kanto Denshi Applied Development CP431
Measurement program: Kanto Denshi Applied Development CPMA-S2/V2
〔Molding condition〕
Cylinder temperature:
350° C. (Examples 1-6 and 8 and Comparative Examples 1-7)
340°C (Example 7)
Mold temperature: 80°C
Injection speed: 33mm/sec
Holding pressure: 60MPa
<はんだ耐熱性>
下記成形条件で、液晶性樹脂組成物を射出成形して120mm×12.7mm×3.2mmの1/8燃焼試験片を得、下記条件でリフローに供し、以下の基準に従って評価した。
○(良好):リフロー前後で試験片の外観に変化はなかった。
△(不良):リフローにより試験片は、表面の光沢が喪失し、又は、粗さが悪化した。
×(極めて不良):リフローにより試験片が溶融し、又は、大きく変形した。
[成形条件]
成形機:住友重機械工業(株)、SE100DU
シリンダー温度:
350℃(実施例1~6及び8並びに比較例1~7)
340℃(実施例7)
金型温度:90℃
射出速度:33mm/sec
[リフロー条件]
測定機:(株)二葉科学製コンベア式熱風循環乾燥機DFC-27-022S
試料送り速度:0.45m/min
リフロー炉通過時間:4分44秒
プレヒートゾーンの温度条件:185℃
リフローゾーンの温度条件:295℃
ピーク温度:258℃
温度が255℃以上であった時間:11秒
<Solder heat resistance>
A liquid crystalline resin composition was injection molded under the following molding conditions to obtain a ⅛ combustion test piece of 120 mm×12.7 mm×3.2 mm, subjected to reflow under the following conditions, and evaluated according to the following criteria.
○ (Good): There was no change in the appearance of the test piece before and after reflow.
Δ (bad): The test piece lost surface gloss or deteriorated in roughness due to reflow.
x (extremely poor): The test piece was melted or greatly deformed by reflow.
[Molding condition]
Molding machine: Sumitomo Heavy Industries, Ltd., SE100DU
Cylinder temperature:
350° C. (Examples 1-6 and 8 and Comparative Examples 1-7)
340°C (Example 7)
Mold temperature: 90°C
Injection speed: 33mm/sec
[Reflow conditions]
Measuring machine: Conveyor type hot air circulation dryer DFC-27-022S manufactured by Futaba Kagaku Co., Ltd.
Sample feed speed: 0.45m/min
Reflow oven passage time: 4 minutes and 44 seconds Preheat zone temperature conditions: 185°C
Temperature condition of reflow zone: 295°C
Peak temperature: 258°C
Time the temperature was above 255°C: 11 seconds
表1に記載の結果から明らかなように、実施例の液晶性樹脂組成物は、誘電特性及び耐熱性に優れ、流動性が良好であった。 As is clear from the results shown in Table 1, the liquid crystalline resin compositions of Examples were excellent in dielectric properties and heat resistance, and had good fluidity.
Claims (5)
(B)環状オレフィン系樹脂、及び
(C)中空フィラー
を含有し、
(A)液晶性樹脂の融点は、300℃以上であり、
(B)環状オレフィン系樹脂のガラス転移温度は、100℃以上であり、
(A)液晶性樹脂と(B)環状オレフィン系樹脂との合計100容量部に対して、
(A)液晶性樹脂の含有量は、55~85容量部、
(B)環状オレフィン系樹脂の含有量は、15~45容量部、
(C)中空フィラーの含有量は、20~75容量部
である液晶性樹脂組成物。 (A) a liquid crystalline resin,
(B) a cyclic olefin-based resin, and (C) a hollow filler,
(A) the liquid crystalline resin has a melting point of 300° C. or higher;
(B) the cyclic olefin resin has a glass transition temperature of 100° C. or higher;
With respect to a total of 100 parts by volume of (A) liquid crystalline resin and (B) cyclic olefin resin,
(A) the content of the liquid crystalline resin is 55 to 85 parts by volume;
(B) the content of the cyclic olefin resin is 15 to 45 parts by volume;
(C) A liquid crystalline resin composition in which the content of the hollow filler is 20 to 75 parts by volume.
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