JP6576808B2 - Liquid crystal polymer - Google Patents
Liquid crystal polymer Download PDFInfo
- Publication number
- JP6576808B2 JP6576808B2 JP2015230430A JP2015230430A JP6576808B2 JP 6576808 B2 JP6576808 B2 JP 6576808B2 JP 2015230430 A JP2015230430 A JP 2015230430A JP 2015230430 A JP2015230430 A JP 2015230430A JP 6576808 B2 JP6576808 B2 JP 6576808B2
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- JP
- Japan
- Prior art keywords
- liquid crystal
- crystal polymer
- acid
- group
- polymerizable monomer
- 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.)
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- 229920000106 Liquid crystal polymer Polymers 0.000 title claims description 102
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 title claims description 100
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 70
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 68
- 239000000178 monomer Substances 0.000 claims description 50
- -1 aromatic dicarboxylic acids Chemical class 0.000 claims description 45
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 38
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 35
- 125000003118 aryl group Chemical group 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 30
- 229920001577 copolymer Polymers 0.000 claims description 27
- 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 claims description 23
- 239000000203 mixture Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims description 16
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 14
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 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 claims description 10
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 claims description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000011256 inorganic filler Substances 0.000 claims description 7
- 239000012766 organic filler Substances 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 6
- NUDSREQIJYWLRA-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=CC=2)=C1 NUDSREQIJYWLRA-UHFFFAOYSA-N 0.000 claims description 5
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 4
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 229960001755 resorcinol Drugs 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 27
- 239000000047 product Substances 0.000 description 22
- 239000008188 pellet Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 19
- 239000011347 resin Substances 0.000 description 19
- 239000000155 melt Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 239000013078 crystal Substances 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000004984 aromatic diamines Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229910052736 halogen Chemical group 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000003513 alkali Substances 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
- 125000003277 amino 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
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical group NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical group C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 description 1
- DDAPSNKEOHDLKB-UHFFFAOYSA-N 1-(2-aminonaphthalen-1-yl)naphthalen-2-amine Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3N)=C(N)C=CC2=C1 DDAPSNKEOHDLKB-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- PFHTYDZPRYLZHX-UHFFFAOYSA-N 2-(2,5-dihydroxyphenyl)benzene-1,4-diol Chemical compound OC1=CC=C(O)C(C=2C(=CC=C(O)C=2)O)=C1 PFHTYDZPRYLZHX-UHFFFAOYSA-N 0.000 description 1
- HQRSOHFIGHYESQ-UHFFFAOYSA-N 2-butan-2-yl-4-[9-(3-butan-2-yl-4-hydroxyphenyl)fluoren-9-yl]phenol Chemical compound C1=C(O)C(C(C)CC)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C(O)=CC=2)C(C)CC)=C1 HQRSOHFIGHYESQ-UHFFFAOYSA-N 0.000 description 1
- VFIWRWAGUSQPKU-UHFFFAOYSA-N 2-butyl-4-[9-(3-butyl-4-hydroxyphenyl)fluoren-9-yl]phenol Chemical compound C1=C(O)C(CCCC)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(CCCC)C(O)=CC=2)=C1 VFIWRWAGUSQPKU-UHFFFAOYSA-N 0.000 description 1
- UQFAPXHGDUABRM-UHFFFAOYSA-N 2-cyclohexyl-4-[9-(3-cyclohexyl-4-hydroxyphenyl)fluoren-9-yl]phenol Chemical compound OC1=CC=C(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C(O)=CC=2)C2CCCCC2)C=C1C1CCCCC1 UQFAPXHGDUABRM-UHFFFAOYSA-N 0.000 description 1
- MQSVWTXCKSCUBT-UHFFFAOYSA-N 2-ethyl-4-[9-(3-ethyl-4-hydroxyphenyl)fluoren-9-yl]phenol Chemical compound C1=C(O)C(CC)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(CC)C(O)=CC=2)=C1 MQSVWTXCKSCUBT-UHFFFAOYSA-N 0.000 description 1
- LODHFNUFVRVKTH-ZHACJKMWSA-N 2-hydroxy-n'-[(e)-3-phenylprop-2-enoyl]benzohydrazide Chemical compound OC1=CC=CC=C1C(=O)NNC(=O)\C=C\C1=CC=CC=C1 LODHFNUFVRVKTH-ZHACJKMWSA-N 0.000 description 1
- BHEUHZKBYVNFKH-UHFFFAOYSA-N 2-tert-butyl-4-[9-(3-tert-butyl-4-hydroxyphenyl)fluoren-9-yl]phenol Chemical compound C1=C(O)C(C(C)(C)C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C(O)=CC=2)C(C)(C)C)=C1 BHEUHZKBYVNFKH-UHFFFAOYSA-N 0.000 description 1
- AJHPGXZOIAYYDW-UHFFFAOYSA-N 3-(2-cyanophenyl)-2-[(2-methylpropan-2-yl)oxycarbonylamino]propanoic acid Chemical compound CC(C)(C)OC(=O)NC(C(O)=O)CC1=CC=CC=C1C#N AJHPGXZOIAYYDW-UHFFFAOYSA-N 0.000 description 1
- VZQSBJKDSWXLKX-UHFFFAOYSA-N 3-(3-hydroxyphenyl)phenol Chemical group OC1=CC=CC(C=2C=C(O)C=CC=2)=C1 VZQSBJKDSWXLKX-UHFFFAOYSA-N 0.000 description 1
- GSYIVQLTSZFJRV-UHFFFAOYSA-N 3-(4-carboxyphenyl)benzoic acid Chemical group C1=CC(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1 GSYIVQLTSZFJRV-UHFFFAOYSA-N 0.000 description 1
- BWBGEYQWIHXDKY-UHFFFAOYSA-N 3-(4-hydroxyphenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=CC(O)=C1 BWBGEYQWIHXDKY-UHFFFAOYSA-N 0.000 description 1
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- LQZZZAFQKXTFKH-UHFFFAOYSA-N 4'-aminobiphenyl-4-ol Chemical group C1=CC(N)=CC=C1C1=CC=C(O)C=C1 LQZZZAFQKXTFKH-UHFFFAOYSA-N 0.000 description 1
- FMRQKJAIESQKBU-UHFFFAOYSA-N 4-(3-amino-7-thiabicyclo[4.1.0]hepta-2,4-dien-6-yl)phenol Chemical compound C1=CC(N)=CC2SC21C1=CC=C(O)C=C1 FMRQKJAIESQKBU-UHFFFAOYSA-N 0.000 description 1
- SVNRPIDQIDMFJX-UHFFFAOYSA-N 4-(4-carboxyphenyl)-3-phenylbenzoic acid Chemical group C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1C1=CC=CC=C1 SVNRPIDQIDMFJX-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical group C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- AHEUDCCTNVTJEP-UHFFFAOYSA-N 4-[9-(4-carboxyphenyl)fluoren-9-yl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1(C=2C=CC(=CC=2)C(O)=O)C2=CC=CC=C2C2=CC=CC=C21 AHEUDCCTNVTJEP-UHFFFAOYSA-N 0.000 description 1
- FLMZHPQIDVOWEJ-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-phenylphenyl)fluoren-9-yl]-2-phenylphenol Chemical compound OC1=CC=C(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C(O)=CC=2)C=2C=CC=CC=2)C=C1C1=CC=CC=C1 FLMZHPQIDVOWEJ-UHFFFAOYSA-N 0.000 description 1
- PSLSQHVPMSZQGS-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-propan-2-ylphenyl)fluoren-9-yl]-2-propan-2-ylphenol Chemical compound C1=C(O)C(C(C)C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C(O)=CC=2)C(C)C)=C1 PSLSQHVPMSZQGS-UHFFFAOYSA-N 0.000 description 1
- GUGCDEVISPTZJD-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-propylphenyl)fluoren-9-yl]-2-propylphenol Chemical compound C1=C(O)C(CCC)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(CCC)C(O)=CC=2)=C1 GUGCDEVISPTZJD-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-PZFLKRBQSA-N 4-amino-3,5-ditritiobenzoic acid Chemical compound [3H]c1cc(cc([3H])c1N)C(O)=O ALYNCZNDIQEVRV-PZFLKRBQSA-N 0.000 description 1
- ABJQKDJOYSQVFX-UHFFFAOYSA-N 4-aminonaphthalen-1-ol Chemical compound C1=CC=C2C(N)=CC=C(O)C2=C1 ABJQKDJOYSQVFX-UHFFFAOYSA-N 0.000 description 1
- QGNGOGOOPUYKMC-UHFFFAOYSA-N 4-hydroxy-6-methylaniline Chemical compound CC1=CC(O)=CC=C1N QGNGOGOOPUYKMC-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-M 4-hydroxybenzoate Chemical compound OC1=CC=C(C([O-])=O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-M 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 1
- NZTPZUIIYNYZKT-UHFFFAOYSA-N 6-aminonaphthalene-2-carboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(N)=CC=C21 NZTPZUIIYNYZKT-UHFFFAOYSA-N 0.000 description 1
- JCJUKCIXTRWAQY-UHFFFAOYSA-N 6-hydroxynaphthalene-1-carboxylic acid Chemical compound OC1=CC=C2C(C(=O)O)=CC=CC2=C1 JCJUKCIXTRWAQY-UHFFFAOYSA-N 0.000 description 1
- FSXKKRVQMPPAMQ-UHFFFAOYSA-N 7-hydroxynaphthalene-2-carboxylic acid Chemical compound C1=CC(O)=CC2=CC(C(=O)O)=CC=C21 FSXKKRVQMPPAMQ-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- GAVUQMVOBQTWMZ-UHFFFAOYSA-N C(=O)(O)C1=C(C=C(C=C1)C1(C2=CC=CC=C2C=2C=CC=CC12)C1=CC(=C(C=C1)C(=O)O)C(C)(C)C)C(C)(C)C Chemical compound C(=O)(O)C1=C(C=C(C=C1)C1(C2=CC=CC=C2C=2C=CC=CC12)C1=CC(=C(C=C1)C(=O)O)C(C)(C)C)C(C)(C)C GAVUQMVOBQTWMZ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
本発明は、誘電特性に優れた液晶ポリマーに関する。 The present invention relates to a liquid crystal polymer having excellent dielectric properties.
サーモトロピック液晶ポリマー（以下、液晶ポリマーまたはＬＣＰと略称する）は、機械特性、成形性、耐薬品性、ガス遮断性、耐湿性、電気特性などに優れるため、多種多様な分野の部品に用いられている。特に、耐熱性、薄肉成形性および絶縁性に優れることから、電子部品等への使用が拡大しつつある。 Thermotropic liquid crystal polymers (hereinafter abbreviated as liquid crystal polymers or LCPs) are excellent in mechanical properties, moldability, chemical resistance, gas barrier properties, moisture resistance, electrical properties, etc., and are therefore used in parts in a wide variety of fields. ing. In particular, since it is excellent in heat resistance, thin-wall formability, and insulation, its use for electronic parts and the like is expanding.
近年、高度情報化社会の発展とともに、パーソナル・コンピューターや携帯電話等の情報・通信分野において、情報通信機器の伝送情報量および伝達速度が爆発的に増大している。特に、マイクロ波およびミリ波の高周波領域において適応できる高性能な高周波用電子部品のニーズがより強くなってきている。 In recent years, with the development of a highly information-oriented society, the amount of information transmitted and the transmission speed of information communication devices have increased explosively in the field of information and communication such as personal computers and mobile phones. In particular, the need for high-performance high-frequency electronic components that can be applied in the high-frequency region of microwaves and millimeter waves is becoming stronger.
しかしながら、誘電率の高い液晶ポリマーを電気コネクタの基板として使用した場合、高周波信号が減衰してしまい、信号伝播速度が低下するといった問題が生じる。そのため、これらの電子部品に使用する液晶ポリマーは、低誘電率であることが求められている。 However, when a liquid crystal polymer having a high dielectric constant is used as the substrate of the electrical connector, the high-frequency signal is attenuated, resulting in a problem that the signal propagation speed is reduced. Therefore, the liquid crystal polymer used for these electronic components is required to have a low dielectric constant.
一般に、液晶ポリマーにガラス繊維およびガラスバルーンが配合された液晶性ポリエステル樹脂組成物（特許文献１）は誘電率が低いことが知られている。また、液晶ポリマーの誘電率を低下させるために、アスペクト比４以上の繊維状充填材および特定粒子径の無機球状中空体が配合された液晶ポリエステル組成物が提案されている（特許文献２）。 In general, it is known that a liquid crystalline polyester resin composition (Patent Document 1) in which glass fibers and glass balloons are blended with a liquid crystal polymer has a low dielectric constant. Moreover, in order to reduce the dielectric constant of a liquid crystal polymer, a liquid crystal polyester composition in which a fibrous filler having an aspect ratio of 4 or more and an inorganic spherical hollow body having a specific particle diameter have been proposed (Patent Document 2).
しかしながら、上記液晶ポリエステル組成物は、液晶ポリマー中でガラスビーズや無機球状中空体が破損したり、均一に分散しないといったことにより、組成物の物性が低下したり、物性にムラが発生するなどの問題があった。 However, the liquid crystal polyester composition is such that the glass beads and the inorganic spherical hollow body are broken in the liquid crystal polymer, or the physical properties of the composition are deteriorated or the physical properties are uneven due to non-uniform dispersion. There was a problem.
したがって、液晶ポリマーの物性を低下させることなく、樹脂自体の誘電率が低く、誘電特性に優れた液晶ポリマーが求められていた。 Therefore, there has been a demand for a liquid crystal polymer having a low dielectric constant and excellent dielectric properties without deteriorating the physical properties of the liquid crystal polymer.
本発明の目的は、液晶ポリマーの物性を低下させることなく、樹脂自体が低誘電率化された、誘電特性に優れた液晶ポリマーを提供することにある。 An object of the present invention is to provide a liquid crystal polymer having excellent dielectric properties in which the resin itself has a low dielectric constant without deteriorating the physical properties of the liquid crystal polymer.
本発明者等は、液晶ポリマーの低誘電率化について鋭意検討した結果、フルオレン構造を有するビフェニル化合物に由来する繰返し単位を液晶ポリマーの構成成分とすることによって、得られる液晶ポリマーの誘電率が低下することを見出し、本発明を完成させるに至った。 As a result of diligent studies on the reduction of the dielectric constant of the liquid crystal polymer, the present inventors have reduced the dielectric constant of the liquid crystal polymer obtained by using a repeating unit derived from a biphenyl compound having a fluorene structure as a constituent component of the liquid crystal polymer. As a result, the present invention has been completed.
すなわち本発明は、式（Ｉ）で表されるビフェニルフルオレン化合物、およびそれらの反応性誘導体からなる群から選択される重合性単量体（Ａ）と、他の重合性単量体（Ｂ）とから構成される液晶ポリマーを提供する。 That is, the present invention relates to a polymerizable monomer (A) selected from the group consisting of a biphenylfluorene compound represented by the formula (I) and a reactive derivative thereof, and another polymerizable monomer (B). A liquid crystal polymer composed of:
本発明の液晶ポリマーは、液晶ポリマーの物性を低下させることなく、樹脂自体が低誘電率化されているため、高周波用電子部品などの成形用樹脂として好適に用いられる。 The liquid crystal polymer of the present invention is suitably used as a molding resin for high-frequency electronic parts and the like because the resin itself has a low dielectric constant without reducing the properties of the liquid crystal polymer.
本発明の液晶ポリマーは、異方性溶融相を形成するポリエステルまたはポリエステルアミドであり、当該技術分野においてサーモトロピック液晶ポリエステル又はサーモトロピック液晶ポリエステルアミドと呼ばれるものであれば特に限定されない。 The liquid crystal polymer of the present invention is a polyester or polyester amide that forms an anisotropic molten phase, and is not particularly limited as long as it is called a thermotropic liquid crystal polyester or a thermotropic liquid crystal polyester amide in the technical field.
本明細書において、重合性単量体の「反応性誘導体」とは、目的とする構成単位を導入できる反応性を有する単量体の誘導体を言うものとする。本発明において用い得る好適なフルオレン構造を含むビスフェノール化合物またはジカルボン酸化合物の反応性誘導体としては、フルオレン構造を含むビスフェノール化合物またはジカルボン酸化合物のアルキル、アルコキシまたはハロゲン置換体、アシル化物、エステル誘導体、酸ハロゲン化物などのエステル形成性誘導体、ならびにこれら置換体のアシル化物、エステル誘導体、酸ハロゲン化物などのエステル形成性誘導体が例示される。置換基としてのアルキル基またはアルコキシ基としては、炭素原子数６までのものが好適に用いられる。式（Ｉ）で表されるフルオレン構造を含むビスフェノール化合物またはジカルボン酸化合物、およびその反応性誘導体からなる群から選択される重合性単量体（Ａ）として、１種のみの化合物を用いてもよく、２種以上の化合物を組み合わせて用いてもよい。 In the present specification, the “reactive derivative” of a polymerizable monomer shall mean a derivative of a monomer having reactivity capable of introducing a target structural unit. Suitable reactive derivatives of bisphenol compounds or dicarboxylic acid compounds containing a fluorene structure that can be used in the present invention include alkyl, alkoxy or halogen substituted products, acylated products, ester derivatives, acids of bisphenol compounds or dicarboxylic acid compounds containing a fluorene structure. Examples thereof include ester-forming derivatives such as halides, and ester-forming derivatives such as acylated products, ester derivatives, and acid halides of these substituents. As the alkyl group or alkoxy group as a substituent, those having up to 6 carbon atoms are preferably used. Even if only one kind of compound is used as the polymerizable monomer (A) selected from the group consisting of a bisphenol compound or dicarboxylic acid compound containing a fluorene structure represented by the formula (I) and a reactive derivative thereof. Alternatively, two or more compounds may be used in combination.
本明細書において、「芳香族」とは縮合環数が４までの芳香族基を含む化合物を意味するものとする。また、「脂肪族」とは、炭素原子数２〜１２の、分岐を有していてもよい飽和または不飽和炭素鎖を含む化合物を示すものとする。 In the present specification, “aromatic” means a compound containing an aromatic group having up to 4 condensed rings. The term “aliphatic” refers to a compound containing a saturated or unsaturated carbon chain having 2 to 12 carbon atoms, which may have a branch.
本発明の液晶ポリマーに用いる、式（Ｉ）で表されるフルオレン構造を含むビスフェノール化合物またはジカルボン酸化合物としては、９，９−ビス（４−ヒドロキシフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−エチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−ｎ−プロピルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−イソプロピルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−ｎ−ブチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−ｓｅｃ−ブチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−ｔｅｒｔ−ブチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−シクロヘキシルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−フェニルフェニル）フルオレン、９，９−ビス（４−カルボキシフェニル）フルオレン、９，９−ビス（４−カルボキシ−３−メチルフェニル）フルオレン、９，９−ビス（４−カルボキシ−３−エチルフェニル）フルオレン、９，９−ビス（４−カルボキシ−３−ｎ−プロピルフェニル）フルオレン、９，９−ビス（４−カルボキシ−３−イソプロピルフェニル）フルオレン、９，９−ビス（４−カルボキシ−３−ｎ−ブチルフェニル）フルオレン、９，９−ビス（４−カルボキシ−３−ｓｅｃ−ブチルフェニル）フルオレン、９，９−ビス（４−カルボキシ−３−ｔｅｒｔ−ブチルフェニル）フルオレン、９，９−ビス（４−カルボキシ−３−シクロヘキシルフェニル）フルオレン、９，９−ビス（４−カルボキシ−３−フェニルフェニル）フルオレン等が挙げられ、液晶ポリマーの低誘電率化効果に優れる点で、９，９−ビス（４−ヒドロキシフェニル）フルオレンまたは９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンが好ましい。 Examples of the bisphenol compound or dicarboxylic acid compound having a fluorene structure represented by the formula (I) used in the liquid crystal polymer of the present invention include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4- Hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-n-propylphenyl) fluorene, 9,9-bis (4-hydroxy-3-isopropylphenyl) fluorene, 9,9-bis (4-hydroxy-3-n-butylphenyl) fluorene, 9,9-bis (4-hydroxy-3-sec-butylphenyl) fluorene, 9,9-bis (4-hydroxy-3-tert-butylphenyl) fluorene, 9,9-bis (4-hydroxy -3-cyclohexylphenyl) fluorene, 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene, 9,9-bis (4-carboxyphenyl) fluorene, 9,9-bis (4-carboxy-3- Methylphenyl) fluorene, 9,9-bis (4-carboxy-3-ethylphenyl) fluorene, 9,9-bis (4-carboxy-3-n-propylphenyl) fluorene, 9,9-bis (4-carboxy) -3-isopropylphenyl) fluorene, 9,9-bis (4-carboxy-3-n-butylphenyl) fluorene, 9,9-bis (4-carboxy-3-sec-butylphenyl) fluorene, 9,9- Bis (4-carboxy-3-tert-butylphenyl) fluorene, 9,9-bis (4-carboxy-3-cyclo Xylphenyl) fluorene, 9,9-bis (4-carboxy-3-phenylphenyl) fluorene, and the like, and 9,9-bis (4-hydroxyphenyl) is excellent in reducing the dielectric constant of the liquid crystal polymer. Fluorene or 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred.
本発明の液晶ポリマーに用いる、式（Ｉ）で表されるフルオレン構造を含むビスフェノール化合物またはジカルボン酸化合物およびその反応性誘導体からなる群から選択される重合性単量体（Ａ）の合計量は、他の重合性単量体（Ｂ）の合計量１００モル部に対して、０．０１〜３０モル部であることが好ましく、０．１〜２０モル部であることがより好ましく、０．５〜１５モル部であることがさらに好ましい。重合性単量体（Ａ）の合計量が他の重合性単量体（Ｂ）の合計量１００モル部に対して３０モル部を超えると、重合が困難になる傾向がある。重合性単量体（Ａ）の合計量が他の重合性単量体（Ｂ）の合計量１００モル部に対して０．０１モル部未満であると、低誘電率化効果が得られない傾向がある。 The total amount of the polymerizable monomer (A) selected from the group consisting of a bisphenol compound or dicarboxylic acid compound containing a fluorene structure represented by formula (I) and a reactive derivative thereof used in the liquid crystal polymer of the present invention is: The amount of the other polymerizable monomer (B) is preferably 0.01 to 30 mol parts, more preferably 0.1 to 20 mol parts, with respect to 100 mol parts. More preferably, it is 5-15 mol part. When the total amount of the polymerizable monomer (A) exceeds 30 mol parts with respect to 100 mol parts of the total amount of the other polymerizable monomers (B), the polymerization tends to be difficult. When the total amount of the polymerizable monomer (A) is less than 0.01 mol part with respect to 100 mol parts of the total amount of the other polymerizable monomers (B), the effect of reducing the dielectric constant cannot be obtained. Tend.
本発明の液晶ポリマーに用いる他の重合性単量体（Ｂ）としては、従来の液晶ポリマーに用いられる単量体、例えば芳香族ヒドロキシカルボン酸、芳香族ジカルボン酸、芳香族ジオール、芳香族アミノカルボン酸、芳香族ヒドロキシアミン、芳香族ジアミン、脂肪族ジオールおよび脂肪族ジカルボン酸が挙げられる。これら化合物は１種のみを用いてもよく、２種以上を組み合わせて用いてもよいが、ヒドロキシ基および／またはアミノ基を有する単量体を少なくとも１種用いることが望ましい。 Examples of the other polymerizable monomer (B) used in the liquid crystal polymer of the present invention include monomers used in conventional liquid crystal polymers, such as aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic amino acids. Carboxylic acids, aromatic hydroxyamines, aromatic diamines, aliphatic diols and aliphatic dicarboxylic acids. These compounds may be used alone or in combination of two or more, but it is desirable to use at least one monomer having a hydroxy group and / or an amino group.
本発明の液晶ポリマーに用いる他の重合性単量体（Ｂ）は、前記化合物の１種以上が結合してなるオリゴマーであってもよい。なお、本明細書および特許請求の範囲における、他の重合性単量体（Ｂ）の量については、「重合性単量体」をオリゴマーとして用いる場合であっても、当該オリゴマーを構成する単量体ユニットに基づいて算出するものとする。 The other polymerizable monomer (B) used in the liquid crystal polymer of the present invention may be an oligomer formed by bonding one or more of the above compounds. The amount of the other polymerizable monomer (B) in the present specification and claims is the same as that of the oligomer constituting the oligomer even when “polymerizable monomer” is used as the oligomer. It shall be calculated based on the mass unit.
芳香族ヒドロキシカルボン酸の具体例としては、４−ヒドロキシ安息香酸、３−ヒドロキシ安息香酸、２−ヒドロキシ安息香酸、６−ヒドロキシ−２−ナフトエ酸、２−ヒドロキシ−５−ナフトエ酸、２−ヒドロキシ−７−ナフトエ酸、２−ヒドロキシ−３−ナフトエ酸、４’−ヒドロキシフェニル−４−安息香酸、３’−ヒドロキシフェニル−４−安息香酸、４’−ヒドロキシフェニル−３−安息香酸およびそれらのアルキル、アルコキシまたはハロゲン置換体ならびにこれらのアシル化物、エステル誘導体、酸ハロゲン化物などのエステル形成性誘導体等が挙げられる。これらの中でも、４−ヒドロキシ安息香酸もしくは６−ヒドロキシ−２−ナフトエ酸またはその組み合わせが、得られる液晶ポリマーの耐熱性および機械強度ならびに融点を調節し易いという点でより好ましい。なお、本発明における芳香族ヒドロキシカルボン酸には、上記式（Ｉ）で示される化合物は包含されないものとする。 Specific examples of the aromatic hydroxycarboxylic acid include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 2-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 2-hydroxy-5-naphthoic acid, 2-hydroxy -7-naphthoic acid, 2-hydroxy-3-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid and their Examples thereof include alkyl, alkoxy or halogen-substituted products, and ester-forming derivatives thereof such as acylated products, ester derivatives, and acid halides. Among these, 4-hydroxybenzoic acid or 6-hydroxy-2-naphthoic acid or a combination thereof is more preferable in that the heat resistance and mechanical strength and melting point of the obtained liquid crystal polymer can be easily adjusted. In the present invention, the aromatic hydroxycarboxylic acid does not include the compound represented by the above formula (I).
芳香族ジカルボン酸の具体例としては、テレフタル酸、イソフタル酸、２，６−ナフタレンジカルボン酸、１，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸、４，４’−ジカルボキシビフェニル、３，４’−ジカルボキシビフェニルおよび４，４’−ジカルボキシターフェニル、これらのアルキル、アルコキシまたはハロゲン置換体ならびにそれらのエステル誘導体、酸ハロゲン化物などのエステル形成性誘導体等が挙げられる。これらの中でも、テレフタル酸、イソフタル酸および２，６−ナフタレンジカルボン酸が好適に用いられ、特に得られる液晶ポリマーの耐熱性を効果的に高められる点で、テレフタル酸が好ましい。なお、本発明における芳香族ジカルボン酸には、上記式（Ｉ）で示される化合物は包含されないものとする。 Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl, 3 , 4′-dicarboxybiphenyl and 4,4′-dicarboxyterphenyl, alkyl, alkoxy or halogen-substituted products thereof, ester derivatives thereof, ester-forming derivatives such as acid halides, and the like. Among these, terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid are preferably used, and terephthalic acid is particularly preferable because the heat resistance of the obtained liquid crystal polymer can be effectively enhanced. The aromatic dicarboxylic acid in the present invention does not include the compound represented by the above formula (I).
芳香族ジオールの具体例としては、ハイドロキノン、レゾルシン、２，６−ジヒドロキシナフタレン、２，７−ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレン、３，３’−ジヒドロキシビフェニル、３，４’−ジヒドロキシビフェニル、４，４’−ジヒドロキシビフェニル、４，４’−ジヒドロキシビフェノールエーテル、２，２’−ジヒドロキシビナフチルおよびビスフェノールＡ、これらのアルキル、アルコキシまたはハロゲン置換体ならびにそれらのアシル化物などのエステル形成性誘導体等が挙げられる。これらの中でも、ハイドロキノン、レゾルシン、４，４’−ジヒドロキシビフェニル、２，６−ジヒドロキシナフタレンが好適に用いられ、特に重合時の反応性に優れる点において、ハイドロキノン、４，４’−ジヒドロキシビフェニルまたは２，６−ジヒドロキシナフタレンが好ましい。なお、本発明における芳香族ジオールには、上記式（Ｉ）で示される化合物は包含されないものとする。 Specific examples of the aromatic diol include hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 3,3′-dihydroxybiphenyl, 3,4′-dihydroxybiphenyl, Ester-forming derivatives such as 4,4′-dihydroxybiphenyl, 4,4′-dihydroxybiphenol ether, 2,2′-dihydroxybinaphthyl and bisphenol A, alkyl, alkoxy or halogen substituted products thereof, and acylated products thereof Can be mentioned. Among these, hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, and 2,6-dihydroxynaphthalene are preferably used. In particular, hydroquinone, 4,4′-dihydroxybiphenyl, or 2 in terms of excellent reactivity during polymerization. , 6-Dihydroxynaphthalene is preferred. In the present invention, the aromatic diol does not include the compound represented by the above formula (I).
芳香族アミノカルボン酸の具体例としては、４−アミノ安息香酸、３−アミノ安息香酸、６−アミノ−２−ナフトエ酸、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにそれらのアシル化物、エステル誘導体、酸ハロゲン化物などのエステル形成性誘導体等が挙げられる。 Specific examples of the aromatic aminocarboxylic acid include 4-aminobenzoic acid, 3-aminobenzoic acid, 6-amino-2-naphthoic acid, their alkyl, alkoxy or halogen-substituted products, and acylated products and ester derivatives thereof. And ester-forming derivatives such as acid halides.
芳香族ヒドロキシアミンの具体例としては、４−アミノフェノール、Ｎ−メチル−４−アミノフェノール、３−アミノフェノール、３−メチル−４−アミノフェノール、４−アミノ−１−ナフトール、４−アミノ−４’−ヒドロキシビフェニル、４−アミノ−４’−ヒドロキシビフェニルエーテル、４−アミノ−４’−ヒドロキシビフェニルメタン、４−アミノ−４’−ヒドロキシビフェニルスルフィドおよび２，２’−ジアミノビナフチル、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにそれらのアシル化物などのエステル形成性誘導体等が挙げられる。これらの中でも、４−アミノフェノールが得られる液晶ポリマーの耐熱性および機械強度のバランスをとりやすいことから好ましく用いられる。 Specific examples of the aromatic hydroxyamine include 4-aminophenol, N-methyl-4-aminophenol, 3-aminophenol, 3-methyl-4-aminophenol, 4-amino-1-naphthol, 4-amino- 4'-hydroxybiphenyl, 4-amino-4'-hydroxybiphenyl ether, 4-amino-4'-hydroxybiphenylmethane, 4-amino-4'-hydroxybiphenyl sulfide and 2,2'-diaminobinaphthyl, their alkyl , Alkoxy- or halogen-substituted products, and ester-forming derivatives such as acylated products thereof. Among these, 4-aminophenol is preferably used because it easily balances the heat resistance and mechanical strength of the liquid crystal polymer from which 4-aminophenol is obtained.
芳香族ジアミンの具体例としては、１，４−フェニレンジアミン、１，３−フェニレンジアミン、１，５−ジアミノナフタレン、１，８−ジアミノナフタレン、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにそれらのアシル化物などのアミド形成性誘導体等が挙げられる。 Specific examples of the aromatic diamine include 1,4-phenylenediamine, 1,3-phenylenediamine, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, alkyl, alkoxy or halogen substituted products thereof, and their Examples include amide-forming derivatives such as acylated products.
脂肪族ジオールの具体例としては、エチレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオール、ならびにそれらのアシル化物等が挙げられる。また、ポリエチレンテレフタレートやポリブチレンテレフタレートなどの脂肪族ジオールを含有するポリマーを、前記の芳香族オキシカルボン酸、芳香族ジカルボン酸、芳香族ジオールおよびそれらのアシル化物、エステル誘導体、酸ハロゲン化物などと反応させてもよい。 Specific examples of the aliphatic diol include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and acylated products thereof. Also, polymers containing aliphatic diols such as polyethylene terephthalate and polybutylene terephthalate react with the above aromatic oxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols and their acylated products, ester derivatives, acid halides, etc. You may let them.
脂肪族ジカルボン酸の具体例としては、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカン二酸等が挙げられる。これらの中でも、シュウ酸、コハク酸、アジピン酸、スベリン酸、セバシン酸、ドデカン二酸が重合時の反応性に優れることから好ましく用いられる。 Specific examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid and the like. Among these, oxalic acid, succinic acid, adipic acid, suberic acid, sebacic acid, and dodecanedioic acid are preferably used because of excellent reactivity during polymerization.
本発明の液晶ポリマーは、本発明の目的を損なわない範囲で、チオエステル結合を含むものであってもよい。このような結合を与える単量体としては、メルカプト芳香族カルボン酸、芳香族ジチオールおよびヒドロキシ芳香族チオールなどが挙げられる。これらの単量体の使用量は、他の重合性単量体（Ｂ）の合計量に対して１０モル部以下であるのが好ましい。 The liquid crystal polymer of the present invention may contain a thioester bond as long as the object of the present invention is not impaired. Examples of the monomer that gives such a bond include mercapto aromatic carboxylic acid, aromatic dithiol, and hydroxy aromatic thiol. It is preferable that the usage-amount of these monomers is 10 mol part or less with respect to the total amount of another polymerizable monomer (B).
他の重合性単量体（Ｂ）として、芳香族ヒドロキシカルボン酸、芳香族ジカルボン酸、芳香族ジオール、芳香族アミノカルボン酸、芳香族ヒドロキシアミン、芳香族ジアミン、脂肪族ジオールおよび脂肪族ジカルボン酸からなる群から選択される２種以上の化合物を併用することは、本発明の好ましい態様の一つである。これら重合性単量体のうち、芳香族ヒドロキシカルボン酸を含む組合せがより好適に用いられ、芳香族ヒドロキシカルボン酸、芳香族ジカルボン酸および芳香族ジオールを含む組合せがさらに好適に用いられる。これらの中でも、他の重合性単量体（Ｂ）が４−ヒドロキシ安息香酸、６−ヒドロキシ−２−ナフトエ酸、芳香族ジカルボン酸および芳香族ジオールである組合せが特に好適に用いられる。 As other polymerizable monomer (B), aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic aminocarboxylic acid, aromatic hydroxyamine, aromatic diamine, aliphatic diol and aliphatic dicarboxylic acid The combined use of two or more compounds selected from the group consisting of is one of the preferred embodiments of the present invention. Among these polymerizable monomers, a combination containing an aromatic hydroxycarboxylic acid is more preferably used, and a combination containing an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid and an aromatic diol is more preferably used. Among these, a combination in which the other polymerizable monomer (B) is 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, aromatic dicarboxylic acid and aromatic diol is particularly preferably used.
本発明の液晶ポリマーに用いる他の重合性単量体（Ｂ）の具体例としては、例えば下記の組み合わせからなるものが挙げられる：
１）４−ヒドロキシ安息香酸／６−ヒドロキシ−２−ナフトエ酸共重合体
２）４−ヒドロキシ安息香酸／テレフタル酸／４，４’−ジヒドロキシビフェニル共重合体
３）４−ヒドロキシ安息香酸／テレフタル酸／イソフタル酸／４，４’−ジヒドロキシビフェニル共重合体
４）４−ヒドロキシ安息香酸／テレフタル酸／イソフタル酸／４，４’−ジヒドロキシビフェニル／ハイドロキノン共重合体
５）４−ヒドロキシ安息香酸／テレフタル酸／ハイドロキノン共重合体
６）４−ヒドロキシ安息香酸／テレフタル酸／４，４’−ジヒドロキシビフェニル／ハイドロキノン共重合体
７）６−ヒドロキシ−２−ナフトエ酸／テレフタル酸／ハイドロキノン共重合体
８）４−ヒドロキシ安息香酸／６−ヒドロキシ−２−ナフトエ酸／テレフタル酸／４，４’−ジヒドロキシビフェニル共重合体
９）６−ヒドロキシ−２−ナフトエ酸／テレフタル酸／４，４’−ジヒドロキシビフェニル共重合体
１０）４−ヒドロキシ安息香酸／６−ヒドロキシ−２−ナフトエ酸／テレフタル酸／ハイドロキノン共重合体
１１）４−ヒドロキシ安息香酸／６−ヒドロキシ−２−ナフトエ酸／テレフタル酸／ハイドロキノン／４，４’−ジヒドロキシビフェニル共重合体
１２）４−ヒドロキシ安息香酸／２，６−ナフタレンジカルボン酸／４，４’−ジヒドロキシビフェニル共重合体
１３）４−ヒドロキシ安息香酸／テレフタル酸／２，６−ナフタレンジカルボン酸／ハイドロキノン共重合体
１４）４−ヒドロキシ安息香酸／２，６−ナフタレンジカルボン酸／ハイドロキノン共重合体
１５）４−ヒドロキシ安息香酸／６−ヒドロキシ−２−ナフトエ酸／２，６−ナフタレンジカルボン酸／ハイドロキノン共重合体
１６）４−ヒドロキシ安息香酸／テレフタル酸／２，６−ナフタレンジカルボン酸／ハイドロキノン／４，４’−ジヒドロキシビフェニル共重合体
１７）４−ヒドロキシ安息香酸／テレフタル酸／４−アミノフェノール共重合体
１８）６−ヒドロキシ−２−ナフトエ酸／テレフタル酸／４−アミノフェノール共重合体
１９）４−ヒドロキシ安息香酸／６−ヒドロキシ−２−ナフトエ酸／テレフタル酸／４−アミノフェノール共重合体
２０）４−ヒドロキシ安息香酸／テレフタル酸／４，４’−ジヒドロキシビフェニル ／４−アミノフェノール共重合体
２１）４−ヒドロキシ安息香酸／テレフタル酸／エチレングリコール共重合体
２２）４−ヒドロキシ安息香酸／テレフタル酸／４，４’−ジヒドロキシビフェニル／エチレングリコール共重合体
２３）４−ヒドロキシ安息香酸／６−ヒドロキシ−２−ナフトエ酸／テレフタル酸／エチレングリコール共重合体
２４）４−ヒドロキシ安息香酸／６−ヒドロキシ−２−ナフトエ酸／テレフタル酸／４，４’−ジヒドロキシビフェニル／エチレングリコール共重合体
２５）４−ヒドロキシ安息香酸／テレフタル酸／２，６−ナフタレンジカルボン酸／４，４’−ジヒドロキシビフェニル共重合体。
Specific examples of the other polymerizable monomer (B) used in the liquid crystal polymer of the present invention include, for example, those comprising the following combinations:
1) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid copolymer 2) 4-hydroxybenzoic acid / terephthalic acid / 4,4′-dihydroxybiphenyl copolymer 3) 4-hydroxybenzoic acid / terephthalic acid / Isophthalic acid / 4,4′-dihydroxybiphenyl copolymer 4) 4-hydroxybenzoic acid / terephthalic acid / isophthalic acid / 4,4′-dihydroxybiphenyl / hydroquinone copolymer 5) 4-hydroxybenzoic acid / terephthalic acid / Hydroquinone copolymer 6) 4-hydroxybenzoic acid / terephthalic acid / 4,4′-dihydroxybiphenyl / hydroquinone copolymer 7) 6-hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone copolymer 8) 4- Hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / 4,4 ′ Dihydroxybiphenyl copolymer 9) 6-hydroxy-2-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl copolymer 10) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone Copolymer 11) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone / 4,4′-dihydroxybiphenyl copolymer 12) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / 4,4′-dihydroxybiphenyl copolymer 13) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer 14) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / Hydroquinone Copolymer 15) 4-Hydroxybenzoic acid / 6-H Droxy-2-naphthoic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer 16) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone / 4,4′-dihydroxybiphenyl copolymer 17) 4-hydroxybenzoic acid / terephthalic acid / 4-aminophenol copolymer 18) 6-hydroxy-2-naphthoic acid / terephthalic acid / 4-aminophenol copolymer 19) 4-hydroxybenzoic acid / 6-hydroxy 2-naphthoic acid / terephthalic acid / 4-aminophenol copolymer 20) 4-hydroxybenzoic acid / terephthalic acid / 4,4′-dihydroxybiphenyl / 4-aminophenol copolymer 21) 4-hydroxybenzoic acid / Terephthalic acid / ethylene glycol copolymer 22) 4-hydroxybenzoate Acid / terephthalic acid / 4,4′-dihydroxybiphenyl / ethylene glycol copolymer 23) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / ethylene glycol copolymer 24) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / 4,4′-dihydroxybiphenyl / ethylene glycol copolymer 25) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / 4,4′- Dihydroxybiphenyl copolymer.
これらの中でも、１０）、１１）および１５）のモノマー構成単位からなる液晶ポリマーが好ましい。また、上記の液晶ポリマーは単独で用いてもよく、２種以上をブレンドして用いてもよい。 Among these, liquid crystal polymers composed of the monomer structural units of 10), 11) and 15) are preferable. Moreover, said liquid crystal polymer may be used independently, and 2 or more types may be blended and used for it.
以下、本発明の液晶ポリマーの製造方法について説明する。 Hereinafter, the manufacturing method of the liquid crystal polymer of this invention is demonstrated.
本発明の液晶ポリマーを製造する方法に特に制限はなく、式（Ｉ）で表されるフルオレン構造を含むビスフェノール化合物またはジカルボン酸化合物およびその反応性誘導体からなる群から選択される重合性単量体（Ａ）ならびに他の重合性単量体（Ｂ）を、エステル結合またはアミド結合を形成させる公知の縮重合方法、たとえば溶融アシドリシス法、スラリー重合法などに供することにより本発明の液晶ポリマーを得ることができる。 The method for producing the liquid crystal polymer of the present invention is not particularly limited, and is a polymerizable monomer selected from the group consisting of a bisphenol compound or dicarboxylic acid compound containing a fluorene structure represented by formula (I) and a reactive derivative thereof. The liquid crystal polymer of the present invention is obtained by subjecting (A) and other polymerizable monomer (B) to a known condensation polymerization method for forming an ester bond or an amide bond, such as a melt acididation method or a slurry polymerization method. be able to.
溶融アシドリシス法は、本発明の液晶ポリマーを製造するのに好ましい方法である。この方法は、最初に重合性単量体を加熱して反応物質の溶融溶液を形成し、次いで縮重合反応を続けて溶融ポリマーを得るものである。なお、縮合の最終段階で副生する揮発物（たとえば酢酸、水など）の除去を容易にするために真空を適用してもよい。 The melt acidolysis method is a preferred method for producing the liquid crystal polymer of the present invention. In this method, a polymerizable monomer is first heated to form a molten solution of a reactant, and then a condensation polymerization reaction is continued to obtain a molten polymer. A vacuum may be applied to facilitate removal of volatiles (for example, acetic acid, water, etc.) by-produced in the final stage of condensation.
スラリー重合法とは、熱交換流体の存在下で重合性単量体を反応させる方法であって、固体生成物は熱交換媒質中に懸濁した状態で得られる。 The slurry polymerization method is a method in which a polymerizable monomer is reacted in the presence of a heat exchange fluid, and a solid product is obtained in a state suspended in a heat exchange medium.
溶融アシドリシス法およびスラリー重合法のいずれの場合においても、液晶ポリマーを製造する際に使用される重合性単量体（Ａ）ならびに他の重合性単量体（Ｂ）はいずれも、常温において、ヒドロキシル基および／またはアミノ基をアシル化した変性形態、すなわち低級アシル化物として反応に供することもできる。 In any case of the melt acidolysis method and the slurry polymerization method, the polymerizable monomer (A) and the other polymerizable monomer (B) used in producing the liquid crystal polymer are both at room temperature, The hydroxyl group and / or amino group can be subjected to the reaction as a modified form obtained by acylation, that is, a lower acylated product.
低級アシル基は炭素原子数２〜５のものが好ましく、炭素原子数２または３のものがより好ましい。特に好ましくは前記重合性単量体のアセチル化物を反応に用いる方法が挙げられる。 The lower acyl group preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms. Particularly preferred is a method using an acetylated product of the polymerizable monomer in the reaction.
重合性単量体の低級アシル化物は、別途アシル化して予め合成したものを用いてもよいし、液晶ポリマーの製造時に重合性単量体に無水酢酸等のアシル化剤を加えて反応系内で生成せしめることもできる。 The lower acylated product of the polymerizable monomer may be separately acylated and synthesized beforehand, or an acylating agent such as acetic anhydride may be added to the polymerizable monomer during the production of the liquid crystal polymer. It can also be generated with
溶融アシドリシス法またはスラリー重合法のいずれの場合においても、重合反応は、温度１５０〜４００℃、好ましくは２５０〜３８０℃で、常圧および／または減圧下で行うのがよく、必要に応じて触媒を用いてもよい。 In any case of the melt acidification method or the slurry polymerization method, the polymerization reaction is carried out at a temperature of 150 to 400 ° C., preferably 250 to 380 ° C. under normal pressure and / or reduced pressure. May be used.
触媒の具体例としては、ジアルキルスズオキシド（たとえばジブチルスズオキシド）、ジアリールスズオキシドなどの有機スズ化合物；二酸化チタン；三酸化アンチモン；アルコキシチタンシリケート、チタンアルコキシドなどの有機チタン化合物；カルボン酸のアルカリおよびアルカリ土類金属塩（たとえば酢酸カリウム）；ルイス酸（たとえば三フッ化硼素）、ハロゲン化水素（たとえば塩化水素）などの気体状酸触媒などが挙げられる。 Specific examples of the catalyst include organotin compounds such as dialkyltin oxide (for example, dibutyltin oxide) and diaryltin oxide; titanium dioxide; antimony trioxide; organotitanium compounds such as alkoxytitanium silicate and titanium alkoxide; alkali and alkali of carboxylic acid Examples include earth metal salts (for example, potassium acetate); gaseous acids catalysts such as Lewis acids (for example, boron trifluoride) and hydrogen halides (for example, hydrogen chloride).
触媒を使用する場合、該触媒の量は他の重合性単量体（Ｂ）全量に対し、好ましくは１〜１０００ｐｐｍ、より好ましくは２〜１００ｐｐｍである。 When a catalyst is used, the amount of the catalyst is preferably 1 to 1000 ppm, more preferably 2 to 100 ppm, based on the total amount of the other polymerizable monomer (B).
このようにして重縮合反応されて得られた本発明の液晶ポリマーは、通常、溶融状態で重合反応槽より抜き出された後に、ペレット状、フレーク状、または粉末状に加工される。 The liquid crystal polymer of the present invention obtained by the polycondensation reaction in this way is usually processed into a pellet, flake, or powder after being extracted from the polymerization reaction tank in a molten state.
ペレット状、フレーク状、または粉末状の液晶ポリマーは、分子量を高め耐熱性を向上させる目的などで、減圧下、真空下、または窒素、ヘリウムなどの不活性ガス雰囲気下において、実質的に固相状態で熱処理を行ってもよい。 A liquid crystal polymer in the form of pellets, flakes, or powders is substantially a solid phase under reduced pressure, vacuum, or an inert gas atmosphere such as nitrogen or helium for the purpose of increasing molecular weight and improving heat resistance. You may heat-process in a state.
上記のようにして得られた、本発明の液晶ポリマーには、無機充填剤および／または有機充填材、以下に説明する他の添加剤、および他の樹脂成分から選択される一種以上を配合して、液晶ポリマー組成物としてもよい。 The liquid crystal polymer of the present invention obtained as described above is blended with one or more selected from inorganic fillers and / or organic fillers, other additives described below, and other resin components. A liquid crystal polymer composition may be used.
本発明の液晶ポリマーに配合してもよい無機または有機充填材は、繊維状、板状または粒状のものであってよく、たとえばガラス繊維、ミルドガラス、シリカアルミナ繊維、アルミナ繊維、炭素繊維、アラミド繊維、チタン酸カリウムウイスカ、ホウ酸アルミニウムウイスカ、ウォラストナイト、タルク、マイカ、グラファイト、炭酸カルシウム、ドロマイト、クレイ、ガラスフレーク、ガラスビーズ、硫酸バリウム、および酸化チタンが挙げられる。これらの中では、ガラス繊維が物性とコストのバランスが優れている点で好ましい。これらの充填材は、２種以上を併用してもよい。 The inorganic or organic filler that may be blended in the liquid crystal polymer of the present invention may be in the form of fibers, plates, or granules, such as glass fibers, milled glass, silica alumina fibers, alumina fibers, carbon fibers, aramids. Examples include fibers, potassium titanate whiskers, aluminum borate whiskers, wollastonite, talc, mica, graphite, calcium carbonate, dolomite, clay, glass flakes, glass beads, barium sulfate, and titanium oxide. In these, glass fiber is preferable at the point which the balance of a physical property and cost is excellent. Two or more of these fillers may be used in combination.
本発明の液晶ポリマー組成物における、無機または有機充填材の合計量は、液晶ポリマー１００重量部に対して、好ましくは１〜２００重量部、より好ましくは５〜１００重量部である。前記の無機または有機充填材の合計量が液晶ポリマー１００重量部に対して２００重量部を超える場合には、液晶ポリマー組成物の成形加工性が低下する傾向や、成形機のシリンダーや金型の磨耗が大きくなる傾向がある。 The total amount of the inorganic or organic filler in the liquid crystal polymer composition of the present invention is preferably 1 to 200 parts by weight, more preferably 5 to 100 parts by weight with respect to 100 parts by weight of the liquid crystal polymer. When the total amount of the inorganic or organic filler exceeds 200 parts by weight with respect to 100 parts by weight of the liquid crystal polymer, the molding processability of the liquid crystal polymer composition tends to decrease, or the cylinder or mold of the molding machine Wear tends to increase.
本発明の液晶ポリマーには、本発明の効果を損なわない範囲で、他の添加剤、例えば高級脂肪酸、高級脂肪酸エステル、高級脂肪酸アミド、高級脂肪酸金属塩（ここで高級脂肪酸とは、炭素原子数１０〜２５のものをいう）、ポリシロキサン、フッ素樹脂などの離型改良剤；染料、顔料などの着色剤；酸化防止剤；熱安定剤；紫外線吸収剤；帯電防止剤；界面活性剤などを配合してもよい。これらの添加剤は１種のみを配合してもよく、または２種以上を組み合わせて配合してもよい。 In the liquid crystal polymer of the present invention, other additives such as higher fatty acid, higher fatty acid ester, higher fatty acid amide, higher fatty acid metal salt (here, higher fatty acid means the number of carbon atoms) within the range not impairing the effect of the present invention. 10-25), release agents such as polysiloxanes and fluororesins; coloring agents such as dyes and pigments; antioxidants; thermal stabilizers; ultraviolet absorbers; antistatic agents; You may mix | blend. These additives may be blended alone or in combination of two or more.
本発明の液晶ポリマー組成物における他の添加剤の合計量は、液晶ポリマー１００重量部に対して、好ましくは０．１〜１０重量部、より好ましくは０．５〜５重量部である。他の添加剤の合計量が液晶ポリマー１００重量部に対して１０重量部を超える場合には、液晶ポリマー組成物の成形加工性が低下する傾向や、熱安定性が悪くなる傾向がある。 The total amount of other additives in the liquid crystal polymer composition of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the liquid crystal polymer. When the total amount of other additives exceeds 10 parts by weight with respect to 100 parts by weight of the liquid crystal polymer, the molding processability of the liquid crystal polymer composition tends to decrease and the thermal stability tends to deteriorate.
また、本発明の液晶ポリマーもしくは液晶ポリマー組成物を成形するに際し、上記他の添加剤のうち高級脂肪酸、高級脂肪酸エステル、高級脂肪酸金属塩、フルオロカーボン系界面活性剤等の外部滑剤効果を有する添加剤を、予め、液晶ポリマーのペレット表面に付着せしめてもよい。 Further, in molding the liquid crystal polymer or liquid crystal polymer composition of the present invention, among the other additives, an additive having an external lubricant effect such as higher fatty acid, higher fatty acid ester, higher fatty acid metal salt, fluorocarbon surfactant, etc. May be previously attached to the pellet surface of the liquid crystal polymer.
本発明の液晶ポリマーには、他の樹脂成分を添加してもよい。他の樹脂成分としては、たとえばポリアミド、ポリエステル、ポリアセタール、ポリフェニレンエーテル、およびその変性物、ならびにポリスルホン、ポリエーテルスルホン、ポリエーテルイミド、ポリアミドイミドなどの熱可塑性樹脂や、フェノール樹脂、エポキシ樹脂、ポリイミド樹脂などの熱硬化性樹脂が挙げられる。他の樹脂成分は、単独で、あるいは２種以上を組み合わせて配合することができる。他の樹脂成分の配合量は特に限定的ではなく、液晶ポリマーの用途や目的に応じて適宜定めればよい。一つの典型的な例において、他の樹脂成分の合計量は、液晶ポリマー１００重量部に対して０．１〜１００重量部、特に０．１〜８０重量部である。 Other resin components may be added to the liquid crystal polymer of the present invention. Examples of other resin components include polyamide, polyester, polyacetal, polyphenylene ether, and modified products thereof, and thermoplastic resins such as polysulfone, polyethersulfone, polyetherimide, and polyamideimide, phenol resin, epoxy resin, and polyimide resin. And other thermosetting resins. Other resin components can be blended alone or in combination of two or more. The blending amount of the other resin components is not particularly limited, and may be appropriately determined according to the use and purpose of the liquid crystal polymer. In one typical example, the total amount of the other resin components is 0.1 to 100 parts by weight, particularly 0.1 to 80 parts by weight, based on 100 parts by weight of the liquid crystal polymer.
本発明の液晶ポリマー組成物は、無機充填剤、有機充填剤、他の添加剤および／または他の樹脂成分等を液晶ポリマー中に添加し、これをバンバリーミキサー、ニーダー、一軸もしくは二軸押出機などを用いて、液晶ポリマーの結晶融解温度近傍から結晶融解温度プラス１００℃までの温度範囲で溶融混練して得ることができる。 In the liquid crystal polymer composition of the present invention, an inorganic filler, an organic filler, other additives and / or other resin components are added to a liquid crystal polymer, and this is added to a Banbury mixer, kneader, single-screw or twin-screw extruder. Etc. can be obtained by melt-kneading in the temperature range from the vicinity of the crystal melting temperature of the liquid crystal polymer to the crystal melting temperature plus 100 ° C.
以下、実施例により本発明を詳細に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
実施例における特性値は以下の方法によって測定した。 The characteristic values in the examples were measured by the following methods.
〈溶融粘度〉
溶融粘度測定装置（東洋精機（株）製キャピログラフ１Ｄ）により、０．７ｍｍφ×１０ｍｍのキャピラリーを用いて、溶融粘度を測定した。
溶融粘度が低いほど成形時の流動性に優れることを意味する。
<Melt viscosity>
The melt viscosity was measured using a 0.7 mmφ × 10 mm capillary with a melt viscosity measuring apparatus (Capillograph 1D manufactured by Toyo Seiki Co., Ltd.).
The lower the melt viscosity, the better the fluidity during molding.
〈結晶融解温度〉
示差走査熱量計（セイコーインスツルメンツ（株）製ＥｘｓｔＡｒ６０００）を用いて、試料を室温から２０℃／分の昇温条件で測定した際に観測される吸熱ピーク温度（Ｔｍ１）を測定した後、Ｔｍ１より２０〜５０℃高い温度で１０分間保持した。次いで、２０℃／分の降温条件で室温まで試料を冷却し、さらに再度２０℃／分の昇温条件で測定した際の吸熱ピークを観測し、そのピークトップを示す温度を結晶融解温度（Ｔｍ）とした。
<Crystal melting temperature>
Using a differential scanning calorimeter (ExstAr6000 manufactured by Seiko Instruments Inc.), after measuring the endothermic peak temperature (Tm1) observed when the sample was measured at room temperature to 20 ° C./min, from Tm1 The temperature was kept at 20-50 ° C. for 10 minutes. Next, the sample was cooled to room temperature under a temperature drop condition of 20 ° C./min, and an endothermic peak was measured again when measured under a temperature rise condition of 20 ° C./min. The temperature showing the peak top was the crystal melting temperature (Tm ).
〈誘電率〉
試料を、射出成形機（日精樹脂工業株式会社製ＮＥＸ-15-１Ｅ）を用いて表１に記載の条件で、長さ８５ｍｍ、幅１．７０ｍｍ、厚さ１．７０ｍｍのスティック状試験片に成形し、その試験片を用いて、ネットワークアナライザー（アジレントテクノロジー社製ＰＮＡシリーズＥ８３１６Ａ）にて１０ＧＨｚにおける誘電率をＪＩＳ Ｃ２５６５に準拠する空洞共振器摂動法により測定した。
<Dielectric constant>
The sample was formed into a stick-shaped test piece having a length of 85 mm, a width of 1.70 mm, and a thickness of 1.70 mm under the conditions shown in Table 1 using an injection molding machine (NEX-15-1E manufactured by Nissei Plastic Industry Co., Ltd.). The dielectric constant at 10 GHz was measured by a cavity resonator perturbation method based on JIS C2565 with a network analyzer (PNA series E8316A manufactured by Agilent Technologies) using the test piece.
実施例１
下記化合物を攪拌翼、留出管を備えた反応容器に仕込み、窒素ガス雰囲気下に２５〜１７０℃の間を５０分かけて昇温し、１７０℃で３０分保った後、３７５℃まで４時間かけて昇温し、さらに３７５℃で１０分反応させた後、３７５℃で減圧を行った。次いで１時間かけて１０ｔｏｒｒまで減圧し、所定の撹拌トルクに達した時点で重縮合を完結させた。反応容器から内容物を取り出し、粉砕機により液晶ポリマーのペレットを得た。
４−ヒドロキシ安息香酸： ３１４．２ｇ（３５モル部）
６−ヒドロキシ−２−ナフトエ酸： ６１．２ｇ（５モル部）
ハイドロキノン： １１４．５ｇ（１６モル部）
４，４’−ビフェノール： １５７．３ｇ（１３モル部）
テレフタル酸： ３２３．９ｇ（３０モル部）
９，９−ビス（４−ヒドロキシフェニル）フルオレン： ２２．８ｇ（１モル部）
無水酢酸： ６８８．４ｇ（１０３モル部）
Example 1
The following compounds were charged into a reaction vessel equipped with a stirring blade and a distillation pipe, heated between 25-170 ° C. over 50 minutes in a nitrogen gas atmosphere, maintained at 170 ° C. for 30 minutes, and then increased to 375 ° C. 4 The temperature was raised over time, and the mixture was further reacted at 375 ° C. for 10 minutes, and then reduced in pressure at 375 ° C. Subsequently, the pressure was reduced to 10 torr over 1 hour, and when the predetermined stirring torque was reached, the polycondensation was completed. The contents were taken out from the reaction vessel, and liquid crystal polymer pellets were obtained by a pulverizer.
4-hydroxybenzoic acid: 314.2 g (35 mole parts)
6-hydroxy-2-naphthoic acid: 61.2 g (5 mol parts)
Hydroquinone: 114.5 g (16 mol parts)
4,4′-biphenol: 157.3 g (13 mole parts)
Terephthalic acid: 323.9 g (30 mole parts)
9,9-bis (4-hydroxyphenyl) fluorene: 22.8 g (1 mol part)
Acetic anhydride: 688.4 g (103 parts by mole)
得られたペレットを成形し、誘電率を測定した。その結果を得られた樹脂の溶融粘度および結晶融解温度とともに表２に示した。 The obtained pellets were molded and the dielectric constant was measured. The results are shown in Table 2 together with the melt viscosity and crystal melting temperature of the obtained resin.
実施例２
下記化合物を反応容器に仕込んだ以外は実施例１と同様にして液晶ポリマーのペレットを得た。
４−ヒドロキシ安息香酸： ３１４．２ｇ（３５モル部）
６−ヒドロキシ−２−ナフトエ酸： ６１．２ｇ（５モル部）
ハイドロキノン： ８５．９ｇ（１２モル部）
４，４’−ビフェノール： １５７．３ｇ（１３モル部）
テレフタル酸： ３２３．９ｇ（３０モル部）
９，９−ビス（４−ヒドロキシフェニル）フルオレン： １１３．９ｇ（５モル部）
無水酢酸： ６８８．７ｇ（１０３モル部）
Example 2
Liquid crystal polymer pellets were obtained in the same manner as in Example 1 except that the following compounds were charged in a reaction vessel.
4-hydroxybenzoic acid: 314.2 g (35 mole parts)
6-hydroxy-2-naphthoic acid: 61.2 g (5 mol parts)
Hydroquinone: 85.9 g (12 mol parts)
4,4′-biphenol: 157.3 g (13 mole parts)
Terephthalic acid: 323.9 g (30 mole parts)
9,9-bis (4-hydroxyphenyl) fluorene: 113.9 g (5 mol parts)
Acetic anhydride: 688.7 g (103 mole parts)
得られたペレットを成形し、誘電率を測定した。その結果を得られた樹脂の溶融粘度および結晶融解温度とともに表２に示した。 The obtained pellets were molded and the dielectric constant was measured. The results are shown in Table 2 together with the melt viscosity and crystal melting temperature of the obtained resin.
実施例３
下記化合物を反応容器に仕込んだ以外は実施例１と同様にして液晶ポリマーのペレットを得た。
４−ヒドロキシ安息香酸： ３１４．２ｇ（３５モル部）
６−ヒドロキシ−２−ナフトエ酸： ６１．２ｇ（５モル部）
ハイドロキノン： ６８．０ｇ（９．５モル部）
４，４’−ビフェノール： １５７．３ｇ（１３モル部）
テレフタル酸： ３２３．９ｇ（３０モル部）
９，９−ビス（４−ヒドロキシフェニル）フルオレン： １７０．８ｇ（７．５モル部）
無水酢酸： ６８９．０ｇ（１０３モル部）
Example 3
Liquid crystal polymer pellets were obtained in the same manner as in Example 1 except that the following compounds were charged in a reaction vessel.
4-hydroxybenzoic acid: 314.2 g (35 mole parts)
6-hydroxy-2-naphthoic acid: 61.2 g (5 mol parts)
Hydroquinone: 68.0 g (9.5 mol parts)
4,4′-biphenol: 157.3 g (13 mole parts)
Terephthalic acid: 323.9 g (30 mole parts)
9,9-bis (4-hydroxyphenyl) fluorene: 170.8 g (7.5 mol parts)
Acetic anhydride: 689.0 g (103 mole parts)
得られたペレットを成形し、誘電率を測定した。その結果を得られた樹脂の溶融粘度および結晶融解温度とともに表２に示した。 The obtained pellets were molded and the dielectric constant was measured. The results are shown in Table 2 together with the melt viscosity and crystal melting temperature of the obtained resin.
実施例４
下記化合物を反応容器に仕込んだ以外は実施例１と同様にして液晶ポリマーのペレットを得た。
４−ヒドロキシ安息香酸： ３１４．２ｇ（３５モル部）
６−ヒドロキシ−２−ナフトエ酸： ６１．２ｇ（５モル部）
ハイドロキノン： ５０．１ｇ（７モル部）
４，４’−ビフェノール： １５７．３ｇ（１３モル部）
テレフタル酸： ３２３．９ｇ（３０モル部）
９，９−ビス（４−ヒドロキシフェニル）フルオレン： ２２７．８ｇ（１０モル部）
無水酢酸： ６８９．２ｇ（１０３モル部）
Example 4
Liquid crystal polymer pellets were obtained in the same manner as in Example 1 except that the following compounds were charged in a reaction vessel.
4-hydroxybenzoic acid: 314.2 g (35 mole parts)
6-hydroxy-2-naphthoic acid: 61.2 g (5 mol parts)
Hydroquinone: 50.1 g (7 mol parts)
4,4′-biphenol: 157.3 g (13 mole parts)
Terephthalic acid: 323.9 g (30 mole parts)
9,9-bis (4-hydroxyphenyl) fluorene: 227.8 g (10 mole parts)
Acetic anhydride: 689.2 g (103 mole parts)
得られたペレットを成形し、誘電率を測定した。その結果を得られた樹脂の溶融粘度および結晶融解温度とともに表２に示した。 The obtained pellets were molded and the dielectric constant was measured. The results are shown in Table 2 together with the melt viscosity and crystal melting temperature of the obtained resin.
実施例５
下記化合物を反応容器に仕込んだ以外は実施例１と同様にして液晶ポリマーのペレットを得た。
４−ヒドロキシ安息香酸： ３１４．２ｇ（３５モル部）
６−ヒドロキシ−２−ナフトエ酸： ６１．２ｇ（５モル部）
ハイドロキノン： ８５．９ｇ（１２モル部）
４，４’−ビフェノール： １５７．３ｇ（１３モル部）
テレフタル酸： ３２３．９ｇ（３０モル部）
９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン： １２３．０ｇ（５モル部）
無水酢酸 ： ６８８．１ｇ（１０３モル部）
Example 5
Liquid crystal polymer pellets were obtained in the same manner as in Example 1 except that the following compounds were charged in a reaction vessel.
4-hydroxybenzoic acid: 314.2 g (35 mole parts)
6-hydroxy-2-naphthoic acid: 61.2 g (5 mol parts)
Hydroquinone: 85.9 g (12 mol parts)
4,4′-biphenol: 157.3 g (13 mole parts)
Terephthalic acid: 323.9 g (30 mole parts)
9,9-bis (4-hydroxy-3-methylphenyl) fluorene: 123.0 g (5 mol parts)
Acetic anhydride: 688.1 g (103 parts by mole)
得られたペレットを成形し、誘電率を測定した。その結果を得られた樹脂の溶融粘度および結晶融解温度とともに表２に示した。 The obtained pellets were molded and the dielectric constant was measured. The results are shown in Table 2 together with the melt viscosity and crystal melting temperature of the obtained resin.
実施例６
下記化合物を反応容器に仕込んだ以外は実施例１と同様にして液晶ポリマーのペレットを得た。
４−ヒドロキシ安息香酸： ３８５．１ｇ（４２．９モル部）
６−ヒドロキシ−２−ナフトエ酸： １９２．１ｇ（１５．７モル部）
ハイドロキノン： １１２．４ｇ（１５．７モル部）
テレフタル酸： ２２３．５ｇ（２０．７モル部）
９，９−ビス（４−ヒドロキシフェニル）フルオレン： １１３．９ｇ（５モル部）
無水酢酸： ６８８．３ｇ（１０３モル部）
Example 6
Liquid crystal polymer pellets were obtained in the same manner as in Example 1 except that the following compounds were charged in a reaction vessel.
4-hydroxybenzoic acid: 385.1 g (42.9 mol parts)
6-Hydroxy-2-naphthoic acid: 192.1 g (15.7 mol parts)
Hydroquinone: 112.4 g (15.7 mol parts)
Terephthalic acid: 223.5 g (20.7 mol parts)
9,9-bis (4-hydroxyphenyl) fluorene: 113.9 g (5 mol parts)
Acetic anhydride: 688.3 g (103 mole parts)
得られたペレットを成形し、誘電率を測定した。その結果を得られた樹脂の溶融粘度および結晶融解温度とともに表２に示した。 The obtained pellets were molded and the dielectric constant was measured. The results are shown in Table 2 together with the melt viscosity and crystal melting temperature of the obtained resin.
比較例１
下記化合物を攪拌翼、留出管を備えた反応容器に仕込み、窒素ガス雰囲気下に４０〜１７０℃の間を１時間かけて昇温し、１７０℃で３０分保った後、３５０℃まで７．５時間かけて昇温し、さらに３５０℃で１０分反応させた後、３５０℃で減圧を行った。次いで１．５時間かけて５ｔｏｒｒまで減圧し、所定の撹拌トルクに達した時点で重縮合を完結させた。反応容器から内容物を取り出し、粉砕機により液晶ポリマーのペレットを得た。
４−ヒドロキシ安息香酸： ３１４．２ｇ（３５モル部）
６−ヒドロキシ−２−ナフトエ酸： ６１．２ｇ（５モル部）
ハイドロキノン： １２１．７ｇ（１７モル部）
４，４’−ビフェノール： １５７．３ｇ（１３モル部）
テレフタル酸： ３２３．９ｇ（３０モル部）
無水酢酸： ６８４ｇ（１０３モル部）
Comparative Example 1
The following compounds were charged into a reaction vessel equipped with a stirring blade and a distillation pipe, heated between 40-170 ° C. in a nitrogen gas atmosphere over 1 hour, kept at 170 ° C. for 30 minutes, and then increased to 350 ° C. The temperature was raised over 5 hours, and the reaction was further continued at 350 ° C. for 10 minutes, followed by decompression at 350 ° C. Subsequently, the pressure was reduced to 5 torr over 1.5 hours, and the polycondensation was completed when a predetermined stirring torque was reached. The contents were taken out from the reaction vessel, and liquid crystal polymer pellets were obtained by a pulverizer.
4-hydroxybenzoic acid: 314.2 g (35 mole parts)
6-hydroxy-2-naphthoic acid: 61.2 g (5 mol parts)
Hydroquinone: 121.7 g (17 mole parts)
4,4′-biphenol: 157.3 g (13 mole parts)
Terephthalic acid: 323.9 g (30 mole parts)
Acetic anhydride: 684 g (103 mole parts)
得られたペレットを成形し、誘電率を測定した。その結果を得られた樹脂の溶融粘度および結晶融解温度とともに表２に示した。 The obtained pellets were molded and the dielectric constant was measured. The results are shown in Table 2 together with the melt viscosity and crystal melting temperature of the obtained resin.
比較例２
下記化合物を反応容器に仕込んだ以外は比較例１と同様にして液晶ポリマーのペレットを得た。
４−ヒドロキシ安息香酸： ３７７．０ｇ（４２モル部）
６−ヒドロキシ−２−ナフトエ酸： １９５．７ｇ（１６モル部）
ハイドロキノン： １５０．３ｇ（２１モル部）
テレフタル酸： ２２６．７ｇ（２１モル部）
無水酢酸： ６８４ｇ（１０３モル部）
Comparative Example 2
Liquid crystal polymer pellets were obtained in the same manner as in Comparative Example 1 except that the following compounds were charged into the reaction vessel.
4-hydroxybenzoic acid: 377.0 g (42 mol parts)
6-hydroxy-2-naphthoic acid: 195.7 g (16 mole parts)
Hydroquinone: 150.3 g (21 mole parts)
Terephthalic acid: 226.7 g (21 mole parts)
Acetic anhydride: 684 g (103 mole parts)
得られたペレットを成形し、誘電率を測定した。その結果を得られた樹脂の溶融粘度および結晶融解温度とともに表２に示した。 The obtained pellets were molded and the dielectric constant was measured. The results are shown in Table 2 together with the melt viscosity and crystal melting temperature of the obtained resin.
表２に示される通り、ビフェニルフルオレン化合物を含む液晶ポリマー（実施例１〜６）は、ビフェニルフルオレン化合物を含まない液晶ポリマー（比較例１〜２）と比較して、１０ＧＨｚにおける誘電率が低いことがわかる。したがって、本発明の液晶ポリマーは、液晶ポリマー自体が低誘電率化されているため、ガラスビーズやガラスバルーン等を含有させることによる物性の低下を生じさせることなく用いることができることが理解される。
本発明の好ましい態様は以下を包含する。
〔１〕式（Ｉ）で表されるビフェニルフルオレン化合物、およびそれらの反応性誘導体からなる群から選択される重合性単量体（Ａ）と、他の重合性単量体（Ｂ）とから構成される共重合体である、液晶ポリマー。
〔２〕Ｘ １ およびＸ ２ がいずれもヒドロキシル基である、〔１〕に記載の液晶ポリマー。
〔３〕重合性単量体（Ａ）が、９，９−ビス（４−ヒドロキシフェニル）フルオレンおよび／または９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン、およびそれらの反応性誘導体からなる群から選択される、〔１〕または〔２〕に記載の液晶ポリマー。
〔４〕重合性単量体（Ａ）の合計量が、他の重合性単量体（Ｂ）の合計量１００モル部に対して０．０１〜３０モル部である、〔１〕〜〔３〕のいずれかに記載の液晶ポリマー。
〔５〕他の重合性単量体（Ｂ）が、芳香族ヒドロキシカルボン酸、芳香族ジカルボン酸、芳香族ジオール、芳香族アミノカルボン酸、芳香族ヒドロキシアミン、芳香族ジアミンおよび脂肪族ジオールからなる群から選択される１種以上の化合物である、〔１〕〜〔４〕のいずれかに記載の液晶ポリマー。
〔６〕他の重合性単量体（Ｂ）が芳香族ヒドロキシカルボン酸を含む、〔１〕〜〔５〕のいずれかに記載の液晶ポリマー。
〔７〕他の重合性単量体（Ｂ）が、芳香族ヒドロキシカルボン酸、芳香族ジカルボン酸および芳香族ジオールを含む、〔１〕〜〔６〕のいずれかに記載の液晶ポリマー。
〔８〕芳香族ヒドロキシカルボン酸が、４−ヒドロキシ安息香酸および／または６−ヒドロキシ−２−ナフトエ酸である、〔５〕〜〔７〕のいずれかに記載の液晶ポリマー。
〔９〕他の重合性単量体（Ｂ）が、４−ヒドロキシ安息香酸、６−ヒドロキシ−２−ナフトエ酸、芳香族ジカルボン酸および芳香族ジオールである、〔１〕〜〔８〕のいずれかに記載の液晶ポリマー。
〔１０〕芳香族ジカルボン酸が、テレフタル酸、イソフタル酸および２，６−ナフタレンジカルボン酸からなる群から選択される１種以上の化合物である、〔５〕、〔７〕または〔９〕に記載の液晶ポリマー。
〔１１〕芳香族ジオールが、ハイドロキノン、レゾルシン、４，４’−ジヒドロキシビフェニル、２，６−ジヒドロキシナフタレンおよびビスフェノールＡからなる群から選択される１種以上の化合物である、〔５〕、〔７〕または〔９〕に記載の液晶ポリマー。
〔１２〕〔１〕〜〔１１〕のいずれかに記載の液晶ポリマーと無機充填剤および／または有機充填材を含む液晶ポリマー組成物。
〔１３〕〔１〕〜〔１１〕のいずれかに記載の液晶ポリマーまたは〔１２〕に記載の液晶ポリマー組成物から構成される、射出成形品、フィルムおよび繊維からなる群から選択される成形品。
As shown in Table 2, the liquid crystal polymer containing biphenylfluorene compounds (Examples 1 to 6) has a lower dielectric constant at 10 GHz than the liquid crystal polymer containing no biphenylfluorene compounds (Comparative Examples 1 to 2). I understand. Therefore, it is understood that the liquid crystal polymer of the present invention can be used without causing deterioration in physical properties due to the inclusion of glass beads, glass balloons, or the like because the liquid crystal polymer itself has a low dielectric constant.
Preferred embodiments of the present invention include:
[1] From a polymerizable monomer (A) selected from the group consisting of a biphenylfluorene compound represented by formula (I) and a reactive derivative thereof, and another polymerizable monomer (B) A liquid crystal polymer that is a copolymer.
[2] The liquid crystal polymer according to [1], wherein X 1 and X 2 are both hydroxyl groups.
[3] The polymerizable monomer (A) is 9,9-bis (4-hydroxyphenyl) fluorene and / or 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and their reactivity The liquid crystal polymer according to [1] or [2], which is selected from the group consisting of derivatives.
[4] The total amount of the polymerizable monomer (A) is 0.01 to 30 mol parts relative to 100 mol parts of the total amount of the other polymerizable monomers (B). 3] The liquid crystal polymer according to any one of the above.
[5] The other polymerizable monomer (B) is composed of aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic aminocarboxylic acid, aromatic hydroxyamine, aromatic diamine and aliphatic diol. The liquid crystal polymer according to any one of [1] to [4], which is one or more compounds selected from the group.
[6] The liquid crystal polymer according to any one of [1] to [5], wherein the other polymerizable monomer (B) contains an aromatic hydroxycarboxylic acid.
[7] The liquid crystal polymer according to any one of [1] to [6], wherein the other polymerizable monomer (B) includes an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, and an aromatic diol.
[8] The liquid crystal polymer according to any one of [5] to [7], wherein the aromatic hydroxycarboxylic acid is 4-hydroxybenzoic acid and / or 6-hydroxy-2-naphthoic acid.
[9] Any of [1] to [8], wherein the other polymerizable monomer (B) is 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, aromatic dicarboxylic acid and aromatic diol Liquid crystal polymer according to any one of the above.
[10] The aromatic dicarboxylic acid is one or more compounds selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid, [5], [7] or [9] Liquid crystal polymer.
[11] The aromatic diol is one or more compounds selected from the group consisting of hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, 2,6-dihydroxynaphthalene and bisphenol A. [5], [7 ] Or the liquid crystal polymer according to [9].
[12] A liquid crystal polymer composition comprising the liquid crystal polymer according to any one of [1] to [11] and an inorganic filler and / or an organic filler.
[13] A molded product selected from the group consisting of an injection molded product, a film and a fiber, comprising the liquid crystal polymer according to any one of [1] to [11] or the liquid crystal polymer composition according to [12]. .
Claims (10)
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| JP2015230430A JP6576808B2 (en) | 2015-11-26 | 2015-11-26 | Liquid crystal polymer |
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| JP2015230430A JP6576808B2 (en) | 2015-11-26 | 2015-11-26 | Liquid crystal polymer |
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| JP6576808B2 true JP6576808B2 (en) | 2019-09-18 |
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