JP2021183678A - Liquid crystal polymer - Google Patents
Liquid crystal polymer Download PDFInfo
- Publication number
- JP2021183678A JP2021183678A JP2020089693A JP2020089693A JP2021183678A JP 2021183678 A JP2021183678 A JP 2021183678A JP 2020089693 A JP2020089693 A JP 2020089693A JP 2020089693 A JP2020089693 A JP 2020089693A JP 2021183678 A JP2021183678 A JP 2021183678A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- crystal polymer
- acid
- mol
- aromatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920000106 Liquid crystal polymer Polymers 0.000 title claims abstract description 115
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 title claims abstract description 115
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- 239000000178 monomer Substances 0.000 claims abstract description 43
- 125000003118 aryl group Chemical group 0.000 claims abstract description 42
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 78
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 58
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 39
- -1 aromatic diol Chemical class 0.000 claims description 39
- 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 27
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 20
- 239000000470 constituent Substances 0.000 claims description 19
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 12
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 12
- 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 11
- 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 9
- 239000000835 fiber Substances 0.000 claims description 7
- 239000011256 inorganic filler Substances 0.000 claims description 7
- 239000012766 organic filler Substances 0.000 claims description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 5
- 150000004984 aromatic diamines Chemical class 0.000 claims description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 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
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 39
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 30
- 239000008188 pellet Substances 0.000 description 26
- 238000000034 method Methods 0.000 description 25
- 229920001577 copolymer Polymers 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 22
- 239000000155 melt Substances 0.000 description 19
- 238000005452 bending Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 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 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 230000000052 comparative effect Effects 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
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- LULATDWLDJOKCX-UHFFFAOYSA-N 5-[(2,5-dihydroxyphenyl)methylamino]-2-hydroxybenzoic acid Chemical compound C1=C(O)C(C(=O)O)=CC(NCC=2C(=CC=C(O)C=2)O)=C1 LULATDWLDJOKCX-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 6
- 150000001793 charged compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- FQJXYULOQZUKBZ-UHFFFAOYSA-N 4-[6-(4-carboxyphenoxy)hexoxy]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OCCCCCCOC1=CC=C(C(O)=O)C=C1 FQJXYULOQZUKBZ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- IUJMPBDJRAXYCK-UHFFFAOYSA-N 6-[2-(6-carboxynaphthalen-2-yl)oxyethoxy]naphthalene-2-carboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(OCCOC3=CC4=CC=C(C=C4C=C3)C(=O)O)=CC=C21 IUJMPBDJRAXYCK-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 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 compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 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
- 230000005540 biological transmission Effects 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
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-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
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound 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
- UIAFKZKHHVMJGS-UHFFFAOYSA-N 2,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-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
- 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
- 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
- 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
- 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
- XRDKWFXOXXUQJS-UHFFFAOYSA-N 4-[10-(4-carboxyphenoxy)decoxy]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OCCCCCCCCCCOC1=CC=C(C(O)=O)C=C1 XRDKWFXOXXUQJS-UHFFFAOYSA-N 0.000 description 1
- VAXBLYWAVAIJJJ-UHFFFAOYSA-N 4-[2-(4-carboxyphenoxy)ethoxy]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OCCOC1=CC=C(C(O)=O)C=C1 VAXBLYWAVAIJJJ-UHFFFAOYSA-N 0.000 description 1
- VBISQLWPGDULSX-UHFFFAOYSA-N 4-[3-(4-carboxyphenoxy)propoxy]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OCCCOC1=CC=C(C(O)=O)C=C1 VBISQLWPGDULSX-UHFFFAOYSA-N 0.000 description 1
- IEKYHZQEIOTJOK-UHFFFAOYSA-N 4-[4-(4-carboxyphenoxy)butoxy]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OCCCCOC1=CC=C(C(O)=O)C=C1 IEKYHZQEIOTJOK-UHFFFAOYSA-N 0.000 description 1
- ZYCRTOPQKAMKGM-UHFFFAOYSA-N 4-[5-(4-carboxyphenoxy)pentoxy]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OCCCCCOC1=CC=C(C(O)=O)C=C1 ZYCRTOPQKAMKGM-UHFFFAOYSA-N 0.000 description 1
- KYUMFUHAEPSERT-UHFFFAOYSA-N 4-[7-(4-carboxyphenoxy)heptoxy]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OCCCCCCCOC1=CC=C(C(O)=O)C=C1 KYUMFUHAEPSERT-UHFFFAOYSA-N 0.000 description 1
- VTNYRTRISNPIRI-UHFFFAOYSA-N 4-[9-(4-carboxyphenoxy)nonoxy]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OCCCCCCCCCOC1=CC=C(C(O)=O)C=C1 VTNYRTRISNPIRI-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
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 1
- BOZQLJCAAZQLOA-UHFFFAOYSA-N 6-[3-(6-carboxynaphthalen-2-yl)oxypropoxy]naphthalene-2-carboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(OCCCOC3=CC4=CC=C(C=C4C=C3)C(=O)O)=CC=C21 BOZQLJCAAZQLOA-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
- XABCHXCRWZBFQX-UHFFFAOYSA-N 7-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=C(O)C=C2C(C(=O)O)=CC=CC2=C1 XABCHXCRWZBFQX-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000004605 External Lubricant Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- UABTUJOPLYDVJN-UHFFFAOYSA-N OC1(C=O)C(C(C2=CC=CC=C2C=C2)=C2O)=C(C=CC=C2)C2=CC1 Chemical compound OC1(C=O)C(C(C2=CC=CC=C2C=C2)=C2O)=C(C=CC=C2)C2=CC1 UABTUJOPLYDVJN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
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- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
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- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
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- 125000002252 acyl group Chemical group 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
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- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical group C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 239000003086 colorant Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QCOXCILKVHKOGO-UHFFFAOYSA-N n-(2-nitramidoethyl)nitramide Chemical compound [O-][N+](=O)NCCN[N+]([O-])=O QCOXCILKVHKOGO-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- VAWFFNJAPKXVPH-UHFFFAOYSA-N naphthalene-1,6-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC2=CC(C(=O)O)=CC=C21 VAWFFNJAPKXVPH-UHFFFAOYSA-N 0.000 description 1
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Abstract
Description
本発明は、機械強度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 mechanical strength.
液晶ポリマーは、耐熱性、剛性等の機械物性、耐薬品性、寸法精度等に優れているため、成形品用途のみならず、繊維やフィルムといった各種用途にその使用が拡大しつつある。特に電気・電子部品の高集積度化、小型化、薄肉化、低背化等が急速に進んでおり０．５ｍｍ以下の非常に薄い肉厚部が形成されるケースが多く、液晶ポリマーの優れた成形性、すなわち、流動性が良好であり、かつバリが出ないという他のポリマーにない特徴を活かして、その使用量が大幅に増大している。 Since liquid crystal polymers are excellent in mechanical properties such as heat resistance and rigidity, chemical resistance, dimensional accuracy, etc., their use is expanding not only for molded products but also for various applications such as fibers and films. In particular, high integration, miniaturization, thinning, and low profile of electrical and electronic components are rapidly progressing, and in many cases, very thin thick parts of 0.5 mm or less are formed, which is an excellent liquid crystal polymer. Taking advantage of the moldability, that is, the characteristics that other polymers do not have, that is, good fluidity and no burrs, the amount used has been greatly increased.
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の爆発的な増加に伴い、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 an advanced information society, in the information and communication fields such as personal computers and mobile phones, with the explosive increase in the amount and speed of transmission of information and communication equipment, the high frequency region of microwaves and millimeter waves. There is a growing need for high-performance high-frequency electronic components that can be adapted in.
一方、情報処理等に伴う高周波・大容量の電気信号の送受信等により、電子回路基板は発熱する傾向にあるが、発熱に伴う消費電力量は無視できないものとなりつつある。 On the other hand, electronic circuit boards tend to generate heat due to transmission / reception of high-frequency and large-capacity electric signals associated with information processing, etc., but the amount of power consumption associated with the heat generation is becoming non-negligible.
一般に電子回路基板の成形材料の誘電正接が小さいほど発熱量が減少し、発熱に伴う消費電力量を抑えることができる。この点に着目した例として、低誘電正接の成形材料として液晶性芳香族ポリエステルを用いることが知られている。例えば、特許文献１には、ｐ−ヒドロキシ安息香酸に由来する構造単位と６−ヒドロキシ−２−ナフトエ酸に由来する構造単位とからなり、ｐ−ヒドロキシ安息香酸に由来する構造単位の含有割合がおよそ２０〜３５モル％の組成を有する液晶性芳香族ポリエステルが提案されている。 Generally, the smaller the dielectric loss tangent of the molding material of an electronic circuit board, the smaller the amount of heat generated, and the amount of power consumed due to heat generation can be suppressed. As an example focusing on this point, it is known to use a liquid crystal aromatic polyester as a molding material having a low dielectric loss tangent. For example, Patent Document 1 comprises a structural unit derived from p-hydroxybenzoic acid and a structural unit derived from 6-hydroxy-2-naphthoic acid, and the content ratio of the structural unit derived from p-hydroxybenzoic acid is Liquid liquid aromatic polyesters having a composition of approximately 20-35 mol% have been proposed.
しかしながら、特許文献１に記載の液晶性芳香族ポリエステルは、機械強度、特にＩｚｏｄ衝撃強度に劣るものであり、機械的強度については更なる改善が求められている。 However, the liquid crystal aromatic polyester described in Patent Document 1 is inferior in mechanical strength, particularly Izod impact strength, and further improvement in mechanical strength is required.
本発明の目的は、Ｉｚｏｄ衝撃強度などの機械強度が改善さ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 improved mechanical strength such as Izod impact strength.
本発明者等は、上記課題に鑑み、鋭意検討した結果、特定の構造を有するジカルボン酸成分を他の重合性単量体と共重合させることによって、機械強度が向上した成形品等を形成し得る液晶ポリマーが得られることを見出し、本発明を完成させるに至った。 As a result of diligent studies in view of the above problems, the present inventors have formed a molded product or the like having improved mechanical strength by copolymerizing a dicarboxylic acid component having a specific structure with another polymerizable monomer. They have found that the obtained liquid crystal polymer can be obtained, and have completed the present invention.
すなわち本発明は、以下の好適な態様を包含する。
〔１〕式（１）
で表される化合物ならびにそれらの反応性誘導体からなる群から選択される１種以上の重合性化合物（Ａ）に由来する構成単位と、重合性単量体（Ｂ）に由来する構成単位とを含む液晶ポリマーであって、重合性化合物（Ａ）に由来する構成単位の合計量が、液晶ポリマーを構成する全構成単位１００モル％に対して０．０１〜７モル％である、液晶ポリマー。
〔２〕Ａｒは式（２）または式（３）
〔３〕Ａｒは式（２）で表される芳香族基であり、ｎは６である、〔１〕または〔２〕に記載の液晶ポリマー。
〔４〕重合性単量体（Ｂ）は、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１種以上である、〔１〕〜〔３〕のいずれかに記載の液晶ポリマー。
〔５〕重合性単量体（Ｂ）は芳香族ヒドロキシカルボン酸を含む、〔１〕〜〔４〕のいずれかに記載の液晶ポリマー。
〔６〕重合性単量体（Ｂ）は、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〕〜〔４〕のいずれかに記載の液晶ポリマー。
〔７〕芳香族ヒドロキシカルボン酸は、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、〔４〕〜〔６〕のいずれかに記載の液晶ポリマー。
〔８〕芳香族ジカルボン酸は、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種以上である、〔４〕〜〔７〕のいずれかに記載の液晶ポリマー。
〔９〕芳香族ジオールは、ハイドロキノン、４,４'−ジヒドロキシビフェニルおよび２，６−ジヒドロキシナフタレンからなる群から選択される１種以上である、〔４〕〜〔８〕のいずれかに記載の液晶ポリマー。
〔１０〕重合性単量体（Ｂ）は、４−ヒドロキシ安息香酸および６−ヒドロキシ−２−ナフトエ酸である、〔１〕〜〔３〕のいずれかに記載の液晶ポリマー。
〔１１〕液晶ポリマーを構成する全構成単位１００モル％に対して、重合性化合物（Ａ）に由来する構成単位が０．０１〜７モル％、４−ヒドロキシ安息香酸に由来する構成単位が１５〜４０モル％、６−ヒドロキシ−２−ナフトエ酸に由来する構成単位が６０〜８５モル％である、〔１０〕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または有機充填材と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を加工してなる、成形品、フィルムまたは繊維からなる物品。
That is, the present invention includes the following preferred embodiments.
[1] Equation (1)
A structural unit derived from one or more polymerizable compounds (A) selected from the group consisting of the compound represented by the above and reactive derivatives thereof, and a structural unit derived from the polymerizable monomer (B). A liquid crystal polymer containing, wherein the total amount of the structural units derived from the polymerizable compound (A) is 0.01 to 7 mol% with respect to 100 mol% of all the structural units constituting the liquid crystal polymer.
[2] Ar is Eq. (2) or Eq. (3)
[3] The liquid crystal polymer according to [1] or [2], wherein Ar is an aromatic group represented by the formula (2) and n is 6.
[4] The polymerizable monomer (B) is an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid, an aromatic diol, an aromatic aminocarboxylic acid, an aromatic hydroxyamine, an aromatic diamine, an aliphatic diol and an aliphatic dicarboxylic acid. The liquid crystal polymer according to any one of [1] to [3], which is one or more selected from the group consisting of acids.
[5] The liquid crystal polymer according to any one of [1] to [4], wherein the polymerizable monomer (B) contains an aromatic hydroxycarboxylic acid.
[6] The liquid crystal polymer according to any one of [1] to [4], wherein the polymerizable monomer (B) contains an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid and an aromatic diol.
[7] The liquid crystal polymer according to any one of [4] to [6], wherein the aromatic hydroxycarboxylic acid is 4-hydroxybenzoic acid and / or 6-hydroxy-2-naphthoic acid.
[8] The liquid crystal polymer according to any one of [4] to [7], wherein the aromatic dicarboxylic acid is at least one selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid. ..
[9] The aromatic diol is one or more selected from the group consisting of hydroquinone, 4,4'-dihydroxybiphenyl and 2,6-dihydroxynaphthalene, according to any one of [4] to [8]. Liquid liquid polymer.
[10] The liquid crystal polymer according to any one of [1] to [3], wherein the polymerizable monomer (B) is 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid.
[11] With respect to 100 mol% of all the structural units constituting the liquid crystal polymer, 0.01 to 7 mol% of the structural units are derived from the polymerizable compound (A) and 15 are the structural units derived from 4-hydroxybenzoic acid. The liquid crystal polymer according to [10], wherein the constituent unit derived from ~ 40 mol% and 6-hydroxy-2-naphthoic acid is 60 to 85 mol%.
[12] A liquid crystal polymer composition containing the liquid crystal polymer according to any one of [1] to [11] and an inorganic or organic filler.
[13] An article made of a molded product, a film or a fiber obtained by processing the liquid crystal polymer according to any one of [1] to [11] or the liquid crystal polymer composition according to [12].
本発明の液晶ポリマーによると、Ｉｚｏｄ衝撃強度などの機械強度が改善された成形品等の物品を形成することができる。 According to the liquid crystal polymer of the present invention, it is possible to form an article such as a molded product having improved mechanical strength such as Izod impact strength.
本発明の液晶ポリマーは、好適には、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る。これらは、通常、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るが、特に限定されない。 The liquid crystal polymer of the present invention is preferably a polyester or polyester amide that forms an anisotropic molten phase. These are usually called thermotropic liquid crystal polyesters or thermotropic liquid crystal polyester amides in the art, but are not particularly limited.
本発明の液晶ポリマーは、式（１）で表される化合物ならびにそれらの反応性誘導体からなる群から選択される１種以上の重合性化合物（Ａ）に由来する構成単位の合計量を、液晶ポリマーを構成する全構成単位１００モル％に対して０．０１〜７モル％有する。 In the liquid crystal polymer of the present invention, the total amount of structural units derived from one or more polymerizable compounds (A) selected from the group consisting of the compound represented by the formula (1) and its reactive derivative is liquid crystal. It has 0.01 to 7 mol% with respect to 100 mol% of all the constituent units constituting the polymer.
Ａｒは、式（２）または式（３）
ｎは２〜１８の整数であり、好ましくは２〜１０であり、より好ましくは２〜６であり、特に好ましくは６である。 n is an integer of 2 to 18, preferably 2 to 10, more preferably 2 to 6, and particularly preferably 6.
式（１）で表される化合物としては、１，２−ビス（４−カルボキシフェノキシ）エタン、１，３−ビス（４−カルボキシフェノキシ）プロパン、１，４−ビス（４−カルボキシフェノキシ）ブタン、１，５−ビス（４−カルボキシフェノキシ）ペンタン、１，６−ビス（４−カルボキシフェノキシ）ヘキサン、１，７−ビス（４−カルボキシフェノキシ）ヘプタン、１，８−ビス（４−カルボキシフェノキシ）オクタン、１，９−ビス（４−カルボキシフェノキシ）ノナン、１，１０−ビス（４−カルボキシフェノキシ）デカン、６，６’−（エチレンジオキシ）ビス−２−ナフトエ酸、６，６’−（プロピレンジオキシ）ビス−２−ナフトエ酸、６，６’−（ブテンジオキシ）ビス−２−ナフトエ酸、６，６’−（ペンテンジオキシ）ビス−２−ナフトエ酸、６，６’−（ヘキセンジオキシ）ビス−２−ナフトエ酸、６，６’−（ヘプテンジオキシ）ビス−２−ナフトエ酸、６，６’−（オクテンジオキシ）ビス−２−ナフトエ酸、６，６’−（ノネンジオキシ）ビス−２−ナフトエ酸、６，６’−（デセンジオキシ）ビス−２−ナフトエ酸などが挙げられる。 Examples of the compound represented by the formula (1) include 1,2-bis (4-carboxyphenoxy) ethane, 1,3-bis (4-carboxyphenoxy) propane, and 1,4-bis (4-carboxyphenoxy) butane. , 1,5-bis (4-carboxyphenoxy) pentane, 1,6-bis (4-carboxyphenoxy) hexane, 1,7-bis (4-carboxyphenoxy) heptane, 1,8-bis (4-carboxyphenoxy) ) Octane, 1,9-bis (4-carboxyphenoxy) nonane, 1,10-bis (4-carboxyphenoxy) decane, 6,6'-(ethylenedioxy) bis-2-naphthoic acid, 6,6' -(Propanedioxy) bis-2-naphthoic acid, 6,6'-(butendioxy) bis-2-naphthoic acid, 6,6'-(pentendioxy) bis-2-naphthoic acid, 6,6'- (Hexenedioxy) bis-2-naphthoic acid, 6,6'-(heptenedioxy) bis-2-naphthoic acid, 6,6'-(octendioxy) bis-2-naphthoic acid, 6,6'-( Nonendioxy) bis-2-naphthoic acid, 6,6'-(decendioxy) bis-2-naphthoic acid and the like can be mentioned.
これらの中でも、より機械強度の改善効果が高いことから、式（４）で表される１，６−ビス（４−カルボキシフェノキシ）ヘキサン、式（５）で表される１，２−（４−カルボキシフェノキシ）エタンおよび式（６）で表される６，６’−（エチレンジオキシ）ビス−２−ナフトエ酸が好ましく、特に１，６−ビス（４−カルボキシフェノキシ）ヘキサンがより好ましい。
本発明の液晶ポリマーを得るために用いる、式（１）で表される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１種以上の重合性化合物（Ａ）の合計量は、液晶ポリマーに含まれる重合性化合物（Ａ）に由来する構成単位の合計量に相当する。用いる重合性化合物（Ａ）の合計量、すなわち液晶ポリマーに含まれる重合性化合物（Ａ）に由来する構成単位の合計量は、用いる重合性化合物および重合性単量体の合計量、すなわち液晶ポリマーを構成する全構成単位１００モル％に対して、０．０１〜７モル％であり、好ましくは０．０５〜５モル％であり、より好ましくは０．０７〜４モル％であり、さらに好ましくは０．１〜３モル％である。重合性化合物（Ａ）に由来する構成単位の合計量が液晶ポリマーを構成する全構成単位１００モル％に対して７モル％を超えると、耐熱性及び機械物性が低下する。重合性化合物（Ａ）に由来する構成単位の合計量が液晶ポリマーを構成する全構成単位１００モル％に対して０．０１モル％未満であると、Ｉｚｏｄ衝撃強度をはじめとする機械的性質の改善効果が得られない。 The total amount of one or more polymerizable compounds (A) selected from the group consisting of the compound represented by the formula (1) and their reactive derivatives used to obtain the liquid crystal polymer of the present invention is the liquid crystal polymer. Corresponds to the total amount of the structural units derived from the polymerizable compound (A) contained in. The total amount of the polymerizable compound (A) used, that is, the total amount of the structural units derived from the polymerizable compound (A) contained in the liquid crystal polymer is the total amount of the polymerizable compound and the polymerizable monomer used, that is, the liquid crystal polymer. It is 0.01 to 7 mol%, preferably 0.05 to 5 mol%, more preferably 0.07 to 4 mol%, still more preferably, with respect to 100 mol% of all the constituent units constituting the above. Is 0.1 to 3 mol%. When the total amount of the structural units derived from the polymerizable compound (A) exceeds 7 mol% with respect to 100 mol% of all the structural units constituting the liquid crystal polymer, the heat resistance and the mechanical properties are deteriorated. When the total amount of the structural units derived from the polymerizable compound (A) is less than 0.01 mol% with respect to 100 mol% of all the structural units constituting the liquid crystal polymer, the mechanical properties such as Izod impact strength are exhibited. No improvement effect can be obtained.
本発明の液晶ポリマーを得るために用いる重合性単量体（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。これらの化合物は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。 The polymerizable monomer (B) used to obtain the liquid crystal polymer of the present invention includes a monomer used in a conventional liquid crystal polymer, for example, aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, and aromatic. Examples include aminocarboxylic 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 or an amino group.
本発明の液晶ポリマーを得るために用いる重合性単量体（Ｂ）は、前記化合物の１種または２種以上の複数個が互いに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、重合性単量体（Ｂ）の量については、重合性単量体がオリゴマーである場合であっても、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 polymerizable monomer (B) used to obtain the liquid crystal polymer of the present invention may be an oligomer in which one kind or a plurality of two or more kinds of the above compounds are bonded to each other. Regarding the amount of the polymerizable monomer (B) in the present specification and claims, even if the polymerizable monomer is an oligomer, the monomer unit constituting the oligomer is used. It shall be calculated based on.
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、６−ヒドロキシ−１−ナフトエ酸、７−ヒドロキシ−２−ナフトエ酸、３−ヒドロキシ−２−ナフトエ酸、７−ヒドロキシ−１−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。 Specific examples of aromatic hydroxycarboxylic acids include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 2-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 6-hydroxy-1-naphthoic acid, and 7-hydroxy. -2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 7-hydroxy-1-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxy Examples thereof include phenyl-3-benzoic acid and its alkyl, alkoxy or halogen substituents and ester-forming derivatives such as acylated products, ester derivatives and acid halides thereof. Among these, 4-hydroxybenzoic acid or 6-hydroxy-2-naphthoic acid or a combination thereof is more preferable in that the heat resistance, mechanical strength and melting point of the obtained liquid crystal polymer can be easily adjusted.
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が挙げられる。 Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 4,4'-dicarboxybiphenyl. , 4'-Dicarboxybiphenyl and 4,4'-dicarboxyterphenyl, their alkyl, alkoxy or halogen substituents and their ester derivatives, ester-forming derivatives such as acid halides.
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からなる群から選択される１種以上が好適に用いられる。 Among these, one or more selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid is preferably used.
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、および２,２'−ジヒドロキシビナフチル、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が挙げられる。 Specific examples of aromatic diols include hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 3,3'-dihydroxybiphenyl, and 3,4'-dihydroxybiphenyl. Examples thereof include ester-forming derivatives such as 4,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenol ether, and 2,2'-dihydroxybinaphthal, their alkyl, alkoxy or halogen substituents and their acylated products.
これらの中でも、ハイドロキノン、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からなる群から選択される１種以上が好適に用いられ、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が好ましい。 Among these, at least one selected from the group consisting of hydroquinone, 4,4'-dihydroxybiphenyl, and 2,6-dihydroxynaphthalene is preferably used, and hydroquinone, 4 is particularly excellent in reactivity during polymerization. , 4'-Dihydroxybiphenyl is preferred.
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が挙げられる。 Specific examples of aromatic aminocarboxylic acids include 4-aminobenzoic acid, 3-aminobenzoic acid, 6-amino-2-naphthoic acid, alkyl, alkoxy or halogen substituents thereof, and acylated products and ester derivatives thereof. , 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 aromatic hydroxyamines include 4-aminophenol, N-methyl-4-aminophenol, 3-aminophenol, 3-methyl-4-aminophenol, 4-amino-1-naphthol, and 4-amino-. 4'-Hydroxybiphenyl, 4-amino-4'-hydroxybiphenyl ether, 4-amino-4'-hydroxybiphenylmethane, 4-amino-4'-hydroxybiphenyl sulfide and 2,2'-diaminobinaphthyl, alkyl of these , Alkoxy or halogen substituents, as well as ester-forming derivatives such as their acylated products. Among these, 4-aminophenol is preferably used because it is easy to balance the heat resistance and mechanical strength of the obtained liquid crystal polymer.
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が挙げられる。 Specific examples of aromatic diamines include 1,4-phenylenediamine, 1,3-phenylenediamine, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, their alkyl, alkoxy or halogen substituents, and theirs. Examples thereof 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単位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. Further, a polymer containing an aliphatic diol unit such as polyethylene terephthalate or polybutylene terephthalate can be used with the above-mentioned aromatic oxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol and its acylated products, ester derivatives, acid halides and the like. It may be reacted.
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、ドデカン二酸が挙げられる。 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, and dodecanedioic acid.
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、芳香族ジアミンおよび脂肪族ジオール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。 The polymerizable monomer (B) is selected from the group consisting of aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic aminocarboxylic acid, aromatic hydroxyamine, aromatic diamine and aliphatic diol. The combined use of two or more compounds is one of the preferred embodiments of the present invention.
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、ならびに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好適に用いられる。 Among these polymerizable monomers, a combination containing an aromatic hydroxycarboxylic acid and a combination containing an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid and an aromatic diol are preferably used.
これらの中でも、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−ナフトエ酸である組合せ、ならびに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の組合せが特に好適に用いられる。 Among these, the combination in which the polymerizable monomer (B) is 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, as well as 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid and aromatic dicarboxylic acid. A combination of acid and aromatic diol is particularly preferably used.
本発明の液晶ポリマーに用いる重合性単量体（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 polymerizable monomer (B) used in the liquid crystal polymer of the present invention include those composed of 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-hydroxy-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 co-weight Combined 20) 4-hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / 4-aminophenol copolymer 21) 4-hydroxybenzoic acid / terephthalic acid / ethylene glycol copolymer 22) 4- Hydroxybenzoic 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-hydroxy Hydroxybenzoic acid / 6-hydroxy-2-naphthic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / ethylene glycol copolymer 25) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / 4,4 '-Dihydroxybiphenyl copolymer.
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本発明の液晶ポリマーを形成してもよい。 The above liquid crystal polymer may be used alone or may be used by blending two or more kinds to form the liquid crystal polymer of the present invention.
本発明の好適な液晶ポリマーにおいて、重合性単量体（Ｂ）が４−ヒドロキシ安息香酸および６−ヒドロキシ−２−ナフトエ酸である場合、以下の２つの態様がより好適である。 In the preferred liquid crystal polymer of the present invention, when the polymerizable monomer (B) is 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, the following two embodiments are more preferable.
（Ｉ）液晶ポリマーを構成する全構成単位１００モル％に対して、重合性化合物（Ａ）に由来する構成単位が０．０１〜７モル％、４−ヒドロキシ安息香酸に由来する構成単位が１５〜４０モル％、６−ヒドロキシ−２−ナフトエ酸重合性単量体に由来する構成単位が６０〜８５モル％である液晶ポリマー。 (I) The constituent unit derived from the polymerizable compound (A) is 0.01 to 7 mol%, and the constituent unit derived from 4-hydroxybenzoic acid is 15 with respect to 100 mol% of all the constituent units constituting the liquid crystal polymer. A liquid crystal polymer containing up to 40 mol% and 60 to 85 mol% of a constituent unit derived from a 6-hydroxy-2-naphthoic acid polymerizable monomer.
４−ヒドロキシ安息香酸に由来する構成単位は、好ましくは１８〜３６モル％、より好ましくは２０〜３４モル％、さらに好ましくは２１〜３２モル％、特に好ましくは２２〜３０モル％である。 The constituent unit derived from 4-hydroxybenzoic acid is preferably 18 to 36 mol%, more preferably 20 to 34 mol%, still more preferably 21 to 22 mol%, and particularly preferably 22 to 30 mol%.
また、６−ヒドロキシ−２−ナフトエ酸に由来する構成単位は、好ましくは６４〜８２モル％、より好ましくは６６〜８０モル％、さらに好ましくは６８〜７９モル％、特に好ましくは７０〜７８モル％である。 The constituent unit derived from 6-hydroxy-2-naphthoic acid is preferably 64 to 82 mol%, more preferably 66 to 80 mol%, still more preferably 68 to 79 mol%, and particularly preferably 70 to 78 mol%. %.
（ＩＩ）液晶ポリマーを構成する全構成単位１００モル％に対して、重合性化合物（Ａ）に由来する構成単位が０．０１〜７モル％、４−ヒドロキシ安息香酸に由来する構成単位が５０〜９０モル％、６−ヒドロキシ−２−ナフトエ酸重合性単量体に由来する構成単位が１０〜５０モル％である液晶ポリマー。 (II) The constituent unit derived from the polymerizable compound (A) is 0.01 to 7 mol%, and the constituent unit derived from 4-hydroxybenzoic acid is 50, based on 100 mol% of all the constituent units constituting the liquid crystal polymer. A liquid crystal polymer containing up to 90 mol% and 10 to 50 mol% of a constituent unit derived from a 6-hydroxy-2-naphthoic acid polymerizable monomer.
４−ヒドロキシ安息香酸に由来する構成単位は、好ましくは６０〜８８モル％、より好ましくは６５〜８５モル％、さらに好ましくは７０〜８０モル％である。 The constituent unit derived from 4-hydroxybenzoic acid is preferably 60 to 88 mol%, more preferably 65 to 85 mol%, still more preferably 70 to 80 mol%.
また、６−ヒドロキシ−２−ナフトエ酸に由来する構成単位は、好ましくは１２〜４０モル％、より好ましくは１５〜３５モル％、さらに好ましくは２０〜３０モル％である。 The constituent unit derived from 6-hydroxy-2-naphthoic acid is preferably 12 to 40 mol%, more preferably 15 to 35 mol%, still more preferably 20 to 30 mol%.
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 method for producing the liquid crystal polymer of the present invention will be described.
本発明の液晶ポリマーは、式（１）で表される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１種以上の重合性化合物（Ａ）と、重合性単量体（Ｂ）とを重合させて成る液晶ポリマーである。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、ジオール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化合物（Ａ）ならびに重合性単量体（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重縮合方法、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 liquid crystal polymer of the present invention comprises one or more polymerizable compounds (A) selected from the group consisting of the compound represented by the formula (1) and reactive derivatives thereof, and the polymerizable monomer (B). It is a liquid crystal polymer formed by polymerizing. The method for producing the liquid crystal polymer of the present invention is not particularly limited, and a polymerizable compound (A) and a polymerizable monomer (B) selected from the group consisting of a diol compound and a reactive derivative thereof are ester-bonded or bonded. The liquid crystal polymer of the present invention can be obtained by subjecting it to a known polycondensation method for forming an amide bond, for example, a molten acidlysis method, a slurry polymerization method, or the like.
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、最初に重合性化合物および／または重合性単量体を加熱して反応物質の溶融溶液を形成し、次いで重縮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 acidlysis method is a preferred method for producing the liquid crystal polymer of the present invention. In this method, a polymerizable compound and / or a polymerizable monomer is first heated to form a molten solution of a reactant, and then a polycondensation reaction is continued to obtain a molten polymer. A vacuum may be applied to facilitate the removal of by-products (eg, acetic acid, water, etc.) 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化合物および／または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 compound and / or a polymerizable monomer is reacted in the presence of a heat exchange fluid, and the solid product is obtained in a state of being 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化合物（Ａ）ならびに重合性単量体（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 both the melt acidlysis method and the slurry polymerization method, the polymerizable compound (A) and the polymerizable monomer (B) used in producing the liquid crystal polymer are both hydroxyl groups and hydroxyl groups at room temperature. / Or it can be subjected to the reaction as a modified form in which the amino group is acylated, 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化合物および／または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, and more preferably 2 or 3 carbon atoms. Particularly preferred is a method using the acetylated product of the polymerizable compound and / or the polymerizable monomer in the reaction.
重合性化合物および／または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化合物および／または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 compound and / or the polymerizable monomer may be separately acylated and pre-synthesized, or may be anhydrous with the polymerizable compound and / or the polymerizable monomer during the production of the liquid crystal polymer. It can also be produced in the reaction system by adding an acylating agent such as acetic anhydride.
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２５０〜３７０℃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 either the melt acidlysis method or the slurry polymerization method, the polymerization reaction is preferably carried out at a temperature of 150 to 400 ° C., preferably 250 to 370 ° C., under normal pressure and / or reduced pressure, and if necessary, a catalyst. 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 organic tin compounds such as dialkyl tin oxide (eg dibutyl tin oxide) and diaryl tin oxide; titanium dioxide; antimony trioxide; organic titanium compounds such as alkoxytitanium silicates and titanium alkoxides; alkalis and alkalis of carboxylic acids. Earth metal salts (eg potassium acetate); examples include gaseous acid catalysts such as Lewis acid (eg boron trifluoride), hydrogen halides (eg hydrogen chloride) and the like.
触媒を使用する場合、該触媒の量は重合性単量体（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 polymerizable monomer (B).
このようにして重縮合反応させ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 manner is usually processed into pellets, flakes, or powders after being withdrawn 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。 Pellet-like, flake-like, or powder-like liquid crystal polymers have a substantially solid phase under reduced pressure, vacuum, or an atmosphere of an inert gas such as nitrogen or helium for the purpose of increasing the molecular weight and improving heat resistance. The heat treatment may be performed in the 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 an inorganic or organic filler, other additives described below, and other resin components, and is a liquid crystal polymer. It may be a composition.
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 which may be blended in the liquid crystal polymer of the present invention may be fibrous, plate-like or granular, and may be, for example, glass fiber, milled glass, silica-alumina fiber, alumina fiber, carbon fiber or aramid. Examples include fiber, potassium titanate whiskers, aluminum borate whiskers, wollastonite, talc, mica, graphite, calcium carbonate, dolomite, clay, glass flakes, glass beads, barium sulfate, and titanium oxide. Among these, glass fiber is preferable because it has an excellent balance between physical properties and cost. Two or more kinds 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質量部に対して、好ましくは１〜２００質量部、より好ましくは５〜１００質量部である。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質量部に対して２００質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 mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the liquid crystal polymer. When the total amount of the inorganic or organic filler exceeds 200 parts by mass with respect to 100 parts by mass of the liquid crystal polymer, the molding processability of the liquid crystal polymer composition tends to decrease, and the cylinder or mold of the molding machine has a tendency to deteriorate. Wear tends to be large.
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、通常、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。 The liquid crystal polymer of the present invention includes other additives such as higher fatty acids, higher fatty acid esters, higher fatty acid amides, and higher fatty acid metal salts (where, higher fatty acids are usually carbon) as long as the effects of the present invention are not impaired. Release improver such as (10 to 25 atoms), polysiloxane, fluororesin; colorants such as dyes and pigments; antioxidants; heat stabilizers; ultraviolet absorbers; antistatic agents; surfactants Etc. may be blended. 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質量部に対して、好ましくは０．１〜１０質量部、より好ましくは０．５〜５質量部である。他の添加剤の合計量が液晶ポリマー１００質量部に対して１０質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 the other additives in the liquid crystal polymer composition of the present invention is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal polymer. When the total amount of the other additives exceeds 10 parts by mass with respect to 100 parts by mass 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, when molding the liquid crystal polymer or the liquid crystal polymer composition of the present invention, among the above other additives, additives having an external lubricant effect such as higher fatty acid, higher fatty acid ester, higher fatty acid metal salt, fluorocarbon-based surfactant, etc. May be attached to the surface of the pellet of the liquid crystal polymer in advance.
本発明の液晶ポリマーは、他の樹脂成分を含有してもよい。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、ポリオレフィン、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、または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質量部に対して、通常０．１〜１００質量部、特に０．５〜８０質量部である。 The liquid crystal polymer of the present invention may contain other resin components. Other resin components include, for example, polyamides, polyesters, polyolefins, polyacetals, polyphenylene ethers and their modifications, thermoplastic resins such as polysulfones, polyethersulfones, polyetherimides, polyamideimides, phenolic resins, epoxy resins, etc. Examples thereof include thermocurable resins such as polyimide 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 usually 0.1 to 100 parts by mass, particularly 0.5 to 80 parts by mass, relative to 100 parts by mass of the liquid crystal polymer.
本発明の液晶ポリマーの溶融粘度は、キャピラリーレオメーターを用いて、せん断速度１０００ｓ−１の条件で測定した場合、好ましくは１〜３００Ｐａ・ｓ、より好ましくは５〜１００Ｐａ・ｓ、さらに好ましくは１０〜５０Ｐａ・ｓである。尚、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。 The melt viscosity of the liquid crystal polymer of the present invention, by using a capillary rheometer, when measured under the conditions of a shear rate of 1000 s -1, preferably 1~300Pa · s, more preferably 5~100Pa · s, more preferably 10 ~ 50 Pa · s. The lower the melt viscosity, the better the fluidity during molding.
本発明の液晶ポリマー組成物は、無機または有機充填材、他の添加剤および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 or organic filler, other additives, other resin components, etc. are added to the liquid crystal polymer, and this is added to the liquid crystal polymer using a Banbury mixer, a kneader, a single-screw or twin-screw extruder, or the like. It can be obtained by melt-kneading in a temperature range from the vicinity of the crystal melting temperature of the liquid crystal polymer to the crystal melting temperature plus 100 ° C.
このようにして得られた本発明の液晶ポリマーまたは液晶ポリマー組成物は、射出成形、圧縮成形、押出成形、ブロー成形など公知の加工方法によって成形品、フィルムまたは繊維などの物品に加工される。 The liquid crystal polymer or liquid crystal polymer composition of the present invention thus obtained is processed into an article such as a molded product, a film or a fiber by a known processing method such as injection molding, compression molding, extrusion molding or blow molding.
本発明の液晶ポリマーまたは液晶ポリマー組成物は、Ｉｚｏｄ衝撃強度等の機械強度が改善され、好適には機械物性に優れるため、電気・電子部品、機械機構部品、自動車部品等として特に有用である。 The liquid crystal polymer or liquid crystal polymer composition of the present invention is particularly useful as electrical / electronic parts, mechanical mechanical parts, automobile parts, etc. because it has improved mechanical strength such as Izod impact strength and is preferably excellent in mechanical properties.
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。 Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
実施例中の溶融粘度、引張強度、曲げ強度およびＩｚｏｄ衝撃強度は、以下に記載の方法で測定した。 The melt viscosity, tensile strength, bending strength and Izod impact strength in the examples were measured by the methods described below.
（１）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、剪断速度１０００ｓｅｃ−１の条件下、３５０℃で測定した。
(1) Melt Viscosity Measured at 350 ° C. using a melt viscosity measuring device (Capillary Graph 1D manufactured by Toyo Seiki Co., Ltd.) using a 0.7 mmφ × 10 mm capillary under the condition of a shear rate of 1000 sec -1.
（２）引張強度
射出成形機（日精樹脂工業（株）製ＵＨ１０００−１１０）を用いて、シリンダー設定温度３５０℃、金型温度７０℃で、ＡＳＴＭ４号ダンベル試験片を成形し、これを用いてＡＳＴＭ Ｄ６３８に準拠して測定した。
(2) Tensile strength Using an injection molding machine (UH1000-110 manufactured by Nissei Jushi Kogyo Co., Ltd.), an ASTM No. 4 dumbbell test piece was molded at a cylinder set temperature of 350 ° C. and a mold temperature of 70 ° C. using this. Measured according to ASTM D638.
（３）曲げ強度
型締め圧１５ｔの射出成形機（住友重機械工業（株）製ＭＩＮＩＭＡＴ Ｍ２６／１５）を用いて、シリンダー設定温度３５０℃、金型温度７０℃で射出成形し、短冊状試験片（長さ６５ｍｍ×幅１２．７ｍｍ×厚さ２．０ｍｍ）を作製した。曲げ試験は、３点曲げ試験をＩＮＳＴＲＯＮ５５６７（インストロンジャパンカンパニイリミティッド社製万能試験機）を用いて、ＡＳＴＭ Ｄ７９０に準拠し、スパン間距離４０．０ｍｍ、圧縮速度１．３ｍｍ／分で行った。
(3) Bending strength Using an injection molding machine with a mold clamping pressure of 15 tons (MINIMAT M26 / 15 manufactured by Sumitomo Heavy Industries, Ltd.), injection molding was performed at a cylinder set temperature of 350 ° C and a mold temperature of 70 ° C, and a strip-shaped test was performed. Pieces (length 65 mm × width 12.7 mm × thickness 2.0 mm) were prepared. The bending test was performed by using INSTRON5567 (universal testing machine manufactured by Instron Japan Company Limited) at a distance between spans of 40.0 mm and a compression speed of 1.3 mm / min in accordance with ASTM D790.
（４）Ｉｚｏｄ衝撃強度
射出成形機（日精樹脂工業（株）製ＵＨ１０００−１１０）を用いて、シリンダー設定温度３５０℃、金型温度７０℃で、長さ１２７．０ｍｍ、幅１２．７ｍｍ、厚さ３．２ｍｍの短冊状試験片を成形した。この試験片の中央を長さ方向と垂直に切断し、長さ６３．５ｍｍ、幅１２．７ｍｍ、厚さ３．２ｍｍの短冊状試験片を得、ＡＳＴＭ Ｄ２５６に準拠して測定した。
(4) Izod Impact Strength Using an injection molding machine (UH1000-110 manufactured by Nissei Jushi Kogyo Co., Ltd.), the cylinder set temperature is 350 ° C, the mold temperature is 70 ° C, the length is 127.0 mm, the width is 12.7 mm, and the thickness is 12.7 mm. A strip-shaped test piece having a thickness of 3.2 mm was formed. The center of this test piece was cut perpendicular to the length direction to obtain a strip-shaped test piece having a length of 63.5 mm, a width of 12.7 mm and a thickness of 3.2 mm, and measured according to ASTM D256.
実施例において、下記の略号は以下の化合物を示す。
ＰＯＢ：４−ヒドロキシ安息香酸
ＢＯＮ６：６−ヒドロキシ−２−ナフトエ酸
ＨＱ：ハイドロキノン
ＢＰ：４,４'−ジヒドロキシビフェニル
ＴＰＡ：テレフタル酸
ＮＤＡ：２，６−ナフタレンジカルボン酸
In the examples, the abbreviations below refer to the following compounds.
POB: 4-Hydroxybenzoic acid BON6: 6-hydroxy-2-naphthoic acid HQ: Hydroquinone BP: 4,4'-Dihydroxybiphenyl TPA: Terephthalic acid NDA: 2,6-naphthalenedicarboxylic acid
また、重合性単量体（Ａ）として、以下のものを用いた。
ＨＤＢＡ：１，６−ビス（４−カルボキシフェノキシ）ヘキサン
ＢＣＨ：１，２−（４−カルボキシフェノキシ）エタン
ＥＤＮＡ：６，６’−（エチレンジオキシ）ビス−２−ナフトエ酸
Moreover, the following was used as the polymerizable monomer (A).
HDBA: 1,6-bis (4-carboxyphenoxy) hexane BCH: 1,2- (4-carboxyphenoxy) ethane EDNA: 6,6'-(ethylenedioxy) bis-2-naphthoic acid
［実施例１］
トルクメーター付き攪拌装置および留出管を備えた反応容器に下記化合物を仕込み、さらに全単量体の水酸基量（モル）に対して１．０３倍モルの無水酢酸を仕込み、次の条件で脱酢酸重合を行った。
ＨＤＢＡ：２３．３ｇ（１．０モル％）
ＰＯＢ：２１３．７ｇ（２３．８モル％）
ＢＯＮ６：９１９．８ｇ（７５．２モル％）
[Example 1]
The following compounds were charged in a reaction vessel equipped with a stirrer with a torque meter and a distilling tube, and 1.03 times the molar amount of acetic anhydride with respect to the amount of hydroxyl groups (moles) of all the monomers was charged, and the mixture was removed under the following conditions. Acetic anhydride polymerization was performed.
HDBA: 23.3 g (1.0 mol%)
POB: 213.7 g (23.8 mol%)
BON6: 919.8 g (75.2 mol%)
窒素ガス雰囲気下に室温から１５０℃まで１時間で昇温し、同温度にて３０分間保持した。次いで、副生する酢酸を留去しながら２１０℃まで速やかに昇温し、同温度にて３０分間保持した。その後、３５０℃まで４時間かけて昇温した後、８０分かけて１０ｍｍＨｇにまで減圧した。所定のトルクを示した時点で重合反応を終了し、反応容器内容物を取り出し、粉砕機により液晶ポリマーのペレットを得た。重合時の留出酢酸量は、ほぼ理論値どおりであった。得られたペレットを用いて上記の方法により溶融粘度、引張強度、曲げ強度およびＩｚｏｄ衝撃強度を測定した。結果を表１に示す。 The temperature was raised from room temperature to 150 ° C. in 1 hour under a nitrogen gas atmosphere, and the temperature was maintained at the same temperature for 30 minutes. Then, the temperature was rapidly raised to 210 ° C. while distilling off the acetic acid produced as a by-product, and the temperature was maintained at the same temperature for 30 minutes. Then, the temperature was raised to 350 ° C. over 4 hours, and then the pressure was reduced to 10 mmHg over 80 minutes. When a predetermined torque was exhibited, the polymerization reaction was terminated, the contents of the reaction vessel were taken out, and pellets of the liquid crystal polymer were obtained by a pulverizer. The amount of distillen acetic acid at the time of polymerization was almost the same as the theoretical value. Using the obtained pellets, the melt viscosity, tensile strength, bending strength and Izod impact strength were measured by the above method. The results are shown in Table 1.
［実施例２〜５、比較例１〜２］
式（１）で表される化合物（重合性化合物）、ＰＯＢおよびＢＯＮ６を表１に示す割合（モル％）となるように用いたこと以外は実施例１と同様にして、液晶ポリマーのペレットを得た。得られたペレットを用いて上記の方法により溶融粘度、引張強度、曲げ強度およびＩｚｏｄ衝撃強度を測定した。結果を表１に示す。
[Examples 2 to 5, Comparative Examples 1 to 2]
The pellets of the liquid crystal polymer were prepared in the same manner as in Example 1 except that the compound represented by the formula (1) (polymerizable compound), POB and BON6 were used in the proportions (mol%) shown in Table 1. Obtained. Using the obtained pellets, the melt viscosity, tensile strength, bending strength and Izod impact strength were measured by the above method. The results are shown in Table 1.
［実施例６］
トルクメーター付き攪拌装置および留出管を備えた反応容器に下記化合物を仕込み、さらに全単量体の水酸基量（モル）に対して１．０３倍モルの無水酢酸を仕込み、次の条件で脱酢酸重合を行った。
ＨＤＢＡ：２３．３ｇ（１．０モル％）
ＰＯＢ：３９０．５ｇ（４３．５モル％）
ＢＯＮ６：１９４．５ｇ（１５．９モル％）
ＨＱ：１４１．７ｇ（１９．８モル％）
ＴＰＡ：２１３．８ｇ（１９．８モル％）
[Example 6]
The following compounds were charged in a reaction vessel equipped with a stirrer with a torque meter and a distilling tube, and 1.03 times the molar amount of acetic anhydride with respect to the amount of hydroxyl groups (moles) of all the monomers was charged, and the mixture was removed under the following conditions. Acetic anhydride polymerization was performed.
HDBA: 23.3 g (1.0 mol%)
POB: 390.5 g (43.5 mol%)
BON6: 194.5 g (15.9 mol%)
HQ: 141.7 g (19.8 mol%)
TPA: 213.8 g (19.8 mol%)
窒素ガス雰囲気下に室温から１５０℃まで１時間で昇温し、同温度にて３０分間保持した。次いで、副生する酢酸を留去しながら２１０℃まで速やかに昇温し、同温度にて３０分間保持した。その後、３４５℃まで５時間かけて昇温した後、９０分かけて２０ｍｍＨｇにまで減圧した。所定のトルクを示した時点で重合反応を終了し、反応容器内容物を取り出し、粉砕機により液晶ポリマーのペレットを得た。得られたペレットを用いて上記の方法により溶融粘度、引張強度、曲げ強度およびＩｚｏｄ衝撃強度を測定した。結果を表１に示す。 The temperature was raised from room temperature to 150 ° C. in 1 hour under a nitrogen gas atmosphere, and the temperature was maintained at the same temperature for 30 minutes. Then, the temperature was rapidly raised to 210 ° C. while distilling off the acetic acid produced as a by-product, and the temperature was maintained at the same temperature for 30 minutes. Then, the temperature was raised to 345 ° C. over 5 hours, and then the pressure was reduced to 20 mmHg over 90 minutes. When a predetermined torque was exhibited, the polymerization reaction was terminated, the contents of the reaction vessel were taken out, and pellets of the liquid crystal polymer were obtained by a pulverizer. Using the obtained pellets, the melt viscosity, tensile strength, bending strength and Izod impact strength were measured by the above method. The results are shown in Table 1.
［比較例３］
仕込み化合物を以下のように変更した以外は、実施例６と同様にして液晶ポリマーのペレットを得た。得られたペレットを用いて上記の方法により溶融粘度、引張強度、曲げ強度およびＩｚｏｄ衝撃強度を測定した。結果を表１に示す。
ＰＯＢ：３９５．０ｇ（４４．０モル％）
ＢＯＮ６：１９５．７ｇ（１６．０モル％）
ＨＱ：１４３．１ｇ（２０．０モル％）
ＴＰＡ：２１６．０ｇ（２０．０モル％）
[Comparative Example 3]
Liquid crystal polymer pellets were obtained in the same manner as in Example 6 except that the charged compound was changed as follows. Using the obtained pellets, the melt viscosity, tensile strength, bending strength and Izod impact strength were measured by the above method. The results are shown in Table 1.
POB: 395.0 g (44.0 mol%)
BON6: 195.7 g (16.0 mol%)
HQ: 143.1 g (20.0 mol%)
TPA: 216.0 g (20.0 mol%)
［実施例７］
トルクメーター付き攪拌装置および留出管を備えた反応容器に下記化合物を仕込み、さらに全単量体の水酸基量（モル）に対して１．０３倍モルの無水酢酸を仕込み、次の条件で脱酢酸重合を行った。
ＨＤＢＡ：２３．３ｇ（１．０モル％）
ＰＯＢ：３１７．８ｇ（３５．４モル％）
ＢＯＮ６：４８．９ｇ（４．０モル％）
ＨＱ：１１３．８ｇ（１５．９モル％）
ＢＰ：１６８．２ｇ（１３．９モル％）
ＴＰＡ：３２１．８ｇ（２９．８モル％）
[Example 7]
The following compounds were charged in a reaction vessel equipped with a stirrer with a torque meter and a distilling tube, and 1.03 times the molar amount of acetic anhydride with respect to the amount of hydroxyl groups (moles) of all the monomers was charged, and the mixture was removed under the following conditions. Acetic anhydride polymerization was performed.
HDBA: 23.3 g (1.0 mol%)
POB: 317.8 g (35.4 mol%)
BON6: 48.9 g (4.0 mol%)
HQ: 113.8 g (15.9 mol%)
BP: 168.2 g (13.9 mol%)
TPA: 321.8 g (29.8 mol%)
窒素ガス雰囲気下に室温から１４５℃まで１時間で昇温し、同温度にて３０分間保持した。次いで、副生する酢酸を留去しながら２１０℃まで速やかに昇温し、同温度にて３０分間保持した。その後、３５０℃まで７時間かけて昇温した後、８０分かけて５ｍｍＨｇにまで減圧した。所定のトルクを示した時点で重合反応を終了し、反応容器内容物を取り出し、粉砕機により液晶ポリマーのペレットを得た。得られたペレットを用いて上記の方法により溶融粘度、引張強度、曲げ強度およびＩｚｏｄ衝撃強度を測定した。結果を表１に示す。 The temperature was raised from room temperature to 145 ° C. in 1 hour under a nitrogen gas atmosphere, and the temperature was maintained at the same temperature for 30 minutes. Then, the temperature was rapidly raised to 210 ° C. while distilling off the acetic acid produced as a by-product, and the temperature was maintained at the same temperature for 30 minutes. Then, the temperature was raised to 350 ° C. over 7 hours, and then the pressure was reduced to 5 mmHg over 80 minutes. When a predetermined torque was exhibited, the polymerization reaction was terminated, the contents of the reaction vessel were taken out, and pellets of the liquid crystal polymer were obtained by a pulverizer. Using the obtained pellets, the melt viscosity, tensile strength, bending strength and Izod impact strength were measured by the above method. The results are shown in Table 1.
［比較例４］
仕込み化合物を以下のように変更した以外は、実施例７と同様にして液晶ポリマーのペレットを得た。得られたペレットを用いて上記の方法により溶融粘度、引張強度、曲げ強度およびＩｚｏｄ衝撃強度を測定した。結果を表１に示す。
ＰＯＢ：３２３．２ｇ（３６．０モル％）
ＢＯＮ６：４８．９ｇ（４．０モル％）
ＨＱ：１１４．５ｇ（１６．０モル％）
ＢＰ：１６９．５ｇ（１４．０モル％）
ＴＰＡ：３２４．０ｇ（３０．０モル％）
[Comparative Example 4]
Liquid crystal polymer pellets were obtained in the same manner as in Example 7 except that the charged compound was changed as follows. Using the obtained pellets, the melt viscosity, tensile strength, bending strength and Izod impact strength were measured by the above method. The results are shown in Table 1.
POB: 323.2 g (36.0 mol%)
BON6: 48.9 g (4.0 mol%)
HQ: 114.5 g (16.0 mol%)
BP: 169.5 g (14.0 mol%)
TPA: 324.0 g (30.0 mol%)
［実施例８］
トルクメーター付き攪拌装置および留出管を備えた反応容器に下記化合物を仕込み、さらに全単量体の水酸基量（モル）に対して１．０３倍モルの無水酢酸を仕込み、次の条件で脱酢酸重合を行った。
ＨＤＢＡ：２３．３ｇ（１．０モル％）
ＰＯＢ：６３４．７ｇ（７０．７モル％）
ＢＯＮ６：３０．６ｇ（２．５モル％）
ＨＱ：９２．３ｇ（１２．９モル％）
ＮＤＡ：１８１．３ｇ（１２．９モル％）
[Example 8]
The following compounds were charged in a reaction vessel equipped with a stirrer with a torque meter and a distilling tube, and 1.03 times the molar amount of acetic anhydride with respect to the amount of hydroxyl groups (moles) of all the monomers was charged, and the mixture was removed under the following conditions. Acetic anhydride polymerization was performed.
HDBA: 23.3 g (1.0 mol%)
POB: 634.7 g (70.7 mol%)
BON6: 30.6 g (2.5 mol%)
HQ: 92.3 g (12.9 mol%)
NDA: 181.3g (12.9 mol%)
窒素ガス雰囲気下に室温から１４５℃まで１時間で昇温し、同温度にて３０分間保持した。次いで、副生する酢酸を留去しながら２１０℃まで速やかに昇温し、同温度にて３０分間保持した。その後、３４５℃まで７時間かけて昇温した後、８０分かけて１０ｍｍＨｇにまで減圧した。所定のトルクを示した時点で重合反応を終了し、反応容器内容物を取り出し、粉砕機により液晶ポリマーのペレットを得た。得られたペレットを用いて上記の方法により溶融粘度、引張強度、曲げ強度およびＩｚｏｄ衝撃強度を測定した。結果を表１に示す。 The temperature was raised from room temperature to 145 ° C. in 1 hour under a nitrogen gas atmosphere, and the temperature was maintained at the same temperature for 30 minutes. Then, the temperature was rapidly raised to 210 ° C. while distilling off the acetic acid produced as a by-product, and the temperature was maintained at the same temperature for 30 minutes. Then, the temperature was raised to 345 ° C. over 7 hours, and then the pressure was reduced to 10 mmHg over 80 minutes. When a predetermined torque was exhibited, the polymerization reaction was terminated, the contents of the reaction vessel were taken out, and pellets of the liquid crystal polymer were obtained by a pulverizer. Using the obtained pellets, the melt viscosity, tensile strength, bending strength and Izod impact strength were measured by the above method. The results are shown in Table 1.
［比較例５］
仕込み化合物を以下のように変更した以外は、実施例８と同様にして液晶ポリマーのペレットを得た。得られたペレットを用いて上記の方法により溶融粘度、引張強度、曲げ強度およびＩｚｏｄ衝撃強度を測定した。結果を表１に示す。
ＰＯＢ：６４１．９ｇ（７１．５モル％）
ＢＯＮ６：３０．６ｇ（２．５モル％）
ＨＱ：９３．０ｇ（１３．０モル％）
ＮＤＡ：１８２．７ｇ（１３．０モル％）
[Comparative Example 5]
Liquid crystal polymer pellets were obtained in the same manner as in Example 8 except that the charged compound was changed as follows. Using the obtained pellets, the melt viscosity, tensile strength, bending strength and Izod impact strength were measured by the above method. The results are shown in Table 1.
POB: 641.9 g (71.5 mol%)
BON6: 30.6 g (2.5 mol%)
HQ: 93.0 g (13.0 mol%)
NDA: 182.7 g (13.0 mol%)
［実施例９］
トルクメーター付き攪拌装置および留出管を備えた反応容器に下記化合物を仕込み、さらに全単量体の水酸基量（モル）に対して１．０３倍モルの無水酢酸を仕込み、次の条件で脱酢酸重合を行った。
ＨＤＢＡ：２３．３ｇ（１．０モル％）
ＢＯＮ６：６５３．２ｇ（５３．４モル％）
ＨＱ：１４．３ｇ（２．０モル％）
ＢＰ：２５１．８ｇ（２０．８モル％）
ＴＰＡ：２４６．２ｇ（２２．８モル％）
[Example 9]
The following compounds were charged in a reaction vessel equipped with a stirrer with a torque meter and a distilling tube, and 1.03 times the molar amount of acetic anhydride with respect to the amount of hydroxyl groups (moles) of all the monomers was charged, and the mixture was removed under the following conditions. Acetic anhydride polymerization was performed.
HDBA: 23.3 g (1.0 mol%)
BON6: 653.2 g (53.4 mol%)
HQ: 14.3 g (2.0 mol%)
BP: 251.8 g (20.8 mol%)
TPA: 246.2 g (22.8 mol%)
窒素ガス雰囲気下に室温から１４５℃まで１時間かけて昇温し、１４５℃で３０分保持した。次いで、副生する酢酸を留出させつつ３５０℃まで７時間かけて昇温した後、８０分かけて５ｍｍＨｇにまで減圧した。所定の攪拌トルクを示した時点で重合反応を終了し、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。重合時の留出酢酸量は、ほぼ理論値どおりであった。得られたペレットを用いて上記の方法により、溶融粘度、引張強度およびＩｚｏｄ衝撃強度を測定した。結果を表１に示す。 The temperature was raised from room temperature to 145 ° C. over 1 hour under a nitrogen gas atmosphere, and the temperature was maintained at 145 ° C. for 30 minutes. Then, the temperature was raised to 350 ° C. over 7 hours while distilling acetic acid produced as a by-product, and then the pressure was reduced to 5 mmHg over 80 minutes. When the predetermined stirring torque was shown, the polymerization reaction was terminated, the contents were taken out from the reaction vessel, and pellets of the liquid crystal polymer were obtained by a pulverizer. The amount of distillen acetic acid at the time of polymerization was almost the same as the theoretical value. Using the obtained pellets, the melt viscosity, tensile strength and Izod impact strength were measured by the above method. The results are shown in Table 1.
［比較例６］
仕込み化合物を以下のように変更した以外は、実施例８と同様にして液晶ポリマーのペレットを得た。得られたペレットを用いて上記の方法により溶融粘度、引張強度、曲げ強度およびＩｚｏｄ衝撃強度を測定した。結果を表１に示す。
ＢＯＮ６：６６０．５ｇ（５４．０モル％）
ＨＱ：１４．３ｇ（２．０モル％）
ＢＰ：２５４．２ｇ（２１．０モル％）
ＴＰＡ：２４８．４ｇ（２３．０モル％）
[Comparative Example 6]
Liquid crystal polymer pellets were obtained in the same manner as in Example 8 except that the charged compound was changed as follows. Using the obtained pellets, the melt viscosity, tensile strength, bending strength and Izod impact strength were measured by the above method. The results are shown in Table 1.
BON6: 660.5 g (54.0 mol%)
HQ: 14.3 g (2.0 mol%)
BP: 254.2 g (21.0 mol%)
TPA: 248.4 g (23.0 mol%)
［実施例１０］
トルクメーター付き攪拌装置および留出管を備えた反応容器に下記化合物を仕込み、さらに全単量体の水酸基量（モル）に対して１．０３倍モルの無水酢酸を仕込み、次の条件で脱酢酸重合を行った。
ＨＤＢＡ：２３．３ｇ（１．０モル％）
ＰＯＢ：６５０．９ｇ（７２．５モル％）
ＢＯＮ６：３２４．１ｇ（２６．５モル％）
[Example 10]
The following compounds were charged in a reaction vessel equipped with a stirrer with a torque meter and a distilling tube, and 1.03 times the molar amount of acetic anhydride with respect to the amount of hydroxyl groups (moles) of all the monomers was charged, and the mixture was removed under the following conditions. Acetic anhydride polymerization was performed.
HDBA: 23.3 g (1.0 mol%)
POB: 650.9 g (72.5 mol%)
BON6: 324.1 g (26.5 mol%)
窒素ガス雰囲気下に室温から１５０℃まで１時間で昇温し、同温度にて３０分間保持した。次いで、副生する酢酸を留去しながら２１０℃まで速やかに昇温し、同温度にて３０分間保持した。その後、３２５℃まで５時間かけて昇温した後、９０分かけて２０ｍｍＨｇにまで減圧した。所定のトルクを示した時点で重合反応を終了し、反応容器内容物を取り出し、粉砕機により液晶ポリマーのペレットを得た。重合時の留出酢酸量は、ほぼ理論値どおりであった。得られたペレットを用いて上記の方法により溶融粘度、引張強度、曲げ強度およびＩｚｏｄ衝撃強度を測定した。結果を表１に示す。 The temperature was raised from room temperature to 150 ° C. in 1 hour under a nitrogen gas atmosphere, and the temperature was maintained at the same temperature for 30 minutes. Then, the temperature was rapidly raised to 210 ° C. while distilling off the acetic acid produced as a by-product, and the temperature was maintained at the same temperature for 30 minutes. Then, the temperature was raised to 325 ° C. over 5 hours, and then the pressure was reduced to 20 mmHg over 90 minutes. When a predetermined torque was exhibited, the polymerization reaction was terminated, the contents of the reaction vessel were taken out, and pellets of the liquid crystal polymer were obtained by a pulverizer. The amount of distillen acetic acid at the time of polymerization was almost the same as the theoretical value. Using the obtained pellets, the melt viscosity, tensile strength, bending strength and Izod impact strength were measured by the above method. The results are shown in Table 1.
［比較例７］
仕込み化合物を以下のように変更した以外は、実施例１０と同様にして液晶ポリマーのペレットを得た。得られたペレットを用いて上記の方法により溶融粘度、引張強度、曲げ強度およびＩｚｏｄ衝撃強度を測定した。結果を表１に示す。
ＰＯＢ：６５５．４ｇ（７３．０モル％）
ＢＯＮ６：３３０．３ｇ（２７．０モル％）
[Comparative Example 7]
Liquid crystal polymer pellets were obtained in the same manner as in Example 10 except that the charged compound was changed as follows. Using the obtained pellets, the melt viscosity, tensile strength, bending strength and Izod impact strength were measured by the above method. The results are shown in Table 1.
POB: 655.4 g (73.0 mol%)
BON6: 330.3 g (27.0 mol%)
表１に示すように、特定の脂肪族ジカルボン酸を含有する本発明の液晶ポリマー（実施例１〜１０）は、それらを含有しない液晶ポリマー（比較例１および比較例３〜７）とそれぞれ比較して、いずれも引張強度、曲げ強度およびＩｚｏｄ衝撃強度等の機械特性が改善され、機械強度向上効果があることが理解される。 As shown in Table 1, the liquid crystal polymers of the present invention containing specific aliphatic dicarboxylic acids (Examples 1 to 10) are compared with the liquid crystal polymers not containing them (Comparative Examples 1 and Comparative Examples 3 to 7, respectively). Therefore, it is understood that all of them have improved mechanical properties such as tensile strength, bending strength and Izod impact strength, and have an effect of improving mechanical strength.
Claims (13)
で表される化合物ならびにそれらの反応性誘導体からなる群から選択される１種以上の重合性化合物（Ａ）に由来する構成単位と、重合性単量体（Ｂ）に由来する構成単位とを含む液晶ポリマーであって、重合性化合物（Ａ）に由来する構成単位の合計量が、液晶ポリマーを構成する全構成単位１００モル％に対して０．０１〜７モル％である、液晶ポリマー。 Equation (1)
A structural unit derived from one or more polymerizable compounds (A) selected from the group consisting of the compound represented by the above and reactive derivatives thereof, and a structural unit derived from the polymerizable monomer (B). A liquid crystal polymer containing, wherein the total amount of the structural units derived from the polymerizable compound (A) is 0.01 to 7 mol% with respect to 100 mol% of all the structural units constituting the liquid crystal polymer.
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