JP2018012789A - Liquid crystal polymer - Google Patents
Liquid crystal polymer Download PDFInfo
- Publication number
- JP2018012789A JP2018012789A JP2016143471A JP2016143471A JP2018012789A JP 2018012789 A JP2018012789 A JP 2018012789A JP 2016143471 A JP2016143471 A JP 2016143471A JP 2016143471 A JP2016143471 A JP 2016143471A JP 2018012789 A JP2018012789 A JP 2018012789A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- liquid crystal
- crystal polymer
- aromatic
- 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.)
- Granted
Links
- 229920000106 Liquid crystal polymer Polymers 0.000 title claims abstract description 89
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 title claims abstract description 89
- 239000000178 monomer Substances 0.000 claims abstract description 64
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 72
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 54
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 44
- -1 aromatic diol Chemical class 0.000 claims description 38
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 28
- 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 26
- 125000003118 aryl group Chemical group 0.000 claims description 23
- QNVNLUSHGRBCLO-UHFFFAOYSA-N 5-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(O)=CC(C(O)=O)=C1 QNVNLUSHGRBCLO-UHFFFAOYSA-N 0.000 claims description 20
- 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 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 15
- 239000000203 mixture Substances 0.000 claims description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000011256 inorganic filler Substances 0.000 claims description 7
- 239000012766 organic filler Substances 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 6
- 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 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 150000004984 aromatic diamines Chemical class 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 3
- 229960001755 resorcinol Drugs 0.000 claims description 3
- 239000003990 capacitor Substances 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 claims description 2
- 206010061592 cardiac fibrillation Diseases 0.000 abstract description 35
- 230000002600 fibrillogenic effect Effects 0.000 abstract description 35
- 229920005989 resin Polymers 0.000 abstract description 26
- 239000011347 resin Substances 0.000 abstract description 26
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 230000002209 hydrophobic effect Effects 0.000 abstract description 3
- 230000000740 bleeding effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 36
- 239000000047 product Substances 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- 239000000155 melt Substances 0.000 description 18
- 239000013078 crystal Substances 0.000 description 17
- 238000002844 melting Methods 0.000 description 17
- 230000008018 melting Effects 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 238000006068 polycondensation reaction Methods 0.000 description 13
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000004821 distillation Methods 0.000 description 11
- 238000000465 moulding Methods 0.000 description 11
- 239000008188 pellet Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 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
- 125000000217 alkyl group Chemical group 0.000 description 7
- 238000005452 bending Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 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
- 150000004820 halides Chemical class 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 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
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052736 halogen Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009257 reactivity Effects 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
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000004974 Thermotropic liquid crystal Substances 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
- 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
- 230000006866 deterioration Effects 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000010954 inorganic particle 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
- 230000020477 pH reduction Effects 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
- 230000000379 polymerizing effect Effects 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical group NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-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
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-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
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 1
- AJHPGXZOIAYYDW-UHFFFAOYSA-N 3-(2-cyanophenyl)-2-[(2-methylpropan-2-yl)oxycarbonylamino]propanoic acid Chemical group 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
- 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
- FDHZNXYLISNHCG-UHFFFAOYSA-N 4-[2-(4-carboxyphenyl)phenyl]benzoic acid Chemical group C1(=CC=C(C=C1)C(=O)O)C=1C(=CC=CC1)C1=CC=C(C=C1)C(=O)O FDHZNXYLISNHCG-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
- SMAMQSIENGBTRV-UHFFFAOYSA-N 5-hydroxynaphthalene-2-carboxylic acid Chemical compound OC1=CC=CC2=CC(C(=O)O)=CC=C21 SMAMQSIENGBTRV-UHFFFAOYSA-N 0.000 description 1
- NZTPZUIIYNYZKT-UHFFFAOYSA-N 6-aminonaphthalene-2-carboxylic acid Chemical group C1=C(C(O)=O)C=CC2=CC(N)=CC=C21 NZTPZUIIYNYZKT-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 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
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 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
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007334 copolymerization reaction 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
- 238000001125 extrusion Methods 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle 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
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 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
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical group 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
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 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
- 238000013001 point bending Methods 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
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 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
- 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
- 238000003672 processing method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- 230000000007 visual effect Effects 0.000 description 1
- 239000003039 volatile agent Substances 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
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
本発明は、成形品のフィブリル化が抑制された液晶ポリマーに関する。 The present invention relates to a liquid crystal polymer in which fibrillation of a molded product is suppressed.
液晶ポリマーは、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、薄肉成形性に優れることから、精密機器等の電子部品への使用が拡大しつつある。 Liquid crystal polymers are excellent in mechanical properties, moldability, chemical resistance, gas barrier properties, moisture resistance, electrical properties, etc., and are therefore used in parts in various fields. In particular, since it is excellent in heat resistance and thin-wall moldability, its use for electronic parts such as precision instruments is expanding.
一方、液晶ポリマーの成形品は、超音波洗浄や他部材との摺動によって、樹脂表面が剥離し、毛羽立つ現象(以下、「フィブリル化」と称する)が生じることが知られている。 On the other hand, it is known that a molded product of a liquid crystal polymer causes a phenomenon of fluffing (hereinafter referred to as “fibrillation”) due to peeling of the resin surface by ultrasonic cleaning or sliding with another member.
精密機器、特にレンズがあるような光学機器の場合、わずかなゴミや埃が機器性能に影響を与える。例えば、カメラモジュールのような光学機器に用いられる部品においては、小さなゴミ、油分、埃などがレンズに付着すると、カメラモジュールの光学特性を著しく低下させる原因となる。 In the case of precision equipment, especially optical equipment with a lens, a small amount of dust and dirt affects the performance of the equipment. For example, in a part used in an optical device such as a camera module, if small dust, oil, dust or the like adheres to the lens, it causes a significant deterioration in the optical characteristics of the camera module.
このような光学特性の低下を防ぐ目的で、通常、カメラモジュールを構成する部品は、組み立て前に超音波洗浄され、表面に付着している小さなゴミや埃等が除去される。 In order to prevent such deterioration of the optical characteristics, usually, the parts constituting the camera module are ultrasonically cleaned before assembly to remove small dust or dust adhering to the surface.
しかしながら、上述したように超音波洗浄によって、液晶ポリマー成形品表面のフィブリル化によって生じる粉が、カメラモジュール組立時およびカメラ使用時に異物となり、カメラモジュールの光学特性を著しく低下させるという問題があった。 However, as described above, there has been a problem that the powder generated by the fibrillation of the surface of the liquid crystal polymer molded product by ultrasonic cleaning becomes a foreign substance when the camera module is assembled and when the camera is used, and the optical characteristics of the camera module are significantly deteriorated.
フィブリル化を抑える方法として、疎水性シリカ等の無機粒子を樹脂に添加することが知られている。しかし、シリカ等の無機粒子は樹脂との吸着力が弱く、ブリードアウトするという問題があった。ブリードアウトした微粒子は、ごく微小かつ微量であっても、カメラモジュールの光学特性を低下させる異物となり得る。 As a method for suppressing fibrillation, it is known to add inorganic particles such as hydrophobic silica to a resin. However, inorganic particles such as silica have a problem of bleed out due to their weak adsorption force with the resin. Even if the fine particles bleed out are very minute and minute, they can be a foreign substance that deteriorates the optical characteristics of the camera module.
また、粒子径1μm以下の硫酸バリウムを含有させることにより、フィブリル化が抑制された液晶ポリエステル樹脂組成物が提案されている(特許文献1)。しかし、この樹脂組成物は5〜40容量部もの大量の硫酸バリウムを含有させるものであり、やはり硫酸バリウムがブリードアウトするという問題が避けられないものであった。 Moreover, the liquid crystal polyester resin composition by which fibrillation was suppressed by containing barium sulfate with a particle diameter of 1 micrometer or less is proposed (patent document 1). However, this resin composition contains a large amount of 5 to 40 parts by volume of barium sulfate, and the problem that the barium sulfate bleeds out is inevitable.
したがって、ブリードアウトする物質を含有させることなく、樹脂自体がフィブリル化抑制効果を有する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 in which the resin itself has an effect of suppressing fibrillation without containing a substance that bleeds out.
本発明は、疎水性シリカや硫酸バリウム等のブリードアウトする物質を含まずとも、樹脂自体にフィブリル化を抑制する効果を有する液晶ポリマーを提供することを目的とする。 An object of the present invention is to provide a liquid crystal polymer having an effect of suppressing fibrillation in a resin itself without containing a bleed-out substance such as hydrophobic silica or barium sulfate.
本発明者らは、液晶ポリマー成形品のフィブリル化抑制について鋭意検討した結果、3,5−置換芳香族カルボン酸を他の重合性単量体と共重合させることによって、フィブリル化が抑制された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 intensive studies on the suppression of fibrillation of liquid crystal polymer molded products, the present inventors have suppressed fibrillation by copolymerizing 3,5-substituted aromatic carboxylic acids with other polymerizable monomers. The present inventors have found that a liquid crystal polymer can be obtained and have completed the present invention.
すなわち、本発明は、式(I)で表される芳香族カルボン酸(以下、3,5−置換芳香族カルボン酸ともいう)およびその反応性誘導体からなる群より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、つまり上記重合性単量体(A)と他の重合性単量体(B)とを重合させて成る液晶ポリマーを提供する。
本発明の液晶ポリマーは、成形品表面のフィブリル化が抑制されるという効果を有するため、超音波洗浄を必要とする部品や、他の部材との摺動を伴う摺動部材などの電子部品の成形用樹脂として好適に用いることができる。 Since the liquid crystal polymer of the present invention has the effect of suppressing the fibrillation of the surface of the molded product, it can be used for electronic parts such as parts that require ultrasonic cleaning and sliding members that slide with other members. It can be suitably used as a molding resin.
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3,5−置換芳香族カルボン酸の反応性誘導体としては、3,5−置換芳香族カルボン酸のアルキル、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、炭素数6までのものが好適に用いられる。3,5−置換芳香族カルボン酸、およびその反応性誘導体からなる群より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 3,5-substituted aromatic carboxylic acids that can be used in the present invention include alkyl, alkoxy or halogen substituted products, acylated products, ester derivatives, acid halides of 3,5-substituted aromatic carboxylic acids. 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. As the polymerizable monomer (A) selected from the group consisting of 3,5-substituted aromatic carboxylic acids and reactive derivatives thereof, only one kind of compound may be used, or two or more kinds of compounds are combined. May be used.
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、3,5−置換芳香族カルボン酸としては、式(II)で表される5−ヒドロキシイソフタル酸、式(III)で表されるα−レゾルシン酸および式(IV)で表されるトリメシン酸が挙げられ、液晶ポリマーのフィブリル化抑制能に優れる点で、5−ヒドロキシイソフタル酸またはα−レゾルシン酸が好ましく、特に5−ヒドロキシイソフタル酸が好ましい。
本発明の液晶ポリマーに用いる、3,5−置換芳香族カルボン酸、およびその反応性誘導体からなる群より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、0.01〜10モル部であることが好ましく、0.1〜5モル部であることがより好ましく、1.0〜3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10モル部を超えると、生成するポリマーがゲル化しやすくなり、液晶性が損なわれる傾向がある。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、生成するポリマーのフィブリル化が抑制されない傾向がある。 The total amount of the polymerizable monomer (A) selected from the group consisting of 3,5-substituted aromatic carboxylic acids and reactive derivatives thereof used in the liquid crystal polymer of the present invention is different from other polymerizable monomers. It is preferable that it is 0.01-10 mol part with respect to 100 mol part of total amounts of (B), It is more preferable that it is 0.1-5 mol part, It is 1.0-3 mol part. Is more preferable. When the total amount of the polymerizable monomer (A) exceeds 10 parts by mole with respect to 100 parts by mole of the total amount of the other polymerizable monomers (B), the resulting polymer is easily gelled, and the liquid crystallinity is reduced. There is a tendency to be damaged. 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), fibrillation of the produced polymer is not suppressed. 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 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)として、前記化合物の1種以上が結合してなるオリゴマーを、3,5−置換芳香族カルボン酸およびその反応性誘導体からなる群より選択される重合性単量体(A)との共重合に供してもよい。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毎にカウントするものとする。 As another polymerizable monomer (B) used in the liquid crystal polymer of the present invention, an oligomer formed by bonding one or more of the above compounds is a group consisting of a 3,5-substituted aromatic carboxylic acid and a reactive derivative thereof. You may use for a copolymerization with the polymerizable monomer (A) selected more. 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 counted for each unit of mass.
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、5−ヒドロキシ−2−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、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−安息香酸および4’−ヒドロキシフェニル−3−安息香酸、およびこれらのアルキル、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、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結晶融解温度を調節し易いという観点から、4−ヒドロキシ安息香酸および6−ヒドロキシ−2−ナフトエ酸からなる群から選択される1種以上の化合物が好ましい。 Specific examples of the aromatic hydroxycarboxylic acid include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 2-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 5-hydroxy-2-naphthoic acid, and 7-hydroxy. 2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid and 4'-hydroxyphenyl-3-benzoic acid, and these And alkyl-substituted, alkoxy- or halogen-substituted compounds thereof, and ester-forming derivatives thereof such as acylated products, ester derivatives and acid halides thereof. Among these, one or more selected from the group consisting of 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid from the viewpoint of easy adjustment of heat resistance and mechanical strength and crystal melting temperature of the obtained liquid crystal polymer Are preferred.
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、およびこれらのアルキル、アルコキシまたはハロゲン置換体ならびにこ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。これらの中でも、得られる液晶ポリマーの耐熱性を効果的に高められる観点から、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種以上の化合物が好ましく、テレフタル酸および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種以上の化合物がより好ましい。 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, and alkyl-, alkoxy- or halogen-substituted products thereof, and ester-forming derivatives thereof such as ester derivatives and acid halides thereof. Among these, one or more compounds selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid are preferable from the viewpoint of effectively improving the heat resistance of the obtained liquid crystal polymer. And more preferably one or more compounds selected from the group consisting of 2,6-naphthalenedicarboxylic acid.
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ニルエーテルおよびビスフェノールA、およびこれらのアルキル、アルコキシまたはハロゲン置換体ならびにこ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、重合時の反応性に優れる観点から、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からなる群より選択される1種以上の化合物が好ましく、ハイドロキノンおよび4,4’−ジヒドロキシビフェニルからなる群から選択される1種以上の化合物がより好ましい。 Specific examples of the aromatic diol include hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 3,3′-dihydroxybiphenyl, 3,4′-dihydroxybiphenyl, Examples include ester-forming derivatives such as 4,4′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl ether and bisphenol A, and alkyl, alkoxy or halogen substituents thereof and acylated products thereof. Among these, from the viewpoint of excellent reactivity during polymerization, one or more compounds selected from the group consisting of hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, 2,6-dihydroxynaphthalene and bisphenol A are preferable, One or more compounds selected from the group consisting of hydroquinone and 4,4′-dihydroxybiphenyl are more 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−アミノ安息香酸および6−アミノ−2−ナフトエ酸、およびこれらのアルキル、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。 Specific examples of the aromatic aminocarboxylic acid include 4-aminobenzoic acid, 3-aminobenzoic acid and 6-amino-2-naphthoic acid, and alkyl, alkoxy or halogen substituted products thereof, and acylated products and esters thereof. Examples thereof include ester-forming derivatives such as derivatives and 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、およびこれらのアルキル、アルコキシまたはハロゲン置換体ならびにこ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、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観点から、4−アミノフェノールが好ましい。 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, and their Examples include alkyl-, alkoxy- or halogen-substituted products and ester-forming derivatives such as acylated products thereof. Among these, 4-aminophenol is preferable from the viewpoint of easily balancing 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および1,8−ジアミノナフタレン、およびこれらのアルキル、アルコキシまたはハロゲン置換体、ならびにこ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 the aromatic diamine include 1,4-phenylenediamine, 1,3-phenylenediamine, 1,5-diaminonaphthalene and 1,8-diaminonaphthalene, and alkyl, alkoxy or halogen substituted products thereof, and these And 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−ブタンジオールおよび1,6−ヘキサンジオール、およびこ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を含有するポリマーを、前記の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 and 1,6-hexanediol, and acylated products thereof. Also, polymers containing aliphatic diols such as polyethylene terephthalate and polybutylene terephthalate react with the above aromatic hydroxycarboxylic 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、テトラデカン二酸、フマル酸、マレイン酸およびヘキサヒドロテレフタル酸が挙げられる。これらの中でも、重合時の反応性に優れる観点から、シュウ酸、コハク酸、アジピン酸、スベリン酸、セバシン酸およびドデカン二酸が好ましい。 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, tetradecanedioic acid, fumaric acid, maleic acid And hexahydroterephthalic acid. Among these, oxalic acid, succinic acid, adipic acid, suberic acid, sebacic acid and dodecanedioic acid are preferred from the viewpoint 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%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% 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。 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.
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。 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.
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
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
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
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
5)4−ヒドロキシ安息香酸/テレフタル酸/ハイドロキノン
6)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
7)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
8)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
9)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
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/4,4’−ジヒドロキシビフェニル
11)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
12)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
13)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
14)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
15)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
16)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
17)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
18)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
19)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
20)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
21)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
22)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
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/4,4’−ジヒドロキシビフェニル/エチレングリコール
24)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。
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 2) 4-hydroxybenzoic acid / terephthalic acid / 4,4′-dihydroxybiphenyl 3) 4-hydroxybenzoic acid / terephthalic acid / isophthalic acid / 4 4'-dihydroxybiphenyl 4) 4-hydroxybenzoic acid / terephthalic acid / isophthalic acid / 4,4'-dihydroxybiphenyl / hydroquinone 5) 4-hydroxybenzoic acid / terephthalic acid / hydroquinone 6) 6-hydroxy-2-naphthoic acid / Terephthalic acid / hydroquinone 7) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl 8) 6-hydroxy-2-naphthoic acid / terephthalic acid / 4,4 ' -Dihydroxybiphenyl 9) 4-hydroxybenzoic acid / 6-hydroxy 2-naphthoic acid / terephthalic acid / hydroquinone 10) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone / 4,4′-dihydroxybiphenyl 11) 4-hydroxybenzoic acid / 2,6 -Naphthalenedicarboxylic acid / 4,4'-dihydroxybiphenyl 12) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone 13) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone 14 ) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone 15) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone / 4,4 ′ -Dihydroxybiphenyl 16) 4 -Hydroxybenzoic acid / terephthalic acid / 4-aminophenol 17) 6-hydroxy-2-naphthoic acid / terephthalic acid / 4-aminophenol 18) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / 4-Aminophenol 19) 4-hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / 4-aminophenol 20) 4-hydroxybenzoic acid / terephthalic acid / ethylene glycol 21) 4-hydroxybenzoic acid / terephthalic acid / 4,4′-dihydroxybiphenyl / ethylene glycol 22) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / ethylene glycol 23) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / Terephthalic acid / 4,4'-dihydroxy Cibiphenyl / ethylene glycol 24) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / 4,4′-dihydroxybiphenyl.
これらの中でも、1)、9)、10)または14)のモノマー構成単位からなる液晶ポリマーが好ましい。 Among these, a liquid crystal polymer composed of the monomer structural unit of 1), 9), 10) or 14) is preferable.
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は、上記3,5−置換芳香族カルボン酸およびその反応性誘導体からなる群より選択される重合性単量体(A)と、他の重合性単量体(B)とを重合させて成る液晶ポリマーである。 The liquid crystal polymer of the present invention comprises a polymerizable monomer (A) selected from the group consisting of the 3,5-substituted aromatic carboxylic acid and its reactive derivative, and another polymerizable monomer (B). Is a liquid crystal polymer obtained by polymerizing
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、3,5−置換芳香族カルボン酸およびその反応性誘導体からなる群より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 the polymerizable monomer (A) selected from the group consisting of 3,5-substituted aromatic carboxylic acids and reactive derivatives thereof and other polymerizable monomers. The liquid crystal polymer of the present invention can be obtained by subjecting the monomer (B) to a known polycondensation method for forming an ester bond or an amide bond, such as a melt acidolysis method or a slurry polymerization method.
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 both cases of the melt acidification 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. Further, it can be subjected to the reaction as a modified form obtained by acylating a hydroxyl group and / or an amino group, 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。本発明の好ましい実施態様において、前記重合性単量体のアセチル化物を反応に供する。 The lower acyl group preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms. In a preferred embodiment of the present invention, the acetylated product of the polymerizable monomer is subjected to 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250〜370℃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 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 370 ° 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).
また、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1〜1000Pa・s、より好ましくは5〜300Pa・sである。 Further, the melt viscosity of the liquid crystal polymer of the present invention is preferably 1 to 1000 Pa · s, more preferably 5 to 300 Pa · s, when measured using a capillary rheometer under conditions of a shear rate of 1000 s −1 .
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。液晶ポリマー組成物の例としては、本発明の液晶ポリマーと無機または有機充填材とを含む電子部品用液晶ポリマー組成物等が挙げられる。 The liquid crystal polymer of the present invention obtained as described above is blended with one or more selected from inorganic or organic fillers, other additives described below, and other resin components, and the liquid crystal polymer It is good also as a composition. Examples of the liquid crystal polymer composition include a liquid crystal polymer composition for electronic parts containing the liquid crystal polymer of the present invention and an inorganic or organic filler.
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含有量が液晶ポリマー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 content of the inorganic or organic filler exceeds 200 parts by weight with respect to 100 parts by weight of the liquid crystal polymer, the moldability 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、カーボンブラックなどの着色剤;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良い。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 polysiloxane and fluororesin; coloring agents such as dyes, pigments and carbon black; antioxidants; thermal stabilizers; ultraviolet absorbers; antistatic agents; An agent or the like 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。他の樹脂成分の含有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 content of 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、無機または有機充填剤、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 and other resin components are added to the liquid crystal polymer, and this is added using a Banbury mixer, a kneader, a single or twin screw extruder, and the like. It can be obtained by melt-kneading in the temperature range from near 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に加工することができる。 The liquid crystal polymer or liquid crystal polymer composition of the present invention thus obtained can be processed into a molded product 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はフィブリル化が抑制されるため、精密機器等の電子部品として好適に使用される。
このような電子部品としては、コネクタ、スイッチ、リレー、コンデンサ、コイル、トランス、カメラモジュール、アンテナおよびチップアンテナからなる群から選択されるものを構成する部品が挙げられる。
特に、超音波洗浄を必要とする電子部品、例えばカメラモジュールや、他の部材との摺動を伴う摺動部材用電子部品、例えばコネクタ、スイッチ、リレー、カメラモジュールからなる群から選択されるものを構成する部品として好適に使用される。
Since the liquid crystal polymer of the present invention is suppressed from fibrillation, it is suitably used as an electronic component such as precision equipment.
Examples of such an electronic component include a component constituting a component selected from the group consisting of a connector, a switch, a relay, a capacitor, a coil, a transformer, a camera module, an antenna, and a chip antenna.
In particular, electronic components that require ultrasonic cleaning, such as camera modules, and electronic components for sliding members that involve sliding with other members, such as connectors, switches, relays, and camera modules. It is suitably used as a component that constitutes.
これらの中でも、本発明の液晶ポリマーは、成形品表面のフィブリル化に起因する光学特性の低下を阻止することから、カメラモジュールの部品として特に好適に使用される。カメラモジュールの部品としては、レンズバレル部(レンズが載る部分)、マウントホルダー部(バレルを装着し、基板に固定する部分)、CMOS(イメージセンサー)の枠、シャッター、シャッタープレート、シャッターボビン部、絞りのリング、ストッパー(レンズを押さえる部分)などが挙げられる。 Among these, the liquid crystal polymer of the present invention is particularly preferably used as a part of a camera module because it prevents a decrease in optical properties due to fibrillation of the surface of the molded product. The parts of the camera module include a lens barrel part (the part where the lens is placed), a mount holder part (the part where the barrel is mounted and fixed to the substrate), a CMOS (image sensor) frame, a shutter, a shutter plate, a shutter bobbin part, Examples include aperture rings and stoppers (portions that hold the lens).
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。
なお、実施例における特性値は以下の方法によって測定した。
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
In addition, the characteristic value in an Example was measured with the following method.
〈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、せん断速度1000s−1の条件で溶融粘度を測定した。実施例1〜6および比較例1〜3は350℃で測定し、実施例7および比較例4は320℃で測定した。
<Melt viscosity>
The melt viscosity was measured under the condition of a shear rate of 1000 s −1 using a 0.7 mmφ × 10 mm capillary with a melt viscosity measuring apparatus (Capillograph 1D manufactured by Toyo Seiki Co., Ltd.). Examples 1 to 6 and Comparative Examples 1 to 3 were measured at 350 ° C., and Example 7 and Comparative Example 4 were measured at 320 ° C.
〈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 (Exstar 6000 manufactured by Seiko Instruments Inc.), after measuring the endothermic peak temperature (Tm1) observed when the sample was measured from room temperature at a temperature rising condition of 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 ).
〈曲げ強度、曲げ弾性率〉
型締め圧15tの射出成形機(住友重機械工業(株)製 MINIMAT M26/15)を用いて結晶融解温度+20〜40℃のシリンダー温度、金型温度70℃で射出成形し、短冊状曲げ試験片(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、スパン間距離40.0mm、圧縮速度1.3mm/minで行った。
<Bending strength, flexural modulus>
Using an injection molding machine with a clamping pressure of 15 tons (MINIMAT M26 / 15 manufactured by Sumitomo Heavy Industries, Ltd.), injection molding is performed at a cylinder temperature of 20-40 ° C and a mold temperature of 70 ° C, and a strip-shaped bending test. A piece (length 65 mm × width 12.7 mm × thickness 2.0 mm) was produced. For the bending test, a three-point bending test was performed at an interspan distance of 40.0 mm and a compression speed of 1.3 mm / min using an INSTRON 5567 (universal testing machine manufactured by Instron Japan Ltd.).
〈フィブリル化の評価〉
型締め圧15tの射出成形機(住友重機械工業(株)製 MINIMAT M26/15)を用いて結晶融解温度+20〜40℃のシリンダー温度、金型温度70℃で射出成形し、ダンベル状引張試験片(長さ63.5mm×幅3.5mm×厚さ2.0mm)を作製した。試験片の表面を、JIS S 6050に規定の消しゴムでMD方向に30往復擦り、目視および、マイクロスコープ(キーエンス社製VHX−2000)による表面状態の確認によって、フィブリルの有無を確認した。
フィブリル化が確認されなければ○、確認されれば×とした。
<Evaluation of fibrillation>
Using an injection molding machine with a clamping pressure of 15 tons (MINIMAT M26 / 15 manufactured by Sumitomo Heavy Industries, Ltd.), injection molding is performed at a cylinder temperature of 20-40 ° C. and a mold temperature of 70 ° C., and a dumbbell tensile test A piece (length 63.5 mm × width 3.5 mm × thickness 2.0 mm) was prepared. The surface of the test piece was rubbed 30 times in the MD direction with an eraser specified in JIS S 6050, and the presence or absence of fibrils was confirmed by visual observation and confirmation of the surface condition with a microscope (VHX-2000 manufactured by Keyence Corporation).
If no fibrillation was confirmed, it was marked as ◯, and if confirmed, it was marked as x.
実施例1
下記化合物を撹拌翼、留出管を備えた反応容器に仕込み、窒素ガス雰囲気下に40〜150℃の間を1時間かけて昇温し、150℃で30分保った後、340℃まで7時間かけて昇温し、さらに340℃で10分間反応させた後、340℃で減圧を行った。次いで80分かけて10torrまで減圧した後、所定の攪拌トルクに達した時点で重縮合を完結させた。重合中の留去酢酸量は、ほぼ理論値どおりであった。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 :628g(70モル部)
6−ヒドロキシ−2−ナフトエ酸 :24g(2モル部)
ハイドロキノン :100g(14モル部)
2,6−ナフタレンジカルボン酸 :196g(14モル部)
5−ヒドロキシイソフタル酸 :11g(1モル部)
無水酢酸 :675g(全モノマーのヒドロキシ基100モル部に対して101モル部)
得られたペレットを成形し、曲げ強度、曲げ弾性率ならびにフィブリル化の評価を行った。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1に示した。また、フィブリル化評価前および評価後の試験片表面のマイクロスコープ図をそれぞれ、図1および図2に示した。
Example 1
The following compounds were charged into a reaction vessel equipped with a stirring blade and a distillation tube, heated between 40-150 ° C. in a nitrogen gas atmosphere over 1 hour, maintained at 150 ° C. for 30 minutes, and then increased to 340 ° C. The temperature was raised over time, and the mixture was further reacted at 340 ° C. for 10 minutes, and then reduced in pressure at 340 ° C. Subsequently, the pressure was reduced to 10 torr over 80 minutes, and the polycondensation was completed when a predetermined stirring torque was reached. The amount of acetic acid distilled off during the polymerization was almost the same as the theoretical value. The contents were taken out from the reaction vessel, and liquid crystal polymer pellets were obtained by a pulverizer.
4-hydroxybenzoic acid: 628 g (70 mole parts)
6-hydroxy-2-naphthoic acid: 24 g (2 mole parts)
Hydroquinone: 100 g (14 mol parts)
2,6-Naphthalenedicarboxylic acid: 196 g (14 mol parts)
5-hydroxyisophthalic acid: 11 g (1 mol part)
Acetic anhydride: 675 g (101 mol parts with respect to 100 mol parts of hydroxy groups of all monomers)
The obtained pellets were molded and evaluated for bending strength, flexural modulus and fibrillation. The results are shown in Table 1 together with the melt viscosity and crystal melting temperature of the obtained resin. Moreover, the microscope figure of the test piece surface before and after fibrillation evaluation was shown in FIG. 1 and FIG. 2, respectively.
実施例2
下記化合物を攪拌翼、留出管を備えた反応容器に仕込み、実施例1と同様の手順で重縮合、成形を行い、曲げ強度、曲げ弾性率ならびにフィブリル化の評価を行った。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1に示した。
4−ヒドロキシ安息香酸 :628g(70モル部)
6−ヒドロキシ−2−ナフトエ酸 :24g(2モル部)
ハイドロキノン :100.2g(14モル部)
2,6−ナフタレンジカルボン酸 :196g(14モル部)
5−ヒドロキシイソフタル酸 :35g(3モル部)
無水酢酸 :689g(全モノマーのヒドロキシ基100モル部に対して101モル部)
Example 2
The following compounds were charged into a reaction vessel equipped with a stirring blade and a distillation pipe, subjected to polycondensation and molding in the same procedure as in Example 1, and evaluated for flexural strength, flexural modulus and fibrillation. The results are shown in Table 1 together with the melt viscosity and crystal melting temperature of the obtained resin.
4-hydroxybenzoic acid: 628 g (70 mole parts)
6-hydroxy-2-naphthoic acid: 24 g (2 mole parts)
Hydroquinone: 100.2 g (14 mol parts)
2,6-Naphthalenedicarboxylic acid: 196 g (14 mol parts)
5-hydroxyisophthalic acid: 35 g (3 mole parts)
Acetic anhydride: 689 g (101 mol parts with respect to 100 mol parts of hydroxy groups of all monomers)
実施例3
下記化合物を攪拌翼、留出管を備えた反応容器に仕込み、実施例1と同様の手順で重縮合、成形を行い、曲げ強度、曲げ弾性率ならびにフィブリル化の評価を行った。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1に示した。
4−ヒドロキシ安息香酸 :628g(70モル部)
6−ヒドロキシ−2−ナフトエ酸 :24g(2モル部)
ハイドロキノン :100g(14モル部)
2,6−ナフタレンジカルボン酸 :196g(14モル部)
5−ヒドロキシイソフタル酸 :59g(5モル部)
無水酢酸 :702g(全モノマーのヒドロキシ基100モル部に対して101モル部)
Example 3
The following compounds were charged into a reaction vessel equipped with a stirring blade and a distillation pipe, subjected to polycondensation and molding in the same procedure as in Example 1, and evaluated for flexural strength, flexural modulus and fibrillation. The results are shown in Table 1 together with the melt viscosity and crystal melting temperature of the obtained resin.
4-hydroxybenzoic acid: 628 g (70 mole parts)
6-hydroxy-2-naphthoic acid: 24 g (2 mole parts)
Hydroquinone: 100 g (14 mol parts)
2,6-Naphthalenedicarboxylic acid: 196 g (14 mol parts)
5-hydroxyisophthalic acid: 59 g (5 mol parts)
Acetic anhydride: 702 g (101 mol parts with respect to 100 mol parts of hydroxy groups of all monomers)
実施例4
下記化合物を攪拌翼、留出管を備えた反応容器に仕込み、実施例1と同様の手順で重縮合、成形を行い、曲げ強度、曲げ弾性率ならびにフィブリル化の評価を行った。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1に示した。
4−ヒドロキシ安息香酸 :628g(70モル部)
6−ヒドロキシ−2−ナフトエ酸 :24g(2モル部)
ハイドロキノン :100g(14モル部)
2,6−ナフタレンジカルボン酸 :196g(14モル部)
α−レゾルシン酸 :10.0g(1モル部)
無水酢酸 :683g(全モノマーのヒドロキシ基100モル部に対して101モル部)
Example 4
The following compounds were charged into a reaction vessel equipped with a stirring blade and a distillation pipe, subjected to polycondensation and molding in the same procedure as in Example 1, and evaluated for flexural strength, flexural modulus and fibrillation. The results are shown in Table 1 together with the melt viscosity and crystal melting temperature of the obtained resin.
4-hydroxybenzoic acid: 628 g (70 mole parts)
6-hydroxy-2-naphthoic acid: 24 g (2 mole parts)
Hydroquinone: 100 g (14 mol parts)
2,6-Naphthalenedicarboxylic acid: 196 g (14 mol parts)
α-resorcinic acid: 10.0 g (1 mol part)
Acetic anhydride: 683 g (101 mol parts with respect to 100 mol parts of hydroxy groups of all monomers)
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、実施例1と同様の手順で重縮合、成形を行い、曲げ強度、曲げ弾性率ならびにフィブリル化の評価を行った。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1に示した。また、フィブリル化評価前および評価後の試験片表面のマイクロスコープ図をそれぞれ、図3および図4に示した。
4−ヒドロキシ安息香酸 :628g(70モル部)
6−ヒドロキシ−2−ナフトエ酸 :24g(2モル部)
ハイドロキノン :100g(14モル部)
2,6−ナフタレンジカルボン酸 :196g(14モル部)
無水酢酸 :669g(全モノマーのヒドロキシ基100モル部に対して101モル部)
Comparative Example 1
The following compounds were charged into a reaction vessel equipped with a stirring blade and a distillation pipe, subjected to polycondensation and molding in the same procedure as in Example 1, and evaluated for flexural strength, flexural modulus and fibrillation. The results are shown in Table 1 together with the melt viscosity and crystal melting temperature of the obtained resin. Moreover, the microscope figure of the test piece surface before and after fibrillation evaluation was shown in FIG. 3 and FIG. 4, respectively.
4-hydroxybenzoic acid: 628 g (70 mole parts)
6-hydroxy-2-naphthoic acid: 24 g (2 mole parts)
Hydroquinone: 100 g (14 mol parts)
2,6-Naphthalenedicarboxylic acid: 196 g (14 mol parts)
Acetic anhydride: 669 g (101 mol parts with respect to 100 mol parts of hydroxy groups of all monomers)
実施例5
下記化合物を撹拌翼、留出管を備えた反応容器に仕込み、窒素ガス雰囲気下に40〜150℃の間を1時間かけて昇温し、150℃で30分間保った後、350℃まで7.5時間かけて昇温し、さらに350℃で10分間反応させた後、350℃で減圧を行った。次いで1.5時間かけて5torrまで減圧し、所定の攪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 :314g(35モル部)
6−ヒドロキシ−2−ナフトエ酸 :61g(5モル部)
ハイドロキノン :121g(17モル部)
4,4’−ジヒドロキシビフェニル :157g(13モル部)
テレフタル酸 :323g(30モル部)
5−ヒドロキシイソフタル酸 :12g(1モル部)
無水酢酸 :689g(全モノマーのヒドロキシ基100モル部に対して103モル部)
Example 5
The following compounds were charged into a reaction vessel equipped with a stirring blade and a distillation pipe, heated between 40-150 ° C. in a nitrogen gas atmosphere over 1 hour, kept at 150 ° 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 g (35 mole parts)
6-hydroxy-2-naphthoic acid: 61 g (5 mol parts)
Hydroquinone: 121 g (17 mol parts)
4,4'-dihydroxybiphenyl: 157 g (13 mole parts)
Terephthalic acid: 323 g (30 mol parts)
5-hydroxyisophthalic acid: 12 g (1 mol part)
Acetic anhydride: 689 g (103 parts by mole based on 100 parts by mole of hydroxy groups of all monomers)
得られたペレットを成形し、曲げ強度、曲げ弾性率ならびにフィブリル化の評価を行った。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 evaluated for bending strength, flexural modulus and fibrillation. The results are shown in Table 2 together with the melt viscosity and crystal melting temperature of the obtained resin.
比較例2
下記化合物を攪拌翼、留出管を備えた反応容器に仕込み、実施例5と同様の手順で重縮合、成形を行い、曲げ強度、曲げ弾性率ならびにフィブリル化の評価を行った。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。
4−ヒドロキシ安息香酸 :314g(35モル部)
6−ヒドロキシ−2−ナフトエ酸 :61g(5モル部)
ハイドロキノン :121g(17モル部)
4,4’−ジヒドロキシビフェニル :157g(13モル部)
テレフタル酸 :323g(30モル部)
無水酢酸 :682g(全モノマーのヒドロキシ基100モル部に対して103モル部)
Comparative Example 2
The following compounds were charged into a reaction vessel equipped with a stirring blade and a distillation pipe, subjected to polycondensation and molding in the same procedure as in Example 5, and evaluated for flexural strength, flexural modulus and fibrillation. The results are shown in Table 2 together with the melt viscosity and crystal melting temperature of the obtained resin.
4-hydroxybenzoic acid: 314 g (35 mole parts)
6-hydroxy-2-naphthoic acid: 61 g (5 mol parts)
Hydroquinone: 121 g (17 mol parts)
4,4'-dihydroxybiphenyl: 157 g (13 mole parts)
Terephthalic acid: 323 g (30 mol parts)
Acetic anhydride: 682 g (103 mol parts relative to 100 mol parts of hydroxy groups of all monomers)
実施例6
下記化合物を撹拌翼、留出管を備えた反応容器に仕込み、窒素ガス雰囲気下に40〜150℃の間を1時間かけて昇温し、150℃で30分間保った後、350℃まで7.5時間かけて昇温し、さらに350℃で10分間反応させた後、350℃で減圧を行った。次いで2時間かけて10torrまで減圧し、所定の攪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 :385g(43モル部)
6−ヒドロキシ−2−ナフトエ酸 :192g(16モル部)
ハイドロキノン :148g(20.5モル部)
テレフタル酸 :223g(20.5モル部)
5−ヒドロキシイソフタル酸 :35g(3モル部)
無水酢酸 :696g(全モノマーのヒドロキシ基100モル部に対して102モル部)
Example 6
The following compounds were charged into a reaction vessel equipped with a stirring blade and a distillation pipe, heated between 40-150 ° C. in a nitrogen gas atmosphere over 1 hour, kept at 150 ° 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 10 torr over 2 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: 385 g (43 mol parts)
6-hydroxy-2-naphthoic acid: 192 g (16 mole parts)
Hydroquinone: 148 g (20.5 mol parts)
Terephthalic acid: 223 g (20.5 mol parts)
5-hydroxyisophthalic acid: 35 g (3 mole parts)
Acetic anhydride: 696 g (102 mol parts relative to 100 mol parts of hydroxy groups of all monomers)
得られたペレットを成形し、曲げ強度、曲げ弾性率ならびにフィブリル化の評価を行った。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3に示した。 The obtained pellets were molded and evaluated for bending strength, flexural modulus and fibrillation. The results are shown in Table 3 together with the melt viscosity and crystal melting temperature of the resulting resin.
比較例3
下記化合物を攪拌翼、留出管を備えた反応容器に仕込み、実施例6と同様の手順で重縮合、成形を行い、曲げ強度、曲げ弾性率ならびにフィブリル化の評価を行った。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3に示した。
4−ヒドロキシ安息香酸 :385g(43モル部)
6−ヒドロキシ−2−ナフトエ酸 :192g(16モル部)
ハイドロキノン :223g(20.5モル部)
テレフタル酸 :148g(20.5モル部)
無水酢酸 :677g(全モノマーのヒドロキシ基100モル部に対して102モル部)
Comparative Example 3
The following compounds were charged into a reaction vessel equipped with a stirring blade and a distillation tube, subjected to polycondensation and molding in the same procedure as in Example 6, and evaluated for flexural strength, flexural modulus and fibrillation. The results are shown in Table 3 together with the melt viscosity and crystal melting temperature of the resulting resin.
4-hydroxybenzoic acid: 385 g (43 mol parts)
6-hydroxy-2-naphthoic acid: 192 g (16 mole parts)
Hydroquinone: 223 g (20.5 mol parts)
Terephthalic acid: 148 g (20.5 mol parts)
Acetic anhydride: 677 g (102 mol parts relative to 100 mol parts of hydroxy groups of all monomers)
実施例7
下記化合物を撹拌翼、留出管を備えた反応容器に仕込み、窒素ガス雰囲気下に40〜150℃の間を1時間かけて昇温し、150℃で30分間保った後、350℃まで7.5時間かけて昇温し、さらに350℃で10分間反応させた後、350℃で減圧を行った。次いで1.5時間かけて10torrまで減圧し、所定の攪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 :655g(73モル部)
6−ヒドロキシ−2−ナフトエ酸 :330g(27モル部)
5−ヒドロキシイソフタル酸 :35g(3モル部)
無水酢酸 :696g(全モノマーのヒドロキシ基100モル部に対して102モル部)
Example 7
The following compounds were charged into a reaction vessel equipped with a stirring blade and a distillation pipe, heated between 40-150 ° C. in a nitrogen gas atmosphere over 1 hour, kept at 150 ° 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 10 torr over 1.5 hours, 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: 655 g (73 mol parts)
6-hydroxy-2-naphthoic acid: 330 g (27 mol parts)
5-hydroxyisophthalic acid: 35 g (3 mole parts)
Acetic anhydride: 696 g (102 mol parts relative to 100 mol parts of hydroxy groups of all monomers)
得られたペレットを成形し、曲げ強度、曲げ弾性率ならびにフィブリル化の評価を行った。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4に示した。 The obtained pellets were molded and evaluated for bending strength, flexural modulus and fibrillation. The results are shown in Table 4 together with the melt viscosity and crystal melting temperature of the obtained resin.
比較例4
下記化合物を攪拌翼、留出管を備えた反応容器に仕込み、実施例7と同様の手順で重縮合、成形を行い、曲げ強度、曲げ弾性率ならびにフィブリル化の評価を行った。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4に示した。
4−ヒドロキシ安息香酸 :655g(73モル部)
6−ヒドロキシ−2−ナフトエ酸 :330g(27モル部)
無水酢酸 :677g(全モノマーのヒドロキシ基100モル部に対して102モル部)
Comparative Example 4
The following compounds were charged into a reaction vessel equipped with a stirring blade and a distillation pipe, subjected to polycondensation and molding in the same procedure as in Example 7, and evaluated for flexural strength, flexural modulus and fibrillation. The results are shown in Table 4 together with the melt viscosity and crystal melting temperature of the obtained resin.
4-hydroxybenzoic acid: 655 g (73 mol parts)
6-hydroxy-2-naphthoic acid: 330 g (27 mol parts)
Acetic anhydride: 677 g (102 mol parts relative to 100 mol parts of hydroxy groups of all monomers)
表1〜4に示される通り、3,5−置換芳香族カルボン酸をモノマー成分として用いた実施例1〜4、実施例5、実施例6および実施例7の液晶ポリマーはそれぞれ、3,5−置換芳香族カルボン酸をモノマー成分として用いなかった比較例1、比較例2、比較例3および比較例4の液晶ポリマーと比べてフィブリル化が抑制されると共に、電子部品等の成形品に用いるために十分な溶融粘度、結晶融解温度、曲げ強度、曲げ弾性率を有することが分かる。 As shown in Tables 1 to 4, the liquid crystal polymers of Examples 1 to 4, Example 5, Example 6, and Example 7 using 3,5-substituted aromatic carboxylic acid as a monomer component were 3,5 and 5, respectively. -Compared with the liquid crystal polymers of Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4 in which the substituted aromatic carboxylic acid was not used as a monomer component, fibrillation was suppressed and used for molded products such as electronic parts. Therefore, it can be seen that it has sufficient melt viscosity, crystal melting temperature, flexural strength, and flexural modulus.
Claims (17)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016143471A JP6787713B2 (en) | 2016-07-21 | 2016-07-21 | Liquid crystal polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016143471A JP6787713B2 (en) | 2016-07-21 | 2016-07-21 | Liquid crystal polymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2018012789A true JP2018012789A (en) | 2018-01-25 |
JP6787713B2 JP6787713B2 (en) | 2020-11-18 |
Family
ID=61021277
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2016143471A Active JP6787713B2 (en) | 2016-07-21 | 2016-07-21 | Liquid crystal polymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP6787713B2 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111825833A (en) * | 2019-04-16 | 2020-10-27 | 上野制药株式会社 | Liquid crystalline polyester resin |
US11086200B2 (en) | 2019-03-20 | 2021-08-10 | Ticona Llc | Polymer composition for use in a camera module |
US11722759B2 (en) | 2019-03-20 | 2023-08-08 | Ticona Llc | Actuator assembly for a camera module |
US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
US12032272B2 (en) | 2021-07-14 | 2024-07-09 | Ticona Llc | Polymer composition for use in a camera module |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11147945A (en) * | 1997-11-18 | 1999-06-02 | Nippon Oil Co Ltd | Optical film |
JP2001011733A (en) * | 1999-07-01 | 2001-01-16 | Toray Ind Inc | Polyester for melt-spinning, partially oriented undrawn fiber of polyester and its production |
JP2002293951A (en) * | 2001-03-29 | 2002-10-09 | Toray Ind Inc | Thermoplastic crosslinked resin |
JP2009052150A (en) * | 2007-08-23 | 2009-03-12 | Toray Ind Inc | Fiber |
JP2011080092A (en) * | 2006-03-30 | 2011-04-21 | Toray Ind Inc | Dendritic polyester, production method therefor and thermoplastic resin composition |
JP2016060997A (en) * | 2014-09-19 | 2016-04-25 | 上野製薬株式会社 | Forgery prevention paper |
JP2016060163A (en) * | 2014-09-19 | 2016-04-25 | 上野製薬株式会社 | Forgery-proof card |
JP2016132248A (en) * | 2015-01-22 | 2016-07-25 | 上野製薬株式会社 | Laminate |
-
2016
- 2016-07-21 JP JP2016143471A patent/JP6787713B2/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11147945A (en) * | 1997-11-18 | 1999-06-02 | Nippon Oil Co Ltd | Optical film |
JP2001011733A (en) * | 1999-07-01 | 2001-01-16 | Toray Ind Inc | Polyester for melt-spinning, partially oriented undrawn fiber of polyester and its production |
JP2002293951A (en) * | 2001-03-29 | 2002-10-09 | Toray Ind Inc | Thermoplastic crosslinked resin |
JP2011080092A (en) * | 2006-03-30 | 2011-04-21 | Toray Ind Inc | Dendritic polyester, production method therefor and thermoplastic resin composition |
JP2009052150A (en) * | 2007-08-23 | 2009-03-12 | Toray Ind Inc | Fiber |
JP2016060997A (en) * | 2014-09-19 | 2016-04-25 | 上野製薬株式会社 | Forgery prevention paper |
JP2016060163A (en) * | 2014-09-19 | 2016-04-25 | 上野製薬株式会社 | Forgery-proof card |
JP2016132248A (en) * | 2015-01-22 | 2016-07-25 | 上野製薬株式会社 | Laminate |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11086200B2 (en) | 2019-03-20 | 2021-08-10 | Ticona Llc | Polymer composition for use in a camera module |
US11722759B2 (en) | 2019-03-20 | 2023-08-08 | Ticona Llc | Actuator assembly for a camera module |
CN111825833A (en) * | 2019-04-16 | 2020-10-27 | 上野制药株式会社 | Liquid crystalline polyester resin |
US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
US12032272B2 (en) | 2021-07-14 | 2024-07-09 | Ticona Llc | Polymer composition for use in a camera module |
Also Published As
Publication number | Publication date |
---|---|
JP6787713B2 (en) | 2020-11-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6844968B2 (en) | Liquid crystal polymer composition | |
JP6885687B2 (en) | Liquid crystal polymer composition | |
JP6576808B2 (en) | Liquid crystal polymer | |
US10377851B2 (en) | Liquid crystal polymer | |
KR102556126B1 (en) | Liquid crystal polyester resin | |
CN107236265B (en) | Liquid crystalline polymer composition | |
JP6503272B2 (en) | Liquid crystal polymer | |
JP6787713B2 (en) | Liquid crystal polymer | |
JP6576802B2 (en) | Liquid crystal polymer | |
JP7355523B2 (en) | liquid crystal polymer composition | |
JP6258771B2 (en) | Liquid crystal polymer | |
JP2017014357A (en) | Liquid crystal polymer for electronic component | |
JP2017043705A (en) | Liquid crystal polymer | |
JP7175834B2 (en) | liquid crystal polyester resin | |
JP7174640B2 (en) | liquid crystal polymer | |
JP6433211B2 (en) | Liquid crystal polymer | |
WO2020070904A1 (en) | Liquid crystal polyester resin | |
JP7498641B2 (en) | Liquid crystal polymer composition | |
JP2023035021A (en) | liquid crystal polymer composition | |
CN112341609A (en) | Liquid crystalline polyester resin | |
JP2016113511A (en) | Method for producing liquid crystal polymer | |
JP2018203810A (en) | Liquid crystal polymer composition | |
JP2022129986A (en) | liquid crystal polyester amide resin | |
JP2024077781A (en) | Liquid crystal polymer composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20170817 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20190529 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20200217 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200225 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200422 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200609 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200731 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20201013 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20201029 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6787713 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |