JP2018016754A - Liquid crystal polymer composition - Google Patents
Liquid crystal polymer composition Download PDFInfo
- Publication number
- JP2018016754A JP2018016754A JP2016149976A JP2016149976A JP2018016754A JP 2018016754 A JP2018016754 A JP 2018016754A JP 2016149976 A JP2016149976 A JP 2016149976A JP 2016149976 A JP2016149976 A JP 2016149976A JP 2018016754 A JP2018016754 A JP 2018016754A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- crystal polymer
- acid
- polymer composition
- 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 112
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 title claims abstract description 112
- 239000000203 mixture Substances 0.000 title claims abstract description 72
- 239000002245 particle Substances 0.000 claims abstract description 79
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000835 fiber Substances 0.000 claims abstract description 36
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011521 glass Substances 0.000 claims abstract description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 55
- -1 aromatic hydroxycarboxylic acids Chemical class 0.000 claims description 54
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 32
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 30
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 26
- 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 18
- 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 16
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000006229 carbon black Substances 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 12
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 12
- 230000003287 optical effect Effects 0.000 claims description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- 150000004984 aromatic diamines Chemical class 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
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- 239000003990 capacitor Substances 0.000 claims description 3
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- 239000000178 monomer Substances 0.000 description 25
- 239000008188 pellet Substances 0.000 description 23
- 238000006116 polymerization reaction Methods 0.000 description 20
- 239000013078 crystal Substances 0.000 description 17
- 238000002844 melting Methods 0.000 description 16
- 230000008018 melting Effects 0.000 description 16
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
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- 238000002156 mixing Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
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- 229920000642 polymer Polymers 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
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 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 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
- 239000003054 catalyst Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011342 resin composition Substances 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
- 208000010444 Acidosis Diseases 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 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
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 2
- 230000007950 acidosis Effects 0.000 description 2
- 208000026545 acidosis disease Diseases 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-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
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 206010061592 cardiac fibrillation Diseases 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
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- 230000002600 fibrillogenic effect Effects 0.000 description 2
- 229910052736 halogen Chemical group 0.000 description 2
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- 150000004706 metal oxides Chemical class 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
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- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
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- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
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- 229910015900 BF3 Inorganic materials 0.000 description 1
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- 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 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
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 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
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 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
- 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
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 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
- 239000011261 inert gas Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium 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
- 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
- 239000012778 molding material Substances 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
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-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
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000010287 polarization Effects 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
- 238000006068 polycondensation reaction Methods 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
- 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
- 239000000376 reactant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 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
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Images
Abstract
Description
本発明は、カメラモジュール部品などの電子部品に使用される液晶ポリマー組成物に関する。 The present invention relates to a liquid crystal polymer composition used for electronic parts such as camera module parts.
液晶ポリマーは、耐熱性、強度等の機械物性、耐薬品性、寸法精度等に優れているため、各種用途にその使用が拡大しつつあり、近年は、精密機器に用いられる電子部品を構成する成形品の成形用材料などにも用いられている。 Since liquid crystal polymers are excellent in mechanical properties such as heat resistance and strength, chemical resistance, dimensional accuracy, etc., their use is expanding to various applications, and in recent years, they constitute electronic parts used in precision equipment. It is also used as a molding material for molded products.
精密機器、特にレンズなどを有する光学機器、例えば、レンズバレル（レンズが載る部品）およびマウントホルダー（バレルを装着し、基板に固定する部品）からなるレンズホルダー、ＣＭＯＳ（イメージセンサー）の枠、シャッターおよび、シャッターボビン、絞りのリング、ストッパー（レンズを押さえる部品）などのカメラモジュールを構成する光学電子部品（以下、「カメラモジュール部品」）を構成する成形品にも、液晶ポリマー組成物は使用されている。 Precision instruments, especially optical instruments with lenses, such as lens barrels (components on which lenses are mounted) and mount holders (components that mount barrels and fix to substrates), CMOS (image sensor) frames, shutters Liquid crystal polymer compositions are also used in molded products that make up optical electronic parts (hereinafter referred to as “camera module parts”) that make up camera modules such as shutter bobbins, aperture rings, and stoppers (parts that hold the lens). ing.
カメラモジュールにおいては、小さなゴミ、塵や埃がレンズやＣＭＯＳ（イメージセンサー）に付着すると、光学特性が著しく低下する。このような光学特性の低下を防ぐ目的で、通常、カメラモジュール部品用部材は、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、埃等が除去される。 In a camera module, when small dust, dust, or dust adheres to a lens or a CMOS (image sensor), the optical characteristics are significantly deteriorated. In order to prevent such deterioration of the optical characteristics, the camera module component member is usually ultrasonically cleaned before assembly to remove small dust, dust and the like adhering to the surface.
液晶ポリマー組成物からなる成形品は、成形品表面が剥離しやすく、超音波洗浄すると表面が剥離して起毛するフィブリル化が生じやすい。そして、このフィブリル化した部分からは小さな粉や塵（パーティクル）が発生しやすくなる。 The molded product made of the liquid crystal polymer composition is easily peeled off from the surface of the molded product, and is easily fibrillated when the surface is peeled off by ultrasonic cleaning. And it becomes easy to generate | occur | produce small powder and dust (particle) from this fibrillated part.
また、カメラモジュールの組立においてレンズとイメージセンサー間の距離を調整する際に、カメラモジュール部品用の成形品表面は摩擦を受け、やはりフィブリル化が生じてパーティクルが発生し易い状態となる。 Further, when the distance between the lens and the image sensor is adjusted in the assembly of the camera module, the surface of the molded product for the camera module component is subjected to friction, and fibrillation also occurs and particles are likely to be generated.
したがって、カメラモジュール部品に使用する材料として、パーティクル発生の少ない液晶ポリマー組成物の提供が求められていた。 Therefore, it has been demanded to provide a liquid crystal polymer composition with less generation of particles as a material used for camera module parts.
パーティクル発生を抑えた液晶ポリマー組成物として、液晶ポリマーに特定の充填材（タルク、ガラス繊維、カーボンブラックなど）やオレフィン系共重合体などを含有させた樹脂組成物が提案されている（特許文献１−６）。しかし、これらの樹脂組成物については、無機充填材と液晶ポリマーとの濡れ性が悪く、超音波洗浄の際のパーティクル発生抑制効果が不十分であった。したがって、超音波洗浄に際して、パーティクルの発生が抑制された液晶ポリマー組成物が求められていた。 As a liquid crystal polymer composition in which particle generation is suppressed, a resin composition in which a liquid crystal polymer contains a specific filler (talc, glass fiber, carbon black, etc.) or an olefin copolymer has been proposed (Patent Literature). 1-6). However, these resin compositions have poor wettability between the inorganic filler and the liquid crystal polymer, and the particle generation suppressing effect during ultrasonic cleaning is insufficient. Therefore, there has been a demand for a liquid crystal polymer composition in which the generation of particles is suppressed during ultrasonic cleaning.
本発明の目的は、パーティクルの発生数が抑制された液晶ポリマー組成物を提供することにある。 An object of the present invention is to provide a liquid crystal polymer composition in which the number of generated particles is suppressed.
本発明者らは、液晶ポリマーに繊維状酸化チタンを配合することにより、液晶ポリマー組成物についてパーティクル発生が顕著に抑制されることを見出し、本発明を完成するに至った。 The present inventors have found that particle generation is remarkably suppressed in the liquid crystal polymer composition by blending fibrous titanium oxide with the liquid crystal polymer, and the present invention has been completed.
具体的には本発明は以下のものを提供する。
（１） 液晶ポリマー１００重量部に対して、数平均繊維長（Ｌ）が１μｍ〜５０μｍ、数平均繊維径（Ｄ）が０．０５μｍ〜２．０μｍであり、かつＬ／Ｄが３〜５０である繊維状酸化チタンを１〜１５０重量部含有し、以下の定義によるパーティクル数が１０００個以下である、液晶ポリマー組成物。
パーティクル数：長さ６４ｍｍ、幅１３ｍｍ、厚み２ｍｍの成形片を純水５０ｍＬを備えた円筒形ガラス容器に載置し、３８ｋＨｚ、１００Ｗの出力にて１０分間超音波照射した後、純水１ｍＬ中に含まれる粒子径が２μｍ以上である粒子の数
（２） 液晶ポリマーが、芳香族ヒドロキシカルボン酸、芳香族ジカルボン酸、芳香族ジオール、芳香族アミノカルボン酸、芳香族ヒドロキシアミン、芳香族ジアミン、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種以上の化合物から構成される共重合体である、（１）に記載の液晶ポリマー組成物。
（３） 液晶ポリマーが、芳香族ヒドロキシカルボン酸、芳香族ジカルボン酸および芳香族ジオールからなる群から選択される２種以上の化合物から構成される共重合体である、（１）に記載の液晶ポリマー組成物。
（４） 芳香族ヒドロキシカルボン酸が、４−ヒドロキシ安息香酸および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種以上の化合物である、（２）または（３）に記載の液晶ポリマー組成物。
（５） 芳香族ジカルボン酸が、テレフタル酸、イソフタル酸および２，６−ナフタレンジカルボン酸からなる群から選択される１種以上の化合物である、（２）または（３）に記載の液晶ポリマー組成物。
（６） 芳香族ジオールが、ハイドロキノン、レゾルシン、４，４’−ジヒドロキシビフェニルおよび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種以上の化合物である、（２）または（３）に記載の液晶ポリマー組成物。
（７） カーボンブラックを更に含む、（１）〜（６）のいずれかに記載の液晶ポリマー組成物。
（８） （１）〜（７）のいずれかに記載の液晶ポリマー組成物から構成される成形品。
（９） 成形品が電子部品である、（８）に記載の成形品。
（１０） 電子部品が、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より選択されるものを構成する部品である、（９）に記載の電子部品。
（１１） 電子部品が超音波洗浄を必要とする電子部品である、（９）または（１０）に記載の電子部品。
（１２） 電子部品が摺動部材用電子部品である、（９）〜（１１）のいずれかに記載の電子部品。
（１３） 電子部品がカメラモジュールを構成する光学電子部品である、（９）〜（１２）のいずれかに記載の電子部品。
（１４） 液晶ポリマー組成物から構成される成形品表面におけるパーティクル発生の抑制方法であって、
液晶ポリマー１００重量部に対して、数平均繊維長（Ｌ）が１μｍ〜５０μｍ、数平均繊維径（Ｄ）が０．０５μｍ〜２．０μｍであり、かつＬ／Ｄが３〜５０である繊維状酸化チタンを１〜１５０重量部を配合することを特徴とする、パーティクル発生の抑制方法。
Specifically, the present invention provides the following.
(1) The number average fiber length (L) is 1 μm to 50 μm, the number average fiber diameter (D) is 0.05 μm to 2.0 μm, and the L / D is 3 to 50 with respect to 100 parts by weight of the liquid crystal polymer. A liquid crystal polymer composition containing 1 to 150 parts by weight of fibrous titanium oxide and having 1000 or less particles according to the following definition.
Number of particles: A molded piece having a length of 64 mm, a width of 13 mm, and a thickness of 2 mm was placed on a cylindrical glass container equipped with 50 mL of pure water, and subjected to ultrasonic irradiation for 10 minutes at an output of 38 kHz and 100 W, and then in 1 mL of pure water. The number of particles having a particle diameter of 2 μm or more (2) The liquid crystal polymer is an aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic aminocarboxylic acid, aromatic hydroxyamine, aromatic diamine, The liquid crystal polymer composition according to (1), which is a copolymer composed of two or more compounds selected from the group consisting of aliphatic diols and aliphatic dicarboxylic acids.
(3) The liquid crystal according to (1), wherein the liquid crystal polymer is a copolymer composed of two or more compounds selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids and aromatic diols. Polymer composition.
(4) The liquid crystal according to (2) or (3), wherein the aromatic hydroxycarboxylic acid is one or more compounds selected from the group consisting of 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid. Polymer composition.
(5) The liquid crystal polymer composition according to (2) or (3), wherein the aromatic dicarboxylic acid is one or more compounds selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid. object.
(6) The aromatic diol is one or more compounds selected from the group consisting of hydroquinone, resorcin, 4,4′-dihydroxybiphenyl and 2,6-dihydroxynaphthalene, described in (2) or (3) Liquid crystal polymer composition.
(7) The liquid crystal polymer composition according to any one of (1) to (6), further comprising carbon black.
(8) A molded article comprising the liquid crystal polymer composition according to any one of (1) to (7).
(9) The molded product according to (8), wherein the molded product is an electronic component.
(10) The electronic component according to (9), wherein the electronic component constitutes 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.
(11) The electronic component according to (9) or (10), wherein the electronic component is an electronic component that requires ultrasonic cleaning.
(12) The electronic component according to any one of (9) to (11), wherein the electronic component is an electronic component for a sliding member.
(13) The electronic component according to any one of (9) to (12), wherein the electronic component is an optical electronic component that constitutes a camera module.
(14) A method for suppressing the generation of particles on the surface of a molded article composed of a liquid crystal polymer composition,
A fiber having a number average fiber length (L) of 1 μm to 50 μm, a number average fiber diameter (D) of 0.05 μm to 2.0 μm, and an L / D of 3 to 50 with respect to 100 parts by weight of the
本発明の液晶ポリマー組成物により、パーティクル発生量が抑制された成形品が提供される。 The liquid crystal polymer composition of the present invention provides a molded product in which the amount of generated particles is suppressed.
本発明に係る液晶ポリマーは、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 according to 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.
異方性溶融相の性質は、直交偏光子を利用した慣用の偏光検査法により確認することができる。より具体的には、異方性溶融相の確認は、Ｌｅｉｔｚ偏光顕微鏡を使用し、Ｌｅｉｔｚホットステージにのせた試料を窒素雰囲気下で４０倍の倍率で観察することにより実施することができる。本発明の液晶ポリマーは光学的に異方性を示すもの、即ち、直交偏光子の間で検査したときに光を透過させるものである。試料が光学的に異方性であると、たとえ静止状態であっても偏光は透過する。 The property of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the anisotropic molten phase can be confirmed by observing a sample placed on a Leitz hot stage at a magnification of 40 times in a nitrogen atmosphere using a Leitz polarizing microscope. The liquid crystal polymer of the present invention is optically anisotropic, that is, transmits light when inspected between crossed polarizers. If the sample is optically anisotropic, polarized light is transmitted even if it is stationary.
本発明に係る液晶ポリマーに用いる重合性単量体としては、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もよい。 Examples of the polymerizable monomer used in the liquid crystal polymer according to the present invention include monomers used in conventional liquid crystal polymers, such as aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic aminocarboxylic acids, aromatics. Aromatic hydroxyamines, aromatic diamines, aliphatic diols and aliphatic dicarboxylic acids. These compounds may use only 1 type and may combine 2 or more types.
重合性単量体として、１種以上が結合してなるオリゴマーを共重合に供してもよい。なお、本発明における、重合性単量体の量については、「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 the polymerizable monomer, an oligomer formed by combining one or more kinds may be used for copolymerization. In addition, about the quantity of the polymerizable monomer in this invention, even if it is a case where "polymerizable monomer" is used as an oligomer, it shall count for every monomer unit which comprises the said oligomer.
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または６−ヒドロキシ−２−ナフトエ酸を単独で、あるいは両者を組み合わせて用いることが、得られる液晶ポリマーの耐熱性や機械強度、融点を調節しやすいという点で、より好ましい。 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 their 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, 4-hydroxybenzoic acid or 6-hydroxy-2-naphthoic acid alone or in combination can be used to easily adjust the heat resistance, mechanical strength, and melting point of the obtained liquid crystal polymer. More preferable.
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、４，４’’−ジカルボキシターフェニル、ビス（４−カルボキシフェニル）エーテル、ビス（４−カルボキシフェノキシ）ブタン、ビス（４−カルボンキシフェニル）エタン、ビス（３−カルボキシフェニル）エーテルおよびビス（３−カルボキシフェニル）エタン、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、テレフタル酸、イソフタル酸および２，６−ナフタレンジカルボン酸が好適に用いられ、特に得られる液晶ポリマーの耐熱性を効果的に高められる点で、テレフタル酸または２，６−ナフタレンジカルボン酸が好ましい。 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, 4,4 ″ -dicarboxyterphenyl, bis (4-carboxyphenyl) ether, bis (4-carboxyphenoxy) butane, bis (4-carboxylphenyl) ethane, bis (3 -Carboxyphenyl) ether and bis (3-carboxyphenyl) ethane, their alkyl, alkoxy or halogen substituents and their ester-forming derivatives such as their ester derivatives, acid halides. Among these, terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid are preferably used, and terephthalic acid or 2,6-naphthalenedicarboxylic acid is particularly effective in improving the heat resistance of the obtained liquid crystal polymer. Is preferred.
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、ビス（４−ヒドロキシフェニル）エタンおよび２，２’−ジヒドロキシビナフチル、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、ハイドロキノン、レゾルシン、４，４’−ジヒドロキシビフェニル、２，６−ジヒドロキシナフタレンが好適に用いられ、特に重合時の反応性に優れる点において、ハイドロキノン、４，４’−ジヒドロキシビフェニルまたは２，６−ジヒドロキシナフタレンが好ましい。 Specific examples of the aromatic diol include hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 3,3′-dihydroxybiphenyl, 3,4′-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenol ether, bis (4-hydroxyphenyl) ethane and 2,2'-dihydroxybinaphthyl, and their alkyl, alkoxy or halogen substituted products and their acylated products, etc. The ester-forming derivatives of Among these, hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, and 2,6-dihydroxynaphthalene are preferably used. In particular, hydroquinone, 4,4′-dihydroxybiphenyl, or 2 in terms of excellent reactivity during polymerization. , 6-Dihydroxynaphthalene is preferred.
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 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, acylated products, and ester derivatives thereof. And ester-forming derivatives such as acid halides.
芳香族ヒドロキシアミンの具体例としては、４−アミノフェノール、Ｎ−メチル−４−アミノフェノール、３−アミノフェノール、３−メチル−４−アミノフェノール、４−アミノ−１−ナフトール、４−アミノ−４’−ヒドロキシビフェニル、４−アミノ−４’−ヒドロキシビフェニルエーテル、４−アミノ−４’−ヒドロキシビフェニルメタン、４−アミノ−４’−ヒドロキシビフェニルスルフィドおよび２，２’−ジアミノビナフチル、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点から好ましい。 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 thereof include ester-forming derivatives such as alkyl, alkoxy or halogen-substituted products and acylated products thereof. Among these, 4-aminophenol is preferable because it easily balances 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、２，６−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 the aromatic diamine include 1,4-phenylenediamine, 1,3-phenylenediamine, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene and 1,8-diaminonaphthalene, and alkyls and alkoxys thereof. Alternatively, amide-forming derivatives such as halogen-substituted products and acylated products thereof can be mentioned.
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. In addition, polymers containing aliphatic diols such as polyethylene terephthalate and polybutylene terephthalate are mixed with the above aromatic oxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols and their acylated products, ester derivatives, acid halides, etc. You may make it react.
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、コハク酸、アジピン酸、セバシン酸およびドデカン二酸が重合時の反応性に優れる点から好ましい。 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, succinic acid, adipic acid, sebacic acid, and dodecanedioic acid are preferable from the viewpoint of excellent reactivity during polymerization.
本発明に係る液晶ポリマーは、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、および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。これらの単量体は、他の重合性単量体に対して１０モル％以下であるのが好ましい。 The liquid crystal polymer according to 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. These monomers are preferably 10 mol% or less with respect to other polymerizable monomers.
重合性単量体として、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。上記態様には、重合性単量体として、２種以上の芳香族ヒドロキシカルボン酸を用いる場合も包含される。 The polymerizable monomer is selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic aminocarboxylic acids, aromatic hydroxyamines, aromatic diamines, aliphatic diols and aliphatic dicarboxylic acids. It is one of the preferable embodiments of the present invention to use two or more kinds of compounds in combination. The above embodiment also includes a case where two or more aromatic hydroxycarboxylic acids are used as the polymerizable monomer.
また、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、１種以上の芳香族ヒドロキシカルボン酸、１種以上の芳香族ジカルボン酸および１種以上の芳香族ジオールの混合物が高耐熱性を示す点から好ましい。 A combination comprising an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid and an aromatic diol is more preferably used, and one or more aromatic hydroxycarboxylic acids, one or more aromatic dicarboxylic acids and one or more aromatics are used. A mixture of a group diol is preferred from the viewpoint of high heat resistance.
本発明に係る液晶ポリマーに用いる、重合性単量体の具体例としては、例えば下記の組合わせからなる混合物が挙げられる。
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 polymerizable monomer used in the liquid crystal polymer according to the present invention include, for example, a mixture composed of 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′-dihydroxybiphenyl / ethylene glycol,
24) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / 4,4′-dihydroxybiphenyl.
以下、本発明に係る液晶ポリマーの製造方法について説明する。 Hereafter, the manufacturing method of the liquid crystal polymer which concerns on this invention is demonstrated.
本発明に係る液晶ポリマーを製造する方法に特に制限はなく、重合性単量体を、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液晶ポリマーを得ることができる。 The method for producing the liquid crystal polymer according to the present invention is not particularly limited, and by subjecting the polymerizable monomer to a known condensation polymerization method for forming an ester bond or an amide bond, for example, a melt acidosis method, a slurry polymerization method, or the like. A liquid crystal polymer can be obtained.
溶融アシドリシス法は、本発明に係る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 acidosis method is a preferable method for producing the liquid crystal polymer according to 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は、ヒドロキシル基および／またはアミノ基をアシル化した変性形態、すなわち低級アシル化物として反応に供することもできる。 In any of the melt acidification method and the slurry polymerization method, the polymerizable monomer used in producing the liquid crystal polymer is a modified form obtained by acylating a hydroxyl group and / or an amino group, that is, a lower acylated product. It can also be used for the reaction.
低級アシル基は炭素原子数２〜５のものが好ましく、炭素原子数２または３のものがより好ましい。特に好ましくは前記重合性単量体の成分のアセチル化物を反応に用いる方法が挙げられる。 The lower acyl group preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms. Particularly preferred is a method using an acetylated product of the polymerizable monomer component in the reaction.
重合性単量体の低級アシル化物は、別途アシル化して予め合成したものを用いてもよいし、液晶ポリマーの製造時に重合性単量体に無水酢酸等のアシル化剤を加えて反応系内で生成せしめることもできる。 The lower acylated product of the polymerizable monomer may be separately acylated and synthesized beforehand, or an acylating agent such as acetic anhydride may be added to the polymerizable monomer during the production of the liquid crystal polymer. It can also be generated with
溶融アシドリシス法またはスラリー重合法のいずれの場合においても、重合反応は、温度１５０〜４００℃、好ましくは２５０〜３７０℃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；二酸化チタンなどの金属酸化物；三酸化アンチモンなどのアンチモン化合物；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 dialkyltin oxide (eg dibutyltin oxide) and diaryltin oxide; metal oxides such as titanium dioxide; antimony compounds such as antimony trioxide; organics such as alkoxytitanium silicate and titanium alkoxide. Examples include titanium compounds; alkali and alkaline earth metal salts of carboxylic acids (for example, potassium acetate); gaseous acid 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、該触媒の量は重合性単量体全量に対し、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 polymerizable monomers.
このようにして重縮合反応されて得られた本発明に係る液晶ポリマーは、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 according to the present invention obtained by the polycondensation reaction in this manner 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.
固相状態において行う熱処理の温度は、液晶ポリマーが溶融しない限り特に限定されないが、２００〜３５０℃、好ましくは２３０〜３２０℃で行うのがよい。 The temperature of the heat treatment performed in the solid phase is not particularly limited as long as the liquid crystal polymer is not melted, but is preferably 200 to 350 ° C, preferably 230 to 320 ° C.
本発明の液晶ポリマー組成物におけるパーティクル数は、１０００個以下であり、好ましい場合には８００個以下であり、より好ましい場合には５００個以下であり、特に好ましい場合には２００個以下である。パーティクル数が１０００個を超える場合には、電子部品の光学特性は不十分となる傾向にある。
パーティクル数とは、長さ６４ｍｍ、幅１３ｍｍ、厚み２ｍｍの成形片を純水５０ｍＬを備えた円筒形ガラス容器に載置し、３８ｋＨｚ、１００Ｗの出力にて１０分間超音波照射した後、純水１ｍＬ中に含まれる粒子径が２μｍ以上である粒子の数をいう。
なお、粒子径が２μｍ以上である粒子の数とは、パーティクルカウンター（スペクトリス社製ＬｉＱｕｉｌａｚ−０５）での測定に際し、粒子投影面の粒子径が２μｍ以上である粒子（パーティクル）の数を意味する。パーティクルには、本発明の液晶ポリマー組成物から構成される成形品から剥落した樹脂や充填材等の脱落物が含まれる。
The number of particles in the liquid crystal polymer composition of the present invention is 1000 or less, preferably 800 or less, more preferably 500 or less, and particularly preferably 200 or less. When the number of particles exceeds 1000, the optical characteristics of the electronic component tend to be insufficient.
The number of particles means that a molded piece having a length of 64 mm, a width of 13 mm, and a thickness of 2 mm is placed on a cylindrical glass container equipped with 50 mL of pure water, and subjected to ultrasonic irradiation for 10 minutes at an output of 38 kHz and 100 W. The number of particles having a particle size of 2 μm or more contained in 1 mL.
The number of particles having a particle diameter of 2 μm or more means the number of particles (particles) having a particle projection surface with a particle diameter of 2 μm or more when measured with a particle counter (LiQuilaz-05 manufactured by Spectris). . The particles include a fallen product such as a resin or a filler that has been peeled off from a molded article composed of the liquid crystal polymer composition of the present invention.
本発明では、パーティクル数の測定は、以下の通り行った。液晶ポリマー組成物のペレットを型締め圧１５ｔの射出成形機（住友重機械工業株式会社製 ＭＩＮＩＭＡＴ Ｍ２６／１５）を用いて、＃８０００相当の鏡面仕上げを施した金型により、結晶融解温度（Ｔｍ）よりも２０℃高いシリンダー温度および金型温度７０℃で、長さ６４ｍｍ、幅１２．７ｍｍ、厚み２ｍｍの短冊状曲げ試験片を作製した。この試験片を、純水５０ｍＬを備えた外径５０ｍｍ、内径４５ｍｍ、高さ１００ｍｍの円筒ガラス容器に、図１の通りゲート部が水に浸からないように載置した後、円筒ガラス容器を、水１０００ｍＬを備えた縦１４０ｍｍ、横２４０ｍｍ、深さ１００ｍｍの超音波洗浄槽（株式会社エスエヌディ製ＵＳ−１０２）に設置した。３８ｋＨｚ、１００Ｗの出力で１０分間超音波洗浄を行った後、純水１ｍＬ中に含まれる粒子径が２μｍ以上である粒子〔試験片から剥落した脱落物（パーティクル）〕の数を、パーティクルカウンター（スペクトリス社製ＬｉＱｕｉｌａｚ−０５）を使用して３回測定し、平均値を測定結果とした。 In the present invention, the number of particles was measured as follows. The crystal melting temperature (Tm) of the pellets of the liquid crystal polymer composition was measured using a mold with a mirror finish equivalent to # 8000 using an injection molding machine (MINIMAT M26 / 15 manufactured by Sumitomo Heavy Industries, Ltd.) with a clamping pressure of 15 t. A strip-shaped bending test piece having a length of 64 mm, a width of 12.7 mm, and a thickness of 2 mm was prepared at a cylinder temperature of 20 ° C. and a mold temperature of 70 ° C. The test piece was placed in a cylindrical glass container having an outer diameter of 50 mm, an inner diameter of 45 mm, and a height of 100 mm with 50 mL of pure water so that the gate portion was not immersed in water as shown in FIG. The sample was placed in an ultrasonic cleaning tank (US-102 manufactured by SND Corporation) having a length of 140 mm, a width of 240 mm, and a depth of 100 mm equipped with 1000 mL of water. After performing ultrasonic cleaning for 10 minutes at an output of 38 kHz and 100 W, the number of particles having a particle diameter of 2 μm or more contained in 1 mL of pure water (dropped material (particles) peeled off from the test piece) Spectris Co., Ltd. LiQuilaz-05) was used three times for measurement, and the average value was taken as the measurement result.
本発明における繊維状酸化チタンの数平均繊維長（Ｌ）については、１μｍ〜５０μｍ、好ましくは２μｍ〜４０μｍであり、より好ましくは３μｍ〜３０μｍである。繊維状酸化チタンの数平均繊維長（Ｌ）が１μｍ未満であると機械強度が維持できず、５０μｍ超であるとパーティクル発生の抑制効果が不十分となる傾向がある。 The number average fiber length (L) of the fibrous titanium oxide in the present invention is 1 μm to 50 μm, preferably 2 μm to 40 μm, more preferably 3 μm to 30 μm. If the number average fiber length (L) of the fibrous titanium oxide is less than 1 μm, the mechanical strength cannot be maintained, and if it exceeds 50 μm, the effect of suppressing particle generation tends to be insufficient.
繊維状酸化チタンの数平均繊維径（Ｄ）については、０．０５μｍ〜２．０μｍであり、好ましくは０．１μｍ〜１．５μｍであり、より好ましくは０．１μｍ〜１．０μｍである。繊維状酸化チタンの数平均繊維径（Ｄ）が０．０５μｍ未満であると機械強度が維持できず、２．０μｍ超であるとパーティクル発生の抑制効果が不十分となる傾向がある。 The number average fiber diameter (D) of the fibrous titanium oxide is 0.05 μm to 2.0 μm, preferably 0.1 μm to 1.5 μm, more preferably 0.1 μm to 1.0 μm. If the number average fiber diameter (D) of the fibrous titanium oxide is less than 0.05 μm, the mechanical strength cannot be maintained, and if it exceeds 2.0 μm, the effect of suppressing the generation of particles tends to be insufficient.
また、剛性とパーティクル発生抑制をバランスよく実現するためには、数平均繊維長（Ｌ）と数平均繊維径（Ｄ）の比Ｌ／Ｄが、３〜５０であることが必要であり、好ましくは３．５〜４０であり、より好ましくは４〜３０である。Ｌ／Ｄが３未満であると機械強度が維持できず、５０超であるとパーティクル発生の抑制効果が不十分となる傾向がある。 Further, in order to achieve a good balance between rigidity and particle generation suppression, the ratio L / D of the number average fiber length (L) to the number average fiber diameter (D) needs to be 3 to 50, preferably Is from 3.5 to 40, more preferably from 4 to 30. If the L / D is less than 3, the mechanical strength cannot be maintained, and if it exceeds 50, the effect of suppressing the generation of particles tends to be insufficient.
なお、数平均繊維長（Ｌ）および数平均繊維径（Ｄ）の測定方法は、走査型電子顕微鏡（日立製作所製Ｓ２１００Ａ）を用いて、１００００倍で写真撮影し、ランダムに５００本サンプリングし、各繊維（粒子）の最長部の長さの数平均値を数平均繊維長、最短部の長さの数平均値を数平均繊維径とした。 In addition, the number average fiber length (L) and the number average fiber diameter (D) are measured using a scanning electron microscope (S2100A manufactured by Hitachi, Ltd.) at a magnification of 10,000 times and randomly sampled 500 pieces. The number average value of the length of the longest part of each fiber (particle) was taken as the number average fiber length, and the number average value of the length of the shortest part was taken as the number average fiber diameter.
本発明に使用する繊維状酸化チタンとしては、針状酸化チタンおよび棒状酸化チタンが挙げられる。 Examples of the fibrous titanium oxide used in the present invention include acicular titanium oxide and rod-like titanium oxide.
本発明に使用する繊維状酸化チタンの結晶構造は、特に限定されないが、ルチル型、アナターゼ型およびブルサイト型からなる群から選択される一種以上のものを用いることができ、超音波洗浄の際のパーティクル発生低減効果に優れる点でルチル型が好ましい。また、樹脂への分散を良くするためにマグネシウム、カルシウムなど他の金属酸化物がドープされたものであってもよい。 The crystal structure of the fibrous titanium oxide used in the present invention is not particularly limited, but one or more selected from the group consisting of rutile type, anatase type and brucite type can be used. The rutile type is preferable because of its excellent particle generation reduction effect. Moreover, in order to improve the dispersion | distribution to resin, what doped other metal oxides, such as magnesium and calcium, may be used.
本発明に使用する繊維状酸化チタンは、その表面を公知のカップリング剤（例えば、シラン系カップリング剤、チタネート系カップリング剤、アルミ系カップリング剤など）、その他の表面処理剤で処理して用いることもできる。 The surface of the fibrous titanium oxide used in the present invention is treated with a known coupling agent (for example, silane coupling agent, titanate coupling agent, aluminum coupling agent, etc.) or other surface treatment agents. Can also be used.
本発明の液晶ポリマー組成物中における繊維状酸化チタンの含有量は、液晶ポリマー１００重量部に対して１〜１５０重量部であり、２〜１２０重量部が好ましく、５〜１１０重量部がより好ましく、１０〜８０重量部が特に好ましい。含有量が１重量部未満であるとパーティクル発生の抑制効果が不十分であり、１５０重量部超であると流動性が不十分となるうえに、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 content of fibrous titanium oxide in the liquid crystal polymer composition of the present invention is 1 to 150 parts by weight, preferably 2 to 120 parts by weight, more preferably 5 to 110 parts by weight with respect to 100 parts by weight of the liquid crystal polymer. 10 to 80 parts by weight is particularly preferable. If the content is less than 1 part by weight, the effect of suppressing the generation of particles is insufficient, and if it exceeds 150 parts by weight, the fluidity is insufficient and the wear of the cylinder and mold of the molding machine increases. Tend.
液晶ポリマーに繊維状酸化チタンを含有させると、液晶ポリマーと繊維状酸化チタンとの界面の濡れ性が良いことから、パーティクル発生を低減すると考えられる。 When fibrous titanium oxide is contained in the liquid crystal polymer, the wettability of the interface between the liquid crystal polymer and the fibrous titanium oxide is good, and it is considered that the generation of particles is reduced.
本発明の液晶ポリマー組成物には、本発明の効果を損なわない範囲で、その他の添加剤、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；界面活性剤などから選ばれる１種または２種以上を組み合わせて配合してもよい。これらの中でも、成型品について黒色が選好される点においてカーボンブラックが好ましい。 In the liquid crystal polymer composition of the present invention, other additives such as higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher fatty acid metal salts (here, higher fatty acid is carbon) within the range not impairing the effects of the present invention. Release agents such as polysiloxanes and fluororesins; coloring agents such as dyes, pigments and carbon black; antioxidants; thermal stabilizers; ultraviolet absorbers; antistatic agents; You may mix | blend 1 type chosen from surfactant etc. or 2 or more types in combination. Among these, carbon black is preferable in that black is preferred for molded products.
これらの他の添加剤の液晶ポリマー組成物中における含有量は、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０．５〜７重量部であるのがよい。これらの他の添加剤の含有量が液晶ポリマー１００重量部に対して１０重量部を超える場合には、成形加工性が低下したり、成形安定性が不十分となって成形品にブリスターが発生しやすくなる傾向がある。他の添加剤の含有量が０．１重量部を下回る場合、添加剤の機能を実現することができない。 The content of these other additives in the liquid crystal polymer composition is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 7 parts by weight with respect to 100 parts by weight of the liquid crystal polymer. Good. When the content of these other additives exceeds 10 parts by weight with respect to 100 parts by weight of the liquid crystal polymer, molding processability is deteriorated or molding stability is insufficient and blisters are generated in the molded product. It tends to be easy to do. When the content of the other additive is less than 0.1 part by weight, the function of the additive cannot be realized.
また、本発明の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などの外部滑剤効果を有するものについては、予め、液晶ポリマーおよび／または液晶ポリマー組成物のペレットの表面に付着せしめてもよい。 Further, when molding the liquid crystal polymer composition of the present invention, among the above-mentioned other additives, those having an external lubricant effect such as higher fatty acid, higher fatty acid ester, higher fatty acid metal salt, fluorocarbon surfactant, etc. The liquid crystal polymer and / or liquid crystal polymer composition pellets may be adhered to the surface.
また、本発明の液晶ポリマー組成物には、本発明の目的を損なわない範囲で、本発明の液晶ポリマーと同様の温度域で成形加工可能である他の樹脂成分を配合してもよい。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。液晶ポリマー組成物が他の樹脂成分を含む場合、他の樹脂成分の含有量は特に限定されないが、液晶ポリマー１００重量部に対して通常０．１〜３０重量部、特に０．５〜１０重量部であるのがよい。 In addition, the liquid crystal polymer composition of the present invention may be blended with other resin components that can be molded and processed in the same temperature range as the liquid crystal polymer of the present invention as long as the object of the present invention is not impaired. 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. When the liquid crystal polymer composition contains another resin component, the content of the other resin component is not particularly limited, but is usually 0.1 to 30 parts by weight, particularly 0.5 to 10 parts by weight with respect to 100 parts by weight of the liquid crystal polymer. Good part.
さらには、本発明の液晶ポリマー組成物には、本発明の効果を損なわない範囲で、他の無機または有機の、繊維状、板状または粒状の充填材、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、および粒状酸化チタン等の非繊維状酸化チタンなどを、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。これらの中でも、ガラス繊維、ミルドガラスもしくは粒状酸化チタンが物性とコストのバランスが優れている点で好ましい。 Furthermore, the liquid crystal polymer composition of the present invention includes other inorganic or organic fibrous, plate-like, or granular fillers, such as glass fiber, milled glass, silica alumina, as long as the effects of the present invention are not impaired. Fiber, alumina fiber, carbon fiber, aramid fiber, potassium titanate whisker, aluminum borate whisker, wollastonite, talc, mica, graphite, calcium carbonate, dolomite, clay, glass flakes, glass beads, barium sulfate, and granular oxidation Non-fibrous titanium oxides such as titanium can be blended alone or in combination of two or more. Among these, glass fiber, milled glass, or granular titanium oxide is preferable in that the balance between physical properties and cost is excellent.
本発明の液晶ポリマー組成物が無機または有機充填材を含有する場合、液晶ポリマー組成物中の無機または有機充填材の含有量は、液晶ポリマー１００重量部に対して、通常０．１〜１００重量部であるのが好ましい。 When the liquid crystal polymer composition of the present invention contains an inorganic or organic filler, the content of the inorganic or organic filler in the liquid crystal polymer composition is usually 0.1 to 100 weights per 100 parts by weight of the liquid crystal polymer. Part.
これらの繊維状酸化チタン、その他の添加剤、他の樹脂成分、他の充填材などは、液晶ポリマーに添加され、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ないし結晶融解温度＋２０℃で溶融混練して液晶ポリマー組成物とすることができる。 These fibrous titanium oxides, other additives, other resin components, other fillers, etc. are added to the liquid crystal polymer, and the crystal of the liquid crystal polymer is obtained using a Banbury mixer, kneader, uniaxial or biaxial extruder, etc. It can be melt-kneaded at around the melting temperature or at the crystal melting temperature + 20 ° C. to obtain a liquid crystal polymer composition.
このようにして得られた、本発明の液晶ポリマー組成物は、射出成形機、押出機などを用いる公知の成形方法によって、射出成形品、フィルム、シート、および不織布などの成形品に加工される。 The liquid crystal polymer composition of the present invention thus obtained is processed into a molded product such as an injection molded product, a film, a sheet, and a nonwoven fabric by a known molding method using an injection molding machine, an extruder or the like. .
本発明の液晶ポリマー組成物は、パーティクル発生が抑制されるため、超音波洗浄等が必要である精密機器の電子部品の製造に用いられる材料として好適に使用される。 Since the liquid crystal polymer composition of the present invention suppresses the generation of particles, it is suitably used as a material used in the manufacture of electronic parts for precision instruments that require ultrasonic cleaning or the like.
このような、本発明の液晶ポリマー組成物が使用される電子部品としては、コネクタ、スイッチ、リレー、コンデンサ、コイル、トランス、アンテナ、チップアンテナおよびカメラモジュールからなる群から選択される部品が挙げられる。 Examples of the electronic component in which the liquid crystal polymer composition of the present invention is used include components selected from the group consisting of connectors, switches, relays, capacitors, coils, transformers, antennas, chip antennas, and camera modules. .
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等を構成する光学電子部品や、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の製造に好適に使用される。 In particular, from electronic components that require ultrasonic cleaning, such as optical electronic components that constitute camera modules, etc., and electronic components for sliding members that involve sliding with other members, such as connectors, switches, relays, and camera modules It is suitably used for the production of a part constituting a member selected from the group consisting of
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、カメラモジュールを構成する光学電子部品の製造に特に好適に使用される。カメラモジュールを構成する光学電子部品としては、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 for the production of optical electronic components constituting a camera module because it prevents a decrease in optical properties due to fibrillation of the surface of the molded product. The optical electronic components that make up the camera module include a lens barrel (the part on which the lens is mounted), a mount holder (the part on which the barrel is mounted and fixed to the substrate), a CMOS (image sensor) frame, a shutter, a shutter plate, Examples include shutter bobbins, aperture rings, and stoppers (portions that hold the lens).
本発明のパーティクル発生の抑制方法は、液晶ポリマー組成物から構成される成形品表面におけるパーティクル発生の抑制方法であり、液晶ポリマー１００重量部に対して、数平均繊維長（Ｌ）が１μｍ〜５０μｍ、数平均繊維径（Ｄ）が０．１μｍ〜１．０μｍであり、かつＬ／Ｄが３〜５０である繊維状酸化チタンを１〜１５０重量部配合することを特徴とするパーティクル発生の抑制方法である。 The particle generation suppression method of the present invention is a method for suppressing particle generation on the surface of a molded article composed of a liquid crystal polymer composition, and the number average fiber length (L) is 1 μm to 50 μm with respect to 100 parts by weight of the liquid crystal polymer. 1 to 150 parts by weight of fibrous titanium oxide having a number average fiber diameter (D) of 0.1 μm to 1.0 μm and an L / D of 3 to 50 is suppressed. Is the method.
本発明のパーティクル発生の抑制方法では、液晶ポリマー１００重量部に対して上述の繊維状酸化チタンを１〜１５０重量部を配合する。繊維状酸化チタンの配合量が１重量部未満であるとパーティクル発生の抑制効果が不十分であり、１５０重量部超であると液晶ポリマー組成物の流動性が不十分となるうえに、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。繊維状酸化チタンの配合量は、液晶ポリマー１００重量部に対して２〜１２０重量部が好ましく、５〜１１０重量部がより好ましく、１０〜８０重量部が特に好ましい。 In the particle generation suppression method of the present invention, 1 to 150 parts by weight of the above-described fibrous titanium oxide is blended with 100 parts by weight of the liquid crystal polymer. If the blending amount of the fibrous titanium oxide is less than 1 part by weight, the effect of suppressing the generation of particles is insufficient, and if it exceeds 150 parts by weight, the liquid crystal polymer composition has insufficient fluidity and a molding machine. The wear of cylinders and molds tends to increase. The blending amount of the fibrous titanium oxide is preferably 2 to 120 parts by weight, more preferably 5 to 110 parts by weight, and particularly preferably 10 to 80 parts by weight with respect to 100 parts by weight of the liquid crystal polymer.
本発明のパーティクル発生の抑制方法において用いる液晶ポリマーは、液晶ポリマーを構成する重合性単量体および製造方法などについて上述の本発明の液晶ポリマー組成物において説明したものと同様であってよい。 The liquid crystal polymer used in the particle generation suppression method of the present invention may be the same as that described in the above-described liquid crystal polymer composition of the present invention for the polymerizable monomer constituting the liquid crystal polymer and the production method.
本発明のパーティクル発生の抑制方法において用いる繊維状酸化チタンは、数平均繊維長（Ｌ）、数平均繊維径（Ｄ）、Ｌ／Ｄおよび結晶構造について、上述の本発明の液晶ポリマー組成物において説明した繊維状酸化チタンのものと同様であってよい。また、繊維状酸化チタンは、その表面を公知のカップリング剤（例えば、シラン系カップリング剤、チタネート系カップリング剤、アルミ系カップリング剤など）、その他の表面処理剤で処理してもよい。 The fibrous titanium oxide used in the particle generation suppression method of the present invention is the number average fiber length (L), number average fiber diameter (D), L / D and crystal structure in the liquid crystal polymer composition of the present invention described above. It may be similar to that of the fibrous titanium oxide described. The surface of the fibrous titanium oxide may be treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, etc.) or other surface treatment agents. .
液晶ポリマーには、繊維状酸化チタンの他に、上述のその他の添加剤、他の樹脂成分、他の充填材などを配合することができる。配合する方法としては、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ないし結晶融解温度＋２０℃で溶融混練して液晶ポリマー組成物とする方法が挙げられる。このようにして得られた液晶ポリマー組成物は、射出成形機、押出機などを用いる公知の成形方法によって、射出成形品、フィルム、シート、および不織布などの成形品に加工される。 In addition to fibrous titanium oxide, the above-mentioned other additives, other resin components, other fillers, and the like can be blended in the liquid crystal polymer. Examples of the compounding method include a method of using a Banbury mixer, a kneader, a uniaxial or biaxial extruder, etc. to melt and knead the liquid crystal polymer near the crystal melting temperature or at the crystal melting temperature + 20 ° C. to obtain a liquid crystal polymer composition. . The liquid crystal polymer composition thus obtained is processed into a molded product such as an injection molded product, a film, a sheet, and a nonwoven fabric by a known molding method using an injection molding machine, an extruder or the like.
本発明のパーティクル発生の抑制方法によれば、液晶ポリマー組成物の成形品を輸送する場合や、成形品を摺動部材用電子部品として用いる場合、成形品を超音波洗浄する場合等に振動や擦れが生じても成形品表面からパーティクルの発生を抑制することができる。 According to the particle generation suppression method of the present invention, vibrations are generated when a molded product of a liquid crystal polymer composition is transported, when the molded product is used as an electronic component for a sliding member, when the molded product is subjected to ultrasonic cleaning, and the like. Even if rubbing occurs, generation of particles from the surface of the molded product can be suppressed.
本発明のパーティクル発生の抑制方法によれば、上述の本発明の液晶ポリマー組成物に関する説明において定義したパーティクル数（長さ６４ｍｍ、幅１３ｍｍ、厚み２ｍｍの成形片を純水５０ｍＬを備えた円筒形ガラス容器に載置し、３８ｋＨｚ、１００Ｗの出力にて１０分間超音波照射した後、純水１ｍＬ中に含まれる粒子径が２μｍ以上である粒子の数）は、１０００個以下であり、好ましい場合には８００個以下であり、より好ましい場合には５００個以下であり、特に好ましい場合には２００個以下である。 According to the method for suppressing particle generation of the present invention, the number of particles defined in the description relating to the liquid crystal polymer composition of the present invention described above (cylindrical shape having a molded piece having a length of 64 mm, a width of 13 mm, and a thickness of 2 mm with 50 mL of pure water. When placed on a glass container and irradiated with ultrasonic waves for 10 minutes at an output of 38 kHz and 100 W, the number of particles having a particle diameter of 2 μm or more contained in 1 mL of pure water is 1000 or less, which is preferable. Is 800 or less, more preferably 500 or less, and particularly preferably 200 or less.
以下、実施例により本発明を説明するが、本発明は以下の実施例に何ら限定されるものではない。なお、実施例中の結晶融解温度、溶融粘度、曲げ強度およびパーティクル発生数の測定、評価は以下に記載の方法で行った。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to a following example at all. In addition, the measurement and evaluation of the crystal melting temperature, the melt viscosity, the bending strength, and the number of particles generated in the examples were performed by the methods described below.
〈結晶融解温度〉
示差走査熱量計としてセイコーインスツルメンツ株式会社製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５０℃高い温度で１０分間保持する。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 an Exstar 6000 manufactured by Seiko Instruments Inc. as a differential scanning calorimeter, the endothermic peak temperature (Tm1) observed when the sample was measured at a temperature rising condition of 20 ° C./min from room temperature was measured, and then 50 ° C. from Tm1. Hold at high temperature 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 ).
〈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、１．０ｍｍφ×１０ｍｍのキャピラリーを用いて、剪断速度１０００ｓｅｃ−１の条件下、試料の結晶融解温度（Ｔｍ）＋２０℃での溶融粘度をそれぞれ測定した。
<Melt viscosity>
Using a 1.0 mmφ × 10 mm capillary with a melt viscosity measuring apparatus (Capillograph 1D manufactured by Toyo Seiki Co., Ltd.), melt viscosity at 20 ° C. of crystal melting temperature (Tm) of the sample under the condition of a shear rate of 1000 sec −1. Was measured respectively.
〈曲げ強度〉
射出成形機（日精樹脂工業株式会社製ＵＨ−１０００−１１０）を用いて結晶融解温度（Ｔｍ）よりも２０℃高いシリンダー温度、金型温度７０℃で射出成形し、長さ１２７ｍｍ、幅１２．７ｍｍ、厚み３．２ｍｍの短冊状曲げ試験片を作成した。曲げ試験は、ＡＳＴＭ Ｄ７９０に準拠して行った。
<Bending strength>
Using an injection molding machine (Nissei Plastic Industries, Ltd. UH-1000-110), injection molding was performed at a cylinder temperature 20 ° C. higher than the crystal melting temperature (Tm) and a mold temperature 70 ° C., length 127 mm, width 12. A strip-shaped bending test piece having a thickness of 7 mm and a thickness of 3.2 mm was prepared. The bending test was performed according to ASTM D790.
〈パーティクル発生数〉
得られた樹脂組成物のペレットを型締め圧１５ｔの射出成形機（住友重機械工業株式会社製 ＭＩＮＩＭＡＴ Ｍ２６／１５）を用いて、＃８０００相当の鏡面仕上げを施した金型により、結晶融解温度（Ｔｍ）よりも２０℃高いシリンダー温度および金型温度７０℃で、長さ６４ｍｍ、幅１２．７ｍｍ、厚み２ｍｍの短冊状曲げ試験片を作製し、パーティクル数測定の試験片とした。
純水５０ｍＬを備えた外径５０ｍｍ、内径４５ｍｍ、高さ１００ｍｍの円筒ガラス容器に、図１の通り各試験片１個をゲート部が水に浸からないように載置した後、円筒ガラス容器を、水１０００ｍＬを備えた縦１４０ｍｍ、横２４０ｍｍ、深さ１００ｍｍの超音波洗浄槽（株式会社エスエヌディ製ＵＳ−１０２）に設置した。
３８ｋＨｚ、１００Ｗの出力で１０分間超音波洗浄を行った後、純水１ｍＬ中に含まれる粒子径が２μｍ以上である粒子〔試験片から剥落した脱落物（パーティクル）〕の数を、パーティクルカウンター（スペクトリス社製ＬｉＱｕｉｌａｚ−０５）を使用して３回測定し、平均値を測定結果とした。
<Number of particles generated>
The obtained resin composition pellets were subjected to a crystal melting temperature by using a mold having a mirror finish equivalent to # 8000 using an injection molding machine (MINIMAT M26 / 15 manufactured by Sumitomo Heavy Industries, Ltd.) with a clamping pressure of 15 t. A strip-shaped bending test piece having a length of 64 mm, a width of 12.7 mm, and a thickness of 2 mm was produced at a cylinder temperature 20 ° C. higher than (Tm) and a mold temperature of 70 ° C., and used as a test piece for particle number measurement.
After placing each test piece as shown in FIG. 1 in a cylindrical glass container having an outer diameter of 50 mm, an inner diameter of 45 mm, and a height of 100 mm with 50 mL of pure water so that the gate portion is not immersed in water, the cylindrical glass container Was installed in an ultrasonic cleaning tank (US-102 manufactured by SND Co., Ltd.) having a length of 140 mm, a width of 240 mm, and a depth of 100 mm equipped with 1000 mL of water.
After performing ultrasonic cleaning for 10 minutes at an output of 38 kHz and 100 W, the number of particles having a particle diameter of 2 μm or more contained in 1 mL of pure water (dropped material (particles) peeled off from the test piece) Spectris Co., Ltd. LiQuilaz-05) was used three times for measurement, and the average value was taken as the measurement result.
実施例および比較例において下記の略号は以下の化合物を表す。
ＰＯＢ：４−ヒドロキシ安息香酸
ＢＯＮ６：６−ヒドロキシ−２−ナフトエ酸
ＢＰ：４，４’−ジヒドロキシビフェニル
ＨＱ：ハイドロキノン
ＴＰＡ：テレフタル酸
ＮＤＡ：２，６−ナフタレンジカルボン酸
In the examples and comparative examples, the following abbreviations represent the following compounds.
POB: 4-hydroxybenzoic acid BON6: 6-hydroxy-2-naphthoic acid BP: 4,4'-dihydroxybiphenyl HQ: hydroquinone TPA: terephthalic acid NDA: 2,6-naphthalenedicarboxylic acid
［合成例１（ＬＣＰ−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、ＰＯＢ：６４１．９ｇ（７１．５モル％）、ＢＯＮ６：３０．６ｇ（２．５モル％）、ＨＱ：９３．０ｇ（１３モル％）およびＮＤＡ１８２．７ｇ（１３モル％）を仕込み、さらに全モノマーの水酸基量（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。
[Synthesis Example 1 (LCP-1)]
POB: 641.9 g (71.5 mol%), BON 6: 30.6 g (2.5 mol%), HQ: 93.0 g (13 mol) %) And 182.7 g (13 mol%) of NDA, 1.03 times mol acetic anhydride with respect to the amount of hydroxyl groups (mol) of all monomers, and deacetic acid polymerization was carried out under the following conditions.
窒素ガス雰囲気下に室温〜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、反応容器から内容物を取り出し、粉砕機により液晶ポリエステル樹脂のペレットを得た。重合時の留出酢酸量は、ほぼ理論値どおりであった。得られたペレットの結晶融解温度（Ｔｍ）は３２１℃であった。 The temperature was raised from room temperature to 145 ° C. over 1 hour under a nitrogen gas atmosphere, and maintained at 145 ° C. for 30 minutes. Next, the temperature was raised to 345 ° C. over 7 hours while acetic acid produced as a by-product was distilled off, and then the pressure was reduced to 10 mmHg over 80 minutes. When the predetermined torque was exhibited, the polymerization reaction was terminated, the contents were taken out from the reaction vessel, and liquid crystal polyester resin pellets were obtained using a pulverizer. The amount of acetic acid distilled during the polymerization was almost as theoretical. The crystal melting temperature (Tm) of the obtained pellet was 321 ° C.
［合成例２（ＬＣＰ−２）］
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、ＰＯＢ：３２３．２ｇ（３６モル％）、ＢＯＮ６：４８．９ｇ（４モル％）、ＢＰ：１６９．４ｇ（１４モル％）、ＨＱ：１１４．５ｇ（１６モル％）およびＴＰＡ：３２３．９ｇ（３０モル％）を仕込み、さらに全モノマーの水酸基量（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。
[Synthesis Example 2 (LCP-2)]
In a reaction vessel equipped with a stirrer with a torque meter and a distillation pipe, POB: 323.2 g (36 mol%), BON 6: 48.9 g (4 mol%), BP: 169.4 g (14 mol%), HQ : 114.5 g (16 mol%) and TPA: 323.9 g (30 mol%), and 1.03 times mol acetic anhydride with respect to the amount of hydroxyl groups (mol) of all monomers were charged under the following conditions: Deacetic acid polymerization was performed.
窒素ガス雰囲気下に室温〜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エステル樹脂のペレットを得た。重合時の留出酢酸量は、ほぼ理論値どおりであった。得られたペレットの結晶融解温度（Ｔｍ）は３３５℃であった。 The temperature was raised from room temperature to 145 ° C. over 1 hour under a nitrogen gas atmosphere, and maintained at 145 ° C. for 30 minutes. Next, the temperature was raised to 350 ° C. over 7 hours while distilling off the acetic acid produced as a by-product, and then the pressure was reduced to 5 mmHg over 80 minutes. When the predetermined torque was exhibited, the polymerization reaction was terminated, the contents were taken out from the reaction vessel, and liquid crystal polyester resin pellets were obtained using a pulverizer. The amount of acetic acid distilled during the polymerization was almost as theoretical. The crystal melting temperature (Tm) of the obtained pellet was 335 ° C.
［合成例３（ＬＣＰ−３）］
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、ＰＯＢ：６５５．４ｇ（７３モル％）およびＢＯＮ６：３３０．２ｇ（２７モル％）を仕込み、さらに全モノマーの水酸基量（モル）に対して１．０２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。
[Synthesis Example 3 (LCP-3)]
POB: 655.4 g (73 mol%) and BON6: 330.2 g (27 mol%) were charged into a reaction vessel equipped with a stirrer with a torque meter and a distillation pipe, and the hydroxyl amount (mol) of all monomers was further increased. On the other hand, 1.02 moles of acetic anhydride was charged and deacetic acid polymerization was performed under the following conditions.
窒素ガス雰囲気下に室温〜１４５℃まで１時間で昇温し、１４５℃にて３０分間保持した。次いで、副生する酢酸を留去させつつ３２０℃まで 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、反応容器から内容物を取り出し、粉砕機により液晶ポリエステル樹脂のペレットを得た。重合時の留出酢酸量は、ほぼ理論値どおりであった。得られたペレットの結晶融解温度（Ｔｍ）は２７９℃であった。 The temperature was raised from room temperature to 145 ° C. over 1 hour in a nitrogen gas atmosphere, and maintained at 145 ° C. for 30 minutes. Next, the temperature was raised to 320 ° C. over time while acetic acid produced as a by-product was distilled off, and then the pressure was reduced to 10 mmHg over 80 minutes. When the predetermined torque was exhibited, the polymerization reaction was terminated, the contents were taken out from the reaction vessel, and liquid crystal polyester resin pellets were obtained using a pulverizer. The amount of acetic acid distilled during the polymerization was almost as theoretical. The obtained pellet had a crystal melting temperature (Tm) of 279 ° C.
［合成例４（ＬＣＰ−４）］
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、ＢＯＮ６：６６０．４ｇ（５４モル％）、ＢＰ：２６０．２ｇ（２１．５モル％）、ＨＱ：１０．７ｇ（１．５モル％）およびＴＰＡ２４８．３ｇ（２３モル％）を仕込み、さらに全モノマーの水酸基量（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。
[Synthesis Example 4 (LCP-4)]
In a reaction vessel equipped with a stirrer with a torque meter and a distillation pipe, BON6: 660.4 g (54 mol%), BP: 260.2 g (21.5 mol%), HQ: 10.7 g (1.5 mol) %) And 248.3 g (23 mol%) of TPA, 1.03 mol mol of acetic anhydride with respect to the amount of hydroxyl groups (mol) of all monomers, and deacetic acid polymerization was performed under the following conditions.
窒素ガス雰囲気下に室温〜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、反応容器から内容物を取り出し、粉砕機により液晶ポリエステル樹脂のペレットを得た。重合時の留出酢酸量は、ほぼ理論値どおりであった。得られたペレットの結晶融解温度（Ｔｍ）は３４０℃であった。 The temperature was raised from room temperature to 145 ° C. over 1 hour under a nitrogen gas atmosphere, and maintained at 145 ° C. for 30 minutes. Next, the temperature was raised to 345 ° C. over 7 hours while acetic acid produced as a by-product was distilled off, and then the pressure was reduced to 10 mmHg over 80 minutes. When the predetermined torque was exhibited, the polymerization reaction was terminated, the contents were taken out from the reaction vessel, and liquid crystal polyester resin pellets were obtained using a pulverizer. The amount of acetic acid distilled during the polymerization was almost as theoretical. The crystal melting temperature (Tm) of the obtained pellet was 340 ° C.
以下の実施例および比較例で使用した充填材を示す。
繊維状酸化チタン−１：石原産業（株）社製、針状酸化チタン「ＦＴＬ−４００」（数平均繊維長（Ｌ）＝１０．１μｍ、数平均繊維径（Ｄ）＝０．５μｍ、Ｌ／Ｄ＝２０）
繊維状酸化チタン−２：石原産業（株）社製、棒状酸化チタン「ＰＦＲ４０４」（数平均繊維長（Ｌ）＝２．４１μｍ、数平均繊維径（Ｄ）＝０．５４μｍ、Ｌ／Ｄ＝４．５）
粒状酸化チタン：石原産業（株）社製、粒状酸化チタン「ＣＲ−６０」、数平均粒子径 ０．２μｍ）
タルク：富士タルク（株）社製、「ＤＳ−３４」（数平均粒径２３μｍ）
ガラス繊維：日東紡績（株）社製、ＰＦ７０Ｅ−００１（数平均繊維長（Ｌ）＝５８μｍ、数平均繊維径（Ｄ）＝１０．４μｍ）
カーボンブラック：三菱化学（株）製、三菱カーボンブラック ＃９５０
オレフィン系共重合体：住友化学（株）社製、ボンドファーストＢＦ−２Ｃ
表１〜４に記載の各配合量は、ＬＣＰ１００重量部に対する重量部とする。
The filler used in the following examples and comparative examples is shown.
Fibrous titanium oxide-1: manufactured by Ishihara Sangyo Co., Ltd., acicular titanium oxide “FTL-400” (number average fiber length (L) = 10.1 μm, number average fiber diameter (D) = 0.5 μm, L / D = 20)
Fibrous titanium oxide-2: manufactured by Ishihara Sangyo Co., Ltd., rod-shaped titanium oxide “PFR404” (number average fiber length (L) = 2.41 μm, number average fiber diameter (D) = 0.54 μm, L / D = 4.5)
Granular titanium oxide: manufactured by Ishihara Sangyo Co., Ltd., granular titanium oxide “CR-60”, number average particle size 0.2 μm)
Talc: “DS-34” (number average particle size 23 μm), manufactured by Fuji Talc Co., Ltd.
Glass fiber: PF70E-001 manufactured by Nitto Boseki Co., Ltd. (number average fiber length (L) = 58 μm, number average fiber diameter (D) = 10.4 μm)
Carbon black: Mitsubishi Carbon Black # 950, manufactured by Mitsubishi Chemical Corporation
Olefin copolymer: manufactured by Sumitomo Chemical Co., Ltd., Bond First BF-2C
Each compounding amount described in Tables 1 to 4 is parts by weight with respect to 100 parts by weight of LCP.
実施例１
熱風乾燥器中で１３０℃にて６時間乾燥したＬＣＰ−１を１００重量部に対して、繊維状酸化チタン−１を５．４重量部、カーボンブラックを３．３重量部配合して得られた混合物を、シリンダーの最高温度３６０℃に設定した２軸押出機（（株）池貝社製ＰＣＭ−３０）を用い溶融混練して目的の液晶ポリマー組成物のペレットを得た。得られたペレットを用い、前記の試験方法にて、各物性の測定を行った。結果を表１に示す。
Example 1
Obtained by blending 5.4 parts by weight of fibrous titanium oxide-1 and 3.3 parts by weight of carbon black with 100 parts by weight of LCP-1 dried at 130 ° C. for 6 hours in a hot air dryer The obtained mixture was melt-kneaded using a twin-screw extruder (PCM-30 manufactured by Ikegai Co., Ltd.) set at a maximum temperature of 360 ° C. to obtain pellets of the desired liquid crystal polymer composition. Each physical property was measured by the test method using the obtained pellet. The results are shown in Table 1.
比較例１
ＬＣＰ−１を単独で用いて、前記の試験方法にて各物性の測定を行った。結果を表１に示す。
Comparative Example 1
Using LCP-1 alone, each physical property was measured by the above test method. The results are shown in Table 1.
実施例２〜５及び比較例２〜８
実施例１と同様にＬＣＰ−１、繊維状酸化チタン−１、繊維状酸化チタン−２、粒状酸化チタン、タルク、ガラス繊維、カーボンブラック、オレフィン系共重合体を、表１に記載した組成としたこと以外は、実施例１と同様の設備、操作方法により、それぞれの液晶ポリマー組成物のペレットを製造した。得られたペレットを用い、実施例１と同様にして、前記の試験方法にて、各物性の測定を行った。結果を表１に示す。
Examples 2 to 5 and Comparative Examples 2 to 8
In the same manner as in Example 1, LCP-1, fibrous titanium oxide-1, fibrous titanium oxide-2, granular titanium oxide, talc, glass fiber, carbon black, olefin-based copolymer and the composition described in Table 1 Except that, pellets of each liquid crystal polymer composition were produced by the same equipment and operation method as in Example 1. Using the obtained pellets, each physical property was measured by the above test method in the same manner as in Example 1. The results are shown in Table 1.
実施例６
熱風乾燥器中で１３０℃にて６時間乾燥したＬＣＰ−２を１００重量部に対して、繊維状酸化チタン−１を４４．８重量部およびカーボンブラックを４．５重量部配合して得られた混合物を、シリンダーの最高温度３６０℃に設定した２軸押出機（（株）池貝社製ＰＣＭ−３０）を用い溶融混練して目的の液晶ポリマー組成物のペレットを得た。得られたペレットを用い、前記の試験方法にて、各物性の測定を行った。結果を表２に示す。
Example 6
Obtained by blending 44.8 parts by weight of fibrous titanium oxide-1 and 4.5 parts by weight of carbon black with 100 parts by weight of LCP-2 dried at 130 ° C. for 6 hours in a hot air dryer The obtained mixture was melt-kneaded using a twin-screw extruder (PCM-30 manufactured by Ikegai Co., Ltd.) set at a maximum temperature of 360 ° C. to obtain pellets of the desired liquid crystal polymer composition. Each physical property was measured by the test method using the obtained pellet. The results are shown in Table 2.
比較例９
ＬＣＰ−２を単独で用いて、前記の試験方法にて、各物性の測定を行った。結果を表２に示す。
Comparative Example 9
Using LCP-2 alone, each physical property was measured by the above test method. The results are shown in Table 2.
実施例７
熱風乾燥器中で１３０℃にて６時間乾燥したＬＣＰ−３を１００重量部に対して、繊維状酸化チタン−１を５．４重量部、カーボンブラックを３．３重量部配合して得られた混合物を、シリンダーの最高温度３００℃に設定した２軸押出機（（株）池貝社製ＰＣＭ−３０）を用い溶融混練して目的の液晶ポリマー組成物のペレットを得た。得られたペレットを用い、前記の試験方法にて、各物性の測定を行った。結果を表３に示す。
Example 7
Obtained by blending 5.4 parts by weight of fibrous titanium oxide-1 and 3.3 parts by weight of carbon black with 100 parts by weight of LCP-3 dried at 130 ° C. for 6 hours in a hot air dryer. The obtained mixture was melt-kneaded using a twin-screw extruder (PCM-30 manufactured by Ikegai Co., Ltd.) set at a maximum temperature of 300 ° C. to obtain pellets of the desired liquid crystal polymer composition. Each physical property was measured by the test method using the obtained pellet. The results are shown in Table 3.
比較例１０
ＬＣＰ−３を単独で用いて、前記の試験方法にて、各物性の測定を行った。結果を表３に示す。
Comparative Example 10
Using LCP-3 alone, each physical property was measured by the above test method. The results are shown in Table 3.
実施例８
熱風乾燥器中で１３０℃にて６時間乾燥したＬＣＰ−４を１００重量部に対して、繊維状酸化チタン−２を４４．８重量部、カーボンブラックを４．５重量部配合して得られた混合物を、シリンダーの最高温度３６０℃に設定した２軸押出機（（株）池貝社製ＰＣＭ−３０）を用い溶融混練して目的の液晶ポリマー組成物のペレットを得た。得られたペレットを用い、前期の試験方法にて、各物性の測定を行った。結果を表４に示す。
Example 8
Obtained by blending 44.8 parts by weight of fibrous titanium oxide-2 and 4.5 parts by weight of carbon black with 100 parts by weight of LCP-4 dried at 130 ° C. for 6 hours in a hot air dryer. The obtained mixture was melt-kneaded using a twin-screw extruder (PCM-30 manufactured by Ikegai Co., Ltd.) set at a maximum temperature of 360 ° C. to obtain pellets of the desired liquid crystal polymer composition. Each physical property was measured by the test method of the previous term using the obtained pellet. The results are shown in Table 4.
比較例１１
ＬＣＰ−４を単独で用いて、前記の試験方法にて、各物性の測定を行った。結果を表４に示す。
Comparative Example 11
Each physical property was measured by the above test method using LCP-4 alone. The results are shown in Table 4.
表１〜４に示したように、本発明の液晶ポリマー組成物（実施例１〜８）は、粒子径２μｍ以上のパーティクル数が１０００個未満であって、曲げ強度が良好なものであった。それに対し、比較例１〜１１のように、本発明の範囲から外れる場合は、パーティクル発生または曲げ強度の少なくとも一方について好ましくない結果となった。 As shown in Tables 1 to 4, the liquid crystal polymer compositions (Examples 1 to 8) of the present invention had less than 1000 particles having a particle diameter of 2 μm or more and good bending strength. . On the other hand, when it was outside the scope of the present invention as in Comparative Examples 1 to 11, unfavorable results were obtained with respect to at least one of particle generation and bending strength.
また、本発明の液晶ポリマー組成物（実施例１〜８）については、ＬＣＰ−１〜４を単独で用いた場合（比較例１、９、１０および１１）よりも粒子径２μｍ以上のパーティクル数が少なく、本発明のパーティクル発生抑制効果が良好であることが示された。 Moreover, about the liquid crystal polymer composition (Examples 1-8) of this invention, when LCP-1-4 is used independently (Comparative Examples 1, 9, 10, and 11), the number of particles whose particle diameter is 2 micrometers or more It was shown that the particle generation suppression effect of the present invention is good.
１ 円筒ガラス容器
２ 純水
３ 試験片
４ ゲート部
DESCRIPTION OF
Claims (14)
パーティクル数：長さ６４ｍｍ、幅１３ｍｍ、厚み２ｍｍの成形片を純水５０ｍＬを備えた円筒形ガラス容器に載置し、３８ｋＨｚ、１００Ｗの出力にて１０分間超音波照射した後、純水１ｍＬ中に含まれる粒子径が２μｍ以上である粒子の数。 A fiber having a number average fiber length (L) of 1 μm to 50 μm, a number average fiber diameter (D) of 0.05 μm to 2.0 μm, and an L / D of 3 to 50 with respect to 100 parts by weight of the liquid crystal polymer A liquid crystal polymer composition containing 1 to 150 parts by weight of titanium oxide and having 1000 or less particles according to the following definition.
Number of particles: A molded piece having a length of 64 mm, a width of 13 mm, and a thickness of 2 mm was placed on a cylindrical glass container equipped with 50 mL of pure water, and subjected to ultrasonic irradiation for 10 minutes at an output of 38 kHz and 100 W, and then in 1 mL of pure water. The number of particles having a particle diameter of 2 μm or more.
液晶ポリマー１００重量部に対して、数平均繊維長（Ｌ）が１μｍ〜５０μｍ、数平均繊維径（Ｄ）が０．０５μｍ〜２．０μｍであり、かつＬ／Ｄが３〜５０である繊維状酸化チタンを１〜１５０重量部を配合することを特徴とする、パーティクル発生の抑制方法。 A method for suppressing particle generation on the surface of a molded article composed of a liquid crystal polymer composition,
A fiber having a number average fiber length (L) of 1 μm to 50 μm, a number average fiber diameter (D) of 0.05 μm to 2.0 μm, and an L / D of 3 to 50 with respect to 100 parts by weight of the liquid crystal polymer 1 to 150 parts by weight of titanium oxide is blended, and a method for suppressing particle generation.
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| JP2019127556A (en) * | 2018-01-26 | 2019-08-01 | 上野製薬株式会社 | Liquid crystal polyester resin composition |
| US11258184B2 (en) | 2019-08-21 | 2022-02-22 | Ticona Llc | Antenna system including a polymer composition having a low dissipation factor |
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| US11555113B2 (en) | 2019-09-10 | 2023-01-17 | Ticona Llc | Liquid crystalline polymer composition |
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| US11729908B2 (en) | 2020-02-26 | 2023-08-15 | Ticona Llc | Circuit structure |
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