JP6840455B2 - Liquid crystal polymer composition - Google Patents
Liquid crystal polymer composition Download PDFInfo
- Publication number
- JP6840455B2 JP6840455B2 JP2015177811A JP2015177811A JP6840455B2 JP 6840455 B2 JP6840455 B2 JP 6840455B2 JP 2015177811 A JP2015177811 A JP 2015177811A JP 2015177811 A JP2015177811 A JP 2015177811A JP 6840455 B2 JP6840455 B2 JP 6840455B2
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- JP
- Japan
- Prior art keywords
- liquid crystal
- crystal polymer
- polymer composition
- weight
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920000106 Liquid crystal polymer Polymers 0.000 title claims description 115
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 title claims description 112
- 239000000203 mixture Substances 0.000 title claims description 61
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 36
- 239000000194 fatty acid Substances 0.000 claims description 36
- 229930195729 fatty acid Natural products 0.000 claims description 36
- -1 fatty acid ester Chemical class 0.000 claims description 35
- 125000003118 aryl group Chemical group 0.000 claims description 30
- 238000000465 moulding Methods 0.000 claims description 30
- 239000000945 filler Substances 0.000 claims description 29
- 239000012765 fibrous filler Substances 0.000 claims description 27
- 239000000155 melt Substances 0.000 claims description 20
- 150000004665 fatty acids Chemical class 0.000 claims description 17
- 239000000835 fiber Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 15
- 239000004973 liquid crystal related substance Substances 0.000 claims description 14
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- 239000003365 glass fiber Substances 0.000 claims description 9
- 229920001225 polyester resin Polymers 0.000 claims description 9
- 239000004645 polyester resin Substances 0.000 claims description 9
- 239000000454 talc Substances 0.000 claims description 9
- 229910052623 talc Inorganic materials 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000010445 mica Substances 0.000 claims description 5
- 229910052618 mica group Inorganic materials 0.000 claims description 5
- 238000001746 injection moulding Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 3
- 229920006231 aramid fiber Polymers 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 229910052570 clay Inorganic materials 0.000 claims description 3
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 3
- 239000010459 dolomite Substances 0.000 claims description 3
- 229910000514 dolomite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000010456 wollastonite Substances 0.000 claims description 3
- 229910052882 wollastonite Inorganic materials 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 48
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 46
- 206010042674 Swelling Diseases 0.000 description 34
- 230000008961 swelling Effects 0.000 description 34
- 239000000047 product Substances 0.000 description 27
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 24
- 239000000178 monomer Substances 0.000 description 23
- 229920001577 copolymer Polymers 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 19
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 239000002253 acid Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 241000790917 Dioxys <bee> Species 0.000 description 8
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 8
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 150000004820 halides Chemical class 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000012792 core layer Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- BCEQKAQCUWUNML-UHFFFAOYSA-N 4-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(O)C(C(O)=O)=C1 BCEQKAQCUWUNML-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 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 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
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- FIASKJZPIYCESA-UHFFFAOYSA-L calcium;octacosanoate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O FIASKJZPIYCESA-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- VZQSBJKDSWXLKX-UHFFFAOYSA-N 3-(3-hydroxyphenyl)phenol Chemical group OC1=CC=CC(C=2C=C(O)C=CC=2)=C1 VZQSBJKDSWXLKX-UHFFFAOYSA-N 0.000 description 1
- BWBGEYQWIHXDKY-UHFFFAOYSA-N 3-(4-hydroxyphenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=CC(O)=C1 BWBGEYQWIHXDKY-UHFFFAOYSA-N 0.000 description 1
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 description 1
- XFDUHJPVQKIXHO-UHFFFAOYSA-N 3-aminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1 XFDUHJPVQKIXHO-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- TVBXXOVRWRDFMB-UHFFFAOYSA-N 3-hydroxynaphthalene-2,7-dicarboxylic acid Chemical compound C1=C(O)C(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 TVBXXOVRWRDFMB-UHFFFAOYSA-N 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
- 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
- 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
- ZBIBQNVRTVLOHQ-UHFFFAOYSA-N 5-aminonaphthalen-1-ol Chemical compound C1=CC=C2C(N)=CC=CC2=C1O ZBIBQNVRTVLOHQ-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 compound 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
- 235000021357 Behenic acid Nutrition 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 101100256637 Drosophila melanogaster senju gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 235000021353 Lignoceric acid Nutrition 0.000 description 1
- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MWKGOHCHXBLCSH-UHFFFAOYSA-L [Zn+2].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O MWKGOHCHXBLCSH-UHFFFAOYSA-L 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
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- VCZQCLHBLSUGML-UHFFFAOYSA-K aluminum octacosanoate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O VCZQCLHBLSUGML-UHFFFAOYSA-K 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- RAVAZXZOSFZIRB-UHFFFAOYSA-L barium(2+);hexadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O RAVAZXZOSFZIRB-UHFFFAOYSA-L 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- HRBZRZSCMANEHQ-UHFFFAOYSA-L calcium;hexadecanoate Chemical compound [Ca+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O HRBZRZSCMANEHQ-UHFFFAOYSA-L 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 229960000735 docosanol Drugs 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
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- 229940063002 magnesium palmitate Drugs 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- ABSWXCXMXIZDSN-UHFFFAOYSA-L magnesium;hexadecanoate Chemical compound [Mg+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O ABSWXCXMXIZDSN-UHFFFAOYSA-L 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
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- 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
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-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
- 239000004745 nonwoven fabric Substances 0.000 description 1
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- 230000003287 optical effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
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- 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
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- BXFXQPLYASVMSV-UHFFFAOYSA-M potassium;octacosanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O BXFXQPLYASVMSV-UHFFFAOYSA-M 0.000 description 1
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- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- YKIBJOMJPMLJTB-UHFFFAOYSA-M sodium;octacosanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O YKIBJOMJPMLJTB-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
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- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Injection Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacturing Of Electrical Connectors (AREA)
- Connector Housings Or Holding Contact Members (AREA)
Description
本発明は、成形加工時における成形品表面の膨れおよびリフロー後のブリスタの発生を抑制できる液晶ポリマー組成物に関する。 The present invention relates to a liquid crystal polymer composition capable of suppressing swelling of the surface of a molded product during molding and generation of blister after reflow.
サーモトロピック液晶ポリマー（以下、液晶ポリマーまたはＬＣＰと略称する）は、耐熱性、剛性等の機械物性、耐薬品性、寸法精度等に優れているため、各種用途にその使用が拡大しつつある。 Thermotropic liquid crystal polymers (hereinafter abbreviated as liquid crystal polymers or LCPs) are excellent in mechanical properties such as heat resistance and rigidity, chemical resistance, dimensional accuracy, etc., and therefore their use is expanding in various applications.
特にパーソナル・コンピューターや携帯電話等の情報・通信分野においては、部品の高集積度化、小型化、薄肉化、低背化が急速に進んでおり、非常に薄い部分が形成されるケースが多い。そこで、液晶ポリマーはその優れた成形性、すなわち流動性が良好であり、かつバリが出ないという他の樹脂にない特徴を生かして、その使用量が大幅に増大している。 Especially in the information and communication fields such as personal computers and mobile phones, the degree of integration, miniaturization, thinning, and low profile of parts are rapidly advancing, and very thin parts are often formed. .. Therefore, the amount of the liquid crystal polymer used has been significantly increased by taking advantage of its excellent moldability, that is, good fluidity and no burrs, which are not found in other resins.
また液晶ポリマーは、反りの発生抑制や機械強度の向上を目的に、通常タルクやマイカなどの充填材を添加した液晶ポリマー組成物として、成形に供することが知られている。
近年、成形品の更なる小型化や薄肉化とともに、成形時の射出速度を高めるハイサイクル成形が要求されており、液晶ポリマーにもより一層の高流動性が求められている。
ハイサイクル成形に適した高流動性の液晶ポリマーを得るためには、タルクやマイカなどの充填材の配合量を少なくし、低粘度化する方法が考えられる。
Further, it is known that a liquid crystal polymer is usually used for molding as a liquid crystal polymer composition to which a filler such as talc or mica is added for the purpose of suppressing the occurrence of warpage and improving the mechanical strength.
In recent years, along with further miniaturization and thinning of molded products, high-cycle molding that increases the injection speed during molding has been required, and liquid crystal polymers are also required to have even higher fluidity.
In order to obtain a highly fluid liquid crystal polymer suitable for high-cycle molding, a method of reducing the blending amount of a filler such as talc or mica to reduce the viscosity can be considered.
しかし、充填材の配合量を少なくした液晶ポリマーをハイサイクル成形に供した場合、成形時に成形品表面に膨れが発生するとともに、リフロー後にブリスタが発生するという問題があった。 However, when a liquid crystal polymer in which the amount of the filler is reduced is subjected to high cycle molding, there is a problem that swelling occurs on the surface of the molded product during molding and blister is generated after reflow.
成形品表面に膨れが発生する原因は、液晶ポリマーが成形機の金型内を通過する際に、金型と接触するスキン層（樹脂表面層）が先に固化するためコア層（樹脂中心部）との境界に歪みが生じ、金型を開いた際の応力によって歪み部分に空洞（膨れ）が生じるものと考えられる。ハイサイクル成形のような高速で射出した場合、スキン層とコア層との歪みが増大するため、膨れの発生個数もより顕著となる。 The cause of swelling on the surface of the molded product is that when the liquid crystal polymer passes through the mold of the molding machine, the skin layer (resin surface layer) that comes into contact with the mold solidifies first, so the core layer (resin center). ) Is distorted, and it is considered that a cavity (bulge) is generated in the distorted part due to the stress when the mold is opened. When injection is performed at a high speed such as high cycle molding, the distortion between the skin layer and the core layer increases, so that the number of swellings generated becomes more remarkable.
また、コア層とスキン層との境界に歪みが生じた状態の成形品は、成形直後の表面に膨れが発生していない場合であっても、リフロー後にスキン層とコア層の間の空洞が熱膨張してブリスタが発生するという問題もあった。 Further, in the molded product in which the boundary between the core layer and the skin layer is distorted, even if the surface immediately after molding does not swell, the cavity between the skin layer and the core layer remains after the reflow. There was also a problem that blister was generated due to thermal expansion.
成形時の膨れを抑制する方法として、液晶ポリエステルに充填材とともに特定の脂肪酸エステルおよび脂肪酸金属塩を含有させた液晶性樹脂組成物が提案されている（特許文献１）。 As a method for suppressing swelling during molding, a liquid crystal resin composition in which a liquid crystal polyester contains a specific fatty acid ester and a fatty acid metal salt together with a filler has been proposed (Patent Document 1).
しかしながら、特許文献１は、樹脂中に存在するガス（気泡）を低減することにより、気泡に起因する膨れの発生を防止するものであり、ハイサイクル成形のような高速射出においても膨れの発生を抑制し得るものではなかった。 However, Patent Document 1 prevents the occurrence of swelling due to bubbles by reducing the gas (bubbles) existing in the resin, and causes swelling even in high-speed injection such as high cycle molding. It could not be suppressed.
本発明の目的は、成形時の流動性に優れるとともに、成形直後の膨れおよびリフロー後のブリスタの発生を抑制できる液晶ポリマー組成物を提供することにある。また本発明の目的は、ハイサイクル成形に適し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 which is excellent in fluidity during molding and can suppress swelling immediately after molding and generation of blister after reflow. Another object of the present invention is to provide a liquid crystal polymer composition suitable for high cycle molding.
本発明者等は、液晶ポリマーの成形時における成形品表面の膨れの発生およびリフロー後のブリスタの発生について鋭意検討した結果、液晶ポリマーに、ガラス繊維および板状無機充填材とともに高級脂肪酸エステルおよび／または高級脂肪酸金属塩を含有させて、液晶ポリマー組成物を所定の溶融粘度とすることによって、ハイサイクル成形に供した場合であっても、膨れやブリスタの発生が著しく抑制されることを見出し、本発明を完成させるに至った。 As a result of diligent studies on the generation of swelling on the surface of the molded product during molding of the liquid crystal polymer and the generation of blister after reflow, the present inventors have made the liquid crystal polymer a higher fatty acid ester and / or a glass fiber and a plate-like inorganic filler. Alternatively, they have found that by adding a higher fatty acid metal salt to make the liquid crystal polymer composition a predetermined melt viscosity, swelling and blister generation are remarkably suppressed even when subjected to high cycle molding. The present invention has been completed.
すなわち本発明は、液晶ポリマー１００重量部、ガラス繊維１〜３０重量部、板状無機充填材１〜４０重量部、および高級脂肪酸エステルおよび／または高級脂肪酸金属塩０．０１〜１．３重量部を含有し、溶融粘度が１０〜２５Ｐａ・ｓである液晶ポリマー組成物を提供する。 That is, the present invention relates to 100 parts by weight of liquid crystal polymer, 1 to 30 parts by weight of glass fiber, 1 to 40 parts by weight of plate-like inorganic filler, and 0.01 to 1.3 parts by weight of higher fatty acid ester and / or higher fatty acid metal salt. To provide a liquid crystal polymer composition containing 10 to 25 Pa · s and having a melt viscosity of 10 to 25 Pa · s.
本発明の液晶ポリマー組成物は、成形時の流動性に優れるとともに、膨れの発生が著しく抑制されるという効果を有するため、小型化、薄肉化の成形品をハイサイクル成形するため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 composition of the present invention has an effect of excellent fluidity during molding and remarkably suppressing the occurrence of swelling, it is a molding resin for high-cycle molding of a compact and thin-walled molded product. Can be suitably used as.
本発明の液晶ポリマー組成物に用いる液晶ポリマーは、当業者にサーモトロピック液晶ポリマーと呼ばれる異方性溶融相を形成する液晶ポリエステル樹脂または液晶ポリエステルアミド樹脂である。 The liquid crystal polymer used in the liquid crystal polymer composition of the present invention is a liquid crystal polyester resin or a liquid crystal polyesteramide resin that forms an anisotropic molten phase, which is called a thermotropic liquid crystal polymer by those skilled in the art.
液晶ポリマーの異方性溶融相の性質は、直交偏向子を利用した通常の偏向検査法、すなわち、ホットステージにのせた試料を窒素ガス雰囲気下で観察することにより確認できる。 The properties of the anisotropic molten phase of the liquid crystal polymer can be confirmed by a usual deflection inspection method using an orthogonal deflector, that is, by observing a sample placed on a hot stage in a nitrogen gas atmosphere.
本発明に用いる液晶ポリマーは、一種の液晶ポリエステル樹脂または液晶ポリエステルアミド樹脂であってもよく、二種以上の液晶ポリエステル樹脂および／または液晶ポリエステルアミド樹脂の混合物であってもよい。 The liquid crystal polymer used in the present invention may be one kind of liquid crystal polyester resin or liquid crystal polyesteramide resin, or may be a mixture of two or more kinds of liquid crystal polyester resins and / or liquid crystal polyesteramide resins.
本発明に用いる液晶ポリマーは、分子鎖中に脂肪族基を有する半芳香族液晶ポリマー、または分子鎖が全て芳香族基より構成される全芳香族液晶ポリマーの何れを用いてもよい。これらの液晶ポリマーの中では、難燃性や機械物性が良好であることから全芳香族液晶ポリマー、特に全芳香族液晶ポリエステル樹脂を用いるのが好ましい。 As the liquid crystal polymer used in the present invention, either a semi-aromatic liquid crystal polymer having an aliphatic group in the molecular chain or a total aromatic liquid crystal polymer in which the molecular chain is entirely composed of aromatic groups may be used. Among these liquid crystal polymers, it is preferable to use a totally aromatic liquid crystal polymer, particularly a totally aromatic liquid crystal polyester resin, because it has good flame retardancy and mechanical properties.
本発明に用いる液晶ポリマーを構成する繰返し単位としては、芳香族オキシカルボニル繰返し単位、芳香族ジカルボニル繰返し単位、芳香族ジオキシ繰返し単位、芳香族アミノオキシ繰返し単位、芳香族ジアミノ繰返し単位、芳香族アミノカルボニル繰返し単位、芳香族オキシジカルボニル繰返し単位、および脂肪族ジオキシ繰返し単位などが挙げられる。 The repeating unit constituting the liquid crystal polymer used in the present invention includes an aromatic oxycarbonyl repeating unit, an aromatic dicarbonyl repeating unit, an aromatic dioxy repeating unit, an aromatic aminooxy repeating unit, an aromatic diamino repeating unit, and an aromatic amino. Examples include carbonyl repeating units, aromatic oxydicarbonyl repeating units, and aliphatic dioxy repeating units.
芳香族オキシカルボニル繰返し単位を与える単量体の具体例としては、例えばパラヒドロキシ安息香酸、メタヒドロキシ安息香酸、オルト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、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、４’−ヒドロキシフェニル−３−安息香酸、これらのアルキル、アルコキシまたはハロゲン置換体、ならびに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。これらの中では、パラヒドロキシ安息香酸、６−ヒドロキシ−２−ナフトエ酸が、得られる液晶ポリマーの特性や結晶融解温度を調整しやすいという点から好ましい。 Specific examples of the monomer giving the aromatic oxycarbonyl repeating unit include parahydroxybenzoic acid, metahydroxybenzoic acid, orthohydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and 5-hydroxy-2-naphthoic acid. , 3-Hydroxy-2-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid, alkyl, alkoxy or halogens thereof. Substitutes and ester-forming derivatives such as these acylated products, ester derivatives and acid halides can be mentioned. Among these, para-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are preferable because the characteristics of the obtained liquid crystal polymer and the crystal melting temperature can be easily adjusted.
芳香族ジカルボニル繰返し単位を与える単量体の具体例としては、例えばテレフタル酸、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、１，４−ナフタレンジカルボン酸、４,４’−ジカルボキシビフェニル等の芳香族ジカルボン酸、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにそれらのエステル誘導体、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。これらの中では、テレフタル酸、２,６−ナフタレンジカルボン酸が、得られる液晶ポリマーの機械物性、耐熱性、結晶融解温度、成形性を適度なレベルに調整しやすいことから好ましい。 Specific examples of the monomer giving an aromatic dicarbonyl repeating unit include, for example, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1, Examples thereof include 4-naphthalenedicarboxylic acids, aromatic dicarboxylic acids such as 4,4'-dicarboxybiphenyl, alkyl, alkoxy or halogen substituents thereof, and ester-forming derivatives such as ester derivatives thereof and acid halides. Among these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable because the mechanical properties, heat resistance, crystal melting temperature, and moldability of the obtained liquid crystal polymer can be easily adjusted to appropriate levels.
芳香族ジオキシ繰返し単位を与える単量体の具体例としては、例えばハイドロキノン、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、１，４−ジヒドロキシナフタレン、４,４’−ジヒドロキシビフェニル、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エーテル等の芳香族ジオール、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにそれらのアシル化物などのエステル形成性誘導体が挙げられる。これらの中では、ハイドロキノンおよび４,４’−ジヒドロキシビフェニルが、重合時の反応性、得られる液晶ポリマーの特性などの点から好ましい。 Specific examples of the monomer giving an aromatic dioxy repeating unit include, for example, hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4 , 4'-Dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether and other aromatic diols, alkyl, alkoxy or halogen substituents thereof, and theirs. Examples include ester-forming derivatives such as acylates. Among these, hydroquinone and 4,4'-dihydroxybiphenyl are preferable from the viewpoints of reactivity at the time of polymerization, characteristics of the obtained liquid crystal polymer and the like.
芳香族アミノオキシ繰返し単位を与える単量体の具体例としては、例えばｐ−アミノフェノール、ｍ−アミノフェノール、４−アミノ−１−ナフトール、５−アミノ−１−ナフトール、８−アミノ−２−ナフトール、４−アミノ−４’−ヒドロキシビフェニル等の芳香族ヒドロキシアミン、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにそれらのアシル化物などのエステル形成性誘導体が挙げられる。 Specific examples of the monomer giving the aromatic aminooxy repeating unit include, for example, p-aminophenol, m-aminophenol, 4-amino-1-naphthol, 5-amino-1-naphthol, 8-amino-2-. Examples include aromatic hydroxyamines such as naphthol, 4-amino-4'-hydroxybiphenyl, alkyl, alkoxy or halogen substituents thereof, and ester-forming derivatives such as acylated products thereof.
芳香族ジアミノ繰返し単位を与える単量体の具体例としては、例えばｐ−フェニレンジアミン、ｍ−フェニレンジアミン、１，５−ジアミノナフタレン、１，８−ジアミノナフタレン等の芳香族ジアミン、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにそれらのアシル化物などのアミド形成性誘導体が挙げられる。 Specific examples of the monomer giving the aromatic diamino repeating unit include aromatic diamines such as p-phenylenediamine, m-phenylenediamine, 1,5-diaminonaphthalene, and 1,8-diaminonaphthalene, and alkyls thereof. Examples include alkoxy or halogen substituents, as well as amide-forming derivatives such as their acylated products.
芳香族アミノカルボニル繰返し単位を与える単量体の具体例としては、例えばｐ−アミノ安息香酸、ｍ−アミノ安息香酸、６−アミノ−２−ナフトエ酸等の芳香族アミノカルボン酸、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにそれらのアシル化物、エステル誘導体、酸ハロゲン化物などのエステル形成性誘導体が挙げられる。 Specific examples of the monomer giving the aromatic aminocarbonyl repeating unit include aromatic aminocarboxylic acids such as p-aminobenzoic acid, m-aminobenzoic acid, and 6-amino-2-naphthoic acid, alkyls thereof, and the like. Examples thereof include alkoxy or halogen substituents, and ester-forming derivatives such as acylated products, ester derivatives, and acid halides thereof.
芳香族オキシジカルボニル繰返し単位を与える単量体の具体例としては、例えば３−ヒドロキシ−２，７−ナフタレンジカルボン酸、４−ヒドロキシイソフタル酸、および５−ヒドロキシイソフタル酸等のヒドロキシ芳香族ジカルボン酸、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにそれらのアシル化物、エステル誘導体、酸ハロゲン化物などのエステル形成性誘導体が挙げられる。 Specific examples of the monomer giving the aromatic oxydicarbonyl repeating unit include hydroxyaromatic dicarboxylic acids such as 3-hydroxy-2,7-naphthalenedicarboxylic acid, 4-hydroxyisophthalic acid, and 5-hydroxyisophthalic acid. , These alkyl, alkoxy or halogen substituents, and ester-forming derivatives such as their acylated products, ester derivatives, acid halides and the like.
脂肪族ジオキシ繰返し単位を与える単量体の具体例としては、例えば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どの脂肪族ジオール、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キシ繰返し単位を含有するポリマーを、前記の芳香族オキシカルボン酸、芳香族ジカルボン酸、芳香族ジオールおよびそれらのアシル化物、エステル誘導体、酸ハロゲン化物などと反応させることによっても、脂肪族ジオキシ繰返し単位を含む液晶ポリマーを得ることができる。 Specific examples of the monomer giving the aliphatic dioxy repeating unit include aliphatic diols such as ethylene glycol, 1,4-butanediol, and 1,6-hexanediol, and acylates thereof. Further, a polymer containing an aliphatic dioxy repeating unit such as polyethylene terephthalate or polybutylene terephthalate can be used as an aromatic oxycarboxylic acid, an aromatic dicarboxylic acid, an aromatic diol and an acylated product thereof, an ester derivative, or an acid halide. A liquid crystal polymer containing an aliphatic dioxy repeating unit can also be obtained by reacting with the above.
本発明に用い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。これらの単量体の使用量は、芳香族オキシカルボニル繰返し単位、芳香族ジカルボニル繰返し単位、芳香族ジオキシ繰返し単位、芳香族アミノオキシ繰返し単位、芳香族ジアミノ繰返し単位、芳香族アミノカルボニル繰返し単位、芳香族オキシジカルボニル繰返し単位、および脂肪族ジオキシ繰返し単位を与える単量体の合計量に対して１０モル％以下であることが好ましい。 The liquid crystal polymer used in the present invention may contain a thioester bond as long as the object of the present invention is not impaired. Examples of the monomer giving such a bond include mercapto aromatic carboxylic acid, aromatic dithiol and hydroxyaromatic thiol. The amounts of these monomers used are: aromatic oxycarbonyl repeating unit, aromatic dicarbonyl repeating unit, aromatic dioxy repeating unit, aromatic aminooxy repeating unit, aromatic diamino repeating unit, aromatic aminocarbonyl repeating unit, It is preferably 10 mol% or less based on the total amount of the aromatic oxydicarbonyl repeating unit and the monomer giving the aliphatic dioxy repeating unit.
これらの繰返し単位を組み合わせたポリマーは、単量体の構成や組成比、ポリマー中での各繰返し単位のシークエンス分布によっては、異方性溶融相を形成するものとしないものが存在するが、本発明に用いる液晶ポリマーは異方性溶融相を形成するものに限られる。 Some polymers that combine these repeating units may or may not form an anisotropic molten phase depending on the composition and composition ratio of the monomer and the sequence distribution of each repeating unit in the polymer. The liquid crystal polymer used in the invention is limited to one that forms an anisotropic molten phase.
本発明の液晶ポリマー組成物に使用される液晶ポリマーとしては、流動性に優れ、かつ膨れやブリスタの発生を抑制できる観点から、式（Ｉ）〜（ＩＶ）の繰返し単位から構成される全芳香族液晶ポリエステル樹脂が好適に使用される。 The liquid crystal polymer used in the liquid crystal polymer composition of the present invention has a total aromatic composition composed of repeating units of the formulas (I) to (IV) from the viewpoint of excellent fluidity and suppression of swelling and generation of blister. Group liquid crystal polyester resins are preferably used.
ここで、「芳香族基」は、６員の単環または環数２の縮合環である芳香族基を示す。 Here, the "aromatic group" indicates an aromatic group which is a 6-membered monocyclic ring or a condensed ring having 2 rings.
流動性に優れ、かつ膨れやブリスタの発生を抑制できる観点から、Ａｒ１およびＡｒ２はそれぞれ、下記の芳香族基（１）〜（４）から選択される１種以上のものであることが好ましく、Ａｒ１が式（１）および／または（４）で表される芳香族基であり、Ａｒ２が式（１）および／または（３）で表される芳香族基であることがより好ましく、Ａｒ１が式（１）で表される芳香族基であり、Ａｒ２が式（１）および（３）で表される芳香族基であることが特に好ましい。 From the viewpoint of excellent fluidity and capable of suppressing the generation of swelling and blister, Ar 1 and Ar 2 are each one or more selected from the following aromatic groups (1) to (4). More preferably, Ar 1 is an aromatic group represented by the formulas (1) and / or (4), and Ar 2 is an aromatic group represented by the formulas (1) and / or (3). It is particularly preferable that Ar 1 is an aromatic group represented by the formula (1) and Ar 2 is an aromatic group represented by the formulas (1) and (3).
本発明に用いる好ましい液晶ポリマーの具体例としては、例えば下記の単量体構成単位からなるものが挙げられる。
１）４−ヒドロキシ安息香酸／２−ヒドロキシ−６−ナフトエ酸共重合体
２）４−ヒドロキシ安息香酸／テレフタル酸／４,４'−ジヒドロキシビフェニル共重合体
３）４−ヒドロキシ安息香酸／テレフタル酸／イソフタル酸／４,４'−ジヒドロキシビフェニル共重合体
４）４−ヒドロキシ安息香酸／テレフタル酸／イソフタル酸／４,４'−ジヒドロキシビフェニル／ハイドロキノン共重合体
５）４−ヒドロキシ安息香酸／テレフタル酸／ハイドロキノン共重合体
６）２−ヒドロキシ−６−ナフトエ酸／テレフタル酸／ハイドロキノン共重合体
７）４−ヒドロキシ安息香酸／２−ヒドロキシ−６−ナフトエ酸／テレフタル酸／４,４'−ジヒドロキシビフェニル共重合体
８）２−ヒドロキシ−６−ナフトエ酸／テレフタル酸／４,４'−ジヒドロキシビフェニル共重合体
９）４−ヒドロキシ安息香酸／２−ヒドロキシ−６−ナフトエ酸／テレフタル酸／ハイドロキノン共重合体
１０）４−ヒドロキシ安息香酸／２−ヒドロキシ−６−ナフトエ酸／テレフタル酸／ハイドロキノン／４,４'−ジヒドロキシビフェニル共重合体
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共重合体
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／ハイドロキノン共重合体
１３）４−ヒドロキシ安息香酸／２,６−ナフタレンジカルボン酸／ハイドロキノン共重合体
１４）４−ヒドロキシ安息香酸／２−ヒドロキシ−６−ナフトエ酸／２,６−ナフタレンジカルボン酸／ハイドロキノン共重合体
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共重合体
１６）４−ヒドロキシ安息香酸／テレフタル酸／４−アミノフェノール共重合体
１７）２−ヒドロキシ−６−ナフトエ酸／テレフタル酸／４−アミノフェノール共重合体
１８）４−ヒドロキシ安息香酸／２−ヒドロキシ−６−ナフトエ酸／テレフタル酸／４−アミノフェノール共重合体
１９）４−ヒドロキシ安息香酸／テレフタル酸／４,４'−ジヒドロキシビフェニル ／４−アミノフェノール共重合体
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共重合体
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共重合体
２２）４−ヒドロキシ安息香酸／２−ヒドロキシ−６−ナフトエ酸／テレフタル酸／エチレングリコール共重合体
２３）４−ヒドロキシ安息香酸／２−ヒドロキシ−６−ナフトエ酸／テレフタル酸／４,４'−ジヒドロキシビフェニル／エチレングリコール共重合体
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共重合体。
Specific examples of the preferable liquid crystal polymer used in the present invention include, for example, those composed of the following monomer constituent units.
1) 4-Hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid copolymer 2) 4-hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl copolymer 3) 4-hydroxybenzoic acid / terephthalic acid / Isophthalic acid / 4,4'-dihydroxybiphenyl copolymer 4) 4-hydroxybenzoic acid / terephthalic acid / isophthalic acid / 4,4'-dihydroxybiphenyl / hydroquinone copolymer 5) 4-hydroxybenzoic acid / terephthalic acid / Hydroquinone copolymer 6) 2-hydroxy-6-naphthoic acid / terephthalic acid / hydroquinone copolymer 7) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl Copolymer 8) 2-Hydroxy-6-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl copolymer 9) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / hydroquinone Combined 10) 4-Hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / hydroquinone / 4,4'-dihydroxybiphenyl copolymer 11) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / 4 , 4'-Dihydroxybiphenyl copolymer 12) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer 13) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone Polymer 14) 4-Hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone copolymer 15) 4-Hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / Hydroquinone / 4,4'-dihydroxybiphenyl copolymer 16) 4-hydroxybenzoic acid / terephthalic acid / 4-aminophenol copolymer 17) 2-hydroxy-6-naphthoic acid / terephthalic acid / 4-aminophenol co-weight Combined 18) 4-Hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / 4-aminophenol copolymer 19) 4-hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / 4-amino Phenol copolymer 20) 4-hydroxybenzoic acid / terephthalic acid / ethylene glycol copolymer 21) 4-hydroxybenzoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / ethylene glycol copolymer 22) 4-Hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / ethylene glycol copolymer 23) 4-hydroxybenzoic acid / 2-hydroxy-6-naphthoic acid / terephthalic acid / 4,4'-dihydroxybiphenyl / Ethylene glycol copolymer 24) 4-Hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / 4,4'-dihydroxybiphenyl copolymer.
以上の中でも、１）、９）、１０）および１２）の単量体構成単位からなる液晶ポリマーが好ましく、特に１０）の単量体構成単位からなる液晶ポリマーがより好ましい。 Among the above, a liquid crystal polymer composed of the monomer constituent units of 1), 9), 10) and 12) is preferable, and a liquid crystal polymer composed of the monomer constituent unit of 10) is more preferable.
以下、本発明に用いる液晶ポリマーの製造方法について説明する。 Hereinafter, a method for producing the liquid crystal polymer used in the present invention will be described.
本発明に用いる液晶ポリマーの製造方法に特に制限はなく、前記の単量体の組み合わせからなるエステル結合またはアミド結合を形成させる公知の重縮合方法、例えば溶融アシドリシス法、スラリー重合法などを用いることができる。 The method for producing the liquid crystal polymer used in the present invention is not particularly limited, and a known polycondensation method for forming an ester bond or an amide bond composed of the above-mentioned combination of monomers, for example, a molten acidlysis method, a slurry polymerization method, or the like is used. Can be done.
溶融アシドリシス法とは、本発明で用いる液晶ポリマーの製造方法に用いるのに好ましい方法であり、この方法は、最初に単量体を加熱して反応物質の溶融液を形成し、続いて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（例えば、酢酸、水等）の除去を容易にするために真空を適用してもよい。 The molten acidlysis method is a method preferable to be used in the method for producing a liquid crystal polymer used in the present invention. In this method, a monomer is first heated to form a melt of a reactant, and then a reaction is carried out. The molten polymer is subsequently obtained. A vacuum may be applied to facilitate the removal of volatiles (eg, acetic acid, water, etc.) that are 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 of reacting in the presence of a heat exchange fluid, and the solid product is obtained in a state of being suspended in a heat exchange medium.
溶融アシドリシス法およびスラリー重合法の何れの場合においても、液晶ポリマーを製造する際に使用する重合性単量体成分は、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。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単量体のアセチル化物を反応に用いる方法が挙げられる。 In both the melt acidlysis method and the slurry polymerization method, the polymerizable monomer component used in producing the liquid crystal polymer is a modified form in which a hydroxyl group and / or an amino group is acylated at room temperature, that is, a lower grade. It can also be subjected to the reaction as an acylated product. The lower acyl group preferably has 2 to 5 carbon atoms, and more preferably 2 or 3 carbon atoms. Particularly preferably, a method using the acetylated product of the monomer in the reaction can be mentioned.
単量体のアシル化物は、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。 As the acylated product of the monomer, a product that is separately acylated and synthesized in advance may be used, or an acylating agent such as acetic anhydride may be added to the monomer during the production of the liquid crystal polymer to generate the acylated product in the reaction system. it can.
溶融アシドリシス法またはスラリー重合法の何れの場合においても反応時、必要に応じて触媒を用いてもよい。 In either case of the melt acidlysis method or the slurry polymerization method, a catalyst may be used at the time of the reaction, if necessary.
触媒の具体例としては、ジアルキルスズオキシド（例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またはアルカリ土類金属塩（例えば酢酸カリウム）；無機酸塩類（例えば硫酸カリウム）；ルイス酸（例えば三フッ化硼素）；ハロゲン化水素（例えば塩化水素）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 (for example, dibutyltin oxide) and diaryltin oxide; organic titanium compounds such as titanium dioxide, antimony trioxide, alkoxytitanium silicate, and titanium alkoxide; alkalis or alkalis of carboxylic acids. Examples include earth metal salts (eg potassium acetate); inorganic acid salts (eg potassium sulfate); Lewis acids (eg boron trifluoride); gaseous acid catalysts such as hydrogen halides (eg hydrogen chloride).
触媒の使用割合は、通常単量体全量に対して１〜１０００ｐｐｍ、好ましくは２〜１００ｐｐｍである。 The ratio of the catalyst used is usually 1 to 1000 ppm, preferably 2 to 100 ppm, based on the total amount of the monomers.
このようにして重縮合反応されて得られた液晶ポリマーは、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 obtained by the polycondensation reaction in this manner is extracted from the polymerization reaction tank in a molten state and then processed into pellets, flakes, or powders.
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、減圧下または不活性ガス雰囲気下において、実質的に固相状態において熱処理を行ってもよい。 The pellet-shaped, flake-shaped, or powder-shaped liquid crystal polymer may be heat-treated in a substantially solid phase state under reduced pressure or under an inert gas atmosphere for the purpose of increasing the molecular weight and improving the heat resistance.
固相状態で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、２６０〜３５０℃、好ましくは２８０〜３２０℃で行うのがよい。 The temperature of the heat treatment performed in the solid phase state is not particularly limited as long as the liquid crystal polymer is not melted, but it is preferably performed at 260 to 350 ° C., preferably 280 to 320 ° C.
本発明の液晶ポリマー組成物は、上記のようにして得られた液晶ポリマー１００重量部に加えて、繊維状充填材１〜３０重量部、板状または粉状充填材１〜４０重量部、および高級脂肪酸エステルおよび／または高級脂肪酸金属塩０．０１〜１．３重量部を含有し、溶融粘度が１０〜２５Ｐａ・ｓである。 In the liquid crystal polymer composition of the present invention, in addition to 100 parts by weight of the liquid crystal polymer obtained as described above, 1 to 30 parts by weight of the fibrous filler, 1 to 40 parts by weight of the plate-like or powder-like filler, and It contains 0.01 to 1.3 parts by weight of higher fatty acid ester and / or higher fatty acid metal salt, and has a melt viscosity of 10 to 25 Pa · s.
繊維状充填材の含有量は、１〜３０重量部、好ましくは２〜２５重量部、より好ましくは３〜２０重量部であり、板状または粉状充填材の含有量は、１〜４０重量部、好ましくは２〜３５重量部、より好ましくは３〜３０重量部である。繊維状充填剤または粒状充填材の含有量が上記下限値以上であると、液晶ポリマー組成物の耐熱性や機械強度にさらに優れる。繊維状充填剤または粒状充填材の含有量が上記上限値以下であると、流動性にさらに優れる。繊維状充填材の含有量が１重量部を下回る場合、および板状または粒状充填材の含有量が１重量部を下回る場合、いずれも液晶ポリマー組成物の耐熱性や機械強度が不足するとともに反りが発生しやすくなる。繊維状充填材の含有量が３０重量部を上回る場合、および板状または粒状充填材の含有量が４０重量部を上回る場合、いずれも流動性が悪くなるとともに膨れが発生しやすくなる。 The content of the fibrous filler is 1 to 30 parts by weight, preferably 2 to 25 parts by weight, more preferably 3 to 20 parts by weight, and the content of the plate-like or powder-like filler is 1 to 40 parts by weight. Parts, preferably 2-35 parts by weight, more preferably 3-30 parts by weight. When the content of the fibrous filler or the granular filler is at least the above lower limit, the heat resistance and mechanical strength of the liquid crystal polymer composition are further excellent. When the content of the fibrous filler or the granular filler is not more than the above upper limit value, the fluidity is further excellent. When the content of the fibrous filler is less than 1 part by weight, and when the content of the plate-like or granular filler is less than 1 part by weight, the heat resistance and mechanical strength of the liquid crystal polymer composition are insufficient and warpage is performed. Is likely to occur. When the content of the fibrous filler exceeds 30 parts by weight, and when the content of the plate-like or granular filler exceeds 40 parts by weight, the fluidity becomes poor and swelling is likely to occur.
また、繊維状充填材と板状または粒状充填材との合計量は、液晶ポリマー１００重量部に対して、２〜５０重量部が好ましく、４〜４８重量部がより好ましく、６〜４５重量部がさらに好ましい。繊維状充填材と板状または粒状充填材の合計量が上記下限値以上であると、液晶ポリマー組成物の耐熱性や機械強度にさらに優れるとともに反りが発生しにくい。繊維状充填材と板状または粒状充填材との合計量が上記上限値以下であると、流動性にさらに優れ、また膨れが発生しにくい。 The total amount of the fibrous filler and the plate-shaped or granular filler is preferably 2 to 50 parts by weight, more preferably 4 to 48 parts by weight, and 6 to 45 parts by weight with respect to 100 parts by weight of the liquid crystal polymer. Is even more preferable. When the total amount of the fibrous filler and the plate-shaped or granular filler is at least the above lower limit value, the heat resistance and mechanical strength of the liquid crystal polymer composition are further improved, and warpage is unlikely to occur. When the total amount of the fibrous filler and the plate-shaped or granular filler is not more than the above upper limit value, the fluidity is further excellent and swelling is less likely to occur.
高級脂肪酸エステルの含有量は、０．０１〜１．３重量部、好ましくは０．０３〜１．２重量部、より好ましくは０．０５〜１．０重量部である。高級脂肪酸エステルの含有量が上記下限値以上であると、膨れの発生がさらに抑制され、また高級脂肪酸エステルの含有量が上記上限値以下であると、ブリスタがさらに発生し難い。高級脂肪酸エステルおよび／または高級脂肪酸金属塩の含有量が０．０１重量部を下回ると、膨れが発生しやすくなり、１．３重量部を上回ると、ブリスタが発生しやすくなる。 The content of the higher fatty acid ester is 0.01 to 1.3 parts by weight, preferably 0.03 to 1.2 parts by weight, and more preferably 0.05 to 1.0 parts by weight. When the content of the higher fatty acid ester is at least the above lower limit value, the occurrence of swelling is further suppressed, and when the content of the higher fatty acid ester is at least the above upper limit value, blister is less likely to occur. If the content of the higher fatty acid ester and / or higher fatty acid metal salt is less than 0.01 parts by weight, swelling is likely to occur, and if it exceeds 1.3 parts by weight, blister is likely to occur.
本発明において使用される繊維状充填材の具体例としては、ガラス繊維、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、チタン酸カリウム繊維、ホウ酸アルミニウム繊維およびウォラストナイトからなる群より選択される１種以上のものが挙げられる。 Specific examples of the fibrous filler used in the present invention are selected from the group consisting of glass fiber, silica-alumina fiber, alumina fiber, carbon fiber, aramid fiber, potassium titanate fiber, aluminum borate fiber and wollastonite. One or more kinds of things to be done are mentioned.
本発明において用いる繊維状充填材の平均繊維径および平均繊維長は、本発明の目的を損なわない限り特に制限されないが、平均繊維径が０．１〜５０μｍであり、平均繊維長が５０〜７００μｍであることが好ましい。 The average fiber diameter and the average fiber length of the fibrous filler used in the present invention are not particularly limited as long as the object of the present invention is not impaired, but the average fiber diameter is 0.1 to 50 μm and the average fiber length is 50 to 700 μm. Is preferable.
これらの繊維状充填材の中でも、機械強度の点でガラス繊維が好適に使用される。 Among these fibrous fillers, glass fiber is preferably used in terms of mechanical strength.
本発明において使用される板状または粉状の充填材の具体例としては、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、酸化チタン、および珪藻土からなる群より選択される１種以上のものが挙げられる。これらの中で、寸法安定性の点でタルクが好ましい。 Specific examples of the plate-like or powder-like filler used in the present invention include a group consisting of talc, mica, graphite, calcium carbonate, dolomite, clay, glass flakes, glass beads, barium sulfate, titanium oxide, and diatomaceous earth. One or more selected from the above can be mentioned. Of these, talc is preferred in terms of dimensional stability.
本発明において使用される高級脂肪酸エステルおよび／または高級脂肪酸金属塩の原料となる高級脂肪酸は、好ましくは炭素原子数１０以上のものである。高級脂肪酸の例としては、カプリン酸、ラウリン酸、ミリスチン酸、バルミチン酸、ステアリン酸、アラキン酸、ベヘン酸、リグノセリン酸、モンタン酸等が挙げられる。この中でステアリン酸およびモンタン酸が好ましい。 The higher fatty acid used as a raw material for the higher fatty acid ester and / or higher fatty acid metal salt used in the present invention preferably has 10 or more carbon atoms. Examples of higher fatty acids include capric acid, lauric acid, myristic acid, balmitic acid, stearic acid, araquinic acid, behenic acid, lignoceric acid, montanic acid and the like. Of these, stearic acid and montanic acid are preferred.
エステルの原料となるアルコールとしては、ステアリルアルコール、ベヘニルアルコール、グリセリン、ソルビタン、プロピレングリコール、ペンタエリスリトール、ポリオキシエチレンビスフェノールＡ等が挙げられる。 Examples of the alcohol used as a raw material for the ester include stearyl alcohol, behenyl alcohol, glycerin, sorbitan, propylene glycol, pentaerythritol, polyoxyethylene bisphenol A and the like.
また、金属塩を構成する金属としては、リチウム、ナトリウム、カリウム等のアルカリ金属、マグネシウム、カルシウム、バリウム等のアルカリ土類金属、あるいは亜鉛などが挙げられ、特にアルカリ土類金属が好ましく用いられる。高級脂肪酸金属塩の具体例としては、ステアリン酸カルシウム、ステアリン酸バリウム、ステアリン酸亜鉛、ステアリン酸マグネシウム、モンタン酸ナトリウム、モンタン酸カルシウム、モンタン酸マグネシウム、モンタン酸カリウム、モンタン酸リチウム、モンタン酸亜鉛、モンタン酸バリウム、モンタン酸アルミニウム、パルミチン酸カルシウム、パルミチン酸マグネシウムおよびパルミチン酸バリウム等が挙げられる。これらの中でもコストの点および成形品の物性維持の点で、ステアリン酸カルシウムおよびモンタン酸カルシウムが好ましく用いられる。 Examples of the metal constituting the metal salt include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium, calcium and barium, zinc and the like, and alkaline earth metals are particularly preferably used. Specific examples of higher fatty acid metal salts include calcium stearate, barium stearate, zinc stearate, magnesium stearate, sodium montanate, calcium montanate, magnesium montanate, potassium montanate, lithium montanate, zinc montanate, and montanate. Examples thereof include barium acid, aluminum montanate, calcium palmitate, magnesium palmitate and barium palmitate. Among these, calcium stearate and calcium montanate are preferably used in terms of cost and maintenance of physical properties of the molded product.
本発明に用いられる高級脂肪酸エステルおよび／または高級脂肪酸金属塩は、液晶ポリエステル樹脂組成物との混合を容易にするため、粉末または粒子形状であることが好ましい。また、高級脂肪酸エステルおよび／または高級脂肪酸金属塩の粒径は、平均粒子径１００μｍ未満が好ましく、粒径５０μｍ未満がさらに好ましい。粒径が上記上限値以上未満の場合は、成形加工時に可塑化を安定させる効果に優れる。 The higher fatty acid ester and / or higher fatty acid metal salt used in the present invention is preferably in the form of powder or particles in order to facilitate mixing with the liquid crystal polyester resin composition. The particle size of the higher fatty acid ester and / or higher fatty acid metal salt is preferably less than 100 μm in average particle size, and more preferably less than 50 μm in particle size. When the particle size is less than the above upper limit value, the effect of stabilizing plasticization during molding is excellent.
液晶ポリマー、繊維状充填材、板状または粉状充填材、および高級脂肪酸エステルおよび／または高級脂肪酸金属塩を含有する本発明の液晶ポリマー組成物は、溶融粘度が１０〜２５Ｐａ・ｓ、好ましくは１２〜２３Ｐａ・ｓ、より好ましくは１３〜２０Ｐａ・ｓであり、溶融粘度が比較的低い高流動性の液晶ポリマー組成物である。なお、溶融粘度は、液晶ポリマー組成物の結晶融解温度以上で測定される溶融粘度、例えば結晶融解温度＋１０℃における溶融粘度であり、好ましくは３５０℃における溶融粘度である。溶融粘度は、液晶ポリマーや充填材等の液晶ポリマー組成物に含まれる液晶ポリマーや添加剤等の種類および含有比率等のより調整することができる。 The liquid crystal polymer composition of the present invention containing a liquid crystal polymer, a fibrous filler, a plate-like or powder-like filler, and a higher fatty acid ester and / or a higher fatty acid metal salt has a melt viscosity of 10 to 25 Pa · s, preferably 10 to 25 Pa · s. It is a highly fluid liquid crystal polymer composition having a melt viscosity of 12 to 23 Pa · s, more preferably 13 to 20 Pa · s, and having a relatively low melt viscosity. The melt viscosity is a melt viscosity measured at a crystal melting temperature or higher of the liquid crystal polymer composition, for example, a melt viscosity at a crystal melting temperature of + 10 ° C., preferably a melt viscosity at 350 ° C. The melt viscosity can be adjusted by adjusting the type and content ratio of the liquid crystal polymer and additives contained in the liquid crystal polymer composition such as the liquid crystal polymer and the filler.
液晶ポリマー組成物の溶融粘度が上記下限値以上であると、膨れの抑制効果が高く、また、液晶ポリマー組成物の溶融粘度が上記上限値以下であると、流動性にさらに優れる。液晶ポリマー組成物の溶融粘度が１０Ｐａ・ｓを下回る場合、膨れ抑制効果が得られず、２５Ｐａ・ｓを上回る場合、流動性が低下するため成形性が悪くなる。 When the melt viscosity of the liquid crystal polymer composition is at least the above lower limit value, the effect of suppressing swelling is high, and when the melt viscosity of the liquid crystal polymer composition is at least the above upper limit value, the fluidity is further excellent. If the melt viscosity of the liquid crystal polymer composition is less than 10 Pa · s, the effect of suppressing swelling cannot be obtained, and if it exceeds 25 Pa · s, the fluidity is lowered and the moldability is deteriorated.
本発明の液晶ポリマー組成物は、本発明の目的を損なわない範囲で、上述した繊維状充填材、板状または粉状充填材、高級脂肪酸エステルおよび／または高級脂肪酸金属塩以外に、さらに添加剤を含有してもよい。さらに含有してもよい添加剤としては、高級脂肪酸、高級脂肪酸アミド、ポリシロキサン、フッ素樹脂などの離型改良剤；染料、顔料などの着色剤；酸化防止剤；熱安定剤；紫外線吸収剤；帯電防止剤；界面活性剤などから選ばれる１種または２種以上が挙げられる。 The liquid crystal polymer composition of the present invention is further added to the above-mentioned fibrous filler, plate-like or powder-like filler, higher fatty acid ester and / or higher fatty acid metal salt, as long as the object of the present invention is not impaired. May be contained. Further, additives that may be contained include mold release improvers such as higher fatty acids, higher fatty acid amides, polysiloxanes, and fluororesins; colorants such as dyes and pigments; antioxidants; heat stabilizers; ultraviolet absorbers; Antistatic agent; one or more selected from surfactants and the like can be mentioned.
また、本発明の液晶ポリマー組成物は、本発明の目的を損なわない範囲で、さらに、他の樹脂成分を含有してもよい。他の樹脂成分としては、例えばポリアミド、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含有させることができる。他の樹脂成分の含有量は特に限定的ではなく、液晶ポリマー組成物の用途や目的に応じて適宜定めればよい。典型的には液晶ポリマー１００重量部に対する他の樹脂の合計含有量が０．１〜１００重量部、特に０．１〜８０重量部となる範囲で添加される。 Further, the liquid crystal polymer composition of the present invention may further contain other resin components as long as the object of the present invention is not impaired. Other resin components include, for example, polyamide, polyester, polyacetal, polyphenylene ether, and modified products thereof, thermoplastic resins such as polysulfone, polyethersulfone, polyetherimide, and polyamideimide, and phenol resins, epoxy resins, and polyimide resins. Examples thereof include thermosetting resins such as. Other resin components can be contained alone or in combination of two or more. The content of the other resin components is not particularly limited, and may be appropriately determined according to the use and purpose of the liquid crystal polymer composition. Typically, the total content of the other resin with respect to 100 parts by weight of the liquid crystal polymer is added in the range of 0.1 to 100 parts by weight, particularly 0.1 to 80 parts by weight.
上述した繊維状充填材、板状または粉状充填材および高級脂肪酸エステルと、必要によりその他の添加剤並びに他の樹脂成分などは、液晶ポリマー中に添加され、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。 The fibrous fillers, plate or powder fillers and higher fatty acid esters described above and, if necessary, other additives and other resin components are added to the liquid crystal polymer and are added to the liquid crystal polymer, such as a Banbury mixer, kneader, uniaxial or biaxial. A liquid crystal polymer composition can be obtained by melt-kneading the liquid crystal polymer near the crystal melting temperature or at a crystal melting temperature of + 20 ° C. using an extruder or the like.
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。これら成形品は、本発明の液晶ポリマーから構成され、つまり、本発明の液晶ポリマー組成物を成形して得られる。 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 non-woven fabric by a known molding method using an injection molding machine, an extruder, or the like. These molded articles are composed of the liquid crystal polymer of the present invention, that is, are obtained by molding the liquid crystal polymer composition of the present invention.
本発明の液晶ポリマー組成物から構成される成形品としては、スイッチ、リレー、コネクタ、チップ、光ピックアップ、インバータトランス、コイルボビン、アンテナおよび基板などが挙げられる。 Molded products composed of the liquid crystal polymer composition of the present invention include switches, relays, connectors, chips, optical pickups, inverter transformers, coil bobbins, antennas, substrates and the like.
本発明の液晶ポリマー組成物は、高流動性であるため射出速度が通常１００〜５００ｍｍ／ｓｅｃ、好ましくは１１０〜４８０ｍｍ／ｓｅｃ、より好ましくは１２０〜４５０ｍｍ／ｓｅｃ、さらに好ましくは１３０〜３２０ｍｍ／ｓｅｃであるハイサイクル成形に好適に使用することが可能である。 Since the liquid crystal polymer composition of the present invention has high fluidity, the injection rate is usually 100 to 500 mm / sec, preferably 110 to 480 mm / sec, more preferably 120 to 450 mm / sec, still more preferably 130 to 320 mm / sec. It can be suitably used for high cycle molding.
しかもハイサイクル成形時の課題であった膨れが著しく抑制されるため、本発明の液晶ポリマー組成物は、小型化および薄肉化が求められる電気電子部品、特にコネクタの成形材料として好適に用いられる。 Moreover, since swelling, which has been a problem during high-cycle molding, is remarkably suppressed, the liquid crystal polymer composition of the present invention is suitably used as a molding material for electrical and electronic parts, particularly connectors, which are required to be miniaturized and thinned.
以下、実施例により本発明を詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
ＬＣＰの合成例
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、パラヒドロキシ安息香酸３１４．２ｇ（３５モル％）、６−ヒドロキシ−２−ナフトエ酸６１．２ｇ（５モル％）、４，４’−ジヒドロキシビフェニル１６９．４ｇ（１４モル％）、ハイドロキノン１１４．５ｇ（１６モル％）およびテレフタル酸３２３．９ｇ（３０モル％）を仕込み、さらに全単量体の水酸基量（モル）に対して１．０３倍モルの無水酢酸を仕込み、次の条件で脱酢酸重合を行った。
Example of LCP synthesis In a reaction vessel equipped with a stirrer with a torque meter and a distillate, 314.2 g (35 mol%) of parahydroxybenzoic acid, 61.2 g (5 mol%) of 6-hydroxy-2-naphthoic acid, Add 169.4 g (14 mol%) of 4,4'-dihydroxybiphenyl, 114.5 g (16 mol%) of hydroquinone and 323.9 g (30 mol%) of terephthalic acid, and further add the amount of hydroxyl groups (mol) of all the monomers. 1.03 times the molar amount of acetic anhydride was charged, 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、同温度で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（液晶ポリマー）のペレットを得た。重合時の留出酢酸量は、ほぼ理論値どおりであった。 The temperature was raised from room temperature to 145 ° C. over 1 hour under a nitrogen gas atmosphere, and the temperature was maintained at the same temperature for 30 minutes. Then, the temperature was raised to 350 ° C. over 7 hours while distilling acetic acid produced as a by-product, and then the pressure was reduced to 5 mmHg over 80 minutes. When a predetermined torque was exhibited, the polymerization reaction was terminated, the contents were taken out from the reaction vessel, and pellets of liquid crystal polyester resin (liquid crystal polymer) were obtained by a pulverizer. The amount of distillate acetic acid at the time of polymerization was almost the same as the theoretical value.
実施例１〜２および比較例１〜５
合成例で得られた液晶ポリマー１００重量部に、繊維状充填材、板状充填材および高級脂肪酸エステルを表１に記載の重量比でそれぞれ配合し、二軸押出機（株式会社ＪＳＷ、ＴＥＸ−３０）にて溶融混練したものをペレット化し、液晶ポリマー組成物を調製した。繊維状充填材、板状充填材および高級脂肪酸エステルは以下のものを使用した。
〈繊維状充填材〉
ＣＰＩＣ社製ガラス繊維ＥＣＳ３０１０Ａ（平均繊維径：１０．５μｍ）
〈板状充填材〉
富士タルク株式会社製タルクＨＫ−Ａ（平均粒子径２４．０μｍ、含水量０．１３重量％）
〈高級脂肪酸エステル〉
クラリアント ジャパン社製Ｌｉｃｏｗａｘ Ｅ ｆｌａｋｅｓ ｐｏｗｄｅｒ（融点：８２℃）
Examples 1-2 and Comparative Examples 1-5
A fibrous filler, a plate-like filler, and a higher fatty acid ester were blended in 100 parts by weight of the liquid crystal polymer obtained in the synthesis example at the weight ratios shown in Table 1, respectively, and a twin-screw extruder (JSW, TEX- The melt-kneaded product in 30) was pelletized to prepare a liquid crystal polymer composition. The following fibrous fillers, plate-like fillers and higher fatty acid esters were used.
<Fibrous filler>
CPIC glass fiber ECS3010A (average fiber diameter: 10.5 μm)
<Plate-shaped filler>
Talc HK-A manufactured by Fuji Tarku Co., Ltd. (average particle size 24.0 μm, water content 0.13% by weight)
<Higher fatty acid ester>
Clariant Japan's Licowax E flakes powerer (melting point: 82 ° C)
得られた液晶ポリマー組成物のペレットについて、溶融粘度を以下に示す方法にて測定した。結果を表１に示す。 The melt viscosity of the pellets of the obtained liquid crystal polymer composition was measured by the method shown below. The results are shown in Table 1.
（１）溶融粘度
溶融粘度測定装置（東洋精機（株）製キャピログラフ１Ｄ）により、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（液晶ポリマー組成物のペレット）の３５０℃での溶融粘度を測定した。
(1) Melt Viscosity Using a melt viscosity measuring device (Capillary Graph 1D manufactured by Toyo Seiki Co., Ltd.), using a capillary of 1.0 mmφ × 10 mm, a sample (pellet of liquid crystal polymer composition) under the condition of a shear rate of 1000 sec -1. The melt viscosity at 350 ° C. was measured.
得られた液晶ポリマー組成物のペレットについて、膨れ発生率およびブリスタ発生率を以下に示す方法にて測定した。結果を表２に示す。 For the pellets of the obtained liquid crystal polymer composition, the swelling occurrence rate and the blister occurrence rate were measured by the methods shown below. The results are shown in Table 2.
（２）膨れ発生率
射出成形機（日精樹脂株式会社製、ＮＥＸ−１５−１Ｅ）を用いて、表３に示す成形条件にて、縦３０ｍｍ、横６．０ｍｍ、高さ５．０ｍｍ、厚さ０．２ｍｍの箱型試験片を成形した。
この試験片１００個について、成形直後の試験片表面の膨れを目視にて確認し、膨れが発生した試験片の個数をカウントした。膨れ発生率は、試験片１００個に対する、膨れが発生した試験片の個数の割合を算出することによって決定した。
○：膨れ発生率０％、△：膨れ発生率１〜１０％、×：膨れ発生率：１１％以上
(2) Occurrence rate of swelling Using an injection molding machine (NEX-15-1E, manufactured by Nissei Resin Co., Ltd.), under the molding conditions shown in Table 3, the length is 30 mm, the width is 6.0 mm, the height is 5.0 mm, and the thickness is A box-shaped test piece having a size of 0.2 mm was formed.
With respect to 100 of these test pieces, the swelling of the surface of the test piece immediately after molding was visually confirmed, and the number of test pieces in which the swelling occurred was counted. The swelling occurrence rate was determined by calculating the ratio of the number of swelling test pieces to 100 test pieces.
◯: swelling occurrence rate 0%, Δ: swelling occurrence rate 1 to 10%, ×: swelling occurrence rate: 11% or more
（３）ブリスタ発生率
膨れ発生試験で作成した箱型試験片について、膨れが発生していない試験片を２３℃、相対湿度５０％の条件で２４時間静置した後、ＩＲリフロー装置（千住金属工業社製、ＳＡＩ−２６０４）を用いて、各試験片について以下の条件でリフロー処理を行った。
リフロー後、試験片表面のブリスタを目視にて確認し、ブリスタが発生した試験片の個数をカウントした。ブリスタ発生率は、試験片１００個に対する、ブリスタが発生した試験片の個数の割合を算出することによって決定した。
○：ブリスタ発生率０％、△：ブリスタ発生率１〜１０％、×：ブリスタ発生率：１１％以上
(3) Blister generation rate For the box-shaped test piece prepared in the swelling generation test, the test piece without swelling was allowed to stand for 24 hours under the conditions of 23 ° C. and 50% relative humidity, and then an IR reflow device (Senju Metals). Using SAI-2604) manufactured by Kogyo Co., Ltd., each test piece was reflowed under the following conditions.
After the reflow, the blister on the surface of the test piece was visually confirmed, and the number of test pieces in which the blister was generated was counted. The blister occurrence rate was determined by calculating the ratio of the number of test pieces in which blister was generated to 100 test pieces.
◯: Blister occurrence rate 0%, Δ: Blister occurrence rate 1 to 10%, ×: Blister occurrence rate: 11% or more
＜リフロー処理条件＞
予備加熱：１９０℃、３０〜５０秒、本加熱：２５０℃以上、２０〜３０秒、ピーク温度：２６０〜２６５℃
<Reflow processing conditions>
Preheating: 190 ° C, 30 to 50 seconds, main heating: 250 ° C or higher, 20 to 30 seconds, peak temperature: 260 to 265 ° C
表２に示される通り、実施例１および２の液晶ポリマー組成物は、射出速度が低い場合だけでなく、射出速度が高い場合であっても膨れ発生率およびブリスタ発生率が共に０％である、これより、本発明の液晶ポリマー組成物はハイサイクル成形に非常に好適であることが分かる。一方、比較例１〜５の液晶ポリマー組成物は、射出速度が低い場合において膨れおよびブリスタの発生が観察され、また射出速度が高い場合においては、膨れ発生率およびブリスタ発生率が非常に高い結果となり、本発明の課題を達成できない。
本発明の好ましい態様は以下を包含する。
〔１〕液晶ポリマー１００重量部、繊維状充填材１〜３０重量部、板状または粉状充填材１〜４０重量部、および高級脂肪酸エステルおよび／または高級脂肪酸金属塩０．０１〜１．３重量部を含有し、溶融粘度が１０〜２５Ｐａ・ｓである液晶ポリマー組成物。
〔２〕液晶ポリマーが、式（Ｉ）〜（ＩＶ）の繰返し単位から構成される液晶ポリエステル樹脂である、〔１〕に記載の液晶ポリマー組成物。
〔３〕Ａｒ １ およびＡｒ ２ がそれぞれ、下記の芳香族基（１）〜（４）から選択される１種以上である、〔２〕に記載の液晶ポリマー組成物。
〔５〕Ａｒ １ が式（１）で表される芳香族基であり、Ａｒ ２ が式（１）および（３）で表される芳香族基である、〔３〕に記載の液晶ポリマー組成物。
〔６〕繊維状充填材と板状または粉状充填材との合計量が、液晶ポリマー１００重量部に対して、２〜５０重量部である、〔１〕〜〔５〕のいずれかに記載の液晶ポリマー組成物。
〔７〕繊維状充填材が、ガラス繊維、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、チタン酸カリウム繊維、ホウ酸アルミニウム繊維、およびウォラストナイトからなる群より選択される１種以上である、〔１〕〜〔６〕のいずれかに記載の液晶ポリマー組成物。
〔８〕板状または粉状充填材が、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、酸化チタン、および珪藻土からなる群より選択される１種以上である、〔１〕〜〔７〕のいずれかに記載の液晶ポリマー組成物。
〔９〕繊維状充填材がガラス繊維であり、板状または粉状充填材がタルクである、〔１〕〜〔８〕のいずれかに記載の液晶ポリマー組成物。
〔１０〕〔１〕〜〔９〕の何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。
〔１１〕成形品がコネクタである〔１０〕に記載の成形品。
〔１２〕〔１〕〜〔９〕の何れかに記載の液晶ポリマー組成物を、１００〜５００ｍｍ／ｓｅｃの射出速度で成形する射出成形方法。
As shown in Table 2, the liquid crystal polymer compositions of Examples 1 and 2 have both a swelling occurrence rate and a blister occurrence rate of 0% not only when the injection rate is low but also when the injection rate is high. From this, it can be seen that the liquid crystal polymer composition of the present invention is very suitable for high cycle molding. On the other hand, in the liquid crystal polymer compositions of Comparative Examples 1 to 5, swelling and blister generation were observed when the injection rate was low, and the swelling occurrence rate and blister generation rate were very high when the injection rate was high. Therefore, the subject of the present invention cannot be achieved.
Preferred embodiments of the present invention include:
[1] 100 parts by weight of liquid crystal polymer, 1 to 30 parts by weight of fibrous filler, 1 to 40 parts by weight of plate-like or powder-like filler, and higher fatty acid ester and / or higher fatty acid metal salt 0.01 to 1.3. A liquid crystal polymer composition containing parts by weight and having a melt viscosity of 10 to 25 Pa · s.
[2] The liquid crystal polymer composition according to [1], wherein the liquid crystal polymer is a liquid crystal polyester resin composed of repeating units of the formulas (I) to (IV).
[3] The liquid crystal polymer composition according to [2], wherein Ar 1 and Ar 2 are one or more selected from the following aromatic groups (1) to (4), respectively.
[5] The liquid crystal polymer composition according to [3], wherein Ar 1 is an aromatic group represented by the formula (1) and Ar 2 is an aromatic group represented by the formulas (1) and (3). Stuff.
[6] The method according to any one of [1] to [5], wherein the total amount of the fibrous filler and the plate-like or powder-like filler is 2 to 50 parts by weight with respect to 100 parts by weight of the liquid crystal polymer. Liquid crystal polymer composition.
[7] The fibrous filler is one or more selected from the group consisting of glass fiber, silica-alumina fiber, alumina fiber, carbon fiber, aramid fiber, potassium titanate fiber, aluminum borate fiber, and wollastonite. The liquid crystal polymer composition according to any one of [1] to [6].
[8] The plate-like or powder-like filler is one or more selected from the group consisting of talc, mica, graphite, calcium carbonate, dolomite, clay, glass flakes, glass beads, barium sulfate, titanium oxide, and diatomaceous earth. The liquid crystal polymer composition according to any one of [1] to [7].
[9] The liquid crystal polymer composition according to any one of [1] to [8], wherein the fibrous filler is glass fiber and the plate-like or powder-like filler is talc.
[10] A molded product composed of the liquid crystal polymer composition according to any one of [1] to [9].
[11] The molded product according to [10], wherein the molded product is a connector.
[12] An injection molding method for molding the liquid crystal polymer composition according to any one of [1] to [9] at an injection rate of 100 to 500 mm / sec.
Claims (8)
液晶ポリマーは、式（Ｉ）〜（ＩＶ）の繰返し単位から構成される液晶ポリエステル樹脂であり、
The liquid crystal polymer is a liquid crystal polyester resin composed of repeating units of the formulas (I) to (IV).
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