JP2022070568A - Liquid crystal polyester resin, liquid crystal polyester resin composition and molded products made from the same. - Google Patents
Liquid crystal polyester resin, liquid crystal polyester resin composition and molded products made from the same. Download PDFInfo
- Publication number
- JP2022070568A JP2022070568A JP2020179696A JP2020179696A JP2022070568A JP 2022070568 A JP2022070568 A JP 2022070568A JP 2020179696 A JP2020179696 A JP 2020179696A JP 2020179696 A JP2020179696 A JP 2020179696A JP 2022070568 A JP2022070568 A JP 2022070568A
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- JP
- Japan
- Prior art keywords
- liquid crystal
- polyester resin
- crystal polyester
- parts
- weight
- 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.)
- Pending
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 144
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 142
- 239000004645 polyester resin Substances 0.000 title claims abstract description 142
- 239000000203 mixture Substances 0.000 title claims description 25
- 239000000945 filler Substances 0.000 claims description 29
- 238000004804 winding Methods 0.000 abstract description 43
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract description 40
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 abstract description 38
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 abstract description 20
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 abstract description 19
- 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 abstract description 19
- 239000007788 liquid Substances 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 34
- 238000003756 stirring Methods 0.000 description 33
- 238000006116 polymerization reaction Methods 0.000 description 29
- 238000000034 method Methods 0.000 description 25
- 239000000835 fiber Substances 0.000 description 20
- 239000000155 melt Substances 0.000 description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 229910001873 dinitrogen Inorganic materials 0.000 description 11
- -1 aromatic diol Chemical class 0.000 description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004898 kneading Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000006068 polycondensation reaction Methods 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 241000790917 Dioxys <bee> Species 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 210000000078 claw Anatomy 0.000 description 3
- 125000004989 dicarbonyl group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- XCZKKZXWDBOGPA-UHFFFAOYSA-N 2-phenylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(C=2C=CC=CC=2)=C1 XCZKKZXWDBOGPA-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
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000010295 mobile communication Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-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
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- GDBUZIKSJGRBJP-UHFFFAOYSA-N 4-acetoxy benzoic acid Chemical compound CC(=O)OC1=CC=C(C(O)=O)C=C1 GDBUZIKSJGRBJP-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NFTLBCXRDNIJMI-UHFFFAOYSA-N 6-acetyloxynaphthalene-2-carboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(OC(=O)C)=CC=C21 NFTLBCXRDNIJMI-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004132 Calcium polyphosphate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- RQMBBMQDXFZFCC-UHFFFAOYSA-N [4-(4-acetyloxyphenyl)phenyl] acetate Chemical group C1=CC(OC(=O)C)=CC=C1C1=CC=C(OC(C)=O)C=C1 RQMBBMQDXFZFCC-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 235000019827 calcium polyphosphate Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
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- 229920001577 copolymer Polymers 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 description 1
- HPGJOUYGWKFYQW-UHFFFAOYSA-N diphenyl benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OC=2C=CC=CC=2)C=CC=1C(=O)OC1=CC=CC=C1 HPGJOUYGWKFYQW-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 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 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
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- GJLNWLVPAHNBQN-UHFFFAOYSA-N phenyl 4-hydroxybenzoate Chemical compound C1=CC(O)=CC=C1C(=O)OC1=CC=CC=C1 GJLNWLVPAHNBQN-UHFFFAOYSA-N 0.000 description 1
- ZCGDGMQYRJIQSU-UHFFFAOYSA-N phenyl 6-hydroxynaphthalene-2-carboxylate Chemical compound C1=CC2=CC(O)=CC=C2C=C1C(=O)OC1=CC=CC=C1 ZCGDGMQYRJIQSU-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 238000003825 pressing Methods 0.000 description 1
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- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
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- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
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Images
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- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
【課題】円筒状成形品の巻き線強度およびスナップフィット性に優れた液晶ポリエステル樹脂の提供。【解決手段】ｐ－ヒドロキシ安息香酸（Ｉ）、６－ヒドロキシ－２－ナフトエ酸（ＩＩ）、４，４’－ジヒドロキシビフェニル（ＩＩＩ）、テレフタル酸（ＩＶ）を重合して得られる液晶ポリエステル樹脂であって、下記式（Ａ）～（Ｅ）を満たす液晶ポリエステル樹脂。４４≦［Ｉ］≦５９・・・（Ａ）、２≦［ＩＩ］≦１０・・・（Ｂ）、１８．５≦［ＩＩＩ］≦２６・・・（Ｃ）、１８．５≦［ＩＶ］≦２６・・・（Ｄ）、９９≦［Ｉ］＋［ＩＩ］＋［ＩＩＩ］＋［ＩＶ］≦１００・・・（Ｅ）（［Ｉ］～［ＩＶ］は、液晶ポリエステル樹脂の全構造単位１００モル％に対する、各構造単位（Ｉ）～（ＩＶ）の含有量（モル％）を示す。）【選択図】なしAn object of the present invention is to provide a liquid crystalline polyester resin excellent in winding strength and snap-fitting properties of a cylindrical molded article. A liquid crystal polyester resin obtained by polymerizing p-hydroxybenzoic acid (I), 6-hydroxy-2-naphthoic acid (II), 4,4'-dihydroxybiphenyl (III) and terephthalic acid (IV). A liquid crystalline polyester resin which satisfies the following formulas (A) to (E). 44≦[I]≦59 (A), 2≦[II]≦10 (B), 18.5≦[III]≦26 (C), 18.5≦[IV ] ≤ 26 (D), 99 ≤ [I] + [II] + [III] + [IV] ≤ 100 (E) ([I] to [IV] are all liquid crystal polyester resin Shows the content (mol%) of each structural unit (I) to (IV) with respect to 100 mol% of the structural unit.) [Selection] None
Description
本発明は、液晶ポリエステル樹脂、液晶ポリエステル樹脂組成物およびそれからなる成形品に関する。より詳しくは、液晶ポリエステル樹脂、液晶ポリエステル樹脂組成物、ならびにそれを用いて得られる成形品に関するものである。 The present invention relates to a liquid crystal polyester resin, a liquid crystal polyester resin composition, and a molded product comprising the same. More specifically, the present invention relates to a liquid crystal polyester resin, a liquid crystal polyester resin composition, and a molded product obtained by using the liquid crystal polyester resin.
液晶ポリエステル樹脂は、液晶構造を有するため、耐熱性、流動性、寸法安定性に優れる。このため、それらの特性が要求される電気・電子部品を中心に需要が拡大している。特に近年では、それら部品の小型化、精密化と、それに伴う部品点数低減やねじレス化のためにスナップフィット部の適用が拡大している。一方で、円筒状成形品の巻き線強度に代表される小型薄肉成形品の強度や、スナップフィット部の強度が不十分である課題があった。 Since the liquid crystal polyester resin has a liquid crystal structure, it is excellent in heat resistance, fluidity, and dimensional stability. For this reason, demand is expanding mainly for electrical and electronic components that require these characteristics. In particular, in recent years, the application of snap-fit portions has been expanding in order to reduce the size and precision of these parts, and to reduce the number of parts and screwless parts. On the other hand, there is a problem that the strength of the small thin-walled molded product represented by the winding strength of the cylindrical molded product and the strength of the snap-fit portion are insufficient.
液晶ポリエステル樹脂は、芳香族ヒドロキシカルボン酸、芳香族ジオール、芳香族ジカルボン酸などを共重合した樹脂であり、共重合成分の種類や共重合量で特性が変化するため、これまで多くの組み合わせが提案されている。例えば、ｐ－ヒドロキシ安息香酸、６－ヒドロキシ－２－ナフトエ酸、４，４’－ジヒドロキシビフェニル、テレフタル酸に由来する構造単位を含む液晶ポリエステル樹脂において、製造時の無水酢酸量を規定したり、さらにハイドロキノンを共重合することによりブリスターを抑制した液晶ポリエステル樹脂（例えば、特許文献１、２）、さらにイソフタル酸を共重合することにより靭性を向上させた液晶ポリエステル樹脂（例えば、特許文献３）、６－ヒドロキシ－２－ナフトエ酸の割合を多くすることにより耐熱性を向上させた液晶ポリエステル樹脂（例えば、特許文献４）が提案されている。
The liquid crystal polyester resin is a resin obtained by copolymerizing an aromatic hydroxycarboxylic acid, an aromatic diol, an aromatic dicarboxylic acid, etc., and since the characteristics change depending on the type of copolymerization component and the amount of copolymerization, many combinations have been used so far. Proposed. For example, in a liquid crystal polyester resin containing a structural unit derived from p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4'-dihydroxybiphenyl, and terephthalic acid, the amount of anhydrous acetic acid at the time of production may be specified. Further, a liquid crystal polyester resin in which blister is suppressed by copolymerizing hydroquinone (for example,
前記特許文献１～４に記載された方法では、円筒状成形品の巻き線強度が低く、小型薄肉成形品への適用に課題があるほか、スナップフィット性に課題があった。
In the methods described in
本発明の課題は、円筒状成形品の巻き線強度に代表される小型薄肉成形品の強度、およびスナップフィット性に優れた液晶ポリエステル樹脂、液晶ポリエステル樹脂組成物およびそれからなる成形品を提供することを課題とする。 An object of the present invention is to provide a liquid crystal polyester resin, a liquid crystal polyester resin composition, and a molded product comprising the liquid crystal polyester resin, which is excellent in the strength of a small thin-walled molded product represented by the winding strength of the cylindrical molded product and the snap fit property. Is the subject.
本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、ｐ－ヒドロキシ安息香酸、６－ヒドロキシ－２－ナフトエ酸、４，４’－ジヒドロキシビフェニル、テレフタル酸に由来する構造単位を一定量含むことにより、円筒状成形品の巻き線強度およびスナップフィット性に優れた液晶ポリエステル樹脂となることを見出し、本発明に到達した。 As a result of diligent studies to solve the above problems, the present inventors have conducted structural units derived from p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4'-dihydroxybiphenyl, and terephthalic acid. We have found that a liquid crystal polyester resin having excellent winding strength and snap-fitting property of a cylindrical molded product can be obtained by containing a certain amount of the above, and have reached the present invention.
すなわち本発明は以下のとおりである：
（１）下記構造単位（Ｉ）～（ＩＶ）を含む液晶ポリエステル樹脂であって、下記式（Ａ）～（Ｅ）を満たす液晶ポリエステル樹脂。
４４≦［Ｉ］≦５９ ・・・（Ａ）
２≦［ＩＩ］≦１０ ・・・（Ｂ）
１８．５≦［ＩＩＩ］≦２６ ・・・（Ｃ）
１８．５≦［ＩＶ］≦２６ ・・・（Ｄ）
９９≦［Ｉ］＋［ＩＩ］＋［ＩＩＩ］＋［ＩＶ］≦１００ ・・・（Ｅ）
（［Ｉ］～［ＩＶ］は、液晶ポリエステル樹脂の全構造単位１００モル％に対する、各構造単位（Ｉ）～（ＩＶ）の含有量（モル％）を示す。）
That is, the present invention is as follows:
(1) A liquid crystal polyester resin containing the following structural units (I) to (IV) and satisfying the following formulas (A) to (E).
44 ≤ [I] ≤ 59 ... (A)
2 ≦ [II] ≦ 10 ・ ・ ・ (B)
18.5 ≤ [III] ≤ 26 ... (C)
18.5 ≤ [IV] ≤ 26 ... (D)
99 ≤ [I] + [II] + [III] + [IV] ≤ 100 ... (E)
([I] to [IV] indicate the content (mol%) of each structural unit (I) to (IV) with respect to 100 mol% of all structural units of the liquid crystal polyester resin.)
（２）さらに、下記式（Ｆ）を満たす（１）に記載の液晶ポリエステル樹脂。
３＜［ＩＩ］≦５．７ ・・・（Ｆ）
（３）さらに、下記式（Ｇ）を満たす（１）または（２）に記載の液晶ポリエステル樹脂。
１０＜［Ｉ］／［ＩＩ］＜１５ ・・・（Ｇ）
（４）（１）～（３）のいずれかに記載の液晶ポリエステル樹脂１００重量部に対し、充填材１０～２００重量部を含有する、液晶ポリエステル樹脂組成物。
（５）（１）～（３）のいずれかに記載の液晶ポリエステル樹脂、または（４）に記載の液晶ポリエステル樹脂組成物からなる成形品。
（６）成形品が、成形品が、コネクタ、リレー、スイッチ、コイルボビン、カメラモジュール、およびランプソケットからなる群から選択されるいずれかである（５）に記載の成形品。
(2) Further, the liquid crystal polyester resin according to (1), which satisfies the following formula (F).
3 <[II] ≤ 5.7 ... (F)
(3) The liquid crystal polyester resin according to (1) or (2), which further satisfies the following formula (G).
10 <[I] / [II] <15 ... (G)
(4) A liquid crystal polyester resin composition containing 10 to 200 parts by weight of a filler with respect to 100 parts by weight of the liquid crystal polyester resin according to any one of (1) to (3).
(5) A molded product comprising the liquid crystal polyester resin according to any one of (1) to (3) or the liquid crystal polyester resin composition according to (4).
(6) The molded product according to (5), wherein the molded product is one in which the molded product is selected from the group consisting of a connector, a relay, a switch, a coil bobbin, a camera module, and a lamp socket.
本発明の液晶ポリエステル樹脂により、円筒状成形品の巻き線強度およびスナップフィット性に優れる成形品を得ることができる。特に、小型の電気・電子部品用途などへの提供に好適であり、巻き線部やスナップフィット部を有する電気・電子部品に用いることができる。 With the liquid crystal polyester resin of the present invention, it is possible to obtain a molded product having excellent winding strength and snap-fitting property of the cylindrical molded product. In particular, it is suitable for providing small electric / electronic parts, and can be used for electric / electronic parts having a winding portion and a snap-fit portion.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明における円筒状成形品の巻き線強度（以下、巻き線強度と記載することがある）とは、円筒状成形品に対し線を巻き付ける際、円筒状成形品が形状を保つことのできる巻き付け強度のことをいう。巻き線強度は、円筒状成形品に荷重を掛け、その一次ピーク圧（Ｎ）を測定することで擬似的に評価可能である。
本発明におけるスナップフィット性とは、突起部を有する成形品の突起部に対し、その突起部に嵌合する板状成形品（角板）をはめ込む際に、突起部を有する成形品の突起部が折れることなく板状成形品をはめ込むことができることをいう。
The winding strength of the cylindrical molded product in the present invention (hereinafter, may be referred to as winding strength) is the winding that allows the cylindrical molded product to maintain its shape when the wire is wound around the cylindrical molded product. It refers to strength. The winding strength can be evaluated in a pseudo manner by applying a load to the cylindrical molded product and measuring its primary peak pressure (N).
The snap fit property in the present invention means a protrusion of a molded product having a protrusion when a plate-shaped molded product (square plate) fitted to the protrusion is fitted into the protrusion of the molded product having the protrusion. It means that the plate-shaped molded product can be fitted without breaking.
＜液晶ポリエステル樹脂＞
液晶ポリエステル樹脂は、異方性溶融相を形成するポリエステルである。このようなポリエステル樹脂としては、例えば、後述するオキシカルボニル単位、ジオキシ単位、ジカルボニル単位などから異方性溶融相を形成するよう選ばれた構造単位から構成されるポリエステルなどが挙げられる。
<Liquid crystal polyester resin>
The liquid crystal polyester resin is a polyester that forms an anisotropic molten phase. Examples of such a polyester resin include polyesters composed of structural units selected to form an anisotropic molten phase from oxycarbonyl units, dioxy units, dicarbonyl units and the like, which will be described later.
次に、液晶ポリエステル樹脂を構成する構造単位について説明する。
本発明の液晶ポリエステル樹脂は、液晶ポリエステル樹脂の全構造単位１００モル％に対して、オキシカルボニル単位として、下記構造単位（Ｉ）を４４モル％以上含む。構造単位（Ｉ）はｐ－ヒドロキシ安息香酸に由来する構造単位である。構造単位（Ｉ）が４４モル％未満である場合、巻き線強度をはじめとした成形品の強度が大幅に低下し、スナップフィット性も大幅に低下する。巻き線強度およびスナップフィット性を向上させる観点から、構造単位（Ｉ）は４６モル％以上であることが好ましく、４９モル％以上であることがより好ましく、５２モル％以上がさらに好ましい。
Next, the structural units constituting the liquid crystal polyester resin will be described.
The liquid crystal polyester resin of the present invention contains 44 mol% or more of the following structural unit (I) as an oxycarbonyl unit with respect to 100 mol% of the total structural unit of the liquid crystal polyester resin. The structural unit (I) is a structural unit derived from p-hydroxybenzoic acid. When the structural unit (I) is less than 44 mol%, the strength of the molded product including the winding strength is significantly reduced, and the snap fit property is also significantly reduced. From the viewpoint of improving the winding strength and the snap fit, the structural unit (I) is preferably 46 mol% or more, more preferably 49 mol% or more, still more preferably 52 mol% or more.
一方、本発明の液晶ポリエステル樹脂は、液晶ポリエステル樹脂の全構造単位１００モル％に対して、下記構造単位（Ｉ）を５９モル％以下含む。構造単位（Ｉ）が５９モル％より多い場合、結晶性が高いため脆くなり、巻き線強度やスナップフィット性が大幅に低下する。巻き線強度およびスナップフィット性を向上させる観点から、構造単位（Ｉ）は５８モル％以下が好ましく、５７モル％以下がより好ましい。 On the other hand, the liquid crystal polyester resin of the present invention contains the following structural unit (I) in an amount of 59 mol% or less with respect to 100 mol% of the total structural unit of the liquid crystal polyester resin. When the structural unit (I) is more than 59 mol%, it becomes brittle due to its high crystallinity, and the winding strength and snap-fitting property are significantly lowered. From the viewpoint of improving the winding strength and the snap fit, the structural unit (I) is preferably 58 mol% or less, more preferably 57 mol% or less.
本発明の液晶ポリエステル樹脂は、液晶ポリエステル樹脂の全構造単位１００モル％に対して、オキシカルボニル単位として、下記構造単位（ＩＩ）を２モル％以上含む。構造単位（ＩＩ）は６－ヒドロキシ－２－ナフトエ酸に由来する構造単位である。構造単位（ＩＩ）が２モル％未満である場合、結晶性が高いため脆くなり、巻き線強度やスナップフィット性が大幅に低下する。巻き線強度およびスナップフィット性を向上させる観点から、構造単位（ＩＩ）は２．５モル％以上であることが好ましく、３モル％より多いことがより好ましい。 The liquid crystal polyester resin of the present invention contains the following structural unit (II) in an amount of 2 mol% or more as an oxycarbonyl unit with respect to 100 mol% of the total structural unit of the liquid crystal polyester resin. The structural unit (II) is a structural unit derived from 6-hydroxy-2-naphthoic acid. When the structural unit (II) is less than 2 mol%, it becomes brittle due to its high crystallinity, and the winding strength and snap-fitting property are significantly lowered. From the viewpoint of improving the winding strength and the snap fit, the structural unit (II) is preferably 2.5 mol% or more, and more preferably 3 mol% or more.
一方、本発明の液晶ポリエステル樹脂は、液晶ポリエステル樹脂の全構造単位１００モル％に対して、下記構造単位（ＩＩ）を１０モル％以下含む。構造単位（ＩＩ）が１０モル％より多い場合、巻き線強度をはじめとした成形品の強度が大幅に低下し、スナップフィット性も大幅に低下する。巻き線強度およびスナップフィット性を向上させる観点から、構造単位（ＩＩ）は８モル％以下が好ましく、５．７モル％以下がより好ましい。 On the other hand, the liquid crystal polyester resin of the present invention contains the following structural unit (II) in an amount of 10 mol% or less with respect to 100 mol% of the total structural unit of the liquid crystal polyester resin. When the structural unit (II) is more than 10 mol%, the strength of the molded product including the winding strength is significantly lowered, and the snap fit property is also significantly lowered. From the viewpoint of improving the winding strength and the snap fit, the structural unit (II) is preferably 8 mol% or less, more preferably 5.7 mol% or less.
本発明の液晶ポリエステル樹脂は、成形品の強度を向上させ、巻き線強度およびスナップフィット性を向上させる観点から、構造単位（Ｉ）と（ＩＩ）の含有量のモル比（［Ｉ］／［ＩＩ］）が、１０より大きいことが好ましく、１０．５より大きいことが好ましい。一方、結晶性を制御し、巻き線強度およびスナップフィット性を向上させる観点から、［Ｉ］／［ＩＩ］は１５より小さいことが好ましく、１４．５より小さいことが好ましい。 The liquid crystal polyester resin of the present invention has a molar ratio of the contents of the structural units (I) and (II) ([I] / [] from the viewpoint of improving the strength of the molded product and improving the winding strength and the snap fit. II]) is preferably greater than 10, preferably greater than 10.5. On the other hand, from the viewpoint of controlling the crystallinity and improving the winding strength and the snap fit, [I] / [II] is preferably smaller than 15, preferably smaller than 14.5.
他に、オキシカルボニル単位として、ｍ－ヒドロキシ安息香酸などに由来する構造単位を、後述する構造単位（Ｉ）～（ＩＶ）の合計量を満足する範囲で使用することができる。 In addition, as the oxycarbonyl unit, a structural unit derived from m-hydroxybenzoic acid or the like can be used within a range satisfying the total amount of the structural units (I) to (IV) described later.
本発明の液晶ポリエステル樹脂は、液晶ポリエステル樹脂の全構造単位１００モル％に対して、ジオキシ単位として、下記構造単位（ＩＩＩ）を１８．５モル％以上含む。構造単位（ＩＩＩ）は、４，４’－ジヒドロキシビフェニルに由来する構造単位である。構造単位（ＩＩＩ）が１８．５モル％未満である場合、結晶性が高いため脆くなり、巻き線強度やスナップフィット性が大幅に低下する。巻き線強度およびスナップフィット性を向上させる観点から、構造単位（ＩＩＩ）は１９モル％以上であることが好ましく、１９．５モル％以上であることがより好ましい。 The liquid crystal polyester resin of the present invention contains the following structural unit (III) in an amount of 18.5 mol% or more as a dioxy unit with respect to 100 mol% of the total structural unit of the liquid crystal polyester resin. The structural unit (III) is a structural unit derived from 4,4'-dihydroxybiphenyl. When the structural unit (III) is less than 18.5 mol%, it becomes brittle due to its high crystallinity, and the winding strength and snap-fitting property are significantly lowered. From the viewpoint of improving the winding strength and the snap fit, the structural unit (III) is preferably 19 mol% or more, and more preferably 19.5 mol% or more.
一方、本発明の液晶ポリエステル樹脂は、液晶ポリエステル樹脂の全構造単位１００モル％に対して、下記構造単位（ＩＩＩ）を２６モル％以下含む。構造単位（ＩＩＩ）が２６モル％より多い場合、巻き線強度をはじめとした成形品の強度が大幅に低下し、スナップフィット性も大幅に低下する。巻き線強度およびスナップフィット性を向上させる観点から、構造単位（ＩＩＩ）は２４モル％以下が好ましく、２２モル％以下がより好ましい。 On the other hand, the liquid crystal polyester resin of the present invention contains the following structural unit (III) in an amount of 26 mol% or less with respect to 100 mol% of the total structural unit of the liquid crystal polyester resin. When the structural unit (III) is more than 26 mol%, the strength of the molded product including the winding strength is significantly reduced, and the snap fit property is also significantly reduced. From the viewpoint of improving the winding strength and the snap fit, the structural unit (III) is preferably 24 mol% or less, more preferably 22 mol% or less.
他に、ジオキシ単位として、ハイドロキノン、レゾルシノール、ｔ－ブチルハイドロキノン、フェニルハイドロキノン、クロロハイドロキノン、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、３，４’－ジヒドロキシビフェニル、２，２－ビス（４－ヒドロキシフェニル）プロパン、４，４’－ジヒドロキシジフェニルエーテル、４，４’－ジヒドロキシジフェニルスルホン、４，４’－ジヒドロキシジフェニルスルフィド、４，４’－ジヒドロキシベンゾフェノンなどの芳香族ジオールに由来する構造単位；エチレングリコール、プロピレングリコール、１，４－ブタンジオール、１，６－ヘキサンジオール、ネオペンチルグリコールなどの脂肪族ジオールに由来する構造単位；１，４－シクロヘキサンジオール、１，４－シクロヘキサンジメタノールなどの脂環式ジオールに由来する構造単位を、後述する構造単位（Ｉ）～（ＩＶ）の合計量を満足する範囲で使用することができる。 In addition, as dioxy units, hydroquinone, resorcinol, t-butylhydroquinone, phenylhydroquinone, chlorohydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 3,4'-dihydroxybiphenyl, 2,2-bis ( 4-Hydroxyphenyl) Structural units derived from aromatic diols such as propane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxybenzophenone. Structural units derived from aliphatic diols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol; 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, etc. The structural unit derived from the alicyclic diol can be used within a range satisfying the total amount of the structural units (I) to (IV) described later.
本発明の液晶ポリエステル樹脂は、液晶ポリエステル樹脂の全構造単位１００モル％に対して、ジカルボニル単位として、下記構造単位（ＩＶ）を１８．５モル％以上含む。構造単位（ＩＶ）は、テレフタル酸に由来する構造単位である。構造単位（ＩＶ）が１８．５モル％未満である場合、結晶性が高いため脆くなり、巻き線強度やスナップフィット性が大幅に低下する。巻き線強度およびスナップフィット性を向上させる観点から、構造単位（ＩＶ）は１９モル％以上であることが好ましく、１９．５モル％以上であることがより好ましい。 The liquid crystal polyester resin of the present invention contains the following structural unit (IV) in an amount of 18.5 mol% or more as a dicarbonyl unit with respect to 100 mol% of the total structural unit of the liquid crystal polyester resin. The structural unit (IV) is a structural unit derived from terephthalic acid. When the structural unit (IV) is less than 18.5 mol%, it becomes brittle due to its high crystallinity, and the winding strength and snap-fitting property are significantly lowered. From the viewpoint of improving the winding strength and the snap fit, the structural unit (IV) is preferably 19 mol% or more, and more preferably 19.5 mol% or more.
一方、本発明の液晶ポリエステル樹脂は、液晶ポリエステル樹脂の全構造単位１００モル％に対して、下記構造単位（ＩＶ）を２６モル％以下含む。構造単位（ＩＶ）が２６モル％より多い場合、巻き線強度をはじめとした成形品の強度が大幅に低下し、スナップフィット性も大幅に低下する。巻き線強度およびスナップフィット性を向上させる観点から、構造単位（ＩＶ）は２４モル％以下が好ましく、２２モル％以下がより好ましい。 On the other hand, the liquid crystal polyester resin of the present invention contains the following structural unit (IV) in an amount of 26 mol% or less with respect to 100 mol% of the total structural unit of the liquid crystal polyester resin. When the structural unit (IV) is more than 26 mol%, the strength of the molded product including the winding strength is significantly lowered, and the snap fit property is also significantly lowered. From the viewpoint of improving the winding strength and the snap fit, the structural unit (IV) is preferably 24 mol% or less, more preferably 22 mol% or less.
他に、ジカルボニル単位として、イソフタル酸、２，６－ナフタレンジカルボン酸、４，４’－ジフェニルジカルボン酸、３，３’－ジフェニルジカルボン酸、２，２’－ジフェニルジカルボン酸、１，２－ビス（フェノキシ）エタン－４，４’－ジカルボン酸、１，２－ビス（２－クロロフェノキシ）エタン－４，４’－ジカルボン酸、４，４’－ジフェニルエーテルジカルボン酸などの芳香族ジカルボン酸に由来する構造単位；アジピン酸、アゼライン酸、セバシン酸、ドデカンジオン酸、ヘキサヒドロテレフタル酸などの脂肪族ジカルボン酸に由来する構造単位；１，４－シクロヘキサンジカルボン酸、１，３－シクロヘキサンジカルボン酸などの脂環式ジカルボン酸に由来する構造単位を、後述する構造単位（Ｉ）～（ＩＶ）の合計量を満足する範囲で使用することができる。 In addition, as the dicarbonyl unit, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 3,3'-diphenyldicarboxylic acid, 2,2'-diphenyldicarboxylic acid, 1,2- For aromatic dicarboxylic acids such as bis (phenoxy) ethane-4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid, and 4,4'-diphenylether dicarboxylic acid. Derived structural units; structural units derived from aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecandionic acid, hexahydroterephthalic acid; 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, etc. The structural unit derived from the alicyclic dicarboxylic acid of No. 1 can be used within a range satisfying the total amount of the structural units (I) to (IV) described later.
本発明の液晶ポリエステル樹脂は、前記構造単位（Ｉ）～（ＩＶ）の合計量が９９モル％以上である。構造単位（Ｉ）～（ＩＶ）の合計量が９９モル％未満であると、巻き線強度をはじめとした成形品の強度が大幅に低下し、スナップフィット性も大幅に低下する。巻き線強度およびスナップフィット性を向上させる観点から、構造単位（Ｉ）～（ＩＶ）の合計量は９９．５モル％以上が好ましく、１００モル％がより好ましい。 The liquid crystal polyester resin of the present invention has a total amount of the structural units (I) to (IV) of 99 mol% or more. When the total amount of the structural units (I) to (IV) is less than 99 mol%, the strength of the molded product including the winding strength is significantly lowered, and the snap fit property is also significantly lowered. From the viewpoint of improving the winding strength and the snap fit, the total amount of the structural units (I) to (IV) is preferably 99.5 mol% or more, more preferably 100 mol%.
また、液晶ポリエステル樹脂には、上記構造単位（Ｉ）～（ＩＶ）に加えて、ｐ－アミノ安息香酸、ｐ－アミノフェノールなどから生成した構造単位を、前述の構造単位（Ｉ）～（ＩＶ）の合計量を満足する範囲でさらに有することができる。 Further, in the liquid crystal polyester resin, in addition to the above-mentioned structural units (I) to (IV), structural units produced from p-aminobenzoic acid, p-aminophenol and the like are added to the above-mentioned structural units (I) to (IV). ) Can be further held within a satisfactory range.
上記の各構造単位を構成する原料となるモノマーは、各構造単位を形成しうる構造であれば特に限定されない。また、そのようなモノマーの水酸基のアシル化物、カルボキシル基のエステル化物、酸ハロゲン化物、酸無水物などのカルボン酸誘導体などが使用されてもよい。 The monomer as a raw material constituting each of the above structural units is not particularly limited as long as it has a structure capable of forming each structural unit. Further, an acylated product of a hydroxyl group of such a monomer, an esterified product of a carboxyl group, an acid halide, a carboxylic acid derivative such as an acid anhydride, or the like may be used.
液晶ポリエステル樹脂について、各構造単位の含有量の算出法を以下に示す。まず、液晶ポリエステル樹脂を粉砕後、水酸化テトラメチルアンモニウムを添加し、島津製ＧＣＭＳ－ＱＰ５０５０Ａを用いて、熱分解ＧＣ／ＭＳ測定を行うことによって求めることができる。検出されなかった、あるいは検出限界以下の構造単位の含有量は０モル％として計算する。 The calculation method of the content of each structural unit of the liquid crystal polyester resin is shown below. First, it can be obtained by crushing the liquid crystal polyester resin, adding tetramethylammonium hydroxide, and performing pyrolysis GC / MS measurement using Shimadzu GCMS-QP5050A. The content of structural units not detected or below the detection limit is calculated as 0 mol%.
液晶ポリエステル樹脂の融点（Ｔｍ）は、巻き線強度およびスナップフィット性を向上させる観点から、２２０℃以上が好ましく、２５０℃以上がより好ましく、２８０℃以上がさらに好ましい。一方、結晶性を適度に制御し、巻き線強度およびスナップフィット性を向上させる観点から、液晶ポリエステル樹脂の融点（Ｔｍ）は、３６０℃以下が好ましく、３５０℃以下がより好ましい。 The melting point (Tm) of the liquid crystal polyester resin is preferably 220 ° C. or higher, more preferably 250 ° C. or higher, still more preferably 280 ° C. or higher, from the viewpoint of improving winding strength and snap-fitting property. On the other hand, from the viewpoint of appropriately controlling the crystallinity and improving the winding strength and the snap fit, the melting point (Tm) of the liquid crystal polyester resin is preferably 360 ° C. or lower, more preferably 350 ° C. or lower.
液晶ポリエステル樹脂の溶融粘度は、巻き線強度およびスナップフィット性を向上させる観点から、１Ｐａ・ｓ以上が好ましく、５Ｐａ・ｓ以上がより好ましく、１０Ｐａ・ｓ以上がさらに好ましい。一方、流動性がよく小型薄肉成形品を容易に射出成形可能な観点から、液晶ポリエステル樹脂の溶融粘度は、２００Ｐａ・ｓ以下が好ましく、１００Ｐａ・ｓ以下が好ましく、５０Ｐａ・ｓ以下がさらに好ましい。 The melt viscosity of the liquid crystal polyester resin is preferably 1 Pa · s or more, more preferably 5 Pa · s or more, still more preferably 10 Pa · s or more, from the viewpoint of improving winding strength and snap fit. On the other hand, from the viewpoint of good fluidity and easy injection molding of a small thin-walled molded product, the melt viscosity of the liquid crystal polyester resin is preferably 200 Pa · s or less, preferably 100 Pa · s or less, and even more preferably 50 Pa · s or less.
なお、この溶融粘度は、液晶ポリエステル樹脂の融点（Ｔｍ）＋２０℃の温度において、かつ、せん断速度１０００／秒の条件下で、高化式フローテスターによって測定した値である。 The melt viscosity is a value measured by a high-grade flow tester at a temperature of the melting point (Tm) + 20 ° C. of the liquid crystal polyester resin and under the condition of a shear rate of 1000 / sec.
＜液晶ポリエステル樹脂の製造方法＞
本発明で使用する液晶ポリエステル樹脂を製造する方法は、特に制限がなく、公知のポリエステルの重縮合法に準じて製造できる。具体的には、ｐ－ヒドロキシ安息香酸に由来する構造単位、６－ヒドロキシ－２－ナフトエ酸に由来する構造単位、４，４’－ジヒドロキシビフェニルに由来する構造単位、およびテレフタル酸に由来する構造単位からなる液晶ポリエステル樹脂を例に、以下が挙げられる。
<Manufacturing method of liquid crystal polyester resin>
The method for producing the liquid crystal polyester resin used in the present invention is not particularly limited, and can be produced according to a known polycondensation method for polyester. Specifically, a structural unit derived from p-hydroxybenzoic acid, a structural unit derived from 6-hydroxy-2-naphthoic acid, a structural unit derived from 4,4'-dihydroxybiphenyl, and a structure derived from terephthalic acid. The following can be mentioned as an example of a liquid crystal polyester resin composed of units.
（１）ｐ－アセトキシ安息香酸、６－アセトキシ－２－ナフトエ酸および４，４’－ジアセトキシビフェニルとテレフタル酸から脱酢酸縮重合反応によって液晶ポリエステル樹脂を製造する方法。 (1) A method for producing a liquid crystal polyester resin from p-acetoxybenzoic acid, 6-acetoxy-2-naphthoic acid, 4,4'-diacetoxybiphenyl and terephthalic acid by a deacetic acid polycondensation reaction.
（２）ｐ－ヒドロキシ安息香酸、６－ヒドロキシ－２－ナフトエ酸、４，４’－ジヒドロキシビフェニル、テレフタル酸に無水酢酸を反応させて、フェノール性水酸基をアセチル化した後、脱酢酸重合することによって液晶ポリエステル樹脂を製造する方法。 (2) Acetic anhydride is reacted with p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4'-dihydroxybiphenyl, and terephthalic acid to acetylate the phenolic hydroxyl group, and then deacetic acid polymerization is performed. A method of manufacturing liquid crystal polyester resin by.
（３）ｐ－ヒドロキシ安息香酸フェニル、６－ヒドロキシ－２－ナフトエ酸フェニルおよび４，４’－ジヒドロキシビフェニルとテレフタル酸ジフェニルから脱フェノール重縮合反応により液晶ポリエステル樹脂を製造する方法。 (3) A method for producing a liquid crystal polyester resin from phenyl p-hydroxybenzoate, phenyl 6-hydroxy-2-naphthoate, 4,4'-dihydroxybiphenyl and diphenyl terephthalate by a dephenol polycondensation reaction.
（４）ｐ－ヒドロキシ安息香酸、６－ヒドロキシ－２－ナフトエ酸およびテレフタル酸に所定量のジフェニルカーボネートを反応させて、それぞれフェニルエステルとした後、４，４’－ジヒドロキシビフェニルを加え、脱フェノール重縮合反応により液晶ポリエステル樹脂を製造する方法。 (4) P-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid and terephthalic acid are reacted with a predetermined amount of diphenyl carbonate to form phenyl esters, respectively, and then 4,4'-dihydroxybiphenyl is added to dephenolize. A method for producing a liquid crystal polyester resin by a polycondensation reaction.
なかでも（２）ｐ－ヒドロキシ安息香酸、６－ヒドロキシ－２－ナフトエ酸、４，４’－ジヒドロキシビフェニル、テレフタル酸に無水酢酸を反応させて、フェノール性水酸基をアセチル化した後、脱酢酸重合することによって液晶ポリエステル樹脂を製造する方法が、液晶ポリエステル樹脂の重合度の制御に工業的に優れる点から、好ましく用いられる。 Among them, (2) p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4'-dihydroxybiphenyl, and terephthalic acid are reacted with acetic anhydride to acetylate the phenolic hydroxyl group, and then deacetic acid polymerization. The method for producing the liquid crystal polyester resin by the above method is preferably used because it is industrially excellent in controlling the degree of polymerization of the liquid crystal polyester resin.
本発明で使用する液晶ポリエステル樹脂の製造方法として、固相重合法により重縮合反応を完了させることも可能である。固相重合法による処理としては、例えば、以下の方法が挙げられる。まず、液晶ポリエステル樹脂のポリマーまたはオリゴマーを粉砕機で粉砕する。粉砕したポリマーまたはオリゴマーを、窒素気流下、または、減圧下において加熱し、所望の重合度まで重縮合することで、反応を完了させる。上記加熱は、液晶ポリエステルの融点－５０℃～融点－５℃（例えば、２００～３００℃）の範囲で１～５０時間行うことが好ましい。 As a method for producing the liquid crystal polyester resin used in the present invention, it is also possible to complete the polycondensation reaction by a solid phase polymerization method. Examples of the treatment by the solid phase polymerization method include the following methods. First, the polymer or oligomer of the liquid crystal polyester resin is crushed with a crusher. The reaction is completed by heating the pulverized polymer or oligomer under a nitrogen stream or under reduced pressure and polycondensing to a desired degree of polymerization. The heating is preferably performed in the range of the melting point of the liquid crystal polyester to −50 ° C. to the melting point of −5 ° C. (for example, 200 to 300 ° C.) for 1 to 50 hours.
液晶ポリエステル樹脂の重縮合反応は、無触媒でも進行するが、酢酸第一錫、テトラブチルチタネート、酢酸カリウムおよび酢酸ナトリウム、三酸化アンチモン、金属マグネシウムなどを触媒として使用することもできる。 The polycondensation reaction of the liquid crystal polyester resin proceeds without a catalyst, but stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, metallic magnesium and the like can also be used as catalysts.
＜充填材＞
本発明の液晶ポリエステル樹脂は、液晶ポリエステル樹脂の機械強度その他の特性を付与するために充填材を含有してもよい。本発明で使用される充填材は、特に限定されるものではないが、例えば、繊維状、ウィスカー状、板状、粉末状、粒状などの充填材を挙げることができる。具体的には、繊維状、ウィスカー状充填材としては、ガラス繊維、ＰＡＮ系やピッチ系の炭素繊維、ステンレス繊維、アルミニウム繊維や黄銅繊維などの金属繊維、芳香族ポリアミド繊維や液晶ポリエステル繊維などの有機繊維、石膏繊維、セラミック繊維、アスベスト繊維、ジルコニア繊維、アルミナ繊維、シリカ繊維、酸化チタン繊維、炭化ケイ素繊維、ロックウール、チタン酸カリウムウィスカー、チタン酸バリウムウィスカー、ホウ酸アルミニウムウィスカー、窒化ケイ素ウィスカー、および針状酸化チタンなどが挙げられる。板状充填材としては、マイカ、タルク、カオリン、ガラスフレーク、クレー、二硫化モリブデン、およびワラステナイトなどが挙げられる。粉状、粒状の充填材としては、シリカ、ガラスビーズ、酸化チタン、酸化亜鉛、ポリリン酸カルシウムおよび黒鉛などが挙げられる。本発明に使用される上記の充填材は、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など）、その他の表面処理剤で処理されていてもよい。また、本発明に使用される上記の充填材は、２種以上を併用してもよい。
<Filler>
The liquid crystal polyester resin of the present invention may contain a filler in order to impart mechanical strength and other characteristics of the liquid crystal polyester resin. The filler used in the present invention is not particularly limited, and examples thereof include fibrous, whisker-like, plate-like, powder-like, and granular-like fillers. Specifically, the fibrous and whisker-like fillers include glass fibers, PAN-based and pitch-based carbon fibers, stainless fibers, metal fibers such as aluminum fibers and brass fibers, aromatic polyamide fibers and liquid crystal polyester fibers. Organic fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker , And needle-shaped titanium oxide and the like. Plate-like fillers include mica, talc, kaolin, glass flakes, clay, molybdenum disulfide, warastenite and the like. Examples of the powdery and granular fillers include silica, glass beads, titanium oxide, zinc oxide, calcium polyphosphate and graphite. The surface of the above-mentioned filler used in the present invention may be treated with a known coupling agent (for example, a silane-based coupling agent, a titanate-based coupling agent, etc.) or another surface treatment agent. Further, two or more kinds of the above-mentioned fillers used in the present invention may be used in combination.
上記充填材中、特に引張強度や曲げ強度などの機械的強度、耐熱性、寸法安定性に優れる点から、ガラス繊維を使用することが好ましい。ガラス繊維の種類は、一般に樹脂の強化用に用いるものであれば特に限定はなく、例えば、長繊維タイプや短繊維タイプのチョップドストランド、ミルドファイバーなどを挙げることができる。また、薄肉流動性に優れる点から、マイカを使用することが好ましい。 Among the fillers, it is preferable to use glass fiber because it is excellent in mechanical strength such as tensile strength and bending strength, heat resistance, and dimensional stability. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing the resin, and examples thereof include long fiber type, short fiber type chopped strand, and milled fiber. In addition, it is preferable to use mica because it is thin and has excellent fluidity.
上記充填材は、その表面が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など）、その他の表面処理剤により処理されていてもよい。また、ガラス繊維は、エチレン／酢酸ビニル共重合体などの熱可塑性樹脂、エポキシ樹脂などの熱硬化性樹脂で被覆あるいは集束されていてもよい。 The surface of the filler may be treated with a known coupling agent (for example, a silane-based coupling agent, a titanate-based coupling agent, etc.) or another surface treatment agent. Further, the glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.
本発明の液晶ポリエステル樹脂組成物には、本発明の効果を損なわない範囲でさらに酸化防止剤、熱安定剤（例えば、ヒンダードフェノール、ハイドロキノン、ホスファイト、チオエーテル類およびこれらの置換体など）、紫外線吸収剤（例えば、レゾルシノール、サリシレート）、亜リン酸塩、次亜リン酸塩などの着色防止剤、滑剤および離型剤（モンタン酸およびその金属塩、そのエステル、そのハーフエステル、ステアリルアルコール、ステアラミドおよびポリエチレンワックスなど）、染料または顔料を含む着色剤、導電剤あるいは着色剤としてカーボンブラック、結晶核剤、可塑剤、難燃剤（臭素系難燃剤、燐系難燃剤、赤燐、シリコーン系難燃剤など）、難燃助剤、および帯電防止剤から選択される通常の添加剤を配合することができる。 The liquid crystal polyester resin composition of the present invention may further contain an antioxidant, a heat stabilizer (eg, hindered phenol, hydroquinone, phosphite, thioethers and their substitutes, etc.) as long as the effects of the present invention are not impaired. Anticolorants such as UV absorbers (eg resorcinol, salicylate), phosphite, hypophosphite, lubricants and mold release agents (montanoic acid and its metal salts, their esters, their half esters, stearyl alcohols, (Stearamid and polyethylene wax, etc.), colorants containing dyes or pigments, carbon black as conductive or colorants, crystal nucleating agents, plasticizers, flame retardants (bromine-based flame retardants, phosphorus-based flame retardants, red phosphorus, silicone-based flame retardants) Ordinary additives selected from (fuel agents, etc.), flame retardant aids, and antistatic agents can be blended.
本発明の液晶ポリエステル樹脂組成物において、充填材の含有量は、液晶ポリエステル樹脂１００重量部に対し、１０～２００重量部が好ましい。充填材含有量が１０重量部以上であれば、成形品の機械強度を向上させることができ、巻き線強度が向上するため好ましい。１５重量部以上がより好ましく、２０重量部以上がさらに好ましい。一方、充填材含有量が２００重量部以下であれば、成形性および薄肉流動性に優れ、小型薄肉成形品を容易に射出成形可能な液晶ポリエステル樹脂組成物が得られるため好ましい。１５０重量部以下がより好ましく、１００重量部以下がさらに好ましい。 In the liquid crystal polyester resin composition of the present invention, the content of the filler is preferably 10 to 200 parts by weight with respect to 100 parts by weight of the liquid crystal polyester resin. When the content of the filler is 10 parts by weight or more, the mechanical strength of the molded product can be improved and the winding strength is improved, which is preferable. 15 parts by weight or more is more preferable, and 20 parts by weight or more is further preferable. On the other hand, when the content of the filler is 200 parts by weight or less, it is preferable because a liquid crystal polyester resin composition which is excellent in moldability and thin-walled fluidity and can be easily injection-molded into a small thin-walled molded product can be obtained. 150 parts by weight or less is more preferable, and 100 parts by weight or less is further preferable.
上記の充填材および添加剤を配合する方法としては、例えば、液晶ポリエステル樹脂に充填材およびその他の固体状の添加剤等を配合するドライブレンド法や、液晶ポリエステル樹脂に充填材およびその他の液体状の添加剤等を配合する溶液配合法、充填材およびその他の添加剤を液晶ポリエステル樹脂の重合時に添加する方法、液晶ポリエステル樹脂に充填材およびその他の添加剤を溶融混練する方法を用いることができ、なかでも溶融混練する方法が好ましい。 Examples of the method for blending the above-mentioned filler and additive include a dry blend method in which a filler and other solid additives are blended with the liquid crystal polyester resin, and a filler and other liquid state in the liquid crystal polyester resin. It is possible to use a solution compounding method for blending the additives and the like, a method of adding a filler and other additives at the time of polymerization of the liquid crystal polyester resin, and a method of melt-kneading the filler and other additives to the liquid crystal polyester resin. Above all, the method of melt-kneading is preferable.
溶融混練には、公知の方法を用いることができる。例えば、バンバリーミキサー、ゴムロール機、ニーダー、単軸もしくは二軸押出機などを挙げることができる。なかでも二軸押出機が好ましい。溶融混練温度は、液晶ポリエステル樹脂の融点以上融点＋５０℃以下が好ましい。 A known method can be used for melt-kneading. For example, a Banbury mixer, a rubber roll machine, a kneader, a single-screw or twin-screw extruder, and the like can be mentioned. Of these, a twin-screw extruder is preferable. The melt-kneading temperature is preferably equal to or higher than the melting point of the liquid crystal polyester resin and not higher than the melting point of + 50 ° C.
混練方法としては、１）液晶ポリエステル樹脂、充填材やその他の添加剤を元込めフィーダーから一括で投入して混練する方法（一括混練法）、２）液晶ポリエステル樹脂とその他の添加剤を元込めフィーダーから投入して混練した後、充填材およびその他の添加剤をサイドフィーダーから添加して混練する方法（サイドフィード法）、３）液晶ポリエステル樹脂とその他の添加剤を高濃度に含む液晶ポリエステル組成物（マスターペレット）を作製し、次いで規定の濃度になるようにマスターペレットを液晶ポリエステル樹脂、充填材と混練する方法（マスターペレット法）などが挙げられる。また、充填材およびその他の添加剤を添加する方法としては、一括混練法、逐次添加法、高濃度組成物（マスター）を添加する方法等が挙げられ、いずれの方法でもかまわない。 As the kneading method, 1) the liquid crystal polyester resin, the filler and other additives are added in a batch from the feeder and kneaded (batch kneading method), and 2) the liquid crystal polyester resin and other additives are added. A method in which a filler and other additives are added from a side feeder and kneaded after being charged from a feeder and kneaded (side feed method), and 3) a liquid crystal polyester composition containing a high concentration of liquid crystal polyester resin and other additives. Examples thereof include a method of preparing a product (master pellet) and then kneading the master pellet with a liquid crystal polyester resin and a filler so as to have a specified concentration (master pellet method). In addition, examples of the method of adding the filler and other additives include a batch kneading method, a sequential addition method, a method of adding a high-concentration composition (master), and the like, and any method may be used.
本発明の液晶ポリエステル樹脂および液晶ポリエステル樹脂組成物は、通常の射出成形、押出成形、プレス成形、溶液キャスト製膜、紡糸などの成形方法によって、優れた表面外観（色調）、機械的性質、耐熱性を有する成形品に加工することが可能である。ここでいう成形品としては、射出成形品、押出成形品、プレス成形品、シート、パイプ、未延伸フィルム、一軸延伸フィルム、二軸延伸フィルムなどの各種フィルム、未延伸糸、超延伸糸などの各種繊維などが挙げられる。特に加工性の観点から射出成形であることが好ましい。溶融成形する場合、液晶ポリエステル樹脂組成物の劣化を抑制し、機械強度を向上させる観点から、３７０℃以下で溶融成形するのが好ましく、３６０℃以下がより好ましい。 The liquid crystal polyester resin and the liquid crystal polyester resin composition of the present invention have excellent surface appearance (color tone), mechanical properties, and heat resistance by molding methods such as ordinary injection molding, extrusion molding, press molding, solution casting film forming, and spinning. It is possible to process it into a molded product with properties. The molded products referred to here include injection-molded products, extrusion-molded products, press-molded products, sheets, pipes, unstretched films, uniaxially stretched films, biaxially stretched films and other various films, unstretched yarns, super-stretched yarns and the like. Various fibers and the like can be mentioned. In particular, injection molding is preferable from the viewpoint of workability. In the case of melt molding, from the viewpoint of suppressing deterioration of the liquid crystal polyester resin composition and improving the mechanical strength, melt molding is preferably performed at 370 ° C. or lower, and more preferably 360 ° C. or lower.
本発明の液晶ポリエステル樹脂および液晶ポリエステル樹脂組成物を成形して得られる成形品は、電気・電子部品として好ましく用いることができる。電気・電子部品としては、例えば、パソコン、ＧＰＳ内蔵機器、携帯電話、衝突防止用レーダーなどのミリ波および準ミリ波レーダー、タブレットやスマートフォンなどの移動通信・電子機器のアンテナに用いられるフレキシブルプリント基板、積層用回路基板、プリント配線基板および三次元回路基板；ＬＥＤなどのランプリフレクターやランプソケット、移動通信端末の通信基地局スモールセルやマイクロセル部材、アンテナカバー、筐体、センサー、カメラモジュール、コネクタ、リレーケースおよびベース、スイッチ、コイルボビン、コンデンサーなどが挙げられる。なかでも、巻き線強度やスナップフィット性に優れることから、巻き線部や他部品との嵌合部を有するコネクタ、リレー、スイッチ、コイルボビン、カメラモジュール、ランプソケットなどに有用である。 The molded product obtained by molding the liquid crystal polyester resin and the liquid crystal polyester resin composition of the present invention can be preferably used as electric / electronic parts. Electrical and electronic components include, for example, millimeter-wave and quasi-millimeter-wave radars such as personal computers, GPS built-in devices, mobile phones, collision prevention radars, and flexible printed circuit boards used for antennas of mobile communication / electronic devices such as tablets and smartphones. , Stacked circuit boards, printed wiring boards and three-dimensional circuit boards; lamp reflectors and lamp sockets such as LEDs, communication base stations for mobile communication terminals, small cells and microcell members, antenna covers, housings, sensors, camera modules, connectors , Relay cases and bases, switches, coil bobbins, capacitors, etc. Among them, since it is excellent in winding strength and snap fit, it is useful for connectors, relays, switches, coil bobbins, camera modules, lamp sockets, etc. that have a winding portion or a fitting portion with other parts.
以下、実施例を用いて本発明を説明するが、本発明が実施例により限定されるものではない。実施例中、液晶ポリエステル樹脂の組成および特性評価は以下の方法により測定した。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the examples. In the examples, the composition and characteristic evaluation of the liquid crystal polyester resin were measured by the following methods.
（１）液晶ポリエステル樹脂の組成分析
粉砕した液晶ポリエステル樹脂ペレット０．１ｍｇに、水酸化テトラメチルアンモニウム２５％メタノール溶液２μＬを添加し、島津製ＧＣＭＳ－ＱＰ５０５０Ａを用いて熱分解ＧＣ／ＭＳ測定を行い、液晶ポリエステル樹脂中の各構成成分の組成比を求めた。
(1) Composition analysis of liquid crystal polyester resin To 0.1 mg of crushed liquid crystal polyester resin pellets, 2 μL of a 25% methanol solution of tetramethylammonium hydroxide was added, and pyrolysis GC / MS measurement was performed using GCMS-QP5050A manufactured by Shimadzu. , The composition ratio of each component in the liquid crystal polyester resin was determined.
（２）液晶ポリエステルの融点（Ｔｍ）測定
示差走査熱量計ＤＳＣ－７（パーキンエルマー製）により、液晶ポリエステル樹脂を室温から２０℃／分の昇温条件で加熱した際に観測される吸熱ピーク温度（Ｔｍ１）の観測後、Ｔｍ１＋２０℃の温度で５分間保持した後、２０℃／分の降温条件で室温まで一旦冷却し、再度２０℃／分の昇温条件で加熱した際に観測される吸熱ピーク温度を融点（Ｔｍ）とした。
(2) Measurement of melting point (Tm) of liquid crystal polyester The heat absorption peak temperature observed when the liquid crystal polyester resin is heated from room temperature to 20 ° C./min with a differential scanning calorimeter DSC-7 (manufactured by Parkin Elmer). After observing (Tm 1 ), it was held at a temperature of Tm 1 + 20 ° C. for 5 minutes, then cooled to room temperature under a temperature decrease condition of 20 ° C./min, and then heated again under a temperature rise condition of 20 ° C./min. The heat absorption peak temperature was taken as the melting point (Tm).
（３）液晶ポリエステル樹脂の溶融粘度
高化式フローテスターＣＦＴ－５００Ｄ（オリフィス０．５φ×１０ｍｍ）（島津製作所製）を用いて、Ｔｍ＋２０℃で、せん断速度１０００／ｓの条件で液晶ポリエステル樹脂の溶融粘度を測定した。
(3) Melt viscosity of liquid crystal polyester resin Using a flow tester CFT-500D (operator 0.5φ x 10 mm) (manufactured by Shimadzu Corporation), the liquid crystal polyester resin is prepared at Tm + 20 ° C. and a shear rate of 1000 / s. The melt viscosity was measured.
（４）円筒状成形品の巻き線強度評価
液晶ポリエステル樹脂を、熱風乾燥機を用いて１５０℃で３時間乾燥した後、ファナックα３０Ｃ射出成形機（ファナック製スクリュー径２８ｍｍ）に供し、シリンダー温度を液晶ポリエステル樹脂の融点＋１０℃、金型温度を９０℃として、高さ１５ｍｍ、φ８ｍｍ、壁厚０．１５ｍｍの円筒状成形品を成形した。得られた成形品について、オリエンテック製テンシロンＵＴＲ－１Ｔにより先端角度Ｒ：０．５の治具を速度０．５ｍｍ／分で降下させて荷重を掛け、その一次ピーク圧（Ｎ）を測定し、巻き線強度を評価した。一次ピーク圧が高いほど、巻き線強度に優れる。
(4) Evaluation of winding strength of cylindrical molded product The liquid crystal polyester resin was dried at 150 ° C. for 3 hours using a hot air dryer, and then subjected to a Fanac α30C injection molding machine (Fanac screw diameter 28 mm) to adjust the cylinder temperature. A cylindrical molded product having a height of 15 mm, a diameter of 8 mm, and a wall thickness of 0.15 mm was molded by setting the melting point of the liquid crystal polyester resin to + 10 ° C. and the mold temperature to 90 ° C. With respect to the obtained molded product, a jig with a tip angle R: 0.5 was lowered at a speed of 0.5 mm / min with a Tensilon UTR-1T manufactured by Orientech, a load was applied, and the primary peak pressure (N) was measured. , The winding strength was evaluated. The higher the primary peak pressure, the better the winding strength.
（５）スナップフィット性の評価
液晶ポリエステル樹脂を、熱風乾燥機を用いて１５０℃で３時間乾燥した後、ファナックα３０Ｃ射出成形機（ファナック製、スクリュー径２８ｍｍ）に供し、シリンダー温度を液晶ポリエステル樹脂の融点＋１０℃、金型温度を９０℃として、図１に示すスナップフィット部を有する成形品と、図２に示す縦５ｍｍ×横３９．５ｍｍ×高さ２．７ｍｍの角板を成形し、角板の中心を押して、スナップフィット部を有する成形品へのはめ込みテストを３０個行った。スナップフィット部を有する成形品の爪が折れず、かつ角板がはまった個数でスナップフィット性を評価した。個数が多いほどスナップフィット性に優れる。
(5) Evaluation of snap-fitting property The liquid crystal polyester resin was dried at 150 ° C. for 3 hours using a hot air dryer, and then subjected to a Fanac α30C injection molding machine (manufactured by Fanac, screw diameter 28 mm) to set the cylinder temperature to the liquid crystal polyester resin. With a melting point of + 10 ° C. and a mold temperature of 90 ° C., a molded product having a snap-fit portion shown in FIG. 1 and a square plate having a length of 5 mm, a width of 39.5 mm, and a height of 2.7 mm shown in FIG. 2 were molded. By pressing the center of the square plate, 30 fitting tests were performed on a molded product having a snap-fit portion. The snap-fitting property was evaluated by the number of the claws of the molded product having the snap-fitting portion that did not break and the square plates were fitted. The larger the number, the better the snap fit.
［実施例１］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ－ヒドロキシ安息香酸９０５重量部、６－ヒドロキシ－２－ナフトエ酸８８重量部、４，４’－ジヒドロキシビフェニル４３６重量部、テレフタル酸３８９重量部および無水酢酸１３１４重量部（フェノール性水酸基合計の１．１０当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４５℃で１２０分反応させた後、１４５℃から３６０℃まで４時間かけて昇温した。その後、重合温度を３６０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ－１）を得た。
[Example 1]
905 parts by weight of p-hydroxybenzoic acid, 88 parts by weight of 6-hydroxy-2-naphthoic acid, 436 parts by weight of 4,4'-dihydroxybiphenyl, 389 parts by weight of terephthalic acid in a 5 L reaction vessel equipped with a stirring blade and a distillate. A portion and 1314 parts by weight of anhydrous acetic acid (1.10 equivalent of the total phenolic hydroxyl group) were charged and reacted at 145 ° C. for 120 minutes while stirring in a nitrogen gas atmosphere, and then ascended from 145 ° C. to 360 ° C. over 4 hours. It was warm. Then, the polymerization temperature was maintained at 360 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm 2 (0.1 MPa), the polymer is discharged in a strand shape via a mouthpiece having one circular discharge port having a diameter of 10 mm, and the liquid crystal is pelletized by a cutter. A polyester resin (A-1) was obtained.
この液晶ポリエステル樹脂（Ａ－１）のＴｍは３４２℃、溶融粘度は２７Ｐａ・ｓであった。 The Tm of this liquid crystal polyester resin (A-1) was 342 ° C., and the melt viscosity was 27 Pa · s.
［実施例２］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ－ヒドロキシ安息香酸８５７重量部、６－ヒドロキシ－２－ナフトエ酸１１０重量部、４，４’－ジヒドロキシビフェニル４５８重量部、テレフタル酸４０８重量部および無水酢酸１３１４重量部（フェノール性水酸基合計の１．１０当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４５℃で１２０分反応させた後、１４５℃から３６０℃まで４時間かけて昇温した。その後、重合温度を３６０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ－２）を得た。
[Example 2]
857 parts by weight of p-hydroxybenzoic acid, 110 parts by weight of 6-hydroxy-2-naphthoic acid, 458 parts by weight of 4,4'-dihydroxybiphenyl, 408 parts by weight of terephthalic acid in a 5 L reaction vessel equipped with a stirring blade and a distillate. A portion and 1314 parts by weight of anhydrous acetic acid (1.10 equivalent of the total phenolic hydroxyl group) were charged and reacted at 145 ° C. for 120 minutes while stirring in a nitrogen gas atmosphere, and then ascended from 145 ° C. to 360 ° C. over 4 hours. It was warm. Then, the polymerization temperature was maintained at 360 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm 2 (0.1 MPa), the polymer is discharged in a strand shape via a mouthpiece having one circular discharge port having a diameter of 10 mm, and the liquid crystal is pelletized by a cutter. A polyester resin (A-2) was obtained.
この液晶ポリエステル樹脂（Ａ－２）のＴｍは３４０℃、溶融粘度は２６Ｐａ・ｓであった。 The Tm of this liquid crystal polyester resin (A-2) was 340 ° C., and the melt viscosity was 26 Pa · s.
［実施例３］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ－ヒドロキシ安息香酸９１６重量部、６－ヒドロキシ－２－ナフトエ酸７３重量部、４，４’－ジヒドロキシビフェニル４３６重量部、テレフタル酸３８９重量部および無水酢酸１３１４重量部（フェノール性水酸基合計の１．１０当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４５℃で１２０分反応させた後、１４５℃から３６０℃まで４時間かけて昇温した。その後、重合温度を３６０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ－３）を得た。
[Example 3]
916 parts by weight of p-hydroxybenzoic acid, 73 parts by weight of 6-hydroxy-2-naphthoic acid, 436 parts by weight of 4,4'-dihydroxybiphenyl, 389 parts by weight of terephthalic acid in a 5 L reaction vessel equipped with a stirring blade and a distillate. A portion and 1314 parts by weight of anhydrous acetic acid (1.10 equivalent of the total phenolic hydroxyl group) were charged and reacted at 145 ° C. for 120 minutes while stirring in a nitrogen gas atmosphere, and then ascended from 145 ° C. to 360 ° C. over 4 hours. It was warm. Then, the polymerization temperature was maintained at 360 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm 2 (0.1 MPa), the polymer is discharged in a strand shape via a mouthpiece having one circular discharge port having a diameter of 10 mm, and the liquid crystal is pelletized by a cutter. A polyester resin (A-3) was obtained.
この液晶ポリエステル樹脂（Ａ－３）のＴｍは３５２℃、溶融粘度は３１Ｐａ・ｓであった。 The Tm of this liquid crystal polyester resin (A-3) was 352 ° C., and the melt viscosity was 31 Pa · s.
［実施例４］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ－ヒドロキシ安息香酸８０８重量部、６－ヒドロキシ－２－ナフトエ酸１３２重量部、４，４’－ジヒドロキシビフェニル４７９重量部、テレフタル酸４２８重量部および無水酢酸１３１４重量部（フェノール性水酸基合計の１．１０当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４５℃で１２０分反応させた後、１４５℃から３６０℃まで４時間かけて昇温した。その後、重合温度を３６０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ－４）を得た。
[Example 4]
808 parts by weight of p-hydroxybenzoic acid, 132 parts by weight of 6-hydroxy-2-naphthoic acid, 479 parts by weight of 4,4'-dihydroxybiphenyl, 428 parts by weight of terephthalic acid in a 5 L reaction vessel equipped with a stirring blade and a distillate. A portion and 1314 parts by weight of anhydrous acetic acid (1.10 equivalent of the total phenolic hydroxyl group) were charged and reacted at 145 ° C. for 120 minutes while stirring in a nitrogen gas atmosphere, and then ascended from 145 ° C. to 360 ° C. over 4 hours. It was warm. Then, the polymerization temperature was maintained at 360 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm 2 (0.1 MPa), the polymer is discharged in a strand shape via a mouthpiece having one circular discharge port having a diameter of 10 mm, and the liquid crystal is pelletized by a cutter. A polyester resin (A-4) was obtained.
この液晶ポリエステル樹脂（Ａ－４）のＴｍは３３８℃、溶融粘度は２４Ｐａ・ｓであった。 The Tm of this liquid crystal polyester resin (A-4) was 338 ° C., and the melt viscosity was 24 Pa · s.
［実施例５］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ－ヒドロキシ安息香酸９０５重量部、６－ヒドロキシ－２－ナフトエ酸８８重量部、４，４’－ジヒドロキシビフェニル４３６重量部、テレフタル酸３６９重量部、イソフタル酸１９重量部および無水酢酸１３１４重量部（フェノール性水酸基合計の１．１０当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４５℃で１２０分反応させた後、１４５℃から３６０℃まで４時間かけて昇温した。その後、重合温度を３６０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ－５）を得た。
[Example 5]
905 parts by weight of p-hydroxybenzoic acid, 88 parts by weight of 6-hydroxy-2-naphthoic acid, 436 parts by weight of 4,4'-dihydroxybiphenyl, 369 parts by weight of terephthalic acid in a 5 L reaction vessel equipped with a stirring blade and a distillate. , 19 parts by weight of isophthalic acid and 1314 parts by weight of anhydrous acetic acid (1.10 equivalent of the total phenolic hydroxyl groups) were charged and reacted at 145 ° C. for 120 minutes while stirring in a nitrogen gas atmosphere, and then 145 ° C. to 360 ° C. The temperature was raised over 4 hours. Then, the polymerization temperature was maintained at 360 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm 2 (0.1 MPa), the polymer is discharged in a strand shape via a mouthpiece having one circular discharge port having a diameter of 10 mm, and the liquid crystal is pelletized by a cutter. A polyester resin (A-5) was obtained.
この液晶ポリエステル樹脂（Ａ－５）のＴｍは３３８℃、溶融粘度は２６Ｐａ・ｓであった。 The Tm of this liquid crystal polyester resin (A-5) was 338 ° C., and the melt viscosity was 26 Pa · s.
［実施例６］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ－ヒドロキシ安息香酸９４６重量部、６－ヒドロキシ－２－ナフトエ酸７７重量部、４，４’－ジヒドロキシビフェニル４１４重量部、テレフタル酸３６９重量部および無水酢酸１３１４重量部（フェノール性水酸基合計の１．１０当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４５℃で１２０分反応させた後、１４５℃から３６０℃まで４時間かけて昇温した。その後、重合温度を３６０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ－６）を得た。
[Example 6]
946 parts by weight of p-hydroxybenzoic acid, 77 parts by weight of 6-hydroxy-2-naphthoic acid, 414 parts by weight of 4,4'-dihydroxybiphenyl, 369 parts by weight of terephthalic acid in a 5 L reaction vessel equipped with a stirring blade and a distillate. A portion and 1314 parts by weight of anhydrous acetic acid (1.10 equivalent of the total phenolic hydroxyl group) were charged and reacted at 145 ° C. for 120 minutes while stirring in a nitrogen gas atmosphere, and then ascended from 145 ° C. to 360 ° C. over 4 hours. It was warm. Then, the polymerization temperature was maintained at 360 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm 2 (0.1 MPa), the polymer is discharged in a strand shape via a mouthpiece having one circular discharge port having a diameter of 10 mm, and the liquid crystal is pelletized by a cutter. A polyester resin (A-6) was obtained.
この液晶ポリエステル樹脂（Ａ－６）のＴｍは３４４℃、溶融粘度は３０Ｐａ・ｓであった。 The Tm of this liquid crystal polyester resin (A-6) was 344 ° C., and the melt viscosity was 30 Pa · s.
［実施例７］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ－ヒドロキシ安息香酸７１１重量部、６－ヒドロキシ－２－ナフトエ酸１７６重量部、４，４’－ジヒドロキシビフェニル５２３重量部、テレフタル酸４６７重量部および無水酢酸１３１４重量部（フェノール性水酸基合計の１．１０当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４５℃で１２０分反応させた後、１４５℃から３６０℃まで４時間かけて昇温した。その後、重合温度を３６０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ－７）を得た。
[Example 7]
711 parts by weight of p-hydroxybenzoic acid, 176 parts by weight of 6-hydroxy-2-naphthoic acid, 523 parts by weight of 4,4'-dihydroxybiphenyl, 467 parts by weight of terephthalic acid in a 5 L reaction vessel equipped with a stirring blade and a distillate. A portion and 1314 parts by weight of anhydrous acetic acid (1.10 equivalent of the total phenolic hydroxyl group) were charged and reacted at 145 ° C. for 120 minutes while stirring in a nitrogen gas atmosphere, and then ascended from 145 ° C. to 360 ° C. over 4 hours. It was warm. Then, the polymerization temperature was maintained at 360 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm 2 (0.1 MPa), the polymer is discharged in a strand shape via a mouthpiece having one circular discharge port having a diameter of 10 mm, and the liquid crystal is pelletized by a cutter. A polyester resin (A-7) was obtained.
この液晶ポリエステル樹脂（Ａ－７）は、Ｔｍは３２５℃、溶融粘度は２２Ｐａ・ｓであった。 The liquid crystal polyester resin (A-7) had a Tm of 325 ° C. and a melt viscosity of 22 Pa · s.
［比較例１］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ－ヒドロキシ安息香酸８７０重量部、４，４’－ジヒドロキシビフェニル３５２重量部、ハイドロキノン８９重量部、テレフタル酸２９２重量部、イソフタル酸１５７重量部および無水酢酸１２７８重量部（フェノール性水酸基合計の１．０７当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４５℃で１２０分反応させた後、１４５℃から３２５℃まで４時間かけて昇温した。その後、重合温度を３２５℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状物に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ－８）を得た。
[Comparative Example 1]
870 parts by weight of p-hydroxybenzoic acid, 352 parts by weight of 4,4'-dihydroxybiphenyl, 89 parts by weight of hydroquinone, 292 parts by weight of terephthalic acid, 157 parts by weight of isophthalic acid in a 5 L reaction vessel equipped with a stirring blade and a distillate. And 1278 parts by weight of anhydrous acetic acid (1.07 equivalent of the total phenolic hydroxyl group) was charged and reacted at 145 ° C. for 120 minutes while stirring in a nitrogen gas atmosphere, and then the temperature was raised from 145 ° C. to 325 ° C. over 4 hours. bottom. Then, the polymerization temperature was maintained at 325 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm 2 (0.1 MPa), the polymer is discharged into a strand-like material via a mouthpiece having one circular discharge port having a diameter of 10 mm, and the polymer is pelletized by a cutter. A liquid crystal polyester resin (A-8) was obtained.
この液晶ポリエステル樹脂（Ａ－８）のＴｍは３１４℃、溶融粘度は２５Ｐａ・ｓであった。 The Tm of this liquid crystal polyester resin (A-8) was 314 ° C., and the melt viscosity was 25 Pa · s.
［比較例２］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ－ヒドロキシ安息香酸９１４重量部、６－ヒドロキシ－２－ナフトエ酸６７重量部、４，４’－ジヒドロキシビフェニル３７７重量部、テレフタル酸３３６重量部および無水酢酸１２１５重量部（フェノール性水酸基合計の１．０８当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４０℃で１２０分反応させた後、１４０℃から３５０℃まで４時間かけて昇温した。その後、重合温度を３５０℃に保持し、１．０時間かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ－９）を得た。
[Comparative Example 2]
914 parts by weight of p-hydroxybenzoic acid, 67 parts by weight of 6-hydroxy-2-naphthoic acid, 377 parts by weight of 4,4'-dihydroxybiphenyl, 336 parts by weight of terephthalic acid in a 5 L reaction vessel equipped with a stirring blade and a distillate. 1215 parts by weight of anhydrous acetic acid (1.08 equivalent of the total phenolic hydroxyl group) was charged and reacted at 140 ° C. for 120 minutes while stirring in a nitrogen gas atmosphere, and then ascended from 140 ° C. to 350 ° C. over 4 hours. It was warm. Then, the polymerization temperature was maintained at 350 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 1.0 hour, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm 2 (0.1 MPa), the polymer is discharged in a strand shape via a mouthpiece having one circular discharge port having a diameter of 10 mm, and the liquid crystal is pelletized by a cutter. A polyester resin (A-9) was obtained.
この液晶ポリエステル樹脂（Ａ－９）のＴｍは３３６℃、溶融粘度は２４Ｐａ・ｓであった。 The Tm of this liquid crystal polyester resin (A-9) was 336 ° C., and the melt viscosity was 24 Pa · s.
［比較例３］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ－ヒドロキシ安息香酸７７６重量部、６－ヒドロキシ－２－ナフトエ酸６６重量部、４，４’－ジヒドロキシビフェニル５３０重量部、テレフタル酸４２２重量部、イソフタル酸５８重量部および無水酢酸１２２６重量部（フェノール性水酸基合計の１．０３当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１４０℃で６０分反応させた後、１４０℃から３６０℃まで５．５時間かけて昇温した。その後、重合温度を３６０℃に保持し、２０分かけて１．０ｍｍＨｇ（１３３Ｐａ）に減圧し、更に反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ－１０）を得た。
[Comparative Example 3]
776 parts by weight of p-hydroxybenzoic acid, 66 parts by weight of 6-hydroxy-2-naphthoic acid, 530 parts by weight of 4,4'-dihydroxybiphenyl, 422 parts by weight of terephthalic acid in a 5 L reaction vessel equipped with a stirring blade and a distillate. Parts, 58 parts by weight of isophthalic acid and 1226 parts by weight of anhydrous acetic acid (1.03 equivalent of the total phenolic hydroxyl groups) were charged and reacted at 140 ° C. for 60 minutes while stirring in a nitrogen gas atmosphere, and then 140 ° C. to 360 ° C. The temperature was raised over 5.5 hours. Then, the polymerization temperature was maintained at 360 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) over 20 minutes, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm 2 (0.1 MPa), the polymer is discharged in a strand shape via a mouthpiece having one circular discharge port having a diameter of 10 mm, and the liquid crystal is pelletized by a cutter. A polyester resin (A-10) was obtained.
この液晶ポリエステル樹脂（Ａ－１０）のＴｍは３６１℃、溶融粘度は１７Ｐａ・ｓであった。 The Tm of this liquid crystal polyester resin (A-10) was 361 ° C., and the melt viscosity was 17 Pa · s.
［比較例４］
撹拌翼および留出管を備えた５Ｌの反応容器にｐ－ヒドロキシ安息香酸６７９重量部、６－ヒドロキシ－２－ナフトエ酸３５２重量部、４，４’－ジヒドロキシビフェニル４５８重量部、テレフタル酸４０８重量部および無水酢酸１２３１重量部（フェノール性水酸基合計の１．０３当量）を仕込み、窒素ガス雰囲気下で撹拌しながら１５０℃で９０分反応させた後、１５０℃から３５０℃まで７時間かけて昇温した。その後、重合温度を３５０℃に保持し、８０分かけて５．０ｍｍＨｇ（６６５Ｐａ）に減圧し、更に反応を続け、撹拌に要するトルクが２０ｋｇ・ｃｍに到達したところで重合を完了させた。次に反応容器内を１．０ｋｇ／ｃｍ２（０．１ＭＰａ）に加圧し、直径１０ｍｍの円形吐出口を１ケ持つ口金を経由してポリマーをストランド状に吐出し、カッターによりペレタイズして液晶ポリエステル樹脂（Ａ－１１）を得た。
[Comparative Example 4]
679 parts by weight of p-hydroxybenzoic acid, 352 parts by weight of 6-hydroxy-2-naphthoic acid, 458 parts by weight of 4,4'-dihydroxybiphenyl, 408 parts by weight of terephthalic acid in a 5 L reaction vessel equipped with a stirring blade and a distillate. A portion and 1231 parts by weight of anhydrous acetic acid (1.03 equivalent of the total phenolic hydroxyl group) were charged and reacted at 150 ° C. for 90 minutes while stirring in a nitrogen gas atmosphere, and then ascended from 150 ° C. to 350 ° C. over 7 hours. It was warm. Then, the polymerization temperature was maintained at 350 ° C., the pressure was reduced to 5.0 mmHg (665 Pa) over 80 minutes, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm 2 (0.1 MPa), the polymer is discharged in a strand shape via a mouthpiece having one circular discharge port having a diameter of 10 mm, and the liquid crystal is pelletized by a cutter. A polyester resin (A-11) was obtained.
この液晶ポリエステル樹脂（Ａ－１１）のＴｍは３３０℃、溶融粘度は１９Ｐａ・ｓであった。 The Tm of this liquid crystal polyester resin (A-11) was 330 ° C., and the melt viscosity was 19 Pa · s.
実施例１～７および比較例１～４で得られたペレットについて、上記（１）に記載の方法で組成分析を行った結果、および（４）（５）の評価を行った結果を表１に示す。 Table 1 shows the results of composition analysis of the pellets obtained in Examples 1 to 7 and Comparative Examples 1 to 4 by the method described in (1) above, and the evaluation results of (4) and (5). Shown in.
実施例１～７および比較例１～４で得られた液晶ポリエステル樹脂に対して、さらに充填材を加えて、液晶ポリエステル樹脂組成物を作製した。各実施例および比較例において用いた充填材を次に示す。 A filler was further added to the liquid crystal polyester resins obtained in Examples 1 to 7 and Comparative Examples 1 to 4 to prepare a liquid crystal polyester resin composition. The filler used in each Example and Comparative Example is shown below.
充填材（Ｂ）
（Ｂ－１）日本電気硝子製 ミルドファイバー（４０Ｍ－１０Ａ）
（Ｂ－２）ヤマグチマイカ製 マイカ（Ａ－２１）
［実施例８～９、比較例５～６］
サイドフィーダーを備えた東芝機械製ＴＥＭ３５Ｂ型２軸押出機で、各製造例で得られた液晶ポリエステル樹脂（Ａ－１、Ａ－９）を表２に示す配合量でホッパーから投入し、充填材（Ｂ－１、Ｂ－２）を表２に示す配合量でサイドから投入し、シリンダー温度を液晶ポリエステル樹脂の融点＋１０℃に設定し、溶融混練してペレットとした。得られた液晶ポリエステル樹脂組成物のペレットを熱風乾燥後、（４）の評価を行った結果、および図１のスナップフィット部を有する成形品について、爪長さを１．９ｍｍ、爪高さを１．５ｍｍとした以外は（５）と同様に評価を行った結果を表２に示す。
Filler (B)
(B-1) Nippon Electric Glass Milled Fiber (40M-10A)
(B-2) Mica made by Yamaguchi Mica (A-21)
[Examples 8 to 9, Comparative Examples 5 to 6]
With a TEM35B type twin-screw extruder manufactured by Toshiba Machine Co., Ltd. equipped with a side feeder, the liquid crystal polyester resins (A-1, A-9) obtained in each production example are charged from the hopper in the blending amounts shown in Table 2 and used as a filler. (B-1, B-2) were added from the side in the blending amounts shown in Table 2, the cylinder temperature was set to the melting point of the liquid crystal polyester resin + 10 ° C., and melt-kneaded to obtain pellets. After drying the pellets of the obtained liquid crystal polyester resin composition with hot air, the evaluation of (4) was performed, and the molded product having the snap-fit portion of FIG. 1 had a claw length of 1.9 mm and a claw height. Table 2 shows the results of evaluation in the same manner as in (5) except that the thickness was 1.5 mm.
表１および表２の結果から、構造単位（Ｉ）～（ＩＶ）を所定量含む液晶ポリエステル樹脂、または該樹脂を用いた液晶ポリエステル樹脂組成物を用いることにより、円筒状成形品の巻き線強度およびスナップフィット性に優れる成形品を得ることができる。 From the results in Tables 1 and 2, by using a liquid crystal polyester resin containing a predetermined amount of structural units (I) to (IV) or a liquid crystal polyester resin composition using the resin, the winding strength of the cylindrical molded product is obtained. And a molded product having excellent snap-fitting property can be obtained.
本発明の液晶ポリエステル樹脂および液晶ポリエステル樹脂組成物は、円筒状成形品の巻き線強度およびスナップフィット性に優れるため、巻き線部や他部品との嵌合部を有するコネクタ、リレー、スイッチ、コイルボビン、カメラモジュール、ランプソケットなどの電気・電子部品や機械部品用途に好適である。 Since the liquid crystal polyester resin and the liquid crystal polyester resin composition of the present invention are excellent in winding strength and snap fit of a cylindrical molded product, a connector, a relay, a switch, and a coil bobbin having a winding portion and a fitting portion with other parts are provided. , Suitable for electrical / electronic parts such as camera modules and lamp sockets, and mechanical parts.
１ スナップフィット部を有する成形品
２ スナップフィット部を有する成形品へはめ込む角板
1 Molded product with a snap-
Claims (6)
４４≦［Ｉ］≦５９ ・・・（Ａ）
２≦［ＩＩ］≦１０ ・・・（Ｂ）
１８．５≦［ＩＩＩ］≦２６ ・・・（Ｃ）
１８．５≦［ＩＶ］≦２６ ・・・（Ｄ）
９９≦［Ｉ］＋［ＩＩ］＋［ＩＩＩ］＋［ＩＶ］≦１００ ・・・（Ｅ）
（［Ｉ］～［ＩＶ］は、液晶ポリエステル樹脂の全構造単位１００モル％に対する、各構造単位（Ｉ）～（ＩＶ）の含有量（モル％）を示す。）
44 ≤ [I] ≤ 59 ... (A)
2 ≦ [II] ≦ 10 ・ ・ ・ (B)
18.5 ≤ [III] ≤ 26 ... (C)
18.5 ≤ [IV] ≤ 26 ... (D)
99 ≤ [I] + [II] + [III] + [IV] ≤ 100 ... (E)
([I] to [IV] indicate the content (mol%) of each structural unit (I) to (IV) with respect to 100 mol% of all structural units of the liquid crystal polyester resin.)
３＜［ＩＩ］≦５．７ ・・・（Ｆ） The liquid crystal polyester resin according to claim 1, which further satisfies the following formula (F).
3 <[II] ≤ 5.7 ... (F)
１０＜［Ｉ］／［ＩＩ］＜１５ ・・・（Ｇ） The liquid crystal polyester resin according to claim 1 or 2, which further satisfies the following formula (G).
10 <[I] / [II] <15 ... (G)
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