JP2018203810A - Liquid crystal polymer composition - Google Patents
Liquid crystal polymer composition Download PDFInfo
- Publication number
- JP2018203810A JP2018203810A JP2017107023A JP2017107023A JP2018203810A JP 2018203810 A JP2018203810 A JP 2018203810A JP 2017107023 A JP2017107023 A JP 2017107023A JP 2017107023 A JP2017107023 A JP 2017107023A JP 2018203810 A JP2018203810 A JP 2018203810A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- crystal polymer
- polymer composition
- acid
- unit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000106 Liquid crystal polymer Polymers 0.000 title claims abstract description 124
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 title claims abstract description 123
- 239000000203 mixture Substances 0.000 title claims abstract description 66
- 239000000945 filler Substances 0.000 claims abstract description 24
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 17
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 15
- -1 melamine compound Chemical class 0.000 claims description 36
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 14
- 239000005977 Ethylene Substances 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 14
- 229920000877 Melamine resin Polymers 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 10
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 9
- 238000005452 bending Methods 0.000 claims description 8
- 239000004973 liquid crystal related substance Substances 0.000 claims description 7
- 239000000454 talc Substances 0.000 claims description 7
- 229910052623 talc Inorganic materials 0.000 claims description 7
- 239000004927 clay Substances 0.000 claims description 5
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 5
- 229920001225 polyester resin Polymers 0.000 claims description 5
- 239000004645 polyester resin Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 3
- 229910052570 clay Inorganic materials 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-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
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- HPJKLCJJNFVOEM-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;hydrochloride Chemical compound Cl.NC1=NC(N)=NC(N)=N1 HPJKLCJJNFVOEM-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical group CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- IUTYMBRQELGIRS-UHFFFAOYSA-N boric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OB(O)O.NC1=NC(N)=NC(N)=N1 IUTYMBRQELGIRS-UHFFFAOYSA-N 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 claims description 2
- QCTJRYGLPAFRMS-UHFFFAOYSA-N prop-2-enoic acid;1,3,5-triazine-2,4,6-triamine Chemical compound OC(=O)C=C.NC1=NC(N)=NC(N)=N1 QCTJRYGLPAFRMS-UHFFFAOYSA-N 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 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 44
- 239000000047 product Substances 0.000 description 29
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 24
- 239000000178 monomer Substances 0.000 description 23
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 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 15
- 150000001875 compounds Chemical class 0.000 description 15
- 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 14
- 238000000465 moulding Methods 0.000 description 14
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 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 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000194 fatty acid Substances 0.000 description 8
- 229930195729 fatty acid Natural products 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 3
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-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
- 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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229960001755 resorcinol Drugs 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical group NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical group C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 description 1
- DDAPSNKEOHDLKB-UHFFFAOYSA-N 1-(2-aminonaphthalen-1-yl)naphthalen-2-amine Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3N)=C(N)C=CC2=C1 DDAPSNKEOHDLKB-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- OHLSHRJUBRUKAN-UHFFFAOYSA-N 2,3-dihydroxyterephthalic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C(O)=C1O OHLSHRJUBRUKAN-UHFFFAOYSA-N 0.000 description 1
- LODHFNUFVRVKTH-ZHACJKMWSA-N 2-hydroxy-n'-[(e)-3-phenylprop-2-enoyl]benzohydrazide Chemical compound OC1=CC=CC=C1C(=O)NNC(=O)\C=C\C1=CC=CC=C1 LODHFNUFVRVKTH-ZHACJKMWSA-N 0.000 description 1
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 1
- AJHPGXZOIAYYDW-UHFFFAOYSA-N 3-(2-cyanophenyl)-2-[(2-methylpropan-2-yl)oxycarbonylamino]propanoic acid Chemical compound CC(C)(C)OC(=O)NC(C(O)=O)CC1=CC=CC=C1C#N AJHPGXZOIAYYDW-UHFFFAOYSA-N 0.000 description 1
- VZQSBJKDSWXLKX-UHFFFAOYSA-N 3-(3-hydroxyphenyl)phenol Chemical group OC1=CC=CC(C=2C=C(O)C=CC=2)=C1 VZQSBJKDSWXLKX-UHFFFAOYSA-N 0.000 description 1
- GSYIVQLTSZFJRV-UHFFFAOYSA-N 3-(4-carboxyphenyl)benzoic acid Chemical group C1=CC(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1 GSYIVQLTSZFJRV-UHFFFAOYSA-N 0.000 description 1
- BWBGEYQWIHXDKY-UHFFFAOYSA-N 3-(4-hydroxyphenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=CC(O)=C1 BWBGEYQWIHXDKY-UHFFFAOYSA-N 0.000 description 1
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- LQZZZAFQKXTFKH-UHFFFAOYSA-N 4'-aminobiphenyl-4-ol Chemical group C1=CC(N)=CC=C1C1=CC=C(O)C=C1 LQZZZAFQKXTFKH-UHFFFAOYSA-N 0.000 description 1
- FMRQKJAIESQKBU-UHFFFAOYSA-N 4-(3-amino-7-thiabicyclo[4.1.0]hepta-2,4-dien-6-yl)phenol Chemical compound C1=CC(N)=CC2SC21C1=CC=C(O)C=C1 FMRQKJAIESQKBU-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical group C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- FDHZNXYLISNHCG-UHFFFAOYSA-N 4-[2-(4-carboxyphenyl)phenyl]benzoic acid Chemical group C1(=CC=C(C=C1)C(=O)O)C=1C(=CC=CC1)C1=CC=C(C=C1)C(=O)O FDHZNXYLISNHCG-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-PZFLKRBQSA-N 4-amino-3,5-ditritiobenzoic acid Chemical compound [3H]c1cc(cc([3H])c1N)C(O)=O ALYNCZNDIQEVRV-PZFLKRBQSA-N 0.000 description 1
- ABJQKDJOYSQVFX-UHFFFAOYSA-N 4-aminonaphthalen-1-ol Chemical compound C1=CC=C2C(N)=CC=C(O)C2=C1 ABJQKDJOYSQVFX-UHFFFAOYSA-N 0.000 description 1
- QGNGOGOOPUYKMC-UHFFFAOYSA-N 4-hydroxy-6-methylaniline Chemical compound CC1=CC(O)=CC=C1N QGNGOGOOPUYKMC-UHFFFAOYSA-N 0.000 description 1
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 1
- SMAMQSIENGBTRV-UHFFFAOYSA-N 5-hydroxynaphthalene-2-carboxylic acid Chemical compound OC1=CC=CC2=CC(C(=O)O)=CC=C21 SMAMQSIENGBTRV-UHFFFAOYSA-N 0.000 description 1
- NZTPZUIIYNYZKT-UHFFFAOYSA-N 6-aminonaphthalene-2-carboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(N)=CC=C21 NZTPZUIIYNYZKT-UHFFFAOYSA-N 0.000 description 1
- 208000010444 Acidosis Diseases 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000004605 External Lubricant Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000007950 acidosis Effects 0.000 description 1
- 208000026545 acidosis disease Diseases 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-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
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229910052736 halogen Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011835 investigation Methods 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
- 238000004898 kneading Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical group C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- VAWFFNJAPKXVPH-UHFFFAOYSA-N naphthalene-1,6-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC2=CC(C(=O)O)=CC=C21 VAWFFNJAPKXVPH-UHFFFAOYSA-N 0.000 description 1
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
Landscapes
- Package Frames And Binding Bands (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
本発明は、柔軟性、伸び性および成形時の流動性に優れた液晶ポリマー組成物に関する。 The present invention relates to a liquid crystal polymer composition excellent in flexibility, extensibility, and fluidity during molding.
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、高強度、耐薬品性、寸法精度、低吸水性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 polymer (hereinafter abbreviated as liquid crystal polymer or LCP) is excellent in heat resistance, high strength, chemical resistance, dimensional accuracy, low water absorption, etc., and therefore its 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、スマートフォン、自動車等の電気・電子分野においては、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、これに伴う樹脂部材の薄肉化が求められている。そこで、液晶ポリマーはその優れた成形性、すなわち薄肉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。 In particular, in the electrical and electronic fields such as personal computers, mobile phones, smartphones, automobiles, etc., there is a rapid increase in the degree of integration, miniaturization, thinning, and low profile of parts. Is required. Therefore, the amount of the liquid crystal polymer used is greatly increased by taking advantage of its excellent moldability, i.e., thin-walled fluidity, and no characteristics of other resins such as no burrs.
しかし、液晶ポリマーは分子構造が剛直であるが故に柔軟性や伸び性に劣るといった欠点がある。電気・電子分野で重要な部品の１つであるコネクタ部品においては、部品同士の接続に嵌合が必要であるため、柔軟性や伸び性も求められる。材料評価の観点では、引張強度と引張破断伸びの積である抗張積が１つの基準となり、強度と伸びを兼ね備えた、抗張積の大きい液晶ポリマーが求められている。 However, since the liquid crystal polymer has a rigid molecular structure, it has a drawback of being inferior in flexibility and extensibility. In connector parts that are one of the important parts in the electric / electronic field, fitting is required for connection between the parts, so flexibility and stretchability are also required. From the viewpoint of material evaluation, the tensile product, which is the product of tensile strength and tensile elongation at break, is one criterion, and a liquid crystal polymer having a high tensile product that has both strength and elongation is required.
特許文献１には、靱性に優れた液晶ポリエステルアミド樹脂組成物について記載されている。しかし、特許文献１に記載の樹脂組成物は成形加工温度ならびに溶融粘度が高いため、成形加工性が不十分であるといった課題があった。 Patent Document 1 describes a liquid crystal polyesteramide resin composition having excellent toughness. However, since the resin composition described in Patent Document 1 has a high molding process temperature and melt viscosity, there is a problem that the moldability is insufficient.
特許文献２には、引張物性に優れた液晶ポリマー組成物として、液晶ポリマーにエポキシ基含有エチレン共重合体および表面無処理のガラス繊維を含有させた組成物が提案されている。しかしながら、特許文献２に記載の液晶ポリマー組成物は、表面無処理のガラス繊維を含有することによって溶融粘度が高くなり、引張伸びの改善が不十分であるといった課題があった。 Patent Document 2 proposes a composition in which an epoxy group-containing ethylene copolymer and non-surface-treated glass fibers are contained in a liquid crystal polymer as a liquid crystal polymer composition having excellent tensile properties. However, the liquid crystal polymer composition described in Patent Document 2 has a problem that the melt viscosity is increased by containing glass fibers having no surface treatment, and improvement in tensile elongation is insufficient.
本発明の目的は、流動性および機械強度を損なうことなく、柔軟性および伸び性が改良された液晶ポリマー組成物を提供することにある。 An object of the present invention is to provide a liquid crystal polymer composition having improved flexibility and extensibility without impairing fluidity and mechanical strength.
本発明者らは、液晶ポリマーの柔軟性および伸び性の改善について鋭意検討した結果、液晶ポリマーに、エポキシ基含有エチレン共重合体および板状充填材を含有させることにより、流動性および機械強度を損なうことなく柔軟性および伸び性が改善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 intensive investigations on the improvement of flexibility and elongation of the liquid crystal polymer, the inventors of the present invention have improved fluidity and mechanical strength by adding an epoxy group-containing ethylene copolymer and a plate-like filler to the liquid crystal polymer. The present inventors have found that the flexibility and extensibility can be improved without impairing the present invention, and have completed the present invention.
すなわち本発明は、液晶ポリマー１００重量部、エポキシ基含有エチレン共重合体１〜３０重量部、および板状充填材１〜３０重量部を含有する液晶ポリマー組成物を提供する。 That is, the present invention provides a liquid crystal polymer composition containing 100 parts by weight of a liquid crystal polymer, 1 to 30 parts by weight of an epoxy group-containing ethylene copolymer, and 1 to 30 parts by weight of a plate-like filler.
本発明の液晶ポリマー組成物は、流動性および機械強度を損なうことなく、柔軟性および伸び性に優れるため、接続に嵌合等が求められる部品や小型化および薄肉化が求められる部品の成形用樹脂として好適に用いることができる。 The liquid crystal polymer composition of the present invention is excellent in flexibility and extensibility without impairing fluidity and mechanical strength, and therefore, for molding parts that require fitting or the like for connection or parts that require miniaturization and thinning. It can be suitably used as a resin.
本発明の液晶ポリマー組成物に用いる液晶ポリマーは、異方性溶融相を形成するポリエステルまたはポリエステルアミドであり、当該技術分野においてサーモトロピック液晶ポリエステルまたはサーモトロピック液晶ポリエステルアミドと呼ばれるものであれば特に限定されない。 The liquid crystal polymer used in the liquid crystal polymer composition of the present invention is a polyester or polyester amide that forms an anisotropic molten phase, and is particularly limited as long as it is called a thermotropic liquid crystal polyester or a thermotropic liquid crystal polyester amide in the technical field. Not.
異方性溶融相の性質は、直交偏光子を利用した慣用の偏光検査法により確認することができる。より具体的には、異方性溶融相の確認は、Ｌｅｉｔｚ偏光顕微鏡を使用し、Ｌｅｉｔｚホットステージにのせた試料を窒素雰囲気下で４０倍の倍率で観察することにより実施できる。本発明における液晶ポリマーは光学的に異方性を示すもの、即ち、直交偏光子の間で検査したときに光を透過させるものである。試料が光学的に異方性であると、たとえ静止状態であっても偏光は透過する。 The property of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarizing microscope and observing a sample placed on a Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times. The liquid crystal polymer in the present invention is optically anisotropic, that is, transmits light when inspected between orthogonal polarizers. If the sample is optically anisotropic, polarized light is transmitted even if it is stationary.
本発明における液晶ポリマーを構成する重合性単量体としては、例えば芳香族ヒドロキシカルボン酸、芳香族ジカルボン酸、芳香族ジオール、芳香族アミノカルボン酸、芳香族ヒドロキシアミン、芳香族ジアミン、脂肪族ジオールおよび脂肪族ジカルボン酸が挙げられる。液晶ポリマーを構成する重合性単量体は、これら化合物は１種のみであってもよく、２種以上の化合物を組み合わせてもよいが、少なくとも１種のヒドロキシ基およびカルボキシル基を有する重合性単量体を含むことが望ましい。 Examples of the polymerizable monomer constituting the liquid crystal polymer in the present invention include aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic aminocarboxylic acid, aromatic hydroxyamine, aromatic diamine, and aliphatic diol. And aliphatic dicarboxylic acids. The polymerizable monomer constituting the liquid crystal polymer may be only one kind of these compounds or a combination of two or more kinds of compounds. However, the polymerizable monomer having at least one kind of hydroxy group and carboxyl group may be used. It is desirable to include a monomer.
液晶ポリマーを構成する重合性単量体は、前記化合物の１種以上が結合してなるオリゴマー、つまり１種以上の前記化合物から構成されるオリゴマーであってもよい。 The polymerizable monomer constituting the liquid crystal polymer may be an oligomer formed by bonding one or more of the compounds, that is, an oligomer composed of one or more of the compounds.
芳香族ヒドロキシカルボン酸の具体例としては、４−ヒドロキシ安息香酸、３−ヒドロキシ安息香酸、２−ヒドロキシ安息香酸、６−ヒドロキシ−２−ナフトエ酸、５−ヒドロキシ−２−ナフトエ酸、７−ヒドロキシ−２−ナフトエ酸、３−ヒドロキシ−２−ナフトエ酸、４’−ヒドロキシフェニル−４−安息香酸、３’−ヒドロキシフェニル−４−安息香酸、４’−ヒドロキシフェニル−３−安息香酸およびそれらのアルキル、アルコキシまたはハロゲン置換体ならびにこれらのアシル化物、エステル誘導体、酸ハロゲン化物などのエステル形成性誘導体が挙げられる。これらの中でも、得られる液晶ポリマーの耐熱性および機械強度ならびに融点を調節し易いという観点から、４−ヒドロキシ安息香酸および６−ヒドロキシ−２−ナフトエ酸からなる群から選択される１種以上の化合物が好ましい。 Specific examples of the aromatic hydroxycarboxylic acid include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 2-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 5-hydroxy-2-naphthoic acid, and 7-hydroxy. 2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 4′-hydroxyphenyl-4-benzoic acid, 3′-hydroxyphenyl-4-benzoic acid, 4′-hydroxyphenyl-3-benzoic acid and their Examples include alkyl-, alkoxy- or halogen-substituted products and ester-forming derivatives thereof such as acylated products, ester derivatives, and acid halides. Among these, one or more compounds selected from the group consisting of 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid from the viewpoint of easily adjusting the heat resistance and mechanical strength and melting point of the obtained liquid crystal polymer Is preferred.
芳香族ジカルボン酸の具体例としては、テレフタル酸、イソフタル酸、２，６−ナフタレンジカルボン酸、１，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸、４，４’−ジカルボキシビフェニル、３，４’−ジカルボキシビフェニルおよび４，４’’−ジカルボキシターフェニル、これらのアルキル、アルコキシまたはハロゲン置換体ならびにそれらのエステル誘導体、酸ハロゲン化物などのエステル形成性誘導体が挙げられる。これらの中でも、得られる液晶ポリマーの耐熱性を効果的に高められる観点から、テレフタル酸、イソフタル酸および２，６−ナフタレンジカルボン酸からなる群から選択される１種以上の化合物が好ましく、テレフタル酸および２，６−ナフタレンジカルボン酸がより好ましい。 Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl, 3 , 4′-dicarboxybiphenyl and 4,4 ″ -dicarboxyterphenyl, alkyl, alkoxy or halogen-substituted products thereof, and ester-forming derivatives thereof such as ester derivatives and acid halides thereof. Among these, one or more compounds selected from the group consisting of terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid are preferable from the viewpoint of effectively improving the heat resistance of the obtained liquid crystal polymer. And 2,6-naphthalenedicarboxylic acid is more preferred.
芳香族ジオールの具体例としては、ハイドロキノン、レゾルシン、２，６−ジヒドロキシナフタレン、２，７−ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレン、３，３’−ジヒドロキシビフェニル、３，４’−ジヒドロキシビフェニル、４，４’−ジヒドロキシビフェニル、４，４’−ジヒドロキシビフェニルエーテルおよび２，２’−ジヒドロキシビナフチル、これらのアルキル、アルコキシまたはハロゲン置換体ならびにそれらのアシル化物などのエステル形成性誘導体が挙げられる。これらの中でも、重合時の反応性に優れる観点から、ハイドロキノン、レゾルシン、４，４’−ジヒドロキシビフェニルおよび２，６−ジヒドロキシナフタレンからなる群から選択される１種以上の化合物が好ましく、ハイドロキノン、４，４’−ジヒドロキシビフェニルおよび２，６−ジヒドロキシナフタレンからなる群から選択される１種以上の化合物がより好ましい。 Specific examples of the aromatic diol include hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 3,3′-dihydroxybiphenyl, 3,4′-dihydroxybiphenyl, Examples include ester-forming derivatives such as 4,4′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl ether and 2,2′-dihydroxybinaphthyl, alkyl, alkoxy or halogen substituents thereof, and acylated products thereof. Among these, from the viewpoint of excellent reactivity during polymerization, one or more compounds selected from the group consisting of hydroquinone, resorcin, 4,4′-dihydroxybiphenyl, and 2,6-dihydroxynaphthalene are preferable. More preferred is one or more compounds selected from the group consisting of 4,4'-dihydroxybiphenyl and 2,6-dihydroxynaphthalene.
芳香族アミノカルボン酸の具体例としては、４−アミノ安息香酸、３−アミノ安息香酸、６−アミノ−２−ナフトエ酸、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにそれらのアシル化物、エステル誘導体、酸ハロゲン化物などのエステル形成性誘導体が挙げられる。 Specific examples of the aromatic aminocarboxylic acid include 4-aminobenzoic acid, 3-aminobenzoic acid, 6-amino-2-naphthoic acid, their alkyl, alkoxy or halogen-substituted products, and acylated products and ester derivatives thereof. And ester-forming derivatives such as acid halides.
芳香族ヒドロキシアミンの具体例としては、４−アミノフェノール、Ｎ−メチル−４−アミノフェノール、３−アミノフェノール、３−メチル−４−アミノフェノール、４−アミノ−１−ナフトール、４−アミノ−４’−ヒドロキシビフェニル、４−アミノ−４’−ヒドロキシビフェニルエーテル、４−アミノ−４’−ヒドロキシビフェニルメタン、４−アミノ−４’−ヒドロキシビフェニルスルフィドおよび２，２’−ジアミノビナフチル、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにそれらのアシル化物などのエステル形成性誘導体が挙げられる。これらの中でも、得られる液晶ポリマーの耐熱性および機械強度のバランスをとりやすい観点から、４−アミノフェノールが好ましい。 Specific examples of the aromatic hydroxyamine include 4-aminophenol, N-methyl-4-aminophenol, 3-aminophenol, 3-methyl-4-aminophenol, 4-amino-1-naphthol, 4-amino- 4'-hydroxybiphenyl, 4-amino-4'-hydroxybiphenyl ether, 4-amino-4'-hydroxybiphenylmethane, 4-amino-4'-hydroxybiphenyl sulfide and 2,2'-diaminobinaphthyl, their alkyl , Alkoxy- or halogen-substituted products, and ester-forming derivatives thereof such as acylated products thereof. Among these, 4-aminophenol is preferable from the viewpoint of easily balancing the heat resistance and mechanical strength of the obtained liquid crystal polymer.
芳香族ジアミンの具体例としては、１，４−フェニレンジアミン、１，３−フェニレンジアミン、１，５−ジアミノナフタレン、１，８−ジアミノナフタレン、これらのアルキル、アルコキシまたはハロゲン置換体、ならびにそれらのアシル化物などのアミド形成性誘導体が挙げられる。 Specific examples of the aromatic diamine include 1,4-phenylenediamine, 1,3-phenylenediamine, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, alkyl, alkoxy or halogen substituted products thereof, and their Examples include amide-forming derivatives such as acylated products.
脂肪族ジオールの具体例としては、エチレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオール、ならびにそれらのアシル化物が挙げられる。また、ポリエチレンテレフタレートやポリブチレンテレフタレートなどの脂肪族ジオールを含有するポリマーを、前記の芳香族オキシカルボン酸、芳香族ジカルボン酸、芳香族ジオールおよびそれらのアシル化物、エステル誘導体、酸ハロゲン化物などと反応させてもよい。 Specific examples of the aliphatic diol include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and acylated products thereof. Also, polymers containing aliphatic diols such as polyethylene terephthalate and polybutylene terephthalate react with the above aromatic oxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols and their acylated products, ester derivatives, acid halides, etc. You may let them.
脂肪族ジカルボン酸の具体例としては、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ドデカン二酸、テトラデカン二酸、フマル酸、マレイン酸、１，４−シクロヘキサンジカルボン酸およびヘキサヒドロテレフタル酸が挙げられる。これらの中でも、重合時の反応性に優れる観点から、シュウ酸、コハク酸、アジピン酸、スベリン酸、セバシン酸、ドデカン二酸および１，４−シクロヘキサンジカルボン酸が好ましい。 Specific examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, fumaric acid, maleic acid 1,4-cyclohexanedicarboxylic acid and hexahydroterephthalic acid. Among these, oxalic acid, succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid and 1,4-cyclohexanedicarboxylic acid are preferred from the viewpoint of excellent reactivity during polymerization.
本発明において液晶ポリマーは、本発明の目的を損なわない範囲で、ジヒドロキシテレフタル酸、４−ヒドロキシイソフタル酸、５−ヒドロキシイソフタル酸、トリメリット酸、１，３，５−ベンゼントリカルボン酸、ピロメリット酸またはこれらのアルキル、アルコキシもしくはハロゲン置換体、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を重合性単量体として含むものであってもよい。これらの重合性単量体の使用量は、他の重合性単量体の合計量に対して１０モル％以下であるのが好ましい。 In the present invention, the liquid crystal polymer is dihydroxyterephthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, trimellitic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid, as long as the object of the present invention is not impaired. Alternatively, these alkyl, alkoxy, or halogen-substituted products and ester-forming derivatives thereof such as acylated products, ester derivatives, and acid halides may be contained as polymerizable monomers. The amount of these polymerizable monomers used is preferably 10 mol% or less with respect to the total amount of other polymerizable monomers.
本発明において液晶ポリマーは、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重合性単量体としては、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。これらの重合性単量体の含有量は、他の重合性単量体の合計量に対して１０モル％以下であるのが好ましい。 In the present invention, the liquid crystal polymer may contain a thioester bond as long as the object of the present invention is not impaired. Examples of the polymerizable monomer that gives such a bond include mercapto aromatic carboxylic acids, aromatic dithiols, and hydroxy aromatic thiols. The content of these polymerizable monomers is preferably 10 mol% or less with respect to the total amount of other polymerizable monomers.
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異方性溶融相を形成するものと異方性溶融相を形成しないものとが存在するが、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。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は、異方性溶融相を形成する液晶ポリマーが得られるように当業者であれば適宜選択および調節することができる。 Polymers combining these repeating units are those that form an anisotropic molten phase and those that do not form an anisotropic molten phase depending on the composition and composition ratio of the monomers and the sequence distribution of each repeating unit in the polymer. However, the liquid crystal polymer used in the present invention is limited to those forming an anisotropic melt phase. Those skilled in the art can appropriately select and adjust the constitution and composition ratio of the monomer and the sequence distribution of each repeating unit in the polymer so that a liquid crystal polymer forming an anisotropic melt phase can be obtained.
本発明の液晶ポリマー組成物に用いる液晶ポリマーを構成する重合性単量体の組み合わせの具体例としては、例えば下記のものが挙げられる。
１）４−ヒドロキシ安息香酸／６−ヒドロキシ−２−ナフトエ酸、
２）４−ヒドロキシ安息香酸／テレフタル酸／４，４’−ジヒドロキシビフェニル、
３）４−ヒドロキシ安息香酸／テレフタル酸／イソフタル酸／４，４’−ジヒドロキシビフェニル、
４）４−ヒドロキシ安息香酸／テレフタル酸／イソフタル酸／４，４’−ジヒドロキシビフェニル／ハイドロキノン、
５）４−ヒドロキシ安息香酸／テレフタル酸／ハイドロキノン、
６）６−ヒドロキシ−２−ナフトエ酸／テレフタル酸／ハイドロキノン、
７）４−ヒドロキシ安息香酸／６−ヒドロキシ−２−ナフトエ酸／テレフタル酸／４，４’−ジヒドロキシビフェニル、
８）６−ヒドロキシ−２−ナフトエ酸／テレフタル酸／４，４’−ジヒドロキシビフェニル、
９）４−ヒドロキシ安息香酸／６−ヒドロキシ−２−ナフトエ酸／テレフタル酸／ハイドロキノン、
１０）４−ヒドロキシ安息香酸／６−ヒドロキシ−２−ナフトエ酸／テレフタル酸／ハイドロキノン／４，４’−ジヒドロキシビフェニル、
１１）４−ヒドロキシ安息香酸／２，６−ナフタレンジカルボン酸／４，４’−ジヒドロキシビフェニル、
１２）４−ヒドロキシ安息香酸／テレフタル酸／２，６−ナフタレンジカルボン酸／ハイドロキノン、
１３）４−ヒドロキシ安息香酸／２，６−ナフタレンジカルボン酸／ハイドロキノン、
１４）４−ヒドロキシ安息香酸／６−ヒドロキシ−２−ナフトエ酸／２，６−ナフタレンジカルボン酸／ハイドロキノン、
１５）４−ヒドロキシ安息香酸／テレフタル酸／２，６−ナフタレンジカルボン酸／ハイドロキノン／４，４’−ジヒドロキシビフェニル、
１６）４−ヒドロキシ安息香酸／テレフタル酸／４−アミノフェノール、
１７）６−ヒドロキシ−２−ナフトエ酸／テレフタル酸／４−アミノフェノール、
１８）４−ヒドロキシ安息香酸／６−ヒドロキシ−２−ナフトエ酸／テレフタル酸／４−アミノフェノール、
１９）４−ヒドロキシ安息香酸／テレフタル酸／４，４’−ジヒドロキシビフェニル／４−アミノフェノール、
２０）４−ヒドロキシ安息香酸／テレフタル酸／エチレングリコール、
２１）４−ヒドロキシ安息香酸／テレフタル酸／４，４’−ジヒドロキシビフェニル／エチレングリコール、
２２）４−ヒドロキシ安息香酸／６−ヒドロキシ−２−ナフトエ酸／テレフタル酸／エチレングリコール、
２３）４−ヒドロキシ安息香酸／６−ヒドロキシ−２−ナフトエ酸／テレフタル酸／４，４’−ジヒドロキシビフェニル／エチレングリコール、
２４）４−ヒドロキシ安息香酸／テレフタル酸／２，６−ナフタレンジカルボン酸／４，４’−ジヒドロキシビフェニル。
Specific examples of the combination of polymerizable monomers constituting the liquid crystal polymer used in the liquid crystal polymer composition of the present invention include the following.
1) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid,
2) 4-hydroxybenzoic acid / terephthalic acid / 4,4′-dihydroxybiphenyl,
3) 4-hydroxybenzoic acid / terephthalic acid / isophthalic acid / 4,4′-dihydroxybiphenyl,
4) 4-hydroxybenzoic acid / terephthalic acid / isophthalic acid / 4,4′-dihydroxybiphenyl / hydroquinone,
5) 4-hydroxybenzoic acid / terephthalic acid / hydroquinone,
6) 6-hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone,
7) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / 4,4′-dihydroxybiphenyl,
8) 6-hydroxy-2-naphthoic acid / terephthalic acid / 4,4′-dihydroxybiphenyl,
9) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone,
10) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone / 4,4′-dihydroxybiphenyl,
11) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / 4,4′-dihydroxybiphenyl,
12) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone,
13) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone,
14) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone,
15) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / hydroquinone / 4,4′-dihydroxybiphenyl,
16) 4-hydroxybenzoic acid / terephthalic acid / 4-aminophenol,
17) 6-hydroxy-2-naphthoic acid / terephthalic acid / 4-aminophenol,
18) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / 4-aminophenol,
19) 4-hydroxybenzoic acid / terephthalic acid / 4,4′-dihydroxybiphenyl / 4-aminophenol,
20) 4-hydroxybenzoic acid / terephthalic acid / ethylene glycol,
21) 4-hydroxybenzoic acid / terephthalic acid / 4,4′-dihydroxybiphenyl / ethylene glycol,
22) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / ethylene glycol,
23) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / 4,4′-dihydroxybiphenyl / ethylene glycol,
24) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalenedicarboxylic acid / 4,4′-dihydroxybiphenyl.
上記の液晶ポリマーは単独で用いてもよく、２種以上の液晶ポリマーの混合物として用いてもよい。 Said liquid crystal polymer may be used independently and may be used as a mixture of 2 or more types of liquid crystal polymers.
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、流動性および機械特性に優れる点で、式（Ｉ）および／または式（ＩＩ）で表される繰返し単位を含む液晶ポリエステル樹脂が好適に使用される。
また、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、流動性および機械特性に優れる点で、式（Ｉ）および式（ＩＩ）で表される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。 In addition, the liquid crystal polymer used in the liquid crystal polymer composition of the present invention is a wholly aromatic compound composed of repeating units represented by the formulas (I) and (II) in terms of excellent fluidity and mechanical properties. A liquid crystal polyester resin is preferably used.
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の結晶融解温度は、特に限定されないが、エポキシ基含有エチレン共重合体の成形加工時の滞留熱安定性の観点から、成形加工時の樹脂温度を比較的低く設定できる、３５０℃以下であるものが好ましく、３４０℃以下であるものがより好ましく、３３０℃以下であるものがさらに好ましい。また、結晶融解温度が１７０℃以上である液晶ポリマーが好ましく、１８０℃以上である液晶ポリマーがより好ましく、１９０℃以上であるものがさらに好ましい。 The crystal melting temperature of the liquid crystal polymer used in the liquid crystal polymer composition of the present invention is not particularly limited, but from the viewpoint of residence heat stability during the molding process of the epoxy group-containing ethylene copolymer, the resin temperature during the molding process Is preferably 350 ° C. or lower, more preferably 340 ° C. or lower, and further preferably 330 ° C. or lower. Moreover, the liquid crystal polymer whose crystal melting temperature is 170 degreeC or more is preferable, The liquid crystal polymer which is 180 degreeC or more is more preferable, and what is 190 degreeC or more 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。 Hereafter, the manufacturing method of the liquid crystal polymer used for this invention is demonstrated.
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、重合性単量体を、エステル結合またはアミド結合を形成させる公知の重縮合方法、たとえば溶融アシドリシス法、スラリー重合法などに供することにより液晶ポリマーを得ることができる。 There is no particular limitation on the production method of the liquid crystal polymer used in the present invention, and the liquid crystal polymer is subjected to a known polycondensation method for forming an ester bond or an amide bond, such as a melt acidosis method, a slurry polymerization method, etc. A polymer can be obtained.
溶融アシドリシス法は、本発明の液晶ポリマー組成物に用いる液晶ポリマーを製造するのに好ましい方法である。この方法は、最初に重合性単量体を加熱して反応物質の溶融溶液を形成し、次いで重縮合反応を続けて溶融ポリマーを得るものである。なお、縮合の最終段階で副生する揮発物（たとえば酢酸、水など）の除去を容易にするために真空を適用してもよい。 The melt acidolysis method is a preferable method for producing the liquid crystal polymer used in the liquid crystal polymer composition of the present invention. In this method, the polymerizable monomer is first heated to form a molten solution of the reactants, and then the polycondensation reaction is continued to obtain a molten polymer. A vacuum may be applied to facilitate removal of volatiles (for example, acetic acid, water, etc.) by-produced in the final stage of condensation.
スラリー重合法とは、熱交換流体の存在下で重合性単量体を反応させる方法であって、固体生成物は熱交換媒質中に懸濁した状態で得られる。 The slurry polymerization method is a method in which a polymerizable monomer is reacted in the presence of a heat exchange fluid, and a solid product is obtained in a state suspended in a heat exchange medium.
溶融アシドリシス法およびスラリー重合法のいずれの場合においても、液晶ポリマーを製造する際に使用される重合性単量体は、常温において、ヒドロキシル基および／またはアミノ基をアシル化した変性形態、すなわち低級アシル化物として反応に供することもできる。 In any of the melt acidification method and the slurry polymerization method, the polymerizable monomer used in producing the liquid crystal polymer is a modified form in which a hydroxyl group and / or an amino group are acylated at room temperature, that is, lower It can also be subjected to the reaction as an acylated product.
低級アシル基は炭素原子数２〜５のものが好ましく、炭素原子数２または３のものがより好ましい。本発明の好ましい実施態様において、前記重合性単量体のアセチル化物を反応に供する。 The lower acyl group preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms. In a preferred embodiment of the present invention, the acetylated product of the polymerizable monomer is subjected to the reaction.
重合性単量体の低級アシル化物は、別途アシル化して予め合成したものを用いてもよいし、液晶ポリマーの製造時に重合性単量体に無水酢酸等のアシル化剤を加えて反応系内で生成せしめることもできる。 The lower acylated product of the polymerizable monomer may be separately acylated and synthesized beforehand, or an acylating agent such as acetic anhydride may be added to the polymerizable monomer during the production of the liquid crystal polymer. It can also be generated with
溶融アシドリシス法またはスラリー重合法のいずれの場合においても、重縮合反応は、温度１５０〜４００℃、好ましくは２５０〜３７０℃で、常圧および／または減圧下で行うのがよく、必要に応じて触媒を用いてもよい。 In either case of the melt acidification method or the slurry polymerization method, the polycondensation reaction is carried out at a temperature of 150 to 400 ° C., preferably 250 to 370 ° C. under normal pressure and / or reduced pressure. A catalyst may be used.
触媒の具体例としては、ジアルキルスズオキシド（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およびアルカリ土類金属塩（例えば酢酸カリウム）；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 organotin compounds such as dialkyltin oxide (eg dibutyltin oxide) and diaryltin oxide; titanium dioxide; antimony trioxide; organotitanium compounds such as alkoxytitanium silicate and titanium alkoxide; alkali and alkali of carboxylic acid Examples include earth metal salts (for example, potassium acetate); gaseous acids catalysts such as Lewis acids (for example, boron trifluoride) and hydrogen halides (for example, hydrogen chloride).
触媒を使用する場合、該触媒の量は重合性単量体全量に対し、好ましくは１〜１０００ｐｐｍ、より好ましくは２〜１００ｐｐｍである。 When a catalyst is used, the amount of the catalyst is preferably 1 to 1000 ppm, more preferably 2 to 100 ppm, based on the total amount of polymerizable monomers.
このようにして重縮合反応させて得られた液晶ポリマーは、通常、溶融状態で重合反応槽より抜き出された後に、ペレット状、フレーク状、または粉末状に加工される。 The liquid crystal polymer obtained by the polycondensation reaction in this manner is usually 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、真空下、または窒素、ヘリウムなどの不活性ガス雰囲気下において、実質的に固相状態で熱処理を行ってもよい。 A liquid crystal polymer in the form of pellets, flakes, or powders is substantially a solid phase under reduced pressure, vacuum, or an inert gas atmosphere such as nitrogen or helium for the purpose of increasing molecular weight and improving heat resistance. You may heat-process in a state.
固相状態において行う熱処理の温度は、液晶ポリマーが溶融しない限り特に限定されないが、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 is not particularly limited as long as the liquid crystal polymer is not melted, but is preferably 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、エポキシ基含有エチレン共重合体１〜３０重量部、および板状充填材１〜３０重量部を含有する。 The liquid crystal polymer composition of the present invention comprises 1 to 30 parts by weight of an epoxy group-containing ethylene copolymer and 1 to 30 parts by weight of a plate-like filler in addition to 100 parts by weight of the liquid crystal polymer obtained as described above. contains.
エポキシ基含有エチレン共重合体の含有量は、液晶ポリマー１００重量部に対して好ましくは５〜２５重量部、より好ましくは５〜１５重量部である。前記のエポキシ基含有エチレン共重合体の含有量が液晶ポリマー１００重量部に対して３０重量部を上回る場合、液晶ポリマー組成物の流動性が低下する。前記のエポキシ基含有エチレン共重合体の含有量が１重量部を下回る場合、液晶ポリマー組成物の柔軟性および伸び性の向上効果を発現させることができない。 The content of the epoxy group-containing ethylene copolymer is preferably 5 to 25 parts by weight, more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the liquid crystal polymer. When the content of the epoxy group-containing ethylene copolymer exceeds 30 parts by weight with respect to 100 parts by weight of the liquid crystal polymer, the fluidity of the liquid crystal polymer composition is lowered. When content of the said epoxy group containing ethylene copolymer is less than 1 weight part, the improvement effect of the softness | flexibility and elongation property of a liquid crystal polymer composition cannot be expressed.
エポキシ基含有エチレン共重合体としては、エチレン単位とグリシジルメタクリレート単位からなる共重合体、エチレン単位とグリシジルメタクリレート単位およびアクリル酸メチル単位からなる共重合体、エチレン単位とグリシジルメタクリレート単位およびアクリル酸エチル単位からなる共重合体、エチレン単位とグリシジルメタクリレート単位および酢酸ビニル単位からなる共重合体、およびエチレン単位とグリシジルエーテル単位からなる共重合体からなる群から選択される１種以上が挙げられ、これらの中でも、液晶ポリマー組成物の機械強度を保持できる点でエチレン単位とグリシジルメタクリレート単位およびアクリル酸メチル単位からなる共重合体が好ましい。 As the epoxy group-containing ethylene copolymer, a copolymer comprising an ethylene unit and a glycidyl methacrylate unit, a copolymer comprising an ethylene unit, a glycidyl methacrylate unit and a methyl acrylate unit, an ethylene unit, a glycidyl methacrylate unit and an ethyl acrylate unit One or more selected from the group consisting of a copolymer consisting of an ethylene unit, a glycidyl methacrylate unit and a vinyl acetate unit, and a copolymer consisting of an ethylene unit and a glycidyl ether unit. Especially, the copolymer which consists of an ethylene unit, a glycidyl methacrylate unit, and a methyl acrylate unit is preferable at the point which can maintain the mechanical strength of a liquid crystal polymer composition.
エポキシ基含有エチレン共重合体は、通常、エチレン単位を与える化合物と、不飽和カルボン酸グリシジルエステル単位または不飽和グリシジルエーテル単位を与える化合物と、必要に応じてエチレン系不飽和エステル単位を与える化合物を、ラジカル発生剤の存在下、５００〜４０００気圧、１００〜３００℃の条件で、適当な溶媒や連鎖移動剤の存在下または不存在下に共重合させる方法により製造することができるものである。 The epoxy group-containing ethylene copolymer usually comprises a compound that gives an ethylene unit, a compound that gives an unsaturated carboxylic acid glycidyl ester unit or an unsaturated glycidyl ether unit, and a compound that gives an ethylenically unsaturated ester unit if necessary. The copolymer can be produced by copolymerization in the presence of a radical generator in the presence or absence of a suitable solvent or chain transfer agent under conditions of 500 to 4000 atm and 100 to 300 ° C.
本発明において板状充填材とは、３次元的形状において２方向への広がりを持ち、残りの１方向へは広がりを持たない円盤状、方形板状、短冊状および不定形板状である充填材を意味し、具体的には、タルク、マイカ、グラファイト、ドロマイト、クレイ、ガラスフレーク、カオリン、バーミキュライト、ケイ酸カルシウム、ケイ酸アルミニウム、長石粉、酸性白土、ロウ石クレー、セリサイト、シリマナイト、ベントナイト、スレート粉、シラン等のケイ酸塩、炭酸カルシウム、胡粉、炭酸バリウム、炭酸マグネシウム、バライト粉、沈降性硫酸カルシウム、焼石膏、硫酸バリウム等の硫酸塩、水和アルミナ等の水酸化物、アルミナ、酸化アンチモン、マグネシア、酸化チタン、亜鉛華、シリカ、珪砂、石英、ホワイトカーボン、珪藻土等の酸化物、二硫化モリブデン等の硫化物、板状のウォラストナイトおよび金属粉粒体からなる群より選択される１種以上が挙げられる。これら板状充填材の中でも、液晶ポリマー組成物の柔軟性および成形時の流動性の向上効果に優れる点でタルク、マイカ、グラファイト、ドロマイト、クレイおよびガラスフレークからなる群より選択される１種以上が好ましく、特にタルクが好適に使用される。 In the present invention, the plate-shaped filler is a disk-shaped, rectangular-plate-shaped, strip-shaped or irregular-shaped plate-shaped material that has a three-dimensional shape and spreads in two directions and does not spread in the remaining one direction. Means wood, specifically, talc, mica, graphite, dolomite, clay, glass flake, kaolin, vermiculite, calcium silicate, aluminum silicate, feldspar powder, acid clay, waxy clay, sericite, silimanite, Bentonite, slate powder, silicates such as silane, calcium carbonate, hum powder, barium carbonate, magnesium carbonate, barite powder, precipitated calcium sulfate, calcined gypsum, sulfate such as barium sulfate, hydroxide such as hydrated alumina, Alumina, antimony oxide, magnesia, titanium oxide, zinc white, silica, silica sand, quartz, white carbon, diatomaceous earth, etc. Oxide, disulfide sulfides such as molybdenum, one or more can be mentioned which is selected from the group consisting of plate-like wollastonite and metal powders granules. Among these plate-like fillers, one or more selected from the group consisting of talc, mica, graphite, dolomite, clay, and glass flakes in that they are excellent in improving the flexibility of the liquid crystal polymer composition and the fluidity during molding. In particular, talc is preferably used.
板状充填材の平均粒子径は特に限定されないが、レーザ回折／散乱式粒度分布測定法で測定されるメディアン径は、流動性の観点から５０μｍ以下であることが好ましい。また、板状充填剤の平均粒子径は通常、０．５μｍ以上である。 The average particle diameter of the plate-like filler is not particularly limited, but the median diameter measured by the laser diffraction / scattering particle size distribution measurement method is preferably 50 μm or less from the viewpoint of fluidity. Further, the average particle size of the plate-like filler is usually 0.5 μm or more.
板状充填材の含有量は、液晶ポリマー１００重量部に対して好ましくは５〜２５重量部、より好ましくは５〜１５重量部である。前記の板状充填材の含有量が液晶ポリマー１００重量部に対して３０重量部を上回る場合、液晶ポリマー組成物の柔軟性改善効果が低下する。前記の板状充填材の含有量が１重量部を下回る場合、液晶ポリマー組成物の柔軟性および成形時の流動性の向上効果を発現させることができない。 The content of the plate-like filler is preferably 5 to 25 parts by weight, more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the liquid crystal polymer. When the content of the plate-like filler exceeds 30 parts by weight with respect to 100 parts by weight of the liquid crystal polymer, the flexibility improving effect of the liquid crystal polymer composition is lowered. When the content of the plate-like filler is less than 1 part by weight, the effect of improving the flexibility of the liquid crystal polymer composition and the fluidity at the time of molding cannot be exhibited.
本発明の液晶ポリマー組成物の抗張積は８００ＭＰａ・％以上が好ましく、より好ましくは９００ＭＰａ・％以上であり、さらに好ましくは１０００ＭＰａ・％以上である。 The tensile product of the liquid crystal polymer composition of the present invention is preferably 800 MPa ·% or more, more preferably 900 MPa ·% or more, and further preferably 1000 MPa ·% or more.
抗張積とは、引張強度と引張破断伸びとの積（ＭＰａ・％）であり、高分子化合物の破断エネルギーの尺度として用いられ、抗張積の値が大きいほど強度と伸びのバランスの良い材料であることを示す。 Tensile product is the product (MPa ·%) of tensile strength and tensile elongation at break, and is used as a measure of the breaking energy of polymer compounds. The larger the tensile product, the better the balance between strength and elongation. Indicates material.
本明細書において、引張強度および引張破断伸びは厚み３．２ｍｍのＡＳＴＭ４号ダンベルを使用し、標線間２５ｍｍの接触式の伸び計を用い、試験速度５ｍｍ／ｍｉｎ、チャック間距離６４ｍｍの条件で、ＡＳＴＭ Ｄ６３８に準拠して測定される。 In this specification, the tensile strength and tensile elongation at break were measured using a ASTM No. 4 dumbbell with a thickness of 3.2 mm, a contact type extensometer with a 25 mm gap between the marked lines, a test speed of 5 mm / min, and a chuck distance of 64 mm. , Measured according to ASTM D638.
本発明の液晶ポリマー組成物の引張弾性率は１０ＧＰａ以下が好ましく、より好ましくは９ＧＰａ以下であり、さらに好ましくは８ＧＰａ以下である。本明細書において、引張弾性率は厚み３．２ｍｍのＡＳＴＭ４号ダンベルを使用し、試験速度５ｍｍ／ｍｉｎ、チャック間距離６４ｍｍの条件で、ＡＳＴＭ Ｄ６３８に準拠して測定され、値が小さいほど柔軟性に優れることを示す。 The tensile modulus of the liquid crystal polymer composition of the present invention is preferably 10 GPa or less, more preferably 9 GPa or less, and still more preferably 8 GPa or less. In this specification, the tensile modulus is measured in accordance with ASTM D638 using an ASTM No. 4 dumbbell with a thickness of 3.2 mm, at a test speed of 5 mm / min, and a distance between chucks of 64 mm. It is excellent in.
本発明の液晶ポリマー組成物の曲げ弾性率は７ＧＰａ以下が好ましく、より好ましくは６．５ＧＰａ以下であり、さらに好ましくは６ＧＰａ以下である。 The flexural modulus of the liquid crystal polymer composition of the present invention is preferably 7 GPa or less, more preferably 6.5 GPa or less, and even more preferably 6 GPa or less.
本明細書において、曲げ弾性率は短冊状曲げ試験片（長さ１２７ｍｍ×幅１２．７ｍｍ×厚さ３．２ｍｍ）を使用し、試験速度１．３ｍｍ／ｍｉｎ、スパン間距離５０ｍｍの条件で、ＡＳＴＭ Ｄ７９０に準拠して測定され、値が小さいほど柔軟性に優れることを示す。 In this specification, the bending elastic modulus is a strip-shaped bending test piece (length 127 mm × width 12.7 mm × thickness 3.2 mm), with a test speed of 1.3 mm / min and a span distance of 50 mm. Measured in accordance with ASTM D790, the smaller the value, the better the flexibility.
本発明の液晶ポリマー組成物は、成形時の流動性向上の観点からさらにメラミン化合物を０．０１〜２０重量部含有することが好ましい。 The liquid crystal polymer composition of the present invention preferably further contains 0.01 to 20 parts by weight of a melamine compound from the viewpoint of improving fluidity during molding.
本発明において使用されるメラミン化合物としては、メラミンシアヌレート、メラミンアクリレート、メラミン塩酸塩、メラミンスルホン酸塩、メラミンホウ酸塩、およびメラミンピロリン酸塩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。これらの中でも、流動性および機械強度に優れる点でメラミンシアヌレートが好ましい。 The melamine compound used in the present invention includes one or more selected from the group consisting of melamine cyanurate, melamine acrylate, melamine hydrochloride, melamine sulfonate, melamine borate, and melamine pyrophosphate. It is done. Among these, melamine cyanurate is preferable in terms of excellent fluidity and mechanical strength.
メラミン化合物の含有量が液晶ポリマー１００重量部に対して２０重量部を上回る場合、液晶ポリマー組成物の伸び改善効果が低下する傾向がある。前記のメラミン化合物の含有量が０．０１重量部を下回る場合、液晶ポリマー組成物の難燃性および成形時の流動性の向上効果を発現させることができない。 When content of a melamine compound exceeds 20 weight part with respect to 100 weight part of liquid crystal polymers, there exists a tendency for the elongation improvement effect of a liquid crystal polymer composition to fall. When content of the said melamine compound is less than 0.01 weight part, the flame retardance of a liquid crystal polymer composition and the improvement effect of the fluidity | liquidity at the time of shaping | molding cannot be expressed.
本発明において液晶ポリマー組成物は、本発明の効果を損なわない範囲で、他の添加剤、例えば高級脂肪酸、高級脂肪酸エステル、高級脂肪酸アミド、高級脂肪酸金属塩（ここで高級脂肪酸とは、炭素原子数１０〜２５のものをいう）、ポリシロキサン、フッ素樹脂などの離型改良剤、カーボンブラック、染料、顔料などの着色剤、酸化防止剤、熱安定剤、紫外線吸収剤、帯電防止剤、界面活性剤などを含有してもよい。本発明において液晶ポリマー組成物は、これらの添加剤を１種のみ含有してもよく、または２種以上を組み合わせて含有してもよい。これらの中でもカーボンブラックが好ましい。本発明の液晶ポリマー組成物がカーボンブラックを含有する場合、その含有量は、液晶ポリマー１００重量部に対して好ましくは２０重量部以下、より好ましくは１０重量部以下、さらに好ましくは５重量部以下である。本発明の液晶ポリマー組成物がカーボンブラックを２０重量部以下含有する場合、着色剤としての機能が得られると共に抗張積を向上させる効果が得られ易い傾向がある。 In the present invention, the liquid crystal polymer composition may contain other additives such as higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher fatty acid metal salts (where higher fatty acids are carbon atoms within the range not impairing the effects of the present invention. 10 to 25), release agents such as polysiloxane and fluororesin, colorants such as carbon black, dyes and pigments, antioxidants, heat stabilizers, ultraviolet absorbers, antistatic agents, interfaces An activator or the like may be contained. In the present invention, the liquid crystal polymer composition may contain only one of these additives, or may contain two or more kinds in combination. Among these, carbon black is preferable. When the liquid crystal polymer composition of the present invention contains carbon black, the content thereof is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, further preferably 5 parts by weight or less with respect to 100 parts by weight of the liquid crystal polymer. It is. When the liquid crystal polymer composition of the present invention contains 20 parts by weight or less of carbon black, the function as a colorant can be obtained and the effect of improving the tensile product tends to be easily obtained.
本発明の液晶ポリマー組成物は、板状充填材以外の充填材、例えば球状充填材（バルーン、ガラスビーズ等）や繊維状充填材（ガラス繊維等）を含んでもよい。板状充填材以外の充填材を含む場合は液晶ポリマー１００重量部に対して１重量部未満が好ましく、０．５重量部未満がより好ましく、０．１重量部未満がさらに好ましく、これらの充填材を含まないことが特に好ましい。 The liquid crystal polymer composition of the present invention may contain a filler other than the plate-like filler, for example, a spherical filler (balloon, glass beads, etc.) or a fibrous filler (glass fiber, etc.). When a filler other than the plate-like filler is included, the amount is preferably less than 1 part by weight, more preferably less than 0.5 part by weight, further preferably less than 0.1 part by weight, based on 100 parts by weight of the liquid crystal polymer. It is particularly preferred that no material be included.
液晶ポリマー組成物における他の添加剤の合計量は、液晶ポリマー１００重量部に対して、好ましくは０．１〜１０重量部、より好ましくは０．５〜５重量部である。他の添加剤の合計量が液晶ポリマー１００重量部に対して１０重量部を超える場合には、液晶ポリマー組成物の成形加工性が低下する傾向や、熱安定性が悪くなる傾向がある。他の添加剤の合計量が０．１重量部を下回る場合、添加剤の機能を実現することができない。 The total amount of other additives in the liquid crystal polymer composition is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the liquid crystal polymer. When the total amount of other additives exceeds 10 parts by weight with respect to 100 parts by weight of the liquid crystal polymer, the molding processability of the liquid crystal polymer composition tends to decrease and the thermal stability tends to deteriorate. When the total amount of other additives is less than 0.1 parts by weight, the function of the additive cannot be realized.
また、本発明の液晶ポリマー組成物を成形するに際し、上記他の添加剤のうち高級脂肪酸、高級脂肪酸エステル、高級脂肪酸金属塩、フルオロカーボン系界面活性剤等の外部滑剤効果を有する添加剤を、予め、液晶ポリマーのペレット表面に付着せしめてもよい。 In addition, when molding the liquid crystal polymer composition of the present invention, among the above-mentioned other additives, additives having an external lubricant effect such as higher fatty acid, higher fatty acid ester, higher fatty acid metal salt, fluorocarbon surfactant, Alternatively, it may be adhered to the pellet surface of the liquid crystal polymer.
本発明の液晶ポリマー組成物は、他の樹脂成分を添加してもよい。他の樹脂成分としては、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、または２種以上を組み合わせて含有することができる。液晶ポリマー組成物が他の樹脂成分を含む場合、他の樹脂成分の含有量は特に限定的ではないが、一つの典型的な例において、他の樹脂成分の合計量は、液晶ポリマー１００重量部に対して、通常０．１〜１００重量部、特に０．１〜８０重量部である。 Other resin components may be added to the liquid crystal polymer composition of the present invention. Examples of other resin components include polyamide, polyester, polyacetal, polyphenylene ether, and modified products thereof, and thermoplastic resins such as polysulfone, polyethersulfone, polyetherimide, and polyamideimide, phenol resin, epoxy resin, and polyimide resin. And other thermosetting resins. Other resin components can be contained alone or in combination of two or more. When the liquid crystal polymer composition contains other resin components, the content of the other resin components is not particularly limited, but in one typical example, the total amount of the other resin components is 100 parts by weight of the liquid crystal polymer. The amount is usually 0.1 to 100 parts by weight, particularly 0.1 to 80 parts by weight.
上述したエポキシ基含有エチレン共重合体、板状充填材、メラミン化合物、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℃までの温度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 above-mentioned epoxy group-containing ethylene copolymer, plate-like filler, melamine compound, other additives and other resin components are added to the liquid crystal polymer, and a Banbury mixer, kneader, single-screw or twin-screw extruder is used. The liquid crystal polymer composition can be used by melting and kneading at a temperature close to the crystal melting temperature of the liquid crystal polymer or up to the crystal melting temperature + 20 ° C.
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 nonwoven 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, 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は、柔軟性および伸び性に優れるため、小型化および薄肉化が求められる成形用樹脂として好適に使用することが可能であり、柔軟性が求められる点で結束バンド、コネクタ、チューブ、クリップ等に好適に用いられ、特に結束バンドに好適に用いられる。 Since the liquid crystal polymer composition of the present invention is excellent in flexibility and elongation, it can be suitably used as a molding resin that is required to be reduced in size and thickness, and is a binding band in that flexibility is required. It is preferably used for connectors, tubes, clips, etc., and particularly preferably used for binding bands.
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。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
〈液晶ポリマー〉
まず、実施例および比較例において使用する液晶ポリマーの合成例を記す。
<Liquid crystal polymer>
First, synthesis examples of liquid crystal polymers used in Examples and Comparative Examples will be described.
合成例における略号は以下の化合物を表す。
［液晶ポリマーの合成に用いた重合性単量体］
ＰＯＢ： ４−ヒドロキシ安息香酸
ＢＯＮ６： ６−ヒドロキシ−２−ナフトエ酸
The abbreviations in the synthesis examples represent the following compounds.
[Polymerizable monomer used for the synthesis of liquid crystal polymer]
POB: 4-hydroxybenzoic acid BON6: 6-hydroxy-2-naphthoic acid
合成例で得られた液晶ポリマーの結晶融解温度は以下の方法で測定した。
〈結晶融解温度〉
示差走査熱量計としてセイコーインスツルメンツ（株）製Ｅｘｓｔａｒ６０００を用いて、試料を室温から２０℃／分の昇温条件で測定した際に観測される吸熱ピーク温度（Ｔｍ１）を測定した後、Ｔｍ１より５０℃高い温度で１０分間保持する。次いで、２０℃／分の降温条件で室温まで試料を冷却し、さらに再度２０℃／分の昇温条件で測定した際の吸熱ピークを観測し、そのピークトップを示す温度を結晶融解温度（Ｔｍ）とした。
The crystal melting temperature of the liquid crystal polymer obtained in the synthesis example was measured by the following method.
<Crystal melting temperature>
Using an Exstar 6000 manufactured by Seiko Instruments Inc. as a differential scanning calorimeter, the endothermic peak temperature (Tm1) observed when the sample was measured at a temperature rising condition of 20 ° C./min from room temperature was measured. Hold at elevated temperature for 10 minutes. Next, the sample was cooled to room temperature under a temperature drop condition of 20 ° C./min, and an endothermic peak was measured again when measured under a temperature rise condition of 20 ° C./min. The temperature showing the peak top was the crystal melting temperature (Tm ).
［合成例（ＬＣＰ）］
トルクメーター付き攪拌装置および留出管を備えた２Ｌの反応容器に、ＰＯＢ：６５５．４ｇ（７３モル％）およびＢＯＮ６：４７６．０ｇ（２７モル％）を仕込み、さらに全単量体の水酸基量（モル）に対して１．０１倍モルの無水酢酸を仕込み、次の条件で脱酢酸重合を行った。
[Synthesis Example (LCP)]
POB: 655.4 g (73 mol%) and BON6: 476.0 g (27 mol%) were charged into a 2 L reaction vessel equipped with a stirrer with a torque meter and a distillation tube, and the hydroxyl groups of all monomers. 1.01 moles of acetic anhydride was charged with respect to (mol), and deacetic acid polymerization was performed under the following conditions.
窒素ガス雰囲気下に室温〜１４５℃まで１時間かけて昇温し、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３３０℃まで７時間かけて昇温した後、８０分かけて１０ｍｍＨｇにまで減圧した。所定のトルクを示した時点で重合反応を終了し、反応容器から内容物を取り出し、粉砕機により液晶ポリエステル樹脂のペレットを得た。重合時の留出酢酸量は、ほぼ理論値どおりであった。得られたペレットの結晶融解温度（Ｔｍ）は２７８℃であった。 The temperature was raised from room temperature to 145 ° C. over 1 hour under a nitrogen gas atmosphere, and kept at that temperature for 30 minutes. Next, the temperature was raised to 330 ° C. over 7 hours while acetic acid produced as a byproduct was distilled off, and then the pressure was reduced to 10 mmHg over 80 minutes. When the predetermined torque was exhibited, the polymerization reaction was terminated, the contents were taken out from the reaction vessel, and liquid crystal polyester resin pellets were obtained using a pulverizer. The amount of acetic acid distilled during the polymerization was almost as theoretical. The crystal melting temperature (Tm) of the obtained pellet was 278 ° C.
［実施例１〜５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、エチレン系共重合体、板状充填材およびメラミン化合物を表１に記載の重量比でそれぞれ配合し、二軸押出機（（株）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。
[Examples 1 to 5 and Comparative Examples 1 to 5]
In 100 parts by weight of the liquid crystal polymer obtained in the synthesis example, an ethylene copolymer, a plate-like filler, and a melamine compound were respectively blended at a weight ratio shown in Table 1, and a twin screw extruder (JSW, TEX) The material melt-kneaded in -30) was pelletized to prepare a liquid crystal polymer composition.
エチレン系共重合体、板状充填材およびメラミン化合物は以下のものを使用した。 The following were used for the ethylene copolymer, the plate-like filler and the melamine compound.
〈エチレン系共重合体−１〉
住友化学（株）製 ボンドファースト ＢＦ−２Ｃ（エチレン−グリシジルメタクリレート共重合体）
<Ethylene copolymer-1>
Bond First BF-2C (ethylene-glycidyl methacrylate copolymer) manufactured by Sumitomo Chemical Co., Ltd.
〈エチレン系共重合体−２〉
住友化学（株）製 ボンドファースト ＢＦ−７Ｍ（エチレン−グリシジルメタクリレート−アクリル酸メチル共重合体）
<Ethylene copolymer-2>
Bond First BF-7M (ethylene-glycidyl methacrylate-methyl acrylate copolymer) manufactured by Sumitomo Chemical Co., Ltd.
〈板状充填材〉
富士タルク工業（株）製 ＲＨ４１５（板状タルク、平均粒子径１４μｍ）
<Plate-shaped filler>
RH415 (Plate-like talc, average particle size 14 μm) manufactured by Fuji Talc Kogyo Co., Ltd.
〈メラミン化合物〉
日産化学（株）製 メラミンシアヌレート ＭＣ−６０００
<Melamine compound>
Melamine cyanurate MC-6000 manufactured by Nissan Chemical Co., Ltd.
〈ガラス繊維〉
セントラルグラスファイバー（株）製 ＥＦＨ１５０−０１（表面無処理ガラス繊維、平均繊維長１５０μｍ、平均繊維径１１μｍ）
<Glass fiber>
EFH150-01 manufactured by Central Glass Fiber Co., Ltd. (surface untreated glass fiber, average fiber length 150 μm, average fiber diameter 11 μm)
〈カーボンブラック〉
三菱化学（株）製 ＃９５０Ｂ
<Carbon black>
# 950B manufactured by Mitsubishi Chemical Corporation
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、荷重たわみ温度、引張強度、引張弾性率、引張破断伸び、曲げ強度、曲げ弾性率およびＩｚｏｄ衝撃強度を以下に示す方法にて測定した。結果を表１に示す。 About the pellet of the obtained liquid crystal polymer composition, melt viscosity, load deflection temperature, tensile strength, tensile elastic modulus, tensile breaking elongation, bending strength, bending elastic modulus and Izod impact strength were measured by the following methods. The results are shown in Table 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、３２０℃にて、せん断速度１０００ｓｅｃ−１での値を測定した。
<Melt viscosity>
Using a melt viscosity measuring apparatus (Capillograph 1D manufactured by Toyo Seiki Co., Ltd.), a value at a shear rate of 1000 sec −1 was measured at 320 ° C. using a capillary of 1.0 mmφ × 10 mm.
〈荷重たわみ温度〉
射出成形機（日精樹脂工業（株）製ＵＨ１０００−１１０）を用いて、結晶融解温度＋２０〜４０℃のシリンダー温度、金型温度７０℃で射出成形し、短冊状試験片（長さ１２７ｍｍ×幅１２．７ｍｍ×厚さ３．２ｍｍ）を作製した。これを用いてＡＳＴＭ Ｄ６４８に準拠し、荷重１．８２ＭＰａ、昇温速度２℃／分で所定たわみ量（０．２５４ｍｍ）になる温度を測定した。
<Load deflection temperature>
Using an injection molding machine (UH1000-110 manufactured by Nissei Plastic Industry Co., Ltd.), injection molding was performed at a crystal melting temperature of +20 to 40 ° C. and a mold temperature of 70 ° C., and a strip-shaped test piece (length 127 mm × width) 12.7 mm × thickness 3.2 mm). Using this, the temperature at which a predetermined deflection amount (0.254 mm) was obtained at a load of 1.82 MPa and a heating rate of 2 ° C./min was measured in accordance with ASTM D648.
〈引張強度、引張弾性率および引張破断伸び〉
射出成形機（日精樹脂工業（株）製ＵＨ１０００−１１０）を用いて結晶融解温度＋２０〜４０℃のシリンダー温度、金型温度７０℃で射出成形し、厚み３．２ｍｍのＡＳＴＭ４号ダンベル試験片を作製した。ＩＮＳＴＲＯＮ５５６７（インストロンジャパン カンパニイリミテッド社製万能試験機）を用いて、標線間２５ｍｍの接触式の伸び計を使用し、試験速度５ｍｍ／ｍｉｎ、チャック間距離６４ｍｍの条件で、ＡＳＴＭ Ｄ６３８に準拠して測定した。
<Tensile strength, tensile modulus and tensile elongation at break>
Using an injection molding machine (UH1000-110, manufactured by Nissei Plastic Industry Co., Ltd.), injection molding is performed at a cylinder temperature of 20 to 40 ° C. and a mold temperature of 70 ° C., and an ASTM No. 4 dumbbell test piece having a thickness of 3.2 mm Produced. Using INSTRON5567 (Instron Japan Company Limited universal testing machine), using a contact type extensometer with a 25 mm gap between marks, conforming to ASTM D638 with a test speed of 5 mm / min and a distance between chucks of 64 mm. Measured.
〈曲げ強度、曲げ弾性率〉
荷重たわみ温度測定に用いた成形片と同条件にし、短冊状曲げ試験片（長さ１２７ｍｍ×幅１２．７ｍｍ×厚さ３．２ｍｍ）を作製した。曲げ試験は、３点曲げ試験をＩＮＳＴＲＯＮ５５６７（インストロンジャパンカンパニイリミテッド社製万能試験機）を用いて、試験速度１．３ｍｍ／ｍｉｎ、スパン間距離５０ｍｍの条件で、ＡＳＴＭ Ｄ７９０に準拠して測定した。
<Bending strength, flexural modulus>
A strip-shaped bending test piece (length 127 mm × width 12.7 mm × thickness 3.2 mm) was produced under the same conditions as those of the molded piece used for measuring the deflection temperature under load. The bending test was performed in accordance with ASTM D790 using a INSTRON 5567 (universal testing machine manufactured by Instron Japan Company Limited) at a test speed of 1.3 mm / min and a span distance of 50 mm. .
〈Ｉｚｏｄ衝撃強度〉
荷重たわみ温度測定に用いた試験片と同じ試験片を用いて、試験片の中央を長さ方向に垂直に切断し、ノッチを付けた。長さ６３．５ｍｍ、幅１２．７ｍｍ、厚さ３．２ｍｍの短冊状試験片を得、ＡＳＴＭ Ｄ２５６に準拠して測定した。
<Izod impact strength>
Using the same specimen as the specimen used for measuring the deflection temperature under load, the center of the specimen was cut perpendicularly in the length direction to give a notch. A strip-shaped test piece having a length of 63.5 mm, a width of 12.7 mm, and a thickness of 3.2 mm was obtained and measured according to ASTM D256.
表１に示す通り、エポキシ基含有エチレン共重合体および板状充填材を含有する実施例１〜５の液晶ポリマー組成物は、比較例１、比較例２、比較例４および比較例５の液晶ポリマー組成物と比較して、流動性および機械強度を損なうことなく、低弾性率化による柔軟性の改善、および伸びが向上することが理解される。 As shown in Table 1, the liquid crystal polymer compositions of Examples 1 to 5 containing an epoxy group-containing ethylene copolymer and a plate-like filler are the liquid crystals of Comparative Example 1, Comparative Example 2, Comparative Example 4 and Comparative Example 5. It is understood that the improvement in flexibility and the elongation are improved by lowering the elastic modulus without impairing the fluidity and mechanical strength as compared with the polymer composition.
比較例３の液晶ポリマー組成物は、柔軟性に優れるものの、溶融粘度が高く流動性が劣るものであった。 Although the liquid crystal polymer composition of Comparative Example 3 was excellent in flexibility, it had high melt viscosity and poor fluidity.
また、実施例１〜５の液晶ポリマー組成物は、比較例１〜５の液晶ポリマー組成物と比較して抗張積が大きく、強度と伸びのバランスの良い材料であることが理解される。 In addition, it is understood that the liquid crystal polymer compositions of Examples 1 to 5 are materials having a large tensile product and a good balance between strength and elongation as compared with the liquid crystal polymer compositions of Comparative Examples 1 to 5.
Claims (13)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017107023A JP6878149B2 (en) | 2017-05-30 | 2017-05-30 | Liquid crystal polymer composition |
| JP2021076127A JP7266633B2 (en) | 2017-05-30 | 2021-04-28 | liquid crystal polymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017107023A JP6878149B2 (en) | 2017-05-30 | 2017-05-30 | Liquid crystal polymer composition |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2021076127A Division JP7266633B2 (en) | 2017-05-30 | 2021-04-28 | liquid crystal polymer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2018203810A true JP2018203810A (en) | 2018-12-27 |
| JP6878149B2 JP6878149B2 (en) | 2021-05-26 |
Family
ID=64956435
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017107023A Active JP6878149B2 (en) | 2017-05-30 | 2017-05-30 | Liquid crystal polymer composition |
| JP2021076127A Active JP7266633B2 (en) | 2017-05-30 | 2021-04-28 | liquid crystal polymer composition |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2021076127A Active JP7266633B2 (en) | 2017-05-30 | 2021-04-28 | liquid crystal polymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JP6878149B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024204594A1 (en) * | 2023-03-30 | 2024-10-03 | ポリプラスチックス株式会社 | Liquid crystalline resin composition and camera module using same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005054017A (en) * | 2003-08-01 | 2005-03-03 | Polyplastics Co | Flame retardant resin composition |
| JP2005290370A (en) * | 2004-03-10 | 2005-10-20 | Matsushita Electric Works Ltd | Metal-coated resin molded product and method for producing the same |
| WO2007043701A1 (en) * | 2005-10-13 | 2007-04-19 | Polyplastics Co., Ltd. | Liquid crystalline resin composition for use in injection molding |
| JP2008019400A (en) * | 2006-07-14 | 2008-01-31 | Wintech Polymer Ltd | Flame-retardant polybutylene terephthalate resin composition |
| WO2013129338A1 (en) * | 2012-02-29 | 2013-09-06 | ポリプラスチックス株式会社 | Liquid crystal resin composition for camera modules |
| JP2017066353A (en) * | 2015-09-30 | 2017-04-06 | 東レ株式会社 | Liquid crystal polyester resin composition and molded article made of the same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05117506A (en) * | 1991-10-25 | 1993-05-14 | Mitsubishi Petrochem Co Ltd | Polyester resin composition improved in fluidity |
| US5216073A (en) * | 1992-07-01 | 1993-06-01 | Hoechst Celanese Corp. | Thermoset LCP blends |
| JP3269219B2 (en) * | 1993-10-15 | 2002-03-25 | 東レ株式会社 | Flame retardant resin composition |
| JPH10237323A (en) * | 1996-10-16 | 1998-09-08 | Toray Ind Inc | Resin composition and molded product |
-
2017
- 2017-05-30 JP JP2017107023A patent/JP6878149B2/en active Active
-
2021
- 2021-04-28 JP JP2021076127A patent/JP7266633B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005054017A (en) * | 2003-08-01 | 2005-03-03 | Polyplastics Co | Flame retardant resin composition |
| JP2005290370A (en) * | 2004-03-10 | 2005-10-20 | Matsushita Electric Works Ltd | Metal-coated resin molded product and method for producing the same |
| WO2007043701A1 (en) * | 2005-10-13 | 2007-04-19 | Polyplastics Co., Ltd. | Liquid crystalline resin composition for use in injection molding |
| JP2008019400A (en) * | 2006-07-14 | 2008-01-31 | Wintech Polymer Ltd | Flame-retardant polybutylene terephthalate resin composition |
| WO2013129338A1 (en) * | 2012-02-29 | 2013-09-06 | ポリプラスチックス株式会社 | Liquid crystal resin composition for camera modules |
| JP2017066353A (en) * | 2015-09-30 | 2017-04-06 | 東レ株式会社 | Liquid crystal polyester resin composition and molded article made of the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024204594A1 (en) * | 2023-03-30 | 2024-10-03 | ポリプラスチックス株式会社 | Liquid crystalline resin composition and camera module using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2021119242A (en) | 2021-08-12 |
| JP6878149B2 (en) | 2021-05-26 |
| JP7266633B2 (en) | 2023-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8696932B2 (en) | Liquid-crystalline polymer composition | |
| JP2019043996A (en) | Liquid crystal polyester resin | |
| JP6821316B2 (en) | Liquid crystal polymer composition | |
| WO2016043091A1 (en) | Liquid crystal polymer | |
| JP6533880B1 (en) | Liquid crystal polyester resin | |
| CN111944278B (en) | Liquid crystalline polymer composition | |
| JP2016065228A (en) | Liquid crystal polymer | |
| JPWO2020070904A1 (en) | Liquid crystal polyester resin | |
| JP6776099B2 (en) | Liquid crystal polymer composition | |
| JP2020193261A (en) | Liquid crystal polymer composition | |
| JP2018012789A (en) | Liquid crystal polymer | |
| JP7266633B2 (en) | liquid crystal polymer composition | |
| JP2017095600A (en) | Liquid crystal polymer | |
| JP6258771B2 (en) | Liquid crystal polymer | |
| JP2015040249A (en) | Liquid crystal polymer composition | |
| JP2017214460A (en) | Thermoplastic resin composition | |
| JP2017043705A (en) | Liquid crystal polymer | |
| WO2020070904A1 (en) | Liquid crystal polyester resin | |
| WO2020070903A1 (en) | Liquid crystal polyester resin | |
| CN112341609A (en) | Liquid crystalline polyester resin | |
| JP2021134312A (en) | Liquid crystal polymer composition | |
| JP2017014357A (en) | Liquid crystal polymer for electronic component | |
| JP6433211B2 (en) | Liquid crystal polymer | |
| JP7498641B2 (en) | Liquid crystal polymer composition | |
| JP7469138B2 (en) | Liquid Crystal Polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20170817 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20200116 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20201006 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20201201 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20210125 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20210406 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20210428 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6878149 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |