JP3147315B2 - Thermal liquid crystalline polyester and molded articles made thereof - Google Patents
Thermal liquid crystalline polyester and molded articles made thereofInfo
- Publication number
- JP3147315B2 JP3147315B2 JP19695991A JP19695991A JP3147315B2 JP 3147315 B2 JP3147315 B2 JP 3147315B2 JP 19695991 A JP19695991 A JP 19695991A JP 19695991 A JP19695991 A JP 19695991A JP 3147315 B2 JP3147315 B2 JP 3147315B2
- Authority
- JP
- Japan
- Prior art keywords
- structural unit
- acid
- polymer
- polyester
- mol
- 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.)
- Expired - Fee Related
Links
- 229920000728 polyester Polymers 0.000 title claims description 89
- 239000007788 liquid Substances 0.000 title claims description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 34
- 239000001301 oxygen Substances 0.000 claims description 34
- 229910052760 oxygen Inorganic materials 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 58
- -1 polyethylene terephthalate Polymers 0.000 description 43
- 230000004888 barrier function Effects 0.000 description 28
- 230000001965 increasing effect Effects 0.000 description 26
- 229920000106 Liquid crystal polymer Polymers 0.000 description 21
- 229920000139 polyethylene terephthalate Polymers 0.000 description 20
- 239000005020 polyethylene terephthalate Substances 0.000 description 20
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 19
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 19
- 239000011112 polyethylene naphthalate Substances 0.000 description 19
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 18
- 239000012071 phase Substances 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000007789 gas Substances 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 15
- 238000000113 differential scanning calorimetry Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 230000035699 permeability Effects 0.000 description 14
- 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 13
- 238000005452 bending Methods 0.000 description 13
- 230000009477 glass transition Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 11
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 10
- 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 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 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 8
- 239000004973 liquid crystal related substance Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000005022 packaging material Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 238000005917 acylation reaction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000006059 cover glass Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 2
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 2
- LTFHNKUKQYVHDX-UHFFFAOYSA-N 4-hydroxy-3-methylbenzoic acid Chemical compound CC1=CC(C(O)=O)=CC=C1O LTFHNKUKQYVHDX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 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 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 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
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000012360 testing method Methods 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
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- 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
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- QGNLHMKIGMZKJX-UHFFFAOYSA-N 3-chloro-4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(Cl)=C1 QGNLHMKIGMZKJX-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- PSAGPCOTGOTBQB-UHFFFAOYSA-N 4-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(O)C2=C1 PSAGPCOTGOTBQB-UHFFFAOYSA-N 0.000 description 1
- NYYMNZLORMNCKK-UHFFFAOYSA-N 5-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1O NYYMNZLORMNCKK-UHFFFAOYSA-N 0.000 description 1
- FSXKKRVQMPPAMQ-UHFFFAOYSA-N 7-hydroxynaphthalene-2-carboxylic acid Chemical compound C1=CC(O)=CC2=CC(C(=O)O)=CC=C21 FSXKKRVQMPPAMQ-UHFFFAOYSA-N 0.000 description 1
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- YWMLORGQOFONNT-UHFFFAOYSA-N [3-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC(CO)=C1 YWMLORGQOFONNT-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
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- HQCVEGNPQFRFPC-UHFFFAOYSA-N carboxy acetate Chemical compound CC(=O)OC(O)=O HQCVEGNPQFRFPC-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000005165 hydroxybenzoic acids Chemical class 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 238000009884 interesterification Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 235000015095 lager Nutrition 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 150000002736 metal compounds Chemical class 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- 125000001038 naphthoyl group Chemical group C1(=CC=CC2=CC=CC=C12)C(=O)* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000014214 soft drink Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 235000013555 soy sauce Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Liquid Crystal Substances (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は成形性の改良された光学
的に異方性の溶融相を形成する共重合ポリエステル、お
よびそれからなる酸素バリヤー性に優れた成形品に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a copolymerized polyester which forms an optically anisotropic molten phase having improved moldability, and a molded article comprising the same which has excellent oxygen barrier properties.
【０００２】[0002]
【従来の技術】ポリエステル、とりわけポリエチレンテ
レフタレート（以下ＰＥＴと略称することがある）は、
衛生性、保香性、加工性等の優れた性質を有しているた
めに、醤油、ソース等の調味料、ジュース、コーラ、ラ
ムネ等のソフトドリンク、生ビール、化粧品、医薬品な
どの容器として広く利用されている。さらに上記のよう
な性能に加えて、ガラスよりも軽量であること、適度の
耐圧力性、ガスバリヤー性を有することから、今後ガラ
ス瓶の代替としての一層の伸長が期待されている。しか
しながら、ガラス瓶代替として最も市場が大きいと予想
されるラガービール、ワイン等ではシェルフライフが長
くなること、また炭酸飲料等では容器の小型化により内
容量当たりの容器の表面積が増大することから、外部か
らの酸素の侵入や炭酸ガスの散逸をさらに減少させるた
めに容器のガスバリヤー性の向上が強く要望されてい
る。ＰＥＴ自体のガスバリヤー性の改良については、す
でにかなりのハイレベルにあること、また容器成形性能
や耐圧力性等の機械的性質を損なうことなく改良する必
要があることから、その実現はきわめて困難である。従
来ＰＥＴ容器のガスバリヤー性を改良する方法は種々提
案されている。例えば、容器の内外層にポリ塩化ビニリ
デン等をコーティングする方法や、エチレン−酢酸ビニ
ル共重合体ケン化物等を用いて２層〜５層の多層構造と
する方法（特開昭５６−７７１４３号公報）等が提案さ
れているが、これらの方法は従来のポリエステルの成形
設備にさらにコーティングや多層容器とするための設備
が必要となり工業上不利であるばかりでなく、異種のポ
リマーを用いるために多層容器の場合には層間剥離を起
こしやすい点、さらには使用済みの容器の回収再利用や
焼却等についても不都合な点を有している。またあらか
じめポリエステルとナイロン等の異種ポリマーをブレン
ドしたものから容器を製造する方法も提案されている
（特公昭５３−３３６１８号公報、特開昭５６−６４８
３９号公報）。この場合、既存の設備で容器の製造は可
能であるが、容器の物性低下を伴うことと、回収再利用
の点から不利である。2. Description of the Related Art Polyester, especially polyethylene terephthalate (hereinafter sometimes abbreviated as PET), is
Due to its excellent properties such as hygiene, fragrance retention, and processability, it is widely used as containers for seasonings such as soy sauce and sauces, soft drinks such as juice, cola, and ramune, draft beer, cosmetics, and pharmaceuticals. It's being used. Furthermore, in addition to the above-mentioned performance, it is lighter than glass, has moderate pressure resistance, and has gas barrier properties. Therefore, further growth as a substitute for glass bottles is expected in the future. However, lager beer and wine, which are expected to be the largest markets for glass bottles, have a longer shelf life, and carbonated beverages and other beverages have a smaller container, which increases the surface area of the container per unit volume. In order to further reduce the intrusion of oxygen from the atmosphere and the dissipation of carbon dioxide gas, there is a strong demand for improving the gas barrier properties of the container. It is extremely difficult to improve the gas barrier properties of PET itself because it is already at a very high level and it is necessary to improve the mechanical properties such as container molding performance and pressure resistance. It is. Conventionally, various methods for improving the gas barrier properties of PET containers have been proposed. For example, a method of coating the inner and outer layers of a container with polyvinylidene chloride or the like, or a method of forming a multilayer structure of two to five layers using a saponified ethylene-vinyl acetate copolymer (Japanese Patent Application Laid-Open No. 56-77143) However, these methods are not only industrially disadvantageous because equipment for coating and forming a multilayer container are required in addition to the conventional polyester molding equipment, but are also industrially disadvantageous. In the case of containers, delamination is apt to occur, and further, there is an inconvenience in the recovery and reuse of used containers and incineration. Also, a method of manufacturing a container from a blend of different polymers such as polyester and nylon in advance has been proposed (JP-B-53-33618, JP-A-56-648).
No. 39). In this case, the container can be manufactured with the existing equipment, but it is disadvantageous in that the physical properties of the container are deteriorated and that the container is recovered and reused.
【０００３】一方、光学的に異方性の溶融相を形成する
いわゆるサーモトロピック液晶ポリマーをガスバリヤー
材として用いる方法も近年提案されている（特開昭６１
−１９２７６２号公報、特開昭６２−１１９２６５号公
報、特開昭６２−１８７０３３号公報、特開昭６４−４
５２４２号公報、特開平１−２８８４２１号公報）。ま
た、Ｐｏｌｙｍ．Ｐｒｅｐｒ．（Ａｍ．Ｃｈｅｍ．Ｓｏ
ｃ．，Ｄｉｖ．Ｐｏｌｙｍ．Ｃｈｅｍ．），３０
（１），３−４（１９８９）には、４０モル％のポリエ
チレンテレフタレートと６０モル％の４−アセトキシ安
息香酸とから製造されるサーモトロピック液晶ポリマー
より得られる溶融押出しフイルムの３５℃での酸素ガス
透過量は３６ｍｌ・２０μ ｍ／ｍ↑2・ｄａｙ・ａｔｍ
であることが報告されている。On the other hand, a method using a so-called thermotropic liquid crystal polymer, which forms an optically anisotropic molten phase, as a gas barrier material has recently been proposed (Japanese Patent Application Laid-Open No. 61-1986).
JP-A-192762, JP-A-62-119265, JP-A-62-187033, JP-A-64-4
No. 5242, JP-A-1-288421). Also, Polym. Prepr. (Am. Chem. So
c. , Div. Polym. Chem. ), 30
(1), 3-4 (1989) disclose that a melt-extruded film obtained from a thermotropic liquid crystal polymer produced from 40 mol% of polyethylene terephthalate and 60 mol% of 4-acetoxybenzoic acid at 35 ° C. Gas permeation amount is 36ml ・ 20μm / m ↑ 2 ・ day ・ atm
Is reported.
【０００４】なお、特公昭５６−１８０１６号公報に
は、式−ＯＣ−Ｒ↓1−ＣＯ−Ｏ−Ｒ↓2−Ｏ−（ここで
Ｒ↓1は炭素数４〜２０の脂環族２価ラジカル、炭素数
１〜４０の脂肪族２価ラジカル、または少なくとも３個
の炭素原子で隔てられたカルボニル結合をもつ炭素数６
〜１６の芳香族２価ラジカルを、Ｒ↓2は炭素数２〜４
０の脂肪族２価ラジカル、炭素数４〜２０の脂環族２価
ラジカル、炭素数６〜２０の芳香族２価ラジカルまたは
分子量２００〜８０００のポリ（アルキレンオキシド）
２価ラジカルを示す）で表される繰り返し単位を有する
ポリエステルとアシルオキシ芳香族カルボン酸とを反応
させることによる共重合ポリエステルの製造方法が開示
されているが、アシルオキシ芳香族カルボン酸として
は、具体的にはアシルオキシ安息香酸類が例示されてい
るのみである。Japanese Patent Publication No. 56-18016 discloses a compound represented by the formula -OC-R ↓ 1-CO-OR- ↓ 2-O- (where R ↓ 1 is an alicyclic group having 4 to 20 carbon atoms). Radical, an aliphatic divalent radical having 1 to 40 carbon atoms, or 6 carbon atoms having a carbonyl bond separated by at least 3 carbon atoms
１６16 aromatic divalent radicals, and R ↓ 2 has 2 to 4 carbon atoms.
An aliphatic divalent radical having 0, an alicyclic divalent radical having 4 to 20 carbon atoms, an aromatic divalent radical having 6 to 20 carbon atoms, or poly (alkylene oxide) having a molecular weight of 200 to 8000
A method for producing a copolymerized polyester by reacting a polyester having a repeating unit represented by a divalent radical) with an acyloxy aromatic carboxylic acid is disclosed, but specific examples of the acyloxy aromatic carboxylic acid include: Only acyloxybenzoic acids are exemplified.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、従来提
案されているサーモトロピック液晶ポリマーを酸素バリ
ヤー用の成形体として用いる場合には多くの問題点があ
る。すなわち、第一の問題点としては、従来提案されて
いるサーモトロピック液晶ポリマーから得られる成形品
は概して結晶化度が高く、力学的物性の異方性が大であ
り、伸度が小であり実質的には延伸が不可能である点で
ある。従って、このようなポリマーから酸素バリヤー用
の各種の成形体、例えば、フイルム、シート、ボトル、
カップ、トレイ、袋等に成形加工することは非常に困難
である。However, there are many problems when using the conventionally proposed thermotropic liquid crystal polymer as a molded product for an oxygen barrier. That is, the first problem is that molded products obtained from the conventionally proposed thermotropic liquid crystal polymer generally have high crystallinity, large mechanical property anisotropy, and small elongation. The point is that stretching is substantially impossible. Therefore, from such polymers, various molded articles for oxygen barrier, for example, films, sheets, bottles,
It is very difficult to form into cups, trays, bags and the like.
【０００６】そのため、特開昭６２−１８７０３３号公
報では熱（サーモトロピック）液晶ポリエステルからな
る層と少なくともその片面にポリエチレンテレフタレー
ト成分を含有するポリエステルからなる層を有する積層
延伸成形品が提案されている。該公報中には（光学的に
異方性を形成しない）ポリエステルからなる層と熱液晶
ポリエステルからなる層の厚み比は、積層延伸成形品の
全厚みに対してポリエステル層が５０〜９８％、熱液晶
ポリエステル層が２〜５０％、好ましくは５〜２０％で
あることが開示されており、熱液晶ポリエステル層が５
０％以上である場合には、ポリエステル単独で延伸した
場合に比べて延伸させにくいと記載されている。一方、
力学物性の異方性の小なる成形品を与えるサーモトロピ
ック液晶ポリマーに関する提案もなされている。例え
ば、特開昭６０−２８４２８号公報には、テレフタロイ
ル基、１，３−ジオキシフェニレン基および２−置換−
１，４−ジオキシフェニレン基からなるサーモトロピッ
ク液晶ポリエステルが提案されている。このように、イ
ソ骨格、および置換基の導入により、サーモトロピック
液晶ポリマーの成形性が向上し、必ずしも充分ではない
が、各種の成形体を製造することは容易となる方向では
ある。For this reason, Japanese Patent Application Laid-Open No. 62-187033 proposes a laminated stretch-formed product having a layer made of a thermo (thermotropic) liquid crystal polyester and a layer made of a polyester containing a polyethylene terephthalate component on at least one surface thereof. . In the publication, the thickness ratio of the layer made of polyester (which does not form optically anisotropic) to the layer made of thermo-liquid crystalline polyester is such that the polyester layer is 50 to 98% of the total thickness of the laminated stretch-formed product, It is disclosed that the thermal liquid crystal polyester layer is 2 to 50%, preferably 5 to 20%.
It is described that when it is 0% or more, it is difficult to stretch as compared with the case where polyester is stretched alone. on the other hand,
Proposals have also been made regarding thermotropic liquid crystal polymers that provide molded articles with small anisotropy in mechanical properties. For example, JP-A-60-28428 discloses a terephthaloyl group, a 1,3-dioxyphenylene group and a 2-substituted-
A thermotropic liquid crystal polyester comprising a 1,4-dioxyphenylene group has been proposed. As described above, the moldability of the thermotropic liquid crystal polymer is improved by the introduction of the isoskeleton and the substituent, and although it is not always sufficient, it is easy to manufacture various molded articles.
【０００７】また、従来提案されているサーモトロピッ
ク液晶ポリマーを酸素バリヤー用の成形体として用いる
場合に生じうる第二の問題点としては、サーモトロピッ
ク液晶ポリマーから得られる成形品の中には、酸素バリ
ヤー性が必ずしも充分に高いとは言い難いものも含まれ
ていることである。例えば前述したＰｏｌｙｍ．Ｐｒｅ
ｐｒ．（Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，Ｄｉｖ．Ｐｏｌｙ
ｍ．Ｃｈｅｍ．），３０（１），３−４（１９８９）に
記載された４０モル％のポリエチレンテレフタレートと
６０モル％の４−アセトキシ安息香酸とから製造される
サーモトロピック液晶ポリマーから得られるフイルムの
酸素ガス透過量は、３６ｍｌ・２０μｍ／ｍ↑2・ｄａ
ｙ・ａｔｍであることが報告されているように、該ポリ
マーは必ずしも高性能の酸素バリヤー材とは言えないレ
ベルである。また本発明者等の検討によると、前述の特
開昭６０−２８４２８号公報に記載されたサーモトロピ
ック液晶ポリエステルから得られるフイルムの酸素バリ
ヤー性も、必ずしも高いレベルではないことが判明し
た。A second problem that may arise when the conventionally proposed thermotropic liquid crystal polymer is used as a molded body for an oxygen barrier is that a molded article obtained from the thermotropic liquid crystal polymer contains oxygen. The barrier properties are not necessarily high enough. For example, Polym. Pre
pr. (Am. Chem. Soc., Div. Poly.
m. Chem. ), 30 (1), 3-4 (1989). Oxygen gas permeation of a film obtained from a thermotropic liquid crystal polymer produced from 40 mol% of polyethylene terephthalate and 60 mol% of 4-acetoxybenzoic acid. The volume is 36ml ・ 20μm / m ↑ 2 ・ da
As reported to be y · atm, the polymer is at a level that is not necessarily a high performance oxygen barrier material. According to the study by the present inventors, it has been found that the oxygen barrier property of the film obtained from the thermotropic liquid crystal polyester described in the above-mentioned JP-A-60-28428 is not always at a high level.
【０００８】また、特開昭６２−６８８１３号公報に
は、ｐ−アセトキシ安息香酸と６−アセトキシ−２−ナ
フトエ酸とのアセトキシ芳香族カルボン酸混合物をポリ
エチレンテレフタレートまたはポリブチレンテレフタレ
ートと反応させることにより得られる共重合ポリエステ
ルが開示されており、アセトキシ芳香族カルボン酸とし
てｐ−アセトキシ安息香酸のみを用いた場合に較べて曲
げ強度、曲げ弾性率、および熱変形温度が改善されると
記載されている。しかしながら、かかる公報には、該共
重合ポリエステルからなる包装材料も容器も記載されて
おらず、しかも、該共重合ポリエステルが優れたガスバ
リヤー性、成形性（延伸性）、低温流動性などの優れた
特性を有するか否かについてさえも何ら開示されていな
い。Japanese Patent Application Laid-Open No. Sho 62-68813 discloses that an acetoxy aromatic carboxylic acid mixture of p-acetoxybenzoic acid and 6-acetoxy-2-naphthoic acid is reacted with polyethylene terephthalate or polybutylene terephthalate. The obtained copolymerized polyester is disclosed, and it is described that the bending strength, the bending elastic modulus, and the heat distortion temperature are improved as compared with a case where only p-acetoxybenzoic acid is used as the acetoxy aromatic carboxylic acid. . However, this publication does not describe a packaging material or a container comprising the copolymerized polyester, and furthermore, the copolymerized polyester has excellent gas barrier properties, moldability (stretchability), low-temperature fluidity, and the like. No disclosure is made as to whether or not it has the characteristics described above.
【０００９】[0009]
【課題を解決するための手段】このような状況に鑑み、
本発明者等は、従来の熱液晶ポリマーが達成し得ない優
れた成形性を有し、かつ成形品において高度なガスバリ
ヤー性を備えた熱液晶ポリマーおよびそれからなる成形
品を提供すべく鋭意検討を重ねた結果、本発明を完成す
るに至った。In view of such a situation,
The present inventors have studied diligently to provide a thermo-liquid crystal polymer having excellent moldability that cannot be achieved by the conventional thermo-liquid crystal polymer and having a high gas barrier property in the molded product and a molded product comprising the same. As a result, the present invention has been completed.
【００１０】すなわち本発明は、第一に新規な熱液晶ポ
リエステルを提供するものであり、それは、実質的に下
記化５That is, the present invention firstly provides a novel thermal liquid crystalline polyester, which is substantially the following:
【００１１】[0011]
【化５】 Embedded image
【００１２】で示される構成単位（１）、下記化６Structural unit (1) represented by the following formula:
【００１３】[0013]
【化６】 Embedded image
【００１４】で示される構成単位（２）、下記化７The structural unit (2) represented by the following formula:
【００１５】[0015]
【化７】 Embedded image
【００１６】で示される構成単位（３）および下記化８Structural unit (3) represented by the following formula and
【００１７】[0017]
【化８】 Embedded image
【００１８】で示される構成単位（４）からなり、構成
単位（１）と構成単位（２）を実質的に等しいモル数で
含み、構成単位（１）および構成単位（２）の合計量が
１５〜９０モル％、構成単位（３）および構成単位
（４）の合計量が１０〜８５モル％であり、構成単位
（３）および構成単位（４）の合計量に対する構成単位
（３）の割合が１０モル％以上である熱液晶ポリエステ
ルである。The structural unit (4) comprises the structural unit (1) and the structural unit (2) in substantially equal moles, and the total amount of the structural unit (1) and the structural unit (2) is 15 to 90 mol%, the total amount of the structural unit (3) and the structural unit (4) is 10 to 85 mol%, and the ratio of the structural unit (3) to the total amount of the structural unit (3) and the structural unit (4) is This is a thermal liquid crystalline polyester having a ratio of 10 mol% or more.
【００１９】本発明は、第二に、改善されたガスバリヤ
ー性、とりわけ高度の酸素バリヤー性を有する成形品を
提供するものであり、その成形品は本発明の新規な熱液
晶ポリエステルからなる成形品である。尚、本明細書に
おいて用いられる用語「成形品」とは主として飲食品、
医薬品等の包装用途に適する成形物品を意味する。この
ような成形物品は本発明の熱液晶ポリエステルを成形し
て得られるシート；フイルム；ボトル、トレイ、カッ
プ、袋等の有底容器などを含む。The present invention secondly provides a molded article having an improved gas barrier property, especially a high oxygen barrier property, wherein the molded article comprises the novel thermo-liquid crystalline polyester of the present invention. Goods. In addition, the term "molded article" used in the present specification mainly refers to food and drink,
It means a molded article suitable for packaging use such as pharmaceuticals. Such molded articles include sheets obtained by molding the thermal liquid crystalline polyester of the present invention; films; bottomed containers such as bottles, trays, cups, and bags.
【００２０】以下本発明を詳細に説明する。本発明の熱
液晶ポリエステルの構成単位（１）は、２，６−ナフタ
レンジカルボン酸、あるいはそのエステル形成性誘導体
によって導入されるような２，６−ナフタレンジカルボ
ニル基である。構成単位（１）の一部、好ましくは構成
単位（１）の２０モル％以下は、他のジカルボン酸また
はそのエステル形成性誘導体によって導入されうる構成
単位に置き換えられていてもよい。他のジカルボン酸と
しては例えば、テレフタル酸、イソフタル酸、２，７−
ナフタレンジカルボン酸、１，４−ナフタレンジカルボ
ン酸、１，４−シクロヘキサンジカルボン酸、コハク
酸、アジピン酸、セバシン酸などが挙げられる。また得
られるポリエステルが溶融成形可能である範囲内の量で
あれば、構成単位（１）の一部をトリメリット酸、トリ
メシン酸、ピロメリット酸などの多価カルボン酸または
そのエステル形成性誘導体によって導入されうる構成単
位に置き換えることも可能である。Hereinafter, the present invention will be described in detail. The structural unit (1) of the thermal liquid crystalline polyester of the present invention is a 2,6-naphthalenedicarbonyl group as introduced by 2,6-naphthalenedicarboxylic acid or an ester-forming derivative thereof. A part of the structural unit (1), preferably 20 mol% or less of the structural unit (1), may be replaced by a structural unit that can be introduced by another dicarboxylic acid or an ester-forming derivative thereof. Other dicarboxylic acids include, for example, terephthalic acid, isophthalic acid, 2,7-
Examples include naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid and the like. Further, if the obtained polyester is in an amount within a range capable of being melt-molded, a part of the structural unit (1) may be converted to a polycarboxylic acid such as trimellitic acid, trimesic acid, and pyromellitic acid or an ester-forming derivative thereof. It is also possible to replace with a structural unit that can be introduced.
【００２１】また、本発明の熱液晶ポリエステルにおけ
る構成単位（２）とは、エチレングリコールにより導入
されるようなエチレンジオキシ基であるが、その一部、
好ましくは構成単位（２）の２０モル％以下は、他のグ
リコールにより導入されうる構成単位に置き換えられて
いてもよい。エチレングリコール以外のグリコールとし
ては、例えば、１，２−プロパンジオール、１，３−プ
ロパンジオール、１，４−ブタンジオール、１，３−ブ
タンジオール、２−メチル−１，３−プロパンジオー
ル、１，５−ペンタンジオール、ネオペンチルグリコー
ル、１，６−ヘキサンジオール、３−メチル−１，５−
ペンタンジオール、１，４−シクロヘキサンジメタノー
ル、ジエチレングリコール、トリエチレングリコール、
ｏ−、ｍ−またはｐ−キシリレングリコールなどが挙げ
られる。また得られるポリエステルが溶融成形可能であ
る範囲内の量であれば、構成単位（２）の一部を、グリ
セリン、トリメチロールプロパン、トリエチロールプロ
パン、ペンタエリスリトールなどの多価アルコールによ
り導入されうる構成単位に置き換えることも可能であ
る。The structural unit (2) in the thermal liquid crystalline polyester of the present invention is an ethylenedioxy group introduced by ethylene glycol.
Preferably, 20 mol% or less of the structural unit (2) may be replaced by a structural unit that can be introduced by another glycol. Examples of glycols other than ethylene glycol include 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, , 5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-
Pentanediol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol,
o-, m- or p-xylylene glycol and the like. If the amount of the obtained polyester is within the range that can be melt-molded, a part of the structural unit (2) can be introduced by a polyhydric alcohol such as glycerin, trimethylolpropane, triethylolpropane, and pentaerythritol. It is also possible to replace with a unit.
【００２２】本発明の熱液晶ポリエステルにおける構成
単位（１）および（２）は、通常は、主たる出発物質と
して２，６−ナフタレンジカルボン酸、またはそのエス
テル形成性誘導体とエチレングリコールを用いる反応に
よって得られるポリエチレンナフタレート系のポリエス
テルを原料のひとつとして用いることによって本発明の
熱液晶ポリエステルの分子中に導入される。The structural units (1) and (2) in the thermal liquid crystalline polyester of the present invention are usually obtained by a reaction using ethylene glycol with 2,6-naphthalenedicarboxylic acid or its ester-forming derivative as a main starting material. By using the obtained polyethylene naphthalate-based polyester as one of the raw materials, it is introduced into the molecules of the thermo-liquid crystalline polyester of the present invention.
【００２３】本発明の熱液晶ポリエステルの製造におい
て用いるポリエチレンナフタレート系のポリエステル
は、従来ポリエチレンナフタレートの製造に際して提案
されている方法で製造することができる。例えば、ジカ
ルボン酸とグリコールとをエステル化反応したあと重縮
合する方法、ジカルボン酸エステルとグリコールとをエ
ステル交換したあと重縮合する方法等によって得られ
る。その際、エステル化触媒、エステル交換触媒、重縮
合触媒、安定剤等を使用することが好ましい結果を与え
る場合があるが、これらの触媒、安定剤等としては、ポ
リエステル、特にポリエチレンナフタレートの製造にお
いて使用しうる触媒、安定剤等として知られているもの
を用いることができる。例えば、これらの反応を促進す
る触媒としては、ナトリウム、マグネシウム、カルシウ
ム、亜鉛、マンガン、錫、タングステン、ゲルマニウ
ム、チタン、アンチモン等の金属化合物が、また安定剤
としてはリン酸、リン酸エステル類、亜リン酸、亜リン
酸エステル類などのリン化合物を例示することができ
る。さらに、必要に応じて他の添加剤（着色剤、紫外線
吸収剤、光安定化剤、帯電防止剤、難燃剤、結晶化促進
剤等）を添加することもできる。The polyethylene naphthalate-based polyester used in the production of the thermal liquid crystalline polyester of the present invention can be produced by a method conventionally proposed for producing polyethylene naphthalate. For example, it can be obtained by a method of subjecting a dicarboxylic acid and a glycol to an esterification reaction followed by polycondensation, a method of subjecting a dicarboxylic acid ester and a glycol to interesterification and then a polycondensation. In this case, it is sometimes preferable to use an esterification catalyst, a transesterification catalyst, a polycondensation catalyst, a stabilizer, etc., but these catalysts, stabilizers, etc. may be used for production of polyester, especially polyethylene naphthalate. What is known as a catalyst, a stabilizer, etc. which can be used in the above can be used. For example, catalysts that promote these reactions include sodium, magnesium, calcium, zinc, manganese, tin, tungsten, germanium, titanium, antimony and other metal compounds, and as stabilizers phosphoric acid, phosphate esters, Phosphorus compounds such as phosphorous acid and phosphites can be exemplified. Further, other additives (a coloring agent, an ultraviolet absorber, a light stabilizer, an antistatic agent, a flame retardant, a crystallization accelerator, etc.) can be added as needed.
【００２４】本発明の熱液晶ポリエステルを製造する際
に原料ポリエステルとして用いるポリエチレンナフタレ
ート系ポリエステルの重合度に関しては、特に規定はな
いが、フェノール／テトラクロロエタン等重量混合溶媒
中、３０℃で測定した極限粘度が０．０１〜１．５ｄｌ
／ｇのものを用いることが望ましい。The degree of polymerization of the polyethylene naphthalate-based polyester used as a raw material polyester in producing the thermal liquid crystalline polyester of the present invention is not particularly limited, but was measured at 30 ° C. in a mixed solvent such as phenol / tetrachloroethane by weight. Intrinsic viscosity is 0.01-1.5dl
/ G is desirably used.
【００２５】構成単位（１）および構成単位（２）は、
それらの合計量において熱液晶ポリエステル中、１５〜
９０モル％の範囲内、好ましくは２５〜８５モル％の範
囲内、より好ましくは３０〜８０モル％の範囲内で存在
する。The structural unit (1) and the structural unit (2) are
In their total amount in the thermal liquid crystalline polyester, 15-
It is present in the range of 90 mol%, preferably in the range of 25-85 mol%, more preferably in the range of 30-80 mol%.
【００２６】本発明の熱液晶ポリエステルにおける構成
単位（３）および構成単位（４）は、それぞれ、６−ヒ
ドロキシ−２−ナフトエ酸もしくはそのエステル形成性
誘導体により導入されるような６−オキシ−２−ナフト
イル基およびｐ−ヒドロキシ安息香酸もしくはそのエス
テル形成性誘導体により導入されるような４−オキシベ
ンゾイル基である。構成単位（３）および構成単位
（４）の一部、好ましくはそれらを合わせたものの１０
モル％以下は、他のヒドロキシ芳香族カルボン酸または
そのエステル形成性誘導体によって導入されうる構成単
位に置き換えられていてもよい。６−ヒドロキシ−２−
ナフトエ酸およびｐ−ヒドロキシ安息香酸以外のヒドロ
キシ芳香族カルボン酸としては、例えば、ｍ−ヒドロキ
シ安息香酸、４−ヒドロキシ−３−クロロ安息香酸、４
−ヒドロキシ−３，５−ジメチル安息香酸、４−ヒドロ
キシ−３−メチル安息香酸、７−ヒドロキシ−２−ナフ
トエ酸、４−ヒドロキシ−１−ナフトエ酸、５−ヒドロ
キシ−１−ナフトエ酸等が挙げられる。The structural unit (3) and the structural unit (4) in the thermal liquid crystalline polyester of the present invention are each 6-oxy-2 as introduced by 6-hydroxy-2-naphthoic acid or an ester-forming derivative thereof. -A naphthoyl group and a 4-oxybenzoyl group as introduced by p-hydroxybenzoic acid or its ester-forming derivative. Structural unit (3) and part of structural unit (4), preferably 10
Up to mol% may be replaced by structural units which can be introduced by other hydroxyaromatic carboxylic acids or their ester-forming derivatives. 6-hydroxy-2-
Examples of hydroxy aromatic carboxylic acids other than naphthoic acid and p-hydroxybenzoic acid include m-hydroxybenzoic acid, 4-hydroxy-3-chlorobenzoic acid,
-Hydroxy-3,5-dimethylbenzoic acid, 4-hydroxy-3-methylbenzoic acid, 7-hydroxy-2-naphthoic acid, 4-hydroxy-1-naphthoic acid, 5-hydroxy-1-naphthoic acid and the like. Can be
【００２７】また、本発明の熱液晶ポリエステルにおい
て、構成単位（３）および構成単位（４）の含有量の合
計は、１０〜８５モル％の範囲が適当であり、好ましく
は１５〜７５モル％であり、より好ましくは２０〜７０
モル％である。構成単位（３）および構成単位（４）の
含有量の合計が８５モル％を越えると、溶融重合が困難
となること、成形性が著しく損なわれることなどの不都
合が生じ、１０モル％未満であると、得られるポリエス
テルは熱液晶を形成せず、ガスバリヤー性が大きく低下
するので好ましくない。In the thermal liquid crystalline polyester of the present invention, the total content of the structural units (3) and (4) is suitably in the range of 10 to 85 mol%, preferably 15 to 75 mol%. And more preferably 20 to 70
Mol%. When the total content of the structural units (3) and (4) exceeds 85 mol%, disadvantages such as difficulty in melt polymerization and remarkable impairment of moldability occur, and when the total content is less than 10 mol%. If so, the resulting polyester does not form a thermal liquid crystal, and the gas barrier property is greatly reduced.
【００２８】また、構成単位（３）および構成単位
（４）の合計量に対する構成単位（３）の量の割合が１
０モル％以上であることが必要であり、このことによ
り、酸素ガスバリヤー性に極めて優れた成形品を与える
ポリエステルが得られる。The ratio of the amount of the structural unit (3) to the total amount of the structural unit (3) and the structural unit (4) is 1
It is necessary that the content be 0 mol% or more, whereby a polyester which gives a molded article having extremely excellent oxygen gas barrier properties can be obtained.
【００２９】本発明の熱液晶ポリエステルにおける構成
単位（３）および構成単位（４）は、通常対応するアシ
ルオキシカルボン酸を原料として用いることによりポリ
マー分子中に導入される。アシルオキシカルボン酸とし
ては、対応するヒドロキシカルボン酸と無水酢酸との反
応によって得られるようなアセトキシカルボン酸が好ま
しい。The structural units (3) and (4) in the thermal liquid crystalline polyester of the present invention are usually introduced into the polymer molecule by using the corresponding acyloxycarboxylic acid as a raw material. As the acyloxycarboxylic acid, an acetoxycarboxylic acid obtained by a reaction between the corresponding hydroxycarboxylic acid and acetic anhydride is preferable.
【００３０】本発明の熱液晶ポリエステルは溶融相にお
いて液晶を形成する（光学的異方性を示す）性質を有す
る。溶融相におけるこのような光学的異方性の確認は、
当業者によく知られているように、加熱装置を備えた偏
光顕微鏡を用いて、直光ニコル下で試料の薄片、好まし
くは５〜２０μｍ程度の薄片をカバーグラス間にはさみ
一定の昇温速度下で観察し、一定温度以上で光を透過す
ることを見ることにより行ない得る。尚、本観察におい
ては高温度下でカバーグラス間にはさんだ試料に軽く圧
力を加えるか、あるいはカバーグラスをずり動かすこと
によってより確実に偏光の透過を観察し得る。本観察に
おいて偏光の透過し始める温度が、光学的に異方性の溶
融相への転移温度である。溶融成形の容易さの点から、
この転移温度は３５０℃以下、より好ましくは３００℃
以下であることが望ましい。The thermo-liquid crystalline polyester of the present invention has a property of forming a liquid crystal (having optical anisotropy) in a molten phase. Confirmation of such optical anisotropy in the molten phase,
As is well known to those skilled in the art, using a polarizing microscope equipped with a heating device, a thin section of a sample, preferably about 5 to 20 μm, is sandwiched between cover glasses under direct light Nicols, and a constant heating rate is used. This can be done by observing below and seeing that light transmits above a certain temperature. In this observation, the transmission of polarized light can be observed more reliably by applying light pressure to the sample sandwiched between the cover glasses at a high temperature or by sliding the cover glass. In this observation, the temperature at which polarized light starts to pass is the transition temperature to an optically anisotropic molten phase. From the point of ease of melt molding,
This transition temperature is 350 ° C. or less, more preferably 300 ° C.
It is desirable that:
【００３１】本発明の熱液晶ポリエステルの光学的に異
方性の溶融相への転移温度は、従来提案されている熱液
晶ポリエステルとは異なり、示差走査熱量計により決定
することは難しい。すなわち、あとの実施例から明らか
なように、本発明のポリエステルを示差走査熱量計によ
り測定した場合には、組成によっては明確な吸熱ピーク
が観測されない場合があり、例え吸熱ピークが観測され
る場合にも、該ピークは必ずしも、結晶から液晶への転
移に基づくものではない。ポリエステル中、構成単位
（３）および構成単位（４）の割合が増加するにしたが
って吸熱ピークが小となり、構成単位（３）および構成
単位（４）の割合の合計が３５モル％以上では吸熱ピー
クが観測されなくなることが多い。The transition temperature of the thermal liquid crystalline polyester of the present invention to the optically anisotropic molten phase is difficult to determine with a differential scanning calorimeter, unlike the conventionally proposed thermal liquid crystalline polyester. That is, as is clear from the examples below, when the polyester of the present invention is measured by a differential scanning calorimeter, a clear endothermic peak may not be observed depending on the composition, for example, when an endothermic peak is observed. However, the peak is not necessarily based on the transition from the crystal to the liquid crystal. In the polyester, the endothermic peak becomes smaller as the ratio of the structural unit (3) and the structural unit (4) increases, and the endothermic peak is obtained when the total ratio of the structural unit (3) and the structural unit (4) is 35 mol% or more. Are often not observed.
【００３２】本発明の熱液晶ポリエステルの製造は、例
えば先ずポリエチレンナフタレート系ポリエステルを６
−アシルオキシ−２−ナフトエ酸およびｐ−アシルオキ
シ安息香酸でアシドリシスすることによってポリエステ
ルフラグメントを調製し、引き続いてこのポリエステル
フラグメントの重合度を上昇させることによって目的と
する熱液晶ポリエステルを調製する方法で行なわれる。
第一段階のアシドリシスは、通常、窒素、アルゴン、二
酸化炭素のような不活性ガス雰囲気下２５０〜３００℃
で行なわれる。６−アシルオキシ−２−ナフトエ酸およ
びｐ−アシルオキシ安息香酸としては、通常は６−アセ
トキシ−２−ナフトエ酸およびｐ−アセトキシ安息香酸
をそれぞれ用いることが望ましい。In the production of the thermal liquid crystalline polyester of the present invention, for example, polyethylene naphthalate polyester
A polyester fragment is prepared by acidolysis with acyloxy-2-naphthoic acid and p-acyloxybenzoic acid, and subsequently the desired thermal liquid crystalline polyester is prepared by increasing the degree of polymerization of the polyester fragment. .
The acidification in the first stage is usually performed at 250 to 300 ° C. in an atmosphere of an inert gas such as nitrogen, argon, or carbon dioxide.
It is done in. As 6-acyloxy-2-naphthoic acid and p-acyloxybenzoic acid, it is usually desirable to use 6-acetoxy-2-naphthoic acid and p-acetoxybenzoic acid, respectively.
【００３３】原料化合物として６−アシルオキシ−２−
ナフトエ酸およびｐ−アシルオキシ安息香酸の代わり
に、対応するヒドロキシカルボン酸（６−ヒドロキシ−
２−ナフトエ酸およびｐ−ヒドロキシ安息香酸）をそれ
ぞれ用いることもできる。その場合には、該ヒドロキシ
カルボン酸と低級脂肪族酸無水物、好ましくは無水酢酸
を反応させ、実質的にすべてのヒドロキシル基をアシル
オキシ基、好ましくはアセトキシ基に変換（アシル化）
したのちに生成した対応するアシルエステルを単離する
ことなく所定の原料ポリエステルと反応させることによ
り本発明の熱液晶ポリエステルが製造される。この場
合、原料ポリエステルは、６−ヒドロキシ−２−ナフト
エ酸およびｐ−ヒドロキシ安息香酸のアシル化反応の前
後の任意の時期に系に加えることができる。この６−ヒ
ドロキシ−２−ナフトエ酸およびｐ−ヒドロキシ安息香
酸のアシル化反応段階では、６−ヒドロキシ−２−ナフ
トエ酸の含有量が多い組成の場合、反応の進行に伴って
生成する６−アシルオキシ−２−ナフトエ酸が系内に析
出して攪拌が困難になり、その結果、重合を円滑に進行
させることが難しくなることがあるので、それを未然に
防止するために、目的とするアシル化反応に悪影響を及
ぼさず、かつ１００〜２００℃程度の沸点を有する溶
媒、特に好ましくは酢酸を系内に存在させておくことが
望ましい。As the starting compound, 6-acyloxy-2-
Instead of naphthoic acid and p-acyloxybenzoic acid, the corresponding hydroxycarboxylic acid (6-hydroxy-
2-naphthoic acid and p-hydroxybenzoic acid) can also be used. In that case, the hydroxycarboxylic acid is reacted with a lower aliphatic acid anhydride, preferably acetic anhydride, to convert substantially all of the hydroxyl groups into acyloxy groups, preferably acetoxy groups (acylation).
Thereafter, the corresponding acyl ester produced is reacted with a predetermined raw material polyester without isolation to produce the thermo-liquid crystalline polyester of the present invention. In this case, the raw material polyester can be added to the system at any time before and after the acylation reaction of 6-hydroxy-2-naphthoic acid and p-hydroxybenzoic acid. In the acylation reaction step of 6-hydroxy-2-naphthoic acid and p-hydroxybenzoic acid, in the case of a composition having a large content of 6-hydroxy-2-naphthoic acid, 6-acyloxy -2-Naphthoic acid precipitates in the system, making it difficult to stir, and as a result, it may be difficult to make the polymerization proceed smoothly. In order to prevent this, the target acylation is carried out. It is desirable that a solvent which does not adversely affect the reaction and has a boiling point of about 100 to 200 ° C., particularly preferably acetic acid, be present in the system.
【００３４】６−アシルオキシ−２−ナフトエ酸および
ｐ−アシルオキシ安息香酸と原料ポリエステルとのアシ
ドリシス反応の段階で生成する低級脂肪族酸は理論留出
量の大半が系外に出る。次いで系中に残存するアシドリ
シス反応の生成物を減圧下２５０〜３５０℃でさらに脱
低級脂肪族酸させて、所望の物品を成形するのに好適
な、好ましくは０．１ｄｌ／ｇ以上の対数粘度にまで重
合度を増大させる。この場合、重合温度は、反応速度の
点から２７０℃以上、また生成ポリエステルの分解を抑
制する点から３５０℃以下の温度であることが好ましい
が、特に好ましくは２７０〜３２０℃である。この重合
段階においては減圧度を徐々に高め、最終的に１mmHg以
下、好ましくは０．５mmHg以下にすることが望ましい。
またさらに分子量を高める方法として、 業界周知の固相
重合法等を用いることも可能である。Most of the theoretically distilled amount of the lower aliphatic acid generated in the acidolysis reaction between 6-acyloxy-2-naphthoic acid and p-acyloxybenzoic acid and the starting polyester leaves the system. The product of the acidolysis reaction remaining in the system is then further de-lowered at 250 to 350 ° C. under reduced pressure to obtain a desired article, preferably having a logarithmic viscosity of at least 0.1 dl / g or more, suitable for forming a desired article. To increase the degree of polymerization. In this case, the polymerization temperature is preferably 270 ° C. or higher from the viewpoint of reaction rate and 350 ° C. or lower from the viewpoint of suppressing decomposition of the formed polyester, and particularly preferably 270 to 320 ° C. In this polymerization step, it is desirable that the degree of reduced pressure is gradually increased, and finally the pressure is reduced to 1 mmHg or less, preferably 0.5 mmHg or less.
Further, as a method for further increasing the molecular weight, a solid phase polymerization method well-known in the art can be used.
【００３５】本発明の熱液晶ポリエステルの、ペンタフ
ルオロフェノール中、６０℃で測定した対数粘度は、得
られる成形品の力学強度の点から、０．１ｄｌ／ｇ以
上、好ましくは０．３ｄｌ／ｇ以上、より好ましくは
０．５ｄｌ／ｇ以上であることが望ましい。また、対数
粘度に臨界的な上限値はないが、溶融重合の容易さ、成
形性等の点から３．０ｄｌ／ｇ以下、好ましくは２．０
ｄｌ／ｇ以下であることが望ましい。The logarithmic viscosity of the thermal liquid crystalline polyester of the present invention measured in pentafluorophenol at 60 ° C. is at least 0.1 dl / g, preferably 0.3 dl / g, in view of the mechanical strength of the obtained molded article. More preferably, it is more preferably at least 0.5 dl / g. Although there is no critical upper limit for the logarithmic viscosity, it is 3.0 dl / g or less, preferably 2.0 dl / g or less, from the viewpoint of ease of melt polymerization and moldability.
dl / g or less is desirable.
【００３６】尚、本発明の熱液晶ポリエステルの構成単
位（１）、（２）、（３）および（４）の組成比に関し
ては、ポリマーを適当な溶媒に溶解させ、該溶液のＮＭ
Ｒスペクトルを測定することにより決定され、通常、仕
込み原料組成比と実質的に同一の組成を有するポリマー
が得られる。With respect to the composition ratio of the structural units (1), (2), (3) and (4) of the thermal liquid crystalline polyester of the present invention, the polymer is dissolved in an appropriate solvent,
Determined by measuring the R spectrum, a polymer having substantially the same composition as the charged raw material composition ratio is usually obtained.
【００３７】本発明の熱液晶ポリエステルは、従来公知
の熱液晶ポリマーと異なり、溶融状態から急冷して得ら
れる成形品の結晶化度が極めて低く、通常の場合にはＸ
線回折により求められる結晶化度は２０％以下である。
ポリエステル中の構成単位（３）および構成単位（４）
の割合が増加するにしたがって結晶化度が低下する。そ
のため本発明の熱液晶ポリエステルから得られるフイル
ム形態などの成形品は、従来提案されている熱液晶ポリ
エステルとは異なり、一軸方向および二軸方向の熱延伸
が可能であり、多くの場合２×２倍以上または３×３倍
以上の同時、あるいは逐次の二軸延伸が可能である。し
かも、本発明の熱液晶ポリエステルからなる成形品は優
れたガスバリヤー性を有している。これらの際立った特
性は、ヒドロキシ芳香族カルボン酸成分としてｐ−ヒド
ロキシ安息香酸、あるいはそのエステル形成性誘導体の
みを用いた熱液晶ポリエステルではまったく発現せず、
また、ヒドロキシ芳香族カルボン酸成分として２種のヒ
ドロキシ安息香酸、あるいはそのエステル形成性誘導体
のみを用いた熱液晶ポリエステルでもまったく発現しな
い。The thermal liquid crystalline polyester of the present invention is different from the conventionally known thermal liquid crystalline polymer in that the molded product obtained by quenching from the molten state has a very low crystallinity.
The crystallinity determined by line diffraction is 20% or less.
Structural unit (3) and structural unit (4) in polyester
The crystallinity decreases as the ratio increases. Therefore, a molded article such as a film obtained from the thermo-liquid polyester of the present invention can be subjected to uniaxial and bi-axial heat stretching, unlike the conventionally proposed thermo-liquid polyester, and in many cases, 2 × 2 Simultaneous or sequential biaxial stretching of 3 times or more or 3 × 3 times or more is possible. Moreover, the molded article made of the thermal liquid crystalline polyester of the present invention has excellent gas barrier properties. These remarkable properties are not exhibited at all in the thermal liquid crystal polyester using only p-hydroxybenzoic acid or its ester-forming derivative as the hydroxy aromatic carboxylic acid component,
Further, even a thermo-liquid crystalline polyester using only two kinds of hydroxybenzoic acids or their ester-forming derivatives as the hydroxyaromatic carboxylic acid component does not show any expression.
【００３８】本発明の熱液晶ポリエステルは、熱延伸が
可能であることから特にシートやフイルムなどの成形品
の製造に適している。また、ダイレクトブローと呼ばれ
る押出し吹き込み成形やインジェクションブロー成形、
二軸延伸ブロー成形などにより中空成形体を得ることも
できる。The thermal liquid crystalline polyester of the present invention is suitable for the production of molded articles such as sheets and films since it can be thermally stretched. In addition, extrusion blow molding and injection blow molding called direct blow,
A hollow molded article can also be obtained by biaxial stretch blow molding or the like.
【００３９】さらに、本発明で用いる熱液晶ポリエステ
ルは、他のポリマー、例えばポリエチレン、ポリプロピ
レン等のポリオレフィン樹脂、ポリエチレンテレフタレ
ート、ポリブチレンテレフタレート、ポリエチレンナフ
タレート等のポリエステル樹脂、ナイロン等のポリアミ
ド樹脂等と積層することも可能であり、共押出し、ドラ
イラミネーション、サンドイッチラミネーションなどに
よりフイルム状、シート状、チューブ状などの積層体と
し、さらに射出成形、ブロー成形、二軸延伸ブロー成
形、真空成形、圧縮成形などによりカップ状、ボトル状
などの積層体の容器とすることができる。Further, the thermal liquid crystalline polyester used in the present invention is laminated with another polymer, for example, a polyolefin resin such as polyethylene and polypropylene, a polyester resin such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, and a polyamide resin such as nylon. It is also possible to form a laminate such as a film, sheet, tube, etc. by co-extrusion, dry lamination, sandwich lamination, etc., and furthermore, injection molding, blow molding, biaxial stretching blow molding, vacuum molding, compression molding, etc. Thus, a container of a laminated body such as a cup shape and a bottle shape can be obtained.
【００４０】本発明の熱液晶ポリエステルから得られる
成形体は、酸素バリヤー性に優れており、ポリエチレン
テレフタレートの２０〜４００倍以上の性能を有してお
り、しかもその優れた酸素バリヤー性の湿度依存性は極
めて小さい。例えば、本発明の熱液晶ポリエステルを急
冷して得られるフイルムは、通常、２０℃で測定した酸
素透過量が２０ｍｌ・２０μｍ／ｍ↑2・ｄａｙ・ａｔ
ｍ以下である。酸素バリヤー性は成形品に対して熱処理
を施すことにより更に向上する場合がある。The molded article obtained from the thermal liquid crystalline polyester of the present invention has excellent oxygen barrier properties, has a performance of 20 to 400 times or more that of polyethylene terephthalate, and has excellent oxygen barrier properties depending on humidity. Sex is extremely small. For example, a film obtained by quenching the thermal liquid crystalline polyester of the present invention usually has an oxygen permeation amount measured at 20 ° C. of 20 ml · 20 μm / m ・ 2 · day · at.
m or less. The oxygen barrier property may be further improved by subjecting the molded article to heat treatment.
【００４１】このように、本発明の熱液晶ポリエステル
は従来の熱液晶ポリマーと比較して飛躍的に改善された
成形性を有しており、延伸も可能であるとともに成形品
の酸素バリヤー性にも極めて優れていることから、酸素
バリヤー性の要求される各種包装材料、容器として好適
に用いられる。従ってその用途は多岐にわたり、例え
ば、食品、医薬品、化粧品、繊維製品、工業薬品等の分
野における気体遮断性包装材料に用いることが出来る。
本発明の熱液晶ポリエステルからなる容器（包装材料を
含む）においては、その壁面の２０℃で測定された酸素
透過量は通常２０ｍｌ・２０μｍ／ｍ↑2・ｄａｙ・ａ
ｔｍ以下である。As described above, the thermal liquid crystal polyester of the present invention has a significantly improved moldability as compared with the conventional thermal liquid crystal polymer, and can be stretched and has a reduced oxygen barrier property of the molded article. Is very excellent, so that it is suitably used as various packaging materials and containers requiring oxygen barrier properties. Therefore, it has a wide variety of uses, and for example, can be used as a gas barrier packaging material in the fields of foods, pharmaceuticals, cosmetics, textiles, industrial chemicals, and the like.
In the container (including the packaging material) made of the thermo-liquid crystalline polyester of the present invention, the oxygen permeation amount of the wall surface measured at 20 ° C. is usually 20 ml · 20 μm / m ↑ 2 · day · a.
tm or less.
【００４２】さらに、本発明の熱液晶ポリエステルは、
繊維、コーティング剤等として利用することができ、ま
た従来の熱液晶ポリマーとは特異的に異なる低温流動性
を利用して、接着剤、塗料等として用いることも可能で
ある。Further, the thermal liquid crystalline polyester of the present invention comprises
It can be used as a fiber, a coating agent, or the like, and can be used as an adhesive, a paint, or the like by utilizing a low-temperature fluidity that is different from a conventional thermal liquid crystal polymer.
【００４３】[0043]
【実施例】以下実施例により本発明を具体的に説明す
る。本実施例中の物性値の測定は次の方法に従った。The present invention will be described in detail with reference to the following examples. The measurement of the physical properties in this example was performed according to the following methods.
【００４４】１）対数粘度（η↓inh ) ペンタフルオロフェノール溶媒を用いて０．１ｇ／ｄｌ
の濃度で６０℃で測定した。1) Logarithmic viscosity (η ↓ inh) 0.1 g / dl using a pentafluorophenol solvent
At 60 ° C.
【００４５】η↓inh＝［ｌｎ（ｔ↓1／ｔ↓0）］／ｃΗ ↓ inh = [ln (t ↓ 1 / t ↓ 0)] / c
【００４６】［式中、η↓inhは対数粘度（ｄｌ／ｇ）
を表し、ｔ↓0は溶媒の流下時間（秒）を表し、ｔ↓1は
試料溶液での流下時間（秒）を表し、ｃは溶液中の試料
の濃度（０．１ｇ／ｄｌ）を表す。］[Where η ↓ inh is the logarithmic viscosity (dl / g)
, T ↓ 0 represents the flow time (second) of the solvent, t ↓ 1 represents the flow time (second) in the sample solution, and c represents the concentration of the sample in the solution (0.1 g / dl). . ]
【００４７】２）熱分析 示差走査熱量計（ＤＳＣ；メトラー社製、ＴＡ−３００
０型）を用いて、溶融状態から急冷した試料に対し、１
０℃／分の昇温速度にて融点（Ｔｍ）およびガラス転移
点（Ｔｇ）を測定した。2) Thermal analysis Differential scanning calorimeter (DSC; manufactured by Mettler, TA-300)
0), the sample was quenched from the molten state.
The melting point (Tm) and the glass transition point (Tg) were measured at a heating rate of 0 ° C./min.
【００４８】３）酸素透過量（ＰＯ↓2） ガス透過率測定装置（ＭＯＤＥＲＮ ＣＯＮＴＯＲＯＬ
Ｓ社製 ＯＸ−ＴＲＡＮ１０／５０Ａ）を使用して２０
℃、相対湿度６５％の条件下で、熱プレスフイルム、延
伸フイルムまたはＰＥＴとの積層延伸フイルムについて
測定した。単位はｍｌ・２０μｍ／・ｍ↑2・ｄａｙ・
ａｔｍである。3) Oxygen Permeation (PO ↓ 2) Gas Permeability Measurement System (MODERN CONTROL)
S company OX-TRAN10 / 50A)
The measurement was performed on a hot press film, a stretched film, or a laminate stretched film with PET under the conditions of ° C and a relative humidity of 65%. The unit is ml ・ 20μm / ・ m ↑ 2 ・ day ・
atm.
【００４９】４）延伸性 温度２６０〜２９０℃で厚さ約１００μｍの熱プレスフ
イルムを作製し、このフイルムを柴山科学器械製作所二
軸延伸装置を用いて１００〜２４０℃の温度で３×３倍
の二軸延伸に付した。尚、延伸性の評価に関しては、厚
みむらの少ない均一な二軸延伸フイルムが得られたもの
を「良好」、延伸性が全く認められず、フイルムが破断
したものを「延伸不可」と評価した。4) Stretchability A hot press film having a thickness of about 100 μm was prepared at a temperature of 260 to 290 ° C., and this film was 3 × 3 times at a temperature of 100 to 240 ° C. using a biaxial stretching device of Shibayama Scientific Instruments. For biaxial stretching. In addition, regarding the evaluation of the stretchability, those in which a uniform biaxially stretched film having small thickness unevenness was obtained were evaluated as “good”, and those in which no stretchability was observed and the film was broken were evaluated as “unstretchable”. .
【００５０】５）ポリマー組成 得られたポリマーをトリフルオロ酢酸溶液とし、５００
ＭＨｚ ↑1Ｈ−ＮＭＲ（日本電子製、ＪＮＭ ＧＸ−
５００型）にて測定した。尚、本測定の結果、実施例お
よび比較例でそれぞれ得られた熱液晶ポリエステルの各
構成単位の組成は、いずれの場合も仕込み原料組成と分
析精度内で一致していることが確認された。5) Polymer composition The obtained polymer was converted to a trifluoroacetic acid solution,
MHz @ 1H-NMR (manufactured by JEOL, JNM GX-
500 type). As a result of this measurement, it was confirmed that the composition of each structural unit of the thermal liquid crystal polyester obtained in each of the examples and comparative examples was consistent with the composition of the charged raw material within the analytical accuracy in any case.
【００５１】実施例１ フェノール／テトラクロロエタン等重量混合溶媒を用い
て３０℃で測定した極限粘度が０．６５ｄｌ／ｇのポリ
エチレンナフタレート９７５ｇ（４．０モル）、６−ア
セトキシ−２−ナフトエ酸１１５０ｇ（５．０モル）、
およびｐ−アセトキシ安息香酸１８０ｇ（１．０モル）
を、攪拌機、蒸留塔および窒素ガス吹き込み口を備えた
内容積８ｌの反応器に仕込み、反応系内を３回窒素置換
したのち窒素気流下２９０℃にて１時間攪拌加熱し、そ
の後徐々に系内を減圧にして約３０mmHgで約２時間反応
させた。本操作の結果、理論留出酢酸量の約９０％が留
出した。次いで反応系内の真空度をさらに上昇させ、１
mmHg以下で５時間反応させたのち生成ポリエステルを取
り出した。Example 1 975 g (4.0 mol) of polyethylene naphthalate having an intrinsic viscosity of 0.65 dl / g measured at 30 ° C. using a phenol / tetrachloroethane equal weight mixed solvent, 6-acetoxy-2-naphthoic acid 1150 g (5.0 mol),
And 180 g (1.0 mol) of p-acetoxybenzoic acid
Was charged into a reactor having an internal volume of 8 liters equipped with a stirrer, a distillation column and a nitrogen gas injection port. After the inside of the reaction system was replaced with nitrogen three times, the mixture was stirred and heated at 290 ° C. for 1 hour under a nitrogen stream, and then gradually cooled. The reaction was carried out at a reduced pressure of about 30 mmHg for about 2 hours. As a result of this operation, about 90% of the theoretical amount of acetic acid distilled out. Next, the degree of vacuum in the reaction system was further increased, and 1
After the reaction at 5 mmHg or less for 5 hours, the formed polyester was taken out.
【００５２】得られたポリマーをトリフルオロ酢酸に溶
解させ↑1Ｈ−ＮＭＲスペクトルを測定した結果、本ポ
リマーの構成単位比は、［構成単位（１）＋構成単位
（２）］／［構成単位（３）＋構成単位（４）］のモル
比で５７／４３であることが判明した。これは仕込みの
原料組成比と実質的に同一である。得られたポリマーの
微小片をリンカム（Ｌｉｎｋａｍ）社製、顕微鏡用加熱
装置ＴＨ−６００内で窒素雰囲気下、１０℃／分の速度
で昇温し、偏光顕微鏡直交ニコル下で観察したところ、
１６０℃付近から光を透過し始め、その後昇温に伴って
透過光量はさらに増大し、最終的に３５０℃まで昇温し
ても光学的に異方性の溶融相を形成したままであった。
また、本ポリマーを溶融状態から急冷した試料を１０℃
／分の昇温速度でＤＳＣで分析した結果、８６℃にガラ
ス転移点が観測された以外、吸熱ピークはまったく観測
されなかった。さらに本ポリマーを溶融状態から急冷し
た試料の結晶化度をＸ線広角散乱で測定した結果、該試
料の結晶化度は１０％であった。次に本ポリマーから、
田端機械製小型射出成形機（ＴＫ１４−１ＡＰ型）を用
いて、シリンダー温度２８０℃、射出圧力８００kg／cm
↑2、金型温度３０℃で７５×１５×２mmの大きさの試
験片を作製した。得られた試験片をＪＩＳ Ｋ７２０３
に準じた方法により、曲げ強度および曲げ弾性率を測定
したところ、次に示す結果が得られた（いずれも樹脂の
流動方向）。The obtained polymer was dissolved in trifluoroacetic acid, and the @ 1 H-NMR spectrum was measured. As a result, the structural unit ratio of the present polymer was [(structural unit (1) + structural unit (2)] / [structural unit ( 3) + Structural unit (4)] in a molar ratio of 57/43. This is substantially the same as the charged raw material composition ratio. When the temperature of the obtained polymer fine pieces was increased at a rate of 10 ° C./min under a nitrogen atmosphere in a heating device for microscope TH-600 manufactured by Linkam Inc., and observed under a polarizing microscope orthogonal Nicols,
The light began to transmit at around 160 ° C., and thereafter, the amount of transmitted light further increased as the temperature was raised. Even when the temperature was finally raised to 350 ° C., an optically anisotropic molten phase was still formed. .
A sample obtained by rapidly cooling the present polymer from a molten state was placed at 10 ° C.
As a result of DSC analysis at a heating rate of / min, no endothermic peak was observed except for the glass transition point at 86 ° C. Furthermore, the crystallinity of the sample obtained by quenching the polymer from the molten state was measured by wide-angle X-ray scattering. As a result, the crystallinity of the sample was 10%. Next, from this polymer,
Using a small injection molding machine (Model TK14-1AP) manufactured by Tabata Machine, cylinder temperature 280 ° C, injection pressure 800kg / cm
# 2, a test piece having a size of 75 × 15 × 2 mm was prepared at a mold temperature of 30 ° C. The obtained test piece was subjected to JIS K7203.
When the bending strength and the bending elastic modulus were measured by the method according to the above, the following results were obtained (in each case, the flow direction of the resin).
【００５３】曲げ強度：２２５４kg／cm↑2Bending strength: 2254 kg / cm ↑ 2
【００５４】曲げ弾性率：１３．３×１０↑4kg／cm↑2Flexural modulus: 13.3 × 10 ↑ 4 kg / cm ↑ 2
【００５５】次に、本ポリマーを２８０℃で溶融熱プレ
スしたのち水冷式冷却プレスで急冷することにより得ら
れた厚み約１００μｍのフイルムの酸素透過量を、ＭＯ
ＤＥＲＮ ＣＯＮＴＯＲＯＬＳ社製ガス透過率測定装置
ＯＸ−ＴＲＡＮ１０／５０Ａを使用して２０℃、相対
湿度６５％の条件下で測定した結果、酸素透過量は１．
２ｍｌ・２０μｍ／ｍ↑2・ｄａｙ・ａｔｍであった。
さらに同様にして得られた厚み約１００μｍの熱プレス
フイルムを、柴山科学器械製作所製二軸延伸装置を用い
て１５０℃で３×３倍の同時二軸延伸に付した結果、厚
み約１０μｍの均一なフイルムが得られた。Next, this polymer was hot-pressed at 280 ° C. and then rapidly cooled by a water-cooled cooling press to obtain an oxygen permeation amount of a film having a thickness of about 100 μm.
As a result of measurement using a gas permeability measuring device OX-TRAN10 / 50A manufactured by DERN Controls under the conditions of 20 ° C. and a relative humidity of 65%, the oxygen permeation amount was 1.
It was 2 ml · 20 μm / m ・ 2 · day · atm.
Further, the hot press film having a thickness of about 100 μm obtained in the same manner was subjected to simultaneous biaxial stretching of 3 × 3 times at 150 ° C. using a biaxial stretching apparatus manufactured by Shibayama Kagaku Kikai Seisakusho, Ltd. Film was obtained.
【００５６】尚、本ポリマーの対数粘度、ＤＳＣ分析結
果、プレスフイルムの酸素透過量、および延伸性（３×
３倍同時二軸延伸）の評価結果を表１に示す。The logarithmic viscosity of the polymer, the result of DSC analysis, the oxygen permeability of the press film, and the stretchability (3 ×
Table 1 shows the evaluation results of the three-fold simultaneous biaxial stretching.
【００５７】実施例２ 実施例１において、ポリエチレンナフタレート／６−ア
セトキシ−２−ナフトエ酸／ｐ−アセトキシ安息香酸の
モル比を４０／３０／３０にした以外は実施例１と同様
にしてポリエステルを得た。本ポリマーを、実施例１で
用いた装置により偏光顕微鏡直交ニコル下で観察したと
ころ、１５０℃付近から光を透過し始め、その後昇温に
伴って透過光量はさらに増大し、最終的に３５０℃まで
昇温しても光学的に異方性の溶融相を形成したままであ
つた。また、本ポリマーを実施例１と同様にしてＤＳＣ
で分析した結果、８１℃にガラス転移点が観測された以
外、吸熱ピークはまったく観測されなかった。さらに本
ポリマーの結晶化度を実施例１と同様にして測定した結
果、結晶化度は１１％であった。次に実施例１と同様の
条件で射出成形を行ない、曲げ強度および曲げ弾性率を
測定したところ、次に示す結果が得られた（いずれも樹
脂の流動方向）。Example 2 A polyester was prepared in the same manner as in Example 1 except that the molar ratio of polyethylene naphthalate / 6-acetoxy-2-naphthoic acid / p-acetoxybenzoic acid was 40/30/30. I got When this polymer was observed under a polarizing microscope crossed Nicols using the apparatus used in Example 1, light began to be transmitted from around 150 ° C., and thereafter, the amount of transmitted light increased further with an increase in temperature, and finally increased to 350 ° C. Even when the temperature was raised, an optically anisotropic molten phase was still formed. The polymer was subjected to DSC in the same manner as in Example 1.
As a result, no endothermic peak was observed at all except for the glass transition point at 81 ° C. Further, the crystallinity of this polymer was measured in the same manner as in Example 1, and as a result, the crystallinity was 11%. Next, injection molding was performed under the same conditions as in Example 1, and the bending strength and the bending elastic modulus were measured. The results shown below were obtained (in each case, the flow direction of the resin).
【００５８】曲げ強度：２１３４kg／cm↑2Flexural strength: 2134 kg / cm ↑ 2
【００５９】曲げ弾性率：１２．７×１０↑4kg／cm↑2Flexural modulus: 12.7 × 10 4 kg / cm 2
【００６０】本ポリマーの対数粘度、ＤＳＣ分析結果、
プレスフイルムの酸素透過量、および延伸性（３×３倍
同時二軸延伸）の評価結果を表１に示す。The logarithmic viscosity of the polymer, the result of DSC analysis,
Table 1 shows the evaluation results of the oxygen permeability of the press film and the stretchability (3 × 3 simultaneous biaxial stretching).
【００６１】実施例３ 実施例１において、ポリエチレンナフタレート／６−ア
セトキシ−２−ナフトエ酸／ｐ−アセトキシ安息香酸の
モル比を４０／１０／５０にした以外は実施例１と同様
にしてポリエステルを得た。本ポリマーを、実施例１で
用いた装置により偏光顕微鏡直交ニコル下で観察したと
ころ、１４０℃付近から光を透過し始め、その後昇温に
伴って透過光量はさらに増大し、最終的に３５０℃まで
昇温しても光学的に異方性の溶融相を形成したままであ
った。また、本ポリマーを実施例１と同様にしてＤＳＣ
で分析した結果、７５℃にガラス転移点が観測された以
外、吸熱ピークはまったく観測されなかった。さらに本
ポリマーの結晶化度を実施例１と同様にして測定した結
果、結晶化度は１２％であった。次に実施例１と同様の
条件で射出成形を行ない、曲げ強度および曲げ弾性率を
測定したところ、次に示す結果が得られた（いずれも樹
脂の流動方向）。Example 3 Polyester was prepared in the same manner as in Example 1 except that the molar ratio of polyethylene naphthalate / 6-acetoxy-2-naphthoic acid / p-acetoxybenzoic acid was changed to 40/10/50. I got When this polymer was observed under a polarizing microscope crossed Nicols using the apparatus used in Example 1, light began to transmit at around 140 ° C., and thereafter, the amount of transmitted light further increased with increasing temperature, and finally increased to 350 ° C. Even when the temperature was raised to the maximum, an optically anisotropic molten phase was still formed. The polymer was subjected to DSC in the same manner as in Example 1.
As a result, no endothermic peak was observed except for the glass transition point at 75 ° C. Further, the crystallinity of this polymer was measured in the same manner as in Example 1, and as a result, the crystallinity was 12%. Next, injection molding was performed under the same conditions as in Example 1, and the bending strength and the bending elastic modulus were measured. The results shown below were obtained (in each case, the flow direction of the resin).
【００６２】曲げ強度：２０５５kg／cm↑2Bending strength: 2055 kg / cm ↑ 2
【００６３】曲げ弾性率：１２．３×１０↑4kg／cm↑2Flexural modulus: 12.3 × 10 ↑ 4 kg / cm ↑ 2
【００６４】本ポリマーの対数粘度、ＤＳＣ分析結果、
プレスフイルムの酸素透過量、および延伸性（３×３倍
同時二軸延伸）の評価結果を表１に示す。The logarithmic viscosity of the polymer, the result of DSC analysis,
Table 1 shows the evaluation results of the oxygen permeability of the press film and the stretchability (3 × 3 simultaneous biaxial stretching).
【００６５】実施例４ 実施例１において、ポリエチレンナフタレート／６−ア
セトキシ−２−ナフトエ酸／ｐ−アセトキシ安息香酸の
モル比を３０／６０／１０にした以外は実施例１と同様
にしてポリエステルを得た。本ポリマーを、実施例１で
用いた装置により偏光顕微鏡直交ニコル下で観察したと
ころ、１６０℃付近から光を透過し始め、その後昇温に
伴って透過光量はさらに増大し、最終的に３５０℃まで
昇温しても光学的に異方性の溶融相を形成したままであ
った。また、本ポリマーを実施例１と同様にしてＤＳＣ
で分析した結果、８９℃にガラス転移点が観測された以
外、吸熱ピークはまったく観測されなかった。さらに本
ポリマーの結晶化度を実施例１と同様にして測定した結
果、結晶化度は８％であった。Example 4 A polyester was prepared in the same manner as in Example 1 except that the molar ratio of polyethylene naphthalate / 6-acetoxy-2-naphthoic acid / p-acetoxybenzoic acid was 30/60/10. I got When this polymer was observed under a polarizing microscope crossed Nicols using the apparatus used in Example 1, light began to be transmitted from around 160 ° C., and thereafter, the amount of transmitted light increased further with an increase in temperature. Even when the temperature was raised to the maximum, an optically anisotropic molten phase was still formed. The polymer was subjected to DSC in the same manner as in Example 1.
As a result of the analysis, no endothermic peak was observed except for the glass transition point at 89 ° C. Further, the crystallinity of this polymer was measured in the same manner as in Example 1, and as a result, the crystallinity was 8%.
【００６６】本ポリマーの対数粘度、ＤＳＣ分析結果、
プレスフイルムの酸素透過量、および延伸性（３×３倍
同時二軸延伸）の評価結果を表１に示す。The logarithmic viscosity of the polymer, the result of DSC analysis,
Table 1 shows the evaluation results of the oxygen permeability of the press film and the stretchability (3 × 3 simultaneous biaxial stretching).
【００６７】実施例５ 実施例１において、ポリエチレンナフタレート／６−ア
セトキシ−２−ナフトエ酸／ｐ−アセトキシ安息香酸の
モル比を３０／３５／３５にした以外は実施例１と同様
にしてポリエステルを得た。本ポリマーを、実施例１で
用いた装置により偏光顕微鏡直交ニコル下で観察したと
ころ、１５０℃付近から光を透過し始め、その後昇温に
伴って透過光量はさらに増大し、最終的に３５０℃まで
昇温しても光学的に異方性の溶融相を形成したままであ
った。また、本ポリマーを実施例１と同様にしてＤＳＣ
で分析した結果、８０℃にガラス転移点が観測された以
外、吸熱ピークはまったく観測されなかった。さらに本
ポリマーの結晶化度を実施例１と同様にして測定した結
果、結晶化度は１０％であった。Example 5 Polyester was prepared in the same manner as in Example 1 except that the molar ratio of polyethylene naphthalate / 6-acetoxy-2-naphthoic acid / p-acetoxybenzoic acid was 30/35/35. I got When this polymer was observed under a polarizing microscope crossed Nicols using the apparatus used in Example 1, light began to be transmitted from around 150 ° C., and thereafter, the amount of transmitted light increased further with an increase in temperature, and finally increased to 350 ° C. Even when the temperature was raised to the maximum, an optically anisotropic molten phase was still formed. The polymer was subjected to DSC in the same manner as in Example 1.
As a result, no endothermic peak was observed except for the glass transition point at 80 ° C. Further, the crystallinity of this polymer was measured in the same manner as in Example 1, and as a result, the crystallinity was 10%.
【００６８】本ポリマーの対数粘度、ＤＳＣ分析結果、
プレスフイルムの酸素透過量、および延伸性（３×３倍
同時二軸延伸）の評価結果を表１に示す。The logarithmic viscosity of the polymer, the result of DSC analysis,
Table 1 shows the evaluation results of the oxygen permeability of the press film and the stretchability (3 × 3 simultaneous biaxial stretching).
【００６９】実施例６ 実施例１において、ポリエチレンナフタレート／６−ア
セトキシ−２−ナフトエ酸／ｐ−アセトキシ安息香酸の
モル比を３０／１０／６０にした以外は実施例１と同様
にしてポリエステルを得た。本ポリマーを、実施例１で
用いた装置により偏光顕微鏡直交ニコル下で観察したと
ころ、１５０℃付近から光を透過し始め、その後昇温に
伴って透過光量はさらに増大し、最終的に３５０℃まで
昇温しても光学的に異方性の溶融相を形成したままであ
った。また、本ポリマーを実施例１と同様にしてＤＳＣ
で分析した結果、７２℃にガラス転移点が観測された以
外、吸熱ピークはまったく観測されなかった。さらに本
ポリマーの結晶化度を実施例１と同様にして測定した結
果、結晶化度は１４％であった。Example 6 Polyester was prepared in the same manner as in Example 1 except that the molar ratio of polyethylene naphthalate / 6-acetoxy-2-naphthoic acid / p-acetoxybenzoic acid was 30/10/60. I got When this polymer was observed under a polarizing microscope crossed Nicols using the apparatus used in Example 1, light began to be transmitted from around 150 ° C., and thereafter, the amount of transmitted light increased further with an increase in temperature, and finally increased to 350 ° C. Even when the temperature was raised to the maximum, an optically anisotropic molten phase was still formed. The polymer was subjected to DSC in the same manner as in Example 1.
As a result, no endothermic peak was observed except for the glass transition point at 72 ° C. Further, the crystallinity of this polymer was measured in the same manner as in Example 1, and as a result, the crystallinity was 14%.
【００７０】本ポリマーの対数粘度、ＤＳＣ分析結果、
プレスフイルムの酸素透過量、および延伸性（３×３倍
同時二軸延伸）の評価結果を表１に示す。The logarithmic viscosity of the polymer, the result of DSC analysis,
Table 1 shows the evaluation results of the oxygen permeability of the press film and the stretchability (3 × 3 simultaneous biaxial stretching).
【００７１】実施例７ ６−ヒドロキシ−２−ナフトエ酸１３１６ｇ（７．０モ
ル）、ｐ−ヒドロキシ安息香酸１３８ｇ（１．０モ
ル）、無水酢酸９１８ｇ（９．０モル）、フェノール／
テトラクロロエタン等重量混合溶媒を用いて３０℃で測
定した極限粘度が０．６５ｄｌ／ｇのポリエチレンナフ
タレート４８４ｇ（２．０モル）、および反応溶媒とし
ての酢酸９６０ｇ（１６．０モル）を、攪拌機、蒸留塔
および窒素ガス吹き込み口を備えた内容積８ｌの反応器
に仕込み、反応系内を３回窒素置換したのち窒素気流
下、還流条件下で約２時間攪拌加熱した。その後、約３
時間かけて２９０℃まで昇温した後、徐々に系内を減圧
にして約３０mmHgで約２時間反応させた結果、理論留出
量の約９５％の酢酸および無水酢酸が留出した。次に反
応系内の真空度をさらに上昇させ、１mmHg以下で１時間
反応させたのち生成ポリエステルを取り出した。Example 7 1316 g (7.0 mol) of 6-hydroxy-2-naphthoic acid, 138 g (1.0 mol) of p-hydroxybenzoic acid, 918 g (9.0 mol) of acetic anhydride, phenol /
Using a stirrer, 484 g (2.0 mol) of polyethylene naphthalate having an intrinsic viscosity of 0.65 dl / g measured at 30 ° C. using a mixed solvent of tetrachloroethane and the like, and 960 g (16.0 mol) of acetic acid as a reaction solvent. The reaction system was charged to a reactor having an internal volume of 8 liters equipped with a distillation column and a nitrogen gas injection port. After the inside of the reaction system was replaced with nitrogen three times, the mixture was stirred and heated under a nitrogen stream under reflux conditions for about 2 hours. Then, about 3
After elevating the temperature to 290 ° C. over a period of time, the pressure inside the system was gradually reduced, and the reaction was carried out at about 30 mmHg for about 2 hours. As a result, about 95% of the theoretical amount of acetic acid and acetic anhydride were distilled off. Next, the degree of vacuum in the reaction system was further increased, and the reaction was carried out at 1 mmHg or less for 1 hour, and then the produced polyester was taken out.
【００７２】本ポリマーを、実施例１で用いた装置によ
り偏光顕微鏡直交ニコル下で観察したところ、１６０℃
付近から光を透過し始め、その後昇温に伴って透過光量
はさらに増大し、最終的に３５０℃まで昇温しても光学
的に異方性の溶融相を形成したままであった。また、本
ポリマーを実施例１と同様にしてＤＳＣで分析した結
果、９６℃にガラス転移点が観測された以外、吸熱ピー
クはまったく観測されなかった。さらに本ポリマーの結
晶化度を実施例１と同様にして測定した結果、結晶化度
は７％であった。The polymer was observed under a polarizing microscope crossed Nicols using the apparatus used in Example 1.
Light began to be transmitted from the vicinity, and thereafter, the amount of transmitted light increased further as the temperature was increased. Even when the temperature was finally increased to 350 ° C., an optically anisotropic molten phase was still formed. In addition, the polymer was analyzed by DSC in the same manner as in Example 1. As a result, no endothermic peak was observed except for the glass transition point at 96 ° C. Further, the crystallinity of this polymer was measured in the same manner as in Example 1, and as a result, the crystallinity was 7%.
【００７３】本ポリマーの対数粘度、ＤＳＣ分析結果、
プレスフイルムの酸素透過量、および延伸性（３×３倍
同時二軸延伸）の評価結果を表１に示す。The logarithmic viscosity of the polymer, the result of DSC analysis,
Table 1 shows the evaluation results of the oxygen permeability of the press film and the stretchability (3 × 3 simultaneous biaxial stretching).
【００７４】実施例８ 実施例７において、６−ヒドロキシ−２−ナフトエ酸５
６４ｇ（３．０モル）、ｐ−ヒドロキシ安息香酸１３８
ｇ（１．０モル）、無水酢酸４９０ｇ（４．８モル）、
酢酸４８０ｇ（８．０モル）およびポリエチレンナフタ
レート１４５２ｇ（６．０モル）を反応器に仕込んだこ
と以外は実施例７と同様にしてポリエステルを得た。本
ポリマーを、実施例１で用いた装置により偏光顕微鏡直
交ニコル下で観察したところ、２５０℃付近から光を透
過し始め、その後昇温に伴って透過光量はさらに増大
し、最終的に３５０℃まで昇温しても光学的に異方性の
溶融相を形成したままであった。また、本ポリマーを実
施例１と同様にしてＤＳＣで分析した結果、７８℃にガ
ラス転移点、２５２℃に吸熱ピークが観測された。Example 8 In Example 7, 6-hydroxy-2-naphthoic acid 5
64 g (3.0 mol), p-hydroxybenzoic acid 138
g (1.0 mol), 490 g (4.8 mol) of acetic anhydride,
A polyester was obtained in the same manner as in Example 7, except that 480 g (8.0 mol) of acetic acid and 1452 g (6.0 mol) of polyethylene naphthalate were charged into the reactor. When this polymer was observed under a polarizing microscope crossed Nicols with the apparatus used in Example 1, light began to be transmitted from around 250 ° C., and thereafter, the amount of transmitted light further increased with increasing temperature, and finally increased to 350 ° C. Even when the temperature was raised to the maximum, an optically anisotropic molten phase was still formed. The polymer was analyzed by DSC in the same manner as in Example 1. As a result, a glass transition point was observed at 78 ° C and an endothermic peak was observed at 252 ° C.
【００７５】本ポリマーの対数粘度、ＤＳＣ分析結果、
プレスフイルムの酸素透過量、および延伸性（３×３倍
同時二軸延伸）の評価結果を表１に示す。The logarithmic viscosity of the polymer, the result of DSC analysis,
Table 1 shows the evaluation results of the oxygen permeability of the press film and the stretchability (3 × 3 simultaneous biaxial stretching).
【００７６】実施例９ 実施例７において、６−ヒドロキシ−２−ナフトエ酸３
７６ｇ（２．０モル）、ｐ−ヒドロキシ安息香酸１３８
ｇ（１．０モル）、無水酢酸３６７ｇ（３．６モル）、
酢酸３６０ｇ（６．０モル）およびポリエチレンナフタ
レート１６９４ｇ（７．０モル）を反応器に仕込んだこ
と以外は実施例７と同様にしてポリエステルを得た。本
ポリマーを、実施例１で用いた装置により偏光顕微鏡直
交ニコル下で観察したところ、２５５℃付近から光を透
過し始め、その後昇温に伴って透過光量はさらに増大
し、最終的に３５０℃まで昇温しても光学的に異方性の
溶融相を形成したままであった。また、本ポリマーを実
施例１と同様にしてＤＳＣで分析した結果１２２℃にガ
ラス転移点、２５６℃に吸熱ピークが観測された。Example 9 In Example 7, 6-hydroxy-2-naphthoic acid 3
76 g (2.0 mol), p-hydroxybenzoic acid 138
g (1.0 mol), 367 g (3.6 mol) of acetic anhydride,
A polyester was obtained in the same manner as in Example 7, except that 360 g (6.0 mol) of acetic acid and 1694 g (7.0 mol) of polyethylene naphthalate were charged into the reactor. When this polymer was observed under a polarizing microscope crossed Nicols using the apparatus used in Example 1, light began to be transmitted from around 255 ° C., and thereafter, the amount of transmitted light further increased with an increase in temperature. Even when the temperature was raised to the maximum, an optically anisotropic molten phase was still formed. The polymer was analyzed by DSC in the same manner as in Example 1. As a result, a glass transition point at 122 ° C. and an endothermic peak at 256 ° C. were observed.
【００７７】本ポリマーの対数粘度、ＤＳＣ分析結果、
プレスフイルムの酸素透過量、および延伸性（３×３倍
同時二軸延伸）の評価結果を表１に示す。The logarithmic viscosity of the polymer, the result of DSC analysis,
Table 1 shows the evaluation results of the oxygen permeability of the press film and the stretchability (3 × 3 simultaneous biaxial stretching).
【００７８】[0078]
【表１】 [Table 1]
【００７９】比較例１ 実施例１において６−アセトキシ−２−ナフトエ酸の代
わりにｐ−アセトキシ安息香酸を用いた、すなわちアセ
トキシ芳香族カルボン酸成分（６．０モル）をすべてｐ
−アセトキシ安息香酸にした以外は実施例１と同様にし
てポリエステルを得た。本ポリマーを、実施例１で用い
た装置により偏光顕微鏡直交ニコル下で観察したとこ
ろ、２５５℃付近から光を透過し始め、その後昇温に伴
って透過光量はさらに増大し、最終的に３５０℃まで昇
温しても光学的に異方性の溶融相を形成したままであっ
た。また、本ポリマーを実施例１と同様にしてＤＳＣで
分析した結果、ガラス転移点は観測されず、２５８℃に
吸熱ピークが観測されたのみであった。さらに本ポリマ
ーの結晶化度を実施例１と同様にして測定した結果、結
晶化度は２７％であった。Comparative Example 1 In Example 1, p-acetoxybenzoic acid was used in place of 6-acetoxy-2-naphthoic acid, that is, all of the acetoxyaromatic carboxylic acid component (6.0 mol) was p-type.
-A polyester was obtained in the same manner as in Example 1 except that acetoxybenzoic acid was used. When this polymer was observed under a polarizing microscope crossed Nicols using the apparatus used in Example 1, light began to be transmitted from around 255 ° C., and thereafter, the amount of transmitted light further increased with an increase in temperature. Even when the temperature was raised to the maximum, an optically anisotropic molten phase was still formed. Further, the polymer was analyzed by DSC in the same manner as in Example 1. As a result, no glass transition point was observed, and only an endothermic peak was observed at 258 ° C. Furthermore, as a result of measuring the crystallinity of the present polymer in the same manner as in Example 1, the crystallinity was 27%.
【００８０】本ポリマーの対数粘度、ＤＳＣ分析結果、
プレスフイルムの酸素透過量、および延伸性（３×３倍
同時二軸延伸）の評価結果を表２に示す。The logarithmic viscosity of the polymer, the result of DSC analysis,
Table 2 shows the evaluation results of the oxygen permeability of the press film and the stretchability (3 × 3 simultaneous biaxial stretching).
【００８１】比較例２ 比較例１においてポリエチレンナフタレートの代わり
に、フェノール／テトラクロロエタン等重量混合溶媒を
用いて３０℃で測定した極限粘度が０．７ｄｌ／ｇのポ
リエチレンテレフタレート（４．０モル）を用い、重合
温度を２８０℃に変更した以外は比較例１と同様にして
ポリエステルを得た。本ポリマーを、実施例１で用いた
装置により偏光顕微鏡直交ニコル下で観察したところ、
２００℃付近から光を透過し始め、その後昇温に伴って
透過光量はさらに増大し、最終的に３５０℃まで昇温し
ても光学的に異方性の溶融相を形成したままであった。
また、本ポリマーを実施例１と同様にしてＤＳＣで分析
した結果、ガラス転移点は明確には観測されず、２０５
℃に吸熱ピークが観測されたのみであった。さらに本ポ
リマーの結晶化度を実施例１と同様にして測定した結
果、結晶化度は２５％であった。次に実施例１と同様の
条件で射出成形を行ない、曲げ強度および曲げ弾性率を
測定したところ、次に示す結果が得られた（いずれも樹
脂の流動方向）。Comparative Example 2 Polyethylene terephthalate (4.0 mol) having an intrinsic viscosity of 0.7 dl / g measured at 30 ° C. using a mixed solvent of phenol / tetrachloroethane and the like in place of polyethylene naphthalate in Comparative Example 1 And a polyester was obtained in the same manner as in Comparative Example 1 except that the polymerization temperature was changed to 280 ° C. When this polymer was observed under a polarizing microscope orthogonal Nicols using the apparatus used in Example 1,
Light began to be transmitted at around 200 ° C., and thereafter, the amount of transmitted light further increased as the temperature was raised. Even when the temperature was finally raised to 350 ° C., an optically anisotropic molten phase was still formed. .
The polymer was analyzed by DSC in the same manner as in Example 1. As a result, the glass transition point was not clearly observed.
Only an endothermic peak was observed at ° C. Further, the crystallinity of this polymer was measured in the same manner as in Example 1, and as a result, the crystallinity was 25%. Next, injection molding was performed under the same conditions as in Example 1, and the bending strength and the bending elastic modulus were measured. The results shown below were obtained (in each case, the flow direction of the resin).
【００８２】曲げ強度：９７０kg／cm↑2Bending strength: 970 kg / cm @ 2
【００８３】曲げ弾性率：８．１×１０↑4kg／cm↑2Flexural modulus: 8.1 × 10 ↑ 4 kg / cm ↑ 2
【００８４】本ポリマーの対数粘度、ＤＳＣ分析結果、
プレスフイルムの酸素透過量、および延伸性（３×３倍
同時二軸延伸）の評価結果を表２に示す。The logarithmic viscosity of the polymer, the result of DSC analysis,
Table 2 shows the evaluation results of the oxygen permeability of the press film and the stretchability (3 × 3 simultaneous biaxial stretching).
【００８５】比較例３ 実施例１において、ポリエチレンナフタレート／６−ア
セトキシ−２−ナフトエ酸／ｐ−アセトキシ安息香酸の
モル比を９０／５／５にしたこと以外は実施例１と同様
にしてポリエステルを得た。本ポリマーを、実施例１で
用いた装置により偏光顕微鏡直交ニコル下で観察した
が、３５０℃以下のいかなる温度においても光学的に異
方性の溶融相を形成しなかった。また、本ポリマーを実
施例１と同様にしてＤＳＣで分析した結果、１２３℃に
ガラス転移点、２６０℃に吸熱ピークが観測された。Comparative Example 3 The procedure of Example 1 was repeated, except that the molar ratio of polyethylene naphthalate / 6-acetoxy-2-naphthoic acid / p-acetoxybenzoic acid was 90/5/5. Polyester was obtained. This polymer was observed under a polarizing microscope crossed Nicols using the apparatus used in Example 1, and did not form an optically anisotropic molten phase at any temperature of 350 ° C. or lower. The polymer was analyzed by DSC in the same manner as in Example 1. As a result, a glass transition point was observed at 123 ° C., and an endothermic peak was observed at 260 ° C.
【００８６】本ポリマーの対数粘度、ＤＳＣ分析結果、
プレスフイルムの酸素透過量、および延伸性（３×３倍
同時二軸延伸）の評価結果を表２に示す。The logarithmic viscosity of the polymer, the result of DSC analysis,
Table 2 shows the evaluation results of the oxygen permeability of the press film and the stretchability (3 × 3 simultaneous biaxial stretching).
【００８７】比較例４ 実施例１で用いたポリエチレンナフタレートのＤＳＣ分
析結果、プレスフイルムの酸素透過量、および延伸性の
評価結果を表２に示す。Comparative Example 4 Table 2 shows the DSC analysis results of the polyethylene naphthalate used in Example 1, the oxygen permeation amount of the press film, and the evaluation results of the stretchability.
【００８８】[0088]
【表２】 [Table 2]
【００８９】実施例１０〜１１、比較例５〜７ 実施例１あるいは実施例２で得られた熱液晶ポリマー
と、フェノール／テトラクロロエタン等重量混合溶媒中
３０℃で測定した極限粘度が０．７５ｄｌ／ｇのＰＥＴ
樹脂とを用いて多層シートを成形した。すなわち、熱液
晶ポリマーとＰＥＴ樹脂とをそれぞれ８０℃、および１
５０℃で一昼夜真空乾燥した後２台の押出し機により共
押出ししてＰＥＴ／熱液晶ポリマー／ＰＥＴの３層のシ
ートを得た。得られたシートのＰＥＴ／熱液晶ポリマー
／ＰＥＴの各層の厚みは２８０μｍ／２０μｍ／２００
μｍであった。この積層シートを実施例１で用いた二軸
延伸装置を使用して１００〜１２０℃で３×３倍に同時
二軸延伸して延伸フイルムを得た（実施例１０、１
１）。Examples 10 to 11 and Comparative Examples 5 to 7 The liquid crystalline polymer obtained in Example 1 or Example 2 had an intrinsic viscosity of 0.75 dl measured at 30 ° C. in a mixed solvent of phenol / tetrachloroethane and the like. / G PET
A multilayer sheet was formed using a resin. That is, the thermal liquid crystal polymer and the PET resin were heated at 80 ° C and 1 ° C, respectively.
After vacuum drying at 50 ° C. for 24 hours, co-extrusion was performed with two extruders to obtain a three-layer sheet of PET / thermo-liquid crystal polymer / PET. The thickness of each layer of PET / thermal liquid crystal polymer / PET of the obtained sheet is 280 μm / 20 μm / 200.
μm. The laminated sheet was simultaneously biaxially stretched 3 × 3 times at 100 to 120 ° C. using the biaxial stretching apparatus used in Example 1 to obtain a stretched film (Examples 10 and 1).
1).
【００９０】また比較例１あるいは比較例２の熱液晶ポ
リマーを用いて同様のＰＥＴ／熱液晶ポリマー／ＰＥＴ
の二種三層フイルムの成形を試みたが、中間層（熱液晶
ポリマー層）の延伸ができず、いずれの場合にも良好な
フイルムを得ることができなかった（比較例５、６）。The same PET / thermo-liquid crystal polymer / PET was obtained using the thermo-liquid crystal polymer of Comparative Example 1 or Comparative Example 2.
Was attempted, but the intermediate layer (thermal liquid crystal polymer layer) could not be stretched, and in each case, a good film could not be obtained (Comparative Examples 5 and 6).
【００９１】次に、ＰＥＴ樹脂だけを使用して上記押出
し機の１台のみを用いて厚み約５００μｍの単層シート
を得た。このシートを上記の二軸延伸装置を用いて１２
０℃で３×３倍に同時二軸延伸し、延伸フイルムを作製
した（比較例７）。Next, a single-layer sheet having a thickness of about 500 μm was obtained using only one of the extruders using only the PET resin. This sheet is subjected to 12-
The film was simultaneously biaxially stretched 3 × 3 times at 0 ° C. to produce a stretched film (Comparative Example 7).
【００９２】これらのフイルムの酸素バリヤー性能は、
前述の方法で評価した。その結果を表３に示す。The oxygen barrier performance of these films is as follows:
Evaluation was performed by the method described above. Table 3 shows the results.
【００９３】[0093]
【表３】 [Table 3]
【００９４】[0094]
【発明の効果】本発明の熱液晶ポリエステルは優れた成
形性を有しており、またそれから得られる成形品は優れ
たガスバリヤー性を有しているため、高度なガスバリヤ
ー性を必要とする各種の包装材料として有用である。The thermal liquid crystalline polyester of the present invention has excellent moldability, and the molded article obtained therefrom has excellent gas barrier properties, and therefore requires a high degree of gas barrier properties. Useful as various packaging materials.
Claims (2)
構成単位（２）を実質的に等しいモル数で含み、構成単
位（１）および構成単位（２）の合計量が１５〜９０モ
ル％、構成単位（３）および構成単位（４）の合計量が
１０〜８５モル％であり、構成単位（３）および構成単
位（４）の合計量に対する構成単位（３）の量の割合が
１０モル％以上であり、かつ２０℃、相対湿度６５％で
測定した酸素透過量が２０ｍｌ・２０μｍ／ｍ 2 ・ｄａ
ｙ・ａｔｍ以下の熱プレスフィルム を与える熱液晶ポリ
エステル。(1) Substantially the following chemical formula (1) Structural unit (1) represented by the following formula 2 The structural unit (2) represented by the following formula 3 And a structural unit (3) represented by the following formula: Wherein the structural unit (1) and the structural unit (2) are contained in substantially equal moles, and the total amount of the structural unit (1) and the structural unit (2) is 15 to 90. Mol%, the total amount of the structural unit (3) and the structural unit (4) is 10 to 85 mol%, and the ratio of the amount of the structural unit (3) to the total amount of the structural unit (3) and the structural unit (4) Ri der There least 10 mol%, and 20 ° C., 65% relative humidity
Measured oxygen permeation amount is 20ml ・ 20μm / m 2 ・ da
Thermal liquid crystalline polyester which gives a hot pressed film of y · atm or less .
なる成形品。2. A molded article comprising the thermal liquid crystalline polyester according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19695991A JP3147315B2 (en) | 1990-07-10 | 1991-07-10 | Thermal liquid crystalline polyester and molded articles made thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18327890 | 1990-07-10 | ||
| JP2-183278 | 1990-07-10 | ||
| JP19695991A JP3147315B2 (en) | 1990-07-10 | 1991-07-10 | Thermal liquid crystalline polyester and molded articles made thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH051140A JPH051140A (en) | 1993-01-08 |
| JP3147315B2 true JP3147315B2 (en) | 2001-03-19 |
Family
ID=26501787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19695991A Expired - Fee Related JP3147315B2 (en) | 1990-07-10 | 1991-07-10 | Thermal liquid crystalline polyester and molded articles made thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3147315B2 (en) |
-
1991
- 1991-07-10 JP JP19695991A patent/JP3147315B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH051140A (en) | 1993-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5326848A (en) | Thermotropic liquid crystal polyester | |
| EP1436340B1 (en) | Anisotropic melt-forming polymers having a high degree of stretchability | |
| EP1116739B1 (en) | Composition and process for producing stretchable polymers and shaped articles produced by same | |
| US6666990B2 (en) | Stretchable liquid crystal polymer composition | |
| EP1116736B1 (en) | Process for producing amorphous anisotropic melt-forming polymers having a high degree of stretchability and polymers produced by same | |
| JP3067049B2 (en) | Containers and packages | |
| JP3178737B2 (en) | Polyester film | |
| EP0466085B1 (en) | Thermotropic liquid crystal polyester | |
| US6222000B1 (en) | Process for producing amorphous anisotropic melt-forming polymers having a high degree of stretchability | |
| JP3147315B2 (en) | Thermal liquid crystalline polyester and molded articles made thereof | |
| US6207790B1 (en) | Process for producing amorphous anisotropic melt-forming polymers having a high degree of stretchability and polymers produced by same | |
| JP3185988B2 (en) | Thermal liquid crystalline polyester and molded articles made thereof | |
| JP3119453B2 (en) | Thermal liquid crystalline polyester and molded articles made thereof | |
| JPH05186578A (en) | Production of thermotropic liquid-crystalline polyester | |
| JP3096514B2 (en) | Multilayer containers and packages | |
| JP3067048B2 (en) | Multilayer containers and packages | |
| JPH05186575A (en) | Thermotropic liquid-crystalline polyester and molded article prepared therefrom | |
| JPH055028A (en) | Gas-barrier vessel | |
| JPH05186577A (en) | Thermotropic liquid-crystalline polyester and its production | |
| JPH05186576A (en) | Molded article for water vapor barrier | |
| JPH0532771A (en) | Thermal liquid crystal polyester and film comprising the same | |
| JPH02172738A (en) | Polyester laminated body and use thereof | |
| JP2023150538A (en) | Polyalkylene ether glycol copolyester and molding | |
| JP2605766B2 (en) | Copolyester | |
| JPH05186671A (en) | Thermotropic liquid crystal polyester composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080112 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090112 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090112 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100112 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110112 Year of fee payment: 10 |
|
| LAPS | Cancellation because of no payment of annual fees |