JPH04272922A - Polyester and polyester for packaging material - Google Patents
Polyester and polyester for packaging materialInfo
- Publication number
- JPH04272922A JPH04272922A JP5362791A JP5362791A JPH04272922A JP H04272922 A JPH04272922 A JP H04272922A JP 5362791 A JP5362791 A JP 5362791A JP 5362791 A JP5362791 A JP 5362791A JP H04272922 A JPH04272922 A JP H04272922A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- acid
- group
- ester
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 93
- 239000005022 packaging material Substances 0.000 title claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 67
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 33
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 29
- 150000002009 diols Chemical class 0.000 claims abstract description 7
- -1 polyethylene terephthalate Polymers 0.000 claims description 64
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 47
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 28
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000004806 packaging method and process Methods 0.000 claims 1
- 230000004888 barrier function Effects 0.000 abstract description 31
- PPZYHOQWRAUWAY-UHFFFAOYSA-N 2-[2-(carboxymethoxy)phenoxy]acetic acid Chemical compound OC(=O)COC1=CC=CC=C1OCC(O)=O PPZYHOQWRAUWAY-UHFFFAOYSA-N 0.000 abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 74
- 238000006116 polymerization reaction Methods 0.000 description 41
- 239000007789 gas Substances 0.000 description 34
- 230000035699 permeability Effects 0.000 description 26
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 20
- 229910001882 dioxygen Inorganic materials 0.000 description 20
- 238000000034 method Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- ZVMAGJJPTALGQB-UHFFFAOYSA-N 2-[3-(carboxymethoxy)phenoxy]acetic acid Chemical compound OC(=O)COC1=CC=CC(OCC(O)=O)=C1 ZVMAGJJPTALGQB-UHFFFAOYSA-N 0.000 description 11
- 238000005886 esterification reaction Methods 0.000 description 11
- 150000001991 dicarboxylic acids Chemical class 0.000 description 10
- 229920001225 polyester resin Polymers 0.000 description 10
- 239000004645 polyester resin Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- JXXILZQFWRQHHZ-UHFFFAOYSA-N 2-(carboxymethylperoxy)acetic acid Chemical compound OC(=O)COOCC(O)=O JXXILZQFWRQHHZ-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 229920005992 thermoplastic resin Polymers 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 6
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000000071 blow moulding Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920001634 Copolyester Polymers 0.000 description 3
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 229940119177 germanium dioxide Drugs 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- JOBHEGVWWCJZPO-UHFFFAOYSA-N methyl 2-(2-hydroxyethoxy)benzoate Chemical compound COC(=O)C1=CC=CC=C1OCCO JOBHEGVWWCJZPO-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) 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
- 239000010959 steel Substances 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
- FBYFHODQAUBIOO-UHFFFAOYSA-N 2-(1-carboxyethoxy)propanoic acid Chemical compound OC(=O)C(C)OC(C)C(O)=O FBYFHODQAUBIOO-UHFFFAOYSA-N 0.000 description 1
- RUARALYJHUDLAX-UHFFFAOYSA-N 2-(1-carboxypropoxy)butanoic acid Chemical compound CCC(C(O)=O)OC(CC)C(O)=O RUARALYJHUDLAX-UHFFFAOYSA-N 0.000 description 1
- QRUWNLWDXIBBCK-UHFFFAOYSA-N 2-(1-carboxypropylamino)butanoic acid Chemical compound CCC(C(O)=O)NC(CC)C(O)=O QRUWNLWDXIBBCK-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- VQUBZTADBUIIIK-UHFFFAOYSA-N 2-(carboxymethoxy)acetic acid Chemical compound OC(=O)COCC(O)=O.OC(=O)COCC(O)=O VQUBZTADBUIIIK-UHFFFAOYSA-N 0.000 description 1
- LGFMOLKMVUSAOD-UHFFFAOYSA-N 2-[2-(carboxymethoxy)-4-chlorophenoxy]acetic acid Chemical compound OC(=O)COC1=CC=C(Cl)C=C1OCC(O)=O LGFMOLKMVUSAOD-UHFFFAOYSA-N 0.000 description 1
- QKDMOXIUBIOGEQ-UHFFFAOYSA-N 2-[3-(carboxymethoxy)-2-methylphenoxy]acetic acid Chemical compound CC1=C(OCC(O)=O)C=CC=C1OCC(O)=O QKDMOXIUBIOGEQ-UHFFFAOYSA-N 0.000 description 1
- MMVMXXHXCHWNAB-UHFFFAOYSA-N 2-[3-(carboxymethoxy)-4-chlorophenoxy]acetic acid Chemical compound OC(=O)COC1=CC=C(Cl)C(OCC(O)=O)=C1 MMVMXXHXCHWNAB-UHFFFAOYSA-N 0.000 description 1
- XGJGRYWIXWFAFI-UHFFFAOYSA-N 2-[3-(carboxymethoxy)-4-methoxyphenoxy]acetic acid Chemical compound COC1=CC=C(OCC(O)=O)C=C1OCC(O)=O XGJGRYWIXWFAFI-UHFFFAOYSA-N 0.000 description 1
- GIBXEGOBIUWGQL-UHFFFAOYSA-N 2-[3-(carboxymethoxy)-4-methylphenoxy]acetic acid Chemical compound CC1=CC=C(OCC(O)=O)C=C1OCC(O)=O GIBXEGOBIUWGQL-UHFFFAOYSA-N 0.000 description 1
- ZRKPKMNAEDFBJD-UHFFFAOYSA-N 2-[3-(carboxymethoxy)-5-ethylphenoxy]acetic acid Chemical compound CCC1=CC(OCC(O)=O)=CC(OCC(O)=O)=C1 ZRKPKMNAEDFBJD-UHFFFAOYSA-N 0.000 description 1
- AGXNXMTZPKVKSA-UHFFFAOYSA-N 2-[3-(carboxymethoxy)-5-methoxyphenoxy]acetic acid Chemical compound COC1=CC(OCC(O)=O)=CC(OCC(O)=O)=C1 AGXNXMTZPKVKSA-UHFFFAOYSA-N 0.000 description 1
- UOBAJSWXHKDRKK-UHFFFAOYSA-N 2-[3-(carboxymethoxy)-5-methylphenoxy]acetic acid Chemical compound CC1=CC(OCC(O)=O)=CC(OCC(O)=O)=C1 UOBAJSWXHKDRKK-UHFFFAOYSA-N 0.000 description 1
- DNXOCFKTVLHUMU-UHFFFAOYSA-N 2-[4-(carboxymethoxy)phenoxy]acetic acid Chemical compound OC(=O)COC1=CC=C(OCC(O)=O)C=C1 DNXOCFKTVLHUMU-UHFFFAOYSA-N 0.000 description 1
- FIOHTMQGSFVHEZ-WUCPZUCCSA-N 2-[[(1s)-1-carboxyethyl]amino]propanoic acid Chemical compound OC(=O)C(C)N[C@@H](C)C(O)=O FIOHTMQGSFVHEZ-WUCPZUCCSA-N 0.000 description 1
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 1
- ZKIZCEAXOZFPMA-UHFFFAOYSA-N 3-(1-carboxypropan-2-ylamino)butanoic acid Chemical compound CC(CC(O)=O)NC(C)CC(O)=O ZKIZCEAXOZFPMA-UHFFFAOYSA-N 0.000 description 1
- TXIMLYCDYRESBF-UHFFFAOYSA-N 3-(1-carboxypropan-2-yloxy)butanoic acid Chemical compound OC(=O)CC(C)OC(C)CC(O)=O TXIMLYCDYRESBF-UHFFFAOYSA-N 0.000 description 1
- FOSIWKADJDNVMJ-UHFFFAOYSA-N 3-(2-carboxyethoxy)propanoic acid Chemical compound OC(=O)CCOCCC(O)=O FOSIWKADJDNVMJ-UHFFFAOYSA-N 0.000 description 1
- TXPKUUXHNFRBPS-UHFFFAOYSA-N 3-(2-carboxyethylamino)propanoic acid Chemical compound OC(=O)CCNCCC(O)=O TXPKUUXHNFRBPS-UHFFFAOYSA-N 0.000 description 1
- VGUWZCUCNQXGBU-UHFFFAOYSA-N 3-[(4-methylpiperazin-1-yl)methyl]-5-nitro-1h-indole Chemical compound C1CN(C)CCN1CC1=CNC2=CC=C([N+]([O-])=O)C=C12 VGUWZCUCNQXGBU-UHFFFAOYSA-N 0.000 description 1
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 1
- HAYIPGIFANTODX-UHFFFAOYSA-N 4,6-dimethylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC(C)=C(C(O)=O)C=C1C(O)=O HAYIPGIFANTODX-UHFFFAOYSA-N 0.000 description 1
- RHIVLTKIJSCFNW-UHFFFAOYSA-N 4-(3-carboxypropoxy)butanoic acid Chemical compound OC(=O)CCCOCCCC(O)=O RHIVLTKIJSCFNW-UHFFFAOYSA-N 0.000 description 1
- HBUXNNBOWNIKNE-UHFFFAOYSA-N 4-(3-carboxypropylamino)butanoic acid Chemical compound OC(=O)CCCNCCCC(O)=O HBUXNNBOWNIKNE-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 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
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 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
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- NWAXPHKYKCLVAA-UHFFFAOYSA-N benzenesulfonylbenzene;2-(carboxymethylperoxy)acetic acid Chemical compound OC(=O)COOCC(O)=O.C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 NWAXPHKYKCLVAA-UHFFFAOYSA-N 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
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- RXSUQXMNIPVFDH-UHFFFAOYSA-N ethyl 2-[3-(2-ethoxy-2-oxoethoxy)phenoxy]acetate Chemical compound CCOC(=O)COC1=CC=CC(OCC(=O)OCC)=C1 RXSUQXMNIPVFDH-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 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
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 235000014101 wine Nutrition 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は特定のポリエステル及び
その組成物と、それを成形してなる包装材に関する。本
発明のポリエステルは透明性及びガスバリヤ―性に優れ
、容器、フィルム等の包装材料として有用である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a specific polyester, a composition thereof, and a packaging material formed from the polyester. The polyester of the present invention has excellent transparency and gas barrier properties, and is useful as a packaging material for containers, films, etc.
【従来の技術】ポリエチレンテレフタレ―トは機械的強
度、化学的安定性、透明性、衛生性などに優れており、
また軽量、安価であるために、各種の容器・フィルムと
して幅広く包装材料に用いられている。しかしながら、
ポリエチレンテレフタレ―トのガスバリヤ―性は、ポリ
オレフィンなど他の樹脂に比べれば優れているものの、
まだ十分なレベルとは言えなかった。例えば、炭酸飲料
、ビ―ル、ワイン等の用途においては、内容物保存の点
から特に厳しい酸素ガスバリヤ―性、炭酸ガスバリヤ―
性が要求されており、通常に使用される二軸配向したポ
リエチレンテレフタレ―トからなる中空容器ではガスバ
リヤ―性が不十分である。このため、ポリエチレンテレ
フタレ―ト製容器のガスバリヤ―性をさらに向上させる
方法が各種提案されている。例えば、１）ガスバリヤ―
性材料をポリエチレンテレフタレ―ト製容器にラベル、
あるいはコ―ティングする方法、２）ポリエチレンテレ
フタレ―トとガスバリヤ―性材料の多層容器とする方法
、３）ガスバリヤ―性材料をポリエチレンテレフタレ―
トにブレンドした材料で容器を製造する方法等があげら
れる。[Prior art] Polyethylene terephthalate has excellent mechanical strength, chemical stability, transparency, hygiene, etc.
Also, because it is lightweight and inexpensive, it is widely used as packaging materials for various containers and films. however,
Although the gas barrier properties of polyethylene terephthalate are superior compared to other resins such as polyolefin,
I still couldn't say it was at a high enough level. For example, in applications such as carbonated drinks, beer, and wine, oxygen gas barrier properties and carbon dioxide gas barrier properties are particularly demanding from the perspective of preserving the contents.
However, the normally used hollow containers made of biaxially oriented polyethylene terephthalate have insufficient gas barrier properties. For this reason, various methods have been proposed to further improve the gas barrier properties of polyethylene terephthalate containers. For example, 1) Gas barrier
labels on polyethylene terephthalate containers,
2) A method of forming a multilayer container of polyethylene terephthalate and a gas barrier material; 3) A method of forming a multilayer container of polyethylene terephthalate and a gas barrier material;
Examples include a method of manufacturing containers using materials blended with other materials.
【０００２】１）及び２）の方法においては、ポリ塩化
ビニリデン、エチレン−酢酸ビニル共重合体ケン化物、
メタキシリレンジアミン系ナイロン等がガスバリヤ―性
材料として提案されている。しかしこれらの方法では、
ガスバリヤ―性材料をコ―ティングする製造工程が増え
たり、多層容器を製造するための新たな装置を必要とす
るなどの製造面での負担が大きいほか、ガスバリヤ―層
とポリエチレンテレフタレ―ト層との間の接着性が悪い
と層間剥離を起こしたりする等の欠点があった。また、
３）の方法では、通常の製造装置、工程を利用してガス
バリヤ―性容器を製造できるという利点があるが、ブレ
ンド物の透明性を保つためには、ポリエチレンテレフタ
レ―トに対する相溶性が良く、屈折率の近い材料が必要
とされ、ガスバリヤ―性能が優れているだけではこの方
法のガスバリヤ―材料として用いることができなかった
。この要件を満たすようなガスバリヤ―材料として、ポ
リエチレンイソフタレ―トやそのコポリエステルも提案
されているが、そのガスバリヤ―性のレベルは、ポリエ
チレンテレフタレ―トのガスバリヤ―性を改善するため
には充分なものではなかった。また、イソフタル酸とジ
フェニルスルホンジオキシジ酢酸を主成分とするガスバ
リヤー性を改良した共重合ポリエステルおよびそれから
なる容器も知られてはいる（特開昭６４−８７６１９、
特開平２−１６９６２２）。In methods 1) and 2), polyvinylidene chloride, saponified ethylene-vinyl acetate copolymer,
Meta-xylylene diamine-based nylon and the like have been proposed as gas barrier materials. However, these methods
In addition to the increased manufacturing process of coating with gas barrier material and the need for new equipment to manufacture multilayer containers, there is also a heavy burden on the manufacturing side, including the need for gas barrier layer and polyethylene terephthalate layer. If the adhesion between the two layers is poor, there are drawbacks such as delamination between the layers. Also,
Method 3) has the advantage of being able to manufacture gas-barrier containers using normal manufacturing equipment and processes, but in order to maintain the transparency of the blend, it is necessary to have good compatibility with polyethylene terephthalate. , a material with similar refractive index is required, and it has not been possible to use it as a gas barrier material in this method just by having excellent gas barrier performance. Polyethylene isophthalate and its copolyester have also been proposed as gas barrier materials that meet this requirement, but their gas barrier properties are insufficient to improve the gas barrier properties of polyethylene terephthalate. It wasn't enough. Copolymerized polyesters with improved gas barrier properties and containers made of the same are also known (Japanese Unexamined Patent Application Publication No. 64-87619,
JP-A-2-169622).
【０００３】0003
【発明が解決しようとする課題】しかしながら、この共
重合ポリエステルレジンおよびそれからなる容器は、ガ
スバリヤー性についてはかなりの程度の改良効果が見ら
れるものの、イソフタル酸成分が多いためにレジン製造
時に昇華物が発生し、配管を閉塞させるトラブルが生じ
る問題点があり、また容器とした場合に強度物性が不十
分であり、必ずしも実用的とは言い難い。本発明は、こ
うした実情の下に機械的強度、透明性などの物性に優れ
、ガスバリヤ―性の優れたポリエステル包装材料を提供
することを目的とする。[Problems to be Solved by the Invention] However, although this copolymerized polyester resin and the containers made from it show a considerable improvement in gas barrier properties, they contain a large amount of isophthalic acid, which causes problems with sublimation during resin production. This causes problems such as clogging of pipes, and when used as a container, the strength and physical properties are insufficient, so it cannot necessarily be said to be practical. Under these circumstances, an object of the present invention is to provide a polyester packaging material that has excellent physical properties such as mechanical strength and transparency, and has excellent gas barrier properties.
【０００４】0004
【課題を解決するための手段】本発明者らは前記欠点を
解消するために鋭意検討した結果、特定の共重合ポリエ
ステルがガスバリヤ―材料として有効であることを見出
し、本発明に至ったものである。すなわち本発明は以下
の二つの態様からなりその第１の態様は、（Ａ）下記一
般式（ＩＩＩ）で表されるジカルボン酸またはそのエス
テル形成性誘導体と、（Ｂ）一般式（ＩＶ）で表される
ジカルボン酸またはそのエステル形成性誘導体を、（Ａ
）成分単位と（Ｂ）成分単位の和が全酸成分単位の少な
くとも５０モル％以上の割合で含むジカルボン酸成分と
、ジオ―ル成分とを重合させて得られる包装材料用ポリ
エステルに関するものである。[Means for Solving the Problems] As a result of intensive studies to eliminate the above-mentioned drawbacks, the present inventors discovered that a specific copolymerized polyester is effective as a gas barrier material, leading to the present invention. be. That is, the present invention consists of the following two aspects, the first aspect of which is (A) a dicarboxylic acid represented by the following general formula (III) or its ester-forming derivative; The dicarboxylic acid represented or its ester-forming derivative (A
) A polyester for packaging materials obtained by polymerizing a dicarboxylic acid component containing a sum of component units (B) and (B) component units in a ratio of at least 50 mol% or more of the total acid component units and a diol component. .
【０００５】[0005]
【化９】
（Ｒ１ 、Ｒ２ 、Ｒ３ 、Ｒ４ 、Ｒ５ 、Ｒ６ 、
Ｒ７ 、Ｒ８ は水素、炭素数１から６のアルキル基ま
たはアルコキシ基、フェニル基、アラルキル基、Ｃｌ、
ＢｒまたはＦを表す。）embedded image (R1 , R2 , R3 , R4 , R5 , R6 ,
R7 and R8 are hydrogen, an alkyl group or alkoxy group having 1 to 6 carbon atoms, a phenyl group, an aralkyl group, Cl,
Represents Br or F. )
【化１０】
（Ｒ９ 、Ｒ１０、Ｒ１１、Ｒ１２は水素、炭素数１か
ら１０のアルキル基またはアルコキシ基、フェニル基、
アラルキル基、Ｃｌ、ＢｒまたはＦを表す。）embedded image (R9, R10, R11, R12 are hydrogen, an alkyl group or alkoxy group having 1 to 10 carbon atoms, a phenyl group,
Represents an aralkyl group, Cl, Br or F. )
【０００６】又、本発明の第２の態様は、（Ａ）上記一
般式（ＩＩＩ）で表されるジカルボン酸またはそのエス
テル形成性誘導体と、（Ｅ）イソフタル酸またはそのエ
ステル形成性誘導体を、（Ａ）成分が全酸成分の５２〜
９９モル％、（Ｅ）成分が全酸成分の４８〜１モル％の
割合で含むジカルボン酸成分と、ジオ―ル成分とを共重
合させて得られる包装材料用ポリエステルに関するもの
である。上記一般式（ＩＩＩ）中のＲ１ 、Ｒ２ 、Ｒ
３ 、Ｒ４ 、Ｒ５ 、Ｒ６ 、Ｒ７ 、Ｒ８は水素、
炭素数１から６のアルキル基またはアルコキシ基、フェ
ニル基、アラルキル基、Ｃｌ、Ｂｒ、またはＦを表すが
、アルキル基としてはメチル基やエチル基等の低級アル
キル基、アルコキシ基としてはメトキシ基やエトキシ基
等の低級アルコキシ基、アラキル基としてはベンジル基
が好ましく挙げられる。[0006] A second aspect of the present invention also provides (A) a dicarboxylic acid represented by the above general formula (III) or an ester-forming derivative thereof, and (E) isophthalic acid or an ester-forming derivative thereof, (A) Component is 52~ of total acid component
The present invention relates to a polyester for packaging materials obtained by copolymerizing a dicarboxylic acid component containing 99 mol% of the total acid components and a dicarboxylic acid component containing component (E) in a proportion of 48 to 1 mol% of the total acid components. R1, R2, R in the above general formula (III)
3, R4, R5, R6, R7, R8 are hydrogen,
It represents an alkyl group or alkoxy group having 1 to 6 carbon atoms, a phenyl group, an aralkyl group, Cl, Br, or F, and the alkyl group includes a lower alkyl group such as a methyl group and an ethyl group, and the alkoxy group includes a methoxy group and Preferred examples of lower alkoxy groups such as ethoxy groups and aralkyl groups include benzyl groups.
【０００７】一般式（ＩＩＩ）で示されるジカルボン酸
としては、２，２´−ジフェニルスルホンジオキシジ酢
酸、３，３´−ジフェニルスルホンジオキシジ酢酸、４
，４´−ジフェニルスルホンジオキシジ酢酸、２，３´
−ジフェニルスルホンジオキシジ酢酸、２，４´−ジフ
ェニルスルホンジオキシジ酢酸、３，４´−ジフェニル
スルホンジオキシジ酢酸、２−メチル−４，４´−ジフ
ェニルスルホンジオキシジ酢酸、３−メチル−４，４´
−ジフェニルスルホンジオキシジ酢酸、２，３−ジメチ
ル−４，４´−ジフェニルスルホンジオキシジ酢酸、２
，５−ジメチル−４，４´−ジフェニルスルホンジオキ
シジ酢酸、２，６−ジメチル−４，４´−ジフェニルス
ルホンジオキシジ酢酸、２，２´−ジメチル−４，４´
−ジフェニルスルホンジオキシジ酢酸、２，３´−ジメ
チル−４，４´−ジフェニルスルホンジオキシジ酢酸、
３，３´−ジメチル−４，４´−ジフェニルスルホンジ
オキシジ酢酸、２−エチル−４，４´−ジフェニルスル
ホンジオキシジ酢酸、３−エチル−４，４´−ジフェニ
ルスルホンジオキシジ酢酸、２−メトキシ−４，４´−
ジフェニルスルホンジオキシジ酢酸、３−メトキシ−４
，４´−ジフェニルスルホンジオキシジ酢酸、３−クロ
ロ−２，２´−ジフェニルスルホンジオキシジ酢酸、２
−クロロ−３，３´−ジフェニルスルホンジオキシジ酢
酸、２−クロロ−４，４´−ジフェニルスルホンジオキ
シジ酢酸、２−クロロ−３，４´−ジフェニルスルホン
ジオキシジ酢酸などが挙げられる。これらのうち好まし
くはジフェニルスルホンジオキシジ酢酸の２，２´−、
３，３´−、４，４´−、２，３´−、２，４´−、３
，４´−構造異性体であり、なかでも４，４´−ジフェ
ニルスルホンジオキシジ酢酸が特に好ましい。Examples of dicarboxylic acids represented by the general formula (III) include 2,2'-diphenylsulfonedioxydiacetic acid, 3,3'-diphenylsulfonedioxydiacetic acid, and 4-diphenylsulfonedioxydiacetic acid.
, 4'-diphenylsulfonedioxydiacetic acid, 2,3'
-Diphenylsulfonedioxydiacetic acid, 2,4'-diphenylsulfonedioxydiacetic acid, 3,4'-diphenylsulfonedioxydiacetic acid, 2-methyl-4,4'-diphenylsulfonedioxydiacetic acid, 3- Methyl-4,4'
-diphenylsulfonedioxydiacetic acid, 2,3-dimethyl-4,4'-diphenylsulfonedioxydiacetic acid, 2
, 5-dimethyl-4,4'-diphenylsulfonedioxydiacetic acid, 2,6-dimethyl-4,4'-diphenylsulfonedioxydiacetic acid, 2,2'-dimethyl-4,4'
-diphenylsulfonedioxydiacetic acid, 2,3'-dimethyl-4,4'-diphenylsulfonedioxydiacetic acid,
3,3'-dimethyl-4,4'-diphenylsulfone dioxydiacetic acid, 2-ethyl-4,4'-diphenylsulfone dioxydiacetic acid, 3-ethyl-4,4'-diphenylsulfone dioxydiacetic acid , 2-methoxy-4,4'-
diphenylsulfonedioxydiacetic acid, 3-methoxy-4
, 4'-diphenylsulfonedioxydiacetic acid, 3-chloro-2,2'-diphenylsulfonedioxydiacetic acid, 2
-Chloro-3,3'-diphenylsulfonedioxydiacetic acid, 2-chloro-4,4'-diphenylsulfonedioxydiacetic acid, 2-chloro-3,4'-diphenylsulfonedioxydiacetic acid, etc. . Among these, preferably 2,2'- of diphenylsulfone dioxydiacetic acid,
3,3'-, 4,4'-, 2,3'-, 2,4'-, 3
, 4'-structural isomer, and 4,4'-diphenylsulfone dioxydiacetic acid is particularly preferred.
【０００８】又、上記一般式（ＩＶ）中のＲ９ 、Ｒ１
０、Ｒ１１、Ｒ１２は水素、炭素数１から１０のアルキ
ル基またはアルコキシ基、フェニル基、アラルキル基、
Ｃｌ、Ｂｒ、またはＦを表すが、アルキル基としてはメ
チル基やエチル基等の低級アルキル基、アルコキシ基と
してはメトキシ基やエトキシ基等の低級アルコキシ基、
アラルキル基としてはベンジル基が好ましく挙げられる
。前記一般式（ＩＶ）で示されるジカルボン酸としては
、１，２−フェニレンジオキシジ酢酸、１，３−フェニ
レンジオキシジ酢酸、１，４−フェニレンジオキシジ酢
酸、２−メチル−１，３−フェニレンジオキシジ酢酸、
４−メチル−１，３−フェニレンジオキシジ酢酸、５−
メチル−１，３−フェニレンジオキシジ酢酸、４−エチ
ル−１，３−フェニレンジオキシ酢酸、５−エチル−１
，３−フェニレンジオキシジ酢酸、４−メトキシ−１，
３−フェニレンジオキシジ酢酸、５−メトキシ−１，３
−フェニレンジオキシジ酢酸、４−クロロ−１，２−フ
ェニレンジオキシジ酢酸、４−クロロ−１，３−フェニ
レンジオキシジ酢酸等が挙げられる。本発明のポリエス
テルにおいて、これら一般式（ＩＶ）で示されるジカル
ボン酸またはそのエステル形成性誘導体はいずれも使用
することができるが、フェニレンジオキシジ酢酸の１，
２−、１，３−、１，４−構造異性体が好ましく、なか
でも１，３−フェニレンジオキシジ酢酸が特に好ましい
。[0008] Furthermore, R9 and R1 in the above general formula (IV)
0, R11, R12 are hydrogen, an alkyl group or alkoxy group having 1 to 10 carbon atoms, a phenyl group, an aralkyl group,
It represents Cl, Br, or F, and the alkyl group is a lower alkyl group such as a methyl group or an ethyl group, and the alkoxy group is a lower alkoxy group such as a methoxy group or an ethoxy group.
As the aralkyl group, a benzyl group is preferably mentioned. The dicarboxylic acids represented by the general formula (IV) include 1,2-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, 1,4-phenylenedioxydiacetic acid, 2-methyl-1, 3-phenylenedioxydiacetic acid,
4-Methyl-1,3-phenylenedioxydiacetic acid, 5-
Methyl-1,3-phenylenedioxydiacetic acid, 4-ethyl-1,3-phenylenedioxyacetic acid, 5-ethyl-1
, 3-phenylenedioxydiacetic acid, 4-methoxy-1,
3-phenylenedioxydiacetic acid, 5-methoxy-1,3
-phenylenedioxydiacetic acid, 4-chloro-1,2-phenylenedioxydiacetic acid, 4-chloro-1,3-phenylenedioxydiacetic acid, and the like. In the polyester of the present invention, any of these dicarboxylic acids represented by the general formula (IV) or their ester-forming derivatives can be used, but phenylenedioxydiacetic acid 1,
2-, 1,3-, 1,4-structural isomers are preferred, and 1,3-phenylenedioxydiacetic acid is particularly preferred.
【０００９】本発明で使用する各カルボン酸類は酸のま
まで本発明のポリエステルの原料として使用してもよい
し、酸ハライド、エステル、特に低級アルキルエステル
等のエステル形成性誘導体として重合に用いても良い。
また、グリコ―ル類と反応させて数量体化したものを重
合に用いても良い。また、グリコ―ル類と反応させて数
量体化したものを重合に供しても良い。本発明の第１の
態様の包装材料用ポリエステル樹脂においては、前記式
（ＩＩＩ）から得られる（Ａ）成分単位と前記式（ＩＶ
）から得られる（Ｂ）成分単位のモル比は、２０〜１０
０：８０〜０、好ましくは３０〜１００：７０〜０、更
に好ましくは４０〜１００：６０〜０の範囲である。
一般式（ＩＶ）で表されるジカルボン酸単位を使用する
量がこの範囲を越えた場合には、得られるポリエステル
樹脂のガラス移転温度（Ｔｇ）が低下し過ぎるために成
形前の樹脂の乾燥が困難になるし、また得られたポリエ
ステル樹脂をポリエチレンテレフタレ―トとブレンドし
て成形したときの耐熱性が低下してしまう。又、本発明
の第２の態様の包装材料用ポリエステルにおいては、（
Ｅ）成分のイソフタル酸単位と前記一般式（ＩＩＩ）か
ら得られる（Ａ）成分のジカルボン酸単位とのモル比は
、４８〜１：５２〜９９、好ましくは４５〜２：５５〜
９８、更に好ましくは４０〜５：６０〜９５の範囲であ
る。Each carboxylic acid used in the present invention may be used as an acid as a raw material for the polyester of the present invention, or may be used in polymerization as an ester-forming derivative such as an acid halide, an ester, and especially a lower alkyl ester. Also good. Alternatively, a merized product obtained by reacting with glycols may be used for polymerization. Alternatively, a quantifier obtained by reacting with glycols may be subjected to polymerization. In the polyester resin for packaging materials according to the first aspect of the present invention, the component unit (A) obtained from the formula (III) and the formula (IV
The molar ratio of component units (B) obtained from ) is 20 to 10
The range is 0:80-0, preferably 30-100:70-0, more preferably 40-100:60-0. If the amount of dicarboxylic acid units represented by general formula (IV) exceeds this range, the glass transition temperature (Tg) of the resulting polyester resin will drop too much, making it difficult to dry the resin before molding. Moreover, when the obtained polyester resin is blended with polyethylene terephthalate and molded, the heat resistance decreases. In addition, in the polyester for packaging materials according to the second aspect of the present invention, (
The molar ratio of the isophthalic acid unit of component E) to the dicarboxylic acid unit of component (A) obtained from the general formula (III) is 48 to 1:52 to 99, preferably 45 to 2:55.
98, more preferably 40-5:60-95.
【００１０】（Ｅ）成分の量がこの範囲を越える場合に
は、この共重合ポリエステルを製造する際に昇華物の発
生が著しいために製造設備の配管閉塞等のトラブルが問
題となり、さらにボトル物性の面からは強度が不十分と
なるために好ましくない。本発明のポリエステルにおい
ては、第１の態様では（Ａ）、（Ｂ）酸成分単位の和が
、全繰り返し単位の少なくとも５０モル％以上、好まし
くは６０モル％以上、更に好ましくは７０％以上を占め
ることが好ましく、又第２の態様では（Ａ）、（Ｅ）酸
成分単位の和が、全繰り返し単位の６０モル％以上、好
ましくは７０％以上を占めることが好ましい。また、（
Ａ）、（Ｂ）酸成分又は（Ａ）、（Ｅ）酸成分が前述の
モル％で含有されているかぎり、その他の小量のジカル
ボン酸またはそのエステル形成性誘導体やオキシ酸また
はそのエステル形成性誘導体を使うこともできる。これ
らのジカルボン酸としては、本発明の第１の態様におい
ては、フタル酸、下記一般式（Ｖ）で表されるジカルボ
ン酸、４，４´−ビフェニルジカルボン酸、４，４´−
ジフェノキシエタンジカルボン酸、４，４´−ジフェニ
ルスルホンジカルボン酸及びこれらの構造異性体、マロ
ン酸、コハク酸、アジピン酸等の脂肪族ジカルボン酸、
オキシ酸またはその誘導体としては、ヒドロキシ安息香
酸、グリコ―ル酸、ヒドロキシエトキシ安息香酸メチル
などが挙げられる。[0010] If the amount of component (E) exceeds this range, problems such as clogging of pipes in the production equipment may occur due to the significant generation of sublimated substances during the production of this copolymerized polyester, and furthermore, the physical properties of the bottle may deteriorate. From this point of view, it is not preferable because the strength is insufficient. In the polyester of the present invention, in the first aspect, the sum of the acid component units (A) and (B) accounts for at least 50 mol% or more, preferably 60 mol% or more, and more preferably 70% or more of the total repeating units. In the second embodiment, the sum of the acid component units (A) and (E) preferably accounts for 60 mol% or more, preferably 70% or more of the total repeating units. Also,(
As long as A), (B) acid component or (A), (E) acid component is contained in the above-mentioned mol%, other small amounts of dicarboxylic acids or their ester-forming derivatives, oxyacids or their esters can be formed. Sexual derivatives can also be used. In the first aspect of the present invention, these dicarboxylic acids include phthalic acid, dicarboxylic acid represented by the following general formula (V), 4,4'-biphenyldicarboxylic acid, 4,4'-
Diphenoxyethane dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid and structural isomers thereof, aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid,
Examples of the oxyacid or its derivative include hydroxybenzoic acid, glycolic acid, and methyl hydroxyethoxybenzoate.
【００１１】又、第２の態様においてはフタル酸、前記
一般式（ＩＶ）で表されるジカルボン酸、下記一般式（
Ｖ）で表されるジカルボン酸、４，４´−ビフェニルジ
カルボン酸、４，４´−ジフェノキシエタンジカルボン
酸、４，４´−ジフェニルスルホンジカルボン酸及びこ
れらの構造異性体、マロン酸、コハク酸、アジピン酸等
の脂肪族ジカルボン酸、オキシ酸またはその誘導体とし
ては、ヒドロキシ安息香酸、グリコ―ル酸、ヒドロキシ
エトキシ安息香酸メチルなどが挙げられる。
ＨＯＯＣ−Ｒ１３− Ｘ−Ｒ１４−ＣＯＯＨ
（Ｖ）（Ｒ１３、Ｒ１
４は２価の脂肪族基、ＸはＯまたはＮＨを表す。）前記
一般式（Ｖ）で示されるジカルボン酸としては、２，２
´−オキシジ酢酸（ジグリコ―ル酸）、３，３´−オキ
シジプロピオン酸（ジエチルエ―テル−β，β´−ジカ
ルボン酸）、２，２´−オキシジプロピオン酸、４，４
´−オキシジ酪酸、３，３´−オキシジ酪酸、２，２´
−オキシジ酪酸、２，２´−イミノジ酢酸、３，３´−
イミノジプロピオン酸、２，２´−イミノジプロピオン
酸、４，４´−イミノジ酪酸、３，３´−イミノジ酪酸
、２，２´−イミノジ酪酸等が挙げられる。本発明のポ
リエステルにおいて、これら一般式（Ｖ）で示されるジ
カルボン酸またはそのエステル形成性誘導体はいずれも
使用することができるが、特に２，２´−イミノジ酢酸
が好ましい。In the second embodiment, phthalic acid, a dicarboxylic acid represented by the general formula (IV), and a dicarboxylic acid represented by the general formula (IV) shown below,
Dicarboxylic acid represented by V), 4,4'-biphenyldicarboxylic acid, 4,4'-diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid and structural isomers thereof, malonic acid, succinic acid Examples of aliphatic dicarboxylic acids such as adipic acid, oxyacids, and derivatives thereof include hydroxybenzoic acid, glycolic acid, and methyl hydroxyethoxybenzoate. HOOC-R13-X-R14-COOH
(V) (R13, R1
4 represents a divalent aliphatic group, and X represents O or NH. ) As the dicarboxylic acid represented by the general formula (V), 2,2
'-Oxydiacetic acid (diglycolic acid), 3,3'-oxydipropionic acid (diethyl ether-β,β'-dicarboxylic acid), 2,2'-oxydipropionic acid, 4,4
'-oxydibutyric acid, 3,3'-oxydibutyric acid, 2,2'
-oxydibutyric acid, 2,2'-iminodiacetic acid, 3,3'-
Examples include iminodipropionic acid, 2,2'-iminodipropionic acid, 4,4'-iminodibutyric acid, 3,3'-iminodibutyric acid, and 2,2'-iminodibutyric acid. In the polyester of the present invention, any of these dicarboxylic acids represented by the general formula (V) or their ester-forming derivatives can be used, but 2,2'-iminodiacetic acid is particularly preferred.
【００１２】本発明のポリエステルに使われるジオ―ル
成分としては、エチレングリコ―ル、１，２−プロパン
ジオ―ル、１，３−プロパンジオ―ル、１，４−ブタン
ジオ―ル、ペンタメチレングリコ―ル、ヘキサメチレン
グリコ―ル、ネオペンチルグリコ―ル、ジエチレングリ
コ―ル等の脂肪族グリコ―ル、シクロヘキサンジメタノ
―ルのような脂環式グリコ―ルやさらにはビスフェノ―
ルＡ、ビスフェノ―ルＳ等の芳香族ジヒドロキシ化合物
誘導体などを挙げることができる。これらのうちで、一
般的にはエチレングリコ―ルが最も好ましい。また、本
発明のポリエステルは、本発明の目的を逸脱しない範囲
でトリメチロ―ルエタン、トリメチロ―ルプロパン、ペ
ンタエリスリト―ル、グリセリン、トリメリット酸、ト
リメシン酸、ピロメリット酸、芳香族ジヒドロキシ化合
物のグリシジルエ―テル、例えばビスフェノ―ルＡジグ
リシジルエ―テル等の多官能化合物や、Ｏ−ベンゾイル
安息香酸等の単官能化合物を共存させても良い。かかる
多官能化合物や単官能化合物はジオ―ル成分の２０モル
％以下、好ましくは１０モル％以下、更に好ましくは５
モル％以下の範囲で使用される。本発明のポリエステル
は、その極限粘度（フェノ―ル／テトラクロロエタン（
重量比１／１）の混合溶媒を用いて３０℃で測定した単
位：ｄｌ／ｇ）が、０．４〜２．０、好ましくは０．５
〜１．５の範囲であることが望ましい。極限粘度が０．
４未満では、得られるポリエステルの強度が低く、重合
反応終了後、反応缶から抜き出しチップに切断する際や
、ポリエチレンテレフタレ―トとブレンドしてフィルム
やシ―ト、また瓶やたる、缶等の容器として成形する際
に実用上必要な物性が得られない。極限粘度が２．０を
越える場合には溶融粘度が高くなりすぎて射出、押出、
ブロ―等の成形が困難となるなどの問題がある。The diol components used in the polyester of the present invention include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and pentamethylene. Glycol, aliphatic glycols such as hexamethylene glycol, neopentyl glycol, and diethylene glycol, alicyclic glycols such as cyclohexanedimethanol, and even bisphenols.
Examples include aromatic dihydroxy compound derivatives such as alcohol A and bisphenol S. Of these, ethylene glycol is generally the most preferred. In addition, the polyester of the present invention includes glycidyl esters of trimethylol ethane, trimethylol propane, pentaerythritol, glycerin, trimellitic acid, trimesic acid, pyromellitic acid, and aromatic dihydroxy compounds within the scope of the invention. A polyfunctional compound such as bisphenol A diglycidyl ether or a monofunctional compound such as O-benzoylbenzoic acid may also be present. Such polyfunctional compounds and monofunctional compounds account for 20 mol% or less, preferably 10 mol% or less, more preferably 5 mol% or less of the diol component.
It is used in a range of mol% or less. The intrinsic viscosity of the polyester of the present invention (phenol/tetrachloroethane (
Unit: dl/g) measured at 30°C using a mixed solvent with a weight ratio of 1/1) is 0.4 to 2.0, preferably 0.5
It is desirable that it is in the range of 1.5 to 1.5. Intrinsic viscosity is 0.
If it is less than 4, the strength of the obtained polyester will be low, and it will be difficult to remove it from the reaction can after the polymerization reaction and cut it into chips, or blend it with polyethylene terephthalate to make films, sheets, bottles, barrels, cans, etc. The physical properties required for practical use cannot be obtained when molded into a container. If the intrinsic viscosity exceeds 2.0, the melt viscosity will be too high and injection, extrusion,
There are problems such as difficulty in blow molding.
【００１３】本発明のポリエステルは、ポリエチレンテ
レフタレ―トについて従来から公知の任意の重合方法で
製造することができる。本発明の第１の態様について言
えば、例えば、一般式（ＩＩＩ）で示されるジカルボン
酸、例えば４，４´−ジフェニルスルホンジオキシジ酢
酸と、一般式（ＩＶ）で示されるジカルボン酸、例えば
１，３−フェニレンジオキシジ酢酸、およびエチレング
リコ―ルを用いて加圧下で直接エステル化反応を行った
後、更に昇温すると共に次第に減圧とし重縮合反応させ
る方法がある。あるいは、一般式（ＩＩＩ）で示される
ジカルボン酸のエステル誘導体、例えば４，４´−ジフ
ェニルスルホンジオキシジ酢酸ジメチルエステルと、一
般式（ＩＶ）で示されるジカルボン酸のエステル誘導体
、例えば１，３−フェニレンジオキシジ酢酸ジエチルエ
ステル、およびエチレングリコ―ルを用いてエステル交
換反応を行い、その後得られた反応物を更に重縮合する
ことで製造できる。又、本発明の第２の態様について言
えば、例えばイソフタル酸、一般式（ＩＩＩ）で示され
るジカルボン酸、例えば４，４´−ジフェニルスルホン
ジオキシジ酢酸、およびエチレングリコ―ルを用いて加
圧下で直接エステル化反応を行った後、更に昇温すると
共に次第に減圧とし重縮合反応させる方法がある。ある
いは、イソフタル酸のエステル誘導体、例えばイソフタ
ル酸ジメチルエステルと、一般式（ＩＩＩ）で示される
ジカルボン酸のエステル誘導体、例えば４，４´−ジフ
ェニルスルホンジオキシジ酢酸ジエチルエステル、およ
びエチレングリコ―ルを用いてエステル交換反応を行い
、その後得られた反応物を更に重縮合することで製造で
きる。The polyester of the present invention can be produced by any conventionally known polymerization method for polyethylene terephthalate. Regarding the first aspect of the present invention, for example, a dicarboxylic acid represented by general formula (III), e.g. 4,4'-diphenylsulfone dioxydiacetic acid, and a dicarboxylic acid represented by general formula (IV), e.g. There is a method in which a direct esterification reaction is carried out under pressure using 1,3-phenylenedioxydiacetic acid and ethylene glycol, and then the temperature is further raised and the pressure is gradually reduced to carry out a polycondensation reaction. Alternatively, an ester derivative of a dicarboxylic acid represented by the general formula (III), such as dimethyl 4,4'-diphenylsulfonedioxydiacetate, and an ester derivative of a dicarboxylic acid represented by the general formula (IV), such as 1,3 It can be produced by carrying out a transesterification reaction using -phenylenedioxydiacetic acid diethyl ester and ethylene glycol, and then further polycondensing the obtained reaction product. Regarding the second aspect of the present invention, for example, isophthalic acid, a dicarboxylic acid represented by the general formula (III), such as 4,4'-diphenylsulfone dioxydiacetic acid, and ethylene glycol are used. There is a method in which a direct esterification reaction is carried out under pressure, and then the temperature is further raised and the pressure is gradually reduced to carry out a polycondensation reaction. Alternatively, an ester derivative of isophthalic acid, such as dimethyl isophthalic acid, an ester derivative of dicarboxylic acid represented by general formula (III), such as diethyl 4,4'-diphenylsulfonedioxydiacetate, and ethylene glycol. It can be produced by carrying out a transesterification reaction using a transesterifying agent, and then further polycondensing the obtained reaction product.
【００１４】かかるポリマ―の製造においては、エステ
ル化触媒、エステル交換触媒、重縮合触媒、安定剤など
を使用することが好ましい。エステル交換触媒としては
、公知の化合物、例えばカルシウム、マンガン、亜鉛、
ナトリウム、およびリチウム化合物などの１種以上を用
いることができるが、透明性の観点からマンガン化合物
が特に好ましい。重合触媒としては公知のアンチモン、
ゲルマニウム、チタン、およびコバルト化合物等の１種
以上を用いることができるが、好ましくはアンチモン、
ゲルマニウム、及びチタン化合物が用いられる。また本
発明では、必要に応じて、従来から公知の添加剤、例え
ば酸化防止剤、紫外線吸収剤、蛍光増白剤、離型剤、帯
電防止剤、分散剤、及び染顔料等の着色剤をポリエステ
ル製造時のいずれかの段階で添加しても良く、成形加工
前にいわゆるマスタ―バッチ処方で添加しても良い。[0014] In the production of such polymers, it is preferable to use esterification catalysts, transesterification catalysts, polycondensation catalysts, stabilizers, and the like. As transesterification catalysts, known compounds such as calcium, manganese, zinc,
One or more of sodium and lithium compounds can be used, but manganese compounds are particularly preferred from the viewpoint of transparency. Known antimony as a polymerization catalyst,
One or more of germanium, titanium, and cobalt compounds can be used, but preferably antimony,
Germanium and titanium compounds are used. In addition, in the present invention, conventionally known additives such as antioxidants, ultraviolet absorbers, optical brighteners, mold release agents, antistatic agents, dispersants, and colorants such as dyes and pigments may be added as necessary. It may be added at any stage during polyester production, or may be added in a so-called master batch formulation before molding.
【００１５】本発明のポリエステルは、必要に応じて更
に、加熱処理を実施し、低アセトアルデヒド化あるいは
、低オリゴマ―化してから使用してもよい。加熱処理は
、通常、３０℃以上〜樹脂の粘着温度直下の温度で数時
間〜数百時間以下の範囲内に於て実施するのが好ましい
。このようにして得られた本発明のポリエステルは、溶
融成形して成形品とされる。この際、該ポリエステルだ
けで成形品としても良いし、他の熱可塑性樹脂と組合わ
せて成形品としてもよい。具体的には、ポリエチレンテ
レフタレ―ト、ポリブチレンテレフタレ―ト、ポリエチ
レンナフタレンジカルボキシレ―ト、ポリブチレンナフ
タレンジカルボキシレ―ト、ポリエステルエラストマ―
、ポリカ―ボネ―トやポリアミド等の他の熱可塑性樹脂
成分と、本発明のポリエステル成分をブレンドして一体
構造に形成することも可能であるし、更にはポリエチレ
ンテレフタレ―ト成分や上記のような熱可塑性樹脂成分
と本発明のポリエステル成分とを多層構造に形成するこ
ともできる。ブレンドする際の熱可塑性樹脂としてはポ
リエチレンテレフタレ―トが好ましく、ポリエチレンテ
レフタレ―トと本発明のポリエステルのブレンドの割合
は、該ポリエステルが組成物中の３〜８０重量％を占め
ることが好ましい。ポリエステルの割合が３重量％未満
では、ポリエチレンテレフタレ―トのガスバリヤ―性改
良効果がそれ程顕著でないし、８０重量％を越えると、
機械的強度や耐熱性の点で性能の低下が見られる。
ここで用いられるポリエチレンテレフタレートの極限粘
度は本発明のポリエステルと同様に０．４〜２．０程度
が好ましい。[0015] The polyester of the present invention may be used after being further subjected to a heat treatment to reduce the amount of acetaldehyde or oligomer, if necessary. The heat treatment is usually preferably carried out at a temperature of 30° C. or higher to just below the adhesive temperature of the resin for a period of several hours to several hundred hours. The thus obtained polyester of the present invention is melt-molded into a molded article. At this time, the polyester may be used alone as a molded article, or may be made in combination with other thermoplastic resins. Specifically, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalene dicarboxylate, polybutylene naphthalene dicarboxylate, polyester elastomer
It is also possible to form an integral structure by blending the polyester component of the present invention with other thermoplastic resin components such as polycarbonate or polyamide. The thermoplastic resin component and the polyester component of the present invention can also be formed into a multilayer structure. The thermoplastic resin to be blended is preferably polyethylene terephthalate, and the blend ratio of polyethylene terephthalate and the polyester of the present invention is preferably such that the polyester accounts for 3 to 80% by weight of the composition. . When the proportion of polyester is less than 3% by weight, the effect of improving gas barrier properties of polyethylene terephthalate is not so remarkable, and when it exceeds 80% by weight,
A decrease in performance is seen in terms of mechanical strength and heat resistance. The intrinsic viscosity of the polyethylene terephthalate used here is preferably about 0.4 to 2.0, similarly to the polyester of the present invention.
【００１６】本発明のポリエステル組成物は、ポリエチ
レンテレフタレート等の成形において一般的に使用され
る溶融成形法のすべてが適用でき、これら成形法により
フィルム、シート、トレイ、中空容器、その他の包装材
料として成形し、未延伸の状態でもガスバリヤー性の高
い材料として使用可能である。また、該ポリエステル組
成物を少なくとも１軸方向に延伸することにより、更に
ガスバリヤー性や機械的強度を改善することが可能であ
る。本発明のポリエステル組成物の延伸シートは、射出
成形や押出成形でシート状に成形された本発明のポリエ
ステル組成物を、通常ポリエチレンテレフタレートの延
伸に用いられる１軸延伸、逐次２軸延伸、同時２軸延伸
のうちの任意の延伸方法を用いて成形される。また、圧
空成形によりカップ状やトレイ状に成形することもでき
る。本発明のポリエステル組成物の延伸シートを製造す
るに当っては、延伸温度は本発明のポリエステルのガラ
ス転移温度ないしガラス転移温度より８０℃高い温度の
間に設定すればよい。延伸倍率は１軸延伸の場合であれ
ば通常１．１倍から１０倍、好ましくは１．１倍から８
倍の範囲で行い、２軸延伸の場合であれば、縦方向及び
横方向ともそれぞれ１．１倍から８倍、好ましくは１．
１倍から５倍の範囲で行えばよい。このようにして得ら
れた、本発明のポリエステル組成物の延伸シートは、透
明性、ガスバリヤー性、機械的強度に優れ、フィルム状
、カップ状、トレイ状などの包装材料として有用である
。[0016] The polyester composition of the present invention can be applied to all melt molding methods commonly used for molding polyethylene terephthalate, etc., and can be used as films, sheets, trays, hollow containers, and other packaging materials by these molding methods. Even when molded and unstretched, it can be used as a material with high gas barrier properties. Moreover, by stretching the polyester composition in at least one direction, it is possible to further improve gas barrier properties and mechanical strength. The stretched sheet of the polyester composition of the present invention can be produced by forming the polyester composition of the present invention into a sheet by injection molding or extrusion molding, by uniaxial stretching, sequential biaxial stretching, or simultaneous biaxial stretching, which is usually used for stretching polyethylene terephthalate. Shaped using any stretching method among axial stretching. Moreover, it can also be molded into a cup shape or a tray shape by air pressure molding. In producing a stretched sheet of the polyester composition of the present invention, the stretching temperature may be set between the glass transition temperature of the polyester of the present invention and a temperature 80° C. higher than the glass transition temperature. In the case of uniaxial stretching, the stretching ratio is usually 1.1 times to 10 times, preferably 1.1 times to 8 times.
In the case of biaxial stretching, it is 1.1 to 8 times in both the longitudinal and transverse directions, preferably 1.
It may be done within the range of 1 to 5 times. The thus obtained stretched sheet of the polyester composition of the present invention has excellent transparency, gas barrier properties, and mechanical strength, and is useful as a packaging material in the form of a film, cup, tray, etc.
【００１７】本発明のポリエステル中空成形体は、本発
明のポリエステル組成物から成形したプリフォームをブ
ロー成形してなるもので、従来よりポリエチレンテレフ
タレートブロー成形で用いられる装置を用いることがで
きる。具体的には、例えば押出吹込み法、射出吹込み法
、射出成形または押出し成形で一旦プリフォームを成形
し、そのままであるいは口栓部、底部を加工後それを再
加熱し、二軸延伸するホットパリソン法あるいはコール
ドパリソン法等の吹込み成形法が適用される。延伸温度
は７０ないし１３０℃、好ましくは８０ないし１２０℃
で、延伸倍率は縦方向に１．５倍から３．５倍、円周方
向に２倍から５倍の範囲で行えばよい。また、本発明の
ポリエステル中空成形体を製造するに当って、本発明の
ポリエステル組成物を主体とする層と、ポリエチレンテ
レフタレートを主体とするポリアルキレンテレフタレー
トよりなる層を積層したプリフォームを成形し、これを
２軸延伸ブロー成形して多層中空成形容器としてもよい
。この際、その層構成に特に限定はなく、３〜５層程度
の構成が好ましい。また多層容器の場合も、従来のポリ
エチレンテレフタレート等の成形方法に順じて製造する
ことができる。すなわち、通常の射出成形機または、複
数個の射出装置を有する射出成形機により成形された多
層パリソン、または多層押出成形機により成形された多
層チューブの一端を有底化して得られた多層パリソンを
、例えば８５ないし１３０℃のポリエチレンテレフタレ
ートの延伸温度で延伸する方法で製造可能である。本発
明のポリエステルを多層容器に成形する場合、その層構
成に特に限定はなく、また、層の数も何ら限定はないが
、３〜５層程度の構成が好ましい。The polyester blow molded article of the present invention is obtained by blow molding a preform molded from the polyester composition of the present invention, and can be produced using equipment conventionally used in polyethylene terephthalate blow molding. Specifically, for example, a preform is once formed by extrusion blowing method, injection blowing method, injection molding, or extrusion molding, and then it is reheated as it is or after processing the spout and bottom part, and then biaxially stretched. A blow molding method such as a hot parison method or a cold parison method is applied. The stretching temperature is 70 to 130°C, preferably 80 to 120°C.
The stretching ratio may be 1.5 to 3.5 times in the longitudinal direction and 2 to 5 times in the circumferential direction. Furthermore, in producing the polyester hollow molded body of the present invention, a preform is formed by laminating a layer mainly composed of the polyester composition of the present invention and a layer composed of polyalkylene terephthalate mainly composed of polyethylene terephthalate, This may be biaxially stretched and blow molded to form a multilayer blow molded container. At this time, there is no particular limitation on the layer structure, and a structure of about 3 to 5 layers is preferable. Also, in the case of a multilayer container, it can be manufactured according to a conventional molding method for polyethylene terephthalate or the like. That is, a multilayer parison molded by a normal injection molding machine or an injection molding machine having a plurality of injection devices, or a multilayer parison obtained by bottoming one end of a multilayer tube molded by a multilayer extrusion molding machine. For example, it can be produced by a method of stretching polyethylene terephthalate at a stretching temperature of 85 to 130°C. When the polyester of the present invention is molded into a multilayer container, there is no particular limitation on the layer structure, and there is also no limitation on the number of layers, but a structure of about 3 to 5 layers is preferable.
【００１８】また射出成形によりシート化した後、１軸
または２軸延伸フィルムとしたり、真空成形あるいは圧
空成形により缶状の容器やトレイ等に成形することもで
きるし、多層押出成形機により、例えば、ポリエチレン
テレフタレートとの多層シートとし、同様に１軸延伸あ
るいは２軸延伸したフィルムや缶状容器、トレイに成形
することも可能である。本発明のポリエステルと、前記
の各熱可塑性樹脂をブレンドして包装材料を成形する場
合には、両成分を押出機で溶融混練して混合チップを得
、次いでこれを成形に供することも可能であるし、また
、それぞれの成分をドライブレンドし、直接成形に供す
ることも可能である。本発明の対象とする、かかる成形
品としては、具体的には、瓶、たる、缶等の容器や未延
伸シ―トを深絞り成形して得られる容器、更にはシ―ト
を真空または圧空成形して得られるトレイ等の容器が挙
げられる。After forming into a sheet by injection molding, it can be made into a uniaxially or biaxially stretched film, or it can be formed into a can-shaped container or tray by vacuum forming or pressure forming, or by using a multilayer extrusion molding machine, for example. It is also possible to make a multilayer sheet with polyethylene terephthalate and to form it into a monoaxially or biaxially stretched film, a can-shaped container, or a tray. When molding a packaging material by blending the polyester of the present invention and each of the above-mentioned thermoplastic resins, it is also possible to melt and knead both components in an extruder to obtain mixed chips, which are then subjected to molding. However, it is also possible to dry blend the respective components and directly mold them. Specifically, such molded products that are the object of the present invention include containers such as bottles, barrels, and cans, containers obtained by deep drawing an unstretched sheet, and furthermore, a sheet formed by vacuum or Examples include containers such as trays obtained by pressure forming.
【００１９】[0019]
【実施例】以下、実施例により本発明を更に詳細に説明
するが、本発明はその要旨を越えない限り以下の実施例
に限定されるものではない。なお、実施例中「部」は「
重量部」を意味するものとし、本実施例で使用した種々
の測定法を以下に示す。
・極限粘度
フェノ―ル／テトラクロロエタン（重量比１／１）中、
３０℃で測定した。
・Ｈ−ＮＭＲ
日本電子製 ＪＮＭ−ＧＸ２７０ ＦＴ−ＮＭＲを
使用し、溶媒に重水素化ジメチルスルホキシドまたは重
水素化クロロホルム、内部基準にテトラメチルシランを
用いて、２７℃で測定した。
・酸素透過率
約２００μ肉厚の押出シ―トサンプル、または内容積１
．５リットル、肉厚約３３０μ、有効表面積７００ｃｍ
２ のボトルサンプルを作成し、２３℃、１００％ＲＨ
条件下、「ＯＸ−ＴＲＡＮ １０／５０Ａ」酸素透過
率測定装置（米国Ｍｏｄｅｒｎ Ｃｏｎｔｒｏｌｓ社
製）で測定し、ｃｃ・ｍｍ／ｍ２ ・ｄａｙ・ａｔｍま
たはｃｃ／ボトル・ｄａｙ・ａｔｍで示した。EXAMPLES The present invention will be explained in more detail with reference to examples below, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In addition, "part" in the example is "
The various measurement methods used in this example are shown below.・In intrinsic viscosity phenol/tetrachloroethane (weight ratio 1/1),
Measured at 30°C. -H-NMR Measurement was performed at 27°C using JNM-GX270 FT-NMR manufactured by JEOL, using deuterated dimethyl sulfoxide or deuterated chloroform as a solvent and tetramethylsilane as an internal standard.・Extruded sheet sample with oxygen permeability of approximately 200μ wall thickness or internal volume 1
．． 5 liters, wall thickness approximately 330μ, effective surface area 700cm
2. Create a bottle sample and store it at 23℃ and 100% RH.
It was measured under the following conditions using an "OX-TRAN 10/50A" oxygen permeability measuring device (manufactured by Modern Controls, Inc., USA), and expressed in cc/mm/m2/day/atm or cc/bottle/day/atm.
【００２０】実施例１
４，４´−ジフェニルスルホンジオキシジ酢酸１９，０
００部、エチレングリコ―ル３，９００部をオ―トクレ
―プに仕込み、窒素雰囲気の加圧（２．５Ｋｇ／ｃｍ２
）下、撹拌しつつ２２０〜２４５℃で３時間エステル化
反応を行い、この間生成する水を系外へ留去した。
このエステル化物に、チタンテトラブトキシド７．０部
を加え、重合槽内は常圧より漸次減圧にするとともに、
徐々に昇温し、２６０℃、１ｔｏｒｒの真空下、全重合
時間５時間で極限粘度０．７２の透明なポリエステルを
得た。このポリエステルのＨ−ＮＭＲチャ―トを図１に
示す。４，４´−ジフェニルスルホンジオキシジ酢酸成
分由来のベンゼン環プロトンの吸収が７．８ｐｐｍおよ
び７．１ｐｐｍに観測され、４，４´−ジフェニルスル
ホンジオキシジ酢酸成分およびエチレングリコ―ル成分
由来のメチレンプロトンの吸収が４．９ｐｐｍおよび４
．３ｐｐｍに観測され、このポリエステルが下記の繰返
し構造であることが確認された。Example 1 4,4'-diphenylsulfonedioxydiacetic acid 19,0
00 parts and 3,900 parts of ethylene glycol were placed in an autoclave and pressurized in a nitrogen atmosphere (2.5 kg/cm2).
), the esterification reaction was carried out at 220 to 245° C. for 3 hours with stirring, and the water produced during this period was distilled out of the system. 7.0 parts of titanium tetrabutoxide was added to this esterified product, and the pressure inside the polymerization tank was gradually reduced from normal pressure.
The temperature was gradually raised to 260° C. under a vacuum of 1 torr for a total polymerization time of 5 hours to obtain a transparent polyester having an intrinsic viscosity of 0.72. An H-NMR chart of this polyester is shown in FIG. Absorption of benzene ring protons derived from the 4,4'-diphenylsulfonedioxydiacetic acid component was observed at 7.8 ppm and 7.1 ppm, and absorption of benzene ring protons derived from the 4,4'-diphenylsulfone dioxydiacetic acid component and the ethylene glycol component was observed. The absorption of methylene protons is 4.9 ppm and 4
．． 3 ppm, and it was confirmed that this polyester had the following repeating structure.
【化１１】[Chemical formula 11]
【００２１】実施例２
４，４´−ジフェニルスルホンジオキシジ酢酸１５，０
００部、１，３−フェニレンジオキシジ酢酸４，０００
部、エチレングリコ―ル４，４００部をオ―トクレ―ブ
に仕込み、窒素雰囲気の加圧（２．５Ｋｇ／ｃｍ２ ）
下、撹拌しつつ２２０〜２４５℃で３時間エステル化反
応を行い、この間生成する水を系外へ留去した。このエ
ステル化物に、チタンテトラブトキシド７．０部を加え
、重合槽内は常圧より漸次減圧にするとともに、徐々に
昇温し、２６０℃、１ｔｏｒｒの真空下、全重合時間５
時間で極限粘度０．７０の透明なポリエステルを得た。
このポリエステルのＨ−ＮＭＲチャ―トを図２に示す。
４，４´−ジフェニルスルホンジオキシジ酢酸成分およ
び１，３−フェニレンジオキシジ酢酸成分由来のベンゼ
ン環プロトンの吸収が７．８ｐｐｍ、７．１ｐｐｍおよ
び６．５ｐｐｍに観測され、４，４´−ジフェニルスル
ホンジオキシジ酢酸成分、１，３−フェニレンジオキシ
ジ酢酸成分およびエチレングリコ―ル成分由来のメチレ
ンプロトンの吸収が４．９ｐｐｍ、４．７ｐｐｍおよび
４．３ｐｐｍに観測され、このポリエステルが下記の繰
返し構造であることが確認された。Example 2 4,4'-diphenylsulfonedioxydiacetic acid 15,0
00 parts, 1,3-phenylenedioxydiacetic acid 4,000
and 4,400 parts of ethylene glycol were charged into an autoclave and pressurized in a nitrogen atmosphere (2.5 kg/cm2).
Under stirring, the esterification reaction was carried out at 220 to 245°C for 3 hours, and the water produced during this time was distilled out of the system. 7.0 parts of titanium tetrabutoxide was added to this esterified product, and the pressure inside the polymerization tank was gradually reduced from normal pressure, and the temperature was gradually raised to 260°C under a vacuum of 1 torr for a total polymerization time of 5.
A transparent polyester with an intrinsic viscosity of 0.70 was obtained. FIG. 2 shows an H-NMR chart of this polyester. Absorption of benzene ring protons derived from 4,4'-diphenylsulfonedioxydiacetic acid component and 1,3-phenylenedioxydiacetic acid component was observed at 7.8 ppm, 7.1 ppm, and 6.5 ppm, and 4,4' Absorption of methylene protons derived from -diphenylsulfonedioxydiacetic acid component, 1,3-phenylenedioxydiacetic acid component and ethylene glycol component was observed at 4.9 ppm, 4.7 ppm and 4.3 ppm, and this polyester It was confirmed that it has the following repeating structure.
【化１２】 （繰返し単位；ｍ：ｎ＝７０：３０）[Chemical formula 12] (Repeat unit; m:n=70:30)
【００２２】実施例３
４，４´−ジフェニルスルホンジオキシジ酢酸ジメチル
２０，０００部、１，３−フェニレンジオキシジ酢酸ジ
エチル１，６００部、エチレングリコ―ル７，０００部
、および酢酸マンガン４水塩３．０部を反応缶に加え、
１６０℃から２３０℃まで漸次昇温して、流出液が出な
くなるまでエステル交換反応を行なった。この系に、正
リン酸３．０部、二酸化ゲルマニウム３．０部を加え、
２３０℃から徐々に昇温するとともに重合槽内は常圧か
ら漸次減圧にし、２６０℃、１ｔｏｒｒの真空下、全重
合時間４．５時間で極限粘度０．６８の高透明なポリエ
ステルを得た。
実施例４
４，４´−ジフェニルスルホンジオキシジ酢酸を９，５
００部、１，３−フェニレンジオキシジ酢酸を８，８０
０部、エチレングリコ―ルを４，８００部用いる以外は
実施例２と同様にして重合を行った。得られたポリマ―
の極限粘度は０．６９であった。Example 3 20,000 parts of dimethyl 4,4'-diphenylsulfonedioxydiacetate, 1,600 parts of diethyl 1,3-phenylenedioxydiacetate, 7,000 parts of ethylene glycol, and manganese acetate. Add 3.0 parts of tetrahydrate salt to the reaction vessel,
The temperature was gradually raised from 160°C to 230°C, and the transesterification reaction was carried out until no effluent was produced. To this system, 3.0 parts of orthophosphoric acid and 3.0 parts of germanium dioxide were added,
The temperature was gradually raised from 230°C and the pressure inside the polymerization tank was gradually reduced from normal pressure to obtain a highly transparent polyester with an intrinsic viscosity of 0.68 at 260°C and under a vacuum of 1 torr for a total polymerization time of 4.5 hours. Example 4 4,4′-diphenylsulfonedioxydiacetic acid with 9,5
00 parts, 8,80 parts of 1,3-phenylenedioxydiacetic acid
Polymerization was carried out in the same manner as in Example 2 except that 4,800 parts of ethylene glycol and 4,800 parts of ethylene glycol were used. Obtained polymer
The intrinsic viscosity of was 0.69.
【００２３】実施例５
４，４´−ジフェニルスルホンジオキシジ酢酸の代わり
に３，３´−ジフェニルスルホンジオキシジ酢酸を用い
る以外は実施例２と同様にして重合を行った。得られた
ポリマ―の極限粘度は０．６７であった。
実施例６
４，４´−ジフェニルスルホンジオキシジ酢酸の代わり
に３，４´−ジフェニルスルホンジオキシジ酢酸を用い
る以外は実施例２と同様にして重合を行なった。得られ
たポリマ―の極限粘度は０．６９であった。
実施例７
４，４´−ジフェニルスルホンジオキシジ酢酸１３，０
００部、１，３−フェニレンジオキシジ酢酸４，８００
部、エチレングリコ―ル６，２００部をオ―トクレ―ブ
に仕込み、窒素雰囲気の加圧（２．５Ｋｇ／ｃｍ２ ）
下、撹拌しつつ２２０〜２４５℃で３時間エステル化反
応を行い、この間生成する水を系外へ留去した。このエ
ステル化物に、２，２´−オキシジ酢酸１，６００部、
チタンテトラブトキシド７．５部を加え、重合槽内は常
圧より漸次減圧にするとともに、徐々に昇温し、２６０
℃、１ｔｏｒｒの真空下、全重合時間５時間で極限粘度
０．６８の透明なポリエステルを得た。Example 5 Polymerization was carried out in the same manner as in Example 2 except that 3,3'-diphenylsulfonedioxydiacetic acid was used instead of 4,4'-diphenylsulfonedioxydiacetic acid. The intrinsic viscosity of the obtained polymer was 0.67. Example 6 Polymerization was carried out in the same manner as in Example 2 except that 3,4'-diphenylsulfonedioxydiacetic acid was used instead of 4,4'-diphenylsulfonedioxydiacetic acid. The intrinsic viscosity of the obtained polymer was 0.69. Example 7 4,4′-diphenylsulfonedioxydiacetic acid 13,0
00 parts, 1,3-phenylenedioxydiacetic acid 4,800
and 6,200 parts of ethylene glycol were charged into an autoclave and pressurized in a nitrogen atmosphere (2.5 kg/cm2).
Under stirring, the esterification reaction was carried out at 220 to 245°C for 3 hours, and the water produced during this time was distilled out of the system. To this esterified product, 1,600 parts of 2,2'-oxydiacetic acid,
7.5 parts of titanium tetrabutoxide was added, the pressure inside the polymerization tank was gradually reduced from normal pressure, and the temperature was gradually raised to 260
A transparent polyester having an intrinsic viscosity of 0.68 was obtained under a vacuum of 1 torr and a total polymerization time of 5 hours.
【００２４】実施例８
２，２´−オキシジ酢酸の代わりに２，２´−イミノジ
酢酸を用いる以外は実施例７と同様にして重合を行った
。得られたポリマ―の極限粘度は０．７０であった。
実施例９
２，２´−オキシジ酢酸の代わりにグリコ―ル酸を１，
１００部、エチレングリコ―ルを５，２００部用いる以
外は実施例７と同様にして重合を行なった。得られたポ
リマ―の極限粘度は０．６７であった。
比較例１
イソフタル酸１７，０００部、エチレングリコ―ル７，
７００部をオ―トクレ―プに仕込み、窒素雰囲気の加圧
（２．５Ｋｇ／ｃｍ２ ）下、撹拌しつつ２２０〜２４
５℃で３時間エステル化反応を行い、この間生成する水
を系外へ留去した。このエステル化物に、チタンテトラ
ブトキシド７．０部を加え、重合槽内は常圧より漸次減
圧にするとともに、徐々に昇温し、２７０℃、１ｔｏｒ
ｒの真空下、全重合時間４時間で極限粘度０．６９の透
明なポリエステルを得た。Example 8 Polymerization was carried out in the same manner as in Example 7 except that 2,2'-iminodiacetic acid was used instead of 2,2'-oxydiacetic acid. The intrinsic viscosity of the obtained polymer was 0.70. Example 9 Glycolic acid was used in place of 2,2'-oxydiacetic acid at 1,
Polymerization was carried out in the same manner as in Example 7 except that 100 parts of ethylene glycol and 5,200 parts of ethylene glycol were used. The intrinsic viscosity of the obtained polymer was 0.67. Comparative Example 1 17,000 parts of isophthalic acid, 7 parts of ethylene glycol,
700 parts were placed in an autoclave, and under pressure (2.5 kg/cm2) in a nitrogen atmosphere, the mixture was heated to 220 to 24
The esterification reaction was carried out at 5° C. for 3 hours, and the water produced during this period was distilled out of the system. 7.0 parts of titanium tetrabutoxide was added to this esterified product, and the pressure inside the polymerization tank was gradually reduced from normal pressure, and the temperature was gradually raised to 270°C and 1 Torr.
A transparent polyester with an intrinsic viscosity of 0.69 was obtained in a total polymerization time of 4 hours under a vacuum of r.
【００２５】実施例１〜９及び比較例１で得られたポリ
エステル樹脂を約２００μのシ―トに押出し、酸素透過
率を測定した。結果を表１に示す。表１からわかるよう
に、ポリエチレンイソフタレ―トに比較し、一般式（Ｉ
Ｉ）または（ＩＶ）で示されるジカルボン酸の相当量を
含有するポリエステル樹脂のガス透過率は、大幅に小さ
いことが明白であり、ガスバリヤ―性包装材料としてふ
さわしいことがわかった。さらに、一般式（ＩＩＩ）お
よび（ＩＶ）で示されるジカルボン酸と共に、一般式（
Ｖ）で示されるジカルボン酸、またはグリコ―ル酸より
選ばれる１種以上の成分の相当量を含有する共重合ポリ
エステルに関しても、ガス透過がより小さいことが明白
であり、ガスバリヤ―性包装材料としてふさわしいこと
がわかった。The polyester resins obtained in Examples 1 to 9 and Comparative Example 1 were extruded into sheets of about 200 μm, and the oxygen permeability was measured. The results are shown in Table 1. As can be seen from Table 1, compared to polyethylene isophthalate, general formula (I
It is clear that the gas permeability of polyester resins containing significant amounts of dicarboxylic acids of I) or (IV) is significantly lower, making them suitable as gas-barrier packaging materials. Furthermore, together with dicarboxylic acids represented by general formulas (III) and (IV), general formula (
It is clear that the copolyester containing a considerable amount of one or more components selected from dicarboxylic acid or glycolic acid represented by V) has lower gas permeation, and can be used as a gas barrier packaging material. It turned out to be appropriate.
【００２６】[0026]
【表１】 ┛[Table 1] ┛
【００２７】実施例１０
実施例１で得られたポリエステルをポリエチレンテレフ
タレ―ト（日本ユニペット製ＲＴ５４３Ｃ）と後記表２
に示す割合で溶融混練し、ブレンド物を厚さ約２００μ
のシ―トに押出した。得られた押出し未延伸シ―トにつ
いて酸素ガス透過率を測定した結果を表２に示す。
実施例１１
実施例１で得られたポリエステルをポリエチレンテレフ
タレ―ト（日本ユニペット製ＲＴ５４３Ｃ）と後記表２
に示す割合でペットブレンドして射出成形（日鋼０．８
ｏｚ射出成形機）によって、６ｃｍ×６ｃｍの平板を成
形した。これをロング延伸機によって９８℃で縦方向、
横方向ともに３倍に二軸同時延伸し厚さ約１００μの延
伸シ―トとし、酸素ガス透過率を測定した。結果を表２
に示す。
実施例１２〜１５
実施例２で得られた共重合ポリエステルについて、実施
例１０と同様にしてポリエチレンテレフタレ―トとブレ
ンドし、未延伸シ―トの酸素ガス透過率を測定した（実
施例１２）。また実施例１１と同様にしてポリエチレン
テレフタレ―トとのブレンド物の延伸シ―トとし、酸素
ガス透過率を測定した（実施例１３〜１５）。結果を表
２に示す。Example 10 The polyester obtained in Example 1 was mixed with polyethylene terephthalate (RT543C manufactured by Nippon Unipet) in Table 2 below.
Melt and knead the blend in the proportions shown below to a thickness of approximately 200 μm.
It was extruded into a sheet. Table 2 shows the results of measuring the oxygen gas permeability of the obtained extruded unstretched sheet. Example 11 The polyester obtained in Example 1 was mixed with polyethylene terephthalate (RT543C manufactured by Nippon Unipet) and Table 2 below.
PET blended in the ratio shown in the figure and injection molded (Nippon Steel 0.8
A flat plate of 6 cm x 6 cm was molded using an oz injection molding machine. This is stretched in the longitudinal direction at 98℃ using a long stretching machine.
The stretched sheet was biaxially stretched 3 times in both the transverse directions to a thickness of about 100 μm, and the oxygen gas permeability was measured. Table 2 shows the results.
Shown below. Examples 12 to 15 The copolymerized polyester obtained in Example 2 was blended with polyethylene terephthalate in the same manner as in Example 10, and the oxygen gas permeability of the unstretched sheet was measured (Example 12 ). In addition, a stretched sheet of the blend with polyethylene terephthalate was prepared in the same manner as in Example 11, and the oxygen gas permeability was measured (Examples 13 to 15). The results are shown in Table 2.
【００２８】比較例２〜３
ポリエチレンテレフタレ―ト（日本ユニペット製ＲＴ５
４３Ｃ）について、実施例１０と同様にして、未延伸シ
―トの酸素ガス透過率を測定した（比較例２）。また実
施例１１と同様にして延伸シ―トとし、酸素ガス透過率
を測定した（比較例３）。結果を表２に示す。
比較例４〜５
比較例１で得られたポリエチレンイソフタレ―トについ
て、実施例１０と同様にしてポリエチレンテレフタレ―
トとブレンドし、未延伸シ―トの酸素ガス透過率を測定
した（比較例４）。また実施例１１と同様にしてポリエ
チレンテレフタレ―トとのブレンド物の延伸シ―トとし
、酸素ガス透過率を測定した（比較例５）。結果を表２
に示す。Comparative Examples 2 and 3 Polyethylene terephthalate (RT5 manufactured by Nippon Unipet)
43C), the oxygen gas permeability of the unstretched sheet was measured in the same manner as in Example 10 (Comparative Example 2). Further, a stretched sheet was prepared in the same manner as in Example 11, and the oxygen gas permeability was measured (Comparative Example 3). The results are shown in Table 2. Comparative Examples 4 to 5 The polyethylene isophthalate obtained in Comparative Example 1 was treated with polyethylene terephthalate in the same manner as in Example 10.
The oxygen gas permeability of the unstretched sheet was measured (Comparative Example 4). In addition, a stretched sheet of a blend with polyethylene terephthalate was prepared in the same manner as in Example 11, and the oxygen gas permeability was measured (Comparative Example 5). Table 2 shows the results.
Shown below.
【００２９】[0029]
【表２】[Table 2]
【００３０】実施例１６
実施例１で得られたポリエステル樹脂３０部を、ポリエ
チレンテレフタレ―ト（日本ユニペット製ＲＴ５４３Ｃ
）７０部とドライブレンドしてボトル用プリフォ―ムを
射出成形し、これを二軸延伸ブロ―機によって内容積が
１．５リットルの延伸ボトルに成形した。得られたボト
ルの酸素ガス透過性を測定したところ、０．１５ｃｃ／
ボトル・ｄａｙ・ａｔｍであった。
実施例１７
実施例２で得られた共重合ポリエステル３０部とポリエ
チレンテレフタレ―ト（日本ユニペット製ＲＴ５４３Ｃ
）７０部を用いて実施例１６と同様にして内容積１．５
リットルの延伸ボトルを成形した。得られたボトルの酸
素ガス透過率は、０．０９ｃｃ／ボトル・ｄａｙ・ａｔ
ｍであった。
比較例６
ポリエチレンテレフタレ―ト（日本ユニペット製ＲＴ５
４３Ｃ）を用いて実施例１６と同様にして内容積１．５
リットルの延伸ボトルを成形した。得られたボトルの酸
素ガス透過率は、０．４３ｃｃ／ボトル・ｄａｙ・ａｔ
ｍであった。Example 16 30 parts of the polyester resin obtained in Example 1 was mixed with polyethylene terephthalate (RT543C manufactured by Nippon Unipet).
) to injection mold a bottle preform, which was then molded into a stretched bottle with an internal volume of 1.5 liters using a biaxial stretching blow machine. When the oxygen gas permeability of the obtained bottle was measured, it was found to be 0.15cc/
It was a bottle, day, and ATM. Example 17 30 parts of the copolymerized polyester obtained in Example 2 and polyethylene terephthalate (RT543C manufactured by Nippon Unipet)
) to 1.5 parts in the same manner as in Example 16 using 70 parts.
A liter stretched bottle was molded. The oxygen gas permeability of the obtained bottle was 0.09 cc/bottle day at
It was m. Comparative Example 6 Polyethylene terephthalate (RT5 manufactured by Nippon Unipet)
43C) in the same manner as in Example 16, with an internal volume of 1.5
A liter stretched bottle was molded. The oxygen gas permeability of the obtained bottle was 0.43 cc/bottle day at
It was m.
【００３１】比較例７
比較例１で得られたポリエチレンイソフタレ―ト３０部
とポリエチレンテレフタレ―ト（日本ユニペット製ＲＴ
５４３Ｃ）７０部を用いて実施例１６と同様にして内容
積１．５メットルの延伸ボトルを成形した。得られたボ
トルの酸素ガス透過率は、０．２９ｃｃ／ボトル・ｄａ
ｙ・ａｔｍであった。
実施例１８
イソフタル酸ジメチル５，０００部、エチレングリコ―
ル７，０００部、および酢酸マンガン４水塩１．５部を
反応缶に加え、１６０℃から２３０℃まで漸次昇温して
、流出メタノール液が出なくなるまでエステル交換反応
を行った。この系に、４，４´−ジフェニルスルホンジ
オキシジ酢酸１４，０００部、正リン酸３．０部、二酸
化ゲルマニウム３．０部を加え、２３０℃から徐々に昇
温するとともに重合槽内は常圧から漸次減圧にし、２６
０℃、１ｔｏｒｒの真空下、全重合時間４．５時間で極
限粘度０．６７の高透明ポリエステルを得た。このポリ
エステルのＨ−ＮＭＲチャ―トを図３に示す。イソフタ
ル酸成分由来のベンゼン環プロトンの吸収が７．５ｐｐ
ｍ、８．２ｐｐｍおよび８．７ｐｐｍに観測され、４，
４´−ジフェニルスルホンジオキシジ酢酸成分由来のベ
ンゼン環プロトンの吸収が６．９ｐｐｍおよび７．８ｐ
ｐｍに観測され、また４，４´−ジフェニルスルホンジ
オキシジ酢酸成分由来のメチレンプロトンおよびエチレ
ングリコ―ル成分由来のメチレンプロトンの吸収が４．
３〜４．８ｐｐｍの領域に観測され、このポリエステル
が下記の構造であることが確認された。Comparative Example 7 30 parts of polyethylene isophthalate obtained in Comparative Example 1 and polyethylene terephthalate (RT made by Nippon Unipet)
A stretched bottle having an internal volume of 1.5 metre was molded in the same manner as in Example 16 using 70 parts of 543C). The oxygen gas permeability of the obtained bottle was 0.29cc/bottle・da
It was Y・ATM. Example 18 5,000 parts of dimethyl isophthalate, ethylene glycol
7,000 parts of Methanol and 1.5 parts of manganese acetate tetrahydrate were added to the reactor, and the temperature was gradually raised from 160°C to 230°C, and the transesterification reaction was carried out until no methanol solution was discharged. To this system, 14,000 parts of 4,4'-diphenylsulfonedioxydiacetic acid, 3.0 parts of orthophosphoric acid, and 3.0 parts of germanium dioxide were added, and the temperature was gradually raised from 230°C while the inside of the polymerization tank was Gradually reduce the pressure from normal pressure to 26
A highly transparent polyester having an intrinsic viscosity of 0.67 was obtained in a total polymerization time of 4.5 hours at 0° C. under a vacuum of 1 torr. An H-NMR chart of this polyester is shown in FIG. Absorption of benzene ring protons derived from isophthalic acid component is 7.5pp.
m, observed at 8.2 ppm and 8.7 ppm, 4,
Absorption of benzene ring protons derived from 4'-diphenylsulfonedioxydiacetic acid component is 6.9 ppm and 7.8 p
pm, and the absorption of methylene protons derived from the 4,4'-diphenylsulfonedioxydiacetic acid component and methylene protons derived from the ethylene glycol component was observed at 4.pm.
It was observed in the range of 3 to 4.8 ppm, and it was confirmed that this polyester had the following structure.
【００３２】[0032]
【化１３】
（繰返し単位；ｍ：ｎ＝４０：６０）
実施例１９
イソフタル酸３，１００部，エチレングリコ―ル７，０
００部をオ―トクレ―プに仕込み、窒素雰囲気の加圧（
２．５Ｋｇ／ｃｍ２ ）下、撹拌しつつ２２０〜２４５
℃で３時間エステル化反応を行い、この間生成する水を
系外へ留去した。このエステル化物に、４，４´−ジフ
ェニルスルホンジオキシジ酢酸１６，０００部、チタン
テトラブトキシド７．０部を加え、重合構内は常圧より
漸次減圧にするとともに、徐々に昇温し、２６０℃、１
ｔｏｒｒの真空下、全重合時間５時間で極限粘度０．７
０の透明なポリエステルを得た。[Chemical formula 13] (Repeat unit; m:n=40:60) Example 19 Isophthalic acid 3,100 parts, ethylene glycol 7,0
00 parts into an autoclave and pressurized in a nitrogen atmosphere (
220-245 while stirring under 2.5Kg/cm2).
The esterification reaction was carried out at ℃ for 3 hours, and the water produced during this time was distilled out of the system. To this esterified product, 16,000 parts of 4,4'-diphenylsulfonedioxydiacetic acid and 7.0 parts of titanium tetrabutoxide were added, and while the pressure in the polymerization chamber was gradually reduced from normal pressure, the temperature was gradually raised to 260 °C, 1
Intrinsic viscosity of 0.7 with total polymerization time of 5 hours under torr vacuum
0 transparent polyester was obtained.
【００３３】実施例２０
イソフタル酸９００部、４，４´−ジフェニルスルホン
ジオキシジ酢酸１８，０００部エチレングリコ―ル４，
０００部をオ―トクレ―ブに仕込み、窒素雰囲気の加圧
（２．５Ｋｇ／ｃｍ２ ）下、撹拌しつつ２２０〜２４
５℃で３時間エステル化反応を行い、この間生成する水
を系外へ留去した。このエステル化物に、チタンテトラ
ブトキシド７．０部を加え、重合槽内は常圧より漸次減
圧にするとともに、徐々に昇温し、２６０℃、１ｔｏｒ
ｒの真空下、全重合時間５時間で極限粘度０．６９の透
明なポリエステルを得た。
実施例２１
４，４´−ジフェニルスルホンジオキシジ酢酸の代わり
に３，３´−ジフェニルスルホンジオキシジ酢酸を用い
る以外は実施例１９と同様にして重合を行った。得られ
たポリマ―の極限粘度は０．６８であった。
実施例２２
４，４´−ジフェニルスルホンジオキシジ酢酸の代わり
に３，４´−ジフェニルスルホンジオキシジ酢酸を用い
る以外は実施例１９と同様にして重合を行った。得られ
たポリマ―の極限粘度は０．６９であった。Example 20 900 parts of isophthalic acid, 18,000 parts of 4,4'-diphenylsulfonedioxydiacetic acid, ethylene glycol 4,
000 parts were charged into an autoclave, and while stirring under pressure (2.5 kg/cm2) in a nitrogen atmosphere, the
The esterification reaction was carried out at 5° C. for 3 hours, and the water produced during this period was distilled out of the system. 7.0 parts of titanium tetrabutoxide was added to this esterified product, and the pressure inside the polymerization tank was gradually reduced from normal pressure, and the temperature was gradually raised to 260°C and 1 Torr.
A transparent polyester with an intrinsic viscosity of 0.69 was obtained in a total polymerization time of 5 hours under a vacuum of r. Example 21 Polymerization was carried out in the same manner as in Example 19 except that 3,3'-diphenylsulfonedioxydiacetic acid was used instead of 4,4'-diphenylsulfonedioxydiacetic acid. The intrinsic viscosity of the obtained polymer was 0.68. Example 22 Polymerization was carried out in the same manner as in Example 19 except that 3,4'-diphenylsulfonedioxydiacetic acid was used instead of 4,4'-diphenylsulfonedioxydiacetic acid. The intrinsic viscosity of the obtained polymer was 0.69.
【００３４】実施例２３
イソフタル酸２，６００部，エチレングリコ―ル６，０
００部をオ―トクレ―ブに仕込み、窒素雰囲気の加圧（
２．５Ｋｇ／ｃｍ２ ）下、撹拌しつつ２２０〜２４５
℃で３時間エステル化反応を行い、この間生成する水を
系外へ留去した。このエステル化物に、４，４´−ジフ
ェニルスルホンジオキシジ酢酸１７，０００部、１，３
−フェニレンジオキシジ酢酸３，６００部、チタンテト
ラブトキシド７．０部を加え、重合槽内は常圧より漸次
減圧にするとともに、徐々に昇温し、２６０℃、１ｔｏ
ｒｒの真空下、全重合時間５時間で極限粘度０．７２の
透明なポリエステルを得た。
実施例２４
イソフタル酸を２，４００部、４，４´−ジフェニルス
ルホンジオキシジ酢酸を１５，４００部、１，３−フェ
ニレンジオキシジ酢酸の代わりに２，２´−オキシジ酢
酸を１，９００部用いる以外は実施例２３と同様にして
重合を行った。得られたポリマ―の極限粘度は０．６８
であった。
実施例２５
イソフタル酸を２，４００部、４，４´−ジフェニルス
ルホンジオキシジ酢酸を１５，４００部、１，３−フェ
ニレンジオキシジ酢酸の代わりに２，２´−イミノジ酢
酸を１，９００部用いる以外は実施例２３と同様にして
重合を行った。得られたポリマ―の極限粘度は０．６９
であった。Example 23 2,600 parts of isophthalic acid, 6,0 parts of ethylene glycol
00 parts into an autoclave and pressurized in a nitrogen atmosphere (
220-245 while stirring under 2.5Kg/cm2).
The esterification reaction was carried out at ℃ for 3 hours, and the water produced during this time was distilled out of the system. To this esterified product, 17,000 parts of 4,4'-diphenylsulfonedioxydiacetic acid and 1,3
- 3,600 parts of phenylenedioxydiacetic acid and 7.0 parts of titanium tetrabutoxide were added, and the pressure inside the polymerization tank was gradually reduced from normal pressure, and the temperature was gradually raised to 260°C.
A transparent polyester with an intrinsic viscosity of 0.72 was obtained in a total polymerization time of 5 hours under vacuum of RR. Example 24 2,400 parts of isophthalic acid, 15,400 parts of 4,4'-diphenylsulfonedioxydiacetic acid, 1,2'-oxydiacetic acid in place of 1,3-phenylenedioxydiacetic acid, Polymerization was carried out in the same manner as in Example 23 except that 900 parts were used. The intrinsic viscosity of the obtained polymer was 0.68
Met. Example 25 2,400 parts of isophthalic acid, 15,400 parts of 4,4'-diphenylsulfonedioxydiacetic acid, 1,2'-iminodiacetic acid instead of 1,3-phenylenedioxydiacetic acid Polymerization was carried out in the same manner as in Example 23 except that 900 parts were used. The intrinsic viscosity of the obtained polymer was 0.69
Met.
【００３５】実施例２６
イソフタル酸を２，６００部、４，４´−ジフェニルス
ルホンジオキシジ酢酸を１６，８００部、１，３−フェ
ニレンジオキシジ酢酸の代わりにグリコ―ル酸を１，２
００部用いる以外は実施例２３と同様にして重合を行っ
た。得られたポリマ―の極限粘度は０．６７であった。
実施例２７
イソフタル酸１，１００部、エチレングリコ―ル６，０
００部をオ―トクレ―ブに仕込み、窒素雰囲気の加圧（
２．５Ｋｇ／ｃｍ２ ）下、撹拌しつつ２２０〜２４５
℃で３時間エステル化反応を行い、この間生成する水を
系外へ留去した。このエステル化物に、４，４´−ジフ
ェニルスルホンジオキシジ酢酸１４，０００部、１，３
−フェニレンジオキシジ酢酸２，２００部、４，４´−
ビフェニルジカルボン酸２，３００部、チタンテトラブ
トキシド７．０部を加え、重合槽内は常圧より漸次減圧
にするとともに、徐々に昇温し、２６０℃、１ｔｏｒｒ
の真空下、全重合時間５時間で極限粘度０．７２の透明
なポリエステルを得た。
比較例８
イソフタル酸ジメチルの代わりにテレフタル酸ジメチル
１１，０００部を用いる以外は実施例１８と同様にして
重合を行った。得られたポリマ―の極限粘度は０．７０
であった。Example 26 2,600 parts of isophthalic acid, 16,800 parts of 4,4'-diphenylsulfonedioxydiacetic acid, and 1,000 parts of glycolic acid in place of 1,3-phenylenedioxydiacetic acid. 2
Polymerization was carried out in the same manner as in Example 23 except that 0.00 parts were used. The intrinsic viscosity of the obtained polymer was 0.67. Example 27 1,100 parts of isophthalic acid, 6,0 parts of ethylene glycol
00 parts into an autoclave and pressurized in a nitrogen atmosphere (
220-245 while stirring under 2.5Kg/cm2).
The esterification reaction was carried out at ℃ for 3 hours, and the water produced during this time was distilled out of the system. To this esterified product, 14,000 parts of 4,4'-diphenylsulfonedioxydiacetic acid, 1,3
-2,200 parts of phenylenedioxydiacetic acid, 4,4'-
2,300 parts of biphenyldicarboxylic acid and 7.0 parts of titanium tetrabutoxide were added, and the pressure inside the polymerization tank was gradually reduced from normal pressure, and the temperature was gradually raised to 260°C and 1 torr.
A transparent polyester having an intrinsic viscosity of 0.72 was obtained in a total polymerization time of 5 hours under vacuum. Comparative Example 8 Polymerization was carried out in the same manner as in Example 18 except that 11,000 parts of dimethyl terephthalate was used instead of dimethyl isophthalate. The intrinsic viscosity of the obtained polymer was 0.70
Met.
【００３６】比較例９
イソフタル酸ジメチルを１１，０００部、エチレングリ
コールを８，４００部、４，４’−ジフェニルスルホン
ジオキシジ酢酸を８，７００部用いる以外は実施例１８
と同様にして重合を行った。この共重合ポリエステルの
製造中、減圧度が十分に上がらなくなる現象が発生し、
重合速度が極めて遅くなった。最終的に全重合時間７時
間で、極限粘度が０．４９のポリマーを得た。重合反応
終了後、重合装置を解体したところ、減圧用配管の内壁
に白色の昇華物が付着し、閉塞をおこしていた。実施例
１８〜２７及び比較例８、９で得られたポリエステル系
樹脂を約２００μのシ―トに押出し、酸素透過率を測定
した。結果を表３に示す（なお、比較例１も再掲した）
。表３からわかるように、ポリエチレンイソフタレ―ト
、および４，４´−ジフェニルスルホンジオキシジ酢酸
を共重合添加したポリエチレンテレフタレ―トに比較し
、一般式（ＩＩＩ）で示されるジカルボン酸の相当量を
含有する共重合ポリエステルのガス透過率は、より小さ
くなることが明白であり、ガスバリヤ―性包装材料とし
てふさわしいことがわかった。さらに、一般式（ＩＩＩ
）で示されるジカルボン酸と共に、一般式（ＩＶ）で示
されるジカルボン酸、一般式（Ｖ）で示されるジカルボ
ン酸、またはグリコ―ル酸より選ばれる１種以上の成分
の相当量を含有する共重合ポリエステルに関しても、ガ
ス透過がより小さくなることが明白であり、ガスバリヤ
―性包装材料としてふさわしいことがわかった。Comparative Example 9 Example 18 except that 11,000 parts of dimethyl isophthalate, 8,400 parts of ethylene glycol, and 8,700 parts of 4,4'-diphenylsulfonedioxydiacetic acid were used.
Polymerization was carried out in the same manner. During the production of this copolymerized polyester, a phenomenon occurred where the degree of vacuum could not be sufficiently increased.
The polymerization rate became extremely slow. Finally, a polymer with an intrinsic viscosity of 0.49 was obtained in a total polymerization time of 7 hours. When the polymerization apparatus was dismantled after the polymerization reaction was completed, it was found that white sublimate had adhered to the inner wall of the pressure reduction piping, causing a blockage. The polyester resins obtained in Examples 18 to 27 and Comparative Examples 8 and 9 were extruded into sheets of approximately 200 μm, and the oxygen permeability was measured. The results are shown in Table 3 (Comparative Example 1 is also listed again)
. As can be seen from Table 3, compared to polyethylene terephthalate copolymerized with polyethylene isophthalate and 4,4'-diphenylsulfone dioxydiacetic acid, It is clear that the gas permeability of the copolymerized polyester containing a considerable amount is lower, and it was found that it is suitable as a gas barrier packaging material. Furthermore, the general formula (III
), together with dicarboxylic acids represented by formula (IV), dicarboxylic acids represented by general formula (V), or glycolic acids, containing a corresponding amount of one or more components selected from It is clear that polymerized polyester also has lower gas permeation and is suitable as a gas barrier packaging material.
【００３７】[0037]
【表３】[Table 3]
【００３８】実施例２８
実施例１９で得られた共重合ポリエステルをポリエチレ
ンテレフタレ―ト（日本ユニペット製ＲＴ５４３Ｃ）と
後記表４に示す割合で溶融混練し、ブレンド物を厚さ約
１００μのシ―トにプレスした。得られたプレスシ―ト
について酸素ガス透過率を測定した結果を表４に示す。
実施例２９〜３１
実施例１９で得られた共重合ポリエステルをポリエチレ
ンテレフタレ―ト（日本ユニペット製ＲＴ５４３Ｃ）と
後記表２に示す割合でペレットブレンドして射出成形（
日鋼０．８ｏｚ射出成形機）によって６ｃｍ×６ｃｍの
平板を成形した。これをロング延伸機によって９８℃で
縦方向、横方向ともに３倍に二軸同時延伸し厚さ約１０
０μの延伸シ―トとし、酸素ガス透過率を測定した。
結果を表４に示す。
実施例３２、３３
実施例２３で得られた共重合ポリエステルについて、実
施例２８と同様にしてポリエチレンテレフタレ―トとブ
レンドし、未延伸シ―トの酸素ガス透過率を測定した（
実施例３２）。また実施例２９〜３１と同様にしてポリ
エチレンテレフタレ―トとのブレンド物の延伸シ―トと
し、酸素ガス透過率を測定した（実施例３３）。結果を
表４に示す。
比較例１０
比較例１で得られたポリエチレンイソフタレ―トについ
て、実施例２８と同様にしてポリエチレンテレフタレ―
トとブレンドし、未延伸シ―トの酸素ガス透過率を測定
した結果を表４に示す（なお、比較例２，３及び５を再
掲した）。Example 28 The copolymerized polyester obtained in Example 19 was melt-kneaded with polyethylene terephthalate (RT543C manufactured by Nippon Unipet Co., Ltd.) at the ratio shown in Table 4 below, and the blend was formed into a sheet approximately 100μ thick. -Pressed on. Table 4 shows the results of measuring the oxygen gas permeability of the obtained press sheet. Examples 29 to 31 The copolymerized polyester obtained in Example 19 was blended into pellets with polyethylene terephthalate (RT543C manufactured by Nippon Unipet) in the proportions shown in Table 2 below, and injection molded (
A 6 cm x 6 cm flat plate was molded using a 0.8 oz injection molding machine (Nippon Steel Corporation). This was biaxially stretched at 98℃ using a long stretching machine to a thickness of about 10% in both the longitudinal and transverse directions.
A stretched sheet with a thickness of 0μ was prepared, and the oxygen gas permeability was measured. The results are shown in Table 4. Examples 32 and 33 The copolymerized polyester obtained in Example 23 was blended with polyethylene terephthalate in the same manner as in Example 28, and the oxygen gas permeability of the unstretched sheet was measured (
Example 32). In addition, a stretched sheet of the blend with polyethylene terephthalate was prepared in the same manner as in Examples 29 to 31, and the oxygen gas permeability was measured (Example 33). The results are shown in Table 4. Comparative Example 10 The polyethylene isophthalate obtained in Comparative Example 1 was treated with polyethylene terephthalate in the same manner as in Example 28.
The results of measuring the oxygen gas permeability of the unstretched sheet are shown in Table 4 (Comparative Examples 2, 3, and 5 are listed again).
【００３９】[0039]
【表４】[Table 4]
【００４０】実施例３４
実施例１９で得られた共重合ポリエステル３０部を、ポ
リエチレンテレフタレ―ト（日本ユニペット製ＲＴ５４
３Ｃ）７０部とドライブレンドしてボトル用プリフォ―
ムを射出成形し、これを二軸延伸ブロ―機によって内容
積が１．５リットルの延伸ボトルに成形した。得られた
ボトルの酸素ガス透過性を測定したところ、０．１８ｃ
ｃ／ボトル・ｄａｙ・ａｔｍであった。
実施例３５
実施例２３で得られた共重合ポリエステル３０部とポリ
エチレンテレフタレ―ト（日本ユニペット製ＲＴ５４３
Ｃ）７０部を用いて実施例３６と同様にして内容積１．
５リットルの延伸ボトルを成形した。得られたボトルの
酸素ガス透過率は、０．１４ｃｃ／ボトル・ｄａｙ・ａ
ｔｍであった。Example 34 30 parts of the copolyester obtained in Example 19 was mixed with polyethylene terephthalate (RT54 manufactured by Nippon Unipet).
3C) Dry blend with 70 parts and preform for bottles.
The bottle was injection molded and formed into a stretched bottle with an internal volume of 1.5 liters using a biaxial stretching blow machine. When the oxygen gas permeability of the obtained bottle was measured, it was found to be 0.18c.
c/bottle/day/atm. Example 35 30 parts of copolymerized polyester obtained in Example 23 and polyethylene terephthalate (RT543 manufactured by Nippon Unipet)
C) Internal volume 1. in the same manner as in Example 36 using 70 parts.
A 5 liter stretched bottle was molded. The oxygen gas permeability of the obtained bottle was 0.14cc/bottle・day・a
It was tm.
【００４１】[0041]
【発明の効果】本発明のポリエステル樹脂はそれ自体透
明性が高く、優れたガスバリヤ―性を有する。本発明の
ポリエステル樹脂は包装材料として有用であり、他の熱
可塑性樹脂とのブレンドあるいは積層体として、容器、
シ―ト、フィルム等に幅広く利用することができる。特
に、ポリエチレンテレフタレ―ト成分とのブレンドある
いは積層体は、ガス透過性が低いうえ、高透明性を保持
するため、極めて有利に利用することができる。また、
塩化ビニリデンやエチレン−酢酸ビニル共重合ケン化物
のようなガスバリヤ―性素材との併用も可能である。[Effects of the Invention] The polyester resin of the present invention itself has high transparency and excellent gas barrier properties. The polyester resin of the present invention is useful as a packaging material, and can be used as a blend or laminate with other thermoplastic resins for containers,
It can be widely used for sheets, films, etc. In particular, a blend or laminate with a polyethylene terephthalate component has low gas permeability and maintains high transparency, so it can be used extremely advantageously. Also,
It is also possible to use it in combination with gas barrier materials such as vinylidene chloride and saponified ethylene-vinyl acetate copolymer.
【図１】本発明の実施例１で得られたポリエステルのＨ
−ＮＭＲチャ―ト図。FIG. 1: H of polyester obtained in Example 1 of the present invention
-NMR chart diagram.
【図２】本発明の実施例２で得られたポリエステルの同
図。FIG. 2 is the same diagram of the polyester obtained in Example 2 of the present invention.
【図３】本発明の実施例１８で得られたポリエステルの
同図。FIG. 3 is the same diagram of the polyester obtained in Example 18 of the present invention.
Claims (1)
単位２０〜１００モル％、および下記一般式（ＩＩ）で
示される繰り返し単位８０〜０モル％からなり、極限粘
度が０．４〜２ｄｌ／ｇの範囲にあるポリエステル。 【化１】 （Ｒは炭素数１〜２０の２価の炭化水素基を表す。Ｒ１
、Ｒ２ 、Ｒ３ 、Ｒ４ 、Ｒ５ 、Ｒ６ 、Ｒ７
、Ｒ８ は、水素、炭素数１から６のアルキル基または
アルコキシ基、フェニル基、アラルキル基、Ｃｌ、Ｂｒ
、またはＦを表す。） 【化２】 （Ｒ´は炭素数１〜２０の２価の炭化水素基を表す。Ｒ
９ 、Ｒ１０、Ｒ１１、Ｒ１２は水素、炭素数１から１
０のアルキル基またはアルコキシ基、フェニル基、アラ
ルキル基、Ｃｌ、ＢｒまたはＦを表す。） 【請求項２】 （Ａ）下記一般式（ＩＩＩ）で表され
るジカルボン酸またはそのエステル形成性誘導体と、（
Ｂ）一般式（ＩＶ）で表されるジカルボン酸またはその
エステル形成性誘導体を、（Ａ）成分単位と（Ｂ）成分
単位の和が全酸成分単位の少なくとも５０モル％以上の
割合で含むジカルボン酸成分と、ジオ―ル成分とを重合
させて得られる包装材料用ポリエステル。 【化３】 （Ｒ１ 、Ｒ２ 、Ｒ３ 、Ｒ４ 、Ｒ５ 、Ｒ６ 、
Ｒ７ 、Ｒ８ は水素、炭素数１から６のアルキル基ま
たはアルコキシ基、フェニル基、アラルキル基、Ｃｌ、
ＢｒまたはＦを表す。） 【化４】 （Ｒ９ 、Ｒ１０、Ｒ１１、Ｒ１２は水素、炭素数１か
ら１０のアルキル基またはアルコキシ基、フェニル基、
アラルキル基、Ｃｌ、ＢｒまたはＦを表す。） 【請求項３】 請求項２記載の包装材料用ポリエステ
ルにおいて、全酸成分の１〜５０モル％が、（Ｃ）下記
一般式（Ｖ）で表されるジカルボン酸またはそのエステ
ル形成性誘導体、あるいは（Ｄ）グリコ―ル酸またはそ
のエステル形成性誘導体より運ばれる１種以上の成分よ
りなることを特徴とする共重合ポリエステル。 ＨＯＯＣ−Ｒ１３−Ｘ−Ｒ１４−ＣＯＯＨ
（Ｖ）（Ｒ１３
、Ｒ１４は２価の脂肪族基、ＸはＯまたはＮＨを表す。 ） 【請求項４】 請求項１〜３のいずれかに記載のポリ
エステルより選ばれる１種以上のポリエステル、および
ポリエチレンテレフタレ―トからなるポリエステル組成
物。 【請求項５】 請求項４記載のポリエステル組成物を
成形してなる包装材。 【請求項６】 下記一般式（Ｉ）で示される繰り返し
単位９９〜５２モル％、および下記一般式（ＶＩ）で示
される繰り返し単位１〜４８モル％からなり、極限粘度
が０．４〜２ｄｌ／ｇの範囲にあるポリエステル。 【化５】 （Ｒは炭素数１〜２０の２価の炭化水素基を表す。Ｒ１
、Ｒ２ 、Ｒ３ 、Ｒ４ 、Ｒ５ 、Ｒ６ 、Ｒ７
、Ｒ８ は、水素、炭素数１から６のアルキル基または
アルコキシ基、フェニル基、アラルキル基、Ｃｌ、Ｂｒ
またはＦを表す。） 【化６】 （Ｒは炭素数１〜２０の２価の炭化水素基を表す。）【
請求項７】 （Ａ）下記一般式（ＩＩＩ）で表される
ジカルボン酸またはそのエステル形成性誘導体と、（Ｅ
）イソフタル酸またはそのエステル形成性誘導体を、（
Ａ）成分が全酸成分の５２〜９９モル％、（Ｅ）成分が
全酸成分の４８〜１モル％の割合で含むジカルボン酸成
分と、ジオ―ル成分とを共重合させて得られる包装材料
用ポリエステル。 【化７】 （Ｒ１ 、Ｒ２ 、Ｒ３ 、Ｒ４ 、Ｒ５ 、Ｒ６ 、
Ｒ７ 、Ｒ８ 、は水素、炭素数１から６のアルキル基
またはアルコキシ基、フェニル基、アラルキル基、Ｃｌ
、Ｂｒ、またはＦを表す。） 【請求項８】 請求項７記載の包装材料用共重合ポリ
エステルにおいて、全酸成分の１〜４７モル％が、（Ｂ
）下記一般式（ＩＶ）で表されるジカルボン酸またはそ
のエステル形成性誘導体、（Ｃ）下記一般式（Ｖ）で表
されるジカルボン酸またはそのエステル形成性誘導体、
あるいは（Ｄ）グリコ―ル酸またはそのエステル形成性
誘導体より運ばれる１種以上の成分よりなることを特徴
とする包装材料用ポリエステル。 【化８】 （Ｒ９ 、Ｒ１０、Ｒ１１、Ｒ１２は水素、炭素数１か
ら１０のアルキル基またはアルコキシ基、フェニル基、
アラルキル基、Ｃｌ、Ｂｒ、またはＦを表す。） Ｈ
ＯＯＣ−Ｒ１３−Ｘ−Ｒ１４−ＣＯＯＨ
（Ｖ）（Ｒ１３、Ｒ１４は２価
の脂肪族基、ＸはＯまたはＮＨを表す。） 【請求項９】 請求項７、８のいずれかに記載のポリ
エステル、およびポリエチレンテレフタレ―トからなる
ポリエステル組成物。 【請求項１０】 請求項９記載のポリエステル組成物
を成形してなる包装材。[Scope of Claims] [Claim 1] Consisting of 20 to 100 mol% of repeating units represented by the following general formula (I) and 80 to 0 mol% of repeating units represented by the following general formula (II), and having an intrinsic viscosity of A polyester having a value in the range of 0.4 to 2 dl/g. [Chemical formula 1] (R represents a divalent hydrocarbon group having 1 to 20 carbon atoms. R1
, R2 , R3 , R4 , R5 , R6 , R7
, R8 is hydrogen, an alkyl group or alkoxy group having 1 to 6 carbon atoms, a phenyl group, an aralkyl group, Cl, Br
, or F. ) [Chemical formula 2] (R' represents a divalent hydrocarbon group having 1 to 20 carbon atoms.R
9, R10, R11, R12 are hydrogen, carbon number 1 to 1
0 alkyl group or alkoxy group, phenyl group, aralkyl group, Cl, Br or F. ) [Claim 2] (A) a dicarboxylic acid represented by the following general formula (III) or an ester-forming derivative thereof;
B) A dicarboxylic acid containing a dicarboxylic acid represented by the general formula (IV) or its ester-forming derivative in a ratio of at least 50 mol% or more of the total acid component units of the (A) component units and (B) component units. A polyester for packaging materials obtained by polymerizing an acid component and a diol component. [Formula 3] (R1, R2, R3, R4, R5, R6,
R7 and R8 are hydrogen, an alkyl group or alkoxy group having 1 to 6 carbon atoms, a phenyl group, an aralkyl group, Cl,
Represents Br or F. ) [R9, R10, R11, R12 are hydrogen, an alkyl group or alkoxy group having 1 to 10 carbon atoms, a phenyl group,
Represents an aralkyl group, Cl, Br or F. [Claim 3] In the polyester for packaging materials according to Claim 2, 1 to 50 mol% of the total acid component is (C) a dicarboxylic acid represented by the following general formula (V) or an ester-forming derivative thereof; Alternatively, (D) a copolymerized polyester comprising one or more components carried by glycolic acid or its ester-forming derivative. HOOC-R13-X-R14-COOH
(V) (R13
, R14 represents a divalent aliphatic group, and X represents O or NH. ) [Claim 4] A polyester composition comprising one or more polyesters selected from the polyesters according to any one of Claims 1 to 3 and polyethylene terephthalate. 5. A packaging material formed by molding the polyester composition according to claim 4. 6. Consisting of 99 to 52 mol% of repeating units represented by the following general formula (I) and 1 to 48 mol% of repeating units represented by the following general formula (VI), and having an intrinsic viscosity of 0.4 to 2 dl. /g of polyester. [Chemical formula 5] (R represents a divalent hydrocarbon group having 1 to 20 carbon atoms. R1
, R2 , R3 , R4 , R5 , R6 , R7
, R8 is hydrogen, an alkyl group or alkoxy group having 1 to 6 carbon atoms, a phenyl group, an aralkyl group, Cl, Br
Or represents F. ) [Chemical formula 6] (R represents a divalent hydrocarbon group having 1 to 20 carbon atoms.) [
7. (A) a dicarboxylic acid represented by the following general formula (III) or an ester-forming derivative thereof, and (E
) isophthalic acid or its ester-forming derivative, (
Packaging obtained by copolymerizing a dicarboxylic acid component containing component A) in a ratio of 52 to 99 mol% of the total acid component and component (E) in a ratio of 48 to 1 mol% of the total acid component, and a diol component. Polyester for material. embedded image (R1 , R2 , R3 , R4 , R5 , R6 ,
R7 and R8 are hydrogen, an alkyl group or alkoxy group having 1 to 6 carbon atoms, a phenyl group, an aralkyl group, Cl
, Br, or F. ) [Claim 8] In the copolymerized polyester for packaging materials according to claim 7, 1 to 47 mol% of the total acid component is (B
) dicarboxylic acid represented by the following general formula (IV) or its ester-forming derivative; (C) dicarboxylic acid represented by the following general formula (V) or its ester-forming derivative;
Or (D) a polyester for packaging materials, characterized by comprising one or more components carried by glycolic acid or its ester-forming derivatives. embedded image (R9, R10, R11, R12 are hydrogen, an alkyl group or alkoxy group having 1 to 10 carbon atoms, a phenyl group,
Represents an aralkyl group, Cl, Br, or F. )H
OOC-R13-X-R14-COOH
(V) (R13 and R14 are divalent aliphatic groups, and X represents O or NH.) [Claim 9] Consisting of the polyester according to either claim 7 or 8, and polyethylene terephthalate. Polyester composition. 10. A packaging material formed by molding the polyester composition according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5362791A JP2999004B2 (en) | 1991-02-27 | 1991-02-27 | Polyester and polyester for packaging materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5362791A JP2999004B2 (en) | 1991-02-27 | 1991-02-27 | Polyester and polyester for packaging materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04272922A true JPH04272922A (en) | 1992-09-29 |
| JP2999004B2 JP2999004B2 (en) | 2000-01-17 |
Family
ID=12948150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5362791A Expired - Fee Related JP2999004B2 (en) | 1991-02-27 | 1991-02-27 | Polyester and polyester for packaging materials |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2999004B2 (en) |
-
1991
- 1991-02-27 JP JP5362791A patent/JP2999004B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2999004B2 (en) | 2000-01-17 |
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