JPH0214238A - Polyester composition and drawn polyester sheet and hollow polyester vessel made of the same composition - Google Patents
Polyester composition and drawn polyester sheet and hollow polyester vessel made of the same compositionInfo
- Publication number
- JPH0214238A JPH0214238A JP1069039A JP6903989A JPH0214238A JP H0214238 A JPH0214238 A JP H0214238A JP 1069039 A JP1069039 A JP 1069039A JP 6903989 A JP6903989 A JP 6903989A JP H0214238 A JPH0214238 A JP H0214238A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- acid
- polyethylene terephthalate
- dicarboxylic acid
- ester
- 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 69
- 239000000203 mixture Substances 0.000 title claims abstract description 45
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 44
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 34
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 31
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 15
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000002009 diols Chemical class 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 229920001634 Copolyester Polymers 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000001746 injection moulding Methods 0.000 claims description 7
- 238000000071 blow moulding Methods 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 45
- 238000004519 manufacturing process Methods 0.000 description 26
- 239000007789 gas Substances 0.000 description 22
- 230000004888 barrier function Effects 0.000 description 21
- 230000035699 permeability Effects 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229910001882 dioxygen Inorganic materials 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 239000005022 packaging material Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 6
- 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 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 235000014171 carbonated beverage Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- JGJWEXOAAXEJMW-UHFFFAOYSA-N dimethyl naphthalene-1,2-dicarboxylate Chemical compound C1=CC=CC2=C(C(=O)OC)C(C(=O)OC)=CC=C21 JGJWEXOAAXEJMW-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 3
- 235000014101 wine Nutrition 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 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
- 235000013405 beer Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- GYUVMLBYMPKZAZ-UHFFFAOYSA-N dimethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 GYUVMLBYMPKZAZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000006068 polycondensation reaction Methods 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
- 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
- JXXILZQFWRQHHZ-UHFFFAOYSA-N 2-(carboxymethylperoxy)acetic acid Chemical compound OC(=O)COOCC(O)=O JXXILZQFWRQHHZ-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
- 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
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 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
- 244000175448 Citrus madurensis Species 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000017317 Fortunella Nutrition 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
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-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
- 239000006096 absorbing agent Substances 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 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
- 150000005419 hydroxybenzoic acid derivatives Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- SEOVTRFCIGRIMH-UHFFFAOYSA-N indole-3-acetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CNC2=C1 SEOVTRFCIGRIMH-UHFFFAOYSA-N 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- MSBWDNNCBOLXGS-UHFFFAOYSA-L manganese(2+);diacetate;hydrate Chemical compound O.[Mn+2].CC([O-])=O.CC([O-])=O MSBWDNNCBOLXGS-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
- 238000000691 measurement method Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は透明性が高く、かつ強度およびガスバリヤ−性
に優扛たポリエステル組成物およびこnk用いて成形さ
nる包装用材料に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polyester composition having high transparency and excellent strength and gas barrier properties, and a packaging material molded using the same.
ポリエチレンテレフタレートは機械的強度、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、各種のソート、容器として幅広く包装材
料に用いら扛、特に、最近では、炭酸飲料、果汁飲料、
液体調味料、食用油、酒、ワイン用の容器として需要が
急速に伸びている。Polyethylene terephthalate has excellent mechanical strength, chemical stability, transparency, hygiene, etc., and is also lightweight and inexpensive, so it is widely used as a packaging material for various sorting and containers. , carbonated drinks, fruit juice drinks,
Demand is rapidly increasing for containers for liquid seasonings, edible oil, alcohol, and wine.
しかしながら、ポリエチレンテレフタレートのガスバリ
ヤ−性は、ポリオレフィンなト他の樹脂に比べ扛ば優n
ているものの、更に高いレベルが要求さnている分野も
有り、まだ十分なレベルとは言えなかった。例えば、炭
酸飲料、ビール、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nており、通常に使用さnる二軸配向
したポリエチレンテレフタレートからなる中空容器では
必ずしも十分なガスバリヤ−性を有しているとは言えな
い。However, the gas barrier properties of polyethylene terephthalate are superior to those of other resins such as polyolefins.
However, there are some fields that require an even higher level, and the level cannot be said to be sufficient. For example, in applications such as carbonated drinks, beer, and wine, particularly strict oxygen gas barrier properties and carbon dioxide gas barrier properties are required from the viewpoint of content preservation, and biaxially oriented polyethylene terephthalate is commonly used. It cannot be said that a hollow container made of the above necessarily has sufficient gas barrier properties.
このため、ポリエチレンテレフタレート製容器のガスバ
リヤ−性をさらに向上させるものとシテ、ポリエチレン
イソフタレートやそのコポリエステルをポリエチレンテ
レフタレートにフレンドしたガスバリヤ−容器が提案さ
nている(特開昭59−4965g1特開昭67−タ3
乙55)。For this reason, there have been proposals to further improve the gas barrier properties of containers made of polyethylene terephthalate, and gas barrier containers in which polyethylene isophthalate or its copolyester is made friendlier to polyethylene terephthalate (JP-A-59-4965G1). 1986-ta 3
Otsu 55).
しかし、これらのポリエステルではガスバリヤ−性のレ
ベルは筐だ十分ではなく、ポリエチレンテレフタレート
のガスバリヤ−性全犬幅に改善するためにはかなりの割
合金ブレンドする必要があり、この場合には、ポリエチ
レンテレフタレート容器の本来持っている強度や耐熱性
が犠牲となる。However, the level of gas barrier properties of these polyesters is not sufficient, and in order to improve the gas barrier properties to the full range of polyethylene terephthalate, a considerable proportion of gold must be blended, and in this case, polyethylene terephthalate The inherent strength and heat resistance of the container will be sacrificed.
また、一般にガスバリヤ−性の高い材料としては、ポリ
塩化ビニリデン、エチレン−酢ビ共重合体ケン化物やポ
リアミドなどが知らnでいるが、こ扛らのガスバリヤ−
材料では、ポリエチレンテレフタレートとの相溶性が悪
く、屈折率の差も大きいため、ブレンド物の透明性が著
しく損なわ扛てしまう。In addition, polyvinylidene chloride, saponified ethylene-vinyl acetate copolymer, and polyamide are generally known as materials with high gas barrier properties.
The material has poor compatibility with polyethylene terephthalate and has a large difference in refractive index, so the transparency of the blend is significantly impaired.
本発明は、機械的強度、ガスバリヤ−性などの物性に優
扛、透明度の高いポリエステル組成物、及びそ扛より成
るシート、容器を提供すること全目的とする。The entire object of the present invention is to provide a polyester composition that has excellent physical properties such as mechanical strength and gas barrier properties and is highly transparent, and sheets and containers made of the same.
本発明は、
■ ポリエチレンテレフタレート20〜95重量%と、
■ (a)イソフタル酸またはそのエステル形成性誘導
体と(b)下記−取代(1)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を含むジカルボン酸成
分全ジオール成分と共重合して得ら扛る共重合ポリエス
テルgOS−5重量%
とからなるポリエステル組成物であり、該共重合ポリエ
ステルの(a)と(b)との比を(a) : (b)
=−/−θ〜ダ、 s ニー r−ρ→−5)((2モ
ル%比)として、且つ(a)単位と(b)単位との和が
該共重合ポリエステルの全酸成分の50モル9以上であ
ることを特徴とするポリエステル組成物に関する。The present invention comprises: (1) 20 to 95% by weight of polyethylene terephthalate; (2) (a) isophthalic acid or its ester-forming derivative; (b) dicarboxylic acid represented by the following - allowance (1) or its ester-forming derivative; This is a polyester composition consisting of a dicarboxylic acid component containing all diol components and a copolymerized polyester obtained by copolymerizing gOS-5% by weight, and the ratio of (a) and (b) of the copolymerized polyester is ( a) : (b)
=-/-θ~da, s knee r-ρ→-5) ((2 mol% ratio), and the sum of (a) units and (b) units is 50% of the total acid component of the copolymerized polyester. The present invention relates to a polyester composition characterized in that the mole is 9 or more.
また、該ポリエステル組成物を射出成形または押出成形
して得らfしたシート状物を延伸して得られるガスバリ
ヤ−性の優nたシート、さらに該ポリエステル組成物金
−←延伸ブロー成形してなるガスバリヤ−性、透明性、
機械的強度に優扛た中空容器に関するものである。Further, a sheet with excellent gas barrier properties obtained by stretching a sheet obtained by injection molding or extrusion molding of the polyester composition, and a sheet obtained by stretch-blow molding the polyester composition gas barrier properties, transparency,
This relates to a hollow container with excellent mechanical strength.
(式中、Rは、ハロゲン、アルコキシ基、フェニル基、
またはアルキル基から選ば扛る置換基を表す。nはθ〜
qの整数である。)
上記−取代(1)中のRのうち、アルコキン基としては
、炭素数/〜−のものが好ましく、特にメトキシ基が好
ましい。またアルキル基としては、炭素数/〜3のもの
が好ましく、さらに好ましくは、メチル基、エチル基テ
アル。(In the formula, R is a halogen, an alkoxy group, a phenyl group,
or represents a substituent selected from alkyl groups. n is θ~
is an integer of q. ) Among R in the above-mentioned - machining allowance (1), as the alkoxy group, those having carbon number/-- are preferable, and methoxy group is particularly preferable. The alkyl group preferably has a carbon number of 1 to 3, and more preferably a methyl group or an ethyl group.
−取代(1)で示さ扛るジカルボン酸としては、具体的
には/、2−フェニレンジオキシジ酢酸、/、J−フェ
ニレンジオキシジ酢酸、/、’I−フエニレンジオキシ
ジ酢酸、λ−メチル−7,3フエニレンジオキシジ酢酸
、5−メチル−/、3−フェニレンジオキシジ酢酸、6
−メチル−/、、3−フェニレンジオキシジ酢酸、!−
エチルー/、3−フエニレンジオキシジ酢酸、6−ニチ
ルー/、3−フエ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、6−メドキシー
/、3−フェニレンジオキシジ酢酸、ダークロロー/、
2−フエニレンジオキシシ酢酸、p−クロロ−/、3−
フェニレンジオキ7ジ酢酸などが例示さnる。こnらの
うちで好ましいのは/、3−フェニレンジオキシジ酢酸
の誘導体であり、更に好ましいのは、/、3−フェニレ
ンジオキ7ジ酢酸である。- The dicarboxylic acid represented by removal allowance (1) is specifically /, 2-phenylenedioxydiacetic acid, /, J-phenylenedioxydiacetic acid, /, 'I-phenylenedioxydiacetic acid, λ-Methyl-7,3-phenylenedioxydiacetic acid, 5-methyl-/,3-phenylenedioxydiacetic acid, 6
-Methyl-/,,3-phenylenedioxydiacetic acid,! −
Ethyl/, 3-phenylenedioxydiacetic acid, 6-nityl/, 3-phenylenedioxydiacetic acid, 5-methoxy-1,3-phenylenedioxydiacetic acid, 6-medoxy/, 3-phenylenedioxy Diacetic acid, dark roll/,
2-phenylenedioxycyacetic acid, p-chloro-/, 3-
Examples include phenylene dioxy7 diacetic acid. Among these, derivatives of /,3-phenylenedioxydiacetic acid are preferred, and /,3-phenylenedioxydiacetic acid is more preferred.
一般式(1)で示さnるジカルボン酸はそのままでイン
フタル酸と併用してもよいし、酸無水物、酸ハライド、
モノエステル、ジエステル等のエステル形成性誘導体と
して使ってもよい。The dicarboxylic acid represented by the general formula (1) may be used as is in combination with inphthalic acid, or may be used as an acid anhydride, an acid halide,
It may also be used as ester-forming derivatives such as monoesters and diesters.
また、グリコール類と反応させて数量体化した後で添加
してもよい。Alternatively, it may be added after being quantified by reacting with glycols.
インフタル酸もインフタル酸ジメチル、インフタル酸ジ
エチル等のエステル誘導体、インク1’ル酸り0ライド
等のイソフタル酸ハロケン化物等のようにジオール成分
と反応するエステル形成性誘導体の形で使用してもよい
。Inphthalic acid may also be used in the form of ester-forming derivatives that react with diol components, such as ester derivatives such as dimethyl inphthalate and diethyl inphthalate, and isophthalic acid halogenated compounds such as ink 1'yl acid 0ride. .
本発明のポリエステル組成物に用いる共重合ポリエステ
ルにおいては、(a)インフタル酸単位とら)前記−取
代(1)で表されるジカルボン酸単位のモル%比は、l
O〜qs:qo〜5、好ましくは30−90ニア0〜1
0の範囲にある。In the copolymerized polyester used in the polyester composition of the present invention, the molar percentage ratio of (a) inphthalic acid units to) dicarboxylic acid units represented by the above-mentioned removal allowance (1) is l
O~qs: qo~5, preferably 30-90 near 0-1
It is in the range of 0.
−取代(1)で表さnるジカルボン酸単位全使用する量
がこの範囲を超えた場合には、得られる共重合ポリエス
テルのガラス転移点(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、また得られた共重合ポ
リエステルをポリエチレンテレフタレートとブレンドし
て成形体としたときの耐熱性が低下してしまう。一方、
−取代(1)で表さnるジカルボン酸単位を使用する量
がこの範囲に満たないときはガスバリヤ−性のレベルが
十分でないために、ポリエチレンテレフタレートのガス
バリヤ−性を改良して本発明のガスバリヤ−性の優ft
7tポリエステル製包装材料として用いるには適さない
。- If the total amount of dicarboxylic acid units represented by machining allowance (1) exceeds this range, the glass transition point (Tg) of the resulting copolyester will drop too much, so Drying becomes difficult, and the heat resistance of a molded product obtained by blending the obtained copolyester with polyethylene terephthalate decreases. on the other hand,
- If the amount of dicarboxylic acid units represented by machining allowance (1) is less than this range, the level of gas barrier properties will be insufficient. -sexual superiority
7t polyester Not suitable for use as packaging material.
本発明のポリエステル組成物に用いる共重合ポリエステ
ルにおいては、インフタル酸単位と一般式(1)で示さ
nるジカルボン酸単位の和が、全酸成分の繰り返し単位
の少なくともSOモル%以上を占めることが好筐しい。In the copolymerized polyester used in the polyester composition of the present invention, the sum of the inphthalic acid units and the dicarboxylic acid units represented by general formula (1) accounts for at least SO mol% or more of the repeating units of the total acid component. It's nice.
両者の和が5θモル%未満では共重合ポリエステルのガ
スバリヤ−性が十分でないために本発明の包装用材料と
して用いることが出来ない。また、インフタル酸と一般
式(1)で示さnるジカルボン酸が前述のモル比ヲ満足
している限シその他のジカルボン酸やオキシ酸を使うこ
ともできる。If the sum of both is less than 5θ mol %, the copolymerized polyester will not have sufficient gas barrier properties and cannot be used as the packaging material of the present invention. Further, other dicarboxylic acids and oxyacids may be used as long as the molar ratio of inphthalic acid and dicarboxylic acid represented by general formula (1) satisfies the above-mentioned molar ratio.
こnらのジカルボン酸としては、テレフタル酸、フタル
酸、2.6−ナフタレンジカルボン酸、+4’−ジフェ
ノキシエタンジカルボン酸、y、ll’−ジフェニルス
ルホンジカルボン酸及びこn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、ま
たはオキシ酸としては、ヒドロキシ安息香酸誘導体やグ
リコール酸などが挙げら扛る。These dicarboxylic acids include terephthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, +4'-diphenoxyethanedicarboxylic acid, y,ll'-diphenylsulfonedicarboxylic acid, and structural isomers thereof, Examples of aliphatic dicarboxylic acids such as malonic acid, succinic acid, and adipic acid, or oxyacids include hydroxybenzoic acid derivatives and glycolic acid.
本発明のポリエステル組成物に用いる共重合ポリエステ
ルに使わnるジオール成分としては、エチレングリコー
ル、l、2−プロパンジオール、/、3−7’ロパンジ
オール、/、4’−プタンジオール、ペンタメチレング
リコール、ヘキサメチレンクリコール、ネオペンチルグ
リコール、ンクロヘキサンジメタノール、ジエチレング
リコールやさらにはビスフェノールA1ビスフエノール
S等の芳香族ジヒドロキシ化合物誘導体など全挙げるこ
とができる。こnらのうちで、−船釣にはエチレングリ
コールが最も好ましい。Diol components used in the copolymerized polyester used in the polyester composition of the present invention include ethylene glycol, l,2-propanediol, /, 3-7'ropanediol, /, 4'-butanediol, pentamethylene glycol, Examples include hexamethylene glycol, neopentyl glycol, cyclohexanedimethanol, diethylene glycol, and aromatic dihydroxy compound derivatives such as bisphenol A1 and bisphenol S. Among these, ethylene glycol is most preferred for boat fishing.
また、本発明に用いられる共重合ポリエステルは、本発
明の要件を損なわない範囲でトリメチロールプロパン、
ペンタエリスリトール、クリセリン、トリメリット酸、
トリメ7ン酸、ピロメリット酸などの多官能化合物や、
0−ベンゾイル安息香酸等の単官能化合物全共存させて
もよい。かかる多官能化合物や単官能化合物はジオール
成分の20モル%以下の範囲で使用さnる。In addition, the copolymerized polyester used in the present invention may include trimethylolpropane, trimethylolpropane,
pentaerythritol, chrycerin, trimellitic acid,
Polyfunctional compounds such as trimene heptanoic acid and pyromellitic acid,
All monofunctional compounds such as 0-benzoylbenzoic acid may be present. Such polyfunctional compounds and monofunctional compounds are used in an amount of 20 mol% or less of the diol component.
本発明に用いらnる共重合ポリエステル■は、その極限
粘度〔フェノール/テトラクロロエタン(重量比 1/
1)の混合溶媒を用いて30℃で測定した値〕が、o、
lI−コ、O1好ましくは、O,S O〜八への範囲で
あることが望ましい。極限粘度がo、ti未満では、得
らnた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
テレフタレートとブレンドしてフィルムやシート、また
瓶やたる、缶などの容器として成形する際に実用上必要
な物性が得ら扛ない。極限粘度がコ、Qを越える場合に
は溶融粘度が高くなり過ぎて射出、押出、ブロー等の成
形が困難となるなどの問題がある。The copolymerized polyester used in the present invention has an intrinsic viscosity [phenol/tetrachloroethane (weight ratio 1/
The value measured at 30°C using the mixed solvent of 1) is o,
lI-Co, O1 is preferably in the range from O, SO to 8. If the intrinsic viscosity is less than 0 or ti, the strength of the obtained polyester will be low, and it will be difficult to remove it from the reaction vessel after the polymerization reaction and cut it into chips, or blend it with polyethylene terephthalate to make films, sheets, bottles, barrels, etc. The physical properties required for practical purposes cannot be obtained when molded into containers such as cans. If the intrinsic viscosity exceeds Q or Q, the melt viscosity becomes too high, causing problems such as difficulty in molding by injection, extrusion, blowing, etc.
該共重合ポリエステル■は、ポリエチレンテレフタレー
トについて従来から公知の重合方法で製造することがで
きる。例えば、イソフタル酸と一般式(1)で示さ扛る
ジカルボン酸、具体的にはl、3−フェニレンジオキシ
ジ酢酸、およびエチレングリコール金柑いて加圧下で直
接エステル化反応金行っ2t、&、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。The copolyester (1) can be produced by a conventionally known polymerization method for polyethylene terephthalate. For example, a direct esterification reaction is performed under pressure with isophthalic acid and a dicarboxylic acid represented by the general formula (1), specifically l,3-phenylenedioxydiacetic acid, and ethylene glycol kumquat under pressure. There is a method in which the temperature is raised and the pressure is gradually reduced to cause a polycondensation reaction.
あるいは、イン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、−取代(1)で表さnる
ジカルボン酸のエステル誘導体、例えば/、3−フェニ
レンジオキシジ酢酸ジメチルエステル、及ヒエチレング
リコールを用いてエステル交換反応を行い、その後得ら
nた反応物全史に重縮合することで製造できる。その際
、エステル化触媒、エステル交換触媒、重縮合触媒、安
定剤などを使用することが好ましい。Alternatively, an ester derivative of inphthalic acid, such as isophthalic acid dimethyl ester, and an ester derivative of dicarboxylic acid represented by (1), such as /, 3-phenylenedioxydiacetic acid dimethyl ester, and ethylene glycol may be used. It can be produced by carrying out a transesterification reaction, and then polycondensing the entire reaction product obtained. At that time, it is preferable to use an esterification catalyst, a transesterification catalyst, a polycondensation catalyst, a stabilizer, etc.
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、及びリチウム
化合物などの7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、チタン及ヒコバ
ルト化合物などの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nる。As the transesterification catalyst, seven or more known compounds such as calcium, manganese, zinc, sodium, and lithium compounds can be used, but manganese compounds are particularly preferred from the viewpoint of transparency. As the polymerization catalyst, one or more of known antimony, germanium, titanium, and hycobalt compounds can be used, but antimony, germanium, and titanium compounds are preferably used.
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、螢光増白剤、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nかの段階で添加しても良く、成形
加工前にいワユるマスターバッチ処方で添加しても良い
。In addition, in the present invention, conventionally known additives such as antioxidants, ultraviolet absorbers, fluorescent whitening agents, 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 the production of polyester, or may be added as a masterbatch formulation before molding.
このようにして得らnた本発明のポリエステル組成物に
用いる共重合ポリエステル■はポリエチレンテレフタレ
ート■と溶融成形さn成形品とさnる。具体的には、ポ
リエチレンテレフタレートとブレンドして押出機で溶融
混練して混合チップを得、ついでこnt底成形供するこ
ともできるし、マタ、そnぞ扛の成分全トライブレンド
し、直接成形に供することも可能である。ここで、ポリ
エチレンテレフタレートと本発明の共重合ポリエステル
のブレンドの割合は、該共重合体■が組成物中の5〜t
ro重量%を占めることが好ましい。共重合体の割合が
3重量%未満ではポリエチレンテレフタレートのガスバ
リヤ−性改良効果が不十分であるし、go重量%を超え
ると成形体の機械的強度や耐熱性の点で性能の低下がみ
らnる。The thus obtained copolyester (1) used in the polyester composition of the present invention is melt-molded with polyethylene terephthalate (2) to form a molded product. Specifically, it is possible to blend it with polyethylene terephthalate and melt-knead it in an extruder to obtain a mixed chip, which can then be used for molding, or to tri-blend all the components of the mold and mold it directly. It is also possible to provide Here, the ratio of the blend of polyethylene terephthalate and the copolymerized polyester of the present invention is such that the copolymer
Preferably, it accounts for ro% by weight. If the proportion of the copolymer is less than 3% by weight, the effect of improving the gas barrier properties of polyethylene terephthalate will be insufficient, and if it exceeds go% by weight, the performance of the molded product will deteriorate in terms of mechanical strength and heat resistance. nru.
本発明のポリエステル組成物は、ポリエチレンテレフタ
レートなどの成形において一般的に使用さnる溶融成形
法を用いてフィルム、シート、容器、その他の包装材料
全成形することができ、未延伸の状態でもガスバリヤ−
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l軸方向に延伸することによ
りさらにガスバリヤ−性や機械的強度を改善することが
可能である。The polyester composition of the present invention can be molded into films, sheets, containers, and other packaging materials using a melt molding method commonly used in molding polyethylene terephthalate, and even in an unstretched state, it can be used as a gas barrier. −
It can be used as a material with high properties. 'Also, by stretching the polyester composition at least in the l-axis direction, it is possible to further improve gas barrier properties and mechanical strength.
本発明のポリエステル組成物から成る延伸シートは、射
出成形や、押出成形でシート状に成形さf′した本発明
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nるl軸延伸、逐次二軸延伸、同時
二軸延伸のうちの任意の延伸方法を用いて成形さnる。The stretched sheet made of the polyester composition of the present invention is produced by forming the polyester composition of the present invention into a sheet by injection molding or extrusion molding, and then sequentially stretching the polyester composition of the present invention, which is normally used for stretching polyethylene terephthalate, along the nl axis. Shaping is performed using any stretching method among biaxial stretching and simultaneous biaxial stretching.
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。Moreover, it can also be molded into a cup shape or a tray shape by air pressure molding.
本発明のポリエステル組成物から成る延伸シートラ製造
するに当たっては、延伸温度は本発明のポリエステルの
ガラス転移点温度ないしガラス転移点より7θ℃高い温
度の間に設定すればよい。延伸倍率は、l軸延伸の場合
であれば通常1.1倍から70倍、好ましくはへ/倍か
ら3倍の範囲で行い、二軸延伸の場合でろnば、縦方向
及び横方向ともそnぞ扛ハ/倍から3倍、好ましくはハ
1倍から3倍の範囲で行えばよい。When 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 7θ° C. higher than the glass transition point. The stretching ratio is usually in the range of 1.1 to 70 times in the case of l-axis stretching, preferably in the range of 1.1 to 3 times, and in the case of biaxial stretching, in both the longitudinal and transverse directions. It may be carried out within a range of 1 to 3 times, preferably 1 to 3 times.
このようにして得らnた、本発明のポリエステル組成物
から成る延伸シートは、透明性、ガスハIJヤー性、機
械的強度に優n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。The stretched sheet made of the polyester composition of the present invention thus obtained has excellent transparency, gas carryability, and mechanical strength, and is useful as a packaging material in the form of a film, cup, tray, etc. be.
本発明の樹脂組成物から成るポリエステル中空成形体は
プリフォームを延伸プロー成形してなるもので、従来よ
シポリエチレンテレフタレートのブロー成形で用いられ
ている装置を用いることが出来る。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成
形で−H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f’Le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ハリノン法等の吹
込み成形法が適用される。A polyester blow molded article made of the resin composition of the present invention is obtained by stretch blow molding a preform, and the equipment conventionally used for blow molding polyethylene terephthalate can be used. Specifically, for example, a -H preform is molded 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. , a blow molding method such as a hot parison method with biaxial stretching or a cold halinon method is applied.
延伸温度は、70なVし120℃、好ましくは10ない
し110℃で、延伸倍率は縦方向に/、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。The stretching temperature is 70 V and 120°C, preferably 10 to 110°C, and the stretching ratio is 5 to 3.5 in the machine direction.
It may be done in the range of 2 to 5 times in the circumferential direction.
″また、ポリエステル中空成形体を製造するに当たって
、本発明のポリエステル組成物よりなル層ト、ポリエチ
レンテレフタレートを主体とスルポリアルキレンテレフ
タレートよりなる層全積層したプリフォームを形成し、
こn’ff:コ軸延伸プローM、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〜S層程度の構成が好ましい0
〔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
発明はその要旨を超えない限り以下の実施例に限定さn
るものではない0
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全以下に示す。``Also, in producing a polyester blow molded article, a preform is formed in which all the layers are made of the polyester composition of the present invention, the main layer is polyethylene terephthalate, and the layers are made of sulpolyalkylene terephthalate,
This n'ff: co-axial stretching blower M, which may be shaped into a multilayer blow molded container. At this time, there is no particular limitation on the layer structure, and a structure of about 3 to S layers is preferable. [Example] The present invention will be explained in more detail with reference to Examples below. limited to the following examples
Note that "parts" in the examples mean "parts by weight," and all of the various measurement methods used in the examples are shown below.
0極限粘度 フェノール−テトラクロロエタン(t o7s 。0 intrinsic viscosity Phenol-tetrachloroethane (to7s).
重量比)中、30℃で測定した。(weight ratio) at 30°C.
0酸素透過率
約200μ肉厚の押出シートサンプルおよびボトルを作
成し、23℃、10o%RHの条件下、rox−TRA
N to/so AJ酸素透過率測定装置(米国Mo
dern Controls社製)で測定し、cc−I
II/d−day−atm′またはcc/ボトル・da
y−atmで示し友。0 Oxygen permeability Extruded sheet samples and bottles with a wall thickness of approximately 200μ were created, and Rox-TRA was heated at 23°C and 10o%RH.
N to/so AJ oxygen permeability measuring device (USA Mo
cc-I
II/d-day-atm' or cc/bottle/da
Show friends at Y-ATM.
製造例1
ジメチルイソフタレート3g部、ナフタレンジカルボン
酸ジメチルエステルyg部、エチレングリコール11g
部、および酢酸マンガンタ水塩0.0.7部を反応缶に
加え、160℃から230℃までの漸次昇温して、流出
液が出なくなるまでエステル交換反応を行った。Production Example 1 3 g parts of dimethyl isophthalate, yg parts of naphthalene dicarboxylic acid dimethyl ester, 11 g of ethylene glycol
1 part and 0.0.7 part of mangantha acetate hydrate 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 effluent came out.
この系に/、J−フエニレンジオキシジ酢酸sq部、正
リン酸0.02部、二酸化ゲルマニウム0.03部をこ
の順に加え、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、コロ0℃、0.!; t
orrの真空下、全重合時間6時間で極限粘度O0りl
の高透明ポリエステル全得た。To this system, sq parts of J-phenylenedioxydiacetic acid, 0.02 parts of orthophosphoric acid, and 0.03 parts of germanium dioxide were added in this order, and the temperature was gradually raised from 230°C while the inside of the polymerization tank was brought to normal pressure. The pressure was gradually reduced from 0°C to 0. ! ;t
Intrinsic viscosity of 00 l in total polymerization time of 6 hours under vacuum of orr.
Made of highly transparent polyester.
、2μl造汐り 、2
ジノチルイソフタレートf<!;、2部、/、3−フェ
ニレンジ万キ/ジ酢酸30部、ナフタレンジカルボン酸
ジメチルエステル”k A j !B 、エチレングリ
コール66部全用いる以外は製造例/と同様にして重合
全行った。得ら′fしたポリマーの込限粘度はθ、乙9
であった。, 2 μl Shioori, 2 dinotyl isophthalate f<! ;, 2 parts, /, 30 parts of 3-phenylene dicarboxylic acid/diacetic acid, naphthalene dicarboxylic acid dimethyl ester "k A j !B", 66 parts of ethylene glycol, but the entire polymerization was carried out in the same manner as in Production Example/ The limiting viscosity of the obtained polymer is θ, Otsu9
Met.
製造例3
ジメチルイソフタレート5/部、/、3−7エニし/ン
ジオキシジ酢酸g?部、エチレングリコール33部、お
よびチタンテトラブトキサイド0.03部全反応缶に加
え、200℃から、230゛C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全行った。Production Example 3 Dimethyl isophthalate 5/part, /, 3-7 nitrogen/dioxydiacetic acid g? 1 part, 33 parts of ethylene glycol, and 0.03 part of titanium tetrabutoxide were added to the reaction vessel, and the temperature was gradually raised from 200°C to 230°C to carry out the entire transesterification reaction until no effluent came out.
さらに1.230′C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、2bO’C/ torr
の真空下、全重合時間S、O時間で極限粘度0.65の
高透明ポリエステル金得た。Furthermore, the temperature was gradually raised from 1.230'C, and the pressure inside the polymerization tank was gradually reduced from normal pressure to 2bO'C/torr.
A highly transparent polyester gold having an intrinsic viscosity of 0.65 was obtained under vacuum for a total polymerization time of S and O hours.
製造例ケ
ジノチルイソフタレートfg 2部、/、3−ンエニレ
ンジオキ7ジ酢版32部、ナフタレンジカルボン酸ジメ
チルエステル?:3” 部、エチレングリコール70部
全用いる以外は製造例/と同様にして重合を行った。得
らnたポリマーの極限粘度は0.70であった。Production Example: 2 parts of Kejinotyl Isophthalate fg, 32 parts of 3-enylene dioxygenate 7 diacetate, dimethyl naphthalene dicarboxylic acid ester? Polymerization was carried out in the same manner as in Production Example except that 3" parts of ethylene glycol and 70 parts of ethylene glycol were used. The intrinsic viscosity of the obtained polymer was 0.70.
製造例3゛
ジメチルイソフタレートを//り部、/、3−フェニレ
ンジオキシジ酢酸33部、ナフタレンジカルボン酸ジメ
チルエステルkOm、エチレングリコール73部を用い
る以外は製造例/ど同様にして重合全行った。得らnた
ポリマーの極限粘度は0.4 gであった。Production Example 3 Complete polymerization was carried out in the same manner as Production Example 3 except that 1 part of dimethyl isophthalate, 33 parts of 3-phenylenedioxydiacetic acid, 73 parts of naphthalenedicarboxylic acid dimethyl ester, and 73 parts of ethylene glycol were used. Ta. The intrinsic viscosity of the obtained polymer was 0.4 g.
比較製造例/
ジメチルインフタレートに/!r、2部、エチレングリ
コール9り部全用いる以外は製造例/と同様にしてポリ
エチレンイソフタレートの重合全行りt0得らnたポリ
マーの極限粘度は0073であった。Comparative production example / For dimethyl inphthalate /! The polymerization of polyethylene isophthalate was carried out in the same manner as in Production Example, except that 2 parts of ethylene glycol and 9 parts of ethylene glycol were used.The intrinsic viscosity of the obtained polymer was 0,073.
製造例/〜5及び比較製造例/で得らnた共重合ポリエ
ステルを約、2OOμのシートにプレスし、酸素透過率
全測定した。結果全表/にまとめて示す。The copolymerized polyesters obtained in Production Examples 1 to 5 and Comparative Production Example 1 were pressed into sheets of approximately 200μ, and the oxygen permeability was measured in total. The results are summarized in Table/.
実施例/〜2
製造例/−2で得られた共重合ポリエステルヲ極限粘度
が0.7 !;のポリエチレンテレフタレート(日本ユ
ニペット(株)RTrlI3c)と後記表2に示す割合
で溶融混練し、ブレンド物を約−〇θμのシートにプレ
スした。得らnたプレスシートについて酸素透過率を測
定した結果を表2に示す。Example/~2 The copolymerized polyester obtained in Production Example/-2 had an intrinsic viscosity of 0.7! was melt-kneaded with polyethylene terephthalate (RTrlI3c, manufactured by Nippon Unipet Co., Ltd.) at the ratio shown in Table 2 below, and the blend was pressed into a sheet of about -〇θμ. Table 2 shows the results of measuring the oxygen permeability of the obtained press sheets.
実施例3〜グ
製造例/で得ら扛た共重合ポリエステルをポリエチレン
テレフタレート(日本ユニペット類RTsti3C)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(
口調0.g Oz射出成形)によって、AcnLX6
crrtの平板を成形した。こn全ロング延伸機によっ
て縦方向、横方向ともに3倍に同時延伸し厚さ約100
μの延伸シートとし、酸素透過率を測定した。結果を表
コにまとめて示す。The copolymerized polyester obtained in Example 3 to Production Example 3 was blended into pellets with polyethylene terephthalate (Japan Unipet RTsti3C) at the ratio shown in Table 2 below, and injection molded (
Tone 0. g Oz injection molding) by AcnLX6
A flat plate of crrt was molded. Stretched to a thickness of approximately 100 mm by simultaneously stretching 3 times in both the longitudinal and lateral directions using a full length stretching machine.
A stretched sheet of μ was prepared, and the oxygen permeability was measured. The results are summarized in Table 1.
比較例1−コ
ポリエチレンテレフタレート(日本ユニペット製RTタ
グ30)について、実施例/〜ユと同様にして未延伸フ
ィルムの酸素透・過率を測定した。また実施例3〜ヶと
同様にして延伸フィルムとし、この酸素透過率全測定し
た。結果を表2に示す。Comparative Example 1 - Regarding copolyethylene terephthalate (RT Tag 30 manufactured by Nippon Unipet), the oxygen permeability of the unstretched film was measured in the same manner as in Examples. Further, a stretched film was prepared in the same manner as in Examples 3 to 3, and the oxygen permeability of the film was totally measured. The results are shown in Table 2.
比較例3〜q
比較製造例1で得ら扛たポリエチレンイソフタレートに
ついて、実施例3〜グと同様にしてポリエチレンテレフ
タレートとブレンドし、未延伸フィルムの酸素透過率を
測定した。また実施例3〜lIと同様にしてポリエチレ
ンテレフタレートとのブレンド物の延伸フィルムとし、
この酸素透過率を測定した。結果を表ユに示す。Comparative Examples 3 to q The polyethylene isophthalate obtained in Comparative Production Example 1 was blended with polyethylene terephthalate in the same manner as in Examples 3 to q, and the oxygen permeability of the unstretched film was measured. In addition, a stretched film of a blend with polyethylene terephthalate was prepared in the same manner as in Examples 3 to 1I,
This oxygen permeability was measured. The results are shown in Table 1.
表コ
ポリエステル組成物1)の酸素ガス透過量ポリエステル
組成物:ポリエチレンテレフタレート
(日本ユニペラ
ト
RTjダ3C
と共重合ポリニス
チルのブレンド物
2)延伸条件:延伸温度9g℃、2軸間時延伸3)ブレ
ンド量:組成物中の共重合ポリエステル重量%
リ PO2:酸素ガス透過量CG ’ mW/ m ”
day ”tm
実施例り
製造例1で得らnたポリエステル共重合体to部全ポリ
エチレンテレフタレート(日本ユニペット類RT!;1
I3C) 90部とトライブレンドしてボトル用プリフ
ォームを射出成形し、こnを二軸延伸ブロー機によって
内容積が/、!;1(肩部と胴部の平均肉厚0.33m
y、、その合計表面fjt 700crit )の延伸
ボトルに成形した。得らnたボトルの酸素ガス透過性を
測定したところ、o、a i cc/ボトいday@a
tmであった。Table Oxygen gas permeation amount of copolyester composition 1) Polyester composition: Polyethylene terephthalate (Blend of Nippon Uniperat RTj Da 3C and copolymerized polynistil 2) Stretching conditions: Stretching temperature 9g°C, 2-axis time stretching 3) Blend amount : Weight % of copolymerized polyester in the composition PO2: Oxygen gas permeation amount CG 'mW/m''
day "tm Example: The polyester copolymer obtained in Production Example 1 was entirely polyethylene terephthalate (Japan Unipet RT!; 1
Tri-blend with 90 parts of I3C) to injection mold a bottle preform, and use a biaxial stretching blow machine to reduce the internal volume to /,! ;1 (Average wall thickness of shoulder and torso 0.33m
y, its total surface fjt 700crit). When the oxygen gas permeability of the obtained bottle was measured, it was found that o, ai cc/botoiday@a
It was tm.
比較例S
ポリエチレンテレフタレート(日本ユニペット類nTs
ta3c)を用いて実施例Sと同様にして内容積t、s
lの延伸ボトルを成形した。得らnたボトルの酸素ガ
ス透過性を測定したところ0.413cc/ボトル・d
ay@atmであった。Comparative example S Polyethylene terephthalate (Japan Unipets nTs
ta3c) in the same manner as in Example S, the internal volumes t, s
A stretched bottle of 1 liter was molded. When the oxygen gas permeability of the obtained bottle was measured, it was 0.413cc/bottle・d
It was ay@atm.
比較例6
比較製造例/で得られたポリエチレンインフタレート7
0部とポリエチレンテレフタレート(日本ユニベノ)
M RTj+、、? C) 90部を用いて実施例よと
同様にして内容積/、j /!の延伸ボトル全成形した
。得られたボトルの酸素ガス透過性全測定したところ、
θ、3q cc/ボトル・day′atmであった0
比較例7
製造例1で得ら扛たポリエステル共重合体を用いてボト
ル用プリフォームを射出成形し、これを二軸延伸ブロー
機によって内容積が7dlの延伸ボトルに成形した。得
られたボトルの形状はいびつな物となりまたボトルの強
度も低かった。Comparative Example 6 Polyethylene inphthalate 7 obtained in Comparative Production Example/
0 parts and polyethylene terephthalate (Japan Univeno)
M RTj+,,? C) In the same manner as in the example using 90 parts, the internal volume /, j /! The stretched bottle was completely molded. When the oxygen gas permeability of the obtained bottle was completely measured,
θ, 3q cc/bottle/day'atm was 0 Comparative Example 7 A preform for a bottle was injection molded using the polyester copolymer obtained in Production Example 1, and the content was molded using a biaxial stretching blow machine. It was formed into a stretched bottle with a volume of 7 dl. The shape of the obtained bottle was distorted and the strength of the bottle was also low.
製造例6
ジメチルイソフタレート25部、コ、6−ナフタレンジ
カルボン酸ジメチルエステル72部、エチレングリコー
ル66部、および酢酸マンガンダ水塩0.θ3部を反応
缶に加え、/AO℃から、2 、? 05Gまで漸次昇
温しで、流出液が出なくなるまでエステル交換反応を行
った。Production Example 6 25 parts of dimethyl isophthalate, 72 parts of co-,6-naphthalene dicarboxylic acid dimethyl ester, 66 parts of ethylene glycol, and 0.5 parts of manganese acetate hydrate. Add 3 parts of θ to the reaction vessel and from /AO°C, 2, ? The temperature was gradually raised to 05G, and the transesterification reaction was carried out until no effluent was produced.
この系に/、3−フエニレンジオキシジ酢酸32部、正
リン酸0.0.2部、二酸化ゲルマニウム0.03部を
この順に加え、コ3θ℃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℃、0.!;
torrの真空下、全重合時間6時間で極限粘度0.7
0の高透明ポリエステルを得た。To this system, 32 parts of 3-phenylenedioxydiacetic acid, 0.0.2 parts of orthophosphoric acid, and 0.03 parts of germanium dioxide were added in this order, and the temperature was gradually raised from 3θ°C while the temperature was increased inside the polymerization tank. The pressure was gradually reduced from normal pressure to 260°C and 0. ! ;
Intrinsic viscosity is 0.7 under vacuum of torr, total polymerization time is 6 hours.
0 highly transparent polyester was obtained.
製造例7
ジメチルイソフタシートf/3部、/、3−フ工二しン
ジオキシジ酢酸75部、2.6−ナフタレンジカルボン
酸ジメチルエステル’x b s 部、エチレングリコ
ール66部を用いる以外は製造例/と同様にして重合全
行った。得ら扛たポリマーの極限粘度は0.6gであっ
た。Production Example 7 Production Example except that dimethyl isophthasheet f/3 parts, /, 75 parts of 3-phenyl dioxydiacetic acid, 2,6-naphthalene dicarboxylic acid dimethyl ester 'x b s parts, and 66 parts of ethylene glycol were used. The entire polymerization was carried out in the same manner as in /. The intrinsic viscosity of the obtained polymer was 0.6 g.
製造例g
ジメチルインフタレート全29部、/、3−フエニレン
ジオキシジ酢酸g3部、2.6−ナフタレンジカルボン
酸ジメチルエステル2slI部、エチレングリコール7
3部を用いる以外は製造例/と同様にして重合を行った
。得らnたポリマーの極限粘度は0.70であった。Production Example G Total 29 parts of dimethyl inphthalate, 3 parts of 3-phenylenedioxydiacetic acid, 2 slI parts of 2,6-naphthalene dicarboxylic acid dimethyl ester, 7 parts of ethylene glycol
Polymerization was carried out in the same manner as in Production Example except that 3 parts were used. The intrinsic viscosity of the obtained polymer was 0.70.
製造例6〜gで得ら扛た共重合ポリエステルを約200
μのシートにプレスし、酸素透過率全測定した。結果全
表3にま・とめて示す。Approximately 200% of the copolymerized polyester obtained in Production Example 6-g
It was pressed into a μ sheet and the oxygen permeability was completely measured. The results are summarized in Table 3.
実施例6〜7
製造例6〜7で得らnた共重合ポリエステル全極限粘度
が0.75のポリエチレンテレフタレート(日本ユニペ
ット(株) RTsq3C)と後記表ダに示す割合で溶
融混練し、ブレンド物を約200μのシートにプレスし
た。得ら扛たプレスシートについて酸素透過率全測定し
た結果全表1に示す。Examples 6 to 7 The copolymerized polyester obtained in Production Examples 6 to 7 was melt-kneaded and blended with polyethylene terephthalate (Nihon Unipet Co., Ltd. RTsq3C) having a total intrinsic viscosity of 0.75 in the proportions shown in Table 2 below. The material was pressed into sheets of approximately 200μ. The oxygen permeability of the obtained pressed sheet was measured and the results are shown in Table 1.
ポリエチレンテレフタレート(日本ユニベット製xtT
t<z3c)と後記表qに示す割合でペレットブレンド
して射出成形(8鋼o、g ・02射出成形)によっ
て、Acm×1−cynの平板を成形した。Polyethylene terephthalate (xtT made by Nippon Unibet)
The pellets were blended at the ratios shown in Table q below (t<z3c) and injection molded (8 steel o, g.02 injection molding) to form a flat plate of Acm x 1-cyn.
こfl’tロング延伸機によって縦方向、横方向ともに
3倍に同時延伸し厚さ約10oμの延伸シートとし、酸
素透過率全測定した。結果を表グにまとめて示す。The sheet was simultaneously stretched 3 times in both the longitudinal and transverse directions using a fl't long stretching machine to obtain a stretched sheet with a thickness of about 10 μm, and the oxygen permeability was completely measured. The results are summarized in Table 2.
表ダ
ポリエステル組成物′)
の酸素ガス透過量
/)〜q)表コと同じ
実施例IO
製造例6で得らnたポリエステル共重合体20部をポリ
エチレンテレフタレー)(日本=ニペット製RT&11
.?C) g 0部とトライブレンドしてボトル用プリ
フォームを射出成形し、こn全二軸延伸ブロー機によっ
て内容積が7.5で(肩部と胴部の平均肉厚0.33朋
、その合計表面@700di’)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
、0.2 / cc/ボトル・day−atmであった
。Oxygen gas permeation amount of polyester composition') /) ~ q) Same as Table 1 Example IO 20 parts of the polyester copolymer obtained in Production Example 6 was mixed with polyethylene terephthalate) (Japan = RT&11 made by Nippet)
.. ? C) A preform for a bottle was injection molded by tri-blending with 0 parts of g, and the inner volume was 7.5 mm (average wall thickness of the shoulder and body portions: 0.33 mm) using a fully biaxial stretching blow machine. It was molded into a stretched bottle with a total surface of 700 di'. When the oxygen gas permeability of the obtained bottle was measured, it was found to be 0.2/cc/bottle/day-atm.
本発明のポリエステル組成物は透明性が高く、優nたガ
スバリヤ−性を有する。従って、こnを用いて得られる
延伸シートは、ガスバリヤ−tl生かしてフィルム、シ
ート、カップ、トレイなど包装用材料として種々の用途
に用いることができる。さらに本発明のポリエステル中
空成形体においては、優れた透明性及びガスハIJヤー
性の上に、機械的強度も兼ね備えておシ清涼飲料、調味
料、油、ビールやワイン、日本酒等のアルコール飲料、
化粧品などの用途に幅広く用いることが出来る。特に小
型炭酸飲料やビール、ワイン等の用途のように、通常の
ポリエチレンフタレートの二軸延伸ボトルではガスバリ
ヤ−性が不十分で所定の賞味期間保存することができな
い様な用途にも用いることが可能となる。The polyester composition of the present invention has high transparency and excellent gas barrier properties. Therefore, the stretched sheet obtained using this method can be used for various purposes as a packaging material such as a film, sheet, cup, or tray by taking advantage of the gas barrier tl. Furthermore, the polyester hollow molded article of the present invention has not only excellent transparency and gas injection properties but also mechanical strength.
It can be used in a wide range of applications such as cosmetics. In particular, it can be used for applications such as small carbonated drinks, beer, wine, etc., where regular polyethylene phthalate biaxially stretched bottles have insufficient gas barrier properties and cannot be stored for a specified shelf life. becomes.
Claims (4)
量%と、 [2](a)イソフタル酸またはそのエステル形成性誘
導体と(b)下記一般式( I )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を含むジカルボン
酸成分をジオール成分と共重合して得られる共重合ポリ
エステル80〜5重量% とからなるポリエステル組成物であり、該共重合ポリエ
ステル中の(a)と(b)との比を(a):(b)=1
0〜95:90〜5(モル%比)とし、且つ(a)単位
と(b)単位との和が該共重合ポリエステルの全酸成分
の50モル%以上であることを特徴とするポリエステル
組成物。 ▲数式、化学式、表等があります▼( I ) (式中Rは、ハロゲン、アルコキシ基、フェニル基また
はアルキル基から選ばれる置換基を表す。nは0〜4の
整数である。)(1) [1] 20 to 95% by weight of polyethylene terephthalate, [2] (a) isophthalic acid or its ester-forming derivative, and (b) dicarboxylic acid represented by the following general formula (I) or its ester-forming property A polyester composition consisting of 80 to 5% by weight of a copolymerized polyester obtained by copolymerizing a dicarboxylic acid component containing a derivative with a diol component, and the ratio of (a) to (b) in the copolymerized polyester is 80 to 5% by weight. (a):(b)=1
A polyester composition characterized in that the ratio is 0 to 95:90 to 5 (mol% ratio), and the sum of (a) units and (b) units is 50 mol% or more of the total acid components of the copolymerized polyester. thing. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R represents a substituent selected from halogen, alkoxy group, phenyl group, or alkyl group. n is an integer from 0 to 4.)
量%と、 [2](a)イソフタル酸またはそのエステル形成性誘
導体と(b)前記一般式( I )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を含むジカルボン
酸成分をジオール成分と共重合して得られる共重合ポリ
エステル80〜5重量、 とからなるポリエステル組成物であり、該共重合ポリエ
ステル中の(a)と(b)との比を(a):(b)=3
0〜90:70〜10(モル%比)とし、且つ(a)単
位と(b)単位との和が該共重合ポリエステルの全酸成
分の50モル%以上であることを特徴とするポリエステ
ル組成物。(2) [1] 20 to 95% by weight of polyethylene terephthalate, [2] (a) isophthalic acid or its ester-forming derivative, and (b) dicarboxylic acid represented by the above general formula (I) or its ester-forming property 80 to 5 weight of a copolymerized polyester obtained by copolymerizing a dicarboxylic acid component containing a derivative with a diol component, and the ratio of (a) to (b) in the copolyester (a):(b)=3
A polyester composition characterized in that the ratio is 0 to 90:70 to 10 (mol% ratio), and the sum of (a) units and (b) units is 50 mol% or more of the total acid components of the copolymerized polyester. thing.
成形または押出成形して得られたシート状物を少なくと
も一方向に延伸してなるポリエステル延伸シート。(3) A stretched polyester sheet obtained by stretching in at least one direction a sheet obtained by injection molding or extrusion molding the polyester composition according to claim 1.
ブロー成型または該組成物を射出成形もしくは押出成形
によってプリフォームを形成した後、二軸延伸ブロー成
形してなるポリエステル製中空容器。(4) A polyester hollow container formed by stretch blow molding the polyester composition according to claim 1, or forming a preform by injection molding or extrusion molding the polyester composition, and then biaxially stretch blow molding the preform.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6903989A JP2674193B2 (en) | 1988-03-26 | 1989-03-20 | Polyester composition, polyester stretched sheet comprising the same, and polyester hollow container |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7219988 | 1988-03-26 | ||
JP63-72199 | 1988-03-26 | ||
JP6903989A JP2674193B2 (en) | 1988-03-26 | 1989-03-20 | Polyester composition, polyester stretched sheet comprising the same, and polyester hollow container |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0214238A true JPH0214238A (en) | 1990-01-18 |
JP2674193B2 JP2674193B2 (en) | 1997-11-12 |
Family
ID=26410216
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6903989A Expired - Lifetime JP2674193B2 (en) | 1988-03-26 | 1989-03-20 | Polyester composition, polyester stretched sheet comprising the same, and polyester hollow container |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2674193B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02169621A (en) * | 1988-12-21 | 1990-06-29 | Kuraray Co Ltd | Copolyester of excellent gas barrier property |
JPH05293885A (en) * | 1991-02-22 | 1993-11-09 | Osaka Kasei Kk | Sheet consisting of low viscosity polyester resin and its manufacture |
-
1989
- 1989-03-20 JP JP6903989A patent/JP2674193B2/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02169621A (en) * | 1988-12-21 | 1990-06-29 | Kuraray Co Ltd | Copolyester of excellent gas barrier property |
JPH05293885A (en) * | 1991-02-22 | 1993-11-09 | Osaka Kasei Kk | Sheet consisting of low viscosity polyester resin and its manufacture |
Also Published As
Publication number | Publication date |
---|---|
JP2674193B2 (en) | 1997-11-12 |
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