JPH0297518A - Copolyester for heat-resistant packaging material - Google Patents
Copolyester for heat-resistant packaging materialInfo
- Publication number
- JPH0297518A JPH0297518A JP24750688A JP24750688A JPH0297518A JP H0297518 A JPH0297518 A JP H0297518A JP 24750688 A JP24750688 A JP 24750688A JP 24750688 A JP24750688 A JP 24750688A JP H0297518 A JPH0297518 A JP H0297518A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- heat
- copolyester
- resistant packaging
- glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000005022 packaging material Substances 0.000 title claims abstract description 13
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000002253 acid Substances 0.000 claims abstract description 26
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000009477 glass transition Effects 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920000728 polyester Polymers 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 abstract description 6
- 230000004888 barrier function Effects 0.000 abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012046 mixed solvent Substances 0.000 abstract description 3
- 125000003710 aryl alkyl group Chemical group 0.000 abstract 1
- -1 Polyethylene terephthalate Polymers 0.000 description 14
- 238000000034 method Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 150000004702 methyl esters Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 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 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-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
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 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
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 229940119177 germanium dioxide Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 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
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-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
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- UNQWKAVGUZNMJZ-UHFFFAOYSA-N 2,3-dibromoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Br)=C1Br UNQWKAVGUZNMJZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 235000006468 Thea sinensis Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 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
- 230000002411 adverse Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- JXSVIVRDWWRQRT-UYDOISQJSA-N asiatic acid Chemical compound C1[C@@H](O)[C@H](O)[C@@](C)(CO)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(C(O)=O)CC[C@@H](C)[C@H](C)[C@H]5C4=CC[C@@H]3[C@]21C JXSVIVRDWWRQRT-UYDOISQJSA-N 0.000 description 1
- 229940011658 asiatic acid Drugs 0.000 description 1
- LBGFKBYMNRAMFC-PYSQTNCISA-N asiatic acid Natural products C[C@@H]1CC[C@@]2(CC[C@]3(C)C(=CC[C@@H]4[C@@]5(C)C[C@@H](O)[C@H](O)[C@@](C)(CO)[C@@H]5CC[C@@]34C)[C@]2(C)[C@H]1C)C(=O)O LBGFKBYMNRAMFC-PYSQTNCISA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- CLXOLTFMHAXJST-UHFFFAOYSA-N esculentic acid Natural products C12CC=C3C4CC(C)(C(O)=O)CCC4(C(O)=O)CCC3(C)C1(C)CCC1C2(C)CCC(O)C1(CO)C CLXOLTFMHAXJST-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
- 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 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000020333 oolong tea Nutrition 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- IBBQVGDGTMTZRA-UHFFFAOYSA-N sodium;2-sulfobenzene-1,3-dicarboxylic acid Chemical compound [Na].OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O IBBQVGDGTMTZRA-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野１
本発明は、耐熱包装材料用共重合ポリエステルに関し、
さらに詳しくは、ポリマー成形品に対し熱水などの高温
殺菌を施す際に変形や強度低下を起こすことがなく、さ
らにはガスバリヤ−性、透明性及び強度に優れるフィル
ム、容器等の包装材料として有用な耐熱包装材料用共重
合ポリエステルに関する。[Detailed Description of the Invention] [Industrial Application Field 1] The present invention relates to a copolyester for heat-resistant packaging materials,
More specifically, it does not cause deformation or strength loss when polymer molded products are sterilized at high temperatures using hot water, etc., and is useful as a packaging material for films, containers, etc. with excellent gas barrier properties, transparency, and strength. This invention relates to a copolyester for heat-resistant packaging materials.
［従来技術］
ポリエチレンテレフタレートは、その優れた機械的性質
や化学的性質から、繊維、フィルム、工業用樹脂等に広
く用いられているが、最近ではさらにボトル、カップ、
トレイなどの用途にも展開されている。特にその軽量性
などの取り扱い易さなどにより、ポリエステル製のボト
ルが食品や化粧品などの食器として注目されている。ま
た近年、ジュース、ミネラル水、ウーロン茶、コーヒー
などの分野でのポリエステル製ボトルの背反は目ざよし
いものがある、しかしながら、かかる用途においては、
内容物およびボトルの殺菌のため熱水充填また°は高温
下での液充填が必要であるが、通常のポリエチレンテレ
フタレート製ボトルでは耐熱性の不足のため、収縮など
の変形が起こり、ボトル物性が低下し、外観が損われる
などの間顕が生じる。[Prior art] Polyethylene terephthalate is widely used in fibers, films, industrial resins, etc. due to its excellent mechanical and chemical properties, but recently it has also been used in bottles, cups,
It is also being used for applications such as trays. In particular, polyester bottles are attracting attention as tableware for foods, cosmetics, etc. because of their light weight and ease of handling. In addition, in recent years, there have been many problems with polyester bottles in the fields of juice, mineral water, oolong tea, coffee, etc. However, in such applications,
In order to sterilize the contents and the bottle, it is necessary to fill it with hot water or liquid at high temperatures, but due to the lack of heat resistance in ordinary polyethylene terephthalate bottles, deformation such as shrinkage occurs, and the physical properties of the bottle deteriorate. This causes deterioration such as deterioration of appearance and deterioration of appearance.
かかる問題を解消させるために多くの提案がなされてい
る。たとえば、成形方法で耐熱性を向上させる方法（特
開昭６２−７４６２２．特開昭５５−５１５２５など）
が挙げられる。もつとも、この成形方法で耐熱性を向上
させる手段では通常能力が低下したり得られた製品の耐
熱温度にも限界がある。Many proposals have been made to solve this problem. For example, methods for improving heat resistance through molding methods (JP-A-62-74622, JP-A-55-51525, etc.)
can be mentioned. However, when this molding method is used to improve heat resistance, the performance usually decreases, and there is a limit to the heat resistance temperature of the resulting product.
［発明の目的］
本発明の目的は、このような問題を解消し、優れた耐熱
性を有し、ガスバリヤ−性、透明性１機械的強度等の優
れるフィルム、容器などの包装材料として有用な耐熱包
装材料用共重合ポリエステルを提供することにある。[Object of the invention] The object of the present invention is to solve these problems and to provide a film useful as a packaging material for containers, etc., which has excellent heat resistance, gas barrier properties, transparency, mechanical strength, etc. An object of the present invention is to provide a copolyester for heat-resistant packaging materials.
［発明の構成］
本発明は、主たる酸成分がテレフタル酸であり、主たる
グリコール成分がエチレングリコールであるポリエステ
ルであって、（Ｉ）式で示される化合物を全酸成分に対
して３〜２０モル％共重合成分として含有し且つ該共重
合ポリエステルのガラス転移温度か８５℃乃至９０℃で
ある耐熱包装材料用共重合ポリエステルである。[Structure of the Invention] The present invention provides a polyester in which the main acid component is terephthalic acid and the main glycol component is ethylene glycol, and the compound represented by formula (I) is contained in an amount of 3 to 20 moles based on the total acid component. % as a copolymer component, and the copolymerized polyester has a glass transition temperature of 85°C to 90°C for use in heat-resistant packaging materials.
（式中Ｒ１及びＲ２は水素又は炭素原子数１′〜３のア
ルキル基を表わす。また、８３〜１（６は水素又は炭素
原子数１〜１０のアルキル基、アルキルアリール基若し
くはアリール基を表わす。）ここで「主たるＪとは、８
０モル％を超える量をいう、したがって、２０モル％以
下の量ではこれ以外の他のエステル単位を含むことがで
きる。かかる共重合成分としては、テレフタル酸、エチ
レングリコール及び特許請求の範囲で示した化合物以外
のジカルボン酸及びジオール、オキシ酸がある。(In the formula, R1 and R2 represent hydrogen or an alkyl group having 1 to 3 carbon atoms. 83 to 1 (6 represents hydrogen or an alkyl group having 1 to 10 carbon atoms, an alkylaryl group, or an aryl group) .)Here, ``The main J is 8
It refers to an amount exceeding 0 mol %, therefore, it can contain other ester units in an amount of 20 mol % or less. Such copolymerization components include terephthalic acid, ethylene glycol, dicarboxylic acids and diols other than the compounds shown in the claims, and oxyacids.
具体的には芳香族ジカルボン酸、例えばインフタル酸、
ナフタレンジカルボン酸、ジフェニルジカルボン酸、ジ
フェニルエーテルジカルボン酸、ジフェニルスルホンジ
カルボン酸、ジフェニルケトンジカルボン酸、ナトリウ
ム−スルホイソフタル酸、ジブロモテレフタル酸など；
脂環族ジカルボン酸、例えばデカリンジカルボン酸、ヘ
キサヒドロテレフタル酸など；脂肪族ジカルボン酸、例
えばマロン酸、コハク酸、アジピン酸など；脂肪族ジオ
ール、例えは、トリメチレングリコール１．テトラメチ
レンクリコール、ヘキサメチレングリコール、ネオペン
チルグリコール、ジエチレングリコールなど；芳香族ジ
オール、例えば、ヒドロキノン、カテコール、ナフタレ
ンジオール、レゾルシン、ビスフェノールＡ［２，２−
ビス−（４−ヒドロキシフェニル）プロパン］、テトラ
ブロモビスフェノールＡ、ビスヒドロキシニドキシビス
フェノールＡなど；脂環族ジオール、例えばシクロヘキ
サンジオールなど：脂肪族オキシカルボン酸、例えばグ
リコール酸、ヒドロアクリル酸、３−オキシプロピオン
酸など；脂環族オキシカルボン酸、例えば、アジアチン
酸、キノバ酸など：芳香族オキシカルボン酸、例えばサ
リチル酸、ｍ−オキシ安息香酸、ｐ−オキシ安息香酸、
マンデル酸、マトロラクチン酸などを挙げることができ
る６さらに、ポリエステルが実質的に線状である範囲内
で３価以上の多官能化合物、例えば、グリセリン、トリ
メチロールプロパン、ペンタエリスリトール、トリメリ
ット酸、トリメシン酸、ピロメリット酸、トリカルバリ
ル酸、没食子酸などを共重合してもよい、また単官能化
合物、例えば、０ベンゾイル安息香酸、ナフトエ酸等を
添加してもよい。Specifically, aromatic dicarboxylic acids such as inphthalic acid,
Naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ketone dicarboxylic acid, sodium sulfoisophthalic acid, dibromoterephthalic acid, etc.;
Alicyclic dicarboxylic acids, such as decalin dicarboxylic acid, hexahydroterephthalic acid, etc.; Aliphatic dicarboxylic acids, such as malonic acid, succinic acid, adipic acid, etc.; Aliphatic diols, such as trimethylene glycol 1. Tetramethylene glycol, hexamethylene glycol, neopentyl glycol, diethylene glycol, etc.; aromatic diols, such as hydroquinone, catechol, naphthalene diol, resorcinol, bisphenol A [2,2-
Bis-(4-hydroxyphenyl)propane], tetrabromobisphenol A, bishydroxynidoxybisphenol A, etc.; alicyclic diols, such as cyclohexanediol; aliphatic oxycarboxylic acids, such as glycolic acid, hydroacrylic acid, 3- Oxypropionic acid, etc.; Alicyclic oxycarboxylic acids, such as asiatic acid, quinobic acid, etc.; Aromatic oxycarboxylic acids, such as salicylic acid, m-oxybenzoic acid, p-oxybenzoic acid,
Examples include mandelic acid, matrolactin acid, etc. 6 Furthermore, trivalent or higher polyfunctional compounds within the range where the polyester is substantially linear, such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, Trimesic acid, pyromellitic acid, tricarballylic acid, gallic acid, etc. may be copolymerized, and monofunctional compounds such as 0-benzoylbenzoic acid, naphthoic acid, etc. may be added.
本発明の共重合ポリエステルには、下記（Ｉ）式で示さ
れる化合物を全グリコール成分に対して３〜２０モル％
共重合し、且つ該共重合ポリエステルのガラス転移温度
が８５〜９０℃であることが必要がある。The copolymerized polyester of the present invention contains a compound represented by the following formula (I) in an amount of 3 to 20 mol% based on the total glycol component.
It is necessary that the copolymerized polyester be copolymerized and that the glass transition temperature of the copolymerized polyester be 85 to 90°C.
（式中Ｒ１及びＲ２は水素又は炭素原子数１〜３のアル
キル基を表わす、また、Ｒ３−Ｒ６は水素又は炭素原子
数１〜１０のアルキル基、アルキルアリール基もしくは
アリール基を表わす、）化合物としては、４．４′−ジ
フェニルジカルボン酸、４．４°−ジフェニルジカルボ
ン酸メチルエステル、４，４°−ジフェニルジカルボン
酸エチルエステル、４，４゛−ジフェニルジカルボン酸
プロピルエステル、３，３°−ジメチル−４，４゛−ジ
フェニルジカルボン酸、３，３°、５，５°−テトラメ
チル−４，４°−ジフェニルジカルボン酸、３，３°、
５．５“−テ１〜ラメチル４４°−ジフェニルジカルボ
ン酸、３．３’、！１，５テトラメチルー４，４°−ジ
フェニルジカルボン酸、３．３°、５．５’ −ｔｅｒ
ｔ−ブチル−４，４゛−ジフェニルジカルボン酸、３，
３°、５，５°−ｎ−ブチル−４，４°−ジフェニルジ
カルボン酸などが例示がされる。(In the formula, R1 and R2 represent hydrogen or an alkyl group having 1 to 3 carbon atoms, and R3-R6 represent hydrogen or an alkyl group, alkylaryl group, or aryl group having 1 to 10 carbon atoms) Compound Examples include 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyldicarboxylic acid methyl ester, 4,4'-diphenyldicarboxylic acid ethyl ester, 4,4'-diphenyldicarboxylic acid propyl ester, 3,3'- Dimethyl-4,4゛-diphenyldicarboxylic acid, 3,3°, 5,5°-tetramethyl-4,4°-diphenyldicarboxylic acid, 3,3°,
5.5"-tetramethyl44°-diphenyldicarboxylic acid, 3.3',!1,5tetramethyl-4,4°-diphenyldicarboxylic acid, 3.3°,5.5'-ter
t-butyl-4,4'-diphenyldicarboxylic acid, 3,
Examples include 3°, 5,5°-n-butyl-4,4°-diphenyldicarboxylic acid.
本発明において該化合物を３〜２０モル％共重合し、ガ
ラス転移温度が８３℃〜９０゛Ｃ以下であることが必要
である。３モル％未満では、ガラス転移温度が８３℃以
上とならず、しかも結晶化速度も大きくならないため、
耐熱性が十分に出ない。また２０モル％を越える場合は
成形時の延伸が不十分になり、偏肉なとおこり、逆に物
性か低下したりする。In the present invention, it is necessary that the compound be copolymerized in an amount of 3 to 20 mol % and have a glass transition temperature of 83 DEG C. to 90 DEG C. or less. If it is less than 3 mol%, the glass transition temperature will not exceed 83°C, and the crystallization rate will not increase.
Heat resistance is not sufficient. Moreover, if it exceeds 20 mol%, stretching during molding will be insufficient, resulting in uneven thickness and, conversely, deterioration of physical properties.
また、共重合量が多いと剛性が減少するため、成形品の
物性低下したりする。好ましくは５〜１５モル％である
。また該ポリエステルのガラス転移温度は９０℃を超え
る場合高い温度で延伸する必要かあり、その高温に加熱
することにより結晶化速度が高くなって結晶化が進み延
伸が不十分となって逆に物性が低下したりする。Furthermore, if the amount of copolymerization is large, the rigidity will decrease, resulting in deterioration of the physical properties of the molded product. Preferably it is 5 to 15 mol%. In addition, if the glass transition temperature of the polyester exceeds 90°C, it is necessary to stretch it at a high temperature.Heating to such a high temperature increases the crystallization rate and advances crystallization, resulting in insufficient stretching and adversely affecting the physical properties. may decrease.
一般にガラス転移温度を−Ｅけるものとしているいろな
剤が知られている。しかし、それらの多くは一般の共重
合がしめすように添加量を増加すると共に結晶性がそこ
なわれフィルム、ボトルなどのような包装材料として延
伸及びプロー成形して熱セットした際に、十分な熱セッ
トができず、物性が低下したりする。本発明の化な物は
、かかる問題かなく、共重合と共にガラス転移温度、結
晶化速度があがり、良好な耐熱性、透明性を示す。Various agents are known that generally lower the glass transition temperature by -E. However, as shown in general copolymerization, as the amount of addition is increased, the crystallinity of many of them is damaged, and when they are stretched and blow-molded and heat-set as packaging materials such as films and bottles, they are not sufficient. Heat setting may not be possible and physical properties may deteriorate. The fish of the present invention does not have such problems, has a glass transition temperature and a crystallization rate that increase with copolymerization, and exhibits good heat resistance and transparency.
本発明の共重合ポリエステルは固有粘度（フェノール／
テトラクロロエタン（重壁比６０／ ４０ ）の混合溶
媒を用い、３５℃で測定）０，４〜１．５であることか
好ましい、特に０．５以上であることが好ましい、かか
る共重合ポリエステルは、従来からポリエチレンテレフ
タレートの製造に際して蓄積された方法で製造すること
ができる０例えば、テレフタル酸、エチレングリコール
及び（Ｉ）式で示される化合物を用いてエステル反応を
行うか、あるいはテレフタル酸の低級アルキルエステル
（例えばジメチルエステル）、エチレングリコール及び
（Ｉ）式で示される化合物を用いて、エステル交換反応
を行い、得られた反応生成物をさらに重縮合せしめるこ
とによって製造できる。また、これらのポリエステルを
製造する際に、エステル交換触媒９重合触媒、安定剤な
どを使用することが好ましい、これら触媒、安定剤など
はポリエステル、特にポリエチレンテレフタレートの触
媒、安定剤などとして知られているものを用いることか
できる。また、必要に応じて他の添加剤１例えば着色剤
、抗酸化剤、紫外線吸収剤、帯電防止剤。The copolyester of the present invention has an intrinsic viscosity (phenol/
The copolymerized polyester is preferably 0.4 to 1.5 (measured at 35°C using a mixed solvent of tetrachloroethane (heavy wall ratio 60/40), particularly preferably 0.5 or more). For example, an ester reaction may be carried out using terephthalic acid, ethylene glycol and a compound represented by formula (I), or a lower alkyl terephthalate It can be produced by carrying out a transesterification reaction using an ester (for example, dimethyl ester), ethylene glycol, and a compound represented by formula (I), and further polycondensing the obtained reaction product. In addition, when producing these polyesters, it is preferable to use transesterification catalysts, polymerization catalysts, stabilizers, etc. These catalysts, stabilizers, etc. are known as catalysts, stabilizers, etc. for polyesters, especially polyethylene terephthalate. You can use what you have. In addition, other additives 1 such as colorants, antioxidants, ultraviolet absorbers, and antistatic agents may be added as necessary.
難燃剤などを使用してもよい。Flame retardants etc. may also be used.
［発明の効果］
本発明の共重合ポリエステルその成形品に対し熱水など
の高温殺菌を施す際に変形９強度低下を起こすことがな
く、さらにはガスバリヤ−性、透明性及び機械的強度に
潰れている。したがって、高温物を充填するフィルム、
容器などの耐熱包装材料としてきわめて有効である。[Effects of the Invention] When molded products of the copolymerized polyester of the present invention are sterilized at high temperatures using hot water, etc., there is no deformation (9) strength reduction, and furthermore, gas barrier properties, transparency, and mechanical strength are reduced. ing. Therefore, films filled with hot objects,
It is extremely effective as a heat-resistant packaging material for containers, etc.
［実施例］ 以下実施例により、本発明の詳細な説明する。[Example] The present invention will be explained in detail below with reference to Examples.
なお、実施例中［部」は、重量部を意味する。また実施
例中で用いた特性の測定法を以下に示す。In addition, in the examples, [parts] means parts by weight. Further, the method for measuring the characteristics used in the examples is shown below.
・固有粘度
フェノール／テトラクロロエタン（６０／ ４０重量比
）混合溶媒を用い３５℃で測定した溶液粘度から求める
。- Intrinsic viscosity Determined from the solution viscosity measured at 35°C using a mixed solvent of phenol/tetrachloroethane (60/40 weight ratio).
・ガラス転移温度：Ｔｇ及び結晶化温度゛ＦＣポリマー
１０■を３００℃まで昇温し、氷水中にて急冷したもの
をサンプルとし、デュポン社製示差走査熱量計（Ｏ３Ｃ
ｌ０９０Ｂ）により２０℃／Ｉｇｉｎの速度で昇温し、
測定した値である。・Glass transition temperature: Tg and crystallization temperature FC Polymer 10 was heated to 300℃ and rapidly cooled in ice water.
1090B) at a rate of 20°C/Igin,
This is the measured value.
実施例１および比較例１
テレフタル酸ジメチル２７０部、エチレングリコール１
９２部、 ４．４’−ジフェニルジカルボン酸メチルエ
ステル４２部（梢造革位に対して１０モル％）及び＃酸
チタンのエチレングリコール溶液（チタンとして１．０
ｖｔ％） ０．４部をエステル交換反応缶に仕込み、
１５０℃から徐々に昇温し、留出するメタノールを分離
してエステル交換反応させた。Example 1 and Comparative Example 1 270 parts of dimethyl terephthalate, 1 part of ethylene glycol
92 parts, 42 parts of 4.4'-diphenyldicarboxylic acid methyl ester (10 mol % based on the foregrowth position) and an ethylene glycol solution of titanium #acid (1.0% as titanium)
vt%) 0.4 part was charged into a transesterification reactor,
The temperature was gradually raised from 150° C., and the distilled methanol was separated and transesterified.
反応完結時の液晶は２３０℃であった０次いで正リン酸
０，０６部を添加し、反応生成物を重縮合缶に移し、二
酸化ゲルマニウムのエチレングリコールスラリー（二酸
化ゲルマニウムとして１．１５ｗｔ％ ）４．２部を添
加した後、約１０分間常圧下で反応させ、反応系を徐々
に減圧し、３０分後に５０＋＋ｕ＋ｆｌ（］、 ９９０
分に２０闇１１Ｌ １２０分後に０．５簡Ｈｇとした。The liquid crystal temperature at the time of completion of the reaction was 230°C. Next, 0.06 parts of orthophosphoric acid was added, the reaction product was transferred to a polycondensation vessel, and an ethylene glycol slurry of germanium dioxide (1.15 wt% as germanium dioxide) was added. After adding .2 parts, the reaction was carried out under normal pressure for about 10 minutes, the pressure of the reaction system was gradually reduced, and after 30 minutes, 50++u+fl(], 990
20 darkness 11L per minute, 0.5 simple Hg after 120 minutes.
一方液温は２３０℃から徐々に昇温して１２０分後に２
８０℃とし、以降この温度で３時間重縮合反応させたの
ち、重縮合缶から常法により流水中に抜き出してチップ
にした。このチップの固有粘度は０．６３であった。On the other hand, the liquid temperature was gradually increased from 230℃ and after 120 minutes,
The temperature was raised to 80° C., and after a polycondensation reaction was carried out at this temperature for 3 hours, the mixture was extracted from the polycondensation vessel into running water by a conventional method and made into chips. The intrinsic viscosity of this chip was 0.63.
このチップを１６０℃で２時間予備乾燥しな後、３０分
で２１０℃まで昇温し、窒素雰囲気下で、０．５Ｔｏｒ
ｒの減圧下、８時間固相重合させて、固有粘度；０．７
４、Ｔｇ＝８４℃、Ｔｃ１＝１５４℃のポリマーを得た
。After pre-drying this chip at 160°C for 2 hours, the temperature was raised to 210°C in 30 minutes, and the temperature was increased to 0.5 Torr under a nitrogen atmosphere.
Solid phase polymerization was carried out for 8 hours under reduced pressure of r, and the intrinsic viscosity was 0.7.
4. A polymer with Tg=84°C and Tc1=154°C was obtained.
このようにして得られたポリマーを使用し、シリンダー
温度２８５℃の射出成形機を用い重ｉ５０゜の円筒状有
底バリリンを成形し、ついでこのバリリンを内部温度が
９５〜１１０’Ｃになるように再加熱した後、２軸延伸
ブローをおこない、内容８２１！のボトルを得た。この
ボトルは外観良好で、落下させても変形は見られなかっ
た。また、９８℃の熱水を入れたが、変形は見られなか
った。Using the polymer thus obtained, a cylindrical bottomed Vallyline with a weight i of 50° is molded using an injection molding machine with a cylinder temperature of 285°C, and then this Valyline is heated to an internal temperature of 95 to 110°C. After reheating to , biaxial stretching blowing was performed to obtain content 821! Got a bottle of. This bottle had a good appearance and showed no deformation even when dropped. In addition, 98°C hot water was added, but no deformation was observed.
尚、比較例として４．４゛−ジフェニルジカルボン酸メ
チルエステルを除いた以外は同様に行った時の［＾］相
重合後のポリマーの固有粘度は０．７８．’ｒｇは８１
℃、′Ｉ″ｃｉは１７６ ’Ｃであった。また、このポ
リマーを使用して得ちれたボトルは外観良好で落下させ
ても変形は見られなかった。しかし、９８゛Ｃの熱水を
注入すると胴部下部及び底部に変形が見られた。As a comparative example, when the same procedure was carried out except that 4.4'-diphenyldicarboxylic acid methyl ester was removed, the intrinsic viscosity of the polymer after [^] phase polymerization was 0.78. 'rg is 81
℃, 'I''ci was 176'C. Also, the bottle obtained using this polymer had a good appearance and no deformation was observed even when dropped. When injected, deformation was observed in the lower torso and bottom.
したがって本発明のポリマーは耐熱用包装材料としてｆ
憂れていることか判った。Therefore, the polymer of the present invention can be used as a heat-resistant packaging material.
I could tell that he was worried.
［実施例２〜４．比較例２．３１
４．４°−ジフェニルジカルボン酸メチルエステルの添
加量を変える以外は実施例１と同様の条件で実験を行な
った。結果を表１に示す。[Examples 2-4. Comparative Example 2.31 An experiment was conducted under the same conditions as in Example 1 except that the amount of 4.4°-diphenyldicarboxylic acid methyl ester added was changed. The results are shown in Table 1.
表１
［実施例５］
４．４°−ジフェニルジカルボン酸メチルエステルの代
わりに３，３°、５，５°−テトラメチル−４，４゛−
ジフェニルジカルボン酸メチルエステルを用いる以外は
実施例１と同様に行なった。結果を表２に示す。Table 1 [Example 5] 3,3°, 5,5°-tetramethyl-4,4′- instead of 4.4°-diphenyldicarboxylic acid methyl ester
The same procedure as in Example 1 was carried out except that diphenyldicarboxylic acid methyl ester was used. The results are shown in Table 2.
［比較例４．５１
４．４°−ジフェニルジカルボン酸メチルエステルの代
わりに２．２−ビス［４−（２−ヒドロキシエトキシ）
−フェニル］プロパンを用い、その添加量を変える以外
は実施例１と同様に行なった。結果を表２に示した。[Comparative Example 4.51 2.2-bis[4-(2-hydroxyethoxy)] instead of 4.4°-diphenyldicarboxylic acid methyl ester
-Phenyl]propane was used, and the same procedure as in Example 1 was conducted except that the amount added was changed. The results are shown in Table 2.
表
手
続
ネ市
正
書
平成
元年
３月７３日
特賞千庁長も’ｌＴ４ジ
１、事件の表示
特願昭
漬ヲ
２、発明の名称
耐熱包装材料用共重合ポリエステル
（３００）帝人株式会社
明ｉｌｌ占の「発明の詳細な説明」の欄（１）明細書、
第６頁、第１９行、「８５〜９０℃」とあるのを１８３
〜９０℃」と訂正する。Publication Procedures City Official Report March 73, 1989 Special Award Senchocho'lT4J1, Indication of Case Special Application Showzuke 2, Name of Invention Copolyester Polyester (300) for Heat-Resistant Packaging Materials Teijin Ltd. Meiji Co., Ltd. Illustrious “Detailed Description of the Invention” column (1) Specification,
Page 6, line 19, "85-90℃" is 183
〜90℃''.
（２）同、第９頁、第６行目、［３５℃で測定）０，４
〜１．５」とあるのを「３５℃で測定）が０．４〜１．
５」と訂正する。(2) Same, page 9, line 6, [measured at 35°C] 0,4
~1.5'' is 0.4~1.5 (measured at 35°C).
5,” he corrected.
（３）同、第１３頁の表１における実施例３のＴｇの欄
の値「９７」とあるのを「８７」と訂正する。(3) The value "97" in the Tg column of Example 3 in Table 1 on page 13 is corrected to "87".
以上that's all
Claims (1)
成分がエチレングリコールであるポリエステルであって
、下記（ I ）式で示される化合物を全グリコール成分
に対して３〜２０モル％共重合成分として含み、且つ該
共重合ポリエステルのガラス転移温度が８３℃乃至９０
℃である耐熱包装材料用共重合ポリエステル。 ▲数式、化学式、表等があります▼（ I ） （式中Ｒ＿１及びＲ＿２は水素又は炭素原子数１〜３の
アルキル基を表わす。また、Ｒ＿３〜Ｒ＿６は水素又は
炭素原子数１〜１０のアルキル基、アルキルアリール基
若しくはアリール基を表わす。）[Scope of Claims] A polyester whose main acid component is terephthalic acid and whose main glycol component is ethylene glycol, which contains a compound represented by the following formula (I) in an amount of 3 to 20 mol% based on the total glycol component. Contained as a polymerization component, and the copolymerized polyester has a glass transition temperature of 83°C to 90°C.
Copolyester for heat-resistant packaging materials. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R_1 and R_2 represent hydrogen or an alkyl group having 1 to 3 carbon atoms. Also, R_3 to R_6 represent hydrogen or an alkyl group having 1 to 10 carbon atoms. group, alkylaryl group, or aryl group)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24750688A JPH0297518A (en) | 1988-10-03 | 1988-10-03 | Copolyester for heat-resistant packaging material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24750688A JPH0297518A (en) | 1988-10-03 | 1988-10-03 | Copolyester for heat-resistant packaging material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0297518A true JPH0297518A (en) | 1990-04-10 |
Family
ID=17164491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24750688A Pending JPH0297518A (en) | 1988-10-03 | 1988-10-03 | Copolyester for heat-resistant packaging material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0297518A (en) |
-
1988
- 1988-10-03 JP JP24750688A patent/JPH0297518A/en active Pending
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