JPH01170619A - Copolyester - Google Patents
CopolyesterInfo
- Publication number
- JPH01170619A JPH01170619A JP32925087A JP32925087A JPH01170619A JP H01170619 A JPH01170619 A JP H01170619A JP 32925087 A JP32925087 A JP 32925087A JP 32925087 A JP32925087 A JP 32925087A JP H01170619 A JPH01170619 A JP H01170619A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- dicarboxylic acid
- component
- benzene
- bis
- 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
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 13
- 150000002009 diols Chemical class 0.000 claims abstract description 17
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 16
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 229920000728 polyester Polymers 0.000 claims description 34
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 4
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 3
- IAXFZZHBFXRZMT-UHFFFAOYSA-N 2-[3-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=CC(OCCO)=C1 IAXFZZHBFXRZMT-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 75
- -1 hydroxyethoxy Chemical group 0.000 abstract description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 20
- 230000035699 permeability Effects 0.000 abstract description 16
- 239000002253 acid Substances 0.000 abstract description 14
- 239000005022 packaging material Substances 0.000 abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 abstract description 4
- 229920001577 copolymer Polymers 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 125000005113 hydroxyalkoxy group Chemical group 0.000 abstract 1
- 238000000034 method Methods 0.000 description 18
- 229920000139 polyethylene terephthalate Polymers 0.000 description 17
- 239000005020 polyethylene terephthalate Substances 0.000 description 17
- 239000007789 gas Substances 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000005809 transesterification reaction Methods 0.000 description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229960005323 phenoxyethanol Drugs 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 235000014171 carbonated beverage Nutrition 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 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
- 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 2
- 238000000071 blow moulding Methods 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 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 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000015203 fruit juice Nutrition 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
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- VMBKZUJUULLFOS-UHFFFAOYSA-N 3-[3-(3-hydroxypropoxy)phenoxy]propan-1-ol Chemical compound OCCCOC1=CC=CC(OCCCO)=C1 VMBKZUJUULLFOS-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
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 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 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000006384 oligomerization reaction Methods 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
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は共重合ポリエステルに関し、透明性および耐ガ
ス透過性に優れ、容器、フィルム等の包装材料として有
用な包装材料用共重合ポリエステルに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a copolyester, and more particularly to a copolyester for packaging materials that has excellent transparency and gas permeation resistance and is useful as a packaging material for containers, films, and the like.
ポリエチレンテレフタレートで代表されるポリエステル
は、優れた機械的性質および化学的特性のため、広く繊
維、フィルム等に使用されてきたが、近年その優れた透
明性、気体遮断性。Polyester, represented by polyethylene terephthalate, has been widely used in fibers, films, etc. due to its excellent mechanical and chemical properties, but in recent years its excellent transparency and gas barrier properties have been widely used.
安全衛生性などから、炭酸飲料−果汁飲料、液体調味料
１食用油、酒やワイン用の容器また最近ではカップ、ト
レイ等としても使用されている。For reasons of safety and hygiene, they are also used as containers for carbonated drinks, fruit juice drinks, liquid seasonings, edible oils, alcohol and wine, and recently as cups, trays, and the like.
特に、炭酸飲料、果汁飲料、酒、ワイン等の用途におい
ては内容物保存の点で耐ガス透過性が要求されるが、ポ
リエチレンテレフタレートはポリオレフィン等地の樹脂
に比べれば良好な耐ガス透過性を示すものの、必ずしも
充分な耐ガス透過性を有するとは言えない。In particular, gas permeation resistance is required for the preservation of contents in applications such as carbonated drinks, fruit juice drinks, alcohol, and wine, but polyethylene terephthalate has better gas permeation resistance than other resins such as polyolefins. However, it cannot be said that it necessarily has sufficient gas permeability.
ポリエチレンテレフタレートの耐ガス透過性を更に向上
させる方法が各種提案されている。Various methods have been proposed to further improve the gas permeation resistance of polyethylene terephthalate.
例えば、ポリ塩化ビニリデン、エチレン−酢ビ共重合体
ケン化物、ポリエチレンイソフタレート等の耐ガス透過
性材料をコーティングあるいは積層する方法（特開昭Ｓ
ダー／／７Ｓ６ｊＴ、同ｓｂ−ｂｌＩｇ３ｑ等）、耐ガ
ス透過性材料をブレンドする方法（特開昭５ｑ−１０６
ｔａｏ） 、ポリエステルの配向度を上げて耐ガス透過
性を向上させる方法（特開昭ｓｂ−１ｓｌｂａｇ ）等
が提案されている。For example, a method of coating or laminating gas-permeable materials such as polyvinylidene chloride, saponified ethylene-vinyl acetate copolymer, and polyethylene isophthalate (JP-A-Sho S.
7S6jT, sb-blIg3q, etc.), a method of blending gas permeation-resistant materials (Japanese Patent Application Laid-Open No. 5Q-106
tao), a method of improving gas permeability by increasing the degree of orientation of polyester (Japanese Unexamined Patent Application Publication No. 1993-110003), and the like have been proposed.
しかし、ポリ塩化ビニリデンやエチレン−酢ビ共重合体
ケン化物をコーティング又は積層する方法にあっては、
ポリエステルとは異なった樹脂を共に用いるため、ポリ
エステルとの接漬性が悪く層間剥離を起したり、その結
果容器の透明性が失われるばかりでなく回収の点からも
不利である。However, in the method of coating or laminating polyvinylidene chloride or saponified ethylene-vinyl acetate copolymer,
Since a resin different from polyester is used together, the contactability with polyester is poor and delamination may occur, resulting in a loss of transparency of the container as well as disadvantages in terms of recovery.
又、ポリエチレンイソフタレートをコーティング又は積
層する方法も提案されており１両層が同じポリエステル
類であるためこのような欠点はないが、積層してももろ
く、容器としての強度を持たせるためにはポリエチレン
テレフタレートをそれ単独の場合と同じ位の肉厚にする
必要があり、容器全体として重くなり合成樹脂容器の長
所が失われてしまうし又、耐ガス透過性改良効果も充分
とは言えない。また、ポリエステル成形品の配向度を上
げる方法では耐ガス透過性の向上に限界がある。A method of coating or laminating polyethylene isophthalate has also been proposed, and since both layers are made of the same polyester, there is no such drawback. It is necessary to make the wall thickness of polyethylene terephthalate the same as that of polyethylene terephthalate alone, which increases the weight of the container as a whole and loses the advantages of a synthetic resin container, and the effect of improving gas permeability cannot be said to be sufficient. Furthermore, there is a limit to the improvement in gas permeability with methods of increasing the degree of orientation of polyester molded products.
更Ｋ、ポリエチレンテレフタレートにかわる包装材料用
ポリエステルとして炭素数ダから１２の脂肪族ジカルボ
ン酸を共重合させたポリアルキレンイソフタレートが提
案されている（アメリカ特許第ダ、ダ０３，０９０号明
細書）が、このポリエステルはポリエチレンテレフタレ
ート包装材料の耐ガス透過性を改良するには満足するも
のではない。Moreover, polyalkylene isophthalate, which is a polyester copolymerized with an aliphatic dicarboxylic acid having from 1 to 12 carbon atoms, has been proposed as a polyester for packaging materials in place of polyethylene terephthalate (U.S. Patent No. 03,090). However, this polyester is not satisfactory for improving the gas permeation resistance of polyethylene terephthalate packaging materials.
また、テレフタル竣を主とし、２，２′−オキシジ酢酸
＋ ２．Ｚ’−イミノジ酢酸等を併用したジカルボン酸
と、炭素数的ｇ以下のジオールから成るコポリエステル
およびそれから成る容器も知られているが、この場合も
、耐ガス透過性改良は十分とは言えない（アメリカ特許
第りタ３＾ｇａｓ号及びダ、ＳダＡ、／７０号明細書）
。In addition, mainly finished terephthal, 2,2'-oxydiacetic acid + 2. Copolyesters made of dicarboxylic acids combined with Z'-iminodiacetic acid, etc., and diols having carbon atoms of g or less, and containers made of the same, are also known, but in this case as well, the improvement in gas permeability cannot be said to be sufficient. (U.S. Patent No. 3^gas and DA, SDA A, /70 Specification)
.
本発明は、機械的強度、透明性等の物性に優れ、耐ガス
透明性の優れた共重合ポリエステルを提供することを目
的とする。An object of the present invention is to provide a copolyester having excellent physical properties such as mechanical strength and transparency, and excellent gas resistance and transparency.
本発明は、ジカルボン酸成分の主成分がイソフタル酸ま
たはそのエステル形成性誘導体であり、他の成分として
一般式ｍ
ＨＯＯＣ−Ｒ’−Ｘ−Ｒ２−ＣＯＯＨ・・・・・・（１
）（式中、Ｒ１、Ｒ２は同一でも異なっていてもよくコ
価の脂肪族基を表わす。ＸはＯまたはＮＨを表わす。）
で示されるジカルボン酸またはそのエステル形成性誘導
体を全ジカルボン酸成分に対してｌ〜ＳＯモルチ、好ま
しくは／Ｑ〜’ＩＱモルチな含み、全ジオール成分の少
くとも３モルチ、好ましくはｇモルチ以上が一般式（２
）
（式中、Ｒ３、Ｒ４は同一でも異っていてもよく、コ価
の脂肪族基または芳香族基を表わす。）で示されるジオ
ールである共重合ポリエステルに関する。In the present invention, the main component of the dicarboxylic acid component is isophthalic acid or its ester-forming derivative, and other components have the general formula m HOOC-R'-X-R2-COOH (1
) (In the formula, R1 and R2 may be the same or different and represent a covalent aliphatic group. X represents O or NH.) The dicarboxylic acid or its ester-forming derivative represented by 1 to SO molti, preferably /Q to 'IQ molti, relative to the general formula (2
) (In the formula, R3 and R4 may be the same or different and represent a covalent aliphatic group or an aromatic group.)
一般式（１）においてＲ１、Ｒ２は、主鎖の炭素数が通
常、／−ｐの脂肪族炭化水素のユ価残基である。この主
鎖には、水素、炭素数／−１のアルキル基等が結合して
おり−その結合の位置等は特に限定されない。In general formula (1), R1 and R2 are alivalent residues of aliphatic hydrocarbons in which the number of carbon atoms in the main chain is usually /-p. Hydrogen, an alkyl group having carbon number/-1, etc. are bonded to this main chain, and the position of the bond is not particularly limited.
ろ
一般式（１）で示されＩジカルボン酸の具体例としては
、コ、２′−オキシジ酢酸（ジグリコール酸）。A specific example of the I dicarboxylic acid represented by the general formula (1) is co,2'-oxydiacetic acid (diglycolic acid).
３．３′−オキシジプロピオン酸（ジエチルエーテル−
β、β′−ジカルボン酸）、２．ｚ’−オキシジプロピ
オン酸、 ｔＩ、＋’−オキシジ酪酸、２，２′−イミ
ノジ酢酸＋ ３．３’−イミノジプロピオン酸、２．２
’−イミノジプロピオン酸、 ｕ、ｕ’−イミノジ酪酸
、３．３′−イミノジ酪酸等が挙げられ、特に２．２’
−オキシジ酢酸、λ、２′−イミノジ酢酸が好ましく用
いられる。3.3'-oxydipropionic acid (diethyl ether)
β, β′-dicarboxylic acid), 2. z'-oxydipropionic acid, tI, +'-oxydibutyric acid, 2,2'-iminodiacetic acid + 3.3'-iminodipropionic acid, 2.2
Examples include '-iminodipropionic acid, u,u'-iminodibutyric acid, 3.3'-iminodibutyric acid, and especially 2.2'-iminodibutyric acid.
-oxydiacetic acid and λ,2'-iminodiacetic acid are preferably used.
一般式（２）において、Ｒ３、Ｒ４はコ価の脂肪族基又
は芳香族基であり、以下のものが挙げられる。In general formula (2), R3 and R4 are covalent aliphatic groups or aromatic groups, and examples thereof include the following.
（イ）主鎖の炭素数が／−Ｑの脂肪族炭化水素のコ価残
基であって、この主鎖には水素、ハロケン、炭ｆＥ数／
Ｓ−４’のアルキル基、フェニル基、ベンジル基等が
結合している。その結合の位置等は特に限定されない。(a) A covalent residue of an aliphatic hydrocarbon whose main chain has a carbon number of /-Q, and this main chain includes hydrogen, halogen, carbon fE number/
The alkyl group, phenyl group, benzyl group, etc. of S-4' are bonded. The position of the bond is not particularly limited.
このよりなＲ３゜Ｒ４を含む一般式（２）で示されるジ
オールの具体例としてＩｔ”ｉ、 １，Ｊ−ビス（２−
ヒドロキシエトキシ）ベンゼン、ｌ、３−ビス（２−ヒ
ドロキシ−／−クロロエトキシ）ベンゼン−１，３−ビ
ス（２−ヒドロキシ−１，／−ジクロロエトキシ）ベン
ゼン、１，Ｊ−ビス（２−ヒドロキシ−１−メチルエト
キシ）ベンゼン、ｌ、３−ビス（２−ヒドロキシーコー
メチルエトキシ）ベンゼン、ｌ、３−ビス（コーヒドロ
キシー／−エチルエトキシ）ベンゼン、１，、７−ビス
（２−ヒドロキシーコーエチルエトキシ）ベンゼン、ｌ
、３−ビス（２−ヒドロキシ−１，！−ジメチルエトキ
シ）ベンゼン、７．３−ビス（２−ヒドロキシ−ｉ、ｉ
、−ジメチルエトキシ）ベンゼン、ｌ、３−ビス（２−
ヒドロキシ−１，２．２−トリメチルエトキシ）ベンゼ
ン、ｌ、３−ビス（２−ヒドロキシ−１，１，２．２−
テトラメチルエトキシ）ベンゼン、ｌ、３−ビス（２−
ヒドロキシ−１，／−ジエチルエトキシ）ベンゼン、１
，３−ビス（２−ヒドロキシ−２、コージエチルエトキ
シ）ベンゼン、１，３−ビス（コーヒドロキシーｌ−メ
チルー２−エチルエトキシ）ベンゼン、ｌ、３−ビス（
２−ヒドロキシ−７−プロピルエトキシ）ベンゼン、１
，３−ビス（２−ヒドロキシ−２−プロピルエトキシ）
ベンゼン、１，３−ビス（コーヒドロキシーコーベンジ
ルエトキシ）ベンゼン、ｌ、３−ビス（３−ヒドロキシ
プロポキシ）ベンゼン、ｌ、３−ビス（３−ヒドロキシ
−３−７エニルプロポキシ）ベンゼン等が挙げられる。A specific example of the diol represented by the general formula (2) containing R3゜R4 is It''i, 1,J-bis(2-
hydroxyethoxy)benzene, l,3-bis(2-hydroxy-/-chloroethoxy)benzene-1,3-bis(2-hydroxy-1,/-dichloroethoxy)benzene, 1,J-bis(2-hydroxy -1-methylethoxy)benzene, l,3-bis(2-hydroxy-comethylethoxy)benzene, l,3-bis(cohydroxy-/-ethylethoxy)benzene, 1,,7-bis(2-hydroxy-comethylethoxy)benzene, Ceccoethyl ethoxy)benzene, l
, 3-bis(2-hydroxy-1,!-dimethylethoxy)benzene, 7.3-bis(2-hydroxy-i,i
, -dimethylethoxy)benzene, l,3-bis(2-
hydroxy-1,2.2-trimethylethoxy)benzene, l,3-bis(2-hydroxy-1,1,2.2-
tetramethylethoxy)benzene, l,3-bis(2-
Hydroxy-1,/-diethyl ethoxy)benzene, 1
,3-bis(2-hydroxy-2,codiethylethoxy)benzene, 1,3-bis(cohydroxy-l-methyl-2-ethylethoxy)benzene, l,3-bis(
2-hydroxy-7-propylethoxy)benzene, 1
,3-bis(2-hydroxy-2-propylethoxy)
Benzene, 1,3-bis(cohydroxy-cobenzylethoxy)benzene, 1,3-bis(3-hydroxypropoxy)benzene, 1,3-bis(3-hydroxy-3-7enylpropoxy)benzene, etc. It will be done.
（ロ）芳香族基であるフェニレン基でありて、その水素
原子は、炭素数／ −％のアルキル基。(b) A phenylene group which is an aromatic group, the hydrogen atoms of which are an alkyl group having carbon number/-%.
水酸基、ハロゲン等で置換されていてもよい。It may be substituted with hydroxyl group, halogen, etc.
このよりなＲ３、Ｒ４を含む一般式（２）の具体例とし
ては、ｌ、３−ビス（０−ヒドロキシメチルフェノキン
）ベンゼン、ｌ、３−ビス（ｐ−ヒドロキシメチルフェ
ノキシ）ベンゼン、１，３−ビス（ｍ−ヒドロキシメチ
ルフェノキシ）ベンゼン等が挙げられる。Specific examples of general formula (2) containing R3 and R4 include l,3-bis(0-hydroxymethylphenoquine)benzene, l,3-bis(p-hydroxymethylphenoxy)benzene, 1, Examples include 3-bis(m-hydroxymethylphenoxy)benzene.
（ハ）更に上記の（イ）と（ロ）を同時に満足するＲ３
、 Ｒ４も使用できる。このようなＲ３，Ｒ４を含む
一般式（２）の具体例としては１．３−ビス（ｐ−オキ
シベンジルオキシ）ベンゼン％１．３−ビス（０−オキ
シベンジルオキシ）ベンゼン等が挙げられる。(c) Furthermore, R3 satisfies the above (a) and (b) at the same time.
, R4 can also be used. Specific examples of general formula (2) containing such R3 and R4 include 1.3-bis(p-oxybenzyloxy)benzene%1.3-bis(0-oxybenzyloxy)benzene.
これら０）（ロ）（ハ）に例示した化合物は、ｌ、３−
鉢体であるがノ、−一または、１，Ｊ−フェニル核置換
異性体も同様に用いることができる。更に。The compounds exemplified in 0)(b)(c) are l, 3-
Substituted isomers of phenyl, -1, or 1,J-phenyl can be used as well. Furthermore.
−数式（２）において−中心となるフェニル核にはアル
キル基が置換されていてもよい。たとえば。- In formula (2) - the central phenyl nucleus may be substituted with an alkyl group. for example.
ｌ、３−ビス（λ−ヒドロキシエトキシ）−タ〜メチル
ベンゼン１，４ｔ−ビス（０−ヒドロキシメチルフェノ
キシ）−３−エチルベンゼンナトモ同様に用いることが
できる。l,3-bis(λ-hydroxyethoxy)-t-methylbenzene 1,4t-bis(0-hydroxymethylphenoxy)-3-ethylbenzene can be used in the same manner.
イソフタル酸および一般式（１）で示されるジカルボン
酸は、そのまま遊離酸の形で使用することもできるが水
酸基と反応してエステルを形成するエステル形成性誘導
体１例えばモノエステル、ジエステル等のエステル化物
、酸クロライド等の酸ハロゲン化物の形で用いてもよい
。Isophthalic acid and the dicarboxylic acid represented by the general formula (1) can be used as they are in the form of free acids, but they can also be used as ester-forming derivatives 1 that react with hydroxyl groups to form esters, such as esterified products such as monoesters and diesters. It may also be used in the form of acid halides such as acid chlorides.
また、一般式（２）で示されるジオール成分は。Moreover, the diol component represented by general formula (2) is.
全ジオール成分に対して少くとも３モルチ以上、好まし
くは３〜ｇθモルチ、更に好ましくはｇ〜６０モルチ使
用される。It is used in an amount of at least 3 molti or more, preferably 3 to gθ molti, and more preferably g to 60 molti based on the total diol component.
一般式（２）以外のジオール成分としては、エチレング
リコール、トリメチレンクリコール、テトラメチレング
リコール、ペンタメチレングリコール、ヘキサメチレン
グリコール、ネオペンチルグリコール、シクロヘキサン
ジメタツール。Diol components other than general formula (2) include ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, and cyclohexane dimetatool.
ジエチレングリコールや更には、ビスフェノールＡ、ビ
スフェノールＳ等の芳香族ジヒドロキシ化合物誘導体等
を挙げることができる。これらのうちエチレングリコー
ルが最も好ましい。Examples include diethylene glycol and aromatic dihydroxy compound derivatives such as bisphenol A and bisphenol S. Among these, ethylene glycol is most preferred.
これらのうちジオール成分は、前述の条件を満たしてい
る限り数種類を併用することもできる。Among these, several kinds of diol components can be used in combination as long as the above-mentioned conditions are satisfied.
また、本発明の共重合ポリエステルは実質的に線状を維
持する限り、トリメチロールプロパン、ペンタエリスリ
トール、グリセリン、トリの単官能化合物を共重合させ
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モルチ以下の範囲で使用される。Further, the copolymerized polyester of the present invention may be copolymerized with a monofunctional compound of trimethylolpropane, pentaerythritol, glycerin, or tri, as long as it maintains a substantially linear shape. Such polyfunctional compounds and monofunctional compounds are used in an amount of 20 moles or less of the diol component.
本発明の共重合ポリエステルは、重合反応終了后、反応
缶から抜出し、チップに切断する際や、その後の射出、
押出し、ブロー成形時の成形性の観点から、その溶融体
の粘度を、ある水準以上に保持する必要があるし、更に
は、瓶、たる、缶等の容器やフィルム、シート等の成形
体とした際に、実用に耐える物性を有する必要がある事
から、その極限粘度〔フェノール／テトラクロロエタン
（重量比／ ７ ｌ）の混合溶媒を用いて３０℃で測定
した値〕が、通常、０．９以上、２以下、好ましくは、
０．５ｓ以上、１，２以下のものが使用される。The copolymerized polyester of the present invention can be extracted from the reaction vessel after the polymerization reaction is completed and cut into chips, or during subsequent injection.
From the viewpoint of formability during extrusion and blow molding, it is necessary to maintain the viscosity of the melt above a certain level, and furthermore, it is necessary to maintain the viscosity of the melt at a certain level or higher, and furthermore, it is necessary to maintain the viscosity of the melt at a certain level or higher. Because it is necessary to have physical properties that can withstand practical use, the intrinsic viscosity [value measured at 30°C using a mixed solvent of phenol/tetrachloroethane (weight ratio/7 liters)] is usually 0. 9 or more, 2 or less, preferably
A length of 0.5 seconds or more and 1.2 seconds or less is used.
かかる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方法で製造することができ
る。例えば、インフタル酸と一般式（１）のジカルボン
酸、具体的には＋ ２．２’−ジオキシ酢酸、一般式（
２）のジオール、具体的には、１，３−ビス（２−ヒド
ロキシエトキシ）ベンゼン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、得られた反応物
を更に重縮合することで製造できる。Such a copolyester can be produced by a conventionally known method for polyethylene terephthalate. For example, inphthalic acid and dicarboxylic acid of general formula (1), specifically +2,2'-dioxyacetic acid, general formula (
2) Diol, specifically, transesterification using 1,3-bis(2-hydroxyethoxy)benzene and hyethylene glycol, followed by further polycondensation of the resulting reaction product. can.
一般式（１）のジカルボン酸及びそのエステル形成性誘
導体、ならびに一般式（２）のジオールは、エステル化
またはエステル交換反応の初期から加えてもよいし、エ
ステル化または、エステル交換反応終了后あるいは、更
に重縮合時の任意の段階で加える事も可能である。これ
らのエステル化、エステル交換及び重縮合反応の際には
。The dicarboxylic acid of general formula (1) and its ester-forming derivative, and the diol of general formula (2) may be added at the beginning of the esterification or transesterification reaction, or after the completion of the esterification or transesterification reaction. , it is also possible to add it at any stage during polycondensation. During these esterification, transesterification and polycondensation reactions.
エステル化触媒、エステル交換触媒、重縮合触媒および
安定剤等を使用するのが良い。It is preferable to use esterification catalysts, transesterification catalysts, polycondensation catalysts, stabilizers, and the like.
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、亜鉛及びナトリウム、リチウム化
合物等の７種以上を用いることができるが、透明性の点
からマンガン化合物が特に好ましい。As the transesterification catalyst, seven or more known compounds such as calcium, manganese, zinc and sodium, and lithium compounds can be used, but manganese compounds are particularly preferred from the viewpoint of transparency.
重合触媒としては、公知のアンチモン、ゲルマニウム、
チタン及びコバルト化合物等の７種以上を用いることが
できるが、好ましくは、アンチモン、ゲルマニウム及び
チタン化合物が用いられる。As the polymerization catalyst, known antimony, germanium,
Seven or more types of titanium and cobalt compounds can be used, but antimony, germanium and titanium compounds are preferably used.
また本発明では、必要に厄、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れかの段階で添加してもよく、
成形刃ロエ前に、いわゆるマスターバッチ処決で添加し
ても良い。In addition, in the present invention, if necessary, conventionally known additives, such as antioxidants, ultraviolet absorbers, fluorescent brighteners,
Mold release agents, antistatic agents, dispersants, and colorants such as dyes and pigments may be added at any stage during polyester production.
It may be added in a so-called masterbatch process before forming the molding blade.
本発明の共重合ポリエステルは、必要に厄じて更に、固
相重合処理を実施し、高重合度化、低アセトアルデヒド
化あるいは、低オリゴマー化してから使用してもよい。If necessary, the copolymerized polyester of the present invention may be further subjected to a solid phase polymerization treatment to increase the degree of polymerization, reduce acetaldehyde, or reduce oligomerization before use.
固相重合処理は、通常、ｇＯ〜／ １０℃の温度でチッ
プ表面を結晶化した後、１９０℃〜融点直下の温度で数
十時間以下の範囲内に於て実施するのが好ましい。The solid phase polymerization treatment is usually preferably carried out at a temperature of 190°C to just below the melting point for several tens of hours or less after crystallizing the chip surface at a temperature of gO to /10°C.
かくして得られた本発明の共重合ポリエステルは溶融成
形して成形品とされる。The thus obtained copolymerized polyester of the present invention is melt-molded into a molded article.
具体的には、ポリエチレンテレフタレート（ＰＥＴ）、
ポリブチレンテレフタレート、ポリエチレンナフタレー
ト、ポリエステルエラストマー、ポリカーボネートやナ
イロン６、ナイロン６６、メタキシリレンジアミンアジ
パミドのようなポリアミド等の他の熱可塑性樹脂成分と
、本発明の共重合ポリエステルをブレンドして、一体構
造に形成することが可能であるし、更には、ポリエチレ
ンテレフタレート成分や上記のような熱可塑性樹脂成分
と１本発明の共重合ポリエステル成分とを多層構造に成
形することもできる。Specifically, polyethylene terephthalate (PET),
The copolymerized polyester of the present invention is blended with other thermoplastic resin components such as polybutylene terephthalate, polyethylene naphthalate, polyester elastomer, polycarbonate, and polyamides such as nylon 6, nylon 66, and metaxylylene diamine adipamide. It is possible to form a monolithic structure, and furthermore, a polyethylene terephthalate component or a thermoplastic resin component as described above and a copolyester component of the present invention can be formed into a multilayer structure.
この際、ポリエチレンテレフタレート等の成形において
一般的に使用される溶融成形法の全てが適用可能である
。At this time, all melt molding methods commonly used in molding polyethylene terephthalate and the like can be applied.
具体的には１例えば、中空成形体を得るには通常の押出
吹込み法、射出吹込み法、射出成形又は押出成形で一旦
、予備成形体を成形し、そのま＼で、あるいは、口栓部
、底部を加工後それを再加熱し、二軸延伸するホットパ
リソン法あるいはコールドパリンン法等の吹込成形法が
適用される。Specifically, 1. For example, in order to obtain a hollow molded body, a preformed body is first formed by the usual extrusion blowing method, injection blowing method, injection molding, or extrusion molding, and then it can be used as it is or with a spout. A blow molding method such as a hot parison method or a cold parison method, in which the top and bottom parts are processed and then reheated and biaxially stretched, is applied.
また多層容器の場合も、従来のポリエチレンテレフタレ
ート等の成形方法に準じて製造することができる。すな
わち１通常の射出成形機又は、複数個の射出装量を有す
る射出成形機により成形された多層パリソンまたは、多
層押出成形機により成形された多層パリソンの一端を有
底化して得られた多層パリソンを、控えは、１３−１３
０℃のＰＥＴの延伸温度で延伸する方法で製造可能であ
る。Also, in the case of a multilayer container, it can be manufactured according to a conventional molding method for polyethylene terephthalate or the like. Namely, 1. A multilayer parison molded by a normal injection molding machine or an injection molding machine having a plurality of injection loadings, or a multilayer parison obtained by bottoming one end of a multilayer parison molded by a multilayer extrusion molding machine. , the reserve is 13-13
It can be produced by stretching at a PET stretching temperature of 0°C.
本発明の共重合ポリエステルを多層容器に形成する場合
、その層形成に特に限定はなく、また層の数も何ら限定
はないが、３〜５層程度の構成が好ましい。When forming a multilayer container from the copolymerized polyester of the present invention, there is no particular limitation on the layer formation, and there is also no limitation on the number of layers, but a configuration of about 3 to 5 layers is preferred.
また射出成形によりシート化した後、−軸または二軸延
伸フィルムとしたり、真空成形あるいは、圧空成形によ
り缶状の容器やトレイ等に成形することもできるし、多
層押出成形機により、例えば、ポリエチレンテレフタレ
ートとの多層シートとし、同様に、−軸、二軸延伸フィ
ルムや缶状容器、トレイに成形することも可能である。In addition, after forming a sheet by injection molding, it can be made into a -axially or biaxially stretched film, or it can be formed into a can-shaped container or tray by vacuum forming or pressure forming. It is also possible to form a multilayer sheet with terephthalate into a -axially or biaxially stretched film, a can-shaped container, or a tray.
本発明の共重合ポリエステルと、上記の各種ポリマーを
ブレンドして包装材料を形成する場合には、両成分な押
出機で溶融混練して混合チップを得、次いでこれを成形
に供することもできるし、また、それぞれの成分をトラ
イブレンドし、直接成形に供することも可能である。When a packaging material is formed by blending the copolyester of the present invention with the various polymers mentioned above, it is also possible to melt and knead both components in an extruder to obtain mixed chips, which can then be subjected to molding. It is also possible to tri-blend each component and directly mold it.
本発明の対象とするかかる成形品としては。Such molded products that are the object of the present invention include:
具体的には、瓶、たる１缶等の容器や未延伸シートを深
絞り成形して得られる容器、更にはシートを真空または
圧空成形して得られるトレイ等の容器が挙げられる。Specific examples include containers such as bottles and barrels, containers obtained by deep drawing an unstretched sheet, and containers such as trays obtained by vacuum or pressure forming a sheet.
本発明の共重合ポリエステルはそれ自体高透明性を示し
、すぐれた耐ガス透過性を有する。The copolyester of the present invention itself exhibits high transparency and has excellent gas permeation resistance.
本発明の共重合ポリエステルは包装材料として有用であ
り、他の熱可塑性樹脂とのブレンドあるいは積層体とし
て容器、シート、フィルム等に広く利用することができ
る。特に、ポリエチレンテレフタレート成分とのブレン
ドあるいは積層体は−ガス透過性が低いうえ、高透明性
を保持する為、きわめて有利に利用することができる。The copolyester of the present invention is useful as a packaging material, and can be widely used in containers, sheets, films, etc. as a blend or laminate with other thermoplastic resins. In particular, blends or laminates with polyethylene terephthalate components have low gas permeability and maintain high transparency, so they can be used very advantageously.
また、塩化ビニリデンやエチレン−酢酸ビニル共重合ケ
ン化物のような耐ガス透過性素材との併用も可能である
。Further, it is also possible to use it in combination with gas permeable materials such as vinylidene chloride and saponified ethylene-vinyl acetate copolymer.
以下、実施例により本発明を更に詳細に説明するが、本
発明はその要旨を越えない限り以下の実施例に限定され
るものではない。Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded.
なお、実施例中「部」は「重量部」を意味するものとし
、本実施例で使用した種々の測定法を以下に示す。Note that "parts" in the examples mean "parts by weight," and various measuring 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（ＳＯ／ｓｏ重量比）
中＋ ＳＯ℃で測定した。0 Intrinsic viscosity phenol-tetrachloroethane (SO/so weight ratio)
Measured at medium+SO°C.
Ｏ酸素透過率
約２０θμ肉厚の押出シートサンプルを作成し、２３℃
、ｉｏｏチＲＨの条件下。An extruded sheet sample with an O oxygen permeability of approximately 20θμ wall thickness was prepared and heated at 23°C.
, ioochi RH conditions.
ｒ ０Ｘ−ＴＲＡＮ １０／ｓｏ Ａ Ｊ酸素透過率測
定装置（米国Ｍｏｄｅｒｎ Ｃｏｎｔｒｏｌｓ社製）で
測定し、ＣＣ−０部ｍ２・ｄａｙ−ａｔｍで示した。r 0X-TRAN 10/so AJ It was measured with an oxygen permeability measuring device (manufactured by Modern Controls, Inc., USA) and expressed in CC-0 parts m2·day-atm.
Ｏ共重合ポリエステルの組成
トリフルオロ酢酸溶媒を用いて核磁気共鳴スペクトルか
ら求めた。Composition of O copolymerized polyester was determined from nuclear magnetic resonance spectrum using trifluoroacetic acid solvent.
実施例１
インフタル酸／Ａ、０００部、エチレングリコール６．
０００部−２，２′−オキシジ酢酸１，２ｇＱ部、１．
３−ビス（２−ヒドロキシエトキシ）ベンゼン３，２０
０部を反応槽に仕込み、窒素雰囲気加圧（２，ｓ ｋｇ
／ ｃｒｄ ）下、攪拌しつつ、２３０〜２ダ５℃で
３時間、エステル化反応を行い、この間生成する水を系
外へ留去した。Example 1 Inphthalic acid/A, 000 parts, ethylene glycol 6.
000 parts - 1.2 g Q parts of 2,2'-oxydiacetic acid, 1.
3-bis(2-hydroxyethoxy)benzene 3,20
0 part was charged into a reaction tank and pressurized with nitrogen atmosphere (2, s kg
/crd), the esterification reaction was carried out at 230 to 2°C for 3 hours while stirring at 5°C, and the water produced during this time was distilled out of the system.
このエステル化物に、チタンテトラブトキシド／６部を
加え、重合槽内は、常圧より漸次減圧にするとともに、
徐々に昇湿し、２６０℃、／ ｔｏｒｒ の真空下、
全重合時間Ｓ時間で、極限粘度０．６ｇの透明ポリエス
テルを得た。6 parts of titanium tetrabutoxide was added to this esterified product, and the pressure inside the polymerization tank was gradually reduced from normal pressure.
Gradually increase the humidity, 260℃, /torr vacuum,
A transparent polyester having an intrinsic viscosity of 0.6 g was obtained for a total polymerization time of S hours.
このポリエステルの２０ｇμ押出シートで測定した酸素
ガス透過率を表／に示した。The oxygen gas permeability measured on a 20 gμ extruded sheet of this polyester is shown in Table 1.
実施例λ
イソフタル酸ジメチルエステル／ ３，０００ 部、エ
チレングリコール／１，０部０部及び酢酸マンガン・ダ
水塩ｑ部を反応缶に加え、ｉｂｏ℃から２３０Ｃまで漸
次昇温しで留出液が出なくなるまでエステル交換反応を
行った。Example λ 3,000 parts of isophthalic acid dimethyl ester, 1,0 parts of ethylene glycol, and q parts of manganese acetate dahydrate were added to a reaction vessel, and the temperature was gradually raised from ibo°C to 230°C to form a distillate. The transesterification reaction was carried out until no more was produced.
この系に、 ２．２’−イミノジ酢酸２，１−００ ｍ
、７．３−ビス（２−ヒドロキシエトキシ）ベンゼンｓ
、ｑ ｏ ｏ部、ニリン酸コ、７部及び二酸化ゲルマニ
ウム２．０部を加え、実施例１と同様にして、全重合時
間ダ時間で、極限粘度０．７０の透明ポリエステルを得
た。To this system, 2,2'-iminodiacetic acid 2,1-00 m
, 7.3-bis(2-hydroxyethoxy)benzene
, q o parts, 7 parts of diphosphoric acid, and 2.0 parts of germanium dioxide were added, and in the same manner as in Example 1, a transparent polyester having an intrinsic viscosity of 0.70 was obtained in a total polymerization time of d hours.
このポリエステルの２０Ｓμ押出シートで測定した酸素
ガス透過率を表１に示した。Table 1 shows the oxygen gas permeability measured using the 20Sμ extruded sheet of this polyester.
実施例３
実施例１で得たコポリエステル３．ｏｏｏｍと市販の炭
酸飲料用ポリエチレンテレフタレート樹脂７，０００部
をトライブレンドし、実施例１と同様に操作して２２０
μシートを得た。Example 3 Copolyester obtained in Example 13. ooom and 7,000 parts of a commercially available polyethylene terephthalate resin for carbonated drinks were triblended, and the same procedure as in Example 1 was carried out to obtain 220 parts.
A μ sheet was obtained.
このシートをロング延伸機にかけ、槽内温度ｑｏｃで、
７Ｘ、７倍に同時コ軸延伸した。This sheet was put through a long stretching machine, and the temperature inside the tank was set at qoc.
Simultaneous coaxial stretching was carried out 7X and 7 times.
この延伸フィルムの酸素透過率は、１，Ｏｃｃ・−／イ
・ｄａｙ・ａｔｍで、同じ条件下で延伸作製したＰＥＴ
単体延伸フィルムの曇の値を示した。The oxygen permeability of this stretched film was 1, Occ・-/I・day・atm, and the PET produced by stretching under the same conditions
The haze value of a single stretched film is shown.
実施例ｑ
コ、２′−オキシジ酢酸１，２ｇθ部、ｌ、３−ビス（
２−ヒドロキシエトキシ）ベンゼン３，１００部の代わ
りに、２．２′−オキシジ酢酸３．／コθ部、ｌ、ター
ビス（２−ヒドロキシエトキシ）ベンゼン３，２００部
を用いた以外は、実施例１と同様にして極限粘度０．６
ｇの透明ポリエステルを得た。このポリエステルの２９
ｇμ押出シートで測定した酸素ガス透過率を表７に示し
た。Example q 1,2 g θ parts of co,2'-oxydiacetic acid, l,3-bis(
3.2'-oxydiacetic acid instead of 3,100 parts of 2-hydroxyethoxy)benzene. The intrinsic viscosity was 0.6 in the same manner as in Example 1, except that 3,200 parts of terbis(2-hydroxyethoxy)benzene was used.
A transparent polyester of g was obtained. 29 of this polyester
Table 7 shows the oxygen gas permeability measured with the gμ extruded sheet.
実施例５
２．２′−オキシジ酢酸１，２ ｇ Ｑ部の代わりに、
３．３′−オキシジブロビオ、ン酸’７２！θ部を用い
た以外は、実施例１と同様にして極限粘度０．６９の透
明ポリエステルを得た。このポリエステルの２０１μ押
出シートで測定した酸素ガス透過率を表７に示した。Example 5 2.2'-oxydiacetic acid 1,2 g Instead of part Q,
3.3'-Oxydibrobionic acid '72! A transparent polyester having an intrinsic viscosity of 0.69 was obtained in the same manner as in Example 1 except that the θ portion was used. Table 7 shows the oxygen gas permeability measured on the 201μ extruded sheet of this polyester.
比較例１
コ、２′−オキシジ酢酸１，２ Ｋ ０部を１，４（９
０部として、ｌ、３−ビス（２−ヒドロキシエトキシ）
ベンゼンを用いなかった以外は実施例１と同様にして行
った。得られたポリエステルの２０ｇμ押出シートで測
定した酸素ガス透過率を表７に示した。Comparative Example 1 0 parts of 1,2 K of 2'-oxydiacetic acid were mixed with 1,4 (9
0 parts as l,3-bis(2-hydroxyethoxy)
The same procedure as in Example 1 was carried out except that benzene was not used. Table 7 shows the oxygen gas permeability measured on the 20 gμ extruded sheet of the obtained polyester.
比較例λ
イソフタル６１ｔ、、ｏｏｏ部、エチレングリコール７
．２００部を反応槽に仕込み、窒素雰囲気加圧（ｓ、ｓ
’ｑｌ／ｃｕｒ ）下、攪拌しつつ、２ＪＯ〜２＆ｊ
℃で３時間、エステル化反応、を行い、この間生成する
水を系外へ留去した。Comparative example λ Isophthal 61t, ooo part, ethylene glycol 7
．． 200 parts were charged into a reaction tank and pressurized with nitrogen atmosphere (s, s
'ql/cur), while stirring, 2JO~2&j
The esterification reaction was carried out at ℃ for 3 hours, and the water produced during this time was distilled out of the system.
このエステル化物に、チタンテトラブトキシド７６部を
加え１重合槽内は、常圧より漸次減圧にするとともに、
徐々に昇温し、２１．０℃、／ ｔｏｒｒ の真空下
、全重合時間５時間で、極限粘度０．７０の透明ポリエ
ステルを得た。76 parts of titanium tetrabutoxide was added to this esterified product, and the pressure inside the polymerization tank was gradually reduced from normal pressure.
A transparent polyester having an intrinsic viscosity of 0.70 was obtained by gradually raising the temperature to 21.0° C. under a vacuum of /torr for a total polymerization time of 5 hours.
このポリエステルの２０ｇμ押出シートで測定した酸素
ガス透過率を表１に示した。Table 1 shows the oxygen gas permeability measured on a 20 gμ extruded sheet of this polyester.
Claims (4)
なる共重合ポリエステルにおいて、ジカルボン酸成分の
主成分がイソフタル酸またはそのエステル形成性誘導体
であり、他の成分として一般式（１） ＨＯＯＣ−Ｒ＾１−Ｘ−Ｒ＾２−ＣＯＯＨ………（１）
（式中、Ｒ＾１、Ｒ＾２は同一でも異っていてもよく、
２価の脂肪族基を表わす。ＸはＯまたはＮＨを表わす。 ） で示されるジカルボン酸またはそのエステル形成性誘導
体を全ジカルボン酸成分に対して１〜５０モル％を含み
、全ジオール成分の少くとも３モル％が一般式（２） ▲数式、化学式、表等があります▼……（２） （式中、Ｒ＾３、Ｒ＾４は同一でも異っていてもよく、
２価の脂肪族基または芳香族基を表わす。）で示される
ジオールであることを特徴とする共重合ポリエステル。(1) In a copolyester formed by condensing a dicarboxylic acid component and a diol component, the main component of the dicarboxylic acid component is isophthalic acid or its ester-forming derivative, and other components include general formula (1) HOOC-R ^1-X-R^2-COOH……(1)
(In the formula, R^1 and R^2 may be the same or different,
Represents a divalent aliphatic group. X represents O or NH. ) Contains 1 to 50 mol % of the dicarboxylic acid or its ester-forming derivative represented by the formula (2) based on the total dicarboxylic acid components, and at least 3 mol % of the total diol component is represented by the general formula (2) ▲ Numerical formula, chemical formula, table, etc. There is▼...(2) (In the formula, R^3 and R^4 may be the same or different,
Represents a divalent aliphatic group or an aromatic group. ) A copolymerized polyester characterized by being a diol represented by:
量比１／１）の混合溶媒を用いて３０℃で測定した値〕
が０．４〜２であることを特徴とする特許請求の範囲第
１項記載の共重合ポリエステル。(2) Intrinsic viscosity [value measured at 30°C using a mixed solvent of phenol/tetrachloroethane (weight ratio 1/1)]
The copolymerized polyester according to claim 1, characterized in that 0.4 to 2.
′−オキシジ酢酸または２，２′−イミノジ酢酸である
ことを特徴とする特許請求の範囲第１項記載の共重合ポ
リエステル。(3) The dicarboxylic acid represented by the general formula (1) is 2,2
The copolymerized polyester according to claim 1, wherein the copolymerized polyester is '-oxydiacetic acid or 2,2'-iminodiacetic acid.
ス（２−ヒドロキシエトキシ）ベンゼンであることを特
徴とする特許請求の範囲第１項記載の共重合ポリエステ
ル。(4) The copolymerized polyester according to claim 1, wherein the diol represented by the general formula (2) is 1,3-bis(2-hydroxyethoxy)benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32925087A JP2605767B2 (en) | 1987-12-25 | 1987-12-25 | Copolyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32925087A JP2605767B2 (en) | 1987-12-25 | 1987-12-25 | Copolyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01170619A true JPH01170619A (en) | 1989-07-05 |
| JP2605767B2 JP2605767B2 (en) | 1997-04-30 |
Family
ID=18219339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32925087A Expired - Fee Related JP2605767B2 (en) | 1987-12-25 | 1987-12-25 | Copolyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2605767B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0459822A (en) * | 1990-06-29 | 1992-02-26 | Polyplastics Co | Molding polyester resin having high melt thermal stability and its molded article |
| JPH04261423A (en) * | 1990-12-28 | 1992-09-17 | Polyplastics Co | Polyester resin excellent in stability to heat of molding and molding thereof |
| WO2001032738A1 (en) * | 1999-11-04 | 2001-05-10 | Eastman Chemical Company | Poly(hydroxy ester ethers) as barrier resins |
-
1987
- 1987-12-25 JP JP32925087A patent/JP2605767B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0459822A (en) * | 1990-06-29 | 1992-02-26 | Polyplastics Co | Molding polyester resin having high melt thermal stability and its molded article |
| JPH04261423A (en) * | 1990-12-28 | 1992-09-17 | Polyplastics Co | Polyester resin excellent in stability to heat of molding and molding thereof |
| WO2001032738A1 (en) * | 1999-11-04 | 2001-05-10 | Eastman Chemical Company | Poly(hydroxy ester ethers) as barrier resins |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2605767B2 (en) | 1997-04-30 |
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