JPH0524815B2 - - Google Patents
Info
- Publication number
- JPH0524815B2 JPH0524815B2 JP21794785A JP21794785A JPH0524815B2 JP H0524815 B2 JPH0524815 B2 JP H0524815B2 JP 21794785 A JP21794785 A JP 21794785A JP 21794785 A JP21794785 A JP 21794785A JP H0524815 B2 JPH0524815 B2 JP H0524815B2
- Authority
- JP
- Japan
- Prior art keywords
- bottle
- layer
- polyethylene terephthalate
- composition
- thermoplastic polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 34
- -1 polyethylene terephthalate Polymers 0.000 claims description 27
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 21
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 21
- 239000001569 carbon dioxide Substances 0.000 claims description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 17
- 229920000728 polyester Polymers 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 229920001169 thermoplastic Polymers 0.000 claims description 7
- 230000035699 permeability Effects 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-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
- 239000002253 acid Substances 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- RQXXCWHCUOJQGR-UHFFFAOYSA-N 1,1-dichlorohexane Chemical compound CCCCCC(Cl)Cl RQXXCWHCUOJQGR-UHFFFAOYSA-N 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- DWKNOLCXIFYNFV-HSZRJFAPSA-N 2-[[(2r)-1-[1-[(4-chloro-3-methylphenyl)methyl]piperidin-4-yl]-5-oxopyrrolidine-2-carbonyl]amino]-n,n,6-trimethylpyridine-4-carboxamide Chemical compound CN(C)C(=O)C1=CC(C)=NC(NC(=O)[C@@H]2N(C(=O)CC2)C2CCN(CC=3C=C(C)C(Cl)=CC=3)CC2)=C1 DWKNOLCXIFYNFV-HSZRJFAPSA-N 0.000 description 1
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 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
- ARVXKJTZQNPREM-UHFFFAOYSA-N [4-(2-hydroxyethoxy)phenyl] 4-(2-hydroxyethoxy)benzenesulfonate Chemical compound C1=CC(OCCO)=CC=C1OS(=O)(=O)C1=CC=C(OCCO)C=C1 ARVXKJTZQNPREM-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material 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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
Landscapes
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Laminated Bodies (AREA)
Description
〔産業上の利用分野〕
本発明はポリエステルボトル及びその製造法に
関し、更に詳しくはガスバリア性特に炭酸ガスバ
リア性が良好でかつ耐落下衝撃性に優れ、殊に食
品ないし飲料用途に有用な二軸延伸ポリエステル
ボトル及びその製造法に関する。
〔従来技術〕
従来から、二軸延伸ポリエチレンテレフタレー
トボトルは機械的強度、ガスバリア性、透明性、
耐薬品性等に優れた特性を有することから、飲料
用、食品用或いは化粧品用等の容器として使用さ
れている。
しかし、このボトルの特性も使用態様によつて
は十分とは云えず、例えば炭酸飲料或いはビール
を充填した場合、保存期間が長期に及ぶと内容液
中の炭酸ガスが徐々に逃げて商品価値を損うこと
になり、その使用分野が制限される。
そこで、二軸延伸ポリエステルボトルの特性向
上、特に炭酸ガスバリア性向上が研究され、種々
の提案がされている。
炭酸ガスバリア性の改良方法としては、例えば
ガスバリア性の良好なポリマーとポリエチレンテ
レフタレートとを積層化せしめる方法(特開昭60
−89326号等)、ポリエチレンテレフタレートにガ
スバリア性の良好なポリマーを混合せしめる方法
(特開昭60−76325号等)などが提案されている。
しかしながら、前者の積層ボトルは胴部における
ポリエチレンテレフタレート層とバリアポリマー
層との接着力が弱く、層剥離が発生したり、内圧
変形が大きい等の欠点があり、また接着層を介在
させるとそれだけ構造が複雑になるという欠点が
生じ、一方後者のボトルは底部の耐衝撃性が低
く、ボトルを落下させたときに底部が破損すると
いう欠点があり、いずれも実用上問題がある。
〔発明の目的〕
本発明の目的は、かかる問題を解消し、優れた
ガスバリア性特に炭酸ガスバリア性を有し、耐落
下衝撃、耐内圧変形等の特性に優れた二軸延伸ポ
リエステルボトル及びその製造法を提供すること
にある。
〔発明の構成・効果〕
本発明の目的は、本発明によれば、主たる特徴
の、ボトルの口部ないし胴部がポリエチレンテレ
フタレート95〜5重量%と30℃における炭酸ガス
透過係数が1.0×10-13〔c.c.・cm/cm2・sec・cmHg〕
以下の熱可塑性ポリマー5〜50重量部の組成物(イ)
からなり、かつ底部がポリエチレンテレフタレー
トから、或は組成物(イ)の層()とポリエチレン
テレフタレートまたは該熱可塑性ポリマーを胴部
の組成物(イ)より低い割合でポリエチレンテレフタ
レートに混合してなる組成物(ロ)の層(ロ)とを少くと
も有する積層構造からなることを特徴とする二軸
延伸ポリエステルボトル、並びに該二軸延伸ポリ
エステルボトルを製造するに際し、有底プリフオ
ームとしてボトルの口部ないし胴部に相当する部
分が上記組成物(イ)からなり、かつ底部に相当する
部分がポリエチレンテレフタレートから、或は上
記層()と層()とを少くとも有する積層構
造からなる有底プリフオームを用いることを特徴
とする製造法によつて達成される。
本発明においてポリエチレンテレフタレート
は、そのホモポリマーは勿論のこと、テレフタル
酸成分の一部を例えばイソフタル酸、ナフタリン
ジカルボン酸、ジフエニルジカルボン酸、ジフエ
ノキシエタンジカルボン酸、ジフエニルエーテル
カルボン酸、ジフエニルスルホンジカルボン酸等
の如き芳香族ジカルボン酸;ヘキサヒドロテレフ
タル酸、ヘキサヒドロイソフタル酸等の如き脂環
族ジカルボン酸;アジピン酸、セバチン酸、アゼ
ライン酸等の如き脂肪族ジカルボン酸;P−β−
ヒドロキシエトキシ安息香酸、p−安息香酸、ε
−オキシカプロン酸等の如きオキシ酸等の他の二
官能性カルボン酸の1種以上の成分で、及び/又
はエチレングリコール成分の一部を例えばトリメ
チレングリコール、テトラメチレングリコール、
ヘキサメチレングリコール、デカメチレングリコ
ール、ネオペンチレングリコール、ジエチレング
リコール、1,1−ジクロヘキサンジメチロー
ル、1,4−シクロヘキサンジメチロール、2,
2−ビス(4−βーヒドロキシエトキシフエニ
ル)プロパン、ビス(4−β−ヒドロキシエトキ
シフエニル)スルホン酸の他のグリコールの1種
以上の成分で置換したコポリエステルを包含す
る。該コポリエステル中の共重合成分の総割合は
全酸成分に対し2モル%以下であることが好まし
い。これらのうちポリエチレンテレフタレートの
ホモポリマーが好ましい。またポリエチレンテレ
フタレートは0.6以上の固有粘度(o−クロロフ
エノール、35℃)を有することが好ましい。
本発明においてかかるポリエチレンテレフタレ
ートと混合使用する熱可塑性ポリマーは30℃にお
ける炭酸ガス透過係数(Pco2)が1.0×10-13
〔c.c.・cm/cm2・sec・cmHg〕以下である必要があ
り、具体的にはエチレン−酢酸ビニル共重合体を
ケン化して得られるエチレン−ビニルアルコール
共重合体(以下、EVOHと略すことあり)の如
きオレフイン−ビニルアルコール共重合体、メタ
キシリレンジアミンとアジピン酸の重縮合体(以
下、PA−Mと略すことあり)の如きメタキシリ
レン基含有ポリアミド、ポリエチレンイソフタレ
ート(以下、PEIと略すことあり)等が例示され
る。これらは単独でも使用でき、また2種以上を
混合して使用することもできる。上記オレフイン
−ビニルアルコール共重合体は、成形性等の点か
ら、オレフイン含有量が10〜50モル%、特に20〜
45モル%のものが好ましく、またケン化度が90%
以上のものが好ましい。
かかる熱可塑性ポリマーのPco2〔c.c.・cm/cm2・
sec・cmHg〕を例示すると、下表の通りである。
なお、この表には参考としてポリエチレンテレフ
タレート(PET)のPco2も併記する。
[Industrial Field of Application] The present invention relates to a polyester bottle and a method for producing the same, and more specifically to a biaxially oriented polyester bottle that has good gas barrier properties, particularly carbon dioxide gas barrier properties, and excellent drop impact resistance, and is particularly useful for food and beverage applications. This article relates to polyester bottles and their manufacturing method. [Prior art] Biaxially oriented polyethylene terephthalate bottles have traditionally had mechanical strength, gas barrier properties, transparency,
Because it has excellent properties such as chemical resistance, it is used as containers for beverages, foods, cosmetics, etc. However, the characteristics of this bottle may not be sufficient depending on how it is used. For example, if the bottle is filled with carbonated beverages or beer, if it is stored for a long time, the carbon dioxide gas in the content will gradually escape and the product value will decrease. This limits its field of use. Therefore, research has been conducted to improve the properties of biaxially oriented polyester bottles, particularly the carbon dioxide gas barrier properties, and various proposals have been made. As a method for improving carbon dioxide gas barrier properties, for example, a method of laminating a polymer with good gas barrier properties and polyethylene terephthalate (Japanese Patent Application Laid-Open No. 1989-1999)
-89326, etc.), and a method in which a polymer with good gas barrier properties is mixed with polyethylene terephthalate (Japanese Patent Laid-Open No. 60-76325, etc.) have been proposed.
However, the former laminated bottle has drawbacks such as weak adhesion between the polyethylene terephthalate layer and the barrier polymer layer in the body, resulting in layer peeling and large internal pressure deformation. However, the bottom of the latter bottle has a disadvantage of being complicated, and the bottom of the latter bottle has a low impact resistance, which causes the bottom to break when the bottle is dropped, both of which pose practical problems. [Object of the Invention] The object of the present invention is to solve such problems and provide a biaxially stretched polyester bottle that has excellent gas barrier properties, particularly carbon dioxide barrier properties, and excellent properties such as drop impact resistance and internal pressure deformation resistance, and the production thereof. It is about providing law. [Configuration/Effects of the Invention] According to the present invention, the main feature of the present invention is that the mouth or body of the bottle is made of 95 to 5% by weight of polyethylene terephthalate and has a carbon dioxide gas permeability coefficient of 1.0×10 at 30°C. -13 [cc・cm/ cm2・sec・cmHg]
Composition (a) containing 5 to 50 parts by weight of the following thermoplastic polymer
and the bottom part is made of polyethylene terephthalate, or a composition made of a layer (a) of composition (a) and polyethylene terephthalate or the thermoplastic polymer mixed with polyethylene terephthalate in a lower proportion than the composition (a) of the body part. A biaxially oriented polyester bottle characterized by having a laminated structure having at least a layer (b) of the material (b), and when producing the biaxially oriented polyester bottle, the bottle mouth or A bottomed preform in which the part corresponding to the body is made of the composition (a) above, and the part corresponding to the bottom is made of polyethylene terephthalate or has a laminated structure having at least the above layers () and (). This is achieved by a manufacturing method characterized in that it is used. In the present invention, polyethylene terephthalate is not only a homopolymer, but also a part of the terephthalic acid component, such as isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenoxyethane dicarboxylic acid, diphenyl ether carboxylic acid, diphenyl dicarboxylic acid, etc. Aromatic dicarboxylic acids such as sulfonic acid; alicyclic dicarboxylic acids such as hexahydroterephthalic acid, hexahydroisophthalic acid, etc.; aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, etc.; P-β-
Hydroxyethoxybenzoic acid, p-benzoic acid, ε
- one or more components of other difunctional carboxylic acids such as oxyacids such as oxycaproic acid, and/or a portion of the ethylene glycol component, such as trimethylene glycol, tetramethylene glycol,
Hexamethylene glycol, decamethylene glycol, neopentylene glycol, diethylene glycol, 1,1-dichlorohexane dimethylol, 1,4-cyclohexane dimethylol, 2,
It includes copolyesters substituted with one or more components of other glycols such as 2-bis(4-β-hydroxyethoxyphenyl)propane and bis(4-β-hydroxyethoxyphenyl)sulfonic acid. The total proportion of copolymerized components in the copolyester is preferably 2 mol % or less based on the total acid components. Among these, a homopolymer of polyethylene terephthalate is preferred. Moreover, it is preferable that polyethylene terephthalate has an intrinsic viscosity (o-chlorophenol, 35° C.) of 0.6 or more. The thermoplastic polymer mixed with polyethylene terephthalate in the present invention has a carbon dioxide permeability coefficient (Pco 2 ) of 1.0×10 -13 at 30°C.
It must be less than [cc・cm/cm 2・sec・cmHg], and specifically, ethylene-vinyl alcohol copolymer (hereinafter abbreviated as EVOH) obtained by saponifying ethylene-vinyl acetate copolymer Olefin-vinyl alcohol copolymers such as olefin-vinyl alcohol copolymers such as olefin-vinyl alcohol copolymers, metaxylylene group-containing polyamides such as polycondensates of metaxylylene diamine and adipic acid (hereinafter sometimes abbreviated as PA-M), and polyethylene isophthalate (hereinafter abbreviated as PEI). example). These can be used alone or in combination of two or more. The above olefin-vinyl alcohol copolymer has an olefin content of 10 to 50 mol%, particularly 20 to 50 mol%, from the viewpoint of moldability etc.
45 mol% is preferable, and the degree of saponification is 90%.
The above are preferred. Pco 2 [cc・cm/cm 2・
sec・cmHg] is shown in the table below.
This table also includes Pco 2 of polyethylene terephthalate (PET) for reference.
以下、実施例により本発明を詳述する。なお主
な物性値の測定条件は次の通りである。
(1) 固有粘度〔〕:
o−クロロフエノールを溶媒として35℃で測
定。
(2) 炭酸ガス透過係数
スイスLyssy社製GPM−200型ガス透過率測
定機を用い、30℃雰囲気で炭酸ガス透過率を測
定。
(3) 耐落下衝撃性
ボトル内に水1000g及びクエン酸14gを充填
したのち、ポリエチレン製袋内に秤量してある
重炭酸ソーダ14gをボトル内のクエン酸水溶液
と直接混合しない状態でボトル口部内に挿入
し、直ちに、アルミニウム製キヤツプで打栓す
る。打栓後ボトル内に挿入した重炭酸ソーダと
クエン酸水溶液とが十分混り合う様ボトルを振
り混ぜる事により、CO2ガスを発生せしめて、
CO2ガスを加圧溶解せしめた水溶液がボトル内
に充填された状態とする。得られるCO2充填ボ
トルを5℃温度に保ち、24時間後にボトル底部
を下向きとし、1.8メートルの高さよりコンク
リート床面に落下させた際のボトル破裂割合を
調べる。この割合を破裂率〔%〕として表示す
る。
(4) 炭酸ガスバリア性
上記(3)の耐落下衝撃性の測定のときと同様に
してCO2ボトルを得る。但し、下記式で示され
るCO2 Volumeは4とする。このCO2充填ボト
ルを所定温度、所定湿度の雰囲気下で所定時間
保持したのち、20℃の雰囲気に移し、充填液温
度が20℃である状態でボトル内の炭酸ガス圧力
を測定する。この測定値から、検量線によつて
残存するCO2 Volumeを求める。
CO2 Volume=Vco2/VH2O
(ここで、VH2O:ボトル内のH2O液容積
〔ml〕
Vco2:ボトル内のH2O液相中に溶解するCO2
の0℃1 atm下でのガス体換算容積〔ml〕)
実施例−1〜5及び比較例−1〜5
160℃で5時間熱風乾燥したPET(IV=0.75、
Tg=70℃)と130℃で3時間真空乾燥したEVOH
(商品名EVAL−E)とを第1表に示す割合で混合
し、日精ASB機械(株)製、ASB−50EX−T型共射
出配向ブロー成形機のシリンダーA,Bに各々供
給し、成形温度250〜270℃にて、15℃の冷却水に
て冷却してある2個取り金型内に、第1段目はシ
リンダーAより、第2段目はシリンダーBより、
第3段目はシリンダーAより多段射出成形して直
胴部及び底部が第1図に示す如き断面状態のプリ
フオームを得た。射出圧力は、シリンダーAより
射出している際はAの圧力70Kg/cm2G,Bの圧力
は5Kg/cm2Gであり、またシリンダーBより射出
している際はBの圧力100Kg/cm2Gであつた。前
記プリフオームは円筒状胴部の外径が、25〜26
mm、肉厚3.5mm、全長110mm、重量35gで一端が有
底化された形状のものである。
該プリフオームを更に2軸延伸吹込成形して、
内容積730ml〜740ml、胴部外径74mm、全高234mm、
胴部内厚300〜350μmの胴部及び底部断面が第2
図に示す如き二軸延伸ボトルを得た。
得られた二軸延伸ボトルの直胴部及び底部の
PET成分とEVOR成分との比率及びシリンダーA、
シリンダーBより射出した樹脂の重量を第1表に
示す。
更に、得られた二軸延伸ボトルの耐落下衝撃性
及び炭酸ガスバリア性を評価し、その結果を第1
表に示す。
上表より、比較例−1〜4のボトルは、比較例
−5のボトルよりも炭酸ガスバリア性が良好であ
るが、低温下での耐落下衝撃性が不良であり、一
方実施例−1〜5のボトルは、炭酸ガスバリア性
が良好であり、かつ耐落下衝撃性も良好であるこ
とがわかる。
実施例−6〜−8及び比較例−6〜−7
EVOHの代わりにメタキシリレン基含有ポリアミ
ド(繰り返し単位がメタキシレンジアミンとアジ
ピン酸とを重縮合して得られたポリアミド;以下
PA−Mと記す)樹脂を用い、且つその量比を第
2表に示す値とする他は、実施例−1及び比較例
−1と同様にしてポリエステルボトルを成形し、
得られたボトルを評価した。その結果を第2表に
示す。第2表より明らかな如く、実施例−6〜−
8のポリエステルボトルは、炭酸ガスバリア性、
耐落下衝撃性がいずれも良好である。
Hereinafter, the present invention will be explained in detail with reference to Examples. The measurement conditions for the main physical property values are as follows. (1) Intrinsic viscosity [ ]: Measured at 35°C using o-chlorophenol as a solvent. (2) Carbon dioxide permeability coefficient Carbon dioxide permeability was measured in an atmosphere of 30°C using a GPM-200 gas permeability measuring device manufactured by Lyssy, Switzerland. (3) Drop impact resistance After filling a bottle with 1000g of water and 14g of citric acid, insert 14g of bicarbonate of soda weighed into a polyethylene bag into the bottle mouth without directly mixing it with the citric acid aqueous solution inside the bottle. Immediately cap the bottle with an aluminum cap. After capping, shake the bottle so that the bicarbonate of soda and citric acid aqueous solution inserted into the bottle are thoroughly mixed, and CO 2 gas is generated.
The bottle is filled with an aqueous solution in which CO 2 gas is dissolved under pressure. The resulting CO 2- filled bottle was kept at a temperature of 5°C, and after 24 hours, the bottle was dropped from a height of 1.8 meters onto a concrete floor with the bottom facing downwards, and the rupture rate of the bottle was examined. This ratio is expressed as rupture rate [%]. (4) Carbon dioxide gas barrier property A CO 2 bottle is obtained in the same manner as in the measurement of drop impact resistance in (3) above. However, the CO 2 Volume shown by the following formula is 4. After this CO 2 -filled bottle is held in an atmosphere of a predetermined temperature and a predetermined humidity for a predetermined time, it is transferred to an atmosphere of 20°C, and the carbon dioxide pressure inside the bottle is measured while the temperature of the filled liquid is 20°C. From this measured value, the remaining CO 2 volume is determined using a calibration curve. CO 2 Volume = Vco 2 / VH 2 O (where, VH 2 O: Volume of H 2 O liquid in the bottle [ml]) Vco 2 : CO 2 dissolved in the H 2 O liquid phase in the bottle
Converted gas volume [ml] at 0°C 1 atm) Examples-1 to 5 and Comparative Examples-1 to 5 PET dried with hot air at 160°C for 5 hours (IV = 0.75,
Tg=70℃) and E V OH dried under vacuum at 130℃ for 3 hours.
(Product name: E VAL -E) in the proportions shown in Table 1, and supplied to cylinders A and B of an ASB-50EX-T co-injection oriented blow molding machine manufactured by Nissei ASB Machinery Co., Ltd., respectively. In a two-cavity mold cooled with 15°C cooling water at a molding temperature of 250 to 270°C, the first stage is from cylinder A, the second stage is from cylinder B,
In the third stage, multi-stage injection molding was performed from cylinder A to obtain a preform whose straight body and bottom had a cross-sectional state as shown in FIG. The injection pressure is: when injecting from cylinder A, the pressure of A is 70 kg/cm 2 G, and the pressure of B is 5 kg/cm 2 G, and when injecting from cylinder B, the pressure of B is 100 kg/cm 2 G. It was 2 G. The preform has a cylindrical body with an outer diameter of 25 to 26
mm, wall thickness 3.5mm, total length 110mm, weight 35g, and has a bottomed end. The preform is further biaxially stretched and blow molded,
Internal volume 730ml to 740ml, body outer diameter 74mm, total height 234mm,
The body and bottom cross section with an internal thickness of 300 to 350 μm are the second
A biaxially stretched bottle as shown in the figure was obtained. The straight body and bottom of the resulting biaxially stretched bottle
The ratio of PET component to E VOR component and cylinder A,
Table 1 shows the weight of the resin injected from cylinder B. Furthermore, the drop impact resistance and carbon dioxide gas barrier properties of the obtained biaxially stretched bottle were evaluated, and the results were summarized in the first
Shown in the table. From the table above, the bottles of Comparative Examples-1 to 4 have better carbon dioxide gas barrier properties than the bottles of Comparative Example-5, but have poorer drop impact resistance at low temperatures, while the bottles of Examples-1 to It can be seen that bottle No. 5 has good carbon dioxide gas barrier properties and good drop impact resistance. Examples -6 to -8 and Comparative Examples -6 to -7 E Instead of VOH , metaxylylene group-containing polyamide (a polyamide whose repeating units are obtained by polycondensing metaxylene diamine and adipic acid; the following
A polyester bottle was molded in the same manner as in Example-1 and Comparative Example-1, except that the resin (denoted as PA-M) was used and the quantitative ratio was set to the values shown in Table 2.
The resulting bottles were evaluated. The results are shown in Table 2. As is clear from Table 2, Examples-6 to -
The polyester bottle number 8 has carbon dioxide gas barrier properties,
All have good drop impact resistance.
【表】【table】
【表】【table】
【表】
実施例−9〜−10及び比較例−8〜−9
PET(IV=1.0)とPEI(IV−0.75)とを第3表
に示す割合であらかじめ溶融混合押出したペレツ
トをシリンダーA側に用いる他は、実施例−1、
比較例−1と同様にしてボトルを成形し、評価し
た。その結果を第3表に示す。
実施例−11
第3段目のシリンダーAよりの射出を行わなか
つた他は、実施例−1と同様に成形を行い、第3
図、第4図に示す如き断面形状のプリフオーム及
び二軸延伸ボトルを得た。該二軸延伸ボトルの炭
酸ガスバリア性は実施例−1のものと同じように
良好であつたが、耐落下衝撃性テスト時の配裂時
が3〜5%程度であつた。[Table] Examples -9 to -10 and Comparative Examples -8 to -9 PET (IV = 1.0) and PEI (IV - 0.75) were melted and extruded in the ratio shown in Table 3 beforehand, and the pellets were extruded on the cylinder A side. Example-1, except for use in
A bottle was molded and evaluated in the same manner as Comparative Example-1. The results are shown in Table 3. Example-11 Molding was carried out in the same manner as in Example-1 except that injection from cylinder A in the third stage was not performed.
A preform and a biaxially stretched bottle having cross-sectional shapes as shown in FIG. 4 were obtained. The carbon dioxide gas barrier property of the biaxially stretched bottle was as good as that of Example 1, but the rate of splitting during the drop impact resistance test was about 3 to 5%.
第1図、第3図は有底プリフオームの断面状態
を示す概略図であり、第2図、第4図はボトルの
断面状態を示す概略図である。
1 and 3 are schematic diagrams showing the cross-sectional state of the bottomed preform, and FIGS. 2 and 4 are schematic diagrams showing the cross-sectional state of the bottle.
Claims (1)
フタレート95〜50重量%と30℃における炭酸ガス
透過係数が1.0×10-13〔c.c.・cm/cm2・sec・cmHg〕
以下の熱可塑性ポリマー5〜50重量%の組成物(イ)
からなり、かつ底部がポリエチレンテレフタレー
トから、あるいは組成物(イ)の層()とポリエチ
レンテレフタレートまたは該熱可塑性ポリマーを
胴部の組成物(イ)より低い割合でポリエチレンテレ
フタレートに混合してなる組成物(ロ)の層()と
を少くとも有する積層構造からなることを特徴と
する二軸延伸ポリエステルボトル。 2 上記熱可塑性ポリマーがオレフイン・ビニル
アルコール共重合体、メタキシリレン基含有ポリ
アミド及びポリエチレンイソフタレートの群から
選ばれる少くとも一種である特許請求の範囲第1
項記載の二軸延伸ポリエステルボトル。 3 底部の積層構造が、ボトル内側から、層
()、層()の順の二層構造、層()、層
()、層()の順の三層構造あるいはこれらの
組成構造からなる特許請求の範囲第1項記載の二
軸延伸ポリエステルボトル。 4 組成物(ロ)の熱可塑性ポリマーの割合が5重量
%以下である特許請求の範囲第1項または第3項
記載の二軸延伸ポリエステルボトル。[Claims] 1. The mouth or body of the bottle is made of 95 to 50% by weight polyethylene terephthalate and has a carbon dioxide gas permeability coefficient of 1.0×10 -13 [cc・cm/cm 2・sec・cmHg] at 30°C.
Composition (a) containing 5 to 50% by weight of the following thermoplastic polymer:
and the bottom part is made of polyethylene terephthalate, or the composition (a) is made of a layer (a) of composition (a) and polyethylene terephthalate or the thermoplastic polymer is mixed with polyethylene terephthalate in a lower proportion than the body part composition (a). A biaxially oriented polyester bottle characterized by having a laminated structure having at least the layer (b). 2. Claim 1, wherein the thermoplastic polymer is at least one selected from the group of olefin-vinyl alcohol copolymer, metaxylylene group-containing polyamide, and polyethylene isophthalate.
Biaxially oriented polyester bottle as described in Section 2. 3 Patents in which the laminated structure at the bottom consists of a two-layer structure in the order of Layer (), Layer () from the inside of the bottle, a three-layer structure in the order of Layer (), Layer (), Layer (), or a compositional structure thereof. A biaxially stretched polyester bottle according to claim 1. 4. The biaxially oriented polyester bottle according to claim 1 or 3, wherein the proportion of the thermoplastic polymer in the composition (b) is 5% by weight or less.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60217947A JPS6279258A (en) | 1985-10-02 | 1985-10-02 | Polyester bottle and production thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60217947A JPS6279258A (en) | 1985-10-02 | 1985-10-02 | Polyester bottle and production thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6279258A JPS6279258A (en) | 1987-04-11 |
JPH0524815B2 true JPH0524815B2 (en) | 1993-04-09 |
Family
ID=16712197
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60217947A Granted JPS6279258A (en) | 1985-10-02 | 1985-10-02 | Polyester bottle and production thereof |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6279258A (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0234414U (en) * | 1988-08-30 | 1990-03-05 | ||
AU3824897A (en) * | 1996-08-12 | 1998-03-06 | Crown Cork & Seal Technologies Corporation | Improved plastic container and preform for making |
US5989527A (en) * | 1998-01-26 | 1999-11-23 | Inolex Investment Corporation | Compositions and methods for improving the performance of chemical exfoliating agents, sunless tanning agents, skin lightening agents and insect repellents |
JP2002294055A (en) * | 2001-04-02 | 2002-10-09 | Mitsui Chemicals Inc | Polyester composition, method for producing the same and molding comprising the composition |
JP4857739B2 (en) * | 2005-11-30 | 2012-01-18 | ブラザー工業株式会社 | Image forming apparatus and developing cartridge |
JP6013553B1 (en) * | 2015-04-30 | 2016-10-25 | 株式会社イノアックコーポレーション | Resin composition and hollow molded body |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58183243A (en) * | 1982-04-22 | 1983-10-26 | 株式会社吉野工業所 | Biaxial stretched blow molded bottle body made of synthetic resin |
-
1985
- 1985-10-02 JP JP60217947A patent/JPS6279258A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58183243A (en) * | 1982-04-22 | 1983-10-26 | 株式会社吉野工業所 | Biaxial stretched blow molded bottle body made of synthetic resin |
Also Published As
Publication number | Publication date |
---|---|
JPS6279258A (en) | 1987-04-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4618386A (en) | Method of making a multilayered container | |
AU618770B2 (en) | Transparent gas-barrier multilayer structure | |
EP1651527B1 (en) | Composition for making a packaging article having oxygen-scavenging properties and low haze | |
US4844987A (en) | Polyamide molding material and hollow-molded body obtained therefrom | |
JPS6160436A (en) | Multilayer gas barrier property oriented polyester vessel | |
KR100472819B1 (en) | Layered plastic molding | |
JPH05309648A (en) | Multi-layer vessel and its manufacture | |
JPH0524815B2 (en) | ||
JPS58197050A (en) | Multilayer vessel | |
US20070172611A1 (en) | Hollow container and process for producing the same | |
WO1998013266A9 (en) | Transparent oxygen-scavenging article including biaxially-oriented polyester | |
WO1998013266A1 (en) | Transparent oxygen-scavenging article including biaxially-oriented polyester | |
JP2004338163A (en) | Multilayered container improved in delamination | |
JPH04168148A (en) | Polyester resin composition and its use | |
JPH02229023A (en) | Manufacture of multilayer stretch-molded vessel with intermediate layer arranged offset to inside surface side | |
JPS6172051A (en) | Polyester composition and container made thereof | |
JP2807490B2 (en) | Multi-layer bottle, multi-layer preform and method for producing the same | |
JP3737302B2 (en) | New polyester pellets and method for producing polyester pellets | |
JPH0126940B2 (en) | ||
JPS6333242A (en) | Oriented multilayer plastic vessel and manufacture thereof | |
JPS6230912B2 (en) | ||
JPS6344436A (en) | Oriented multilayer plastic vessel and manufacture thereof | |
US20220288900A1 (en) | Resin layered body | |
JPH0427095B2 (en) | ||
JPS61268753A (en) | Polyester packaging material |