JPS61255956A - Thermoplastic resin sheet and container - Google Patents
Thermoplastic resin sheet and containerInfo
- Publication number
- JPS61255956A JPS61255956A JP60096771A JP9677185A JPS61255956A JP S61255956 A JPS61255956 A JP S61255956A JP 60096771 A JP60096771 A JP 60096771A JP 9677185 A JP9677185 A JP 9677185A JP S61255956 A JPS61255956 A JP S61255956A
- Authority
- JP
- Japan
- Prior art keywords
- olefin
- layer
- thermoplastic
- vinyl alcohol
- alcohol copolymer
- 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
Abstract
Description
【発明の詳細な説明】
本発明は熱可塑性樹脂シートおよびそれから成形された
容器に関し、詳しくはガスバリヤ−性に優れ、低い水分
透過性を有する熱可塑性樹脂シートおよびそれから無成
形して得られる容器に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic resin sheet and a container molded from the same, and more particularly to a thermoplastic resin sheet having excellent gas barrier properties and low moisture permeability, and a container obtained by non-molding from the thermoplastic resin sheet. .
〈従来技術〉
ポリエチレンテレフタレートに代表される熱可塑性ポリ
エステルは優れた剛性、低水分透過性、安全衛生性等を
有し℃おり、包装容器用素材として広く用いられている
。<Prior Art> Thermoplastic polyester represented by polyethylene terephthalate has excellent rigidity, low moisture permeability, safety and hygiene properties, etc., and is widely used as a material for packaging containers.
しかしながらポリエステル容器は酸素ガスや炭酸ガスの
バリヤー性（気体透過遮断性）については充分とはいえ
ず更に改良を望まれていた。ガスバリヤ−性を改善する
方法とし。However, polyester containers do not have sufficient oxygen gas and carbon dioxide gas barrier properties (gas permeation barrier properties), and further improvements have been desired. As a method to improve gas barrier properties.
てはオレフィン−ビニルアルコール共重合体等のガスバ
リヤ−材料との積層化等も提案さでなく両層間に接着剤
層を挿入せしめる必要があり、改善が望まれていたう又
、オンフインービニルアルコール共重合本は吸水性が大
きく、吸水した場合にはガスバ９ヤー性能が低下すると
いう欠点もあった。In addition, lamination with a gas barrier material such as an olefin-vinyl alcohol copolymer has not been proposed, and it is necessary to insert an adhesive layer between the two layers. Alcohol copolymer resins have a large water absorption property, and when they absorb water, they have the disadvantage that gas barrier performance deteriorates.
〈発明の目的〉
本発明の目的はガスバリヤ−性に優れ低い水分透過性を
有する熱可塑性シートおよびそれから熱成形された容器
を提供することＫある。<Object of the Invention> An object of the present invention is to provide a thermoplastic sheet having excellent gas barrier properties and low moisture permeability, and a container thermoformed therefrom.
〈発明の構成〉
本発明は、オレフィン−ビニルアルコール共重合体と２
５０℃以下の軟化点を有する熱可塑性ポリエステル７０
：３０乃至ｌＯ：９０（重量比）から成る層を含む熱可
塑性樹脂シートおよびそれから熱成形して得られる容器
である。<Structure of the invention> The present invention provides an olefin-vinyl alcohol copolymer and two
Thermoplastic polyester 70 with a softening point below 50°C
A thermoplastic resin sheet including a layer consisting of:30 to 1O:90 (weight ratio) and a container obtained by thermoforming the same.
本発明でいうオレフィン−ビニルアルコール共重合体と
はオレフィンと酢酸ビニル等のビニルエステルとの共重
合体をケン化して得られる共重合体をいうが、成形性等
を考慮するとオレフィン含量がｌＯ乃至５０モルチ特に
２０〜４５モルチのものでケン化度が９０チ以上のもの
が好適である。The olefin-vinyl alcohol copolymer referred to in the present invention refers to a copolymer obtained by saponifying a copolymer of an olefin and a vinyl ester such as vinyl acetate. 50 mole, especially 20 to 45 mole, and a degree of saponification of 90 or more is preferred.
本発明でいう２５０℃以下の軟化点を有する熱可塑性ポ
リエステルとはビカート軟化温度試験法（ＪＩＳ Ｋ７
２０６ ） Ｋ従って得られた軟化温度が２５０℃以下
である熱可塑性ポリエステルであり、酸成分としてテレ
フタル酸。In the present invention, the thermoplastic polyester having a softening point of 250°C or less is defined by the Bicat Softening Temperature Test Method (JIS K7
206) K is therefore a thermoplastic polyester with a softening temperature of 250°C or less, and contains terephthalic acid as the acid component.
イソフタル酸、２．６−ナフタレンジカルポ１５１、
４．４−ジフェニレンエーテルジカルボン酸等の芳香族
ジカルボン酸若しくはその誘導体、マロン酸、コハク酸
、アジピン酸、 １，１０−ドデカンジカルボン蒙等
の脂肪族ジカルボン酸若しくはその鰐導体、グリコール
成分としてエチレングリフール、フロピレンゲリコール
、１，４−ブタ／ジオール、ネオペンチルグリコール、
ジエチレングリコール、ポリエチレングリコール、ポリ
テトラメチレングリコール、シクロヘキサンジメタツー
ル若しくはその誘導体を例示することができる。もちろ
ん、数種のジカルボン酸、グリフールを含有せしめた共
重合ポリエステルであってもかまわない。かかるポリエ
ステルの軟化温度は２５０℃以下、好ましくは２４０℃
以下であることが必要である。軟化温度が２５０℃を越
えるとシート化に際して高い溶融温度を必要トスるため
オレフィン−ビニル７ ルコール共重合体の分解が生じ
良好なシートが得られない。最も望ましいものとＬ ′
ｃ例えばテレフタル酸以外のジカルボン酸および／また
はエチレングリフール以外のグリコールを５〜３０モル
チ共重合せしめた共重合ポリエチレンテレフタレートが
挙げられる。Isophthalic acid, 2,6-naphthalene dicarpo 151,
4. Aromatic dicarboxylic acids or derivatives thereof such as 4-diphenylene ether dicarboxylic acid, malonic acid, succinic acid, adipic acid, aliphatic dicarboxylic acids such as 1,10-dodecane dicarboxylic acid or its derivatives, ethylene as a glycol component Glyfur, phlopylene gelicol, 1,4-buta/diol, neopentyl glycol,
Examples include diethylene glycol, polyethylene glycol, polytetramethylene glycol, cyclohexane dimetatool, and derivatives thereof. Of course, a copolymerized polyester containing several kinds of dicarboxylic acids and Glyfur may also be used. The softening temperature of such polyester is 250°C or less, preferably 240°C.
It is necessary that the following is true. If the softening temperature exceeds 250 DEG C., a high melting temperature is required to form a sheet, which causes decomposition of the olefin-vinyl 7 alcohol copolymer, making it impossible to obtain a good sheet. The most desirable one and L′
(c) Examples include copolymerized polyethylene terephthalate obtained by copolymerizing 5 to 30 moles of a dicarboxylic acid other than terephthalic acid and/or a glycol other than ethylene glycol.
オレフィン−ビニルアルフール共重合体ト熱可塑性ポリ
エステルの重量比は７０：３０乃至１０ ：９０好まし
くは５０：５０乃至２０：８０である。オレフィン−ビ
ニルアルコール共重合体の重量が７０重量部を越えると
水分吸収および水分透過か大きく所望のシート又は容器
が得られない。また１０重量部未満ではガスバリヤ−性
の大巾な低下が生じるため好ましくない。The weight ratio of olefin-vinyl alfur copolymer to thermoplastic polyester is 70:30 to 10:90, preferably 50:50 to 20:80. If the weight of the olefin-vinyl alcohol copolymer exceeds 70 parts by weight, water absorption and water permeation will be too great, making it impossible to obtain a desired sheet or container. Moreover, if it is less than 10 parts by weight, the gas barrier properties will be greatly reduced, which is not preferable.
本発明においてオレフィン−ビニルアルコール共重合体
と熱可塑性ポリエステルの混合は例えば押出機等を用い
溶融混合される。In the present invention, the olefin-vinyl alcohol copolymer and the thermoplastic polyester are melt-mixed using, for example, an extruder.
本発明においていうエチレンテレフタレートを主たる構
成単位とするポリエステルとはエチレンテレフタレート
単位を８０モルチ以上好ましくは９０モルチ以上含有す
るポリエステルをいい、テレフタル酸以外のジカルボン
酸或いはエチレングリフール以外のグリコール成分を含
有することができる。該ポリエステルの分子量は得られ
るシート或は容器の強度等に大きく影響するので０．４
以上の固有粘度（オルトクロロフェノール溶ｍ中、３５
℃）を有することが望ましい。In the present invention, the polyester having ethylene terephthalate as a main constituent unit refers to a polyester containing 80 molti or more, preferably 90 molti or more of ethylene terephthalate units, and containing a dicarboxylic acid other than terephthalic acid or a glycol component other than ethylene glycol. be able to. The molecular weight of the polyester greatly affects the strength of the resulting sheet or container, so the molecular weight is 0.4.
Intrinsic viscosity of 35 or more (in orthochlorophenol solution m)
℃) is desirable.
本発明の熱可塑性シートはホットメルトラミネーション
、押出ラミネーション又は共押出ラミネーションにより
多層積層化されることができる。かかる多層シートはオ
レフィン−ビニルアルコール共重合体と２５０℃以下の
軟化点を有する熱可塑性ポリエステルからなる熱可塑性
樹脂層とエチレンテレ７タンートを主たる構成単位とす
るポリエステル層から成る積層シートを主とするもので
あるか他種素材の層を含むこともできる。The thermoplastic sheets of the present invention can be multilayer laminated by hot melt lamination, extrusion lamination, or coextrusion lamination. This multilayer sheet is mainly a laminated sheet consisting of a thermoplastic resin layer made of an olefin-vinyl alcohol copolymer and a thermoplastic polyester having a softening point of 250°C or less, and a polyester layer whose main constituent unit is ethylene tere-7tanto. It may also include layers of other materials.
本発明にいう熟成形とは熱可塑性樹脂シートを加熱軟化
して所要の把に押当て型と材料の間！！ｉＪＫある空気
を排除し大気圧により型に密着させて成形する真空成形
、および大気圧以上の圧縮空気或いは真空を併用して成
形する圧空成形等を総称する。The aged type in the present invention is a thermoplastic resin sheet that is heated and softened and pressed into the desired shape between the mold and the material! ! iJK is a general term for vacuum forming, in which a certain amount of air is excluded and the product is molded in close contact with a mold using atmospheric pressure, and pressure forming, in which molding is performed using compressed air or vacuum at a pressure higher than atmospheric pressure.
〈実施例〉 以下実施例によって本発明を更に具体的に説明する。<Example> The present invention will be explained in more detail below using Examples.
尚、本発明で測定した主な特性の測定法を以下に示す。The methods for measuring the main characteristics measured in the present invention are shown below.
（１）水分透過度： ＪＩＳＺ ０２０Ｂ Ｋ準じて実
施（２） ガス透過係数ニスイスＬｙｓｓｙ社ＪＩＩ
ＧＰＭ−２００ｍガス透過率測定機を用い３０℃雰囲気
で酸素ガスの透過量を測定
実施例１−１〜１０−１および比較例１−１〜第１表に
示した各種ポリエステルと４４モルチノエチレンヲ含有
するエチレン−ビニルアル：１″−ル共重合本を３層ｗ
Ｊ２’押出機を用Ｉ−″−℃シリンダ一温度２４０〜２
５０℃にて溶融混練し、約５０ｊ！のフィルムを作成し
た。このフィルムを用いて水分透過度および酸素ガスの
透過係数を測定した。(1) Moisture permeability: Conducted according to JISZ 020B K (2) Gas permeability coefficient Niss Lyssy JII
Measuring the amount of oxygen gas permeation in an atmosphere of 30°C using a GPM-200m gas permeability meter Three layers of ethylene-vinyl alcohol: 1″-ol copolymer containing
For J2' extruder I-''-℃ cylinder temperature 240~2
Melt and knead at 50℃, about 50j! created a film. Using this film, water permeability and oxygen gas permeability coefficient were measured.
結果をｊｌＩ１表に示す。The results are shown in Table jlI1.
実施例１−２〜１０−２および比較例２−２〜第１表に
示した各種ポリエステルとエチレン−ビニルアルコール
共重合体からなる樹脂組成物および固有粘度０．８５の
ポリエチレンテレフタレートを２層の共押出機を用いて
製膜し、ポリエチレンテレフタレート層厚み１２０μ、
上記樹脂組成物層厚み５０μの積層フィルムを作成した
。Two layers of resin compositions made of various polyesters and ethylene-vinyl alcohol copolymers shown in Examples 1-2 to 10-2 and Comparative Examples 2-2 to Table 1 and polyethylene terephthalate with an intrinsic viscosity of 0.85 were prepared. A film was formed using a coextruder, and the thickness of the polyethylene terephthalate layer was 120μ.
A laminated film with a layer thickness of 50 μm was prepared from the above resin composition.
この積層フィルムについて酸素ガス透過係数および両層
間の密着強度を測定した。The oxygen gas permeability coefficient and adhesion strength between both layers of this laminated film were measured.
結果を第２表に示す。The results are shown in Table 2.
実施例１−３〜１０−３および比較例２−３〜実施例１
−２〜１０−２および比較例２−２〜５−２の積層シー
トを用い、底の直径６５ ｗｍ。Examples 1-3 to 10-3 and Comparative Examples 2-3 to Example 1
Using the laminated sheets of -2 to 10-2 and Comparative Examples 2-2 to 5-2, the bottom diameter was 65 wm.
ロ綴部直径８０ガ、高さ４５票の容器を真空成形したと
ころ、実施例１−２〜１０−２および比較例２−２．３
−２の積層フィルムを用いたもの（それぞれ実施例１−
３〜１０−３および比較例２−３． ３−３ ）Ｋつい
ては良好な性状の容器が得られたが比較例４−２．５−
２の積層フィルム（比較例４−３． ５−３）につい℃
は両層間の密着が不充分なため容器端面において剥離を
生じた。When containers with a binding part diameter of 80 ga and a height of 45 ga were vacuum formed, Examples 1-2 to 10-2 and Comparative Example 2-2.3
-2 laminated films (respectively Example 1-
3 to 10-3 and Comparative Example 2-3. 3-3) Although a container with good properties regarding K was obtained, Comparative Example 4-2.5-
2 laminated film (Comparative Example 4-3. 5-3)
Because the adhesion between both layers was insufficient, peeling occurred at the end surface of the container.
Claims (4)
℃以下の軟化点を有する熱可塑性ポリエステル７０：３
０乃至１０：９０（重量比）から成る層を含む熱可塑性
樹脂シート。(1) Olefin-vinyl alcohol copolymer and 250
Thermoplastic polyester with a softening point below 70:3 °C
A thermoplastic resin sheet comprising a layer having a ratio of 0 to 10:90 (weight ratio).
ポリエステル層と積層されている特許請求の範囲第１項
記載の熱可塑性樹脂シート。(2) The thermoplastic resin sheet according to claim 1, which is laminated with a polyester layer containing ethylene terephthalate as a main structural unit.
℃以下の軟化点を有する熱可塑性ポリエステル７０：３
０乃至１０：９０（重量比）から成る層を含む熱可塑性
樹脂シートを熱成形して得られる容器。(3) Olefin-vinyl alcohol copolymer and 250
Thermoplastic polyester with a softening point below 70:3 °C
A container obtained by thermoforming a thermoplastic resin sheet containing a layer of 0 to 10:90 (weight ratio).
ポリエステル層と積層されている特許請求の範囲第３項
記載の容器。(4) The container according to claim 3, which is laminated with a polyester layer containing ethylene terephthalate as a main structural unit.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60096771A JPS61255956A (en) | 1985-05-09 | 1985-05-09 | Thermoplastic resin sheet and container |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60096771A JPS61255956A (en) | 1985-05-09 | 1985-05-09 | Thermoplastic resin sheet and container |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4278760A Division JPH05229075A (en) | 1992-10-16 | 1992-10-16 | Thermoplastic resin sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61255956A true JPS61255956A (en) | 1986-11-13 |
| JPH0541501B2 JPH0541501B2 (en) | 1993-06-23 |
Family
ID=14173894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60096771A Granted JPS61255956A (en) | 1985-05-09 | 1985-05-09 | Thermoplastic resin sheet and container |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61255956A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6485243A (en) * | 1987-05-28 | 1989-03-30 | Kuraray Co | Resin composition and gas-barrier heat-resistant polyester container prepared thereform |
| JPH0216151A (en) * | 1988-07-05 | 1990-01-19 | Polyplastics Co | Polybutylene terephthalate resin composition and molding |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2829217A4 (en) | 2012-03-23 | 2015-12-30 | Olympus Corp | Insertion device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52141785A (en) * | 1976-05-20 | 1977-11-26 | Toyo Seikan Kaisha Ltd | Container |
| JPS5620073A (en) * | 1979-05-11 | 1981-02-25 | Clopay Corp | Gas and moisture preventing wall material composition |
| JPS6076325A (en) * | 1983-10-03 | 1985-04-30 | Mitsui Petrochem Ind Ltd | Biaxially oriented formed product of thermoplastic polyester composition |
| JPS60129256A (en) * | 1983-12-16 | 1985-07-10 | 日本合成化学工業株式会社 | Multilayer structure |
| JPS61211033A (en) * | 1985-03-15 | 1986-09-19 | 東洋製罐株式会社 | Laminated structure |
-
1985
- 1985-05-09 JP JP60096771A patent/JPS61255956A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52141785A (en) * | 1976-05-20 | 1977-11-26 | Toyo Seikan Kaisha Ltd | Container |
| JPS5620073A (en) * | 1979-05-11 | 1981-02-25 | Clopay Corp | Gas and moisture preventing wall material composition |
| JPS6076325A (en) * | 1983-10-03 | 1985-04-30 | Mitsui Petrochem Ind Ltd | Biaxially oriented formed product of thermoplastic polyester composition |
| JPS60129256A (en) * | 1983-12-16 | 1985-07-10 | 日本合成化学工業株式会社 | Multilayer structure |
| JPS61211033A (en) * | 1985-03-15 | 1986-09-19 | 東洋製罐株式会社 | Laminated structure |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6485243A (en) * | 1987-05-28 | 1989-03-30 | Kuraray Co | Resin composition and gas-barrier heat-resistant polyester container prepared thereform |
| JPH0216151A (en) * | 1988-07-05 | 1990-01-19 | Polyplastics Co | Polybutylene terephthalate resin composition and molding |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0541501B2 (en) | 1993-06-23 |
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