JPH04139220A - Modified ethylene-vinyl alcohol copolymer and its laminate - Google Patents
Modified ethylene-vinyl alcohol copolymer and its laminateInfo
- Publication number
- JPH04139220A JPH04139220A JP26266890A JP26266890A JPH04139220A JP H04139220 A JPH04139220 A JP H04139220A JP 26266890 A JP26266890 A JP 26266890A JP 26266890 A JP26266890 A JP 26266890A JP H04139220 A JPH04139220 A JP H04139220A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- vinyl alcohol
- alcohol copolymer
- gas barrier
- laminate
- 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
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 title claims abstract description 39
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical class OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- 230000005855 radiation Effects 0.000 claims abstract description 14
- 230000001678 irradiating effect Effects 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 5
- 238000010030 laminating Methods 0.000 claims abstract description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 230000004888 barrier function Effects 0.000 abstract description 37
- 238000010894 electron beam technology Methods 0.000 abstract description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 9
- 239000005977 Ethylene Substances 0.000 abstract description 9
- 239000005022 packaging material Substances 0.000 abstract description 3
- 230000035699 permeability Effects 0.000 description 27
- 239000007789 gas Substances 0.000 description 26
- 238000012360 testing method Methods 0.000 description 23
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 229910001882 dioxygen Inorganic materials 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- 231100000987 absorbed dose Toxicity 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 230000001143 conditioned effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000000887 hydrating effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LGCMKPRGGJRYGM-UHFFFAOYSA-N Osalmid Chemical compound C1=CC(O)=CC=C1NC(=O)C1=CC=CC=C1O LGCMKPRGGJRYGM-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 1
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229940110728 nitrogen / oxygen Drugs 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、気体遮断性（ガスバリア性）に優れた変性エ
チレン−ビニルアルコール共重合体に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a modified ethylene-vinyl alcohol copolymer having excellent gas barrier properties.
〈従来の技術〉
エチレン−ビニルアルコール共重合体はポリビニルアル
コールのガスバリア性、非帯電性、耐油性、透明性、光
沢なとの優れた性能を受は継ぎながら、ポリビニルアル
コールの欠点となる透湿性、溶融成形性、その他諸物性
の温湿度依存性などをエチレンとの共重合により、ある
程度改良した樹脂であり、特にその乾燥状態での優れた
ガスバリア性から、カスバリア材料として、共押し出し
フィルム、多層ラミネートフィルム、多層ブロー成型容
器などに成形され、ガスバリア性を有する包装材料とし
て、広範な用途に使用されている。<Prior art> Ethylene-vinyl alcohol copolymer inherits the excellent properties of polyvinyl alcohol, such as gas barrier properties, non-static properties, oil resistance, transparency, and gloss, but has the disadvantages of polyvinyl alcohol, such as moisture permeability. It is a resin whose melt moldability and temperature/humidity dependence of other physical properties have been improved to some extent through copolymerization with ethylene.Because of its excellent gas barrier properties in the dry state, it is used as a gas barrier material in coextruded films and multilayered films. It is formed into laminated films, multilayer blow-molded containers, etc., and is used in a wide range of applications as a packaging material with gas barrier properties.
〈発明が解決しようとする課題〉
しかしながら、缶詰、瓶詰などの用途に用いられている
金属葉材やガラスは酸素なとの気体透過性がほとんど零
であるのに対して、エチレン−ビニルアルコール共重合
体は未だ無視てきない程度の量の気体を透過し、特に高
湿度下ではビニルアルコール部の吸湿によりガスバリア
性が著しく低下する、という問題点を有する。<Problem to be solved by the invention> However, metal leaf materials and glass used for purposes such as canning and bottling have almost zero gas permeability to oxygen, while ethylene-vinyl alcohol Polymers still have the problem of permeating a non-negligible amount of gas, and particularly under high humidity, the gas barrier properties are significantly reduced due to moisture absorption in the vinyl alcohol moiety.
これらの問題点を解決する手段として以下のような手法
が考案されている。The following methods have been devised as means to solve these problems.
特開昭５３−６６９８３号公報には、内外層に耐水性の
高い樹脂を、中間層にエチレンービニルアルコール共重
合体を含有し、さらに層間の接着性を高めた積層体が報
告されている。JP-A No. 53-66983 reports a laminate containing highly water-resistant resin in the inner and outer layers and an ethylene-vinyl alcohol copolymer in the middle layer, which further improves the adhesion between the layers. .
また、特開昭６２−２０７３３８号公報にはエチレン−
ビニルアルコール共重合体を含む積層体の包装容器にイ
オン化放射線を照射し、ガスバリア性を高める方法が報
告されている。In addition, ethylene-
A method has been reported in which a packaging container made of a laminate containing a vinyl alcohol copolymer is irradiated with ionizing radiation to improve gas barrier properties.
前者の方法は内外層に用いられた耐水性の高い樹脂が中
間層のエチしンービニルアルコール共重合体の吸湿速度
を低下させ、ガスバリア性の低下を遅くするというもの
だが、最終的な飽和吸湿状態でのガスバリア性能は改良
できない。In the former method, the highly water-resistant resin used in the inner and outer layers reduces the moisture absorption rate of the ethyne-vinyl alcohol copolymer in the intermediate layer, slowing down the deterioration of gas barrier properties, but the final saturated moisture absorption The gas barrier performance cannot be improved under these conditions.
後者の方法は一時的には優れたガスバリア性を示すが、
それは経時で低下し、最終的には通常のエチレン−ビニ
ルアルコール共重合体よりも性能が劣ってしまう。The latter method temporarily shows excellent gas barrier properties, but
It deteriorates over time and eventually becomes inferior in performance to ordinary ethylene-vinyl alcohol copolymers.
本発明の目的は従来のエチレン−ビニルアルコール共重
合体のガスバリア性を著しく高めた変性エチレン−ビニ
ルアルコール共重合体を得ることにある。An object of the present invention is to obtain a modified ethylene-vinyl alcohol copolymer that has significantly improved gas barrier properties than conventional ethylene-vinyl alcohol copolymers.
く課題を解決するための手段〉
本発明者らはガスバリア材料について、特にエチレン−
ビニルアルコール共重合体およびそれを用いたガスバリ
ア材料の研究を続けてきた。Means for Solving the Problems> The present inventors have investigated gas barrier materials, particularly ethylene-
I have continued research on vinyl alcohol copolymers and gas barrier materials using them.
その結果、エチレン−ビニルアルコール共重合体を含水
させた状態で放射線照射することにより得られる変性エ
チレン−ビニルアルコール共重合体は、従来にない高い
ガスバリア性を発現することを見いだし、本発明を完成
させるに至った。As a result, they discovered that a modified ethylene-vinyl alcohol copolymer obtained by irradiating a hydrated ethylene-vinyl alcohol copolymer exhibits unprecedentedly high gas barrier properties, and completed the present invention. I ended up letting it happen.
すなわち本発明は、含水率０．５重量％以上のエチレン
−ビニルアルコール共重合体に放射線を照射することに
より得られる変性エチレン−ビニルアルコール共重合体
である。That is, the present invention is a modified ethylene-vinyl alcohol copolymer obtained by irradiating an ethylene-vinyl alcohol copolymer having a water content of 0.5% by weight or more with radiation.
本発明で用いられるエチレン−ビニルアルコール共重合
体の組成としては、エチレン含有量が２０モル％以上７
０モル％以下、より好ましくは、３０モル％以上５０モ
ル％以下の範囲のものが用いられる。エチレン含有量が
７０モル％よりも大であるとガスバリア性能が大きく低
下し、好ましくない。また、エチレン含有量が２０モル
％以下であると成形加工性が悪化したり、吸湿性が大き
くなりすぎることて諸物性の環境湿度依存性が強くなり
、好ましくない。The composition of the ethylene-vinyl alcohol copolymer used in the present invention is such that the ethylene content is 20 mol% or more.
The amount used is 0 mol% or less, more preferably 30 mol% or more and 50 mol% or less. If the ethylene content is more than 70 mol%, the gas barrier performance will be greatly reduced, which is not preferable. Furthermore, if the ethylene content is less than 20 mol %, molding processability may deteriorate, and hygroscopicity may become too large, resulting in a strong dependence of various physical properties on environmental humidity, which is not preferable.
本発明で用いられるエチレン−ビニルアルコール共重合
体の分子量は用途によっても異なり、フィルム成形可能
な範囲であれば特に制限はないが、重量平均分子量で１
万以上２００万以下が好ましく用いられる。The molecular weight of the ethylene-vinyl alcohol copolymer used in the present invention varies depending on the use, and is not particularly limited as long as it can be formed into a film.
10,000 or more and 2,000,000 or less is preferably used.
また、放射線照射に供するエチレン−ビニルアルコール
共重合体の形状にも特に制限はなく、ボトル、チューブ
、タンク、フィルムなど様々な形状のものが用いられる
。均一照射が容易なシート状態、特に厚み１μｍ以上２
ｍｍ以下のシートが好ましく用いられる。Furthermore, there is no particular restriction on the shape of the ethylene-vinyl alcohol copolymer to be subjected to radiation irradiation, and various shapes such as bottles, tubes, tanks, and films can be used. Sheet form that facilitates uniform irradiation, especially with a thickness of 1 μm or more2
A sheet having a diameter of 1 mm or less is preferably used.
また、それらのシートは１軸延伸、２軸延伸なとの後加
工が成されていてもよい。Further, these sheets may be subjected to post-processing such as uniaxial stretching or biaxial stretching.
本発明で放射線照射に供するエチレン−ビニルアルコー
ル共重合体の含水率は０．５重量％以上飽和含水率以下
である。含水率０．５重量％以下ではガスバリア性向上
効果が小さく、また飽和含水率より多く含水させること
は不可能であり、ともに好ましくない。The water content of the ethylene-vinyl alcohol copolymer subjected to radiation irradiation in the present invention is 0.5% by weight or more and saturated water content or less. If the water content is 0.5% by weight or less, the effect of improving gas barrier properties is small, and it is impossible to increase the water content above the saturated water content, both of which are not preferred.
本発明で用いられるエチレン−ビニルアルコール共重合
体の含水させる方法に特に制限はなく、水中浸漬による
方法や加湿槽でエージングする方法などが用いられる。There is no particular restriction on the method of hydrating the ethylene-vinyl alcohol copolymer used in the present invention, and methods such as immersion in water and aging in a humidifying tank may be used.
本発明で用いられる放射線の種類としては特に制限はな
いが、ガンマ−線、アルファー線、電子線などが好まし
く用いられる。特に、生産速度の向上、安全性の高さな
ど工業的に有利な放射線としては電子線があげられる。The type of radiation used in the present invention is not particularly limited, but gamma rays, alpha rays, electron beams, etc. are preferably used. In particular, electron beams are an example of industrially advantageous radiation such as improved production speed and high safety.
電子線源としては、加速電圧が１００ｋＶ以上３０００
ｋＶ以下の電子線加速機が好ましく用いられる。加速電
圧がｌ００ｋＶより小さいと電子線の透過深さが十分で
なく、３０００ｋＶより大きいと装置的に大がかりなも
のになりすぎてしまう。電子線照射装置の例としては、
パンデグラーフ型なとの電子線走差型装置やエレクトロ
ンカーテン型なとの電子線固定・コンベア移動型装置な
とがあげられる。As an electron beam source, the accelerating voltage is 100 kV or more and 3000
An electron beam accelerator of kV or less is preferably used. If the accelerating voltage is less than 100 kV, the penetration depth of the electron beam will not be sufficient, and if it is greater than 3000 kV, the device will become too large. Examples of electron beam irradiation equipment include:
Examples include electron beam scanning type devices such as the Pandegraaf type, and electron beam fixed/conveyor moving type devices such as the electron curtain type.
本発明で用いられる放射線の線量は、吸収線量で０．１
Ｍｒａｃｆ以上１００Ｍｒａｄ以下、より好ましくは０
．５Ｍｒａｄ以上３０Ｍｒａｄ以下である。吸収線量が
０．１Ｍｒａｄより小さい場合にはガスバリア性の向上
が十分てなく、１００Ｍ ｒ ａ ｄよりも大きい場合
には機械的物性の低下などが見られ、好ましくない。The radiation dose used in the present invention is 0.1 in terms of absorbed dose.
Mracf or more and 100 Mrad or less, more preferably 0
．． It is 5 Mrad or more and 30 Mrad or less. If the absorbed dose is less than 0.1 Mrad, the gas barrier properties are not sufficiently improved, and if it is more than 100 Mrad, mechanical properties may deteriorate, which is not preferable.
本発明で用いられる放射線の照射条件は特に制限はなく
、種々の条件が可能である。照１１雰囲気は窒素下など
不活性ガス雰囲気が好ましいが、空気中でも特に問題は
ない。また、照射速度・時間も所定の吸収線量が照射さ
れておれば、特に制限はない。The radiation irradiation conditions used in the present invention are not particularly limited, and various conditions are possible. The atmosphere in the first step is preferably an inert gas atmosphere such as nitrogen, but there is no particular problem in air. Furthermore, there are no particular limitations on the irradiation speed and time as long as a predetermined absorbed dose is irradiated.
本発明においては、エチレン−ビニルアルコール共重合
体からなる層の少なくとも一方の面に熱可塑性樹脂を積
層してなる積層体のエチレン−ビニルアルコール共重合
体層を含水率０．５重量％以上として、これを放射線照
射することにより、ガスバリア性に優れた変性エチレン
−ビニルアルコール共重合体含有積層体とすることもで
きる。In the present invention, the ethylene-vinyl alcohol copolymer layer of the laminate formed by laminating a thermoplastic resin on at least one side of the ethylene-vinyl alcohol copolymer layer has a moisture content of 0.5% by weight or more. By irradiating this with radiation, a modified ethylene-vinyl alcohol copolymer-containing laminate with excellent gas barrier properties can be obtained.
エチレン−ビニルアルコール共重合体からなる少なくと
も一方の面に積層する熱可塑性樹脂としては、ポリエチ
レン、ポリプロピレン、ポリ−１−ブテン、ポリ−４−
メチル−１−ペンテン、エチレン−プロピレンブロック
共重合体、エチレン−プロピレンランダム共重合体、エ
チレン−１−ブテン共重合体、エチレン−１−ヘキセン
共重合体、エチレン−４−メチル−１−ペンテン共重合
体、エチレン−１−オクテン共重合体、プロピレン−１
−ブテン共重合体、エチレン−酢酸ビニル共重合体、エ
チレン−メタクリル酸メチル共重合体、アイオノマー樹
脂、などのオレフィン系重合体、ポリエチレンテレフタ
レート、ポリブチレンテレフタレートなどのポリエステ
ル樹脂、ポリアミド樹脂、ポリカーボネート樹脂、アク
リロニトリル−スチレン−ブタジェン共重合体、アクリ
ロニトリル−ブタジェン共重合体などのニトリル系樹脂
、ポリ塩化ビニル、ポリ塩化ビニリデンなどを例示する
ことができる。The thermoplastic resin laminated on at least one surface made of ethylene-vinyl alcohol copolymer includes polyethylene, polypropylene, poly-1-butene, poly-4-
Methyl-1-pentene, ethylene-propylene block copolymer, ethylene-propylene random copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer Polymer, ethylene-1-octene copolymer, propylene-1
- Olefin polymers such as butene copolymers, ethylene-vinyl acetate copolymers, ethylene-methyl methacrylate copolymers, ionomer resins, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polycarbonate resins, Examples include nitrile resins such as acrylonitrile-styrene-butadiene copolymer and acrylonitrile-butadiene copolymer, polyvinyl chloride, and polyvinylidene chloride.
本発明に用いられる積層体の製造方法としては、特に限
定されないが、共押し出し成形法、多層ラミネート成形
法、カレンダー成形法、キャスト成形法、ブロー成形法
などが好ましく用いられる。The method for producing the laminate used in the present invention is not particularly limited, but coextrusion, multilayer laminate, calendar, cast, blow molding, and the like are preferably used.
本発明に用いられる積層体の含水方法も、特に限定はな
く、前述の水中浸漬による方法や加湿槽てエージングす
る方法などがあげられる。The method of hydrating the laminate used in the present invention is not particularly limited, and examples include the above-mentioned method of immersion in water and the method of aging in a humidifying tank.
本発明の変性エチレン−ビニルアルコール共重合体は、
本発明の目的を損なわない範囲で、紫外線吸収剤や滑剤
、充填剤、難燃剤、顔料、および他の熱可塑性樹脂、例
えば前述のオレフィン系重合体、ポリエステル樹脂、ポ
リアミド樹脂、ニトリル系樹脂、などを成分として含む
ことができる。The modified ethylene-vinyl alcohol copolymer of the present invention is
Ultraviolet absorbers, lubricants, fillers, flame retardants, pigments, and other thermoplastic resins, such as the aforementioned olefin polymers, polyester resins, polyamide resins, nitrile resins, etc., as long as they do not impair the purpose of the present invention. can be included as an ingredient.
上述した各成分の配合方法は特に限定されず、バンバリ
ーミキサ−、ミキシングロール、押出機などの一般的な
方法で配合することができる。The method of blending the above-mentioned components is not particularly limited, and they can be blended by a common method such as a Banbury mixer, a mixing roll, or an extruder.
く作用〉
本発明の変性エチレン−ビニルアルコール共重合体はエ
チレン−ビニルアルコール共重合体が含水状態で放射線
照射を受けることにより生じた構造変化がガスバリア性
の著しい向上をもたらしていると考えられる。Effects> It is thought that the modified ethylene-vinyl alcohol copolymer of the present invention has a remarkable improvement in gas barrier properties due to structural changes caused by irradiation of the ethylene-vinyl alcohol copolymer in a water-containing state.
本発明の変性エチレン−ビニルアルコール共重合体はエ
チレン−ビニルアルコール共重合体の気相中での放射線
照射であるが、樹脂内にはある程度の水分があり、これ
によって内部構造をガスバリア性が発現するのに理想的
となるような架橋構造が生じていると推定される。The modified ethylene-vinyl alcohol copolymer of the present invention is produced by irradiating the ethylene-vinyl alcohol copolymer with radiation in the gas phase, but there is a certain amount of moisture in the resin, which causes the internal structure to develop gas barrier properties. It is presumed that a crosslinked structure has been formed that is ideal for this purpose.
〈実施例〉
以下、本発明の実施例を示すが、本発明はこれに限定さ
れるものではない。なお実施例中の試験法は次の通りで
ある。<Examples> Examples of the present invention will be shown below, but the present invention is not limited thereto. The test methods in the examples are as follows.
酸素透過度試験
（株）モダンコントｏ−ルｉ！０ＸＴＲＡＮ１００を用
いた。測定条件は以下の通り。Oxygen Permeability Test Co., Ltd. Modern Control i! OXTRAN100 was used. The measurement conditions are as follows.
測定温度３０℃、窒素ガス（１％水素含む）流量１０ｍ
Ｌ／分、酸素ガス流量１０ｍＬ／分、窒素・酸素ガスは
１０℃の恒温水中を通過させたものを用い、サンプルを
セットして１２時間安定後に測定した。Measurement temperature: 30℃, nitrogen gas (including 1% hydrogen) flow rate: 10m
L/min, oxygen gas flow rate 10 mL/min, and nitrogen/oxygen gases passed through constant temperature water at 10°C were used, and the sample was set and measured after being stabilized for 12 hours.
値は単位時間、単位面積当りの酸素ガス透過量を示し、
値が小さいほど酸素ガスバリア性が優れていることを示
す。The value indicates the amount of oxygen gas permeation per unit time and unit area.
The smaller the value, the better the oxygen gas barrier property.
透湿度試験 ＪＩＳ Ｚ ０２０Ｂ に基づき測定した。Moisture permeability test Measured based on JIS Z 020B.
値は単位時間、単位面積当りの水蒸気透過量を示し、値
が小さいほど水蒸気バリア性が優れていることを示す。The value indicates the amount of water vapor permeation per unit time and unit area, and the smaller the value, the better the water vapor barrier property is.
含水量測定 含水前、含水後の重量変化測定により求めた。water content measurement It was determined by measuring weight changes before and after hydration.
実施例１
８０℃、１２時間真空乾燥した（株）クラレ製エバール
ＥＦ−Ｆ （エチレン−ビニルアルコール共重合体 エ
チレン含有率３２モル％ フィルム厚み５μｍ）を３
０℃、水中で２４時時間待させたのち、２３℃、飽和水
蒸気下で２４時間状態調整したフィルムを日新ハイボル
テージ（株）製電子線照射装置キュアトロンＥＢＣ−２
００−２０−１５を用い、加速電圧２００ｋＶ、電子流
２ｍＶ、コンベア速度１２ｍ／分、窒素下の条件で電子
線照射した（吸収線量２Ｍｒａｄ）。照射後オートデシ
ケータ中で乾燥し、酸素透過度試験、透湿度試験をそれ
ぞれ行った。Example 1 Eval EF-F (ethylene-vinyl alcohol copolymer, ethylene content 32 mol%, film thickness 5 μm) manufactured by Kuraray Co., Ltd., vacuum-dried at 80°C for 12 hours, was
After waiting in water at 0°C for 24 hours, the film was conditioned for 24 hours at 23°C under saturated steam, and the film was placed in an electron beam irradiation device Curetron EBC-2 manufactured by Nissin High Voltage Co., Ltd.
Electron beam irradiation was performed using 00-20-15 under nitrogen conditions at an accelerating voltage of 200 kV, an electron current of 2 mV, and a conveyor speed of 12 m/min (absorbed dose of 2 Mrad). After irradiation, it was dried in an auto-desiccator and subjected to an oxygen permeability test and a moisture permeability test.
結果は第１表に示した通り、非常に優れた酸素ガスバリ
ア性を示した。As shown in Table 1, the results showed very excellent oxygen gas barrier properties.
実施例２〜３
電子線照射条件を第１表に示した通りにした以外は、実
施例１と同様にして、酸素透過度試験、透湿度試験をそ
れぞれ行った。Examples 2 to 3 An oxygen permeability test and a moisture permeability test were conducted in the same manner as in Example 1, except that the electron beam irradiation conditions were as shown in Table 1.
結果は第１表に示した通り、非常に優れた酸素ガスバリ
ア性を示した。As shown in Table 1, the results showed very excellent oxygen gas barrier properties.
比較例】
電子線を照射しなかった以外は実施例１と同様にして、
第１表に示したサンプルについて、酸素透過度試験、透
湿度試験をそれぞれ行った。Comparative Example] Same as Example 1 except that electron beam was not irradiated,
An oxygen permeability test and a water vapor permeability test were conducted on the samples shown in Table 1, respectively.
結果は第１表に示した通り、酸素ガスバリア性の劣った
ものであった。As shown in Table 1, the results showed poor oxygen gas barrier properties.
実施例４
８０℃、１２時間真空乾燥した（株）クラレ製エバール
ＥＦ−Ｅ （エチしンービニルアルコール共重合体 エ
チレン含有率４４モル％ フィルム厚み５μｍ）を３
０℃、水中で２４時間経時させたのち、２３℃、飽和水
蒸気下で２４時間状態調整したフィルムを日新ハイボル
テージ（株）！！’Ｈ子線照射装置キュアトロンＥＢＣ
−２００−２０−１５を用い、加速電圧２００ｋＶ、電
子流５ｍＶ、コンへア速度１２ｍ／分、窒素下の条件で
電子線照射した（吸収線量５Ｍｒａｄ）。照射後オート
デシケータ中て乾燥し、酸素透過度試験、透湿度試験を
それぞれ行った。Example 4 Eval EF-E (ethyshin-vinyl alcohol copolymer, ethylene content 44 mol%, film thickness 5 μm) manufactured by Kuraray Co., Ltd., vacuum-dried at 80° C. for 12 hours, was dried in a vacuum for 3 hours.
After aging in water at 0°C for 24 hours, the film was conditioned for 24 hours at 23°C under saturated steam, and then produced by Nissin High Voltage Co., Ltd. ! 'H-ion beam irradiation device Curetron EBC
-200-20-15, electron beam irradiation was performed under nitrogen conditions at an accelerating voltage of 200 kV, an electron current of 5 mV, and a conhair speed of 12 m/min (absorbed dose: 5 Mrad). After irradiation, it was dried in an auto-desiccator, and an oxygen permeability test and a moisture permeability test were conducted.
結果は第２表に示した通り、優れた酸素カスバリア性を
示した。As shown in Table 2, the results showed excellent oxygen gas barrier properties.
実施例５
電子線照射条件を第２表に示した通りにした以外は、実
施例４と同様にして、酸素透過度試験、透湿度試験をそ
れぞれ行った。Example 5 An oxygen permeability test and a moisture permeability test were conducted in the same manner as in Example 4, except that the electron beam irradiation conditions were as shown in Table 2.
結果は第２表に示した通り、優れた酸素ガスバリア性を
示した。As shown in Table 2, the results showed excellent oxygen gas barrier properties.
比較例２
電子線を照射しなかった以外は実施例４と同様にして、
第２表に示したサンプルについて、酸素透過度試験、透
湿度試験をそれぞれ行った。Comparative Example 2 Same as Example 4 except that the electron beam was not irradiated,
An oxygen permeability test and a moisture permeability test were conducted on the samples shown in Table 2.
結果は第２表に示した通り、酸素ガスバリア性の劣った
ものであった。As shown in Table 2, the results showed poor oxygen gas barrier properties.
実施例６
８０℃、１２時間真空乾燥した（株）クラレ製エバール
フィルムＥＦ−Ｆ （エチレン−ビニルアルコール共重
合体 エチレン含有率３２モル％フィルム厚み１５μｍ
）を２３℃、飽和水蒸気下で経時させ、フィルム中の含
水率を約２．０重量％に調湿したものを日新ハイボルテ
ージ（株）製電子線照射装置キュアトロンＥＢＣ−２０
０−２０−１５を用い、加速電圧２００ｋＶ、電子流５
ｍＶ、コンベア速度６ｍ／分、窒素下の条件で電子線照
射した（吸収線量１０Ｍｒａｄ）。照射後オートデシケ
ータ中て乾燥し、酸素透過度試験を行った。 結果は第
３表に示した通り、非常に優れた酸素ガスバリア性を示
した。Example 6 EVAL Film EF-F (ethylene-vinyl alcohol copolymer, ethylene content 32 mol%, film thickness 15 μm, manufactured by Kuraray Co., Ltd., vacuum dried at 80°C for 12 hours)
) was aged at 23°C under saturated steam, and the moisture content in the film was adjusted to approximately 2.0% by weight using an electron beam irradiation device Curetron EBC-20 manufactured by Nissin High Voltage Co., Ltd.
0-20-15, acceleration voltage 200kV, electron current 5
Electron beam irradiation was performed under conditions of mV, conveyor speed of 6 m/min, and nitrogen (absorbed dose: 10 Mrad). After irradiation, it was dried in an autodesicator and an oxygen permeability test was conducted. As shown in Table 3, the results showed very excellent oxygen gas barrier properties.
実施例７〜９
サンプルおよび調湿条件を第３表に示した通りにした以
外は実施例６と同様にして、ｒ１１ｇ透過度試験を行っ
た。Examples 7 to 9 An r11g permeability test was conducted in the same manner as in Example 6, except that the samples and humidity control conditions were as shown in Table 3.
結果は第３表に示した通り、非常に優れた酸素ガスバリ
ア性を示した。As shown in Table 3, the results showed very excellent oxygen gas barrier properties.
比較例３〜４
調湿および電子線照射を行わなかった以外は実施例６と
同様にして、第３表に示したサンプルについて酸素透過
度試験を行った。Comparative Examples 3-4 An oxygen permeability test was conducted on the samples shown in Table 3 in the same manner as in Example 6, except that humidity control and electron beam irradiation were not performed.
結果は第３表に示した通り、酸素ガスバリア性の劣った
ものであった。As shown in Table 3, the results showed poor oxygen gas barrier properties.
実施例１０
東洋紡（株）製バイレン（２軸延伸ポリプロピレン 厚
さ１５μｍ）を外層に、（株）クラレ製エバールＥＦ−
Ｆ （エチレン−ビニルアルコール共重合体 エチレン
含有１Ｆ３２モル％ 厚さ１５μｍ）を中間層に、出光
興産（株）類ユニラックスＬＳ７００Ｃ（線状低密度ポ
リエチレン 厚さ５０μｍ）を内層に、眉間の接着剤と
して東洋モートン（株）製アトコートＡＤ３０８Ｂ （
ウレタン系接着剤接着剤Ｍ５ｇ／ｍ２’）を用い、康井
精機（株）製テストコーターにて積層体を作成した。こ
の積層体を３０℃、水中で７２時間経時させたのち、２
３℃、飽和水蒸気下で２４時間状態調整したフィルムを
日新ハイボルテージ（株＞Ｕ電子線照射装置キュアトロ
ンＥＢＣ−２００−２０−１５を用い、加速電圧２００
ｋＶ、電子流２ｍＶ、コンベア速度２４ｍ／分、窒素下
の条件で電子線照射した（吸収線ｊｌ Ｉ Ｍ ｒ ａ
ｄ ）。照射後オートデシケータ中て乾燥し、酸素透
過度試験、透湿度試験を行った。Example 10 Bilene (biaxially oriented polypropylene, thickness 15 μm) manufactured by Toyobo Co., Ltd. was used as the outer layer, and EVAL EF- manufactured by Kuraray Co., Ltd.
F (ethylene-vinyl alcohol copolymer, ethylene content 1F 32 mol%, thickness 15 μm) as the middle layer, Idemitsu Kosan Co., Ltd. Unilux LS700C (linear low-density polyethylene, thickness 50 μm) as the inner layer, glabellar adhesive. Atcoat AD308B manufactured by Toyo Morton Co., Ltd. (
A laminate was prepared using a test coater manufactured by Yasui Seiki Co., Ltd. using a urethane adhesive (M5 g/m2'). After aging this laminate in water at 30°C for 72 hours,
The film was conditioned for 24 hours at 3°C under saturated water vapor and then exposed to an acceleration voltage of 200 using Nissin High Voltage Co., Ltd.'s Curetron EBC-200-20-15 electron beam irradiation device.
Electron beam irradiation was carried out under nitrogen conditions, with an electron current of 2 mV and a conveyor speed of 24 m/min (absorption line jl I M r a
d). After irradiation, it was dried in an auto-desiccator, and an oxygen permeability test and a moisture permeability test were conducted.
結果は第４表に示した通り、非常に優れた酸素ガスバリ
ア性を示した。As shown in Table 4, the results showed very excellent oxygen gas barrier properties.
実施例１１〜１２
電子線照射条件として第４表に示したものを用いた以外
には、実施例１０と同様にして、酸素透過度試験、透湿
度試験を行った。Examples 11-12 An oxygen permeability test and a moisture permeability test were conducted in the same manner as in Example 10, except that the electron beam irradiation conditions shown in Table 4 were used.
結果は第４表に示した通り、非常に優れた酸素ガスバリ
ア性を示した。As shown in Table 4, the results showed very excellent oxygen gas barrier properties.
比較例５
電子線照射および水浸漬をしなかった以外は実施例１０
と同様にして、第４表に示した通りのフィルムで酸素透
過度試験、透湿度試験を行った。Comparative Example 5 Example 10 except that electron beam irradiation and water immersion were not performed
In the same manner as above, oxygen permeability tests and moisture permeability tests were conducted using the films shown in Table 4.
結果は第４表に示した通り、酸素力゛スバワア性の劣っ
たものであった。As shown in Table 4, the results showed that the oxygen permeability was poor.
〈発明の効果〉
本発明によれば、含水率０．５重量％以上のエチレン−
ビニルアルコール共重合体に放射線を照射することによ
り得られる変性エチレン−ビニルアルコール共重合体は
著しく優れたガスバリア性を有することが解る。また、
本発明の変性エチレン−ビニルアルコール共重合体は水
蒸気透過性なとの諸物性についても損なわれることはな
い。<Effects of the Invention> According to the present invention, ethylene-
It can be seen that the modified ethylene-vinyl alcohol copolymer obtained by irradiating the vinyl alcohol copolymer with radiation has extremely excellent gas barrier properties. Also,
The modified ethylene-vinyl alcohol copolymer of the present invention does not lose its physical properties such as water vapor permeability.
本発明の変性エチしンービニルアルコール共重合体およ
び本発明の製造方法からなる積層体は単層フィルム、多
層フィルム、袋、紋り容器、ボトル、チューブ、タンク
なと種々の相形に成形して種々の用途のガスバリア性包
装材料として有用に用いられる。The laminate made of the modified ethylene-vinyl alcohol copolymer of the present invention and the production method of the present invention can be molded into various shapes such as a single-layer film, a multilayer film, a bag, a printed container, a bottle, a tube, and a tank. It is usefully used as a gas barrier packaging material for various purposes.
Claims (2)
コール共重合体に放射線を照射することにより得られる
変性エチレン−ビニルアルコール共重合体。(1) A modified ethylene-vinyl alcohol copolymer obtained by irradiating an ethylene-vinyl alcohol copolymer with a water content of 0.5% by weight or more.
ール共重合体からなる樹脂の少なくとも一方の面に熱可
塑性樹脂を積層してなる積層体に、放射線を照射するこ
とにより得られる変性エチレン−ビニルアルコール共重
合体含有積層体。(2) Modified ethylene obtained by irradiating radiation to a laminate made by laminating a thermoplastic resin on at least one side of a resin made of an ethylene vinyl alcohol copolymer with a water content of 0.5% by weight or more. Laminate containing vinyl alcohol copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26266890A JP3234944B2 (en) | 1990-09-28 | 1990-09-28 | Modified ethylene-vinyl alcohol copolymer and its laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26266890A JP3234944B2 (en) | 1990-09-28 | 1990-09-28 | Modified ethylene-vinyl alcohol copolymer and its laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04139220A true JPH04139220A (en) | 1992-05-13 |
| JP3234944B2 JP3234944B2 (en) | 2001-12-04 |
Family
ID=17378949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26266890A Expired - Fee Related JP3234944B2 (en) | 1990-09-28 | 1990-09-28 | Modified ethylene-vinyl alcohol copolymer and its laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3234944B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10168133A (en) * | 1996-12-09 | 1998-06-23 | Kuraray Co Ltd | Ethylene-vinyl alcohol copolymer |
| JP2003071998A (en) * | 2001-09-04 | 2003-03-12 | Toppan Printing Co Ltd | Gas-barrier functional film |
| JP2007253615A (en) * | 2006-02-22 | 2007-10-04 | Nippon Synthetic Chem Ind Co Ltd:The | Laminated structure |
| JP2011174982A (en) * | 2010-02-23 | 2011-09-08 | Kuraray Co Ltd | Method for manufacturing polyvinyl alcohol based polymer film |
-
1990
- 1990-09-28 JP JP26266890A patent/JP3234944B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10168133A (en) * | 1996-12-09 | 1998-06-23 | Kuraray Co Ltd | Ethylene-vinyl alcohol copolymer |
| JP2003071998A (en) * | 2001-09-04 | 2003-03-12 | Toppan Printing Co Ltd | Gas-barrier functional film |
| JP4576777B2 (en) * | 2001-09-04 | 2010-11-10 | 凸版印刷株式会社 | Gas barrier functional film and method for producing the same |
| JP2007253615A (en) * | 2006-02-22 | 2007-10-04 | Nippon Synthetic Chem Ind Co Ltd:The | Laminated structure |
| JP2011174982A (en) * | 2010-02-23 | 2011-09-08 | Kuraray Co Ltd | Method for manufacturing polyvinyl alcohol based polymer film |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3234944B2 (en) | 2001-12-04 |
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