JPH06306198A - Olefin resin molding having gas-barrier properties - Google Patents
Olefin resin molding having gas-barrier propertiesInfo
- Publication number
- JPH06306198A JPH06306198A JP10100293A JP10100293A JPH06306198A JP H06306198 A JPH06306198 A JP H06306198A JP 10100293 A JP10100293 A JP 10100293A JP 10100293 A JP10100293 A JP 10100293A JP H06306198 A JPH06306198 A JP H06306198A
- Authority
- JP
- Japan
- Prior art keywords
- film
- polyolefin
- modified
- polypropylene
- thin film
- 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
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、食品、電子部品等を保
護する為に用いられるガスバリアー性の優れた包装用樹
脂成形品に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin molded product for packaging which is used for protecting foods, electronic parts and the like and has an excellent gas barrier property.
【0002】[0002]
【従来の技術】食品、電子工業部品等をフィルム、容器
で包装し、酸素の透過を抑制することにより内容物の酸
化を防止し、品質を長期間保つことが提案されている。
例えば、特公昭53−12953号公報には、厚さが5
〜300μmのポリエチレンテレフタレート、セロファ
ン、ナイロン、ポリプロピレン、ポリエチレン等のフレ
キシブルなプラスチックフィルムの少なくとも片面に、
一般式Six O y (x=1または2、y=0,1,2ま
たは3)なる組成の珪素酸化物の厚さ100〜3000
オングストロームの透明薄膜層を設けた高度の耐透気性
と耐透湿性を有する透明フレキシブルプラスチックフィ
ルムが開示されている。2. Description of the Related Art Foods, electronic industrial parts, etc. are used as films and containers.
The contents of the
It has been proposed to prevent deterioration and maintain quality for a long time.
For example, in Japanese Patent Publication No. 53-12953, the thickness is 5
~ 300μm polyethylene terephthalate, cellophane
Frame, nylon, polypropylene, polyethylene, etc.
On at least one side of a kisible plastic film,
General formula SixO y(X = 1 or 2, y = 0, 1, 2 or
Or 3) the thickness of the silicon oxide having a composition of 100 to 3000
High degree of air resistance with a transparent thin film layer of Angstrom
And a transparent flexible plastic film with moisture resistance
Rum is disclosed.
【0003】また、特開昭63−237940号公報に
は、上記フレキシブルプラスチックフィルムの少なくと
も一方の面に、In、Sn、Zn、ZrおよびTiから
なる群から選ばれた一種の金属の金属酸化物がスパッタ
リングにより形成され、更にこの上に透明なヒートシー
ル性樹脂膜がコートされた透明ガスバリアーフィルムが
開示されている。Further, Japanese Patent Laid-Open No. 63-237940 discloses a metal oxide of one kind of metal selected from the group consisting of In, Sn, Zn, Zr and Ti on at least one surface of the flexible plastic film. Is disclosed by sputtering, and a transparent heat-sealable resin film is coated on the transparent gas barrier film.
【0004】フィルム素材がポリエチレンテレフタレー
ト、ナイロン、セロファンのような極性基を有する樹脂
であるときは、フィルムと無機酸化膜との密着力が十分
で、ガスバリアー性も良好である。しかし、ポリプロピ
レン、ポリエチレンのような極性基を有しないポリオレ
フィンの成形品の表面に、上記のような無機酸化物から
なる蒸着薄膜を形成させても、ポリオレフィン成形品と
薄膜との密着力が弱いので、この蒸着物にヒートシール
性を付与するために成形品を構成するポリオレフィンの
融点よりも低い融点を有するヒートシール性樹脂をラミ
ネートする場合や、このラミネート物を用い、製袋や蓋
シールの二次加工を行う際や、これら袋を用いたり、容
器内に収容物を充填し、更にはレトルト殺菌する際に外
部応力や熱が成形品に加わって無機酸化薄膜がポリオレ
フィン成形品より剥離し、ガスバリアー性が低下し、実
用に耐えない問題がある。When the film material is a resin having a polar group such as polyethylene terephthalate, nylon or cellophane, the film and the inorganic oxide film have sufficient adhesion and a good gas barrier property. However, even if a vapor-deposited thin film made of the above inorganic oxide is formed on the surface of a polyolefin molded product having no polar groups such as polypropylene and polyethylene, the adhesion between the polyolefin molded product and the thin film is weak. When laminating a heat-sealable resin having a melting point lower than that of the polyolefin constituting the molded article in order to impart heat-sealing property to the vapor-deposited product, or by using this laminated product, it can be used for bag making or lid sealing. When performing the next processing, using these bags, filling the contents in a container, further when external sterilization or heat is applied to the molded product during retort sterilization, the inorganic oxide thin film peels from the polyolefin molded product, There is a problem that the gas barrier property is lowered and it cannot be put to practical use.
【0005】[0005]
【発明が解決しようとする課題】本発明は、無機酸化薄
膜が蒸着されたオレフィン系樹脂成形品であっても、こ
れの二次加工時や使用時に無機酸化薄膜が剥離せず、ガ
スバリアー性が低下しない樹脂成形品を提供することを
目的とするものである。DISCLOSURE OF THE INVENTION The present invention has a gas barrier property even when an olefin resin molded article having an inorganic oxide thin film deposited thereon is not peeled off during secondary processing or during use. It is an object of the present invention to provide a resin molded product that does not deteriorate.
【0006】[0006]
【課題を解決する手段】本発明は、ポリオレフィンに
α,β−エチレン性不飽和カルボン酸をグラフトして変
性した変性ポリオレフィンであって、該変性ポリオレフ
ィン中の不飽和カルボン酸に基づく構成単位濃度が0.
01〜10重量%である変性ポリオレフィンの成形品の
表面に、無機酸化物薄膜を形成した、ガスバリアー性の
付与されたオレフィン系樹脂成形品を提供するものであ
る。The present invention is a modified polyolefin obtained by modifying an polyolefin by grafting an α, β-ethylenically unsaturated carboxylic acid, wherein the concentration of the constituent unit based on the unsaturated carboxylic acid in the modified polyolefin is 0.
Provided is an olefin-based resin molded product having a gas barrier property, in which an inorganic oxide thin film is formed on the surface of a modified polyolefin molded product in an amount of 01 to 10% by weight.
【0007】[0007]
【作用】本発明では、基材の変性ポリオレフィンがカル
ボキシル基(−COOH)を有しているので、無機酸化
物蒸着膜との密着性が強固となる。In the present invention, since the modified polyolefin of the substrate has a carboxyl group (-COOH), the adhesiveness with the inorganic oxide vapor deposition film becomes strong.
【0008】[0008]
【発明の具体的な説明】変性ポリオレフィン フィルム、容器に成形される変性ポリオレフィンは、
α,β−エチレン性不飽和カルボン酸(その無水物も含
む)をポリオレフィンにグラフト重合させることにより
得られる。グラフト重合させる手法としては、ポリオレ
フィン、α,β−エチレン性不飽和カルボン酸、及び触
媒を押出機中で溶融混練する方法(特公昭43−274
21号、特公昭59−15127号)、または適当な溶
媒中に溶解しているポリオレフィンにグラフト用の不飽
和カルボン酸及び触媒を添加して加熱攪拌する方法(特
公昭44−15422号、特公昭52−30546)等
がある。DETAILED DESCRIPTION OF THE INVENTION Modified polyolefin films, modified polyolefins molded into containers,
It is obtained by graft-polymerizing α, β-ethylenically unsaturated carboxylic acid (including its anhydride) on polyolefin. As a method of graft polymerization, a method of melt-kneading a polyolefin, α, β-ethylenically unsaturated carboxylic acid, and a catalyst in an extruder (Japanese Patent Publication No. 43-274).
No. 21, JP-B-59-15127), or a method in which an unsaturated carboxylic acid for grafting and a catalyst are added to a polyolefin dissolved in a suitable solvent and the mixture is heated and stirred (JP-B-44-15422, JP-B-44152). 52-30546) and the like.
【0009】変性させるポリオレフィンとしては、エチ
レン、プロピレン、ブテン−1、ペンテン−1等の炭素
数が2〜8のα−オレフィンの単独重合体の他に、エチ
レンと他のα−オレフィンとの共重合体、例えばエチレ
ン−プロピレン共重合体、エチレン−ブテン−1共重合
体、及びエチレン−ヘキセン−1共重合体やプロピレン
−ブテン−1、プロピレン−エチレン−ブテン−1共重
合体等のα−オレフィン同士の結晶性重合体も含む。こ
れらの重合体、共重合体をブレンドして使用しても良
い。Examples of the polyolefin to be modified include homopolymers of α-olefins having 2 to 8 carbon atoms such as ethylene, propylene, butene-1, and pentene-1, as well as copolymers of ethylene with other α-olefins. Α-of polymers such as ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-hexene-1 copolymer and propylene-butene-1, propylene-ethylene-butene-1 copolymer Also included are crystalline polymers of olefins. You may blend and use these polymers and copolymers.
【0010】グラフトさせる不飽和カルボン酸として
は、アクリル酸、マレイン酸、フマル酸、イタコン酸、
ハイミック酸またはそれらの無水物等が挙げられる。中
でもアクリル酸、または無水マレイン酸が望ましい。変
性したポリオレフィンを未変性のポリオレフィンで希釈
して用いても良い。成形品のα,β−エチレン性不飽和
カルボン酸に基づく構成単位濃度が上記範囲より少ない
と、無機酸化物薄膜との結合力が十分でなく、また上記
範囲より多くしても結合力の向上が見られず、さらにグ
ラフト反応時にポリプロピレン系では分解反応が、また
ポリエチレン系では架橋反応が平衡して起こるため、ポ
リプロピレン系では低分子量分が増加し結合力が低下し
たり、ポリエチレン系ではゲルが多く延伸フィルムが生
産できないなどの問題が発生する。As the unsaturated carboxylic acid to be grafted, acrylic acid, maleic acid, fumaric acid, itaconic acid,
Hymic acids or their anhydrides may be mentioned. Of these, acrylic acid or maleic anhydride is preferable. The modified polyolefin may be diluted with an unmodified polyolefin before use. When the concentration of the constituent unit based on α, β-ethylenically unsaturated carboxylic acid in the molded product is less than the above range, the binding force with the inorganic oxide thin film is insufficient, and even if it exceeds the above range, the binding force is improved. In addition, since the decomposition reaction occurs in the polypropylene type during the grafting reaction and the crosslinking reaction occurs in equilibrium in the polyethylene type during the grafting reaction, the low molecular weight component in the polypropylene type increases and the binding force decreases, and the gel type in the polyethylene type decreases. There are problems such that many stretched films cannot be produced.
【0011】変性ポリオレフィン、もしくは未変性ポリ
オレフィンで希釈された変性ポリオレフィンのMFR
(JIS K−7210)は、成形品が得られれば良
く、通常0.1〜100g/10分が好ましく、さらに
好ましくは0.5〜20g/10分である。MFR of modified polyolefin or modified polyolefin diluted with unmodified polyolefin
(JIS K-7210) is sufficient as long as a molded product can be obtained, and is preferably 0.1 to 100 g / 10 minutes, more preferably 0.5 to 20 g / 10 minutes.
【0012】成形品 成形品は押出成形、射出成形、真空成形、中空成形等に
よりフィルム、シート、容器、箱等に成形される。又、
変性ポリオレフィンとポリエチレン、ポリプロピレン、
エチレン・酢酸ビニル共重合体、ポリアミド、ポリブチ
レンテレフタレート、ポリエチレンテレフタレート、ポ
リフェニレンスルフィド、ポリフェニレンエーテル、ポ
リカーボネート等の熱可塑性樹脂との積層体構造として
も良い。又、フィルム、シートは延伸されていても良
い。 Molded Article A molded article is formed into a film, sheet, container, box or the like by extrusion molding, injection molding, vacuum molding, hollow molding or the like. or,
Modified polyolefin and polyethylene, polypropylene,
It may have a laminate structure with a thermoplastic resin such as an ethylene / vinyl acetate copolymer, polyamide, polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide, polyphenylene ether, or polycarbonate. Further, the film or sheet may be stretched.
【0013】肉厚はフィルムにおいて5〜200μm、
シートにおいて200〜1,500μm、小型容器、箱
型等のハウジングにおいて300〜2,500μm、タ
ンク容器、20リットルの薬品容器において1〜10m
mが一般である。成形品は必要によりその変性ポリオレ
フィンの表面をコロナ放電処理、オゾン処理、グロー放
電処理、プラズマ処理、化学薬品による酸化処理を施し
ても良い。しかし、一般に無機酸化物の薄膜の蒸着がこ
れら酸化処理を伴って行われることが多いので、成形
中、あるいは成形後にわざわざかかる酸化処理をする必
要はない。The thickness of the film is 5 to 200 μm,
200 to 1,500 μm for sheets, 300 to 2,500 μm for small containers, box-shaped housings, etc., 1 to 10 m for tank containers and 20 liter chemical containers.
m is common. If necessary, the molded product may be subjected to corona discharge treatment, ozone treatment, glow discharge treatment, plasma treatment, or oxidation treatment with a chemical agent on the surface of the modified polyolefin. However, in general, a thin film of an inorganic oxide is often vapor-deposited together with these oxidation treatments, and thus it is not necessary to perform the oxidation treatment during or after the molding.
【0014】無機酸化物の蒸着 無機酸化物の薄膜としては、SiOx 、SnOx 、Zn
Ox 、IrOx 等の200〜4,000オングストロー
ム、好ましくは300〜3,000オングストロームの
ものが利用される。蒸着膜の厚み200〜4,000オ
ングストロームは、透明性、蒸着速度、ガスバリアー
性、フィルムの巻き取り性等から制約される。蒸着法と
しては、高周波誘導加熱方式の蒸着機内で成形品を真空
下(1×10 -3〜1×106 トール)で無機酸化物を蒸
着する方法(特公昭53−12963号);予め排気
し、真空化した蒸着機内で揮発した有機シリコン化合
物、酸素及び不活性ガスを含むガス流をマグネトロング
ロー放電によってプラズマを発生させてSiOx を該蒸
着機内で成形品に蒸着させる方法(特開昭64−877
72号、USP4、557、946号、USP4、59
9、678号)等がある。又、1990年11月発刊の
工業材料、第38巻、第14号の第104〜105頁
で、イオンプレーティング法、高周波プラズマCVD
法、電子ビーム(EB)蒸着法、スパッタリング法とし
て分類され、その原理が紹介されている。[0014]Inorganic oxide deposition As a thin film of inorganic oxide, SiOx, SnOx, Zn
Ox, IrOx200-4,000 ang straws
Preferably 300-3,000 Angstroms
Things are used. Evaporated film thickness 200-4,000
Ngstrom has transparency, deposition rate, gas barrier
However, it is restricted by the film properties, film winding properties, and the like. Evaporation method
Then, the molded product is vacuumed in the high frequency induction heating type vapor deposition machine.
Bottom (1 x 10 -3~ 1 x 106Steam the inorganic oxide with
How to wear (Japanese Patent Publication No. 53-12963); Exhaust in advance
Then, the organic silicon compound volatilized in the vacuumed evaporator.
Magnetron for gas flow containing gas, oxygen and inert gas
Plasma is generated by low discharge to generate SiOxThe steam
A method of vapor depositing a molded article in a machine (Japanese Patent Laid-Open No. 64-877).
72, USP 4,557,946, USP 4,59
9, 678) and the like. Also published in November 1990
Industrial Materials, Vol. 38, No. 14, pp. 104-105
With ion plating method, high frequency plasma CVD
Method, electron beam (EB) vapor deposition method, sputtering method
The principle is introduced.
【0015】[0015]
【実施例】以下、実施例により、本発明を詳細に説明す
るが、これにより本発明の範囲は特に限定されるもので
はない。The present invention will be described in detail below with reference to examples, but the scope of the present invention is not particularly limited thereby.
【0016】変性ポリプロピレンの製造例 例1 ポリプロピレン(MFR 2g/10分、密度 0.9
05g/cm3 )のパウダー100重量部に、過酸化ベ
ンゾイル0.8重量部、無水マレイン酸1.2重量部を
添加後、ヘンシェルミキサーにて混合し、押出機にてダ
イより220℃でストランド状に押出し、水冷後、カッ
ティングしてペレットを得た。この変性ポリプロピレン
のペレットを沸騰したキシレンに溶解して大量のアセト
ンにて再沈させた後、赤外吸収スペクトル分析法で変性
ポリプロピレン中に占める無水マレイン酸に基づく構成
単位濃度を測定したところ、0.7重量部%がグラフト
共重合していた。[0016] Production of modified polypropylene Example 1 Polypropylene (MFR 2 g / 10 min, density 0.9
(05 g / cm 3 ) powder (100 parts by weight), benzoyl peroxide (0.8 parts by weight) and maleic anhydride (1.2 parts by weight) were added, and the mixture was mixed with a Henschel mixer. The mixture was extruded into a shape, cooled with water, and then cut to obtain pellets. The modified polypropylene pellets were dissolved in boiling xylene, reprecipitated with a large amount of acetone, and then the concentration of the constituent unit based on maleic anhydride in the modified polypropylene was measured by infrared absorption spectroscopy. Graft copolymerization was carried out in an amount of 0.7% by weight.
【0017】例2 エチレン−プロピレン共重合体(エチレン含有5%、M
FR 1g/10分、密度 0.89g/cm3 )のパ
ウダーを100重量部に過酸化ベンゾイル0.8重量
部、無水マレイン酸1.2重量部を添加し、例1と同様
に変性共重合体を製造した。変性共重合体に占める無水
マレイン酸成分濃度を測定したところ0.9重量%であ
った。Example 2 Ethylene-propylene copolymer (ethylene content 5%, M
FR 1 g / 10 min, density 0.89 g / cm 3 ) 100 parts by weight of powder, 0.8 parts by weight of benzoyl peroxide and 1.2 parts by weight of maleic anhydride were added, and the modified copolymer was added in the same manner as in Example 1. A coalesce was manufactured. The concentration of the maleic anhydride component in the modified copolymer was measured and found to be 0.9% by weight.
【0018】変性ポリエチレンの製造例 例3 直鎖状低密度ポリエチレン(MFR 2g/10分、密
度 0.920g/cm3 、エチレン含有が91.0重
量%、ヘキセン含有が9.0重量%)100重量部に
2,5−ジメル−2,5−ジ(t−ブチルパ−オキシ)
ヘキサン0.04重量部および無水マレイン酸2重量部
を添加後、ヘンシェルミキサーにて混合し、押出機にて
ダイより180℃でストランド状に押出し、水冷後、カ
ッティングしてペレットを得た。この変性ポリプロピレ
ンのペレットを沸騰したキシレンに溶解して大量のアセ
トンにて再沈させた後、赤外吸収スペクトル分析法で変
性ポリエチレン中に占める無水マレイン酸に基づく構成
単位濃度を測定したところ、1.9重量%がグラフト共
重合していた。[0018] Production of modified polyethylene Example 3 linear low-density polyethylene (MFR 2 g / 10 min, density 0.920 g / cm 3, ethylene content is 91.0 wt%, hexene containing 9.0 wt%) 100 2,5-dimel-2,5-di (t-butylperoxy) in parts by weight
Hexane (0.04 parts by weight) and maleic anhydride (2 parts by weight) were added, mixed with a Henschel mixer, extruded into a strand at 180 ° C. from a die with an extruder, cooled with water, and cut to obtain pellets. The modified polypropylene pellets were dissolved in boiling xylene and reprecipitated with a large amount of acetone, and then the concentration of the structural unit based on maleic anhydride in the modified polyethylene was measured by infrared absorption spectroscopy. Graft copolymerization was performed in an amount of 0.9% by weight.
【0019】実施例1 例1で得た変性ポリプロピレンを押出機で溶融し、T−
ダイより238℃でシート状に押し出し、金属ロールで
冷却して厚さ1mmのシートを得た。このシートを12
0℃に加熱し、ロール群の周速差を利用して縦方向に5
倍延伸した。ついで、テンターオーブン内に導き、15
7℃に再加熱した後、テンターを用いて横方向に10倍
延伸し、163℃でアニーリング処理し、コロナ放電処
理して肉厚が20μmの二軸延伸フィルムを得た。Example 1 The modified polypropylene obtained in Example 1 was melted in an extruder to obtain T-
A sheet having a thickness of 1 mm was obtained by extruding a sheet at 238 ° C. from a die and cooling with a metal roll. This sheet 12
Heat to 0 ° C, and use the difference in peripheral speed of the rolls to move vertically 5
It was stretched twice. Then, lead it into the tenter oven, 15
After reheating to 7 ° C., it was stretched 10 times in the transverse direction using a tenter, annealed at 163 ° C., and corona discharge treated to obtain a biaxially stretched film having a thickness of 20 μm.
【0020】このコロナ放電処理された二軸延伸フィル
ムを、プラズマ蒸着装置内に置き、装置内を1×10-6
トールの減圧下にしたのち、ヘキサメチルジシロキサン
3容量部、酸素3容量部、ヘリウム20容量部、アルゴ
ン13容量部の混合気体を導き、不平衡型マグネトロン
よりグロー放電を行ってプラズマを発生させSiO2の
薄膜を二軸延伸フィルム状に蒸着させた。蒸着時のグロ
ー放電の条件は、得られたSiO2 蒸着二軸延伸フィル
ムの酸素透過率が5.0cc/m2 ・atm・day
(JIS 1707−35)となるように設定した。This biaxially stretched film subjected to corona discharge treatment was placed in a plasma deposition apparatus, and the inside of the apparatus was set at 1 × 10 -6.
After reducing the pressure under a reduced pressure of torr, a mixed gas of 3 parts by volume of hexamethyldisiloxane, 3 parts by volume of oxygen, 20 parts by volume of helium, and 13 parts by volume of argon was introduced, and glow discharge was performed from the unbalanced magnetron to generate plasma. A thin film of SiO 2 was deposited in the form of a biaxially stretched film. The glow discharge conditions during vapor deposition were such that the obtained SiO 2 vapor-deposited biaxially stretched film had an oxygen permeability of 5.0 cc / m 2 · atm · day.
(JIS 1707-35).
【0021】実施例2 例1で得た変性ポリプロピレン5重量部を、未変性ポリ
プロピレン(MFR0.8g/10分、密度 0.95
0g/cm3 )95重量部で希釈したもの(希釈物中の
マレイン酸の構成単位濃度 0.35重量%)を変性ポ
リプロピレンの代わりに用いる他は実施例1と同様にし
てSiO2 蒸着二軸延伸ポリプロピレンフィルムを製造
した。Example 2 5 parts by weight of the modified polypropylene obtained in Example 1 was added to unmodified polypropylene (MFR 0.8 g / 10 min, density 0.95).
0 g / cm 3 ) SiO 2 vapor-deposited biaxial in the same manner as in Example 1 except that the diluted polypropylene (concentration of maleic acid in the diluted product: 0.35 wt%) diluted with 95 parts by weight is used instead of the modified polypropylene. A stretched polypropylene film was produced.
【0022】実施例3 例2で得た変性共重合体と実施例2で使用した未変性ポ
リプロピレンを、別々の押出機で溶融したものを一台の
ダイに供給し、ダイ内で層状に重ね、押し出して変性共
重合体の層の厚さが0.1mm、未変性ポリプロピレン
層の厚さが0.9mm、合計厚さが1mmのシートを作
成し実施例1と同様にして延伸し厚さ20μmのフィル
ムを作成し、変性共重合体側をコロナ放電処理後、実施
例1と同様にしてSiO2 蒸着二軸延伸フィルムを製造
した。Example 3 The modified copolymer obtained in Example 2 and the unmodified polypropylene used in Example 2 were melted by different extruders and fed to one die, which was layered in the die. Then, a sheet having a thickness of the modified copolymer layer of 0.1 mm, an unmodified polypropylene layer of 0.9 mm, and a total thickness of 1 mm was extruded to form a sheet and stretched in the same manner as in Example 1. A 20 μm film was prepared, the modified copolymer side was subjected to corona discharge treatment, and then a SiO 2 vapor-deposited biaxially stretched film was produced in the same manner as in Example 1.
【0023】比較例1 未変性ポリプロピレン(MFR 0.8g/10分、密
度 0.905g/cm3 )を変性ポリプロピレンの代
わりに用いる他は実施例1と同様にしてSiO 2 蒸着二
軸延伸ポリプロピレンフィルムを製造した。Comparative Example 1 Unmodified polypropylene (MFR 0.8 g / 10 min, dense polypropylene)
Degree 0.905g / cm3) For modified polypropylene
SiO 2 is used in the same manner as in Example 1 except that it is used instead. 2Vapor deposition
An axially oriented polypropylene film was produced.
【0024】比較例2 例1で得た変性ポリプロピレン1重量部を、未変性ポリ
プロピレン(MFR0.8g/10分、密度 0.90
5g/cm3 )99重量部で希釈したもの(マレイン酸
の構成単位濃度 0.07重量%)を変性ポリプロピレ
ンの代わりに用いる他は実施例1と同様にしてSiO2
蒸着二軸延伸ポリプロピレンフィルムを製造した。Comparative Example 2 1 part by weight of the modified polypropylene obtained in Example 1 was added to unmodified polypropylene (MFR 0.8 g / 10 min, density 0.90).
5 g / cm 3 ) 99 parts by weight diluted (constituent unit concentration of maleic acid 0.07% by weight) was used instead of the modified polypropylene, and SiO 2 was used in the same manner as in Example 1.
A vapor-deposited biaxially oriented polypropylene film was produced.
【0025】実施例4 例3で得た変性ポリエチレンを、押出機で溶融し、イン
フレダイより160℃で筒状に押し出し、バブルの内部
に空気を吹き込んでブロー比2まで膨張させた後、コロ
ナ放電処理を行い、肉厚が40μmの変性ポリエチレン
フィルムを得た。このフィルムを用いて実施例1と同様
にSiO2 蒸着ポリエチレンフィルムを製造した。Example 4 The modified polyethylene obtained in Example 3 was melted by an extruder and extruded into a cylindrical shape from an inflation die at 160 ° C., air was blown into the bubbles to expand them to a blow ratio of 2, and then the corona was used. Electric discharge treatment was performed to obtain a modified polyethylene film having a thickness of 40 μm. Using this film, a SiO 2 vapor-deposited polyethylene film was produced in the same manner as in Example 1.
【0026】比較例3 未変性直鎖状低密度ポリエチレン(MFR 2g/10
分、密度 0.920g/cm3 )を変性ポリエチレン
の代わりに用いる他は、実施例4と同様にしてSiO2
蒸着ポリエチレンフィルムを製造した。なお、全ての延
伸フィルムの酸素透過率が5.0cc/m2 ・atm・
dayとなるようにグロー放電の条件を変えて行った。Comparative Example 3 Unmodified linear low-density polyethylene (MFR 2 g / 10
Min, except for using a density 0.920 g / cm 3) in place of the modified polyethylene, the same procedure as in Example 4 SiO 2
A vapor-deposited polyethylene film was produced. The oxygen permeability of all stretched films was 5.0 cc / m 2 · atm ·
The glow discharge conditions were changed so as to obtain the day.
【0027】評価 (1)外応力に対する変化 実施例1〜4、および比較例1〜3で得たSiO2 蒸着
フィルムを、各立計器(株)製ゲルボテスターを用い、
フィルムを筒状に丸めたのち、この筒の両端をテスター
の把持器具に固定し、10回、±90度回転ねじりの繰
り返しを行った後、酸素透過率を測定した。その測定値
を表1に示す。 (2)二次加工に対する変化 実施例1〜2、および比較例1〜2で得たSiO2 蒸着
フィルムのSiO2 蒸着面に、ラミネータ装置を用い、
メルトインデックス5g/10分、密度0.922g/
cm3 の低密度ポリエチレンを320℃で20μmの肉
厚のフィルム状にT−ダイより押し出し、ラミネートし
た。このラミネート物の酸素透過率を表1に示す。 Evaluation (1) Change with respect to external stress The SiO 2 vapor-deposited films obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were used in a gel votester manufactured by each instrumental analyzer,
After rolling the film into a tube shape, both ends of the tube were fixed to a gripping device of a tester, and a twist of ± 90 ° was repeated 10 times, and then the oxygen transmission rate was measured. The measured values are shown in Table 1. (2) secondary processing varies Examples 1-2 against, and the SiO 2 deposition surface of the SiO 2 deposited film obtained in Comparative Examples 1-2, using a laminator apparatus,
Melt index 5g / 10min, density 0.922g /
cm 3 of low density polyethylene was extruded from a T-die at 320 ° C. into a film having a thickness of 20 μm and laminated. The oxygen transmission rate of this laminate is shown in Table 1.
【0028】[0028]
【表1】 [Table 1]
【0029】[0029]
【発明の効果】本発明の無機酸化物が蒸着したカルボキ
シル基を有する結晶性オレフィン共重合体の成形品は、
二次加工時や使用時に、熱や力が加わってもガスバリア
ー性が低下しない樹脂成形品である。従って、レトルト
パウチ包装材、IC包装材としても有用である。EFFECTS OF THE INVENTION A molded article of a crystalline olefin copolymer having a carboxyl group, on which the inorganic oxide of the present invention is vapor deposited, is
It is a resin molded product whose gas barrier properties do not deteriorate even when heat or force is applied during secondary processing or use. Therefore, it is also useful as a retort pouch packaging material and an IC packaging material.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 水野 明 三重県四日市市東邦町1番地 三菱油化株 式会社四日市総合研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akira Mizuno 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Petrochemical Co., Ltd. Yokkaichi Research Institute
Claims (1)
和カルボン酸をグラフトして変性した変性ポリオレフィ
ンであって、該変性ポリオレフィン中の不飽和カルボン
酸に基づく構成単位濃度が0.01〜10重量%である
変性ポリオレフィンの成形品の表面に、無機酸化物薄膜
を形成した、ガスバリアー性の付与されたオレフィン系
樹脂成形品。1. A modified polyolefin obtained by graft-modifying a polyolefin α, β-ethylenically unsaturated carboxylic acid, wherein the concentration of the constituent unit based on the unsaturated carboxylic acid in the modified polyolefin is 0.01 to 10% by weight. An olefin resin molded product having a gas barrier property, in which an inorganic oxide thin film is formed on the surface of the modified polyolefin molded product.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10100293A JP3430551B2 (en) | 1993-04-27 | 1993-04-27 | Olefin resin molded product with gas barrier properties |
DE69425296T DE69425296T2 (en) | 1993-04-27 | 1994-04-21 | Products based on olefin resins with properties for gas impermeability |
EP19940106233 EP0622399B1 (en) | 1993-04-27 | 1994-04-21 | Olefin resin-based articles having gas barrier properties |
US08/583,859 US5763088A (en) | 1993-04-27 | 1996-01-11 | Olefin resin-based articles having gas barrier properties |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10100293A JP3430551B2 (en) | 1993-04-27 | 1993-04-27 | Olefin resin molded product with gas barrier properties |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH06306198A true JPH06306198A (en) | 1994-11-01 |
JP3430551B2 JP3430551B2 (en) | 2003-07-28 |
Family
ID=14289065
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10100293A Expired - Lifetime JP3430551B2 (en) | 1993-04-27 | 1993-04-27 | Olefin resin molded product with gas barrier properties |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3430551B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002179068A (en) * | 2000-12-20 | 2002-06-26 | Toppan Printing Co Ltd | Vessel with barrier property |
JP2002522609A (en) * | 1998-08-17 | 2002-07-23 | トレスパファン、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツング | Method for applying a polysilicate barrier coating to a polyolefin object and articles produced thereby |
WO2018047422A1 (en) * | 2016-09-07 | 2018-03-15 | リンテック株式会社 | Gas barrier laminate and sealed body |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7151338B2 (en) | 2018-09-28 | 2022-10-12 | 凸版印刷株式会社 | Laminated films and packaging containers |
-
1993
- 1993-04-27 JP JP10100293A patent/JP3430551B2/en not_active Expired - Lifetime
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002522609A (en) * | 1998-08-17 | 2002-07-23 | トレスパファン、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツング | Method for applying a polysilicate barrier coating to a polyolefin object and articles produced thereby |
JP2002179068A (en) * | 2000-12-20 | 2002-06-26 | Toppan Printing Co Ltd | Vessel with barrier property |
WO2018047422A1 (en) * | 2016-09-07 | 2018-03-15 | リンテック株式会社 | Gas barrier laminate and sealed body |
Also Published As
Publication number | Publication date |
---|---|
JP3430551B2 (en) | 2003-07-28 |
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