JPH06298264A - Polyethylene modified-container - Google Patents
Polyethylene modified-containerInfo
- Publication number
- JPH06298264A JPH06298264A JP5087636A JP8763693A JPH06298264A JP H06298264 A JPH06298264 A JP H06298264A JP 5087636 A JP5087636 A JP 5087636A JP 8763693 A JP8763693 A JP 8763693A JP H06298264 A JPH06298264 A JP H06298264A
- Authority
- JP
- Japan
- Prior art keywords
- polyethylene
- container
- irradiated
- ethylene
- electron beam
- 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
【０００１】[0001]
【産業上の利用分野】本発明は、絞り出しチューブ状円
筒容器やカップなどのヒートシールもしくは超音波シー
ルのように融着により内容物を密封することが求められ
るポリエチレン製改質容器に関するものであって、より
詳しくは、特定の透過度を有する電子線を照射した、耐
熱性及び耐薬品性に優れ、かつ融着性に優れた特定のポ
リエチレン組成物からなるポリエチレン製改質容器に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyethylene reforming container which is required to seal the contents by fusion such as heat sealing or ultrasonic sealing of a squeezed tubular cylindrical container or cup. More specifically, the present invention relates to a polyethylene reforming container made of a specific polyethylene composition which is irradiated with an electron beam having a specific transmittance and is excellent in heat resistance, chemical resistance, and fusion property.
【０００２】ポリエチレンを代表とするポリオレフィン
が、電子線などの放射線によって架橋反応を起こし、耐
熱性、耐薬品性機械的強度が向上することは良く知られ
ており、例えば、ケーブル、熱収縮フィルム等において
工業化されている。これら耐熱性等の物性向上は、架橋
により分子が三次元網状構造となることに起因するが、
この三次元網状構造となったポリエチレンは、通常、融
点以上の温度においても溶融せず、そのためヒートシー
ルもしくは超音波シールなどの手段での融着性に劣って
おり、経時もしくは高温殺菌処理時にシール部が剥離し
てしまい、絞り出しチューブ状円筒容器などのヒートシ
ールや超音波シールなどの融着によって内容物を密封す
ることが求められる容器の素材としては不適当なもので
あった。It is well known that a polyolefin typified by polyethylene undergoes a cross-linking reaction by radiation such as an electron beam to improve heat resistance, chemical resistance and mechanical strength. For example, a cable, a heat shrink film, etc. Have been industrialized in. The improvement in physical properties such as heat resistance results from the fact that the molecule becomes a three-dimensional network structure due to crosslinking,
Polyethylene with this three-dimensional network structure does not usually melt even at temperatures above the melting point, and therefore has poor fusion properties by means such as heat sealing or ultrasonic sealing, and therefore seals over time or during high temperature sterilization treatment. Since the parts are peeled off, it is unsuitable as a material for a container which is required to hermetically seal the contents by fusion such as heat sealing or ultrasonic sealing such as a squeezed tubular cylindrical container.
【０００３】本発明者らは、さきに、密度が０．９００
ないし０．９７５ｇ／ｃｍ3 のポリエチレンおよびエチ
レン−α−オレフィン共重合体の組成物からなる絞り出
しチューブ状円筒容器に電子線を照射することによっ
て、高温での殺菌処理によっても収縮率が少なく、かつ
柔軟性を有するチューブ状円筒容器が得られるという知
見を得、特願平４−２８７９０６号として特許出願し
た。The present inventors have previously found that the density is 0.900.
To 0.975 g / cm 3 by irradiating a squeezed tubular cylindrical container made of a composition of polyethylene and an ethylene-α-olefin copolymer with an electron beam, the shrinkage rate is small even by sterilization treatment at high temperature, and We obtained the finding that a flexible tubular container can be obtained, and filed a patent application as Japanese Patent Application No. 4-287906.
【０００４】本発明者らは、上記先願発明を追試する一
方で、さらにヒートシール性が優れたポリエチレン系組
成物からなる容器が求められているという現状を認識
し、研究を重ねてきたところ、先願発明における容器に
照射される電子線の透過度を調整することによって、ヒ
ートシールや超音波シールなどの融着性に優れた容器用
素材が得られるという知見を得、本発明を完成した。The inventors of the present invention have repeated the above-mentioned prior invention and, while recognizing the present situation in which a container made of a polyethylene-based composition having further excellent heat-sealing property is required, have made repeated studies. The present invention was completed by obtaining the finding that a container material having excellent fusion properties such as heat seal and ultrasonic seal can be obtained by adjusting the transmittance of the electron beam with which the container in the prior invention is irradiated. did.
【０００５】[0005]
【発明の目的】すなわち、本発明の目的は、耐熱性や耐
薬品性などの架橋ポリエチレンの優れた物性を損なうこ
となく、優れた融着性を有するポリエチレン製改質容器
を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a polyethylene reforming container having excellent fusion-bonding properties without impairing the excellent physical properties of crosslinked polyethylene such as heat resistance and chemical resistance. .
【０００６】[0006]
【課題を解決するための手段】本発明は前記目的を達成
するために提案されたもので、容器、特に優れた融着性
が求められる容器の素材として、特定のポリマー組成物
を使用し、これに特定の透過度を有する電子線による照
射処理をすることを特徴とするものである。すなわち、
本発明によれば、電子線の被照射物に対する透過度を被
照射物表面の相対線量を１００％とした時、被照射物の
厚み方向の中間において６０ないし８０％また裏面にお
いて４０％以下となるように照射した、密度０．９００
ないし０．９７５ｇ／ｃｍ3 のポリエチレンと、エチレ
ン−α−オレフィン共重合体からなる組成物を素材とす
るポリエチレン製改質容器が提供される。DISCLOSURE OF THE INVENTION The present invention has been proposed in order to achieve the above object, and uses a specific polymer composition as a material for a container, particularly a container for which excellent fusion bonding property is required, This is characterized in that irradiation treatment with an electron beam having a specific transmittance is performed. That is,
According to the present invention, the transmittance of the electron beam to the object to be irradiated is 60 to 80% in the middle of the thickness direction of the object to be irradiated and 40% or less on the back surface when the relative dose to the surface of the object is 100%. Irradiated so that the density is 0.900
Provided is a polyethylene reforming container made of a composition comprising polyethylene of 0.975 g / cm 3 and ethylene-α-olefin copolymer.
【０００７】ポリエチレンに対するエチレン−α−オレ
フィン共重合体の配合割合は、重量比で５ないし５０
％、特に１０ないし４０％であることが好ましい。電子
線の被照射物に対する透過度は、電子線発生装置の加速
電圧、もしくは照射窓と被照射物との距離によって適宜
調整することができる。また、本発明によれば、被照射
物の表面の電子線の吸収線量が５０ないし５００ｋＧ
ｙ、好ましくは１００ないし３００ｋＧｙである時に好
適な融着性を有するポリエチレン製改質容器が提供され
る。The mixing ratio of the ethylene-α-olefin copolymer to polyethylene is 5 to 50 by weight.
%, Particularly preferably 10 to 40%. The transmittance of the electron beam to the object to be irradiated can be appropriately adjusted by the acceleration voltage of the electron beam generator or the distance between the irradiation window and the object to be irradiated. Further, according to the present invention, the absorbed dose of the electron beam on the surface of the irradiation object is 50 to 500 kG.
Provided is a polyethylene reforming container having a suitable fusion property when y, preferably 100 to 300 kGy.
【０００８】[0008]
【発明の具体的説明】本発明における最大の技術的特徴
は、前記ポリエチレンとエチレン−α−オレフィン共重
合体との組成物を、射出成形、押出成形等、自体公知の
成形方法により成形した容器に、被照射物に対する特定
の透過度を有する電子線を照射する点にある。本発明に
おいては、電子線の透過度を被照射物表面の相対線量を
１００％とした時、厚み方向の中間を６０ないし８０
％、裏面を４０％以下となるように、電子線の加速電
圧、もしくは照射窓と被照射物との距離を規定し、被照
射物の表面に吸収線量５０ないし５００ｋＧｙ照射をす
ることも重要な特徴である。DETAILED DESCRIPTION OF THE INVENTION The most technical feature of the present invention is a container obtained by molding the composition of polyethylene and an ethylene-α-olefin copolymer by a molding method known per se such as injection molding or extrusion molding. In addition, it is a point of irradiating an electron beam having a specific transmittance with respect to the object to be irradiated. In the present invention, the electron beam transmittance is 60 to 80 in the middle of the thickness direction when the relative dose on the surface of the irradiation object is 100%.
%, It is important to define the accelerating voltage of the electron beam or the distance between the irradiation window and the irradiation target so that the back surface becomes 40% or less, and irradiate the surface of the irradiation target with an absorbed dose of 50 to 500 kGy. It is a feature.
【０００９】このように、特殊な電子線の照射を行うこ
とによって、被照射物が層状に架橋度の異なるポリエチ
レン組成物が得られる。この架橋ポリエチレンは、未照
射ポリエチレンと同等の融着性を持ち、かつ電子線を被
照射物に均一に透過させたものに比較して遜色ない耐熱
性を有する架橋ポリエチレン製容器が提供される。As described above, by irradiating with a special electron beam, a polyethylene composition having a different degree of cross-linking can be obtained in a layer to be irradiated. This cross-linked polyethylene has a fusion bonding property equivalent to that of unirradiated polyethylene, and provides a container made of cross-linked polyethylene having heat resistance comparable to that of a material in which an electron beam is evenly transmitted through an object to be irradiated.
【００１０】本発明で用いるポリエチレンとは、密度が
０．９００ｇ／ｃｍ3 ないし０．９７５ｇ／ｃｍ3 、好
ましくは０．９２０ないし０．９５０ｇ／ｃｍ3 、特に
好ましくは０．９３５ないし０．９４０ｇ／ｃｍ3 、メ
ルトフローレイト（ＭＦＲ）が０．０１ないし１０ｇ／
１０ｍｉｎ、好ましくは０．１ないし５ｇ／１０ｍｉｎ
のエチレンの単独重合体、または、エチレンと他のα−
オレフィン、例えば、プロピレン、１−ブテン等との共
重合体をいう。The polyethylene used in the present invention has a density of 0.900 g / cm 3 to 0.975 g / cm 3 , preferably 0.920 to 0.950 g / cm 3 , and particularly preferably 0.935 to 0.940 g. / Cm 3 , melt flow rate (MFR) 0.01 to 10 g /
10 min, preferably 0.1 to 5 g / 10 min
Ethylene homopolymer, or ethylene and other α-
It refers to a copolymer with an olefin such as propylene or 1-butene.
【００１１】本発明で用いるエチレン−α−オレフィン
共重合体とは、 密度が０．８５０ないし０．９００ｇ
／ｃｍ3 、特に０．８６０ないし０．８９５ｇ／ｃｍ
3 、ＭＦＲは０．１ないし１０ｇ／１０ｍｉｎ、特に
０．２ないし５ｇ／１０ｍｉｎの低結晶ないし非晶性の
エチレン−α−オレフィン共重合体が好ましく使用され
る。The ethylene-α-olefin copolymer used in the present invention has a density of 0.850 to 0.900 g.
/ Cm 3 , especially 0.860 to 0.895 g / cm
3 , a low crystalline or amorphous ethylene-α-olefin copolymer having an MFR of 0.1 to 10 g / 10 min, particularly 0.2 to 5 g / 10 min is preferably used.
【００１２】エチレンと共重合されるα−オレフィンと
しては、プロピレン、ブテン−１、ペンテン−１、４−
メチルペンテン−１などが例示されるが、なかんずく、
プロピレン及びブテン−１がコモノマー成分として好ま
しく使用される。エチレン−α−オレフィン共重合体に
おけるエチレンとα−オレフィンの構成比は、モル比
で、エチレン／α−オレフィン＝９５／５ないし７０／
３０、好ましくは９０／１０ないし７５／２５であるこ
とが望ましい。The α-olefin copolymerized with ethylene includes propylene, butene-1, pentene-1, 4-.
Methylpentene-1 and the like are exemplified, but above all,
Propylene and butene-1 are preferably used as comonomer components. The constituent ratio of ethylene and α-olefin in the ethylene-α-olefin copolymer is a molar ratio of ethylene / α-olefin = 95/5 to 70 /.
Desirably, it is 30, preferably 90/10 to 75/25.
【００１３】本発明のポリエチレン製改質容器を構成す
るポリマー組成物には、本発明の目的を損なわない範囲
で、充填剤、安定剤、滑剤、帯電防止剤、難燃剤、発泡
剤等の自体公知の添加剤を配合する事ができる。The polymer composition constituting the polyethylene reforming container of the present invention contains fillers, stabilizers, lubricants, antistatic agents, flame retardants, foaming agents, etc. per se as long as the object of the present invention is not impaired. Known additives can be added.
【００１４】また容器の成形においては、前記ポリエチ
レン組成物を単独で使用するか、、またはこれを融着層
とし、これにナイロン、エチレン−酢酸ビニル共重合体
などのガスバリヤー性樹脂をそれぞれ組み合わせた２層
以上の多層構成からなる積層体とすることもできる。こ
の際、前記ポリエチレン組成物をガスバリヤー性樹脂と
組み合わせる場合は、両層の接着性をよくするために、
ポリエチレンを不飽和カルボン酸またはその無水物など
で変性するか、コロナ放電などの接着性改善手段を採用
することができる。In the molding of the container, the polyethylene composition may be used alone, or may be used as a fusion layer, and a gas barrier resin such as nylon or ethylene-vinyl acetate copolymer may be combined therewith. It is also possible to form a laminate having a multilayer structure of two or more layers. At this time, in the case of combining the polyethylene composition with a gas barrier resin, in order to improve the adhesiveness of both layers,
Polyethylene can be modified with unsaturated carboxylic acid or its anhydride, or adhesion improving means such as corona discharge can be adopted.
【００１５】[0015]
【発明の効果】本発明によれば、特定のポリエチレン組
成物からなるポリエチレン製改質容器に対して特定の透
過度の電子線を照射することにより、被照射物が層状に
異なる架橋度を有する円筒容器が形成され、この架橋ポ
リエチレンは、未架橋のポリエチレンと同等の融着性を
有すると共に、耐熱性、ならびに耐薬品性に優れたポリ
エチレン製改質容器が提供され、この容器は、絞り出し
チューブ状円筒容器やカップ状容器のように、融着によ
って密封することが求められる容器の素材として好適に
使用することができる。According to the present invention, by irradiating a polyethylene reforming container made of a specific polyethylene composition with an electron beam having a specific transmittance, the object to be irradiated has a different degree of crosslinking in a layered manner. A cylindrical container is formed, and this crosslinked polyethylene has a fusion bonding property equivalent to that of uncrosslinked polyethylene, and is provided with a polyethylene modified container having excellent heat resistance and chemical resistance. It can be suitably used as a material for containers, such as cylindrical containers and cup-shaped containers, which are required to be sealed by fusion.
【００１６】[0016]
【実施例】つぎに実施例を挙げて本発明を更に具体的に
説明するが、本発明はその要旨を超えない限りこれら実
施例になんら制約されるものではない。なお、実施例に
よって得られたポリエチレン製改質容器の物性の評価は
次の方法で行った。 ・熱水自由収縮率とは、試料をオートクレーブに入れ、
１２１度、３０分間処理した後の収縮率をいい、３％以
下であることが好ましい耐熱性を有するものとして評価
される。 ・融着性の評価は、幅１５ｍｍの短冊状に切った試料切
片をシール幅３ｍｍでヒートシールし、これを１８０°
の方向に速度１００ｍｍ／ｍｉｎで引張った時の破断強
度（ｋｇ／１５ｍｍ）で示し、この値が４．５ｋｇ以上
であることが好ましい融着性を有するものとして評価さ
れる。 ・ゲル分率とは、試料をキシレンで２４時間煮沸した後
の残存重量％であり、耐薬品性を評価する指標であり、
４０％以上であることが好ましい耐薬品性を有するもの
として評価される。なお、積層品サンプル（実施例４、
比較例５，６）では、酸素バリヤー樹脂層（エバール）
を除いた部分で評価した。 ・電子線の試料に対する透過度は、厚さ３８μｍのＣＴ
Ａ（三酢酸セルロース）線量計（富士写真フイルム社
製）を使用し、相対線量を測定した。 ・抗力とは、柔軟性を必要とされる例えば、チューブ状
円筒容器などを評価する指標であり、詳しくは、チュー
ブ状円筒容器の筒部上方より筒部表面に、荷重（圧縮速
度１００ｍｍ／ｍｉｎ）をかけて同チューブ状円筒容器
を短径１０ｍｍの楕円筒状態まで圧縮した際の応力をい
い、この値が１．５ｋｇｆ以下であることが好ましい柔
軟性を有するものとして評価される。EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. The physical properties of the polyethylene reforming containers obtained in the examples were evaluated by the following methods.・ Hot water free shrinkage means that the sample is placed in an autoclave,
The shrinkage percentage after treatment at 121 ° C. for 30 minutes is said to be 3% or less, which is evaluated as having heat resistance. -For evaluation of the fusion property, a sample piece cut into a strip shape with a width of 15 mm was heat-sealed with a seal width of 3 mm, and this was 180 °.
The breaking strength (kg / 15 mm) when pulled in the direction of at a speed of 100 mm / min, and a value of 4.5 kg or more is evaluated as having a preferable fusion property. -Gel fraction is a residual weight% after boiling a sample with xylene for 24 hours, and is an index for evaluating chemical resistance,
It is evaluated as having a chemical resistance of preferably 40% or more. In addition, a laminated product sample (Example 4,
In Comparative Examples 5 and 6, the oxygen barrier resin layer (EVAL) is used.
It was evaluated in the part excluding.・ Transmittance of electron beam to the sample is 38μm thick CT
The relative dose was measured using an A (cellulose triacetate) dosimeter (manufactured by Fuji Photo Film Co., Ltd.). -Drag is an index for evaluating, for example, a tubular cylindrical container requiring flexibility, and more specifically, a load (compression speed of 100 mm / min from the upper part of the tubular part of the tubular cylindrical container to the surface of the tubular part). ) Is the stress when the tubular cylindrical container is compressed to a state of an elliptic cylinder having a short diameter of 10 mm, and a value of 1.5 kgf or less is evaluated as having flexibility.
【００１７】＜実施例１＞密度０．９３８ｇ／ｃｍ3 、
融点１２５℃の中密度ポリエチレンと、エチレン−プロ
ピレン共重合体（エチレン含量８０モル％）を７０：３
０（重量比）の割合で混合したポリエチレン組成物（ポ
リマー組成物の密度は０．９１６ｇ／ｃｍ 3 ）を押出成
形により、肉厚０．４５ｍｍ、内径４０ｍｍ、長さ１５
０ｍｍのチューブ状成形体を得た。このチューブ状成形
体の端部をヒートシールし、チューブ状円筒容器を得
た。このチューブ状円筒容器を２５０ｋＶの加速電圧、
窓下距離７．５ｃｍで表面の吸収線量３００ｋＧｙで照
射した。その時の相対線量は、被照射物の表面、中間、
裏面において、それぞれ１００、７０、３％であった。
このチューブ状円筒容器の熱水自由収縮率、ヒートシー
ル強度、ゲル分率、抗力を表１に示した。<Example 1> Density 0.938g / cm3 ,
Medium density polyethylene with a melting point of 125 ° C and ethylene-pro
Pyrene copolymer (ethylene content 80 mol%) 70: 3
0 (weight ratio) mixed polyethylene composition (po
The density of the limmer composition is 0.916 g / cm 3 ) Extruded
Depending on shape, wall thickness 0.45mm, inner diameter 40mm, length 15
A 0 mm tubular molded body was obtained. This tubular molding
Heat seal the ends of the body to obtain a tubular cylindrical container.
It was This tube-shaped cylindrical container has an acceleration voltage of 250 kV,
Illuminate at a distance of 7.5 cm below the window with a surface absorbed dose of 300 kGy
Shot The relative dose at that time is the surface of the irradiated object, the middle,
On the back side, they were 100, 70 and 3%, respectively.
Free shrinkage rate and heat seal of this tubular cylindrical container
The strength, gel fraction and drag are shown in Table 1.
【００１８】＜実施例２＞密度０．９２４ｇ／ｃｍ3 、
融点１１７℃の直鎖状低密度ポリエチレンと、エチレン
−プロピレン共重合体（エチレン含量８０モル％）を９
０：１０（重量比）の割合で混合したポリエチレン組成
物（ポリマー組成物の密度は０．９１６ｇ／ｃｍ3 ）を
押出成形により、肉厚０．４５ｍｍ、内径４０ｍｍ、長
さ１５０ｍｍのチューブ状成形体を得た。このチューブ
状成形体の端部をヒートシールし、チューブ状円筒容器
を得た。このチューブ状円筒容器を２５０ｋＶの加速電
圧、窓下距離７．５ｃｍで表面の吸収線量３００ｋＧｙ
で照射した。その時の相対線量は、被照射物の表面、中
間、裏面において、それぞれ１００、７０、３％であっ
た。このチューブ状円筒容器の熱水自由収縮率、ヒート
シール強度、ゲル分率、抗力を表１に示した。< Example 2 > Density 0.924 g / cm 3 ,
Linear low density polyethylene having a melting point of 117 ° C. and ethylene-propylene copolymer (ethylene content 80 mol%)
A polyethylene composition (density of the polymer composition is 0.916 g / cm 3 ) mixed at a ratio of 0:10 (weight ratio) is extruded to form a tube having a thickness of 0.45 mm, an inner diameter of 40 mm, and a length of 150 mm. Got the body The end of this tubular molded body was heat-sealed to obtain a tubular cylindrical container. This tubular cylindrical container was subjected to an acceleration voltage of 250 kV, a window distance of 7.5 cm, and an absorbed dose on the surface of 300 kGy.
Illuminated. The relative doses at that time were 100%, 70%, and 3% on the surface, the middle, and the back of the object to be irradiated, respectively. Table 1 shows the hot water free shrinkage rate, heat seal strength, gel fraction, and drag of this tubular cylindrical container.
【００１９】＜実施例３＞密度０．９３８ｇ／ｃｍ3 、
融点１２５℃の中密度ポリエチレンと、エチレン−プロ
ピレン共重合体（エチレン含量８０モル％）を７０：３
０（重量比）の割合で混合したポリエチレン組成物（ポ
リマー組成物の密度は０．９１６ｇ／ｃｍ 3 ）を押出成
形により、肉厚０．４５ｍｍ、内径４０ｍｍ、長さ１５
０ｍｍのチューブ状成形体を得た。このチューブ状成形
体の端部をヒートシールし、チューブ状円筒容器を得
た。このチューブ状円筒容器を２６０ｋＶの加速電圧、
窓下距離７．５ｃｍで表面の吸収線量３００ｋＧｙで照
射した。その時の相対線量は、被照射物の表面、中間、
裏面において、それぞれ１００、７５、２０％であっ
た。このチューブ状円筒容器の熱水自由収縮率、ヒート
シール強度、ゲル分率、抗力を表１に示した。<Example 3> Density 0.938g / cm3 ,
Medium density polyethylene with a melting point of 125 ° C and ethylene-pro
Pyrene copolymer (ethylene content 80 mol%) 70: 3
0 (weight ratio) mixed polyethylene composition (po
The density of the limmer composition is 0.916 g / cm 3 ) Extruded
Depending on shape, wall thickness 0.45mm, inner diameter 40mm, length 15
A 0 mm tubular molded body was obtained. This tubular molding
Heat seal the ends of the body to obtain a tubular cylindrical container.
It was This tubular cylindrical container is operated at an acceleration voltage of 260 kV,
Illuminate at a distance of 7.5 cm below the window with a surface absorbed dose of 300 kGy
Shot The relative dose at that time is the surface of the irradiated object, the middle,
On the back side, 100, 75 and 20% respectively
It was Hot water free shrinkage and heat of this tubular cylindrical container
The seal strength, gel fraction, and drag are shown in Table 1.
【００２０】 [0020]
【００２１】＜比較例１＞密度０．９３８ｇ／ｃｍ3 、
融点１２５℃の中密度ポリエチレンと、エチレン−プロ
ピレン共重合体（エチレン含量８０モル％）を７０：３
０（重量比）の割合で混合したポリエチレン組成物（ポ
リマー組成物の密度は０．９１６ｇ／ｃｍ 3 ）を押出成
形により、肉厚０．４５ｍｍ、内径４０ｍｍ、長さ１５
０ｍｍのチューブ状成形体を得た。このチューブ状成形
体の端部をヒートシールし、チューブ状円筒容器を得
た。このチューブ状円筒容器を３００ｋＶの加速電圧、
窓下距離７．５ｃｍで表面の吸収線量３００ｋＧｙで照
射した。その時の相対線量は、被照射物の表面、中間、
裏面において、それぞれ１００、９０、５０％であっ
た。このチューブ状円筒容器の熱水自由収縮率、ヒート
シール強度、ゲル分率、抗力を表２に示した。<Comparative Example 1> Density 0.938g / cm3 ,
Medium density polyethylene with a melting point of 125 ° C and ethylene-pro
Pyrene copolymer (ethylene content 80 mol%) 70: 3
0 (weight ratio) mixed polyethylene composition (po
The density of the limmer composition is 0.916 g / cm 3 ) Extruded
Depending on shape, wall thickness 0.45mm, inner diameter 40mm, length 15
A 0 mm tubular molded body was obtained. This tubular molding
Heat seal the ends of the body to obtain a tubular cylindrical container.
It was This tubular cylindrical container is operated at an acceleration voltage of 300 kV,
Illuminate at a distance of 7.5 cm below the window with a surface absorbed dose of 300 kGy
Shot The relative dose at that time is the surface of the irradiated object, the middle,
On the back side, 100%, 90% and 50% respectively
It was Hot water free shrinkage and heat of this tubular cylindrical container
The seal strength, gel fraction, and drag are shown in Table 2.
【００２２】＜比較例２＞密度０．９２４ｇ／ｃｍ3 、
融点１１７℃の直鎖状低密度ポリエチレンと、エチレン
−プロピレン共重合体（エチレン含量８０モル％）を９
０：１０（重量比）の割合で混合したポリエチレン組成
物（ポリマー組成物の密度は０．９１６ｇ／ｃｍ3 ）を
押出成形により、肉厚０．４５ｍｍ、内径４０ｍｍ、長
さ１５０ｍｍのチューブ状成形体を得た。このチューブ
状成形体の端部をヒートシールし、チューブ状円筒容器
を得た。このチューブ状円筒容器を２００ｋＶの加速電
圧、窓下距離７．５ｃｍで表面の吸収線量３００ｋＧｙ
で照射した。その時の相対線量は、被照射物の表面、中
間、裏面において、それぞれ１００、２０、０％であっ
た。このチューブ状円筒容器の熱水自由収縮率、ヒート
シール強度、ゲル分率、抗力を表２に示した。< Comparative Example 2 > Density 0.924 g / cm 3 ,
Linear low density polyethylene having a melting point of 117 ° C. and ethylene-propylene copolymer (ethylene content 80 mol%)
A polyethylene composition (density of the polymer composition is 0.916 g / cm 3 ) mixed at a ratio of 0:10 (weight ratio) is extruded to form a tube having a thickness of 0.45 mm, an inner diameter of 40 mm, and a length of 150 mm. Got the body The end of this tubular molded body was heat-sealed to obtain a tubular cylindrical container. This tubular cylindrical container was subjected to an acceleration voltage of 200 kV, a window distance of 7.5 cm, and a surface absorbed dose of 300 kGy.
Illuminated. The relative doses at that time were 100, 20, and 0% on the surface, the middle, and the back of the object to be irradiated, respectively. Table 2 shows the free shrinkage rate of hot water, heat seal strength, gel fraction, and drag force of this tubular cylindrical container.
【００２３】＜比較例３＞密度０．９２４ｇ／ｃｍ3 、
融点１１７℃の直鎖状低密度ポリエチレンと、エチレン
−プロピレン共重合体（エチレン含量８０モル％）を９
０：１０（重量比）の割合で混合したポリエチレン組成
物（ポリマー組成物の密度は０．９１６ｇ／ｃｍ3 ）を
押出成形により、肉厚０．４５ｍｍ、内径４０ｍｍ、長
さ１５０ｍｍのチューブ状成形体を得た。このチューブ
状成形体の端部をヒートシールし、チューブ状円筒容器
を得た。このチューブ状円筒容器の熱水自由収縮率、ヒ
ートシール強度、ゲル分率、抗力を表２に示した。< Comparative Example 3 > Density 0.924 g / cm 3 ,
Linear low density polyethylene having a melting point of 117 ° C. and ethylene-propylene copolymer (ethylene content 80 mol%)
A polyethylene composition (density of the polymer composition is 0.916 g / cm 3 ) mixed at a ratio of 0:10 (weight ratio) is extruded to form a tube having a thickness of 0.45 mm, an inner diameter of 40 mm, and a length of 150 mm. Got the body The end of this tubular molded body was heat-sealed to obtain a tubular cylindrical container. Table 2 shows the free shrinkage rate of hot water, heat seal strength, gel fraction, and drag force of this tubular cylindrical container.
【００２４】＜比較例４＞密度０．９３８ｇ／ｃｍ3 、
融点１２５℃の中密度ポリエチレンと、エチレン−プロ
ピレン共重合体（エチレン含量８０モル％）を７０：３
０（重量比）の割合で混合したポリエチレン組成物（ポ
リマー組成物の密度は０．９１６ｇ／ｃｍ 3 ）を押出成
形により、肉厚０．４５ｍｍ、内径４０ｍｍ、長さ１５
０ｍｍのチューブ状成形体を得た。このチューブ状成形
体の端部をヒートシールし、チューブ状円筒容器を得
た。このチューブ状円筒容器の熱水自由収縮率、ヒート
シール強度、ゲル分率、抗力を表２に示した。<Comparative Example 4> Density 0.938g / cm3 ,
Medium density polyethylene with a melting point of 125 ° C and ethylene-pro
Pyrene copolymer (ethylene content 80 mol%) 70: 3
0 (weight ratio) mixed polyethylene composition (po
The density of the limmer composition is 0.916 g / cm 3 ) Extruded
Depending on shape, wall thickness 0.45mm, inner diameter 40mm, length 15
A 0 mm tubular molded body was obtained. This tubular molding
Heat seal the ends of the body to obtain a tubular cylindrical container.
It was Hot water free shrinkage and heat of this tubular cylindrical container
The seal strength, gel fraction, and drag are shown in Table 2.
【００２５】 [0025]
【００２６】＜実施例４＞無水マレイン酸が０．１７ｗ
ｔ％グラフトされた密度０．９３８ｇ／ｃｍ3 の変性中
密度ポリエチレンとエチレン−プロピレン共重合体（エ
チレン含量８０モル％）を７０：３０の割合で配合した
組成物を内外層とし、中間層に酸素バリヤー性樹脂とし
て、株式会社クラレ社製の「エバール」（登録商標）Ｅ
Ｐ−Ｆ（ＭＦＲ１．３）を用いこれを共押出成形によ
り、外層／中間層／内層＝１５０／５０／２５０μ、内
径４０ｍｍ，長さ１５０ｍｍのチューブ状成形体を得
た。このチューブ状成形体の端部をヒートシールし、チ
ューブ状円筒容器を得た。このチューブ状円筒容器を２
５０ｋＶの加速電圧、窓下距離７．５ｃｍで表面の吸収
線量３００ｋＧｙで照射した。その時の相対線量は被照
射物の表面、中間、裏面においてそれぞれ１００、７
０、３％であった。このチューブ状円筒容器の熱水自由
収縮率、ヒートシール強度、ゲル分率、抗力、酸素透過
量を表３に示した。<Example 4> Maleic anhydride 0.17 w
t% grafted modified medium density polyethylene with a density of 0.938 g / cm 3 and an ethylene-propylene copolymer (ethylene content 80 mol%) in a ratio of 70:30 were used as inner and outer layers, and a middle layer was formed. "Eval" (registered trademark) E manufactured by Kuraray Co., Ltd. as an oxygen barrier resin
This was coextruded using PF (MFR1.3) to obtain a tubular molded body having an outer layer / middle layer / inner layer = 150/50/250 μ, an inner diameter of 40 mm, and a length of 150 mm. The end of this tubular molded body was heat-sealed to obtain a tubular cylindrical container. This tubular cylindrical container
Irradiation was carried out at an acceleration voltage of 50 kV and a window distance of 7.5 cm with a surface absorbed dose of 300 kGy. The relative dose at that time was 100, 7 on the front, middle, and back of the irradiated object, respectively.
It was 0, 3%. Table 3 shows the free shrinkage rate of hot water, heat seal strength, gel fraction, drag force, and oxygen permeation amount of this tubular cylindrical container.
【００２７】＜比較例５＞無水マレイン酸が０．１５ｗ
ｔ％グラフトされた、密度０．９２０ｇ／ｃｍ3の変性
低密度ポリエチレンを内外層とし、中間層に酸素バリヤ
ー性樹脂として、株式会社クラレ社製の「エバール」
（登録商標）ＥＰ−Ｆ（ＭＦＲ１．３）を用いこれを共
押出成形により、外層／中間層／内層＝１５０／５０／
２５０μ、内径４０ｍｍ，長さ１５０ｍｍのチューブ状
成形体を得た。このチューブ状成形体の端部をヒートシ
ールし、チューブ状円筒容器を得た。このチューブ状円
筒容器を３００ｋＶの加速電圧、窓下距離７．５ｃｍで
表面の吸収線量２００ｋＧｙで照射した。その時の相対
線量は被照射物の表面、中間、裏面においてそれぞれ１
００、９０、５０％であった。このチューブ状円筒容器
の熱水自由収縮率、ヒートシール強度、ゲル分率、抗
力、酸素透過量を表３に示した。<Comparative Example 5> 0.15 w of maleic anhydride
"Eval" manufactured by Kuraray Co., Ltd. with t% grafted modified low density polyethylene having a density of 0.920 g / cm 3 as the inner and outer layers and an oxygen barrier resin in the middle layer.
(Registered trademark) EP-F (MFR1.3) was coextruded to form outer layer / middle layer / inner layer = 150/50 /
A tubular molded body having a size of 250 μ, an inner diameter of 40 mm and a length of 150 mm was obtained. The end of this tubular molded body was heat-sealed to obtain a tubular cylindrical container. This tubular cylindrical container was irradiated with an accelerating voltage of 300 kV, a distance under the window of 7.5 cm, and an absorbed dose on the surface of 200 kGy. The relative dose at that time is 1 on the front, middle, and back of the irradiated object, respectively.
It was 00, 90 and 50%. Table 3 shows the free shrinkage rate of hot water, heat seal strength, gel fraction, drag force, and oxygen permeation amount of this tubular cylindrical container.
【００２８】＜比較例６＞無水マレイン酸が０．１５ｗ
ｔ％グラフトされた密度０．９２０ｇ／ｃｍ3 の変性低
密度ポリエチレンを内外層とし、中間層に酸素バリヤー
性樹脂として、株式会社クラレ社製の「エバール」（登
録商標）ＥＰ−Ｆ（ＭＦＲ１．３）を用いこれを共押出
成形により、外層／中間層／内層＝１５０／５０／２５
０μ、内径４０ｍｍ，長さ１５０ｍｍのチューブ状成形
体を得た。このチューブ状成形体の端部をヒートシール
し、チューブ状円筒容器を得た。このチューブ状円筒容
器の熱水自由収縮率、ヒートシール強度、ゲル分率、抗
力、酸素透過量を表３に示した。<Comparative Example 6> 0.15 w of maleic anhydride
t% grafted modified low-density polyethylene having a density of 0.920 g / cm 3 as the inner and outer layers, and an oxygen barrier resin in the middle layer, "Eval" (registered trademark) EP-F (MFR 1. 3), which is coextruded to form outer layer / middle layer / inner layer = 150/50/25
A tube-shaped molded body having 0 μ, an inner diameter of 40 mm and a length of 150 mm was obtained. The end of this tubular molded body was heat-sealed to obtain a tubular cylindrical container. Table 3 shows the free shrinkage rate of hot water, heat seal strength, gel fraction, drag force, and oxygen permeation amount of this tubular cylindrical container.
【００２９】 [0029]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 吉井 文男 群馬県高崎市綿貫町1233番地 日本原子力 研究所高崎研究所内 (72)発明者 串田 秀男 東京都江東区大島３丁目２番６号 株式会 社吉野工業所内 (72)発明者 中島 静 東京都江東区大島３丁目２番６号 株式会 社吉野工業所内 (72)発明者 栗原 孝弘 群馬県藤岡市岡ノ郷字高木350番地 株式 会社吉野工業所群馬工場内 (72)発明者 菅原 良二 千葉県松戸市稔台310番地 株式会社吉野 工業所松戸工場内 (72)発明者 二見 靖男 千葉県市原市千種海岸３番地 三井石油化 学工業株式会社内 (72)発明者 石山 正信 千葉県市原市千種海岸３番地 三井石油化 学工業株式会社内 (72)発明者 宮本 元 千葉県市原市千種海岸３番地 三井石油化 学工業株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Fumio Yoshii 1233 Watanuki-cho, Takasaki-shi, Gunma Japan Atomic Energy Research Institute Takasaki Research Institute (72) Inventor Hideo Kushida 3-2-6 Oshima, Koto-ku, Tokyo Stock Company Yoshino Kogyosho (72) Inventor Shizuka Nakajima 3-2 Oshima, Koto-ku, Tokyo Stock company Yoshino Kogyosho (72) Inventor Takahiro Kurihara 350 Takagi, Okanogo, Fujioka-shi Gunma Yoshino Kogyo Gunma Inside the factory (72) Ryoji Sugawara, 310 Minoridai, Matsudo City, Chiba Prefecture Yoshino Industry Co., Ltd. within the Matsudo Factory (72) Inventor Yasuo Futami, No. 3, Chikusaigan, Ichihara City, Chiba Mitsui Sekiyu Kagaku Kogyo Co., Ltd. (72) Inventor Masanobu Ishiyama 3 Chikusaigan, Ichihara-shi, Chiba Mitsui Sekiyu Kagaku Kogyo Co., Ltd. (72) Inventor Gen Miyamoto Chi, Ichihara-shi, Chiba Coast 3 address Mitsui Oil Chemical Industry Co., Ltd. in
Claims (5)
射物表面の相対線量を１００％とした時、被照射物の厚
み方向の中間において６０ないし８０％また裏面におい
て４０％以下となるように照射した、密度０．９００な
いし０．９７５ｇ／ｃｍ3 のポリエチレンと、エチレン
−α−オレフィン共重合体からなる組成物を素材とする
ポリエチレン製改質容器。1. The transmittance of an electron beam to an object to be irradiated is 60 to 80% in the middle of the thickness direction of the object to be irradiated and 40% or less on the back surface when the relative dose to the surface of the object is 100%. A modified container made of polyethylene, which is made of a composition composed of an ethylene-α-olefin copolymer and polyethylene having a density of 0.900 to 0.975 g / cm 3 which has been irradiated as above.
レフィン共重合体の配合割合が、重量比で５ないし５０
％の範囲である請求項１記載のポリエチレン製改質容
器。2. The blending ratio of ethylene-α-olefin copolymer to polyethylene is 5 to 50 by weight.
The polyethylene reforming container according to claim 1, which is in the range of%.
を有する請求項１記載のポリエチレン製改質容器。3. The polyethylene reforming container according to claim 1, wherein the container has a portion sealed by fusion.
子線発生装置の加速電圧、もしくは照射窓と被照射物と
の距離によって変えられる請求項１記載のポリエチレン
製改質容器。4. The polyethylene reforming container according to claim 1, wherein the transmittance of the electron beam to the object to be irradiated is changed by the acceleration voltage of the electron beam generator or the distance between the irradiation window and the object to be irradiated.
０ないし５００ｋＧｙである請求項１記載のポリエチレ
ン製改質容器。5. The absorbed dose of electron beam on the surface of the object to be irradiated is 5
The polyethylene reforming container according to claim 1, wherein the reforming container is from 0 to 500 kGy.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08763693A JP3442812B2 (en) | 1993-04-14 | 1993-04-14 | Polyethylene reforming container |
| DE69311497T DE69311497T2 (en) | 1992-10-26 | 1993-10-22 | Compressible tubular container and method for its manufacture |
| EP93117180A EP0595220B1 (en) | 1992-10-26 | 1993-10-22 | Squeezable tubular container and process for the production thereof |
| TW082108912A TW300190B (en) | 1992-10-26 | 1993-10-23 | |
| AU49197/93A AU664651B2 (en) | 1992-10-26 | 1993-10-25 | Squeezable tubular container and process for the production thereof |
| CA002109127A CA2109127A1 (en) | 1992-10-26 | 1993-10-25 | Squeezable tubular container and process for the production thereof |
| KR1019930022282A KR100216638B1 (en) | 1992-10-26 | 1993-10-26 | Squeezable tubular container and process for the production thereof |
| CN93120228A CN1065478C (en) | 1992-10-26 | 1993-10-26 | Squeezable tubular container and process for the production thereof |
| US08/453,673 US5565160A (en) | 1992-10-26 | 1995-05-30 | Squeezable tubular container and process for the production thereof |
| US08/674,406 US5725715A (en) | 1992-10-26 | 1996-07-02 | Squeezable tubular container and process for the production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08763693A JP3442812B2 (en) | 1993-04-14 | 1993-04-14 | Polyethylene reforming container |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06298264A true JPH06298264A (en) | 1994-10-25 |
| JP3442812B2 JP3442812B2 (en) | 2003-09-02 |
Family
ID=13920471
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08763693A Expired - Lifetime JP3442812B2 (en) | 1992-10-26 | 1993-04-14 | Polyethylene reforming container |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3442812B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS565834A (en) * | 1979-06-22 | 1981-01-21 | Bayer Ag | Bridged polymer film and manufacture thereof |
| JPS6377957A (en) * | 1986-09-19 | 1988-04-08 | Mitsubishi Kasei Corp | Polyethylene resin composition |
-
1993
- 1993-04-14 JP JP08763693A patent/JP3442812B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS565834A (en) * | 1979-06-22 | 1981-01-21 | Bayer Ag | Bridged polymer film and manufacture thereof |
| JPS6377957A (en) * | 1986-09-19 | 1988-04-08 | Mitsubishi Kasei Corp | Polyethylene resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3442812B2 (en) | 2003-09-02 |
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