JP4758018B2 - Chemical container - Google Patents

Description

【００２８】
〔式(1) 中、Ｒ¹ およびＲ² は同一または異なって、水素、炭化水素残基、またはハロゲン、エステル、ニトリル、ピリジル等の極性基を示す。また、Ｒ¹ およびＲ² は互いに結合して環を形成してもよい。ｍは１以上の整数、ｎは０または１以上の整数である。〕
および／または一般式(2) ：
【００２９】
【化２】

【００３０】
〔式(2) 中、Ｒ³ およびＲ⁴ は同一または異なって、水素、炭化水素残基、またはハロゲン、エステル、ニトリル、ピリジル等の極性基を示す。また、Ｒ³ およびＲ⁴ は互いに結合して環を形成してもよい。ｘおよびｚは１以上の整数、ｐは０または１以上の整数である。〕
で表される構成単位を有するポリマーを挙げることができる。
一般式(1) で表される構成単位を有するポリマーは、１種または２種以上の単量体を公知の開環重合方法によって重合させ、こうして得られる開環重合体を常法に従って水素添加したものである。
【００３１】
当該ポリマーの具体例としては、日本ゼオン（株）製の水添重合体〔商品名「ゼオノア」、比重１．０１、ＭＦＲ７０ｇ／１０分（１９０℃）、ガラス転移温度（Ｔｇ）１００℃〕、日本合成ゴム（株）製の商品名「ＡＲＴＯＮ(R) 」等が挙げられる。
一般式(2) で表される構造単位を有するポリマーは、単量体としての、１種または２種以上のノルボルネン系モノマーと、エチレンとを公知の方法によって付加共重合させたもの、および／またはこれを常法に従って水素添加したものである。
【００３２】
当該ポリマーの具体例としては、三井化学（株）製の〔商品名「アペル６５０９」、比重１．０２、ＭＦＲ４０ｇ／１０分（１９０℃）、ガラス転移温度（Ｔｇ）８０℃〕、ＴＩＣＯＮＡ社製の商品名「ＴＯＰＡＳ(R) 」等が挙げられる。
上記一般式(1) および(2) で表される構成単位を有するポリマーを含む、前記共重合体の水素添加物は、いずれも飽和ポリマーであるので、先端が鋭利ではない筒状部材に対する刺通性に優れるだけではなく、ガス遮蔽性、水分遮蔽性、耐熱性、安定性の点でも優れている。
【００３３】
上記環状オレフィン系重合体は、そのガラス転移温度（Ｔ_g ）が８０℃以上であるのが好ましく、１０５〜１５０℃であるのがより好ましい。ガラス転移温度Ｔ_g が８０℃を下回ると、樹脂フィルムの伸び特性が増大して、先端が鋭利ではない筒状部材によって容易に開裂させることができなくなるおそれがある。一方、ガラス転移温度Ｔ_g が１５０℃を超えると、環状オレフィン系重合体の脆弱性が増大して、弾性体を被覆する用途に適さなくなるおそれがある。
【００３４】
また、環状オレフィン系重合体の分子量の範囲は、シクロヘキサンを溶媒とするゲル浸透クロマトグラフィ（ＧＰＣ）分析により測定した数平均分子量＜Ｍｎ＞において１万〜１０万であるのが好ましく、２万〜５万であるのがより好ましい。当該共重合体の分子鎖中に残留する不飽和結合を水素添加により飽和させる場合において、その水添率は、９０％以上、好ましくは９５％以上、特に好ましくは９９％以上となるように設定される。
【００３５】
環状オレフィン系重合体の引張破断伸び（％）は、ＡＳＴＭ Ｄ６３８の規定に準じて測定した値で５％以下であるのが好ましく、１〜４％であるのがより好ましい。引張破断伸びが５％を超えると、樹脂フィルムの伸び特性が増大して、先端が鋭利ではない筒状部材によって容易に開裂させることができなくなるおそれがある。
（他の重合体）
本発明のスリット入り弾性封止体において、弾性体の表面を被覆するのに用いられる樹脂フィルムには、前述のように、環状オレフィン系重合体からなる層を単独で用いるだけではなく、例えば環状オレフィン系重合体からなる層とポリオレフィン系重合体からなる層との積層体等を用いることができる。
【００３６】
前記ポリオレフィン系重合体としては、例えばポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）等が挙げられる。
環状オレフィン系重合体からなる層との積層体を構成する樹脂としては、ポリオレフィン系重合体のほかに、例えばエチレン−酢酸ビニル共重合体、ポリエステル、ポリアミド等が挙げられる。
（樹脂フィルムの物性）
本発明のスリット入り弾性封止体において、弾性体の表面を被覆する樹脂フィルムの厚みは、その引裂強さと機械的強度とを両立させるという観点から、２０〜５００μｍの範囲に設定するのが適当であって、２０〜１００μｍの範囲とするのがより好ましい。また、この場合において、環状オレフィン系重合体からなる層の厚みの割合は、樹脂フィルム全体の１０〜９０％とするのが好ましく、１０〜５０％とするのがより好ましい。
【００３７】
樹脂フィルムの厚さが上記範囲を上回ったり、樹脂フィルム全体に占める環状オレフィン系重合体の厚みの割合が上記範囲を下回ったりすると、樹脂フィルム全体で環状オレフィン系重合体以外の樹脂の影響を無視し得なくなり、樹脂フィルムの伸びが大きくなるおそれがある。一方、樹脂フィルムの厚さが上記範囲を下回ったり、樹脂フィルム全体に占める環状オレフィン系重合体の厚みの割合が上記範囲を超えたりすると、樹脂フィルムが弱くなってしまうおそれがある。
【００３８】
〔弾性体〕
本発明に係るスリット入り弾性封止体における弾性体には、従来の薬液容器等における栓として用いられている種々の材料を用いることができる。例えば、天然ゴム、シリコーンゴム、ブチルゴム、イソプレンゴム、スチレン−ブタジエンゴム等のゴムや、熱可塑性エラストマー等の弾性部材が挙げられる。
本発明のスリット入り弾性封止体を輸液容器等のキャップに適用する場合において、当該キャップの外枠体と弾性体とを一体成形するには、外枠体を形成するプラスチックとともに熱成形が可能な熱可塑性エラストマーを弾性体として使用するのが好ましい。この場合、キャップの製造工程を簡易なものとすることができる。
【００３９】
本発明に使用可能な熱可塑性エラストマーとしては、例えばスチレン−エチレン／ブチレンースチレンブロック共重合体（ＳＥＢＳ）、スチレン−ブタジエン−スチレンブロック共重合体（ＳＢＳ）、スチレン−イソプレン−スチレンブロック共重合体（ＳＩＳ）、スチレン−エチレン／プロピレン−スチレンブロック共重合体（ＳＥＰＳ）、マレイン酸変性等の変性ＳＥＢＳ、スチレン−エチレン／ブチレンブロック共重合体（ＳＥＢ）、スチレン−エチレン／プロピレンブロック共重合体（ＳＥＰ）等のスチレン系エラストマー；エチレン−プロピレンブロック共重合体等のオレフィン系エラストマー；ポリウレタン系エラストマー等が挙げられる。
【００４０】
本発明に使用可能な弾性体の特性については特に限定されるものではなく、一般に、医療用注入針を貫通させるのが困難なほどに強靭または高硬度のものではなく、かつ、通常の保管時に容易に変形したり、破損したりすることのない程度の強度を有するものであればよい。
本発明に使用可能な弾性体の硬度は、ＪＩＳ Ａ硬度〔ＪＩＳ Ｋ ６３０１に記載の方法にて測定したスプリング硬さＨｓ（ＪＩＳ Ａ）〕が２０〜７０であるのが好ましく、３０〜５０であるのがより好ましい。また、弾性体の圧縮永久歪みは、医療用注入針を繰り返し抜き差ししても破損することがないように、ＪＩＳ Ｋ ６３０１に記載の方法にて測定した値〔圧縮永久ひずみ率ＣＳ（％），熱処理温度・時間：７０℃，２２時間〕が３０以下であるのが好ましい。
【００４１】
〔スリット〕
本発明に係るスリット入り弾性封止体において、弾性体の内部に形成されるスリットは、先端が鋭利ではない筒状の部材を容易に挿通させることのできるものであればよい。従って、その幅、長さ（弾性体の全長に占める割合）、形状等については特に限定されるものではないが、通常、スリット部分の横断面の形状（弾性体の表面に現れる形状）が直線（−）状であって、その幅が０．５〜１０ｍｍ、好ましくは１〜７ｍｍ、より好ましくは２〜４ｍｍ程度となるように設定するのが適当である。
【００４２】
なお、スリットの幅等は、使用する筒状部材の形状に応じて適宜設計変更することができる。また、その形状も上記のものに限定されるものではない。また、これに限定されるものではないが、筒状部材等を挿通していない状態では、弾性体の反発力によりスリット部分が塞がれているように設計するのが好ましい。
【００４３】
【実施例】
次に、実施例および比較例を挙げて、本発明を説明する。
〔スリット入り弾性封止体の製造〕
実施例１
厚さ５ｍｍ、直径２０ｍｍの円柱状のゴム栓（弾性体１１，天然ゴム製，ＪＩＳ Ａ硬度３５）の中央に、幅が３ｍｍで、ゴム栓の天面から底面にまで連通したスリット１４を設けた（図１参照）。
【００４４】
次いで、エチレン・テトラシクロドデセン共重合体〔三井化学（株）製の商品名「アペルＡＰＬ６０１３」，ガラス転移温度１２５℃，引張破断伸び３％〕のフィルムの両面に、直鎖状低密度ポリエチレン〔ＬＬＤＰＥ，密度０．９２０〕のフィルムを積層してなる３層フィルム（樹脂フィルム１５）を使用し、この３層フィルムを前記スリット入りゴム栓の、筒状部材の貫通位置１７を含む面１３に被覆することにより、スリット入り弾性封止体１０を得た。
【００４５】
前記３層フィルムの厚みは全体で３０μｍであって、当該３層フィルムを構成する各フィルムの厚みの割合は、一方の表面から順に３０％，４０％，３０％であった。
比較例１
実施例１で用いたのと同様のスリット入りゴム栓の一方の表面に、ＬＬＤＰＥ（前出）からなる厚さ３０μｍの樹脂フィルムを被覆して、スリット入り弾性封止体を得た。
【００４６】
〔被覆フィルムの開裂試験〕
試験例１
上記実施例１および比較例１で得られたスリット入り弾性封止体１０について、以下の試験を行った。
筒状部材の穿刺位置１６（樹脂フィルム１５が設けられていない側の面１２におけるスリット１４の露出位置）から、弾性体１１に対して、注射器のシリンジにおける先端部（金属製中空針等を接続するための円柱状の部分）を差し込み、樹脂フィルム１５の開裂の有無を確認した。
【００４７】
上記試験に使用したシリンジ３０の先端部３１は、その外径Ｄが４．２ｍｍ、中空部３２の内径ｄが１．８５ｍｍ、長さＴが９ｍｍであった（図５(b) 参照）。
また、上記試験は、実施例１および比較例１の双方とも、１０個のサンプルについて行った。
その結果、実施例１で得られたスリット入り弾性体では、全てのサンプルについて樹脂フィルムの開裂が生じたのに対し、比較例１で得られたスリット入り弾性体では、図６に示すように樹脂フィルム１５が伸びたために、シリンジの先端部３１を奥まで差し込んでも開裂を生じさせることができなかった。
【００４８】
試験例２
上記実施例１および比較例１に使用した樹脂フィルムについて、前出のシリンジ３０の先端部３１（Ｄ＝４．２ｍｍ，ｄ＝１．８５ｍｍ，Ｔ＝９ｍｍ，円柱状）で突き破るのに必要な力を、オートグラフ〔島津（株）製の「ＡＧＳ−１００Ｄ」〕により、２００ｍｍ／分の速度で測定した。
測定に際して、実施例１および比較例１に使用した樹脂フィルム１５は、直径６．５ｍｍの孔を有する２枚の板９０に挟み込んで使用した。また、シリンジの先端部３１は、前記孔の中央部分にて樹脂フィルム１５に当接され、かつ、樹脂フィルム１５に対して先端部３１が垂直に当たるように調節した。
【００４９】
上記測定は、実施例１および比較例１で使用した樹脂フィルムの双方とも、１０枚のサンプルについて行った。
その結果、実施例１で使用した樹脂フィルムは、いずれも先端が鋭利ではないシリンジの先端部で突き破ることができた。樹脂フィルムの開裂に要した力は、平均０．７ｋｇｆであった。これに対し、比較例１で使用した樹脂フィルムは、シリンジの先端部による押圧ではフィルムが伸びるだけで、いずれのサンプルについても開裂するには至らなかった。
【図面の簡単な説明】
【図１】本発明に係るスリット入り弾性封止体の一実施形態を示す図であって、(a) はその断面図、(b) はその平面図である。
【図２】本発明に係るスリット入り弾性封止体の他の実施形態を示す断面図である。
【図３】本発明に係るスリット入り弾性封止体のさらに他の実施形態を示す断面図である。
【図４】本発明に係るスリット入り弾性封止体のさらに他の実施形態を示す断面図である。
【図５】 (a) は樹脂フィルムの引裂強度測定試験の方法を示す説明図であって、(b) および(c) は注射器のシリンジにおける先端部の形状を説明するための部分拡大図である。
【図６】従来の、樹脂フィルムを備えたスリット入り弾性体の問題点を示す説明図である。
【符号の説明】
１０ スリット入り弾性封止体， １１ 弾性体， １４ スリット， １５樹脂フィルム， １６ 穿刺位置， １７ 貫通位置， ｘ 挿通方向[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a chemical solution container containing a drip solution, an injection solution or the like.In a vesselRelated.
[0002]
[Prior art]
The mouth of a chemical container that contains drip solution, injection solution, etc. and the infusion port of an infusion circuit (infusion line) used for infusion of drip solution etc. are generally sealed with a sealing material such as a rubber stopper. A member having a sharp tip, such as a metal hollow needle (injection needle), has been used when injecting and mixing a drug solution / drug from a mouth or a mixed injection port.
On the other hand, in recent years, attempts have been made to reduce as much as possible the use of sharp hollow needles with sharp tips that may accidentally stab fingers from the viewpoint of measures against infectious diseases and the like.
[0003]
Japanese Patent Laid-Open No. 7-236697 discloses a rubber plug that seals a mixed injection port as a means for realizing injection and mixing of a chemical solution and a drug using a cylindrical member (hollow blunt needle) whose tip is not sharp. Proposes an infusion circuit with a cut in advance. If a cut is provided in advance like a rubber plug provided in this infusion circuit, even a cylindrical member having a sharp tip can be easily inserted.
However, when the rubber plug is cut in advance as in the above publication, there arises a new problem that the sealing performance of the mouth portion and the mixed injection port is impaired. In particular, depending on the chemical solution / drug filled in the chemical container, it may be necessary to apply a sterilization treatment such as high-pressure steam sterilization or hot water sterilization after filling, but it can be used as a sealing material such as a rubber plug to seal the mouth. If the cut is provided, it is impossible to prevent steam or hot water from entering during sterilization. Therefore, there is a problem that the method of providing a cut in the rubber stopper in advance cannot be used depending on the type of the chemical solution / drug filled in the chemical solution container.
[0004]
[Problems to be solved by the invention]
As a sealing material that solves the above problems, Japanese Patent Application Laid-Open No. 5-124664 discloses a cover film made of a somewhat elastic material having low tear strength, such as aluminum foil, on the top surface of a sealing body provided with a cut portion. An example in which is provided is disclosed (see column [0022] of FIG. 4 and FIG. 4). According to this sealing material, the sealing material as a whole retains sufficient hermeticity while maintaining the piercing property of a cylindrical member whose tip is not sharp, such as the tip of a syringe (syringe) of a syringe. be able to.
[0005]
However, a metal thin film such as an aluminum foil used as a material for the cover film has a characteristic that there is a risk of generating cocoon-like metal scraps (so-called burrs) by puncturing with a syringe or the like of a syringe. There is also a risk that it will enter the body via chemicals. Moreover, the problem at the time of an incineration process is also anxious about containing a metal.
On the other hand, when a thin film made of a resin film is used as a cover film instead of a metal thin film such as an aluminum foil, there is generally no risk of debris such as burrs.
[0006]
However, the resin film is usually a material having a large elongation. For this reason, for example, as shown in FIG. 6, when the sealing material 80 is punctured with a cylindrical member whose tip is not sharp, such as the tip 31 of the syringe 30 of the syringe, the elastic body 11 provided with the slit 14 is penetrated. However, the cover film 85 has a problem that it cannot be cleaved because the resin film itself stretches. On the other hand, if an attempt is made to reduce the elongation by increasing the thickness of the resin film, the tubular member cannot be cleaved.
[0007]
  Therefore, the object of the present invention is to allow piercing even a member whose tip is not sharp, such as the tip of a syringe of a syringe or a hollow blunt needle, and before piercing the member. An elastic sealing body with slits that can maintain sufficient sealing performanceEquipped with a chemical containerIs to provide.
[0008]
[Means for Solving the Problems and Effects of the Invention]
  According to the present invention for solving the above problemsChemical containerAn elastic body having a slit extending along the insertion direction of the tubular member, and the elastic bodyTubeCover the surface including the penetrating position of the memberTreeSlit elastic sealing body comprising a fat filmAnd a container body that contains a drip solution or an injection solution, and the elastic sealing body has a bottom surface that includes the penetrating position. It is arrange | positioned at the said opening part, The said resin film is a laminated body of the layer which consists of a cyclic olefin type polymer, and the layer which consists of a polyolefin-type polymer.
[0009]
According to the elastic sealing body with a slit according to the present invention, since the slit is provided in advance in the elastic body constituting the elastic sealing body, even if the tip of the cylindrical member is not sharp, it is elastic. Can penetrate the body. Therefore, for example, even if the injection needle is not connected to the distal end portion of the syringe of the syringe, the distal end portion (cylindrical portion where the distal end is not sharp) is directly pushed in at the puncture position of the elastic member, thereby being elastic. Can penetrate the body.
[0010]
Moreover, since the resin film covering the elastic body includes a layer made of a cyclic olefin polymer and has a low tear strength, a cylindrical member whose tip is not sharp like the tip of a syringe Even so, the cleavage can be easily caused by the pressing force at the time of pushing it in.
Therefore, the elastic sealing body with slits according to the present invention can be used not by a hollow needle having a sharp tip but by a hollow member having a sharp tip. Further, by arranging the elastic sealing body with slits of the present invention at the mouth of the drug solution container, etc., for example, without connecting a hollow needle with a sharp tip to the cylinder of the syringe, the internal solution can be directly removed from the syringe. Injection, mixing can be performed, or an internal solution such as a drug solution container can be collected with the syringe.
[0011]
  Moreover, according to the elastic sealing body with a slit concerning this invention, the cylindrical member of an elastic bodyContinuityThe surface including the through position (the mouth of the chemical containerPartWhen placedTo the bottomSurface)RingSince a resin film including a layer made of an olefin polymer is coated, even if a slit penetrating the elastic body is provided, a chemical solution container equipped with the elastic sealing body with the slit is provided.VesselmouthPartThere is no loss of sealing performance.
[0012]
  Therefore, the slit-sealed elastic sealing body of the present invention is provided with the mouth of the infusion container.PartBy applying, while maintaining the piercing property that can be easily inserted even with a cylindrical member whose tip is not sharp, the sealing property before the resin film is cleaved (before the elastic sealing body is used) It is possible to provide a mouth closing system that can be sufficiently secured and used for sterilization or the like as it is.
  Moreover, it is included in the resin filmRingOlefin polymers have physical properties such as excellent gas barrier properties and water vapor barrier properties, and are excellent in heat resistance.VesselIt is suitable for maintaining the sealing property. In addition, because it has excellent chemical resistance and there is no problem of elution, etc., even if a resin film is formed directly on the surface that is in contact with the chemical solution / drug, it may become an obstacle to the use of the chemical solution container etc. Absent. In addition,RingSince the olefin polymer is a material that does not generate toxic gas even when incinerated, it is not bothered by disposal after using the elastic sealing body.
[0013]
  As is clear from these reasons, the slit-sealed elastic sealing body according to the present invention is provided in the mouth of the chemical container.PartAs a sealing member, especially chemical solutionVesselAs one that enhances safety when used, it is preferably used in medical practice. The resin film in the elastic sealing body with slits of the present invention is a laminate of a layer made of a cyclic olefin polymer and a layer made of a polyolefin polymer.The Moreover, it is preferable that the said resin film is a 3 layer film which consists of a layer which consists of a cyclic olefin polymer, and a layer which consists of a polyolefin polymer laminated | stacked on both surfaces of the said layer.
[0014]
  The cyclic olefin polymer in the resin film has a glass transition temperature of 80 ° C.~ 150 ° CInTheBy using such a cyclic olefin polymer, physical properties such as tear strength, strength and stretchability of the resin film can be adjusted to an appropriate range.
  In addition, the cyclic olefin polymer has a tensile elongation at break.1-4%AhTheBy using such a polymer, the degree of cleavage of the resin film can be adjusted to an appropriate range.
[0015]
  In the present invention, “tensile elongation at break” indicates an elongation amount (%) corresponding to the tensile fracture strength, and is measured in accordance with ASTM D638.
  The resin film has an overall thickness of 20 to 20100μmThe Also,The thickness of the layer made of the cyclic olefin polymer is preferably 10 to 90% of the entire resin film. The degree of cleavage of the resin film can be adjusted to an appropriate range by adjusting the thickness of the resin film and the ratio of the thickness of the layer made of the cyclic olefin polymer to the above range.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Next, the slit-containing elastic sealing body according to the present invention will be described in detail with reference to the drawings.
[Embodiment of Elastic Sealed Body with Slit]
As one embodiment of the elastic sealing body 10 with a slit according to the present invention, for example, as shown in FIG. 1, an elastic body 11 having a slit 14 extending along the insertion direction x of the tubular member, And a resin film 15 covering the surface 13 including the penetrating position 17 of the cylindrical member.
[0017]
In FIG. 1, the elastic sealing body 10 with a slit is shown in a state where it is arranged in the mouth portion 20 such as a chemical solution container. The surface 12 of the elastic body 11 is a surface including the puncture position of the cylindrical member 16, and becomes a top surface when disposed in the mouth portion 20 of the chemical solution container. On the other hand, the surface 13 of the elastic body 11 is a surface including a portion (penetration position) 17 through which the cylindrical member penetrates the elastic body 11, and becomes the bottom surface when disposed in the mouth portion 20 of the chemical liquid container.
In the embodiment shown in FIG. 1, the slit 14 penetrates from the surface 12 including the puncture position 16 of the elastic body 11 to the surface 13 including the penetrating position 17. However, since one of them (the surface 13 including the penetrating position 17) is covered with the resin film 15, the slit-shaped elastic sealing body 10 as a whole is in a state where the mouth portion 20 is sealed.
[0018]
According to the elastic sealing body 10 with a slit shown in FIG. 1, for example, a cylindrical member whose tip is not sharp like a tip of a syringe of a syringe is directed from the puncture position 16 to the penetration position 17 of the elastic body 11 ( Even when pushed in (in the insertion direction x), the resin film 15 can be cleaved to penetrate the entire elastic sealing body 10 (as shown in FIG. 6, the cover film 85 only expands). And does not cause the phenomenon of not cleaving).
[0019]
In the embodiment shown in FIG. 1, the piercing property when penetrating through the elastic body 11 by a cylindrical member whose tip is not sharp is ensured by the slit 14 penetrating the elastic body 11. Moreover, the piercing property of the resin film part is ensured by the fact that the resin film includes a layer made of a cyclic olefin polymer.
According to the slit-sealed elastic sealing body 10 shown in FIG. 1, the surface 13 side including the penetrating position 17 of the elastic body 11 is covered with the resin film 15 including a layer made of a cyclic olefin polymer. For example, it is possible to prevent the chemical liquid filled in the chemical liquid container or the like from directly contacting the elastic body 11 constituting the elastic sealing body 10. In addition, since the cyclic olefin polymer is a material having excellent chemical resistance and no problem of eluate as described above, it can be suitably used for applications that directly come into contact with chemicals and chemicals. .
[0020]
As other embodiment of the elastic sealing body containing a slit which concerns on this invention, what is shown, for example in FIGS. 2-4 is mentioned.
The elastic sealing body 10a with a slit shown in FIG. 2 has an elastic sealing body with a slit shown in FIG. 1 except that the slit 14a does not penetrate the elastic body 11a and a thin portion 18 is formed in the vicinity of the puncture position 16. The same as the stationary body 10. If the strength (particularly tear strength) of the thin-walled portion 18 can be easily cleaved by a cylindrical member whose tip is not sharp, as in the embodiment shown in FIG. It does not have to penetrate. In FIG. 2, as in FIG. 1, the slit-like elastic sealing body 10 a is shown in a state where it is arranged in the mouth portion 20 such as a chemical solution container. The same applies to the embodiments shown in FIGS. 3 and 4 below.
[0021]
In the case where the slit 14a is not exposed to the surface 12 side as in the case of the elastic sealing body 10a with a slit shown in FIG. 2, the elastic body 11a is formed for the purpose of clarifying the puncture position 16 of the elastic body 11a. It is preferable to provide a mark such as a recess 19 or a protrusion on the surface 12.
3 includes an elastic body 11b having a slit 14b and a resin film 15 that covers the surface 12 of the elastic body 11b including the puncture position 16 of the cylindrical member. is there.
[0022]
In the embodiment shown in FIG. 3, the slit 14 b penetrates from the surface 12 including the puncture position 16 of the elastic body 11 b to the surface 13 including the penetrating position 17. However, since one of the surfaces (surface 12 including the puncture position) is covered with the resin film 15, the slit-shaped elastic sealing body 10b as a whole is in a state where the mouth portion 20 is sealed.
According to the slit-sealed elastic sealing body 10b shown in FIG. 3, the surface 12 including the puncture position 16 of the elastic body 11b is coated with the resin film 15 including a layer made of a cyclic olefin polymer. For example, it is possible to eliminate the possibility that dust attached on the surface 12 of the elastic body 11b may enter the slit 14b from the puncture position 16 during storage of the chemical solution container.
[0023]
4 includes an elastic body 11c having a slit 14c, a resin film 15a covering the surface 12 of the elastic body 11c including the puncture position 16 of the cylindrical member, and a cylindrical member. And a resin film 15b covering the surface 13 including the penetrating position 17.
In the embodiment shown in FIG. 4, the slit 14 c penetrates from the surface 12 including the puncture position 16 of the elastic body 11 b to the surface 13 including the penetration position 17. However, since both the surfaces 12 and 13 are covered with the resin films 15a and 15b, the slit-shaped elastic sealing body 10c as a whole is in a state where the mouth portion 20 is sealed.
[0024]
According to the slit-sealed elastic sealing body 10c shown in FIG. 4, a layer made of a cyclic olefin polymer on both the surface 12 side including the puncture position 16 and the surface 13 side including the penetrating position 17 of the elastic body 11c. Since the resin films 15a and 15b containing the liquid are covered, for example, the direct contact between the elastic body 11c and the chemical liquid filled in the chemical liquid container or the like can be prevented, and the contamination at the puncture position 16 can be prevented. it can.
[Resin film]
In the slit-sealed elastic sealing body of the present invention, the resin film used to coat the surface of the elastic body has a low tear strength, and the tip of the syringe syringe tip (portion to which the injection needle is connected) It is required that a cylindrical member that is not sharp can be easily cleaved.
[0025]
The above-described characteristics that can easily cause cleavage even by a cylindrical member having a sharp tip can be achieved, for example, by using a resin film including a layer made of a cyclic olefin polymer.
In addition, such a resin film is made of a cyclic olefin polymer in order to ensure sufficient mechanical strength and the like at the stage before the resin film is cleaved, and to prevent the resin film from being cracked. A laminate of a layer and a layer made of a polyolefin polymer such as polyethylene (PE) or polypropylene (PP) is preferable.
[0026]
(Cyclic olefin polymer)
Examples of the cyclic olefin polymer used in the present invention include a copolymer of ethylene and dicyclopentadiene or norbornene compound, and a hydrogenated product thereof. Among these, it is preferable to use a hydrogenated product of a copolymer of ethylene and a norbornene compound.
As the hydrogenated product, for example, the general formula (1):
[0027]
[Chemical 1]

[0028]
[In formula (1), R¹And R²Are the same or different and each represents hydrogen, a hydrocarbon residue, or a polar group such as halogen, ester, nitrile, or pyridyl. R¹And R²May combine with each other to form a ring. m is an integer of 1 or more, and n is 0 or an integer of 1 or more. ]
And / or general formula (2):
[0029]
[Chemical 2]

[0030]
[In formula (2), R^ThreeAnd R^FourAre the same or different and each represents hydrogen, a hydrocarbon residue, or a polar group such as halogen, ester, nitrile, or pyridyl. R^ThreeAnd R^FourMay combine with each other to form a ring. x and z are integers of 1 or more, and p is 0 or an integer of 1 or more. ]
The polymer which has the structural unit represented by these can be mentioned.
The polymer having the structural unit represented by the general formula (1) is obtained by polymerizing one or more monomers by a known ring-opening polymerization method, and hydrogenating the ring-opened polymer thus obtained according to a conventional method. It is a thing.
[0031]
Specific examples of the polymer include a hydrogenated polymer manufactured by Nippon Zeon Co., Ltd. [trade name “ZEONOR”, specific gravity 1.01, MFR 70 g / 10 min (190 ° C.), glass transition temperature (Tg) 100 ° C.], A trade name “ARTON®” manufactured by Nippon Synthetic Rubber Co., Ltd. may be mentioned.
The polymer having the structural unit represented by the general formula (2) is obtained by addition copolymerization of one or more norbornene monomers as a monomer and ethylene by a known method, and / or Or this is hydrogenated according to a conventional method.
[0032]
Specific examples of the polymer include [trade name “Apel 6509”, specific gravity 1.02, MFR 40 g / 10 min (190 ° C.), glass transition temperature (Tg) 80 ° C.], manufactured by Mitsui Chemicals, Inc., manufactured by TICONA Product name “TOPAS®” and the like.
Since the hydrogenated product of the copolymer including the polymer having the structural units represented by the general formulas (1) and (2) is a saturated polymer, it is inserted into a cylindrical member having a sharp tip. Not only is it excellent in permeability, it is also excellent in terms of gas shielding properties, moisture shielding properties, heat resistance, and stability.
[0033]
The cyclic olefin polymer has a glass transition temperature (T_g) Is preferably 80 ° C. or higher, more preferably 105 to 150 ° C. Glass transition temperature T_gWhen the temperature is lower than 80 ° C., the elongation characteristic of the resin film increases, and there is a possibility that it cannot be easily cleaved by a cylindrical member whose tip is not sharp. On the other hand, the glass transition temperature T_gIf the temperature exceeds 150 ° C., the fragility of the cyclic olefin-based polymer increases, which may make it unsuitable for use in coating an elastic body.
[0034]
The molecular weight range of the cyclic olefin polymer is preferably 10,000 to 100,000 in the number average molecular weight <Mn> measured by gel permeation chromatography (GPC) analysis using cyclohexane as a solvent. More preferably, it is 10,000. When the unsaturated bond remaining in the molecular chain of the copolymer is saturated by hydrogenation, the hydrogenation rate is set to 90% or more, preferably 95% or more, particularly preferably 99% or more. Is done.
[0035]
The tensile rupture elongation (%) of the cyclic olefin polymer is preferably 5% or less, more preferably 1 to 4%, as measured according to ASTM D638. If the tensile elongation at break exceeds 5%, the elongation characteristics of the resin film increase, and there is a possibility that it cannot be easily cleaved by a cylindrical member whose tip is not sharp.
(Other polymers)
In the elastic sealing body with slits of the present invention, as described above, the resin film used to coat the surface of the elastic body not only uses a layer composed of a cyclic olefin polymer alone, but also, for example, a cyclic film. A laminate of a layer made of an olefin polymer and a layer made of a polyolefin polymer can be used.
[0036]
Examples of the polyolefin polymer include polyethylene (PE) and polypropylene (PP).
Examples of the resin constituting the laminate with the layer made of the cyclic olefin polymer include, in addition to the polyolefin polymer, ethylene-vinyl acetate copolymer, polyester, polyamide and the like.
(Physical properties of resin film)
In the slit-sealed elastic sealing body of the present invention, the thickness of the resin film covering the surface of the elastic body is suitably set in the range of 20 to 500 μm from the viewpoint of achieving both tear strength and mechanical strength. And it is more preferable to set it as the range of 20-100 micrometers. In this case, the ratio of the thickness of the layer made of the cyclic olefin polymer is preferably 10 to 90%, more preferably 10 to 50% of the entire resin film.
[0037]
If the thickness of the resin film exceeds the above range or the ratio of the thickness of the cyclic olefin polymer to the entire resin film falls below the above range, the influence of the resin other than the cyclic olefin polymer is ignored on the entire resin film. And the elongation of the resin film may increase. On the other hand, if the thickness of the resin film is less than the above range, or the ratio of the thickness of the cyclic olefin polymer in the entire resin film exceeds the above range, the resin film may be weakened.
[0038]
[Elastic body]
For the elastic body in the elastic sealing body with slits according to the present invention, various materials used as stoppers in conventional chemical liquid containers and the like can be used. Examples thereof include rubbers such as natural rubber, silicone rubber, butyl rubber, isoprene rubber, and styrene-butadiene rubber, and elastic members such as thermoplastic elastomers.
When the slit-sealed elastic sealing body of the present invention is applied to a cap such as an infusion container, in order to integrally mold the outer frame body and the elastic body of the cap, thermoforming is possible together with the plastic forming the outer frame body. Preferably, a thermoplastic elastomer is used as the elastic body. In this case, the cap manufacturing process can be simplified.
[0039]
Examples of the thermoplastic elastomer usable in the present invention include a styrene-ethylene / butylene-styrene block copolymer (SEBS), a styrene-butadiene-styrene block copolymer (SBS), and a styrene-isoprene-styrene block copolymer. (SIS), styrene-ethylene / propylene-styrene block copolymer (SEPS), modified SEBS such as maleic acid modification, styrene-ethylene / butylene block copolymer (SEB), styrene-ethylene / propylene block copolymer ( SEP) and the like; olefin elastomers such as ethylene-propylene block copolymers; polyurethane elastomers and the like.
[0040]
The characteristics of the elastic body that can be used in the present invention are not particularly limited. In general, the elastic body is not so strong or hard that it is difficult to penetrate the medical injection needle, and during normal storage. What is necessary is just to have the intensity | strength of the grade which does not deform | transform easily or break.
The elastic body usable in the present invention preferably has a JIS A hardness [spring hardness Hs (JIS A) measured by the method described in JIS K 6301] of 20 to 70, preferably 30 to 50. More preferably. In addition, the compression set of the elastic body is a value measured by the method described in JIS K 6301 [compression set rate CS (%), Heat treatment temperature / time: 70 ° C., 22 hours] is preferably 30 or less.
[0041]
〔slit〕
In the elastic sealing body with a slit according to the present invention, the slit formed inside the elastic body may be any one that can easily insert a cylindrical member whose tip is not sharp. Accordingly, the width, length (ratio of the total length of the elastic body), shape, etc. are not particularly limited, but usually the shape of the cross section of the slit portion (the shape appearing on the surface of the elastic body) is a straight line. It is appropriate to set it to have a (−) shape and a width of 0.5 to 10 mm, preferably 1 to 7 mm, more preferably about 2 to 4 mm.
[0042]
The width of the slit and the like can be appropriately changed depending on the shape of the cylindrical member to be used. Further, the shape is not limited to the above. Although not limited to this, it is preferable to design the slit portion to be closed by the repulsive force of the elastic body when the cylindrical member or the like is not inserted.
[0043]
【Example】
Next, an Example and a comparative example are given and this invention is demonstrated.
[Manufacture of elastic sealing body with slits]
Example 1
A slit 14 is provided in the center of a cylindrical rubber plug (elastic body 11, made of natural rubber, JIS A hardness 35) with a thickness of 5 mm and a diameter of 20 mm. (See FIG. 1).
[0044]
Next, linear low-density polyethylene is formed on both sides of a film of an ethylene / tetracyclododecene copolymer (trade name “Apel APL6013” manufactured by Mitsui Chemicals, Inc., glass transition temperature 125 ° C., elongation at break 3%). A three-layer film (resin film 15) formed by laminating a film of [LLDPE, density 0.920] is used, and this three-layer film is a surface 13 of the rubber stopper with a slit including the through-hole 17 of the tubular member. The elastic sealing body 10 with a slit was obtained by covering with.
[0045]
The total thickness of the three-layer film was 30 μm, and the ratio of the thickness of each film constituting the three-layer film was 30%, 40%, and 30% in order from one surface.
Comparative Example 1
One surface of a rubber plug with slits similar to that used in Example 1 was coated with a resin film having a thickness of 30 μm made of LLDPE (supra) to obtain an elastic sealing body with slits.
[0046]
[Cleavage test of coated film]
Test example 1
The following tests were conducted on the elastic sealing body 10 with slits obtained in Example 1 and Comparative Example 1.
From the puncture position 16 of the tubular member (the exposed position of the slit 14 on the surface 12 where the resin film 15 is not provided), the tip of the syringe of the syringe (a metal hollow needle or the like) is connected to the elastic body 11 The columnar part) was inserted, and the presence or absence of cleavage of the resin film 15 was confirmed.
[0047]
The distal end portion 31 of the syringe 30 used in the above test had an outer diameter D of 4.2 mm, an inner diameter d of the hollow portion 32 of 1.85 mm, and a length T of 9 mm (see FIG. 5B).
Moreover, the said test was done about ten samples in both Example 1 and Comparative Example 1.
As a result, in the elastic body with slits obtained in Example 1, the resin film was cleaved for all samples, whereas in the elastic body with slits obtained in Comparative Example 1, as shown in FIG. Since the resin film 15 stretched, it was not possible to cause cleavage even when the distal end portion 31 of the syringe was inserted all the way.
[0048]
Test example 2
About the resin film used in Example 1 and Comparative Example 1 above, it is necessary to break through at the tip 31 (D = 4.2 mm, d = 1.85 mm, T = 9 mm, cylindrical shape) of the syringe 30 described above. The force was measured at a speed of 200 mm / min by an autograph [“AGS-100D” manufactured by Shimadzu Corporation].
In the measurement, the resin film 15 used in Example 1 and Comparative Example 1 was used by being sandwiched between two plates 90 having a hole having a diameter of 6.5 mm. Further, the tip 31 of the syringe was adjusted so that it abuts the resin film 15 at the central portion of the hole and the tip 31 hits the resin film 15 perpendicularly.
[0049]
The measurement was performed on 10 samples for both of the resin films used in Example 1 and Comparative Example 1.
As a result, all of the resin films used in Example 1 were able to break through the tip of the syringe whose tip was not sharp. The average force required for cleaving the resin film was 0.7 kgf. On the other hand, the resin film used in Comparative Example 1 only stretched when pressed by the tip of the syringe, and none of the samples was cleaved.
[Brief description of the drawings]
FIG. 1 is a view showing an embodiment of an elastic sealing body with slits according to the present invention, in which (a) is a cross-sectional view thereof and (b) is a plan view thereof.
FIG. 2 is a cross-sectional view showing another embodiment of an elastic sealing body with slits according to the present invention.
FIG. 3 is a cross-sectional view showing still another embodiment of an elastic sealing body with slits according to the present invention.
FIG. 4 is a cross-sectional view showing still another embodiment of the elastic sealing body with slits according to the present invention.
FIGS. 5A and 5B are explanatory views showing a method of a tear strength measurement test for a resin film, and FIGS. 5B and 5C are partially enlarged views for explaining the shape of a tip portion of a syringe of a syringe. FIGS. is there.
FIG. 6 is an explanatory view showing a problem of a conventional elastic body with a slit provided with a resin film.
[Explanation of symbols]
10 elastic sealing body with slit, 11 elastic body, 14 slit, 15 resin film, 16 puncture position, 17 penetration position, x insertion direction

Claims (3)

An elastic sealing body with a slit, comprising: an elastic body having a slit extending along the insertion direction of the tubular member; and a resin film covering a surface including a through position of the tubular member of the elastic body;
It has a mouth portion sealed by the elastic sealing body, and comprises a container main body for storing a drip solution or an injection solution,
The elastic sealing body is disposed in the mouth so that a surface including the penetrating position is a bottom surface, and the resin film is a layer made of a cyclic olefin polymer and a layer made of a polyolefin polymer laminate der with is,
The glass transition temperature of the cyclic olefin polymer is 80 ° C to 150 ° C,
The cyclic olefin polymer has a tensile elongation at break of 1 to 4%,
Overall thickness of Ru 20~100μm der drug solution container of the resin film.   The chemical solution container according to claim 1, wherein the resin film is a three-layer film including a layer made of a cyclic olefin polymer and a layer made of a polyolefin polymer laminated on both surfaces of the layer. Drug solution container according to claim 1 or 2 thickness of the layer made of the previous SL cyclic olefin polymer is 10-90% of the total resin film.

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